JPS58157821A - Preparation of gelled granular polymer having imide group - Google Patents

Abstract

PURPOSE:To prepare the titled polymer having excellent heat resistance, at a low cost, by reacting a polyisocyanate having >=3 functional value with a polycarboxylic acid containing acid anhydride group in the presence of a specific insoluble or soluble solvent and dispersion stabilizer. CONSTITUTION:A gelled granular polymer having imide group can be prepared by reacting (A) a polyisocyanate having >=3 functionality with (B) a polycarboxylic acid having acid anhydride group in the presence of (C) (i) a non- aqueous organic liquid which is a non-solvent of the produced granular polymer having imide group, (ii) a dispersion stabilizer soluble in the component (i) and (iii) the second non-aqueous organic liquid which dissolves or swells the produced granular polymer having imide group and immiscible with the component (i), until the produced granular polymer having imide group becomes insoluble in the component (iii), thereby dispersing the polymer in the component (i).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a gelled particulate polymer having a nonimide group, and more specifically to a heat-resistant polymer that can be applied to 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 excellent imide groups.

A polyisocyanate and a polycarboxylic acid having an acid anhydride group are combined into N-methyl-2-pyrrolidone.

Polymer solution 9 having imide groups by reacting in a solution state in a polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, etc. For example, a polyamide-imide solution,
It is known to obtain polyimide solutions and the like.

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 finally 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 round polymer polymer is in a crushed form and cannot be obtained in a spherical form. Aqueous suspension polymerization is generally known as a method for obtaining spherical cross-linked 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. In particular, it is impossible to carry out aqueous suspension polymerization in S mountains, as the isocyanate reacts 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 9. Completed a method for producing a particulate polymer having the following properties.

The present invention provides a first non-aqueous organic liquid that is insoluble in a particulate polymer having imide groups to be produced.

It is soluble or swellable with respect to the dispersion stabilizer soluble in the first organic liquid and the resulting particulate polymer having imide groups, and is essentially immiscible with the first non-aqueous organic liquid. In the presence of a second non-aqueous organic liquid, a trifunctional or higher functional polyisocyanate (I
), a polycarboxylic acid (group) having an acid anhydride group and optionally a particulate polymer having an imide group that produces a polycarboxylic acid (II) having an acid anhydride group (other than wound). Gelled particles having imide groups are formed by reacting the particles until they become insoluble in a second non-aqueous organic liquid to form particulate polymers having imide groups dispersed in the first non-aqueous organic liquid. The present invention relates to a method for producing a polymer.

The first non-aqueous organic liquid in the present invention is:

A non-aqueous organic liquid is used that is insoluble in the particulate polymer having an imide group and has an inert property that does not inhibit the monopolymerization reaction.

For example, n-hexane, octane, dodecane.

l80PAR-E, l5OPAR-H, l5OPA
R-K (That's all.

Etsusu, manufactured by TANDART Oil Co., Ltd. Product name p Boiling point range is 4
aliphatic or alicyclic hydrocarbons such as petroleum-based saturated aliphatic or alicyclic hydrocarbons (approximately 0 to 300°C), benzene, toluene, xylene.

Nl88EKI HI30L-100, Nl58EKI
Aromatic hydrocarbons such as HI30L-150 (trade name manufactured by Nippon Petrochemical Co., Ltd.; a petroleum-based aromatic hydrocarbon with a boiling point range of about 80 to 300°C) are used.

In consideration of 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 an anodizing layer on the surface of the resulting imide group-containing particulate polymer, and at least during the polymerization process. It can be used as long as it has the function of stabilizing the dispersion state of particles, and there is no limit to 1%. Examples of such dispersion stabilizers include 1, for example, a polymer having an imide group that becomes a dispersed phase, or a reactant solution that forms a polymer (polyincyanate, polycarboxylic acid having an acid anhydride group, and a second non-aqueous organic A resin is used that shares a first organic component that has an affinity for the first non-aqueous organic liquid and a second organic component that is soluble in the first non-aqueous organic liquid and serves as a continuous phase.

