Arizona Chemical-Tailored Sustainable Products for the Tire Industry

Tailored Sustainable Products for the Tire Industry

Tire Technology Expo 2015 Cologne, Germany Dr. Wolfgang Pille-Wolf

BIOBASED SOLUTIONSTM

Outline Who is Arizona Chemical Tread Enhancement Additives ● Effect in Elastomers ● Application Examples

Process Enhancement Additive ● SYLVATRAXX™ 1001

Summary Acknowledgements

Copyright ©2015 Arizona Chemical B.V.

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Arizona Chemical Long Term Supplier to the Tire & Rubber Industry Arizona Chemical as a leading producer and refiner supplies ● Since 50 years to the Rubber Industry ― Emulsifiers ― Polymerization Control Agents ― Tackifiers

● Since 25 years to the Tire Manufacturers ― Vulcanization Enhancers ― Tackifiers ― Processing Aids

● Since 15 years focusing on Tread Enhancement Additives Copyright ©2015 Arizona Chemical B.V.

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Leading Producer Of Pine Chemicals The largest producer of pine chemicals ● 80 years of experience in Bio-refining ● Greatest Crude Tall Oil distillation capacity in the world ● Largest integrated producer of resins from pine chemicals

World class manufacturing practices and facilities ● Generating the highest value from Crude Tall Oil ● Minimized emissions and waste ● High energy efficiency

Committed to continuous improvement ● ISO 14001 ● ISO 9000 ● Responsible Care® program


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Diversified Refining & Value Added Downstream Products TIRES Fuel Additives Alkyds for Paints Oil field Exploration Surfactants

CRUDE TALL OIL Tall Oil Fatty Acids Distilled Tall Oil Tall Oil Rosin Tall Oil Pitch

Terpene Monomers

Polyamide Resins

Dimer Acids

Esters TIRES Alkyd for paints

Rosin Resins Sterols

Hydraulic Fluids Machinery Lubricants Engine Lubricants Ink Solvents

Printing Protective Coatings Hot Melt Adhesives Thixotropic Additives for Alkyds

TIRES Adhesives Roadmarking Paper Size Neutraceuticals

Biofuels & Performance Blends

Mining

Terpene Resins

CRUDE SULFATE TURPENTINE CRUDE ORANGE OIL

TIRES Chemical Intermediates for Flavour and Fragrances Adhesives

External Raw Materials eg vinyl aromatics, phenol Copyright ©2015 Arizona Chemical B.V.

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Value From The Tree

Using renewable raw material

Utilising the co-product of pulp production

Refining and producing chemicals

Providing sophisticated products for the global chemical industry

PULP MILL

ARIZONA CHEMICAL


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Serving Customers Globally


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Traditional Use of Resins in Rubber Compounds Building Tack ● ● ● ●

Rosin Polyterpene resins Phenolic Resins Lowest possible dosage level of 0.5 to 4 phr ― Impact on visco-elastic rubber characteristics

Homogenizing Resins Reinforcing resins Dispersing resins Curing resins Copyright ©2015 Arizona Chemical B.V.

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Tread Enhancement Additives (TEA) Show Growth due to Regulatory Changes Number of Patent Applications

Paradigm Change

Non-labeled Oil Regulation in Practice

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● Use of Resins to improve Traction of Passenger Car Tires (PCR)

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Non-labeled Oil Regulation announced

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● Resin dosages as high as 18 phr described

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Rubber Dust Study

15 10 5 0 1980

1985

1990

1995

2000

2005

2010

2015

2020

Year of Publication

SYLVATRAXX™ Copyright ©2015 Arizona Chemical B.V.

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Tread Enhancement Additives (TEA) influence Visco-elastic Properties of Rubber Polymers Right Shift tan δ = positive for Wet Traction

Loss Factor tan δ

Storage Modulus G’

Reduced G’ = negative for RR

Rubber Rubber + TEA

Rubber Rubber + TEA

Increasing Temperature

Increasing Temperature

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Factors influencing Performance Miscibility ● Single Tg

Compatibility ● Single Tg, (micro) heterogeneous phase ― Molecular structure ― Molecular weight

Compound Formulations ● Polymer Matrix ● Process Oil ● Filler

Dosage Mixing SYLVATRAXX™ Copyright ©2015 Arizona Chemical B.V.

