Abstract
m-Aminostyrene has been synthesised from acetophenone by the known route. It has been homopolymerised and copolymerised with styrene by means of 2,2'-azoisobutyronitrile as initiator. Two homopolymers, prepared with different initiator concentrations, and the copolymer have been converted into their acetyl derivatives, and these compounds have been characterised by intrinsic viscosity determinations in benzyl alcohol and elemental analyses. A kinetic study has been made of the hydrolysis, in homogeneous solution by benzyl alcoholic potassium hydroxide at 145 , of these polymeric compounds and also acetanilide and acetyl-m-cumidide. The rate constants for the hydrolysis of the polymeric compounds have been compared with those of acetanilide and acetyl-m-cumidide in order to assess the contribution of the polymeric structure to the rate of hydrolysis, and to ascertain if any specifically macromolecular reactivity factors operate in the hydrolysis of those polymeric acetyl-amino compounds. It is inferred that hydrogen bonding between side-groups is an important factor. Two homopolymers of m-aminostyrene have been diazotised, yielding poly-(m-styrenediazonium chloride) which has been subjected to the standard diazonium reactions in which nitrogen atoms are retained in the final molecule, namely, reduction to the corresponding hydrazine, and coupling with amines and phenols. An impure polyhydrazine was prepared. Poly(styrene-m-diazonium chloride) undergoes azo coupling substantially to completion with B-naphthol, and to a considerable degree with 2,5-dimethyl- and 2,5-dimethoxy-aniline. The latter products underwent further diazotisation and coupling to yield polymeric disazo compounds.