The first organic component that has an affinity for the dispersed phase is an ether group, an ester group, or an amide group.

Mainly aromatic chain polymers formed through polar bonding groups such as imide groups 9 For example, chain polyesters obtained from terephthalic acid or inphthalic acid and dihydric alcohols, polyamides, polyamideimides, polyimides, polyetheramides, polyester amide, polyester amide,
Polyester ibado, bisphenol type epoxy resin,
Vinyl monomers 1 containing polar groups, such as polymers or copolymers of acrylonitrile, acrylamide, vinylpyrrolidone, vinylpyridine, vinyllactam, etc., are used. As the second organic component soluble in the continuous phase (first non-aqueous organic liquid), a mainly aliphatic chain polymer with low polarity is used. For example, a polymer or copolymer of butyl, hexyl, 2-ethylhexyl, octyl, lauryl or stearyl ester of acrylic acid or methacrylic acid, 1 alkoxide product with a degree of polymerization, 9 a monoalkoxide product of polypropylene oxide with a polymerization degree of 3 to 100, and its Monomethacrylates, e.g. NK ester M-90, M-
23G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) polymer or copolymer, polybutadiene.

Vinyl polymer such as polyisoprene; 9. One end-capped product of polyhydroquine fatty acid ester having a molecular weight of 1000 or more; 2. For example, one end-capped product of a self-condensate of 12-hydroxystearic acid with a monohydric carboxylic acid or monohydric alcohol; and its glycidyl methacrylate. Adduct polymers or copolymers, monolyzed natural rubber, cell p-s derivatives, and the like are used. The first organic component and the second organic component are obtained as a random polymer, a block polymer, or a graft polymer linked through a chemical bond.

Other examples that can be used as dispersion stabilizers include one incyanate group, acid A resin having one or more functional groups that can react with either an anhydride group or a carboxyl group is used. Examples of such functional groups include, for example, hydroxyl group, carboxyl group, methylol group, amino group, acid anhydride group, and epoxy group for incyanate group. Preferably hydroxyl groups are used. 1 for acid anhydride groups and carboxyl groups, such as incyanate groups, hydroxyl groups,
Ami7 groups, epoxy groups, 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. As a resin having such a functional group, 9
For example, alkoxy-modified resins such as butylated benzoguanamine formaldehyde resin, butylated melanformaldehyde resin, hydroxyl group, carboxyl group,
Telechelic rubber or decomposed natural rubber having an average molecular weight of several thousand degrees, which has an acid anhydride group, an epoxy group, an incyanate group, or a mercaptan group, is used. In addition, as a dispersion stabilizer, the first organic component of a polymer, a block polymer, or a kraft polymer in which the first organic component and the second organic component are linked through a chemical bond. Nine types are used by introducing functional groups into them.

Also used is the second organic component that is soluble in the continuous phase (first non-aqueous organic liquid) and has a functional group introduced therein. A method for introducing a functional group into these resins is to copolymerize a vinyl monomer having a functional group when the dispersion stabilizer is a vinyl polymer. Examples of vinyl monomers having a hydroxyl group include allyl alcohol, droxyethyl or hydroxyglobyl ester of acrylic acid or methacrylic acid, and acrylic acid of polyethylene oxide with a polymerization degree of 3 to 100 or polypropylene oxide with a polymerization degree of 3 to 100. Alternatively, methacrylic acid ester and the like are used. Examples of the vinyl monomer having a carboxyl group include acrylic acid and methacrylic acid.

Itaconic acid and the like 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 acryl azide or the like is used.

