EP1713588A2 - Procede de fabrication de polymerisats en perles monodisperses contenant des acryliques - Google Patents

Procede de fabrication de polymerisats en perles monodisperses contenant des acryliques

Info

Publication number
EP1713588A2
EP1713588A2 EP05701149A EP05701149A EP1713588A2 EP 1713588 A2 EP1713588 A2 EP 1713588A2 EP 05701149 A EP05701149 A EP 05701149A EP 05701149 A EP05701149 A EP 05701149A EP 1713588 A2 EP1713588 A2 EP 1713588A2
Authority
EP
European Patent Office
Prior art keywords
monodisperse
acrylic
weight
monomer feed
aqueous
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Withdrawn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
EP05701149A
Other languages
German (de)
English (en)
Inventor
Wolfgang Podszun
Pierre Vanhoorne
Dmitri 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
Lanxess Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP1713588A2 publication Critical patent/EP1713588A2/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/142—Amino acids; Derivatives thereof
    • A23K20/147—Polymeric derivatives, e.g. peptides or proteins
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/163—Sugars; Polysaccharides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/179—Colouring agents, e.g. pigmenting or dyeing agents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K40/00—Shaping or working-up of animal feeding-stuffs
    • A23K40/10—Shaping or working-up of animal feeding-stuffs by agglomeration; by granulation, e.g. making powders
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K50/00—Feeding-stuffs specially adapted for particular animals
    • A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
    • A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K50/00—Feeding-stuffs specially adapted for particular animals
    • A23K50/80—Feeding-stuffs specially adapted for particular animals for aquatic animals, e.g. fish, crustaceans or molluscs
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/40—Colouring or decolouring of foods
    • A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
    • A23L5/43—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
    • A23L5/44—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives using carotenoids or xanthophylls
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/01—Hydrocarbons
    • A61K31/015—Hydrocarbons carbocyclic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0002—Grinding; Milling with solid grinding or milling assistants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0092—Dyes in solid form
    • 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 process for the production of monodisperse acrylic ion exchangers, the intermediates necessary for this, which are referred to as monodisperse acrylic bead polymers and which preferably have a particle size of 5 to 500 ⁇ m, and the use of the mohodisperse acrylic ion exchanger.
  • Weakly acidic cation exchangers are generally obtained by hydrolysis of crosslinked acrylic bead polymers.
  • Crosslinked polymethylacrylate or polyacrylonitrile bead polymers are converted into beads containing carboxylate by reaction with sulfuric acid or sodium hydroxide solution.
  • weakly basic anion exchangers can also be obtained by reacting the acrylate groups with diamines. By alkylating these weakly basic anion exchangers, strongly basic anion exchangers can be produced.
  • monodisperse ion exchangers with a particle size that is as uniform as possible
  • monodisperse ion exchangers with a particle size that is as uniform as possible
  • monodisperse ion exchangers can achieve economic advantages.
  • Monodisperse ion exchangers can be functionalized by monodisperse bead polymer can be obtained.
  • seed / feed process After which a monodisperse polymer (“seed”) is swollen in the monomer and this is then polymerized.
  • seed / feed processes are described, for example, in EP-00 98 130 B1 and EP 0 101 943 B1.
  • EP-A 0 826 704 discloses a seed feed method 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 seeds.
  • a frequently used method is the fractionation of bead polymers with conventional, i.e. 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 0051 210 B1. A common characteristic of these atomization processes is their very high technical expenditure. The atomization processes usually lead to ion exchanger with a particle size of 500 to 1200 ⁇ m. Ion exchangers with smaller particle sizes cannot be produced or can only be produced with significantly increased effort.
  • EP-A 0 448 391 discloses a process for producing polymer particles of uniform particle size in the range from 1 to 50 ⁇ m.
  • an emulsion polymer with particle sizes of preferably 0.05 to 0.5 ⁇ m is used as the seed.
  • the small diameter of the seed particles used is unfavorable because many repetitions of the feed steps are necessary.
  • Cross-linked monodisperse bead polymers with a particle size of 1 to 30 ⁇ m are known from EP-A 0 288 006. These bead polymers are obtained by a seed-feed process in which cross-linked seed particles are used.
  • DE-A 102 37601 discloses monodisperse gel-shaped ion exchangers with a diameter of up to 500 ⁇ m, where a monomer mixture is added to a seed polymer as feed which contains 50 to 99.9% by weight of styrene and compounds which can be copolymerized as comonomers, such as eg Contains methyl methacrylate, ethyl methacrylate, ethyl acrylate, hydroxyethyl methacrylate or acrylonitrile.
  • Narrowly distributed acrylic bead polymers or narrowly distributed weakly acidic cation exchangers in the range from 30 to 500 ⁇ m are usually obtained by fractionating bead polymers or weakly acidic cation exchangers with a broad particle size distribution.
