Catalyst–accelerator method for the preparation of wood–polymer composites at ambient temperature

Wood–polymer composites (WPC) are materials which may be prepared by impregnating wood with a variety of monomers which are subsequently polymerized by either gamma irradiation or by conventional radical initiators. The inclusion of the polymer into the wood matrix improves the physical properties of the composite compared to plain wood. The catalyst–accelerator method allows in situ polymerization of vinyl monomers at ambient conditions and thus reduces the loss of the volatile monomer during curing, which is a major disadvantage of the heat–catalyst method. The combination of peroxide initiators with an aromatic amine accelerator was optimized for the methyl methacrylate system. Polymer loadings and mechanical properties of WPC prepared from Pinus radiata using the catalyst–accelerator method were compared with those obtained using the gammaradiation method. © 1995 John Wiley & Sons, Inc.     

Thermal properties of tropical wood–polymer composites

Wood–polymer composites (WPC) of Geronggang (GE; Cratoxylon arborescens), a light tropical hardwood, impregnated with methyl methacrylate (MMA), styrene-co-acrylonitrile (3: 2; STAN), methyl methacrylate-co-bis (2-chloroethyl) vinyl phosphonate (3 : 1; MVP) and methyl methacrylate-co-bis (chloropropyl)-2-propene phosphonate (3:1;MPP), were prepared by in situ polymerization using γ-radiation or catalyst-heat treatment. Thermal characterization of these WPC by limiting oxygen index measurements (LOI), thermogravimetry (TG), and differential scanning calorimetry (DSC) showed that the impregnants greatly modified the wood properties. The LOI values of the GE–MVP and GE–MPP composites were much higher than that for GE and the other composites, indicating the effectiveness of the phosphonates as flame retardants. Concomitantly, the flaming characteristics also compared favorably against that for GE and the other composites. The decomposition temperature and maximum rate of weight loss determined by TG for GE–MVP and GE–MPP were substantially reduced, whereas the char yields were greatly higher. These observations again indicate that phosphonates imparted flame-retarding properties to their composites. The thermal properties of GE–MMA and GE–STAN composites were not vastly different from that of untreated GE. Flame retardancy in the phosphonate-containing composites was effected through both the condensed- and gaseous-phase mechanisms due to the presence of phosphorus and chlorine, respectively. Indication of grafting of polymer to wood was found for GE–STAN, GE–MVP, and GE–MPP composites, but not for GE–MMA. Composites prepared by γ-radiation or by the catalyst-heat treatment had similar thermal characteristics.     

Dynamic mechanical analysis of tropical wood–polymer composites

Wood–polymer composites (WPC) of Geronggang (GE; Cratoxylon arborescens), a light tropical hardwood, impregnated with methyl methacrylate (MMA) and styrene-co-acrylonitrile (3 : 2; STAN), were prepared by in situ polymerization using γ radiation or catalystheat treatment. The dynamic flexural storage modulus, E′, for oven-dried GE, moist GE, and GE–MMA and GE–STAN composites decreased with increasing temperature. The percentage decreases for GE with 10 and 16.5% moisture contents were 74.5 and 98.2%, respectively, which were higher than those for GE and GE composites, which ranged between 40 and 50%. The impregnated polymers were not as effective as water in acting as plasticizers, due to their nonpolar nature and much higher molecular weights. The α-transition peaks for moist GE and GE composites were more distinct and were shifted to lower temperatures than those for oven-dried GE. The values ranged between 75 and 150°C for moist GE and between 102 and 170°C for the GE composites. The α-transitions of the catalyst–heat-treated GE composites were lower than that of the radiation-induced counterparts. GE–STAN composites were also observed to have lower α-transition temperatures than those for GE–MMA for the respective treatment process, which seems to suggest that STAN interacted to a greater extent with cell wall components than did MMA.     

Modification of rubber wood with styrene in combination with diethyl allyl phosphate as the flame‐retardant agent

Rubber wood (Hevea brasiliensis) polymer composite was prepared using styrene as the monomer in combination with diethyl allyl phosphate (DEAP) to improve flame‐retardant property. DEAP was synthesized, characterized and incorporated into wood with styrene. The polymerization was accomplished by catalyst heat treatment using AIBN as the catalyst. The properties of wood–polymer composites (WPC) like water absorption, swelling in water, hardness, modulus of elasticity (MOE), modulus of rupture (MOR) etc. were improved on treatment. The thermal degradation behavior of WPC was evaluated using thermogravimetric analysis (TGA) and the flammability of the WPC was evaluated using the limiting oxygen index (LOI) test. It was observed that fire retardancy of WPC improved on incorporation of DEAP. FTIR spectroscopy and SEM study showed the interaction between wood and the polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

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.     

