Syntheses of polynorbornadienes by ring-opening metathesis polymerizations of symmetric and non-symmetric 2,3-bis(alkoxycarbonyl)norbornadienes and their conversion to half-ester derivatives

Abstract

Libraries of polynorbornadienes were synthesized with good yields with a ruthenium-containing 2nd generation Grubbs catalyst by ring-opening metathesis polymerization (ROMP) of a variety of symmetric and non-symmetric 2,3-bis(alkoxycarbonyl)norbornadiene monomer units prepared from the half-esters obtained efficiently by the selective monohydrolysis reactions of symmetric diesters we reported earlier. Among these polymers, the polynorbornadienes with t-butoxycarbonyl groups derived from non-symmetric monomer units were converted to the half-ester derivatives by deprotection with trifluoroacetic acid, yielding amphiphilic polymers. The hydrogenation reactions of the obtained polymers were carried out to yield polymers having saturated structures in the main chains for improvement of the thermal stabilities. All these polymers were characterized by their molecular weights and thermal properties along with the spectroscopic data. Our selective monohydrolysis reactions have been proven to be a versatile tool for production of relatively homogeneous polymer libraries.