TWI423995B - A reaction catalyst for forming a isocyanurate link, and a method for producing the modified polyisocyanate mixture containing the isocyanurate link - Google Patents

Description

Reaction catalyst for forming isomeric cyanurate chain, and method for producing modified polyisocyanate mixture containing isomeric cyanate chain using the same

The present invention relates to a method for producing a modified polyisocyanate mixture containing a hetero-cyanate chain used for a high-performance hardener for a two-liquid type polyurethane dye coating, and the like The reaction catalyst for the polycyanate chain.

The modified polyisocyanate containing an isocyanurate chain obtained from toluene diisocyanate (TDI) is particularly suitable for use as a polyisocyanate curing agent for coatings because of its excellent quick-drying property and characteristics. The modified polyisocyanate containing an iso-cyanate chain obtained by TDI, the content of TDI (monomer) of the raw material is as small as possible from the viewpoint of labor safety when using paint or the like. good.

Such a method for producing a modified polyisocyanate containing an isomeric cyanate chain using TDI as a raw material is generally used in various forms in order to avoid an unfavorable increase in viscosity of a liquid which is formed by a high polymer of isocyanate. In the reaction catalyst of the isomeric cyanate chain, a polymerization method for forming an isomeric cyanate chain is carried out at a low temperature as far as possible without generating an isocyanate high polymer; however, isomeric cyanide is formed at a low temperature. The reaction of the acid ester chain is slow, and it takes a long time to manufacture, and there is a problem that the reaction time is shortened to a complicated step. Further, the reaction for forming an isomeric cyanate chain at a low temperature for suppressing the formation of a high polymer of isocyanate is carried out in a short period of time, and the production of TDI (monomer) by distillation is carried out to contain iso-cyanuric acid. The method of modifying the polyisocyanate of the ester chain is also widely known; this method cannot be carried out without the distillation step, and is industrially very disadvantageous from the viewpoint of economy.

Therefore, Patent Document 1 discloses a heterotrimeric cyanate chain containing a solvent having a TDI (monomer) content of 0.1% by mass or less from TDI using a mixture of an acid-based catalyst containing a dialkylaminomethyl group. A proposal for a simple method of producing a modified polyisocyanate without performing distillation.

Patent Document 1: JP-A-2004-250662

However, in the method disclosed in Patent Document 1, in order to reduce the content of TDI (monomer), a long-term reaction is required, and as the reaction time is extended, the content of the modified polyisocyanate containing the isomeric cyanate chain is lowered. At the same time, there is a problem of high viscosity of the isocyanate high polymer.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for producing a modified polyisocyanate mixture containing an isomeric cyanate chain having a very high isocyanate polymer and a reaction catalyst for forming an isomeric cyanate. In particular, it is possible to produce an organic polyisocyanate (monomer) which is a hardener for coatings and a high efficiency in a short period of time and has practically no problem in practical use, even if the step of purifying by distillation is not carried out after the reaction. a method of modifying a polyisocyanate mixture of a different isocyanate chain having a low content and a low viscosity, and a reaction catalyst for forming an isomeric cyanate chain.

In order to achieve the above object, the working colleagues of the present invention have intensively studied the reaction catalyst for forming an isomeric cyanate chain, and found that by using a compound having a specific chemical structure as a heterotrimer. The catalyst for the reaction of the cyanate ester chain can solve the above problems and complete the present invention.

That is, the present invention is the following [1] to [10].

[1] A reaction catalyst for forming an isomeric cyanate chain, which comprises a compound represented by the following general formula (1),

(wherein M is an alkaline earth metal; R ¹ and R ² may each be the same or different alkyl groups having 6 to 10 carbon atoms; n is an integer of 0 or 1).

[2] The reaction catalyst for forming an isomeric cyanate chain according to the above [1], which further contains a hydroxyl group-containing organic compound as an auxiliary catalyst.

[3] The reaction catalyst for forming an isomeric cyanurate chain according to the above [1], which further contains water.

[4] The reaction catalyst for forming an isomeric cyanurate chain according to the above [1], wherein the M is calcium or strontium.

[5] The reaction catalyst for forming an isomeric cyanurate chain according to the above [1], wherein the M is calcium.

[6] The reaction catalyst for forming an isomeric cyanate chain according to the above [1], wherein both R ¹ and R ² are an alkyl group having 8 carbon atoms.

[7] A process for producing a modified polyisocyanate mixture containing an isomeric cyanate chain, characterized in that the isomeric cyanate chain is formed according to any one of the above [1] to [6] In the presence of a reaction catalyst of the knot, the organic polyisocyanate is subjected to a formation reaction of an iso-cyanate chain, followed by addition of a reaction inhibitor to terminate the reaction.

