WO2012147937A1 - イオン交換繊維とその製造方法、水中の化学物質の除去・吸着方法及び水中の化学物質の除去・吸着装置 - Google Patents
イオン交換繊維とその製造方法、水中の化学物質の除去・吸着方法及び水中の化学物質の除去・吸着装置 Download PDFInfo
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- WO2012147937A1 WO2012147937A1 PCT/JP2012/061415 JP2012061415W WO2012147937A1 WO 2012147937 A1 WO2012147937 A1 WO 2012147937A1 JP 2012061415 W JP2012061415 W JP 2012061415W WO 2012147937 A1 WO2012147937 A1 WO 2012147937A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
- B01J47/127—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes in the form of filaments or fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
- G21F9/125—Processing by absorption; by adsorption; by ion-exchange by solvent extraction
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Definitions
- the present invention relates to an ion exchange fiber and a method for producing the same, a method for removing and adsorbing chemical substances in water, and a device for removing and adsorbing chemical substances in water.
- the present invention relates to ion exchange fibers having practically sufficient fiber strength and ion exchange capacity, and use thereof.
- the shape of the adsorbent used in the solid phase adsorption method is various, but among them, the ion exchange fiber generally has an excellent adsorption rate because it has a larger specific surface area than the bead-shaped ion exchange resin. Further, the ion exchange fiber can be processed into an arbitrary form such as a nonwoven fabric, a woven fabric, a thread shape, a molding shape, or the like. Focusing on such characteristics, various fibrous adsorbents have been developed so far.
- Patent Document 1 discloses a method in which wastewater discharged from a copper pyrophosphate plating process is treated with a weakly basic anion exchange fiber having a polyethylene polyamino group to remove and adsorb copper ions in the wastewater. Yes.
- this method is intended only for removing copper ions, and a technique capable of removing and adsorbing various other chemical substances present in water has been desired.
- an amino group-containing fiber obtained by treating an acrylic fiber with an amine compound and simultaneously introducing a crosslinked structure and an amino group is known (see Patent Document 2).
- Patent Document 2 there is a description that a modacrylic fiber having high chemical resistance obtained by copolymerizing vinyl chloride or the like can be used as an acrylic fiber in addition to a normal fiber. There is no description of modacrylic fiber.
- the fiber strength decreases due to the dehydrohalogenation reaction that occurs as a side reaction during the reaction, and an ion exchange fiber that can withstand practical processing and use cannot be obtained. there were.
- an ion exchange fiber in which a cation exchange group or an anion exchange group is introduced into a fiber obtained by polymer blending a modacrylic polymer and an epoxy group-containing polymer is known (see Patent Document 3).
- a modacrylic fiber can be used to make an ion exchange fiber.
- introduction of substituents proceeds only to the epoxy group, there is a limit to the amount of ion-exchangeable substituents that can be introduced, and an improvement in ion exchange capacity has been desired.
- an anion exchange resin obtained by reacting an aromatic crosslinked copolymer having a haloalkyl group with an amine in the presence of a predetermined amount of water and an inorganic salt Patent Document 4
- an ion exchange fiber obtained by introducing a primary to quaternary amine into polyvinyl alcohol see Patent Document 5
- a polymer containing a predetermined amount of a potassium salt-type carboxyl group and having a crosslinked structure see Patent Document 6
- chitosan A polymer in which molecules are cross-linked with a specific structure see Patent Document 7
- a cation exchange fiber Patent Document 8 in which a predetermined amount of carboxyl group is introduced into an acrylic fiber, and the like
- nuclear power plants particularly in the nuclear reactor cooling system and exhaust system, if there is damage such as pinholes in the nuclear fuel rods, fission products, such as 129 I and 131 I are discharged.
- 129 I has a very long half-life of 107 years, but is characterized by low emissions and low energy.
- 131 I has a short half-life of 8 days, but has a feature of high emission and high energy. Therefore, the most dangerous fission product in the reactor drainage / exhaust system is 131 I, which is subject to measurement and evaluation at nuclear facilities.
- the main chemical forms of radioactive iodine discharged from nuclear facilities are said to be iodine (I 2 ), hydroiodic acid (HI), and methyl iodide (CH 3 I). Among these, nonionic methyl iodide is most difficult to remove.
- the following method is used as a method for removing radioactive iodine discharged from nuclear facilities.
- KI potassium iodide
- 131 I which is radioactive iodine
- the iodine-containing gas or liquid is removed by bringing it into contact with an impregnated activated carbon impregnated with triethylenediamine (TEDA) or a strongly basic anion exchanger to react a tertiary amino group with methyl iodide.
- TDA triethylenediamine
- Iodine-containing gas or liquid is brought into contact with silver zeolite and collected as silver iodide.
- the removal techniques (2) and (3) are applied to the removal of methyl iodide.
- hydroiodic acid is acidic, it can be removed with an alkali-impregnated activated carbon or a strongly basic anion exchanger.
- a method for removing molecular iodine (I 2 ) there are a method in which KI is absorbed, a method using a polymer material obtained by graft polymerization of polyvinylpyrrolidone, and the like.
- the method of using the impregnated activated carbon impregnated with potassium iodide or TEDA described above requires a large amount of activated carbon, and at the same time, the cost becomes high, and the treatment of the activated carbon after use becomes a problem.
- the method using silver zeolite is expensive, and at the same time, the process is complicated such that dehydration and heating at 150 ° C. are necessary, and the removal rate of radioactive iodine is not satisfactory. .
- ionic substances such as iodine (I 2 ) and hydroiodic acid and non-ionic substances such as methyl iodide are completely different in the removal method. Therefore, both techniques must be used in combination, and the removal method becomes complicated.
- an ion exchange fiber and a method for removing and adsorbing chemical substances in water that can efficiently remove and adsorb chemical substances such as radioactive iodine compounds as well as various chemical substances in wastewater are desired.
- JP-A-52-23861 JP 2009-7728 A Japanese Patent Laid-Open No. 55-50032 Japanese Patent Laid-Open No. 9-150066 Japanese Patent Laid-Open No. 62-238337 JP 2001-11320 A Japanese Patent Laid-Open No. 6-227813 JP-A-1-234428
- the present invention has been made in view of such circumstances, and has an ion exchange capacity that has practically sufficient fiber strength and ion exchange capacity, and is useful for removal and adsorption of various chemical substances present in liquids such as water. It is an object of the present invention to provide a fiber and a method for producing the same, a method and an apparatus for removing and adsorbing chemical substances in water.
- the present inventors have obtained a fiber obtained by blending an epoxy group-containing polymer with an acrylic polymer obtained by polymerizing a monomer composition containing a predetermined amount of acrylonitrile.
- an ion exchange fiber capable of solving the above-mentioned problems can be obtained by reacting an amine compound, and the present invention has been completed.
- one of the features of the present invention is that the polymer A in which an ion exchange substituent is introduced into 100 parts by weight of an acrylic polymer obtained by polymerizing a monomer composition containing 30% by weight or more of acrylonitrile in 100% by weight of the composition; 1 part by weight or more and 100 parts by weight or less of an epoxy group-containing polymer and a polymer B in which an ion-exchangeable substituent is introduced, and each of the ion-exchangeable substituents is introduced by reaction with an amine compound.
- the acrylic polymer is 30% by weight to 70% by weight of acrylonitrile, 30% by weight or more of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer in 100% by weight of the composition.
- An ion exchange fiber characterized in that it is a modacrylic polymer obtained by polymerizing a monomer composition containing 70% by weight or less and a vinyl monomer copolymerizable therewith in an amount of 0% by weight to 10% by weight.
- Another feature of the present invention is an ion-exchange fiber characterized in that the amine compound includes a compound having a total number of amino groups of 2 or more in one molecule.
- Another feature of the present invention is an ion-exchange fiber characterized in that the amine compound includes a compound having 1 total amino group in one molecule.
- the ion exchange is introduced into the polymer A in which the ion-exchangeable substituent is introduced into 100 parts by weight of the modacrylic polymer and the epoxy group-containing polymer in an amount of 1 part by weight to 70 parts by weight. It is an ion exchange fiber characterized by including the polymer B which introduce
- the ion exchange is performed on the polymer A in which the ion-exchangeable substituent is introduced into 100 parts by weight of the modacrylic polymer and the epoxy group-containing polymer in an amount of 1 to 50 parts by weight. It is an ion exchange fiber characterized by including the polymer B which introduce
- Another feature of the present invention is that the ion exchange is performed between the polymer A in which the ion-exchangeable substituent is introduced into 100 parts by weight of the modacrylic polymer and the epoxy group-containing polymer of 1 to 30 parts by weight. It is an ion exchange fiber characterized by including the polymer B which introduce
- Another feature of the present invention is an ion-exchange fiber wherein the amine compound includes a compound in which at least one of amino groups is a primary amine.
- Another feature of the present invention is an ion-exchange fiber, wherein the amine compound includes a compound having at least one polar substituent in addition to an amino group.
- Another feature of the present invention is an ion exchange fiber characterized in that the fiber strength is 0.8 cN / dtex or more and the ion exchange capacity is 0.8 mmol / g or more.
- Another feature of the present invention is an ion exchange fiber characterized in that an increase in nitrogen content by reaction with the amine compound is 1.0% by weight or more.
- the ion-exchange fiber is characterized in that the acrylic polymer contains a halogen atom, and the decrease in halogen content due to the reaction with the amine compound is 1.0% by weight or more. It is.
- Another feature of the present invention is an ion exchange fiber characterized in that the ion exchange capacity is 1.0 mmol / g or more.
- Another feature of the present invention is a crosslinked acrylic fiber in which an ion-exchangeable substituent derived from the amine compound is introduced by reaction with an amine compound and is crosslinked by the amine compound, Ion exchange characterized by an increase in nitrogen content by reaction with an amine compound of 1.0 wt% or more, fiber strength of 0.8 cN / dtex or more, and ion exchange capacity of 0.8 mmol / g or more Fiber.
