Determining the mechanical properties of epoxy resin (DGEBA) composites by ultrasonic velocity measurement

In this study, the composites of diglycidyl ether of bisphenol A (DGEBA) epoxy resin that have been formed by mixing epoxy resin with allyl glycidyl ether (AGE) and 2,3‐epoxypropyl methacrylate [glycidyl methacrylate (GMA)] were prepared in weight % ratios of 90 : 10, 80 : 20, and 70 : 30. A computer controlled analyzer with 35 MHz and a digital oscilloscope with 60 MHz were used for measuring the velocities of ultrasonic wave. The measurement of ultrasonic velocity carried out by pulse echo method at frequencies of 2.25 and 3.5 MHz at room temperature. The values of acoustic impedance (Z), Poisson ratio (μ), and coefficients of elasticity (L, G, K, E) of composites were calculated by values of densities and velocities that obtained. Thus, the effect of modificating epoxy resin (DGEBA) by AGE and GMA on mechanical properties of DGEBA was investigated using the ultrasonic method. Atomic force microscopy has been used for determining the microstructure of composites. By the results obtained from the investigation, it have been established that the longitudinal and shear ultrasonic wave velocities, and the values of all the elasticity constants of DGEBA were increased by modification with AGE and GMA. Also the most suitable combination ratio for the compound of DGEBA : AGE and DGEBA : GMA has been found as 80 : 20. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

(Salen)chromium Complex Mediated Asymmetric Ring Opening of meso‐ and Racemic Epoxides with Different Fluoride Sources

The asymmetric ring opening of five meso‐ and three racemic epoxides with different fluorinating reagents in the presence of stoichiometric or slightly sub‐stoichiometric amounts of Jacobsen's enantiopure (salen)chromium chloride complex A gave the corresponding optically active vicinal fluorohydrins. Silver fluoride was used as one of the fluoride sources either in the presence of Bu₄N⁺H₂F₃⁻ in diethyl ether or in acetonitrile. The latter reactions starting from cyclohexene oxide ( 1 ) showed maximum 72% ee in the formed fluorohydrin 2 isolated in 90% yield. From other meso‐epoxides such as cyclopentene oxide and cycloheptene oxide the corresponding fluorohydrins were isolated in 80% and 82% yield with 65% and 62% ee, respectively. In case of ring opening under similar conditions of the racemic styrene oxide or phenyl glycidyl ether 83% and 75% of the fluorohydrins with fluorine in the primary position were isolated with 74% ee and 65% ee, respectively. Tetrahydronaphthalene oxide yielded a 2:1 mixture of trans‐ (23% ee) and cis‐2‐fluoro‐3,4‐benzocyclohexenol (2% ee) suggesting competing S_N2 and S_N1 type ring openings. Other epoxides such as cyclooctene oxide, cis‐stilbene oxide and α‐methylstyrene oxide did not react or gave the fluorohydrins with very small enantiomeric excess.     

RAFT‐mediated graft polymerization of glycidyl methacrylate in emulsion from polyethylene/polypropylene initiated with γ‐radiation

The successful reversible addition‐fragmentation (RAFT)‐mediated graft polymerization of glycidyl methacrylate (GMA) in emulsion phase from polyethylene/polypropylene nonwoven fabric using 4‐cyano‐4‐[(phenylcarbonothioyl)thio]pentanoic acid under γ‐irradiation at ambient condition is reported. While conventional graft polymerization in emulsion phase yielded grafted materials with low of grafting (Dg) values [<7.5% at 10% (wt/wt) GMA], addition of RAFT agent to the graft polymerization system allowed the synthesis of polyethylene/polypropylene‐g‐poly(GMA) with more tunable Dg (8% ≤ Dg ≤ 94%) by controlling the grafting parameters. Relatively good control (PDI ～1.2 for selected grafting conditions) during polymerization was attained at 100:1 monomer‐to‐RAFT agent molar ratio. The number average molecular weight of free poly(glycidyl methacrylate) (PGMA) increased as a function of monomer conversion. NMR analyses of the free PGMA homopolymers indicate the presence of dithiobenzoate group from 4‐cyano‐4‐((phenylcarbonothioyl)thio) pentanoic acid on the polymer chain. The reactive pendant oxirane group of the grafted GMA can be modified for various environmental and industrial applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45270.     

