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Title: Controllable synthesis of bio-based polylactide diols using an organocatalyst in solvent-free conditions
Authors: Li, H
Gu, L 
Keywords: Living polymerization
Polylactide diol
Renewable resource
Ring-opening polymerization
Issue Date: 2018
Publisher: John Wiley & Sons
Source: Journal of polymer science. Part A, Polymer chemistry, 2018, v. 56, no. 9, p. 968-976 How to cite?
Journal: Journal of polymer science. Part A, Polymer chemistry 
Abstract: Controllable synthesis of bio-based polylactide (PLA) diols was realized by the ring-opening polymerization (ROP) of lactide (LA) in the presence of 1,4-butanediol (BDO) using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an organocatalyst in solvent-free conditions. The catalytic activity and conversion of LA could reach ∼1 kg g−1 DBU and >97%, respectively, and the polymerization yielded polymers with narrow polydispersity index (PDI) (1.15–1.29). Interestingly, the number average molecular weight (Mn) of the obtained PLA diol was in excellent linear relation with the molar ratio of LA and BDO, and hence can be precisely controlled. The structure of the diol was clearly confirmed by 1H and 13C NMR, FTIR, and MALDI-TOF mass spectra, proving BDO as an initiation-transfer agent to participate in the polymerization. Kinetic study of the ROP demonstrates a pseudo-first-order kinetic model and a controlled “living” nature. Notably, it is found that the glass transition temperature (Tg) of the diol significantly depends on the Mn. Furthermore, various chain transfer agents and organocatalysts can also be used to successfully synthesize well-defined PLA diols. Especially, functional bio-based dihydric alcohols such as 2,5-furandimethanol (FDMO)-initiated ROP in this system could result in fully bio-based PLA diols with functionality.
ISSN: 0887-624X
EISSN: 1099-0518
DOI: 10.1002/pola.28974
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