DE2258535A1 - CHELATING AMINO ACID ADDITIONAL POLYMER - Google Patents

Description

MITSUBISHI CHEMICAL INDUSTRIES LTD., Tokyo, Japan

Amino acid addition chelating polymer

The invention relates to a new chelating amino acid addition polymer. In particular, it relates to a new chelating amine acid addition polymer having amino acid units. The invention also relates to the new use of the new Polymers.

Some time ago there was a call for heavy metals to be removed from wastewater from mining or chemical industries, to prevent pollution. In order to remove heavy metals in wastewater, it has been suggested to adjust the pH of the Controlling wastewater to precipitate the metals as metal hydroxide or using an ion exchange resin to adsorb.

In the first procedure, it is very difficult to prevent that a small amount of heavy metal ions remains and, in addition, filtration is not easy. With the latter In the process, on the other hand, it is difficult to selectively adsorb the metal ions because other ions appear at the same time. It is known to remove metal ions using a chelating compound. However, if a well-known chelating agents such as ethylenediamine tetraacetic acid and

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Nitriloacetic acid etc. a chelate complex with heavy metal ions forms, the complex is water-soluble.

The known chelating agents thus have certain uses. So you can use them as additives to detergents use, but they cannot be used to remove heavy metals from an aqueous solution.

The present invention is based on the problem of the disadvantages to overcome the known treatment agents and appropriate means for the selective removal of heavy metal ions to provide from an aqueous solution with high effectiveness. It has been found that a suitable Chelating polymer can be made by using a particular acryloyl compound and an amino acid Subjects to addition polymerization.

The invention relates to a new chelating amino acid addition polymer, which allows excellent chelation. The invention also relates to a method for removing a heavy metal compound in an aqueous solution using the novel chelating agent Amino acid addition polymers.

The invention relates to a new chelating amino acid addition polymer, produced by addition polymerization of an acryloyl compound containing X acryloyl groups, where the acryloyl groups have the formula

CH-C-C-

<- t It

R 0

where R is a hydrogen atom or a hydrocarbon radical, the amino acid Y containing active hydrogen atoms which are reactive in the Michael addition reaction and where
Y mean £ 2.

and where X and Y are integers and X = 2 and

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Under the Michael addition reaction or the Michael condensation reaction it is understood that a compound with active hydrogen atoms is added to a C = C double bond.

In the present invention, the Michael addition conversion used. ¥ ¥ a compound that contains two aryloyl groups'

ROOR

1 !! 1It

CH ₂ = C - C - A - C - C = CH ₂

reacted with a compound that has two active hydrogen atoms Contains H-B-H, a linear polymer is obtained which has the following units

RO OR -fB - CH ₂ - CH.- C - A - C - CH - CH ₂ -) -

contains. "

The resulting polymer is water-soluble and has the Ability to form chelates derived from the amino acid group.

Is the resulting polymer with a heavy metal ion in reacted with an aqueous solution to form a complex, a water-insoluble precipitate of the complex is formed.

When at least one of the acryloyl compound and the amino acid contains three or more than three active groups, that is, when X + Y } are 4, the combinations can be classified into the following three kinds.

The first option is the acryloyl compound that contains at least three acryloyl groups, reacted with the amino acid containing at least three active hydrogen atoms. ,. ■

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The second option is the acryloyl compound that contains two acryloyl groups, reacted with three or more than three active hydrogen atoms.

The third option is the acryloyl compound that contains at least three acryloyl groups, reacted with an amino acid that contains two active hydrogen atoms. However In more complicated cases, a mixture can be used instead of a compound containing at least three active groups a compound containing a bifunctional group, and that compound can then be used.

For example, in the first and the second possibility, lysine is used as the amino acid with at least three active hydrogen atoms, and glycine is used as the amino acid with at least two active hydrogen atoms added. By doing In the first, second and third case it is possible to add an auxiliary crosslinking agent, i.e. a compound which contains at least three active hydrogen atoms for the Michael addition reaction such as an N-unsubstituted oliamine triol, Trithiol etc. along with the amino acid.

In the above cases, a water-insoluble polymer is obtained in accordance with the Michael addition reaction, since the polymer containing the amino acid units is different from each other derives the chelating property, is polymerized with two- or three-dimensional cross-links. The polymer of the present invention can also be produced by the following method.

