EP1530596A1 - Verfahren zur herstellung von monodispersen gelf rmigen ione naustauschern - Google Patents

Verfahren zur herstellung von monodispersen gelf rmigen ione naustauschern

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Publication number
EP1530596A1
EP1530596A1 EP03793680A EP03793680A EP1530596A1 EP 1530596 A1 EP1530596 A1 EP 1530596A1 EP 03793680 A EP03793680 A EP 03793680A EP 03793680 A EP03793680 A EP 03793680A EP 1530596 A1 EP1530596 A1 EP 1530596A1
Authority
EP
European Patent Office
Prior art keywords
monomer mixture
exchangers
polymer
particle size
seed
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Withdrawn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
EP03793680A
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German (de)
English (en)
French (fr)
Inventor
Wolfgang Podszun
Reinhold Klipper
Dmitry Chernyshov
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
Bayer Chemicals 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 Bayer Chemicals AG filed Critical Bayer Chemicals AG
Publication of EP1530596A1 publication Critical patent/EP1530596A1/de
Withdrawn legal-status Critical Current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
    • 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
    • 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
    • C08F8/36—Sulfonation; Sulfation
    • 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

Definitions

  • the invention relates to a method for producing monodisperse gel-like
  • Ion exchangers are generally obtained by functionalizing crosslinked styrene bead polymers.
  • covalently bonded sulfonic acid groups are obtained by reacting aromatic units of the polymer skeleton with a sulfonating agent, e.g. Produces sulfuric acid.
  • Anion exchangers contain covalently bound amino groups or ammonium groups, which can be generated, for example, by chloromethylation and subsequent amination.
  • monodisperse ion exchangers have become increasingly important because, in many applications, economic advantages can be achieved from monodisperse ion exchangers due to the more favorable hydrodynamic properties of an exchange bed.
  • Monodisperse ion exchangers can be
  • seed / feed process After which a monodisperse bead polymer ("seed") is swollen in the monomer and this is then polymerized.
  • seed / feed processes » 5 are described, for example, in EP 0 098 130 B1 and EP 0 101 943 B1.
  • EP-A 826 704 discloses a seed / feed process in which microencapsulated crosslinked bead polymer is used as the seed.
  • a problem with the known methods for producing monodisperse ion exchangers by seed-feed technology is the provision of monodisperse Persian seeds.
  • a frequently used method is the fractionation of bead polymers with conventional, ie broad particle size distribution.
  • a disadvantage of this process is that the yield of the desired target fraction during screening decreases sharply with increasing monodispersity.
  • Spraying techniques can be used to produce monodisperse bead polymers in a targeted manner.
  • Atomization processes suitable for ion exchangers are described, for example, in EP 0 046 535 B1 and EP 0 051 210 B2. A common characteristic of these atomization processes is their very high technical expenditure. The atomization processes usually lead to ion exchangers with a
  • EP 0 448 391 B1 discloses a process for producing polymer particles of uniform particle size in the range from 1 to 50 ⁇ m. In this process, an emulsion polymer with particle sizes of preferably 0.05 to 0.5 ⁇ m is used as the seed.
  • US Pat. No. 6,239,224 B1 describes a seed-feed process for producing expandable polystyrene beads with a particle size of at least 200 ⁇ m.
  • Cross-linked monodisperse bead polymers with a particle size of 1-30 ⁇ m are known from EP 0 288 006 B1. These bead polymers are obtained by a seed-feed process in which cross-linked seed particles are used.
  • the present invention relates to a process for the production of monodisperse gel-shaped ion exchangers with a particle size of 5 to 500 ⁇ m, which is characterized in that
  • the monomer mixture swells into the seeds and polymerizes at elevated temperature, the steps of adding monomer mixture, swelling and polymerizing, if necessary, repeated one or more times, the monomer mixture containing 2 to 50 wt .-% crosslinking agent in the last addition and
  • the particle size of the ion exchanger according to the invention is 5 to 500 ⁇ m, preferably 10 to 400 ⁇ m, particularly preferably 20 to 300 ⁇ m. Conventional methods such as sieve analysis or image analysis are suitable for determining the average particle size and the particle size distribution.
  • the ratio of the 90% value (0 (90) and the 10% value (0 (10) of the volume distribution is formed as a measure of the width of the particle size distribution of the ion exchangers according to the invention.
  • the 90% value (0 (90) gives the diameter below which 90% of the particles fall below.
