JPH05202007A - New diguanamine and production process thereof - Google Patents

Abstract

PURPOSE:To obtain a new diguanamine which is widely used as a starting material for resins and a variety of resin-curing agents because it has excellent weathering resistance, ultraviolet resistance, heat resistance, amino group reactivity, high water dilution of methylolated products. CONSTITUTION:2.5- or 2,6-Bis(4,6-diamino-1,3,5-triazin-2-yl)-bicyclo[2,2,1]heptane of formula I. The compound is prepared by reaction of a compound of formula II (the CN-bonding position is 2,5-or 2,6-site) dicyandiamide, preferably in the presence of at least one of basic catalysts selected from alkali metal, its hydroxide or alcoholate, alkaline earth metal hydroxide, alkali metal or alkaline earth metal salt of dicyandiamide, amines and ammonia, preferably in a nonaqueous protonic solvent and/or an aprotic solvent at 80 to 200 deg.C. Further, the compound is also useful as a modifier for rubber materials and a flame retarder for organic materials.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polymerizable monomer, a coating resin, an adhesive resin, a paper processing resin, a fiber processing resin, a resin raw material such as a molding material and a laminated material, a raw material of a guanamine compound derivative, The present invention relates to a novel diguanamine useful as a curing agent for epoxy resins, urethane resins, etc., a modifier for rubber materials, a flame retardant for organic materials, etc., and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, resins for paints, resins for adhesives, resins for paper processing, resins for fiber processing, resin raw materials such as molding materials and laminated materials, curing agents for various resins, and modification of rubber materials. As a flame retardant for chemicals and organic materials, it has high hardness and good luster, is colorless and transparent, has high chemical resistance and water resistance, and has excellent abrasion resistance and electrical properties, and is flame retardant. However, guanamines such as melamine and benzoguanamine having an aminotriazine group have been widely used because they have excellent points such as an excellent resin pot life as a curing agent. Further, various researches and developments have been conducted on melamine and guanamines having such an aminotriazine group, and the resin has excellent properties such as flexibility, toughness, high hardness, water resistance, curability, and flame retardancy. Polyfunctional guanamines having four or more functional groups capable of expressing are also provided to the world. Incidentally, such polyfunctional guanamines are completely different in structure from the novel diguanamine according to the present invention, and it is extremely difficult to compare and contrast, but for the purpose of reference,

[0003]

[Chemical 3] Phthaloguanamine represented by

[0004]

[Chemical 4] There is spiroguanamine represented by.

However, since the former compound is remarkably inferior in ultraviolet resistance and weather resistance of the resin obtained from such compound as a raw material, resin such as exterior paint, weather resistant paint, automobile paint, resin for building materials, etc. It cannot be used as a raw material at all, or has significant restrictions, and the water dilutability of methylated phthaloguanamine resin, which is a derivative of such a compound, is still somewhat improved as compared with methylated melamine resin. It is not practically sufficient, and has drawbacks such as significant restrictions when used as a resin raw material such as a resin for water-based paints. Further, the latter compound is poor in heat resistance of a resin obtained from such a compound, weather resistance of the resin, ultraviolet resistance, water resistance is poor, therefore, an exterior coating,
As a weather resistant paint, a paint for automobiles, a resin for building materials, etc., it has a defect that it is difficult to maintain a desired function outdoors for a long time. Further, the methylolation reaction of the latter compound is slower in the reaction rate than melamine, benzoguanamine and the like, and the reactivity of the amino group in such a compound is poor. Therefore, useful guanamine provided by reacting the amino group Various derivatives, resins,
There are drawbacks such as the production of various resin curing agents and formaldehyde copolycondensates of such compounds with compounds such as melamine and benzoguanamine being significantly limited. Furthermore,
The reaction mixture obtained by the methylolation reaction of such a compound is difficult to obtain a transparent solution, and therefore, when used as a resin raw material for an aqueous resin, for example, an aqueous coating resin, an adhesive resin, a paper processing resin, a fiber processing resin, or the like. However, it is difficult to obtain sufficient performance such as smoothness, curability, and physical properties of the coating film, and it cannot be used for these applications at all, or has a serious restriction. Further, in the production of the latter compound, the production of spironitrile, which is a raw material for producing such a compound, requires a long and complicated process and the purification process is complicated. It has defects such as being damaged. As mentioned above, these compounds have been technically and economically restricted in use and production.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above defects in guanamines, and as a result,
Since it has an active amino group that shows extremely excellent reactivity with compounds having various functional groups, and has 8 active hydrogens, it is possible to widely select the degree of methylolation, weather resistance, ultraviolet resistance, It has excellent heat resistance and can maintain its desired function outdoors for a long time. Furthermore, the water dilutability of the methylol compound, curability, water resistance, stain resistance, flexibility, hardness, toughness, difficulty The present invention has arrived at the present invention by discovering a novel diguanamine which has excellent properties such as flammability and is completely different in structure and characteristics from the above-mentioned polyfunctional guanamines for reference. Such novel diguanamine is used for rubber materials, optical materials, resist materials, automotive paints, home appliance paints, fluorescent paints, weather resistant paints, building resins, water-based paints, paper processing resins, fiber processing resins, adhesives. It is a very useful compound that can provide polymers, compounds and compositions which are excellent as resins, heat resistant resins, corrosion resistant resins, flame retardants, surfactants, agricultural chemicals, pharmaceuticals and the like. Furthermore, in the production of such a novel diguanamine, the desired target compound is obtained in a highly pure form with extremely few by-products, the production such as purification and separation steps is simple, and the dinitrile that is available at a low cost is used to obtain the desired target compound. Has arrived at the present invention by finding an excellent production method capable of obtaining a high yield. That is, the present invention is

