WO2020067175A1 - イオン交換膜及び電解装置 - Google Patents

イオン交換膜及び電解装置 Download PDF

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Publication number
WO2020067175A1
WO2020067175A1 PCT/JP2019/037629 JP2019037629W WO2020067175A1 WO 2020067175 A1 WO2020067175 A1 WO 2020067175A1 JP 2019037629 W JP2019037629 W JP 2019037629W WO 2020067175 A1 WO2020067175 A1 WO 2020067175A1
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Prior art keywords
ion exchange
exchange membrane
yarn
reinforcing
group
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PCT/JP2019/037629
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English (en)
French (fr)
Japanese (ja)
Inventor
草野　博光
悟 宮本
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Ａｇｃ株式会社
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Priority to JP2020513660A priority Critical patent/JP6801822B2/ja
Priority to CN201980063590.3A priority patent/CN112771211B/zh
Publication of WO2020067175A1 publication Critical patent/WO2020067175A1/ja

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    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/41—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads with specific twist
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres

Definitions

  • the present invention relates to an ion exchange membrane and an electrolysis apparatus having excellent durability.
  • Patent Literature 1 discloses an ion exchange membrane having a woven fabric formed using polytetrafluoroethylene fibers and a fluoropolymer, and reinforced by the woven fabric.
  • the term "excellent durability of the ion exchange membrane” means that the ion exchange membrane may be damaged (for example, the components constituting the ion exchange membrane may be dropped due to various factors) when the electrolytic apparatus provided with the ion exchange membrane is operated. Or perforation of the ion exchange membrane).
  • the present inventors have evaluated the durability of an ion exchange membrane having a reinforcing cloth as described in Patent Literature 1, and found that the process of incorporating the ion exchange membrane into an electrolytic device, a dialysis device, or the like, or the process of using the same for a long period of time In the above, it was found that the ion exchange membrane may be variously damaged.
  • an object of the present invention is to provide an ion exchange membrane and an electrolytic device having excellent durability.
  • the inventor of the present invention has conducted intensive studies on the above problems, and has found that, in an ion exchange membrane having a fluorine-containing polymer having an ion exchange group and a reinforcing cloth, a loop stiffness value R2 along a second reinforcing yarn constituting the reinforcing cloth,
  • the above problem can be solved by making the ratio of the loop stiffness value R1 along the first reinforcing yarn fall within a predetermined range, and more preferably by making the ratio of the crimp ratio of the first reinforcing yarn to the crimp ratio of the second reinforcing yarn fall within a predetermined range.
  • the present invention has the following aspects.
  • a fluoropolymer having an ion exchange group, and a reinforcing cloth The reinforcing cloth includes a first reinforcing thread and a second reinforcing thread intersecting the first reinforcing thread,
  • R1 loop stiffness value in the direction along the first reinforcing yarn
  • R2 loop stiffness value in the direction along the second reinforcing yarn
  • the ratio of R1 to R2 is 0.60 to 1
  • An ion-exchange membrane characterized in that the ion-exchange membrane is 2.0.
  • the ion exchange membrane according to [1] wherein a ratio of the R1 to the R2 is 0.60 or more and less than 0.80.
  • At least one of the first reinforcing yarn and the second reinforcing yarn is selected from the group consisting of a yarn made of polytetrafluoroethylene, a yarn made of polyphenylene sulfide, a yarn made of nylon, and a yarn made of polypropylene.
  • the ion exchange membrane according to any one of [1] to [6] which is at least one kind.
  • the fluorine-containing polymer having an ion exchange group includes a unit based on a fluorine-containing olefin and a unit based on a monomer having a carboxylic acid type functional group and a fluorine atom represented by the following formula (1C):
  • the ion exchange membrane according to any one of [1] to [12].
  • X and X ' are each independently a fluorine atom or a trifluoromethyl group .
  • M C are hydrogen atom, an alkali metal or quaternary ammonium cation .p is 0 or 1 .q is , Is an integer from 0 to 12. r is an integer from 0 to 3. s is 0 or 1.
  • t is an integer from 0 to 12.
  • u is an integer from 0 to 3.
  • the above-mentioned fluorine-containing polymer having an ion exchange group comprises a unit based on a fluorinated olefin, a unit based on a sulfonic acid type functional group and a monomer having a fluorine atom, and a sulfonic acid type functional group represented by the following formula (2S). And the unit based on a monomer having a fluorine atom.
  • N is 1 or 2.
  • A is a group which can be converted to a sulfonic acid type functional group.
  • the present invention in the process of installing an ion-exchange membrane in an electrolytic device or the like, or in the process of operating an electrolytic device or the like in which an ion-exchange membrane is installed, damage to the ion-exchange membrane (for example, ion-exchange membrane) Can be suppressed, and the ion exchange membrane and the electrolysis apparatus with excellent durability can be provided.
  • damage to the ion-exchange membrane for example, ion-exchange membrane
  • FIG. 3 is a schematic enlarged view of a cross section of a reinforcing cloth for explaining a method of measuring a crimp rate of a reinforcing thread.
  • the meanings of the terms in the present invention are as follows.
  • the “sulfonic acid type functional group” means a sulfonic acid group (—SO 3 H) or a sulfonic acid group (—SO 3 M 2 , where M 2 is an alkali metal or quaternary ammonium cation). I do.
