KR840001344B1 - Process for the preparation of triisocyanates - Google Patents

Abstract

Triisocyanate I was prepd. by dehydrogenation of the corresponding triamines and phosgenation of the resulting amines. I are useful for prepn. of coatings having good weathering properties. Thus, 90.0g 1, 3, 5-tris(aminomethyl) benzene was added to 1200ml 0-dichlorobenzene followed by phosgenating with phosgen to give 112.9g 1, 3, 5-tris (isocya-nate methyl)benzene.

Description

Preparation of Triisocyanate Compounds

The present invention relates to a method for producing a novel triisocyanate compound which is excellent in weather resistance when made of plastics, especially a polyurethane resin, and which can be a good solvent-free or high sound urethane coating, especially when a urethane paint is used. The present invention also relates to a method for producing a polyurethane from the triisocyanate.

As an isocyanate compound which is a raw material of polyurethane, aromatic isocyanates such as trienediisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are used in large quantities, but the polyurethane obtained from these aromatic isocyanate compounds has elapsed over time. In addition, there is a big drawback of yellowing (黄 變化), this drawback is one of the restrictions on use.

Many attempts have been made to obtain a polyurethane compound having improved yellowing resistance, and hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), nuclear hydrogenated xylene diisocyanate (H ⁹ XDI), The application of aliphatic or aromatic aliphatic polyisocyanates such as nucleated hydrogen, diphenylmethane diisocyanate (H ₁₂ MDI), isophorone diisocyanate (IPDI), and lysine diisocyanate ester (LDI) to polyurethane resins has been attempted. However, since they have a small number of functional groups per molecule and high vapor pressure at room temperature, when applied as a paint or the like, they are adducts, dimers, trimers, carbs with polyfunctional alcohols, amines, water and the like. It was necessary to make it an adduct of mutual isocyanate, such as a body imide. However, since these isomers use isocyanate groups because of the addition reaction, the content of available isocyanate groups is lowered and the viscosity is higher. Therefore, it is necessary to use a solvent-free or high-sound paint which is strongly desired in terms of pollution control in recent years. Very difficult. In addition, in order to reduce the content of isocyanate monomer, which is a major problem in the sanitation field at the time of additive manufacturing, complicated technology and expensive manufacturing equipment are required.

Therefore, polyisocyanates that do not have the drawbacks of currently used isocyanate compounds, which are excellent in weatherability when made of urethane resins, and which are free of solvents or capable of high sonication have been strongly desired.

The inventors of the present application have made intensive studies for the purpose of obtaining a polyisocyanate compound having such a requirement from small raw materials that are readily available and relatively inexpensive. As a result, the present invention has been completed.

That is, the present invention

General Formula (Ⅰ)

은

또는

를 나타냄)으로 표시되는 트리이소시아네이트 화합물.(Meal,

silver

or

Triisocyanate compound).

2. General formula (Ⅱ)

은

또는

를 나타냄)으로 표시되는 트리아민화합물과 포스겐을 반응시키는 것을 특징으로 하는 일반식 (Ⅰ)(Meal,

silver

or

To react with a triamine compound represented by the formula (I)

은 상기와 동의(同義)이다.)로 표시되는 트리이소시아네이트화합물의 제조법.(Meal

Is synonymous with the above.) The manufacturing method of the triisocyanate compound represented by these.

3. General formula (Ⅰ)

또는

를 나타냄)으로 표시되는 트리이소시아네이트화합물과 활성수소화합물을 반응시키는 것을 특징으로 하는 폴리우레탄수지의 제조법이다.(Meal silver

or

It is a method for producing a polyurethane resin, characterized in that the triisocyanate compound and the active hydrogen compound represented by.

The triisocyanate compound represented by the said general formula (I) is a novel compound of a literature non-material.