  • a disadvantage of this process is that the yield of the desired target fraction in the fractionation decreases sharply with increasing monodispersity.
  • the object of the present application was therefore to provide a process for the targeted production of monodisperse acrylic ion exchangers.
  • the present invention relates to a process for the preparation of monodisperse acrylic ion exchangers, characterized in that a) an uncrosslinked monodisperse seed polymer having a particle size of 0.5 to 20 ⁇ m is obtained by radical-initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent generated,
  • a monomer feed is added to an aqueous dispersion of the seed polymer in the presence of a dispersant, which
  • the monomer feed can swell into the seeds and polymerize at elevated temperature to form crosslinked monodisperse acrylic-containing bead polymers, preferably with a particle size of 5 to 500 ⁇ m
  • At least one monomer feed in a process step a ') can be added to an aqueous dispersion of the seed polymer from process step a) in the presence of a dispersant
  • Process step a ') can be repeated one or more times before the process is continued with process step b). This measure enables uncured seed polymers of any particle size in the range from 1 to 300 ⁇ m to be obtained.
  • the present invention relates to both the monodisperse acrylic ion exchangers according to process step c) and the intermediates obtainable after process step b), the crosslinked monodisperse acrylic bead polymers.
  • the monodisperse acrylic-containing bead polymers have a particle size of 5 to 500 ⁇ m, preferably 10 to 400 ⁇ m, particularly preferably 20 to 300 ⁇ m, very particularly preferably 51 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 monodisperse acrylic ion exchangers according to the invention.
  • the 90% value (0 (90)) indicates the diameter, which is below 90% of the particles.
  • 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 (9O) / 0 (10) ⁇ 1.5, preferably 0 (9O) / 0 (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.
  • Monoethylenic compounds suitable according to the invention are: styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, esters of acrylic acid and methacrylic acid such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl acrylate Dodecyimethacrylate, stearyl methacrylate, and iso-bornyl methacrylate. Styrene, methyl acrylate and butyl acrylate are preferred. Mixtures of different monoethylenically unsaturated compounds are also very suitable.
  • the abovementioned monoethylenically unsaturated compound (s) are polymerized in the presence of a non-aqueous solvent using an initiator.
  • Suitable solvents according to the invention are dioxane, acetone, acetonitrile, dimemylformamide and 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 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 in proportions of up to 50% by weight.
  • the ratio of monoethylenically unsaturated compounds to solvents is 1: 2 to 1:30, preferably 1: 3 to 1:15.
  • the seed polymer according to process step a) is preferably produced 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.
  • Polyvinyl pyrrolidone 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 or non-ionic surfactants can also be used.
  • Suitable surfactants for the purposes of the present invention are e.g. Sulfosuccinic acid sodium salt, memyltricaprylammonium 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 preparation of the seed polymer to be prepared in process step a) 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 and tert-amylperoxy-2-ethylhexane, and further azo compounds such as 2,2'-azobis (isobutyronitrile) or 2,2 azobis (2-methylisobutyronitrile). If the solvent contains water, sodium or potassium peroxydisulfate is also suitable as an initiator.
  • peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide, bis (p-chlorobenzoyl) peroxide, dicyclohexylperoxydicarbonate and tert-amylperoxy-2-ethylhexane
  • azo compounds such
  • Aliphatic peroxyesters are also very suitable. Examples of these are tert-butyl peroxy acetate, tert-butyl peroxy isobutyrate, tert-butyl peroxypivalate, tert-butyl peroxy octoate, tert-buryl peroxy-2-ethylhexanoate, tert-butyl peroxy neodecanoate, tert-amyl peroxypivalate, tert-amyl peroxy-octylate -2-ethylhexanoate, tert-a ylperoxyneodecanoate, 2,5-bis (2-ethylhexanoylperoxy) - 2,5-dimethylhexane, 2,5-dipivaloyl-2,5-dimethylhexane, 2,5-bis (2-neodecanoylperoxy) -2,5-dimethylhexane, di-
  • the initiators are generally used in amounts of 0.05 to 6.0% by weight, preferably 0.2 to 5.0% by weight, particularly preferably 1 to 4% by weight, based on the sum of the monoethylenically unsaturated Connections.
  • 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 or isopropylhydroxylamine.
  • resorcinol is preferred as an inhibitor.
  • the concentration of the inhibitor is 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the sum of 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 advantageous to polymerize at the boiling point of the solvent with constant stirring, for example using a grid stirrer. Low stirring speeds are used. In the case of 4 liter laboratory reactors, the stirring speed of a lattice stirrer is 100 to 250 rpm, preferably 100 rpm.
  • the polymerization time is generally several hours, e.g. 2 to 30 hours.
  • the seed polymers produced according to method step a) are highly monodisperse and have particle sizes of 0.5 to 20 ⁇ m, preferably 2.2 to 15 ⁇ m.
  • the particle size can be influence by the choice of 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 monoethylenically unsaturated compounds to be used in process step a ') are: styrene, vinyl toluene, ⁇ -methylstyrene, chlorostyrene, esters of acrylic acid and methacrylic acid, such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, hexyl ethyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate , Decyl methacrylate, dodecyl methacrylate, stearyl methacrylate, and iso-bornyl methacrylate.
