WO1998022217A1 - Materiau polymere pour le traitement de l'eau, resine d'echange cationique et resine d'echange anionique - Google Patents

Materiau polymere pour le traitement de l'eau, resine d'echange cationique et resine d'echange anionique Download PDF

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Publication number
WO1998022217A1
WO1998022217A1 PCT/JP1997/004189 JP9704189W WO9822217A1 WO 1998022217 A1 WO1998022217 A1 WO 1998022217A1 JP 9704189 W JP9704189 W JP 9704189W WO 9822217 A1 WO9822217 A1 WO 9822217A1
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Prior art keywords
group
exchange resin
antioxidant function
water treatment
covalently bonded
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PCT/JP1997/004189
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English (en)
Japanese (ja)
Inventor
Masa-Aki Wakita
Masato Yamaguchi
Tsuneyasu Adachi
Toshihiro Ueno
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Kurita Water Industries Ltd.
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Priority claimed from JP32219896A external-priority patent/JPH10137736A/ja
Priority claimed from JP28191497A external-priority patent/JP3911794B2/ja
Priority claimed from JP30870597A external-priority patent/JP3911801B2/ja
Application filed by Kurita Water Industries Ltd. filed Critical Kurita Water Industries Ltd.
Publication of WO1998022217A1 publication Critical patent/WO1998022217A1/fr

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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
    • 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
    • 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

Definitions

  • the present invention relates to a polymer water treatment material, a cation exchange resin, and an anion exchange resin. More specifically, the present invention relates to a coagulant, a dehydrating agent, and a dispersing agent, in which a group having an antioxidant function is covalently bonded, and there is little risk of deterioration in performance due to oxidative deterioration and contamination of water quality due to oxidative decomposition products during use.
  • Polymer water treatment material that can be used for water treatment as a membrane, etc., cation exchange resin with excellent resistance to oxidative decomposition and less elution of resin components, and anion with excellent resistance to oxidative decomposition and less elution of resin components Regarding exchange resin.
  • an ion exchange resin has a structure in which an ion exchange group such as a sulfonic acid group or a trimethylammonium group is bonded to a polymer matrix having a three-dimensional network structure represented by a styrene-divinylbenzene copolymer. It is an insoluble solid acid or solid base that has been widely used in the production of ultrapure water used in the manufacture of semiconductors and pharmaceuticals, and in the condensate treatment of nuclear power plants.
  • the flocculant, dehydrating agent, and dispersant include monomers having a carboxyl group such as acrylamide, acrylic acid, and methacrylic acid, 2-acrylamide 2-methylpropanesulfonic acid, vinylsulfonic acid, and styrenesulfonic acid. Homopolymers or copolymers of monomers having a sulfonic acid group, such as dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates, etc .; A modified polymer having a structure or the like, a natural polymer such as chitosan, starch or the like, or a modified product thereof is used. As the membrane, cellulose acetate, polyimide, polyamide, High molecular compounds such as polysulfone are used.
  • Organic polymers generally undergo oxidative decomposition gradually in the presence of oxygen.
  • the conventional polymer water treatment material ion exchange resin has the following problems caused by oxidative decomposition. For example, when ion-exchange resins and membranes are used in the production of ultrapure water used in semiconductor and pharmaceutical manufacturing, if the ion-exchange resins and membranes are oxidized and decomposed to elute constituent components, the quality of treated water will decrease. Occur.
  • Oxidative degradation products such as sulfobenzoic acid, phenolsulfonic acid, and styrenesulfonic acid polymers are eluted from the strongly acidic cation exchange resin in which sulfonic acid groups are introduced into styrene divinylbenzene crosslinked copolymer particles. .
  • These effluents not only degrade the quality of the treated water, but also decompose during heat exchange of the condensate to produce corrosive sulfate ions. It also contaminates the anion exchange resin, which is often used simultaneously.
  • Styrene divinylbenzene cross-linked copolymer Decomposition products such as etc. are eluted, similarly deteriorating the treated water quality and contaminating the cation exchange resin often used at the same time. In addition, as the oxidative decomposition of the ion exchange resin proceeds, the ion exchange resin itself deteriorates.
  • Coagulants and dehydrating agents are added to wastewater and sludge as aqueous solutions to coagulate suspended solids and perform solid-liquid separation.However, the coagulant effect of coagulants and dispersants is greatly affected by their molecular weight, so oxidation When the molecular weight is reduced by decomposition, the performance is significantly reduced. That is, in the case of the polymer water treatment material, there is a problem that even if the oxidative decomposition is slight, the function is lowered or the water quality is lowered.