이

인 화합불은 1,35-토리스(이소시아네이트메틸) 벤젠(이하 MTI라고 약칭할 때가 있음.)이며,

이

인 화합물은 1,3,5-토리스(이소시아네이트메틸) 시클로헥산(이하 H₆MTI라고 약칭할 때가 있음.)이지만, 이들은 각기 대응하는 트리아민화합물(Ⅱ), 즉1,3,5-토리스(아미노메틸) 벤젠(이하 MTA라고 약칭할때가 있음.) 및 1,3,5-토리스(아미노 메틸) 시클로헥산(이하 H₆MTA라고 약칭할 때가 있음.)을 포스겐화함으로써 제조할 수 있다.In the above formula (I),

this

Phosphorus compound is 1,35-Toris (methyl isocyanate) benzene (hereinafter sometimes abbreviated as MTI),

this

Phosphorus compounds are 1,3,5-toris (isocyanate methyl) cyclohexane (hereinafter sometimes abbreviated as H ₆ MTI), but these are the corresponding triamine compounds (II), i.e., 1,3,5-toris ( aminomethyl) benzene (which is time to below abbreviated as MTA.) and 1,3,5 Inc. (aminomethyl) cyclohexane (hereinafter abbreviated as H ₆ that time to MTA.) a can be prepared by phosgenation.

The phosgenation of triamine compound (II) can be performed according to a method known per se. One of them is a method called so-called hodopgenization, by stirring and dropping an organic solvent solution of a raw triamine compound or an itriamine compound into a cooled liquid solvent of organic phosgene or phosgene, followed by dropping of phosgene. It is a method of raising reaction temperature and supplying and completing reaction under supply. In another method, a salt of a raw material triamine compound is added to an organic solvent to form a slurry, or an acid is added to an organic solvent solution of a triamine compound to obtain a slurry of a triamine salt, and gradually heated up while supplying phosgene thereto. It is a method to proceed and complete the phosgenation reaction.

Although the raw material triamine compound may use a high purity, even if it is a raw material containing a small amount of by-product impurities at the time of manufacture of this triamine compound, it can be used similarly.

Examples of the organic solvent used in the case of the phosgenation reaction include aromatic hydrocarbons, halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated substituted hydrocarbons, and the like, but halogenated aromatic hydrocarbons such as chlorobenzene 0-dichlorobenzene are particularly preferable. Examples of the salt of the triamine compound include acetates, hydrochlorides, sulfates, and carbamate salts. Among them, carbamate salts obtained by reacting triamine with carbon dioxide are preferred. The phosgene can be used in any of a gas phase and a liquid phase, and a phosgene dimer (trichloromethyl chloroformate) which is regarded as a precursor of the phosgene known in the art can also be used. Regarding the reaction temperature between the triamine compound (II) and the phosgene, it is preferable to select between -20 and 180 ° C because the reaction temperature is low at the excessively high temperature and the reaction rate is low at the excessively low temperature. Thus, the desired triisocyanate compound (I) can be obtained with high purity by removing excess phosgene and a reaction solvent from the reaction solution which completed phosgenation, and then vacuum distillation.

The triamine compound of the general formula (II) is also a novel compound of non-documentation, and can be produced, for example, by the method described below.

That is, 1,3,5-Toris (aminomethyl) benzene (MTA) can be obtained by hydrogenating, for example, 1,3,5-Tricycyanobenzene (hereinafter sometimes referred to as MTN) in the presence of a catalyst. , H ₆ MTA can be obtained by hydrogenating MTA in the presence of a catalyst, hydrogenation of cyano groups and nuclear reduction of benzene nuclei in a single step in the presence of MTN in the catalyst.

First, MTN production by hydrogenation of MTN can be carried out in the presence of liquid hydrogen and can be more appropriately carried out by using a solvent.

As the solvent, a solvent stable under the reaction conditions such as benzene, toluene, xylene, methanol, ethanol, propanol, isopropanol, isobutanol, dioxane, tetrahydrofuran, liquid ammonia and water may be used alone or as a mixture of two or more thereof. Alternatively, even when the aromatic hydrocarbon-alcohol-based solvent uses an inexpensive catalyst or reduces the amount of catalyst, the yield is less likely to be a more preferable solvent.

