JPS60190414A - Production of gel particle polymer - Google Patents

Abstract

PURPOSE:An alkali metal salt of an aromatic sulfonated dicarboxylic acid and a compound bearing NCO group are allowed to react by a specific method to produce the titled polymer in balls with high heat resistance directly, which is useful as a heat-resistant ion-change resin. CONSTITUTION:In the presence of (A) an aliphatic hydrocarbon, (B) an aprotonic polar solvent which is inmiscible with component A and dissolving or swelling the particle polymer before gelling and (C) a dispersion stabilizer soluble in component A, (D) a compound of the formula (Ar is trivalent aromatic group; M is alkali or alkaline earth metal), preferably 3,5-dicarboxybenzenesulfonate sodium salt, and (E) a compound bearing 2 or more isocyanate groups, when necessary, (F) a compound of bearing 2 or more carboxyls and/or acid anhydride groups are allowed to react with one another until the polymer formed becomes insoluble in solvent B to give the objective polymer in the form of a dispersion in component A.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a gelled particulate polymer useful for heat-resistant ion exchange resins etc. obtained by a non-aqueous dispersion polymerization method.

(Prior art) The inadequacy of introducing sulfonic acid groups having ion exchange ability into heat-resistant resins such as aromatic polyamide resins and aromatic polyamideimide resins is disclosed in Japanese Patent No. 44-11168 and Japanese Patent Publication No. 45-34776. It is described in the official gazette and Japanese Patent Publication No. 51-6770. These are intended to improve the glossiness and dyeability of fibers.

In addition, the use of polyamideimide resin into which sulfonic acid groups have been introduced as an ion exchange resin was disclosed in Japanese Patent Application Laid-Open No. 58-16.
It is described in Publication No. 3445.

Ion exchange resins used in metal ion adsorbents9 reaction catalysts are usually spherical in shape in terms of ion exchange capacity9mechanical strength, infusibility and insolubility against heat and solvents, and gelation (three-dimensional (building bridges) is required.

5- However, since the above-described conventional heat-resistant resin into which sulfonic acid groups have been introduced can only be obtained by solution polymerization, the resulting resin is substantially linear.

It can only be obtained from a resin solution dissolved in synthesis solvents such as N-methylpyrrolidone and dimethylacetamide. Synthesizing a gelled resin by a solution polymerization method is not industrial in that it is impossible to reuse the reaction vessel. In addition, a method for obtaining 9 spherical particles by pouring a resin solution obtained by solution polymerization into water in the form of droplets and removing the solvent is disclosed in Japanese Patent Application Laid-Open No. 58-1634.
It is described in Publication No. 45. However, this method requires a complicated process to obtain spherical particles, and since the resin of the obtained spherical particles is substantially linear, it is necessary to maintain the spherical shape (to avoid fusion between particles, etc.). ) desolvation requires an industrially extremely uneconomical process.

(Object of the invention) The present inventors have discovered that the shape without such defects is spherical,
6- It is an object of the present invention to provide a method for producing a gelled particulate polymer having excellent heat resistance using a direct synthesis system.

(Structure of the invention) The present invention is.

(al: aliphatic hydrocarbons (bl: aprotic polar solvents that are essentially immiscible with aliphatic hydrocarbons and soluble or swellable with respect to the formed particulate polymer before gelation; (C) A compound represented by the formula HOOC-A r -C0OH in the presence of a dispersion stabilizer soluble in aliphatic hydrocarbons.

OaM A compound (1) containing a divalent or higher in7anate group and optionally a compound (11) containing a divalent or higher carboxyl group and/or an acid anhydride group, (1) and (11). At least one of them is a compound with a valence of 3 or more, and the resulting particulate polymer is reacted until it becomes insoluble in an aprotic polar solvent, and is dispersed in an aliphatic hydrocarbon to form a gelled particulate polymer. The present invention relates to a method for producing a gelled particulate polymer.

Examples of aliphatic hydrocarbons in the present invention include 9, for example, n-
Hexane, octane, dodecane, liquid paraffin, l5
OPAR-E, l5OPAR-H, l80PAR-K (
The above are product names manufactured by Etsuzo Standard Oil Company.

Petroleum-based saturated aliphatic or alicyclic hydrocarbons having a boiling point range of about 40 to 300°C are used. Considering the reaction temperature, those having a boiling point of 80° C. or higher are preferred. These may be used alone or in combination.

