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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 5–30 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 8–10 min of gel time and a storage modulus about 3000 MPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

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 1 H NMR, 13 C 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.

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 (Tg) of 4MP-ESO and P4VP-ESO-in situ were found as −10.5 and 70.5 (32.3 as shoulder) °C respectively, by DMA analysis. Storage moduli of 4MP-ESO and P4VP-ESO-in situ at 25°C were 13.7 and 187.2 MPa, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 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

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 (Mn) = 9000, and low-molecular-weight maleinized polybutadiene (MMPBD-L), maleate content = 15%, Mn = 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°C, respectively, whereas the storage moduli of the two polymers at 25°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. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

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 1H-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° and 94° for 26 and 2.5% SOMAP and SONCO concentrations in toluene, respectively, while the ungrafted side gives contact angle of 48°. 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. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Two different blocked isocyanates, diphenylmethane–bis-4,4′-ethyleneurea and diphenylmethane–bis-4,4′-carbamoil–ϵ-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 1H-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. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 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%, Mn = 3900 and Polybond 3200, maleate content 1%, Mn = 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°C, respectively, probably due to the melting transition of the MMPP backbone. Storage moduli of the two polymers at 35°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. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 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 1 H-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 Tg's for ethylene glycol polythiourethane at −39 and 58°C, for glycerol polythiourethane at −39 and 126°C, for castor oil polythiourethane at −38°C and −17°C, for ethylene diamine polythiourea at −45°C, and for triethylene tetra amine poly thiourea at −39°C. Additionally, DSC analysis of polythioureas showed an endotherm at around 100°C. All of the polymers started to decompose around 200°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. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 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 H1 NMR spectroscopy. The results of SFFT showed that the maximum numbers of fragments increased 23% on using silylated polyester. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 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 1H 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. © 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 acid reacts with two epoxy groups to give a network polymer. In the course of this 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 relative rates, foams of controlled density were produced. 1H NMR spectrum of the synthesized foams showed that increasing the temperature increases the rate of decarboxylation reaction of MAME and decreases crosslink density 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 to determine rate of biodegradation of foam samples. A half-life of 815 days showed that foam samples are highly biodegradable. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Short chain alcohol esters of fatty acids can be used as diesel fuel. In this study, one step and two step base catalyzed room temperature transesterification reaction of used cooking oil was compared. In the two step base catalyzed process, for 1000 g of used cooking oil 4.2 g NaOH and 140 ml MeOH was used in the first step and 1.8 g NaOH and 60 ml MeOH was used in the second step. All reactions were done at 25 °C; the effects of water content and suspended particles on the yield were studied. The yields were easily determined by Thermo Gravimetric Analysis (TGA) instead of the usual Gas chromatography (GC) and the viscosity of products was measured by Ubbelohde type viscosimeter. It was found that two step processes gives a better yield (96%) than the one step process (86%).

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 done 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 stabili...

In this study, an easy and efficient synthesis of unsaturated plant oil triglycerides having isocyanate groups is reported. In the first step of the synthesis, the triglyceride was brominated at the allylic positions by a reaction with N-bromosuccinimide, and in the second step, these brominated species were reacted with AgNCO to convert them to isocyanate-containing triglycerides. At the end of the reaction, approximately 60–70% of the bromine was replaced by NCO groups, and the double bonds of the triglyceride were not consumed. When the amount of AgNCO was increased, the yield also increased. The final products were characterized with IR and 1H-NMR, and polyurethanes and polyureas were obtained from these fatty isocyanates with alcohols and amines, respectively. The polymers were characterized by differential scanning calorimetry and thermogravimetric analysis. Differential scanning calorimetry curves showed that glycerin polyurethane showed a glass-transition temperature at 19°C, castor oil polyurethane showed two glass-transition temperatures at −43 and 36°C, and triethylene tetraamine polyurea showed a glass-transition temperature at 31°C. Some properties of the polymers, such as the tensile strength and swelling ratios, were also determined. The swelling rate of glycerin polyurethane was higher than that of castor oil polyurethane in dichloromethane. The equilibrium swelling ratio was highest for the castor oil polyurethane. The polyurethanes synthesized in this study had a Young's modulus around 50 kPa and a tensile strength around 0.01 N/mm2 (100 kPa). The tensile strength of glycerin polyurethane was higher than that of castor oil polyurethane. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

