Progress in Polymer Science 33 (2008) 1199–1215

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Progress in Polymer Science
journal homepage: www.elsevier.com/locate/ppolysci

Condensation polymers from natural oils
Vinay Sharma, P.P. Kundu ∗
Department of Chemical Technology, Sant Longowal Institute of Engineering and Technology, Sangrur, Punjab 148106, India

a r t i c l e

i n f o

a b s t r a c t
Innovative technologies and competitive industrial products are reducing the dependence on petrochemicals for the production of polymers. Increasing concerns about the deteriorating environment caused by conventional polymers have directed worldwide research toward renewable resources. Vegetable oils are one of the most readily available alternative renewable resources. The functional groups present in natural oils can be activated for condensation polymerization. Accordingly, various types of useful condensation polymers, such as polyurethanes, polyesters and polyethers, are being produced by this route. The incorporation of natural oils into the polymer chain allows tailoring the properties of polyurethane products, for their widespread applications. © 2008 Published by Elsevier Ltd.

Article history: Received 23 August 2007 Received in revised form 1 June 2008 Accepted 1 July 2008 Available online 23 August 2008 Keywords: Soybean oil Castor oil Nahar seed oil Polyols Condensation polymers Polyurethanes Polyesters

Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1. Polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2. Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Polymers based on soybean oil polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Polymers and IPNs based on castor oil polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Polymers based on castor oil polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Interpenetrating and semi-interpenetrating networks based on castor oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Polymers based on nahar seed oil polyol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Other polymers based on oil polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1199 1200 1200 1200 1205 1205 1209 1212 1213 1214 1214

2. 3.

4. 5. 6.

1. Introduction Since the synthesis of polyurethanes by Bayer in 1937 [1], their utilization has become ubiquitous. These polymers are synthesized by reacting three basic components: polyisocyanate, polyhydroxyl containing polymer

∗ Corresponding author. E-mail address: ppk23@yahoo.com (P.P. Kundu). 0079-6700/$ – see front matter © 2008 Published by Elsevier Ltd. doi:10.1016/j.progpolymsci.2008.07.004

(i.e., polyester or polyether polyol) and a chain extender (usually a low molecular weight diol or diamine). Currently, the majority of polyols (polyether and polyester polyols) is derived from petrochemicals, a resource subject to depletion. Hence, bio-based materials are receiving wide attention as the oil crisis and threat of global warming deepen. The synthesis of bio-based materials from natural oils affords an alternative route [2–4] to natural oil-based addition polymers, which we discussed in an earlier review [5].

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Vegetable oils are becoming extremely important as renewable resources for the preparation of polyols required for the polyurethane industry. Polyols from natural oils, such as soybean, castor, and palm oils are increasingly being viewed by industry as a viable alternative to hydrocarbonbased feedstocks. These oils are annually renewable, and are cost-competitive as well as environment friendly. According to a market summary published by the United Soybean Board in February 2000, vegetable oil-based polyurethanes are best suited to three markets namely: polyurethane foams, polyurethane binders and agricultural films (the last may not be polyurethanes). Currently, the total U.S. annual market size is approximately 3000 million pounds for polyurethane foams and 400 million pounds for polyurethane binders and fillers. The introduction of natural oils as polyols into the polyurethane supply chain can provide an opportunity for polyurethane suppliers and customers to reduce their dependence on natural gas and crude oil, whose highly volatile and increasing costs continue to make it difficult for them to compete. Vegetable oils are excellent renewable source of raw materials for the manufacture of polyurethane components such as polyols. The transformations of the double bonds of triglycerides of oils to hydroxyls and their application in polyurethanes have been the subject of many studies [6]. The main technological advantages of these polyurethanes from vegetable oils are high strength as well as stiffness, environmental resistance and long life. 1.1. Polyols Oil-based polyols are often oligomers with a wide distribution of molecular weights and a considerable degree of branching, which affect the viscosity and processing properties of polyurethane foams produced from them. Precise characterization of the polyol composition and its properties are very important for understanding synthetic processes as well as for quality control. Polyols are a component in the production of polyurethanes used in appliances, automotive parts, adhesives, building insulation, furniture, bedding, footwear and packaging. Although, polyols are currently produced from petroleum, vegetable oils are also used extensively for their production. The vegetable oil molecules must be chemically transformed in order to obtain hydroxyl moieties. For example, soybean oil does not contain hydroxyl groups, but it has an average of 4.6 double bonds per molecule. The unsaturated portion of the oil can be converted to hydroxyl groups. 1.2. Polyurethanes Polyurethanes (PU) are polymers containing urethane linkages (–NHCOO–) in the main polymer chain. They can be classified in the following major groups: (a) flexible foams, (b) rigid foams, (c) elastomers, (d) fibers, (e) molding compositions, (f) surface coatings and (g) adhesives. Depending upon the degree of cross-linking, polyurethane foams may be flexible or rigid. Polyester polyols used in the foams are based on industrial waste streams of polyester and depolymerized PET from scrap bottles. Flexible foam is based on a flexible aliphatic

polyester polyol (such as adipic polyester resin) and rigid foam is prepared from aromatic polyester polyol, e.g. depolymerized PET. The biggest challenge for the production of PU using polyols from natural oils is the variation of the unsaturation content among natural oils. If the double bond content in natural oils is not properly controlled, the nature of the polyol will be changed, affecting the performance of the final polyurethane product. Polyurethane foam finds application as one of the most effective insulating materials. Blowing agents are generally used to create a fine cellular foam structure. Upon dissociation the blowing agent generates gases, which are trapped within the small cells (or closed cell) of the foam. This enhances the insulating properties of the PU foam. 2. Polymers based on soybean oil polyols Petrovic and co-workers [7] studied polyurethane foams-based on soybean oil. They prepared both hydrochlorofluorocarbon (HCFC) and pentane blown rigid polyurethane (PU) foams from polyols derived from soybean oil. The effect of process variables on foam properties was studied by varying the amounts and types of catalyst, crosslinker, blowing agent, surfactant and water. The foams prepared from these polyols were found to have mechanical and insulating properties such as compressive strength and thermal strength comparable to those of commercially available polypropylene oxide (PPO)-based foams. The commercial PU foams derived from PPO-based triols have the disadvantages of thermal degradation and thermal oxidation. It was observed that the soybean polyol derived PU foams were more stable. Comparative thermo-gravimetric analysis (TGA) of PU foams-based on PPO triols and soybean polyols in air and in nitrogen N2 is shown in Fig. 1. In air (Fig. 1b), both the PU samples from PPO and soy polyol show higher weight loss, compared with the thermo-gravimetric loss in nitrogen (Fig. 1a). The weight loss of up to 5% is important as PUs are never used beyond this weight loss level because of substantial deterioration in mechanical and other properties. The PUs from soy polyol were observed to be more stable than those from PPO-based polyol at around 200 ◦ C, where the weight loss was less than 5%. Petrovic and co-workers [8] studied the thermal stabilities of PU-based on various vegetable oils. They used TGA and Fourier-transform infra-red (FTIR) spectroscopy for thermal analysis of the polymers. In TGA, PPO-based PU showed single-stage degradation, while the vegetable oil-based PUs degraded in two stages. The isothermal (at 250 ◦ C) thermo-gravimetric loss of PPO-PU, SOY-PU and castor-PU versus time is shown in Fig. 2. The PU from PPO (arcol, as shown in Fig. 2) was more stable at 250 ◦ C than the PUs from soy and castor polyol. The degradation pattern with temperature of these three PUs derived from PPO, castor and soybean oils are shown in Fig. 3. This figure shows four derivative peaks for oil-based and two peaks for PPO-based PUs. The temperature for initial degradation up to 10% by weight was almost the same for all PUs. The residue at 500 ◦ C appeared to correlate with the amount of isocyanate in the polymer, except for PPO-based PU. From

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Fig. 1. Thermal behavior of soybean oil polyol based foam versus PPO-based foam: (a) TGA in N2 . (b) TGA in air. Reproduced from Guo et al. [7] with permission of John Wiley and Sons, Inc.

