α,ω-epoxide, oxetane, and dithiocarbonate telechelic copolyolefins Access by ring-opening metathesis/cross-metathesis polymerization (ROMP/CM) of cycloolefins in the presence of functional symmetric chain-transfer agents

Abstract : Epoxide- and oxetane-α,ω-telechelic (co)polyolefins have been successfully synthesized by the tandem ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of cyclic olefins using Grubbs' second-generation catalyst (G2) in the presence of a bifunctional symmetric alkene epoxide- or oxetane-functionalized chain-transfer agent (CTA). From cyclooctene (COE), trans,trans,cis-1,5,9-cyclododecatriene (CDT), norbornene (NB), and methyl 5-norbornene-2-carboxylate (NBCOOMe), with bis(oxiran-2-ylmethyl) maleate (CTA 1), bis(oxetane-2-ylmethyl) maleate (CTA 2), or bis(oxetane-2-ylmethyl) (E)-hex-3-enedioate (CTA 3), well-defined α,ω-di(epoxide or oxetane) telechelic PCOEs, P(COE-co-NB or -NBCOOMe)s, and P(NB-co-CDT)swere isolated undermild operating conditions (40 or 60 °C, 24 h). The oxetane CTA3 and the epoxide CTA1were revealed to be significantly more efficient in the CM step than CTA 2, which apparently inhibits the reaction. Quantitative dithiocarbonatation (CS2/LiBr, 40 °C, THF) of an α,ω-di(epoxide) telechelic P(NB-co-CDT) afforded a convenient approach to the analogous α,ω-bis(dithiocarbonate) telechelic P(NB-co-CDT). The nature of the end-capping function of the epoxide/oxetane/dithiocarbonate telechelic P(NB-co-CDT)s did not impact their thermal signature, as measured by DSC. These copolymers also displayed a low viscosity liquid-like behavior and a shear thinning rheological behavior.
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E. Vanbiervliet, S. Fouquay, G. Michaud, F. Simon, J.-F. Carpentier, et al.. α,ω-epoxide, oxetane, and dithiocarbonate telechelic copolyolefins Access by ring-opening metathesis/cross-metathesis polymerization (ROMP/CM) of cycloolefins in the presence of functional symmetric chain-transfer agents. Polymers, MDPI, 2018, 10 (11), pp.1241. ⟨10.3390/polym10111241⟩. ⟨hal-01939035⟩

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