In this study silanized acrylated epoxidized soybean oil (silanized-AESO), a multifunctional monomer, was synthesized by reacting acrylated epoxidized soybean oil with 3-Aminopropyltriethoxysilane via a Michael addition reaction using less than equivalent amount of the silane. The characterization of silanized-AESO was done by NMR and IR spectroscopy. Free radically initiated homopolymer of silanized-AESO was synthesized by using the residual acrylate groups. The silanized-AESO homopolymer was characterized by IR spectroscopy. The interfacial adhesion of the polymer on glass surface before and after moisture cure was measured according to ASTM D 4541 Pull-Off Adhesion Test. After moisture curing process, an approximate of eightfold improvement was observed in the adhesion strength. Prolonged exposure to 92% humidity for 48 h caused to approximately 15% decrease in the adhesion strength. Silanized-AESO was copolymerized with styrene in 1 : 1 weight ratio via radical polymerization. The effect of increased crosslink density upon moisture cure on the mechanical and physical properties of silanized-AESO-styrene copolymer was analyzed by DMA (Dynamic Mechanical Analysis), swelling, and surface hardness tests. Upon moisture cure 35% improvement was observed in the storage modulus because of the increase in the crosslink density. According to tan δ curves and surface hardness tests, silanized-AESO-styrene copolymer shows heterogeneous morphology in crosslinked areas. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2244–2253, 2007

Soybean oil triglycerides (SOT) can be used for the synthesis of rigid polymers. This research investigates the potential of using dense (sub/supercritical) CO2 in the reaction medium for the addition of functional groups to SOT. As an alternative and novel method, the reaction of SOT with KMnO4 in the presence of water and dense CO2 is presented. Dense CO2 is utilized to bring the soybean oil and aqueous KMnO4 solution into contact. Experiments are done at 10,25, 34.5, 50 °C and 2.5, 5, 7, 11, 16 MPa. Effects of temperature, pressure, NaHCO3 addition, and KMnO4 amount on the conversion (depletion by bond opening) of soybean-triglyceride double bonds (STDB) are investigated. The highest STDB conversions, about 40%, are obtained at the near-critical conditions of CO2. The addition of NaHCO3 enhances the conversion; one mole of NaHCO3 per mole of KMnO4 gives the highest benefit. Increasing KMnO4 up to 10% increases the conversion of STDB.

The aim of this research is to hydroxybrominate and hydroxychlorinate the double bonds of methyl oleate and soybean oil in dense CO2. The hydroxychlorination reactions of vegetable oils in dense CO2 are the first such report in literature. Experiments were performed at the reaction conditions of 8, 25 and 40 °C and 60, 100, 120 and 150 bar. Effects of temperature, pressure, reaction time and the reactant amounts on the extent of reaction are studied. Hydroxybromination and hydroxychlorination reactions are conducted using sodium hypobromite (NaOBr) and sodium hypochlorite (NaOCl) solutions, respectively. The polymerization of the product is performed by urethane formation with toluenediisocyanate at 40 °C. The products were analyzed by NMR and IR spectrometry. Fifty percent consumption of the double bonds was observed in the hydroxybromination reaction of methyl oleate, but no OH addition was determined. In hydroxychlorination reactions of methyl oleate the consumption of double bonds ranges from 40 to 95%, and the introduction of OH groups ranges from 14 to 30%. Best yields were observed when the mole ratio of NaOCl to methyl oleate double bonds is 5 to 1. The consumption of soybean triglyceride double bonds, in the hydroxychlorination reactions, are observed to range from 18 to 75% and the formation of OH groups ranges from 8 to 33%. The highest conversion for one-step hydroxychlorination of soybean is obtained at 25 °C and 120 bar for a reaction time of 6 h, with 10/1 ratio of NaOCl to double bonds. Better results were obtained when the product of the reaction was reintroduced to the reactor and retreated with NaOCl and 75% consumption of double bonds and 33% formation of OH groups were observed.

