Rubber

“ Chemistry Chemistry and Technology of Rubbers ”  ”  Quingdao  09.05.- 15.05.2011 15.05.2011

Werner Obrecht 

The attached  The attached  files of files of my lecture  my lecture are  lecture are my  are my personal my personal property . For the exclusive  the exclusive  personal use , an elctronic copy  elctronic copy of copy of the files  the files will files will be made  be made available  made available to available to the  participants of the lecture . It is prohibited to make copies  or multiply the files  for commercial use .

Chemistry and Technology of Rubbers  1.

Overview on Rubbers, Definitions, Definitions, Market, Properties, Production and Applications  Applications 

2.1. 2.1. Nat Natura ural Rubb ubber  2.2. 2.2. Synt Synthe heti tic c Poly Polyis isop opre rene  ne  3. 3.1. 3.2. 3.3.

Overview on Emulsion Rubbers  Emulsion-Styrene/Butadiene-Rubber  Polychloroprene  Nitrile Nitrile Rubber  Rubber 

4. Overview on Solution Rubbers 4.1. Overview on Polybutadiene  Polybutadiene  4.2. Li-Polybu Li-Polybutadi tadiene ene and Solution Solution-Sty -Styrene rene/Buta /Butadien diene-Ru e-Rubber bber with an Emphasis Emphasis on Integral Rubber  4.3. Chemistry Chemistry and Producti Production on Technolo Technology gy of High cis-1,4-B cis-1,4-BR R with with a S Speci pecial al Emphasis Emphasis on Nd-BR  4.4. Ethylene/Propene-CoEthylene/Propene-Co- und Terpolymers  4.5. Butyl- and Halobutyl Rubber  5. 5.1. 5.1. 5.2. 5.2. 5.3. 5.3. 5.4.

High Performance Rubbers  Flu Fluoro oro Rub Rubber  Sili Silico con n Rubb Rubber er Hydr Hydrog ogen enat ated ed Nitr Nitril ile e Rubb Rubber er Ethylene/Vinylacetate-Copolymers 

6.

Thermoplastic Elastomers 

7.

Test Questions  

1. Overview on Rubbers, Definitions , Market, Properties , Production , and Applications 

“Elastomer“ and “Thermoplastic • Definition of the Terms “Rubber“, “Elastomer“ Elastomer“  • Nomenclature  • Market • Important Rubbers and Property Profiles  • Rubber Producers  • Production Technologies  • Producers of Synthetic Rubber and Production Capacities  • Available Vulcanization Methods and Network Properties 

Standard Terminology Relating to Rubber  (ASTM D 1566 - 98 )  materi rial al that that is capa capabl ble e of rubber, n-a  mate reco recov verin ering g from from larg large e def defor orma mati tion ons s quic qu ickl kly y and and for forci cibl bly, y, and and can can be, be, or or alre alread ady y is mo modi difi fied ed to a stat state e in which which it is essentially insoluble (but can swell) swell) in boi boiling ling solve solvent, nt, such such as as benzen zene, methyl ethyl ketone, or ethan ethanol ol tolue toluene ne azeotr azeotrope ope..

DISCUSSION

- A rubber in its modified state, fr free of diluents, retrac tractts wit within hin 1 min min to le less than han 1,5 times its original le length after being stre stretc tche hed d at room room temp temper erat atur ure e (18 (18 to 29° 29°C) to twic twice e its its leng length th and and hel held d for for 1 min befor before e release release..

30

1 min 

25 20    ]   a    P 15    M    [   s 10   s   e   r    t    S 5

rubber

1 min 

0 0

50 Elonga Elongatio tion n [%] [%]

100

Comparison of Materials According to ASTM D 1566 

ε =ε

300    ]    %    [   n 200   o    i    t   a   g   n   o    l    E    l   a 100   u    d    i   s   e    R

0

residual

TPO Definition of „Rubber“ accor accordin ding g to ASTM ASTM D 1566 1566 - 98

TPV

Thermoplastic Elastomers

SBS

0

100

200

NR/BR ba NR/BR based sed tyr tyre e tr tread ead NR gum st stock ock 300

Elonga Elongatio tion n (ε) [%]

My personal Definition of “ Unvulcanized  Unvulcanized Rubber “  “,  “ Vulcanized Vulcanized Rubber “  “,  “ Elastomer  Elastomer “  “,  and “ TPE  TPE “  “  Unvul Unvulcan caniz ized ed Rubb Rubber er is an uncr uncros ossl slin inked ked,, amor amorph phou ous s or part partia iall lly  y  crys cr ysta tall llin ine e poly polyme merr (syn (synth thet etic ic or natu natura ral) l) wit with h a Tg < temper temperat atur ure e of use  use  Vulcan Vulcanize ized d Rubber Rubber (or: (or: „Cross „Crosslin linked ked Rubber“ Rubber“ or „Elasto „Elastome mer“) r“) is obtain obtained  ed  by chemica chemically lly crossli crosslinkin nking g (vulca (vulcaniz nizati ation) on) of of unvulc unvulcani anized zed rubber  rubber  Thermop Thermoplas lastic tic Elasto Elastomer mers s (TPE) (TPE) are physica physically lly crossl crosslink inked ed rubber rubbers  s  Thermo Thermopla plasts sts are unvulc unvulcani anized zed polyme polymers rs (synth (syntheti etic c or natura natural)  l) with a softening softening temper temperatu ature re (Tg oder oder Tm) > temper temperatu ature re of use  Thermo Thermoset set resins resins (or duropl duroplast asts) s) are highly highly crossl crosslink inked ed polymer polymers s which which do not soften soften with  with  increasing increasing temperatu temperature, re, but will deterior deteriorate ate at high temperatur temperatures  es 

In Engli English sh,, the the term term „Rub „Rubbe ber“ r“ is ambi ambigu guou ous s as thi this s term term refe refers rs to unv unvulc ulcan aniz ized ed as well as to vulcani vulcanized zed rubber: rubber: • rubber tree • natura naturall rubbe rubberr

unvulcanized (=uncrosslinked) (=uncrosslinked) rubber

• rubber rubber bo boot ot

vulcanized (=crosslinked) (=crosslinked) rubber

Tgs of Polymers with a Saturated C -  -C   Main Chain 

CH3

CH3

O

O

O

O

CH3

Si

Si

O

Si

O

-18°C

Polyvinylacetate

+30°C

Polystyrene (ataktisch / amorph)

+100°C

Silicon Rubber

-120°C

O O

CH3

O

Polypropylene (atactic (atactic / amorphou amorphous) s)

O

O

CH3

O

O

O O

~ -130°C

CH3

O

O O

CH3

Polyethylene

Si

CH3

O

Si

O

Si

O

Si

O

Tgs of Polymers with an Unsaturated C=C Main Chain  Polybutadiene

-115°C (100% 1,4-cis)

Polyisoprene

-75°C (100% 1,4-cis)

Polychloroprene

-45°C (100% 1,4-trans)

Nitrile Nitrile Ru Rubb bber er

-50°C bis -5°C (depending (depending on ACN-content) ACN-content)

Cl

Cl

Cl

Cl CN

CN

Influence of Tg on Rebound of Vulcanized Rubbers ( 50  )  50 phr carbon  black , without plasticizer  80 1,4-cis BR

SBR

NBR

NR

   ] 60    %    [    d   n   u   o 40    b   e    R

EPDM

IIR

20

0 -75

-50

-25

0

25

50

75

100

Temperature [°C] • • • •

With increasing temperature rebound elasticity passes throug a minimum The temperature at the rebound minimum correlates with Tg, except for butyl rubber The temperature at the rebound minimum is significantly higher than the Tg of the respective rubber In this respect, butyl rubber performs different from the other rubbers

Source: Butyl And Halobutyl Compounding Guide For Non-Tyre Applications, 12/92 Bayer AG -KA

Schematic Presentation of the Dependence of the  Shear Modulus on Temperature  NR (raw rubber)

10000

NR/5 phr DCP Polystyrene

1000

   ]   a    P 100    M    [   s   u    l   u 10    d   o    M   r   a 1   e    h    S 0,1 -150

-100

-50

0

50

Temperature [°C]

100

150

200

Designation of Rubbers (DIN/ISO 1629)  ClassChemical Description Designation

Examples

M

Rubbers with fully saturated main chain (polymethylene type rubbers)

CM, CSM, EAM, ACM, EPM, EPDM,

N

Nitrogen containing rubbers

NBR, HNBR

O

Rubbers with oxygen in the main chain (Polyether type rubbers)

CO, ECO, GPO

Q

rubbers with a polysiloxane main chain

MQ, MVQ, PMVQ, FMQ

R

Rubbers with an unsaturated main chain (double bond containing rubbers)

NR, SBR, BR, NBR, CR, IIR

T

Rubbers with sulfur in the main chain (Polythioether type rubbers)

OT, EOT

U

Rubbers which contain carbon, nitrogen and oxygen in the main chain (polyurethane type rubbers)

AU, EU

Z

Rubbers with phosphorus and oxygen in the main chain (polyphosphazenes)

FZ

Abbreviations (DIN / ISO 1629) and Examples  BR

Butadiene-Rubber

CR

Chloroprene Rubber

CM

Chlorinated Polyethylene

CSM

Chlorosufonated Polyethylene

EPM

Ethylene/Propylene-Rubber

EPDM

Ethylene/Propylene/Diene-Rubber

ENR

Epoxidised Natural Rubber

IR

Synthetic Polyisoprene

IIR

Butyl rubber

NR

Natural Rubber

NBR

Nitrile-Butadiene-Rubber

SBR

Styrene-Butadiene-Rubber (E-SBR und S-SBR)

FPM

Fluoro Rubber (DIN / ISO 1629)

FKM

Fluoro Rubber (ASTM D-1418)

Annual Consumption of NR and Synthetic Rubber  14000    ]   s 12000   n   o    t   c    i   r    t   e 10000   m    0    0    0 8000    1    [   n   o    i    t   p 6000   m   u   s   n   o    C 4000    l   a   u   n   n 2000    A

Natural Rubber Synthetic Rubber (Solid + Latex)

0 1920

1930

1940

1950

1960

1970

1980

1990

2000

2010

2020

Sources: IRSG (International Rubber Study Group, Rubber Statistical Bulletin, Wembley, different editions Outlook for Elastomers 1996-97 (Wembley 1998) Rubber World, 21916 (1999) 13-14 European Rubber Journal (Quotation of IISRP Statistics), various editions LMC International Ltd, Rubber March 2005: Verbrauch 2001-2005 • • • • •

Application Areas of Solid Rubber ( rubber   )  rubber latex not included  Automotive 15% Modification of Plastics 14%

Tyres 45%

Cable and Wire Construction 3% 3%

Others 15% Machine building 5%

Price and Volume  of Rubbers ( without  without Latex) FZ FQ FKM HNBR Q AU/EU EVM

Volume Shares

High Performance Rubbers

General Purpose Rubbers: 82%

CR (0.3 Mio t)

  e   c    i   r    P

Special (0.5 Mio t)Rubbers

NBR (0.32 Mio t) IIR/X-IIR

Special Rubbers 17%

High Performance Rubbers 1%

EPM/EPDM (0.9 Mio t)

Shares in Turnover

BR

(2,8 Mio t)

SBR (2,7 Mio t) NR

General Purpose Rubbers: 60%

General Purpose Rubbers

(6.7 Mio t)

High Performance Rubbers 10%

Volume Source: Rubber World, 21916 (1999) 13-14

Special Rubbers 30%

Oil – and Temperature Resistance of Vulcanizates According to ASTM D 2000     ]    C    °    [   e   r   u    t   a   r   e   p   m   e    t   e   c    i   v   r   e   s  .   x   a   m

250

FKM

General GeneralPurpose PurposeRubbers Rubbers Special Rubbers Special Rubbers High HighPerformance PerformanceRubbers Rubbers

MVQ

225 FMVQ

200 FZ

175

40 % VAc

80 % VAc

EVM

ACM HNBR

150

CO/ECO NBR

44 % ACN

125 100

AEM 18 % ACN

CM CSM

(H)IIR

CR

EU

SBR

BR

AU

75

EPDM

NR

50 0

20

40

60

80

100

120

140

Degree of Swelling in ASTM-Oil Nr. 3 [Vol %]

no requirement

Evaluation of Vulcanizate Properties 

1

2

3

4

5

6

7

8

9

10

Improvement

Criteria of Evaluation: • Maximal Service Temperature • Low Temperature Flexibility • Oil Swell • Mechanical Properties • Ozone Resistance

Evaluation of Vulcanizate Performance*  Rubber

Max. Service Low Temperature temperature performance Tg Rating T max. Rating [°C]

NR SBR BR EPDM IIR NBR CR CM CSM EVM AEM ECO AU VMQ ACM HNBR FKM FMVQ FZ

-72 ca. -40 -120 -60 -60 -40 -39 -25 -25 -35 -35 -50 -30 -120 -35 -26 -20 -70 -65

[°C] 8 6 10 5 6 5

4 3 3 4 4 5 4 8 4 3 2 8 8

80 95 85 145 135 125 115 140 135 170 170 130 80 250 170 160 250 215 180

1 3 2 6 5 5 4 6 5 8 8 5 1 10 8 6 10 9 8

Mechanical Properties

Oil Swell (ASTM 2000-90)

Tear Rating Resistance [MPa] 25 22 20 24 15 22 22 15 16 14 15 15 25 10 14 25 14 10 16

10 7 6 8 3 7 7 4 4 3 4 4 10 1 3 10 3 1 4

Rating

Ozone Price Resistance Rating

[Vol.% ] >140 (70) 130 >140 >140 >140 20 bis 50 55 bis 65 80 80 20 bis 100 50 30 3 bis 25 30 bis 50 20 bis 40 15 bis 40 5 10 10

Performance Index Rating

[€/kg] 1 2 1 1 1 7 3 4

4 6

5 6 7 6 7 8 9 9 9

1 1 1 8 6 6 2 5 9 9 9 8 9 10 9 9 10 10 10

1,1 1,1 1,3 2,2 2,7 2,5 3,4 3,1 3,8 3,8 6,9 6,9 7,5 7,5 9,4 28,1 43,8 125 500

21 19 20 28 21 30 20 22 25 30 30 28 31 35 31 36 34 37 39

E-SBR and S-SBR may not be evaluated according to these criteria as SBR is designed for high Tgs (improvement of wet skid) *Ullmann‘s Encyclopedia of Industrial Chemistry, VCH Weinheim 1993, Vol. A23, Rubber 3. Synthetic; W. Obrecht „Introduction“

Correlation of Rubber Price and Vulcanizate  Performance  45 40

  x   e    d   n    I   e   c   n   a   m   r   o    f   r   e    P

FZ HNBR FKM

35

MVQ ACM AU NBREVMAEM EPDM ECO CSM CM IIR CR

30 25

NR BR SBR

20

FMVQ

15 10 5 0 0,1

1

10

100

1000

Price of Rubber [€/kg]

 Ranking of Top 10 Tyre Producers Rank

Company

Sales of Tyres

[Mio US $] 1 2 3 4 5 6 7 8 9 10 11

Michelin Bridgestone Goodyear * Continental Sumitomo** Pirelli Yokohama Cooper Tire Toyo Kumho Hankook

Sums: Total Sales:

13.425,0 12.950,0 12.470,0 4.901,0 2.598,2 2.534,5 2.272,2 1.705,3 1.247,6 1.246,5 118,9

55.469,2 68.500,0

Share of Tyres [%] 95,0 74,0 86,7 49,0 72,7 39,0 71,0 54,0 61,5 60,3 88,9

Return Market on Shares Sales in [%] Tyres [%] [%] 6,6 5,5 2,4 -4,2 7,7 6,1 5,7 3,4 2,1 -13,1 8,5

19,6 18,9 18,2 7,2 3,8 3,7 3,3 2,5 1,8 1,8 0,2

81,0 100,0

* Dunlop is not included ** Goodyear und Sumitomo operate in NA und WE in 75/25 joint ventures (Dunlop) Source: European Rubber Journal, vol. 184, no. 10, Oktober 2002, S. 28-30

Capitalization of Shares Sales

20

15

10

5

0

    e     n     o      t     s     e     g      d      i     r      B

    n      i      l     e      h     c      i      M

    r     a     e     y      d     o     o      G

     l     a      t     n     e     n      i      t     n     o      C

Source: FAZ 18.08.2003

 Ranking of Top 22 Producers of Technical  Rubber  Rubber Products ( without without Tyres ) Rank Company

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

Company Site

Hutchinson SA Bridgestone Corp. Freudenberg Group Tomkins plc. Parker Hannifin Cooper Tire & Rubber Trelleborg AB Continental AG Federal Mogul Corp. Goodyear Tire & Rubber NOK Inc. Tokai Rubber Industries Ltd. Metzeler Automotive Profile Syst. Toyoda Gosei Co. Ltd. Mark IV Automotive GenCorp. Inc. Ansell Ltd. Sumitomo Rubber Ind. Yokohama Rubber Co Ltd. Dana Corp. Toyo Tire Rubber Co. Ltd. Phoenix AG

Sales 2001 [Mio US$]

Return on Sales [%]

2156 2065 2060 1855 1500 1477 1446 1270 1160 1122 1120 987 900 897 812 808 759 750 703 695 670 662

* 0,8 3,7 5,7 5,7 2 2,9

France Japan Germany UK US US Sweden Germany US US Japan Japan Germany Japan US US Australia Japan Japan US Japan Germany

)

)

*

)

*

)

*

)

* 2,7 )

* 1,3 )

* 8,6 )

*

)

* 1,8 )

* 1,3 ) *

*) not available Source: European Rubber Journal 184,9 September 2002

Producers of Synthetic Rubber and Capacities  Lanxess 8.7% Exxon Mobil 5.7%

Others 30%

Goodyear 5.3% JSR Corporation 5.2%

Total: 12,097 KMT ISP Elastomers 2.2% Bridgestone/Firestone 2.8% Nizhnekamskneftekhim Inc. 3.1 Zeon Corporation 3.2% Petroflex 3.3% Michelin 3.3%

Sinopec 5.2% Sibur 5.1% Korea Kumho 4.8%

Dow 4.5% Polimeri 4.2%

Petro-China 3.6%

Source: R. J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008„Globalization of Synthetic Rubber Industry“

Chemical and Technological Features of Rubber Manufacturing Processes  Technological Features

Chemical Aspects

Emulsion E-SBR, CR, NBR, E-BR, ACM, FKM, EVM

Radical Polymerization

Solution

Dispersion

EVM

Bulk

Gas-Phase

AEM EVM

EVM

Ziegler/NattaPolymerization

BR, EPM, EPDM

Anionic Polymerization

BR, L-SBR. IR

Cationic olymerization

ECO, CO

IIR

Q

Polyaddition and Polycondensation

AU, EU

EU

AU

Polymer Modification

CIIR, BIIR, CM, CSM, H-NBR, FZ

CM, CSM, H-NBR*

EPM, EPDM

G-EPM G-EPDM G-BR**

BR* Q

Q

* Technology not established (only patents for the hydrogenation of NBR-latex) ** Technology not established (only patents for the gas phase polymerization of butadiene)

Flow Diagram of an EPDM Solution Process  Water Condenser Settler AzeotropicDestillation

Temperature: Temperature: Pressure: Pressure:

35-65°C 35-65°C 5-10 5-10bar bar

Residence ResidenceTime: Time: Solids Content: Solids Content:

30 30min min 10 -12 10 -12wt.% wt.%

Moisture MoistureContent: Content: <<33ppm ppm Waste Water

Flash Vessel

Condenser

Stripper Dewatering screw Waste Air

Ethene

Propene

Waste water

Reactor

Hexane

steam

External cooler

Purification

Oil

PHControl

Purification

Expeller

Antioxydant

Air bed Dryer Abwasser

Stripping aid

Dryer

Baler

Dryer

Modifier Reactivator Purification/  Drying

Purification/  Drying

EASC VOCl3

Hexane

ENB

Wrapper

Evaluation of Rubber Manufacturing Processes  Polymerization Process Solution

Dispersion Slurry 

Bulk

Gas-Phase

8

2

8

1

10

10

3

8

3

5

max. Solids Cont.

5

2

5

9

5

Stereoregularität

0

10

10

8

10

Waste Water

0

5

5

10

10

Waste Air

5

5

5

8

5

28

27

41

39

45

Aspect Viscosity Heat Removal

Sum Ranking: Prerequistes:

Emulsion

(Gas-Phase) > Dispersion > Bulk >> Emulsion > Solution comparable running times

Available Vulcanization Methods for the  Different Types of Rubber Example

Method of Vulcanization Sulfur

Peroxide

Resin

Other

X (X) X XX XX

X (X) (X) (X) (X) (X) XX XX

(X) (X) XX (X) (X) (X) (X) XX

“R“- Rubbers

NR BR CR SBR NBR HNBR IIR XIIR

XXX XXX XX XXX XXX XXX XX XX

“M“-Rubbers

EPDM EPM FKM CM

XX X

XX XXX XX X

X X

(X) XX X

MVQ

(X)

XX

(X)

XX

Other Rubbers

Influence of Vulcanization Method and Crosslinking  Density on Tensile Strength ( unfilled   )  unfilled NR -  -Vulcanisates   Vulcanisates  30

   ]   a    P    M    [ 20    h    t   g   n   e   r    t    S   e 10    l    i   s   n   e    T

Sx S1 C C C C

accelerated sulfur cure TMTD-cure peroxide cure high energy radiation cure

0 0,2

0,4

0,6

0,8

1,0

1,2

1,4

Reciprocal chain length 1/Mc x 10-4 • For high moduli and high tensile strength the vulcanization method and the length of rubber  chains between two crosslinking sites are decisive factors  • There is an optimum in tensile strength for Mc ~10.000 g/mol  • The tensile strength of rubber vulcanizates is only 1/100 - 1/1000 of the theoretical values  Sources: R. Houwink, H. K. de Dekker „Elasticity, Plasticity and Structure of Matter“ University Press, Oxford 3. Auflage (1971) K. Dinges, Kautschuk und Gummi. Kapitel 2 in H. Batzer „Polymere Werkstoffe“ Georg Thieme Verlag Stuttgart, New York (1984)

Schematic Presentation of the Deformation of a Rubber Network  Type of Bond

C-C

350

C-O

350

C-N

282

C-S-C

272

C-S-S-C

266

-S-S-S-S-

Type of Bond

covalent

TSexpt. = 1/100 - 1/1000 TStheor.

Bond Energy [ KJ/Mol]

physical

< 266

Bond Energy [KJ/Mol] 260 - 350 10 -

20

Influence of Compound Ingredients on Vulcanizate  Performance 

Rubber

•Oil Resistance •Low temperature flexibility •Resistance to heat- and ageing •Adhesion to cord, fibres and fabrics •Covulcanisation of layers •Tensile Strength •Elongation at break •Static and dynamic moduli •Shore A Hardness •Abrasion Resistance •Compression Set •Cut growth Resistance during dynamic stress •Heat-buid-up •Electical conductivity • ……. •…….. •…….. •…….

Vulcanization Method

Filler

2.1. Natural Rubber  Microstructure and Property Profile • NR-Market •

Designation of Grades and Glossary  – Development of Market and Price  – NR-Production, Areas of Application and Important Grades  – 

•

NR-Production NR-Latex and Latex Finishing  – General Features of NR and Hevea brasiliensis  – NR Grades and Specifications  – 

•

Chemical and Physical Properties of NR Solution Fractionation of NR  – M astication of NR  – Crystallization (Spontaneous-and Strain induced)  – 

•

Chemically Modified NR-Grades CV-Grades  – SP-Grades  – ENR-Grades  – 

•

Vulcanization of NR

NR: Microstructure and Property Profile 

Positive: Low price and good ratio of price versus performance • Standardized NR-grades • High level of mechanical properties (Tensile Strength, Modulus Abrasion) • Good Dispersability of Fillers (due to high viscosities at the start of the mixing cycle) • Low rolling resistance (truck tyres) • High abrasion resistance (truck tyres) • Slow spontaneous crystallization • Significant strain induced crystallization •

5

H3C

2

C CH2

1

3

CH 4 CH2

Negative: Poor resistance to swelling with hydrocarbons (fuels, oils and grease) • Need for mastication prior to compounding • bad wet skid performance • Poor resistance to heat ageing •

Physical Properties: Tg: 1,4-cis-content Tm (equilibrium): max. rate of crystallization: max. degree of crystallinity: Strain induced crystallization

-72°C ~ 97% + 30 °C -25°C ~ 30 %

NR: Designation of Grades and Glossary 

General Purpose Grades: TSR SMR SCR GP ADS RSS

Technically Specified Rubber (TSR 10, TSR 20, TSR 50) Standard Malysian Rubber (SMR 5, SMR 10, SMR 20, SMR 50) Standard Chinese Rubber (SCR 5, SCR 10, SCR 20, SCR 50) General Purpose Grade Air Dried Sheet Ribbed Smoked Sheet

Special Grades: OENR Oil Extended NR L-Grades „Light“ Grades (with colour specification) produced by the selection of latices and removal of carotinoids by latex creaming, addition of Na-HSO3, and intenisve wash etc. SP-Grades „Superior Processing“ (Sol/Gel-Blends) CV-Grades „Constant Viscosity“ NR obtained by the addition of hydroxyl amin prior to latex finishing ENR Epoxidized NR

NR: Annual  Consumption (incl. Latex)  14

Naturkautschuk

12

Synthesekautschuk (Fest + Latex) 10

  s 8   n   o    t   o    i    M 6

4

2

0 1880

1900

1920

1940

1960

1980

2000

Source: IRSG (International Rubber Study Group, Rubber Statistical Bulletin, Wembley, different editions Outlook for Elastomers 1996-97 (Wembley 1998) • Rubber World, 21916 (1999) 13-14 • European Rubber Journal (Quotation of IISRP Statistics), different editions • Consumption 2001-2005: LMC international Ltd. „Rubber, March 2005“ • •

2020

Source: European Rubber Journal, January/February 2011, 16

NR: Production  Malaysia Indonesia Thailand others

3500   s   n   o    t   c    i   r    t   e   m    0    0    0    1   x

3000 2500 2000 1500 1000 500

0 1980 Sources:

1985

1990

1995

2000

2005

K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591 LMC International Ltd; Rubber April 2005

•

•

1997 Thailand Indonesia Malysia

2004

1997

2004

1997

1.934 31,90%

2.988 34,50%   India

570 9 ,40 %

741 8,60 %

Ivory coast

87 1,40%

1.530 25,20%

1.942 22,40%   China

400 6 ,60 %

585 6,70 %   Philippines

60 1,00%

1.070 17,60%

1.175 13,58%

113 1,90%

92 1,10%   Camerun

56 0,90%

Sri Lanka Vietnam

110 1 ,80 %

423 4,90 %   Cambodsha

Brasil Liberia Burma Nigeria Total

Source:

4.534

75% 6.105

70%

1.193

20% 1.841

21%

Römpp Lexikon Chemie; Version 1.5; Stuttgart/New York Thieme-Verlag 1998 LMC International Ltd; Rubber April 2005

49 0,80% 35 0,60% 25 0,40% 21 0,40% 13 0,20%

346 5,7%

NR: Application Areas  Tyres 71%

Automotive (other than tyre) 2% Shoes 4%

None automotive 5%

Others 7%

Latex-Products 11%

Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591

Use of NR in Truck Tyres  Year 19 74 19 81 19 83 19 85 19 90 19 94

Trea Tread [wt.%] .%] NR 4 45 5 6 60 0 77 86 86 1 00

SBR 21 12 7 5 5

BR 34 28 16 9 9

Side ide Wall [wt.%] .%] NR 48 44 58 62 75 60

SBR 37 19 6

BR 15 37 36 38 25 40

Carc Ca rca ass [wt.%] .%] NR 71 84 1 00 1 00 1 00 1 00

SBR 20 11

The majo majorr app applica licattion ion of NR NR is in tru truck ck tyre tyres s

Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591

BR 9 4

NR: Production  Share of smallholders in rubber rubber produc productio tion n: Thailand Indonesia India Malaysia Brasil Sri Lanka Ivory Coast

95 % 83 % 83 % 81 % 70 % 33 % 29 %

Source: International Rubber Study Group

Source: http://www.therubbereco http://www.therubbereconomist.com nomist.com

NR-Pro NR-Produc ductio tion n by smallh smallhold olders ers:

Area cultivated pe per smallholder: Number of o f trees: Annual ta t appings pe per tree: Tota Totall numb number er of tapp tappin ings gs per per yea year: r: Annual yield: Annual earnings: Earnings/different source*: Source:

1,25 ha; 625 trees in i n total; 520 trees un u nder ta t ap 180/a 95.0 95.000 00 tapp tappin ings gs for for 625 625 tre trees es/a /a 850 kg/a ca. 250 €/a (0,30 €/kg) 1020 €/a (1,2 €/kg)

K. Baranwal, R. Ohm, R. R. Fell, B. Rodger Rodgers, s, Rubber, Natural in Kirk Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591 *Broadcast in German German TV TV (ZDF) “Mission“ about Charles Goodyear on 17.10.2004 17.10.2004

As of today, only Bridgestone, Bridgestone, Michelin Michelin und Goodyear Goodyear run NR-plantat NR-plantations ions

Features of the Rubber Tree ( Hevea   )  Hevea Brasiliensis  Botanical Family: • Habitat: •

Height: Temperature:  – Humidity: Rain fall:  – Rain  – Soil:  –   – 

max. ag age of of tr tree: • Height of tree: • tapping age of tree: •Tappings: per tree: • Yield pe • Yield per tap: • density of trees: • Rubber yields: •

Plantation:  – Maximum yield:  – Smallholder:  – 

Fungal infection: • Spread Spread of fungus: fungus: •

Euphorbiaceae Equator + 15° < 300 m 25-30°C > 70% 1800-2000 mm/year good drainage (n ( not at a t the bo b ottom of o f vallleys)

30-40 Ja Jahre (plan lantat tation ion), 10 100 Jahre (r (rain for forest) 20 m (plantation), 40 m (rain forest) 5-7 years every 2n 2 nd day = 180 days/year 1-2 kg/a 5-11g 500/ha 400-1.200 kg/ha 1.000 kg/ha 3.000 kg/ha 850 kg/ha

Dothidella Ulei (Yellow leaf blythe) so far, endemic endemic and restricte restricted d to Brasil Brasil

Source: K. Baranwal, R. Ohm, Ohm, R. R. Fell, B. Rodgers, Rodgers, Rubber, Natural Natural in Kirk-Othmer, Encyclopedia of Chemical Chemical Technology, vol 21, 4th ed., 562-591

Features of NR -  -Latex  L   atex  Total solids solids concentrat concentration:(25) ion:(25) 30-40 30-40 wt. % (depend (dependent ent on many parameter parameters) s) 90 - 95 wt. % of total solids • Rubber content: 150-3000 nm (dependent on many parameters) • Particle diameter: • Gel content: dependent on many parameters (latex age, finishing method) • Molar mass: 105-107 g/mol (not constant, constant, dependent dependent on many parmaters parmaters)) stability without the addition of ad additives (NH3, formaldehyd formaldehyde, e, boric acid, • Latex st phenolates, Na2SO3 (0,05 (0,05 Gew.%) Gew.%),, etc.) etc.) latex latex coagul coagulati ation on occurs occurs as a conseq consequence uence of encym encymatic atic decay •

Latex Finishing  Dilution Dilutio n of the the latex latex to 15-2 15-20 0 wt. % solids solids • Remova Removall of heavy heavy impuriti impurities es such such as sand sand by sedime sedimenta ntation tion • Removal Removal of impurities impurities such as wood, wood, leafs, insects insects,, etc. by filtration filtration Latex fract fraction ionatio ation n for the remov removal al of carot carotinoi inoids ds for „L“ (light (light = colour colourles less) s) grade grades s • Latex • Addition of: •

Na2SO3 (0,15 wt.%) wt.%) for pale-crep pale-crepe-gra e-grades des • [HONH ] SO for CV- grades grades (“Constan (“Constantt Viscosity Viscosity“) “) 3 2 4 •

Disc Discont ontin inuo uous us late latex x coag coagula ulati tion on with with form formic ic or acet acetic ic acid acid (5 wt. %) in pH-r pH-ran ange ge 5,0 5,0 - 5,2 5,2 • Comp Comple leti tion on of coag coagul ulat ation ion by matu maturin ring g for for 12-1 12-16 6h • Mechan Mechanica icall water water remova removall by riffle riffle mills mills (6-9 (6-9 passes passes)) Drying in smoke smoke at 60°C/1 week for RSS-produc RSS-production tion (“RSS” (“RSS” = R Ribbed ibbed Smoked Smoked Sheet) Sheet) • Drying Drying ing in air air at 40° 40°C/2 months months (“ADS“ (“ADS“ = Air Air Dried Dried Sheet) Sheet) • Dry •

NR: Range of Grades  Latexconcentration

Acid Coagulation (factory)

Acid Coagulation (Plantation/Smallholder

centrifugation, creaming, evapor evaporati ation on of water

Natural Coagulation of of latex „Cup lump“

Sheet-Material (RSS, ADS)

„Smallholder‘s lump“

SMR 5 60% Baled or Crumb Rubber

Sales latex (60 wt. % solids)

SMR L

SMR CV 50 SMR CV 60

40%

wet and dry blending pr processes

SMR GP

field grades

SMR 10

SMR 20

Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591

multi-s -sta tage ge wet blen blendi ding ng proce process ss with with mecha mechani nica call gene genera ratio tion n of Comminution Comminution Process: Process: multi crumbs, crumbs, crum crumb b blendin blending g and wash washing ing with subseq subsequen uentt crumb crumb drying drying at 100-12 100-120°C 0°C/4/4-5 5 h is used used for for the the homo homoge geni niza zati tion on and and purif purifica icati tion on of cup cup lumps lumps

NR: SMR -  -Grades   Grades und Specifications  The The cont conten entt of none none rubb rubber er like like resi residu dues es is an impo import rtan antt qual qualit ity y crite criteri rium um for NR consequ equenc ence, e, the conten contentt of impu impurit rities ies is a fea featur ture e in the • As a cons designati designation on of NR grades grades •

NR Grade

SMR 5

SMR GP

SMR 10

SMR 20

SMR 50

Strain Strainer er Res Residu idue e [wt.%] [wt.%] (mesh (mesh width: 45 mm) mm)

0,05

0,10

0,10

0,20

0,50

Beside Besi des s NR puri purity ty,, pri price ce is also also an impo import rtan antt fact factor or for for the the se sele lect ctio ion n of an appropr appropriate iate NR grade. grade. As a consequ consequence ence of price price and quality quality,, the rank rankin ing g of NR NR grad grades es for for tyre tyre build buildin ing g is as fol follo lows: ws: SMR 20 > SMR 10 > SMR GP > SMR 5 > RSS

NR: Vulcaniaztion of Different SMR -  -Grades   Grades  Typ    l   e   v   e    L   y    t    i   r   u   p   m    I

SMR CV SMR L SMR 5 SMR 10 SMR 20

Mons onsantonto-Rh Rheo eomet mete er (16 (160°C) Delta F [J [J/cm2] TS 2 [[m min] 29,4 2,2 33,9 1,8 37,2 1,5 40 1,3 41,1 1,2

t90 [[m min] 11,6 9,7 7,8 6,8 6,8

The The impu impuri riti ties es in NR per perfo form rm like like a vulcan vulcaniz izat atio ion n ac accel celer erat ator or

ACS 1- Compou Compound nd NR Stearic Ac Acid ZnO Sulfur: MBT

100 phr 0,5 phr 6,0 phr 3,5 phr 0,5 phr

With increa increasin sing g impurit impurity y lev level, el, the followin following g featur features es are observ observed: ed: reduction ion of scorch scorch time time • reduct reduction ion of vulcaniz vulcanizati ation on time time • reduct • Increa Increase se of crossl crosslinki inking ng density density

Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Rubber, Natural in Kirk-Othmer Kirk-Othmer Encyclopedia of Chemical Chemical Technology, vol 21, 4th ed., 562-591 (ISO (ISO 1658: Natural Rubber - Test Recipes Recipes and Vulcanization Vulcanization Characteristics, Characteristics, International International Organization Organization for Standardization, Standardization, Geneva, Switzerland, Switzerland, 1973

Chemical and Physical Composition of NR 

Solution fractionation of NR by sequential coagulation: 1. Preparation of a NR solution in toluene 2. Incremental addition of methanol

share

Fraction Nr.: bale 1 2 3 4 5 6 Soluble portion

[wt.%]

1,4-trans content [%]

Viscosity (toluene/25°C) [dl/g]

1,2content [%]

100 24,4 19,7 15,5 8,0 12,9 12,8 6,7

2,2 2,0 2,0 2,0 3,4 4,0 5,0 -

11,5 7,7 3,9 1,9 1,16 0,62 0,3 -

0,6 0,6 0,5 0,5 0,7 0,6 0,5 -

Source: Rubber Chem. Technol. 57, 104 (1984) Source: Rubber Chem. Technol. 82, 283-314

NR has a broad distribution of molar masses (“polydispersity“ or “physical inhomogenity“) • The polydispersity increases with the age of the tree • NR fractions with a low molar mass have a higher content of 1,4-trans moieties than the fractions with a higher molar mass (“chemical inhomogenity“) •

NR: Vulcanization with Multifunctinal Isocyantes  NR (TSR 5, Defo 700) Carbon black/Corax N 2200 Stearic Acid Zinc oxide Antilux 654 IPPD (Vulkanox® 4010 NA) TMQ (Vulkanox® HS/LG) Mineral oil/Enerthene 1849 Sulfur TBBS (Vulkacit® NZ) Desmodur® TT

[phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr]

100 3 3 1,5 1 1 3 1,6 1 0

100 3 3 1,5 1 1 3 1,6 1 15

100 3 3 1,5 1 1 3 1,6 1 0

100 3 3 1,5 1 1 3 1,6 1 25

100 50 3 3 1,5 1 1 3 1,6 1 0

100 50 3 3 1,5 1 1 3 1,6 1 10

OCN

NH

NH CH

3

CH 3

IPPD (Vulkanox® 4010 NA)

N

3

S S

NH

CH 3

CH 3

TBBS (Vulkanox® NZ)

H C

N

N

CH

3

3

O

NCO

Desmodur® TT (TDI Uretdione)

First Hint on NR-Vulcanization with Diisocyanates from O. Bayer, Angew. Chemie 59 (1947) 9, 257-272

NR: Vulcanization with Multifunctional Isocyantes  NR (masticated TSR 5) Carbon black (Corax N 220) Desmodur TT

100 0 0

100 0 0

100 0 15

100 0 25

100 50 0

100 50 10

Fmin Fmax-Fmin t10 t80 t90

[dNm] [dNm] [min] [min] [min]

0,30 7,41 4,34 6,21 7,53

0,18 6,30 4,82 6,77 8,24

0,54 24,20 0,74 15,23 17,60

0,96 20,06 0,71 15,56 19,08

1,06 15,94 1,96 4,22 4,99

1,78 36,26 0,34 7,47 9,07

Tensile Strength Elongation at break M50 M100 M200 M300

[MPa] [%] [MPa] [MPa] [MPa] [MPa]

17,8 605 0,6 0,9 1,4 2,2

15,3 650 0,4 0,6 0,7 1,2

25,7 635 1,5 2,0 2,9 5,0

21,8 565 1,8 2,4 3,7 6,0

27,8 540 1,5 2,7 7,3 13,4

25,2 480 1,9 3,1 8,0 14,4

43 45

40 38

66 -

68 65

66 -

75 -

Shore A Härte/23°C Shore A Härte/70°C Rebound/23°C Rebound/70°C

[%] [%]

74 81

69 78

59 -

55 60

-

-

DIN-Abrasion

[mm3]

183

327

155

123

102

133

NR contains polymer bound functional groups (-NH2, -COOH, -OH, -CONH2) which react with isocyanates

Mastication of NR  184 kJ/mol

C*

343 kJ/mol *C C* Pentachlorothiophenol

  n   o    i    t   a   c    i    t   s   a    M    f   o   e   e   r   g   e    D

SH Cl

*C

2,2'-Dibenzamidodiphenyl-Disulfide (DBD) S

S

NH

HN

Cl

Cl

Cl

O O

Cl

By the use of mastication additives the mastication of NR is accelerated (oxidation catalysts and radical scavengers) • Pentachlorothiophenol is an effective mastication aid; it is banned in WE • Today, disulfides as well as Fe-complexes are used for the acceleration of NR mastication •

0

100 Temperature [°C]

200

At low temperatures (<120°C) mechanical chain scission prevails • At temperatures >120°C thermo-oxidative chain scission prevails • In the temperature range 100-130° C the mastication effect shows a minimum •

Source: C. Clarke, M. Hensel, Rubber World, November 2009, 28-31 „Improved natural rubber processing and physical properties by use of selected compounding additives“

NR: Crystallization at - 25  25 °C  35 30    %    [   y    t    i   n    i    l    l   a    t   s   y   r    C

25 20 15

Pale Crepe

10

pale crepe after acetone extraction

5 0 0

5

10

15

20

25

30

time [h] The Shore A Hardness of NR increases due to crystallization during storage at low temperatures • NR can only be processed in the uncrystallized state C-50°C) • Decrystallization can be achieved by storage at elevated temperatures (40° • The decrystallization in the interior of bales needs 2 weeks at 30°C • The maximum degree of crystallinity of unvulcanized NR is ~ 30% • NR contains impurities which accelerate the speed of crystallization • The crystallization accelerators can be removed by acetone extraction (e.g. stearic acid) •

