EP2001592A2 - Matière échangeuse d'ions, colonne échangeuse d'ions et procédé de réalisation associé - Google Patents

Matière échangeuse d'ions, colonne échangeuse d'ions et procédé de réalisation associé

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Publication number
EP2001592A2
EP2001592A2 EP07727789A EP07727789A EP2001592A2 EP 2001592 A2 EP2001592 A2 EP 2001592A2 EP 07727789 A EP07727789 A EP 07727789A EP 07727789 A EP07727789 A EP 07727789A EP 2001592 A2 EP2001592 A2 EP 2001592A2
Authority
EP
European Patent Office
Prior art keywords
ion exchange
groups
group
exchange material
carrier resin
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Withdrawn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
EP07727789A
Other languages
German (de)
English (en)
Inventor
Michael Raskop
Andreas Seubert
Andreas Grimm
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.)
Metrohm AG
Original Assignee
Metrohm AG
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 Metrohm AG filed Critical Metrohm AG
Priority to EP07727789A priority Critical patent/EP2001592A2/fr
Publication of EP2001592A2 publication Critical patent/EP2001592A2/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Withdrawn legal-status Critical Current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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B01J20/3221—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond the chemical bond being an ionic interaction
    • 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
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction, e.g. ion-exchange, ion-pair, ion-suppression or ion-exclusion
    • B01D15/361—Ion-exchange
    • 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
    • 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
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/016—Modification or after-treatment of ion-exchangers

