JP2002102719A - Mixed bed type ion exchange resin bed and anion exchange resin used in the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mixed bed type ion exchange resin bed giving highly purified treated water. SOLUTION: The mixed bed type ion exchange resin bed is formed by mixing an anion exchange resin having repeating units of formula (1) (A is a 3-8C alkylene or a 4-8C alkyleneoxymethyl, B is a primary to tertiary amino or a quaternary ammonium, and when B is a secondary or a tertiary amino or a quaternary ammonium, an organic group bonding to N is a 1-6C alkyl or hydroxyalkyl) with a cation exchange resin having repeating units of formula (2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mixed bed type ion exchange resin bed used for producing ultrapure water and purifying various solutions. The ion exchange resin of the present invention is, for example, metal ions, microorganisms, enzymes, proteins, ionic substances, desalination, removal and purification of organic substances, demineralized water, production of ultrapure water, ions in the gas phase, charged substances It is used for adsorption, purification and removal of water.

[0002] Further, the obtained anion exchange resin is super LS
The present invention relates to an ion-exchange resin for producing high-purity pure water suitable for use in the electronics industry, such as washing water used in the production process of I or the like.

[0003]

2. Description of the Related Art As is well known, ion exchange resins are widely used in fields such as desalination of water and purification of solutions. Currently, the most commonly used anion exchange resins are:
The styrene-divinylbenzene crosslinked copolymer is halomethylated, and the halomethyl group is reacted with ammonia or a primary to tertiary amine. As the cation exchange resin, a sulfonated styrene-divinylbenzene crosslinked copolymer or a copolymer of methacrylic acid and a crosslinker such as alkylene glycol dimethacrylate are generally used.

One method of using an ion exchange resin is to mix an anion exchange resin and a cation exchange resin and use them as a mixed bed type ion exchange resin bed (MIXED BED). It is mainly used to remove trace amounts of impurities in purification steps of various solutions. The most common mixed bed type ion exchange resin bed is composed of an anion exchange resin having a trimethylaminomethyl group or a dimethyl-hydroxyethylaminomethyl group as an ion exchange group, and a cation exchange resin having a sulfonic acid group as an ion exchange group. It is a mixture.

[0005]

The mixed bed type ion exchange resin bed is widely used as an indispensable element for removing a trace amount of impurities in a liquid. It is becoming difficult to satisfy this requirement with the conventional mixed bed type ion exchange resin bed. Therefore, an object of the present invention is to provide a mixed bed type ion exchange resin bed which can satisfy even higher requirements for impurity removal. As a method for reducing the elution from the ion exchange resin, it is general to pass the eluate remaining in the resin through ultrapure water before use. However, this method consumes a part of the product ultrapure water in the manufacturing process, and reduces the efficiency of the process. Therefore, in order to increase the amount of water with high quality, an ion-exchange resin with a fast elution amount and a small elution amount from the resin is desired.

On the other hand, it is said that the concentration of alkylamines in water is greatly related to the defective rate of products in semiconductor production. In order to improve the yield rate of semiconductors, ultrapure water that minimizes leakage of alkylamines such as trimethylamine is desired.

[0007]

The mixed bed type ion exchange resin bed according to the present invention comprises an anion exchange resin having a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2). A mixed bed type ion exchange resin formed by mixing with a cation exchange resin having a unit, a method for producing the same, and pure water when passed under a condition of a space velocity SV30 and a water passing temperature of 25 ° C. The concentration of alkylamines in the pure water passed 6 hours after the start of operation of the production equipment is 10 p.
pt or less.

[0008]

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Wherein A represents an alkylene group having 3 to 8 carbon atoms or an alkyleneoxymethyl group having 4 to 8 carbon atoms;
B represents a primary to tertiary amino group or a quaternary ammonium group. When B represents a secondary or tertiary amino group or a quaternary ammonium group, the organic group bonded to the nitrogen atom is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. )

[0010]

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[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The anion exchange resin and the cation exchange resin used for forming the mixed bed type ion exchange resin bed according to the present invention have an average particle size of 0.1 to 3 mm, similar to a normal ion exchange resin. In particular, it is preferably a spherical shape of 0.3 to 2 mm. The structure of the resin may be either a gel type or a porous type.

The anion exchange resin has a general formula (1)
A compound having a repeating unit represented by the following formula is used.

[0013]

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In the general formula (1), A represents 3 to 8 carbon atoms.
Is a linear or branched alkylene group or an alkyleneoxymethyl group having 4 to 8 carbon atoms, and is bonded to the benzene ring at the methyl group. Examples of the alkylene group represented by A include a trimethylene group, a tetramethylene group, and a hexamethylene group. Examples of the alkyleneoxymethyl group include a tetramethyleneoxymethyl group and a hexamethyleneoxymethyl group. A
May be bonded at any position of the benzene ring, but is usually bonded at the m-position or the p-position.

