JP2002179597A - Method for producing molecular compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for industrially producing a molecular compound, especially a molecular compound with high stability by solid-solid reaction or solid-liquid reaction. SOLUTION: This method for producing a molecular compound comprises the steps of blending/kneading together a solid host compound and a solid guest compound, or a solid host compound and a liquid guest compound, using a kneader, and as necessary making an extruding granulation; wherein at least one step selected from those described below is adopted: step 1 comprising blending/kneading the host compound and guest compound together followed by holding the resultant blend at >=50 deg.C but not higher than the discharge temperature of the guest compound for a specified period of time, step 2 comprising washing the molecular compound formed by blending/kneading the host compound and the guest compound together with a solvent capable of dissolving the guest compound, step 3 comprising grinding the solid host compound in advance, and step 4 comprising adding a poor solvent such as water for the solid host compound, the solid guest compound and the liquid guest compound followed by making a blending/kneading.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for industrially producing a large amount of a molecular compound having improved stability, and more particularly, to a method of improving stability using a solid-solid reaction or a solid-liquid reaction. The present invention relates to an industrial production method of a molecular compound.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a molecular compound represented by an inclusion compound, a method in which a host compound and a guest compound are dissolved in a solvent and reacted in a solution is generally performed. However, in the conventional method using a solvent, a molecular compound may not be generated depending on the type of the solvent, and a compound that includes only the solvent without including the guest molecule or a part of the compound that includes the guest molecule may be used. It has been pointed out that a compound containing a solvent may be obtained, and selection of conditions is sometimes difficult.

[0003] On the other hand, there have been proposed several methods for producing a compound by directly mixing a host compound and a guest compound without using a solvent. For example, JP-A-63-35533
The publication discloses a powdered host compound having a phenyl group and a hydroxyl group in one molecule and having more than 12 carbon atoms, and a powdered guest compound having a phenyl group and a carbonyl group in one molecule, respectively. After crushing into powder,
A method of mixing and reacting, after mixing the host compound and the guest compound, a method of pulverizing and reacting, a method of mixing and reacting the host compound and the guest compound while pulverizing, and the like, are disclosed. As a specific mixing method, a method of crushing and mixing in a mortar and a method of shaking and mixing with a shaker are described. Also, Japanese Patent Application Laid-Open No. Hei.
No. 236 describes a method for producing an inclusion compound in which a solid guest compound is heated and melted at room temperature, and then a powdered host compound which reacts with the guest compound to form an inclusion compound is added. . On the other hand, kneaders and granulators
Conventionally, mixing of food, tableting of pesticides or pharmaceuticals,
Or, it is generally used for modifying and strengthening resins.

[0004]

The conventional methods for producing molecular compounds by the solid-solid reaction are all related to small-scale production, and the production of molecular compounds by the solid-solid reaction is industrially large. It has never been conceived to carry out on a scale, and there is no known example of applying a kneader or a granulator to a solid-solid reaction or a solid-liquid reaction. In addition, when a molecular compound is actually used as various products and product raw materials, a molecular compound having improved stability is required. An object of the present invention is to provide an industrial method for producing a molecular compound by a solid-solid reaction or a solid-liquid reaction, particularly a molecular compound excellent in stability.

[0005]

Means for Solving the Problems The present inventors have been required to carry out industrial production of molecular compounds by a solid-solid reaction or a solid-liquid reaction, and have found the above problems. Mixing and / or kneading the and the guest compound with a kneader or a granulator, or further granulating, to confirm that a large amount of a molecular compound can be industrially produced, and At this time, after mixing and / or kneading the host compound and the guest compound, a step of maintaining the temperature at 50 ° C. or higher and not higher than the release temperature of the guest compound for a predetermined period, mixing and / or kneading the host compound and the guest compound. Washing the molecular compound thus generated with a solvent capable of dissolving the guest compound, crushing the solid host compound in advance, By employing either pressurized to mixing and / or kneading step, to verify that it is possible to produce improved stability molecular compound, and have completed the present invention.

That is, the present invention provides a method for producing a molecular compound having improved stability by mixing and / or kneading a solid host compound and a solid guest compound, or a solid host compound and a liquid guest compound. (A) a method of producing a molecular compound, which comprises performing any one of the following steps (a) to (d): mixing and / or kneading a host compound and a guest compound; Step (b) of maintaining the temperature at a temperature equal to or lower than the release temperature of the guest compound for a predetermined period of time washing the molecular compound produced by mixing and / or kneading the host compound and the guest compound with a solvent capable of dissolving the guest compound. Step (c) Pulverizing the solid host compound in advance Step (d) Poor solvent for the solid host compound, solid guest compound and liquid guest compound The molecular compound according to claim 1, wherein the average particle diameter of the solid host compound is reduced to 1.6 µm or less by the step of adding and mixing and / or kneading (claim 1) or the step (c). 3. The method according to claim 1, wherein the particle diameter of the solid host compound is reduced to 4.0 μm or less by the production method (claim 2) or the step (c).
(Claim 3), a method for producing the molecular compound described in claim 3,
The method for producing a molecular compound according to any one of claims 1 to 3, wherein the particle size of 80% by weight or more of the solid host compound is 2.0 µm or less.
Also, the present invention relates to a method for producing a molecular compound according to any one of claims 1 to 4, wherein the pulverization in the step (c) is airflow pulverization.

In the present invention, in the step (d), the poor solvent may be added to the solid host compound and the solid guest compound, or to the total weight of the solid host compound and the liquid guest compound, by 2%.
The method for producing a molecular compound according to any one of claims 1 to 5, wherein the compound is mixed and / or kneaded by adding 0 to 200% by weight, and a poor solvent is used in step (d). And mixing and / or kneading while heating until the content of the poor solvent becomes 1% by weight or less. 7. The method for producing a molecular compound according to any one of claims 1 to 6, wherein ) Or in step (d), a poor solvent is added, mixed and / or kneaded, and dried until the content of the poor solvent is 1% by weight or less. The method for producing a molecular compound according to claim (claim 8),
The method for producing a molecular compound according to any one of claims 1 to 8, wherein in step (d), the poor solvent is added in an amount of 200 ml or more and 1000 ml or less per 1 mol of the solid host compound (claim 9). And the solubility of the solid host compound, the solid guest compound and the liquid guest compound at room temperature as 1 g / 100 ml as the poor solvent in the step (d).
The method for producing a molecular compound according to any one of claims 1 to 9, wherein the following solvent is used (claim 10).
Further, the present invention relates to the method for producing a molecular compound according to any one of claims 1 to 9, wherein the poor solvent in the step (d) is water.

