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Controlled free radical ring-opening polymerization and chain extension of the living polymer
Abstract
Free radical ring-opening polymerization of 2-methylene-1,3-dioxepane (MDP) in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO) has been achieved to afford a chain polyester (PMDP) with di-t-butyl peroxide (DTBP) as an initiator at 125°C. The polydispersity of the polymers decreases as the concentration of TEMPO is increased. At high TEMPO concentrations, the polydispersity as low as 1.2 was obtained, which is below the theoretical lower limit for a conventional free radical polymerization. A linear relationship between the number-average molecular weight (Mn) and the monomer conversion was observed with the best-fit line passing very close to the origin of the Mn-conversion plot. The isolated and purified TEMPO-capped PMDP polymers have been employed to prepare chain extended polymers upon addition of more MDP monomer. These results are suggestive of the “living” polymerization process. A possible polymerization mechanism might involve thermal homolysis of the TEMPO-PMDP bonds followed by the addition of the monomers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 761–771, 1998
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“It is clear that by varying the monomers or their proportions, or indeed by varying the mode of initiation, e.g., NMP (nitroxide mediated polymerization) [35], RAFT (reversible addition fragmentation transfer polymerization) [36] or ATRP (atom transfer radical polymerization) [37] many and varied polymers can be obtained, optimized for their use in agricultural, medicinal or pharmaceutical fields.”
From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [35]
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- Authors
- Wei, Y., Connors, E. J., Jia, X., & Wang, C.
- Venue
- Journal of Polymer Science Part A: Polymer Chemistry
- Published
- 1998
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- Wei, Y., Connors, E. J., Jia, X., & Wang, C. (1998). Controlled free radical ring-opening polymerization and chain extension of the living polymer. Journal of Polymer Science Part A: Polymer Chemistry. https://doi.org/10.1002/(sici)1099-0518(19980415)36%3A5
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