In this study, castor oil was alcoholyzed with both aliphatic alcohols, such as glycerol and pentaerythritol, and an aromatic alcohol, bisphenol A propoxylate. The resulting alcoholysis products were then malinated and cured in the presence of styrene. Soybean oil pentaerythritol glyceride maleates were also prepared for a direct comparison of the properties of the castor oil and soybean oil based resins. Castor oil was directly malinated as well to see the effect of the alcoholysis step on the properties of the castor oil based resins. The monomers synthesized were characterized by 1 H-NMR spectroscopy, and the styrenated resin liquid properties, such as viscosity and surface energy values, were determined. The conversion of polymerization was determined using time resolved FTIR analysis for the styrenated soybean oil pentaerythritol glyceride maleates, castor oil maleates, and castor oil pentaerythritol glyceride maleates. The effect of monomer identity and styrene content on the conversion of polymerization was explored.

Samples of commercial unsaturated polyester (UPE) resin, filled with phase-changeable fillers (PCMs), were prepared, and the thermal and mechanical properties of the cured samples were examined. Fillers chosen were paraffin and Wood's metal. Samples were prepared by making dispersions of these fillers in liquid unsaturated polyester followed by curing with methyl ethyl ketone peroxide (MEKP) and conaphtanate and rigid thermoset samples filled with PCM particles were obtained. The thermal and mechanical behaviors of such a filled composite around the melting points of fillers are very interesting. Effects of varying proportions of PCM on mechanical and thermal properties of final products were examined. The samples show thermal melting behavior without undergoing a change in physical state. Decreases in the maximum working temperature from 75 to 53°C for metal-filled samples and from 75 to 43°C for paraffin-filled samples were observed by using dynamic mechanical thermal analysis. Differential scanning calorimetry indicated that heat absorption of paraffin samples were higher than that of metal-filled samples. For paraffin-filled samples, heats of fusion were 3.44 cal/g for 10% filled sample and 6.35 cal/g for 20% filled sample. For Wood's metal-filled samples, heats of fusion were 1.18 cal/g for 10% metal-filled sample and 1.54 cal/g for 20% metal-filled sample. Surface hardness was tested with Shormeter D. Surface hardness of metal-filled composites varied from 86 to 34 shore D at 21°C and 80.6 to 35 shore D at 80°C. For paraffin-filled samples, surface hardness changed from 86 to 42 shore D at 21°C and from 80.6 to 13 shore D. Morphology of the samples was determined by scanning electron microscopy, of the crack surfaces. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 832–838, 2006

Maleic anhydride modified soybean- and castor-oil-based monomers, prepared via the malination of the alcoholysis products of the oils with various polyols, such as pentaerythritol, glycerol, and bisphenol A pro- poxylate, were copolymerized with styrene to give hard rigid plastics. These triglyceride-based polymers exhibited a wide range of properties depending on their chemical structure. They exhibited flexural moduli in the 0.8-2.5 GPa range, flexural strength in the 32-112 MPa range, glass transition temperatures (Tg) ranging from 72 to 1528C, and surface hardness values in the 77-90 D range. The polymers prepared from castor oil exhibited signifi- cantly improved modulus, strength, and Tg values when compared with soybean-oil-based polymers. These novel castor and soybean-oil-based polymers show comparable properties to those of the high-performance unsaturated polyester (UP) resins and show promise as an alternative to replace these petroleum-based materials. 2006 Wiley