- Another feature of the present invention is an ion-exchange fiber, wherein the crosslinked acrylic fiber is a crosslinked modacrylic fiber.
- the crosslinked acrylic fiber contains a halogen atom, and the decrease in halogen content due to the reaction with the amine compound is 1.0% by weight or more.
- Fiber Another feature of the present invention is an ion exchange fiber characterized in that the ion exchange capacity is 1.0 mmol / g or more.
- Another feature of the present invention is the above-described method for producing an ion exchange fiber, wherein (1) an acrylic polymer 100 obtained by polymerizing a monomer composition containing 30% by weight or more of acrylonitrile in 100% by weight of the composition. And a step of mixing and spinning 1 part by weight and 100 parts by weight or less of an epoxy group-containing polymer to obtain a precursor fiber, and (2) reacting the precursor fiber and the amine compound at a temperature exceeding 100 ° C. And introducing an ion-exchangeable substituent derived from an amine compound into an acrylic polymer and an epoxy group-containing polymer contained in the precursor fiber.
- Another feature of the present invention is a method for removing and adsorbing chemical substances in water using ion exchange fibers, wherein the ion exchange fibers are the ion exchange fibers described above. This is a method for removing and adsorbing substances. Another feature of the present invention is a method for removing and adsorbing a chemical substance, wherein the chemical substance is an ionic chemical substance.
- the ionic chemical substance is an anion selected from a halide ion, a polyhalide ion, and an oxoacid ion; a heavy metal ion from Group 3 to Group 16, a lanthanide, and an actinide It is an ionic chemical substance containing one or more ions selected from the group consisting of heavy metal element ions or complex ions thereof.
- Another feature of the present invention is the removal of a chemical substance in water, wherein the ionic chemical substance is an ionic chemical substance containing halide ions, and the halide ions are iodide ions. ⁇ Adsorption method.
- Another feature of the present invention is an apparatus for removing and adsorbing chemical substances in water, comprising an adsorbent containing at least one ion exchange fiber selected from the ion exchange fibers described above.
- the ion exchange fiber of the present invention has practically sufficient fiber strength and ion exchange capacity, and is effective for removing and adsorbing various chemical substances present in water.
- the method for producing an ion exchange fiber of the present invention can provide such an ion exchange fiber. Further, according to the method and apparatus of the present invention, various chemical substances in water can be efficiently removed and adsorbed.
- FIG. 6 is an explanatory diagram showing the results of Comparative Examples 13 to 16 in a graph. It is explanatory drawing which showed the result of Examples 24 and 25 and Comparative Examples 17 and 18 in the graph. It is explanatory drawing which showed the result of Examples 26 and 27 and Comparative Examples 19 and 20 on the graph. It is explanatory drawing which showed the result of Examples 28 and 29 and Comparative Examples 21 and 22 on the graph.
- the ion exchange fiber of the present invention its production method, and the removal / adsorption method and apparatus for chemical substances in water will be described in more detail.
- the ion exchange fiber refers to a fiber having an ion exchange substituent in its structure and exhibiting ion exchange ability.
- ion-exchangeable substituents include cation-exchangeable substituents and anion-exchangeable substituents, as well as chelating substituents having two or more polar groups. That is, the ion exchange fiber in the present invention indicates a chelate fiber in addition to a general ion exchange fiber.
- the ion exchange fiber in the present invention includes polymer A and polymer B.
- Polymer A has an ion-exchangeable substituent derived from an amine compound by reaction with an amine compound on 100 parts by weight of an acrylic polymer obtained by polymerizing a monomer composition containing 30% by weight or more of acrylonitrile in 100% by weight of the composition.
- Polymer B is a polymer in which an ion-exchangeable substituent derived from an amine compound is introduced into an epoxy group-containing polymer of 1 part by weight or more and 100 parts by weight or less by reaction with an amine compound.
- Acrylonitrile contained in the acrylic polymer in polymer A has a cyano group, and has an appropriate reactivity with an amine compound and high chemical resistance, and thus is suitable for producing the ion exchange fiber of the present invention.
- an acrylic polymer obtained by polymerizing a monomer composition having an acrylonitrile content of 30% by weight or more of the total amount an ion exchange fiber into which an amine compound is sufficiently introduced can be obtained.
- the polymer A may have a crosslinked structure inside.
- the acrylic polymer in polymer A may contain other monomers copolymerizable with acrylonitrile in the monomer composition.
- a monomer for example, halogen-containing vinylidene monomers such as vinylidene chloride, vinylidene bromide, vinylidene iodide, halogen-containing vinyl monomers such as vinyl chloride, vinyl bromide, vinyl iodide, acrylic acid and its Ester, methacrylic acid and its ester, acrylamide, methacrylamide, vinyl acetate, vinyl sulfonic acid and its salt, methallyl sulfonic acid and its salt, styrene sulfonic acid and its salt, 2-acrylamido-2-methylsulfonic acid and its salt And various vinyl monomers.
- the other monomer copolymerizable with acrylonitrile can be used singly or in combination of two or more.
- the acrylic polymer in the polymer A contains 30% by weight to 70% by weight of acrylonitrile in 100% by weight of the composition, 30% by weight to 70% by weight of the halogen-containing vinylidene monomer and / or halogen-containing vinyl monomer, and A modacrylic polymer obtained by polymerizing a monomer composition containing 0 to 10% by weight of a copolymerizable vinyl monomer is preferred.
- Modacrylic polymers have higher chemical resistance than acrylic polymers, and are suitable for use in ion exchange fibers.
- the fiber strength does not decrease due to the reaction between the modacrylic polymer and the amine compound, and the modacrylic polymer is sufficient.
- a sufficient amount of ion-exchangeable substituents is introduced.
- the ion exchange fiber of the present invention using a modacrylic polymer as the polymer A has practically sufficient fiber strength and ion exchange capacity such as fiber strength of 0.8 cN / dtex or more and ion exchange capacity of 0.8 mmol / g or more. Have.
- the polymer B since the epoxy group-containing polymer has high reactivity with the amine compound, the reactivity with the amine compound as a whole is improved by blending the epoxy group-containing polymer in the acrylic polymer, An ion exchange fiber having a higher ion exchange capacity can be obtained.
- the polymer B may have a crosslinked structure inside.
- a method for producing the ion exchange fiber of the present invention for example, 1) a step of obtaining a precursor fiber serving as a base material by mixing and spinning an acrylic polymer and an epoxy group-containing polymer by a method such as polymer blend (hereinafter referred to as a base material) "Precursor fiber manufacturing process"), 2) An amine compound is reacted with the obtained precursor fiber, and an ion-exchangeable substituent derived from the amine compound is converted into an acrylic polymer and an epoxy group-containing polymer contained in the precursor fiber. And a step of introducing (hereinafter referred to as “ion-exchangeable substituent introduction step”).
- the amine compound is reacted with the precursor fiber obtained by mixing and spinning the modacrylic polymer and the epoxy group-containing polymer to react the amine compound with the modacrylic polymer.
- the conventional problem in the fiber strength of the ion exchange fiber can be solved.
- a known spinning method can be used in the first stage precursor fiber manufacturing process.
- a method according to the purpose such as a melt spinning method, a wet spinning method, or a dry spinning method can be used.
- the wet spinning method is preferable because fibers can be obtained at a low temperature as compared with other methods, and the ring opening reaction of the epoxy group during the spinning process hardly occurs.
- the acrylic polymer used in the first step is not particularly limited as long as it is an acrylic polymer obtained by polymerizing a monomer composition containing 30% by weight or more of acrylonitrile in 100% by weight of the composition. Can be preferably used.
- the modacrylic polymer in the present invention is a polymer obtained by polymerizing a monomer composition containing acrylonitrile, a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer.
- the modacrylic polymer in the present invention may be a polymer obtained by polymerizing a monomer composition containing a vinyl monomer copolymerizable with acrylonitrile, a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer. Good.
- the modacrylic polymer in the present invention contains 30% to 70% by weight of acrylonitrile, preferably 35% to 60% by weight, more preferably 40% to 55% by weight in 100% by weight of the monomer composition. It is obtained by polymerizing the monomer composition containing it.
- halogen-containing vinylidene monomer and the halogen-containing vinyl monomer include vinyl compounds containing halogen in the molecule. More specifically, examples of the halogen-containing vinylidene monomer include vinylidene chloride, vinylidene bromide, and vinylidene iodide. Examples of the halogen-containing vinyl monomer include vinyl chloride, vinyl bromide, and vinyl iodide. However, it is not limited to these. In the present invention, one or more monomers selected from such monomers are used.
- the modacrylic polymer in the present invention is a halogen-containing vinylidene monomer and / or a halogen-containing vinyl monomer in an amount of 30% to 70% by weight, preferably 40% to 65% in addition to acrylonitrile in 100% by weight of the monomer composition. %, More preferably 45% by weight or more and 55% by weight or less is obtained by polymerizing the monomer composition.
- Examples of vinyl monomers copolymerizable with at least one of acrylonitrile, halogen-containing vinylidene monomers, and halogen-containing vinyl monomers include acrylic acid and esters thereof, methacrylic acid and esters thereof, acrylamide, methacrylamide, vinyl acetate, and vinyl sulfonic acid. And various salts thereof such as methallylsulfonic acid and salts thereof, styrenesulfonic acid and salts thereof, 2-acrylamido-2-methylsulfonic acid and salts thereof, and one or more of them. However, it is not limited to these. These monomers are preferably copolymerized by being included in the monomer composition as long as they do not affect the fiber strength. Specifically, the range of 0 wt% or more and 10 wt% or less is preferable in 100 wt% of the monomer composition.