  • 10% of the particles fall below the diameter of the 10% value (0 (10).
  • Monodisperse particle size distributions in the sense of the invention mean 0 (90) / 0 (10) ⁇ 1.5, preferably 0 (90) 70 (10) ⁇ 1.25.
  • Monoethylenically unsaturated compounds are used to produce the uncrosslinked seed polymer according to process step a), no multiply ethylenically unsaturated compounds or crosslinking agents being used.
  • Monoethylenically unsaturated compounds for the purposes of the present invention are: styrene, vinyl toluene, alpha-methyl styrene, chlorostyrene, esters of acrylic acid or methacrylic acid such as methyl methacrylate, ethyl methacrylate, ethyl acrylate, isopropyl methacrylate, butyl acrylate, bulyl methacrylate, hexyl methacrylate, 2-ethylhexyl acrylate, ethyl Dodecyl methacrylate, stearyl methacrylate, or iso-bornyl methacrylate.
  • Styrene, methyl acrylate or butyl acrylate are preferably used. Mixtures of different monoethylenically unsaturated compounds are also very suitable.
  • the abovementioned monoethylenically unsaturated compound (s) are used in the presence of a nonaqueous
  • Non-aqueous solvents suitable according to the invention are dioxane, acetone, acetonitrile, dimethylformamide or alcohols.
  • Alcohols in particular methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and tert-butanol, are preferred.
  • Mixtures of different solvents, in particular mixtures of different alcohols, are also very suitable.
  • the alcohols can optionally also contain up to 50% by weight of water, preferably up to 25% by weight of water.
  • non-polar solvents in particular hydrocarbons, such as hexane, heptane and toluene, can also be used
  • Proportions up to 50 wt .-% can be used.
  • the ratio of monoethylenically unsaturated compounds to solvents is 1: 2 to 1:30, preferably 1: 3 to 1:15.
  • the seed polymer is preferably prepared in the presence of a high molecular weight dispersant dissolved in the solvent.
  • Natural and synthetic macromolecular compounds are suitable as high molecular weight dispersants.
  • examples are cellulose derivatives, such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl acetate, partially saponified polyvinyl acetate, polyvinyl pyrrolidone, copolymers of vinyl pyrrolidone and vinyl acetate, and copolymers of styrene and maleic anhydride.
  • polyvinylpyrrolidone is preferred.
  • the content of high molecular weight dispersant is 0.1 to 20% by weight, preferably 0.2 to 10% by weight, based on the solvent.
  • ionic and non-ionic surfactants can also be used.
  • Suitable surfactants are e.g. Sodium sulfosuccinic acid, methyltricaprylammonium chloride or ethoxylated nonylphenols. Ethoxylated nonylphenols having 4 to 20 ethylene oxide units are preferred.
  • the surfactants can be used in amounts of 0.1 to 2% by weight, based on the solvent.
  • Initiators suitable for the production of the seed polymer are compounds which form free radicals when the temperature rises. Examples include: peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide, bis (p-chlorobenzoyl) peroxide, dicyclohexylperoxydicarbonate or tert-amylperoxy-2-ethylhexane, and further azo compounds such as 2,2'-azobis (isobutyronitrile) or 2,2'- Azobis (2-methylisobutyronitrile). If the solvent contains a share of water, is also
  • Sodium or potassium peroxydisulfate is suitable as an initiator.
  • aliphatic "peroxy esters are tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-Butylper- oxyoctoat, tert-butyl peroxy-2-ethylhexanonate, t-butyl peroxyneodecanoate, tert-
  • the initiators are generally used in amounts of 0.05 to 6.0% by weight, preferably 0.2 to 4.0% by weight, based on the monoethylenically unsaturated compounds).
  • Inhibitors soluble in the solvent can be used.
  • suitable inhibitors are phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butyl pyrocatechol, condensation products from phenols with aldehydes.
  • Other organic inhibitors are nitrogen-containing compounds such as Diethyl hydroxylamine and isopropyl hydroxylamine.
  • Resorcinol is preferred as an inhibitor.
  • the concentration of the rhodium is 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the monoethylenically unsaturated compounds.
  • the polymerization temperature depends on the decomposition temperature of the initiator and on the boiling point of the solvent and is typically in the range from 50 to 150 ° C., preferably 60 to 120 ° C. It is beneficial in the
  • the polymerization time is generally several hours, e.g. 2 to 30 hours.