(A) General formula (1) (formula 5)

[Chemical 5] [In the formula, (4,6-diamino-1,3,5-triazine-2-
The bonding position of the (yl) group is 2,5- or 2,6-position], (b) a general formula (2)

[Chemical 6] (Wherein, the bonding position of the cyano group represents the 2,5- or 2,6-position), which is characterized by reacting norbornanedicarbonitrile and dicyandiamide in the presence of a basic catalyst. Method for producing diguanamine, (C)
The basic catalyst is alkali metal, alkali metal hydroxide,
The novel diguanamine according to the above item (b), which is at least one selected from the group consisting of alkaline earth metal hydroxides, alkali metal alcoholate dicyandiamide alkali metals, alkaline earth salts, amines and ammonia. Of the novel diguanamine according to the above (b) or (c), characterized in that at least one selected from the group consisting of a non-aqueous protic solvent and an aprotic polar solvent is used as the reaction solvent (d). Production method, (e) A method for producing a novel diguanamine according to the above (b), (c) or (d), wherein the reaction temperature is in the range of 80 ° C to 200 ° C.

In the novel diguanamine (1) according to the present invention, (4,6-diamino-1,3,5-triazine-2-
The bonding position of the (yl) group is the 2,5- or 2,6-position,
The configurations of such groups are endo-endo, endo-exo or exo-exo, and all are useful compounds. Further, such a novel diguanamine is a compound selected from the group consisting of isomers having the above-mentioned bonding positions and configurations, and even in the case of an assembly of different compounds selected from such a group, as in the case of a single compound, It is extremely useful in industry. Specific examples of the novel diguanamine (1) include 2,5-bis (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.
1] Heptane (endo-exo type), 2,5-bis (4,6
-Diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1] heptane (exo-exo form), 2,6-bis (4,6-diamino-1,3,5-triazine- 2-yl)
-Bicyclo [2.2.1] heptane (end-end type),
2,6-bis (4,6-diamino-1,3,5-triazine-2
-Yl) -bicyclo [2.2.1] heptane (exo-exo form) and the like, but are not limited to these compounds.

The novel diguanamine according to the present invention has the general formula (2)

[Chemical 7] (In the formula, the bonding position of the cyano group represents the 2,5- or 2,6-position), a method of reacting norbornanedicarbonitrile and dicyandiamide in the presence of a basic catalyst, norbornanedicarbonitrile. It can be obtained by a method of reacting a dicarboxylic acid ester corresponding to (2) with a biguanide in the presence of a basic compound, if necessary. In the former method, the raw materials are easily available and easy to handle, the desired target compound is obtained with a high degree of purity with very few by-products, the purification and separation steps are easy to manufacture, and the raw material loss is extremely small. In addition, technically, from the viewpoint that the desired compound can be obtained in high yield,
It is economically excellent and extremely practical. The method for producing the novel diguanamine is not limited to these methods. In the norbornanedicarbonitrile (2) in the novel method for producing diguanamine according to the present invention, the bonding position of the cyano group is the 2,5- or 2,6-position, but the steric configuration of such group is the end-to-end type. Endo-exo or exo-exo forms are both useful. Also, such norbornane dicarbonitrile is
It is a compound selected from the group consisting of isomers having the above-mentioned bond positions and configurations, but it is also useful as an aggregate of different compounds selected from such groups, as in the case of a single compound.

The above-mentioned norbornanedicarbonitrile (2) is, for example, as disclosed in US Pat. No. 266748, bicyclo [2.2.1] hept-5-ene-2-.
Carbonitrile and hydrogen cyanide were added to Co ₂ (CO) ₈ , Fe (CO)
_5, Ni [P (OC ₆ H _{5) 3]} a method of reacting at a specific presence of a catalyst such as _4, are disclosed in U.S. Pat. No. 3,143,570, etc. 5- (and / or 6) cyano - bicyclo [2.
2.1] Method for reacting hepta-2-carbaldehyde with hydroxylamines, 2,5- (and / or 2,6
-) It can be obtained by a method of reacting dichloro-bicyclo [2.2.1] heptane with a cyanating agent such as an alkali metal cyanide salt or an alkaline earth metal cyanide salt, but is not limited to these methods. Not a thing. Specific examples of the norbornane dicarbonitrile (2) include:
Bicyclo [2.2.1] heptane-2,5-dicarbonitrile (endo-exo type), bicyclo [2.2.1] heptane-2,5-dicarbonitrile (endo-endo type), bicyclo [2.2.1] Heptane-2,6-dicarbonitrile (endo-exo type), bicyclo [2.2.1] heptane-
2,6-dicarbonitrile (exo-exo form) and the like can be mentioned, but not limited to these compounds.
Further, in the novel method for producing diguanamine according to the present invention, the reaction molar ratio of the norbornanedicarbonitrile (2) and dicyandiamide can be appropriately selected as necessary. The reaction molar ratio of the norbornanedicarbonitrile (2) and dicyandiamide is stoichiometrically 1: 2, and when the molar ratio of dicyandiamide to norbornanedicarbonitrile (2) is used in an excessively small amount, Not only the yield of the novel diguanamine according to the present invention is low, but also monoguanamine [norbornanedicarbonitrile (2) and dicyandiamide is 1: 1 (molar ratio).
The amount of the reaction product] is increased and the purification separation step and the like are complicated, which is not preferable, and when a large excess amount is used, removal and separation of unreacted dicyandiamide and the like are complicated, which is not preferable from a technical and economical viewpoint. .. In order to improve the yield of the novel diguanamine according to the present invention and simplify the production such as purification and separation step, the molar ratio of dicyandiamide to norbornanedicarbonitrile (2) is usually 1 mol of norbornanedicarbonitrile (2). Against dicyandiamide 1.5-1
It is preferable to carry out the reaction at a ratio of 0.0 mol, preferably 2.0 to 5.0 mol.