NR: Dependence of Crystallization Rate and Crystallite Melting Temperature on Storage Temperature  1000

40

   ] 100    h    [   e   m    i    t    f    l   a    h 10

   ] 30    C    °    [ 20   e   r   u    t 10   a   r   e   p 0   m   e    t -10   g   n    i    t    l -20   e   m

-30

1

-40 -50

-30

-10

10

-50

U. Eisele Intorduction to Polymer Physics, Springer-Verlag 1990

-10

10

30

storage temperature [°C]

storage temperature [°C]

Source:

-30

Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 21, 4th ed., 562-591

Stress/Strain -  -Performance   Performance of Unfilled NR -  - and SBR -  -  Vulcanizates ( gum   )  gum stocks 

30 25

NR SBR

   ]   a 20    P    M    [   s 15   s   e   r    t   s 10

Strain induced crystallization

5 0 0

200

400

600

800

1000

strain [%]

Dependence of Tack on Testing Temperature  ( Unvulcanized   )  Unvulcanized NR -  - and SBR -  -Compounds   Compounds  25

20

NR SBR

  x   e 15    d   n    I      k   c   a 10    T 5

0 0

20

40

60

80

temper ature [°C]

100

120

Chemically Modified NR -  -Grades  Grades

Modification 

Application 

Hydroxyl amine (“CV”-Grades)

improved compounding, no mastication required

Blend with NR-gel (“SP”-Grades) Improved processability of NR-compounds Epoxydation (ENR)

Improved oil resistance Improved wet skid Improved silica interaction

Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591

NR: CV -  -Grades   Grades  H H O

+

H2 N

- H2O

H H N

H

H

   ]    U    M    [   e   s   a   e   r   c   n    I     y   e   n   o   o    M

10 9 8 7 6 5 4 3 2 1 0

SMR 20 IR/Natsyn 2200 (IR / Ti)

0

5

10

15

20

storage time [days]

During storage at ambient and elevated temperatures, the viscosity of NR increases to a greater extent than for synthetic IR (storge hardening)  • It is assumed that the viscosity increase of NR is caused by the chemical reaction of polymer bound –NH2 and polymer bound –CH=O groups • By the addition of hydroxylamine to the NR latex prior to latex coagulation –CH=O groups are chemically eliminated  •CV-Grades (“Constant Viscosity“) exhibit an improved storage stability  •

NR: CV -  -Grades   Grades  140   +    1    L    M   y    t    i    )   s   C   o   °   c   0   s   0    i    1    V   -    (   y   e   n   o   o    M

130 120 110 100 90 80 70

before hot air ageing after hot air ageing

60 50 0

0,02

0,04

0,06

0,08

Hexanediamine [mol/kg]

H H

NH2

H2N

+

O

Specification of CV-Grades

H +

H O

Grade

- 2 H2O

CV 50 CV 60 CV 70 LV 50

H H

N

N

H

Ml 1+4 (100°C) Minimum 45 55 65 54

Maximum 55 65 75 55

H

NR: CV -  -Grades   Grades 

H H

H2N

+

C

OH

O - H2O

H H

C N

OH

   ] 70    %    [   y 60    t    i   s   o   c 50   s    i    V   y 40   e   n   o   o 30    M    f   o 20   e   s   a   e   r 10   c   n    I

0 0

0,05

0,1

0,15

hydrox yl amine [wt. %]

NR CV-Grades (“Constant Viscosity“) are obtained by the addition of hydroxylammonium chloride to the latex prior to latex finishing

0,2

ENR: Dependence of Properties on the Degree of Epoxidation  40 20 0

Epoxidation with peracids in the latex stage

O

   ]    C    °    [ -20   g    T -40

O -60 -80

O

0

20

40

60

80

Degree of Epoxidation [%]

Epoxydation of NR has the following effects: •

Increase of polarity (Reduction of the swelling in oil)

•

Increase of Tg (Improvement of wet skid and reduction of gas permeation)

•

Resistance to ageing is unchanged (as bad as for unmodified NR)

•

Processability is reduced (supposedly this problem has been solved)

Source: Ullmann‘s Encyclopedia of technical Chemistry

ENR: Dependence of Vulcanizate Properties on the  Degree of Epxidation  NR ENR 25 (Degree of Epoxidation: 25%) ENR 50 (Degree of Epoxidation: 50%) Carbon black (N 220) Shore A Härte/23°C M300 Tensile Strength Elongation at break Elasticity/23°C Goodrich HBU CS/24h/70°C Volume Swell (70h/70°C) ASTM-Oil No. 1 ASTM-Oil No. 2 ASTM Oil No. 3 Air permeability/23°C

[phr] [phr] [phr] [phr]

100 30

100 30

100 30

[MPa] [MPa] [%] [%] [°C] [%]

59 7,8 27,1 550 78 44 17

56 6,9 25,9 590 25 60 46

59 8,8 27,8 560 15 52 17

[%] [%] [%]

66 114 191

73 28 108

-5 6 21

27,0

8,0

2,0

[1018 x m4/s.N]

100

NR: SP -  -Grades   Grades  •

•

•

SP-Grades (“Superior Processing“) are obained by blending crosslinked NR with uncrosslinked NR in the latex stage. The crosslinked NR-latex (NR-gel) is obtained by sulfur cure in the latex The SP-series of grades comprises different blend ratios of ucrosslinked  and unrosslinked NR as well as oil extended grades Grade Precrosslinked Uncrosslinked Oil NR NR [wt.%] [wt.%] [phr] SP 20 20 80 0 SP 21 40 60 0 SP 22 50 50 0 SP 23 80 20 40 SP 24 80 20 0

SP-grades have the following advantageous properties:  reduced die-swell  Increased extrusion out-put  • Reduced roughness on surface and edges  • •

Source: BP 880739; Natural Rubber Producers‘ Association, Appl.: 28.03.1957, Inv.: B. C. Sekhar „Improvement in the Preparation of Superior Processing Rubbers“

NR: Impact of Vulcanization Systems on Vulcanizate  Properties 

NR (SMR 5) N 330 Oil ZnO Stearic Acid Sulfur TBBS CBS TMTD Santoflex 13 TMQ DCP Novor 924 Caloxol ZDMC ZMBT

[phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr]

Schwefel (conv.)

Sulfur (Semi EV)

Sulfur (EV)

Peroxide

Capped Di-IsoCyanate

100 50,0 4,0 5,0 3,0 2,5 0,5 2,0 -

100 50,0 4,0 3,5 2,5 1,2 0,8 0,4 2,0 -

100 50,0 4,0 5,0 2,0 0,33 0,8 0,4 2,0 -

100 50,0 3,0 5,0 2,0 2,5 -

100 50,0 3,0 5,0 2,0 6,7 5,0 2,0 2,0

Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591

NR: Vulcanization with A Capped Diisocyanate ( Novor  Novor 924)  O N N O

N O

NH

O

HN

O

O

O

Novor 924: TDI based diisocyanate Novor 950: MDI based diisocyanate

O N

Thermal Cleavage

Due to health and safety reasons Novor 924 has been replaced by Novor 950

O N N

O

N O H

O C N

O

N C O

O

Tautomerization

Tautomerization

O N

H O N

H O

O H

N

H

O H

O

- H2O

- H2O N N O

N

NH

O

HN

O

N

O

O

Sources: • • • •

F. Barlow „Rubber Compounding“ 2nd edition, Marcel Dekker, Inc. Chapter 7, page 96-98 Vulcanization with Novor 924, NR Technical Bulletin, MRPRA, Brickendonbury, England Novor Application Data Sheet, Solid Tyres, ADS-5H, Rubber Consultants, Brickendonbury, England C. S. L. Baker, Novor Vulcanizing Systems: Their Technical Development and Application Areas, Rubber Manufacture and Technology Seminar, P. R. I. (Malaysian Section), Kuala Lumpur, July 21-23-1981

NR: Dependence of Vulcanizate Properties on Vulcanization System 

Shore A Hardness/23°C M100 [MPa] Tensile Strength [MPa] Elongation at break [%] Rebound/23°C [%] Fatigue to Failure [kZ] Goodrich HBU [°C] CS/24h/70°C [%] [%] ∆ TS (7d/100°C)

Sulfur (konv.)

Sulfur (Semi EV)

65 2,08 28,8 515 70 223 29 27 73

65 2,22 30,1 485 77 106 32 14 54

Sulfur Peroxide (EV) 67 2,34 24,2 390 67 68 36 10 24

61 2,28 21,4 310 72 51 34 11 49

Capped Di-Isocyanate 70 2,60 24,0 460 66 90 30

2.2. Synthetic Polyisoprene (IR)  Contents: • Differences between IR and NR • IR-Grades, Catalysts and Microstructures • Price, Producers, and Production Capacities • Comparison of Unvulcanized NR- and IR- Properties • Vulcanizate properties of NR and IR • Compound and Vulcanizate Properties of Poly-3,4-Isoprene

IR grades and chemical differences between NR und IR: NR cis-1,4-content [mol % ] Need for Mooney adjustment before use Gel functional groups

98 yes yes yes

IR Ti

Li

Nd

93 97 99 no mastication needed -

2.2. Synthetic Polyisoprene (IR)  Isoprene

Poly-3,4-Isoprene

H3C C2

3

C C4

C

1

Poly-cis-1,4-Isoprene

Type of IR Catalyst Trade Name 1)

Cariflex IR-309

Poly-trans-1,4-Isoprene

Solvent

Microstructure cis-1,4 trans-1,4 1,2- 3,4-

Li

unpolar (benzene)

93

0

0

7

Natsyn 200

Ti

unpolar hydrocarbon

97

0

0

3

2)

Li

Hexane/Additive

Nd

unpolar hydrocarbon

1)

Vestogrip IR

3)

Sources:

60 99

-

-

-

1) E. Schoenberg, H. A. Marsh, S. J. Walters, W. M. Saltman, Polyisoprene, Rubber Chemistry and Technology, Vol 52, S. 526-604 2) Data sheet of Hüls AG: “Vestogrip“ (Production by Karbochem / South Africa: ca. 3.000t) 3) WO 02/38635 A1 (Michelin), Erf.: P. Laubry, Prior.: 13.11.2000 3) WO 02/48218 A1 (Michelin), Erf.: P. Laubry, Prior.: 28.11.2001

IR: Development of Prices, Producers and Production  Capacities  3    ] 2,5   g    k    / 2    $    S1,5    U    [   e   c 1    i   r    P

0,5

IR NR (RSS)

0 1980

1985 1990

1995

2000 2005

2010

Company

Plant Location

Capacity [kt]

Goodyear

Beaumont/Texas/USA

90

Kraton Polymers

Rotterdam-Pernis/Nederland

25

Kauchuk Sterlitamak Nishnekamskneftekhim Togliattikauchuk

Sterlitamak/Russia Nishnekamsk /Russia Togliatti

100 200 130

JSR Corporation Zeon Corporation

Kashima / Ibaraki Pref. Mitzushima / Okayama Pref.

36 40

Karbochem

Newcastle / Natal /South Africa

3

Total Capacity [kt]

624

Source: R.J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008 „Globalization of Synthetic Rubber Industry“

Comparison of NR and IR: Stress/Strain -  -Curves   Curves of Unvulcanized  Polyisoprene Compounds  Polyisoprene Compounds 

9 8

NR (SMR 5) High cis-IR/Ti (97%) Low cis-IR/Li (93%)

7

   ]   a    P    M    [   s   s   e   r    t    S

6 5 4 3 2 1 0 0

100

200

Strain [%]

300

400

500

Evaluation of Compound -  - and Vulcanizate Properties of NR and IR  Compound Properties

NR + +

Mastication Mixing cycle Die swell Tack Green strength

Li

IR Ti

Nd

+ + + -

+ + + -

+ + + + +

Li

IR Ti

Nd

-

-

+ + + + +

Vulcanizate Properties

NR Modulus Tensile Strength Cut growth resistance Rebound Elastivity Abrasion resistance

+ + + + +

Poly -  -3,4   3,4 -  -Isoprene:  Isoprene: Compound and Vulcanizate Properties  3,4-content (NMR):

ca. 60 %

3,4-Polyisoprene

100 phr

ML 1+4 (100°C):

65 MU

CB (Corax N 330)

50 phr

Tg

-8°C

HAR-oil

10 phr

Source: Data sheet of Hüls AG „Vestogrip (3,4-Polyisopren-Kautschuk)“

Zinc oxide

3 phr

Stearic acid

2 phr

CBS

1 phr

Sulfur

2 phr

Compound Properties ML 1+4(100°C) [MU] t10/150°C [min] t90/150°C [min]

77 13,8 27,5

Vulcanization (30 min/150°C) Shore A Härte (22°C) Shore A Härte (75°C) M 100 [MPa] M 300 [MPa] TS [MPa] εb [%]

67 52 2,1 8,4 14,7 510

Cut growth resistance [N/mm] Residual elongation [%]

25 20

Rebound / 22°C Rebound / 75°C

2 44

[%] [%]

tan  δδ/25°C tan  δδ/75°C

Source: P. Roch (Goodyear) KGK 48,6 (1995) 430-434“Compounding for Wet Grip“

0,26 0,11

 3.0. Overview on Emulsions Rubbers •

Emulsion Rubbers and Features of the Emulsion Process

•

Essentials of the Emulsion Polymerization

•

Mechanism of Emulsion Polymerization

•

Kinetic Aspects of the Emulsion Polymerization

•

Flow Diagram of Continuous Emulsion Polymerization

•

Flow Diagram of Latex Finishing

•

Finishing of CR-Latex

•

Legal Aspects of Water Usage

 Emulsion Rubbers and Features of the Process Features of the Emulsion Process Advantages: • • • • • •

high reactor output good heat removal low viscosities high solids high molar masses high reproducibility

Disadvantages: • •

•

Waste water Product impurities (residuals from emulsifier and coagulants) no water resistant catalysts available (Stereospecifity)

Emulsionrubber

Latex Coagulation

E-SBR NBR CR ACM FKM

electrolyte electrolyte freezing electrolyte electrolyte

Application Areas for Rubber Latices:  • • •

Carpet backing, paper-, textile- and leather finishing (X-SBR)  Latex dipping process for improvement of cord adhesion  Manufacture of dipped articles such as protection gloves etc. (NR, NBR, CR) 

Principles of Emulsion Polymerization 

Emulsifier Initiator

Monomer

Polymerization  Wasser

Monomer emulsion

Polymer dispersion (Latex or rubber latex)

Mechanism of Emulsions Polymerization  Latex particle Particle diameter: concentration:

Monomer containing emulsifier micelle Diameter: 5-10 nm concentration: 1021 lw-1

10-500 nm 1017 lw-1

M M

M

M

M

Monomer droplet Diameter: concentration:

M

M

M

M

0,1-10*10 -6 m 1013 lw-1

M

M

M

Literature: Polymerization occurs only in P. E. Lovell, M. S. El-Aasser, Emulsion Polymerization, Wiley 1998 monomer loaded micelles and Blackley, Emulsion Polymerization, 1975 H. Gerrens, Advances in Polymer Science, volume 1 not in monomer droplets • • •

Phases in Emulsion Polymerization  Phase I

Phase II

Phase III

80 70   s    t    i   n    U   y   r   a   r    t    i    b   r    A

Surface tenison pressure polymerization rate

60 50 40 30 20 10 0

0

20

40

60

80

100

Monomer Conversion [%] Literature:

P. E. Lovell, M. S. El-Aasser, Emulsion Polymerisation, Wiley 1998 Blackley, Emulsion Polymerisation, 1975 H. Gerrens, Fortschritte der Hochpolymerforschung

 Kinetic Aspects of Emulsion Polymerization Phase I: Phase II:

Phase III:

NL and Vbr increase „free“ emulsifier reduces surface tension NL und Vbr remain constant the monomer concentration in latex particles remains constant the latex particles grow and soap coverage decreases surface tenison increases the monomer droplets have disappeared the monomer contained in latex particles is consumed the number of latex particles remains constant

Number of latex particles formed: x y NL = k * (E-CMC) * I Polymerization rate in Phase II: VBr = NL * kw* [n]* [M] Prediction by the Smith Ewart Theory: NL: E-CMC: I: kw: [n]: [M]:

x = 0,4; y = 0,6 [n]= 0,5

number of latex particles [lw-1] effective emulsifier concentration [lw-1] Initiator concentration [lw-1] propagation rate constant [l * mol-1 * sec-1] average concentration of radicals per particle [without dimension] monomer concentration in latex particle [Mol * l-1]

Flow Diagram of a Continuou  Continuous Emulsion Polymerization (E -  -SBR)   SBR)  Recovered styrene Vapour condensation

Mixer/Settler

Waste water treatment

Recovered butadiene   n   o    i   n    t   o   u    i    l    t   o   u   s    l   o   r   s   e    t    i    f   s    i   s   e   l   y    l    d   u   i    t   a   x   a   m   c   e   e   o   r   n   s   e   e   e   u   p   s   u    i   o   o   o    d   n   e   e   r   a   r   u   d   e    t   y   q   y   u   q   u   t    B   S   A   H   A

  x   e    t   a    L

Puffertank

Mixer/Settler

Brüdenkondensation

Wate water treatment

  a   l   e   s   s    i   s   r   e   e   k   m  s   y  n    l   o   o   i    P   t   -

  a   l   e   s   s    i   s   r   e   e   k   m  s   n   y    l   i   o  o    P   t   -

Stripping column

Flash evaporation

Abstoppkessel

   l   a   e   s  s    i   s   r   e   e   k   m  s   y  n    l   o   o   i    P   t   -

   l   a   s  e   s    i   r  s   e   e    k   m  s   y    l   n   o   o   i    P   t   -

   l   a   s  e   s    i   s   r   e   e   k   m  s   y  n    l   o   o   i    P   t   -

  p   o    t   s    t   r   o    h    S

  r   u   o   p   a    V

Latexstorage

Flow Diagram of Latex Finishing  (E -  -SBR,  SBR, NBR) 

   O    A

   )   c    t   e  ,    l    i   o   s   (    t   n  s   a  e    l   v   u   i    i   g   t   a   d   o   d    C    A

Coagulation tank

  r   e    t   a   w    h   s   a    W

Washtank

Mass Balance: Latex volume : Rubber (25%): Water serum (75%): Wash water: Waste water:

Dewatering screw

Waste water treatment

400.000 t 100.000 t 300.000 t 100.000 t 400.000 t

dryer

Baler and packaging

Finishing of CR -  -Latex   Latex 

stripped Latex

dryer

Latex-surge tank

dewatering rolls

Acidic acid

Freezing roll

Powdering

Chopper

packaging

Waste water treatment

Legal Aspects of Water Surveillance in Germany  Wasserhaushaltsgesetz (WHG) “Legislation on the regulation of the water household" of September 23rd, 1986, BGB1. I, S. 1654

Abwasserabgabegesetz (AbwAG) “Legislation on Charges for the emission of polluted water“ of November 6th, 1990, BGB1. I, S. 2432

Abwasserherkunftsverordnung (AbwHerkV) “Legislation on the provinence of waste water" Of July 3rd, 1987, BGB1.I, S. 1578

Trinkwasserverordnung (TrinkwV) “Legislation on the quality of drinking water and on water which is used in food production” of December, 5th, 1990, BGB1. I, S. 2612 Source : W. Guhl und U. Werner; Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH D-69469 Weinheim, 1997

Legal Aspects of Water Surveillance in Germany  “Legislation on the regulation of the water household“  of September 23rd, 1986, BGB1. I, S. 1654  Water is a natural ressource. It has to be used in a sustainable manner for the benefit of the community as well as for the benefit of individuals. Negative impacts have to be avoided.

Everybody who uses water is obliged under the necessary circumstances to act in a careful and responsible manner in order to avoid water pollution and negative impacts on the properties of water.

Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997

Legal Aspects of Water Surveillance in Germany  “Legislation on Charges for the emission of polluted water“  of November 6th, 1990, BGB1. I, S. 2432 By law, in 1990 one “pollution unit“ was fixed at 70 DM. According to this law, one pollution unit was defined to correspond to: 50 kg O2 (COD) 3 kg Phosphorous 25 kg Nitrogen 2 g organic halides 20 g Hg 100 g Cd 500 g Cr 500 g Ni 500 g Pb 1 kg Cu etc. • • • • • • • • • • •

Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997

Legal Aspects of Water Surveillance in Germany  1. 2. 3. 4. 5.

COD = 0 BOD = 0 COD = BOD COD < BOD BOD < COD

Which equation does not make sense?

COD: Chemical Oxygen Demand BOD: Biological Oxygen Demand

Legal Aspects of Water Surveillance in Germany  Explanation:

COD = 0 BOD = 0

COD = BOD COD < BOD BOD < COD

no impurities present which can be chemically oxidized (very pure water) no biologically degradable substances present (substances which are not biodegradable might be present) all impurities are biodegradable this is not possible The impurities are only partially biodegradable

3.1. Emulsion -  -SBR  S   BR (E -  -SBR)   SBR)  •

Overview  – Microstructure and

Property Profile

 – Market  – Application

Areas, Market, Products and Important Grades  – Producers and Production Capacities

•

Polymerisation  – Polymerization

Recipe („Cold Rubber“)  – Ingredients of a Polymerization Recipe  – Sequence of Reaction Steps  – Copolymerisation of Styrene und Butadiene  – Influence of Chain Modification Agents

•

Product Properties  – Tg  – Influence of

None Polymeric Residues on Compound and Vulcanizate Properties

Microstructure of E -  -SBR   SBR 

4

CH 1 2

2

HC HC

CH2

1

CH2

3 4

C H2

1,4-cis

3

CH

3

CH

CH CH

2

CH2

4

1,4-trans

2

CH2 1

Vinyl

CH CH2

2

1

Styrene

E -  -SBR:  SBR: Property Profile and Application Areas  Positive: •

good mechanical properties of filled vulcanizates (TS, Modulus, Abrasion Resistance) • Good wet skid properties (dependent on amount of incorported styrene/Tg) • short sequences of incorportated styrene (low hysteresis losses and low rolling resistance) • Availability of high Mooney-grades which allow for high loadings of mineral oil (oil extended grades with reduced price) • Great variety of standardized grades • Many competitors/low price (commodity) Application Areas in Western Europe

Negative: •

poor ageing resistance • poor resistance to swelling in oils • no variation of microstructure • low / no profits / no R&D-activities

Tyres 72%

Others 2%

Buildings Shoes Automotive 5% 5% 8%

mechanical parts 8%

E -  -SBR:  SBR: Producers and Production Capacities  Produer

Site

Country Capacity

Copolymer (DSM) Goodyear Ameripol Synpol Bayer

Baton Rouge Houston Port Arthur/Odessa Sarnia

Petroquimica Argentina Petroflex/Coperbo Negromex

Pto. Gral, San Martin Duque de Caxias/Triunfo Altamira

Bayer France Dow Enichem. Shell Dwory Chemopetrol HIP Petrohemija Combinatul Petrochimic Neftochim

La Wantzenau Schkopau Ravenna Pernis Oswiecim Kralupy Zrenjanin Onesti Burgas

JSR Mitsubishi Kasei Corp. Zeon Corp. Sumitomo Chemical Comp. Korea Kumho Hyundai Taiwan Synthetic BST Elastomers Gadjha Tunggal Quenos

Kawasaki Yokkaichi Tokuyama/Kawasaki Chiba Ulsan Daesan Kaohsiung Mab Ta Phut, Rayong

Apar und Synthetics &Chemicals V/O Raznoimport SINOPEC und Petro China

Bombay/Bareilly Omsk/Sterlitamak/Togliatti/Voronezh Lanzhou/JiLin

Altona

Sum

USA USA USA Can.

150.000 267.000 336.000 20.000

Argentinia Brasil Mexico

53.500 255.000 74.500

France Germany Italy Netherlands Poland Czech Rep. Crotia Rumania Bulgaria

90.000 120.000 295.000 120.000 104.000 76.000 40.000 100.000 20.000

Japan Japan Japan Japan Korea Korea Taiwan Thailand Indonesia Australia

195.000 65.000 200.000 50.000 190.000 60.000 105.000 60.000 60.000 35.000

India USSR China

75.000 486.000 200.000

3.902.000 Market: Capacity: Capacity utilization:

2,0 Mio t 3,9 Mio t 51%

Source: Worldwide Rubber Statistics 2001, IISRP, International Institute of Synthetic Rubber Producers, Inc.

E -  -SBR:  SBR: Producers and Capacities in Europe ( without   ): without Latex Capacities  700 600 500

Company

Site

Country

Capacity

Lanxess France Dow Enichem. Dow (prior owner: Shell)

La Wantzenau Schkopau Ravenna Pernis

France Germany Italy Netherlands

45.000 120.000 295.000 120.000

Sum

   ]    t    [   n 400   o    i    t   c   u    d 300   o   r    P

580.000 415.000

Dwory Chemopetrol HIP Petrohemija Combinatul Petrochimic Neftochim

200

Oswiecim Kralupy Zrenjanin Onesti Burgas

Poland Czech Republic Croatia Rumania Bulgaria

Sum

104.000 76.000 40.000 100.000 20.000

340.000

100 0 1990

1992

1994

1996 1998

2000

2002

Market Volume in WE: Capacities in WE: Formal Capacity Utilization in WE:

666 k t 415 kt 160 %

Dow Chemical shuts down ESBR-Plant in Pernis/ end of March 2004 (Chemical Week of 24.03.2004) Lanxess shuts down E-SBR production in La ‚Wantzenau effective by July 2008 Source: Worldwide Rubber Statistics 2001, IISRP, International Institute of Synthetic Rubber Producers, Inc.

Range of E -  -SBR S   BR Grades Cold Rubber Hot Rubber High Styrene Rubber

number of grade assignation 1000 1500 1600 1700 1800 1900

Cold Rubber without Carbon Blackadditives Masterbatch X X X -

Oil-extension (<14 phr) X -

Oil extension (>14 phr) X X -

Hot Rubber

High styrene rubber

X -

X

Source: The Synthetic Rubber Manual, 14th edition IISRP (International Institute of Synthetic Rubber Producers, Houston (1999)

E -  -SBR: S   BR: Selected Grades  E-SBR Styrenegrade content [wt.%]

ML 1+4 (100°C) [MU]

Antioxydant System

Mineral Oil grade loading [phr]

Carbon Black grade loading [phr]

1500

23,5

50-52

S

-

-

-

-

1502

23,5

50-52

NS

-

-

-

-

1507

23,5

30-35

NS

-

-

-

-

1509

23,5

30-35

NS

-

-

-

-

1707

23,5

49-55

NS

NAPH

37,5

-

-

1712 1721

23,5 40

49-56 50-55

S S

HAR HAR

37,5 37,5

-

-

1609

23,5

61-68

S

HAR

5

N 110

4

1808

23,5

48-58

S

HAR

47,5

N 330

76

S:

staining

NAPH:

NS:

none staining

HAR:

Remarks & Application Areas General purpose rubber for tyre treads and for technical rubber goods uncoloured technical goods Compounds with good processability (calandered and injection moulded products) E-SBR with low ash content and low w ater swell (cables and electronic industry) lught colourd rubber goods (hoses and profiles) Tyre treads, transportation belts, dark colured technical Abrasion resistant compounds für retreading tyre treads, dark colured technical rubber goods

naphthenic oil highly aromatic

Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)

E -  -SBR: S   BR: Recipe for Cold Rubber Production  Monomers: Butadiene Styrene

23,2 9,5

wt.% wt.%

t-DDM

0,07

wt.%

Water

65,4

wt.%

Emulsifier System: K-salt of disproportionated rosin Na-salt of methylen-bis-naphthalinsulfonic acid

1,5 0,03

wt.% wt.%

Initiator-System: p-Menthylhydroperoxide FeSO4 * 7 H20 Di-sodium salt of ethylenediaminotetraacetic acid Na-salt of Formaldehydesulfoxylate Na3PO4*12 H2O

0,04 0,01 0,02 0,03 0,16

wt.% wt.% wt.% wt.% wt.%

Modifier: Reaction medium:

E -  -SBR: S   BR: Ingredients of Polymerization Recipe I  ( Emulsifiers   )  Emulsifiers  Disproportionation of Abietic Acid

CH3

Na-Salt of Methylene-bis (Naphthalin-sulfonic Acid) (Baykanol PQ(R))

H COOH

CH3

SO3

Abietic Acid

2 Na +

CH2

Pd

CH3

SO3

CH3

CH3

+

+ H CH3 COOH

Dehydroabietic Acid

H

H CH3 COOH

CH3 COOH

Dihydroabietic Acid Tetrahydroabietic Acid

E -  -SBR:  SBR: Ingredients of Polymerization Recipe II  p-Menthanehydroperoxide (p-MHP) CH3

CH2 CH2

Oil soluble hydroperoxide

CH3 CH

CH

CH2 CH2

O

O

H

CH3

Na-Formaldehydesulfoxylate Na-Hydroxymethanesulfinate O

H

Reducing agent

H

O

S

O

+

Na

H Ethylenedinitrilotetraacetic Acid (EDTA) O

Sequestering agent for Fe-Ions

HO

O CH2 N

HO

CH2 O

CH2

OH

CH2

OH

CH2 CH2 N

O

E -  -SBR:  SBR: Sequence of Reaction Steps  Redox Initiation: R-OOH Fe3+  R-O*

+ Fe2+ + Reducing agent + Monomer

R-O* + OH- + Fe3+ Fe2+ + oxydized reducing agent R-O-Mon*

Growth Reaction: R-O-Mon* + n Monomer

P*

Regulation of Molar Mass with Mercaptanes: P* + HS - R R - S* + n Monomer R - S - Mn* + HS - R

P- H R - S - Mn* R - S - Mn - H

+ R - S* + R - S*

Transfer Reaction: P*

+ R-H

R - H + P*

Termination Reaction: P*

+ P*

P- P

E -  -SBR:  SBR: Influence of Thiols  100

175

   ] 80    %  .    t   w 60    [    t   n   e    t   n 40   o   c    l   e    G 20

   ]    E 140    M    [    )    C    ° 105    0    0    1    ( 70    4    +    1    L 35    M    (

0

0

0

0,2

0,4

Tert-dodecylmercaptane [phm]

0

0,2

0,4

Tert-dodecylmercaptane [phm]

E -  -SBR:  SBR: Styrene/Butadiene -  -Copolymerization   Copolymerization (Differential Styrene Incorporation)     ] 100    %  .    t 90   w    [ 80   r   e   m 70   y    l   o    P 60    f   o 50    t   n   e 40    t   n 30   o    C   e 20   n   e   r 10   y    t    S 0

Copolymerization Parameters (Styrene = M1; Butadiene = M2) r1 = 0,7 r2 = 1,4 As a Consequence of these copolymerization parameters there is no azeotropic composition

0

10

20

30

40

50 60 70

80

90 100

r1 =

k11 k12

r2 =

k22 k21

Styrene Content of Monomer Feed [wt. %]

E -  -SBR:  SBR: Copolymerization of Butadiene and Styrene  (Integral Styrene Incorporation)  100

   ]    %  .    t   w 80    [    t   n   e    t   n 60   o    C   e   n   e   r 40   y    t    S    l   a   r   g   e 20    t   n    I

Copolymerization Parameter: r1 (Styrene) = 0,78 r2 (Butadiene) = 1,39

Ideal (random) Copolymerization for Monomer Feed Styrene/Butadiene: 30/70

Monomer Feed Styrene/Butadiene: 30/70 Polymerization Temperature: + 50°C Hot Polymerisation - 20°C (Cold Polymerisation)

0 0

20

40

60

80

Monomer Conversion [%]

100

E -  -SBR:  SBR: Distribution of Styrene Sequences  in E -  -SBR  SBR 1502  Copolymerizationparameter Styrol = M1 Butadien= M2 r1 = 0,7 r2 = 1,4

80    ]    %    [   y    t    i    l    i    b   a    b   o   r    P

70 60 50 40 30

r1 =

k11 k12

r2 =

k22 k21

20 10 0 1

2

3

4

5

6

7

8

9

10 11 12

Number of Styrene Units

E -  -SBR: S   BR: Microstructure 

Polymerizationtemperature [°C] -20 5 50 100

BR-Microstructure 1,4-cis 1,4-trans Vinyl [%] [%] [%] 0,8 7,7 14,8 27,6

79,6 71,5 62,0 51,4

19,6 20,8 23,2 21,0

Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)

E -  -SBR:  SBR: Dependence of Tg on Styrene Content  expt. data

100

Tg of atactic polystyrene

Fox-Flory-equation

80 60

   ]    C    °    [   g    T

40 20 0

Fox-Flory-Equation

-20

1

-40

Tg

-60

Tg: Tg1: Tg2: wn:

-80 -100

=

Tg of E-BR

0

20

40

w1 Tg1

+

w2 Tg2

Tg of copolymers in K Tg of homopolymer 1 in K Tg of homopolymer 2 in K weight fraction of copolymers 1 und 2

60

80

100

Styrene Content [Gew.%] Source: T. G. Fox, P. J. J. Flory; Appl. Sci., 21,581 (1950)

Influence of None Polymeric Residues on Compound and Vulcanizate Properties : Analytical Data  Product

Mw [g/mol]

Mw/Mn

ML 1+4 (100°C) [ME]

[°C]

45 51 52 54

-51 -53 -50 -50

Tg

Krylene 1500 mod. Krylene 1500* Krylene 1712 mod. Krynol 1712*

424.280 429.210 740.170 716.760

3,46 3,51 3,69 3,74

Product

Ash cont. (850°C) [wt.%]

Na

Al

chloride

[ppm]

[ppm]

0,33 0,23 0,41 0,20

1105 910 1502 355

655 1

Krylene 1500 mod.* Krylene 1500 Krynol 1712 mod.* Krynol 1712

137,5 phr of Krynol 1712 contains 37,5 phr oil ==>

27,27 wt.% oil

[ppm]

waterextract [wt.%]

acetoneextract [wt.%]

0,110 0,079 0,230 0,045

0,33 0,23 0,41 0,20

6,9 2,4 32,3 30,1

* Modification of latex finishing (coagulation and crumb wash) in order to obtain a rubber with a reduced content of residues with low molar mass

Influence of None Polymeric Residues on Compound and Vulcanizate Properties : Compound Composition  Krylene 1712 Krylene 1500 mod. Krylene 1712* mod. Krylene 1500* Carbon black N 339 Carbon black N 234 Mineral oil TMQ IPPD DTBD Stearic acid Zinc oxide Sulfur CBS DPG

[phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr]

103,13 25,0 80,0 10,0 0,5 0,75 0,75 2,5 2,5 1,9 1,1 0,55

103,13 25,0 80,0 10,0 0,5 0,75 0,75 2,5 2,5 1,9 1,1 0,55

68,75 50 80 20,0 0,5 0,75 0,75 2,0 2,5 1,9 1,2 0,3

68,75 50 80 20,0 0,5 0,75 0,75 2,0 2,5 1,9 1,2 0,3

* Modification of latex finishing (coagulation and crumb wash) in order to obtain a rubber with a reduced content of residues with low molar mass

Influence of None Polymeric Residues on Compound on Vulcanizate Properties  103,13 25,0 -

103,13 25,0

68,75 50 -

68,75 50

Compound-Mooney ML1+4 (100°C) [MU]

67,0

71,0

73,5

77,0

Rheometer (160°C) ΜL ∆ F ts1 t50 t90

[dNm] [dNm] [min] [min] [min]

8,3 35,3 4,8 7,5 11,2

8,8 38,2 4,3 6,8 9,3

9,1 37,3 4,7 8,2 12,6

10,1 39,2 4,5 7,9 11,1

[MPa] [%] [MPa] [MPa]

17,3 425 2,5 12,6 69 63 25 38

18,5 410 2,7 14,3 71 64 27 42

17,9 480 2,3 10,9 72 64 22 33

18,9 470 2,3 11,8 71 64 25 36

Krylene 1712 Krylene 1500 mod. Krylene 1712* mod. Krylene 1500*

Vulcanizate Properties: Tensile Strength Elongation at break M100 M300 Shore A Hardness/23°C Shore A Hardness/70°C Rebound/23°C Rebound/70°C

[phr] [phr] [phr] [phr[

[%] [%]

3.2. Polychloropren  Polychloroprene    (CR)  Overview

•

– – –

Property Profile and Application Areas Producers and Poroduction Capacities Grades and Application Areas

Manufacturing

•

– – –

CR-Microstructure Monomer Manufacturing Processes Basic Features of Polymerization Recipes

Influence of CR-Microstructure on Chemical and Physical Properties

•

–

Crystallization, Glass Transition Temperature, CR-Vulkanization

Rubber Grades

•

– – –

Standard Grades Sulfur Grades Precrosslinked Grades

CR-Vulcanization

•

–

Mechanism

Substitution of CR

•

Sources: - W. Obrecht, Houben Weyl-Müller Makromolekulare Stoffe (1987), volume E20/Teil 2, S. 842-859 - P. R. Johnson, Rubber Chem. Technol. 49 (1976) 650-702

CR: Property Profile and Application  reas  pplication Areas Positive Aspects: • • • • • • • • • • • •

High loadability gute Vulkanisationsfähigkeit Adjustable crystallization rate Good vulcanizate properties Good dynamic properties High weather an ozone resistance Good adhesion to metals Good resistance against fungi, mould and bacteria Fair insulation properties Excellent fire resistance Low gas permeability Broad range of grades

Negative Aspects: • • • • •

High density (2,5 g/cm3) High compound price Modest resistance against chemicals and oils Crystallization at low temperatures poor ageing resistance at elevated temperatures

CR: Producers  and Production  Capacities  (2010)  Producer

Capacity Site

Butadiene Acetylene

Denki Kagaku Kogyo KK Lanxess

100 75

Omi/Japan Dormagen/Germany

X

X -

DuPont Tosoh Chonquin Changshou Chemicals Shanxi Syntheic Rubber Co

45 32 28 25

Pontchartrin/USA Nanyo/Japan Chongquing/China Datong/China

X X -

X X

Pidilite Showa Denko KK Nairit Scientific Industrial

25 20 10

India Kawasaki/Japan Yerewan/Armenia

X X -

X

Total

360 Plant Closures Producer

Stagnant CR-Consumption in WE and USA Growing Consumption in South-East Asia

Source: Various Press Releases

Capacity Site

DuPont

30 50

Maydown/N.-Ireland Louisville/USA

Bayer

25

Houston/USA

Polimeri (BP)

25

Grenoble/France

 Monomer Manufacturing Processes 2-Chlorobutadiene-1,3 (Chloroprene) Acetylene Route (1930) 2 HC

CH

H2C

CuCl/NH4Cl/HCl Nieuwland

HC

Butadiene Route (Gas phase chlorination / 1956)

CH CH2

Cl Cl

Cl H2C

C

Cl

Cl + CH2 CH CH CH2+ CH2 CH CH CH2 (ca. 60 %) (ca. 40 %) Side products: chlorinated C8-Compounds   Tetrachlorobutane CuCl Cl Cl H2C CH CH CH2 + NaOH - HCl   (85°C)

Cl H2C

CH CH CH2 + Cl2

HCl/CuCl (30-60°C)

2,3-Dichlorobutadiene 1,3 (DCB)

CH CH2 + Cl2

Cl Cl H2C

C

+ NaOH/85°C

Cl

CH CH2 - HCl

Cl Cl H2C

C

C

CH2

Cl CH CH2 + HC

2-Chloroprene DE 1149001; Knapsack AG, Prior.:10.07.1961 Erf.: W. Vogt, K. Kaiser, H. Weiden

CH CH CH2

1-Chloroprene (impurity) GB 804254; Distillers Co. Ltd. , Prior.:21.03.1956; Erf.: F. J. Bellringer

Only DuPont, Lanxess und Denki produce DCB

CR: Grades and Aplication Areas CR Application Areas (2006) Rubber Applications 60%

Latex applications 5%

Latex based adhesives 5%

   ] 45    C    °    [   e   r 40   u    t   a 35   r   e   p 30   m   e    T 25   n   o    i    t 20   a   z    i 15   r   e   m10   y    l   o    P 0

Solvent based adhesives 30%

Application Areas of Rubber Grades Profiles 11%

Hoses 44%

Belts 12%

50

Latex Grades

(Standard Grades, precrosslinked grades and sulfur grades)

Adhesive Grades

0

Conveyor Belts 12%

Cables 21%

Rubber Grades

1

2

3

4

5

6

7

DCB-Content of Monomer Feed [phm]

CR: Influence of Polymerization Temperature on  Microstructure CH2 C

1,4-trans

C

Cl

CH2

Cl

H

1,4-cis

C

C

CH2

Cl

1,2

C

H CH2 C

2

3

CH2

3,4

CH2 C

3

H

2

CH2

C

Cl

CH2

Microstructure trans-1,4 cis-1,4 > 89% > 95% Tg [°C] Tm [ °C]

Polymerization temperature [°C] +12 +30 +42 +57 +75

H

-45 105

-20 70

   ] 95    %    l   o    M    [    t   n   e    t   n 90   o    C     s   n   a   r    t      4  ,    1

85 0

Adhesive grades 10

20

1,4-trans- 1,4-cis [%] [%] 94,5 3,8 93,5 4,5 93,5 4,5 91,5 5,8 88,5 8,4

1,2 [%] 1,0 1,2 1,2 1,4 1,5

3,4 [%] 0,8 1,0 1,1 1,3 1,4

Rubber- and Latex Grades

30

40

50

60

70

Polymerization Temperature [°C]

