WO2010110311A1 - イオン交換体及びその製造方法 - Google Patents
イオン交換体及びその製造方法 Download PDFInfo
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- WO2010110311A1 WO2010110311A1 PCT/JP2010/055075 JP2010055075W WO2010110311A1 WO 2010110311 A1 WO2010110311 A1 WO 2010110311A1 JP 2010055075 W JP2010055075 W JP 2010055075W WO 2010110311 A1 WO2010110311 A1 WO 2010110311A1
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- ion
- ion exchange
- exchange resin
- ion exchanger
- weight
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- 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
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
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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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—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
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/018—Granulation; Incorporation of ion-exchangers in a matrix; Mixing with inert materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92695—Viscosity; Melt flow index [MFI]; Molecular weight
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92723—Content, e.g. percentage of humidity, volatiles, contaminants or degassing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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
- C08J2425/00—Characterised by the use 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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
Definitions
- the present invention relates to an ion exchanger and a method for producing the same, and more particularly to an ion exchanger obtained by extrusion molding and suitably applied to electrodeposition coating and a method for producing the same.
- the ion exchanger is a membrane for electrodialysis in the form of a membrane (that is, an ion exchange membrane) used for various purposes, for example, seawater concentration, salt water desalination, separation of ionic and nonionic substances, etc. It is widely used as a diaphragm for electrolysis of an alkali metal salt aqueous solution or an organic solution.
- the ion exchanger as described above is generally used in the form of a flat membrane, but recently, it is often used in the form of a tube.
- an ion exchanger in the form of a flat membrane it causes inconveniences such as an increased installation area of the ion exchanger in the electrolytic cell (for example, an electroplating bath or an electrodeposition coating bath)
- the portion occupied by the ion exchanger in the electrolytic cell becomes compact.
- a rib for supporting the flat membrane is required to prevent the deformation of the membrane, or a gasket or a spacer is required between adjacent membranes.
- the tubular ion exchanger has a problem that it is difficult to achieve both mechanical strength and electrical characteristics. That is, an ion exchanger of such a form is usually formed by using a resin composition containing ion exchange resin particles and a thermoplastic resin as a binder as a raw material, and melt extruding the resin composition. . For this reason, the surface of the ion exchange resin particles is covered with a thermoplastic resin that does not have ion exchange properties, and the electrical characteristics such as ion exchange ability are deteriorated (that is, the resistance of the membrane is increased). ). In order to avoid such inconvenience, the amount of ion-exchange resin particles used should be increased and the amount of thermoplastic resin as a binder should be reduced. In this case, however, the mechanical strength is reduced. For example, the liquid pressure is likely to cause deformation, and as a result, there arises a problem that inconvenience such as water permeability is likely to occur during use.
- Patent Document 1 discloses a polyethylene resin having a melt index of 2 g / 10 min or less and ion exchange resin particles.
- Tubular ion exchangers obtained by mixing at a weight ratio of 3: 7 to 5: 5 and extruding into a tubular shape have been proposed.
- the tubular ion exchanger proposed in Patent Document 1 uses a polyethylene resin having a low melt index (MI) as a binder resin, and the quantity ratio between the ion exchange resin particles and the binder resin (low MI polyethylene resin). Is set to a certain ratio to suppress the thermal decomposition of the ion exchange groups during extrusion molding, and to reduce the amount of ion exchange groups that lose the ion exchange ability due to the surface coating of the ion exchange resin particles with the binder resin. As a result, it is possible to achieve both good electrical characteristics (low resistance of the film) and mechanical strength.
- MI low melt index
- Patent Document 1 Although the tubular ion exchanger of Patent Document 1 is satisfactory in terms of excellent electrical characteristics and mechanical strength, there is a new problem of reduced contamination resistance. That is, in Patent Document 1, in order to achieve both electrical properties and mechanical strength, the amount of ion-exchange resin particles is increased, and a low melt index polyethylene resin is used as a binder resin. The surface of the molded body becomes rough, and as a result, foreign matter adheres to the surface and contamination easily occurs. Such a problem appears as a serious drawback when an ion exchanger is used for electrodeposition coating.
- the treatment liquid contains fine lumps of paint, and the fine lumps in the paint adhering to the surface of the ion exchanger grow by aggregation between individuals, and solid paints called “butsu” are formed. This is because a defect such as desorption from the surface of the ion exchanger and adhesion to the object to be coated occurs.
- a method of cleaning the surface of the ion exchanger is effective in order to suppress the generation of fuzz, but this results in a significant reduction in productivity.
- an object of the present invention is to provide an ion exchanger excellent in electrical characteristics, mechanical strength, and at the same time excellent in stain resistance, and a method for producing the same.
- Another object of the present invention is to provide an ion exchanger produced in particular by extrusion and in particular having a tubular shape.
- the present invention comprises a melt-extruded product of a resin composition comprising ion-exchange resin particles and a low-melting-point polyolefin resin having a melting point of 170 ° C. or less.
- the ion exchange resin particles are contained in a proportion of 30% by weight or more and less than 50% by weight, and the low melting point polyolefin resin is more than 100 parts by weight and less than 150 parts by weight per 100 parts by weight of the ion exchange resin particles.
- the melt index measured at 190 ° C. is in the range of 1 to 5 g / 10 min;
- C having a water content of 30% or more
- the ion exchanger of the present invention (1) Being tubular, (2) the water content of the ion exchange resin particles is greater than 50%; (3)
- the low melting point polyolefin resin is polyethylene, Is preferred.
- the moisture content of the ion exchanger is a saturated water amount that can be absorbed by the ion exchanger.
- the ion exchanger is immersed in salt water at 60 ° C. for 24 hours or more.
