Abstract
13C NMR spectroscopy has been used to study branching and sequence distributions in copolymers of vinyl acetate (VAc) and n-butyl acrylate (BA) prepared by semibatch emulsion copolymerization. All copolymerizations proceeded via a seed stage that was carried out under monomer-flooded conditions, followed by a growth stage that operated under monomer-starved conditions. The 13C NMR spectra of the copolymers have been fully interpreted both in terms of the structural features arising from chain transfer to polymer and the repeat unit sequence distributions. The sequence distributions for copolymers formed in the seed stage are in reasonable agreement with predictions from the standard terminal-unit first-order Markov statistical model, showing that normal copolymerization kinetics operate under monomer-flooded conditions. However, the sequence distributions for copolymers produced in the growth stage are closely represented by a random Bernoullian distribution, showing that copolymers with random repeat uni...
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