B is a primary to tertiary amino group or a quaternary ammonium group. When B is a secondary or tertiary amino group or a quaternary ammonium group, the organic group bonded to the nitrogen atom is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. As B, for example, an amino group, a methylamino group, a dimethylamino group, a diethylamino group,
Examples include a trimethylammonium group, a triethylammonium group, a dimethylhydroxyethylammonium group, and a dimethylhydroxypropylammonium group. B is preferably a quaternary ammonium group represented by the general formula (3), particularly a trimethylamino group or a dimethylhydroxyethylammonium group.

[0016]

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(In the formula, R ¹ , R ² and R ³ each independently represent an alkyl group or a hydroxyalkyl group having 1 to 6 carbon atoms.) In the present invention, formation of a mixed bed type ion exchange resin bed Is essentially composed of a repeating unit having an anion exchange group represented by the general formula (1) and a crosslinking group. The most common crosslinking group is a divinylbenzene unit. The anion exchange resin having a divinylbenzene unit as a crosslinking group is usually composed of 1 to 99 mol% of a repeating unit having an anion exchange group represented by the general formula (1) and 0.1 to 50 of a divinylbenzene unit.
Although it essentially consists of mol%, it is generally preferable that the ion exchange capacity is large. Therefore, the proportion of the repeating unit represented by the general formula (1) is preferably as large as possible.

When the anion exchange resin is essentially composed of a repeating unit having a quaternary ammonium group represented by the general formula (3) as an anion exchange group and a divinylbenzene unit, the neutralization The salt decomposition capacity is usually 0.05 to 4.0 meq / g of dry resin, and 2.
It is preferably from 5 to 4.0 meq. 1m wet resin
The neutral salt decomposition capacity per L is usually 0.01 to 2.0 meq, but is preferably 0.5 to 1.3 meq.

Anion exchange resins having a repeating unit having an anion exchange group represented by the general formula (1) are known, for example, JP-A-4-349949 and JP-A-7-349.
It can be produced by the method described in JP-A-291882. The components eluted from the anion exchange resin used in the present invention are roughly divided into two. One is eluted substances (unpolymerized monomers, oligomers, etc.) derived from decomposition of anion exchange groups and (oxidized) decomposition of resin skeleton, and the other is derived from styrene derivatives and reaction products generated during the resin production process. And eluates derived from the solvents and raw materials used in the reaction. The eluate from these resins can be reduced by washing in each manufacturing process.

In the polymer stage, for example, after polymerization, it is effective to wash the polymer with benzene, toluene, xylene, dichloroethane, methylene chloride, chloroform, THF and alcohols which are good solvents for the polymer. It is preferable to contact the crosslinked copolymer with an organic solvent in a range of 1.5 to 10 volumes. Examples of a method for contacting with an organic solvent include a method of stirring in a suspended state, or a method of filling a resin with a column and passing the solution through the column.

As a method for reducing the amount of elution at the stage of the anion exchange resin, a loading type (Cl type or Br type, hydrogen carbonate ion) or a regenerating type (OH type) can be used to reduce the amount of resin from several times the resin volume to 10%. If a volume of the water-soluble organic solvent is used, the elution amount from the resin is extremely small. Preferably, it is in contact with the ion exchange resin in a regenerated form that swells most. Others
A method of washing in the presence of an alkaline solution may be mentioned.
When treating with an alkaline solution, the type of the solution does not matter. Usually, caustic, alkali carbonate, alkali bicarbonate,
Washing is preferably performed for at least 30 minutes or more under conditions of pH 12 or higher and a temperature of 50 ° C. or higher, more preferably at a reflux condition of the solution or 120 ° C. or lower using a solution such as an alcohol alkali.

In addition, there is a method in which the anion exchange resin is washed in water / hot water in a loaded type or a regenerated type. in this case,
There is a method in which an anion exchange resin is suspended in water or hot water and contacted for at least 30 minutes, or a method in which the resin is packed in a column and hot water is passed through to wash the resin. In addition, a method of washing the anion exchange resin of the load type or the regeneration type with an organic solvent which swells more easily than water is also effective.
For example, methanol, ethanol, and isopropyl alcohol are particularly preferable. Further, in consideration of the economy of the washing solvent, washing with methanol using a regenerated resin is optimal. The washing of the resin is selected in consideration of the type of the organic solvent and the washing efficiency, but it is preferable to perform the washing at a high temperature in order to increase the washing efficiency.

