Simple access to alkoxysilyl telechelic polyolefins from ruthenium-catalyzed cross-metathesis depolymerization of polydienes

Michel, Xiaolu; Fouquay, Stéphane; Michaud, Guillaume; Simon, Frédéric; Brusson, Jean-Michel; Carpentier, Jean‐François; Guillaume, Sophie M.

doi:10.1016/j.eurpolymj.2017.09.027

Cited by 27 publications

(33 citation statements)

References 37 publications

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“…For years, the cross metathesis involving double bonds in the polymer backbone was considered as an undesired chain-transfer process that broadens molecular mass distribution, leads to the formation of cyclooligomers and reshuffling of monomer units in the course of the polymer synthesis [77]. The cross metathesis reactions on polymers were mostly studied with regard to the intramolecular polymer–catalyst interactions [77–79] or intermolecular degradation of polymers via the cometathesis with different olefins [77,80–81]. Only recently, the cross metathesis between macromolecules, or macromolecular cross metathesis (MCM), began to be considered as a promising reaction for various applications [82–93].…”

Section: Reviewmentioning

confidence: 99%

Olefin metathesis in multiblock copolymer synthesis

Gringolts

Denisova

Финкельштейн

et al. 2019

Beilstein J. Org. Chem.

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Multiblock copolymers constitute a basis for an emerging class of nanomaterials that combine various functional properties with durability and enhanced mechanical characteristics. Our mini-review addresses synthetic approaches to the design of multiblock copolymers from unsaturated monomers and polymers using olefin metathesis reactions and other ways of chemical modification across double C=C bonds. The main techniques, actively developed during the last decade and discussed here, are the coupling of end-functionalized blocks, sequential ring-opening metathesis polymerization, and cross metathesis between unsaturated polymers, or macromolecular cross metathesis. The last topic attracts special interest due to its relative simplicity and broad opportunities to tailor the structure and hence the properties of the copolymer products. Whenever possible, we analyze the structure–property relations for multiblock copolymers and point to their possible practical applications.

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Section: Reviewmentioning

confidence: 99%

Olefin metathesis in multiblock copolymer synthesis

Gringolts

Denisova

Финкельштейн

et al. 2019

Beilstein J. Org. Chem.

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“…[23][24][25] Nitrile butadiene rubber (NBR) is of primary interest in the automotive industry, on oil fields, and in aerospace due to its excellent oil and chemical resistance, low temperature flexibility, and high pressure and wear resistance. [26][27][28] Despite its many advantages, NBR has some disadvantages, including its swelling in aromatic and polar solvents and a maximum continuous operating temperature below 110°C. To enable its use at higher temperatures (maximum 150°C), we carried out the selective hydrogenation of NBR to prepare hydrogenated nitrile butadiene rubber (HNBR) [29] (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

“…Nitrile butadiene rubber (NBR) is of primary interest in the automotive industry, on oil fields, and in aerospace due to its excellent oil and chemical resistance, low temperature flexibility, and high pressure and wear resistance . Despite its many advantages, NBR has some disadvantages, including its swelling in aromatic and polar solvents and a maximum continuous operating temperature below 110 °C.…”

Section: Introductionmentioning

confidence: 99%

One‐step Synthesis of End‐Functionalized Hydrogenated Nitrile‐Butadiene Rubber by Combining the Functional Metathesis with Hydrogenation

Liu

Sun²,

Zhang

et al. 2020

ChemistryOpen

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End‐functionalized hydrogenated polymers obtained from nitrile‐butadiene rubber (NBR) yield new materials with suitable properties for a number of applications as sealing material and adhesives. We investigated the one‐step synthesis of ester end‐functionalized hydrogenated nitrile‐butadiene rubber (EF‐HNBR) by combining the functional metathesis with the hydrogenation of NBR in the presence of the 2nd generation Grubbs catalyst and a functionalized olefin as a chain transfer agent (CTA). We established the operating conditions for the effective production of saturated functional polymers with a high degree of hydrogenation, high chemo‐selectivity and moderate molecular weight. The structures of the products were confirmed by FT‐IR and 1H‐NMR spectroscopy, rubber molecular weight, and distribution determined by using gel permeation chromatography (GPC); their thermal properties were determined by thermo‐gravimetric analysis (TGA) and different scanning calorimetry (DSC).

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“…Tandem ROMP/CM of various cyclic olefins have, thus, enabled the synthesis of a wide range of α,ω-difunctional POs featuring end-capping groups as diverse as acetoxy, carboxylate, halide, pseudo-halide, hydroxyl, and cross-linkable epoxide or methacrylate [14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33]. Recent advances in our group enlarged the family of telechelic (co)polyolefins ((co)POs) derived from methathesis routes to alkoxysilyl, azlactone, (thio)carbonate, and epoxide end-capped polymers [34,35,36,37,38,39,40,41,42]. We report herein on the synthesis and characterization of epoxide, oxetane, and dithiocarbonate α,ω-difunctional (co)POs through the ROMP/CM of some cyclic olefins, namely cyclooctene (COE), trans , trans , cis -1,5,9-cyclododecatriene (CDT), norbornene (NB), and methyl 5-norbornene-2-carboxylate (NB COOMe ), using G2 in the presence of the corresponding epoxide or oxetane functional symmetrical CTA.…”

Section: Introductionmentioning

confidence: 99%

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

Vanbiervliet

Fouquay²,

Michaud³

et al. 2018

Polymers

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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.

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Simple access to alkoxysilyl telechelic polyolefins from ruthenium-catalyzed cross-metathesis depolymerization of polydienes

Abstract: The first functional cross-metathesis (CM) depolymerization of commercial (co)polydienes using a ruthenium catalyst and an acyclic bis (

Cited by 27 publications

References 37 publications

Olefin metathesis in multiblock copolymer synthesis

Olefin metathesis in multiblock copolymer synthesis

One‐step Synthesis of End‐Functionalized Hydrogenated Nitrile‐Butadiene Rubber by Combining the Functional Metathesis with Hydrogenation

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

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