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WO2016060114A1 - Tube à perméabilité sélective à la vapeur d'eau - Google Patents

Tube à perméabilité sélective à la vapeur d'eau Download PDF

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Publication number
WO2016060114A1
WO2016060114A1 PCT/JP2015/078927 JP2015078927W WO2016060114A1 WO 2016060114 A1 WO2016060114 A1 WO 2016060114A1 JP 2015078927 W JP2015078927 W JP 2015078927W WO 2016060114 A1 WO2016060114 A1 WO 2016060114A1
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WIPO (PCT)
Prior art keywords
fluororubber
water vapor
fluorine
cation exchange
selective permeable
Prior art date
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Ceased
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PCT/JP2015/078927
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English (en)
Japanese (ja)
Inventor
齋藤　孝博
健 射矢
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AGC Engineering Co Ltd
AGC Inc
Original Assignee
Asahi Glass Co Ltd
AGC Engineering Co Ltd
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Publication date
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Publication of WO2016060114A1 publication Critical patent/WO2016060114A1/fr
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Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04—Tubular membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D71/24—Rubbers
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to a water vapor selective permeable tube.
  • a hollow fiber membrane made of a fluorine-based cation exchange resin having a cation exchange group selectively selects water vapor from the higher one to the lower one according to the water vapor partial pressure inside and outside the hollow fiber membrane. Can be transmitted. Therefore, it is used as a water vapor selective permeable tube for dehumidification and humidification.
  • the water vapor selective permeable tube can be used, for example, in a condensed water remover provided in the middle of a pipe for supplying a sample gas to an analyzer or the like (Patent Document 1).
  • JP 2009-072701 A International Publication No. 2009/0554036
  • the tube may be provided with flexibility.
  • a method for imparting flexibility it is conceivable to mix rubber with a fluorine-based cation exchange resin.
  • a hydrocarbon-based synthetic rubber such as ethylene / propylene / diene rubber because it is not compatible with the fluorine-based resin and cannot be uniformly kneaded.
  • an object of the present invention is to provide a water vapor selective permeable tube that can sufficiently reduce a bending radius and has high resistance to bending elongation stress.
  • the present invention has the following aspects.
  • Fluorine cation exchange resin (A) having a cation exchange group and fluorine rubber (B), and the fluorine rubber (B) is 20 mass of sodium hydroxide measured in accordance with JIS K6258: 2003
  • the volume change rate when kept in a 100% aqueous solution at 100 ° C. for 3 days is less than 40%, and the fluororubber (B) relative to the total mass of the fluorocation exchange resin (A) and the fluororubber (B) )
  • the mass ratio (B) / [(A) + (B)] is 15 to 70% by mass.
  • X 1 and X 2 are each independently a fluorine atom, a chlorine atom, or a trifluoromethyl group
  • X 3 is a fluorine atom or a trifluoromethyl group
  • s is 0 or 1
  • t is an integer from 1 to 5
  • W is a precursor group that can be converted to —SO 3 ⁇ M + (wherein M + is an alkali metal ion or hydrogen ion) by hydrolysis
  • X 4 is a fluorine atom or a trifluoromethyl group
  • m is 0 or 1
  • n is an integer of 1 to 5
  • Y is a precursor group that can be converted into —COO ⁇ M + (where
  • Step 1 A precursor composition is obtained by kneading a precursor of a fluorine-based cation exchange resin (A) that can be converted into a fluorine-based cation exchange resin (A) by hydrolysis and a fluororubber (B).
  • Step 2 Mold the precursor composition into a tube.
  • Step 3 The obtained tube is hydrolyzed and further acidified as necessary.
  • the water vapor selective permeable tube of the present invention can sufficiently reduce the bending radius and has high resistance to bending elongation stress.
  • a monomer represented by the formula (1) is referred to as a monomer (1).
  • the following definitions of terms apply throughout this specification and the claims.
  • the “cation exchange group” is a group in which at least a part of the cation contained in the group can exchange ions with other cations.