  • the seed polymers produced in process step a) according to the invention are highly monodisperse and have particle sizes of 0.5 to 20 ⁇ m, preferably 2 to 15 ⁇ m. It was found in the context of the present work that the particle size can be influenced, among other things, by the choice of the solvent. For example, higher alcohols such as n-propanol, iso-propanol, n-butanol, iso-butanol and tert-butanol provide larger particles than methanol. The particle size can be shifted to lower values by a proportion of water or hexane in the solvent. The addition of toluene increases the particle size.
  • the seed polymer can be isolated by conventional methods, such as sedimentation, centrifugation or filtration. To separate the dispersing agent, it is washed with alcohol and / or water and dried.
  • the seed polymer is mixed with an activated styrene-containing monomer mixture as a feed.
  • styrene-containing means that the mixture contains 50 to 99.9, preferably 80 to 99.9% by weight of styrene.
  • the remaining components of the mixture are
  • Suitable comonomers are compounds which can be copolymerized with styrene, e.g. Methyl methacrylate, ethyl methacrylate, ethyl acrylate, hydroxyethyl methacrylate or acrylonitrile.
  • Crosslinkers are compounds with two or more polymerizable olefinically unsaturated double bonds in the molecule.
  • Examples include divinyl benzene, allyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, butanediol divinyl ether and octadiene.
  • Divinylbenzene is preferred.
  • the divinylbenzene can be used in commercially available quality, which in addition to the isomers of divinylbenzene also contains ethylvinylbenzene.
  • the initiators for process step b) are the radical formers described in process step a).
  • the initiators are generally in Amounts of 0.1 to 4.0 wt .-%, preferably 0.5 to 2.5 wt .-% based on the monomer mixture used.
  • mixtures of the aforementioned radical formers can also be used, for example mixtures of initiators with different decomposition temperatures.
  • the weight ratio of seed polymer to monomer mixture is 1: 1 to 1: 1000, preferably 1: 2 to 1: 100, particularly preferably 1: 3 to 1:30.
  • the monomer mixture is generally added to the seed polymer in such a way that an aqueous dispersion of the seed polymer is used
  • Emulsion of the monomer mixture is added. Finely divided emulsions with average particle sizes of 1 to 10 ⁇ m, which are produced using rotor-stator mixers or mixed jet nozzles using an emulsifying agent, such as e.g. Isoctyl sulfosuccinic acid sodium salt can be prepared.
  • an emulsifying agent such as e.g. Isoctyl sulfosuccinic acid sodium salt
  • the monomer mixture can be added at temperatures below the decomposition temperature of the initiator, for example at room temperature. It is advantageous to stir the emulsion containing the monomer mixture with stirring for a longer period, e.g. meter in within 0.25 to 3 hours. After the emulsion has been added completely, stirring is continued until the monomer has completely penetrated the seed particles. This usually takes 0.5 to 2 hours and can be easily checked by observing a sample with light microscopy. The amounts of water used in the production of the seed polymer suspension and monomer mixture emulsion are large
  • the mixture of seed polymer, monomer mixture and water obtained is mixed with at least one dispersing aid, natural and synthetic water-soluble polymers, such as gelatin, starch, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid or copolymers of (meth) acrylic acid or (meth) acrylic acid esters are suitable.
  • Cellulose derivatives, in particular cellulose esters or cellulose ethers, such as carboxymethyl cellulose or hydroxyethyl cellulose, are also very suitable.
  • the amount of dispersant used is generally 0.05 to 1%, preferably 0.1 to 0.5%, based on the water phase.
  • the water phase can also contain a buffer system which adjusts the pH of the water phase to a value between 12 and 3, preferably between 10 and 4.
  • buffer systems contain phosphate, acetate,
  • inorganic and organic substances can be considered as inhibitors.
  • inorganic inhibitors are nitrogen compounds such as hydroxylamine, hydrazine, sodium nitrite and potassium nitrite.
  • organic inhibitors are phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butyl pyrocatechol, condensation products from phenols with aldehydes.
  • Other organic inhibitors are nitrogen-containing compounds such as Diethylhydroxylamine or isopropylhydroxylamine.
  • resorcinol is preferred as an inhibitor.
  • the concentration of the inhibitor is 5-1000, preferably 10-500, particularly preferably 20-250 ppm, based on the aqueous phase.
  • the polymerization of the monomer mixture swollen in the seed particles is initiated at 60-130 ° C.
  • the polymerization takes several hours, e.g. 3 to 10 hours.
