JP2000044528A - Alicyclic diisocyanate composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an alicyclic diisocyanate composition for extremely activating a urethanization reaction, containing no impurity, capable of providing a polyurethane having improved weather resistance, etc., by including an alicyclic diisocyanate compound containing a fixed amount of a protonic acid as a main component. SOLUTION: This composition comprises an alicyclic diisocyanate compound of formula I (Y1 is a bifunctional saturated hydrocarbon, preferably a 1-10C alkylene) (e.g. 3-isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate) containing a protonic acid (preferably a saturated organic acid) as a main component. The compound of formula I is obtained by reacting a dialkyl carbonate prepared without using phosgene with an alicyclic diamine of formula II. The amount of the protonic acid added to the alicyclic diisocyanate compound of formula I is preferably 1×10-7 to 1×10-1 equivalent based on 1 equivalent of NCO group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition containing, as a main component, an alicyclic diisocyanate compound represented by the general formula (1) (hereinafter referred to as alicyclic diisocyanate compound A). More specifically, the present invention relates to a composition containing, as a main component, an alicyclic diisocyanate compound A having improved reactivity by containing a certain amount of protonic acid.

[0002]

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[0003]

2. Description of the Related Art Most of isocyanate compounds except those having a special structure are produced by isocyanating an amine compound with phosgene. Among these isocyanate compounds, the diisocyanate compound reacts with a compound having active hydrogen such as a hydroxyl group or an amino group to become a very useful polyurethane resin such as a paint, a heat insulating material, a cushion material, and a mechanical component, and is used in automobiles. It is widely used for many things necessary for our daily life, such as parts, home appliances, office equipment, clothing, furniture, etc. The urethane reaction for producing this polyurethane resin is as follows:
The reaction mechanism of the isocyanate group (reaction scheme (I)) shown below is Journal of Paint
Technology, vol. 43, no. 562 (19
71).

[0004]

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[0005] That is, it is presumed that the protons present in the reaction system act as catalysts, and the carbonyl of the isocyanate group attacks the hydroxyl group electrophilically. However, when examining conventional diisocyanate compounds and production processes, many diisocyanate compounds are produced by isocyanating an amine compound with phosgene as described above.As impurities of the diisocyanate compound, in addition to a trace amount of residual phosgene, a carbamoyl group, Compounds having a functional group such as a carboxyl group and hydrogen chloride were included. Their content is 100 to 1 in terms of chlorine.
000 ppm. Therefore, it is presumed that the protons released from these impurities acted as catalysts to activate the urethanation reaction.

[0006]

However, the contents of chlorine compounds in diisocyanate compounds starting from dialkyl carbonate and diamine are as follows. That is, in the case of a diisocyanate compound produced using a dialkyl carbonate and a diamine as starting materials produced via phosgene, 5 to 50 ppm in terms of chlorine, starting from a dialkyl carbonate and a diamine produced without using phosgene In the case of diisocyanate produced as a raw material, 1 pp in chlorine conversion
m or less. The diisocyanate compound having a small content of the chlorine compound has low reactivity at the time of the urethanization reaction.

[0007]

SUMMARY OF THE INVENTION The reactivity of these diisocyanate compounds is determined by comparing the reactivity of these diisocyanate compounds with conventional phosgene and diamine, that is, with a chlorine compound content of 100 to 10%.
In order to express a reactivity equivalent to or higher than that of the diisocyanate compound of about 00 ppm, intensive studies were repeated. As a result, when used as a composition mainly containing an alicyclic diisocyanate compound represented by the general formula (1) to which a proton acid capable of releasing protons was added,
Surprisingly, it has been found that the urethanization reaction is highly activated, leading to the present invention.

[0008]

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That is, the first aspect of the present invention is a composition containing a protonic acid and containing an alicyclic diisocyanate compound represented by the general formula (1) as a main component.

[0010]

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In the second aspect of the present invention, an alicyclic diisocyanate compound is prepared in a process substantially without using phosgene and a dialkyl carbonate and an alicyclic diamine represented by the general formula (2) (hereinafter referred to as an alicyclic diisocyanate compound). The present invention is the first composition of the present invention, which is an alicyclic diisocyanate compound represented by the general formula (1), which is produced from a cyclic diamine B).

[0012]

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[0013]

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A third aspect of the present invention is the first or second composition of the present invention, wherein Y ₁ in the general formulas (1) and / or (2) is an alkylene group having 1 to 10 carbon atoms. . A fourth aspect of the present invention is the first or second composition of the present invention, wherein the compound represented by the general formula (1) is 3-isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The composition containing the alicyclic diisocyanate compound A of the present invention as a main component is produced as follows. The composition of the present invention can be produced by adding a certain amount of a protonic acid described below to the alicyclic diisocyanate compound A.

The alicyclic diisocyanate compound A which can be applied for producing the composition of the present invention is not particularly limited, but is obtained by reacting a dialkyl carbonate represented by dimethyl carbonate with an alicyclic diamine B. Those produced by isocyanation, that is, those having a small content of chlorine compounds are preferred because of their large effect of addition.

The alicyclic diisocyanate compound A used in the composition of the present invention is a compound represented by the above general formula (1). In the general formula (1), the divalent saturated aliphatic hydrocarbon group represented by Y ₁ may be straight-chain or branched, and further, the branch may be a straight-chain carbon. The same carbon atom in the hydrogen group may be substituted with two alkyl groups.

Examples of the divalent saturated aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a trimethylene group, a 2-methyltrimethylene group, a 2,2-dimethyltrimethylene group, a tetramethylene group, Examples thereof include an alkylene group having 1 to 10 carbon atoms such as a methyltetramethylene group, a 2,2-dimethyltetramethylene group, a pentamethylene group, and a hexamethylene group. Preferred linear or branched alkylene groups are alkylene groups having 2 to 8 carbon atoms,
Particularly, an alkylene group having 2 to 6 carbon atoms is preferable. Specifically, the alkylene group is a 2,2-dimethyltrimethylene group, and examples of the alicyclic polyisocyanate represented by the general formula (1) include 3-isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate. it can.