The amount of the solvent used is in the range of 0.5 to 10 times the capacity of the raw material trinitrile compound, and preferably 1 to 6 times the capacity of the solvent. Of course, the use of a solvent above this does not have a major obstacle to the reaction, but from an industrial standpoint, it is sometimes economically disadvantageous to use a large amount of the solvent. Moreover, more preferable reducing conditions can be obtained by adding 0.05-40 weight%, preferably 0.5-20 weight% of alkali metal hydroxides, such as LiOH, NaOH, and KOH, with respect to a raw material trinitrile compound. Hydrogenation uses hydrogen gas, preferably in a pressure resistant vessel such as an autoclave. The reaction pressure is 30 ~ 300kg / cm ² G, preferably 30 ~ 150kg / cm ² G, the reaction rate is -10 ~ 150 ℃, preferably 40 ~ 120 ℃. In the case of hydrogenation, it is preferable to use a catalyst normally. Examples of the catalyst include Rani cobalt, Ra nickel, Ra nickel chromium, platinum, palladium, ruthenium, rhodium, and the like. These catalysts are used alone or as two or more kinds of mixed fires. Among them, Ra nickel nickel gives a more preferable result. In addition, by selecting an appropriate amount of solvent and alkali, it is possible to obtain a condition in which the yield decrease is relatively low even if a cheaper nickel nickel catalyst is used or the amount of the catalyst is reduced.

This MTA is colorless crystals at room temperature, and becomes a colorless and transparent liquid by heating to about 50 ° C. What is refine | purified in normal conditions show melting | fusing point 49-51 degreeC and boiling point 136-139 degreeC / 0.4mmHg. H ₆ MTA is obtained by hydrogenating MTA or hydrogenating MTN.

In hydrogenating MTA, it is common to carry out by liquefaction and presence of hydrogen, and a solvent is used as needed. As a solvent, for example, water, ethanol, methanol, propanol, isopropanol, isobutanol, dioxane, acetic acid, tetrahydrofuran, etc. may be used alone or as a mixture of two or more kinds, but is advantageous in that water is inexpensive, and alcohol Even when the mixed solvent of water reduces the amount of the catalyst, the yield decreases little, which is more preferable. The solvent is not necessarily required in the reaction conditions to be selected, but when used, it is a range in which 0.05 to 10 times the capacity, preferably 0.1 to 5 times the volume of the raw material MTA gives good results. Also, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, alkaline earth metal hydroxide or these carbonates is added in an amount of 0.05 to 20% by weight, preferably 0.1 to 10% by weight, based on MTA. By doing so, more preferable nuclear reduction conditions are obtained. Hydrogenation uses hydrogen gas, and the reaction vessel is not particularly limited as long as it withstands the corresponding reaction conditions. However, when the reaction pressure is high, the reaction vessel may be reacted in an internal pressure vessel such as an autoclave. The reaction pressure is 5 to 300 kg / cm ² G, preferably 5 to 150 kg / cm ² G, and the reaction temperature is -10 to 200 ° C, preferably 50 to 150 ° C. In hydrogenation, it is preferable to use a catalyst normally. Examples of the catalyst may include nickel nickel, chromium, palladium, platinum, rhodium, and tuninium. These catalysts may be used alone or as a mixture of two or more thereof, and may be activated carbon, silica gel, alumina, diatomaceous earth, pumice, or the like. More preferable catalysts can be obtained by being supported on the same carrier. Among these, when the runenium catalyst uses a water, an alcohol, or a mixture of both containing a small amount of alkali metal hydroxide or carbonate as a solvent, even if the amount of addition of the catalyst is reduced, the yield is small and is very preferable. have.

H ₆ MTA can also be obtained by directly hydrogenating MTN. In the hydrogenation of MTN, more preferable results can be obtained by performing in the presence of hydrogen under liquid phase and using a solvent. As the solvent, benzene, toluene, xylene, methanol, ethanol, propanol, isopropanol, isobutanol, dioxane, tetrahydrofuran, acetic acid, liquid ammonia, water and the like can be used alone or as a mixture of two or more kinds, among which water, ethanol or It is a preferred solvent that gives the desired product in high yield of both mixtures. At the time of reaction, when ammonia is present at the same time or in a liquid ammonia solvent, the formation of by-products can be prevented as much as possible, but the same effect is 0.01 to 5% in the solvent, preferably about 0,05 to 3.0%. It can also be obtained by adding and reacting caustic alkali, such as caustic soda and caustic. The usage-amount of a solvent is the range which 50-1000V / W%, Preferably 100-600V / W% gives favorable result with respect to MTN.

