JP7025162B2 - Method for producing xylylene diisocyanate composition and isocyanurate - Google Patents

Description

The present invention relates to a xylylene diisocyanate composition and a method for producing an isocyanurate.

Polyurethane resins are usually produced by the reaction of polyisocyanates with active hydrogen group-containing compounds, and are widely used in various industrial fields as, for example, paints, adhesives, elastomers and the like.

As a polyisocyanate used for producing a polyurethane resin, for example, a polyisocyanurate composition obtained by subjecting xylylene diisocyanate to an isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst has been proposed (for example, Patent Document 1). reference.).

International release WO2015 / 133494 Pamphlet

On the other hand, industrially produced xylylene diisocyanate is usually added with paratoluene sulfonamide, dodecylbenzene sulfonic acid, or the like as a storage stabilizer.

These storage stabilizers may act as catalyst deactivating agents in the isocyanurate-forming reaction described in Patent Document 1. Therefore, the xylylene diisocyanate containing these storage stabilizers is excellent in storage stability, but may not be suitable for producing a polyisocyanurate composition.

INDUSTRIAL APPLICABILITY The present invention is a xylylene diisocyanate composition excellent in storage stability and also excellent in isocyanurate formation reaction efficiency, and a method for producing isocyanurate using the xylylene diisocyanate composition.

The present invention [1] is a xylylene diisocyanate composition for producing an isocyanurate of xylylene diisocyanate, wherein the xylylene diisocyanate composition contains a xylylene diisocyanate and an acid component, and contains the acid component. The xylylene diisocyanate composition having a ratio of 20 to 80 ppm with respect to the total amount of the xylylene diisocyanate composition in terms of hydrogen chloride is included.

In the present invention [2], the xylylene diisocyanate composition according to the above [1] is prepared, and the xylylene diisocyanate composition is subjected to an isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst. It comprises a method for producing an isocyanurate, comprising a reaction step of obtaining an isocyanurate of a range isocyanate.

Since the xylylene diisocyanate composition of the present invention contains an acid component in a predetermined ratio, it is excellent in storage stability. Further, since the acid component has a lower inhibitory effect on the isocyanurate-forming reaction than the catalytic deactivating agent, the xylylene diisocyanate composition of the present invention is also excellent in the isocyanurate-forming reaction efficiency.

Since the xylylene diisocyanate composition of the present invention is used in the method for producing isocyanurate of the present invention, isocyanurate can be produced with excellent efficiency.

(1) Raw Material Ingredients In the method for producing isocyanurate of the present invention, isocyanurate of xylylene diisocyanate is produced.

In this method for producing isocyanurate, first, a raw material component containing a xylylene diisocyanate composition containing xylylene diisocyanate is prepared (preparation step).

The xylylene diisocyanate composition contains a xylylene diisocyanate and an acid component, preferably essentially composed of a xylylene diisocyanate and an acid component. In other words, the xylylene diisocyanate composition does not contain an isocyanate other than xylylene diisocyanate and has a predetermined acidity (described later).

Xylylene diisocyanate (hereinafter, may be referred to as XDI) has 1,2-XDI (o-XDI), 1,3-XDI (m-XDI), and 1,4-XDI (hereinafter, may be referred to as XDI) as structural isomers. p-XDI) is included. The structural isomers of XDI may be used alone or in combination of two or more.

The XDI preferably includes 1,3-XDI and 1,4-XDI, and more preferably 1,3-XDI.

The acid component is not particularly limited, and examples thereof include inorganic acids such as hydrogen chloride (hydrochloric acid), sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as sulfonic acid and acetic acid. These can be used alone or in combination of two or more. The acid component preferably includes an inorganic acid, and more preferably hydrogen chloride.

The content ratio of the acid component is 20 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, and 80 ppm or less, preferably 75 ppm or less, more preferably 70 ppm, based on the total amount of the xylylene diisocyanate composition. It is as follows.

The content ratio of the acid component is measured as a hydrogen chloride conversion value (that is, acidity) in accordance with JIS K-1603-2: 2007 (the same applies hereinafter).

The content ratio (acidity) of the acid component is, for example, the xylylene diisocyanate composition containing xylylene diisocyanate, a known acid such as hydrogen chloride, or a xylylene diisocyanate having a high acidity (for example, xylylene diisocyanate having an acidity of 2000 ppm or more). It can be adjusted by adding (isocyanate composition, etc.).

It should be noted that such an acid component acts as a negative catalyst for the isocyanurate-forming reaction (described later).

Further, the xylylene diisocyanate composition essentially does not contain a storage stabilizer such as a catalytic deactivating agent described later.

The content ratio of the catalyst deactivating agent (storage stabilizer) is, for example, 10 ppm or less, preferably 1 ppm or less, more preferably 0.1 ppm or less, particularly, with respect to the total amount of the xylylene diisocyanate composition (raw material component). Preferably, it is 0 ppm.

