Catalysts for the ring-opening polymerization of ε-caprolactone and L-lactide and the mechanistic study

被引:99
作者
Yu, TL [1 ]
Wu, CC [1 ]
Chen, CC [1 ]
Huang, BH [1 ]
Wu, JC [1 ]
Lin, CC [1 ]
机构
[1] Natl Chung Hsing Univ, Dept Chem, Taichung 402, Taiwan
关键词
magnesium; catalyst; L-lactide;
D O I
10.1016/j.polymer.2005.04.079
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Two novel magnesium aryloxides have been prepared and their catalytic activities toward ring-opening polymerization (ROP) of epsilon-caprolactone and L-lactide have been investigated. The reaction of 2,2'-(2-methoxybenzylidene)-bis(4,6-di(1-methyl-1-phenylethyl)phenol) (MEMPEP-H-2) (1) and 2,2'-methylene-bis(4,6-di(1-methyl-1-phenylethyl)phenol) (MMPEP-H-2) with "Bu2Mg yield dimeric magnesium complexes [Mg(mu-MEMPEP)(THF)](2) (2) and [Mg(mu-MMPEP)(THF)](2) (3), respectively. Catalytic studies of complexes 2 and 3 illustrate that both 2 and 3 are good catalysts in epsilon-caprolactone and L-lactide polymerization. Theoretical study of the ROP mechanism of epsilon-caprolactone catalyzed by 2 demonstrates that the initiator, benzyl alcohol, is activated by the formation of a hydrogen bond with the phenoxy oxygen of MEMPEP2- ligand. (c) 2005 Elsevier Ltd. All rights reserved.
引用
收藏
页码:5909 / 5917
页数:9
相关论文
共 82 条
[51]   Polymerization of L,L-lactide initiated by aluminum isopropoxide trimer or tetramer [J].
Kowalski, A ;
Duda, A ;
Penczek, S .
MACROMOLECULES, 1998, 31 (07) :2114-2122
[52]   Polymerization of L,L-dilactide initiated by tin(II) butoxide [J].
Kowalski, A ;
Libiszowski, J ;
Duda, A ;
Penczek, S .
MACROMOLECULES, 2000, 33 (06) :1964-1971
[53]   Polylactones 48.: SnOct2-initiated polymerizations of lactide:: A mechanistic study [J].
Kricheldorf, HR ;
Kreiser-Saunders, I ;
Stricker, A .
MACROMOLECULES, 2000, 33 (03) :702-709
[54]   A highly efficient catalyst for the "living" and "immortal" polymerization of ε-caprolactone and L-lactide [J].
Liu, YC ;
Ko, BT ;
Lin, CC .
MACROMOLECULES, 2001, 34 (18) :6196-6201
[55]  
MA H, 2005, J CHEM SOC DA, P721
[56]  
MA HY, 2003, J CHEM SOC DA, P4773
[57]  
Majerska K, 2000, MACROMOL RAPID COMM, V21, P1327, DOI 10.1002/1521-3927(20001201)21:18<1327::AID-MARC1327>3.0.CO
[58]  
2-9
[59]   Unprecedented reversible migration of amide to Schiff base ligands attached to tin: Latent single-site initiators for lactide polymerization [J].
Nimitsiriwat, N ;
Marshall, EL ;
Gibson, VC ;
Elsegood, MRJ ;
Dale, SH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (42) :13598-13599
[60]   Stereoselective ring-opening polymerization of racemic lactide using aluminum-achiral ligand complexes: Exploration of a chain-end control mechanism [J].
Nomura, N ;
Ishii, R ;
Akakura, M ;
Aoi, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (21) :5938-5939