  • “Fluorine-based cation exchange resin” means a cation exchange resin having fluorine atoms in the molecule.
  • “Monomer” means a compound having a polymerization-reactive carbon-carbon double bond.
  • Structural unit means a unit derived from a monomer formed by polymerization of the monomer.
  • the structural unit may be a unit directly formed by a polymerization reaction of monomers, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
  • the “precursor group” means a group that can be converted into a cation exchange group by a known treatment such as hydrolysis treatment or acidification treatment.
  • “Fluoro rubber” means an elastic copolymer (fluorine-containing elastomer) having fluorine atoms in the molecule.
  • the water vapor selective permeable tube of the present invention is a tube containing a fluorine-based cation exchange resin (A) and a fluorine rubber (B).
  • the outer diameter of the tube is preferably 1 mm or more, more preferably 4 to 30 mm, and particularly preferably 6 to 30 mm.
  • the larger the outer diameter of the tube the more difficult it is to make the bending radius small, and it is easy to use it in a situation where repeated bending and stretching are necessary, so the effect of the present invention is useful.
  • the thickness of the tube can be appropriately set according to the outer diameter of the tube. Usually, 0.05 to 5.0 mm is preferable, and 0.1 to 2.5 mm is more preferable.
  • the fluorine-based cation exchange resin (A) is an ion exchange resin having a cation exchange group and a fluorine atom in the molecule.
  • the cation exchange group include a carboxylic acid group, a sulfonic acid group, a sulfonimide group, and a sulfonemethide group. From the viewpoint of ion selectivity and industrial productivity, a sulfonic acid group or a carboxylic acid group is preferable. The group is particularly preferred.
  • the cation exchange group may be either acid type or alkali metal salt type.
  • the fluorine-based cation exchange resin (A) is preferably a perfluorocarbon polymer having a cation exchange group (which may contain an etheric oxygen atom) from the viewpoint of the chemical durability of the membrane.
  • Particularly preferred are copolymers comprising units based on perfluorovinyl ether having Specifically, the fluorine-based cation exchange resin shown below (A1) (hereinafter sometimes referred to as “resin (A1)”) or the fluorine-based cation exchange resin (hereinafter “A2”).
  • Resin (A2) ” may be preferable), and resin (A1) is particularly preferable.
  • a copolymer containing a unit based on tetrafluoroethylene and a unit based on a perfluorovinyl ether having a sulfonic acid group is preferable.
  • CF 2 CX 1 X 2 (1)
  • CF 2 CF (OCF 2 CFX 3 ) s O (CF 2 ) t W (2)
  • CF 2 CF (OCF 2 CFX 4 ) m O (CF 2 ) n Y (3)
  • X 1 and X 2 are each independently a fluorine atom, a chlorine atom or a trifluoromethyl group, and a fluorine atom is preferred from the viewpoint of the durability of the film.
  • X 3 is a fluorine atom or a trifluoromethyl group.
  • s is 0 or 1.
  • t is an integer of 1 to 5.
  • W is a precursor group that can be converted into a sulfonic acid group or a salt thereof (—SO 3 ⁇ M + , where M + is an alkali metal ion or a hydrogen ion) by hydrolysis.
  • W is —SO 2 X 5 (where X 5 is a fluorine atom, chlorine atom or bromine atom), —SO 2 R 1 (where R 1 is an alkyl group having 1 to 4 carbon atoms). ) Is preferred, —SO 2 X 5 is more preferred, and —SO 2 F is particularly preferred.
  • CF 2 CFOCF 2 CF (CF 3 ) OCF 2 CF 2 CF 2 SO 2 F
  • CF 2 CFOCF 2 CF (CF 3 ) OCF 2 CF 2 SO 2 F
  • CF 2 CFOCF 2 CF 2 CF 2 SO 2 F
  • CF 2 CFOCF 2 CF 2 SO 2 F.
  • X 4 is a fluorine atom or a trifluoromethyl group.
  • m is 0 or 1.
  • n is an integer of 1 to 5.