Fig. 2. Isothermal TGA curve at 250 ◦ C of three polyurethanes in nitrogen. Reproduced from Javni et al. [8] with permission of John Wiley and Sons, Inc.

Fig. 3, the PPO-based PU showed the fastest rate of weight loss and the smallest residue at 300 ◦ C. On the other hand, at the same temperature the oil-based PUs were thermally more stable than PPO-based PU. From these studies, Petrovic et al. proposed three mechanisms of decomposition of urethane bonds, as shown in Scheme 1. All three reactions may proceed simultaneously. The Petrovic group [9] also studied the structure and properties of PUs prepared from halogenated as well as non-halogenated soybean polyols. They determined the structure and properties of these polymers by spectroscopic, chemical and physical methods. In this study, they modified epoxidized soybean oil (ESBO) with hydrochloric acid, hydrobromic acid, methanol and hydrogen. The effects of these modifications on PUs were studied by infra-red (IR) spectroscopy, nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and rheological methods. The properties of polyols obtained from ESBO are given in Table 1. From these polyols, four types of polyol polyurethanes were prepared [10]. The properties of these polyurethanes followed the same pattern as those of the polyols. For example, the brominated PU had higher density, followed by chlorinated, then by methoxylated and, finally, hydrogenated PUs. For the preparation of PUs, two types of isocyanates PAPI-2143L (a crude MDI) and Isonate 2143L (a liquid MDI prepolymer containing carbodiimide

Fig. 3. Derivative TGA curves of PPO-based PU, castor-based PU and soybean-based PU in air. Reproduced from Javni et al. [8] with permission of John Wiley and Sons, Inc.

Scheme 1. Mechanisms of decomposition of urethane bonds. Reproduced from Javni et al. [8] with permission of John Wiley and Sons, Inc.

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Table 1 Properties of polyols derived from epoxidized soybean oila Polyol Soy-H2 Soy-Met Soy-HClb Soy-HBrb
a b

Reagent H2 CH3 OH HCl HBr

Yield (%) 89 93 94 100

Hydroxyl no. (mg KOH/g) 212 199 197 182

Equivalent weight (g/equivalent) 265 282 285 308

Functionality 3.5 3.7 3.8 4.1

Polyol, Mn 938 1053 1071 1274

Physical state at room temperature Grease Liquid Grease Grease

Reproduced from Guo and Petrovic [9] with permission of John Wiley and Sons, Inc. All values were calculated on the basis of the analyzed Cl and Br contents and under the assumption that each halogen is accompanied by a hydroxyl group.

bonds) were used. The PUs from both of these isocyanates showed comparable thermal stability, mechanical strength and dielectric properties. The PU networks from soybean oil had numerous valuable properties. These properties solely depended upon the chemical composition and cross-link density. The NCO/OH mole ratios (isocyanate index) in the polyol directly affected the physical and mechanical properties of the resulting PU networks [11]. NCO/OH molar ratios were varied from 1.05 to 0.4 with the resulting properties shown in Table 2. With a decrease in the NCO/OH mole ratio, the glass transition temperature Tg decreased linearly from 64 to −3 ◦ C. The tensile strength of the networks decreased from 47.3 to 0.3 MPa with a decreasing NCO/OH mole ratio. The polyurethane networks, prepared with lowering of the molar ratio of NCO and OH groups, had an increasing amount of imperfections in the form of dangling chain ends. Therefore, the properties of the networks deteriorated with a decrease in the NCO/OH molar ratio. Petrovic et al. [12] also studied the properties of vegetable oil-based PUs through hydroformylation. Hydroformylation is an aldehyde synthesis process that falls under the general classification of a Fischer–Tropsch reaction. Hydroformylation, also known as the oxo synthesis, is an important industrial process for the production of aldehydes from alkenes. This chemical reaction entails the addition of a formyl (CHO) group and a hydrogen atom to a carbon–carbon double bond. The double bonds of the soybean oil were first converted to aldehydes using either rhodium or cobalt as catalyst. The aldehydes were hydrogenated to alcohols forming a triglyceride polyol. Polyols from a rhodium-catalyzed reaction (95% conversion) resulted in a rigid polyurethane,

while polyols from a cobalt-catalyzed reaction (67% conversion) resulted in hard PU rubbers with lower mechanical strength. The soybean-based polyurethanes were prepared from aliphatic, cycloaliphatic and aromatic isocyanates [13]. The isocyanates used in this study were 4,4 -diphenylmethane diisocyanate (MDI), 2,4:2,6-toluene diisocyanate (TDI), hydrogenated MDI (RMDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), Desmodur N-100 and Desmodur N-3300 (triisocyanates derived from 1,6-hexamethylene diisocyanate), Desmodur RF-E (a tris (p-isocyanato-phenyl)-thiophosphate) and Desmodur CB 75N a (trimethylol propane TDI-based prepolymer). A higher cross-link density of the PU networks resulted for triisocyanates than for diisocyanates. The density, glass transition temperature [measured by differential scanning calorimetry (DSC), thermal mechanical analysis (TMA) and dynamic mechanical analysis (DMA)] and the degree of swelling in toluene are reported in Table 3. In comparison with diisocyanates, the triisocyanates resulted in better overall properties such as density, Tg , swelling and mechanical properties. The triisocyanates RF-E [a tris (p-isocyanato-phenyl)thiophosphate-based prepolymer] and CB 75N (a trimethylol propane TDI-based prepolymer) showed flexural moduli of the order of 2480 and 2040 MPa and tensile strengths of 48 and 65 MPa, respectively. Petrovic et al. [14,15] also studied the properties of polyisocyanurate cast resins and foams from soybean oil-based polyols. Polyisocyanurate cast resins are heat resistant materials obtained by polycyclotrimerization of diisocyanates or isocyanate-terminated prepolymers (Scheme 2). The formation of polyisocyanurate from the prepolymer took place at higher temperatures com-

Table 2 Molecular weights Mc between crosslinks and concentration (between 1.05 and 0.4)a NCO/OH mole ratio Density (g/cm3 )

e

of ENAC for polyurethanes (based on soybean polyol and MDI) withNCO/OH mole ratios

Degree of swelling (W1 /W0 )

Sol fraction (%)

Affine model
e

Phantom model Mc (g/mol) 404 451 509 574 741 981 1415 2601 7118
e

(mol/cm3 )

(mol/cm3 )

Mc (g/mol) 257 282 313 348 435 556 769 1372 3333

1.05 1 0.95 0.9 0.8 0.7 0.6 0.5 0.4
a

1.104 1.104 1.104 1.101 1.095 1.088 1.083 1.074 1.064

1.5199 1.5528 1.5911 1.6334 1.7299 1.8480 2.0165 2.350 3.060

0.82 1.02 1.29 1.55 2.78 5.20 8.68 11.67 24.78

2.73 × 10−3 2.45 × 10−3 2.17 × 10−3 1.92 × 10−3 1.48 × 10−3 1.12 × 10−3 7.65 × 10−4 4.13 × 10−4 1.49 × 10−4

4.30 × 10−3 3.91 × 10−3 3.52 × 10−3 3.17 × 10−3 2.52 × 10−3 1.96 × 10−3 1.41 × 10−3 8.09 × 10−4 3.19 × 10−4

Reproduced from Petrovic et al. [11] with permission of Plenum Publishing Corp.