These aliphatic hydrocarbon groups have various substituents, for example, an amino group, a hydroxyl group, and a group having 1 carbon atom.
To 4 alkoxy groups, carboxyl groups, alkoxycarbonyl groups, alicyclic hydrocarbon groups (cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, etc.), aromatic hydrocarbon groups (aryl groups such as phenyl groups), and halogen groups ,
A nitro group or the like may be substituted at an appropriate position.

Next, a method for producing the alicyclic diisocyanate represented by the general formula (1) according to the present invention will be described. The alicyclic diisocyanates represented by the general formula (1) reduce the 3-formylcycloalkanones represented by the general formula (3) or the 3-formylcycloalkenones represented by the general formula (4) It can be produced by further isocyanating after the specific amination.

[0021]

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In the general formulas (3) and (4), Y ₂ is a divalent saturated or unsaturated aliphatic hydrocarbon;
The chain may be linear or branched, and the branched hydrocarbon group may have the same carbon atom substituted by two alkyl groups. Examples of the divalent saturated aliphatic hydrocarbon include a methylene group, an ethylene group, a propylene group, a trimethylene group, a 2-methyltrimethylene group,
2,2-dimethyltrimethylene group, tetramethylene group,
Examples thereof include an alkylene group having 1 to 10 carbon atoms such as a 2-methyltetramethylene group, a 2,2-dimethyltetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the divalent unsaturated aliphatic hydrocarbon include alkenylene groups such as a propenylene group, a 2-methylpropenylene group, a 2,2-dimethylpropenylene group, a butylene group, and a pentylene group. Preferred linear or branched alkylene groups or alkenylene groups are alkylene groups or alkenylene groups having 2 to 8 carbon atoms, and particularly those having 2 to 2 carbon atoms.
6 alkylene groups or alkenylene groups.

The 3-formylcycloalkanones represented by the general formula (3) or the 3-formylcycloalkenones represented by the general formula (4) are cyclic ketones having a formyl group at the β-position. Specific examples include 3-formylcyclopentanone, 3-formylcyclohexanone,
-Methyl-3-formylcyclohexanone, 3-formylcycloheptanone, 5,5-dimethyl-3-formylcyclohexanone, 3-formylcyclooctanone, 5
-Methyl-3-formylcyclooctanone, 5-phenyl-3-formylcyclohexanone and the like. Specific examples of the latter are 3-formylcyclopentenone, 3-formylcyclohexenone, 5-methyl- 3-
Formylcyclohexenone, 3-formylcycloheptenone, 5,5-dimethyl-3-formylcyclohexenone, 3-formylcyclooctenone, 5-methyl-3-
Formylcyclooctenone, 5-phenyl-3-formylcyclohexenone and the like can be mentioned. In addition, if it has the above structure, a bicyclic fused ring compound sharing two or more carbon atoms (for example, 4-formylbicyclo [4.4.0] decane-3-ene-2-ene) ON etc.)
It may be.

The 3-formylcycloalkanones represented by the general formula (3) or the 3-formylcycloalkenones represented by the general formula (4) (hereinafter, these may be collectively referred to simply as “reaction substrates”) ) Is reductively aminated in the presence of a catalyst to produce a 3-aminomethylcycloalkylamine represented by the general formula (2). Incidentally, Y ₁ in the general formula (2) is the same as Y ₁ in the general formula (1).

Specific examples of such a 3-aminomethylcycloalkylamine include 3-aminomethylcyclopentylamine, 3-aminomethylcyclohexylamine, 3-aminomethyl-5-methylcyclohexylamine, and 3-aminomethylcycloheptyl. Amine, 3-aminomethyl-5,5-dimethylcyclohexylamine, 3
-Aminomethylcyclooctylamine, 3-aminomethyl-5-methylcyclooctylamine, 5-phenyl-
Examples of 3-aminomethylcyclohexylamine include 3-aminomethyl-5,5-dimethylcyclohexylamine as a preferred 3-aminomethylcycloalkylamine.

The reductive amination of the reaction substrate can be carried out by reacting hydrogen and ammonia in the presence of a catalyst. As the catalyst used for the reductive amination reaction, preferred catalysts include nickel compounds, cobalt compounds, platinum compounds, palladium compounds, cobalt-rhenium-molybdenum catalysts alone or, for example, activated carbon, alumina, carbon black, silicon carbide, and the like. , Silica-alumina, bentonite, zeolite, barium sulfate or the like, and used as a solid catalyst. The amount of these catalysts varies depending on the type of the catalyst, but is generally selected from the range of 1 to 50% by weight in terms of the catalytically active component with respect to the reaction substrate.

In the reductive amination reaction according to the present invention, either hydrogen gas or hydrogen-containing gas can be used as hydrogen for catalytic reduction, and high purity hydrogen gas may be used as the former, and hydrogen may be used as the former. For example, a gas inert to the reaction, for example, a mixed gas diluted with nitrogen, helium, argon or the like may be supplied to the reaction system. The hydrogen pressure in the reaction system is usually 1 to 200 kgf /
A range of cm ² is preferred.

As the ammonia source used for the amination according to the present invention, ammonia alone or an ammonia-containing gas is usually used, but a compound that produces ammonia (for example, an ammono salt) can also be used. The ammonia source has three forms, gas, liquid, and solid, and any form can be used. When used as a gas, a high-purity gas may be used. If necessary, the gas may be diluted with a gas inert to the reaction, for example, nitrogen, helium, argon, or the like, and supplied to the reaction system. These ammonia sources can be used alone or in combination of two or more depending on the type of the target compound.

Regardless of the above-mentioned ammonia source, the amount of the ammonia used in the present invention is preferably 2 to 100 mole times with respect to the reaction substrate such as 3-formylcycloalkanone or 3-formylcycloalkenone. .

The reductive amination reaction according to the present invention may be performed in the absence of a solvent, or may be performed in a solvent inert to the reaction. Solvents that can be used in the reductive amination reaction include solvents (aliphatic hydrocarbons, alicyclic hydrocarbons, esters, amides, ethers, etc.) used in the oxidation reaction described later, methanol, ethanol, propanol, isopropanol, Alcohols such as butanol, ethylene glycol, diethylene glycol, 1,4-butanediol and the like can be mentioned. As the solvent for the reductive amination reaction, alcohols and ethers are usually used. These solvents can be used as a mixture of two or more kinds.