In the first part of this study, simultaneous addition of bromine and acrylate to the double bonds of castor oil was achieved. In the second part of the study, bromoacrylated castor oil (BACO) was reacted with toluenediisocyanate (TDI), to form a prepolyurethane (BACOP). The prepolyurethanes were reacted with styrene (STY), 2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA), and 3-(acryloxy)-2-hydroxy propyl methacrylate (AHPMA) free radically, using the acrylate functional group to prepare the simultaneous interpenetrating polymer networks (SINs). 2,2′-Azobis (isobutyronitrile) (AIBN) was used as the initiator and diethylene glycol dimethacrylate (DEGDMA) was used as the crosslinker. BACO and BACOP were characterized by IR, 1H-NMR, and 13C-NMR techniques. Synthesized polymers were characterized by their resistance to chemical reagents, thermogravimetric analysis, and dynamic mechanical thermal analyzer (DMTA). All the polymers decomposed with 6–10% weight loss in a temperature range of 25–240°C. MMA-type SIN showed the highest Tg (126°C), while STY-type SINs showed the highest storage modulus (8.6 × 109 Pa) at room temperature, with respect to other synthesized SINs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2947–2955, 2006

The Ritter reaction of plant oil triglycerides (such as soybean and sunflower oil) with acrylonitrile was used to introduce acrylamide functionality on the triglyceride. Acrylonitrile and triglycerides were reacted in the presence of H2SO4, and acrylamide derivatives were obtained in yields of 45 and 50% for sunflower oil and soybean oil, respectively. Radical initiated copolymerization of the acrylamide derivatives of the triglycerides with styrene produced semirigid polymers. Characterization of new monomers and polymers was done by 1H-NMR, 13C-NMR, IR, and MS. The swelling behavior of the crosslinked network polymers was determined in different solvents. Glass transiton temperature (Tg) of the cured resin was also determined by differential scanning calorimeter to be 40°C for soybean based polymer and 30°C for sunflower-based polymer. Homo- and copolymerization behavior of acrylamide derivatives of methyl oleate (MOA) and methyl 10-undecenoate (MUA) were also investigated. The reactivity ratios of these monomers with respect to styrene were determined by the Fineman–Ross method using 1H-NMR spectroscopic data. The reactivity ratios were rsty = 1.776; rmoa = 0512 for MOA, and rsty = 1.142; rmua = 0.507 for MUA, respectively. Photopolymerization behaviors of MOA and MUA were also investigated using the photoDSC technique and the rate of polymerization of MUA is higher than that of MOA under the same conditions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2264–2272, 2005

In this study self-supporting, resilient, load bearing polybutadiene - soybean oil gels were obtained. The gels were made by dissolving polybutadiene (PBD) in soybean oil (SO) and selectively crosslinking PBD with a free radical source. PBD concentration, free radical source concentration, and the temperature and time of the crosslinking reaction were varied, and the effects of these changes on the mechanical properties of the gels were examined. Our experiments show that successful gelation is possible within PBD concentration limits of 7.5 to 12%, peroxide concentration between 25 to 100% (based on PBD), temperature between 110°C and 130°C and reaction times of 3 hours with tert.butyl-peroxybenzoate as the free radical source. The crosslinking reaction was followed by IR and H-NMR spectra, and the crosslinking density was followed by compression testing and swelling behavior. Higher radical source concentration and higher PBD concentration gave gels with better mechanical properties. The spectra and the viscosity increase of SO extracted from the gels indicate that there is dimer and trimer formation of SO during the reaction. The spectra of the PBD extracted from gels indicate that SO was added to PBD in a small but measurable amount. Integration of peak intensities in the NMR spectrum of methylene groups of PBD and methylene groups of triglyceride indicated one triglyceride molecule for approximately 45 repeating units in PBD. The modulus of the best gel sample (PBD 10%. peroxide 50%) was 1.96 × 10−2 MPa. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2240–2246, 2005

