DE2447305A1 - CHELATING POLYMERIZES - Google Patents

Description

The present invention relates to chelating agents
Polymers for simple, cheap and effective development _; removal of unwanted heavy metal ions from industrial
Wastewater such as wastewater from the mining industry, electrolysis, '. wire fabrication, semiconductor fabrication / plating,; catalysis, fiber, pigment and dye production, as well as dyeing and similar industries, the precipitated; or adsorbed Sehwermetallionen easily _recovered: can be. The invention is further concerned with chelate 'forming polymers by which the heavy metal ions easily
can be recovered. In particular, the invention describes chelating polymers which contain heavy metal ions
which are harmful to health enter into reactions, such as
with mercury, cadmium, zinc, copper and lead being the
Heavy metal ions are precipitated or adsorbed and these '- heavy metal ions easily from the chelating polymers

can be recovered.

Up to now have been used as chelating polymers for the removal of
Heavy metal ions styrene-divinylbenzene copolymerization resins
with a. Iminodiacetic acid group (-N (CH ₂ COOH) ₂ ) or polyamine group (- (NHCH ₂ CH ₂ ) _n 10NH ₂ ), and thiourea type resins
or dithiocarbamic acid resins produced by incorporation into phenolic

5O9ai 7/1 042 - -

resins of a sulfur or nitrogen group opposite from Heavy metal ions have a greater affinity are known. However, these plastics have low heavy metal ion adsorption (Exchange) values as well as low rates of adsorption (exchange). From an economic point of view, these are Polymers are expensive and heavy metal ions that have been adsorbed are difficult to remove. Recently was on reactivity a mercapto group and suggested chelating polymers by incorporating a mercapto group into cellulose to manufacture. Although these plastics are actually attractive, they are only in the laboratory test stage and have been made not yet used in practice.

It has now been found that a water-soluble or insoluble Polymer with at least 2 tertiary amino groups and at least 1 carboxyl group in the molecule effective for removal and recovery heavy metal ions can be used. Further if the polymer has a greater affinity for metal ions so that better chelation is obtained. The resin can also be used as a dye, binder, anti-static agent in synthetic fibers and plastics, electrical conductive plastic, anti-fogging agent, and the like such as dispersing agent and the Precipitation promoters are used. A water-soluble plastic of said type can be used as a rust preventive, latex additive, Thickeners, swelling agents, and can be used for similar purposes. The plastic of the invention can be made by the following 3 step reaction can be produced.

In a first stage are in a solvent or ϊη a Solvent-free medium poly-N-substituted polyamines or poly-N-substituted polyalkylenimines, which can be obtained by substitution which is on the nitrogen atom., the polyamines or polyalkylenimines located active hydrogen atoms by alkali metal salts or Obtained alkyl esters of a carboxyalkyl or a cyanoalkyl group at least 2 active hydrogen atoms bound to the nitrogen atom should remain in the molecule, with diepoxide compounds subjected to a polyaddition reaction.

509817/1042

In a second reaction stage, the product obtained is through
Addition of known hardeners for epoxy resins to one:

Plastic cured with an epoxy end group, the
The epoxy compound in "a molar excess in the first
Stage is used, or the prepolymer by a molar
Excess of poly-N-substituted polyamines or poly-N-substituted polyalkyleneimines is cured.

The third stage comprises an acidic or an alkaline saponification of the cured plastic or the cured prepolymer of the second stage or of the reaction product of the
first stage if the N-substituent of the poly-N-substituted
Polyamines or the poly-N-substituted polyalkylene imides

Is an alkyl ester of a carboxyalkyl or a cyanoalky group. :

The reaction in the second stage can be obtained by one of the methods described below, two · werdenr performed ■ '\

1. 'Formation of the plastic obtained in the first stage to a film and hardening of the film. This film can be used as such can be set or it becomes a powdery ■ or granular hardened product of suitable grain size processed. . ;

2. The plastic obtained in the first stage is under ^!

Heating in an aqueous solution of one or more water-soluble plastics or non-ionic surface-active substances
poured to thereby obtain a slurry. ;

The hardening of the plastic is preceded in the slurry; taken so that a cured powdery or granular '' ■ plastic of suitable grain size is obtained.

Through the second curing process described above
Use of water-soluble plastics or non ionogenic Upper ^ -, surface active substances is a cured plastics material with a '> particle size from 4.7 to 0.05 mm barren obtain finer.
The particle size can be changed without a special granulation process
can be set. - '"■ .- · ■■■

5O9 8'-17/1 CU Τ

The chelating plastics of the present invention are characterized by the simplicity of their manufacture. The polymers produced in this way have a high ion exchange rate with reference to various heavy metal ions as well as a pronounced selectivity which makes it possible, for example, to trace to remove a certain heavy metal ion selectively and completely from an aqueous solution by adsorption without further metal ions which are present in greater concentration are precipitated. The insoluble plastic can contain high amounts adsorb various heavy metal ions, the plastic also has good properties with regard to chemical resistance / Resistance to alkali and resistance to pollution.

The present invention will be described in more detail below explained.

In a first stage, poly-N-substituted polyamines or poly-N-substituted polyalkyleneimines with at least 2 active hydrogen atoms bonded to a nitrogen atom are mixed with diepoxide compounds in a solvent (which facilitates stirring, prevents gel formation and the physical adsorption of heavy metal ions through the porosity the plastic material is produced which subsequently cured is ^improved); or reacted in the absence of a solvent at a temperature between 50 and 150 ^° C. for 1 to 15 hours.

Poly-N-substituted polyamines or poly-N-substituted polyalkyleneimines having at least 2 active hydrogen atoms on one nitrogen atom which are in the first stage of the present invention can be used include ethylenediamino-diacetonitrile, ethylenediamino-dipropionitrile, ethylenediamino-di- (2-methylpropionitrile), Propylenediamino-diacetonitrile, propylenediamino-propionitrile, propylenediamino-di- (2-methyl-propionitrile), hexamethylenediamonodiacetonitrile, Hexamethylene diamino dipropionitrile,

Hexamethylenediamino-di (2-methyl-propionitrile), m-xylene diamino diacetonitrile, m-xylenediamino-dipropionitrile, m-xylenediamino-di (2-methyl-propionitrile); and alkali metal salts or alkyl esters (C-J-C ^) of ethylenediamino-diacetic acid, ethylenediamino-dipro-

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pionic acid, ethylenediamino-di- (1-methyl-proplonic acid), '', · Ethylenediamino-di (2-methyl-propionic acid), propylenediamine © -; diacetic acid, propylenediamino-dipropionic acid, propylenediamino-di:

