Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

Linear polyphosphonates with the generic formula -[P(Ph)(X)OR ' O](n)- (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt2)(2)and a diol (HOR ' OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt2)(2)and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula -[P(Ph)(X)OR ' O]((x + 2))-[P(Ph)(X)OR ' O]((x + 3))- (X = S or Se) have been synthesized by the polycondensations of Et2N[P(Ph)(X)OR ' O]((x + 2))P(Ph)NEt(2)oligomers with HOR ' O[P(Ph)(X)OR ' O]((x + 3))H oligomers followed by reaction with a chalcogen. The Et2N[P(Ph)(X)OR ' O]((x + 2))P(Ph)NEt(2)oligomers are prepared by the reaction of an excess of P(Ph)(NEt2)(2)with a diol while the HOR ' O[P(Ph)(X)OR ' O]((x + 3))H oligomers are prepared by the reaction of P(Ph)(NEt2)(2)with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using(1)H,C-13{H-1}, and(31)P{H-1} NMR spectroscopy, TGA, DSC, and SEC.P-31{H-1} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to similar to 300 degrees C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures andT(g)profiles. The polymers have weight average MWs of up to 3.8 x 10(4) Da.