Homo-, co- and terpolymerization of 1,5-hexadiene using a methylalumoxane activated mono-Cp-amido-complex

Homo- and copolymerizations of 1,5-hexadiene with ethene and styrene using halfsandwich metallocene catalyst Me2Si(Me4Cp)(N-tert-butyl)TiCl2 / MAO (Cp=cyclopentadienyl, Me=methyl, MAO=methylalumoxane) were investigated. According to 13C-NMR spectroscopic microstructure analysis, cyclopolymerization of 1,5-hexadiene afforded randomly distributed cis- and trans-cyclopentane rings in the homo- and copolymer backbone. 1,5-hexadiene incorporation reached 52 mol-%. The ratio of vinyl side chains to cyclopentane rings was controlled by 1,5-hexadiene concentration, where low 1,5-hexadiene concentration promoted cyclopolymerization. Copolymer glass transition temperatures increased with increasing content of cyclic units in the backbone. Styrene was used successfully as termonomer in ethene/1,5-hexadiene polymerization, resulting in a semicrystalline terpolymer with cyclic and styrenic units in the polymer backbone.