JP2000044527A - Alicyclic polyisocyanates, their production and their polyurethane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new alicyclic polyisocyanate compound having characteristics such as a high reaction rate with a hydroxyl group, etc., capable of providing a polyurethane resin having high weather resistance such as not yellowing, etc. SOLUTION: This alicyclic diisocyanate compound is shown by formula I (Y1 is a bifunctional aliphatic hydrocarbon, preferably a 1-10C alkylene) such as 3-isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate. The compound of formula I can be obtained by reductively aminating a 3-formylcycloalkane of formula II (Y2 is a bifunctional hydrocarbon) or a 3-formylcycloalkenone of formula III and then isocyanating the resultant substance. The reductive amination is preferably carried out by introducing hydrogen into a reaction system containing the compound of formula II or formula III, ammonia and a solvent in the presence of a catalyst. Consequently the compound of formula I can exhibit high reactivity and be expected as a raw material for a polyurethane useful as a resin, a coating material, an adhesive, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel alicyclic polyisocyanate, a method for producing the same, and a polyurethane using the same. More specifically, the present invention relates to alicyclic polyisocyanates having a high reactivity and specific properties due to having an isocyanate methyl group with less hindrance, a process for producing the same, and a polyurethane resin having specific properties using the same.

[0002]

2. Description of the Related Art Polyisocyanates are used in paints, polyurethane resins and the like by reacting with compounds having active hydrogen such as hydroxyl groups or amino groups. In particular, isophorone diisocyanate is a paint, a binder for ink,
It is widely used in industrial fields, such as coatings and adhesives. However, since toxic hydrocyanic acid is used as a raw material for production, there is a problem as an industrial production method.

On the other hand, polyurethane resin has poor weather resistance,
Due to the disadvantage of yellowing, non-yellowing isophorone diisocyanate is used for applications requiring weather resistance. However, isophorone diisocyanate has a drawback in that the urethanization reaction rate with a polyol having a hydroxyl group is slow, and it has been desired to develop a polyisocyanate in which these drawbacks are improved.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel polyisocyanate, which has a characteristic such as a high reaction rate with a hydroxyl group or the like. It is an object of the present invention to provide a method for producing a polyisocyanate which does not have any problems in its class and production, and a polyurethane resin having high weather resistance such as non-yellowing.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, oxidized methylcycloalkanone having a specific structure to introduce a formyl group. The alicyclic polyisocyanate compound obtained by reductive amination and further converting the amino group of the obtained alicyclic polyamine into an isocyanate group was found to be a useful substance for the purpose of the present invention. Completed the invention. The gist of the present invention is as follows.
The first invention relates to alicyclic polyisocyanates represented by the following general formula (1).

[0006]

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The second invention relates to the alicyclic polyisocyanate of the first invention, wherein Y ₁ is an alkylene group having ₁ to ₁₀ carbon atoms. The third invention relates to the alicyclic polyisocyanate of the first invention, wherein the compound represented by the general formula (1) is 3-isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate. According to a fourth aspect of the present invention, a 3-formylcycloalkanone represented by the following general formula (2) or a 3-formylcycloalkenone represented by the following general formula (3) is reductively aminated and then isocyanated. The present invention also relates to a method for producing an alicyclic polyisocyanate represented by the general formula (1).

[0008]