In addition polymerization of an acryloyl compound, the contains at least two acryloyl groups, and the amino acid containing at least two active hydrogen atoms for the Michael addition reaction, it is possible to produce an addition polymer which is unreacted terminal

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Contains acryloyl groups when the equivalent amount of acryloyl groups of the acryloyl compound is higher than the equivalent amount of active hydrogen atoms of the amino acid (if A moles of acryloyl compound and B moles of amino acid are used, AX ₁ ) must be BY).

When the resulting polymer is in the presence or absence of a comonomer using a free radical initiator is polymerized, or when the resulting polymer with a compound that has at least three in the Michael addition reaction contains active hydrogen atoms through Michael reaction is addition polymerized, one can use polymers manufacture that have three-dimensional structure.

The method is preferably used to produce water-insoluble, high strength solids if that Addition polymer of the acryloyl compound and the amino acid is water-soluble or is a weak gel-forming product. The chelating amino acid addition polymer of the present invention also includes addition polymers of the acryloyl compound and the amino acid and modified polymers made by performing radical polymerization or Michael reaction.

As acryloyl compounds that contain at least two acryloyl groups can contain alkylene-bisacryl-amide, alkylene-bismethacryl-amide use, (These can be implemented by implementing

a) formaldehyde with acrylamide or methacrylamide or

b) alkylenediamine with acrylic or methacrylic acid or their esters

getting produced.)

substituted methylenebisacrylamide, substituted methylenebismethacrylamide (these can be implemented by implementing

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a) Adehyd with at least two carbon atoms in the molecule with acrylamide or methacrylamide or

b) Ketone acetal with acrylamide or methacrylamide, according to the procedure of Journal of Polymer Science Part A-I, Volume 8 1970-1972 ('7O)), dihydroxyalkylene-bisacryl-amide and dihydroxyalkylene-bismethacryl-amide (these can be prepared by reaction a dialdehyde such as glyoxal with acrylamide or methacrylamide), methylene bisacrylamide, methylene bisacrylamide, dihydroxyethylene bisacrylamide, dihydroxyethylene bismethacrylamide, etc.

It is also possible to use an alkylene glycol diacrylate or alkylene glycol dimethacrylate. These compounds can be a reaction product of acrylic acid or methacrylic acid with glycol, for example methacrylic acid with glycol, for example ethylene glycol, propylene glycol _f butylene glycol, polyethylene glycol and polypropylene glycol, etc. such as glycol diacrylate and glycol dimethacrylate.

It is also possible to use 1 ₍ 3- (bisacrylic acid amide methyl) -2-imidazolidone-hexahydro-s-triazine derivatives containing two acryloyl groups in the 1- and 3-positions.

As acryloyl compounds that contain at least three acryloyl groups may contain hexahydro-1,3,5-triacryloyl-s-triazine alkylene polyol polyacrylate or alkylene polyol polymethacrylate use. The last two compounds can be the reaction product of a polyol such as glycerin, trimethylolpropane, Pentaerythritol, sorbitol, etc. with acrylic acid or methacrylic acid. -

When defining the amino acids that contain active hydrogen atoms, "active hydrogen atom ¹¹ " is understood to mean an atom that is active in the Michael addition reaction,

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like a hydrogen atom attached to a nitrogen atom of the amino group is bonded, a hydrogen atom of an active methylene group, a hydrogen atom of an -OH group and a hydrogen atom of an -SH group, etc.

Amino acids containing two active hydrogen atoms include α-amino acids such as glycine, α-alanine, glutamic acid, and aspartic acid; ß-amino acids such as ß-alanine and also other amino acids such as N ₁ N- (or N, N ^l -) - dimethyllysine, ethylenediamine-N, N (or N, N ') - diacetic acid, N, N-bis- (hydroxyethyl) glycine etc.

As an amino acid that has at least three active hydrogen atoms contains, one can use lysine, alginine (alginine), ornithine, threonine, cysteine and serine.

