Enthalpic relaxation in semi-crystalline PEEK

The effect of crystallisation on the glass transition temperature and enthalpic relaxation in poly(ether ether ketone) (PEEK) has been investigated. The increase in glass transition temperature and the activation enthalpy of ageing is explained in terms of the amorphous phase being constrained by the crystallites. The extent of enthalpic relaxation with time has been analysed in terms of the Cowie-Ferguson model and the β value was found to be dependent on both temperature and the crystalline morphology, changes in the co-operativity of the relaxations are used to explain this observation.     

Synthesis and characterization of novel diimide–dinaphthols and resulting poly(urethane–imide)s

Novel diols containing imide groups were prepared via condensation of aromatic dianhydrides with 5‐amino‐1‐naphthol. The diimide–dinaphthols prepared were characterized by conventional methods and used to synthesize new poly(urethane–imide)s (PUIs). All the polymers were characterized and their physical properties, such as solubility, solution viscosity, thermal stability, and thermal behaviour were studied. The polymers obtained showed more thermal stability than typical polyurethanes because of the presence of the imide groups. Copyright © 2003 Society of Chemical Industry     

纳米镓/聚甲基丙烯酸甲酯复合材料的原位超声合成与表征

超声作用于低熔点金属镓,使其超细化为纳米级的镓粒子,并采用无引发剂的乳液聚合方法制备出GA/聚甲基丙烯酸甲酯(PMMA)纳米复合粒子,并分析了其微观结构。结果表明纳米镓的形态和结构因有无表面改性剂而不同;乳液聚合得到的纳米镓复合粒子是核壳结构型,粒子大小为50~80 NM,内核金属镓粒径为30~50 NM,与聚合物存在一定的化学作用。     

Preparation and properties of silicone‐containing poly(methyl methacrylate) gels

Poly(methyl methacrylate) (PMMA) gels with varying amounts of silicone and solvent and constant amounts of crosslinker were prepared by solution free radical crosslinking copolymerization of methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDM), tetraethoxysilane (TEOS) and vinyltriethoxysilane (VTES) comonomer systems. They were then studied in benzene at a total monomer concentration of 3.5 mol L^?1 and 70 °C. The conversion of monomer, volume swelling ratio, weight fraction and gel point were measured as a function of the reaction time, silicone concentration and benzene content up to the onset of macrogelation. Structural characteristics of the gels were examined by using equilibrium swelling in benzene, gel fraction and Fourier‐transform infrared (FTIR) analysis. The morphology of the copolymers was also investigated by SEM. Based on the obtained results, it was concluded that the FTIR data did not have the capacity to show the presence of the VTES or TEOS moiety in these kinds of copolymers. On the other hand, the variation of weight fraction of gel, W_g, and its equilibrium volume swelling ratio in benzene, q_v, exhibited the same behaviour as that of MMA/EGDM copolymers. Also, the dilution of the monomer mixture resulted in an increase in the gel point and swelling degree and a decrease in the percent of conversion and gel fraction. Finally, TEOS is not an ideal silicone compound for reaction in the MMA/EGDM copolymerization system, whereas VTES is a suitable silicone comonomer for this system and it has been proved useful. Copyright © 2005 Society of Chemical Industry     

Conducting composites of poly(N‐vinylcarbazole), polypyrrole,and polyaniline with 13X‐zeolite

N‐vinylcarbazole (NVC) was polymerized by 13X zeolite alone in melt (65°C) or in toluene (110°C) and a poly(N‐vinylcarbazole) (PNVC)‐13X composite was isolated. Composites of polypyrrole (PPY) and polyaniline(PANI) with 13X zeolite were prepared via polymerization of the respective monomers in the presence of dispersion of 13X zeolite in water (CuCl₂ oxidant) and in CHCl₃ (FeCl₃ oxidant) at an ambient temperature. The composites were characterized by Fourier transform infrared analyses. Scanning electron microscopic analyses of various composites indicated the formation of lumpy aggregates of irregular sizes distinct from the morphology of unmodified 13X zeolite. X‐ray diffraction analysis revealed some typical differences between the various composites, depending upon the nature of the polymer incorporated. Thermogravimetric analyses revealed the stability order as: 13X‐zeolite > polymer‐13X‐zeolite > polymer. PNVC‐13X composite was essentially a nonconductor, while PPY‐13X and PANI‐13X composites showed direct current conductivity in the order of 10^?4 S/cm in either system. However, the conductivity of PNVC‐ 13X composite could be improved to 10^?5 and 10^?6 S/cm by loading PPY and PANI, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 913–921, 2006     

