EP2175994A2 - Résines chélatantes - Google Patents

Résines chélatantes

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Publication number
EP2175994A2
EP2175994A2 EP08774968A EP08774968A EP2175994A2 EP 2175994 A2 EP2175994 A2 EP 2175994A2 EP 08774968 A EP08774968 A EP 08774968A EP 08774968 A EP08774968 A EP 08774968A EP 2175994 A2 EP2175994 A2 EP 2175994A2
Authority
EP
European Patent Office
Prior art keywords
series
chelate
stands
compound
polymer
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.)
Withdrawn
Application number
EP08774968A
Other languages
German (de)
English (en)
Inventor
Reinhold Klipper
Michael Schelhaas
Stefan Neumann
Duilio Rossoni
Wolfgang Zarges
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
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Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP2175994A2 publication Critical patent/EP2175994A2/fr
Withdrawn legal-status Critical Current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
    • C08F12/00—Homopolymers and 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
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F12/36—Divinylbenzene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/10—Complex coacervation, i.e. interaction of oppositely charged particles
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/90—Chelants
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present application relates to novel chelating resins which contain, as a functional group, quaternary nitrogen atoms in structures of the general formula (I)
  • radicals R] to R 3 are an optionally substituted radical of the series picolyl, methylquinoline or methylpiperidine
  • M is the polymer matrix and m is an integer from 1 to 4
  • X is a counterion of the series hydroxide OH " , Halide, preferably Cl " , Br ⁇ or sulfate SO 4 2" -, a process for their preparation and their use, in particular the use of the new chelating resins in hydrometallurgy and electroplating.
  • chelate exchangers can be used for the purification and workup of waters in the chemical industry and electronics industry, in particular for the production of ultrapure water or in combination with gelformigen and / or macroporous cation exchangers for demineralization of aqueous solutions and / or condensates.
  • Q is, inter alia, an alkylene or -NH radical.
  • the chelating resins of this prior art are prepared by halomethylation of a styrene-divinylbenzene-based bead polymer, on average 0.1 to 1.0 halomethyl groups per aromatic nucleus being introduced as a reactive group for the addition of the amino-methyl pyridyl chelate functionality.
  • halomethylation method for introducing the functional group described in US Pat. No. 4,098,867 has disadvantages which lead to a limitation of the degree of functionalization. These disadvantages are described in EP-A 0 481 603. For example, post-crosslinking occurs in the halomethylation, which leads to a loss of halomethyl groups. Due to the resulting loss of halomethyl groups that could be reacted with ammomethylpyridines, the resulting chelating resins have fewer functional groups available for the recovery of valuable metal species, significantly limiting their use in metallurgy.
  • the object of the present invention is now to provide chelate exchange resins with the above-described requirement profile for the removal of substances, preferably polyvalent anions, from liquids, preferably aqueous media or gases, as well as to provide a process for their preparation. Substances within the meaning of the present invention also include valuable metals.
  • the solution and thus the subject of the present invention are novel monodisperse or heterodisperse, gel or macroporous, medium or strong base Che ⁇ attooler on Basis of at least one monovinylaromatic compound and / or (meth) acrylic compound and at least one polyvinylaromati see compound containing as a functional group quaternary Stickstoffatorae structures of the general formula (I)
  • Ri to R 3 is an optionally substituted radical of the series methylpyridine, methylquinoline or methylpiperidine
  • radicals independently of one another are a radical of the series C 1 -C 4 -alkyl or hydroxy-C 1 -C 4 -alkyl, preferably a radical of the series CH 3 , -CH 2 OH, -C 2 H 4 OH, -CH 2 CH 2 CH 2 OH or -CH 2 CH 2 CH 2 CH 2 OH and
  • n is an integer 1, 2, 3 or 4,
  • X is a counterion of the series hydroxide OH " , halide, preferably Cl ' , Br " , or sulfate
  • the chelate exchangers according to the invention for the functional group according to the general formula (I) may optionally also contain additional functional groups of the general formula (III)
  • Ri and R 2 are each independently a radical of the series Ci-C 4 alkyl or hydroxy-Ci-C 4 alkyl, preferably a radical of the series -CH 3 , -CH 2 OH, - C 2 H 4 OH , -C 3 H 6 OH or -C 4 H 8 OH,
  • n stands for an integer 1, 2, 3 or 4 and M stands for the polymer matrix.
