SYNTHESES AND RADICAL RING-OPENING POLYMERIZATIONS OF 1,1-BIS(HYDROXYMETHYL)-2-VINYLCYCLOPROPANE AND 1,1-BIS(METHOXYMETHYL)-2-VINYLCYCLOPROPANE

Syntheses and radical ring-opening polymerization of 1,1-bis(hydroxyme thyl)-2-vinylcyclopropane (1a) and 1,1-bis(methoxymethyl)-2-vinylcyclo propane (1b) were examined. Novel polymers bearing hydroxyl and methyl ether moieties in the side chains as well as olefinic moieties in the main chain were obtained. The main structure of the polymers, obtaine d by radical polymerization, originated from the cleavage of the cyclo propane ring near the hydroxymethyl or methoxymethyl groups. The diffe rence in the two-center energies and bond orders of the C-C bonds of t he cyclopropane ring well explained the selectivity in the direction o f the cleavage. The number-average molecular weights ((M) over bar(n)) of poly(1a) and poly(1b) were 94200 and 11200 in the polymerization i n bulk at 60 degrees C, respectively. The intermolecular hydrogen bond ing of la might increase the radical polymerizability. The oxygen perm eability of poly(1a) was 6.19 mL.20 mm.m(-2).day(-1).atm(-1) at 35 deg rees C, demonstrating that poly(1a) could be a good oxygen barrier mat erial.