For commercially available CR-grades small differences in the polymerization temperature and in the 1,4-trans content are an important factor

80

CR: Basic Features of CR- Polymerization Recipes Recipe Ingredients [wt.-parts]

Adhesive grade

Chloroprene 2,3-Dichlorobutadiene Water Disproportionated abietic acid NaOH or KOH Na-methylene-bis(naphthalinsulfonate) n-dodecylmercaptane Potassiumpersulfate Na-Anthrachinon-2-Sulfonate

Latex grade

Standard grades

Sulfur grades

Precrosslinked grades

100 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125

100 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125

90-100 0 - 10 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125

90-100 0 - 10 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125

100 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125

Sulfur

-

-

-

0,3-0,7

-

Dimethacrylates of alkanediols

-

-

-

-

0,1-0,3

Polymerization temperature [°C] Monomer conversion [%]

5 - 20 60 - 85

20-50 60 - 85

30-50 60 - 85

30-50 60 - 85

30-50 70 - 85

CH3

CH3

H CH3 COOH

Dehydroabietic Acid Dihydroabietic Acid

2 Na +

CH2

+

+

H CH3 COOH

SO3

CH3

SO3

H CH3 COOH Tetrahydroabietic Acid

Na-Methylene-Bis(Naphthalinsulfonate) (Baykanol PQ R)

CR: Determination of Crystallization Rate Dependence of Shore A Hardness on Crystallization Rate

Mercury dilatometry for the determination of crystallization rate (Tc =-5°C pretreatment: 30 min at 80°C)

He

0 10

  s   s   e   n    d   r   a    H    A   e   r   o    h    S

He-Hi

20    ]   m30   m    [   e 40   m   u 50    l   o    V

   3

1/2(He- Hi) Hi

60

t1/2

70 80

0,1

1

10

100

1000 10000

0,1

Storage time [h] Source: U. Eisele: Internal Bayer-Reporting System

1

10

Storage time [h]

100

1000

CR: Crystallization Rate and Crystallite Melting Temperature Dependence of t1/2 on Storage Temperature

Dependence of Crystallite Melting Temperatures on Polymerization Temperature

(Baypren 210; Pretreatment: 1 h / 60°C)

30

80

25 20    ] 15    h    [    2    /    1

   t

10 5 0 -20

-15

-10

-5

0

5

10

15

20

   ]    C    °    [   e   r   u    t   a   r   e   p   m   e    t   g   n    i    t    l   e   m   e    t    i    l    l   a    t   s   y   r    C

70 60 50 40 30 20

lowest figures highest figures

10 0 -60

Storage Temperature [°C]

-10

40

Polymeriz ation temperature [°C]

Source: U. Eisele „Introduction to Polymer Physics“ Springer Verlag

 Dependence of Tg and Crystallization Rate at -10°C on  Monomer Feed  and  and Polymerization Temperature Sym- T bol [°C] 45 35 25 15 5

- 31 - 33 - 34    ]    C    °    [ - 35   g    T - 36

Polymerizationtemperature [°C]

103 45

102

35

25

15

5

   ]    h    [

1    2    / 10    1

   t

100

- 37 - 38 0

3

6

9

12

15

DCB-Content of Monomer Feed [%]

10-1

0

3

6

9

12

15

DCB-Content of Monomer Feed [%]

Crystalliaztion Rates of Unvulcanized CR, Unvulcanized CRCompounds and CR-Vulcanizates at - 10°C  500 400

   ] 300    h    [    2    /    1

   t

200

B. 110 VSC

    s     e       t     a      z      i     n     a     c      l     u v     s     e     s     a       b        R      C

 d s    R  n  u  C  p o   d  m   e    i  z  - c o   n   R  C   c  a  d    l  e   z   u  a n  i   n  v   c CR   l    U  n v u   U

Carbon black (N 762) Polyetherthioether Vulkanox DDA Vulkanox 4010 NA Stearic acid Magnesium oxide Zinc oxide

B. 110 KA 8418 B. 112

100

100,0 75,0 10,0 2,0 0,5 0,5 4,0 5,0

phr phr phr phr phr phr phr phr

B. 210

0 0

100

200

300

400

500

600

700

800

t1/2 [h] (unvulcanized CR)

 Dependence of Crystallization Rate on Blending Ratio of Two CR-Grades and on Type of Plasticizer 25

Influence of Plasticizers

Unvulcanized ISO- 2475-1975 Compounds; Measurements at - 10°C CR Stearic acid Magnesium oxide Phenyl-2-Naphthylamin Carbon black (N 772) Zinc oxide (active) Vulkacit® NP

20

100 0,5 0,5 2,0 30 5,0 0,5

(CR-grade: Neoprene® W (~ Baypre® 210)

phr phr phr phr phr phr phr

300 Neoprene® W + mineral oil

250

15

200

   ]    h    [ 10    2    /    1    t

   ] 150    h    [    2    /    1

   t

100

5

Neoprene® W + Butyloleate

50 0

0 -20 -15 -10

100 80 60 40 20 0 Baypren 110 VSC (slowly crystallizing)

-5

0

5

10

15

20

Temperature [°C] 0

20

40

60

80

Baypren 210 (normally crystallizing)

100 Source:

R. M. Murray, J. D. Detenber Rubber Chem . Technol. 34 (1961) 668-685 “First and Second Order Transitions in Neoprene“

 Dependence of Compression Set (CS) of Different CRGrades on Storage Temperature    ) 100   s   e   r 90   u    t   a   r 80   e   p 70   m   e    t 60   e    l    b 50   a    i   r   a 40   v    /    h 30    8 20    6    1    (    S 10    C

DCB-containing rubber grade (Baypren® 110) DCB-free rubber grade (Baypren® 210) CR Adhesive grade (Baypren® 320)

0

-60

- 40

-20

0

20

40

60

80

100 120

140

160 180

Temperature [°C]

Bayer-Brouchure: „Chloropren-Kautschuk von Bayer: Der vielseitig einsetzbare Werkstoff“

Recipe  Features which  are  specific  for  Different CR -  -Rubber   Rubber  Grades  Cl 2 - Chloro - 1,3 - Butadiene •

CH2

Standard CR-Grade

CH CH2 Cl

2,3 - Dichloro - 1,3 - Butadiene

CH2

CH2

S •

Sulfur Grade

Cl

S

S

S

S

S

Sulfur

S

S

CH3 O •

Precrosslinked CR-Grade

Dimethacrylate

CH2

O O

CH2 O n

CH3 CH2

 Molar Mass Control  by  by Mercaptanes and by  Xanthogendisulfides Molar mass control by mercaptanes P*

+ HS - R

P- H

+ R - S*

R - S*

+ nM

R - S - M n*

R - S - M n*

+ HS - R

R - S - Mn - H

+ R - S*

Molar mass control by Xanthogendisulfides P*

+ (RO - CS - S -)2

P - S - CS - OR

RO - CS - S*

+ Mn

RO - CS - S - M n*

RO - CS - S - M n* + (RO - CS - S -) 2

+ RO - CS - S*

RO - CS - S - M n - S - CS - OR + RO - CS - S*

Molar mass control by Xanthogendisulfides results in the formation of polymer molecules with two identical (xanthate) end groups. Xanthate end groups participate in vulcanization. As a consequence, vulcanizates based on xanthate modified CR exhibit better mechanical properties than mercaptane modified CR

CR: Influence of End Groups on Vulcanizate  Properties ISO-Compound 2475 CR 100,0 phr Carbon black N 762 30,0 phr Stearic Acid 0,5 phr MgO 4,0 phr Phenyl-2-Naphthylamine 2,0 phr ZnO active 5,0 phr Vulkacit NPV/C 0,5 phr

CR-grade with xanthate end groups Mercaptan modified CR-grade

16 Vulcanization: 40 min/150°C

22

   ]   a    P 21    M    [    h    t   g   n 20   e   r    t    S   e    l    i   s 19   n   e    T

15 14

   ]   a    P 13    M    [    0    0    3

   M

12 11 10

18 30

40

50

60

70

80

ML 1+4 (100°C)

90

100 110

10

11

12

13

Modulus M300 [MPa]

14

15

 Dynamic Resistance of CR-Standard Grades (   Monsanto Test) Xanthate modified CR-Grade (Baypren 121)

unaged 7 days / 100°C

Mercaptane modfied CR-grade (Baypren 110 VSC)

250

   ]   s   e    l   c   y   c    k    [   e   r   u    l    i   a    f    l    i    t   n   u   s   e    l   c   y    C

unaged 7 days / 100°C

ISO-Compound 2475

200

CR 100,0 phr Carbon black N 762 30,0 phr Stearic Acid 0,5 phr MgO 4,0 phr Phenyl-2-Naphthylamine 2,0 phr ZnO active 5,0 phr Vulkacit NPV/C 0,5 phr

150

100

Vulcanization: 40 min/150°C

50

0 52

54

56

58

60

62

64

68

66

Strain Amplitude[%] Source: R. Musch presented at the 140th ACS Rubber Division Meeting, Detroit October 8-11, 1991

CR -  -Sulfur   Sulfur  Grades  S

Cl

Cl

S

NR2 C S ( CH2 C CH CH2 )v S (CH2 C CH CH2 ) xSy C NR2 w u

 Application: Vulcanizates which are based on CR sulfur grades perform particularly well in dynamic  applications. As a consequence, belts which meet the requirements of different applications are  a major application area (conveyor belts, V-belts, poly-v-belts, timing belts)

 Production: CR-Sulfur Grades are obtained by two consecutive production steps (1. Polymerization and 2. Chemical break down of high molar masses)  In the 1st production step chloroprene and sulfur are copolymerized. The copolymers obtained   have a high molar mass and long sulfur bridges. In the 2nd production step, the molar mass of  the copolymers is reduced by a break down of sulfur bridges (peptization). As a consequence of  the chemical breakt down of the sulfur bridges dithiocarbamate end groups are incorporated. These end group participate in vulcanization.. As a consequence, the number of dangling chain ends is reduced and vulcanizate properties are improved.

Compounding and Vulcanization:  During compounding residual sulfur bridges are broken down "Mastication". Sulfur grades  can be vulcanized by the addition of ZnO and/or MgO (without the addition of accelerators).

Critical Aspects:  During storage, the Mooney viscosity of sulfur modified CR can increase or decrease. Heat  resistance of vulcanizates based on sulfur modified CR is inerior to that of standard CR.

Production  of CR -  -Sulfur  S   ulfur  Grades  1)

Copolymerization of Chloroprene and Sulfur

Cl CH2 C CH

2)

CH2

S8

+

Chemical break down of high molar masses by the use of disulfides, particularly Thiuramdisulfides

Cl Sa ( CH2

Cl

S NR2

S S

S

NR2

S

Cl Sa ( CH2

CH CH2)x

CH CH2 )n Sv Sw ( CH2

CH CH2)n S v S

S NR2

NR2

S

CH CH2) x

Sw ( CH2

 Impact of the Amount of Incorporated Sulfur on Mastication  and Ageing Performance 50

80

Baypren 510

   ] 48    E 46    M    [ 44    )    C    ° 42    0    0 40    1    (    4 38    +    1 36    L    M 34

Baypren 610

  r   u    f    l   u    S    d   e    t   a   r   o   p   r   o   c   n    I

32 30 0

2

4

6

8

Mastication time [min] Mastication: Mill size: Friction: Revolutions: Width: Amount:

200 x 400 mm 1:1,2 20 min-1 1,2 mm 600 mg

10

   ]    %    [    )    C    °    0    0    1    /    d    7    (    0    0    1    M    f   o   e   g   n   a    h    C

70 60 50 40 30 20 10 0 0

0,2

0,4

0,6

Sulfur [phm]

Compound Ingredients: CR Ruß (N 762) Polyetherthioether Vulkanox DDA Vulkanox 4010 NA Stearic acid Magnesium oxide Zinc oxide

100 75 10 2,0 0,5 0,5 4,0 5,0

phr phr phr phr phr phr phr phr

Vulcanization of CR-Sulfur Grades H

H

H

C S

N S

N Sx S

S H

H

H

C

N S

S

N Sx

S

S N

CR-Sulfur grades (which are fully  commercially available) contain  dithiocarbamate end groups which are  attached via sulfur bridges. These end  groups are active in vulcaniaztion. CR-Sulfur grades can be considered as "rubber bound intermediates“ which are  known from theoretical considerations  on the mechanism of sulfur cure.  As a consequence, CR sulfur grades are vulcanized by the use of ZnO and MgO (+ Stearinsäure) without using  accelerators. CR sulfur grades exhibit a critical   stability of Mooney viscosities during  storage particularly at elevated   temperatures.

SH S

 Precrosslinked CR-Grades  Production:  Precrosslinked CR-rades are blends of  gelled CR and ungelled (soluble) CR. The  two blend components are produced   separately by emulsion polymerization.  Prior to finishing, the two latices are  blended. By the latex blending process a  good dispersion of the gelled CR paricles in the soluble CR phase is achieved.

CR-Gel

Ungelled (soluble) CR

 Application: Unvulcanized CR compounds which  contain CR gel exhibit good processing  features, particularly a low die swell.  Major application areas are extruded   articles (wiper blades as well as window  and door seals In these applications CR is being substituted by EPDM and TPEs.

Die swell Rubber Compound

=

de do

x 100 d0

de

 Properties of Precrosslinked CR-Grades 20 50

   ]   a    P18    M    [    h    t   g16   n   e   r    t    S   e 14    l    i   s   n   e    T12

46    ]    %    [ 42    l    l   e   w 38    S   e    i    D 34

30

10

26 0

10

20

30

40

50

60

70

0

10

Gel content [wt.% %]

Mechanism of CR-Vulcanization according to Pariser/Du Pont

CH2

CH2 + Cl S

CH2

NH

CH

CH

+ ZnO - ZnCl +

S

Cl NH

CH2 S

O NH

NH

CH2 O

CH2

-

S

NH

Cl

CH2 CH2

+ CH CH2 S

S N CH3 CH2CH2

NH

CH2

CH2 CH CH2

+ ZnCl +

CH CH2

CH2 CH CH2

NR2

S

"cyclic Dithiocarbamate" (Vulkacit (R) CRV)

Dithiocarbamate end groups are present in sulfur modified CR

Sx S

S

- ZnCl2

Ethylenethiourea (ETU/Vulkacit (R) NPV)

End groups which participate in CR-Vulcanization S

CH2

CH2 CH2

NH

CH2

NH NH CH2CH2 S

S NH

70

S

CH

CH

O

NH

CH2 CH2 CH2

CH2 CH2

60

NH

CH2 CH2 CH2

CH2

CH2

50

Chemicals for CR-Vulcanization

NH

CH2 CH2

CH

40

Vulcanization  of CR 

CH

Cl

+ NH

30

Gel content [wt.% %]

S CH2

20

S

O R

Xanthate end groups are present in in xanthate modified CR

Substitution of CR  250    ]    C    °    [   e   r   u    t   a   r   e   p   m   e    t   e   c    i   v   r   e   s  .   x   a   m

FKM

MVQ

225 FMVQ

200

FZ 80 Resistance to high temperatures % VAc

175

EVM

ACM

AEM to high temperatures, Resistance

HNBR

150

Resistance to dynamic stress

125

NBR

100 AU

75

CM CSM

(H)IIR

EPDM

Price

CR

EU

flame resistance

SBR

BR NR

50 0

20

40

60

80

100

120

max. Volume Swell in ASTM-Öl Nr. 3 [Vol %]

140

no requirements

 Nitrile Rubber (NBR) •

Overview – – – – – –

•

Polymerisation – – – –

•

Emulsifiers Initiator systems Molar mass regulation Copolymerization

Product groups and Properties – – –

•

NBR-Microstructure Basic Features of NBR and Range of NBR Grades Application Areas of NBR and Market Producers and Production Capacities Range of NBR Grades Dependence of Properties on Acrylonitrile Content

Standard grades Carboxylated grades Precrosslinked grades

Vulcanization and Vulcanizate Properties

 NBR: Microstructure N

C C N

CH 1 2

2

HC HC

3 4

C H2

1,4-cis

4

CH2

CH2 CH

3

CH2

C

CH 2

CH2 1

1,4-trans

δ+

CH

CH

Vinyl

δ−

N

CH 2 CH 2 1

Acrylonitrile

 Dependence of the Microstructure of Incorporated  Butadiene Moieties on Polymerization Temperature

Polymerizationtemperature [°C] -20 5 50 100

Microstructure of Butadiene Sequences 1,4-cis 1,4-trans Vinyl [%] [%] [%] 0,8 7,7 14,8 27,6

79,6 71,5 62,0 51,4

19,6 20,8 23,2 21,0

Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)

Standard grades

 Basic Features of NBR Fast curing / Low mould fouling (Injection moulding) slow cure peroxide cure

Special grades

Positive: •

Low degree of swelling in oil, fuels, greases and fats High kevel of mechanical properties High abrasion resistance especiall for carboxalated grades Broad range of grades Low gas permeability Low price level / high competition • •

• • •

Negative: •

•

Maximal service temperature: < 110 °C (Criterium: 1000 h / εb=0,5*εb0) Standard grades are not applicable for outdoor use (contrary to NBR/PVC-Blends)

X-NBR Precrosslinked NBR NBR/PVC-Blends NBR-powder grades liquid NBR -HO-terminated -COO-terminated -NH2-terminated NBR mit bound antioxydant

 NBR- Application Areas in Western Europe Automotive 35%

Rubber Goods (without automotive) 34% Rubber modification of Thermoplastic and duroplastic polymers 11%

Adhesives 1% Others 4%

300    ]    %    [ 250    l    l   e 200   w   s 150   e   m100   u    l   o    V 50 0

Cable and shoes 5% wiring 5%

building 5%

NR

SBR CR NBR 21

0

14 7 time in ASTM-ÖL3 [days]

 NBR:Market- und Development 450 400 350    ]   y 300    /    j    [    n    o 250    i    t    p    m 200   u    s    n    o 150    C

100 50 0    5    8    9    1

   0    9    9    1

   5    9    9    1

   0    0    0    2

   5    0    0    2

   0    1    0    2

 NBR: Production Capacities

(European Rubber Journal 181, n o 4, April, S. 10 1999; updated in July 2010) Zeon

Tokuyama / JP Kawasaki /JP Louisville / USA Houston / USA Barry/Wales / GB (Baton Rouge / USA)

Goodrich Goodyear BP (Copolymer)

Lanxess

La Wantzenau / FR Leverkusen / DE Sarnia / CAN Triunfo / BRA

Polysar Bayer Polysar Petroflex

JSR Polimeri Paratec Korean Kumho Lucky Gold President Eliokem

Yokkaichi / JP Porto Torres / IT Altamira / Mexico Ulsan

Nitriflex PASA S&C Sibur

Negromex/Uniroyal

Hyundai Kaoshing / Taiwan Sandouville / FR Goodyear Valia /Gujarat - Indien Goodyear Duque de Caxais / BRA Santa Fe Bareilly Omsk

Total:

45 20 35 28 15 15

Nipol Nipol Hycar Chemigum Breon (Nysin)

100 35 25 30

Perbunan / Krynac Perbunan Perbunan / Krynac Perbunan

35 30 25 20 16 15 11 25 10 5 2

JSR NBR Europrene Paratec Kumho NBR Chemigum (Powder) Chemigum (bales) Nitriflex/Nitriclean

424

 NBR-Standard Grades 50

   ]    %  .    t   w    [    t   n   e    t   n   o   c   e    l    i   r    t    i   n   o    l   y   r   c    A

45 40 35 30 25 20 15 20

30

40

50

60

70

80

90

Mooney Viscosity ML 1+ 4 (100°C) without pretreatment ( DIN 53523)

100

125

 NBR: Dependence of Tg on Acrylonitrile Content PAN

100 80 60

   ] 40    C    °    [ 20   g +0    T

 e  s   d   r a  g     l   i a  c   r  e   m  o  m   C  o  f  e   n g   a   R

-20 -40 -60

Gordon-Taylor-Equation* TgCopolymer = w1*Tg1 + w2*Tg2 TgE-BR = - 80°C TgPAN = + 100°C *Gordon M., Taylor J. S., J. Appl. Sci., 21, 581 (1950)

-80

E-BR

-100 0

10

20 30 40

50

60 70

80 90 100

Acrylonitrile content [wt.%]

 NBR: Dependence of Volume Swelling on  Acrylonitrile Content 90 80

Expt. Conditions: 14 days Fuel B and C: 20°C ASTM-Oils: 140°C

   ] 70    %    [ 60   e   g   n   a 50    h    C 40    t    h 30   g    i   e 20    W   v   v 10   v   v   v 0 -10

Fuel C (Isooctan/Toluene: 50/50) Fuel B (Isooctan/Toluene: 70/30) ASTM Öl Nr. 3 (aromatic/naphthenic) ASTM Öl Nr. 1 (paraffinic)

0

5

10 15 20 25 30 35 40 45 50

Acrylonitrile content [wt.%]

 Dependence of Shore A- Hardness and Rebound on  Acrylonitrile Content

90

50

80

40

20°C

  s   s   e   n 70    d   r   a    H    A 60   e   r   o    h 50    S

40

75°C

0 5 10 15 20 25 30 35 40 45 50

Acrylonitrile content [wt.%]

75°C

   ]    %    [    d 30   n   u   o    b   e 20    R 10

20°C

0 0

5 10 15 20 25 30 35 40 45 50 Acrylonitrile [wt.%]

Source: Rubber, 3 Synthetic Ullmann‘ s Encyclopedia of Technical Chemistry, Vol A 23 (1993)

 Dependence of Compression Set on Acrylonitrile Content 50

   ]    %    [    ) 40    C    °    0    0    1    / 30    h    0    7    (    t   e 20    S   n   o    i   s 10   s   e   r   p   m   o 0    C 0

5

10 15 20 25 30 35 40 45 50

Acrylonitrile-content [wt.%] Source: Rubber, 3 Synthetic Ullmann‘ s Encyclopedia of Technical Chemistry, Vol A 23 (1993)

 NBR- Polymerization: Activation of Polymerization ,  Molar Mass Regulation and Deactivation Redox Initiation: R-OOH Fe3+ R-O*

R-O* + OH- + Fe3+ Fe2+ + oxydized Reducing agent R-O-Mon*

+ Fe2+ + Reducing agent + Monomer

Growth reaction: R-O-Mon* + n Monomer

P*

Molar Mass Regulation by Mercaptanes: P* + HS - R R - S* + n Monomer R - S - M n* + HS - R

P- H R - S - M n* R - S - Mn - H

+ R - S* + R - S*

Transfer Reaction: P*

+ R-H

R - H + P*

Deactivation: P*

+ P*

P- P

 Emulsifiers for  or NBR- Polymerization Disproportionated Abietic Acid

CH3

CH3

Pd

+

+ H CH3 COOH

H COOH CH3

Abietic Acid

CH3

CH3

H CH3 COOH

 Dehydro abietic acid

H CH3 COOH

Dihydro abietic acid  Tetrahydro abietic acid

Partially hydrogenated tallow fatty acids Producer Brand name BAX Holm Oleon Unichema Cognis

AG IS/1 THT 1618W Radiacid 40 Prifac 5910 Edenor C1618

C14 ges. C14 ges. C18 ges. C18 unges. 3,1 0,4 3,5 2,6 1,2

32,5 27,5 35,1 37,7 40,3

33,5 34,8 24,8 31,5 26,4

31 37,3 36,6 28,3 32,1

Methylen-Bis (Naphthalinsulfonsäure), Na-Salz (Baykanol PQ(R)) SO3

Sulfates- und Sulfonates (Examples) Na-Laurylsulfate Na-Alkylarylsufonate Na-Alkylsufonate

(Texapon) (Marlon) (Mersolat)

CH2

2 Na + SO3

 Activatator Systems for NBR- Polymerization “Organic“ Activation System p-Menthylhydroperoxide (p-MHP) CH2 CH2 CH3 CH

CH3

CH

O

O

H

(NH4)2 S2O8

CH2 CH2

Ammoniumperoxodisulfate

CH3 Na-Formaldehydesulfoxylate Na-Hydroxymethanesulfinate O

H H

“Inorganic“ Activation System

O

S

O

CH2

+

Na

N

H Ethylenedinitrilotetraacetic acid (EDTA) O O HO

CH2 N

HO

CH2

OH

CH2

OH

CH2 CH2 N

CH2

CH2 OH

HO

CH2

CH2

CH2

CH2 OH

Triethanolamine

O

O Ion-(II) sulfate

Fe SO4

Copolymerization Diagram for the Copolymerisation of  Butadiene/ACN - (   for incremental  conversions  conversions )    ] 100    %  . 90    t   w    [ 80   r   e   m 70   y    l   o   p 60    f   o    t 50   n   e    t 40   n   o   c 30   e    l    i   r    t    i 20   n   o 10    l   y   r   c    A 0

Ideal Copolymerisation Azeotropic Composition

0

10 20 30 40 50 60 70 80 90 100

Acrylonitrile content of monomer feed [wt.%] Source: W. Hofmann, Nitrilkautschuk, Berliner Union Verlag

Copolymerization Parameters (ACN = M1; Butadiene = M2) 5°C: r1 = 0,02; r2 = 0,28 50°C: r1 = 0,04; r2 = 0,42 Azeotropic composition: (calculated for 5°C) Acrylonitrile: ca. 38+5 Gew.% Butadiene: ca. 62+ 5 Gew.%

r1 =

k11 k12

r2 =

k22 k21

 NBR: Dependence of Integral Copolymer Composition on Monomer Conversion    ] 100    %  .   w   e 90    G    [ 80   r   e 70   m   y    l   o    P 60    f   o    t 50   n   e 40    t   n   o    C 30   e    l    i   r 20    t    i   n   o 10    l   y   r   c 0    A 0

Modellierungsparameter (ACN = M1; Butadien = M2): r1 = 0,02; r2 = 0,28

Acrylonitrile content of monomer feed: 60 wt.% 50 wt.% 38 wt.% 33 wt.% 28 wt.% 20 wt.% 10 wt.% 5 wt.%

10 20 30 40 50 60 70 80 90 100 Monomer Conversion [%]

W. Hofmann, Nitrilkautschuk, Berliner Union Verlag

 NBR: Dependence of Incremental  and  and Integral  Acrylonitrile Content on Monomer Conversion    ] Incorporation of ACN during batch-polymerization    % 100  .    t   w 90    [   r   e   m 80   y    l   o 70   p    f   o    t 60   n   e 50    t   n   o   c 40   e    l    i   r 30    t    i   n   o 20    l    i   r    t    i 10   n    l   y 0   r   c    A 0 10 20 30 40 50 60 70 80 90 100

Monomer conversion [%]

Incremental composition Integral composition Monomer Feed: Acrylonitrile: 73,7 wt.% Butadiene: 26,3 Gew.% Copolymerizatin parameters: r1 = 0,023; r2 = 0,30 For the production of a NBR-grade with a high chemical homogenity one or both of the two monomers (ACN respectively butadiene) have to be incrementally added during the course of the polymerization in order to compensate for changes in the composition of the monomer feed, unless polymerization is performed in the azeotropic monomer composition

 NBR:  Dependence of Tg on Polymerization Parameters (   Batch- Polymerization ) Sample

Bound Polymerization ACN temperature

ACN-addition during polymerization

Monomer Conversion

Tg Lower Tg Upper Tg

[wt.%]

[°C]

-

[%]

[°C]

[°C]

A

38,9

5

-

>57

B

32,8

5

-

>57

C

25,8

5

-

>57

D

44,8

50

-

>57

-13

E

34

50

-

>57

-26

F

29,2

50

-

>57

-46

-32

G

28,5

50

-

>57

-49

-33

H

23

50

-

>57

-64

-40

I

21,1

50

+

>57

-53

K

31,4

50

-

57

-31

-19 -22 -61

-33

Batchwise NBR-Polymerization may result in chemically inhomogenous blends which exhibit two separate Tg-peaks Source: V. R. Landi (Uniroyal) Presented at a meeting of the Divison of Rubber Chemistry of the American Chemical Society, Cleveland, Ohio, October 12-15 (1971) Rubber Chemistry and Technology

 Influence of TDM -Quality on the Efficiency of  Molar Mass Regulation 160 140   y    t    i    )   s   C   o   °   c   0   s   0    i    1    V   (   y   4   e   +   n   1   o   L   o   M    M

120 100 TDM / Lanxess 80

TDM / Phillips Chevron

60 40 20 0 0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

Amount of TDM [phm]

• • • •

For NBR-Production C12-Mercaptans are efficient molar mass modifiers Tert.-Dodecylmercaptane (TDM) is specifically important TDM by Chevron Phillips is based on propene-tetramers TDM by Lanxess is based on isobutene-trimers

 Molar Mass Regulation by TDM Based  on  on TIB 1. TIB- Production by Isobutene-Oligomerisation 2

+

H

Wagner- MeerweinRearrangement +

+

+

+

- H

+

+ "Triisobutene (TIB)"

2. TDM-Production by the Addition of H2S to TIB SH

H2S / Cat. + "Triisobutene (TIB)"

2,2',4,6,6'-Pentmethylheptanthiol-4

Patent No.

Company

Priority

Patent Title

Jp 07 316 126

Zeon

27.12.1994

Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol

Jp 07 316 127

Zeon

27.12.1994

Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol

Jp 07 316 128

Zeon

27.12.1994

Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol

DE 102007024009

Lanxess

22.05.2007

TDM-Mischung: Herstellung und Anwendung

 Reaction of Incorporated TDM - End Groups During Vulcanization 3. Thermal Decomposition of TDM-End Groups CH3 H3C

C

CH3

CH2 CH2 CH CH CH2 S

C

CH2

CH

Vulcanization

CH2

SH

+

CH3 CH3

CH2 H3C

CH

C

CH3

H3C

C CH3

CH3

CH3 CH2 C

CH C

CH3

CH3

CH3

TDM derived end groups result in: • • •

Acceleration of speed of cure Reduction of free (dangling) chain ends / Improvement of mechanical properties During vulcanization TIB is released which causes odour Patent No.

Company

Priority

Patent Title

EP 0692496 EP 0779300 EP 0779301

Zeon Zeon Zeon

30.03.1993 (Jp) 29.08.1994 (Jp) 29.08.1994 (Jp)

Unsatuarated Nitrile/Conjugated Diene copolymer, process for Producing the same, and Rubber Composition

 Dependence of NBR- Properties on Content of  Metal Ions cCa Ion-Number

=

3

40

cM

+

cNa

 _ 

24

23

cK +

ppm

39

Atomic weight

Influence of Ions on Speed of Cure: accelerating: Na-, K- Ions retarding: Mg-, Ca- Ions

Patent No.

Company

Priority

Patent Title

DE 102007024011 DE 102007014010 DE 102007024010

Lanxess Lanxess Lanxess

22.05.2007 22.05.2007 22.05.2007

Nitrile Rubber with Specific Ion Number Nitrile Rubber with Specific Ion Number Nitrile Rubber with Specific Ion Number

 Dependence of NBR- Properties on Content of  Metal Ions cCa Ion-Number

=

3

40

+

cMg

 _ 

cNa

24

23

cK +

39

ppm Atomic Weight

70

   )    C    ° 60    0    2    1    ( 50    5    S    ] 40    M    n    h   i    c    r    m    [ 30    o    c    s 20   y    e    n    o 10    o    M

0 0,00

20,00

40,00

60,00

Ion-Number (IN)

80,00

100,00

120,00

 Dependence of NBR- Properties on Metal Ion Content cCa Ion-Number =

3

40

cMg

+

 _ 

24

cNa 23

+

cK

ppm

39

Atomic Weight

10 9 8    ]   a    P    M    [    0    0    3    M

7 6 5 4 3 2 1 0 -20

0

20

40

60

80

100

120

Ion-Number (IN)

 NBR: Peroxyde Curable Grades Rubber O O

2

O (R*)

2 C

O

+

+ 2 R-H

C

Crosslinking efficiency 1,0

NBR

Avoidance of phenoland amine based antioxydants (=radical scavengers) H O

C C

X -  -linking  l inking efficiency  =

Type of Rubber

Number of x -  -links  l inks  Peroxide -  -functions   functions  Theoretical X-linking efficiency

M - Rubber

1

R - Rubber

>1

Degradating rubbers

<1

H O

H O

H O

H O S

Vulcanization of NBR: Compound Study Ingredients NBR (18 wt.% ACN)* [phr] Zinc oxide [phr] Stearic acid Vulkanox OCD TMQ Vulkanox MB-2 Carbon black (N 550) Carbon black (N 772) Dioctylphthalat (Vestinol/Hüls) Etherthioether (Vulkanol OT) Vulkalent E Sulfur (Rhenocure IS-60-50) Vulkacit CZ Vulkazit NZ Vulkacit Thiuram Perkadox BC 40 (Akzo) Vulcanization t [min]/T [°C]

EV 1 100 5,0 0,5 1,0 50 5,0 0,4 2,0 2,0 25/160

EV 3 EV 2 100 100 5,0 5,0 0,5 1,0 2,5 1,5 2,5 1,5 80 30 50 20 6,0 1,0 1,0 0,3 0,3 1,5 1,5 2,5 2,0 16/160 25/160

Peroxide 100 1,0 40 5,0 4,0 12/180

* Perbunan NT 1845 (ACN; 18 Gew. %; ML 1+4 (100°C): 50 ME; MR: 14%)

Vulcanization of NBR: Results of Compound Study Vulcanization System ML1+4 (100°C) ts t90 Shore A TS εb

[ME] [min] [min]

[MPa] [%]

EV 1

EV 2 EV 3 Peroxide

78 3,2 7,2

87 1,8 2,6

67 3,4 7,0

77 0,6 4,9

71 16,9 310 4,3 16,3

72 19,5 365 4,4 17,3

71 15,8 310 4,7 15,4

70 18,3 260 4,2 13,0

M100 M300

[MPa] [MPa]

CS (70h/100°C) CS (70h/120°C) CS (70h/125°C)

[%] [%] [%]

12 -

20 31

16 -

14

Brittleness Point Tg CS (24h/-20°C)

[°C] [°C] [%]

-60 -49 -

-62 -53,5 17

-62 -60 20

-

Carboxylated  NBR  NBR (X - NBR) C

N

Carboxl-containing monomers: Methacrylic acid Itaconic acid Maleic Acid • •

C

•

N

COOH

Advantages:

High tensile strength High moduli Good dynamic performance (cut growth resistance) High abrasion resistance

• • • •

Disadvantages:

Scorchiness of Compounds Cost of ZnO2 in relation to ZnO high Compression Set high heat-built-up bei dyn. Beanspruchung Reduced ageing resistance

• • • • •

Application ApplicationAreas: Areas:

Spinning SpinningCods Codsund undspinning spinninghoses hoses high performance shoe soles high performance shoe soles pump pumpstators stators/ /Pump Pumpseals seals belts belts Hydraulic Hydraulichoses hoses

• • • • • • • • • •

Chemistry of Vulcanization with Metal oxides CH2

CH2

C CH3  _  CH3 CH3  _  OOC  _   _  C OOC COO 2+ COO Zn + ZnOH 2+ ZnO CH3 Zn _  2+ ZnO Zn  _   _  + C COO  _  OOC ZnOH COO CH3  _   _  CH2 H3C OOC C C CH2 CH2 C

CH3 8

CH2

C COOH

• • • • • •

CH2

+ ZnO - H2O

CH3 C CH2 CH3 C CH2

Vulcanization with metal oxides is used for X-NBR and CSM. The following metal oxides are used: CaO, MgO, ZnO and ZnO 2  For scorch safety ZnO 2  is superior over ZnO  Usually, vulcanization with metal oxides is combined with sulfur cure  Dual vulcanization results in a „hybride-network-structure“  In a hybride network chemical as well as physical networks are present.

Sources: Eisenberg, A. Macromolecules, Vol 3, 2 (1974) 147 „Clustering of Ions in Organic Polymers - A Theoretical Approach“ Ibarra, L., Alzorriz, M. Polym. Int. 48: 580-586 (1999) Naskar, N., Debnath, S. C., Basu, D. K.; J. Appl. Pol. Sc., Vol 80, 1725-1736 (2001) Brown, H. P. Rubber Chemistry and Technol, 30 (1957) 1347 Crosslinking Reactions of Carboxylated Elastomers“

Compound - and Vulcanizate Properties of NBR and X - NBR 100,0

X-NBR NBR Fmin.

[Nm]

50,0

0

0

50,0

100,0

9,0

10,2

8,0

86,3

78,7

60,0

100

50

0

NBR

0

50

100

ts

[min]

3,0

2,7

2,8

CB (N 660)

40

40

40

t90

[min]

10,0

7,0

6,8

Dibutylphthalate

5

5

5

t95

[min]

21,5

11,0

8,3

Stearic acid

2

2

2

Shore A

83

80

67

Wingstay 29

1

1

1

M100

[MPa]

5,2

4,5

1,7

Sulfur

0,5

0,5

0,5

M200

[MPa]

11,0

10,0

4,8

2

15,5

11,0

TMTD

2

[MPa]

18,6

2

M300 TS

[MPa]

25,5

21,0

18,2

MBS

1

1

1

εb

[%]

430

415

500

Zinc oxide

5

5

5

493

159

73

∆ elongation [%]

- 42

- 35

- 30

CS

34,1

27,1

14,7

X - NBR

Fmax.

Abrasion Index Ageing at 70h/121°C [%]

 Precrosslinked  NBR  NBR Properties: Properties:

Reduction Reductionofofdie dieswell swell Increased Increaseddimension dimensionstability stabilityafter afterextrusion extrusion Improvement of surface quality of extruded/calendered Improvement of surface quality of extruded/calenderedarticles articles Increase of Moduli Increase of Moduli Improvement ImprovementofofCS CS Reduction ReductionofofTS TS Reduction of elongation Reduction of elongationatatbreak break

• • • • • • • • • • • • • •

Precrosslinked NBR

High Mooney NBR Krynac 34.80

Precrosslinked NBR-grades provide for high dimensional stability after extrusion which is only matched by standard NBR-grades with considerably increased Mooney viscosities

 Precrosslinked  NBR: Compound Study NBR* (34 Gew.% ACN)

Krynac VP KA 8769

phr

10

20

30

40

NBR (34 Gew.% ACN)

Krynac 34.50

phr

90

80

70

60

Zincoxide

Lanxess

phr

3,0

3,0

3,0

3,0

Stearic acid

Henkel KGaA

phr

1,0

1,0

1,0

1,0

TMQ (Vulkanox HS)

Lanxess

phr

1,5

1,5

1,5

1,5

Zincmethylmercaptobenzimidazol Lanxess

phr

1,5

1,5

1,5

1,5

Carbon black (Corax N 550)

Degussa

phr

30

30

30

30

Vulkanol 81

Lanxess

phr

10

10

10

10

Sulfur

Kali Chemie

phr

0,3

0,3

0,3

0,3

TBBS (Vulkacit NZ)

Lanxess

phr

1,5

1,5

1,5

1,5

TMTD (Vulkacit Thiuram)

Lanxess

phr

1,5

1,5

1,5

1,5

* Precrosslinked NBR Source: Bayer AG, Marinelli/Welle, KALIS-Nr.: 9588 vom 05. 10. 2000

 Precrosslinked  NBR: Results of Compound Study NBR* (34 Gew.% ACN) NBR (34 Gew.% ACN) Compound-ML [ME] Mooney-Relax. [%] Die swell /linear [%] Fmin. [dNm] Fmax. [dNm] ts1 [min] t90 [min] t95 [min] Shore A/23°C Shore A/70°C M100 [MPa] M200 [MPa] M300 [MPa] Tensile Strength [MPa] Elongation at break [%] Rebound/23°C [%] Rebound/70°C [%] CS (70h/23°C) [%] CS (70h/100°C) [%]

10 90 42 5,8 42,9 0,77 10,63 1,85 5,31 6,61 51 49 1,2 2,4 4,5 19,8 677 40 54 13 34

20 30 80 70 44 47 5,6 5,5 31,7 31,2 0,95 1,15 11,31 12,1 1,77 1,68 4,76 4,58 5,84 5,57 53 55 50 52 1,4 1,5 2,9 3,2 5,2 5,8 16,4 15,5 563 560 39 39 56 57 13 13 32 30

40 60 51 5,7 16,8 1,44 13 1,64 4,5 5,48 57 54 1,7 3,6 6,4 14,1 488 39 61 12 28

4. Overview on Solution Rubbers  •

•

•

Features of the Solution Process Definition of “Solution Rubbers“ Isolation of Rubbers from their Solutions  – 

 – 

 – 

 – 

Dry Finishing with Extruders Dry Finishing with Heated Mills (under vacuum) Solvent Removal by „Steam Striping“ Expeller Screw for Mechanical Water Removal from Rubber

Advantages: •

• •

Use of water sensitive catalyst systems (Z/N, anionic, cationic) evaporation cooling low cooling costs if semi- or total adiabatic processses are applied

Disadvantages: • •

•

• •

•

low content of solids high viscosities reactor fouling waste air waste water (depending on finishing technology) high drying costs for recycled solvents (depending on finishing technology)

 Definition of Solution Rubbers and Examples  A “solution rubber” is prepared in the presence of an organic solvent in which the rubber is either dissolved or dispersed. Examples Reaction Medium

Catalyst/Process

Ti-BR Ni-BR Co-BR Nd-BR

solvent solvent solvent solvent

Z/N* Z/N* Z/N* Z/N*

Li-BR

solvent

anionic

L-SBR EPM/EPDM

solvent solvent

anionic Z/N*

CM/CSM HNBR

solvent solvent

polymer modif. polymer modif .

