HU185621B - Method for producing sorption materials of sulfur content - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention relates to a vinyl monomer styrene, acrylonitrile, vinylpyridine, Ν, ρ-ρρ'-diphenylmethane bis-maloimide, acrylic acid, and the like. methyl ester or a mixture of vinyl pyridine and divinylbenzene are used, 0.014-1.4 moles of divinyl sulfide are calculated per mole of monomer, and the copolymerization is carried out at 50-90 ° C in the presence of an initiator, and the resulting copolymer is optionally chloromethylated and subsequently \ t animated or hydrolyzed or sulfonated or aminated, and then optionally carboxylated. The copolymers prepared as described above, depending on the type, proportion, and subsequent chemical treatment of the starting vinyl monomer, are high-capacity sorption materials for different materials. -1-

Description

The present invention relates to a process for the preparation of sulfur-containing sorption materials, preferably ion-exchange materials. The sorption materials produced can be used, for example, in the hydrometallurgy to recover copper, silver and other metals, or in the pharmaceutical industry for the recovery of N-methyl-α, L-glucosaminido-O, L-streptosido-streptide known as streptomycin.

The various industries are known as the so-called. sorption materials, including ion exchangers, are increasingly used. Practical application has shown that sorption materials exhibit pressure, friction, and osmotic wear.

Therefore, in recent years, research has sought to develop sorption materials with improved performance properties.

Known processes for the preparation of backbone polymers by copolymerization of a vinyl-containing monomer with a plurality of vinyl-containing monomers (e.g., divinylbenzene) (British Patent Nos. 1,050,207 and 1,058,625, French Patent No. 1,483,946, 1,113). German Patent No. 570, Japanese Patent No. 14,739-71, Soviet Patent No. 280,843). The particulate, internally porous or gel-like backbone polymer is further treated to introduce ionic groups.

However, the functional properties of the ion exchangers prepared according to the above process are not satisfactory. This is because the small divinylbenzene molecule promotes the dense arrangement of the molecules. Therefore, ion-exchangers based on such polymers are less permeable to larger ions, and have low mechanical strength and osmotic stability. When the amount of crosslinker in the ion exchange polymer backbone is reduced, the ion exchange capacity is increased to some extent, but the mechanical strength and osmotic stability are noticeably reduced.

The mechanical strength in this specification is defined as the amount of particles remaining intact, expressed as a percentage of the ion exchanger treated in a ball mill under defined conditions.

Osmotic stability refers to the remainder expressed as a percentage of the total amount of ion exchanger treated with acid, water, and alkali.

Ion exchangers with a macrocellular structure have made progress due to their higher mechanical strength and osmotic stability.

For example, the preparation of copolymers with a macrocellular structure is described in U.S. Pat. U.S. Pat. The process is based on bulk polymerization with the exclusion of oxygen. The reaction mixture consists of one vinyl-containing aromatic hydrocarbon (s) and multiple vinyl-containing aromatic hydrocarbons. Divinyl sulfide is used as a crosslinking salt. Prior to polymerization, the reaction mixture is diluted with water to a concentration of 5-70%. Polymerization control agents are also used. Functional groups are incorporated into the resulting crosslinked copolymer.

By the described technology, a cross-linked block polymer can be produced, which is disadvantageous for the subsequent introduction of functional (ion-exchange) groups.

No. 529,176. According to the process described in U.S. Patent No. 5,194, divinyl sulfide is also used as a crosslinker in the copolymerization of styrene or acrylic acid or methacrylic acid esters in an amount of 0.16 to 0.2 moles per vinyl monomer. Polymerisation uses azoiso2-butanoic acid dinitrile. The resulting particulate sorption material has a macrocellular structure.

The particles are treated to inoculate the ionic groups and washed at 50-100 ° C with 10-30% hydrogen peroxide solution.

However, the mechanical strength and osmotic stability of the sorption materials obtained as described above are not sufficient, so that ion exchangers are not used in industrial practice.

It is an object of the present invention to provide sulfur-containing sorption materials with high mechanical strength and osmotic stability.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a process by which the mechanical strength and osmotic stability of a sorption material is good by providing a highly flexible backbone polymer.

The present invention relates to a process for the preparation of sulfur-containing sorption materials by copolymerization of vinyl-containing monomers with divinylsulfide. The process according to the invention is characterized in that as the vinyl monomer is used filters, acrylonitrile, vinylpyridine, N, N '- pp'-diphenylmethane bis-maleimide, acrylic acid methyl ester or a mixture of vinylpyridine and divinylbenzene in a ratio of 1: 0.02-1: 0.15 -1.4 moles of divinyl sulfide are used.

Polymerization of divinyl sulfide with vinyl moiety monomers in the above quantitative ratio results in a highly elastic crosslinked polymer. The macroporous sulfur-containing sorption materials produced according to the invention therefore have good mechanical strength and high osmotic stability. Even with rapid ion exchange and complexation, ions can penetrate sorption materials well.

The ion exchangers prepared according to the invention are particularly applicable to products of biological origin such as lipase. σ amylase, streptomycin, and selective extraction and purification of amino acids such as lysine (2,6-diaminohexanoic acid).

Sulfur in sulfide bonds in ion exchangers, in particular by interacting with other foreign atoms, renders the resin selective for the separation of volatile metals and platinum group metals. Therefore, sulfur-containing ion exchangers can be used, for example, for the recovery, selective separation of copper, nickel, cobalt, tungsten, molybdenum, mercury, lead, gold, silver, platinum from technical solutions, wastewater and solvent solutions. Some of the sorption materials obtained in the process of the invention, such as copolymers of vinylpyridine and divinylsulfide, also have ion-exchange properties, for example, adsorbing halide ions from aqueous solutions. Other sorption materials, on the other hand, adsorb metal ions from organic solvent solutions as ion exchangers containing carboxyl groups.

Preferably 0.12-0.14 moles of divinyl sulfide are used per mole of vinyl monomer. The vinyl monomer is preferably vinyl pyridine. The resulting sorption material has a high, selective ion exchange capacity for platinum metals.

