Synthesis of new multiblock copolymers via cross-metathesis reaction of polytrimethylsilylnorbornene and polycyclooctene

Abstract

The cross-metathesis reaction between polytrimethylsilylnorbornene and polycyclooctene is investigated for the first time. Using the Grubbs Ru-carbene complex of the first generation, the synthesis of random multiblock copolymers of trimethylsilylnorbornene and cyclooctene is carried out. The effect of the reaction conditions on the block length and thermal and crystalline properties of new copolymers is studied by NMR, GPC, and DSC methods. With the use of in situ 1Н NMR spectroscopy, the kinetics of the crossmetathesis reaction is investigated. As for unsubstituted polynorbornene (Polym. Sci., Ser. B 58, 292 (2016)), the catalyst interacts initially with polycyclooctene, giving a polymer carbene complex [Ru]=PCO. Further, this complex attacks the polytrimethylsilylnorbornene chain via cross reaction with formation of complex [Ru]=PNB-Si and a diblock copolymer of trimethylsilylnorbornene and cyclooctene as reaction products. The subsequent cross reactions form a multiblock copolymer with gradually increasing block length. Throughout the entire process, the concentration of [Ru]=PCO exceeds the concentration of [Ru]=PNB-Si by more than two orders of magnitude. Simultaneously, the total concentration of carbene complexes decreases in time through their decay. The reaction kinetics is satisfactorily described by a model proposed previously for interaction between polycyclooctene and polynorbornene.