KR840000720B1 - Process for the preparation of novel triamine - Google Patents

Abstract

The aine II, useful as epoxy resin and corrosion inhibitor, was prepd. and hydrogenated to the cyclohexane analog I and converted to triiosocyanate IV by COC12. Thus, a mixt. of 15g 1,3,5-(NC)3C6H3 and 15g Raney Ni-Cr in MeOH-m-xylene was heated at 100≰C and 100kg/cm2 H to give 12.8g II, which (30g) was hydrogenated over 3g 5% Ru-Al2O3 at 115≰C and 120kg/cm2 H to give 26.8g I. CO2 was introduced to 90.0g II followed y COCl2 at 10-130≰C to give 112.9g IV, which was formulated in a coating compn.

Description

Method for preparing new triamine

1 is an IR spectrum of the H ₆ MTA obtained in Example 1

The present invention relates to a process for the production of novel lightamines useful as raw materials for the production of plastics, in particular polyurethane resins.

Polyamines such as toluenediamine and diaminodiphenylmethane, which are intermediate raw materials for obtaining urethane resins, and corresponding polyisocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) derived from them are used in addition to the raw material of polyurethane resin. It has many uses and is an industrially important material. However, the polyurethane compounds produced from these polyisocyanate compounds have a great drawback of poor weather resistance, that is, yellowing with time, and this drawback is due to the use of these isocyanate compounds. It is one of the restrictions.

Many tests have been conducted to obtain a polyurethane compound with improved weather resistance, and hexamethylene diisocyanate (HDI) obtained from polyamines and polyamines such as xylenediamine and isoprodiamine, which have already added hexamethylenediamine and xylenediamine water. The production of polyisocyanate compounds, such as xylene diisocyanate (XDI), xylene diisocyanate (H ₆ XDI), water isophorone diisocyanate (IPDI), etc., has been industrialized, and various applications to polyurethane resins have been tested. have. However, since these have few functional groups per molecule and have high vapor pressure at room temperature, they need to be used as adducts with polyfunctional alcohols, adducts with isocyanate or the like when used as paints. Since these adducts have a lower content of isocyanate art group and higher viscosity, it is very difficult to use a solvent-free or high-sound paint which is strongly demanded in terms of pollution regulations in recent years. In addition, in the production of adducts, in order to lower the monomer content, which is a major problem in hygiene at work sites using these resins, complicated manufacturing processes and expensive manufacturing equipment are required.

As such, there is an urgent need for an intermediate raw material that does not have the same drawbacks as the various raw materials currently used, and is applied to a polyurethane resin to provide a polyisocyanate that is excellent in weather resistance and that can be solvent-free or high-sorted.

The inventors of the present invention have made a thorough study for the purpose of obtaining an intermediate raw material having such a requirement in a simple and simple process from industrial raw materials and relatively inexpensive small raw materials. Reached.

In other words, the present invention is a tree characterized by hydrogenating 1,3,5-toris (aminomethyl) benzene (hereinafter sometimes referred to as triamine (II) or MAT) represented by formula (II) in the presence of a catalyst. Method for preparing amine (I).

It is about. Triamine (II) having an aromatic ring is easily obtained by hydrogenation of trinitrile (III).

Trinitrile (III) serving as this raw material can be obtained by the ammoxidation reaction of mesitylene which is present in a large amount of petroleum oil. That is, a catalyst including vanadium, chromium, uranium, barium, germanium, hafnium, tenium, and thorium oxides is charged into a conventional fixed bed reactor, and the reaction temperature is maintained at 300 to 500 ° C to provide 0.1 to 3 mol% of A mixed gas consisting of 0.3-20 mol% ammonia and 80-99 mol% air of mesitylene is obtained by carrying out ammoxidation reaction at a space velocity of 300-3,000 ^{hr −1} at normal pressure. The catalyst to be used is not necessarily limited to the above, and a catalyst suitable for other ammoxidation reaction can be used depending on the conditions. In addition, the most preferable one can be selected from the reaction conditions which combined reaction rate and mixed gas composition also accordingly.