  • the present application also relates to a process for the preparation of these novel monodisperse or heterodisperse, gelatinous or macroporous, medium- or strongly basic chelate exchangers which carry quaternary nitrogen atoms in structures of the general formula (I) as a functional group,
  • process step a at least one monovinylaromatic compound and / or one (meth) acrylic compound and at least one polyvinylaromatic compound or a multifunctionally ethylenically unsaturated compound are used.
  • monovinylaromatic compound and / or one (meth) acrylic compound and at least one polyvinylaromatic compound or a multifunctionally ethylenically unsaturated compound are used.
  • monovinylaromatic compounds for the purposes of the present invention, in process step a), preference is given to using monoethylenically unsaturated compounds, particularly preferably styrene, vinyltoluene, ethylstyrene, ⁇ -methylstyrene, chlorostyrene, chloromethylstyrene.
  • monoethylenically unsaturated compounds particularly preferably styrene, vinyltoluene, ethylstyrene, ⁇ -methylstyrene, chlorostyrene, chloromethylstyrene.
  • Acrylic esters or methacrylic esters with branched or unbranched C 1 -C 6 -alkyl radicals are preferably used as (meth) acrylic compounds. Preference is given to using methyl acrylate, acrylonitrile or methacrylonitrile.
  • the preparation of heterodisperse, crosslinked bead polymers and (meth) acryl-based ion exchangers obtainable therefrom is described, for example, in US Pat. No. 4,082,564, the contents of which are fully encompassed by the present description in relation to the preparation process.
  • Preferred crosslinkers in the context of the present invention are, for process step a), multifunctional ethylenically unsaturated compounds, particularly preferably butadiene, isoprene, divinylbenzene, diumvinyltoluene, trivinylbenzene, divinylnaphthalene, trivinylnaphthalene, divinylcyclohexane, trivinylcyclohexane, triallycyanurate, triallylamine, 1,7-octadiene, 1 , 5-hexadiene, cyclopentadiene, norboradiene, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butanediol divinyl ether, ethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, hexanediol divinyl ether, trimethylolpropane tri
  • the polyvinylaromatic compounds are preferably used in amounts of 1-20% by weight, more preferably 2-12% by weight, particularly preferably 4-10% by weight, based on the monomer or its mixture with other monomers.
  • the type of polyvinylaromati see compounds (crosslinker) is selected with regard to the subsequent use of the bead polymer.
  • the base polymers on which the chelate exchangers according to the invention are based can be present in heterodisperse bead size distribution or monodisperse bead size distribution.
  • the preparation of the heterodisperse crosslinked base polymers according to process step a) can be carried out by known methods of suspension polymerization; see. Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A 21, 363-373, VCH Verlagsgesellschaft mbH, Weinheim 1992.
  • the water-insoluble monomer / crosslinker mixture is added to an aqueous phase, preferably to stabilize the monomer / crosslinked droplets in the dispersed Phase and the resulting bead polymers contains at least one protective colloid.
  • microencapsulated monomer droplets are used, the materials suitable for microencapsulation of the monomer droplets being suitable for use as complex coenzyme, in particular polyesters, natural or synthetic polyamides, polyurethanes, polyureas.
  • a natural polyamide gelatin is preferably used. This is used in particular as coacervate and complex coacervate.
  • Gelatin-containing complex coacervates in the context of the present invention are understood to mean, in particular, combinations of gelatin with synthetic polyelectrolytes.
  • Suitable synthetic polyelectrolytes are copolymers with incorporated units, preferably of maleic acid, acrylic acid, methacrylic acid, acrylamide and methacrylamide.
  • Gelatin-containing capsules can be cured with conventional curing agents such as formaldehyde or glutardialdehyde.
  • the encapsulation of monomer droplets with gelatin, gelatin-containing coacervates or gelatin-containing complex coacervates is described in detail in EP-A 0 046 535.
  • the methods of encapsulation with synthetic polymers are known. For example, phase interfacial condensation in which a reactive component (for example an isocyanate or an acid chloride) dissolved in the monomer droplet is reacted with a second reactive component (for example an amine) dissolved in the aqueous phase is well suited.
  • the optionally microencapsulated monomer droplets contain an initiator or mixtures of initiators to initiate the polymerization.