(1-methyl-propionic acid) j propylenediamino-ß-methyl-propionic acid), hexamethylenediamino-diacetic acid, hexamethylenediamino-dipropionic acid / hexamethylenediamino-di- (1-methyl-propionic acid), hexamethylenediamine- (2-methyl-propionic acid), m-xylenediaminodiacetic; acid, m-xylenediamino-dipropionic acid, m-xylenediamino-di- (l-methyl ~ propionic acid), m-xylenediamino-di- (2-methyl-dipropionic acid) and those which by substitution by cyanoalkyl groups ie

(CHR ¹ J _n CN (where R ¹ is H or CH ₃ and η is a number between 1 or 2), or alkali metal salts or alkyl • esters of a carboxyalkyl group ie (CHR ¹ J _n COOR (where R ¹ a Hydrogen atom or CH ₃ , η a number between 1 or 2 and R is an alkali metal or a hydrocarbon group with C, bis

C. represent carbon atoms), of N-alkylethylenediamine,:

! N-alkyl-propylenediamine, N-alkylhexamethylenediamine, N-alkyl-m- | xylenediamine, N-alkylrdiäthylentriamin, N-alkyl-triethylenetetramine, N-alkyl-triethylenetetramine, tetraethylenepentamine-N-alkyl, N-alkyl 'pentaethylenehexamine, diethylenetriamine, triethylenetetramine, tetra-, äthylenpentamin, pentaethylenehexamine, polyethyleneimine, poly (2', methyl-ethylene-imine), poly (2-ethyl-ethylene-imine), poly (2,2-dimethyl-ethylene-imine), poly (cis-2,3-dimethyl-ethylene-imine), and the like. \ As poly-N-substituted polyalkyleneimines which are obtained from copolymers of ethyleneimine and N-substituted ethyleneimine I, the polymers of the following compounds can be enumerated: ethyleneimine with N-cyanomethylethyleneimine, ethyleneimine with methyl ester of N-ethylene glycine, ethyleneimine with N- Cyano-dimethylethyleneimine, and ethyleneimine with methyl ester ] of N-carboxyäthyläthylenimins.

The invention is of course not limited to the poly-N-substituted polyamines and poly-N-substituted polyalkyleneimines just mentioned. The AlRyI group mentioned above consists atoms of an alkyl group having 1 to 8 carbon \ j or atoms of a hydroxyalkyl group having from 2nd to 8 carbon. · ■. ■ J

Diepoxydverbindungen which are used in the first stage j

"-" 609817/1042 "'

may include: 1,3-bis (1,2-epoxypropoxy) benzene, 1,4-bis (1 t 2-epoxypropoxy) benzene, 2,2-bis (pl, 2-epoxypropoxyphenyl) propane, N , N'-bis- (2,3-epoxypropyl) piperazine, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, pentaerithritol diglycidyl ether, glycelol diglycidyl ether, sorbitol diglycidyl ether, pylyethylene diglycidyl ether, 2-epoxy-phenylene glycol, 2-epoxy-propylene glycol, 2-epoxy-2-epoxy-2-epoxy, 2-epoxy-2-epoxy, 2-epoxy-glycol-propylene-propylene-propylene-propylene-glycol, 2-hexylene-propyleneoxy-propylene-propylene-propylene-propylene-propylene-propylene , Butadiene dioxide and the like. The above-mentioned diepoxide compounds can be used alone or in a mixture. The invention is not limited to the diepoxide compounds mentioned above.

Organic solvents which can be used in the first stage are e.g. benzene, toluene, xylene, butylene glycol monobutyl wires, Ethanol, isopropyl alcohol, dimethylformamide, dimethyl sulfoxide, N-methy, pyrrolidone, dioxane, carbon tetrachloride, Chloroform, η-hexane, cyclohexane and the like. These can alone or used as a mixture. In addition, water can also be used as a solvent.

The curing of the plastic can be carried out in one of the 2 following processes:

1. The plastic obtained from the first stage is processed into a film which is at a temperature between and 180 ° C for 2 to 24 hours (if in the first stage | If a solvent was used, the curing is carried out with removal of the solvent) is cured.

2. The plastic obtained in the first stage is heated to a temperature between 60 and 100 C with stirring in an aqueous solution of one or more water-soluble polymers or non-ionic surface-active substances poured so that the plastic slurried in the aqueous phase and spherical cured particles of a uniform particle size are formed. The curing time is 5 to 30 hours. ;

Hardeners for epoxy resins which can be used in the second stage include diethylenetriamine, tri ~ '

509817/1042

ethylene tetramine, tetraethyline pentamine, ethylenediamine,
m-xylenediamine, m-aminoethylpiperazine, methaphenylenediamine, j diaminodiphenylmethane , diaminodiphenyl sulfone, phthalic anhydride. and similar. Water-soluble plastics which are used as a medium
can be used include carboxymethyl cellulose, \ polyvinyl alcohol, polyvinyl pyrolidone, polyethylene glycol,
(Molecular weight 400 to 6000) and the like. Not ionogenic
surfactants having a polyoxyethylene group or
Polyoxypropylene groups are preferred. ";

In the third stage, the procedure is that, if in the;

first stage poly-N-substituted polyamines or poly-N- |

substituted polyalkylenimines which as N-substituent a ■

Cyanoalkyl group or an alkyl ester of a carboxylalkyl group; wear are used, the linear arts toff from the first · j

Step with a suitable amount of an aqueous alkali solution j

or a mineral acid (5 to 30% by weight) at a temperature j

between 60 and 100 ⁰ C for 1 to 5 hours are saponified ^:

so, in most cases, a water-soluble plastic |

is obtained. i

The hardened plastic (solid plastic) which is in the '

second stage is obtained is i in an aqueous alkali

solution or a mineral acid solution (Ibis 20% by weight) at a j

Temperature between 60 and 100 ⁰ C for 1 to 10 hours. ; saponified so that a water-insoluble plastic is obtained.

The reaction between methyl ester of methylenediamine propionic acid: and a diepoxyd compound in equimolar amounts can be like
described below. Since equimolar ■

Amounts of each reactive substance can be used
Curing in the second stage can be omitted.

First stage reaction (equimolar reaction)

NH-CH ₀ -CH ₀ -NH + CH "- CH - R - CH - CH ₀ j

I ²² I n2 / \ / ²

CH ₀ CH ₀ -0 0 ■!

CH ₂ -COOCh ₃ -CH ₂ -COOCH ₃ . ■

Polyaddition reaction

509817/10 42

ORIGINAL INSPECTED

-N-CH-CH ₀ -N-CH ₀ -CH-R'-CH-CH

CH.