Definitions

  • the invention relates to the field of particular particle-shaped ion exchange materials and their preparation.
  • Ion exchange materials can be built up on a carrier resin, which is functionalized with negatively charged groups (so-called cation exchange groups) or positively charged groups (so-called anion exchange groups).
  • the functionalization of a styrene-divinylbenzene copolymer resin with sulfonate groups takes place, for example, in common practice by treatment with SO 3.
  • ion exchange materials are fixed via ionic interactions, which have charges that are opposite to the functionalization of the carrier resin particles.
  • anion exchange materials are known which are built up on support resin particles modified with (negatively charged) sulfonate groups, on which anion exchange materials having (positively charged) anion exchange groups are fixed via ionic interaction.
  • ion exchange materials which are obtained by grafting a molecule containing an ion exchange function on a divinylbenzene carrier resin using the radical initiator 2, 2 '-Azo-di (isobutyronitrile), AIBN. With the method described there, an ion exchange material is obtained, which has an extremely high capacity (therefore unacceptably long retention times), with at the same time only a small theoretical plate number.
  • An ion exchange material according to the invention comprises a hydrophobic carrier resin having grafted side chains, which side chains in particular comprise hydrophilic ion exchange groups, and wherein the side chains have a surfactant-like structure.
  • a surfactant-like structure comprises at least one hydrophilic and one hydrophobic functional group. Hydrophilic and hydrophobic parts must be coordinated with one another in such a way that alignment at the interface between aqueous phase and the other (solid, liquid or gaseous) phase (in this case: the hydrophobic carrier resin) is made possible.
  • the surfactant-like structure of the side chains makes it possible to achieve regioselectivity and coverage in the anchoring of these side chains on the support resin, which is superior to conventional ion exchange materials. It turns out that the surfactant-like structure allows alignment of the side chains before grafting, which is very homogeneous.
  • the hydrophobic carrier resin (such as, for example, polystyrene-divinylbenzene copolymers) is wetted by the surfactant-type reagent, but not in the tightest packing.
  • the surfactant-like molecules strive to move away from each other until the electrostatic repulsion of the equally charged molecules loses its effect. This leads to a very regular distribution of the surfactant-like molecules on the carrier material.
  • the surfactant-like molecules hardly penetrate into the pore structure of the carrier material and anchor it there. Both the non-use of the pores, as well as the fact that the side chains are not arranged in the tightest packing, also allows a uniform and fairly complete hydration of the ion exchange groups, which in particular also manifests itself in a lower signal asymmetry.
  • graft polymerization offers the great advantage of easy controllability of the ion exchange capacity resulting from the degree of coverage.
  • monomers are preferably polymerized onto prefabricated polymers; In this case, the monomers already have the desired ion exchange functionality, for example a sulfonate group (or a sulfonic acid salt), so that subsequent conversion after the grafting is no longer necessary.
  • the grafting is compared to conventional methods ren for the introduction of ion exchange groups different steric environment of the exchange group generated, which also can be widely varied by targeted selection of the grafting agent in particular in the hydrophobic part (structure, chain length, etc.).
  • the ion exchange material according to the invention can be obtained by free radical grafting of the side chains using a free radical initiator containing at least one peroxide group, very particularly preferably a peroxodisulfate (S 2 O g " ) based radical initiator Compared to those known from WO 02/18464, using According to the invention, ion exchange materials obtainable with AIBN are ion exchange materials which have a significantly increased plate count with sufficient capacity (ie, tolerable retention time.) Suitable representatives of the radical initiators containing peroxide groups are, for example, hydrogen peroxide (H2O2) and the organic peroxides dibenzoyl peroxide and di-t-butyl peroxide.
  • H2O2 hydrogen peroxide
  • organic peroxides dibenzoyl peroxide and di-t-butyl peroxide.
  • suitable inorganic peroxides are insobesondere peroxosulfuric acid (H 2 SO 5), peroxo sulfate (SO ⁇ ") based free radical initiator such as. (NH 4) 2 SO 5, Na 2 SO 5, and K 2 SO 5 suitable , as well as peroxodisulfuric acid (H 2 S 2 Os) t peroxodisulfone At (S 2 O g " ) based radical initiators such as. (NH 4 ) 2 S 2 Os, Na 2 S 2 Os and, most preferably, K 2 S 2 Os.
  • the carrier resin comprises or consists of polymers selected from the group consisting of styrene-divinylbenzene copolymers; Divinylbenzene-ethylvinylbenzene copolymers; Divinylbenzene-acrylic acid copolymers; Polyacrylates and / or polymethacrylates; Amine-epichlorohydrin copolymers; Graft polymers of styrene on polyethylene and / or polypropylene; Poly (2-chloromethyl-1,3-butadiene; poly (vinylaromatic)) resins, in particular based on styrene, alpha-methylstyrene, chlorostyrene, chloromethylstyrene, vinyl toluene, vinylnaphthalene, vinylpyridine; amino resins; celluloses; Polyvinyl alcohols, phenol-formaldehyde resins.
