JPH074537B2 - Chelate resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a chelate resin.

[Conventional technology]

Chloromethylation by reacting a copolymer of an aromatic monovinyl compound and a polyvinyl compound having two or more vinyl groups with chloromethyl ether or the like in the presence of a Friedel-Crafts catalyst such as anhydrous tin chloride, zinc chloride or aluminum chloride. After that, for example, a chelate resin obtained by reacting iminodiacetic acid ethyl ester or the like and then introducing a chelate forming group such as a sodium iminodiacetate group substituted with chlorine of a chloromethyl group by saponification is conventionally known (for example, Kyoritsu Publishing Co., Ltd. "Polymer Experimental Studies" Vol. 7 34-35
page).

[Problems to be solved by the invention]

However, the above-mentioned conventional chelate resins are poor in heat resistance and chemical resistance, and are different from metal ions such as high-temperature wastewater and wastewater of university laboratories, garbage incinerators, landfill sites, hospitals, mines, factories of various industries, etc. When used for the treatment of wastewater containing many substances, the chelate resin deteriorates and the life of the resin is significantly shortened, and durability is also problematic. There was a drawback that it decreased. Furthermore, since the chelating group is present in a ratio of at most 1 per aromatic nucleus in the resin, the adsorbability of metal ions was not sufficient.

[Means for solving problems]

As a result of earnest studies in view of the above points, the present inventors have found that alkyl substitution in the aromatic ring of an aromatic monovinyl component of a copolymer of an alkyl-substituted aromatic monovinyl compound and a polyvinyl compound having two or more vinyl groups. A chelate resin that has a specific chelate-forming group that is introduced by substituting a part of the halogen in a halogen-substituted derivative in which halogen is bonded to a group, and that contains a specific proportion of halogen has durability and heat resistance. The inventors have found that they have excellent chemical resistance as well as metal ion adsorption compared to conventional chelate resins, and have completed the present invention.

The chelate resin of the present invention has the general formula Alkyl-substituted aromatic monovinyl compound component represented by 9
Halogen is bonded to an alkyl substituent bonded to an aromatic ring of an aromatic monovinyl compound component of a copolymer composed of 9.5 to 60% by weight and a polyvinyl compound component having two or more vinyl groups from 0.5 to 40% by weight. Examples of the chelate-forming group introduced by substituting a part of the halogen in the halogen-substituted derivative include iminopropionic acid group, iminoacetic acid group, iminodiacetic acid group, iminodipropionic acid group, amino acid group, aminoalkylene phosphate group. , Iminoalkylene phosphate group,
It is characterized by having at least one of a phosphoric acid group, a dithiocarbamic acid group, a thiol group, or a salt thereof, a polyamino group and an amidoxime group, and having a halogen content of 1 to 30% by weight.

Examples of the alkyl-substituted aromatic monovinyl compound constituting the resin matrix of the chelate resin of the present invention include vinyltoluene, ethylstyrene, dimethylstyrene, diethylstyrene, α
-Methyl vinyl toluene and the like. Examples of polyvinyl compounds having two or more vinyl groups include divinylbenzene, diallyl phthalate, dialin maleate, diallylamine, ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate. The alkyl-substituted aromatic monovinyl compound component and polyvinyl compound component in the resin matrix are the same, but 2
It may be different in kind or more.

The chelate resin of the present invention uses a halogen-substituted derivative of a copolymer of the above alkyl-substituted aromatic monovinyl compound and a polyvinyl compound as a resin matrix, and the ratio of the alkyl-substituted aromatic monovinyl compound component and the polyvinyl compound component in the copolymer is Alkyl-substituted aromatic monovinyl compound 9
9.5-60 wt%, polyvinyl compound 0.5-40 wt%
In particular, it is preferable that the polyvinyl compound is 5 to 20% by weight with respect to 95 to 80% by weight of the aromatic monovinyl compound. When the ratio of the polyvinyl compound component in the copolymer of the alkyl-substituted aromatic monovinyl compound and the polyvinyl compound is less than 0.5% by weight, the strength and chemical resistance of the chelate resin are extremely poor, and when it exceeds 40% by weight, the degree of crosslinking is high. Has a drawback that the resin becomes hard and brittle at the same time, resulting in poor impact resistance.

