ma6b02137_si_001.pdf (3.57 MB)
From Epoxide to Cyclodithiocarbonate Telechelic Polycyclooctene through Chain-Transfer Ring-Opening Metathesis Polymerization (ROMP): Precursors to Non-Isocyanate Polyurethanes (NIPUs)
journal contributionposted on 2016-12-22, 18:34 authored by Elise Vanbiervliet, Stéphane Fouquay, Guillaume Michaud, Frédéric Simon, Jean-François Carpentier, Sophie M. Guillaume
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 α-(glycidyl alkenoate),ω-propenyl functional (IMF) PCOEs. The use of 1,4-benzoquinone (BZQ) as additive completely inhibited the CC isomerization process, thereby leading selectively to α-(glycidyl alkenoate),ω-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 α,ω-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 CC double bond and the glycidyl moiety. Subsequent dithiocarbonatation of the α,ω-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.
telechelic PCOEsepoxide-functionalized chain-transfer agentsSubsequent dithiocarbonatationDSC analysestriethylene glycolFTIR spectroscopyalkenoatemonofunctional epoxide oxiran -2-ylmethyl acrylate CTANon-Isocyanate PolyurethanesbiCyclodithiocarbonate Telechelic Polycyclooctenedifunctional epoxide CTAsMFmethylene group in-betweenBZQpresenceROMPDFring-opening metathesis polymerizationCMIMFTGAChain-Transfer Ring-Opening Metathesis Polymerizationglycidyl moietyRCMconfigurated CTAsroom temperatureCS 2diamine JEFFAMINE EDR -148CNFNIPUG 2Ensuing aminolysisTelechelic polycyclooctenes