In general, the Michael reaction is carried out in an organic solvent or in an aqueous medium in the presence an acidic or alkaline compound. It is possible to use various addition polymerization conditions, and it is preferred to carry out the reaction in carry out aqueous solution. However, it is also possible the reaction in a polar solvent which is inactive to the system as in lower alcohols, for example Methyl alcohol, ethyl alcohol, dimethylformamide, dimethyl sulfoxide, esters, for example ethyl acetate, methyl acetate, and ketones, for example acetone.

It is possible to use a non-polar solvent such as hydrocarbons in some cases. The Michael reaction can be carried out in the presence of an acidic compound such as a mineral acid, for example sulfuric acid and nitric acid, can be carried out smoothly, but then generally longer reaction times are required than in the presence of an alkaline compound. In the case of

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According to the invention, the better results are obtained in the presence an alkaline compound such as alkali metal hydroxide, alkali metal carbonate, alkali metal bicarbonate, Alkali metal alcoholate, piperidine and hydroxybenzyltrimethylammonium, Compared to the results in the presence of an acidic compound, it is best to check the reactants to implement in an alkaline aqueous medium.

If the reaction temperature is too low, it is from the standpoint of the reaction rate and from the standpoint of Cooling measures disadvantageous. If the reaction temperature is too high, it is disadvantageous because the acryloyl group radical polymerizes can be. Suitable temperatures are in the range from 0 to 200 C, preferably in the range from 20 to

ο °

100 C, particularly preferably in the range from 30 to 80 G.

In order to inhibit the polymerization of the acrylic groups even in the reaction, it is preferred to use a radical polymerization inhibitor to add. If the acryloyl compound is reacted with the amino acid under the conditions AX> BY, and then unreacted acryloyl groups are reacted with a compound that has at least three active hydrogen atoms in the Michael addition reaction, it is possible to use polyamines, polyalcohols, polythiols and amino alcohols such as Polyamines and substituted polyamines, for example ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, Triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, phenylene diamine, N-methylethylene diamine, N-methylpropylene diamine, Polyols, for example glycerol, sorbitol, thiols, for example 1,2-dimercaptopropanol, amino alcohols, for example, monoethanolamine, diethanolamine, aminothiol, for example 2-aminoethanthiol, and ammonia to be used.

In the preparation of the addition polymer according to the invention by adding this compound it is possible in two stages

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to implement, i.e. first the acryloyl compound with the Amino acid reacted and then with the compound that has at least three hydrogen active in the Michael addition reaction contains atoms. It is also possible to implement the three components at the same time in one step. Although The order of addition is not an important factor, however, it is necessary to include both the amino acid as well the other compound, which has at least three active hydrogen atoms contains, with the acryloyl groups of the acryloyl compound to implement.

If an excess of the acryloyl compound is reacted with the amino acid so that unreacted acryloyl groups in the addition polymer remain, and then the addition polymer is free-radical-polymerized, it is possible to carry out the free-radical polymerization perform by using a radical polymerization catalyst. if desired together with to a comonomer, with or without separation of the addition polymer from the reaction mixture.

The suitable comonomers can be vinyl compounds which can be copolymerized with an acrylic group such as Acrylic acid amide, methacrylic acid amide, acrylic acid ester, methacrylic acid ester, Acrylic acid, methacrylic acid, styrene and vinyl acetate. Can be used as radical polymerization catalysts use radical polymerization initiator catalysts such as persulfate, peroxide and benzoyl peroxide.

The amounts of the acryloyl compound and the amino acid used in the reaction are given below explained.

If a water soluble addition polymer is desired, it is preferred to use substantially equimolar amounts of both compounds. If a water-insoluble addition

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polymer is desired, the molar ratio and the number of active groups in the compounds should be chosen be that essentially the equilibrium

AX = BX

is present. However, when a water-insoluble addition polymer by additional radical polymerization or additional Michael reaction is obtained, it is necessary to add an excess of the acryloyl compound. Accordingly, the value of AX / BY is higher than 1 and preferably higher than 1.2, particularly higher than 1.5 from the viewpoint of crosslink density. However, if the value ΑΧ / BY is too large, the number of amino acid units per weight of the resulting addition polymer too low. From the above standpoint, it is possible to find an optimal Value should be selected depending on this fact, and this value is generally less than 10 and is generally less than 5.

