DE1918399A1 - Process for the production of a porous, crosslinked mixed polymer, in particular for use as an ion exchange resin - Google Patents

Description

Process for the production of a porous, cross-linked mixed polymer, particularly for use as an ion exchange resin. The invention relates to a Process for the production of a porous, crosslinked mixed polymer. In particular the invention relates to ion exchange resin.

Such a copolymer should have a large effective surface area and a have great porosity. The production takes place starting from a monovinyl compound and a polyvinyl compound with the introduction of ion exchange groups into the porous, cross-linked copolymer.

There are already various processes for the production of a porous, insoluble, non-meltable mixed polymer and an ion exchange resin known where the production from a monovinyl monomer and a polyvinyl monomer takes place in the following way: According to the first known embodiment, a Partial polymerization of a monovinyl monomer or a dissolution of a linear polymer, which was initially made from a monovinyl monomer. Then a Polyvinyl Monomar added to the copolymerization so that you get a crosslinked copolymer receives. Finally, the linear polymer is made from the crosslinked mill polymer by means of an appropriate organic solvent extracted so that a porous, cross-linked copolymer obtained. This mixed polymer can be used as required by Introduction of ion exchange groups iii converted to an ion exchange resin will.

A second known method uses suspension polymerization a monovinyl monomer and a polyvinyl monomer in one water-insoluble one organic solvent suitable for swelling a mixed polymer. This mixed polymer is then by the introduction of ion exchange groups in converted to an ion exchange resin.

The third procedure is followed by a. Interpolymerization of a Monovinyl monomer and a polyvinyl monomer in the presence of a precipitant such as Heptane, tertiary amyl alcohol or the like for the resulting polymer and one polar compound such as acrylic acid or acrylonitrile with subsequent incorporation of ion exchange groups in the copolymer obtained.

The fourth known method polymerizes a monovinyl monomer and a polyvinyl monomer in suspension in the presence of a precipitant for the resulting polymer. Ion exchange groups then become in the resulting polymer brought in.

Each of these known methods results in manufacture such a mixed polymer difficulties, its effective surface as well as the porosity should be large.

An ion exchange resin with a support body has also proven itself egg shape of such a mixed polymer is insufficient. E.g.

can after the block polymerization in the context of the process according to the first example the interpolymerization can be carried out fairly easily; the more of the polymer, however, according to the suspension polymerization in the frame dissolves in the monomer mixture using the same process, the more viscous the monomer phase becomes, so that only the polymer is obtained in large grain size, what for the formation of a Ion exchange resin is not appropriate. As part of the procedure according to The second exemplary embodiment results when the polymerization is carried out In itself no difficulty in obtaining a resin with a large effective surface area and great porosity, however, a large proportion is polyvinyl monomer and organic solvent required from the economical point of view is disadvantageous; this also brings a difficulty for the introduction of ion exchange grooves into the copolymer with itself.

It should also be noted that the use of a large proportion an organic solvent for the deterioration of the properties of the ischpolymers is responsible, namely with regard to the physico-chemical Resistance and mechanical strength.

The known methods for technical application have thus become established proved to be unusable because the polymerization treatment itself already had difficulties brings with it or the properties of the mixed polymer below expectations remain behind if the manufacturing process itself does not cause any difficulties.

As a result, the inventors of the present application have extensive Investigations of the above-mentioned copolymerization processes carried out, in particular with regard to the quantities that determine the properties of the interpolymers obtained.

The production of a porous, crosslinked mixed polymer became particularly important investigated with a large effective surface and large porosity.

The object of the invention is to provide a crosslinked mixed polymer with a large active surface and large porosity, which is used as an adsorber and / or as Ion exchange resin in a column is useful. The method according to the invention should with regard to the desired active surface and the desired porosity be adjustable by changing the polymerization conditions.

This object is achieved according to the invention by interpolymerization of Monovinyl and polyvinyl monomer in the presence of an organic solvent which dissolves the monomers Solvent and a linear monovinyl polymer, being a swollen interpolymer educated becomes, in which the linear polymer with the monomers and the solvent is a homogeneous Phase forms, and by subsequent extraction of the linear polymer from the egg polymer solved.

In a further embodiment of the invention it is proposed that for representation an ion exchange resin in addition to the extraction of the linear polymer the interpolymer simultaneously or subsequently with ion exchange properties is equipped.

A detailed description of the invention now follows. As starting materials Monovinyl monomers used in the process according to the invention are aromatic Monovinyl compounds which contain lower alkyl groups or halogen atoms in addition to the vinyl group may contain. Specifically, there are examples of such aromatic monovinyl compounds Styrene, vinyl toluene, vinyl xylene, vinyl chlorobenzene, α-methyl styrene, ar-methyl styrene ar-dimethylatyrene, ar-ethylvinylbenzene, ar-chlorostyrene, and the like. Others are preferred Monovinyl monomers are alkyl esters of aliphatic monovinyl carboxylic acids and especially lower alkyl esters of acrylic acid and methacrylic acid. Examples of such Alkyl esters are methyl acrylates, ethyl acrylates, butyl acrylates, propyl acrylates, methyl methacrylates, Ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like. As a crosslinking agent Polyvinyl monomers can serve, for example aromatic polyvinyl compounds diglycol esters of unsaturated, aliphatic carboxylic acids and unsaturated alcohol esters of aliphatic dicarboxylic acids. Preferred embodiments of such polyvinyl monomers are divinylbenzene, ar-divinyltoluQl, ar-ditinyl xylene, ar-divinylchlorobensol, Divinylnaphthalene, ar-Dijinyl- ethylbenzene, trivinylbenzene, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, divinyl adipate, maleate and diallyl fumarate.