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In a fifth aspect, the method for reductive amination comprises introducing hydrogen into a reaction system containing 3-formylcycloalkanones or 3-formylcycloalkenones, ammonia and a solvent in the presence of a catalyst. The present invention relates to a method for producing an alicyclic polyisocyanate according to the fourth aspect of the present invention, wherein A sixth invention relates to a 3-formylcycloalkanone of the general formula (2) or a general formula represented by the formula (2) produced by oxidizing a 3-methylcycloalkanone or a 3-methylcycloalkenone.
The present invention also relates to the method for producing alicyclic polyisocyanates according to the fourth or fifth aspect of the present invention using the 3-formylcycloalkenones of (3). A seventh invention relates to a polyurethane obtained by reacting the alicyclic polyisocyanate according to any one of the first to third inventions with a polyol and / or a polyamine.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The alicyclic polyisocyanate according to the present invention is represented by the general formula (1). In the general formula (1), the divalent saturated aliphatic hydrocarbon group represented by Y ₁ may be linear or branched.
In addition, the branch may be 2 to the same carbon atom in the linear hydrocarbon group
May be substituted with one or more 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, C ₁ -C ₁₀ carbon atoms such as methyltetramethylene group, 2,2-dimethyltetramethylene group, pentamethylene group, hexamethylene group, etc.
Can be exemplified. Preferred linear or branched alkylene groups are alkylene groups having ₂ to ₈ carbon atoms, particularly alkylene groups having ₂ to ₆ carbon atoms. Specifically, the alkylene group is a 2,2-dimethyltrimethylene group, and 3-isocyanatomethyl-5,5 is an alicyclic polyisocyanate represented by the general formula (1).
-Dimethylcyclohexyl isocyanate.

These aliphatic hydrocarbon groups have various substituents such as amino group, hydroxyl group and C.sub.
_{1 to} C ₄ alkoxy groups, carboxyl groups, alkoxycarbonyl groups, alicyclic hydrocarbon groups (cycloalkyl groups,
A cycloalkenyl group, a cycloalkynyl group or the like), an aromatic hydrocarbon group (aryl group such as a phenyl group), a halogen group, a nitro group or the like may be substituted at an appropriate position.

Next, a method for producing the alicyclic polyisocyanate represented by the general formula (1) according to the present invention will be described. The alicyclic polyisocyanates represented by the general formula (1) are 3-formylcycloalkanones represented by the general formula (2) or 3-formylcycloalkenones represented by the general formula (3) Can be produced by reductive amination followed by isocyanation.

In the general formulas (2) and (3), Y ₂ is 2
Is a saturated or unsaturated aliphatic hydrocarbon, which may be linear or branched, and further has two alkyl groups at the same carbon atom in the linear hydrocarbon group. It may be replaced. Examples of the divalent saturated aliphatic hydrocarbon include a methylene group, an ethylene group, a propylene group,
Trimethylene group, 2-methyltrimethylene group, 2,2-
Dimethyl trimethylene group, tetramethylene group, 2-methyl-tetramethylene group, 2,2-dimethyl tetramethylene group, pentamethylene group, an alkylene group of carbon number and hexamethylene groups C ₁ -C ₁₀ may be exemplified. Examples of the divalent unsaturated aliphatic hydrocarbon include a propenylene group and 2-
Alkenylene groups such as a methylpropenylene group, a 2,2-dimethylpropenylene group, a butylene group and a pentylene group can be exemplified. Preferred linear or branched alkylene groups or alkenylene groups are C ₂ -C ₈ alkylene groups or alkenylene groups, and especially C ₂ -C ₆ carbon atoms.
Or an alkylene group or alkenylene group.

The 3-formylcycloalkanones represented by the general formula (2) or the 3-formylcycloalkenones represented by the general formula (3) are cyclic ketones having a formyl group at the β-position. Specific examples include 3-formylcyclopentanone, 3-formylcyclohexanone, 5-methyl-3-formylcyclohexanone, 3-formylcycloheptanone, 5,5-dimethyl-3-formylcyclohexanone, and 3-formylcyclooctane. Non-, 5-methyl-3-formylcyclooctanone, 5-phenyl-
3-formylcyclohexanone and the like,
Specific examples of the latter include 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 (2) or the 3-formylcycloalkenones represented by the general formula (3) (hereinafter collectively referred to simply as "reaction substrate") Is reductively aminated in the presence of a catalyst to produce a 3-aminomethylcycloalkylamine represented by the general formula (4). Incidentally, Y ₁ in the general formula (4) is the same as Y ₁ in the general formula (1).