  • the initiators described under process step a) can be used as mandatory initiators in the monomer feed of process step a ').
  • the initiators are generally used in amounts of 0.1 to 5.0% by weight, preferably 0.5 to 3% by weight, based on the monomer feed.
  • Free radical formers are used, for example mixtures of initiators with different decomposition temperatures.
  • the weight ratio of seed polymer to monomer feed of process step a ') is 1: 1 to 1: 1000, preferably 1: 2 to 1: 100, particularly preferably 1: 3 to 1.30.
  • the addition of the monomer feed to the seed polymer of process step a) or an upstream process step a ') is generally carried out in such a way that a finely divided aqueous emulsion of the monomer feed is added to an aqueous dispersion of the seed polymer.
  • Finely divided emulsions with average particle sizes of 1 to 10 ⁇ m are particularly suitable, which are prepared with the aid of rotor-stator mixers or mixed jet nozzles using emulsifying aids, e.g. Isoctyl sulfosuccinic acid sodium salt can be prepared.
  • the constituents of the monomer feed according to process step a ') can be added together or else individually to the seed polymer, the individual constituents being added in each step in the form of a finely divided emulsion as described above.
  • the composition of the sum of all added organic phases (monomer feed) is decisive for the present invention. In the case of metering in several metering steps, it may be advantageous to add the total amount of initiator in the first metering step.
  • the monomer feed in process step a ') can be added at temperatures below the decomposition temperature of the initiator, for example at room temperature. It is advantageous to mix the emulsion (s) containing the monomer feed with stirring for a relatively long period of time, e.g. meter in within 0.25 to 5 hours. After the emulsion (s) have been completely added, stirring is continued, the monomer feed penetrating into the seed particles. A subsequent stirring time of 1 to 15 hours is favorable.
  • the amounts of water used in the production of the seed polymer suspension and monomer mixture emulsion are not critical within wide limits. In general, 5 to 50% suspensions or emulsions are used.
  • the resulting mixture of seed polymer, monomer feed and water is also mixed in process step a ') with at least one dispersing aid, natural and synthetic water-soluble polymers, such as gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, 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 dispersion aid used is generally 0.05 to 1%, preferably 0.1 to 0.5%, based on the water phase.
  • the water phase of process step a ') 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 which are particularly suitable contain phosphate, acetate, citrate or borate salts.
  • inorganic inhibitors are nitrogen compounds such as hydroxylamine, hydrazine, sodium nitrite or Kdiirmnitrit.
  • organic inhibitors are phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butyl pyrocatechol or condensation products from phenols with aldehydes.
  • Other organic additives are nitrogenous compounds such as Diethylhydroxyla in or Isopropylhydroxylarnin.
  • Resorcinol is preferred as an inhibitor according to the invention.
  • the concentration of the inhibitor is 5 to 1000 ppm, preferably 10 to 500 ppm, particularly preferably 20 to 250 ppm, based on the aqueous phase.
  • an elevated temperature for process step a ') in the sense of the present invention to increase the temperature to the decomposition temperature of the initiator, generally 60 to 130.degree. This initiates the polymerization of the monomer feed swollen into the seed particles. The polymerization takes several hours, e.g. 3 to 10 hours.
  • the monomer feed is added over a longer period of 1 to 6 hours at a temperature at which at least one of the initiators used is active.
  • temperatures of 60 to 130 ° C., preferably 60 to 95 ° C., are used in this procedure.
  • the monodisperse, uncrosslinked seed polymer from process step a ') can be carried out using the customary methods, e.g. isolated by filtration or decanting and, if necessary, dried once or several times and, if desired, sieved and stored.
  • the seed polymer from a) or a ') is mixed with a feed of an acrylic monomer with initiator and crosslinker.
  • the monomer feed of process step b) contains 30 to 98.9% by weight of acrylic monomer, preferably 50 to 97.9% by weight of acrylic monomer.
  • acrylic monomers are esters of acrylic acid and methacrylic acid, such as, for example, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl acrylate, ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, dodecyl methacrylate, N'-dimemylaminoethyl acrylate, N, N'-dimethylaminoethyl methacrylate, glycidyl acrylate and glycidyl methacrylate, further acrylonitrile, methacrylonitrile, acrylamide or methacrylamide.
  • the monomer feed of process step b) can optionally contain further comonomers.
  • Suitable comonomers are compounds copolymerizable with acrylic monomers, such as e.g. ⁇ -methyl styrene, ethyl vinyl ether, methyl vinyl ether, tert-butyl vinyl ether, N-vinyl pyrrolidones, N-vinyl pyridines, 2-vinyl pyridines and 4-vinyl pyridines.
  • the amount of co onomers is 0 to 68.9% by weight, preferably 0 to 48.9% by weight, based in each case on the activated monomer feed added.
  • the monomer feed of process step b) contains 1 to 60% by weight crosslinking agent, based on the activated monomer feed added.
