A. Takasu, M. Ishii, Y. Inai
Aug 16, 2003
Citations
0
Influential Citations
12
Citations
Journal
Macromolecules
Abstract
(E,E)-Methyl sorbate (MS) and (E,E)-ethyl sorbate (ES), i.e., methyl 2,4-hexadienoate and ethyl 2,4-hexadienoate, underwent anionic polymerization in toluene at −60 to 0 °C in the presence of organoaluminum Lewis acids. The NMR, wide-angle X-ray diffraction (WAXD), and semiempirical molecular orbital calculation demonstrated that 1,4-trans-threo-disyndiotactc polymerization occurred (tritactic polymerization). Coordination of methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) (MAD/t-BuLi = 3) played three important roles, stabilization of the propagating anion, the activation of the monomer, and dissociation of tert-butyllithium (t-BuLi) aggregated in toluene to give polymers with relatively narrow molecular weight distribution (Mw/Mn = 1.3) using t-BuLi−(−)-menthyl ethyl ether (MEE) complex as the initiator. Hydrogenations of poly(MS) and poly(ES) with p-toluenesulfonylhydrazide (TSH) produced head-to-head (H−H) poly(propylene-alt-methyl acrylate) and poly(propylene-alt-ethyl acrylate), respec...