Modification of some mechanical properties of spruce by radiation induced copolymerization of acrylonitrile and methyl methacrylate with allyl glycidyl ether

In this study, spruce samples were impregnated with acrylonitrile (AN), methyl methacrylate (MMA), allyl glycidyl ether (AGE), AGE/AN or AGE/MMA monomers and monomer mixtures. In situ polymerization (copolymerization) was achieved by gamma irradiation. The relationship between the mechanical properties of the wood‐polymer(copolymer) composites and the kind and quantity of polymers and copolymers, irradiation dose and artificial aging treatment of the wood was investigated. The fine structure of wood‐polymer(copolymer) composites was determined by Scanning Electron Microscopy. The presence of homopolymer and copolymers increased the mechanical properties of the wood. The compressive strength and Brinell Hardness Numbers, determined for untreated and treated wood samples, indicated that the mechanical strength of wood‐polymer (copolyrner) was significantly increased in the presence of P(AGE/MMA). At maximum percent conversion, the percentage increase in the compressive strength with regard to the applied force perpendicular to the fibers in spruce was 218%. After aging for 28 days, it was found that there were no significant changes in mechanical stability.     

Preparation and properties of some wood/(co)polymer composites

Beech and spruce samples which were impregnated with acrylonitrile (AN), methyl methacrylate (MMA), allyl glycidyl ether (AGE), AGE + AN, AGE + MMA monomers and monomer mixtures were subjected to (co)polymerization by gamma radiation. The dimensional stabilization and resistance against biodegradation of wood/(co)polymer composites was investigated. The water uptake capacities of wood/(co)polymer composites were observed to decrease by more than 70% as compared to untreated samples. There were no noticeable changes in the structure of the wood/(co)polymer composites after treatment with artifical acid rain. It was found that the wood/(co)polymer composites were stable against the biological attacks of microorganisms like mould and bacteria.     

Improvement of mechanical stability of beechwood by radiation‐induced in situ copolymerization of allyl glycidyl ether with acrylonitrile and methyl methacrylate

Acrylonitrile (AN), methyl methacrylate (MMA), allyl glycidyl ether (AGE), AGE + AN monomer, AGE + MMA monomer, and monomer mixtures were used to conserve and consolidate beechwood. After the impregnation of these monomer mixtures in the wood, polymerization was accomplished by gamma irradiation. The fine structures of wood + polymer(copolymer) composites were investigated by scanning electron microscopy (SEM). The copolymer obtained from AGE + MMA monomer mixtures showed the optimum compatibility with the wood. The compressive strength and Brinell hardness numbers determined for untreated and treated wood samples indicated that the mechanical strength was greater in wood + polymer(copolymer) composites than in untreated wood and was greatest in the samples containing AGE + AN and AGE + MMA copolymers. All monomer couples used in this study increased the mechanical strength of the wood and protected the samples against aging. AGE + MMA copolymers were the most effective in protecting the wood against various environmental attacks. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1515–1523, 1999     

A comparative study of using allyl alcohol based copolymers in the preservation of wood: Oak vs. cedar

Wood is an important raw material that is cheap and easily worked. However, wooden objects are subject to environmental attack and mechanical shocks. In this study, our aim is to preserve wooden objects against envrironmental deterioration and mechanical shocks on to consolidate objects already degraded. Allyl alcohol (AA), acrylonitrile (AN), methyl methacrylate (MMA) and AA/AN, AA/MMA monomer mixtures were impregnated into oak and cedar. Polymerization was accomplished by gamma irradiation. The mechanical properties and the dimensional stability of the wood‐copolymer composites were determined. The presence of polymer and copolymer in the wood increased the mechanical durability of the wood. The results of the hardness tests and the compressive strengths determined in parallel and perpendicular directions to the fibers revealed that P(AA/MMA), P(AA/AN) copolymers are effective in increasing the mechanical durability of pristine‐oak and cedar woods. Similar results were also obtained from hardness tests. The decrease in the mechanical durability of pristine‐oak and cedar woods after aging for 28 days is slight. The water uptake capacity of wood + copolymer composites was observed to decrease by more than 50% compared with the original samples. In the cedar wood, where the density is low and the quantity of copolymer is high, this decrease ranged from 100% to 50%.     