[0017]

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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 performed by reacting hydrogen and ammonia in the presence of a catalyst. Examples of the catalyst (hereinafter sometimes referred to as “catalytically active component”) used in the reductive amination reaction include nickel compounds (reduced nickel, Raney nickel, etc.), cobalt compounds (cobalt, Raney cobalt, etc.), platinum compounds (platinum, etc.). Black, platinum oxide, etc.), palladium compounds (palladium, palladium black, etc.), metal catalysts such as rhodium, ruthenium, cobalt-rhenium-molybdenum, copper chromite, and copper-chromium. Among these, preferred catalysts are nickel compounds, cobalt compounds, platinum compounds, palladium compounds, cobalt-rhenium-molybdenum catalysts and the like. Although these catalysts can be used alone as a catalyst, they may be supported on a carrier and used as a solid catalyst.

The carrier for supporting the above-mentioned catalytically active component may be a conventional carrier such as activated carbon, carbon black, alumina, silica, silicon carbide, silica-alumina, bentonite, magnesia, titania, vanadia, zirconia, zeolite, diatomaceous earth. Inorganic carriers such as soil, kaolin and barium sulfate and organic carriers such as styrene-divinylbenzene copolymer are included. Among these, preferred carriers include porous carriers such as activated carbon, alumina, carbon black, silicon carbide, silica-alumina, bentonite, zeolite, and barium sulfate.

The specific surface area of the carrier used is not particularly limited, but is preferably 0.01 to 4,500 m
It is a ² / g, more preferably 0.1~4,000m ² /
g, usually about 0.2 to 3,000 m ² / g. The amount of the catalyst supported on the carrier is not particularly limited, and can be selected in a range where the catalytic activity can be further improved.
00 parts by weight, more preferably 0.1 to 50 parts by weight, further preferably about 0.5 to 30 parts by weight, and particularly preferably about 1 to 20 parts by weight.

The catalyst can be supported on the carrier by a conventional method such as an impregnation method, a coating method, a spray method, an adsorption method, a precipitation method, and the like. In particular, an impregnation method, an adsorption method, and the like can be used as a method capable of uniformly and highly dispersing and supporting a catalytically active component on a carrier. 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 /
cm ² is preferred, more preferably ^{5~150kgf / cm 2, 10~100kgf / cm} 2 approximately ranges are further 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 use amount of ammonia according to the present invention is preferably 2 to 100 mole times with respect to the reaction substrate such as 3-formylcycloalkanone or 3-formylcycloalkenone. , 2
A range of about 50 mole times is more preferable.

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 to be used is preferably about 1 to 100 times by weight, more preferably about 3 to 50 times by weight, particularly preferably 5 to 50 times by weight, based on the 3-formylcycloalkanone or 3-formylcycloalkenone. About 30 times by weight is preferable. 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, more preferably from 50 to 250 ° C, and even more preferably from about 100 to 200 ° 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 polyamine represented by the above general formula (4) produced by the reaction can be used in various separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization and column chromatography. By using the separation means alone,
Alternatively, it can be easily separated and purified by using a combination.

The 3-aminomethylcycloalkylamines represented by the general formula (4) can be obtained by converting an amino group into an isocyanate group by a known method.
It is converted to the alicyclic polyisocyanate represented by (1). Many methods for converting an amino group into an isocyanate group have been proposed, and by using these methods,
The alicyclic polyisocyanate represented by the general formula (1) according to the present invention can be produced. Among these known methods, the method using phosgene is still widely used for the industrial production of isocyanates, and there are many facilities that can utilize existing facilities and the yield of the process is high. Practical in terms of point. As a specific example, phosgene is added to polyamines at a low temperature in a solvent having no active hydrogen (for example, chlorobenzenes) according to the following process, followed by dehydrochlorination, and then further dehydrochlorination at a high temperature to obtain a polyamine. A method for obtaining isocyanates can be mentioned.

RNH ₂ + COCl ₂ → (−HCl) → R
NHCOCl → (−HCl) → RN = C = O

In another embodiment, the polyamines are converted to their corresponding carbamates according to the following process:
Subsequently, a method of obtaining a polyisocyanate by dealcoholization can be mentioned (method via carbamate).

