Catalytic hydroprocessing of cottonseed oil in petroleum diesel mixtures for production of renewable diesel

The conversion of the esters included in refined cottonseed oil into hydrocarbon molecules compatible with petroleum diesel, which are named renewable diesel, has been studied at conventional hydrotreatment conditions. The vegetable oil was fed in mixture with desulphurized petroleum diesel to the hydrotreater containing a conventional CoMo/Al₂O₃ hydrotreatment catalyst. Conversion of esters was determined in the temperature range of 305-345 °C, at 30 bar and for 5 h⁻¹ < WHSV < 25 h⁻¹. Catalyst deactivation was followed for a period of 450 h in operation. A simple kinetic model of ester conversion suitable for scale-up and simulation studies has been tested.     

New sheet molding compound resins from soybean oil. I. Synthesis and characterization

Thermosetting resins were synthesized from soybean oil, which are suited to sheet molding compound (SMC) applications. It was achieved by introducing acid functionality and CC groups onto triglyceride molecules. The acid groups can react with divalent metallic oxides and/or hydroxides to form the sheet, while CC groups undergo free radical polymerization. An acrylated epoxidized soybean oil (AESO), which has an average of 3.4 acrylates per triglyceride, was used as starting material. The hydroxyl groups on AESO reacted with maleic anhydride (MA) to render acid groups on the molecule. The resulting monomer was then copolymerized with 33 wt% styrene to form rigid polymers. Dynamic mechanical analysis showed storage moduli (E′) for these polymers ranging from 1.9 to 2.2 GPa at room temperature, and the glass transition temperatures (T_g) in the range of 100-115 °C. Both the E′ and T_g were increased by increasing the molar ratio of MA to AESO, and the transition from the glassy to the rubbery state was broadened by increasing the amount of MA. The effect of styrene as a comonomer was also examined, and a final formulation for SMC was optimized. The resulting resins exhibited appropriate viscosity during the SMC thickening process.     

Fatty acid‐based comonomers as styrene replacements in soybean and castor oil‐based thermosetting polymers

In this study, a fatty acid‐based comonomer is employed as a styrene replacement for the production of triglyceride‐based thermosetting resins. Styrene is a hazardous pollutant and a volatile organic compound. Given their low volatility, fatty acid monomers, such as methacrylated lauric acid (MLA), are attractive alternatives in reducing or eliminating styrene usage. Different triglyceride‐derived cross‐linkers resins were produced for this purpose: acrylated epoxidized soybean oil (AESO), maleinated AESO (MAESO), maleinated soybean oil monoglyceride (SOMG/MA) and maleinated castor oil monoglyceride (COMG/MA). The mechanical properties of the bio‐based polymers and the viscosities of bio‐based resins were analyzed. The viscosities of the resins using MLA were higher than that of resins with styrene. Decreasing the content of MLA increased the glass transition temperature (T_g). In fact, the T_g of bio‐based resin/MLA polymers were on the order of 60°C, which was significantly lower than the bio‐based resin/styrene polymers. Ternary blends of SOMG/MA and COMG/MA with MLA and styrene improved the mechanical properties and reduced the resin viscosity to acceptable values. Lastly, butyrated kraft lignin was incorporated into the bio‐based resins, ultimately leading to improved mechanical properties of this thermoset but with unacceptable increases in viscosity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

High performance bio‐based thermosetting resins composed of tung oil and bismaleimide

The reaction of tung oil (TO) and 1,1′‐(methylenedi‐4,1‐phenylene)bismaleimide (BMI) in 1,3‐dimethyl‐2‐imidazolidinone (DMI) at 150°C for 4 h and subsequent precipitation gave TO/BMI prepolymer, which was cured at 200°C for 2 h gave crosslinked TO/BMI product with CC ratio from 1/1 to 1/4. The FE‐SEM analysis revealed that all the cured products are homogeneous and no phase separation was observed. The glass transition temperature and 5% weight loss temperature of the cured TO/BMI increased with increasing BMI content. The maximal tensile strength (38.1 MPa) and modulus (2.6 GPa) were obtained for the cured products with the CC ratios of 1/2 and 1/3, respectively. To evaluate the reaction of TO and BMI, the model reaction products of TO and N‐phenylmaleimide (PMI) in DMI were analyzed by ¹H‐NMR spectroscopy. The NMR data of the reaction products of TO/PMI with the CC ratio 2/1, 1/1, 1/2, 1/3, and 1/4 at 150°C for 24 h revealed that Diels‐Alder reaction preferentially occurred at 2/1, and that ene reaction and other reactions such as radical homo and copolymerization gradually increased with decreasing CC ratio of TO/PMI. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of urethane alkyd based on a castor oil/jatropha oil mixture