In order to obtain triamine (II) which has an aromatic ring which is an application raw material in this invention, the method of hydrogenating trinitrile (III) is preferable. In the hydrogenation, it is carried out in the presence of hydrogen under liquid phase and using a solvent gives better results.

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, for example, alcohols such as methanol, ethanol, propanol, isopropanol, and isobutanol, and ethers such as dioxane and tetrahydrofran. Although inert solvents can be used alone or in combination of two or more kinds under reaction conditions such as ammonia, water, etc., the yield decreases even when an alcohol-based or aromatic hydrocarbon-alcohol-based solvent uses an inexpensive catalyst or reduces the amount of catalyst. Since it is few, it can be said that it is a more preferable solvent.

Although there is no restriction | limiting in particular about the usage-amount of a solvent, 50-1000V / W% and preferably 100-600V / W% with respect to raw material trinitrile (III) give a favorable result. Of course, using the above solvent does not significantly affect the reaction, but from an industrial standpoint, it is uneconomical to use a large amount of the solvent. Further, by adding hydroxides of alkali metals such as LiOH, NaOH, KOH, NaOCH ₃ , NaOC ₂ H ₅ , and Alcoaart to 0.05 to 40% by weight, preferably 0.5 to 20% by weight, based on the raw material trinitrile (III), Desirable results are obtained. Hydrogenation is carried out using hydrogen gas, preferably in a pressure-resistant vessel such as auto crepe. The reaction pressure is 30 to 300 kg / cm ₂ G, preferably 30 to 150 kg / cm ² G, and the reaction temperature is -10 to 150 ° C, preferably 40 to 12 ° C. It is preferable to use a catalyst normally in hydrogenation. Examples of the catalyst include Rani cobalt, Ra nickel, Ra nickel Nickel, Platinum, Palladium, Ruthenium, Rhodium, etc. These may be used alone or in combination of two or more of them, of which Ra nickel Nickel results in more preferable results give. In addition, by selecting an appropriate solvent system and an alkali addition amount, even if a cheaper nickel nickel catalyst is used or the amount of catalyst is reduced, a relatively low yield decrease can be obtained.

Triamine (II) having an aromatic ring thus obtained is colorless crystals at room temperature, and becomes colorless and transparent liquid by heating to about 50 ° C.

In order to obtain the triamine (I) of this invention, the method of hydrogenating a triamine (II) is taken.

The hydrogenation of triamine (II) having an aromatic ring is usually carried out in the presence of liquid hydrogen, and an appropriate solvent is used as necessary. As a solvent, for example, water, methanol, ethanol, propanol, isopropanol, dioxane, acetic acid, tetrahydrofran and the like can be used alone or in combination of two or more. However, it is advantageous in that water is inexpensive, and alcohol-water mixing. It is preferable at the point that the fall of a yield is small also when a solvent reduces the amount of catalyst. The solvent is not necessarily required among the reaction conditions to be selected, but when used, 0.05 to 10 times the volume, preferably 0.1 to 5 times the volume of the raw material triamine (II), gives good results. In addition, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, alkaline earth metal oxides or their carbonates are 0.05 to 20% by weight, preferably 0.1 to 20%, based on the raw material amine (II). A more preferable result can be obtained by adding 10 weight%. 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 is preferably carried out in a pressure resistant container 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. It is preferable to use a catalyst normally in hydrogenation. Examples of the catalyst include ranickel, chromium, palladium, platinum, rhodium, ruthenium, and the like, which are used alone or in combination of two or more kinds, and in some cases activated carbon, silica gel, alumina, diatomaceous earth, pumice, etc. More preferable properties can be obtained by supporting on a carrier. Among these, when a ruthenium catalyst especially uses a small amount of alkali metal hydroxide or carbonate, water, alcohol, or a mixture of both as a solvent, even if the addition amount of a catalyst is reduced, it can be said that it is very preferable because there is little fall of a yield. .