The hydrogenation is not particularly limited as long as the hydrogen gas is used and the reaction vessel withstands the reaction conditions selected. However, when the reaction pressure is particularly high, the reaction vessel is preferably reacted in an internal pressure vessel such as an autoclave. The reaction pressure is 5 ~ 300kg / cm ² G, preferably 30 ~ 200kg / cm ² G, the reaction temperature is -10 ~ 250 ℃, preferably 50 ~ 200 ℃.

In the case of hydrogenation, it is preferable to use a normal catalyst. Examples of the catalyst include lanicobalt, lannickel, lannickel, gromium, palladium, platinum, rhodium ruthenium, and the like, which are used alone or as a mixture of two or more thereof, among which a rhodium catalyst has a high yield and gives H ₆ MTA. It is preferable as a catalyst. In particular, in the case of using water, ethanol or a mixture of both as a solvent, high yields of hydrogenation, it may be the most preferred reaction conditions in the case obtained the H ₆ MTA in the first stage by the MTA. H ₆ MTA is a colorless and transparent liquid at room temperature, and does not solidify or precipitate even when cooled to 0 ° C.

The triisocyanate compound according to the present invention has various advantages over conventionally known polyisocyanates. In other words, it is a colorless transparent liquid that is completely odorless and non-irritant at room temperature, and has a very low viscosity. The value is very high.

The triisocyanate compound according to the present invention can make various polyurethanes by various polyaddition processes using reactions of isocyanates and active hydrogen compounds known in the art. The triisocyanate of the present invention can be used in the form as it is, and can also be used as various modified bodies known in the art (dimer, trimer, carbodiimide, etc.), and also reacted with polyol, polyamine, amino alcohol, water and the like. It can also be used as a form of the prepolymer. In the case of applications such as hot pressing paint, this may also be used in the form of so-called masked isocyanate using various known blocking agents.

Suitable masking agents include, for example, phenols such as phenol, cresol, and isononylphenol, oximes such as butanone oxime and benzophenol oxime, tatams such as caprolactam, alcohols such as methanol, acetoacetic acid esters, and maronic acid esters. Triazoles mercaptan, such as ester, such as these, and benzotriazole, etc. are mentioned.

Examples of suitable active hydrogen compounds for reaction with the polyisocyanate according to the present invention or a masked polyisocyanate corresponding thereto include compounds containing at least two isocyanate-reactive hydrogen atoms and generally having a molecular weight of 400 to 10,000. Can be. Among the compounds of this kind, a very suitable compound is a polyhydroxyl compound, and a compound having 2 to 8 hydroxyl groups, particularly a compound having a molecular weight of 800 to 10000 (more preferably 100 to 6000) is preferable. For example, polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyesteramides having at least two, generally two to eight, preferably two to four hydroxyl groups, or Similar compounds can be used. In general, compounds of this kind are known per se as a raw material for the production of polyurethanes.

Examples of suitable hydroxyl group-containing polyesters include reaction products of polyhydric, preferably dihydric alcohols (you may add trihydric alcohols) to polybasic, preferably dibasic carboxylic acids. Can be. Examples of such acids include succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, maleic acid, maleic anhydride, fumaric acid, and the like. Examples of suitable polyalcohols include ethylene glycol, propylene glycol (1, 2) and-(1, 30, butylene glycol (1, 4) and-(2, 3), hexanediol (1, 6), neo Pentylglycool, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), glycerol, trimetholol propane, ventaacetool, diethylene glycol, triethylene glycol, tetraethylene glycol And polyethylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, and the like.

In addition to the above polyhydroxypolyesters, polyhydroxy polyethers known in the polyurethane chemistry field can also be used for this novel triisocyanate. Examples of such polyhydroxypolyethers include polyethers which are known per se having at least two hydroxyl groups, generally 2 to 8, preferably 2 to 3, hydroxyl groups.

This polyether may be prepared by polymerizing an epoxide such as ethylene oxide, propylene oxide butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, for example in the presence of boron trifluoride, or These epoxides can be prepared by chemical addition to the reactive hydrogen atom-containing starting components in the form of a mixture, or in turn. Examples of reactive hydrogen-containing starting components include water, alcohols, amines such as ethylene glycol, propylene glycol,-(1, 3) or-(1, 2), trimethiroolpropane, aniline, ammonia, ethanol Amines and ethyleneamines.