Further, the xylylene diisocyanate purity (that is, the content ratio of XDI (monomer) with respect to the total amount of the xylylene diisocyanate composition) of the xylylene diisocyanate composition is, for example, 98.0% by mass or more, preferably 98. It is 5.5 or more, more preferably 99.0% by mass or more, and usually less than 100% by mass.

Since such a xylylene diisocyanate composition contains an acid component in a predetermined ratio as described above, it is excellent in storage stability even if it does not contain a storage stabilizer such as a catalyst deactivating agent described later. .. Further, since the acid component has a lower inhibitory effect on the isocyanurate-forming reaction than the catalytic deactivating agent, the above-mentioned xylylene diisocyanate composition (raw material component) is also excellent in the isocyanurate-forming reaction efficiency.

Therefore, the xylylene diisocyanate composition is suitably used in the following isocyanurate-forming reaction.

The raw material component can contain only the above-mentioned xylylene diisocyanate composition, and for example, the xylylene diisocyanate composition and the recovered component described later can be contained in the ratio described below.

(2) Isocyanurate-forming reaction In the production of the isocyanurate of the present invention, the above-mentioned raw material components are subjected to an isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst (reaction step).

The isocyanurate-forming catalyst is not particularly limited as long as it is a catalyst effective for isocyanurate-forming, and for example, tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium and trimethylbenzylammonium, and organic thereof. Hydroxides of trialkylhydroxyalkylammonates such as weak salts such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium and triethylhydroxyethylammonium and their organic weak salts such as acetic acid, caproic acid and octyl acid, Alkali metal salts of alkylcarboxylic acids such as myristic acid, eg metal salts of the above alkylcarboxylic acids such as tin, zinc, lead, eg β-diketone metal chelate compounds such as aluminum acetylacetone, lithium acetylacetone, eg aluminum chloride. , Friedel-Crafts catalysts such as boron trifluoride, and various organic metal compounds such as titanium tetrabutyrate, tributylantimon oxide, for example, aminosilyl group-containing compounds such as hexamethylsilazane.

Specific examples thereof include Zwitterion type hydroxyalkyl quaternary ammonium compounds, and more specifically, for example, N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2. -Ethyl hexanoate, N, N-dimethyl-N-hydroxyethyl-N-2-hydroxypropylammonium hexanoate, triethyl-N-2-hydroxypropylammonium hexadecanoate, trimethyl-N-2-hydroxypropyl Ammonium phenyl carbonate, trimethyl-N-2-hydroxypropylammonium formate and the like can be mentioned.

These isocyanurate-forming catalysts can be used alone or in combination of two or more.

The isocyanurate-forming catalyst is preferably a tetraalkylammonium hydroxide, and more preferably a tetrabutylammonium hydroxide.

The form of use of the isocyanurate-forming catalyst is not particularly limited, and the solid content of the isocyanurate-forming catalyst may be directly used, or a catalyst solution in which the isocyanurate-forming catalyst is dissolved in an organic solvent may be used. ..

Preferably, the isocyanurate-forming catalyst is used as a catalytic solution.

In the catalyst solution, examples of the organic solvent include alcohols (eg, methanol, ethanol, propanol, butanol, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), nitriles (eg, acetonitrile, etc.). ), Alkyl esters (eg, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, etc.), glycol ether esters (eg, methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl). Ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc.), ethers (eg, diethyl ether, tetrahydrofuran, dioxane, etc.), polar aprotons (eg, diethyl ether, tetrahydrofuran, dioxane, etc.) , N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, etc.) and the like. The organic solvent can be used alone or in combination of two or more.

Among the organic solvents, glycol ether esters are preferable, and propylene glycol methyl ether acetate is more preferable.

The solid content concentration (content ratio of the isocyanurate-forming catalyst) of the catalyst solution is, for example, 60.0% by mass or less, preferably 50.0% by mass or less.

Then, in this method, an isocyanurate-forming catalyst is collectively added or dividedly added to the raw material component to mix and disperse, and then the xylylene diisocyanate (monomer) in the raw material component is subjected to an isocyanurate-forming reaction.

The addition ratio of the isocyanurate-forming catalyst (in terms of solid content) is, for example, 0.001 part by mass or more, preferably 0.005 part by mass or more, for example, 0.1 part by mass or less with respect to 100 parts by mass of the raw material component. , Preferably 0.05 parts by mass or less.

When the addition ratio of the isocyanurate-forming catalyst is not less than the above lower limit, the raw material component can be surely reacted with the isocyanurate-forming reaction. When the addition ratio of the isocyanurate-forming catalyst is not more than the above upper limit, gel generation can be stably suppressed when the isocyanurate-forming catalyst is added to the raw material component.

