293

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Prog. Polym. Sci. 31 (2006) 633670 www.elsevier.com/locate/ppolysci
Polymers from triglyceride oils

F. Seniha Gunera, Yusuf Yagcb,, A. Tuncer Erciyesa
a
Chemical Engineering Department, Istanbul Technical University, Maslak 34469 Istanbul, Turkey b Department of Chemistry, Istanbul Technical University, Maslak 34469 Istanbul, Turkey Received 8 December 2005; received in revised form 7 July 2006; accepted 17 July 2006
Abstract Recently, the use of renewable sources in the preparation of various industrial materials has been revitalized because of the environmental concerns. Natural oils are considered to be the most important class of renewable sources. They can be obtained from naturally occurring plants, such as sunower, cotton, linseed. They consist predominantly of triglycerides. This review covers the structure, property and modication of triglyceride oils and synthesis of polymers there from. Polymers from triglyceride oils are prepared via conceptually different strategies. Various polymerization methods, including condensation, radical, cationic and methathesis procedures have been applied. The scope, limitations, and possibility of utilizing such methods for various applications have been highlighted. r 2006 Elsevier Ltd. All rights reserved.
Keywords: Renewable sources; Triglyceride oils; Oxypolymerized oils; Polymers; Composites; Inorganicorganic hybrid materials
Contents 1. 2. 3. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634 Structure of triglyceride oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634 Oil-based polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637 3.1. Oxypolymerized oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637 3.2. Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638 3.2.1. Alkyd resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638 3.2.2. Liquid crystalline alkyd resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640 3.2.3. High-solid content alkyd resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640 3.2.4. Water-soluble alkyd resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642 3.2.5. Polyhydroxyalkanoates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642 3.3. Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642 3.3.1. Organic solvent-soluble polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642 3.3.2. Water-soluble polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644 3.3.3. Interpenetrating polymer networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644 3.3.4. Urethane alkyds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
Corresponding author. Tel.: +90 212 285 3241; fax: +90 212 285 6389.
E-mail address: yusuf@itu.edu.tr (Y. Yagc). 0079-6700/$ - see front matter r 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.progpolymsci.2006.07.001
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4. 5. 6. 7.
Polyamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645 Vinyl polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645 3.5.1. Classical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645 3.5.2. Macroinitiator/macromonomer method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654 3.5.3. Fatty acid- or oil-grafted polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 656 3.6. Epoxy resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657 3.7. Polyesteramides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659 3.8. Polynaphthols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659 Metathesis of oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660 Composites from oil-based polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662 Oil-based inorganicorganic hybrid materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
3.4. 3.5.
1. Introduction Polymers are widely used for technical purposes. Depending in their usage area, it should be expected that they exhibit some specic properties such as thermal stability, exibility, resistance to chemicals, biocompatibility, biodegradability, adhesion to metallic substances, gas permeability, electrical conductivity and non-ammability. The structure of monomer used in polymer preparation is directly effective on these properties. Aromatic polymers, for example, should be resistant to high temperatures, polymers having high halogen content are inherently nonammable, and uorine-containing polymers resist both water and solvents. In many cases the properties are signicant in specialty products. Degradable polyesters, for example, are already used as disappearing surgical sutures. For the coating purposes, triglyceride oils are subjected to heat treatment or air blowing to yield bodied and blown oils, respectively. While in the bodied oils, triglyceride molecules combined with each other through the DielsAlder reaction, the corresponding linkages are achieved by the coupling of the free radicals, formed from the decomposition of hydroperoxides. These hyrdoperoxides are introduced during the air-blowing process. In order to improve end-product properties, triglyceride oils have been used in the preparation of polymers. Although they have been used since 19th century in the paint formulation, in the last decade investigation on oil-based polymers have been focused for different purposes. Particularly, after the petroleum shortage, preparation of polymers from renewable sources has become more important. Nowadays, there is a growing interest to produce biopolymers. Triglyceride oils are one of the most
important sources for biopolymers. Oil-based biopolymers have many advantages compared with polymers prepared from petroleum-based monomers. They are biodegradable and, in many cases, cheaper than petroleum polymers. The life cycle of polymers based on triglyceride oils is given in Fig. 1. 2. Structure of triglyceride oils The word oil is used for triglycerides that are liquid at ordinary temperatures. They are waterinsoluble products of plants. A triglyceride is an ester product obtained from one molecule of glycerol and three molecules of fatty acids (Scheme 1). They can also be articially produced from the reaction of glycerol and fatty acids (Scheme 2). The fatty acids contribute from 9496% of the total weight of one molecule triglyceride oil. The most common fatty acids in natural oil compositions are given in Table 1. As shown, some fatty acids are saturated (Scheme 3a) and some of them are unsaturated (Scheme 3b). Saturated fatty acids have no double bonds. On the other hand, unsaturated fatty acids have one or more than one double bond. If the double bonds in the carbon
Plant oils Extraction Synthesis Biomass Assimilation Degradation Waste Use Polymers
Modification
Fig. 1. Life cycle of polymers based on triglyceride oils.
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chain are separated by at least 2 carbon atoms, double bonds are called isolated (Scheme 3c). If single and double bonds alternate between certain carbon atoms, double bonds are called conjugated (Scheme 3d). Additionally, some natural fatty acids have different structures, with acid chains having hydroxyl, epoxy or oxo groups, or triple bonds. Because of their structural differences, each fatty acid has various physical properties (Table 2). Among the triglyceride oils, linseed, sunower, castor, soybean, oiticica, palm, tall and rapseed oils are commonly used for synthesis of oil-modied polymers. Although fatty acid pattern varies between crops, growth conditions, seasons, and
CH2
CO
R1 R2 R3
CH CH2
CO
CO
R1, R2, R3: fatty acid chain

Scheme 1. A triglyceride molecule.
purication methods, each of triglyceride oils has special fatty acid distribution. Linseed oil, for example, consists of largely linoleic and linolenic acids. In castor oil, the greater part of fatty acids is ricinoleic acid (12-hydroxy-9-octadecenoic acid). Fatty acid compositions of these oils are shown in Table 3 [1,2]. Depending on the fatty acid distribution, each type of oil has specic physical and chemical properties (Table 4). One of the most dominant parameter affecting of fatty acid and oil properties is the degree of unsaturation. The average degree of unsaturation is measured by iodine value. It is calculated from the amount of iodine (mg) reacted with double bonds for 100 g sample under specied conditions. Triglyceride oils are divided into three groups depending on their iodine values; drying, semi-drying and nondrying oils. The iodine value of a drying oil is higher than 130. This value is between 90 and 130 for semidrying oils. If the iodine value is smaller than 90, oil is called non-drying oil. Iodine values of some common fatty acids and their triglycerides are given in Table 5 [3].
CH2 CH CH2
OH OH + 3RCOOH OH
CH2 CH CH2
O O O
CO CO CO
R R R
(a) CH2CH2CH2CH2 (b) CH2CH=CHCH2 (c) CH2CH=CHCH2CH=CHCH2 (d) CH2CH=CHCH=CHCH2

