CA1149418A - Triamines and method for production thereof - Google Patents

Abstract

Abstract of the Disclosure Novel triamines represented by the formula:
wherein stands for or

Description

11'~9~18 The present invention relates to novel triamines useful as raw mate-rials for producing plastics, particularly polyurethane resins, and to pro-cesses for preparing the same.
Polyamine compounds such as tolylenediamine (TDA) and diaminodiphenyl-methane as well as corresponding polyisocyanate compounds derived therefrom such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) find their application not only as raw materials for polyurethane resins but also in many other areas, and have been regarded as very important material. However, polyurethane compounds which are produced from these polyisocyanate compounds suffer from the great defect of inferior weatherability, or the tendency to yel-low with elapse of time, and such defect constitutes one of the limitations on the utility of these polyisocyanates.
As the resùlt of a variety of efforts made so far to obtain polyur-ethane compounds with improved weatherability, there have been already produced on a commercial scale polyamine compounds, such as hexamethylenediamine, xyly-lenediamine, hydrogenated xylylenediamine and isophoron diamine, and also poly-isocyanate compounds derived from these polyamine compounds, such as hexamethyl-ene diisocyanate (HDI), xylylene diisocyanate (XDI), hydrogenated xylylene di-isocyanate (H6XDI), and isophoron diisocyanate (IPDI), while different approach-es are under way with the aim of their application to polyurethane resins.Nevertheless, these compounds have a smaller number of functional groups per molecule and a high vapor pressure at ambient temperature, and are therefore required to be modified onto adducts with polyfunctional alcohols or with iso-cyanate compounds themselves. However, the reduced available-isocyanate content of these adducts, coupled with their raised viscosity, makes it quite difficult to formulate them into solvent-free or high-solids coatings which currently are strongly demanded rrom the standpoint of strengthened control of environmental 9~18 pollution. In manufacturing such adducts, furthermore, complex manufacturing steps and costly facilities are required, so as to decrease their monomer con-tent, which presents a hygienically serious problem at working sites where these resins are used.
As may be obvious from the above, strong demand exists for inter-mediate materials for the production of polyisocyanates that are free from the defects of currently utilized raw materials and that, in the case of their ap-plication to polyurethane resins, can offer the superior weatherability and permit the manufacture of solvent-free or high-solids coatings.
The present inventors, with the specific view of producing an inter-mediate material meeting such requirements from commercially available, rela-tively cheap starting materials in simplified and lessened production steps, have conducted extensive and comprehensive research and study.
Thus, the present invention relates to novel triamines represented by the following formula:

~ [I]

wherein ~ H2NH2C , and to processes for producing the novel triamines [I].
When ~ stands for ~ in the above formula [I], the triamine 2Q is 1,3,5-tris(aminomethyl)benzene (hereinafter referred to as "MTA"), and when ~ stands for ~ in the above formula [I], the triamine is 1,3,5-tris-(aminomethyl)cyclohexane (hereinafter referred to as "H6MTA"). That is, the triamines [I] comprise MTA and H6MTA.

9~18 The process for producing the novel triamines of formula ~I) as defined above comprises:
(a) for producing 1,3,5-tris(aminomethyl)-benzene, hydrogenating 1,3,5-tricyanobenzene in the liquid phase in the presence of a Raney-nickel or Raney-nickel-chromium catalyst at a pressure of from 30 to 300 kg/cm G and a temperature of from -10 to 150C;
(b) from producing 1,3,5-tris(aminomethyl)-cyclohexane, hydrogenating 1,3,5-tris(aminomethyl)-benzene in the liquid phase in the presence of a ruthenium catalyst at a pressure of from 5 to 300 kg/cm2G and a temperature of from -10 to 200C; or (c) from producing 1,3,5-tris(aminomethyl)-cyclohexane, hydrogenating 1,3,5-tricyanobenzene in the liquid phase in the presence of a rhodium catalyst at a pressure of from 5 to 300 kg/cm2G and a temperature of from -10 to 250C.