  • Crosslinkers are compounds with two or more polymerizable olefinic double bonds in the molecule. Examples include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, butanediol divinyl ether, diethylene glycol divinyl ether or octadiene. Divinylbenzene, octadiene or diethylene glycol divinyl ether are preferred.
  • the divinylbenzene can be used in commercially available quality, which contains not only the isomers of divinylbenzene but also ethyl vinylbenzenes.
  • the amount of crosslinker in the monomer feed of process step b) is preferably 2 to 30% by weight, particularly preferably 3 to 18% by weight, based in each case on the activated monomer feed added.
  • the initiators described under process step a) can be used as mandatory initiators in the monomer feed of process step b).
  • the initiators are generally used in amounts of 0.1 to 2.0% by weight, preferably 0.5 to 2% by weight, based on the monomer feed.
  • 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 feed in process step b) is 1: 1 to 1: 1000, preferably 1: 2 to 1: 100, particularly preferably 1: 3 to 1:30.
  • the addition of the monomer feed in process step b) to the seed polymer from a) or a ') is generally carried out in such a way that a finely divided aqueous emulsion of the monomer feed is added to an aqueous dispersion of the seed polymer.
  • Finely divided emulsions with average particle sizes of 1 to 10 ⁇ m which are produced using rotor-stator mixers or mixing jet nozzles using emulsifying aids such as e.g. Sulfobern- stemklakladylester Natrivurisalz, can be prepared.
  • the constituents of the monomer feed in process step b) can be added together or else individually to the seed polymer from a) or a '), the individual constituents being added in each step in the form of a finely divided emulsion as described above.
  • the composition of the sum of all added organic phases (monomer feed) is decisive for the present invention. In the case of metering in several metering steps, it may be advantageous to add the total amount of initiator in the first metering step.
  • the monomer feed in process step b) can be added at temperatures below the decomposition temperature of the initiator, for example at room temperature. It is advantageous to keep the emulsion (s) containing the monomer feed under stirring for a longer period, e.g. meter in within 0.25 to 5 hours. After the emulsion (s) have been completely added, stirring is continued, the monomer feed penetrating into the seed particles. A subsequent stirring time of 1 to 15 hours is favorable.
  • the amounts of water used in the production of the seed polymer suspension and monomer mixture emulsion are not critical within wide limits. In general, 5 to 50% suspensions or emulsions are used.
  • the mixture of seed polymer, monomer feed and water obtained in process step b) is mixed with at least one dispersing agent, natural and synthetic water-soluble polymers, such as e.g. 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 dispersion aid used in process step b) is generally 0.05 to 1%, preferably 0.1 to 0.5%, based on the water phase.
  • the water phase of process step b) 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 which are particularly suitable contain phosphate, acetate, citrate or borate salts. It can be advantageous to use an inhibitor dissolved in the aqueous phase in process step b).
  • both inorganic and organic substances are suitable as inhibitors. Examples of inorganic inhibitors are nitrogen compounds such as hydroxylamine, hydrazine, sodium trimetrite or potassium nitrite.
  • organic inhibitors examples include phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butylpyrocatecliin or condensation products from phenols with aldehydes.
  • Other organic inhibitors are nitrogen-containing compounds such as, for example, die ylhydroxylamine or isopropyl ydroxylarnine.
  • Resorcinol is preferred as an inhibitor according to the invention.
  • the concentration of the inhibitor is 5 to 1000 pm, preferably 10 to 500 ppm, particularly preferably 20 to 250 ppm, based on the aqueous phase.
  • elevated temperature for process step b) as an increase in temperature to the decomposition temperature of the initiator, generally 60 to 130 ° C. This initiates the polymerization of the monomer feed swollen into the seed particles. The polymerization takes several hours, e.g. 3 to 10 hours.
  • the monomer feed in process step b) is added over a longer period of 1 to 6 hours at a temperature at which at least one of the initiators used is active.
  • temperatures of 60 to 130 ° C., preferably 60 to 95 ° C., are used in this procedure.
  • Process step b) makes monodisperse acrylic polymer beads, preferably with particle sizes of up to 500 ⁇ m, accessible from monodisperse seed polymers of process steps a) or a ').
  • the enlargement factor results from the polymerization conversion and the weight ratio of seed polymer from a) or a ') to the monomer feed of process step b).
  • the monodisperse acrylic-containing bead polymer from process step b) can be processed using the customary methods, e.g. isolated by filtration or decanting and, if necessary, dried once or several times and, if desired, sieved and stored.
  • the monodisperse, acrylic-containing bead polymers are used as starting materials for the production of monodisperse ion exchangers.
  • the bead polymers can be converted into ion exchangers by known processes.
  • Weakly acidic cation exchangers are produced by hydrolysis of the monodisperse acrylic bead polymers from process step b). Suitable hydrolysis agents are strong bases or strong acids such as. B. sodium hydroxide solution or sulfuric acid. After the hydrolysis, the reaction mixture of the hydrolysis product and the remaining hydrolysis agent is cooled to room temperature and first diluted with water and washed.
  • the weakly acidic cation exchanger is obtained in the sodium form.