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.     

IR studies of wood plastic composites

Wood plastic composites (WPC) of simul were prepared by gamma radiation using butylacrylate (BA) and methylmethacrylate (MMA) as the monomer and methanol as the swelling agent at 9:1 (v/v) ratio. IR spectra of simul, bulk polymer of BA (or MMA) film, and WPC of different polymer loadings ranging from 18 to 115% were studied. Increase of the characteristic peak intensity at 1735 cm^?1 (C?O vibration for acetyl groups) over that of 1620 cm^?1 (conjugated aryl carbonyl groups) along with the increase of polymer loading of simul with the monomer indicates that the graft copolymerization took place between the monomer and the simul wood matrix. © 1993 John Wiley & Sons, Inc.     

木粉疏水改性对HDPE基木塑复合材料性能的影响

采用一种操作简便且易于工业推广的方法对木粉进行疏水改性，具体过程为：将3种可热聚合的单体，即甲基丙烯酸甲酯（MMA）、甲基丙烯酸丁酯（BMA）和苯乙烯（St）均匀喷洒在木粉上，经过预热处理后，与配方中其他组分，如高密度聚乙烯（HDPE）和马来酸酐接枝聚乙烯（MAPE）等通过高速混合机混合均匀，采用双螺杆挤出机造粒后，注射制备木塑复合材料（WPC）样条，测试其力学性能。另外，考察了疏水改性对WPC接触角、维卡软化温度、洛氏硬度、吸水性能、热性能的影响规律。结果表明：疏水改性后WPC的接触角增大，木粉和HDPE的界面相容性改善，力学性能得到明显提高。其中，当MMA、BMA和St的添加量为3%时，WPC的力学性能最好，与疏水改性前相比，弯曲强度分别提高了17.3%、26.3%和27.5%，弯曲模量分别提高了24.4%、24.4%和26.0%，冲击强度分别提高了54.7%、57.7%和60.5%。 此外，疏水改性后WPC的维卡软化温度、洛氏硬度、耐水性和耐热性也得到改善。     

Phase Morphology,Thermal, Thermomechanical and Interfacial Properties of PP/SAN/SBS Blend Systems

The effect of styrene–butadiene–styrene content on morphology, melting, crystallinity, dynamic mechanical properties and relaxation processes of polypropylene/poly(styrene-co-acrylonitrile)/styrene–butadiene–styrene blends was investigated. Styrene–butadiene–styrene reduced the average size of dispersed particles and generated complex aggregates in the matrix. Morphology development examined by dynamic mechanical thermal analysis showed increased damping of poly(styrene-co-acrylonitrile) domains at high styrene–butadiene–styrene contents. All blends showed reduced crystallinity and melting point compared with neat polypropylene. Poorer nucleation effect of dispersed particles at high styrene–butadiene–styrene loadings was observed. Compatibilization accelerated the form relaxation of dispersed particles. Additional relaxation process probably due to styrene–butadiene–styrene chains was observed in blends containing 10% and higher styrene–butadiene–styrene content.     

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.     

Effect of silica nanopowder on the properties of wood flour/polymer composite

Low‐density polyethylene (LDPE), high‐density polyethylene (HDPE), polypropylene (PP), and polyvinyl chloride (PVC) (1:1:1:0.5) were solution blended by using a mixture of solvents consisting of xylene and tetrahydrofuran (THF) (70:30). SiO₂ nanoparticles were modified by cetyl trimethyl ammonium bromide (CTAB). Wood polymer composites (WPC) were prepared by using polymer mixture, polyethylene‐co‐glycidyl methacrylate (PE‐co‐GMA), wood flour, and modified SiO₂. X‐ray diffraction (XRD) studies showed that the intensity of the peaks of polymer mixture decreased due to incorporation of SiO₂. The dispersion of SiO₂ nanoparticles and morphological characteristics were examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The interaction between SiO₂ nanoparticles, PE‐co‐GMA, polymer mixture, and wood was studied by Fourier transform infrared spectroscopy (FTIR). Tensile and flexural properties of the composites improved significantly due to the incorporation of SiO₂ nanoparticles. Thermal stability, hardness, flame retardancy, and water resistance capacity were also found to enhance. Maximum improvement in properties was observed by the inclusion of 3 phr modified SiO₂ in WPC. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Improvement of the mechanical stability of oak by radiation-induced in-situ copolymerization of allyl glycidyl ether with acrylonitrile and methyl methacrylate

