Cationic, thermally cured coatings using epoxidized soybean oil

Cycloaliphatic epoxy resins are used in coatings and inks because of their exceptionally low viscosity and reactivity with a variety of co-reactants, thus permitting high-solids and zero VOC coatings. The low viscosity of epoxidized soybean oil (ESBO), its reactivity, and relatively low cost make it an inexpensive candidate co-resin in cationic thermally cured coatings and inks using blocked acid catalysts. Formulations with up to 40% ESBO in the epoxy resin blend were investigated. Blending of cycloaliphatic resin with 10% ESBO gave a bake coating with the same results as the standard formulation except pencil hardness was one unit lower when cured for 12 min at 120°C with a heat de-blocked catalyst. The hardness of coatings with ESBO is adjustable by changing the epoxy/polyol ratio, using harder polyols and harder epoxy resins. Coatings Research Institute, 430 W. Forest Ave., Ypsilanti, MI 48197.     

Mechanical and rheological properties of epoxidized soybean oil plasticized poly(lactic acid)

Poly(lactic acid) (PLA) is a well known biodegradable thermoplastic with excellent mechanical properties that is a product from renewable resources. However, the brittleness of PLA limits its general applications. Using epoxidized soybean oil (ESO) as a novel plasticizer of poly(lactic acid), the composite blend with the twin‐screw plastic extruder at five concentrations, 3, 6, 9, 12, and 15 wt %, respectively. Compared with pure PLA, all sets of blends show certain improvement of toughness to different extents. The concentration with 9 wt % ESO increases the elongation at break about 63%. The melt flow rates of these blends with respect to different ESO ratio have been examined using a melt flow indexer. Rheological behaviors about shear viscosity and melt strength analysis are discussed based on capillary rheology measurements. The tensile strength and melt strength of the blends with 6 wt % ESO simultaneity reach the maximums; whereas the elongation at break of the blends is the second highest level. ESO exhibits positive effect on both the elongation at break and melt strength. The results indicate that the blend obtained better rheological performance and melt strength. The content of 6 wt % ESO in PLA has been considered as a better balance of performance. The results have also demonstrated that there is a certain correlation between the performance in mechanical properties and melt rheological characterization for the PLA/ESO blends.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal stability of epoxidized soybean oil and its absorption and migration in poly(vinylchloride)

Thermal analyses of epoxidized soybean oil (ESO) were conducted and showed that it was stable up to temperatures as high as 240–260°C in air‐free environment. The solubility and transport characteristics of ESO in poly(vinylchloride) (PVC) were also investigated under various conditions. The absorption study showed that the resin had a void volume of ～0.3 cm³/g. Furthermore, ESO was found to be sufficiently soluble in the PVC matrix to function as an effective plasticizer, with equilibrium solubility of 72 g/100 g PVC at 80°C and 163 g/100 g PVC at 120°C. The absorption of ESO in PVC grains was a three step process comprising “induction,” “swelling,” and “saturation” periods. Torque rheometer studies showed that higher mixer temperature and/or speed facilitated uptake of plasticizer in PVC and ultimate fusion. Migration studies of plasticized and stabilized PVC compositions showed no change in mass at 40°C, but increasingly greater mass loss as the temperature was raised up to 120°C. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

A new biobased plasticizer for poly(vinyl chloride) based on epoxidized cottonseed oil

The use of epoxidized cottonseed oil as plasticizer for poly(vinyl chloride) was studied. The plasticizer content was set to 70 phr and the optimum isothermal curing conditions were studied in the temperature range comprised between 160 and 220 °C with varying curing times in the 7.5–17.5 min range. The influence of the curing conditions on overall performance of cured plastisols was followed by the evolution of mechanical properties (tensile tests with measurements of tensile strength, elongation at break, and modulus), change in color, surface changes of fractured samples by scanning electron microscopy (SEM), thermal transitions by differential scanning calorimetry, and migration in n‐hexane. The optimum mechanical features of cured plastisols are obtained for curing temperatures in the 190–220 °C range. For these curing conditions, fractography analysis by SEM gives evidences of full curing process as no PVC particles and free plasticizer can be found. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43642.     

