Synthesis of Four-Arm Star Poly(L-Lactide) Oligomers Using an In Situ-Generated Calcium-Based Initiator
Identifieur interne : 003427 ( PascalFrancis/Curation ); précédent : 003426; suivant : 003428Synthesis of Four-Arm Star Poly(L-Lactide) Oligomers Using an In Situ-Generated Calcium-Based Initiator
Auteurs : Karina A. George [Australie] ; François Schue [France] ; Traian V. Chirlla [Australie] ; Edeline Wentrup-Byrne [Australie]Source :
- Journal of polymer science. Part A. Polymer chemistry [ 0887-624X ] ; 2009.
Descripteurs français
- Pascal (Inist)
English descriptors
- KwdEn :
Abstract
Using an in situ-generated calcium-based initiating species derived from pentaerythritol, the bulk synthesis of well-defined four-arm star poly(L-lactide) oligomers has been studied in detail. The substitution of the traditional initiator, stannous octoate with calcium hydride allowed the synthesis of oligomers that had both low PDIs and a comparable number of polymeric arms (3.7-3.9) to oligomers of similar molecular weight. Investigations into the degree of control observed during the course of the polymerization found that the insolubility of pentaerythritol in molten L-lactide resulted in an uncontrolled polymerization only when the feed mole ratio of L-lactide to pentaerythritol was 13. At feed ratios of 40 and greater, a pseudoliving polymerization was observed. As part of this study, in situ FT-Raman spectroscopy was demonstrated to be a suitable method to monitor the kinetics of the ring-opening polymerization of lactide. The advantages of using this technique rather than FTIR-ATR and 1H NMR for monitoring L-lactide consumption during polymerization are discussed.
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<front><div type="abstract" xml:lang="en">Using an in situ-generated calcium-based initiating species derived from pentaerythritol, the bulk synthesis of well-defined four-arm star poly(L-lactide) oligomers has been studied in detail. The substitution of the traditional initiator, stannous octoate with calcium hydride allowed the synthesis of oligomers that had both low PDIs and a comparable number of polymeric arms (3.7-3.9) to oligomers of similar molecular weight. Investigations into the degree of control observed during the course of the polymerization found that the insolubility of pentaerythritol in molten L-lactide resulted in an uncontrolled polymerization only when the feed mole ratio of L-lactide to pentaerythritol was 13. At feed ratios of 40 and greater, a pseudoliving polymerization was observed. As part of this study, in situ FT-Raman spectroscopy was demonstrated to be a suitable method to monitor the kinetics of the ring-opening polymerization of lactide. The advantages of using this technique rather than FTIR-ATR and <sup>1</sup>
H NMR for monitoring <sub>L</sub>
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