This report presents the synthesis and chemical modification of hyperbranched poly(ether ketones). The polymer was conveniently prepared by direct polycondensation of an AB 2 monomer, 3,5-diphenoxybenzoic acid, using phosphorus pentoxide/methanesulfonic acid (PPMA) as the condensing agent and solvent. The hyperbranched poly(ether ketone) could be modified via the electrophilic aromatic substitution of the active phenoxy groups at the chain ends with a variety of carboxylic acids. The thermal properties of the hyperbranched poly(ether ketones) depend heavily on the nature of the chain end, with glass transition temperature ranging from Ϫ 24ЊC to 180ЊC. Moreover, the length of the terminal alkyl groups significantly influences the solubility of the hyperbranched poly(ether ketones). By varying the chain ends, hyperbranched poly(ether ketones) soluble in either a polar or nonpolar solvent could be obtained.

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Star‐shaped polymers with two different core sizes were prepared by step polymerization. Their structures were confirmed by FTIR and 1H NMR studies. X‐ray diffraction studies showed highly crystallized patterns for this type of star polymer. Thermogravimetric analysis curves displayed an excellent thermal stability and a two‐step degradation mechanism for these materials. In addition, it indicated that if the length of the triol segment were longer, the degradation temperature at 10% weight loss would be higher. © 2002 Society of Chemical Industry

Liquid‐crystalline, segmented polyurethanes with methoxy–biphenyl mesogens pendant on the chain extender were synthesized by the conventional prepolymer technique and esterification reaction. Two, side‐chain, liquid‐crystalline (SCLC) polyurethanes with mesogens having spacers of six and eight methylene units were prepared. The structures of the mesogenic units and SCLC polyurethanes were confirmed by Fourier transform infrared spectroscopy and 1H NMR. Polymer properties were also examined by solubility tests, water uptakes, and inherent viscosity measurements. Differential scanning calorimetry studies indicated that the transition temperature of the isotropic to the liquid‐crystalline phase decreased with increasing spacer length. Wide‐angle X‐ray diffraction (WAXD) studies revealed the existence of liquid‐crystalline phases for both SCLC polyurethanes. Polarized optical microscopic investigations further confirmed the thermotropic liquid‐crystalline behaviors and nematic mesophases of both samples. Thermogravimetric analysis displayed better thermal stabilities for both SCLC polymers and indicated that the presence of mesogenic side chains may increase the thermal stability of segmented polyurethanes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 290–302, 2004

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