Aliphatic hydrocarbons are essentially immiscible in aprotic polar solvents and insoluble in the resulting particulate polymer; liquid).

In the present invention. The aprotic polar solvent that is essentially immiscible with aliphatic hydrocarbons and soluble or swellable with the generated particulate polymer before gelation is at least represented by the above formula. It is preferable to use a solvent that dissolves the compound, contacts the reaction between the end groups during the polymerization reaction process, and acts as a solvent to increase the molecular weight of the resulting polymer. Here, "essentially immiscible with aliphatic hydrocarbons" means not only completely insoluble in aliphatic hydrocarbons, but also those which are not completely insoluble in aliphatic hydrocarbons, but which are compatible with two liquids at a certain mixing ratio. This is meant to include those that are immiscible to the extent that phase separation occurs. Examples of such aprotic polar solvents include N-methylpyrrolidone, N-vinylpyrrolidone, dimethylformamide, dimenalacetamide, ε-caprolactone, γ-butyrolactone, nitrobenzene, and nitrotoluennate. These may be used alone or in combination.

Considering the solubility and safety of the compound represented by the above formula, aprotic basic polar solvents are preferred, and N-methylpyrrolidone is particularly preferred. The aprotic polar solvent forms a dispersed phase with the resulting particulate polymer to maintain the shape of the particles in a spherical form. It has the function of an agent.

The dispersion stabilizer used in the present invention is soluble in aliphatic hydrocarbons, forms a stabilizing layer on the surface of the resulting particulate polymer, and at least stabilizes the dispersion state of the particles during the polymerization process. It can be used as long as it has the function to do so, and there is no limit to 9%.

Examples of such dispersion stabilizers include 9, for example, a polymer that becomes a dispersed phase or a reactant solution that forms a polymer (a compound represented by the above formula, a compound formed from the above compound (Yamakai and an aprotic polar solvent), A resin is used that shares a first organic component that has an affinity for the solution) and a second organic component that is soluble in the aliphatic hydrocarbon that forms the continuous phase.

The dispersion stabilizer contains lauryl methacrylate, stearyl methacrylate, lauryl acrylate or stearyl methacrylate as a second organic component soluble in aliphatic hydrocarbons and glycidyl methacrylate, methacrylate as a first organic component that has an affinity for the dispersed phase. 2-hydroxyethyl acid.

Random copolymers with glycidyl acrylate and/or -210-human-1xethyl acrylate are preferred.

The molecular weight of this random copolymer dispersion stabilizer is 60.
It is preferable that it is 00 or more. When the molecular weight is less than 6,000, aggregation tends to occur during the polymerization process. Molecular weight is 600
A range of 0 to 300,000 is considered to be more preferable. The molecular weight of the dispersion stabilizer can be measured using, for example, a gel permeation chromatography method using polystyrene of known molecular weight as a calibration curve.

Also, the dispersion stabilizer is a random copolymer.

The molar ratio of the first organic component and the second organic component is 1/1 to 1.
It is preferable to react within the range of /6.

If it is less than 1/6, the dispersion stabilizer cannot bond with the particulate polymer to be produced, and as a result, a stabilizing layer cannot be formed on the particle surface of the dipolymer, which tends to cause aggregation. Also.

If the ratio exceeds 1/1, the resulting particulate polymer may undergo undesirable gelation.

The compound represented by the formula HOOC-A r-COOH used in the present invention is, for example, 3,5-dicarboxybenzenesulfone [
, 2,5-dicarboxybenzenesulfonic acid, 2゜6
- aromatic sulfonated dicarboxylic acids such as sulfonated benzene dicarboxylic acids such as dicarboxybenzenesulfonic acid, sulfonated naphthalene dicarboxylic acids such as 3-sulfoxy-thronaphthalene dicarboxylic acid, and 3-sulfoxy-2,6-naphthalene dicarboxylic acid; Alkali metal salts or alkaline earth metal salts are used. Alkali metals and l~
For example, lithium, sodium, potassium, etc.
As the alkaline earth metal, for example, calcium is used. Considering cost and reactivity, sodium 3,5-dicarboxybenzenesulfonate is preferred.