- the water ratio at the time is shown and is calculated by the following formula.
- the water content of the ion exchange resin is a saturated amount of water that can be absorbed by the ion exchange resin.
- the ratio is shown, and is calculated by the following formula, similarly to the water content of the ion exchanger.
- Water content (%) [(AB) / B] ⁇ 100
- A is the weight of the ion exchanger after the excess water on the outer surface is removed after the saturated water content is absorbed in the ion exchanger and water is absorbed into the ion exchanger.
- B is the weight of the ion exchanger in the dry state.
- the water content of the ion exchanger can be adjusted by the ion exchange capacity and the degree of crosslinking of the ion exchange resin particles used. For example, the greater the amount of ion exchange groups introduced into the ion exchange resin particles, the higher the moisture content of the ion exchange resin particles, and the degree of crosslinking of the ion exchange resin constituting the particles (used for resin formation).
- the water content of the ion exchange resin particles increases the ion exchange group amount to increase the ion exchange capacity, and at the same time, reduces the amount of crosslinkable monomer to lower the degree of crosslinking, thereby making the ion exchange resin relatively loose.
- the moisture content can be increased, and by adjusting the blending amount of the low-melting-point polyolefin resin powder according to the moisture content of the ion-exchange resin particles, the moisture content of the ion exchanger is within an appropriate range. Can be adjusted.
- the ion exchanger of the present invention is produced by melt extrusion molding. Particularly, as a binder resin used in combination with ion exchange resin particles, a low melting point polyolefin resin having a melting point of 170 ° C. or lower is used, and the ion exchange resin is used.
- the amount of particles is relatively small (the ion exchange resin particle content is 30 wt% or more and less than 50 wt%), the low melting point polyolefin resin is used more than the ion exchange resin particles, and the ion exchange resin particles and the binder resin (low
- the melt index (MI, 190 ° C.) of the melt-extruded product containing the melting point polyolefin resin) is set in the range of 1 to 5 g / 10 minutes (the above conditions (a) and (b)).
- MI melt index
- this ion exchanger has high mechanical strength and at the same time, the smoothness of the surface of the ion exchanger is enhanced (for example, its surface roughness Ra is 50 ⁇ m or less).
- the contamination resistance is extremely excellent. For example, even when electrodeposition coating or the like is continuously performed over a long period of time, it is possible to effectively prevent the adhesion of fouling to the surface of the ion exchanger.
- the ion exchanger of the present invention has the characteristics of low electrical resistance while having excellent mechanical strength and contamination resistance as described above. That is, although the content of ion exchange resin particles in the ion exchanger is less than 50% by weight, the water content of the ion exchanger is adjusted to 30% or more. High moisture content, in other words, having a high moisture content contributes greatly. Therefore, the ion exchanger after extrusion is in a dry state and does not contain moisture, but since the ion exchange resin used has a high water content, the ion exchanger is immersed in various salt aqueous solutions. When used, the ion exchange resin particles in the ion exchanger swell greatly. As a result, a fine gap is formed between the ion exchange resin particles and the binder resin (low MI resin), and the treatment liquid containing salts enters the gap, and the electrical resistance value is reduced. .
- the ion exchanger of the present invention has excellent electrical properties and mechanical strength while being formed by extrusion molding, and also has high surface smoothness, and is therefore included in the processing liquid. It is possible to effectively prevent the adhesion of fine lumps of paint and the like, and exhibits excellent stain resistance.
- the ion exchanger of the present invention is obtained by melt-extruding an ion exchange resin composition containing ion exchange resin particles and a low melting point polyolefin resin in a predetermined quantitative ratio and further containing appropriate additives.
- the water content is adjusted to 30% or more, particularly 30 to 40%, and the melt index (190 ° C.) is 1 to 5 g / 10 min, particularly 1 to 3 g / 10. In the range of minutes.
- ion exchange resin particles The ion exchange resin particles blended in the ion exchange resin composition to be subjected to melt extrusion molding are used for imparting ion exchange properties to the ion exchanger of the present invention. , Known per se are used.
- the water content of the ion exchange resin particles is preferably greater than 50%, and more preferably greater than 50 and 60% or less.
- the water content of the finally obtained ion exchanger is set so that the amount of the ion exchange resin particles and the low melting point resin is within a certain range. However, it is possible to adjust within the above range.
- Such ion exchange resin particles are obtained by polymerizing a polymerizable monomer suitable for introducing an ion exchange group and a crosslinkable monomer (crosslinking agent) in the presence of a polymerization initiator, and then introducing the ion exchange group. Finally, it is manufactured by adjusting to an appropriate particle size by pulverization or the like.
- polymerizable monomer suitable for the introduction of ion exchange groups known monomers used for the formation of ion exchange resins can be used without any limitation.
- ⁇ -halogenated vinyl sulfonic acid ⁇ , ⁇ , ⁇ ′-halogenated vinyl sulfonic acid, methacrylic acid, acrylic acid, styrene sulfonic acid, vinyl sulfonic acid, maleic acid, Itaconic acid, styrenephosphonic acid, maleic anhydride, vinyl phosphoric acid, and salts and esters thereof are suitable.
- the above-mentioned monomers may be used alone or in combination of two or more kinds that can be copolymerized with each other.
- the crosslinking agent used in combination with the polymerizable monomer is used to increase the particle strength and stably maintain the particle shape of the ion exchange resin during melt extrusion molding.
- m-, Divinyl compounds such as p- or o-divinylbenzene, divinylsulfone, butadiene, chloroprene, isoprene, trivinylbenzene, divinylnaphthalene, diallylamine, triallylamine, and divinylpyridine are used alone or in combination of two or more.