Castor oil is the only major natural vegetable oil that contains a hydroxyl group and so it is widely used in many chemical industries, especially in the production of polyurethanes. In this work, castor oil was interesterified with jatropha oil and the product was subsequently reacted with toluene diisocyanate to obtain urethane alkyd. The prepared urethane alkyd was characterized and its properties were determined and compared with those of the conventional (glycerol/jatropha oil) and commercial urethane alkyds. The castor oil/jatropha oil-based urethane alkyd had a lower molecular weight and viscosity, a slightly lower hardness and greatly longer drying time than the conventional and commercial urethane alkyds, but otherwise the film properties were broadly similar, including being very flexible, with an excellent adhesion and high impact resistance. In addition, they also exhibited excellent resistance to water and acid.     

Effect of phytosterol structure on thermal polymerization of heated soybean oil

This study determined the effect of phytosterol structure, including the degree of unsaturation and the presence of an ethylidene group in the side chain, on the thermal polymerization of heated soybean oil. Indigenous tocopherols and phytosterols were removed from soybean oil by molecular distillation. Pure phytosterols were added back to the stripped soybean oil at concentrations of 0.5, 1.0, and 5 mg/g oil (0.05, 0.1, and 0.5 wt-%). These oils were heated at 180 °C over a period of 8 h, and triacylglycerol dimers and polymers, fatty acid composition, and residual phytosterol content were determined. None of the phytosterols prevented triacylglycerol dimer and polymer formation when used at 0.5 mg/g; however, phytosterols with two or more double bonds, regardless of the presence of an ethylidene group in the side chain, provided slight protection when added at 1 mg/g. Ergosterol addition at 5 mg/g reduced polymer formation by 16–20% compared to the control oil, but at this level none of the other phytosterols provided protection of any practical significance. Thus, under the conditions used for this heating study, the degree of phytosterol unsaturation was more important for its anti-polymerization activity than the presence of an ethylidene group.     

Rapid transesterification of soybean oil with phase transfer catalysts

Biodiesel is a renewable, non-toxic and biodegradable alternative fuel for compression ignition engines. Biodiesel is produced mainly through base-catalyzed transesterification of animal fats or vegetable oils. However, the conventional base-catalyzed transesterification is characterized by slow reaction rates at both initial and final reaction stages limited by mass transfer between polar methanol/glycerol phase and non-polar oil phase.In our study we used phase transfer catalysts (PTCs) to facilitate anion transfer between polar methanol/glycerol phase and non-polar oil phase to speed up transesterification. The benefits of transesterification by PTCs include no need for expensive aprotic solvents, potentially simpler scaleup and higher activity (shorter reaction time). Various PTCs were investigated for base-catalyzed transesterification. Experimental results showed that base-catalyzed transesterification was enhanced with an effective PTC, indicated by the formation of high methyl ester (ME) content within a relatively short time. Individual operating variables such as molar ratios of methanol to oil, total OH⁻ to oil, PTC to base catalyst and agitation including ultrasound were investigated for transesterification with PTC. Product analyses showed that ME content higher than 96.5 wt.% was achieved after only 15 min of rapid transesterification with PTC (tetrabutylammonium hydroxide or tetrabutylammonium acetate as PTC, MeOH/oil molar ratio of 6, total OH⁻/oil molar ratio of 0.22, PTC/KOH molar ratio of 1 and 60 °C). Free and total glycerol contents in the final product from 15 min rapid transesterification with PTC were lower than maximum allowable limits in the standard specification for biodiesel.     