Examples of the chelate-forming group in the chelate resin of the present invention include iminopropionic acid group, iminoacetic acid group, iminodiacetic acid group,
Iminodipropionic acid group, amino acid group, aminoalkylene phosphoric acid group, iminoalkylene phosphoric acid group, phosphoric acid group, dithiocarbamic acid group, thiol group or alkali metal salt such as sodium salt or potassium salt, calcium salt, magnesium salt Alkaline earth metal salts such as Further, examples of the chelate-forming group include a polyamino group and an amidoxime group, and the chelate resin of the present invention has at least one of these chelate-forming groups.

The chelate resin of the present invention has a structure in which a halogen is bonded to an alkyl substituent bonded to an aromatic ring of an aromatic monovinyl compound component of a resin matrix, and thus has excellent heat resistance and chemical resistance, and also has the same chelate-forming group. The chelate resin has a higher adsorbability for metal ions than that of the chelate resin, but the halogen content in the chelate resin is 1 to 30% by weight in order to sufficiently exert these effects.

The chelate resin of the present invention comprises 99.5-60% by weight of an alkyl-substituted aromatic monovinyl compound and 0.5-40% by weight of a polyvinyl compound.
And a halogen-substituted derivative obtained by reacting a copolymer obtained by polymerizing a polymerizable composition comprising a halogen with a halogen to the alkyl substituent of the alkyl-substituted aromatic monovinyl compound component in the copolymer. Then, it is obtained by substituting a part of halogen in the halogen-substituted derivative with a chelating group.

For the polymerization of an alkyl-substituted aromatic monovinyl compound and a polyvinyl compound, a bulk polymerization method is usually used to obtain a gel type resin, but when a porous type chelate resin is obtained, 1% by weight of the polymerizable composition is used. Polymerization is carried out using 0.1 to 10 parts by weight of organic solvent per part. As the organic solvent, carbon tetrachloride, isooctane, n-hexane, petroleum benzine,
Ligroin, benzene, toluene, xylene, chloroform, chlorobenzene, methyl ethyl ketone, etc. are used. Further, when it is obtained as a spherical resin, suspension polymerization is carried out in a surfactant or an aqueous solution of a water-soluble polymer. As a polymerization initiator, azobisisobutyronitrile, 2,2'-azobis (2-isobutyl-4-methylvaleronitrile),
1,1'-azobis (cyclohexane-1-carbonitrile), lauroyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), etc. Is used at 40-120 ℃,
Polymerization is preferably carried out by heating and stirring at 60 to 90 ° C.

The copolymer thus obtained is treated with halogen in an amount of 50 to 120
The halogen-substituted derivative can be obtained by heating and stirring at ℃, preferably 60 to 90 ℃. The halogenation is carried out in a chlorine-based solvent which is inert to halogens such as carbon tetrachloride, ethylene dichloride, tetrachloroethylene, dichlorobenzene and trichloroethane. Although chlorine, fluorine, iodine, bromine, etc. are used as the halogen,
Usually, it is preferable to use chlorine. Halogen is used in an amount of 1 to 5 equivalents, preferably 1.2 to 2.5 equivalents, based on the alkyl substituent bonded to the aromatic nucleus in the copolymer, and a halogen content of 20 to 70% by weight, particularly 25 to 50% by weight. Preferably. As the halogenation catalyst, the azo polymerization initiator such as phosphorus trichloride or azobisisobutyronitrile can be used. Further, when the halogenation reaction is carried out under UV irradiation, the selectivity of halogenation of the alkyl substituent bonded to the aromatic nucleus is improved, and the chelate-forming group introduced by substituting the halogen bonded to the alkyl group is introduced. The ratio of the above in the chelate resin increases, and a resin having a higher metal ion adsorbing property can be obtained. Therefore, at least more than 1 equivalent to the alkyl substituent attached to the aromatic nucleus,
In particular, halogenation under UV irradiation using 1.2 to 2.5 equivalents of halogen can increase the number of chelate-forming groups in the chelate resin finally obtained and leave the halogen in the chelate resin matrix. It is possible to obtain a chelating resin which has excellent heat resistance, chemical resistance, and durability as well as excellent metal adsorption ability.