RNH ₂ → RNHCOOR ′ → (−R′O
H) → RN = C = O

As a method of carbamate, a method of reacting a carbonate such as dimethyl carbonate with an amine, a method of reacting urea and an alcohol with an amine, and the like have been proposed, and both can be applied. Further, in the above process, as a method of de-alcoholizing the carbamate and converting it into an isocyanate, a method of thermally decomposing the carbamate in the presence of a metal acid catalyst and separating the by-product alcohol by distillation or the like to recover the target isocyanate is preferable. . This method via carbamate is excellent as a process which does not use highly toxic phosgene in high yield.

The polyisocyanates obtained by the above-mentioned various methods can be separated from the crude reaction solution by conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column separation means, and separation means combining these. To purify to the required purity.

The 3-formylcycloalkanone represented by the general formula (2) or (3) used as a raw material of the alicyclic polyisocyanate represented by the general formula (1) according to the present invention. Or 3-formylcycloalkenones can be prepared by various methods, for example, using 3-methylcycloalkanones represented by the following general formula (5) or 3-methylcycloalkenones represented by the general formula (6) in the presence of a catalyst. It can be obtained by oxidation below.

[0037]

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Here, the oxidation in the presence of a catalyst means, for example, a metal oxide (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 -Sn
O ₂ , V ₂ O ₅ —SnO ₂ —Fe ₂ O ₃ , V ₂ O ₅ —F
How to oxygen oxidation in the presence of a catalyst e ₂ O _3, etc.) or the like, iron as described in JP-A-58-154528, ruthenium, presence of at least one metal salt selected from rhodium and cobalt Oxygen oxidation method under, refers to a method of oxidizing heteropolyacid or a salt thereof as a catalyst,
A preferred method is to oxidize 3-methylcycloalkenones represented by the general formula (6) in the presence of a heteropolyacid as an oxidation catalyst or a catalyst relating to a combination of the acid and a salt thereof, and represented by the general formula (3) This is a method for obtaining 3-formylcycloalkenones.

The heteropolyacid is a condensate of an oxyacid containing two or more different types of central ions, and is also called a heteronuclear condensed acid. Heteropoly acids include, for example, P, As, S
Oxygen ions of elements such as n, Si, Ti and Zr (for example, phosphoric acid, silicic acid, etc.) and oxygen acids of elements such as V, Mo, W (for example, vanadic acid, molybdic acid, tungstic acid, etc.) It is possible to obtain various heteropolyacids which are used as a catalyst.

A preferred heteropolyacid anion composition can be represented by XM ₁₂ O ₄₀ , where X is S
i is an element such as P, and M is an element such as Mo, W, and V. As a heteropolyacid having such a composition,
For example, phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, phosphovanadomolybdic acid and the like can be preferably exemplified, but phosphomolybdic acid and phosphovanadomolybdic acid are more preferable. In particular, phosphorus vanadomolybdic acid is most preferred. Here, the phosphorus vanadomolybdic acid or a salt thereof is represented by the following general formula (7). A _{3 + n} [PV _n Mo _12-n O ₄₀ ] (7) (where A represents a heteropolyacid cation and n is an integer of 1 to 10) The heteropolyacid cation represented by A is In addition to the hydrogen atom, other cations such as NH ₄ , alkali metals (Cs, Rb, K, Na, Li, etc.), alkaline earth metals (Ba, Sr, Ca, Mg, etc.) may be used.

The heteropolyacid exhibits a sufficiently high activity as a free heteropolyacid, but when the heteropolyacid cation is a hydrogen atom, it is possible to substitute at least a part thereof. By substituting a part of the hydrogen of the heteropolyacid cation, the heteropolyacid becomes insoluble, the stability and heat resistance can be improved, and a more useful catalyst can be obtained. The type of the substitutable cation is not particularly limited. For example, NH ₄ , an alkali metal (Cs,
Rb, K, Na, Li, etc.), alkaline earth metals (B
a, Sr, Ca, Mg, etc.). In particular,
Part of the heteropoly acid is replaced with an ammonium cation,
When the cation is composed of both H ⁺ and NH ₄ ⁺ ,
Activity and stability can be further improved, in this case,
The ratio of NH _{4 to} hydrogen atoms is preferably NH ₄ / H (molar ratio) = 0.1 to 10, more preferably NH ₄ / H (molar ratio) = 0.2 to 8, and furthermore NH ₄ / H (Molar ratio) = about 0.3 to 5 is more preferable.