CH.

OH

OH

CH ₂ -COOOH ₃ CH ₂ -COOCH ₃

Reaction in the third stage

NaOH saponification

N-CH ₀ -CH ₀ -N-CH ₀ -CH-R ¹ -CH-CH ₀ -

CH ₀ ι 2

CH ι

CH ₂ -COONa CH ₂ -COONa

Tbsp

Thus, as described above, water-soluble, or insoluble chelating plastics easily and cheaply produced will. The chelating plastics can advantageously be used to remove harmful heavy metal ions from industrial wastewater as well as for the recovery of such heavy metal ions. The plastics produced in this way can also be used advantageously in paints, binders, electrically conductive plastics, electrostatic inhibitors, refractories, ion exchange films, ion exchange fibers and the like can be used.

For a better understanding of the invention, reference is made to the following BeispMe in which the part and Percentages are based on weight.

example 1

50 parts of ethylenediamine di (methyl propionate), 73.2 parts 2,2-bis- (p-1,2-epoxypropoxyphenyl) propane and 50 parts toluene performed a polyaddition reaction in a stream of nitrogen

509817/1042

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subjected to a temperature between 80 and 90 ^° C. for 4 hours. After this reaction, the product became 60.2 parts
an aqueous 30% caustic soda solution at a
Saponified temperature between 80 and 100 C for 2 hours.

Water, methanol μήχϊ-ΦοΙύαΙ · '^ / urdeii ^ äbdesifeiKLert. That
resulting; Polymer 'Murde iünter ^ ermindeirtem: Pressure dried: by repeated Ausfällun ^ ^/ from -ebnete- ¹ water-Äcetonmedium
cleaned and dried again under reduced pressure. the
The yield was 94.5%. The resulting. Plastic -was a
water-soluble, white, hard powder. The plastic had a nitrogen content of 4.68% determined by the Kjeldahl method (calculated 4.765). ; :

3.0 g of a 15% aqueous solution of the plastic
were each 2 1 ej.ner aqueous copper sulfate, cadmium sulfate,
Lead nitrate or Queeksilberchloridlösuhg added (starting; concentration 20 ppm). After 5 minutes of shaking, the | Filtered off precipitate. By atmospheric absorption spectrum analysis
of the filtrate it was found that 98.5% of the copper ions,! 99.1% of the cadmium ions, 99.5% of the lead ions and 87.6% of the I.

Mercury ions had been removed. - · \

Example 2. ; . -: '·' ί

100 parts. Sodium ethylenediamine diacetate, 22Ο parts l, l-bis (p- '■ l ^ -epoxyphenylJ ^^ B-propanediol (epoxy equivalent; 219.1) and ^;
300% of water were subjected to a polyaddition reaction in a j stream of nitrogen at a temperature between 80 and 90 ° C '' ■ \ during 5 Hour. After the reaction was finished
The aqueous solution obtained is poured into a large amount of acetone (7 to 10 times the amount of the solution) around the plastic
to fail. The plastic was separated and dried under reduced pressure. By dissolving and failing the | Plastic from a water-acetone medium, the plastic was cleaned and dried again under reduced pressure. ' the
Yield was 80.5%. The product was a viscous, white and
water soluble plastic. The nitrogen content, determined by
the Kjeldahl process was 4.12%. (calc.t, 4,, 32%). ...- ■ · ■■ ■ \

3.0 g of a 15% strength aqueous solution of the plastic ¹ were used as described in Example 1 to remove copper and lead ions

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t, '65 / 2% "der Icüpferioneh t £ nd 72/3% d'er'-wurderi 'ent ferrit."' ^x '"' * '"'"" ~ "'-''■" · "-

Example; - 'X -' ■ «■ .-> l ~ lr: ----. ^ I. * - ■> ,: · Lvv ~ redr-.
50 parts; Hexamethylenediamino propiönaittii, -j 3Z &. ^ X Part: Pol; y-:. · .. · <S c "L athyleneglykoldiglycidylather '(EpoKydaguivalieTxti.2fiS, 0 ^f ): and 5Ό;." ., · Y.Teile ethanol were added to a polyaddition reaction in a nitrogen atmosphere at a "temperature ZWischeh 70 and 80 ° C for 1.5 hours unterworfen.Nach completion of ^Reaction 'was the" product with 360 filing of a 10%' aqueous caustic Soda solution was saponified at a temperature between 80 and 100 ° C. for 4 hours until no more ammonia odor was detectable. After completion of the saponification, a 5% hydrochloric acid was slowly added at a temperature between 50 and. 60 ° C was added until a pH between 6.5 and 7.0 was obtained. The precipitated plastic was filtered off _? washed with water and dried under reduced pressure. The plastic was precipitated twice from an acetone-DMF medium so that a polymer of the acid type was obtained ... The product obtained was a white, soft plastic powder. The yield was 84.5%. The nitrogen content was 2.75% (calculated 2.86%). The plastic was dissolved in a suitable amount of a 5% aqueous caustic soda solution at a temperature between 70 and 80 ° C. and the water was distilled off. After drying under reduced pressure, a soda type polymer was obtained in the form of a white, hard powder. 2.6 g of a 15% aqueous solution of the plastic were / as described in Example 1, used to remove copper and cadmium ions. 89.4% of the copper ions and 90.2%: the cadmium ions were thus removed from the solution.

Example 4

20 parts of ethylenediamine diacetonitrile and 12.5 parts of butadiene dioxide were placed in an autoclave and at * one Temperature between 70 and 75P.C for 4 hours for reaction brought. After completion of the reaction, the product was at a temperature between 80 and 100 ° C for 4 hours with 115.8 Saponified parts of a 10% aqueous caustic soda solution. Thus, a polymer of the acid type was described as in Example 3

509817/1042

ORiGWAL INSPECTED

- .. - ~ "<- ■■■■ - \; · - ■ '■■" · .- ■■: - ■ * -11.-' -. 'ϊ: - ■■■: "■" .- ■ ■■■: - ■ -; ■■■; - ■ - -ν ",. γ.: ■■ ■ ^: -,

ben received. The received Kuriststpff consisted of -a * - which,!

fragile powder. The yield was: 9iv5 * ', --- ""jP'eE..' StiQks "tQ.ffgeha; L ^: t; was 10.45% (calculated 10.68%). The polymer of the acid type
was further treated as described in Example 3 so that a

Soda type polymer was obtained. The polymerization _;

product was a white, hard powder. '

The procedure of Example 1 was repeated with the exception ^:

that 1.4. g of a 15% aqueous solution of the plastic j

were used to remove copper ions and cadmium alloys. ',

A removal of 45.3% for copper ions and 47.1% for. _;

Cadmium ion was obtained ... '

Example 5;

100 parts of methyl ester of m-xylenediamine diacetate, 93.5 parts of j

Glyceloldiglycidylather (epoxy equivalent: 139.5) and 20O parts ·;

Ethanol as a solvent were a polyaddition reaction! in a stream of nitrogen at a temperature between 70 and 80 ° C

subjected for 2 hours with stirring. The saponification I

was at a temperature between 80 and 100 C with 245 parts of j

a 10% aqueous hydrochloric acid solution. \

■ '"" - ■ "■!

