Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003     

The Improvement of Bond Strength Properties and Surface Characteristics of Resinous Woods

Apitong (Dipterocarpus spp.) and Caribbean pine (Pinus caribaea Morelet) contain high amounts of extractives that contribute to poor bonding. To reduce, if not to eliminate, the effects of these extraneous substances, surfaces of small wood blocks were Soxhlet-extracted for 8 hours by different solvents. Wettability of the wood surfaces was then measured by droplet and dynamic methods using water and dilute NaOH as liquids. Tensile shear strengths of extracted wood bonded with aqueous vinyl polymer isocyanate (API), resorcinol formaldehyde (RF) and polyvinyl acetate (PVAc) resin adhesives were also measured. Results revealed that although Caribbean pine had much higher resin content than Apitong, the former had better wettability than the latter. Solvent extraction of the adherend with either hexane or ethanol-benzene (1:2) for 8 hours was not enough to improve its wettability but enough to improve its gluability. However, successive extraction with hexane, methanol and ethanol benzene rendered the wood satisfactorily wettable. Generally, a direct relationship between wettability and bond strength could not be observed. In a separate experiment to improve bonding strengths, test specimens were either overheated or autoclaved for 4 minutes at 125°C during the pressing period. Autoclave treatment was found to be useful in increasing the bond strengths of API, RF, PVAc and urea formaldehyde (UF)-bonded Apitong and Caribbean pine.     

Free‐radical grafting of trans‐ethylene‐1,2‐dicarboxylic acid onto molten ethylene‐vinyl acetate copolymer

Distinctive features of free‐radical grafting of trans‐ethylene‐1,2‐dicarboxylic acid (TEDA) onto macromolecules of molten ethylene‐vinyl acetate copolymer (EVA) in the course of reactive extrusion have been investigated along with structure, mechanical characteristics, and high‐elastic properties of molten functionalized products (EVA‐g‐TEDA). It is shown that EVA‐g‐TEDA yield depends on both the peroxide initiator concentration and content of vinyl acetate units in the copolymer molecular structure. At functionalization, acid grafting is accompanied by secondary reactions of macromolecular degradation and crosslinking. With a low‐peroxide initiator concentration (0.1 wt %), degradation prevails; with a higher (0.3 wt %) concentration, crosslinking of macromolecules prevails. It is reported that monomers being grafted attach mostly over secondary carbon atoms in the polymer chain. EVA‐g‐TEDA appears to have a less perfect crystal structure with a lower‐melting temperature and crystallinity as against the starting polymer. The functionalized products display enhanced rigidity and lower deformability in comparison with the initial copolymer. Variations in the swelling ratio and melt strength of EVA‐g‐TEDA depend on the course of competing secondary processes of macromolecular degradation and crosslinking. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Semicontinuous heterophase copolymerization of vinyl acetate and butyl acrylate

Vinyl acetate (VAc) and butyl acrylate (BuA) were copolymerized in heterophase by a semicontinuous process (unseeded) and compared with the seeded semicontinuous microemulsion polymerization of the same monomers. A mixture of sodium dodecyl sulfate (SDS) and poly(ethylene oxide) dodecyl ether (Brij‐35®) were used as surfactants. The effects of monomer addition rate (R_a) and surfactants concentrations (4 or 1 wt % with respect to the initial mixture of reaction) on polymer and latex properties were studied. High copolymer content latexes (24–36 wt %) with average particle diameters (D_p) from 38 to 55 nm and relatively narrow particle size distributions, high polymerization rates, weight ratios of polymer to surfactant (P/S) from 13.3 to 32.8 were obtained. The number‐average molecular weights (M_n) were between 96,000 and 188,000 g/mol. Homogeneous copolymer compositions were obtained throughout the reaction for both, seeded and unseeded processes, which is not possible by the usual batch microemulsion process. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Adhesion properties of eco-friendly PVAc emulsion adhesive using nonphthalate plasticizer

An eco-friendly poly (vinyl acetate) emulsion adhesive was synthesized without phthalate. Four types of eco-friendly plasticizers for use in these adhesives were selected to confirm their primary properties by injecting the eco-friendly plasticizer without any prior change to its processing or cost. The four types of eco-friendly plasticizers used were dibutyl phthalate DBP-based product, dialkyl ester, acetyl tributyl citrate, and pentandiol-di-isobutyrate. Their properties were determined by comparison with the existing (DBP)-based product. As a result, an emulsion adhesive was produced without addition of phthalate or need for additional additives, resulting in a significant decrease in cost. However, the low temperature characteristics of the eco-friendly plasticizers were slightly inferior to those of DBP. These adhesives containing eco-friendly plasticizer were studied and their characteristics for adhesion strength, water resistance, ability for low temperature film formation, excellent storage stability, and lack of volatile organic compounds productions (including phthalate) were confirmed.     