Triamine (I) by this invention is a colorless and transparent liquid at normal temperature, and it hardens even if it cools to 0 degreeC, and a precipitate does not arise. Itriamine (I) can be derived to the corresponding triisocyanate (V) (sometimes referred to as H ₆ MTI) by reacting with phosgene by means known per se.

The phosgenation of triamine (I) can be performed according to a method known per se. One of them is the so-called Could. In a method called hot phosgenation, triamine (I) or an organic solvent solution of this triamine is added dropwise to the cooled liquid solvent of organic phosgene or phosgene under stirring, and then the reaction temperature is increased under the supply of phosgene. It is a method of advancing and completing reaction. In another method, the salt of the raw material triamine is added to an organic solvent to form a slurry, or an acid is added to the triamine organic solvent solution to obtain a slurry of the triamine salt, and gradually heated up while supplying phosgene to the phosgenation reaction. It is a way to complete it.

Although triamine may use a high purity, even if it is a raw material containing a small amount of the by-products impurity at the time of manufacture of this triamine, 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 alicyclic hydrocarbons, and the like, but halogenated aromatic hydrocarbons such as chlorobenzene and 0-dichlorobenzene are particularly preferable. As the salt of the triamine, acetate, hydrochloride, sulfate, carbamate and the like can be used. Among them, carbamate salts of triamine and carbon dioxide are preferred. The phosgene can be used in any of a gas phase and a liquid phase, and a phosgene dimer (trichloromethylchloroformate), which is considered as a precursor of phosgene known in the art, may be used in place of the phosgene.

Regarding the reaction temperature of phosgenation, it is preferable to select between -20 and 180 ° C because the reaction temperature is low at excessively high temperatures and the reaction rate is low at excessively low temperatures. Thus, the corresponding isocyanate (IV) can be obtained by removing excess phosgene and a reaction solvent from the reaction liquid which complete | finished phosgenation, and then performing vacuum distillation. Thus obtained triisocyanate (IV) has various advantages compared with the conventionally known polyisocyanate. That is, it is a colorless, transparent liquid that is odorless, non-irritating, and very low viscosity at room temperature, and thus is particularly useful as a solvent-free or high-sound urethane paint component, and has a relatively low cost of raw materials, and a simple manufacturing method. The industrial value is very high.

This triisocyanate (IV) can make various polyurethane resins by various heavy addition processes using half of the isocyanate and other active hydrogen compounds known in the art. This triisocyanate can be used as it is, but of course, it can also be used as various modifications known in the art (dimer, trimer, carbodiimide, etc.), and a prepolymer reacted with polyol polyamine, amino alcohol, water, and the like. In the case of applications such as heat-compression coating, it can also be used in the form of so-called masked isocyanate using various known blocking agents. When the coating film is formed by the reaction of, the workability is very good, and the physical properties and weather resistance of the resulting cured coating film are also excellent.

In addition, the triisocyanate derived from the object of the present invention is particularly suitable for the use of urethane paint, but can be applied to various isocyanate uses such as adhesives, foams, artificial leather, fillers and the like known in the art.

Reference Example 1

18.2 parts of vanadium pentoxide was added to 150 parts of 33% aquatic solution, heated to about 100 ° C. in a bath, and dissolved in vanadium pentoxide as A solution. Similarly, 150 parts of 33% aquatic solution of chromium oxide ( VI) The solution which melt | dissolved 20 parts was made into B liquid, and A and B nutrient solution are mixed uniformly.

300 parts of anatase titanium anoxide powder calcined at 800 ° C. was added to the mixed solution, and water was evaporated while mixing to form a paste, and wet extrusion was performed with a 4 mm diameter × 5 mm length. . The obtained molded product was dried at 100 ° C. for 15 hours and then calcined at 500 ° C. in air for 4 hours to obtain a catalyst.

