Living polymerization of substituted acetylenes by a novel binary catalyst, MoOCl4-n-BuLi

被引:28
作者
Hayano, S [1 ]
Masuda, T [1 ]
机构
[1] Kyoto Univ, Dept Polymer Chem, Kyoto 6068501, Japan
关键词
D O I
10.1021/ma971575s
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A novel MoOCl4-based binary catalyst, MoOCl4-n-BuLi, induced the living polymerization of o-CF3-phenylacetylene. A catalyst composition of MoOCl4:n-BuLi = 1:1 and anisole as polymerization solvent were favorable. The polydispersity ratio of the polymer was as small as 1.02; the initiator efficiency was no more than 1.5-2.5%. The living nature was confirmed by both multistage polymerization and time dependence of the polymerization. Ethanol in catalytic amounts decelerated the polymerization but hardly affected its living nature. n-Alkyllithiums were generally useful as second catalyst components. The polymerization proceeded in a living manner in the temperature range 0-30 degrees C. o-Me3Si-phenylacetylene, o-i-Pr-phenylacetylene, and 1-chloro-1-octyne also polymerized in a living fashion; their polydispersity ratios were 1.03, 1.08, and 1.08, respectively.
引用
收藏
页码:3170 / 3174
页数:5
相关论文
共 18 条
[1]  
BRANDSMA L, 1985, RECL TRAV CHIM PAY B, V104, P226
[2]  
CARPITA A, 1984, SYNTHESIS-STUTTGART, P571
[3]   Well-defined ruthenium olefin metathesis catalysts: Mechanism and activity [J].
Dias, EL ;
Nguyen, ST ;
Grubbs, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (17) :3887-3897
[4]   LIVING CYCLOPOLYMERIZATION OF 1,6-HEPTADIYNE DERIVATIVES USING WELL-DEFINED ALKYLIDENE COMPLEXES - POLYMERIZATION MECHANISM, POLYMER STRUCTURE, AND POLYMER PROPERTIES [J].
FOX, HH ;
WOLF, MO ;
ODELL, R ;
LIN, BL ;
SCHROCK, RR ;
WRIGHTON, MS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (07) :2827-2843
[5]   LIVING CYCLOPOLYMERIZATION OF DIETHYL DIPROPARGYLMALONATE BY MO(CH-T-BU)(NAR)[OCME(CF3)2]2 IN DIMETHOXYETHANE [J].
FOX, HH ;
SCHROCK, RR .
ORGANOMETALLICS, 1992, 11 (08) :2763-2765
[6]   TITANACYCLOBUTANES DERIVED FROM STRAINED CYCLIC OLEFINS - THE LIVING POLYMERIZATION OF NORBORNENE [J].
GILLIOM, LR ;
GRUBBS, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (04) :733-742
[7]   Living polymerization of substituted acetylenes by a novel ternary catalyst, MoOCl4-Et2Zn-EtOH [J].
Hayano, S ;
Masuda, T .
MACROMOLECULAR CHEMISTRY AND PHYSICS, 1997, 198 (10) :3041-3049
[8]  
HAYANO S, IN PRESS
[9]  
KANESHIRO H, IN PRESS
[10]   LIVING POLYMERIZATION OF PHENYLACETYLENES INITIATED BY RH(C-CC6H5)(2,5-NORBORNADIENE)[P(C6H5)(3)](2) [J].
KISHIMOTO, Y ;
ECKERLE, P ;
MIYATAKE, T ;
IKARIYA, T ;
NOYORI, R .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (26) :12131-12132