Enhancement of Tensile and Impact Properties of Thermoplastic Lignocellulose Composites by Incorporation of Chemically Treated Alcell Lignin as Compatibilizer

This study focused on the effects of chemical treatment of Alcell lignin using glycidyl methacrylate (GMA) and allyl glycidyl ether (AGE) on the properties of thermoplastic-lignocellulosic composites. In the first stage, Alcell lignin was treated with GMA and AGE in different ratios (1:1, 1:2 and 1:3, based on equivalent weight). The level of treatment was monitored by (i) weight percentage gain (WPG), (ii) Fourier Transformed Infrared (FTIR) analysis and (iii) iodine number determination (Hanus method). In the second stage, treated lignin was used as compatibilizer at different percentages (1%, 3% and 5%, based on filler weight) in the preparation of lignocellulosic-thermoplastic composites. The results indicated that GMA and AGE had successfully attached to the lignin and enhanced the mechanical properties of lignocellulosic-thermoplastic composites. By comparison, the GMA treated lignin exhibited greater enhancement in mechanical properties as compared to AGE treated lignin.     

Studies on the synthesis of a methacrylate-based dental restorative resin

The synthesis of bisphenol A–glycidyl methacrylate (BIS–GMA), the resin component in most dental composite restorative materials, catalyzed by different tertiary amine accelerators such as N,N′-dimethyl-p-toluidine (DMPT), N,N′-dimethylamino phenethyl alcohol (DMAPEA), and N,N′-dimethylamino ethyl methacrylate (DMAEMA) is reported in this work. The effect of varying concentrations of accelerators and the reaction conditions of the synthesis as a function of time is studied in detail. The kinetics of the reaction between epoxide and carboxyl group during the formation of BIS–GMA is monitored using infrared (IR) and chemical techniques. The reaction is found to follow first-order and zero-order kinetics with respect to epoxide and acid, respectively. The degree of epoxide and acid conversion has been calculated as a function of time. The percentages of various isomers, formed under different reaction conditions have been reported. Characterization procedures for BIS–GMA have been developed.     

Kinetics of the copolymerization of alkylene oxides with glycidyl methacrylate

In the present study, the kinetics of copolymerization reaction of propylene oxide (PO) and butylene oxide (BO) with glycidyl methacrylate (GMA) in the presence of BF₃ · O(C₂H₅)₂ catalyst were investigated. The kinetic parameters and activation energy of the copolymerization reaction were calculated. The amounts of reacting PO, BO, and GMA during copolymerization were determined by chromatographic method, because the same copolymerization conditions were carried out for them. It was determined that the copolymerization rate of PO (r₀) and BO (r₀) was higher than that of GMA, but activation energy (E) of GMA was higher than that of PO and BO. The rate of reaction, the rate constant, and activation energy were calculated from the amount of copolymer obtained with respect to time. The structures of synthesized copolymers were determined by the spectral and chemical analysis methods. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Kinetic parameters using an immobilized tetrahexylammonium chloride catalyst in glycidyl methacrylate reaction with carbon dioxide

A soluble copolymer-supported catalyst containing pendant tetrahexylammonium chloride was synthesized by the radical copolymerization of p-chloromethylated styrene with styrene followed by the addition reaction of the resulting copolymer with trihexylamine. Initial absorption rate of carbon dioxide into glycidyl methacrylate (GMA) solutions containing the catalyst was measured in a semi-batch stirred tank with a plane gas-liquid interface at 101.3 kPa. The reaction rate constants of the elementary reaction between carbon dioxide and GMA were evaluated from analysis of the mass transfer mechanism accompanied by the elementary reactions based on film theory. Solvents such as toluene, N-methyl-2-pirrolidinone, and dimethyl sulfoxide influenced the reaction rate constants. Furthermore, this catalyst was compared to monomeric tetrahexylammonium chloride under the same reaction conditions.     

Grafting of glycidyl methacrylate onto high‐density polyethylene with reaction time in the batch mixer

The melt grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene (HDPE) in the presence of free radical initiators was investigated in the batch mixer. The graft content was determined with the titration and FTIR spectroscopy. The graft content increased with the increase of peroxide and initially introduced GMA concentration. Increase of the grafted GMA content resulted in decrease of the melt index. Interestingly, there was a sudden drop of GMA grafting content with the reaction time. It is assumed that depolymerization of GMA have taken place over the ceiling temperature. The crystallinity of the prepared glycidyl methacrylate grafted high density polyethylene (HDPE‐g‐GMA) was determined by the measurement of the heat of fusion. GMA grafted site acted as defect and crystallinity of the HDPE‐g‐GMA decreased with the increase of grafting reaction. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on dimensional stability and thermal properties of rubber wood chemically modified with styrene and glycidyl methacrylate