Scheme 3. Type of fatty acid chain; saturated (a), unsaturated (b), isolated (c) and conjugated (d).
Scheme 2. Synthesis of triglyceride.
Table 1 Some fatty acids in natural oils Name Myristic acid Palmitic acid Palmitoleic acid Stearic acid Oleic acid Linoleic acid Linolenic acid a-Eleostearic acid Ricinoleic acid Formula C14H28O2 C16H32O2 C16H30O2 C18H36O2 C18H34O2 C18H32O2 C18H30O2 C18H30O2 C18H33O3 Structure CH3(CH2)12COOH CH3(CH2)14COOH CH3(CH2)5CH CH(CH2)7COOH CH3(CH2)16COOH CH3(CH2)7CH CH(CH2)7COOH CH3(CH2)4CH CH-CH2-CH CH(CH2)7COOH CH3-CH2-CH CH-CH2-CH CH-CH2-CH CH(CH2)7COOH CH3-(CH2)3-CH CH-CH CH-CH CH(CH2)7COOH CH3(CH2)4CH-CH-CH2-CH=CH(CH2)7COOH
OH CH3(CH2)4CH-CH-CH2-CH=CH(CH2)7COOH O CH3(CH2)3CH=CH-CH=CH-CH=CH(CH2)4C-(CH2)2COOH O
Vernolic acid Licanic acid
C18H32O3 C18H28O3
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636 F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670 Table 2 Some physical properties of fatty acids Name Myristic acid Palmitic acid Stearic acid Oleic acid
a
Viscosity (cP, 110 1C) 2.78 3.47 4.24 3.41
Density (g/cm3, 80 1C) 0.8439 0.8414 0.8390 0.850
Melting point (1C) 54.4 62.9 69.6 16.3
Refractive index (n70) D 1.4273 1.4209 1.4337 1.4449a
Value at 60 1C.
Table 3 Fatty acid composition of various oils Fatty acid Castor oil (%) Linseed oil (%) 5 4 22 17 52 Oiticica oil (%) 6 4 8 8 74 Palm oil (%) Rapeseed oil (%) 39 5 45 9 2 4 2 56 26 10 2 Rened tall oil (%) 4 3 46 35 12 Soybean oil (%) 12 4 24 53 7 Sunower oil (%) 6 4 42 47 1
Palmitic acid 1.5 Stearic acid 0.5 Oleic acid 5 Linoleic acid 4 Linolenic 0.5 acid Ricinoleic 87.5 acid Licanic acid Other
Table 4 Some physical properties of triglyceride oils Name Castor oil Linseed oil Palm oil Soybean oil Sunower oil Viscosity (cSt at 37.8 1C) 293.4 29.6 30.92 28.49 33.31 Specic gravity (201/4 1C) 0.9510.966 0.9250.932 0.8900.893 0.9170.924 0.9160.923 Refractive index (n20) D 1.4731.480 1.4801.483 1.4531.456 1.4731.477 1.4731.477 Melting point ( 1C) 20 to 10 20 3340 23 to 20 18 to 16
Table 5 Iodine values of unsaturated fatty acids and their triglycerides Fatty acid Number of carbon atoms Number of double bonds Iodine value of acid Iodine value of triglyceride 95.0 86.0 173.2 261.6 81.6 258.6
Palmitoleic acid Oleic acid Linoleic acid Linolenic acid and a-Eleostearic acid Ricinoleic acid Licanic acid
16 18 18 18 18 18
1 1 2 3 1 3
99.8 89.9 181.0 273.5 85.1 261.0
Since triglyceride oils vary widely in their physical properties depending on fatty acids in their structure, the choice of triglyceride oil plays
an important role on polymer properties. Linseed oil, for example, is commonly used for the preparation of paint binder, because it consists of
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reactive unsaturated fatty acids curing with atmospheric oxidation. Castor oil is an important reactant for interpenetrating polymer networks (IPNs) because it contains hydroxyl groups capable of reacting with isocyanate and carboxyl groups. It is possible to select fatty acid distribution function of oils via computer simulation and the molecular connectivity in order to produce linear, branched, or cross-linked polymers [4]. Materials prepared by this way can be used to produce pressure-sensitive adhesives, elastomers, rubbers and composites. The most widely used method to characterize material is infrared spectroscopy, particularly Fourier transform infrared (FTIR) spectroscopy. It can also be used for the structural analysis of oils [5]. In Table 6, the absorption bands and the corresponding function/groups are assigned. Nuclear magnetic resonance (NMR) spectroscopy is another important technique for the descriptions of the chemical microstructure of an organic material. The assignment of the relevant peaks for the protons present in triglyceride oils is reported in Table 7. It is possible to calculate the fatty acid content of triglyceride oil from NMR data. The calculation of the surfaces of the peaks corresponding to the methylene groups, for example, gave an assessment of the linoleic acid content [5]. Gas chromatography is also widely used for the determination of fatty acid composition of the oils.
Table 7 Some representative 1H chemical shift values for fatty acids

1
H chemical shift (ppm) Protons (CH3(CH2)nCH CHwhere n 4 3) (CH3CH2CH CH) CH2 CH2C O CH2CH2CH CH CH2C O CH2CH CH Protons of the glyceride moiety CH CH
0.88 0.97 1.21.3 1.6 2.0 2.3 2.8 4.14.3 5.3
3. Oil-based polymers Although the biggest usage area is in the coating industry, in the last decade triglyceride oil-based polymers have been used for many different applications. Some type of polymers prepared from triglyceride oils are listed below.