The amount of the solvent used is preferably about 1 to 100 times by weight of the 3-formylcycloalkanone or the 3-formylcycloalkenone. The reaction temperature for reductive amination can be appropriately selected in consideration of the reaction rate and selectivity, and is preferably from 30 to 300 ° C.

The above reaction can be carried out according to a conventional reductive amination reaction. When a solvent is used, hydrogen is introduced into a reaction system containing 3-formylcycloalkanones or 3-formylcycloalkenones, ammonia and a solvent in the presence of a hydrogenation catalyst. In particular, when hydrogen is introduced into a reaction system containing 3-formylcycloalkenones, ammonia and a solvent in the presence of a hydrogenation catalyst to carry out the reaction, by-products can be suppressed. In this way, 3-aminomethylcycloalkylamines of alicyclic polyamines are obtained.

The alicyclic polyamines represented by the general formula (2) produced by the reaction can be used in various separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like. Separation and purification can be easily performed by using the separation means alone or in combination.

The alicyclic polyisocyanate represented by the general formula (1) according to the present invention, which is used as a raw material,
3- represented by the general formula (3) or (4), respectively.
Formylcycloalkanones or 3-formylcycloalkenones can be produced by various methods, for example, 3-methylcycloalkanones represented by the following general formula (5) or 3-methylcycloalkenones represented by the general formula (6) Can be oxidized in the presence of a catalyst.

[0035]

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Here, the oxidation in the presence of a catalyst refers to, for example, metal oxides (selenium dioxide, chromium oxide, dichromic acid,
Copper, silver, oxides such as lead), naphthenate (cobalt salts such as chromium), vanadium oxide-based catalyst (V ₂ O ₅ -SnO
_{2, V 2 O 5 -SnO 2} -Fe 2 O 3, V 2 O 5 -Fe 2 O 3 , etc.)
Oxidation in the presence of a catalyst such as
No. 54528 describes a method of oxidizing oxygen in the presence of a salt of at least one metal selected from iron, ruthenium, rhodium and cobalt, and a method of oxidizing using a heteropoly acid or a salt thereof as a catalyst, but is preferable. The method comprises oxidizing 3-methylcycloalkenones represented by the general formula (6) in the presence of a heteropolyacid as an oxidation catalyst or a catalyst based on a combination of the acid and a salt thereof to obtain a compound represented by the general formula (4). A process for obtaining formylcycloalkenones.

The carrier for supporting the catalyst component includes conventional carriers such as activated carbon, alumina, silica, silicon carbide, silica-alumina, bentonite, magnesia, titania, vanadia, zirconia, zeolite, diatomaceous earth, and kaolin. Organic carriers such as inorganic carriers and styrene-divinylbenzene copolymers are included.

The amount of the heteropolyacid or salt thereof carried on the carrier can be selected within a range that does not impair the catalytic activity, and is usually preferably 0.1 to 100 parts by weight, more preferably 5 to 20 parts by weight, per 100 parts by weight of the carrier. The degree is preferred.

As a method for supporting the heteropolyacid or its salts on the carrier, a conventional impregnation method, coating method, spraying method, adsorption method, precipitation method, etc. can be adopted. For example, an impregnation method, an adsorption method, or the like, which can be dispersed and supported on the substrate, is used. In carrying a heteropoly acid or salts thereof, a solvent such as water is usually used to carry the catalyst solution uniformly in many cases. The amount of these heteropoly acids or salts thereof used varies depending on the type of heteropoly acids or salts thereof, but is usually 0 in terms of heteropoly acids or salts thereof with respect to the raw material represented by the general formula (5) or (6). 0.1 to 50% by weight.

As the oxidizing source of the raw material represented by the general formula (5) or (6) according to the present invention, in addition to oxygen and an oxygen-containing gas, a compound generating oxygen can be used. Here, as the oxygen, for example, high-purity oxygen gas may be used, and as the oxygen-containing gas, the oxygen gas is diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide or the like as necessary. May be. When diluting with an inert gas, air may be used instead of oxygen, and nitrogen in the air may be used as the inert gas.

The amount of oxygen used is 0.1 to 1 mole of the reaction raw material.
5 to 1,000 mol is preferred. The oxidation reaction may be either gas phase oxidation or liquid phase oxidation. The reaction may be performed in the absence of a solvent, or may be performed in a solvent inert to the reaction. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; carbon tetrachloride, chloroform, dichloromethane, 1,2 Halogenated hydrocarbons such as dichloroethane; carboxylic acids such as acetic acid, propionic acid and butyric acid; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; diethyl ether, dibutyl ether and dimethoxyethane , Dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, 1-
Ethers such as methoxy-2-propanol; N, N-
Amides such as dimethylformamide and N, N-dimethylacetamide; and nitriles such as acetonitrile, propionitrile, and benzonitrile. These solvents can be used alone or in combination of two or more. The reaction temperature can be appropriately selected in consideration of the reaction rate and selectivity, and is preferably from 30 to 300 ° C, more preferably from about 50 to 200 ° C.

The dialkyl carbonate itself was once produced using phosgene as a raw material, but today it is also produced using carbon monoxide as a raw material, and new industrialization techniques are being established.

When a diisocyanate compound is produced by reacting a dialkyl carbonate produced using phosgene as a raw material with a diamine, a dialkyl carbonate produced using carbon monoxide, an alcohol and oxygen is used as compared with a dialkyl carbonate produced using phosgene as a raw material. The amount of the chlorine compound in the diisocyanate compound varies between 10 and 50 ppm as described above. When the amount of the chlorine compound fluctuates in this way, it is somewhat difficult to control the amount of the protonic acid added.
That is, it is necessary to measure the content of the chlorine compound in advance to determine the amount to be added.

On the other hand, a urethane compound is produced by using a dialkyl carbonate and a diamine compound produced without using phosgene so that chlorine is hardly brought in, and then the urethane compound is thermally decomposed. It is not necessary to measure the amount of chlorine in advance for the diisocyanate produced by the above method. That is, the content of the chlorine compound is as small as 1 ppm or less and constant.

