EP1713588A2

EP1713588A2 - Method for the production of monodispersed pearl polymers containing acrylic

Info

Publication number: EP1713588A2
Application number: EP05701149A
Authority: EP
Inventors: Wolfgang Podszun; Pierre Vanhoorne; Dmitri Chernyshov
Original assignee: Lanxess Deutschland GmbH
Current assignee: Lanxess Deutschland GmbH
Priority date: 2004-02-06
Filing date: 2005-01-25
Publication date: 2006-10-25
Also published as: CN1938091A; NO20063981L; WO2005075078A3; WO2005075078A2; DE102004006115A1; US20080255258A1; JP2007534793A

Abstract

The invention relates to a method for the production of monodispersed pearl polymers containing acrylic, preferably having a particle size of 5 - 500 µm, in addition to the functionalization for the formation of ion exchangers.

Description

Process for the preparation of monodisperse acrylic-containing pearl pormer products

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 μm, 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. On the basis of crosslinked acrylic bead polymers, 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.

In recent times, ion exchangers with a particle size that is as uniform as possible (hereinafter referred to as “monodisperse”) have become increasingly important because in many applications, because of the more favorable hydrodynamic properties of an exchange bed, monodisperse ion exchangers can achieve economic advantages. Monodisperse ion exchangers can be functionalized by monodisperse bead polymer can be obtained.

One of the possibilities for producing monodisperse bead polymers is the so-called 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 μm. 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 μm. In this process, an emulsion polymer with particle sizes of preferably 0.05 to 0.5 μm 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 μm 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.

Although numerous methods and processes for producing monodisperse bead polymers or monodisperse ion exchangers have been described above, all known methods are based almost entirely on styrene-containing bead polymers.

In Chemistry of Materials 1998, Vol. 10, pages 385-291, Frechet et al. the production of cross-linked, monodisperse, acrylic-containing bead polymers with a diameter of up to 5 μm based on uncrosslinked monodisperse seed polymers.

DE-A 102 37601, on the other hand, discloses monodisperse gel-shaped ion exchangers with a diameter of up to 500 μm, 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 μm 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.

So far there is no process for the targeted production of monodisperse acrylic ion exchangers made from monodisperse acrylic bead polymers with a particle size of 5 to 500 μm.

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 μm is obtained by radical-initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent generated,

b) a monomer feed is added to an aqueous dispersion of the seed polymer in the presence of a dispersant, which

0.1 to 2% by weight of initiator, 1 to 60% by weight of crosslinking agent and 30 to 98.9% by weight of acrylic monomer, of which up to 49.9% by weight can be replaced by styrene, 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 μm

c) these crosslinked monodisperse acrylic-containing bead polymers are converted into monodisperse acrylic-containing ion exchangers by functionalization.

In one embodiment variant of the present invention, in a process step a ') at least one monomer feed can be added to an aqueous dispersion of the seed polymer from process step a) in the presence of a dispersant

0.1 to 5 wt .-% initiator and

95 to 99.9% by weight of monoethylenically unsaturated compounds but contains no crosslinking agent,

allows this monomer feed to swell into the seeds and polymerizes at elevated temperature to form uncrosslinked monodisperse seed polymers. 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 μm 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.

Multiple in the sense of the present invention means up to ten times, preferably up to eight times, particularly preferably up to six times, of the monomer feed. After process step b), the monodisperse acrylic-containing bead polymers have a particle size of 5 to 500 μm, preferably 10 to 400 μm, particularly preferably 20 to 300 μm, very particularly preferably 51 to 300 μm. 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. Correspondingly, 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, α-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.

In the preparation of the uncrosslinked seed polymer, 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. When using solvent mixtures, 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.

In addition to the dispersants, 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.

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-tert-butyl peroxyazelate or di-tert-amyl peroxyazelate.

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.

If necessary, inhibitors soluble in the solvent can be used. Examples of 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. According to the invention, 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 μm, preferably 2.2 to 15 μm. 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, α-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. Styrene, methyl acrylate and butyl acrylate are preferred. Mixtures of different monoethylenically unsaturated compounds are also very suitable. In a preferred embodiment of process step a '), the proportion of acrylic monomer is increased with each repetition. For the definition of the acrylic monomer, reference is made to process step b).

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. Of course, mixtures of the above can also be used 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 μm 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.

It can also be advantageous in process step a ') to use a JiJiibitor dissolved in the aqueous phase. Both inorganic and organic substances can be used as inhibitors. Examples of inorganic inhibitors are nitrogen compounds such as hydroxylamine, hydrazine, sodium nitrite or Kdiirmnitrit. Examples of 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.