  • Y is a precursor group that can be converted into a carboxylic acid group or a salt thereof (—COO ⁇ M + , where M + is an alkali metal ion or a hydrogen ion) by hydrolysis.
  • Y is preferably —COOR 2 (wherein R 2 is an alkyl group having 1 to 4 carbon atoms), —CN, —COZ (where Z is a halogen atom), and —COOR 2 is more preferable.
  • -COOCH 3 is particularly preferred.
  • CF 2 CFOCF 2 CF (CF 3 ) OCF 2 CF 2 COOCH 3
  • CF 2 CFOCF 2 CF 2 COOCH 3
  • CF 2 CFOCF 2 CF 2 CF 2 COOCH 3
  • CF 2 CFOCF 2 CF 2 CF 2 OCF 2 CF 2 COOCH 3
  • CF 2 CFOCF 2 CF 2 CF 2 CF 2 COOCH 3
  • CF 2 CFOCF 2 CF (CF 3) OCF 2 CF 2 CF 2 COOCH 3.
  • the weight average molecular weight of the fluorinated cation exchange resin (A) is preferably 150,000 to 3,000,000, more preferably 300,000 to 1,000,000 from the viewpoint of performance in terms of performance.
  • the weight average molecular weight of the fluorine-based cation exchange resin (A) is determined by gel permeation chromatography and converted from a calibration curve prepared using a standard polystyrene sample having a known molecular weight.
  • the ion exchange capacity of the fluorine-based cation exchange resin (A) is preferably 0.1 to 4 meq / g dry resin, more preferably 0.8 to 1.8 meq / g dry resin. If the ion exchange capacity is at least the preferred lower limit, sufficient water vapor permeability can be obtained. If the ion exchange capacity is less than or equal to the preferred upper limit, synthesis of a polymer having a high molecular weight is easy, and swelling of the polymer is suppressed.
  • the ratio (molar ratio) between the structural unit based on the monomer (1) and the structural unit based on the monomer (2) is set to be the above-mentioned preferable ion exchange capacity. Specifically, it is preferably 99: 1 to 60:40, and more preferably 97: 3 to 80:20.
  • the resin (A1) may contain other units other than the structural unit based on the monomer (1) and the structural unit based on the monomer (2) as long as the effects of the present invention are not impaired.
  • the ratio (molar ratio) between the structural unit based on the monomer (1) and the structural unit based on the monomer (3) is set to be the above-mentioned preferable ion exchange capacity.
  • the resin (A2) may contain other units other than the structural unit based on the monomer (1) and the structural unit based on the monomer (3) as long as the effects of the present invention are not impaired.
  • the fluororubber (B) has a fluorine atom in the molecule and is an elastic copolymer (fluorine-containing elastomer), which is 100 ° C. in a 20% by mass aqueous solution of sodium hydroxide measured according to JIS K6258: 2003.
  • the volume change rate when held for 3 days is less than 40%.
  • a hollow fiber membrane made of a fluorinated cation exchange resin having a cation exchange group is hydrolyzed with an aqueous solution of an alkali metal hydroxide or the like in order to impart water vapor selective permeability, and if necessary, hydrochloric acid, It is necessary to acidify with an aqueous solution of nitric acid or sulfuric acid.
  • the present inventors initially predicted that fluororubbers can withstand these aqueous solutions, but some fluororubbers cannot be used as products because they are decomposed by an alkaline aqueous solution in the hydrolysis step. I found out. Further, it has been found that the fluororubber having a volume change rate of less than 40% can sufficiently withstand the alkaline aqueous solution in the hydrolysis step.
  • the volume change rate is preferably less than 30%, and more preferably less than 20%.
  • the fluororubber (B) satisfying the above volume change rate is a copolymer shown in the following (B1) and (B2) (hereinafter, the copolymer shown in (B1) is referred to as “fluororubber (B1)”).
  • the copolymer shown in (B2) may contain any one or more of “fluororubber (B2)”, and preferably contains fluororubber (B1) and fluororubber ( More preferably, it consists of any one or more of B2), more preferably any of fluororubber (B1) and fluororubber (B2), and particularly preferably fluororubber (B1).
