danДоклады Национальной академии наук БеларусиDoklady of the National Academy of Sciences of Belarus1561-83232524-2431The Republican Unitary Enterprise Publishing House "Belaruskaya Navuka"10.29235/1561-8323-2018-62-6-694-702dan-569Research ArticleХИМИЯCHEMISTRYВлияние «жесткости» осадителя в формовочном растворе на структуру и свойства полиэфирсульфоновых мембранInfluence of different non-solvent additives to the casting solution on the structure and properties of PES membranesБильдюкевичА. В.BildyukevichA. V.

академик, д-р хим. наук, профессор, директор

Academician, D. Sc. (Chemistry), Professor, Director

uf@ifoch.bas-net.byГлевицкаяТ. А.HliavitskayaT. A.

мл. науч. сотрудник

Junior researcher

hlyavitskaya1706@gmail.comШустиковА. А.ShustikovA. A.

мл. науч. сотрудник

Junior researcher

a.shustikov@tut.byИнститут физико-органической химии Национальной академии наук Беларуси, МинскInstitite of Physical Organic Chemistry of the National Academy of Science of Belarus, Minsk201813012019626694702Copyright © Бильдюкевич А.В., Глевицкая Т.А., Шустиков А.А., 20192019Бильдюкевич А.В., Глевицкая Т.А., Шустиков А.А.Bildyukevich A.V., Hliavitskaya T.A., Shustikov A.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://doklady.belnauka.by/jour/article/view/569

Изучено влияние чисел осаждения (ЧО) смесей жесткого и мягкого осадителей на фазовое состояние и вязкость растворов полиэфирсульфон(ПЭС)/диметилацетамид(ДМАА)/осадитель, структуру и свойства мембран, получаемых на их основе. В качестве добавок осадителей в растворы ПЭС в ДМАА использовали ПЭГ-400 (ЧО > 1000), воду (ЧО = 10,6), 85 %-ную фосфорную кислоту (ЧО = 13,0), глицерин (ЧО = 27,8) и их смеси. На примере смеси Гл/ПЭГ-400 установлено, что с увеличением ЧО добавки область существования стабильных гомогенных растворов расширяется, а при постоянной концентрации смеси Гл/ПЭГ-400 вязкость растворов уменьшается. Показано, что с увеличением ЧО добавки Гл/ПЭГ-400 при постоянной степени насыщения формовочного раствора (0,94–0,95) происходит возрастание удельной производительности мембран по воде с 13 до 150 л/м2 ч. Наиболее резко возрастание потока происходит в интервале ЧО 39,7–125 г/дл. Электронно-микроскопическое исследование показало, что структура мембран в поперечном сечении не претерпевает существенных изменений при варьировании ЧО добавки, однако с увеличением ЧО наблюдается возрастание толщины селективного слоя мембран: при переходе от ЧО = 39,7 г/дл к ЧО = 750 г/дл толщина селективного слоя возрастает с 1 до 4,5 мкм. Таким образом, проведенные исследования позволяют сделать вывод о том, что структура и свойства ультрафильтрационных мембран определяются не только степенью насыщения формовочного раствора, но и жесткостью осадителя, введенного в состав формовочного раствора.

The effect of the precipitation value (PV) of mixtures of strong and weak non-solvent additives (NSA) on the phase state and viscosity of polyethersulfone(PES)/dimethylacetamide(DMAc)/non-solvent solutions and on the structure and performance of PES membranes were studied. Polyethylene glycol 400 (PEG-400, PV > 1000), water (PV = 10.6), 85 % phosphoric acid (PV = 13.0), glycerol (Gly, PV = 27.8) and mixtures thereof were used as NSA for PES-DMAc solutions. Using Gly/PEG-400 mixtures it was established that the increase in PV of NSA leads to the increase of a miscibility gap on the phase diagram. At a constant concentration of Gly/PEG-400 mixture, the viscosity of the solutions decreases. For a constant ratio (0.94–0.95) of the NSA amount added to the polymer-solvent system to the NSA amount causes a phase separation of the casting solution (coagulation value) increase in PV of NSA Gly/PEG-400 leads to an increase of the membrane pure water flux (PWF) from 13 up to 150 l/m2 h at 1 bar. The most dramatic increase in PWF occurs in the range of PV 39.7–125 g/dL. The results of SEM study don’t show significant differences in the cross-section morphology of membranes for different PV of NSA. However, the thickness of the selective membrane layer increases from 1 up to 4.5 μm when PV increased from 39.7 up to 750 g/dL. Thus, these studies allow us to conclude that the structure and properties of ultrafiltration membranes depend not only on the coagulation value of the casting solution, but also on the precipitation value of NSA.

