Two different bisoxazolines, 2,2'-(1,3-phenylene) bis(2-oxazoline) (1,3-PBO) and 2,2'-bis(2-oxazoline) (BO) were investigated as chain extenders for short chain unsaturated polyesters (UPEs). These extenders reacted readily with carboxyl ends of unsaturated polyesters, leading to rapid molecular weight increase through coupling of oligomeric chains. Commercially available unsaturated polyesters commonly have molecular weights around 1500, usually reached after a 20-h polyesterification reaction. When bisoxazolines were reacted with short UPE chains obtained at the 6th hour of a commercial polyesterification reaction, the molecular weight of UPE reached 1500 within 530 min, which provides economies and prevents the glycol loss and yellowing which are associated with extended reaction times. Styrene solubility, gel time, and thermal and mechanical properties of the chain extended polyesters remained comparable to the commercial UPE, with 810 min of gel time and a storage modulus about 3000 MPa. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

In this study 4-methylpyridine (4MP), 4-vinylpyridine (4VP) and poly(4-vinylpyridine) (P4VP) were separately reacted with epoxidized soybean oil triglycerides (ESO) to give plant oil based thermoset polymers. The addition reaction of pyridine with epoxide followed by a rearrangement results in formation of pyridone units and these were polymerized via a Diels-Alder reaction. DMA, DSC, TGA and IR spectroscopy were used for the characterization of the products. 4MP-ESO, P4VP-ESO and P4VP-ESO-in situ polymers were crosslinked yielding rigid infusible polymers. Glass transition temperatures (T-g) of 4MP-ESO and P4VP-ESO-in situ were found as -10.5 and 70.5 (32.3 as shoulder) degrees C respectively, by DMA analysis. Storage moduli of 4MP-ESO and P4VP-ESO-in situ at 25 degrees C were 13.7 and 187.2 MPa, respectively. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121:2976-2984, 2011

In this work, the Diels–Alder reaction between the acrylate groups of acrylated epoxidized soybean oil and the furan rings of p-tertiary butyl phenol furfural resin (TBPF) is described. The reaction was carried out at 110°C in presence of FeCl3 catalyst, and tough polymers were obtained in 1 h. Surprisingly, samples that were heated and cooled 5, 10, and 20 times to 140°C and room temperature had better mechanical properties than samples that were kept at 140°C for the same total duration. This unexpected behavior is attributed to a series of forward and retro Diels–Alder reactions between the functional groups. To prove this hypothesis, a model reaction between TBPF and n-butyl acrylate was studied. At 100°C, 1H-nuclear magnetic resonance signals of the furan ring protons disappeared, only to reappear at 140°C. Thermogravimetric analysis of the adduct showed a weight loss at 140–150°C, which was in quantitative agreement with the amount of butyl acrylate. Infrared analysis showed that furan rings were not completely consumed by extended heating at 110°C. After five heating and cooling cycles of much shorter duration at 140°C, the furan absorption in the infrared disappeared. The storage modulus of acrylated epoxidized soybean oil-TBPF samples after 20 heating cycles was 1.15 GPa. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

In this work new radically polymerizable triglyceride based monomers were synthesized by the reaction of epoxidized methyl oleate (EMO) and epoxidized soybean oil (ESO) with 4-vinyl benzene sulfonic acid (4VBSA). The products are 1-(4-vinylbenzene sulfonyl)oxy-2-alkonols of epoxidized soybean oil (SESO) and 1-(4-vinylbenzene sulfonyl)oxy-2-alkonols of epoxidized methyl oleate (SEMO). These adducts were characterized by 1H NMR, 13C NMR, IR and CHNS elemental analysis. SESO was found to contain, on the average, 2.47 4VBSA units per triglyceride. SESO was free radically polymerized and co-polymerized with styrene and the mechanical and thermal properties of the resulting thermosets were determined by DMA, DSC and TGA. SEMO was used as a model compound to determine the efficiency of metathesis catalysts for these fatty acid derivatives. The second generation Hoveyda–Grubbs catalyst was found to give best yields. ADMET polymerization of SESO with this catalyst with and without solvent gave ∼80% yield of a thermoset polymer. Polymers obtained by free radical route swelled in water at room temperature, and hydrolyzed in water at 60°C.