Examples of the divalent or higher isocyanate group-containing compound (1) used in the present invention include 9, for example, tolylene diisocyanate, xylylene diincyanate), 4,4'-diphenyl ether diincyanate, aromatic diisocyanates such as naphthalene-1,5-diisocyanate), 4,4'-diphenylmethane diisocyanate, ethylene diisocyanate),
Aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate), 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutene 1,3-diinocyanate, cyclohexane 1,3
- and alicyclic diisocyanates such as 1,4-diisocyanate and isophorone diisocyanate.

Examples of trivalent or higher incyanate group-containing compounds include 1, for example, isocyanurate ring-containing polyincyanate obtained by the trimerization reaction of the above-described divalent incyanate group-containing compound, and triphenylmethane-4,44"-triyne. cyanate, polyphenylmethyl polyisocyanate represented by the formula (integer of about 5 to 5), etc. are used. Considering heat resistance, cost, etc., as a divalent incyanate group-containing compound, 4,4'-diphenylmethane diisocyanate is used. , 4.4'-diphenyl ether diisocyanate, tolylene diisocyanate are preferred,
4.4 as a trivalent or higher incyanate group-containing compound
The isocyanurate ring-containing polyicanate obtained by trimerization reaction of 4,4'-diphenyl ether diisocyanate or tolylene diisocyanate, and the above-mentioned polyphenylmethyl polyincyanate are preferred.

These divalent or higher incyanate group-containing compounds control the reaction rate during the polycondensation reaction process and are used in combination with methanol, n-butanol, benzyl alcohol, ε-caprolactam, methyl ethyl ketone oxime, Phenol.

It is also possible to use a polymer partially or completely stabilized with a suitable blocking agent having one active hydrogen in the molecule, such as cresol.

The divalent or higher carboxyl group- and/or acid anhydride group-containing compound (11) used as necessary in the present invention is 1. For example, the divalent carboxyl group- and/or acid anhydride group-containing compound is terephthalic acid; Isophthalic acid, 2
．． 5-. 2.6- or 3,6-dicarboxytoluene,
2.6-dicarboxynaphthalene, 3.3'-also c4.
4'-dicarboxybiphenyl.

Bis(3- or 4-carboxyphenyl)ether, bis(3- or 4-carboxyphenyl)ketone, bis(
3- or 4-carboxyphenyl) sulfone, bis(3
- or 4-carboxyphenyl) methane, bis(3- or 4-carboxyphenyl) dimethylmethane, succinic acid, adipic acid.

Dicarboxylic acids such as sebacic acid and dodecanedicarboxylic acid,
Tricarboxylic acid anhydrides such as trimellitic anhydride, 1,2.4-butanetricarboxylic acid-1,2-anhydride, 3,4.4'-benzophenonetricarboxylic acid-3,4-anhydride, 1, 2,3.4-butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, ethylenetetracarboxylic acid, bicyclo-[2,2+2]-octo-(carene-
2:3,5:6-tetracarboxylic acid, pyromellitic acid,
3. a: 4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 2
, 3,6.7-naphthalenetetracarboxylic acid, 1,2,
5.6-Naphthalenetetracarboxylic acid, ethylene glycol bistrimelitate.

2.2-bis(3,4-biscarboxyphenyl)propane, 2.2:3.3'- or 3.3:4.4'-biphenyltetracarboxylic acid, perylene-3,4,9,1
0-tetracarfonic acid, his-3,4-dicarboxyphenylsulfone, 2,2-bis[4-(2,3-sense is 3
,4-dicarpoxyphenoxy)phenyl]furopane.

4-(2,3-dicarboxyphenoxy)-4'-(3
,4-dicarboxyphenoxy)-diphenyl-2,2
Dianhydrides of tetrabasic acids such as -propane, thiophene-2,3,4,5-tetracarboxylic acid, and pyrazinetetracarboxylic acid are used.

Compounds containing trivalent or higher carboxyl groups and/or acid anhydride groups include trimellitic acid, trimesic acid, tris(
Polycarboxylic acids such as 2-carboxyethyl) isocyanurate, nitrilotriacetic acid, nitrilotripropionic acid, and citric acid are used. In consideration of heat resistance, cost, etc., isophthalic acid, trimellitic anhydride, and trimesic acid are preferred.

In the present invention, the above-mentioned compound (1) containing an isocyanate group with a valence of 2 or more and the carboxyl group and/or acid anhydride group-containing compound (11) with a valence of 2 or more used as necessary are used.
), a trivalent or higher valent compound is used for at least one of them. That is, the trivalent or higher-valent compound is a branching component of the gelled particulate polymer in the present invention, and has the function of three-dimensionally crosslinking the bipolymer.

