JP2019059823A - Xylylene diisocyanate composition and method for producing isocyanurate - Google Patents

Abstract

To provide a xylylene diisocyanate composition having excellent storage stability and also excellent isocyanuration reaction efficiency and to provide a method for producing an isocyanurate using the xylylene diisocyanate composition.SOLUTION: There is provided a xylylene diisocyanate composition for producing an isocyanurate of xylylene diisocyanate, wherein the xylylene diisocyanate composition contains xylylene diisocyanate and an acid component, the content ratio of the acid component is 20 to 80 ppm in terms of hydrogen chloride value based on the total amount of the xylylene diisocyanate composition. Further, there is provided an isocyanurate of xylylene diisocyanate by subjecting the xylylene diisocyanate composition to isocyanuration reaction in the presence of an isocyanuration catalyst.SELECTED DRAWING: None

Description

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

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

  For example, polyisocyanurate compositions obtained by subjecting xylylene diisocyanate to an isocyanurate reaction in the presence of an isocyanurate catalyst is proposed as a polyisocyanate used for producing a polyurethane resin (for example, Patent Document 1) reference.).

International Publication WO2015 / 133493 Brochure

  On the other hand, industrially produced xylylene diisocyanate is usually added with p-toluene sulfonamide, dodecyl benzene sulfonic acid and the like as a storage stabilizer.

  These storage stabilizers may act as catalyst deactivators in the isocyanuration reaction described in Patent Document 1. Therefore, although xylylene diisocyanate containing these storage stabilizers is excellent in storage stability, it may not be suitable for production of polyisocyanurate compositions.

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

  The present invention [1] is a xylylene diisocyanate composition for producing isocyanurate of xylylene diisocyanate, wherein the xylylene diisocyanate composition contains xylylene diisocyanate and an acid component, and contains the acid component. The composition contains a xylylene diisocyanate composition having a ratio of 20 to 80 ppm based on the total amount of the xylylene diisocyanate composition as a hydrogen chloride conversion value.

  In the present invention [2], the preparation step of preparing the xylylene diisocyanate composition described in the above [1], and the xylylene diisocyanate composition is subjected to an isocyanurate reaction in the presence of an isocyanurate catalyst, And B. a process for producing an isocyanurate comprising the steps of: obtaining an isocyanurate of diisocyanate.

  The xylylene diisocyanate composition of the present invention is excellent in storage stability because it contains an acid component at a predetermined ratio. Furthermore, since the acid component has a lower inhibitory effect on the isocyanurate reaction than the catalyst deactivator, the xylylene diisocyanate composition of the present invention is also excellent in the isocyanurate reaction efficiency.

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

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

  In this method for producing isocyanurate, first, raw material components including xylylene diisocyanate composition containing xylylene diisocyanate are prepared (preparation step).

  The xylylene diisocyanate composition contains xylylene diisocyanate and an acid component, and preferably consists essentially of xylylene diisocyanate and an acid component. In other words, the xylylene diisocyanate composition contains no isocyanate other than xylylene diisocyanate, and has a predetermined acidity (described later).

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

  As XDI, preferably, 1,3-XDI and 1,4-XDI can be mentioned, and more preferably, 1,3-XDI can be mentioned.

  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. As an acid component, Preferably, an inorganic acid is mentioned, More preferably, hydrogen chloride is mentioned.

  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 below.

  In addition, the content rate of an acid component is measured as a hydrogen chloride conversion value (namely, acidity) based on JISK-1603-2: 2007 (following same).

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

  In addition, such an acid component acts as a negative catalyst with respect to the isocyanuration reaction (after-mentioned).

  In addition, the xylylene diisocyanate composition essentially does not contain a storage stabilizer such as a catalyst deactivating agent described later.

  The content 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, based on the total amount of the xylylene diisocyanate composition (raw material component). Preferably, it is 0 ppm.

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

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

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

  In addition, a raw material component can contain only said xylylene diisocyanate composition, Moreover, the xylylene diisocyanate composition and the collection | recovery component mentioned later can also be contained by the below-mentioned ratio, for example.