  • sulfuric acid at a concentration of 5 to 50%, preferably 10 to 20%.
  • the weakly acidic cation exchanger obtained according to the invention can be treated for cleaning with deionized water at temperatures from 70 to 145 ° C., preferably from 105 to 130 ° C.
  • Weakly basic anion exchangers can be produced, for example, by reacting the monodisperse acrylic-containing bead polymers prepared by process step b) with an amino alcohol or emembifunctional amine by the process according to the invention.
  • a preferred amino alcohol is N-N'-dimemyl-2-aminoethanol.
  • a preferred bifunctional amine is (N-N'-dimethyl) -3-ammopropylamine ("Amine Z").
  • strongly basic anion exchangers can be prepared by quaternization with alkylating agents such as e.g. Methyl chloride can be produced.
  • the monodisperse acrylic ion exchangers obtained by the process according to the invention are notable for high monodispersity and particularly high stability and, like the monodisperse acrylic bead polymers according to process step b), are the subject of the present invention.
  • the present invention therefore also provides monodisperse acrylic ion exchangers obtainable from
  • initiator 0.1 to 2% by weight of initiator, 1 to 60% by weight of crosslinker and Contains 30 to 98.9% by weight of acrylic monomer, of which up to 49.9% by weight can be replaced by styrene,
  • the present invention also provides monodisperse acrylic ion exchangers obtainable from
  • a monomer feed to an aqueous dispersion of the seed polymer from process step a ') in the presence of a dispersant, this monomer feed having 0.1 to 2 wt.% initiator, 1 to 60 wt.% crosslinking agent and 30 to 98.9 wt .- contains acrylic monomer, of which up to 49.9 wt .-% can be replaced by styrene,
  • the present application also relates to the monodisperse acrylic-containing bead polymers, preferably with a particle size of 5 to 500 ⁇ m, obtainable from a) producing an uncrosslinked monodisperse seed polymer having a particle size of 0.5 to 20 ⁇ m by free-radically initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent,
  • the present invention also relates to monodisperse acrylic-containing bead polymers, preferably with a particle size of 5 to 500 ⁇ m, obtainable by
  • a ' adding at least one monomer feed to an aqueous dispersion of the seed polymer from process step a) in the presence of a dispersant, this monomer feed containing 0.1 to 5% by weight of initiator and 95 to 99.9% by weight of monoethylenically unsaturated compounds Allowing the monomer feed to swell into the seeds and polymerizing to an uncrosslinked monodisperse seed polymer at elevated temperature,
  • the monodisperse acrylic anion exchangers produced according to the invention are used for removing anions from aqueous or organic solutions and their vapors for removing color particles from aqueous or organic solutions and their vapors
  • glucose solutions whey, thin gelatin broths, fruit juices, fruit musts 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
  • the present invention therefore also relates
  • Process for removing organic components from aqueous solutions, for example humic acids from surface water, using the monodisperse acrylic-containing anion exchanger according to the invention Processes for the separation and purification of biologically active components such as antibiotics, enzymes, peptides and nucleic acids from their solutions, for example from reaction mixtures and from fermentation broths, using the monodisperse acrylic-containing anion exchangers according to the invention.
  • biologically active components such as antibiotics, enzymes, peptides and nucleic acids from their solutions, for example from reaction mixtures and from fermentation broths.
  • - Method for analyzing the ion content of aqueous solutions by ion exchange chromatography using the monodisperse acrylic anion exchanger according to the invention.
  • the monodisperse acrylic-containing anion exchangers according to the invention can be used for cleaning and processing water in the chemical industry and electronics industry.
  • the monodisperse acrylic-containing 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, in particular in the sugar industry.
  • the monodisperse acrylic-containing cation exchangers produced according to the invention are used in different applications. For example, they are also used in drinking water treatment and for the chromatographic separation of glucose and fructose.
  • the present invention therefore relates to the use of the monodisperse acrylic-containing cation exchangers according to the invention for removing cations, color particles or organic components from aqueous or organic solutions, for softening by neutral exchange of aqueous or organic solutions, for cleaning and processing water from the chemical industry and electronics -Industry and from power plants,
  • the present invention therefore also relates Process for the purification and processing of water from the chemical industry, the electronics industry and from power plants, characterized in that the monodisperse acrylic-containing cation exchangers according to the invention are used.
  • the monodisperse acrylic-containing bead polymers prepared in accordance with process step b) can also be used in a variety of applications, such as for the separation and purification of biologically active components from their solutions, for the removal of color particles or organic components from aqueous or organic solutions and as a carrier for organic molecules such as chelating agents, enzymes and antibodies.
  • the present invention therefore relates to the use of the monodisperse acrylic bead polymers according to the invention from process step b)