Two different blocked isocyanates, diphenylmethane- bis-4,4'-ethyleneurea and diphenylmethane-bis-4,4'-carbamoil-epsilon-caprolactam, and isocyanated soybean oil were used as chain extenders for low-molecular-weight unsaturated polyesters. Oligomeric polyesters (molecular weight = 600-700), taken from a manufacturing process in the sixth hour of a 16-h polyesterification reaction, were reacted with these chain extenders, and the desired chain lengths (molecular weight = 1000-1500) were obtained in a very short time through the reaction of the chain extenders with the polyester end groups. The increase in the molecular weight was monitored with gel permeation chromatography. The obtained polymers were characterized with Fourier transform infrared and H-1-NMR and with styrene solubility and gel time measurements. After dilution with styrene, the polyesters were cured with a radical initiator. The thermal and mechanical properties of the cured polyesters were examined with dynamic mechanical analysis and thermogravimetric analysis tests and then compared to those of a commercially available reference unsaturated polyester. The results show that unsaturated polyesters can be chain-extended with these compounds to shorten the polyesterification time substantially without alterations of the styrene solubility or gel time of the polyesters. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 1102-1110, 2011

In this study, maleinized soybean oil triglycerides (SOMA) were reacted with epoxidized soybean oil triglycerides (ESO) to give plant oil-based thermoset polymers. To increase fracture toughness of the product, different amounts of SOMA was replaced by maleic anhydride grafted polypropylene (MMPP) (Epolene E43, maleate content 2.9%, M-n = 3900 and Polybond 3200, maleate content 1%, M-n = 1,10,000). The improvement in mechanical properties was monitored. The characterizations of the products were done by DMA, DSC, TGA, and IR spectroscopy. ESO-SOMA and ESO-SOMA-MMPP polymers are crosslinked rigid infusible polymers. ESO-SOMA-MMPP(E43) and ESO-SOMA-MMPP(PB3200) showed a phase change at 146 and 169 degrees C, respectively, probably due to the melting transition of the MMPP backbone. Storage moduli of the two polymers at 35 degrees C were 54.6 and 246.1 MPa, respectively. Storage moduli and the impact strength of the polymers increased with MMPP content and with MMPP molecular weight. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 3311-3317, 2010

In this article, a novel two step synthesis of soy oil based isothiocyanate is described. Allylicaly brominated soybean oil (ABSO) was reacted first with ammonium thiocyanate in tetrahydro furan to form allylic thiocyanates. These compounds were then converted to isothiocyanated soybean oil (ITSO) by a thermal rearrangement. Conversion was found to be 70%. The structure of the ITSO was characterized by IR and H-1-NMR techniques. Then ITSO was reacted with ethylene glycol, glycerol, and castor oil to produce polythiourethanes and ethylene diamine and triethylene tetra amine to produce polythioureas. Thermal properties of the products were determined by DSC and TGA techniques. DSC traces showed 7(g)'s for ethylene glycol polythiourethane at -39 and 58 degrees C, for glycerol polythiourethane at -39 and 126 degrees C, for castor oil polythiourethane at -38 degrees C and -17 degrees C, for ethylene diamine polythiourea at -45 degrees C, and for triethylene tetra amine poly thiourea at -39 degrees C. Additionally, DSC analysis of polythioureas showed an endotherm at around 100 degrees C. All of the polymers started to decompose around 200 degrees C. Tensile properties of the polymers were determined. Polythiourethanes showed higher tensile strength and lower elongation when compared with their urea analogs. Stress at break values of the polymers were 1.2 MPa for glycerol polythiourethane, 0.6 MPa for ethylene glycol polythiourethane, 0.5 MPa for ethylene diamine polythiourea, and 0.9 MPa for triethylene tetra amine polythiourea polymers. Unfortunately, polymers synthesized showed poor solvent resistance. All polymers swelled and disintegrated in CH2Cl2 in 5 h. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 125-131, 2010