  • JP-A-1-1191345 and JP-A-2-91946 disclose that an ion-exchange resin is stored in a low-dissolved oxygen concentration water or oxygen-free atmosphere, There is disclosed a method of avoiding contact with oxygen by lowering the dissolved oxygen concentration of an elephant fluid and passing the solution.
  • Japanese Patent Publication No. 40-239398 discloses the oxidation of polyphenylene ether, fluorine-containing polymers, polyimides, polyamideimides, etc.
  • a method for preparing a polymer water treatment material or an ion exchanger from a special material having a chemical structure that is difficult to receive is disclosed.
  • these materials are not only more expensive than conventional polymer water treatment materials and ion exchangers, but also have problems in that it is difficult to control the shape and porosity of the product.
  • Japanese Patent No. 25174111 discloses a method of suppressing oxidation by bringing a cation exchange resin into contact with an antioxidant and incorporating the antioxidant. ing.
  • Japanese Patent Publication No. 491-27622, Japanese Patent Publication No. 52-272, and Japanese Patent Publication No. 58-47414 include acrylamide-based polymers.
  • a stabilization method is disclosed by blending thiourea, formic acid, ammonia, potassium iodide, and 2-mercaptobenzoimidazole.
  • the auxiliary compounded for stabilization is physically incorporated or mixed, so that the auxiliary compound is eluted into the treated water. is there.
  • the present invention has excellent resistance to oxidative decomposition, and is less likely to cause deterioration in performance due to oxidative degradation during use and to cause contamination of water quality due to oxidized decomposed substances, and is used in water treatment as a coagulant, a dehydrating agent, a dispersant, a membrane, etc.
  • Polymer water treatment materials that can be used, cation exchange resin with excellent resistance to oxidative decomposition and low elution of resin components during use, and anion exchange with excellent resistance to oxidative decomposition and low elution of resin components during use The purpose was to provide resin. Disclosure of the invention
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, oxidative decomposition of the polymer water treatment material has already occurred in some parts immediately after synthesis, and oxidative decomposition even under ordinary storage or use conditions. Gradually progresses, and by covalently bonding a group having an antioxidant function to the polymer matrix of the polymer water treatment material, the antioxidant is simply mixed and impregnated or bonded by ionic bonds. It is more stable against oxidation than the ones that have been made, and it has been found that the performance is stably maintained for a long time as a polymer water treatment material or ion exchange resin.
  • the group having an antioxidant function is a hindered amine group, a monocyclic or polycyclic hindered phenol group, a thioester group, a thioether group, an amine group, a phosphorus group, a benzophenone group, a salicylate group or a triazole group.
  • R 1 is hydrogen or a methyl group.
  • Fig. 1 is a graph showing the change over time in the amount of eluted material from the cation exchange resin.
  • the group having an antioxidant function introduced by a covalent bond is not particularly limited.
  • 2,2,6,6-tetramethyl-4-piperidine, 1,2,2 Hindered amines such as 2,6,6-pentamethyl-1-piperidine, monocyclic phenols such as 2,6-di-t-butyl-1-p-cresol, tetrakis [methylene-1- (3 ' Polycyclic phenols such as, 5'-di-t-butyl-4'-hydroxyphenylpropionate] methane, bis [2-methyl-1- (3-n-alkylthiopropionyloxy)- thioesters such as [t-butyl phenyl] sulfide; thioethers such as dilauryl thiodipropionate; phenyl- ⁇ -naphthylamine; N, N'-diphenyl ⁇ _phenylene Phosphorus antioxidants such as
  • Salicylates such as benzophenone, phenyl salicylate, p-t-butylphenyl salicylate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1 Hindered amide-based light stabilizers such as 1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and triazole-based heavy metals such as 3- (N-salicyloyl) amine 1,2,4-triazole Examples include groups derived from compounds having an antioxidant function, such as blocking agents.
  • the amount of the group having an antioxidant function that is covalently bonded is not particularly limited. It is preferably 10 mol%, more preferably 0.01 to 8 mol%, and still more preferably 0.01 to 7 mol%. If the bonding amount of the group having an antioxidant function is less than 0.01 mol% of the monomer unit, the polymer water treatment material may not be provided with sufficient oxidation stability. The amount of binding of the group having an antioxidant function is usually 10 mol% is sufficient. The amount of groups attached decreases, and in many cases, it is economically disadvantageous.
  • a method of covalently bonding a group having an antioxidant function is not particularly limited.
  • a method of reacting a compound having an antioxidant function with a polymer water treatment material to form a polymer water A group having an antioxidant function can be covalently bonded to the treatment material, and after copolymerizing a monomer having an antioxidant function with another monomer, a functional group having a water treatment function is introduced by reaction.
