WO2021161800A1 - Agent d'hydrophilisation, procédé de modification d'un film poreux hydrophobe, et film poreux hydrophile - Google Patents

Agent d'hydrophilisation, procédé de modification d'un film poreux hydrophobe, et film poreux hydrophile Download PDF

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Publication number
WO2021161800A1
WO2021161800A1 PCT/JP2021/003110 JP2021003110W WO2021161800A1 WO 2021161800 A1 WO2021161800 A1 WO 2021161800A1 JP 2021003110 W JP2021003110 W JP 2021003110W WO 2021161800 A1 WO2021161800 A1 WO 2021161800A1
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WO
WIPO (PCT)
Prior art keywords
porous membrane
hydrophilic
hydrophobic porous
porous film
mass
Prior art date
Application number
PCT/JP2021/003110
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English (en)
Japanese (ja)
Inventor
吉田　俊也
利公 中西
麻依 菅原
Original Assignee
東洋濾紙株式会社
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Publication date
Application filed by 東洋濾紙株式会社 filed Critical 東洋濾紙株式会社
Priority to JP2022500312A priority Critical patent/JPWO2021161800A1/ja
Publication of WO2021161800A1 publication Critical patent/WO2021161800A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals

Definitions

  • a method for producing a porous membrane having different internal properties from the surface properties by directly coating a crosslinked polymer formed from a polyfunctional monomer over the entire surface of a hydrophobic porous substrate for example, Patent Document 1.
  • Patent Document 2 a method of covering the inside of the pores of the porous membrane and the surface of the membrane with a crosslinked polymer containing polyethylene glycol diacrylate has been proposed (for example, Patent Document 2).
  • Patent Document 3 a solution containing a monofunctional acrylate monomer has been proposed.
  • the hydrophilic porous membrane obtained by modifying the hydrophobic porous membrane maintain the filtration rate of the hydrophobic porous membrane before modification as much as possible, that is, the filtration rate after modification has a high retention rate. Is done. Further, the hydrophilic porous membrane is required to have excellent wettability even after being placed in various environments and to have a small amount of total organic carbon (TOC) elution.
  • TOC total organic carbon
  • the present invention provides a hydrophilic porous film having a high maintenance rate of filtration rate after modification, excellent wettability even after being placed in various environments, and a reduced TOC elution amount. It is an object of the present invention to provide an agent, a method for modifying a hydrophobic porous film using such a hydrophilic agent, and a hydrophilic porous film.
  • hydrophobic porous with a hydrophilic agent consisting of an aqueous solution containing a specific bifunctional monomer and a thermal polymerization initiator in a predetermined amount.
  • a hydrophilic porous film having a high maintenance rate of filtration rate after modification, excellent wettability even after being placed in various environments, and a reduced TOC elution amount can be obtained. I found that.
  • the present invention is a method for modifying a hydrophobic porous film, which is a step of impregnating the hydrophobic porous film with the above-mentioned hydrophilic agent, and the above-mentioned hydrophobic porous film impregnated with the hydrophilic agent.
  • Hydrophobicity comprises a step of heating the film to 80 ° C. or higher, a step of washing the hydrophobic porous film after heating with pure water, and a step of drying the hydrophobic porous film after washing. This is a method for modifying a porous film.
  • the present invention is a hydrophilic porous membrane obtained by modifying a hydrophobic porous membrane by the above-mentioned method, and has a wet surface tension of 75 mN / m or more and a TOC elution amount of 200 ppb or less, defined by the following formula. It is a hydrophilic porous membrane characterized by having a filtration rate maintenance rate of 80% or more after modification.
  • a hydrophilic porous film having a high maintenance rate of filtration rate after modification, excellent wettability even after being placed in various environments, and a reduced TOC elution amount can be obtained.
  • An agent, a method for modifying a hydrophobic porous film using such a hydrophilic agent, and a hydrophilic porous film can be obtained.
