JPS61129173A - Production of compound having isocyanurate ring and isocyanate group - Google Patents

Abstract

PURPOSE:To facilitate the reaction in the production of the titled compound from an isocyanate compound using a hydroxyalkyl quaternary ammonium compound as a catalyst, and to prevent to coloring and clouding of the product, by using an organic phosphorous acid ester as a cocatalyst. CONSTITUTION:The titled compound is produced by reacting an isocyanate compound, e.g. an organic polyisocyanate in the presence of an organic phosphorous acid ester, e.g. organic phosphorous acid dior triester, using a catalyst consisting of a hydroxyalkyl quaternary ammonium compound, e.g. hydroxyalkyl quaternary ammonium carboxylate or hydroxide. Since the objective compound can be produced in a transparent and almost colorless state, it can be used as a curing agent for a polyurethane coating without using filtration or decoloration treatment. The process is economical because of e.g. extremely small amount of catalyst, high catalytic activity, easily controllable reaction, free from the gelatinization of the reaction liquid, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Industrial Application Field The present invention relates to incyanurate rings and ylangana-1, which are useful as curing agents in the production of polyurethane paints, for example.
The present invention relates to a method for producing a compound having a group. More specifically, it contains an isocyanurate ring and an isocyanate group from an isocyanate compound characterized by using a hydroxyalkyl quaternary ammonium compound as a catalyst and an organic phosphite ester as a co-catalyst. Concerning a method for producing a compound.

B. Prior art A compound having an isocyanurate ring and an isocyanate group is generally called an isocyanate trimer and usually has three or more reactive isocyanate groups at the end, and has weather resistance and heat resistance within the molecule.

It has an isocyanurate ring that has excellent chemical resistance, and it has a low vapor pressure and is easy to handle, so it is used, for example, as a curing agent in the production of polyurethane paints.

Such isocyanate trimers are usually manufactured by using organic polyisocyanate as a raw material and applying a catalyst to the organic polyisocyanate. As catalysts capable of producing such incyanurates, a large number of compounds have been proposed and have been developed, including, for example, tertiary amines, metal salts of organic acids, and tertiary phosphines. Recently, hydroquine argyl quaternary ammonium compounds, especially hydroxyalkyl quaternary ammonium hydroxides (e.g., JP-A-55-38380, JP-A-55-38380; Showa 54
-119480) or hydroxyalkyl quaternary ammonium carboxylates (for example, JP-A-52-17484, JP-A-55-143978)
(see Publication No. 1) has been reported to be effective.

Problems to be Solved by the C0 Invention The quaternary ammonium compound catalyst described above exhibits catalytic action just by using a comparatively raw material, but its action is easily affected by impurities present in extremely small amounts in the raw materials. In particular, when using industrially produced and sold organic polyisoneanate as a raw material, the effect may be difficult to develop, and once the effect occurs, the isocyanurate reaction proceeds rapidly, causing the reaction solution to deteriorate. There are still problems such as gelation. Further, in general, in the isocyanurate reaction using a catalyst, it is inevitable that the product becomes colored and cloudy. These coloring and turbidity depend on the type of catalyst and the temperature, but are also greatly affected by the amount of catalyst used. The above-mentioned quaternary ammonium compound is more effective in coloring the product than in the conventionally known incyanurate catalysts.
Although there has been some improvement in terms of turbidity, these problems have not yet been resolved.

The inventors of the present application have conducted intensive studies on incyanurate catalysts that are easy to control the isocyanurate reaction and do not cause coloration or turbidity in the reaction product, and found that a hydroxyalkyl quaternary ammonium compound was used as a catalyst. It was discovered that when this catalyst is further used in combination with an organic phosphite, strong catalytic activity is exhibited even when the amount of catalyst used is extremely small. In other words, it has been found that although organic phosphite itself does not have a catalytic effect on incyanurate formation, it has an effect as a so-called co-catalyst that significantly enhances the catalytic effect of quaternary ammonium. The present invention has been made based on this knowledge.

Means for Solving Problem D1 The present invention is characterized by reacting an isocyanate compound with an isocyanate group in the presence of an organic phosphite using a hydroxyalkyl quaternary ammonium compound as a catalyst. This is a method for producing a compound having a nato group.

Examples of the hydroxyalkyl quaternary ammonium compounds used as catalysts in the present invention include hydroxyalkyl quaternary ammonium carboxylate (hereinafter sometimes abbreviated as carboxylate catalyst) and hydroquine alkyl quaternary ammonium hydroxide ( below,
Sometimes abbreviated as hydroxide catalyst. And! can be mentioned. These compounds are all known as catalysts for converting organic polyisocyanates into isocyanurates.
These known catalysts can be used as they are.