As indicated above, the addition polymers of the invention contain Nitrogen atoms and carbonyl atoms in the polymer chain and carboxyl groups close to the nitrogen atoms (corresponding to the position of the amino group and the carboxyl group of the amino acid). These are basic properties. The reason why the addition polymers of the present invention have the ability to remove heavy metals is not fully known. However, it is believed that this property is related to the chelating structure provided by the amino acid originates, related. Process for removing heavy metal ions in aqueous solution using the Polymers according to the invention are explained in more detail below.

If the water-soluble polymer is used, one adds to the aqueous solution containing the heavy metal ions

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Solution slightly in the excess equilibrium of the chelating agent Amino acid addition polymers, so that the water-insoluble polymer that coordinates the heavy metal ions contains bound as chelate, precipitates.

It has been found that when copper ions are treated, the characteristic blue color of the amino acid-copper complex is obtained in which precipitation occurs.

In the formation of the precipitate of the water-soluble addition polymer Due to the heavy metal ion, the amino acid has a relatively high chelation constant, but has they only have two ligands. The heavy metal ions have coordination numbers of 4 or 5 and therefore two or three moles of amino acids are coordinated to a heavy metal ion .

In the chelation between the heavy metal and the inventive Addition polymers are certain crosslinks in the molecule of the addition polymer or between the molecules of the addition polymer formed by the heavy metal. The reason for the formation of the water-insoluble Polymers arises from these considerations.

To remove the heavy metal ions from the chelate addition polymer, the chelate polymer is suspended in water and a mineral acid such as hydrochloric acid is added until an acidic pH is adjusted, and then is the suspension is stirred so that the addition polymer, which now does not form a chelate, is dissolved again, and the Heavy metal ions are separated in the form of their salts in water. You then add a to the resulting solution Alcohol or acetone and the chelating reaction polymer precipitates again; however, the heavy metal ions are now dissolved in the filtrate in the form of their salts, and therefore it is possible

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borrowed to separate and recover the addition polymer.

When the addition polymer is a water-insoluble polymer, it is possible to take it in the form of powder or various Shapes to use. The addition polymer can also be used as a resin in spherical or pellet form (ball pelet resin) can be produced as an ion exchange resin by mixing the compounds in suspension in an aqueous solution, which contains the starting material, in an inert solvent which is immiscible with water, and in which the starting material does not dissolve compared to water.

The fact that the resulting addition polymer has the property possesses to form chelates can be confirmed as follows.

According to the rating of ion exchange resins, that becomes Addition polymers are packed in a column and an aqueous solution containing heavy metal ions is passed through the column poured, wherein the heavy metal ions are adsorbed according to the molar ratio of amino acid in the addition polymer will. When copper ions are treated, just as with water-soluble addition polymers, one finds that the Coloring begins at the top of the column and that the color layer is progressively enlarged, depending on the flow rate the aqueous solution.

To remove heavy metal ions from the resin that adsorbs them, the heavy metal ions can be easily removed, when an acidic aqueous solution containing mineral acid such as hydrochloric acid is passed through the column. Regardless of whether a water-soluble or insoluble polymer is used, the method for removing Heavy metal ions from an aqueous medium in the following

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Characteristics the same. The aqueous medium that contains the heavy metals is treated with the chelating amino acid addition polymer of the present invention and then the aqueous medium and the polymer which forms a chelate with the heavy metals, separated, the chelating polymer is treated with an acidic solution to restore the chelating ability, and then the recovered can Polymers can be reused for re-treatment. The chelating amino acid addition polymer of the present invention adsorbs metals with high chelation constants such as ions such as nickel, cobalt, lead, cadmium, Mercury, rhodium and palladium etc. as well as copper and heavy metal ions.

According to the invention, a new and valuable chelating amino acid addition polymer is created, the heavy metal ions selectively adsorbed in aqueous solution without attacking the other ions.

The following examples illustrate the invention without restricting it.

example 1

3.08 g of methylenebisacrylamide were placed in a 100 cm four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, a drying tube and a condenser, and the mixture was stirred at 45.degree. A solution of 1.50 g of glycine and 0.80 g of sodium hydroxide in 14.6 g of water was added to the compound and the mixture was ^{reacted at 45 °} C. for 5 hours.