The reaction of soybean oil with aqueous KMnO4 solution, in the presence of dense CO2, is investigated by monitoring the amount of carbon–carbon double bonds and the fatty acid distribution of soybean oil. Experiments are performed with soybean oil and a model compound (methyl oleate) at 25 and 50 °C and 70, 120 and 130 bar. Reactor configuration (batch and semi-batch), reaction time, and product-storage period on the extent of the reaction are studied. With the semi-batch configuration, water feed rates ranging from 0.023 to 0.250 ml/min are studied. Effect of reaction time is investigated with batch periods of 1, 3, 8, 12, 16, 24, 32 and 40 h. Physical inspections and tests, as well as instrumental analysis are carried out on the soybean-oil-derived products, which are observed to change their characteristics in time in storage vials. The consumption of soybean triglyceride double bonds (STDB) are observed to increase from 23.5 to 32.6%, when the water feed rate in the semi-batch experiments was increased from 0.023 to 0.250 ml/min. A saturation behavior is observed for the consumption of STDB with increasing batch reaction time. STDB consumption is 8% for one-hour reaction time, increasing to 30.1% for 16 h and 42% for 40 h. The samples obtained continued to react during storage, losing more than 80% of their carbon–carbon double bonds and attaining a rubber-like structure. Since there is no permanganate remaining in the collected samples, the change in the remaining fatty acid distribution and the observations about the product physical properties suggest that the depletion of STDB is due to air-oxidation polymerization, possibly initiated at the oil–water interface and accelerated by permanganate in the presence of dense CO2.

In this study, methyl oleate was bromoacrylated in the presence of N-bromosuccinimide and acrylic acid in one step. Homopolymers and copolymers of bromoacrylated methyl oleate (BAMO) were synthesized by free radical bulk polymerization and photopolymerization techniques. Azobisisobutyronitrile (AIBN) and 2,2-dimethoxy-2-phenyl-acetophenone were used as initiators. The new monomer BAMO was characterized by FTIR, GC-MS, 1H, and 13C-NMR spectroscopy. Styrene (STY), methylmethacrylate (MMA), and vinyl acetate (VA) were used for copolymerization. The polymers synthesized were characterized by FTIR, 1H-NMR, 13C-NMR, and differential scanning calorimetry (DSC). Molecular weight and polydispersities of the copolymers were determined by GPC analysis. Ten different feed ratios of the monomers STY and BAMO were used for the calculation of reactivity ratios. The reactivity ratios were determined by the Fineman–Ross and Kelen–Tudos methods using 1H-NMR spectroscopic data. The reactivity ratios were found to be rsty = 0.891 (Fineman–Ross method), 0.859 (Kelen–Tudos method); rbamo = 0.671 (Fineman–Ross method), 0.524 (Kelen–Tudos method). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2475–2488, 2004

Hydroxybromination of methyl oleate, oleic acid and new sunflower oil (high oleic), in an acetone/water mixture by a one step reaction using N-bromosuccinimide, was studied. The yield of bromohydrin products from oleic acid, methyl oleate and sunflower oil were 90%, 78% and 40%, respectively. Reaction products were analyzed by 1 H and 13 C nuclear magnetic resonance spectroscopy, infrared spectroscopy, gas chromatography, and mass spectrometry. The hydrobromide derivative of new sunflower oil was acrylated and polymerized to a new polymer.

The ene reaction between plant oil triglycerides (such as soybean and sunflower oils) and paraformaldehyde was used to introduce a homoallylic hydroxyl functionality on the triglyceride. Paraformaldehyde and triglyceride were reacted in the presence of a Lewis acid catalyst, ethylaluminum dichloride, and hydroxymethyl derivatives were obtained at yields of 42 and 55% for sunflower oil and soybean oil, respectively. In the next step, hydroxymethyl products were reacted with maleic anhydride at 100°C to produce the maleate half esters. The average number of maleate groups per triglycerides was found to be 1.7 for soybean oil and 1.3 for sunflower oil. In the final step, the free-radical–initiated copolymerization of the maleinized triglycerides with styrene produced rigid polymers. Characterization of new monomers and polymers was done by 1H-NMR, 13C-NMR, and infrared and mass spectrometries. The swelling behavior of the crosslinked network polymers was determined in different solvents. The glass-transition temperature of the cured resin was also determined by differential scanning calorimetry to be 40°C for soybean-based polymer and 30°C for sunflower-based polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4037–4046, 2004

