Materials Applications of Olefin Metathesis Polymerization

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The synthesis of new polymeric materials is proposed, using olefin matathesis and olefin metathesis polymerization catalysis. This work is intended to demonstrate whether these reactions are versatile routes to a range of molecular topologies and are useful in polymer interface applications. Block copolymers will be prepared by the metathesis of vinyl-terminated polymers, the use of polymeric chain-transfer agents and the sequential addition of two specific monomers to a metathesis polymerization. Graft copolymers will be synthesized by the cometathesis of cyclic olefins and cyclic olefin-terminated polymers (macromonomers). Macrocyclic polymers will be prepared by metathesis of divinyl-terminated polymers using a heterogeneous catalyst. Single polymer and copolymer networks will be prepared by metathesis of dicyclic-olefin-terminated polymers and cometathesis of cyclic olefins and a crosslinking agent. The development of a versatile crosslinking agent is an objective of this work as well. Star polymers will be prepared by cyclic oligomerization of cyclic olefin-terminated polymers. Gradient modulus materials will be prepared by varying the crosslink density across one dimension of macroscopic poly(alkenamer) objects. Catalytic adhesion processes for polymers will be developed using both poly(alkenamers) and cyclic olefin- surface-modified vinyl polymers, metals and metal oxides. Thin film coatings of poly(alkenamers) will be constructed by surface graft metathesis from modified metal, metal oxide, and vinyl polymer surfaces. This research uses innovative methods to produce a variety of new materials, including some that have new types of structure on the surfaces of polymers. The properties of these new materials should be of considerable interest.