200 ml of the catalyst was charged to a conventional fixed bed reactor, and the mixed gas consisting of 0.5 mol% of mesitylene, 7 mol% of ammonia, and 92.5 mol% of air was kept at atmospheric pressure while maintaining the reaction tube bath temperature at 360 ° C. The reaction was carried out under the conditions of a space velocity of 1,000 hr ⁻¹ (in terms of NTP) to give 1,3,5-tricyanobenzene (MTN) in a yield of 51.2 mol%.

Reference Example 2

別)하고, 용매를 유거후 감압증착했더니 1,3,5-토리스(아미노메틸)벤젠(MTA) 12.8g이 얻어졌다.Ranikal which developed 15 g of 1,3,5-tricyanobenzene obtained by the reference example 1 by the conventional method. 15 g of chromium (atomic ratio Ni: Cr = 49: 1), 27 ml of methanol, 63 ml of m-xylene, and 0.18 g of caustic soda were enclosed in a 300 ml electronic stirring autoclave with high pressure hydrogen at an initial pressure of 100 kg / cm ² G. Was pressed and reacted at 100 ° C., whereby 0.59 mol of hydrogen was absorbed in 35 minutes. By catalyst

Viii), and the solvent was distilled off under reduced pressure, and then 12.8 g of 1,3,5-toris (aminomethyl) benzene (MTA) was obtained.

Example 1

30 g of 1,3,5-Toris (aminomethyl) benzene (MTA) obtained in Reference Example 2 was mixed with 5% ruthenium-alumina catalyst (manufactured by Engelhardt, Japan), 3 g, water 60 g, and sodium hydroxide 0.75 g. It was enclosed in the electronic stirring autoclave of and the high pressure hydrogen of 120 kg / cm <^{2> of} ultracancer was indented, and it was made to react at 115 degreeC for 25 minutes, and the hydrogen absorption of 0.61 mol occurred.

The catalyst was filtered off, and the solvent was distilled off, and then distilled under reduced pressure to obtain 26.8 g of 1,3,5-Toris (aminomethyl) cyclohexane (H ₆ MTA). This H ₆ MTA is a colorless, transparent, low viscosity liquid having a boiling point of 127 to 8 ° C./1 mmHg, and the IR spectrum thereof is shown in FIG. 1.

145 mg of H ₆ MTA thus obtained was dissolved in about 20 ml of ethyl ether, and acetic anhydride was added dropwise to precipitate white crystals immediately. When no new crystals were observed, dropping was stopped and the crystals were dried separately to obtain 248 mg of triacetyl derivative. Its melting point was 278 to 9.5 ° C and the elemental analysis value was consistent with C ₁₅ H ₂₇ N ₃ O ₃ as toris (acetylaminomethyl) cyclohexane as shown below.

As C ₁₅ H ₂₇ N ₃ O ₃

Calculated Value: C 60.58% H 9.15% N 14.13%

Found: C 60.66% H 9.22% N 14.03%

Next, a 10 ml ethanol solution containing 176 mg of H ₆ MTA was added dropwise to a mixed solution of 20 ml of ethanol and 1 ml of 35% hydrochloric acid, followed by stirring for about 1 hour. After filtration, the crystals were dried to give 195 mg of hydrochloride. Its melting point was 300 ° C. or higher, and the elemental analysis value was consistent with the calculated value C ₉ H ₂₄ N ₃ Cl ₃ as the trihydrochloride as shown below.

As C ₉ H ₂₄ N ₃ Cl ₃

Calculated Value: C 38.51% H 8.62% N 14.97% Cl: 37.89%

Found: C 38.39% H 8.83% N 14.73% Cl: 37.94%

In addition, 210 mg of H ₆ MTA was dissolved in 25 ml of ethanol, and carbon dioxide was passed through it to precipitate crystals. It was passed through carbon dioxide gas until the formation of new crystals was not seen, and the resultant was dried under reduced pressure at room temperature to give 284 mg of white crystals (melting point 85 to 86.5 ° C).