Oxypolymerized oils Polyesters Polyurethanes (urethane oils) Polyamides Acrylic resins Epoxy resins Polyesteramides
In the following sections preparation methods, properties and uses of oil-based polymers are discussed in more detail. 3.1. Oxypolymerized oils Oxypolymerization is one of the common methods used for the modication of triglyceride oils. When the oils having double bonds are oxidized, they undergo polymerization. During the reaction, the double bonds were consumed (Scheme 4). Some investigators have focused on oxypolymerization mechanism of drying oils [68]. New methods for the analysis of oxidized samples have also received interest [9,10]. Oxidized oils are widely used in the manufacturing of oil-based binders because they give the nal products having high viscosity and good lm properties [3,11]. From the point of design and process control, knowledge of some physical properties such as viscosity and density is essential. How these properties
Table 6 Some representative IR absorpsion band values for fatty acids Absorpsion bands (cm1) 3500 29302850 Functionality
1745 1160 720 1650, 3010 990 970
OH functions corresponding to free glycerol and/or residual moisture CH2 groups (with an additional weak shoulder around 2960 cm1 reecting the presence of terminal methyl groups) COOH groups COC functions of the ester group (CH2)n sequences of the aliphatic chains of the fatty acids Non-conjugated unsaturation of linoleic acid chain for linseed oil Conjugated unsaturation of eleostearic acid chain for tung oil Trans conguration of eleostearic acid chain for tung oil
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change during reaction should be monitored. At that point, in literature, changes in some properties of oxidized oils such as viscosity, density, refractive index, iodine and peroxide values were determined during the reaction and some empirical equations were obtained [12]. Additionally, a kinetic investigation was carried out and, the reaction order and the rate constant were determined. Change in the reaction order with the temperature could be explained with different reaction mechanism for each temperature. Rheological behavior of the nal product was investigated using Bingham, Power-law and Casson
equations. It was found that the sample behaved as non-Newtonian uid at high temperature. It was reported that oxidized soybean oil was prepared via permanganate oxidation with sub/ supercritical CO2 [13]. By this way, a semi-drying oil can be oxidized without using a drying agent as activator. 3.2. Polyesters Polyesters can be synthesized via several routes: polycondensation of hydroxyl acids or a diacid and a diol or by ring-opening polymerization of lactones (Scheme 5). In the last decade, synthesis and usage of biodegradable polymers have been very popular. Especially, biodegradable polyesters are useful materials for medical purposes. In this respect, ricinoleic acid-based copolymers were successfully prepared and characterized [14]. 3.2.1. Alkyd resins One of the oldest polymers prepared from triglyceride oils is alkyd resin produced by the esterication of polyhdroxy alcohols with polybasic acids and fatty acids (Fig. 2). Actually, the preparation of polyester resin from tartaric acid and glycerin was reported by Berzelius dates back as early as 1847. However, the resulting polymer was brittle. In 1901 Watson and Smith used phthalic acid instead of tartaric acid. The resin was also not exible. In 1914 Kienle used fatty acids in the preparation of polyester resin. The resulting alkyd resin exhibited good lm properties. Obviously, chemistry and applications alkyd resins have attracted the interests of many chemists from both academia and industry as can be seen from the huge number of papers and patents covering this eld. This article aims by no means at reviewing all published work but rather intends to illustrate some prominent examples. In this connection the readers attention is also directed to the book solely devoted to this eld [2].
Scheme 4. Oxypolymerization reaction.
(a) (b)
(c)
Scheme 5. Poyester synthesis; polycondensation of hydroxyl acid (a), polycondensation of diacid and diol (b), ring-opening polymerization of lactones (c).
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Fig. 2. Structure of alkyd resin (PA: polyalcohol, PAc: polyacid, FA: fatty acid).
Scheme 6. Preparation of alkyd resin.
Alkyd resins have acquired a good reputation because of their economy and ease of application. Additionally, they are to a greater extent biologically degradable polymers because of the oil and glycerol parts. In general, monoglyceride and fatty acid methods are used to prepare alkyd resin [2]. In the former case, the rst stage is alcoholysis of the oil by a part of the polyol. Then, the free hydroxyls of the
alcoholysis product are esteried by a polyacid. The related reactions are schematically represented in Scheme 6 when glycerol and phthalic anhydride (PA) are used as polyol and polyacid components, respectively. The later method is more often used than the former because it requires no intermediate step. Polyacid, polyalcohol and fatty acid are added from the start and heated. Alkyd resins obtained by this
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640 F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670 Table 8 The chemical structures, molecular weights and acid values of anhydrides Anhydride Code Acid Value (mg KOH/g) 983.4 Formula
way have high viscosity, good drying and hardness properties. Alkyd resins are classied according to their oil length. Oil length refers to the oil percentage of an alkyd. A short oil alkyd contains below 40% of oil. When oil amounts increase between 60% and 40%, it is called medium oil length. Above 60%, the resin is a long alkyd. Oil length is the important factor, which affects the properties of the nal product [3]. Short oil alkyds are most used for baked nishes on automobiles, refrigerators, stoves, washing machines, etc. Long oil alkyds are used in brushing enamels. Generally, a few drying and semi-drying oils, such as sunower, soybean and linseed oils are used in the preparation of oil-modied polyesters. Additionally, new vegetable oils, such as rubber seed, karinatta, orange seed and melon seed oils were used for polyester resin synthesis [1517]. Alkyd resins modied by triglyceride oils are also very common components for offset printing inks [5]. The most commonly used alkyd resins in the printing industry are linseed and soybean oils-based resins. For economical reasons, sunower and rapeseed oils were utilized as oil components for printing ink formulations [18,19]. The viscosity and lm properties of alkyd resins depend on the type and amount of raw materials used for the synthesis. In the literature, four types of anhydride, namely glutaric anhydride (GA), maleic anhydride (MA), PA and succinic anhydride (SA), were used in alkyd resin formulation, and the ow and lm properties were determined [20]. The chemical structures of anhydrides are presented in Table 8. One of the most important lm properties of a coating material is drying time that is the lm formation time. Comparing the drying times of the polymers prepared from different type and amount of anhydride (Fig. 3), for the same anhydride-based samples while anhydride amount increases, drying time decreases. For the same amount of anhydridebased samples, resin prepared from MA has the shortest drying time. 3.2.2. Liquid crystalline alkyd resins Liquid crystalline (LC) polymers are widely used in plastic and ber industry. LC alkyd resins have been studied for reducing volatile organic compound and improving properties of alkyd-type coatings [21,22]. LC phases were formed by grafting: (a) p-hydroxybenzoic acid (PHBA) to hydroxyterminated alkyd resin (Scheme 7a), (b) PHBA to
Glutaric anhydride
GA
Maleic anhydride
MA
1144.2
Phthalic anhydride
PA
757.5
Succinic anhydride
SA
1121.1
carboxy-terminated alkyd resin (Scheme 7b), (c) PHBA to an excess SA-modied alkyd resin (Scheme 7c). Reaction was carried out at room temperature in the presence of p-toluene sulfonic acid (p-TSA) as catalyst. Formed water was removed from the reaction medium by using dicyclohexylcarbodiimide (DCC) for promoting esterication of PHBA with alkyd. Such prepared LC alkyd resin had low viscosity and good lm properties.
3.2.3. High-solid content alkyd resin Production of high-quality organic coatings with low solvent amount is important target in coating industry. Decreasing the viscosity of the polymer reduces the amount of organic solvent. Preparation of a low viscosity coating requires the use of polymers having either a low molecular weight or a narrowed molecular weight distribution. For this purpose, many investigators suggested new methods for preparation of low viscosity resins [2224]. One of the methods involves reaction of carboxylic acids/anhydrides and alcohols with DCC in the presence of pyridine at room temperature. Alkyd resins prepared by this way, have lower Mn and Mw/Mn, and consequently lower viscosity, than those of the corresponding resins obtained by the conventional method.
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350 300 250 200 150 100 50 0 6.24x10-4 MA based-resin PA based-resin SA based-resin GA based-resin Conventional resin
641
Drying Time (min)
8.91x10-4
11.6x10-4
14.3x10-4
Anhydride Amount (mol) for 1 g Oil Part
Fig. 3. Drying times of the resins.
(a)
(b)
(c)
Scheme 7. Preparation of liquid crystalline alkyd resin by three methods.
Reducing organic solvent amount can also be achieved by synthesizing resins having a highly branched structure [25]. For this purpose, star
and hyperbranched structure resins were prepared and tested in the form of varnishes and white enamels. For synthesizing alkyd resins having a
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hyperbranched structure, trimethylpropane and dimethylolpropionic acid were used. In the rst step, saturated polyester with hydroxyl end groups was obtained. Then, alkyd resin was obtained by esterication of polyester with unsaturated fatty acids. On the other hand, star-like-resins with three or four arms formed by esterication of dipenthaerythritol with fatty acids. 3.2.4. Water-soluble alkyd resins Water-based organic coatings are ecologically friendly materials and more economic than solvent-based coatings. For water-soluble applications, mostly alkyd resins with high acid numbers are prepared and neutralized with amines [2628]. Aigbodion et al. [29] used rubber seed oil in the production of alkyd emulsion. Oil was initially treated with different amounts of 220% of MA. Then maleinized rubber seed oils were used to prepare water-soluble alkyd samples. Nakayama [30] described several specic examples of the oil-based resin blend for water-borne paints. Scheme 8 shows the structure of some watersoluble resins used for the preparation of polymer blends. The rst resin (Scheme 8a) was synthesized by the copolymerization of acrylic acid, glycidyl methacrylate esteried with unsaturated fatty acid, styrene and methyl methacrylate. For obtaining the second resin (Scheme 8b), rst, styrene-allylalcohol copolymer was esteried with linseed oil fatty acids and then addition reaction of MA was achieved.
3.2.5. Polyhydroxyalkanoates To alleviate problems associated with degreasing organic solvent amount in paint formulation, polyhydroxyalkanoates (PHAs) are alternative polyesters [3135]. They are optically active, biodegradable, water-insoluble polyesters of carbon, oxygen and hydrogen. The majority of PHAs are aliphatic polyesters. Their general formula is shown in Scheme 9. PHAs are naturally synthesized by a large variety of bacteria. The rst PHA prepared in plants was the homopolymer, polyhydroxybutyrate. But it was too stiff and brittle. Oils have been studied as substrates for PHA preparation. Incorporation of a low amount of longer chain monomers into the polymer increases toughness and exibility, since the crystallinity of the polymer decreases. For this purpose, olive [36], castor [37], tallow [32,38], soybean, sunower (high oleic) and coconut oils [39] and, soybean [40], linseed, tall oil fatty acids [34,41] and other fatty acids obtained from regional oils [42] were used. 3.3. Polyurethanes Polyurethanes are the reaction products of diisocyanates with hydroxyl-containing materials as shown in Scheme 10. Aromatic and aliphatic diisocyanates are used in the polyurethane formulation. Monomers used are directly affective on the polymer properties. The most widely used diisocyanate components are listed in Table 9. 3.3.1. Organic solvent-soluble polyurethanes To obtain oil-modied organic solvent-soluble polyurethanes (urethane oils), diisocyanates were reacted with hydroxyl-containing oils, such as castor oil, or with partial glycerides prepared from oil and glycerol. The overall reaction for the preparation of oil-modied polyurethanes from partial glycerides using hexamethylenediisocyanate (HMDI) may be generalized in Scheme 11.
(a)
Scheme 9. General formula of PHAs.
(b)
Scheme 8. Structure of water-soluble resins. Scheme 10. Preparation of polyurethane.
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F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670 Table 9 Diisocyanate components Component Toluenediisocyanate Code TDI Structure 643
CH3 NCO NCO
Methylene-4, 40 -diphenyldiisocyanate Nafhthalene-1, 5-diisocyanate
MDI NDI
NCO
NCO
Isophoronediisocyanate IPDI
Hexamethylenediisocyanate
HMDI
OCN-(CH2)6-NCO)
Triglyceride oil + Glycerol
Partial glyceride
OCN CH3
OCN
CH2
NCO
O O NH-C-O-((CH2))4O)n-C-NH
CH3 NCO
O O CH2 CH CH2 O C O R O C NH CH2

6 NH
O C n
Scheme 12. Formula of PBTDI.
Scheme 11. Preparation of partial glycerides and oil-based polyurethane.
When the polymers are prepared from drying and semi-drying oils, such as sunower and linseed oils, they can be used in the paint formulation because of their good lm properties. In a study, polymers were prepared from three kinds of diisocyanates, toluene 2,4-diisocyanate (TDI), HMDI and poly(1,4-butandiol) TDI (PBTDI) [43]. Sunower oil partial glycerides were used as polyol component. In this study, the effects of amount and type of diisocyanate component on the lm properties of polymer were investigated. Depending on the monomer structure used, polymers showed various lm properties. Polymers based on aromatic diisocyanates (TDI and PBTDI), for example, had good water resistance. Additionally, with greater amounts of diisocyanate components in the polyurethane formulation, the shorter drying time was achieved. The monomer structure is also effective on the ow properties. For investigating the effects of
monomer ratio and type on the ow properties, polymers were prepared from two different diisocyanates at three different monomer concentrations [44]. TDI and PBTDI were used as diisocyanate components, and sunower oil partial glycerides were used as polyol component. In the polymer preparation, the lowest diisocyanate concentration was 6.38 104 mol/g polyol, and the highest diisocyanate concentration was 12.61 104 mol/g polyol. Although both diisocyanates have aromatic structure, for the same monomer concentration PBTDI-based samples have higher viscosity than TDI-based samples. Because of the existence of two aromatic rings per a molecule in PBTDI (Scheme 12), the chain of polymer was not exible. Apparently, this causes an increase of viscosity. Some various seed oils, Ecballium elaterium and P. mahaleb, were used as the oil component for the preparation of oil-modied polyurethanes [45]. Since these oils contain conjugated trienoic acids, polymers prepared from them have good lm properties such as short drying time, good water, alkali and acid resistances. Oil-modied polyurethane lms were prepared from HMDI and/or MDI for wound-dressing applications [46]. It was found that the amount and type of diisocyanates affected the lm and
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mechanical properties, and gas permeabilities of polymeric membranes. Notably, lms were exible and permitted to ow oxygen and carbon dioxide. For the preparation of millable polyurethane elastomers, difunctional castor oil or its blends with poly(propylene glycol) with two different ratios of 1,4-butane diol as chain extender and TDI were used as reactants [47]. Investigation of physical, mechanical and thermal properties showed that the elastomers obtained could be used for industrial applications. 3.3.2. Water-soluble polyurethanes Water dispersion of polyurethanes is usually prepared by quarternizing carboxyl acid groups on the backbone by tertiary amines. The most used acid monomer is dimethylol propionic acid. In order to prepare oil-based polyurethane resin, malenized fatty acid can be used instead of dimethylol propionic acid [48]. While malenized fatty acid part provides water dispersion, fatty acid chain provides air drying. Malenized oil product could be prepared by two procedures; a. reaction of oil with MA and then addition of glycerol (Scheme 13), b. reaction of glycerol, methylethyl ketone (MEK) and fatty acid, and addition of MA (Scheme 14). After preparation of malenized oil product, diisocyanate component was reacted with the prepared product to give oilbased polyurethane. Polyurethanes thus obtained exhibited good physical and mechanical properties. 3.3.3. Interpenetrating polymer networks IPNs are combinations of two or more polymer in network form [49,50]. One or more polymer(s) is
synthesized and/or crosslinked in the presence of the other. Polyurethanes, polystyrene, poly(methyl methacrylate) and poly(ethyl acrylate) are the most common polymers that can be used in the preparation of IPNs. Castor oil is widely used for the preparation of polyurethane for IPNs. For this purpose, castor oil is reacted with a diisocyanate to form a polyur-
CH2-OH CH -OH CH2-OH
+ O C
CH3 CH2-CH3
CH2-OH O CH3 O CH2 -CH3
+ H2O
Fatty acid
CH2-O-COO CH3 O CH2 -CH3 O O O O O CH2-O-COO CH3 O CH2 -CH3