Single fiber fragmentation test (SFFT) was used to investigate the interfacial adhesion in glass fiber-unsaturated polyester composites. A simplified approach was developed for SFFT based on determination of the maximum number of fragments on the fiber at the end of the test. This approach does not involve length measurements and shortens the experiment time to a few minutes. By using a digital camera attached to the microscope, photographs of the coupon were taken during the test, and the number of fragments within the gauge length were counted later. This method allows quick, quantitative comparison of different fibers and matrices. The test samples were prepared by using commercial polyester resin and E-glass fibers having different commercial sizings. SFFT results were in excellent agreement with the macromechanical test done on samples prepared with the same glass fiber and same polyester. The crack modes and debonding phenomena were examined from the microscopic images. Atomic force microscopic (AFM) images of the fiber were examined to get detailed topographic information about fiber surfaces. To improve interfacial adhesion, commercial unsaturated polyester was reacted with 3-aminopropyltriethoxy silane via Michael Addition reaction on the maleate double bonds of the polyester. The resulting silylated polyester was characterized by H-1 NMR spectroscopy. The results of SFFT showed that the maximum numbers of fragments increased 23% on using silylated polyester. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 748-755, 2010

In this study, maleinized (SOMAP) and isocyanated soybean oil (SONCO) triglycerides have been successfully grafted onto one surface of poly(vinyl alcohol)(PVA) films to give films that are hydrophilic on one side and hydrophobic on the other. The surface grafting was accomplished by the reaction of succinic anhydride or isocyanate functionalities of soybean oil derivatives and the hydroxyl groups of PVA films. The reaction was run in toluene, using PVA films on glass slides so that only one side of the film was accessible. After grafting, the films were rinsed with hot toluene to remove ungrafted triglycerides from the surface. The reaction on the surface was confirmed by ATR-FTIR and H-1-NMR spectroscopic techniques. A series of films were prepared at different concentrations of SOMAP or SONCO in toluene. The increase in hydrophobicity with an increase in SOMAP or SONCO concentrations was observed by water contact angle measurements. The contact angles on the grafted side of the film reach their maximum value of 88 degrees and 94 degrees for 26 and 2.5% SOMAP and SONCO concentrations in toluene, respectively, while the ungrafted side gives contact angle of 48 degrees. Surface morphologies of PVA-g-SOMAP and PVA-g-SONCO films were investigated by atomic force microscopy, whereas optical microscopy and staining was used to determine the homogeneity of the films. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 2431-2438, 2011

In this study a novel and simple route for the synthesis of the iodine isocyanate (INCO) adduct of soybean oil triglycerides is described. Soybean oil iodo isocyanate (ISONCO) was synthesized by the reaction of iodine isocyanate and soybean oil at room temperature. ISONCO was then polymerized With polyols, such as, castor oil, pentamethylene, glycol, and glycerol to give the corresponding polyurethanes and with polyamines, Such as, ethylene diamine, hexamethylene diamine, and triethylene tetramine to give corresponding polyureas. The structures of the monomer and the polymers were determined by FTIR and H-1-NMR analyses. Thermal properties of the polymers were determined by DSC and TGA. Thermal degradation of the polyurethanes started at 150 degrees C. Stability of the polyureas was higher than polyurethanes. Almost all polymers showed a T-g around -50 degrees C. The mechanical properties of the polymers were determined by tensile tests. Among the polymers synthesized, castor oil polyurethane showed the highest elongation at break and the lowest tensile strength of 140 KPa. The highest tensile strength of 900 KPa was observed in the pentamethylene glycol polyurethanes. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 2433-2440, 2010