This study deals with the improvement of the mechanical stability of oak, which belongs to the hardwoods, by radiation-induced in-situ copolymerization of certain monomers. Acrylonitrile (AN), methyl methacrylate (MMA), allyl glycidyl ether/acrylonitrile (AGE/AN), and allyl glycidyl ether/methyl methacrylate (AGE/MMA) monomers and monomer mixtures were employed to conserve and consolidate the wood. After impregnating oak with these monomer mixtures, polymerization was accomplished by γ-irradiation. The relationships between the mechanical properties of the wood/(co)polymer composites and the anatomic structure of the wood, the types and the quantity of the polymer and copolymer, the irradiation dose and the aging process were explored. The fine structure of the wood/(co)polymer composites and the compatibility of wood with polymer and copolymer were investigated by scanning electron microscopy. The existence of polymer and copolymer in the wood enhanced the mechanical durability of the wood. The results of the hardness and the compressive strength tests applied in the parallel and perpendicular directions to the fibers of the wood/(co)polymer composites show that P(AGE/MMA), P(AGE/AN) copolymers are effective in raising the mechanical durability. In the case of P(AGE/MMA), the increase in the compressive strength perpendicular to the fibers in the oak wood is 179% at highest conversion. Similar results were also acquired from hardness tests. The decrease in the mechanical durability after aging for 28 d was very little.     

Effects of acrylic‐based processing aids on processibility,rheology, thermal and structural stability,and mechanical properties of PVC/wood–sawdust composites

Methyl methacrylate and ethylacrylate (MMA‐co‐EA) and methyl methacrylate and butylacrylate (MMA‐co‐BA) copolymeric processing aids were introduced into poly(vinyl chloride) (PVC)/33.3 wt % wood–sawdust composites containing 0.6 and 2.4 phr of calcium stearate lubricant. The properties of the composites were monitored in terms of processibility, rheology, thermal and structural stability, and mechanical properties. It was found that the mixing torque, wall shear stress, and extrudate swell ratio increased with increasing processing aid content because of increased PVC entanglement. MMA‐co‐BA (PA20) was found to be more effective than MMA‐co‐EA (K120 and K130), this being associated with the flexibility of the processing aids, and the dipole–dipole interactions between sawdust particles and polymeric processing aids. The sharkskin characteristic of the composite extrudate at high extrusion rate was moderated by the presence of processing aids. Adding the acrylic‐based processing aids and lubricant into PVC/sawdust composites improved the thermal and structural stability of the composites, which were evidenced by an increase in glass transition and decomposition temperatures and a decrease in polyene sequences, respectively. The changes in the mechanical properties of the composites involved a composite homogeneity, which was varied by degree of entanglement and the presence of wood sawdust, and un‐reacted processing aids left in the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 782–790, 2004     

Effect of compatibilizer in acrylonitrile‐butadiene‐styrene toughened nylon 6 blends: Ductile–brittle transition temperature

The ductile–brittle transition temperatures were determined for compatibilized nylon 6/acrylonitrile‐butadiene‐styrene (PA6/ABS) copolymer blends. The compatibilizers used for those blends were methyl methacrylate‐co‐maleic anhydride (MMA‐MAH) and MMA‐co‐glycidyl methacrylate (MMA‐GMA). The ductile–brittle transition temperatures were found to be lower for blends compatibilized through maleate modified acrylic polymers. At room temperature, the PA6/ABS binary blend was essentially brittle whereas the ternary blends with MMA‐MAH compatibilizer were supertough and showed a ductile–brittle transition temperature at ?10°C. The blends compatibilized with maleated copolymer exhibited impact strengths of up to 800 J/m. However, the blends compatibilized with MMA‐GMA showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2643–2647, 2003     

Preparation of core-shell emulsion polymer and optimization of shell composition with respect to opacity of paint film

A series of core-shell latexes comprising a poly(n-butyl acrylate-co-methyl methacrylate-co-methacrylic acid) (PBA/MMA/MAA) core and a poly(styrene-co-acrylonitrile) (PS/AN), poly(butyl acrylate-co-methyl methacrylate) (PBA/MMA) shell were prepared at different shell composition ratios. These core-shell binders were used for preparation of decorative coatings. The latexes were synthesized by a semi-continuous sequential emulsion polymerization and characterized by using transmission electron microscopy (TEM), particle size analyser, viscometry and opacity of paint film. The core-shell emulsion with styrene/acrylonitrile ratio 60/40 as shell composition shows the best optical properties.     

