Problems of the Kinetics and the Topochemistry of Heterophase Copolymerisation

The kinetics and the mechanism of binary heterophase copolymerisation are discussed by analogy with the differences in the kinetics and the statistics of homophase and heterophase polymerisation. The appearance of an interface, even in the absence of interphase interactions, leads to changes in the composition of the copolymer macromolecules and to departures in the overall process from the Mayo–Lewis canonical scheme even when r_A and r_B are constant. In order to record heterophase effects it is hence impossible to use the standard treatment of equilibrium diagrams or to estimate the mean compositions of the copolymers: the composition distribution functions must be analysed. Work is therefore discussed in which copolymerisation was conducted (wittingly or unwittingly) under heterophase conditions, practical criteria of heterophase character are examined, and its possible effects on the kinetics and the mechanism of the reaction are determined qualitatively. Possible methods for the quantitative analysis of copolymerising systems diverging from the general Mayo–Lewis scheme are also discussed. A list of 88 references is included.