Photopolymerizable bisallylcarbonate and bisacrylic monomers useful in the formulation of dental composite resins and in the crosslinking of methyl methacrylate

Two new bisallylic monomers [allyl p‐allyl carbonate benzoate (ApACBz) and 1,4‐phenylenbis(methylene)diallyl carbonate (1,4‐FMDAC)] and one bisacrylic monomer [1,4‐bis(acryloyloxymethyl)benzene (1,4‐BAMB)] were synthesized and used as crosslinking agents of methyl methacrylate (MMA) at different mass ratios (10, 20, 40, and 50%). All of the obtained copolymers showed improved thermal stability in comparison with that of the MMA homopolymer. Also, ApACBz and 1,4‐FMDAC were used as bisphenol A glycidyl methacrylate (Bis‐GMA) eluents to prepare dental resin composites. When compared to the control, the Bis‐GMA–new eluent composites had a higher double‐bond conversion, a higher solubility (p < 0.05) and a lower flexural strength (p < 0.05), whereas the elastic modulus and water sorption values were not statistically different (p > 0.05). The 1,4‐FMDAC and ApACBz monomers are promising eluents of Bis‐GMA for the preparation of dental composites with high degrees of conversion. In addition, the ApACBz, 1,4‐FMDAC, and 1,4‐BAMB monomers are potentially useful crosslinking agents when polymer networks of poly(methyl methacrylate) with a high thermal stability are desired. The application‐oriented tests of the monomers in dental composite formulations showed a sufficient storage stability, high photocuring activity, excellent crosslinking of MMA, and good thermal and mechanical properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42920.     

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.     

Rubberwood–polymer composites based on diallyl phthalate and methyl methacrylate

Wood–polymer composites (WPC) of rubberwood (Hevea brasiliensis), were prepared by impregnating the wood with methyl methacrylate (MMA), and the combinations of MMA and diallyl phthalate (MMA/DAP). Polymerization was carried out by catalyst heat treatment. Impregnated samples showed significant improvements in compressive and impact strengths, hardness, and dimensional stability (toward water) over that the untreated rubberwood. © 1995 John Wiley & Sons, Inc.     

Dimensional stability of wood–polymer composites

Wood–polymer composites (WPC) were prepared by impregnation of polymeric monomers in wood and in situ polymerization. Three polymeric chemicals were chosen for this study: methyl methacrylate (MMA), hydroxyethylene methacrylate (HEMA), and ethylene glycol dimethacrylate (EGDMA). The effects of polymeric monomers and their combinations on moisture adsorption (M), anti–moisture adsorption efficiency (AME), liquid water uptake (D), water repellency efficiency (WRE), longitudinal, radial, tangential, and volumetric swelling properties (S) after soaking, and antiswelling efficiency (ASE) were investigated. It was found that M was different for different methacrylate combinations and depended not only on the composition of the impregnants, but also on wood properties. Liquid water uptake was similar regardless of the formulation of the WPC. Wood–polymer composites with high MMA content displayed enhanced dimensional stabilities, but WPCs with high HEMA content did not. Tangential and volumetric ASEs were strongly dependent on the type of treatment. Mold growth tests showed that wood treated with HEMA alone had no surface mold growth, and wood treated with MMA alone also showed less mold growth than did the control samples. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 5085–5094, 2006     

乳聚丁苯互穿网络型热塑性弹性体的制备

以丁苯胶乳为种子乳液,苯乙烯、甲基丙烯酸甲酯、丙烯腈或它们的混合物的硬单体,用氧化还原引发体系,经种子乳液聚合法同备出复合乳液,絮凝干燥后所得互穿聚合物网络可热塑性反复加工。考察了硬单体的种类和用量、交联剂的种类及用量、反复加工次数对聚合物力学性能的影响。用透射电子显微镜观察了乳胶粒微观形态,结果表明：用混合单体,聚合物力学性能较优,以３５份Ｓｔ＾＋ＭＭＡ为第二单体制备的聚合物的攫断伸长率为４００％,拉伸强度为９．３ＭＰａ,３００％定伸应力为７．６ＭＰ,撕裂强度为７３．９ｋＮ．Ｍ＾－１,邵尔Ａ型硬度为８４。     