  • a polymer water treatment material in which a group having an antioxidant function is covalently bonded by copolymerization of a monomer having an antioxidant function and a monomer having a water treatment function can be obtained. .
  • Examples of the monomer having an antioxidant function include a monomer having an antioxidant function and a monomer for addition polymerization having an unsaturated bond, and a structure having an antioxidant function and two functional groups having condensation reactivity.
  • Condensation polymerization monomer having the above structure with antioxidant function is ring-opening polymerizable Ring-opening polymerization monomers bonded to the structure can be exemplified.
  • these methods there is a method of copolymerizing a monomer for addition polymerization having a structure having an antioxidant function and an unsaturated bond with or without a water treatment function and a monomer for addition polymerization. Synthesis is easy and preferred.
  • Examples of the monomer for addition polymerization having a structure having an antioxidant function and an unsaturated bond include, for example, 1,2,2,6,6, -pentanomethyl-4-piperidinyl methacrylate [Asahi Denka Kogyo Co., Ltd. ), Adekastab LA-82], 2,2,6,6-tetramethyl-14-piperidinyl methacrylate [Asahi Denka Kogyo Co., Ltd., Adekastab LA-87], etc.
  • hindered drugs such as 2,6-di-t-butyl-14-vinylphenol and derivatives thereof described in Makromol. Chem., Vol. 181, p. 557 (1980).
  • Biperidine and its derivatives 4-[(bicyclo [2.2.1] hept-5-en-1-ynole) methoxy] -1,2,2,6,6-tetramethylpiperidine and its derivatives, J.
  • antioxidants such as hindered amine, monocyclic or polycyclic hindered phenol, thioester, thioether, amine, phosphorus, benzophenone, salicylate, triazole, etc.
  • Monomer into which polymerizable group having unsaturated bond such as vinyl group, aryl group, styryl group, acryloyl group, methacryloyl group, N-vinylamino group, N-arylamino group, acrylamide group, methacrylamide group is introduced. Etc. can be used.
  • antioxidants have a polymerizable group capable of undergoing polycondensation or ring-opening polymerization, for example, an amino group, a carboxyl group, a hydroxyl group, ethylene oxide, / 3-propiolactone, and / 3-pro- Monomers having a structure such as piolactam or ⁇ -force prolactam can be used.
  • radical polymerization and cationic polymerization may be used.
  • Polymerization methods such as addition polymerization such as anion polymerization and condensation polymerization and ring-opening polymerization can be appropriately selected.
  • the method for covalently bonding a group having an antioxidant function to a polymer water treatment material having no antioxidant function is not particularly limited.
  • a functional group such as a hydroxyl group, an amino group, a carboxyl group, or a halogenated alkyl group may be used.
  • the high-molecular-weight water treatment material and an antioxidant capable of forming a covalent bond by reacting with these functional groups can be reacted. If the high molecular weight water treatment material does not have an appropriate functional group, it can react with an antioxidant after introducing an appropriate functional group, or can be combined with an antioxidant having an appropriate functional group and a polymer water treatment. Can react with the material.
  • a group having an antioxidant function is covalently bonded via a sulfonamide bond represented by the general formula [1].
  • R 1 is hydrogen or a methyl group.
  • the method for producing the cation exchange resin of the present invention is not particularly limited.
  • a chlorosulfone group and a sulfonate group are introduced into an insoluble carrier made of a polymer having a three-dimensional network structure, Compounds with groups with antioxidant function It can be produced by reacting with a methyl sulfone group.
  • the structure, shape, and manufacturing method of the insoluble carrier made of a polymer having a three-dimensional network structure are not particularly limited, and examples thereof include organic polymers such as a copolymer of styrene and divinylbenzene, a cross-linked polyethylene, and a cross-linked polypropylene.
  • Insoluble carriers such as spheres, membranes, and fibers can be used.
  • Crosslinked particles made of a styrene-divinylbenzene copolymer are obtained by dispersing styrene and divinylbenzene in water containing a dispersant such as polyvinyl alcohol, polyvinylpyrrolidone, and calcium phosphate.
  • Such a radical polymerization initiator can be obtained by adding the radical polymerization initiator, and heating and stirring to carry out suspension polymerization.
  • the ratio of styrene to divinyl benzene is not particularly limited, it is usually preferable that the content of divinyl benzene is 6 to 20% by weight, more preferably 8 to 12% by weight.
  • the method of introducing a group having an antioxidant function into a cation exchange resin via a sulfonamide bond is not particularly limited.
  • a chlorosulfone group is introduced into an insoluble carrier, and a primary or secondary amino group is further introduced. It can be easily introduced by reacting a group with a compound having a group having an antioxidant function.