Further, the present invention is characterized in that a solid host compound and a required amount of a solid guest compound, or a solid host compound and a required amount of a liquid guest compound are mixed at a time. The method for producing a molecular compound according to any one of claims 1 to 12, wherein the method for producing a molecular compound according to any one of claims 1 to 12 and the method of mixing and / or kneading using a kneader (claim 13). Or mixing and / or mixing a solid host compound and a solid guest compound or a solid host compound and a liquid guest compound using a kneader.
Or a method for producing a molecular compound characterized by kneading (claim 14), or a method for producing a molecular compound according to claim 13 or 14, wherein the kneader is a multiaxial kneader (claim 15). ) Or before mixing and / or kneading the solid host compound and the solid guest compound, or the solid host compound and the liquid guest compound using a kneader, the solid host compound and the solid guest compound, or the solid host compound and the liquid guest compound in advance. The method for producing a molecular compound according to any one of claims 13 to 15, wherein the compound and the compound are uniformly mixed, and a solid host compound, a guest compound, and a generated molecule using a kneader. The method for producing a molecular compound according to any one of claims 13 to 16, wherein the compound is mixed and / or kneaded in a stable temperature range. Section 17) and the solid host compounds with solid guest compound, or solid host compound and a liquid guest compound are mixed and / or kneaded in a kneader,
The extrusion granulation is further performed.
A method for producing a molecular compound according to any one of the above (Claim 18)
19. The method for producing a molecular compound according to claim 1, wherein the solid host compound is 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane. ) Or the guest compound is 2-ethyl-4-methylimidazole, and the method for producing a molecular compound according to any one of claims 1 to 19 (claim 20).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a molecular compound of the present invention includes the steps of (1) mixing and / or mixing a solid host compound and a solid guest compound, or a solid host compound and a liquid guest compound.
Or a method for producing a molecular compound having improved stability by kneading, wherein at least (a) after mixing and / or kneading the host compound and the guest compound, the mixture is heated to 50 ° C.
The step of maintaining the temperature at a temperature equal to or lower than the release temperature of the guest compound for a predetermined period, and (b) dissolving the guest compound in the molecular compound generated by mixing and / or kneading the host compound and the guest compound. One of the step of washing with a solvent, the step of (c) previously grinding the solid host compound, and the step of (d) adding and mixing and / or kneading a poor solvent for the solid host compound, the solid guest compound and the liquid guest compound. The method is not particularly limited as long as it is a method of performing one step, or (2) a method of mixing and / or kneading a solid host compound and a solid guest compound, or a solid host compound and a liquid guest compound using a kneader. Here, a molecular compound is a compound that can exist stably alone by two or more component compounds. It refers to a compound bound by a relatively weak interaction other than a covalent bond represented by a force,
Includes hydrates, solvates, adducts, clathrates and the like.
In addition, the above-mentioned clathrate is a compound in which a three-dimensional structure formed by bonding atoms or molecules has pores of an appropriate size, in which other atoms or molecules have non-covalent interaction. Means a substance that enters at a constant composition ratio. Such a molecular compound is obtained by mixing a host compound and a guest compound, and has a function of enabling selective separation of a guest compound as a useful substance, chemical stabilization of the guest compound, non-volatilization and powderization. It is a useful substance in that
Further, the molecular compound of the present invention also includes a molecular compound composed of three or more components and obtained by reacting two or more types of guest compounds. Further, the crystallinity of the molecular compound can be confirmed mainly by examining the X-ray diffraction pattern. The presence of the polymorph in the molecular compound having the same composition can be confirmed by thermal analysis, X-ray diffraction pattern, solid N
It can be confirmed by MR or the like.

The solid host compound used in the present invention has a specific structure in which other atoms or molecules are incorporated into a vacancy inside a three-dimensional structure formed by bonding atoms or molecules with a certain composition. Is not particularly limited as long as it is a compound capable of constructing, specifically, tetrakisphenols,
1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol, 1,6-bis (2-chlorophenyl) -1,6-diphenylhexane-2,4-diyne-1,6 -Diol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 2,5-bis (2,
4-dimethylphenyl) hydroquinone, 1,1-bis (2,4-dimethylphenyl) -2-propyn-1-ol, 1,1,2,2-tetraphenylethane-1,2
-Diol, 1,1'-bi-2-naphthol, 9,10
-Diphenyl-9,10-dihydroxyanthracene,
1,1,6,6-tetra (2,4-dimethylphenyl)
-2,4-hexadiyne-1,6-diol, 9,10
-Bis (4-methylphenyl) -9,10-dihydroxyanthracene, 1,1-bis (4-hydroxyphenyl) cyclohexane, N, N, N ', N'-tetrakis (cyclohexyl)-(1,1'- Biphenyl) -2-
2'-dicarboxamide, 4,4'-sulfonylbisphenol, 4,4'-butylidenebis (3-methyl-
6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (4-chlorophenol),
2,2'-methylenebis (4-chlorophenol), deoxycholic acid, cholic acid, α, α, α ', α'-tetraphenyl-1,1'-biphenyl-2,2'-dimethanol, t- Butylhydroquinone, 2,5-di-ter
t-butylhydroquinone, granular corn starch, 1,
4-diazabicyclo- (2,2,2) -octane, 3,
Examples thereof include 3'-bisphenylsulfonyl-4,4'-dihydroxyphenylsulfone and tri-o-thymotide.

The above tetrakisphenols include, for example, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (hereinafter referred to as “TEP”),
1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane, 1,
1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-
(Methoxy-4-hydroxyphenyl) ethane, 1,1,
2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,3,3-tetrakis (4
-Hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-fluoro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-chloro-4
-Hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methoxy-4
-Hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1,4,4-tetrakis (4-hydroxyphenyl) butane, 1,1, 4,4-tetrakis (3-fluoro-4-hydroxyphenyl) butane,
1,1,4,4-tetrakis (3-chloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methyl-4-hydroxyphenyl) butane, 1,
1,4,4-tetrakis (3-methoxy-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,1,5,5- Tetrakis (4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-fluoro-4-hydroxyphenyl) pentane, 1,1,
5,5-tetrakis (3-chloro-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3-methyl-4-hydroxyphenyl) pentane, 1,1,
5,5-tetrakis (3-methoxy-4-hydroxyphenyl) pentane, 1,1,5,5-tetrakis (3
Tetrakis (hydroxyphenyl) alkanes such as 5-dimethyl-4-hydroxyphenyl) pentane can be specifically exemplified, and TEP is particularly preferred for practical use.

The solid or liquid guest compound used in the present invention can be incorporated into a vacancy inside a three-dimensional structure formed by bonding atoms or molecules with a certain composition to form a specific structure. The compound is not particularly limited as long as it is a compound, for example, water, methanol, ethanol, isopropanol, n-butanol, n-octanol, 2-ethylhexanol, allyl alcohol, propargyl alcohol, 1,2-butanediol, 3-butanediol, 1,4-butanediol, cyclohexanediol, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, 4-
Alcohols such as chlorophenyl-3-iodopropargyl formal, aldehydes such as formaldehyde, acetaldehyde, n-butyraldehyde, propionaldehyde, benzaldehyde, phthalaldehyde, α-bromocinnamaldehyde, phenylacetaldehyde, acetone, methyl ethyl ketone, diethyl ketone, dibutyl Specific examples thereof include ketones such as ketone, methyl isobutyl ketone, cyclohexanone, acetylacetone and 2-bromo-4'-hydroxyacetophenone.

The guest compounds include acetonitrile, acrylonitrile, n-butyronitrile, malononitrile, phenylacetonitrile, benzonitrile, cyanopyridine, 2,2-dibromomethylglutarnitrile, 2,3,5,6-tetrachloroisophthalonitrile. , 5-chloro-2,4,6-trifluoroisophthalonitrile, nitriles such as 1,2-dibromo-2,4-dicyanobutane, diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, tetrahydropyran, dioxolan, trioxane Ethers such as methyl acetate, ethyl acetate, butyl acetate, n-heptyl acetate, esters such as bis-1,4-bromoacetoxy-2-butene, sulfonamides such as benzenesulfonamide, and N-methyl Amides such as lumamide, N, N-dimethylformamide, dicyandiamide, dibromonitrilepropionamide, 2,2-dibromo-3-nitrilopropionamide, N, N-diethyl-m-toluamide, dichloromethane, chloroform, dichloroethylene, tetrachloroethylene Lactams such as ε-caprolactone, lactones such as ε-caprolactone, oxiranes such as aryl glycidyl ether, morpholines, phenols such as phenol, cresol, resorcinol and p-chloro-m-cresol. Can be specifically exemplified.