H2O
CH2-COOH CH -COOH CH2-O-CO CH -OH CH2-OH
Scheme 14. Maleinization of triglyceride oil.
O O CH2-O-CO CH-O-CO CH2-O-CO O + O O Glycerol CH2-COOH CH-CO-O-CH2 CH-OH CH2-OH CH2-O-CO CH-O-CO CH2-O-CO O
CH2-O-CO CH-O-CO CH-O-CO
Scheme 13. Maleinization of triglyceride oil.
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(a)
(b)
Scheme 15. Structures of a semi-IPN (a) and an IPN (b).
ethane network, followed by swelling with vinyl or acrylic monomer using an initiator. If a crosslinking agent is not used for the second polymerization, only a polyurethane network will result. In this case, the polymer network is called a semi-IPN. The structures of an IPN and a semi-IPN are shown in Scheme 15 [51]. IPN was rst synthesized from castor oil by Yenwo et al. [52]. The same research group prepared IPN from castor oil and TDI to form polyurethane, followed by polymerization of styrene and divinylbenzene in the presence of benzoyl peroxide at 80 1C [53]. In almost all the published studies, researchers focused on physical, thermal and/or mechanical properties of IPNs. A large number of examples are presented in tabular form in Table 10 [5499]. 3.3.4. Urethane alkyds Urethane alkyds (uralkyds) are one of the most common oil-based polymers for coating purposes, because they have superior lm properties as compared to traditional alkyd resins. In the rst step of the synthesis, triglyceride oil was reacted with a polyol, and then a dianhydride and a diisocyanate were added separately to the reaction mixture. Since cured uralkyds is elastomeric in nature, they are used to develop IPNs (Scheme 16) [100102]. 3.4. Polyamides The most common application of oil-modied polyamides is in paint industry. For modifying paint ow some thixotropes can be prepared from dimer acids obtained from tall and soybean oils, and amines (Scheme 17) [103]. Thixotropy prevents setting and sagging, and cause easy application and improves lm appearance.
Thixotropy is an increase of viscosity in a state of rest and a decrease of viscosity when submitted to a constant shear stress [104]. In other words, thixotropy is time-dependent uid behavior in which the apparent viscosity decreases with the time of shearing and in which the viscosity recovers to, or close to, its original value when shearing ceases [105,106]. In polymer systems, weak intermolecular interactions, such as hydrogen bonds can cause a thixotropic behavior [107]. Chemical bonds can be broken reversibly under ow achieved by mechanical actions. In Schemes 18 and 19, hydrogen bonding between different groups is shown. One of the most commercially used polymer, Nylon 11, was developed from castor oil [99,108]. The product had a wide range of exibility, excellent dimensional stability and electrical properties, good chemical resistance and low cold brittleness temperature. 3.5. Vinyl polymers 3.5.1. Classical methods One of the oldest methods for the modication of triglyceride oils is the copolymerization of drying and semi-drying oils with vinyl monomers like styrene, a-methylstyrene or cyclopentadiene. Since the products have improved lm properties, they can be used in the formulation of surface-coating materials. Styrene is the most important monomer for this purpose [3]. Styrene polymerization with oils involves free radical initiated polymerization in classical method. Generally, free radical type initiator, such as benzoyl peroxide and ditertiarybutyl peroxide, has been used to accelerate the copolymerization reaction. Hewitt and Armitage [109] proposed two types of reaction mechanism for conjugated and non-conjugated oils (Scheme 20). According to these authors, styrene chains are propagated across the conjugated dienes as in the styrene-butadiene reaction, while non-conjugated fatty acid radicals serve to modify the growth of styrene chains by a chain transfer mechanism. Styrene-oil copolymerization has been investigated by several other researchers [110114]. Saxena et al. discussed the polymerization in view of reaction mechanisms, preparation techniques, raw materials and, analysis and properties of the products [115,116]. Linseed, tung, soybean, sunower and oiticica oils and dehydrated castor oil (DCO) obtained by dehydration of castor oil, are widely used in the
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646 F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670 Table 10 Interpenetrating polymer networks based on castor oil-polyurethanes and vinyl/acrylic components Polyurethane component Polyol CO Isocyanate TDI St Preparation of both toughed plastic and reinforced elastomer compositions, and determination of their stress-strain and impact loading behavior Both the plastic and the elastomeric IPNs proved tougher than their corresponding homopolymer networks. Elongations at break of about 816 percent were found for the plastics, while the elastomers ranged from 55 to 125 percent. [54] Vinyl/Acrylic component Aim of study Comment Reference
CO
TDI
St
Determination of morphology and glass transition behavior of IPNs Determination of correlation of mechanical property, crosslinked density and thermogravimetric behavior of IPNs Investigation of the effect of PU/polystyrene ratio on morphology, chemical resistance, thermal and mechanical properties
A two-phase morphology and [55] two well-dened glass transitions near their respective homopolymer glass transitions emerged. A marginal increase in tensile [56] strength and crosslink density from CO polyurethane to IPN prepared from the ratio of 60% polyurethane:40% polystyrene divinyl benzene. [57] The incorporation of polystyrene component into PU improved the tensile modulus. Thermal decomposition of IPNs occurred in four different steps because of complicated structure of IPNs. Two distinct phases were indicated. Mechanical properties showed [58] a signicant improvement beyond a critical styrene level (25% by weight). % elongation at break was determined a maximum at 40% styrene. With increasing concentration of crosslinker mechanical properties improved. IPNs exhibited good mechanical properties and phase mixing behaviour. Transparency and hardness increased because of increasing in crystal size and strain. [59]
CO
TDI
DVB, St
CO
MDI
St
CO
MDI
St
Investigation of the effect of PU/polystyrene ratio and amount of crosslinking agent on mechanical properties
CO
MDI
St
Synthesis of IPNs and determination of morphogical and mechanical properties Characterization of physical, optical and X-ray diffraction properties of IPNs before and after extraction of polystyrene Generation of computersimulated concentration
CO
MDI
St
[60]
CO
MDI
St
Computer-simulated [61] concentration proles of aqueous salt solutions through
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F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670 Table 10 (continued ) Polyurethane component Polyol Isocyanate proles in IPNs membranes IPN membranes were generated with Fick s secondorder differential equation, and the results were examined in terms of diffusion anomalies. Tough and transparent lm [62] wer obtained by the transfer moulding technique. Vinyl/Acrylic component Aim of study Comment Reference 647
CO
IPDI
St
Investigation of the mechanical, thermal and dielectric relaxation properties, and morphology of IPNs Determination morphology and mechanical properties of IPNs Preparation of novel dielectrics from IPNs, and determination of the effects of monomer type, composition on the dielectric properties Determination of the effect of vinyl polymer or polyurethane amount in IPN on morphology and thermalproperties
CO
TDI
St
The tougness of IPNs [63] increased with degreasing domain size of the polystyrene dispersed phase. IPNs behave like [64] homogeneous materials due to topological interpenetration of the components during IPN formation The polystyrene phase size of [65] IPN was shown to decrease with increased crosslinking of the CO component and with increased polystyrene contents. Two distinct glass transitions were observed for IPNs. [66] IPNs exhibited better resistance to chemical reagents and poor solubilities in organic solvents. They possessed greater thermal stability than that of homopolymers (PU and PMMA).They behaved like semiconductors. Toughness in the elastomeric PU increased with the increase in the PMMA content of the IPNs. [67] SEM micrographs indicated homogeneous phase domains of PU and PMMA. IPNs were less resistance to alkali. They showed complete weight loss around 550 1C. They were ranked as insulators. IPNs showed excellent mechanical properties and thermal stability. [68]
CO
TDI
BMA, MMA, St
CO
TDI
MMA, St
CO
MDI
MMA
Preparation of IPNs and determination of morphology, their resistance to chemicals, thermal behavior, and mechanical and dielectric properties
CO
HMDI
MMA
Investigation of the effect of reaction conditions and NCO/OH ratio on morphology, chemical resistance, thermal, dielectric and mechanical properties Determination of properties and morphology of IPNs
CO
TDI
MMA
CO
TDI
MMA
[69]
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648 Table 10 (continued ) Polyurethane component Polyol Isocyanate Preparation of BaTiO3 superne ber/IPNs nanocomposites Synthesis of polyaniline lled IPNs and determination of their physico-mechanical, electrical, chemical, thermal and surface morphology The domains of the simultaneous systems were on a nanometer scale. Incorporation of polyaniline [70] into IPNs improved tensile strength. All the electrical properties of polyaniline lled IPNs were increased with increase in polyaniline content. Thermal decomposition of lled IPNs occurred in three different stages. There were two distinct phases due to individual component networks. The crystal growth was observed above 5% polyaniline addition to IPN. Thermogravimetric analysis of [71] the polymers was conducted using a computer analysis method for assigning the kinetic mechanism. [72] All IPNs decomposed by about 95 wt% in the temperature range 400500 1C. The degree of crystallinity increased with increase of the prepolymer content. The heterogeneity gradually degreased and the morphology changed from a discontinuous to a continuous phase, when the prepolymer content increased from 35 to 45%. IPNs decomposed around 600 1C [73] Vinyl/Acrylic component Aim of study Comment Reference F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670
CO
TDI
MMA
CO
IPDI
AA, MAM
Synthesis of IPNs and determination of their thermal properties
CO
HMDI
MAM
Investigation of the effect of prepolymer (pre-PU) content on thermal properties, morphology and crystallinity of IPNs
CO
IPDI
AA, MAM
Synthesis of IPNs and determining of their chemical and thermal properties Investigation of the effect of NCO/OH molar ratio on morphology, optical, dielectric and mechanical properties Investigation of the effect of NCO/OH ratio on chemical resistance, thermal, dynamicalmechanical properties Determination of the effects of compositional
CO
MDI
EMA
IPNs exhibited better resistance to chemicals and poor solubility in organic solvents. IPNs exhibited better resistance to chemicals and poor solubility in organic solvents.
[74]
CO
IPDI
EMA
[75]
CO, PEG
TDI
BMA, EMA
Both BMA and EMA were [76] good choice for the monomer
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F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670 Table 10 (continued ) Polyurethane component Polyol Isocyanate variation of IPNs on phase transfer catalytic efciency and mechanical properties, and determination of conductivity of IPNs Synthesis of IPNs and determination of their physicochemical properties Using of HEMA in the IPNs preparation and determination of chemical, mechanical and thermal properties of IPNs in the synthesis of IPNs for use as phase transfer catalysts and ion conducting materials. IPNs showed good mechanical properties. IPNs decomposed at a very [77] high temperature. [78] IPNs were partly soluble in some of the solvents. Interpenetration of PU as a separate phase in polyviniyl brough about the enhanced modication in mechanical properties. There was a rapid weight loss from 40% to 90% in the temperature range of 400500 1C and almost all the IPNs decomposed completly around 600 1C. [79] IPNs were elastomers and exhibited good mechanical properties. They behaved like insulators. Vinyl/Acrylic component Aim of study Comment Reference 649
CO
TDI, HMDI, MDI
BA, BMA, EA, EMA HEMA
CO
HMDI
CO
IPID
BA
Investigation of the effect of NCO/OH molar ratio on morphology, chemical resistance and thermal, dielectric and mechanical properties Investigation of the effect of PU/poylacrylonitrile ratio on physical, chemical, optical and mechanical properties of IPNs
CO
MDI
AN
[80] With increase in content of AN the tensile and tear strengths, and tensile modulus increased. The crystal size distribution changed signicantly with increase of concentration of AN monomer. Optical properties showed improvement with increase of AN content. IPNs were stable in all standart reagents but became brittle and lose their gloss in methyl ketone, toluene snd CCl4. Tg s of all IPNs were determined around 40 1C. All IPNs exhibited good mechanical properties. [81]
CO
TDI
BA
Syntesis of IPNs and determination of their resistance to chemical reagents, thermal stabilities and mechanical properties
CO
TDI
2-Hydroxyethyl methacrylate
