JPH01304052A - Preparation of anion exchange resin - Google Patents

Abstract

PURPOSE:To prepare a highly selective anion exchange resin, by subjecting a crosslinked org. polymer matrix containing reactive halogen and specific amino or phosphine to quaternizing reaction using a specific reaction solvent. CONSTITUTION:A crosslinked org. polymer matrix having a reactive halogen atom and amine or phosphine represented by formula I(wherein D is N or P, R1, R2 and R3 are an alkyl group or an aryl group and further shows wherein the logarithm log P of a distribution coefficient shown by formula III of octanol/ water of a compound represented by formula II becomes -1 or more) are subjected to quaternizing reaction to prepare an anion exchange resin. In this case, as a reaction solvent, an aprotic org. solvent and a polar org. solvent dissolving amine of the formula I and capable of being mixed with the aprotic org. solvent are together used.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for producing anion exchange resins.

(Prior art) Ion exchange resins are used for water softening and pure water production (e.g. seawater desalination, river, lake water purification, etc.), wastewater treatment (e.g. industrial wastewater demolding metal process, Purification of domestic wastewater,
(e.g. desilvering process of photographic processing system waste), purification of industrial products and intermediates (extraction of impurities or target compounds from chemical products, foods, pharmaceuticals, etc.), processes applied to ion exchange chromatography, For environmental management (
Furthermore, it is used in a wide range of fields as a phase transfer catalyst.

Ion-exchange resins, especially anion-exchange resins, do not adsorb anions when a large number of anions coexist in the solution. It will be adsorbed to the resin along with other coexisting anions. Therefore, in order to take this measure, the amount of resin used must be in excess of the amount of anion removed, which causes an increase in costs. Unfortunately, even anions that should not be removed are adsorbed by the resin, reducing the concentration of anions in the solution that are not intended to be removed. This means that if the resin is used in the purification process as the purpose of removal of impurity anions, the extraction of the compound will result in a decrease in the yield of the purified product? If the resin is used in the purification process for the purpose, it may cause a decrease in the purity of the NT product.
It is desired to develop anion exchange resins that are substantially inert with respect to other ions. Such requirements are important in the field of processing methods for silver halide color photographic materials, such as color developing solutions, etc. It is also prominent in the technical field of removing dissolved ions from photographic processing solutions such as developing solutions, bleaching solutions, fixing solutions, and bleach-fixing solutions. [, 5-27/767≠ issue, same,? 5'
/Arjj, US-32r3y2o, Machikai Shoj2-
703120. 17-/1762 Hiro issue, same t/-P
No. JJjλ describes a method for regenerating a developer using an ion exchange resin and an ion exchange membrane. However, fixer solutions containing many anion components in addition to iodide ions are not always capable of satisfactorily removing iodide ions from bleach-fix solutions.

Therefore, it is desired to develop an anion exchanger that can selectively remove halide ions and especially iodide ions from among the many coexisting anions.

Although it is not an anion exchanger, it plays a role in compounds in which the cationic group consisting of a quaternary ammonium group or a quaternary phosphonium group is totally blind.When the anion is an iodide ion or perchlorate ion, the structure surrounding the cationic group is hydrophobic. It is said that the interaction with anions is significantly improved by doing so. For example, in the case of macromolecular compounds, these facts are based on macromolecular chemistry physics (
Makromolecular Chemistry,
Physics ) /! Volume 3, page 3 (2011), the Canadian Journal of Chemistry for low molecular weight compounds.
rnal of chemistry) jr volume /
It was reported in 4L12 Tei (/rito), and is an important characteristic that is specified by functional groups in both high-molecular compounds and low-molecular compounds.

However, it is very difficult to manufacture these hydrophobic cationic group-containing polymer compounds as anion exchange resins. That is, a method for producing an anion exchange resin through quaternary chemical formation (Zk) using an amine or phosphine to a crosslinked organic polymer having a reactive halogen atom (hereinafter referred to as IJ Lux) (hereinafter referred to as a precursor resin), which is an important synthesis method for an anion exchange resin. For example, JP-A No. 3417, US Pat. No. 741. /No.32,
Same 3゜Kota 7. G≠r, same 3. ! Hirori, Yo No. 62, J, No. 637.631, No. 3.117.171, J, r4tj,! At No. 2. tjO, No. 4'27,
Same, l, 30. ≠No. 22, West German patent/ , /j/, 1
No. 27, Special Publication No. 32-17 Hiroshi No. 3, IIL6-/RIO
The methods described in μμ No. A-200541, No. 3-jλ, No. J 3-27, and No. 33-7327 are known. amines (e.g., trimethylamine, dimethylamine, etc.) will warp quickly and have a good quaternization rate. In this case, the progress of the quaternization reaction is very slow, and the reaction rate (quaternization rate) also stops at a low level, which is not a practical method for producing resin. Furthermore, it was reported in the Journal of Industrial Chemistry, Vol. 6, No. Since it is reported on page 123 (/1963), without some new technical breakthrough, the hydrophobic amine or phosphine represented by the above general formula (I) cannot be used without using the hydrophobic amine or phosphine described in the above patent. A synthetic method for anion exchange resin? Hydrophobic cation site used as is? Anion exchange resin with? It is obvious that it cannot be synthesized with a good quaternization rate.