Examples of the basic catalyst in the novel method for producing diguanamine according to the present invention include alkali metals such as potassium and sodium, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide and barium hydroxide. Alkali metal, alkaline earth metal hydroxides, potassium carbonate, sodium carbonate, barium carbonate and other alkali metals, alkaline earth metal carbonates, potassium ethylate, sodium methylate, sodium ethylate and other alkali metal alcoholates, Alkali metal and alkaline earth metal salts of dicyandiamide, 1,8-diazabicyclo [5.4.0] undecene-7, amines such as triethylenediamine, piperidine, ethylenediamine, diethylenetriamine, pyrrolidone and tetrahydroquinoline, and ammonia. It is. Alkali metals, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, dicyandiamide alkali metal salts, alkaline earth metal salts, amines, and ammonia are preferable, and these are used alone or in combination of two or more. May be. Further, the addition amount of such a catalyst is not particularly limited, but from the viewpoint of production conditions and economical efficiency, it is 500 mol% to 0.001 mol% relative to norbornanedicarbonitrile, preferably
The amount is 300 mol% to 0.1 mol% and can be appropriately selected as necessary. Further, as the reaction solvent in the method for producing the novel diguanamine, various solvents are useful, but a solvent that causes the formation of a compound other than the intended target compound and the reaction inhibition, for example, a fatty acid, the acid anhydride, or a trihydrate. Solvents such as fluoroacetic acid, liquid sulfur dioxide, sulfuryl chloride, mineral acids, water are not preferred.

Examples of the reaction solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, tert-butanol, 2-ethylhexanol, dodecyl alcohol,
Allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol, butanediol, glycerin, 1,2,6-hexanetriol, 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, Furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, diacetone alcohol, 2,2,2-tri Fluoroethanol, alcohols such as 1,3-dichloro-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, aceto Ketones such as Enon,
Esters such as ethyl acetate, butyl acetate, benzyl acetate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, crown ether, ethers such as anisole, N, N-dimethylformamide,
Carboxamides such as N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, sulfolane, methylsulfolane, 1,3-propanesultone, etc. , Sulfoxides such as dimethyl sulfoxide, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, butylamine, 2-ethylhexylamine, allylamine, aniline, cyclohexylamine,
Pyridine, piperidine, monoethanolamine, 2-
(Dimethylamino) ethanol, diethanolamine,
Examples thereof include amines such as triethanolamine, isopropanolamine and triisopropanolamine, ammonia and the like, but particularly non-aqueous protic solvents such as alcohols, amines and ammonia, non-carboxylic acid amides, sulfolanes, sulfoxides and the like. Protic polar solvents are preferred. Incidentally, these solvents may be used alone or in a mixed system of two or more kinds such as a mixed solvent of ammonia and alcohol, dimethyl sulfoxide and cellosolves,
It can be appropriately selected if necessary, and the water content of such a solvent is preferably as low as possible, particularly preferably 1.0% by weight or less.

Further, such a reaction is not preferable because the reaction is remarkably slow at a reaction temperature of 80 ° C. or lower, a long time is required for the production, and the yield is remarkably low. Normally 80 ° C
When the above reaction is carried out at a temperature of preferably 100 ° C. or more, the reaction proceeds rapidly and smoothly to obtain the desired target compound in high yield. However, if the reaction temperature exceeds 200 ° C,
A reaction temperature of 200 ° C or higher is not preferable because the production of by-products rapidly increases to a non-negligible level and the product purity is significantly reduced. Therefore, in the method for producing a novel diguanamine according to the present invention, it is more preferable to carry out such production at a reaction temperature in the range of 80 ° C to 200 ° C, more preferably 100 ° C to 180 ° C. The desired target compound can be obtained, production such as a purification separation step can be performed more easily, and the desired target compound can be obtained in a higher yield. The system of such a reaction is not particularly limited, but it can be carried out under normal pressure or under a spontaneously generated pressure in a closed container, and further under pressure, and can be appropriately selected if necessary.