- Such a cross-linking agent is generally used in an amount of 5 to 150 parts by weight per 100 parts by weight of the above-mentioned monomer, and the larger the amount of the cross-linking agent, the more it penetrates into the resulting ion exchange resin particles.
- the amount of water decreases, the water content of the ion exchange resin particles (the amount of water that can be absorbed) decreases, and the less the crosslinking agent, the greater the amount of water that permeates into the resulting ion exchange resin particles.
- the water content of the resin particles increases. Therefore, the amount of the crosslinking agent used is set from the above range so that the moisture content of the ion exchange resin particles is within the above-described range (greater than 50%, particularly greater than 50 and less than 60%).
- a catalyst known per se for example, an organic peroxide such as benzoyl peroxide is used in a catalytic amount.
- the ion exchange group is introduced by means known per se, for example, depending on the type of ion exchange group (cation exchange group or anion exchange group) to be introduced, sulfonation, haloalkylation, amination, phosphoniumation, It is carried out by a per se known process such as sulfoniumation or hydrolysis.
- the amount of ion exchange groups introduced is generally set so that the ion exchange capacity on a dry basis is in the range of 0.1 to 20 meq / g, particularly about 0.5 to 3 meq / g. As the amount increases, the water content of the obtained ion exchange resin particles increases, and as the ion exchange capacity decreases, the water content decreases.
- the amount of ion exchange groups introduced is, for example, the amount of the above-mentioned crosslinking agent so that the water content of the ion exchange resin particles is within a predetermined range (greater than 50%, especially greater than 50 and less than 60%). It will be set accordingly.
- the introduction of the ion exchange group is generally performed after the polymerization of the polymerizable monomer and the crosslinking agent as described above. However, in some cases, the ion exchange group is previously introduced into the polymerizable monomer. After the polymerization, it is possible to carry out the polymerization of the polymerizable monomer and the crosslinking agent.
- the ion exchange resin having a high water content (greater than 50%, particularly greater than 50 and less than 60%) thus obtained is pulverized and then classified by a mesh or the like to obtain a granular material having a predetermined particle size.
- the average particle diameter (D 50 ) in terms of volume measured by, for example, a laser diffraction scattering method is 0.00.
- a range of about 01 to 100 ⁇ m is preferable.
- the particle size is too large, the dispersion state of the ion exchange resin particles present in the ion exchanger becomes non-uniform, and the characteristics of the ion exchanger are likely to vary, and if the particle size is too small, This is because not only the workability such as mixing is deteriorated but also the particles are easily aggregated, and it is difficult to uniformly disperse, and the characteristics of the ion exchanger are likely to vary.
- the low melting point polyolefin resin used in combination with the above ion exchange resin particles has a function as a binder, and is used to give the obtained ion exchanger a predetermined mechanical strength.
- a low melting point polyolefin resin having a melting point of 170 ° C. or lower it is heated to a temperature higher than the melting point of the resin at the time of melt extrusion molding, resulting in thermal decomposition of ion exchange groups in the ion exchange resin particles. This is because the ion exchange performance of the obtained ion exchanger is impaired.
- Examples of such a low melting point polyolefin resin having a melting point of 170 ° C. or lower include thermoplastic resins having no functional group reactive with ion exchange groups, such as low, medium or high density polyethylene, polypropylene, poly 1 -Polyolefin resins such as butene, poly-4-methyl-1-pentene, or random or block copolymers of ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, and ⁇ -olefins
- a modified polyolefin resin grafted with a vinyl monomer such as acrylic acid or methacrylic acid is used.
- the low-melting polyolefin resin has a melt index (MI, 190 ° C.) within a predetermined range (1 to 5 g / 10 min) of the MI (190 ° C.) of the ion-exchangeable resin composition used for melt extrusion.
- MI melt index
- 190 ° C. ° C.
- it should be within a range that can be adjusted to 1 to 3 g / 10 min. Therefore, generally, a range of about 3 to 7 g / 10 min is used. This is because if the MI of the ion exchange resin composition is out of the predetermined range, an ion exchanger having the desired characteristics cannot be obtained.
- low melting point polyolefin resins described above low, medium or high density polyethylene, ethylene copolymer having an ethylene content of 50% by weight or more, or methacrylic acid is grafted. Modified polyethylene and the like are preferred.
- additives known per se can be blended within a range not impairing the object of the present invention.
- Representative examples of such additives include lubricants, stabilizers and antioxidants.
- the lubricant examples include hydrocarbons such as polyethylene wax, aliphatic amides such as stearamide, and fatty acid esters such as butyl stearate.
- the stabilizer or antioxidant examples include lead-based compounds such as dibasic stearic acid, calcium-based compounds, cadmium-based compounds, barium-based compounds, zinc-based compounds, and tin-based compounds.
- the ion exchange resin composition to be subjected to melt extrusion is prepared by mixing the above-described components.
- the conditions required for the obtained ion exchanger that is, (A) The ion exchange resin particles are contained in a proportion of 30% by weight or more and less than 50% by weight, and the low melting point resin is more than 100 parts by weight and less than 150 parts by weight per 100 parts by weight of the ion exchange resin particles. Contained in quantity, (B) MI measured at 190 ° C.
- Moisture content is 30% or more, particularly in the range of 30 to 40%, Is required to obtain an ion exchanger having a small electrical resistance value, excellent electrical characteristics, excellent mechanical strength, and at the same time excellent contamination resistance.
- the above condition (b) regarding MI of the ion exchange resin composition is a condition particularly necessary for maintaining good electrochemical characteristics while forming a smooth surface on the ion exchanger, for example. If the MI is less than the above range, the flowability of the resin composition during melt extrusion molding is too low, so that the surface smoothness of the ion exchanger that is an extrusion molded article is impaired, and the MI is higher than the above range. As a result of the fluidity of the resin composition being too high, the surface of the ion exchange resin particles is completely covered with the low melting point polyolefin resin, and the electrochemical characteristics of the resulting ion exchanger are impaired.
