JPS6065003A - Adsorptive polymer and its production - Google Patents

Abstract

PURPOSE:To obtain an adsorptive polymer having both carbonyl and amino groups, suitable for adsorption of metals, etc., and excellent in chelatability, selectivity for metals, etc., by reacting a specified matrix polymer with a halogenoacetic acid (derivative). CONSTITUTION:A copolymer containing polymer units of formula I (wherein R1 is H or a 1-4C hydrocarbon group, and k and l are each 0-3) is reacted with a compound of formula II (wherein R4 is H, a metal, or a 1-10C hydrocarbon group, and X is a halogen), e.g., chloroacetic acid or ethyl bromoacetate. In this way, the purpose adsorptive polymer containing polymer units of formula III(wherein R2 and R3 are each H or -CH2COOR4, and A1 and A2 are each group of formula IV or V). Examples of the copolymers containing polymer units of formula I include a divinylbenzene/ethylstyrene/p-vinyl-2-[N,N-di-(2-aminoethyl)] aminoethylbenzene terpolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel adsorptive polymers having carbonyl groups and 7-mino groups.

Compounds having an amino group or a carbonyl group are used to adsorb metals, organic substances, etc. by utilizing their adsorption ability.

Representative compounds include ethylenediaminetetraacetic acid II (EDTA) and diethylenetriaminepentaacetic acid (DT
PA), iminodiacetic acid, nitrilotriacetic acid, co-hydroxyethyliminodiacetic acid, cyanomethyliminodiacetic acid, etc., and these substances have different selectivity coefficients to metals due to slight differences in chemical structure.

Those having a three-dimensional chemical structure similar to these are used as chelate resins, and, for example, iminodiacetic acid type ones are commercially available.

Also, Tokukai Akira! Publication No. 0-10317 describes a DTPA type having a benzene skeleton and one methylene chain. However, this product had problems such as insufficient chemical stability.

Also, iminoji vinegar W1. These types generally have low chelating ability and poor selectivity, so they have problems such as being unable to effectively capture metals.

As a result of intensive studies from this standpoint, the present inventors discovered an adsorbent polymer having a novel structure and arrived at the present invention.

That is, the present invention provides an adsorbent polymer containing a polymerized unit represented by the following structural formula (I).

c1 (Here, kawa represents hydrogen or a hydrocarbon group having 7 to 10 carbon atoms, R2, & represents hydrogen or 10H2COOR4, and 电 represents hydrogen, a metal, or a hydrocarbon group having 10 to 10 carbon atoms. .

, and k and l represent the number of O1 eight or three repeats. Each repeating unit of A, , A, may be the same or different.

Any positional relationship between R1, the main chain, and the 7-minoethyl group with respect to the benzene skeleton may be used.

The aminoethyl group has at least 7 -CM! It shall include COOR4. ).

Preferred examples of R1 include hydrogen and ethyl group. R
2, R3 is hydrogen or -C% COOR<, R2
, R3 or A, , one CI (2COOR
Preferred embodiments of No. 4 are carboxymethyl groups and metal salts thereof. Examples of metal salts are K salts
In addition to monovalent ion salts such as Na salts, polyvalent ion salts such as M salts and Ca salts may be used. In the case of a salt of a polyvalent ion, there is no problem even if one metal ion is a salt of one or more carboxyl groups, or a lead metal ion with a solvent or the like.

k%l is the number of repetitions of O182.3, but a preferred example is k=0, l=koi k=1=/i k=1=ko;
)(=/, l=3; etc., among these, k=
1=/ is a more preferable example.

The positional relationship between the R1s main chain and the aminoethyl group with respect to the benzene skeleton may be any, but it is preferable that the main chain and the 7-minoethyl group are in the m- or p-position, and the main chain and R1 are in the m- or p-position. This is an example.

The substance of the present invention provides an adsorbent polymer with excellent chemical stability, and has excellent metal selectivity as, for example, a chelate resin.

From these points of view, R2s R3 and AI,
It is preferable that as much of the hydrogen bonded to N of A2 or 10H2COOR4 as possible be CH2COORn. Quantitatively speaking, the total amount is 10 mol or more, more preferably 0 mol or more. Further, R4 is preferably hydrogen or a metal.