Further, in order to obtain the novel diguanamine according to the present invention, which is the intended target compound, from the reaction mixture of the above-mentioned reaction, it is best to cool the reaction solution and separate the crystallized diguanamine by filtration. However, the reaction mixture may be poured as it is into hot water for crystallization filtration. The unreacted dicyandiamide and / or dinitrile associated with the crude diguanamine is
The crude diguanamine can be easily separated and removed by washing with hot water or methanol. Depending on the purpose of use, when further purification is required, the reaction solvent described above,
For example, alcohols, cellosolves, carboxylic acid amides, sulfolanes, sulfoxides, etc., a mixed solvent of these solvents and water, a method of recrystallization with water, etc., dissolved in the above-mentioned reaction solvent, and hot water Can be used for reprecipitation, or a method of dissolving crude diguanamine in an acidic aqueous hydrochloric acid solution and mixing this with an alkali to reprecipitate the diguanamine. . However, the production method of the novel diguanamine according to the present invention has an extremely good yield,
The diguanamine is simply various solvents such as methanol, water,
The above-mentioned purification method is practically unnecessary because a highly pure product having practically sufficient purity can be obtained by washing with these mixed solvents. The novel diguanamine according to the present invention is
Since it has an active amino group exhibiting excellent reactivity, it is excellent in various types of reactivity and is useful as a raw material for polymerizable monomers and various guanamine compound derivatives, and is particularly useful as a polymerizable monomer. For example, such a novel diguanamine is subjected to a methylolation reaction with an aldehyde, particularly a formaldehyde source such as formaldehyde, paraform, hexamethylenetetramine, methyl hemiformal, butyl hemiformal, and formaldehyde sodium bisulfite adduct, and glyoxal to give a corresponding N- A methylolated diguanamine derivative can be provided. Furthermore, one or more such polymerizable intermediates are polymerized,
Alternatively, it is obtained by polymerizing with other polymerizable monomers such as melamine, guanamines, urea, alkylurea, thiourea, alkylthiourea, aniline and their polymerizable derivatives, or other polymerizable intermediates depending on the application. It can be provided as a polycondensation derivative or the like. Such a methylolation reaction is carried out in a solvent, if necessary in the presence of a basic compound, at pH 7.0 to 13.0, and more preferably
pH 7.5 to 12.0, reaction temperature 30 ° C or higher, preferably 40 to 1
When the reaction is carried out at 00 ° C, the reaction proceeds rapidly and smoothly, and it can be obtained as a derivative having at least one methylol group, or a polycondensation derivative obtained by partially polycondensing these derivatives. .. The degree of methylolation and the degree of polycondensation of such a derivative are determined according to the intended use, but by appropriately selecting the molar ratio and the reaction conditions, the desired product can be provided.

The N-methylol diguanamine derivative, polycondensation derivative and the like are compounds having various functional groups,
Remarkably excellent in reactivity with resins and the like, useful as various guanamine compound derivatives, raw materials for polymerizable monomers, etc., for example, compounds having excellent performance by reacting with alcohols, carboxylic acids, isocyanates, epoxies. , A resin can be provided. Furthermore, a chain extender, a cross-linking agent, a curing agent, a modifying agent, and a flame retardant having excellent properties of various polymers such as acrylic resin, epoxy resin, urethane resin, aminoalkyd resin, phenol resin, fluororesin, vinyl resin and the like. Agents, etc., such as polyester fibers, synthetic fibers such as acrylic fibers, wrinkle-proofing agents such as cotton, natural fibers such as wool, water- and oil-repellent agents, excellent surface-modifying agents such as stain-proofing agents, etc. It can be used, but is not limited thereto. Further, using such an N-methylol diguanamine derivative, a polycondensation derivative and at least one selected from aliphatic alcohols and alicyclic alcohols having 1 to 20 carbon atoms, acidic, preferably pH 1.0 to 5.0 Under the conditions of, at a reaction temperature of 50 to 100 ° C, a solvent or an appropriate amount of the above-mentioned aliphatic alcohol or alicyclic alcohol is used in excess as necessary, and the reaction is carried out in a solution or suspension. It is possible to provide an etherified diguanamine derivative having at least one ROCH ₂ group (R represents a residue obtained by removing a hydroxyl group from the above alcohol), and such a polycondensation derivative. Such etherified diguanamine derivative, polycondensation derivative,
Having at least one ROCH ₂ group (R has the same meaning as in the previous term), it has outstanding reactivity with compounds having various functional groups, resins, etc., and various guanamine compound derivatives, raw materials for polymerizable monomers, etc. Useful as, for example, a compound having excellent performance by reacting with alcohols,
A resin can be provided, and further, a chain extender, a cross-linking agent, and a curing agent having excellent properties of various polymers such as acrylic resin, epoxy resin, urethane resin, aminoalkyd resin, phenol resin, fluororesin, vinyl resin, etc. However, the present invention is not limited thereto.

The novel diguanamine according to the present invention is
Carboxylic acids such as phthalic acid, adipic acid, maleic acid, trimellitic acid, ethylene tetracarboxylic acid, cyclopentane tetracarboxylic acid, pyromellitic acid, 3,3 ′,
4,4'-benzophenone tetracarboxylic acid, 2,2 ', 3,3'-
Benzophenone tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane , Bis (2,3-dicarboxyphenyl) methane, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,
5,8-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid,
1,2,7,8-phenanthrenetetracarboxylic acid, or a precursor thereof, such as a partial esterified product, an acid anhydride, a halogen acylated product and the like, and a compound having excellent performance, a polyamic acid, a polyimide, a polyamide Resins such as 1,6-hexamethylene diisocyanate,
2,2,4-trimethylhexamethylene diisocyanate,
Diisocyanate from dimer acid, bis (2-isocyanatoethyl) fumarate, methylcyclohexane-
2,4-diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate,
Isopropylidene bis (4-cyclohexyl isocyanate), xylylene diisocyanate, m-phenylene diisocyanate, tolidine diisocyanate, dianisidine diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate , 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate or the like, or a polyol, an amine, can be reacted with a polyvalent isocyanate or the like obtained by the reaction with water, etc. to provide a compound having excellent performance, a resin such as polyurea, Further, it can be used as a polymer such as a chain extender having excellent properties such as urethane resin and epoxy resin, a cross-linking agent, a curing agent, a flame retardant, etc., but is not limited thereto.

