Utilization Soya Bean Fatty Acid for Synthesis of Alkyd Resin and Comparation Comparation of Properties Properties with Other Vegetable Oils 1
1*
1
H. Aghaie , A.R. Ilkhani , S. M. Sadat Choobeh 1. Department of Chemistry, Science and Research Branch, Bra nch, Islamic Azad University, Tehran, Iran(
[email protected] Ir an(
[email protected])) ABSTRACT In this study, alkyd resin was synthesized rate of decreasing of resins acid value and increasing of viscosity of resin were measured. FTIR spectroscopy, GPC method and different viscosity measurements employed to determination properties of product. FTIR spectroscopy was employed for identify of structure of resin and gel permeation chromatography (GPC) was used for determination of number average molecular weight (Mn) and polydispersity (PDI). Finally fatty acids composition of vegetable oil such as Coconut, Castor, Linseed, Palm, Sunflower and Tung oils have compared with Soya bean oil. Keywords: Alkyd resin synthesis; Soya bean fatty acid; Unsaturated hydroxylated Polyester; Polyester; Unsaturat ed vegetable oil
INTRODUCTION Alkyd resins are major important binders binders which which they are the largest volume base of coatings and paints especially for decorative applications [1]. The term alkyd is derived from two parts "al" which which referred prefix prefix abbreviation of alcohol and "kyd" which referred suffix abbreviation of acid and they are the products of the esterification of polybasic acids and polyhyd polyhydric ric alcohols alcohols [2]. [ 2]. Alkyd resins are using for decorative painting painting applications applications more than other binders binders because of lower cost; low price of alkyd resins related to inexpensive raw material, easy manufacturing and high solubility of resin in less expensive
solvents. Alkyd resins not only are used in decorative paints but also mainly are applied in air drying and stoving paints, inks, machine toll finishes and clear, matt and semi matt varnishes of wood furniture[3]. The unsaturated hydroxylated polyesters polyesters resins resins which which they have modified with vegetables, marine oils or their fatty acid called alkyd resins [1], therefore alkyd resins are main product of poly condensation reactions between poly carboxyli carboxylicc acids and poly alcohol in present fatty acids or vegetable oils [2]. This kind of reaction had obtained by following following formula: formula: ::
Poly carboxylic acids + Poly alcohols + Fatty acids, Vegetable oils → Alkyd Resin + H 2O
Poly alcohols which mainly are using for condensational polymerization reactions of alkyd resins content Ethylene glycol, propylene glycol, aromatic poly basic acids and aliphatic poly basic acids; for preparation of alkyd binders usually are employing aromatic poly carboxylic acids such as phthalic anhydride, isophthalic acid; but cycloaliphatic anhydrides such as, hexahydrophthalic anhydride, also malic anhydride are using for alkyd resins esterification reactions [3-4]. Suitable chose of types of poly basic acids and poly alcohols in reaction not only will prevent of gelation of alkyd resins reaction but also will give chance to easy control of process of polymerization of alkyd resins to operator. Benzoic acid and others mono
diethylene glycol and pentaerythritol. Inaddition poly carboxylic acids are using for alkyd resins reactions divided to two different branches, basic carboxylic acid are used for alkyd resins formulation including high functionality system to act as chain stopper [5]. Indeed alkyd resins formula is modified with varying amounts of fatty acids with the exception of rosin, almost all of these monobasic fatty acids are derived from the vegetable drying, semidrying oils or marine semidrying oils which these are glycerol esters of their acids. The important and famous vegetable drying and semi drying vegetable oils composition which they usually have used for alkyd resin have shown Table 1.
Table 1: fatty acid composition of some important vegetable oils
Fatty acid
Caprylic Capric Lauric Myristic Palmitic Stearic Oleic Ricinolic Linoleic Linolenic Eleostearic Licanic Iodine Value
r a l a l u u c e l m o r o f M
t e u l d l b n n i u o o o o b c o D C
C8H16O2 C10H20O2 C12H22O2 C14H28O2 C16H32O2 C18H36O2 C18H34O2 C18H34O2 C18H34O2 C18H30O2 C18H30O2 C18H30O2
0 0 0 0 0 0 1 1 2 3 3 3
--------
----
6 6 44 18 11 6 7 ---2 ---------7.510.5
r o l t s i a o C
d e e i s l n o i L
------------2 1 7 87 3 ---------8191
------------6 4 22 ---16 52 ------155136
m l i l a o P
r e w l o i l f o n u S
n a e B l i a o y o S
---------1 48 4 38 ---9 ---------44 54
------------11 6 29 ---52 2 ------120141
------------11 4 25 ---51 9 ------120141
g l n i u o T ------------4 1 8 ---4 3 80 ---160175
Tab 2: Classification of alkyd resins based on length of oil and properties of resins. Variations in the amounts and types of components special for fatty acids given enormous varieties of alkyd resins with different mechanical and reological
properties, thus alkyd resins are often classified with the oil type, the oil length and application. Tab.2 show classification of alkyd resins based on
Parameter of Resins Length of Oil % Fatty Acid % Phethalic Anhydride Suitable Solvent % Solid of Resin Preparation of Film
Short Oil 25-47
Classification of Alkyd Resins Based on Length of Oil Medium Medium Long Long Very Long Short Oil Oil Medium Oil Oil Oil 43-47 47-56 53-56 56-74 74-85
30-39
40-45
45-50
50-55
55-70
70-80
38-50
36-38
33-36
30-33
20-30
10-20
Aromatic
Aromatic
Aliphatic
Aliphatic
Aliphatic
Aliphatic
45-50
50
50-55
60
60-70
70-100
Thermoset High Temperature
Thermoset High-Low Temperature
Thermoset Low Temperatur
Thermoplast
Thermoplast
Thermoplast
different items such as length of oil, percentage of fatty acids and phethalic anhydride which they used in EXPERIMENTAL The experimental materials have used for experimental tests such as titrations and others test which exact measurement of values were important of them and industrial materials have used for synthesis of alkyd resins because of industrial aims. Potassium hydroxide, Potassium dichromate, Potassium iodide, Potassium hydrogen phthalate, Bromine, Chloroform, Acetic acid, Phenolphthalein, Iodine, Isopropyl alcohol and Sodium tiosulphate have used as experimental materials and all this material had produced by Merk company. Industrials materials have utilized for syntheses of resins, content: Soya fatty acid from Paxan Company of Iran, titer ◦ point 23 C and Iodine number 123 mg KOH/g fatty acid, Phetalic anhydride from IG. Petrochemical Company of ◦ India, melting point 133 C and acid number 391 mg KOH/g fatty acid, maleic anhydride from USP Technology Group of Taiwan, melting point 54 ◦C and acid number 522 mg KOH/g fatty acid, Glycerin from EVYAP Company from Turkey, purity percent 99.5%,
formulation of resins and properties of alkyd resin [5-7].
other
Pentaerythritol from Koninda Canada, ◦ melting point 248 C, White sprit solvent from Petrochemical Company ◦ of Iran, boiling point149 C, Toluene from Petrochemical Company of Iran, boiling point 111 ◦C have used. Equipments as have used in this work, classified to three sections: glass equipments which they applied for titrations .Equipments as applied for producing process of alkyd resin and tests for control the products during the process and after finishing. These are: Ben marry thermostat NLW-8, ◦ sensitivity 0.1 C; Glass separator, sensitivity 0.1 M; Blender Heidolph model RZR2020, 80-2000 cycle per minute; Stanlees steel turbine agitator; Glass reactor, volume
2Liter; Glass condenser, length 70 cm length; Gardner viscometer model MT, BYK Company of Germany; Gardner color meter model MT, BYK Company of Germany; Electrical melting pointer, Tebazma Company of Iran; Electrical heater up to 350 ◦C, sensitivity 1 ◦C.
Equipment for identification of structure of resin and viscosities tests, these are: FTIR spectrometer model BRUKER-IF
548, Gel Chromatographer GPC model MAXIMA 820 and Brookfield viscometer model ST-DIGIT R.
Figure 1: scheme of Alkyd Resin Reactor [5] Alkyd resin which it synthesized in this study is according fallowing formulation: Toluene
Glycerin
2.47
13.47
Penta erythritol 8.05
RESULTS AND DISCUSSION Acid value curve of synthesized alkyd resins (figure2) illuminate that in condensation polymerization reaction of
Malic Anhydride 0.86
Phetalic Anhydride 28.99
Soya Fatty acid 46.16
alkyd resin acid value of binder has decreased, also viscosity of alkyd resin has increased.
60
, ) n i s 50 e R ) k g / c o 40 H t O S ( y 30 K t g i s o m ( c e s i 20 u l V a v 10 d i c A
Ac id value Viscosity
0
6:00 8:00 9:30 10:50 11:50 12:30 13:20 13:50 Time after start Reflux( hr)
◦
Figure 2: Acid number and Viscosity curve of synthesized long oil alkyd resin at 25 C.
For synthesized resin FTIR spectroscopy have done which it is a powerful method for evaluation of chemical structure of organic compound (figure 3a) for estimated position
functional groups in polymer molecule of resin. Determination of distribution of average molecular weight of alkyd resin synthesized is very important for
characterizing of products. Gel Permeation Chromatography (GPC) have employed for evaluation of average molecular weight and for determination of maximum peak of alkyd resin product. Figure 3b clearly shows distribution of molecular weight for alkyd resin synthesized. In gel chromatographs unit of X axe is minutes times 10 and unit of Y axe is -1 volts multiplied on 10 .
(a)
GPC method not only have used for determination of distribution of molecular weight of resins it called polydispersity (PDI), but also have applied for determination of numeric average molecular weight (Mn), weight average molecular weight (Mw) and viscosity average molecular weight (Mv).
(b)
Figure 3: FTIR (a) and GPC (b) spectrums of alkyd resin CONCLUSION Viscosity of synthesized alkyd resin 60% in White Sprite at 25 ◦C have measured two different methods; Brookfield viscometer by spindle R4 have shown 5500 centi poise and viscosity Ford cup 6 have measured 180 seconds. Determination of distribution of average molecular weight of synthesized alkyd resin has shown M n 12179, Mw and Mv 18666 also PDI, 1.5325 which they are normal range of alkyd resin properties. Peaks 3503, 1732 -1 and 2926, 2854 cm involve – O – H acid and alcohol , – C = O ester , – CH2 stretching of alkyd resin. REFERENCES 1- M.A.Mazandarani, Paint and Resin Technology, vol.2, 3nd ed, Pishro Publication, Iran, 1992 2- M.A.Mazandarani, Paint and Resin Technology, vol.1, 3nd ed, Pishro Publication, Iran, 1992
3- M. N. S. Kumar , Z. Y. Maimunah, S. R. S. Abdullah ,Synthesis of Alkyd Resin from Non-Edible Jatropha Seed Oil, J. Polym. Environ., vol.18, 2010 4- Zeno W. Wicks, JR , Frank N. Jones , and S.Peter Pappas , Organic Coating Science and Technology , 2nd ed , Wiley –Inter science Publication, Canada ,1999 5- L. M. Santos, E. Coser, J., E. L. Dullius, S. Einloft ,Utilization of palm oil in the alkyd resin synthesis, Faculdade de Quimica - Laboratório de Organometálicos e Resinas,2005 6- Dutta, N.; Karak, N.; Dolui, S. K. Prog. Org. Coat., 146-152 , vol.49, 2004 7- T C .Patton Baker, Alkyd Resin Technology: Formulating Techniques and Allied Caster Oil Company, InterScience Publication, 1962