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

  The isocyanurate conversion catalyst is not particularly limited as long as it is an effective catalyst for isocyanurate conversion, and, for example, a hydroxide of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, trimethylbenzylammonium or the like, or an organic compound thereof Weak acid salts such as, for example, hydroxides of trialkylhydroxyalkylammoniums such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium and the like, organic weak acid salts thereof, such as acetic acid, caproic acid, octylic acid, Alkali metal salts of alkyl carboxylic acids such as myristic acid, eg, tin, zinc, lead of the above alkyl carboxylic acids Which metal salt, for example, a metal chelate compound of β-diketone such as aluminum acetylacetone, lithium acetylacetone, etc., eg, Friedel-Crafts catalyst such as aluminum chloride, boron trifluoride, etc., eg, titanium tetrabutylate, tributylantimony oxide etc. And various organic metal compounds such as, for example, aminosilyl group-containing compounds such as hexamethyl silazane.

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

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

  As the isocyanurate conversion catalyst, preferably, a hydroxide of tetraalkylammonium is mentioned, and more preferably, a hydroxide of tetrabutylammonium is mentioned.

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

  Preferably, the isocyanuration catalyst is used as a catalyst 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-ethoxy propionate Etc.), ethers (eg, diethyl ether, tetrahydrofuran, dioxane, etc.), polar aprotics (eg, N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide etc.) Etc. The organic solvents can be used alone or in combination of two or more.

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

  The solid content concentration (content ratio of the isocyanurate conversion 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, the isocyanurate conversion catalyst is added to the raw material components at one time or in divided portions, mixed and dispersed, and then xylylene diisocyanate (monomer) in the raw material components is subjected to an isocyanurate reaction.

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

  If the addition ratio of the isocyanurate catalyst is equal to or more than the above lower limit, the isocyanurate reaction of the raw material components can be surely performed. When the addition ratio of the isocyanurate catalyst is equal to or less than the above upper limit, when the isocyanurate catalyst is added to the raw material component, the generation of gel can be stably suppressed.

  This isocyanuration reaction is carried out, for example, under an inert gas atmosphere such as nitrogen gas under normal pressure (atmospheric pressure). The reaction temperature is, for example, room temperature (for example, 25 ° C.) or more, preferably 40 ° C. or more, more preferably 60 ° C. or more, for example 100 ° C. or less, preferably 90 ° C. 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, more preferably 8 hours or less. is there.

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

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

  As an additive, Preferably, antioxidant is mentioned.

  As an antioxidant, a phenol type antioxidant and a hindered phenol type antioxidant are mentioned, for example, From a hygienic point of view, preferably, a hindered phenol type antioxidant is mentioned. Specifically, for example, 2,6-di (tert-butyl) -4methylphenol (alias: dibutyl hydroxytoluene, hereinafter sometimes abbreviated as BHT) as a hindered phenol-based antioxidant. [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 Co., Ltd., trade name), 3- (4-hydroxy) Ci-3,5-diisopropylphenyl) propionic acid octyl ester (IRGANOX 1135, manufactured by Ciba Japan KK, trade name), bis [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propionic acid Ethylenebisoxybisethylene (Irganox 245, manufactured by Ciba Japan Ltd., trade name) and the like.

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

  As the antioxidant, from the viewpoint of hygiene, preferably, hindered phenol-based antioxidants other than BHT are mentioned, and more preferably octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) 2. Propionate (Irganox 1076, manufactured by Ciba Japan, Inc., trade name).

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

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

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

  For blending the alcohols, for example, first, the raw material component and the alcohol are subjected to a urethanization reaction, and then the above-described isocyanurate catalyst is added to the urethane reaction solution to react the raw material component (the reaction with the alcohols The product is subjected to isocyanuration reaction and, if necessary, unreacted xylylene diisocyanate is removed.

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

  As the alcohols, for example, a monohydric alcohol (for example, a linear monohydric alcohol having 1 to 20 carbon atoms, a branched monohydric alcohol having 1 to 20 carbon atoms, etc.), a dihydric alcohol (for example, 2 carbon atoms) -20 linear dihydric alcohol, C2-C20 branched dihydric alcohol, C6-C20 alicyclic dihydric alcohol, etc., trihydric alcohol (eg, glycerin, trimethylol) Propane and the like), alcohols of tetravalent or higher (for example, tetramethylolmethane, D-sorbitol, xylitol, D-mannitol and the like) and the like can be mentioned.

  In addition, as long as 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 effects of the present invention. For example, the alcohol can have an ester group, an ether group, a cyclohexane ring, an aromatic ring and the like in the molecule.