When a 1: 0.02-1: 0.15 molar mixture of vinylpyridine and divinylbenzene is used as the vinyl monomer, 0.12-0.14 molar divinyl sulfide is also used. The sorption material thus obtained has a high mechanical strength and a high selective ion exchange capacity for platinum metals.

-2185 621

When styrene is used as a monomer containing vinyl groups, 0.046-0.14 moles of divinyl sulfide are used per mole of styrene. The resulting copolymer

8 to 20 parts by weight of monochloromethyl ether and then 2 to 6 parts by weight of a 1: 3 mixture of dimethylformamide and 20% alkaline. A slightly basic ion exchanger is obtained. It has good mechanical strength, osmotic stability and, in particular, high selectivity and capacity for gold, silver in technical cyanide alkalis. 10

When an acrylic acid methyl ester is used as the vinyl-containing monomer, 0.014-0.124 mole of divinyl sulfide is used per mole of monomer. The resulting resin is then treated with 5-10 parts by weight of 20-25% alkali, based on 1 part by weight of copolymer. The resulting ion exchanger has good mechanical strength and osmotic stability; the resin contains carboxyl groups and is particularly suitable for recovering dissolved streptomycin.

Also using acrylic acid methyl ester as a monomer containing vinyl groups, but using 20 0.014-0.11 moles divinylsulfide per mole of monomer and washing the resulting copolymer with 5-15 parts by weight of a 15-20% aqueous solution of an aliphatic amine in a copolymer, which, with high mechanical strength and osmotic stability, has excellent selectivity and high capacity for the recovery of dissolved lysine. Preferably, dimethylamine, diethylamine, ethylenediamine, hexamethylenediamine, monomethylethanolamine or diethanolamine are used as the aliphatic amine.

The vinyl monomer used is acrylic acid methyl ester 30 and the divinyl sulfide is also used in an amount of 0.014-0.11 mole per mole of monomer, but the resulting copolymer is treated with 5-20 parts by weight of anhydrous aliphatic amine. The resulting ion exchanger is slightly basic, with high mechanical strength and ³⁵ osmotic stability, characterized by its high ion exchange capacity for the recovery of molybdenum dissolved in technical nitrate solutions. Anhydrous aliphatic amine is preferably diethylamine, ethylenediamine, hexamethylenediamine, monomethylethanolamine, diethanolamine or hydroxylamine.

Further, 0.0460.14 moles of divinyl sulfide per mole of styrene can be used and the resulting copolymer is first treated with 8-20 parts by weight of monochlorodimethyl ether, followed by 10-20 by weight of 20-20 parts by weight of an aqueous solution of trimethylamine. The received ion exchanger has a high basic, high osmotic stability. The resulting sorbent is well suited for purification of a lipase solution obtained from fungal cultures. The anion exchanger can be used several times without loss of clarity. 50

Alternatively, the acrylic acid methyl ester may be used as the vinyl monomer, the divinyl sulfide is added in an amount of 0.0140.11 moles per mole of monomer, and the resulting copolymer is then treated with the monomer mixture of the above composition. Subsequently, the product is re-hermized in 55 emulsifying media and treated with 5 to 0.5 parts by weight of 2025% alkali per copolymer. A cation exchanger containing carboxyl groups is obtained which, with high mechanical strength and osmotic stability, has a high ion exchange capacity to adsorb copper ions dissolved in acidic or ammonium carbonate solutions.

The copolymers obtained according to the process of the invention, after treatment with anhydrous amine, are based on 1 part by weight of copolymer of the sodium salt of monochloroacetic acid.

It can also be treated with an aqueous solution of 2-6 parts by weight. In this case, an amphoteric ion exchanger is obtained which is particularly suitable for adsorbing nickel ions in sulfate solutions with high osmotic stability.

When acrylonitrile is used as the vinyl monomer, 0.11-0.60 moles of divinyl sulfide per mole of monomer are expected. 4-10 parts by weight of 20-25% alkali are treated with 1 part by weight of copolymer. A cation exchanger containing carboxyl groups is obtained which is particularly suitable for adsorption of cadmium ions in ammonium carbonate solutions at high osmotic stability.

Copolymerization of acrylonitrile and divinylsulfide in the above molar ratio, but treating the resulting copolymer with 1 to 6 parts by weight of ethylenediamine or hydroxylamine gives a weakly basic ion exchanger having a high osmotic stability, its capacity to bind chlorine ions.

The sulfur-containing sorption materials of the present invention can be prepared on conventional machines for the preparation of Io-exchange resins. The vinyl-containing monomer and the divinyl sulfide are polymerized in a continuous or batch reactor made of stainless steel or enameled metal. The reactor is equipped with a reflux condenser and some heating and cooling jacket.

The calculated amount of vinyl monomer divinyl sulfide and azoleobutanedio dinitrile used as initiator in the emulsified condenser reactor is distributed in the emulsifier system. The emulsifier is prepared in a manner known per se, for example by boiling the starch. Stirring is continued with stirring to ensure uniform mixing. The reaction temperature and reaction time are a function of the vinyl monomer used, as follows:

Monomer Re-Action-Reaction- temperature, C time, hour vinylpyridine 80-90 34 Ν, Ν, ρρ'-difenilmetánbiszmaleimid 60-70 4-6 a mixture of vinylpyridine and divinylbenzene 80-90 34 oh ilnitril 50-70 4 k ils acid methyl ester 60-80 7 styrene 70-85 8

The resulting polymer was separated from the liquid, washed with hot water and dried. The copolymers obtained with the monomers vinylpyridine, Ν, Ν'-ρρ'drenylmethane-bis-maleimide and vinylpyridine divinylbenzene were washed with acetone before washing with water. The polymers are washed on stainless steel filters and then dried in a batch drying oven at temperatures not exceeding 80 ° C.

The process may be carried out in various variants.