V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215 Table 3 Density, Tg (measured by DSC, TMA, and DMA), and degree of swelling in toluene of soybean oil-based polyurethanesa Isocyanate MDI TDI RMDI IPDI HDI N100 N3300 RFE CB 75N
a

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Density (kg/m3 ) 1104 1104 1062 1061 1066 1082 1096 1272 1186

Tg by DSC (◦ C) 59 47 50 48 10 26 25 NA 93

Tg by TMA (◦ C) 55 53 47 48 15 25 25 64 85

Tg by DMA (◦ C) 74 62 69 68 22 41 37 84 92

Swelling degree (%) 55 64 75 79 79 52 59 22 12

Reproduced from Javni and Petrovic [13] with permission of John Wiley and Sons, Inc.

pared to the reaction temperature for the formation of polyurethane [14]. As a result, the isocyanate terminated prepolymers (PU) also reacted with themselves, producing strong isocyanurate chains (Scheme 2). These cross-links were stronger than normal bonds in polyurethane. For example, polyisocyanurate foam from soy polyol (59 MPa) showed nearly double the stress at break than PPO-based polyisocyanurate foam (31 MPa). Thus, the resulting polyisocyanurate foam was chemically and thermally more stable (disintegration started above 400 ◦ C). Polyisocyanurates are used in applications where the material is exposed for an extended period of time at an elevated temperature. Two polyols (PPO 168 and Soypolyol 173) having the same hydroxyl number, functionality and molecular weight, but with significant structural differences, were used. PPO 168 had terminal OH groups, which on reaction with isocyanate of polyisocyanurate formed polyurethane. Soypolyol 173 had internal hydroxyl groups positioned in the middle of the fatty chain. Thus, Soypolyol 173 exhibited higher crosslink density of the polyisocyanurate network than PPO 168. The soybean polyol-based polyisocyanurate showed a higher Tg (about 30 ◦ C higher) than PPO 168-based polyisocyanurates. All the PU foam samples showed a -transition at about −30 to −20 ◦ C [15]. The PPO 168-based PUs decomposed at a higher rate at 235 ◦ C, while the maximum rate of decomposition for soy polyol-based PUs was 370 ◦ C. The compression strength (measured at a stress of 10, 20 and 30% strains with applied force parallel to the foam rise of soy polyol-based PU foams was much higher than for PPObased PU foams, as shown in Fig. 4. The PPO-based foams

were semi-rigid at an isocyanate index of 110, but the soy polyol foams had a higher density at an index of 110 and showed higher compressive stress. The thermal and mechanical properties of glass reinforced soybean oil-based polyurethane composites were also studied by Petrovic [16]. PUs in this study were derived from a soybean oil-based polyol (Soypolyol 204) and petrochemical polyol (Jeffol G30-650). Although the Tg of jeffol composites was slightly higher than that of soy polyol composites, the oxidative, thermal and hydrolytic stability of the latter was superior to propylene glycolbased polyurethanes [17–19], suggesting that it could find increasing applications in the composites area. The structure–property relationships were further studied by Petrovic et al. [20]. They prepared two types of soybean polyols, one from epoxidation of soybean oil, followed by methanolysis and the other from hydroformylation of soybean oil, followed by hydrogenation [18,19]. The mechanistic paths of these processes are shown in Scheme 3. The polyol II in Scheme 3 was more reactive than polyol I, because polyol II contains a primary hydroxyl group as well as one additional carbon atom in the crosslinking chain after hydroformylation, while polyol I contains a secondary hydroxyl group and methoxy groups as side chains.

Scheme 2. Schematic representation of polyisocyanurate structure. Reproduced from [14] with permission of John Wiley and Sons, Inc.

Fig. 4. Compression stress of soybean-based foams and PPO-based foams. Reproduced from Javni et al. [15] with permission of Plenum Publishing Corporation.

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Scheme 3. Schematic representation of methanolysis and hydroformylation of soybean oil. Reproduced from Guo et al. [20] with permission of Springer Science and Business Media, LLC.

Dunjic and co-workers [21] prepared a series of urethane acrylates derived from soybean fatty acid modified hyperbranched aliphatic polyesters through a two step process. The material obtained was used as oligomer in radiation curable compositions. The UV cured acrylates exhibited good mechanical and thermal properties. The tensile strengths of these samples ranged from 15.73 to 72.53 MPa and they showed 5% weight loss at around 300 ◦ C during thermal degradation. Fan et al. [22] reported soybased polyamide resins via condensation polymerization from different dimer acids and diamines. The polyamide prepared from 1,4-phenylenediamine showed a rapid increase in molecular weight above 260 ◦ C. Polyamide from 1,4-phenylenediamine showed higher Tg , melting temperature (Tm ), decomposition temperature and mechanical strength than aliphatic polyamides. The flexibility of dimer

acid and its macrostructure, such as the contents of monomer and trimer acids, directly affected the resulting polymer properties. Deng et al. [23] reported the synthesis of soybased copolyamides with different -amino acids. The contents of amino acids were varied, keeping the contents of dimer acid and phenylenediamine constant. The copolyamides thus prepared showed a drastic decrease in mechanical strength. For instance, Young’s modulus for homopolymer was 2116.0 MPa; and that for copolymers containing tyrosine, glutamic acid and phenylalanine were 330.8, 242.9 and 183.2 MPa, respectively. John et al. [24] studied PU foams derived from soybean oil. The reaction was monitored by FTIR spectroscopy. The introduction of soybean oil caused an increase in hydroxyl values and acid values as well as molecular

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Fig. 5. SEM micrographs of (a) soybean polyol foam at 3-php water and (b) voranol polyol foam at 3-php water. Reproduced from Singh and Bhattacharya [25] with permission of John Wiley and Sons, Inc.