A preferred combination of the above compound (1) and compound (11) is 1, for example, divalent compound (1) and trivalent compound + 11. divalent compound (11) and trivalent compound (1).
Only monovalent compound (1), divalent compound (1) and 3
valent compound (II), divalent compound (1), tli)
and trivalent compound ti11. Examples include trivalent compound (1) and trivalent compound (11).

17- A compound represented by the above formula and the above compound (I).

(11) means that the ratio of all incyanate groups to all carboxyl groups and/or acid anhydride groups is 0.65 to 2.0, (
(equivalent ratio). In order to avoid leaving free carboxyl groups, acid anhydride groups, or incyanate groups in the resulting gelled particulate polymer, it is preferable to use approximately equivalent amounts.

In addition, the compound having a valence of 3 or more is the above compound (11 if the total incyanate group is 5), the above compound (Ill if the total carboxyl group and/or acid anhydride group is 5, respectively)
It is preferable to use it in small quantities.

If the amount is less than 5 equivalents, gelation will be insufficient.

Aliphatic hydrocarbons are compounds represented by the above formula.

50 to 3 for the total amount of the above compounds K) and (11)
It is preferable to use it within a range of 0.00 weight. From the viewpoint of production efficiency and cost, the content is particularly preferably 200% by weight or less.

The aprotic polar solvent is 1°18 with respect to the total amount of the compound represented by the above formula and the above compounds (1) and (11).
- It is preferable to use it in the range of 150% by weight.

If it exceeds 150% by weight, it tends to aggregate during the synthesis process, which is disadvantageous in terms of cost. If it is less than 10% by weight, it is insufficient to dissolve the compound represented by the above formula.

The dispersion stabilizer is a compound represented by the above formula, compound (1)
It is preferably used in an amount of 0.1 to 20% by weight based on the total amount of (11) and (11). In consideration of heat resistance and cost, a 10-weight board is particularly preferable.

In the present invention, the resulting particulate polymer is reacted until it becomes insoluble in an aprotic polar solvent to form a gelled particulate polymer dispersed in an aliphatic hydrocarbon.

The reaction temperature is preferably 80 to 250°C.

Preferably, the polymerization reaction is carried out in substantially anhydrous conditions. Therefore, it is desirable to carry out the process under an inert atmosphere such as nitrogen gas. As a matter of course.

The gelled particulate polymer obtained by the production method of the present invention uses water as a dispersion medium because the above incyanate group-containing compound (1) is quickly transformed into an inert compound when it comes into contact with water. It is impossible to manufacture as In the reaction, all the raw materials may be charged at the same time, or one reaction may be carried out in stages depending on the purpose.

A solution obtained by heating and dissolving the compound represented by the above formula or the above trivalent or higher valent compound in an aprotic polar solvent in advance is heated at a reaction temperature from room temperature to around 100°C, and then the aliphatic hydrocarbon didispersion stabilizer and the above compound are heated. A liquid mixture containing (1) and (11) or an aliphatic hydrocarbon.

A method of adding a dispersion stabilizer and the above-mentioned compounds (1) and (11) to a mixed solution containing a divalent or less compound is preferred as a method for stably producing spherical particles.

The stirring method used in the reaction involves high-speed shearing using an emulsifier (homomixer).

Mechanical cutting of particles with a propeller-type stirrer.

A stirring method that does not involve pulverization is used.

The emulsifier is preferably used in areas where the conversion of reactants to polymer is not very high. A desirable stirring method is to use an emulsifier to reduce the particle size at the beginning of the reaction, and then use a propeller-type stirrer to proceed with the reaction at a point near the polymerization rate where the dispersion stability of the particles is good. . According to this method, a gelled particulate polymer having a relatively small particle size and uniform particle size can be obtained. Depending on the synthesis system, it is also possible to use an emulsifier to form small particles before the reaction.

The gelled particulate polymer in nature has an average particle size of 0.
．． It is obtained in approximately spherical particle morphology ranging from 0.05 to 2000 μm and above.

The recovery and purification of the gelled particulate polymer dispersed in the aliphatic hydrocarbon obtained according to the present invention is generally carried out by well-known methods. For example, the gelled particulate polymer separated and recovered from aliphatic hydrocarbons by filtration may be directly heated to desolvent at 200 to 250°C, or a washing solvent miscible with an aprotic polar solvent (e.g., water, The solvent can be removed by boiling and washing with alcohols, ketones, ethers).

