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

被引:183
作者
Ko, BT [1 ]
Lin, CC [1 ]
机构
[1] Natl Chung Hsing Univ, Dept Chem, Taichung 402, Taiwan
关键词
D O I
10.1021/ja010604i
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Three novel mixed-ligand lithium aggregates, [(mu3-EDBP)Li-2](2)[(mu (3)-Bu-n)Li(0.5Et(2)O)](2) (1), E(mu (3)-EDBP)Li-2](2)[(mu (3)-OBn)Li](2) (2), and [(mu (3)-EDBP)Li-2](2)[(mu3-OCH2CH2OCH2CH3)Li](2) (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 (BuLi)-Bu-n 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.
引用
收藏
页码:7973 / 7977
页数:5
相关论文
共 61 条
[1]   LIVING AND IMMORTAL POLYMERIZATIONS [J].
AIDA, T .
PROGRESS IN POLYMER SCIENCE, 1994, 19 (03) :469-528
[2]   Metalloporphyrins as initiators for living and immortal polymerizations [J].
Aida, T ;
Inoue, S .
ACCOUNTS OF CHEMICAL RESEARCH, 1996, 29 (01) :39-48
[3]  
Andrews PC, 2000, ANGEW CHEM INT EDIT, V39, P4516, DOI 10.1002/1521-3773(20001215)39:24<4516::AID-ANIE4516>3.3.CO
[4]  
2-M
[5]  
[Anonymous], 1992, Polym. Prepr. (Am. Chem Soc. Div. Polym Chem.)
[6]  
[Anonymous], ACS SYM SER
[7]   THERMOCHEMICAL COMPARISON OF ORGANOLITHIUM BASES [J].
ARNETT, EM ;
MOE, KD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (18) :7068-7069
[8]   Intermolecular chain transfer to polymer with chain scission: General treatment and determination of k(p)/k(tr) in L,L-lactide polymerization [J].
Baran, J ;
Duda, A ;
Kowalski, A ;
Szymanski, R ;
Penczek, S .
MACROMOLECULAR RAPID COMMUNICATIONS, 1997, 18 (04) :325-333
[9]   ORTHO METALATIONS - ADVANTAGE OF THE AMIDE FUNCTIONS [J].
BEAK, P ;
BROWN, RA .
JOURNAL OF ORGANIC CHEMISTRY, 1979, 44 (24) :4463-4464
[10]   COMPARISON OF THE X-RAY CRYSTAL-STRUCTURES OF THE SODIUM AND POTASSIUM 2,4,6-TRIS(TRIFLUOROMETHYL)PHENOXIDES (RO-) AND 2,4,6-TRIS(TRIFLUOROMETHYL)BENZENETHIOLATES (RS-) - [NA(OR)(THF)2]2, [K(OR)(THF)2(MU-THF)]2, [NA(SR)(THF)2.0.25THF]X AND [K(SR)(THF)]X (THF = TETRAHYDROFURAN) [J].
BROOKER, S ;
EDELMANN, FT ;
KOTTKE, T ;
ROESKY, HW ;
SHELDRICK, GM ;
STALKE, D ;
WHITMIRE, KH .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (03) :144-146