As the guest compound, formic acid, acetic acid,
Carboxylic acids such as propionic acid, oxalic acid, citric acid, adipic acid, tartaric acid, benzoic acid, phthalic acid, salicylic acid and thiocarboxylic acids, sulfamic acids, thiocarbamic acids, thiosemicarbazides, urea, phenylurea, diphenylurea, thiourea And ureas such as phenylthiourea, diphenylthiourea, N, N-dimethyldichlorophenylurea and the like, thioureas, isothioureas, sulfonylureas, thiophenol, allyl mercaptan, n
Thiols such as butyl mercaptan and benzyl mercaptan, sulfides such as benzyl sulfide and butyl methyl sulfide, disulfides such as dibutyl disulfide, dibenzyl disulfide, tetramethyl thiuram disulfide, dimethyl sulfoxide, dibutyl sulfoxide, and sulfoxide such as dibenzyl sulfoxide. , Dimethyl sulfone, phenyl sulfone, phenyl-
Specific examples include sulfones such as (2-cyano-2-chlorovinyl) sulfone, hexabromodimethyl sulfone, and diiodomethyl paratolyl sulfone; thiocyanic acids such as methyl thiocyanate and methyl isothiocyanate; and isothiocyanic acids. be able to.

Examples of the guest compound include amino acids such as glycine, alanine, leucine, lysine, methionine and glutamine, amide and urethane compounds, acid anhydrides, aromatic hydrocarbons such as benzene, toluene and xylene, and alkanes. , Alkenes, alkynes, butyl isocyanate, cyclohexyl isocyanate, isocyanates such as phenyl isocyanate, methylene bisthiocyanate, thiocyanates and isothiocyanates such as methylenebisisothiocyanate, nitro compounds such as tris (hydroxymethyl) nitromethane, Ammonia, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine,
Allylamine, hydroxylamine, ethanolamine, benzylamine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, dipropylenediamine, N, N-dimethylethylenediamine, N,
N'-dimethylethylenediamine, N, N-dimethyl-
Non-functional compounds such as 1,3-propanediamine, N-ethyl-1,3-propanediamine, trimethylhexamethylenediamine, alkyl-t-monoamine, menthanediamine, isophoronediamine, guanidine, and N- (2-hydroxypropyl) aminomethanol Cycloaliphatic amines can be specifically exemplified.

Examples of the guest compound include cyclohexylamine, cyclohexanediamine, bis (4-aminocyclohexyl) methane, pyrrolidine, azetidine, piperidine, piperazine, N-aminoethylpiperazine, N, N'-dimethylpiperazine and the like. Crosslinking of cyclic aliphatic amines such as piperazines and pyrrolines, 1,8-diazabicyclo [5,4,0] undecene-7, 1,5-diazabicyclo [4,3,0] non-5-ene, etc. Aromatic amines such as type amines, aniline, N-methylaniline, N, N-dimethylaniline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and m-killenediamine; Epoxy compound added polyamine, Michael Modified polyamines of pressurized polyamines, such as Mannich addition polyamine, thiourea addition polyamine, ketone blocked polyamine, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropyl imidazole, 2-n-propyl imidazole, 2
-Ethyl-4-methylimidazole, 1-benzyl-2
-Methylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 2-
Specific examples of imidazoles such as phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole and 1-benzyl-2-methylimidazole can be given.

As the guest compound, pyrrole, pyridine, picoline, pyrazine, pyridazine, pyrimidine, pyrazole, triazole, benzotriazole,
Triazine, tetrazole, purine, indole, quinoline, isoquinoline, carbazole, imidazoline, pyrroline, oxazole, piperine, pyrimidine, pyridazine, benzimidazole, indazole, quinazoline, quinoxaline, phthalimide, adenine, cytosine, guanine, uracil, 2-methoxycarbonylbenz Imidazole, 2,3,5,6-tetrachloro-4-
Methanesulfonylpyridine, 2,2-dithio-bis-
(Pyridine-1-oxide), N-methylpyrrolidone, methyl 2-benzimidazolecarbamate, 2-
Sodium pyridinethiol-1-oxide, hexahydro-1,3,5-tris (2-hydroxyethyl)-
s-triazine, hexahydro-1,3,5-triethyl-s-triazine, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine,
N- (fluorodichloromethylthio) phthalimide, 1
Nitrogen-containing heterocyclic compounds such as -bromo-3-chloro-5,5-dimethylhydantoin, 2,4,6-trichlorophenylmaleimide, furan, furfuryl alcohol, tetrahydrofurfuryl alcohol, furfurylamine,
Oxygen-containing heterocyclic compounds such as pyran, coumarin, benzofuran, xanthene and benzodioxane, oxazole, isoxazole, benzoxazole, benzisoxazole, 5-methyloxazolidine, 4- (2-nitrobutyl) morpholine, 4,4'- Specific examples include nitrogen-containing and oxygen heterocyclic compounds such as (2-ethyl-2-nitrotrimethylene) dimorpholine.

Further, thiophene, 3,3,4,4-tetrahydrothiophene-1,1 is used as a guest compound.
-Dioxide, 4,5-dichloro-1,2-dithiolan-3-one, 5-chloro-4-phenyl-1,2-dithiolan-3-one, 3,3,4,4-tetrachlorotetrahydrothiophene Sulfur-containing heterocyclic compounds such as -1,1-dioxide, thiazole, benzothiazole, 5-chloro-2-methyl-4-isothiazolin-3-one,
-Methyl-4-isothiazolin-3-one, 4,5-dichloro-3-n-octylisothiazolin-3-one,
2-octyl-4-isothiazolin-3-one, 1,2
-Nitrogen-containing and sulfur heterocyclic compounds such as benzisothiazolin-3-one, 2-thiocyanomethylbenzothiazole, 2- (4-thiazolyl) benzimidazole and 2-thiocyanomethylbenzothiazole, steroids such as cholesterol, brucine , Quinine, alkaloids such as theophylline, cineole, hinokitiol, menthol, terpineol, borneol, nopol, citral, citronellol, citronellal, geraniol, mentone, eugenol, linalool, natural essential oils such as dimethyl octanol, primrose, jasmine, lemon and the like Specific examples thereof include synthetic fragrances, vitamins such as ascorbic acid, nicotinic acid, and nicotinamide, and related compounds.

As described above, the method of producing a molecular compound having improved stability according to the present invention includes mixing and / or kneading a solid host compound and a solid guest compound, or a solid host compound and a liquid guest compound. A method for producing a molecular compound, comprising: (a) mixing and / or kneading a host compound and a guest compound, and then maintaining the mixture at a temperature of 50 ° C. or higher and a guest compound release temperature for a predetermined period; Washing the molecular compound produced by mixing and / or kneading the host compound and the guest compound with a solvent capable of dissolving the guest compound,
(c) a step of previously grinding the solid host compound, (d)
A method of adding one or more of the steps of mixing and / or kneading by adding a poor solvent to the solid host compound, the solid guest compound, and the liquid guest compound may be mentioned. The `` compound '' refers to a molecular compound capable of improving the bonding state between the host compound and the guest compound and appropriately controlling the release of the guest compound from the molecular compound. This will be described more specifically by taking the case of using as an example. Reaction-curable resin paint,
For example, a thermosetting paint such as an epoxy paint contains an epoxy oligomer and a resin curing catalyst, and if the curing of the resin proceeds during storage and the viscosity increases, it becomes difficult to use the paint as a final paint. For example, a curing accelerator for epoxy resin, 2-ethyl-4-methylimidazole (2E4M
Z) is excellent in curing catalyst performance, but when coexisted with an epoxy oligomer, has the disadvantage that the curing of the resin proceeds during storage and the usable time (working time) is short, At present, it is used only in the two-pack type, in which the catalyst and resin are mixed immediately before use, and is not used as a one-pack type in which the catalyst and resin are mixed in advance. There was a drawback that the properties were poor. From these facts, a molecular compound having improved stability when a substance having a resin curing catalytic activity is used as a guest compound has a long pot life, and does not increase the viscosity of the coating during its storage, thereby improving the coating efficiency. In this case, it can be said that the compound is a molecular compound having an excellent performance of rapidly curing by heating or the like.