Example 2

100 g of 1,3,5-Toris (aminomethyl) benzene was charged into a 500 ml electrostirring autoclave together with 5 g of a commercially available 5% ruthenium carbon (carrier) catalyst, 200 ml of water, and 3 g of caustic, and weighed 120 kg. / cm ² G of high-pressure hydrogen was reacted at 115 ° C. for 3 hours, whereby 1.82 mol of hydrogen was absorbed and H ₆ MTA was obtained at a yield of 84.7 mol%.

[Examples 3 to 10]

20 g of 1,3,5-Toris (aminomethyl) benzene was nuclear-reduced in an internal volume 300ml electronic stirring autoclave under the following conditions, and H ₆ MTA was obtained in the following yields, respectively.

TABLE 1

* 1 A: Commercial 5% ruthenium alumina catalyst * 2: 90 ml of solvent

B: commercially available 5% ruthenium carbon catalyst

Reference Example 3

70.0 g of 1,3,5-Toris (aminomethyl) cyclohexane obtained in Example 1 was dissolved in 1200 ml of 0-dichlorobenzene in 2 L four-necked 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. After stirring for this slurry-like substance and holding phosgene gas for 30 minutes at 10 degrees C or less, it heated up to 120 degreeC for 6 hours, continuing supplying phosgene, and further phosgenation reaction at 120 degreeC for 6 hours. As the reaction proceeded, the slurry became a solution and finally a uniform slightly yellowish transparent solution.

After completion of the phosgenation reaction, nitrogen gas was blown to remove dissolved phosgene, and then the solvent was distilled off under reduced pressure. The obtained crude isocyanate was distilled under reduced pressure to obtain 91.80 g of 1,3,5-Toris (isocyana artmethyl) cyclohexane (VI) (H ₆ MTI) having a boiling point of 170 to 174 ° C / 0.53 mmHg (molar yield). 90.1%). It was odorless as a low viscosity liquid even at 5 ° C. Found amine equivalents was 84.71 (theoretical 83.08).

Experimental Example 1

Highly volatile two-component urethane paint was prepared using 1,3,5-Toris (isocyana artmethyl) cyclohexane (H ₆ MTI) obtained in Reference Example 3.

Component A: ① Acrylic polyol (50% of styrene, 2-hydroxyethyl methacrylate)

23, 2%, n-butyl acrylate 26.8 toluene-butyl acetate (1: 1)

Non-volatile content 65% OH 65 copolymerized in 863 parts

② 430.4 parts titanium oxide powder

③ 277.4 parts of ethyl acetate / butyl acetate / cellosol acetate (1/1/1)

Component B: H ₆ MTI 84.7 parts

The component A and the component B, which were sufficiently dispersed in a bowl mill, were mixed at the above ratio so that NCO / OH = 1/1. The nonvolatile content of this mixture was 65% and its viscosity (25 ° C) was 26 seconds with Pood Cup # 4.

This was spray-coated on a mild steel plate subjected to surface phosphate treatment immediately so as to have a coating film thickness of 30 to 40 / μ. After curing for 7 days at 25 ° C., the physical properties of the coating film and the weather resistance test were performed.

Experimental Example 2

Using the H ₆ MTI obtained in Example 1 and a polyol, a high volatile two-component urethane paint was prepared in the same manner as in Experimental Example 1, and the coating film properties and weather resistance were examined. The results are shown in the second table.

TABLE 2

* Polyester polyol: 2 mol of azipic acid, 1 mol of diethylene glycol, 2 mol of trimetholol propane, 1 mol of palm oil fatty acid, 100% nonvolatile matter (NV), OH value 230

Claims (1)

A process for producing 1,3,5-toris (aminomethyl) cyclohexane, wherein the 1,3,5-toris (aminomethyl) benzene is hydrogenated in the presence of a catalyst.

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