  • the “carboxylic acid type functional group” means a carboxylic acid group (—COOH) or a carboxylate group (—COOM 1 , where M 1 is an alkali metal or quaternary ammonium cation).
  • the “precursor membrane” is a membrane containing a polymer having a group that can be converted into an ion exchange group.
  • the “group that can be converted into an ion-exchange group” means a group that can be converted into an ion-exchange group by a treatment such as a hydrolysis treatment, an acid-formation treatment, or a salt exchange with a metal cation.
  • the “group that can be converted into a sulfonic acid type functional group” means a group that can be converted into a sulfonic acid type functional group by a treatment such as a hydrolysis treatment or an acidification treatment.
  • the “group that can be converted into a carboxylic acid type functional group” means a group that can be converted into a carboxylic acid type functional group by a known treatment such as a hydrolysis treatment and an acidification treatment.
  • The“ unit ”in the polymer means an atomic group derived from one molecule of the monomer, formed by polymerization of the monomer.
  • the unit may be an atomic group directly formed by a polymerization reaction, or an atomic group obtained by treating a polymer obtained by a polymerization reaction and converting a part of the atomic group to another structure. .
  • the “reinforcing yarn” is a yarn that constitutes a reinforcing cloth, and is a yarn that does not elute under the operating environment of an apparatus including an ion exchange membrane.
  • the numerical range represented by using “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit. When the units of the lower limit and the upper limit are the same, the unit of the lower limit may be omitted.
  • the “MD direction” (Machine Direction) refers to the transport direction of the membrane during the manufacture of the ion exchange membrane, and refers to the long direction when the ion exchange membrane is manufactured using a long membrane.
  • the “TD direction” Transverse Direction
  • “Loop Stiffness Value” refers to the repulsive force of a loop formed by forming a loop using a strip cut into a predetermined size and crushing the loop by a predetermined amount in the radial direction. And an index representing the rigidity (stiffness) of the film.
  • the ion exchange membrane of the present invention (hereinafter, also referred to as the present ion exchange membrane) has a fluoropolymer having an ion exchange group (hereinafter, also referred to as a fluoropolymer I) and a reinforcing cloth.
  • a fluoropolymer having an ion exchange group hereinafter, also referred to as a fluoropolymer I
  • a reinforcing cloth A first reinforcing yarn and a second reinforcing yarn intersecting the first reinforcing yarn, wherein a loop stiffness value in a direction along the first reinforcing yarn is R1, and a loop stiffness in a direction along the second reinforcing yarn is R1
  • the ratio of the R1 to the R2 (R1 / R2) is 0.60 to 1.0.
  • R1 / R2 is preferably 0.60 or more and less than 0.95, more preferably 0.60 or more and less than 0.85, and particularly preferably 0.60 or more and less than 0.80.
  • the values of R1 and R2 vary depending on the crimp rate of the reinforcing yarn, the type of polymer constituting the ion exchange membrane and the layer structure including the thickness, and the like.
  • R1 is preferably 50 to 165 mN, and is preferably 75 to 150 mN. Is more preferable, and R2 is preferably 70 to 200 mN, more preferably 90 to 180 mN.
  • This ion exchange membrane is excellent in durability. The details of this reason have not been clarified, but are presumed to be due to the following reasons.
  • the present inventor has found that the durability of the ion exchange membrane may be reduced when the ion exchange membrane is installed in the tank of the electrolysis apparatus and continuously operated.
  • the present inventor believes that one of the causes of the decrease in the durability of the ion-exchange membrane is that the ion-exchange membrane is installed in a tank with wrinkles. As described above, when the ion exchange membrane in the tank has wrinkles, the wrinkle portion of the ion exchange membrane comes into strong contact with the member (for example, an electrode) to which the ion exchange membrane is attached, and the ion exchange membrane is removed.
  • the member for example, an electrode
  • the inventors of the present invention have repeatedly studied focusing on the loop stiffness value, which is a physical property representing the stiffness of the ion exchange membrane, and found that the ratio of the loop stiffness value in a predetermined direction of the ion exchange membrane (R1 / R2) It was found that when the value was within the above range, the handleability of the ion-exchange membrane was improved, and when the ion-exchange membrane was installed in the tank, it was difficult for wrinkles to enter the ion-exchange membrane. Thus, it is considered that an ion exchange membrane having excellent durability was obtained.
  • the present ion exchange membrane contains a fluoropolymer (I).
  • the ion exchange capacity of the fluoropolymer (I) is preferably at least 0.90 meq / g resin, more preferably at least 1.00 meq / g resin, and more preferably 1.20 meq / g, from the viewpoint that the electrolysis voltage of the electrolytic device can be further reduced. It is more preferably resin or more, and preferably 2.00 meq / g resin or less, and more preferably 1.90 meq / g resin or less from the viewpoint that the strength of the ion exchange membrane is more excellent.
  • the above meq / g resin represents the meq per dry mass (1 g) of the resin containing the fluoropolymer (I) in the present ion exchange membrane.
  • the dry mass of the resin containing the fluoropolymer (I) in the present ion exchange membrane is intended to mean the mass after the present ion exchange membrane is left at 90 ° C. for 16 hours under reduced pressure of 1/10 atm (76 mmHg) or less. I do.
  • the fluoropolymer (I) used in the present ion exchange membrane may be one type, or two or more types may be laminated or mixed.