Rubber wood (Hevea brasiliensis) was impregnated with styrene and glycidyl methacrylate (GMA) as the crosslinking monomer. After impregnation, the polymerization was accomplished by catalyst heat treatment. Water uptake (%) and water vapor exclusion (%) of the rubber wood were found to be improved on treatment. Dimensional stability expressed in terms of volumetric swelling in water vapor (90% relative humidity) as well as in liquid water and water repellent effectiveness (WRE) of the treated samples were determined and also found to be improved. The wood–polymer interaction was confirmed by FTIR spectroscopy. Thermal properties of untreated and treated wood samples were evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetery (DSC) and an improvement in thermal stability was observed for the wood–polymer composites. The improvement in properties observed as more with styrene–GMA (1:1) combination. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1938–1945, 2004     

Investigations on the curing of epoxides with phthalic anhydride

The anhydride curing of epoxides was studied by performing copolymerizations of epichlorohydrin, phenyl glycidyl ether (PGE), or bisphenol-A-diglycidyl ether (BADGE) with phthalic anhydride (PSA). As initiators, tertiary amines or ammonium salts were used. In the case of epichlorohydrin, linear polyesters were obtained at 100°C. At higher temperatures (140–160°C), a side reaction of the CH₂Cl group took place which caused branching and partial crosslinking of the polymer. The reaction of phenyl glycidyl ether with phthalic anhydride gave linear, strongly alternating copolymers at temperatures of 120–160°C. Molecular weights (M¯_n) were in the range of 4000–87,000, depending on the purity of the starting materials and the initiator used. The reaction of the diepoxide BADGE with phthalic anhydride yielded highly crosslinked products. Their crosslink densities (which correlate with the glass transition temperature T_g). however, did not show the same dependence on initiator and purity of the starting materials as the molecular weights of the linear polyesters obtained by the “model reaction” of PGE with PSA. Possible reasons for this effect are discussed.     

Immobilization of mushroom polyphenol oxidase on poly(allyl glycidyl ether-co-ethylene glycol dimethacrylate) macroporous beaded copolymers

Functional, macroporous, beaded copolymers containing epoxy groups were synthesized for immobilization of polyphenol oxidase (PPO) from edible mushroom (Agaricus bisporus). The effect of incorporation of two different sets of monomers such as glycidyl methacrylate (GMA) and allyl glycidyl ether (AGE) and the effect of cross-linking agent ethylene glycol dimethacrylate (EGDM) with varying cross-link densities on binding and expression of mushroom PPO activity were studied. The effect of porogen viz. cyclohexanol and hexanol on PPO immobilization was studied. AGE copolymers with hexanol as a porogen were found to give higher binding and expression of PPO activity than GE polymers. Cross-linking of amino groups of enzyme with 5% glutaraldehyde for 6 h gave a stable binding of PPO on AGE-75(Hex) polymer with storage half-life of approximately 25 days. Under optimum conditions, AGE-75(Hex) polymer gave 70.3% of activity yield while percent retention of PPO activity was found to be 83.5%. Immobilized PPO showed a broader pH, higher temperature and excellent storage stability.     

Preparation,thermal properties,and morphology of graft copolymers in reactive blends of PHBV and PPC

Chemical modification of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) with glycidyl methacrylate (GMA) monomer, followed by reactively blending with end‐capped poly(propylene carbonate) (PPC) (50 wt%) was carried out during melt processing with dicumyl peroxide (DCP) initiation. The two kinds of graft copolymers of PHBV‐g‐GMA and PHBV‐g‐PPC were extracted with Soxhlet's apparatus, respectively. These grafting reaction mechanisms were proposed and the presence of grafting copolymers was confirmed by weight analysis, FTIR and NMR. The methyne carbon of GMA is confirmed to attach to quaternary carbon of the PHBV backbone. The epoxy groups in the copolymer of PHBV‐g‐GMA were capable to react with the carboxyl groups of end‐capped PPC, resulting in the formation of PHBV‐g‐PPC copolymer in situ. Their thermal properties and morphology were also characterized by DSC, WAXD, POM, and AFM. It revealed that after GMA grafting, the degradation of PHBV decreased and the nucleation of PHBV improved. The crystallinity degree, spherulites dimension and phase segregation between the two macromolecules decreased after PHBV grafted with PPC. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Gloss reduction and morphological properties of polycarbonate and poly(methyl methacrylate‐acrylonitrile‐butadiene‐styrene) blends with SAN‐co‐GMA as a reactive compatibilizer

