JP2014058452A - New isocyanurate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new isocyanurate compound having an amino group.SOLUTION: There is provided an isocyanurate compound represented by the chemical formula (1) and the like.

Description

  The present invention relates to a novel isocyanurate compound, and more particularly to a novel isocyanurate compound having an amino group.

Conventionally, various uses of isocyanurate compounds have been studied. For example, when an isocyanurate compound is present when a polymer is formed by polymerizing monomers or oligomers, the rigid triazine skeleton of the isocyanurate compound is present. Attempts have been made to incorporate into the polymer.
In other words, isocyanurate compounds are useful for polymer modification, and products obtained using the modified polymer have mechanical strength, dimensional stability, heat resistance, chemical resistance, hydrolysis resistance, weather resistance, and the like. It is used to show properties such as lightness (light resistance).

By the way, conventionally, an organic compound having an amino group has been used as a curing agent for an epoxy resin or a raw material for a polyimide resin.
For example, in Patent Document 1 below, an isocyanurate compound having an aminoalkyl group on three nitrogen atoms constituting a triazine skeleton (tris (3-aminoethyl) isocyanurate, tris (3-aminopropyl) isocyanurate, etc. ) Is described.

Since the isocyanurate compound described in Patent Document 1 has a triazine skeleton as described above, when it is used as a curing agent for an epoxy resin, the cured product is different from a conventional cured epoxy resin. The effect of exhibiting the characteristics can be expected.
Furthermore, when the isocyanurate compound is used as a raw material for the polyimide resin, it can be expected that a polyimide resin having different characteristics from the conventional one can be obtained.
However, there are almost no reported cases of isocyanurate compounds having amino groups other than this patent document, and even if an epoxy resin cured product or polyimide resin having characteristics different from those of conventional ones is obtained by such a compound, the compound is used. The situation is limited.
In addition, such a problem is not only when the isocyanurate compound is used as an epoxy resin curing agent or when used as a raw material for polyimide resin, but also when used as a main raw material for other polymers, and as a polymer modifier or the like. This is also common when used.

Japanese Patent Publication No. 48-2959

  An object of the present invention is to provide a novel isocyanurate compound having an amino group in view of the above situation.

In order to solve the above problems, the present invention provides an isocyanurate compound represented by any one of the following chemical formulas (1) to (4).

According to the present invention, a novel isocyanurate compound having an amino group is provided.
Therefore, according to the present invention, for example, when an isocyanurate compound having an amino group is used to impart a property derived from a triazine skeleton to a cured epoxy resin, or when a polyimide resin having properties different from conventional ones is formed. The options can be expanded compared to the conventional one.

1 is an IR spectrum chart of the isocyanurate compound of Example 1. FIG. 2 is an IR spectrum chart of the isocyanurate compound of Example 2. FIG. 4 is an IR spectrum chart of the isocyanurate compound of Example 3. FIG.

  In the isocyanurate compound according to the first embodiment of the present invention, a group having a phenylamine (aniline) structure at the end is bonded to one or two of three nitrogen atoms forming a triazine ring, A specific group is bonded to the remaining nitrogen atom. Specifically, it is represented by either the following chemical formula (1) or (2).

  Specific substance names represented by the chemical formula (1) or (2) include 1,3-bis [(4-aminophenyl) methyl] -5-methylisocyanurate, 1,3-bis [(4 -Aminophenyl) methyl] -5-propylisocyanurate, 1- (4-aminophenyl) methyl-3,5-dimethylisocyanurate, 1- (4-aminophenyl) methyl-3,5-dipropylisocyanurate Can be mentioned.

  The isocyanurate compound of the present invention represented by the chemical formula (1) or (2) can be synthesized based on the reaction scheme shown below.

  The isocyanurate compound of the present invention represented by the chemical formula (1) or (2) is any one of 1-methylisocyanurate, 1,3-dimethylisocyanurate, 1-allyl isocyanurate, and 1,3-diallyl isocyanurate. To prepare a reaction liquid (hereinafter referred to as reaction liquid (A)) by containing the isocyanurate compound, nitrobenzyl compound, and basic substance in an appropriate solvent, A second reaction liquid (hereinafter referred to as reaction liquid (B)) containing an isocyanurate compound obtained by reacting under appropriate conditions in a solvent together with a catalyst is prepared, and isocyanurate in the reaction liquid (B). The compound can be synthesized by reducing under appropriate conditions.

