Macromolecules, Vol.28, No.15, 5198-5208, 1995
Composition Fluctuation Effects in Chain Copolymerization
We discuss the effects of local fluctuations in monomer composition during chain copolymerization reactions on sequence distributions and phase behavior. In particular, we show that near critical mixtures of type A and B monomers (or macromonomers) with equal reactivity ratios can polymerize to form very blocky random copolymers. We further argue that this blockiness can be sufficient to induce liquid-liquid phase separation or mesophase separation within the reaction medium. Applications to bulk and emulsion polymerizations are briefly discussed.
Keywords:DIFFUSION-CONTROLLED REACTION;DENSE POLYMER SYSTEMS;NON-SIMPLE MOLECULES;SPINODAL DECOMPOSITION;MORPHOLOGY;KINETICS;DYNAMICS;STYRENE;BLENDS