- the above-mentioned condition (c) concerning the moisture content is a condition particularly necessary for ensuring the electric characteristics of the ion exchanger, and since the moisture content is within the above range, the obtained ion exchanger has a water absorption As a result of swelling due to, a gap is formed between the ion-exchange resin particles and the low-melting-point polyolefin resin, and a highly conductive medium such as an aqueous salt solution penetrates into this space, resulting in low electrical resistance of the ion exchanger, That is, the increase in electrical resistance due to the use of the low melting point polyolefin resin can be effectively suppressed.
- the degree of swelling due to water absorption is small, so that a space in which a conductive medium can enter is formed between the ion exchange resin particles and the low melting point polyolefin resin. As a result, it becomes impossible to obtain an ion exchanger with low electrical resistance.
- the water content of this resin composition is preferably in the above-mentioned preferred range (30 to 40%).
- the use amounts of the ion exchange resin particles and the low melting point resin are the conditions (a).
- ion-exchange resin particles having a moisture content in the above-described range are selected so that the MI in condition (b) and the moisture content in condition (c) can be satisfied. It is necessary to select a low-melting-point polyolefin resin having MI, and various additives that are optionally used will be used in amounts that do not inhibit these conditions.
- the temperature of this melt kneading should be 150 degrees C or less. This is because, when this temperature is high, the ion exchange groups of the ion exchange resin particles are thermally decomposed and lost, and the electric characteristics of the obtained ion exchanger may be impaired.
- the ion exchanger of the present invention can be obtained by melt-extruding an ion exchange resin composition that satisfies the above conditions.
- This melt extrusion is performed, for example, by putting pellets obtained by melt kneading using an extruder into an extruder having a die corresponding to the shape of the ion exchanger to be molded.
- it is necessary to carry out at a temperature of 150 ° C. or lower in order to avoid thermal decomposition of ion exchange groups.
- melt extrusion is performed by setting the temperature of the cylinder portion of the extruder to 90 to 140 ° C. and the die portion temperature to 100 to 150 ° C.
- the ion exchanger of the present invention obtained by melt extrusion as described above satisfies the above-mentioned conditions (a) to (c), and is obtained by melt extrusion using a low melting point polyolefin resin in combination.
- it has excellent mechanical strength and electrical characteristics, and also has a high surface smoothness and therefore excellent stain resistance.
- a swelling treatment is performed after melt extrusion in order to express excellent electrical characteristics.
- the water content reaches a saturated state (specifically, the water content rises to the above-mentioned water content level), and between the surface of the ion exchange resin particles and the low melting point polyolefin resin. A gap will be formed.
- Such swelling treatment is performed, for example, by spraying hot water or immersing in hot water, and the treatment time is about several minutes to several tens of hours.
- Such swelling treatment can also be performed by immersing the ion exchanger in various salt aqueous solutions to be treated.
- the ion exchanger of the present invention may have an arbitrary shape such as a flat membrane shape or a tubular shape.
- it may have a tubular shape from the viewpoint that the treatment tank for electrolysis or dialysis can be made compact. Is preferred.
- the thickness is preferably in the range of about 1 to 5 mm from the standpoint of its self-sustainability and shape retention.
- the ion exchanger of the present invention is excellent in surface smoothness.
- the average surface roughness Ra JIS-B-0601-1994
- the ion exchanger of the present invention is particularly suitably applied to the field of electrodeposition coating where the occurrence of scum is a problem.
- the surface having the smoothness as described above can be realized by surface polishing or the like after the extrusion molding.
- a surface having high smoothness is obtained without performing such a process such as surface polishing. Therefore, it is extremely advantageous from the viewpoint of productivity.
- MI Melt index
- 10 g of an ion exchanger melt-extruded using an ion exchange resin and a low-melting polyolefin resin was cut into pieces having a size of 2 mm or less.
- the melt flow index of the ion exchanger was measured at 190 ° C. (load: 2.16 kgf) in accordance with JIS-K-6760 using a small melt indexer manufactured by TECHNOL SEVEN.
- Moisture content (%) (Wet weight (g) -dry weight (g)) ⁇ 100 / wet weight (g) ... (1)
- Ra Surface roughness
- the obtained tubular ion exchanger (outer diameter: 6.3 cm, length: 200 cm) was immersed in an electrodeposition bath for 6 months to conduct a mounting test, and visually confirmed whether or not there was any flaws on the membrane surface before and after the test. did.
- the tubular ion exchanger obtained by melt extrusion is cut into a size of about 2 cm square and immersed in a 0.5N sodium chloride aqueous solution for 1 hour three times, and the counter-ion in the membrane is completely Cl—
- Na + type was used, and the membrane resistance in a 0.5N sodium chloride aqueous solution was measured by an alternating current method under the conditions of a frequency of 1.0 kHz, a measurement area of 1 cm 2 and 25 ° C.
- Example 1 A suspension copolymer of styrene-divinylbenzene (6% by weight containing divinylbenzene) is chloromethylated and then quaternized with trimethylamine to give an anion exchange resin (ion exchange capacity 3.0 meq / g) having a water content of 55%. Produced. The anion exchange resin was dried at 60 ° C. for 16 hours, and then classified with a 100 mesh sieve, and the passing portion of the sieve was used as an anion exchange resin powder.
- Anion-exchange resin powder 100 parts by weight Low-density polyethylene powder 110 parts by weight Calcium stearate 3 parts by weight Barium stearate 1 part by weight, these components were mixed well in advance and then pelletized by a hot-cut method using a kneading extruder. .