In the case of addition polymers and condensation polymers, they 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 polyincyanate or polyamine, carboxyl groups, acid anhydride groups, incyanate groups, amino groups, etc. may remain. Preferred resins as dispersion stabilizers are obtained by radical polymerization in the first non-aqueous organic liquid, aliphatic or alicyclic hydrocarbon. When the main chain is formed from a long chain alkyl ester of acrylic acid or methacrylic acid having 12 or more carbon atoms, the main chain is a monoalkoxy monomethacrylate of polypropylene oxide having a degree of polymerization of 20 or more, Hydroxyl group-containing vinyl polymers formed from alkoxy monoacrylates are used.

It is preferable that the molecular weight of the dispersion stabilizer is Filo00 or more. When it is less than 1000, aggregation tends to occur during the polymerization process. Especially when the molecular weight is 1,000~s o, o o o
A range of is preferred. As a concrete 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 weight percent, and the number of carbon atoms soluble in aliphatic or alicyclic hydrocarbons. The range consists of one type of acrylic monomer having a long chain alkyl group of 12 or more, or 80 to 98 weight percent of an acrylic monomer containing a monoalkoxide of polypropylene oxide having a degree of polymerization of 28 or more and/or a degree of polymerization of 20 or more.

It is soluble or swellable in the particulate polymer having imide groups produced in the present invention.

The second non-aqueous organic liquid is essentially non-miscible with the first non-aqueous organic liquid, and the second non-aqueous organic liquid is a non-aqueous organic liquid that has inert properties that do not inhibit the polymerization reaction. A solvent is used that is soluble or swellable in the polymer and acts as a solvent for contacting the reaction between end groups in the polymerization reaction and increasing the molecular weight of the resulting imide group-containing polymer. . Here, essentially immiscible with the first non-aqueous organic liquid includes in addition to completely insoluble in the first non-aqueous organic liquid.

This means that it also includes non-aqueous organic liquids that are not completely insoluble, but are immiscible to the extent that the two liquids phase separate at a certain mixing ratio. The second non-aqueous organic liquid is a polar liquid, and the first non-aqueous organic liquid also has a large affinity for the generated imide group-containing polymer or reactant contained in the dispersed phase. is 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,
an aliphatic or alicyclic hydrocarbon as the first non-aqueous organic liquid;
A combination with N-methyl-2-pyrrolidone is used as the second non-aqueous organic liquid.

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

Examples of trifunctional or higher-functional polyisocyanates used in the present invention include compounds 1 obtained by trimerizing diisocyanates, such as tolylene diisocyanate, xylylene diisocyanate, 44'-diphenyl ether diisocyanate, naphthalene-1,5-diisocyanate, 4′
- Trimer of aromatic diincyanate based on diphenylmethane diincyanate, ethylene diincyanate, 1.
4-tetramethylene diinsyanate.

1.6-hexamethylene diisocyanate, 1.12
- trimer of aliphatic diincyanate such as dodecane diisocyanate, cyclobutene 1,3-diincyanate,
Cyclohexane 1.3- and cyclohexane.

4-diincyanate, a trimer of alicyclic diincyanate of infopn diincyanate 4.

Triincyanate compound 1 For example, triphenylmethane-44:4''-triincyanate, polyphenylmethyl polyisocyanate, for example, a compound prepared by reacting a condensate of aniline and formaldehyde with phosgene, etc. are used. 3 amounts of diisocyanate Because it contains incyanurate rings, it is not only useful as a crosslinking component, but also provides excellent heat resistance.

Examples of the trifunctional incyanate used in combination if necessary include tolylene diisocyanate.

Aromatic diisocyanates such as xylylene diincyanate, 4,4'-diphenyl ether diisocyanate, naphthalene-15-diisocyanate, 44'-diphenylmethane diincyanate, ethylene/diincyanate, 1,4-tetramethylene diisocyanate, 1,
Aliphatic diisocyanates such as 6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutene 1,3-diisocyanate, cyclohexane/
l, 3- and 1,4-diisocyanates.

Alicyclic diisocyanates such as isophor/diincyanate are used. Considering heat resistance etc., tolylene diisocyanate is preferred.

44'-diphenyl ether diisocyanate.

