Synthesis of comblike poly(butyl methacrylate) using reversible addition-fragmentation chain transfer and an activated ester

Comblike polymers of poly(n-butyl methacrylate) were prepared using an activated ester-type comonomer (N-acryloxysuccinimide, NAS) to generate branch points. The conventional solution free-radical copolymerization kinetics of n-butyl methacrylate (BMA) and NAS were first investigated by following individual monomer consumption rates by H-1 NMR spectrometry and reactivity ratios of BMA and NAS determined using the terminal model. The reactivity ratios so obtained are both close to 0.2; the joint confidence interval is also determined. Reversible addition-fragmentation chain transfer (RAFT) was then used to grow polymers with controlled backbone and branch chain length. Because both reactivity ratios have similar values, this implies that the copolymer will have a random distribution of NAS and hence of branch points. RAFT-mediated polymerization was first used to synthesize linear poly(BMA-co-NAS) chains. Primary hydroxy-functionalized RAFT agents were then immobilized on this linear poly(BMA-co-NAS) through nucleophilic substitution on the activated ester units of the NAS. From these immobilized RAFT agents, branches were grown upon addition of a further aliquot of monomer (BMA) and initiator (AIBN). The amount of NAS in the starting BMA/NAS composition was varied without adversely affecting the uniformity of the NAS distribution along the resulting linear poly(BMA-co-NAS) backbone. This results in branched polymers whose molecular weight, branching density, and degree of polymerization of branches are all relatively narrow and controlled.