Journal
EUROPEAN POLYMER JOURNAL
Volume 45, Issue 7, Pages 2142-2149Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.eurpolymj.2009.02.013
Keywords
Addition polymerization and copolymerization; Silyl-substituted polynorbornenes; Poly(tricyclononenes); [2+2]-Cyclodimerization; Ni-catalysts
Categories
Funding
- Russian Foundation of Basic Research [09-03-00342-a]
- Russian Science Support Foundation
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Addition polymerization and copolymerization of bis(Me3Si)-substituted norbornene-type monomers such as 5,5-bis(trimethylsilyl)norbornene-2,2,3-bis(trimethylsilyl)norbornadiene-2,5 and 3,4-bis(trimethylsilyl)tricyclo[4.2.1.0(2.5)]nonene-7, in the presence of Ni(II) naphtenate/MAO catalyst were studied. Disubstituted norbornene and norbornadiene were found to be practically inactive in homopolymerization. On the other hand, their copolymerization with norbornene proceeded with moderate yields of copolymers containing predominantly norbomene units. Under studied reaction conditions 2,3-bis(trimethylsilyl)norbornadiene-2,5 was transformed into the only exo-trans-exo-dimer as a result of the [2+2]-cyclodimerization reaction. Moving Me3Si-substituents one carbon atom away from norbomene double bond made 3,4-bis(trimethylsilyl)tricyclo[4.2.1.0(2.5)]nonene-7 active in homopolymerization and allowed to obtain addition homo-polymer with two Me3Si-substituents in each elementary unit. The reaction mechanism and steric effect of Me3Si-substituents are also discussed. (C) 2009 Published by Elsevier Ltd.
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