Bis(2‐ethylhexyl) succinate in mixtures with epoxidized soybean oil as bio‐based plasticizers for poly(vinylchloride)

Mixtures of bis(2‐ethylhexyl) succinate and epoxidized soybean oil (ESO) have been evaluated as bio‐based plasticizers for poly(vinylchloride). The rate of absorption of the bioplasticizers and their mixtures in the polymer was fast and, unlike that of petroleum‐derived plasticizers, did not vary significantly with molecular weight. These bio‐derived plasticizers and their mixtures were compatible with the polymer even at high loadings. The succinate was the most volatile and efficient plasticizer, but on heat aging of the polymer compositions, it also had the greatest deleterious effects. Diffusion coefficients and apparent activation energies of formulations containing bioplasticizer mixtures were controlled by the more volatile succinate. Mixtures comprising up to 50 wt% of the succinate yielded acceptably high‐tensile properties after thermal aging as well as better plasticization efficiency than the epoxy bioplasticizer. Although the succinate resulted in inferior volume resistivity of the polymer compositions, improvements were obtained with increasing proportions of the epoxidized derivative in plasticizer mixtures. Melt state viscosity‐shear rate curves of compositions containing dioctyl succinate (DOS) were similar to those made with two of the petroleum‐derived plasticizers, but a DOS/ESO mixture yielded extended non‐Newtonian behavior at low‐shear rates. POLYM. ENG. SCI., 55:634–640, 2015. © 2014 Society of Plastics Engineers     

A study of mechanical properties of biobased epoxy network: Effect of addition of epoxidized soybean oil and poly(furfuryl alcohol)

A novel biobased thermoset interpenetrating network was introduced in this study. Epoxidized soybean oil (ESO) and poly(furfuryl alcohol) (PFA) were added to a commercial biobased epoxy resin. It was hypothesized that addition of ESO and PFA can decrease brittleness of bioepoxy resin and also increase biobased content. Mechanical properties of samples were evaluated using tensile and impact test. It was found that the addition of ESO and PFA increased notched Izod impact energy by 76.6%. This significant increase was related to incorporation of long flexible chains of ESO into the matrix. Hybridization of ESO and PFA in bioepoxy reduced tensile strength (around 70%), tensile modulus (around 90%), and glass transition temperature in comparison to neat bioepoxy. Tensile strength and modulus of hybridized system can be further improved by addition of natural fibers and the resultant composite may be considered as a good candidate for applications in which damping properties are important. Crosslink density was calculated using dynamic mechanical analysis and a decrease in crosslink density was observed in hybridized system. PFA domains were observed in the matrix using atomic force microscopy in peak force quantitative nano‐mechanical mode and it revealed inhomogeneity in the crosslinked structure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44352.     

Effect of surface treatment of ramie fiber on the interfacial adhesion of ramie/acetylated epoxidized soybean oil (AESO) green composite

Recently, many researchers have attempted to convert soybean oil into useful polymers. One of the ways to make soybean oil into a matrix of green composites is to modify its triglyceride structure to obtain the acrylated epoxidized soybean oil (AESO) through epoxidization and acrylation. In this study, the effects of ramie fiber surface treatments such as acetylation, silane, and peroxide treatments on the chemical, morphological, and interfacial adhesion properties of a ramie/AESO green composite were studied. Surface-treated fibers were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and dynamic contact angle analysis. The crystallinity and thermal stability of chemically treated fibers were investigated by wide angle X-ray diffraction and thermogravimetric analyzer. It was demonstrated that surface treatments lead to several morphological changes, including the formation of micro-cracks and removal of impurities by acetylation and peroxide treatment as well as surface smoothing by silane treatment. Surface energy of acetylated fiber decreased with treatment time and showed the lowest value for silane treated fiber. The interfacial shear strength (IFSS) of a fiber/AESO composite was investigated through the microbond test. The IFSS of silane treated ramie was higher than that of others. The result indicates that silane treated fibers improve the interfacial property, which is the most important characteristic for the end use of green composites.     

