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The reaction of red phosphorus with poly(methyl methacrylate) under pyrolysis conditions was investigated with a number of physical techniques. A random methyl methacrylate/cyclic anhydride copolymer is formed from atatic PMMA, whereas a random methyl methacrylate/methacrylic acid copolymer is obtained with isotactic PMMA. The backbones of both these copolymers are more stable toward depolymerization than that of PMMA. The flame‐retardant activity of red phosphorus with PMMA may arise in part from stabilization of the polymer toward depolymerization via modification of the sidechains.

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SynopsisPolyphenylenes made by reaction of benzene, biphenyl, or p-terphenyl with metal halide catalyst-oxidant systems are complex mixtures of dissimilar oligomers, which include halogenated and polynuclear structures, according to positive and negativeion laser desorptionl Fourier transform mass-spectral analyses. Polymerization of benzene with metalchloride salts that terminate chain elongation by chlorination of the end rings appears to decrease formation of polynuclear structures by providing a competing pathway for chain termination. Polynuclear structures occur to a greater extent with oligomerization of biphenyl than with benzene, presumably because of isomerization and increased opportunity for x overlap during propagation. Electrical conductivities of polyphenylenes made by various routes should not be discussed solely in terms of the linear poly(p-phenylene) structure.