Highly efficient syntheses of acetoxy- and hydroxy-terminated telechelic poly(butadiene)s using ruthenium catalysts containing N-heterocyclic ligands

被引：94

作者：

Bielawski, CW ^{[1
]}

Scherman, OA ^{[1
]}

Grubbs, RH ^{[1
]}

机构：

[1] CALTECH, Div Chem & Chem Engn, Arnold & Mabel Beckman Labs Chem Synthesis, Pasadena, CA 91125 USA

来源：

POLYMER | 2001年 / 42卷 / 11期

基金：

美国国家科学基金会;

关键词：

hydroxy end-terminated telechelic poly(butadiene) (HTPBD); ring-opening metathesis polymerization (ROMP); ruthenium;

D O I：

10.1016/S0032-3861(00)00504-8

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Bis(acetoxy)-tenninated telechelic poly(butadiene) (PBD) with molecular weights controllable up to 3.0 X 10(4) have been prepared via the ring-opening metathesis polymerization (ROMP) of cyclooctadiene when 1,4-bis(acetoxy)-2-butene was included as a chain transfer agent (CTA). The polymerizations were catalyzed by a highly active ruthenium catalyst 1,3-bis(2,4,6-trimethylphenyl)imidazol-2- ylidene)(PCp3)(Cl2Ru = CHCHC(CH3)(2) (Cp = cyclopentyl) (6) with monomer/catalyst ratios as high as 9.8 X 10(4). Removal of the acetoxy groups with sodium hydroxide afforded hydroxy end-terminated telechelic PBD (HTPBD). Examination of the telechelic PBDs revealed an exclusive 1,4-PBD microstructure with a predominately trans geometry (up to 90%). The high activity and stability of 6 permitted a one-step synthesis of HTPBD using the unprotected free alcohol, 2-butene-1,4-diol, as the CTA. (C) 2001 Elsevier Science Ltd. All rights reserved.

引用

页码：4939 / 4945

页数：7

共 37 条

[1] Ruthenium carbene complexes with imidazolin-2-ylidene ligands allow the formation of tetrasubstituted cycloalkenes by RCM [J].