  • a process for binding organic molecules such as chelating agents, enzymes and antibodies to a support characterized in that the monodisperse acrylic bead polymers according to the invention are used as a support in process step b).
  • Pearl polymer with a diameter of 6 ⁇ m is produced.
  • the product is sedimented overnight. Then the supernatant solution is decanted off.
  • the sediment is washed by taking up 2 times in 2 liters of methanol and 2 times in 2 liters of deionized water, stirring, sedimenting and decanting. An approximately 20% aqueous suspension is then prepared and the solids content is determined. A yield of 85.5% is obtained.
  • 332.01 g of the 20.09% seed suspension produced in la) are placed in 801.49 g deionized water and 16.89 g 75% dioctyl sodium sulfosuccinate in a 4 liter paddle jar with grid stirrer, cooler, temperature sensor, thermostat and temperature recorder Stirring at 150 rpm and Stikl material supply homogenized.
  • the stirring speed was increased to 300 rpm for 2 minutes. After returning to 150 rpm, the nitrogen flow was shut off.
  • the reaction mixture was kept at 80 ° C for 20 h.
  • the reaction mixture was then cooled to room temperature, the resulting polymer was isolated by centrifugation, washed twice with methanol and twice with water. This gave 2970 g of an aqueous Dispersion of the seed polymer 2 with a solids content of 10% by weight.
  • the particle size was 2.9 ⁇ m, 0 (90) / 0 (10) was 1.29.
  • Step 2a'-1 was repeated, but the following were used:
  • the resulting bead polymer was washed four times with water and dispersed in water. 1420 g of an aqueous dispersion of the seed polymer 2 '-2 with a solids content of 9.9% by weight were obtained. The particle size was 10.6 ⁇ m, 0 (90) / 0 (10) was 1.37.
  • Step 2a was repeated, except that: an emulsion HI prepared analogously to emulsion I with a mixture of 100 g styrene and 200 g methyl acrylate and 404 g of the dispersion from 2a'-2) was used, the emulsion HI was kept at 0 to 5 ° C. during production and metering and the batch was left at room temperature for 14 hours after the metering was complete and heated to 80 ° C. for 7 hours.
  • the resulting bead polymer was washed four times with water and dispersed in water. 1370 g of an aqueous dispersion of the seed polymer 2'-3 with a solids content of 9.1% by weight were obtained. The particle size was 21 ⁇ m, 0 (90) / 0 (10) was 1.41.
  • a solution of 10 g of methylhydroxyethylceUulose in 2245 g of deionized water, 440 g of aqueous dispersion of 2a'-3) and 460 g of deionized water was introduced into a 4 liter three-necked flask which was flushed with a nitrogen stream of 20 l / h.
  • the fine emulsion IV which was kept between 0 and 5 ° C., was pumped in at a constant rate over the course of 3 hours. The mixture was then left at room temperature for a further 14 hours and then heated to 80 ° C. for 5 hours.
  • the reaction mixture was then cooled to room temperature, the resulting polymer was isolated by centrifugation, washed twice with methanol and twice with water and dispersed in water. In this way, 622 g of an aqueous dispersion of the acrylic bead polymer 2 having a solids content of 26.2% by weight were obtained.
  • the particle size was 39 ⁇ m, 0 (9O) / 0 (10) was 1.44.
  • a solution of 10 g of methylhydroxyethylceUulose in 2245 g of deionized water, 440 g of aqueous dispersion of 2a'-3) and 460 g of deionized water was introduced into a 4 liter three-necked flask which was flushed with a nitrogen stream of 20 l / h.
  • the fine emulsion V was pumped in at a constant rate over the course of 3 hours. The mixture was then left at room temperature for a further 14 hours and then heated to 80 ° C. for 6 hours.
  • the reaction mixture was then cooled to room temperature, and the resulting polymer was isolated by centrifugation, washed twice with dimethylformamide and twice with water and dispersed in water. This gave 761 g of an aqueous dispersion of the acrylic bead polymer 3 with a solids content of 12.9% by weight.
  • the particle size was 43 ⁇ m, 0 (9O) / 0 (10) was 1.38.
  • the reaction mixture was then cooled to room temperature, the viscous, light-colored dispersion was diluted with 5 liters of water and the cation exchange beads were washed extensively with water on a sieve.
  • the cation exchanger obtained in the sodium form was in the with 3 liters of 6% sulfuric acid Converted into H form and washed on a sieve with deionized water for neutrality. After suction on a suction filter, 550 g of finely divided, weakly acidic, water-moist cation exchange beads in the H-shape were obtained.
  • the solids content was 22%, the particle size was 50 ⁇ m, 0 (90) / 0 (10) was 1.42.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Zoology (AREA)
  • Animal Husbandry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Birds (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Nutrition Science (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Insects & Arthropods (AREA)
  • Marine Sciences & Fisheries (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un procédé de fabrication de polymérisats en perles monodispersés contenant des acryliques, présentant de préférence une granulométrie de 5 à 500 µm, ainsi que la fonctionnalisation desdits polymérisats en échangeurs ioniques.
EP05701149A 2004-02-06 2005-01-25 Procede de fabrication de polymerisats en perles monodisperses contenant des acryliques Withdrawn EP1713588A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004006115A DE102004006115A1 (de) 2004-02-06 2004-02-06 Verfahren zur Herstellung von monodispersen acrylhaltigen Perlpolymerisaten
PCT/EP2005/000670 WO2005075078A2 (fr) 2004-02-06 2005-01-25 Procede de fabrication de polymerisats en perles monodisperses contenant des acryliques