In this study soybean oil triglycerides were reacted with maleic anhydride in an ene reaction to introduce more than two maleate residues per triglycerides. The maleinized soybean oil (SOMA) was then polymerized with diols to the half-ester stage only. Two different types of alcohols was used in this work: (1) short-chain polyhydroxy linear or cyclic alcohols having 2, 3, 4, or 6 hydroxyl groups; and (2) long-chain dihydroxy alcohols. The aim was to determine the effect of functionality and chain length by choosing alcohols with increasing number of hydroxyl groups and different chain lengths. The reaction of alcohols with anhydride functionalized soybean oil to give a polymeric half-ester is a reaction that proceeds without the formation of byproducts and is different from complete polyesterification of maleinized oils, which are well known. To improve the reaction yields, different catalysts and different reaction conditions were examined. The structural analysis of the products was done with 1H-NMR and IR spectroscopy. All of the new polymers obtained were resilient and soft rubbers at room temperature. Castor oil polymer mixed with 60% CaCO3 and 12% cork powder gave a resilient and nontacky linoleum composition. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 197–202, 2003

Epoxidized soybean oil was reacted with cinnamic acid with triphenyl phosphine as a catalyst. Cinnamic acid reacted with 79% of the available epoxy groups, and this yielded cinnamate esters of epoxidized soybean oil (ESOCA). 1H-NMR, IR, and mass spectra of the new cinnamate derivatives confirmed the proposed structure. The mass spectra revealed that the average number of cinnamate groups per triglyceride molecule was 3.33. ESOCA could be photopolymerized with UV light. ESOCA could also be homopolymerized into a soft and insoluble polymer by free-radical initiation and copolymerized with styrene, vinyl acetate, and methyl methacrylate. A mixture of ESOCA with 25 wt % styrene had a viscosity of 410 cP and could be free-radically polymerized with benzoyl tert-butyl peroxide at elevated temperatures. Differential scanning calorimetry confirmed the formation of copolymers. The ESOCA homopolymer and its copolymers all showed a first-order transition by differential scanning calorimetry around −1.5°C that was attributable to side-chain relaxations of the triglyceride fatty acids. The styrene copolymer of ESOCA showed a tan δ peak at 66.6°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3882–3888, 2003

Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides was achieved. In the first part of the study, methyl oleate was bromoacrylated in the presence of acrylic acid and N-bromosuccinimide as a model compound for the application of the reaction to the triglycerides. Next, soybean oil and high oleic sunflower oil were bromoacrylated by using the same procedure. The products were characterized by GC, IR, 1H-NMR, 13C-NMR, and mass spectrometry. The bromoacrylation yields for soybean oil and sunflower oil were 75 and 55%, respectively. A rigid thermoset polymer was prepared from the radical copolymerization of bromoacrylated soybean oil with styrene. The bromoacrylated sunflower oil–styrene copolymer showed semirigid properties. The crosslinked network structure of the copolymers was examined by their swelling behavior in different solvents. Glass-transition temperatures were also determined and soybean oil–based polymer and sunflower oil–based polymer showed a glass transition at 55–65 and 20–30°C, respectively. The storage moduli of the soybean-based and sunflower-based polymers at room temperature were approximately 1.0 × 1010 and 1.1 × 108 Pa, respectively. Photopolymerization was also carried out by using 2,2-dimethoxy-2-phenyl-acetophenone as initiator. The response of the cured polymers to the thermal energy produced by a small flame was also tested by the ignition respond index method according to ASTM D 3713-78 and was found to be 5 B at 2.00 mm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91:2700–2710, 2004