Using acrylic acid methyl ester and 0.014-0.11.11 molar vinyl sulfide as the monomer in the presence of azo-isobutanoic acid dinitrile, the polymerization was carried out as described above, and the resulting monomer mixture was mixed with 2-3 parts by weight of the monomer mixture. 7 hours at 60-80 ° C 3

-3185,621. The product thus obtained is treated with 5-10 parts by weight of 20-25% alkali.

0.046-0.14 moles divinyl sulfide per mole of styrene to form a copolymer in the presence of Friedel-Crafts catalysts or iron oxide at 35-45 ° C for 4-8 hours with 8-20 parts by weight of monochlorodimethyl ether and then at 60-70 ° C. - Treat with 2-6 parts by weight of a 1: 3 mixture of 20% alkaline and dimethylformamide for 6 hours.

The product obtained by copolymerization of divinyl sulfide and styrene can be treated with 10 to 15 parts by weight of 98% sulfuric acid at 80 to 100 ° C for 4 to 6 hours per part by weight copolymer.

using 0.11-0.60 moles of divinyl sulfide per mole of acrylonitrile to form a copolymer as described above, treated with 4-10 parts by weight of 2025% alkaline copolymer at 115-120 ° C for 8-10 hours. The same copolymer can be treated with 3-6 parts by weight of ethylenediamine or hydroxylamine at 110-120 ° C.

16 to 20 hours.

In a further embodiment of the invention, 0.014-0.124 mol of divinyl sulfide is used per mole of methyl acrylic acid, and the resulting polymer is treated with 4-10 parts by weight of 20-25% alkali at 100-110 ° C for 4-8 parts by weight. hours. When only 0.0140.11 mol of divinyl sulfide is used per mole of acrylic acid methyl ester, the resulting copolymer is treated with 5-15 parts by weight of a 15-20% aqueous solution of an aliphatic amine at 80-100 ° C for 12-16 hours. Aliphatic amine is selected from those already listed.

However, the resulting polymer can also be treated with 5-20 parts by weight of anhydrous aliphatic amine at 100-130 ° C for 5-15 hours. Subsequently, 3-4 parts by weight of an aqueous solution of monochloroacetic acid, sodium salt, in an aqueous solution at 70-80 ° C for 3-4 hours.

The sorption materials obtained were tested for mechanical strength, osmotic stability, specific volume and ion exchange capacity in a manner known per se.

The invention is further illustrated by the following examples.

Example 1

105 g of vinylpyridine, 10.32 g of divinyl sulfide and 1.6 g of azo-isobutanoic acid dinitrile are mixed in 440 ml of emulsifier. The emulsifier is a 1.5% aqueous starch solution which has been pre-boiled. The reaction mixture was heated to 80 ° C and maintained for 24 hours. The temperature was then raised to 90 ° C and maintained for 10 hours.

The reaction vessel is a three-necked flask equipped with a stirrer and a reflux condenser.

The polymer is formed in the form of transparent particles. The granules are filtered off, washed with acetone and water, then dried at a temperature of up to 80 ° C. Yield: 85%. The polymer parameters are given in Table 1.

Example 2

In 600 ml of the emulsifier of Example 1, 105 g of vinylpyridine, 11.18 g of divinyl sulfide and 1.8 g of azoisobutanoic acid dinitrile are mixed. The reaction mixture was heated at 80 ° C for 24 hours and then at 90 ° C for 10 hours. The reaction flask was a three-necked flask as described in Example 1. The copolymer is formed in the form of transparent particles. The polymer was treated as described in Example 1. The properties of the copolymer in 85% yield are shown in Table 1.

Example 3

In the same manner as in Example 1, a mixture of 105 g of vinylpyridine, 12.04 g of divinyl sulfide and 1.8 g of azo-isobutanoic acid nitrile in 500 ml of emulsifier was copolymerized. The properties of the copolymerate obtained in 85% yield are given in Table 1.

Table 1

Parameter First Second example Third Ion exchange capacity 0, ln for HCl (mval / g) 5.2 5.0 4.6 Sorption capacity (mg / g) for a solution containing 1.5 · 10 ⁶ platinum metals 30.0 40.5 46.2 Mechanical strength (%) 98.0 99.0 99.7 Osmotic Stability (%) 98.5 '99.7 99.8

Example 4

In the same manner as in Example 1, 105 g of vinylpyridine, 3.96 g of divinyl sulfide, 2.6 g of divinylbenzene, 40 g of isooctane and 1.8 g of azo-isobutanoic acid dinitrile are mixed in 800 ml of emulsifier. The copolymer was formed in 85% yield as transparent granules, which were treated as described in Example 1. The sorption properties are given in Table 2.

Example 5

In the same manner as in Example 1, a mixture of 105 g of vinylpyridine, 6.88 g of divinylsulfide, 50 g of isooctane, 10.0 g of divinylbenzene, 1.8 g of azoisobutanoic acid dinitrile and 800 ml of emulsifier is prepared. let's start. The properties of the polymer formed in the form of 85% transparent granules are given in Table 2.

Example 6

All proceed as in Example 1, but starting with a mixture of 105 g of vinylpyridine, 9.46 g of divinylsulfide, 50 g of isooctane, 19.5 g of divinylbenzene and 1.8 g of azo-isobutanoic acid dinitrile in 800 ml of emulsifier. The properties of the copolymer obtained in the form of 85% transparent granules are given in Table 2.

185,621

Table 2

Parameter 4th 5th example 6th Ion exchange capacity For 0.1 n HCl (mval / g) 4.2 3.8 3.1 Sorption capacity (mg / g) for a solution containing 1.5 · 10 I- ⁶ g / l platinum metal 40.3 34.5 30.2 Mechanical strength (%) • 99.0 98.5 98.0 Osmotic Stability (%) 99.5 98.0 98.5

Example 7

In the apparatus of Example 1 and 500 ml of the emulsifier described therein, 52.0 g of acrylonitrile, 9.46 g of divinyl-20 sulfide and 2.5 g of azo-isobutanoic acid dinitrile were mixed and the mixture was heated at 50 ° C for 2 hours. and then at 70 ° C for a further 2 hours. The copolymer (85% yield, clear particles) was washed with water and dried at a temperature not exceeding 80 ° C. Product characteristics are listed in Table 3.