  • the present ion exchange membrane may contain a polymer other than the fluoropolymer (I), but the polymer in the present ion exchange membrane is preferably substantially composed of the fluoropolymer (I).
  • substantially consisting of the fluoropolymer (I) means that the content of the fluoropolymer (I) is 95% by mass or more based on the total mass of the polymer in the present ion exchange membrane.
  • the upper limit of the content of the fluoropolymer (I) is 100% by mass based on the total mass of the polymer in the present ion exchange membrane.
  • the fluoropolymer (I) has an ion exchange group.
  • Preferred examples of the ion exchange group include a carboxylic acid type functional group and a sulfonic acid type functional group.
  • the fluoropolymer (I) has a carboxylic acid type functional group (hereinafter, also referred to as a fluoropolymer (C)) and a sulfonic acid type functional group because the ion exchange performance is more excellent.
  • At least one selected from the group consisting of fluoropolymers hereinafter also referred to as fluoropolymers (S) is preferred.
  • fluoropolymers hereinafter also referred to as fluoropolymers (S)
  • the fluorine-containing polymer (C) preferably contains units based on a fluorine-containing olefin and units based on a monomer having a carboxylic acid type functional group and a fluorine atom.
  • the fluorine-containing olefin include fluoroolefins having one or more fluorine atoms in the molecule and having 2 to 3 carbon atoms. Specific examples thereof include tetrafluoroethylene (TFE), chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and hexafluoropropylene.
  • TFE is particularly preferred from the viewpoint of excellent monomer production cost, reactivity with other monomers, and properties of the obtained fluoropolymer.
  • the unit based on the fluorine-containing olefin may be contained alone or in combination of two or more.
  • a unit represented by the formula (1C) is preferable.
  • M C is a hydrogen atom, an alkali metal or a quaternary ammonium cation.
  • p is 0 or 1.
  • q is an integer of 0 to 12.
  • r is an integer of 0 to 3.
  • s is 0 or 1.
  • t is an integer of 0 to 12.
  • u is an integer of 0 to 3.
  • the fluorinated polymer (C) may contain units based on other monomers other than units based on a fluorinated olefin and units based on a monomer having a carboxylic acid type functional group and a fluorine atom.
  • the other monomer include CF 2 CFCFR f (R f is a perfluoroalkyl group having 2 to 10 carbon atoms), and CF 2 CFCF—OR f1 (R f1 is a C 1-10 carbon atom).
  • CF 2 CFCFO (CF 2 ) v CF CF 2 (v is an integer of 1 to 3).
  • the content of the unit based on another monomer is preferably 30% by mass or less based on all units in the fluoropolymer (C) from the viewpoint of maintaining ion exchange performance.
  • the fluorine-containing polymer (S) preferably contains units based on a fluorine-containing olefin and units based on a monomer having a sulfonic acid type functional group and a fluorine atom.
  • the fluorinated olefin include those exemplified above.
  • the unit based on the fluorine-containing olefin may be contained alone or in combination of two or more.
  • L is an n + 1-valent perfluorohydrocarbon group which may contain an oxygen atom.
  • the oxygen atom may be located at a terminal in the perfluorohydrocarbon group or may be located between carbon atoms.
  • the number of carbon atoms in the n + 1-valent perfluorohydrocarbon group is preferably 1 or more, more preferably 2 or more, preferably 20 or less, and more preferably 10 or less.
  • the divalent perfluoroalkylene group may be linear or branched.
  • A is a group that can be converted to a sulfonic acid type functional group.
  • the group that can be converted to a sulfonic acid type functional group is preferably a functional group that can be converted to a sulfonic acid type functional group by hydrolysis.
  • Specific examples of the group that can be converted to a sulfonic acid type functional group include —SO 2 F, —SO 2 Cl, and —SO 2 Br.
  • M S is a hydrogen atom, an alkali metal or a quaternary ammonium cation.
  • the unit represented by the formula (2S) includes a unit represented by the formula (2S-1), a unit represented by the formula (2S-2), and a unit represented by the formula (2S-3). preferable.
  • Formula (2S-1) [CF 2 —CF (—O—R f1 —SO 3 M S )] —
  • R f1 is a perfluoroalkylene group which may contain an oxygen atom between carbon atoms.
  • the number of carbon atoms in the perfluoroalkylene group is preferably 1 or more, more preferably 2 or more, preferably 20 or less, and more preferably 10 or less.
  • R f2 is a single bond or a perfluoroalkylene group which may contain an oxygen atom between carbon atoms.
  • the number of carbon atoms in the perfluoroalkylene group is preferably 1 or more, more preferably 2 or more, preferably 20 or less, and more preferably 10 or less.
  • r is 0 or 1.
  • M S is a hydrogen atom, an alkali metal or a quaternary ammonium cation.
  • w is an integer of 1 to 8
  • x is an integer of 1 to 5.
  • M S in the formula is as described above. -[CF 2 -CF (-O- (CF 2 ) w -SO 3 M S )]- -[CF 2 -CF (-O-CF 2 CF (CF 3 ) -O- (CF 2 ) w -SO 3 M S )]- -[CF 2 -CF (-(O-CF 2 CF (CF 3 )) x -SO 3 M S )]-
  • w is an integer of 1 to 8.
  • M S in the formula is as described above. -[CF 2 -CF (-(CF 2 ) w -SO 3 M S )]- -[CF 2 -CF (-CF 2 -O- (CF 2 ) w -SO 3 M S )]-
  • the unit represented by the formula (2S-3) is preferably a unit represented by the formula (2S-3-1). Defining M S in the formula is as described above.