Methods for producing a dialkyl carbonate without using phosgene are described in JP-A-63-57522, JP-A-63-72650, and JP-A-63-72.
No. 651, Japanese Patent Application Laid-Open No. Hei 01-28706, Japanese Patent Publication No. 60-58739, Japanese Patent Publication No. 56-8020, Japanese Patent Publication No. 60-23662, and Japanese Patent Publication No. 61-88.
No. 16, JP-B-61-43338, JP-B-6
It is disclosed in Japanese Patent Publication No. 3-38018 and Japanese Patent Publication No. 62-8113. The starting materials for this method are carbon monoxide, alcohol and oxygen, which are reacted in the presence of a catalyst under normal pressure or pressure.

As another method for producing a dialkyl carbonate without using phosgene, first, an alkylene carbonate is synthesized using alkylene oxide and carbon dioxide as starting materials, and this is further reacted with methanol to give dimethyl carbonate. This is a method for obtaining carbonate.
A method for synthesizing an alkylene carbonate using alkylene oxide and carbon dioxide as starting materials is described in, for example, JP-B-48-27314, JP-A-51-13720, JP-A-51-19722, and JP-A-51-19722. 1
No. 9723, JP-A-51-118763, JP-A-59-128382 and the like.

A method for synthesizing a dialkyl carbonate from an alkylene carbonate and an alcohol is disclosed, for example, in JP-B-60-22697 and JP-B-60-22.
No. 698, JP-B-61-4381, JP-B-5
6-40708, JP-B-61-16267, JP-B-60-27658, and JP-B-59-28.
542 and Japanese Patent Application No. 1-178347,
It is disclosed in Japanese Patent Application No. 1-178348.

Needless to say, even if the alicyclic diisocyanate compound A produced from the dialkyl carbonate and the alicyclic diamine B obtained by these methods is used, the composition containing the alicyclic diisocyanate compound A of the present invention as a main component Can be manufactured.

Recently, a production technique for converting a diamine into isocyanate with dimethyl carbonate has been disclosed (Japanese Patent Application Laid-Open No.
4-89556) can be mentioned as one of the production methods of the alicyclic diisocyanate A used in the present invention. More specifically, an alicyclic diamine B is reacted with dimethyl carbonate in the presence of an alkali catalyst to form a corresponding alicyclic urethane compound represented by the general formula (7) (hereinafter referred to as alicyclic urethane compound C). ), And then subjecting the alicyclic urethane compound C to a high boiling point solvent in the presence of one or more compound catalysts selected from the group consisting of manganese, molybdenum, tungsten, and zinc at 1 to 700 Torr.
Is thermally decomposed under reduced pressure to obtain the corresponding alicyclic diisocyanate compound A.
Can be manufactured.

[0050]

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The amine compound which can be used in the present invention is an alicyclic diamine represented by the general formula (2). The alicyclic diamine B has an amino group —NH ₂ and an aminomethyl group —
CH ₂ NH ₂ may be in the cis position or in the trans position in the cycloalkane ring. Both isomers are used as raw materials, and a mixture of the cis and trans isomers may be used.

The basic substance used as a catalyst in the first-stage reaction is an alkali metal or alkaline earth metal alcoholate, such as methyl, ethylate, lithium, sodium, potassium, calcium and barium.
Tertiary butyrate and the like can be mentioned as examples.

The amount of the alkali catalyst used is determined according to the activity of the catalyst so that the reaction is completed in a practical time.
In the case of sodium methylate, 0.001-
The reaction proceeds with the addition of 5% by weight, preferably 0.1 to 3% by weight.

It is practically possible to select the reaction temperature from 0 ° C. to the boiling point of the crude reaction solution. However, the reaction is slow at low temperatures and the boiling of by-produced methanol becomes intense at high temperatures. It is preferable to select in the range of 30 ° C to 80 ° C.

When the raw material is solid or when it is desired to prevent the precipitation of the resulting alicyclic urethane compound C, a solvent may be used, and for example, the raw material and product such as methanol, ethanol, tetrahydrofuran, dioxane, benzene and toluene may be used. Can be used.

When the basic catalyst is heated together with the alicyclic urethane compound C, it further changes the alicyclic urethane compound C to an undesired high-boiling substance. Neutralize the neutral catalyst. The alicyclic urethane compound C is purified to a required purity by a general purification method such as distillation, crystallization, washing with water, and reprecipitation from the neutralized crude product of the reaction product and taken out.

The alicyclic urethane compound C can be converted into the alicyclic diisocyanate compound A with high yield by the second stage reaction of thermal decomposition. The alicyclic urethane compound C is thermally decomposed in an inert solvent under reduced pressure in the presence of a simple metal of manganese, molybdenum, tungsten, zinc, or an inorganic compound or an organic compound, so that elimination of alcohol occurs. The alicyclic diisocyanate compound A is produced corresponding to the skeleton of the raw urethane.

The compounds used as catalysts include metal manganese, manganese oxide (MnO or Mn ₂ O ₃ ) manganese chloride, manganese sulfate, manganese phosphate, manganese borate, manganese carbonate, manganese acetate, manganese naphthenate, manganese (II) acetylacetonate, manganese (III) acetylacetonate, metal molybdenum, molybdenum trioxide, molybdenum acetylacetonate (Mo
O ₂ (acac) ₂ ) molybdenum dioxide, metallic tungsten, tungsten hexacarbonyl, tungstic anhydride, tungstic acid, and the like. These can be used in the form of a hydrated salt or in the form of an anhydride. Manganese chloride, manganese sulfate, manganese acetate and manganese naphthenate are particularly suitable because of their industrial availability, low cost and high activity. In particular, manganese acetate is preferable because it has a sufficient activity at a low concentration in the crude reaction solution. Usually, the use amount of the catalyst is most preferably in the region where the amount of the catalyst in the solvent is 0.0005% by weight to 5% by weight.

When the reaction temperature is lower than 150 ° C., the generation of isocyanate groups is delayed, which is not practical, and when the reaction temperature is higher than 300 ° C., it is difficult to carry out the reaction industrially and disadvantageously.

The solvent needs to be inert to the alicyclic diisocyanate compound A and the alicyclic urethane compound C, and is selected from aliphatic compounds, aromatic compounds, alkylated aromatic compounds, ether compounds and the like. Can be used. A solvent may be used even if it contains an inert group such as a halogen group. Further, a solvent whose boiling point is not close to that of the alicyclic diisocyanate compound A is easily purified and separated, and thus is preferable. The solvent having a boiling point lower than that of the alicyclic diisocyanate compound A to be formed is distilled together with the alicyclic diisocyanate compound A, which disadvantageously complicates the process in practical use. Those having a high boiling point are preferred.

