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  • LA_BL_copolymerization_revised_manuscript_FINAL_2020_10_23

    Rights statement: 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

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

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Precise Microstructure Control in Poly(hydroxybutyrate- co-lactic Acid) Copolymers Prepared by an Yttrium Amine Bis(phenolate) Complex. / Platel, R.H.; Hurst, A.R.
In: Macromolecules, Vol. 53, No. 24, 22.12.2020, p. 10773-10784.

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Platel RH, Hurst AR. Precise Microstructure Control in Poly(hydroxybutyrate- co-lactic Acid) Copolymers Prepared by an Yttrium Amine Bis(phenolate) Complex. Macromolecules. 2020 Dec 22;53(24):10773-10784. Epub 2020 Dec 4. doi: 10.1021/acs.macromol.0c01214

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@article{9079714f27a344a2bd690f7032996a9b,
title = "Precise Microstructure Control in Poly(hydroxybutyrate- co-lactic Acid) Copolymers Prepared by an Yttrium Amine Bis(phenolate) Complex",
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. ",
keywords = "Amides, Lactic acid, Microstructure, Monomers, Nuclear magnetic resonance spectroscopy, Amide complexes, Composition ranges, Copolymer compositions, Copolymer microstructures, Hydroxybutyrate, Microstructure control, Reaction monitoring, Ring opening copolymerization, Yttrium compounds",
author = "R.H. Platel and A.R. Hurst",
note = "This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright {\textcopyright} 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",
year = "2020",
month = dec,
day = "22",
doi = "10.1021/acs.macromol.0c01214",
language = "English",
volume = "53",
pages = "10773--10784",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "24",

}

RIS

TY - JOUR

T1 - Precise Microstructure Control in Poly(hydroxybutyrate- co-lactic Acid) Copolymers Prepared by an Yttrium Amine Bis(phenolate) Complex

AU - Platel, R.H.

AU - Hurst, A.R.

N1 - 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

PY - 2020/12/22

Y1 - 2020/12/22

N2 - 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.

AB - 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.

KW - Amides

KW - Lactic acid

KW - Microstructure

KW - Monomers

KW - Nuclear magnetic resonance spectroscopy

KW - Amide complexes

KW - Composition ranges

KW - Copolymer compositions

KW - Copolymer microstructures

KW - Hydroxybutyrate

KW - Microstructure control

KW - Reaction monitoring

KW - Ring opening copolymerization

KW - Yttrium compounds

U2 - 10.1021/acs.macromol.0c01214

DO - 10.1021/acs.macromol.0c01214

M3 - Journal article

VL - 53

SP - 10773

EP - 10784

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 24

ER -