The amount of the organic solvent used varies depending on the washing method and the purpose of use of the obtained pure water.
The amount is double to 20 times, and more preferably 2 times or more and 10 times or less. Thereafter, the organic solvent is completely extruded with demineralized water or ultrapure water. When a non-aqueous organic solvent is used, after once replacing with a polar organic solvent, washing with 0.5 to 20 times the amount of a non-aqueous organic solvent, further replacing with a polar organic solvent, and washing with water. Is preferred. Considering this complicated process, it is clear that it is preferable to use a water-soluble organic solvent as the organic solvent used for washing. The method of washing the resin is a method in which an anion exchange resin is packed in a column and an organic solvent is passed in a downward or upward flow, a method in which an organic solvent is put in a stirring tank, and the resin is stirred and suspended, and washing is performed. There are methods. The washing method may be appropriately selected depending on the purpose. Combine the above several cleaning methods,
It becomes possible to produce an anion exchange resin for ultrapure water with reduced eluate.

The cation exchange resin forming the mixed bed type ion exchange resin bed according to the present invention in combination with the above-mentioned anion exchange resin has a repeating unit represented by the general formula (2). It is a sulfonated copolymer of styrene and a crosslinking agent, usually divinylbenzene. The ratio of the crosslinking agent in the copolymer is usually 1 to 50% by weight, but preferably 3 to 30% by weight.

The mixing ratio between the anion exchange resin and the cation exchange resin in forming the mixed bed type ion exchange resin bed according to the present invention varies depending on the intended use of the ion exchange resin bed to be formed. 10: 1 to 1:10 in exchange capacity ratio
It is. 2: 1-1: 2, especially 1: 0.7-0.7: 1
Is preferable. When the ion exchange group of the anion exchange resin is a quaternary ammonium group, the above exchange capacity ratio is a neutral salt decomposition capacity ratio.

The anion exchange resin and the cation exchange resin are preferably present in the ion exchange resin bed in a state of being mixed as uniformly as possible. By doing so, the ion exchange reaction near an infinite stage is repeated in the ion exchange resin bed, and impurities are removed to the utmost. In general, when an anion exchange resin and a cation exchange resin are mixed, as is well known, both resins form aggregates and swell due to electrostatic force, forming a uniform mixed state of both resins. Is hindered. An anion exchange resin having a repeating unit represented by the general formula (1) also has a tendency to form an aggregate and swell when mixed with a cation exchange resin, like a common anion exchange resin. Several methods are known to eliminate this swelling, such as strong stirring, but the simplest and most effective is a water-soluble polymer having a dissociable group with the opposite sign to the ion exchange group of the ion exchange resin. This is a method in which the ion exchange resin is treated to neutralize the surface charge of the ion exchange resin. The treatment with the water-soluble polymer having a dissociable group may be performed on only one of the anion exchange resin and the cation exchange resin, or may be performed on both. Usually, the ion exchange resin is made of a water-soluble polymer having a dissociable group so that 0.02 to 1.0 meq (meq) of the dissociable group is contained per liter of the wet ion exchange resin in a free state. To process. When the water-soluble polymer is a free type as described below, it is preferable that 0.05 to 0.3 meq, particularly 0.1 to 0.2 meq, of a dissociable group is contained per liter of the ion exchange resin. In the case of the Na-type water-soluble polymer, the water content is 0.1 mL per liter of ion exchange resin.
It is preferably from 0.5 to 0.8 meq, particularly preferably from 0.1 to 0.5 meq. If the content of the dissociable group is too small, aggregation occurs when both resins are mixed, and the effect of suppressing the generation of fine particles from the ion exchange resin becomes small. That is, when the treatment is carried out using an appropriate amount of a water-soluble polymer having a dissociable group, not only the aggregation of the resin is prevented, but also the generation of fine particles from the resin is suppressed for unknown reasons.
The generation of fine particles from the ion-exchange resin is a problem that cannot be ignored with ultrapure water for cleaning used in the semiconductor manufacturing process, and an apparatus for capturing fine particles may be provided.

Examples of the water-soluble polymer having a dissociable group include:
Usually, those having a number average molecular weight of 1 × 10 ³ to 1 × 10 ⁶ by gel permeation chromatography are used. If the molecular weight of the water-soluble polymer is too small, the water-soluble polymer whose surface charge is to be neutralized is diffused into the ion exchange resin, which is not preferable. Conversely, if the molecular weight is too large, diffusion of ions is undesirably inhibited.
The preferable number average molecular weight of the water-soluble polymer having a dissociable group is 5 × 10 ^{3 to} 5 × 10 ⁵ , particularly 5 × 10 ³ to 1 × 10 5.
The range is ⁵ .