  • B1 Tetrafluoroethylene / propylene copolymer.
  • (B2) Tetrafluoroethylene / propylene / vinylidene fluoride copolymer.
  • vinylidene fluoride / hexafluoropropylene copolymer vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, and the like are difficult to satisfy the above volume change rate.
  • a ratio of a structural unit based on tetrafluoroethylene (hereinafter sometimes referred to as “TFE”) and a structural unit based on propylene (hereinafter sometimes referred to as “P”) (TFE”) and a structural unit based on propylene (hereinafter sometimes referred to as “P”) (
  • the molar ratio is preferably 40/60 to 70/30, more preferably 45/55 to 65/35, and most preferably 50/50 to 60/40.
  • the fluororubber (B1) may contain a structural unit based on a comonomer other than a structural unit based on TFE and a structural unit based on P as long as the effects of the present invention are not impaired.
  • Other comonomers include fluorinated olefins, perfluoroalkyl vinyl ethers, hydrocarbon olefins, alkyl vinyl ethers, vinyl esters and the like.
  • the fluororubber (B1) contains a constituent unit based on another comonomer, the content is preferably 20 mol% or less with respect to the total content of the constituent unit based on TFE and the constituent unit based on P. 15 mol% or less is more preferable, and 10 mol% or less is particularly preferable.
  • the fluororubber (B2) contains a structural unit based on vinylidene fluoride (hereinafter sometimes referred to as “VdF”).
  • VdF vinylidene fluoride
  • the ratio (molar ratio) of [the structural unit based on TFE and the structural unit based on P] / the structural unit based on VdF is preferably 90/10 to 50/50, 85/15 to 55/45 is more preferable, 80/20 to 60/40 is more preferable, and 80/20 to 70/30 is particularly preferable.
  • the molar ratio of the structural unit based on TFE / the structural unit based on P is preferably 40/60 to 70/30, more preferably 50/50 to 65/35, and most preferably 51/49 to 58/42.
  • a commercially available product of fluororubber (B2) AFLAS200P manufactured by Asahi Glass Co., Ltd. may be mentioned.
  • the fluororubber (B2) may contain one or more structural units based on other comonomers.
  • Other comonomers include fluorinated olefins, perfluoroalkyl vinyl ethers, hydrocarbon olefins, alkyl vinyl ethers, vinyl esters and the like.
  • the fluororubber (B2) contains a constituent unit based on another comonomer, the content is based on the total content of the constituent unit based on TFE, the constituent unit based on P, and the constituent unit based on VdF. 0.01 to 20 mol% is preferable, 0.1 to 15 mol% is more preferable, and 1 to 10 mol% is particularly preferable.
  • the fluorine atom content of the fluorororubber (B) is preferably 40 to 75% by mass, more preferably 45 to 75% by mass, and particularly preferably 50 to 75% by mass.
  • the fluorine atom content of the fluororubber (B) is the ratio of the total mass of all fluorine atoms to the total mass of the fluororubber.
  • the Mooney viscosity of the fluorororubber (B) according to JIS K6300 (ML 1 + 10 , 100 ° C., hereinafter may be simply referred to as “Mooney viscosity”) is preferably from 1 to 200, more preferably from 5 to 190, 180 is particularly preferred.
  • Mooney viscosity is equal to or higher than the preferable lower limit value, flexibility is improved, and when the Mooney viscosity is equal to or lower than the preferable upper limit value, workability is improved.
  • the glass transition temperature Tg of the fluororubber (B) is preferably ⁇ 40 to 20 ° C., more preferably ⁇ 30 to 15 ° C., and particularly preferably ⁇ 20 to 10 ° C. When the glass transition temperature Tg is at least the preferred lower limit, the balance between flexibility and strength at low temperatures is good, and when it is at most the preferred upper limit, low-temperature flexibility is good.