  • Initiators which are preferably suitable for the process according to the invention are peroxy compounds, particularly preferably dibenzoyl peroxide, dilauroyl peroxide, bis (p-chlorobenzoyl) peroxide, dicyclohexyl peroxydicarbonate, tert-butyl peroctoate, tert-butyl peroxy-2-ethylhexanoate, 2,5-bis ( 2-ethylhexanoylperoxy) -2,5-dimethylhexane or tert-amylperoxy-2-ethylhexane, and azo compounds, more preferably 2,2'-azobis (isobutyronitrile) or 2,2'-azobis (2-methylisobutyronitrile) ,
  • the initiator (s) is or are preferably used in amounts of from 0.05 to 2.5% by weight, particularly preferably 0.1 to 1.5% by weight, based on the monomer mixture.
  • monodisperse are those bead polymers or chelate resins in which at least 90% by volume or by mass of the particles have a diameter which is in the interval with the width + 10% of the most common diameter around the most common diameter.
  • a monodisperse, crosslinked, vinylaromatic base polymer according to process step a) can be prepared by the processes known from the literature. For example, such processes are described in US Pat. No. 4,444,961, EP-A 0 046 535, US Pat. No. 4,419,245 or WO 93/12167, the contents of which are fully understood by the present application with respect to process step a).
  • monodisperse bead polymers and the monodisperse chelate resins to be produced therefrom are obtained by atomization (jetting) or seed-feed processes (seed / feed process). According to the invention, the achievement of a monodisperse particle size distribution in process step a) is preferred.
  • microporous or gel or macroporous have already been described in detail in the specialist literature.
  • Preferred bead polymers in the context of the present invention, prepared by process step a) have a macroporous structure.
  • macroporous bead polymers can be carried out, for example, by adding inert materials (porogens) to the monomer mixture during the polymerization.
  • inert materials prorogens
  • especially organic substances are suitable which dissolve in the monomer, but poorly dissolve or swell the polymer (precipitant for polymers), for example aliphatic hydrocarbons (Farbenfabriken Bayer DBP 1045102, 1957, DBP 1113570, 1957).
  • alcohols having from 4 to 10 carbon atoms are used as porogen for the preparation of monodisperse, macroporous styrene / divmylbenzene-based bead polymers.
  • macroporous bead polymers are preferred as porogen organic solvents which dissolve the poorly formed polymer or swell.
  • Hexane, octane, ⁇ sooctane, isododecane, methyl ethyl ketone, butanol or octanol and their isomers may be mentioned as preferred.
  • the optionally microencapsulated monomer droplets may optionally also contain up to 30% by weight (based on the monomer) of crosslinked or uncrosslinked polymer.
  • Preferred polymers are derived from the abovementioned monomers, more preferably from styrene.
  • the mean pond size of the optionally encapsulated monomer droplets is 10-1000 ⁇ m, preferably 100-1000 ⁇ m.
  • the aqueous phase may optionally contain a dissolved polymerization inhibitor.
  • Suitable inhibitors for the purposes of the present invention are both inorganic and organic substances. Examples of inorganic inhibitors are nitrogen compounds such as hydroxylamine, hydrazine, sodium nitrite or 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 or ammonia.
  • organic inhibitors are phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butylpyrocatechol, pyrogallol or condensation products of phenols with aldehydes.
  • phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butylpyrocatechol, pyrogallol or condensation products of phenols with aldehydes.
  • resorcinol pyrocatechol
  • tert-butylpyrocatechol pyrogallol
  • condensation products of phenols with aldehydes pyrogallol
  • hydroxylamine derivatives preferably N, N-diethylhydroxylamine or N-isopropylhydroxylamine, and also sulfonated or carboxylated N-alkylhydroxylamine or N, N-dialkylhydroxylamine derivatives, hydrazine derivatives, preferably N, N-hydrazinodiacetic acid, nitroso compounds, preferably N-nitroso-phenylhydroxylamine, 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 micro-rare rare monomer droplets to the spherical bead polymer is, as already mentioned above, optionally in the presence of one or more protective colloids in the aqueous phase.
  • Suitable protective colloids are natural or synthetic water-soluble polymers, such as, for example, gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid or copolymers of (meth) acrylic acid and (meth) acrylic acid esters.
  • cellulose derivatives in particular cellulose esters and cellulose ethers, such as carboxymethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose and hydroxyethylcellulose.
  • Particularly suitable is gelatin.
  • the amount used of the protective colloids is generally 0.05 to 1 wt .-% based on the aqueous phase, preferably 0.05 to 0.5 wt .-%.