Publications (1)

Publication Number Publication Date
EP1713588A2 true EP1713588A2 (fr) 2006-10-25

Family

ID=34801731

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05701149A Withdrawn EP1713588A2 (fr) 2004-02-06 2005-01-25 Procede de fabrication de polymerisats en perles monodisperses contenant des acryliques

Country Status (7)

Country Link
US (1) US20080255258A1 (fr)
EP (1) EP1713588A2 (fr)
JP (1) JP2007534793A (fr)
CN (1) CN1938091A (fr)
DE (1) DE102004006115A1 (fr)
NO (1) NO20063981L (fr)
WO (1) WO2005075078A2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007020688A1 (de) * 2007-05-03 2008-11-06 Lanxess Deutschland Gmbh Konditionierung von Ionenaustauschern zur Adsorption von Oxoanionen
DE102007034732A1 (de) * 2007-07-23 2009-01-29 Lanxess Deutschland Gmbh Verfahren zur Herstellung von Chelatharzen
JP6540049B2 (ja) * 2015-01-28 2019-07-10 東洋インキＳｃホールディングス株式会社 樹脂組成物およびその製造方法、粘着剤、粘着シート
JP6901968B2 (ja) * 2015-06-04 2021-07-14 株式会社日本触媒 有機重合体微粒子
FR3056080B1 (fr) * 2016-09-20 2019-09-13 West Invest S.A. Procede de desacidification d’un jus de fruit, notamment d’un jus de canneberge
CN106589222A (zh) * 2016-12-05 2017-04-26 黄晖 一种单分散高分子微球及其制备方法
DE102017222295B4 (de) * 2017-12-08 2019-12-05 Axagarius Gmbh & Co. Kg Kits und Verfahren zur Entfernung von Verunreinigungen aus einer Nukleinsäure enthaltenden Probe