Example 10

86.0 g of acrylic acid methyl ester, 1.22 g of divinyl sulfide and

A dispersion of 1.5 g of azoisobutanoic acid dinitrile in 400 ml of 1.5% aqueous starch was heated at 60 ° C for 3 hours and then at 80 ° C for 4 hours. The polymer is formed in the form of transparent particles in 95% yield. The granules are filtered off, washed with water and dried below 80 ° C. The sorption properties are shown in Table 4.

Example 11

In a 600 L reactor, a stirred mixture of 300 L of 1.5% aqueous starch, 86.00 kg of acrylic acid methyl ester, 9.41 kg of divinyl sulfide and 1.5 kg of azo-isobutanoic acid dinitrile is prepared. The reaction mixture was heated at 60 ° C for 3 hours and then at 80 ° C for 4 hours, stirring all the time. At the end of the copolymerization, the mixture was cooled to 30 ° C and placed on a pressure filter. The product is filtered with nitrogen at atmospheric pressure. The copolymer was washed with water, removed from the filter, and dried in a dryer at 85 ° C. 93 kg of dry copolymer having the characteristics a4. table.

Example 8

52.0 g of acrylonitrile, 25.80 g of divinyl sulfide and 4.6 g of azoisobutanoic acid dinitrile are mixed with 600 ml of emulsifier. A boiling 1.8% starch solution is used as the emulsifier. The mixture was stirred and refluxed in a 3-necked flask for 2 hours at 50 ° C and then for a further 2 hours at 70 ° C. The polymer is formed in the form of transparent particles. The granules were filtered off with suction, washed with water and dried below 80 ° C. The properties of the polymer are shown in Table 3.

Example 9

In 500 ml of the emulsifier according to Example 8, 52.0 g of acrylonitrile, 51.6 g of divinyl sulfide and 4.6 g of azoisobutanoic acid dinitrile were emulsified. In the following, the procedure of Example 8 is followed. The sorption characteristics of the sorption material at 85% yield are given in Table 3.

Table 3 _55

specific 7th 8th example 9th Sorption capacity (mg / g) for 0,5 g Cu / l copper bromide acetone solution 80.7 97.5 114.1 Mechanical strength (%) 97.0 97.2 97.5 Osmotic Stability (%) 97.1 97.5 98.0

Example 72

A mixture of 86.00 g of acrylic acid methyl ester, 10.66 g of divinyl sulfide and 1.3 g of azoisobutanoic acid dinitrile in 600 ml of 1.5% aqueous starch was treated as in Example 10. The yield of the polymer in the form of transparent granules is 97%. The characteristics of the polymer are given in Table 4.

Table 4

Known 10th 11th 12th specific process example Contains 0.5 g Cu / l copper acetone copper bromide sorption solution capacity (mg / g) 50.0 75.4 79.2 81.3 Mechanical strength (%) 29.0 99.5 99.3 99.0 Osmotic stability (%) 35.5 99.8 99.7 99.6

Example 13

104 g of styrene, 9.41 g of dinylsulfide and 1.6 g of azoisobutanoic acid dinitrile are dispersed in the apparatus of Example 1 and 500 ml of the emulsifier specified therein. The mixture was heated at 70 ° C for 4 hours and then at 85 ° C for 4 hours. The polymer formed in the clear granules is washed with water and then dried at a temperature below 80 ° C. Yield: 90%. The characteristics of the copolymer are given in Table 5.

-5185 621 is removed from the filter and dried in a dryer below 80 ° C. 147 kg of dry copolymer were obtained; properties are given in Table 6.

Example 19

Example 14

Example 13 was repeated except that 104.00 g of styrene, 8.07 g of divinyl sulfide and 1.7 g of azoisobutanoic acid dinitrile were used. Yield: 89%. The characteristics of the copolymer are given in Table 5.

bow. example

A dispersion of 104 g of styrene, 4.03 g of divinyl sulfide and 1.5 g of azo-isobutanoic acid dinitrile in 600 ml of 1.5% starch solution was treated as in Example 13. The characteristics of the polymer obtained in 90% yield are given in Table 5.

Table 5

13th 14th 15th specific example Contains 0.5 g Cu / l copper acetone solution of copper bromide sorption capacity (Mg / g) 90.3 75.6 61.5 Mechanical strength (%) 99.5 99.5 99.0 Osmotic Stability (%) 99.6 99.5 99.5

Example 16

10 g of the copolymer obtained in Example 10 are soaked in a mixture of 3.63 g of divinyl sulfide, 296.27 g of acrylic acid methyl ester and 4.5 g of azoisobutanic acid dinitrile. The polymer so treated was dispersed in 1200 mL of 1.5% starch solution and the dispersion was heated at 60 ° C for 3 hours and then at 80 ° C for 4 hours. The resulting granules are filtered, washed with water and dried at a temperature below 80 ° C. The characteristics of the polymer obtained in 98% yield are given in Table 6.

100 g of the polymer obtained according to Example 11 are impregnated with a mixture of 28.23 g of divinyl sulfide, 271.77 g of acrylic acid methyl ester and 4.5 g of azo10 isobutanoic acid dinitrile. The treated copolymer was mixed with 1100 mL of 1.5% aqueous starch and heated at 60 ° C for 3 hours and then at 80 ° C for 4 hours as described in Example 1. The polymer particles are filtered off, washed with water and dried at temperatures below 80 ° C. The properties of the copolymer in 98% yield are given in Table 6.

Table 6

Parameter

16. 17. 18. 19.

example

In the case of a solution of copper containing 25 g of Cu per liter of copper in acetone

capacity (mg / g) 50.1 62.3 80.1 79.5 Mechanical strength (%) 98.0 95.9 98.5 96.0 “Osmotic Stability ³⁰ % 98.5 97.0 99.5 96.5

Example 20

358.0 g of Ν, Ν'-ρρ'-diphenylmethane-bis-maleimide, 1.3 g of divinylsulfide, 1200 ml of benzene and 5.4 g of azo-isobutanic acid dinite with 6000 ml of 1.5% starch solution of the dispersion prepared by stirring and kept at 60 ° C for 6 hours in a 10 liter reactor with reflux.