  • the hydrophilic agent of the present invention comprises an aqueous solution containing 1.0 to 2.5% by mass of polyethylene glycol dimethacrylate and 0.5 to 2.0% by mass of a thermal polymerization initiator.
  • a thermal polymerization initiator 0.5 to 2.0% by mass of a thermal polymerization initiator.
  • polyethylene glycol dimethacrylate (PEGDMA) as a bifunctional monomer is represented by the following formula (1).
  • the molecular weight of PEGDMA represented by the above formula (1) is about 492 to 1180, preferably about 536 to 1136. More specifically, PEG400DMA, PEG600DMA, and PEG1000DMA can be mentioned. PEG400DMA, PEG600DMA and PEG1000DMA correspond to PEGDMA having n values of 9, 14 and 23 in the above formula (1), respectively. For example, two or more types of PEGDMA having different n values may be included around a predetermined n value in the range of 8 to 24.
  • the content of polyethylene glycol dimethacrylate in the aqueous solution is defined as 1.0 to 2.5% by mass. Even if the hydrophobic porous membrane is modified by using an aqueous solution containing less than 1.0% by mass of polyethylene glycol dimethacrylate as a hydrophilic agent, a hydrophilic porous membrane having excellent wettability cannot be obtained. On the other hand, if the polyethylene glycol dimethacrylate in the aqueous solution exceeds 2.5% by mass, the filtration rate of the hydrophilic porous membrane after the treatment cannot be maintained high.
  • the content of polyethylene glycol dimethacrylate is preferably 1.0 to 2.5% by mass, more preferably 1.5 to 2.0% by mass.
  • Ammonium persulfate is generally used as the thermal polymerization initiator, but potassium persulfate or the like can also be used.
  • the content of the thermal polymerization initiator in the aqueous solution is 0.5 to 2.0% by mass. If it is too small, no effect will be obtained, and if it is excessively contained, the effect will not be significantly increased.
  • the content of the thermal polymerization initiator is preferably 0.5 to 2.0% by mass, more preferably 0.8 to 1.2% by mass.
  • the hydrophilic agent of the present invention comprises an aqueous solution containing 1.0 to 2.5% by mass of polyethylene glycol dimethacrylate and 0.5 to 2.0% by mass of a thermal polymerization initiator, it is hydrophobically porous.
  • a hydrophilic porous film having a high maintenance rate of filtration rate after modification, excellent wettability, and a reduced TOC elution amount.
  • hydrophobic means the property that even if water is developed on the porous membrane, it does not soak into the porous membrane and becomes water droplets, and the porous membrane is 0.05 to 5. Refers to a film having fine pores of about 0 ⁇ m.
  • Specific examples of the hydrophobic porous membrane include a polyether sulfone (PES) membrane.
  • the method for modifying a hydrophobic porous film of the present invention is a step of impregnating the hydrophobic porous film with the hydrophilic agent of the present invention, and 80 of the hydrophobic porous film impregnated with the hydrophilic agent. It includes a step of heating to a temperature of ° C. or higher, a step of washing the hydrophobic porous film after heating with pure water, and a step of drying the hydrophobic porous film after washing.
  • each step will be described.
  • the hydrophobic porous membrane impregnated with the hydrophilic agent is sandwiched between plastic films and the like and heated at 80 ° C. or higher, preferably 85 to 95 ° C.
  • a hot plate can be used for heating, but the heating is not limited to this, and any means can be adopted.
  • the heating time can be appropriately selected according to the heating temperature. For example, in the case of 80 ° C., it can be 3 to 25 minutes. It is presumed that the hydrophilic agent forms a hydrophilic crosslinked polymer on the surface of the hydrophobic porous membrane by heating, and the hydrophobic porous membrane is modified into the hydrophilic porous membrane.