  • the polymerization into a bead polymer in process step a) can also be carried out in the presence of a buffer system.
  • buffer systems which adjust the pH of the aqueous phase to between 14 and 6, preferably between 12 and 5, at the beginning of the polymerization.
  • protective colloids with carboxylic acid groups are wholly or partially present as 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 in the sense 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 0.5-500 mmol / l, preferably 2.5-100 mmol / l.
  • the stirring speed in the polymerization is less critical and has no influence on the particle size in contrast to conventional bead polymerization.
  • Low stirring rates are used which are sufficient to suspend the suspended monomer droplets and to promote the dissipation of the heat of polymerization.
  • Different types of stirrers can be used. Particularly suitable are lattice stirrers with axial action.
  • the volume ratio of encapsulated monomer droplets to aqueous phase is preferably 1: 0.75 to 1:20, more preferably 1: 1 to 1: 6.
  • the polymerization temperature in process step a) depends on the decomposition temperature of the initiator used. It is generally between 50 to 180 ° C, preferably between 55 and 130 ° C. The polymerization takes 0.5 to a few hours. It has proven useful to use a temperature program in which the polymerization at low temperature, preferably about 60 ° C is started and the reaction temperature is increased with increasing polymerization sationsumsatz. In this way, for example, the demand for safe reaction course and high polymerization conversion can be fulfilled very well. After the polymerization, the polymer is isolated by customary methods, preferably by filtration or decantation, and optionally washed.
  • the crosslinked bead polymer based on monovinyl aromatics prepared in process step a) is functionalized with tertiary amino groups by the phthalimide process.
  • the amidomethylating reagent is first prepared in process step b).
  • phthalimide or a phthalimide derivative is preferably dissolved in a solvent and admixed with formalin. Subsequently, with elimination of water from this one
  • the bis (phthalimido) ether may optionally be converted to the phthalimido ester.
  • Preferred phthalimide derivatives within the meaning of the present invention
  • Invention are phthalimide itself or substituted phthalimides, preferably methylphthalimide.
  • EP-A 1 323 473 The preparation of a monodisperse bead polymer based on (meth) acrylic compounds is described in EP-A 1 323 473, the content of which is included in the present invention.
  • the subject of EP-A 1 323 473 is namely a process for the preparation of monodisperse anion exchangers of the poly (meth) acrylamide type, characterized in that
  • Acrylic compounds and crosslinkers by a seed-feed method converts (feeds) and polymerized and b) the product obtained from the first stage is introduced into liquid amines of the diamine type, the suspension is heated to temperatures greater than 100 0 C and optionally stirred while distilling off emerging components for several hours, and the aminated bead polymer washes amine-free.
  • the intermediate obtained is a bead polymer to be used according to the invention in stage b) of the process according to the invention, based on (meth) acrylic compounds.
  • (meth) acrylic compounds includes compounds based on acrylic acid or based on methacrylic acid.
  • Suitable solvents used in process step b) are inert solvents which are suitable for swelling the polymer, preferably chlorinated hydrocarbons, particularly preferably dichloroethane or methylene chloride.
  • the bead polymer is condensed with phthalimide derivatives.
  • the catalyst used is oleum, sulfuric acid or sulfur trioxide.
  • the cleavage of the phthalic acid radical and thus the exposure of the aminomethyl group is carried out in process step c) by treating the phthalimidomethylated crosslinked bead polymer with aqueous or alcoholic solutions of an alkali hydroxide, preferably sodium hydroxide or potassium hydroxide, at temperatures between 100 and 250 0 C, preferably 120 -190 0 C.
  • an alkali hydroxide preferably sodium hydroxide or potassium hydroxide
  • Concentration of the sodium hydroxide solution is preferably in the range of 10 to 50 wt .-%, particularly preferably in the range of 20 to 40 wt .-%. This process enables the preparation of aminoalkyl-containing, crosslinked bead polymers with a substitution of the aromatic
  • the resulting aminomethylated bead polymer is finally washed with demineralized water (fully desalted water) alkali-free.
  • crosslinked bead polymer based on (meth) acrylic compounds is functionalized in such a way with tertiary amino groups that the bead polymer either reacted with dimethylaminopropylamine or reacted with other diamines such as ethylenediamine, diethylenetriamines, triethylenediamines and then further functionalized to form tertiary amines becomes.
