EP2794106A1 - Résine d'acrylate contenant des groupes thiol - Google Patents

Résine d'acrylate contenant des groupes thiol

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Publication number
EP2794106A1
EP2794106A1 EP12797931.8A EP12797931A EP2794106A1 EP 2794106 A1 EP2794106 A1 EP 2794106A1 EP 12797931 A EP12797931 A EP 12797931A EP 2794106 A1 EP2794106 A1 EP 2794106A1
Authority
EP
European Patent Office
Prior art keywords
divinyl ether
acrylate
compounds
aqueous phase
acrylonitrile
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Withdrawn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
EP12797931.8A
Other languages
German (de)
English (en)
Inventor
Pierre Vanhoorne
Michael Schelhaas
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
Priority to EP12797931.8A priority Critical patent/EP2794106A1/fr
Publication of EP2794106A1 publication Critical patent/EP2794106A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/016—Modification or after-treatment of ion-exchangers
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Definitions

  • the present invention is a process for the preparation of novel ion exchange resins based on crosslinked bead polymers of acrylic compounds having thiol groups as a functional group, which have a high absorption capacity for heavy metals, and their use for the removal of heavy metals from liquids, preferably process waters in or from the electronics industry , the electroplating industry and the mining industry.
  • Ion exchangers have long been used to remove valuable metals and heavy metals such as tin, cobalt, nickel, copper, zinc, lead, uranium, bismuth, vanadium, platinum group elements such as ruthenium, osmium, iridium, rhodium, rhenium, palladium, platinum and precious metals Gold and silver used in particular from aqueous solutions.
  • thiol-functionalized resins are preferably used in addition to cation or anion exchangers.
  • Thiol-functionalized resins based on Styrolperlpolymerisaten are known and are sold, for example, from Rohm & Haas under the name Ambersep® ® GT74.
  • Other resins are commercially available Ionac ® SR4, Purolite ® S-920 or Resintech ® SIR 200th All of these resins have a polystyrene backbone and a benzylthiol or a phenylthiol functionality, respectively. (WSRC-TR-2002-00046, Rev.
  • Styrene-based resins generally have low osmotic stability and are lipophilic, i. they are sensitive to organic contaminants.
  • Hydroxythiolharze methacrylate are also represented in the market: Spheron ® thiol 1000.
  • methacrylic resins are also brittle and sensitive to osmotic stress.
  • the sulfur content of the molecule is low due to the other hydroxy functionality, which corresponds to a low specific capacity.
  • Polymers with thiol-functionalized acrylates are described in the literature. Nobuharu Hisano et al .: "Entrapment of islets into reversible disulfide hydrogels", J. Biomed. Mater. Res. 1998, 40 (1), 115-123.
  • Valessa Barbier et al . "Comb-like copolymer as self-coating, low-viscosity and high-resolution matrices for DNA sequencing", Electrophoresis 2002, 23, 1441-1449. Stephanie A. Robb et al .: Simultaneously Physically and Chemically Gelling Polymer System Utilizing a Poly (NIPAAm-co-cysteamine) -Based Copolymer, Biomacromolecules 2007, 8, 2294-2300.
  • Acrylate ion exchangers are known and commercially readily available, for example under the trade names Lewatit ® CNP80 or Amberlite ® IRA67.
  • the present invention relates to acrylate-based ion exchangers having at least one thiol functionality, preferably having a sulfur content of at least 20%, obtainable by a) reacting an organic phase comprising monomer droplets of at least one acrylic compound and at least one multifunctionally ethylenically unsaturated compound and optionally at least a porogen and / or optionally an initiator or an initiator combination in an aqueous phase to form a crosslinked bead polymer and b) reacting this crosslinked bead polymer with at least one aminothiol by adding it to the aqueous phase or after intermediate isolation of the bead polymers obtained from a), preferably by filtration, Decanting or centrifuging, by resuspension in an aqueous phase and addition of the aminothiol.
  • the conversion of the acrylate-based ion exchanger having thiol functionality obtained from stage b) into the Na form can also follow step b
  • the present invention further relates to a process for the preparation of acrylate-based ion exchangers having thiol functionality, characterized in that a) an organic phase containing monomer droplets of at least one acrylic compound and at least one multifunctional ethylenically unsaturated compound and optionally at least one porogen and / or optionally one B) this crosslinked bead polymer with at least one amino thiol by adding it to the aqueous phase or after intermediate isolation of the bead polymers obtained from a), preferably by filtration, decanting or centrifuging, and their renewed Suspension in an aqueous phase and adding the aminothiol reacts.
  • the acrylate-based ion exchangers obtainable according to step b) with thiol functionality preferably functional groups of the structures C (0) NH-alkyl-SH and / or C (0) NH-alkyl-SNa (in the case of transhipment), wherein alkyl represents a linear or branched alkyl chain having 2 to 6 carbon atoms.