  Among alcohols, preferred are dihydric alcohols, more preferably branched dihydric alcohols having 3 to 20 carbon atoms. As a branched dihydric alcohol having 3 to 20 carbon atoms, for example, 1,2-propanediol, 1,3-butylene glycol (alias: 1,3-butanediol), 1,2-butylene glycol, neopentyl glycol And 3-methyl-1,5-pentanediol and the like, preferably, 1,3-butylene glycol (1,3-butanediol).

  The alcohols may be used alone or in combination of two or more.

  The blending ratio of the alcohol is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and 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. Preferably, it is 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 hydroxyl group of the alcohol is, for example, 5 or more, preferably 10 or more, more preferably 20 or more, and usually 1000 or less.

  Such mixing of the raw material component and the alcohol is performed, for example, under an inert gas atmosphere such as nitrogen gas under normal pressure (atmospheric pressure). As mixing conditions, the mixing temperature is, for example, room temperature (eg, 25 ° C.) or more, preferably 40 ° C. or more, for example, 100 ° C. or less, preferably 90 ° C. or less, and the mixing time is, for example, 3 minutes or more Preferably, it is 12 minutes or more, for example, 10 hours or less, preferably 6 hours or less.

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

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

  In the reaction step, the catalyst deactivator is added after the conversion reaches the target value (for example, 10% or more, preferably 20% or more, for example, 40% or less), thereby the isocyanurate reaction Is stopped (post-reaction addition step, reaction termination step).

  As a catalyst deactivating agent, a phosphoric acid compound, a sulfonic acid compound, a sulfonamide compound etc. are mentioned, for example.

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

  As a sulfonic acid compound, a sulfonic acid, a sulfonic acid ester, etc. are mentioned, for example. As a sulfonic acid, dodecylbenzenesulfonic acid, para-toluenesulfonic acid etc. are mentioned, for example. Examples of sulfonic acid esters include alkyl dodecylbenzene sulfonate alkyl esters such as methyl dodecyl benzene sulfonate, ethyl dodecyl benzene sulfonate, propyl dodecyl benzene sulfonate, butyl dodecyl benzene sulfonate, and the like, for example, methyl para-toluene sulfonate, para-toluene Examples thereof include p-toluenesulfonic acid alkyl esters such as ethyl sulfonate, propyl p-toluenesulfonate and butyl p-toluenesulfonate.

  Examples of sulfonamide compounds include aromatic sulfonamides (eg, benzene sulfonamide, dimethyl benzene sulfonamide, sulfanyl amide, o- and p-toluene sulfonamide, hydroxy naphthalene sulfonamide, naphthalene-1-sulfonamide, naphthalene -2-sulfonamide, m-nitrobenzene sulfonamide, p-chlorobenzene sulfonamide, etc., aliphatic sulfonamides (eg, methane sulfonamide, N, N-dimethyl methane sulfonamide, N, N-dimethyl ethane sulfonamide, N, N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide Donado), and the like.

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

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

  The catalyst deactivator also acts as a storage stabilizer for the above-mentioned isocyanurate reaction solution.

  The catalyst deactivator preferably includes a phosphoric acid compound and / or a sulfonic acid compound. In other words, the catalyst deactivator preferably includes phosphoric acid and / or sulfonic acid or an ester thereof.

  By using these, in a separation step to be described later, a catalyst component (storage stabilizer) can be contained in a product component (described later) containing isocyanurate, and storage stability of the product component is improved. be able to. Furthermore, when the above-mentioned catalyst deactivating agent is used, it is possible to suppress the mixing of the catalyst deactivating agent (storage stabilizer) into 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 as described later, the recovered component can be reused in the reaction step.

  From such a viewpoint, as the catalyst deactivator, more preferably, sulfonic acid is mentioned, and particularly preferably, dodecylbenzenesulfonic acid is mentioned.

  The use mode of the catalyst deactivator is not particularly limited, and the active component of the catalyst deactivator may be used directly, or a catalyst deactivator solution in which the catalyst deactivator is dissolved in the above organic solvent is used. You may use it. Preferably, a catalyst quencher solution is used.

  When the catalyst deactivator is used as a catalyst deactivator solution, preferred organic solvents include glycol ether esters, more preferably propylene glycol methyl ether acetate.