  • the water used here is preferably water having a specific resistance of 17.8 M ⁇ ⁇ cm or more. Further, it is preferably water at room temperature. By using such water as the washing water, it is possible to avoid the influence of TOC derived from the washing water and obtain a hydrophilic porous membrane in which the amount of TOC elution is reduced.
  • the drying temperature and time can be appropriately set according to the size of the reforming target. For example, when modifying a hydrophobic porous membrane having a diameter of 47 mm, it is sufficient to dry at 60 ° C. for 20 minutes.
  • the hydrophilic porous membrane of the present invention can be evaluated by the following method.
  • (Filtration rate) A hydrophilic porous membrane having a diameter of 47 mm is prepared. This hydrophilic porous membrane is fixed to a holder for vacuum filtration (effective filtration area 9.6 cm 2 ), and 200 mL of pure water is filtered under reduced pressure while applying a negative pressure of 69.3 kPa. The time (s) required for the entire amount of pure water to be filtered is measured and defined as t. Using the measured time t, the filtration rate (mL / min ⁇ cm 2 ) can be calculated by the following mathematical formula (2).
  • the hydrophilic porous membrane of the present invention has a post-modification filtration rate maintenance rate of 80% or more, preferably 85% or more.
  • the wet surface tension of the hydrophilic porous membrane of the present invention is 75 mN / m or more, preferably 80 mN / m or more, and more preferably 85 mN / m or more.
  • TOC elution amount A hydrophilic porous membrane having a diameter of 47 mm is fixed to a stainless steel holder (KST-47, manufactured by Toyo Filter Paper Co., Ltd.), ultrapure water is filtered, and about 100 mL of the filtrate is collected from the initial stream.
  • the TOC in the filtrate was measured using a wet oxidation TOC meter (TOC-Vws, manufactured by Shimadzu Corporation) and used as a sample value (TOC (s)).
  • TOC-Vws wet oxidation TOC meter
  • Ultrapure water was flowed using a stainless steel holder on which a hydrophilic porous membrane was not set, and the water recovered in the same manner was measured in the same manner to obtain a blank value (TOC (b)).
  • the TOC elution amount (ppb) was determined by ((TOC (s))-(TOC (b))).
  • the TOC elution amount of the hydrophilic porous membrane of the present invention is 200 ppb or less, preferably 100 ppb or less.
  • the hydrophilic porous membrane of the present invention is obtained by modifying the hydrophobic porous membrane with the hydrophilic agent of the present invention having a predetermined composition, the wet surface tension is 75 mN / m or more. It has the characteristics that the TOC elution amount is 200 ppb or less and the post-modification filtration rate maintenance rate defined by the above formula (1) is 80% or more.
  • PEGDMA Polyethylene glycol dimethacrylate
  • PEG1000DMA is a PEGDMA with a molecular weight of 1136
  • PEG400DMA is a PEGDMA with a molecular weight of 536
  • PEGDA Polyethylene glycol diacrylate
  • PEG600DA is a PEGDA with a molecular weight of 708.
  • APS Ammonium persulfate
  • HEMA Hydroxyethyl methacrylate
  • Sample 1 contains less than 1.0% by mass of bifunctional monomer, and Sample 6 contains more than 2.5% by mass of bifunctional monomer.
  • Sample 10 contains a monofunctional monomer.
  • the sample 11 is PEGDMA having a molecular weight of less than 690.
  • test membrane 1 and the test membrane 2 were made into circular test pieces having a diameter of 47 mm.
  • the test piece was immersed in the hydrophilic agent contained in the glass container for 1 minute, and the test piece was impregnated with the hydrophilic agent.
  • the test piece impregnated with the hydrophilic agent was sandwiched between two plastic films and heated at 90 ° C. for 5 minutes using a hot plate. After heating, the test piece is washed with water at room temperature having a specific resistance of 17.8 M ⁇ ⁇ cm or more for 10 minutes, and dried at 60 ° C. for 20 minutes or more using a blower dryer (FV-430, manufactured by Toyo Engineering Works, Ltd.). To obtain a hydrophilic porous membrane.