Oxidative stability of soybean oil fatty acid methyl esters by oil stability index (OSI)

Biodiesel, an alternative diesel fuel derived from transesterification of vegetable oils or animal fats, is composed of saturated and unsaturated long-chain FA alkyl esters. During long-term storage, oxidation caused by contact with air (autoxidation) presents a legitimate concern with respect to monitoring and maintaining fuel quality. Extensive oxidative degradation may compromise quality by adversely affecting kinematic viscosity, acid value, or PV. This work examines the oil stability index (OSI) as a parameter for monitoring the oxidative stability of soybean oil FAME (SME). SME samples from five separate sources and with varying storage and handling histories were analyzed for OSI at 60°C using an oxidative stability instrument. Results showed that OSI may be used to measure relative oxidative stability of SME samples as well as to differentiate between samples from different producers. Although addition of α-tocopherol or TBHQ increased OSI, responses to these antioxidants varied with respect to SME sample. Variations in response to added antioxidant were attributed to aging and other effects that may have caused oxidative degradation in samples prior to acquisition for this study. Results showed that OSI was more sensitive than iodine value in detecting the effects of oxidative degradation in its early stages when monitoring SME during storage.     

Effect of epoxidized soybean oil grafted poly(12-hydroxy stearate) on mechanical and thermal properties of microcrystalline cellulose fibers/polypropylene composites

A new green compatibilizer named epoxidized soybean oil grafted poly(12-hydroxy stearate) (ESO-g-PHS) was successfully synthesized using 12-hydroxy stearic acid and epoxidized soybean oil (ESO). The chemical structure of ESO-g-PHS was investigated through Fourier transformed infrared spectroscopy, thermogravimetric analysis, and gel permeation chromatography. ESO-g-PHS was used as a compatibilizer to enhance the interfacial compatibility between polypropylene (PP) and microcrystalline cellulose fibers (MCF). The results showed that the impact strength and tensile strength were 33.55 and 27.57 MPa when the content loading of MCF reached 10 wt% and ESO-g-PHS was 4 wt%, which enhanced by 75.4 and 30.04 %, respectively, compared to that of composites without ESO-g-PHS. In addition, the SEM images of the fracture surfaces display that PP was highly bonded to MCF with ESO-g-PHS treated. In addition, the wide angle X-ray diffraction measurement revealed that the addition of ESO-g-PHS did not change the crystal structure of PP. Moreover, there was a slight improvement in thermal properties for PP composites with the addition of ESO-g-PHS.     

Absorption and migration of bio‐based epoxidized soybean oil and its mixtures with tri(2‐ethylhexyl) trimellitate in poly(vinylchloride)

The efficacy of epoxidized soybean oil (ESO), tri(2‐ethylhexyl) trimellitate, and mixtures thereof as plasticizers for poly(vinylchloride) has been studied. At 80°C, the trimellitate was slower to absorb in this polymer than ESO and was also less soluble, but the former exhibited higher solubility at 120°C. Plasticization efficiencies of stabilized polymeric compositions were similar with ESO and the trimellitate (despite their very different molecular weights). The trimellitate yielded greater mass loss during heat aging of the plasticized compositions, but substituting even minor amounts of it with ESO decreased mass loss synergistically. The trimellitate also resulted in more of an increase in hardness than ESO over time at elevated temperatures, but when aged at 120°C, mixtures of the two surprisingly had more deleterious effects. Thus, although ESO can replace part or all of trimellitates in plasticized PVC, using it as sole plasticizer would be preferable when heat aging performance is a requirement. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41966.     