- a modacrylic polymer in the above range generally has higher chemical resistance than an acrylic polymer having an acrylonitrile content of 85% by weight or more, and is suitable for use as a base polymer for ion exchange fibers.
- the modacrylic polymer in the above preferred range and the more preferred range has higher chemical resistance.
- the epoxy group-containing polymer used together with the acrylic polymer refers to a homopolymer or copolymer of a monomer containing an epoxy group in the molecule.
- the epoxy group-containing monomer is not particularly limited as long as this condition is satisfied.
- glycidyl methacrylate is preferably used.
- the number of epoxy groups in one molecule in the epoxy group-containing polymer is not particularly limited, but is preferably 50 to 1500, more preferably 100 to 1000. It is desirable that the amount of the epoxy group-containing polymer is appropriately adjusted according to the type of amine compound used and the desired fiber strength and ion exchange capacity.
- the copolymer When a copolymer is used as the epoxy group-containing polymer, the copolymer contains an epoxy group-containing monomer and a monomer copolymerizable therewith.
- the monomer copolymerizable with the epoxy group-containing monomer is not particularly limited as long as it is copolymerizable with the epoxy group-containing monomer.
- the compounding amount of the epoxy group-containing polymer in the ion exchange fiber of the present invention is 1 part by weight or more and 100 parts by weight or less, preferably 1 part by weight or more and 70 parts by weight or less, based on 100 parts by weight of the acrylic polymer. Preferably they are 1 weight part or more and less than 50 weight part, More preferably, they are 1 weight part or more and 30 weight part or less. This is because an ion exchange fiber having fiber strength and ion exchange ability can be obtained by using an acrylic polymer and an epoxy group-containing polymer in combination within a preferred range and reacting this with an amine compound as a precursor fiber.
- the amine compound is reacted with the precursor fiber obtained in the first-stage precursor fiber manufacturing process, whereby the acrylic polymer and the epoxy group-containing polymer are converted into amines.
- An ion-exchangeable substituent derived from the compound is introduced.
- An amine compound that reacts with at least one of a cyano group of an acrylic polymer, a cyano group and a halogeno group in a modacrylic polymer, an epoxy group in an epoxy group-containing polymer, and the like can be used.
- various compounds can be arbitrarily used. For example, monoamines having one total amino group in one molecule, and two or more total amino groups in one molecule. Examples include polyamines, polyfunctional amines having at least one polar substituent in addition to amino groups in one molecule.
- the type of amine compound can be selected as appropriate in consideration of the type of chemical substance in water that is the purpose of removal and adsorption, or the reactivity with the above substituents (cyano group, halogeno group, epoxy group, etc.) It is.
- Examples of monoamines having 1 amino acid group per molecule include trimethylamine, dimethylamine, monomethylamine, triethylamine, diethylamine, ethylamine, dimethylbenzylamine, dimethylbenzylamine and the like. Monoamines can be used singly or in combination of two or more.
- low molecular polyamines can be suitably used as the polyamines having 2 or more total amino groups in one molecule.
- the low molecular weight polyamine include primary diamines such as ethylenediamine, 1,4-diaminobutane and 1,6-diaminohexane; primary-tertiary diamines such as dimethylaminopropylamine and diethylaminopropylamine; diethylenetriamine 1,9-diamino-5-azanonane, 1,13-diamino-7-azatridecane, triethylenetetramine, tetraethylenepentamine, a mixture of oligomeric diaminopolyethyleneimine marketed under the registered trademark of Polymin, etc.
- Diprimary-secondary amines such as piperidine, piperazine, di-n-butylamine, morpholine, and diamines.
- secondary amines such as piperidine, piperazine, di-n-butylamine, morpholine, and diamines.
- polymeric polyamines such as polyethyleneimine and polyallylamine, can be used as polyamines.
- Polyamines can be used singly or in combination of two or more.
- Preferred low molecular weight polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, triethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenetetramine, pentaethylenehexamine, hexamethyleneheptamine and the like. It is done.
- the low molecular weight polyamine is used as the amine compound
- both the polymer A and the polymer B contain a substituent that reacts with the amine
- the polymer A An ion exchange fiber in which a crosslinked structure is also introduced between the polymer B and the polymer B is obtained. This is because in such an ion exchange fiber, the elution of the polymer A and / or the polymer B into which the hydrophilic substituent is introduced is less.
- Polyfunctional amines having at least one polar substituent in addition to an amino group in one molecule include arginine, lysine, hydroxylysine, histidine, glycine, alanine, valine, leucine, isoleucine, serine, threonine, asparagine Various amino acids such as glutamine, cystine, cysteine, methionine, phenylalanine, tyrosine, tryptophan, proline, hydroxypurine, aspartic acid, and glutamic acid; N-methyl-D-glucamine (also referred to as “N-methylglucamine”), Examples include polyfunctional amine compounds such as iminodiacetic acid, phosphophenylamine, ethanolamine, diethanolamine and diisopropanolamine. Polyfunctional amines can be used singly or in combination of two or more.
- One or two or more selected from the group consisting of the monoamines, polyamines and polyfunctional amines described above can be used as the amine compound.
- the resulting ion exchange fibers are various metal ions, etc. Has a chelating substituent having selectivity.
- the ion exchange fiber obtained by such a method can be given adsorption characteristics according to the application by selecting a substituent according to the intended application.
- an amine compound containing two or more amino groups can be selected.
- a cross-linked structure is introduced simultaneously with the introduction of the ion-exchangeable substituent, so that characteristics such as chemical resistance and heat resistance are improved.
- a crosslinked structure is also introduced between the acrylic polymer as the base polymer and the epoxy group-containing polymer as the blend polymer, and this effect is more easily exhibited. By improving such characteristics, it can be more suitably used as an ion exchange fiber.
- such an amine compound may contain a substituent other than an amino group.
- a reagent capable of reacting with an acrylic polymer or an epoxy group-containing polymer may be reacted simultaneously with or after reacting the precursor fiber with such an amine compound.
- an ion-exchangeable substituent by utilizing the reactivity of the amino group introduced by the above method.
- a reaction include introduction of a carboxyl group using a carboxyl group introduction reagent such as haloacetic acid, introduction of various substituents utilizing amidation, and generation of an imine by reaction with an aldehyde, a ketone, or the like.
- the amine compound preferably contains at least one primary amine as an amino group. This is because primary amines are more reactive than secondary amines and tertiary amines, and ion exchange fibers having a high ion exchange capacity are easily obtained.
- the reaction between the precursor fiber and the amine compound can be performed using an aqueous solvent.
- the reaction proceeds by immersing the precursor fiber in an aqueous solution of an amine compound and heating it.
- the reaction rate at the time of introducing the ion-exchangeable substituent derived from the amine compound can be adjusted by the concentration of the amine compound, the reaction temperature, and the reaction time.
- concentration of the amine compound the higher the reaction temperature, or the longer the reaction time, the better the reaction proceeds, and the amount of amine compound introduced increases.
- the reaction proceeds excessively, the fibers are eluted into the reaction solution, so it is preferable to select appropriate reaction conditions.
- a temperature condition used at the time of introducing the ion-exchangeable substituent derived from the amine compound it is necessary to set it to 80 ° C. or higher.
- the amine condition reacts not only with an epoxy group but also with a cyano group or a halogeno group in the modacrylic polymer by sufficiently increasing the temperature condition to 100 ° C.
- An ion-exchangeable fiber having an ion-exchange capacity is obtained.
- This temperature condition is more preferably 110 ° C. or higher, and further preferably 120 ° C. or higher.
- the upper limit of the temperature condition is preferably about 180 ° C.
- the reaction may not proceed easily only by adjusting the above conditions.
- the progress of the reaction can be promoted by using an aqueous solution of a hydrophilic organic solvent such as alcohol as a solvent.
- a hydrophilic organic solvent such as alcohol as a solvent.
- Such an organic solvent may be appropriately selected according to the reactivity of the amine.
- methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, acetone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc. Can be used.
- These hydrophilic organic solvents can be used in combination, or can be used by mixing with a hydrophilic organic solvent and water.
- the reaction may be performed using a beaker or the like as long as the amount is small.
- various reaction containers according to the objective or the form of a fiber.
- various dyeing machines can be suitably used. For example, when a cut cotton is desired to be reacted, an overmeier dyeing machine can be used.
- the amino group contained in the amine compound is a cyano group derived from acrylonitrile in the acrylic polymer, or an acrylic polymer in which a halogen atom is substituted with a carbon atom in the molecule (hereinafter referred to as “acrylic having a halogen atom”). It reacts with both of the halogeno group (preferably chloro group) in “the acrylic polymer containing a halogen atom” and the epoxy group in the epoxy group-containing polymer. For this reason, when the method of the present invention is used, a sufficient amount of ion-exchangeable substituents can be introduced regardless of the amount of the epoxy group-containing polymer.
- introduction of an ion-exchangeable substituent derived from an amine compound is preferably 1.0% by weight or more, more preferably 2.0% by weight or more. It is.
- the nitrogen content in the present invention refers to the nitrogen content in the fiber measured by elemental analysis.
- the increase in nitrogen content is an increase in nitrogen content before and after reaction with an amine compound. Since the amount of increase in nitrogen content indicates the amount of ion-exchangeable substituents derived from the introduced amine compound, this value is preferably as large as possible.
- the ion exchange fiber in the present invention is preferably a cross-linked acrylic fiber into which a cross-linked structure has been introduced by a reaction between an acrylic polymer and an amine compound and / or a reaction between an epoxy group-containing polymer and an amine compound.
- a crosslinked structure By introducing a crosslinked structure, an ion exchange fiber having chemical resistance and fiber strength sufficient for practical use can be obtained.
