EP4341309A1 - Procédé de production d'échangeurs d'anions - Google Patents

Procédé de production d'échangeurs d'anions

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Publication number
EP4341309A1
EP4341309A1 EP22729551.6A EP22729551A EP4341309A1 EP 4341309 A1 EP4341309 A1 EP 4341309A1 EP 22729551 A EP22729551 A EP 22729551A EP 4341309 A1 EP4341309 A1 EP 4341309A1
Authority
EP
European Patent Office
Prior art keywords
formula
chloromethylated
polymer
iii
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22729551.6A
Other languages
German (de)
English (en)
Inventor
Bernd Koop
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP4341309A1 publication Critical patent/EP4341309A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/16—Halogens
    • C08F212/18—Chlorine
    • 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
    • C08F8/12—Hydrolysis
    • 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
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/24—Haloalkylation

Definitions

  • the present invention relates to a new method for the production of
  • Anion exchangers is the reaction of chloromethylated, vinylaromatic polymer with ammonia to produce anion exchangers with primary amine groups.
  • a disadvantage of this process is the low yield that is achieved in the reaction.
  • the chloromethylated, vinylaromatic polymers are therefore usually reacted with primary, secondary or tertiary amines and used as anion exchangers.
  • DD-A 79152 describes the reaction of a chloromethylated, vinylaromatic polymer with hexamethylenetetramine to form an aminomethylated, vinylaromatic polymer.
  • the disadvantage here is that only a small part of the nitrogen is bound to the polymer.
  • anion exchangers with primary amine functionalities Another process for preparing anion exchangers with primary amine functionalities is known from EP-B 1078688.
  • the vinylaromatic polymer is amidomethylated with a bis(phthalimidomethyl)ether and then hydrolyzed.
  • the bis(phthalimidomethyl) ether is usually first prepared from phthalimide and formaldehyde in the presence of sulfuric acid and then the vinyl aromatic polymer is added.
  • the anion exchanger with primary amine functionalities is prepared from the amidomethylated polymer by hydrolysis with acids or bases. This anion exchanger can be converted further by functionalization with alkylating agents to give strongly, weakly and mixedly basic anion exchangers with secondary, tertiary and quaternary amine functionalities.
  • chloromethylated, vinylaromatic polymers can be converted in good yield by reaction with a nitrile in the presence of a metal-containing catalyst and subsequent hydrolysis to give anion exchangers.
  • R 1 straight-chain, cyclic or branched C Cs -alkyl, phenyl or benzyl, and the phenyl and benzyl can be substituted by at least one straight-chain, cyclic or branched C Cs -alkyl radical, in the presence of a metal-containing catalyst to form an amidomethylated, vinylaromatic polymer of the formula (IV) is reacted and R 1 has the meaning given above and the amidomethylated, vinylaromatic polymer of the formula (IV) is hydrolyzed in a step b) by reaction with an acid or base to give the anion exchanger of the formula (I).
  • R 1 is preferably a straight-chain or branched CrC4-alkyl.
  • R 1 is particularly preferably methyl, ethyl, n-propyl or isopropyl.
  • R 1 is very particularly preferably methyl.
  • R 1 phenyl or benzyl, then this is preferably unsubstituted. If the phenyl and benzyl are substituted, then preferably by a straight-chain, cyclic or branched C Cs -alkyl radical.
  • CrCs-alkyl represents a straight-chain, cyclic or branched alkyl radical having 1 to 8 (CrCs) carbon atoms, more preferably having 1 to 4 (C1-C4) carbon atoms.
  • CrCs-alkyl is preferably methyl, ethyl, n-propyl, isopropyl, n-, i-, s- or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, n-hexyl, cyclohexyl, n-pentyl, 1-methylbutyl, 2 -methylbutyl, 3-methylbutyl.
  • CrCs-alkyl or CrC4-alkyl is particularly preferably ethyl, methyl, n-propyl or isopropyl.
