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Conformational influence of fluorinated building blocks on the physical properties of polyesters

Conformational influence of fluorinated building blocks on the physical properties of polyesters
Conformational influence of fluorinated building blocks on the physical properties of polyesters

The interplay of the relative configuration of diastereomeric vicinal difluoride groups on the conformational properties of polyesters has been investigated and compared to their non-fluorinated and per-fluorinated counterparts. The incorporation of syn and meso vicinal difluoride units in the polymer backbone was expected to influence the rigidity and stacking behaviour of the polymers in a significant way, and therefore to result in different thermal properties, such as melting point and melting enthalpy. Both syn and meso-2,3-difluoro butanediol have been reacted with the diester dimethyl succinate, leading to the formation of polyesters that have been characterized with 1H, 13C and 19F NMR. The polyesters showed molar masses up to 20 kg/mol (SEC). Surprisingly, the syn and meso-polymers displayed identical crystallization and melting behaviour. In contrast, differences were observed in the crystallization kinetics and melting points of syn and meso oligomers. Relying on time-resolved synchrotron SAXS and WAXD experiments, the complex multiple melting behaviour of these oligomers was explained in terms of crystal size and surface effects. The slower crystallization kinetics for the meso oligomers was tentatively associated with a stronger tendency to adopt gauche configurations. Apparently, such effects no longer affect the crystallization kinetics when larger polymers crystallize. It was also found that the syn and meso-polymers have identical equilibrium melting points and melting enthalpies notwithstanding molecular and crystallographic differences.

Diastereoisomers, Fluorinated building blocks, Polyesters
0032-3861
134-141
Lingier, Sophie
bda2b353-6fe0-4e59-ba6e-307770976906
Szpera, Robert
fc00a238-112f-4646-9783-6f9309456c09
Goderis, Bart
cff5edb4-d636-4e06-a8ef-b2a880b41182
Linclau, Bruno
19b9cacd-b8e8-4c65-af36-6352cade84ba
Du Prez, Filip E.
55b97c45-9cda-4d94-a22a-656f301a17ba
Lingier, Sophie
bda2b353-6fe0-4e59-ba6e-307770976906
Szpera, Robert
fc00a238-112f-4646-9783-6f9309456c09
Goderis, Bart
cff5edb4-d636-4e06-a8ef-b2a880b41182
Linclau, Bruno
19b9cacd-b8e8-4c65-af36-6352cade84ba
Du Prez, Filip E.
55b97c45-9cda-4d94-a22a-656f301a17ba

Lingier, Sophie, Szpera, Robert, Goderis, Bart, Linclau, Bruno and Du Prez, Filip E. (2019) Conformational influence of fluorinated building blocks on the physical properties of polyesters. Polymer, 164, 134-141. (doi:10.1016/j.polymer.2019.01.014).

Record type: Article

Abstract

The interplay of the relative configuration of diastereomeric vicinal difluoride groups on the conformational properties of polyesters has been investigated and compared to their non-fluorinated and per-fluorinated counterparts. The incorporation of syn and meso vicinal difluoride units in the polymer backbone was expected to influence the rigidity and stacking behaviour of the polymers in a significant way, and therefore to result in different thermal properties, such as melting point and melting enthalpy. Both syn and meso-2,3-difluoro butanediol have been reacted with the diester dimethyl succinate, leading to the formation of polyesters that have been characterized with 1H, 13C and 19F NMR. The polyesters showed molar masses up to 20 kg/mol (SEC). Surprisingly, the syn and meso-polymers displayed identical crystallization and melting behaviour. In contrast, differences were observed in the crystallization kinetics and melting points of syn and meso oligomers. Relying on time-resolved synchrotron SAXS and WAXD experiments, the complex multiple melting behaviour of these oligomers was explained in terms of crystal size and surface effects. The slower crystallization kinetics for the meso oligomers was tentatively associated with a stronger tendency to adopt gauche configurations. Apparently, such effects no longer affect the crystallization kinetics when larger polymers crystallize. It was also found that the syn and meso-polymers have identical equilibrium melting points and melting enthalpies notwithstanding molecular and crystallographic differences.

Text
Lingier et al - Fluorpolymers REVISION-14122018_BL - Accepted Manuscript
Restricted to Repository staff only until 8 January 2020.
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Accepted/In Press date: 6 January 2019
e-pub ahead of print date: 8 January 2019
Published date: 15 February 2019
Keywords: Diastereoisomers, Fluorinated building blocks, Polyesters

Identifiers

Local EPrints ID: 427867
URI: https://eprints.soton.ac.uk/id/eprint/427867
ISSN: 0032-3861
PURE UUID: 7f38e877-9ae7-4ca7-8e32-46d503d1148c
ORCID for Bruno Linclau: ORCID iD orcid.org/0000-0001-8762-0170

Catalogue record

Date deposited: 30 Jan 2019 17:30
Last modified: 20 Jul 2019 01:07

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Contributors

Author: Sophie Lingier
Author: Robert Szpera
Author: Bart Goderis
Author: Bruno Linclau ORCID iD
Author: Filip E. Du Prez

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