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Comparison of Cyclic and Linear Poly(lactide)s Using Small-Angle Neutron Scattering

Yang, Philip B. ; Davidson, Matthew G. ; Edler, Karen J. LU orcid ; Leaman, Niamh LU ; Bathke, Elly K. LU ; McCormick, Strachan N. ; Matsarskaia, Olga and Brown, Steven (2022) In Macromolecules 55(24). p.11051-11058
Abstract
Small-angle neutron scattering (SANS) experiments were conducted on cyclic and linear polymers of racemic and l-lactides
(PLA) with the goal of comparing chain configurations, scaling, and
effective polymer–solvent interactions of the two topologies in acetone-d6 and THF-d8.
There are limited reports of SANS results on cyclic polymers due to the
lack of substantial development in the field until recently. Now that
pure, well-defined cyclic polymers are accessible, unanswered questions
about their rheology and physical conformations can be better
investigated. Previously reported SANS experiments have used cyclic and
linear polystyrene samples; therefore, our work... (More)
Small-angle neutron scattering (SANS) experiments were conducted on cyclic and linear polymers of racemic and l-lactides
(PLA) with the goal of comparing chain configurations, scaling, and
effective polymer–solvent interactions of the two topologies in acetone-d6 and THF-d8.
There are limited reports of SANS results on cyclic polymers due to the
lack of substantial development in the field until recently. Now that
pure, well-defined cyclic polymers are accessible, unanswered questions
about their rheology and physical conformations can be better
investigated. Previously reported SANS experiments have used cyclic and
linear polystyrene samples; therefore, our work allowed for direct
comparison using a contrasting (structurally and sterically) polymer. We
compared SANS results of cyclic and linear PLA samples with various
microstructures and molecular weights at two different temperatures,
allowing for comparison with a wide range of variables. The results
followed the trends of previous experiments, but much greater
differences in the effective polymer–solvent interaction parameters
between cyclic and linear forms of PLA were observed, implying that the
small form factor and hydrogen bonding in PLA allowed for much more
compact conformations in the cyclic form only. Also, the polymer
microstructure was found to influence polymer–solvent interaction
parameters substantially. These results illustrate how the difference in
polymer–solvent interactions between cyclic and linear polymers can
vary greatly depending on the polymer in question and the potential of
neutron scattering as a tool for identification and characterization of
the cyclic topology. (Less)
Please use this url to cite or link to this publication:
author
; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Macromolecules
volume
55
issue
24
pages
8 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:36590371
  • scopus:85144058211
ISSN
0024-9297
DOI
10.1021/acs.macromol.2c02020
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2022 American Chemical Society. All rights reserved.
id
8836e5f7-ca4a-480a-86ad-91ec9e5d16aa
date added to LUP
2023-01-18 08:56:37
date last changed
2024-05-30 14:14:45
@article{8836e5f7-ca4a-480a-86ad-91ec9e5d16aa,
  abstract     = {{Small-angle neutron scattering (SANS) experiments were conducted on cyclic and linear polymers of racemic and l-lactides<br>
 (PLA) with the goal of comparing chain configurations, scaling, and <br>
effective polymer–solvent interactions of the two topologies in acetone-<i>d</i><sub>6</sub> and THF-<i>d</i><sub>8</sub>.<br>
 There are limited reports of SANS results on cyclic polymers due to the<br>
 lack of substantial development in the field until recently. Now that <br>
pure, well-defined cyclic polymers are accessible, unanswered questions <br>
about their rheology and physical conformations can be better <br>
investigated. Previously reported SANS experiments have used cyclic and <br>
linear polystyrene samples; therefore, our work allowed for direct <br>
comparison using a contrasting (structurally and sterically) polymer. We<br>
 compared SANS results of cyclic and linear PLA samples with various <br>
microstructures and molecular weights at two different temperatures, <br>
allowing for comparison with a wide range of variables. The results <br>
followed the trends of previous experiments, but much greater <br>
differences in the effective polymer–solvent interaction parameters <br>
between cyclic and linear forms of PLA were observed, implying that the <br>
small form factor and hydrogen bonding in PLA allowed for much more <br>
compact conformations in the cyclic form only. Also, the polymer <br>
microstructure was found to influence polymer–solvent interaction <br>
parameters substantially. These results illustrate how the difference in<br>
 polymer–solvent interactions between cyclic and linear polymers can <br>
vary greatly depending on the polymer in question and the potential of <br>
neutron scattering as a tool for identification and characterization of <br>
the cyclic topology.}},
  author       = {{Yang, Philip B. and Davidson, Matthew G. and Edler, Karen J. and Leaman, Niamh and Bathke, Elly K. and McCormick, Strachan N. and Matsarskaia, Olga and Brown, Steven}},
  issn         = {{0024-9297}},
  language     = {{eng}},
  month        = {{12}},
  number       = {{24}},
  pages        = {{11051--11058}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Macromolecules}},
  title        = {{Comparison of Cyclic and Linear Poly(lactide)s Using Small-Angle Neutron Scattering}},
  url          = {{http://dx.doi.org/10.1021/acs.macromol.2c02020}},
  doi          = {{10.1021/acs.macromol.2c02020}},
  volume       = {{55}},
  year         = {{2022}},
}