By adopting the above-mentioned step (a), that is, after mixing and / or kneading the host compound and the guest compound, the mixture is kept at a temperature of 50 ° C. or more and the guest compound release temperature for a predetermined period (hereinafter referred to as “the temperature”). "Heat retention"
By doing so, it is possible to enhance the stability of the generated molecular compound, for example, when using a substance having a resin curing catalytic activity as a guest compound, when using the guest compound alone or when using a molecular compound that has not been heated and held. As compared with the case of using the resin curing agent, the expression of the resin curing catalyst activity can be appropriately controlled, and the pot life of the powder coating or the like can be greatly extended. Although the lower limit of the temperature range of the heating and holding treatment is not limited as long as it is 50 ° C. or more,
C. or higher is preferable, and if it is lower than 50 ° C., the effect of improving the stability of the molecular compound cannot be sufficiently expected. Also,
The release temperature (release temperature) of the guest compound, which is the upper limit of the temperature range of the heating and holding treatment, varies depending on the type of the molecular compound. For example, in the case of a molecular compound composed of TEP and 2E4MZ, it is in the range of 180 to 200 ° C. . In this case, the temperature range of the heating and holding treatment can be 50 to 170C, preferably 70 to 150C.

By adopting the above-mentioned step (b), that is, a molecular compound produced in a solvent capable of dissolving the guest compound, preferably a solvent capable of dissolving the guest compound without dissolving the host compound, By washing, the stability of the molecular compound after washing can be increased.For example, when a substance having a resin curing catalytic activity is used as a guest compound, compared with the case of using an unwashed molecular compound, The development of curing catalyst activity can be appropriately controlled, and the pot life in powder coatings and the like can be greatly extended. The washing solvent is not particularly limited as long as it can dissolve the guest compound, but a solvent having a strong dissolving power for the guest compound is preferable.

By adopting the above-mentioned step (c), that is, in producing a molecular compound by mixing and kneading the above-mentioned solid host compound with a guest compound, the solid host compound pulverized by a gas pulverization method or the like as the solid host compound is used. By using a compound, it is possible to enhance the stability of the generated molecular compound.For example, when a substance having a resin curing catalytic activity is used as a guest compound, or when a molecular compound made from an unmilled solid host compound is used. As compared with the above, the expression of the activity of the resin curing catalyst can be appropriately controlled, and the pot life of the powder coating or the like can be greatly extended. Examples of the pulverized product of the solid host compound include a solid host compound having an average particle size of 1.6 μm or less, preferably 1.1 μm or less, and a particle size of 4.0 μm or less, preferably 3.7 μm or less. A certain solid host compound and a solid host compound having a particle size of 80% by weight or more of 2.0 μm or less, preferably 1.8 μm or less can be suitably exemplified.

By employing the above step (d), that is, when mixing and / or kneading the host compound and the guest compound using a kneader or the like, the poor solvent for the solid host compound, the solid guest compound and the liquid guest compound is removed. By adding and mixing and / or kneading, the stability of the generated molecular compound can be increased. For example, when a substance having a resin curing catalytic activity is used as a guest compound, the compound is formed without adding a poor solvent. Compared with the case where a molecular compound is used, the expression of the resin curing catalyst activity can be appropriately controlled, and the pot life of a powder coating or the like can be greatly extended. The mixing and / or kneading with the addition of the poor solvent may be performed by adding 20 to 200 to the total weight of the solid host compound and the solid guest compound, or the total weight of the solid host compound and the liquid guest compound.
By adding and mixing and / or kneading by weight% of a poor solvent,
Mixing and / or kneading while adding a poor solvent and heating until the content of the poor solvent becomes 1% by weight or less, or mixing and / or kneading with the addition of the poor solvent to reduce the content of the poor solvent to 1% by weight or less. Mixing and / or kneading in the coexistence of a poor solvent, such as drying to the extent that it is possible, is particularly preferable to make the content of the poor solvent of the produced molecular compound 1% by weight or less, and to further enhance the stability of the produced molecular compound. Can be. The amount of the poor solvent is not particularly limited, but is preferably 200 ml or more and 1000 ml per 1 mol of the solid host compound.
The stability of the resulting molecular compound can be enhanced by adding the compound in an amount of preferably 400 ml or more and 600 ml or less. In this case, a molecular compound having excellent stability can be obtained even if the poor solvent content slightly exceeds 1% by weight. Can be. Examples of the poor solvent include a solvent in which the solubility of the solid host compound, the solid guest compound, and the liquid guest compound at room temperature is 1 g / 100 ml or less,
Specifically, water can be preferably exemplified.

The means for mixing and / or kneading the solid host compound and the solid guest compound or the solid host compound and the liquid guest compound in the above-described method for producing a molecular compound is not particularly limited. It is preferable to mix and / or knead using a compound, since it is suitable for mass production on a factory scale. The method for producing a molecular compound of the present invention is further characterized in that a solid host compound and a solid guest compound or a solid host compound and a liquid guest compound are mixed and / or kneaded using a kneader (including a kneader). Therefore, the kneader and the mixing and kneading using the kneader will be described below.

The kneader used in the present invention may be any device that can sufficiently mix and / or knead a host compound and a guest compound on a large scale. Any kneading machine or kneading machine generally used in the field or the like can be used. As the kneading machine, a single-shaft or two-shaft type is preferably a device that can mix and / or knead a substance by rotating a paddle mounted on a shaft, and further have a small clearance between a paddle and a body, for example, JP-A-3-8
It is more preferable to use a device equipped with a jacket capable of cooling or heating the apparatus body, as described in JP-A-6223 and JP-A-9-173825. Further, the kneading machine is preferably a kneading machine mainly composed of a barrel called a barrel and a screw equipped with various screw elements, and usually having a structure in which a screw passes through a plurality of barrels. The screw elements include trapezoidal screw elements, trapezoidal cut screw elements, trapezoidal reverse cuts, ball screw elements, kneading paddles, and the like, and any combination thereof can be performed. The substance sent into the barrel is moved in the barrel by a screw, and is subjected to processing such as shearing and mixing in the barrel by a screw element such as a kneading paddle. In addition, if the kneading machine has basic characteristics such as a conveying function, a mixing function, a shearing function, a compressing function, a crushing function, and a heating function which are generally used in a food field, a plastic field, and the like, it can be used as it is. Can be. In particular, a twin-screw kneader such as a non-meshing type different direction or co-rotating kneader or a complete or partially intermeshing type different direction or co-rotating kneader is preferable.

As a method of mixing and / or kneading the host compound and the guest compound by using a kneader or the like, the host compound or the guest compound is charged into the kneader or the like, and then the guest compound or the host compound which is the partner is sequentially or at once. A method of charging and mixing and / or kneading; a method of simultaneously charging and mixing and / or kneading the host compound and the guest compound in a kneader; a method of mixing and / or kneading the host compound and the guest compound in advance so as to be uniform. After that, it is possible to adopt a method in which the mixture is charged into a kneader or the like and mixed and / or kneaded. Further, when the host compound and the guest compound are mixed and / or kneaded at once, it is necessary to use a necessary amount of the solid guest compound or a necessary amount of the liquid guest compound with respect to the solid host compound.
This is advantageous in removing unreacted guest compounds from the guest compound reaction system. In addition, when the melting point of the solid host compound or the solid guest compound is 100 ° C. or less, the mixture is heated and melted in a water bath or the like, and stirred and mixed so that both are uniform.
It is preferable that the mixture is put into a kneader and mixed and / or kneaded. As for the degree of uniformity, it is sufficient that the two are uniformly mixed visually.