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3031737A1 (de) * 1980-08-22 1982-04-01 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von perlpolymerisaten einheitlicher teilchengroesse
CA1166413A (fr) * 1980-10-30 1984-05-01 Edward E. Timm Methode et dispositif pour la preparation de perles de polymere dimensionnellement uniformes
US4419245A (en) * 1982-06-30 1983-12-06 Rohm And Haas Company Copolymer process and product therefrom consisting of crosslinked seed bead swollen by styrene monomer
US5068255A (en) * 1982-08-02 1991-11-26 The Dow Chemical Company Ion exchange resins prepared by sequential monomer addition
DE3888564T2 (de) * 1987-04-22 1994-10-20 Mitsubishi Chem Ind Verfahren zur Herstellung von vernetzten Polymerteilchen.
US5147937A (en) * 1990-03-22 1992-09-15 Rohm And Haas Company Process for making controlled, uniform-sized particles in the 1 to 50 micrometer range
DE19634393A1 (de) * 1996-08-26 1998-03-05 Bayer Ag Verfahren zur Herstellung vernetzter Polymerisate
DE10061544A1 (de) * 2000-12-11 2002-06-13 Bayer Ag Weiche, momodisperse, kugelförmige Perlpolymerisate
DE10122896A1 (de) * 2001-05-11 2002-11-14 Bayer Ag Verfahren zur Herstellung von monodispersen gelförmigen Kationenaustauschern
DE10214844A1 (de) * 2002-04-04 2003-10-16 Bayer Ag Verfahren zur Herstellung von grobkörnigen gelförmigen Anionenaustauschern
DE10237601A1 (de) * 2002-08-16 2004-02-26 Bayer Ag Verfahren zur Herstellung von monodispersen gelförmigen Ionenaustauschern

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005075078A2 *

Also Published As

Publication number Publication date
US20080255258A1 (en) 2008-10-16
CN1938091A (zh) 2007-03-28
DE102004006115A1 (de) 2005-08-25
JP2007534793A (ja) 2007-11-29
NO20063981L (no) 2006-09-06
WO2005075078A2 (fr) 2005-08-18
WO2005075078A3 (fr) 2005-10-20

Similar Documents

Publication Publication Date Title
EP1713845A2 (fr) Procede de fabrication d'echangeurs ioniques monodisperses contenant des pores
WO2005075078A2 (fr) Procede de fabrication de polymerisats en perles monodisperses contenant des acryliques
EP1078688B1 (fr) Méthode pour la préparation d'échangeurs d'anions monodisperses
EP1350563B1 (fr) Procédé de préparation de resin anionique en form de gel ayant des particules larges
EP2077158A2 (fr) Procédé de fabrication d'échangeurs de cations
DE10237601A1 (de) Verfahren zur Herstellung von monodispersen gelförmigen Ionenaustauschern
EP1110982A1 (fr) Procédé pour la production de perles de polymères réticulés monodispersés
DE19852666A1 (de) Verfahren zur Herstellung von monodispersen gelförmigen Anionenaustauscher
DE10122896A1 (de) Verfahren zur Herstellung von monodispersen gelförmigen Kationenaustauschern
EP1748051A1 (fr) Echangeur de cations monodispersé
EP1380344A1 (fr) Méthode pour la production d'échangeurs d'ions sous forme de gel
DE3427441C2 (fr)
EP1000659B1 (fr) Méthode de préparation d'échangeurs cationiques monodispersés sous forme de gel
EP1757652B1 (fr) Resine echangeuse de cations faiblement acide
EP1908521A1 (fr) Echangeurs d'anions thermiquement stables
EP0964002B1 (fr) Utilisation de polymères spériques réticulés
EP1149630A2 (fr) Méthode de préparation d'échangeurs de cations monodispersés sous forme de gel
DE10105103A1 (de) Verfahren zur Herstellung von gelförmigen Kationenaustauschern
EP1512698B1 (fr) Procédé de préparation de polymères en perles non microencapsulés monodispersés
EP0870772A2 (fr) Procédé de préparation de polymères sphériques réticulés
DE69024569T2 (de) Herstellungsverfahren von Verbundwerkstoff aus porösen, hohlen Teilchen
DE19847050A1 (de) Verfahren zur Herstellung mikroverkapselter kugelförmiger Polymerisate
DE102007009073A1 (de) Schwachsaure Kationenaustauscher
EP0964001A1 (fr) Procédé de préparation polymères micro-encapsulés
EP0897939A1 (fr) Procédé de préparation de polymères sphériques

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060906

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: VANHOORNE, PIERRE

Inventor name: CHERNYSHOV, DMITRI

Inventor name: PODSZUN, WOLFGANG

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20070806

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20080219