WO2024106985A1 - Composition de diisocyanate de xylène et son procédé de préparation - Google Patents

Composition de diisocyanate de xylène et son procédé de préparation Download PDF

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Publication number
WO2024106985A1
WO2024106985A1 PCT/KR2023/018490 KR2023018490W WO2024106985A1 WO 2024106985 A1 WO2024106985 A1 WO 2024106985A1 KR 2023018490 W KR2023018490 W KR 2023018490W WO 2024106985 A1 WO2024106985 A1 WO 2024106985A1
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Prior art keywords
composition
compound
xylene diisocyanate
clause
boiling point
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PCT/KR2023/018490
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English (en)
Korean (ko)
Inventor
심유진
박주영
박종성
우은지
Original Assignee
한화솔루션 주식회사
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Priority claimed from KR1020230159228A external-priority patent/KR20240072076A/ko
Publication of WO2024106985A1 publication Critical patent/WO2024106985A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
    • C07C265/04—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a xylene diisocyanate composition with controlled low boiling point compound content and a method for producing the same.
  • xylylene diisocyanate (hereinafter referred to as It is a very useful compound as a raw material.
  • aliphatic isocyanates are produced by a phosgenation method in which raw amine is reacted with phosgene.
  • a phosgenation method in which raw amine is reacted with phosgene.
  • XDI it is manufactured by reacting xylylene diamine (XDA) with phosgene.
  • XDA xylylene diamine
  • XDI has high amino group reactivity, so many side reactions occur during the phosgenation reaction, and impurities formed through side reactions affect the reaction in which polyurethane resin is formed, causing a decrease in resin quality. There is a problem.
  • Korean Patent Publication No. 1994-0001948 describes the use of ester-based compounds such as amyl acetate or hexyl acetate as a reaction solvent in the production of xylene diisocyanate through the reaction of xylene diamine or its hydrochloride and phosgene to produce XDI with high purity.
  • a manufacturing method is disclosed. However, this method has the problem that the solvent is expensive and the purity and yield are still low.
  • Korean Patent Registration No. 0953019 discloses that amine hydrochloride is prepared through a salt formation process in which chain-shaped or cyclic aliphatic amines are reacted with hydrogen chloride, and then isocyanate is formed through phosgene reaction to solve the problem of transport of amine hydrochloride.
  • a method of pressurizing the salt formation process is disclosed.
  • Korean Patent Registration No. 1318828 involves reacting a diamine compound with alkyl chloroformate or dialkyl carbonate to produce biscarbamate, and then thermally decomposing it to decompose and remove alcohol with a relatively low boiling point.
  • a method for producing xylene diisocyanate through a biphosgene method is disclosed.
  • this method is not only disadvantageous in terms of price compared to the phosgene method, but also difficult to apply to industrial mass production.
  • the present invention relates to a xylene diisocyanate composition with controlled low boiling point compound content and a method for producing the same.
  • the present invention provides a method for producing high purity xylene diisocyanate compounds in high yield by controlling the purity of the amine compound and controlling the content range of a specific low boiling point compound in the reactant when producing xylene diisocyanate using phosgene.
  • the purpose is to provide a method for producing rene diisocyanate.
  • the present invention provides a production method that can economically produce a high-purity xylene diisocyanate compound by performing a salt formation reaction under specific conditions and increasing the process efficiency of the phosgene reaction by utilizing the reaction heat generated in the reaction. It is for.
  • the low boiling point compound is contained in an amount of 1% or less based on the total content of the composition
  • a xylene diisocyanate composition is provided.
  • a first step of obtaining an amine salt compound by reacting an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and normal pressure;
  • the solvent is at least one selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene,
  • the purity of the amine compound is 99.0% or more
  • the xylene diisocyanate composition includes a low boiling point compound of 1% or less based on the total content of the composition, and the low boiling point compound includes isocyanomethylbenzaldehyde and isocyanomethylbenznitrile.
  • a manufacturing method is provided.
  • a first step of obtaining an amine salt compound by reacting an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and normal pressure;
  • a third step of preparing a xylene diisocyanate composition by removing the solvent and unreacted phosgene from the reaction mixture;
  • the solvent is at least one selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene,
  • the purity of the amine compound is 99.0% or more
  • the xylene diisocyanate composition includes a low boiling point compound of 1% or less based on the total content of the composition, and the low boiling point compound includes isocyanomethylbenzaldehyde and isocyanomethylbenznitrile.