  • the storage shear elastic modulus G ′ of the fluororubber (B) is preferably 60 to 600, more preferably 200 to 550, and particularly preferably 250 to 500.
  • the value of the storage shear modulus G ′ (hereinafter sometimes simply referred to as “G ′”) is measured at a temperature of 100 ° C. according to ASTM D5289 and D6204 using a viscoelasticity measuring device (product name: RPA2000) manufactured by Alpha Technologies. The value obtained by measuring at an amplitude of 0.5 degrees and a frequency of 50 times / minute. The larger the value of G ′, the higher the molecular weight.
  • the method for polymerizing the monomer in the method for producing the fluororubber (B) is not particularly limited, and a known polymerization method such as an emulsion polymerization method or a solution polymerization method can be used.
  • the emulsion polymerization method is preferred because it is excellent in adjustment of molecular weight and copolymer composition and productivity.
  • a monomer mixture is radically copolymerized in the presence of an aqueous medium, a radical polymerization initiator, an emulsifier, a chain transfer agent and the like.
  • Known emulsifiers, aqueous media, radical polymerization initiators, and chain transfer agents can be used.
  • a step of introducing a crosslinking site is performed as necessary. If it has a crosslinking site, the crosslinking reaction will proceed easily.
  • the crosslinking site in the fluororubber (B2) include a double bond, a bromine group, an iodine group, and a cyano group.
  • a method for introducing a crosslinking site a known method can be used. For example, when the crosslinking site is a double bond, an alkali is added to the fluororubber (B), and the main chain is deHFed. A method of forming a double bond can be used.
  • the content of the crosslinking site is preferably 0.01 to 5 mol%, more preferably 0.05 to 3 mol%, and more preferably 0.1 to 2 mol% with respect to the total of the structural units constituting the fluororubber (B). % Is particularly preferred.
  • the content of the crosslinking site can be measured by a spectroscopic method such as infrared absorption analysis, nuclear magnetic resonance, or fluorescent X-ray elemental analysis.
  • the fluororubber (B) may contain a crosslinking agent.
  • the content of the crosslinking agent is 0.1 to 5 parts by mass, preferably 0.2 to 4 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the fluororubber (B). It is.
  • a crosslinking agent a well-known crosslinking agent can be used suitably. In particular, it is preferable to use an organic peroxide.
  • Any organic peroxide that generates radicals in the presence of heat or a redox system is used, and those that are mainly used as polymerization initiators, curing agents, or crosslinking agents for resins or synthetic rubbers are used. it can.
  • an organic peroxide is a derivative of hydrogen peroxide, and due to the presence of an oxygen bond in the molecule, it is thermally decomposed at a relatively low temperature and easily generates free radicals.
  • the reaction caused by the generated free radical includes an addition reaction to an unsaturated double bond and an extraction reaction such as hydrogen.
  • the latter hydrogen abstraction reaction is utilized to be used as a crosslinking agent or crosslinking accelerator for various synthetic rubbers or synthetic resins, a modifier for polypropylene, and the like.
  • a crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the fluorinated cation exchange resin (A) and the fluorinated rubber (B) in the water vapor selective permeable tube of the present invention is a fluorinated rubber relative to the total mass of the fluorinated cation exchange resin (A) and the fluorinated rubber (B).
  • the mass ratio (B) / [(A) + (B)] of (B) is 15 to 70 mass%.
  • (B) / [(A) + (B)] is preferably 20 to 65% by mass, and more preferably 25 to 60% by mass.
  • Preferred (B) / [(A) + (B)] varies depending on the application.
  • the water vapor selective permeable tube of the present invention can contain a known additive to be added as necessary, in addition to the fluorine-based cation exchange resin (A) and the fluororubber (B).
  • the additive include processing aids and fillers.
  • the processing aid include polyethylene wax, metal stearate, polytetrafluoroethylene, and examples of the filler include carbon black and white carbon.
  • the addition amount is preferably 5% by mass or less, preferably 3% by mass or less, based on the total content of the fluorine-based cation exchange resin (A) and the fluororubber (B). It is more preferable.