This isocyanurate-forming reaction is carried out under an atmosphere of an inert gas such as nitrogen gas and normal pressure (atmospheric pressure). As the reaction conditions for the isocyanurate-forming reaction, the reaction temperature is, for example, room temperature (for example, 25 ° C.) or higher, preferably 40 ° C. or higher, more preferably 60 ° C. or higher, for example, 100 ° C. or lower, preferably 90 ° C. or higher. The reaction time is, for example, 30 minutes or more, preferably 1 hour or more, more preferably 2 hours or more, for example, 12 hours or less, preferably 10 hours or less, still more preferably 8 hours or less. be.

Thereby, an isocyanurate reaction solution containing an isocyanurate of xylylene diisocyanate and an unreacted xylylene diisocyanate (monomer) can be obtained.

Further, in the above-mentioned isocyanurate-forming reaction, known additives such as, for example, an antioxidant and a co-catalyst (for example, an organic phosphite ester) can be added, if necessary.

Preferred examples of the additive include antioxidants.

Examples of the antioxidant include a phenol-based antioxidant and a hindered phenol-based antioxidant, and from the viewpoint of hygiene, a hindered phenol-based antioxidant is preferable. Specific examples of the hindered phenolic antioxidant include 2,6? Di (tert-butyl) -4? Methylphenol (also known as dibutylhydroxytoluene, hereinafter abbreviated as BHT). [3- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyloxy] -2,2-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propanoyloxymethyl] propyl] 3- (3,5-ditert-butyl-4-hydroxyphenyl) propanoate (Irganox 1010, manufactured by Ciba Japan, trade name), octadecyl 3- (3,5-di) -Tert-Butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Japan, trade name), 3- (4-hydroxy-3,5-diisopropylphenyl) propionic acid octyl ester (Irganox 1135, Ciba) -Japan, trade name), bis [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propionic acid] ethylenebisoxybisethylene (Irganox 245, Ciba Japan, trade name) ) And so on.

These antioxidants can be used alone or in combination of two or more.

As the antioxidant, from the viewpoint of hygiene, a hindered phenolic antioxidant other than BHT is preferable, and octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) is more preferable. ) Propionate (Irganox 1076, manufactured by Ciba Japan, trade name) can be mentioned.

The timing of adding the additive is not particularly limited, and may be added to the raw material component before the isocyanurate conversion reaction, may be added to the isocyanurate reaction solution during the isocyanurate conversion reaction, and further. May be added to the isocyanurate reaction solution after the isocyanurate conversion reaction. Preferably, it is added to the raw material component before the isocyanurate-forming reaction.

The addition ratio of the additive is appropriately set according to the purpose and application.

Further, in the above-mentioned isocyanurate-forming reaction, alcohols can be blended if necessary in order to adjust the viscosity of the product component (described later).

To add alcohols, for example, first, the raw material component and the alcohols are subjected to a urethanization reaction, and then the above-mentioned isocyanurate-forming catalyst is added to the urethane reaction solution to cause the raw material component (reaction with alcohols). After the isocyanurate-forming reaction (including the product), unreacted xylylene diisocyanate is removed if necessary.

Specifically, first, a raw material component containing xylylene diisocyanate and alcohols are mixed and subjected to a urethanization reaction.

Examples of alcohols include monohydric alcohols (for example, linear monohydric alcohols having 1 to 20 carbon atoms, branched monohydric alcohols having 1 to 20 carbon atoms, etc.) and dihydric alcohols (for example, 2 carbon atoms). Linear dihydric alcohols of up to 20; branched dihydric alcohols of 3 to 20 carbons, alicyclic dihydric alcohols of 6 to 20 carbons, etc.) Trihydric alcohols (eg, glycerin, trimethylol) Examples include tetrahydric or higher alcohols (eg, tetramethylolmethane, D-sorbitol, xylitol, D-mannitol, etc.).

Further, as long as the alcohols have one or more hydroxy groups in the molecule, the other molecular structures are not particularly limited as long as they do not inhibit the excellent effect of the present invention. For example, alcohols may have an ester group, an ether group, a cyclohexane ring, an aromatic ring, or the like in the molecule.

Among the alcohols, a dihydric alcohol is preferable, and a branched dihydric alcohol having 3 to 20 carbon atoms is more preferable. Examples of branched dihydric alcohols having 3 to 20 carbon atoms include 1,2-propanediol, 1,3-butylene glycol (also known as 1,3-butanediol), 1,2-butylene glycol, and neopentyl glycol. , 3-Methyl-1,5-pentanediol and the like, preferably 1,3-butylene glycol (1,3-butanediol).

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

The mixing ratio of the alcohols is, for example, 0.1 part by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, for example, 40 parts by mass or less with respect to 100 parts by mass of the raw material component. It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

The equivalent ratio (NCO / OH) of the isocyanate group of the raw material component to the hydroxy group of the alcohol is, for example, 5 or more, preferably 10 or more, more preferably 20 or more, and usually 1000 or less.

