Ultraproductive, zinc-mediated, immortal ring-opening polymerization of trimethylene carbonate.
Helou
Marion
M
Catalysis and Organometallics, UMR 6226 CNRS - Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex (France), Fax: (+33) 2-2323-6939.
Miserque
Olivier
O
Total Petrochemicals Research, Zone Industrielle C, 7181 Feluy (Belgium).
Brusson
Jean-Michel
JM
Total Petrochemicals Research, Zone Industrielle C, 7181 Feluy (Belgium).
Carpentier
Jean-François
JF
Catalysis and Organometallics, UMR 6226 CNRS - Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex (France), Fax: (+33) 2-2323-6939.
Guillaume
Sophie M
SM
Catalysis and Organometallics, UMR 6226 CNRS - Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex (France), Fax: (+33) 2-2323-6939.
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The moderate broadness of molar mass distribution values is typical for bulk polymerizations and reflects the occurrence of side processes (transfer and/or transesterification reactions) all along the propagation step.[2c, 4a]
For low-molar-mass PTMCs, determination of the number-average molar mass by 1H NMR spectroscopy [from the relative intensity of the signals of the methylene protons of the PTMC chains -CH2OC(O) to the α-hydroxymethylene or the benzyloxycarbonate hydrogen atoms] gave values in close agreement with the calculated ones; for instance, Mn=5750, 2800, and 11 000 for Table 1, entries 5, 6, and 11, respectively.
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Evaluation of the performances of the ZnEt2/BnOH analogous system revealed a similar activity and a control of the polymer molar features as good (M̄n theory=1950; M̄n SEC=2600, M̄w/M̄n=1.15; TOF=360) as those obtained with [Zn(bdi){N(SiMe3)2}]/BnOH (Table, 1, entry 9) under similar experimental conditions. Yet commercially available ZnEt2 displayed a lower efficiency with a similar conversion (90 %) being obtained within 2 h compared to 20 min for the β-diketiminate amide derivative. However, this ZnEt2/BnOH system was no longer active at higher [TMC]0/[BnOH]0 ratios.