  • styrene-divinylbenzene copolymers and di-vinylbenzene-ethylvinylbenzene copolymers; In this case, the divinylbenzene content and thus the degree of crosslinking of the carrier resin can be varied over a wide range.
  • carrier resins and their preparation are known to the person skilled in the art, for example from US Pat. No. 5,324,752 and EP 883 574; the description of these documents with respect to the carrier resins is hereby incorporated by reference into the disclosure.
  • the side chain has a hydrophobic part with an aromatic structural unit.
  • the ratio of the aromatic structural units present in the hydrophobic parts of the side chains to the number of hydrophilic areas, in particular to the number of ion exchange groups in the hydrophilic areas, is preferably ⁇ 1, in particular 2 2, ⁇ 3 or ⁇ 4 a single ion exchange group per side chain just this ion exchange group understood.
  • a plurality of ion exchange groups may also be present in this hydrophilic region.
  • several anchoring points can be provided on the carrier resin per side chain.
  • the side chain comprises an aromatic structural unit which is selected from the group consisting of benzyl derivatives, Naphtylderivaten, biphenyl derivatives.
  • the side chain has a hydrophobic part with a particularly aliphatic carbon chain of ⁇ 6 carbon atoms, preferably of ⁇ 8 carbon atoms, more preferably of ⁇ 10 carbon atoms.
  • This aliphatic carbon chain can be special be provided in addition to aromatic structural units in the side chain, or in particular at chain lengths of ⁇ 10 carbon atoms alone form the hydrophobic part of the side chain.
  • the carrier resin is formed from a polymer which has pendant, unsaturated groups, in particular vinyl groups.
  • unsaturated groups are preferred grafting substrates for the side chains having the ion exchange groups.
  • the grafted side chains can themselves be polymers.
  • a block (co) polymer with a vinyl function, with one or more ion-exchange groups and one or more hydrophobic regions can be used.
  • a polymeric side chain with vinyl group-containing, surfactant-type monomers which have an ion-exchange group.
  • the carrier resin is particulate, with average particle diameters in the range of 2 to 100 .mu.m, preferably 3 to 25 .mu.m, particularly preferably 4 to 10 microns.
  • a separation efficiency in the range of about 25,000 to about 50,000 theoretical plates per meter is typically achieved (eluent: 7.5 mmol / l Na2CO3, flow rate: 1 ml / min 20 ° C; analytes: 10 mg / ml fluoride, 20 mg / ml chloride, 5 mg / ml nitrite, 5 mg / ml phosphate, 40 mg / ml bromide, 20 mg / ml sulfate, 10 mg / ml nitrate).
  • ion exchange materials are polymers having charged groups as a constituent of the main chain, for example the so-called ionene.
  • ionene is understood here and hereinafter to mean polymers which have quaternary ammonium groups in the main chain. It has been attempted in the art to apply such ionene to support materials via ionic interactions to make them available for column chromatography.
  • an efficient ion exchange material such can be understood which has> 2,000 theoretical plates per column meters, preferably> 5,000, even more preferably> 10,000 (for anion exchangers: with isocratic elution with 1 mmol / L Na 2 CC> 3/3 mmol / L NaHCC> 3 of organic and inorganic anions such as fluoride, chloride, bromide, nitrite, nitrate, phosphate, sulfate).
  • synthetic resin support materials such as, for example, polystyrene-divinylbenzene copolymers
  • synthetic resin support materials such as, for example, polystyrene-divinylbenzene copolymers
  • their mechanical properties For example, it would be desirable to be able to fix the above-described polymers with charged groups as constituent of the main chain or side chains, in particular the ions, reproducibly and with sufficient resulting ion exchange efficiency via ionic interaction on such synthetic resin support materials.
  • An ion exchange material comprises a support resin having cation exchange groups, and anion exchange material fixed to said support resin by ionic interactions, said anion exchange material being a polymer having cationic groups as a constituent of the main chain.
  • the cationic groups are particularly preferably selected as constituent of the main chain of the anion exchange material selected from the group consisting of ammonium groups, sulfonium groups, phosphonium groups, arsonium groups and mixtures thereof.
  • the cationic groups comprise quaternary ammonium groups as part of the backbone of the anion exchange material.
  • Such polymers having quaternary ammonium groups as a constituent of the main chain are often referred to in the literature as ionene.
  • ionene can be obtained via multiple Menshutkin reaction (N-alkylation), according to the following reaction scheme:
  • R 1 , R 2 , R 3 , R 4 each represent any organic radicals, with short chain, unbranched alkyl groups, in particular, such as CH 3 and C 2 H 5 being preferred;
  • X represents a leaving group, preferably a halogen. More preferably, R 1 , R 2 , R 3 , R 4 are all CH 3 groups.
  • the number x of repeating units is controlled during the polymerization and the chain lengths n and m of the reactants are preferably selected such that polymers having an average molecular weight of from about 2,000 to about 100,000 g / mol result, preferably from about 5,000 to about 75,000 g / mol, more preferably from about 8,000 to about 30,000 g / mol. Polymers of this molecular weight range have proven to be particularly advantageous in terms of the efficiency and stability of the resulting ion exchange materials.
  • the anion exchange material comprises repeating units selected from the group consisting of:
  • R 1 CH 3 , C 2 H 5 ;
  • R2 CH 3, C 2 H 5;
  • R 3 CH 3 , C 2 H 5 ;
  • R 4 CH 3 , C 2 H 5 ;
  • the aforementioned carrier resins can in turn also be used for this aspect of the invention.
  • the carrier resin is particularly preferably particulate, with average particle diameters in the range from 2 to 100 ⁇ m, preferably from 3 to 50 ⁇ m, particularly preferably from 4 to 25 ⁇ m.
  • the carrier resin comprises cation exchange groups which are selected from the group consisting of sulfonate groups, carboxyl groups, chelating agents, and mixtures thereof. Most preferably, the carrier resin comprises sulfonate groups.
  • the cation exchange capacity of the carrier resin is set by the abovementioned cation exchange groups to 1 to 250 ⁇ eq / g, preferably 3 to 70 ⁇ equiv / g, particularly preferably 5 to 50 ⁇ equiv / g.
  • the cation exchange capacity of the carrier resin is of great importance for the possibility of fixing the anion exchange material thereon: if the cation exchange capacity is too low, the (oppositely charged) anion exchange material can not be fixed, whereas if the cation exchange capacity is too high, the anion exchange material can be fixed, However, the charges of the anion exchange material are compensated (over) and thus no Anionenaus- exchange effect more results.
  • the cation exchange capacity must therefore be carefully controlled, and preferably also be tailored to the particular polymeric anion exchange material to be used with cationic groups as part of the main chain.
  • processes for sulfonation for example with SO 3
  • such a control of the cation exchange capacity is difficult to achieve.
  • the production of ion exchange materials according to the invention succeeds simply and excellently reproducibly with the method described below.
  • Another aspect of the invention relates to a process for preparing an ion exchange material comprising the steps of: (a) providing a hydrophobic carrier resin; (b) free-radical grafting of a grafting agent having a surfactant-like structure onto the carrier resin, wherein the grafting reagent comprises at least one in particular hydrophilic ion exchange group, and wherein the free-radical initiator used is a free-radical initiator containing at least one peroxide group, in particular selected from the group consisting of hydrogen peroxide, Dibenzoyl peroxide and di-t-butyl peroxide, peroxosulfuric acid, peroxosulfate-based radical starters, in particular (NH 4 ) 2 SO 5 , Na 2 SO 5 and K 2 SO 5 , peroxodisulfuric acid, peroxodisulfate-based radical initiators, in particular (NH 4 ) 2 S 2 Os , Na 2 S 2 Os and, most preferably, K 2
  • the grafting reaction as such is familiar to the person skilled in the art;
  • the radical initiator is added in customary amounts. It has been found that it is particularly advantageous if the grafting reagent is purified before grafting onto the carrier resin.
  • the grafting reagents can be obtained, for example, by nucleophilic substitution of vinylbenzyl halide, in particular chloride, with an amine.
  • the vinylbenzyl chloride is preferably used here in an inhibitor-stabilized form (both for reasons of price and for suppressing undesired autopolymerization). However, the inhibitor, as well as solvents and by-products, may adversely affect the grafting reaction in step (b).
  • the grafting reagent has a hydrophobic part having an aromatic structural unit.
  • the grafting reagent may have a hydrophobic part with a particularly aliphatic carbon chain of ⁇ 6 carbon atoms, preferably of ⁇ 8 carbon atoms, more preferably of ⁇ 10 carbon atoms.
  • Suitable carrier resins are in particular the polymers which are mentioned at the front, and which in particular has pendant, unsaturated groups, in particular vinyl groups.
  • the grafting reaction can be carried out as a graft block (co) polymerization (grafting of a polymeric side chain) or as a graft (co) polymerization (polymer formation of the side chain from monomers).
  • the grafting reagent comprises a vinyl function, in particular a structural unit which is selected from the group consisting of vinylbenzyl derivatives
  • Vinylnaphtylderivaten uncondensed vinyl polyaromatics, especially vinyl biphenyl derivatives.
  • grafting reagents which carry quaternary ammonium groups as ion exchange groups are preferred; particularly preferred are those having a diethanol-methylammonium group.
  • the grafting reagent is preferably selected from the group consisting of:
  • M + is an alkali cation, preferably Na + ;
  • X is a halide, preferably Cl "
  • Preferred grafting reagents (( ⁇ ) here in each case denotes a vinyl group-containing organic radical, preferably the vinyl group itself) are in particular:
  • R, Rl, R2 SO 3, COOH, H, CH 2 CH 3, CH 3, CH 2 COOH, CH 2 CH 3 COOH, vinyl, hexyl, phenyl;
  • Rl SO 3, COOH, H, CH 2 CH 3, CH 3, CH 2 COOH, CH 2 CH 3 COOH, vinyl, hexyl, phenyl;
  • R SO 3 , COOH, H, CH 2 CH 3 , CH 3 , CH 2 COOH, CH 2 CH 3 COOH,
  • surfactant-type grafting reagents comprising pyrolidine, piperidine, morpholine, pyrol, pyridine, pyrimidine, pyrazine, triazine, pyridone, quinoline, purine, indole, oxazole, thiazole, Imidazole ring systems and combinations of such ring systems.
  • an ion exchanger is not understood in particular as meaning: 2-hydroxyethyl methacrylate; N-vinylpyrrolidone; N-vinyl caprolactam.
  • the method comprises the steps:
  • the cationic groups as part of the main chain of the anion exchange material particularly preferably comprise quaternary ammonium groups, sulfonium groups, phosphonium groups, arsonium groups and optionally mixtures thereof.