Is the reaction solvent devised to activate a hydrophobic amine represented by the general formula (1) with a halogen? An attempt to quaternize it with a low-molecular-weight compound is described in "Organic Reaction Mechanism" J edition, page R (Toki Kagaku Dojin, page R). However, when all of these aprotic organic solvents are used in the production of this resin, the amine represented by formula (I) or the phosphine used in the quaternization reaction is insoluble in these aprotic organic solvents. Unfortunately, this leads to non-uniformity of the reaction system, and the quaternization rate of the resulting resin is not satisfactory.

(Problems to be Solved by the Present Invention) The first object of the present invention is to obtain a high quaternization rate in the production of an anion exchange resin having a hydrophobic cation site f by a quaternization reaction of a precursor resin. Synthesis method that can be obtained? It is about providing.

A second object of the present invention is to provide an inexpensive method for synthesizing a highly selective anion exchange resin.

A third object of the present invention is to provide a method for synthesizing a highly selective anion exchange resin that is easy to produce.

(Ninth Means for Solving Section @) As a result of intensive study, the present inventors have discovered that the above object can be achieved by using the following method as a manufacturing method.

In a method for producing an anion exchange resin by carrying out the entire quaternization reaction using a crosslinked organic polymer matrix having a reactive halogen atom and an amine or phosphine represented by the following formula (I), ( The combined use of 1) an aprotic organic solvent and (2) a polar organic solvent that can dissolve the amine or phosphine represented by the following general formula (1) and can be mixed with the aprotic organic solvent is defined as A method for producing an anion exchange resin.

General formula (I) In the formula, each represents a nitrogen atom or a phosphorus atom.

R1, R2, and R3 are alkyl groups that may be the same or different, and are aryl groups, which are bonded to each other to form a ring structure. may be formed, and R1, R2
, R3 is a compound represented by the following general formula (It) whose logarithm (togP) of the partition coefficient P of octatool/water is -1
Is this the basis? represent.

General formula (n) Calculation formula for P To explain in more detail, in the preferred method for producing an anion exchange resin of the present invention, preferred examples of the aprotic organic solvent are 2) IJ sils such as acetonitrile, cyanoethane, benzonitrile; ), amides (e.g. dimethylformamide, dimethylacetamide, dimethylbenbrozoic acid amide, diethylformamide), sulfoxy/de*11. These solvents include dimethyl sulfoxide (7), sulfones (eg, dimethyl sulfone, sulfolane), and phosphoric acid amides (eg, tetramethyl phosphoric acid triamide), and these solvents may be used in combination with gold.

Among these, acetonitrile, cyanoethane, dimethylformamide, dimethylacetamide, and dimethylsulfoxide are preferred. WK preferred is acetonide l
), dimethylformamide, dimethylacetamide,
Dimethyl sulfoxide.

The polar organic solvent is one that is dissolved in the amine or phosphine represented by the general formula (1) and mixed with the aprotic organic solvent. Preferred examples thereof include alcohols (e.g., ethyl alcohol, n-propyl alcohol, , isopropyl alcohol, n-i methyl alcohol) halogen-containing solvents (e.g. dichloromethane, chloroform, /.

Kodichloroethane, chlorobenzene, dichloro(benzene, /, /, /-)dichloroethane, chloropropane)
, ketones (acetone, diethyl ketone, methyl ethyl ketone, acetophenone, etc.), saturated carboxylic acid esters (ethyl acetate, methyl acetate, butyl acetate, etc.), etc., and uffi or higher of these solvents may be used in combination. Among these, ethyl alcohol, isopropyl alcohol, /Iλ-dichloroethane, chloroform, acetone, and methyl ethyl ketone are preferred, and ethyl alcohol, isopropyl alcohol, /, 2-dichloroethane, and methyl ethyl ketone are particularly preferred.

The dielectric constant is preferably 5 or more.

The compound represented by the above general formula (1) may be used in combination with 2a or more.