  • a ketone sulfone group can be easily introduced into the styrenedivinylbenzene crosslinked copolymer particles.
  • the reaction can be promoted by using a solvent that swells the styrene-divinylbenzene crosslinked copolymer particles such as tetrachloroethane and dichloromethane.
  • the chlorosulfonating agent is preferably used in an amount equal to or more than the amount to be introduced.In the case of styrene-divinylbenzene crosslinked copolymer particles, use 2 to 3 times the benzene ring in the particles. Is preferred.
  • the temperature and time for the sulphonation reaction can be carried out by immersing in an ice-water bath or stirring at room temperature for several hours. After completion of the chlorosulfonation reaction, the reaction mixture is preferably filtered and washed with a solvent that does not react with chlorosulfone groups, such as chloroform, dichloromethane, and acetone.
  • a compound having a primary or secondary amino group and a group having an antioxidant function include, for example,
  • Hindered amide compounds such as 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6,6-pentamethylpiperidine, and 2,6-di-t— Butyl-4-aminomethylphenol, 2,6-di-t-butyl-4-methylethylaminophenol, 2,6-di-t-butyl-4-aminophenol, 2, Hindered phenolic compounds such as 6-di-t-butyl-14-aminopropylphenol and the like can be mentioned.
  • the amount of the group having an antioxidant function to be introduced is not particularly limited, but is usually preferably from 0.01 to 10% by weight of the cation exchange resin.
  • reaction temperature and time are not particularly limited, but usually the reaction can be terminated by stirring at room temperature for several hours.
  • the hydrolysis method is not particularly limited.
  • a product obtained by reacting a compound having an amino group and a group having an antioxidant function can be dispersed in water to perform a hydrolysis reaction.
  • the hydrolysis reaction usually proceeds efficiently by heating at 40 to 50 ° C.
  • hydrochloric acid is generated to lower the pH of the system.
  • a compound having a buffering action such as sodium acetate, may be coexistent, or hydroxylated. It is preferable to add an alkali such as sodium to prevent the system from becoming strongly acidic.
  • the antioxidant since a group having an antioxidant function is introduced by a covalent bond, the antioxidant is more oxidatively prevented than a conventional method in which an antioxidant is ionically adsorbed or physically retained. Prevents the agent from falling off, maintains excellent antioxidant properties over a long period of time, and effectively prevents the elution of resin components during use Can be.
  • the anion exchange resin of the present invention is a resin in which a group having an antioxidant function is covalently bonded via an iminoalkylene bond represented by the general formula [2].
  • R 2 is hydrogen or a methyl group
  • n is an integer of 1 to 4.
  • the method for producing the anion exchange resin of the present invention is not particularly limited.
  • a halogenated alkyl group is introduced into an insoluble carrier made of a polymer having a three-dimensional network structure, and a part of the halogenated alkyl group is amino.
  • a group having an antioxidant function is introduced by reacting the group with a compound having an antioxidant function, and an amine is reacted with the remaining alkyl halide group to form a quaternary ammonium group. Can be manufactured.
  • an alkyl halide group is introduced into an insoluble carrier made of a polymer having a three-dimensional network structure, and most of the alkyl halide group is reacted with an amine to form a quaternary ammonium group, and the remaining halogen is added. It can also be produced by introducing a group having an antioxidant function by reacting a compound having an amino group with an antioxidant function with an alkyl group.
  • the structure, shape, and production method of the insoluble carrier comprising a polymer having a three-dimensional network structure are not particularly limited, and examples thereof include organic polymers such as a copolymer of styrene and divinylbenzene, a crosslinked polyethylene, and a crosslinked polypropylene.
  • Insoluble carriers such as polymer spheres, membranes, and fibers can be used.
  • Crosslinked particles composed of a styrene-divinylpentene copolymer are obtained by dispersing styrene and divinylbenzene in water containing a dispersant such as polyvinyl alcohol, polyvinylpyrrolidone, and calcium phosphate.
  • a radical polymerization initiator can be obtained by adding the above radical polymerization initiator, heating and stirring to carry out suspension polymerization.
  • the halogenated alkyl group introduced into the insoluble carrier is a halogenated alkyl group having 1 to 4 carbon atoms, and is preferably a chloromethyl group.
  • the number of carbon atoms in the halogenated alkyl group is 5 or more, the ion exchange capacity per unit weight of the anion exchange resin becomes small, and the hydrophobicity of the anion exchange resin becomes too strong. There is a risk.
  • the insoluble carrier is a copolymer of styrene
  • the chloromethyl group is reacted by reacting chloromethyl methyl ether in the presence of a catalyst such as anhydrous aluminum chloride, tin tetrachloride, stannic chloride, or anhydrous zinc chloride.