According to the determination of the decrease in double bond, the conversion was 86.5%. The reaction mixture was in poured a large amount of acetone to remove the white polymer

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to fall. The polymer was dried under reduced pressure, whereby 4.98 g of the dried polymer was obtained. The dried polymer was a white powder and very hygroscopic. 10 g of a 1% solution of the polymer were added to 10 g of a 1% copper (II) sulfation, with a dark blue colored polymer precipitated. The precipitate was insoluble in water and organic solvent and was not hygroscopic.

Example 2

According to the method of Example 1, a solution of 1.78 g of β-alanine, 0.80 g of sodium hydroxide in 5.7 g of water was added to 3.08 g of methylenebisacrylamide and the mixture was ^{reacted at 60 °} C. for 3 hours. According to the determination of the decrease in the double bond, the conversion was 93.9%.

The reaction mixture was added to a large amount of acetone to obtain a colorless polymer. The polymer was dried under reduced pressure to obtain 5.1 g of the dried polymer. The dried one Polymer was highly hygroscopic and was mixed with a 1% aqueous copper (II) sulfate solution, the same being said dark blue colored polymers as in Example 1 precipitated.

Example 3

Following the procedure of Example 1, a solution of 2.94 grams of L-glutamic acid, 1.6 grams of sodium hydroxide in 7.7 grams of water was made added to 3.08 g of methylenebisacrylamide and the mixture was reacted at 80 ° C. for 5 hours. After the determination the double bond decrease, the conversion was 59.5%. The reaction mixture became a large amount Acetone added to give a colorless polymer. The polymer was treated with an aqueous 1% strength copper (II) sulfate solution mixed, the same dark blue-colored polymer as in Example 1 precipitated.

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Example 4

In a 100 ecm four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, 3.08 g of methylenebisacrylamide were added and the mixture was stirred at 50 ^° C. A solution of 1.83 g of L-lysine monohydrochloride and 0, 80 g of sodium hydroxide in 5 | 8 g of water were added to the compound and the mixture was ^{reacted at 50 °} C. for 30 minutes, a transparent, viscous solution being formed and then a gelled product being formed. The gel-like product was reacted for a further hour , then removed from the flask, washed with water and with methanol, and then the gel-like product was filtered. The filtered, gel-like product was ground in a mortar and dried under reduced pressure. The dried, gel-like product was a white powder. The yield was 4.5 g.

2.0 g of the obtained. Product (content of carboxyl groups 3.51 χ 10 "mol) were placed in a column and washed with water Washed and then added to the upper part of the column 10 ecm of an aqueous IJfigen copper (II) sulfate solution (content of copper ions 4.01 χ 10 ~ mol, the solution was pale blue).

The polymer changed its color to a deep blue color by the formation of a chelate compound of copper ions and the water that came out of the column was colorless and transparent. Chelation titration with EDTA showed that there were no copper ions in the water running off were included.

A large amount of aqueous 1N hydrochloric acid solution poured onto the top of the column and the polymer turned colorless, and the water that came off the column was blue 'which confirmed the presence of copper ions. The procedure could be repeated »

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Example 5

The procedure of Example 4 was followed and the reaction vessel described there was also used. 3.08 g of methylenebisacrylamide were stirred at 50.degree. A solution of 1.685 g ornithine hydrochloride and 0.80 g sodium hydroxide in 5-6 g water was added to the compound. The mixture was ^{reacted at 50 °} C. for 10 minutes, a transparent, viscous solution of a gel-like product being obtained. The gel-like product was further reacted for 1 hour and then, if one worked according to Example 4, a colorless powder was obtained. The yield was 4.3 g

Following the procedure of Example 4, 2.0 g of the product (content of carboxyl groups 3.59 × 10 "- * mol) in given a column and with water and 10 ecm of an aqueous 1 # strength copper (II) sulfate solution (content of copper ions 4.01 χ 10 "moles; pale blue) was placed on the top of the column. The polymer changed color to deep blue color due to chelation with the copper ions, and the water draining from the column was colorless. By Chelation titration with EDTA failed to find any copper ion in the effluent Water can be determined. Became the polymer that had adsorbed the copper ions with hydrochloric acid Treated according to the procedure of Example 4, the polymer became colorless and recovered.