These polyvinyl monomers are normally used in a proportion of 1 - 60 percent by weight of the total proportion of vinyl monomers used, each in Depending on the property of the mixed polymer to be formed. A preferred range for the poly vinyl nonomer is 2-30% for the Production of a carrier for the ion exchange resin or 10 - 60 for the production a porous mixed polymer for adsorber purposes.

An organic solvent to increase the active surface of the mixed polymer according to the invention should be used to dissolve the starting monomer, suitable for swelling of the resulting mixed polymer and also insoluble or be sparingly soluble in water. Examples of such a solvent are aromatic Hydrocarbons, halogenated aromatic hydrocarbons and halogenated aliphatic hydrocarbons. The choice of solvent is made in practice depending on the type of monovinyl starting monomer used in each case. if For example, an aromatic vinyl compound such as styrene is used as the starting monomer the selection is made from benzene, toluene, xylene, chlorobenzene, carbon tetrachloride, Tetrachloroethane and trichlorethylene. When an aliphatic vinyl compound like an acrylic acid ester or a methacrylic acid ester is used, the selection is made under benzene, toluo and dichloroethane. If further a suspension polymerization Is used, the preferred organic solvent should be water-insoluble or be sparingly soluble in water. The proportion of this organic solvent changes depending on the proportion of polyvinyl monomer used and of the added linear polymer. Generally, the greater the proportion of the polyvinyl monomer the proportion of the solvent is so smaller, while with a smaller proportion of the polyvinyl nonomers a comparatively larger proportion of the solvent is used. Hence leave no particular limits are set for the proportion of organic solvent. The proportion of the organic solvent is usually in a range between 20-300 percent by volume, preferably between 50 and 150 percent by volume per gram Monomer. In carrying out the process of the present invention, one must add the reaction mixture add a linear monovinyl polymer, which can be of any type, however should not be related to the starting monomer.

Preferred examples of such a polymer are polystyrene, polymethylstyrene, Polyethylstyrene, polyvinyl acetate, polyisobutylene, polymethyl acrylate, polyethyl acrylate, Polymethyl methacrylate, polyethylene methacrylate and polybutyl methacrylate. The e from choice among these additional polymers, however, must be carefully made so that the selected polymer has a homogeneous liquid phase with the mixture of the starting monomers and the organic solvent forms. The degree of polymerization of the selected Polymer is on the order of 3,000 to 300,000, preferably on the order of 10,000 to 100,000 of the molecular weight, the solubility of the polymer being in the solvent must be taken into account. There is a tendency that with larger Proportion of the polymer used, the greater the porosity of the product; the appropriate polymer content will normally be in a range of 1-100%, preferably determined in a range of 6 - 90 percent by weight of the monomer mixture, each depending on the desired properties of the mixed polymer product.

A catalyst is usually used in carrying out the polymerization used so that the polymerization reaction proceeds quantitatively. One such catalyst can be among the known catalysts for the polymerization of vinyl compounds to be selected. Such catalysts are benzoyl peroxide, tertiary butyl peroxide, Lauroyl peroxide and azobisisobutyronitrile.

The invention can either be achieved by using suspension polymerization or the blook polymerization can be carried out.

However, suspension polymerization is used for the production of a Mixed polymer in the form of a spheroid is preferred, especially for an ion exchange resin. A suspension stabilizer is expedient for carrying out the suspension polymerization to be added to the reaction system so that the reaction is facilitated. It can be known Stabilizers for such reactions are used, examples of which are Polyvinyl alcohol, sodium polyacrylate, sodium polymethacrylate, Calcium carbonate, Calcium Sulphate, Oarboxymethyl Cellosolve and Starch. The interpolymerization should at a temperature above the dissociation temperature of a radical generator are executed. Under normal pressure, the temperature is usually between 60 and 900 C. If a porous resin alone is desired, the extraction treatment is carried out of the resulting mixed polymer in a solvent that is used to dissolve the linear Polymers is suitable for the linear polymer that is formed in the course of the polymerization has been added, can be removed from the copolymer. The one used for this The solvent is preferably the same as that used in the reaction system has been added during the polymerization. The extraction can be done either after the Soxhlet procedure or a chamber procedure.

On the other hand, for the production of a porous ion exchange resin Ion exchange groups built into a porous resin that undergoes an extraction treatment was subjected, or also into a copolymer which is not subjected to such an extraction treatment was exposed, namely when there is a possibility that this extraction in gaitendem Extent due to the treatment stages following the incorporation of the ion exchange groups is effected.

The incorporation of an ion exchange group into a copolymer can be carried out by means of a treatment similar to a known method. E.g. with a resin On the basis of styrene, sulfonation using sulfuric acid or chlorosulfonic acid Sulfur trioxide, so that a cation exchange resin is obtained.

