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Enantiopure Isotactic PCHC Synthesized by Ring-Opening Polymerization of Cyclohexene Carbonate

Abstract : The ring-opening polymerization (ROP) of racemic trans-cyclohexene carbonate (rac-CHC) and enantiopure trans-(R,R)-CHC is successfully carried out with various catalyst systems. Poly(cyclohexene carbonate) (PCHC) with a slight isotactic bias (Pm = ca. 60–76%) is obtained by ROP of rac-CHC catalyzed by zinc diaminophenolate, zinc β-diketiminate, yttrium bis(phenolate), or 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) in combination with an alcohol as a co-initiator. Purely isotactic PCHC is synthesized for the first time via ROP of enantiopure (R,R)-CHC with a zinc/benzyl alcohol catalyst system. All reactions proceed without decarboxylation, affording well-defined PCHCs with Mn,NMR up to 17 000 g mol–1 and ĐM = ca. 1.2. Purely isotactic PCHC is semicrystalline, with Tg = 130 °C, Tc = 162 °C, and Tm = 248 °C. DFT computations further highlight the significant favorable impact of the trans-cyclohexane ring-strain to enable the ROP of CHC, as opposed to meso-CHC which is unreactive.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01114335
Contributor : Laurent Jonchère <>
Submitted on : Monday, February 9, 2015 - 11:38:24 AM
Last modification on : Thursday, March 5, 2020 - 2:06:15 PM

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William Guerin, Abdou Khadri Diallo, Evgueni Kirilov, Marion Helou, Martine Slawinski, et al.. Enantiopure Isotactic PCHC Synthesized by Ring-Opening Polymerization of Cyclohexene Carbonate. Biomacromolecules, American Chemical Society, 2014, 47 (13), pp.4230-4235. ⟨10.1021/ma5009397⟩. ⟨hal-01114335⟩

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