As described above, the novel diguanamine according to the present invention is excellent in reactivity and polymerizability with various compounds. Such polymerization includes solution polymerization, emulsion polymerization, suspension polymerization,
Any form of polymerization such as bulk polymerization and interfacial polymerization may be used, and it may be appropriately selected if necessary. The novel diguanamine according to the present invention is excellent in weather resistance, ultraviolet resistance, and heat resistance and can maintain a desired function in the outdoors for a long time, and the water dilutability of the methylol compound of the compound is extremely excellent. There are almost no restrictions as raw materials and excellent characteristics are obtained, and it has an active amino group that is extremely excellent in reactivity with aldehydes, epoxies, carboxylic acids, isocyanates, etc. It has peculiar properties such as a wide selection of methylolation degree, etc., and also has excellent properties such as flexibility, toughness, high hardness, water resistance, curability and flame retardancy. Then
It is an extremely useful compound that can provide various guanamine derivatives and resins having excellent performance. Further, the method for producing a novel diguanamine according to the present invention uses the above-mentioned specific compound and appropriately selects the reaction catalyst, the solvent, the reaction temperature, the molar ratio of the raw materials, etc., whereby the amount of by-products is extremely small and the purity is high. It is possible to obtain the desired target compound in a high yield by using a raw material that can obtain the desired product and can be purified and separated in a simple process, and the raw material loss is extremely small, and can be obtained at low cost. Excellent and extremely practical. Such a novel diguanamine is excellent in polymerizability with various compounds such as aldehydes, epoxies, carboxylic acids, and isocyanates, and is also excellent in various reactivity, and can be used as a resin raw material or a derivative raw material, a rubber material,
Optical materials, resist materials, home appliances, automotive paints, antifouling paints, anticorrosion paints, weather resistant paints, fluorescent paints, powder paints, water-based paints, building materials, molding materials, laminating materials, paper processing agents, curtains Stainproofing of interior products such as sofas, wall cloths and carpets, moisture permeation prevention of fibers, sweat absorption processing,
Fiber processing agents such as SP processing, wrinkle prevention processing, water and oil repellent processing, acrylic resin, urethane resin, polystyrene, polyolefin, vinyl chloride resin, polyphenylene ether and other organic material flame retardant, adhesive resin, leather treatment It is possible to provide a guanamine derivative, a resin and a composition which are extremely useful industrially as an agent, a heat resistant resin, a corrosion inhibitor, a surfactant and the like.

[0018]

Next, the present invention will be described in detail with reference to reference examples, examples and application examples. However, the description of these Reference Examples, Examples, and Application Examples is not intended to limit the scope of the present invention thereto. Reference Example 1 Production of norbornanedicarbonitrile: In a 500 ml flask equipped with a stirrer, a thermometer, a liquid introduction tube, and a condenser,
Bicyclo [2.2.1] hept-5-ene-2-carbonitrile 297.92 g (2.50 mol), Ni [P (OC ₆ H _{5) 3] 4} 8.7
7 g (6.75 mmol), ZnCl ₂ 4.80 g (35.22 mmol) and P (OC ₆ H ₅ ) ₃ 32.27 g (0.104 mol) were charged, and after the system was sufficiently replaced with nitrogen gas, the reaction mixture was stirred. It was kept at 65 ° C. Next, 94.59 g of ice-cold liquid hydrocyanic acid
(3.50 mol) was supplied to the reactor at a flow rate of 45 to 55 ml / hr for 3 hours, and then the reaction was further performed for 1 hour. next,
After substituting the inside of the system with nitrogen gas, deionized water was added, and the aqueous layer portion was separated and removed to obtain a semi-solid oily substance. This oily substance was filtered and distilled under reduced pressure to obtain 362.20 g (yield 99.1%) of bicyclo [2.2.1] heptane-2,5-dicarbonitrile and bicyclo [2.2.1] heptane-2,6-dicarbonitrile. (Boiling point 129 to 137 ° C / 1 mmHg) was obtained. The results of elemental analysis of the target product are shown below. Elemental analysis CHN Measured value: 73.9% 6.9% 19.2% Calculated value: 73.94% 6.90% 19.16%

Reference Example 2 Preparation of bicyclo [2.2.1] heptane-2,5-dicarbonitrile: A 2-liter flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 5-cyano-bicyclo [2.2.1] hepta. -2
-Carbaldehyde 179.0 g (1.2 mol), N, O-bis (trifluoroacetyl) hydroxylamine 292.6 g
(1.3 mol), 197.8 g (2.5 mol) of pyridine and 600 ml of benzene were charged. The mixture was stirred and heated for 3 hours while gradually heating and refluxing. Next, 500 ml of deionized water was added to this reaction mixture, and the aqueous layer portion was separated and removed to obtain an oily substance. This oily substance was distilled under reduced pressure to obtain 128.0 g (yield 73
%) Bicyclo [2.2.1] heptane-2,5-dicarbonitrile (boiling point 131-136 [deg.] C./1 mmHg). The results of elemental analysis of the target product are shown below. Elemental analysis CHN Measured value: 74.0% 6.9% 19.1% Calculated value: 73.94% 6.90% 19.16%