~..
~ - 2a -9~18 f~Y~ MTA can be produced by hydrogenation of 1,3,5-tricyanobenzene (here-inafter referred to as "MTN") in the presence of a catalyst.
H6MTA can be produced either by hydrogenation of MTA in the presence of a catalyst, or by direct hydrogenation of MTN in the presence of a catalyst.
The trinitrile MTN can be obtained by the ammoxidation of mesitylene existing abundantly in petroleum distillates. For example, a catalyst contain-ing oxides of vanadium, chromium, uranium, barium, germanium, hafnium, rhenium and thorium is filled in a conventional fixed-bed reactor, and a mixed gas com-posed of 0.1 to 3 mole % of mesitylene, 0.3 to 20 mole % of ammonia and 80 to 99 mole % of air is subjected to ammoxidation at atmospheric pressure at a spacevelocity of 300 to 3000 hr 1, with the reaction temperature maintained at about 300 to 500C, whereby to obtain the trinitrile MTN. The catalyst to be employed is not necessarily limited to the above-mentioned, and other catalysts suited for the ammoxidation, depending upon the conditions, may be usable. As to the reaction temperature and mixed gas composition, moreover, the most preferred may be selected accordingly within the scope of reaction conditions combined therewith.
In order to obtain MTA, it is desirable to rely upon the process of hydrogenating the trinitrile MTN in the presence of a catalyst.
Said hydrogenation is conducted in the liquid phase in the presence of hydrogen, whereby the use of a solvent provides good results. As the solvent there may be used singly or as a mixture of two or more kinds, aromatic hydro-carbons such as benzene, toluene and xylene, alcohols such as methanol, ethanol,propanol, isopropanol and isobutanol, ethers such as dioxane and tetrahydro-furane, and other solvents inert under the reaction conditions such as water and liquid ammonia, although solvents based on alcohols or aromatic hydrocarbon-alcohol mixtures, allowing a reduction in the catalyst amount with a lessened decrease in the yield, are more preferably used. As to the amount of solvent used, which is no~ specifically restricted, 50 to 1000 V/W %, preferably 100 to 600 V/W ~, relative to the starting MTN provides satisfactory results.
Naturally, the use of larger quantities of the solvent does not interfere with the reaction but, use of a large amount of solvents is not economical from a commercial point of view. By adding at the same time a basic substance, for example, a hydroxide or alcoholate of an alkali metal, such as lithium hydrox-ide, sodiu~ hydroxide, potassium hydroxide, sodium methylate or sodium ethylate at a rate of 0.05 to 40% by weight, preferably 0.5 to 20~ by weight, based on the starting MTN, there may be obtained desirable results such as a decreased addition amount of a catalyst and shortened reaction time. In conducting the hydrogenation, use is made of hydrogen. While the reaction vessel is not speci-fically limited in design and construction, it must withstand the reaction con-ditions, and it is advisable to conduct the reaction in a pressure vessel such as an autoclave in the case of a higher reaction pressure being applied. The reaction pressure is generally in the region of 30 to 300 kg/cm2G, preferably in the region of 30 to 150 kg/cm2G, whereas the reaction temperature is general-ly in the range of -10 to 150C, preferably in the range of 40 to 120C. In carrying out the hydrogenation, it is normally desirable to use a catalyst. As examples of suitable catalysts there may be mentioned Raney cobalt, Raney nick-el, Raney nickel-chromium, platinum, palladium, ruthenium and rhodium. These are used singly or as a mixture of two or more kinds and Raney nickel-chromium, among others, produces the preferable results. By selecting a suitable reaction system, furthermore, there may be produced such conditions as may bring about a relatively small decrease in yield, even when a lower-priced nickel catalyst is utilized or the amount of added catalyst is reduced.
The novel triamine MTA according to the present invention is in the 11~9418 form of colorless crystals at ambient temperature and, upon heating to about 50C, turns into a colorless, transparent liquid.
In order to obtain the triamine H6MTA of the present invention, ei-ther the process of hydrogenating the triamine MTA or direct hydrogenation of the trinitrile MTN can be employed.