Specific examples of these compounds that can be used in the present invention are described, for example, in the following publications. `` High Polymers: Vol. 16, Polyurethane Chemistry and Technology, '' Sanders Fry, Intercience Publishers, New York and London, Vol. 1, 1962, pages 32-42, Pages 44--54, Volume 2, 1964, pages 5-6, pages 198-199.

化物)도 폴리올로서 사용할 수 있다.Hydroxyl group-containing vinyl polymers can also be used as reactants for the triisocyanates according to the invention. These vinyl polymers are known compounds composed of copolymers of hydroxyl group-containing ethylenically unsaturated monomers and other ethylenically unsaturated compounds such as ethylenically unsaturated esters and hydrocarbons. Examples thereof include a copolymer including the following hydroxyl monomer component. Monohydroxy and polyhydroxyalkylmaleates and fmarates such as hydroxyethylphmarate and the like, acrylates and methacrylates having hydroxyl groups such as trimethyrololpropane monomethacrylate, 2-hydroxyethylacrylate and 2-hydroxymethacrylate, 2 (or 3) -hydroxypropylacrylate and methacrylate, 4-hydroxybutylacrylate and methacrylate and hydroxyvinyl compounds For example hydroxyethyl vinyl ether and aryl alcohol, copolymers of homopolymers such as vinyl acetate or copolymers with other ethylenically unsaturated compounds (

Compound) can also be used as a polyol.

Acid group-containing polymers obtained by copolymerization of unsaturated acids such as maleic acid, acrylic acid or methacrylic acid can also be used in the lacquer.

When the novel triisocyanate according to the present invention or the masked cryisocyanate corresponding thereto is used in the two-component polyurethane lacquer, they are not only the above-mentioned relatively high molecular weight polyhydroxy compounds, but also those having a molecular weight within the range of 62 to 400. It can also be mixed with the low molecular weight polyol of. In most cases it is advantageous to use mixtures of the above relatively high molecular weight polyhydroxyl compounds with low molecular weight polyhydroxyl compounds of this kind. The NCO / OH ratio in this two-component polyurethane lacquer is generally 0.8: 1-1.2: 1.

Examples of suitable low molecular weight polyhydroxyl compounds having a molecular weight within the above ranges include diols and / or triols having hydroxyl groups bound by aliphatic or cyclic aliphatic binding methods, for example ethylene glycol, propane-1,2 -Diol, propane-1,3-diol, hexamethylenediol, trimethirool propane, glycerol, trihydroxyhexane, 1, 2-hydroxycyclohexane, 1,4-dihydroxycyclohexane are mentioned. . Also suitable are low molecular weight polyols having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.

As a far side, the mixture of the said polyhydroxy compound can also be used. However, each component of them is not compatible with each other and should not. Lacquers prepared using the novel triisocyanate or the corresponding masked triisocyanate according to the invention have the following great advantages. In other words, the lacquer can be used without a solvent, whereby a weatherproof coating (coating) having excellent mechanical properties can be produced without the occurrence of bubbles.

In the production of this lacquer mixture (lacquer composition), the addition of a water absorbent or a dehydrating agent is generally unnecessary.

The lacquer of the present invention can be mixed with pigments and fillers in devices which are commercially available in the lacquer industry. Other lacquer raw materials and / or preparations such as cellulose esters, leveling agents, plasticizers, silicone oils, resins and / or other conventional materials may of course be added. In order to adjust the reactivity of this polyurethane lacquer, a well-known catalyst can be used. This lacquer can be coated on the surface to be coated according to the conventional method. This is particularly useful for the coating of any article made from wood, metal, plastic or other materials. In addition to the urethane paint, the triisocyanate compound according to the present invention can be used as a raw material such as polyurethane adhesive, foam, artificial leather and filler.

Reference Example 1

15g of Ranickel-Chromium (atomic ratio Ni: Cr = 49: 1), 15g of 1,3,5-tricyanobenzene (MTN) in a conventional method, 27mℓ of methanol, 63mℓ of xylene, 0.18g of sodium hydroxide and 300l capacity It enclosed in the electronic stirring autoclave of, and high pressure hydrogen was pressed at the superpressure of 100 kg / cm <^2> G, and it reacted at 100 degreeC, and 0.59 mol hydrogen absorption was generated in 35 minutes. The catalyst was filtered off, the solvent was distilled off, and 12.8 g of 1,3,5-toris (aminomethyl) benzene (MTA) was obtained by distillation under reduced pressure.