The copolymer was separated from the liquid, washed with acetone and water, and dried. The properties of the polymer obtained in 96% yield are given in Table 7.

Example 17

All. 100 g of the copolymer obtained in Example 1b are impregnated with a mixture of 20.16 g of divinyl sulfide, 279.84 g of acrylic acid methyl ester and 4.5 g of azoisobutanoic acid dinitrile. The impregnated polymer particles were dispersed in 600 mL of 1.5% starch solution and proceeded as in Example 16 below. The properties of the copolymer in 98% yield are given in Table 6.

Example 18

50 kg of the polymer obtained according to Example 11 are thoroughly stirred in a 600 L reactor for 30 minutes with a mixture of 89.06 kg of acrylic acid methyl ester, 10.94 g of divinylsulfide and 1.5 kg of azo-isobutanoic acid dinitrile. Then 350 liters

A 1.5% starch solution is added to the mass. The mixture was heated at 60 ° C for 3 hours and then at 80 ° C for 4 hours. The mixture was then cooled to 40 ° C, applied to a pressure filter and filtered with nitrogen gas (1 at). Wash the copolymer with water

Example 21

Example 20 was repeated except that 120.4 g of divinyl sulfide and 8.8 g of azoisobutanoic acid dinitrile were used and the reaction mixture was kept at 70 ° C for 4 hours. The properties of the copolymer obtained in 97% yield are given in Table 7.

Table 7

Parameter 20th examples 21st da Weight loss at 300 ° C (%) 5.5 5.0 Degree of purification (%) of copper bromide solution 0.13 g Cu / l copper solution in n-octanol (%) sorption material: solution = 1:80 80 80 The temperature of the solution to be cleaned is ° C 220 220

-6185 621 Example

100 g of the dry copolymer obtained in Example 15 are treated with 800 g of monochloromethyl ether for 8 hours at 45 ° C in the presence of 30 g of zinc chloride. The copolymer was separated from the liquid and washed with dimethoxymethane. The copolymer had a chlorine content of 22.6%. The copolymer was then treated with 2000 ml of 20% aqueous trimethylamine solution at 35 ° C for 4 hours. The resulting highly basic ion exchange beads were separated and washed with 5% hydrochloric acid to neutral. 10

The anion exchange resin thus obtained is useful for clarifying a lipase solution obtained from a culture of microorganisms. The activity of the purified enzyme is 5.5 times higher than before purification. The yield of enzyme activity was 97.5%.

The ion exchange parameters are given in Table 8. 15

Example 23

In essence, the procedure of Example 22 was repeated except that the copolymer was treated with 2000 g of monochlorodimethyl ether at 35 ° C for 8 hours in the presence of 60 g of zinc chloride, and the resulting copolymer containing 21.2% chlorine was treated with 45 ° C of trimethylamine. C is carried out for 6 hours.

It is useful for purifying the resulting anion exchange lipase solutions. The activity of the purified enzyme increased 5-fold.

97% of the enzyme activity was recovered. The properties of the anion exchanger are given in Table 8.

Table 8

Parameter 22. 23. example Specific volume of Cl form resin in water (cm ³ / g) 48.5 51.3 Ion exchange capacity at 0.1 n HCl (mval / g) 5.0 5.4 Nitrogen content (%) 5.2 5.6 Osmotic Stability (%) 98 97

Example 26

10 g of the copolymer obtained in Example 10 are boiled in 400 g of 35% 20% sodium hydroxide solution for 8 hours.

The copolymer filtered from the alkali is washed with water until neutral. The resulting cation exchanger contains carboxyl groups;

its characteristics are given in Table 10.

Example 24

100 g of the copolymer obtained in Example 14 are treated with 2000 g of monochloromethyl ether in the presence of 40 g of iron oxide catalyst at 45 ° C for 4 hours. The copolymer was separated from the liquid and washed with acetone. The copolymer containing 21.5% 50 chlorine was treated with a mixture of 300 g of dimethylformamide and 600 g of 20% alkaline at 60 ° C for 6 hours. The resulting granular anion exchanger is slightly basic in nature. After separation, the copolymer is washed with 5% hydrochloric acid and then with water. The anion exchanger 55 prepared as described has selective ion exchange capabilities to recover gold and silver in cyanide bases. The copolymer parameters are shown in Table 9.

Example 25

100 g of the dry copolymer obtained in Example 13 are treated with 800 g of monochloromethyl ether for 6 hours in the presence of 20 g of iron oxide at 35 ° C. The product was then filtered and washed with acetone. Copolymer containing 21.3% chlorine; The mixture is treated with 00 g of dimethylformamide and 300 g of 20% alkaline at 70 ° C for 3 hours. The particulate mildly basic ion exchanger was filtered off and washed to neutral with 5% hydrochloric acid and water. The anion exchanger has a selective ion exchange capability to extract gold and silver in cyanide alkalis. The characteristics of the anion exchanger are given in Table 9.

Table 9

24th 25th

example

Specific volume of Cl form resin in water (cm ³ / g) 3.0 2.9 Ion exchange capacity at 0.1 n HCl (mval / g) 3.9 4.1 Nitrogen content (%) 4.8 5.0 Osmotic Stability (%) 96 96.5 Mechanical strength (%) 95 95.5 Sorption capacity (mg / g) for technical solutions of 16.35 mg Au / l and 43.0 mg Ag / l gold 34.4 35.6 silver 21.2 22.7

Example 27

10 g of the particulate copolymer obtained in Example 10 are treated with 800 g of 25% sodium hydroxide solution at 105 for 45 hours. The copolymer separated from the alkali is washed with water until neutral. The resulting ion exchanger contains carboxyl groups, suitable for sorption of streptomycin. Its characteristics are shown in Table 10.

