Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Effects of hydrolysis on the physical properties of short glass-fibre reinforced poly(ethylene terephthalate)

The mechanical fracture strength and toughness of short-fibre composites, injection moulded from compounds of poly(ethylene terephthalate) (PET) containing 10 and 30% (by weight) (w/o) glass, have been investigated and the dependence upon matrix hydrolytic stability determined. Mouldings have been characterised by several physical techniques to evaluate molecular weight, degradation rates, crystallinity and morphology, whilst time-dependent gravimetric data were derived to quantify sorption kinetics and allow comparisons with theoretical reaction rates to be made. During melt processing, PET is hydrolysed extremely rapidly by traces of moisture (<0.02w/o). yet the inherent strength of moulded composites declines significantly only below an apparently critical molecular weight. However, on long-term humid ageing in hot water, impact behaviour especially is rendered more complex by simultaneous crystallisation, molecular reorder and losses of interfacial bond strength.     

Synthesis and characterization of poly(ethylene aspartate)-metal complexes

Poly(ethylene aspartate) [PEA] was synthesized by the melt condensation of D,L-aspartic acid and ethylene glycol. PEA containing pendent amino and carbonyl groups in its repeating chain was used as the polymeric ligand for complexation with transition metal ions, viz. Co(II), Ni(II), Cu(II), Mn(II), Zn(II), Cd(II), Ca(II), Mg(II), Pb(II) and Hg(II). Complexation was found to be most effective in DMSO. The resulting polyester-metal complexes were solid coloured materials which have been characterized by IR spectroscopy, elemental analysis and magnetic susceptibility measurements. The thermal stability of the polyester-metal complexes was investigated by thermogravimetric analysis (TGA). On the basis of the physico-chemical studies, an oxygen and nitrogen coordinated structure for the polyester-metal complexes is proposed.     

Liquid viscosities and densities of HFC-134a+glycol mixtures

Liquid viscosity and density of six binary mixtures of HFC-134a with glycols [ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (400), and polypropylene glycol (2000)] have been measured in the temperature range from 273 to 333 K. The viscosity was measured by a rolling-ball viscometer calibrated with standard liquids of viscosities and densities (JS5, JS10, JS20, and JS50). The density was measured with a glass pycnometer. The uncertainties of the measurements were estimated to be less than 3.4 % for viscosity and 0.04 % for density, respectively. An equation is given to represent the obtained viscosity values as a function of weight fraction and temperature.     

Probing the early stages of polymerization of ethylene on a model chromium/silica catalyst by Fourier transform infrared spectroscopy

The nature of the interaction of monomer, and the early stages of growth of oligomers of ethylene on a rather more uniform surface of Cr/SiO₂ catalyst than hitherto studied has been investigated by differenceFTIR spectroscopy using C₂D₄ and C₂H₄ as reactants both with and without subsequent treatment of the catalyst with CO andTHF. The active catalyst was prepared by reaction of vapour phase CrO₂Cl₂ with the vicinal hydroxyls of the silica surface. Three distinct kinds of methylene groups were detected. Arguments are given for assigning the peaks at 2935 and 2860 cm^–1 to CH₂ groups directly bound to the active site and those at 2920 and 2850 to CH₂s in the growing chain well removed from the Cr. The peaks at 2160 and 2165 cm^–1 are attributed to CD₂ groups hydrogen bonded to surface hydroxyls.     

Crystallization behavior of star-shaped poly(ethylene oxide) with cubic silsesquioxane (CSSQ) core

The crystallization behavior of well-defined star-shaped cubic silsesquioxane-poly(ethylene oxide) (CSSQ-PEO) and linear PEO were studied in terms of differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). It was found in DSC analysis that the glass transition temperature (T_g) and the crystallization temperature (T_c) of CSSQ-PEO are different from those of linear PEO. The presence of CSSQ in PEO reduced the overall crystallization growth rate. This effect can be ascribed to the reduction of the mobility of the PEO crystallites in the presence of CSSQ and the star structure of the polymer. The Ozawa method is qualitatively satisfactory for describing the nonisothermal crystallizations of linear PEO and CSSQ-PEO. The presence of CSSQ leads to the diffusion- and nucleation-controlled mechanisms in the crystallization process of CSSQ-PEO whilst only the nucleation-controlled mechanism was observed in the case of linear PEO. The apparent activation energy required for crystallization was calculated using the Kissinger method. The isothermal crystallization morphology of PEO and CSSQ-PEO were also examined by cross-polarizing optical microscopy (CPOM). The CPOM images indicated the spherulite growth is slower in CSSQ-PEO as compared to linear PEO. It was also investigated that more number of PEO spherulites in CSSQ-PEO were observed, which sizes are markedly smaller than the spherulites developed in linear PEO. Wide-angle X-ray scattering (WAXS) studies showed that the crystallization peaks for linear PEO and CSSQ-PEO appeared at different temperature revealing the crystallization process and crystal growth rate are different from each other. However, no significant distortion of the crystal structure of PEO was evaluated in the presence of CSSQ.     

负载化非茂单活性中心催化剂乙烯聚合的研究

在硅胶上负载了双(N-环己基-3-叔丁基水杨醛亚胺基)二氯化锆配合物,得到负载化非茂单活性中心催化剂。该催化剂用于乙烯聚合,考察了配合物用量、共聚单体1-己烯用量、聚合温度、聚合压力、聚合时间、三乙基铝用量对乙烯聚合性能的影响及对聚合物的相对分子质量、相对分子质量分布、熔体流动指数和密度的影响。实验结果表明,负载化非茂单活性中心催化剂保持了原均相催化剂的乙烯聚合性能;该催化剂在淤浆聚合工艺中聚合平稳,所得聚合物的颗粒形态良好。     

复合聚全氟乙丙烯材料的介电及高频击穿性能研究

在聚全氟乙丙烯(FEP)中添加 TiO_2和 Al_2O_3,通过热压成型的方法制备了 FEP/TiO_2复合材料和 FEP/Al_2O_3复合材料,研究了氧化物添加量对复合材料介电常数、介电损耗和高频击穿性能的影响。结果表明,随氧化物含量的增加,复合材料的介电常数和介电损耗均增加;在同一添加量下,TiO_2对复合体系的介电性能影响较大。FEP/TiO_2复合材料的高频击穿性能随 TiO_2含量的增加而下降,在 TiO_2含量为4.0%(质量分数,下同)时,复合材料的损伤阈值已降为 FEP 材料损伤阈值的48.9 %。而 FEP/Al_2O_3复合材料的高频击穿性能随 Al_2O_3含量的增加而升高,当 Al_2O_3含量为1.2%时,复合材料的损伤阈值已增大到 FEP 材料损伤阈值的2倍,达到313 J/m~2。