As a solvent used for the preparation of this reaction liquid (A), an aprotic polar solvent such as N, N-dimethylformamide and dimethyl sulfoxide, an ether solvent such as tetrahydrofuran and 1,4-dioxane, etc. should be adopted. Can do.
Further, as the nitrobenzyl compound used for the preparation of the reaction solution (A), nitrobenzyl chloride, nitrobenzyl bromide, nitrobenzyl iodide and the like can be adopted, and these nitrobenzyl compounds are usually the nitrobenzyl compounds. It can be used at a ratio of 1.0 equivalents to 3.0 equivalents with respect to the isocyanurate compound to be reacted with the benzyl compound.
Furthermore, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride and the like can be adopted as the basic substance used in the preparation of the reaction liquid (A). Usually, it can be used in a ratio of 1.0 equivalent to 3.0 equivalent.
The reaction temperature and reaction time of the reaction solution (A) can usually be 25 ° C to 100 ° C, 3 hours to 24 hours.

Solvents used for the preparation of the reaction liquid (B) include chlorinated solvents such as chloroform and 1,2-dichloroethane, protic solvents such as methanol, ethanol and 2-propanol, N, N-dimethylformamide, dimethyl sulfoxide and the like. An aprotic polar solvent, ether solvents such as tetrahydrofuran and 1,4-dioxane can be employed.
Moreover, as a catalyst used for the preparation of the reaction liquid (B), for example, a palladium-based catalyst such as palladium carbon or palladium alumina can be employed, and the catalyst is usually used at a ratio of 0.5 mol% to 10 mol%. It ’s fine.
The reduction reaction using this reaction liquid (B) is usually performed at a reaction temperature of 25 ° C. to 100 ° C. and a reaction time of 6 hours to 24 hours.

The isocyanurate compound of the present invention can be isolated from the reaction solution (B) by appropriate treatment.
As a specific example of this treatment, first, the catalyst is filtered off from the reaction solution (B), and then the reaction solution (B) is concentrated to dryness, and then water is added to the concentrated dry product, Subsequently, chloroform was added, mixed and shaken, allowed to stand, and then subjected to a chloroform extraction operation for separating the organic layer (hereinafter referred to as an extract). The resulting extract was dried over sodium sulfate and the volatile matter was removed. The method of isolating the isocyanurate compound of this invention from the said reaction liquid (B) by distilling off and refine | purifying by silica gel chromatography is mentioned.

Next, the isocyanurate compound according to the second embodiment of the present invention will be described.
The isocyanurate compound according to the second embodiment of the present invention is specific to the remaining nitrogen atoms by bonding ethylamine or propylamine to one or two of the three nitrogen atoms forming the triazine ring. Specifically, it is represented by the following chemical formula (3) or (4).

  Specific substance names represented by the chemical formula (3) or (4) include 1- (2-aminoethyl) -3,5-dimethylisocyanurate, 1- (3-aminopropyl) -3,5. -Dimethyl isocyanurate, 1- (2-aminoethyl) -3,5-dipropyl isocyanurate, 1- (3-aminopropyl) -3,5-dipropyl isocyanurate, 1,3-bis (3-amino) Propyl) -5-methylisocyanurate, 1,3-bis (3-aminopropyl) -5-propylisocyanurate.

  The isocyanurate compound represented by the chemical formula (3) or (4) can be synthesized based on the reaction scheme shown below.

  The isocyanurate compound of the present invention represented by the chemical formula (3) or (4) includes 1-cyanomethyl-3,5-dimethylisocyanurate, 1- (2-cyanoethyl) -3,5-dimethylisocyanurate, 1, 3-diallyl-5-cyanomethyl isocyanurate, 1,3-diallyl-5- (2-cyanoethyl) isocyanurate, 1,3-bis (2-cyanoethyl) -5-methyl isocyanurate, 1-allyl-3, 5-bis (2-cyanoethyl) isocyanurate can be synthesized as a raw material, and the raw material is contained in acetic acid together with a catalyst to prepare a reaction solution, which is reacted under pressurized hydrogen conditions to obtain a chemical formula (3) or ( The isocyanurate compound of the present invention represented by 4) can be synthesized.

In this reaction, the pressurized hydrogen condition can be usually 0.1 MPa to 2.0 MPa. As the catalyst, a palladium catalyst such as palladium carbon or palladium alumina is used in a proportion of 0.5 mol% to 10 mol%, for example. Can be used.
Moreover, reaction temperature and reaction time can be normally made into 20 to 100 degreeC and 5 to 10 hours.