The reaction is carried out under reduced pressure at which the alicyclic diisocyanate compound A generated from the reaction system is distilled off.
Thereby, the concentration of the alicyclic diisocyanate compound A in the system is kept low, side reactions are suppressed, and a high reaction yield is achieved. This effect is particularly effective when the reaction is carried out under boiling of the solvent. From this point, it is preferable to carry out the reaction at a reaction temperature at a reduced pressure at which the solvent boils. If the degree of decompression is too high, it is difficult to collect alcohol as a by-product, and it is disadvantageous in terms of equipment and utility. Therefore, the pressure is usually preferably 1 Torr or more and 700 Torr or less.

Preferred solvents are o-terphenyl, m-
Terphenyl, p-terphenyl, mixed diphenylbenzene, partially hydrogenated triphenyl, dibenzylbenzene, dibenzyltoluene, biphenyl, phenylcyclohexane, bicyclohexyl, phenylether, benzylether, diphenylmethane, xylene, trimethylbenzene, ethylbenzene, Examples include dodecylbenzene, chlorobenzene, dichlorobenzene, hexadecane, tetradecane, octadecane, eicosane, tetramethylene sulfone, and the like.

A continuous reaction in which the solvent containing the catalyst is boiled under reduced pressure and the alicyclic urethane compound C is charged therein is advantageous. The by-product alcohol and the alicyclic diisocyanate compound A generated in the reaction can be satisfactorily purified by introducing the gas from the reactor to the condenser as it is and condensing only the alicyclic diisocyanate compound A. The obtained alicyclic diisocyanate compound A can be further purified if necessary.

As mentioned above, one example of the production technique of the alicyclic diisocyanate compound A suitable for use in producing the composition of the present invention has been described, but the method of producing the dialkyl carbonate and the alicyclic urethane compound C is as follows. Not limited. For example, a technique for obtaining urethane from dimethyl carbonate and an amine compound using a Lewis acid catalyst is disclosed (JP-B-51-33095), but it can be used in the first-stage reaction. As for the second-stage reaction, a technique of performing pyrolysis in the gas phase (Japanese Patent Application Laid-Open No. 59-205352,
9-205353) and different liquid phase technologies (Japanese Patent Publication No.
No. 45736) may be used without any problem.

In the present invention, the alicyclic diisocyanate compound A
The term "protonic acid" as used herein is a general term for a Bronsted acid that releases a proton in accordance with an acid dissociation constant pKa specific to a compound as in the chemical formula (II).

[0066]

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In the present invention, the alicyclic diisocyanate compound A
Examples of the protic acids to be added to are: nitric acid, sulfuric acid, phosphoric acid, mineral acids such as phosphorous acid, formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid , saturated organic acids C ₁ -C _18, such as stearic acid, acrylic acid, methacrylic acid, vinyl acetate, sorbic acid, oleic acid, linoleic acid, unsaturated organic acids and their dimers of C ₃ -C _18, such as linolenic acid C such as acids, cinnamic acid, benzoic acid and salicylic acid
_{1- C18} alkyl group, alkenyl group-substituted aromatic organic acid, oxalic acid, adipic acid, malonic acid, palmitic acid,
Phthalic acid, isophthalic acid, trimellitic acid, polybasic acids and partial ester compounds of C ₂ -C _18, such as pyromellitic acid, lauryl sulfuric, p- toluenesulfonic acid, C ₁ -C _18, such as dodecylbenzene sulfonic acid Alkyl sulfates, C ₂ -C ₁₈ alkenyl sulfates and C ₆ -C ₂₄ alkylphenyl sulfates, dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, dimethylphosphonic acid, diethylphosphonic acid, diphenylphosphonic acid and the like. ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ phosphinic and phosphonic acids having an alkyl phenyl group of alkenyl group and C ₆ -C ₂₄ of, dimethyl phosphite, diethyl phosphite, diphenyl phosphite, dimethyl phosphate, diethyl Phosphate, diphenyl phosphate, 2 C ₁ such as ethylhexyl phosphate -
A C ₁₈ alkyl group, a C ₂ -C ₁₈ alkenyl group and C ₆
Phosphites and phosphates esters having an alkyl phenyl group -C _24, and the like.

Among them, most of the saturated organic acids are liquid at room temperature or liquefy immediately upon heating, have high solubility in the alicyclic diisocyanate compound A, and are generally inexpensive and easily available. It is one of the particularly useful proton acids among the protic acids that promote the chemical reaction.

An alicyclic diisocyanate compound A prepared from a dialkyl carbonate and an alicyclic diamine B in the present invention substantially without using phosgene in the process.
The amount of the protonic acid to be added is 1 × 10 ^-7 to 1 × 10 ^-1 equivalent, preferably 1 × 10 ^-6 equivalent, per equivalent of NCO group.
It is desirably about 1 × 10 ^-2 equivalents. When the amount of the protonic acid added is less than 1 × 10 ⁻⁷ equivalents per equivalent of NCO group, the amount added is too small, and only a composition having a low urethane-forming reaction rate can be obtained. Conversely, in the alicyclic diisocyanate compound A composition containing more than 1 × 10 ^-1 equivalent of the protonic acid per equivalent of NCO group, the protonic acid reacts with the alicyclic diisocyanate compound A to obtain a quality. However, it is not preferable because it is expected that the performance will be lowered.

The method for adding the protonic acid for accelerating the urethanization reaction of the alicyclic diisocyanate compound A produced from the dialkyl carbonate and the alicyclic diamine B in the present invention includes the following steps. To a predetermined amount, and it is possible to prepare the reactivity of the urethanization, and at the same time, as in the other urethanization catalysts, at the same time as the other urethanization catalyst, charge it in the reactor together with the alicyclic diisocyanate compound A. It is also possible to use it.

At this time, it is important to keep the water content of the protonic acid used as low as possible. If a large amount of water is mixed in the alicyclic diisocyanate compound A, Ureaization and allohanation occur, leading to a decrease in quality.

