Precise Microstructure Control in Poly(hydroxybutyrate- co-lactic Acid) Copolymers Prepared by an Yttrium Amine Bis(phenolate) Complex

Platel, R.H. and Hurst, A.R. (2020) Precise Microstructure Control in Poly(hydroxybutyrate- co-lactic Acid) Copolymers Prepared by an Yttrium Amine Bis(phenolate) Complex. Macromolecules, 53 (24). pp. 10773-10784. ISSN 0024-9297

[thumbnail of LA_BL_copolymerization_revised_manuscript_FINAL_2020_10_23]
Text (LA_BL_copolymerization_revised_manuscript_FINAL_2020_10_23)
LA_BL_copolymerization_revised_manuscript_FINAL_2020_10_23.pdf - Accepted Version
Available under License Creative Commons Attribution-NonCommercial.

Download (919kB)

Abstract

A diamino-bis(phenolate) yttrium amide complex, 1, was used as an initiator in the ring-opening copolymerization of rac-lactide (rac-LA) and rac-β-butyrolactone (rac-β-BL) in toluene at ambient temperature. Copolymers were prepared across a wide composition range (10-89% LA content), and the copolymer composition closely matched the monomer feed ratio. The copolymers had Tg values ranging from 3.8 °C (for a copolymer with 10% LA content) to 44.0 °C (for a copolymer with 89% LA content). Tm ranged from 132 to 144 °C for copolymers with LA composition 48-10%. The copolymer microstructure was determined using 1H and 13C{1H} NMR spectroscopy of copolymers and through reaction monitoring by NMR spectroscopy. This revealed that no BB diads are formed in the copolymer in the presence of any rac-LA monomer, even at very high concentrations of rac-β-BL. However, when [LA] = 0, rac-β-BL is rapidly polymerized. The copolymers thus have a microstructure consisting of two distinct regions, one containing both LA and BL units in an even distribution and one containing solely BL or LA units, depending on the monomer feed ratio.

Item Type:
Journal Article
Journal or Publication Title:
Macromolecules
Additional Information:
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.macromol.0c01214
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/2500/2505
Subjects:
?? amideslactic acidmicrostructuremonomersnuclear magnetic resonance spectroscopyamide complexescomposition rangescopolymer compositionscopolymer microstructureshydroxybutyratemicrostructure controlreaction monitoringring opening copolymerizationyttrium comp ??
ID Code:
151196
Deposited By:
Deposited On:
29 Jan 2021 21:12
Refereed?:
Yes
Published?:
Published
Last Modified:
12 Dec 2023 01:50