Soybean oil monoglycerides (SOMG), obtained by the glycerolysis of soybean oil, were reacted with maleic anhydride to produce SOMG maleate half esters. The copolymers of the SOMG maleates with styrene produced rigid thermosetting polymers. The dynamic mechanical analysis (DMA) of this polymer showed a glass-transition temperature (Tg) around 133°C and a storage modulus (E′) value around 0.94 GPa at 35°C. The tensile tests performed on this polymer showed a tensile strength of 29.36 MPa and a tensile modulus of 0.84 GPa. Mixtures of SOMG with neopentyl glycol (NPG) and SOMG with bisphenol A (BPA) were also maleinized under the same reaction conditions and the resulting maleates were then copolymerized with styrene. The resulting polymers were analyzed for their mechanical properties. The Tg of the copolymers of the SOMG/NPG maleates with styrene was 145°C and the E′ value at 35°C was 2 GPa. The tensile strength of this polymer as calculated from the stress–strain data was 15.65 MPa and the tensile modulus was 1.49 GPa. The Tg of the copolymers of SOMG/BPA maleates, on the other hand, was found to be around 131°C and the E′ value was 1.34 GPa at 35°C. The changes observed in the mechanical properties of the resulting polymers with the introduction of NPG maleates and BPA maleates to the SOMG maleates can be explained by the structural changes on the polymer backbone. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 972–980, 2002

Triglyceride oils derived from plants have been used to synthesize several different monomers for use in structural applications. These monomers have been found to form polymers with a wide range of physical properties. They exhibit tensile moduli in the 1–2 GPa range and glass transition temperatures in the range 70–120 °C, depending on the particular monomer and the resin composition. Composite materials were manufactured utilizing these resins and produced a variety of durable and strong materials. At low glass fiber content (35 wt %), composites produced from acrylated epoxidized soybean oil by resin transfer molding displayed a tensile modulus of 5.2 GPa, a flexural modulus of 9 GPa, a tensile strength of 129 MPa, and flexural strength of 206 MPa. At higher fiber contents (50 wt %) composites produced from acrylated epoxidized soybean oil displayed tensile and compression moduli of 24.8 GPa each, and tensile and compressive strengths of 463.2 and 302.6 MPa, respectively. In addition to glass fibers, natural fibers such as flax and hemp were used. Hemp composites of 20% fiber content displayed a tensile strength of 35 MPa and a tensile modulus of 4.4 GPa. The flexural modulus was ∼2.6 GPa and the flexural strength was in the range 35.7–51.3 MPa, depending on the test conditions. The flax composite materials had tensile and flexural strengths in the ranges 20–30 and 45–65 MPa, respectively. The properties exhibited by both the natural- and synthetic fiber-reinforced composites can be combined through the production of “hybrid” composites. These materials combine the low cost of natural fibers with the high performance of synthetic fibers. Their properties lie between those displayed by the all-glass and all-natural composites. Characterization of the polymer properties also presents opportunities for improvement through genetic engineering technology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 703–723, 2001

In this study, rigid thermoset polymers were prepared from radical copolymerization of the soybean oil monoglyceride maleates with styrene. In the first part of the study, soybean oil monoglycerides (SOMGs) were obtained from the reaction of soybean oil with glycerol at 220–240°C with an optimization of the reaction to maximize the monoglyceride yield. In the following step, SOMG were reacted with maleic anhydride at temperatures around 100°C to produce the SOMG maleate half esters. Different catalysts and different reaction conditions were examined to increase the maleate half esters' yields. The reactions were followed by IR and 1H NMR, and the products were characterized by mass spectrometry. In the final step, the radical initiated copolymerization of the SOMG maleates with styrene produced rigid, thermoset polymers. The emulsion copolymerization of the SOMG maleates with styrene was also carried out successfully without the addition of an emulsifier. The obtained polymers were characterized by IR and the crosslinked network structure of the copolymers was examined with the swelling behavior in different solvents. Mechanical properties of the cured resin such as Tg, dynamic flexural modulus, and surface hardness were also determined. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 69–77, 2001

2-Hydroxymethyl-but-1-ene-3-one [α-hydroxymethyl methyl vinyl ketone (HMVK)] was synthesized from methyl vinyl ketone using paraformaldehyde and a tertiary amine catalyst. Free-radical polymerization of this monomer created transparent, tough polymers that were insoluble in organic solvents. HMVK was converted to trimethylsilyl, acetate, and chloride derivatives. When the hydroxyl group was thus protected or removed, all these monomers could be free radically polymerized in bulk to make soluble polymers. The chlorination reaction is complicated by the formation of 1,1-bischloromethylacetone, which dehydrohalogenated unexpectedly to the desired α-chloromethyl methyl vinyl ketone. HMVK will self-condense to an ether dimer in the presence of a catalytic acid. This reagent is capable of crosslinking many alkene monomers through hydrolytically stable ether bonds. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 509–516, 2000