  • the acrylate-based thiol-functional ion exchangers obtainable according to step b) have at least one functional group of the structure
  • R 1 is H or a C 1 -C 3 -alkyl radical, preferably H
  • R 2 is a linear or branched C 2 to e alkyl chain, preferably a linear C 2 chain, and
  • X is H or, after transposing Na, the n-indexed region for the polymer backbone of the acrylate-based ion exchanger having thiol functionality and X is Na when transposed in step c).
  • the acrylate-based ion exchangers according to the invention with thiol functionality have a gel-like or macroporous structure, preferably they have a macroporous structure which is obtained by adding at least one porogen to the organic phase.
  • At least one acrylic compound is used as monomer and at least one multifunctionally ethylenically unsaturated compound is used as crosslinker.
  • at least one acrylic compound is used as monomer and at least one multifunctionally ethylenically unsaturated compound is used as crosslinker.
  • acrylic acid esters having branched or unbranched C 1 -C 6 -alkyl radicals and nitriles of acrylic acid are preferably used in process step a).
  • Particularly preferred are methyl acrylate, butyl acrylate or acrylonitrile.
  • Very particular preference is given to using mixtures of the acrylic compounds, particularly preferably mixtures of methyl acrylate and acrylonitrile, or of butyl acrylate and acrylonitrile.
  • the monovmylaromatic compounds added in a preferred embodiment are preferably styrene, methylstyrene, ethylstyrene, chlorostyrene or vinylpyridine.
  • these monovmylaromatic compounds are added preferably in amounts of from 0.1 to 20% by weight, preferably from 0.1 to 10% by weight, based on the total sum of monomers and crosslinkers.
  • Multifunctional ethylenically unsaturated compounds - also called crosslinkers - for the crosslinked bead polymers are preferably compounds of the series butadiene, isoprene, divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene, trivinylnaphthalene, divinylcyclohexane, trivinylcyclohexane, triallycyanurate, triallylamine, 1, 7-octadiene, 1, 5 Hexadiene, cyclopentadiene, norbornadiene, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butanediol divinyl ether
  • Hexanediol divinyl ether or trimethylolpropane trivinyl ether Particular preference is given to divinyl benzene, 1,7-octadiene or Diethylenglykoldivinylether used. Commercial divinylbenzene grades which also contain ethylvinylbenzene in addition to the isomers of divinylbenzene are sufficient. In a preferred embodiment, it is also possible to use mixtures of different crosslinkers, more preferably mixtures of divinylbenzene and divinyl ether. Very particular preference is given to using mixtures of divinylbenzene, 1,7-octadiene or diethylene glycol divinyl ether. Especially preferred are mixtures of divinylbenzene and 1,7-octadiene.
  • the multifunctionally ethylenically unsaturated 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 total sum of monomers and crosslinkers.
  • the type of multifunctional ethylenically unsaturated compounds to be used as crosslinkers is selected with regard to the subsequent use of the bead polymer.
  • the monomer droplets in a preferred embodiment of the present invention contain an initiator or mixtures of initiators to initiate the polymerization.
  • Initiators preferably used for the process according to the invention are peroxy compounds, more preferably peroxy compounds of the series 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, preferably 2,2'-azobis (isobutyronitrile) or 2,2'-azobis (2-methylisobutyronitrile). Very particular preference is given to dibenzoyl peroxide.
  • the initiators are preferably used in amounts of 0.05 to 2.5 wt .-%, particularly preferably 0.1 to 1.5 wt .-%, based on the total of monomers and crosslinkers.
  • Preferred bead polymers in the context of the present invention, prepared by process step a), have a macroporous structure.
  • the terms macroporous or gel have already been described in detail in the specialist literature (see Pure Appl. Chem., Vol. 76, No. 4, pp. 900, 2004).
  • porogen is used in the monomer droplets.
  • organic solvents are suitable which dissolve or swell the resulting polymer poorly.
  • porogens are compounds of the series hexane, octane, isooctane, isododecane, methyl ethyl ketone, dichloroethane, dichloropropane, butanol or octanol and their isomers. It is also possible to use mixtures of porogens.
  • the porogen or porogen mixture is used in amounts of from 5 to 70% by weight, preferably from 10 to 50% by weight, based on the total sum of monomers and crosslinkers.
  • porogen gel-like resins are obtained, which are also part of the present invention.
  • the aqueous phase in a preferred embodiment may contain at least one dissolved polymerization inhibitor.
  • polymerization inhibitors in the context of the present invention are preferably both inorganic and organic substances in question.
  • Particularly preferred inorganic polymerization inhibitors are nitrogen compounds of the series hydroxylamine, hydrazine, sodium nitrite or potassium nitrite, salts of phosphorous acid, in particular sodium hydrogenphosphite, and sulfur-containing compounds, in particular sodium dithionite, sodium thiosulfate, sodium sulfate, sodium bisulfite, sodium thiocyanate or ammonium thiocyanate.
