Polypropylene membranes prepared via non-solvent/thermally induced phase separation: Effect of non-solvent nature

The goal of this work was to investigate the effect of non-solvent nature on the formation of porous membranes via non-solvent/thermally induced phase separation (N-TIPS). The hot solution of polypropylene (PP) in a mixture of dioctyl phthalate (DOP) and dibutyl phthalate (DBP) at 210 °C was placed...

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Published inJournal of membrane science Vol. 703; p. 122839
Main Authors Pochivalov, Konstantin, Basko, Andrey, Yurov, Mikhail, Lebedeva, Tatyana, Shalygin, Maxim, Lavrentyev, Viktor, Yushkin, Alexey, Anokhina, Tatiana, Volkov, Alexey
Format Journal Article
LanguageEnglish
Published Elsevier B.V 01.06.2024
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Online AccessGet full text
ISSN0376-7388
1873-3123
DOI10.1016/j.memsci.2024.122839

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Abstract The goal of this work was to investigate the effect of non-solvent nature on the formation of porous membranes via non-solvent/thermally induced phase separation (N-TIPS). The hot solution of polypropylene (PP) in a mixture of dioctyl phthalate (DOP) and dibutyl phthalate (DBP) at 210 °C was placed as a thin film on a polyethylene terephthalate (PET) substrate, and then precipitated by immersion in the non-solvent (water, iso-propanol, 1-hexanol, or 1-decanol) at room temperature. It was found that the non-solvent nature greatly affected the morphology of the thin skin layer of the membrane facing the precipitation bath, which can be attributed to non-solvent induced phase separation (NIPS). The affinity between the polymeric solution and corresponding non-solvent was evaluated by using Hansen solubility parameters of components taken at room temperature and extrapolated to the temperature of 210 °C. An increase in the affinity between the non-solvent and the polymer transformed the surface layer structure from almost monolithic to cellular (with different pore sizes and porosity) and to spherulitic types. The non-solvent nature played a less pronounced role in the formation of the porous structure of the membrane bulk and the back side of the membrane (facing the PET substrate). Since the morphology of the rest of the membrane was correlated with thermophysical properties of non-solvents, it was concluded that the membrane formation took place due to temperature induced phase separation (TIPS). In the case of water, which has the highest cooling rate, the polypropylene crystallized by forming a “smectic” structure, while the standard α-lamellar structure was observed for other non-solvents. To gain insight into the TIPS process, a model of unsteady one-dimensional heat transfer was applied to simulate the change in the temperature profile of the hot, thin film of polymeric solution placed in the corresponding non-solvent. The resulting membranes were mainly in the microfiltration range with a mean through pore size of 0.05–0.61 μm, and iso-propanol permeance of 2.1–8.4 m3 m−2∙h−1∙bar−1. The rejection of 500 nm polystyrene microspheres was in the range of 45–98 %. The tensile strength was in the range of 2.9–3.2 MPa, and elongation at break was 30–190 % with respect to the non-solvent used. [Display omitted] •Membranes from hot polypropylene solution were cast by precipitation in different non-solvents.•Effect of non-solvent nature in N-TIPS process was highlighted.•Membrane morphology, mechanical properties and pore size were subject of non-solvent nature.•Change of temperature profile of polymeric films during N-TIPS process was simulated.
AbstractList The goal of this work was to investigate the effect of non-solvent nature on the formation of porous membranes via non-solvent/thermally induced phase separation (N-TIPS). The hot solution of polypropylene (PP) in a mixture of dioctyl phthalate (DOP) and dibutyl phthalate (DBP) at 210 °C was placed as a thin film on a polyethylene terephthalate (PET) substrate, and then precipitated by immersion in the non-solvent (water, iso-propanol, 1-hexanol, or 1-decanol) at room temperature. It was found that the non-solvent nature greatly affected the morphology of the thin skin layer of the membrane facing the precipitation bath, which can be attributed to non-solvent induced phase separation (NIPS). The affinity between the polymeric solution and corresponding non-solvent was evaluated by using Hansen solubility parameters of components taken at room temperature and extrapolated to the temperature of 210 °C. An increase in the affinity between