Decarboxylation of the 6-nitrobenzisoxazole-3-carboxylate anion catalyzed by cross-linked poly(4-vinylpyridinium) salts

Summary Catalysis of cationic polyelectrolytes for the decarboxylation of 6-nitrobenzisoxazole-3-carboxylate anion was studied in a buffer solution (pH=9.0). Cross-linked poly (4-vinylpyridinium) salts prepared from 4-vinylpyridine and , -dibromides were used as cationic catalysts. The cross-linked catalysts were found to accelerate markedly the decarboxylation in comparison with the linear water-soluble analogues. Effect of the polymer structure such as the length of (CH₂)_x linkages between positive charges on the catalytic activity was examined. It was suggested that the acceleration by the cross-linked polymer catalysts would be due to the hydrophobic microenvironment around the catalytic sites.     

Inhibition of soybean oil oxidation by extracts of dry beans (Phaseolus vulgaris)

Polyphenolic compounds were extracted from pinto, kidney, white (Great Northern), pink, and black beans by hot methanol extraction and added to soybean oil. Oil oxidation was assayed by thiobarbituric acid-reactive substances (TBARS). All bean polyphenolics extracts exhibited similar antioxidant capacity in delaying the onset of iron-catalyzed oxidation better than butylated hydroxyanisole (BHA), propyl gallate (PG), and ascorbic acid. Bean polyphenolic compounds were stable after heating to 50°C and maintained their antioxidant potential after 3 mon at 4°C. Bean extracts effectively inhibited iron-catalyzed oxidation of soybean oil, probably by chelating metal ions, because no antioxidant effect was observed when soybean oil was oxidized without an iron catalyst.     

Oleophilic modification of poly(vinyl alcohol) films by functionalized soybean oil triglycerides

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     

Properties of poly(vinyl chloride) incorporated with a novel soybean oil based secondary plasticizer containing a flame retardant group

A novel bio‐based plasticizer containing flame retardant groups based on soybean oil (SOPE) was synthesized from epoxidized soybean oil (ESO) and diethyl phosphate through a ring‐opening reaction. PVC blends plasticized with ESO and SOPE were prepared, respectively. Properties including rheological behavior, thermal stability, flame retardant performance, mechanical properties of PVC plasticized with ESO and SOPE were carefully studied. The results showed that the plasticized PVC blends indicated better compatibility, thermal, and mechanical properties. As a novel bio‐based plasticizer containing flame retardant groups, the TGA data indicated that the thermal degradation temperature of PVC blends plasticized with SOPE could reach to 275.5°C. LOI tests and SEM indicated that the LOI value of PVC blends could increase from 24.2 to 33.6%, the flame retardant performance of SOPE was put into effect by promoting polymer carbonization and forming a consolidated and thick flame retardant coating quickly, which is effective to prohibit the heat flux and air incursion. The enhancement in flame retardancy will expand the application range of PVC materials plasticized with SOPE. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42111.     

Synthesis and study of properties of new oligoesters based on soybean oil as potential poly(vinyl chloride) plasticizers

New compounds as potential poly(vinyl chloride) plasticizers based on soybean oil and oligoesters of adipic acid and different glycols by one-pot transesterification are synthesized. In the first step of the plasticizer synthesis oligoesters of adipic acid and diethylene glycol, triethylene glycol, or dipropylene glycol are synthesized, and then in situ in the second step, a defined amount of soybean oil is introduced. By degradation of soybean oil with oligoesters, and transesterification reaction, different compounds are obtained. Their physicochemical properties are determined by NMR, SEC, DSC, TGA, and volatility analyses. The properties of synthesized plasticizers are compared with commercial products: monomeric (DEHP) and aliphatic oligoster of adipic acid and 1,3-butanediol (H-1).     