weight, whereas iodine values and fatty acid content decreased. Singh and Bhattacharya [25] also studied PU foams from soybean oil. They studied the viscoelastic changes and cell opening by using vane geometry in a straincontrolled rheometer. They identified four stages of modulus development during the foaming reaction namely, (i) bubble nucleation and growth, (ii) packing of bubble network/liquid foam, (iii) urea microphase separation and cell opening, and (iv) final curing. In their study, they further investigated the effects of temperature, voranol (a synthetic polyol), water and straining frequency on the properties of PU foam. A SEM micrograph for soybean oil polyol foam and voranol polyol foam at 3-php (parts per hundred parts) water is shown in Fig. 5. The size and shape of the cells was less uniform for soybean polyol foams compared to synthetic voranol foams (Fig. 5). Soybean polyol-based foams had more pinhole openings and more partially open cell structures rather than completely open cells. Rosch and Mulhaupt [26] synthesized polyester resins and blends from anhydride-cured epoxidized soybean oil. The mechanical and thermal properties of the casting resins were dependent upon the type of anhydride used. At low epoxy conversions, i.e., using low accelerator content or less reactive anhydrides such as cycloaliphatic anhydrides, the crosslinked polyesters were highly flexible. For example, norbornene dicarboxylic acid anhydride resulted in

polyester with a Tg of −5 ◦ C, which indicated the rubbery nature of the polyester. With maleic and phthalic anhydrides, stiffer polyesters with flexural moduli in the range of 500–1000 MPa and Tg between 43 and 75 ◦ C were obtained. Eren et al. [27] polymerized maleinized soybean oil with different alcohols such as low molecular weight polyols and long chain diols [glycerol, pentaerythritol, polyethylene glycol (PEG) 160, PEG 400, PEG 600, etc.]. The material obtained was highly crosslinked and become jellylike in common solvents like acetone and chloroform. Mohanty and co-workers [28] evaluated the thermomechanical properties of PU-based on soybean phosphate ester polyols and polymeric dipenylmethane diisocyanate (pMDI). The glass transition temperature of the PUs varied from 69 to 82 ◦ C and the values of storage moduli were between 4 × 108 and 1.3 × 109 Pa. The PU samples were postcured at 100 and 150 ◦ C. The crosslink density e of the samples postcured at 100 ◦ C was lower than for those postcured at 150 ◦ C, despite a longer postcure time. Monteavaro et al. [29] investigated the thermal properties of soybean oil-based PUs by thermogravimetric analysis. The TGA was carried out under nitrogen at a heating rate of 10 ◦ C min−1 for dynamic TG, and isothermal measurements were carried out at 230, 240 and 250 ◦ C. Fig. 6a presents the rate of weight loss in isothermal measurements at 230, 240 and 250 ◦ C for the PU samples. The curves show an increase in the rate of weight loss with an increase in temperature. The rate of weight loss was highest in the initial period (up to approximately 100 min). From Fig. 6a, one can measure the time for weight loss of 4, 5 and 7% at 230, 240 and 250 ◦ C. Fig. 6b shows the log–log plot of time versus temperature for 4, 5 and 7% weight loss of PU. The vertical lines in Fig. 6b correspond to iso-conversional (for same weight loss) plots and the plots along the temperature axis correspond to isothermal lines. If the PU had followed the same decomposition pattern at different temperatures, the isothermal lines would be expected to be parallel. Instead, they are not parallel, indicating different decomposition processes at different temperatures. Pechar et al. [30] synthesized PU networks from soybean oil polyol, petroleum-based polyols and their blends. The soybean polyols were prepared by air oxidation of raw soybean oil and hydroxylation of epoxidized soybean oil. The Tg of the PU samples ranged from −21 to +83 ◦ C and was linearly related with the hydroxyl numbers (55–237 mg KOH/g) of the soybean oil polyols. Quintero et al. [31] developed the vegetable oil macro-monomer (VOMM) technology for application to aqueous coatings. This would help to reduce the volatile organic content in waterborne coatings. They used soybean acrylated macro-monomer (SAM) as a copolymerizable hydrophobe for miniemulsion polymerization. This system allowed an improvement in flow and smoothing of the coated film before crosslinking and cessation of flow. 3. Polymers and IPNs based on castor oil polyols 3.1. Polymers based on castor oil polyols The use of castor oil in the polyurethane industry adds value to the crop. Bao et al. [32] studied the effect of the

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Scheme 4. Preparation of modified castor oil polyurethane dispersions. Reproduced from Bao et al. [32] with permission of Iran Polymer and Petrochemical Institute.

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Fig. 7. Avrami plots for castor oil, sodium benzoate and related PET compositions during isothermal crystallization from the melt at 220 ◦ C. Reproduced from Barrett et al. [33] with the permission of John Wiley and Sons, Inc.

Fig. 6. (a) Isothermal TG curves for PU04 (from toluenediisocyanate and soy polyol with NCO/OH ratio 0.80) at 230, 240 and 250 ◦ C in nitrogen (b) Variation of degradation time (isothermal) with temperature (dynamic TGA) in nitrogen to achieve the same conversion level at three temperatures (isothermal and isoconversion lines) for PU04. Reproduced from Monteavaro et al. [29] with permission of Associacao Brasileira de Polimeros.

NCO/OH mole ratio on the structure and properties of aqueous PU from modified castor oil (MCO). The synthesis of the PU from modified castor oil (MCPU) is shown in Scheme 4 where acid-ended modified castor oil used for the production of PU-polyamide forms salts with a triamine, leading to the formation of a water-soluble polymer. A three step degradation was observed for all the PU-polyamide samples. In the first stage, a weight loss of less than 5% occurred at about 210–240 ◦ C. In the second stage, a rapid weight loss started at 250 ◦ C and continued up to 360 ◦ C. Barrett et al. [33] studied the crystallization kinetics of poly ethylene terephthalate (PET) from a mixture containing naturally functionalized triglyceride oil. The crystallization of PET was dependent on several factors such as plasticization due to the presence of the triglyceride oil, nucleation from added agents, bond interchange reactions and the formation of a crosslinked triglyceride oil network. The identification of such factors allowed some control over microstructure of these products and similar blends and semi-IPNs. The Avrami analysis supported the effec-

tiveness of castor oil. Avrami plots for castor oil, sodium benzoate and related PET compositions during isothermal crystallization from the melt at 220 ◦ C are shown in Fig. 7. In the presence of castor oil, a high curvature appeared in the Avrami plot for the crystallization of PET. This showed a smooth transition from the primary to secondary crystallization. The sodium benzoate blends displayed a rapid transition from primary to secondary crystallization. The mixture of castor oil and sodium benzoate showed a gradual transition. Kansara et al. [34] statistically studied the reaction kinetics of castor oil (CO)-based polyol and TDI. They used a second-order rate expression for the equimolar reaction between polyol and TDI. For a specific case, a moles of both of the reactants are present at the start of the reaction and at a specific instant t, x moles of the reactants are reacted. Then, one can find from the bimolecular rate expression that the quantity x/a(a − x) is directly proportional to the time t. Thus, plots of x/a(a − x) versus time were linear. They studied the reactivity of ortho and para—NCO groups in TDI with varying temperature, catalyst ratio and polyol chain length of. The prepolymers R60 and R92 were polyolsbased on castor oil. The hydroxyl value, equivalent weight and Brookfield viscosity (cP) of R60 and R92 were reported to be 5, 220, 620 and 6, 190, 700, respectively. R60 and R92 showed higher conversion compared with the parent castor oil at all temperatures and catalyst concentrations. Kansara and co-workers [35] also studied castor oilbased polyurethane adhesives. They used two teak wood pieces and applied the adhesive solution to a thickness of 0.1 mm and joined the pieces together under a load of 2.5 kg for 12 h. These samples were found to have 10 times more lap shear strength as compared with commercially available wood adhesives. The adhesive films were also tested for thermal stability and chemical resistance. Yeganeh and Mehdizadeh [36] investigated millable PU elastomers from castor oil-based polyols. Millable PU elastomers (MPE) are a special type of synthetic rubber. MPEs can serve the rubber industry as they can be

