α,ω-Bis(trialkoxysilyl) difunctionalized polycyclooctenes from ruthenium-catalyzed chain-transfer ring-opening metathesis polymerization

Abstract

The ring-opening metathesis polymerization/cross-metathesis (ROMP/CM) of cyclooctene (COE) using bis(trialkoxysilyl)alkenes as chain-transfer agents (CTAs) and Ru catalysts to afford difunctionalized polyolefins is reported. The formation of α,ω-bis(trialkoxysilyl) telechelic polycycloolefins (DF) with controlled molar mass values takes place quite selectively (>90 wt%), along with minor amounts of cyclic non-functionalized polymers (CNF), as evidenced by NMR, MALDI-ToF MS, SEC analyses and fractionation experiments. The nature of the CTA and catalyst influenced much the efficiency and selectivity of the reaction. (MeO)₃SiCH₂CHCHCH₂Si(OMe)₃ (2) and (MeO)₃Si(CH₂)₃NHC(O)OCH₂CHCHCH₂OC(O)NH(CH₂)₃Si(OMe)₃ (5) proved to be the most efficient CTAs in terms of reactivity, catalyst productivity and selectivity towards DF. Diurethane CTA 5 is easily prepared, and can also be conveniently generated in situ during the ROMP/CM. Grubbs’ 2^nd-generation catalyst (G2) and Hoveyda–Grubbs's catalyst (HG2) afforded the best compromise in terms of selectivity and productivity, with turnover numbers of up to 95 000 mol(COE) mol(Ru)⁻¹ and 5000 mol(CTA) mol(Ru)⁻¹.