Carboxylate catalysts are obtained by reacting a tertiary amine with an alkylene oxide in the presence of an organic carboxylic acid in a solvent such as dipropylene glycol. As such, for example trimethyl-N-2
-Hydroxypropylammonium 2-ethylhexanoate, N.

N-dimethyl-N-hydroquinoethyl-N-2-hydroxypropylammonium hexanoate, weighed methyl-N-2-hydroxypropylammonium hequinadecanoate, trimethyl-N-2-hydroxypropylammonium, phenyl carbonate, trimethyl −
Examples include, but are not limited to, N-2-hydroquinopropylammonium formate. Alternatively, a hydroxide catalyst can be obtained by reacting a tertiary amine with an alkylene oxide in water/methanol. These include, for example, 2-hydroxyethyl-trimethylammonium hydroxide, 2-hydroxyethyl-dimethylammonium hydroxide, 2-hydroxyethyl-dimethyl-2,2'-dihydroxymethyl-butylammonium hydroxide, ethylene Mankisitodo 1p
Examples include, but are not limited to, monoadducts of 4-diazabicyclo-2,2,2-octane.

Examples of the organic phosphorous ester used as a cocatalyst in the present invention include organic phosphorous diesters and organic phosphorous triesters.

0-= These compounds have P(0)H or 10' 10- in the molecule. It has one or more (usually 1 to 4) partial structures such as po-o- (however, one hand of the oxygen atom is bonded to a carbon atom). In the present invention, it is preferable to use organic phosphorous acid triesters, and specific examples of such ones include the following.

(1) (R, -0b iP (however, 几 is the same or different and is an alkyl having 1 to 20 carbon atoms or 1 to 20 carbon atoms)
A compound represented by an aryl which may be substituted with an alkyl group (Aryl is, for example, phenyl). Examples of such substances include, for example, ethyl phosphite, tributyl phosphite, tris(2-ethylhexylnophosphite, tridecyl phosphite,
Trilauryl phosphite, l-lis (tridecyl) phosphite, tristearyl phosphite; triphenyl phosphite, tris (nonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite); or diphenyl Monophosphites such as decyl phosphite, diphenyl (tridecyl) phosphite, (1) e.g. distearyl pentaerythrityl diphosphite, di-tridecyl pentaerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite, tetraphenyl・Di-, tri- or tetraphosphites derived from polyhydric alcohols such as tetra-tridecyl-pentaerythrityl-tetraphosphite, tetraphenyl-diglobyringlycol-diphosphite, tripentaerythritol-triphosphite, and (iii For example, diphosphites derived from bisphenol compounds such as di-alkyl (Ct-20) bisphenol A diphosphite, 4,4'-butylidene-bis<8-!thi-6-t-butylphenyl-di-tridecyl) phosphite, etc. class, and (1v
) Others, such as hydrogenated bisphenol A phosphite polymers (polyphosphites with a molecular weight of 2,400 to 30,002). significance〕
Examples of such diesters include dilauryl hydrogen phosphite and diphenyl hydrogen phosphite. The delkyl group represented by the numeral may be substituted with a halogen such as syl, for example, tris(2,8-dichloropropyl laphosphite). The oxygen atom of may be replaced by a sulfur atom, such that
An example is trilauryltrithiophosphite.

In the process of the present invention, such a cocatalyst is used in combination with a catalyst, and the catalyst itself may be used in an amount less than the most effective amount when used alone. For example, in the case of a carboxylate catalyst, the ratio (the same applies hereinafter) is 0.002 to 0.00% relative to the raw material isocyanate compound.
05 military song% (preferably 0°006~o, oig weight%
), and in the case of hydrokid catalysts, 0.001 to 0.
05% by weight (preferably 0.002-0.009% by weight)
) shows sufficient catalytic activity.

Further, the amount of phosphorous acid ester used as a cocatalyst is approximately '/1. -10 times the amount, preferably the same amount to 6 times the amount. If the amount is less than this amount, the action as a cocatalyst will not be sufficient, and if it exceeds this amount, the product obtained by the reaction! used. There is a fear that it may adversely affect the physical properties of the final product.

Furthermore, examples of the isocyanate compound that can be used as a raw material in the present invention include compounds having an isocyanate group that have been conventionally used in the production of isocyanate trimers.

Examples of such compounds include organic polyisocyanates. Examples of organic polyisocyanates include trimethylene diisocyanate.