- the obtained pellets were put into an extruder having a cylinder part temperature of 90 to 140 ° C. and a die part temperature of 130 to 150 ° C., and extruded into a tubular shape having an inner diameter of 30 mm, an outer diameter of 35 mm, and a thickness of 2.5 mm by a sizing plate device.
- the tubular ion exchanger thus obtained was immersed in a 0.2N sodium chloride aqueous solution at 60 ° C. for 24 hours for swelling treatment. Thereafter, the moisture content, surface roughness, membrane resistance and burst strength of the ion exchanger were measured.
- Table 1 shows the types, blending amounts and physical properties (moisture content, MI), etc., of the ion exchange resin (IER) and low melting point resin (polyethylene) used in the molding of the extruded product, and Table 2 shows various measurement results. .
- Example 2 a tubular ion exchanger was prepared in the same manner except that high-density polyethylene powder (HDPE) was used instead of low-density polyethylene, and the moisture content, surface roughness, membrane resistance, and burst strength were respectively determined. It was measured. The results are shown in Tables 1 and 2.
- HDPE high-density polyethylene powder
- Example 3 A styrene-divinylbenzene suspension copolymer (8% by weight containing divinylbenzene) was chloromethylated, then quaternized with trimethylamine to give an anion exchange resin (ion exchange capacity 3.0 meq / g) having a water content of 52%. Produced. Using this ion exchange resin, a tubular ion exchanger was prepared in the same manner as in Example 1, and the water content, surface roughness, membrane resistance and burst strength were measured. The results are shown in Tables 1 and 2.
- Example 4 a tubular ion exchanger was prepared in the same manner except that the addition amount of the low density polyethylene powder was 150 parts by weight with respect to 100 parts by weight of the ion exchange resin powder, and the moisture content, surface roughness, membrane Resistance and burst strength were measured respectively. The results are shown in Tables 1 and 2.
- Example 5 In Example 1, the low density polyethylene powder seed was changed, and the MI of the mixture was 4.5 g / 10 min. Except for the above, a tubular ion exchanger was prepared in the same manner, and the water content, surface roughness, membrane resistance and burst strength were measured. The results are shown in Tables 1 and 2.
- Example 6 A suspension copolymer of styrene-divinylbenzene (6% by weight containing divinylbenzene) was sulfonated to prepare a cation exchange resin (ion exchange capacity: 3.0 meq / g) having a water content of 55%. Otherwise, a tubular ion exchanger was prepared in the same manner as in Example 1, and the water content, surface roughness, membrane resistance and burst strength were measured. The results are shown in Table 1.
- Example 2 a tubular ion exchanger was prepared in the same manner except that the amount of the low density polyethylene powder added was 80 parts by weight with respect to 100 parts by weight of the ion exchange resin powder, and the water content, surface roughness, membrane Resistance and burst strength were measured respectively. The results are shown in Tables 1 and 2.