[8] A method for producing a modified polyisocyanate mixture containing an isomeric polyisocyanate chain having an organic polyisocyanate (monomer) content of 0.5% by mass or less, which is characterized by the above items [1] to [6] In the presence of a reaction catalyst for forming an isomeric cyanate chain according to any one of them, the organic polyisocyanate is subjected to a formation reaction of an iso-cyanate chain, followed by addition of a reaction inhibitor to terminate the reaction.

[9] The method for producing a modified polyisocyanate mixture containing an isomeric cyanate chain according to the above [7], wherein the organic polyisocyanate is toluene diisocyanate.

[10] The method for producing a modified polyisocyanate mixture containing an isomeric cyanate chain according to the above [7], wherein the above-mentioned from the first to the end of the isocyanate chain formation reaction The reaction catalyst for forming the isomeric cyanate chain of [1] is divided into several divided additions to carry out a reaction for forming an isomeric cyanate chain.

By the present invention, for the first time, by using a specific reaction catalyst for forming an isomeric cyanate chain, the content of the organic polyisocyanate (monomer) can be low, and the high isocyanate polymer can be produced without performing the distillation step. A modified polyisocyanate mixture containing an isomeric cyanate chain. In particular, after the reaction, the step of purifying by distillation is not carried out, and the content of the organic polyisocyanate (monomer) which is hard to be used as a coating material and the like in a short period of time and has practically no problem in labor hygiene can be produced. A modified polyisocyanate mixture of a low isocyanate chain having a low viscosity.

[Embodiment of the Invention]

The invention is described in detail below.

The reaction catalyst for forming an isomeric cyanate chain of the present invention contains the compound represented by the following general formula (1).

(wherein M is an alkaline earth metal; R ¹ and R ² may each be the same or different alkyl groups having 6 to 10 carbon atoms; n is an integer of 0 or 1).

In the general formula (1), M is preferably calcium or strontium, and more preferably calcium.

In the general formula (1), when R ¹ and R ² are alkyl groups having a carbon number of less than 6, the compound represented by the general formula (1) lacks solubility in an organic solvent or an organic polyisocyanate, Insufficient catalyst concentration, sufficient catalyst effect cannot be obtained. Further, in the general formula (1), when R ¹ and R ² are an alkyl group having a carbon number of 11 or more, the compound represented by the general formula (1) is almost completely insoluble in an organic solvent or an organic polyisocyanate, and is not suitable for uniformity. The reaction to form an isomeric cyanate chain.

The compound represented by the general formula (1) is specifically, for example, bis(dihexyl phosphate) calcium, bis(di-n-octyl phosphate) calcium, bis(di-2-ethylhexyl phosphate) calcium, or bis ( Dimercaptophosphate) Calcium, bis(dihexyl phosphate) ruthenium, bis(di-n-octyl phosphate) ruthenium, bis(di-2-ethylhexyl phosphate) ruthenium, bis(dimercaptophosphate) Bismuth, bis(di-2-ethylhexyl phosphate) magnesium, bis(di-2-ethylhexyl phosphate) ruthenium, bis(hexyl-hexylphosphonate) calcium, bis(n-octyl-n-octyl) Phosphonate) calcium, bis(2-ethylhexyl-2-ethylhexylphosphonate) calcium, bis(indenyl-decylphosphonate) calcium, bis(n-octyl-n-octylphosphonate)锶, bis(2-ethylhexyl-2-ethylhexylphosphonate) ruthenium, bis(2-ethylhexyl-2-ethylhexylphosphonate) magnesium, bis(2-ethylhexyl-2) -ethylhexylphosphonate), etc.

These may be used alone or in combination of two or more.

Among these, bis(dioctylphosphonate) calcium such as bis(di-n-octyl phosphate) calcium or bis(di-2-ethylhexyl phosphate) calcium; and bis(n-octyl-n-octyl) Phosphonate) calcium, bis(octyl-octylphosphonate) calcium such as calcium bis(2-ethylhexyl-2-ethylhexylphosphonate); and bis(di-n-octylphosphonate) ruthenium Bis(dioctylphosphonate) ruthenium such as bis(di-2-ethylhexyl phosphate) ruthenium; and bis(n-octyl-n-octylphosphonate) ruthenium, bis(2-ethylhexyl-2) A bis(octyl-octylphosphonate) ruthenium such as -ethylhexylphosphonate) is preferred. Calcium bis(di-2-ethylhexyl phosphate) and calcium bis(2-ethylhexyl-2-ethylhexylphosphonate) are more preferred.

The amount of the compound represented by the general formula (1) varies depending on the type of the catalyst to be used, the reaction temperature, etc., and is usually 0.01 to 5% by mass based on the organic polyisocyanate, and more preferably 0.1 to 3% by mass. .

