Effect of halogen substituents on polymer membrane hydrophobicity, swelling and transport mechanism: chlorine versus fluorine
While the role of fluorine on mass transport in polymers has been the subject of extensive research efforts, less attention has been paid to the role played by other halogens, such as chlorine. These efforts favored the synthesis of a plethora of perfluoropolymers which, although exhibiting enhanced...
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| Published in | Journal of membrane science Vol. 662; p. 120964 |
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| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
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Elsevier B.V
15.10.2022
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| Abstract | While the role of fluorine on mass transport in polymers has been the subject of extensive research efforts, less attention has been paid to the role played by other halogens, such as chlorine. These efforts favored the synthesis of a plethora of perfluoropolymers which, although exhibiting enhanced physical aging resistance relative to conventional hydrocarbon-based polymers, suffer from swelling and plasticization in the presence of hydrocarbons.
In this study, we show that the presence of chlorine in perfluoropolymers alters their hydrophobicity while enhancing swelling resistance and size-sieving ability. Model polar vapors, such as methanol and water, and non-polar hydrocarbon vapors were selected for a fundamental transport study in a series of co-polymers of perfluoro(2-methylene-4-methyl-1,3-dioxolane (PFMMD) and chlorotrifluoroethylene (CTFE), namely poly(PFMMD-co-CTFE), exhibiting systematically varied molar amount of CTFE (i.e., chlorine). Fundamental structure-property correlations were developed and possible applications in the field of membrane separations were outlined. Finally, a series of solubility data of chlorinated fluids in polar liquids was discussed to support our conclusions.
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•Chlorine alters perfluoropolymers hydrophobicity.•Poly(PFMMD-co-CTFE)'s interaction with hydrocarbons is more unfavorable than in conventional perfluoropolymers.•Poly(PFMMD-co-CTFE) exhibits better swelling resistance relative to conventional perfluoropolymers. |
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| AbstractList | While the role of fluorine on mass transport in polymers has been the subject of extensive research efforts, less attention has been paid to the role played by other halogens, such as chlorine. These efforts favored the synthesis of a plethora of perfluoropolymers which, although exhibiting enhanced physical aging resistance relative to conventional hydrocarbon-based polymers, suffer from swelling and plasticization in the presence of hydrocarbons.
In this study, we show that the presence of chlorine in perfluoropolymers alters their hydrophobicity while enhancing swelling resistance and size-sieving ability. Model polar vapors, such as methanol and water, and non-polar hydrocarbon vapors were selected for a fundamental transport study in a series of co-polymers of perfluoro(2-methylene-4-methyl-1,3-dioxolane (PFMMD) and chlorotrifluoroethylene (CTFE), namely poly(PFMMD-co-CTFE), exhibiting systematically varied molar amount of CTFE (i.e., chlorine). Fundamental structure-property correlations were developed and possible applications in the field of membrane separations were outlined. Finally, a series of solubility data of chlorinated fluids in polar liquids was discussed to support our conclusions.
[Display omitted]
•Chlorine alters perfluoropolymers hydrophobicity.•Poly(PFMMD-co-CTFE)'s interaction with hydrocarbons is more unfavorable than in conventional perfluoropolymers.•Poly(PFMMD-co-CTFE) exhibits better swelling resistance relative to conventional perfluoropolymers. While the role of fluorine on mass transport in polymers has been the subject of extensive research efforts, less attention has been paid to the role played by other halogens, such as chlorine. These efforts favored the synthesis of a plethora of perfluoropolymers which, although exhibiting enhanced physical aging resistance relative to conventional hydrocarbon-based polymers, suffer from swelling and plasticization in the presence of hydrocarbons. In this study, we show that the presence of chlorine in perfluoropolymers alters their hydrophobicity while enhancing swelling resistance and size-sieving ability. Model polar vapors, such as methanol and water, and non-polar hydrocarbon vapors were selected for a fundamental transport study in a series of co-polymers of perfluoro(2-methylene-4-methyl-1,3-dioxolane (PFMMD) and chlorotrifluoroethylene (CTFE), namely poly(PFMMD-co-CTFE), exhibiting systematically varied molar amount of CTFE (i.e., chlorine). Fundamental structure-property correlations were developed and possible applications in the field of membrane separations were outlined. Finally, a series of solubility data of chlorinated fluids in polar liquids was discussed to support our conclusions. |
| ArticleNumber | 120964 |
| Author | Box, William J. Condes, Lucas C. Deng, Jing Okamoto, Yoshiyuki Galizia, Michele |
| Author_xml | – sequence: 1 givenname: Jing surname: Deng fullname: Deng, Jing organization: School of Chemical, Biological and Materials Engineering, University of Oklahoma, 100 E. Boyd Street, Norman, OK, 73019, USA – sequence: 2 givenname: William J. surname: Box fullname: Box, William J. organization: School of Chemical, Biological and Materials Engineering, University of Oklahoma, 100 E. Boyd Street, Norman, OK, 73019, USA – sequence: 3 givenname: Lucas C. surname: Condes fullname: Condes, Lucas C. organization: School of Chemical, Biological and Materials Engineering, University of Oklahoma, 100 E. Boyd Street, Norman, OK, 73019, USA – sequence: 4 givenname: Yoshiyuki surname: Okamoto fullname: Okamoto, Yoshiyuki organization: Department of Chemical and Biomolecular Engineering, Tandon School of Engineering, New York University, 6 MetroTech Center, Brooklyn, NY, 11201, USA – sequence: 5 givenname: Michele orcidid: 0000-0001-5430-4964 surname: Galizia fullname: Galizia, Michele email: mgalizia@ou.edu organization: School of Chemical, Biological and Materials Engineering, University of Oklahoma, 100 E. Boyd Street, Norman, OK, 73019, USA |
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| SubjectTerms | Chlorine composite polymers fluorine Hydrophobicity mass transfer methanol Perfluoropolymers Size-sieving ability solubility Swelling resistance |
| Title | Effect of halogen substituents on polymer membrane hydrophobicity, swelling and transport mechanism: chlorine versus fluorine |
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