The gelled particulate polymer obtained by the present invention can be heated,
It is insoluble and insoluble in solvents and can be easily removed.

The gelled particulate polymer in the present invention has a sulfonic acid group having ion exchange ability, and is usually used as a sulfonic acid group treated with hydrochloric acid.

The main core of the bipolymer is polyamide or polyamideimide, and has the shape of a single spherical particle.

It can be used at high temperatures of 200°C or higher.

It has sufficient mechanical strength to adsorb metal ions in nuclear wastewater, which requires use at high temperatures and high pressures.

Since it is infusible and insoluble with respect to heat and solvents, it is also useful as a reaction catalyst at high temperatures and in polar solvents.

(Example) The present invention will be explained below using comparative examples and examples.

Example 1 (1) Synthesis of dispersion stabilizer A thermometer, a stirrer, and a four-tube cooler equipped with a 9-ball tube cooler were filled with l5OPAR-H (aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) 1529° Lacryl. Add 87.59 g of methacrylate and 20.59 g of 2-hydroxyethyl methacrylic acid, io.

The temperature was raised to ℃. While passing nitrogen gas, lauryl methacrylate 87.09. 2-Hydroxyethyl methacrylate 5.09. Benzoyl peroxide paste (benzoyl peroxide content 50% by weight) 2.09
The mixture was added dropwise over 2 hours while stirring. Subsequently, 1100 g of Isopm-) was added dropwise at the same temperature, and after the completion of one drop, the temperature was raised to 140°C and reacted for 2 hours. This dispersion stabilizer solution had a nonvolatile content of 40% by weight and 31% when dried at 170°C for 2 hours, and the number average molecular weight of the dispersion stabilizer (gel permeation chromatography method using polystyrene of known molecular weight as a calibration curve) (The same applies hereafter) is 7
It was 0.000.

(2) Synthesis of gelled particulate polymer While passing nitrogen gas through a 500 ml four-bottle flask equipped with a thermometer, a stirrer, and a bulb-and-tube condenser, 4°4'-diphenylmethane diisocyanate) 46.79゜Dispersion stabilizer solution obtained in (1) (nonvolatile content 40% by weight) 5 g, l80PAR
-H1509 was added, and the temperature was raised to 90° C. while stirring at 380 r and I) 6 m. By the way.

Pre-prepared sodium 3,5-dicarboxybenzenesulfonate 259 and trimesic acid 13.19 were mixed with N
-Add a heated solution of methylpyrrolidone 809 to 105°C for 1 hour, 120°C for 3 hours, and 150°C for 1 hour.
After reacting for 2 hours at 170°C, the bipolymer becomes N
- After confirming that it was insoluble in methylpyrrolidone, it was cooled. A dark yellow gelled particulate polymer dispersed in the continuous phase 15OPAR-H was obtained, which was recovered by filtration and further boiled in methanol twice to remove nitrogen.
-Methylpyrrolidone and then dried at 80° C. for 7 hours under reduced pressure. The shape of this gelled particulate polymer was spherical, and even when immersed in N-methylpyrrolidone at 150°C, it did not dissolve and remained spherical. The main particle diameter is approximately 1
It was 30 to 160 μm. Furthermore, in the infrared absorption spectrum, absorption of amide groups was observed at 1650 mark-1 and 1540 cm'. FIG. 1 shows a scanning electron micrograph (150 times magnification) of the gelled particulate polymer obtained.

Example 2 Example 1, (Using the same equipment as in 21 and passing nitrogen gas, Millionate MR-100 (trade name, polyphenylmethyl polyisocyanate, manufactured by Nippon Polyurethane Industry Co., Ltd.)) 38G, Example 1, ( Dispersion stabilizer solution obtained in step 11 (non-volatile content 40% by weight) 4.59゜l5OPAR
-H1379 was added and the temperature was raised to 90°C while stirring. A solution of 37.59 sodium 3,5-dicarboxybenzenesulfonate prepared in advance dissolved in N-methylpyrrolidone 759 was added, and the mixture was heated at 105°C for 1 hour, 120°C for 3 hours, and 150°C for 1 hour. 17
After confirming that the dipolymer was insoluble in N-methylpyrrolidone by reacting at 0° C. for 2 hours, the mixture was cooled. A dark yellow gelled particulate polymer dispersed in the continuous phase 180PAR-H was obtained, which was recovered by filtration and boiled in methanol twice to remove N-methylpyrrolidone, followed by depressurization. It was dried at 80° C. for 7 hours. The shape of this gelled particulate polymer is spherical, and 150
Even when immersed in N-methylbi-25-rolidone at 0.degree. C., it did not dissolve and remained in the form of two spheres. The main particle size was approximately 80-100 μm. In addition, the infrared absorption spectrum includes 1650cm-' and 1540c.
Absorption of amide group was observed at m-1.