Table 10

Parameter 26th 27th example 28th The specific volume of the Na form in water is cm ³ / g 30.5 28.3 29.6 slurry capacity at 0.1 n NaOH (mval / g) 12.5 11.9 12.1 Exchange capacity for streptomycin (mval / g) 7.45 7.31 7.41 Osmotic Stability (%) 99.8 99.9 99.8 Mechanical strength (%) 99.5 99.7 99.6

-185,621

Example 20

10 g of the copolymer obtained in Example 10 are treated with 600 g of 22% sodium hydroxide solution at 110 ° C for 4 hours. The copolymer separated from the alkali is washed with water until neutral. The resulting cation exchange resin containing carboxyl groups is suitable for sorption of streptomycin and is shown in Table 10.

Example 29

100 kg of the particulate copolymer obtained in Example 11 and 500 kg of 20% sodium hydroxide solution were charged into an 800 L reactor. The reaction mixture was heated to 105 ° C and maintained at this temperature for 7 hours. The mixture was stirred continuously. The mixture is then cooled to 30 ° C and placed on a pressure filter, where the polymer is separated from the liquid with a nitrogen pressure of 1 at. The 350 kg carboxyl group cation exchange resin is washed with water to neutral. The product is suitable for extraction of copper from solutions of ammonium carbonate and sulfuric acid. The features of the ion exchanger are all. table.

Example 30

100 g of the particulate copolymer obtained in Example 12 are refluxed with 800 g of 25% sodium hydroxide solution for 6 hours. It is then separated from the liquid and washed with water until neutral. The resulting carboxyl-containing cation exchange resin can be used to extract copper from extraction solutions of ammonium carbonate. The features of the ion exchanger are all. table.

Table 11

specific 29th 30th example 31st Known process The specific volume of the Na form in water is cm ³ / g 3.5 3.8 3.7 4.5 Ion exchange capacity at 0.1 n NaOH (mval / g) 12.1 11.9 12.0 9.7 CU (g / l) extracted from a solution containing 5,0 g / l Cu, 10 g / l CO ₂ and 20 g / l ammonia 67.0 66.9 66.8 45.0 Cu (g / l) extracted from a solution of sulfuric acid containing 2,5 g / l Cu, 50 g / l Na ₂ SO ₄ 68.1 67.9 68.0 44.7 Osmotic Stability (%) 100.0 100.0 100.0 31.5 Mechanical strength (%) 99.5 99.6 99.5 25.6 Cu (mg / g) extracted from 1.54 g Cu / l acetonitrile CuBr ₂ solution 140.1 135.9 137.8 86.9

Example 31

All. The granular copolymer obtained in Example 1b is treated with 100 g of 600 g of 22% sodium hydroxide solution at 110 ° C for 7 hours. The copolymer was separated from the liquid and washed neutral with water. The resulting ion exchange contains carboxyl groups. It can be used to extract copper ions from solutions of ammonium carbonate and sulfuric acid. The properties of the ion exchanger are all. table.

Example 32

100 g of the particulate copolymer obtained in Example 10 are treated with 2000 g of 15% aqueous hexamethylenediamine solution at 90 ° C for 10 hours, then separated from the liquid and washed with water to neutral. The resulting cation exchanger containing carboxyl groups is suitable for the selective extraction of lysine. The product characteristics are given in Table 12.

Example 33

Example 32 except that 100 g of copolymer was treated with 500 g of 20% aqueous hexamethylenediamine solution at 100 ° C for 12 hours. The product obtained is also suitable for selective extraction of lysine, its characteristics are shown in Table 12.

Table 12

33 examples

The specific volume of Na form in water, cm / g 15.2 16.1 Ion exchange capacity at 0.1 n NaOH (mval / g) 8.2 8.4 Sorption capacity for lysine, g / g 0.9 0.9 Osmotic Stability (%) 99.5 99.6 Mechanical strength (%) 99.7 99 (5

Example 34

As in Example 32, except that 100 g of copolymer are treated with 1500 g of 15% aqueous diethanolamine. The ion exchanger characteristics for selective extraction of lysine are shown in Table 13.

Example 35

Example 32 was repeated except that 100 g of copolymer were treated with 500 g of 20% aqueous dimethylamine solution at 80 ° C for 12 hours. The cation exchanger containing carboxyl groups is suitable for the selective extraction of lysine, its characteristics are given in Table 13.

185,621

Table 13

specific 34th 35th Known example process The specific volume of the Na form in water is cm ³ / g 18.5 17.7 3.7 Ion exchange capacity at 0.1 n NaOH (mval / g) 10.1 9.8 5.7 Sorption capacity for lysine (g / g) 1.0 0.95 0.48 Osmotic Stability (%) 99.5 99.6 36.3 Mechanical strength (%) 99.2 99.4 28.9

Example 36

100 g of the copolymer obtained in Example 14 are refluxed with 1000 g of 98% sulfuric acid for 4 hours. The liquid is then separated and the product is washed neutral with distilled water. The resulting cation exchanger contains sulfonic acid groups, which can be used to extract yeast cells from yeast cultures. The properties of the ion exchanger are given in Table 14.

Example 37

Example 36 was repeated but 100 g of the copolymer obtained in Example 13 were treated with 1500 g of 98% sulfuric acid at 80 ° C for 6 hours. The ion exchanger obtained has the same nature and field of use as Example 36. The properties of the ion exchanger are given in Table 14.

Table 14

36. 37.

The specific volume of Form H in water is cm ³ lg 25.5 28.3 Ion exchange capacity at 0.1 n NaOH (mval / g) 5.5 5.4 Ion exchange capacity at 0.1 n CaCl ₂ (mval / g) 4.8 4.7 Sorption capacity for yeast cells (mg / g) 47.3 46.8

Example 38

100 g of the copolymer obtained in Example 12 are treated with 300 g of anhydrous ethylenediamine at 110 ° C for 10 hours. The copolymer is then separated and washed to neutral with water. The resulting anion exchange copolymer can be used to extract molybdenum ions from molybdenum-containing nitrate solutions. The characteristics of the ion exchanger are listed in Table 15.

