Branched methacrylate copolymers from multifunctional monomers: chemical composition and physical architecture distributions

Soluble, branched (meth)acrylic copolymers have been made via facile, one-step, batch solution polymerisations taken to high conversion. Methyl methacrylate has been copolymerised with a bifunctional monomer using a chain transfer agent to inhibit gelation. Conventional chain transfer using a mercaptan has been compared to catalytic chain transfer (CCT) using a cobalt porphyrin. The polymerisations have been monitored as a function of monomer conversion and the polymer prepared at high conversion has been fractionated across the molecular weight distribution. The polymerisations remain isotropic, with both the chemical composition and physical architecture distribution varying systematically as a function of monomer conversion and copolymer molecular weight. A mechanism for the polymerisation is proposed based on the experimental data.