Ring-Opening Metathesis Polymerization (ROMP)

By: William Sommer, Aldrich ChemFiles 2009, 9.6, 8.

Aldrich ChemFiles 2009, 9.6, 8.

ROMP has become an important reaction for the formation of well defined polymers. Ziegler and Natta's early studies on ethylene and polypropylene polymerization lead to extensive research efforts on the investigation of transition metal catalyzed polymerization and its mechanism, which ultimately lead to the development of ROMP.1 In 1992, the Grubbs group reported the synthesis of the first well defined ruthenium alkylidene, paving the way to a new generation of highly functional group tolerant ROMP catalysts.2 These catalysts are also utilized in living ROMP, allowing control of the molecular weight, a low polydispersity, and clean polymer end-capping. These advantages made ROMP the method of choice for the synthesis of complex polymeric architectures. Norbornene's strained bicyclic structure makes it an ideal monomer for ROMP and polymerization using the Grubbs family of catalysts leads to high reaction control. Furthermore, the monomer can be readily functionalized, which many groups have exploited to synthesize polynorbornene side chain functionalities such as catalysts, biological reagents, hydrogen bonding units or trapping molecules. This living character also allows for the introduction of two monomers resulting in the formation of alternative, block or random copolymers. These copolymers can impart a wide range of properties to the bulk polymer.

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  1. (a) Ziegler, H. et al. Angew. Chem. 1955, 67, 541.(b) Natta, G. Angew. Chem. 1956, 68, 393.
  2. Nguyen, S. T. et al. J. Am. Chem. Soc. 1992, 114, 3974.

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