The value of n in the general formula (7) can be appropriately selected in consideration of oxidizing power and stability, and is preferably 1 to 10, more preferably 4 to 10, and most preferably about 5 to 8. It is suitable. When the heteropolyacid cation is composed of H and another cation (such as NH ₄ ⁺ ), the value of n is 4 to 1
In many cases, about 0 is preferable. These heteropolyacids or salts thereof can be used alone or in combination of two or more, but when used alone, they may be supported on a carrier and used as a solid catalyst. By supporting on a carrier in this manner, the catalytic activity is increased.

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. Preferred carriers include porous carriers such as activated carbon, alumina, titania, silicon carbide, silica-alumina, bentonite, and zeolite, with activated carbon being particularly preferred. When activated carbon is used, the selectivity of the oxidation reaction of the 3-position methyl group of the reaction raw material can be further improved. The activated carbon may be in the form of granules or fibers.

The specific surface area of the carrier is not particularly limited.
0-4500 m < ² > / g is preferable, and 50-4,000 m < ² >.
/ G is more preferable. Usually 100-3,000m
Those of about ² / g are preferably used. In the case of activated carbon as a preferred carrier, the specific surface area is 300 to 4,000.
m ² / g are preferred, more preferably about 400~3,000m ² / g, usually often used activated carbon of about 500~2,000m ² / g.

The average pore size of the activated carbon is preferably from 5 to 200 angstroms, and more preferably from about 10 to 100 angstroms. The pore volume of activated carbon is 0.1 to 10
It is preferably about ml / g, more preferably about 0.3-5 ml / g.

The amount of the heteropolyacid or salt thereof supported on the carrier can be selected within a range that does not impair the catalytic activity. Usually, 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, per 100 parts by weight of the carrier Parts is more preferable, but is more preferably about 5 to 30 parts by weight, and particularly preferably about 5 to 20 parts by weight.

The heteropolyacid or salt thereof can be supported on the carrier by a conventional impregnation method, coating method, spraying method, adsorption method, precipitation method, etc. 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 heteropolyacids or salts thereof used depends on the type of heteropolyacid or salts thereof, but the general formula (5) or (6)
Is usually selected from the range of 0.1 to 50% by weight in terms of a heteropoly acid or salts thereof.

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 mol of the reaction raw material.
It is preferably from 5 to 1,000 mol, and more preferably a large excess of from 1 to 1,000 mol. 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; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane and 1,2-dichloroethane; carboxylic acids such as acetic acid, propionic acid and butyric acid; ketones such as acetone and methyl ethyl ketone; methyl acetate; Esters such as ethyl acetate, isopropyl acetate and butyl acetate; ethers such as diethyl ether, dibutyl ether, dimethoxyethane, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, 1-methoxy-2-propanol;
Amides such as N, N-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, but is preferably from 50 to 20 ° C.
About 0 ° C. is more preferable.

Next, a polyurethane using the polyisocyanate obtained as described above will be described. A polyurethane is obtained by reacting a polyisocyanate with a known polyol and / or polyamine. In terms of the number of functional groups, polyols such as diols, triols, tetrols, pentols and the like can be used. In terms of molecular weight, low molecular weight polyols, high molecular weight polyether polyols, and high molecular weight polyester polyols are examples of polyols. In terms of the number of functional groups, polyamines include polyamines such as diamine, triamine, tetramine, and pentamine. In order to produce polyurethane, various chain extenders, curing agents, crosslinking agents, water and the like can be added. Further, a catalyst is used if necessary. Examples of additives of the polyurethane resin include a foaming agent, a surfactant, an ultraviolet stabilizer, an antioxidant, an antistatic agent, and an inorganic or organic filler. The polyisocyanate of the present invention has a higher reaction rate than isophorone diisocyanate and the like, and is advantageous in terms of the reaction temperature, the type of catalyst, and the low amount used. Further, the obtained polyurethane can be used for various conventional applications. In particular, urethane corresponding to the 3-position isocyanatemethyl group of the raw material polyisocyanate in an alicyclic skeleton forming a hard segment of polyurethane,
The free mobility around the urea bond is high, and more flexible physical properties can be obtained with respect to temperature change, and it is suitable for non-yellowing paints and adhesives.