полиэфирсульфонмембранаинверсия фазчисло осажденияморфология мембрантранспортные характеристикиpolyethersulfonemembranephase inversionprecipitation valuemorphology of membranestransport propertiesРабота выполнена при финансовой поддержке БРФФИ в рамках научного проекта № Х18М044.The work was sponsored by the Belarusian Republican Foundation for Fundamental Research within the framework of the research project no. Х18М-044.ReferencesLiu, Y. Characterization of morphology controlled polyethersulfone hollow fiber membranes by the addition of polyethylene glycol to the dope and bore liquid solution / y. liu, G. H. koops, H. Strathmann // J. Membrane Science. – 2003. – Vol. 223, N 1–2. – P. 187–199. https://doi.org/10.1016/s0376-7388(03)00322-3Liu Y., Koops G. H., Strathmann H. Characterization of morphology controlled polyethersulfone hollow fiber membranes by the addition of polyethylene glycol to the dope and bore liquid solution. Journal of Membrane Science, 2003, vol. 223, no. 1–2, pp. 187–199. https://doi.org/10.1016/s0376-7388(03)00322-3Wang, Z. The role of nonsolvent in-diffusion velocity in determining polymeric membrane morphology / Z. Wang, J. Ma // Desalination. – 2012. – Vol. 286. – P. 69–79. https://doi.org/10.1016/j.desal.2011.11.006Wang Z., Ma J. The role of nonsolvent in-diffusion velocity in determining polymeric membrane morphology. Desalination, 2012, vol. 286, pp. 69–79. https://doi.org/10.1016/j.desal.2011.11.006Holda, A. k. Understanding and guiding the phase inversion process for synthesis of solvent resistant nanofiltration membranes / A. k. Holda, I. F. J. Vankelecom // J. Applied Polymer Sci. – 2015. – Vol. 132, N 27. – App. 42130. https://doi. org/10.1002/app.42130Holda A. k., Vankelecom I. F. J. Understanding and guiding the phase inversion process for synthesis of solvent resistant nanofiltration membranes. Journal of Applied Polymer Science, 2015, vol. 132, no. 27, app. 42130. https://doi. org/10.1002/app.42130Xu, Z. l. Polyethersulfone (PES) hollow fiber ultrafiltration membranes prepared by PES/non-solvent/NMP solution / Z. l. Xu, F. A. Qusay // J. Membrane Sci. – 2004. – Vol. 233, N 1–2. – P. 101–111. https://doi.org/10.1016/j.memsci.2004.01.005Xu Z. l., Qusay F. A. Polyethersulfone (PES) hollow fiber ultrafiltration membranes prepared by PES/non-solvent/ NMP solution. Journal of Membrane Science, 2004, vol. 233, no. 1–2, pp. 101–111. https://doi.org/10.1016/j.memsci.2004.01.005Idris, A. Synthesis, characterization and performance of asymmetric polyethersulfone (PES) ultrafiltration membranes with polyethylene glycol of different molecular weights as additives / A. Idris, M. J. Norashikin, M. y. Noordin // Desalination. – 2007. – Vol. 207, N 1–3. – P. 324–339. https://doi.org/10.1016/j.desal.2006.08.008Idris A., Norashikin M. J., Noordin M. y. Synthesis, characterization and performance of asymmetric polyethersulfone (PES) ultrafiltration membranes with polyethylene glycol of different molecular weights as additives. Desalination, 2007, vol. 207, no. 1–3, pp. 324–339. https://doi.org/10.1016/j.desal.2006.08.008Chakrabarty, B. Effect of molecular weight of PEG on membrane morphology and transport properties / B. Chakrabarty, A. k. Glishal, M. k. Purkait // J. Membrane Sci. – 2008. – Vol. 309, N 1–2. – P. 209–221. https://doi.org/10.1016/j. memsci.2007.10.027Chakrabarty B., Ghoshal A. k., Purkait M. k. Effect of molecular weight of PEG on membrane morphology and transport properties. Journal of Membrane Science, 2008, vol. 309, no. 1–2, pp. 209–221. https://doi.org/10.1016/j.memsci. 2007.10.027Preparation and characterization of polyethersulfone microfiltration membranes by a 2-methoxyethanol additive / S.-J. Shin [et al.] // Desalination. – 2005. – Vol. 186, N 1–3. – P. 1–10. https://doi.org/10.1016/j.desal.2005.03.092Shin S.-J., kim J.-P., kim H.-J., Jeon J.