Mixing of such raw material components with alcohols is carried out under an atmosphere of an inert gas such as nitrogen gas and normal pressure (atmospheric pressure). As the mixing conditions, the mixing temperature is, for example, room temperature (for example, 25 ° C.) or higher, preferably 40 ° C. or higher, for example, 100 ° C. or lower, preferably 90 ° C. or lower, and the mixing time is, for example, 3 minutes or longer. It is preferably 12 minutes or more, for example, 10 hours or less, preferably 6 hours or less.

Next, the above-mentioned isocyanurate-forming catalyst is added to the obtained urethane reaction solution at the above-mentioned compounding ratio, and the raw material components (including reaction products with alcohols) are subjected to the isocyanurate-forming reaction. The reaction conditions in the isocyanurate-forming reaction are the same as described above.

Thereby, an isocyanurate reaction solution containing an isocyanurate of xylylene diisocyanate and an unreacted xylylene diisocyanate (monomer) can be obtained.

Further, in the reaction step, the isocyanurate-forming reaction is carried out by adding the catalyst deactivating agent after the conversion rate reaches the target value (for example, 10% or more, preferably 20% or more, for example, 40% or less). Is stopped (addition step after reaction, reaction stop step).

Examples of the catalytic deactivator include a phosphoric acid compound, a sulfonic acid compound, a sulfonamide compound and the like.

Examples of the phosphoric acid compound include phosphoric acid and phosphoric acid esters. Examples of the phosphoric acid ester include methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, dipropyl phosphate, butoxyethyl phosphate, 2-ethylhexyl phosphate, bis (2-ethylhexyl) phosphate, and phosphoric acid. (C12-18) Alkyl, isotridecyl phosphate, oleyl phosphate, tetracosyl phosphate, ethylene glycol phosphate, 2-hydroxyethyl methacrylate phosphate, dibutyl phosphate and the like can be mentioned.

Examples of the sulfonic acid compound include sulfonic acid and sulfonic acid ester. Examples of the sulfonic acid include dodecylbenzene sulfonic acid and paratoluene sulfonic acid. Examples of the sulfonic acid ester include dodecylbenzenesulfonic acid alkyl esters such as methyl dodecylbenzenesulfonate, ethyl dodecylbenzenesulfonate, propyl dodecylbenzenesulfonate, and butyl dodecylbenzenesulfonic acid, and for example, methyl paratoluenesulfonate and paratoluene. Examples thereof include paratoluene sulfonic acid alkyl esters such as ethyl sulfonate, propyl paratoluene sulfonate, and butyl paratoluene sulfonate.

Examples of the sulfonamide compound include aromatic sulfonamides (eg, benzenesulfonamide, dimethylbenzenesulfonamide, sulfanylamide, o- and p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene). -2-Sulphonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, etc.), aliphatic sulfonamides (eg, methanesulfonamide, N, N-dimethylmethanesulfonamide, N, N-dimethylethanesulfonamide, N, N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide, etc.) and the like.

In addition to the above, examples of the catalyst deactivating agent include monochloroacetic acid and benzoyl chloride.

These catalyst deactivating agents can be used alone or in combination of two or more.

The catalytic deactivating agent also acts as a storage stabilizer for the above-mentioned isocyanate reaction solution.

Preferred examples of the catalytic deactivator include a phosphoric acid compound and / or a sulfonic acid compound. In other words, the catalytic deactivating agent is preferably phosphoric acid and / or sulfonic acid, or an ester thereof.

By using these, in the separation step described later, the catalyst deactivating agent (storage stabilizer) can be contained in the product component (described later) containing isocyanurate, and the storage stability of the product component is improved. be able to. Further, when the above-mentioned catalyst deactivating agent is used, it is possible to prevent the catalyst deactivating agent (storage stabilizer) from being mixed with the recovered component (described later) containing unreacted xylylene diisocyanate in the separation step described later. Therefore, a recovered component having excellent reactivity can be obtained, and the recovered component can be reused in the reaction step as described later.

From this point of view, the catalyst deactivating agent is more preferably sulfonic acid, and particularly preferably dodecylbenzene sulfonic acid.

The form of use of the catalyst deactivating agent is not particularly limited, and the active ingredient of the catalyst deactivating agent may be directly used, or a catalyst deactivating agent solution in which the catalyst deactivating agent is dissolved in the above organic solvent may be used. You may use it. Preferably, a catalytic deactivating agent solution is used.

When the catalyst deactivating agent is used as a catalyst deactivating agent solution, the organic solvent preferably includes glycol ether esters, and more preferably propylene glycol methyl ether acetate.

The concentration of the active ingredient of the catalyst deactivating agent (content ratio of the catalyst deactivating agent) is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 70% by mass or less, preferably 60% by mass or less. Is.