The reaction proceeds rapidly, and the reaction is completed in about 10 to 20 minutes after the starting materials are charged into the apparatus and mixing and / or kneading is started. Although the reaction proceeds even at room temperature, when the generated molecular compound has particularly good crystallinity, a large load is applied to the reaction apparatus and mixing or kneading may be hindered. In a temperature range in which the molecular compound is stable,
The reaction is preferably performed in a temperature range of 120 ° C. In addition, when the reaction is very fast and the release temperature of the guest compound is high, the host compound and the guest compound solidify immediately from the contact point, so that the whole may not be uniformly mixed even if stirring is performed using a kneader. . In such a case, once the reaction mixture is taken out and finely ground,
The molecular compound can be efficiently produced by mixing or kneading again using the kneader.

When the molecular compound finally obtained has a high melting point and good crystallinity, it is ground during mixing and / or kneading, and can be taken out of the kneader after the reaction and used as it is. If necessary, it can be ground. Further, regardless of the melting point and the crystallinity, after mixing and / or kneading, it is also possible to granulate into a specific shape using an extrusion granulator according to the application. Further, the obtained molecular compound can be used after it is aged while keeping it at a temperature not higher than the decomposition point of the molecular compound to prepare a crystal system and the like.

As the extrusion granulator used in the present invention, any general equipment widely used in the fields of pharmaceuticals, agricultural chemicals, foods, plastic molding and the like can be used. Any type such as a roll type, a blade type, a self-molding type, and a ram type can be used.

In particular, when a multi-screw extruder is used, mixing, kneading, and granulation operations can be performed collectively, which is preferable from the viewpoint of industrial production. The main part of the extruder is mainly composed of a cylinder called a barrel, a die corresponding to an outlet, and a screw equipped with various screw elements, and is preferably one having a structure in which a screw usually passes through a plurality of barrels. . The screw elements include trapezoidal screw elements, trapezoidal cut screw elements, trapezoidal reverse cuts, ball screw elements, kneading paddles, and the like, and any combination thereof can be performed.
Then, the substance sent into the barrel moves in the barrel by a screw, and is subjected to processing such as shearing and mixing in the barrel by a screw element such as a kneading paddle, and is extruded from the pores of the die. Normally, each barrel and die can be independently temperature-controlled.

The number of rotations of the screw can be appropriately set according to the type and type of the extruder, the raw material, the shape of the screw, and the like. In addition, the discharge die can be appropriately replaced according to the purpose, and specifically, a circular discharge die having various diameters for obtaining a columnar processed product, a flat die for obtaining a plate-shaped processed product. A discharge die or the like can be used. As a specific model of a multi-axis extruder,
Examples include Labo Luder Mark II (manufactured by Japan Steel Works, Ltd.) and PCM series twin screw extruder (manufactured by Ikegai Co., Ltd.).

The use form of the molecular compound of the present invention is not particularly limited. For example, two or more kinds of molecular compounds each composed of different component compounds can be used in combination. The molecular compound of the present invention can be used in combination with other substances as long as the intended function is not impaired.
An excipient or the like may be added to the molecular compound of the present invention to form granules or tablets for use. Further, they can be used by adding them to resins, paints, and their raw materials and raw material compositions. In addition, the molecular compound of the present invention can be used as it is as a raw material for organic synthesis or as a specific reaction field.

For example, using 3,3'-bis (phenylsulfonyl) -4,4'-dihydroxyphenylsulfone as a host compound, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4 -Isothiazolone bactericides such as isothiazolin-3-one, antibacterial and insecticide / insect repellents such as hinokitiol and 1,8-cineole, fragrances such as rosemary, antifoulants such as isothiazolone compounds, phthalic anhydride, tetrahydroanhydride Curing agents for resins such as phthalic acid and 1,8-diazabicyclo [5,4,0] undecene-7,1,5-diazabicyclo [4,3,0]
A catalyst such as a curing accelerator for epoxy resin such as non-5-ene or 2-ethyl-4-methylimidazole or an inclusion compound using an organic solvent such as toluene, xylene or pyridine as a guest has an action inherent to the guest compound. Besides, functions such as sustained release, reduction of skin irritation, chemical stabilization, non-volatility, powderization, selective separation of useful substances, etc. are newly added,
It is extremely useful as a catalyst and organic solvent for fungicides, antibacterial agents, insecticides / insect repellents, fragrances, antifouling agents, resin curing agents, etc. having new properties.

[0034]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

Example 1 [Production of molecular compound using kneader] As a guest compound, 2-ethyl-4-methylimidazole (2E4MZ) which is a curing accelerator for epoxy resin was used. 33.3 g of TEP (75 mmol, purity 90)
%), 17.0 g of 2E4MZ (150
mmol, purity 97%) was added with good stirring, and stirring was continued for another 5 minutes. The mixture thus obtained was gradually added to the mixer section while rotating the rotor of a kneader (Brabender Plasticorder PLV151 type, manufactured by Brabender) set at 25 ° C., and after the addition was completed, the mixture was further added for 10 minutes. The stirring was continued for another minute, and the reaction product was taken out. ¹ H-NMR and powder X
When a line diffraction measurement was performed, formation of a molecular compound of host compound: guest compound = 1: 2 was observed. Also,
When the thermal behavior of the reaction product was observed by TG-DTA measurement, weight loss was observed at 180 ° C., and it was confirmed that a molecular compound was generated. FIG. 1 shows the ¹ H-NMR spectrum, FIG. 2 shows the powder X-ray diffraction pattern, and FIG. 3 shows the thermal analysis (TG-DTA) chart.

Example 2 [Production of molecular compound using kneader (investigation of kneading temperature)] The reaction was carried out in the same manner as in Example 1 except that the kneading temperature was changed to 70 ° C, 100 ° C, and 120 ° C. As a result, a molecular compound showing the same TG-DTA, powder X-ray diffraction, and infrared absorption spectrum measurement results as in Example 1 was obtained. As described above, in the reaction between TEP and 2E4MZ, no difference in reactivity depending on the reaction temperature was observed.

Example 3 [Production of molecular compound using kneader (investigation of mixing ratio of host and guest)] 8.5 g of 2E4MZ (75 mmol, purity 97)
%), Except that it was changed to
The obtained molecular compound is a host compound: guest compound =
1: 2 mixture. From this, it was found that the molecular compound obtained even when the mixing ratio between the guest compound and the host compound was changed was always a molecular compound having a constant composition ratio. In addition, the above host compound: guest compound = 1:
8.5 g of 2E4MZ (75 mm
ol, purity: 97%), and the mixture was subjected to various instrumental analysis in the same manner as in Example 1. As a result, the molecular compound obtained was a host compound: guest compound = 1: 2.

Example 4 [Production of molecular compound using kneader] TEP 222.0 g (510 mmol, purity 91.5 g)
%) Was added to a bench kneader (manufactured by Irie syoukai) as a kneading machine, and the mixture was heated and melted with stirring.
14.6 g (1.02 mol, purity 98.05%) was added, stirring was further continued for 20 minutes, and sampling was arbitrarily performed from three places. Thereafter, the mixture was heated to 90 ° C. and stirred for 20 minutes to complete the reaction. After cooling, various instrumental analyzes were performed as in Example 1. From the measurement of the sample before heating,
No formation of molecular compounds was observed. After ¹ H-NMR and powder X-ray diffraction measurements were performed on the product after the reaction, a molecular compound of host compound: guest compound = 1: 2 was obtained.