Preferably, aromatic diisocyanates such as 4.4'-diphenylmethane diincyanate are used. A suitable method for producing incyanurate-containing polyinsyanate is shown in Japanese Patent Application No. 148820/1982.

Polyisocyanate controls the reaction rate during the polycondensation reaction process and obtains a stable particulate polymer using methanol, n
-Butanol, benzyl alcohol, C-caprolactam. Part or all of the incyanate groups may be stabilized with a suitable blocking agent having one active hydrogen in the molecule, such as methyl ethyl ketone oxime, phenol, or cresol.

As a polycarboxylic acid having an acid anhydride group.

For example, trimellitic anhydride, 1. Tricarboxylic acid anhydrides such as λ4-butanetricarboxylic acid-1,2-anhydride, a4L;-hensiphenonetricarboxylic acid-3,4'-anhydride, 1. λmi-4-butanetetodicarboxylic acid, cyclopentantetetodicarboxylic acid, bicyclo-(2,1)-octene-(7)-su & 5,6-tetracarboxylic acid, ethylenetetracarboxylic acid, bicyclo-[2 , S2]-oct-(7)-2/-2:3,5:6-tetracarboxylic dianhydride and aliphatic and alicyclic tetrabasic acids.

Pyromellitic acid, &3',44'-benzophenonetetracarboxylic acid, bis(a,4-dicarboxyphenyl)ether, λ3,6.7-1-phthalentithoracarboxylic acid, 1.2.5.6-naphthalene Tetracarboxylic acid, ethylene glycol bis trimellitate, 42'-bis(tortoise 4-biscarboxyphenyl)furopane, sτ,
3.3'-diphenyltetracarboxylic acid, perylene-3
, 49,10-tetracarboxylic acid, aromatic tetrabasic acids such as 4-dicarboxyphenylsulfone, thiophene-Z
Examples include tetrabasic acid di- or -anhydrides such as heterocyclic tetrabasic acids such as &45-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, a polyimide can be obtained from a polycarboxylic acid having only an acid anhydride group, such as tetracarboxylic dianhydride, and a polyisocyanate. Generally, considering heat resistance, cost, etc., trimellitic anhydride'tlkJ,
3.3', 4.4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride and the like are preferred.

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)in cyanurate, terephthalic acid, inphthalic acid, succinic acid, and adipic acid.

Sebacic acid, dodecanedicarboxylic acid, etc. are used.

Among these polycarboxylic acids, trifunctional or higher functional polycarboxylic acids also act as a branching component for obtaining a gelled particulate polymer, which is the object of 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 incyanate groups) is preferably in the range of 0.1 to 3.0, particularly preferably in the range of 0.3 to zO. Here, the IHI hydrate of the polycarboxylic acid is treated as the equivalent of the hydrate group (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 where 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, the content is particularly preferably 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 ratio of the amount of the second non-aqueous organic liquid to the reactant is such that the amount of the second non-aqueous organic liquid is 0.5 to 70% by weight based on the total amount of the second non-aqueous organic liquid and the reactant. preferable. If the amount is less than 0.5 weight percent, the polymerization reaction will be considerably difficult to proceed. When the amount 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. It becomes difficult.

Even if a dispersed phase is formed, aggregation tends to occur during the polymerization reaction. Particularly preferably a range of 2 to 40'li weight percent is used.

The reaction of the trifunctional or higher functional polyisocyanate, the polycarboxylic acid having a WI 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 organic liquid is determined 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-? 'N-methyl- not soluble in lolidone
2-pyrrolidone is not colored.

Preferably, the polymerization reaction is carried out in a substantially anhydrous atmosphere. 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 rapidly transformed into an inert compound when its reactant, particularly polyisocyanate, comes into contact with water. is not possible to produce as a dispersion medium. The reaction is
All the raw materials may be charged at the same time, or the reaction may be carried out in stages depending on the purpose.