新型低烟无卤阻燃电缆料的制备及表征

研究了以磷酸三甲苯酯(TCP)、水滑石(LDHs)、氢氧化铝(ATH)复配得到的复合阻燃剂对乙烯-醋酸乙烯酯共聚物(EVM:AV含量大于40%)性能的影响。分别通过氧指数、水平燃烧和拉伸性能测试考察了TCP/LDHs/ATH/EVM复合材料的阻燃性能和力学性能。结果表明,当TCP/LDHs/ATH/EVA为20/35/35/100(质量份数)时,复合材料的极限氧指数(LOI)达到35.2,阻燃级别为FH-1;断裂伸长率达到280%,拉伸强度达到11.0MPa。此复合材料可用于制造阻燃电缆。     

Preparation and characterization of ethylene‐vinyl acetate nanocomposites: enhanced flame retardant

Ethylene‐vinyl acetate (EVA) nanocomposites with enhanced flame retardance were prepared by the sol–gel process in the melt. Two EVAs with different vinyl acetate (VA) contents and aluminium isopropoxide were used as organic and inorganic phases. The nanocomposites were prepared in a batch mixer under constant processing conditions and were analysed by several characterization techniques. Aluminium isopropoxide presented low activation energy, which allows the synthesis of the nanoparticles without a post step treatment. The reaction mechanism is proposed. Nanocomposites with smaller and well dispersed metal nanoparticles were produced with an EVA with higher VA content. EVA nanocomposites achieve the requirements for 94 V‐0 classification. © 2013 Society of Chemical Industry     

Preparation and Properties of Ethylene Vinyl Acetate (EVA)/Organoclay/Compatibilizer Nanocomposites: Effects of Organoclay Loading and Methyl Ethyl Ketone

Ethylene vinyl acetate (EVA)/organoclay/compatibilizer nanocomposites were produced using a melt compounding technique in an internal mixer, Haake Rheometer, at 120°C and 50 rpm rotor speed. Effects of organoclay loading (from 2 to 10 phr—parts per hundred of resin and methyl ethyl ketone (MEK), used as a compatibilizer, on the processing properties, tensile properties, morphology, thermal degradation, and water absorption behavior of EVA/organoclay nanocomposites were studied. Results indicate that the presence of organoclay increase the processing torque, tensile properties, thermal degradation, and resistance to water absorption. The optimum organoclay loading was achieved at 2 phr. This was caused by the dispersion state of individual silicate layers (intercalation/exfoliation) in EVA matrix. The intercalation/exfoliation structure affects the properties of EVA/organoclay nanocomposites as evidenced from the morphology studies such as x-ray diffraction (XRD) and transmission electron microscopy (TEM) evaluation. The addition of MEK has the ability to improve the tensile properties, thermal degradation, and slightly reduces the resistance of water permeation of EVA/organoclay nanocomposites. The enhanced properties were seen as a result of the better matrix and filler interaction. The EVA/organoclay/MEK nanocomposites shows better intercalation/exfoliation of individual silicate layers in the EVA matrix as indicated by TEM. Moreover, the XRD evaluation shows that intercalation/exfoliation of the organoclay was formed in the EVA matrix.     

Synthesis and Characterization of Maize Starch Acetates and its Biodegradable Film

Starch acetates (SA) were synthesized by maize starch reacting with acetic acid/acetic anhydride, using sulfuric acid as catalyst. The biodegradable films were produced by thermal gelatinization of starch suspensions blending raw starch or SA with different degree of esterification (DS) and polyvinyl alcohol (PVA). Fourier transform infrared spectrogram (FT-IR) data showed acetate was introduced into the molecule chain of starch. Different structure of aggregation supported between the modified starch and the raw starch was determined by the scanning electron microscopy (SEM). Differential scanning calorimetry indicated SA glass transition temperature reduced with increasing of its DS. X-ray diffraction pattern of SA revealed the crystallinity of chain starch was destroyed, forming many completely even amorphous areas. SEM studies showed that amorphous was raised with DS of starch acetates. The mechanical and hydrophobic properties of the films were better than those of raw starch/PVA. In 50 days outdoor soil burial biodegradable experiment in summer, the weight loss of the films was almost 50%.     

Experimental investigation and prediction of bonding strength of Oriental beech (Fagus orientalis Lipsky) bonded with polyvinyl acetate adhesive

Adhesive bond strength of solid wood plays a key role in the efficient use of wood in a large number of engineering applications. In this study, the effects of amount of adhesive, pressing pressure, and pressing time on bonding strength of beech wood bonded with polyvinyl acetate adhesive were investigated and predicted by developing an artificial neural network (ANN) model. Experimental results have showed that bonding strength of wood samples increased generally by increasing amount of adhesive, pressing pressure, and pressing time. Besides, ANN analysis has yielded highly satisfactory results. The designed neural network model allows predicting the bonding strength of wood samples with mean absolute percentage error of 2.454% and correlation coefficient of 97.8% for testing phase. It is clear from the results that the model has a good learning and generalization ability. This model therefore can be used to predict bonding strength of beech samples bonded with polyvinyl acetate adhesive under given conditions. Consequently, this study provides beneficial insights for practitioners in terms of the safe and efficient use of wood as an engineering material in applications related to the strength of the bond between wood and adhesive.