  • a catalyst such as anhydrous aluminum chloride, tin tetrachloride, stannic chloride, or anhydrous zinc chloride.
  • the reaction can be promoted by using a solvent such as tetrachloroethane or dichloromethane that swells the styrene-divinylbenzene bridge copolymer particles.
  • Chloromethyl methyl ether is usually used in an amount equal to or greater than the amount to be introduced, and when the insoluble carrier is a styrene-divinylbenzene cross-linked copolymer particle, it is 2-3 equivalent times the benzene ring in the particle. It is preferable to use
  • the reaction temperature and reaction time are not particularly limited, and can be appropriately set depending on the catalyst used. For example, when stannic chloride is used, the reaction may be performed at 50 to 70 ° C for 4 to 6 hours. When anhydrous aluminum chloride is used, the activity is high. The reaction may take up to 3 hours. After completion of the reaction, the reaction mixture is preferably filtered to separate chloromethylated particles, and washed with a solvent that does not react with chloromethyl groups, such as chloroform and dichloromethane.
  • particles such as styrene-divinylbenzene cross-linked copolymer particles into which a halogenated alkyl group has been introduced are dispersed in a solvent such as benzene, chloroform, and dichloromethane to form a primary or secondary amino group and an antioxidant function.
  • a solvent such as benzene, chloroform, and dichloromethane
  • a group having an antioxidant function can be covalently bonded via an iminoalkylene group.
  • Examples of the compound having a primary or secondary amino group and a group having an antioxidant function include, for example, 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6, Hindered amine compounds such as 6-pentamethylpiperidine, 2,6-di-tert-butyl-1-aminomethylphenol, 2,6-di-tert-butyl-14-methylaminomethylphenol, 2,6 Hindered phenolic compounds such as di-tert-butyl-4-aminophenol and 2,6-di-tert-butyl-4-aminopropylphenol;
  • the amount of the group having an antioxidant function to be introduced is not particularly limited, but is usually preferably from 0.01 to 10% by weight of the anion exchange resin.
  • Reaction temperature and anti The reaction time is not particularly limited. For example, the reaction can be completed by a reaction at room temperature for several hours.
  • the amine that is reacted to convert the halogenated alkyl group into a quaternary ammonium group examples thereof include trialkylamines such as trimethylamine and dialkylmonoamines such as dimethylmonoethanolamine. Alkanolamine and the like can be mentioned.
  • the ammoniating reaction can be terminated by blowing the amine into the reaction system and, for example, reacting at room temperature for 10 to 12 hours.
  • the antioxidant since a group having an antioxidant function is introduced by a covalent bond, the antioxidant is more oxidized than the conventional method in which the antioxidant is ionically adsorbed or physically retained.
  • the agent does not easily fall off, maintains excellent resistance to oxidative decomposition over a long period of time, and can effectively prevent elution of resin components and deterioration of the resin during use.
  • a dispersant composed of sodium polystyrenesulfonate having a 2,2,6,6-tetramethyl-14-piperidinyl group covalently bonded thereto was synthesized.
  • the infrared absorption spectrum of the obtained product shows an absorption band derived from the benzene ring at 3070 cm-3030 cm1 600 cm-1500 cm-835 cm- 1.
  • a 0.5% by weight aqueous solution of this copolymer was prepared, and the viscosity of the solution was measured at 20 ° C. using a B-type viscometer.
  • 200 ml of this solution was placed in a beaker, a 6% by weight aqueous solution of hydrogen peroxide was added at 50 // 1, and the mixture was placed in a 50 ° C water bath and heated for 4 days. Thereafter, when the temperature was returned to 20 ° C. and the solution viscosity was measured, it was 22 cP, and there was no change in the solution viscosity.
  • a dispersant consisting of sodium polystyrene sulfonate was synthesized.
  • Example 1 A 0.5% by weight aqueous solution of the obtained sodium polystyrene sulfonate was prepared, and in the same manner as in Example 1, the solution viscosity immediately after preparation and hydrogen peroxide were added, and the mixture was heated for 4 hours in a 50 ° C water bath. The solution viscosity afterwards was measured. The solution viscosity immediately after preparation was 56 cP, and the solution viscosity after adding a hydrogen peroxide solution and heating was 15 cP. As shown in Example 1 and Comparative Example 1, a group having an antioxidant function is covalently bonded.
  • a powdered cation exchange resin having a 2,2,6,6-tetramethyl-14-piperidinyl group covalently bound as a group having an antioxidant function was synthesized.