In another way, the resin is chloromethylated of chloromethyl ether or a mixture of hydrogen chloride and formaldehyde with subsequent amination to form an anion exchange resin. The usage of trimethylamine, dimethylethanolamine or the like. To amination leads to a strong basic anion exchange resin, whereas the use of polyalkylene polyamines like ethylenediamine and diethylenetriamine to a weakly basic anion exchange resin leads. Furthermore, nitration of a mixed polymer by means of nitric acid and the following provides Reduction a weakly basic anion exchange resin.

On the other hand, the use of an acrylate or methacrylate based resin results a weakly acidic, carboxylic acid type cation exchange resin when this resin is hydrolyzed.

Subsequent amidization of the hydrolyzed resin gives a weakly basic anion exchange resin. If the need arises, it can obtained mixed polymer are amidized immediately.

According to the invention, the reaction conditions can be within those mentioned Limits can be selected as desired to contain an interpolymer that is in its properties depending on and in combination with the added polymer as well as the selected reaction conditions can be different. Generally speaking, the active surface area will increase with an increase in the proportion of solvent, whereby the porosity remains essentially unchanged; with an increasing polymer content the porosity can be increased. In addition, the properties of the Change the product by changing the proportion of polyvinyl monomer. E.g. receives when using styrene as the monovinyl nonomer and divinylbenzene as the polyvinyl nonomer (Divinylbenzene is referred to below as DVB, contains commercially available DVB about 44.4 attiylvinylbenzene) and when using polystyrene as an additional polymer as well as toluene as a swelling solvent, each in different proportions various interpolymers having different properties according to the following Table 1.

Table 1 Composition of the monomer phase Properties of the copolymers obtained No. Styrene DVB EVB Toluene Polysty- active surface portion of the absorbed rol (BET method) cyclohexane %%%% m² / g-copolymer cm³ / g-copolymer 1 64 20 16 0 0 0 0 2 64 20 16 100 0 0 0.1> 3 64 20 16 0 10 3.3 0.1 4 64 20 16 100 10 35.0 0.84 5 64 20 16 140 10 41.5 0.80 6 28 40 32 100 0 0 0.75 7 28 40 32 0 10 17.1 0.20 8 28 40 32 100 10 120.0 1.20 1) The respective proportions of styrene, ethylvinylbenzene and DVB are calculated in percent by weight of the total monomer mixture.

2) The respective proportion of toluene and polystyrene is in percent by weight based on the total monomer mixture.

3) The active surface area was determined by nitrogen adsorption after BET method using a Shibata Scientific-Devices SA-200 device Industries Std.

certainly.

4) The proportion of the absorbed cyclohexane was determined in such a way that that a dried copolymer was immersed in cyclohexane overnight; attached, Excess cyclohexane was separated off by means of a centrifugal separator, whereupon the weight gain was measured. As cyclohexane precipitates a gel mixed polymer is suitable, such a copolymer never absorbs cyclohexane. Hence is the greater this absorption value, the greater the porosity.

In the following Table 2, the copolymers are in each case according to Invention with copolymers according to the prior art with regard to their properties compared depending on the composition of the monomer phase.

Table 2 Composition of the monomer phase properties of the obtained Mixed polymer No. DVB EVB toluene polystyrene act. Surface pore volume %%%% N x 104 m² / g mixed pole. cm³ / g mix. 1 50 40 75 10 3.2 429.0 0.741 2 50 40 100 10 3.2 560.0 0.988 3 50 40 140 10 3.2 630.0 1.167 4 50 40 100 20 3.2 175.0 1.199 5 50 40 100 10 4.0 513.0 0.974 6 20 16 100 10 4.0 20.0 0.507 7 50 40 100 7 3.2 471.0 0.753 8 50 40 100 0 - 0 0.100 9 50 40 0 20 3.2 4.6 0.206 10 50 40 * 100 0 - 328.7 1.284 11 20 16 * 100 0 - 65.5 1.044 12 20 16 100 0 - 0 0.1> 13 20 16 0 10 3.2 3.3 0.1 14 20 16 0 0 - 0 0 15 50 40 100 10 4.3 12.0 0.90 16 50 40 140 10 4.3 33.7 0.49 1) The values in table 2 have the same meaning as in table 1.

2) In the examples "*", haptan was used as the precipitant instead of Toluene used as a solvent.

For the above examples, the pore radius and pore volume were measured by means of an AG-65 Hg porosimeter from Carloerba Company. The respective Results are in Figures 1 to 3 of the drawings for the pore distribution and the relationship between the polymerization conditions and the active surface area as well as the pore volume recorded.

The relationship between the properties of the interpolymer and the Manufacturing conditions can be summarized as follows.

1. Active surface: 1) The maximum value for the active surface is made by selecting the proportion of the additive polymer, the molecular weight of the polymer and the proportion of solvent achieved.

2) The maximum value of the active surface is shown by enlarging the proportion of the additional polymer or by increasing the proportion of solvent enlarged together with a polymer of lower molecular weight.

3) The active surface increases with an increasing proportion of the crosslinking agent to.

4) The active surface area is reduced when the copolymer is converted into an ion exchange resin.

2. Pore radius: 1) With increasing proportion of the additional polymer, increasing Molecular weight of the polymer and increasing proportion of the crosslinking agent the. Pore radius larger.