Examples of the method for introducing a chelate-forming group include a method in which a halogen-substituted derivative is reacted with iminodiacetic acid ester, iminopropionic acid ester, iminodipropionic acid ester and then saponified (iminodiacetic acid sodium base, iminopropionic acid sodium base). , In the case of introducing sodium iminodipropionate as a chelate forming group), a method of reacting a halogen-substituted derivative with a polyamine such as ethylenediamine, propylenediamine, diethylenetriamine and triethylenetetramine (in the case of introducing a polyamino group as a chelating group) , A method in which a halogen-substituted derivative is reacted with phosphorus trichloride in the presence of anhydrous aluminum chloride (when a phosphate group is introduced as a chelate-forming group), a polyamino group is introduced by the above method, and then disulfide A method of reacting with carbon (when introducing a dithiocarbamic acid group as a chelate-forming group), a method of introducing a polyamino group by the above method, and then reacting an aldehyde with hypophosphorous acid (iminoalkylphosphoric acid group, aminoalkylphosphoric acid group) When an acid group is introduced as a chelate-forming group), a polyamino group is introduced by the above-mentioned method, then reacted with acrylonitrile, and then hydroxylamine hydrochloride is reacted (when an amidoxime group is introduced as a chelate-forming group), halogen. A method in which a substituted derivative is reacted with thiourea, hydrogen sulfide, etc., and then treated with an alkali such as sodium hydroxide, or treated with an acid such as hydrochloric acid (sodium salt of thiol, thiol group (When introduced as a chelate-forming group). Of the chelate resins obtained as described above, those having an acid type chelate-forming group may be treated with an alkali metal hydroxide, an alkaline earth metal hydroxide or the like to give a metal salt type. The product may be treated with an acid such as hydrochloric acid to give an acid form.

The chelate resin of the present invention obtained as described above is usually
Used in spherical or granular form.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 90 parts by weight of paramethylstyrene, 4 ethylvinylbenzene
Benzene insoluble porous spherical copolymer resin (particle size 10-48 mesh) consisting of 1 part by weight and 6 parts by weight divinylbenzene
400 g, 800 g of ethylene dichloride and 7 g of phosphorus trichloride were charged into a reaction vessel, and while refluxing ethylene dichloride, chlorine gas was introduced into the reaction vessel under UV irradiation for 3 hours to chlorinate, then washed with water and dried. Chlorine content 28.3% by weight
A chlorine-substituted derivative of was obtained. Next, 50 g of this derivative, 80 g of iminodiacetic acid ethyl ester, and 200 g of water were charged into a reaction vessel, and sodium hydroxide aqueous solution was added thereto, and the pH was maintained at pH 7 while maintaining the pH at 8 ° C. for 8 hours.
After reacting for a time, the resin was separated after cooling. The obtained resin was saponified by heating in 300 g of a 20% sodium hydroxide aqueous solution at 90 to 100 ° C. for 5 hours to obtain a chelate resin (Na type resin) having a sodium iminodiacetate base as a chelate forming group. This resin was hydrolyzed with 2N hydrochloric acid to obtain a chelate resin (H-type resin) having an iminodiacetic acid group as a chelate forming group. After drying, the resin had a nitrogen content of 4.4% by weight and a chlorine content of 15.8% by weight.

Example 2 400 g of a benzene-insoluble gel-type spherical copolymer resin (particle size 20 to 60 mesh) consisting of 80 parts by weight of dimethylstyrene, 8 parts by weight of ethylvinylbenzene, and 12 parts by weight of divinylbenzene.
Charge carbon tetrachloride (800 g) and azobisisobutyronitrile (15 g) into the reaction vessel. While refluxing carbon tetrachloride, introduce chlorine gas into the reaction vessel over 7 hours to chlorinate, then wash with water and dry to remove chlorine. A chlorine-substituted derivative having a content of 40.6% by weight was obtained. Next, 100 g of this derivative, 150 g of toluene, and 300 g of ethylenediamine were charged into a reaction vessel and the reaction was carried out at 90 to 100 ° C for 12 hours. After the reaction was completed, the resin was separated, washed with water, then washed with a large amount of methanol, and then washed with water to give a polyamino A chelate resin having a group as a chelate-forming group was obtained. After drying, the resin had a nitrogen content of 12.5% by weight and a chlorine content of 21.8% by weight.