Investigation of the effect of PU content, activator, acrylic cross-linker on the kinetics of formation for IPN Investigation of the effect of NCO/OH ratio on
The rate of formation of the [82] IPN was found faster than were the rates of the individual network formation. Increasing the NCO/OH [83] ratios in the IPNs, the thermal stability increased because of
CO
TDI, HMDI
2-Hydroxy-4methacryloyloxy acetophenone
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650 Table 10 (continued ) Polyurethane component Polyol Isocyanate morphology and thermal behavior more crosslinking. With increase in the monomer content, nature of homogeneity of the phase increased. [84] IPN decomposed in three distinct steps. The activation energy for the second step is higher, which suggests that the recrosslinking occurs at a lower rate. The activation energy for the second step is lower, which suggests that the depolymerisation occurs at a faster rate. IPNs are tough materials having synergistic properties of their corresponding homopolymers. [85] Vinyl/Acrylic component Aim of study Comment Reference F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670
CO
IPDI
Cardanyl methacrylate
Synthesis of IPNs and determination of the kinetic parameters involved in the thermal degradation, by using the computerised LOTUS package method
CO
TDI
Mixture of EA and EGDMA
Determination of thermal, mechanical, mechanothermal, morphological and dielectric properties of IPNs Investigation of the effect of vinyl/acrylic monomer type, and NCO/OH molar ratio on mechanical and thermal properties of IPNs
CO TDI Various monomers AN was the best monomer in [86] the formulation of one type of IPNs. The apparent crosslink density and tensile strength of the IPNs increased with NCO/ OH molar ratio. [87] AN is a good monomer for synthesizing (polyether-castor oil) PU/vinyl or methacrylic polymer, but is a poor monomer for preparing (polybutadiene-castor oil) PU/ vinyl or methacrylic polymer. Both polyether-based and polybutadiene-based behaved as elastomers at optimum conditions of the synthesis. Dynamic mechanical and [88] dielectric spectroscopies can be used for stuying semi-IPNs. Each method has shed light on different aspect of the molecular motions. [89]
CO
NCO-terminated polyether, NCOterminated polybutadiene
AN, BMA, EMA, Investigation of the effect MMA, St of synthesis conditions on mechanical properties of IPNs
CO
TDI
PVP
Investigation of the structure of semi-IPNs by associated dynamic mechanical and dielectric spectroscopies. Semi- and full IPNs were prepared with similar composition by swelling the base networks with the appropriate methacrylate monomers.
CO
Isocyanatoethyl methacrylate
Preparation of UV-curable IPNs
TDI
MMA
[90]
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F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670 Table 10 (continued ) Polyurethane component Polyol Linseed oil modied CO Isocyanate Investigation of the effect of linseed oil amount on mechanical an thermal properties of IPNs MMA Modied castor oil with 30 wt% linseed oil showed higher tensile and hardness and lower elongation. Vinyl/Acrylic component Aim of study Comment Reference 651
Linseed or tung IPDI oil modied CO
Determination of the effect IPNs prepared from linseed oil [91] of oil type on the IPNs modied CO, showed higher properties tensile strength, hardness, and better compatibility than unmodied CO-based IPNs. Determination of mechanical and thermal behavior of semi- and fullIPNs [92] Semi-IPNs exhibited higher tensile strength and density but lower elongation than the corresponding full-IPNs. Semi-IPNs showed two Tg values. Full-IPNs showed single Tg. Enhanced mechanical [93] properties were obtained with an increase in the NCO/OH ratios. Semi-IPNs with 2030% [94] chlorinated rubber were found to possess sperior physical and morphological properties [95] IPNs prepared by modiedCO showed improved properties over unmodied CO. Incorperation of poly(2EOEMA) to modied-CO polyurethane increased the toughness, degreased the elongation, and improved the thermal stability. [96] Glycerol modied PU IPNs exhibited good tensile and tear strengths and chemical resistance. Thermal and chemical resistance of IPNs were unaffected by the change in NCO/OH ratio and PU/ PMMA composition.
CO and hydrogenated CO
IPDI
MMA
Hydrogenated CO
IPDI
BMA
Determination of the effect of NCO/OH ratio on the mechanical properties of IPNs Investigation of the effect of NCO/OH molar ratio on morphology, thermal, electrical and mechanical properties of semi-IPNs Synthesis of IPNs and determination of the effect of NCO/OH ratio of the PU on morphology, chemical, mechanical and thermal properties of IPNs
Crosslinking CO TDI, HMDI
Chlorinated rubber
Glycerol modied-CO
HMDI
2-EOEMA, EGDMA
Glycerol modied CO
TDI
MMA
Investigation of the effect of polyol modication, change in NCO/OH ratio and PU/PMMA composition on the chemical, thermal and mechanical properties of IPNs
Castor oil based IPNs A review 50, 97, 98, 99
CO, castor oil; IPN, interpenetrating polymer network; PEG, poly(ethylene glycol); PU, polyurethane; PMMA, poly methyl methacrylate. HMDI, hexamethyle diisocyanate; IPDI, Isophorone diisocyanate; MDI, diphenyl methane diisocyanate; TDI, toluene diisocyanate. AA, acrylamide; AN, acrylonitrile; BA, butyl acrylate; BMA, n-butyl methacrylate; DVB, diviniyl benzene; EA, ethyl acrylate; 2-EOEMA, 2-Ethoxyethyl methacrylate; EGDMA, Ethylene glycol dimethacrylate; EMA, ethyl methacrylate; HEMA, 2-hydroxyethylmethacrylate; MAM, methacrylamide; MMA, methyl methacrylate; PVP, polyvinylpyrrolidone; St, styrene.
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Triglyceride oil + Glycerol Partial glycerides O C O C O O (C O C O CH2 CH CH2 O)n O CO R
OCN (CH2 )6 NCO
O (NH CO (CH2 )6 NH CO O CH2 CH CH2 O (C O CO R Uralkyd resin (UAR)
O C O CH2 CH CH2 O)n )m O CO R
UAR + CH2 CH
IPN
Scheme 16. Synthesis of IPN based on uralkyd resin/polystyrene.
Scheme 17. Preparation of an oil-based polyamide.
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Scheme 18. Hydrogen bonding causing thixotropy.
H C-C
O N-H
H N-C
O N-H O-C
O N-H Urethane
Amide
Urea
Scheme 19. Potential hydrogen bonding structures.
preparation of styrenated-oil products. DCO, tung and oiticica are the ideal oils for styrenation due to their conjugation. Other oils are used after applying some modications, such as blowing, isomerization, or blending with conjugated oils, in order to get homogeneous product. Thermosetting oil-based polymers were also obtained by cationic copolymerization of regular soybean oil, low saturation soybean oil and conjugated low saturation soybean oil with divinylbenzene [117]. Conjugated low saturation soybean oil-based polymers exhibited the highest moduli and thermal stabilities, because of their low unreacted free oil content.
Scheme 20. Styrenation of conjugated and non-conjugated fatty acids.
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Although vinyl modied triglyceride oils are mainly used in paint industry, in recent years there has been increasing trend towards their use as biopolymers [118,119]. For example, Li and Larock [120123] reported the preparation of tung oilstyrene-divinylbenzene copolymers by thermal polymerization. The resulting polymers were light yellow color, transparent, rigid, tough and thermally stable below 300 1C. The same research group prepared thermosetting polymers by cationic polymerization of tung, soybean and sh oils. The polymerization was initiated by boron triuoride diethyl etherate. 3.5.2. Macroinitiator/macromonomer method An alternative method, macroinitiator method, was suggested for styrenation of oils [124]. First, a low molecular weight azo initiator incorporated to oil part into two steps, and then in the presence of styrene free radicals were generated by the thermal decomposition of the azo groups and the oil-styrene copolymers was obtained (Scheme 21). This process does not require an additional initiator and allows styrenation of drying and semidrying oils without any pre-treatment. Since active radical sites were directly generated on the oil backbone, homopolys-
tyrene did not form as a by-product. By using this technique, coating polymers were prepared using thermally splitted secondary esters of castor oil (Scheme 22) and interesterication product of linseed and castor oils (Scheme 23) [125,126]. The styrenated products obtained by the macroinitiator method showed good lm properties. Another method, namely the macromonomer (macromer) technique, has been reported [127,128]. In this case, rst the macromer of the following structure (Scheme 24) was prepared through the reaction of hydroxyl containing oil specimens with a vinyl monomer such as acrylic acid and methyl methacrylate. Then this monomer was homopolymerized and copolymerized with styrene. In another study, rst, transesterication product of linseed oil and castor oil was used to obtain a macromer. Subsequently, the macromer was subjected to homo- and copolymerization reactions in the same manner (Scheme 25) [129]. In some studies, styrenated samples were prepared via hydroxymethylation, followed by maleinization, of soybean and sunower oils [130132]. The resulting maleate half esters were copolymerized with styrene by free radical initiation
Scheme 21. Styrenation of triglyceride oil via macroinitiator method.
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Scheme 22. Modication of castor oil.
Scheme 23. interesterication of castor oil and linseed oil.
Scheme 24. Styrenation of triglyceride oil via macromonomer method.
(Scheme 26). Another method involving epoxidation and ring opening processes for styrenation of triglyceride oils was suggested. In the rst step,
epoxidation of double bonds in fatty acid chain was achieved. Subsequently, ring opening of epoxy groups with acrylic acid yielded hydroxyl acrylated triglyceride oils [130,133]. As shown in Scheme 27, free radical polymerization of hydroxyl acrylated macromonomer gave the desired polymers. Simultaneous addition of bromine and acrylate to the triglyceride double bonds was achieved by Eren and Kusefoglu [134]. By this way, soybean and sun ower oils were bromoacrylated by a one-step route. Soybean oil gave a higher acrylate substitution than the other. The bromoacrylation yields for soybean and sunower oils were 75% and 55%, respectively. Homopolymers and copolymers of bromoacrylated sample were obtained by thermal and photopolymerization techniques. While soybean oil-based polymer was a rigid, bromoacrylated sunower oil-styrene copolymer-exhibited semi-rigid properties. The authors suggested that by
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mixing bromoacrylated soybean- and sunower oils with small amount of antimony oxide or hydrated zinc borate, polymers having good ame-retardant properties could be prepared. An improved method was also described for hydroxybromination of triglycerides and fatty acid methyl esters in one step, with good conversion, using NBS/acetone/ water mixture (Scheme 28) [135]. After preparing acrylated hydrobromide derivative of sunower oil
it was successfully homo- and copolymerized in the presence of thermal or photo initiator. 3.5.3. Fatty acid- or oil-grafted polymers The blending of immiscible two or more polymers has become increasingly important way for developing new materials having good properties [50,136]. Since it is difcult to obtain good mechanical properties and stable morphology via simple blend, some preformed graft or block copolymers are usually added as compatibilizers. Moreover, these copolymers are synthesized during the blending through polymerpolymer grafting reactions using functionalized polymers. Acrylic acid, methacrylic acid, glycidyl methacrylate, etc. are the most commonly used monomers for preparing functionalized polymers obtained by graft copolymerization. Additionally, a number of studies on long-chain unsaturated fatty acids as graft monomer have been reported. In these studies, the mechanism, reactivity and kinetics of grafting of long-chain carboxylic acids onto acrylonitrile-butadiene-styrene (ABS) terpolymer were investigated [136138]. For biomedical applications, graft copolymers were prepared from linseed and soybean oils and methyl methacrylate, styrene or n-butyl methacrylate [139,140]. Oils were rstly converted to polymeric peroxide under atmospheric conditions or O2 gas at room temperature. Then, it was used to initiate the graft copolymerization of vinyl monomer. It was found that poly(methyl methacrylate)based graft copolymers can be used for biomedical applications.
CH2-O-CO CH -O-CO CH2-O-CO CH2-OH
Castor oil + Linseed oil
Interesterification products CH2=CH COOH CH O CO CH=CH2
Styrene
(CH2
CH O CO CH)n
(CH2-CH)m
Styrenated oil
Scheme 25. Styrenation of castor oil and linseed oil mixture via macromonomer method.
CH2-O-CO CH -O-CO CH2-O-CO
Paraformaldehyde EtAlCl2 0C, 2 hr O O
CH2-O-CO CH -O-CO CH2-O-CO CH2-OH O
CH2-O-CO CH -O-CO CH2-O-CO CH2-O-CO-CH Styrene HOOC-CH
Polymer Network
Scheme 26. Stynthesis and polymerization of maleate half ester-based triglyceride oil.
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O O O O O O O COOH O O O O O OH O O O
O O O
Polymer
O O
Scheme 27. Synthesis of macromonomers by ring opening of epoxy groups and subsequent polymerization.
CH2-O-CO CH -O-CO
NBS/Acetone/H2O
CH2-O-CO CH -O-CO CH2-O-CO Br OH
CH2-O-CO
CH2=CH-COCl
CH2-O-CO CH -O-CO CH2-O-CO Br