New ester derivatives of ethyl α-hydroxymethylacrylate were synthesized. Derivatives obtained include the formate, acetate, hexanoate, stearate, benzoate, trifluoroacetate, and adamantanoate. Bulk polymerizations with AIBN gave high molecular weight polymers with intrinsic viscosities of over 2 dL/g and molecular weights of several million. These high molecular weights were the result of autoacceleration in the bulk. Solution polymerization in benzene gave more typical polymers

Ethyl-α-hydroxymethylacrylate (EHMA) was esterified with hexanoyl chloride in 80% yield. The homopolymer of the hexanoate ester was found to be a glassy thermoplastic and soluble polymer. Copolymerization of the hexanoate ester with EHMA in varying ratios gave polymers that were thermoplastic and more soluble as a result of internal lubrication of the long alkyl pendant groups. Copolymers with styrene were synthesized with relatively high conversion. Reaction of EHMA with adipoyl chloride gave a bis-ester which served as crosslinking agent when copolymerized with different monomers including EHMA itself. In a separate synthesis EHMA was reacted with toluenediisocyanate (TDI). In the absence of catalyst a monourethane was formed. This monomer still contains one isocyanate function and is capable of further reactions subsequent to double bond addition polymerization. This reaction was also carried out on poly-EHMA, with or without catalyst. The products were the mono and the crosslinked bisurethanes as expected. Thus, acyl chlorides and isocyanates were found to be excellent reagents for derivatization of EHMA. © 1993 John Wiley & Sons, Inc.

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 1H-NMR analyses. Thermal properties of the polymers were determined by DSC and TGA. Thermal degradation of the polyurethanes started at 150°C. Stability of the polyureas was higher than polyurethanes. Almost all polymers showed a Tg around −50°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. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 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 showed Tg's at 70 and 66°C, respectively. Dynamic moduli of the two polymers were 11.73 and 3.34 Mpa respectively. SMA-epoxidized methyl oleate, poly[styrene-co-(maleic anhydride)]-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. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

The synthesis of various esters of α-hydroxymethylacrylate are summarized along with a brief description of their properties and polymerizability. Polymer characterization is given, including thermal behavior, solubility and spectroscopic properties. Derivatives of the acrylates are generated through reaction of the alcohol group to give halides, esters, ethers, and ether dimers. The last, along with additional multifunctional acrylates generated through the chemistry inherent in the synthetic approach, allow formation of a number of cyclopolymers, Michael polyadducts, and crosslinked systems.

Poly-2-vinylfuran, synthesized by free-radical polymerization of 2-vinylfuran, was characterized by nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy. The pendant furan rings on the polymer backbone were then used as the diene component of a Diels-Alder reaction with maleic anhydride. The juxtaposition of the furan rings at first suggested an “avalanche” Diels-Alder reaction, in which the product of one cyclization would be the reactant of the next. A lack of polymer stereoregularity and the reversibility of the Diels-Alder reaction, however, prevented its formation. On the other hand, when the dienophile was used in a 1:1 molar ratio with respect to furan the smooth reaction produced a new polymer, the maleic anhydride adduct of poly-2-vinylfuran, which characterized by NMR and IR spectroscopy, was air stable and soluble in a number of solvents up to 70% transformation. When heated to 160°C the polymer reverted to maleic anhydride and somewhat decomposed poly-2-vinylfuran.

Synthese et cyclopolymerisation du compose obtenu par reaction de l'acrylate de methyle avec le formaldehyde

Polymerisation de l'α(hydroxymethyl) acrylate de methyle par chauffage a 80°C ou photo-amorcage en presence d'isopropylether de benzoine ou par AIBN en masse ou en solution. Copolymerisation avec MMA ou St en masse