The reaction catalyst for forming an isomeric cyanurate chain of the present invention is preferably one which contains water in the compound represented by the general formula (1). The content of the water is within 50% by mass of the compound represented by the general formula (1) from the viewpoint of enhancing the activity of the isomeric cyanate chain reaction and preventing side reactions such as urea formation. Good, more suitable in the range of 0.1 to 20% by mass.

The reaction catalyst for forming an isomeric cyanate chain of the present invention further contains, as an auxiliary catalyst, methanol, ethanol, butanol, ethylene glycol, 1,3-butylene glycol, and pentaerythritol. Further, an organic compound containing a hydroxyl group such as 2-ethyl-1,3-hexanediol, trimethylolpropane, polypropylene glycol, phenol or a mixture of two or more kinds thereof is preferred.

Further, in the case where the reaction catalyst forming the isomeric cyanate chain does not contain the auxiliary catalyst, in the method for producing the modified polyisocyanate mixture containing the isocyanurate chain of the present invention, the auxiliary The catalyst may be added simultaneously with the polymerization catalyst forming the hetero-cyanate chain before the reaction step of forming the iso-cyanate chain; or the addition of the iso-cyanate chain may be added. Before the polymerization catalyst, it is previously reacted with an organic polyisocyanate described later to form a urethane group.

In the reaction catalyst for forming an isomeric cyanate chain of the present invention, the compound represented by the general formula (1) and the auxiliary catalyst according to the demand can be dissolved in a solvent. The solvent is pentane, hexane, heptane, octane, cyclopentane, cyclohexane, decalin, petroleum ether, petroleum benzene, lamp oil, mineral spirits, diethyl ether, tetrahydrofuran, ethyl acetate, acetic acid. Butyl ester, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tris(2-ethylhexyl) phosphate, a mixture of two or more kinds thereof, etc., which are inert to the isocyanate group.

The organic polyisocyanate used in the method for producing a modified polyisocyanate mixture containing an isomeric cyanate chain of the present invention, specifically, for example, 2,4-TDI, 2,6-TDI, xylene- 1,4-diisocyanate, xylene 1,3-diisocyanate, tetramethylxylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4, 4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-di Methyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene-1,4-di Aromatic diisocyanates such as isocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate , an aliphatic diisocyanate such as decamethylene diisocyanate or lysine diisocyanate; isophorone diisocyanate, hydrogen An alicyclic diisocyanate such as toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate or hydrogenated tetramethylxylene diisocyanate; or a mixture of two or more kinds thereof.

Among these, TDI is preferred, and 2,4-TDI alone or a mixture of 2,4-TDI and 2,6-TDI is more suitable.

Further, these organic polyisocyanates may contain an antioxidant as described later.

In the method for producing a modified polyisocyanate mixture containing an isomeric cyanate chain according to the present invention, triphenyl phosphate and three may be used as needed in the reaction for forming an isomeric cyanate chain. Nonylphenyl phosphate, tricresyl phosphate, 3,5-di-tert-butyl-4-hydroxytoluene, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid An antioxidant such as an ester or a mixture of two or more of these.

Further, when a reaction for forming an isomeric cyanate chain is carried out, a solvent can be used as needed. The solvent is, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, or a mixture of two or more kinds thereof, which is inert to the isocyanate group.

In the method for producing a modified polyisocyanate mixture containing an isocyanurate chain of the present invention, a reaction for forming an isomeric cyanate chain is a reaction catalyst for forming an isomeric cyanate chain In the presence of the organic polyisocyanate, the reaction is carried out to a predetermined isocyanate group content (hereinafter referred to as 150 ° C or less, preferably 20 to 120 ° C, usually 50 hours or less, preferably 10 minutes to 15 hours). NCO). When the reaction for forming the isomeric cyanate chain is carried out at a low temperature, it is preferred to lower the content of the organic polyisocyanate (monomer) at the time of termination of the reaction for forming the isomeric cyanate chain.

In the method for producing a modified polyisocyanate mixture containing an isomeric cyanate chain of the present invention, it is desirable to reduce the NCO content of the modified polyisocyanate mixture containing the isomeric cyanurate chain, once added to form a different In the reaction catalyst of the cyanurate chain, the initial heat generation of the reaction liquid increases, and the temperature is too high, so that the difference between the first to the end of the reaction in which the hetero-cyanate chain is formed will be formed. The reaction catalyst of the cyanurate chain is divided into several divided additions, and it is preferred to carry out a reaction for forming an isomeric cyanate chain.