  • the carrier resin is functionalized with at least one grafting reagent which contains at least one vinyl group, and which further contains a functionality selected from the group consisting of sulfonate groups, carboxyl groups, chelating agents, and mixtures thereof.
  • the graft polymerization is preferably controlled in such a way that an ion exchange capacity, in particular a cation exchange capacity of the functionalized carrier resin of 1 to 250 ⁇ eq / g is achieved.
  • the carrier resin is functionalized with at least one grafting reagent containing at least one vinyl group and further containing a functionality selected from the group consisting of sulfonate groups, carboxyl groups, chelating agents, and mixtures thereof.
  • FIG. 1 elution profile of an anion exchanger material according to the invention
  • FIG. 2 elution profile of the commercial anion exchanger A SUPP 10-100, Metrohm AG; in comparison to Fig. 1;
  • FIG. 3 elution profile of an anion exchanger material according to the invention (radical initiator: K 2 S 2 O 8);
  • FIG. 4 elution profile of an anion exchange material using AIBN as radical initiator
  • FIG. 6 shows the net retention of various anions as a function of the amount of the ion fixed on the carrier resin
  • FIG. 7 Long-term stability of an ion exchanger column according to the invention (using 6-6 ions on PS / DVBB as an example, sulfonate-functionalized by means of graft polymerization and a cation exchange capacity of 20 ⁇ Equiv / g).
  • FSDEMA N-divinylbenzyl-N, N-diethanolmethylammonium chloride
  • the suspension is maintained at 343 K over the reaction time of 4 hours Inert gas stirred.
  • the suspension is then cooled to 278 K and the solid is filtered off and washed with ethanol.
  • the product obtained is sedimented in 200 ml of sedimentation solution (175 ml of ethanol and 25 ml of cyclohexanol) for 24 hours.
  • the supernatant solution is removed, the solid washed again with ethanol and dried.
  • 1 shows by way of example an elution profile of this anion exchanger (1-dead volume, 2-fluoride, 3-chloride, 4-nitrite, 5-bromide, 6-nitrate, 7-phosphate, 8-sulfate), under the following elution conditions: Column temperature 318K; Eluent: 7.5 mmol / l sodium carbonate; Flow rate: 1.0 ml / min; Column dimension: 100x4 mm.
  • FIG. 2 exemplarily shows an elution profile of a high performance, commercial anion exchanger (A SUPP 10-100 (serial number 040907-S42), Metrohm AG with identical peak assignment as in Fig. 1 under the following elution conditions: column temperature 318K; eluent: 5 , 0 mmol / l sodium carbonate, 5.0 mmol / l sodium bicarbonate, flow rate: 1.2 ml / min.
  • a SUPP 10-100 serial number 040907-S42
  • Metrohm AG with identical peak assignment as in Fig. 1 under the following elution conditions: column temperature 318K; eluent: 5 , 0 mmol / l sodium carbonate, 5.0 mmol / l sodium bicarbonate, flow rate: 1.2 ml / min.
  • FIG. 3 shows an elution profile of an ion exchanger column according to the invention (radical initiator K 2 S 2 Os, "preparation method as outlined above for FSDMA functionalization, but here with vinylbenzyltrimethylammonium chloride), in comparison to the elution profile of an ion exchanger column according to WO 02/18464, Ex. 11 (FIG. 4, radical initiator AIBN, likewise with vinylbenzyltrimethylammonium chloride).
  • FIG. 5 shows, by way of illustration, the electrostatic fixation of ions on support resins functionalized with cation exchange groups.
  • the lower part illustrates a sufficient but low degree of functionalization of the support resin which, after fixing the ion, results in a net positive charge, thus giving anion exchange capacity.
  • the method according to the invention makes it particularly easy to set a defined, suitable degree of functionalization.
  • the resulting cation exchange capacity (proton exchange capacity) of the carrier material can be controlled easily and reproducibly by adding the amount of 4-vinylbenzenesulfonic acid sodium salt.
  • 5 ⁇ Eq / g was obtained, at 0.050 g of 10 ⁇ Eq / g at 0.075 g 15 ⁇ Eq / g, 0.150 g 30 ⁇ Eq / g, 0.225 g 45 ⁇ Eq / g, 0.350 g 70 ⁇ Eq / g, and 0.425 g 85 ⁇ Eq / g.
  • FIG. 5 shows this using the example of 6-6 ions on 20 ⁇ Equiv / g PS / DVB carrier material prepared as described above.
  • As Testanion served phosphate under Standardchromatographie discipline (eluent: 1 mmol / 1 Na2CC> 3, 3 mmol / 1 NaHCO 3, - flow rate: 0.8 ml / min; temperature: 30 0 C). Not even the flow of 100 mmol / l NaOH during one day resulted in a significant change in the retention factors or the efficiency (data not shown).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne des matières échangeuses d'ions comprenant une résine support hydrophobe dotée de chaînes latérales greffées qui ont une structure de type tensioactif et comportent des groupes échangeurs d'ions. La matière échangeuse d'ions est obtenue par greffage radicalaire des chaînes latérales au moyen d'une amorce radicalaire contenant au moins un groupe peroxyde. La structure de type tensioactif et l'amorce radicalaire spécifique permettent d'obtenir une disposition régiospécifique particulièrement régulière des chaînes latérales sur la résine support, cette disposition permettant en outre une hydratation exceptionnelle et homogène des groupes échangeurs d'ions, ce qui se traduit notamment par des asymétries de signal améliorées pour le bromure et le nitrate.
EP07727789A 2006-04-04 2007-04-04 Matière échangeuse d'ions, colonne échangeuse d'ions et procédé de réalisation associé Withdrawn EP2001592A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07727789A EP2001592A2 (fr) 2006-04-04 2007-04-04 Matière échangeuse d'ions, colonne échangeuse d'ions et procédé de réalisation associé