  • Chloromethylated, vinylaromatic polymers of the formula (II) are preferably copolymers of at least one monovinylaromatic monomer selected from the group consisting of styrene, vinyltoluene, ethylstyrene, a-methylstyrene, chlorostyrene or chloromethylstyrene and mixtures of at least one of these monomers with at least one polyvinylaromatic compound (crosslinkers) selected from the group consisting of divinylbenzene, divinyltoluene, trivinylbenzene, triallyl isocyanurate, divinylnaphthalene and/or trivinylnaphthalene or mixtures of these polyvinylaromatic compounds.
  • monovinylaromatic monomer selected from the group consisting of styrene, vinyltoluene, ethylstyrene, a-methylstyrene, chlorostyrene or chloro
  • a styrene copolymer is particularly preferably used as the chloromethylated, vinylaromatic polymer of the formula (II).
  • a styrene-divinylbenzene copolymer is a copolymer crosslinked through the use of divinylbenzene.
  • the chloromethylated vinyl aromatic polymer of formula (II) preferably has a spherical shape.
  • the chloromethylated, vinylaromatic polymers of the formula (II) used according to the invention preferably have a macroporous structure.
  • microporous or gel-like or macroporous have already been described in detail in the specialist literature, for example in Seidl, Malinsky, Dusek, Heitz, Adv. Polymer Sci., 1967, Vol. 5, pp. 113 to 213.
  • the possible measuring methods for macroporosity e.g. mercury porosimetry and BET determination, are also described there.
  • the pores of the macroporous polymers of the chloromethylated, vinylaromatic polymers of the formula (II) used according to the invention have an average diameter of from 20 nm to 100 nm. The pore diameter is preferably determined using mercury porosimetry.
  • the chloromethylated, vinylaromatic polymers of the formula (II) used according to the invention preferably have a monodisperse distribution.
  • substances are referred to as monodisperse if at least 90% by volume or mass of the particles have a diameter that lies in the interval with a width of +/-10% of the most common diameter around the most common diameter.
  • a substance with a most common diameter of 0.5 mm at least 90% by volume or mass lies in a size interval between 0.45 mm and 0.55 mm
  • a substance with a most common diameter of 0.7 mm at least 90% by volume or mass in a size interval between 0.77 mm and 0.63 mm.
  • the chloromethylated, vinylaromatic polymer of the formula (II) preferably has a diameter of 200 to 1500 ⁇ m.
  • the chloromethylated vinyl aromatic polymer of formula (II) preferably has a spherical shape.
  • the chloromethylated vinyl aromatic polymer of formula (II) contains from 88 mole percent to 98 mole percent monovinyl aromatic monomers, based on the total moles of the polymer.
  • the chloromethylated vinyl aromatic polymer of formula (II) contains from 2 mole percent to 12 mole percent polyvinyl aromatic monomers, based on the total moles of the polymer.
  • the anion exchanger of the formula (I) preferably has a diameter of 200 to 1500 ⁇ m.
  • the anion exchanger of the formula (I) preferably has a macroporous structure.
  • the anion exchanger of the formula (I) preferably has a monodisperse distribution.
  • the anion exchanger of the formula (I) preferably contains 88 mol % to 98 mol % of monovinylaromatic monomers, based on the total amount of moles of the polymer.
  • the anion exchanger of the formula (I) preferably contains 2 mol % to 12 mol % of polyvinylaromatic monomers, based on the total amount of substances of the polymer.
  • the preparation of the chloromethylated, vinylaromatic polymers of the formula (II) used in step a) is preferably carried out by reacting in a step 1a) la) monomer droplets of at least one monovinylaromatic compound and at least one polyvinylaromatic compound and at least one initiator and lb) the Polymer from step 1a) is chloromethylated.
  • At least one monovinylaromatic compound and at least one polyvinylaromatic compound are used in step 1a). However, it is also possible to use mixtures of two or more monovinylaromatic compounds and mixtures of two or more polyvinylaromatic compounds.
  • Styrene, vinyl toluene, ethyl styrene, ⁇ -methyl styrene, chlorostyrene or chloromethyl styrene are preferably used as monovinylaromatic compounds for the purposes of the present invention in step 1a).
