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Updated: Feb 27, 2026

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
Published on: November 27, 2015
Isospecific, Chain Shuttling Polymerization of Propylene Oxide Using a Bimetallic Chromium Catalyst: A New Route to
M Ian Childers1, Andrew K Vitek2, Lilliana S Morris1
1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853-1301, United States.
Abstract:
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 °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.
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