the non-solvent and the polymer transformed the surface layer structure from almost monolithic to cellular (with different pore sizes and porosity) and to spherulitic types. The non-solvent nature played a less pronounced role in the formation of the porous structure of the membrane bulk and the back side of the membrane (facing the PET substrate). Since the morphology of the rest of the membrane was correlated with thermophysical properties of non-solvents, it was concluded that the membrane formation took place due to temperature induced phase separation (TIPS). In the case of water, which has the highest cooling rate, the polypropylene crystallized by forming a “smectic” structure, while the standard α-lamellar structure was observed for other non-solvents. To gain insight into the TIPS process, a model of unsteady one-dimensional heat transfer was applied to simulate the change in the temperature profile of the hot, thin film of polymeric solution placed in the corresponding non-solvent. The resulting membranes were mainly in the microfiltration range with a mean through pore size of 0.05–0.61 μm, and iso-propanol permeance of 2.1–8.4 m3 m−2∙h−1∙bar−1. The rejection of 500 nm polystyrene microspheres was in the range of 45–98 %. The tensile strength was in the range of 2.9–3.2 MPa, and elongation at break was 30–190 % with respect to the non-solvent used. [Display omitted] •Membranes from hot polypropylene solution were cast by precipitation in different non-solvents.•Effect of non-solvent nature in N-TIPS process was highlighted.•Membrane morphology, mechanical properties and pore size were subject of non-solvent nature.•Change of temperature profile of polymeric films during N-TIPS process was simulated.
ArticleNumber 122839
Author Volkov, Alexey
Anokhina, Tatiana
Pochivalov, Konstantin
Lebedeva, Tatyana
Yushkin, Alexey
Shalygin, Maxim
Yurov, Mikhail
Basko, Andrey
Lavrentyev, Viktor
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  givenname: Konstantin
  orcidid: 0000-0002-4570-0284
  surname: Pochivalov
  fullname: Pochivalov, Konstantin
  organization: G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Akademicheskaya ul. 1, Ivanovo, 153045, Russia
– sequence: 2
  givenname: Andrey
  orcidid: 0000-0002-8772-5236
  surname: Basko
  fullname: Basko, Andrey
  organization: G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Akademicheskaya ul. 1, Ivanovo, 153045, Russia
– sequence: 3
  givenname: Mikhail
  surname: Yurov
  fullname: Yurov, Mikhail
  organization: G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Akademicheskaya ul. 1, Ivanovo, 153045, Russia
– sequence: 4
  givenname: Tatyana
  orcidid: 0000-0003-0537-0927
  surname: Lebedeva
  fullname: Lebedeva, Tatyana
  organization: G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Akademicheskaya ul. 1, Ivanovo, 153045, Russia
– sequence: 5
  givenname: Maxim
  orcidid: 0000-0002-5139-2265
  surname: Shalygin
  fullname: Shalygin, Maxim
  organization: A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991, Russia
– sequence: 6
  givenname: Viktor
  surname: Lavrentyev
  fullname: Lavrentyev, Viktor
  organization: Institute of Macromolecular Compounds of the Russian Academy of Sciences, 31 Bolshoy pr., 199004, St. Petersburg, Russia
– sequence: 7
  givenname: Alexey
  surname: Yushkin
  fullname: Yushkin, Alexey
  organization: A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991, Russia
– sequence: 8
  givenname: Tatiana
  surname: Anokhina
  fullname: Anokhina, Tatiana
  organization: A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991, Russia
– sequence: 9
  givenname: Alexey
  surname: Volkov
  fullname: Volkov, Alexey
  email: avolkov@ips.ac.ru
  organization: A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991, Russia
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Keywords Polypropylene
Phase diagram
Morphology
Non-solvent-thermally induced phase separation
Membrane
Membrane performance
N-TIPS
Language English
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Snippet The goal of this work was to investigate the effect of non-solvent nature on the formation of porous membranes via non-solvent/thermally induced phase...
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SubjectTerms Membrane
Membrane performance
Morphology
N-TIPS
Non-solvent-thermally induced phase separation
Phase diagram
Polypropylene
Title Polypropylene membranes prepared via non-solvent/thermally induced phase separation: Effect of non-solvent nature
URI https://dx.doi.org/10.1016/j.memsci.2024.122839
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