Effect of polymerization conditions on the syndiotactic-specificity in radical polymerization of N-isopropylacrylamide and fractionation of the obtained polymer according to the stereoregularity

Radical polymerization of N-isopropylacrylamide (NIPAAm) was examined in the presence of hexamethylphosphoramide (HMPA). The addition of an excess amount of HMPA induced syndiotactic-specificity that gradually enhanced as the feed monomer was consumed. The syndiotacticity of the obtained poly(NIPAAm)s was improved by increasing the [HMPA]0/[NIPAAm]0 ratio to five and prolonging the polymerization time to 96 h (racemo=72%). It was also revealed that more stereoregulated poly(NIPAAm) could be fractionated by reprecipitating the resulting polymers from hexane-THF mixture. This result suggested that more stereoregulated poly(NIPAAm) showed a lower solubility than less stereoregulated poly(NIPAAm)s. Furthermore, unusual hysteresis was observed in transmittance analysis of an aqueous solution of the fractionated syndiotactic poly(NIPAAm).