{"title":"聚苯砜基多孔膜的后磺化亲水性研究","authors":"E.S. Dmitrieva , D.A. Razlataya , A.Yu Raeva , G.A. Shandryuk , J.V. Kostina , T.S. Anokhina , I.L. Borisov , E.A. Grushevenko , S.Yu Khashirova , A.V. Volkov","doi":"10.1016/j.reactfunctpolym.2025.106482","DOIUrl":null,"url":null,"abstract":"<div><div>Polyphenylene sulfone (PPSU) is an attractive membrane material due to its good mechanical properties and hydrolytic stability; however, its semi-hydrophobic nature typically results in low water permeance. In this work, we propose, for the first time, a method for the hydrophilization of fabricated asymmetric PPSU membranes via post-sulfonation. This approach allows the fabrication of a membrane with predetermined parameters, followed by tuning of its hydrophilic/hydrophobic balance by controlling the post-treatment conditions. In contrast, prior sulfonation of the PPSU polymer (a common method) necessitates a revision of casting conditions, as varying the degree of sulfonation alters the polymer solubility parameter and affects the properties of the membrane formed via the non-solvent induced phase separation (NIPS) process. Aqueous sulfuric acid solutions (62–98 wt%) were used as the sulfonating agent, and the treatment time was varied from 1 min to 20 days. Both commercial (BASF) and in-house synthesized PPSU samples were studied. Sulfonation significantly reduced the water contact angle: from 89 to 92° to 0° for dense films, and from 67 to 69° to 44–50° for porous membranes. Consequently, the water permeance of the sulfonated PPSU membranes approximately doubled, increasing from 0.20 to 0.34 to 0.42–0.47 kg/m<sup>2</sup>·h·bar. It should be noted that maximizing the water permeance of the pristine membrane (by using pore-forming agents etc.) was beyond the scope of this study. The membranes demonstrated a high rejection rate of 99 % for Blue Dextran dye (MW 70,000 g/mol). It was proposed that the residual NMP solvent in the membrane might also undergo the sulfonation.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"217 ","pages":"Article 106482"},"PeriodicalIF":5.1000,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hydrophilization of porous membranes based on polyphenylene sulfone by post-sulfonation\",\"authors\":\"E.S. Dmitrieva , D.A. Razlataya , A.Yu Raeva , G.A. Shandryuk , J.V. Kostina , T.S. Anokhina , I.L. Borisov , E.A. Grushevenko , S.Yu Khashirova , A.V. Volkov\",\"doi\":\"10.1016/j.reactfunctpolym.2025.106482\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Polyphenylene sulfone (PPSU) is an attractive membrane material due to its good mechanical properties and hydrolytic stability; however, its semi-hydrophobic nature typically results in low water permeance. In this work, we propose, for the first time, a method for the hydrophilization of fabricated asymmetric PPSU membranes via post-sulfonation. This approach allows the fabrication of a membrane with predetermined parameters, followed by tuning of its hydrophilic/hydrophobic balance by controlling the post-treatment conditions. In contrast, prior sulfonation of the PPSU polymer (a common method) necessitates a revision of casting conditions, as varying the degree of sulfonation alters the polymer solubility parameter and affects the properties of the membrane formed via the non-solvent induced phase separation (NIPS) process. Aqueous sulfuric acid solutions (62–98 wt%) were used as the sulfonating agent, and the treatment time was varied from 1 min to 20 days. Both commercial (BASF) and in-house synthesized PPSU samples were studied. Sulfonation significantly reduced the water contact angle: from 89 to 92° to 0° for dense films, and from 67 to 69° to 44–50° for porous membranes. Consequently, the water permeance of the sulfonated PPSU membranes approximately doubled, increasing from 0.20 to 0.34 to 0.42–0.47 kg/m<sup>2</sup>·h·bar. It should be noted that maximizing the water permeance of the pristine membrane (by using pore-forming agents etc.) was beyond the scope of this study. The membranes demonstrated a high rejection rate of 99 % for Blue Dextran dye (MW 70,000 g/mol). It was proposed that the residual NMP solvent in the membrane might also undergo the sulfonation.</div></div>\",\"PeriodicalId\":20916,\"journal\":{\"name\":\"Reactive & Functional Polymers\",\"volume\":\"217 \",\"pages\":\"Article 106482\"},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2025-09-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Reactive & Functional Polymers\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1381514825003347\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Reactive & Functional Polymers","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1381514825003347","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Hydrophilization of porous membranes based on polyphenylene sulfone by post-sulfonation
Polyphenylene sulfone (PPSU) is an attractive membrane material due to its good mechanical properties and hydrolytic stability; however, its semi-hydrophobic nature typically results in low water permeance. In this work, we propose, for the first time, a method for the hydrophilization of fabricated asymmetric PPSU membranes via post-sulfonation. This approach allows the fabrication of a membrane with predetermined parameters, followed by tuning of its hydrophilic/hydrophobic balance by controlling the post-treatment conditions. In contrast, prior sulfonation of the PPSU polymer (a common method) necessitates a revision of casting conditions, as varying the degree of sulfonation alters the polymer solubility parameter and affects the properties of the membrane formed via the non-solvent induced phase separation (NIPS) process. Aqueous sulfuric acid solutions (62–98 wt%) were used as the sulfonating agent, and the treatment time was varied from 1 min to 20 days. Both commercial (BASF) and in-house synthesized PPSU samples were studied. Sulfonation significantly reduced the water contact angle: from 89 to 92° to 0° for dense films, and from 67 to 69° to 44–50° for porous membranes. Consequently, the water permeance of the sulfonated PPSU membranes approximately doubled, increasing from 0.20 to 0.34 to 0.42–0.47 kg/m2·h·bar. It should be noted that maximizing the water permeance of the pristine membrane (by using pore-forming agents etc.) was beyond the scope of this study. The membranes demonstrated a high rejection rate of 99 % for Blue Dextran dye (MW 70,000 g/mol). It was proposed that the residual NMP solvent in the membrane might also undergo the sulfonation.
期刊介绍:
Reactive & Functional Polymers provides a forum to disseminate original ideas, concepts and developments in the science and technology of polymers with functional groups, which impart specific chemical reactivity or physical, chemical, structural, biological, and pharmacological functionality. The scope covers organic polymers, acting for instance as reagents, catalysts, templates, ion-exchangers, selective sorbents, chelating or antimicrobial agents, drug carriers, sensors, membranes, and hydrogels. This also includes reactive cross-linkable prepolymers and high-performance thermosetting polymers, natural or degradable polymers, conducting polymers, and porous polymers.
Original research articles must contain thorough molecular and material characterization data on synthesis of the above polymers in combination with their applications. Applications include but are not limited to catalysis, water or effluent treatment, separations and recovery, electronics and information storage, energy conversion, encapsulation, or adhesion.