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Synthesis and polymerization of vinylcyclopropanes
Author(s) -
Moszner Norbert,
Zeuner Frank,
Völkel Thomas,
Rheinberger Volker
Publication year - 1999
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/(sici)1521-3935(19991001)200:10<2173::aid-macp2173>3.0.co;2-a
Subject(s) - polymerization , polymer chemistry , monomer , copolymer , chemistry , polymer , ring opening polymerization , vinyl polymer , radical polymerization , materials science , organic chemistry
Vinylcyclopropanes are important synthetic intermediates in organic chemistry and are mostly synthesized by the simultaneous introduction of the cyclopropane and the vinyl unit, e. g., by the reaction of trans ‐1,4‐dihalobutenes with β ‐dicarbonyl compounds or the addition of carbenes to dienes. The polymerization of vinylcyclopropane itself results in vinyl polymers with predominantly 1,2‐structural units. The radical polymerization of substituted vinylcyclopropanes results in polymers with mainly 1,5‐ring‐opened units, whereby radical stabilizing substituents or electron‐withdrawing groups increase the radical polymerizability and the ring‐opening ability. The vinylcyclopropanes undergo a radical copolymerization with other vinyl monomers, such as methacrylates, and, in comparison to the polymerization of these linear vinyl monomers, the vinylcyclopropanes show a significantly lower volume shrinkage during ring‐opening polymerization. Hybrid vinylcyclopropanes are polymerized step‐by‐step under formation of reactive polymers or polymer networks. Multifunctional cross‐linking vinylcyclopropanes can be used as new low‐shrinking matrix monomers for photopolymerizable materials. In addition, the sol‐gel process of trialkoxysilyl‐functionalized vinylcyclopropanes affords low shrinking organic‐inorganic nanocomposites.