  • Method for producing a polyisocyanate composition This is provided.
  • a polymerizable composition comprising at least one of i) a polyfunctional thiol-based compound and ii) a polyfunctional episulfide-based compound.
  • An optical article comprising a polythiourethane polymer prepared from the polymerizable composition is provided.
  • the content range of a specific low boiling point compound is controlled, so that a high purity polyisocyanate compound can be produced in high yield without generating additional impurities during polyisocyanate synthesis.
  • the method for producing a xylene diisocyanate composition according to the present invention provides a high purity xylene diisocyanate compound in high yield through a simple manufacturing process that adjusts the purity of the reaction composition and at the same time controls the content range of specific low boiling point compounds in the by-products. It can be manufactured with
  • the method for producing a xylene diisocyanate composition according to the present invention can economically produce a high-purity xylene diisocyanate compound by adjusting the salt formation reaction conditions of the amine compound to an appropriate range to increase process efficiency in the subsequent phosgene reaction. You can.
  • the method for producing a polyisocyanate composition according to the present invention can produce a high-purity polyisocyanate compound in high yield by controlling the purity of the reaction composition and simultaneously controlling the content range of a specific low boiling point compound in the by-product.
  • the production of isocyanate compounds using a phosgenation reaction is performed by reacting an amine compound with phosgene, and at this time, various impurities are produced as side reactants.
  • the present inventors determined the impact of applying polyisocyanate polymerized using isocyanate containing various impurities to actual products, controlled the purity of the solvent and amine compound as reactants, and simultaneously reduced the content of low boiling point compounds in the reaction mixture.
  • the present invention was completed by confirming that high purity isocyanate can be produced in high yield by controlling it to a specific range (about 1% or less).
  • low boiling point compounds among reaction by-products may generate additional impurities when synthesizing polyisocyanate and may affect the reaction rate by interfering with the activity of the catalyst, thereby affecting the quality of the product.
  • By adjusting the content to an appropriate range it is possible to manufacture high-quality products without such problems, and such high-purity polyisocyanate compounds can significantly reduce the defect rate and improve reproducibility when applied to optical products.
  • the amine compound used in the phosgene reaction is produced in the form of a chloride through a salt formation reaction.
  • the salt formation reaction proceeds under relatively mild conditions in a specific solvent, thereby providing additional cooling or heating in the phosgene reaction.
  • the phosgene reaction can be easily performed without going through any process, making it highly economical.
  • a xylene diisocyanate compound and a low boiling point compound including isocyanomethylbenzaldehyde and isocyanomethylbenznitrile, wherein the low boiling point compound is contained in an amount of 1% or less based on the total content of the composition.
  • the content range of the low boiling point compound is the GC area (%) measured according to gas chromatography (GC) analysis, and the specific measurement method will be described in more detail in the experimental examples described later.
  • the low boiling point compound is included in more than 1% in the composition, additional impurities may be generated during polyisocyanate synthesis and may interfere with the activity of the catalyst, thereby affecting the reaction rate. This affects the quality of the product.
  • the xylene diisocyanate composition adjusted to the appropriate content range as described above, it is possible to manufacture high purity polyisocyanate without such problems, and these polyisocyanate compounds are used in optical products. When applied to, the defect rate can be significantly reduced and reproducibility can be improved.
  • the content of the low boiling point compound may preferably be 0.7% or less, 0.5% or less, or 0.3% or less based on the total content of the xylene diisocyanate composition.
  • the lower limit of the low boiling point compound is 0% or more, preferably 0.0001% or more, 0.0001% to 0.7%, or 0.001 to 0.5%, and is suitable for realizing the above-described effects in the above content range.
  • the isocyanomethylbenzaldehyde (IMBAl) may be included in an amount of 0.0001 to 0.15%, preferably 0.001 to 0.15%, or 0.0003 to 0.11%, based on the total content of the composition.
  • the isocyanomethylbenznitrile (IMBN) may be included in an amount of 0.0001 to 0.1%, preferably 0.0003 to 0.1%, or 0.0008 to 0.06%, based on the total content of the composition.
  • the low boiling point compound may further include chloromethylbenzyl isocyanate (CMBI).