The person skilled in the art understands 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.

In a further embodiment of the present invention, 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. In general, temperatures of 60 to 130 ° C., preferably 60 to 95 ° C., are used in this procedure.

By repeating the feed steps multiple times, i.e. The addition of monomer feed, swelling and polymerisation are ultimately accessible from monodisperse seed polymers with particle sizes from 0.5 to 20 μm uncrosslinked monodisperse seed polymers with particle sizes up to 300 μm.

After the polymerization, 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.

In process step b), the seed polymer from a) or a ') is mixed with a feed of an acrylic monomer with initiator and crosslinker. According to the invention, 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. For the purposes of this invention, 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. Acrylonitrile, acrylamide, methyl acrylate, methyl methacrylate, butyl acrylate and glycidyl methacrylate are preferred. Mixtures of different acrylic monomers are also suitable.

In a particularly preferred variant of the present invention, no styrene is present in the monomer feed of process step b). However, the monomer feed of process step b) can optionally contain further comonomers. Suitable comonomers are compounds copolymerizable with acrylic monomers, such as e.g. α-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.

According to the invention, 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. Of course, 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 μm, which are produced using rotor-stator mixers or mixing jet nozzles using emulsifying aids such as e.g. Sulfobern- stemsäureisooctylester 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). In 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. Examples of organic inhibitors are 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.

The person skilled in the art understands 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.

In a further embodiment of the present invention, 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. In general, 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 μm, 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).

After the polymerization, 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.

In process step c), 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.

When sodium hydroxide solution is used as the hydrolysis agent, the weakly acidic cation exchanger is obtained in the sodium form. For some applications it is beneficial to convert the cation exchanger from the sodium form to the acid form. This transfer is carried out with sulfuric acid at a concentration of 5 to 50%, preferably 10 to 20%.

If desired, 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").

From the weakly basic anion exchangers, 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

a) Generation of an uncrosslinked monodisperse seed polymer having a particle size of 0.5 to 20 μm by radical-initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent.

b) adding a monomer feed to an aqueous dispersion of the seed polymer from process step a) in the presence of a dispersant, the monomer feed

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,

Swelling of the monomer feed into the seeds and polymerization at elevated temperature to form crosslinked monodisperse acrylic-containing bead polymers, preferably with a particle size of 5 to 500 μm and

c) functionalizing these crosslinked monodisperse acrylic-containing bead polymers.

The present invention also provides monodisperse acrylic ion exchangers obtainable from

a) producing an uncrosslinked monodisperse seed polymer having a particle size of 0.5 to 20 μm by free-radically initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent,

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 0.1 to 5% by weight of initiator and 95 to 99.9% by weight of monoethylenically unsaturated Contains compounds, swelling of the monomer feed into the seeds and polymerization to uncrosslinked monodisperse seed polymers at elevated temperature,

b) adding 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,

Swelling of the monomer feed into the seeds and polymerization at elevated temperature to form crosslinked monodisperse acrylic-containing bead polymers, preferably to crosslinked monodisperse acrylic-containing bead polymers with a particle size of 5 to 500 μm and

The present application also relates to the monodisperse acrylic-containing bead polymers, preferably with a particle size of 5 to 500 μm, obtainable from a) producing an uncrosslinked monodisperse seed polymer having a particle size of 0.5 to 20 μm by free-radically initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent,

b) adding at least one monomer feed to an aqueous dispersion of the seed polymer in the presence of a dispersant which

0.1 to 2 wt .-% initiator, 1 to 60 wt .-% crosslinker and 30 to 98.9 wt .-% acrylic monomer, of which up to 49.9 wt .-% can be replaced by styrene, swelling of Monomer feed into the seeds and polymerizing at elevated temperature.

The present invention also relates to monodisperse acrylic-containing bead polymers, preferably with a particle size of 5 to 500 μm, 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,

b) adding a monomer feed to an aqueous dispersion of the seed polymer from process step a ') in the presence of a dispersant which

Contains 0.1 to 2% by weight of initiator, 1 to 60% by weight of crosslinking agent and 30 to 98.9% by weight of acrylic monomer, of which up to 49.9% by weight can be replaced by styrene,

Squeezing the monomer feed into the seeds and polymerizing 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

- for decolorization and desalination of 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,

for removing organic components from aqueous solutions, for example humic acids from surface water,

For the separation and cleaning of biologically active components such as Antibiotics, enzymes, peptides and nucleic acids from their solutions, for example from reaction mixtures and from fermentation broths,

- For the analysis of the ion content of aqueous solutions by ion exchange chromatography. The present invention therefore also relates

Process for removing anions from aqueous organic solutions and their vapors or color particles from aqueous or organic solutions and their vapors using the monodisperse acrylic-containing anion exchangers according to the invention.

