JPH032886B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a gelled particulate polymer having imide groups, and more specifically to a method for producing a gelled particulate polymer having excellent heat resistance that can be applied as an adsorbent for inorganic elements, a material for separating organic compounds, etc. The present invention relates to a method for producing a gelled particulate polymer having imide groups.

Polyisocyanate, polycarboxylic acid having an acid anhydride group, N-methyl-2-pyrrolidone, N,
It is known to react in a solution form in a polar solvent such as N-dimethylformamide or N,N-dimethylacetamide to obtain a polymer solution having an imide group, such as a polyamide-imide solution or a polyimide solution.

However, when solution polymerization is proceeded with a resin composition containing a crosslinking component in an amount sufficient to cause gelation, a non-flowable gel containing a solvent is ultimately produced.

Obtaining a solid crosslinked polymer from a gel requires removal or recovery of the solvent by an extremely uneconomical process, which poses a major cost problem in industrial scale production. In addition, there is a drawback that the obtained solid polymer is in a crushed form and cannot be obtained in a spherical form.
In addition, aqueous suspension polymerization is generally known as a method for obtaining spherical crosslinked polymers, but the reaction between polyisocyanate and polycarboxylic acid having an acid anhydride group requires reaction at a high temperature of 100°C or higher. ,
It is not possible to carry out aqueous suspension polymerization for reasons such as the reaction of isocyanates with water.

As a result of repeated studies on an inexpensive method for producing a particulate polymer having gelled imide groups with excellent heat resistance, the present inventors discovered that gelled imide groups dispersed in a non-aqueous organic liquid We have completed a method for producing particulate polymers having the following properties.

The present invention provides a first non-aqueous organic liquid that is insoluble in a particulate polymer having an imide group to be produced, a dispersion stabilizer soluble in the first organic liquid, and a particulate polymer having an imide group to be produced. in the presence of a second non-aqueous organic liquid that is soluble or swellable in the organic liquid and is essentially immiscible with the first non-aqueous organic liquid, optionally with a di-functional isocyanate. polyisocyanate (), polycarboxylic acid () having an acid anhydride group, and optionally a particulate polymer having an imide group that produces a polycarboxylic acid () other than the polycarboxylic acid () having an acid anhydride group. Gelled imide groups characterized in that the polymer is reacted until the coalescence becomes insoluble in the second non-aqueous organic liquid to form a particulate polymer having imide groups dispersed in the first non-aqueous organic liquid. The present invention relates to a method for producing a particulate polymer having the following.

The first non-aqueous organic liquid in the present invention includes:
A nonaqueous organic liquid is used that is insoluble in the particulate polymer having imide groups and has inert properties that do not inhibit the polymerization reaction.

For example, n-hexane, octane, dodecane,
Aliphatic or aliphatic hydrocarbons such as ISOPAR-E, ISOPAR-H, ISOPAR-K (trade names manufactured by Etsuo Standard Oil Co., Ltd., petroleum-based saturated aliphatic or alicyclic hydrocarbons with a boiling point range of about 40 to 300°C) Cyclic hydrocarbons, benzene, toluene, xylene, NISSEKI
Aromatic hydrocarbons such as HISOL-100 and NISSEK HISOL-150 (all trade names manufactured by Nippon Petrochemical Co., Ltd., petroleum-based aromatic hydrocarbons with a boiling point range of about 80 to 300°C) are used. Considering the reaction temperature, those having a boiling point of 100°C or higher are preferred. These can be used alone or in combination.

The dispersion stabilizer used in the present invention is soluble in the first non-aqueous organic liquid, forms a stabilizing layer on the surface of the formed particulate polymer having imide groups, and forms a stabilizing layer on the surface of the particulate polymer having imide groups at least during the polymerization process. Any material can be used as long as it has the function of stabilizing the dispersed state of the material, and there are no particular restrictions. Examples of such a dispersion stabilizer include a polymer having an imide group that becomes a dispersed phase, or a reactant solution that forms a polymer (polyisocyanate, polycarboxylic acid having an acid anhydride group, and a second non-aqueous organic solution formed from liquid)
A resin is used that shares a first organic component that has an affinity for the non-aqueous organic liquid and a second organic component that is soluble in the first non-aqueous organic liquid serving as a continuous phase.