After completion of the saponification, 270 parts of a 10% strength;

aqueous solution of caustic soda into the reaction mixture \

given and water, ethanol and methanol were distilled off. j

The resulting plastic was j

dried. As described in Example 1, the plastic | further cleaned. The obtained plastic consisted of one
white, hard and brittle powder of low water solubility.
The yield was 49.4%. The nitrogen content was 4.55%
(calculated 4.91%).

The procedure of Example 1 was repeated with the exception
that 3.0 g of a 15% aqueous solution were used
Remove copper and cadmium ions. 87.6% of the copper ions
and 85.9% of the cadmium ions were so removed.

Example 6

100 parts of ethyl ester of Ν, Ν, Ν ¹ - (tricarboxy-ethyl) -diethylen-

triamine, 52.6 parts of 1,3-bis (1,2-epoxypropoxy) benzene and 150 parts

509817/1 0A2

Benzene was reacted as described in Example 1. The product obtained was further purified as described in Example 1. However, the saponification was carried out so that 297.4 parts of a 10% strength aqueous solution of caustic soda were used. The yield was 74.5%. A pale yellow one soft powdery polymer was obtained. The nitrogen content was 6.91% by weight (calculated 7.03%).

2.0 g of a 15% aqueous solution of the plastic were used to remove copper ions and lead ions, as in Example 1 described to remove. 92.5% of the copper ions and 95.3% of the lead ions could be removed in this way.

Example 7

70 parts of methyl ester of N, N, N ', N "- (tetra-carboxyethyl) -triethylenetetramine and 28.3 parts of Ν, Ν'-bis (2,3-epoxypropyl) -piperazine underwent a polyaddition reaction with stirring in a stream of nitrogen at a temperature between 90 and 100 ° C subjected for 1.5 hours. The saponification and cleaning of the plastic were as described in Example 1 carried out. A pale yellow, hard, powdery polymer with good solubility in water was obtained. The yield was 79.4%. The nitrogen content was 11.50% (calculated 11.66%).

The process of Example 1 was repeated with the exception that 1.2 g of a 15% strength aqueous solution of the plastic were used and 91.4% of the copper ions and 92.0% of the cadmium ions could be removed.

Example 8

50 parts of methyl ester of N-octyl-N ^L _{carboxyethylethylenediamine f} 31.8 parts of ethylene glycol diglycidyl ether and 55 parts of toluene-ethanol (1: 1) were subjected to a polyaddition reaction with stirring in a stream of nitrogen at a temperature between 75 and 80 ° C for 3 hours. The saponification and cleaning of the plastic were carried out as described in Example 1. The resulting plastic was a white, hard powder with poor water solubility. The yield was 92.5%. The nitrogen content was 6.39% (calculated 6.51%).

509817/1042

50 parts of methyl ester of N-methyl-N'-carboxyethylethylenediamine, 51.2 parts of ethylene glycol diglycidyl ether and 30 parts of toluene-ethanol (1: 1) were reacted as described above
brought. The resulting polymer was a white, hard one
Powder with a low solubility in water.

2.2 g of a 10% strength aqueous solution of a plastic
obtained from N-octyl-N'-carboxyethylethylenediamine as
Starting material were as described in Example 1 for
Copper ion removal used. 97.5% of the copper ions could be removed. ;

1.8 g of a 15% aqueous solution of a plastic j

obtained from Methyles' ^ r from N-methyl-N'-carboxymethylethylene- j diamine as a starting material were used to make copper ions

and remove cadmium ions. 82.4% of the copper ions and 84.7% ■

the cadmium ions could thus be removed. ι

Example 9 ■ j

lOo parts of N- (2-hydroxyoctyl) -N ¹ - (propionitrile) ethylenediamine '

(where the 2-hydroxyalkyl group is between 20 and 30 carbon!

atoms) 157.4 TeUe of polypropylene glycol diglycidyl ether

(Epoxy equivalent: 190.0) and 100 parts of isopropanol became one:

i polyaddition reaction in a stream of nitrogen at a j Subjected to temperature between 80 and 85 ° C for 3 hours. ' The saponification was carried out with 75.3 parts of an aqueous 20% strength! Hydrochloric acid solution at a temperature between 80 and 100 C ■ made for 4 hours and the saponified product was with ' neutralized with a 5% aqueous caustic soda solution. j

The mixture was concentrated and dried under reduced pressure. By precipitating twice from a DMF-acetone medium
The product was cleaned and an acid type plastic
obtain. The product thus obtained was a white hygroscopic: plastic. The yield was 82.0% and the nitrogen content
was 4.23% (calculated 4.37%). The acid type plastic was made
Treated as described in Example 3 so that a plastic
of the soda type was obtained. The plastic obtained was white
and elastic and easily soluble in water. · '

■ ι

3.0 g of a 15% aqueous solution of the plastic were j

ORIGINAL .INSPECTED

for the removal of copper, cadmium and lead ions as in Example 1 described used. 99.2% of the copper ions, 99.4% of the cadmium ions and 99.3% of the lead ions could be removed.

Example 10

65 parts of butyl esters of Aethylendiamindipropionsäure and 82.6 parts Sorbitoldiglycidylather (Epoxydäquivalents 150) were subjected to a polyaddition reaction in a nitrogen stream at a temperature between 70 and 80 ⁰ C for 1.5 hours and cooled to a temperature of 30 to 40 ° C. 2.85 parts of diethylenetriamine were added to the reaction mixture. 80% of the resulting mixture was made into a film. The remaining 20% of the mixture was diluted with 20 parts by volume of toluene and applied in a thin layer to a pretreated nylon fabric. The film and the fabric were heated to a temperature between 130 and 150 ° C. for 7 hours in order to cure the plastic. The cured film was colorless, crystal clear, elastic and brittle so that it could not be crushed to a particle size between 0.31 and 0.327 mm. The nylon fabric covered with the mixture was white and less flexible. The finely crushed plastic and the nylon fabric coated with the mixture were saponified in an aqueous 10% solution of caustic soda at a temperature between 80 and 100 ° C. for 2 hours. The products were washed with distilled water and dried under reduced pressure. The finely divided plastic and the nylon fabric coated with the mixture were white, hard and insoluble in water.

