Atmospheric pressure plasma enhanced synthesis of flame retardant cellulosic materials

Flame retardant cellulosic materials have been produced using a silicon dioxide (SiO₂) network coating. SiO₂ network armor was prepared through hydrolysis and condensation of the precursor tetraethyl orthosilicate (TEOS), prior coating the substrates, and was cross linked on the surface of the substrates using atmospheric pressure plasma (APP) technique. Because of protection effects of the SiO₂ network armor, the cellulosic based fibers exhibit enhanced thermal properties (characterized by TGA and DSC) and improved flame retardant (proven by ASTM D1230‐99). Furthermore, the surface analysis (XPS and SEM) confirmed the presence of the SiO₂ network attached to the substrates even after intense ultrasound washes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crosslinking of epoxidized natural oils with diepoxy reactive diluents

The different natural oils epoxidized with 3‐chloroperbenzoic acid were crosslinked with diepoxy reactive diluents, bisphenol A propoxylate diglycidyl ether, and 3,4‐epoxycyclohexylmethyl‐3,4‐epoxyclohexane‐carboxylate, using cationic initiator at 60°C and photoinitiators at the room temperature. The insoluble fraction of the polymeric products was 59–90%. The Young modulus of the crosslinked polymer films ranged from 2 to 861 MPa. The 10% weight loss temperatures of the crosslinked polymers estimated by thermogravimetric analysis were in the range from 250 to 420°C. The water vapor transmission rate of the crosslinked biopolymer films ranged from 6 to 49 g/m²/24 h. Biochemical oxygen demand and biodegradation in soil of the crosslinked polymers were studied. The crosslinked polymers showed higher biodegradation rate than cellulose, starch, and polyvinylalcohol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reactivity ratios and copolymer composition evolution during styrene/dimethacrylate free‐radical crosslinking copolymerization

In this article, experimental and simulated results are presented for the evolution of the copolymer composition as unsaturations are consumed in the free‐radical cross‐linking copolymerization of Styrene(St) and BisphenolA glycerolate dimethacrylate (BDMA). Real time FTIR measurements were performed to monitor the depletion of each comonomer double bond during the isothermal curing reaction at 80°C. From the experimental data corresponding to different feed compositions, the initial reactivity ratios and their evolution with conversion were determined via a nonlinear least squares optimization of the integrated form of the copolymerization equation. The reactivity ratio of St increases continuously and exponentially with the overall reaction conversion, while that of BDMA decreases linearly. A modified terminal copolymerization model including the dependence of the reactivity ratios with the overall conversion was proposed. The application of this model provides a consistent fitting for the conversion of each comonomer during all reaction stages, even at high conversion values where large diffusion and topological restrictions for chain movements are present. Simulations show that the concentration of styrene units added to the copolymer increases with the overall reaction conversion, while that for the BDMA double bonds diminishes. Structures rich in homopolymerized styrene are predicted at later stages of the reaction.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of biodegradable crosslinked polymers from 5‐hydroxylevulinic acid and α,ω‐diols

Novel biodegradable chemically crosslinked polymers, poly(5‐hydroxylevulinic acid‐co‐α,ω‐diol)s (PHLA‐diols), were synthesized from 5‐hydroxylevulinic acid and α,ω‐diols and characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. The gel content, swelling ratio, tensile properties, and hydrolytic degradation behaviors were also measured and assessed. The glass‐transition temperature of the PHLA‐diols could be adjusted within a wide range (?50 to 30°C) by the type and feed ratio of the diol. Because of the low glass‐transition temperature and crosslink structure, they exhibited certain elastic properties. The tensile modulus, strength, and elongation at break measured at 37°C were 1.4–6.3 MPa, 0.8–1.6 MPa, and 10–25%, respectively. These polymers could be hydrolytically degraded. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

New polymers from plant oil derivatives and styrene‐maleic anhydride copolymers

In this study, styrene maleic anhydride copolymer (SMA2000, Styrene : Maleic Anhydride 2 : 1) is grafted and/or crosslinked with epoxidized methyl oleate, epoxidized soybean oil, methyl ricinoleate (MR), castor oil (CO), and soybean oil diglyceride. Base catalyzed epoxy‐anhydride and alcohol‐anhydride polyesters were synthesized by using the anhydride on SMA, the epoxy or secondary alcohol groups on the triglyceride based monomers. The characterizations of the products were done by DMA, TGA, and IR spectroscopy. SMA‐epoxidized soy oil and SMA‐CO polymers are crosslinked rigid infusible polymers. SMA‐epoxidized soy oil and SMA‐CO showed T_g's at 70 and 66°C, respectively. Dynamic moduli of the two polymers were 11.73 and 3.34 Mpa respectively. SMA‐epoxidized methyl oleate, poly[styrene‐co‐(maleic anhydride)]‐graft‐(methyl ricinoleate), and SMA‐soy oil diglyceride polymers were soluble and thermoplastic polymers and were characterized by TGA, GPC, DSC, NMR, and IR spectroscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the vinyl concentration on the structural and rheological characteristics of peroxide‐modified high‐density polyethylenes