The isocyanurate compound of the present invention can be isolated by performing an appropriate treatment from the reaction solution after the completion of the above reaction.
Specific examples of this treatment are as follows. First, the catalyst is removed from the reaction solution, and the reaction solution is concentrated under reduced pressure to obtain a concentrated dry product, and then the concentrated dry product is methanol, ethanol, 2-propanol. A solution is prepared by dissolving in a protic solvent such as, and a basic substance such as sodium carbonate or potassium carbonate is added to the solution, and the mixture is stirred for about 30 minutes under ice-cooling. A method of concentrating the solution again is mentioned.

  The isocyanurate compound of the present invention was used as a raw material for modifying polymers such as conventionally known thermoplastic resins and thermosetting resins, as well as cationic curable, anionic curable, and photocurable resin raw materials. In some cases, the rigid triazine skeleton of the same compound is incorporated into the polymer molecule, so that the mechanical strength, dimensional stability, heat resistance, chemical resistance, and hydrolysis resistance of the product obtained by the polymer are increased. In addition, weather resistance (light resistance), flame retardancy, electrical characteristics, and the like can be improved as compared with the case where an unmodified polymer is used.

  A polyimide resin, an epoxy resin (compound), a silicon resin (compound), or the like is further bonded to the polymer in which the isocyanurate compound of the present invention is incorporated in the molecular structure, or these resins (compounds) are simply mixed. It is also expected to enhance the above improvement effect.

  The isocyanurate compound and the polymer thereof of the present invention are materials such as light emitting diodes, plastic lenses, prisms, optical fibers, substrates for information recording media, optical components such as filters, specifically semiconductor elements / integrated circuits (ICs and others). ), Individual semiconductors (diodes, transistors, thermistors, etc.), LEDs (LED lamps, chip LEDs, light receiving elements, optical semiconductor lenses, etc.), sensors (temperature sensors, optical sensors, magnetic sensors), passive components (high-frequency devices, resistors) Equipment, capacitors, etc.), mechanical parts (connectors, switches, relays, etc.), automotive parts (circuit systems, control systems, sensors, lamp seals, etc.), adhesives (optical parts, optical discs, pickup lenses, etc.), optical use Resin used for film surface coating agent, lithium battery , Battery materials such as electrolyte and the electrolyte membrane, such as a capacitor, protein immobilization materials used in medicines, agricultural chemicals field, and is utilized as a raw material of the resist material is expected.

The isocyanurate compound of this invention can be utilized as a hardening | curing agent of an epoxy resin, for example.
Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol type epoxy resins, phenol novolak type epoxy resins, and cresol novolak type epoxy resins. In addition to glycidyl ether type epoxy resins such as novolak type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, etc., nitrogen-containing ring epoxy resins such as alicyclic epoxy resins, triglycidyl isocyanurates, hydantoin type epoxy resins, dicyclo Examples include cyclic epoxy resins and aliphatic epoxy resins.

  Epoxy resins other than those described above include epoxy-modified organopolysiloxanes that are addition reaction products by hydrosilylation of organic compounds having carbon-carbon double bonds and glycidyl groups reactive with SiH groups and silicon compounds having SiH groups. Examples thereof include siloxane compounds (for example, epoxy-modified organopolysiloxane compounds disclosed in JP 2004-99751 A and JP 2006-282898 A).

  When the epoxy resin as described above is cured using the isocyanurate compound of the present invention, a conventionally known curing agent or curing accelerator can be used in combination as necessary.

  Examples of the curing agent include diethylenediamine, triethylenetetramine, hexamethylenediamine, dimer acid-modified ethylenediamine, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenol ether, 1,8-diazabicyclo [ 5,4,0] undecene-7 and other amine curing agents, methyltetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, trimellitic anhydride, nadic acid anhydride, highmic acid anhydride, Methyl nadic acid anhydride, methyl dicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methyl norbornane-2,3 -Acid anhydride curing agents such as dicarboxylic acid, bisphenol A, bisphenol F, bis Phenolic curing such as Enol S, Tetramethylbisphenol A, Tetramethylbisphenol F, Tetramethylbisphenol S, Tetrachlorobisphenol A, Tetrabromobisphenol A, Dihydroxynaphthalene, Phenol novolak, Cresol novolak, Bisphenol A novolak, Brominated phenol novolak Agent, mercaptopropionic acid ester, mercaptan curing agent such as epoxy resin-terminated mercapto compound, imidazole curing agent such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, triphenylphosphine, diphenylnaphthyl Organic phosphine curing agents such as phosphine and diphenylethylphosphine, aromatic phosphonium salts, aromatic diazonium salts, aromatic Iodonium salts, and the like cationic curing agents such as aromatic selenium salts.