The first organic component having an affinity for the dispersed phase is mainly an aromatic chain polymer formed through a polar bonding group such as an ether group, an ester group, an amide group, or an imide group, such as terephthalic acid or Chain polyester, polyamide, polyamideimide, polyimide, polyetheramide, polyesteramide, obtained from isophthalic acid and dihydric alcohol,
Polyester amide imide, polyester imide, bisphenol type epoxy resin, vinyl monomer containing a polar group, such as acrylonitrile,
Polymers or copolymers of acrylamide, vinylpyrrolidone, vinylpyridine, vinyllactam, etc. are used. Continuous phase (first non-aqueous organic liquid)
As the second organic component which is soluble in , a mainly aliphatic chain polymer with low polarity is used. For example, polymers or copolymers of butyl, hexyl, 2-ethylhexyl, octyl, lauryl, or stearyl esters of acrylic acid or methacrylic acid, monoalkoxides of polyethylene oxide with a degree of polymerization of 3 to 100, and monoalkoxides of polyethylene oxide with a degree of polymerization of 3 to 100. Monoacoxides of polypropylene oxide and monomethacrylates thereof, such as NK ester M-9G,
Polymers or copolymers of M-23G (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name), vinyl polymers such as polybutadiene and polyisoprene, single-end-capped products of polyhydroxy fatty acid esters with a molecular weight of 1000 or more, such as 12 -Hydroxystearic acid self-condensate 1
Used are polymers or copolymers of monoend-blocked products with monohydric carboxylic acids or monohydric alcohols, glycidyl methacrylate adducts thereof, decomposed natural rubber, cellulose derivatives, and the like. The first organic component and the second organic component are obtained as a random polymer, block polymer, or graft polymer linked through chemical bonds.

Other examples used as dispersion stabilizers include isocyanate groups and acid anhydrides possessed by reactants (polyisocyanates, polycarboxylic acids having acid anhydride groups, and other polycarboxylic acids used as necessary; the same applies hereinafter). A resin having one or more functional groups capable of reacting with either a group or a carboxyl group is used. Examples of such functional groups include, for example, hydroxyl groups, carboxyl groups, methylol groups, amino groups, acid anhydride groups, and epoxy groups for isocyanate groups. Preferably hydroxyl groups are used. For the acid anhydride group and carboxyl group, for example, isocyanate group, hydroxyl group, amino group, epoxy group, etc. are used. Preferably, a hydroxyl group is used for the acid anhydride group, and a hydroxyl group or an epoxy group is used for the carboxyl group. Examples of resins having such functional groups include butylated benzoguanamine formaldehyde resins,
Alkoxy-modified amino resins such as butylated melamine formaldehyde resins, telechelic rubber or decomposed natural rubber with an average molecular weight of several thousand having hydroxyl groups, carboxyl groups, acid anhydride groups, epoxy groups, isocyanate groups, and mercaptan groups are used. It will be done. In addition, as a dispersion stabilizer, a random polymer, a block polymer, or a craft polymer, in which the first organic component and the second organic component are linked through a chemical bond, is functionalized to the first organic component. Those into which groups are introduced are used. Furthermore, a material obtained by introducing a functional group into the second organic component that is soluble in the continuous phase (first non-aqueous organic liquid) is also used. When the dispersion stabilizer is a vinyl polymer, a method for introducing a functional group into these resins may be to copolymerize a vinyl monomer having a functional group. As a vinyl monomer having a hydroxyl group,
For example, allyl alcohol, hydroxyethyl or hydroxypropyl ester of acrylic acid or methacrylic acid, acrylic acid or methacrylic ester of polyethylene oxide with a polymerization degree of 3 to 100, or polypropylene oxide with a polymerization degree of 3 to 100 are used. As the vinyl monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, itaconic acid, etc. are used. As the vinyl monomer having an acid anhydride group, for example, maleic anhydride, itaconic anhydride, etc. are used. As the vinyl monomer having an epoxy group, for example, glycidyl ester or aryl glycidyl ester of acrylic acid or methacrylic acid is used. As the vinyl monomer having a methylol group, methylol acrylamide or the like is used.

