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From Epoxide to Cyclodithiocarbonate Telechelic Polycyclooctene through Chain-Transfer Ring-Opening Metathesis Polymerization (ROMP): Precursors to Non-Isocyanate Polyurethanes (NIPUs)

Abstract : Telechelic polycyclooctenes (PCOEs) have been successfully synthesized by ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of cyclooctene (COE) using Grubbs' second-generation catalyst (G2) in the presence of epoxide-functionalized chain-transfer agents (CTAs). The monofunctional epoxide oxiran-2-ylmethyl acrylate CTA (1) afforded the isomerized alpha-(glycidyl alkenoate),omega-propenyl functional (IMF) PCOEs. The use of 1,4-benzoquinone (BZQ) as additive completely inhibited the C=C isomerization process, thereby leading selectively to alpha-(glycidyl alkenoate),omega-vinyl telechelic (MF) PCOE. On the other hand, difunctional epoxide CTAs, bis(oxiran-2-ylmethyl) fumarate (3), bis(oxiran-2-ylmethyl) maleate (4), bis(oxiran-2-ylmethyl) (E)-hex-3-enedioate (5), and (Z)-1,4-bis(oxiran-2-ylmethoxy)but-2-ene (6), selectively afforded the corresponding alpha,omega-di(glycidyl alkenoate) telechelic PCOEs (DF) along with minor amounts of cyclic nonfunctional (CNF) PCOE. In the presence of these difunctional symmetric CTAs, the mechanism is proposed to proceed through a tandem one-pot CM/ROMP/ring-closing metathesis (RCM) approach. CM was more effective with Z- than E-configurated CTAs (4 > 6 >> 3 >> 5), regardless of the presence of a methylene group in-between the C=C double bond and the glycidyl moiety. Subsequent dithiocarbonatation of the alpha,omega-diepoxide telechelic PCOEs upon reaction with CS2 in the presence of LiBr quantitatively afforded the first examples of bis(cyclodithiocarbonate) end-functional PCOEs. Ensuing aminolysis of the bis(cyclodithiocarbonate) telechelic PCOEs with the polyether (triethylene glycol) diamine JEFFAMINE EDR-148 quantitatively afforded, at room temperature without any added catalyst, the desired poly(mercaptothiourethane)s NIPUs, as evidenced from FTIR spectroscopy, TGA, and DSC analyses.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01475457
Contributor : Laurent Jonchère <>
Submitted on : Monday, March 20, 2017 - 4:35:21 PM
Last modification on : Friday, July 10, 2020 - 4:19:49 PM

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Elise Vanbiervliet, Stéphane Fouquay, Guillaume Michaud, Frédéric Simon, Jean-François Carpentier, et al.. From Epoxide to Cyclodithiocarbonate Telechelic Polycyclooctene through Chain-Transfer Ring-Opening Metathesis Polymerization (ROMP): Precursors to Non-Isocyanate Polyurethanes (NIPUs). Macromolecules, American Chemical Society, 2017, 50 (1), pp.69-82. ⟨10.1021/acs.macromol.6b02137⟩. ⟨hal-01475457⟩

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