The main feature of the present invention is a polymer containing a polymer unit represented by formula (1), and this polymer is preferably a three-dimensional 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, cyhinyldiphenyl sulfite,
Divinyl diphenylamine, divinyl sulfone, divinyl ketone, divinyl pyridine, diallyl heptalate, diallyl maleate, diallyl fumarate, diallyl fumarate, diallyl oxalate, diallyl adipate, diallyl sebacate, diallylamine, triallylamine 7, N, N
'-methylene diacrylamide, N,N'-methylene diacrylamide, N,N'-methylene dimethacrylamide, ethylene glycol dimethacrylate, ethylene glycol diacrylate, l,3-butylene glycol diacrylate, triallyl isocyanurate,
enoic acid, tri7lyl, trimethyl
It is a polymerized unit corresponding to tri7lyl lithic acid, triallyl cyanurate, etc. There is no problem even if a plurality of these crosslinking units are combined. The number of these crosslinked polymer units is preferably 1 to 50 mol, more preferably 1 to 30 mol. Furthermore, there is no problem even if other polymer units are included as a third component in addition to these. These third components include styrene, vinyltoluene, ethylstyrene, l-methylstyrene,
In addition to polymerized units corresponding to known monomers such as butadiene, methacrylic acid, acrylic acid, methyl methacrylate, ethyleneimine, vinyl acetate, etc., conventionally known functional groups such as iminodiacetic acid and diethylenetriaminepentaacetic acid are used. It may be a polymerized unit having.

Furthermore, the present invention is characterized in that a copolymer containing a polymerized unit represented by the following structural formula (1) is reacted with X CTo COOR4, which contains a polymerized unit represented by the above formula (1). The present invention relates to a method for producing adsorbent polymers.

A polymer having the structural formula (1) as a raw material (hereinafter referred to as raw material polymer) can be obtained by copolymerizing a corresponding monomer with another crosslinkable monomer or the like. At the stage of synthesizing this raw material polymer, it is a preferable embodiment to use a technique such as suspension polymerization or emulsion polymerization, or to form it into granules by a technique such as crushing the polymer.

As a preferable example of (1), R1 is hydrogen, ethyl group, etc., and k and 1 are =0,1=k=l=/
1k=1=koi k=/, 1=J, etc.

XCH2COOR4 to be reacted with the raw material polymer is α
- octoacetic acid or its salt or ester.

For X, any of 2% C1, Br, and I can be used, but CI and Br are preferable from the viewpoint of obtaining raw materials.

Preferred examples of R4 include hydrogen, methyl group, ethyl group, propyl group, glutyl group, phenyl group, Na, and K.

Specific examples of XCH2COORa include chloroacetic acid, bromoacetic acid, fluoroacetic acid, and their Na and K salts, as well as methyl chloroacetate, methyl chloroacetate, PP propyl acetate, 2-butyl acetate, phenyl chloroacetate, These include ethyl bromoacetate, ethyl bromoacetate, butyl bromoacetate, ethyl bromoacetate, ethyl fluoroacetate, ethyl fluoroacetate, propyl fluoroacetate, butyl fluoroacetate, phenyl fluoroacetate, methyl iodoacetate, and the like.

Next, a specific manufacturing method will be described.

XCH2COOR4 is 1 relative to the active amine hydrogen in the polymerization unit represented by formula (11) in the raw material polymer.
It is preferably ~-0 times by mole, and more preferably 7 to 70 times by mole.

There are no particular restrictions on the temperature and time of the reaction. The temperature is 20
℃ to 200℃, more preferably 30℃
to 110°C. The reaction time is S hours to 10
0 hours is preferred, and more preferably 70 to 40 hours.

The reaction may optionally be carried out in the presence of an inert liquid. The inert liquid refers to the raw material polymer and
Refers to substances that are substantially inert to COOR4, such as water, alcohols such as methanol, ethanol, furopanol, butanol, and coethylhexyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, and hexane. , aliphatic hydrocarbons such as heptane and octane, substituted aromatic compounds such as chlorobenzene, bromobenzene and nido-benzene, halogenated hydrocarbons such as chloroform and dichloroethane, ketones such as methyl ethyl ketone and acetone, diethyl ether, Ethers such as tetrahydro-7rane and dibutyl ether, amides such as dimethylformamide and dimethylacetamide, 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 is preferable to carry out the reaction in the presence of a basic substance, and the effect is particularly remarkable when R4=H. Basic substances include sodium hydroxide,
Inorganic-alkali metal salts such as potassium hydroxide, sodium carbonate, potassium carbonate, as well as organic basic compounds can also be used.

When R4 is a metal or a hydrocarbon group, that is, when a salt or an ester is reacted, the basic compound is mainly used as a dehydrohalogenating agent in the reaction. In this case, the so-called hindered amine (hind
A substance called ered amine is effective. Examples of these include tributylamine, tribupylamine, λ,6-dimethylpyridine, lupetidine, and the like. Further, when R4 is 11, that is, when it is a carboxylic acid, an inorganic alkali metal compound is an example of a preferred embodiment, and it is further preferred to add a hindered amine in addition to this. These basic compounds are used in an amount of 0.1 to 10 times the amine hydrogen in the raw material polymer,
More preferably, it is used in the range of O, S - & times the mole.