  • R f3 is a linear perfluoroalkylene group having 1 to 6 carbon atoms
  • R f4 is a linear bond having 1 to 6 carbon atoms which may contain an oxygen atom between a single bond or a carbon atom. It is a perfluoroalkylene group. Defining r and M S in the formula is as described above.
  • Units based on a monomer having a sulfonic acid type functional group and a fluorine atom may be used alone or in combination of two or more.
  • the fluoropolymer (S) may contain units based on other monomers other than the units based on the fluoroolefin and the units based on the monomer having a sulfonic acid type functional group and a fluorine atom. Specific examples of other monomers include those exemplified above.
  • the content of the unit based on another monomer is preferably 30% by mass or less based on all units in the fluoropolymer (S) from the viewpoint of maintaining ion exchange performance.
  • the ion exchange membrane has a reinforcing cloth including a first reinforcing yarn and a second reinforcing yarn intersecting the first reinforcing yarn.
  • the reinforcing cloth is located on at least one of the inside and the surface of the present ion exchange membrane, and is preferably located inside the present ion exchange membrane.
  • the reinforcing cloth is arranged in a direction substantially parallel to the TD direction so that the first reinforcing yarn is along the TD direction of the ion exchange membrane, and is substantially MD-like so that the second reinforcing yarn is along the MD direction of the ion exchange membrane. Preferably, they are arranged in a direction parallel to the direction.
  • the reinforcing cloth is preferably a woven cloth in which the first reinforcing yarn and the second reinforcing yarn are plain-woven.
  • the first reinforcing yarn and the second reinforcing yarn intersect and preferably intersect at right angles.
  • Each of the first reinforcing yarn and the second reinforcing yarn may be a weft or a warp of the reinforcing cloth, but it is easy to set the ratio (R1 / R2) of the loop stiffness value to the range described later. Therefore, it is preferable that the first reinforcing yarn is a weft yarn and the second reinforcing yarn is a warp yarn.
  • the weft means a thread in the TD direction when weaving a woven fabric
  • the warp means a thread in the MD direction when weaving a woven fabric.
  • the denier of the first reinforcing yarn and the second reinforcing yarn is preferably 50 or more, more preferably 80 or more from the viewpoint that the strength of the reinforcing cloth can be increased, and is preferably 200 or less from the viewpoint of being excellent in the effect of reducing the electrolytic voltage. It is more preferably at most 150.
  • the denier number is a value (g / 9000 m) expressing the mass of the yarn of 9000 m in grams.
  • the density of the first reinforcing yarn and the second reinforcing yarn in the reinforcing cloth is preferably 15 yarns / inch or more, more preferably 20 yarns / inch or more, because the strength of the present ion exchange membrane is excellent. From the viewpoint of superiority, the number is preferably 100 lines / inch or less, and more preferably 90 lines / inch or less.
  • the first reinforcing yarn and the second reinforcing yarn may be composed of any one of a monofilament composed of one filament and a multifilament composed of two or more filaments, and a monofilament is preferable.
  • the first reinforcing yarn and the second reinforcing yarn are preferably made of a material which does not elute when the reinforcing cloth is immersed in an alkaline aqueous solution (for example, a sodium hydroxide aqueous solution having a concentration of 32% by mass).
  • the first reinforcing yarn and the second reinforcing yarn include a yarn made of polytetrafluoroethylene (hereinafter, also referred to as PTFE), a yarn made of polyphenylene sulfide, a yarn made of nylon, and a yarn made of polypropylene.
  • the ratio of the crimp rate of the first reinforcing thread to the crimp rate of the second reinforcing thread is preferably 0.5 to 4.5, more preferably 0.5 to 3.0. Preferably, it is more preferably from 0.5 to 2.0.
  • the crimp rate of the first reinforcing yarn is preferably 0.5 to 2.0%, more preferably 0.5 to 1.8%, and particularly preferably 0.5 to 1.5%.
  • the crimp rate of the first reinforcing yarn is 0.5% or more, an ion exchange membrane having excellent strength can be obtained.
  • the crimp rate of the first reinforcing yarn is 2.0% or less, an ion exchange membrane with less wrinkles can be obtained.
  • the crimp rate of the second reinforcing yarn is not particularly limited, but is preferably 0.1 to 2.0%, more preferably 0.1 to 1.8%, and more preferably 0.1 to 1.8%, from the viewpoint that the effect of the present invention can be further exhibited. Particularly preferred is 1-1.5%.
  • the crimp rates of the first reinforcing yarn and the second reinforcing yarn are calculated as follows based on the cross-sectional image of the reinforcing cloth.
  • a method for calculating the crimp rate of the first reinforcing yarn will be described.
  • the ion exchange membrane is cut in a direction along the first reinforcing yarn, and an enlarged image (for example, 100 times) of a cross section of the reinforcing cloth is photographed by an optical microscope (product name: BX-51, manufactured by Olympus Corporation). .
  • the distance between the centers of the second reinforcing yarns located at both ends in the enlarged image (a distance L 0 in FIG. 1 described later) and the second reinforcing yarns located at both ends in the enlarged image are determined.
  • the length (distance L in FIG. 1 to be described later) of the first reinforcing yarn existing therebetween is measured and calculated by the following equation 1.
