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Published June 22, 1992 | public
Journal Article

Aqueous ring-opening metathesis polymerization of carboximide-functionalized 7-oxanorbornenes


The ring-opening metathesis polymerization (ROMP) of exo-N-methyl-7-oxabicyclo[2.2.1]-hept-5-ene-2,3-dicarboximide (1) was accomplished in aqueous solution under mild conditions using the simple ruthenium(II) coordination complex Ru^(II)(H_2O)_6(tos)_2 (tos = p-toluenesulfonate) (2). The polymerization yield was nearly quantitative. The resultant high molecular weight polymer (poly-1) exhibited a glass transition temperature (T_g) of 225 °C and was thermally stable up to 402 °C. The thermal and radiative stabilities of poly-1 were further investigated. Poly-1 was hydrogenated to yield its saturated analogue, which had a lower T_g (170 °C) but a higher temperature of decomposition (430 °C). Complex 2 was deactivated by coordination of free maleimides formed during the polymerization of carboximide-functionalized monomers capable of undergoing retro Diels-Alder chemistry. The scope of this polymerization was therefore limited to carboximide-functionalized monomers that are stable toward retro Diels-Alder reactions at the polymerization temperature. Both ruthenium (II)-1 and ruthenium(II)-N-methylmaleimide olefin complexes were identified.

Additional Information

© 1992 American Chemical Society. Received November 14, 1991; Revised Manuscript Received March 3, 1992. This work was supported by the National Science Foundation and the Caltech Chemical Consortium (DuPont, Kodak, Shell, and 3M). C.L. acknowledges the CNRS and the NSF for a postdoctoral fellowship. D.V.M. is the recipient of a Department of Education Graduate Fellowship, for which he is grateful. We would also like to thank Dr. T. Sasaki and Prof. W. K. Risse (University of Marburg) for additional DSC analysis.

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