Vinyl acetate polymerization intramolecular

This is however not the case. Therefore, the propagating radical of vinyl benzoate is not considered to be more stabilized than that of vinyl acetate, the intramolecular complex mechanism being ruled out owing to the low rate of bulk polymerization of vinyl benzoate121. ... 

Backbiting is an intramolecular chain transfer reaction. If transfer reactions occur between different chains, long-chain branched polymers are formed. Well-known examples include ethylene and vinyl acetate. Vinyl acetate polymerization could lead to gel formation under certain conditions. It should be pointed out that chain transfer to polymer reaction alone generates only T-type branch structures that do not result in gel formation. Theoretically, some mechanism such as radical termination by combination that brings two chains together to form H-type branch structures is an essential condition for gelation. 

Sorokin, A., Influence of the Intramolecular distribution of vinyl acetate groups in polyvinyl alcohols on their physiochemical and biological properties, Polymeric Materials Science and Engineering of the American Chemical Society Meeting, Vol. 78, Spring, Dallas TX 1998. 

It has been shown that intramolecular chain transfer to polymer occurs during the polymerization of vinyl acetate, leading to short-chain branching (81,235—238). The number of short-chain branches has been estimated by nmr to be in the range of 0.12—1.7 mol % (81). The number of short-chain branches increases significantly at low monomer concentration. 

For certain monomers such as vinyl acetate and ethylene, branching is much more significant. The free-radical (high-pressure) polymerization of low-density polyethylene (LDPE) includes a back-biting internal chain-transfer reaction that results in the formation of a short branch. It is this branching that results in an upper limit for the crystallinity of LDPE of about 60%-70% and a melt temperature of 110 C the backbiting reaction preferentially occurs with the formation of an intramolecular six-membered ring that results in preferential formation of a C4 short-chain branch as shown in Scheme 1.41. 

The thermal elimination process can be applied to most substituted groups in vinyl polymers by controlled pyrolysis at 600 to TOO C, producing poly vinylene compoimds, e.g., by the splitting off of acetic acid from poly(vinyl acetate). By careful temperature control, one can achieve bifunctional reactions and/or intramolecular cyclizations. This has been developed commercially at relatively high temperatures, in the case of the polymerization of methacrylamide above 65°C, to yield a polymer with a substantial proportion of imide groups ... 

Deffieux et al. have already prepared a-styrenyl-cw-acetal heterodifunctional vinylic polymers using living anionic polymerizations [26-30]. The heterotelechelic polystyrene chains containing a-hydroxy-cw-carboxy end groups using free radical polymerization were also prepared, and the intramolecular cyclization (unimolecular process) was examined [37]. The... 

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