FIG. 2 shows a scanning electron micrograph (250 times magnification) of the gelled particulate polymer obtained.

Example 3 Using the same equipment as in Examples 1 and (2), while passing nitrogen gas, Millionate MR10050, 69° was prepared using the dispersion stabilizer solution obtained in Example 1 (il) (non-volatile content: 40
Weight%) 4.7 g, l5OPAR-H1509
was added, and the temperature was raised to 100°C while stirring. A solution prepared in advance in which sodium 7,3,5-dicarboxybenzenesulfonate 259 was heated and dissolved in N-methylpyrrolidone 709 was added, and then 17.9 g of trimellitic anhydride was added. Raise the temperature to 105℃ for 1 hour, 1
The reaction was carried out at 20°C for 2 hours, at 140°C for 1 hour, at 160°C for 1 hour, and further at 170°C for 1 hour, and after confirming that the polymer 9 was insoluble in N-methylpyrrolidone, it was cooled. Reaction 26 - A dark yellow gelled particulate polymer dispersed in the subsequent phase 15OPAR-H was obtained, which was recovered by filtration and further boiled in methanol twice to remove N-methylpyrrolidone. Thereafter, it was dried at 80° C. for 7 hours under reduced pressure. The shape of this gelled particulate polymer is spherical,
Even when immersed in N-methylpyrrolidone at 150°C, it did not dissolve and remained in the form of a single sphere. Main particle size is approximately 65-80μ
It was m. The infrared absorption spectrum has 1780cm-
The absorption of imide group at ' is 1650 cm-' and 154
Absorption of amide group was observed at 0 cm-1. FIG. 3 shows a scanning electron micrograph (250 times magnification) of the particulate polymer obtained and formed into a crab gel.

Example 4 Using the same equipment as in Example 1, (21, passing nitrogen gas, 51.3 g of 4,4'-diphenylmethane diisocyanate, dispersion stabilizer solution obtained in Example 1, (11) (non-volatile min 40] 1-jl h) 4.79, l
5 OPAR.

-H1509 was added, and the temperature was raised to 100'C while stirring. Pre-prepared sodium 3,5-dicarboxybenzenesulfonate 27.59+! :) A solution of 6.2 g of rimesic acid dissolved in NMP 809 was added and reacted for 1 hour at 105°C, 2 hours at 120°C, 1 hour at 140°C, 1 hour at 165°C, and further 1 hour at 175°C. After confirming that the polymer 1 was insoluble in N-methylpyrrolidone, the mixture was cooled. Continuous phase l5OPAR-
A brown gelled particulate polymer dispersed in H was obtained, which was recovered by filtration and further boiled in methanol twice to remove N-methylpyrrolidone.

It was dried at 250°C for 2 hours. The shape of this gelled particulate polymer was spherical, and even when immersed in N-methylpyrrolidone at 150° C., it did not dissolve and remained spherical. The main particle size was approximately 80-100 μm. 1650C1ll-' and 1540c11 in the infrared absorption spectrum
Absorption of amide group was observed at 1-''.

Example 5 Using the same equipment as in Examples 1 and (2), Millionate MFL-10057, 69,
Example 1. Dispersion stabilizer solution obtained in (1) (non-volatile content: 4
0% by weight) 3.79. 15OPAR-H1509 was added and the temperature was raised to 100°C while stirring. A solution prepared by heating and dissolving 4 g of sodium 3,5-dicarboxybenzenesulfonate (ta) prepared in advance in 30 g of N-methylpyrrolidone was added, and then 36.79 g of trimellitic anhydride was added. Increase the temperature to 105℃ for 1 hour, 1
The reaction was carried out at 20°C for 2 hours, at 140°C for 1 hour, at 160°C for 1 hour, and further at 170°C for 1 hour to confirm that the polymer 1 was insoluble in N-methylpyrrolidone, and then cooled.