IIR

solvent

cationic

Rubber

H 1  i    ,4   g -B  h  R  c  i    s  -

 S   o l    u  t   i    o n -B  R

 S   o l    u  t   i    o n R  u  b   b   e  r   s 

* Z/N = Ziegler-Natta Catalysis

 Dry Finishing with Extruders ( Under Under Vacuum ) Dry Finishing:

Recovery of rubbers from their solutions by direct evaporation with extruders without the use of steam

Vent for Devolatilizing Srew press

US 4124306 (French Oil Mill Machinery) Prior.: 30.11.1977 Inv.: D. K. Bredesen, G. C. Craig, W. W. Gilius, C. R. Johnson

 Dry Finishing with Hot Mills ( Under Under Vacuum ) Dry Finishing:

Recovery of rubbers from their solutions by direct evaporation under vacuum with „heated mills“without the use of steam

Source: DE 4032598 (Bayer AG) Prior.: 16.04.1992 Inv.: B. von der Linden, K. Goth

Solvent Removal by Steam Stripping Isolation of CSM from Solution

Stripping unit

Dewatering (expeller) screw

oil

Steam

Antioxydant

Expander screw

Steam PHControl

Waste water

US 2,592,814 (Du Pont) Prior.: 20.12.1947 Inventor: J. L. Ludlow

Stripping aid

Process for Precipitating Polymers

US 5266211 Bunawerke Huels GmbH Prior.: 13.06.19990 Inventor: W. Breuker, H. Wagner, E. Moeller, B. Schleimer

 Expeller Screw for Mechanical  Removal  Removal of Water from Rubbers After steam stripping a dispersion of rubber crumbs in water is otained. Before thermal drying water is removed mechanically

In order to obtain rubber crumbs a cutting device is often attached at the end of a dewatering screw

Source:

US 3672641 (French Oil Mill Machinery) Prior.: 14.09.1970 Inv.: R. K. Slaby

Source:

US 2003007709 (Bayer AG) Prior.: 05.07.2001 Inv.: N. Schweigler H. Goebel, T.-O. Neuner

 4.1. Overview on Polybutadiene Rubbers (BR): CH2 CH

CH2

CH2 CH2

CH CH

CH CH

CH CH CH2 CH2

1,4-cis

1,4-trans

CH2 CH CH2 1,2- bzw. Vinyl

• BR: Overview – – – –

Property Profile and Areas of Application Microstructure, Glass Transition Temperature and Crystallization Producers and Production Capacities Market- und Market Development

• Application of BR for Tyres and for Impact Modification (HIPS/ABS) – Comparison of BR grades in Tyre Performance • Unvulcanized Compound Properties (Green Strength and Tac) • Vulcanizate Performance (Dynamic Performance and Abrasion Resistance)

– Comparison of BR-Grades for the Impact Modification of Thermoplastics (HIPS/ABS) • Principle of Rubber Toughening • BR Branching and Viscosity of Solutions • Correlation of Mooney- and Solution Viscosities

• Performance Requirements for Tyres and Impact Modification • Comparison of Production Technologies for High-cis-BR • Summary

 Property Profile and Areas of Application Positive: • Low price and good performance/price-ratio • Broad range of BR-grades with different molar masses, oil extenison, Tgs etc. • Brod spectrum of applications(tyres, modification of thermoplastics, TRP, golf balls) • Dependence of strain induced crystallization on 1,4-cis content • Low glass transition temperature

Negative: • Poor resistance to heat and ageing • High degreee of swelling in fuels, oils and greases • high gas permeability •Spontaneous crystallization

Application Areas Tyres 71%

Technical Rubber Products 5% Rubber Toughening 23%

Golf ball cores 1%

 BR: Microstuctures  nd Glass Transition Temperatures 2

CH2 CH

1

CH2

1

4

CH2

1

3

CH2

CH CH

CH CH

2

3

2

CH2

3

4

CH CH2

4

1,4-cis Catalyst Tg

1,4-trans

Li* -93

Co -106

Ni -107

1,2- bzw. Vinyl Ti -103

Nd -109

E-BR** -80

Microstructure (according to manufacturer‘s product specifications) [%] 1,4-cis 1,4-trans Vinyl

36-38 52 10-11

97 1 2

97 2 1

93 3 3-4

98 1 <1

12,9 68,3 18,8

4,0 5,4 4,6

<1 0,6 0,7

18,1 17,7 17,8

Microstructure (according to Thorn-Csanyi et al.) [%] Vinyl/ 1H-NMR*** Vinyl/FT-IR*** Vinyl/Metathese***

10,4 11,4 10,7

1,9 1,0 1,7

* aliphatic, cycloaliphatic aromatic solvents without polar additives ** Polymer Handbook/Polymerisation temperature: 25°C *** E. Thorn-Csanyi, H.-D. Luginsland, Rubber Chem. Technol. (1977) 222-230

Crystallization Rate of Unvulcanized  and  and Vulcanized  BR  BR (Nd catalyzed  BR)  BR) 100

Raw Rubber Vulcanizate    ] 10   n    i   m    [    2    /    1    t 1

0,1 -100

-80

-60

-40

-20

Temperature [°C]

Source: U. Eisele Introduction to Polymer Physics, Springer-Verlag 1990

0

 BR: Impact of 1,4- cis-Content on Crystalization Rate and  Melting Temperature of Crystallites 0

250 Nd Ni Co Ti

200    ]   n    i   m 150    [    )    C    °    0    2   - 100    (    2    /    1    t

50

0 90

92,5

95

97,5

100

  s   e    t    i    l    l -5   a    t   s   y   r   c    f -10   o   e   r    ]   u   C    °    t    [-15   a   r   e   p   m   e -20    t   g   n    i    t    l   e -25    M

Nd Ni Co Ti

90

1,4-cis-content [%]

92,5

95

97,5

100

1,4-cis-content [%]

 BR: Producers and Production Capacities 500 450 400 350    ]    t    k    [   y    t    i   c   a   p   a    C

300 250 200 150 100 50 0

  i   d   i  m   C   b  e   S  R  a  h  i   o  n   e  r s  s s   e a  r   e  l  i  n   p  e c   /  F  S   h  o   i  b  u  r   e  r   o  w    n   R   h   e a   U   J   A s    Z  e   t  h   y c   i  n  o   B  S   K  u  m   S   o  l  i  m   D   h a  i  l   f  t  e c    T  S   n  x   o  d   i   h   o  a   M   S   P   L   G  o    T   n  e  s  k   m  a   k   n  e   h   z   N  i

Source: IISRP Worldwide Rubber Statistics 2001 / Amendments 2011

Selected  BR  BR- Producers and BR-Grades Polimeri, Ravenna, IT Lanxess, Dormagen, DE Chemizna D wory, SA, Kralupy, CZ

Li Ni Ti Co Nd Li/Co/Nd Ni/Nd

Ube, Chiba, JP Nizhnekamskneftechim Michelin, Bassens, FR Dow, Schkopau, DE Petroflex, Cabo, BR Lanxess, Port Jérôme, FR Korea Kumho, Yeochin, Yeosu BS/FS, Lake Charles, La Lanxess, Orange, Texas Sinopec, GaoQiao, Caojing ASRC (Michelin), Louisville, Ky Goodyear Tyre&Rubber Co., Beaumont, Tx 0

50

100

150

200

250

300

350

400

Capac ity [kt]

 BR: Application Areas Application Areas of BR Technical Rubber Goods 5% HIPS/ABS 23%

not assigned 7% Li-BR 7% Nd-BR 8%

Tyres 71%

Golf balls 1%

Tyre Market (2.2 Mio t)

HIPS/ABS-Market (0,68 Mio t) Ni-BR 38%

Li-BR 48%

Co-BR 22%

Ti-BR 18%

Co-BR 52%

Anatomy of a Passenger Tire and Use of BR 

Tread SBR/BR: 70/30 Sub Tread NR/BR: 80/20

Sidewall NR/BR: 60/40

Carcass NR/BR: 90/10

Rim Cushion NR/BR: 80/20 Apex NR/BR: 80/20

Source:

Comparison of BR-Grades for the Application in Tyres (   ASTM -Compound  3189  3189 – 90) BR (Nd-, Co-, Ti-, Li-)

100,0 phr

Zinc oxide

3,0 phr

Sulfur

1,5 phr

Stearic acid

2,0 phr

Carbon black (NBS 378)

60,0 phr

TBBS

0,9 phr

Oil (ASTM Type 103)

15,0 phr

Vulcanization:

145°C/35 min

Source: Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98 ASTM Designation: D 3189 - 90 „Standard Test Methods for Rubber-Evaluation of Solution BR

Green Strength of BR-Compounds 5 4

   ] 3   a    P    M    [ 2   s   s   e   r    t    S 1

Li-BR

Ti-BR

Co-BR

Nd-BR

0 0

250

500

750

1000

Strain [%] Source: Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98

Tack of Unvulcaniuzed  BR  BR-Compounds 350

   t   n   e   m   e   v   o   r   p   m    I

Li-BR

   ]   c300   e   s    [   n250   o    i    t   a   r 200   a   p   e   s150    l    i    t   n   u100   e   m    i    t 50 0 100

Ti-BR Co-BR Nd-BR

1000

10000

critical load for separation [g] Source: „

Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98

Vulcanizate Properties of BR Grades BR Grade

Nd

Co

Ti

Li

Vulcanizate properties Tensile Strength

[MPa]

15,3

14,5

13,4

13,0

Elongation at break

[%]

400

525

510

480

M300

[MPa]

9,4

8,6

8,1

8,0

65

63

64

66

Shore A-Hardness Rebound

[%]

49

47

45

47

DIN-Abrasion

[mm3]

23

27

33

52

Asphalt, dry

85

85

85

89

Asphalt, wet

33

33

33

35

Pendulum -Skid

Dynamic properties Goodrich-HBU

[°C]

27

32

36

18

De-Mattia crack growth

[mm/kc]

1,9

6,0

1,5

5,6

Monsonto-FTF/ε =100%

[cycles]

460

50

115

63

Source: “

Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98

1,4- cis BR: Dynamic Performance of BRVulcanizates (   Monsanto Fatigue to Failure Test)

   t   n   e   m   e   v   o   r   p   m    I

  e   r   u 40    l    i   a    F35    l    i    t 30   n   u   s 25   e    l   c   y 20   c   o    l    i 15    K    f   o 10   r   e    b 5   m   u 0    N

Ti

Ni

Co

Nd

Source: D. J. Wilson „Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes“ Makromol. Chem., Macromol. Symp. 66, 273-288 (1993)

1,4- cis BR: Abrasion Resistance of BR-Vulcanizates (   DIN - Abrasion ) 50 Ti-BR

   t   n   e   m   e   v   o   r   p   m    I

45

Ni-BR

   ]    3   m 40   m    [   n 35   o    i   s   a   r    b 30    A

Co-BR Nd-BR

25 20 0 Source:

5 10 Modulus at 300% elongation [MPa]

15

D. J. Wilson „Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes“ Makromol. Chem., Macromol. Symp. 66, 273-288 (1993)

Phase Morphology of Rubber Modified  Thermoplastics and Thermoset Resins  Grafted Shell „Compatibilizer“ Hard Phase (coherent phase or matrix) Soft (dispersed) Phase

The impact resistance of hard and brittle thermoplastic and duroplastic polymers is improved by rubber particles Prerequisites for an efficient impact modification are: 1) good dispersion of the rubber phase in the matrix 2) good mechanical bonding across the phase boundaries 3) x-linking of the rubber phase

Rubber Modified Thermoplastics

Soft Phase

Hard Phase

Examples

BR BR EPDM EPM NBR

SAN PS SAN PP PP

ABS HIPS AES EPM/PP NBR/PP

Source: C. Schade, H.-J Renner, W. Heckmann (BASF) „Predictive property Adjustment“ Kunststoffe international 7/2010, 36-39

Influence of Rubber Content on Notched Impact Resistance of EPM/PP -  -Blends   Blends 

   ]    2   m 80    /    J    k    [   e   c   n60   a    t   s    i   s   e   r    t   c40   a   p   m    i 20    d   e    h   c    t   o    N

0

52

47

33

37

25 Rubber content [wt.%]

h o 

20

h e  -40

-20

0

20

Temperature [°C]

Source: H. Schwager (BASF); Kunststoffe 82, 499 (1992) T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 „New Polymers from New Catalysts“

 Impact of Branching on Solution Viscositiy  of Li- BR in Styrene 100000

   ] 10000   s    *   a    P 1000   m    [   y 100    t    i   s   o   c 10   s    i    V 1

HX 565 Mooney: 65

Degree of Branching: 50-55

HX 501 Mooney: 40

Degree of Branching: ca. 18

HX 530 Mooney: 65

Degree of Branching: ca. 10

5

7

9

Solid Contents of BR solution [wt.%] Source: Rubbers as Impact Modifiers for Plastics Bayer AG Rubber Business Group Order No.: KA 34271e

Correlation of Solution and Mooney Viscosities of  Different BR-Grades    ]   s 260    *   a    P 240   m    [ 220    )   e   n   e 200   u    l   o 180    t   n 160    i

Li-BR (commercial grades) Co-BR (commercial grades)

   %  . 140    t   w    3 120    4  ,    5    ( 100   y    t    i   s 80   o   c   s 60    i    V 40   n   o    i    t 20   u    l   o    S 0 0

  t   l  y  d  e  s    h   g    a   s   l   i   g   r   n  d   B   R   a   a  r   h  e  d   e   n   c    L   i  r  a  n    b 10 20 30

Star shaped BR

40

50

60

70

80

Mooney-Viscosity (ML1+4/100°C) [MU] Source: „Rubbers as Impact Modifiers for Plastics“ Bayer AG, Rubber Business Group, Order No.: KA 34271e

 Performance Requirements for the  Application of BR in Tyres and HIPS/ABS Property

Performance Requirements for tyres for HIPS/ABS Tg as low as possible as low as possible Vinyl content > 1 Mol% Gel content not crical <500 ppm Solution viscosity <21 mPas (5,2% / toluene) colour colourless Tack yes Green strength yes Strain induced crystallization yes dynamic resistance yes Abrasion resistance yes -

The performance profiles for HIPS/ABS und for tyres  differ significantly

 High- cis- BR Production Technologies Transition Metal

Co

Solvent Residence time Conversion

[min] [%]

Tendency towards gel formation Heat removal

Molar Mass Control agents Formation of 4VCH Transition metal content

Benzene, Benzene Toluene Toluene (Aliphatics) Hexane 150 120

[ppm]

Ti

Nd

Benzene Toluene

Hexane Aliphatics

120

100-120

55-80

<85

<95

<100

high

high

low

Very low

partially adiabatic 14-22

Solids Content

Ni

partially partially adiabatic adiabatic 15-16 11-12

fully adiabatic 18-22

yes

yes

no

no

high

high

low

10-50

50-100

Very high 200-250

100-200

Positive feature

Formation of 4-VCH by a Diels-Alder-Reaction Butadiene

4-Vinylcyclohexene (4-VCH)

Summary From the different BR grades, Nd-BR is advantageous from two points of view: • Tyre applications (particularly tyre treads) • Production technology

For the impact modification of thermoplatics (HIPS and ABS) • Li-BR and Co-BR are superior • for Nd-BR a highly branched grade with a low solution viscosity is required

 4.2. LiBR and S-SBR

With a Special Emphasis on Integral Rubber • Selected Milestones in Rubber History • Capacities of Multi-Purpose Solution Plants • Origins of S-SBR Technology and Basic Features • Chemical Aspects of the Anionic Polymerization and Consequences – Reaction Mechanism and Catalyst Costs – Vinyl-Content and Impact on Tg – Branching and Impact on Processability – Styrene/Butadiene-Copolymers, Preparation and Properties – Integral Rubber

• Green Tyre Technology • Recent Developments in S-SBR Technology Towards Improving Tyre Performance – Functionalisation of S-SBR

Selected  Milestones  Milestones in Rubber History with a Special Emphasis on Anionic Polymerization 1839 1888 1910 1914-18 1926 1929 1929 1936 1938 1939-45 1952 1960ies

Charles Goodyear discovers the vulcanization by sulfur John Dunlop patents pneumatic tire Matthews, Strange (England), Harries (Germany) and Schlenk (Germany) discover sodium as a catalyst for polymerization Start-up of Methyl-Rubber production in Germany (2,3-dimethylbutadiene/Na-catalyst) Butadiene rubber developed in Germany (Buna) Ziegler discovers BuLi to be a polymerization catalyst First laboratory scale E-SBR by Tschunkur & Bock (Buna S) Ziegler describes the features of the anionic polymerization Invention of redox activation by Bock (“cold E-SBR“) BR-production in Russia (catalysts based on Na and K) Start-up of R&D into diene base rubbers/Li-metal by Firestone Start- up of commercial productions using anionic initiators by Firestone, Shell and by Phillips Petroleum

Source: H. L. Hsieh, R. P. Quirk, Anionic Polymerization, Principles and Practical Consequences, Marcel Dekker Inc. New. York, Basel 1996

Capacities of Multi- Purpose Solution Plants* (BR/S-SBR-SBS-TPE‘ s)

Plant Location

Capacity [kt]

Remarks Origin of basic technology

Western Europe EniChem Bayer Michelin Repsol Qimica Fina Polymers Dow

incl. TPE‘s

Firestone/Asahi Phillips-Petroleum technology origin not assigned

Ravenna Grangemouth Lillebonne Bassens Santander Antwerp Schkopau

100.000 80.000 120.000 85.000 80.000 80.000 60.000

Louisville, Ky Lake Charles Orange Orange Beaumont, Tx Cabo Salamanca Altamira

110.000 180.000 125.000 30.000 360.000 35.000 30.000 10.000

Oita Tokuyama Yokkaichi

48.000 296.500 30.000

incl. TPE‘s incl. E-SBR incl. Hydrogenated polymers

Yeochon Kaohsiung Newcastle

145.000 210.000 30.000

incl. TPE‘s

incl. TPE‘s incl. TPE‘s

Americas ASR Bridgestone/Firestone Bayer Goodyear Petroflex Negromex

incl. TPE‘s incl. TPE‘s

Japan Asahi Japan Elastomer Nippon Zeon JSR

Others Korean Kumho Taiwan Synthetic Dow (Carbochem)

Total Capacity

2.274.500

* Source: IISRP Worldwide Rubber Statistics 2001

Origin of S-SBR-Technologies and Basic Features Feature

Technology

Initiator Solvent Randomizer branching agent/chain end coupling short stop process temperature control sequential monomer addition Vinyl content of BR-moieties molar mass distribution of base polymer

Firestone/Asahi

Phillips

n-Bu-Li n-hexane none DVB water continuous adiabatic butadiene ~ 10% broader

sec.-Bu-Li cyclohexane glymes DVB, SiCl4, SnCl4 stearic acid discontinuous, batch isotherm one shot > 20% narrower

Until today, the technologies have merged and there are only  small differencies in the technologies of the leading companies Basic Patents: Firestone:

Phillips: Bridgestone:

US 3317918, CA 966949, US 3205211, FR 1546396, FR 1539429, FR 1539427, BE 718549, US 3681304, OS 2134656, US 3558575, US 3726844, US 3726844, US 3787377 US 3458490, US 3438952, US 3502746 JP 75-015271

 Mechanism of the Anionic Polymerization Initiation: R

+

Li

CH2

+

R

+

Li

Chain growth: CH2

+

Li

R

CH2 +

n

R

Transfer reactions:

ideally none

Termination reactions:

ideally none

+

Li

n

• Under ideal polymerization conditions, there is neither chain transfer nor  termination reactions and the active species are truly living. • All polymer chains are initiated at the start of the polymerization and all  chains grow up to total monomer consumption. • The resulting polymer molecules have a narrow molar mass distribution  and a high chemical homogeinity

 Features of a “   Living Polymerization“  nMonomer DP =

   ]    l   o   m    /   g    [    )   n    M    (   s   s   a    M   r   a    l   o    M

nInitiator * f 

X

nMonomer * MWMonomer Mn = Mn

nInitiator * f  =

C

=

m

=

X

DP: degree of po0lymerization Mn: number average of molar mass X: monomer conversion nMonomer : amount of monomer [moles] MWMonomer : molar mass of monomer nInitiator : amount of i nitiator [moles] f: functionality of initiator u, v, w: amounts of initiator

m *X + C

nInitiator = u

0

nInitiator = v

n Monomer * MGMonomer nInitiator * f 

nInitiator = w u
0

0,5 Monomer Conversion X

1,0

Living Polymerization: Rational for Uniform Terminology T.r. Darling, T. P. Davis, M. Fryd, A. A. Gridnev, D. M. Haddleton, S. D. Ittel, R. R. Matheson, jr., G. Moad, E. Rizzardo, Journal of Polym. Chemistry, Vol 38, 1706-1708 (2000)

 Impact of Initiator Concentration on Molar  Masses and on Catalyst Costs    ]   r   e 25    ]    b   g    b    k   u    /   r    f   g 20    P    [    k    [    /    f    i    P    L 15    [   u    i    L    B     r 10   u   o    B    f   r   s   o    t    f   s 5   s    t   o   s    C   o    C 0

Basis of calculation: • 65 DM/kg BuLi (4 DM/mol BuLi; MwBuLi: 61 g/mol) • Ideally “Living Polymerization“

0

50000

100000 150000 200000 250000 300000 350000 400000

Molar mass [g/mol]

Molar mass [g/mol]

Consequences from the living nature of the polymerization: • Catalyst costs increase with decreasing molar masses. • Star shaped polymers are obtained by the coupling of low molar mass  polymers. Therefore star shaped polymers are bound to be more expensive  than standard rubbers at the same molar mass.

 Impact of the Gegenion and of the Solvent  on the Vinyl -Content Gegenion

Li Na K Cs

Microstructure (Benzene) cis-1,4 trans-1,4 1,2[%] [%] [%] 35 10 15 6

55 25 40 35

1,4-insertion:

-

P

10 65 45 59

Hexane Toluene THF

Microstructure cis-1,4 trans-1,4 1,2[%] [%] [%] 35 35 0

55 52 9

10 13 91

P

-

1,2-insertion:

-

P Solvent

Li +

Li +

P

+

+

Li

Li

X

X

X

X

X

Ether with two coordination sites

Sources: R. Casper in Ullmann‘s Encyclopedia of Technical Chemistry G. Sylvester u. P. Müller in Houben Weyl, Methoden der organischen Chemie, Band E 20/Teil2, Makromolekulare Stoffe, S. 801

X

 Dependence of the Vinyl -Content on Polymerization Temperature and Modifier (Type and Concentration) 90 80

DME 30°C

   ] 70    %    l   o   m 60    [    t   n   e 50    t   n   o 40    C      l   y 30   n    i    V 20

THF 30°C THF 50°C

DME 50°C

THF 70°C

DME 70°C

Modifier: DME: Dimethoxyethane THF: Tetrahydrofuran

10 0

0,1

1,0

10

100

Ether [mol/mol Li] Source: Ullmann‘s Encyclopedia of Technical Chemistry

 Impact of the Vinyl Content of Li- BR on Tg +0

VI-BR

-10 -20

Range of commercial Vinyl-BR grades

-30 -40    ] -50    C    °    [   g -60    T -70

-80 -90

Standard-Li-BR (without modifiers)

-100 0

10

20

30 40

50

60

70 80

90 100

Vinyl-Content [%] S. L. Aggarwal, T. G. Hargis, R. A. Livigni, H. J. Fabris, L. F. Marker, „Advances in Elastomers & Rubber Elasticity, J. Lal a. J. E. Mark, Eds., Plenum Press, New York, 1986, p. 17

 Li- BR: Dependence of Wet Skid  and  and Abrasion Resistance  on Vinyl Content Vinyl-BR 64 21 15

66 18 16

88 7 5

SBR 1712 18 8 74

Wet Skid Performance (Laboratory) Portable Test Device* 84

109

104

120

100

Retreaded Tyre Concrete Asphalt

70 70

95 90

92 92

93 93

-

100 100

Abrasion Resistance

140

100

80

Vinyl Content 1,4-cis 1,4-trans

10 40 50

47 26 27

100

* Road Research Laboratory Instrument, on wet Syenite-Glass Surface

 Branching by the Copolymerization with  Divinylbenzene Copolymerization with multifunctional monomers (DVB):

R

n

CH2 Li

+

R

n

+

CH

Li

CH

Li

+

+

CH2 Li

R n

R n

+

 Branching by Chain End Coupling Chain end coupling with SiCl4, SnCl4 etc.: C

4

Li

Coupling with SiCl4: • Reduction of Cold-Flow • low viscosity of BR-solutions • Application for HIPS and Bulk-ABS • Highly filler loaded rubber compounds with good processability and high ShoreA Hardness (roll covers, tyre beads etc.)

+

SiCl4 (SnCl4 as alternative)

Coupling with SnCl4: +

+ 4 Li Cl

Si

exclusive úse is for tyres; during compound preparation the Sn-C bonds seems to break and the bound rubber content is increased. As a consequence hysteresis of vulcanizates is reduced. Many patents in this area, for example: US 6271317 (Goodyear) Prior.: 19.01.1998, Inv.: A. F. Halasa, S. Futamura, W. L. Hsu, B. A. Matrana „Asymmetrical Tin-Coupled Rubbery Polymers and Method of Making“ (Star shaped rubbers with at least 3 brances; 1 branch with MW <40.000 g/mol and 1 branch with MW>80.000 g/mol)

 Impact of Chain Branching on Processability Cold  flow

  y    t    i   s   o   c   s    i    V

   t   n   e   m   e   v   o   r   p   m    I

Mooneymeasure ment

Com- CalanEx- Injection Spinpression dering trusion moulding drawing moul ding

   t   n   e   m   e   v   o   r   p   m    I Narrow molar mass distribution Highly branched (Star shaped) 100

101

102

103

Broad molar mass distribution 104

105

106

Shear rate [sec-1] Source: U. Eisele, Introduction to Polymer Physics, Springer Verlag 1990

 Li- BR: Influence of Branching on Cold Flow 14 Linear Chain

12    ]   n    i   m    /   g   m    [   w   o    l    F    d    l   o    C

10 8

Star shaped polymer with 3 branches

6

Divinylbenzene [phm]

4

0,03

2

0,06

0

0

20

40

60

80

100

Mooney-Viscosity ML 1+4 (100°C) [MU] Linear BR has an extremely high cold flow which results in the instability of rubber bales. BR has to be branched in order to improve the stability of bales.

 Properties of Linear and Star Branched  Li  Li- BR Li-BR

linear

star branched

Coupling agent

without

SiCl4

Mw [g/Mol] Mn [g/Mol] Mw /Mn Cold flow [mg/min] ML 1+4(100°C) Compound-Mooney ML 1+4 (100°C) Shore A Hardness S300 [Mpa] Tensile Strength [Mpa] heat-build-up [°C] Rebound [%]

256.000 188.000 1,4 16 53 98 64 8,0 16,5 32 77

310.000 158.000 2,0 0 54 80 61 8,1 16,2 40 71

Compound Preparation: BR: 100 phr, Ruß (IRB Nr. 2): 50 phr, Zink oxide: 3 phr, Mineral oil : 10 phr, Stearic acid: 2 phr, Sulfur: 1,75 phr, Accelerator: 0,8 phr; Vulcanization: 135 °C/35 min

S-SBR: Solution-SBR

 L-SBR: Market and Market Development Introduction of “Green Tyre Technology by Michelin“ 700 600

   ]    t    [   n 500   o    i    t 400   p   m   u 300   s   n   o 200    C 100 0 1989

1991

1993

1995

1997

1999

Source: IISRP; Evaluation by Bayer AG (Wachholz/BPO-IIS-BPSC-SP)

2001

Copolymerization of Styrene and Butadiene at  Differential Monomer Conversions 100

   ]    %90  .    t 80   w    [ 70   r   e   m 60   y    l   o 50 E-SBR   p    f   o    t 40 S-SBR   n   e 30    t in hexane   n   o   c 20   e 10   n   e   r 0   y    t    S 0 10 20 30 40 50 60 70 80 90 100

Parameters of copolymerization (styrene = M1; butadiene = M2) Radical copolymerization (emulsion) r1 = 0,7 r2 = 1,4 Anionic colymerisation in hexane (Bu-Li/no randomizers/50°C) r1 = 0,04 r2 = 11,8

Styrene-content of monomer feed [wt. %]

Copolymerization of Styrene and Butadiene

The anionic copolymerization of styrene and butadiene in an unpolar solvent (hexane) yields a block copolymer with the following features: • high chemical homogeinity • narrow molar mass distribution • tapered intermediate sequence

Course of the copolymerization in hexane (full batch process): start up of the reaction Butadiene block

tapered sequence

styrene block

 For tyre applications block styrene blocks have to be  avoided  as  as they cause high hysteresis losses .

Styrene/Butadiene-Copolymerisation   r   e 100   m   y 90    l   o   p 80   e    h    t 70   n    i    t 60   n   e    ]    t E-SBR   n    %50   o  .   c    t  R    40   e    [   w S-SBR  m   a    n  d       n i    30 in Hexane   e  z   o  -     r e    r      y  s      t 20   s    l   a 10    i    t   n   e 0   r   e    f 0 10 20 30 40 50 60 70 80 90 100    f    i    D Styrene content in the monomer feed [wt. %]

 Impact of Randomizers on the Copolymerization  Behaviour of Styrene and Butadiene (Styrene = M1; Butadiene = M2)

T [°C]

r1

Cyclohexane; 25/75 Styrene/Butadiene

r2

Benzene Cyclohexane Hexane

25 25 25

0,04 0,04 0,03

10,8 15,5 12,5

THF Diethylether Triethylamine Anisol Diphenylether

25 25 25 25 25

4,0 0,4 0,5 0,3 0,1

0,3 1,7 3,5 3,4 2,8

THF THF THF

-78 0 25

11,0 5,3 4,0

0,04 0,2 0,3

70

n-Butyl-Lithium

  r   e 60   m   y    l   o    P 50    f   o    t 40   n   ]   e    t   n   %  .   o   t30   w    C   [   e   n   e   r 20   y    t    S    l   a 10    t   o    T

t-BuOK/n-Buli: 0,067/1 t-BuOK/n-Buli: 0,38/1

0 0

20

40

60

80

100

Monomer Conversion [%]

Source: H. L. Hsieh, R. P. Quirk, Anionic Polymerization, Principles and Practical Applications, Marcel Dekker, Inc. Y. Melenevskaya, V. Zgonnik, V. Denisov, E. Dolinskaya, K. Kalnish; Polym. Sci. (USSR), 21, 2215 (1979)

Tg of S-SBR: The Impact of Styrene and Vinyl Content 40

   ]    %  . 30    t   w    [    t   n   e 20    t   n   o    C   e 10   n   e   r   y    t    S

0

   t   u   o    h    t    i   w   y  s   g  r   e   o   i   z    l   o  m   n  o    h   c   d   e  n    t   a   n  r   o    i    t   u    l   o    S

0

10

+10°C

  y   g   o    l   o   n    h   c   e    T   n   o    i   s    l   u   m    E    d   r   a    d   n   a    t    S

+ 0°C - 10°C

S olu ti on te ch nolo gy with

- 20°C

 ra n do mi ze rs - 30°C - 40°C - 70°C

20

30

- 50°C

- 60°C

40

50

60

Vinyl [%]

 In the variation of the microstructure ( vinyl  vinyl - content )  ) the S-SBR  technology has a greater versatility than the E-SBR- technology. Source: H. Mouri, J. E. Hall, (Firestone) 146th ACS meetin in Pittsburgh, PA., USA

 Impact of Tg on Important Tyre Tread  Properties  Properties S-SBR (25% Styrene, 55% Vinyl)  E-SBR 1516 (40% Styrene) S-SBR (34% Styrene, 32% Vinyl)

-20 -40

   ]    C    °    [ -60   g    T -80 -100

 E-SBR 1500 (23.5% Styrene)  E-SBR (15% Styrene) S-SBR (18% Styrene, 10% Vinyl)  Emulsion BR  Li-BR  high cis Nd-BR  Decrease of Rolling Resistance  and Abrasion  Increase of Heat Build Up  and Wet Skid Resistance

 In order to comply with many conflicting tyre tread  properties  properties the  preparation of rubber blends is essential in rubber technology. An  alternative to macroscopic blending would  be  be microscopic blending  as with integral rubber.

The „ Integral Rubber“ Concept Li- NR SBR BR 1500

SBR 1700

1 10-1        δ

  n 10-2   a    t

Integralrubber

10-3

-100 -80 -60 -40 -20

0

20

40

60

80

100

Temperature [°C]

Integral Rubber is a multi block copolymer the building blocks of which have well defined Tgs Source: K. H. Nordsiek, K. M. Kiepert, Kautschuk Gummi Kunststoffe 38 (1985), p. 178-185

 Routes for the Preparation of Integral Rubbers Integral-Rubber 1 based on butadiene, styrene and isoprene (full batch process without the sequential addition of either monomer or modifier)

Segment: Tg [°C]

Vinyl-BR -90°C

S-SBR -20°C

3,4-IR ~ 0°C

Integral-Rubber 2 based on butadiene, styrene and isoprene (batch process with sequential monomer- and modifier addition) butadiene

Segment: Tg [°C]

randomizer styrene

Medium-cis BR -90°C

Vinyl-BR -50°C

isoprene

S-SBR -20°C

3,4-IR ~ 0°C

 Performance Comparison of Standard S-SBR with  E-SBR in a Carbon Black Compound  E-SBR

S-SBR

+ + +

-

t10 t90 t90 - t10

+ 0

+ +

Moduli Tensile Strength Tear resistance Abrasion resistance Heat build up Rolling resistance Wet grip

+ + + + + +*

Processability Black incorporation time Tack Green Strength

Vulcanization  In a carbon black loaded  compound  compound  there is no real advantage for S-SBR.

Mechanical Properties

Price

Therefore there was no major break through for S-SBR until  the  the green tyre  technology emerged   .

+ + + -

* fully depreciated plants

Green Tyre Technology Et-O Et-O Et-O

Si OH

SiO2

Si

Si

Et-O Et-O Et-O

OH

Performance of the green tyre

Si

CH2 CH2 CH2 S

CH2 CH2 S CH2

150 Rubber

100

Filler Silane Additive

50

Raw Materials Mixing Costs

0

S

Additional costs for the green tyre

Rolling Resistance Carbon black loaded tread Green tyre

S

Ruß Compound

Silica Compound

E-SBR Ruß -

L-SBR NR BR Silika Si 69 DPG

++ ++

---

Patents:

Abrasion Resistance

Wet Skid

DE 2447614; Degussa, Prior.: 05.10.1974; Erf.: K. Burmester, S. Wolf, E. Klötzer, F. Thurn US 4,709,065; Shin-Etsu; Prior.: 20.09.1985; Erf.: H. Yoshioka et al. EP 299074; Bridgestone; Prior.: 03.10.1987; Erf.: T. Hamada et al. DE 3813678; Bridgestone; Prior.: 23.04.1987; Erf.: M. Takeshita et al. EP 501 227; Michelin, Prior.: 25. 02. 1991; Erf.: R. Rauline EP 447066; Bridgestone; Prior.: 27.02.1991; Erf.: T. Hamada

 Recent Developments in S-SBR Technology Towards Improving Tyre Performance

Functionalisation of S-SBR • Partial or total substitution of activator • Improvement of silica dispersion • Iprovement of silica reinforcement • Reduction of hysteresis loss • Improvement of wet skid • Reduction of abrasion loss

 Functionalization of Living Chain Ends OR R1 R

n

C

Li

+

+

N C

91

R2

Li

R

Si OR CH2 OR

n

+

OR Si OR N C CH2 OR R1 R2 80

EP 1113024 A1; Prior.: 02.12.1999, Bridgestone, Inv.: K. Morita, H. Kondo "Polymer process for making the polymer and rubber composition using the polymer“

 Functionalization with Polyether Segments O 2 R

CH2

n

Li

+

+

- 2 Li

Cl +

n

Cl

Cl

O R

n

n

nR

DE 10057508; Bayer AG, Prior.: 21.11.2000; Erf.: T. Scholl, W. Obrecht, Braubach, E. Giebeler, Grün, A. Müller, M. Graf  „Polyether/Diolefin-Kautschuke enthaltende Kautschukmischung“

 Incorporation of Aminoisoprene CH3

CH3 N CH2

CH2

C CH

CH2

Dimethyl-Aminoisoprene • is incorporated initially at the chain end • it acts as a randomizer during the whole course of the polymerization • the aminoisoprene containing rubber exhibits increased interaction with silica

EP 01165641; Bayer AG, Prior.: 03.02.1999; Erf.: T. Scholl, W. Obrecht, R. Stadler, R. Morschhäuser, G. Mannebach "Kautschukmischungen basierend auf Aminoisopren"

 Functionalization of the Living Chain End with  a Polysiloxane Building Block H3C

CH3 Si

R n

+ H3C

+

CH2

Li

O

O

Si

Si O

H3C

CH3 CH3

 D3

CH3 CH3 CH3 CH CH3 CH3 3 Si R

O

n

Si

Si

O

O

+

Li

Source: EP 0778 311; Michelin, Prior.: 07.11.1995; Erf.: J.-L. Cabioch „Composition de caoutchouc à base de silice et de polymère diénique fonctionnalisé ayant une fonction silanol terminale“

 Modification of S-SBR with Hydroxyl - Moieties H

X S X

SH

X: - OH (US 6252008) X: - COOH (US 6365668)

Sources: US 6252008; Bayer AG; Prior.: 18.07.1998; Inv.: T. Scholl, U. Eisele, J. Trimbach, S. Kelbch WO 02/31028 A1; Bayer AG; Prior.: 10. 10. 2000; Inv.: Th. Scholl, J. Trimbach, W. Nentwig, R. Engehausen US 6365668; Bayer AG; Prior.: 16.11.1998; Inv.: Th. Scholl, J. Trimbach

 4.3. Chemistry and Production Technology of High  cis-1,4 BR with an Emphasis on Nd - BR •

Technically Relevant Catalyst Systems for the Production of High cis-1,4 BR Influence of Halides on 1,4-cis Content – Role of Halides and Electron Donors on Microstructure – Trans-1,4 BR: Dependence of Melting Temperature on 1,4-cis-Content – Reaction Scheme of Butadiene Insertion –

•

Mechanism of Nd-Catalyzed Butadiene Polymerization Activity of Rare Earth Naphthenates (Cocatalyst: RnAlCl3-n) – Influence of Solvents – Influence of Molar Neodymium/Chloride-Ratio on 1,4-cis Content – Reaction Scheme of Butadiene Polymerization by Nd-Catalysis – Mechanism of Nd-Catalyzed Butadiene Polymerization –

•

Technical Options for the Control of Molar Mass in Nd-BR-Production

Technically  Relevant Catalyst Systems for the  Production of High cis- BR BR

Catalyst System

Molar Ratios

Li-BR

nBu-Li

Co-BR

Co(II)Octanoate / DEAC / H20

Ni-BR

Ni(II)Naphthenate /Bu2O.HF/TIBA

Ti-BR

TiJ3(OEt) / TiCl4 / TEA

Nd-BR

Nd(III)Versatate / DIBAH / EASC

cis-1,4 Content 36 - 38

1 / 7 0-80 / 20-30

97

1 / 100 / 40

97

1 / 0,7 / 5

93

1 / 10-15 / 3

98

Abbreviations: nBu-Li DEAC TIBA TEA DIBAH EASC

n-Butyl-Lithium Diethyl Aluminum Chloride Triisobutyl Aluminum Triethyl Aluminum Diisobutyl Aluminum Chloride Ethylaluminum Sesquichloride

 Influence of Halides on 1,4- cis-Content    ] 98    %    [    t 97   n   e 96    t   n   o 95    C   - 94    4  ,    1   - 93   s    i   c 92

Metal Component of Halide Catalyst System Ti Co Ni Nd F Cl Br J

35 75 87 93

93 98 91 50

98 85 80 10

95,7 96,2 96,8 96,7

0

1

2

3

4

Molar Cl/Nd - Ratio Source: Zhinquan Shen, Jun Ouyang, Fasong Wang, Zehnya Hu, Fusheng Yu, Baogong Qian; J. Pol. Sci., Chem. Ed. 18 (1980) 3345-3357

Sources: •Lars Friebe: Diploma Thesis TU Munich 2000 •L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

 Role of Halides and Electron Donors on Microstructure Nd(OR)3 Nd(OR)3

+ TIBA + DIBAC

trans -1,4-BR cis -1,4-BR

Nd(COOR)3

+ TIBA

Nd(COOR)3

+ DIBAC

trans -1,4-BR cis -1,4-BR

Nd(COOR)3

+ Mg (Allyl)2

trans -1,4-BR

Nd(COOR)3

+ Mg (Allyl)2  + R-Cl

cis -1,4-BR

Nd(CH2Ph)3

+ TIBA

trans -1,4-BR cis -1,4-BR

Nd(CH2Ph)Cl2 + TIBA

Co(Oct)2 + AlR2Cl + H2O Co(Oct)2 + AlR2Cl + H2O + PPh3

cis - 1,4-BR

Co(Oct)2 + AlR3 + CS2

s - 1,2 - BR

Ni(Oct)2 + BF3 - OEt2 + AlR3 Ni(Oct)2 + BF3 - OEt2 + AlR3 + PPh3

s - 1,2 - BR

cis - 1,4 - BR trans - 1,4 - BR

 For the achievement of  high 1,4-cis contents the  presence of a halide  source is essential  Source: Shiro Kobayashi; Transition in Precision Polymerization (1997) Part 1. H. Watanabe, T. Masuda, Diene Polymerization, pages 55-66

The coordination of electron  donors to vacant catalyst  sites results in a significant  reduction of 1,4-cis contents.  As a consequence, syndiotactic  BR or trans-1,4 BR are  obtained.