In the case of addition polymers and condensation polymers, it can be easily introduced by leaving a functional group possessed by the monomer forming the polymer or a functional group generated by reaction at the end of the polymer. In the case of polyethylene oxide, polypropylene oxide, etc., hydroxyl groups can remain. In the case of polyesters obtained from polycarboxylic acids or their anhydrides and polyalcohols, carboxyl groups, acid anhydride groups, or hydroxyl groups may remain. In the case of polyamide, polyimide or polyamideimide obtained from polycarboxylic acid or its anhydride and polyisocyanate or polyamine, carboxyl groups, acid anhydride groups, isocyanate groups, amine groups, etc. may remain. A resin preferable as a dispersion stabilizer is a long chain having 12 or more carbon atoms of acrylic acid or methacrylic acid, which is obtained by radical polymerization in an aliphatic or alicyclic hydrocarbon, which is the first non-aqueous organic liquid. A hydroxyl group-containing vinyl polymer formed from an alkyl ester and a hydroxyl group-containing vinyl polymer whose main chain is formed from monoalkoxy monomethacrylate or monoalkoxy monoacrylate of polypropylene oxide having a degree of polymerization of 20 or higher are used.

The molecular weight of the dispersion stabilizer is preferably 1000 or more. When it is less than 1000, aggregation tends to occur during the polymerization process. Particularly preferred is a molecular weight in the range of 1,000 to 50,000. As a specific example, a preferred monomer composition of the hydroxyl group-containing vinyl polymer used as a dispersion stabilizer is one or more acrylic monomers containing hydroxyl groups, 2 to 20% by weight, and an aliphatic or alicyclic hydrocarbon. Soluble carbon number
The range includes one or more acrylic monomers having a long chain alkyl group of 12 or more and/or an acrylic monomer containing a monoalkoxide of polypropylene oxide having a degree of polymerization of 20 or more at a polymerization percentage of 80 to 98.

The second non-aqueous organic liquid that is soluble or swellable with respect to the particulate polymer having imide groups produced in the present invention and is essentially immiscible with the first non-aqueous organic liquid is used for polymerization reaction. A non-aqueous organic liquid having inert properties that does not inhibit
In the polymerization reaction process, a solvent is used that contacts the reaction between end groups and acts as a solvent to increase the molecular weight of the resulting imide group-containing polymer. Here, "essentially immiscible with the first non-aqueous organic liquid" means that in addition to being completely insoluble in the first non-aqueous organic liquid, the two liquids are not completely insoluble in the first non-aqueous organic liquid at a certain mixing ratio. This is meant to include non-aqueous organic liquids that are immiscible to the extent that they phase separate. The second non-aqueous organic liquid is a polar liquid and has a greater affinity for the resulting imide group-containing polymer or reactant contained in the dispersed phase than the first non-aqueous organic liquid. Preferably used. Examples of such a second nonaqueous organic liquid include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, γ-butyrolactone, phenol, and cresol. These may be used alone or in combination.
Preferably, the first non-aqueous organic liquid is an aliphatic or alicyclic hydrocarbon, and the second non-aqueous organic liquid is N.
A combination with -methyl-2-pyrrolidone is used.

In the present invention, a trifunctional or higher functional polyisocyanate is used as the polyisocyanate, but a difunctional isocyanate may be used in combination if necessary. The trifunctional or higher functional polyisocyanate serves as a crosslinking component for obtaining a particulate polymer having a gelled imide group, which is the object of the present invention.