Scheme 28. Hydroxybromination and acrylation of triglycerides.
O-CO-CH=CH2
3.6. Epoxy resins Epoxidized oils are important plasticizers and stabilizers for PVC. Mono- and di-unsaturated fatty acids and their esters can be converted to epoxy (oxirane) derivatives by chemical oxidation [3]. The reaction occurred at the double bonds on the fatty acid chains. Oxidation of oleic acid in the presence of peracetic acid is given in Scheme 29. Enzymatic epoxidation of unsaturated fatty acids was also achieved by Uyama et al. [141]. Epoxidized oils can be used for obtaining various types of polymers by taking advantage of the reaction of the active hydrogen such as those present in alcohol, amine and carboxylic acid. In this approach, polymer preparation is achieved in two steps. Typically, an intermediate product
CH3(CH2)7CH = CH (CH2)7 COOH + CH3CO3H (oleic acid)
CH3(CH2)7CH - CH (CH2)7 COOH + CH3CO2H O (9,10-Epoxystearic acid)

Scheme 29. Epoxidation of oleic acid.
having hydroxyl groups was prepared in the rst step (Scheme 30) and subjected to subsequent condensation to yield desired polymers, such as
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polyurethane, polyester, etc. Linseed oil basedpolyurethanes can be obtained from the reaction of hydoxylated linseed oil prepared from epoxidized linseed oil, and diisocyanate (Scheme 31) [142]. In
OH RC H CH R + R' OH O RC H CH OH R' OH RC H CH R + O R' NH 2 R CH CH NH R' OH RC H CH R + R' COOH O RC H CH OC O R R' R R
Scheme 30. Reaction of epoxides with active hydrogen containing compounds.
another study, epoxidized linseed oil was polymerized with anhydrides in one-step in the presence tertiary amines or imidazoles catalysts [143]. Epoxidized oils can undergo homopolymerization as well [144]. Vernonia seed oil contains naturally epoxy acids in its structure (Scheme 32). A UV-curable resin was synthesized via transesterication of vernonia fatty acids with a hyperbranched hydroxy functional polyether [145]. The resin was cationically polymerized in the presence of vernolic acid methyl ester as diluents. Epoxidized seed oils are widely used for the synthesis of cationic UV-curable coatings [146 154]. Interestingly, epoxynorbornene oils showed higher photopolymerization rate than epoxidized oils [155]. Epoxynorbornene oils were prepared via DielsAlder reaction of dicyclopentadiene with oil at high pressure, followed by epoxidation. Additionally, epoxynorbornene oils were successfully
CH3COOH + H2O2 CH=CH
H+
CH3COOOH + H2O + CH3COOOH H+
O CH - CH O CH - CH + CH3COOH H2O2, H+ OH2 OH CH - CH OH2 -H+ OH CH3 NCO OH CH - CH OH CH - CH
NCO O )n CH - CH NH-CO O CH3 ( NH