Trans 1,4- BR: Dependence of Melting Temperature  on 1,4- trans Content 160

120

   ]    C    °    [

Data from: US 5134199 Enoxy Chem Ltd. GB 2161169 (Asahi) US 4931376 (Asahi) US 5596053 (Bridgestone/Firestone)*

80

  m 40

   T

Goodyear +0

- 40 60

70

90

80

100

1,4 - trans-content [Mol %] *US 5596053 (Bridgestone/Firestone) Prior. 31. 05. 1995; Erf.: J. W. Kang; J. T. Poulton "High Trans-1,4-BR and Catalyst and Process for Preparing Crystalline High Trans-1,4-BR“ US-A-5089574 (trans-1,4-BR-Herstellung/Goodyear) EP-A-1092565 Prior.: 11.10.99 D. J. Zanzig, P. H. Sandstrom, J. J. Verthe, E. J. Blok, G. M. Holtzapple „Tire with silica-reinforced tread comprised of trans-1,4-BR, solution-SBR, polyisoprene and defined amount of carbon black and amorphous silica“

 Reaction Scheme of Butadiene Insertion Allyl-Komplex Bd  Bd 

M 8

C

M 15

M

M

C C

C

29

22

`

Bd 

M 36

C

M

M 43

C

54

C

Bd 

M 60

C

 For the achievement of high 1,4-cis contents, a vacant coordination site  on the transition metal is a prerequisite. To this site butadiene has to be  coordinated in a cisoid mode. The formation of trans-1,4-BR is thermodynamically favourable whereas the formation of 1,4-cis-BR ist kinetically controlled. Source: Porri, Giarrusso, J. Polymer Science, Vol. 4, 93

 Mechanism of Neodymium Catalyzed  Butadiene  Butadiene  Polymerization Activity of Rare Earth Napthenates (Cocatalyst: RnAlCl3-n) 100

Only rare earth metals in the oxydation state +III show polymerization activity

90 80 70

Al-alkyls reduce Pm, Sm and Eu salts to the oxydation stage +II

   ]    %    [ 60    z    t    a 50    s    m 40    U

30 20 10 0    a    e    r    L    C    P    d    N    m    m    u    P    S    E    d    b    y    o    G    T    D    H    r    E    m    b    u    T    Y    L

Source: Zhinquan Shen, Jun Ouyang, Fasong Wang, Zehnya Hu, Fusheng Yu, Baogong Qian J. Pol. Sci., Chem. Ed. 18 (1980)3345-3357

 Mechanism of Neodymium Catalyzed  Butadiene  Butadiene  Polymerization: Influence of Solvents

Contrary to other Ziegler–Catalysts, aromatic solvents have a negative impact on Nd-based catalyst systems

Source: F. Cabassi,G. Ricci, L. Porri; Transition Metal Catal. Polym. (Proc. Int. Symp. 1988, 2nd vol. 655-670) „Neodymium Catalysts For 1,3-Diene Polymerization. Some Observations On their Activity And Steoreospecificity“

 Mechanism of Neodymium Catalyzed  Butadiene  Butadiene  Polymerization O Nd

R1

O

Cl Cl Al Al Et Et Cl Et

R2 R3

H

Al

3

NdV 1

DIBAH 10 - 15

EASC 3

Literature: http://dx.doi.org/10.1007/12_094 Neodymium-Based Ziegler/Natta Catalysts and their Application in Diene Polymerization 1) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner; Adv. Polym. Sci. (2006) 204, 1-154 (Review);

2) Friebe, Lars; Mueller, Julia; Nuyken, Oskar; Obrecht, Werner; Journal of Macromolecular Science, Part A: Pure and Applied Chemistry (2006), 43(6), 841-854. Comparison of the solvents n-hexane, tert-butyl benzene and toluene in the polymerizationof 1,3-butadiene with the Ziegler catalyst system neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride. 3) Friebe, Lars; Mueller, Julia M.; Nuyken, Oskar; Obrecht, Werner. Pure and Applied Chemistry (2006), 43(1), 11-22. Molar mass control by diethyl zinc in the polymerization of butadiene initiated by the ternary catalyst system neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride. Journal of Macromolecular Science, Part A: 4) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner. Macromolecular Science, Part A: Pure and Applied Chemistry (2005), A42(7), 839-851. A Comparison of Neodymium Versatate, Neodymium Neopentanolate and Neodymium Bis(2-ethylhexyl)phosphate in Ternary Ziegler Type Catalyst Systems With Regard to their Impact on the Polymerization of 1,3-Butadiene. 5) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) (2004), 45(1), 758-759. Novel investigationsand applications for neodymiumbased catalysts. 6) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Abstracts of Papers, 227th ACS National Meeting, Anaheim, CA, United States, March 28-April 1, 2004 (2004) Novel investigationsand applications for neodymiumbased catalysts. 7) Friebe, Lars; Windisch, Heike; Nuyken, Oskar; Obrecht, Werner. Journal of Macromolecular Science, Pure and Applied Chemistry (2004), A41(3), 245-256. Polymerization of 1,3-Butadiene Initiated by Neodymium Versatate/Triisobutylaluminum/EthylaluminumSesquichloride: Impact of the Alkylaluminum Cocatalyst Component. 8) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Macromolecular Materials and Engineering (2003), 288(6), 484-494. In situ preparation of a compatibilized poly(cis-1,4-butadiene)/poly(e -caprolactone) blend. 9) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Macromolecular Chemistry and Physics (2002), 203(8), 1055-1064. Polymerization of 1,3-butadiene initiated by neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride: kinetics and conclusions about the reaction mechanism.

 Reaction Scheme of Butadiene Polymerization  by Nd -Catalysis 1) Formation of Nd-Alcoholate by the Reduction od Nd-Versatate Nd ( OOC - R )3 + 6 H Al

Nd (O-CH2- R )3 + 3

Al

O

Nd ( OOC - R )3 +

3H

Al

Nd (O-CHR- R )3 + 1

Al

O

Al

Al

O O

Al

2) Formation of a Nd-Hydrodo Compound (Precursor of Active Nd-Species) (R-CH2-O)3 Nd + H

Al

  (R-CH2-O)2 Nd - H

Nd (O-CH2- R )3 + H Al

+

RCH2

O

Al

+ R-CH2-O

  (R-CH2-O)2 Nd

Al

H

CH3   (R-CH2-O)2 Nd

CH2 C H

CH3

(R-CH2-O)2 Nd - H

+

H2C

CH3 CH3

Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

 Reaction Scheme of  Butadiene utadiene Polymerization  olymerization  by Nd -Catalysis 3)

Hydride transfer and Formation of a Nd-Allyl Compound (R-CH2 - O)2 Nd - H

4)

  AlR 3

+

CH3 (R-CH2 - O)2 Nd

Halogenation of the Nd-Allyl Compound CH3

CH3 Al2Et3Cl3

(R-CH2 - O)2 Nd

Cl2 Nd

Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

 Reaction Scheme of Butadiene Polymerization  by Nd -Catalysis 5) Formation of polymerization active Nd species (cationic Nd allyl complex) and first butadiene insertion

-

AlR3 Cl Nd

Nd

Cl R

ClAlR3

+

-

AlR3

AlR3

ClAlR3

+

Nd

Cl

Cl R

AlR3

-

Nd

+

Cl R

AlR3

-

Nd

Nd

Cl R

ClAlR3

+

Cl

AlR3

ClAlR3

Cl R

AlR3

R

Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

 Reaction Scheme of Butadiene Polymerization  by Nd -Catalysis 6) Control of Molar Mass by Al-Alkyls and by Al-Hydrido Compounds

Nd

L L

+

H Al

+

Al

H Nd L L

+ R

Al

L L

+ R

Al

R Nd

L L

Nd

R

Active “living“ polymer chain (attached to Nd)

inactive “dormant“ polymer chain (attached to Al)

Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht, Journal of Macromol. Sci.

 Mechanism of Nd -Catalyzed  Butadiene  Butadiene Polymerization Experimental Conditions:

Addition Sequence:

Solve nt n-He xane Butadiene 1,85 mol/l NdV 0,20 mmol/l EASC DIBAH

0,13 mmol/l (nCl /nNd = 2/1) 2,0; 4,0; 6,0; 10,0 mmol/l nDIBAH /nNd = 10, 20, 30, 50

Conversion/time-plots

   ] 100    %    [   n 80   o    i   s   r   e 60   v   n   o    C 40   r   e   m20   o   n   o    M 0

1. He xane 2. B utadiene 3. DIBAH 4. Ne odymve rsatate 5. EASC Polymerization temperature: 60°C

Plot for 1st order monomer consumption 0 -1

nDIBAH /nNd = 10 nDIBAH /nNd = 20 nDIBAH /nNd = 30 nDIBAH /nNd = 50

   ) -2   x      1    ( -3   n    l

nDIBAH /nNd = 10 nDIBAH /nNd = 20 nDIBAH /nNd = 30 nDIBAH /nNd = 50

-4 -5

0

50

100

150

time [min]

200

250

0

50

100

150

200

Time [min]

Sources: Lars Friebe: Diplomarbeit and der TU München, Dezember 2.000 L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

250

300

 Mechanism of Nd -Catalyzed  Butadiene  Butadiene Polymerization Dependence of Molar Mass Distribution on Monomer Conversion

Dependence of PDI (Mw /Mn) on Monomer Conversion

conversio n / %

nDIBAH /nNd = 10 nDIBAH /nNd = 20 nDIBAH /nNd = 30 nDIBAH /nNd = 50

82.5

  s   e   c    i    d   n    I   e   x   v   e    i    d    t   n    i   c   n   a   o    i    t   r   c    f   a   r   e    f   e    R   r    f   o   n   e    i   c   n   e   e   r   c   e    f   n    f    i   e    d   r   e    f    f    i    D

4,0

66.4

3,5

55.1

50.0

43.5

35.6 

  n 3,0

   M    /  w2,5    M

30.7 

22.7 

12.2

2,0 1,5 1,0 0

7 .8 

4 .8 

30

35

30

35

40

40

45

45

50

50

55

55

60

60

10

20

30 40

50

60 70

80

90 100

Monomer Conversion [%] 65

65

elution time / min

Elution time[min] Source: L. Friebe: Diploma Thesis at TU Munich, December 2.000 L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

 Mechanism of Nd -Catalyzed  Butadiene  Butadiene Polymerization Dependence of Mn on Monomer Conversion 2,5*105 2,0*105

   ]   o 1,5*105   m  .   g    [ 1,0*105

   1      l

nDIBAH /nNd = 10 nDIBAH /nNd = 20 nDIBAH /nNd = 30 nDIBAH /nNd = 50

  n

   M 0,5*105 0 0 10 20 30 40 50 60 70 80 90 100

Molar Mass Control with Al-Component   r  m 16   e  o    t   m 14   y    l   A     o   d 12    P    f   N   o  r   e10   r  p   e    b   d   e 8   m   u  m   r 6    N   o    f    l   a  s 4   n    i   m   r  a 2   o   h    F    C0

nDIBAH /nNd = 10 nDIBAH /nNd = 20 nDIBAH /nNd = 30 nDIBAH /nNd = 50

0

10

Monomer Conversion [%]

20

30

nDIBAH /nNd nDIBAH /nNd = 4,4

Source: L. Friebe: Diploma Thesis at TU Munich, December 2000 L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

40

50

Technical Options for the Control  of  of Molar Mass in  Nd - BR Production Influence of Polymerization Temperature Contrary to Catalysts based on Co, Ni and Ti, for Nd-based catalysts there is no agents for the control of molar mass available. Therefore in Nd-BR technology molar mass has to be controlled by: Nd/Al-ratio Monomer/Nd-ratio • Monomer Conversion • Polymerization temperature • •

G. Sylve ster, B. Stollfuss ACS, Rubber Div. Dalla s 1988 „Synthesis of cis-1,4-Polybutadienes by rare earth catalysts“ 2500    )   v 2000    M    (    ]   s   l   s   o 1500   a   /   m    M  g 1000   r    k   a   [    l   o 500    M

0 0

10

20

30

40

50

60

70

80

90

Polymeriz ation Temperature [°C]

Influence of Monomer Conversion

Influence of Butadiene/Nd-ratio

M. Bruzzone ACS Symposium Serie s No. 3 (1982) 33-55

D. J. W ilson, Polymer 1993, 34,16, 3504-3508 900

60

800    )   v 700    M    (    ] 600   s   l   s   o   a   /   m 500    M  g   r    k   a   [ 400    l   o 300    M 200

   ) 50    C    °    040    0    1    (    430   +    1    L20    M 10

100 0

0 0

0,05

0,1

0,15

0,2

0,25

0,3

0

20

40

60

80

100

Monomer Conversion [%]

Nd (mmol/100 wt.-parts of butadiene]

Comparison of Technologies  for  or the Production of  High cis-1,  4- BR 1,4 Co

Ni

Ti

Nd

Solvents

Benzene

Benzene

Benzene

N-Hexane Cylcohexane

Hexane Toluene 120 min

Toluene

Residence time

Toluene Aliphates 150 min

120 min

100-120 min

55-80 %

< 85%

< 95%

< 100%

high

high

low

Very low

Partially adiabatic 11-12%

fully adiabatic 18-22%

Monomer conversion Gel formation process Max. solids concentation Molar mass regulator Formation of VCH Residual transition metal Content [ppm]

Partially adiabatic Partially  /isothermal adiabatic 14-22% 15-16% yes

yes

none

none

high 10-50

high 50-100

very high 200-250

low 100-200

Advantage * Formation of VCH by   Diels-Alder-Reaction Butadiene

Vinylcyclohexene (VCH

 4.4. Ethene/Propene-Co- and Terpolymers (EPM/EPDM)

•

Overview –

•

EPDM-Production –

•

EPM and EPDM, Termonomers, Market, Range of Grades and Property Profiles Chemistry of Polymerization , Producers, Capacities, Brand Names and Production Technologies

Production Technologies (Flow Charts) Solution Process – High Temperature Solution Process – Gase Phase Process – Comparison of Manufacturing Technologies –

•

Metallocenes Ovewrview on Metallocene Patents – Metallocene Activation – Comparison of Catalyst Costs –

 Ethene/Propene-Co- und Terpolymers (EPM/EPDM) Method of Vulcanization EPM Peroxides

EPDM

EPM

Sulfur Peroxides Phenol resins etc.

(15%)

EPDM

(85%)

Ethene/Propene-Copolymers

Ethene/Propene/Diene-Terpolymers

Major areas of application:

Major areas of application:

• •

Oil additives Impact modification of thermoplastic polymers (PP)

(30% of grades are oil extended)

• • •

Technical rubber goods Cables and wires TPEs

 EPDM -Termonomers Relative polymerization rates of termonomer double bonds in Vanadium catalysed polymerizations

5-Ethyliden-2-norbornene (ENB)

~ 40 : 1

Dicyclopentadiene (DCPD)

~ 15 : 1

1,4-Hexadiene (HD)

~5:1

Criteria for the selection of the termonomer: Large reactivity difference of double bonds during polymerization • Low impact on the reduction of the polymerization rate • Low impact on the reduction of the molar mass during polymerization • Sufficiently long scorch time and high crosslinking efficiency during vulcanization • Low termonomer costs •

 Impact of the Termonomer  on the Curing Characteristics ENB

DCPD

HD

70

ENB DCPD 1,4-HD

60      ] 50     m 40      N      [     e     u 30     q     r     o      T 20

10 0 0

1,0

2,0

3,0

time [min]

4,0

5,0

6,0

Property Profile of EPM/EPDM based  Vulcanizates  Advantages: – good price/performance-ratio – high maximum service temperature – good low temperature performance – broad spectrum of grades (oil extended grades etc.) – ability for vulcanization with sulfur, peroxides and others – high loadability with extender oils and fillers (reduction of compound price) – good mechanical properties of vulcanizates – good weathering and ozone resistance (outdoor applications) – good electrical insulation (low salt content) – Low density Disadvantages: – low resistance to oil and chemicals – fair ability to covulcanization – low resistance to fungi and bacteria

 Main Application Areas of EPM/EPDM  13% 15%

16%

9%

6%

41%

Automotive Thermoplast Modification Building Technikcal Rubber Goods Electro/Electronics Oil Additives

700 EPDM Consumption (world)    t    k 600    /   n   o    i    t 500   p   m400   u   s   n   o 300    C   Automotive production (world)    M200    D    P    E 100 0    6    8    9    1

   7    8    9    1

   8    8    9    1

   9    8    9    1

   0    9    9    1

   1    9    9    1

   2    9    9    1

   3    9    9    1

   4    9    9    1

55  .   o    i    M    /   n   o 50    i    t   c   u    d   o   r    P 45   e   v    i    t   o   m   o    t   u 40    A    5    9    9    1

Market: 1,050 Mio t (2004) Growth rate:

3,5 %/a

Source: European Chemical News 10, März 2005, 13

 Range of  EP(D)M -Grades

Ethene Content

[wt.%]

50 - 75

ENB-Content:

[wt.%] 0

1,7 - 3

Mooney Viscosity: [MU] 16 - 20 [ML 1+4 (125°C)] Oil Content:

4-7

20 - 60

[phr]

8 - 12 60 - 90

0, 25, 30, 50, 100

 Dependence of Tg on the Ethene- and the ENB-Content ( V  V-  catalysed  commercial   commercial  products  products )

-45

EPDM/2% ENB EPDM/1% ENB EPM /0% ENB

-47,5 -50 -52,5

   ]    C    °    [ -55    g    T

-57,5 -60

Tg(EPDM) = Tg(EPM) + 1,2°C/wt.% ENB

-62,5 -65 40

45

50

55

60

65

Ethene content [wt.%] Source: M. Hoch, M. Arndt-Rosenau, Bayer-Report ARO 1, HCM 40 of 16.02.2001

70

 Dependence of the Cristallinity on the Ethene Content and  on the Polymerization Temperature of V -Catalysed  EPM   EPM  30 35-39°C 25

  g    /    J    [   n 20   o    i   s   u    f    f 15   o   y   p    l   a 10    h    t   n    E

40-44°C 45-49°C 50-54°C 55-59°C 60-64°C 65-70°C

5

0 46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

Ethene content [wt.%] Source: M. Hoch, M. Arndt-Rosenau, Bayer-Report ARO 1, HCM 40 of 16.02.2001

Chemical and Process Aspects in EPM/EPDM  Manufacturing Technologies Chemical Aspects free radical Polymerization Ziegler/NattaPolymerization

Process Features Emulsion E-SBR, CR, NBR, E-BR, ACM,FKM, EVM

Solution EVM

Dispersion

Bulk AEM, EVM, (ENM)

EVM

(G-BR)

BR

EPM/EPDM

EPM/EPDM

anionionic Polymerization

BR, LSBR. IR

cationic Polymerization

ECO, CO

IIR

Q

Polyaddition und Polycondensation

AU, EU

EU

AU, Q

Polymermodification

CIIR, BIIR, CM, CSM, H-NBR, FZ

Gas-Phase

Q

CM, CSM, (H-NBR)

(G-EPM/EPDM)

 Features of the EPDM - Manufacturing Technologies Source: R. T. Sylvest, J. A. Riedel, J. R. Pillow; GAK 6/1997 (50) 478-483

Process

Solution

Solvent: Catalyst System Catalysts: Cocatalysats: Reactivators: Modifier: Short stos: Antioxidans: Stripping aids: Oil:

Hexane

Slurry

High temperature solution (Dow)

Propene/ethene Hydrocarbon mix. Ziegler/Natta CGC/Borane VOCl3, VCl4, V(acac)3,VO(OR)3, TiCl4 CGC-Catalyst EASC, DEAC Borane (MMAO) PDCAE, TCAE, BPCC H2, ZnEt2,(NH3) Stearic acid, water, antioxidants sterically hindered phenols, phosphites water soluble polymers etc. mineral oil fraction with high b. p. -

Gas phase (UCC) Ziegler/Natta V(acac)3 Al-Alkyl CHCl3 H2 ? ? -

Reactivators: PDCAE

BPCC Cl

O

O

Cl O

C2H5

Cl

Cl

Cl O

Cl

Cl

C4H9

9

Cl

Cl

TCAE O O

C2H5

Cl

Speculation  on the Active Species in the Vanadium -Catalysed  EPDM   EPDM - Polymerization +V VOCl3 +IV VCl4 +III

VX3 + R2 AlX

+

{R2VX}

{R2V }

  r   o    t   a   v    i    t heat    k    A

+II

VX2 + R3 Al

heat

[R2V] R2AlX

{homogeneously soluble species}

-

+ R2AlX2

[RVX] R3Al

[heterogeneous species]

Source: K.J. Cann, J.W. Nicoletti, X. Bai, F.D. Hussein, K.H. Lee, D.P. Zilker, Presentation at FLEXPO `97

 EPDM   Producers, Capacities (   kt )  ) and Brand Names Exxon DSM DPDE Lanxess Lion Copolymer Polimeri Mitsui JSR Sumitomo Kumho Petro China Nizhnekamsk Herdillia

Baton Rouge, Louisiana Notre Dame de Gravenchon Geleen, Niederlande Triunfo, Brasilien Plaquemine, Louisiana Seadrift, Texas Marl, Deutschland Orange, Texas Geismar, Louisiana Ferrara, Italien Chiba, Japan Kashima, Japan Yokkaichi, Japan Chiba, Japan Yeochon, Südkorea Jilin, China Nizhnekamsk, Russland Maharashtra, Indien

total capacity

180 Vistalon 85 135 Keltan 35 Nitriflex EP 100 Nordel-IP 90 Elastoflo (UCC) 60 Buna EP G 55 Buna EP T 91 Royalene / Trilene 85 Dutral 60 Mitsui EPT 25 JSR EP 45 40 Esprene 40 KEP 30 30 10

1076

Source: European Chemical News 10, März 2005, 13

 EPDM -Solution- Process with Fully Flooded  Reactor Water containing azeotrope

ENB Condenser Settler External cooling loop

Boiling point:

146°C

Max. exposure limit/MAK:

1 ppm

Smell limit:

3-5 ppm

Waste water Condenser

Azeotropic destillation

Flash drum Stripper

Waste air

Propene dewtering screwg

Hexane Ethene

destillation Polymerization reactor

Steam Expeller

Settler Steam

destillation

drier Waste water

PHControl

Stripping aid

drier

Precoller -32/-35°C

Water Modifier Reactivator

Drier

Hexane

drier

VNB/ENB

EASC VOCl3 /VCl 4 3/1

oil drier Antioxydant Waste water

Process Features Propene precooling: Temperature: Pressure: Residence time: Soldis conc.: H2 O:

-32°C/-35°C 20-65°C 5-10 bar 6-15 Min. 3 -7 Gew.% < 3 ppm

baling

Packaging

 Dow‘ s High-Temperature Solution Process ( Source Source: Dow- Patents, Publications etc.) Plant location: Plaquemine/Lousiana Destillation

Solvent and monomer

Condenser

Evaporator

Flashdrum

High boiling residue

In the Dow-HT-Process low amounts of CGC- catalyst are required. The catalyst is not washed out and no steam stripping is applied („leave-in-catalyst“)

Evaporator

(ENB, AO, etc.)

Ta Antioxidant (AO) Polymerization reactor

baler Ageing drum

"Insite-Kat."

Scavenger

Purification

Purification

Ethene

Propene

Temperature: Ta: Pressure: Residence time:

Purification

ENB

packaging

MMAO

40 - 80 °C 80°C (>130°C) 9-15 bar < 20 Min.

Borane

 Metal Content of Commercial EPDM  Activation of Metallocenes Cl

R

Alkylation

Zr

Zr

Cl

R

Activation by MAO  (molar excess of MAO: 10.000 - 10.000 fold)

Activation by Borane/Borates: (with molar B/Zr-ratios)

R Zr +

Product V Ti Fe

Al

Dow-CGC

Ca Na Sum

<1 1,0

1,3

1,7

<1

<1

8,0

EPDM # 2 8,0 <1

4,3

31

1,7

1,8

22,3

EPDM #3

1,9 <1

4,3

31

1,7

1,8

48,8

EPDM #4

2,4 <1

2,0

6,7

64

5,7

EPDM #5

5,1 <1

2,8

9,6

160

4,6

82,8 184,1

EPDM#6

4,8 1,9

63

440

64

9,4

584,1

A

Source: J. G. Pillow (Dow) „Ethylene Elastomers made using Constrained Geometry Catalyst Technology“ Kautschuk Gummi Kunststoffe 51, 12/98, 855-859

Crystallinity Crystallinity of Metallocene- Based  EPDM   EPDM  30

EBTHI-Cat.

CH2 CH2

DOW-Insite-Cat.

CH2

25    ]    g    /    J    [    n 20    o    i    s    u    f    f 15    o    y    p    l    a 10    h    t    n    E

CH2 ZrCl2

CH2

Me2Si N

CH2

CMe3

CH2 CH 2

X

Ti X

V-Catalysis

5 0 40

42

44

46

48 50 52 54 Ethene Content [wt.%]

56

58

60

62

 Impact of Cristallinity on Low-Temperature Compression Set of EPDM - Based Vulcanizates DOW-Insite-Cat.    ]    %    [    t    e    S      n    o    i    s    s    e    r    p    m    o    C      e    r    u    t    a    r    e    p    m    e    T      w    o    L

100 90 Me2Si

80

X

Ti

70

N

60

CMe3

X

50 40

EPDM/V-Cat. EPDM/CGC (Dow)

30 20 10 0   0

3

5

7

7

  0    5    5  ,     8 ,     8 ,    0  0   1

  1  2

   8   1

Enthalpy of Fusion [J/g]

   5    5  0    5  ,     3  ,     7   5  ,    2  1   2   5  ,     7    3    7    3   4    3

UCC ‘ s EPDM -Gas- Phase- Process (   now Dow)

Flow-Chart: US 4994534

Plant location: Seadrift/Texas

Filter Compressor

Temperature: Pressure: Residence time:

< 90 °C (40°C-60°C) 9-15 bar 0,5 - 1 h

Cooler ENB

Purification

Fluidizing Aid

Patents:

Product

EP 1099715 EP 1099473 EP 1086995 EP 1083192 US 6180738 WO 0000333 WO 9965953

Desactivation

Suported Catalyst

Ethene

Purification

Propene

Purification

Modifier

Purification

Monomer degassing unit

ENB Boiling point:

146°C

Maximum exposure level:

1 ppm

Smell limit

3-5 ppm

Baling of Product etc.

Source: „Carbide starts up Seadrift plant with new technology“ European Chemical News, 1-8 February 1999 ($ 12m charge for replacing the purge unit)

Comparison of EPM/EPDM - Manufacturing Technologies Ranking: 1-10; 1= modest; 10=excellent Process

Solution

Slurry

HT-Solution Gas-Phase

V-Catalysis

V-Catalysis

CGC/Dow

V-Catalysis

4

5

7

10

EPM EPDM Low Mooney High Mooney Oil Extended Grades

10 10 10 5 7

10 10 8 10 10

10 10 10 3 3

10 0 0 10 0

Process Flexibility

42

48

36

20

Overall Process Performance

46

43

30

Process Economy

53

••The Thewell wellestablished establishedvanadium vanadiumbased basedsolution solutionand andslurry slurryprocesses processes

are areinferior inferiorin ininvestment investmentand andoperation operationcosts, costs,but butprovide provideaahigher higher flexibility. flexibility. ••The TheHT-solution HT-solutionand andthe thegas-phase gas-phasetechnology technologyare arelow lowcostcosttechnologies, technologies,which whichare aresuperior superiorin inthe theproduction productionof ofspecific specificgrades grades

 Metallocene- Patents 1980- 2000 ( Oct Oct .  . 2000) 250

2.923 Documents

 .    l    p    p    A   - 200  .    t    a    P   +    ) 150    S    U    (    s    t    n 100    e    t    a    P    f    o    r 50    e    b    m    u    N 0

USUS-Patents and EPEP- and WOWO-Patent Applications

    I     i     t    w     F    s    r     l     l     t    y    e    r     l    n     l  .    u     M     P     i   s    a     N    n    s     l    o    e    l     C    C     t   e     l    y   e    o     l    n    s    S     b    p    m    o     B     h    g     a   r    o    r     i     i     t    S     E    o     i    g     a     t     l     h    e    x     i    o   c     A     U     D     l    r     F    n     D     P    e    e     i    a     P    S     h    m     B     h     M    u     G    m     B   a    r   e    o     C     E   x    o   e    e     T    o    e     2     i     P     M     i     I   d     H     D     b   a     l     B     b    u    u     i     A    r    2  .     t   s     t   s     i     C     i     N     M     M WPIDS-Recherche Dr. Karjetta vom 29. 09. 2000

 Activation of Metallocenes Cl Zr

  Alkylation (BuLi, AlR3 or MAO)

Cl

  Alkylation (BuLi, AlR3 or MAO)

R Zr

Cl

Activation by MAO

R Zr

R

Activation by borates and boranes

R Zr + A

Cossee- Mechanism of Metallocene Catalysed  Olefin Insertion R Zr +

R

CH2 CH2

Zr +

R Zr +

CH2

CH2

CH2

CH2

R + Zr

CH2

CH2

 Key Patents in Metallocene- und Single-Site-Catalysts 1.1. Bis Cyclopentadienes

X Zr X

X B

Zr X

Me2C

ZrCl2

Me2Si

ZrCl2

B = Bridge

EP 35242 EP 129368 EP 468537 (29.12.1980) (06.06.1983) (30.01.1987) BASF Exxon Exxon (Kaminsky) (Ewen) (Turner) EP 69951 (09.07.1981) Hoechst (Kaminsky) MAOMAOBorateActivation Activation* Activation HDPE, LLDPE, a-PP HDPE, LLDPE, i-PP, EP(D)M

EP 351392 (15.07.1988) Fina (Ewen, Razavi)

EP 4858821 (12.11.1990) Hoechst (Spaleck)

MAO-Activation HDPE, s-PP, COC

HDPE, i-PP

* H. C. Welborn, Jr.; J. A. Ewen US 5324800 (Exxon) Prior.: 30.08.1991 „MAO-Activation of Bridged Metallocenes“

 Key Patents in Metallocene- und Single-Site-Catalysts 1.2. Isoelectronic Bicyclopentadienyl Systems N

E X Zr

B R´

Zr B

N

R´

R

US 5539124 (19.12.1994) Lyondell

Me

Cl X

B

X

P

Cl

Me

Me P

Zr Cl

Ph Ph

B Y

US 5554775 (17.01.1995) Lyondell

Cl

Zr

X

E

EP 638593 (02.08.1993) Shell

B

X

X

E = N, P

Y

R

Me2Si

Ph

ZrCl2

SiMe3

WO 96/34021 WO 98/01455 (25.04.1995) (05.07.1996) Lyondell Bayer AG (Ostoja-Starzewski)

WO 98/50392 (08.05.1997) Nova Chemicals (Spence)

WO 97/2351 (22.12.1995) Hoechst AG (Herberich)

MAO-/Borate- MAO-/BorateActivation Activation Polyolefins

HDPE, PP

PE, PP

HDPE, LLDPE, PP, EPM, EPDM, COC

HDPE, LLDPE, PP, EPM, EPDM

 Key Patents in Metallocene- und Single-Site-Catalysts  2. 1. Mono-Cyclopentadienyl Systems

Me2Si

Ti MeO MeO

Ti N

OMe

EP 210615 (29.07.1985) Idemitsu Kosan US 5206197 Dow (04.03.1991) MAOActivation S-PS

CMe3

EP 416 815 (31.08.1998) Dow EP 420436 (13.09.1989) Exxon MAO-/BorateActivation HDPE LLDPE EP(D)M ES

(IV)

X X

Ti

Ti RxE

III

X X E= N, O

NR2

X X

US 5132380 (12.09.1991) Dow

WO 96/13529 DSM (Lovocat)

Borate-Activation

MAO_/BorateActivation HDPE LLDPE EPM

PO

 Key Patents in Metallocene- und Single-Site-Catalysts  2.2. Mono Cyclopentadienyl Systems

F F

Ti

F F Ti N

F t-Bu t-Bu

N

CH 3

N

CH 3 CH 3

O

C

CH 3

Ti

N

P

N P

t-Bu

X

WO 2005/005496 DSM

WO 2008/095687 DSM

US 6063879 (29.10.1997) Nova

MMAO-Activation

MMAO-Activation

MMAO-Activation

EP(D)M

EP(D)M

PE, LLDPE

 Key Patents in Metallocene- und Single-Site-Catalysts  3.1. Post Metallocenes Ar

Ar

Ar

X

X X´

P

X

Ti

Ti

Pd

Ar

S

N

P

Ar

EP 121965 (05.04.1983) Shell

O O

X

N Ar

X

t-Bu

O

X Zr X

O N

t-Bu

WO 92/12162 (27.12.1990) Exxon

N

JP 5230133 (19.02.1992) Mitsui Toatsu

EP 606125 (08.01.1993) Shell

US 5637660 (17. 04. 1995) Lyondell

Polyacetylens

Polyolefins, Polyacetylens

HDPE, PP

EP 571945 (29.05.1992) Sumitomo Alternating Olefin/CO-Copolymers („Carilon“)

Polyolefins

 Key Patents in Metallocene- und Single-Site-Catalysts  3.2. Post Metallocenes

R R´

R X´

N M N

R´

N Cl

X

N

R

Fe

Cl

N

R

Cl N

Cl N

Ti O

O

M = Ni, Pd WO 96/23010

DuPont

(24. 01. 1996) DuPont

(Brookhart)

BP

EP 0874005

EP 1881014

(24.01.1998)

(10.05.2006)

Mitsui

Mitsui

HDPE, EPM

EPM, EPDM

(Brookhart) polar/unpolar Copolymers, LDPE

HDPE, (PP)

HDPE(PP)

 Features of the Activation by MAO Chemical Structure of Methylalumoxane (MAO): (CH3)2 Al - [O - Al - CH3]n- O - Al(CH3)2 (CH3) Al - [O - Al - CH3]n- O - Al(CH3)

n

:

6 - 20

MW : 2.000-2.500

O

Features of the activation by MAO: The details on the mechanism of the activation by MAO are not known • A 1.000-10.000 fold molar excess of MAO is needed in solution polymerizations • A 50-100 fold molar excess is needed for supported catalysts (gas phase) • MAO is capable of alkylating metallocenedichlorides • MAO is able to abstract chlorides from metallocenemono- or dichlorides • MAO is an efficient scavenger for impurities •

(Polymerizations performed in the presence of MAO are very robust towards impurities)

 Activation of Metallocenes by Boranes and Borates Abstraction of Alkyl-Anions by Borane and Borates F

R Zr

R -R

F

F

F F

F F

B

F F

-

F F

F

H

N+

Ph Me

R Zr +

F F

F F

 _ 

F

Anilinium Borate

F

B

Me

Ph

+

Ph

Borane

F

F

F

F

4  _ 

Triphenylcarbenium Borate

F

B Ph

F

4

F

For the Activation of metallocenes molar quantities of borane/borates are required • Polymerizations activated by boranes/borates are very susceptible to impurities •

 ctivation of Metallocenes  Activation R

R. F. Jordan Turner M. Bochmann Turner (1990) (1986) 1987 1987

Zr

R -R

-

 M. D. Rausch, J. C. W. Chien (1991)

Ag

+

H

-

N+

BPh4

Ph Me

-

+R CH3CN

Ph

B

Ph

-

F5

+R

R Zr +

Ph

A

Me A

+R - RH

+

T. J. Marks (1991; JACS 113, 3623) F5

-

+R

N Ph Me

Ag+1/2 R2 + BPh4

-

F

F

F F

F F

F F

B F

F

- F

F F

F

Ph Ph

A

-

F5

B

F5

EP (Exxon) EP468 468537 537 (Exxon) Priorität: Priorität:1987 1987 EP 561 479 (Exxon) Priorität: 1987 EP 561 479 (Exxon) Priorität: 1987 Nicht Nicht oder oderschwach schwachkoordinierende koordinierendeAnionen Anionen "NCA"oder "WCA" "NCA"oder "WCA" (insbesondere: (insbesondere:Tetrakis(Pentafluorophenylborat) Tetrakis(Pentafluorophenylborat)

F

FF

Ph

F5

F

A : F

Me A

-

-

R

R -

-

F5

F

US Priorität: US5599761 5599761(Exxon) (Exxon) Priorität:04.02.1987 04.02.1987 Erfinder: H. W. Turner Erfinder: H. W. Turner „Ionic „IonicMetallocene MetalloceneCatalyst CatalystCompositions“ Compositions“

Comparison  of Catalyst Costs Example

Catalyst [EUR/100 kg]

Cocat. Reactivator Total Cat-Costs [EUR/100 kg] [EUR/100 kg] [EUR/100 kg]

Plant 1

VOCl3

EASC

[EUR/kg]

0,50

3,75

2,00

Plant 2

V(acac)3

DEAC

TEA

[EUR/kg]

1,25

1,30

0,65

Exxon- Pat.

Et(Ind)2ZrCl2

MAO

-

[EUR/kg]

13,00

151,00

-

Exxon- Pat.

Et(Ind)2ZrMe2

Borate

-

3,45

-

[EUR/100 kg] 2,25

DCPEE 6,25 3,20 164,00 5,70

• • MAO-activation MAO-activationof ofmetallocenes metallocenesisisnot noteconomical economicalin inaasolution solutionprocess process • • Borate-activation Borate-activationresults resultsin incatalyst catalystcosts costswhich whichare arecomparable comparablewith with Vanadium-systems Vanadium-systems • • For Foran animprovement improvementin inoverall-economy overall-economymetallocene-technology metallocene-technologyhas hasto tobe be combined combinedwith withprocess processimprovements improvements • • Increased catalyst costs Increased catalyst costsmight mightbe becompensated compensatedby bythe theimproved improvedproperty property profile profileof ofnew newproducts products

 4.5. Butyl - and Halobutyl Rubber  Abbreviations: Butyl Rubber: Bromo Butyl Rubber: Chloro Butyl Rubber: Brominated Isobutene Paramethylstyrene Rubber: IIR-Terpolymer (mainly with Divinyl benzene):

IIR BIIR CIIR BIMS XLIIR

Contents •

Overview Products, Property Profiles and Areas of Application – Market, Market Shares, Producers and Range of Grades –

•

Polymerization Mechanism and Production Technologies Standard-Butyl Rubber (IIR) – Halo Butyl Rubber (XIIR) –

•

Vulcanization and Vulcanizate Properties

 Butyl -  and  nd Halo Butyl Rubber CH3 CH2 C

CH3 CH2 C

CH3

CH CH2 CH2 C

CH2 C

CH3

CH3

CH3

n

20

CH3

Butyl Rubber (IIR)

CH 2 35 CH3 CH2 C CH3

CH3 CH2 C CH3

CH3

CH2 CH2 C

CH CH2 CH2 C

n

X

CH2 C CH3

CH3

CH3 CH2 C

CH2 CH CH2 CH CH2 C

CH3 n

CH3

CH2Br

C

CH3

123°

CH 2 21 16

15

29

30

CH3

CH2

CH3 C27

C CH 2 26

H3C

CH 28

45

CH 2 C 23 H3C

Standard Angle: 109,5°

Basic Features: Isoprene content: 0,5 - 2,5 Mol% Incorporation of Isoprene: random 1,4-trans Tg: ca. -72°C Mw /Mn: 3-5

CH3

Brominated Isobutene-co-p-Methylstyrene Rubber (BIMS) Isobutene-Terpolymers

19

CH3

CH3

X = Cl: Chloro Butyl Rubber (CIIR) X = Br: Bromo Butyl Rubber (BIIR)

CH3

38

39

CH3

 Butyl - and Halo Butyl Rubber (X)IIR: Property Profile and  Areas of Application Property Profile Positive: Low gas permeability • high resistance to heat and vapour • high resistance to chemicals • good insulation properties • good covulcanization (XIIR)) • product purity (grades without antioxydants) •

Tyres Others Chewing gum

5%

Pharmaceutical Adhesives Automotive

4%

3% 1%1%

Negative: low elasticity /highly damping

Areas of Applications: XIIR based Innerliners (passenger tyres) • IIR b ased tubes (truck tyres) • bladders (IIR) • ABC-protection clothes • Cable and wiring • Pharmaceutical stoppers • Adhesives and sealants • absorbers for noise and fenders • chewing gum •

86%

Source: CHEManager 20/2006, Seite 8 (GIT Verlag Darmstadt)

 Butyl and Halobutyl Rubber (X)IIR: Grades CH3 CH2 C

CH3 CH2 C

CH3

CH3

CH3 CH2 C

CH3

CH CH2 CH2 C CH3

n

Butyl Rubber (IIR) X2 (Cl2 / Br2) CH3 CH2 C

CH3 CH2 C

CH3

CH3

CH3

CH2 CH2 C n

CH CH2 CH2 C X

CH3

Halo Butyl Rubber (XIIR)  X = Cl: Chloro Butyl Rubber (CIIR)  X = Br: Bromo Butyl Rubber (BIIR)

Advantages of XIIR over IIR: Higher speed of vulcanization •Improved covulcanization without deterioration of basic IIR properties •

Characteristic Features of IIR based Vulcanizates Air permeability of vulcanized rubbers (50 phr SRF, without plasticizers)

Rebound

Temperature [°C]

(50 phr SRF, without plasticizer) 70

60

50

100

80

1,4-cis BR

   ]    %    [ 60   y    t    i   c    i    t   s   a 40    l    E    d   n   u   o    b20   e    R

NR

NBR EPDM

IIR

0 -75

-50

-25

0 25 50 Temperature [°C]

75

1,4-cis-BR

   )    8   p   x   e    0    1   x 10    Q    (    t    i   e    k   g    i   s   s    ä    l    h 1   c   r   u    d    t    f   u    L

SBR

NR EPDM SBR NBR/28 ACN NBR/33 ACN NBR/38 ACN IIR

100 0,1 0,0029

0,00295

0,003

0,00305

0,0031

1/T x 10exp4

Source: Butyl And Halobutyl Compounding Guide For Non-Tyre Applications, 12/92 Bayer AG -KA 34 166)

(X)IIR: Market, Market Development ,  , Producers  and Production Capacities Main Areas of Application:

 Market Growth (Basis: 2.000):  IIR:  XIIR: Sum:

- 2,3 %/ p.a. + 2,3 % p.a. + 1,2 % p.a.