Examples of trifunctional or higher-functional polyisocyanates used in the present invention include compounds obtained by trimerizing diisocyanates, such as tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenyl ether diisocyanate, and naphthalene diisocyanate.
Trimers of aromatic diisocyanates such as 1,5-diisocyanate and 4,4'-diphenylmethane diisocyanate, ethylene diisocyanate, 1,
4-tetramethylene diisocyanate, 1,6-
Trimers of aliphatic diisocyanates such as hexamethylene diisocyanate and 1,12-dodecane diisocyanate, trimers of alicyclic diisocyanates such as cyclobutene 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, and isophorone diisocyanate. triisocyanate compounds, e.g. triphenylmethane-
4,4',4''-triisocyanate, polyphenylmethyl polyisocyanate, for example, a product obtained by reacting a condensate of aniline and formaldehyde with phosgene, etc. are used. The trimer of diisocyanate contains an isocyanurate ring. Therefore, it is not only useful as a crosslinking component, but also provides excellent heat resistance.

Examples of difunctional isocyanates used in combination if necessary include tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, naphthalene-1,5
- diisocyanate, aromatic diisocyanate such as 4,4'-diphenylmethane diisocyanate,
Aliphatic diisocyanates such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutene 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, Alicyclic diisocyanates such as isophorone diisocyanate are used. Considering heat resistance etc., tolylene diisocyanate, 4,
4'-diphenyl ether diisocyanate, 4,
Preferably, aromatic diisocyanates such as 4'-diphenylmethane diisocyanate are used.
A suitable method for producing isocyanurate ring-containing polyisocyanates is shown in Japanese Patent Application No. 148820/1983.

Polyisocyanates contain active hydrogen molecules such as methanol, n-butanol, benzyl alcohol, ε-caprolactam, methyl ethyl ketone oxime, phenol, and cresol in order to control the reaction rate in the polycondensation reaction process and obtain stable particulate polymers. It is also possible to use one in which part or all of the isocyanate groups are stabilized with a suitable blocking agent.

As a polycarboxylic acid having an acid anhydride group,
For example, trimellitic anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, 3,4,
Tricarboxylic acid anhydrides such as 4'-benzophenone tricarboxylic acid-3,4'-anhydride, 1,2,3,4
-butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, bicyclo-(2,2,2)-octene-(7)-2,3,5,6-tetracarboxylic acid,
Ethylenetetracarboxylic acid, bicyclo-[2,
2,2] -Octo-(7)-En-2:3,5:6-
Aliphatic and alicyclic tetrabasic acids such as tetracarboxylic dianhydride, pyromellitic acid, 3,3',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'-diphenyltetracarboxylic acid , perylene-3,4,9,10-tetracarboxylic acid, aromatic tetrabasic acids such as 3,4-dicarboxyphenylsulfone, thiophene-2,3,4,5-
Examples include tetrabasic acid di- or monoanhydrides such as heterocyclic tetrabasic acids such as tetracarboxylic acid and pyrazinetetracarboxylic acid.

A polyamideimide is obtained from a polycarboxylic acid containing an acid anhydride group having a free carboxyl group, such as tricarboxylic anhydride, and a polyisocyanate. Further, polyimide can be obtained from a polycarboxylic acid having only an acid anhydride group such as tetracarboxylic dianhydride and a polyisocyanate. In general, trimellitic anhydride, 3,3',
Preferred are 4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, and the like.

If necessary, polycarboxylic acids other than the polycarboxylic acids having acid anhydride groups described above can also be used. Examples of such polycarboxylic acids include trimellitic acid, trimesic acid, tris(2-carboxyethyl)isocyanurate, terephthalic acid,
Isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, etc. are used. Among these polycarboxylic acids, trifunctional or higher functional polycarboxylic acids also act as branching components for obtaining the gelled particulate polymer targeted by the present invention. The amount of polyisocyanate, polycarboxylic acid having an acid anhydride group, and other polycarboxylic acids used as necessary is determined by the equivalent ratio of all carboxyl groups of polycarboxylic acid to all isocyanate groups of polyisocyanate ( The ratio (total carboxyl groups/total isocyanate groups) is preferably in the range of 0.1 to 3.0, particularly preferably in the range of 0.3 to 2.0. Here, 1 equivalent of acid anhydride group of polycarboxylic acid is treated as 1 equivalent of carboxyl group. The quantitative ratio of the first non-aqueous organic liquid serving as the continuous phase and the reactant serving as the dispersed phase is within a range such that the amount of the reactant is 10 to 80% by weight based on the total amount of the first non-aqueous organic liquid and the reactant. is preferred. From the viewpoint of production efficiency and cost, it is particularly preferable that the content is 40% by weight or more.

