Stereospecific polymerization of methyl methacrylate with single-component zirconocene complexes:: Control of stereospecificity via catalyst symmetry

被引：80

作者：

Frauenrath, H ^{[1
]}

Keul, H ^{[1
]}

Höcker, H ^{[1
]}

机构：

[1] Rhein Westfal TH Aachen, Inst Tech Chem & Makromol Chem, D-52056 Aachen, Germany

来源：

MACROMOLECULES | 2001年 / 34卷 / 01期

关键词：

D O I：

10.1021/ma001251v

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

We report the stereospecific polymerization of methyl methacrylate (MMA) with single-component cationic zirconocene catalysts. The complexes Me(2)CCpIndZrMe(thf)+BPh4- (1) and Me2CCp2ZrMe(thf)+BPh4- (2) are active catalysts for the polymerization of MMA, in remarkable contrast to other cationic zirconocenes. While 1 yields highly isotactic poly(methyl methacrylate) (PMMA), 2 is syndiospecific at low temperatures. This is the first example for a rational control of PMMA microstructure via catalyst symmetry. Polymerization kinetics and stereospecificity control in MMA polymerization with 1 and 2 are discussed. On the basis of the experimental data, a possible polymerization mechanism is proposed.

引用

页码：14 / 19

页数：6

共 23 条

[21] SYNTHESIS OF HIGH-MOLECULAR-WEIGHT POLY(METHYL METHACRYLATE) WITH EXTREMELY LOW POLYDISPERSITY BY THE UNIQUE FUNCTION OF ORGANOLANTHANIDE(III) COMPLEXES [J].

YASUDA, H ;

YAMAMOTO, H ;

YAMASHITA, M ;

YOKOTA, K ;

NAKAMURA, A ;

MIYAKE, S ;

KAI, Y ;

KANEHISA, N .

MACROMOLECULES, 1993, 26 (26) :7134-7143

[22] RARE-EARTH-METAL INITIATED POLYMERIZATIONS OF POLAR AND NONPOLAR MONOMERS TO GIVE HIGH-MOLECULAR-WEIGHT POLYMERS WITH EXTREMELY NARROW MOLECULAR-WEIGHT DISTRIBUTION [J].

YASUDA, H ;

IHARA, E .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 1995, 196 (08) :2417-2441

[23] SYNTHESIS OF MONODISPERSED HIGH-MOLECULAR-WEIGHT POLYMERS AND ISOLATION OF AN ORGANOLANTHANIDE(III) INTERMEDIATE COORDINATED BY A PENULTIMATE POLY(MMA) UNIT [J].

YASUDA, H ;

YAMAMOTO, H ;

YOKOTA, K ;

MIYAKE, S ;

NAKAMURA, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (12) :4908-4910

← 1 2 3 →