IIR: XIIR: •BIMS: •

IIR XIIR Sum

   ]    t    k    [   n   o    i    t   p   m   u   s   n   o    C

Tyres and Tyre Production) Inner liners Truck tyre tubes heating bladders

Pricing (1996):

700 600

(90%: •XIIR: •IIR: •IIR:

500

•

Production capacities (2008) Company

400 300 200 100 0    9    2    5    8    1    7    0    7    8    8    8    9    9  4    9    9    0    9    9    9    9    9    9    0    1    1    1    1    1    1    1    2

ca. 1,80 €/kg ca. 2 €/kg ca. 3,5 €/kg

Butyl Halo- Total butyl [kt]

Exxon

X

X

414

Lanxess

X

X

252

Nizhnekamsk

X

X

180

Togliatti

X

Sinopec

X

(X)

45

Japan Butyl Co.

X

X

80

Total Capacity

50

1.041

 Range of Commercial IIR and XIIR Grades Range of Standard Butyl Grades

Range of XIIR Grades

100

100

90

90

80

80

  y    C    t    i   s    °    5   o    2   c   s    i    1    V   )    8    +   y   e    1   n   (   o    L   o    M   M

  y    C    t    i   s    °    5   o    2   c   s    i    1    V   )    8    +   y   e    1   n   (   o    L   o    M   M

70 60 50 40 30

70 60 50 40 30

20

20

10

10

0

0 0

2

4

6

8

10

   l   y   t    l   u   t  y    b   o  r    b  u    l    h   m   C   r  o    B

0

Content of double bonds [M ol%]

2

4

6

8

10

Halogen Content [Mol%]

 IIR: Flow Chart of Slurry Polymerization (Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993) compressor

CH3Cl

AlCl3solution drum

dryer

compressor

Al2O3 Cond enser

“catalyst cocatalyst drum“ H2O

„slop isoprene“

H2O

Storage tank for „mixed feed“ Storage units for IIR-slurry in water

NH3EtheneHeat exchangers Isobutene- Isoprene drying unit

Reactor

Steam- Flashunit

Strippingunit

 Features of IIR Production Technology Process: Catalyst: Cocatalysts:

Slurry polymerization AlCl 3 HCl (Exxon) H2O (Lanxess) Diluents: CH3Cl (Exxon and Lanxess) „mixed feed“(GUS) Make-up of AlCl3-solution 30 - 45 °C Polymerization temperature: -90 °C bis - 100 °C Residence time 0,5 - 1 h Conversion of monomers: Isobutene 75 - 95 % Isoprene 45 - 85 % Concentration of IIR-Slurry 25 - 35 wt.% Reactor output: 2 - 4 t/h*Reactor Operation time of reactors: 18 - 60 h Additives: Antiagglomerants: (Stearic acid/Zn-stearate) 0,4 - 1,0 wt.% Antioxydants: 0,02-0,15 wt.% -discolouring: alkylated Phenylene Diamines -None discolouring: phenolic AO (+ alk. Phenyl phsophites) -chewing gum: without AO

Ethylene (gas)

Ethylene (liquid)

Inlet and Drain for light hydrocarbon wash catalyst

Sources:

mixed feed

catalyst

Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993 US 2,356,128; US 2,491,752; US 2,491,710; US3,968,076; US 4,474,924; US 4,068,051; US 5,532,312

 IIR: Reaction Scheme of Cationic Polymerization Formation of Cation: +

AlCl3

+

HCl

H

AlCl3

+

H2O

H

H

-

+ AlCl4

+ AlCl3OH

CH3 C

-

n

CH2 C

H

Transfer Reaction: CH3 CH3 +

-

n

CH3

n

+

H

n

CH3

CH3

H

n

CH3

+ C + CH3 C AlCl4

CH3

CH3 CH2 C Cl + AlCl 3

CH2 C n

CH3

CH3

-

CH

CH2 C

CH3

-

CH3

CH3

CH3

CH3

CH2 C AlCl4

CH2 C

CH3

CH3

Termination Reaction: CH3 CH3 H

-

+ CH2 C AlCl4

CH2 C CH3

CH2 C AlCl4 +CH2 C

CH2 C

CH3

CH3

CH3

CH3

H

AlCl4

CH3

Chain Propagation (Growth) Reaction: CH3 CH3 AlCl4 +

-

+

CH3 C

+ CH2 C CH3

+

-

CH3

Initiation of Polymerization: CH3 +

+

+ AlCl4

CH3

CH3

 IIR: Living Cationic Polymerization Generation of Carbo Cation:

-

+

R - Cl + MX n

+ MX n+1

R

Initiation:

CH3

CH3 R

+

+ CH C 2

CH3

CH3 R

CH2 C MX n+1

+

n

R

CH2 C

n

CH3

Reversible Termination: CH3 CH R

CH2 C

CH2 C

+

-

R

MXn+1

CH3 CH2 C

CH2 C n

n

CH3

CH3

CH3

MXn (Metal halides) and R-Cl used for the preparation of Isobutylene based blockcopolymers: Cl

BCl3 and TiCl4

MX n+1

CH3

CH3

3

-

+

CH2 C

CH2 C

CH3

CH3

CH3

CH3

CH3

-

+

MX n+1

CH2 C

CH3

Propagation:

-

+

R

Cl

+

MX n

CH3 Cl

Cl

Cl

Cl

 Influence of Polymerization Temperature on Molar Mass (   Polyisobutylene / without Isoprene ) 13

-25

-50

-75

-90

-106

-120

107

-143 EtAlCl2 /H2O AlCl3 /H2O

γ -Strahlung    ]    l   o 106   m    /   g    [   n

   M

105

Molar Masses: BF3 /H2O

γ -Strahlung > EtAlCl2 > BF3 > AlCl3

104 3,5

4,0

4,5

5,0

5,5

6,0

6,5

1/T *103 [K-1] Source: J. Kennedy, P. D. Trivedi, Adv. Pol. Sci. (1978) 28, 113-151

7,0

 XIIR: Flow Chart of IIR- Halogenation Storage tank

Halogenation reactor

Neutralization reactor

Br2 bzw. Cl2 IIR-solution in hexane

Addition of AO exane

water X-IIRSlurry in water

Antiagglomerants

steam

Caustic soda

Source: Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993)

 XIIR: Mechanism of IIR- Halogenation

CH3 CH2 C

CH3

CH2 C

CH3

CH3

CH3

CH3

CH2 C

CH2 C

CH3

CH3 CH2 C CH3

CH3

CH3

CH3

CH CH2 CH2 C

CH2 C n

CH3 H CH2 C n

CH3

C

CH3

X

CH2 CH2 C CH3

X

CH3 CH2 C

+

CH3 H CH2 C n

+

C

X

CH3

CH2 C CH3 CH3 CH2 C CH3

CH3 CH2 C CH3

CH3 X

n

CH3 CH2 C CH3

X

Source:

n

CH3

Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993

CH CH2 CH2 C - HX

CH2 X CH2 C

Hexane 20 - 25 wt.%: 1:1 Mol/Mol 40 – 60 °C lh 2 - 2 kg/ kg XIIR Ca-Stearate, Epoxydized Soy bean oil (ESB)

CH3

X

CH2 C

Solvent: IIR-solids Ratio of Halogen/Isoprene: Reaction temperature : Residence time: Stripping-Vapour : Antioxydants / stabilizers:

CH2 CH2 C

- HX CH3

Reaction Conditions:

CH3

X2

CH3 CH3

CH CH2 CH2 C CH3

Patents: US 2631984; US 3099644; US 4288575; US 4554326; US 4632963; US 4681921; US 4650831; US 4384072; US 4513116; US 5681901

Crosslinking Efficiencies in Vulcanization by  Peroxides (   Dicumyl  Peroxide  Peroxide ) Rubbber O O

O

2 C

2

O

+

(R*)

efficiency Vi-BR

+ 2 R-H

C

C

Number  of crosslinks 

Type of Rubber

1)

~ 100

(98% Vinyl)

C

X -  -linking  l inking  efficiency  = 

X-linking

Peroxide  Functions 

Theoretical Crosslinking efficiencies

SBR

12,5

cis 1,4-BR

10,5

EPDM

1,5

EPM

0,4 - 0,7

NBR

1,0

IR

1,0

CR

0,5

M - Rubbers

1

IIR

<<1

R - Rubbers

>1

PE

1,0

Degradating polymers

<1

PP

<<1

1)

Dissertation Th. Früh, TU Hannover 1995

 Properties of Sulfur- and Peroxide Cured  IIR  IIR and XLIIR IIR

Polysar Butyl 402

IIR -Terpolymer*

100

-

Polysar Butyl XL 10000

-

100

N 762

Carbon black

50

50

Hard Clay

Silicate

-

20

Polarite 102R/EEC Int

Silanised calcinated Clay

130

80

Pb3O4

-

10

-

Stearic acid

-

1

1

Bis(t-butylperoxy-isopropyl)benzene

Perkadox 14-40 B/Akzo

-

1,5

Trimethylolpropanetrimethacrylate

Sartomer 350/Sartomer

-

1,5

Dibenzoyl chinone dioxime

Actor DQ/Kawaguchi

6

-

Dibenzo thiazyldisulfide

Vulkacit DM / Lanxess

1

-

* IIR-Terpolymer mit Divinylbenzol (XLIIR) Source: C. A. Moakes, Bayer „Polynotes“ No B11 „An Improved Seal for Chemical Condensers Based on Polysar Butyl Terpolymer“

 Properties of Sulfur- and Peroxide Cured  IIR  IIR and XLIIR Butyl Rubber Grade Compound Properties Compound Mooney (ML 1+4/100°C) Mooney-Scorch (125°C) [min.] Vulkanizate Properties (160°C/12 min.) Shore A Härte (23°C) S100 [MPa] Elongationat break [%] Tensile Strength [MPa] Compression Set (70h/105°C [%]) Hot air ageing (100°C/96h) Shore A Härte (23°C) S100 [MPa] Elongation at break [%] Tensile Strength [MPa] Electrolyte permeability (g*mm/day*m2) Ethylenglycol g-Butyrolactone Dimethyl formamide

IIR

XLIIR

105 4,0

98 6,2

81 6,0 155 6,8 75

76 6,5 105 7,5 15

83 7,8 110 8,0

78 95 8,2

0,38 1,0 7,8

0,21 0,8 1,8

Vulcanization of BIIR by Peroxides

CH3 CH2 C CH3

CH3 CH2 C CH3

CH3

CH2 CH2 C

CH CH2 CH2 C

X

n

CH3

CH3

CH2 C

+ DCP

- 2 X* CH3 CH2 C CH3

X

CH3 CH2 C CH3

CH2 C n

CH2

CH3

CH CH2 CH2 C CH3

CH3 CH2 C

CH3

CH3

CH3

CH3

CH2 C CH3

CH2 C CH3

CH2 CH2 C

CH3 CH CH2 CH2 C CH3

n

CH3 CH2 C n

CH2

CH CH2 CH2 C CH3

Vulcanization of BIIR by ZnO/NN ‘- m- Phenylene  Bismaleic Imide CH3 CH3 CH2 C CH3

CH3 CH2 C CH3

X

CH2 C

CH3

CH CH2 CH2 C

CH2 C n

CH2 C

CH3

CH2

CH3

CH3 CH2 C

CH3

n

CH2

CH2 C CH3

CH3 CH2 C

C

CH3

C

N

C

N

O

O CH3

CH2 CH2 C

CH3

CH3

+ ZnO - ZnOHX CH3

CH CH CH2 C

O CH CH CH2 C

n

CH3

C CH3 CH2 C

CH3 CH2 C

CH3

CH3

CH3

CH2 CH2 C

O

CH CH CH2 C

n

CH3

 IIR and XIIR: Methods of Vulcanization and  nd Vulcanizate Properties IIR (Lanxess Butyl 301) XIIR (Bromo butyl Carbon black (N 330) Carbon black (N 774) Zinc oxide Lead Oxide (Pb3O4) Stearic Acid Sulfur MBT Benzochinondioxim PF-Resin (Amberol) CR (Baypren 110) Dicumyl peroxide Zinc oxide Dicumyl peroxide BMI (HVA 2) temperature time

[phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [°C] [min]

100 50 5 1,0 1,25 1,5 160 25

100 50 5 10 1,0 6 150 12

100 50 5 6 1,0 10 5 190 30

100 50 1,0 1,5 180 15

100 50 5 1,0 5 180 3

100 50 5 1,0 -

100 50 5 1,0 -

1,5 0,5 180 4

1,5 180 20

Source: Butyl and Halobutyl Compounding Guide for Non-Tyre Applications, Bayer AG, Rubber Business Group KA 34166, ed. 12/92 J. Rogers, W. H. Waddell (Exxon) „Isobutylenkautschuke im Kraftfahrzeug: Eine Literaturübersicht, GAK 9/1999-Jahrgang 52, 670-682

 IIR und XIIR: Methods of Vulcanization  and Vulcanizate  Properties IIR XIIR Carb. black (N 330) Carb. black (N 774)

[phr] [phr] [phr] [phr]

Vulcanization Compound Properties ML 1+4 (100°C) MS5 (125°C)

[MU] [min]

MS5 (135°C)

[min]

Physical Properties Shore A Hardnes M100 [MPa] M300 [MPa] Tensile Strength [MPa] Elongation at break [%] CS (70h/150°C)

[%]

100

100

100

-

-

-

-

-

-

-

100

100

100

100

50

50

50

-

-

-

-

-

-

-

50

50

50

50

S/MBT

Chinon

Resin

ZnO

DCP

DCP/BMI

ZnO/BMI

91

94

82

83

88

88

89

17

7

>30

-

-

-

-

-

-

-

16

12

14

16

66

64

64

48

40

54

58

2,5

2,1

1,9

0,9

0,5

0,12

0,19

5,2

1,8

9,5

10,2

16,6

12,8

15,8

12,4

8,9

10,5

13,6

530

400

590

580

680

325

360

68

68

12

58

53

28

13

Source: Butyl and Halobutyl Compounding Guide for Non-Tyre Applications, Bayer AG, Rubber Business Group KA 34166, ed. 12/92 J. Rogers, W. H. Waddell (Exxon) „Isobutylenkautschuke im Kraftfahrzeug: Eine Literaturübersicht, GAK 9/1999-Jahrgang 52, 670-682

 Influence of Oil Loading on Properties of BIIRVulcanizates

BIIR

Polysar Brombutyl 2030

100

100

Carbon black

N 660

60

60

Paraffin Oil

Sunpar/Sunoco Inc.

-

7

Resin

Pentalyn A / Hercules

4

4

1

1

1,3

1,3

Zinc oxide

3

3

Sulfur

0,5

0,5

Stearic Acid MBTS

Vulkacit DM / Lanxess

 Influence of Oil Loading on Properties of BIIRVulcanizates BIIR

BIIR

-

7

Compound-Mooney (ML 1+4/100°C)

72

62

Mooney-Relaxation (MR30) [%]

5,1

5,5

Monsanto-Tack [N]

2,3

2,2

Zugfestigkeit [MPa]

10,5

8,9

Bruchdehnung [%]

650

670

S 50

[MPa]

0,9

0,8

S 100 [MPa]

1,7

1,1

S 300 [MPa]

5,4

4,0

Shore A Härte/23°C

60

58

Shore A Härte/70°C

47

40

Rückprallelastizität/23°C [%]

9

9

Rückprallelastizität/70°C [%]

30

29

Luftdurchlässigkeit/70°C (DIN 53536) [m2/s*Pa])

2,3

3,0

Butylkautschuk-Typ Paraffinöl Mischungseigenschaften

Vulkanisateigenschaften (160°C/12 min.)

 Influence of Carbon Black Loading on BIIR Vulcanizates BIIR

Polysar Brombutyl 2030

100

100

100

100

100

Carbon Black

N 660

60

40

30

20

0

Paraffin Oil

Sunpar/Sunoco Inc.

-

-

-

-

-

Resin

Pentalyn A / Hercules

4

4

4

4

4

1

1

1

1

1

1,3

1,3

1,3

1,3

1,3

Zinc Oxide

3

3

3

3

3

Sulfur

0,5

0,5

0,5

0,5

0,5

Stearic Acid MBTS

Vulkacit DM / Lanxess

 Influence of Carbon Black Loading on BIIR Vulcanizates BIIR (Butyl rubber 2030) Carbon black (N 660) Compound Properties Compound-Mooney (ML 1+4/100°C) Mooney-Relaxation (MR30) [%] Monsanto Rheometer MDR 165°C minimal torque [Nm] t50 [min] t90 [min] Maximal torque [Nm] Vulcanizate properties (160°C/12 min.) Tensile Strength [MPa] Elongation at break [%] M50 [MPa] M100 [MPa] M300 [MPa] Shore A Hardness/23°C Shore A Hardness/70°C Rebound at 23°C [%] Rebound at 70°C [%] Air permeation at 70°C/E+17 [m2 /s*Pa]) tan  δ δ / 0°C (Roelig-test) tan  δ δ /70°C (Roelig-test)

100 60

100 40

100 30

100 20

100 0

72 5,1

62 7,4

56 7,6

51 7,8

40 7,2

2,3 2,9 6,2 7,9

1,7 3,3 6,8 5,5

1,4 1,3 7,1 4,3

1,2 3,3 7,8 3,4

0,8 3,3 6,8 2,2

11,8 730 0,9 1,3 5,4 55 43 10 32 2,14 0,647 0,251

13,1 865 0,7 0,9 2,4 46 33 10,7 39 2,27 0,809 0,215

13,7 975 0,7 0,8 1,8 39 27 11,9 42 2,39 0,863 0,190

13,5 1055 0,6 0,7 1,2 33 23 12,2 44 2,58 0,900 0,178

7,3 1100 0,4 0,5 0,6 22 17 13,8 49 2,78 0,945 0,151

 Influence of (   X)IIR/NR- Blend  Ratio  Ratio on Vulcanizate  Properties BIIR

100

CIIR

0

100

NR

0

Carbon black (N 660)

-

60

-

40

-

0

80

0

60

0

40

0

20

20

40

40

60

60

60

60

60

60

60

60

60

60

Paraffin oil

7

7

7

7

7

7

7

7

Pentalyn A*

4

4

4

4

4

4

4

4

Stearic acid

1

1

1

1

1

1

1

1

Zinc oxide

3

3

3

3

3

3

3

3

MBTS

1,0

1,0

1,0

1,0

1,0

1,0

1,0

1,0

Sulfur

0,5

0,5

0,5

0,5

0,5

0,5

0,5

0,5

-

80

Source: W. Hopkins, R. H. Jones, J. Walter “Bromobutyl and Chlorobutyl. A Comparison of Their Chemistry, Properties and Uses“ paper 16A10 presented at IRC ‘85 Kyoto; International Rubber Conference

 Influence of (   X)IIR/NR- Blend  Ratio  Ratio on Vulcanizate  Properties BIIR [phr] CIIR [phr] NR [phr] Unaged: M300 [MPa] Tensile Strength [MPa] Elongation at break [%] Aged (168h/100°C) M300 [MPa] Tensile Strength [MPa] Elongation at break [%] Air permeation at 50psi/65°C (Q x 10-8] Adhesion at 100°C Self adhesion / tack [kN/m] Adhesion to NR [kN/m] Fatigue to failure after ageing at 168h/120°C [kcycles]

80 20

80 20

4,2 3,7 9,3 9,9 740 770

5,7 10,0 620

5,1 7,1 5,7 8,9 4,3 10,7 12,8 10,3 14,7 9,7 620 560 560 490 580

6,8 10,0 550 2,9

7,6 9,8 420 5,4

7,9 11,0 465 5,7

8,4 9,3 320 9,2

14,7 10,0

4,7 1,6

15,2 9,1 14,7 1,9

61,8 72,7 23,6

3,9

0,3

5,5 10,9 640 2,9

16,8 4,4 7,5 1,3

60 40

60 40

40 60

100 100 -

7,7 9,2 365 7,5

0,1

40 60

6,7 8,8 370 13,8

3,6 5,8 475 13,2

15,4 5,2 20,8 2,9 0,0

0,0

5. Rubber Specialities :  :  Performance Profiles of Vulcanizates 

Maximal Service Temperature 100 80 Processability

60

Low Temperature Performance

40 20 0

Mechanical Properties

Silicon Rubber Hydrogenated Nitrile Rubber Fluoro Rubber Ethylene-Vinylacetate-Copolymers

Ozone Resistance

Oil Swelling

5.1. Fluoro Rubber (FKM / FPM)  Bond

Bond energy [J/mol]

Radius of atoms [A]

C-H

413

0,37

C-F

485

0,72

Maximum Service Temperature: 3.000 h 1.000 h 240 h 48 h

232°C 260°C 288°C 316°C

Properties of FKM-Vulcanizates: Areas of Application: 60 % 10 % 10 %

Positive: • • • • •

Excellent resistance to ozone, UV- and weather High service temperature Low oil swell High resistance to chemicals and acids High flame resistancy

20 %

Rubber goods:

Negative: • • • • •

High price Poor low temperature flexibility (except Kalrez) Poor resistance to amines and bases Poor compounding Necessity to oven ageing after vulcanization

Sources:

Automotive (75% in Europe) Aviation and Aerospace Chemical planty s (Fume treatment of incineration and power plants) rest

30-40 % 30-40 % 10-15 % ~5% 4.5 % 10 %

O-Rings and seals crank shaft seals hoses and profiles Modification of polyolefins pipes and tubings rest

J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons A. L. Logothetis „Chemistry of Fluorocarbon Elastomers“ Prog. Polym. Sci., Vol. 14, 251-296 (1989)

 Fluoro Rubber: Market, Producers and Capacities World Market

Market:

2002: ca. 15.000 t

Prices:

Top price:

20 - 50 EUR/kg (correlated with F-content) ~ 500 €/kg (Kalrez)

Growth:

8 - 10% p. a.

 Return on Sales: 20 - 25%

Asia 22 %

USA 45 %

WEurope 33%

Source: Kunststof En Rubber; 11 November 2003

 Producer

Trade  names

 Market Share [%] 

Site

Capacity*  [kt] 

Du Pont

Viton/Kalrez

43

3,0 1,0 1,0

Dyneon

Fluorel

22

Deepwater, NJ Dordrecht, NL Utsonomiya, Jp Kawasaki, Jp Decatur, AL

Solvay (Ausimont) Daikin Kogyo Asahimont Asahi Glass Unimatec

Tecnoflon

15

Daiel

10

Aflas Noxtite

5 5

DuPont-Showa

Zwijndrecht, BE Gendorf, DE Spinetta, I Osaka, Jp Chiba, Jp Chiba, Jp Jp

Estimated total capacity: 20 kt; capacity utilization: 80-100%

2,0 2,1 2,0 1,0 2,0 1,0 1,0

 FKM: Composition of Standard Grades HFP     0     8

     ]       %     t .     w      [       0      P     4      F      H

Z

    0     6

Fluorine containing monomers

 P     o    (     o    r     r    u      y    l      p    b      m    b     e    h    o   e    u     r     r     s     s     s      )    X

    0     2

H

V      2     0     D     F       [      w     t     . %     4     0       ]       A     m   

F C

H

F

F

F C

F CF3 C

C

F

8     0    

TFE

C

F F

6     0    

VDF

C

HFP F

Y Copolymers

[wt.%]

TFE

80

60 40 TFE [wt.%] VDF [%] 33 55 22

X Y Z Soures:

fluorine cont.

TFE [%] 33 23 12

20

VDF

HFP [%] 33 22 65

TFE/P

54

VDF/HFP

65

VDF/HFP/TFE

67

VDF/HFP/TFE/CSM*

69

TFE/PMVE/CSM*

71

*Cure Site Monomer

J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons A. L. Logothetis „Chemistry of Fluorocarbon Elastomers“ Prog. Polym. Sci., Vol. 14, 251-296 (1989)

 FKM: Performance of Standard Grades Copolymers

Fluorine Cont. Volume swell [wt.%] benzene gear oil 21°C 121°C VDF/HFP 65 20 171 VDF/HFP/TFE 67 15 127 VDF/HFP/TFE/CSM* 69 7 45 TFE/PMVE/CSM* 71 3 10 TFE/P 54 -

Tg [°C]

-18 -8 -5 -19 -2 (0)

Storage in motor oil which contains amines (163°C)

180

Benzene/21°C

160

10    t   a 0   n   o    i -10    t   a   g   ] -20   n   %   o   [ -30    l   e   k    f   a -40   o   e   r   n   b -50   o    i    t -60   c   u -70    d   e   r -80

Gear Oil/121°C

   % 140    [    l    l   e 120   w    S 100   e 80   m 60   u    l   o 40    V

d

20 0 60

65

70

Fluorine Content [wt.%]

75

HNBR FKM (68% F)

0

200

400

600

time [h]

800

1000

 FKM: Glass Transition Temperatures H

   ] 0    C    °    [   e   r -5   u    t   a   r -10   e   p   m-15   e    t   n   o -20    i    t    i   s   n -25   a   r    t   s -30   s   a    l    G-35

TFE/VDF/PMVE TFE/VDF/HFP

0

0,5

1

1,5

2

F

H

F

F

CF3

VDF Vinylidene fluoride (59% fluorine)

HFP Hexafluoropropene (76% fluorine)

F

F

F

F

F

F

F

O

F

F

H

CH3

H

H

TFE

Tetrafluoroethylene (76% fluorine)

CF3 PMVE Perfluoromethylvinyl ether (69% fluorine) P

Propen

Hydrogen content [wt.%]

Source: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons

 Range of FKM -Grades and Vulcanization   s   e   v    i    t    i    d    d    A   c    i   s   a    B    h    t    i   w   a    i    d   e    M   n    i   e   c   n   a    t   s    i   s   e    R   g   n    i   e   g    A

Vulcanization with Peroxides

peroxidisch

Vulcanization with Bisphenols

Vulcanization with Diamines

Viton A Aflas  PVDF

55

Viton B, GF 

Viton GLT  Kalrez  PTFE

65 Fluorine Content [wt. %]

75

 FKM: Vulcanization with Diamines

1. Elimination of HF by MgO, CaO und PbO. CF3 CF2

CF3

- HF CF2

CH2 CF2 CH2 CF2

CF3

- HF

CH CF2 CH2 CF2

CH CF CH CF2

CF2

F

2. Crosslinking by Diamines, which are used in "capped form" (such as carbamates) in order to increase scorch resistance CF CF 3

3

CH CF CH2 CF2

CF2

CF3 CF2

CH CF CH CF2

CF2

CH CF CH CF2

H2N

R

CF2

CH

NH

NH2

N - 2HF

R

R

NH

CF3

CF2

CH2 CF2

N CF2

CH CF CH2 CF2 CF3

CH

CH2 CF2

CF3

Diamine cure yields crosslinks which are liable to hydrolysis (not steam resistant) CF3

CF3 CF2

CH

CF2

CH2 CF2

CH O

N

H2O

R

CH

O CH2 CF2

CF2

CF3

Sources:

NH2 R

N CF2

CH2 CF2

CH

NH2 CH2 CF2

CF3

W. W. Schmiegel, Kaut. Gummi Kunst., 31, 137 (1978) W. W. Schmiegel, Angew. Macromol. Chem., 76/77, 39 (1979)

 FKM: Vulcanization with Bisphenols 1. Elimination of HF by MgO, CaO and PbO CF3 CF2

CF3

- HF CF2

CH2 CF2 CH2 CF2

CF3

- HF CH CF2 CH2 CF2

CF2

CH CF CH CF2

F

2. Crosslinking with Bisphenols ( such as Bisphenol AF) in the presence of BTPPC (Benzyl triphenyl phosphonium chloride) BTPPC acts as phase transfer catalyst and is often referred to as "accelerator" +

CF3 OH +

HO

CH2 P

+

Cl

CF3

- HCl

CH2 P

O

HO

CF3

CF3 n

n CF3

CH CF CH CF2

CF2

CH CF CH CF2

CH CF CH2 CF2 O

O

HO

CF2

CF3

CF2

CF3

CF3

Sources:

+

CF3

CF3

CF3

T. L. Smith, W. H. Chu, J. Polym. Sci A-2, 10, 133 (1972) O A. W. Fogiel, J. Polym. Sci., Symp., 53, 333 (1975) W. W. Schmiegel, Kaut. Gummi Kunst., 31, 137 (1978) CF2 CH CF CH2 CF2 W. W. Schmiegel, Angew. Macromol. Chem., 76/77, 39 (1979) CF3 A. Neppel, M. v. Kuzenko, J. Guttenberger, Rubber Chem. T echnol., 56, 866 (1983) D. J. Plazek, I. C. Choy, F. N. Kelley, ‚E. von Meerwall, L.-J. Su, Rubber Chem. Technol., 56, 866 (1983) A. N. Theodore, M. Zinbo, R. O. Carter, III, J. Appl. Polym. Sci., 61, 2065 (1996)

 FKM: Vulcanization with  Peroxides CF CF3

CF2

CF2

CF2

CF

CF2

CF2

CF

CF2

J

3

CF2

CF2

Br

CF2 CF2

Br/J-Content: 0,5-1 wt.%

n

C H2J2 C F2J2 J - ( C F2) - J 4 -6

Type of  bond C-F C-H C-Br C-J

Bond energy [kJ/mol] 480 405 270 200

CF 2

CF 2

CFBr

CF 2

CHBr

CF Br

O

CF 2 CF 2 Br

CF 2 CF 2 Br

C-F bonds bonds have have a high high bond bond energy energy.. As As a conseq consequen uence, ce, F-radic F-radicals als cannot cannot be abstra abstracted cted by peroxi peroxides des and  FKM with high fluorine contents (> 70 wt.%) cannot be vulcanized by the use of peroxides. •

 For the vulcanization of FKM with F-contents > 70 wt% special cure sites are required. For this purpose  bromine and iodine are incorporated into FKM. C-Br and C-I bonds have a lower bond energy thqn C-F  bonds. Therefore Br- and I-radicals can be abstracted by the use of peroxides. •

 Br- and I- based cure sites are incorporated by chain modifiers and by special comonomers which  contain Br- and/or iodine. •

 In the presence of Br- and I- containing compounds (modifiers and monomers) the polymerization  proceeds as a „living radical polymerization“ (this probably was the first example of a living radical   polymerization). During the course of the polymerization Br- and I are incorporated as end groups.  During peroxide cure of Br- and I- containing FKM and during subsequent annealing toxic compounds  are released which contain bromine and iodine. Source:

D. F. Lyons GAK 3/2005, Jahrgang 58 „ Einfluss der Molmasse auf die Eigenschaften von Bisphenol-AF-vernetzten Fluorkautschuken“

 FKM: Vulcanization The The meth method od of FKMFKM-cu cure re depe depend ndss on the the fluo fluori rine ne cont conten ent. t.

•

Copoly Copolymer merss based based on vinyl vinylide idene ne fluori fluoride de and propen propenee (Aflas (Aflas)) are cross crosslin linked ked by  the use of peroxides. •

 Fluoro rubbers with a fluorine content<70 wt.% (such (such as copolymers copolymers based on VDF VDF and HFP HFP)) are liab liable le to HFHF-el elim imin inat atio ion n whic which h is a prer prereq equi uisi site te for for the the vulcan vulcaniza izatio tion n with with diamin diamines es and bisph bispheno enols. ls. MgO MgO and Ca(OH Ca(OH)) 2 are added to the  rubber compound in order order to react with HF which is eliminated during vulcanization. •

 FKM vulcanizates which are cured by diamines and bisphenols contain double  bonds. As a result, their resistance to heat and ageing is inferior to FKM without  double bonds. Also, Also, diamine cured FKM is liable to hydrolysis. •

 Fluor rubbers with a fluorine content > 70 wt. % (FKM which contains no or only  a small amount of VDF) cannot elimiminate HF. Therefore vulcanization cannot  be achieved by diamines or bisphenols. FKM with F-contents > 70 wt.% requires requires  special cure site monomers which enable peroxide cure. •

Source:

J. Scheirs Scheirs „Modern Fluoropolymers“ Fluoropolymers“ High Performance Performance Polymers Polymers for Diverse Applications John Wiley & Sons

5.2. Silicon Rubber (Q)  CH3

CH3 (

Si

(

O

CH3

CH3

CH3 O

O ) n

Si

CH3

Si

Grade

VMQ

 

CH2



 

O

Si

Si

PVMQ

CH2 CH2 O



Low temperature performance High temperature resistance Low dependence dependence of properties properties on temperature temperature changes Ozone-, Ozone-, UV- and Weather Weather resistan resistance ce Hydrophopic character Physiological Physiological inertness Low reista reistance nce against against acids, acids, bases, bases, vapour vapour and hydrocarb hydrocarbons ons (signifi (significant cant improvem improvement ent with FMVQ) Mechanical properties RTV: TV: poor poor HTV: bett etter / DVR ! High gas permeability permeability

Bond energies

CF3

O ) n

Si





CH2

CH3 (

O ) n

CH

CH3

Si-O C-O C-C C-S S-S

FMQ

CH3

CH3

- 45 - 45 - 70

Negative:

CH3 Si

- 120 - 120 - 120 - 69

Positive:



(

Tm [°C]

Vulcaniza Vulcanizate te Properti Properties: es:

CH

CH3

MQ VMQ PVMQ FMQ FMQ

MQ

O ) n

Si

Tg [°C]

[kJ / mol] 444 33 9 34 8 2 72 266

Silicon Rubber: Properties and Application Areas Applicati Application on Areas: Areas:

Haushalt 20%

Medical Applications 25%

Automotive industry 40%

Machine buildi b uilding ng 15%

Temper Temperatur aturee [°C] [°C]

duration

90 121 150 200 250 315

40 years 10-20 years 5-10 years 2-5 years 3 months 2 months



Pharmaceutic Pharmaceuticalal- and medical medical rubber rubber goods



Rubbe Rubberr goods goods with with food food contac contactt



Cable Cable insulation insulation



Adhesives



Moulded Moulded articles articles



Hoses, Hoses, sealants sealants (Automotive (Automotive,, Machine Machine building building and E&E)

Sources: Chemistry •K. Polmanteer, Rubber Chemistry

Technology, Technology, Vol 61: 471-502“Sili 471-502“Silicon con Rubber, its Development Development and Technological Technological Progress“ Progress“ Maxson GAK 12/1995, Jahrgang 48, 873-884 „Fluor-Silikonkautschuk“ •D. Klages, U. Raupbach, GAK 4/1995, Jahrgang 48, 49-51 „Fluorsilicon-Kautschuk: Ein sehr moderner Werkstoff“ O. R. Pierce, K. E. E. Polmanteer, J. C. Saam, Rubber Chemistry Technology, Vol 52: 437-526 „Silicone „Silicone Elastomer Developments 1967-1977“ •E. L. Warrick, O. Polymere. Wiley-VCH, 2005 •Winnacker/Küchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. •T.

 Producers Capacities  nd Silicon Rubber Rubber Market Manufacturer*

Site

SiloxaneCapacity [kt]

Silicone RubberBrand Name

Dow Corning

Carollton, USA

260.000

Silastic® 

Barry, GB

110.000

Waterford, USA

110.000

Ohta, Japan

40.000

Leverkusen, DE

65.000

Silopren® 

Shin-Etsu

Isobe, Japan

95.000

KE, Sylon® 

Wacker

Burghausen, DE

90.000

Elastosil® 

Nünchritz, DE

30.000

Rousillon, FR

60.000

Momentive (formerly: GE + Bayer)

Rhodia

S Western World (2000)

Rhodorsil® 

850.000

*Evonik *Evonik and Crompton Crompton are active active in this this market market withou withoutt proprie proprietary tary siloxa siloxane ne produc productio tion n

Japan 25%

Nordamerika 44%

Year 1995 Cons Consum umpt ptio ion n /t: /t: ~ 110. 110.00 0000 Growth rate 2005: ca. 3,5 % / a;

2005 ~ 200. 200.00 0000 LSR ca. 10 % / a

Europe 31%

Source: Winnacker/Küchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Polymere. Wiley-VCH, 2005

Silicon Rubber: Production Synthesis Synthesis of Silicium: SiO2 + C

Si

+ CH3

Rochow-Process: 2 CH3-Cl

+

2 CO

Cl

Si

Si Cl CH3 H3C O

H3C

Si

H3C CH3 n

Cl

Si Cl CH3

+

4 H2O

- HCl

CH3 Si

O

O CH3

Si

CH3

H3C CH3 O Si CH3 H3C Si O O Si H3C H3C H3C

O

 D3

 D4

Si CH 3 CH3 CH3

Si O

n

 Dn

Silicon Rubber: Production H3C CH3 O Si CH3 H3C Si O O Si H3C H3C

O

CH3

85 % O

Si O

Si OH n

15 %

Si CH 3 CH3

CH3

CH3

CH3

Übliche Temperaturen: KOH 140°C NaOH 170°C

Katalysatoren: Säuren, Lewis Säuren, Saure Silikate, Basen

After After short short-sto -stoppin pping g of the „polymer „polymerizat ization“ ion“ residual residual monome monomers rs are removed removed under vacuum. vacuum. For standar standard d grades grades residual residual monome monomerr contents contents are specified specified < 1 wt.% (for (for specialit specialities: ies: <0,5 <0,5 wt.%) wt.%)

CH2

CH2

HC CH O Si CH3 H3C Si O O H3C

Si CH

Si CH 3 CH

CH2

CH2

O

CF3 H3C Si

O

CH3

H2C CH2 O Si Si CH3 H3C O O

Si

O Si O H3C

CF3

O Si

H3C

CH3

Si

O

CH2

CF3

Si CH 3 C H2

CF3

Modif Modified ied silico silicon n rubbe rubbers rs are obtain obtained ed by the copoly copolyme meriz rizati ation on with with the respec respectiv tivee cyclic cyclic monom monomers ers.. As a consequenc consequencee multiblo multiblocc copolyme copolymers rs are obtained obtained initiall initially. y. At extended extended reaction reaction times times randomiz randomizatio ation n occurs. occurs.

Silicon Rubber: Vulcanization Chain Chain length length [nSi] Viscosity processing Crosslinkin Crosslinking g method method Peroxides Addition Cure temperature temperature

HTV-Kautschuk

Liquid Rubber

predominantly 1C- und 2C-systems 2C-systems

predominantly 2C-Systeme

110 -300 °C

110 - 200 °C

RTV-Rubber

10.000 1.000 Greasy/Highly Greasy/Highly viscous viscous Highly Highly viscou viscouss Transfer moulding Transfer moulding Extrusion Transfer Moulding

200 liquid / pourable

RTV-1: Condensation RTV-2: Addition 25 - 150 °C

Vulcanization Method

Products

Condensation at room temperature (RTV)

Silanol containing Silicon rubbers

Platinum catalyzed hydrosilylation at low or el e levated te t emperature (RT to 80°C, LSR: 110-200° 110-200°C C)

Silicon rubbers with silanol an a nd vinyl groups

High temperature-Vulcanization with peroxides peroxides (HTV: 120-180°C)

MQ, PVMQ PVMQ,, MVQ, FVMQ

RT -  -Vulcanization   Vulcanization of Silicon Rubber (2K -  -System)   System)  1a)

Condensation of polysiloxanes which contain silanol groups by multifunctional alkoxysilanes R R

R

Si

OH

R R

HO

OR RO

Si

O

R

- 4 ROH

R

R HO

O

R

O

R Si

Si

Si

R

O Si

R

OR

OH

Si

Si

Si

OR

Si

R

R

R

R

Typical mulftifunctional alkoxysilanes are: OR

R

RO Si OR

RO Si OR

OR

OR

OR

OR O ( Si

RO Si OR

O )

n

R = Me, Et

OR

Metal carboxylates are often used for catalysis : Metals: Pb, Zn, Zr, Sb, Fe Sn Ba, Ca Carboxylates: Naphthenate, Octoate, Hexoate, Laurate, Acetate Typical examples are:

Tin-(II)-octoate

und

Dibutyl tin dilaurate in the presence of chloroacetic acid

RT -  -Vulcanization   Vulcanization of Silicon Rubber (1K -  - und 2K -  -Systems)  Systems) 1b)

Condensation of polysiloxanes which contain capped silanol groups by multifunctional alkoxysilanes R Si

O

C

R

R

O

O

CH3 C

CH3 RO

O

Si R

OR Si

R Si R

O

O

RO

C

CH3

OR

R + H2O - CH3COOH

R

CH3 C

O

Si

Si

Si O

R

O

R

O

R

Si R

O

R

O

Si

Si R

R

R

For the condensation reaction the catalysts quoted under 1a) are being used.

