DIMENSIONS OF CROSS-LINKED POLYMERS FORMED IN LIVING VINYL DIVINYL COPOLYMERIZATION

A new kinetic theory for network formation in living copolymerization of vinyl and divinyl monomers is proposed. This theory is based on the distribution of cross-linked units in the primary polymer molecule al ong the direction of growth. The formed cross-linked structure, such a s the molecular weight distribution and the spatial distribution of cr oss-linked polymer chains, is investigated under the classical ring-fr ee model. The molecular weight distribution can be multimodal if the P oisson distribution is valid for the primary polymer molecules. The ra dius of gyration is found to be smaller than that for the random cross -linking of linear polymer chains having the most probable distributio n at the THETA state. The fractal dimension of the cross-linked polyme r molecules is less than 3 except for extremely large polymer molecule s, i.e., gel molecule in practice.