Controlled Alternating Metathesis Copolymerization of Terminal Alkynes.

Abstract

Terminal alkynes display high reactivity toward Ru-carbene metathesis catalysts. However, the formation of a less reactive bulky carbene hinders their homopolymerization. Simultaneously, the higher reactivity of alkynes does not allow efficient cross propagation with sterically less-hindered cycloalkene monomers, resulting in inefficient copolymerization. Nonetheless, terminal alkynes undergo rapid cross-metathesis with vinyl ethers. Therefore, an efficient cross propagation can be achieved with terminal alkynes and cyclic enol ether monomers. Here, we show that terminal alkyne derivatives can be copolymerized in an alternating fashion with 2,3-dihydrofuran using Grubbs' third generation catalyst (G3). A linear relationship of the number-average molecular weight versus monomer to initiator ratio and block copolymer synthesis confirmed a controlled copolymerization. The SEC and NMR analyses of the synthesized copolymers confirmed the excellent control over molecular weight and exclusive alternating nature of the copolymer. The regioselective chain transfer of G3 to vinyl ether and the high reactivity of the Fischer-type Ru carbene toward terminal alkynes was also exploited for polymer conjugation. Finally, the presence of an acid labile backbone functionality in the synthesized alternating copolymers allowed complete degradation of the copolymer within a short time interval which was confirmed by SEC analyses.