Branching Regulation in Olefin Polymerization via Lewis Acid Triggered Isomerization of Monomers

被引：29

作者：

Basbug Alhan, Hatice E. ^{[1
]}

Jones, Glen R. ^{[1
]}

Harth, Eva ^{[1
]}

机构：

[1] Univ Houston, Ctr Excellence Polymer Chem, Dept Chem, 3585 Cullen Blvd, Houston, TX 77204 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 12期

关键词：

block copolymers; branching; chain-walking; Lewis acids; olefins; TRANSITION-METAL COMPOUNDS; PRECISION CHAIN-WALKING; ALPHA-DIIMINE NICKEL; THERMOPLASTIC ELASTOMERS; ALKENE INSERTION; ETHYLENE; COPOLYMERIZATION; POLYETHYLENE; PALLADIUM; CATALYSTS;

D O I：

10.1002/anie.201914742

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We present a new strategy to regulate branching in chain-walking olefin polymerization by triggering a rapid isomerization of 1-alkene monomers into internal olefins by adding a Lewis acid. Polymerization of internal alkenes proceeds via chain-walking to give polymers with much higher branching than 1-alkene analogues. The utility of this approach is exemplified by synthesis of well-defined block copolymers with distinct branching characteristics per block by addition of Lewis acid midway through a reaction. We propose a novel mechanism whereby Lewis acid undergoes a counterion swap with the complex which favors isomerization as well as forming adducts with ancillary ligands, freeing coordination sites for internal alkene coordination polymerization.

引用

页码：4743 / 4749

页数：7

共 37 条

[11] Synthesis of polyolefin elastomers from unsymmetrical -diimine nickel catalyzed olefin polymerization [J].

Fang, Jun ;

Sui, Xuelin ;

Li, Yougui ;

Chen, Changle .

POLYMER CHEMISTRY, 2018, 9 (30) :4143-4149

[12] Influence of short chain branching on the miscibility of binary polymer blends: Application to polyolefin mixtures [J].

Freed, KF ;

Dudowicz, J .

MACROMOLECULES, 1996, 29 (02) :625-636

[13] Living and block copolymerization of ethylene and α-olefins using palladium(II)-α-diimine catalysts [J].

Gottfried, AC ;

Brookhart, M .

MACROMOLECULES, 2003, 36 (09) :3085-3100

[14] Chain walking: A new strategy to control polymer topology [J].

Guan, ZB ;

Cotts, PM ;

McCord, EF ;

McLain, SJ .

SCIENCE, 1999, 283 (5410) :2059-2062

[15] Semicrystalline thermoplastic elastomeric polyolefins: Advances through catalyst development and macromolecular design [J].

Hotta, Atsushi ;

Cochran, Eric ;

Ruokolainen, Janne ;

Khanna, Vikram ;

Fredrickson, Glenn H. ;

Kramer, Edward J. ;

Shin, Yong-Woo ;

Shimizu, Fumihiko ;

Cherian, Anna E. ;

Hustad, Phillip D. ;

Rose, Jeffrey M. ;

Coates, Geoffrey W. .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2006, 103 (42) :15327-15332

[16] Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium(II) catalysts [J].

Johnson, LK ;

Mecking, S ;

Brookhart, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (01) :267-268

[17] NEW PD(II)-BASED AND NI(II)-BASED CATALYSTS FOR POLYMERIZATION OF ETHYLENE AND ALPHA-OLEFINS [J].

JOHNSON, LK ;

KILLIAN, CM ;

BROOKHART, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (23) :6414-6415

[18] Photochemical regulation of a redox-active olefin polymerization catalyst: controlling polyethylene microstructure with visible light [J].

Kaiser, Jordan M. ;

Anderson, W. Curtis, Jr. ;

Long, Brian K. .

POLYMER CHEMISTRY, 2018, 9 (13) :1567-1570

[19] Diametrically opposite trends in alkene insertion in late and early transition metal compounds: Relevance to transition-metal-catalyzed polymerization of polar vinyl monomers [J].

Kang, MS ;

Sen, A ;

Zakharov, L ;

Rheingold, AL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (41) :12080-12081

[20]

Kennedy J. P., 1970, FORTSCHR HOCHPOLYMER, P369

← 1 2 3 4 →