Synthesis of novel phosphinic acid-containing polymers

Three arylene difluoride monomers containing phosphine oxide (1), phosphini c acid (2), or phosphinate ester (3) groups were prepared and polymerized w ith bisphenol A to give novel poly-(arylene ether)s (4, 5, and 6). The poly mers obtained had moderate molecular weights (eta (inh): 0.14-0.30 dL g(-1) in N-methylpyrrolidinone) and glass-transition temperatures (T-g: 102-200 degreesC), depending on the phosphine group in the main chain. Using bis(4- fluorophenyl)sulfone as a comonomer improved the polymerization to give cop olymers with higher solution viscosities. The stoichiometric investigation revealed that 7 mol % excess of fluoride monomer gave the highest molecular weight copolymer a with eta (inh) of 0.78 dL g(-1), which had a T-g of 176 degreesC, a T-d10% of 432 degreesC, and formed a hard film by casting from solution. (C) 2001 John Wiley & Sons. Inc.