[0051]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. (Example 1) [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, (NH ₄ ) ₅ H ₆ [PV ₈ Mo ₄ O ₄₀ ] · 9.6H _{2 was obtained.}
O composition. Activated carbon 18 was added to a solution of 200 mg of the obtained ammonium salt of heteropolyacid and 4000 ml of water.
After adding 00 mg, 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. [Production of 3-formyl-5,5-dimethylcyclohexenone] 175 g of the catalyst prepared above and 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). [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 placed in a magnetically stirred autoclave (3 liters in volume), and ℃, hydrogen partial pressure 50kgf /
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 . [Polyisocyanate reaction] 3 obtained by the above method
-Aminomethyl-5,5-dimethylcyclohexylamine (78 g) and dimethyl carbonate (360 g) were charged into a round-bottom flask equipped with a stirrer, and heated to 70 ° C. while stirring under a nitrogen atmosphere. Next, 28 of sodium methylate
8.9 g of a methanol solution of 10% by weight was added dropwise over 10 minutes.
After further aging for 50 minutes, the reaction crude liquid was analyzed by gas chromatography to find that the dicarbamate compound of the following formula (8) corresponding to 3-aminomethyl-5,5-dimethylcyclohexylamine had a yield based on the amine of the above-mentioned raw material. At 9
It was confirmed that 2 wt% was generated.

[0052]

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A 300 ml flask was set in a glass 10-stage Oldershaw tower equipped with a reflux condenser, and partially hydrogenated triphenyl (trade name: Therm S900, manufactured by Nippon Steel Chemical Co., Ltd.)
g, and manganese acetate tetrahydrate (0.05 g) were charged and heated under reduced pressure, and the degree of reduced pressure was adjusted so that the can solution boiled at 230 ° C. Next, the dicarbamate compound of the above formula (8) was dropped into the flask at a rate of 60 g / hour from a double-tube dropping funnel heated with a heating medium to a temperature at which the compound maintained fluidity. After the start of charging, 3-isocyanatomethyl-
Since a liquid rich in 5,5-dimethylcyclohexyl isocyanate (formula (9) below) came up, it was distilled from the top of the column at a distilling rate corresponding to the dropping rate of the dicarbamate compound.

[0054]

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After the operation for 2 hours, the distillation was continued until the generation of the alicyclic polyisocyanate compound disappeared, and then the operation was stopped. The distillate was collected and subjected to gas chromatography analysis. As a result, the yield of the alicyclic polyisocyanate compound based on the starting amine compound was 93% by weight. Further, it was confirmed by the following elemental analysis, infrared absorption spectrum, NMR spectrum and isocyanate group content that the produced alicyclic polyisocyanate compound was 3-isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate. 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 content of the isocyanate group in the alicyclic polyisocyanate compound was determined by a titration method. As a result, the theoretical value was 39.4% by weight with respect to 40.4% by weight.

(Example 2) 3-aminomethyl-5,5-dimethylcyclohexylamine 78 obtained in Example 1
g was dissolved in 500 g of ortho-dichlorobenzene,
After 1 mol of phosgene was blown in for 1 hour, dehydrochlorination was performed at 40 ° C. under reduced pressure, dehydrochlorination was further performed at 130 ° C., and the reaction product was filtered off as a crystal and further recrystallized. . As a result of gas chromatography analysis, the content of 3-isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate in the obtained purified crystal was 98%.
Area%.