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V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215 Reproduced from Yeganeh and Shamekhi [38] with permission of John Wiley and Sons, Inc. [38]. Each sample has NCO/OH mole ratio 1.0. Quantities in parentheses are in g. PHC-I, PHC-II and PHC-III contain castor oil, polyethylene glycol, polyethylene terephthalate and zinc acetate. The curing agent is toluene diisocyanateand trimethylol propane dissolved in a minimum amount of dimethyl formamide and N-methyl aniline. Sample thickness: 17 mil (0.017 in.).
b

mixed, extruded, calendared, and compression or injection molded in conventional rubber processing equipments [37]. The MPEs were prepared by the reaction of difunctional castor oil and TDI dimer in an inert atmosphere. The synthesis of difunctional castor as reported by Yeganeh and Mehdizadeh [36] is as follows. In a three-necked, roundbottomed flask equipped with a stirrer, dropping funnel and thermometer, dried castor oil (100 g) was added. The temperature was brought to 100 ◦ C, followed by dropwise addition of phenyl isocyanate (8.33 g) under stirring. The reaction was continued for 2 h, before cooling. These MPEs showed two-step degradations, one at 270 ◦ C and the second one at 380 ◦ C. The mechanical properties of these MPE were dependant on the contents of castor oil and the chain extenders. On comparison with a commercially available elastomer (Urepan 600), these MPEs exhibited comparable tensile strength, compression set, resilience and slightly inferior abrasion resistance and elongation at break. Novel PU insulating coatings from glycolyzed PET (GPET) and castor oil were also investigated by Yeganeh and Shamekhi [38]. First, they synthesized polyhydroxy compounds from different compositions of CO and GPET. Several types of reactions can occur during the preparation of polyhydroxy compounds (PHC). So, proper analysis such as measurement of hydroxyl values and acid values was carried out to ascertain the transesterification as the major reaction. The thermal and electrical properties of the PUs obtained from the PHCs are shown in Table 4. The Tg of the samples ranged from 47 to 61 ◦ C. The tensile strength was between 19 and 47 MPa and the elongation was 8–24%. It was observed that with a decrease in the hydroxyl value of PHC, the crosslink density also decreased. Yeganeh and Hojati-Talemi [39] also studied biodegradable PU networks obtained from the PHCs of castor oil and PEG. The PU networks obtained were characterized by their physical, mechanical and viscoelastic properties. The stress–strain curves for the castor oil PUs (CPU) are shown in Fig. 8. Fig. 8 shows a smooth transition in stress–strain behavior for CPU1 and CPU2 samples similar to that in lightly crosslinked amorphous rubber. However, the stress–strain behavior of CPU3 and CPU4 was different: these showed a yield point due to presence of a crystalline phase. Because of the higher crystallinity of CPU4, it showed higher initial modulus and tensile strength and lower elongation at break. The tensile strength of these CPUs ranged from 0.66 to 2.51 MPa. The Tg of the samples was below room temperature (between −2.0 and 5.1 ◦ C). Preparation of PU nanoparticles by miniemulsion polymerization from castor oil polyol was reported by Zanetti-Ramos et al. [40]. The PU particle size measured by dynamic light scattering ranged from 200 to 300 nm. Ogunniyi et al. [41] reported the preparation and properties of PU foams from the reaction of TDI with a mixture of castor oil polyol and polyether polyol. The introduction of castor oil polyol in the formulation of PU foams increased the tensile strength from 3.33 to 138.89 kN/m2 and compression set from 5.2 to 49.25% with increasing oil content.

Dielectric strength (V/mil)a Q factor Dielectric constant (60 Hz) Dissipation factor (60 Hz) Char (%)@600 (o C) T 50% (◦ C) T 10% (◦ C) Tg (◦ C) Table 4 Thermal and electrical propertiesa Sampleb

Pu1[PHC-I(0.99) + curing agent (1.3) + DMF(0.86) + xylene(2.57)] Pu4[PHC-II(1.01) + curing agent (1.3) + DMF(0.86) + xylene(2.59)] Pu7[PHC-III(1.1) + curing agent (1.3) + DMF(0.9) + xylene(2.7)]

61 57 47

262 267 272

345 326 320

8.0 3.8 8.7

0.0082 0.0226 0.0283

5.00 5.45 5.10

121.95 44.24 35.33

2159 2117 1926

a

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Fig. 8. Stress–strain curves for CPU 1–4. CPU1 containing100% epoxy modified PU prepolymer-based on castor oil (EPU1) and 0% epoxy modified PU-based on polyethylene glycol (EPU2), CPU2 containing 90% EPU1 and 10% EPU2, CPU3 containing 70% EPU1 and 30% EPU2 and CPU4 containing 50% EPU1 and 50% EPU2. Reproduced from Yeganeh and Hojati-Talemi [39] with permission of Elsevier Ltd.

3.2. Interpenetrating and semi-interpenetrating networks based on castor oil Polymer systems comprising of two or more networks, which are at least partially interlaced on a molecular scale, but not covalently bonded to each other, are called interpenetrating polymer networks (IPN). These polymer networks cannot be separated unless chemical bonds are broken. Polymer systems comprising one polymer network and another of linear or branched polymer, characterized by the penetration on a molecular scale of the linear or branched macromolecules in the polymer networks, are called semi-interpenetrating networks. Semi-interpenetrating polymer networks are distinguished from interpenetrating polymer networks because the constituent linear or branched polymers could, in principle, be separated from the constituent polymer network(s) without breaking chemical bonds. When they can be separated, they are called polymer blends. Attempts have been made to synthesize interpenetrating polymer networks (IPN) and a series of cross-linked copolymers and IPNs from epoxidized vegetable oils and maleinized tung oil [42]. Cross-linked copolymers were synthesized by mixing epoxidized vegetable oils and adduct of tung oil with maleic anhydride in different proportions. The IPNs were tested by dynamic mechanical spectroscopy (DMS) to investigate compatibility and damping properties. The IPNs formed by triglycerides were found to increase the toughness and fracture resistance in conventional thermoset polymers. There are reports of development of IPNs consisting of cross-linked polystyrene and epoxidized linseed oil elastomers [43]. IPNs from crosslinked polystyrene and castor oil elastomers have also been reported [44–46]. Suthar and co-workers [47–50] prepared IPNs from polyurethanes-based on castor oil with other vinyl monomers. They found that the IPNs