- the fiber strength value in the crosslinked acrylic fiber of the present invention is 0.8 cN / dtex or more, preferably 1.0 cN / dtex or more.
- the value of the ion exchange capacity in the present invention is 0.8 mmol / g or more, preferably 1.0 mmol / g or more, more preferably 1.5 mmol / g or more.
- Such an ion exchange fiber exhibits sufficient chemical substance removal / adsorption performance and has a strength necessary for processing into various forms.
- the crosslinked acrylic fiber has a crosslinked structure obtained by, for example, reacting an amine compound with a precursor fiber obtained by spinning a blend of an acrylic polymer (preferably a modacrylic polymer) with an epoxy group-containing polymer.
- An acrylic fiber preferably a modacrylic fiber having a crosslinked structure.
- crosslinkable reactive group a method using an amine compound having an ion-exchangeable substituent and a crosslinkable reactive group (hereinafter simply referred to as “crosslinkable reactive group”) that forms a crosslinked structure with heat or a crosslinking agent, acrylic
- crosslinkable reactive group a method using a polymer having a crosslinkable reactive group in a polymer and / or an epoxy group-containing polymer.
- a method using polyamines as an amine compound a method of reacting a precursor fiber and an amine compound in the presence of a crosslinking agent such as glycerin, an acrylic polymer having a hydroxyl group and an epoxy-containing polymer having a carboxy group And the like, and the like, and the like.
- a crosslinking agent such as glycerin, an acrylic polymer having a hydroxyl group and an epoxy-containing polymer having a carboxy group And the like, and the like, and the like.
- the introduction of the ion-exchangeable substituent derived from the amine compound and the crosslinking may be performed simultaneously or separately.
- the halogen content is preferably reduced by reaction with an amine compound (introduction of an ion-exchangeable substituent derived from the amine compound). It is 1.0% by weight or more, more preferably 2.0% by weight or more.
- the halogen content in the present invention means the halogen content in the fiber measured by elemental analysis.
- the decrease in halogen content is the decrease in halogen content before and after the reaction with the amine compound.
- the amine compound also reacts with the halogenated vinyl monomer residue in the modacrylic polymer, so that the decrease in the halogen content is reduced by the vinylidene halide monomer and / or halogen. This is because the introduction of an amine compound into the vinyl chloride monomer residue is shown. However, care must be taken because the reactivity of amines with these monomer residues varies greatly depending on the type of amine compound.
- an ion exchange fiber having a high ion exchange capacity may be obtained if the amine compound is sufficiently reacted with the acrylonitrile monomer residue or the epoxy group-containing polymer. is there.
- the ion exchange fiber obtained by the production method of the present invention is characterized in that the fiber strength is hardly lowered even when an acrylic polymer (particularly a modacrylic polymer) is reacted with an amine compound. For this reason, it can endure the processing to a nonwoven fabric and a spun yarn, and can be used by processing into various shapes such as a yarn, a woven fabric, a knitted fabric, a braid, and a nonwoven fabric. Another feature is that an ion exchange fiber with improved chemical resistance can be obtained because the epoxy group functions as a crosslinking agent. Furthermore, since an amine compound reacts not only with an epoxy group but also with a cyano group or a halogeno group, it is possible to obtain an ion exchange fiber having a sufficient ion exchange capacity.
- the epoxy group-containing polymer may be more reactive with the amine compound than the cyano group or the halogeno group depending on the type of the amine compound.
- the epoxy group-containing polymer as a small amount of blend polymer, the ion exchange capacity can be greatly improved as compared with the case where a modacrylic polymer containing no epoxy group-containing polymer is used.
- the method for removing and adsorbing chemical substances in water according to the present invention is a method for removing and adsorbing chemical substances in water using ion-exchange fibers.
- an exchange fiber it is characterized by using at least 1 sort (s) chosen from the ion exchange fiber of this invention which has each structure explained in full detail above.
- s 1 sort
- the main embodiment of the ion-exchangeable fiber of the present invention is an acrylic polymer 100 obtained by polymerizing a monomer composition containing polymer A and polymer B, and polymer A containing 30% by weight or more of acrylonitrile in 100% by weight of the composition. It is a polymer in which an ion-exchangeable substituent derived from an amine compound is introduced into parts by weight, and an ion-exchangeable substituent derived from an amine compound is added to an epoxy group-containing polymer in which polymer B is 1 to 100 parts by weight. The introduced polymer.
- a modacrylic polymer is used as the acrylic polymer in the polymer A.
- the ion exchange fiber used in the removal / adsorption method of the present invention is obtained by introducing an ion exchangeable substituent derived from an amine compound into the precursor fiber.
- the ion exchange fiber used in the present invention has a high adsorption rate for various chemical substances in water, and can efficiently remove and adsorb low concentration chemical substances.
- the feature of the removal / adsorption method of the present invention is that it exhibits an excellent effect particularly on the adsorption rate and the adsorption performance for chemical substances existing at a low concentration.
- impurities (chemical substances) in water can be efficiently removed by the embodiment of the present invention is not clear at present, but ion exchange fibers having a large specific surface area compared to general bead-type ion exchange resins are used.
- the ion exchange fiber obtained by the reaction between the precursor fiber and the amine compound has an appropriate cross-linked structure and substituent distribution.
- the chemical substance that can be removed from water by the removal / adsorption method of the present invention is not particularly limited, and examples thereof include ionic chemical substances and nonionic chemical substances. According to the removal / adsorption method of the present invention, the removal / adsorption can be efficiently performed by appropriately selecting the type of amine compound according to the type of these chemical substances. These chemical substances are adsorbed to the ion exchange fiber through the ionic bond, hydrogen bond, coordination bond, electrostatic interaction, or other interaction with the ion exchange fiber used in the present invention, or the bond. Is done.
- An ionic chemical substance is an organic compound containing ions. Although it does not specifically limit as ion, For example, anions, such as halide ion, polyhalide ion, and oxo acid ion, and its complex ion; Heavy metal ion of Group 3 to 16 of the periodic table and its complex ion, lanthanide, actinide Heavy metal element ions such as complex ions thereof and the like.
- ionic chemical substances may be contained in the water to be removed and adsorbed. By using two or more types of ion exchange fibers having different ion exchange substituents in combination, even if a plurality of ion chemical substances are contained in water, they can be removed and adsorbed simultaneously.
- the nonionic chemical substance is not particularly limited as long as it is an organic compound not containing ions.
- at least one substituent is bonded to various atoms that can have a substituent such as an oligomer, a polymer, or a carbon atom.
- An organic compound etc. are mentioned.
- the chemical substance is an ionic chemical substance
- iodide ions in water by using an ion exchange fiber into which an ion exchangeable substituent derived from a polyamine type amine compound is introduced.
- iodide ions can be removed and adsorbed at high speed and with high efficiency by using the above-mentioned ion exchange fiber after making the iodide ions into iodine and / or polyiodine ions using an oxidizing agent. .
- the oxidizing agent used at this time is not particularly limited as long as it can oxidize iodide ions to iodine and / or polyiodine ions.
- sodium hypochlorite, chlorine, hydrogen peroxide and the like can be preferably used. .
- iodine produced by the reactions shown in (Formula 1) and (Formula 2) and / or polyiodine ions are immediately removed and adsorbed, so that the equilibrium is inclined and the remaining iodine
- the fluoride ions are sequentially converted into iodine molecules and / or polyiodine ions.
- the iodine constituting the iodide ion may be radioactive iodine such as 131 I, 129 I, 123 I or 127 I (stable isotope). Removal and adsorption become possible.
- the ion exchange fiber to be used one having a large iodine saturated adsorption amount is preferable.
- a preferable value is 100 g / kg or more, more preferably 300 g / kg or more, and further preferably 500 g / kg or more.
- polyiodine ions can be efficiently adsorbed.
- the iodine saturated adsorption amount is the maximum amount of iodine that can be adsorbed by 1 kg of fiber.
- the ions contained in the ionic chemical substance may be heavy metal ions or complex ions of heavy metals.
- the type of amine compound according to the type of heavy metal ions it is possible to remove and adsorb heavy metal ions with high selectivity in addition to the adsorption rate and the adsorptivity at a low concentration.
- the apparatus for removing and adsorbing chemical substances in water of the present invention comprises at least one selected from the group consisting of the ion-exchange fibers of the present invention having the various configurations described above. It is characterized by having an adsorbent containing.
- the main embodiment of the ion-exchangeable fiber of the present invention is an acrylic polymer 100 obtained by polymerizing a monomer composition containing polymer A and polymer B, and polymer A containing 30% by weight or more of acrylonitrile in 100% by weight of the composition. It is a polymer in which an ion-exchangeable substituent derived from an amine compound is introduced into parts by weight, and an ion-exchangeable substituent derived from an amine compound is added to an epoxy group-containing polymer in which polymer B is 1 to 100 parts by weight. The introduced polymer.
- a modacrylic polymer is used as the acrylic polymer in the polymer A.
- the form of the adsorbent in the adsorption / removal device of the present invention is not limited as long as it contains the ion exchange fiber of the present invention.
- general fiber products such as yarns, woven fabrics, knitted fabrics, braided cords, non-woven fabrics, etc. It can take the form of a filter or the like.
- the precursor fiber it is possible to use it as a sheet, a film or the like by forming into a sheet form instead of a thread form.
- water-soluble inorganic substance particles can be mixed and immersed in water after forming to dissolve and remove the inorganic substance particles to make it porous.
- adsorbents may be used as they are, or may be used by being housed in a container made of a material that is permeable to liquid.
- a container made of a material that is permeable to liquid.
- examples of such a container include a bag made of paper or cloth, a metal, ceramics, glass, a synthetic resin, and the like, a container having a plurality of holes, a container provided with a filter, and the like.
