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TiCp2Cl-Catalyzed Living Radical and Ring Opening Polymerizations Initiated from Epoxides and Aldehydes in the Synthesis of Linear, Graft and Branched Polymers

Published online by Cambridge University Press:  01 February 2011

Alexandru D. Asandei ,
Isaac W. Moran ,
Gobinda Saha  and
Yanhui Chen
Alexandru D. Asandei
Affiliation:
Institute of Materials Science, Polymer Program, University of Connecticut, Storrs, CT 06269. Department of Chemistry, University of Connecticut, Storrs, CT 06269.
Isaac W. Moran
Affiliation:
Institute of Materials Science, Polymer Program, University of Connecticut, Storrs, CT 06269.
Gobinda Saha
Affiliation:
Institute of Materials Science, Polymer Program, University of Connecticut, Storrs, CT 06269.
Yanhui Chen
Affiliation:
Department of Chemistry, University of Connecticut, Storrs, CT 06269.
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Abstract

Ti(III)Cp2Cl-catalyzed radical ring opening (RRO) of epoxides or single electron transfer (SET) reduction of aldehydes generates Ti alkoxides and carbon centered radicals which add to styrene, initiating a radical polymerization. This polymerization is mediate in a living fashion by the reversible termination of growing chains with the TiCp2Cl metalloradical. In addition, polymers or monomers containing pendant epoxide groups (glycidyl methacrylate) can be used as substrates for radical grafting or branching reactions by self condensing vinyl polymerization. In addition, Ti alkoxides generated in situ by both epoxide RRO and aldehyde SET initiate the living ring opening polymerization of ε-caprolactone. Thus, new initiators and catalysts are introduced for the synthesis of complex polymer architectures.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 856: Symposium BB – Multicomponent Polymer Systems-Phase Behavior, Dynamics, and Applications , 2004 , BB11.9
Copyright
Copyright © Materials Research Society 2005

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