Scheme 31. Preparation of polyurethane prepared from epoxidized oil.
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Scheme 32. Structure of vernonia seed oil.
used in the formulation of UV-curable organic inorganic hybrid lms [156]. From the sunlight-cured methacrylate of vernonia oil, IPNs were prepared in combination with a cured epoxy resin [157]. For the preparation of water-soluble polymers, epoxy resins are reacted with drying oils/drying oil fatty acids [158,159]. The obtained polymers were either half esters of dicarboxylic epoxy esters, or maleinised epoxy esters of unsaturated fatty acids. All polymers become water soluble on neutralization with dimethyl ethanolamine. The former type of polymers was prepared by a two-step procedure. In the rst step, preparation of epoxy resin esters from drying oil fatty acids and epoxy resin was achieved. In the second step, the free hydroxyl groups present in the epoxy resin esters were semi-esteried with polybasic acid anhydrides (Scheme 33). Maleinised fatty acid epoxy resin esters are also prepared in two stages (Scheme 34). Drying oil fatty acids were reacted with epoxy resin, followed by the reaction with MA. The product has very good hydrolytic stability when compared with half esters of dicarboxylic epoxy esters, and maleinised epoxy resin fatty acid esters. 3.7. Polyesteramides Alternating polyesteramides are regular copolymers and combine the good properties of polyester and polyamide [160]. 1,4-Diaminebutane terephthalate is a typical example for polyesteramide family (Scheme 35(a)). If the alkyl chain (R1) is long enough, the Tg of the polymer is below room temperature, so the material shows thermoplastic elastomer behavior. If the R1 is a short chain alkyl, the Tg is above room temperature and the polymers can be used as an engineering plastic. Oil-modied polyesteramide resins are amidemodied alkyds that have improved properties over normal alkyds (Scheme 35(b)). A number of linseed oil-based polyesteramides were obtained for using
Scheme 33. Half esters of dicarboxylic short oil epoxy esters.
as surface coating materials [161163]. Polymers were synthesized into two steps; preparation of N, N-bis(2 hydroxyethyl) linseed oil (HELA) from oil and diethanolamine, and preparation of polyesteramide from HELA and phthalic acid (Scheme 36). In order to improve lm properties, linseed oilbased polyesteramid was modied with TDI. The presence of urethane linkage in the polymer improves adhesion, toughness, and water and chemical resistances [164,165]. Nahar (Mesua ferrea) seed, soybean and Pongamia glabra oils were also used in the preparation of polyesteramides [166168]. Soybean oil-based polyesteramide urethane was suggested for biomedical applications after lling with boron, because it exhibited anti-microbial properties. 3.8. Polynaphthols In the preparation of articial urushi, triglyceride oils were used. Urushi is a typical Japanese traditional lacquer extensively used in art and household materials. The main components of urushi are urushiols and catechol derivatives bearing a C15 unsaturated hydrocarbon chain. For the preparation of articial urushi, C18 unsaturated
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Scheme 34. Maleinised epoxy ester of unsaturated fatty acids.
4. Metathesis of oils Catalytic metathesis of olens was rst investigated by Banks and Bailey [176]. In metathesis reactions, olens are converted into new olens via an exchange of alkylidene groups (Scheme 37(a)). The catalytic metathesis of fatty acid esters was rst described by Van Dam et al. [177]. Methyl oleate was converted into equimolar amounts of 9-octadecene and dimethyl ester of 9-octadecene dioic acid in the presence of WCl6(CH3)4Sn (Scheme 37(b)). Boelhouwer discussed the metathesis of fatty acid esters in detail [178]. Using the same catalyst system, Erhan et al. [179] achieved metathesis of soybean oil. The olen metathesis of vegetable oils has been suggested to produce an improved drying oil. Chlorinated
(a)
(b)
Scheme 35. Structure of polyesteramides.
hydrocarbon chain derived from plant oils was connected with the catechol group through as ester linkage [169172]. Cross-linkable polyphenols were obtained from triglyceride oils [173175].
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Scheme 36. Synthesis of polyesteramides from triglyceride oils.
(a) (b)
(c)
(d)
Scheme 37. Catalytic metathesis reactions.
solvent or chlorobenzene is used as a solvent in this catalyst system. It should be pointed out that WCl6(CH3)4Sn system is extremely sensitive to moisture and oxygen, and has disposal problem because of the solvent. Alternative effective catalyst system, Grubbs ruthenium catalyst (Cy3P)2Cl2Ru CHPh was used in the metathesis of oils [180]. Notably, the preparation process in the case of this catalyst is environmentally friendly. Olen metathesis has a variety of polymer preparation through ring-opening metathesis polymerization (ROMP) (Scheme 37(c)) and acrylic diene metathesis polymerization (ADMET) (Scheme 37(d)). Grubbs ruthenium catalyst has been employed in ADMET polymerization of soybean oil [181]. In this work, after evaluation of ADMET polymerization catalysts, Mo-based and
Ru-based catalysts, ethylene glycol dioleate and glyceryl trioleate were prepared as a model reactant and their ADMET polymerization was investigated (Scheme 38). Then, ADMET polymerization of soybean oil was succeeded and a variety of polymers, from sticky oils to rubbers, were prepared. Olen metathesis was applied to triglyceride oils in order to prepare various types of polymers, such as polyolens, polyesters, polyethers (Scheme 39) [182,183]. For this purpose, unsaturated fatty acid methyl esters were obtained from oils, followed by conversion of methyl esters to o-unsaturated esters and a-olens by metathesis with ethylene. In the reaction, heterogeneous rhenium or homogeneous ruthenium catalysts were used. To prepare polyolens, o-unsaturated esters were copolymerized with ethylene. Polyesters were obtained by
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(a)
(b)
Scheme 38. ADMET polymerization of fatty acid esters.
Scheme 39. Preparation of various polymers via metathesis reaction.
metathetical dimerization of o-unsaturated esters, followed by alcoholysis with diols or by acidic transesterication with diols, followed by ADMET. In order to synthesize polyether, o-unsaturated esters rst were achieved enzymatic epoxidation, and then they were polymerized. Refvik and Larock [184] synthesized a new material by thermal polymerization of metathesized
soybean oil in the presence of air. The product was yellow and brittle. 5. Composites from oil-based polymers Polymer composites are used in a wide range of application areas, such as aerospace, military, construction, electrical and electronics, medicine,
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marine, transportation etc. [50]. It is known that composites consist of two or more materials forming separate phase. Some of the llers used for composite preparation are carbon or graphite, glass, boron, steel, aromatic polyamide. In recent years, composites prepared from oilbased polymers have become a special interest in many areas. Polyurethane resin prepared from castor oil, for example, was used to obtain graphite composite as an electrode material [185]. The 60% (graphite, w/w) composite exhibited good mechanical and appropriated electric resistance, easy preparation and surface renovation. The most using oil in the preparation of durable and strong composite material is soybean oil [186]. In another study, epoxidized soybean oil-based composite was prepared and their viscoelastic properties were investigated [187]. Authors suggested that new material prepared exhibited strong viscoelastic solid properties similar to synthetic rubbers. Dweib et al. [188,189] manufactured materials from soybean oil-based resin and natural bers for using as the roof, oors or walls of a house or low-rise commercial buildings. For preparing soybean oil-based resin, rst, soybean oil was epoxidized and then vinylated by styrene or acrylic acid. Husic et al., [190] rst, synthesized polyurethanes with soybean oil-based polyol or petrochemicalbased polyol, and then prepared glass-reinforced composites from them. Investigation of their mechanical behaviors revealed that properties of the soybean oil-based composites were comparable with those based on petrochemical polyol. Additionally, oxidative, thermal and hydrolytic stability of soybean oil-based composites were superior to those of the latter. All results indicated that polyurethane matrix based on soybean oil is a preferable alternative to the petrochemical polyurethanes in glass-reinforced composites. In another study, modied soybean oil matrix material was used in the preparation of composites with different glass/ax ratios and different ber arrangements [191]. In recent years, nanocomposites has become one of the most important area in polymer science Biodegradable nanocomposites obtained from natural oil-based polymers led to plant oil silica hybrid coatings endowed with excellent exibility [192,193]. Epoxy-exfoliated clay nanocomposites were prepared using long-chain alkylammonium-exchanged smectite clay [194].
6. Oil-based inorganicorganic hybrid materials Hybrids are composites formed or composed of heterogeneous elements. Inorganicorganic hybrids can be classied in different morphological combinations; (i) the inorganic matrix, where organic materials are embedded in an inorganic polymer, (ii) the organic matrix, where inorganic materials are embedded in an organic polymer, (iii) the interpenetrating network, where inorganic and organic polymeric networks are independently formed without mutual chemical bonds, and (iv) true hybrids, where inorganic and organic polymeric systems with mutual chemical bonds are formed [195,196]. The primary goal is to combine the best properties of the inorganic phase with the best properties of the organic phase. The properties of new materials are showing in many cases surprising improvements. The inorganicorganic hybrid materials, for example, provide improved the durability, the mechanical and chemical resistances, and adhesion of composites. During the last decades the use of solgel process has gradually increased for preparing inorganicorganic hybrid products and materials. In this method
Organic-rich region
Inorganic-rich region
Fig. 4. A theoretical inorganicorganic hybrid material prepared with solgel process.
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664 F. Seniha Guner et al. / Prog. Polym. Sci. 31 (2006) 633670 [9] Yldz G, Wehling R L, Cuppet S L. Method for determining oxidation of vegetable oils by nearinfrared spectroscopy. J Am Oil Chem Soc 2001;78(5): 495502. [10] Asadauskas S, Erhan S Z. Thin-lm test to investigate liquid oxypolymerization of nonvolatile analytes. J Am Oil Chem Soc 2001;78(10):102935. [11] Guner F S, Erciyes A T, Kabasakal O S, Yagci Y. New aspects on the modication of triglyceride oils. In: Pandalai SG, editor. Recent Research Developments in Oil Chemistry, vol. 2. India: Transworld Research Network; 1998. p. 3151. [12] Guler OK, Guner FS, Erciyes AT. Some empirical equations for oxypolymerization of linseed oil. Prog Org Coat 2004;51:36571. [13] Mercangoz M, Kusefoglu S, Akman U, Hortacsu O. Polymerization of soybean oil via permanganate oxidation with sub/superciritical CO2. Chem Eng Process 2004;43: 101527. [14] Slivniak R, Domb AJ. Lactic acid and ricinoleic acid based copolymers. Macromolecules 2005;38:554553. [15] Nair MN, Unnikrishnan KG, Unnikrishnan M, Nair CSB. Utilization of rubber seed oil and karinnotta oil for preparation of air-drying oil-modied alkyd resins. Paintindia 1881;31(5):59. [16] Khandelwal SM, Gogte B. Alkyds from orangeseed Oil. Paintindia 1976;26(9):158. [17] Igwe IO, Ogbobe O. Studies on the properties of polyester and polyester blends of selected vegetable oils. J Appl Polym Sci 2000;75:14416. [18] Sabin P, Benjelloun-mlayah B, Delmas M. Offset printing inks based on rapeseed and sunower oil. Part Isynthesis and characterization of rapeseed oil- and sunower oil-modied alkyd resins. J Am Oil Chem Soc 1997;74: 4819. [19] Sabin P, Benjelloun-Mlayah B, Delmas M. Offset printing inks based on rapeseed and sunower oil. Part II varnish and ink formulation. J Am Oil Chem Soc 1997;74: 122733. [20] Aydn S, Akcay H, Ozkan E, Guner FS, Erciyes AT. The effects of anhydride type and amount on viscosity and lm properties of alkyd resin. Prog Org Coat 2004;51: 2739. [21] Chiang WY, Yan CS. Preparation and properties of liquid crystalline alkyd resin with para-hydroxybenzoic acid mesogenic side chain. J Appl Polym Sci 1992;46: 127990. [22] Chen DS, Jones FN. Binders for higher-solids coatings, part IIImodel alkyd resins modied by liquid crystalline groups. J Coat Technol 1988;60(756):3945. [23] Kangas LS, Jones FN. Binders for higher-solids coatings, part Isynthesis of model alkyd resins. J Coat Technol 1987;59(744):8997. [24] Kangas LS, Jones FN. Binders for higher-solids coatings, part IIproperties of model alkyd resins. J Coat Technol 1987;59(744):99103. [25] Manczyk K, Szewczyk P. Highly branched high solids alkyd resins. Prog Org Coat 2002;44:99109. [26] Bergenstahl B, Hoand A, Ostberg G, Larson A. Alkyd emulsions. In: Salamone JC, editor. Polymeric materials encyclopedia, vol. 1. New York: CRC Press; 1996. p. 15460.
inorganic macro-molecular solgel networks incorporate into organic polymer structures (Fig. 4). This process is also used for preparing triglyceride-based inorganicorganic hybrid coatings known as ceramers [144,156,197215]. Depending on the amount and type of solgel precursors, nal properties of the ceramer coatings could be adjusted within a wide range. 7. Conclusion As far as the environmental and energytical issues are considered, triglyceride oils are expected to play a key role during the 21st century as enabling to synthesize polymers from renewable sources. Polymers form triglyceride oils may be prepared by using various strategies. The choice of the strategy is important to succeed the polymerization and related to the structure of the oil and monomer. The presence of oil/fatty acid chain in the polymer structure improves some physical properties of polymer in terms of exibility, adhesion, resistances of water and chemicals. Because of their source and structural nature, triglyceride oils can widely be used as themselves. In bio-applications their biocompatibility and/or biodegradability play an important role. Even only these factors make triglyceride oils as essential raw materials to be used in various applications in the future. References
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Prog. Polym. Sci. 31 (2006) 633670 www.elsevier.com/locate/ppolysci