As the water-soluble polymer used for treating the anion exchange resin, those having a sulfonic acid group or a carboxylic acid group, for example, polystyrenesulfonic acid, polyvinylbenzylsulfonic acid, polymaleic acid, poly (meth) acrylic acid are usually used. Acid, polyvinyl sulfonic acid and the like. Among them, it is preferable to use polystyrene sulfonic acid or polyvinyl sulfonic acid. As the water-soluble polymer for treating the cation exchange resin, a polymer having a primary to tertiary amino group or a quaternary ammonium group is used. For example, poly (trimethylammonium methylstyrene), polyallylamine, poly (trimethylaminoethyl (meth) acrylate), poly (trimethylaminoethyl (meth) acrylamide), polyvinylpyridine and the like are used. Among them, those having a quaternary ammonium group as a dissociable group are preferably used. The water-soluble polymer having a dissociable group is usually used in a free form, but may be used in a salt form such as Na form or Cl form if desired.

The present inventors have found that the effect of the polymer electrolyte has an effect of suppressing fine particles generated from the resin, in addition to suppressing entanglement and aggregation of both ion exchange resins.
The fine particles referred to here are particles having a size of 0.05 μm or more. The constituent components of the fine particles are presumed to be fragments of the ion exchange resin resin and aggregates of the eluate, but the process of forming the fine particles is not clear. These fine particles were measured by a fine particle measuring instrument.

The effect of suppressing the fine particles by the treatment with the polymer electrolyte may be any treatment of an anion exchange resin or a cation exchange resin. For example, when an anion exchange resin is treated with an anionic water-soluble polymer electrolyte, not only the amount of fine particles from the anion exchange resin resin is reduced,
It was found that fine particles generated from the resin can be reduced even with the mixed bed resin. In general-purpose applications, leakage of fine particles from resin does not pose a problem, but generation of fine particles from resin is an important problem in ultrapure water for cleaning semiconductors.

It is said that alkylamines such as trimethylamine and dimethylamine and ammonia have a correlation with the defective product rate in semiconductor production, and it is considered that reducing the amount of alkylamines will greatly increase the yield of semiconductors. ing. For this reason, an ion exchange resin with less leakage of alkylamines is required. The concentration of alkylamines in the water at the column outlet varies greatly depending on the water flow rate (space velocity) and the water flow temperature. here,
The space velocity is a parameter indicating how many times the volume of the resin is passed in one hour. Generally, the water flow rate of the resin tower when producing ultrapure water is from SV10 to SV300. More preferably, it is SV30 to SV150. It is known that the alkylamine concentration increases as the passing water temperature increases, but ultrapure water is generally produced at 50 ° C. or lower. When ultrapure water was passed at a space velocity SV30 at a water passing temperature of 25 ° C, the concentration of alkylamines 6 hours after the start of water passing was set as a standard condition in the present invention.

Here, it is assumed that the ultrapure water used in the present invention is highly purified pure water. The quality of the ultrapure water used in the present invention is roughly 18.24 MΩ.
· Cm, TOC 0.5 ppb, number of fine particles of 0.05 μm or more is 1 / mL or less, trimethylamine concentration 5 ppt
The dimethylamine concentration is 1 ppt. Here, the ultrapure water used as raw water is produced by the existing anion exchange resin, and the raw water also contains alkylamines.
For this reason, the concentration of the alkylamines was defined as the difference between the amine concentration in the raw water and the amine concentration eluted from the resin. Alkylamines such as trimethylamine and dimethylamine in water, and ammonia concentration were measured by ion chromatography after column concentration.

In the mixed-bed resin bed using the present invention, the space velocity S
V30, when water is passed at a water temperature of 25 ° C, 6 minutes from the start of water flow
The concentration of trimethylamines in the passing pure water (outlet water) after time is generally 10 ppt or less. When the space velocity is increased to SV100, the concentration of alkylamines is diluted with pure water to 50 ppt or less. The mixed bed type ion exchange resin of the present invention is an aqueous solution containing an ionic substance, charged fine particles, a coloring substance, a radioactive substance, a polymer electrolyte, an organic solvent, an aqueous solution thereof, a gas phase, and desalination, filtration, ionization. Used for exchange reaction, adsorption and purification. For example, ultrapure water for semiconductor production where high water quality is required, for the production of medical water, for the production of demineralized water for nuclear power,
In addition, it is also used as a mixed bed resin for general purpose desalination. The mixed bed type ion exchange resin has little elution from the resin even at a high temperature, and can be suitably used for desalination at a high temperature. Conventionally, high-temperature ultrapure water is produced by a heat exchanger, but the mixed-bed resin of the present invention increases the amount of elution from the resin as compared with room temperature. Normally, ultrapure water up to 70 ° C. is produced, but if the amount of elution does not matter, water can be passed at 90 ° C. When water is passed through the mixed bed resin bed of the present invention at a space velocity of SV30 and a water passing temperature of 90 ° C., the elution amount (TOC) from the resin is 10 ppb or less.