When X is a halogen other than iodine, it may be preferable to add a small amount of iodide ion in the form of potassium iodide, sodium iodide, or the like. There is no particular limit to the amount added, but it is 0.01-// for XCH2COOR4.
θO morti is preferred, more preferably θ/-! ;0
It's morchi.

In addition, in the substances of the present invention, those in which R4 in formula (i) is a hydrocarbon group can be converted to R4=H, that is, a carboxylic acid type, by hydrolysis using an alkali catalyst or the like. It is also possible to convert this into a metal salt type using an i-liquid containing metal ions such as Ha and K.

The polymer of the present invention can be used as an adsorbent for metals, organic substances, and the like. Adsorption refers to so-called trapping and adsorption of metals through chelation, adsorption through ion exchange, physical adsorption, chemical affinity adsorption, and the like.

Among these, the polymer of the present invention has excellent performance as a chelate adsorbent. Compared to conventional chelate resins, the polymers of the present invention had good chemical stability and could withstand long-term continuous operation.

Conventional known methods can be used to use the substance of the present invention as a chelating agent. For example, the purpose can be achieved by bringing it into contact with a liquid containing metal ions.

In addition to being a chelating agent, it also showed good properties as an adsorbent for organic substances. Furthermore, the polymer showed good biocompatibility.

Examples are shown below, but these are not intended to limit the scope of the invention.

Precedent 1 m-divinylbenzene, Of, p-vinylruco (N
, N-di(λ-7minoethyl)]aminoethylbenzene got, toluene 10. After mixing Of and adding 7zobisin buti + = 2) ril θ, /f to this and putting it in an SQ- ampoule tube and sealing the tube, ? The reaction was carried out at 0'C for 1S time. After the reaction, a sealed tube was created and the reaction product was taken out. The product was completely solidified. After crushing this in a mortar, it was washed successively with 7 setsone and water. This product is 6
The particles were sequentially classified using a mesh of 0 mesh and /00 mesh to obtain particles with a particle size of 60 mesh or less and #70 mesh or more. Elemental analysis of this material revealed that a polymer was obtained with the same mortar as the charging composition. Also,
The weak base capacity of this substance is j: 'l g meq/f
Met.

Reference Example: Commercially available 36% divinylbenzene (39% m-divinylbenzene, 17% p-divinylbenzene, 3% ethylstyrene, diethylstyrene/%) 4'! A mixture of f, p-bierucault (N, N-di(co-aminoethyl)) aminoethylbenzene 5&r, and azobisisobutylnitrile lOf was polymerized by a conventional suspension polymerization method to obtain a product. From analysis, divinylbenzene, ethylstyrene, p-vinyl-1-CN
, N-di(two-aminoethyl)]aminoethylbenzene was found to be completely polymerized. Moreover, the weak base capacity of this product was Q, Ofmq/l.

Example/Bromoacetic acid/9.0? (/J?mmol) to AJtd
of water and cooled to 70°C. The temperature of this solution is
While maintaining the temperature at about θ℃, perform normal hydroxide) IJum solution/,? ? - was added dropwise with stirring. Reference Example 1
Polymer obtained with JOf and potassium iodide 0.3
Nia 9 (3 dammol) was added and heated to 0°C.

The reaction was continued at this temperature for 22 hours with stirring. During the course of the reaction, pulverized potassium carbonate JOf (co/7 rnmol) was gradually added so as to keep the PL of the reaction solution at about 7.

The product thus obtained was subjected to p-passing and washing with water to obtain a product. The average particle size was SOOμ. When the weakly acidic ion exchange capacity of the product was measured, it was II! ;
It was 3 meq/f. In addition, when elemental analysis was performed on the product as a carboxylic acid type, C: 64ff? ,
H: 10/, N: 10. s9. O: /Mori 3
Met. From these experimental results, it was found that 111% of carboxymethyl groups were introduced with respect to the hydrogen atoms in the 7 raw material amino groups.

EXAMPLE Cobromoacetic acid Jgf/cobromoacetic acid is dissolved in water and cooled to 70°C. While maintaining this solution at about io'c, 27 g of 1N sodium hydroxide solution was added dropwise with stirring. To this solution were added the polymer S, Of obtained as in Example/1 and potassium iodide, 7f, and qO was added at 50°C.
Allowed time to react. 1 zry of potassium carbonate was added halfway in the same manner as in Example.

The average particle size of the product is sopμ, and the weak acid ion exchange capacity is μ1.
9 meq/l, elemental analysis value is C: Ruyu Q9, H Near 3
/.

