JPH0469166B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel chelating adsorbent and a method for producing the same. Ion exchange resins, chelate resins, and the like are widely used industrially, including in wastewater treatment. However, conventionally known products do not necessarily have excellent chemical stability, and have poor long-term stability depending on changes in pH, and furthermore, have poor thermal stability. As a result of intensive studies from this standpoint, the present inventors have discovered a chelate adsorbent having a novel chemical structure and have completed the present invention. The novel chelating adsorbent in the present invention is
It is an adsorbent polymer having a functional group represented by the following structural formula (a). (Here, R ₁ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ₂ represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. The position of the vinyl group with respect to the quinoline skeleton is the 2- or 4-position. (The position of R ₂ may be any position.) Preferred examples of R ₁ include hydrogen, a methyl group, an ethyl group, and a phenyl group, among which hydrogen is preferred. Preferred examples of R ₂ include hydrogen and a methyl group, among which hydrogen is a preferred example. The vinyl position relative to the quinoline skeleton is preferably the 2-position. There are no particular restrictions on the form of bonding of the functional group shown in (a) to the polymer, but some preferred examples include those in which hydrogen is directly substituted in the methylene chain of the main chain, The functional group of and (a) is (-
Those bonded by CH ₂ )- _o or -O(-CH ₂ )- _o , and those substituted with hydrogen in the benzene skeleton of styrene or alkylstyrene polymers (the following structural formula (a)), etc. . (Here, R ₃ represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms.) The substance of the present invention is a polymer having a functional group represented by the structural formula (A), and this polymer is a three-dimensional Preferably, it is a crosslinked polymer. There are no particular limitations on the crosslinking agent, and it is a polymerized unit corresponding to a difunctional or polyfunctional monomer. Examples of these polymerized units include divinylbenzene, divinyltoluene, divinylxylene, divinylethylbenzene, trivinylbenzene, divinyldiphenyl,
Divinyldiphenylmethane, divinyldibenzyl, divinylphenyl ether, divinyldiphenyl sulfide, divinyldiphenylamine, divinylsulfone, divinylketone, divinylpyridine, diallyl phthalate, diallyl maleate,
Diallyl fumarate, diallyl succinate, diallyl oxalate, diallyl adipate, diallyl sebacate, diallylamine, triallylamine, N,
N'-ethylene diacrylamide, N,N'-methylene diacrylamide, N,N'-methylene dimethacrylamide, ethylene glycol dimethacrylate, ethylene glycol diacrylate,
It is a polymerized unit corresponding to 1,3-butylene glycol diacrylate, triallyl isocyanurate, triallyl citrate, triallyl trimellitate, triallyl cyanurate, etc. There is no problem even if a plurality of types of these crosslinking units are included. These cross-linked polymer units range from 1 to 50
It is preferably 1% to 30% by weight, more preferably 1 to 30% by weight. Furthermore, there is no problem even if other polymerized units are included as a third component in addition to these. These third components include styrene, vinyltoluene, ethylstyrene, chloromethylstyrene, butadiene, methacrylic acid, acrylic acid, methyl methacrylate, ethyleneimine, vinyl acetate, vinylimidazole, vinylpyridine, vinylcarbazole, etc. It may also contain polymerized units corresponding to known monomers. The substance of the present invention is an adsorbent polymer with excellent metal selectivity and excellent thermal and chemical stability. It is preferable that In quantitative terms, the basic exchange capacity is preferably 0.5 m mol/g or more, more preferably 2.0 m mol/g or more.
It is mol/g or more. Furthermore, the present invention provides a method for producing the chelating adsorbent, which includes a polymer having a group represented by the following structural formula (C) and an 8-hydroxyquinoline represented by (D). This is a method for producing a chelating adsorbent having a functional group represented by the following structural formula (A), which is characterized by reacting the following.

