Synthesis of AB diblock and ABA triblock copolymers comprised of polyisobutylene and poly(vinylferrocene) segments

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Tomoya Higashihara, tomoya_higashihara@uml.edu and Rudolf Faust, Rudolf_Faust@uml.edu. Department of Chemistry, University of Massachusetts Lowell, One University Avenue, Lowell, MA 01854
A novel series of AB diblock and ABA triblock copolymers (A = polyisobutylene (PIB), B= poly(vinylferrocene) (PVFe)) has been synthesized by efficient coupling reactions between living PVFe anions and highly reactive chlorosilyl mono- or di-functional PIBs that were successfully prepared via hydrosilation of the corresponding allyl functional PIBs using Karstedt's Pt(0) catalyst. The coupling efficiencies were excellent (> 95%) in all cases. The block copolymers synthesized possess predictable molecular weights, narrow molecular weight distributions, and compositional homogeneities as confirmed by GPC-MALLS and 1H NMR analyses. The two glass transition temperatures of PVFe-b-PIB-b-PVFe ABA triblock copolymer at –65 and 198 °C observed from DSC thermogram suggest microphase separated morphology.