formed were tougher than the corresponding homopolymers. Patel and Suthar [51] synthesized liquid prepolyurethanes from castor oil and TDI under different conditions and with varying NCO/OH ratios. Then, the pre-polyurethane was reacted with poly (ethyl acrylate) to obtain IPNs. These IPNs were characterized by chemical, mechanical and thermal methods. The glass transition temperature of these IPNs ranged from 38 to 41 ◦ C. The chemical resistance of the IPNs was studied in different reagents: 25% H2 SO4 , 15% HCl, 5% HNO3 , 5% NaOH, 25% acetic acid, 5% H2 O2 , 40% NaCl, methylethyl ketone, distilled water, carbon tetrachloride and toluene for seven 7 days. The IPNs were stable in all the media except methylethyl ketone, carbon tetrachloride and toluene. The IPNs were stable up to 300 ◦ C with 7–9% weight loss; 54–57% weight loss was observed around 400 ◦ C and decomposition was complete beyond 550 ◦ C. Mechanical properties of these IPNs are given in Table 5. Suthar and Patel [52] studied IPNs from castor oilbased PU and poly (methyl acrylate). The castor oil was reacted with 4,4 -diphenylmethanediisocyante to obtain pre-polyurethane, which was further reacted with methyl acrylate monomer and ethylene glycol dimethacrylate as a crosslinker. These IPNs showed low chemical resistance towards CCl4 , methylethyl ketone and toluene. They showed high light transmittance (49–81%). These polymers were stable up to 300 ◦ C, lost 45% weight rapidly at around 450 ◦ C and decomposed completely beyond 600 ◦ C. The tensile strength of these polymers was between 0.43 and 1.87 mN/m2 and they had elongations in the range of 84–102%. Suthar et al. [53] also studied the IPNs from castor oil-based polyesters and poly (methyl methacrylate). The polyesters were synthesized from castor oil and dibasic acids such as malonic, succinic, glutaric, adipic, suberic and sebacic acids. These IPNs showed two glass transitions corresponding to their individual component networks. The first Tg was in the range of −76 to −70 ◦ C and the second was between 25 and 34 ◦ C. The tensile strength was between 140 and 280 kPa and Young’s modulus was 730–1200 kPa. These polymers were stable upto 300 ◦ C showing only 2–4% weight loss, whereas they showed 50% weight loss at around 400 ◦ C. The samples decomposed completely beyond 500 ◦ C. Suthar et al. [54] synthesized three series of IPNsbased on PU from castor oil and TDI with polystyrene, poly (methyl methacrylate) and poly (n-butyl methacrylate). They studied the effects of structural variables such as composition, type of vinyl monomer and the effect of interaction of phases on the dielectric properties. These IPNs were characterized in terms of the variation of dielectric permittivity E , dissipation factor E and tan ı versus temperature. The dielectric relaxation studies showed that these IPNs behaved like homogeneous materials. Sperling and co-workers [55,56] reported the preparation of interpenetrating networks from castor oil-based polyurethanes and styrene monomer. The resulting IPNs were characterized by electron microscopy, modulus-temperature measurements and stress–strain analysis. The interpenetrating networks (IPN) showed stress–strain behavior

1210 Table 5 Mechanical properties of IPNsa Sampleb , c IPN-1 (PPU-25 + EA-75) IPN-2 (PPU-35 + EA-65) IPN-3 (PPU-45 + EA-55) IPN-4 (PPU-25 + EA-75) IPN-5 (PPU-35 + EA-65) IPN-6 (PPU-45 + EA-55) IPN-7 (PPU-25 + EA-75) IPN-8 (PPU-35 + EA-65) IPN-9 (PPU-45 + EA-55) PEAd
a b c d

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Tensile strength (mN/m2 ) 3.41 3.66 2.85 3.37 7.10 6.38 9.38 10.60 8.67 62.30

Young’s modulus (mN/m2 ) 1.64 2.17 1.90 3.67 3.01 2.99 4.67 4.13 3.84 2500

Elongation @ break (%) 194 182 188 148 225 200 183 186 178 16

Hardness shore A 79 83 95 81 73 80 86 87 79 92

Reproduced from Patel and Suthar [51] with permission of John Wiley and Sons, Inc. Contents of pre-polyurethane (PPU) and ethyl acrylate (EA) are given in parenthesis. NCO/OH molar ration for IPNs 1–3 is 1.6, for IPNs 4–6 is 1.8 and for IPNs 7–9 is 2.0. PEA is the homopolymer of ethyl acrylate.

similar to reinforced elastomers. The properties of the IPN showed a dependence on the NCO/OH ratio in the castor oilbased PU and the content of polystyrene. At a fixed NCO/OH ratio of 0.75, with a decrease in the polystyrene content in the IPN from 53 to 50%, the IPNs exhibited an increase in elongation from 130 to 140% and in tensile stress from 1000 to 2500 psi. For a fixed 50% content of polystyrene, a decrease in elongation (from 140 to 130%) and in tensile stress (from 2500 to 1200 psi) was observed for an increase in the NCO/OH ratio from 0.75 to 0.85. The decrease in polystyrene content and NCO/OH ratio caused a decrease in the amount of stiff material in the IPN, leading to an increase in elongation. The decrease in stiff material was expected to cause a decrease in tensile stress; but contrary to expectation, the tensile stress increased with a decrease in stiffer material. This phenomenon has not been explained [56], but may possibly be due to synchronization of the phases. Prashantha et al. [57] studied IPNs-based on polyol modified castor oil polyurethane and poly (2hydroxyethylmethacrylate). They investigated mechanical and thermal properties of the IPNs such as tensile strength, elongation, hardness, Tg and degradation. The tensile strength ranged from 27 to 38 MPa and elongation at break was between 58 and 120%. All the IPNs showed about 2–4% decomposition at 200 ◦ C, about 10% at 300 ◦ C and about 40% at 400 ◦ C. There was a rapid weight loss from 40 to 90% in temperature ranges of 400–500 ◦ C. Sanmathi et al. [58] synthesized and characterized IPNs from modified castor oil-based polyurethane and poly (2ethoxyethyl methacrylate). The preparation of these IPNs is shown in Scheme 5. The triglyceride of castor oil was exchanged with glycerol, followed by reaction with a diisocyanate to form castor-based PU (GC-PU). 2-Ethoxyethyl methacrylate was subsequently polymerized in the presence of GC-PU to prepare the IPNs. The presence of H-bonding between poly (2-ethoxyethyl methacrylate) and castor PU (GC-PU) is also shown in Scheme 5. The incorporation of poly (2-ethoxyethyl methacrylate) in GC-PU during the formation of IPN caused an increase in tensile strength and decrease in elongation, when compared with the individual components of GC-PU and (2-ethoxyethyl methacrylate). These IPNs exhibited Young’s modulus of the order of 2.9–84 mN/m2 .

Kansara et al. [59,60] also studied the sorption and diffusion behavior of IPNs-based on PU and unsaturated polyester (UPE). The PU was prepared from castor oil polyol. The sorption behavior of these IPNs was studied with changes in crosslink density, NCO/OH mole ratio, composition of the constituents and hydroxyl value. Chlorobenzene was used to study the swelling behavior of the IPNs. Sorption was inversely related to the NCO/OH mole ratio. The crosslink density ranged from 5 to 27 × 104 mol/g for different IPNs, as calculated by the Flory–Rehner equation [61]. An increase in diffusion coefficient was observed with an increase in the NCO/OH molar ratio and the content of unsaturated polyester. Xie and co-workers [62] studied the damping behavior of grafted interpenetrating networks. They prepared IPNs from castor oil, toluene diisocyanate, monohydroxy terminated acrylic prepolymer and acrylic monomer in the presence of dibutyltin dilaurate and redox initiators. The dynamic mechanical properties of the IPNs were observed to exhibit high damping properties over a wide range of temperature. Xie and Guo [63] studied adhesives made from IPNs for bonding with rusted iron without pretreatment. They prepared two types of room-temperature curable IPNs: one from castor oil-based PU and vinyl or acrylic polymer and the other from castor oil PU, unsaturated polyester and vinyl or acrylic polymer. The lap shear strength of joints between rusted iron plates and IPNs (adhesives) ranged from 1.51 to 8 MPa. Nayak and co-workers [64–68] also synthesized and characterized castor oil-based interpenetrating networks. First, they prepared polyurethanes from castor oil and hexamethylene diisocyanate by varying the NCO/OH ratio and then prepared IPNs by reacting polyurethanes with various acrylates such as hydroxyethyl methacrylate and cardanyl methacrylate by using benzoylperoxide as initiator and ethylene glycol dimethacrylate as crosslinker. Infra-red IR spectroscopy, NMR spectroscopy, TGA, etc. were employed to study the properties of resulting IPNs. Cunha et al. [69] employed a statistical method to accurately evaluate the properties of castor oil-based semiinterpenetrating polymer networks (sIPN). They used a 23 factorial experimental design for optimization of the properties. The semi-interpenetrating polymer networks

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Scheme 5. Preparation of GC-PU/poly (2-EOEMA) IPNs. Reproduced from Sanmathi et al. [58] with permission of John Wiley and Sons, Inc.

