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Polymers 2018, 10(11), 1241; https://doi.org/10.3390/polym10111241

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

1
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)—UMR 6226, F-35000 Rennes, France
2
BOSTIK S.A., 253, Avenue du Président Wilson, F-93211 La Plaine Saint-Denis, France
3
BOSTIK, ZAC du Bois de Plaisance, 101, Rue du Champ Cailloux, F-60280 Venette, France
*
Authors to whom correspondence should be addressed.
Received: 16 October 2018 / Revised: 3 November 2018 / Accepted: 4 November 2018 / Published: 9 November 2018
(This article belongs to the Special Issue Olefin Polymerization and Polyolefin)
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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)s were isolated under mild operating conditions (40 or 60 °C, 24 h). The oxetane CTA 3 and the epoxide CTA 1 were 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. View Full-Text
Keywords: chain-transfer agent; dithiocarbonate; epoxide; oxetane; functional polyolefin; ring-opening metathesis polymerization; telechelic polymer chain-transfer agent; dithiocarbonate; epoxide; oxetane; functional polyolefin; ring-opening metathesis polymerization; telechelic polymer
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Vanbiervliet, E.; Fouquay, S.; Michaud, G.; Simon, F.; Carpentier, J.-F.; Guillaume, S.M. 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 2018, 10, 1241.

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