[0034]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. Example 1 A free-form anion exchange resin (produced according to Production Example 2 of JP-A-4-349941) was prepared by reacting trimethylamine with a crosslinked copolymer of 4-bromobutylstyrene and industrial grade divinylbenzene. Formed with quaternary ammonium group, neutral salt decomposition capacity 0.85me
q / mL-OH form) and a free sulfonic acid type cation exchange resin (Diaion SKT 10L, neutral salt decomposition capacity 1.80 meq / mL-H form, Diaion is a registered trademark of Mitsubishi Chemical Corporation) Was used to form a mixed bed type ion exchange resin bed as follows.

In a beaker containing deionized water, 224 mL of the anion exchange resin and 106 mL of the cation exchange resin were mixed, and this was mixed with a glass column containing deionized water (22.
(9 mmφ × 100 cm), the resin was slowly flowed so as not to be separated to form a mixed-bed ion exchange resin bed. The bed height of the resin bed was 82 cm. Example 2 The same anion exchange resin as used in Example 1 was placed in a beaker containing deionized water, and polystyrene sulfonic acid having an average molecular weight of 1 × 10 ⁴ was added thereto with stirring. The amount of the sulfonic acid group based on the anion exchange resin is 0.15me.
q / L-resin. This resin slurry was poured into a column, and desalinated water was passed through to sufficiently wash with water. A mixed bed type ion exchange resin bed was formed in exactly the same manner as in Example 1 except that this anion exchange resin treated with polystyrene sulfonic acid was used. The layer height of the resin bed was 80 cm.

COMPARATIVE EXAMPLE 1 165 ml of a free anion exchange resin (Diaion SA12A) having a trimethylaminomethyl group as an ion exchange group, and Diaion SKT10L106m
A mixed bed type ion exchange resin bed was formed in exactly the same manner as in Example 1 except that L was used. The height of the resin bed is 74cm
Met.

Example 3 A free form of anion exchange resin (produced in accordance with Production Example 3 of JP-A-4-349941) was prepared by reacting trimethylamine with a crosslinked copolymer of 6-bromohexylstyrene and industrial grade divinylbenzene. Quaternary ammonium group formed by neutral salt exchange capacity 0.66me
q / mL-OH form) was treated with polystyrene sulfonic acid in exactly the same manner as in Example 2. 210 mL of this anion exchange resin and 106 mL of Diaion SKT10L
A mixed bed type ion exchange resin bed was formed in exactly the same manner as in Example 1 except that

Example 4 An anion exchange resin obtained by reacting trimethylamine with a crosslinked copolymer of 4-bromobutoxystyrene produced according to Production Example 1 of JP-A-7-291882 and industrial grade divinylbenzene was used. The free form was treated with polystyrene sulfonic acid exactly as in Example 2. A mixed bed type ion exchange resin bed was formed in exactly the same manner as in Example 1 except that 290 mL of this anion exchange resin and 106 mL of Diaion SKT10L were used.

Example 5 The same anion exchange resin as used in Example 1 was placed in a beaker containing deionized water, and the average molecular weight was 1 × 10 ^4.
Of sodium polystyrene sulfonate was added with stirring. The amount of the sulfonic acid group based on the anion exchange resin was 0.4 meq / L-resin. This resin slurry was poured into a column, and desalinated water was passed through to sufficiently wash the column. A mixed bed type ion exchange resin was formed in exactly the same manner as in Example 1 except that this anion exchange resin treated with sodium polystyrene sulfonate was used. The height of the resin bed is 80
cm.

Ultrapure water flow test (1) Ultrapure water was passed through the mixed bed type ion exchange resin bed formed in Examples 1, 2, 5 and Comparative Example 1 at 25 ° C. by SV30, The quality of the effluent when the condition was reached was evaluated. The results are shown in Table 1.

[0041]

[Table 1]

* 1 Measured with DKK AQ-11 * 2 Measured with Anatel A-1000XP * 3 Particle size 0.05 with HORIBA PLCA-310
Measurement of a particle larger than μm Electrolyte aqueous solution test: An aqueous electrolyte solution (conductivity: 238 μS / cm) containing 50 ppm of calcium chloride and 50 ppm of sodium chloride was applied to the mixed-bed ion exchange resin beds formed in Examples 1 to 5 by SV20. And the resistivity of the water flowing out was measured. The outflow water of each ion exchange resin bed had a specific resistance of 18.0 MΩ · cm.

