Isospecific, Chain Shuttling Polymerization of Propylene Oxide Using a Bimetallic Chromium Catalyst: A New Route to Semicrystalline Polyols

被引：62
|
作者：
Childers, M. Ian [1 ]
Vitek, Andrew K. [2 ]
Morris, Lilliana S. [1 ]
Widger, Peter C. B. [1 ]
Ahmed, Syud M. [1 ]
Zimmerman, Paul M. [2 ]
Coates, Geoffrey W. [2 ]
机构：
[1] Cornell Univ, Baker Lab, Dept Chem & Chem Biol, Ithaca, NY 14853 USA
[2] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 32期
关键词：
RING-OPENING COPOLYMERIZATION; CARBON-DIOXIDE; ENANTIOSELECTIVE POLYMERIZATION; ALTERNATING COPOLYMERIZATION; IMMORTAL POLYMERIZATION; EPOXIDE POLYMERIZATION; CYCLOHEXENE OXIDE; BLOCK-COPOLYMERS; COBALT CATALYSTS; POLYURETHANES;
D O I：
10.1021/jacs.7b00194
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Hydroxy-telechelic poly(propylene oxide) (PPO) is widely used industrially as a midsegment in polyurethane synthesis. These atactic polymers are produced from racemic propylene oxide using chain shuttling agents and double-metal cyanide catalysts. Unlike atactic PPO, isotactic PPO is semicrystalline with a melting temperature of approximately 67 degrees C. Currently there is no practical route to hydroxy-telechelic isotactic PPO using racemic propylene oxide as the monomer. In this paper, hydroxy-telechelic isotactic PPO is synthesized from racemic propylene oxide with control of molecular weight using enantioselective and isoselective bimetallic catalysts in conjunction with chain shuttling agents. The discovery of an easily accessible bimetallic chromium catalyst is reported for this transformation. Diol, triol, and polymeric chain shuttling agents are used to give hydroxy-telechelic isotactic PPO of varying functionality and structure. Detailed quantum chemical studies are used to reveal the polymerization mechanism and origin of stereoselectivity.
引用
收藏
页码：11048 / 11054
页数：7
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