Towards a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellent Perfluoropolyether-Based Polyurethane Oligomers

Original perfluoropolyether (PFPE)-based oligomeric polyurethanes (FOPUs) with different macromolecular architecture were synthesized (in one step) as low-surface-energy materials. It is demonstrated that the oligomers, especially the ones terminated with CF<sub>3</sub> moieties, can be...

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Main Authors: Liying Wei, Tugba D. Caliskan, Philip J. Brown, Igor Luzinov
Format: Article
Language:English
Published: MDPI AG 2021-04-01
Series:Polymers
Subjects:
Online Access:https://www.mdpi.com/2073-4360/13/7/1128
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spelling doaj-110558346f834532a58feedc1183118b2021-04-02T23:00:39ZengMDPI AGPolymers2073-43602021-04-01131128112810.3390/polym13071128Towards a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellent Perfluoropolyether-Based Polyurethane OligomersLiying Wei0Tugba D. Caliskan1Philip J. Brown2Igor Luzinov3Department of Materials Science and Engineering, Clemson University, Clemson, SC 29634, USADepartment of Materials Science and Engineering, Clemson University, Clemson, SC 29634, USADepartment of Materials Science and Engineering, Clemson University, Clemson, SC 29634, USADepartment of Materials Science and Engineering, Clemson University, Clemson, SC 29634, USAOriginal perfluoropolyether (PFPE)-based oligomeric polyurethanes (FOPUs) with different macromolecular architecture were synthesized (in one step) as low-surface-energy materials. It is demonstrated that the oligomers, especially the ones terminated with CF<sub>3</sub> moieties, can be employed as safer replacements to long-chain perfluoroalkyl substances/additives. The FOPU macromolecules, when added to an engineering thermoplastic (polyethylene terephthalate, PET) film, readily migrate to the film surface and bring significant water and oil repellency to the thermoplastic boundary. The best performing FOPU/PET films have reached the level of oil wettability and surface energy significantly lower than that of polytetrafluoroethylene, a fully perfluorinated polymer. Specifically, the highest level of the repellency is observed with an oligomeric additive, which was made using aromatic diisocyanate as a comonomer and has CF<sub>3</sub> end-group. This semicrystalline oligomer has a glass transition temperature (<i>T</i><sub>g</sub>) well above room temperature, and we associate the superiority of the material in achieving low water and oil wettability with its ability to effectively retain CF<sub>3</sub> and CF<sub>2</sub> moieties in contact with the test wetting liquids.https://www.mdpi.com/2073-4360/13/7/1128oil repellencywater repellencyperfluoropolyethersoligomerfluorinated polyurethanesoleophobicity
collection DOAJ
language English
format Article
sources DOAJ
author Liying Wei
Tugba D. Caliskan
Philip J. Brown
Igor Luzinov
spellingShingle Liying Wei
Tugba D. Caliskan
Philip J. Brown
Igor Luzinov
Towards a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellent Perfluoropolyether-Based Polyurethane Oligomers
Polymers
oil repellency
water repellency
perfluoropolyethers
oligomer
fluorinated polyurethanes
oleophobicity
author_facet Liying Wei
Tugba D. Caliskan
Philip J. Brown
Igor Luzinov
author_sort Liying Wei
title Towards a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellent Perfluoropolyether-Based Polyurethane Oligomers
title_short Towards a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellent Perfluoropolyether-Based Polyurethane Oligomers
title_full Towards a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellent Perfluoropolyether-Based Polyurethane Oligomers
title_fullStr Towards a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellent Perfluoropolyether-Based Polyurethane Oligomers
title_full_unstemmed Towards a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellent Perfluoropolyether-Based Polyurethane Oligomers
title_sort towards a long-chain perfluoroalkyl replacement: water and oil repellent perfluoropolyether-based polyurethane oligomers
publisher MDPI AG
series Polymers
issn 2073-4360
publishDate 2021-04-01
description Original perfluoropolyether (PFPE)-based oligomeric polyurethanes (FOPUs) with different macromolecular architecture were synthesized (in one step) as low-surface-energy materials. It is demonstrated that the oligomers, especially the ones terminated with CF<sub>3</sub> moieties, can be employed as safer replacements to long-chain perfluoroalkyl substances/additives. The FOPU macromolecules, when added to an engineering thermoplastic (polyethylene terephthalate, PET) film, readily migrate to the film surface and bring significant water and oil repellency to the thermoplastic boundary. The best performing FOPU/PET films have reached the level of oil wettability and surface energy significantly lower than that of polytetrafluoroethylene, a fully perfluorinated polymer. Specifically, the highest level of the repellency is observed with an oligomeric additive, which was made using aromatic diisocyanate as a comonomer and has CF<sub>3</sub> end-group. This semicrystalline oligomer has a glass transition temperature (<i>T</i><sub>g</sub>) well above room temperature, and we associate the superiority of the material in achieving low water and oil wettability with its ability to effectively retain CF<sub>3</sub> and CF<sub>2</sub> moieties in contact with the test wetting liquids.
topic oil repellency
water repellency
perfluoropolyethers
oligomer
fluorinated polyurethanes
oleophobicity
url https://www.mdpi.com/2073-4360/13/7/1128
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AT philipjbrown towardsalongchainperfluoroalkylreplacementwaterandoilrepellentperfluoropolyetherbasedpolyurethaneoligomers
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