  Examples of the curing accelerator include 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenetriamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl). Amine curing accelerators such as phenol, imidazole curing accelerators such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenyl Organic phosphine curing accelerators such as phosphine, diphenylphosphine and phenylphosphine, phosphonium curing accelerators such as tetrabutylphosphonium bromide and tetrabutylphosphonium diethylphosphorodithiolate, Tetraphenylboron salt curing accelerators such as phenylphosphonium / tetraphenylborate, 2-methyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, lead acetate, tin octylate, cobalt hexanoate, etc. And aliphatic acid metal salts.

Furthermore, the isocyanurate compound of this invention can be made into a polyimide resin by making it react with the tetracarboxylic anhydride shown by following Chemical formula (A).
That is, the isocyanurate compound of the present invention can be used as a raw material for producing a polyimide resin.

（ただし、式中のｍは１〜１２を示し、Ｒ¹¹、Ｒ¹²は同一でも異なっていてもよく、水素原子、炭素数１〜１２の脂肪族炭化水素、ヒドロキシル基、フェニル基、ハロゲン原子を表す。なお、ｍ、Ｒ¹¹、Ｒ¹²の意味は、以降の式においても同じである。）

(In the formula, m represents 1 to 12, and R ¹¹ and R ¹² may be the same or different, and are a hydrogen atom, an aliphatic hydrocarbon having 1 to 12 carbon atoms, a hydroxyl group, a phenyl group, or a halogen atom. The meanings of m, R ¹¹ and R ¹² are the same in the following formulas.)

  Moreover, the isocyanurate compound of this invention can manufacture a polyimide resin also by making it react with the tetracarboxylic acid anhydride shown to following Chemical formula (B)-(G) or Chemical formula (H).

（ただし、式中のＸは、下記化学式（ｘ１）〜（ｘ１２）に示すいずれかの構造を表す。なお、Ｘの意味は、以降の式においても同じである。）

(However, X in the formula represents any structure shown in the following chemical formulas (x1) to (x12). The meaning of X is the same in the following formulas.)

（ただし、式中のＹは、下記化学式（ｙ1）〜（ｙ４）に示すいずれかの構造を表す。）

(However, Y in the formula represents any of the structures shown in the following chemical formulas (y1) to (y4).)

Such a polyimide resin using the isocyanurate compound of the present invention represented by chemical formulas (1) to (4) as a raw material has excellent transparency, heat resistance, adhesion to other members, dimensional stability, gas barrier properties, Expected to exhibit mechanical properties.
The polyimide resin can be expected to be used in the following applications.
・ Film for thin film transistors formed from silicon, metal oxide, or organic matter ・ Color filter film ・ Film with transparent electrode ・ Gas barrier film ・ Film with inorganic or organic glass laminated ・ Film for organic EL ・ Film for electronic paper ・Films for solar cells, touch panel films, microlenses, adhesives, surface protection films for semiconductor elements, and interlayer resist films, solder resist materials for flexible wiring boards, thermal transfer, thermal coloring, ink jet, silver salt photography, electrophotography, etc. Base materials for printed materials, optical compensation films, enameled wire coatings, copper-clad printed circuit board films, α-ray blocking films, liquid crystal display (LCD) alignment films, sealing materials, biological information acquisition devices, etc. Biometric authentication device, light guide, vehicle, mine, For wood machinery, aircraft, mill, motor insulation materials and electric cable, such as for water pumps (universal electric cables; aircraft, rocket, missile flight lines; large computer internal wiring, etc.)
・ Paints for civil engineering and construction ・ FRP
・ Electrical and electronic materials such as LED sealants

  Needless to say, the isocyanurate compound of the present invention can be used in various applications other than those described above.

EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.
Example 1
As a first example of the present invention, 1,3-[(4-aminophenyl) methyl] -5-methylisocyanurate was synthesized.
The synthesis of the isocyanurate compound of Example 1 was performed according to the above reaction scheme.
The main raw materials used for the synthesis of the isocyanurate compound of Example 1 are as follows.