Process for decolorization and desalination of glucose solutions, whey, thin gelatine broths, fruit juices, freight costs 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, using the monodisperse acrylic-containing anion exchanger according to the invention.

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. - Method for analyzing the ion content of aqueous solutions by ion exchange chromatography, using the monodisperse acrylic anion exchanger according to the invention.

Furthermore, 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.

Furthermore, 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,

For analyzing the ion content of aqueous solutions by ion exchange chromatography.

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.

Process for the removal of cations, color particles or organic components from aqueous or organic solutions, characterized in that the monodisperse acrylic-containing cation exchangers according to the invention are used.

Process for the softening in the neutral exchange of aqueous or organic solutions, characterized in that the monodisperse acrylic-containing cation exchangers according to the invention are used.

Process for the separation and purification of biologically active components, e.g. Antibiotics, enzymes, peptides and nucleic acids from their solutions, for example from reaction mixtures and from fermentation broths, characterized in that the monodisperse acrylic-containing cation exchangers according to the invention are used.

Method for analyzing the ion content of aqueous solutions by ion exchange chromatography, 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)

For removing color particles or organic components from aqueous or organic solutions, As a carrier for organic molecules such as chelating agents, enzymes and antibodies, which are either adsorbed on the carrier or fixed covalently or ionically by reaction with a functional group present on the carrier. The present invention therefore also relates

- Process 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, characterized in that the monodisperse acrylic bead polymers according to the invention are used in accordance with process step b),

Process for removing color particles or organic components from aqueous or organic solutions, characterized in that the monodisperse acrylic bead polymers according to the invention are used in 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).

Examples

Example 1 la) Production of the seed polymer 1

2681.14 g of methanol, 205.71 g of polyvinylpyrroHdon K 30 from Aldrich, 6.86 g of ethyl methacrylate and 336.00 g of methyl methacrylate are placed in a 4 liter flat ground vessel with a grid stirrer, cooler, temperature sensor and thermostat and temperature recorder. The mixture, which is stirred at 100 rpm, is heated to 55 ° C. under nitrogen within 1 hour. A solution consisting of 10.29 g of 2,2-azobis (isobutyronitrile) and 188.57 g of methanol is then added. The monomer mixture is polymerized at 55 ° C. for 20 hours, then cooled to room temperature. Pearl polymer with a diameter of 6 μm 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.

lb) Production of the Acrylic Pearl Polymer 1

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.

180.0 g of methyl acrylate, 20.0 g of diethylene diglycol divinyl ether and 2.67 g of 75% dibenzoyl peroxide are mixed with an Ultraturrax for 1 min at 24,000 rpm in 100 g of deionized water and 2.0 g of 75% dioctyl sodium emulsified sulfosuccinate. These are rinsed into the template with 100 g of deionized water. After a swelling time of 2 hours, beads of 8.6 μm are obtained. This corresponds to an efficiency of 63.3%. The mixture is then heated to 80 ° C. in 1 hour and polymerized at 80 ° C. for 12 hours. Then cooled to room temperature. The entire batch is sedimented overnight, then the supernatant solution is decanted off. The sediment is washed by taking up 3 times in 2 liters of deionized water, stirring, sedimenting and decanting. An approximately 20% suspension is then prepared and the solids content is determined. The yield is 75.8%. lc) saponification of the acrylic bead polymer 1

549 g of deionized water with 366 g of 50% NaOH solution at 200 rpm are placed in a 4 liter flat ground vessel with a grid stirrer, destiUation bridge, temperature sensor, thermostat and temperature recorder. 150 g of acrylic polymer bead 1 are added in portions with stirring. The mixture is heated to 100 ° C. within 1.5 hours. The mixture is then stirred at this temperature for 6 hours and then cooled to room temperature. The saponified product has a diameter of 12.1 μm. It is made up to 5 liters with deionized water, allowed to settle and decanted. The whole is repeated until the pH is neutral (5 times in the example). An approximately 20% suspension is prepared and the solids content is determined. The yield of monodisperse, weakly acidic cation exchanger 1 in the sodium form is 99%.