Example 39

100 g of the copolymer obtained in Example 10 are treated with 350 g of anhydrous ethylenediamine at 100 ° C for 15 hours. The polymer is then separated and neutralized with water. Neutrality! is determined with phenolphthalein. The nature and field of application of the ion exchanger with one of the copolymers described in Example 38 are shown in Table 15.

Example 40

They are fed into a 300 liter reactor underneath. 100 kg and 400 kg of anhydrous ethylenediamine. After stirring for 13 hours at 105 ° C, the reaction mixture was cooled to 30 ° C and placed on a pressure filter. The copolymer is filtered with 1 att nitrogen gas and washed to neutral with 5% hydrochloric acid and / or taste. 450 kg anion exchanger gate of the type and scope as in Example 38; its characteristics are given in Table 15.

Example 41

Example 39 was repeated except that the 100 g copolymer was treated with 400 g of anhydrous ethylenediamine at 105 ° C. The characteristics of the ion exchanger are given in Table 15.

Table 15

specific 38th 39. 40. example 41st Known process The specific volume of Form C1 in water is cm ³ 'g 4.6 7.4 4.4 8.0 3.6 Ion exchange capacity 0.1 n HCl case tin (mval / g) 6.3 6.0 6.2 5.9 4.9 Nitrogen content (%) 14.1 13.8 14.0 13.7 10.5 Amount of molybdenum extracted from ₅ solutions (2 g / J molybdenum, 100 g NH ₄ Cl, 50 g / l NaCl and 40 g / l NO ₃ ) (rng / g): 540.1 529.3 531.8 519.4 320.9 Osmotic Stability (7c) 96.1 95.2 96.0 95.5 37.9 Mec Phanic Strength (%) 96.0 95.0 95.7 95.0 35.0

Table 17

185 '521

Example 42

100 g of the copolymer obtained in Example 10 are soaked in 350 g of dimethylformamide. Thereafter, the copolymer was treated with 450 g of anhydrous diethanolamine for 10 hours at 110 ° C. The liquid was then separated and the copolymer was washed to neutral with 5% hydrochloric acid and water. The characteristics of the slightly basic anion exchanger are given in Table 16.

4J. example

The procedure of Example 42 was followed except that the 100 g copolymer was soaked in 260 g of dimethylformamide and then treated with diethanolamine for 5 hours at 130 ° C. The characteristics of the slightly basic anion exchanger are shown in Table 16.

Table 16

42. 43. Known

Specific volume of Cl form

in water, cm ³ / g 26.8 25.4 30.5 Ion exchange capacity at 0.1 n HCl (mval / g) 7.0 7.2 5.9 Osmotic Stability (%) 98.5 98.9 30.5 Mechanical strength (%) 99.3 99.6 25.7

specific 44th 45th example 46th The specific volume of the Na form in water is cm ³ / g 5.0 5.2 4.9 Ion exchange capacity at 0.1 n NaOH (mval / g) 8.8 8.9 8.5 Cadmium extracted from a solution containing 5 g Cd, 20 g NH ₃ , 10 g CO ₃ (g / D) 83.1 83.6 81.2 Osmotic Stability (%) 97.1 97.5 98.0

Example 47

100 g of the polymer obtained in Example 7 are treated with 500 g of hydroxylamine at 110 ° C for 20 hours, then separated from the liquid and washed neutral with 5% hydrochloric acid and water. A weakly basic ion exchanger is obtained, the characteristics of which are given in Table 18.

Example 48

Example 47 was repeated except that 100 g of the copolymer obtained in Example 8 were treated with 500 g of hydroxylamine at 115 ° C for 18 hours. The characteristics of the resulting anion exchanger are given in Table 18.

Example 44

100 g of the copolymer obtained in Example 7 are treated with 800 g of 20% sodium hydroxide solution at 120 ° C for 8 hours. The copolymer is then separated and washed neutral with water. The resulting cation exchanger contains carboxyl groups to extract cadmium ions from ammonium carbonate solutions. The characteristics of the ion exchanger are given in Table 17,

Example 45

Example 44 was repeated except that 100 g of the copolymer obtained in Example 8 were treated with 400 g of 22% sodium hydroxide solution at 117 ° C for 9 hours. The ion exchanger obtained has the same nature and range of use as in Example 44. Its characteristics are shown in Table 17.

Example 49

Example 47 was repeated except that 100 g of the copolymer obtained in Example 9 were treated with 400 g of hydroxylamine at 120 ° C for 16 hours. The characteristics of the resulting anion exchanger are shown in Table 18.

Table 18

specific 47th 48th example 49th The specific volume of the Cl form in water is cm ³ / g 2.0 2.1 2.0 Ion exchange capacity 0.1 n For HCl, (mval / g) 4.9 4.8 4.8 Osmotic Stability (%) 96.1 96.0 96.3

Example 46

100 g of the copolymer obtained in Example 9 are treated with 1000 g of 25% sodium hydroxide solution at 115 ° C for 10 hours. The resulting cation exchanger has the same application as Example 44. Its characteristics are given in Table 17.

Example 50

100 g of the copolymer obtained in Example 7 are treated with 300 g of ethylenediamine at 120 DEG C. for 20 hours, then separated from the liquid and washed neutral with 5% hydrochloric acid and water. The properties of the resulting slightly basic ion exchanger are shown in Table 19.

-10185 621

Example 57

100 g of the copolymer obtained in Example 8 are treated with 600 g of ethylenediamine at 115 ° C for 16 hours, then separated from the liquid and washed with 5% hydrochloric acid and then with water. The resulting slightly basic ion-exchange properties are shown in Table 19.

Example 52

The procedure of the previous example was followed except that 100 g of the copolymer of Example 9 were treated with 500 g of ethylenediamine at 110 ° C for 18 hours. The characteristics of the copolymer are given in Table 19.