<Raw material>
・ 1-methyl isocyanurate (manufactured by Shikoku Chemicals)
・ 1-allyl isocyanurate (manufactured by Shikoku Chemicals)
・ 4-Nitrobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 5% palladium carbon (Pd / C, 50 wt% water-containing product, manufactured by NE Chemcat)
・ Potassium carbonate (Wako Pure Chemical Industries)

(Step 1: Synthesis of 1-methyl-3,5-[(4-nitrophenyl) methyl] isocyanurate)
In a 100 mL flask equipped with a thermometer and a stirrer, 1.43 g (10.0 mmol) of 1-methylisocyanurate, 3.77 g (22.0 mmol) of 4-nitrobenzyl chloride, 3.04 g (22.0 mmol) of potassium carbonate And 20 mL of N, N-dimethylformamide were added to prepare a reaction solution.
Next, the reaction solution was stirred at 100 ° C. for 12 hours, and then concentrated to dryness under reduced pressure. To the obtained concentrated dry product, 10 mL of water was added, and subsequently 30 mL of chloroform was added, mixed and shaken, and allowed to stand. After that, the organic layer (hereinafter referred to as extract) was separated.
This chloroform extraction operation was further performed twice, and these extracts were mixed and dried over sodium sulfate.
Subsequently, volatile components were distilled off from the extract, and then recrystallization was performed with a mixed solvent of ethyl acetate and hexane.
The obtained crystals were dried to obtain 2.89 g of pale yellow crystals.
¹ H-NMR spectrum data of the obtained crystal was as follows, and it was identified that the crystal was the title isocyanurate compound represented by the following chemical formula (5) (yield 70%).

¹ H-NMR (CDCl ₃ ) δ: 8.20 (d, 4H), 7.62 (d, 4H), 5.13 (s, 4H), 3.37 (s, 3H).

(Step 2: Synthesis of 1,3-[(4-aminophenyl) methyl] -5-methylisocyanurate)
A 100 mL flask equipped with a thermometer and a stirrer was charged with 500 mg (1.21 mmol) of 1-methyl-3,5-[(4-nitrophenyl) methyl] isocyanurate, 50 mg of Pd / C, and 25 mL of 1,2-dichloroethane. The reaction solution was added to prepare a reaction solution. The reaction solution was stirred at 80 ° C. for 24 hours in a hydrogen atmosphere, and then cooled to room temperature.
Pd / C was removed from the reaction solution by filtration, and the filtrate was concentrated to dryness under reduced pressure.
10 mL of water was added to the resulting concentrated dried product, followed by 30 mL of chloroform, mixed and shaken, allowed to stand, and then the organic layer (extract) was separated.
This chloroform extraction operation was further performed twice, and these extracts were mixed and dried over sodium sulfate.
Subsequently, the volatile component was distilled off from the extract, and then purified by silica gel chromatography (chloroform / methanol = 90/1, v / v) to obtain 300 mg of white crystals.
The IR spectrum chart of the crystal was as shown in FIG.
The melting point (Mp) and ¹ H-NMR spectrum data of the obtained crystal are as follows, and it was identified that the crystal was the title isocyanurate compound represented by the following chemical formula (6) (yield: 70 %).

Mp: 90.5 ° C to 91.4 ° C
¹ H-NMR (CDCl ₃ ) δ: 7.29 (d, 4H), 6.61 (d, 4H), 4.92 (s, 4H), 3.67 (br, 4H), 3.30 (S, 3H).

(Example 2)
As a second example of the present invention, 1,3-[(4-aminophenyl) methyl] -5-propyl isocyanurate was synthesized as follows based on the above reaction scheme.

(Step 1: Synthesis of 1-allyl-3,5-[(4-nitrophenyl) methyl] isocyanurate)
In a 100 mL flask equipped with a thermometer and a stirrer, 1.69 g (10.0 mmol) of 1-allyl isocyanurate, 3.77 g (22.0 mmol) of 4-nitrobenzyl chloride, 3.04 g (22.0 mmol) of potassium carbonate And 20 mL of N, N-dimethylformamide were added to prepare a reaction solution.
The reaction solution was stirred at 100 ° C. for 12 hours and then concentrated to dryness under reduced pressure. After adding 10 mL of water to the resulting concentrated dry product, 30 mL of chloroform was added and mixed, shaken, and allowed to stand. The organic layer (extract) was separated.
This chloroform extraction operation was further performed twice, and these extracts were mixed and dried over sodium sulfate.
Subsequently, after the volatile component was distilled off from the extract, recrystallization was performed using a mixed solvent of ethyl acetate and hexane, and the obtained crystal was dried to obtain 3.56 g of a pale yellow crystal.
¹ H-NMR spectrum data of the obtained crystal was as follows, and it was identified that the crystal was the title isocyanurate compound represented by the following chemical formula (7) (yield 81%).