- Example 3 a tubular ion exchanger was prepared in the same manner except that the kind of the low density polyethylene powder was changed and the MI of the mixture was changed to 0.5, and the moisture content, surface roughness, membrane resistance, and burst strength were prepared. Was measured respectively. The results are shown in Tables 1 and 2.
- Example 4 a tubular ion exchanger was prepared in the same manner except that the kind of the low density polyethylene powder was changed and the MI of the mixture was changed to 5.6, and the moisture content, surface roughness, membrane resistance and burst strength were prepared. Was measured respectively. The results are shown in Tables 1 and 2.
- Example 6 a tubular ion exchanger was prepared in the same manner except that the kind of the low density polyethylene powder was changed and the MI of the mixture was changed to 0.7, and the water content, surface roughness, membrane resistance and burst strength were prepared. Was measured respectively. The results are shown in Tables 1 and 2.
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Abstract
Description
本発明の他の目的は、特に押出成形により製造され、特に管状形状を有しているイオン交換体を提供することにある。
(a)前記イオン交換樹脂粒子を30重量%以上50重量%未満の割合
で含有し、且つ、前記低融点ポリオレフィン樹脂を該イオン交換樹脂
粒子100重量部当り100重量部より多く、150重量部以下の量
で含有していること、
(b)190℃で測定されるメルトインデックスが1~5g/10分の
範囲にあること、
(c)30%以上の含水率を有していること、
を満足していることを特徴とするイオン交換体が提供される。
(1)管状を成していること、
(2)前記イオン交換樹脂粒子の含水率が50%より大きいこと、
(3)前記低融点ポリオレフィン樹脂がポリエチレンであること、
が好適である。
イオン交換樹脂粒子と融点が170℃以下の低融点ポリオレフィン樹脂とを含み、該イオン交換樹脂粒子を30重量%以上50重量%未満の割合で含有し、該低融点ポリオレフィン樹脂を該イオン交換樹脂粒子100重量部当り100重量部より多く150重量部以下の量で含有しており、190℃で測定されるメルトインデックスが1~5g/10分の範囲で且つ含水率が30%以上に調整された樹脂組成物を用意し、
前記樹脂組成物を溶融押出し、
得られた押出成形体を膨潤処理して含水率を30%以上に調整すること、
を特徴とするイオン交換体の製造方法が提供される。
含水率(%)=[(A-B)/B]×100
式中、Aは、塩水に浸漬し、イオン交換体へ飽和水分量を吸水させた
後、外表面の余剰な水分を除去した後のイオン交換体重量であり、
Bは、乾燥状態のイオン交換体の重量である。
このイオン交換体の含水率は、用いるイオン交換樹脂粒子のイオン交換容量と架橋度とにより調整することができる。例えば、イオン交換樹脂粒子に導入されているイオン交換基の量が多いほどイオン交換樹脂粒子の含水率は高く、この粒子を構成しているイオン交換樹脂の架橋度(樹脂の形成に用いているジビニルベンゼン等の架橋性モノマーの使用割合に相当)が高いほど、含水率は低くなる。従って、イオン交換樹脂粒子の含水率は、イオン交換基量を多くしてイオン交換容量を高めると同時に、架橋性モノマーの量を少なくして架橋度を低くし、イオン交換樹脂を比較的ルーズな構造とすることにより、含水率を高めることができ、イオン交換樹脂粒子の含水率に応じて該低融点ポリオレフィン樹脂粉末の配合量を調整することにより、イオン交換体の含水率を適宜の範囲に調整することができる。
溶融押出成形に供されるイオン交換性樹脂組成物中に配合されるイオン交換樹脂粒子は、本発明のイオン交換体にイオン交換性を持たせるために使用されるものであり、基本的には、それ自体公知のものが使用される。
特にカチオン交換樹脂粒子を形成する場合には、α-ハロゲン化ビニルスルホン酸、α,β,β’-ハロゲン化ビニルスルホン酸、メタクリル酸、アクリル酸、スチレンスルホン酸、ビニルスルホン酸、マレイン酸、イタコン酸、スチレンホスホニル酸、無水マレイン酸、ビニルリン酸、及びこれらの塩類、エステル類などが好適である。
また、アニオン交換樹脂粒子を形成する場合には、ビニルピリジン、メチルビニルピリジン、エチルビニルピリジン、ビニルピロリドン、ビニルカルバゾール、ビニルイミダゾール、アミノスチレン、アルキルアミノスチレン、ジアルキルアミノスチレン、トリアルキルアミノスチレン、メチルビニルケトン、クロルメチルスチレン、アクリル酸アミド、アクリルアミド、オキシウム、スチレン、ビニルトルエンなどが好適である。
上述した単量体は、1種単独で使用してもよいし、或いは互いに共重合可能である2種以上を組み合わせて使用することもできる。
このような架橋剤は、一般に、前述した単量体100重量部当り5乃至150重量部の量で使用されるが、この架橋剤の量が多いほど、得られるイオン交換樹脂粒子中に浸透する水の量が少なくなり、イオン交換樹脂粒子の含水率(吸水し得る水分量)が低くなり、架橋剤が少ないほど、得られるイオン交換樹脂粒子中に浸透する水の量が多くなり、イオン交換樹脂粒子の含水率は増大する。従って、架橋剤の使用量は、イオン交換樹脂粒子の含水率が前述した範囲内(50%より大きく、特に50より大きく60%以下)となるように、上記範囲内から設定される。
イオン交換基の導入量は、一般に、乾燥基準でのイオン交換容量が0.1~20meq/g、特に0.5~3meq/g程度の範囲となるように設定されるが、このイオン交換容量が多いほど、得られるイオン交換樹脂粒子の含水率が多くなり、イオン交換容量が少ないほど、その含水率は低下する。従って、イオン交換基の導入量は、イオン交換樹脂粒子の含水率が所定の範囲内(50%より大きい、特に50より大きく60%以下)となるように、たとえば前述した架橋剤の使用量に応じて設定されることとなる。
このようなイオン交換樹脂粒子は、後述するバインダー樹脂(低融点樹脂)中に均一に分散させるために、例えばレーザ回折散乱法によって測定される体積換算での平均粒径(D50)が0.01~100μm程度の範囲であることが好適である。即ち、この粒径が大きすぎると、イオン交換体中に存在するイオン交換樹脂粒子の分散状態が不均一となり、イオン交換体の特性にバラツキを生じ易くなり、また、この粒径が小さ過ぎると、混合等の作業性が低下するばかりか、粒子同士の凝集を生じ易くなり、やはり、均一分散が困難となり、イオン交換体の特性にバラツキを生じ易くなるからである。
上記のイオン交換樹脂粒子と併用される低融点ポリオレフィン樹脂は、バインダーとしての機能を有するものであり、得られるイオン交換体に所定の機械的強度を持たせるために使用される。