The amount ratio of the dispersion stabilizer to the reactant is preferably within a range of 0.5 to 20% by weight based on the total amount of the dispersion stabilizer and the reactant. The amount ratio of the second non-aqueous organic liquid and the reactant is such that the amount of the second non-aqueous organic liquid to the total amount of the second non-aqueous organic liquid and the reactant is
A range of 0.5 to 70 weight percent is preferred.
If the amount is less than 0.5 weight percent, the polymerization reaction will be considerably difficult to proceed. If it exceeds 70% by weight, a continuous phase with a high specific gravity is formed in which the reactant is dissolved in the second non-aqueous organic liquid, and as a result, phase separation occurs from the first non-aqueous organic liquid with a low specific gravity to form a dispersed phase. Even if a dispersed phase is formed, aggregation is likely to occur during the polymerization reaction. Particularly preferably a range of 2 to 40 weight percent is used.

The reaction of a trifunctional or higher functional polyisocyanate, a polycarboxylic acid having an acid anhydride group, and other polycarboxylic acids used as necessary causes the resulting imide group-containing polymer to become a second non-aqueous organic liquid. Proceed until insoluble. The reaction temperature for this reaction is preferably 80 to 250°C.

The insolubility of the resulting particulate polymer in the second non-aqueous organic liquid is confirmed by removing the resulting particulate polymer from the dispersion and dissolving it in, for example, N-methyl-2-pyrrolidone. If the particulate polymer is gelled, the particulate polymer is N-methyl-2.
- Does not dissolve in pyrrolidone and does not color N-methyl-2-pyrrolidone.

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. Naturally, the imide group-containing particulate polymer obtained by the production method of the present invention is quickly transformed into an inert compound when its reactant, particularly polyisocyanate, comes into contact with water. Therefore, it is not possible to use water as a dispersion medium. The reaction may be carried out by charging all the raw materials at the same time, or by charging them in stages depending on the purpose.

The method of charging the reactant in the present invention requires some modification depending on the properties of the reactant. Preferably, at least one component of the reactant is soluble or swellable in the second non-aqueous organic liquid, or is liquid at the reaction temperature. Preferred specific examples include a homogeneous solution in which all components except the acid component are mixed, or a heterogeneous solution in which a homogeneous solution of polyisocyanate and a second non-aqueous organic liquid is dispersed in the form of oil droplets in the first non-aqueous organic liquid. The reaction proceeds by adding a finely powdered acid component to the solution. According to this method, the polymerization reaction can proceed at a relatively low reaction temperature, and undesirable side reactions can be suppressed.

Polyisocyanate is added to a homogeneous solution in which all components except the polyisocyanate are mixed, or to a heterogeneous solution in which a homogeneous solution of an acid component and a second non-aqueous organic liquid is dispersed in the form of oil droplets in the first non-aqueous organic liquid. The reaction may proceed as follows.

In order to maintain the dispersion stability of the particulate polymer during the polymerization reaction and reduce the particle size, a method may be used in which the dispersion stabilizer is introduced in stages. The dispersion stabilizer may be used as a solution.

The particulate polymer having an imide group obtained by the present invention may be prepared by adding methanol, n-butanol, benzyl alcohol, etc. as necessary during or after the reaction.
Stabilization can be achieved by adding a suitable blocking agent having one active hydrogen in the molecule, such as ε-caprolactam, methyl ethyl ketone oxime, acetaldoxime, phenol, and cresol.

Stirring methods used in the reaction include stirring methods involving high-speed shearing using an emulsifier (homomixer), mechanical cutting of particles using a propeller-type stirrer, and stirring methods that do not involve pulverization. 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 diameter at the beginning of the reaction, and then use a propeller-type stirrer to further advance the reaction at around the polymerization rate at which the dispersion stability of the particles is good. . According to this method, a particulate polymer having a relatively small particle size and uniform particle size can be obtained.