  • the water vapor selective permeable tube of the present invention preferably contains substantially no polymer component other than the fluorine-based cation exchange resin (A) and the fluorine rubber (B). Note that “substantially not contained” means that inevitable contaminants exist and that other polymer components are allowed to be mixed within a range that does not substantially affect the effects of the present invention. To do.
  • a reinforcing material may be embedded in the water vapor selective permeable tube of the present invention. Further, a reinforcing material may be laminated on one or both of the outer surface and the inner surface. Examples of the reinforcing material include woven fabric, non-woven fabric, fibril, and porous material, and woven fabric is preferable from the viewpoint of strength. Examples of the reinforcing material include fluorine-based polymers such as polytetrafluoroethylene.
  • the water vapor selective permeable tube of the present invention can be manufactured, for example, by the following steps.
  • Process 1 The process of knead
  • Step 2 A step of molding the precursor composition into a tube.
  • Step 3 A step of subjecting the obtained tube to a hydrolysis treatment and, if necessary, an acidification treatment.
  • the precursor of the fluorine-based cation exchange resin (A) is a resin that can be converted into the fluorine-based cation exchange resin (A) by a known treatment such as hydrolysis treatment or acidification treatment. Specifically, it is a resin having a precursor group in the molecule and containing a fluorine atom.
  • the fluorine-based cation exchange resin (A) is the resin (A1)
  • the precursor is a co-polymer having a structural unit based on the monomer (1) described above and a structural unit based on the monomer (2) described below. It is a coalescence.
  • the precursor is a copolymer having a structural unit based on the monomer (1) described above and a structural unit based on the monomer (3) described below. It is a coalescence.
  • step 1 it is preferable to obtain a precursor composition which is melt-kneaded with a melt-kneader and formed into a pellet.
  • the precursor of the fluorine-based cation exchange resin (A), the fluororubber (B), the additive blended as necessary is melt-kneaded with a melt-kneader, and then the strand from the die
  • the precursor composition formed into pellets is obtained by extruding, cooling the strands, and cutting the strands into appropriate lengths with a cutter or the like.
  • the melt kneader examples include an internal mixer, a single screw kneader, a twin screw kneader, a single screw extruder, a twin screw extruder, and a multi-screw extruder.
  • an extrusion molding machine such as a twin-screw extruder or a multi-screw extruder is preferable.
  • the kneading temperature may be a temperature at which all polymer components (a precursor of the fluorine-based cation exchange resin (A) and the fluororubber (B)) flow.
  • the kneading temperature is typically 50 to 300 ° C, preferably 100 to 250 ° C.
  • the temperature of the die is preferably from 100 to 300 ° C, particularly preferably from 150 to 250 ° C.
  • the strand is usually cooled using air, warm water or the like, and it is preferable to use water at 10 to 30 ° C.
  • kneading may be performed at a temperature lower than the melting point of the precursor of the fluorine-based cation exchange resin (A) instead of melt kneading.
  • the kneading equipment in this case include rubber kneading equipment such as two rolls, a Banbury mixer, and a kneader.
  • step 2 the pellet obtained in step 1 is melted to form a tube.
  • a pellet can be put into a horizontal single-screw melt extruder and extruded at around 250 degrees to form a tube.
  • the reinforcing material, the precursor of the fluorine-based cation exchange resin (A), and the kneaded product of the fluororubber (B) may be coextruded.
  • step 3 the obtained tube is hydrolyzed. Further, if necessary, acidification treatment is performed. In the hydrolysis treatment, the precursor group of the precursor of the fluorine-based cation exchange resin (A) is converted into an alkali metal salt type group.
  • the fluorine-based cation exchange resin (A) is the resin (A1)
  • the precursor group is converted into an alkali metal salt of sulfonic acid.
  • the fluorine-based cation exchange resin (A) is the resin (A2)
  • the precursor group is converted into an alkali metal salt of carboxylic acid.