In the above general formulas (I) and (It), D is a nitrogen atom or a phosphorus atom, and a nitrogen atom is particularly preferred.

In the above general formulas (I) and (It), R1, R2 and R3 are each preferably an alkyl group having 6 or more carbon atoms (for example, n-butyl, isobutyl, 5ec- butyl, tert-butyl,
n-pentyl, n-hexyl, cyclohexyl, n-peptyl, n-octyl, n-nonyl, n-decyl, phenoxyethyl, benzyl, phenethyl, chlorobenzyl, methylbenzyl, methoxybenzyl), aryl group with 6 or more carbon atoms (phenyl, naphthyl, tolyl, methoxyphenyl, chlorophenyl) Ti, particularly preferably an alkyl group having ≠ to 10 carbon atoms, a phenyl group, and a benzyl group.

The crosslinked organic polymer matrix of the present invention is preferably obtained by polymerizing a mixed Zimmer's solution containing a monomer having at least λ ethylenically unsaturated groups in the molecule. Crosslinked organic polymer matrix? Is the polymerized fraction formed an ethylenically unsaturated group capable of co-electrification? It may contain a repeating unit obtained by copolymerizing one monomer in the molecule. The above copolymerizable heptamer is -
It may also be a mixture of more than one type of monomer.

The series of monomers having two or more copolymerizable ethylenically unsaturated groups in the whole molecule include O-divinylbenzene, m-
Divinylbenzene, p-divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate,
/, A-hexanediol dimethacrylate, etc.
It is also preferable to use a mixture of λ or more of these.

This '), o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, and ethylene glycol dimethacrylate are preferred. These monomers having two or more copolymerizable ethylenically unsaturated groups in the molecule take a value of 1 to λO% in mole percentage to the total amount of the resin, and preferably 1 to λO%. Percentage, especially preferably! No/!・It is secent.

"-" of monomers having one copolymerizable ethylenically unsaturated group in all molecules means ethylene, vinyl chloride, vinylidene chloride, propylene, /-butene, isobutyne, styrene, α-methylstyrene, vinyltoluene. , 0-ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-vinylacetophenone, 0-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, hydroxymethylstyrene, monoethylene of aliphatic acids Unsaturated esters (e.g. vinyl acetate, allyl acetate), amides of ethylenically unsaturated monocarboxylic acids or dicarboxylic acids (e.g. N-isopropylacrylamide, N-butylacrylamide, N-tertbutylacrylamide N.

N-diptylacrylamide, pJ-tert octylacrylamide, diacetone acrylamide, N,
N'-dibenzylmaleic acid diamide), esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (
For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate%/chlorohexyl methacrylate, benzyl methacrylate, /-adamantyl methacrylate, /-(j
, t-dimethyladamantyl) methacrylate, n-butyl acrylate-1, n-hexyl acrylate, -1-ethylhexyl acrylate), monoethylenically unsaturated compounds (e.g. acrylonitrile, methacrylateryl, methyl vinyl ketone, ethyl vinyl ketone) ), dienes (eg, butadiene, isoprene), etc., and it is also preferable to use a mixture of 21 or more of these. This house, styrene/, α-methylstyrene, 0-
Ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, hydroxymethylstyrene, methyl methacrylate, vinylidene chloride, acrylonitrile, methacrylaterile, methyl vinyl ketone, etc. is generally preferred.

Among these, which compound is represented by general formula (1)? A copolymerizable ethylenically unsaturated group that does not contain a cation introduced in the quaternization reaction used? Monomers with 7 r
The repeating unit obtained by polymerization is expressed as a molar percentage based on the total amount of the resin. The amount is preferably 0 to 20%, most preferably 0 to 70%.

Compound represented by general formula (I)? The cations introduced in the quaternization reaction may be included in the repeating units in mole percentages based on the total amount of resin, preferably up to 10%, preferably 1% to 10%. up to 0%, particularly preferably up to 0%.

Octatool/water, partition coefficient P is a saliva that indicates the distribution of a certain compound into octatool and water given by the measurement method and calculation formula below. The smaller the togP value, the more water-soluble (hydrophilic) the compound is, and the larger the a+ value, the more oil-soluble (hydrophobic) the compound is.

Measurement method: Sample j x 10-5 mol dissolved in gold water,
Add Octatool/Mizugo to this and shake for λ time while maintaining the temperature at 200C. After stopping the shaking, let it stand and determine the concentration of the sample in Octatool, water, and each phase. From the obtained concentration value, the octatool/water distribution coefficient Pt is calculated using the following formula.

Calculation formula In the present invention, the compound represented by the formula (It) above has a togP value of 1/ or more, preferably a value of t from 1/ to IO, and 9, most preferably 10, from j to r
That's it.