Ultrapure water flow test (2): The same ultrapure water as in the water test (1) was passed through the ion-exchange resin bed formed in Example 1 at 40 ° C., 70 ° C. and 90 ° C. by SV30. Water was drained and the quality of the effluent was evaluated. Table 2 shows the results.

[0044]

[Table 2]

Test for generation of fine particles from ion exchange resin;
Each column was filled with the anion exchange resin of Example 2 treated with polystyrene sulfonic acid and the Diaion SA12A used in Comparative Example 1, and charged into ultrapure water (resistivity 1).
8.25 MΩ · cm, TOC 0.50 ppb, number of fine particles <1 (particles / mL)) were flowed through SV30. The quality of the effluent is shown in Table-3.

[0046]

[Table 3]

Example 6 Production of 4- (4-bromobutyl) styrene A nitrogen gas introducing pipe, a Dimro cooling pipe, a constant pressure dropping funnel with a branch pipe, a mercury thermometer, and a jacket 3 equipped with a stirring blade
136.1 g of metallic magnesium in an L (liter) reactor
{5.60 gram atom, 1.40 equivalents / 4-chlorostyrene (hereinafter abbreviated as PCST)} was added, the atmosphere was sufficiently replaced with nitrogen gas, and the jacket temperature was set at 20 ° C. On the other hand, 808 g (2.8 equivalents / PCST) of dry tetrahydrofuran (THF), 737 g (2.0 equivalents / PCST) of dry toluene, and 554 g (4.0 g) of dry 4-chlorostyrene (PCST) were placed in a dropping funnel with a branch pipe. Mol) was prepared. First, add 40 ml of dry THF,
When a THF-toluene solution of ST (30 ml) was added dropwise and 0.3 ml of 1,2-dibromoethane was added dropwise thereto, the solution foamed and ethylene was generated, and at the same time, the internal temperature was temporarily increased to 38 ° C. After a few minutes, the solution turns light gray-green
After a minute a dark green solution resulted. The solution was dropped continuously for 3 hours so that the temperature of the solution became 28 ° C, and the jacket temperature was adjusted so that the internal temperature became 28 ° C. After dropping and aging for 3 hours, the PCST of the raw material decreased to 0.3% or less (HPLC analysis). The prepared Grignard reagent was cooled to 10 ° C. and subjected to the next step Grignard reaction.

For a Grignard reaction, a jacketed 5 L reactor equipped with a nitrogen gas inlet tube, a Dimro cooling tube, a mercury thermometer, a stirring blade, and a Grignard solution dropping tube was replaced with dry nitrogen. On the other hand, THF 58 g (0.2 equivalent / PCS
T), 8.1 g of catalyst CuCl ₂ (0.06 mol, 1.5 mol% / PCST) and 5.0 g of LiCl (0.12 mol,
(3.0 mol% / PCST) and dissolved. Furthermore, 1,4
3454 g (16.0 mol, 4.0 equivalents / PCST) of dibromobutane was added, and the mixture was cooled to 10 ° C. Into this, about 20 ml of the Grignard reagent prepared above was first added dropwise over 3 hours so that the internal temperature did not exceed 15 ° C., and the solution turned from an orange transparent solution to a dark (black) green It became a clear solution. After dropwise addition of all Grignard reagents, the mixture was stirred at 15 ° C. for 2 hours to complete the reaction. After aging,
19.2 g of methanol was dropped into the solution to stop the reaction. The yield of the desired product, 4- (4-bromobutyl) styrene, was 86%. Other components are 0.24% of 4,4′-divinylbiphenyl, 1,4-bis (vinylphenyl)
Butane 6.9%, styrene 2.4%, vinylphenol 0.3%.

Demineralized water was added to the above reaction mixture, the mixture was allowed to stand for separation, and the aqueous phase was removed. Under reduced pressure, the solvent THF and toluene, and styrene partially generated in the reaction were removed. After removing the 1,4-dibromobutane used in a large excess, finally, the desired product, 4- (4-bromobutyl) styrene (slightly yellowish transparent solution, boiling point 105 ° C./40 Pa) was obtained. . The obtained 4- (4-bromobutyl) styrene (BB
The purity of S) was 97%, and the impurities were 1,4-bis (vinylphenyl) butane 0.7%, 4,4'-divinylbiphenyl 0.2%, 4-vinylphenol 0.08%,
4-Dibromobutane was 1.8%.