- the adsorption / removal device of the present invention includes an adsorbent and an interior space that can accommodate water containing the adsorbent and the chemical substance, and includes a facility or an apparatus (for example, a feed / drain pump) that enables water supply and drainage.
- a facility or an apparatus for example, a feed / drain pump
- Measurement was performed using a tensilon meter (trade name: RTC-1210A, manufactured by ORIENTEC). In addition, it is necessary to have a fiber strength of 0.8 cN / dtex or more for processing into a non-woven fabric, spun yarn and other forms.
- ion exchange capacity adjusted to the standard type was used, and ion exchange capacity was measured by the method shown in the above-mentioned “Diaion Ion Exchange Resin / Synthetic Adsorbent Manual Basics”.
- a larger value of ion exchange capacity is preferable because more electrolytic mass can be adsorbed.
- the practical value is preferably 0.8 mmol / g or more, more preferably 1.0 mmol / g or more, and further preferably 1.5 mmol. / G or more.
- the nitrogen content was measured using an elemental analyzer (trade name: JM10, manufactured by J Science Laboratories). The nitrogen content before and after the reaction with the amine compound was measured, and the increase in the nitrogen content was determined from the difference.
- halogen content is determined by ion chromatography after burning the sample using a combustion device (trade name: QF02, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and absorbing the halogen released as hydrogen halide with sodium hydroxide. Quantification was performed using an apparatus (trade name: IC-2010, manufactured by Tosoh Corporation). The halogen content before and after the reaction with the amine compound was measured, and the decrease in the halogen content was determined from the difference.
- iodine saturation adsorption amount 0.2 g of the adsorbent was immersed in 20 g of 0.05N iodine standard solution and left to stand for 3 days. Thereafter, 2 mL of the supernatant was collected, and 10 mL of ion-exchanged water and starch solution were added. This solution was titrated with a 0.01N aqueous sodium thiosulfate solution to determine the iodine concentration of the supernatant. From the result, the iodine saturated adsorption amount was determined by the following (Equation 3).
- A (0.05 ⁇ a) ⁇ 253.8 ⁇ 20 / 0.2 (Formula 3) (A: iodine saturation adsorption amount, a: iodine concentration of supernatant after adsorption)
- the saturated iodine adsorption amount is expressed in g / kg, and 1 g / kg indicates that 1 kg of adsorbent adsorbs 1 g of iodine in a saturated state.
- Example 1 100 parts by weight of a modacrylic polymer composed of 56% by weight of acrylonitrile, 42% by weight of vinyl chloride, 2% by weight of sodium parastyrenesulfonate, and 67 parts by weight of polyglycidyl methacrylate (hereinafter also referred to as “PGMA”) are dissolved in acetone. A spinning dope with a concentration of 30% by weight was obtained. This spinning dope was wet-spun to obtain a precursor fiber. Next, 5 g of this precursor fiber was reacted at 120 ° C. for 6 hours in 200 g of a 60 wt% triethylenetetramine aqueous solution to obtain an ion exchange fiber.
- PGMA polyglycidyl methacrylate
- the ion exchange capacity of this ion exchange fiber was 4.67 mmol / g, the fiber strength was 1.12 cN / dtex, the increase in nitrogen content was 6.9% by weight, and the decrease in halogen content was 20.5% by weight. .
- Example 2 When producing the precursor fiber, an ion exchange fiber was obtained using the same method as in Example 1 except that the amount of modacrylic polymer was 100 parts by weight and the amount of polyglycidyl methacrylate was 25 parts by weight.
- the ion exchange capacity of this ion exchange fiber was 4.45 mmol / g, the fiber strength was 1.22 cN / dtex, the increase in nitrogen content was 6.6% by weight, and the decrease in halogen content was 15.7% by weight. .
- Example 3 When producing the precursor fiber, an ion exchange fiber was obtained using the same method as in Example 1 except that the amount of modacrylic polymer was 100 parts by weight and the amount of polyglycidyl methacrylate was 10 parts by weight.
- the ion exchange capacity of this ion exchange fiber was 4.39 mmol / g, the fiber strength was 1.33 cN / dtex, the increase in nitrogen content was 6.6% by weight, and the decrease in halogen content was 12.9% by weight. .
- Example 4 When producing the precursor fiber, an ion exchange fiber was obtained using the same method as in Example 1 except that the amount of modacrylic polymer was 100 parts by weight and the amount of polyglycidyl methacrylate was 5 parts by weight.
- the ion exchange capacity of this ion exchange fiber was 4.35 mmol / g, the fiber strength was 1.22 cN / dtex, the increase in nitrogen content was 6.4% by weight, and the decrease in halogen content was 13.5% by weight. .
- Example 5 When producing the precursor fiber, an ion exchange fiber was obtained using the same method as in Example 1 except that the amount of modacrylic polymer was 100 parts by weight and the amount of polyglycidyl methacrylate was 1 part by weight.
- the ion exchange capacity of this ion exchange fiber was 4.30 mmol / g, the fiber strength was 1.10 cN / dtex, the increase in nitrogen content was 6.4% by weight, and the decrease in halogen content was 13.5% by weight. .
- Example 6 Precursor fibers were obtained in the same manner as in Example 1. Next, 5 g of this precursor fiber was reacted at 120 ° C. for 6 hours in a 22.9 wt% cysteine aqueous solution to obtain an ion exchange fiber.
- the ion exchange capacity of this ion exchange fiber was 3.57 mmol / g
- the fiber strength was 1.01 cN / dtex
- the increase in nitrogen content was 3.5% by weight
- the decrease in halogen content was 15.3% by weight. .
- Example 7 When producing the precursor fibers, ion exchange fibers were obtained in the same manner as in Example 6 except that the amount of modacrylic polymer was 100 parts by weight and the amount of polyglycidyl methacrylate was 43 parts by weight.
- the ion exchange capacity of this ion exchange fiber was 2.68 mmol / g, the fiber strength was 1.16 cN / dtex, the nitrogen content was increased by 3.2% by weight, and the halogen content was decreased by 12.5% by weight. .
- Example 8 When producing the precursor fiber, an ion exchange fiber was obtained in the same manner as in Example 6 except that the amount of modacrylic polymer was 100 parts by weight and the amount of polyglycidyl methacrylate was 25 parts by weight.
- the ion exchange capacity of this ion exchange fiber was 1.92 mmol / g, the fiber strength was 1.23 cN / dtex, the increase in nitrogen content was 2.5% by weight, and the decrease in halogen content was 9.4% by weight. .
- Example 9 When producing the precursor fiber, an ion exchange fiber was obtained in the same manner as in Example 6 except that the amount of modacrylic polymer was 100 parts by weight and the amount of polyglycidyl methacrylate was 5 parts by weight.
- the ion exchange capacity of this ion exchange fiber was 1.37 mmol / g, the fiber strength was 1.42 cN / dtex, the increase in nitrogen content was 2.1% by weight, and the decrease in halogen content was 8.0% by weight. .
- Example 10 Precursor fibers were obtained in the same manner as in Example 2. Next, 5 g of this precursor fiber was reacted in an 18.4 wt% iminodiacetic acid aqueous solution at 120 ° C. for 6 hours to obtain an ion exchange fiber.
- the ion exchange capacity of this ion exchange fiber was 1.69 mmol / g
- the fiber strength was 1.27 cN / dtex
- the increase in nitrogen content was 3.0% by weight
- the decrease in halogen content was 3.7% by weight. .
- Example 11 When producing the precursor fiber, an ion exchange fiber was obtained in the same manner as in Example 10 except that the amount of modacrylic polymer was 100 parts by weight and the amount of polyglycidyl methacrylate was 5 parts by weight.
- the ion exchange capacity of this ion exchange fiber was 1.12 mmol / g, the fiber strength was 1.45 cN / dtex, the increase in nitrogen content was 2.0% by weight, and the decrease in halogen content was 2.5% by weight. .
- Example 1 Ion exchange fibers were obtained in the same manner as in Example 1 except that polyglycidyl methacrylate was not used when preparing the precursor fibers.
- the ion exchange capacity of this ion exchange fiber was 4.26 mmol / g, but the fiber strength was so low that it could not be measured with a tensilon meter.
- the increase in nitrogen content was 6.3% by weight, and the decrease in halogen content was 15.8% by weight.
- Comparative Example 2 Precursor fibers were obtained in the same manner as in Comparative Example 1. Next, 5 g of this precursor fiber was reacted in a 22.9 wt% cysteine aqueous solution at 120 ° C. for 6 hours to obtain an ion exchange fiber.
- the ion exchange capacity of this ion exchange fiber was 0.25 mmol / g, the fiber strength was 1.83 cN / dtex, the increase in nitrogen content was 0.3% by weight, and the decrease in halogen content was 0.3% by weight. .
- Example 4 An acrylic polymer composed of 93% by weight of acrylonitrile and 7% by weight of methyl acrylate was wet-spun by a known method to obtain a precursor fiber. Next, 5 g of this precursor fiber was reacted under the same conditions as in Example 1 to obtain an ion exchange fiber.
- the ion exchange capacity of this ion exchange fiber was 4.68 mmol / g, the fiber strength was 2.32 cN / dtex, and the increase in nitrogen content was 7.0% by weight.
- Example 5 Ion exchange fibers were obtained in the same manner as in Example 1. However, the reaction temperature was 80 ° C. when the reaction with triethylenetetramine was performed. The ion exchange capacity of this ion exchange fiber was 0.21 mmol / g, the fiber strength was 1.88 cN / dtex, the nitrogen content was increased by 0.3% by weight, and the halogen content was decreased by 0.2% by weight. .
- Table 1 summarizes the ion exchange capacity, fiber strength, and the like of the ion exchange fibers obtained in Examples 1 to 11 and Comparative Examples 1 to 5.
- each of the ion exchange fibers of the present invention had a sufficient exchange capacity and fiber strength.