Modification of odd-chain length unsaturated fatty acids by hepatocytes of rainbow trout (Oncorhynchus mykiss) fed diets containing fish oil or olive oil

Hepatocytes isolated from rainbow trout fed on diets containing either fish oil or olive oil were incubated with individual odd-chain length unsaturated fatty acids (19∶1n−9, 19∶2n−6, 19∶3n−3, 21∶2n−6, 21∶3n−6, 21∶4n−6, 21∶3n−3, and 21∶5n−3) to examine whether these fatty acids were substrates for modification by desaturation and elongation. All odd-chain length fatty acids were readily assimilated into the lipids of hepatocytes from both dietary groups of fish, but their conversion to longer-chain, more unsaturated derivatives was more pronounced with cells from trout fed olive oil. Thus, the conversion of 19∶2n−6 and 21∶2n−6 to 21∶3n−6 and 21∶4n−6, and of 19∶3n−3 to 21∶4n−3 and 21∶5n−3, was most obvious in cells from the olive oil group, as was the conversion of 21∶3n−6 and 21∶3n−3 to 21∶4n−6 and 21∶4n−3, respectively. Elongation of 19∶1n−9 to 21∶1n−9 and 23∶1n−9 occurred in cells from both groups. No 23∶6n−3 was detectable as a product of 19∶3n−3 or 21∶3n−3. However, this fatty acid was a major product formed by cells from fish fed olive oil presented with 21∶5n−3. Cells from both groups of fish incorporated 21∶4n−6 and 21∶5n−3 into their lipids largely without modification but chain-shortened around 40, 23, and 19% of the incorporated 21∶2n−6, 21∶3n−3, and 19∶1n−9, respectively. The results demonstrate that odd-chain length unsaturated fatty acids can act as substrates for the desaturation, elongation, and chain-shortening systems of trout hepatocytes.     

Conversion of soybean oil into ion exchange resins: Removal of copper (II), nickel (II), and cobalt (II) ions from dilute aqueous solution using carboxylate‐containing resin

An ion‐exchange resin containing carboxylic acid groups was prepared by reaction of epoxidized soybean oil with triethylene tetramine, followed by hydrolysis of glycerides by using sodium hydroxide solution. The cation exchange capacity of the resins was determined to be 3.50 mequiv/g. The adsorption capacity for Cu²⁺, Ni²⁺, and Co²⁺ on the obtained resin at pH 5.0 was found to be 192, 96, and 78 mg/g, respectively. Effect of pH on the adsorption capacity for copper (II), nickel (II), and cobalt (II) ions were also studied. Cu²⁺, Ni²⁺, and Co²⁺ were adsorbed at a pH above 3. These metal ions adsorbed on the resin are easily eluted by using 1N HCl solution. The selectivity of the resin for Cu²⁺ from mixtures containing Cu²⁺/Co²⁺/Ni²⁺ ions in the presence of sodium chloride was also investigated © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2386–2396, 2002     

Ring‐opening metathesis polymerization of bicyclo[2.2.1]hepta‐2,5‐diene (norbornadiene) initiated by new ruthenium(II) complex

The polymerization of norbornadiene (NBD) initiated by a novel ruthenium (Ru)(II) complex ( 3 ) containing 1,1′‐pyridine‐2,6‐diylbis[3‐(dimethylamino)prop‐2‐en‐1‐one] ( 1 ) as ligand has been investigated. Ru complexes exhibit more catalytic activity in the ring‐opening metathesis polymerization (ROMP) of NBD when activated with trimethylsilyldiazomethane (TMSD). The influence of the various experimental parameters such as reaction time and temperature, nature of the solvent and catalyst, ratio of the NBD/Ru, and TMSD addition has been investigated. The polymers have been obtained in high yields with a relatively low polydispersity index for ROMP and a high $ \bar M_n $ and $ \bar M_w $ values in a monomodal distribution. Their structures have been determined by means of FTIR and ¹H‐NMR spectroscopy. Thermal properties have been determined via thermogravimetric analysis and DTG methods. The NBD polymerization results that initiated by Ru‐based catalyst coordinated to amine ligand have been compared to initiated by [RuCl₂(p‐cymene)]₂. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013