  • the ion exchanger according to the invention is prepared by reacting the tertiary amino-containing monodisperse or heterodisperse crosslinked, vinylaromatic bead polymers from step b) in aqueous suspension with, if appropriate substituted Chlormethylstickstofflieterocyclen preferably with chloromethylpyridine or its hydrochloride, 2-Chlormethylcb.inolm or 2-chloromethylpiperidine.
  • Chloromethylpyridine or its hydrochloride can be used as 2-chloromethylpyridine, 3-chloromethylpyridine or 4-chloromethylpyridine.
  • the preferred reagent used in process step c) is 2-chloromethylpyridine hydrochloride, preferably in aqueous solution.
  • the reaction in process step c) is carried out with addition of alkali, particularly preferably of potassium hydroxide solution or sodium hydroxide solution, particularly preferably of sodium hydroxide solution.
  • alkali particularly preferably of potassium hydroxide solution or sodium hydroxide solution, particularly preferably of sodium hydroxide solution.
  • the pH in the reaction is kept in the range 4-10.
  • the pH is maintained in the range 6-8.
  • the ion exchangers prepared according to the invention with chelating functional groups are suitable for the adsorption of metals, in particular heavy metals and noble metals and their compounds, from aqueous solutions, organic liquids or gases, preferably from acidic, aqueous solutions.
  • the ion exchangers with chelating groups prepared according to the invention are particularly suitable for removing heavy metals or noble metals from aqueous solutions, in particular from aqueous solutions of alkaline earths or alkalis, from alkalines of alkali chloride electrolysis, from aqueous hydrochloric acids, from wastewaters or flue gas scrubbers, but also from liquid or gaseous hydrocarbons , Carboxylic acids such as adipic acid, glutaric or succinic acid, natural gases, natural gas condensates, petroleum or halogenated hydrocarbons, such as chlorinated or fluorinated hydrocarbons or fluorine / chlorine hydrocarbons.
  • Carboxylic acids such as adipic acid, glutaric or succinic acid, natural gases, natural gas condensates, petroleum or halogenated hydrocarbons, such as chlorinated or fluorinated hydrocarbons or fluorine / chlorine hydrocarbons.
  • the erf ⁇ ndungshacken ion exchangers for the removal of alkaline earth metals from brines, as they are commonly used in the alkali chloride electrolysis.
  • the ion exchangers according to the invention are also suitable for the removal of heavy metals, in particular iron, chromium, cadmium or lead from substances which are reacted during an electrolytic treatment, for example a dimerization of acrylonitrile to adiponitrile.
  • the ion exchangers according to the invention for removing mercury, iron, chromium, cobalt, nickel, copper, zinc, lead, cadmium, manganese, uranium, vanadium, platinum group elements and gold or silver from the solutions, liquids or gases.
  • the inventive ion exchangers are suitable for removing rhodium or elements of the platinum group and gold, silver or rhodium or noble metal-containing catalyst residues from organic solutions or solvents.
  • the monodisperse or heterodisperse chelate exchangers according to the invention with a quaternary nitrogen atom in the functional group of the general formula (I) are outstandingly suitable for a very wide variety of applications in the chemical industry, the electronics industry, waste disposal / recycling Industry or electroplating or surface technology.
  • the resin is washed with deionised water and rinsed in a beaker. It is mixed with 100 ml of 1 N hydrochloric acid and allowed to stand for 30 minutes. The entire suspension is rinsed in a glass column. Another 100 ml of hydrochloric acid are filtered through the resin. The resin is washed with methanol. The procedure is made up to 1000 ml with deionised water. Of these, about 50 ml are titrated with 1 N sodium hydroxide solution.
  • the amount of strongly basic groups is equal to the sum of NaNO 3 number and HCl number.
  • the amount of weakly basic groups is equal to the HCl number.
  • demineralized water is characterized in that it has a conductivity of from 0.1 to 10 ⁇ S, the content of dissolved or undissolved metal ions being not greater than 1 ppm, preferably not greater than 0.5 ppm, for Fe, Co, Ni, Mo, Cr, Cu as individual components and not greater than 10 ppm, preferably not greater than 1 ppm for the sum of said metals.
  • a conductivity of from 0.1 to 10 ⁇ S, the content of dissolved or undissolved metal ions being not greater than 1 ppm, preferably not greater than 0.5 ppm, for Fe, Co, Ni, Mo, Cr, Cu as individual components and not greater than 10 ppm, preferably not greater than 1 ppm for the sum of said metals.