  • the obtained product does not dissolve in water, and the infrared absorption spectrum of the product is determined by comparing the sodium styrenesulfonate obtained in Example 1 with 2,2,6,6-tetramethyl-1-piperidine.
  • the product obtained is sodium styrenesulfonate, styrene, divinylbenzene and 2,266-tetramethyl-14-piperidinium, since the absorption spectrum is the same as that of the methyl methacrylate copolymer. It was confirmed that it was a copolymer of nilmethacrylate.
  • a group having an antioxidant function was bonded to form an L-type powdered cation exchange resin.
  • Example 2 using 16.06 g (78.0 mimol) of sodium styrenesulfonate, 1.54 g (14.8 mimol) of styrene and 1.75 g (7.4 mimol) of divinylbenzene [55% by weight of active ingredient] The synthesis was performed to obtain 13.61 g of a copolymer of sodium styrenesulfonate, styrene and divinylbenzene.
  • the amount of organic carbon in the supernatant of the cation exchange resin to which a group having an antioxidant function is covalently bonded is determined by the amount of the group having an antioxidant function. Since the amount of the organic carbon in the supernatant of the cation exchange resin that has not been subjected to the reaction is smaller than that of the supernatant, it is understood that the decomposition and elution of the resin are suppressed by covalently bonding a group having an antioxidant function.
  • a lid equipped with a Teflon blade for stirring and a nitrogen gas inlet tube was attached, and stirring was performed at 150 rpm while blowing nitrogen gas at a rate of 15 OmlZ.
  • the separable flask was placed in a constant temperature water bath maintained at 70 ° C., and the nitrogen gas was blown at a rate of 1 O OmlZ, and heated for 17 hours.
  • the resulting white particles were collected by filtration through No. 5A filter paper, washed with water, methanol, chloroform, and methanol in that order, and dried in vacuo at room temperature to obtain 45.95 g of a particulate product. .
  • the product was poured into water, filtered, and washed with acetone and water in this order.
  • the product after washing, 40.00 g of sodium acetate and 200 ml of water are placed in a 500 ml separable flask, immersed in a constant temperature water bath maintained at 40 ° C, and blown with nitrogen gas at 75 ml / min. Stirred for hours.
  • the product was collected by filtration and washed with water.
  • the infrared absorption spectrum of the product, 120 Ocnr 1 1 derived from a sulfonic acid group An absorption band of 13 Ocm ⁇ 1040cm-1010cm- 1 was observed.
  • a lid equipped with a Teflon blade for stirring and a nitrogen gas inlet tube was attached, and the mixture was stirred at 15 Orpm while blowing nitrogen gas at 15 OmlZ.
  • the separable flask was placed in a thermostatic water bath maintained at 70 ° C, and the nitrogen gas was blown at 10 OnilZ minutes, and heated for 17 hours.
  • the resulting white particles were collected by filtration through a No. 5A filter paper, washed with water, methanol, chloroform, and methanol in that order, and vacuum dried at room temperature to obtain 23.76 g of a particulate product. Obtained.
  • the absorption band of 172 Ocnr 1 based on the vibration and the absorption band of 361 Ocm- 1 based on the 0-H stretching vibration were observed, indicating that the obtained products were styrene, divinylbenzene and 2- [1-1 (2 , 1-hydroxy_3 ', 5'-di-t-pentylphenyl) ethyl] —4,6-di-t-pentylphenylacrylate.
  • the product was thrown into water, filtered, and washed with acetone and water in that order. Transfer the washed product, sodium acetate (25.00 g) and water (120 ml) to a 300 ml separable flask, immerse it in a constant temperature water bath maintained at 40 ° C, and blow nitrogen gas at 75 ml for 6 hours at 4 Orpm. Stirred. The product was collected by filtration and washed with water.
  • a cation exchange resin having a 2,2,6,6-tetramethyl-4-piberidinyl group covalently bound as a group having an antioxidant function was synthesized.
  • styrene-divinylbenzene crosslinked copolymer particles [manufactured by Supe 1 c 0. Inc., specific surface area 330 m 2 / g, average pore size 9 OA] are mixed with water, methanol, chloroform, and tetrachlorene. And washed in this order.
  • the crosslinked particles and Tet 85 ml of lachlorethane was placed in a 50 Oml separable flask, fitted with a lid equipped with a Teflon blade for stirring, a nitrogen gas inlet tube, and a cooling tube, heated at 60 ° C for 30 minutes, and then returned to room temperature.
  • Nitrogen gas was blown near the liquid surface at 60 ml / min, and while stirring at 60 rpm, 75 ml of chlorosulfonic acid [manufactured by Wako Pure Chemical Industries, Ltd.] was added little by little. .