High‐performance bio‐based thermosetting resins composed of dehydrated castor oil and bismaleimide

The reaction of dehydrated castor oil (DCO) and 1,1′‐(methylenedi‐4,1‐phenylene)bismaleimide (BMI) in 1,3‐dimethyl‐2‐imidazolidinone (DMI) at 130°C for 6 h and subsequent precipitation gave DCO/BMI prepolymer, which was cured at 200°C for 2 h gave DCO/BMI cured product. The FE‐SEM analysis revealed that the cured products with C?C ratio 2/1 and 1/1 are homogeneous, whereas phase separation occurs for the 1/2 product. The glass transition temperature, 5% weight loss temperature, and tensile modulus of the cured DCO/BMI increased with increasing BMI content. Regarding the tensile strength, the cured DCO/BMI 1/1 product showed the highest value. To evaluate the reaction of DCO and BMI, the model reaction products of DCO and N‐phenylmaleimide (PMI) in DMI were analyzed by ¹H NMR spectroscopy. The ¹H NMR data of DCO revealed that DCO has about 4.8 CH?CH bonds per triglyceride and that the ratio of conjugated and nonconjugated diene moieties is about 41/59. The NMR data of the reaction products of DCO/PMI with the C?C ratio 2/1 and 1/1 at 200°C for 24 h revealed that both Diels–Alder and ene reactions occurs in addition to radical polymerization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel thermosetting resins for SMC applications from linseed oil: Synthesis,characterization, and properties

New thermosetting resins for applications of sheet‐molding compounds (SMCs) were successfully synthesized from linseed oil, which is the most molecularly unsaturated of all plant oils. The carbon–carbon double bonds were opened by epoxidation, followed by acrylation, and then maleinization, which provided more crosslink sites and added acid functionality on the triglyceride molecules to develop thickening. Dynamic mechanical analysis showed that the storage modulus of these new polymers was approximately 2.5 GPa at 30°C, and the glass‐transition temperature was above 100°C. During maturation the resins reached a molding viscosity quickly and stayed stable. Mechanical tests showed a flexural strength of 100 MPa and a flexural modulus of 2.8 GPa. Thermogravimetric analysis showed a single degradation ranging from 300°C–480°C, which was a result of the carbonization of the crosslinked network. These bio‐based resins are promising as replacements of some petroleum‐based resins in the SMC industry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis and interfacial properties of aminosilane derivative of acrylated epoxidized soybean oil

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-based,aqueous cationic polyurethane dispersions: Synthesis and properties

A variety of soybean oil-based, aqueous cationic polyurethane dispersions (PUDs) have been successfully synthesized from methoxylated soybean oil polyols (MSOLs) with hydroxyl functionalities ranging from 2.4 to 4.0. The effects of the hydroxyl functionality of the MSOLs on the particle size of the PUDs and the thermal and mechanical properties of the resulting polyurethane films have been carefully investigated by Fourier transform infrared, transmission electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, thermal gravimetric analysis and measurement of the mechanical properties. The particle size diameter of the PUDs ranges from 45 to 115 nm. The resulting polyurethane films are thermally stable up to 200 °C and exhibit tensile stress–strain behavior ranging from elastomeric polymers to ductile plastics, depending on the hydroxyl functionality of the MSOLs. This work provides a new way of utilizing biorenewables for the preparation of value-added polymers with high performance, contributing to a sustainable chemical industry.     

New path in the thermal cracking of triacylglycerols (canola and soybean oil)

Triacylglycerols (TGs) are naturally occurring oils abundant in many crops. A series of batch uncatalyzed thermal decomposition experiments were performed using canola and soybean oils to explore pathways of TG cracking. A detailed gas chromatographic protocol based on mass spectrometric identification and flame ionization quantification was applied to the organic liquid product generated upon cracking. Reaction conditions were identified that resulted in a novel organic liquid product (OLP) composition compared to previously reported work. Under these conditions (temperatures within a 420-440 °C range) a new route for TG thermolysis was discovered in which cracking reactions of original TG-bound fatty acids were nearly complete and led to the formation of 15-25 wt.% C₂-C₁₀ linear saturated monocarboxylic acids and ca. 30% linear alkanes. Less than 2 wt.% C₁₆-C₁₈ fatty acids which were originally present in the feedstocks as glycerol triesters were found in the OLP. These reactions appear to be kinetically controlled due to abundant hydrogen formation. This route provides a significant enrichment of low-MW compounds in the OLP (65-70 wt.% being <C₁₁) and thus may be considered as a new option for the production of replacement products for petroleum-based fuels and chemicals.     