Example 3 Benzene-insoluble porous spherical copolymer resin (particle size 20 to 60 mesh) 400 g, consisting of 57 parts by weight of methvinyltoluene, 38 parts by weight of paravinyltoluene, 2 parts by weight of ethylvinylbenzene, and 3 parts by weight of divinylbenzene. Charge 800 g of carbon chloride and 6 g of azobisisobutyronitrile into a reaction vessel, and while refluxing carbon tetrachloride, introduce chlorine gas into the reaction vessel for 4 hours under UV irradiation and chlorinate, then wash with water and dry. Thus, a chlorine-substituted derivative having a chlorine content of 29.8% by weight was obtained.
Next, 50 g of this derivative and 300 g of diethylenetriamine were charged into a reaction vessel and reacted at 120 ° C. for 15 hours, then the resin was separated and washed in the same manner as in Example 2 to obtain a chelate resin having a polyamino group as a chelate forming group. It was The nitrogen content of this resin after drying was 12.7% by weight, and the chlorine content was 16.7% by weight.

Example 4 50 g of a chlorine-substituted derivative obtained in the same manner as in Example 1, 145 g of anhydrous aluminum chloride and 680 g of phosphorus trichloride were charged in a reaction vessel, and the reaction was carried out at 50 to 60 ° C. for 5 hours with stirring. After completion of the reaction, the resin was separated and washed with water to obtain a chelate resin having a phosphate group as a chelate forming group. After the resin was dried, the phosphorus content was 18.4% by weight and the chlorine content was 4.6% by weight.

Example 5 50 g of a chelate resin obtained in the same manner as in Example 2, 21.5 g of sodium hydroxide, and 200 g of water were charged into a reaction vessel and stirred at 50 to 50%.
41 g of carbon disulfide was added dropwise at 60 ° C. over 1 hour, and after completion of the dropping, reaction was carried out at 80 ° C. for 7 hours. After completion of the reaction, the product was hydrolyzed in 1N hydrochloric acid, the resin was separated and washed with water to obtain a chelate resin having a dithiocarbamic acid group as a chelate forming group.
The sulfur content of this resin after drying is 24.1% by weight,
The chlorine content was 22.9% by weight.

Example 6 Chelate resin obtained in the same manner as in Example 3 30 g, 32% hydrochloric acid 15
0 g was placed in a reaction vessel, heated and stirred under reflux of carbon tetrachloride for 1 hour, cooled, and the resin was separated and washed with water. Next, 35 g of orthophosphorous acid and 10 g of trioxymethylene were added to this resin.
g, 32% hydrochloric acid 20 g, water 150 g, reacted at reflux temperature for 3 hours, after the reaction was completed, the resin was separated and washed with water to form a chelate resin having aminomethyl phosphate groups and iminomethyl phosphate groups as chelate forming groups. Got The nitrogen content after drying of this resin was 7.1% by weight, the phosphorus content was 10.4% by weight,
The chlorine content was 21.2% by weight.

Example 7 120 g of a methyl acrylate adduct of diethylenetriamine obtained by adding 215 g of methyl acrylate to 103 g of a chlorine-substituted derivative obtained in the same manner as in Example 1 and 103 g of diethylenetriamine were added to a reaction vessel and stirred. The mixture was reacted at 90 to 100 ° C for 10 hours, and after the reaction was completed, the resin was separated. The obtained resin is 20% sodium hydroxide aqueous solution 30
After saponification in 0 g at 100 ° C. for 3 hours, the resin was separated and washed with water to obtain a chelating resin having sodium iminopropionate base and sodium iminopropionate base as chelate forming groups. The resulting chelate resin was hydrolyzed with 2N hydrochloric acid to give an H-type resin. After drying, the H-type resin had a nitrogen content of 6.8% by weight and a chlorine content of 19.7% by weight.