  Further, 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 It is.

  The addition ratio (in terms of active ingredient) of the catalyst deactivator is, for example, 400 ppm or more, preferably 500 ppm or more, more preferably 600 ppm or more, for example, 3000 ppm or less, based on the total amount of the isocyanurate reaction solution. Preferably, it is 1000 ppm or less, more preferably 800 ppm or less.

  If the addition ratio of the catalyst deactivator is in the above range, the catalyst deactivator (storage stabilizer) can be contained in the product component (described later) containing isocyanurate in the separation step to be described later. Storage stability can be improved. Furthermore, when the above-mentioned catalyst deactivating agent is used, it is possible to suppress the mixing of the catalyst deactivating agent (storage stabilizer) into 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 as described later, the recovered component can be reused in the reaction step.

  Moreover, the isocyanurate reaction liquid obtained preferably contains an acid component.

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

  If the acidity of the isocyanurate reaction liquid is in the above range, the acidity of the recovered component obtained in the separation step described later can be adjusted to a predetermined range, and a recovered component excellent in reusability can be obtained.

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

(3) Suppression of gelation Further, in the above-mentioned isocyanurate reaction, xylylene diisocyanate may react rapidly at the initial stage of the isocyanurate 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 deactivator can be added to the raw material component before the above-mentioned reaction step, if necessary (pre-reaction addition step).

  Examples of the catalyst deactivator include the above-described phosphoric acid compound, the above-described sulfonic acid compound, the above-described sulfonamide compound, monochloroacetic acid, benzoyl chloride and the like.

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

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

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

  Further, as the catalyst deactivator added in the pre-reaction addition step, preferably, a phosphoric acid compound and / or a sulfonic acid compound can be mentioned. In other words, the catalyst deactivator preferably includes phosphoric acid and / or sulfonic acid or an ester thereof.

  The use mode of the catalyst deactivator is not particularly limited, and the active component of the catalyst deactivator may be used directly, or a catalyst deactivator solution in which the catalyst deactivator is dissolved in the above organic solvent is used. You may use it. Preferably, a catalyst quencher solution is used.

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

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

  By adding a predetermined amount of catalyst deactivator to the raw material component prior to the isocyanurate reaction, it is possible to suppress the rapid progress of the isocyanurate reaction at the initial stage of the reaction, and it is possible to suppress the generation of gel.

  Moreover, in this method, preferably, a catalyst deactivator is first added before the isocyanurate reaction (addition step before reaction), and after the isocyanurate reaction is further carried out, the catalyst for the isocyanurate reaction solution obtained is further added A deactivator is added (post-reaction addition step).

  In such a case, in the post-reaction addition step, as described above, the catalyst deactivator is added so as to be a predetermined amount relative to the isocyanurate reaction liquid.

  In addition, the addition ratio of the catalyst deactivator to the isocyanurate reaction liquid and the content ratio of the catalyst deactivator in the isocyanurate reaction liquid are clearly distinguished. That is, the catalyst deactivator added in the pre-reaction addition step and the catalyst deactivator added in the post-reaction addition step are contained in the isocyanurate reaction liquid.

  The addition ratio of the catalyst deactivator in the post-reaction addition step (addition ratio (ppm) of the catalyst deactivator to the raw material component) is the addition ratio of the catalyst deactivator in the pre-reaction addition step (catalyst deactivation to the isocyanurate reaction liquid) With respect to the addition ratio (ppm) of the agent, 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 less than 15 times.

  If the ratio of the addition ratio of the catalyst deactivator is in the above-mentioned range, it is possible to suppress the generation of gel particularly efficiently. In addition, since the total content ratio of the catalyst deactivator in the isocyanurate reaction liquid is adjusted, the catalyst deactivator can be contained in the product component (described later) in the separation step to be described later, and the storage stability of the product component It is possible to improve the quality. Furthermore, the catalyst deactivating agent (storage stabilizer) can be prevented from being mixed into the recovered component (described later). Therefore, a recovered component having excellent reactivity can be obtained, and as described later, the recovered component can be reused in the reaction step.

(4) Separation And, in this method for producing isocyanurate, after completion of the above isocyanurate reaction, from the isocyanurate reaction liquid, a product component containing isocyanurate of xylylene diisocyanate and unreacted xylylene diisocyanate. The separated recovery components are separated from each other (separation step).