In the method for producing a modified polyisocyanate mixture containing an isomeric cyanate chain of the present invention, an inhibitor for forming a reaction of an isomeric cyanate chain is, for example, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, or trifluoroethylene. An acid such as acetic acid, p-toluenesulfonic acid or benzenesulfonic acid; an acid such as dimethyl phosphate, dimethylphosphonate, benzamidine chloride, acetonitrile chloride or a mixture of two or more thereof. Chloride and the like.

Any of these may be used singly or in combination of two or more kinds.

Among these, an acid, especially phosphoric acid is preferred.

The amount of the inhibitor forming the isomeric cyanate chain reaction is preferably from 1 to 2 times the equivalent of the neutralized compound of the general formula (1) used.

An inhibitor that forms a reaction of an isomeric cyanate chain, which is soluble in a solvent. The solvent is petroleum ether, petroleum benzene, tetrahydrofuran, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, a mixture of two or more of these, etc., which are relatively simple with respect to isocyanate. Solvent.

In the method for producing a modified polyisocyanate mixture containing an isomeric cyanate chain according to the present invention, when the reaction for forming the isomeric cyanate chain reaches the target NCO content, the addition of the isomeric cyanate chain is added. The inhibitor of the reaction is generally treated at 20 to 120 ° C, preferably 40 to 80 ° C, usually 15 minutes to 3 hours, preferably 30 minutes to 1.5 hours, to terminate the formation of isomeric cyanurate. The reaction of the chain.

The content of the organic polyisocyanate (monomer) in the modified polyisocyanate mixture containing the isocyanurate chain of the reaction product is preferably 0.5% by mass or less in order to sufficiently exhibit the performance and the operating environment.

The modified polyisocyanate mixture containing the iso-cyanate chain obtained by the present invention is used for adhesives, pressure-sensitive adhesives, adhesives, and synthetics in addition to coatings for woodworking, metal, and plastics. Leather, magnetic recording material adhesives, foams, flooring materials, molded articles, waterproof materials, primers, etc., are most suitable for use in woodworking coatings.

Further, the modified polyisocyanate mixture containing the isomeric cyanate chain obtained by the present invention is used as a two-liquid polyurethane coating to react with two or more isocyanate-containing activities. A combination of hydrogen hydroxy compounds is preferred. Specifically, it can be mixed with a saturated or unsaturated polyester polyol, a saturated or unsaturated oil modified or a fatty acid modified alkyd resin polyol, an amino alkyd resin polyol, a polycarbonate polyol, an acrylic polymer. Alcohol, polyether polyol, epoxy polyalcohol, polycaprolactone polyalcohol, fluorine-containing polyalcohol, polyoxymethylene-containing polyalcohol, urea resin and the like are used in combination. Among these, a compound having an active hydrogen group other than a hydroxyl group such as a polyamine or a polyamide may be used.

In the polyurethane coating, in addition to the above-described polyvalent hydroxy compound, well-known additives such as a coloring agent, a filler pigment, cellulose, a planarizing agent, an antifoaming agent, an anti-sagging agent, and an amine group may be added. Formate catalyst, organic solvent, diluent, plasticizer, and the like.

[Examples]

The invention is described in more detail below by way of examples, and the invention is not limited thereto. In addition, in the synthesis examples, the examples, and the comparative examples, "%" means "mass%" in addition to the GPC analysis result of the reaction product.

<Synthesis of Reaction Catalyst Forming Iso-Isolate Chains>

(Synthesis Example 1) 32.2 g (0.1 mol) of bis(2-ethylhexyl)phosphate was dissolved in 75 g of petroleum benzene, and placed in a separatory funnel. 3.7 g (0.05 mol) of calcium hydroxide was suspended in 50 g of water, and heat was added while slowly adding to a separatory funnel. The separatory funnel was vigorously shaken, and the organic phase and the aqueous phase were thoroughly mixed, and left for about 5 minutes. Further, 3.0 g (0.04 mol) of calcium hydroxide powder was directly added to a separatory funnel, and the mixture was uniformly mixed by shaking. The mixture was allowed to stand until the aqueous phase was separated from the organic phase, and it was confirmed that the pH of the aqueous phase was 10 or more. The aqueous phase was discarded, and the white turbid organic phase was transferred to a sample bottle, and allowed to stand at room temperature for several days to precipitate a white suspension. The upper clear liquid was taken out and the solvent was removed therefrom to obtain a white solid of bis(di-2-ethylhexyl phosphate) calcium.

The moisture content of this white solid was measured by the Karl Fischer method, and the water content was 2.5%.