An Investigation of the Reaction of Epoxides with Wood

Abstract

The reaction of wood with two functionalised epoxides, allyl glycidyl ether (AGE) and glycidyl methacrylate (GMA), has been studied. For the reaction with whole wood samples of Scots Pine (Pinus sylvestris), maximum weight percent gains (WPG's) of 20% (GMA) and 7% (AGE) were obtained using pyridine as a solvent/catalyst. However, reaction of the epoxides with thermomechanically pulped Spruce fibre yielded WPG's of 15% (GMA) and 0% (AGE) under the same reaction conditions. In addition, the use of hydroquinone as an inhibitor of polymerisation yielded variable results. The observed WPG's obtained were found to be strongly influenced by the clean-up procedure used at the end of the reaction. The results suggest that, under the conditions used in this study, no reaction with the wood hydroxyl groups is occurring but that homopolymerisation of the epoxides is responsible for the observed data.     

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.     

含氟单体对环氧丙烯酸酯树脂性能的影响

以甲基丙烯酸甲酯（MMA）、甲基丙烯酸缩水甘油酯（GMA）、丙烯酸六氟丁酯（F6BA）为原料,采用溶液聚合法制备了含氟环氧丙烯酸酯共聚物。采用FT-IR、¹³C NMR 、DSC和GPC等手段对共聚物的化学结构、玻璃化转变温度和分子量及其分布的分析表明：产物是含氟类环氧丙烯酸酯共聚物,玻璃化转变温度随含氟单体用量的增大而降低,分子量分布较窄,分布指数在1.35～1.65之间。采用JC2000C1静滴接触角/界面张力仪考察了共聚物膜的表面能,发现随着共聚物中氟单体含量的增加,表面能下降,当氟单体含量达到20％时,其表面能降低到38.27 mJ·m^-2,吸水率随氟单体用量的增大从18.72％下降至4.55％,耐酸碱性能明显提高,涂膜铅笔硬度从3H下降至2H。     

Synthesis and thermal self-crosslinking reaction of copolymers from 2,3-epoxypropyl methacrylate and p-substituted phenyl methacrylates

Copolymers of 2,3-expoxypropyl (glycidyl) methacrylate (GMA) with various phenyl methacrylates such as 4-nitrophenyl methacrylate (NPMA), 4-chlorophenyl methacrylate (CPMA), or phenyl methacrylate (PMA), and other monomers such as methyl methacrylate (MMA), ethyl acrylate (EA), or styrene (ST) were synthesized by radical copolymerization, and then thermal self-crosslinking reactions of the obtained copolymers were carried out using various catalysts such as quarternary ammonium salts, tert-amines, or the crown ether/potassium salt systems at 100–150°C. Although the copolymer of GMA–NPMA–MMA does not produce any gel products without catalyst upon heating at 110°C for 5 h, this copolymer gives gel products in 82% yield using 10 mol% of tetrabutylammonium bromide as a catalyst under the same conditions. The rate of gel production of the copolymer of NPMA is faster than those of copolymers of CPMA and PMA. The rate of the gel production of the copolymer of GMA–NPMA–EA is also faster than those of copolymers of MMA and ST. Furthermore, it was found that the rate of gel production of the copolymer was strongly affected by the kind of catalyst, the catalyst concentration, and the reaction temperature.     

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     

FTIR characterization of tropical wood–polymer composites

Wood–polymer composites (WPC) of Geronggang (Cratoxylon arborescens), a light tropical hardwood, impregnated with methyl methacrylate (MMA), methyl methacrylate-co-acrylonitrile (1 : 1; MAN), and styrene-co-acrylonitrile (3 : 2; STAN), were prepared by in situ polymerization using gamma radiation or the catalyst–heat treatment. The FTIR spectra of the three types of WPC, with polymer loadings ranging from 10 to 70%, were compared with that of the wood itself and the respective polymers. Characteristic peaks due to C?O vibration of MMA, C?N stretching of acrylonitrile, and ring stretching and bending of styrene monomers, were prominent in the samples that had higher polymer loadings. For the copolymeric systems, quantitation of the FTIR spectra of these characteristic peaks enabled calculations of incorporated acrylonitrile and styrene monomers in the composites to be made. The FTIR spectra of the residues remaining, after exhaustive extraction to remove homopolymer, showed that graft copolymerization of wood components with acrylonitrile and styrene monomers was possible, but not with MMA. Composites prepared by the two methods, gamma radiation and the catalyst–heat treatment, were shown to be chemically very similar.     