Reloading the weakly acidic cation exchanger 1

472 g of the 16.95% suspension produced in c) are placed in a 4 liter paddle jar with a grid stirrer, cooler, temperature sensor, thermostat and temperature recorder. At 200 rpm, 274.67 g of 14.56% strength sulfuric acid solution (6% with respect to the w phase) are added dropwise within 6 hours. The suspension is stirred overnight for about 15 hours. The loaded product has a diameter of 10 μm. It is sedimented and decanted. Then it is washed with deionized water. Make up to 2 liters, sediment and decant. The whole is repeated until the pH is neutral (6 times in the example). An approx. 20% suspension is prepared and the solids content is determined. The yield is 63.2 g.

Example 2

2a) Preparation of the seed polymer 2

2400 g of n-butanol and 180 g of polyvinylpyrrolidone (Luviskol® K30) were stirred in a 4 liter three-necked flask for 60 minutes, a homogeneous solution being obtained. The reactor was then flushed with a nitrogen stream of 201 / h and 300 g of styrene were added within a few minutes with further stirring at 150 rpm. The reactor was heated to 80 ° C. When a temperature of 71 ° C. was reached, a solution of 3 g of azodiisobutyric acid and 117 g of n-butanol which had been heated to 40 ° C. was added all at once. 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 μm, 0 (90) / 0 (10) was 1.29.

2a'-l) Production of the seed polymer 2'-l

300 g of styrene, 9.24 g of 75% by weight dibenzoyl peroxide, 500 g of water, 3.62 g of ethoxylated nonylphenol (Arkopal® N060), 0.52 g of sulfosuccinic acid isooctyl ester sodium salt and 2 g of 3 ', 3 "5,5'5" -hexa-tert-butyl-alpha, alpha', alpha "- (mesitylene-2,4,6-triyl) tri-p-cresol (inhibitor Irganox® 1330) with a Ultraturrax (3 min. At 13500 rpm) produced a fine emulsion I. In a 4 liter three-necked flask, which was flushed with a nitrogen stream of 20 l / h, a solution of 5 g of methylhydroxyethyl cellulose in 2245 g of deionized water and 404 was g of aqueous dispersion from 2a) The fine emulsion Emulsion I was pumped in at a constant rate over the course of 3 hours at room temperature with stirring, the batch was then left at room temperature for a further 13 hours and then heated to 80 ° C. for 9 hours Cooled reaction mixture to room temperature, the resulting polymer isohe by centrifugation rt, washed twice with methanol and twice with water and dispersed in water. In this way, 1300 g of an aqueous dispersion of the seed polymer 2'-1 with a solids content of 22.6% by weight were obtained. The particle size was 6.6 μm, 0 (90) / 0 (10) was 1.33.

2a'-2) Production of the Seed Polymer 2'-2

Step 2a'-1 was repeated, but the following were used:

- An emulsion LT manufactured analogous to emulsion I with a mixture of 200 g styrene and 100 g methyl acrylate 170 g of the dispersion from 2a'-l)

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 μm, 0 (90) / 0 (10) was 1.37.

2a'-3) Production of the Room Polymer 2'-3

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 μm, 0 (90) / 0 (10) was 1.41.

2b) Production of the Acrylic Pearl Polymer 2

285 g of methyl acrylate, 15 g of diethylene glycol divinyl ether, 0.03 g of hydroquinone, 9.24 g of dibenzoyl peroxide, 500 g of water, 3.62 g of ethoxylated nonylphenol (Arkopal® N060) were added to a plastic container at a temperature between 0 and 5 ° C. 0.52 g of sulfosuccinic acid isooctyl ester sodium salt and 2 g of 3,3 ', 3 "5,5'5" -hexa-tert-butyl-alpha, alpha', alpha "- (mesitylene-2,4,6-triyl ) tri-p-cresol (inhibitor Irganox® 1330) with an Ultraturrax (3 min. at 10000 rpm) produces a fine emulsion IV.

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. At room temperature, 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 μm, 0 (9O) / 0 (10) was 1.44.