The addition ratio (in terms of active ingredient) of the catalyst deactivating agent is, for example, 400 ppm or more, preferably 500 ppm or more, more preferably 600 ppm or more, and for example, 3000 ppm or less with respect to the total amount of the isocyanate reaction solution. It is preferably 1000 ppm or less, more preferably 800 ppm or less.

When the addition ratio of the catalyst deactivating agent is within the above range, the catalyst deactivating agent (storage stabilizer) can be contained in the product component (described later) containing isocyanurate in the separation step described later, and the product component can be contained. The storage stability can be improved. Further, when the above-mentioned catalyst deactivating agent is used, it is possible to prevent the catalyst deactivating agent (storage stabilizer) from being mixed with the recovered component (described later) containing unreacted xylylene diisocyanate in the separation step described later. Therefore, a recovered component having excellent reactivity can be obtained, and the recovered component can be reused in the reaction step as described later.

Further, the obtained isocyanurate reaction solution preferably contains an acid component.

The content ratio (acidity) of the acid component in the isocyanurate reaction solution is, for example, 50 ppm or more, preferably 70 ppm or more, and for example, 200 ppm or less, preferably 150 ppm or less, based on the total amount of the isocyanurate reaction solution. ..

When the acidity of the isocyanate reaction solution is within the above range, the acidity of the recovered component obtained in the separation step described later can be adjusted to a predetermined range, and the recovered component having excellent reusability can be obtained.

In this method, if necessary, a known acid such as hydrogen chloride or a high acidity xylylene diisocyanate (for example, a xylylene diisocyanate composition having an acidity of 2000 ppm or more) is added to the above isocyanurate reaction solution. By doing so, the acidity can also be adjusted.

(3) Inhibition of gelation In the above-mentioned isocyanurate-forming reaction, xylylene diisocyanate may react rapidly at the initial stage of the isocyanurate-forming reaction to form a film-like gel on the surface of the reaction vessel or the like.

Therefore, in order to suppress the generation of gel in the initial stage of the reaction, the above-mentioned catalyst deactivating agent can be added to the raw material component before the above-mentioned reaction step, if necessary (pre-reaction addition step).

Examples of the catalyst deactivating agent include the above-mentioned phosphoric acid compound, the above-mentioned sulfonic acid compound, the above-mentioned sulfonamide compound, monochloroacetic acid, benzoyl chloride and the like.

These catalyst deactivating agents can be used alone or in combination of two or more.

The catalyst deactivating agent added in the pre-reaction addition step and the catalyst deactivating agent added in the post-reaction addition step may be of the same type or may be different types.

Preferably, the catalyst deactivating agent added in the pre-reaction addition step and the catalyst deactivating agent added in the post-reaction addition step are of the same type.

Further, as the catalyst deactivating agent added in the pre-reaction addition step, a phosphoric acid compound and / or a sulfonic acid compound is preferable. In other words, the catalytic deactivating agent is preferably phosphoric acid and / or sulfonic acid, or an ester thereof.

The form of use of the catalyst deactivating agent is not particularly limited, and the active ingredient of the catalyst deactivating agent may be directly used, or a catalyst deactivating agent solution in which the catalyst deactivating agent is dissolved in the above organic solvent may be used. You may use it. Preferably, a catalytic deactivating agent solution is used.

In the catalyst deactivating agent solution, the concentration of the active component of the catalytic deactivating agent (content ratio of the catalytic deactivating agent) is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 70% by mass or less, preferably 70% by mass or less. , 60% by mass or less.

The addition ratio (in terms of active ingredient) of the catalyst deactivating agent is not particularly limited, but is, for example, 10 ppm or more, preferably 50 ppm or more, more preferably 60 ppm or more, and for example, 200 ppm, based on the total amount of the raw material components. Hereinafter, it is preferably 100 ppm or less, more preferably 90 ppm or less.

By adding a predetermined amount of a catalytic deactivating agent to the raw material component before the isocyanurate-forming reaction, it is possible to suppress the rapid progress of the isocyanurate-forming reaction at the initial stage of the reaction, and it is possible to suppress the generation of gel.

Further, in this method, preferably, first, a catalyst deactivating agent is added before the isocyanurate-forming reaction (pre-reaction addition step), the isocyanurate-forming reaction is carried out, and then the catalyst is further added to the obtained isocyanurate reaction solution. A deactivating agent is added (addition step after reaction).

In such a case, in the post-reaction addition step, as described above, the catalyst deactivating agent is added so as to have a predetermined amount with respect to the isocyanate reaction solution.

The ratio of the catalyst deactivating agent added to the isocyanate reaction solution and the content ratio of the catalyst deactivating agent in the isocyanate reaction solution are clearly distinguished. That is, the catalyst deactivating agent added in the pre-reaction addition step and the catalyst deactivating agent added in the post-reaction addition step are contained in the isocyanurate reaction solution.