Tetramethylene diisonanate, hexamethylene diisonoanate, pentamethylene diisocyanate-Fp1p
2-Brobyline diisocyanate.

2.3-butyline diisocyanate, 1,3-butyline diisocyanate, 2,4.4- or 2゜2,4-
Aliphatic diisocyanates such as trinotylhexamethylene diisonanate, dodecamethylene diisocyanate, 2.6=diisocyanate methyl caproate, e.g. 1.1-i/clopentane diisocyanate+1+
4-Cyclohequinane diisocyanate 1jita-cyclohechitin diisocyanate, 3-isocyanatomethyl-3,5,5-to! J Methylcyclohexyl isocyanate, 4,4'-methylenebis(cyclohexylisonanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-i/cyclochitin diisocyanate, 1,4-bis(isoanate) Cycloalkylene diisocyanates such as methylnonchlorohequinane, 1,3-bis(isocyanatomethylcyclohequinane), e.g. m-phenylene diisocyanate 1-,
p-71 nylene diisonanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisonoanate, 2.4- or 2.6-1-lylene diisocyanate, 4 .4'-Toluidine diisocyanate.

Aromatic diisocyanates such as dianidine diisocyanate, 4,4'-diphenyl ether diisocyanate, such as ω,ω'-diisocyanate 1,
3-dimethylbenzene, ω, ω'-diyne 7nate 1,4-dimethylbenzene, ω, ω'-diisocyanate 1--1,4-diethylbenzene.

1.3-tetramethylxylylene diisocyanate 1jl
Aroaliphatic diisocyanates such as t4-tetramethylxylylene diisocyanate, e.g. triphenylmethane-4,4',4''-)lyisocyanate, l,8
．． 5-triisocyanatebenzene, 1. l, 5-triisonoanate cyclohexitine, 2,4,6-triisocyanate toluene, ω-ynyanate ethyl 2,
Examples include triisocyanates such as 6-diisocyanate caproate. Among these organic polyisocyanates, aliphatic diisocyanates and cycloalkylene diisocyanates are isocyanate compounds that can be advantageously used in the present invention.

Further, organic polyisocyanates may be used in a mixture of two or more types (for example, a mixture of hequinamethylene isocyanate and 3-isocyanatomethyl-8,5,5-trinotylcyclohexyl isocyanate). moreover,
Terminals obtained by reacting these organic borysonanates with mono- to tetrahydric alcohols or polyols such as polyester polyols and polyether polyols at a ratio such that the NC010H value is approximately 20-30. NCO group! A urethane prepolymer having the following properties can be used as a raw material in the present invention.

An example of a monohydric alcohol is methanol.

Butanol, 2-ethyl hequinanol, ethylene glycol 7-methyl ether, etc.; examples of dihydric alcohols include ethylene glycol;

1.3-butanediol, 1,4-butanediol, propinone glycol, neopentyl glycol, l, 6
-Hexanediol, 2-ethylhexinediol, 2
, 2,4-trimethylpentadiol, etc.; Trihydric alcohols include, for example, trimethylolpropane, glycerol; Tetravalent alcohols include, for example, pentaerythryl; Polyester polyols include, for example, neopentyl glycol hivalate; esters; and polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.
Each can be mentioned.

In the method of the present invention, such an isocyanate compound is used as a raw material, a catalyst and a co-catalyst are added thereto, and the compound is subjected to an incyanurate reaction. The incyanurate reaction of the present invention is usually carried out at 30 to 100°C, preferably 40 to 80°C.
It is carried out at ℃. The progress of the reaction can be monitored by measuring the concentration of NCO group-containing groups. The reaction is carried out until the specified stage (in the present invention, the NCO group content is approximately 90% at the start of the reaction).
After progressing until it decreased to ~50%, anti-Lc:
Add a stop agent to stop the process. An acidic substance is used as the reaction terminator. Examples of acidic substances include inorganic acids such as hydrochloric acid and phosphoric acid, and organic acid chlorides such as benzoyl chloride and acetyl chloride. These terminators may be added in an amount of about 4 to 2 times the weight of the catalyst used.

The method of the present invention can proceed without a solvent, but if necessary, acetic acid esters such as ethyl acetate, butyl acetate, celonorbacetate, etc., or phosphoric esters such as trimethyl phosphate, triethyl phosphate, etc. can be used as a solvent. It may also be used. After the reaction is completed, unreacted isocyanate monomer usually remains in the reaction solution, but this can be distilled off under reduced pressure. The same applies to solvents.

It is preferable to use a vacuum thin film distillation apparatus to distill off unreacted isonanoate monomers. By this method, the content of unreacted isocyanate monomers can be reduced to approximately 3% by weight or less, and if necessary to approximately 1% by weight or less.