2c) hydrolysis to weakly acidic cation exchanger 2

681 g of the aqueous dispersion from 2b) were filtered off and filled with 580 ml of deionized water in a 41 three-necked flask. The mixture was heated to reflux with stirring (100 rpm). 256 g of a 50% sodium hydroxide solution were then added over a period of 2 h, then 1280 g over a period of 75 min. The batch was kept at reflux by a suitable increase in temperature. The total response time was 7 hours. After the end of the metering, 230 ml of water were distilled off. The final temperature was 120 ° C. The reaction mixture was then cooled to room temperature, the viscous 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 converted into the H form with 3 liters of 6% sulfuric acid and washed to neutrality on a sieve with deionized water. After suction on a suction filter, 660 g of finely divided, weakly acidic, water-moist cation exchange beads in the H-shape were obtained. The solids content was 23%, the particle size was 50 μm, 0 (90) / 0 (10) was 1.29. The content of weakly acidic groups was 2.12 mmol per ml of wet resin. Example 3

Starting from the aqueous dispersion from 2a'-3), the procedure was as follows:

3b) Production of the Acrylic Pearl Polymer 3

In a plastic container, 285 g of acrylonitrile, 15 g of diethylene glycol divinyl ether, 9.24 g of dibenzoyl peroxide, 500 g of water, 4.50 g of ethoxy-hardened nonylphenol (Arkopal® N060), 0.80 g of sulfobemstemic acid isooctyl ester salt and 6 g of 3.3 ', 3 "5,5'5" -hexa-tert-butyl-alρha, alpha ', alρha "- (mesitylene-2,4,6-triyl) tri-p-cresol (inhibitor Irganox® 1330) with an Ultraturrax (3rd Min. At 10000 rpm) a fine emulsion V is generated.

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. At room temperature, 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 μm, 0 (9O) / 0 (10) was 1.38.

3c) hydrolysis to weakly acidic cation exchanger 3

711 g of the dispersion from 3b) were filtered off and introduced with 300 ml of deionized water in a 4 liter three-necked flask. The mixture was heated to reflux with stirring (100 rpm). 132 g of a 50% sodium hydroxide solution were then added over a period of 2 h, then 638 g within 75 min. The batch was kept at reflux by a suitable increase in temperature. The total reaction time was 7 hours. After the end of the metering, 450 ml of water were distilled off. The final temperature was 120 ° C. 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 μm, 0 (90) / 0 (10) was 1.42.

Claims

Patentansprflche

1. 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 μm is produced by radically initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent, b) to an aqueous one Dispersion of the seed polymer in the presence of a dispersant adds a monomer feed which contains 0.1 to 2% by weight of initiator, 1 to 60% by weight of crosslinker and 30 to 98.9% by weight of acrylic monomer, of which up to 49.9 % By weight can be replaced by styrene, allows the monomer feed to swell into the seeds and polymerizes at elevated temperature to form crosslinked monodisperse acrylic bead polymers, preferably with a particle size of 5 to 500 μm, and c) these crosslinked monodisperse acrylic bead polymers by functionalizing in monodisperse acrylic ion exchangers leads.

2. Monodisperse, acrylic-containing ion exchangers, obtainable by a) producing an uncrosslinked monodisperse seed polymer having a particle size of 0.5 to 20 μm by radical-initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent, b) adding a monomer feed to an aqueous dispersion of the seed - Polymer in the presence of a dispersant, the monomer feed

Contains 0.1 to 2% by weight of initiator, 1 to 60% by weight of crosslinking agent and 30 to 98.9% by weight of acrylic monomer, of which up to 49.9% by weight can be replaced by styrene, Swelling of the monomer feed into the seeds and polymerizing at elevated temperature to form crosslinked monodisperse acrylic bead polymers, preferably with a particle size of 5 to 500 μm, and c) functionalizing these crosslinked monodisperse acrylic bead polymers.

3. Monodisperse, acrylic-containing bead polymers, preferably with a particle size of 5 to 500 μm, obtainable by a) producing an uncrosslinked monodisperse seed polymer with a particle size of 0.5 to 20 μm by means of radically initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent , b) adding a monomer feed to an aqueous dispersion of the seed polymer from process step a) in the presence of a dispersant, the monomer feed

Contains 0.1 to 2% by weight of initiator, 1 to 60% by weight of crosslinking agent and 30 to 98.9% by weight of acrylic monomer, of which up to 49.9% by weight can be replaced by styrene, and

Swelling of the monomer feed into the seeds and polymerization at elevated temperature.

