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Published May 14, 2013 | Supplemental Material
Journal Article Open

Catalyst-Dependent Routes to Ring-Opening Metathesis Alternating Copolymers of Substituted Oxanorbornenes and Cyclooctene


The alternating copolymerization of cis-cyclooctene and 1-substituted oxanorbornenes with commercially available ruthenium-based olefin metathesis catalysts was investigated. We determined that RuCl2(CHPh)(PCy3)2 performs a standard alternating copolymerization with these monomers. Unexpectedly, another route to the desired alternating copolymer was revealed. The "sequence editing" route involves the initial polymerization of cis-cyclooctene, followed a ring-opening cross metathesis step that introduces the 1-substituted oxanorbornene monomer in the polycyclooctene chain and largely avoids oxanorborene homopolymerization. Selectivity for alternating diads in the polymer exceeds 90%. Polymer molecular weight can be controlled by linear olefin chain-transfer reagents during sequence editing.

Additional Information

© 2013 American Chemical Society. Received: January 21, 2013; Revised: March 27, 2013; Published: April 17, 2013. This work was financial supported by the Department of Energy (DOE). Catalysts A, B, C, and D were gifts from Materia, Inc. C.S.D. would like to thank Dr. Garret Miyake and Brendan Quigley for helpful discussions.

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