SBR/P(St-MMA-AN)互穿网络聚合物的加工和力学性能

以丁苯胶乳为种子乳液，苯乙烯、甲基丙烯酸甲酯、丙烯腈的混合物为硬单体，二乙烯基苯为交联剂，在氧化还原引发体系下，以种子乳液聚合法得复合乳液，絮凝干燥后得到共聚物。研究了硬单体用量、硬单体配比、加工次数对聚合物力学性能的影响规律。结果表明，聚合物可反复进行热塑性加工，聚合物微观相畴随加工次数增多而变小。     

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.     

Epoxy-functional thermoplastic copolymers and their incorporation into a thermosetting resin

The customization of polymer networks can be made possible via dual-functional monomers, molecules characterized by two different reactive substituents that allow for versatile methods of polymerization. The dual-functional, epoxy-methacrylate monomers, glycidyl methacrylate (GMA), and vanillyl alcohol epoxy-methacrylate (VAEM), were polymerized with methyl methacrylate (MMA) via reversible addition-fragmentation chain transfer (RAFT) polymerization to form low molecular weight (~10–20 kDa) epoxy-functional thermoplastic copolymers, poly(VAEM-co-MMA), and poly(GMA-co-MMA). The copolymers were blended at 5 wt% into an epoxy resin system containing EPON Resin 828 and EPIKURE W Curing Agent and cured thermally to create unique interpenetrating polymer networks (IPNs). The resulting IPNs were compared to the cured neat resin and evaluated for thermal and mechanical properties, where maintained thermal properties and enhancements of stiffness and toughness were demonstrated.     

Acrylonitrile–butadiene–styrene toughened nylon 6: The influences of compatibilizer on morphology and impact properties

Polymer alloys have been used as an alternative to obtain polymeric materials with unique physical properties. Generally, the polymer mixture is incompatible, which makes it necessary to use a compatibilizer to improve the interfacial adhesion. Nylon 6 (PA6) is an attractive polymer to use in engineering applications, but it has processing instability and relatively low notched impact strength. In this study, the acrylonitrile–butadiene–styrene (ABS) triblock copolymer was used as an impact modifier for PA6. Poly(methyl methacrylate‐co‐maleic anyhydride) (MMA‐MA) and poly(methyl methacrylate‐co‐glycidyl methacrylate) (MMA‐GMA) were used as compatibilizers for this blend. The morphology and impact strength of the blends were evaluated as a function of blend composition and the presence of compatibilizers. The blends compatibilized with maleated copolymer exhibited an impact strength up to 800 J/m and a morphology with ABS domains more efi8ciently dispersed. Moderate amounts of MA functionality in the compatibilizer (～5%) and small amounts of compatibilizer in the blend (～5%) appear sufficient to improve the impact properties and ABS dispersion. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 842–847, 2003     

Vapor phase photografting on low-density polyethylene film in binary monomer systems

Vapor phase photografting of monomer mixtures on low-density polyethylene film, on which benzoyl peroxide is coated, was investigated at 60°C using various vinyl, allyl, and solid monomers. Styrene (St) itself was difficult to graft on the film substrate, but the combinations of St with vinyl monomers such as acrylonitrile (AN), glycidyl methacrylate (GMA), acrylic acid, and methacrylic acid led to the accelerated grafting, affording a maximum percent grafting at an certain monomer ratio. The same combination effect was observed for AN–N-vinyl pyrrolidone and –GMA monomer mixtures. The monomer combinations such as allyl aldehyde–St and allyl alcohol–maleic anhydride were useful for performing the grafting of allyl monomers effectively. Maleic anhydride and maleimide as solid monomers were also possible to introduce into the film substrate by means of the monomer combination, where St, N-vinyl pyrrolidone, vinyl ethers, and benzyl methacrylate were available as comonomers. Thus, the monomer combinations affording an accelerating effect on grafting may be monomer pairs rich in an alternative copolymerizability, suggesting that monomer reactivity ratio controls a major factor for the combination effect. It was confirmed from IR study on grafted films that both monomer components are introduced in the film substrate as the grafted chain component.