Example 5 [Production of molecular compound using kneader] As a guest compound, 1,8-diazabicyclo [5,4,0] -undecene-7 which is a curing accelerator for epoxy resin is used.
(DBU) was used. 33.3 g of TEP (75 mmo
l, purity 90%), 22.9 g of DBU (150 mmo)
1, purity 99%) with good stirring and continued stirring for another 5 minutes. The mixture thus obtained is
While rotating the rotor of a kneading machine (Brabender Plasticorder PLV151, manufactured by Brabender) set at 0 ° C., gradually add the mixture to the mixer section, and after completion of the addition, continue stirring for another 10 minutes to remove the reaction product. I took it out.
When ¹ H-NMR and powder X-ray diffraction measurement were performed on the reaction product, a host compound: guest compound =
Formation of a 1: 2 molecular compound was observed. Further, when the thermal behavior of the reaction product was observed by TG-DTA measurement, weight loss was observed at 169 ° C. and 316 ° C., and it was confirmed that a molecular compound was generated. ¹ H-NM
The R spectrum is shown in FIG. 4 and the powder X-ray diffraction pattern is shown in FIG.
FIG. 6 shows a thermal analysis (TG-DTA) chart. When the thermal behavior of the mixture before kneading by the kneader was observed by TG-DTA measurement,
The weight loss was observed in three stages from ℃, suggesting that some molecular compounds were formed.

Example 6 [Production of molecular compound by step (a)] A 1 L bench kneader (Irie syoukai) was used at 82 ° C.
2E4MZ (purity 98.05%) 1
Then, 06.7 g (0.95 mol) was charged with stirring, and then 203.5 g (0.5%) of TEP (purity: 97.9%).
Mol) was added, and the mixture was stirred and mixed at the same temperature for 2 hours to prepare a molecular compound. When the prepared molecular compound was taken out from the kneader, the weight was 289.7 g.
From the measurement result of ¹ H-NMR of the obtained molecular compound, T
The molar ratio of EP: 2E4MZ was 1: 1.85. This molecular compound is kept in an oven heated to 70 ° C.,
Samples were taken every 1, 3, 4, and 6 weeks and subjected to evaluation of catalytic activity as a curing accelerator for epoxy resins. In addition,
For comparison, the catalytic activity of the sample immediately after the preparation of the molecular compound and the sample of 2E4MZ alone as a control were also evaluated. Further, as the evaluation of the catalyst activity, a [lifetime measurement test for epoxy resin] and a [resin curing test for epoxy resin] described below were performed. The results are shown in Table 1 below and the results are shown in Table 2.

[Test for measuring pot life for epoxy resin] A thermosetting resin powder coating, for example, an epoxy powder coating contains an epoxy oligomer and a resin curing catalyst such as 2E4MZ. Since it becomes difficult to use as a paint eventually, it is desired that the curing catalyst used has a performance of rapidly curing by heating or the like at the time of coating without increasing the viscosity during storage. (2E4MZ is excellent in curing catalyst performance, but has a drawback of short pot life and has not been actually used until now.) Therefore, the pot life, which is one of the evaluation indices of the curing catalyst, was measured to evaluate the performance of the molecular compound of the present invention as follows. Adeka resin EP4100E (manufactured by Asahi Denka Kogyo KK) was used as the epoxy oligomer. Weigh 100 g of uncured epoxy resin in a mayonnaise bottle,
It was immersed in a constant temperature water bath set at 5 ° C. for 1 hour. This is 2E
The molecular compound adjusted so that 4 MZ became 3% by weight was added, mixed well for 5 minutes, and the viscosity was measured over time while immersed in a thermostatic water bath. The time at which the initial viscosity doubled was defined as the pot life. The constant temperature water tank is a circulation type constant temperature water tank TRL-40SP manufactured by Thomas Kagaku Kikai, and the viscometer is Tokyo Keiki B
Each type viscometer was used.

[Resin Curing Test for Epoxy Resin] In order to directly examine the curing catalyst performance, a resin curing test for epoxy resin was carried out by measuring differential scanning calorimetry (DSC). Adeka resin EP4100E (manufactured by Asahi Denka Kogyo KK) was used as the epoxy oligomer.
20 g of an uncured epoxy resin was weighed into a mayonnaise bottle, a molecular compound adjusted so that 2E4MZ was 3% by weight was added thereto, mixed well for 5 minutes, and the mixture was measured for DSC. DSC is a differential scanning calorimeter (“DSC 220” manufactured by Seiko Instruments Inc.).
C "), using sample amount: 3-4 mg, measuring temperature range: 30-300 ° C., heating rate: 20 ° C./min, measuring atmosphere: N ₂ (30 ml / min) under flowing aluminum sealing pan conditions. Was measured.

[0043]

[Table 1]

[0044]

[Table 2]

From Table 1 showing the results of the pot life measurement test for the epoxy resin, when the sample obtained by heating the molecular compound at 70 ° C. for 1 to 6 weeks was used, the preparation of the molecular compound having a holding period of “0” was used. Immediate sample and 2E4MZ
Since the pot life was greatly increased as compared with the case where a single sample was used, it was found that the stability of the molecular compound was improved by keeping the molecular compound in a heated state after preparation. It is considered that the effect of improving the stability is due to the fact that the state of the clathrate became stronger by the heating and holding treatment. Also, from Table 2 showing the results of the resin curing test for the epoxy resin, there is almost no effect of the heating and holding treatment on the curing of the epoxy resin, and rather, the temperature (° C.) width up to the top peak is narrow, so that until the polymerization. It can be seen that the rise of the curing speed is fast and the curing speed is fast.
For reference, FIG. 7 shows a DSC chart in a resin curing test using a sample in which a molecular compound was heated and maintained at 70 ° C. for 6 weeks.

Example 7 [Production of molecular compound by step (b)] A 1 L bench kneader (manufactured by Irie Syoukai) was used at 80 ° C.
2E4MZ (purity 98.05%) 1
06.7 g (0.95 mol) were charged with stirring, and then 60.0 g of TEP (purity 97.9%) was added.
The mixture was stirred and mixed at the same temperature for 1 hour, and then 60.0 g of TEP was further added. The mixture was further stirred and mixed at the same temperature for 2 hours.
83.5 g (total 203.5 g, 0.5 mol) of P was added, and stirring and mixing were continued for 12 hours to prepare a molecular compound. 20 g of the obtained molecular compound was added to 2E4M
Xylene 20m, a solvent that can dissolve Z
1 and 50 ml of n-hexane, stirred for 20 minutes, separated by filtration, dried under reduced pressure at 100 ° C. for 30 minutes, washed with xylene 19.0 g, washed with n-hexane 18.8 g
Was prepared respectively. Each of the obtained washed samples and the sample before washing were subjected to catalytic activity evaluation in the same manner as in Example 6. The results are shown in Tables 3 and 4. When ¹ H-NMR was measured, the molar ratio of TEP: 2E4MZ of the molecular compound after washing with xylene and after washing with n-hexane was 1: 1.85 and 1: 1.58, respectively.

[0047]

[Table 3]

[0048]

[Table 4]

From Table 3 showing the results of the pot life measurement test for the epoxy resin, it can be seen that when the sample obtained by washing the molecular compound with xylene or n-hexane was used, the unwashed sample after preparing the molecular compound was used. Since the pot life was significantly increased, it was found that the stability of the molecular compound was improved by washing with xylene or n-hexane after preparing the molecular compound. It is considered that the effect of improving the stability is due to the fact that unreacted 2E4MZ was washed away by washing with xylene or n-hexane. Also, from Table 4 showing the results of the resin curing test for the epoxy resin, there is almost no effect of the cleaning treatment on the curing of the epoxy resin, and considering the pot life, the cleaned product can be advantageously used as a curing catalyst for powder coatings. I knew I could do it. For reference, FIG. 8 shows a DSC chart in a resin curing test using a sample in which the generated molecular compound was washed with xylene.