This MTA was colorless crystals at room temperature of melting point 49-51 degreeC and boiling point 136-139 degreeC / 0.4mmHg, and it heated to about 50 degreeC, and became a colorless and transparent liquid.

Reference Example 2

30g of 1,3,5-Toris (aminomethyl) benzyl (MTA) with 300g of capacity with 3g of 5% ruthenium-alumina catalyst (manufactured by Engelhard, Japan), 60g of water, and 0.75g of caustic soda It enclosed in the clave, pressurized the high pressure hydrogen of 120 kg / m <^2> of pressure, and made it react at 115 degreeC for 25 minutes, and the hydrogen absorption of 0.61 mol generated.

The catalyst was filtered off, and the solvent was distilled off to obtain 26.8 g of 1,3,5-Toris (aminomethyl) cyclohexane (H ₆ MTA) under reduced pressure. This H ₆ MTA obtained by this method was a colorless and transparent low viscosity liquid having a boiling point of 127 to 8 ° C / 1 mmHg.

Reference Example 3

20 g of 1,3,5-tricyanobenzene (MTN) was enclosed in a 300 ml electrostirring autoclave with 80 ml of 25% NH ₃ water, 300 mg of caustic soda and 4 g of a commercially available 5% rhodium-alumina catalyst, 120 kg of super-pressure When the reaction was carried out at a high pressure hydrogenation of / cm ² for 70 minutes at 105 DEG C, 0.95 mol of hydrogen was absorbed, and H ₆ MTA obtained by reducing both of the nitrile and the nucleus was obtained in a yield of 45%.

Example 1

90.0 g of 1,3,5-Toris (aminomethyl) benzene (MTA) was heated and dissolved in 1200 ml of 0-dichlorobenzene in 2 L four-neck Frasco. Carbon dioxide gas was passed through the obtained amine solution until no increase in weight was obtained, thereby obtaining a slurry of colorless crystals. The slurry was stirred and kept at 10 ° C. or lower for 30 minutes while blowing phosgene gas. The mixture was kept at 130 ° C. for 2 hours while continuing to supply phosgene, and maintained at 130 ° C. for 5 hours. With the progress of the phosgenation reaction, the slurry turned into a solution, and finally became a uniform slightly yellowish transparent solution.

The phosgenation reaction termination liquid was blown with nitrogen gas to remove dissolved phosgene, and then distilled off 0-dichlorbenzene in a solvent under reduced pressure. The resulting crude isocyanate was vacuum distilled to give 112.9 g of 1,3,5-Toris (isocyanimethylmethyl) benzene (MTI) having a boiling point of 173 to 175 ° C / 0.4 mmHg (molar yield 85.2%). This MTI was a low-viscosity liquid at 5 ° C and had no odor of isocyanates. The amine equivalent was measured and found to be 83.25 (theoretical 81.1). The IR spectrum of the obtained MTI is shown in Table 1.

In addition, since a small amount of impurities were contained in the obtained MTI, the following experiment was conducted in order to remove this and to ensure identification. That is, a small amount of impurity MTI was reacted with a large amount of methyl alcohol to obtain a methylurethane, and this was recrystallized using acetone as a solvent to obtain white MTI trimethylurethane crystals. (71.5% of the water purification rate). Purified trimethylurethane compound was in agreement with the theoretical value as a result of elemental analysis and its melting point was 155 ~ 156 占 폚.

Elemental Analysis Values (as C ₁₅ H ₂₁ N ₃ O ₆ )

Example 2

Instead of 1,3,5-Toris (aminomethyl) benzene (MTA), 70.0 g of 1,3,5-Toris (aminomethyl) cyclohexane (H ₆ MTA) was used, and it took 6 hours from 10 to 120 ° C. The phosgenation was carried out in the same manner as in Example 1 except that the temperature was elevated and held at 120 ° C. for 6 hours. 1,3,5-Toris (isocyanatemethyl) cyclohexane (H ₆ MTI) having a boiling point of 170 to 174 / 0.53 mmHg was 91.8. g was obtained (molar yield 90.1%). H ₆ MTI was a low viscosity liquid and odorless even at 5 ° C. Found amine equivalents was 84.71 (theoretical 83.08). The IR spectrum of the obtained H ₆ MTI is shown in Table 2.