  • the monovinylaromatic compounds are preferably used in amounts >50% by weight, based on the monomer or its mixture with other monomers, especially preferably between 55% by weight and 70% by weight, based on the monomer or its mixture with other monomers.
  • styrene or mixtures of styrene with the aforementioned monomers preferably with ethyl styrene.
  • Preferred polyvinylaromatic compounds for the purposes of the present invention are, for step 1a), divinylbenzene, divinyltoluene, trivinylbenzene, triallyl isocyanurate, divinylnaphthalene or trivinylnaphthalene, particularly preferably divinylbenzene.
  • the polyvinylaromatic compounds are preferably used in amounts of 1-20% by weight, particularly preferably 2-12% by weight, particularly preferably 4-10% by weight, based on the monomer or its mixture with other monomers.
  • the nature of the polyvinylaromatic compounds (crosslinkers) is selected with a view to the subsequent use of the polymer. If divinylbenzene is used, commercial grades of divinylbenzene which also contain ethylvinylbenzene in addition to the isomers of divinylbenzene are sufficient.
  • Macroporous, vinylaromatic polymers are preferably formed by adding inert materials, preferably at least one porogen, to the monomer mixture during the polymerization in order to produce a macroporous structure in the polymer.
  • porogens are hexane, octane, isooctane, isododecane, pentamethylheptane, methyl ethyl ketone, butanol or octanol and their isomers.
  • organic substances are suitable which dissolve in the monomer but dissolve or swell the polymer poorly (precipitating agent for polymers), for example aliphatic hydrocarbons (Bayer paint factory DBP 1045102, 1957; DBP 1113570, 1957).
  • Porogens are preferably used in an amount of 25% by weight to 45% by weight, based on the amount of the organic phase.
  • At least one porogen is preferably added in step 1a).
  • the vinylaromatic polymers produced according to step 1a) can be produced in heterodisperse or monodisperse form.
  • Heterodisperse vinylaromatic polymers are prepared by general processes known to those skilled in the art, for example with the aid of suspension polymerization.
  • Monodisperse, vinylaromatic polymers are preferably prepared in step 1a).
  • microencapsulated monomer droplets are used in step 1a) in the production of monodisperse, vinylaromatic polymers.
  • the materials known for use as complex coacervates are suitable for the microencapsulation of the monomer droplets, in particular polyesters, natural and synthetic polyamides, polyurethanes or polyureas.
  • Gelatine is preferably used as the natural polyamide. This is used in particular as a coacervate and complex coacervate.
  • gelatin-containing complex coacervates are understood to mean, in particular, combinations of gelatin with synthetic polyelectrolytes.
  • Suitable synthetic polyelectrolytes are copolymers with built-in units of, for example, maleic acid, acrylic acid, methacrylic acid, acrylamide and methacrylamide. Acrylic acid and acrylamide are particularly preferably used.
  • Capsules containing gelatin can be hardened with conventional hardening agents such as formaldehyde or glutaric dialdehyde.
  • the heterodisperse or optionally microencapsulated, monodisperse monomer droplets contain at least one initiator or mixtures of initiators (initiator combination) to initiate the polymerization.
  • initiators preferred for the process according to the invention are peroxy compounds, particularly preferably dibenzoyl peroxide, dilauroyl peroxide, bis(p-chlorobenzoyl) peroxide,
  • the initiators are preferably used in amounts of from 0.05 to 2.5% by weight, particularly preferably from 0.1 to 1.5% by weight, based on the monomer mixture.
  • the optionally monodisperse, microencapsulated monomer droplet can optionally also contain up to 30% by weight (based on the monomer) of crosslinked or uncrosslinked polymer.
  • Preferred polymers are derived from the aforementioned monomers, particularly preferably from styrene.
  • the aqueous phase can, in a further preferred embodiment, contain a dissolved polymerization inhibitor.
  • a dissolved polymerization inhibitor inorganic and organic substances can be used as inhibitors.