【formula】 【formula】

(Here, R ₁ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ₂ represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. The position of the vinyl group with respect to the quinoline skeleton is the 2- or 4-position. (The position of R ₂ may be in any position.) The polymer having the group (c) (hereinafter referred to as the raw material polymer), which serves as a raw material, can be produced by several methods. The first method is to copolymerize the monomer having the group (c) with other crosslinkable monomers as necessary. Examples of monomers having group (c) include acrolein, methyl vinyl ketone, ethyl vinyl ketone, vinyl phenyl ketone, vinyl benzyl ketone, formyl styrene, ethyl formyl styrene, acetylstyrene, ethylacetylstyrene, 4- Examples include vinyl diphenyl ketone. Among these, formylstyrene is a preferred example, and a typical method is to copolymerize this formylstyrene with divinylbenzenes to produce the raw material polymer. The second method for producing the raw material polymer is to introduce -COR ₁ into the polymer. As a method for introducing R ₁ =H, that is, a formyl group, a known method can be used, for example, a method using an oxidation reaction of a methyl group or a chloromethyl group, a Gutterman-Kotto reaction, etc. can be used. Even when R ₁ is other than hydrogen, known methods can be applied, such as reaction of a hydroxyl group with an acid halide, Friedel-Crafts reaction, etc. When producing a raw material polymer, it is preferable to form it into granules in advance by using a method such as suspension polymerization or emulsion polymerization, or by crushing the polymer. In the quinolines represented by the structural formula (d), the methyl group is at the 2-position or the 4-position. R ₂ is preferably hydrogen or a methyl group, with hydrogen being particularly preferred. The position of R ₂ may be any of the 2nd to 7th positions. To give a specific example of (d), 2-methyl-8-
Hydroxyquinoline, 4-methyl-8-hydroxyquinoline, 2,4-dimethyl-8-hydroxyquinoline, 2,5-dimethyl-8-hydroxyquinoline, 2,6-dimethyl-8-hydroxyquinoline, 4,5-dimethyl -8-hydroxyquinoline, 4,6-dimethyl-8-hydroxyquinoline, and the like. Next, a specific manufacturing method will be described. The amount of quinoline used is preferably 0.5 to 10 times the mole of the group represented by (c), more preferably 1
~3 times the mole. There are no particular restrictions on the temperature and time of the reaction. The temperature is preferably 80-250℃, and the reaction time is 5-24℃.
time is preferable. The reaction is preferably carried out in the presence of an inert liquid. Inert liquid is raw material polymer,
Refers to substances that are substantially inert to quinolines and products. For example, alcohols such as methanol, ethanol, propanol, butanol, and 2-ethylhexyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, and octane, chlorobenzene, bromobenzene, and nitrobenzene. substituted aromatic compounds such as chloroform, halogenated hydrocarbons such as dichloroethyl, ketones such as methyl ethyl ketone, acetone, ethers such as diethyl ether, tetrahydrofuran, dibutyl ether, amides such as dimethylformamide, dimethylacetamide, etc. Carboxylic acids such as vinegar, acetic acid, acetic anhydride, and propionic acid and their anhydrides, dimethyl sulfoxide, and the like can be used. There is no problem even if two or more of these inert liquids are used as a mixture. When carrying out the reaction, it may be preferable to carry out the reaction in the presence of an acid. Especially acetic anhydride,
Although acetic acid or the like can be used as a solvent, it is preferable to treat it with an alkali or the like after that. Further, in this reaction, it is preferable to coexist a dehydrating agent. The chelating adsorbent of the present invention is useful as an adsorbent for metals, organic substances, and the like. Adsorption refers to capture adsorption of metals etc. by so-called chelation, adsorption by ion exchange, physical adsorption, chemical affinity adsorption, etc. Among these, the chelating adsorbent of the present invention showed good adsorption properties for various metals. Although there are no particular restrictions on the type of metal, metal ions that have the ability to chelate oxine are generally preferred. That is, typically, groups such as copper, zinc, cadmium, uranium, thorium, etc.
Groups such as cerium, aluminum, gallium, and indium; Groups such as lead, tin, titanium, and zirconium; Groups such as vanadium, niobium, and antimony; Groups such as molybdenum, chromium, and tungsten; Groups such as iron, cobalt, nickel, and palladium. metals. Particularly good adsorbents are copper, uranium, gallium and iron. As a method for using the adsorbent of the present invention, conventionally known methods can be used, and the purpose can be achieved, for example, by contacting it with a liquid containing metal ions or the like. Examples are shown below, but these are not intended to limit the scope of the present invention. Example 1 1 of 4 equipped with thermometer, reflux and stirrer
Add commercially available polyvinyl alcohol 2.0 to the neck flask.
g, 400 g of pure water with 25 g of sodium chloride dissolved in it
and while stirring, 52.8 g of formylstyrene (mixture of meta-form: para-form = 6:4), divinylbenzene (purity 56%, meta-form: para-form = 6:4,
7.2 g (containing 44% ethylstyrene), 50 g m-xylene, 2,2'-azobisisobutyronitrile
0.6 g of the mixture was added, and stirring was continued at 60°C for 1 hour, at 70°C for 2 hours, and further at 80°C for 4 hours. After cooling and washing, the particles obtained were spherical particles with a particle size of 0.1 to 1.0 mm. After thoroughly washing the obtained particles with acetic anhydride, the entire amount was placed in an autoclave having a capacity of 1, and then 300 ml of an acetic anhydride solution in which 127.2 g of 8-hydroxy-2-methylquinoline was dissolved was added. After purging the inside of the autoclave with nitrogen, the autoclave was placed in an oil bath heated to 180°C and reacted for 15 hours. After cooling, the contents were taken out and washed. Next, put the entire amount into a 500ml 3-necked flask equipped with a thermometer and stirrer, and add 1N sodium hydroxide solution.
300 ml was added and stirring was continued at 90°C for 3 hours. After cooling and washing with water, the anion exchange capacity was measured.
It was 2.98meq/g. The main peaks of the infrared absorption spectrum are as follows. 3070, 2950, 1600, 1515, 1465, 1250, 970,
835, 755 The elemental analysis values of this particle are as follows. C: 83.8, H: 5.72, N: 4.79, O: 5.69 From the above analysis values and yield, it is clear that the 2-vinyloxine type product is obtained at a yield of 95% or more based on the raw material aldehyde. I understand. 20ml of a solution with a copper ion concentration of 50mM/PH=5.0 was prepared, 1g of the resin obtained as described above was added thereto, and after stirring overnight, the copper ion concentration was measured. 75% was adsorbed. When similar experiments were conducted for iron () ions, uranyl ions, and gallium ions, the respective adsorption rates were 30%, 35%, and 74%.

Claims (1)

[Scope of Claims] 1. A chelating adsorbent having a functional group represented by the following structural formula (A). (Here, R ₁ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ₂ represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. The position of the vinyl group with respect to the quinoline skeleton is the 2- or 4-position. and R ₂ may be in any position.) 2 The following structure is characterized by reacting a polymer having a group represented by the following structural formula (C) with an 8-hydroxyquinoline represented by (D). A method for producing a chelating adsorbent having a functional group represented by formula (A). [Formula] [Formula] (Here, R ₁ represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ₂ represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. The position of the vinyl group with respect to the quinoline skeleton is the 2- or 4-position. (The position of R ₂ can be any position.)