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End-functional poly(methyl methacrylate)s via group transfer polymerization
Authors:Rudhramyna Gnaneshwar  Swaminathan Sivaram
Institution:Division of Polymer Science and Engineering, National Chemical Laboratory, Pune 411 008, India
Abstract:Hydroxyl-, amine-, and lactone-end-functional poly(methyl methacrylate)s (PMMA) were prepared with controlled molecular weights and Mw/Mn = 1.06–1.19 via group transfer polymerization. This was achieved by the electrophilic termination of silyl ketene acetal ended PMMAs with benzaldehyde, N-trimethylsilyl benzaldimine, and 5,6-dihydro-2H-pyran-2-one, respectively. The number-average degree of functionalization, as determined by NMR/SEC, was in the range of 0.70–0.85. A Lewis acid was used for terminating silyl ketene acetal ended PMMA with N-trimethylsilyl benzaldimine, whereas tetra-n-butyl ammonium bibenzoate was used in the case of benzaldehyde and 5,6-dihydro-2H-pyran-2-one. MALDI-TOF MS analysis of the end-functional polymers indicated the competing formation of cyclic end groups due to a back-biting reaction along with end-functional PMMAs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2514–2531, 2007
Keywords:α  β-unsaturated lactones  back-biting  degree of functionality  electrophilic termination  end-functional polymers  functionalization  GTP  hydroxyl  amine-terminal polymers  living anionic polymerization  MALDI-TOF MS  PMMA  silyl ketene acetal ended poly(methyl methacrylate)
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