  • Preferred inorganic inhibitors are nitrogen compounds, particularly preferably hydroxylamine, hydrazine, sodium nitrite and potassium nitrite, salts of phosphorous acid such as sodium hydrogen phosphite and sulfur-containing compounds such as sodium dithionite, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium thiocyanate and ammonium thiocyanate.
  • organic inhibitors examples include phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butylpyrocatechol, pyrogallol and condensation products of phenols with aldehydes. Further preferred organic inhibitors are nitrogen-containing compounds.
  • hydroxylamine derivatives such as N,N-diethylhydroxylamine, N-isopropylhydroxylamine and sulfonated or carboxylated N-alkylhydroxylamine or N,N-dialkylhydroxylamine derivatives, hydrazine derivatives such as N,N-hydrazinodiacetic acid, nitroso compounds such as N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine ammonium salt or N-nitrosophenylhydroxylamine aluminum salt.
  • concentration of the inhibitor is 5-1000 ppm (based on the aqueous phase), preferably 10-500 ppm, particularly preferably 10-250 ppm.
  • the polymerization of the optionally microencapsulated, monodisperse monomer droplets to form the monodisperse, vinylaromatic polymer preferably takes place in the presence of one or more protective colloids in the aqueous phase.
  • Suitable protective colloids are natural or synthetic water-soluble polymers, preferably gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid or copolymers of (meth)acrylic acid and (meth)acrylic esters.
  • cellulose derivatives in particular cellulose esters and cellulose ethers, such as carboxymethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and hydroxyethyl cellulose.
  • Gelatin is particularly preferred.
  • the amount of protective colloids used is generally 0.05 to 1% by weight, based on the aqueous phase, preferably 0.05 to 0.5% by weight.
  • the polymerization to form the monodisperse, vinylaromatic polymer can be carried out in the presence of a buffer system be performed.
  • Buffer systems which adjust the pH of the aqueous phase to a value between 14 and 6, preferably between 12 and 8, at the beginning of the polymerization are preferred.
  • protective colloids with carboxylic acid groups are wholly or partly in the form of salts. In this way, the effect of the protective colloids is favorably influenced.
  • Particularly suitable buffer systems contain phosphate or borate salts.
  • the terms phosphate and borate within the meaning of the invention also include the condensation products of the ortho forms of corresponding acids and salts.
  • the concentration of the phosphate or borate in the aqueous phase is preferably 0.5-500 mmol/l, particularly preferably 2.5-100 mmol/l.
  • the stirring speed during the polymerisation to form the monodisperse, vinyl aromatic polymer is less critical and, in contrast to conventional polymerisation, has no influence on the particle size. Low agitation speeds are used, sufficient to keep the suspended monomer droplets in suspension and to aid in the removal of the heat of polymerization.
  • Various stirrer types can be used for this task. Grid stirrers with an axial effect are particularly suitable.
  • the volume ratio of encapsulated monomer droplets to aqueous phase is preferably 1:0.75 to 1:20, particularly preferably 1:1 to 1:6.
  • the polymerization temperature to form the monodisperse, vinylaromatic polymer depends on the decomposition temperature of the initiator used. It is preferably between 50 and 180.degree. C., particularly preferably between 55 and 130.degree.
  • the polymerization preferably lasts from 0.5 to about 20 hours. It has proven useful to use a temperature program in which the polymerization is started at a low temperature, preferably 60° C., and the reaction temperature is increased as the polymerization conversion progresses. In this way, for example, the requirement for a safe course of the reaction and high polymerization conversion can be met very well.
  • the monodisperse, vinylaromatic polymer is isolated using customary methods, for example by filtering or decanting, and washed if necessary.
  • the monodisperse, vinylaromatic polymers are preferably prepared using the jetting principle or the seed-feed principle.
  • a macroporous, monodisperse, vinylaromatic polymer is preferably prepared in step 1a).