  The product component is an isocyanurate of xylylene diisocyanate (an isocyanurate composition mainly containing trimers of xylylene diisocyanate and further containing pentamers, heptamers and the like of xylylene diisocyanate), and the above. It is a composition containing a catalyst deactivator.

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

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

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

  Further, 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.

  Also, the feed amount of the isocyanurate reaction liquid 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.

  Thereby, 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.

  In addition, the isocyanate monomer concentration (the 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.

  In addition, the solid content concentration can be adjusted by adding the above-mentioned organic solvent at an appropriate ratio to the product component, if necessary.

  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 catalyst deactivator added in the isocyanuration 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, for example, 2500 ppm or less, preferably 2000 ppm or less, based on the total amount of the product components.

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

  If necessary, the above-mentioned catalyst deactivator (storage stabilizer) may be further added to the separated product component to adjust the content ratio to the above range.

  Further, the product components may, if necessary, be known additives, for example, plasticizers, antiblocking agents, heat resistant stabilizers (such as the sulfonamide compounds mentioned above), light stabilizers, antioxidants, mold release agents, Pigments, dyes, lubricants, fillers, hydrolysis inhibitors 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 unreacted xylylene diisocyanate (monomer), an acid component and (in addition, an optional organic solvent).

  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, for example, 80 ppm or less, preferably 75 ppm, based on the total amount of recovered components. Below, it is 70 ppm or less more preferably.

  In addition, if necessary, a known acid such as hydrogen chloride or xylylene diisocyanate having high acidity (for example, xylylene diisocyanate composition having an acidity of 2000 ppm or more, etc.) is added to the above-mentioned recovered components to obtain acidity. It can be adjusted.

  Also, the recovered component is essentially free of a catalyst deactivating agent (storage stabilizer).

  Specifically, by using phosphoric acid and / or sulfonic acid, or an ester thereof as a catalyst deactivator (storage stabilizer), the catalyst deactivator (storage stabilizer) in the product component in the above separation step ), While the recovered component may not contain a catalyst 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, particularly preferably 0 ppm, based on the total amount of the recovered components.

  In addition, the xylylene diisocyanate purity (that is, the content ratio of XDI (monomer) to the total amount of recovered components) of the recovered components 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.

  Since the recovered component contains the acid component at a predetermined ratio as described above, the storage stability is excellent even if it does not contain the catalyst deactivator (storage stabilizer) described above. Furthermore, since the acid component has a lower inhibitory effect on the isocyanurate reaction than the catalyst deactivator, the above-mentioned recovered component is also excellent in the isocyanurate reaction efficiency. Therefore, the recovered component can be suitably used in the above-mentioned isocyanurate 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 reaction (reuse step).

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

  Although the mixing ratio in such a case is not particularly limited, for example, 10 parts by mass or more of the recovered component is, for example, 100 parts by mass in total of the recovered component and the newly prepared xylylene diisocyanate composition. Preferably, it is 20 parts by mass or more, for example, 90 parts by mass or less, preferably 80 parts by mass or less. In addition, the amount of 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.

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

(6) Action and Effect The above-described xylylene diisocyanate composition (raw material component) contains an acid component at a predetermined ratio, and thus is excellent in storage stability. Furthermore, since the acid component has a lower inhibitory effect on the isocyanurate reaction than the catalyst deactivator, the xylylene diisocyanate composition is also excellent in the isocyanurate reaction efficiency.

  Moreover, in the method for producing isocyanurate described above, since the xylylene diisocyanate composition containing the acid component at a predetermined ratio is used, it is possible to produce the isocyanurate with excellent efficiency.

  Although an example is shown below and the present invention is explained still more concretely, the present invention is not limited to them. Specific numerical values such as blending ratios (content ratios), physical property values, parameters, etc. used in the following description are the blending ratios (content ratios) corresponding to those described in the above-mentioned "embodiments for carrying out the invention" ), Physical property values, parameters, etc. may be substituted for the upper limit (numerical values defined as “below”, “less than”) or lower limit (numerical values defined as “above”, “exceed”), etc. it can. In addition, "part" and "%" are mass references | standards unless there is particular mention.