A brown gelled particulate polymer dispersed in the continuous phase 15OPAR-H was obtained, which was recovered by filtration and further repeated boiling in methanol twice.

After removing N-methylpyrrolidone, it was heated at 80°C under reduced pressure for 7 days.
Let dry for an hour. The shape of this gelled particulate polymer was spherical, and even when immersed in N-methylpyrrolidone at 150°C, it did not dissolve and remained spherical. The main particle size was approximately 80-100 μm. In addition, in the infrared absorption spectrum, there is an imide group absorption at 178〇29-cm-1, and an absorption at 1650cm-' and 1
Absorption of amide group was observed at 540 cm'-'.

Reference Example The gelled particulate polymer particles obtained in Examples 2 and 3, each 0.59 g, were placed in a glass filter and treated with hydrochloric acid.
The sodium sulfonate group is used as a sulfonic acid group. After thoroughly washing with water/methanol = 1/1 (volume ratio) to make it neutral, 200 mJ of 5T sodium chloride aqueous solution was flowed, and the filtrate was 0.0 mJ. The ion exchange capacity was determined by titration with IN sodium hydroxide.

The results are shown in Table 1.

Separately, the gelled particulate polymers obtained in Examples 2 and 3 were left in the air at 250° C. for 5 days, and then the ion exchange capacity was determined in the same manner as above. The results are shown in Table 1.

30- Comparative Example 1 4.4'-diphenylmethane diisocyanate 452.59, 48.5 g of sodium 3.5-dicarboxybenzenesulfonate, in a 21 four-bottle flask equipped with a thermometer, a shaker and a 9-ball condenser. Trimellitic anhydride 312
．． 79. Add 1485.79 N-methylpyrrolidone,
1 hour at 100°C with stirring in a nitrogen stream, 115
℃ for 2 hours, 120℃ for 2 hours, and then 13
The reaction was proceeded by raising the temperature to 5°C. The obtained polyamideimide resin was diluted with N-methylpyrrolidone to make the resin content (calculated value) in the varnish 30% by weight. The initial viscosity of the varnish (B-type viscometer, 30°C) was 31 poise, and the reduced viscosity of the polyamideimide resin (0.59/dl, dimethylformamide, 30°C) was 0.38. This polyamide-imide resin solution was diluted to 15% by weight with N-methylpyrrolidone and added in the form of droplets to ion-exchanged water to obtain one spherical particle. These spherical particles were only covered with polyamideimide precipitated on the surface, and the contents remained in a solution state.

Therefore, when these spherical particles were boiled in ion-exchanged water, they were deformed and their spherical shape completely collapsed. Several days were spent at room temperature in ion-exchanged water to remove the N-methylpyrrolidone contained in the spherical particles.

Comparative Example 2 Using the same equipment as in Example 1, f21, passing nitrogen gas, 4,4'-diphenylmethane diisocyanate 45.49. Example 1. Dispersion stabilizer solution obtained in (1) (nonvolatile content 40% by weight) 8 g, 15OPA
150g of R-H was added and the temperature was raised to 90°C while stirring. A solution prepared in advance by heating and dissolving 24.39 grams of sodium 3,5-dicarboxybenzenesulfonate in 909 grams of N-methylpyrrolidone was added, and then 17.59 grams of trimellitic anhydride was added. Raise the temperature to 10
1 hour at 5°C, 2 hours at 120°C, 1 hour at 140°C.

The reaction was carried out at 160° C. for 1 hour and then at 170° C. for 1 hour to obtain a brown particulate (spherical) polymer dispersed in the continuous phase of 15OPAR-H. This particulate polymer is heated
- It was confirmed that this particulate polymer was substantially linear because it completely dissolved in methylpyrrolidone and turned into an almost transparent solution state. Further, the obtained particulate polymer was collected by filtration, boiled in methanol and turned over twice to remove N-methylpyrrolidone, and then dried at 80° C. for 7 hours under reduced pressure. The shape of this particulate polymer was crushed, and the spherical shape before solvent removal was not maintained. The main particle size was approximately 20-40 μm.

In addition, in the infrared absorption spectrum, there is absorption of imide group at 1780 cm-', 1650 cm-'', 1540 mark-1
Absorption of amide groups was observed. FIG. 4 shows a scanning electron micrograph (500 times magnification) of the particulate polymer obtained.