- polyglycidyl methacrylate when polyglycidyl methacrylate was not used, an ion exchange fiber having a low fiber strength and sufficient processability was not obtained in the reaction with triethylenetetramine, although the exchange capacity was sufficient. Further, when polyglycidyl methacrylate was not used, the reaction with cysteine or iminodiacetic acid did not sufficiently proceed, so that the exchange capacity was low and a practical ion exchange fiber could not be obtained.
- Example 12 to 20 Comparative Examples 6 to 12
- Production Examples 7 to 22 The ion exchange fibers 1 to 16 obtained were evaluated for ion exchange capacity, fiber strength, nitrogen content, chlorine content, and iodine saturated adsorption amount.
- Experiments performed using ion exchange fibers 1 to 9 correspond to Examples 12 to 20, and experiments performed using ion exchange fibers 10 to 16 correspond to Comparative Examples 6 to 12.
- Table 3 shows these production conditions and results.
- Example 19 and Comparative Example 4 are the same as Example 1 and Comparative Example 1, respectively, but they are shown again to show the iodine saturated adsorption amount.
- Comparative Examples 9 to 12 the production results of the ion exchange fibers 13 to 16 when using a modacrylic fiber not containing an epoxy group-containing polymer as a precursor fiber are shown.
- the reaction hardly proceeded and ion exchange fibers having a sufficient ion exchange capacity were not obtained.
- Comparative Example 9 when triethylenetetramine was used as the amine compound, although ion exchange fibers could be obtained, the fiber strength was insufficient and measurement was performed. I could not.
- Examples 15 to 20 when a modacrylic fiber containing an epoxy group-containing polymer is used as a precursor fiber, an ion exchange fiber having sufficient fiber strength is obtained. I was able to.
- activated carbon silver impregnated activated carbon (product name: TS, manufactured by Kuraray Chemical Co., Ltd., iodine saturated adsorption amount: 644 g / kg) was used.
- zeolite silver-impregnated zeolite (product name: Zeorum A3, manufactured by Tosoh Corporation, iodine saturated adsorption amount: 0.03 g / kg) was used.
- ion exchange resin an ion exchange resin (product name: MC-850, manufactured by Sumika Chemtex Co., Ltd., iodine saturated adsorption amount is 500 g / kg) was used.
- a cerium hydroxide-based adsorbent (product name: READ-F, manufactured by Nihonkaikai Co., Ltd., iodine saturated adsorption amount: 0.05 g / kg) was used.
- an ion exchange resin product name: MC-700, manufactured by Sumika Chemtex Co., Ltd.
- a cerium hydroxide-based adsorbent product name: READ-B, manufactured by Nihonkaikai Co., Ltd.
- the adsorbent of any one of activated carbon (Comparative Example 13), zeolite (Comparative Example 14), ion exchange resin (Comparative Example 15), or inorganic adsorbent (Comparative Example 16) was added to the standard solution. 15 g was added, and 0.2 g of 30% hydrogen peroxide was added under hydrochloric acid acidity. These were stirred at room temperature, and adsorbents were removed by filtration after 5 minutes, 10 minutes, 30 minutes, 60 minutes and 11 hours, respectively. The remaining amount of iodide ion at each time was quantified by ion chromatography.
- the iodine adsorption amount in each time was quantified by the same titration operation as the quantification of the iodine saturated adsorption amount. From these measurement results, the concentrations of iodide ions and iodine contained in the filtrate at each time were determined, and the total iodine adsorption rate at each time was determined by comparison with the initial concentration. In addition, the total iodine adsorption rate was calculated
- Total iodine adsorption rate [C 0 ⁇ (C I ⁇ + C I2 ⁇ 2)] ⁇ 100 / C 0 (Formula 4) (In the formula, C I ⁇ represents an iodide ion concentration, C I2 represents an iodine concentration, and C 0 represents an initial iodide ion concentration.) Table 4 shows the iodide ion and iodine concentrations in the filtrate at each time. In addition, Table 5 shows the total iodine adsorption rate at each time obtained from these values.
- FIG. 1 is a graph showing the results of Examples 21 to 23, and FIG. 2 is a graph showing the results of Comparative Examples 13 to 16.
- FIG. 3 shows a summary of Table 6 in a graph.
- FIG. 5 shows a summary of Table 8 in a graph.
- borate ions when borate ions were adsorbed by the method of the present invention, the borate ion adsorption rate was 90% or more within 60 minutes.
- iodide ions when iodide ions were adsorbed in a mode other than the method of the present invention, it took 6 hours or more for the total iodine adsorption rate to be 90% or more. This shows that borate ions can be removed and adsorbed at high speed and with high efficiency by using the method of the present invention.
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Abstract
Description
(1)ヨウ化カリウム(KI)を添着したアルカリ添着活性炭を大量に使用して、放射性ヨウ素である131Iを非放射性のヨウ素と同位体交換することによって捕集する。
(2)ヨウ素含有気体又は液体を、トリエチレンジアミン(TEDA)を添着した添着活性炭や強塩基性アニオン交換体に接触させて、3級アミノ基とヨウ化メチルとを反応させることによって除去する。
(3)ヨウ素含有気体又は液体を、銀ゼオライトに接触させて、ヨウ化銀として捕集する。
このように、排水中の各種化学物質は勿論のこと、放射性ヨウ素化合物といった化学物質をも効率良く除去・吸着できるようなイオン交換繊維及び水中の化学物質の除去・吸着方法が望まれている。
本発明の別の特徴の一つは、前記アミン化合物が、アミノ基の他に少なくとも1つの極性置換基を有する化合物を含むことを特徴とするイオン交換繊維である。