The purified monomer was further added to a silica gel packed in a column (7% loading based on the monomer).
To remove 4-vinylphenol, and the content was reduced to 10 ppm or less. 2 L of a 20% CaCl2 aqueous solution and a solution prepared by adjusting PVA (manufactured by GM-20 Kuraray) to be a 0.7% aqueous solution were placed in a 3 L baffled polymerization vessel. To this solution, a monomer solution was prepared by adding 465 g of 4-bromobutylstyrene purified by the above silica gel, 35 g of 80% divinylbenzene, and 2.3 g of benzoyl peroxide. After stirring at 120 rpm for 1 hour at room temperature using an anchor type stirring blade, the temperature was raised to 80 ° C. for 1 hour. After stirring at 80 rpm at 100 rpm for 8 hours, the solution was cooled. A part of the obtained polymer was taken out and dried, and the polymerization yield was measured.

50 g of the obtained polymer was placed in a flask, 300 g of toluene was added, and the mixture was stirred at room temperature for 2 hours.
After completion, the toluene solution was filtered on a Nutsche, then returned to the flask, 200 g of toluene was added, and the mixture was stirred at room temperature for 2 hours. This operation was repeated two more times to extract unpolymerized monomers and impurities. Finally, the toluene was filtered on a Nutsche.

In a 500 ml four-necked flask equipped with a cooling tube, 50 g of the above resin, 50 ml of toluene, and 200 ml of a 30% aqueous solution of trimethylamine were added.
The temperature was raised to 50 ° C., and the mixture was stirred for 5 hours. After the reaction, the polymer was taken out and washed with water. The polymer was packed in a column, 5 volumes of MeOH were passed through SV1, and demineralized water was further added to 5 BV
Water passed.

The following treatment was carried out to convert this resin from a bromide ion form to a regenerated form. First, a 5% aqueous solution of sodium chloride, which was 20 times the amount of the resin, was passed, and then 5 volumes of ultrapure water were passed. Further, a 50% aqueous solution of 5% sodium hydrogen carbonate was passed through the resin, and 10 volumes of ultrapure water were passed through. Further, a 2N-sodium hydroxide aqueous solution was passed 50 times by volume with SV5, and 10 volumes of ultrapure water were passed.

The obtained resin was placed in a flask, and a 5-fold aqueous 1N-NaOH solution was stirred at 90 ° C. for 5 hours. The resin is taken out, packed in a column, and 1N-NaOH
10 volumes of the aqueous solution were passed, and then ultrapure water was passed until the pH of the outlet water became neutral. Further, 20 volumes of special grade methanol were passed at room temperature with SV2. Finally, rinse with ultrapure water,
An ultrapure water specification anion exchange resin was used. The neutral salt decomposition ability was 1.03 meq / mL (OH form), and the water content was 61% (OH form). Test Example-1 Ultrapure water evaluation The resin of Example 5 was used as the resin for ultrapure water. Diaion ^R SMT100 the (Mitsubishi Chemical) was used as a comparative example 2.

The resin of Example 6 was packed in a column having an inner diameter of 30 mm (column length of about 78 cm), and was added to ultrapure water (TO
0.5 ppb) were passed through SV30. The concentration of alkylamines in the column outlet water was determined by ion chromatography. The results are shown in Table 6 (SV30). Test Example-2 Method for Analyzing Amines In a class 1000 clean room, an ion chromatography apparatus was installed in an online environment in which ultrapure water did not come into contact with outside air. Various ions in the ultrapure water of the column outlet water are captured by ion exchange resin, concentrated and eluted with an eluent.
It was measured with an electric conductivity detector. The empty tower in Table 4 means that ultrapure water is charged into a column not packed with mixed bed resin at a space velocity SV30
The amine concentration of the outlet water when water was passed was shown. The unit of the amine concentration in Table 4 is ppt. Although each amine is detected as an ammonium salt, it is described in Table 4 as a free form.

[0056]

[Table 4]

[0057]

The mixed bed type ion exchange resin of the present invention can not only reduce the generation of fine particles from the resin but also reduce the alkylamine concentration by neutralizing at least the surface of the anion exchange resin with a polymer electrolyte. Can be reduced to the limit. Further, even at high temperatures, there is little elution from the resin, and it is optimal not only for the production of ultrapure water at room temperature but also for the production of hot water or high-temperature ultrapure water. Ultrapure water using the anion exchange resin produced according to the present invention is expected to greatly improve the product yield in semiconductor production. According to the present invention, this effect is remarkable in semiconductor manufacturing applications requiring high-quality pure water.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toyoka Sugawara 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu City, Fukuoka Prefecture Inside the Kurosaki Office of Mitsubishi Chemical Corporation (72) Inventor Masako Yasutomi 1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu City, Fukuoka Prefecture No. 1 Mitsubishi Chemical Corporation Kurosaki Plant F-term (reference) 4D025 AA04 AA10 AB02 AB03 AB34 AB36 AB39 BA08 BA13 BB04 CA06 CA08 4J002 BC10W BC12X GD01