As is clear from the above-mentioned Examples and Comparative Examples.

The gelled particulate polymer obtained by the production method of the present invention is spherical in shape, and the polymer is completely three-dimensionally cross-linked, so it can be used at high temperatures in polar solvents such as N-methylpyrrolidone. Becomes insoluble.

It has sufficient heat resistance and ion exchange ability, and the iR production process, including the solvent removal process, is industrially extremely simple.
It is also superior in terms of cost. Sub-33: Reaction catalysts in polar solvents at high temperatures, adsorbents (column agents) for metal ions in nuclear reactor water discarded at high temperatures,
It is extremely effective industrially as a general-purpose ion exchange resin.

[Brief explanation of the drawing]

Figures 1 to 3 are scanning electron micrographs showing the particle structure of the gelled particulate polymer obtained in the Examples of the present invention, and Figure 4 is the particulate polymer obtained in Comparative Example 2. This is a scanning electron micrograph showing the particle structure of . 34- No. 1 National flute 3 B Tokukai Sho GO-190414 (10) Tonto 2 Mouth 4th- Mouth

Claims (1)

[Scope of Claims] 1. (a) Aliphatic hydrocarbon (bl) Essentially immiscible with aliphatic hydrocarbons and soluble in the formed particulate polymer before gelation or a compound represented by the formula HOOC-A r -C0OH in the presence of a swelling aprotic polar solvent and (C) a dispersion stabilizer soluble in aliphatic hydrocarbons. 03M Incyanate with a valence of 2 or more The group-containing compound (1) and optionally a divalent or higher carboxyl group- and/or acid anhydride group-containing compound (11), and at least one of (1) and (11) is a trivalent or higher compound. Gelled particles characterized in that the resulting particulate polymer is reacted until it becomes insoluble in an aprotic polar solvent to form a gelled particulate polymer dispersed in an aliphatic hydrocarbon. 2. A method for producing a gelled particulate polymer according to claim 1, wherein the aprotic polar solvent is an aprotic basic polar solvent. 3. Aprotic The method for producing a gelled particulate polymer according to claim 1 or 2, wherein the polar solvent is N-methylpyrrolidone. 4. The dispersion stabilizer is lauryl methacrylate. Stearyl methacrylate, lauryl acrylate, or stearyl. Acrylate and 2-hydroxyethyl methacrylate, glycidyl methacrylate.Claim 1, 2 or 2 is a random copolymer of 2-hydroxyethyl acrylate and/or glycidyl acrylate. A method for producing a gelled particulate polymer according to claim 3. 5. Claim 1, wherein the compound OaM m represented by the formula HOOC-A r -C0OH is sodium 3,5-dicarboxybenzenesulfonate. , a method for producing a gelled particulate polymer according to Item 2, Item 3, or Item 4. 6. A compound containing a divalent or higher carboxyl group and/or an acid anhydride group (11), which is optionally used. ) is trimellitic anhydride, isophthalic acid or trimesic acid, the method for producing a gelled particulate polymer according to claim 1, 2, 3, 4 or 5 7. The isocyanate group-containing compound (1) having a valence of 4 or more is
．． 4'-diphenylmethane diisocyanate, 4°4'
- Diphenyl ether diisocyanate, tolylene diisocyanate, isocyanurate ring-containing polyisocyanate obtained by trimerization reaction thereof (wherein n is an integer of about 0 to 5) BoIJ phenylmethyl polyisocyanate is claimed. 1st term, 2nd term, 3rd term, 4th term. A method for producing a gelled particulate polymer according to item 5 or 6. 8. Compound (I) and compound (50 to 300% by weight based on the previous total amount of aliphatic hydrocarbons)Claims 1, 2, 3, 4, and 5 Item 9. A method for producing a gelled particulate polymer according to Item 6 or 7. 9. Adding an aprotic polar solvent to Compound (I) and Compound (I)
10 to 150% by weight based on the total amount of rl; 7'c Claims 1, 2, 3, 4, 5,
A method for producing a gelled particulate polymer according to item 6, 7, or 8. 10. Claims 1, 2, 3, 4, and 10 in which the dispersion stabilizer is 0.1 to 20% by weight based on the total amount of compound (I) and compound (II). Sections 5 and 6. A method for producing a gelled particulate polymer according to item 7, 8, or 9.