Example 1
Hydrogen chloride is added to 1,3-xylylene diisocyanate (m-XDI, manufactured by Mitsui Chemicals, Inc.) to adjust the acidity (according to JIS K-1603-2: 2007) to the acidity (20 ppm) described in Table 1 did. Thereby, the raw material component which consists of a XDI composition of predetermined acidity was obtained (preparation process).

  In a nitrogen atmosphere, 787.470 parts by mass of XDI composition and octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (hindered phenolic antioxidant, trade name: Irganox 1076, 0.161 parts by mass of Ciba Japan Co., Ltd.) 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, catalyst deactivator) was added to the mixture. The addition amount was adjusted so that DDBSA was 0.064 parts by mass (addition rate was 80 ppm with respect to the total amount of the raw material components) (pre-reaction addition step).

  Next, 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 urethane reaction reaction.

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

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

  Next, a solution of dodecylbenzenesulfonic acid (DDBSA, catalyst deactivator) in propylene glycol methyl ether acetate (active ingredient concentration: 50% by mass) was added to the obtained isocyanurate reaction liquid to terminate the isocyanurate 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 isocyanurate reaction solution) (reaction stopping step, addition step after reaction).

  Then, the obtained isocyanurate 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 previously prepared high acidity (acidity 2400 ppm) XDI composition was added to the isocyanurate reaction solution, stirred for 30 minutes, and then cooled to 50 ° C. or less.

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

  And ethyl acetate (EA) was added to the obtained product component, the solid content density | concentration was adjusted to 75 mass%, 0.333 mass parts (heat-resistant stabilizer) of para-toluene sulfonamide was added.

Examples 2 to 4 and Comparative Examples 1 to 2
The isocyanurate 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 described in Table 1.

Reference Examples 1 to 12
Tolylene diisocyanate (TDI, Mitsui Chemicals) or hexamethylene diisocyanate (HDI, Tosoh) is used in place of m-XDI (Mitsui Chemical Co., Ltd.) and the acidity of the raw material component is described in Tables 2-3 The isocyanurate was reacted in the same manner as in Example 1 except that the acidity was adjusted to

<Evaluation>
1. Storage stability The raw material component which adjusted acidity was stored at 40 degreeC for 2 months, and the external appearance was observed visually. And the presence or absence of generation | occurrence | production of the turbidity originating in dimerization, nylon formation, gelatinization etc. was evaluated. The criteria for evaluation are as follows.
○: no turbidity occurred.
X: turbidity occurred.

2. The progress of the reactive isocyanurate reaction was evaluated. The criteria for evaluation are as follows. In addition, when the isocyanurate reaction advanced rapidly and gelatinization generate | occur | produced, it evaluated as "x (gelation)." Moreover, when the isocyanurate reaction did not advance, it evaluated as "x (non-progress)."
○: The reaction has progressed.
X: gelation occurred or reaction did not proceed.

<Discussion>
As Comparative Example 1 is referred to, it was confirmed that the storage stability is not sufficient when the acidity of the raw material component is excessively low (when it is less than 20 ppm). In addition, it was confirmed that when the amount of the acid component is small, the isocyanurate reaction proceeds rapidly, thus causing gelation.

  On the other hand, as Comparative Example 2 is referred to, when the acidity of the raw material component is excessively high (when it exceeds 80 ppm), although the storage stability is excellent, the isocyanurate reaction does not proceed, so the raw material of isocyanurate It has been confirmed that it can not be used.

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

  Moreover, it was confirmed from each reference example that the above-mentioned range of acidity is unique to XDI.

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

  Further, as Reference Examples 9 to 11 are referred to, when HDI is used, gelation does not occur even if the acidity is less than 20 ppm, while reactivity is sufficient even if the acidity is 80 ppm or less. It was confirmed that there was not.

Claims (2)

A xylylene diisocyanate composition for producing isocyanurate of xylylene diisocyanate, which composition comprises
The xylylene diisocyanate composition contains xylylene diisocyanate and an acid component,
The xylylene diisocyanate composition, wherein the content ratio of the acid component is 20 to 80 ppm with respect to the total amount of the xylylene diisocyanate composition as a hydrogen chloride conversion value. A preparation step of preparing the xylylene diisocyanate composition according to claim 1;
A reaction step of obtaining an isocyanurate of xylylene diisocyanate by subjecting the xylylene diisocyanate composition to an isocyanurate reaction in the presence of an isocyanurate catalyst to obtain an isocyanurate.