Aj. Holder et al., A semiempirical quantum mechanical study of cationically catalyzed homopolymerization and copolymerization of vinyl ethers and epoxides, J MOL ST-TH, 507, 2000, pp. 63-73
The purpose of this study was to use the semiempirical quantum mechanical c
omputational method, AM1, to investigate vinyl ether cationic homopolymeriz
ation, epoxide homopolymerization, and copolymerization of selected vinyl e
thers with a model epoxide (cyclohexene oxide). Homopolymerization studies
of 19 vinyl ethers showed that activation enthalpies ranged between 0.0 and
15 kcal/mol, and that the enthalpies of reaction for homopolymerization we
re nearly all exothermic, Homopolymerization of three epoxides predicted lo
w activation enthalpies, some of which were virtually activationless. All r
ing opening epoxide polymerizations were exothermic, Copolymerization of th
ree vinyl ethers with cyclohexene oxide gave activation enthalpies that var
ied between 2.7 and 4.0 kcal/mol, and the enthalpies of reaction for copoly
merization were all exothermic. (C) 2000 Elsevier Science B.V. All rights r
eserved.