Example 8 [Production of Molecular Compound by Step (c)] A 1-liter bench kneader (manufactured by Irie Syoukai) was used.
The mixture was heated to 3 ° C., and was subjected to a stream pulverization using an Urmax pulverizer (“Ulmax air pulverizer” manufactured by Nisso Engineering Co., Ltd.), and 150 g (purity: 97.9%) of TEP (purity: 97.9%) was obtained.
Mol). Table 5 shows the particle size distribution of TEP after pulverizing by air current and the particle size distribution of unpulverized TEP. Then, with stirring, the molten 2E4MZ (purity 98.05)
%) 78.65 g (0.70 mol) was added, and the mixture was stirred at the same temperature, sampled after 1.0, 2.5, and 4.5 hours, respectively, and subjected to the evaluation of catalytic activity in the same manner as in Example 6. .
The results are shown in Tables 6 and 7.

[0051]

[Table 5]

[0052]

[Table 6]

[0053]

[Table 7]

From Table 6 showing the results of the pot life measurement test for the epoxy resin, it can be seen that the sample using the host compound pulverized by air current was used as compared with the sample using the host compound not pulverized. Since the pot life has been increased, by using a stream-pulverized one as the host compound, especially by increasing the kneading time with the guest compound using a stream-pulverized one as the host compound, It was found that the stability was improved. Further, it is considered that the effect of improving the stability is due to the fact that the molecular compound was homogenized by using the host compound subjected to the airflow pulverization treatment. Also, from Table 7, which shows the results of the resin curing test for the epoxy resin, there is almost no effect of the use of the airflow-pulverized host compound on the curing of the epoxy resin. It has been found that a molecular compound using is advantageously used as a curing catalyst for powder coatings. For reference, FIG. 9 shows a DSC chart in a resin curing test using a sample kneaded for 4.5 hours using a host compound pulverized by air current.

Example 9 [Production of molecular compound by step (d)] A 1 L bench kneader (manufactured by Irie Syoukai) was used at 80 ° C.
And TEP (purity 97.9%) 203.5 g
(0.50 mol), 250 ml of water was added thereto, and the mixture was stirred and mixed for 10 minutes.
8.05%) 106.7 g (0.95 mol) were added in one portion. The mixture was stirred at 80 ° C. for 4 hours, and the weight of the removed powder was 294 g. When the obtained powder was vacuum-dried at 70 ° C. for 5 hours, the powder weight after drying was 293 g,
The water content was 0.25% by weight. From the measurement result of ¹ H-NMR of the obtained molecular compound, TEP: 2E4MZ
Was 1: 1.68. This dried product was subjected to catalytic activity evaluation in the same manner as in Example 6. The results are shown in Tables 8 and 9 together with the results of Example 10 below.

Example 10 [Production of molecular compound by step (d)] A 1 L bench kneader (Irie syoukai) was used at 80 ° C.
And TEP (purity 97.9%) 203.5 g
(0.50 mol), 250 ml of water was added thereto, followed by stirring and mixing for 10 minutes, and then 2E4MZ (purity: 98.05)
%) 112.32 g (1.0 mol) were added over 5 minutes. The mixture was stirred and mixed at 80 ° C., sampled after 2.5 hours and 5 hours, and the water content was measured by a conventional method to be 0.23% by weight and 0.21% by weight, respectively. These samples were subjected to catalytic activity evaluation in the same manner as in Example 6. The results are shown in Tables 8 and 9 together with the results of Example 9 above.

[0057]

[Table 8]

[0058]

[Table 9]

From Table 8 showing the results of the pot life measurement test for the epoxy resin, a sample (Example 9) in which water was added and mixed and then dried, and water was added and mixed under heating to reduce the water content Sample with 1% by weight or less (Example 10)
In the case of using water, the pot life is increased as compared with the case of using a sample without water, so that the host compound and the guest compound are stirred, mixed, and kneaded in the presence of water to form a molecular compound. It was found that the stability of was improved. It is considered that the effect of improving the stability is due to homogenization of the molecular compound by reacting in the presence of water. In addition, from Table 9 showing the results of the resin curing test for the epoxy resin, there is almost no effect of stirring, mixing, and kneading in the presence of water in curing the epoxy resin. It was found that the molecular compound prepared by stirring, mixing and kneading in the presence can be advantageously used as a curing catalyst for powder coatings. For reference, DS in a resin curing test using a sample of Example 10 (kneading for 5 hours)
The C chart is shown in FIG.

Examples 11 to 14 [Production of molecular compound by step (d)] A 1 L bench kneader (manufactured by Irie Syoukai) was prepared as shown in Table 10.
And heated to the specified temperature as shown in TEP (purity 97.9%).
203.5 g (0.50 mol) were charged, and 25
After adding 0 ml and stirring and mixing for 3 minutes, 106.7 g of 2E4MZ (purity 98.05%) was melted while stirring was continued.
(0.95 mol) was added all at once. The stirring and mixing were continued at the same predetermined temperature, sampled at a predetermined reaction time shown in Table 10, and subjected to catalytic activity evaluation in the same manner as in Example 6. Also,
A part of the sample sampled at a predetermined time is
After drying for an hour, the catalyst was similarly evaluated. Table 1 shows the results
0, shown in Table 11.

[0061]

[Table 10]

[0062]

[Table 11]

From Table 10 showing the results of the pot life measurement test for the epoxy resin, the host compound and the guest compound were stirred, mixed and kneaded in the presence of water to obtain a water content of 1% by weight.
By reacting until the water content is below, or by drying the reaction product until the water content is 1% by weight or less, regardless of the reaction temperature, the sample in which the water content of the molecular compound is 1% by weight or less, Water content is 1% by weight
Since the pot life of the epoxy resin can be greatly increased compared to a sample exceeding the above, if the reaction is performed in the presence of water and the water content is 1% by weight or less, the stability as a molecular compound is improved. I understood. It is considered that the effect of improving the stability is due to the fact that the molecular compound was homogenized by causing the reaction in the presence of water to reduce the water content to 1% by weight or less. Further, from Table 11 showing the results of the resin curing test for the epoxy resin, the samples in which the water content of the molecular compound was 1% by weight or less were as follows:
Curing of the epoxy resin occurs sharply and quickly because the curing temperature rises, the temperature range up to the top peak decreases, and the calorific value increases, compared to a sample having a water content exceeding 1% by weight. I understood. Considering the results of the resin curing test for the epoxy resin and the above-mentioned improvement of the pot life, the epoxy resin was reacted in the presence of water to reduce the water content to 1%.
It is understood that the molecular compound prepared by adjusting the content to not more than% by weight can be advantageously used as a curing catalyst for powder coatings.

Examples 15 to 17 [Production of molecular compound by step (d)] A 1 L bench kneader (Irie syoukai) was used at 70 ° C.
And TEP (purity 97.9%) 203.5 g
(0.50 mol), a predetermined amount of water shown in Table 12 was added thereto, and the mixture was stirred and mixed for 3 minutes. Then, 106.7 g of 2E4MZ (purity: 98.05%) melted while stirring was continued.
(0.95 mol) was added all at once. The stirring was continued at the same temperature, and sampling was performed at a predetermined time shown in Table 12.
The catalyst activity was evaluated in the same manner as described above. One hour later, a part of the sample was dried at 75 ° C. for 4.5 hours, and then subjected to the evaluation of the catalytic activity. Table 12 and Table 1 show the results.
3 collectively.