(Synthesis Example 2) 32.2 g (0.1 mol) of bis(2-ethylhexyl)phosphate was dissolved in 97 g of petroleum benzene, and placed in a separatory funnel. 3.7 g (0.05 mol) of calcium hydroxide was suspended in 50 g of water, and heat was added while slowly adding to a separatory funnel. The separatory funnel was vigorously shaken, and the aqueous phase was thoroughly mixed with the organic phase, and left for about 5 minutes. Further, 3.0 g (0.04 mol) of calcium hydroxide powder was directly added to a separatory funnel, and the mixture was uniformly mixed by shaking. The mixture was allowed to stand until the aqueous phase was separated from the organic phase, and it was confirmed that the pH of the aqueous phase was 10 or more. The aqueous phase was discarded, and the white turbid organic phase was transferred to a sample bottle, and allowed to stand at room temperature for several days to precipitate a white suspension. That is, a solution of bis(di-2-ethylhexyl phosphate) calcium petroleum benzene is obtained. Also, the residual portion of petroleum benzene removed from the petroleum benzene solution was 27.5%.

(Synthesis Example 3) Calcium bis(di-2-ethylhexyl phosphate) having a water content of 2.5% obtained in Synthesis Example 1 was completely dissolved in a large amount of ethyl acetate while being heated. The solution was allowed to cool to room temperature, and allowed to stand overnight to precipitate white crystals. The precipitate was filtered through a filter paper, and the filtered solid was dried at 10 mmHg at 100 ° C for 5 hours to obtain a white powdery solid of bis(di-2-ethylhexyl phosphate) calcium.

The moisture content of the white powdery solid was measured by the Karl Fischer method, and the water content was 0.2%.

(Synthesis Example 4) 32.2 g (0.1 mol) of bis(2-ethylhexyl)phosphate was dissolved in 75 g of diethyl ether, and placed in a separatory funnel. 26.6 g (0.1 mol) of cesium hydroxide was dissolved in about 1 liter of water, and 200 ml of this solution was slowly added to the separatory funnel. The separatory funnel was vigorously shaken, and the aqueous phase and the organic phase were thoroughly mixed, and then left to separate into two layers, and the pH of the aqueous phase was measured. Repeat several times until the pH is 10 or more, and the organic phase is taken out to remove the solvent; then it is dried by heating to obtain a white solid of bis(di-2-ethylhexyl phosphate) hydrazine.

The moisture content of this white solid was measured by the Karl Fischer method, and the water content was 10%.

(Synthesis Example 5) A white solid of bis(di-2-ethylhexyl phosphate) ruthenium was obtained in the same manner as in Synthesis Example 4 except that 31.6 g (0.1 mol) of cesium hydroxide was used instead of cesium hydroxide.

The moisture content of this white solid was measured by the Karl Fischer method, and the water content was 11%.

(Synthesis Example 6) 32.2 g (0.1 mol) of bis(2-ethylhexyl)phosphate and 75 g of petroleum ether were placed in a beaker. In another beaker, 4.4 g (0.11 mol) of sodium hydroxide was dissolved in 10 g of water, and the mixture was added to the previously prepared solution with a small amount of stirring at the same time. After stirring for 10 minutes, the water and oil were removed by heating and drying. Ether, a white solid of sodium bis(2-ethylhexyl)phosphate.

The moisture content of this white solid was measured by the Karl Fischer method, and the water content was 1.5%.

(Synthesis Example 7) In the same manner as in Synthesis Example 6, except that 6.2 g (0.11 mol) of potassium hydroxide was used instead of sodium hydroxide, a white solid of potassium di(2-ethylhexyl)phosphate was obtained.

The moisture content of this white solid was measured by the Karl Fischer method, and the water content was 1.1%.

(Synthesis Example 8)

In the same manner as in Synthesis Example 1, except that 30.6 g (0.1 mol) of 2-ethylhexyl-2-ethylhexylphosphonate was used instead of 32.2 g (0.1 mol) of di(2-ethylhexyl)phosphate, A white solid of bis(2-ethylhexyl-2-ethylhexylphosphonate) calcium was obtained.

The moisture content of this white solid was measured by the Karl Fischer method, and the water content was 3.6%.