Table 19

specific 50th 51st example 52nd The specific volume of the Cl form in water is cm ³ / g 2.4 2.3 2.2 Ion exchange capacity 0.1 n For HCl (mval / g) 5.4 5.1 5.2 Osmotic Stability (%) 97.1 96.9 96.5

Example 53

100 g of the basic anion exchanger obtained in Example 39 are treated with a mixture of 60.8 g of sodium salt of monochloroacetic acid, 20 g of sodium carbonate and 320 g of water at 80 ° C for 4 hours, separated from the liquid and neutralized with 5% hydrochloric acid and water. washed. The characteristics of the resulting ampholite are shown in Table 20. The ampholite can be used to extract nickel ions from nickel sulfate-containing sulfate solutions.

Example 54

Example 53 was repeated except that 100 g of the anion exchanger obtained in Example 40 were treated at 75 ° C with 90 g of monochloroacetic acid sodium salt, 25 g of sodium carbonate and 470 g of water for 3.5 hours. The characteristics of the resulting ampholite are shown in Table 20. Its area of use is given in Example 53.

Table 20

specific 53rd 54th example 55th Specific volume in water, cm ³ / g 2.4 2.5 2.3 Ion exchange capacity at 0.1 n HCL, mval / g 6.1 6.2 5.9 Nickel (mg / g) from sulphate solution containing 2,5 gNi / 1 nickel 320 325 315 Osmotic Stability (%) 98.0 97.1 97.5

Example 55

Starting from 100 g of the anion exchanger obtained in Example 41, the procedure of Example 53 was followed except that 70 g of monochloroacetic acid sodium salt, 25 g of sodium carbonate and 400 g of water were used and the reaction time was 70 hours at 70 ° C. The characteristics of the resulting ampholite are shown in Table 20.

Claims (14)

A process for the preparation of sulfur-containing sorption, preferably ion-exchange materials, by copolymerization of monomers containing vinyl groups and divinylsulfide, characterized in that the vinyl monomer is styrene, acrylonitrile, vinylpyridine, Ν, Ν-ρρ'-diphenylmethane-bis-maleimide, and a mixture of divinylbenzene of 0.02 to 1: 0.15 molar ratio, from 0.014 to 1.4 molar vinyl sulfide per mole of monomer, including 0.008-0.05 moles of azo- vinyl sulfide initiator, preferably one mole of vinyl monomer. isobutyric acid in the presence of dinitrile at a temperature of 50-90 ° C, optionally chloromethylating the copolymer and subsequently hydrolyzing or sulfonating or aminating the resulting polymer and then optionally carboxylating. 2. The process according to claim 1, wherein the vinyl monomer is vinylpyridine and 0.12-0.14 moles of civinyl sulfide are used per mole of vinylpyridine. 3. The process of claim 1 wherein the vinyl monomer is a mixture of vinylpyridine and divinylbenzene, and 0.12-0.14 moles of divinyl sulfide are calculated per mole of vinyl monomer. 4. The process of claim 1 wherein the vinyl monomer is styrene mica coated with 0.046-0.14 mole of divinyl sulfide per mole of vinyl monomer, and the resulting copolymer is first 8-20 parts by weight of monochloro. chloromethylated with dimethyl ether and then aminated with 2-6 parts by weight of a 1: 3 mixture of dimethylformamide and 20% alkali metal hydroxide. 5. The process of claim 1 wherein the vinyl monomer is acrylic acid methyl ester, 0.014-0.124 mol divinyl sulfide is used per mole of vinyl monomer, and the resulting copolymer is 5 to 10 parts by weight based on 1 part by weight of copolymer. It is basically hydrolysed with 25% alkali metal hydroxide solution. 6. The process of claim 1 wherein the vinyl monomer is acrylic acid methyl ester, 0.014-0.11 mole divinylsulfide per mole of vinyl monomer, and the resulting copolymer is 15-20% c per mole of copolymer. 5 to 15 parts by weight of the aqueous solution. 7. The process according to claim 6, wherein the aliphatic amine is dimethylamine, diethylamine, ethylenediamine, hexamethylenediamine, mono-anolamine or diethanolamine. 8. A process according to claim 1 wherein the vinyl monomer is acrylic -112 185,621 acid methyl esters were used, 0.014-0.11 moles divinyl sulfide were calculated per mole of vinyl monomer, and the resulting copolymer was aminated with 5-20 parts by weight of anhydrous aliphatic amine, 9. The process of claim 8, wherein the anhydrous aliphatic amine is dimethylamine, diethylamine, ethylenediamine, hexamethylenediamine, monoethyl ethanolamine, diethanolamine or hydroxylamine. 10. The process of claim 1 wherein the vinyl monomer is styrene, 0.046-0.14 mole of divinyl sulfide is used per mole of monomer, and the resulting copolymer is chloromethylated with 8-20 parts by weight of monochlorodimethyl ether. Aminate with -20 parts by weight of aqueous trimethylamine solution. 11. A process according to claim 1, wherein the acrylic acid methyl ester / divinyl sulfide is copolymerized in a molar ratio of 1: 0.014 to 1: 0.11, the resulting polymer is impregnated with a mixture of the above composition, and the resulting polymer is again polymerized. - 1 part by weight to copolymer - 5-20 parts by weight with 20-25% alkali metal hydroxide solution. 12. A process according to claim 1, 8 or 9, wherein after treatment with the anhydrous amine, the copolymer is carboxylated with 2-6 parts by weight of an aqueous solution of monochloroacetic acid, based on 1 part by weight of the copolymer. 13. The process according to claim 1, wherein acrylonitrile is used as the vinyl monomer by reacting 0.11-0.6 mole divinyl sulfide per mole of vinyl monomer, and the resulting copolymer is - per part by weight copolymer - 4-10 parts by weight with 20-25% alkali metal hydroxide solution 15 hydrolyze. 14. The process according to claim 1, wherein the vinyl monomer is acrylonitrile, and 0.11-0.60 mole of divinyl sulfide is charged per mole of monomer and the resulting copolymer is Aminated with 3-6 parts by weight of ethylene diamine or hydroxylamine, based on 23 parts by weight of copolymer. Without illustration