Epoxidized soybean oil (ESO) triglycerides were reacted with maleinized polybutadiene (MMPBD) to give plant-oil-based thermoset polymers. MMPBD samples were of two different molecular weights [high-molecular-weight maleinized polybutadiene (MMPBD-H), maleate content = 10%, number-average molecular weight (M-n) = 9000, and low-molecular-weight maleinized polybutadiene (MMPBD-L), maleate content 15%, M-n = 5000]. To increase the crosslink density of the product, a free-radical initiator, benzoyl peroxide, was added to this mixture to further crosslink MMPBD through its double bonds. The characterizations of the products were done by dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis, and IR spectroscopy. The ESO-MMPBD polymers were crosslinked rigid infusible polymers. ESO-MMPBD-H-1 : 1 and ESO-MMPBD-L-1 : 1 showed glass-transition temperature values at -23, 78 and -17, 64 degrees C, respectively, whereas the storage moduli of the two polymers at 25 degrees C were 13 and 16 MPa, respectively. The storage moduli of the polymers remained the same or decreased with the addition of a free-radical initiator. The storage moduli also decreased with increasing ESO concentration above a 1 : 1 epoxy-to-anhydride molar ratio. The surface hardness increased dramatically, and the equilibrium swelling ratio decreased with the addition of free-radical initiator. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120: 116-123, 2011

In this study, linseed oil was directly polymerized with different oil soluble resoles. p-Ethyl (PEP), p-tertiary butyl (PTB), p-tertiary octyl (PTO), and p-phenyl (PPP) phenols were separately reacted with formaldehyde to give linseed oil soluble resoles. These were then reacted with linseed oil to give transparent rubbery polymers. A model reaction was performed with methyl oleate and PTB phenol resole to clarify the reaction mechanism. Reaction products were characterized with (1)H-NMR and IR techniques. Spectral examination of the model reaction showed that polymerization reaction proceeded via ene reaction of the quinone methide formed at the end group of the resole with the allylic positions of the fatty ester. Rubbery polymers were obtained with linseed oil using 10 to 40% of the different resoles. Hard, load bearing and tough materials were obtained at 40% phenolic resin loading. Mechanical properties of the materials were characterized by dynamic mechanical analyzer (DMA) and stress strain tests. The best mechanical and thermal properties were obtained with PEP resole which showed a storage modulus of 350 MPa and a tan 8 peak at 65 degrees C. Storage moduli of 275, 250, and 30 were obtained for PPP, PTB, and PTO resoles-linseed oil polymers, respectively. At the same phenolic resin loading, elongation at break and swelling ratios in CH(2)Cl(2) increased with the longer alkyl substitution on the resole resins. The highest thermal stability was observed by PEP resole linseed oil polymer which has a 5% weight loss temperature of 340 degrees C as determined by TGA. The lowest thermal stability was observed for PTB resole-linseed oil polymer at 220 degrees C. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 849-856, 2010

In this study, styrene maleic anhydride copolymer (SMA2000, Styrene : Maleic Anhydride 2 : 1) is grafted and/or crosslinked with epoxidized methyl oleate, epoxidized soybean oil, methyl ricinoleate (MR), castor oil (CO), and soybean oil diglyceride. Base catalyzed epoxy-anhydride and alcohol-anhydride polyesters were synthesized by using the anhydride on SMA, the epoxy or secondary alcohol groups on the triglyceride based monomers. The characterizations of the products were done by DMA, TGA, and IR spectroscopy. SMA-epoxidized soy oil and SMA-CO polymers are crosslinked rigid infusible polymers. SMA-epoxidized soy oil and SMA-CO slioxved T-g's at 70 and 66 degrees C, respectively. Dynamic moduli of the two polymers were 11.73 and 3.34 Mpa respectively. SMA-epoxidized methyl oleate, poly[styrene-co-(maleic anydride)]-graft-(methyl ricinoleate), and SMA-soy oil diglyceride polymers were soluble and thermoplastic polymers and were characterized by TGA, GPC, DSC, NMR, and IR spectroscopy. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 355-365, 2010