凝胶过滤色谱测定高分子量聚乙烯醇分子量和分子量分布

用凝胶过滤色谱对高分子量聚乙烯醇分子量、分子量分布进行剖析。采用Plaquagel-OH色谱柱,0.25mol/LNaNO3,0.01mol/L Na2HPO4-NaH2PO,pH=7的缓冲溶液流动相,流速1ml/min,示差折光检测器,柱温30℃,聚环氧乙烷作标准物。该方法能显著缩短分析时间,提高准确性,可用于对高聚合度聚乙烯醇进行研究和指导生产。     

A positive‐working photosensitive polyimide based on thermal cross‐linking and acidolytic cleavage

A novel positive‐working photosensitive polyimide (PSPI) based on a poly(hydroxyimide) (PHI), a crosslinking agent having vinyl ether groups, and a photoacid generator (PAG) was prepared. The PHI as a base resin of the three‐component PSPI was synthesized from 4,4′‐oxydiphthalic anhydride and 2,2′‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane through ring‐opening polymerization and subsequent thermal cyclization. 2,2′‐bis(4‐(2‐(vinyloxy)ethoxy)phenyl)propane (BPA‐DEVE) was used as a vinylether compound and diphenyliodonium 5‐hydroxynaphthalene‐1‐sulfonate was used as a PAG. The phenolic hydroxyl groups of the PHI and the vinyl ether groups of BPA‐DEVE are thermally crosslinked with acetal structures during prebake step, and the crosslinked PHI becomes completely insoluble in an aqueous basic solution. Upon exposure to UV light (365 nm) and subsequent postexposure bake (PEB), a strong acid generated from the PAG cleaves the crosslinked structures, and the exposed area is effectively solubilized in the alkaline developer. The dissolution behavior of the PSPI containing each 11.5 wt % of BPA‐DEVE and of the PAG was studied after UV exposure (365 nm) and PEB. It was found that the difference in dissolution rates between exposed and unexposed areas was enough to get high resolution. A fine positive pattern with a resolution of 5 μm in a 3.7‐μm‐thick film was obtained from the three‐component PSPI. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel approach in investigation of the poly(acrylic acid) hydrogel swelling kinetics in water

The swelling kinetics curves of structurally defined poly(acrylic acid) hydrogel in bidistilled water at temperatures: 25, 30, 35, 40, and 45°C were determined. The possibility of kinetically explaining the isothermal swelling process by applying the following models: reaction controlled by diffusion, first order chemical reaction kinetics, and second order chemical reaction kinetics, was investigated. It was found that kinetically explaining the swelling process using these methods was limited to only certain parts of the process. The swelling process in bidistilled water was described in full range assuming that the hydrogel's swelling rate was a kinetically controlled reaction by the rate of the movement of reactive interface of hydrogel. Based on that model, the kinetic parameters, activation energy (E_a) and preexponential factor (A), of the swelling process were determined to be E_a = 35 kJ/mol and lnA = 8.6. A possible mechanism of the investigated swelling process was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of post‐treatments on the properties of porous poly(vinyl alcohol) membranes

Porous poly(vinyl alcohol) (PVA) membranes were prepared by a phase‐inversion method. The influence of chemical crosslinking and heat treatments on the swelling degree, resistance to compaction, mechanical strength, and morphology of porous PVA membranes was extensively studied. The crosslinking degree and crystallinity of the membranes, calculated from IR spectra, increased with the treatment time. The porosity, calculated on the basis of swelling experiments, showed a decreasing trend for heat‐treated membranes but remained almost at a constant value for crosslinked membranes. Such a change was further proved with scanning electron microscopy pictures. The behavior was explained by the rearrangement of PVA chains during the heat‐treatment process, which led to morphological changes in the membranes. The mechanical properties of the porous membranes in dry and wet states were measured, and a great difference was observed between crosslinked and heat‐treated membranes in the dry and wet states. The crosslinked membranes showed good mechanical properties in the dry state but became fragile in the wet state. On the contrary, the heat‐treated membranes were more flexible in the wet state than in the dry state. This change was explained by the turnaround of inner stress in the systems during the swelling process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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