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Influence of PVAc/PVA Hydrolysis on Additive Surface Activity

This aims to establish design rules for the influence of complex polymer matrices on the surface properties of small molecules. Here, we consider the dependence of the surface behaviour of some model additives on polymer matrix hydrophobicity. With stoichiometric control over hydrolysis, we generate...

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Autores principales: Squillace, Ophélie, Fong, Rebecca, Shepherd, Oliver, Hind, Jasmine, Tellam, James, Steinke, Nina-Juliane, Thompson, Richard L.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7023474/
https://www.ncbi.nlm.nih.gov/pubmed/31947559
http://dx.doi.org/10.3390/polym12010205
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author Squillace, Ophélie
Fong, Rebecca
Shepherd, Oliver
Hind, Jasmine
Tellam, James
Steinke, Nina-Juliane
Thompson, Richard L.
author_facet Squillace, Ophélie
Fong, Rebecca
Shepherd, Oliver
Hind, Jasmine
Tellam, James
Steinke, Nina-Juliane
Thompson, Richard L.
author_sort Squillace, Ophélie
collection PubMed
description This aims to establish design rules for the influence of complex polymer matrices on the surface properties of small molecules. Here, we consider the dependence of the surface behaviour of some model additives on polymer matrix hydrophobicity. With stoichiometric control over hydrolysis, we generate systematic changes in matrix chemistry from non-polar, hydrophobic PVAc to its hydrolysed and hydrophilic analogue, PVA. With the changing degree of hydrolysis (DH), the behaviour of additives can be switched in terms of compatibility and surface activity. Sorbitol, a polar sugar-alcohol of inherently high surface energy, blooms to the surface of PVAc, forming patchy domains on surfaces. With the increasing DH of the polymer matrix, its surface segregation decreases to the point where sorbitol acts as a homogeneously distributed plasticiser in PVA. Conversely, and despite its low surface energy, octanoic acid (OA) surprisingly causes the increased wettability of PVAc. We attribute these observations to the high compatibility of OA with PVAc and its ability to reorient upon exposure to water, presenting a hydrophilic COOH-rich surface. The surfactant sodium dodecyl sulfate (SDS) does not show such a clear dependence on the matrix and formed wetting layers over a wide range of DH. Interestingly, SDS appears to be most compatible with PVAc at intermediate DH, which is consistent with the amphiphilic nature of both species under these conditions. Thus, we show that the prediction of the segregation is not simple and depends on multiple factors including hydrophobicity, compatibility, blockiness, surface energy, and the mobility of the components.
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spelling pubmed-70234742020-03-12 Influence of PVAc/PVA Hydrolysis on Additive Surface Activity Squillace, Ophélie Fong, Rebecca Shepherd, Oliver Hind, Jasmine Tellam, James Steinke, Nina-Juliane Thompson, Richard L. Polymers (Basel) Article This aims to establish design rules for the influence of complex polymer matrices on the surface properties of small molecules. Here, we consider the dependence of the surface behaviour of some model additives on polymer matrix hydrophobicity. With stoichiometric control over hydrolysis, we generate systematic changes in matrix chemistry from non-polar, hydrophobic PVAc to its hydrolysed and hydrophilic analogue, PVA. With the changing degree of hydrolysis (DH), the behaviour of additives can be switched in terms of compatibility and surface activity. Sorbitol, a polar sugar-alcohol of inherently high surface energy, blooms to the surface of PVAc, forming patchy domains on surfaces. With the increasing DH of the polymer matrix, its surface segregation decreases to the point where sorbitol acts as a homogeneously distributed plasticiser in PVA. Conversely, and despite its low surface energy, octanoic acid (OA) surprisingly causes the increased wettability of PVAc. We attribute these observations to the high compatibility of OA with PVAc and its ability to reorient upon exposure to water, presenting a hydrophilic COOH-rich surface. The surfactant sodium dodecyl sulfate (SDS) does not show such a clear dependence on the matrix and formed wetting layers over a wide range of DH. Interestingly, SDS appears to be most compatible with PVAc at intermediate DH, which is consistent with the amphiphilic nature of both species under these conditions. Thus, we show that the prediction of the segregation is not simple and depends on multiple factors including hydrophobicity, compatibility, blockiness, surface energy, and the mobility of the components. MDPI 2020-01-14 /pmc/articles/PMC7023474/ /pubmed/31947559 http://dx.doi.org/10.3390/polym12010205 Text en © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Squillace, Ophélie
Fong, Rebecca
Shepherd, Oliver
Hind, Jasmine
Tellam, James
Steinke, Nina-Juliane
Thompson, Richard L.
Influence of PVAc/PVA Hydrolysis on Additive Surface Activity
title Influence of PVAc/PVA Hydrolysis on Additive Surface Activity
title_full Influence of PVAc/PVA Hydrolysis on Additive Surface Activity
title_fullStr Influence of PVAc/PVA Hydrolysis on Additive Surface Activity
title_full_unstemmed Influence of PVAc/PVA Hydrolysis on Additive Surface Activity
title_short Influence of PVAc/PVA Hydrolysis on Additive Surface Activity
title_sort influence of pvac/pva hydrolysis on additive surface activity
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7023474/
https://www.ncbi.nlm.nih.gov/pubmed/31947559
http://dx.doi.org/10.3390/polym12010205
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