According to the production method of the present invention, a particulate polymer having imide groups is obtained by being dispersed in a first non-aqueous organic liquid, and the dispersed phase contains, in addition to this particulate polymer, a second particulate polymer. Non-aqueous organic liquids, dispersion stabilizers, reactants, etc. are included, but these are removed by purification.

The particulate polymer having imide groups obtained in the present invention is obtained in the form of non-agglomerated particles with an average particle size ranging from 0.05 to 2000 microns and above. The preferred average particle size is between 0.1 and 500 microns, most preferably between 0.5 and 100 microns. The particulate polymer can be recovered from the dispersion solution by filtration or decantation and then drying under normal pressure or reduced pressure.

The recovered gelled particulate polymer having imide groups is heated at 100 to 400°C, preferably at 200°C, as necessary.
By heat-treating at ~300°C, the dispersion stabilizer contained in the gelled particulate polymer can be thermally decomposed and the heat resistance can be improved.

The particulate polymer having imide groups obtained by the production method of the present invention is obtained in the form of gelled spheres or crushed particles that are insoluble in solvents, and exhibits good heat resistance. Such gel particles are useful as adsorbents for inorganic elements, separation materials for organic compounds, and the like.

The present invention will be explained below by carrying out the invention.

Example 1 (1) Synthesis of dispersion stabilizer 152 g of ISOPAR-H (aliphatic hydrocarbon manufactured by Etsuo Standard Oil Co., Ltd., trade name) was placed in a four-necked flask equipped with a thermometer, stirrer, and bulb condenser.
The temperature was raised to 120℃. 183 g of lauryl methacrylate prepared in advance while passing nitrogen gas,
17g of 2-hydroxyethyl methacrylate, benzoyl peroxide paste (content of benzoyl peroxide)
50% by weight) was added dropwise over 2 hours with stirring. Subsequently, the temperature was raised to 140°C, and the reaction was continued at the same temperature for 4 hours. This dispersion stabilizer solution has a non-volatile content when baked at 170℃ for 30 minutes.
The number average molecular weight of the dispersion stabilizer was 14,000.

(2) Synthesis of tolylene diisocyanate trimer Place 1000 g of tolylene diisocyanate in a four-necked flask equipped with a thermometer, stirrer, and bulb condenser.
Anisic acid 0.52g, dimethylaminoethanol
0.300g was added, and the temperature was raised to 80°C while passing nitrogen. The reaction was carried out at the same temperature until the content of isocyanate groups (initial concentration: 48 weight percent) became 32 weight percent. In the infrared absorption spectrum of this product, absorption of isocyanurate rings was observed at 1710 cm ^-1 and 1410 cm ^-1 , and absorption of isocyanate groups was observed at 2260 cm ^-1 .

(3) Synthesis of gelled particulate polymer having imide groups While passing nitrogen gas through a four-necked flask equipped with a thermometer, stirrer, and bulb condenser, 4,4'-diphenylmethane diisocyanate 48.4 g, 48.4 g of tolylene diisocyanate trimer obtained in (2), 19.0 g of the dispersion stabilizer solution obtained in (1) (nonvolatile content 50.5% by weight), ISOPAR-H (aliphatic hydrocarbon manufactured by Etsuo Standard Oil Co., Ltd.) , product name) 150g, N-
33 g of methyl-2-pyrrolidone was added, and the temperature was raised to 110°C while stirring. Add 37.2g of trimellitic anhydride, which has been finely powdered in advance, and heat it at 110℃ for 1 hour.
The reaction was carried out for 1 hour at 120°C, 1 hour at 130°C, 1 hour at 140°C, 1 hour at 150°C, and 2 hours at 160°C. When a part of the brown particulate polymer dispersed in ISOPAR-H was taken out using a hippet and added to N-methyl-2-pyrrolidone, the particulate polymer was dissolved in N-methyl-2-pyrrolidone. Zu, N
-Methyl-2-pyrrolidone did not cause any coloring. This was then collected by filtration, washed with n-hexane and then with acetone, and then dried at 60° C. for 5 hours under reduced pressure. The infrared absorption spectrum of this particulate polymer includes an imide bond at 1780 cm ^-1 , an imide bond at 1650 cm ^-1 ,
Absorption of amide bond was observed at 1540 cm ^-1 . When this particulate polymer was observed with a scanning electron microscope, it was found to be spherical in shape, and the main particle diameter was about 10 to 80 μm.
The starting temperature of thermal decomposition of this product was 390°C (measurement conditions: temperature increase rate 10°C/min, air atmosphere, sample amount 10mg).

