The synthesis, processing, and engineering of halogen-free, low heat release, fire-resistant materials present important challenges in polymer materials chemistry. One approach to this problem involves the use of polymers that char upon decomposition, reducing the evolution of flammable gas and acting as an insulating layer. Demonstrated here is the synthesis of novel char-forming polyarylates prepared by interfacial polycondensation of 4,4′-bishydroxydeoxybenzoin (BHDB) and isophthaloyl chloride. A variety of copolyarylates containing BHDB, bisphenol A (BPA), and isophthaloyl chloride were prepared and shown to exhibit superior fire resistance to many polymers in the low flammability category. A char yield of 42% and heat release capacity of 62 J/(g K) were measured for the BHDB-containing polyarylate, while polyarylates containing both BHDB and BPA combined desirable fire-resistant properties with appreciable polymer solubility and processability.

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Deoxybenzoin‐based copolymers containing various relative ratios of arylate and phosphonate units in the backbone were synthesized by solution polycondensation. These copolymers were characterized by gel permeation chromatography, Fourier Transform infrared spectrometry, and proton, carbon, and phosphorous nuclear magnetic resonance spectroscopy (1H, 13C, and 31P NMR). Pyrolysis combustion flow calorimetry (PCFC) performed on these copolymers revealed their very low heat release capacity, making them attractive for applications in which halogen‐free, low flammability materials are desired. Integration of phosphonate units into the polymer backbone is advantageous for achieving high molecular weight polymers with solution processbility while retaining the low flammability inherent to deoxybenzoin‐based polymers. Char yields greater than 50% and heat release capacities of 40–60 J/g K, were observed for these copolymers by PCFC. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4573–4580, 2007

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