In the method for producing an anion exchange resin of the present invention, the amount of the amine or phosphine represented by the above general formula (1) used in the quaternization reaction is 1710 times or more in mole relative to the reactive halogen atom in the precursor resin. It can be used from Preferably, the amount is from 772 times the mole to 10 times the mole, and preferably from the same mole to the times the mole.

In the method for producing an anion exchange resin of the present invention, the amount of the polar organic solvent used in the quaternization reaction is t/r times the amount of the amine represented by the general formula (I) based on the weight of the phosphine. The above can be used. Preferably // ko times or more up to IO times, most preferably / times or more j times! It is up to t.

In the method for producing an anion exchange resin of the present invention, the amount of the aprotic organic solvent used in the quaternization reaction can be 7710 times or more the weight of the organic solvent used.

Preferably//! Of these, the amine or phosphine coated with the above general formula (1) used for convenience and the above polar organic solvent used for convenience are mixed in a uniform amount. A range that provides a suitable solution is preferred.

The quaternization reaction can be carried out at a temperature of up to 00C-λ000C. Among these, preferably ≠00C or more/200
Up to C, preferably t.

0C or higher, up to the reflux temperature of the solvent.

In the method for producing an anion exchange resin of the present invention, the precursor resin used is generally
No., U.S. Patent Co., f7 Hiroshi, /32, 3,1 7,6
≠No. 1, No. 3. ! 117, No. 562, 3. t37,
1! ! No. 3. ZaA7. r7r issue, same 3, llA3
,! At No. 2,430゜G No. 27, No. 2, 63
0, ≠ 2P issue, West German government permit/ , /j/ , /27 issue, ¥j Kosho 32-Hiro/4L3 issue, same lit -/P01
4 (No. 7, No. 4-200jlA, No. 4-200jlA, No. 33-27, No. 6, No. 33-7327, and those synthesized by methods similar to these) It is.

(Implementation Criteria) Examples of the present invention are given below. The present invention will be explained in more detail, but the present invention is not limited to these examples.

The togP of the benzyl chloride quaternized product of t-amine (corresponding to the -throw formula (n)) used in the examples is as follows.

Compound AogP Example 1 (Synthesis of precursor resin (1)) Precursor resin (1): Poly(divinylbenzene-cochloromethylstyrene) z:y=10: TaO Stirrer, thermometer, and cooling tube Installation 7-C3 into a Mitsuro flask with water/! at room temperature! 007, polyvinyl alcohol (commercially available as Gohsenol from Nippon Gosei Kagaku Kogyo Co., Ltd.)2. r9, sodium chloride toy2
Add and stir gently to dissolve the liquid. Add chloromethylstyrene (CMS- from Seimi Chemical Co., Ltd.) to this solution.
commercially available as AM) 201. f, divinylbenzene/ri, jr, benzoyl peroxide, 0? toluene λO
The solution dissolved in O2 is added at room temperature and stirred for 7 hours under a nitrogen stream at a speed of /lO revolutions per 7 minutes.

After raising the temperature to 70°C and reacting for 7 hours, the resulting resin sphere was removed, immersed in hot water at RO 0C, and ultrasonically cleaned for 30 minutes. 2t,
Acetone 21. Washed with ethyl acetate λt and dried under reduced pressure for 100 min.
Dry at °C, spherical resin 2λ/ particle size less than 1fIIR
, 27f Toku9. The chlorine content of the resin is determined by elemental analysis.
/2 resin ats, j, r ri x l0-3 mole of chlorine amount? Confirm to (synthesis of precursor resin (n)) Previous 11 = body resin (If): poly(divinylbenzene-costyrene-cochloromethylstyrene) x:y:z:ri:/1. tnia 7 Stirring device, thermometer and cooling pipe tone number are your friend! Add 300 f of water, polyvinyl alcohol (same as above), oy, sodium chloride/
Add A Off, stir thoroughly, and dissolve.90 Add chloromethylstyrene (same as above) g/λV to this solution.
, styrene j2 , / ? , divinylbenzene 4
t3. tl? , benzoyl peroxide r, oyy2 dissolved in toluene zooyy was added at room temperature, and 72
Stir for 30 minutes under a stream of methane at a speed of 0 rotations? Continued by Higo, 7
9. Raise the temperature to 00C and react for 7 hours. Thereafter, the reaction system was cooled to room temperature, and the solid content (spherical particles) was collected. This resin ball 2r.