Example 2 Using the same apparatus as in Example 1, (3), while passing nitrogen gas, 19.0 g of the dispersion stabilizer solution obtained in Example 1, (1) (nonvolatile content 50.5% by weight), Example 1. Triweight of lylene diisocyanate obtained in (2)
Add 94.3 g, ISOPAR-H (aliphatic hydrocarbon manufactured by Etsuo Standard Oil Co., Ltd., trade name) 150 g, and 33 g of N-methyl-2-pyrrolidone, and add while stirring.
The temperature was raised to 110℃. Add 37.7 g of trimellitic anhydride, which has been pulverized in advance, and heat at 110°C for 1 hour.
1 hour at 120℃, 1 hour at 130℃, 1 hour at 140℃,
The reaction was carried out at 150°C for 1 hour and at 160°C for 2 hours. After confirming the gelation of the particulate polymer in the same manner as in Example 1.
The brown particulate polymer dispersed in ISOPAR-H was recovered by filtration, washed with n-hexane and then acetone, and then dried under reduced pressure at 60°C for 5 hours.

The infrared absorption spectrum of this particulate polymer includes:
Imide bond absorption was observed at 1780 cm ^-1 , and amide bond absorption was observed at 1650 cm ^-1 and 1540 cm ^-1 . When this particulate polymer was observed with a scanning electron microscope, it was found to be spherical in shape, and the main particle diameter was about 10 to 80 μm. The starting temperature of thermal decomposition of this material was 290℃ (measurement conditions:
Heating rate: 10℃/min, air atmosphere, sample amount: 10
mg) Example 3 While passing nitrogen gas through a four-necked flask equipped with a thermometer, stirrer, and bulb condenser, 37.8 g of 4,4'-diphenylmethane diisocyanate obtained in Example 1, (2) was added. Tolylene diisocyanate trimer
36.2g, Example 1, dispersion stabilizer solution obtained in (1) (non-volatile content 50.5% by weight) 19.0g, ISOPAR-
H (aliphatic hydrocarbon manufactured by Etsuso Standard Oil Co., Ltd.,
Product name) 150g, N-methyl-2-pyrrolidone 33
g was added thereto, and the temperature was raised to 110°C while stirring. Pre-pulverized trimellitic anhydride 58.0g
1 hour at 110℃, 1 hour at 120℃, 130℃
℃ for 1 hour, 140℃ for 1 hour, 150℃ for 1 hour,
The reaction was carried out at 160°C for 2 hours and at 180°C for 5 hours. After confirming the gelation of the particulate polymer in the same manner as in Example 1.
The brown particulate polymer dispersed in ISOPAR-H was recovered by filtration, washed with n-hexane and then acetone, and then dried under reduced pressure at 150° C. for 5 hours.

The infrared absorption spectrum of this particulate polymer includes:
Imide bond absorption was observed at 1780 cm ^-1 , and amide bond absorption was observed at 1650 cm ^-1 and 1540 cm ^-1 . When this particulate polymer was observed with a scanning electron microscope, it was found to be spherical in shape, and the main particle diameter was about 10 to 80 μm.