Example 1 Production of Diguanamine: In a 3 l flask equipped with a stirrer, a thermometer, and a reflux condenser, 146.2 g (1.0 mol) of norbornanedicarbonitrile obtained by the method of Reference Example 1 and 210.2 g (2.5 g of dicyandiamide). Mol), caustic potash 16.8 g,
1000 ml of methyl cellosolve was charged and gradually heated. As the temperature rises, the reaction solution becomes transparent and the temperature rises to 105
When the temperature was close to 0 ° C, the reaction rapidly proceeded, and the heat generation was remarkable, and the solvent was refluxed. After a while after the start of reflux, the reaction solution became cloudy. This solution is stirred at a temperature of 120-125 ° C for 10
The reaction was carried out over time. Next, the reaction mixture was desolvated, 3 l of deionized water was poured, and the white precipitate deposited was filtered off. The solids were washed with deionized water, washed with methanol and dried under reduced pressure. Further, this solid content was dissolved in ethyl cellosolve, deionized water was added to this solution, reprecipitation was performed, and then filtration was performed, and the obtained solid content was washed with water. The solid content is dried under reduced pressure to give 2,5-bis (4,6-diamino-1,
3,5-Triazin-2-yl) -bicyclo [2.2.1] heptane and 2,6-bis (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1] A mixture of heptane [white powdery crystals, melting point 317 to 324 ° C. (DSC measurement)] was obtained. In addition, as a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above-mentioned diguanamine was 98.2% (based on the amount of norbornanedicarboxylic nitrile charged), except for the raw material and the desired target compound. Was 0.08% by weight (based on the amount of norbornanedicarbonitrile charged). The results of elemental analysis and'H nuclear magnetic resonance absorption spectrum analysis of the target product are shown below. The infrared absorption spectrum analysis result of the target product is shown in FIG. 1, and the mass spectrum analysis result is shown in FIG. Elemental analysis CHN Measured value: 49.7% 5.8% 44.5% Calculated value: 49.67% 5.77% 44.56% 'H Nuclear magnetic resonance absorption spectrum analysis (internal standard: TM
S, solvent: d ₆ -DMSO) Absorption based on NH ₂ group δ value 6.50ppm (singlet) 6.72ppm (singlet)

Example 2 2,5-bis (4,6-diamino-1,3,5-triazine-2
-Yl) -bicyclo [2.2.1] heptane: Reference Example 2 instead of 146.2 g (1.0 mol) of norbornanedicarbonitrile obtained by the method of Reference Example 1 in Example 1.
Bicyclo [2.2.1] heptane-2,5-
The reaction was performed and the reaction mixture was treated by the same procedure as in Example 1 except that 160.8 g (1.1 mol) of dicarbonitrile was used. The obtained solid content is dried under reduced pressure,
2,5-bis (4,6-diamino-1,3,5-triazine-2
-Yl) -bicyclo [2.2.1] heptane [white powdery crystals, melting point 318-321 ° C (DSC measurement)] was obtained. As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above-mentioned diguanamine was 9
It was 6.4% (vs. the amount of norbornanedicarbonitrile charged). In the infrared absorption spectrum of the target substance, the absorption of nitrile (2235 cm ^-1 ) possessed by the raw material compound disappeared, and the absorption of triazine ring (821 cm ^-1 ) newly appeared, and the measured values of elemental analysis were calculated as follows. Good agreement with the value. Elemental analysis CHN Measured value: 49.7% 5.7% 44.6% Calculated value: 49.67% 5.77% 44.56%

Example 3 Production of diguanamine: The reaction and treatment were carried out in the same procedure as in Example 1 by changing the charged amount (mol) of dicyandiamide and the kind of reaction solvent in Example 1. The yield of the target compound, diguanamine, is shown in Table 1.

[0023]

[Table 1] (Note 1) The value calculated from the liquid chromatography analysis result of the obtained reaction mixture (before treatment) is shown.

Example 4 Production of Diguanamine: 146.2 g (1.0 mol) of norbornanedicarbonitrile obtained by the method of Reference Example 1 and 210.2 g (2.5 mol) of dicyandiamide were placed in a 3 l flask equipped with a stirrer, a thermometer and a reflux condenser. Mol), sodium methylate 54.0 g, dimethyl sulfoxide 1000 ml,
Heated slowly. When the temperature was close to 105 ° C, the reaction rapidly proceeded and the heat generation became remarkable. Then gradually increase the temperature
Raised to 140 ° C. This solution was reacted at a temperature of 140 to 145 ° C. for 2 hours while stirring. Then, the reaction mixture was treated in the same manner as in Example 1 to give 2,5-bis (4,6-diamino-1,3,5-triazin-2-yl) -bicyclo [2.2.1] heptane. And 2,6-bis (4,6-diamino-
1,3,5-triazin-2-yl) -bicyclo [2.2.1]
A mixture of heptane was obtained. As a result of analyzing this reaction mixture (before treatment) by liquid chromatography, the yield (mol%) of the above-mentioned diguanamine was 99.7% (based on the amount of norbornanedicarbonitrile charged).

As shown in Examples 1 to 4, the novel diguanamine according to the present invention can be provided, and further, a reaction catalyst, a solvent, a reaction temperature and a molar ratio of raw materials are used by using a specific norbornanedicarbonitrile and dicyandiamide. According to the production method of appropriately selecting and reacting, etc., byproducts were remarkably excellent in that the amount of by-products was extremely small, the purity was high, the purification separation step was simple, and the desired compound could be obtained in high yield. .. Application Example 1 Production of N-methylol derivative of diguanamine and test of water dilutability of the compound: 15.7 g (0.05 mol) of diguanamine obtained by the method of Example 1 was added to a 1% aqueous solution of caustic soda to give a pH of 1
42.2 g (formaldehyde 0.52 mol) of 37% formalin adjusted to 0.5 was added. This mixture at a temperature of 60-65 ℃
Heat for 30 minutes with stirring. The reaction mixture was a uniform and transparent liquid, and as a result of analysis, it was found that 7.2 mol of formaldehyde was bound to methylol with respect to 1 mol of the diguanamine. Further, 50 g of deionized water was gradually added to the obtained N-methylol compound solution at room temperature, and the solution was a uniform and transparent liquid.