  • step 1b) the vinyl aromatic polymer becomes the chloromethylated vinyl aromatic polymer of formula (II) where WWW represents a vinyl aromatic polymer, reacted by chloromethylation.
  • chloromethyl methyl ether is preferably used as the chloromethylating agent.
  • the chloromethyl methyl ether can be used in unpurified form, and it can contain, for example, methylal and methanol as secondary components.
  • the chloromethyl methyl ether is preferably used in excess in step 1b).
  • the chloromethylation reaction is catalyzed by the addition of a Lewis acid. Suitable Lewis acids are preferably ferric chloride, zinc chloride, tin(IV) chloride and aluminum chloride.
  • the reaction temperature in step 1b) is preferably in the range from 40 to 80.degree. In a preferred embodiment, step 1b) is carried out at normal pressure and at a temperature of 50 to 60.degree.
  • the volatile constituents such as preferably hydrochloric acid, methanol, methylal, formaldehyde and some chloromethyl methyl ether, are removed, preferably by evaporation.
  • washing is preferably carried out with a mixture of methylal, methanol and water.
  • a macroporous chloromethylated vinylaromatic polymer of the formula (II) is preferably prepared in step 1b).
  • the chloromethylated, vinylaromatic polymer of the formula (II) prepared in step 1b) is preferably used as starting material in step a).
  • Acetonitrile, propionitrile, butyronitrile, isovaleryl nitriles, benzonitrile, o-methylbenzonitrile, m-methylbenzonitrile, p-methylbenzonitrile and phenylacetonitrile are preferably used as nitriles of the formula (III) in step a).
  • benzonitrile o-methylbenzonitrile, m-methylbenzonitrile, p-methylbenzonitrile and phenylacetonitrile
  • step a preference is given to using inorganic or organic metal(II), metal(III) or metal(IV) salts or mixtures of such salts as metal-containing catalysts.
  • Iron(II) salts, iron(III) salts, zinc(II) salts, tin(II) salts or tin(IV) salts and mixtures of these compounds are preferably used as metal-containing catalysts.
  • Zinc(II) perchlorate in particular the hexahydrate, is very particularly preferably used as the metal-containing catalyst.
  • the nitriles of the formula (III) are preferably used in a ratio of 100:1 to 1:1, particularly preferably in a ratio of 50:1 to 1:1, based on the amount of chlorine in the chloromethylated, vinylaromatic polymer used of the formula (II) used.
  • the metal-containing catalyst is preferably used in a ratio of 1:100 to 1:1, particularly preferably in a ratio of 1:50 to 1:0.5, based on the amount of chlorine in the chloromethylated, vinylaromatic polymer of the formula (II ) used.
  • Step a) of the process according to the invention can be carried out in the presence or absence of polar or non-polar, inert solvents.
  • Step a) of the process according to the invention is preferably carried out in the absence of solvents.
  • Water or alcohols, such as preferably methanol, ethanol, propanol or butanol, or mixtures of these polar, inert solvents are preferably used as polar, inert solvents.
  • Halogenated, aliphatic or aromatic hydrocarbons such as preferably dichloromethane, dichloroethane, dibromomethane, trichloromethane, carbon tetrachloride or benzotrifluoride or mixtures of these solvents are preferably used as non-polar, inert solvents.
  • the chloromethylated, vinylaromatic polymers of the formula (II) are introduced and then with the nitrile of the formula
  • the reaction temperature in step a) is preferably between 60 and 140°C, preferably between 70 and 110°C.
  • the pressure is preferably in a range from 0.8 to 3 bar.
  • the reaction is preferably completed within 1 to 24 hours, preferably within 4 to 12 hours.
  • the hydrolysis of the amidomethyl group and thus the exposure of the aminomethyl group takes place in step b) by treatment with at least one base or at least one acid.
  • the bases used in step b) for the hydrolysis of the amidomethylated, vinylaromatic polymers of the formula (IV) are preferably alkali metal hydroxides, alkaline earth metal hydroxides, ammonia or hydrazine.
  • the acids used in step b) are preferably nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfurous acid or nitrous acid.
