Radical copolymerization of n-butyl acrylate (A) and 2,2-dicyano-l-[2-(2-(acryloyloxy)ethyl)dimethylammonioethoxy] ethenolate (B) initiated at 60°C by 4,4'-azobis-4-cyanovaleric acid (ACVA) was studied in two complementary systems: homogeneous phase in dimethylformamide (DMF) and heterogeneous phase in aqueous ethanol (water volume fraction 0.4). In DMF ([-A + B] ~ 0.6-1 moll 1, [-ACVA]/[A + B] = 5 ? 10 -3, molar fraction of monomer B in the comonomer feed f~ ~< 0.7), the copolymerization obeys the terminal unit model and the two monomers of identical acrylate structure behave as an ideal azeotropic comonomer pair: reactivity ratios r A ~ r~ ~ 1. In aqueous ethanol ([A + B] ~ 0.6-2 mol 1 1, [ACVA]/[A + B] = 5 z 10-3,fB ~< 0.8), the unusual composition diagram (apparent reactivity ratios rA, r B > 1) probably results from preferential sorption of either monomer by the insoluble growing macroradicals: the experimental data may be reconciled with the terminal unit model and with invariant 'intrinsic' reactivity ratios (r A ~ r B ~ l) within the simplified framework that stresses the major importance of the ratio of the binding constants of monomers A and B to the growing chain (K=kAA/kBB~0.49). Moreover, copolymerization in heterogeneous phase leads to higher molecular weights. The zwitterionic units significantly increase the copolymer chain sensitivity towards thermal degradation: an irreversible and rather slow first-order rearrangement of the zwitterionic structure occurs for temperatures higher than 150°C (K ~ 2.8 ? 10 6s t at 160°C), well before the initial weight loss observed at about 260°C under nitrogen.
Посилання на статтю:
n-Butyl acrylate zwitterionomers of the ammonioethoxydicyanoethenolate type: 1. Synthesis / Catherine Gingreau and Jean-Claude Galin // Polymer. – 1994. – Vol 35. – P. 4669-4677.