<Manufacture of modified polyisocyanate mixture (hereinafter referred to as terpolymer) containing an isomeric cyanate chain> [Example 1]

In a reaction vessel equipped with a stirrer, a thermometer and a reflux cooling tube, 500 g of toluene diisoacrylate (80/20 mixture of 2,4-TDI and 2,6-TDI, manufactured by Japan Polyurethane Industry Co., Ltd.) Internal poly-T-80), 500 g of butyl acetate, 1.0 g of phenol, 1.2 g of bis(di-2-ethylhexyl phosphate) calcium solids having a water content of 2.5% obtained in Synthesis Example 1, and triphenyl as an antioxidant 0.5 g of phosphatidyl ester (JP-360 manufactured by Seiki Chemical Co., Ltd.) and 0.5 g of 3,5-di-tert-butyl-4-hydroxytoluene (Kishinokus BHT manufactured by Jifu Pharmaceutical Co., Ltd.) Nitrogen substitution. Do this When the solution was stirred while raising the temperature to 60 ° C, heat generation started about 20 minutes after reaching 60 ° C. The heater was taken out, and the reaction vessel was water-cooled while maintaining at 55 to 65 ° C. The heater was installed at the end of the heat generation, and stirred at the same temperature for about 2.5 hours to carry out a reaction for forming an isomeric cyanate chain. After 3.5 hours from the start of the reaction, phosphoric acid (manufactured by Jisida Chemical Co., Ltd.), which is a reaction inhibitor for forming an isomeric cyanate chain, was added to a 30% solution of butyl acetate in 0.6 g, and then at 55 to 65. After stirring at ° C for 1 hour, the reaction for forming an isomeric cyanate chain was terminated.

[Example 2]

In addition to Example 1, 2.4 g of a bis(di-2-ethylbutyl phosphate) calcium solid having a water content of 2.5% obtained in Synthesis Example 1 was used instead of 1.2 g; in addition, a butyl acetate solution (phosphoric acid) was used. /butyl acetate = 3 / 7) 1.2 g instead of 0.6 g, and a reaction for forming an isomeric cyanate chain for 15 hours was carried out in the same manner to produce a terpolymer.

[Example 3]

In a reaction vessel equipped with a stirrer, a thermometer and a reflux cooling tube, 500 g of toluene diisoacrylate (80/20 mixture of 2,4-TDI and 2,6-TDI, manufactured by Japan Polyurethane Industry Co., Ltd.) Internal poly-T-80), 500 g of butyl acetate, 1.0 g of phenol, 1.2 g of bis(di-2-ethylhexyl phosphate) calcium solids having a water content of 2.5% obtained in Synthesis Example 1, and triphenyl as an antioxidant 0.5 g of phosphatidyl ester (JP-360 manufactured by Seiki Chemical Co., Ltd.) and 0.5 g of 3,5-di-tert-butyl-4-hydroxytoluene (Kishinokus BHT manufactured by Jifu Pharmaceutical Co., Ltd.) Nitrogen substitution. When the solution was stirred while raising the temperature to 60 ° C, heat generation was started about 20 minutes after reaching 60 ° C. The heater was taken out, and the reaction vessel was water-cooled while maintaining at 55 to 65 ° C, and stirred for about 0.5 hour to carry out a reaction for forming an isomeric cyanate chain. The heater was installed at the end of the heat generation, and after stirring at 55 to 65 ° C for 1.5 hours, 1.2 g of a solid of bis(di-2-ethylhexyl phosphate) calcium having a water content of 2.5% obtained in Synthesis Example 1 was dissolved in acetic acid. Butyl butyl 2.8g. After the addition, the mixture was stirred at 55 to 65 ° C for about 2 hours to carry out a reaction for forming an isomeric cyanate chain. After 4.5 hours from the start of the reaction, 1.2 g of a solution of butyl acetate as a reaction inhibitor for forming an isomeric cyanate chain (phosphoric acid/ethyl acetate = 3/7) was added, followed by stirring at 55 to 65 ° C. The reaction to form the isomeric cyanate chain was terminated in 1 hour.

[Example 4] In Example 1, except that the bis(di-2-ethylhexyl phosphate) calcium having a water content of 2.5% obtained in Synthesis Example 1 was dissolved in a 25% solution of tetrahydrofuran, 8.0 g, instead of Synthesis Example 1, 1.2 g of bis(di-2-ethylhexyl phosphate) calcium solids having a water content of 2.5%; further, 1.0 g of butyl acetate solution (phosphoric acid/butyl acetate = 3/7) was used instead of 0.6 g. A terpolymer was produced in the same manner as in the case of a reaction for forming an isomeric cyanate chain for 2.0 hours.

[Example 5] In Example 1, 500 g of toluene diisocyanate (2,4-TDI, manufactured by Nippon Polyurethane Industrial Co., Ltd.) was used instead of toluene diisocyanate (2,4-TDI and 2,6-TDI 80/). 20 mixture, manufactured by Nippon Polyurethane Industry Co., Ltd., Oropoly T-80) 500 g; and, in addition, 2.7 g of a petroleum benzene solution of bis(di-2-ethylhexyl phosphate) obtained in Synthesis Example 2 was used. 1.2 g of a solid of bis(di-2-ethylhexylphosphate) calcium having a water content of 2.5% obtained in Synthesis Example 1 was replaced by the reaction of forming an isomeric cyanate chain for 3.5 hours, and was also produced in the same manner. Terpolymer.