  • Particularly preferred organic polymerization inhibitors are phenolic compounds of the series hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butylpyrocatechol, pyrogallol and condensation products of phenols with aldehydes.
  • Other suitable organic polymerization inhibitors are nitrogen-containing compounds.
  • hydroxylamine derivatives preferably of the series ⁇ , ⁇ -diethylhydroxylamine, N-isopropylhydroxylamine and also sulfonated or carboxylated N-alkylhydroxylamine or N, N-dialkylhydroxylamine derivatives, hydrazine derivatives, preferably ⁇ , ⁇ -hydrazinodiacetic acid, nitroso compounds, preferably N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine Ammonium salt or N-nitrosophenylhydroxylamine aluminum salt.
  • the concentration of the polymerization inhibitor to be used in a preferred embodiment is 5-1000 ppm (based on the aqueous phase), preferably 10-500 ppm, particularly preferably 10-250 ppm.
  • Suitable protective colloids are natural or synthetic water-soluble polymers, the series gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid or copolymers of acrylic acid or acrylic acid esters. Gelatine is preferred according to the invention.
  • cellulose derivatives in particular cellulose esters or cellulose ethers, very particularly preferably carboxymethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose or hydroxyethylcellulose.
  • condensation products of aromatic sulfonic acids and formaldehyde Particularly preferred are naphthalenesulfonic acid-formaldehyde condensates.
  • the protective colloids can be used singly or as mixtures of different protective colloids. Very particular preference is given to a mixture of hydroxyethyl cellulose and naphthalenesulfonic acid-formaldehyde condensate or its Na salt.
  • the amount used for the sum of the protective colloids is preferably 0.05 to 1 wt .-% based on the aqueous phase, particularly preferably 0.05 to 0.5 wt .-%.
  • the polymerization of the spherical 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 at the beginning of the polymerization to a value between 14 and 6, preferably between 12 and 8.
  • protective colloids with carboxylic acid groups are wholly or partially present as salts. In this way, the effect of 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 0.5-500 mmol / l, preferably 2.5-100 mmol / l.
  • the polymerization of the spherical bead polymer in process step a) can also be carried out in the presence of a salt in the aqueous phase.
  • a salt in the aqueous phase.
  • Preferred salts are halides, sulfates or phosphates of the alkali and alkaline earth metals. They can be used in the concentration range up to the saturation of the aqueous phase. The optimal range is therefore different for each salt and must be tested.
  • the stirring rate in the polymerization has a significant influence on the particle size, especially at the beginning of the polymerization. Basically, smaller particles are obtained at higher stirring speeds. By adjusting the stirring speed, the skilled person can control the particle size of the bead polymers in the desired range.
  • Various types of stirrers can be used. Particularly suitable are lattice stirrers with axial action. Stirrer speeds of 100 to 400 rpm (revolutions per minute) are typically used in a 4 liter laboratory glass reactor.
  • the polymerization temperature depends on the decomposition temperature of the initiator used.
  • the polymerization preferably lasts 0.5 to a few hours, more preferably 2 to 20 hours, most preferably 5 to 15 hours. It has been proven to use a temperature program in which the polymerization at low temperature, for example 60 ° C is started and the reaction temperature is increased with increasing polymerization conversion. In this way, for example, the demand for safe reaction course and high polymerization conversion can be fulfilled very well.
  • the bead polymer is isolated by conventional methods, preferably by filtering, decanting or centrifuging, and optionally washed.
  • acrylonitrile methyl acrylate
  • divinylbenzene 1,7-octadiene
  • dibenzoyl peroxide dibenzoyl peroxide or dichloroethane are used.
  • the bead polymers obtainable from process step a) preferably have a bead diameter in the range of 100 ⁇ m to 2,000 ⁇ m.
  • the crosslinked bead polymers based on acrylic compounds prepared according to process step a) are further processed in process step b) by reaction with at least one aminothiol.
  • Aminothiols which are preferably used according to the invention are liquid at room temperature.
  • Aminothiols which are particularly preferred for use in accordance with the invention are compounds of the general formula H 2 N-alkyl-SH which are liquid at room temperature, in which alkyl is a linear or branched alkyl chain having 2 to 6 carbon atoms.
  • Very particular preference is given to compounds of the general formula R 1 NH-alkyl-SH which are liquid at room temperature, in which alkyl is a linear or branched alkyl chain having 2 to 4 carbon atoms and R 1 is H or a C 1 -C 3 -alkyl radical, preferably H.
  • Particularly preferred compounds which are liquid at room temperature are of the general formula H 2 N-alkyl-SH, in which alkyl is an alkyl chain of 2 carbon atoms, such that the total molecule is cysteamine.
