混合配体锂聚集体的合成、表征及催化性能，L-丙交酯开环聚合的优异引发剂。

Synthesis, characterization, and catalysis of mixed-ligand lithium aggregates, excellent initiators for the ring-opening polymerization of L-lactide.

作者信息

Ko B T, Lin C C

机构信息

Department of Chemistry, National Chung-Hsing University, Taichung 402, Taiwan, ROC.

出版信息

J Am Chem Soc. 2001 Aug 22;123(33):7973-7. doi: 10.1021/ja010604i.

DOI:10.1021/ja010604i

PMID:11506552

Abstract

Three novel mixed-ligand lithium aggregates, (mu(3)-EDBP)Li(2)(mu(3)-(n)Bu)Li(0.5Et(2)O) (1), (mu(3)-EDBP)Li(2)(mu(3)-OBn)Li (2), and (mu(3)-EDBP)Li(2)(mu(3)-OCH(2)CH(2)OCH(2)CH(3))Li (3), have been synthesized and structurally characterized. The reaction of 2,2'-ethylidene-bis(4,6-di-tert-butylphenol) (EDBP-H(2)) with 3.6 molar equiv of (n)BuLi gives 1 in high yield. 1 further reacts with benzyl alcohol and 2-ethoxyethanol respectively to yield the corresponding products 2 and 3. Experimental results show that 2 and 3 efficiently initiate the ring-opening polymerization of L-lactide in a controlled fashion, yielding polymers with very narrow polydispersity indexes in a wide range of monomer-to-initiator ratios.

摘要

合成并表征了三种新型混合配体锂聚合物，即[(μ₃-EDBP)Li₂]₂[(μ₃-(n)Bu)Li₀.₅Et₂O]₂ (1)、[(μ₃-EDBP)Li₂]₂[(μ₃-OBn)Li]₂ (2) 和 [(μ₃-EDBP)Li₂]₂[(μ₃-OCH₂CH₂OCH₂CH₃)Li]₂ (3)。2,2'-亚乙基双(4,6-二叔丁基苯酚)(EDBP-H₂) 与 3.6 摩尔当量的(n)BuLi 反应，高产率得到 1。1 分别与苄醇和 2-乙氧基乙醇进一步反应，得到相应产物 2 和 3。实验结果表明，2 和 3 能以可控方式有效引发 L-丙交酯的开环聚合，在广泛的单体与引发剂比例范围内得到具有非常窄的多分散指数的聚合物。