  • the filtration rate and the wet surface tension were determined in the same manner for the hydrophilic porous membrane after each treatment after washing with methanol, heating with steam, and immersing in hot alkali.
  • Methanol washing The hydrophilic porous membrane was washed by Soxhlet extraction using a Soxhlet extractor and methanol as a solvent for 16 hours or more.
  • Steam heating A hydrophilic porous membrane was placed in a stainless steel container and heated with steam at 140 ° C. for 30 minutes.
  • Thermo-alkali immersion The hydrophilic porous membrane was immersed in a 2 mass% sodium hydroxide aqueous solution at 90 ° C. for 2 hours, and then washed with running water for 10 minutes.
  • the hydrophilic porous membranes modified with the hydrophilic agents of Samples 2 to 5, 7 to 9, and 11 all have a filtration rate maintenance rate after modification.
  • the wet surface tension is 75 mN / m or more
  • the TOC elution amount is 200 ppb or less.
  • the hydrophilic agents of Samples 2 to 5, 7 to 9, and 11 all started thermal polymerization of PEGDMA as a bifunctional monomer in an amount of 1.0 to 2.5% by mass and 0.5 to 2.0% by mass. Since it is an aqueous solution containing an agent, a hydrophilic porous film having desired properties could be obtained.
  • the test membrane 1 when the sample 1 in which the bifunctional monomer is less than 1.0% by mass is used, the wettability is inferior, and the sample 6 in which the bifunctional monomer exceeds 2.5% by mass is used. After reforming, the filtration rate maintenance rate drops to 76%.
  • the sample 10 containing the monofunctional monomer is used, the wettability after modification is inferior, and the TOC elution amount is as large as 283 ppb.
  • Test Membrane 1 was modified by the same method as described above except that a hydrophilic agent using 2.5% by mass of PEG600DA as a bifunctional monomer and 1.0% by mass of a thermal polymerization initiator was used. The quality was obtained to obtain a hydrophilic porous membrane. The wet surface tension of the obtained hydrophilic porous membrane is evaluated in the same manner as described above, and the results are summarized in Table 9 below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention est caractérisée en ce qu'elle comprend une solution aqueuse contenant de 1,0 à 2,5 % en masse d'un diméthacrylate de polyéthylène glycol et de 0,5 à 2,0 % en masse d'un initiateur de polymérisation thermique.
PCT/JP2021/003110 2020-02-14 2021-01-28 Agent d'hydrophilisation, procédé de modification d'un film poreux hydrophobe, et film poreux hydrophile WO2021161800A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0369673A (ja) * 1989-08-07 1991-03-26 Mitsubishi Rayon Co Ltd 耐熱親水化多孔質ポリオレフイン中空糸
JPH0824602A (ja) * 1994-07-08 1996-01-30 Chikyu Kankyo Sangyo Gijutsu Kenkyu Kiko 表面改質気体分離膜及びその製造方法
JPH11188247A (ja) * 1997-10-27 1999-07-13 Pall Corp 親水性膜
JP2013534464A (ja) * 2010-06-01 2013-09-05 スリーエム イノベイティブ プロパティズ カンパニー 被覆された多孔質材料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0369673A (ja) * 1989-08-07 1991-03-26 Mitsubishi Rayon Co Ltd 耐熱親水化多孔質ポリオレフイン中空糸
JPH0824602A (ja) * 1994-07-08 1996-01-30 Chikyu Kankyo Sangyo Gijutsu Kenkyu Kiko 表面改質気体分離膜及びその製造方法
JPH11188247A (ja) * 1997-10-27 1999-07-13 Pall Corp 親水性膜
JP2013534464A (ja) * 2010-06-01 2013-09-05 スリーエム イノベイティブ プロパティズ カンパニー 被覆された多孔質材料

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