Trehalose‐based thermosetting resins. I. Synthesis and thermal properties of trehalose vinylbenzyl ether

Trehalose vinylbenzyl ether was synthesized from trehalose and p‐chloromethylstyrene (CMS) in DMSO in the presence of powdered NaOH. The structure of the product was characterized by IR and ¹H NMR spectroscopy. Degree of substitution (DS) on a trehalose unit calculated from the ¹H NMR spectrum varied from 2.4 to 3.2 by changing the feed ratio of p‐chloromethylstyrene to trehalose. Thermal properties of the resin were analyzed by differential scanning calorimetry (DSC). DSC analysis revealed that the resin DS 2.4 has one exothermal peak at 132°C, whereas the resins DS 2.8 and 3.0 have two exothermal peaks. Furthermore, the resin DS 3.2 was found to have only one exothermal peak at 191°C. Dynamic mechanical analysis (DMA) and thermomechanical analysis (TMA) revealed that the cured resin has one transition, implying a glass transition. Biodegradability was assayed by the BOD method, and several percent of the cured resin was found to be degraded with activated sludge for 50 days. Further degradation, however, was not observed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 46–51, 2004     

Soft polyurethane elastomers with adhesion properties based on palm olein and palm oil fatty acid methyl ester polyols

Soft polyurethane (PU) elastomers with >70% bio-based content and with properties characteristic of pressure sensitive adhesives were prepared from an equimolar ratio of a polyol derived from palm oil fatty acid methyl ester (PolyFAME-EG polyol) and palm olein polyols (Pioneer E-135 and Pioneer M-60) cured with 2,4′- and 4,4′- diphenylmethane diisocyanate isomeric mixture at isocyanate to hydroxyl equivalent weight ratio (Isocyanate Index) of 1.02 and 0.73. FTIR analyses of the resulting elastomers indicate high levels of free non-hydrogen bonded urethanes, indicating phase mixing of hard and soft segments, which explains the transparent nature of the elastomers. The physical properties of the elastomers were correlated with the cross-link density of the palm olein polyols and Isocyanate Index. Elastomers produced at an Isocyanate Index of 1.02 ranges in hardness from 21 to 67 Shore A which correlated with the average polyol functionality. However, at an Isocyanate Index of 0.72 the resulting elastomers were very soft with hardness ranging from 1 to 4 Shore A and with T-peel adhesion to polypropylene in the range from 2.27 to 1.98 N/25 mm. Based on these results, a polyurethane matrix with a high renewable content of palm oil polyols can be used as a platform for the development of transparent elastomers that can be used as soft energy-absorbing materials with potential use in pressure sensitive adhesives.     

Synthesis and solution properties of water soluble copolymers based on acrylamide and quaternary ammonium acrylic comonomer

We have prepared cationic polyelectrolytes with a large range of compositions by the redox polymerization and copolymerization of acrylamide and (N,N,N-trimethyl) aminoethyl chloride acrylate. Molecular weights of the various samples were determined by light scattering, and the intrinsic viscosities of these polymers measured in aqueous solutions of various ionic strengths. We propose empirical laws between viscosity, composition in comonomers, molecular weight and ionic strength. Results also give the radius of gyration of macromolecules in NaCl solution (between 10^?2M and 1 M).     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. I. Synthesis and characterization

The cationic copolymerization of regular soybean oil, low‐saturation soybean oil (LoSatSoy oil), or conjugated LoSatSoy oil with styrene and divinylbenzene initiated by boron trifluoride diethyl etherate (BF₃·OEt₂) or related modified initiators provides viable polymers ranging from soft rubbers to hard, tough, or brittle plastics. The gelation time of the reaction varies from 1 × 10² to 2 × 10⁵ s at room temperature. The yields of bulk polymers are essentially quantitative. The amount of crosslinked polymer remaining after Soxhlet extraction ranges from 80 to 92%, depending on the stoichiometry and the type of oil used. Proton nuclear magnetic resonance spectroscopy and Soxhlet extraction data indicate that the structure of the resulting bulk polymer is a crosslinked polymer network interpenetrated with some linear or less‐crosslinked triglyceride oil–styrene–divinylbenzene copolymers, a small amount of low molecular weight free oil, and minor amounts of initiator fragments. The bulk polymers possess glass‐transition temperatures ranging from approximately 0 to 105°C, which are comparable to those of commercially available rubbery materials and conventional plastics. Thermogravimetric analysis (TGA) indicates that these copolymers are thermally stable under 200°C, with temperatures at 10% weight loss in air (T₁₀) ranging from 312 to 434°C, and temperatures at 50% weight loss in air (T₅₀) ranging from 445 to 480°C. Of the various polymeric materials, the conjugated LoSatSoy oil polymers have the highest glass‐transition temperatures (T_g) and thermal stabilities (T₁₀). The preceding properties that suggest that these soybean oil polymers may prove useful where petroleum‐based polymeric materials have found widespread utility. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 658–670, 2001     

