Addition homo- and copolymerization of 3-triethoxysilyltricyclo[4.2.1.02,5]non-7-ene

Аннотация

New norbornene type monomer bearing reactive triethoxysilyl group was synthesized, and its addition homo- and copolymerization with 3-trimethylsilyltricyclonon-7-ene was studied. The target monomer was obtained using regio- and stereospecific [2σ+2σ+2π] cyclo-addition of quadricyclane with vinyltrichlorosilane followed by the reaction of the formed cycloadduct with ethanol in the presence of triethylamine. Addition polymerization was investigated over the three-component Pd-containing catalytic system (Pd complex, Na+[B(3,5-(CF₃)₂C₆H₃)₄]–(cocatalyst) and tricyclohexylphosphine). The N-heterocyclic carbene Pd complex (SIPrPd(cinn)Cl) with high activity and tolerance to the Si—O—C moieties was used as a catalyst. The yields of the homo- and copolymers were 24—68% depending on the monomer (comonomer): Pd: B: PCy₃ ratio. The obtained addition polymers are high-molecular-weight amorphous products, the glass transition temperature of which exceeds 300 °C. The presence of reactive Si(OC₂H₅)₃ groups in the homo- and copolymers made it possible to carry out a hard-to-realize cross-linking involving side substituents and followed by the formation of insoluble polymers.