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Synthesis, Morphology, and Particle Size Control of Acidic Aqueous Polyurethane Dispersions

Quane, Ellen J. LU orcid ; Elders, Niels ; Ryan, Anthony J. and Mykhaylyk, Oleksandr O. (2024) In Macromolecules p.10623-10634
Abstract
A range of charge-stabilized aqueous polyurethane (PU) dispersions
comprising hard segments formed from hydrogenated methylene diphenyl
diisocyanate (H12MDI) with dimethylolpropionic acid (DMPA)
and ethylenediamine, and soft segments of poly(tetramethylene oxide) of
different molecular weights are synthesized. Characterization of the
dispersions by mass spectrometry, gel permeation chromatography,
small-angle X-ray scattering, atomic force microscopy, and infrared
spectroscopy shows that they are composed of PUs self-assembled into
spherical particles (primary population) and supramolecular structures
formed by hydrogen-bonded H12MDI and DMPA acid-rich fragments
... (More)
A range of charge-stabilized aqueous polyurethane (PU) dispersions
comprising hard segments formed from hydrogenated methylene diphenyl
diisocyanate (H12MDI) with dimethylolpropionic acid (DMPA)
and ethylenediamine, and soft segments of poly(tetramethylene oxide) of
different molecular weights are synthesized. Characterization of the
dispersions by mass spectrometry, gel permeation chromatography,
small-angle X-ray scattering, atomic force microscopy, and infrared
spectroscopy shows that they are composed of PUs self-assembled into
spherical particles (primary population) and supramolecular structures
formed by hydrogen-bonded H12MDI and DMPA acid-rich fragments
(secondary population). Analysis of the scattering patterns of the
dispersions, using a structural model based on conservation of mass,
reveals that the proportion of supramolecular structures increases with
DMPA content. It is also found that the PU particle radius follows the
predictions of the particle surface charge density model, originally
developed for acrylic statistical copolymers, and is controlled by
hydrophile (DMPA) content in the PU molecules, where an increase in PU
acidity results in a decrease in particle size. Moreover, there is a
critical fractional coverage of hydrophiles stabilizing the particle
surface for a given polyether soft-segment molecular weight, which
increases with the polyether molecular weight, confirming that more acid
groups are required to stabilize a more hydrophobic composition. (Less)
Please use this url to cite or link to this publication:
author
; ; and
contributor
Newman, Anna S. ; van Mourik, Sophia ; Williams, Neal S. J. and van den Berg, Keimpe J.
publishing date
type
Contribution to journal
publication status
published
subject
in
Macromolecules
pages
12 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85209569071
  • pmid:39619248
ISSN
1520-5835
DOI
10.1021/acs.macromol.4c02046
language
English
LU publication?
no
id
0746be0f-9445-49fd-92fd-29bc30c0b951
date added to LUP
2024-11-28 10:11:20
date last changed
2025-04-04 14:52:03
@article{0746be0f-9445-49fd-92fd-29bc30c0b951,
  abstract     = {{A range of charge-stabilized aqueous polyurethane (PU) dispersions <br>
comprising hard segments formed from hydrogenated methylene diphenyl <br>
diisocyanate (H<sub>12</sub>MDI) with dimethylolpropionic acid (DMPA) <br>
and ethylenediamine, and soft segments of poly(tetramethylene oxide) of <br>
different molecular weights are synthesized. Characterization of the <br>
dispersions by mass spectrometry, gel permeation chromatography, <br>
small-angle X-ray scattering, atomic force microscopy, and infrared <br>
spectroscopy shows that they are composed of PUs self-assembled into <br>
spherical particles (primary population) and supramolecular structures <br>
formed by hydrogen-bonded H<sub>12</sub>MDI and DMPA acid-rich fragments<br>
 (secondary population). Analysis of the scattering patterns of the <br>
dispersions, using a structural model based on conservation of mass, <br>
reveals that the proportion of supramolecular structures increases with <br>
DMPA content. It is also found that the PU particle radius follows the <br>
predictions of the particle surface charge density model, originally <br>
developed for acrylic statistical copolymers, and is controlled by <br>
hydrophile (DMPA) content in the PU molecules, where an increase in PU <br>
acidity results in a decrease in particle size. Moreover, there is a <br>
critical fractional coverage of hydrophiles stabilizing the particle <br>
surface for a given polyether soft-segment molecular weight, which <br>
increases with the polyether molecular weight, confirming that more acid<br>
 groups are required to stabilize a more hydrophobic composition.}},
  author       = {{Quane, Ellen J. and Elders, Niels and Ryan, Anthony J. and Mykhaylyk, Oleksandr O.}},
  issn         = {{1520-5835}},
  language     = {{eng}},
  month        = {{11}},
  pages        = {{10623--10634}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Macromolecules}},
  title        = {{Synthesis, Morphology, and Particle Size Control of Acidic Aqueous Polyurethane Dispersions}},
  url          = {{http://dx.doi.org/10.1021/acs.macromol.4c02046}},
  doi          = {{10.1021/acs.macromol.4c02046}},
  year         = {{2024}},
}