4. Process for the production of monodisperse acrylic ion exchangers, characterized in that a) an uncrosslinked monodisperse seed polymer having a particle size of 0.5 to 20 μm is produced by radically initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent, a ') to an aqueous dispersion of the seed polymer from a) in the presence of a dispersant, add at least one monomer feed which contains 0.1 to 5% by weight of initiator and 95 to 99.9% by weight of monoethylenically unsaturated compounds but no crosslinker, allowing the monomer feed to cool in into the seeds and polymerize, b) to an aqueous dispersion of the seed polymer from process step a ') in the presence of a dispersant, a monomer feed which 0.1 to 2 wt .-% initiator, 1 to 60 wt .-% crosslinker and 30 to 98.9 wt .-% acrylic monomer, of which up to 49.9 wt .-% can be replaced by styrene, the monomer feed can be sown into the seeds and polymerized at elevated temperature to form crosslinked monodisperse acrylic-containing bead polymers, preferably with a particle size of 5 to 500 μm

Monodisperse, acrylic ion exchangers available from

a) producing an uncrosslinked monodisperse seed polymer with a particle size of 0,

5 to 20 μm by radical initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent,

a ') adding at least one monomer feed to an aqueous dispersion of the seed polymer from a) in the presence of a dispersant, this monomer feed 0.1 to 5% by weight of initiator and 95 to 99.9% by weight of monoethylenically unsaturated compounds but none Crosslinker, swelling of the monomer feed into the seeds and polymerization into a crosslinked monodisperse bead polymer at elevated temperature,

b) adding a monomer feed to an aqueous dispersion of the seed polymer from process step a ') in the presence of a dispersant, the monomer feed

Swelling of the monomer feed into the seeds and polymerization at elevated temperature to form crosslinked monodisperse acrylic-containing bead polymers, preferably with a particle size of 5 to 500 μm, and

6. Monodisperse, acrylic-containing bead polymers, preferably with a particle size of 5 to 500 μm, obtainable by a) producing an uncrosslinked monodisperse seed polymer with a particle size of 0.5 to 20 μm by radically initiated polymerization of monoethylenically unsaturated compounds in the presence of a non-aqueous solvent , 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, the monomer feed 0.1 to 5 wt .-% initiator and 95 to 99.9 wt .-% monoethylenically unsaturated compounds but does not contain a crosslinker. Allowing the monomer feed to swell into the seeds and polymerize to an uncrosslinked bead polymer at elevated temperature. b) adding a monomer feed to an aqueous dispersion of the seed polymer from process step a ') in the presence of a dispersant, this monomer feed

Contains 0.1 to 2% by weight of initiator, 1 to 60% by weight of crosslinker and 30 to 98.9% by weight of acrylic monomer, of which up to 49.9% by weight can be replaced by styrene, and swelling of the monomer feed into the seeds and polymerizing at elevated temperature.

7. The method according to claims 1 or 4, characterized in that the monomer feed in process step b) is added in the form of a fine aqueous emulsion.

8. Monodisperse acrylic-containing bead polymers according to spoke 6, characterized in that in process step a) styrene as the monoethylene compound and in process step a contains at least one monomer feed between 20 and 49.9% styrene.

9. A process for the preparation of monodisperse weakly acidic cation exchangers, characterized in that in process step c) of claims 1 and 4, the monodisperse, acrylic-containing bead polymers from process step b) are hydrolyzed with strong bases or strong acids.

10. A process for the preparation of anion exchangers, characterized in that the monodisperse, acrylic-containing bead polymers obtained according to process step b) of claims 1 and 4 are reacted in process step c) with diamines or alcohols.

11. Use of the monodisperse acrylic-containing cation exchanger obtained according to spoke 9 for removing cations, color particles or organic components from aqueous or organic solutions, for softening in the neutral exchange of aqueous or organic solutions, - for cleaning and processing water from the chemical industry, the elec - tiomk industry and from power plants, for decolorization and desalination of whey, thin gelatin broths, fruit juices, fruit must and aqueous solutions of sugar,

12. Use of the monodisperse, acrylic-containing anion exchanger obtained according to spoke 10 for removing anions from aqueous or organic solutions and their vapors for removing color particles from aqueous or organic solutions and their vapors, - for decolorization and desalination of glucose solutions, whey, thin gelatin broths, Fruit juices, fruit musts and sugars, preferably of mono- or disaccharides, in particular cane sugar, beet sugar solutions, fractose solutions, for removing organic components from aqueous solutions, for example humic acids from surface water, 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, for analysis of the ion content of aqueous solutions by ion exchange chromatography.

13. Use of the monodisperse, acrylic-containing bead polymers obtained according to spoke 3 or 6 for the separation and purification of biologically active components such as e.g. Antibiotics, enzymes, peptides and nucleic acids from their solutions, for example from reaction mixtures and from fermentation broths, for removing color particles or organic components from aqueous or organic solutions. as a carrier for organic molecules such as chelating agents, enzymes and antibodies.