  • the monomer mixture is added over a longer period of 1 to 6 hours at Temperature at which at least one of the initiators used is active. In general, temperatures of 60-130 ° C., preferably 60-95 ° C., are used in this procedure.
  • the feed step i.e. Addition of monomer mixture, swelling and polymerizing can be done one or more times, e.g. Repeat 2 to 10 times. This means that the product produced in a previous feed step is used as a seed polymer for the subsequent feed step. Due to the repeated repetition of the feed steps, monodisperse seed polymers with particle sizes of 0.5 to 20 ⁇ m are ultimately monodisperse polymers
  • Particle sizes of up to 500 ⁇ m accessible Particle sizes of up to 500 ⁇ m accessible.
  • the enlargement factor results from the weight ratio of seed polymer to monomer mixture. This is again 1: 1 to 1: 1000, preferably 1: 2 to 1: 100, particularly preferably 1: 3 to 1:30.
  • crosslinker content in the monomer mixture is important for the high monodispersity of the ion exchangers obtained. If the feed steps are repeated several times, crosslinkers are only used in the last feed step.
  • the amount of crosslinker in the last feed step is 2 to 50% by weight, preferably 3 to 20% by weight, in each case based on the activated styrene-containing monomer mixture added.
  • the polymer formed can be processed using the usual methods, e.g. isolated by filtration or decanting and, if necessary, dried once or several times and sieved if desired.
  • the polymer from process step b) can be converted to the ion exchanger according to process step c) by known processes.
  • Cation exchangers are manufactured by sulfonation. Suitable sulfonating agents are sulfuric acid, sulfur trioxide and chlorosulfonic acid. Is preferred
  • the temperature during the sulfonation is generally 50-200 ° C., preferably 90-130 ° C.
  • a swelling agent such as chlorobenzene, dichloroethane, dichloropropane or methylene chloride can be used in the sulfonation.
  • the reaction mixture is stirred.
  • stirrers such as blade, anchor, grid or turbine stirrers, can be used. It has been shown that a radially demanding double turbine stirrer is particularly well suited.
  • reaction mixture of sulfomerization product and residual acid is cooled to room temperature and first diluted with decreasing concentrations of sulfuric acids and then with water.
  • the cation exchanger obtained according to the invention can be any suitable cation exchanger obtained according to the invention.
  • Form for cleaning with deionized water at temperatures of 70 - 145 ° C, preferably from 105 - 130 ° C are treated.
  • Concentration of 10-60%, preferably 40-50% In the context of the present work, it was determined that the temperature is important during transhipment. It has been shown that at charge temperatures of 60-120 ° C, preferably 75-100 ° C, there are no defects on the ion exchange balls and the purity is particularly high.
  • Anion exchangers can be obtained, for example, by amidoalkylation of the polymer from process step b) and subsequent hydrolysis.
  • N-hydroxymethylphthalimide and bis (phthalimidomethyl) ether are particularly suitable as Ajxiidoalkyl réellesstoff.
  • aminomethylated crosslinked polystyrene bead polymerizates are obtained which are weakly basic anion exchangers.
  • weakly basic anion exchangers can be converted into medium-based ones by reaction with formic acid / formaldehyde after the LeuckartAVallach reaction
  • Anion exchangers or quaternization with alkyl halides such as chloromethane or ethyl chloride can be converted into strongly basic anion exchangers.
  • Anion exchangers can also be prepared by haloalkylation of the polymer from process step b) and subsequent amination.
  • a preferred haloalkylating agent is chloromethyl methyl ether.
  • Weakly basic anion exchangers can be obtained from the haloalkylated polymers by reaction with a secondary amine, such as dimethylamine. The reaction of the haloalkylated polymers with tertiary amines, such as
  • Trimethylamine, dimethylisopropylamine or dimethylaminoethanol strongly basic anion exchangers.
  • Chelate resins can also be produced in a simple manner from the polymers according to the invention.
  • the reaction of a haloalkylated polymer with iminodiacetic acid gives chelate resins of the iminodiacetic acid type.
  • the ion exchangers obtained by the process according to the invention are notable for high monodispersity, particularly high stability and purity.