[0065]

[Table 12]

[0066]

[Table 13]

From Table 12 showing the results of the pot life measurement test for the epoxy resin, the host compound and the guest compound are stirred, mixed and kneaded in the presence of water to react until the water content becomes 1.2% by weight. Even if the water content exceeds 1% by weight, the sample obtained by adding 500 ml of water to 1 mol of the solid host compound (Example 15) has a different water content. It was found that the pot life with respect to the epoxy resin can be greatly increased as in the case of the sample having a content of 1% by weight or less. Further, it is considered that the effect of improving the stability is due to the fact that the molecular compound was homogenized by reacting in the presence of about 500 ml of water with respect to 1 mol of the solid host compound. Also, from Table 13 showing the results of the resin curing test for the epoxy resin, a sample (Example 15) in which 500 ml of water was added to 1 mol of the solid host compound was obtained.
As in the case of samples with a water content of 1% by weight or less with different amounts of water added, the curing temperature rises, the temperature range to the top peak decreases, and the calorific value increases, so the curing of the epoxy resin is sharp. And quickly occurred. The result of the resin curing test for this epoxy resin,
Considering the above improvement in the pot life, the solid host compound 1
It can be seen that the molecular compound prepared by reacting in the presence of about 500 ml of water with respect to the mole can be advantageously used as a curing catalyst for powder coatings.

[0068]

According to the method for producing a molecular compound of the present invention, a large amount of the molecular compound can be produced industrially without using a solvent. In addition, unlike the case of using the solvent method, the obtained molecular compound can be a uniform product in a short time, and can be a molecular compound with improved stability.

[Brief description of the drawings]

FIG. 1 shows a ¹ H-NMR spectrum (DMSO-d ₆ solvent) of a molecular compound having a composition ratio of TEP and 2-ethyl-4-methylimidazole of 1: 2 (molar ratio) in Example 1 of the present invention. FIG.

FIG. 2 is a view showing a powder X-ray diffraction pattern of a molecular compound having a composition ratio of TEP and 2-ethyl-4-methylimidazole of 1: 2 (molar ratio) in Example 1 of the present invention.

FIG. 3 is a diagram showing a thermal analysis (TG-DTA) chart of a molecular compound having a composition ratio of TEP and 2-ethyl-4-methylimidazole of 1: 2 (molar ratio) in Example 1 of the present invention.

FIG. 4 shows a ¹ H-NMR spectrum (DMSO-d ₆ solvent) of a molecular compound having a composition ratio of TEP and 2-ethyl-4-methylimidazole of 1: 2 (molar ratio) in Example 5 of the present invention. FIG.

FIG. 5 is a powder X-ray of a molecular compound having a composition ratio of 1: 2 (molar ratio) of TEP and 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU) of Example 5 of the present invention. It is a figure which shows a diffraction pattern.

FIG. 6 is a thermal analysis of a molecular compound having a composition ratio of TEP and 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU) of 1: 2 (molar ratio) according to Example 5 of the present invention ( T
FIG. 3 is a diagram showing an (A / DTA) chart.

FIG. 7 shows D in a resin curing test using a sample obtained by heating the molecular compound of Example 6 of the present invention at 70 ° C. for 6 weeks.
It is a figure showing an SC chart.

FIG. 8 shows D in a resin curing test using a sample obtained by washing the generated molecular compound of Example 7 of the present invention with xylene.
It is a figure showing an SC chart.

FIG. 9 is a view showing a DSC chart in a resin curing test using a sample kneaded for 4.5 hours using the host compound pulverized by air current of Example 8 of the present invention.

FIG. 10 shows the results obtained by adding water of Example 10 of the present invention and heating to 5
It is a figure which shows the DSC chart in the resin hardening test using the sample which knead | mixed for time and made water content below 1 weight%.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shigeru Kawamukai 12-54 Goi-minamikaigan, Ichihara-shi, Chiba Japan Soda Co., Ltd. F term in Odawara Research Laboratory (reference) 4D067 CA02 GA20 4G004 LA00 4H006 AA02 AC90 AD15 BC10 BC33 BD60 FC52 FE13

Claims (20)

[Claims] 1. A solid host compound and a solid guest compound,
Or a method for producing a molecular compound having improved stability by mixing and / or kneading a solid host compound and a liquid guest compound, wherein at least the following (a) to
(D) A method for producing a molecular compound, wherein any one of the steps is performed. (a) a step of mixing and / or kneading the host compound and the guest compound, and maintaining the mixture at a temperature of 50 ° C. or higher and a temperature lower than the release temperature of the guest compound for a predetermined period; and (b) mixing and / or mixing the host compound and the guest compound. Or a step of washing the molecular compound produced by kneading with a solvent capable of dissolving the guest compound (c) a step of previously pulverizing the solid host compound (d) for the solid host compound, the solid guest compound and the liquid guest compound Step of adding and mixing and / or kneading a poor solvent 2. The method for producing a molecular compound according to claim 1, wherein the average particle size of the solid host compound is reduced to 1.6 μm or less in the step (c). 3. The method according to claim 1, wherein the particle size of the solid host compound is reduced to 4.0 μm or less in the step (c). 4. The solid host compound of claim 8
The method for producing a molecular compound according to any one of claims 1 to 3, wherein a particle size of 0% by weight or more is 2.0 µm or less. 5. The method for producing a molecular compound according to claim 1, wherein the pulverization in the step (c) is air pulverization. 6. In the step (d), a poor solvent is added to the solid host compound and the solid guest compound, or 20 to 200% by weight based on the total weight of the solid host compound and the liquid guest compound, and mixed and / or mixed. The method for producing a molecular compound according to claim 1, wherein the molecular compound is kneaded. 7. The method according to claim 1, wherein in step (d), a poor solvent is added and mixed and / or kneaded while heating until the content of the poor solvent is 1% by weight or less. Or a method for producing a molecular compound. 8. The method according to claim 1, wherein in step (d), a poor solvent is added, mixed and / or kneaded, and dried until the content of the poor solvent is 1% by weight or less. Or a method for producing a molecular compound. 9. The process for producing a molecular compound according to claim 1, wherein in step (d), the poor solvent is added in an amount of 200 ml or more and 1000 ml or less per 1 mol of the solid host compound. . 10. The method according to claim 1, wherein a solvent having a solubility of 1 g / 100 ml or less at room temperature of the solid host compound, the solid guest compound and the liquid guest compound is used as the poor solvent in the step (d). Or a method for producing a molecular compound. 11. The method for producing a molecular compound according to claim 1, wherein the poor solvent in the step (d) is water. 12. The solid host compound and a required amount of a solid guest compound, or a solid host compound and a required amount of a liquid guest compound are mixed at a time.
12. The method for producing a molecular compound according to any one of 11. 13. The method for producing a molecular compound according to claim 1, wherein mixing and / or kneading are performed using a kneader. 14. A method for producing a molecular compound, comprising mixing and / or kneading a solid host compound and a solid guest compound or a solid host compound and a liquid guest compound using a kneader. 15. The method for producing a molecular compound according to claim 13, wherein the kneader is a multi-screw kneader. 16. Before mixing and / or kneading the solid host compound and the solid guest compound or the solid host compound and the liquid guest compound using a kneader, the solid host compound and the solid guest compound, or the solid host compound and the solid host compound are mixed in advance. The method for producing a molecular compound according to any one of claims 13 to 15, wherein the liquid guest compound and the liquid guest compound are uniformly mixed. 17. The molecule according to claim 13, wherein the solid host compound, the guest compound, and the generated molecular compound are mixed and / or kneaded in a stable temperature range using a kneader. A method for producing a compound. 18. The method according to claim 13, wherein the solid host compound and the solid guest compound, or the solid host compound and the liquid guest compound are mixed and / or kneaded using a kneader, and further extruded and granulated. A method for producing the molecular compound according to any one of the above. 19. The method according to claim 19, wherein the solid host compound is 1,1,2,2.
The method for producing a molecular compound according to any one of claims 1 to 18, wherein the compound is -tetrakis (4-hydroxyphenyl) ethane. 20. The method according to claim 1, wherein the guest compound is 2-ethyl-4-methylimidazole.
9. The method for producing a molecular compound according to any one of the above items 9.