  • the aminothiols are preferably in a molar ratio, based on the reacted Ester precipit. Nitrile groups, from 0.7 to 8 mol, preferably in amounts of 0.8 to 3 mol of aminothiol per mol of ester or nitrile groups, more preferably 1.0 to 1.5 mol of aminothiol per mole of ester or nitrile groups.
  • the reaction in process step b) is preferably carried out at temperatures of 80 to 250 ° C., more preferably at 115 to 160 ° C.
  • the reaction time is generally chosen so that the nitrile or ester groups are quantitatively reacted; the achievable conversion is at least 80%, preferably at least 90%, in particular at least 95%>.
  • the thiol-functional acrylate-based ion exchangers obtained from process step b) contain in a preferred embodiment of the present invention at least 20% by weight of> sulfur, based on the dry mass of the exchanger.
  • the thiol-functional acrylate-based ion exchangers obtained from process step b) can be used in the SH form or after being transposed in the SNa form.
  • the transhipment takes place in the process step c) to be carried out in a preferred embodiment with aqueous sodium hydroxide solution, preferably in the presence of sodium chloride or sodium sulfate.
  • the transhipment is preferably carried out in a column or stirred in a kettle. For complete transhipment, a molar ratio of 1.1 to 5 mol of NaOH per mol is preferred
  • the acrylate-based ion exchangers with thiol functionality to be prepared according to the invention are suitable for the adsorption of metals, in particular heavy metals and noble metals and their compounds, from aqueous solutions and organic liquids, preferably from acidic, aqueous solutions.
  • the acrylate-based ion exchangers with thiol functionality to be prepared according to the invention are particularly suitable for the removal of 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.
  • the acrylate-based ion exchangers according to the invention with thiol functionality are also suitable for the removal of heavy metals, in particular mercury, silver, cadmium or lead from substances which are reacted during an electrolytic treatment, for example a dimerization of acrylonitrile to adiponitrile.
  • acrylate-based ion exchangers according to the invention with thiol functionality for removing mercury, iron, chromium, cobalt, nickel, copper, zinc, Lead, cadmium, manganese, uranium, vanadium, ruthenium, rhodium, palladium, iridium, osmium, platinum and gold and silver from the solutions, liquids or gases listed above.
  • the acrylate-based ion exchangers according to the invention having thiol functionality are suitable for removing mercury, copper, cadmium, ruthenium, rhodium, palladium, iridium, osmium, platinum and also gold and silver from the abovementioned solutions, liquids or gases.
  • the acrylate-based ion exchangers with thiol functionality are ideal for a wide variety of applications in the chemical industry, the electronics industry, the waste disposal / recycling industry or electroplating or surface technology.
  • demineralized water means water which has a conductivity of 0.1 to 10 ⁇ 8 and has a soluble metal ion content of not more than 1 ppm, preferably not more 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.
  • the polymerization was carried out in a 3 liter glass planer vessel with glass stirrer, temperature sensor, reflux condenser, water separator and thermostat with control unit.
  • the aqueous phase was initially charged and the premixed organic phase was added. The mixture was then heated to 64 ° C. with stirring in 90 minutes and this temperature was maintained for 12 hours. It was then heated to 100 ° C in 30 minutes and held this temperature for 3 h. It was then cooled and washed through a sieve.
  • the yield was 1130 ml and 966 g of wet product, respectively.
  • the dry weight was 0.72 g / ml.
  • the polymerization was carried out in a 3 liter glass planer vessel with glass stirrer, temperature sensor, reflux condenser, water separator and thermostat with control unit.
  • the aqueous phase was initially charged and the premixed organic phase was added. The mixture was then heated to 61 ° C. with stirring in 90 minutes and this temperature was kept for 7 hours. Then it was heated to 100 ° C in 30 minutes and held this temperature for 4 h. It was then cooled and washed through a sieve.
  • the yield was 855 ml or 696 g of wet product.
  • the dry weight was 0.72 g / ml.
  • Cysteamine hydrochloride presented and added at room temperature with stirring 111 g of 50% sodium hydroxide solution by means of dropping funnel. The mixture was then heated at reflux for 24 h.
  • the cooled mixture was washed in a column of demineralized water until the effluent reached about pH 8.
  • the yield was 238 ml or 205 g of moist product.
  • the dry weight was 0.61 g 1 ml.
  • the silver capacity was 96.7 grams of silver / liter of resin, equivalent to 0.90 eq / liter of resin.
  • the cooled mixture was washed in a column of demineralized water until the effluent reached about pH 8.
  • the yield was 209 ml or 180 g of wet product.
  • the dry weight was 0.68 g / ml.
  • the silver capacity was 47.7 grams of silver / liter of resin, equivalent to 0.44 eq / liter of resin.