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06112215A EP1842592A1 (fr) 2006-04-04 2006-04-04 Materiau échangeur d'ions, colonne échangeuse d'ions et méthode de préparation
EP07727789A EP2001592A2 (fr) 2006-04-04 2007-04-04 Matière échangeuse d'ions, colonne échangeuse d'ions et procédé de réalisation associé
PCT/EP2007/053320 WO2007122085A2 (fr) 2006-04-04 2007-04-04 Matière échangeuse d'ions, colonne échangeuse d'ions et procédé de réalisation associé

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EP2001592A2 true EP2001592A2 (fr) 2008-12-17

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EP07727789A Withdrawn EP2001592A2 (fr) 2006-04-04 2007-04-04 Matière échangeuse d'ions, colonne échangeuse d'ions et procédé de réalisation associé

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US (1) US20090118382A1 (fr)
EP (2) EP1842592A1 (fr)
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WO (1) WO2007122085A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5980831B2 (ja) * 2013-03-26 2016-08-31 富士フイルム株式会社 高分子機能性膜の製造方法
EP3181227A4 (fr) * 2014-08-14 2017-08-23 Fujifilm Corporation Membrane fonctionnelle polymère pour éliminer les ions nitrate, procédé pour sa production, module à membrane de séparation et dispositif d'échange d'ions
US11717202B2 (en) 2019-04-10 2023-08-08 Foothold Labs Inc. Mobile lab-on-a-chip diagnostic system
WO2022245080A1 (fr) * 2021-05-17 2022-11-24 고려대학교 산학협력단 Procédé de fabrication d'une membrane composite à film mince pour l'électrolyse d'eau alcaline
US20250319443A1 (en) * 2022-05-25 2025-10-16 Korea University Research And Business Foundation Method for manufacturing a thin-film composite membrane for water treatment, having extreme acid and alkaline stability

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3290415A (en) * 1959-03-26 1966-12-06 Du Pont Graft copolymer of polymeric hydrocarbon and organic acid bearing radical
DE2446375C2 (de) * 1973-10-02 1982-03-25 The Dow Chemical Co., 48640 Midland, Mich. Ionenaustauschzusammensetzung und deren Verwendung
CA1331254C (fr) * 1989-02-27 1994-08-02 Victor Berber Barretto Composition echangeuse d'ions fixee a un dispersant au moyen d'une resine et methode de preparation
US5648400A (en) * 1992-08-04 1997-07-15 Japan Atomic Energy Research Inst. Process for producing polymeric electrolyte complex and ion-exchange resin
JP3245454B2 (ja) * 1992-08-04 2002-01-15 日本原子力研究所 イオン交換樹脂の製造法
WO1997031864A1 (fr) * 1996-03-01 1997-09-04 Dionex Corporation Resines d'echange d'anions portant au moins deux groupes differents d'echange d'ions contenant de l'azote
JP3740958B2 (ja) * 2000-07-05 2006-02-01 三菱化学株式会社 固体表面の修飾方法
NZ523914A (en) * 2000-08-29 2004-02-27 Mallinckrodt Baker Inc Functionalized polymeric media for separation of analytes
JP4664609B2 (ja) * 2003-05-27 2011-04-06 株式会社荏原製作所 スルホン酸基を有する有機高分子材料及びその製造方法
JP4147202B2 (ja) * 2003-09-30 2008-09-10 三井化学株式会社 改質酸性イオン交換樹脂触媒およびそれを用いたビスフェノール類の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007122085A2 *

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WO2007122085A3 (fr) 2008-01-17
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US20090118382A1 (en) 2009-05-07
JP2009532551A (ja) 2009-09-10

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