  • Crimp rate (%) of first reinforcing yarn 100 ⁇ (L ⁇ L 0 ) / L 0 Equation 1
  • FIG. 1 is an enlarged cross-sectional view of a reinforcing cloth for explaining a method of measuring a crimp rate of a reinforcing yarn.
  • the reinforcing cloth 10 includes a first reinforcing thread 11, a second reinforcing thread 12 ⁇ / b> A, a second reinforcing thread 12 ⁇ / b> B, and a second reinforcing thread 12 ⁇ / b> C crossing the first reinforcing thread 11.
  • the distance L 0 is represents a distance between the centers of the second reinforcing threads located at both ends of the enlarged image, in the example of FIG. 1, the shortest distance connecting the center of the second reinforcing thread 12A, the center of the second reinforcing threads 12C It is.
  • the distance L represents the length of the first reinforcing thread existing between the second reinforcing threads located at both ends of the enlarged image, and in the example of FIG. 1, the distance between the second reinforcing thread 12A and the second reinforcing thread 12C. Is the sum of the distances L 1 , L 2 , L 3 , L 4 , L 5, and L 6 , which are the lengths of the first reinforcing yarns 11 existing in the first position.
  • one reinforcement thread 11 has a plurality of extreme points (positions indicating the maximum value and the minimum value of the first reinforcement thread 11 in the XY coordinates).
  • the total of the distances L 1 to L 6 connecting the adjacent extreme points at the shortest distance is the distance L.
  • the distance connecting the midpoint of the thickness of the first reinforcing thread 11 at the extreme value point is measured.
  • the calculation of the crimp rate of the second reinforcing thread is performed by replacing the first reinforcing thread with the second reinforcing thread in the description of the method of calculating the crimp rate of the first reinforcing thread, and replacing the second reinforcing thread with the first reinforcing thread. It is read and performed.
  • the method of adjusting the crimp ratio of the first reinforcing yarn and the second reinforcing yarn include a method of adjusting a tensile ratio in a direction along the first reinforcing yarn during heat setting of the ion exchange membrane (reinforcing cloth), and a method of reinforcing.
  • the reinforcing cloth is a plain woven cloth, the reinforcing cloth is manufactured by repeating the operation of passing the weft while the warp is stretched. Therefore, the crimp rate of the warp tends to be constant.
  • the crimp rate of the weft can be adjusted by the way of passing the weft. That is, the crimp rate of the weft can be adjusted more easily than the crimp rate of the warp.
  • the reinforcement fabric may include a sacrificial thread.
  • the sacrificial yarn is a yarn that at least partially elutes under the operating environment of the electrolytic device including the ion exchange membrane, and is preferably a yarn made of a material that elutes in the alkaline aqueous solution when the reinforcing cloth is immersed in the alkaline aqueous solution.
  • the sacrificial yarn may be a monofilament composed of one filament or a multifilament composed of two or more filaments.
  • the strength of the ion-exchange membrane is maintained by the sacrificial yarn, but the sacrificial yarn dissolves in the operating environment of the device, and the ion-exchange membrane dissolves.
  • the resistance of the film can be reduced.
  • a PET yarn made of polyethylene terephthalate hereinafter, also referred to as PET
  • a PET / PBT yarn made of a mixture of PET and polybutylene terephthalate (hereinafter, also called PBT)
  • PBT yarns made of PBT PTT yarns made of polytrimethylene terephthalate (hereinafter also referred to as PTT) are preferred, and PET yarns are particularly preferred.
  • the denier number of the sacrificial yarn is preferably 7 or more, more preferably 12 or more, and particularly preferably 9 or more. If the denier number of the sacrificial yarn is 7 or more, the stiffness of the ion exchange membrane is increased, so that the ion exchange membrane is excellent in mountability when mounted on the electrolytic device.
  • the denier number of the sacrificial yarn is preferably 100 or less, more preferably 60 or less, and particularly preferably 30 or less. If the denier of the sacrificial yarn is 100 or less, cracks are less likely to be formed on the surface of the ion exchange membrane, and a decrease in mechanical strength is suppressed.
  • the denier of the sacrificial yarn means the denier of the multifilament.
  • the density of the sacrificial yarn in the reinforcing cloth is preferably 40 yarns / inch or more, more preferably 50 yarns / inch or more, and particularly preferably 54 yarns / inch or more.
  • the density of the sacrificial yarn is 54 yarns / inch or more, the stiffness of the ion exchange membrane becomes strong, and thus the ion exchange membrane is excellent in mounting property when mounted on the electrolytic device.
  • the density of the sacrificial yarn is preferably 198 yarns / inch or less, more preferably 180 yarns / inch or less, and particularly preferably 110 yarns / inch or less. If the density of the sacrificial yarn is 110 yarns / inch or less, excellent woven fabric properties are obtained.
  • the present ion exchange membrane may have a hydrophilic layer on its surface.
  • the hydrophilic layer is preferably provided on at least one surface of the outermost surface of the present ion exchange membrane, and more preferably provided on both surfaces.
  • the hydrophilic layer can suppress the gas from adhering to the surface of the ion exchange membrane.
  • Specific examples of the hydrophilic layer include an inorganic particle layer containing inorganic particles. The inorganic particles preferably have excellent corrosion resistance to acids or alkalis and have hydrophilicity.
  • the hydrophilizing layer may include a binder.