-H., Min B. Preparation and characterization of polyethersulfone microfiltration membranes by a 2-methoxyethanol additive. Desalination, 2005, vol. 186, no. 1–3, pp. 1–10. https://doi.org/10.1016/j. desal.2005.03.092Torrestiana-Sanchez, B. Effect of nonsolvents on properties of spinning solutions and polyethersulfone hollow fiber ultrafiltration membranes / B. Torrestiana-Sanchez, R. I. ortiz-Basurto, E. Brito-De la Fuente // J. Membrane Sci. – 1999. – Vol. 152, N 1. – P. 19–28. https://doi.org/10.1016/s0376-7388(98)00172-0Torrestiana-Sanchez B., ortiz-Basurto R. I., Brito-De la Fuente E. Effect of nonsolvents on properties of spinning solutions and polyethersulfone hollow fiber ultrafiltration membranes. Journal of Membrane Science, 1999, vol. 152, no. 1, pp. 19–28. https://doi.org/10.1016/s0376-7388(98)00172-0Phase separation phenomena of polysulfone/solvent/organic nonsolvent and polyethersulfone/solvent/organic nonsolvent systems / D. Wang [et al.] // J. Applied Polymer Sci. – 1993. – Vol. 50, N 10. – P. 1693–1700. https://doi.org/10.1002/ app.1993.070501003Wang D., li k., Sourirajan S., Teo W. k. Phase separation phenomena of polysulfone/solvent/organic nonsolvent and polyethersulfone/solvent/organic nonsolvent systems. Journal of Applied Polymer Science, 1993, vol. 50, no. 10, pp. 1693– 1700. https://doi.org/10.1002/app.1993.070501003Wang, D. Relationship between mass ratio of nonsolvent-additive to solvent in membrane casting solution and its coagulation value / D. Wang, k. li, W. k. Teo // J. Membrane Sci. – 1995. – Vol. 98, N 3. – P. 233–240. https://doi. org/10.1016/0376-7388(94)00191-zWang D., li k., Teo W. k. Relationship between mass ratio of nonsolvent-additive to solvent in membrane casting solution and its coagulation value. Journal of Membrane Science, 1995, vol. 98, no. 3, pp. 233–240. https://doi.org/10.1016/0376-7388(94)00191-zПраценко, С. А. Структура формовочных растворов и ее влияние на характеристики полиамидных мембран / С. А. Праценко, А. В. Бильдюкевич // Высокомолекулярные соединения. Сер. А. – 1994. – T. 36, № 3. – С. 457–460.Pratsenko S. A., Bildyukevich A. V. Structure of casting solutions and its effect on the characteristics of polyamide membranes. Polymer science, Ser. А, 1994, vol. 36, no. 3, pp. 457–460 (in Russian).Бильдюкевич, А. В. Влияние порообразователей на свойства полиэфирсульфоновых мембран / А. В. Бильдюкевич, С. А. Праценко, Т. В. Плиско // Хим. технология. – 2012. – T. 13, № 3. – C. 174–178.Bildyukevich A. V., Pratsenko S. A., Plisko T. V. Influence of pore-generators on properties of polyethersulfone membranes. Khimicheskaya Tekhnologiya [Chemical Technology], 2012, vol. 13, no. 3, pp. 174–178 (in Russian).Effects of polyethylene glycol on membrane formation and properties of hydrophilic sulfonated polyphenylenesulfone (sPPSU) membranes / y. Feng [et al.] // J. Membrane Sci. – 2017. – Vol. 531. – P. 27–35. https://doi.org/10.1016/j. memsci.2017.02.040Feng y., Han G., Chung T.-S., Weber M., Widjojo N., Maletzko C. Effects of polyethylene glycol on membrane formation and properties of hydrophilic sulfonated polyphenylenesulfone (sPPSU) membranes. Journal of Membrane Science, 2017, vol. 531, pp. 27–35. https://doi.org/10.1016/j.memsci.2017.02.040Effect of nonsolvent additives on the porosity and morphology of asymmetric TPX membranes / J.-y. lai [et al.] // J. Membrane Sci. – 1996. – Vol. 118, N 1. – P. 49–61. https://doi.org/10.1016/0376-7388(96)00084-1lai J.-y., lin F.-C., Wang C.-C., Wang D.-M. Effect of nonsolvent additives on the porosity and morphology of asymmetric TPX membranes. Journal of Membrane Science, 1996, vol. 118, no. 1, pp. 49–61. https://doi.org/10.1016/0376-7388(96)00084-1Effects of solvent on the pore formation in asymmetric 6FDA–4,4′oDA polyimide membrane: terms of thermodynamics, precipitation kinetics, and physical factors / k.-y. Chun [et al.] // J. Membrane Sci. – 2000. – Vol. 169, N 2. – P. 197–204. https://doi.org/10.1016/s0376-7388(99)00336-1Chun k.-y., Jang S.-H., kim H.-S., kim y.-W., Han H.-S., Joe y. Effects of solvent on the pore formation in asymmetric 6FDA–4,4′oDA polyimide membrane: terms of thermodynamics, precipitation kinetics, and physical factors. Journal of Membrane Science, 2000, vol. 169, no. 2, pp. 197–204. https://doi.org/10.1016/s0376-7388(99)00336-1

The authors declare that there are no conflicts of interest present.