2) With increasing proportion of the solvent with unchanged others Conditions, the pore radius decreases.

3) The conversion of the mixed polymer into an ion exchange resin is effected a more or less strong increase in the pore radius.

3. Pore volume: 1) With an increase in the proportion of the additional polymer, des The molecular weight of the polymer and the crosslinking agent becomes the pore volume greater.

2) The maximum pore volume is determined by applying an appropriate Solvent content achieved.

3) The pore volume decreases when the copolymer in ion exchange resin is converted.

4. Pore distribution: 1) With an increase in the proportion of the additional polymer, the molecular weight of the polymer and the proportion of the crosslinking agent is the Pore distribution more pronounced.

2) As the proportion of solvent increases, the pore distribution becomes wider.

3) Conversion of the mixed polymer into an ion exchange resin brings about no significant change in the pore distribution.

Accordingly, one can adjust the properties of the mixed polymer as desired and the ion exchange resin by changing the proportion of the additional polymer, the molecular weight of the polymer and the proportion of the solvent in addition to the proportion of the crosslinking agent changes in the context of the polymerization conditions.

The copolymer obtained according to the invention, which is particularly with regard to porosity and active surface area is advantageous as an adsorbent very useful for numerous applications. These copolymers turn out to be, for example for the adsorption of organic substances with large molecules in an aqueous medium like alkylbenzenesulfonate especially useful because recovery is easy, because they show essentially no polarization, they are also used as carriers useful for catalysts and as absorbents in gas chromatography The ion exchange resins made from such copolymers have used a higher exchange rate for the ion exchange reaction in comparison to known resins, improved properties for resistance to stress by osmotic pressure as well as mechanical and other shocks. As a result of the larger Porosity can also be achieved by ion exchange reactions in a non-aqueous solution perform with a noticeably higher yield.

The invention is explained with reference to a few exemplary embodiments explains where the active surface area is measured by the BET method; the porosity was determined based on the proportion of an absorbed organic solvent, which causes essentially no swelling of the porous material; the solvent content are within the starting composition and the proportion of linear polymer given in percent by weight in relation to the total weight of the monomer mixture; Divinylbenzene (DVB) and the monovinyl monomer are each in percent by weight given based on the monomer mixture.

Example 1 A homogeneous solution mixture of 256 g of styrene, commercially available Divinylbenzene with 55.6% purity, 400 g of toluene, 40 g of polystyrene with a medium Molecular weight of 37,000 and 2 g of benzoyl peroxide were dissolved in an aqueous solution of 128 g of sodium chloride and 3.2 g of commercial polyvinyl alcohol dissolved in 3 200 g of water were introduced. The monomer phase was stirred appropriately and heating to 80 OC for a period of 8 hours homogeneously distributed, with nitrogen the reaction was initiated. The mixed polymer parts obtained were filtered off, Washed out in water to remove excess solvent and water heated as well as dried. Benzene in an amount about five times dry Mixed polymer was then added and the mixture was allowed to stand for 4 hours at room temperature stirred for the purpose of extracting the polystyrene. The copolymer obtained was filtered off, washed out with benzene and heated to dryness. The copolymer thus obtained (I) became as white, opaque spheroids weighing 360 g won. The active surface area of the mixed polymer according to the BET method was found to 35.0 m2 per g of the mixed polymer The mixed polymer (II), which according to the same Process sequence with the exception of a polystyrene addition, produced for comparison purposes had an active surface area of 0 m2 per g.

The mixed polymer (III) was obtained in a similar manner, but without the addition of toluene and had an active surface area of 3.3 m2 per g.

The copolymer obtained by the process of the invention and the copolymers produced for comparison purposes absorbed cyclohexane in Portions of 0.84 cm3, 0.1 cm3 each or a little more and 0.1 cm3 per g of the mixed polymer. The mixed polymer according to the invention was thus found superior in terms of porosity.

The three kinds of mixed polymers were subjected to adsorption tests with respect to alkylbenzenesulfonate, hereinafter referred to as ABS will.

Test method: Stock solution .: Aqueous 1% ABS solution, whereby the ÄBS by purifying a commercially available alkylbenzenesulfonate with a purity of 99.5% is preserved.

Mixed polymer content: 40 cm3 Adsorption process: A column with 1 cm in diameter was filled with the copolymer, 40 cm3 of stock solution flowed then through the column at a liquid space velocity (LSV) of 4; then 40 cm3 of water with a LSV of 4 was allowed to flow through for washing out.

Regeneration process: 80 cm3 of methanol flowed through the column a LSV value of 4.

The measured values obtained are given in Table 3 below.

Table 3 ABS adsorption regeneration Mixed polymer Share share g / 40 cc% g / 40 cc (I) 0.16 40 0.136 85 (II) OOOO (III) OOOO According to Table 3, the copolymer (I) proves to be a superior adsorbent in the process of the present invention.