The addition ratio of the catalyst deactivating agent in the post-reaction addition step (the addition ratio of the catalyst deactivating agent to the raw material component (ppm)) is the addition ratio of the catalyst deactivating agent in the pre-reaction addition step (catalyst deactivation to the isocyanurate reaction solution). The addition ratio (ppm) of the agent is, for example, 2 times or more, preferably 2 times or more, more preferably 5 times or more, for example, 30 times or less, preferably 20 times or less, more preferably. Is 15 times or less.

When the ratio of the addition ratio of the catalyst deactivating agent is within the above range, the generation of gel can be suppressed particularly efficiently. Further, since the total content ratio of the catalyst deactivating agent in the isocyanate reaction solution is adjusted, the catalyst deactivating agent can be contained in the product component (described later) in the separation step described later, and the storage stability of the product component can be achieved. It is possible to improve the sex. Further, it is possible to prevent the catalyst deactivating agent (storage stabilizer) from being mixed in the recovered component (described later). Therefore, a recovered component having excellent reactivity can be obtained, and the recovered component can be reused in the reaction step as described later.

(4) Separation Then, in this method for producing isocyanurate, after the completion of the above-mentioned isocyanurate-forming reaction, the product component containing the isocyanurate of xylylene diisocyanate and the unreacted xylylene diisocyanate are separated from the isocyanurate reaction solution. The recovered components contained therein are separated from each other (separation step).

The product components are isocyanurate of xylylene diisocyanate (isocyanurate composition containing mainly a trimer of xylylene diisocyanate and further containing pentamers, heptamers and the like of xylylene diisocyanate) and the above. It is a composition containing a catalytic deactivating agent.

The recovered component is a composition containing an unreacted xylylene diisocyanate and an acid component, and is preferably a composition consisting essentially of an unreacted xylylene diisocyanate and an acid component.

The method for separating these product components and the recovered components is not particularly limited, but for example, a thin film distillation apparatus is used.

As the distillation conditions in the thin film distillation, the distillation temperature is, for example, 120 ° C. or higher, preferably 150 ° C. or higher, and for example, 250 ° C. or lower, preferably 200 ° C. or lower. Further, the distillation pressure (absolute pressure) is, for example, 1 PaA or more, and for example, 60 PaA or less.

The water vapor pressure (gauge pressure) is, for example, 0.1 MPaG or more, preferably 0.5 MPaG or more, and for example, 3 MPaG or less, preferably 1 MPaG or less.

The feed amount of the isocyanate reaction solution is, for example, 10 kg / hr or more, preferably 100 kg / hr or more, and for example, 1000 kg / hr or less, preferably 500 kg / hr or less.

As a result, the product component containing the isocyanurate of xylylene diisocyanate is separated as a high boiling point component.

The isocyanate group concentration of the product component is, for example, 15% by mass or more, preferably 16% by mass or more, for example, 22% by mass or less, preferably 21% by mass or less.

The isocyanate monomer concentration (concentration of unreacted xylylene diisocyanate) of the product component is, for example, 5% by mass or less, preferably 2% by mass or less, and more preferably 1% by mass or less.

Further, if necessary, the above-mentioned organic solvent can be added to the product components in an appropriate ratio to adjust the solid content concentration.

The solid content concentration of the product component is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 100% by mass or less, preferably 90% by mass or less.

In addition, the product component contains a catalytic deactivating agent added in the isocyanurate-forming reaction as a storage stabilizer.

The content ratio of the catalyst deactivating agent (storage stabilizer) is, for example, 400 ppm or more, preferably 500 ppm or more, and for example, 2500 ppm or less, preferably 2000 ppm or less, based on the total amount of the product components.

When the content ratio of the catalyst deactivating agent (storage stabilizer) is within the above range, the product component is excellent in storage stability.

If necessary, the above-mentioned catalyst deactivating agent (storage stabilizer) can be further added to the separated product components to adjust the content ratio within the above range.

In addition, if necessary, known additives such as plasticizers, blocking inhibitors, heat-resistant stabilizers (such as the above-mentioned sulfonamide compounds), light-resistant stabilizers, antioxidants, and mold release agents may be added to the product components. Pigments, dyes, lubricants, fillers, antioxidants and the like can be added.

(5) Reuse In the above separation step, the recovered component containing unreacted xylylene diisocyanate (monomer) is separated as a low boiling point component. More specifically, the recovered component to be separated contains an unreacted xylylene diisocyanate (monomer), an acid component (further, an organic solvent to be blended if necessary).

The content ratio (acidity) of the acid component in the recovered component is, for example, 20 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, and for example, 80 ppm or less, preferably 75 ppm, based on the total amount of the recovered component. Below, it is more preferably 70 ppm or less.

If necessary, the acidity can be adjusted by adding a known acid such as hydrogen chloride or a high acidity xylylene diisocyanate (for example, a xylylene diisocyanate composition having an acidity of 2000 ppm or more) to the above-mentioned recovered components. Can be adjusted.