As in the case of MTI, elemental analysis values of trimethylurethane of H ₆ MTI purified by methylurethanation and recrystallization (solvent acetone) were as follows.

Elemental Analysis Values (as C ₁₅ H ₂₇ N ₃ O ₆ )

Example 3

)하고, 빙냉하에 포스겐을 흡수시켰다. 포스겐가스를 불어 넣으면서 미리 45.2g의 1,3,5-토리스(아미노 메틸) 벤젠(MTA)을 0-디클로로 벤젠 500g에 용해시킨 용액을 100분간에 걸쳐서 적하했다. 적하가 진행됨에 따라서 프라스코 내부의 액의 점도가 상승하고, 슬러리상으로 되었다. 아민 적하 종료후, 30분간은 10℃ 이하로 유지한 후, 포스겐을 불어 넣으면서 반응액을 5시간에 걸쳐서 130℃까지 승온시키고, 130℃로 6시간 반응시킴으로써 포스겐화가 완료했다.250 g of 0-dichlorobenzene was added to a 1 L four-neck Frasco.

And phosgene was absorbed under ice-cooling. While blowing phosgene gas, a solution in which 45.2 g of 1,3,5-Toris (amino methyl) benzene (MTA) was dissolved in 500 g of 0-dichlorobenzene was previously added dropwise over 100 minutes. As the dropping proceeded, the viscosity of the liquid in the Frasco rose and became a slurry. After completion | finish of amine dropping, after maintaining at 10 degreeC or less for 30 minutes, phosgenation was completed by heating a reaction liquid to 130 degreeC over 5 hours, blowing in a phosgene, and making it react at 130 degreeC for 6 hours.

By the same operation as in Example 1, 54.8 g (yield 82.4%) of MTI were obtained.

Example 4

In the same manner as in Example 3, 42.3 g of 1,3,5-toris (amino methyl) cyclohexane (H ₆ MTA) was phosgenated to give 53.0 g (yield 86.1%) of H ₆ MTI.

Example 5

Using the MTI obtained in Example 1, a highly volatile two-component urethane paint was prepared.

Component A: ① acryl polyol

[50% of styrene and 23.2% of 2-hydroxyethyl methacrylate and 26.8% of n-butyl acrylate were copolymerized in toluene-butyl acetate (1: 1) to obtain a nonvolatile content of 65%,

OH 65] 863

② Titanium oxide powder 429.5 parts

③ 276.1 parts of ethyl acetate / butyl acetate / cellosolve acetate (1/1/1)

Component B: 83.3 parts MTI

A component and B component which were fully pigment-dispersed with a bowl mill were mixed at the said ratio so that NCO / OH = 1/1. The non volatile matter of this mixture was 65%, and the viscosity was 24 seconds using the Poor Cup # 4 measured at 25 degreeC. This was spray-coated on a mild steel plate subjected to surface iron phosphate treatment immediately so as to have a dry coating thickness of 30 to 40 µ. After curing at 25 ° C. for 7 days, the physical properties of the coating and the weather resistance test were performed.

EXAMPLES 6-8

Using the MTI obtained in Example 1 or the H ₆ MTI obtained in Example 2 and various polyols, a highly non-volatile two-component urethane paint was prepared in the same manner as in Example 5, and the coating film properties and weather resistance were examined. The results are shown in the first table.

[Table 1]

Polyester polyol I: It is a co-condensate of 2 mol of adipic acid, 1 mol of dipropylene glycol, 1 mol of trimetholol propane, and 1 mol of mole palm oil fatty acid.

Acryl polyol: 50% of styrene, 23.2% of 2-hydroxyethyl methacrylate, 26.8% of n-butyl acrylate were copolymerized in toluene-butyl acetate (1: 1), and 65% of non volatile matter and 65 of OH.

Polyester polyol II: Co-condensate of 2 mol of adipic acid, 1 mol of diethylene glycol, 2 mol of trimetholol propane, and 1 mol of palm oil fatty acid.

BA: Butyl acetate

EA: ethyl acetate

CA: cellosolve acetate.

[Figure 1]

[Table 2]

Claims (1)

A method for producing a triisocyanate compound represented by the general formula (I), comprising reacting a triamine compound represented by the following general formula (II) with phosgene.