Example 2 A homogeneous mixture of 112 g of styrene, 288 g of commercial grade Divinylbenzene, 400 g of toluene, 40 g of polystyrene and 2 g of benzoyl peroxide was in a aqueous solution of 3,200 g of water and 128 g of sodium chloride and 3, -2 g of commercially available Polyvinyl alcohol introduced. The monomer phase was used to carry out the reaction distributed in the appropriate particle size with stirring, the reaction took place at a temperature of 800C for a period of 8 hours. Thereby nitrogen was in initiated the reaction system. After the completion of the reaction, it was obtained Mixed polymer filtered off, washed out with water to remove excess Water and solvent heated and dried. Benzene in a proportion of five times of dry mixed polymer rare added, the mixture was stirred at room temperature for 4 hours and the polystyrene was extracted by extraction removed. The resulting copolymer was filtered, washed out with benzene and heated to remove the excess benzene. This mixed polymer lay in white, opaque spheroids weighing 340 g. The active surface of the mixed polymer was determined by the BET method.

120 m2 per g of mixed polymer. For comparison purposes, the same procedure was used carried out with the exception that no polystyrene was added to the monomer mixture became. The resulting copolymer then had an active surface area of 0 m² per G. Accordingly, without the addition of toluene, the active surface of the resulting mixed polymer became of only 17.1 m² per g found.

The percentage of absorbed cyclohexane in the various polymers resulted in 1.20 GR3, 0.75 cm3 and 0.2 cm3 per g of copolymer, respectively.

Example 3 The procedure of Example 1 was used to produce of a mixed polymer under the conditions given in Table 4 below was carried out with the following results.

Table 4 I rO (0 1 I <1> 1 d I h (0 0 (0 H la mm ar a, k 1:, k a> æ Ha>: i1a> o 4, F: H Pf Fi a> Jrl H0 LO 1: 1 - . m X p (04, w BH HH bb X frl n a> H o> dd 1: 1: O.r4 to odn N o 0 z R at 1 20 toluene 100 PVAc 10 1.1 8.6 - 2 20 CCl4 100 PST 10 4.1 7.0 - 3 16 toluene 100 PST 10 3.2 25.0 0.20 4 20 toluene 100 PST 10 3.2 36.0 0.35 5 40 toluene 100 PST 10 3.2 282.0 0.76 6 50 toluene 100 PST 10 3.2 560 0.99 Example 4 A homogeneous mixture of 284.7 g of commercially available acrylic acid ester, 115.3 g of commercially available divinylbenzene, 400 g of toluene, 40 g of polystyrene and 2 g of benzoyl peroxide was dissolved in an aqueous solution of 128 g of sodium chloride and 3.2 g of commercially available polyvinyl alcohol in 3 200 g of water were introduced. The monomer phase was distributed by stirring and heated to 80 ° C. for 8 hours while passing in nitrogen. The resulting copolymer was filtered off, washed out with water and heated to remove excess water and solvent. Then toluene was added in five times the proportion of the dry mixed polymer. The mixture was stirred for 4 hours at room temperature, the polystyrene portion was extracted. The excess toluene was then removed from the interpolymer by heating. The copolymer obtained was in the form of white, opaque spheroids weighing 365 g. The active surface area was determined to be 24 m2 / g by the BET method. For comparison purposes, the same procedure was followed with the exception that no polystyrene was added to the monomer mixture. This gave a mixed polymer with an active surface area of 0. A similar process was carried out without the addition of toluene, whereby a mixed polymer with an active surface area of 2.5 m 2 / g was obtained.

Example 5 Decolorization tests were carried out on a glucose solution with the mixed polymer No. 7 according to the invention and the known copolymers no. 8 to 10 carried out according to Table 2.

Stock solution: Dextrose solution, degree of coloration 0.522 (-log T) measured at a wavelength of 430 me using a photoelectric photometer with a 20 m / m cell from Hitachi Ltd.

Volume of the mixed polymer: 50 cm3 each column: 1 cm diameter Working method: continuous process with a space velocity of 5. The outflow with a predetermined amount, the degree of coloration was determined by the aforesaid Photometer measured.

According to Figure 4 of the drawings, the mixed polymer proved to be Invention in terms of the discoloration effect as superior. The Harz No. 7 after the invention had a better one Decolorization properties in comparison to the resin no. 8, during the preparation of which only one solvent was added Results are even better compared to resin no. 9 in its manufacture only Polymer was added; the resin no. 10 was obtained by using a precipitant.

Example 6 a) Production of a carrier body: A homogeneous mixture from 256 g of styrene, 144 g of divinylbenzene of 55.6% purity with the remainder of 44.4 % consists essentially of ethyl vinylbenzene, 400 g of toluene, 40 g of polystyrene with a viscometric average molecular weight of 40,000 and 2 g of benzoyl peroxide were in an aqueous solution of 128 g of sodium chloride and 3.2 g of commercially available Polyvinyl alcohol was introduced into 3,200 g of water. The monomer phase was then under Stir distributed. The reaction took place with introduction of nitrogen for 8 hours long at a temperature of 800C.

The obtained mixed polymer particles were filtered off into water washed out and heated to remove excess solvent and water. The resulting dry copolymer was mixed with benzene in a five-fold proportion mixed and extracted the polystyrene for 4 hours at room temperature ditched. The copolymer was then filtered off, washed out with benzene and dried by heating. The obtained mixed polymer particles (I) were white and opaque weighing 360 g, the active surface resulted according to the BEX process at 25 m2 per g of mixed polymer.

For comparison purposes, the same procedure was followed with the.

