Nonisothermal melt-crystallization kinetics of isotactic polypropylene synthesized with a metallocene catalyst and compounded with different quantities of an α nucleator

The nonisothermal crystallization kinetics of a metallocene-made isotactic polypropylene (m-iPP) and its compounds with 0.1 wt % and 0.3 wt % of a sorbitol derivative [1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS); an α nucleator] were investigated by differential scanning calorimetry at different cooling rates from the melt. The nucleation efficiency was proved by a significant increase in the crystallization temperatures (accompanied by a slight augmentation of the degree of crystallinity and a decrease in the crystal sizes). This increase in the crystallization temperatures led to higher amounts of fractional content in the γ polymorph, even though DMDBS was supposed to be a nucleator for the α form. The Avrami and Ozawa methods effectively described only the early stage of crystallization, whereas a combined Avrami–Ozawa method was valid for the whole crystallization process. The values of the exponent for this method decreased for nucleated samples in the later stage of crystallization, especially in the case of m-iPP with 0.3 wt % DMDBS added (m-iPP03). The activation energy of the process and the surface free energy were also estimated. The production of considerable proportions of the γ polymorph in m-iPP03 corresponded to higher values of the activation energy and lower values of the surface free energy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structure and processability of iodinated poly(vinyl alcohol). IV. Drawability of the films iodinated at solution before casting

The drawability of iodinated at solution before casting (IBC) polyvinyl alcohol films prepared by casting aqueous solutions of 10 wt % PVA containing 15.2, 39.8, 83.2, 117.0, and 140.1% was examined with a tensile tester at 20–60°C. The tensile behavior of IBC films showed that the yield and breaking loads were much lower, and the breaking elongation was even higher than those of the unoriented iodinated after casting (IAC) films as well as the untreated PVA films. The maximum draw ratios of the films with the weight gain of 15.2, 39.8, 83.2, 117, and 140.1% were 4.5, 5.5, 8.5, 8.0, and 7.5, respectively, which were achieved at 20°C in all. The crystallinity of all films increased by the maximum draw, regardless of crystallinity before drawing. The crystalline structure was recovered to the original PVA crystalline lattice by deiodination. Amorphous orientation and initial moduli increased with the maximum draw ratio, while the orientation of crystals was constant. The orientation and moduli increased up to the weight gain of 83.2%, whose highest draw ratio and initial modulus were 8.5 and of 7.1 GPa, respectively, and then decreased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effects and properties of poly(arylene ether benzonitrile)s of various molecular weights blended with sulfonated poly(ether ether ketone)

Poly(arylene ether benzonitrile) (PAEBN) was synthesized with 2,6‐dichlorobenzonitrile and biphenol. PAEBNs with various molecular weights (MWs), 1,640,000 and 185,000 g/mol, were synthesized by control of the stoichiometry of the monomers and were blended with sulfonated poly(ether ether ketone) (SPEEK). The effects of MW on the water uptake, swelling, methanol permeability, and proton conductivity of the SPEEK/PAEBN blend membranes were investigated. The molecular mobility of the SPEEK/PAEBN blends was also examined in this study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Methacrylic acid–acrylamide-g-poly(ethyleneterephthalate) fibres for urea hydrolysis

This paper presents the results of urease immobilization onto methacrylic acid–acrylamide grafted poly(ethyleneterephthalate) fibres. The graft yield strongly affected the maximum activity of the immobilized enzyme up to a value of 70·2%. Higher grafting caused a decline in urease activity and led to the degradation of the fibres. The minor changes observed in K_m and V_max demonstrated that the conformational changes existed during immobilization were not extensive. However, 70·2% methacrylic acid–acrylamide-g-fibres containing urease were more stable towards acidic and alkaline pH, high temperature and storage conditions compared with free enzyme. Apart from the increase in stability to heat inactivation, the initial enzymatic activity of the urease–fibre system remained almost unchanged even after 40 repeated assays corresponding to 10 h of operation in 4 months, indicating the excellent durability of the system.     

Diffusion of additives and plasticizers in poly(vinyl chloride): 4. A programmed temperature technique for the determination of the diffusion parameters of three dialkylphthalates

A programmed temperature technique has been developed for the measurement of the self-diffusion coefficients of additives in polymers. This has been applied to the diffusion of three dialkylphthalate plasticizers in poly(vinyl chloride). Values of the self-diffusion coefficients and the calculated activation energies obtained in this way have been compared with values previously obtained from measurements at constant temperature. It has been shown that the programmed temperature technique gives a very rapid method for the estimation of the activation energy of self-diffusion.     

稀土稳定氧化锆超细粉末的合成机理研究

依据Al(Ⅲ )、Zr(Ⅳ )的水解聚合机理 ,把锆、铝和钇的无机盐溶液按一定组成混合在一起 ,通过加入乙二醇作为络合剂和调节溶液的PH值来获得溶胶 ,并直接蒸馏溶胶来获得干凝胶 ,最后制得ZrO2 (Y2 O3 ) -Al2 O3 系粉末。研究结果表明 :该工艺不仅制粉时间快、成本低、产量大 ,而且粒子均匀 ,粒径在 2 0～ 5 0nm之间 ,具有一定的可行性     

Fractionation of partially stereoregular poly(propylene oxide)

Partially stereoregular poly(propylene oxide) samples were synthesized via reactions catalysed by a preformed analytically defined trimethylaluminium hydrolysate. These samples were fractionated into two contrastingly different fractions.

1. (i) D-polymers: This fraction constituted the major part (up to 90%). It mainly contained cyclic low molecular weight oligomers (MW < 1000). The linear chains found in D-polymers had hydroxyl end groups. No double bonds could be detected spectroscopically.

2. (ii) K-polymers: This fraction was high molecular weight stereoregular polymer. Stepwise thermal precipitation from dilute isooctane solution of K-polymers yielded a succession of fractions which differed in melting point. It appears that the phase equilibria during the thermal precipitations were not controlled by the molecular weights of species.

Determination of the solubility parameter of poly(ethylene oxide) at 25°C by gas-liquid chromatography

The solubility parameter of poly(ethylene oxide) at 25°C has been determined using the method developed by DiPaola-Baranyi and Guillet, by the extrapolation of the values of the interaction parameter χ, at high temperatures, ranging from 70°–90°, 90°–110° and 110°–130°C down to 25°C. The values of the solubility parameter obtained, depending on the temperature ranges employed, are 9.8, 9.9 and 10.1, respectively.     

Selective gas transport in miscible PPO-PS blends

The permeation rates of He, CO₂ and CH₄ though miscible blends of polystyrene and poly(phenylene oxide) at 35°C are reported as a function of pressure. Sorption isotherms for CO₂ and CH₄ are also presented. By using ratios of the permeabilities of the pure gases the separation factors for the gas pairs He---CH₄ and CO₂---CH₄ can be estimated. For both pairs the estimated separation factor goes through a prominent maximum, thus indicating that these blends are more permselective than expected from the behaviour of polystyrene and poly(phenylene oxide). This stems from mobility considerations rather than solubility effects and a qualitative free volume argument is proposed as an explanation. The sorption and transport data have been interpreted and correlated using the dual sorption-mobility models developed previously for glassy polymers. Since the commercial polystyrene used contained a small amount of mineral oil to improve flow behaviour, the effect of this additive on polystyrene properties was explored in some detail.