Example 8 50 g of chlorine-substituted derivative obtained in the same manner as in Example 3, 100 g of acrylonitrile adduct of triethylenetetramine obtained by Michael addition of 185.5 g of acrylonitrile to 146 g of triethylenetetramine, and 150 g of toluene were charged into a reaction vessel and stirred. React at 100 ℃ for 100 hours, and after the reaction is complete, separate the resin,
Washed with water. This resin was then treated with 3% by weight of hydroxylamine hydrochloride in a water-methanol solution (water, methanol 1: 1).
(Weight ratio) Mixture) After reacting at 350 g with stirring at 60 ° C. for 5 hours, the resin was separated and washed to obtain a chelate resin having an amidoxime group as a chelate forming group. The nitrogen content after drying of this resin is 15.2% by weight, and the chlorine content is
It was 15.9% by weight.

Example 9 50 g of chlorine-substituted derivative obtained in the same manner as in Example 1, 300 ml of an ethanol-dioxane mixture (weight ratio 1: 1), thiourea 3
0 g was charged into a reaction vessel, reacted at reflux temperature for 5 hours, and then the resin was separated and washed with water. Then 300 g of this resin
After reacting in a 15% by weight sodium hydroxide aqueous solution at 80 ° C. for 5 hours, the resin was separated, washed with water, further washed with 1N hydrochloric acid and washed again with water to obtain a chelate resin having a thiol group as a chelate forming group. After drying, the resin had a sulfur content of 16.7% by weight and a chlorine content of 8.2% by weight.

Comparative Example 1 200 g of a benzene-insoluble porous spherical copolymer resin (particle size 10 to 48 mesh) consisting of 90 parts by weight of styrene, 4 parts by weight of ethylvinylbenzene, and 6 parts by weight of divinylbenzene, 100 g of ethylene dichloride, 1000 g of chloromethyl ether, chloride 100 g of zinc was charged into a reaction vessel, and chloromethylation was carried out at 50 ° C. for 8 hours with stirring. After completion of the reaction, the resin was separated, washed with water and dried to obtain a chloromethylated resin having a chlorine content of 18.0% by weight. Then 50 g of this resin, 80 methyl iminodiacetate
g and 200 g of water were charged in a reaction vessel and the reaction was carried out in the same manner as in Example 1 to obtain a chelate resin having a sodium iminodiacetate base as a chelate forming group. Next, this resin was hydrolyzed to form an H-type resin. The nitrogen content of this H-type resin after drying was 3.6% by weight, and this resin did not contain chlorine in the resin matrix.

Comparative Example 2 50 g of the chloromethylated resin obtained in Comparative Example 1 and 300 g of diethylenetriamine were charged into a reaction vessel and the reaction was carried out in the same manner as in Example 3 to obtain a chelate resin having a polyamino group as a chelate forming group. The nitrogen content of this resin after drying was 12.7% by weight, and this resin did not contain chlorine in the resin matrix.

The amount of Cu ²⁺ , Cd ²⁺ , Pb ²⁺ , Hg ²⁺ adsorbed on the chelate resins obtained in Examples 1 to 9 and Comparative Examples 1 to 2 was determined by the following method.

First 60ppm of Cu ²⁺ solution (CuSO ₄ used), 100 ppm of Cd ²⁺ solution (CdSO ₄ used), 150 ppm of Pb ²⁺ solution (Pb (NO _{3) 2}
Used) and 200 ppm Hg ²⁺ aqueous solution (using HgCl ₂ ) were prepared, and these four types of aqueous solutions were used as raw water.
Next, 1 ml of the chelate resin was added to each raw water 1 above, and the mixture was stirred at 25 ° C. for 3 hours to perform solid-liquid separation, and then the residual metal ion concentration was measured. It was determined as the amount of adsorption. The results are shown in Table 1.