  • a method for hydrolyzing the precursor group a known method can be adopted, and examples thereof include a method described in JP-A-1-140987.
  • a method for hydrolyzing the precursor group a method using a mixture of a water-soluble organic compound (such as dimethyl sulfoxide) and an alkali metal hydroxide (such as potassium hydroxide) is preferable.
  • Acidification is performed by contacting with an aqueous solution of hydrochloric acid, nitric acid, sulfuric acid or the like after hydrolysis. Hydrolysis and acidification are usually carried out at 0 to 120 ° C., preferably 20 to 60 ° C.
  • (A) -1 a precursor of Flemion (registered trademark) manufactured by Asahi Glass Co., Ltd., which is a sulfonic acid type cation exchange resin.
  • the copolymer corresponds to a precursor of the resin (A1) and has a constitutional unit based on the following monomer (1) -1 and a constitutional unit based on the following monomer (2) -1.
  • the ion exchange capacity after the hydrolysis treatment is 1.1 meq / g dry resin.
  • CF 2 CF 2 (1) -1
  • CF 2 CFOCF 2 CF (CF 3 ) OCF 2 CF 2 —SO 2 F (2) -1
  • the molar ratio (TFE / P) between the structural unit based on TFE and the structural unit based on P is 56/44, which is a peroxide crosslinking type.
  • the fluorine atom content is 57% by mass
  • Mooney viscosity ML 1 + 10 (100 ° C.) is 120
  • glass transition temperature (Tg) is ⁇ 3 ° C.
  • Tm melting point
  • the volume change rate was 0.5%.
  • (C) -1 FKM Daiel G-701 manufactured by Daikin, which is a binary copolymer of VdF / HFP. This is a polyol vulcanization type.
  • the fluorine atom content is 66% by mass
  • the Mooney viscosity ML 1 + 10 (100 ° C.) is 55
  • the glass transition temperature (Tg) is ⁇ 17 ° C.
  • (C) -2 Esprene (registered trademark) 501A manufactured by Sumitomo Chemical Co., which is an ethylene / propylene / diene rubber.
  • the molar ratio of the structural units is 52% of structural units based on ethylene, 44% of structural units based on propylene, and 4% of structural units based on 5-ethylidene-2-norbornenediene.
  • a compound for was obtained.
  • the obtained compound was extruded at around 250 ° C. using a horizontal single-screw melt extruder to form a chew. Thereafter, the tube is hydrolyzed with a mixed aqueous solution of dimethyl sulfoxide and potassium hydroxide, and further acidified with an aqueous hydrochloric acid solution, and the final dimensions are ⁇ 5.87 ⁇ ⁇ 3.74 mm (25 ° C., RH 50%).
  • the tube T of each Example and the comparative example was obtained.
  • the tubes T of the examples and comparative examples are arranged in parallel in a U-shaped state.
  • the movable plate 2 was gradually brought closer to the fixed plate 1 by being sandwiched between the fixed plate 1 and the movable plate 2.
  • the distance 2R between the tube on the fixed plate 1 side and the tube on the movable plate 2 side when the tube was broken or crushed was measured, and R that was 1 ⁇ 2 was taken as the minimum bending radius.
  • the time of occurrence of crushing was the time when the tube outer diameter changed by 5% with respect to the original tube outer diameter.
  • ⁇ Water vapor transmission dew point> An inflow pipe and an outflow pipe were connected to both sides of the tube T (length 140 mm, cut at RH 50%) of each example and comparative example, and immersed in pure water adjusted to 20 to 23 ° C. Dry air (temperature 20 to 24 ° C.) having a dew point under atmospheric pressure of ⁇ 45 ° C. or less was supplied to the inlet pipe at a temperature of 50 kPa (gauge pressure) and allowed to flow through the tube T at a flow rate of 11 L / min. The atmospheric pressure dew point of the humidified air discharged from the outflow pipe side was measured and used as the water vapor transmission dew point. The higher the water vapor transmission dew point, the higher the water vapor permeability of the tube T.