[Example 6]

In the same manner as in Example 1, the bis(di-2-ethylhexyl phosphate) calcium solid obtained by the synthesis example 3 was used in an amount of 4.0 g of the bis(di-2-ethylhexyl phosphate) solid. -ethylhexyl phosphate) 1.2 g of calcium solids; further, using isobutyl acetate solution (phosphoric acid / butyl acetate = 3 / 7) 2.0 g instead of 0.6 g, 3.5 hours of formation of isomeric cyanurate In addition to the reaction of the chain, the terpolymer was produced in the same manner.

[Example 7]

In addition to Example 1, 500 g of toluene diisocyanate (2,4-TDI, manufactured by Japan Polyurethane Industry Co., Ltd.) was used instead of toluene diisocyanate (80/20 mixture of 2,4-TDI and 2,6-TDI, Japanese polyurethane) Industrial Co., Ltd., Oropoly T-80) 500 g; 10.0 g of bis(di-2-ethylhexyl phosphate) ruthenium having a water content of 10% obtained in Synthesis Example 4 was used instead of Synthesis Example 1. Double (2-2-) with a moisture content of 2.5% Ethylhexyl phosphate) 1.2 g of solid calcium; in addition, 4.2 g of phosphoric acid butyl acetate solution (phosphoric acid / butyl acetate = 3 / 7) was used instead of 0.6 g to form an isomeric cyanate chain for 10.0 hours. In addition to the reaction of the knot, the terpolymer was produced in the same manner.

[Example 8]

In addition to Example 1, 500 g of toluene diisocyanate (2,4-TDI, manufactured by Japan Polyurethane Industry Co., Ltd.) was used instead of toluene diisocyanate (80/20 mixture of 2,4-TDI and 2,6-TDI, Japanese polyurethane) Industrial Co., Ltd., Mulhouse-T-80) 500 g; 10.0 g of bis(di-2-ethylhexyl phosphate) ruthenium having a water content of 11% obtained in Synthesis Example 5 was used instead of Synthesis Example 1. 12 g of bis(di-2-ethylhexyl phosphate) calcium solids having a water content of 2.5%; further, using a butyl acetate solution (phosphoric acid/butyl acetate = 3/7) 4.2 g instead of 0.6 g, 45.0 In addition to the reaction to form an isomeric cyanate chain in an hour, a terpolymer was produced in the same manner.

[Example 9]

In addition to Example 1, 2.0 g of bis(di-2-ethylhexyl-2-ethylhexyl phosphate) calcium solids having a water content of 3.6% obtained in Synthesis Example 8 was used instead of the water content of 2.5% obtained in Synthesis Example 1. 1.2 g of bis(di-2-ethylhexyl phosphate) calcium solid; further, using butyl acetate solution (phosphoric acid / butyl acetate = 3 / 7) 1.0 g instead of 0.6 g, for 6.5 hours In addition to the reaction of the isomeric cyanate chain, a terpolymer is produced in the same manner.

[Comparative Example 1] In addition to Example 1, a white lamp oil solution of magnesium naphthenate (4.0 g (manufactured by Nippon Chemical Industry Co., Ltd., Nafite) was used instead of the double water content of 2.5% obtained in Synthesis Example 1. (di-2-ethylhexyl phosphate) 1.2 g of calcium solid; in addition, 1.0 g of butyl acetate solution (phosphoric acid / butyl acetate = 3 / 7) was used instead of 0.6 g, and the formation of isoforms was carried out for 13.0 hours. In addition to the reaction of the polycyanate chain, a trimer was produced in the same manner.

[Comparative Example 2] In addition to Example 1, 4.5 g of a white lamp oil solution of calcium naphthenate (manufactured by Nippon Chemical Industry Co., Ltd.) was used instead of the bis(di-2-ethyl group) having a water content of 2.5% obtained in Synthesis Example 1. Hexyl phosphate) 1.2 g of solid calcium; in addition, 1.0 g of butyl acetate solution (phosphoric acid / butyl acetate = 3 / 7) was used instead of 0.6 g to form an isomeric cyanate chain for 15.0 hours. In addition to the reaction, a terpolymer was produced in the same manner.

[Comparative Example 3] In the first embodiment, 3.3 g (manufactured by Nippon Chemical Industry Co., Ltd.) using a white lamp oil solution of calcium 2-ethylhexanoate was used instead of the double (2-2) having a water content of 2.5% obtained in Synthesis Example 1. -ethylhexyl phosphate) 1.2 g of solid calcium; further, 1.0 g of butyl acetate solution (phosphoric acid / butyl acetate = 3/7) was used instead of 0.6 g to form isomeric cyanurate for 15.0 hours. In addition to the reaction of the chain, the terpolymer was produced in the same manner.