The effect of the hydrogenation of the terminal vinyl groups on the peroxide modification and rheological properties of high‐density polyethylene (HDPE) was investigated. The aim of the study was to determine exclusively the effect of the terminal vinyl groups on the peroxide crosslinking and rheological properties of HDPE with one polymer type. This was achieved by hydrogenation of the terminal vinyl groups of a commercial HDPE to obtain an identical material from a structural point of view, which differed only in the nature of the terminal unsaturations, and the comparison of its level of peroxide crosslinking with that of the original polymer. Hydrogenated and unhydrogenated polymer samples were modified at 170°C with different amounts of organic peroxide ranging from 125 to 5000 ppm. Changes in the molecular structure were determined by Fourier transform infrared spectroscopy, size exclusion chromatography, and rheological measurements. Hydrogenation of the terminal groups of the original polymer significantly reduced the rate of modification or crosslinking. The dynamic viscosity and elasticity increased with the level of peroxide modification. Unhydrogenated samples exhibited rapid increases in viscosity and elastic modulus, whereas their hydrogenated counterparts required about 500% of the amount of peroxide needed for the unhydrogenated sample to attain similar structural changes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hypercrosslinked polystyrene microspheres with bimodal pore size distribution and controllable macroporosity

A combination of suspension polymerization and postcrosslinking was used to prepare hypercrosslinked polystyrene (H‐PS) microspheres with controllably bimodal pore size distribution in the presence of toluene and polypropylene (PP) as a coporogen. The proportion of PP in the coporogen was changed to investigate the influence of the coporogen composition on the pore structure of the H‐PS microspheres. The addition of a small amount of PP achieved the aim of a clearly bimodal pore size distribution and the control of the macroporosity of the H‐PS microspheres, which have potential application in the preparation of catalyst supports. The specific surface area of the H‐PS microspheres could be adjusted in the range 380–790 m²/g by changes in the concentration of PP in the coporogen. Moreover, the H‐PS microspheres displayed all the characteristics of Davankov‐type resins by their ability to be swollen in both thermodynamically poor solvents such as water and good solvents such as toluene. Finally, the possible mechanism of porosity formation during polymerization and postcrosslinking was also examined by a combination of pore structure data and the appearance of the microspheres before and after postcrosslinking. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Optimization of cotton crosslinking with polycarboxylic acids and nano TiO2 using central composite design

The cotton crosslinking with butane tetra carboxylic acid (BTCA) and citric acid (CA) in the presence of sodium hypophosphite (SHP) and nano TiO₂ (NTO) under different curing conditions were optimized using a statistical model. The central composite design (CCD) was used for variables based on Design of Expert software. The appropriate model to create optimum crease recovery angle was obtained for each condition. The X‐ray diffraction (XRD) and scanning electron microscopy (SEM) were also employed to indicate the NTO particles on the fabric surface with the size of nano particles and their crystallinity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of crosslinking on the characteristics of thermally expandable microspheres expanding at high temperature

Free‐radical suspension polymerization was used to synthesize thermally expandable microspheres (TEMS); in this process, a poly(acrylonitrile‐co‐methacrylonitrile) shell encapsulated isooctane. Different amounts of dimethacrylate, diacrylate, or divinyl ether functional crosslinker were added to investigate the effects on the crosslinking density of the polymer and the expansion properties of the TEMS. The optimum amount of crosslinker was found to be approximately 0.05–0.1 mol %. However, a significantly better expansion could be obtained with 1,4‐butanediol dimethacrylate as a crosslinker, compared to 1,4‐butanediol divinyl ether or 1,4‐butanediol diacrylate. From monitoring the conversion of monofunctional analogues by gas chromatography, we suggest that the differences in expansion obtained with different crosslinkers, originated from the difference in the reactivity of the radicals in the system toward the vinyl functionalities of the crosslinkers. This regulated the incorporation of the crosslinker into the polymer and, thereby, the mechanical properties of the microsphere shell. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal property improvement of ethylene‐octene copolymer through the combined introduction of filler and silane crosslink

In many applications, e.g., wire and cable insulation, hot water pipe, high‐temperature properties of polymer are essential. This article presents the use of silane crosslinking together with the addition of particular filler in improving the thermal and mechanical properties of ethylene‐octene copolymer (EOC). The effects of filler surface characteristics on siloxane network structure developed and final properties of the crosslinked products are discussed. The results show an increase in the decomposition temperature of EOC more than 50°C after modification. Only crosslinked composites are able to withstand the high‐temperature environment of aging test which is beyond the melting temperature of the matrix polymer. The crosslinked composites filled with calcium carbonate show superior properties to those with silica, due to a higher crosslink density and tighter network structure formed. The silane coupling mechanism and the presence of bound polymer on silica surfaces cause difficulties for the crosslink formation in the silica filled systems. However, an advantageous influence of both silane coupling and crosslink reaction in the silica filled composites is seen on the enhanced tensile strength and modulus of the materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010