Ruthenium is a versatile catalyst that has revolutionized the field of macromolecular synthesis through techniques such as ring-opening metathesis polymerization (ROMP) and metal-catalyzed living radical polymerization (LRP). Although these two techniques are well-established from decades of research, the merger of ruthenium catalysis with other synthetic methods offers attractive opportunities for the development of novel polymers. In this talk, two such examples involving the combination of ruthenium-catalyzed polymerization with aryne chemistry or cyclic ketene acetal chemistry will be presented. Aryne chemistry was used to synthesize a series of benzonorbornadienes as monomers for ROMP. Previous reports have demonstrated the high susceptibility of poly(benzonorbornadienes) to oxidation at the benzylic/allylic position even under ambient conditions, which has hampered the study and application of these polymers. The use of aryne chemistry enabled access to monomers with substitution at the benzylic/allylic position in excellent yields, and the resulting polymers were stable to air. In the second example, a cyclic ketene acetal was used to introduce degradability to fluorous polymethacrylates synthesized by ruthenium-catalyzed LRP. The fluorous methacrylate content was found to modulate both the reactivity of the growing polymer chain towards ketene acetal as well as the degradation rate of the resulting polymer. The synthesis and characterization of these polymers and their possible applications will be presented.

Syntheses of new polymers using ruthenium catalysis

254th National Meeting (2017)

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