(sIPNs) were prepared from castor oil polyol, toluene diisocyanate and methyl methacrylate. The properties of these sIPNs depended upon the ratio of the contents and the mole ratio NCO/OH. Various techniques were employed

to study the properties of the sIPNs. They showed different swelling properties for different samples. The sample containing maximum methyl methacrylate exhibited low swelling. Mechanical properties were also largely influ-

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enced by the methyl methacrylate content. For instance, the sIPN containing 20% MMA showed 22.6% swelling and 1.48 MPa elastic modulus, whereas the sIPN containing 60% MMA showed 17.4% swelling and 6.49 MPa elastic modulus. 4. Polymers based on nahar seed oil polyol Nahar (Mesua ferrea L.) seed oil contains mainly triglycerides of linoleic, oleic, palmitic and stearic acids [70]. Karak and co-workers [71–74] studied polyester, polyesteramide, polyurethane and polyurethane amide resins from nahar seed oil [71–74]. They prepared polyester resins from nahar seed oil monoglycerides and phthalic and or maleic anhydrides [71]. Nahar seed oil was first converted into monoglycerides by alcoholysis and then the resins were prepared by reacting monoglycerides with phthalic and or maleic anhydrides. The alcoholysis and polycondensation reaction of the oil with acid anhydride is shown in Scheme 6. An increase in the maleic anhydride content in the resin decreased the curing time. Resin with 50% maleic anhydride took 7 h for complete curing, whereas resin with 75% maleic anhydride took 6 h. The polyester films were highly resistant to dilute HCl (10%), aqueous NaCl salt solution (10%) and distilled water. Polyesteramide resins from nahar oil were also studied by Karak and Mahapatra [72]. The oil was first converted

into methyl ester, and then reacted with diethanol amide to form diethanol amide of fatty acids. The fatty acids amide was then reacted with dibasic acid or their derivatives. The hardness of the resins was tested as pencil hardness. The pencil hardness test is used to test coatings for their hardness and resistance to scratches and wear. The principle of operation uses a pressure applied to allow the pencil lead to just crush and therefore, repeatable results for the hardness of the coating can be obtained. These pencils, when pressed for a specified number of times on the coating, will also allow a wear factor to be determined. This wear factor is related to the hardness of the pencil used. Pencils of different grades are used in the test, ranging from 9H to 9B. [H signifies hardness and as one goes to a lower H number, the lead becomes softer, and grades HB to 9B designate increasing softness (B = blackness).] The pencil hardness of the cured resins as reported by Karak and Mahapatra [72] ranged from HB to 2H. The cured resin had a gloss between 81 and 85 at 60◦ and had 100% adhesion. Karak and Dutta [73] studied the effect of the NCO/OH ratio on the properties of nahar seed oil modified PU resins. The resins were prepared by varying NCO/OH molar ratio from 0.8 to 2.0. The coating properties such as pencil hardness, gloss, adhesion was studied. The hardness of the resins ranged from HB to 3H, the gloss at a 60◦ angle was from 109 to 117% and the adhesive strength was

Scheme 6. Alcoholysis and poly-condensation reaction of oil with acid anhydride. Reproduced from Dutta et al. [71] with permission of Elsevier B.V.

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125–336 kN/m. These properties were found to increase with increasing NCO/OH ratio from 0.8 to 2.0. The PU resin with equal proportions of NCO and OH showed three degradation stages at temperatures of 295, 375 and 490 ◦ C. The degradation temperatures were observed to decrease with increasing NCO/OH ratio. Resin with a NCO/OH ratio of 1.5 showed two-stage degradation at 290 and 390 ◦ C and the resin with a NCO/OH ratio of 2 showed a single-stage degradation at 320 ◦ C. Karak and Dutta [74] synthesized poly (urethane amide) resins from nahar seed oil and TDI in the presence of dibutyl tin dilaurate (DBTDL) as catalyst. The coating performance of these resins was tested by measuring gloss, pencil hardness, adhesion and chemical resistance. The gloss at a 45◦ angle ranged from 66 to 70 and the pencil hardness ranged from HB to 2H. Chemical resistance was studied for 10 days insolutions of NaOH, HCl, NaCl, ethyl alcohol and in distilled water. The cured PU amide resin showed average to excellent chemical resistance. 5. Other polymers based on oil polyols There are many vegetable oils other than soybean, castor and nahar that can be used in the synthesis of polyols for PUs, such as rapeseed oil, palm oil, canola oil, linseed oil, olive oil, sunflower oil, safflower oil, etc. Rapeseed oil methyl esters have been synthesized by the reaction of rapeseed oil and methanol at a temperature range of 60–70 ◦ C with sodium hydroxide as a catalyst. They have been produced on an industrial scale for use as biodiesel fuel [75]. Hu et al. [76] prepared rigid polyurethane foam from rapeseed oil polyol. They first converted the oil into polyol by hydroxylation, followed by alcoholysis. The alcoholysis of the hydroxylated rapeseed oil was required because of its low hydroxyl value (ca. 100 mg KOH/g), which is not suitable for the preparation of rigid polyurethanes. The polyol thus prepared was compared with a commercially available polyester polyol, Daltolac P744. The experimental data indicate that the compression strength of the PU foam made from rapeseed oil polyol is lower than that of Daltolac P744-based foam. The other properties of the rapeseed oil polyol foam are similar to those of commercial foam, Daltolac P744. Chian and Gan [77] reported the development of rigid PU foams from palm oil. Their PU foams exhibited high compression strength (1–35 MPa) and densities (200–300 kg/m3 ). Desai and co-workers [78] reported PU adhesive from argemone oil and castor oil for wood bonding applications. The best performing adhesive (argemine oil-based) was compared with various commercially available adhesives such as Dunlop adhesive, Fevicol and Araldite. The average lap shear strength of PU adhesive was 63.1 × 105 N/m2 , while the highest strength for the commercially available adhesives was observed to be 28.3 × 105 N/m2 for araldite. Ahmad et al. [79] synthesized polyesteramide from Pongamia glabra oil for biologically safe anticorrosive coatings. The oil was first converted to N,N-bis(2-hydroxyethyl) P. glabra fatty amine (HEPGA) and then HEPGA was converted into polyesteramide (PGPEA) by reaction with

Fig. 9. Glass transition behavior for several vernonia-sebacic polyester network/PET semi-IPN compositions. First heat data, the materials as synthesized (A) and second heat data, recorded after cooling rapidly from 300 ◦ C. Reproduced from Barrett et al. [81] with permission of John Wiley and Sons, Inc.

phthalic acid. The PGPEA coatings showed 10% weight loss up to 275 ◦ C, 50% weight loss up to 370 ◦ C and 78% weight loss up to 400 ◦ C. Almost all of the physico-mechanical properties such as scratch hardness (3.5 kg), gloss (up to 90% at a 60◦ angle) and adhesion strength (100%) were superior to those of polyesteramides obtained from other seed oils. Ahmad et al. [80] also studied ambient cured PU modified epoxy coatings from linseed oil. The linseed oil was first hydroxylated and then linseed oil PU was prepared. The linseed oil PU obtained by 10% loading of TDI showed the best physico-mechanical and anticorrosive properties. Barrett et al. [81] synthesized semi-IPNs from vernonia oil–sebacic acid polyester network (VOSA) and PET. The semi-IPN containing 50% PET and 50% VOSA was observed to be over 15 times tougher than PET and over 50 times tougher than the neat vernonia oil elastomer. The semiIPN with 50% PET showed better properties than the other semi-IPNs, e.g. the tensile strength for the semi-IPN with 50% PET was 6030 MPa and the modulus was 25.8 MPa. The derivative plots for the first and the second heating scans in DSC heat flow around the Tg region are shown in Fig. 9.