N:t79,0:ko/, 'l/. Moreover, the infrared spectrum of this product (carboxyl group type) is shown in FIG. The introduction rate of carboxymethyl groups to the raw material amine hydrogen in this reaction product was IQ%.

The obtained polymer showed extremely superior chemical resistance compared to conventional polymers. In addition, the following experiment was conducted to examine the metal chelating ability of this product. That is, this polymer SOf was added to a /6 mmol/L solution of cupric chloride, and after a period of time with stirring, the solution was separated and the copper ion concentration was measured. The concentration was high.

Example 3 Ethyl α-bromoacetate &3. Of,) Lee n-thylamine/241 in dimethylformamide (DMF) 50
The polymer obtained in Example λ/θ
t was added thereto, and the mixture was reacted for 1S hours at 90° C. with stirring. After thoroughly washing the reaction product with amethane, it was dried and the weight increase was measured to determine the introduction rate of ethyl acetate groups, which was found to be 39%.

Next, add this to ethanol 3-1 water 22! ;vn
t, mixed with 101 sodium hydroxide and stirred, 90
The reaction was carried out at ℃ for q hours. The weakly acidic ion exchange capacity of the product is more than 7 meq/f - the result of elemental analysis is C: 7
3.9/,, H: tJO, N: K here, O: 9
! ;/Met. From these results, it was found that the production rate of carboxymethyl groups was 3 times higher.

[Brief explanation of drawings]

Figure 1 shows an example (Example 2) of the adsorbent polymer of the present invention.
The infrared spectrum of Patent applicant Toru Hoshino, Patent attorney representing Asahi Kasei Industries Co., Ltd. Procedural amendment (spontaneous) October 21, 1980 Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Indication of the case 1988 Patent 1 No. 172743 2, Invention Name Adsorptive polymer and its manufacturing method 3 Patent applicant related to the amended person case 4, agent address 3-7 Yotsuya, Shinjuku-ku, Tokyo, Shin Building 5B
6 Number of inventions increased by amendment None 7. The statement in the description of the contents of the amendment subject to amendment shall be amended as follows. (1) Amend the scope of the 4I claims as shown in the attached sheet. (2) Lines 7 to 9 of page ``Quantitatively speaking, the total amount is 2o- or more, more preferably 4tθmolti or more.'' is changed to ``Quantitatively speaking, the weak acidic exchange capacity is . It is more than Smeq/SF.'' I am corrected. Representative Patent Attorney Toru Hoshino Claim (1): An adsorbent polymer containing a polymerized unit represented by the following structural formula (1). 1 (Here, R1 represents hydrogen or a hydrocarbon group with carbon number/~da, R2 and Rx are hydrogen or 10H2COOR4
and R4 is hydrogen, metal, or carbon number/~10
represents a hydrocarbon group. where k and 1 represent the number of repetitions of θ, 8λ, or 3. Each repeating unit of A, , A, may be the same or different. Any positional relationship between R1, the main chain, and the aminoethyl group with respect to the benzene skeleton may be used. The aminoethyl group shall contain at least /Tsukuda) -CHz COOR4. ) (2) 9 Weakly acidic exchange capacity is Q! The adsorptive polymer according to claim 1, which has an rmeq/f or more. (3) A method for producing an adsorptive polymer containing a polymerized unit represented by formula (1), which comprises reacting a copolymer containing a polymerized unit represented by the following structural formula (1) with XCH2COOR4. . 1 (In R,, R4, and 1, 1 is the same as above.

Claims (1)

[Scope of Claims] (xl゛An adsorptive polymer containing a polymerized unit represented by the following structural formula (I). ■ h! (Here, R1 represents hydrogen or a hydrocarbon group having l-d carbon atoms. , horse, R3 is hydrogen or -CHI COOR4
, R4 represents hydrogen, a metal, or the number of carbon atoms, and k and 1 represent the number of O18- or 3 repeats. A
, , A, each repeating unit may be the same or different. The positional relationship of R1, the main chain, and the 7-minoethyl group with respect to the benzene skeleton may be any. The aminoethyl group shall contain at least one CH2COOR4. )(2), the adsorption according to claim 1, wherein at least 2Q mole of the total amount of hydrogen and -CH2COOR4 bonded to N of (At)k and (At) of structural formula (1) is -CH2COOR4. Polymer. (8) A method for producing an adsorbent polymer containing a polymerized unit represented by formula (1), which comprises reacting a copolymer containing a polymerized unit represented by the following structural formula (n) with XCH2COOR4. 1 (1) (Rr s R4 and , l are the same as above.X
represents halogen. The position of the substituent on the benzene skeleton with respect to the main chain may be any position. )