Claims (13)

[Claims] 1. A mixture of an anion exchange resin having a repeating unit represented by the general formula (1) and a cation exchange resin having a repeating unit represented by the general formula (2). Mixed bed ion exchange resin bed. Embedded image (In the formula, A is an alkylene group having 3 to 8 carbon atoms or 4 carbon atoms.
To B-8, and B represents a primary to tertiary amino group or a quaternary ammonium group. B
Represents a secondary or tertiary amino group or a quaternary ammonium group, the organic group bonded to the nitrogen atom is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. ) 2. The blend according to claim 1, wherein the anion exchange resin having a repeating unit represented by the general formula (1) has a repeating unit represented by the general formula (3). Bed type ion exchange resin bed. Embedded image (In the formula, A is an alkylene group having 3 to 8 carbon atoms or 4 carbon atoms.
To R 8, R ¹ , R ² and R ³ each independently represent an alkyl group having 6 or less carbon atoms or a hydroxyalkyl group. ) 3. An anion exchange resin having a repeating unit represented by the general formula (1) comprises 1 to 99 mol% of the repeating unit represented by the general formula (1) and 0.1 to 0.2 mol of a divinylbenzene unit as a crosslinking group. 3. The mixed bed type ion exchange resin bed according to claim 1, wherein the mixed bed ion exchange resin bed consists essentially of 1 to 50 mol%. 4. An exchange capacity ratio of an anion exchange resin having a repeating unit represented by the general formula (1) and a cation exchange resin having a repeating unit represented by the general formula (2) of 1:10 to 1:10. The mixed bed type ion exchange resin bed according to any one of claims 1 to 3, wherein the mixed bed is formed so as to be mixed at a ratio of 10: 1. 5. An anion exchange resin having a repeating unit represented by the general formula (1), which is treated with a water-soluble polymer having an anionic dissociable group, wherein the content of the anionic dissociable group is 0. The mixed bed type ion exchange resin bed according to any one of claims 1 to 4, wherein the mixed bed type ion exchange resin bed is a 0.02 to 1.0 meq / L-OH type resin. 6. The water-soluble polymer having an anionic dissociable group is polystyrene sulfonic acid,
The mixed bed type ion exchange resin bed according to claim 5. 7. The mixed-bed ion exchange according to claim 5, wherein the water-soluble polymer having an anionic dissociable group has a number average molecular weight of 1 × 10 ³ to 1 × 10 ^6. Resin floor. 8. The cation exchange resin having a repeating unit represented by the general formula (2) is treated with a water-soluble polymer having a cationic dissociable group, and the content of the cationic dissociable group is 0. The mixed bed type ion exchange resin bed according to any one of claims 1 to 7, wherein the mixed bed type ion exchange resin bed is a 0.22 to 0.5 meq / LH type resin. 9. A method for purifying a liquid to be treated, wherein the liquid to be treated is passed through the mixed bed type ion exchange resin bed according to any one of claims 1 to 8. 10. A resin having a repeating unit represented by the general formula (1) and being treated with a water-soluble polymer having an anionic dissociable group, wherein the content of the anionic dissociable group is 0. 0.2 to 0.5 meq / L-OH resin. Embedded image (In the formula, A is an alkylene group having 3 to 8 carbon atoms or 4 carbon atoms.
To B-8, and B represents a primary to tertiary amino group or a quaternary ammonium group. B
Represents a secondary or tertiary amino group or a quaternary ammonium group, the organic group bonded to the nitrogen atom is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. ) 11. The anion exchange resin essentially comprises 1 to 99 mol% of a repeating unit represented by the general formula (1) and 0.1 to 50 mol% of a divinylbenzene unit which is a crosslinking group; The water-soluble polymer having an anionic dissociable group is polystyrenesulfonic acid having a number average molecular weight of 1 × 10 ³ to 1 × 10 ^6.
Anion exchange resin as described. 12. When water is passed through a mixed bed resin under the conditions of a space velocity SV30 and a water passing temperature of 25 ° C., the concentration of alkylamines in pure water passing therethrough after 6 hours from the start of water passing is 10 p.
The mixed bed type ion exchange resin bed according to any one of claims 1 to 8, wherein the bed is not more than pt. 13. The mixed bed ion exchange according to claim 1, wherein TOC is 10 ppb or less when water is passed under a space velocity SV30 and a water passing temperature of 90 ° C. Resin floor.