Postpolymerization modification of reactive polymers derived from vinylcyclopropane : III. polymer sequential functionalization using a combination of amines with alkoxyamines, hydracides, isocyabares, or acyl halides

A new 1,1-disubstituted-2-vinylcyclopropane monomer bearing a ketone and a pentafluorophenyl ester was synthesized and successfully polymerized to yield a polymer with two side chain moieties readily available for post-polymerization modification. After a quantitative modification of the pentafluorophenyl moiety with amines, a subsequent second functionalization reaction was successfully performed on the ketone moiety leading to a double side-chain functionalized polymer using two different routes. The first route utilized hydrazide and hydroxylamine derivatives leading to a ketone conversion of 25 to 85%. In the second route, the ketone moiety was first reduced to alcohol (reduction conversion up to 100%) and then converted into the corresponding ester or urethane using acyl halides or isocyanates, respectively, with a conversion ratio of up to 90%. A library of functionalized polymers was synthesized to confirm the effectiveness of this approach.