  • the invention therefore relates to monodisperse gel-like anion exchangers or monodisperse gel-like cation exchangers with a particle size of 5 to 500 ⁇ m, obtainable by
  • Seed polymer allowing the monomer mixture to swell into the seeds and polymerizing at elevated temperature, optionally repeating the steps of adding the monomer mixture once or several times, allowing the polymer mixture to swell and polymerizing, the monomer mixture containing 2 to 50% by weight of crosslinking agent in the last addition and
  • sugars preferably of mono- or disaccharides, in particular cane sugar, beet sugar solutions, fructose solutions, for example in the sugar industry, dairies, starch and in the pharmaceutical industry,
  • humic acids for example humic acids from surface water.
  • anion exchangers according to the invention can be used for the reverse amines. Furthermore, the anion exchangers according to the invention can be used for the reverse amines.
  • anion exchangers according to the invention can be used in combination with gel-like and / or macroporous cation exchangers for the complete demineralization of aqueous solutions and / or condensates, in particular in the sugar industry.
  • the cation exchangers produced according to the invention are also used, for example, in drinking water treatment, in the production of ultrapure water (necessary for microchip production for the computer industry), for the chromatographic separation of glucose and fructose and as catalysts for various chemical reactions (such as bisphenol-A -Manufacture from phenol and acetone).
  • ultrapure water non-pure water
  • chromatographic separation of glucose and fructose and as catalysts for various chemical reactions such as bisphenol-A -Manufacture from phenol and acetone
  • the presence of refinements in the water flowing away from the cation exchanger is noticeable in that the conductivity and / or the organic carbon content (TOC content) of the
  • the cation exchangers according to the invention are also extremely suitable for the complete demineralization of water. No increased conductivity is observed even after the desalination plants have been standing for a long time. Even if the structure-property correlation of the cation exchangers according to the invention is not known in all details, it is likely that the favorable leaching properties can be attributed to the special network structure.
  • the present invention therefore relates to the use of the cation exchangers according to the invention
  • aqueous or organic solutions and condensates e.g. Process or turbine condensates
  • the present invention therefore also relates to Process for the complete demineralization of aqueous solutions and or condensates, such as process or turbine condensates, characterized in that, according to the invention, monodisperse cation exchangers are used in combination with heterodisperse or monodisperse, gel-like and / or macroporous anion exchangers,
  • Process for softening by neutral exchange of aqueous or organic solutions and condensates e.g. Process or turbine condensates, characterized in that the monodisperse cation exchangers according to the invention are used,
  • 100 ml of the aminomethylated, crosslinked bead polymer are shaken in a tamping volumeter under water and then transferred to a glass column. 1000 ml of 2 wt. Are added over the resin in 1 hour and 40 minutes. %, aqueous sodium hydroxide solution filtered. Then, fully deionized water is filtered through the resin until 100 ml of the eluate flowing out of the resin mixed with phenol phthalein is used in the titration with 0.1 normal hydrochloric acid not more than 0.05 ml.
  • the amount of ammomethyl groups in the total amount of resin is determined by the above method.
  • the molar amount of aromatic nuclei in the amount of bead polymer is calculated by dividing the amount of bead polymer by the molecular weight.
  • the degree of substitution of the aromatic nuclei in the crosslinked polystyrene bead polymer is then 0.82.
  • the bead polymer to be tested is distributed in a uniform layer thickness between two plastic wipes.
  • the cloths are placed on a firm, horizontally attached support and subjected to 20 working cycles in a rolling apparatus.
  • the work cycle consists of rolling back and forth. After rolling, the number of undamaged beads is determined on representative samples of 100 beads each by counting under the microscope.
  • the resin is washed with deionized water and rinsed in a beaker. 100 ml of 1N hydrochloric acid are added and the mixture is left to stand for 30 minutes. The entire suspension is rinsed into a glass column. A further 100 ml of hydrochloric acid are filtered through the resin. The resin is washed with methanol. The drain is made up to 1,000 ml with deionized water. 50 ml of this are titrated with 1N sodium hydroxide solution.
  • the amount of weakly basic groups is equal to the HO number.
  • chelate resin to be examined 50 ml are poured into a glass column and treated with 0.1 normal sodium hydroxide solution. The effluent is collected in a 250 ml glass flask and the entire amount is titrated against methyl orange with 1 normal hydrochloric acid.
  • a solution of 5 g of methylhydroxyethyl cellulose in 2300 g of deionized water and 200 g of aqueous dispersion from a) is introduced into a 4 1 three-necked flask which has been flushed with a nitrogen stream of 20 l / h.
  • the finely divided emulsion-I is stirred with constant pumped speed.
  • the mixture is then left at room temperature for a further 3 hours at room temperature and then heated to 80 ° C. for 9 hours.