The gloss properties of the polycarbonate (PC)/poly(methyl methacrylate‐acrylonitrile‐butadiene‐styrene) (MABS) blend with styrene‐acrylonitrile‐co‐glycidyl methacrylate (SAN‐co‐GMA) as a compatibilizing agent were investigated. For the PC/poly(MABS)/SAN‐co‐GMA (65/15/20, wt %) blend surface, the reduction of gloss level was observed most significantly when the GMA content was 0.1 wt %, compared with the blends with 0.05 wt % GMA or without GMA content. The gloss level of the PC/poly(MABS)/SAN‐co‐GMA (0.1 wt % GMA) blend surface was observed to be 35, which showed 65% lower than the PC/poly(MABS)/SAN‐co‐GMA blend without GMA content. The gloss reduction was most probably caused by the insoluble fractions of the PC/poly(MABS)/SAN‐co‐GMA blend that were formed by the reaction between the carboxylic acid group in poly(MABS) and epoxy group in SAN‐co‐GMA. The results of optical and transmission electron microscope analysis, spectroscopy study, and rheological properties supported the formation of insoluble structure of the PC/poly(MABS)/SAN‐co‐GMA blend when the GMA content was 0.1 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46450.     

Studies on graft copolymerization of glycidyl methacrylate onto poly(vinyl chloride) and curing behavior of its grafted copolymer

Poly(vinyl chloride) was dehydrochlorinated in an alkali solution and then grafted with glycidyl methacrylate (GMA) using benzol peroxide as the free-radical initator under a nitrogen atmosphere. The efficiency of grafting GMA under the influence of an alkali, GMA concentration, and duration of the grafting reaction, the viscosity properties, and the curing behavior with diamine were investigated. Maximum grafting to the extent of 46.4% was obtained. The optimum curing reaction condition were investigated. © 1995 John Wiley & Sons, Inc.     

Graft copolymerization of perfluoroheptyl methacrylate/glycidyl methacrylate mixtures with cotton fabric using Fe2+-thioureadioxide-H2O2 redox system

The ability of Fe²⁺-thioureadioxide-H₂O₂ redox system to induce polymerization of perfluoroheptyl methacrylate (PFHMA) and glycidyl methacrylate (GMA) individually as well as in binary mixtures was investigated under different conditions. Results obtained indicated that (a) PFHMA monomer could substantially be polymerized with cotton cellulose only in presence of GMA, (b) maximum contribution of PFHMA in the polymer add-on occurred upon using PFHMA mixture at a ratio of 50:50 at 80°C, (c) presence of PFHMA along with GMA offsets the fast termination rate of the latter as temperature increased from 60° to 90°C, (d) GMA activated PFHMA while the latter adversely affected GMA, (e) none of the PFHMA/GMA mixtures at ratios 2:8, 5:5, 8:2 showed synergetic effects, (f) H₂O₂ concentration of 0.01% and thioureadioxide concentration of 0.04% constituted the optimal concentrations for polymerization of PFHMA/GMA at a ratio of 5:5, and (g) the polymerization reaction proceeded initially very fast, then levelled off. (h) The water/oil repellency of the copolymerized cotton samples relied on the percent of PFHMA in total percent polymer add-on; these properties attained maximum at 4.25% PFHMA in a total polymer add-on of 22.5%.     

Synthesis and application of MDPE‐g‐GMA as reactive compatibilizer in blends of MDPE/PET and MDPE/PA6

In the present study, glycidyl methacrylate (GMA) grafted medium density polyethylene (MDPE‐g‐GMA) was synthesized in the molten state and applied as a reactive compatibilizer in MDPE/polyamid6 (PA6) and in MDPE/poly(ethylene terephtalate) (PET) blends. Graft copolymerization of GMA onto MDPE was performed in presence and absence of styrene, with different concentrations of dicumyl peroxide (DCP) as a radical initiator. In the presence of styrene, the MDPE‐g‐GMA with 6% GMA was obtained by addition of only 0.1 phr of DCP. Furthermore, the maximum grafting was reached when 0.6 and 0.7 phr concentration of DCP for styrene containing and styrene free samples were used, respectively. Torque‐time measurement showed faster grafting reaction rate in the presence of styrene. Four MDPE‐g‐GMA samples were selected as compatibilizers in the blends. Furthermore, the effects of melt flow index and grafting content of compatibilizers on mechanical properties and morphology of the blends were investigated through tensile tests and SEM analysis. Tensile test results indicated that the presence of compatibilizers in the blends led to 250 and 133% increase in elongation at break for PA6 and PET blends, respectively. Moreover, the best tensile results for blends were obtained using MDPE‐g‐GMA with high flow ability. The average particle size of the dispersed phase decreased by 350% for PA6 and 300% for PET blends compared with nonreactive blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Microwave-assisted,rapid cycloaddition of allyl glycidyl ether and CO2 by employing pyridinium-based ionic liquid catalysts

