Vinylcyclopropanes are important synthetic intermediates in organic chemist
ry and are mostly synthesized by the simultaneous introduction of the cyclo
propane and the vinyl unit, e.g., by the reaction of trans-1,4-dihalobutene
s with beta-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 substitut
ed vinylcyclopropanes results in polymers with mainly IJ-ring-opened units,
whereby radical stabilizing substituents or electron-withdrawing groups in
crease the radical polymerizability and the ring-opening ability. The vinyl
cyclopropanes undergo a radical copolymerization with other vinyl monomers,
such as methacrylates, and, in comparison to the polymerization of these l
inear vinyl monomers, the vinylcyclopropanes show a significantly lower vol
ume shrinkage during ring-opening polymerization. Hybrid vinylcyclopropanes
are polymerized step-by-step under formation of reactive polymers or polym
er networks. Multifunctional cross-linking vinylcyclopropanes can be used a
s new low-shrinking matrix monomers for photopolymerizable materials. In ad
dition, the sol-gel process of trialkoxysilyl-functionalized vinylcycloprop
anes affords low shrinking organic-inorganic nanocomposites.