RTV -  -Vulcanization   Vulcanization of Silicon Rubber (2K -  -System)   System)  1c)

Condensation of polysiloxanes with silanol groups by means of multifunctional silanes (with evolution of hydrogen)

O

R Si

H

OH

Si

R R

O

R R

O

R

Si

H

HO

Si

- H2

Si

Si

R R

O

R R

R

O

O

Si

O

O

For the condensation reaction the catalysts quoted under 1a) are being used.

Application for Bladder coatings

LT -  -Vulcanization   Vulcanization of Silicon Rubber  (1K und 2K -  -Systems)  Systems) 2)

Platinum catalyzed hydrosylization (50-150°C) CH3 (

(

Si

CH3 O ) Si n

CH3

CH

CH3

H

Si CH3

O ) Si n

CH3 O CH2

( Pt-Compounds as H2PtCl6 (ca. 10 ppm)

O

Si

CH3 O ) Si O n

CH3

CH2

CH3

CH2

( Si

O ) Si O n CH3 CH3

CH3

Inhibitors:

Si R

HT -  -Vulcanization   Vulcanization of Silicon Rubber 3) Peroxide Cure (120-180°C) Temperature °F

Typical Peroxides

(t1/2) = 1 min.) 234 Bis(2,4-dichlorobenzoyl)Peroxide 271 Di-Benzoylperoxide 340 Di-Cumylperoxide 2,5-Dimethyl-2,5-bis(t-butyl peroxy) hexane 354 379 Di-t-Butylperoxide R

R Si

O

Si

O

R

R

R

R

Si

Si

R

R

R O

Si

R O

R*

Si R

Peroxide - 2 H* R Si R

R O

Si R

R O

Si R

R*

R Si R

O

Si R

R O

Si

R

R Si

O

Si

R O

Si

R

R

R

R

R

R

Si R

O

Si R

R

O

Si R

Impact of Vulcanization Method on Cost of Articles  Comparison of Peroxide -  - (HTV) and platinum catalysed LTV -  -Cure   Cure 

Cost Factor

HTV

LTV

Raw materials [$/pound] Vulcanization time [sec] Overhead-Costs [$/h] salaries [$/h] Hours per shift Shifts per week Number of nests per mould Weight per article + 10% loss Number of articles per week Material consumption per week Raw material costs per week [$] Total cost per week [$] Cost per article [$] Savings per article [%] Financial result per year [$] Increase of financial result [%]

3,50 120 60,00 12,00 10 8 3 59,5 7200 885 3.097,31 8.857,31 1,23 0 44.286,55 0

5,00 60 60,00 12,00 10 8 3 59,5 14.400 1.770 8.849,45 14.609,45 1,01 21,25 230.563,76 420,62

Source: Rubber World, 12/1994, S. 20-24 

5.3. Hydrogenated Nitrile Rubber (HNBR)  Range of Products: HNBR (partially and fully hydrogenated grades) XHNBR Low-Tg-HNBR Low-Mooney-HNBR

Overview: • • • • • •

Microstructure, Property Profile and Appliecation Areas Catalytic Hydrogenation of NBR Sequence of Process Steps in NBR- and HNBR-Production Producers and Production Capacities Chemical and Physical Properties Comparison of NBR- and HNBR Properties Speed of Ageing Tg Crystallization Stress/strain-Performance Vulcanizate Properties of Sulfur- und Peroxide crosslinked Vulcanizates Performance of HNBR in Power Transmission Belts » » » »

• •

HNBR: Microstructure 

C

N

C N

δ−

CH2 H3C

CH CH2

Butylidene-Moiety

H CH CH C C H2 H2

H

Ethylidene-Moiety

δ+

C CH 2 CH 2 1

N

Nitrilo-EhylideneMoiety

 HNBR: Property Profile and Application Areas Positive: • •

• • • •

Broad range of grades (Mooney, degree of hydrogenation, acrylonitile content) excellent mechanical properties of vulcanizates (high TS, high abrasion resistance and high dynamic resistance) high oil resistance (depending on acrylonitrile content) good adhesion to fibres and cords (Covulcanization) Low temperature flexibility High filler loadability of compounds

Negativ: • • • •

Max. service temperature < 155°C High Tg >-30°C Bad incorporation of softeners High price (~ € 20/kg)

HNBR: Application Areas and Articles  Blow Out Preventer

Expansion Joints

15% 45% 25% 7%

Ship Couplings Riemen Kabel

4%

Schläuche Ölförderung

4% Dichtungen Sonstige

Rotor/Stator- Pumps Roll Covers

Oil well Packers

Catalytic Hydrogenation of NBR Requirements for Hydrogention Catalyst: Selective and quantitative hydrogenation of C=C- double bonds in the presence of nitrile groups without gel formation Low catalyst loadings and/or catalyst recovery

Selective Hydrogenation of C=C bonds

•

•

C

N

Homogenous Catalyst Systems: (PPh3)3 RhI Cl and (PPh3)4RhI H

(US 3700637, DE 2539132, EP 134023, DE 3541689, DE 3540918, EP 298386, DE 3529252, DE 3433 392, US 4,464,515, US 4,503,196, DE 3921264, US 6084033)

C N H2/Catalyst

Heterogenous(Supported) Catalyst Systems: C

Pd/SiO2; Pd/C; Pd/CaCO3; Pd/BaSO4

N

(DE 3229871, US 4337329, US 4384081, US 4510293, DE 3227650, DE 3046008, EP 0298386)

C

Relative prices of noble metals [€/g]: Rh (150) > Ru (75) > Pd (12,50)

N

Unselective Hydrogenation of Nitrile-Groups Results in Gel Formation

H C NH2

+

H

HN - NH3

C N

HNBR Grades with Low Mooney Viscosities 

R

C

During hydrogenation the Mooney viscosity increases by a factor 2. Due to high stickiness the production of NBR-grades with a Mooney viscosity > 30 MU is not possible. Therefore the range of standard HNBR viscosities was limited to >60 MU until recently.

N

C

Cross-metathesis of NBR with olefins allows for the production of NBR with Mooney viscosities < 30 MU. In-situ hydrogenation of theseNBR-feedstocks yields HNBR-grades with Mooney viscosities < 60 MU.

N

Catalyst

R CH 2 H C C N

C

N

As a consequnece of low TONs, large amounts of catalysts are required for the cross-metathesis of NBR. Metathesis catalysts which are robust towards nitrile groups are protected by patents. Their use implies the payment of licence fees.

Catalysts without Activity in NBR -  -Metathesis   Metathesis *  PCy 3

PPh3 Cl

Cl

Ru

Ru

Cl

Cl

S

PCy 3

PPh3

BH 3

Ph

2Ph

P

Ciba-Catalyst

Cl

Ru

Cl P

Grubbs-I-Catalyst

Cl

Ru

Cl

P

PCy 3

Cl

R1

Cl PCy 3

R3

BH 3

Ph

Catalyst from Prof. Berke' s group (University of Zurich)

Ph

Fürstner-(I)-Nolan-Catalyst (Umicore)

2-

+

Ph

Cl SnCl3

Cl

Ph

N

Ph

+

Ru

Cl

N

SnCl3

P

Ph

2-

SnCl3

Ph P

Ru

Ph 2

2 Catalyst from Prof. Berke' s group (University of Zurich)

Catalyst from Prof. Berke' s group (University of Zurich) *Source: Julia-Maria Müller, Dissertation TU München

Catalysts which are Active in NBR  NB  -  -Metathesis   Metathesis * ( „Number  of Catalytic Steps (TON) “  “ )    Mes

N

N

CF 3CO O

Mes

Mes

N

N

Mes

Mes

N Cl

Cl

Ru

Ru

Cl

CF 3COO

R1 P

O

+

N

Mes

Ru

Cl

PCy 3

R2 R3

Buchmeiser-Nuyken-Catalyst TON = 8 / 23°C Mes

N Cl

N

+

Ru

R2

SnCl3

Ph

PCy 3

BF 4+

Piers-Catalyst

Cl

2K

Mes

Piers-II-Catalyst TON=12 / 55°C

Mes

N

N

Grubbs-II-Catalyst TON=40 / 23°C

Mes

Mes

N

N

Mes

Cl

Ru

Cl O

Cl

N

Ru

Cl

Cl O NO 2

Grubbs-H oveyda-Cata lst TON=53 / 23°C

Grela-Ca talyst TON=78 / 23°C

Ru N

Br

Grubbs-III-Ca talyst TON=120 / 23°C

*Sources: Julia-Maria Müller, Dissertation TU München; M. Schneider, Dissertation TU München, M. Kellner, MSc-Thesis TU München; K. Langfeld, MSc-Thesis TU München; C. Gantner, MSc-Thesis TU München

Br

Sequence of Process Steps in NBR and HNBR -  -  Production   NBR-Production: Sequence of Process Steps: Emulsionspolymerization

Removal of  residual monomers

Latexcoagulation + crumb wash

Mechanical dewatering

Thermal drying

Bale pressing

Bale wrapping Packaging and storage

 HNBR-Production: Sequence of Process Steps Make-up of  Hydrogenation catalyst solution

Catalyst recovery

Bale cutting

Cemement preparation-

Removal of oxygen and hydrogenation

dilution

Catalyst recovery

Wet solvent stripping

Mechanical dewatering of crumbs

Thermal crumbdrying

Bale pressing

Bale wrapping Packaging and storage

 HNBR- Producers and Capacities Producers and Capacities

Company

Site

Capacity [t]

Zeon

Takaoka Houston

Japan USA

Lanxess

Leverkusen Orange

Germany USA

2.800 2.000 3.000 3.600 11.400

Total 14000

Markt- und Marktentwicklung

12000 10000

   ]    t    [   e 8000   m   u    l 6000   o    V

Consumption capacity

4000 2000 0 1992

1994

1996

1998

2000

2002

2004

Solvent removal by evaporation

Ageing  of Unvulcanized NBR and HNBR  ( Increase  Increase of Mooney Viscosity ML 1+4/100 °C)) 

+1

NBR Hydriergrad: 0 % HNBR Hydriergrad: 96 % HNBR Hydriergrad: 99,5 %

+0 -1 -2 -3   r    b

-4

   V   n - 5    l

-6 -7 -8

2,0

2,4

2,6

2,8

3,0

3,2

1/T *103 [K-1] T [°C]

180

160

140

120

100

80

60

40

Source: W. Obrecht, H. Buding, U. Eisele, Z. Szentivani, J. Thörmer, Angew. Makromol Chem. 145/146 (1986) 161-179 (2373) „Hydrierter Nitrilkautschuk: Ein Werkstoff mit neuen Eigenschaften“

Tg of HNBR and NBR E/ACN-Copolymers HNBR (fully hydrogenated)

100

100

 NBR

80

80

60

60

40

40

20

   ]    C    °    [ 20   g    T

0 -20

0

-40 -60

-20

-80

-40

-100

0

20

40

60

80

Acrylonitrile Cont. [wt.%]

100

0

20

40

60

80

Acrylonitrile Cont. [wt.%]

Data for Ethene/Acrylonitrile-Copolymers from: R. E. Uschold, I. B. Finlay, Appl. Polym. Symp. 25 (1974) 205

1

Tg of Ethene/Vinylacetate- und Ethene/Vinylchloride-Copolymers 100 Ethene/Vinylacetate-Copolymers 80

100 80

Levapren Nielsen et al.*

60

Ethene/Vinylchloride-Copolymers

60

40

40

   ]    C    °    [   g 20    T

20

0

0

-20

-20

-40

-40

0

20

40

60

80

100

0

40

60

80

100

Vinylchloride Cont. [wt.%]

Vinylacetate Cont. [wt.%] Source:

20

Ethene/Vinylacete Copolymers: L. E. Nielsen, J. Pol. Sci. 42 (1960) 357-366 Ethene/Vinylchloride Copolymers: F. P. Reding, J. A. Faucher, R. D. Whitman, J. Pol. Sci. 57 (1962) 483-498

 Influence of ACN -Content on Crystallinity of HNBR (DSC) 16 14 1. DSC-Aufheizung

   ] 12    %    [ 10   y    t    i   n 8    i    l    l   a    t   s 6   y   r    C 4

2. DSC-Aufheizung

2 0 0

10

20

30

40

Acrylonitrile Content [wt. %]

50

60

Tgs of Ethylene-Copolymers 100 50 0

   ]    C    °    [ -50   g    T

EPM HNBR EVC EVM

-100 -150 -200

0

10

20

30

40

50

60

70

80

90

100

Comonomer Content [wt.%]

 Influence of Nitrile Content on Tg of HNBR 100

50

   ]    C    °    [   g    T

0

-50

HNBR (fully hydrogenated) NBR

?

-100

-150 0

10

20

30

40

50

60

70

Acrylonitrile Content [wt. %]

80

90

100

 Dependence of Tg on Degree of NBR- Hydrogenation (   ACN Cont .:  .: 34 wt. %) -20

dyn. mech. (11 Hz)

-22

DSC

-24 -26

   ]    C    °    [   g    T

-28 -30 -32 -34 0

20

40

60

80

100

Degree of Hydrogenation [%] Source: U. Eisele. Z. Szentivanyi, W. Obrecht J. Appl. Pol. Sci.: Appl. Polym. Symp. 50, 185-197 (1992) „Correlation Between Network Structure and Properties of Sulfur- and Peroxide-Cured HNBR Vulcanizates“

Influence of Residual Double Bond Content on Stress/Strain -  -  Properties of HNBR -  -based   based Vulcanizates  (34 wt.% ACN; unfilled ; sulfur vulcanized   )  100 phr HNBR 0,07 phr Schwefel 2,63 phr TMTD 2,07 phr DTDC* * Dithiodicaprolactam

12 10    ]   a 8    P    M    [   s 6   s   e   r    t   s 4

11,0% 7,9% 4,0% 1,9% 0,5%

2 0 0

100

200

300

400

500

600

700

strain [%] Source: U. Eisele. Z. Szentivanyi, W. Obrecht J. Appl. Pol. Sci.: Appl. Polym. Symp. 50, 185-197 (1992) „Correlation Between Network Structure and Properties of Sulfur- and Peroxide-Crosslinked HNBR Vulcanizates“

Dependence of E ‘  ‘ and E ‘‘  ‘‘ on Temperature (HNBR with  38,5 wt .% ACN)  10000

1000    ]   a    P    M    [ 100

E' E''

         δ δ

  n   a    t    d   n   a    '    E

10

1

0,1 -200

-150

-100

-50

0

50

100

Temperature [°C]

 NBR and HNBR: Impact of ACN -Content on Stress/Strain- Properties of Unvulcanized  Raw Rubbers 0,8

50

 HNBR

 NBR

0,7

45 40

0,6

18,9 wt.%

35

   ] 0,5   a    P    M    [ 0,4   s   s   e   r 0,3    t    S

19,2 wt.% 28 wt.% 34,2 wt.% 39,1 wt.% 49 wt.%

0,2 0,1

28 wt.%

   ]   a 30    P    M    [ 25   s   s 20   e   r    t   s

33,9 wt.% 38,5 wt.% 48,3 wt.%

15 10 5

0

0

0

1000

2000

elongation [%]

3000

4000

0

500

1000

elongation [%]

1500

Influence of ACN -  -Content  Content of Unvulcanized NBR and HNBR on Maximum Stress (Yield -  -Stress)  Stress) on “ True  True “  “ Tensile Strength  300

   ]   a    P    M    [    h    t   g   n   e   r    t    S   e    l    i   s   n   e    T    "   e   u   r    T    "

250

200

150

100

50

0

   h    t   g   n   ]   e   r   a    t    P    S   -    M    [    d    l   e    i    Y

1 0,8 0,6 0,4 0,2 0 0

10

20

30

40

50

Acrylonitrile Content [wt.%]

Influence of Extention on Permanent Elongation of Fully  Hydrogeanted , Unvulcanized HNBR (Variation of ACN -   )  -Content   Content  extension 120

160

280%

ε = ε bleibend

   ] 140    %    [   n 120   o    i    t   a 100   g   n   o 80    l   e    t   n 60   e   n   a   m   r 40   e   p

48,3 %

   ] 100    %    [   n   o    i    t 80   a   g   n   o 60    l   e    t   n   e 40   n   a   m   r   e 20   p

18,8 %

ASTM D 1566 - 98 Kautschukdefinition

39,0 % 28,2 % 34,9 %

20

200%

120%

80%

0 0 0

100

200

elongation [%]

300

400

0

20

40

ACN-content [wt.%]

60

Influence of Sulfur -  - and Peroxide  Vulcanization  on Properties of Partially Hydrogenated HNBR  H-NBR Sulfur Stearic acid ZnO MgO OCD ZMB-2 N 550 TMTD CBS

100,0 phr 0,5 phr 1,0 phr 2,0 phr 2,0 phr 1,0 phr 0,4 phr 45,0 phr 2,0 phr 0,5 phr

Vulcanization time: 20 min temperature: 160°C H-NBR 100,0 phr ZnO 2,0 phr MgO 2,0 phr DDA 1,0 phr ZMB-2 0,4 phr N 550 45,0 phr TAIC 1,5 phr Perkadox 1440* 7,0 phr Vulcanization time: 15 min Temperature: 180°C Annealing: 6h/150°C Perkadox 1440 Bis(t-butylperoxyisopropylbenzol 40%ig

1706 S HNBR-Grade (Therban) 33,7 ACN-content [wt.%] 4,3 RDB-content [Mol.%] 60 ML 1+4(100°C) [MU] Compound Properties 64 Compound Mooney/ ML 1+4(100°C) 12,5 Mooney-Scorch (120°C) [min.] 56,4 Fmax [N] Vulcanizate-Properties 72 Shore A Hardness(23°C) 69 Shore A Hardness (70°C) 3,4 M 100 [MPa] 8,8 M 200 [MPa] 14,7 M 300 [MPa] 27 TS [MPa] 510 elongation [%] 38 Rebound [%] Compression Set 73 70h/-10°C [%] 70h/23°C [%] 73 70h/100°C [%] 70h/150°C [%] Hot air ageing 55 D/D0 (150°C/ 5 d) [%] D/D0 (150°C/24 d) [%] Degree fo vol. swelling in fuel 100*(V/ V0-1) (48h/50°C) [%] 75

1706 S 33,7 4,3 60

Vulcanizate Properties of Sulfur -  - and Peroxide  Cured HNBR ( Partially   )  Partially and Fully Hydrogenated  HNBR-Grade (Therban) 1706 S ACN-content [wt.%] 33,7 Residual double bond cont. [Mol.%]4,3 ML 1+4(100°C) [ME] 60 Compound Properties Compound Mooney [ML 1+4(100°C)]64 Mooney-Scorch (120°C) [min.] 12,5 Fmax [N] 56,4 Vulcanizate Properties Sulfur Core (Press 160°C/20`) Peroxide Cure (Press 180°C/15`) Shore A Härte (23°C) 72 Shore A Härte (70°C) 69 M 100 [MPa] 3,4 M 200 [MPa] 8,8 M 300 [MPa] 14,7 Tensile Strength [MPa] 27 Elongation [%] 510 Rebound [%] 38 Compression Set 70h/-10°C [%] 73 70h/23°C [%] 70h/100°C [%] 73 70h/150°C [%] Hot Air Ageing D/D0 (150°C/ 5 d) [%] 55 D/D0 (150°C/24 d) [%] Degree of Vol. Swelling in Fuel 100*(V/V0 -1) (48h/50°C) [%] 75

1706 S 33,7 4,3 60

1706 34,5 0,4 63

66 14 51,2

74 16 52

72 70 5,6 17,8 26 295 36

73 71 6,9 17,7 24 280 34

68 10 27

12 28

54

59

65

70

66 14 51,2 72 70 5,6 17,8 26 295 36 68 10 27 54 65

Performance of HNBR in Power Transmission Belts  Materials used for power transmission belts Leather

200

10.000

180

   %    0    5   =1.000

160

140

120

100 [°C]

HNBR / peroxide cured HNBR / sulfur cured

   b

   ε

SBR

CR

  r   o 100    f    h    /    t   g   o 10    l

CR

2,1

2,2

2,3

2,4

2,6 10 -3 (

2,5

-1

HNBR (Sulfur cured)

HNBR (Peroxide cured)

   h    t   w   o   r   g    k   c   a   r   c    f   o   e    t   a   r

1 -1 K ) T

1000

CR

HNBR

100

Tear-Analyzer-Test / Exp. Conditions

10

Frequency: Strain Amplitude: Attenuation mode: Rate of crack growth:

1 0,1

-20

0

20

40

Temperature [°C]

60

80

4 Hz 20% sinuoidal 1/c o (dc/dn) 100

Source: M. Mezger; D. Achten “Therban: The high performance elastomer in power transmission systems” 9. Tagung “Zahnriemengetriebe” am Institut für Feinwerktechnik und Elektronik-Design der TU Dresden

5.4. EVM: Profile of Properties and Applications  O O

C

O

CH3

O

O

C

C

CH3

CH3

O  

Positive:    

  



Ozone-, UV-, and weather resistance Maximum service temperature 175°C High filler loadability FRNC-applicability (Flame resistant non corrosive) Resistance to water/glycole Braod range of grades No necessity for post cure in oven

 

Application Araeas: 

   

Negative:  

  

VAc-content: 40-90 wt.% radical polymerization in solution Random monomer incorporation Low molar masses Significant degree of short chain branches



fair mechanical properties Low temperature flexibility (depending on VAccontent) Fair oil resistance Range of products limited to ML 1+4 = 20 - 35 Vulcanization only peroxides

 



 

Automotive- and engineering: seals and membrandes Hoses in high temperature environment FRNC-products: cables and floorings Sound protection FRNC Conveyor belts Hot Melt and pressure sensitive adhesives Protecting foils Blending component for HNBR, EPDM, CM, NBR) Rubber modification of thermoplasts (PVC, TPU, SAN, PC etc.) Oil additive Shoe soles

Source: H. Bartl, J. Peter, Über Äthylen/Vinylacetat-Copolymerisate und ihre Vernetzung; Kautschuk und Gummi, Jahrgang 14, 2 (1961) WT 23-32

 Production Routes Towards EVM and EVA Producer Process

10000

Exxon, BP, High pressure Escorene Mitsui ctc.

High pressure bulk process 750-3000 bar 120-300°C

1000

Du Pont USI

High pressure Elvax High pressure Vynathene

Lanxess Mitsui

Solution Solution

Solution process 100-500 bar 50-120°C Emulsion process 10-100 bar 30-70°C

   ]   r   a    b    [ 100   e   r   u   s   s   e   r   p

•

•

10

•

•

1

•

40

60

Vinylacetate content [wt.%]

Preferred mprocess for EVA (thermoplastic polymers with VAc-content <40 wt.%) Monomer conversion: < 20% Molar mases decrease with increasing VAc-content

Solution process:

EVM-Rubbers

20

Levapren

High pressure process:

•

0

Products

80

100

Preferred process for EVM-r rubbers (VAc-cont. 40-90%) Monomer conversion: 60- 70% Solvents: t-Butanol; Methanol

Emulsion Process: •

Preferred process for latices with high gel content (paints) Monomer conversion: ~ 100%

High Pressure Bulk Process: US 5089579 (Bayer AG), Prio.: 11. 12.1989; Erf.: H. Sutter, A. Kolwert, W. Obrecht Solution Process: US 4937303 (Bayer AG), Prio.: 0 1.05.1989; Erf.: B. A. Wolf, B. Will, W. Obrecht, R. Casper, W. Baaade, G. Sylvester, K-P. Meurer, H. Zimmermann EP 0632067 (Bayer AG), Prio.: 30.06.1993; Erf.: R. Steiger, E. Asch, W. Baade, W. Obrecht •

 EVM: Physical  Properties  Properties Thermoplast

Rubber 

100    ]    C80   n   °    [   o   )    i    t   g60    i    T   s   (   n   e 40   a   r   r   u    T   t 20   s   a   r   s   e 0   a   p    l    G  m   e-20    T -40

  n   o    i   s   u    F    f   ]   o   C    °    [   e   r   )   p   u    t   F    (   a   r   e   p   m   e    T

  n   o    i   s   ]   u  g    f    f   /    [   o   J    )   y   H   p   D    l   a   (    h    t   n    E

0

20

40 60 Vinyl acetate content [wt.%.]

80

100

0

20

40 60 Vinyl acetate content [wt.%]

80

100

100 80 60 40 20 0 -20 -40

 EVM: Maximum Service Tempeature 0 -10

O

O

CH3 - HAc

O O

CH3 O

CH3 O

   ] -20    %  . -30    t   w    [ -40   s   s -50   o    l    t -60    h   g -70    i   e   w -80

350 °C

-90 -100 200

Elastostab H 02

OCN

NCO

106

Stabaxol P 200 H3C O

nO

n n = ca. 4

O N H

N CN 135

400

500

600

Temperature [°C]

N C N

O

300

N O H

O nCH3

n n = ca. 4

The addition of acid scavengers such as carbodiimides and isocyanates does not improve hot air performance

   h100000   n    i    %    0    5   <   s 10000   e   m   o   c   e    b   n   o    i    t 1000   a   g   n   o    l   e    l    l    i    t   e 100   m    i    t 200

20000 h

1000 h

> 170°C 190

180

170

160

150

137°C 140

temperature in °C

130

120

110

 EVM: Dependence of Oil Swell  and  Limiting  and LOI (  Oxygen Index) on Vinyl Acetate Content Storage time in SAE-oil SAE 90 (3 d/125°C)

LOI according to ASTM-D 2863

80

60 Delta F/F0 x 100 [%]

60

Al2O3: 190 phr

Delta D/D0 x 100 [%]

   ]    %    [   s 40   e    i    t   r   e   p 20   o   r    P    f   o   e   g 0   n   a    h    C

50

Delta V/ V0 x 100 [%]

-20

-40 0

20

40

60

80

Al2O3:

   %    [    )    I    O    L    ( 40   x   e    d   n    I   n30   e   g   y   x    O   g20   n    i    t    i   m    i    L10

100

0 phr

0 0

20

Vinyl acetate content [wt.%]

40

60

80

100

Vinyl acetetate content [wt.%]

Source: E. Rohde; DKG-Bezirksgruppentagung; NRW in Bad Honnef; 07.-08. Mai 1992

 EVM: Dependence Properties on Vinyl Acetat Content EVM

100,0 phr

MgO

2,0 phr

Stearic acid

1,0 phr

Carbon black/N 550 Vulkanox DDA 1)

65,0 phr 1,0 phr

2)

7,5 phr

Plasticizer ODTM

7,5 phr

PE-Wax

2,0 phr

Aktiplast PP

2,0 phr

TAIC

1,5 phr

Peroxide (40%ig) 3)

6,0 phr

Vulkanization time:

10 min

Plasticizer DOS

Temperature:

180°C

no post vulcanization storage in hot air 1)

Styrenated Diphenyl amine (SDPA) Dioctylsebacate (DOS) 3) 1,3-Bis(tert.-butylperoxyisopropyl)benzene (Perkadox 14/40) 2)

Source: E. Rohde DKG-Bezirksgruppentagung NRW in Bad Honnef  07.-08. Mai 1992

Vinyl acetate content [wt.%]

40

45

50

60

70

80

Compound properties Mooney ML 1+4(100°C) t10/180°C [min] t90/180°C [min] FH-FL/180°C [N]

20 1,2 7,2 17

24 1,2 6,6 20

23 1,2 6,6 19

25 1,2 6,2 21

20 1,3 6,9 19

20 1,3 6,1 17

Vulcanised properties (ISO-Stab Nr. 2, 2mm) Shore A Härte (23°C) S 100 MPa] Elongation at break [%] Tenjsile Strength [MPa]

75 5,0 295 11,7

74 5,7 275 13,6

68 4,4 285 12,6

71 5,4 280 12,8

68 4,2 300 11,5

72 4,7 300 10,5

Compression Set 70h/100°C 70h/125°C 70h/150°C

23 25 41

20 23 38

20 25 41

22 26 40

21 24 46

27 31 51

Hot air ageing (14d/150°C) [%] ∆F/F0 x100 [%] ∆D/D0 x100 [%] ∆H/H0 x100

-3 -2 10

-12 -2 9

-10 2 11

-11 -2 12

10 -7 15

-8 -15 14

Storage in SAE Oil90 (3d/150°C) [%] ∆F/F0 x100 [%] ∆D/D0 x100 [%] ∆V/V0 x100

-26 -19 69

-12 -4 47

-8 -4 31

8 2 13

6 8 3

10 -12 -4

[%] [%] [%]

 EVM/HNBR- Blends EVM/HNBR

100,0 phr

Rhenogran P 50 1) var. Carbon black/N 550 50,0 phr Carnuba Wax

2,0 phr

MgO

10,0 phr

ZnO

2,0 phr

TAIC

1,75 phr

Peroxide (40%ig) 2)

7,0 phr

Vulcanization time:

15 min

Temperature:

177°C

Anealing:

16 h

Therban 1707 Levapren 500 Rhenogran P 50

100 -

75 25 1,5

50 50 3

25 75 4,5

100 6

Compounc properties Relative compound price ML 1+4(100°C) [ME] t2/177°C [min] t90/177°C [min]

100 123 1,5 11,7

80 99 1,6 11,0

60 58 1,5 10,2

40 40 1,6 10,2

20 32 1,6 9,5

Vulcanized properties Shore A Härte (23°C) S 100 [MPa] Elongation at break [%] Tensile Strength [MPa]

78 10,7 240 26

80 13,1 190 24

80 12,6 170 22,5

81 12,0 145 18,8

77 8,3 165 18,5

12 20 27

12 17 27

12 17 25,5

14 14 20

14 9 15

Hot air ageing(14d/150°C) F/F0 x100 [%] D/D0 x100 [%] H/H0 x100 [%]

-2,3 -37 +6

-3,8 -26 +5

-10 -29 +4

-7,5 -21 +3

-1,6 -12 +2

Storage in ASTM oil Nr. 3 (7d/150°C) [%] ∆F/F0 x100 [%] ∆D/D0 x100 [%] ∆V/V0 x100

-10 -4 +24

-17 -11 +34

-36 -29 +49

-50 -34 +67

-56 -45 +83

Compression Set 70h/23°C 70h/150°C 70h/175°C

1)

Carbodiimide 2 Vulcup 40 KE

Source: Test Report WR 26/83 (Mobay, Chem. Corp.)

[%] [%] [%]

 EVM: Influence of Post Cure on Physicals 15

O-Ring: Mechanical properties without post with post cure cure Tensile Strength [MPa] 10,4 11,8 [%] 285 230 εb M100 [MPa] 1,8 3,1 CS 72 h / 150°C [%] 63 31 CS 168 h / 150°C [%] 71 50

  e   u  r   r e  c   t  c  u  s   t   p  o  o s   t  h   t  p   i   u   w  o   t  h   w  i

   ] 10

  a    P    M    [   s   s   e   r 5    t    S

0 0

50

100

15 0

200

250

300

strain [%]

10 9 8

   ]   m    N    d    [   e   u   q   r   o    t

7 6 5

= 75 % of total cure

4

Sources:

3

cycle time for IM

2 1 0

0

20

40

60

80 100 120 140 160 180 200 220 240

time [sec ]

H. Meisenheimer, Kautschuk Gummi Kunststoffe, 52 (1999) 724 P. J- Pazur, L. Ferrari, H. Meisenheimer, ACS Rubber Div. 165th Spring Meeting, Grand Rapids, Michigan H. Magg, A. Welle, Nordic Rubber Conf. 2005, Köge, Denmark

 EVM:  Acrylate Reinforcing Technology “ (ART) Zinc diacrylate Saret 633 Sartomer 705 O H2C

CH

C

O

Zn

2+

Levapren grade Levapren TMQ N 762 ZnO ZMB-2 Ficon 153 1) Saret SR 633 2) Vul-CUP 40 KE

500 100

3)

500HV 100 1,0 35 10 1,0 20 6,5

500HV 100 1,0 35 10 1,0 20 6,5

9,9

26,8

77 72 13,5 80 6,6 43 62

77 73 20,8 175 4,2 10,5 46 61

1 -8 6

-5 -29 8

-13 -6 13,7

-22 -29 12,1

2

1) 1,2-BR

(liequid rubber) 2) Zn diacrylate 3) For further ompound ingredients see „Stuey on variation of vinyl acetate content“ Source: T. A. Brown, Polysar Rubber Corporation, Technical Report TR 552.92,17 vom 22.05.92

 „Acrylate-Reinforcing“ is used for  golf ball cores based on high

ART based “Golf-Ball-Core“-Patents EP 0496947, Prior.: 29.01.1991 (Bridgestone) US 6426387, Prior.: 04.08.2000 (Taylor Made Golf Co. EP 1227121, Prior.: 24.01.2001 (JSR) US 6525141, Prior.: 02.04.2001 (Bridgestone) US 6270428, Prior.: 07.08.2001 US 6517451, Prior.: 11.02.2003 (Titleist)

Compound properties Mooney ML 1+4(100°C)

[MU]

Vulcanized properties (ISO-Stab Nr. 2, 2mm) Shore A Härte (23°C) Shore A Härte (150°C) Tensile strength Elongation at break M 50 M100 Rebound/23°C Rebound/100°C

68 [MPa] 12,6 [%] 285 [MPa] [MPa] 4,4 [%] [%] -

Hot air ageing (14d/150°C) F/F0 x100 [%] D/D0 x100 [%] H/H0 x100 [%]

23

-10 2 11

Storage in SAE-oil 90 (3d/150°C) [%] ∆F/F0 x100 [%] ∆D/D0 x100 -8 [%] ∆V/V0 x100 -4 31

6. Thermoplastic Elastomers (TPE)  Principle of Physical Crosslinking, Phase Morphology and Property Profile Nomenclature and Range of Available Grades Selection of Commercially Available TPEs, Producers and Brand Names Market, Areas of Applications and Prices Phase Morphology of Rubber Modified Thermoplastics and Thermoset Resins Comparison of Technological Properties of Different Classes of Engineering Polymers  –  Dependence of Shear Modulus on Temperature  –  Dependence of Residual Elongation on Original Elongation  –  Comparison of Technological Properties of Chemically and Physically Crosslinked Rubbers (Data from Product Data Sheets) • TPE-O and TPE-V  –  PP-Performance and Price of EPDM/PP-Blends  –  Mechanical Properties • • • • • •

• Advanced technologies for the production of PP-based TPEs • TPEs from the viewpoint of a producer of technical rubbber goods

TPE: Phase Morphology and Property Profile  A coherent soft or rubber phase (coherent matrix) is representative for most TPEs The hard phase which contains the physical cross-links is dispersed within the soft phase. The hard phase is only physically and never chemically crosslinked The soft phase can either be uncrosslinked or crosslinked Soft Segment Hard Segment Scheme of the Phase Morphology of A-B-A, (A-B) n and (A-B)xMultiblock Copolymers

Positve:

• Good vulcanizate properties at low / moderate temperatures • No compounding and vulcanization know-how necessary • Short cycle times no time consuming vulcanization • Recycling of waste (due to thermo labile/reversible crosslinks)

Examples for physical crosslinks • • • •

Hydrogen bonds /Crystallization Dipol/Dipol - Interaction Glassy Hardening (vitrification) Ionomers Type of bond covalent physical

Bond energy [kJ / Mol] 260 - 350 10 - 20

Negative: • High permanent set after (tension set, compression set) • Poor mechanical properties at elevated temperatures (tensile strength, compression set) • Deterioratioon of mechanical properties in appropriate solvents • High heat-build-up in dynamic applications • Limited range of grades (particularly no soft grades available) • Anisotropic properties of injection moulded articles (particularly for TPEs with uncrosslinked rubber phase)

Nomenclature and Range of Available TPEs  Examples TPE-O

mechanical and reactor-blends (unvulcanized)

EPM / PP EPDM / PP

Olefin TPE-V

EPDM / PP NBR/ PP

PVC based blends

NBR / PVC EVM / PVC ACM / PVC

Thermoplastic Polyolefins

(dynamically vulcanized)

Polyblends 1

(without dynamic vulcanization)

High Performance TPE-V (without polyolefines (dynamically vulcanized)

Thermoplastic Elastomers

HNBR / PA HNBR / PBT NBR / PA EVM / PA EVM / PBT

TPE-S

SBC (SBS, SIS, SEBS, SIBS)

TPE-U

Polyester-Urethanes, Polyether-Urethanes

TPE-E

COPE based on aromatic Polyesters (Terephthalates) PBT´/ PTHF; PET / PTHF

Styrenic Block-Copolymers

Polyurethane Block Copolymers

Multi-BlockCopolymers 2

Copolyester Block Copolymers

TPE-A

Polyamide Block Copolymers

PEBA based on PA 6 and PA 12

1 Consists of an elastomer finely dispersed in a thermoplastic matrix 2 Rubber and thermoplastic segments are chemically bonded by block- or graft copolymerization

Sources: SRI Elastomers Overview 2008; Stratley Consultants

Selection of Commercially Available TPEs , Producers  and Brand Names  Type of TPE

Crosslinking Principle

Producer

Brand Name

TPE-O (reactor blends)

Crystallization

TPE-V

Crystallization

UCC Bassell Exxon AES (Advanced Elastomer Systems) AES (Advanced Elastomer Systems)

Flexomer®  Spherilene®  Exxtral®  Santoprene®  Geolast® 

PVC-based blends

Dipol/Dipol

Denki KK

Denka LS® 

High performance TPE-V TPE-S SBS, SIS, SEBS

Zeon Glassy hardening Shell (vitrification) BASF Firestone, Polimeri Dow Kaneka Boston Scientific Innovia Hydrogen bonds / Bayer Crystallization BASF Goodrich Crystallization DuPont Toyobo Hydrogen bonds / Atochem Crystallization Dow Ionomer Du Pont

SIBS TPE-U TPE-E TPE-A

? Kraton®  Styrolux®  Sibstar®  Taxus®  SIBS®  Desmopan/Texin®  Elastollan®  Estane®  Hytrel®  Pelprene®  Pebax®  Estamid®  Surlyne® 

TPE: Market, Application Areas and Range of Prices  WO-TPE-Market: 1,5 Mio t SBC

TPO-V

Areas of Application

TPU COPE PEBA Rest

IRP 18%

Hoses 5%

Shoe 15%

Cables 3% Medical Appl. 3%

TPOBlends

Asphalt Mod. 12%

Adhesives 12%

Automotive 32%

W.-Europe:: 576a t (2001) TPE Type SBC's TPO's TPV's TPU's COPE's COPA's Sonstige Sum Source:

2.000 2.005 Growth [%] 195 135 36 62 20 7,5

226 172 59 79 30 10

3 5 10,5 5 8 5

455,5

576

4,5

Price [€/kg]

PP/EPM-Reactor Blends PP/EPM-TPE-V SBC SBS SIS SEBS

0,90-1,20 2,00-2,50 1,00-3,30 1,30-1,50 1,50-1,70 2,60-3,30

TPE-U (TPU) TPE-E (COPE) TPE-A (PEBA)

3,00-4,00 3,50-4,40 3,60-7,00

European Rubber Journal 184,no.1 (January 2002)

Schematic Presentation of the Dependence of the  Shear Modulus on Temperature  104

   ]   a    P    M    [   s   u    l   u    d   o    M   r   a   e    h    S

103

Tempeature of Use

Temperature of Processability

Temperature

Softening Temperature of Thermoplast Phase

102 101 100 10-1 Tg of Rubber Phase

Dependence of Modulus on Temperature : Target and Reality  104    ] 103   a    P    M    [   s 102   u    l   u    d   o 101    M   r   a   e    h 100    S

Target Reality

10-1 -100

- 50

0 50 100 Temperature [°C]

150

200

Schematic Presentation of the Dependence of the Shear  Modulus on Temperature for Different Engineering Polymers  104 3

   ] 10   a    P    M    [ 2   s 10   u    l   u    d   o 1    M 10   r   a   e    h    S 100

10-1 - 100

5

4

3

2

1

6

7

8 - 50

0

50 Temperature

100

150

200

Dependence of Shear Modulus on Temperature for Different Engineering Polymers 

104 1. Thermoplastic Polymer (Polycarbonate, PP.PA)

103

   ]   a    P    M    [ 2   s 10   u    l   u    d   o 1    M 10   r   a   e    h    S 100

2. Thermoplastic (Polystyrene, PMMA) 5

4

3

2

1

3. Rubber Modified Thermoplastic

6

4. Elastomer (crosslinked) 5. TPE

7

6. TPE 7. Elastomer (crosslinked)

10-1 - 100

8. Unvulcanized Rubber

8 - 50

0

50

100

150

200

Temperature

Schematic Presentation of Stress/Strain Diagrams of Block Copoymers  elongation A-B-A, (A-B)n und (A-B)xBlock Copoymers