  • the reaction mixture is then cooled to room temperature, the resulting polymer is isolated by centrifugation and washed twice with water and dispersed in water. In this way, 1500 g of an aqueous dispersion with a solids content of 20% by weight are obtained.
  • the particle size is 8.8 ⁇ m, 0 (90) 70 (10) is 1.10.
  • a solution of 5 g of methylhydroxyethyl cellulose in 2300 g of deionized water and 200 g of aqueous dispersion from B1) is introduced into a 4 1 three-necked flask which has been flushed with a nitrogen stream of 20 l / h.
  • the finely divided emulsion from b2) is pumped in at a constant rate over the course of 3 hours.
  • the mixture is then left at room temperature for a further 3 hours at room temperature and then heated to 80 ° C. for 9 hours.
  • Example 1a a monodisperse seed polymer with a particle size of 4.5 ⁇ m is produced.
  • a solution of 5 g of methylhydroxyethyl cellulose in 2300 g of deionized water and 200 g of aqueous dispersion from a) is introduced into a 4 1 three-necked flask which has been flushed with a nitrogen stream of 20 l / h.
  • the finely divided emulsion-I pumped in at constant speed within 3 hours.
  • the mixture is then left at room temperature for a further 3 hours at room temperature and then heated to 80 ° C. for 9 hours.
  • the reaction mixture is then cooled to room temperature, the resulting polymer is isolated by centrifugation and washed twice with water and in
  • a second feed step is carried out while maintaining the conditions of the first feed step.
  • the resulting bead polymer is washed and dried. 308 g of bead polymer having a particle size of
  • a third feed step is carried out using 813.38 g of emulsion I and 40 g of bead polymer from b2) while maintaining the conditions of the second feed step.
  • the resulting bead polymer is washed and dried. 315 g of bead polymer with a particle size of 26 ⁇ m are obtained. 0 (90) 70 (10) is 1.15.
  • a fourth feed step is carried out while maintaining the conditions of the third feed step.
  • the resulting bead polymer is washed and dries. 318 g of bead polymer with a particle size of 49 ⁇ m are obtained. 0 (9O) / 0 (10) is 1.18.
  • a fifth feed step is carried out while maintaining the conditions of the fourth feed step.
  • the bead polymer obtained is washed and dried. 325 g of bead polymer with a particle size of 99 ⁇ m are obtained ) / 0 (10) is 1.2.
  • Phthalic acid 1.6% bis (phthalimidomethyl) ether: 90.3% 3 c) N-acetoxymethylphthalimide
  • the suspension of bis (phthalimidomethyl) ether obtained is heated to 60 ° C. Then 96.9 g of acetic anhydride are metered in over 5 minutes. After the dosing has been completed, a clear solution is available. The mixture is stirred at 60 ° C. for 15 minutes, then heated to 80 ° C. and stirred at this temperature for 10 minutes. A sample is then taken and the composition is analyzed by thin layer chromatography.
  • the suspension is then heated to 80 ° C. for 2 hours. Then the mixture is stirred for a further 10 hours at this temperature. The pH is adjusted during this time by dosing 20 wt. % sodium hydroxide solution kept at 10.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
EP03793680A 2002-08-16 2003-08-02 Verfahren zur herstellung von monodispersen gelf rmigen ione naustauschern Withdrawn EP1530596A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10237601A DE10237601A1 (de) 2002-08-16 2002-08-16 Verfahren zur Herstellung von monodispersen gelförmigen Ionenaustauschern
DE10237601 2002-08-16
PCT/EP2003/008600 WO2004022611A1 (de) 2002-08-16 2003-08-02 Verfahren zur herstellung von monodispersen gelförmigen ionenaustauschern

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US (1) US20060199892A1 (OSRAM)
EP (1) EP1530596A1 (OSRAM)
JP (1) JP2005535778A (OSRAM)
CN (1) CN100349927C (OSRAM)
AU (1) AU2003255363A1 (OSRAM)
DE (1) DE10237601A1 (OSRAM)
NO (1) NO20051271L (OSRAM)
WO (1) WO2004022611A1 (OSRAM)

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CN1688617A (zh) 2005-10-26
JP2005535778A (ja) 2005-11-24
US20060199892A1 (en) 2006-09-07
NO20051271L (no) 2005-03-11
CN100349927C (zh) 2007-11-21
DE10237601A1 (de) 2004-02-26

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