Vinylcyclopropane derivatives polymerization

Figure 4. Radical ring-opening polymerization of vinylcyclopropane derivatives.

More examples have been quoted of special growth reactions for molecules having two carbon-carbon double bonds. Cyclopolymerization occurs for diallylaminomethyl phenols, allyl esters of unsaturated acids, 2-(2-vinyl-phenoxy)ethyl methacrylate and acrylate, 2-divinylbenzene and some silicon-containing monomers. - Polymerizations of p-xylylene and its derivatives have been considered further. - The radical polymmzation of some disubstituted vinylcyclopropanes has been represented as shown in equation (2), where X and Y=CN or COjEt. The involvement of the ring must be connected with stabilization by the substituents of the product radical. 

A very versatile polymeric scaffold for site-specific double PPM is poly( 1 -aceto-l-pentalluorophenoxycarbonyl-2-vinylcyclopropane) [poly(APVCP)] (see Scheme 8) [139]. In this case, the two-step modification is performed in a sequential batch process. Following aminolysis by treatment with various primary amines, the ketone can be converted in the presence of hydrazide or hydroxylamine derivatives. Fmthermore, the ketone can be reduced to the secondary alcohol, which is subsequently converted into the ester or carbamate through the use of different acyl halides and isocyanates. 

---