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V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215 [16] Husic S, Javni I, Petrovic ZS. Thermal and mechanical properties of glass reinforced soy-based polyurethane composites. Compos Sci Technol 2005;65:19–25. [17] Petrovic Z, Guo A, Javni I. Process for the preparation of vegetable oil-based polyols and electroinsulating casting compounds created from vegetable oil-based polyols, 2000; US Patent 6,107,433. [18] Petrovic Z, Javni I, Guo A. Method of making natural oil-based polyols and polyurethanes there from, 2002; US Patent 6,433,121. [19] Petrovic ZS, Javni I. Process for the synthesis of epoxidized natural oil-based isocyanate prepolymers for application in polyurethanes, 2002; US Patent 6,399,698. [20] Guo A, Zhang W, Petrovic ZS. Structure-property relationships in polyurethanes derived from soybean oil. J Mater Sci 2006;41:4914–20. [21] Dzunuzovic E, Tasic S, Bozic B, Babic D, Dunjic B. UV-curable hyperbranched urethane acrylate oligomers containing soybean fatty acids. Progr Org Coat 2005;52:136–43. [22] Fan XD, Deng Y, Waterhouse J, Pfromm P. Synthesis and characterization of polyamide resins from soy-based dimer acids and different amides. J Appl Polym Sci 1998;68:305–14. [23] Deng Y, Fan XD, Waterhouse J. Synthesis and characterization of soybased copolyamides with different -amino acids. J Appl Polym Sci 1999;73:1081–8. [24] John J, Bhattacharya M, Turner RB. Characterization of polyurethane foams from soybean oil. J Appl Polym Sci 2002;86:3097–107. [25] Singh AP, Bhattacharya M. Viscoelastic changes and cell opening of reacting polyurethane foams from soy oil. Polym Eng Sci 2004;44:1977–86. [26] Rosch J, Mulhaupt R. Polymers from renewable resources: polyester resins and blends based upon anhydride-cured epoxidized soybean oil. Polym Bull 1993;31:679–85. [27] Eren T, Kusefoglu SH, Wool R. Polymerization of maleic anhydridemodified plant oils with polyols. J Appl Polym Sci 2003;90: 197–202. [28] Dwan’Isa JP, Mohanty AK, Misra M, Drzal LT, Kazemizadeh M. Novel biobased polyurethanes synthesized from soybean phosphate ester polyols: thermomechanical properties evaluations. J Polym Environ 2003;11:161–8. [29] Monteavaro LL, Riegel IC, Petzhold CL, Samios D. Thermal stability of soy-based polyurethanes. Polimeros: Ciencia e Technologia 2005;15:151–5. [30] Pechar TW, Sohn S, Wilkes GL, Ghosh S, Frazier CE, Fornof A, et al. Characterization and comparison of polyurethane networks prepared using soybean-based polyols with varying hydroxyl content and their blends with petroleum-based polyols. J Appl Polym Sci 2006;101:1432–43. [31] Quintero C, Mendon SK, Smith OW, Thames SF. Miniemulsion polymerization of vegetable oil macromonomers. Progr Org Coat 2006;57:195–201. [32] Bao LH, Lan YJ, Zhang SF. Effect of NCO/OH molar ratio on the structure and properties of aqueous polyurethane from modified castor oil. Iran Polym J 2006;15:737–46. [33] Barrett LW, Sperling LH, Gilmer J, Mylonakis SG. Crystallization kinetics of poly (ethylene terephthalate) in compositions containing naturally functionalized triglyceride oil. J Appl Polym Sci 1993;48:1035–50. [34] Ajithkumar S, Kansara SS, Patel NK. Kinetics of castor oil based polyoltoluene diisocyanate reactions. Euro Polym J 1998;34:1273–6. [35] Somani KP, Kansara SS, Patel NK, Rakshit AK. Castor oil based polyurethane adhesives for wood-to-wood bonding. Int J Adhesion Adhesives 2003;23:269–75. [36] Yeganeh H, Mehdizadeh MR. Synthesis and properties of isocyanate curable millable polyurethane elastomers based on castor oil as a renewable resource polyol. Euro Polym J 2004;40:1233–8. [37] Hepburn H. Polyurethane elastomers. Essex: Elsevier; 1992. [38] Yeganeh H, Shamekhi MA. Novel polyurethane insulating coatings based on polyhydroxy compounds, derived from glycolyzed PET and castor oil. J Appl Polym Sci 2006;99:1222–33. [39] Yeganeh H, Hojati-Talemi P. Preparation and properties of novel biodegradable polyurethane networks based on castor oil and poly (ethylene glycol). Polym Degrad Stab 2007;92:480–9. [40] Zanetti-Ramos BG, Lemos-Senna E, Soldi V, Borsali R, Cloutet E, Cramail H. Polyurethane nanoparticles from a natural polyol via miniemulsion technique. Polymer 2006;47:8080–7. [41] Ogunniyi DS, Fakayejo WRO, Ola A. Preparation and properties of polyurethane foams from toluene diisocyanate and mixtures of castor oil and polyol. Iran Polym J 1996;5:56–9. [42] Yin Y, Yao S, Zhou X. Synthesis and dynamic mechanical behavior of crosslinked copolymers and IPNs from vegetable oils. J Appl Polym Sci 2003;88:1840–2.

All the semi-IPNs showed two glass transitions in the first scan, which transformed into a single transition in the second scan after rapid cooling from 300 ◦ C. Thus the materials were multiphase as prepared, but after heating to above the melting point of the PET and cooling, they became nearly single phase or microheterogeneous. 6. Conclusions Waste plastic materials are the major concerns of environmentalists. Thus, renewable resources are now greatly favored for the production of polymers. The wide range of mechanical properties and the ability for easy machining and forming cause the plastic foams and elastomers to find wide industrial and consumer applications. In particular, urethane foams and elastomers have been found to be well suited for many applications. The vegetable oils provide a large variety of options for the preparation of polyurethanes. All the vegetable oils are triglycerides of fatty acids and most contain unsaturated groups. Only a few oils contain other groups such as hydroxyl in castor oil, safflower oil and lesquerella oil, and oxirane group in vernonia oil. Soybean and linseed oils are also used in the preparation of polyurethanes by converting them into epoxies or by hydroformylation. The incorporation of oils in the polyurethanes provides a great opportunity to tailor the properties of polyurethane products. References
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