Next, 1000 ml of the chelate resin of Example 1 and Comparative Example 1 were packed in separate columns (inner diameter 25 mmφ), and 5 N hydrochloric acid aqueous solution 10 (10 / -R) and tap water 10 per resin.
/ -R, 2N sodium hydroxide aqueous solution 10 / -R, tap water 10 / -R were passed in this order in order to pass the liquid at a velocity of SV10 and downward flow. Repeated the above liquid-flowing operations 150 times, 25th, 50
10 ml of resin was sampled at the 75th, 100th and 125th cycles, respectively. Next, for the resin that has not been passed through at all and for the resin that has been passed through 25, 50, 75, 100, 125, and 150 times
The adsorption amount of Cd ²⁺ was measured to determine the adsorption rate. Adsorption amount is 100ppm
Cd ²⁺ aqueous solution of is used as raw water, and 1 ml of resin is added to raw water 1
After stirring for 3 hours at 5 ° C. and solid-liquid separation, the residual Cd ²⁺ concentration was measured and determined as the amount per resin from the difference from the Cd ²⁺ concentration in the raw water. The adsorption rate was calculated as the ratio of the adsorption amount to this value, assuming that the adsorption amount by the resin that had not been passed through was 100%. The results are shown in Table 2. The appearance index of the resin used in the above test is also shown in Table 2.

Further, 100 ml of each of the resins of Example 3 and Comparative Example 2 was packed in separate columns (double tube column with an inner diameter of 25 mmφ), and the same liquid passing operation as above was carried out 100 times with the liquid temperature at the time of liquid passing as 60 ° C. , 10 ml of resin was sampled at the 25th, 50th, and 75th passages, respectively. Next, the amount of Cu ²⁺ adsorbed was measured using a resin that was not passed through at all and a resin that was passed 25 times, 50 times, 75 times, and 100 times. Was determined as the adsorption rate. Adsorption amount is 60ppm Cu ²⁺
Aqueous solution was used as raw water, and 1 ml of resin was added to this raw water 1, 25
After stirring at ℃ for 3 hours and solid-liquid separation, the residual Cu ²⁺ concentration was measured and calculated as the amount per resin from the difference from the Cu ²⁺ concentration in the raw water. The relationship between the adsorption rate obtained from this adsorption amount and the number of liquid passing treatments is shown in FIG.

[Advantages of the Invention] As described above, the chelating resin of the present invention has durability,
It has excellent heat resistance and chemical resistance, and it can be used for the treatment of laboratory wastewater, waste incinerator wastewater, hospital wastewater, industrial wastewater, etc. containing many substances in addition to high-temperature wastewater and metal ions. As described above, there is no fear that the resin will be deteriorated by being attacked, that the resin will be crushed by repeated reuse, or the adsorption amount will be significantly reduced, and the life of the resin will be greatly extended.
Further, the chelate resin of the present invention is superior to the conventional chelate resin in adsorbing metal ions, and has an effect that waste water treatment can be efficiently performed.

[Brief description of drawings]

FIG. 1 shows the number of times the resin was passed through the resin of Example 3 and Comparative Example 2 and Cu.
It is a graph which shows the relationship with a ²⁺ adsorption rate.

Continuation of the front page (56) References JP-A-56-163101 (JP, A) JP-A-56-161404 (JP, A) Hojo J. Masamasa "Functional Polymer Series Chelate Resin / Ion Exchange Resin" Second printing (Sho 52-8-30) Kodansha P. 1-26

Claims (1)

[Claims] 1. A general formula Alkyl-substituted aromatic monovinyl compound component represented by 9
Halogen is bonded to the alkyl substituent bonded to the aromatic ring of the aromatic monovinyl compound component of a copolymer composed of 9.5 to 60% by weight and 0.5 to 40% by weight of a polyvinyl compound component having two or more vinyl groups. As the chelate-forming group introduced by substituting a part of the halogen in the halogen-substituted derivative consisting of, an iminopropionic acid group, an iminoacetic acid group, an iminodiacetic acid group, an iminodipropionic acid group, an amino acid group, an aminoalkylene phosphate group , An iminoalkylene phosphate group,
A chelate resin having a phosphoric acid group, a dithiocarbamic acid group, a thiol group, or a salt thereof, at least one of a polyamino group and an amidoxime group, and having a halogen content of 1 to 30% by weight.