The effect of cooling rate on the impact performance and dynamic mechanical properties of rotationally molded metallocene catalyzed linear low density polyethylene

This article examines changes to the morphology of rotationally molded metallocene catalyzed linear low density polyethylene brought about by varying the cooling rate during processing. These changes in morphology lead to variations in the impact performance, which is reflected in the dynamic mechanical characteristics of the materials. Various analytical techniques are used in an attempt to explain the differences in impact behavior. Slow cooling is shown to result in high crystallinity, and in the formation of large spherulites, which in turn is detrimental to the impact performance of the material, particularly at low temperatures. The high crystallinity corresponds with a shift in the β transition of the material to a higher temperature, and is shown to result in a higher brittle–ductile transition. A case study was also carried out on samples from a finished part provided by an industrial molder, one section of which failed in a brittle manner when impact tested while the other failed in a ductile manner. Microscopy results showed that the brittle material had large spherulites at the inside surface, while the ductile material showed incipient degradation at this surface, which has previously been shown to be of benefit to impact strength in rotationally molded parts. Dynamic mechanical studies again showed a β transition at a higher temperature in the brittle samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1963–1971, 2006     

Synthesis of unsaturated polyphosphoester as a potential injectable tissue engineering scaffold materials

Polyphosphoester is a kind of biodegradable polymer with excellent biocompatibility and have been used in drug delivery, tissue engineering, and other bioapplications. A novel unsaturated polyphosphoester (UPPE) based on bis(1,2‐propylene glycol) fumarate (BPGF) and ethyl dichlorophosphate was synthesized by polycondensation reaction, and crosslinkable double bonds was introduced into the resulting polymer through the fumarate groups. NMR results indicate that there are three possible bonding models in polyphosphoester because of three isomers of BPGF. The GPC results express that increase in polymerization time leads to high molecular weight of polyphosphester and narrow distribution of molecular weight. After 18 h of polymerization reaction, the molecular weight reached to 5956 g mol^?1 and the polydispersity index was 1.12. The UPPE was soluble in N‐vinyl pyrrolidone and easily crosslinked by free‐radical polymerization. At the constant temperature (37°C), the maximum temperature due to heat release during crosslinking reaction varied from 41.1°C to 82.30°C and the setting time was between 1.95 and 10.28 min, according to different formulas. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3095–3101, 2006     

Preparation of alginate/poly(N‐isopropylacrylamide) semi‐interpenetrating and fully interpenetrating polymer network hydrogels with γ‐ray irradiation and their swelling behaviors

Semi‐interpenetrating polymer network (semi‐IPN) and fully interpenetrating polymer network (full‐IPN) hydrogels composed of alginate and poly(N‐isopropylacrylamide) were prepared with γ‐ray irradiation. The semi‐IPN hydrogels were prepared through the irradiation of a mixed solution composed of alginate and N‐isopropylacrylamide (NIPAAm) monomer to simultaneously achieve the polymerization and self‐crosslinking of NIPAAm. The full‐IPN hydrogels were formed through the immersion of the semi‐IPN film in a calcium‐ion solution. The results for the swelling and deswelling behaviors showed that the swelling ratio of semi‐IPN hydrogels was higher than that of full‐IPN hydrogels. A semi‐IPN hydrogel containing more alginate exhibited relatively rapid swelling and deswelling rates, whereas a full‐IPN hydrogel showed an adverse tendency. All the hydrogels with NIPAAm exhibited a change in the swelling ratio around 30–40°C, and full‐IPN hydrogels showed more sensitive and reversible behavior than semi‐IPN hydrogels under a stepwise stimulus. In addition, the swelling ratio of the hydrogels continuously increased with the pH values, and the swelling processes were proven to be repeatable with pH changes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4439–4446, 2006     

Miniemulsion and conventional emulsion copolymerization of styrene and butadiene: A comparative kinetic study

The kinetics of conventional and miniemulsion copolymerizations of styrene and butadiene were compared using the Mettler RC1 calorimeter. A two‐step homogenization procedure was applied to obtain miniemulsions of these monomers with hexadecane as the costabilizer. The results indicated that the miniemulsion polymerizations proceeded mainly by nucleation in the monomer droplets, while in the conventional emulsion polymerizations, particle formation occurred by a combination of micellar and homogeneous nucleation. The overall rate of miniemulsion polymerization was faster than the corresponding conventional emulsion system if the surfactant concentration was below the critical micelle concentration (cmc) and slower if the surfactant concentration was above the cmc. The homogenization process is important for making stable miniemulsion systems, but had no effect on the conventional emulsion system (without hexadecane), most likely because of the second stage addition of the butadiene monomer. The dependencies of the rate of polymerization (heat of reaction) and number of particles on the surfactant concentration differed for the two types of polymerization systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2304–2312, 2006     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Effects of heat treatment on tensile properties of diacetate fibers