  • a binder a known binder used for a known hydrophilic layer can be employed, and examples thereof include methylcellulose and a fluoropolymer having a sulfonic acid group.
  • the ratio of R1 to R2 From 0.60 to less than 0.95, more preferably from 0.60 to less than 0.85, more preferably from 0.60 to less than 0.85, from the viewpoint of excellent attachment of the ion exchange membrane to the electrolysis apparatus. Particularly preferably, it is 0.60 or more and less than 0.80.
  • the greater the loop stiffness value the higher the film stiffness. If the loop stiffness value is too large (the stiffness is too high), the adhesion to the electrode when mounted in the electrolytic cell will be poor.
  • the loop stiffness value When the loop stiffness value is too low (the stiffness is too low), wrinkles are easily generated in the ion exchange membrane.
  • the loop stiffness value can be measured using a loop stiffness tester (product name: DA, manufactured by Toyo Seiki Seisaku-sho, Ltd.) according to the method described in the Examples section described later.
  • the shape and size of the present ion exchange membrane may be appropriately determined according to the size of the electrolytic cell to which the present ion exchange membrane is mounted and the type of the electrode.
  • the thickness of the present ion exchange membrane is preferably 30 ⁇ m or more, more preferably 40 ⁇ m or more, from the viewpoint of maintaining a constant strength, and is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and 180 ⁇ m from the viewpoint of increasing current efficiency and voltage efficiency. The following are more preferred.
  • the present ion exchange membrane may have a single-layer structure or a multilayer structure.
  • a multilayer structure for example, an embodiment in which a plurality of layers containing a fluorine-containing polymer (S) and having different ion exchange capacities and units different from each other are stacked.
  • a layer of the fluoropolymer (S) and a layer of the fluoropolymer (C) are laminated.
  • ion exchange membrane examples include various polymer applications such as solid polymer fuel cells, direct methanol fuel cells, redox flow batteries, and air batteries, solid polymer water electrolysis, alkaline water electrolysis, and ozone.
  • electrolysis devices such as water electrolysis, salt electrolysis, organic material electrolysis, and chlorides and oxides can be mentioned, and it is preferable to use them for alkali chloride electrolysis such as salt electrolysis since the effects of the present invention can be more exhibited.
  • it can be used as a separator or a solid electrode in various types of electrochemical cells for selective cation transport at a binding portion of the cells.
  • electrochemical-related applications it can be used for various gas sensors, biosensors, light-emitting devices, optical devices, organic matter sensors, solubilization of carbon nanotubes, actuators, catalysts and the like as sensor applications.
  • the present ion exchange membrane can be obtained by a known method described in, for example, International Publication No. WO 2016/140283. Specifically, a reinforcing cloth is embedded in a fluorine-containing polymer having a group that can be converted to an ion-exchange group, and a membrane containing the reinforcing cloth and a fluorine-containing polymer having a group that can be converted to an ion-exchange group (hereinafter referred to as a reinforced polymer). (Also referred to as a precursor film). Next, a group that can be converted to an ion exchange group in the reinforced precursor membrane is hydrolyzed and converted to an ion exchange group.
  • the present ion exchange membrane is a laminate
  • a membrane containing a fluorine-containing polymer having a group that can be converted to an ion exchange group (hereinafter also referred to as a precursor membrane) without a reinforcing cloth is reinforced
  • An ion exchange membrane may be manufactured using a reinforced precursor membrane obtained by laminating a cloth between the precursor membranes.
  • the method may include a step of forming the above-mentioned hydrophilic layer on the surface of the reinforcing precursor film. After the hydrolysis using the strengthened precursor membrane described above, the counter ion of the ion exchange group may be converted to hydrogen, sodium, potassium, or the like, depending on the application.
  • a film, sheet, or net may be used to protect the hydrophilic layer.
  • the cation can be subjected to alkaline water electrolysis in an environment where the substituted cation exists, and the dimensional stability of the present ion exchange membrane can be improved. The performance is improved.
  • the ion exchange membrane after the hydrolysis or counter ion exchange is generally wetted with the liquid medium used for hydrolysis or counter ion exchange or the water for subsequent washing with water.
  • the wet ion exchange membrane may be used as it is as the present ion exchange membrane, or the dried ion exchange membrane may be used as the present ion exchange membrane after drying.
  • the electrolytic device of the present invention has the above-described ion exchange membrane (the present ion exchange membrane).
  • the electrolytic device is not limited to this, but includes, for example, an electrolytic cell having a cathode and an anode, and the present ion exchange membrane, and the present ion exchange membrane has both electrodes (that is, the cathode and the anode).
  • An embodiment is provided in which the cells are separated from each other in the electrolytic cell. Since the electrolysis apparatus of the present invention has the present ion exchange membrane having excellent durability, it exhibits excellent electrolysis performance even when operated for a long time.
  • the thickness of each film was determined by observing a cross section of each film with an optical microscope and using image analysis software.
  • the ion exchange membrane is cut in the direction along the first reinforcing yarn (weft), and an enlarged image (for example, 2 to 4 mm in width) of a cross section (width 2 to 4 mm) of the reinforcing cloth is observed with an optical microscope (product name: BX-51, manufactured by Olympus Corporation). , 100 ⁇ ), and the distance between the centers (distance L 0 ) of the second reinforcing yarns (warps) located at both ends of the enlarged image and the second reinforcing yarns located at both ends of the enlarged image.