本発明の別の特徴の一つは、前記アミン化合物との反応による窒素含有量の増加が1.0重量%以上であることを特徴とするイオン交換繊維である。
本発明の別の特徴の一つは、前記イオン交換容量が1.0mmol/g以上であることを特徴とするイオン交換繊維である。
本発明の別の特徴の一つは、前記架橋アクリル系繊維がハロゲン原子を含み、前記アミン化合物との反応によるハロゲン含有量の減少が1.0重量%以上であることを特徴とするイオン交換繊維である。
本発明の別の特徴の一つは、前記イオン交換容量が1.0mmol/g以上であることを特徴とするイオン交換繊維である。
本発明の別の特徴の一つは、前記化学物質がイオン性化学物質であることを特徴とする化学物質の除去・吸着方法である。
本発明において、イオン交換繊維とは、その構造中にイオン交換性置換基を持ち、イオン交換能を示す繊維をいう。イオン交換性置換基としては、カチオン交換性置換基、アニオン交換性置換基のほか、2以上の極性基を有するキレート性置換基等が挙げられる。すなわち、本発明におけるイオン交換繊維は一般的なイオン交換繊維に加え、キレート繊維も指すものである。
1000である。エポキシ基含有ポリマーの量は使用するアミン化合物の種類、及び所望の繊維強度やイオン交換容量に応じ、適宜調整することが望ましい。
本発明の水中の化学物質の除去・吸着方法(以下「本発明の除去・吸着方法」とする)は、イオン交換繊維を用いて水中の化学物質の除去・吸着を行なう方法であって、イオン交換繊維として、上記で詳述した各構成を有する本発明のイオン交換繊維から選ばれる少なくとも1種を用いることを特徴としている。なお、本発明のイオン交換繊維を用いれば、水中だけでなく、気体中から化学物質を除去・吸着することもできる。
nI2+I- → I2n+1 - (式2)
この際、用いるイオン交換繊維としては、ヨウ素飽和吸着量が大きいものが好ましい。好ましい値は100g/kg以上、より好ましくは300g/kg以上、さらに好ましくは500g/kg以上である。ヨウ素飽和吸着量の大きいイオン交換繊維を用いることにより、ポリヨウ素イオンを効率的に吸着できる。ここで、ヨウ素飽和吸着量とは、繊維1kgが吸着可能なヨウ素の最大量である。
本発明の水中の化学物質の除去・吸着装置(以下「本発明の吸着・除去装置」とする)は、上記した各種構成を有する本発明のイオン交換繊維からなる群から選ばれる少なくとも1種を含む吸着体を備えていることを特徴とする。
テンシロンメータ(商品名:RTC-1210A、ORIENTEC社製)を用いて測定した。なお、不織布、紡績糸その他の形態への加工には0.8cN/dtex以上の繊維強度を持つことが必要である。
最初に、「ダイヤイオン イオン交換樹脂・合成吸着材マニュアル基礎編」(三菱化学(株)、1995年)P136に示される方法にて処理を行い、イオン交換繊維を基準型に調整した。
窒素含有量は、元素分析装置(商品名:JM10、ジェイ・サイエンス・ラボ社製)を使用して測定した。アミン化合物との反応前後の窒素含有量をそれぞれ測定し、その差から窒素含有量の増加を求めた。
ハロゲン含有量は、燃焼装置(商品名:QF02、(株)三菱化学アナリテック製)を用いて試料を燃焼させた後、ハロゲン化水素として遊離したハロゲンを水酸化ナトリウムで吸収し、イオンクロマトグラフィー装置(商品名:IC-2010、(株)東ソー製)にて定量した。アミン化合物との反応前後のハロゲン含有量をそれぞれ測定し、その差からハロゲン含有量の減少を求めた。
吸着体0.2gを0.05Nヨウ素標準液20gに浸漬し、3日間放置した。その後、上澄み液を2mL採取し10mLのイオン交換水とでんぷん液を加えた。この溶液を0.01Nのチオ硫酸ナトリウム水溶液で滴定し、上澄み液のヨウ素濃度を求めた。その結果から、次の(式3)によりヨウ素飽和吸着量を求めた。
(A:ヨウ素飽和吸着量、a:吸着後の上澄み液のヨウ素濃度)
なお、本明細書においてヨウ素飽和吸着量はg/kgで表され、1g/kgとは、1kgの吸着体が飽和状態で1gのヨウ素を吸着することを示す。
アクリロニトリル56重量%、塩化ビニル42重量%、パラスチレンスルホン酸ナトリウム2重量%よりなるモダアクリル系ポリマー100重量部、及びポリグリシジルメタクリレート(以下「PGMA」とも言う)67重量部をアセトンに溶解し、原液濃度30重量%の紡糸原液を得た。この紡糸原液を湿式紡糸し、前駆繊維を得た。次に、この前駆繊維5gを、200gの60重量%トリエチレンテトラミン水溶液中で120℃にて6時間反応し、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は4.67mmol/g、繊維強度は1.12cN/dtex、窒素含有量の増加は6.9重量%、ハロゲン含有量の減少は20.5重量%であった。
前駆繊維を作製する際、モダアクリル系ポリマーの量を100重量部、ポリグリシジルメタクリレートの量を25重量部とした点を除き、実施例1と同様の方法を用い、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は4.45mmol/g、繊維強度は1.22cN/dtex、窒素含有量の増加は6.6重量%、ハロゲン含有量の減少は15.7重量%であった。
前駆繊維を作製する際、モダアクリル系ポリマーの量を100重量部、ポリグリシジルメタクリレートの量を10重量部とした点を除き、実施例1と同様の方法を用い、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は4.39mmol/g、繊維強度は1.33cN/dtex、窒素含有量の増加は6.6重量%、ハロゲン含有量の減少は12.9重量%であった。
前駆繊維を作製する際、モダアクリル系ポリマーの量を100重量部、ポリグリシジルメタクリレートの量を5重量部とした点を除き、実施例1と同様の方法を用い、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は4.35mmol/g、繊維強度は1.22cN/dtex、窒素含有量の増加は6.4重量%、ハロゲン含有量の減少は13.5重量%であった。
前駆繊維を作製する際、モダアクリル系ポリマーの量を100重量部、ポリグリシジルメタクリレートの量を1重量部とした点を除き、実施例1と同様の方法を用い、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は4.30mmol/g、繊維強度は1.10cN/dtex、窒素含有量の増加は6.4重量%、ハロゲン含有量の減少は13.5重量%であった。
実施例1と同様の方法で前駆繊維を得た。次に、この前駆繊維5gを、22.9重量%システイン水溶液中で120℃にて6時間反応させ、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は3.57mmol/g、繊維強度は1.01cN/dtex、窒素含有量の増加は3.5重量%、ハロゲン含有量の減少は15.3重量%であった。
前駆繊維を作製する際、モダアクリル系ポリマーの量を100重量部、ポリグリシジルメタクリレートの量を43重量部とした点を除き、実施例6と同様の方法でイオン交換繊維を得た。このイオン交換繊維のイオン交換容量は2.68mmol/g、繊維強度は1.16cN/dtex、窒素含有量の増加は3.2重量%、ハロゲン含有量の減少は12.5重量%であった。
前駆繊維を作製する際、モダアクリル系ポリマーの量を100重量部、ポリグリシジルメタクリレートの量を25重量部とした点を除き、実施例6と同様の方法でイオン交換繊維を得た。このイオン交換繊維のイオン交換容量は1.92mmol/g、繊維強度は1.23cN/dtex、窒素含有量の増加は2.5重量%、ハロゲン含有量の減少は9.4重量%であった。
前駆繊維を作製する際、モダアクリル系ポリマーの量を100重量部、ポリグリシジルメタクリレートの量を5重量部とした点を除き、実施例6と同様の方法でイオン交換繊維を得た。このイオン交換繊維のイオン交換容量は1.37mmol/g、繊維強度は1.42cN/dtex、窒素含有量の増加は2.1重量%、ハロゲン含有量の減少は8.0重量%であった。
実施例2と同様の方法で前駆繊維を得た。次に、この前駆繊維5gを、18.4重量%イミノジ酢酸水溶液中で120℃にて6時間反応させ、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は1.69mmol/g、繊維強度は1.27cN/dtex、窒素含有量の増加は3.0重量%、ハロゲン含有量の減少は3.7重量%であった。
前駆繊維を作製する際、モダアクリル系ポリマーの量を100重量部、ポリグリシジルメタクリレートの量を5重量部とした点を除き、実施例10と同様の方法でイオン交換繊維を得た。このイオン交換繊維のイオン交換容量は1.12mmol/g、繊維強度は1.45cN/dtex、窒素含有量の増加は2.0重量%、ハロゲン含有量の減少は2.5重量%であった。
前駆繊維を作製する際、ポリグリシジルメタクリレートを使用しなかった点を除き、実施例1と同様の方法でイオン交換繊維を得た。このイオン交換繊維のイオン交換容量は4.26mmol/gであったが、繊維強度はテンシロンメータで測定できないほどに低かった。また、窒素含有量の増加は6.3重量%、ハロゲン含有量の減少は15.8重量%であった。
比較例1と同様の方法で前駆繊維を得た。次に、この前駆繊維5gを、22.9重量%システイン水溶液中で120℃にて6時間反応し、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は0.25mmol/g、繊維強度は1.83cN/dtex、窒素含有量の増加は0.3重量%、ハロゲン含有量の減少は0.3重量%であった。
比較例1と同様の方法で前駆繊維を得た。次に、この前駆繊維5gを、18.4重量%イミノジ酢酸水溶液中で120℃にて6時間反応し、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は0.08mmol/g、繊維強度は1.65cN/dtex、窒素含有量の増加は0.4重量%、ハロゲン含有量の減少は0.6重量%であった。
アクリロニトリル93重量%、及びアクリル酸メチル7重量%よりなるアクリル系ポリマーを公知の方法にて湿式紡糸し、前駆繊維とした。次に、この前駆繊維5gを、実施例1と同様の条件で反応し、イオン交換繊維を得た。このイオン交換繊維のイオン交換容量は4.68mmol/g、繊維強度は2.32cN/dtex、窒素含有量の増加は7.0重量%であった。
実施例1と同様の方法でイオン交換繊維を得た。ただし、トリエチレンテトラミンとの反応を行う際、反応温度は80℃とした。このイオン交換繊維のイオン交換容量は0.21mmol/g、繊維強度は1.88cN/dtex、窒素含有量の増加は0.3重量%、ハロゲン含有量の減少は0.2重量%であった。
最初に、表2に示すアクリル系ポリマー、モダアクリル系ポリマー、及びアクリロニトリル20重量%と塩化ビニル80重量%からなる塩化ビニル系ポリマーに、必要に応じエポキシ基含有ポリマーとしてポリグリシジルメタクリレートを混合した。これらをジメチルスルホキシドに溶解し、それぞれ紡糸原液を得た。次に、これらの紡糸原液を湿式紡糸し、前駆繊維としてアクリル系繊維、及びモダアクリル系繊維を得た。これらを前駆繊維A~F(製造例1~6)とした。
次に、上記製造例1~6で製造した前駆繊維A~Fをアミン化合物と反応させ、それぞれイオン交換繊維1~16(製造例7~22)を得た。アミン化合物としては、トリエチレンテトラミン、イミノジ酢酸、N-メチルグルカミン、システインを使用した。
製造例7~22得られたイオン交換繊維1~16について、イオン交換容量、繊維強度、窒素含有量、塩素含有量およびヨウ素飽和吸着量を評価した。イオン交換繊維1~9を用いて行った実験は実施例12~20に相当し、イオン交換繊維10~16を用いて行った実験は比較例6~12に相当する。これらの作製条件、及び結果を表3に示す。また、トリエチレンテトラミンを用いて作製したイオン交換繊維については、ヨウ素飽和吸着量の測定値を示す。尚、実施例19及び比較例4は、それぞれ実施例1及び比較例1と同じものであるが、そのヨウ素飽和吸着量を示すために再掲した。