The method of charging the reactants in the present invention requires some modification depending on the properties of the reactants. Is at least one component of the reactant soluble or swellable in the second non-aqueous organic liquid?9
It is desirable that it be liquid at the reaction temperature. Preferred specific examples include:

A fine powder is added to 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 the nonacid component. According to this method.

Polymerization reaction can proceed at a relatively low reaction temperature, and undesirable side reactions can be suppressed.

The 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 by adding it.

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

The imide group-containing particulate polymer obtained by the present invention can be prepared using methanol, n-butanol, benzyl alcohol, or e-caprolactam depending on the necessity during or after the reaction. Methyl ethyl ketone oxime, acetaldoxime, phenol.

Stabilization can be achieved by adding a suitable blocking agent having one active hydrogen in the molecule, such as cresol.

Stirring methods used in the process 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 preferred stirring method is to use an emulsifier to reduce the diameter of the particles at the beginning of the reaction, and then proceed with the reaction further near the polymerization group where the dispersion stability of the particles is good, instead of using a propeller type stirrer. 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.
In addition to this particulate polymer, the dispersed phase contains a second non-aqueous organic liquid 9 dispersion stabilizer.

Reactants and the like 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 0.1 to 500 microns, most preferably 0.5 to 100 microns. Methods for recovering such particulate polymers include filtration or decantation.

It can then be recovered from the dispersion solution by drying under normal or reduced pressure.

The recovered gelled particulate polymer having imide groups is heated at 100 to 400°C, preferably d200 to 30°C, as necessary.
By heat-treating at 0° C., the dispersion stabilizer contained in the gelled particulate polymer is 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 with reference to Examples.

Example 1 (1) Synthesis of dispersion stabilizer A four-loaf flask equipped with a thermometer, a stirrer and a 9-ball condenser 4Cr80PAR-H (Aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) 152? was added and the temperature was raised to 120°C. Lauryl methacrylate 183f prepared in advance, methacrylic acid- while passing nitrogen gas
2-Hydroxyethyl 17i, i benzoyl oxide paste (benzoyl peroxide content 50% by weight) 10
? The mixture was added dropwise over 2 hours while 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 had a nonvolatile content of 50.5 weight percent when baked at 170° C. for 30 minutes, and a number average molecular weight of 1 dispersion stabilizer of 14,000.

(2) Synthesis thermometer of tolylene diisocyanate trimer,
Add 100O5L of tolylene diisocyanate to a 94-hole flask equipped with a stirrer and a 9-ball condenser.

Anisic acid 0.52f, dimethylaminoethanol 0,3
00 F was introduced, and the temperature was raised to 80° C. while passing nitrogen.

The reaction was carried out at the same temperature until the content of incyanate groups (initial concentration: 48 weight percent) reached 321 weight percent. The infrared absorption spectrum of this product is 1710 cr.
An absorption of an isocyanurate ring was observed at 1410 cm-'', and an absorption of an isocyanate group was observed at 2260 cm-'.

(3) Synthesis of gelled particulate polymer having imide groups 4,4'-diphenylmethane diisocyanate 4 & 4P was added while passing nitrogen gas through a four-lobe flask equipped with a thermometer, a stirrer, and a 9-ball condenser. , tolylene diisocyanate trimer obtained in (2) 48.4).

Dispersion stabilizer solution obtained in (1) (non-volatile content 50.5% by weight) 19. Of, l80PAR-H (aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) 150p,
Add N-methyl-2-pyrrolidone 331 and raise the temperature to 110°C while stirring. Add 37.2% of pre-micronized trimellitic anhydride and incubate for 1 hour at 110°C, 1 hour at 120°C, 1 hour at 130°C, 1 hour at 140°C, 1 hour at 150°C, 160' The reaction was carried out at C for 2 hours. When a part of the brown particulate polymer dispersed in 15OPA-H was taken out with a hippet and added to N-methyl-2-pyrrolidone, the particulate polymer dissolved in N-methyl-2-pyrrolidone. No dripping occurred and N-methyl-2-pyrrolidone did not color. This was then collected by passing it through one pass.