Example 4

In a 100 ml four-necked flask equipped with a thermometer, a stirrer and a condenser, 3125 g of hexahydro-1 ^ tS-triacryloyl-s-triazine and 11.17 g of methanol were added and the flask was immersed in a water bath at 40 ° c. A solution of 1.47 g GlyI-n and 0.78 g sodium hydroxide in 3.14 g water was added to the compounds and then the mixture was reacted ^{for about 15 minutes on the water bath at about AO ° C.}

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The reaction mixture solidified. After 20 to 30 minutes the reaction mixture was taken out of the flask and washed with water and methanol, and dried, whereby

Received 5.01 g of the product.

2.0 g of the product were placed in a column and 10 ml of an aqueous 1% copper (II) sulfate solution were up poured onto the column in the same manner as described in Example 4. The color of the polymer turned deep Blue, as a chelate compound formed. The water that flowed through the column was colorless and transparent. The product could be reproduced in the same manner as in Example 4. <Be delighted.

Example 7

Following the procedure of Example 4 and using the The same reaction vessel as in Example 4 were 2.93 g of ethylene glycol diacrylate and 2.9 g of dimethylformamide in the Reaction vessel out and stirred. A solution of 1.55 g of L-lysine monohydrochloride and 0.66 g of sodium hydroxide in

3.2 g of water were added to the compounds. It kicked an exothermic reaction occurred and it formed first a transparent, viscous solution and then a gel-like product a few minutes after the addition. The reaction mixture was stirred for an additional 10 minutes and the reaction mixture was removed from the flask and placed in a mortar ground and then neutralized with 17 ml of 1N hydrochloric acid. Working up according to Example 4 gave a colorless product in powder form. The yield was 4.2 g. Following the procedure of Example 4, it was confirmed that the product exhibited a chelating property.

Example 8

In a 100 ecm four-necked flask, which is equipped with a thermometer, a stirrer, a dropping funnel and a cooler.

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was prepared, 3.08 g of methylenebisacrylamide were added and the mixture was stirred at 80 ° C.

A solution of 0.75 g of glycine and 0.4 g of sodium hydroxide in 8.3 g of water was added to the compound and the mixture was reacted at 80 ° C for 3 hours. A solution of 0.58 g was then added dropwise to the reaction mixture Hexamethylenediamine in 4 g of water. The reaction mixture formed a gel 20 minutes after the addition, with intermittent received a transparent, viscous solution. To the product was added 30 g of water and stirred for 1 hour, and that gel-like product was filtered off, washed with water and methanol, and then dried under reduced pressure. That the resulting product was a white powder and the yield was 4.3 g.

The product was placed in a column with an inner diameter of 15 mm and washed with water. When 10 ml of an aqueous 1% copper (II) sulfate solution was placed on the upper part of the column, the polymer changed its color to deep blue due to chelation with the copper ion, and the water flowing out of the column was colorless and transparent.

Corresponding to the chelate titration with EDTA, no copper ions could be found in the filtrate. When a large amount added to the column of 1N aqueous HCl solution became colorless again, and the water draining from the column was pale blue, which indicates its presence confirmed by copper ions. The polymer was recovered and the process could be repeated.

Example 9

In the reaction vessel of Example 8 were added 3.08 g of methylenebisacrylamide, 0.75 g glycine, 0.4 g sodium hydroxide and 8.3 g water and heated for 3 hours at 80 ° C. Then added

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a solution of 0.52 g of 2-aminoethanethiol in 4 g of water is added dropwise to the reaction mixture. A gel-like product was obtained after heating ^{at 80 ° C. for 5 hours.} The product was dried and ground, and then washed with water and with methanol and dried under reduced pressure to obtain 4.2 g of a colorless powder.

Following the procedure of Example 8, this was made The product was examined and it was found that it had the property of 'chelating'.

Example 10

A solution of 3.4 g of ethylene glycol diacrylate, 3.5 g of dimethylformamide and 1.19 g of α-alanine in 3.2 g of water was added to the reaction vessel from Example 8. A xtfäßrige solution of 10 g of 10% Benzyltrimethylammoniium-hydroxide was added dropwise to the solution at 40 C and the mixture was stirred at 40 ⁰ C for 30 minutes and then admixed with 0.3 g 27% ammonia to the reaction mixture and continued at 40 ^° C. for 60 minutes, a gel-like product being obtained.