In addition, the recovered component essentially does not contain a catalytic deactivating agent (storage stabilizer).

Specifically, by using phosphoric acid and / or sulfonic acid or an ester thereof as the catalyst deactivating agent (storage stabilizer), the catalyst deactivating agent (storage stabilizer) is added to the product component in the above separation step. ), On the other hand, the recovered component may not contain a catalytic deactivating agent (storage stabilizer).

The content ratio of the catalyst deactivating agent (storage stabilizer) is, for example, 10 ppm or less, preferably 1 ppm or less, more preferably 0.1 ppm or less, and particularly preferably 0 ppm, based on the total amount of the recovered components.

The purity of xylylene diisocyanate (that is, the content ratio of XDI (monomer) with respect to the total amount of the recovered component) of the recovered component is, for example, 97.0% by mass or more, preferably 98.0 or more, more preferably. Is 99.0% by mass or more, and usually less than 100% by mass.

As described above, the recovered component contains an acid component in a predetermined ratio, and therefore, it is excellent in storage stability even if it does not contain the above-mentioned catalyst deactivating agent (storage stabilizer). Further, since the acid component has a lower inhibitory effect on the isocyanurate-forming reaction than the catalytic deactivating agent, the above-mentioned recovered component is also excellent in the isocyanurate-forming reaction efficiency. Therefore, the recovered component can be suitably used in the above-mentioned isocyanurate-forming reaction.

Therefore, in this method for producing isocyanurate, preferably, the recovered component obtained in the above separation step is subjected to the reaction step as a raw material component in the isocyanurate conversion reaction (reuse step).

When the recovered component is reused, a mixture of the recovered component and a newly prepared xylylene diisocyanate composition is subjected to a reaction step as a raw material component.

The mixing ratio in such a case is not particularly limited, but for example, the recovered component is, for example, 10 parts by mass or more with respect to 100 parts by mass of the total amount of the recovered component and the newly prepared xylylene diisocyanate composition. It is preferably 20 parts by mass or more, for example, 90 parts by mass or less, preferably 80 parts by mass or less. The newly prepared xylylene diisocyanate composition is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less.

Further, preferably, the mixing ratio of the recovered component and the newly prepared xylylene diisocyanate composition is such that the content ratio (acidity) of the acid component of the obtained mixture (raw material component) is within the above-mentioned predetermined range. To be adjusted.

(6) Action / Effect The above-mentioned xylylene diisocyanate composition (raw material component) contains an acid component in a predetermined ratio, and therefore has excellent storage stability. Further, since the acid component has a lower inhibitory effect on the isocyanurate-forming reaction than the catalytic deactivating agent, the xylylene diisocyanate composition is also excellent in the isocyanurate-forming reaction efficiency.

Further, in the above-mentioned method for producing isocyanurate, since a xylylene diisocyanate composition containing an acid component in a predetermined ratio is used, isocyanurate can be produced with excellent efficiency.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Specific numerical values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following description are the compounding ratios (content ratios) corresponding to those described in the above-mentioned "Mode for carrying out the invention". ), Physical property values, parameters, etc. can be replaced with the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess"). can. In addition, "part" and "%" are based on mass unless otherwise specified.

Example 1
Hydrogen chloride was added to 1,3-xylylene diisocyanate (m-XDI, manufactured by Mitsui Chemicals, Inc.) to adjust the acidity (based on JIS K-1603-2: 2007) to the acidity (20 ppm) shown in Table 1. did. As a result, a raw material component composed of an XDI composition having a predetermined acidity was obtained (preparation step).

Under a nitrogen atmosphere, 787.470 parts by mass of the XDI composition and octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (hindard phenolic antioxidant, trade name: Irganox 1076, 0.161 parts by mass (manufactured by Ciba Japan) was mixed at 60 ° C to 65 ° C.

Then, a propylene glycol methyl ether acetate solution (active ingredient concentration 50% by mass) of dodecylbenzenesulfonic acid (DDBSA, catalytic deactivating agent) was added to the mixture. The addition amount was adjusted so that DDBSA was 0.064 parts by mass (the addition ratio was 80 ppm with respect to the total amount of the raw material components) (addition step before reaction).

Then, 15.726 parts by mass of 1,3-butanediol was added to the mixture at 70 ° C. to 75 ° C. and mixed to cause a urethanization reaction.

Next, a propylene glycol methyl ether acetate solution (solid content concentration 3.7% by mass) of tetrabutylammonium hydroxide (isocyanurate catalyst, TBAOH (37% methanol solution)) was added to the obtained urethane reaction solution. .. The amount added was adjusted so that TBAOH (37% methanol solution) was 0.803 parts by mass (0.3 parts by mass as an active ingredient).

Then, while mixing the urethane reaction solution, XDI was subjected to an isocyanurate conversion reaction at 70 ° C. to 75 ° C. until the conversion rate reached 30% (reaction step).

