Radical polimerization of methyl alpha-crotonyloxymethyl) acrylate to soluble polymer bearing pendant double bonds

Methyl alpha-(crotonyloxymethyl)acrylate (MCRMA) of which the alpha-substit uted acryloyl and crotonyl groups are sterically hindered and reluctant to homopolymerize, respectively, was synthesized and polymerized. The polymeri zation of MCRMA primarily took place through homopolymerization of the alph a-(substituted methyl)acryloyl group to yield a soluble polymer bearing a l arge number of the pendant crotonyloxy groups. The ratio of the rate consta nts for the inter- and intramolecular additions of the propagating radical to form the linear and cyclic repeating units, respectively, indicates that this monomer exhibits an exceptionally low possibility of cyclopolymerizat ion because of the sterically hindered intramolecular addition of the croto nyloxymethyloyl radical to the crotonyl group. Crosslinking by the reaction of the pendant double bond slowly proceeded due to an extremely low reacti vity of the crotonyloxy group towards poly-[alpha-(crotonyloxymethyl)acryla te] radical.