  • 75 ml of chlorosulfonic acid [manufactured by Wako Pure Chemical Industries, Ltd.] was added little by little. .
  • 10 ml of acetic acid was added and the mixture was stirred, and the resulting chlorsulfonated particles were collected by filtration.
  • the chlorsulfonated particles were washed with tetrachloroethane, then put in water, and further washed with acetone and chloroform.
  • the chlorsulfonated particles, 150 ml of black-mouthed form and 10 ml of triethylamine were placed in a 500 ml separable flask, and fitted with a Teflon blade for stirring, a nitrogen gas inlet tube, and a lid equipped with a cooling tube. Nitrogen gas was blown near the liquid surface at a rate of 60 ml / min, and while stirring at 6 O rpm, 4.58 g of 4-amino-2,2,6,6-tetramethylpiberidine was dissolved in 30 ml of Cloth form. The solution was added dropwise and reacted overnight. The generated particles were collected by filtration, and washed with port-form, acetone, and water in this order.
  • the obtained particles 40 g of sodium acetate and 200 ml of water were placed in a 500 ml separable flask, and a lid equipped with a Teflon blade for stirring, a nitrogen gas inlet tube, and a cooling tube was attached.
  • the separable flask was immersed in a thermostatic water bath maintained at 45 ° C, and stirred at 4 Orpm for 6 hours while blowing nitrogen gas at 75 mlZ.
  • the product was collected by filtration and washed with water.
  • organic sulfonic acids such as polymers of sulfobenzoic acid, phenolsulfonic acid, and styrenesulfonic acid can be detected with high sensitivity.
  • the amount of organic sulfonic acid dissolved in the supernatant was calculated from the calibration curve prepared in advance for the concentration of sulfobenzoic acid and the peak area in terms of the amount of sulfobenzoic acid per liter of resin.
  • the elution amount of sulfobenzoic acid was 0 mg before the start of the test, 10 mg after 8 days, 35 nig after 14 and 4 lmg after 21.
  • the dissolution test was performed in the same manner as in Example 5 using a commercially available cation exchange resin [650-C, manufactured by Dow Chemical Co., Ltd.].
  • the dissolution amount of sulfobenzoic acid was 0 mg before the start of the test, 26 mg after 8 days, 79 mg after 14 days, and 149 mg after 21 days.
  • FIG. 1 shows the results of the dissolution test of Example 5 and Comparative Example 3. From this figure, it can be seen that the eluate from a commercially available cation exchange resin increases with time due to oxidative decomposition, whereas the group having an antioxidant function is covalently bonded via a sulfonamide bond, and It can be seen that elution of sulfobenzoic acid and the like is suppressed in the force-exchange resin of the invention.
  • a solution prepared by dissolving 7 g in 3 Oml of form-form was added dropwise and allowed to react overnight.
  • the generated particles were collected by filtration, and washed with black form and benzene.
  • Elementary analysis was conducted by sampling a small amount of these particles, and as a result, 88.8% by weight of carbon and 0.6% by weight of nitrogen were detected, confirming that 4-amino-2,2,6,6-tetramethylbiperidine was introduced.
  • the amount of the group having an antioxidant function based on the weight of the resin was 3% by weight.
  • the particles into which 4-amino-2,2,6,6-tetramethylpiperidine has been introduced are placed in a 300 ml separable flask together with 100 ml of benzene, and a lid equipped with a Teflon blade for stirring, a nitrogen gas inlet tube, and a cooling tube is provided. After mounting and heating at 60 ° C for 30 minutes, the temperature was returned to room temperature. Next, trimethylamine gas was blown at a rate of 5 ml / min for 30 minutes, followed by reaction at room temperature overnight. The resulting anion exchange resin particles were collected by filtration, washed with acetone, and air-dried. When the ion exchange capacity of the anion exchange resin was measured, it was 1.0 meqZ g.
  • Example 6 The same dissolution test as in Example 6 was performed using a commercially available anion exchange resin [Mitsubishi Chemical Corporation, SA10A, OH type] instead of the anion exchange resin to which a group having an antioxidant function was bonded.
  • the amount of eluted organic carbon was 5 Omg per ml of anion exchange resin.
  • the polymer water treatment material of the present invention has a group having an antioxidant function covalently bonded thereto, there is little risk of deterioration in performance due to oxidative deterioration and contamination of water quality due to oxidative decomposition products during use, and a flocculant It can be suitably used for water treatment as a dehydrating agent, a dispersing agent, a membrane and the like.