Unsaturated polyesters (UPE) were chain extended with three different epoxy group containing compounds. The molecular weight increase was monitored using gel permeation chromatography (GPC). The polymers obtained were characterized by FTIR and H-1 NMR, and styrene solubility and gel time. The polyesters were then diluted with styrene and cured with a radical initiator and compared with a commercial reference polyester. Thermal and mechanical properties of the cured polyesters were characterized by dynamic mechanical analysis (DMA) and thermal gravimetric analysis (TGA). The results show that UPE can be chain extended with epoxy containing compounds which substantially shortens the condensation polymerization during manufacture, without compromising their thermal and mechanical properties. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 1184-1191, 2009

In this study, rubbery, bio-based thermoset polymers were synthesized from soybean oil (SO) and p-dinitrosobenzene (DNB) via an ene reaction. Polymeric p-dinitrosobenzene (PDNB) was synthesized from p-quinone dioxime and was thermally depolymerized in the presence of SO. SO/PDNB polymers were synthesized by a two-stage polymerization. During the reaction, the role of different parameters such as mol ratio of SO and PDNB, preheating temperature of SO, polymerization time, and temperature were examined. Polymerization was followed by IR spectroscopy, and the polymers obtained were characterized by dynamic mechanical analysis, thermogravimetric analysis, and differential scanning calorimetry. The polymers have glass transition temperature ranging from −51.5°C to −46.3°C, whereas their storage moduli are between 430 and 210 MPa at −60°C. Thermogravimetric analysis reveals that all of the polymers have temperatures of maximum degradation around 500°C. The crosslinked network structure of the polymers was investigated by swelling behavior and surface hardness test. Methyl oleate was used as a model compound to examine the chemical structure of the products. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

In this study, biodegradable rigid cellular materials were synthesized from the reaction of malonic acid with epoxidized soybean oil. Malonic ester reacts with two epoxy reaction, initially formed malonic acid monoester (MAME) can decarboxylate and produce CO2, which acts as the blowing agent leading to in situ foaming of the polymer. Epoxide addition and decarboxylation reactions of MAME occur competitively and simultaneously and by controlling their relatives rates, foams of controlled density were produced. H-1 NMR spectrum of the synthesized foams showed that increasing the temperature increases the rate of decarboxylation reaction of MAME and decreases crosslink dencity leading to softer and lower density foams. Addition of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a catalyst also increases the rate of decarboxylation. Load deflection curves of the cellular materials showed that decreasing the temperature and addition of DABCO increase compressive modulus of samples. Cell morphology was studied by microscopic images of foam samples that showed that foam samples have a closed cell structure and a wide distribution of cell volume. Soil burial test was done todetermine rate of biodegradation of foam samples. A half-life of 815 days showed that foam samples are highly biodegradable. (c) 2008 Wiley Periodicals, Inc.

Completely bio-based and renewable polymeric nanocomposites have been prepared using an in situ polymerization technique in the presence of organically-modified montmorillonite (MMT) clays in different loading degrees. Acrylated epoxidized soybean oil (AESO) and styrene have been used as matrices, whereas modification of MMT has been clone by using a new renewable soybean-oil-based intercalant. quarternized functionalized acrylated epoxidized soybean oil, which is the first renewable intercalant described in the literature. It was found that the above-mentioned intercalant could be successfully intercalated between the interlayer galleries of montmorillonite which is confirmed by X-ray diffraction (XRD) data and atomic force microscopy (AFM). The nanocomposite formation Studies examined by both XRD and AFM showed that the desired exfoliated nanocomposite structures can be achieved with all nanofiller loadings. The resultant exfoliated nanocomposites were found to have significantly improved thermal stability and dynamic mechanical performance at very low loadings. The nanocomposites from both renewable intercalant and matrix offer a significant potential for new high-volume. low-cost application,,. (C) Koninklijke Brill NV, Leiden, 2008