The yield of finely divided plastic was 98.4%. To After the saponification, an experiment to determine the expansion capacity was carried out with the plastic with a grain size between 0.31 and 0.12 mm for copper, cadmium, lead and mercury

2+ carried out. The capacity was 30.5 g / kg-R for Cu, 54 * 1 g / kg-R for Cd ²⁺ , 96.7 g / kg-R for Pb ²⁺ and 120.0 g / kg-R for mercury ions . To determine the exchange capacity, 1.0 g of the cured plastic was added to one liter of an aqueous solution which contained one g of the metal ions to be examined. For copper, the solution consisted of copper sulphate, for cadmium of cadmium sulphate, for lead of lead nitrate and for jjiisek silver. QuecKsttfes-j'ChLot-iiJl »" ■ i '»€ different mixes ....

were slowly stirred at room temperature for 3 hours and allowed to stand for 20 hours, after which they were filtered. The contents (ppm) of copper, cadmium, lead and mercury ions in the filtrate were determined by atomic absorption spectrum analysis and thus preserve the exchange capacities.

Example 11

1oo parts of m-Xyloldiamih- (2-methyl-propionitrile), 181.8 parts of 2,2-bis (p-1,2-epoxypropoxyphenyl) propane and 150 parts of benzene were added to a polyaddition reaction with stirring in a \ stream of nitrogen at rather Subject to temperature between 70 and 80 C for 4 hours, cooled to a .Temperature of 30 to 40 C, mixed with 4.6 parts of ethylenediamine and formed into one _; Film processed. While removing the benzene, the film was cured at a temperature between 100 and 120 ° C for about 10 hours. The product was a clear, hard, slightly compliant cured pale yellow film. Half of the '. cured film was crushed to a particle size between 1.27 and 0.21 mm and saponified in an aqueous 10% caustic soda solution at a temperature between 70 and 100 ° C. for: 4 hours. The remaining half of the film was saponified in the same manner but in the form of the film. After the saponification, the cured plastics were filtered off, washed first with water, then with acetone and dried under reduced pressure. Pale yellow, hard, tough plastics which were insoluble in water and in organic solvents were obtained. The yield was

2+ 2+

99.5%. The total exchange capacity with respect to Cu and Cd Ions, determined by the method described in Example 10, with the exception that a cured plastic of one grain size between 0.41 and 0.21 mm was used, was 32.9 g kj / R for copper ions and 60.2 g / kg-R for cadmium ions.

Example 12

100 parts of poly (2-methyl-ethylene imine), 94 parts of methacrylonitrile and 100 parts Aethandl-toluene (1: 1) at a temperature zwisehen 70 and 80 ° C for 6 hours to an addition reaction ^1: subjected to a temperature of about 40 ° C cooled and mixed with 41.6 parts of VinyIcyclohexanioxyd (epoxy equivalent: 70.1).

-.609817 / 104.2

The mixture was subjected to a polyaddition reaction in a stream of nitrogen at a temperature between 80 and 90 ° C. for hours, cooled to a temperature between 30 and 40 ° C., mixed with 2.1 parts of diethylenetriamine and processed into a film. The film was cured at a temperature between 150 and 180 ° C. for 20 hours, ethanol and toluene being removed. A clear, pale yellow, hard, brittle, cured film was obtained. The cured film was ground to a particle size between 0.41 and 0.12 mm. The finely divided plastic was saponified in an aqueous 20% hydrochloric acid solution at a temperature between 80 and 100 ^° C. for 3 hours. The mixture was admixed with 309 parts of a 20% caustic soda solution and stirred at a temperature between 60 and 70 ° C. for one hour. The product was filtered off, washed with water and then with acetone and dried under reduced pressure. A pale yellow hardened plastic which is found in most organic

* ι

Solvent insoluble was obtained. The yield was: 98%. The total exchange capacity with respect to mercury and copper ions determined by that described in Example 10 Method with a plastic grain size between 0.41 and 0.21 mm, was 205.5 g / kg-R for mercury ions and 63.2 g / kg-R

for copper ions. j

Example 13. :

100 parts of poly (2-dimethylethyleneimine), 126.1 parts of butylaerylate , and 100 parts of ethanol were subjected to a Michael addition reaction at a temperature between 70 ° and 80 ° C. for 8 hours and cooled to a temperature of around 40 ° C. The [reaction mixture was washed with 88.3 wt. Parts of (2-epoxypropoxy l) 1,4-bis benzene was added and subjected to a polyaddition reaction in a nitrogen stream at a temperature between 70 and 80 ° C for 3 hours, at a temperature between 30 and 40 ⁰ C cooled and mixed with 10 parts of triethylenetetramine. The mixture was processed into a film, the ethanol being removed. The film was cured at a temperature between 120 and 130 ^° C. for 10 hours. A clear, colorless, slightly compliant, tough, cured film was obtained. The cured film was in an aqueous

509817/1 Oi2

gen 10% caustic soda solution at one temperature
saponified between 80 and 100 ° C. for 4 hours. Nabh the
After saponification, the film was washed with water and dried
so that a white, hard, hardened plastic which in
Water and insoluble in organic solvents was retained
became. The yield was 84.6%. The total exchange capacity _; for copper and mercury ions, determined by that in example
10 described method with a cured plastic
a grain size between 0.41 and 0.21 mm was 261 g / kg-R for
Mercury ions and 81.6 g / kg-R for copper ions. ^!

Example 14 ^!