Exception stated that only polystyrene was added without the addition of toluene with which a mixed polymer (II) was obtained, the active surface of which was somewhat 3 m2 / g. A similar process was carried out with the exception that only toluene was added without the addition of polystyrene, making a copolymer (III), which had an active surface area of 0 m2 / g, i.e. essentially no active surface area detectable by the BET method.

b) Preparation of a strongly acidic ion exchange resin: 50 g des Mixed polymer (I), 200 g of water and 50 g of toluene were placed in a flask and swelling of the mixed polymer for one hour at a temperature of 700C-sur stirred. After removing the water and the excess toluene by centrifugal filtering was the swollen copolymer together with 500 g of 98% sulfuric acid in one Flask inserted and kept at a temperature of 11000 for 12 hours with stirring brought to reaction. After the completion of the reaction, the mixture became room temperature cooled, the unused sulfuric acid was diluted with water and filtered off and then washed out with water.

The resulting resin was mixed with an excess of sodium carbonate, so that by converting the sodium expression of the resin with a yield of 270 cm3 received. The resin was yellowish brown and opaque in the form of spheroids, which were completely flawless with no cracks. The resin contained 5.5.2% water a decomposition size of 4.26 meq / g against neutral salts, which is a value of 1.47 meq / cm3. This 11arz and resins made by an equal treatment from the copolymers (II) and (III) were obtained for a measurement of active surface and the toluene absorption. The measurement results are in in Table 5 below.

Table 5 d composition the monomer phase> 43 a> p ( N a OA $ o - 00> 3 r ( H0 XX H0 0 HjU 0 o Sk-1 - I 100 10 18 0X42 Sk-1 - II O 10 1s OOX 11 Sk-1 - III 100 0.04 c) Preparation of a strongly basic ion exchange resin: 50 g of the mixed polymer (I) according to the above process a), 2-5 g of chloromethyl ether and 30 g of zinc chloride were placed in a flask and stirred at a temperature of 50 ° C. for 10 hours. The reaction mixture was poured into an appropriate amount of cold water so that excess chloromethyl ether and zinc chloride were broken down. The chloromethylated copolymer obtained was carefully washed out with water. This interpolymer was then placed in a flask, 150% benzene was added, and the flask was allowed to stand for 30 minutes to allow the interpolymer to swell. The swollen copolymer was then introduced into 100 g of an aqueous 30 percent strength trimethylamine solution, where a reaction took place at a temperature of 50 ° C. with stirring for three hours. After the reaction had ended, the substances were filtered off and washed out with water. The resin obtained was in the form of chlorine in the form of a light yellow, opaque, perfect spheroid.

The yield was 260 cm3. The resin had a water content.

of 49.4%, the decomposition size for neutral salts was 288 meq / g, corresponding to a value of 1.00 meq / cm3. The idi polymers (II) and (III) were treated in the same way.

The resins obtained in each case were dried and tested for active surface and the absorbed toluene content measured.

Table 6 Composition of the active surface absorbed Resin monomer phase (BET process) toluene content Toluene polystyrene m² / g cm³ / g %% SA-1- I 100 10 10 0.51 SA-1- II 0 10 1.0> 0.1 SA-1- III 100 0 0 0 d) Preparation of a weakly basic ion exchange resin: 50 g of copolymer (I) according to process step a) were treated in the same way as in example c) above, so that a chloromethylated copolymer was obtained. This copolymer was placed together with 56 g of an aqueous 40 percent dimethylamine solution and 150 g of an aqueous 40 percent NaOH solution in a pressure vessel, where the reaction lasted at a temperature of 800C for 6 hours, whereupon 190 cm3 of an OH expression were obtained of the resin received. The resin had a water content of 50.0 96, the acid adsorption capacity was 4.02 meq / g, corresponding to 1.32 meq / cm3, the active surface area was 21.0 m2 per g and the pore volume was 0.49 cm3 / g.

Example 7 a) Production of a carrier body: A homogeneous mixture from 284.7 g of styrene, 115.3 g of commercial divinylbenzene with 55.6% purity (der The remainder of 44.4% is mainly ethylvinylbenzene), 400 g toluene, 40 g polystyrene and 2 g of benzoyl peroxide was dissolved in an aqueous solution of 128 g of sodium chloride and 3.2 g of commercially available polyvinyl alcohol - introduced into 3,200 g of water. The monomer phase was distributed by stirring. The reaction with stirring continued at one temperature of 180C for 8 hours while nitrogen was bubbled in. The received Mixed polymer particles were filtered off, washed with water and removed for removal excess solvent and water heated.

The mixed polymer particles were mixed with benzene in a five-fold proportion of the mixed polymer. The extraction was carried out at room temperature with stirring of polystyrene.

The interpolymer was then filtered off and removed to remove the excess Heated benzene. The mixed polymer (I) was in the form of white, opaque particles weighing 370 g. After the BE? Process, it became an active surface of the dry mixed polymer of 14 m2 / g measured.

For comparison purposes, the resin (II) was according to conventional methods produced where the course of the procedure was essentially the same, apart from that only polystyrene and not toluene were added. For the resin (II) a active surface of about 1.0 m2 / g measured. Similarly, the resin (III) using the same procedure except that only toluene and not polystyrene to-0O9S52 / 2O38 BAD ORIGINK were set. The active surface area was found to be 0 m2 / g, i.e. it was by the BET method not measurable.

b) Production of a strongly acidic ion exchange resin: the mixed polymer (I) was sulfonated as in Example 6 above. The resin obtained lay inform of essentially perfect spheroids that were opaque and were yellowish brown in color. The yield of the resin in the Jatriurnausprung was 280 cm3. The resin had a water content of 56.6% and a decomposition size for neutral salts of 4.34 meq / g, corresponding to a value of 1.40 meq / cm3.