  • a mixture of 3200 g of microencapsulated monomer droplets having a narrow particle size distribution of 3.6% by weight of divinylbenzene and 0.9% by weight of ethylstyrene (used as a commercially available isomer mixture of divinylbenzene and ethylstyrene with 80% divinylbenzene) was then added 5% by weight dibenzoyl peroxide, 56.2% by weight styrene and 38.8% by weight isododecane (technical mixture of isomers with high pentamethylheptane content), the microcapsule consisting of a formaldehyde-cured complex coacervate of gelatin and a copolymer of acrylamide and acrylic acid, and 3200 g of aqueous phase having a pH of 12 was added.
  • the mean particle size of the monomer droplets was 460 ⁇ m.
  • the mixture was polymerized with stirring by increasing the temperature after a temperature program at 25 ° C starting and terminated at 95 0 C.
  • the batch was cooled, washed through a 32 micron sieve and then dried in vacuo at 80 0 C. This gave 1893 g of a spherical polymer having a mean particle size of 440 microns, narrow particle size distribution and smooth surface.
  • the bead polymer was chalky white in the plan and had a bulk density of about 370 g / l.
  • amidomethylated polymer beads from Ib were added 773.3 g of 50 wt .-% sodium hydroxide solution and 1511 ml of deionized water at room temperature. The suspension was heated to 18O 0 C in 2 hours and stirred at this temperature for 8 hours. The resulting bead polymer was washed with deionized water.
  • the batch was cooled, the resin was filtered off on a sieve and washed with demineralized water.
  • the batch was cooled.
  • the resulting bead polymer was filtered off through a sieve and washed with demineralized water.
  • the resulting bead polymer was filled in a column; From above, 2000 ml of 4% strength by weight aqueous sodium hydroxide solution were filtered through. Then deionised water was filtered over until the pH value in the outlet was ⁇ 9.
  • the final product contained 94.03 grams of methylpyridine, corresponding to 1.02 moles of methylpyridine.

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Abstract

L'invention concerne de nouvelles résines chélatantes renfermant comme groupes fonctionnels, des atomes d'azote quaternaire dans des structures de formule générale (I), dans laquelle au moins l'un des restes R1 à R3 désigne un reste éventuellement substitué de la série picolyle, méthylquinoléine- ou méthylpipéridine, m désigne un nombre entier de 1 à 4, et M désigne une matrice polymère, et X désigne un ion antagoniste de la série hydroxyde OH-, halogénure, de préférence Cl-, Br-, ou sulfate SO4 2-. L'invention concerne en outre un procédé de production des résines précitées, ainsi que leur utilisation, en particulier l'utilisation des nouvelles résines chélatantes en hydrométallurgie et en galvanisation.
EP08774968A 2007-07-23 2008-07-10 Résines chélatantes Withdrawn EP2175994A2 (fr)

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DE200710034731 DE102007034731A1 (de) 2007-07-23 2007-07-23 Chelatharze
PCT/EP2008/059005 WO2009013142A2 (fr) 2007-07-23 2008-07-10 Résines chélatantes

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WO2010082990A1 (fr) * 2009-01-15 2010-07-22 Dow Global Technologies Inc. Résines échangeuses d'ions comprenant des réseaux polymères à interpénétration et leur utilisation dans le retrait de chrome
CN103012647B (zh) * 2012-11-27 2016-02-24 安徽皖东化工有限公司 一种铅离子吸附树脂的制备方法
EP2835384A1 (fr) * 2013-08-09 2015-02-11 LANXESS Deutschland GmbH Procédé de fabrication de polymères en perles vinylaromatiques amidométhylés monodispersés
JP6497613B2 (ja) * 2014-01-30 2019-04-10 国立大学法人高知大学 ポリ（メタ）アクリル酸イオンコンプレックス
CN104177536A (zh) * 2014-07-25 2014-12-03 南京大学 一种螯合树脂吸附材料及其制备方法

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DE102007034731A1 (de) 2009-01-29
WO2009013142A3 (fr) 2009-06-25
CN101778671B (zh) 2013-04-10
US20130245140A1 (en) 2013-09-19
WO2009013142A2 (fr) 2009-01-29
CN101778671A (zh) 2010-07-14

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