As the dialkyl carbonate described in the present invention, dimethyl carbonate, diethyl carbonate, diallyl carbonate and the like can be used. Also, diphenyl carbonate and the like can be used. Among them, dimethyl carbonate is preferably used.

[0073]

[Examples] Synthetic examples and examples are shown below. [Preparation of oxidation catalyst] Sodium metavanadate 43.9
0 g and 49.32 g of sodium molybdate in water 30
0 ml, heated to 95 ° C. and dissolved,
% Phosphoric acid 45.6 g and water 60 ml, 95 degreeC
For 1 hour under stirring. Thereafter, the mixture was cooled to 0 ° C., and a solution of 35.6 g of ammonium chloride and 126 ml of water was added to obtain a brown precipitate. The precipitate was filtered, and the precipitate was recrystallized twice with water to obtain an ammonium salt of a heteropoly acid.
As a result of analyzing the obtained ammonium salt of the heteropoly acid, the composition was (NH ₄ ) ₅ H ₆ [PV ₈ Mo ₄ O ₄₀ ] · 9.6H ₂ O. Activated carbon 1800 was added to a solution of the obtained heteropolyacid ammonium salt 200 mg and water 4000 ml.
mg was added and the mixture was stirred for 1 hour and left at room temperature. Thereafter, the mixture was filtered, washed with 4000 ml of water, and dried at 80 ° C. to obtain a catalyst supported on activated carbon.

[Synthesis Example 1] [Production of 3-formyl-5,5-dimethylcyclohexenone] 175 g of the catalyst prepared above, isophorone 138
g and 2,000 g of toluene in a glass flask (capacity 5
Liter) and reacted under an oxygen atmosphere under reflux for 20 hours. As a result of analyzing the reaction solution by gas chromatography, 93% of isophorone was reacted, and 62% of reacted isophorone was converted to 3-formyl-5,5-dimethylcyclohexenone (yield: 58% by weight).

[Synthesis Example 2] [Reductive amination reaction] In a solution prepared by dissolving 50 g of 3-formyl-5,5-dimethylcyclohexenone in 1,000 g of methanol, 10 g of Raney nickel and 150 g of ammonia were electromagnetically stirred in an autoclave. (3 liter capacity), and heated to 120 ° C., then hydrogen partial pressure 50 kgf /
cm ² , ² at a rotation speed of the stirrer of 800 to 1,000 rpm.
A time reaction was performed. After the reaction, cool the autoclave,
After the pressure was released, the reaction solution was taken out, the catalyst was filtered off, and methanol was distilled off at normal pressure to obtain 41 g of a substance. 97.4% by weight of the obtained substance was 3-aminomethyl-5,5-dimethylcyclohexylamine. This substance was subjected to mass analysis, elemental analysis, and infrared absorption spectrum analysis. Mass spectrometry result: molecular ion peak (m
/ E) is 156 (theoretical molecular weight 156), 127, 12
6, 113, 70, 56 and 43. Elemental analysis: C = 69.5, N = 12.7, H = 1
7.8% by weight, and the element composition ratio is C ₉ N ₂ H ₂₀ .

[Synthesis Example-3] [Synthesis of dimethyl carbonate produced without using phosgene in the process: Synthesis of dimethyl carbonate using carbon monoxide and methanol as raw materials] Teflon-coated autoclave having an inner volume of 5 liters Was used to carry out a synthesis reaction of dimethyl carbonate. 7.5 mmol / l palladium chloride and 187.5 mmol / l cuprous acetate as catalysts
And 47.5 vol% of nitrogen gas using 526 ml of a methanol solution of magnesium chloride 187.5 mmol / l,
Argon / oxygen (oxygen concentration 33.0 vol%) 22.5
A mixed gas of vol.% was introduced at 12.0 kg / cm ² , and the inside of the autoclave was heated to 130 ° C. and reacted for 1 hour. The reaction crude liquid was distilled to obtain dimethyl carbonate. The above synthesis reaction was repeated 20 times, and 234 g
Of dimethyl carbonate was obtained. The chlorine content in the obtained dimethyl carbonate was about 11 ppm. The chlorine content was measured by ion chromatography (IC-500).
It was used.

[Synthesis Example 4] The synthesis reaction was carried out 20 times in the same manner as in Synthesis Example 3 except that sodium chloride was used instead of magnesium chloride, to obtain about 352 g of dimethyl carbonate. However, the reaction in this case proceeded with the catalyst suspended in the liquid. The chlorine content in the obtained dimethyl carbonate was about 8 ppm.

[Synthesis Example-5] [Synthesis of alicyclic urethane compound C from dimethyl carbonate and alicyclic diamine compound B produced without using phosgene in the process] Dimethyl synthesized in Synthesis Example-3 211 g of carbonate was charged into a round bottom flask equipped with a stirrer, and the temperature was raised to 70 ° C. under a nitrogen stream while stirring. Next, 5.22 g of a 28% methanol solution of sodium methylate and 3-aminomethyl-5,5 were poured into the flask.
5-dimethylcyclohexylamine (hereinafter referred to as MDMCH
45.7 g was charged by two charging pumps at a uniform charging speed over 70 minutes. During this time, the reaction temperature was kept at 70 ° C. Further, after completion of the charging, the reaction mixture was aged at the same temperature for 3 hours, and then neutralized with phosphoric acid.
3-methoxycarbonylaminomethyl corresponding to DA
5,5-dimethyl-1-methoxycarbonylaminocyclohexane (hereinafter referred to as MDMCHDC) is MDMC
It was confirmed that the product was formed in a yield of 99% based on HDA and a yield of 99% based on consumed dimethyl carbonate. The crude reaction solution was deboiled and further washed with water to obtain MDMCHDC, which was used as a raw material in Synthesis Example-7.

[Synthesis Example-6] A synthesis reaction was carried out in substantially the same manner as in Synthesis Example-5 except that the dimethyl carbonate obtained in Synthesis Example-4 was used instead of the dimethyl carbonate obtained in Synthesis Example-3. MDMCHDC was obtained in yield.
The crude reaction solution is deboiled, washed with water and treated with MDM.
CHDC was obtained and used as a starting material for Synthesis Example-8.