Hydrogenation of MTA is conducted in the liquid phase in the presence of hydrogen, with an appropriate solvent being employed if necessary. As the solvent may be employed singly or as a mixture of two or more kinds, for example, water, ethanol, methanol, propanol, isopropanol, isobutanol, dioxane, acetic acid, or tetrahydrofuran, although water is advantageous in terms of cost and an alcohol-water mixed solvent, in allowing a reduction in the catalyst amount with a lessened decrease in the yield, is preferred. Among the various reaction conditions selected, use of a solvent is not essential. Yet, when a solvent is used, 0.05 to 10 times the volume, preferably 0.1 to 5 times the volume, of the triamine MTA may provide satisfactory results. By adding 0.05 to 20% by weight, preferably 0.1 to 10% by weight, based on the MTA of a basic substance, for example an alkali metal hydroxide such as lithium hydroxide, sodium hydrox-ide, potassium hydroxide, calcium hydroxide, barium hydroxide or sodium carbon-ate, or an alkaline earth metal hydroxide or carbonate, there may be obtained the more desirable results. In conducting the hydrogenation, use is made of hydrogen gas. While the reaction vessel is not specifically limited in design and construction, it should naturally withstand the prevailing reaction condi-tions, and it is advisable to conduct the reaction in a pressure vessel such as an autoclave in the case of a higher reaction pressure being applied. The reaction pressure is generally in the region of 5 to 300 kg/cm2G, preferably in the region of 5 to 150 kg/cm2G, whereas the reaction temperature is general-ly in the range of -10 to 200C, preferably in the ~ange of 50 to 150C. In 11~9418 carrying out the hydrogenation, it is normally desirable to use a catalyst.
As examples of suitable catalysts may be mentioned Raney nickel-chromium, palla-dium, platinum, rhodium or ruthenium. These catalysts are used singly or as a mixture of two or more kinds, and, as the case may be, supported on a carrier, such as activated carbon, silica gel, alumina, diatomaceous earth or pumice, to obtain catalysts with more desirable properties. Among these, a ruthenium catalyst can be said to be particularly preferred, because it allows a reduction in the amount of catalyst to be added with a lessened decrease in the yield, especially when water containing a small amount of an alkali metal hydroxide or carbonate, alcohol or a mixture thereof is employed as solvent.
In addition, H6MTA can be directly obtained through hydrogenation of the trinitrile MTN.
In hydrogenating the trinitrile MTN, there may be produced more desir-able results by conducting the liquid-phase reaction in the presence of hydro-gen and employing a solvent. As examples of suitable solvents may be mentioned aromatic hydrocarbons such as benzene, toluene and xylene, alcohols such as methanol, ethanol, propanol, isopropanol and isobutanol, ethers such as dioxane and tetrahydrofuran, and others inclusive of acetic acid, liquid ammonia and water. These can be used singly or as a mixture of two or more kinds, although water, ethanol or their mixture, affording H6MTA in high yield, are the prefer-red solvents. When the reaction is conducted in the coexistence of ammonia or in a liquid ammonia solvent, formation of by-products can be prevented, and a similar effect can be achieved by adding to the solvent for the reaction 0.01 to 5%, preferably 0.05 to 3.0% of, a basic substance, for example caustic soda or caustic potash. As to the amount of solvent to be used, 1 to 10 times the volume of the starting trinitrile MTN, preferably 1 to 6 times the volume there-of, is the range in which satisfactory results can be produced. In carrying 11~9~18 out the hydrogenation, use is made of hydrogen gas. Although the type of re-action vessel is not specifically restricted, it should withstand the selected reaction conditions, and it is advisable, in the case of an increased reaction pressure being applied, to conduct the reaction in a pressure vessel such as an autoclave. The reaction pressure is generally in the region of 5 to 300 kg/
cm G, preferably in the region of 30 to 200 kg/cm2G, while the reaction tempe-rature is generally in the range of -10 to 250C, preferably in the range of 50 to 200C. It is desirable to use a catalyst in the hydrogenation. As ex-amples of suitable catalysts, there may be mentioned Raney cobalt, Raney nickel, Raney nickel-chronium, palladium, platinum, rhodium and ruthenium. These are used singly or as a mixture of two or more kinds, and, among others, the rho-dium catalyst, providing the triamine H6MTA in an increased yield, is preferred.
Especially, when water, ethanol or a mixture thereof is used as solvent, there results a higher yield of the hydrogenation reaction, and this may be consider-ed as the most desirable reaction conditions in the case of a one-step produc-tion of the triamine H6MTA from the trinitrile MTN.
H6MTA of the present invention is a colorless clear liquid at ambient temperature and, upon cooling, neither solidifies nor produces a precipitate.
The triamines (I) can be used as hardening agents for epoxy resins and as corrosion-inhibitors for metals.
The triamines (I) can also be converted into the corresponding tri-isocyanate (II) by the following per se known procedure of reaction with phosgene: CH2NH2 CH2NC0 ~ COC12 [I] [II]

11~9418 wherein ~ stands for ~ or ~ .
When ~ stands for ~ in the above formula [II], the tri-isocyanate compound is 1,3,5-tris(isocyanatomethyl)benzene (hereinafter referred to as '~TI") and when ~ stands for ~ , the triisocyanate compound is 1,3,5-tris(isocyanatomethyl)cyclohexane (hereinafter referred to as "H6MTI").
Phosgenation of the triamines represented by formula ~I) can be car-ried out in accordance with procedures conventional per se. Of these, one is the so-called cold/hot phosgenation, which comprises adding a triamine [I] or a solution of thereof in an organic solvent dropwise, with stirring, to cooled liquid phosgene or a solution of phosgene in an organic solvent, and raising the reaction temperature while feeding in phosgene to allow the reaction to proceed and go to conclusion. Another procedure comprises adding an organic solvent to a salt of the starting triamine to form a slurry or adding an acid to a solution of the triamine in an organic solvent to obtain a slurry of the triamine salt, and gradually elevating the temperature while feeding phosgene to the slurry to allow the phosgenation reaction to proceed and go to conclu-sion.
The triamines with a high degree of purity may be utilized, although the starting triamines containing a small amount of impurities by-produced dur-ing production of said triamines ca~ also be used.
As examples of organic solvents useful in the phosgenation reactionmay be mentioned aromatic hydrocarbons, halogenated aromatic hydrocarbons, halo-genated aliphatic hydrocarbons, and halogenated alicyclic hydrocarbons, and, among these, halogenated aromatic hydrocarbons such as chlorobenzene and o-di-chlorobenzene are preferred. The salts of the triamines which are operable include the acetic acid salt, hydrochloric acid salt, sulfuric acid salt, car-bamic acid salt and the like, and preferred among others is the carbamic acid ~1~9~18 salt formed by reacting the triamine with carbon dioxide gas~ Phosgene can be used either in the gaseous or liquid form, and phosgene dimer(trichloromethyl chloroformate) which is regarded as a precursor of phosgene in this industrial field can be used in place of phosgene.
~ egarding the reaction temperature for the phosgenation, a too ele-vated temperature results in formation of a large amount of by-products, while a too low temperature leads to a lowered reaction rate, and it is desirable to select the reaction temperature in the range of -20 to 180C.
Excessive phosgene and reaction solvent are removed from the reaction solution after completion of phosgenation and vacuum distillation is then ef-fected, thus resulting in the corresponding triisocyanates (II).
The triisocyanates (II) obtained by the above-mentioned procedure of-fer various advantages over conventionally known polyisocyanates. That is to say, they are each an odorless, non-irritant, colorless clear liquid with a very low viscosity at ambient temperature, and are therfore of great utility as a component for solvent-free or high-solids urethane coatings, while, being produced from relatively low-priced raw materials in a simplified production process, they possess the very high industrial importance.
The triisocyanates (II), through various polyaddition processes uti-lizing the reaction between an isocyanate and other active hydrogen-containing compound as known in the relevent industrial fields, can produce a wide variety of polyurethane resins. These triisocyanates, though being utilizable direct-ly in the original form, can also be used as various forms of modified products (e.g., dimer, trimer, carbodiimide, etc.) and in the form of prepolymers result-ing from their reaction with a polyol, polyamine, aminoalcohol, water and the like. ~here they are intended for applications such as backing paint, more-over, they can be utilized in the form of the so-called masked isocyanate formed with a variety of blocking agents being known as well.
In cases where these triisocyanates are reacted with polyol components usually employed in urethane coatings to form coating films, excellent proces-sability or workability is attained, and the resultant cured coating films ex-hibit very good physical properties and weatherability.
Besides being particularly suited for the field of urethane coatings, furthermore, the above-mentioned triisocyanates derived from the objective com-pounds of the present invention can be applied in a great variety of isocyanate-based products known in the relevent business circles, such as adhesive agents, 0 foamed products, artificial leather and filling agents.