50 parts of polyethyleneimine, 92.9 parts of methyl crotonate and 100 parts
Toluene-ethanol (1: 1) were an addition reaction in a
Temperature between 70 and 80 C during. Subjected to 8 hours
and cooled to a temperature around 40 C. The reaction mixture
was mixed with 81.0 parts of 2,2-bis- (p, 2-epoxy-propoxyphenyl) -propane and a polyaddition reaction in a nitrogen; subjected to current at a temperature between 70 and 80 ° C for 2.5 j hours. The reaction solution was cooled to a temperature ^ of 30 to 40 ° C, admixed with 5 parts of diethylene triamine \ and processed into a film using toluene, ethanol and the like; Solvents have been removed. The film was made at a. Cured at a temperature between 120 and 130 ° C for 6 hours.
The plastic obtained was clear, pale yellow, hard and brittle so that it could easily have a particle size between 0.41 and 0.21 mm
could be processed. As described in Example 10
the plastic saponified so that a pale yellow, hard and light, brittle hardened plastic which was insoluble in water and in most organic solvents was obtained. ; The yield was 93.5%. The total exchange capacity with; Relation to copper and mercury ions, determined according to the in '! Method described in Example 10 with the cured polymer one: particle size between 0.41 and 0.21 mm, was 287 g
/ kg-R for mercury ions and 99.7 g / kg-R for copper ions. _;

Example 15

100 parts of methyl ester of ethylenediamine dipropionic acid,

240.3 parts of 2,2-bis- (p-1,2-epoxypropoxyphenyi) -propane and 100

Parts of toluene were subjected to a polyaddition reaction in a stream of nitrogen at a temperature between 80 and 90.degree. C. for 4 hours and cooled to a temperature between 30.degree. And 40.degree. The reaction mixture was admixed with 2.1 parts of diethylenetriamine as a hardening agent. The mixture was slowly poured into 2000 parts of an aqueous 0 _/ 5% polyvinyl alcohol solution (degree of polymerization 1000 to 1500) so that a suspension in the aqueous phase was obtained. This suspension was kept at a temperature between 80 and 180 ° C. for 5 hours, toluene being distilled off and white spherical particles of a hard, resilient, flexible, cured plastic being obtained. The plastic was washed with hot water to remove polyvinyl alcohol and saponified with 1.2 parts of a 5% aqueous caustic soda solution at a temperature between 90 and 100 ° C. for 3 hours. After the saponification, the product was washed with distilled water and dried under reduced pressure so that white spherical particles (0.41 to 0.21 mm) of a hard and slightly flexible, cured chelating plastic were obtained. The yield was 94.8%.

The total exchange capacity with respect to mercury and copper ions determined by that described in Example 10 Process with spherical particles of the cured polymer with a grain size between 0.41 and 0.21 mm was 181 g / kg-R for Mercury and 58.4 g / kg-R for copper ions.

Example 16

100 parts of methyl ester of ethylenediamine dipropionate, 197 parts Polyethylene glycol diglycidyl ether (epoxy equivalent: 170.0) and parts of toluene underwent a polyaddition reaction in a stream of nitrogen at a temperature between 80 and 85 C for 3 hours, to a temperature between -30 and 40 C cooled, and treated with 2.1 parts of diethylenetriamine as a hardener. The curing and saponification were as in example described carried out with the exception that 25OO parts of an aqueous polyethylene lauryl ether solution (molar number of added Ethylene oxide = 10 mol) instead of polyvinyl alcohol

50 9 8 1 7/1 0 ^ 4 2

were used for curing. The resulting plastic was a white, soft product in the form of weak spherical particles which were insoluble in water and organic solvents. The yield was 85%. The total Exchange capacity with respect to mercury ions, determined by the method described in Example 10, with spherical Particles of the hardened plastic from 0.41 to 0.21 mm was 274 g / kg-r.

Example 17

80 parts of methyl ester of m-xylenediamiridiacetic acid, 73.8 parts of 1,3-bis (1,2-epoxypropoxy) benzene and 50 parts of benzene were subjected to a polyaddition reaction in a stream of nitrogen at a temperature between 70 and 80 ° C for 3 hours, cooled to a temperature between 30 and 40 ⁰ C and treated with 2.1 parts of diethylenetriamine as hardening agent. The curing and saponification were carried out as described in Example 15 with the exception that 1000 parts of an aqueous 0.5% strength polyethylene glycol solution (molecular weight = 2000) were used for the curing. The resulting hard and flexible plastic was in the form of white spherical particles which were insoluble in water and in most organic solvents. The yield was 86%. The total one ^!

2+ '■

Exchange capacity with respect to Cu ions, determined by the method described in BeispiellOi, with spherical particles of the cured polymer with a grain size between 0.41 and 0.21 mm, was 36 g / kg-R. _:

Example 18

50 parts of methyl ester of m-xylenediamine dipropionic acid, 4 3.3 parts Propylene glycol diglycidyl ether (epoxy equivalent: 104.6) and Parts of benzene underwent a polyaddition reaction in a stream of nitrogen at a temperature between 70 and 80 ° C subjected for 2 hours to a temperature between 30

ο
and 4o C cooled and treated with 1.1 parts of diethylenetriamine.

The subsequent reactions were as described in Example 15 performed with the exception that 900 parts of an aqueous 1% polyvinylp ^ rolidorilösung (molecular weight τ 10,000) for the Curing, white spherical particles,

50 9 8 17/1 0 Λ 2

(0.21 to 0.07 mm) of a hard and brittle plastic which was insoluble in water and in most organic solvents were obtained. The yield was 76%. The total exchange capacity with respect to Cu, determined by the method described in Example 10 with spherical particles of the cured Plastic with a grain size between 0.21 and 0.12 mm was 76.4 g / kg-r.

Example 19

100 parts of pentaethylenehexamine and 222 parts of methyl acrylate were subjected to a Michael addition reaction at a temperature between 70 and 80 C for 8 hours _T to a temperature around 40 ° C cooled, diluted with 106 parts of 1,3-bis (1,2-epoxypropoxy) benzene and 300 parts of toluene are added to a polyaddition reaction in a stream of nitrogen at a temperature between 70 and 80 ° C. for 4 hours. The reaction mixture was cooled to a temperature between 30 and 40 ° C. and 2.1 parts of ethylenediamine were added as a curing agent. The curing and the saponification were carried out as described in Example 15 with the exception that 3500 parts of an 0.5% aqueous carboxymethyl cellulose solution were used for the curing. Pale spherical particles of a hard and strong shock-resistant plastic which was insoluble in water and in most organic solvents were obtained. The yield was 84%. The total exchange capacity

2+
with reference to Cu, determined by the method described in Example 10 with spherical particles of the cured polymer with a grain size between 0.41 and O _f 23 mm, was 42.4 g / kg-R. The exchange capacity for mercury ions was 278 g / kg-R.

Example 20 ^:

30 parts of poly (2-ethylethyleneimine), 13.4 parts of acrylonitrile and 50 parts of ethanol were subjected to an addition reaction at a temperature between 70 and 80 C for 10 hours, cooled to a temperature of 40 ° C and with 17.9 parts 1,4-bis (1,2-epoxypropoxy) benzene and 50 parts of toluene were added. The mixture underwent a polyaddition reaction in a stream of nitrogen subjected at a temperature between 70 and 80 ° C for 4 hours. The curing and saponification were as in

509817/104 2

Example 15 described carried out. Pale yellow spherical particles (0.635 to 0.15 mm) of a hard and strong, against Shock-resistant plastic which was insoluble in water and organic solvents were obtained. the The yield was 73%. The total exchange capacity with reference to

2+
Cu determined by the method described in Example 10.

with spherical particles of the cured plastic with a grain size between 0.41 and 0.21 mm, was 72.4 g / kg-R.