Next, a propylene glycol methyl ether acetate solution (active ingredient concentration 50% by mass) of dodecylbenzenesulfonic acid (DDBSA, catalytic deactivating agent) was added to the obtained isocyanurate reaction solution to stop the isocyanurate-forming reaction. .. The addition amount was adjusted so that DDBSA was 0.415 parts by mass (the addition ratio of DDBSA was 500 ppm with respect to the isocyanate reaction solution) (reaction stop step, post-reaction addition step).

Then, the obtained isocyanate reaction solution was further stirred at 70 to 75 ° C. for 30 minutes. Next, in order to adjust the acidity, 20.562 parts by mass of a pre-prepared high acidity (acidity 2400 ppm) XDI composition was added to the isocyanate reaction solution, stirred for 30 minutes, and then cooled to 50 ° C. or lower.

Next, the obtained isocyanurate reaction solution is subjected to thin film distillation (pressure: ~ 60 PaA, water vapor pressure: 0.7 MPaG, temperature: 170 ° C., feed amount: 200 kg / hr) to produce a product containing isocyanurate of xylylene diisocyanate. The component and the recovered component containing unreacted xylylene diisocyanate were separated from each other (separation step).

Then, ethyl acetate (EA) was added to the obtained product component to adjust the solid content concentration to 75% by mass, and 0.333 parts by mass (heat stabilizer) of paratoluenesulfonamide was added.

Examples 2-4 and Comparative Examples 1-2
The isocyanurate-forming reaction was carried out in the same manner as in Example 1 except that the acidity of the raw material component was adjusted to the acidity shown in Table 1.

Reference examples 1 to 12
Toluene diisocyanate (TDI, manufactured by Mitsui Chemicals) or hexamethylene diisocyanate (HDI, manufactured by Tosoh) is used instead of m-XDI (manufactured by Mitsui Chemicals, Inc.), and the acidity of the raw material components is shown in Tables 2 to 3. The isocyanurate-forming reaction was carried out in the same manner as in Example 1 except that the acidity was adjusted to.

<Evaluation>
1. 1. Storage stability The raw material components with adjusted acidity were stored at 40 ° C. for 2 months, and their appearance was visually observed. Then, the presence or absence of turbidity due to dimerization, nylonization, gelation, etc. was evaluated. The evaluation criteria are as follows.
◯: No turbidity occurred.
X: Turbidity occurred.

2. 2. The presence or absence of progress of the reactive isocyanurate-forming reaction was evaluated. The evaluation criteria are as follows. When the isocyanurate-forming reaction proceeded rapidly and gelation occurred, it was evaluated as "x (gelation)". When the isocyanurate-forming reaction did not proceed, it was evaluated as "x (non-progressive)".
◯: The reaction progressed.
X: Gelation occurred or the reaction did not proceed.

<Discussion>
As shown in Comparative Example 1, it was confirmed that the storage stability was not sufficient when the acidity of the raw material component was excessively low (less than 20 ppm). It was also confirmed that when the acid component is small, the isocyanurate-forming reaction proceeds rapidly, which causes gelation.

On the other hand, as shown in Comparative Example 2, when the acidity of the raw material component is excessively high (when it exceeds 80 ppm), although the storage stability is excellent, the isocyanurate-forming reaction does not proceed, so that the raw material for isocyanurate is It was confirmed that it cannot be used as.

On the other hand, if the acidity of the raw material component is adjusted to a predetermined range as referred to in each example, storage stability and isocyanurate-forming reactivity can be satisfactorily combined, and the raw material of isocyanurate can be obtained. It was confirmed that it can be suitably used as.

Further, from each reference example, it was confirmed that the above range of acidity is peculiar to XDI.

That is, as referred to in Reference Example 1 and Reference Example 7, it was confirmed that when TDI or HDI is used, the storage stability is excellent even if the acidity is less than 20 ppm.

Further, as referred to in Reference Examples 9 to 11, when HDI is used, gelation does not occur even if the acidity is less than 20 ppm, while the reactivity is sufficient even if the acidity is 80 ppm or less. It was confirmed that there was no such thing.

Claims (2)

A xylylene diisocyanate composition for producing an isocyanurate of xylylene diisocyanate.
The xylylene diisocyanate composition contains xylylene diisocyanate and an acid component, and contains.
The content ratio of the acid component measured in accordance with JIS K-1603-2 (2007) is 20 to 80 ppm with respect to the total amount of the xylylene diisocyanate composition as a hydrogen chloride equivalent value. The xylylene diisocyanate composition. The preparatory step for preparing the xylylene diisocyanate composition according to claim 1 and
A method for producing an isocyanurate, which comprises a reaction step of obtaining an isocyanurate of a xylylene diisocyanate by subjecting the xylylene diisocyanate composition to an isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst.