期刊
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
卷 45, 期 10, 页码 1835-1847出版社
WILEY
DOI: 10.1002/pola.21947
关键词
heterolytic outer-sphere; homolytic inner-sphere; kinetics; kinetic simulation; living polymerization; radical polymerization; simulations; single electron transfer
A mechanistic comparison of the ATRP and SET-LRP is presented. Subsequently, simulation of kinetic experiments demonstrated that, in the heterolytic outersphere single-electron transfer process responsible for the SET-LRP, the activation of the initiator and of the propagating dormant species is faster than of the homolytic inner-sphere electron-transfer process responsible for ATRP. In addition, simulation experiments suggested that in both polymerizations the rate of deactivation is similar. In SET-LRP, the Cu(II)X-2/L deactivator is created by the disproportionation of Cu(I)X/L inactive species, while in ATRP its concentration is mediated by the bimolecular termination. The combination of higher rate of activation with the creation of deactivator via disproportionation provides, via SET-LRP, an ultrafast synthesis of polymers with very narrow molecular weight distribution at room temperature. SET-LRP is mediated by a catalytic amount of Cu(O), and under suitable conditions, bimolecular termination is virtually absent. Kinetic and simulation experiments have also demonstrated that the amount of water available in commercial solvents and monomers is sufficient to induce the disproportionation of Cu(I)X/L into Cu(O) and Cu(II)X-2/L and, subsequently, to change the polymerization mechanism from ATRP to SET-LRP. (c) 2006 Wiley Periodicals, Inc.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据