Transparent poly(methyl methacrylate‐co‐butyl acrylate) nanofibers

Nanofibers of n‐Butyl Acrylate/Methyl Methacrylate copolymer [P(BA‐co‐MMA)] were produced by electrospinning in this study. P(BA‐co‐MMA) was synthesized by emulsion polymerization. The structural and thermal properties of copolymers and electrospun P(BA‐co‐MMA) nanofibers were analyzed using Fourier transform infrared spectroscopy–Attenuated total reflectance (FTIR–ATR), Nuclear magnetic spectroscopy (NMR), and Differential scanning calorimetry (DSC). FTIR–ATR spectra and NMR spectrum revealed that BA and MMA had effectively participated in polymerization. The morphology of the resulting nanofibers was investigated by scanning electron microscopy, indicating that the diameters of P(BA‐co‐MMA) nanofibers were strongly dependent on the polymer solution dielectric constant, and concentration of solution and flow rate. Homogeneous electrospun P(BA‐co‐MMA) fibers as small as 390 ± 30 nm were successfully produced. The dielectric properties of polymer solution strongly affected the diameter and morphology of electrospun polymer fibers. The bending instability of the electrospinning jet increased with higher dielectric constant. The charges inside the polymer jet tended to repel each other so as to stretch and reduce the diameter of the polymer fibers by the presence of high dielectric environment of the solvent. The extent to which the choice of solvent affects the nanofiber characteristics were well illustrated in the electrospinning of [P(BA‐co‐MMA)] from solvents and mixed solvents. Nanofiber mats showed relatively high hydrophobicity with intrinsic water contact angle up to 120°. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4264–4272, 2013     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(styrene‐co‐acrylonitrile)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMAs) (designated as iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(styrene‐co‐acrylonitrile) (abbreviated as PSAN) containing 25 wt % of acrylonitrile in tetrahydrofuran to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PSAN. The aPMMA/PSAN and sPMMA/PSAN blends were found to be miscible because all the prepared films were transparent and showed composition dependent glass transition temperatures (T_gs). The glass transition temperatures of the two miscible blends were fitted well by the Fox equation, and no broadening of the glass transition regions was observed. The iPMMA/PSAN blends were found to be immiscible, because most of the cast films were translucent and had two glass transition temperatures. Through the use of a simple binary interaction model, the following comments can be drawn. The isotactic MMA segments seemed to interact differently with styrene and with acrylonitrile segments from atactic or syndiotactic MMA segments. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2894–2899, 1999     

Comparative Study of Water Absorption Behavior of Wood and Wood Plastic Composites of Simul Using Film Neutron Radiography

Abstract

The film neutron radiography method was adopted for a comparative study of water absorption behavior in wood and wood plastic composites (WPC) of Simul using the thermal neutron radiography facility of 3 MW TRIGA MARK-II research reactor at Atomic Energy Research Establishment, Savar Dhaka, Bangladesh. Variations of optical density values due to water absorption of these samples were measured from neutron radiographic images. The WPC samples were prepared with impregnating monomer methylmethacrylate (MMA) under gamma radiation in order to study their water absorption behavior. The water absorption nature of Simul wood (Salmalia mamabrarica) and its composites, with and without urea as additive, was monitored by optical density measurements. The absorption of water in wood increases continuously with time. Where as, the water absorption by wood plastic composites is less compared to virgin wood; the composites with additive urea showed less water absorption than did those of virgin wood and the composites without urea.     

Wood-Plastic Composite with Methylmethacrylate in Presence of Novel Additives

Wood–plastic composites (WPC) were prepared with kadom and mango wood of Bangladesh under Co-60 gamma irradiation using methylmethacrylate (MMA) as the bulk monomer mixed with methanol (swelling solvent) at different proportions in presence of a number of additives such as N-vinyl pyrrolidone, tripropylene glycol diacrylate, trimethylol propane triacrylate, copper sulfate, sulfuric acid, and urea. Composites prepared with urea, NVP, and CuSO₄ possess better tensile and protective properties.