Example 4 While passing nitrogen gas into a four-neck flask equipped with a thermometer, stirrer, and bulb condenser, 60.0 g of 4,4'-diphenylmethane diisocyanate and the trichloride obtained in Example 1 (2) were added. Diisocyanate trimer
14.4g, dispersion stabilizer solution obtained in Example 1, (1) (non-volatile content 50.5% by weight) 19.0gISOPAR-H
(Aliphatic hydrocarbon manufactured by Etsuso Standard Oil Co., Ltd.,
Product name) 150g, N-methyl-2-pyrrolidone 33
g was added thereto, and the temperature was raised to 110°C while stirring. 57.6g of pre-pulverized trimellitic anhydride
1 hour at 110℃, 1 hour at 120℃, 130℃
℃ for 1 hour, 140℃ for 1 hour, 150℃ for 1 hour,
The reaction was carried out at 160°C for 2 hours and at 180°C for 5 hours. After confirming the gelation of the particulate polymer in the same manner as in Example 1.
The brown particulate polymer dispersed in ISOPAR-H was recovered by filtration, washed with n-hexane and then acetone, and then dried under reduced pressure at 150° C. for 5 hours.

The infrared absorption spectrum of this particulate polymer includes:
Imide bond absorption was observed at 1780 cm ^-1 , and amide bond absorption was observed at 1650 cm ^-1 and 1540 cm ^-1 . When this particulate polymer was observed with a scanning electron microscope, it was found to be spherical in shape, and the main particle diameter was about 10 to 80 μm.

Example 5 Using the same apparatus as in Example 1, (3), while passing nitrogen gas, 19.0 g of the dispersion stabilizer solution obtained in Example 1, (1) (non-volatile content: 50.5% by weight), 70 g % solution of isophorone diisocyanate trimer
Manufactured by AG, product name, IPDI-T 1890S) 146g, N
-Methyl-2-pyrrolidone (33 g) was added and the temperature was raised to 110°C while stirring. Add 30.0 g of trimellitic anhydride that has been finely powdered in advance, and heat at 110°C for 1 hour.
The reaction was carried out for 1 hour at 120°C, 1 hour at 130°C, 1 hour at 140°C, 1 hour at 150°C, and 2 hours at 160°C. After confirming gelation of the particulate polymer in the same manner as in Example 1, the brown particulate polymer dispersed in ISOPAR-H was recovered by filtration, and n-hexane,
After further washing with acetone, the
Let dry for an hour.

The infrared absorption spectrum of this particulate polymer includes:
Imide bond absorption was observed at 1780 cm ^-1 , and amide bond absorption was observed at 1650 cm ^-1 and 1540 cm ^-1 . Further, this particulate polymer did not dissolve completely in N-methyl-2-pyrrolidone. When this particulate polymer was observed with a scanning electron microscope, it was found to be spherical in shape, and the main particle diameter was about 10 to 80 μm.

Claims (1)

[Claims] 1. A first non-aqueous organic liquid that is insoluble in the particulate polymer having an imide group to be produced, a dispersion stabilizer soluble in the first organic liquid, and a particulate polymer having an imide group to be produced. optionally a difunctional isocyanate in the presence of a second non-aqueous organic liquid that is soluble or swellable to the particulate polymer and essentially immiscible with the first non-aqueous organic liquid. In addition, a trifunctional or higher functional polyisocyanate (), a polycarboxylic acid () having an acid anhydride group, and optionally an imide group that produces a polycarboxylic acid () other than the polycarboxylic acid () having an acid anhydride group. A gel comprising a particulate polymer having imide groups dispersed in a first non-aqueous organic liquid by reacting the particulate polymer with the second non-aqueous organic liquid until it becomes insoluble in the first non-aqueous organic liquid. A method for producing a particulate polymer having a converted imide group. 2 The first non-aqueous organic liquid is an aliphatic or alicyclic hydrocarbon, and the second non-aqueous organic liquid is an N-methyl-
A method for producing a particulate polymer having a gelled imide group according to claim 1, which is 2-pyrrolidone. 3. Claim 1 or 2, wherein the polyisocyanate () is a trimer of diisocyanate.
A method for producing a particulate polymer having a gelled imide group as described in 1. 4. The method for producing a particulate polymer having a gelled imide group according to claim 1, 2 or 3, wherein the bifunctional isocyanate is an aromatic diisocyanate. 5. Claim No. 5 in which the polycarboxylic acid () having an acid anhydride group is trimellitic anhydride, pyromellitic dianhydride, or 3,3',4,4'-benzophenonetetracarboxylic dianhydride A method for producing a particulate polymer having a gelled imide group according to item 1, 2, 3, or 4.