Reference Example 1 Production of 1,3,5-tricyanobenzene.
To 150 parts of a 33% aqueous oxalic acid solution was added 18.2 parts of vanadium pentoxide, followed by heating over a hot water bath at about 100C, to dissolve vanadium pentoxide. The solution prepared in this manner was referred to as "solution A". Similarly, a solution of 20 parts of chro-mium oxide (VI) in 150 parts of a 33% aqueous oxalic acid solution was referred to as "solution B". Both solutions A and B were mixed homogeneously.
To the mixed solution was added 300 parts of anatase-type titanium dioxide powder baked at 800C, and water was allowed to evaporate with stirring.
The paste thus obtained was molded by wet extrusion to a size of 4 mm diameter and 5 mm length. The resultant moldings were dried at 100C for 15 hours and then baked in air at 500C for 4 hours to prepare a catalyst.
About 200 ml of the catalyst obtained in this manner was filled in a conventional reactor with fixed beds, and a mixed gas consisting of 0.5 mole %
of mesitylene, 7 mole % of ammonia and 92.5 mole % of air was reacted under the conditions of atmospheric pressure and a space velocity of 1000 hr 1 (con-1~94~8 verted to NTP), while maintaining the temperature of a bath for the reactor at 360C, to give 1,3,5-tricyanobenzene ~MTN) in a yield of 51.2 moles %.
The accompanying Figures 1 and 2 illustrate the IR absorption spectra of products described in Examples I and II.
Example 1 Into an autoclave of 300-ml content equipped with an electromagnetic agitator were placed with tight sealing 15 g of 1,3,5-tricyanobenzene ~MTN), 15 g of Raney-nickel-chromium catalyst (atomic ratio of Ni : Cr = 49 : 1), 27 ml of methanol, 63 ml of m-xylene and 0.18 g of caustic soda, and hydrogen was charged at an initial pressure of 100 kg/cm2G to conduct the reaction at 100C, resulting in absorption of 0.59 mole of hydrogen over a 35-minute period. The catalyst was filtered out and the solvent was distilled off, followed by con-ducting vacuum distillation, thus resulting in 12.8 g of 1,3,5-tris(aminomethyl) benzene (MTA) as colorless crystals. The substance exhibited a melting point of 49 to 51C and a boiling point of 136 to 139C/0.4 mmHg, with the IR absorp-tion spectrum as illustrated in Pigure 1.
75 mg of MTA obtained by the above-mentioned procedure was dissolved in 100 ml of diethyl ether, and acetic anhydride was added dropwise, whereby there were deposited colorless crystals. At the time when no additional crys-tal formation was observed, addition of acetic anhydride was discontinued, andthe crystals were recovered by filtration and dried to give 131 mg of 1,3,5-tris~acetylaminomethyl)benzene. Melting point 223-225C.
Elementary analysis (for C15H21N303);
C H N
Calcd. (%): 61.84 7.27 14.42 Found (%): 61.84 7.09 14.28 400 mg of MTA obtained in the above-mentioned manner was dissolved 11~9~18 in 200 ml of diethyl ether, and a diethyl ether solution containing 2.0 g of benzoic anhydride was added, whereupon colorless crystals separated out imme-diately. The crystals were recovered by filtration and dried, yielding 1.16 g of crystalline 1,3,5-tris~benzoylaminomethyl)benzene. Melting point 240-242C.
Elementary analysis lfor C30H27N3O3);
C H N
Calcd. (%): 75.45 5.70 8.80 Found (%) : 75.16 5.77 8.69 403 mg of 1,3,5-tris(aminomethyl)benzene obtained by the above-men-tioned procedure was dissolved in 60 ml of an ethanol/water (3:1) mixed solvent,and carbon dioxide gas was introduced, whereupon colorless crystals separated out. Introduction of carbon dioxide gas was continued until no additional crystal formation was observed, and the crystals were recovered by filtration and dried. Thus, there was obtained 560 mg of colorless crystals with a melt-ing point of 121.5 to 122.5C.
On the other hand, 330 mg of MTA obtained by the above-mentioned procedure was dissolved in 60 ml of ethanol, and dry hydrochloric acid gas was introduced, whereupon colorless crystals separated out. Introduction of the hydrochloric acid gas was continued until no additional crystal formation was observed, and the crystals were recovered by filtration and dried, resulting in 410 mg of colorless crystals with a melting point of not less than 300C.
Examples 2 through 10 Procedures were carried out in the manner described in Example 1 uti-lizing the reaction conditions as shown in Table 1, and the results as exhibit-ed in Table 1 were obtained.

~1~9~18 Table 1 Ex- Catalyst Alkali Solvent H2- React. React. Yield ample Type Amt., Type _ 7~pe Amt., kx/Cm temp., time mole

2 R-Ni 15 NaOH0.25 MxyOlHenme- 90 100 100 40 76.2 ______ (1/2)

3 CRr*Ni~ 15 NaOH 1.47 EtOH 90 100 72 15 89.4

4 R-Ni 15NaOH 0.52 MeOH/ 100 120 90 30 91.0 (1/1 )ene R-Ni- 7.5 LiOH. 0.37EtOH/m- 90 110 100 5 2 8 6 . 5 Cr~ H20 xylene ~______ 6 CRr~i- 3NaOH 0.4 MylHenme~90 120 105 61 94.3 _ _ ~ (1/2) 7 R-Ni- 15 NaOH 0.27 i-PrOH 90 120 100 100 56.5 _ _ 8 R-Ni- 15 _ _ MeOH/ 138 127 100 165 41.4 Cr~ _ ammonia 9 cRr*Ni~ 15 NaOH 0.05m-PrOH/ 90 120 110 180 19.1 X(Y/ le)ne

5%Rh- 4 _ _ 25% 80 120 65 15 89 .4 A123 aqueous _ _ an~nonia .

11~9418 Remarks *); The ratio of Ni : Cr in R-Ni-Cr was 49:1 (atomic ratio).
**); Yields were determined by gas chromatography.
Example 11 Production of 1,3,5-tris(aminomethyl)cyclohexane Into an autoclave of 300-ml content fitted with an electromagnetic agitator was placed with tight sealing 30 g of 1,3,5-tris~aminomethyl)benzene (MTA), together with 3 g of 5% ruthenium-alumina catalyst (produced by Nippon Engelhard Ltd.), 60 g of water and 0.75 g of caustic soda, and high-pressure hydrogen at 120 kg/cm2G in initial pressure was charged under pressure to react at 115C for 25 minutes, resulting in absorption of 0.61 mole of hydrogen.
The catalyst was filtered out, and the solvent was distilled off, followed by vacuum distillation, resulting in 26.8 g of 1,3,5-tris(aminomethyl)-cyclohexane (H6MTA). H6MTA was a colorless, clear, less viscous liquid having a boiling point of 127 to 128C/l mmHg. Its IR spectrum is illustrated in Figure 2.
Into about 20 ml of ethyl ether was dissolved 145 mg of H6MTA obtain-ed in this manner, and acetic anhydride was added dropwise, immediately yield-ing white crystals as a precipitate. When no additional crystal formation was observed, addition of acetic anhydride was suspended, and the crystals were recovered by filtration and dried to afford 248 mg of a triacetyl derivative.
The compound has a melting point of 278 to 279.5C and was found by elementary analysis to be in agreement with tris(acetylaminomethyl)cyclohexane having the empirical formula C15H27N303, as shown in the following:
Elementary analysis (for C15H27N303);
C H N
Calcd. ~%): 60.58 9.15 14.13 Found (%) : 60.66 9.22 14.03 ~ ~9~18 Then, 10 ml of an ethanol solution containing 176 mg of H6MTA was added to a mixture of 20 ml of ethanol and 1 ml of 35% hydrochloric acid, and stirred for about 1 hour. The crystals were recovered by filtration and dried to give 195 mg of a hydrochloride derivative.
The compound had a melting point of not lower than 300C, and was found by elementary analysis to be in agreement with the trihydrogenchloride having the empirical formula CgH24N3C13.
Elementary analysis (for CgH24N3C13);

C H N Cl Calcd. (%): 38.51 8.62 14.97 37.89 Found (%) : 38.39 8.83 14.73 37.94 Also, 210 mg of H6MTA was dissolved in 25 ml of ethanol, and carbon dioxide gas was introduced, resulting in separating out of crystals. After car-; bon dioxide gas was introduced until no additional crystal formation was ob-served, the crystals were recovered by filtration and dried under reduced pres-sure at ambient temperature to give 284 mg of white crystals (melting point of 85 to 86.5C).
Example 12 Into an autoclave of 500 ml capacity fitted with an electromagnetic agitator was placed with tight sealing 100 g of 1,3,5-tris(aminomethyl)benzene together with 5 g of a commercially available 5% ruthenium-carbon catalyst, 200 ml of water and 3 g of caustic potash, and high-pressure hydrogen gas at 120 kg/cm2G was charged under pressure, followed by conducting the reaction at 115C for 3 hours. 1.82 mole of hydrogen was absorbed, yielding H6MTA in a yield of 84.7 mole %.
Examples 13 through 20 20 g portions of 1,3,5-tris(aminomethyl)benzene were subjected to 119~9d~18 nuclear reduction in an autoclave of 300 ml capacity fitted with an electro-magnetic agitator under the following reaction conditions, to afford H6MTA in the below-mentioned yields.

1~9~18 Table 2 Ex Catalyst *r Alk~li Initial Re- Re- Yield of _ Solvent press., action action H MTA, amples Type*l ~mount, Type Amount, Kg/cm2 temp , time, 6 %
G C min.

13 A _ Water LiOH. 0.5 120 11523 B5 14 A 1 Water _ _ 120 115190 36 B 1 Water/ aOH 0.5 120 115 75 92 e(tl/ha2)nol 16 A 1 Water/n- NaOH 0.5 120 115 55 87 propanol I

17 B 1 Ethanol NaOH 0.15 120 135 165 54 18 5 2 propanol NaOH 0.20 120 145 180 41 19 B 2 Ethanol NaOH 0.18 120 130 128 81 A 1 Water Na2C03 1.0 120 115 36 83 Remarks:
*l) A; A commercially available 5% ruthenium-alumina catalyst B; A commercially available 5% ruthenium-carbon catalyst *2) The amount of the solvent is 80 ml.

11~94~8 Example 21 Into an autoclave of 300-ml content fitted with an electromagnetic agitator was placed with tight sealing 20 g of the 1,3,5-tricyanobenzene ob-tained in Reference Example 1, together with 80 ml of 25% aqueous ammonia, 300 mg of caustic soda and 4 g of a commercially available 5% rhodium-alumina catalyst and the reactants were subjected to reaction under high-pressure hy-drogen at 120 kg/cm G initial pressure at 105C for 70 minutes, resulting in absorption of 0.95 mole of hydrogen. By the above procedure there was obtained, in a yield of 45%, H6MTA having both the nitrile groups and benzene ring reduced.
ExamPle 22 Into an autoclave of 300-ml content fitted with an electromagnetic agitator was placed with tight sealing 20 g of the 1,3,5-tricyanobenzene ob-tained in Reference Example 1, together with 40 ml of 25% aqueous ammonia, 40 ml of ethanol, 500 mg of caustic soda and 4 g of a commercially available 5%
rhodium-alumina catalyst, and the reactants were subjected to reaction under high-pressure hydrogen at 120 kg/cm2C initial pressure at 105C for 180 minutes, resulting in absorption of 1.02 moles of hydrogen. By the above procedure there was obtained, in a yield of 43%, H6MTA having both the nitrile groups and benzene nucleus reduced.
Example 23 Into an autoclave of 300-ml content fitted with an electromagnetic agitator was placed with tight sealing 15 g of the 1,3,5-tricyanobenzene ob-tained in Reference Example 1, together 40 ml of ethanol, 40 ml of m-xylene, 320 mg of caustic soda 15 g of Raeny nickel-chromium (Ni:Cr=49:1) and 4 g of a 5% ruthenium-alumina, and the reactants were subjected to reaction under high-pressure hydrogen at 130 kg/cm2G initial pressure at 125C for 150 minutes, to give H6MTA in a yield of 57.2%.

~1~9418 Reference Example 2 Production of 1,3,5-tris(isocyanatomethyl)benzene Into 1200 ml of o-dichlorobenzene in a 2 liter four-necked flask was dissolved with warming 90.0 g of 1,3,5-tris(aminomethyl)benzene (MTA). Carbon dioxide gas was introduced into the resultant amine solution until no further weight increase was observed, resulting in a slurry of colorless crystals. The slurry material was maintained at a temperature of not higher than 10C for 30 minutes, while blowing phosgene gas with stirring, and the temperature was elevated to 130C over a 2 hour period while feeding phosgene, followed by main-taining a temperature of 130C for 5 hours. As the phosgenation reaction pro-ceeded, the slurry turned to a solution and, eventually, to a uniform slightly yellowish, clear solution.
After the completion of the phosgenation reaction, phosgene was re-leased from the solution by blowing nitrogen gas, and the o-dichlorobenzene solvent was distilled off under reduced pressure. Vacuum distillation of the resultant crude isocyanate gave 112.9 g of 1,3,5-tris(isocyanatomethyl)benzene ~MTI) having a boiling point of 173 to 175C/0.4 mmHg (a molar yield of 85.2%).
The ~TI was a less viscous liquid even at 5C and completely free from odor peculiar to isocyanates. It was found to have an amine equivalent of 83.25 (the theoretical value was 81.1).
The resultant MTI contained trace amounts of impurities, and in or-der to make definite identification thereof, the following experiment was car-ried out. A small amount of MTI was reacted with a large quantity of methanol to obtain the methylurethane derivative, and recrystallization of the same from acetone as the solvent gave the trimethylurethane of MTI as white crystals (recrystallization yield of 71.5%); results of elementary analysis of the puri-fied trimethylurethane compound were found to be in good agreement with the _ ~9 _ 11~9418 theoretical value. Melting point was 155-156C.
Elementary analysis (for C15H21N306);
C H N
Calcd. ~%): 53.09 6.24 12.38 Found (%) : 53.03 6.01 12.09 Reference Example 3 Production of 1,3,5-tris(isocyanatomethyl)cyclohexane Phosgenation was carried out in the same manner as in Reference Ex-ample 2, except that 70.0 g of 1,3,5-tris(aminomethyl)cyclohexane (H6MTA) ~IV) was used in place of 1,3,5-tris(aminomethyl)benzene (MTA) and that the reaction temperature was elevated from 10C to 120C over a 6-hour period, followed by maintaining the temperature at 120C for 6 hours. By the above procedure, there was obtained 91.8 g of 1,3,5-tris(isocyanatomethyl)cyclohexane (H6MTI) having a boiling point of 170 to 174C/0.53 mmHg (molar yield of 90.1%). The H6MTI
was a liquid less viscous even at 5C and free from odor. The amine equivalent was found to be 84.71 (calculated was 83.08).
A trimethylurethane derivative of H6MTI, purified through methyl-urethane formation and recrystallization from acetone as was the case with MTI, had the following values on elementary analysis:
Elementary analysis (for C15H27N306);
C H N
Calcd. (%): 52.16 7.88 12.17 Found (%) : 52.27 8.00 11.88 Experimental Example 1 Using the MTI as obtained in Example 2, a two-can type urethane coat-ing with a high non-volatile content was prepared.