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Matching Solubility is critical for Application Development


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TEA Polarity determines Tire Application Low polar TEA show favorable balance between Wet Grip and Rolling Resistance ● Hydrocarbon or Terpene based ● Pure aromatic ● Modified Hydrocarbon or Terpene Polar TEA show unfavorable balance between Wet Grip and Rolling Resistance ● Rosin Esters ● Terpene Phenols with high Polarity ― Recommended for Racing applications


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TEA Chain Length impacts polymer compatibility

Phase Diagram of Styrene oligomer with 3,5 and 9 repeating units (OS3, OSG5, OSG9) in SBR, NR and BR showing Tg as f(oligomer concentration) Thielen, G.; Schuster, R.; Hallersleben, M.L.; Model resins leading to controlled Phase Morphology; KGK 46(4), p. 263-271, 1993


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TEA effects on polymer matrices Polymer blends cast from solution Polymer blends in full tread compounds


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Polymer Blend NR/SBR in 1:1 ratio is immiscible

Polymer Blend from Solution


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Pure Aromatic TEA concentrates mainly in SSBR Phase of NR/SBR Blend

SSBR/NR/Pure Aromatic TEA = 1:1:2



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Terpene Phenol starts to compatibilize the immiscible Polymer Blend NR/SBR

SSBR/NR/Terpene Phenol TEA = 1:1:2



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Polyterpene compatibilizes broadly immiscible Polymer Blend NR/SBR

SSBR/NR/Polyterpene TEA = 1:1:2



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TEA effects on polymer matrices Polymer blends cast from solution Polymer blends in full tread compounds


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Influence of Polymer Matrices Presence of NR Strongly Enhances Performance Typical Summer Tread Compound

DMA Results: WG and RR Indicators (normalized) higher = better

Polymer Blend 100phr Silica 80phr TEA 8phr TDAE oil 12phr


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Influence of Rubber Matrices Presence of SSBR Strongly Enhances Performance DMA Results: WG and RR Indicators (normalized)

Typical Winter Tread Compound

higher = better

Polymer Blend 100phr Silica 80phr TEA 8phr TDAE oil 12phr


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Tread Enhancement Additives Dosage Effects Complete Tread Compounds


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All TEA Types Improve Wet Traction At Different Optimal Dosage Levels Typical Summer Tread Compound

DMA Results: WG Indicator (normalized) higher = better

SSBR BR Silica TEA+TDAE

100phr 30phr 80phr 20phr


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All TEA Types Affect Rolling Resistance TEAs Outperform Standard Resins Typical Summer Tread Compound

DMA Results: RR Indicator (normalized) higher = better

SSBR BR Silica TEA+TDAE

100phr 30phr 80phr 20phr


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Process Enhancement Additive: SYLVATRAXX™ 1001 Development to improve the process ability of Silane VP Si 363® in collaboration with Objective ● Reduction of Mooney viscosity especially in 1st stage mixing ● Improve compound green strength ● Improve compound surface after extrusion


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SYLVATRAXX™ 1001 - Characteristics Treated rosin based product with high renewable content

Improves processing of tread compounds with high silica content and Evonik’s Silane VP Si 363® Reduces the number of passes and increases production capacity Allows further improvement of rolling resistance to support continuous increasing fuel efficiency demands Available per direct SYLVATRAXX™ Copyright ©2015 Arizona Chemical B.V.

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Slab Surfaces and Feathering Significantly Improved Si 266®

Si 266® + 2.5 phr SYLVATRAXX™1001

VP Si 363®

VP Si 363® + 2.5 phr SYLVATRAXX™1001

2-roll mill passed


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Mooney Viscosity after 1st Stage Significantly Reduced

30% Reduction

18% Reduction


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Presentation Summary TEA Performance is driven by its compatibility with the Polymer Matrix and Dosage Especially with the presence of NR the performance improvement is significant At low dosages the new SYLVATRAXX™1001 improves processability of Silica filled tread compounds with the coupling agent VP Si 363®, without significantly impacting other properties


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Company Summary Unique portfolio of natural, synthetic and hybrid products Wide range of products with different polarities and Glass Transition Temperatures Commercially available products to meet new legislation targets Consistent quality and global supply chain with regional supply points Comprehensive development program in Tread Enhancement Additives Leading supplier and knowledge leader on TEA terpene technology Dedicated rubber lab for tire compounding and testing Strong relationships with universities and institutes

Supplying industry leaders with performance products for many years SYLVATRAXX™ Copyright ©2015 Arizona Chemical B.V.

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Product Portfolio Highlights Polyterpene

SYLVATRAXX™ 4125 SYLVATRAXX™ 4150

Modified Polyterpene

SYLVATRAXX™ 5007

Terpene Phenol

SYLVATRAXX™ 4202

Modified Terpene Phenol

SYLVATRAXX™ 6720

Pure Aromatic – AMS

SYLVATRAXX™ 4401

Rosin Ester

SYLVATRAXX™ 3400

Treated Rosin

SYLVATRAXX™ 1001 SYLVATRAXX™ 1035


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Acknowledgement External Evonik Industries Metravib Twente University QUST ARDL DIK ERT

Arizona Chemical Neil Riddle Hannes van Erp Yvette Verdonk Jochem Vervelde Yubin Wu Godfried Buisman Jeffrey Warmkessel Roelof Luth


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A partner for the Global Tire Industry Please visit us at our booth C050 Contacts: Sander Ridder Global Marketing Manager Tires

[email protected]

Dr. Jérémie Pichereau Technical Manager Tires

[email protected]

Dr. Wolfgang Pille-Wolf Principal Scientist

[email protected] 42 42

Arizona Chemical-Tailored Sustainable Products for the Tire Industry

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