  • Table 1 shows the results of measuring the minimum bending radius, the hydraulic break pressure, and the water vapor permeation dew point of the tube T of each example and comparative example.
  • the minimum bending radius tended to decrease as the blending amount of the fluororubber (B) increased.
  • the blending amount of the fluororubber (B) is too high, the flexibility is improved, but it is easily deformed. Therefore, the minimum bending radius has rather increased.
  • the fact that the minimum bending radius is small indicates that the flexibility is good. Therefore, it was found that if the blending amount of the fluororubber (B) is appropriately high, resistance to bending elongation stress is increased.
  • the water vapor selective permeable tube of the present invention can be used in a condensed water remover provided in the middle of a pipe for supplying a sample gas to an analyzer or the like.
  • a pipe made of a water vapor selective permeable tube is connected in the middle of a pipe that supplies compressed air to a pneumatic drive device, the humidity in the pipe can be adjusted using the humidity difference from the surrounding environment.
  • It can also be used for tubes for medical gas dehumidification, humidification and humidity control.
  • SYMBOLS 1 Fixed plate, 2 ... Movable plate, T ... Tube, 10 ... Water tank 10, 11 ... Joint, 12 ... Joint, 13 ... Water pressure device, 14 ... Piping, 15 ... Plug

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

　L'invention concerne un tube à perméabilité sélective à la vapeur d'eau qui peut être conçu pour avoir un rayon de courbure suffisamment petit et qui a une durabilité pour supporter une contrainte de flexion et d'étirage répétée. Ce tube à perméabilité sélective à la vapeur d'eau comprend une résine échangeuse de cations à base de fluor (A) ayant des groupes d'échange cationiques et un caoutchouc fluoré (B). Le caoutchouc fluoré (B) a un pourcentage de variation de volume inférieur à 40%, mesuré conformément à la norme JIS K6258:2003 lorsqu'il est maintenu pendant 3 jours à 100 °C dans une solution aqueuse d'hydroxyde de sodium à 20 % en masse, et le rapport (B)/[(A) + (B)] de la masse du caoutchouc fluoré (B) sur la quantité totale de la résine échangeuse de cations à base de fluor (A) et du caoutchouc fluoré (B) est de 15 à 70 % en masse.
PCT/JP2015/078927 2014-10-14 2015-10-13 Tube à perméabilité sélective à la vapeur d'eau Ceased WO2016060114A1 (fr)

Applications Claiming Priority (2)

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JP2014-209914 2014-10-14
JP2014209914A JP2017213477A (ja) 2014-10-14 2014-10-14 水蒸気選択透過性チューブ

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CN108295669A (zh) * 2018-03-05 2018-07-20 北京清源洁华膜技术有限公司 一种分离VOCs的复合膜及其制备方法
EP4006526B1 (fr) * 2019-07-25 2025-01-15 National Institute for Materials Science Procédé de mesure reposant sur un capteur de gaz et dispositif de mesure
JP7549973B2 (ja) * 2020-05-19 2024-09-12 Ａｇｃエンジニアリング株式会社 複合粒子、成形体、中空糸膜の製造方法、イオン交換膜の製造方法
WO2022185604A1 (fr) 2021-03-04 2022-09-09 株式会社島津製作所 Dispositif d'analyse de gaz

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07275637A (ja) * 1994-04-08 1995-10-24 Asahi Glass Co Ltd 除湿方法
JP2003236351A (ja) * 2002-02-15 2003-08-26 Mitsubishi Rayon Co Ltd 多孔膜およびその製造方法
JP2013527800A (ja) * 2010-04-21 2013-07-04 ラシルク 蒸気の送達のための装置及び方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07275637A (ja) * 1994-04-08 1995-10-24 Asahi Glass Co Ltd 除湿方法
JP2003236351A (ja) * 2002-02-15 2003-08-26 Mitsubishi Rayon Co Ltd 多孔膜およびその製造方法
JP2013527800A (ja) * 2010-04-21 2013-07-04 ラシルク 蒸気の送達のための装置及び方法

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