Diacetate filaments were heat‐treated (without tension or with tension) under dry‐heat or wet‐heat environment, respectively. The effects of temperature, time, and tension on tensile properties of diacetate fibers after heat treatments were discussed. The results show that diacetate fibers present no obvious improvement on its tensile properties after dry‐heat treatments without tension. It was also found that during dry heat treatments with tension, the increase in tensile properties of fibers mainly depends on temperature and tension. Moreover, being dry‐heat treated with tension instant after wet‐heat treatment without tension, diacetate fibers exhibit a higher improvement on its tensile properties comparing with dry heat method with tension. The shrinking measurement for the fibers indicates different supermolecular structures were developed in the fiber before treatment and after treatment, which leads to the different extent in the improvement of tensile properties for the fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101:787–791, 2006     

Determination of the physicochemical characteristics and electrical performance of postsulfonated and grafted sulfonated derivatives of poly(para‐phenylene) as new proton‐conducting membranes for direct methanol fuel cell

Poly(para‐phenylene)s (PPPs) are an interesting class of rigid‐rod polymers that have excellent thermal and mechanical properties. Because of their high degree of crystallinity and lower permeability to methanol, PPPs are insoluble and infusible. A number of methods have been developed to synthesize substituted sulfonated PPPs bearing lateral chains to improve their solubility. In this work, a comparison of the physicochemical properties of three PPP‐based polymers is made with respect to Nafion membranes. One of these polymers was prepared with the postsulfonation method, and the other two were made with a new method of grafting developed in the Commissariat à l'Energie Atomique laboratory (a grafted sulfonated PPP polymer and a grafted perfluorinated sulfonated polymer). The sulfonated PPP polymers were examined for their mechanical properties, small‐angle X‐ray scattering, water absorption, proton conductivity, and methanol permeability. Relations between structures and properties were also investigated. Performances in fuel‐cell tests were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 944–952, 2006     

Does morphology stick? Tailored particle morphologies by swelling polymerization process

Structured dispersion particles suitable for pressure sensitive adhesives (PSA) were synthesized via swelling polymerization technique (EP 359562). Particles consisting of poly(n‐butyl acrylate) copolymerized with different types of carboxylic acids were used as seeds. The final particles were synthesized by swelling polymerization process, using 6 wt % styrene or 6 wt % methyl methacylate. The resulting particle morphology was analyzed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). From previous works (Coll Surf A 2001, 183–185, 725–737; J Appl Polym Sci 2004, 91, 2610–2623) where two‐step emulsion polymerization was used on similar particles, it is expected that the particle morphology is affected by the polarity of the monomer used for swelling polymerization because of the phase compatibility (thermodynamic parameter). In this work, the seed particles used were always of a glass transition temperature (T_g) below polymerization temperature. The diffusion of the growing polymer chains from the swelling polymerization is therefore mainly affected by their own T_g and the influence of the carboxy groups on the chain length of the entering radicals (kinetic parameter). The different morphologies of the single particles are discussed qualitatively. The effects of reaction parameters are compared with the results given in the previous work. The structure of the corresponding dispersion films was characterized using AFM. Correlations to macroscopic properties such as the cohesive strength and peel adhesion to different substrates are discussed. The results are also compared with the application properties of the corresponding unmodified particles, statistical copolymers, and to blends with small sized PMMA or PS particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1444–1455, 2006     

Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3

Ti‐based Ziegler–Natta catalysts supported on MgCl₂ doped with AlCl₃ were prepared by the reaction of MgCl₂/AlCl₃–ethanol adduct with TiCl₄. No AlCl₃ crystallites were found in the AlCl₃‐doped catalysts by WAXD analysis, suggesting that AlCl₃/MgCl₂ solid solution was formed. The effect of doping on the catalyst performance in ethylene polymerization was investigated. The results showed that the catalysts based on AlCl₃‐doped MgCl₂ support exhibited a slightly higher activity than did the MgCl₂‐supported catalyst and the molecular weight distribution (MWD) of polyethylene (PE) markedly increased (from 10.8 to 47.9) with the increase of AlCl₃ content in catalysts. The changes in catalyst's active center distribution were studied based on nonlinear fitting of the polymer GPC curves by multiple Flory functions. It was found that increase of types of active centers by introducing AlCl₃ into the support should be responsible for the broadening of MWD of PE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1768–1772, 2006     

Phenoxymethylpenicillin–intercalated hydrotalcite as a bacteria inhibitor

Phenoxymethylpenicillin (PMP) has been reversibly intercalated into a layered double hydroxide, and the resulting composite exhibits effective anti‐bacterial activity. Powder X‐ray diffraction studies indicate that the PMP molecules are interdigitated between the inorganic layers, and under mild acidic media, the molecules are released gradually. Therefore a sustained‐release anti‐bacterial medication is envisioned on the basis of this inorganic–drug composite. Copyright © 2005 Society of Chemical Industry