| Abstract: | Based on our recent discovery of the isomerization polymerization of β-(2-acetoxyethyl)-β-propiolactone into poly-δ-ester,1,2 we examined the generality of this phenomenon by using two related monomers. The catalysts were (EtAlO)n and Et(ZnO)2ZnEt. The side-chains in the monomers selected were the (CH3)2CHCOO? CH2CH2? (2) and (CH3)CICHCOO? CH2CH2? (3) groups in which steric effects are almost identical but electronic effects are in opposition. The monomers yielded isomerized poly-δ-ester units, depending on the terminal substituent groups in the side-chain. These observations can be interpreted with the bicyclic intermediate proposed in the earlier work. Monomer (2) was reactive and produced a poly-δ-ester structure most readily, probably because of the higher electron density at the side-chain ester group which coordinated with the catalyst. In contrast, monomer (3) was less reactive, and the probability of isomerization was the lowest, i.e., the electron deficient side-chain ester group apparently interfered with the formation of the intermediate, especially in the Zn-catalysis. Equibinary random copolymers were prepared from (2) and (3) according to the catalyst and polymerization conditions chosen. |