9~18 Component A:
1) Acrylic polyol [a compol~mer solution witll 65% non-volatile content and OH
value of 65 produced by copolymerizing in a toluene/butyl acetate mixed solvent ~1:1) 50% of styrene, 23.2% of 2-hydroxyethyl methacrylate and 26,8% of n-butyl acrylate] 863 parts 2) Titanium dioxide powder 429.5 parts 3) Ethyl acetate/butyl acetate/cellosolve acetate (1/1/1) 276.1 parts Component B:
MTI 83.3 parts The component A, with the pigment well dispersed by means of a ball mill, was mixed with the component B in such a proportion as realized an NCO/OH
ratio of 1/1. The mixture showed 65% non-volatile content and a viscosity, of 24 seconds, as determined with the use of a Ford cup #4 at 25C. The mixture was immediately spray-applied on a soft steel plate surface treated with phos-phoric acid to form a dry coating film of 30 to 40 ~ in thickness. After con-ducting conditioning at 25C for 7 days, determination of physical properties and weathering test were effected on the coating film.
Coating film thickness: 30 to 40 Pencil hardness H
Erichsen extrusion test 8.5 mm Cross cut test 100/100 Sunshine type Weather-O-Meter 500 hr ~E 1.2 Experimental Examples 2 through 4 Using MTI as obtained in Example 2 and H6MTI as obtained in Example 3 in combination with a variety of polyols, two-can type urethane coatings with high non-volatile content were prepared in the same manner as stated in Experi-11~9418 mental Example 1 to investigate physical properties and weatherabilities of resultant coating films. The results obtained are tabulated in Table 3.
Table 3 Experiment No. 3 4 Component A:
Polyol ~parts) PolyesterAcrylic Polyester polyol (I),polyol, polyol (II), 255 863 243.9 Titanium dioxide 255.5430.4 219.1 ~parts) Solvent (parts). BA, 241.6EA/BA/CA BA, 136.9 ~l/2/77)4 Component B (parts)MTI, 83.3H6MTI,84.7 H6MTI,84.7 .
At the time of ~ixin~ of Components, and B:
Non-volatile content 1%) 70 65 80 Viscosity (sec.) 24 26 27 Physical properties:
Thickness of coating 30 to 40 30 to 40 30 to 40 film (~) Pencil hardness HB H HB
Erichsen (mm) 8.58.2 8.0 Cross cut test 100/100100~100 100/lOU

Weatherability, ~E 1.60.3 0.7 Remarks Polyester polyol (I); A condensate, with 100% non-volatile content and OH value of 220 formed from 2 moles of adipic acid, 1 mole of dipropylene glycol, 2 moles of trimethylol propane and 1 mole of coconut-oil based fatty acid.
Acrylic polyol; A copolymer solution with 65% non-volatile content and OH value of 65 produced by copolymerizing 5~% of styrene, 23.2% of 2-hydroxyethyl methacrylate and 26.8% of n-butyl acrylate in toluene-butyl acetate (1:1).
Polyester polyol (II); A condensate, with 100% non-volatile content and OH value of 230 prepared from 2 moles of adipic acid, 1 mole of diethylene glycol, 2 moles of trimethylol propane and 1 mole of coconut-oil based fatty acid.
BA: Butyl acetate EA: Ethyl acetate CA: Cellosolve acetate

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula:

(I) wherein is or .

2. A compound according to Claim 1, wherein in the formula is .

3. A compound according to Claim 1, wherein in the formula is .

4. A process for producing a compound of formula (I) as defined in claim 1, which comprises:
(a) for producing 1,3,5-tris(aminomethyl)-benzene, hydrogenating 1,3,5-tricyanobenzene in the liquid phase in the presence of a Raney-nickel or Raney-nickel-chromium catalyst at a pressure of from 30 to 300 kg/cm2G and a temperature of from -10 to 150°C;
(b) for producing 1,3,5-tris(aminomethyl)-cyclohexane, hydrogenating 1,3,5-tris(aminomethyl)-benzene in the liquid phase in the presence of a ruthen-ium catalyst at a pressure of from 5 to 300 kg/cm2G and a temperature of from -10 to 200°C; or (c) for producing 1,3,5-tris(aminomethyl)-cyclohexane, hydrogenating 1,3,5-tricyanobenzene in the liquid phase in the presence of a rhodium catalyst at a pressure of from 5 to 300 kg/cm2G and a temperature of from -10 to 250°C.

5. A process for the production of 1,3,5-tris(aminomethyl)-benzene, which comprises hydrogenating 1,3,5-tricyanobenzene in the liquid phase in the presence of a Raney-nickel or Raney-nickel-chromium catalyst at a pressure of from 30 to 300 kg/cm2G and a temperature of from -10 to 150°C.

6. A process according to claim 5, wherein the hydrogenation is carried out in the presence of a basic substance and a solvent.

7. A process for the production of 1,3,5-tris(aminomethyl)-cyclohexane, which comprises hydrogenating 1,3,5-tris(aminomethyl)benzene in the liquid phase in the presence of a ruthenium catalyst at a pressure of from 5 to 300 kg/cm2G and a temperature of from -10 to 200°C.

8. A process according to claim 7, wherein the hydrogenation is carried out in the presence of a basic substance and a solvent.

9. A process for the production of 1,3,5-tris(aminomethyl)-cyclohexane, which comprises hydrogenating 1,3,5-tricyanobenzene in the liquid phase in the presence of a rhodium catalyst at a pressure of from 5 to 300 kg/cm2G and a temperature of from -10 to 250°C.

10. A process according to claim 9, wherein the hydrogenation is carried out in the presence of a basic substance and a solvent.