溶融押出成形に供されるイオン交換性樹脂組成物中には、本発明の目的を損なわない範囲でそれ自体公知の添加剤を配合することができる。このような添加剤としては、例えば滑剤、安定剤及び酸化防止剤などが代表的である。
溶融押出に供するイオン交換性樹脂組成物は、上述した各成分を混合することにより調製されるが、かかる樹脂組成物においては、得られるイオン交換体に要求される条件、即ち、
(a)前記イオン交換樹脂粒子を30重量%以上50重量%未満の割合
で含有し、且つ、前記低融点樹脂を該イオン交換樹脂粒子100重量
部当り100重量部より多く、150重量部以下の量で含有している
こと、
(b)190℃で測定されるMIが1~5g/10分、特に1乃至3g
/10分の範囲にあること、
(c)含水率が30%以上、特に30乃至40%の範囲にあること、
を満足していることが、電気抵抗値が小さく、電気特性に優れ、しかも機械的強度に優れていると同時に耐汚染性に優れたイオン交換体を得る上で必要である。
本発明のイオン交換体は、上記のような条件を満足するイオン交換性樹脂組成物を溶融押出することにより得られる。この溶融押出は、例えば押出機を用いての溶融混練により得られたペレットを、成形するイオン交換体の形状に応じたダイスを有する押出機内に投入して行われる。この溶融押出においても、イオン交換基の熱分解を回避するために150℃以下の温度で行うことが必要であり、例えば、用いる低融点樹脂の種類や使用量によっても異なるが、一般的には、押出機のシリンダ部の温度を90~140℃、ダイ部温度を100~150℃の温度に設定して溶融押出が行われる。
尚、以下の例で、用いた材料の各種物性や作製したイオン交換体の各種特性の評価は、以下の方法で行った。
イオン交換樹脂と低融点ポリオレフィン樹脂を用いて溶融押出成形したイオン交換体10gを、2mm以下のサイズに細かく切り出した。次いで、TECHNOL SEVEN社製小型メルトインデクサを用いて、JIS-K-6760に準拠して190℃(荷重:2.16kgf)で該イオン交換体のメルトフローインデックスを測定した。
(イオン交換樹脂の含水率)
イオン交換樹脂を1.0N 塩化ナトリウム水溶液中に1時間浸漬する操作を3回繰り返し、対イオンを完全にアニオン交換樹脂ではCl-型、カチオン交換樹脂ではNa+型とした。
次いで該アニオン交換樹脂を、メスシリンダーを用いて正確に10ml秤量し、これを布で包み径15cm、回転数3000rpmの条件で5分間遠心分離を行い、付着水分を除いた後すばやく秤量ビンに移して密栓し、正確な湿潤重量を得た。その後、該樹脂を105℃±2℃の高温乾燥機中で4時間乾燥し、デシケーター中で30分放冷して乾燥重量を測定した。含水率は以下の(1)式より算出した。
(イオン交換体の含水率)
溶融押出成形により得た管状イオン交換体を、60℃、1.0N塩化ナトリウム水溶液に8時間浸漬する操作を3回繰返し、該イオン交換体中の対イオンを完全にアニオン交換樹脂ではCl-型、カチオン交換樹脂ではNa+型とした。次いで、該イオン交換体を所定の大きさに切断し、表面の付着水分を布で十分に除去したあと、湿潤重量を測定した。その後、該イオン交換体を105℃±2℃の高温乾燥機中で4時間乾燥し、デシケーター中で30分放冷して乾燥重量を測定した。含水率は以下の(1)式より算出した。
含水率(%)
=(湿潤重量(g)-乾燥重量(g))×100/湿潤重量(g)
…(1)
溶融押出成形により得た管状イオン交換体を1cm角程のサイズに切り出し、キーエンス社製カラー3Dレーザ顕微鏡VK-8700を用いて、JIS-B-0601-1994にしたがい、非接触法で10点平均粗さを測定した。
得られた管状イオン交換体(外径6.3cm、長さ200cm)を6ヶ月間電着槽に浸漬して実装試験を行い、試験前後の膜表面へのブツ発生の有無を、目視により確認した。
溶融押出成形により得た管状イオン交換体を、2cm角ほどのサイズに切り出し、0.5N塩化ナトリウム水溶液に1時間浸漬する操作を3回繰返し、膜内対イオンを完全にアニオン交換体ではCl-型、カチオン交換体ではNa+型とした後、交流法により、周波数1.0kHz、測定面積1cm2、25℃の条件にて、0.5N塩化ナトリウム水溶液中での膜抵抗を測定した。
長さ10cmの管状イオン交換体の両端にそれぞれゴム栓を詰めた後、接着剤によって密封し、一方のゴム栓に設けた貫通パイプを使って管状イオン交換体の内部に水を満たし、さらに水圧をかけて管状イオン交換体が破裂したときの水圧値を破裂強度として測定した。
スチレン-ジビニルベンゼンの懸濁共重合体(ジビニルベンゼン含有6重量%)をクロルメチル化後、トリメチルアミンで第4級アンモニウム化して含水率55%のアニオン交換樹脂(イオン交換容量3.0meq/g)を作製した。このアニオン交換樹脂を60℃で16時間乾燥させた後、100メッシュフルイにて分級し、フルイの通過分をアニオン交換樹脂粉末として使用した。
下記処方;
アニオン交換樹脂粉末 100重量部
低密度ポリエチレン粉末 110重量部
ステアリン酸カルシウム 3重量部
ステアリン酸バリウム 1重量部
にしたがい、これらの成分を予め十分に混合した後、混練押出機によりホットカット法によりペレット化した。
得られたペレットをシリンダ部温度90~140℃、ダイ部温度130~150℃の押出機に入れ、サイジングプレート装置により内径30mm、外径35mm、厚み2.5mmの管状に押出成形した。
このようにして得られた管状イオン交換体を、60℃、0.2Nの塩化ナトリウム水溶液に24時間浸漬し膨潤処理を行った。その後、該イオン交換体の含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
押出成形体の成形に用いたイオン交換樹脂(IER)及び低融点樹脂(ポリエチレン)の種類、配合量及び物性(含水率、MI)等を表1に示し、各種の測定結果を表2に示す。
実施例1において、低密度ポリエチレンの代わりに高密度ポリエチレン粉末(HDPE)を使用したこと以外はすべて同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1及び表2に示した。
スチレン-ジビニルベンゼンの懸濁共重合体(ジビニルベンゼン含有8重量%)をクロルメチル化後、トリメチルアミンで第4級アンモニウム化して含水率52%のアニオン交換樹脂(イオン交換容量3.0meq/g)を作製した。このイオン交換樹脂を用いて、実施例1と同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1及び表2に示した。
実施例1において、低密度ポリエチレン粉末の添加量をイオン交換樹脂粉末100重量部に対して150重量部とした以外はすべて同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1及び表2に示した。
実施例1において、低密度ポリエチレン粉末種を変更し、混合物のMIを4.5g/10min.とした以外はすべて同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1及び表2に示した。
スチレン-ジビニルベンゼンの懸濁共重合体(ジビニルベンゼン含有6重量%)をスルホン化して含水率55%のカチオン交換樹脂(イオン交換容量3.0meq/g)を作製した。それ以外は実施例1と同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1に示した。
スチレン-ジビニルベンゼンの懸濁共重合体(ジビニルベンゼン含有12重量%)をクロルメチル化後、トリメチルアミンで第4級アンモニウム化して含水率40%のアニオン交換樹脂(イオン交換容量 meq/g)を作製した。それ以外は実施例1と同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1及び表2に示した。