[Synthesis Example-7] [Alicyclic diisocyanate compound A by thermal decomposition of alicyclic urethane compound C from dimethyl carbonate and alicyclic diamine B produced without using phosgene in the process] Synthesis] 10-stage Aldershaw Tower 2
Example of synthesis using a glass reboiler having a capacity of 00 ml-5
3-methoxycarbonylaminomethyl-5 obtained in
Continuous decomposition of 5-dimethyl-1-methoxycarbonylaminosiloxane (MDMCHDC) was performed. M-terphenyl was used as a solvent. First add 117 ml of m-terphenyl and m-terphenyl 1 to the reboiler.
10 ppm of anhydrous manganese acetate equivalent to 0 ppm
The mixture was heated under a reduced pressure of r until a boiling state was reached. Next, a mixture of 59.0% by weight of MDMCHDC and 41.0% by weight of m-terphenyl was charged into the reactor at a rate of 120 g / Hr. The product, 3-isocyanatomethyl-5,5-dimethylsiloxanehexyl isocyanate (hereinafter referred to as MDMCHDI), is withdrawn from the top of the distillation column at a bottom withdrawing rate such that the reactor liquid level is constant. The operation was performed.

[Synthesis Example-8] Anhydrous manganese acetate was dissolved in methanol so as to be 1% by weight. This solution is
It was diluted 80 times with DMCHDI to obtain a 125 ppm catalyst solution. The liquid was a uniform and low-viscosity liquid. Using the above catalyst solution, the same operation as in Synthesis Example-7 was performed except that MDMCHDC was charged in the bottom five stages of the distillation column and the catalyst preparation stage was changed from the bottom to thirteen stages. When the temperature in the column, the weight of the distillate and the bottoms and the composition were stabilized, the distillate was 1
Distillation was conducted over a period of time, whereby MDMCHDI was 98.1% by weight, monoisocyanate (MDMCHMI) was 1.8% by weight, and m-terphenyl was 0.05% by weight. MDMCHDC conversion 99% by weight, MDMCHDC high boiler conversion 2
% By weight. The yield was 95.5% for MDMCHDI and 1.5 for MDMCHMI based on the charged MDMCHDC.
%Met. The obtained MDMCHDI fraction was further purified to 99.7% purity by batch distillation and used as a raw material in the following Examples. Further, the generated alicyclic polyisocyanate compound is 3-isocyanatomethyl-5,5-
Being dimethylcyclohexyl isocyanate,
It was confirmed by the following elemental analysis, infrared absorption spectrum, NMR spectrum, and isocyanate group content. Elemental analysis results: C = 64.0, H = 7.7, N = 13.
0, the remaining O = 15.3, and the elemental composition ratio C ₁₁ H
It becomes ₁₆ N ₂ O ₂ . The isocyanate group content of the alicyclic diisocyanate compound was determined by a titration method. As a result, it was 39.3% by weight with respect to the theoretical value of 40.4% by weight.

[Example 1] MD obtained in Synthesis Example-8
MCHDI (hereinafter referred to as DMC method MDMCHDI) 10
Acetic acid was added to the isocyanate group in an amount of 5 × 1
0 ^-4 eq was added, the concentration was dissolved in o- xylene 2.0mo
A 1 / l DMC method MDMCHDI solution was prepared. On the other hand,
Reagent grade n-butanol was dissolved in o-xylene to prepare a 2.0 mol / l n-butanol solution. The above-mentioned DMC method MDMCHDI solution and n-butanol solution were placed in 5 ml and 10 m, respectively, in a Pyrex glass reactor having a capacity of 50 ml provided with a cooling tube and a sampling port.
1) The sample was accurately collected using a whole pipette, and 5 ml of a previously prepared 0.8 mol / l diphenyl ether / o-xylene solution was accurately added using a whole pipette. While sufficiently stirring the reaction solution and heating in an oil bath controlled at a temperature of 60 ± 1 ° C., the DMC MDMCHDI
And the urethanation reaction between n-butanol and n-butanol. DMC method MDMCH in reaction solution by gas chromatographic analysis
The change over time in the residual concentrations of DI and n-butanol was measured,
The urethanization reaction was measured and studied. As a result, the reaction time 3
The urethanization of the isocyanate groups is measured for
Method MDMCHDI measured the reactivity. The measurement results are shown in Table 1.

[Examples 2 to 6] The urethane was prepared in the same manner as in Example 1 except that a predetermined amount of the protonic acid shown in Table 1 was added to the DMC method MDMCHDI obtained in Synthesis Example-8. The chemical reactivity was measured. The measurement results are shown in Table 1.

[Comparative Example-1] DM obtained in Synthesis Example-8
Except for not adding acetic acid to Method C MDMCHDI,
The urethanization reactivity was measured in the same manner as in Example-1.
The measurement results are shown in Table 1.

Comparative Example 2 The urethanization reactivity was measured in the same manner as in Example 1 except that MDMCHDI produced by the phosgene method (hereinafter referred to as phosgene method MDMCHDI) was used and acetic acid was not added. It was measured.

[Example 7] In a reactor equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introducing tube, 104.1 g of the DMC MDMCHDI obtained in Synthesis Example-8 and acetic acid were added in an amount of 5 per isocyanate group. 1000 g of polytetramethylene glycol (PTG2000, manufactured by Nippon Polyurethane Industry Co., Ltd.) having 0.4 × 10 ^-4 equivalents and a number average molecular weight of 2,000
And heated immediately to urethanize at 120 ° C. MDMCH in the reaction product by gas chromatography
The time-dependent change in the residual concentration of DI was measured, and the urethanization reaction was measured and examined. As a result, even if the reaction was continued 3 hours after reaching the reaction temperature of 120 ° C., no significant decrease in the residual MDMCHDI concentration and the isocyanate concentration was observed. The measurement results are shown in Table 1.

[Example-8] The urethanization was carried out under the same conditions as in Example-7 except that the reaction temperature was changed to 70 ° C. MDMCH in the reaction product by gas chromatography
As a result of measuring the change over time in the residual concentration of DI and measuring and examining the urethanization reaction, no significant decrease in the residual MDMCHDI concentration and the isocyanate concentration was observed even when the reaction was continued 9 hours after the reaction temperature reached 70 ° C. . The measurement results are shown in Table 1. Table 1 shows the relative consumption rate with the MDMCHDI consumption rate after 3 hours of Comparative Example 1 as 1.