¹ H-NMR (CDCl ₃ ) δ: 8.18 (d, 4H), 7.61 (d, 4H), 5.81-5.92 (m, 1H), 5.29 (dd, 2H) , 5.12 (s, 4H), 4.49 (d, 2H).

(Step 2: Synthesis of 1,3-[(4-aminophenyl) methyl] -5-propyl isocyanurate)
A 100 mL flask equipped with a thermometer and a stirrer was charged with 500 mg (1.13 mmol) of 1-allyl-3,5-[(4-nitrophenyl) methyl] isocyanurate, 50 mg of Pd / C, and 25 mL of 1,2-dichloroethane. The reaction solution was prepared by charging.
The reaction solution was stirred at 80 ° C. for 24 hours under a hydrogen atmosphere and cooled to room temperature.
Pd / C was removed from the reaction solution by filtration, and the filtrate was concentrated to dryness under reduced pressure.
10 mL of water was added to the resulting concentrated dried product, mixed with 30 mL of chloroform, shaken and allowed to stand, and then an extraction operation for separating the extract was performed.
This chloroform extraction operation was further performed twice, and these extracts were mixed and dried over sodium sulfate.
Subsequently, the volatile component was distilled off from the extract, and the residue was purified by silica gel chromatography (chloroform / methanol = 90/1, v / v) to obtain 274 mg of a yellow liquid.
The IR spectrum chart of the obtained liquid was as shown in FIG.
The ¹ H-NMR spectrum data of the obtained liquid was as follows, and it was identified that the liquid was the title isocyanurate compound represented by the following chemical formula (8) (yield 63%).

¹ H-NMR (CDCl ₃ ) δ: 7.29 (d, 4H), 6.61 (d, 4H), 4.91 (s, 4H), 3.78-3.82 (m, 2H) 3.64 (br, 4H), 1.58-1.68 (m, 2H), 0.91 (t, 3H).

(Example 3)
As a third example of the present invention, 1,3-bis (3-aminopropyl) -5-methylisocyanurate was synthesized according to the above reaction scheme.

  The 1-methyl-3,5-dipropanenitrile isocyanurate used for the synthesis of the isocyanurate compound of Example 3 was synthesized according to the method described in US Pat. No. 3,407,200.

The other main raw materials are as follows.
<Raw material>
・ 5% palladium alumina (Pd / Al ₂ O ₃ , manufactured by NE Chemcat)
・ Acetic acid (Wako Pure Chemical Industries)
・ Potassium carbonate (Wako Pure Chemical Industries)
・ Methanol (Wako Pure Chemical Industries)

In a 200 ml autoclave equipped with a heating jacket, stirrer, gas inlet tube, and discharge tube, 0.46 g (2.0 mmol) of 1-methyl-3,5-dipropanenitrile isocyanurate, 85 mg of Pd / Al ₂ O ₃ ( 0.04 mmol) and 40 ml of acetic acid were charged to prepare a reaction solution (hereinafter also referred to as reaction solution (A3)).
After sealing the autoclave container, hydrogen was injected until the pressure became 0.15 MPa, the internal temperature was set to 50 ° C., and the reaction liquid (A3) reacted for 7 hours with stirring was cooled. Pd / Al ₂ O ₃ was filtered off and concentrated under reduced pressure.
Next, the resulting concentrate was dissolved in 10 ml of methanol, and 5 g of potassium carbonate was added under ice cooling to prepare a reaction solution (hereinafter also referred to as reaction solution (B3)).
The reaction solution (B3) was stirred for 30 minutes, then insoluble material was filtered off and concentrated to obtain 0.21 g of a pale yellow liquid.
The IR spectrum chart of the obtained liquid was as shown in FIG.
The ¹ H-NMR spectrum data of the obtained liquid is as follows, and the liquid was identified as the title isocyanurate compound represented by the following chemical formula (9) (yield: 40%).

¹ H-NMR (CDCl ₃ ) δ: 3.99 (t, 4H), 3.35 (s, 3H), 2.73 (t, 4H), 1.80 (quin, 4H).

  From the above, it can be seen that according to the present invention, a novel isocyanurate compound having an amino group can be provided, and a polymer having a novel characteristic can be provided.

  The isocyanurate compound of the present invention is expected to be used, for example, as a curing agent for epoxy resins and a raw material for polyimide resins.

Claims (1)

An isocyanurate compound represented by any one of the following chemical formulas (1) to (4).

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