[Comparative Example 4]

In addition to Example 1, 500 g of toluene diisocyanate (2,4-TDI, manufactured by Japan Polyurethane Industry Co., Ltd.) was used instead of toluene diisocyanate (80/20 mixture of 2,4-TDI and 2,6-TDI, Japanese polyurethane) Industrial Co., Ltd., Oropoly T-80) 500 g; using the solid 1.0 of sodium di(2-ethylhexyl)phosphate having a water content of 1.5% obtained in Synthesis Example 6 instead of the water content of 2.5 obtained in Synthesis Example 1. % bis (di-2-ethylhexyl phosphate) calcium solid 1.2 g; in addition, using butyl acetate solution (phosphoric acid / butyl acetate = 3 / 7) 1.0 g instead of 0.6 g, for 10.0 hours In addition to the reaction to form an isomeric cyanate chain, a terpolymer is produced in the same manner.

[Comparative Example 5]

In addition to Example 1, 500 g of toluene diisocyanate (2,4-TDI, manufactured by Japan Polyurethane Industry Co., Ltd.) was used instead of toluene diisocyanate (80/20 mixture of 2,4-TDI and 2,6-TDI, Japanese polyurethane) Industrial Co., Ltd., Mulhouse T-80) 500 g; using the solid 1.0 of potassium di(2-ethylhexyl)phosphate obtained in Synthesis Example 7 to replace the water content of Synthesis Example 1 % of bis(di-2-ethylhexyl phosphate) calcium solid 1.2 g; in addition, using butyl acetate solution (phosphoric acid / butyl acetate = 3 / 7) 1.0 g instead of 0.6 g, for 3.5 hours In addition to the reaction to form an isomeric cyanate chain, a terpolymer is produced in the same manner.

The composition of each raw material used, the concentration of the reaction catalyst for forming the isomeric cyanate chain, the reaction conditions for forming the isomeric cyanate chain, and the analysis results and properties of the obtained reaction product are shown in Table 1. ~3 is shown.

Claims (10)

A reaction catalyst for forming an isomeric cyanate chain, which comprises a compound represented by the following general formula (1), (wherein M is an alkaline earth metal; R ¹ and R ² may each be the same or different alkyl groups having 6 to 10 carbon atoms; n is an integer of 0 or 1). The reaction catalyst for forming an iso-cyanate chain according to the first aspect of the patent application, which further contains phenol as an auxiliary catalyst, and which is relative to a reaction catalyst for forming an iso-cyanate chain, The molar ratio of phenol is 0.7 to 6.0. The reaction catalyst for forming an iso-cyanate chain according to the first aspect of the patent application, which still contains water. The reaction catalyst for forming an isomeric cyanurate chain according to the first aspect of the patent application, wherein the M is calcium or strontium. The reaction catalyst for forming an isomeric cyanurate chain according to the first aspect of the patent application, wherein the M is calcium. The reaction catalyst for forming an isomeric cyanurate chain according to the first aspect of the patent application, wherein both R ¹ and R ² are alkyl groups having a carbon number of 8. A method for producing a modified polyisocyanate mixture containing an isomeric cyanate chain, characterized by the reaction of forming an isomeric cyanate chain according to any one of claims 1 to 6 of the patent application. General style contained in the media When the compound (1) is present in an amount of 0.01 to 5% by mass based on the organic polyisocyanate, the organic polyisocyanate is subjected to a formation reaction of an isocyanurate chain, and then a reaction inhibitor is added to terminate the reaction. A method for producing a modified polyisocyanate mixture containing an isomeric cyanate chain having an organic polyisocyanate (monomer) content of 0.5% by mass or less, which is characterized by any one of claims 1 to 6 The organic polyisocyanate is subjected to iso-cyanuric acid in the presence of the compound represented by the general formula (1) contained in the reaction catalyst for forming the isomeric cyanate chain in an amount of 0.01 to 5% by mass based on the organic polyisocyanate. The formation of the ester chain is followed by the addition of a reaction inhibitor to terminate the reaction. A process for producing a modified polyisocyanate mixture containing an isomeric cyanate chain according to claim 7, wherein the organic polyisocyanate is toluene diisocyanate. A method for producing a modified polyisocyanate mixture containing an isomeric cyanurate chain as claimed in claim 7 wherein the patent is applied between the initial to the end of the isocyanate chain formation reaction The reaction catalyst for forming the isomeric cyanurate chain in the first item of the range is divided into several times, and is divided and added to carry out a reaction for forming an isomeric cyanate chain.