Example 21 \

100 parts of poly (cis-2,3-dimethylethyleneimine), 94.7 files; Methyl acrylate and 200 parts of toluene-ethanol (1: 1) were subjected to a Michael addition reaction at a temperature between 70 and 80 ° C. for 8 hours. The reaction mixture was cooled to a temperature around 40 ° C, 158.1 parts per weight. 2,2-bis (pl, 2-epoxypropoxyphenyl) propane was added and 'a polyaddition reaction in a nitrogen stream at a temperature between 70 and 80 ⁰ C. subjected for 3 hours. 10 parts by weight of diethylenetriamine were added to the reaction mixture. The curing and saponification were carried out as described in the example. Pale yellow spherical particles

(0.63 to 0.21 mm) of a tough strong shock resistance; Capable plastic which was insoluble in water and in organic solvents were obtained. The yield was 76%. The total exchange capacity with respect to copper and mercury ions, determined by the method described in Example 10 with spherical particles of the cured polymer with a grain size between 0.63 and 0.41 mm, was 251 g / kg-R for mercury ions and 96.5 g / kg-R for copper ions. \

Example 22

100 parts of polyethyleneimine, 140 parts of methyl acrylate and 150 parts Toluene-ethanol (1: 1) were subjected to a Michael addition reaction at a temperature between 70 and 80 ° C. for 3 hours and cooled to a temperature around 40 C. The reaction mixture was added with 74.0 parts of 1,3-Bls- (1,2-epoxypropoxy) benzene added and a polyaddition reaction in a stream of nitrogen at a temperature between 70 and 80 C for 3 hours subject. The curing and saponification were carried out as described in Example 15 with the exception that 1000 parts

■ 609817/1042

a 0.5% aqueous polyoxyethylene nonylphenol solution (adduct with 10 mol of ethylene oxide) were used. Plastic became in the form of pale yellow, hard, spherical particles which are insoluble in water and in most organic solvents were received. The yield was 82%. The total exchange capacity with respect to mercury ions as determined by the spherical particle method described in Example 10 of the cured polymer with a grain size between 0.41 and 0.21 mm, was 291 g / kg-R.

Example 23

100 parts of a copolymer of ethyleneimine and N-cyanomethylethyleneimine (molar ratio: 9), 21.8 parts of 2,2-bis (p-1,2-epoxypropoxyphenyl) propane and 120 parts of toluene underwent a polyaddition reaction in a stream of nitrogen at one temperature between 70 and 80 C for 3 hours. The resulting polymerization solution was slowly added dropwise, with stirring, to an aqueous 0.5% polyvinyl alcohol solution (degree of polymerization 1000-1500) which had been preheated to 70.degree. As a result, the plastic was suspended in the aqueous system. The suspended plastic was then ^{heated further to 88 to 100 °} C. for 5 hours, toluene being distilled off. Yellow, spherical particles of a hard, tough, elastic, hardened plastic were obtained. The plastic was carefully washed with warm water to remove polyvinyl chloride. The plastic was saponified in 1000 parts of a 5% aqueous caustic soda solution at 90 to 100 ° C. for 3 hours. The saponified plastic was washed with distilled water and dried under reduced pressure. A spherical, hard, elastic, yellow, hardened plastic (grain size 0.41 to 0.12 mm) was thus obtained. Yield 89.6%. The total exchange capacity with respect to mercury ions was determined as described in Example IO with the spherical hardened plastic with a grain size between 0.41 and 0.21 mm. A capacity of 274 g / kg-R was measured.

Example 24

200 parts of a copolymer of ethyleneimine and

509817/1042

Methyl ester of N-ethylene glycine (molar ratio 0.5: 9.5), 26.2 parts of pentaerythritol diglycidyl ether and 220 parts of toluene

were subjected to a polyaddition reaction in a stream of nitrogen at a temperature between 70 and 80 ^° C. for 2 hours. The curing and saponification of the plastic obtained were carried out as described in Example 23, with the exception that 1500 parts of a 0.5% strength aqueous polyvinylpyrolidone solution were used instead of polyvinyl alcohol. The plastic obtained was hard, elastic and had a pale yellow color. It was obtained in the form of spherical particles which were hardly soluble in water and in most organic solvents.

The yield was 87.4%. loo ml of the plastic of a grain size between 1.27 and 0.31 mm (moisture content 63.4%) were placed in a column in which, at sv = 20 / 15.6 1 of an aqueous copper sulfate solution, its copper ion concentration 100 ppm were entered (the total exchange capacity with respect to copper ions was 15.6 g / l ~ R). 150 ml of 2N hydrochloric acid were added at sv = 2 to the plastic on which the copper ions had been adsorbed. 78.5% of the Copper ions could thus be recovered. The total Exchange capacity with respect to mercury ions was determined as described in Example 10. It was 267 g / kg-R.

Example 25

230 parts of a copolymer of ethyleneimine and butyl ester of K-ethylene glycine (molar ratio 1: 9), 26.8 parts of polyethylene glycol diglycidyl ether and 240 parts of toluene were subjected to a polyaddition reaction in a stream of nitrogen at a temperature between 00 and 85 ° C. for 4 hours. The following reactions were carried out as described in Example 23, with the exception that 2000 parts of a 0.8% aqueous carboxyinethyl cellulose solution were used for the curing, the plastic produced in this way was soft, brittle, yellow and w- -} ■ - . obtained in the form of spherical particles which were insoluble in water and insoluble in organic solvents. The yield was 78.7%. The total exchange capacity, determined as described in example K) rat spherical »hardened

5 0 9 8 17/10 /.;-

Plastic with a grain size between 0.41 and 0.21 mm was 67/4 g / kg-R for copper ions and 224 g / kg ~ R for mercury ions.

