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Journal articles
alpha,omega-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 alpha,omega-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)(3)SiCH2CH=CHCH2Si(OMe)(3) (2) and (MeO)(3)Si(CH2)(3)NHC(O)OCH2CH=CHCH2OC(O)NH (CH2)(3)Si(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' 2nd-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).
Cited literature [39 references]
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01357417
Contributor : Laurent Jonchère <>
Submitted on : Friday, December 2, 2016 - 1:36:55 PM
Last modification on : Wednesday, April 7, 2021 - 3:18:08 PM
Contributor : Laurent Jonchère <>
Submitted on : Friday, December 2, 2016 - 1:36:55 PM
Last modification on : Wednesday, April 7, 2021 - 3:18:08 PM
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