Example 3 Production of Polyurethane The reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling tube was charged with 3-isocyanatomethyl-5,5- 41.6 g of dimethylcyclohexyl isocyanate and a number average molecular weight of 2,0
200 g of polycaprolactone diol (trade name: PCL-220, manufactured by Daicel Chemical Industries, Ltd.) while stirring in a nitrogen atmosphere, setting the temperature of the reaction system to 80 ° C., and continuing the urethanization reaction for 3 hours. A urethane prepolymer having a content of 3.3% by weight was obtained. After lowering the temperature of the reactor to 40 ° C., 199 g of xylene and methyl isobutyl ketone (MIB) were added to the urethane prepolymer.
K) 161 g was added to make a homogeneous solution. 3-aminomethyl-5,5-dimethylcyclohexylamine 1 obtained in Example 1 was added to the obtained urethane prepolymer solution.
5.4 g, 0.8 g of di-isobutylamine, MIBK3
A solution of 8.0 g and 199 g of isopropanol was added, and a chain extension reaction was performed with a diamine. The reaction temperature was set to 50 ° C., and the reaction was continued for 3 hours to obtain a target polyurethane resin solution. The resulting polyurethane resin solution is
It cures quickly and is useful as an adhesive with excellent weather resistance, heat resistance, and corrosion resistance.

Example 4 Production of Polyurethane Using 41.6 g of 3-isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate obtained by the phosgene method obtained in Example 2 as the diisocyanate, the number average molecular weight was 2,000. Polytetramethylene glycol having a number average molecular weight of 2,000 (trade name: PTG20 manufactured by Hodogaya Chemical Co., Ltd.)
00) A polyurethane resin solution was synthesized using the same apparatus and method as in Example 3 except that 200 g was used. The resulting polyurethane resin solution cures quickly, has weather resistance,
It is useful as an adhesive with excellent heat resistance and corrosion resistance.

[0059]

According to the present invention, the novel alicyclic polyisocyanate compound has high reactivity because the methyl group is not substituted at the position of substitution of the isocyanate methyl group, and is obtained by using it. Polyurethane is useful as a resin, paint, adhesive or the like, and can efficiently produce alicyclic polyisocyanates.

Continued on the front page F-term (reference) 4H006 AA01 AA02 AA03 AB46 AC52 AC55 BA05 BA14 BA20 BA21 BA23 BA24 BA25 BA26 BA61 BA68 BA71 BA75 BA85 BB14 BB15 BC10 BC11 BE14 BE20 BE52 BJ20 4J034 CA03 CA14 CA15 CA16 CB03 CB04 DB03 CB04 DB03 CB04 HA01 HA07 HC17 HC22 HC45 HC46 HC47 HC52 HC61 HC71 HC73 KA01

Claims (7)

[Claims] An alicyclic polyisocyanate represented by the following general formula (1). Embedded image 2. The alicyclic polyisocyanate according to claim ₁ , wherein Y ₁ is an alkylene group having ₁ to ₁₀ carbon atoms. 3. The alicyclic polyisocyanate according to claim 1, wherein the compound represented by the general formula (1) is 3-isocyanatomethyl-5,5-dimethylcyclohexyl isocyanate. 4. A 3-formylcycloalkanone represented by the following general formula (2) or a 3-formylcycloalkanone represented by the following general formula (3):
A general formula characterized in that formylcycloalkenones are reductively aminated and then further isocyanated.
A method for producing the alicyclic polyisocyanate represented by (1). Embedded image 5. A method for reductive amination wherein hydrogen is introduced into a reaction system containing 3-formylcycloalkanones or 3-formylcycloalkenones, ammonia and a solvent in the presence of a catalyst. A method for producing an alicyclic polyisocyanate according to claim 4. 6. A 3-methylcycloalkanone or 3-methylcycloalkanone
General formula formed by oxidation of methylcycloalkenones
The process for producing alicyclic polyisocyanates according to claim 4 or 5, wherein a 3-formylcycloalkanone of the formula (2) or a 3-formylcycloalkenone of the formula (3) is used. 7. A polyurethane obtained by reacting the alicyclic polyisocyanate according to claim 1 with a polyol and / or a polyamine.