Immerse in warm water at 0C and perform ultrasonic cleaning for 30 minutes, then perform ultrasonic cleaning for 20 minutes each using solvents in the order of methanol 2t, acetone 2t, ethyl acetate 2t, and acetone at 10o'C under reduced pressure. Dry with 0 spherical resin particles?
ni*fc. The resin contained 1 t of sodium chloride (11- determined, per 72 of the resin!, 32 x 10 moles of chlorine content was confirmed by elemental analysis. 90 (quaternization of precursor resin) Using the precursor resin separated above Then, the quaternization reaction with tributylamine was carried out according to the production method of the present invention.The combinations and amounts of polar and non-polar solvents used, as well as the quaternization ratios, are shown in Table 7 and the ratios are shown in Table 7. The quaternization rate under the same reaction conditions when a solvent alone is used and when a solvent other than the production method of the present invention is used is shown in the table.Reaction operations and conditions are shown below. and conditions: Precursor resins (1) and (II) synthesized above were weighed into a three-meter flask with a predetermined stirring device, thermometer, and cooling pipe.
Solvent and tributylamine? Add the mixture and let it swell for 30 minutes while stirring at room temperature. Heat this to ♂00C and let it react for 7 hours. After that, the reaction system? Cool to room temperature and solid content? The number of houses. This resin sphere (I) was immersed in warm water at 0C, and after ultrasonic cleaning for 30 minutes, the solvent was washed with 2 tons of methanol, 2 tons of acetone, ethyl acetate λt, and 2 tons of acetone in that order. Using ultrasonic cleaning? ! The spherical resin was dried at 21170C under reduced pressure for 30 minutes each time, and the spherical resin was pulverized to a concentration of 90 chloride ions. Titration using IN silver nitrate as a silver-extreme gold detector! llK, put it out.

As is clear from the comparison between Tables 1 and 2, the production method of the present invention greatly increases the quaternization rate of the precursor resin, and as a result,
High anion exchange capacity? An anion exchange resin containing tributylammonium (tributyl ammonium) is obtained by a simple reaction procedure. Is it a hydrophobic cation site with a low quaternization rate in the production method using other solvents? Only resins that have the following properties can be obtained.

Example Precursor resins (1) and (■) synthesized in Example 1 5 A quaternization reaction is carried out using the amine represented by the above general formula (1) as a mixed solvent of diisopropyl alcohol rO1 and acetonitrile 601 according to the production method of the present invention. The amount of amine used and the quaternization rate of the resulting resin are shown in Table #c3. For comparison, acetonitrile, inpropyl alcohol used as a solvent alone in nine cases,
Table 3 shows the quaternization rate under the same reaction conditions in the case of no solvent and in the case of using a hydrophilic amine (trimethylamine, dimethylhydroxyethylamine) as the amine.

The reaction operation and conditions are the same as in Example 1.

As is clear from Table 3, the production method of the present invention is a hydrophobic cation site that has a high anion exchange capacity tk regardless of the type of amine represented by the above general formula (1). It can be seen that a phosphorescent anion exchange resin can be easily obtained by a two-step reaction.

However, for hydrophilic amines (trimethylamine, dimethylhydroxylamine) other than the amine represented by the above general formula (I), the solvent system of IJ Method 11 of the present invention has a lower quaternization rate. This shows that the effect is particularly significant in the quaternization reaction of precursor resins with hydrophobic amines.

From the implementation of the above two examples, it is clear that the method for synthesizing an anion exchange resin using a mixed solvent consisting of a polar organic solvent and an aprotic organic solvent of the present invention uses a hydrophobic amine or phosphine represented by the above general formula (I). Reaction rate of next grade reaction? Higher, higher ion selectivity? It has become clear that this is a very effective method for using resins with hydrophobic cation groups.

Claims (1)

[Claims] A method for producing an anion exchange resin by carrying out a quaternization reaction using a crosslinked organic polymer matrix having a reactive halogen atom and an amine or phosphine represented by the following general formula (I). , as a reaction solvent (1)
An anion exchange resin characterized in that an aprotic organic solvent and (2) a polar organic solvent that dissolves an amine or phosphine represented by the following general formula (I) and can be mixed with the aprotic organic solvent are used together. manufacturing method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (D represents a nitrogen atom or a phosphorus atom. R_1, R
_2 and R_3 may be the same or different, and are an alkyl group or an aryl group, and may be bonded to each other to form a ring structure, and R_1, R_2
, R_3 represents a group in which the logarithm (logP) of the octanol/water partition coefficient P of the compound represented by the following general formula (II) is -1 or more. General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Calculation formula for P P = Concentration of the compound of general formula (II) in the octanol phase /
Concentration of the compound of general formula (II) in the aqueous phase