Organocatalysts for the controlled "immortal" ring-opening polymerization of six-membered-ring cyclic carbonates: a metal-free, green process |
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Authors: | Helou Marion Miserque Olivier Brusson Jean-Michel Carpentier Jean-François Guillaume Sophie M |
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Institution: | Laboratoire Catalyse et Organométalliques, CNRS, Université de Rennes 1, Sciences Chimiques de Rennes (UMR 6226), Campus de Beaulieu, 35042 Rennes Cedex, France. |
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Abstract: | Six-membered cyclic carbonates, namely trimethylene carbonate (TMC), 3,3-dimethoxytrimethylene carbonate (DMTMC) and 3-benzyloxytrimethylene carbonate (BTMC), undergo controlled "immortal" ring-opening polymerization (iROP) under mild conditions (bulk, 60-150 °C), by using organocatalysts, including an amine 4-N,N-dimethylaminopyridine (DMAP)], a guanidine 1,5,7-triazabicyclo-4.4.0]dec-5-ene (TBD)], or a phosphazene 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP)], in the presence of an alcohol benzyl alcohol (BnOH), 1,3-propanediol (PPD), glycerol (GLY)] that acts as both a co-initiator and a chain-transfer agent. Remarkably, such organocatalysts remain highly active in the iROP of technical-grade, unpurified TMC. Under optimized conditions, as much as 100,000 equivalents of TMC were fully converted by as little as 10 ppm of BEMP with the simultaneous growth of as many as 200 polymer chains, allowing the preparation of high molar mass poly(trimethylene carbonate)s (up to 45,800 g mol(-1)). These catalyst systems enable among the highest activities (TOF=55,800 h(-1)) and productivities (TON=95,000) ever reported for the ROP of TMC. |
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Keywords: | carbonates organocatalysis polycarbonates ring‐opening polymerization trimethylene carbonate |
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