本発明のイオン交換繊維のポリヨウ素イオン吸着性能を比較するために、以下の活性炭、ゼオライト、イオン交換樹脂、及び、無機吸着体を使用した。
ヨウ化カリウムを海水に溶解し、35ppmのヨウ化物イオンを含むヨウ化物イオン標準液を作製した。この標準液15gに、前記製造例13~15で製造したイオン交換繊維7~9(実施例21~23)を0.15g入れ、塩酸酸性下で30%過酸化水素水を0.2g加えた。また、比較として、この標準液に活性炭(比較例13)、ゼオライト(比較例14)、イオン交換樹脂(比較例15)、又は、無機吸着体(比較例16)のいずれかの吸着体0.15gを入れ、塩酸酸性下で30%過酸化水素水を0.2g加えたものを準備した。これらを室温にて攪拌し、5分後、10分後、30分後、60分後、11時間後にそれぞれ吸着体をろ過して除いた。各時間におけるヨウ化物イオンの残量をイオンクロマトグラフィーにて定量した。また、前記ヨウ素飽和吸着量の定量と同様の滴定操作により各時間におけるヨウ素吸着量を定量した。これらの測定結果から、各時間のろ液中に含まれるヨウ化物イオン、及びヨウ素の濃度を求め、初期濃度との比較より各時間における全ヨウ素吸着率を求めた。なお、全ヨウ素吸着率は以下の(式4)により求めた。
(式中、CI-:ヨウ化物イオン濃度、CI2:ヨウ素濃度、C0:初期ヨウ化物イオン濃度をそれぞれ示す。)
各時間におけるろ液中のヨウ化物イオン、及びヨウ素の濃度を表4に示した。また、これらの値から求めた各時間での全ヨウ素吸着率を表5に示した。また、実施例21~23の結果をグラフにしたものを図1に、比較例13~16の結果をグラフにしたものを図2に示した。
1000ppm鉛(II)標準液(和光純薬工業(株)製)を希釈し、10ppm鉛(II)標準液を作製した。この標準液30gに、前記イオン交換繊維1、4(実施例24、25)を0.15g加えた。また、比較としてこの標準液30gにイオン交換樹脂(比較例17)、又は製造例20で製造したイオン交換繊維14(比較例18)のいずれかの吸着体各0.15gを加えたものを準備した。これらを室温にて攪拌し、5分後、10分後、30分後、60分後、6時間後、14時間後、24時間後にそれぞれ吸着体をろ過して除いた。各時間におけるろ液中の鉛(II)イオン濃度をICP発光分析にて定量した。各時間におけるろ液中の鉛(II)イオンの濃度から、各時間での鉛(II)イオン吸着率を求めた。その結果を表6に示した。また、表6をグラフにまとめたものを図3に示した。
次に、1000ppm鉛(II)標準液(和光純薬工業社製)を希釈し、100ppm鉛(II)標準液を作製した。この標準液を用いて実施例24、25、及び比較例17、18と同様の方法にて各時間におけるろ液中の鉛(II)イオンの濃度を測定し、各時間での鉛(II)イオン吸着率を求めた。その結果を表7に示した。また、表7をグラフにまとめたものを図4に示した。
1000ppmホウ酸標準液(和光純薬工業(株)製)を希釈し、10ppmホウ酸標準液を作製した。この標準液30gに、イオン交換繊維2(実施例28)、及びイオン交換繊維5(実施例29)を0.15g加えた。また、比較としてこの標準液30gに無機吸着体(比較例21)、及びイオン交換繊維15(比較例22)のいずれかの吸着体各0.15gを加えたものを準備した。これらを室温にて攪拌し、5分後、10分後、30分後、60分後、6時間後、14時間後、24時間後にそれぞれ吸着体をろ過して除いた。各時間におけるろ液中のホウ酸イオン濃度をICP発光分析にて定量した。各時間におけるろ液中のホウ酸イオンの濃度から、各時間でのホウ酸イオン吸着率を求めた。その結果を表8に示した。また、表8をグラフにまとめたものを図5に示した。
Claims (23)
- 組成物100重量%中にアクリロニトリル30重量%以上を含むモノマー組成物を重合したアクリル系ポリマー100重量部にイオン交換性置換基を導入したポリマーAと、1重量部以上100重量部以下のエポキシ基含有ポリマーにイオン交換性置換基を導入したポリマーBとを含み、前記イオン交換性置換基は、いずれも、アミン化合物との反応により導入される、アミン化合物に由来するイオン交換性置換基であるイオン交換繊維。
- 前記アクリル系ポリマーが、その組成物100重量%中にアクリロニトリル30重量%以上70重量%以下、ハロゲン含有ビニリデンモノマー及び/又はハロゲン含有ビニルモノマー30重量%以上70重量%以下、並びにこれらと共重合可能なビニル系モノマー0重量%以上10重量%以下を含むモノマー組成物を重合したモダアクリル系ポリマーであることを特徴とする、請求項1に記載のイオン交換繊維。
- 前記アミン化合物が、1分子中の全アミノ基数が2以上である化合物を含むことを特徴とする請求項1又は2に記載のイオン交換繊維。
- 前記アミン化合物が、1分子中の全アミノ基数が1である化合物を含むことを特徴とする請求項1又は2に記載のイオン交換繊維。
- 前記モダアクリル系ポリマー100重量部に前記イオン交換性置換基を導入したポリマーAと、1重量部以上70重量部以下の前記エポキシ基含有ポリマーに前記イオン交換性置換基を導入したポリマーBとを含むことを特徴とする請求項2~4のいずれか一項に記載のイオン交換繊維。
- 前記モダアクリル系ポリマー100重量部に前記イオン交換性置換基を導入したポリマーAと、1重量部以上50重量部未満の前記エポキシ基含有ポリマーに前記イオン交換性置換基を導入したポリマーBとを含むことを特徴とする請求項5に記載のイオン交換繊維。
- 前記モダアクリル系ポリマー100重量部に前記イオン交換性置換基を導入したポリマーAと、1重量部以上30重量部以下の前記エポキシ基含有ポリマーに前記イオン交換性置換基を導入したポリマーBとを含むことを特徴とする請求項6に記載のイオン交換繊維。
- 前記アミン化合物が、アミノ基のうち少なくとも1つが1級アミンである化合物を含むことを特徴とする請求項1~7のいずれか一項に記載のイオン交換繊維。
- 前記アミン化合物が、アミノ基の他に少なくとも1つの極性置換基を有する化合物を含むことを特徴とする請求項1~7のいずれか一項に記載のイオン交換繊維。
- 繊維強度が0.8cN/dtex以上、イオン交換容量が0.8mmol/g以上であることを特徴とする請求項1~9のいずれか一項に記載のイオン交換繊維。
- 前記アミン化合物との反応による窒素含有量の増加が1.0重量%以上であることを特徴とする請求項1~10のいずれか一項に記載のイオン交換繊維。
- 前記アクリル系ポリマーがハロゲン原子を含み、前記アミン化合物との反応によるハロゲン含有量の減少が1.0重量%以上であることを特徴とする請求項1~11のいずれか一項に記載のイオン交換繊維。
- 前記イオン交換容量が1.0mmol/g以上であることを特徴とする請求項10~12のいずれか一項に記載のイオン交換繊維。
- アミン化合物との反応により前記アミン化合物に由来のイオン交換性置換基が導入され、かつ、前記アミン化合物により架橋された架橋アクリル系繊維であって、前記アミン化合物との反応による窒素含有量の増加が1.0重量%以上、繊維強度が0.8cN/dtex以上、及び、イオン交換容量が0.8mmol/g以上であることを特徴とするイオン交換繊維。
- 前記架橋アクリル系繊維が、架橋モダアクリル系繊維であることを特徴とする請求項14に記載のイオン交換繊維。
- 前記架橋アクリル系繊維がハロゲン原子を含み、前記アミン化合物との反応によるハロゲン含有量の減少が1.0重量%以上であることを特徴とする請求項14又は15に記載のイオン交換繊維。
- 前記イオン交換容量が1.0mmol/g以上であることを特徴とする請求項14~16のいずれか一項に記載のイオン交換繊維。
- 請求項1~17のいずれか一項に記載のイオン交換繊維の製造方法であって、
(1)組成物100重量%中にアクリロニトリル30重量%以上を含むモノマー組成物を重合したアクリル系ポリマー100重量部と、エポキシ基含有ポリマー1重量部以上100重量部以下とを混合して紡糸し、前駆繊維を得る工程と、
(2)前駆繊維とアミン化合物とを100℃を超える温度下で反応させ、アミン化合物に由来するイオン交換性置換基を前駆繊維に含まれるアクリル系ポリマー及びエポキシ基含有ポリマーに導入する工程とを含むイオン交換繊維の製造方法。 - イオン交換繊維を用いる水中の化学物質の除去・吸着方法であって、前記イオン交換繊維が、請求項1~17のいずれか一項に記載のイオン交換繊維であることを特徴とする水中の化学物質の除去・吸着方法。
- 前記化学物質がイオン性化学物質であることを特徴とする、請求項19に記載の水中の化学物質の除去・吸着方法。
- 前記イオン性化学物質が、ハロゲン化物イオン、ポリハロゲン化物イオン、オキソ酸イオンから選ばれる陰イオン;3族から16族の重金属イオン、ランタニド、アクチニドから選ばれる重金属元素のイオン、もしくはその錯イオン;からなる群より選ばれる1以上のイオンを含むイオン性化学物質であることを特徴とする、請求項20に記載の水中の化学物質の除去・吸着方法。
- 前記イオン性化学物質がハロゲン化物イオンを含むイオン性化学物質であり、前記ハロゲン化物イオンがヨウ化物イオンであることを特徴とする、請求項21に記載の水中の化学物質の除去・吸着方法。
- 請求項1~17のいずれか一項に記載のイオン交換繊維から選ばれる少なくとも1種のイオン交換繊維を含む吸着体を備える、水中の化学物質の除去・吸着装置。
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JP2012251912A (ja) * | 2011-06-03 | 2012-12-20 | Kaneka Corp | ヨウ化物イオンの除去・吸着方法 |
JP5504368B1 (ja) * | 2013-10-23 | 2014-05-28 | ラサ工業株式会社 | 放射性ヨウ素吸着剤、及び放射性ヨウ素の処理方法 |
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JP2015181972A (ja) * | 2014-03-20 | 2015-10-22 | 株式会社化研 | 水溶液からヨウ素を除去するヨウ素除去剤、除去装置および除去方法 |
JP2017529154A (ja) * | 2014-09-08 | 2017-10-05 | エイチシーピー ヘルスケア アジア ピーティーイー.リミテッド | 創傷の治癒に使用するための電気陰性繊維 |
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JP7475780B2 (ja) | 2020-06-23 | 2024-04-30 | 医療法人社団甲友会 | 甲状腺機能検査方法 |
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CL2013003104A1 (es) | 2014-03-14 |
MY185036A (en) | 2021-04-30 |
KR20140019379A (ko) | 2014-02-14 |
TWI556865B (zh) | 2016-11-11 |
KR101913118B1 (ko) | 2018-10-31 |
EP2703556A4 (en) | 2015-01-07 |
US9205422B2 (en) | 2015-12-08 |
US20140048489A1 (en) | 2014-02-20 |
EP2703556B1 (en) | 2021-06-16 |
EP2703556A1 (en) | 2014-03-05 |
JP5545412B2 (ja) | 2014-07-09 |
JPWO2012147937A1 (ja) | 2014-07-28 |
CN103502527B (zh) | 2015-11-25 |
CN103502527A (zh) | 2014-01-08 |
TW201249533A (en) | 2012-12-16 |
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