After washing with n-hexane and acetone, under reduced pressure,
It was dried at 0°C for 5 hours. The infrared absorption spectrum of this particulate polymer includes a 1780y-”t11 imide bond,
Absorption of amide bond was observed at 1650 cm-" and 1540 cm-"9. When this particulate polymer is observed with a scanning electron microscope, it has a spherical shape.

The main particle size was approximately 10-80 μm. The starting temperature of thermal decomposition of this material is 390℃ (measurement conditions: heating rate 1
0°C/min, air atmosphere, sample amount 10 Da) Example 2 Using the same apparatus as in Example 1, (31), while passing nitrogen gas, the dispersion stabilizer solution obtained in Example 1.+11 (non-volatile 50.5% by weight) 19°Of.

Example 1. Tolylene diisocyanate trimer obtained in (2) 94.3 ? , l80PAR-H (aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) 150ψ.

N-methyl-2-pyrrolidone 33? was added, and the temperature was raised to 110°C while stirring. 37.7 p of trimellitic anhydride, which had been pulverized in advance, was added.

1 hour at 110°C, 1 hour at 120°C, 1 hour at 130°C, 1 hour at 140°C, 1 hour at 150°C.

The reaction was carried out 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 15OPAR-H was recovered by f-filtration, washed with n-hexane and then acetone, and then vacuumed at a reduced pressure of τ60. ℃
It was dried for 5 hours.

The infrared absorption spectrum of this particulate polymer.

Imide bond at 1780 crs-”, 1650 amount wr-
Absorption of the amide bond was observed at ", 1540 cm-". When this particulate polymer was observed with a scanning electron microscope, it was found to be spherical in shape, with a main particle diameter of about 10 to 80 μm. The starting temperature of thermal decomposition of this material was 290°C (Measurement test, temperature increase rate 10°C/ml, air atmosphere, sample amount 10cm) Example 3 A four-wheel tube was equipped with a thermometer, a stirrer, and a 9-ball tube cooler. 4.4'-diphenylmethane diisocyanate 37.8SL, '1! while passing nitrogen gas through the double flask. mfl11
, (31 tolylene diisocyanates obtained in 21 36
．． 2f, Example 1. Dispersion stabilizer solution obtained in (1) (nonvolatile content 50.5% by weight) 19.0? .

l5OPAR-H (aliphatic hydrocarbon manufactured by Esso Standard Oil Company, trade name) 150), N-methyl-2-pyrrolidone 33? was added, and the temperature was raised to 110°C while stirring.

Pre-pulverized trimellitic anhydride 58.0
Add F and heat at 110°C for 1 hour and at 120°C for 1 hour.
The reaction was carried out for 1 hour at 30°C, 1 hour at 146°C, 1 hour at 150°C, 2 hours at 160°C, and 5 hours at 180°C. After confirming the gelation of the particulate polymer in the same manner as in Example 1,
The brown particulate polymer dispersed in OPAR-H was collected by filtration, washed with n-hexane and then acetone, and then dried at 150°C under reduced pressure for 5 hours.

The infrared absorption spectrum of this particulate polymer.

Imide bond to 1780tyn-”, 1650cWt person 1
Absorption of an amide bond was observed at 540 cm-''. 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 44'-diphenylmethane diisocyanate was charged at 60% while trapping nitrogen gas in a four-loaf flask equipped with a thermometer, a stirrer, and a 9-bulb condenser. OSJ Actual Example 1, +21
Tolylene diisocyanate trimer 14.4P obtained in Example 1. (Dispersion stabilizer solution obtained in step 11 (non-volatile content 50.
5 weight percent)19. (1゜l5OPAR-H (Aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) 1
5 (add 33 fF of 1,N-methyl-2-pyrrolidone,
The temperature was raised to 110°C while stirring. Add 57.6f of trimellitic anhydride, which has been pulverized in advance, and
℃ for 1 hour, 120℃ for 1 hour, 130℃ for 1 hour, 1
The reaction was carried out at 40°C for 1 hour, at 150°C for 1 hour, 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 l80PAR-H was collected by filtration, and n-
After washing with hexane and acetone, 150℃ under reduced pressure.
It was dried for 5 hours.

