Cross-Metathesis between Polynorbornene and Poly(5,6-epoxy-1-octenamer)
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The macromolecular reaction of interchain cross-metathesis between polynorbornene and poly(5,6-epoxy-1-octenamer) in the presence of the first-generation Grubbs catalyst is studied. Chemically stable poly(5,6-epoxy-1-octenamer) is obtained through metathesis polymerization of 5,6-epoxycyclooct-1-ene with the second-generation Grubbs ruthenium catalyst. New random multiblock copolymers of norbornene and 5,6-epoxycyclooct-1-ene with different average block lengths determined by the reaction time, solvent type, and concentrations of the catalyst and initial homopolymers are synthesized and characterized by NMR, GPC, and DSC. Despite a distance between the epoxy substituent and the reaction center (double bond), poly(5,6-epoxy-1-octenamer) shows a lower activity in the cross-metathesis reaction with polynorbornene compared to unsubstituted polyoctenamer. The influence of epoxy groups present in the backbones of homopolymer and norbornene–cyclooctene multiblock copolymers on their thermal characteristics is studied. It is shown that the glass transition and melting temperatures increase with the concentration of epoxy groups upon the incorporation of an oxirane fragment into both homopolymers and copolymers. The crystallinity of poly(5,6-epoxy-1-octenamer) increases with the content of trans-С=С bonds in the polymer.
The authors are grateful to S.A. Korchagina for the GPC analyses. The structure of the obtained compounds was studied using the equipment of the Shared Research Center of the Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences and the Center for Molecular Structure Studies of the Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences.
This work was supported by the Russian Foundation for Basic Research (project no. 16-33-60213), and carried out within the State Program of Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences.
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