Example 26

100 parts of a copolymer of Äethylenimin and Methylester of N-Karboxyäthyläthylenimin (molar ratio 2: 1) were subjected to a polyaddition reaction in a nitrogen stream at a temperature between 70 and SO ⁰ C. for 4 hours. The reaction mixture was cooled to 30 to 40 ° C. and 3 parts of diethylenetriamine as a hardening agent were added. The polymer obtained was added dropwise with stirring to 1000 parts of an aqueous 0.2% strength polyethylene glycol solution (average molecular weight 6000}. This slurried the plastic in the aqueous system. The slurried plastic was heated to 88 to 100 ° C. for 5 hours, toluene being distilled off A cured pale yellow, hard, tough and elastic plastic was obtained. The obtained product was washed with warm water to remove polyethylene glycol. The saponification was carried out in 1000 parts of an aqueous 5% caustic soda solution at 90 to 100 ° C. for 3 hours After the saponification, the plastic was washed with distilled water and dried under reduced pressure. A spherical, hard, elastic, pale yellow chelating plastic (grain size 0.41 to 0.12 mm) was obtained. The yield was 81.4%. With the spherical hardened plastic with a grain size between The total exchange capacity was determined at 0.41 and 0.21 mm. With respect to copper ions, a capacity of 72.4 g / kg-R was obtained, and with respect to mercury ions a capacity of 278 g / kg-R was advised.

Example 27

The cured films and the nylon fabric coated with the polymer solution of Examples 10 and 11 were with a Vibration electrometer type TR8O4M from Takeda Riken Co. Ltd. subjected to determine the specific surface resistance. The surface resistivity of the coated nylon fabric was 2.3 χ 10 Λ and that of the hardened Films 4.4 χ 10 Ω at a voltage of 100OV and one Trial time of 4 seconds.

5Q9817 / KH2

The coated nylon fabric obtained according to Example 10 was immersed in an aqueous copper sulfate solution for 3 hours. It was then washed with water and dried under reduced pressure. The surface of the nylon fabric on which the copper ions were adsorbed had a surface resistivity of 8.4 χ 10 Xl.

Example 28 '

An aqueous 5% solution of the water-soluble polymer from Example 1 was applied to a metal plate with a brush and at a temperature of 50 ° C for 12 hours dried under reduced pressure to leave a thin clear film on the metal plate. This with the plastic coated metal plate was kept in a room for 6 months. After 6 months there was no rust formation on the Metal plate can be found, thus proving that the plastics of the present invention work well as rust inhibitors suitable. Another plate with a plastic coating was placed in water at a temperature of 50 ° C. after 6 months immersed for one hour and the coating film of the water-soluble plastic was completely detached from the surface of the metal plate.

65 parts of butyl ester of ethylenediamine dipropionic acid and 82.6 parts of sorbitol diglycol ether (epoxy equivalent 15C)) were subjected to a polyaddition reaction as described in Example 10, cooled to a temperature between 30 and 40 ° C. and treated with 2.85 parts of diethylenetriamine and 520 parts of toluene offset. The mixture was applied in thin layers to a soft steel plate and cured at temperatures between 130 and 150 ° C. for 7 hours. The coated plate had a high resistance to corrosion and was also insensitive to the formation of rust, as indicated below:

Coating film of the present invention

Alkali spray (15 hours) no changes noticeable Salt water spray

(500 hours) no changes detectable

Checker test to determine ι

the adhesion 90/100 or more

509817/1042

Claims (12)

Claims 1. Polymer, characterized in that tos by reaction of poly-N-substituted polyamines or poly-H-substituted polyalkyleneimines ^ which are by substitution of the active hydrogen atoms located on the nitrogen of the polyamines or polyalkyleneimines by alkali metal oxides or allyl esters of carboxyalkyl or cyanoalkyl groups are obtained with at least 2 active hydrogen atoms bound to nitrogen must remain in the molecule, is obtained with diepoxy compounds. 2. Polymer according to claim 1, characterized in that the poty-N-substituted polyamines from polyamines d «r general formula R-EJH (R ¹ III) H where R is hydrogen or an alky! Group with 1 to 8 carbon atoms or a ( > -hydroxyalkyl group with 2 to 8 carbon atoms, R ^{1 represents} an iVebhylen, phenylene or xylene group and η represents a number 1 or 2, are obtained. 3. Polymer according to claim 1, characterized kern ^ eichnet, that poly-N ~ substituted polyalkylenimines are obtained from Polymers of ethyleneimine, 2-Methyl'athyleri iniin, 2-Aethyläthy bm inin, 2, 2-Dimethy läthy lenimin, eis-2, 3-1 ame thy 1-äthytfciiiimin or trans-2, 3-dimethylethyleneimine or MiKChpolyiiieriüaten of ethyleninine and li-substituent ethyluriimines nttt:; t will » 4. Polymer according to claim 1 / characterized in that a cyanoalkyl group of the general formula (CHR ¹ ) CN where R ^{1 is} hydrogen or a methyl group and η 1 or 2 is used as the N-substituent. 5. Polymer according to claim 1, characterized in that the N-substituent is an alkali metal salt or an alkyl ester. a carboxyalkyl group of the general formula (CHR'J _n COOR " , where R ^{1 is} hydrogen or a methyl group, R" is an alkali metal or an alkyl group having 1 to 4 carbon atoms and N is a number 1 or 2. 6. Polymer according to claims 1-5, characterized in that that as diepoxy compounds 1,3-bis- (1,2-epoxy-propoxy) -benzene, 509817/1042 1,4-bis (1,2-epoxypropoxy) benzene, 2,2-bis (ρ-1/2-epoxypropoxyphenyl) propane, N, N'-bis (2,3-epoxypropyDpiperazine, 1,1-bis (p -1,2-epoxypropoxyphenyl) -2,3-propanediol, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol diglycidyl ether,
Pentaerythritol diglycidyl ether / sorbitol diglycidyl ether,
Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, vinyl cyclohexene dioxide, butadiene dioxide can be used. 7. Polymer according to claim 1, characterized in that it is saponified with acid or alkali. 8. Polymer according to claim 1, characterized in that it is cured by adding epoxy resin curing agents. 9. Polymer according to claim 8, characterized in that it is saponified with acid or alkali. 10. polymer in the form of powder or spherical particles according to claim 1, characterized in that the polymerization mixture in an aqueous solution of a water-soluble polymer or a non-ionic surface-active agent
is poured and the resulting slurry by addition hardened by epoxy resin hardeners in the aqueous solution
will. ; 11. Polymer according to claim 10, characterized in that it is saponified with acid or alkali. 12. Polymer according to claim 10 and 11, characterized in that the aqueous solution of a polymer in which the
Polymer of the invention cast wi rd! Carboxymethyl cellulose polyvinyl alcohol, polyvinyl pyrolidone and polyethylene glycol
(Molecular weight 400 to 6000) and that, as the nonionic surface active agents, those having a polyoxyalkylene group are used. 509817/1042
BATH ORIGINAL