This study investigated the use of pyridinium-based ionic liquids (ILs) as an efficient catalyst for the rapid solvent-free microwave-assisted cycloaddition of allyl glycidyl ether (AGE) and CO₂ to yield allyl glycidyl carbonate (AGC) under moderate reaction conditions. The cycloaddition reaction occurred over a short reaction time of 30 s, resulting in a high turnover frequency (TOF) ranging from 200 to 7000 h^− 1. The effects of alkyl chain length and anion of pyridinium-based catalysts on the cycloaddition reactivity were studied. The effects of reaction parameters such as the amount of catalyst, microwave power, CO₂ pressure, and reaction time were also investigated.     

Wood–polymer composites prepared by the in situ polymerization of monomers within wood

Wood–polymer composites (WPCs) were prepared from poplar wood (P. ussuriensis Komarov) in a two‐step procedure. Maleic anhydride (MAN) was first dissolved in acetone and impregnated into wood; this was followed by a heat process; and then, glycidyl methacrylate (GMA) and styrene (St) were further impregnated into the MAN‐treated wood, followed by a second thermal treatment. Finally, the novel WPC was fabricated. The reactions occurring in the WPC, the aggregation of the resulting polymers, and their interaction with the wood substrate were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, and dynamic mechanical analysis. The performance of WPC was also evaluated in terms of the mechanical properties and durability, which were then correlated with the structural analysis of the WPC. The test results show that MAN and GMA/St chemically reacted with the wood cell walls in sequence, and the quantity of hydroxyl groups in the wood cell walls was evidently reduced. Meanwhile, St copolymerized with GMA or MAN, and the resulting polymers mainly filled in the wood cell lumen in an amorphous form, tightly contacting the wood cell walls without noticeable gaps. As a result, the mechanical properties, decay resistance, and dimensional stability of the WPC were remarkably improved over those of the untreated wood, and its glass‐transition temperature also increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Studies on properties of softwood (Ficus hispida)/PMMA nanocomposites reinforced with polymerizable surfactant-modified nanoclay

Soft wood (Ficus hispida) was chemically modified by impregnation of methyl methacrylate monomer, glycidyl methacrylate (GMA), a cross-linking agent, and montmorillonite (MMT) using catalyst heat treatment. MMT was modified by using a polymerizable surfactant 2-acryloloxy ethyl trimethyl ammonium chloride (ATAC) and a mixture of surfactants ATAC and cetyl trimethyl ammonium bromide (CTAB) in a molar ratio of (1:1). A comparative study on different properties of the prepared wood polymer nanocomposite (WPNC) based on impregnation of intercalating mixture containing MMA/GMA/clay modified by both the surfactants (ATAC and CTAB) and MMA/GMA/clay modified by only surfactant ATAC were done. FTIR, XRD, and TGA studies were employed for the characterization of clay and WPNC. WPNC prepared by using combined surfactant-modified clay along with MMA/GMA exhibited improved dimensional stability, chemical resistance, thermal stability, mechanical properties, and lower water uptake than that of WPNC prepared by using single surfactant-modified clay and MMA/GMA system.     

Epoxidation of methyl oleate with molecular oxygen in the presence of aldehydes

The epoxidation of methyl oleate with molecular oxygen in the presence of aldehydes was investigated and optimized. Epoxide yields up to 99% were observed in organic solvents. The preponderant radical reaction was started by a single organic radical chain initiator, without using a metal catalyst. The radical character of the reaction was revealed by the concurrent occurrence of trans and cis epoxides and by the prevention of epoxide formation through a radical scavenger. Both branched aldehydes and the linear aldehyde n‐hexanal were well suited in organic solvents. The linear n‐hexanal enabled also a superior epoxide yield of 78% in the green solvent water. The oxidation of high‐oleic sunflower oil under the same conditions with n‐hexanal yielded 39% epoxide groups.