Application Example 2 Curing test of water-based coating resin using N-methylol diguanamine: N of diguanamine obtained by the method of Application Example 1
Methylol compound (7.2 mol bond of formaldehyde to 1 mol of the diguanamine) in a 50% by weight aqueous solution was added to ALMATEX WA911 [Mitsui Toatsu Chemicals, Inc., NV
60%] 40.0 g of dimethylethanolamine was gradually added to the solution with stirring, and then deionized water was added to and mixed with a solution adjusted to a nonvolatile content of 20%. The resin solution thus obtained was applied to a galvanized steel sheet and then heat-treated at 160 ° C. for 20 minutes. The coating film of the treated coated steel sheet was free from cissing, blistering, discoloration, etc., and had a surface gloss of JIS K 5
Measured according to 400 (60 ° specular reflectance), the glossiness is 9
It was 8% and had extremely excellent smoothness and gloss.
Furthermore, the coating film is coated with acetone on the surface of the coating film.
No peeling of the coating film was observed even after rubbing 50 times, and it was an excellent coating film that was sufficiently cured. As shown in Application Examples 1 and 2,
INDUSTRIAL APPLICABILITY The novel diguanamine according to the present invention can extremely easily undergo a polymethylolation reaction with a formaldehyde source under mild conditions, and the reactivity of an amino group in such a compound is very excellent, and melamine, guanamines, ureas, etc. It is an object of the present invention to provide an N-methylol compound of the compound, which is extremely useful as a resin intermediate because it is easy to produce a very useful resin intermediate such as a co-condensation polymer and various derivatives. Further, it has been found that the N-methylol compound of such a compound is extremely excellent in water-dilutability and is not only extremely excellent as a raw material for water-based resins such as water-based paints, but also extremely useful for a wide range of applications.

Application Example 3 Production of N-methoxymethylated product of diguanamine: 5.0 g of N-methylol product of diguanamine obtained by the method of Application Example 1 (formaldehyde to 1 mol of the diguanamine)
The reaction mixture (7.2 mol bond) was dehydrated under reduced pressure, and 50 ml of methanol was added thereto. 20 this mixture
After adjusting the pH to 2.0 with% nitric acid, the mixture was heated at a temperature of 40 to 45 ° C for 2 hours. The reaction mixture was adjusted to pH with 10% aqueous sodium hydroxide solution.
After adjusting at 8.0, methanol and water were removed under reduced pressure, and the solid matter was filtered to obtain a viscous liquid. As a result of analysis of this, 5.3 equivalents of N-methoxymethyl group was bonded to 1 mol of the diguanamine. As shown above, the N-methylol derivative of the novel diguanamine according to the present invention has an extremely excellent reactivity with an alcohol, which easily undergoes an alkyl etherification reaction under a mild condition, and also has an excellent resin intermediate property. It was an object to provide an N-alkoxymethylated product of the compound which is extremely useful as a body. Application Example 4 Polymerization of N-methylol diguanamine and UV resistance test of the resin: N-methylol compound of diguanamine obtained by the method of Application Example 1 (formaldehyde 7.2 mol bond to 1 mol of diguanamine) 5.0 g -Dissolve in 10 ml of butyl alcohol, add 0.025 g of p-toluenesulfonic acid as a curing catalyst, and apply it to a galvanized steel sheet.
It was heat-cured under the conditions of -20 ° C. Using this coated steel sheet, a germicidal lamp (19W made by Toshiba) was used as an ultraviolet light source, and the test steel sheet was irradiated for 200 hours from a height of a vertical distance of 25 cm. The surface gloss of the test steel plate was measured according to JIS K 5400 (60 ° specular reflectance), and the gloss retention was 97%. As indicated above, this new diguanamine N-
The methylol compound had excellent polymerizability, and the compound had very little deterioration in gloss due to ultraviolet rays, and had very excellent properties.

Application Example 5 Curing test of epoxy resin with diguanamine: 100 g of epoxy resin Epicoat # 828 (product of Shell Co.) was dissolved in 200 g of methyl cellosolve, and 19.6 g of diguanamine obtained by the method of Example 1 was added. And dissolved to prepare a resin solution. After this resin solution was applied to a galvanized steel sheet, it was heated at 110 ° C. for 30 minutes and then at 200 ° C. for 30 minutes. The coating film of this heat-treated coated steel sheet was an excellent coating film in which no peeling of the coating film was observed even when the surface of the coating film was rubbed 50 times with a cloth impregnated with toluene, and the coating film was sufficiently cured. As shown above, the amino group of the diguanamine according to the present invention is remarkably excellent in reactivity with an epoxy group, and such a diguanamine sufficiently cures an epoxy resin and is excellent in resin curability and cured resin strength. And a cross-linking agent. Application Example 6 Polymerization of N-methoxymethylated diguanamine and weather resistance test of the resin: N-methoxymethylated product of diguanamine obtained by the method of Application Example 3 (5.3 equivalents of N-methoxymethyl group to 1 mol of the diguanamine). After dissolving 5.0 g in 10 g of methyl isobutyl ketone, Almatex was added to this.
47.2 g of P646 [NV 60% manufactured by Mitsui Toatsu Chemicals, Inc.] was added and mixed. 180 ℃ after applying this resin solution to galvanized steel sheet
It was heat-cured under the condition of -50 minutes. Using this coated steel sheet,
An exposure test was carried out for 500 hours using a weather 0-meter. No blister or discoloration was observed on the surface of the coating film of the test steel sheet, and the surface gloss of the coating film was measured according to JIS K 5400 (60 ° specular reflectance). As a result, the gloss retention rate was 96%. .. As indicated above, this new diguanamine N
The -methoxymethylated product was excellent in polymerizability, and the compound had extremely excellent weather resistance.