This product was dried and ground and washed with water and further methanol and dried to obtain 4.9 g of a colorless powder.

This product was tested according to the procedure of Example 8 and was found to have the property Chelates, to form.

Example 11

In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser was added 3.08 g of methylene bisacrylamide and stirred at 80C Jiine Lcisung from 0.75 β glycine and 0.4 g of sodium

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hydroxide in 8.3 g of water was added to the compound and was then added to 3 hours at 80 ⁰ C. A solution of 0.5 g of acrylamide was added to the reaction mixture with stirring, and then 4.5 g of an aqueous solution of 0.01 g of ammonium persulfate was added dropwise to the mixture.

The reaction mixture formed a gel 5 minutes after the addition. 30 g of water was added and then stirred another hour to grind the gel-like product. The resulting product was filtered, with water and with Washed methanol and dried under reduced pressure. The dried product was a colorless powder and the yield was 4.2 g.

2.0 g of the powdery polymer (carboxyl group content 4.38 10 mol) was placed in a column with an inner diameter of 15 mm and washed with water.

-4 10 ecm 1% copper (II) sulfate (copper content 4.01 χ 10 mol) were added to the column so that all of the cupric sulfate passed through the column within 5 minutes. The polymer Formed a chelate compound with the copper ion and changed its color to deep blue, and that which was drained from the column Water was colorless and transparent. After the chelate titration with EDTA, no copper ions could be found in the filtrate to be established.

A large amount of 1N HCl aqueous solution was applied to the column given. The polymer turned colorless and the water exiting the column was pale blue. This confirmed the presence of copper ions. The polymer regenerates again. The procedure could be repeated.

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Claims (19)

