Cationic polymerization of norbornene derivatives in the presence of boranes
Macromolecules, ISSN: 1520-5835, Vol: 47, Issue: 16, Page: 5470-5483
2014
- 43Citations
- 55Captures
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Article Description
Cationic polymerization of 5-methylene-2-norbornene, 5-ethylidene-2- norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, and norbornadiene-2,5 in the presence of boranes was systematically studied. It was found that B(C F) in combination with caprylic acid, 1-phenylethanol or water was a highly active catalyst for the polymerization of 5-alkylidene-2-norbornenes. The corresponding cationic polymers were obtained with up to yields 95% and with high molecular weights (M ≤ 430 000). The activity of 5-alkylidene-2-norbornenes in the polymerization using B(CF) containing systems was the highest among the other monomers (5-vinyl-2-nobornene, dicyclopentadiene, and norbornadiene-2,5). BF·O(CH) based catalysts turned out to be not so active for cationic polymerization of monomers compared with the systems containing B(C F). They produced polymers predominantly containing the addition (vinyl) units instead of isomerization units. The structure of the polymer main chain units depended on the nature of the monomers: in the case of norbornadiene-2,5, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene the transannular polymerization proceeded, while dicyclopentadiene and 5-vinyl-2-norbornene formed the addition type polymers under the studied conditions. © 2014 American Chemical Society.
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