CYCLOPOLYMERIZATION OF CINNAMATE ESTER DERIVATIVES OF ALKYL ALPHA-(HYDROXYMETHYL) ACRYLATES

Three new monomers for cyclopolymerization were synthesized using phase transfer catalysis of ethyl alpha-(chloromethyl) acrylate (ECMA),t-butyl alpha-(bromomethyl) acrylate (TBBMA) and isobornyl alpha-(bromomethyl)acrylate (IBBMA) with cinnamic acid sodium salt. Bulk and solution polymerization at 70-80 degrees C using AIBN gave soluble cyclopolymers with Mn = 13650 and Mw = 36540 for the ethyl ester, Mn = 47700 and Mw = 86900 for the t-butyl ester and Mn = 3500 and Mw = 4650 for the isobornyl ester monomer. The ester polymerizabilities decreased with increasing substituent bulkiness. FTIR spectra showed ca 30 to 93% cyclic units depending on the concentration of the monomer used in polymerizations. DSC thermograms showed that alkyl group size had little effect on Tg's, with values of 151 degrees C, 156 degrees C, and 164 degrees C for the ethyl, t-butyl and isobornyl esters, respectively.