Examining the Water–Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid Hydrogels
Non-isocyanate polyurethane (NIPU) networks physically modified with octa(3-hydroxy-3-methylbutyldimethylsiloxy)POSS (8OHPOSS, 0–10 wt%) were conditioned in environments of different relative humidities (up to 97%) to study water–polymer interactions. The equilibrium sorption isotherms are of Brunau...
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| Language: | English |
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MDPI AG
2023-12-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/16/1/57 |
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| author | Izabela Łukaszewska Artur Bukowczan Konstantinos N. Raftopoulos Krzysztof Pielichowski |
| author_facet | Izabela Łukaszewska Artur Bukowczan Konstantinos N. Raftopoulos Krzysztof Pielichowski |
| author_sort | Izabela Łukaszewska |
| collection | DOAJ |
| description | Non-isocyanate polyurethane (NIPU) networks physically modified with octa(3-hydroxy-3-methylbutyldimethylsiloxy)POSS (8OHPOSS, 0–10 wt%) were conditioned in environments of different relative humidities (up to 97%) to study water–polymer interactions. The equilibrium sorption isotherms are of Brunauer type III in a water activity range of 0–0.97 and are discussed in terms of the Guggenheim (GAB) sorption model. The study shows that the introduction of 8OHPOSS, even in a large amount (10 wt%), does not hinder the water affinity of the NIPU network despite the hydrophobic nature of POSS; this is attributable to the homogenous dispersion of POSS in the polymer matrix. The shift in the urethane-derived carbonyl bands toward lower wavenumbers with a simultaneous shift in the urethane N-H bending bands toward higher wavenumbers exposes the breakage of polymer–polymer hydrogen bonds upon water uptake due to the formation of stronger water–polymer hydrogen bonds. Upon water absorption, a notable decrease in the glass transition temperature (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></mrow></semantics></math></inline-formula>) is observed for all studied materials. The progressive reduction in <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></mrow></semantics></math></inline-formula> with water uptake is driven by plasticization and slaving mechanisms. POSS moieties are thought to impact slaving indirectly by slightly affecting water uptake at very high hydration levels. |
| first_indexed | 2024-03-08T14:59:41Z |
| format | Article |
| id | doaj.art-c6696fbef16d4339a3ec29098f914f3a |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-08T14:59:41Z |
| publishDate | 2023-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-c6696fbef16d4339a3ec29098f914f3a2024-01-10T15:06:41ZengMDPI AGPolymers2073-43602023-12-011615710.3390/polym16010057Examining the Water–Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid HydrogelsIzabela Łukaszewska0Artur Bukowczan1Konstantinos N. Raftopoulos2Krzysztof Pielichowski3Department of Chemistry and Technology of Polymers, Cracow University of Technology, ul. Warszawska 24, 31-155 Kraków, PolandDepartment of Chemistry and Technology of Polymers, Cracow University of Technology, ul. Warszawska 24, 31-155 Kraków, PolandDepartment of Chemistry and Technology of Polymers, Cracow University of Technology, ul. Warszawska 24, 31-155 Kraków, PolandDepartment of Chemistry and Technology of Polymers, Cracow University of Technology, ul. Warszawska 24, 31-155 Kraków, PolandNon-isocyanate polyurethane (NIPU) networks physically modified with octa(3-hydroxy-3-methylbutyldimethylsiloxy)POSS (8OHPOSS, 0–10 wt%) were conditioned in environments of different relative humidities (up to 97%) to study water–polymer interactions. The equilibrium sorption isotherms are of Brunauer type III in a water activity range of 0–0.97 and are discussed in terms of the Guggenheim (GAB) sorption model. The study shows that the introduction of 8OHPOSS, even in a large amount (10 wt%), does not hinder the water affinity of the NIPU network despite the hydrophobic nature of POSS; this is attributable to the homogenous dispersion of POSS in the polymer matrix. The shift in the urethane-derived carbonyl bands toward lower wavenumbers with a simultaneous shift in the urethane N-H bending bands toward higher wavenumbers exposes the breakage of polymer–polymer hydrogen bonds upon water uptake due to the formation of stronger water–polymer hydrogen bonds. Upon water absorption, a notable decrease in the glass transition temperature (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></mrow></semantics></math></inline-formula>) is observed for all studied materials. The progressive reduction in <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></mrow></semantics></math></inline-formula> with water uptake is driven by plasticization and slaving mechanisms. POSS moieties are thought to impact slaving indirectly by slightly affecting water uptake at very high hydration levels.https://www.mdpi.com/2073-4360/16/1/57non-isocyanate polyurethanesPOSShydrogelswater absorptionglass transition |
| spellingShingle | Izabela Łukaszewska Artur Bukowczan Konstantinos N. Raftopoulos Krzysztof Pielichowski Examining the Water–Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid Hydrogels Polymers non-isocyanate polyurethanes POSS hydrogels water absorption glass transition |
| title | Examining the Water–Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid Hydrogels |
| title_full | Examining the Water–Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid Hydrogels |
| title_fullStr | Examining the Water–Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid Hydrogels |
| title_full_unstemmed | Examining the Water–Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid Hydrogels |
| title_short | Examining the Water–Polymer Interactions in Non-Isocyanate Polyurethane/Polyhedral Oligomeric Silsesquioxane Hybrid Hydrogels |
| title_sort | examining the water polymer interactions in non isocyanate polyurethane polyhedral oligomeric silsesquioxane hybrid hydrogels |
| topic | non-isocyanate polyurethanes POSS hydrogels water absorption glass transition |
| url | https://www.mdpi.com/2073-4360/16/1/57 |
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