This resin as well as resins obtained by sulfonating the copolymers (II) and (III) were obtained for measuring the active surface area and the Toluene absorption dried. The measured values are given in Table 7.

Table 7 Composition of the monomer active toluene phase upper absorption Resin toluene polystyrene surface %% (BET travel) m² / g cm³ / g Sk-2 - I 100 10 8 0.30 Sk-2 - II 0 10 1.0 0.08 Sk-2 - III 100 0 0 0.03 c) Production of a strongly basic ion exchange resin: The mixed polymer (I) according to a) was treated by chloromethylation and subsequent amination in accordance with process c) of Example 6. The resin obtained had a water content of 48.7% and a decomposition size for neutral salts of 3.25 meq / g, corresponding to -1.14 meq / cm3. The copolymers (II) and (III) were treated accordingly. The obtained resins were dried to measure the active surface area and the toluene absorption, respectively. The measured values are given in Table 8 below.

Table 8 Composition of the monomer active toluene phase upper absorption Resin toluene polystyrene surface %% (BET travel) m² / g cm³ / g SA-2 - I 100 10 8.3 0.38 SA-2 - II 0 10 0 0.1 SA-2 - III 100 0 0 0 Example 8 a) Production of a support body: A homogeneous mixture of 284.7 g of commercially available methyl acrylate, 11-5.3 g of commercially available divinylbenzene, 400 g of toluene, 40 g of polystyrene and 2 g of benzoyl peroxide was dissolved in an aqueous solution of 128 g of sodium chloride and 3 , 2 g of commercially available polyvinyl alcohol are added to 3,200 g of water. The monomer phase was distributed by stirring for the reaction, the reaction was carried out at a temperature of 80 ° C. for a period of 8 hours, nitrogen being introduced into the reaction mixture. After the completion of the reaction, was. the copolymer obtained is filtered off, washed out with water and heated to remove excess water and solvent. The dry copolymer thus obtained was mixed with a five-fold amount of toluene and kept for 4 hours at room temperature with stirring to extract the polystyrene. The interpolymer was then filtered off and heated to remove the excess toluene. The obtained mixed polymer (I) was found in the form of a white, opaque spheroid weighing 365 g. The active surface area of the mixed polymer was found to be 24 m2 / g according to the BET method.

For purposes of comparison with known copolymers, the same was used The reaction sequence for a monomer mixture carried out without the addition of polystyrene, with which a copolymer (II) having an active surface area of 0 m 2 / g was obtained A mixed polymer (III) was prepared from a monomer mixture without the addition of toluene. The active surface area of this mixed polymer (III) was found to be 2.5 m² / g.

b) Preparation of a weakly basic ion exchange resin: One Mixture of 100 g of mixed polymer (I) from the above example and 500 g of a. watery 15 percent sodium hydroxide solution was melted with heating. The received Resin was treated with an aqueous N-HCl solution to convert it to the H expression, resulting in a yield of 550 cm3. The resin had a water content of 47.4% and a cation exchange capacity of 8.6 meq / g. After drying it was the active surface of the resin measured by the BE method to be 9.0 m2 / g. In a similar way Way were the copolymers (II) and (III) according to the previous section a) hydrolyzed to give acidic ion exchange resins, the active surface of which: each was only 0 m2 / g or a little more than 1.0 m2 / g.

Example 9 Following the procedure of Example 6, a support body was obtained prepared using instead of polystyrene polyvinyl acetate with a molecular weight used by 13,000. In the same way, a support body was used made of carbon tetrachloride instead of toluene.

These support bodies were sulfonated according to process step b) of Example 6, 8o that a strongly acidic ion exchange resin was obtained. The resulting Na expression of this resin and the support body had the following properties: Table 9 with polyvinyl acetate With CCl4 M¹) Yield in g according to the extraction of the Polymers 355 350 Active surface in mt / g 8.6 7.0 R2) Yield in cm3 240 215 Exchange size in meq / g 4.1'1 4.10 Exchange size in meq / cm) 1.58 1.82 Water content in * 48.1 44.3 Active surface in m² / g 4.0 3.0 Pore volume in cm² / g 0.25 0.27 Note: 1) Support body 2) Resin application example 1 The absorption curve of triethylamine in benzene was determined for four types of strongly acidic cation exchange resins of Examples 6 and 7. The results are plotted in Figure 5 of the drawings.

Figure 5 shows that the produced by the method according to the invention Resin has a surprising influence on the ion exchange reaction in a non-aqueous Medium shows, on the other hand, the resin with the sole addition of toluene and polystyrene little effect on the ion exchange reaction in a non-aqueous Medium yields.