   ]   a    P    M    [   s   s   e   r    t   s

Residual elongation

A-B Block Copolymers

strain [%]

Dependence of Residual Elongation on Original Elongation for Different Engineering Polymers  εresidual = εoriginal

   ] 300    %    [    )    l   a   u    d    i   s   e    R

   ε 200    (   n   o    i    t   a   g   n   o 100    l   e    l   a   u    d    i   s   e   r

0

TPE-O (EPDM / PP: 60/40)

ASTM D 1566 - 98 „Definition of Rubber“

0

100

TPE-V (EPDM / PP: 78/22)

SBS with 27 wt.% styrene NR/BR-tyre tread (with filler) vulcanized gum stock (unfilled NR)

200

original elongation (

300

εoriginal ) [%]

Compression - Set 

h1

ho

CS =

ho

ho- h1 h2 h1

ho- h2

h2

ho- h2 ho- h1

x 100

[%]

In compression set (CS) measurements h o , h 1, compression, exposition time, and exposition temperature are well defined  (DIN, ASTM). Most commonly, the  deformation is 25%. In order to achieve the  same deformation „h o -h 1“ the pressure has to be adjusted to the degree of x-linking 

Comparison of Technological Properties of Chemically and Physically Crosslinked Rubbers (Data from Product Data Sheets   )  S BC Classical Elastomers

S BS

S IS

S hore A

10 to 80

71

52

S hore D

-

Properties

T P E -U

75

93

44

42

25

40

63

32

54

79

36

51

15,4

10 to 35

32

20

34

45

40

E longa tion a t bre a k [

300 to 800

880

1200

500

450

380

60

60

5 to 30 5 to 40 5 to 40

CS (70h/ 150°C)

30 (H NBR , FKM)

TPE-E

92

T e nsile S tre ngth [MP

CS (22h/ 70°C) CS (24h/ 70°C) CS (22h/ 100°C)

TPE-A

S EBS E ste r E the r

715 485 380

62

21

5

TPO me ch. TPV TPV E P DM /P P E PD M /P P E P DM /P P ble nd (pa rtia lly (hig hly x- link e d ) x- link e d ) 78

72

75

47

12

5,5

8,5

880

660

650

350

490

75

60

38

90

53 88

44

Technologische Eigenschaften von TPEs  und von Hauptvalenzelastomeren  klassische Elastomere

200    ]    C    °    [   r   u    t   a   r 100   e   p   m   e    t   s    h   c   u 0   a   r    b   e    G

PEBA TPO TPU COPE SBC

-100 0

50 Shore A Härte

80

100

30

40

50

60 70 Shore D Härte

80

P  PP - Performance Performance and Price of EPDM/P  EPDM/PP - Blends  Blends  7

180

TPE-V (EPDM / PP-blend, highly crosslinked)

160

6

   ]   s    t    i 5   n   u   y   r   a   r    t    i 4    b   r   a    [   e   c 3   n   a   m   r   o    f   r 2   e    P

140

   ]    C    °    [ 120   e   r   u    t   a   r 100   e   p   m   e 80    t   g   n    i    t    l 60   e    M

PP-Properties: PP-Properties: • Low Price

40

• Low Price • High Softening Temperaure • High Softening Temperaure • Good Ageing Resistance • Good Ageing Resistance (Residual Catalyst Content)

20

TPE/SEBSBlends

TPE-V (EPDM/PP partially cross-linked)

TPE-O (mechanical blends)

TPE-O

1

(ReactorBlends)

(Residual Catalyst Content)

0

0 20

40

60

80

100

0

0,5

1

1,5

Price [$/kg]

Isotacticity [%] Source: T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 „New Polymers from New Catalysts“

Source: Robert Eller Associates, Inc. 1996

TPE -  -O   and TPE -  -V:  V: Basic Properties  Properties

TPE-O

TPE-V

(Mechanical PP/EPDM Blend)

(PP/EPDM-Blend with partially crosslinked EPDM-phase)

TPE-V (PP/EPDM-Blend with highly crosslinked EPDM-Phase)

Shore A-Hardness

78

72

75

Tensile Strength [MPa]

12

5,5

20

Elongation at break [%]

650

350

490

75

60

38

soluble

90

50

Compression Set (22 h /70°C) [%] Volume Swell in ASTMOil Nr. 3 [Vol%]

Uncrosslinked rubber phase

Crosslinked rubber phase

 i o n  t  c  e  D i r  F l o w  o f

 i o n  t  c  e  D i r  F l o w  o f

2

TPE -  -O   and TPE -  -V:  V: Mechanical Properties  Properties

no. of recycles 1

2

3

5

M100 [psi]

650

630

620

600

Tensile Strength [psi]

1530

1520

1500

1590

Elongation at break [%]

495

500

505

535

20 Shore D Hardness: 50 15

35

   ]   a    P 30    M    [ 25    h    t   g 20   n   e   r 15    t    S   e 10    l    i   s   n 5   e    T 0

1,0-1,5

Particle diameter [µm] 5,4 17 72

Shore A Hardness: 87

   ]   a    P 10    M    [   s   s   e   r 5    t    S

39

Shore A Hardness: 64

0

0 0

400 200 Elongation at break [%]

100

Filter

Filter

ventilator

PE*

PP**

UCC BASF BP Hoechst Exxon Amoco Montell

Montell Fina Phillips Solvay UCC BASF Amoco/Chisso Sumitomo

* Ind Eng. Res. 33 (1994) 449-479 ** Chem. Systems (April 1992) "Polypropylene"

Cooler

Product outlet

Supported catalyst

Cooler

Ethylene

500

Gas Phase Technology

Sources:

Propylene

400

Elongation [%]

600

TPE -  -O: O   : PP/EPM -  -Reactor  R   eactor -  -Blends   Blends 

ventilator

300

200

Removal of residual monomer

purification purification

Temperature: Pressure: Residence time per reactor:

< 90 °C (40°C-60°C) 9-15 bar 0,5 - 1 h

Source: T. W. Klimek (Quantum Chemical Corp.) ANTEC `91, 1382-1384

packaging

Properties of PP/EPM -  - Reactor -  -Blends   Blends  1000 Catalyst Fragmentation during Polymerization

900 800

Catalyst System A

   ]   a    P    M    [ 700   s   u    l   u 600    d   o    M   - 500    E

Catalyst System B

400 300 20

30

40

50

60

Rubber Content [wt.%] Source: H. Schwager (BASF); Kunststoffe 82, 499 (1992) T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 „New Polymers from New Catalysts“

Preparation of TPE -  -Vs   Vs by Reactive Processing  Blending  Definitions: 1)

“Reactive Processing” stands for a chemical reaction in the course of which polymers are modified without the use of solvents.

2)

“Dynamic Blending” stands for the solvent free blending process during which a chemical reaction occurs.

3)

“Dynamic Vulcanization” is used for vulcanization reactions (without solvent) with simultaneous shearing.

4)

Every vulcanization method can be performed dynamically

5)

Resin cure was the first vulcanization method applied for the production of EPDM/PP based TPE-V

Preparation of a TPE -  -V   by the Dynamic Vulcaniztion  of a EPDM/PP blend with Phenol Resin  1.

Preparation of a PP/EPDM-Block Copolymer in order to partially compatibilize  PP and EPDM 

1a) Reaction of PP with Dimethylol Phenol Resin in order to “activate” PP  OH

PP

HOCH 2

+

CH 2 OH

1) Melting PP at 185°- 190°C 2) Addition of dimethylol resin at 185°-190°C (5 Min.) 3) Addition of the catatalyst SnCl2 x 2H20 (2 Min.)

OH

PP

CH 2

CH 2 OH

Preparation of a TPE -  -V   by the Dynamic Vulcaniztion of a EPDM/PP blend with Phenol Resin  1b) Preparation of block copolymer by the reaction of “activated PP” with EPDM  OH

PP

CH 2

CH 2 OH

+

EPDM

1) Addition of EPDM and additional Phenol Resin at 185°- 190°C (5 Min.) 2) Addition of more SnCl2 x 2H20 at 185°- 190°C (5 Min.)

OH

PP

CH 2

CH 2

EPDM

Preparation of a TPE -  -V   by the Dynamic Vulcaniztion of a EPDM/PP blend with Phenol Resin  2) Addition of PP und EPDM with subsequent vulcanization of the EPDM-Phase  OH

PP

CH 2

EPDM

CH 2

1) Addition of EPDM and PP at 185°- 190°C (5 Min.) 2) Addition of of more SnCl2 x 2H20 at 185°- 190°C (5 Min.)

PP -

EPDM-

OH

PP

CH 2

CH 2

EPDM Phase

Phase

In reality, the series of reactions from 1a), 1b) to 2) do not occur in a sequence of reactions, which are well separated but rather in a concurrent fashion

Compatibilising Effect of Dimethylolphenol Resins in Dynamic Vulcanization of PP/NBR -  -Blends   Blends  185-190°C 5 min. 2 min.

0 0 0

185-190°C Polypropylene 5 min. NBR + Aminino terminated NBR Dimethylolphenol resin + 5 min. SnCl2 . 2 H2O Tensile Strength M100 E-Modulus Elongation at break Permanent elongation

Polypropylene Dimethylolphenol resin SnCl2 . 2 H2O

[MPa] [MPa] [MPa] [%] [%]

50 2 0,4

50 2 0,4

50 2 0,4

50 50 0 0 0

0 50 0 0 0

0 50 0 1,67 0

0 45 5 5 0,5

7,2 0 149 36 0

10,1 0 170 66

10,1 0 157 170

15,3 10,2 107 390 54

Compatibilising Effect of Dimethylolphenol Resins in Dynamic Vulcanization of PP/NBR -  -Blends   Blends  185-190°C Polypropylene 5 min Dimethylolphenol resin 2 min SnCl2 . 2 H2O

25 1 0,2

37,5 1,5 0,3

50 2 0,4

62,5 2,5 0,5

75 3 0,6

5 min Polypropylene 5 min NBR + Aminino terminated NBR Dimethylolphenol resin + SnCl2 . 2 H2O 5 min

67,5 7,5 9,38 1,13 1,13

56,25 6,25 7,81 0,78 0,94

45 5 6,25 0,5 0,75

33,75 3,75 4,69 0,28 0,56

22,5 2,5 3,13 0,13 0,38

Tensile Strength M100 E-Modulus Elongation at break Permanent elongation

17,0 15,8 33 330 20

19,6 15,7 92 400 33

23,0 15,2 221 500 50

22,7 16,2 320 490 63

21,5 17,1 456 480 70

[MPa] [MPa] [MPa] [%] [%]

Reactive Blending von EPDM/SAN: Results  SAN

EPDM

 Reactive Processing  2 wt.% PF-Harz/0,2 wt.% Catalyst/130°C  (without fillers/without oils)  EPDM-grade: EP T 2370 (Lanxess)

   k 1000   a   e   r    b    t 100   a   ]   n   %   o   [    i    t 10   a   g   n   o    l 1   e 40    ]   a    P    M 30    [    h    t   g   n 20   e   r    t    S   e 10    l    i   s   n   e    T 0

0

10

20

30

40

50

60

70

80

90

100

EPDM-content [wt.%]

Sources: • M. Vierle: MSc Thesis TU Munic December 2001

• DE 10127402, Bayer AG, Prior.: 06.06.2001, Inv.: M. Vi erle, N. Steinhauser, O. Nuyken, W. Obrecht • M. Vierle, N. Steinhauser, O. Nuyken, W. Obrecht, Macromol. Mater. Eng. 2003, 288, 209-218„Blend Preparation by Reactive Processing

Advanced technologies for the production of PP -  -  based TPEs  608

R

ataktisches Polymer

R2 Zr

622

595

R1

R

R

Isotaktisches Polymer

R2 Zr

R1 R

Preparation of PP-Blockcopolymers by the use of the „Waymouth-Catalyst“ The length of building blocks is determined by the ratio of propagation rates versus Rotation rate Source: R. Waymouth, J. Coates, A-L. Mogstad, K. Stein, D. Fischer, S. Borkowsky Stepol `94; Milano June 6-10, 1994 "Stereospecific Polymerization and Copolymerization of Functionalized Olefins"

 BP/Amoco started   PP-- based  multi pilot-- plant scale  BP/Amoco started  to manufacture  to manufacture PP  multi- block copolymers  block copolymers in the in the pilot  plant scale in California (   Menlo Park)  Baxter Healthcare Corp., Round Lake, IL cooperates in the performance of tests towards the  replacement of soft PVC in medical  devices  devices  A. Khare ; S. Y. Ding; M. T. K. Ling; L. Wood; Modern  Plastics , September 1999; 94- 99  „ Heat meet tough  tough medical   medical  demands“   catalysts  Heat- resistant ,  , flexible olefins flexible olefins meet  demands“ -SingleSingle-Site metallocene Site metallocene catalysts  yield  autoclavable  autoclavable , high- clarity elastomers with cost/performance benefits of flexible PVC.

Advanced technologies for the production of PP -  -  based TPEs 

Cl Cl Et Et

Cl B P

Zr

Cl Cl

Cl

Temperature

B Zr

Cl Cl P

Et Et

Polymers with high tacticity

atactic polymers

PP-based multi-block copolymer Preparation of PP -  -based   based multiblock copolymers by the  use of Donor/Acceptor Metallocenes ( Ostoja   )  Ostoja Starzewski 

PP -  -Based  B   ased TPE  4

10

   ]   a    P 3    M    [ 10    )    *    )    G   a    (    P 2 10   s    M    (   u    l    l  u    d   u   o    d   m 1   o    b 10   u   m    h   c   x    S   e    l   p 100   m   o    K

Elastomeric PP

G'

G''

-120

-80

-40

0

40

-120

-80

-40

0

40

0

10

  n   a 10-1

-2

10

-160

 Temperatur[° (°C) Temperature C]

Sample from Prof. from Prof. Aladyshev 

PP -  -Based   Based TPE  6 Elast.PP

   ]    ]    2   m 4   m   m    /   m    N    /    [    N    [

   2

   σ    σ σ

  g   s   n   s   u   e   n   r   n    t   a   s   p    S

2

Probenform: S1-Stab Anlieferzustand: Platte Meßdatum: 05.06.02 Dateiname: S14308sd (Graph 1)

0 0

200

400

Dehnung [%] strain (εε) [%]

Sample from Prof. from Prof. Aladyshev 

600

800

PP -  -Based   Based TPE  4

10

   ]   a    P    ] 3    M   a10    [   P    )    M    *    [    l    G   u 2    (   d   o10   s   m   u    l   b   u   u    h   c 1    d    S10   o   r   e   m   x   e    l   x   p 0   e 10    l  m   o   p    k   m   o -1    K10

G' G'

0

10

G" HAIFA 1 G" HAIFA 2

-120

-80

-40

0

40

80

-120

-80

-40

0

40

80

-1

10

   )    δ    (δ   n   a    t

-2

10

-3

10

-160

Temperatur [°C]

120

Temperature [°C]

Sample from Prof. from Prof. Eisen/Haifa 

PP -  -Based  B   ased TPE  6

HAIFA-1 HAIFA-2

   ] 4    ]   m    2   m   m    /   m    N    /    [    N    [

   2

   σ    σ σ

  g   s   n   s   e   u   r   n    t   n   s   a   p    S

2

0 0

100

200

Sample from Prof. from Prof. Eisen/Haifa 

300

400

500

Dehnung [%] strain εεε [%]

600

700

800

900

TPEs from the Viewpoint of a Producer  of Technical  Rubber Goods  • Reduction of Manufacturing Costs   –  Reduction in number of raw materials and associated costs for logistics (ordering, transportation and storage,)   –  Reduction/elimination of compounding costs including energy savings   –  Significant reduction of cycle time and increase of output (seconds instead of minutes)   –  Cost reduction by recycling of waste (no costs for incineration and land fill) 

• New Technology for Rubber Processors   –  Installation of equipment for the processing of thermoplastic materials   –  Know-how in thermoplastics and their processing not available   –  Know-how for the compounding and processing of rubbers becomes abundant 

• TPE- Range of Products and Proeprties   –  Limited availability of soft grades with Shore A Hardness < 50   –  Open questions on the production of composites   –  High hysteresis which results in p high permanent set (after elongation and compression)   –  Losses on dynamic stress bei dynamischer Beanspruchung   –  Irreversible damage of articles if service temperature is increased above threshold  temperature 

7. Test Questions 

Please do not forget to write your name  on each page of the questionnaire  Fami Family ly Name Name Give Given n Name ame 1

Which Abbreviations Are Used for the Following  Rubbers?  Nr.

Rubber

Abbreviation

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Polybutadiene Polychloroprene Chlorinated Polyethylene Chlorosulfonated Chlorosulfonated Polyethylene Ethene/Propene/Diene-Terpolymers Ethene/Propene-Copolymers Epoxydized Epoxydized Natural Natural rubber rubber Fluororubber Acrylic Acrylic Rubber Rubber Synthetic Synthetic Polyisopr Polyisoprene ene Isobutene/Isoprene-Copolymers Styrene/Butadiene-Copolymers Natural Natural Rubber Rubber Silicon Silicon Rubber Rubber with with Viny Groups Groups Butadiene/Acrylonitrile-Copolymers Brominated Isobuylen/Isoprene-Copolymers Isobuylen/Isoprene-Copolymers Vinylmethylsilicon Vinylmethylsilicon Rubber, which also contains fluorine Polyphosp Polyphosphazen hazenee modified modified with perfluorin perfluorinated ated alcohols alcohols Standardiz Standardized ed NR from from Vietnam Vietnam Smoked Smoked Sheets Sheets based based on NR

Family Family Name Name Given Given Name Name

2

Please Assign the following Rubbers to the  Correct Position in the Matrix:  ACM, BIIR, BR, CM, CSM, EVM, FKM, HNBR, IIR, SBR Process Process Featur Features es

Chemical Features

Emulsio lsion n Solut lution ion

Disp ispersion Mass or (slurry) Bulk

GasPhase

Radical Polymerization Ziegler/NattaPolymerization anionic Polymerization Cationic Polymerization Polyaddition und Polycondensation Polymermodification Family Family Name Name 3

Given Given Name Name

Which of the Curves Matches the Performance of the  Materials Mentioned Below ? 300

1

   ]    %    [   n   o    i    t 200   a   g   n   o    l    E    l 100   a   u    d    i   s   e    R

2 3 4 5 6

0

0

100

200

300

elongation elongation [%]

Nr.: Questions 1 2 3 4 5 6 7 8 9 10

Answers

Therm Thermop opllast astic Pol Polymer ymer ? Unvulca nvulcani nized zed HN HNBR at 20° 20°C C? Unvulca nvulcani nized zed HN HNBR at 120° 120°C? Unvulca Unvulcanize nized d BR with with Mn = 10 kg/mol kg/mol at 50° 50°C ? Unvulca Unvulcanize nized d BR with with Mn = 500 kg/mo kg/moll at 20°C? 20°C? SBS at 20°C? SBS at 120°C T PU PU at 20°C NR (un (unfi fille lled d and and vulcan vulcanized ized)) at at 60°C 60°C NR (f (fil illed led and and vulcani vulcanized) zed) at 60° 60°C Family Family Name Name Given Given Name Name

4

Natural Rubber  Please Mark „RIGHT “  “ or „WRONG “  “ 

Nr.: Frage 1 2 3 4 5 6 7 8 9 10

Right W rong

Unvulc nvulcani anized zed NR NR does does not not cryst crystal alllize Today, Today, Malays Malaysiia is is NR NR-Produc Producer er No. No. 1 For NR NR plant plantat atio ions ns Chi China na is is idea ideall. For NR NR pl plant antat atio ions ns Bras Brasil il is ideal ideal.. A smal smalllhol holder der earns earns ~ 100 10000 00 €/ €/a SMR 20 is is a NR NR-grad -gradee with with high high puri puritty SMR CV vulcan vulcaniizes fast faster er than than SMR 10 NR has has tto o be mast mastiicat cated b bef efor oree use use IR has to be mas mastticat cated b bef efor oree use use For the masticati mastication on of NR, NR, m masti asticati cation on aids have to be be used

Fami Family ly Name Name Given Given Name Name 5

Natural Rubber  Please Mark „RIGHT “  “ or „WRONG “  “  Nr.: Frage 1 2 3 4 5 6 7 8 9 10

Right W rong

A tyre tyre tread tread base based d on NR NR perf perform ormss well well on a wet wet road road A tyre tread tread based based on NR NR exhibts exhibts a low rolling rolling resis resistanc tancee The vulcaniza vulcanizatei teion on of NR NR wit with h peroxides peroxides yields yields good dynamic dynamic properties properties NR has has a lower ower Tg tha than n EN ENR NR can be vulcani vulcanized zed with with mult multif ifunct unctiona ionall isocya isocyantes ntes CV grade gradess can be be vulcan vulcaniz ized ed with with dii diisoc socyan yante tess NR can be vulcani vulcanized zed with with phenol phenol/f /formal ormaldehyde dehyde resins resins NR based compounds compounds have have a higher higher tack tack than than SBRSBR-based based compounds compounds NR crys crysta tall lliz izes es at at 35° 35°C NR crystallizes crystallizes faster faster at -50°C than at -20°C -20°C

Fami Family ly Name Name Given Given Name Name 6

Synthetic Polyisoprene  Please Mark „RIGHT “  “ or „WRONG “  “  Nr.: Question 1 2 3 4 5 6 7 8 9 10

RIGHT W RONG

The mechanica mechanicall propert properties ies of IR do depend depend on the 1,4-c 1,4-cisis-cont content ent Li-based Li-based cata catalyst lystss produce produce IR with with a high high 1,4-ci 1,4-cis-c s-cont ontent ent Nd-b Nd-based ased catal catalysts ysts produc producee BR wit with h a high 1,4-c 1,4-cisis-cont content ent Ti-based Ti-based cata catalys lysts ts produc producee IR with with the the highest highest 1,4-ci 1,4-cis-c s-cont ontent ent Tg of IR does does not depend depend on 1,4 1,4-c -cis is conte content nt IR has to me masti masticat cated ed b bef efore ore use IR can be be crossl crosslin inked ked wit with h diis diisocy ocyant antes es IR with with a high high 3,4-c 3,4-cont ontent ent is is good for for tyres tyres with with a high high wt grip grip IR with with a high high cis-1,4 cis-1,4-co -cont ntent ent provi provides des tyres tyres with with good wet grip grip Poly-1,4Poly-1,4-transtrans-Isoprene Isoprene has a lower Tg than Poly-1,4Poly-1,4-ciscis-Isoprene Isoprene

Fami Family ly Name Name Given Given Name Name 7

Emulsion Rubbers  Please Mark „RIGHT “  “ or „WRONG “  “  Nr.: Question

Right Wrong

1

The term "emulsion" "emulsion" is used for for a dispersio dispersion n of polymer polymer particles particles in water water

2 3

The term "latex" "latex" is used for for a dispers dispersion ion of rubber parti particles cles in water water Polymer Polymer dispersi dispersions ons are obtai obtained ned by slurry (precipit (precipitati ation) on) polymeriz polymerizati ation on

4

Latic Lat ices es are are obtai obtained ned by by emul emulsi sion on poym poymeri erizat zatio ion n

5

Latic Lat ices es with with a sol solid idss content content > 50 wt. wt. % can not not be be made made

6

The addition addition of emulsi emulsifi fier er increases increases the the stabil stabilit ityy of latices latices

7

The addition addition of emulsi emulsifi fier er increases increases the the stabil stabilit ityy of emulsion emulsionss

8

At freezing freezing temperat temperatures ures latex latex stabil stabilit ityy is higher higher than than at 23°C

9

At elevated elevated temperat temperatures ures (>100° (>100°C) C) latex latex stabili stability ty is higher higher than at 23°C 23°C

10 The addition addition of electrol electrolytes ytes increases increases latex latex stabil stabilit ityy Family Family Name Name Give Given n Name Name

8

Pollution of Water and Air:  Please Mark „RIGHT “  “ or „WRONG “  “  Nr.

Question

Right Wrong

1

COD = 0

2

BOD = 0

3

BOD = COD

4

COD < BOD

5

BOD < COD

6

There There are no biodeg biodegrad radabl ablee emulsif emulsifier ierss

7

Emulsio Emulsion n rubbe rubbers rs yield yield consid considera erable ble amount amountss of wate waterr water water

8

Dry Dry fini finish shin ing g of soluti solution on rubb rubber erss does does not not caus causee wate waterr pollu polluti tion on

9

Rubb Rubber er recov recover ery y from from a soluti solution on by steam steam stri stripp ppin ing g caus causes es wast wastee wate waterr

10

Emulsion Emulsion rubbers rubbers cause air pollution pollution

Fami Family ly Name Name Given Given Name Name

9

Crystallization of Rubbers  Please Mark „RIGHT “  “ or „WRONG “  “  Nr .: 1 2 3 4 5 6 7 8 9

Fr a ge Addit Additives ives can increas increas the the rate rate of crystall crystallizat ization ion Addit Additives ives can reduce reduce the the rate of crystal crystalli lizati zation on SBR is a cryst crystal alli lizin zing g rubber rubber NBR is a cry cryst stal alli lizin zing g rubber rubber NR is a cryst crystall alliz izin ing g rubber rubber Rubber Rubber compound compounds s crystal crystalli lize ze slower slower than raw rubbers rubbers Vulcanizat Vulcanizate e crystall crystallize ize faste fasterr then the the respective respective rubber rubber compounds compounds Strain Strain induced induced crystall crystallizat ization ion is a wanted wanted property property Low temperat temperature ure performance performance of vulcanizat vulcanizates es is improved improved by spontan spontaneous eous crystallization 10 The compression compression set performance performance of vulcanizat vulcanizates es at low temperat temperatures ures is is improved by spontaneous crys tallization tallization

Right Wr ong

Family Family Name Name Give Given n Name Name

10

Crystallization of Rubbers  Please Mark „RIGHT “  “ or „WRONG “  “  Nr.: Question

Right W rong

1 2 3

SBR exhibit exhibitss spont spontaneo aneous us cryst crystal alli lizat zatio ion n NBR is a crys crysttalli allizi zing ng rubbe rubberr CR is a cryst crystal alli lizi zing ng rubbe rubberr The rate of CR crystall cry stallizati ization on depends on polymerization temperature 4 NR is a cryst crystal alli lizi zing ng rubber rubber 5 Spont Spontane aneous ous cryst crystal alli lizat zatio ion n is a want wanted ed propert propertyy 6 Strain Strain induced induced crystall crystallizat ization ion provides provides high high abrasion abrasion resistanc resistancee 7 The rcrysta rcrystall lliz izat atio ion n rate rate of CR depends depends on on tempera temperatu ture re The crystallization crystallization rate of rubbers shows a temperature maximum 8 The crystall crystallizat ization ion rate of rubbers shows shows a temperat temperature ure mini minimum mum The rate of crystall cr ystallite ite nucleation nucleation increases with with increasing temperature 9 The rate of crstalli crstallite te growth growth decreases decreases wit with h increasi increasing ng temperat temperature ure 10 The rate of crystall crystallizat ization ion of of vulcani vulcanizates zates can can be monit monitored ored by Shore A measurements

Family Family Name Name Given Given Name Name

11

NBR  Please Mark „RIGHT “  “ or „WRONG “  “ 

Nr.: Frage 1 2 3 4 5 6 7 8 9 10

Right W rong

NBR whic which h is polymer polymerize ized d under azeot azeotropi ropicc conditi conditions ons has 2 Tgs NBR whic which h is polymer polymerize ized d under azeot azeotropi ropicc conditi conditions ons has 1 Tg A batch batch polymeri polymerizati zation on with with incremental incremental monomer monomer addition addition can result result in 2 Tgs Low monomer monomer conversi conversions ons result result in in NBR NBR with with chemical chemical heterogenit heterogenityy High High amounts amounts of emulsifi emulsifier er improve improve chemical chemical homogenity homogenity High igh amounts amounts of modifi modifier er improve improve chemi chemical cal homog homogeni enity ty Rebound Rebound of NBR NBR increases increases with with the the content content of acrylonitri acrylonitrile le The degree of oil swelling swelling increases increases with with acrylonit acrylonitrile rile content content Shore A hardness of of NBR NBR vulcanizates vulcanizates dempend dempend on on acrylonit acrylonitrile rile content content The compression set of NBR NBR vulcani vulcaniaztes aztes depend depend on acrylonitril acrylonitrilee content

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12

NBR  Please Mark „RIGHT “  “ or „WRONG “  “  Nr.: Frage

Right Wrong

1 2

The properties of NBR depend on the emulsifier used for polymerization The properties of NBR depend on the electrolytes used for latex coagulation 3 The tendency to gelling increases with increasing polymerization temperature 4 The tendency to gelling decreases with increasing polymerization temperature 5 Molar masses increase with increasing monomer conversion 6 Molar masses do not depend on monomer conversion 7 Molar masses do not depend on modifier level 8 Molar masses decrease with increasing amounts of modifier 9 Molar masses increase with increasing amounts of modifier 10 The properties of NBR depend on the modifier used

Family Name 13

Given Name

NBR  In the literature  you find find the following  Tgs for  for polybutadiene  polybutadiene (BR) (BR) and the literature you  the following Tgs  polyacrylonitrile (PAN: 

BR (Li-catalysis) BR (Ti-catalysis) BR (Nd-catalysis) BR (emulsion polymerization) PAN

-90°C -100°C -110°C -80°C +100°C

Please select the relevant Tgs and calculate the Tg of an NBR grade which contains 50 wt.% acrylonitrile . The calculated Tg is :

………..°C 

Family Name Given Name

14

NBR: 

Please Mark „RIGHT “  “ or „WRONG “  “  Nr.: Frage

Right Wrong

1 The compatability of NBR and PVC depends on acrylonitrile content 2 Vulcanizates based on NBR perform well in ozone containing air 3 Vulcanizates based on CR perform well in ozone containing air 4 NBR/BIIR-Blends are useful for innerliners 5 Blends based on NBR and EPDM are compatible 6 Sulfur cure of NBR/HNBR-Blends result in high temperature resistance 7 Precrosslinked NBR yields compounds with low die swell 8 NBR can be vulcanized with phenol/formaldehyde resins 9 The swelling of NBR vulcanizates in oil increases with acrylonitrile content 10 The swelling of NBR vulcanizates in oil decreases with acry lonitrile content

Family Name Given Name

15

CR  Please Mark „RIGHT “  “ or „WRONG “  “  Nr. Question 1 2 3 4 5 6 7 8 9 10

Right Wrong

The properties of CR do not depend on the temperature of polymerization Vulcanization with ETU* results in crosslinks which contain 1 sulfur atom CR-based adhesive grades contain 2-3-Dichlorobutadiene-1,3 CR rubber grades are polymerized at a lower temperatures than CR adhesive grades CR-latices can not be coagulated with electrolytes CR crystallinity is disturbed by copolymerized sulfur Mercaptane modification results in higher tensile strength of vulcanized CR than the modification with xanthogendisulfides The ageing resistance of vulcanized CR sulfur grades is higher than those of mercaptane modified CR grades CR-sulfur grades have to be masticated prior to use Precrosslinked CR grades are used for vulcanizates with good dynamic performance

Family Name Given Name

16

HNBR:  Please Mark „RIGHT “  “ or „WRONG “  “ 

Nr.: Question 1 2 3 4 5 6 7 8 9 10

Right Wrong

Tg of HNBR does depend on the degree of hydrogenation The rebound of HNBR vulcanizates depends on ACN content HNBR and EVM are fully compatible at all copolymer compositions The compatibility of PVC and HNBR depends on the acrylonitrile content of HNBR Compatibility of HNBR and EVM depends on the vinyl acetate content of EVM The crystallinity of HNBR depends on acrylonitrile content Ethene sequences are prone to crystallization Tg of amorphous PE is at -200°C Tg of amorphous PE ist at + 0°C Unvulcanized HNBR with a low acrylonitrile content performs like a TPE

Family Name Given Name

17

HNBR:  Please Mark „RIGHT “  “ or „WRONG “  “ 

Nr.: Question 1 2 3 4 5 6 7 8 9 10

Right Wrong

Pd-Catalysats can be used for the selective hydrognation of C=C bonds in NBR Raney-Nickel can be used for the selective hydrogenation of C=C bonds in NBR Li[AlH4] can be used for the selctive hydrogenation of C=C bonds in NBR NN=NH can be used for the selective hydrogenation of C=C bonds in NBR Supported catalaysts can be recovered by centrifugation Supported catalaysts are not quantitatively recovered after hydrogenation Homogeneous catalysts can be recovered by filtration Ethene and acrylonitrile can be radically copolymerized Metallocenene-based catalysts readily copolymerize ethene and propene In the hydrogenation on NBR, gel formation is a major problem

Family Name Given Name

18

IIR, CIIR and BIIR:  Please Mark „RIGHT “  “ or „WRONG “  “  Nr.: Question

Right Wrong

1 2 3 4 5 6 7 8 9

At a polymerization temperature of -100°C molar masses of IIR are too high At a polymerization temperature of 23°C °C molar masses of IIR are too low IIR is a feedstock for the preparation of BIIR NR/BIIR-Blends are used for the production of innerliners IIR has a good performancde in the covulcanization of layers BIIR has a good performancde in the covulcanization of layers IIR can be vulcanized by the use of peroxides BIIR can be vulcanized by the use of peroxides Bladders which are used for the vulcanization of tyres are based on resin cured IIR 10 Bromination of IIR is performed in CH3Cl

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19

Thermoplastic Elastomers :  :  Please Mark „RIGHT “  “ or „WRONG “  “  Nr. Question

Right Wrong

1 2 3 4 5 6 7 8 9

The hard phase is not crosslinked The hard phase is crosslinked The soft phase can be polar The soft phase can be crsslinked Tg of soft phase > Tg of hard phase Tg of soft phase < Tg of hard phase Hard- and soft phase have to be mechanically coupled Hard- and soft phase have to be compatible Dynamic vulcanization can be performed in a twin screw extruder 10 Dynamic vulcanization can be performed on a mixing mill

Family Name Given Name

20

Please assign the Curves  104 1

3

   ] 10   a    P    M    [ 102    l   u    d 1   o 10   m    b   u 0 10    h   c    S

4

3

2

5 6 7 8 9

10-1

-100

-50

0 50 100 Temperatur

150

200

Nr.: Frage 1 2 3 4 5 6 7 8 9 10

Number of curve(s)

Which curve(s) matches the performance of unvulcanized NR ? Which curve(s) matches the performance of unvulcanized SBR ? Which curve(s) matches the performance of vulcanized SBR ? Which curve(s) matches the performance of unvulcanized NBR ? Which curve(s) matches the performance of vulcanized NBR ? Which curve(s) matches the performance of isotactic Polypropylene? Which curve(s) matches the performance of Polycarbonate? Which curve(s) matches the performance of atactic Polytyrene? Which curve(s) matches the performance of ABS with 30 wt.% BR ? Which of the curve(s) matches the performance of SBS ?

21

Which series of modified rubbers and which modification  results in the following properties  Rubber A Rubber B Rubber C

[phr [phr] [phr]

100 -

100 -

100

Carbon black (N 220) [phr]

30

30

30

Shore A Hardness/23°C Modulus300 [MPa] Tensile Strength [MPa] Elongation at break [%] Rebound/23°C [%] Goodrich HBU [°C] CS (24h/70°C) [%]

59 7,8 27,1 550 78 44 17

56 6,9 25,9 590 25 60 46

59 8,8 27,8 560 15 52 17

Volume swell (70h/70°C) ASTM-oil Nr. 1 [%] ASTM-oil Nr. 2 [%] ASTM oil Nr. 3 [%]

Rubber A Rubber B Rubber C modification

Family Name 66 114 191

73 28 108

-5 6 21

Air permeation/23°C [1018 x m4 /s.N] 27,0

8,0

1,98

Given Name

22

Which Metal is used for the production of BR in order to obtain  o btain the Properties below ?  2

CH2 CH

1

CH2

1

CH2

4

1

3

CH2

CH CH

CH CH

2

3

2

CH2

3

CH CH2

4

4

Metal Microstructure [%] 1,4-cis

36-38

97

97

93

98

12,9

52

1

2

3

1

68,3

Vinyl

10-11

2

1

3-4

<1

18,8

Vinyl/ 1H-NMR***

10,4

1,9

4,0

<1

18,1

Vinyl/FT-IR***

11,4

1,0

5,4

0,6

17,7

Vinyl/Metathese***

10,7

1,7

4,6

0,7

17,8

-103

-109

-80

1,4-trans

Tg

-93

-106

-107

23

Please Assign Rubber A and Rubber B  Rubber A Rubber B

100 -

75 25

50 50

25 75

100

Compound Properties ML 1+4(100°C) [MU] t2/177°C [min] t90/177°C [min]

123 1,5 11,7

99 1,6 11,0

58 1,5 10,2

40 1,6 10,2

32 1,6 9,5

Vulcanizate Properties Shore A Härte (23°C) Modulus 100 [MPa] Elongation at break [%] Tensile Strength [MPa]

78 10,7 240 26

80 13,1 190 24

80 12,6 170 22,5

81 12,0 145 18,8

77 8,3 165 18,5

[%] [%] [%]

12 20 27

12 17 27

12 17 25,5

14 14 20

14 9 15

Heat ageing (14d/150°C) F/F0 x100 [%] D/D0 x100 [%] H/H0 x100 [%]

-2,3 -37 +6

-3,8 -26 +5

-10 -29 +4

-7,5 -21 +3

-1,6 -12 +2

Compression Set 70h/23°C 70h/150°C 70h/175°C

Oil swelling (7d/150°C) ASTM-Öl Nr. 3 [%] ∆F/F0 x100 [%] ∆D/D0 x100 [%] ∆V/V0 x100

Rubber A Rubber B

Family Name -10 -4 +24

-17 -11 +34

-36 -29 +49

-50 -34 +67

-56 -45 +83

Given Name 24

Please Assign Rubber A and Rubber B  Rubber A Rubber B Fmin. [Nm] Fmax. ts [min] t90 [min] t95 [min] Shore A Modulus100 Modulus200 Modulu300 Tensile Strength Elongation at break Abrasion Index Ageing at 70h/121°C ∆ Dehnung CS (70 h/121°C)

[MPa] [MPa] [MPa] [MPa] [%]

[%] [%]

100,0 0 9,0 86,3 3,0 10,0 21,5 83 5,2 11,0 18,6 25,5 430 493

50,0 0 50,0 100,0 10,2 8,0 78,7 60,0 2,7 2,8 7,0 6,8 11,0 8,3 80 67 4,5 1,7 10,0 4,8 15,5 11,0 21,0 18,2 415 500 159 73

- 42 34,1

- 35 27,1

Rubber A Rubber B

Family Name Given Name

- 30 14,7

25

Please assign 5 polymer blends for which the  scheme below applies  Hard phase (coherent phase or matrix) Soft phase (dispersed phase) Nr.:

Hard phase

Soft phase

1 2 3 4 5

Family Name Given Name 26

Which Series of Rubbers Yields the Properties Given in the Table Below ?  ?  Rubber

A

B

C

D

E

F

Compound properties Mooney ML 1+4(100°C) t10/180°C [min] t90/180°C [min] FH-FL/180°C [N]

20 1,2 7,2 17

24 1,2 6,6 20

23 1,2 6,6 19

25 1,2 6,2 21

20 1,3 6,9 19

20 1,3 6,1 17

Vulcanised properties (ISO-Stab Nr. 2, 2mm) Shore A Härte (23°C) S 100 MPa] Elongation at break [%] Tenjsile Strength [MPa]

75 5,0 295 11,7

Compression Set 70h/100°C 70h/125°C 70h/150°C

Variation 74 5,7 275 13,6

68 4,4 285 12,6

71 5,4 280 12,8

68 4,2 300 11,5

72 4,7 300 10,5

23 25 41

20 23 38

20 25 41

22 26 40

21 24 46

27 31 51

Hot air ageing (14d/150°C) -3 [%] ∆F/F0 x100 [%] -2 ∆D/D0 x100 10 [%] ∆H/H0 x100

-12 -2 9

-10 2 11

-11 -2 12

10 -7 15

-8 -15 14

Storage in SAE Oil90 (3d/150°C) [%] ∆F/F0 x100 [%] ∆D/D0 x100 [%] ∆V/V0 x100

-12 -4 47

-8 -4 31

8 2 13

6 8 3

10 -12 -4

[%] [%] [%]

Rubber

-26 -19 69

Family Name Given Name

Please Assign Rubber A and Rubber B  Rubber A [phr] Rubber B [phr] Unaged: M300 [MPa] Tensile Strength [MPa] Elongation at break [%] Aged (168h/100°C) M300 [MPa] Tensile Strength [MPa] Elongation at break [%] Air permeation at 50psi/65°C (Q x 10-8] Adhesion at 100°C Self adhesion / tack [kN/m] Adhesion to NR [kN/m] Fatigue to failure after ageing at 168h/120°C [kcycles]

100 80 20

60 40

40 60 Rubber A

4,2 5,7 7,1 8,9 9,3 10,0 12,8 14,7 740 620 560 490 6,8 10,0 550 2,9

7,6 9,8 420 5,4

8,4 9,3 320 9,2

Rubber B

6,7 8,8 370 13,8 Family Name

16,8 14,7 15,2 15,4 7,5 10,0 14,7 20,8 61,8 23,6 0,3 0,0

Given Name

28