実施例1において、低密度ポリエチレン粉末の添加量をイオン交換樹脂粉末100重量部に対して80重量部とした以外はすべて同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1及び表2に示した。
実施例1において、低密度ポリエチレン粉末の種類を変更し、混合物のMIを0.5とした以外は全て同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1及び表2に示した。
実施例1において、低密度ポリエチレン粉末の種類を変更し、混合物のMIを5.6とした以外は全て同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1及び表2に示した。
実施例6において、低密度ポリエチレン粉末の種類を変更し、混合物のMIを0.7とした以外は全て同様にして管状イオン交換体を調製し、含水率、表面粗さ、膜抵抗および破裂強度をそれぞれ測定した。
その結果を表1及び表2に示した。
Claims (8)
- イオン交換樹脂粒子と融点が170℃以下の低融点ポリオレフィン樹脂とを含む樹脂組成物の溶融押出成形体よりなり、前記溶融押出成形体は、下記条件;
(a)前記イオン交換樹脂粒子を30重量%以上50重量%未満
の割合で含有し、且つ、前記低融点ポリオレフィン樹脂を該イ
オン交換樹脂粒子100重量部当り100重量部より多く、1
50重量部以下の量で含有していること、
(b)190℃で測定されるメルトインデックスが1~5g/
10分の範囲にあること、
(c)30%以上の含水率を有すること、
を満足していることを特徴とするイオン交換体。 - 管状を成す請求項1記載のイオン交換体。
- 前記イオン交換樹脂粒子の含水率が50%を超える請求項1記載のイオン交換体。
- 前記低融点ポリオレフィン樹脂がポリエチレンである請求項1記載のイオン交換体。
- イオン交換樹脂粒子と融点が170℃以下の低融点ポリオレフィン樹脂とを含み、該イオン交換樹脂粒子を30重量%以上50重量%未満の割合で含有し、該低融点ポリオレフィン樹脂を該イオン交換樹脂粒子100重量部当り100重量部より多く150重量部以下の量で含有しており、190℃で測定されるメルトインデックスが1~5g/10分の範囲に調整された樹脂組成物を用意し、
前記樹脂組成物を溶融押出し、
得られた押出成形体を膨潤処理して含水率を30%以上に調整すること、
を特徴とするイオン交換体の製造方法。 - 管状を成す請求項5に記載のイオン交換体の製造方法。
- 前記イオン交換樹脂粒子として、含水率が50%を超えるものを使用する請求項5記載のイオン交換体の製造方法。
- 前記低融点ポリオレフィン樹脂として、ポリエチレンを使用する請求項5記載のイオン交換体の製造方法。
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EA201171162A EA020718B1 (ru) | 2009-03-25 | 2010-03-24 | Ионообменник |
US13/203,363 US8530018B2 (en) | 2009-03-25 | 2010-03-24 | Ion exchanger and method of producing the same |
EP10756107.8A EP2412751B1 (en) | 2009-03-25 | 2010-03-24 | Ion exchange body and production method therefor |
KR1020117019703A KR101709799B1 (ko) | 2009-03-25 | 2010-03-24 | 이온 교환체 및 그의 제조 방법 |
CN201080010030.0A CN102341439B (zh) | 2009-03-25 | 2010-03-24 | 离子交换体及其制造方法 |
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NL2008516C2 (en) * | 2012-03-21 | 2013-09-25 | Voltea Bv | Method for preparing an anion exchange membrane with ion exchange groups and an apparatus for removal of ions. |
EP2833984A4 (en) * | 2012-04-05 | 2016-01-06 | 3M Innovative Properties Co | COMPOSITE ION EXCHANGE MEDIA FOR LIQUID FILTRATION SYSTEMS |
JP2018176051A (ja) * | 2017-04-11 | 2018-11-15 | パナソニックIpマネジメント株式会社 | イオン交換膜およびそれを備えたイオン交換膜積層体、水処理装置 |
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KR100684836B1 (ko) * | 2005-03-28 | 2007-02-20 | 삼성에스디아이 주식회사 | 연료전지용 촉매 복합체, 이의 제조방법, 이를 포함하는막-전극 어셈블리, 및 이를 포함하는 연료전지 시스템 |
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- 2010-03-24 US US13/203,363 patent/US8530018B2/en active Active
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JPH02259000A (ja) * | 1989-03-30 | 1990-10-19 | Tokuyama Soda Co Ltd | 透析用電極装置 |
JP2557525B2 (ja) | 1989-04-03 | 1996-11-27 | 株式会社トクヤマ | 管状イオン交換体の製造方法 |
JPH09124805A (ja) * | 1995-11-02 | 1997-05-13 | Asahi Glass Co Ltd | 不均質イオン交換体およびその製造方法 |
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EA201171162A1 (ru) | 2012-03-30 |
US20110305861A1 (en) | 2011-12-15 |
JP5349106B2 (ja) | 2013-11-20 |
JP2010222533A (ja) | 2010-10-07 |
EP2412751B1 (en) | 2014-09-03 |
CN102341439B (zh) | 2014-04-16 |
US8530018B2 (en) | 2013-09-10 |
EA020718B1 (ru) | 2015-01-30 |
CN102341439A (zh) | 2012-02-01 |
KR101709799B1 (ko) | 2017-02-23 |
EP2412751A1 (en) | 2012-02-01 |
EP2412751A4 (en) | 2013-07-31 |
KR20120010224A (ko) | 2012-02-02 |
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