Application example 2 The strongly basic anion exchange resins of Examples 6 and 7 were recognized for their ability to adsorb organic substances studied with high molecular weight. The results are plotted in FIG. Commercial fumaric acid was used as the organic substance for the investigations; a glass column with a diameter of about 2 cm was made with 30 cm3 of a Cl expression filled of resin; an aqueous fumaric acid solution at an initial concentration of 10 ppm was passed through the column from above at a space velocity of 10, thus-the fumaric acid content measured in the liquid draining from the column could be.

Table 11 shows the types of resins and compositions used The starting material for the production of these types of resin is indicated. The resin 1 is obtained by the process according to the invention, resins 2 and 3 are comparison resins.

Table 11 No. Resin type Composition of the monomer phase DVB styrene ethyl vinyl toluene polystyrene %% benzene %%% 1 Harz des 20 64 16 100 10 Example 2 also 20 64 16 0 10 SA0-1-II 3 also 20 64 16 100 0 SA-1-III Figure 6 shows that in terms of the effectiveness of removing an organic substance, the resin according to the method of the invention is superior to the prior art resins. Consequently, the resins of the invention are useful for water treatment, which is very important nowadays; the removal of organic matter in water is a vital problem that needs to be solved.

For the tests, 5 cm3 of dry resin stamping was used; a quantity of a triethylamine-benzene solution with an initial concentration of 0.02 N was added to give a 0.75 meq / meq resin ratio; after a briefly the solution was drained to reduce the amount of in the solution existing triethylamine could be determined.

The numbers 1 to 4 in table 10 indicate the respective type of used resin, with resins 1 and 2 by the process according to the invention while Resins 3 and 4 are used for comparison purposes.

Table 10 No. Resin type Composition of the monomer phase DVB styrene ethyl vinyl benzene toluene poly %%%% styrene 1 resin 16 71 13 100 10 Sk-2-I of the game 7 2 resin 20 64 16 100 10 Sk-1-II of the game 6 3 resin 20 64 16 100 0 Sk-1-III of the game 6 4 resin 16 71 13 0 20 Sk-2-II of the game 7

Claims (19)

P a t e n t a n s p r ü c h e 1. Process for the production of a porous, cross-linked mixed polymer, characterized by mixed polymerisation of monovinyl and polyvinyl monomer in the presence of an organic solvent which dissolves the monomers and a linear monovinyl polymer, forming a swollen interpolymer we in which the linear polymer with the monomers and the solution means a homogeneous one Phase forms, and by subsequent extraction of the linear polymer from the copolymer. 2. The method according to claim 1, characterized in that the copolymerization takes place in suspension. 3. The method according to claim 1 or 2, characterized in that as Monovinyl monomer is at least one selected from the group consisting of the aromatic Monovinyl compounds and alkyl esters of unsaturated, aliphatic carboxylic acids includes. 4. The method according to claim 3, characterized by at least one aromatic nonovinyl compound from the group of styrene, ethylstyrene and chlorostyrene. 5. The method according to claim S, characterized by at least one Alkyl ester of an unsaturated, aliphatic carboxylic acid from the group of acrylic acid esters and the methacrylic ester of aliphatic alcohols having 1 to 4 carbon atoms 6. The method according to any one of claims 1 to 5, characterized by at least one Polyvinyl monomer from the group of aromatic polyvinyl compounds, unsaturated, aliphatic n carboxylic acid esters of alkene glycols and the aliphatic dicarboxylic acid esters of unsaturated, aliphatic alcohols. 7. The method according to claim 6, characterized by at least one aromatic polyvinyl compound from the divinyl group benzene, Divinyltoluene, divinylnaphthalene, and trivinylbenzene. 8. The method according to claim 6, characterized by at least one unsaturated, aliphatic carboxylic acid ester of an alkene glycol from the group the acrylic acid ester and the methacrylic ester of ethylene glycol. 9. The method according to any one of claims 1 to 8, characterized by at least one solvent from the group of aromatic hydrocarbons and the chlorinated aliphatic hydrocarbons. 10. The method according to any one of claims 1 to 9, characterized in, that the solvent in an amount of 20-300 percent by volume based on the Weight of monomers used. 11. The method according to claim 10, characterized by at least one aromatic hydrocarbon from the group of benzene, toluene and xylene. 12. The method according to claim 10, characterized by at least one chlorinated hydrocarbons from the group of chlorobenzene, carbon tetrachloride, Tetrachloroethane and trichlorethylene. 13. The method according to any one of claims 1 to 12, characterized by a linear polymer with a molecular weight between 3,000 and 300,000. 14. The method according to any one of claims 1 to 13, characterized in, that the linear polymer in a proportion of 1 to 100 percent by weight of the monomers is used. 15. The method according to any one of claims 1 to 14, characterized in that that for the preparation of an ion exchange resin in addition to the extraction of the linear polymer is the mixed polymer at the same time or afterwards is endowed with ion exchange properties. 16. The method according to claim 15, characterized in that for the display-one Cation exchange resin a sulfonation of the mixed polymer takes place. 17. The method according to claim 15, characterized in that for representation an anion exchange resin, amino groups are introduced into the copolymer, either by chloromethylation with subsequent amination or by nitration with subsequent reduction. 18. The method according to claim 15, characterized in that for representation an anion exchange resin, the copolymer either by amide formation or treated by hydrolysis with subsequent amide formation. 19. The method according to claim 15, characterized in that for representation of a carbonic acid-like cationic resin is a hydrolysis of the copolymer he follows.