  • the cation exchange resin and the anion exchange resin of the present invention have excellent oxidation resistance and little elution of resin components because the group having an antioxidation function is covalently bonded.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Cette invention se rapporte à un matériau polymère, qui possède une si haute résistante à la décomposition oxydative qu'il est moins susceptible de souffrir de la baisse des performances causée par la détérioration oxydative et d'entraîner une pollution de l'eau par les produits d'une décomposition oxydative pendant son utilisation, et qui est utile pour le traitement de l'eau comme coagulant, déshydratant, dispersant, film, etc.; à une résine d'échange cationique qui possède une excellente résistance à la décomposition oxydative et qui déploie une action réduite dans l'élution des constituants de la résine pendant son utilisation; ainsi qu'à une résine d'échange anionique qui possède une excellente résistance à la décomposition oxydative et qui déploie une action réduite dans l'élution de constituants de la résine pendant son utilisation. Ce matériau polymère se caractérise en ce qu'il comporte des groupes qui possèdent une fonction antioxydante et qui ont été liés par covalence. La résine d'échange cationique se caractérise en ce que les groupes ayant une fonction antioxydante ont été liés par covalence par des liaisons sulfonamides représentées par la formule générale (1): -SO2NR1-. La résine d'échange anionique se caractérise en ce que les groupes ayant une fonction antioxydante ont été liés par covalence par des liaisons immunoalkylène représentées par la formule générale (2): -(CH¿2)nNR?2-. Dans ces formules, R1 et R2 représentent chacun hydrogène ou méthyle et n est égal à un nombre entier compris entre 1 et 4.
PCT/JP1997/004189 1996-11-18 1997-11-18 Materiau polymere pour le traitement de l'eau, resine d'echange cationique et resine d'echange anionique WO1998022217A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP8/322198 1996-11-18
JP32219896A JPH10137736A (ja) 1996-11-18 1996-11-18 高分子水処理材料
JP9/281914 1997-10-15
JP28191497A JP3911794B2 (ja) 1997-10-15 1997-10-15 カチオン交換樹脂
JP30870597A JP3911801B2 (ja) 1997-11-11 1997-11-11 アニオン交換樹脂
JP9/308705 1997-11-11

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WO1998022217A1 true WO1998022217A1 (fr) 1998-05-28

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2471598A1 (fr) * 2010-12-29 2012-07-04 Dow Global Technologies LLC Résines d'échange d'ions dotées d'une formation contrôlée de nitrosamine
EP2471599A1 (fr) * 2010-12-29 2012-07-04 Dow Global Technologies LLC Procédé pour inhiber la formation de nitrosamine dans des résines d'échange d'ions
WO2022119904A1 (fr) * 2020-12-01 2022-06-09 The Lubrizol Corporation Membranes échangeuses d'ions sulfonés à substitution par un antioxydant

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5140556B2 (fr) * 1971-11-26 1976-11-04
JPS5417713B2 (fr) * 1972-12-29 1979-07-02
JPS5540054B2 (fr) * 1976-10-12 1980-10-15
JPS5830333B2 (ja) * 1975-06-30 1983-06-28 株式会社トクヤマ カイリヨウイオンコウカンタイノセイゾウホウホウ
JPS6118929B2 (fr) * 1978-10-25 1986-05-15 Tokuyama Soda Kk
JPS6130820B2 (fr) * 1978-09-13 1986-07-16 Sumitomo Chemical Co
JPH05111641A (ja) * 1991-03-07 1993-05-07 Dow Chem Co:The 酸化抵抗性陽イオン交換樹脂

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5140556B2 (fr) * 1971-11-26 1976-11-04
JPS5417713B2 (fr) * 1972-12-29 1979-07-02
JPS5830333B2 (ja) * 1975-06-30 1983-06-28 株式会社トクヤマ カイリヨウイオンコウカンタイノセイゾウホウホウ
JPS5540054B2 (fr) * 1976-10-12 1980-10-15
JPS6130820B2 (fr) * 1978-09-13 1986-07-16 Sumitomo Chemical Co
JPS6118929B2 (fr) * 1978-10-25 1986-05-15 Tokuyama Soda Kk
JPH05111641A (ja) * 1991-03-07 1993-05-07 Dow Chem Co:The 酸化抵抗性陽イオン交換樹脂

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2471598A1 (fr) * 2010-12-29 2012-07-04 Dow Global Technologies LLC Résines d'échange d'ions dotées d'une formation contrôlée de nitrosamine
EP2471599A1 (fr) * 2010-12-29 2012-07-04 Dow Global Technologies LLC Procédé pour inhiber la formation de nitrosamine dans des résines d'échange d'ions
WO2022119904A1 (fr) * 2020-12-01 2022-06-09 The Lubrizol Corporation Membranes échangeuses d'ions sulfonés à substitution par un antioxydant

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