  • the length (distance L) of the reinforcing yarn was measured, and the crimp rate of the first reinforcing yarn was measured according to the above equation (1).
  • the crimp rate of the first reinforcing yarn was obtained as an average value calculated from enlarged images at arbitrary 10 positions.
  • the crimp ratio of the second reinforcing yarn is the same as the crimp rate of the first reinforcing yarn, except that the measured value of the length (distance L) of the second reinforcing yarn existing between the first reinforcing yarns is used. The rate was calculated.
  • the crimp rate of the second reinforcing thread was also obtained as an arithmetic average value calculated from enlarged images at arbitrary 10 positions, similarly to the crimp rate of the first reinforcing thread.
  • loop stiffness value Using a loop stiffness tester (product name "DA", manufactured by Toyo Seiki Seisaku-sho, Ltd.), using a strip-shaped ion exchange membrane test piece having a width of 15 mm and a length of 150 mm, a test piece having a loop length of 60 mm and a test piece The loop stiffness value was measured under the conditions of an indenter pushing amount of 15 mm and a pushing speed of 5 mm / sec. The loop stiffness value was calculated as an arithmetic average of the loop stiffness values of five test pieces. When measuring R1, the test piece was prepared so that the length direction of the test piece was along the first reinforcing yarn (weft), and when measuring R2, the length of the test piece was measured. A test piece was prepared so that the length direction was along the second reinforcing yarn (warp).
  • DA a loop stiffness tester
  • the durability of the ion exchange membrane was evaluated based on the falling rate of the inorganic particle layer formed on the surface of the ion exchange membrane. Specifically, an ion-exchange membrane having an inorganic particle layer formed on its surface is placed in a test electrolytic cell having an effective energization area of 1.5 dm 2 (electrolytic surface size: 150 mm ⁇ 100 mm) and serves as a cathode.
  • Sodium hydroxide concentration is discharged from the cathode chamber: 32 wt%, the sodium chloride concentration is supplied to the anode chamber: while adjusted to 200 g / L, temperature 90 ° C., a current density: 12 kA / m 2 at 2 conditions
  • the operation was performed for a week, and electrolysis of the aqueous sodium chloride solution was performed.
  • the ion exchange membrane was installed so that the MD direction was vertical. After the operation was completed, the ion exchange membrane was taken out of the electrolytic cell, the state of the inorganic particle layer remaining on the surface of the ion exchange membrane was confirmed, the falling rate was calculated, and the durability was evaluated according to the following criteria.
  • Drop-off rate (%) 100 ⁇ ⁇ 1 ⁇ (area of inorganic particle layer after test) / (area of inorganic particle layer before test) ⁇
  • ion exchange membrane is attached to an electrode in an electrolytic cell (manufactured by AGC, product name: AZEC-B1), the state of wrinkling of the ion exchange membrane at the time of attachment, and the gap between the electrode and the ion exchange membrane. The state of occurrence was visually checked.
  • the mountability was measured for 70 ion exchange membranes, and the mountability was evaluated according to the following criteria. ⁇ : Two or less ion-exchange membranes with voids between electrodes and wrinkles. :: 3 to 7 ion exchange membranes with voids or wrinkles between electrodes. ⁇ : 8 to 12 ion-exchange membranes having voids formed between the electrodes and wrinkles. ⁇ : 13 or more ion exchange membranes with voids between the electrodes and wrinkles.
  • TFE is copolymerized with a fluorinated monomer having a group that can be converted to a carboxylic acid type functional group represented by the following formula (X), and a fluorinated polymer having a group that can be converted to a carboxylic acid type functional group (hydrolysis)
  • a fluorinated polymer having a group that can be converted to a carboxylic acid type functional group hydrolysis
  • Subsequent ion exchange capacity: 1.08 meq / g resin) (hereinafter referred to as polymer C) was synthesized.
  • TFE is copolymerized with a fluorine-containing monomer having a group that can be converted to a sulfonic acid type functional group represented by the following formula (Y), and a fluorine-containing polymer having a group that can be converted to a sulfonic acid type functional group (hydrolysis)
  • a fluorine-containing polymer having a group that can be converted to a sulfonic acid type functional group hydrolysis
  • TFE is copolymerized with a fluorine-containing monomer having a group that can be converted to a sulfonic acid type functional group represented by the formula (Y), and a fluorine-containing polymer having a group that can be converted to a sulfonic acid type functional group (after hydrolysis) (Ion exchange capacity: 1.10 meq / g resin) (hereinafter referred to as polymer S2) was synthesized.
  • the polymer C and the polymer S1 are molded by a co-extrusion method, and a precursor layer (C ′) made of the polymer C (thickness: 12 ⁇ m) and a precursor layer (S′a) made of the polymer S1 (thickness: 68 ⁇ m) was obtained.
  • the polymer S2 was molded by a melt extrusion method to obtain a film B of a precursor layer (S′b) (thickness: 30 ⁇ m) composed of the polymer S2.
  • the monofilament obtained by slitting it to a thickness of 100 denier and twisting 2,000 times / m is reinforced with a PTFE yarn, a weft (first reinforcement yarn) and a warp (second reinforcement yarn). Thread).
  • a PET yarn consisting of a 30-denier multifilament obtained by arranging six 5-denier PET filaments was used as a sacrificial yarn. Plain weave was performed so that one reinforcing yarn and four sacrificial yarns were alternately arranged to obtain a reinforcing cloth (reinforcement yarn density: 27 yarns / inch, sacrificial yarn density: 104 yarns / inch).