In this way, a compound having an incyanurate ring and an isocyanate group is obtained. When an organic diisocyanate is used as a raw material, the main component of this product is a trivalent group having one incyanurate ring and three 1-isocyanate groups produced by the reaction of three organic diisonoanates, Other 5@ bodies (contains two incyanurate rings and four incyanurate rings. By the method of the present invention, the triad content is approximately 4
0 to 70% (analysis by liquid chroma 1 graphie; area ratio) can be produced.

In the method of the present invention, the isocyanurate reaction progresses stably at a constant rate regardless of the purity of the raw material, so the reaction is easy to control, and at a certain point the incyanurate reaction rapidly progresses. The reaction solution will not gel.

In addition, the compound having an incyanurate ring and an isocyanate group produced by the method of the present invention is transparent and almost uncolored, so it can be used as a curing agent as it is without passing or decolorizing. The product value is extremely high. That is, the object of the present invention can be widely used as a raw material when reacting with various polyol components for urethane to produce paints, adhesive foams, etc. with excellent physical properties such as weather resistance and heat resistance. , extremely useful.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

(hereinafter referred to as #odor) Example 1 500 g of hexamethylene diisonanate (hereinafter referred to as HDI) was placed in a Y glass concave flask, and this
After heating to 50°C, 0.05 g of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate, then 0.25 g of tetraphenyldipropylene glycol diphosphite, and F. This mixture′! a- When the reaction is continued at 60℃ for 3 hours under stirring, NC
The O group content decreased to about 80% of the initial content. At this point, benzoyl chloride 0.05. FY was added to stop the reaction. The resulting reaction solution was applied to a thin film distillation device (degree of vacuum 0.7ηHg, temperature 150°C) to remove unreacted H.
The DI salt was removed to give a pale yellow transparent product. This product has an NCO group content of 21.0% and a viscosity (25°C) of 2
, 800 cps, and the hue was APHA30. Since the infrared absorption spectrum of this product showed an absorption of 2168 Mt, it was confirmed that it had an incyanurate ring.

Examples 2 to 9 Compounds having an isocyanurate ring and an inanate group were obtained in the same manner as in Example 1 using the formulations and conditions shown in Tables 1-a and 1-b. In addition, in the case of hexamethylene diisonate (HDI), the isocyanurate reaction is performed when the NCO group content is approximately 40%, and 3-isocyanatomethyl-8,5,5-)limethylcyclohexyl In the case of (IPDI), the reaction was stopped when the NCO group content reached approximately 30%. The physical properties of the isocyanurate reaction solution and the product obtained by distilling off unreacted monomers are shown in the lower column of Table 1 ('a and b).

Example 10 500 g of hexamethylene diisocyanate (HDI) and 10 I of ethylene glycol were placed in a 4-diameter glass flask, and a urethane reaction was carried out at 75°C for 2 hours under a nitrogen stream to form a urethane preform having an NCO group at the end. Polymer hot reaction llI! was obtained.

The reaction solution was cooled to 50'C, and trimethyl-N
-2-Hydroquine globylammonium 2-ethylhexanoate 0.05.9 and tetraphenyldi10
Add 0.25g of pyrene glycol diphosphite and 60°
The isocyanurate reaction was carried out at C. The N of this reaction solution
When the CO group content reached approximately 40% (approximately 8 hours), 0.05Ji+ of benzoyl chloride was added to stop the reaction. Unreacted HDI monomer in the reaction solution was distilled off using a thin film distillation apparatus to obtain a pale yellow transparent liquid. This product has an NCO group content of 20.0% and a viscosity (25°C) of 2500
('pS hue was APHA30. Also, since the infrared absorption spectrum contained an absorption power of 153Qcm2, it was confirmed that it had an isocyanurate ring.

Examples 11 to 16 Compounds having an incyanurate ring and an isocyanate group were obtained in the same manner as in Example 10 using the formulation and conditions shown in Table 1. In the case of sonanate raw material (DI), the NCO group content is approximately 40%, and in the case of 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) raw material, the NCO group content is approximately 30%. The reaction was stopped when the amount reached.

The physical properties of the isocyanurate reaction solution and the product obtained by distillation (therefore, the unreacted upper parter was removed by distillation) are shown in the lower column of Table 2.

Claims (1)

[Claims] 1. A method for producing a compound having an isocyanurate ring and an isocyanate group, which comprises reacting an isocyanate compound in the presence of an organic phosphite using a hydroxyalkyl quaternary ammonium compound as a catalyst.