Abstract

La présente invention concerne un procédé de production de nouvelles résines échangeuses d'ions à base de polymérisats en perles réticulés de composés acryliques comprenant des groupes thiol comme groupes fonctionnels qui ont une capacité d'absorption élevée pour les métaux lourds, ainsi que leur utilisation pour éliminer des métaux lourds de liquides, de préférence des eaux de processus dans ou provenant de l'industrie électronique, l'industrie galvanique et l'industrie minière.
EP12797931.8A 2011-12-22 2012-12-07 Résine d'acrylate contenant des groupes thiol Withdrawn EP2794106A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12797931.8A EP2794106A1 (fr) 2011-12-22 2012-12-07 Résine d'acrylate contenant des groupes thiol

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11195334.5A EP2606973A1 (fr) 2011-12-22 2011-12-22 Résine acrylique contenant des groupements thiol
PCT/EP2012/074776 WO2013092249A1 (fr) 2011-12-22 2012-12-07 Résine d'acrylate contenant des groupes thiol
EP12797931.8A EP2794106A1 (fr) 2011-12-22 2012-12-07 Résine d'acrylate contenant des groupes thiol

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EP2794106A1 true EP2794106A1 (fr) 2014-10-29

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CN110813255B (zh) * 2019-12-03 2022-06-03 东华理工大学 一种双功能化聚合物螯合树脂制备及分离与富集铀的方法
CN113083363B (zh) * 2019-12-23 2022-09-16 万华化学集团股份有限公司 一种树脂催化剂及其制备方法和应用
CN117447630B (zh) * 2023-12-22 2024-03-26 上海稀固科技有限公司 巯基树脂及其制备方法与应用

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WO2013092249A1 (fr) 2013-06-27
CN103998135A (zh) 2014-08-20
EP2606973A1 (fr) 2013-06-26

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