Claims 0ί Chelating amino acid addition polymer, obtained by reacting an acryloyl compound having two or more than two acryloyl groups with an amino acid which contains two or more than two active hydrogen atoms bonded to a nitrogen atom of the amino acid. 2. A chelating amino acid addition polymer according to claim 1, wherein the acryloyl compound has two acryloyl groups and the amino acid contains two active hydrogen atoms. The 3 x chelating amino acid addition polymer according to claim 1, wherein the acryloyl compound is more than two Acryloyl groups and the amino acid contain more than two active hydrogen atoms. 4. The amino acid addition chelating polymer according to claim 1, wherein the product (AX) of the mole (A) of the acryloyl compound and the number (X) of acryloyl groups in the compound is higher than the product (BY) from the mole (B) the amino acid and the number (Y) of active hydrogen atoms, which are bonded to the nitrogen atom, the unreacted Acryloyl groups by radical polymerization with each other or with another vinyl monomer or by Michael addition reaction with a compound containing at least three active hydrogen atoms can be reacted. 5. Chelating amino acid addition polymer according to claim 1, wherein the acryloyl compound is an alkylenebisacrylamide, an alkylenebismethacrylamide, a substituted methylenebisacrylamide, a substituted methylenebismethacrylamide, a dihydroxyalkylenebisacrylamide, a dihydroxyalkylenebismethacrylamide, an alkylene glycol diacrylate, - 22 309823/0965 an alkylene glycol dimethacrylate, an alkylene polyol polyacrylate, an alkylene polyol polymethacrylate and / or a hexahydro-striazine derivative, which contains at least two acryloyl groups in 1, 3 or 5 positions, is used. 6. Chelating amino acid addition polymer according to claim 1, wherein the acryloyl compound is methylenebisacrylamide, Methylenebismethacrylamide, Dihydroxyäthylenbisacrylamid, Dihydroxyäthylenbismethacrylamid, Ethyleneglykoldiacrylat, Ethylene glycol dimethacrylate, glycerol trisacrylate, glycerol trismethacrylate and / or hexahydro-1,3,5-triacryloyls-triazine used. 7. Chelating amino acid addition polymer according to claim 1, wherein the amino acid used is glycine, α-alanine, glutamic acid, aspartic acid, β-alanine, N, N (or N, N ¹ ) -dimethyllysine, ethylenediamine-N, N (or N, N ¹ ) diacetic acid, N, N-bis (hydroxyethyl) glycine, lysine, alginine (alginine), ornithine, threonine, cysteine and / or serine are used. 8. Chelating amino acid addition polymer according to claim 1, wherein the reaction of the acryloyl compound with the amino acid is carried out in the presence of an acidic or alkaline catalyst in an aqueous medium. 9. Chelating amino acid addition polymer according to claim 1, wherein the reaction of the acryloyl compound with the aminosäui to be led. of the amino acid at a temperature of 0 to 200 c 10. A method for removing a heavy metal component from an aqueous medium, characterized in that the heavy metal component contained in the aqueous medium with a chelating amino acid addition polymer treated, which is obtained by applying an acryloyl - 23 309823/0965 compound that contains two or more than two acryloyl groups with an amino acid that contains two or more than two contains active hydrogen atoms, and that one that aqueous medium and the polymer which forms a chelate with the heavy metals, separated. 11. A method for removing a heavy metal component from an aqueous medium according to claim 10, characterized in that characterized in that the acryloyl compound has two acryloyl groups and the amino acid contains two active hydrogen atoms. 12. A method for removing a heavy metal component from an aqueous medium according to claim 10, characterized in that characterized in that the acryloyl compound has more than two Contains acryloyl groups or that the amino acid contains more than two active hydrogen atoms. 13. A method for removing a heavy metal component from an aqueous medium according to claim 10, characterized in that characterized in that the chelating amino acid addition polymer is prepared in such a way that the product from the moles of acryloyl compound and the number of acryloyl groups in the compound is higher than the product from the mole of the amino acid and the number of active hydrogen atoms and that the unmixed acryloyl groups through Radical polymerization with each other or with other vinyl monomers or by Michael addition reaction with a compound that contains at least three active hydrogen atoms, \ tfurther implemented. 14. Process for removing a heavy metal component from an aqueous medium according to claim 10, characterized in that the acryloyl compound is an alkylenebisacrylamide, a substituted methylenebisacrylamide 3 09823/0965 substituted methylenebismethacrylamide, an alkylenebismethacrylamide, Dihydroxyalkylenebisacrylamide, dihydroxyalkylenebismethacrylamide, an alkylene glycol diacrylate, an alkylene glycol dimethacrylate, an alkylene polyol polyacrylate Alkylenpolyo! Polymethacrylat and / or a hexahydro-striazine derivative, which contains at least two acryloyl groups in 1-, 3- or 5-positions, is used. 15. A method for removing a heavy metal component from an aqueous medium according to claim 10, characterized in that characterized in that the acryloyl compound is methylenebisacrylamide, Methylenebismethacrylamide, Dihydroxyäthylenbisacrylamid, Dihydroäthylenbismethacrylamid, Ethyleneglykoldiacrylat, Ethylene glycol dimethacrylate, glycerol trisacrylate, glycerol trismethacrylate and / or hexahydro-1, JfS-triacryloyls-triazine used. 16. A method for removing a heavy metal component from an aqueous medium according to claim 10, characterized in that the amino acid glycine, α-alanine, glutamic acid, aspartic acid, β-alanine, N, N (or l ^ N'J-dimethyllysine, ethylenediamine -N, N (or -N, N ¹ ) -diacetic acid, N, N-bis (hydroxyethyl) -glycine, lysine, alginine, ornithine, threonine, cysteine and serine are used. 17. A method for removing a heavy metal component from an aqueous medium according to claim 10, characterized in that characterized in that the reaction of the acryloyl compound with the amino acid is carried out in the presence of an acidic or alkaline catalyst in an aqueous medium. 18. A method for removing a heavy metal component from an aqueous medium according to claim 10, characterized in that the reaction of acryloyl compound is carried out with the amino acid at a temperature from 0 to 200 ⁰ C. - 25 309823/0965 19. Process for removing a heavy metal component from an aqueous medium according to claim 10, characterized in that after the separation of the aqueous medium and treating the chelating polymer with the chelating polymer with an acidic solution, whereby the chelating ability and that the recovered polymer is then reused in the treatment will. 309823/0965