  • At least one base is preferably used in step b) to hydrolyze the amidomethyl group and thus to expose the aminomethyl group.
  • the hydrolysis of the amidomethyl group in step b) is preferably carried out at a temperature of from 80° C. to 250° C., preferably from 80° C. to 190° C., if an acid is used for the hydrolysis.
  • the concentration of the acid in step b) is preferably in the range from 5% by weight to 90% by weight, particularly preferably between 10% by weight and 70% by weight, based on the aqueous phase.
  • the hydrolysis of the amidomethyl group and thus the exposure of the aminomethyl group in step b) is particularly preferably carried out by treating the amidomethylated, vinylaromatic polymer of the formula (IV) with aqueous or alcoholic solutions of an alkali metal hydroxide, such as preferably sodium hydroxide or potassium hydroxide, at temperatures of 80° C. and 250°C, preferably from 120°C to 190°C.
  • an alkali metal hydroxide such as preferably sodium hydroxide or potassium hydroxide
  • the hydrolysis of the amidomethyl group to the aminomethyl group in step b) is preferably carried out in excess of acid and/or base, based on the amount of amidomethyl groups used.
  • the anion exchanger of the formula (I) formed in step b) is generally washed neutral with deionized water. However, it can also be used without post-treatment.
  • anion exchangers of the formula (I) can be further functionalized by known processes by reaction with alkylating agents to give secondary, tertiary and quaternary anion exchangers containing amino groups and chelating resins.
  • Anion exchangers can be produced in large quantities by the process according to the invention.
  • the molar amount of basic groups corresponds to the molar amount of aminomethyl groups in the resin.
  • the amount of chloromethylated groups is calculated by determining the chlorine content of the dried resin via elemental analysis.
  • 3000 g of deionized water are placed in a 10 l glass reactor and a solution of 10 g of gelatin, 16 g of disodium hydrogen phosphate dodecahydrate and 0.73 g of resorcinol in 320 g of deionized water is added and mixed. The mixture is heated to 25°C.
  • the mixture is polymerized with stirring by increasing the temperature according to a temperature program starting at 25°C and ending at 95°C.
  • the batch is cooled, washed through a 32 ⁇ m sieve and then dried at 80° C. in vacuo.
  • Nitrogen content 5.5% by weight (dried resin)
  • Nitrogen content 4.6% by weight (dried resin)
  • Nitrogen content 3.5% by weight (dried resin)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un nouveau procédé de production d'échangeurs d'anions.
EP22729551.6A 2021-05-17 2022-05-16 Procédé de production d'échangeurs d'anions Pending EP4341309A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21174063.4A EP4092054A1 (fr) 2021-05-17 2021-05-17 Procédé de production d'échangeurs d'anions
PCT/EP2022/063207 WO2022243254A1 (fr) 2021-05-17 2022-05-16 Procédé de production d'échangeurs d'anions

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EP4341309A1 true EP4341309A1 (fr) 2024-03-27

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EP22729551.6A Pending EP4341309A1 (fr) 2021-05-17 2022-05-16 Procédé de production d'échangeurs d'anions

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EP (2) EP4092054A1 (fr)
JP (1) JP2024517993A (fr)
KR (1) KR20240008854A (fr)
CN (1) CN117321090A (fr)
WO (1) WO2022243254A1 (fr)

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EP1078688B1 (fr) 1999-08-27 2012-05-09 LANXESS Deutschland GmbH Méthode pour la préparation d'échangeurs d'anions monodisperses
RU2496571C1 (ru) * 2012-03-15 2013-10-27 Закрытое Акционерное общество Научно-технический центр "БиАСеп" (ЗАО НТЦ "БиАСеп") Анионообменный сорбент для одновременного ионохроматографического определения поляризуемых и неполяризуемых неорганических анионов и способ его изготовления
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KR20240008854A (ko) 2024-01-19
EP4092054A1 (fr) 2022-11-23
JP2024517993A (ja) 2024-04-23
CN117321090A (zh) 2023-12-29

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