Reference Example 3 Production of N-methylol compound of phthaloguanamine and water dilutability test of the compound: O-instead of 15.7 g (0.05 mol) of diguanamine obtained by the method of Example 1 in Application Example 1 The reaction was carried out by the same procedure as in Application Example 1 except that 14.8 g (0.05 mol) of phthaloguanamine was used. This reaction mixture is a liquid in which a large amount of insoluble solid is present, which is subjected to solid-liquid separation by hot filtration, and the solid content is dried under reduced pressure to give crystals 1.
3.7 g [from elemental analysis results 0-phthaloguanamine 13.6 g
(Containing 0.046 mol)] was obtained. Furthermore, when 1.0 g of deionized water was added to this filtrate at room temperature, it became extremely cloudy. Reference Example 4 Production of N-methylol compound of spiroguanamine and water dilutability test of the compound: 3,9-bis instead of 15.7 g (0.05 mol) of diguanamine obtained by the method of Example 1 in Application Example 1 [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane [(trade name) CTU guanamine, Ajinomoto Co., Inc.] [Production] The reaction was performed in the same procedure as in Application Example 1 except that 21.7 g (0.05 mol) was used. This reaction mixture is a liquid containing a large amount of insoluble solids, which was subjected to solid-liquid separation by hot filtration, and the solids were dried under reduced pressure to give crystals 18.3 g [CTU guanamine 18.2 g (0.042 mol) based on the elemental analysis results. Containing] was obtained. Furthermore, when 1.0 g of deionized water was added to this filtrate at room temperature, it became extremely cloudy. As shown in Reference Examples 3 and 4, the above-mentioned phthaloguanamine and spiroguanamine have a markedly slow methylolation reaction with the formaldehyde source,
Poor reactivity of the amino group in such compounds, not only difficult to produce resin intermediates such as melamine, guanamines, copolycondensates with ureas and the like, various derivatives, N- methylol compound of such compounds, The water dilutability was extremely poor, and it was not only difficult to use it as a water-based resin raw material for water-based paints, etc., but it also had significant restrictions on its use.

[0030]

INDUSTRIAL APPLICABILITY The novel diguanamine according to the present invention is remarkably excellent in weather resistance, ultraviolet resistance, and heat resistance, and can maintain a desired function for a long period of time outdoors, etc., and a methylol compound of the compound can be diluted with water. Is extremely excellent, has almost no restrictions as a water-based resin raw material for water-based paints, and has excellent performance, and has an active amino group that is remarkably excellent in reactivity with formaldehyde, epoxy compounds, etc.
Compounds, resins, compositions, etc. that have excellent properties, such as the ability to select a wide range of methylolation degree because they have individual active hydrogen, and the ability to impart flame retardancy to various organic materials. Can be provided and is useful in a very wide range of applications. Furthermore, by reacting a specific norbornane dicarbonitrile and dicyandiamide under specific conditions, the amount of by-products is extremely small, the purity is high, the purification separation step is easy to manufacture, and the dinitrile which is easily available at a low cost is used. This is an industrially excellent invention, which provides an excellent production method capable of obtaining the novel diguanamine according to the present invention in a yield.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of an example of a compound according to Example 1.

2 is a mass spectrum diagram of an example of the compound according to Example 1. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08G 18/32 NDT 8620-4J 59/40 NJE 8416-4J // C07B 61/00 300 (72) Inventor Masami Inomata 1900, Togo, Mobara-shi, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor, Izumi Iga, 1900, Togo, Mobara-shi, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor, Atsura Yamauchi Atsushi Mobara, Chiba Prefecture 1900 Togo City, Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] 1. General formula (1) (Chemical formula 1) [In the formula, (4,6-diamino-1,3,5-triazine-2-
The bonding position of the (yl) group represents the 2,5- or 2,6-position]]. 2. General formula (2) (Chemical Formula 2) (Wherein, the bonding position of the cyano group represents the 2,5- or 2,6-position), which is characterized by reacting norbornanedicarbonitrile and dicyandiamide in the presence of a basic catalyst. Method for producing diguanamine. 3. The basic catalyst is selected from the group consisting of alkali metals, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, alkali metals of dicyandiamide, alkaline earth metal salts, amines and ammonia. It is at least 1 sort (s) selected, The manufacturing method of the novel diguanamine of Claim 2 characterized by the above-mentioned. 4. The method for producing a novel diguanamine according to claim 2, wherein at least one selected from the group consisting of a non-aqueous protic solvent and an aprotic polar solvent is used as a reaction solvent. 5. The method for producing a novel diguanamine according to claim 2, 3 or 4, wherein the reaction temperature is in the range of 80 ° C to 200 ° C.