ИСТИНА

The glassy polymers containing Si-O bonds could be employed for membrane gas separation of hydrocarbon mixtures. For instance, addition poly(3-(tris-(trimethylsiloxy)silyl)tricyclononene) possesses a high butane/methane permselectivity [1]. In this work we successfully synthesized a series of metathesis and addition polynorbornenes bearing trialkoxysilyl groups and studied their properties. The 2-stage synthesis of new monomers, 3-trialkoxysilyltricyclo[4.2.1.02,5]non-7-enes (alkoxy = OMe, OEt, OPr, OBu), is described. The synthesis was realized by means of [2σ+2σ+2π]-cycloaddition of quadricyclane and vinyltrichlorosilane followed by treating the product with corresponding alcohol. This monomer series proved to be active in ring opening metathesis polymerization (ROMP) and addition polymerization (AP). For the ROMP 1-st generation Grubbs catalyst was used. The formed polymers turned out to be amorphous, high-molecular weight, and glassy or rubbery products depending on the length of alkoxy group. For AP different Pd-based complexes were used as catalysts with various B-based compounds, as cocatalysts. The optimal conditions of AP were found for this series of monomers. Amorphous high-molecular weight glassy polymers were successfully obtained and studied. Additionally, the synthesis of a new silatrane-containing monomer, 3-silatranyltricyclo[4.2.1.02,5]non-7-ene, was developed. This monomer was obtained by reaction of 3-trimethoxysilyltricyclo[4.2.1.02,5]non-7-ene with equimolar amount of triethanolamine. The silatrane-containing monomer turned out to be active in ROMP, which resulted in the formation of amorphous high-polymeric glassy polymer. AP in the presence of Pd-complexes with various B- or Al-organic compounds led to the formation of insoluble oligomers and polymers. This work was sponsored by RSF grant №17-19-01595.