The infrared absorption spectrum of this particulate polymer.

Imide bond at 1780cm-”, 1650cvr+-”
, absorption of amide bond was observed in 1540-1. 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 Example 1. (19.0) of the dispersion stabilizer solution (nonvolatile content 50.5 weight percent) obtained in Example 1) using the same apparatus as in 31 and passing nitrogen gas.

70% by weight, isophorone diisocyanate amer OS liquid <manufactured by Hiemitsussier-Werke-Hüls AG, trade name, IPDI-T 18908・) 146f,
N-methyl-2-pyrrolidone 33P was added and the temperature was raised to 110° C. with stirring. 30.0 SL of ninetrimellitic anhydride, which had been pulverized in advance, was added thereto, and the mixture was heated at 110°C for 1 hour and at 120°C for 1 hour.

The reaction was carried out at 130°C for 1 hour, at 140°C for 1 hour, 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 15OPAR-H was collected by filtration, and n
- After washing with hexane and then acetone, under reduced pressure 6
It was dried at 0°C for 5 hours.

The infrared absorption spectrum of this particulate polymer.

Imide bond at 1780cm-'', 1650m-', 15
Absorption of amide bond was observed in 406n-”9.
This particulate polymer did not dissolve N-methyl-2-pyrrolidone K at all. When this particulate polymer was observed with a scanning electron microscope, it was found to be spherical in shape, with a main particle diameter of approximately 10 to
It was 80 μm.

Procedural amendment (voluntary) November 1988 88 2. Name of the invention Process for producing particulate polymer having gelled imide groups 3.
Concerns with the case of the person making the amendment Patent applicant name (445) Hitachi Chemical Co., Ltd. 4, representative
Telephone: Tokyo 346-3111 (main representative) 6. Contents of amendment 1) In the second line from the bottom of page 32 of the specification of the present application, there is a line that says “Example (1)
"Example 1. (Corrected to 11.)

Claims (1)

[Scope of Claims] 1. A first non-aqueous organic liquid that is insoluble in the particulate polymer having imide groups to be produced, a dispersion stabilizer soluble in the first organic liquid, and a particulate polymer having imide groups to be produced. in the presence of a second non-aqueous organic liquid that is soluble or swellable with respect to the particulate polymer and is essentially immiscible with the first non-aqueous organic liquid. Trifunctional incyanate and trifunctional or higher functional incyanate 1. Polycarboxylic acids (...) having an acid anhydride group and optionally polycarboxylic acids (other than Ill) having an acid anhydride group (1
) is reacted until the particulate polymer having imide groups is insoluble in the second non-aqueous organic liquid. 1. A method for producing a gelled particulate polymer having imide groups, the particulate polymer having imide groups being dispersed in a first non-aqueous organic liquid. 2. The gelled imide according to claim 1, wherein the first non-aqueous organic liquid is an aliphatic or alicyclic hydrocarbon and the second non-aqueous organic liquid is N-methyl-2-pyrrolidone. A method for producing a particulate polymer having a group. λ polyisocyanate + 11 is 3 of diisocyanate
A method for producing a gelled particulate polymer having a nonaimide group according to claim 1 or 2, which is a polymer. 4. The method for producing a particulate polymer having a gelled imide group according to claim 1, 2 or 3, wherein the trifunctional incyanate is an aromatic diisocyanate. 5. Polycarbonate etn+ having an acid anhydride group can be used as trimellitic acid anhydride, pyromellitic dianhydride or &&'4
．． Claim 1rl which is 4'-benzophenonetetracarboxylic dianhydride. Item 2: A method for producing a particulate polymer having a gelled imide group according to Item 3 or 4.