[0088]

[Table 1]

Example -9 The same conditions as in Example 7 were used except that polycaprolactone diol having a number average molecular weight of 2,000 (Placcel 220, manufactured by Daicel Chemical Industries, Ltd.) was used instead of polytetramethylene glycol. Urethane. As a result of measuring the change over time in the residual concentration of MDMCHDI in the reaction product by gas chromatography and measuring and examining the urethanization reaction, 2 hours after the reaction temperature reached 120 ° C., the residual MDMCHDI concentration was 2.4% by weight,
A urethane prepolymer having an isocyanate concentration of 3.4% by weight was obtained. Even after the reaction is continued, residual MDMCHD
No significant decrease in the I concentration and the isocyanate concentration was observed.

Example 10 A reactor equipped with a cooling pipe, a stirrer, a dropping funnel, a thermometer, and a nitrogen inlet pipe was prepared.
The DMC method MDMCHDI obtained in Synthesis Example-8 was used for 200
0.0 g of acetic acid at 5.4 × 10 ^-4 per isocyanate group
An equivalent amount was charged and heated to 50 ° C. 190.8 g of trimethylolpropane (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.) heated and melted at 70 ° C. was added dropwise over 3 hours. At this time, the reaction temperature rose to 70 ° C. After completion of the dropping, the time-dependent change of the isocyanate group concentration in the reaction product was measured by titration analysis, and the urethanization reaction was measured and examined. A monomer mixture was obtained. Thereafter, even if the reaction was continued, no significant decrease in the isocyanate concentration was observed.

Comparative Example 3 A reactor equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen inlet tube was charged with 104.1 g of the DMC-method MDMCHDI obtained in Synthesis Example 8 and polystyrene having a number average molecular weight of 2,000. Tetramethylene glycol (Nippon Polyurethane Industry Co., Ltd., PTG2000) 100
0 g was charged, immediately heated, and urethanized at 120 ° C. As a result, even if the reaction was continued 6 hours after the reaction temperature reached 120 ° C., no significant decrease in the residual MDMCHDI concentration and the isocyanate concentration was observed.

Comparative Example 4 The urethanization was carried out under the same conditions as in Comparative Example 3 except that the reaction temperature was changed to 70 ° C. MDMCH in the reaction product by gas chromatography
As a result of measuring the change over time of the residual concentration of DI and examining the urethanization reaction, 12 hours after reaching the reaction temperature of 70 ° C.,
With the residual MDMCHDI concentration of 7.7% by weight and the isocyanate concentration of 4.1% by weight, the designed urethane prepolymer was not obtained.

[Comparative Example-5] Polycaprolactone diol having a number average molecular weight of 2000 (Placcel 220, manufactured by Daicel Chemical Industries, Ltd.) was used in place of polytetramethylene glycol under the same conditions as in Comparative Example-4. Urethane. As a result of measuring the change over time of the residual concentration of MDMCHDI in the reaction product by gas chromatography and measuring and examining the urethanization reaction, even if the reaction was continued 4 hours after the reaction temperature reached 120 ° C., the residual MDMCHDI concentration, isocyanate No significant decrease in concentration was seen.

[Comparative Example-6] The DMC method MDMCHDI obtained in Synthesis Example-8 was placed in a reactor equipped with a cooling tube, a stirrer, a dropping funnel, a thermometer and a nitrogen inlet tube.
0.0 g was charged and heated to 50 ° C. 190.8 g of trimethylolpropane (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.) heated and melted at 70 ° C. was added dropwise over 3 hours. At this time, the reaction temperature rose to 70 ° C. 9 hours after the end of dropping,
Although a urethane prepolymer / monomer mixture having an isocyanate concentration of 31.4% by weight was obtained, the viscosity of the prepolymer was extremely high, and the molecular weight distribution was larger than that of a predetermined urethane prepolymer / monomer mixture.

[Comparative Example-7] All of the compounds were urethanized under the same conditions as in Comparative Example-4, except that MDMCHDI produced by the phosgene method (hereinafter referred to as phosgene method MDMCHDI) was used. Four hours after reaching the reaction temperature of 120 ° C., a designed urethane prepolymer was obtained with a residual MDMCHDI concentration of 4.0% by weight and an isocyanate concentration of 3.5% by weight.
Thereafter, even if the reaction was continued, no significant decrease in the residual MDMCHDI concentration and the isocyanate concentration was observed.

[0096]

According to the method of the present invention, it is possible to improve the reactivity of a diisocyanate compound having low reactivity during the urethanization reaction. That is, by adding a protic acid to a diisocyanate compound produced from a dialkyl carbonate and a diamine as in the method of the present invention, a diisocyanate compound equivalent to or more than a diisocyanate compound produced by a phosgene method using a conventional diamine compound. Since it shows the above reactivity and does not contain impurities derived from phosgene, a polyurethane having better weather resistance, corrosion resistance and heat resistance than conventional ones can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 31/02 101 B01J 31/02 101X // C07B 61/00 300 C07B 61/00 300 C08G 18/72 C08G 18/72 F-term (reference) 4H006 AA03 AA05 AB84 AC55 AC56 BA02 BA06 BA07 BA14 BA16 BA30 BA31 BA32 BA35 BA36 BA37 4H039 CA66 CA70 CD40 CD90 4J034 HA01 HA07 HC17 HC22 HC46 HC52 HC61 HC71 HC73 KA01 KB02 KD02 KD11 KD17 KD16 KE02

Claims (4)

[Claims] 1. A composition mainly containing an alicyclic diisocyanate compound represented by the general formula (1), which contains a protonic acid. Embedded image 2. The general formula (1) wherein an alicyclic diisocyanate compound is produced from a dialkyl carbonate produced substantially without using phosgene in the process and an alicyclic diamine represented by the general formula (2). The composition according to claim 1, which is an alicyclic diisocyanate compound represented by the formula: Embedded image Embedded image 3. The compound according to claim 1, wherein Y ₁ in the general formulas (1) and / or (2) is an alkylene group having 1 to 10 carbon atoms.
Or the composition according to 2. 4. A compound represented by the general formula (1):
3. The composition according to claim 1, which is isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate.