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Utilization Soya Bean for Synthesis of Alkyd and Comparation of Properties with Other Vegetable Oils

1 H. Aghaie 1, A.R. Ilkhani 1*, S. M. Sadat Choobeh1 1. Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran([email protected]) Tehran, Iran([email protected])

ABSTRACT In this study, alkyd resin was synthesized rate of decreasing of 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 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 ; Unsaturated vegetable oil

INTRODUCTION Alkyd resins are major important solvents. Alkyd resins not only are used binders which they are the largest in decorative but also mainly are volume base of coatings and paints applied in air drying and stoving paints, especially for decorative applications inks, machine toll finishes and clear, [1]. The term alkyd is derived from two matt and semi matt of wood parts "al" which referred prefix furniture[3]. abbreviation of alcohol and "kyd" which The unsaturated hydroxylated referred suffix abbreviation of acid and resins which they have they are the products of the modified with vegetables, marine oils or esterification of polybasic acids and their fatty acid called alkyd resins [1], polyhydric alcohols [2]. therefore alkyd resins are main product Alkyd resins are using for decorative of poly condensation reactions between painting applications more than other poly carboxylic acids and poly alcohol binders because of lower cost; low price in present fatty acids or vegetable oils of alkyd resins related to inexpensive [2]. This kind of reaction had obtained raw material, easy manufacturing and by following formula: :: high solubility of resin in less expensive

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O Poly carboxylic acids + Poly alcohols + Fatty acids, Vegetable oils → Alkyd Resin + H2O

Poly alcohols which mainly are using diethylene glycol and . for condensational polymerization Inaddition poly carboxylic acids are reactions of alkyd resins content using for alkyd resins reactions divided Ethylene glycol, propylene glycol, to two different branches, aromatic poly basic acids and aliphatic basic carboxylic acid are used for alkyd poly basic acids; for preparation of resins formulation including high alkyd binders usually are employing functionality system to act as chain aromatic poly carboxylic acids such as stopper [5]. phthalic anhydride, isophthalic acid; but Indeed alkyd resins formula is cycloaliphatic anhydrides such as, modified with varying amounts of fatty hexahydrophthalic anhydride, also acids with the exception of rosin, almost malic anhydride are using for alkyd all of these monobasic fatty acids are resins esterification reactions [3-4]. derived from the vegetable drying, Suitable chose of types of poly basic semidrying oils or marine semidrying acids and poly alcohols in reaction not oils which these are esters of only will prevent of gelation of alkyd their acids. The important and famous resins reaction but also will give chance vegetable drying and semi drying to easy control of process of vegetable oils composition which they polymerization of alkyd resins to usually have used for alkyd resin have operator. Benzoic acid and others mono shown Table 1.

Table 1: fatty acid composition of some important vegetable oils

Fatty acid oil oil oil oil oil oil oil oil oil bond bond Palm Palm Tung Tung Castor Castor Double Double Linseed Linseed formula formula Coconut Coconut Molecular Molecular Sunflower Soya Bean Soya Bean

Caprylic C8H16O2 0 6 ------Capric C10H20O2 0 6 ------Lauric C12H22O2 0 44 ------Myristic C14H28O2 0 18 ------1 ------Palmitic C16H32O2 0 11 2 6 48 11 11 4 Stearic C18H36O2 0 6 1 4 4 6 4 1 Oleic C18H34O2 1 7 7 22 38 29 25 8 Ricinolic C18H34O2 1 ---- 87 ------Linoleic C18H34O2 2 2 3 16 9 52 51 4 Linolenic C18H30O2 3 ------52 ---- 2 9 3 Eleostearic C18H30O2 3 ------80 Licanic C18H30O2 3 ------Iodine 7.5- 81- 155- 44 - 120- 120- 160- Value ------10.5 91 136 54 141 141 175

Tab 2: Classification of alkyd resins based on length of oil and properties of resins.

Variations in the amounts and types of properties, thus alkyd resins are often components special for fatty acids given classified with the oil type, the oil enormous varieties of alkyd resins with length and application. Tab.2 show different mechanical and reological classification of alkyd resins based on

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Classification of Alkyd Resins Based on Length of Oil Parameter Short Medium Medium Long Long Very Long of Resins of Resins Oil Short Oil Oil Medium Oil Oil Oil Length of 25-47 43-47 47-56 53-56 56-74 74-85 Oil Oil % Fatty 30-39 40-45 45-50 50-55 55-70 70-80 Acid Acid % Phethalic 38-50 36-38 33-36 30-33 20-30 10-20 A nhydride Anhydride Suitable Aromatic Aromatic Aliphatic Aliphatic Aliphatic Aliphatic Solvent Solvent % Solid of 45-50 50 50-55 60 60-70 70-100 Resin Resin Preparation Thermoset Thermoset Thermoset of Film of Film High High-Low Low Thermoplast Thermoplast Thermoplast Temperature Temperature Temperature Temperatur

different items such as length of oil, formulation of resins and other percentage of fatty acids and phethalic properties of alkyd resin [5-7]. anhydride which they used in

EXPERIMENTAL The experimental materials have used Pentaerythritol from Koninda Canada, for experimental tests such as titrations melting point 248 ◦C, White sprit and others test which exact solvent from Company measurement of values were important of Iran, boiling point149 ◦C, Toluene of them and industrial materials have from Petrochemical Company of Iran, used for synthesis of alkyd resins boiling point 111 ◦C have used. because of industrial aims. Potassium hydroxide, Potassium Equipments as have used in this work, dichromate, Potassium iodide, classified to three sections: glass Potassium hydrogen phthalate, equipments which they applied for Bromine, Chloroform, Acetic acid, titrations .Equipments as applied for Phenolphthalein, Iodine, Isopropyl producing process of alkyd resin and alcohol and Sodium tiosulphate have tests for control the products during the used as experimental materials and all process and after finishing. These are: this material had produced by Merk Ben marry thermostat NLW-8, company. sensitivity 0.1 ◦C; Glass separator, Industrials materials have utilized for sensitivity 0.1 M; Blender Heidolph syntheses of resins, content: Soya fatty model RZR2020, 80-2000 cycle per acid from Paxan Company of Iran, titer minute; Stanlees steel turbine agitator; point 23 ◦C and Iodine number 123 mg Glass reactor, volume KOH/g fatty acid, Phetalic anhydride from IG. Petrochemical Company of India, melting point 133 ◦C and acid 2Liter; Glass condenser, length 70 cm number 391 mg KOH/g fatty acid, length; Gardner viscometer model MT, from USP Technology BYK Company of Germany; Gardner Group of Taiwan, melting point 54 ◦C color meter model MT, BYK Company and acid number 522 mg KOH/g fatty of Germany; Electrical melting pointer, acid, Glycerin from EVYAP Company Tebazma Company of Iran; Electrical from Turkey, purity percent 99.5%, heater up to 350 ◦C, sensitivity 1 ◦C.

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Equipment for identification of structure 548, Gel Chromatographer GPC model of resin and viscosities tests, these are: MAXIMA 820 and Brookfield FTIR spectrometer model BRUKER-IF viscometer model ST-DIGIT R.

Figure 1: scheme of Alkyd Resin Reactor [5] Figure 1: scheme of Alkyd Resin Reactor [5]

Alkyd resin which it synthesized in this study is according fallowing formulation:

Toluene Glycerin Penta Malic Phetalic Soya Fatty erythritol Anhydride Anhydride acid 2.47 13.47 8.05 0.86 28.99 46.16

RESULTS AND DISCUSSION Acid value curve of synthesized alkyd alkyd resin acid value of binder has resins (figure2) illuminate that in decreased, also viscosity of alkyd resin condensation polymerization reaction of has increased.

60

50 Acid value 40 Viscosity

30

20 Viscosity(Stock) 10

Acid value(mg KOH/g Acid KOH/g value(mg Resin), 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 functional groups in molecule spectroscopy have done which it is a of resin. powerful method for evaluation of Determination of distribution of chemical structure of organic compound average molecular weight of alkyd resin (figure 3a) for estimated position synthesized is very important for ٧٢ ٧٢

characterizing of products. Gel GPC method not only have used for Permeation Chromatography (GPC) determination of distribution of have employed for evaluation of molecular weight of resins it called average molecular weight and for polydispersity (PDI), but also have determination of maximum peak of applied for determination of numeric alkyd resin product. Figure 3b clearly average molecular weight (Mn), weight shows distribution of molecular weight average molecular weight (Mw) and for alkyd resin synthesized. In gel viscosity average molecular weight chromatographs unit of X axe is (Mv). minutes times 10 and unit of Y axe is volts multiplied on 10-1.

(a) (b)

Figure 3: FTIR (a) and GPC (b) spectrums of alkyd resin

CONCLUSION Viscosity of synthesized alkyd resin 3- M. N. S. Kumar , Z. Y. Maimunah, 60% in White Sprite at 25◦C have S. R. S. Abdullah ,Synthesis of Alkyd measured two different methods; Resin from Non-Edible Jatropha Seed Brookfield viscometer by spindle R4 Oil, J. Polym. Environ., vol.18, 2010 have shown 5500 centi poise and 4- Zeno W. Wicks, JR , Frank N. Jones , viscosity Ford cup 6 have measured 180 and S.Peter Pappas , Organic Coating seconds. Determination of distribution of Science and Technology , 2nd ed , average molecular weight of Wiley –Inter science Publication, synthesized alkyd resin has shown Mn Canada ,1999 12179, Mw and Mv 18666 also PDI, 5- L. M. Santos, E. Coser, J., E. L. 1.5325 which they are normal range of Dullius, S. Einloft ,Utilization of palm alkyd resin properties. Peaks 3503, 1732 oil in the alkyd resin synthesis, and 2926, 2854 cm-1 involve – O – H Faculdade de Quimica - Laboratório de acid and alcohol , – C = O ester , – CH2 Organometálicos e Resinas,2005 stretching of alkyd resin. 6- Dutta, N.; Karak, N.; Dolui, S. K. Prog. Org. Coat., 146-152 , vol.49, 2004 REFERENCES 7- T C .Patton Baker, Alkyd Resin 1- M.A.Mazandarani, and Resin Technology: Formulating Techniques Technology, vol.2, 3nd ed, Pishro and Allied Caster Oil Company, Inter- Publication, Iran, 1992 Science Publication, 1962 2- M.A.Mazandarani, Paint and Resin Technology, vol.1, 3nd ed, Pishro Publication, Iran, 1992

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