Synthesis and performance of a thermosetting resin: Acrylated epoxidized soybean oil curing with a rosin‐based acrylamide

A synthesized rosin‐based polymeric monomer, N‐dehydroabietic acrylamide (DHA‐AM), was introduced into an acrylated epoxidized soybean oil (AESO)/DHA‐AM system to afford a thermosetting resin through thermocuring. Different molar ratios of the thermosetting AESO/DHA‐AM samples were obtained through curing in the presence of an initiator, and the curing processes of the AESO/DHA‐AM systems were evaluated by differential scanning calorimetry. The structures and performances of the resulting thermosets were characterized by Fourier transform infrared spectroscopy, dynamic mechanical analysis, elemental analysis, thermogravimetric analysis, and contact angle (θ) analysis. The analyses showed that with increasing content of DHA‐AM introduced into the copolymer, the storage modulus, glass‐transition temperature, thermal stability, and θ values of the cured samples all increased. Moreover, the copolymers changed from hydrophilic materials to hydrophobic materials. The results also demonstrate that the rosin acid derivatives showed comparable properties to those of reported petroleum‐based rigid compounds for the preparation of soybean‐oil‐based thermosets. The presence of DHA‐AM moieties in the composite structures could expand the use of AESO into the development of heat‐resistant and hydrophobic materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44545.     

Synthesis of a boron-containing adhesion promoter for improving the adhesion of addition-cure silicone rubber to PPA

Abstract

In this study, a boron-containing adhesion promoter PhBSiO with a high refractive index and MeBSiO with a low refractive index were synthesized by a non-hydrolytic sol-gel reaction. The chemical structures of the synthesized adhesion promoters were firstly characterized by infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). Then, the effects of adhesion promoters on the bonding properties of the cured silicone rubber were analyzed and the compatibility of the adhesion promoters to the silicon rubber was further studied through light transmittance detection. The boron-containing silicone adhesion promoters significantly enhanced the bonding strength of the cured silicone rubber to poly-phthalamide (PPA). When the addition amounts of PhBSiO and MeBSiO was 3.0 phr, the shear strength between silicone rubber and PPA respectively reached 0.761?MPa and 0.809?MPa, which were 145% and 161% higher than that of silicone rubber without adhesion promoter. In addition, the adhesion mechanism of the boron-containing adhesion promoter was investigated. The microscopic morphology of the fractured surface of the cured silicone rubber further demonstrated that boron atoms in the adhesion promoters significantly improved the adhesion strength between silicone rubber and PPA.     

Synthesis and properties of novel conducting polyaniline copolymers

A novel copolymer based on aniline and N‐β‐cyanoethylaniline was chemically prepared and characterized by a number of techniques including UV–vis, FTIR, ESR, XRD, and TGA. According to the systematic studies on the physical properties, it was found that the copolymers had excellent solubility in common organic solvents especially in DMF and pyridine, while the conductivity and yield decreased as the content of cyanoethyl group increased in the system. Moreover, an increase in the feed ratio of N‐β‐cyanoethylaniline induced a blue‐shift of the absorption bands in the UV–vis and IR region and significant line broadening of ESR signals together with a reduction in spin density. The XRD patterns of the copolymers lost the characteristic diffraction peaks of emeraldine salt as the ratio of cyanoethyl group increased. The thermal stability of the copolymer was increased with increasing the feed molar ratio of N‐β‐cyanoethylaniline. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 140–147, 2007