Polymers from triglyceride oils

Fig. 1. Life cycle of polymers based on triglyceride oils.

R1, R2, R3: fatty acid chain

(a) CH2CH2CH2CH2 (b) CH2CH=CHCH2 (c) CH2CH=CHCH2CH=CHCH2 (d) CH2CH=CHCH=CHCH2

Scheme 2. Synthesis of triglyceride.

Vernolic acid Licanic acid

Viscosity (cP, 110 1C) 2.78 3.47 4.24 3.41

Density (g/cm3, 80 1C) 0.8439 0.8414 0.8390 0.850

Melting point (1C) 54.4 62.9 69.6 16.3

Refractive index (n70) D 1.4273 1.4209 1.4337 1.4449a

99.8 89.9 181.0 273.5 85.1 261.0

Table 7 Some representative 1H chemical shift values for fatty acids

0.88 0.97 1.21.3 1.6 2.0 2.3 2.8 4.14.3 5.3

1745 1160 720 1650, 3010 990 970

Scheme 4. Oxypolymerization reaction.

Scheme 6. Preparation of alkyd resin.

Drying Time (min)

Anhydride Amount (mol) for 1 g Oil Part

Fig. 3. Drying times of the resins.

Scheme 7. Preparation of liquid crystalline alkyd resin by three methods.

Scheme 9. General formula of PHAs.

CH3 NCO NCO

Methylene-4, 40 -diphenyldiisocyanate Nafhthalene-1, 5-diisocyanate

Triglyceride oil + Glycerol

O O CH2 CH CH2 O C O R O C NH CH2

Scheme 12. Formula of PBTDI.

Scheme 11. Preparation of partial glycerides and oil-based polyurethane.

CH2-OH CH -OH CH2-OH

CH2-OH O CH3 O CH2 -CH3

CH2-O-COO CH3 O CH2 -CH3 O O O O O CH2-O-COO CH3 O CH2 -CH3

CH2-COOH CH -COOH CH2-O-CO CH -OH CH2-OH

Scheme 14. Maleinization of triglyceride oil.

CH2-O-CO CH-O-CO CH-O-CO

Scheme 13. Maleinization of triglyceride oil.

Computer-simulated [61] concentration proles of aqueous salt solutions through

Synthesis of IPNs and determination of their thermal properties

TDI, HMDI, MDI

BA, BMA, EA, EMA HEMA

Mixture of EA and EGDMA

NCO-terminated polyether, NCOterminated polybutadiene

Preparation of UV-curable IPNs

Linseed or tung IPDI oil modied CO

Crosslinking CO TDI, HMDI

Castor oil based IPNs A review 50, 97, 98, 99

OCN (CH2 )6 NCO

O (NH CO (CH2 )6 NH CO O CH2 CH CH2 O (C O CO R Uralkyd resin (UAR)

O C O CH2 CH CH2 O)n )m O CO R

Scheme 16. Synthesis of IPN based on uralkyd resin/polystyrene.

Scheme 17. Preparation of an oil-based polyamide.

Scheme 18. Hydrogen bonding causing thixotropy.

Scheme 19. Potential hydrogen bonding structures.

Scheme 20. Styrenation of conjugated and non-conjugated fatty acids.

Scheme 21. Styrenation of triglyceride oil via macroinitiator method.

Scheme 22. Modication of castor oil.

Scheme 23. interesterication of castor oil and linseed oil.

Scheme 24. Styrenation of triglyceride oil via macromonomer method.

Castor oil + Linseed oil

Interesterification products CH2=CH COOH CH O CO CH=CH2

CH2-O-CO CH -O-CO CH2-O-CO

Paraformaldehyde EtAlCl2 0C, 2 hr O O

CH2-O-CO CH -O-CO CH2-O-CO CH2-OH O