  • the reinforcing cloth was pulled in the direction along the weft while heating the reinforcing cloth at 200 ° C. so that the crimp rate of the reinforcing yarn constituting the reinforcing cloth in the ion exchange membrane became the value shown in Table 1.
  • the ion exchange membrane of Example 1 was manufactured as follows.
  • the film B, the reinforcing cloth, the film A, the release PET film (thickness: 100 ⁇ m) are stacked in this order, and the precursor layer (C ′) of the film A is on the release PET film side. And laminated.
  • the release PET film was peeled off to obtain a reinforced precursor film.
  • the reinforcing cloth was laminated so that the weft yarns along the MD direction and the warp yarns along the TD direction of the obtained ion exchange membrane.
  • the thickness of each layer in the reinforced precursor film was 12 ⁇ m for the precursor layer (C ′), 68 ⁇ m for the precursor layer (S′a), and 30 ⁇ m for the precursor layer (S′b).
  • the precursor layer (S'a) and the precursor layer (S'b) constitute the precursor layer (S ').
  • Consisting of 29.0% by mass of zirconium oxide (average particle size: 1 ⁇ m), 1.3% by mass of methylcellulose, 4.6% by mass of cyclohexanol, 1.5% by mass of cyclohexane, and 63.6% by mass of water.
  • the paste was transferred to the upper layer side (that is, the precursor layer (S'b)) of the precursor layer (S ') of the reinforced precursor film by a roll press to form an inorganic particle layer.
  • the attached amount of zirconium oxide was 20 g / m 2 .
  • a reinforced precursor film having an inorganic particle layer formed on one surface was heated to 95 ° C. only at the precursor layer (S ′) side with the outer periphery of the film sealed with PTFE packing, and 40% by mass dimethyl sulfoxide and 10% by mass. % Potassium hydroxide in a first alkali aqueous solution and treated for 10 minutes. After removing the first alkali aqueous solution by washing with water, only the precursor layer (C ′) side is contacted with a second alkaline aqueous solution of 5% by mass of dimethyl sulfoxide and 30% by mass of potassium hydroxide heated to 55 ° C. The treatment was performed for 120 minutes, and the second aqueous alkali solution was removed by washing with water.
  • a dispersion was prepared by dispersing zirconium oxide (average particle diameter: 1 ⁇ m) at a concentration of 13% by mass in an ethanol solution containing 2.5% by mass of the acid-type polymer of the polymer S1. This dispersion was sprayed on the layer (C) side of the membrane to form an inorganic particle layer, and an ion exchange membrane having an inorganic particle layer formed on both surfaces was obtained.
  • the attached amount of zirconium oxide was 3 g / m 2 .
  • the dry thickness of the ion exchange membrane thus obtained was 120 ⁇ m.
  • Example 2 The strength at the time of pulling the reinforcing cloth in the direction along the weft while heating the reinforcing cloth at 200 ° C. was adjusted so that the crimp rate of the reinforcing yarn constituting the reinforcing cloth in the ion exchange membrane became the value shown in Table 1. Except for the above, an ion exchange membrane of Example 2 was obtained in the same manner as in Example 1.
  • Example 3 Using a reinforcing cloth plainly woven so that one reinforcing yarn and two sacrificial yarns are alternately arranged (reinforcing yarn density: 27 yarns / inch, sacrificial yarn density: 52 yarns / inch), the ion exchange membrane is used. Except that the strength at the time of pulling in the direction along the weft while heating the reinforcing cloth at 200 ° C. was adjusted so that the crimping ratio of the reinforcing yarns constituting the reinforcing cloth of Example 1 was as shown in Table 1. In the same manner as in Example 1, an ion exchange membrane of Example 3 was obtained.
  • Example 4 The strength at the time of pulling the reinforcing cloth in the direction along the weft while heating the reinforcing cloth at 200 ° C. was adjusted so that the crimp rate of the reinforcing yarn constituting the reinforcing cloth in the ion exchange membrane became the value shown in Table 1. Except for the above, an ion exchange membrane of Example 4 was obtained in the same manner as in Example 3.
  • Example 5 After rapidly stretching the PTFE film, slitting it to a thickness of 50 denier and twisting the monofilament at 2000 times / m, the PTFE yarn is used as a reinforcing yarn, and the weft (first reinforcing yarn) and the warp (second reinforcing yarn). Thread). By adjusting the warp tension and the weft tension at the time of weaving the reinforcing cloth, using a reinforcing cloth in which only the reinforcing yarn is plain-woven (the density of the reinforcing yarn: 80 yarns / inch), the reinforcing cloth is pulled while being heated at 200 ° C. An ion exchange membrane of Example 5 was obtained in the same manner as in Example 1 except that the operation was not performed.

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JP2015158017A (ja) * 2015-05-08 2015-09-03 旭化成ケミカルズ株式会社 陽イオン交換膜及びこれを用いた電解槽
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JP2013163791A (ja) * 2012-02-13 2013-08-22 Asahi Kasei Chemicals Corp 陽イオン交換膜及びそれを用いた電解槽
JP2015158017A (ja) * 2015-05-08 2015-09-03 旭化成ケミカルズ株式会社 陽イオン交換膜及びこれを用いた電解槽
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