  • CMBI chloromethylbenzyl isocyanate
  • the chloromethylbenzyl isocyanate may be included in an amount of 0.01 to 0.2%, preferably 0.05 to 0.15%, based on the total content of the composition.
  • the xylene diisocyanate composition may further include additional additives to maintain storage stability.
  • the type of the additional additive is not particularly limited, and may further include antioxidants, heat stabilizers, polymerization inhibitors, etc. commonly used in the art.
  • the content of the additive is not particularly limited and can be used in an appropriate range as long as it does not impair the purpose of the present invention.
  • the xylene diisocyanate composition can be used in a wide range of fields due to its excellent physical properties, and among these, it can be used as optical products.
  • the xylene diisocyanate composition can be prepared according to the production method described later.
  • a method for producing a xylene diisocyanate composition includes the steps of reacting an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and normal pressure to obtain an amine salt compound; and reacting the amine salt compound with phosgene to obtain a reaction mixture comprising a xylene isocyanate compound; And a third step of preparing a xylene diisocyanate composition by removing the solvent and unreacted phosgene from the reaction mixture.
  • a first step (salt formation reaction) is performed to obtain an amine salt compound by reacting an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and normal pressure.
  • the salt formation reaction to obtain the amine salt compound is carried out in a specific solvent at 20°C to 90°C and normal pressure, the phosgene reaction can be easily performed without additional cooling or heating processes in the subsequent phosgene reaction, resulting in excellent economic efficiency.
  • normal pressure refers to the pressure in a state without applying pressure reducing equipment such as a separate vacuum pump.
  • this may correspond to general atmospheric conditions of approximately 760 mmHg.
  • the salt formation reaction when the salt formation reaction is performed below 20°C, the particle size of the amine salt compound may become non-uniform, thereby inhibiting the subsequent phosgene reaction.
  • the salt formation reaction when carried out above 90°C, there is a problem in that it is difficult to control the salt formation reaction itself.
  • the salt formation reaction may be performed at 30°C to 80°C. Meanwhile, the temperature of the salt formation reaction can be adjusted by the reaction heat resulting from the addition of hydrogen chloride without special temperature control.
  • the solvent is one or more selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene.
  • chlorobenzene 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene.
  • These are inert organic solvents and can contribute to reducing the content of side reactants. Additionally, these solvents have high polarity and can facilitate the reaction by helping to dissolve the amine salt compound. Most preferably, 1,2-dichlorobenzene can be used.
  • a solvent such as n-amyl acetate
  • the particle size of the amine salt compound may become non-uniform, thereby inhibiting the phosgene reaction.
  • the purity of the solvent may satisfy 99.0% or more, and accordingly, side reactions in the phosgenation reaction are minimized, and in particular, the content of low boiling point compounds among side reactants is adjusted to the above-mentioned range to produce high purity xylene dimethyl sulfate. Isocyanate can be produced. More preferably, the purity of the solvent is 99.0% to 99.99%. It is desirable to achieve the above-mentioned effects within the above content range.
  • the purity of the amine compound satisfies 99.0% or more, side reactions in the phosgenation reaction can be minimized, and in particular, high purity xylene diisocyanate compounds can be produced by adjusting the content of low boiling point compounds among side reactants to the above-mentioned range. there is. More preferably, the purity of the amine compound is 99.0% to 99.99%. It is desirable to achieve the above-mentioned effects within the above content range.
  • the amine compound may be one or more selected from the group consisting of m-xylene diamine, p-xylene diamine, o-xylene diamine, and their chlorides (for example, hydrochloride or carbonate, etc.).
  • the chloride of the amine compound may be used, and in this case, it is preferable because the conversion rate to the product can be increased and the content of impurities can be lowered during the production of the xylene isocyanate compound, which will be described later.
  • the amine compound can be obtained through the following reaction and exhibit a purity in the above-mentioned range:
  • XDA is synthesized through ammoxidation of m-xylene in the first step to produce IPN (isophalonitrile) and then through a second-step hydrogenation reaction.
  • Impurities that may be generated during the second-step synthesis are indicated as #1 to #3.
  • Various impurities may be generated, but the content of impurities is trace amounts (about 1% or less).
  • the impurities may affect the content of low boiling point compounds in the process of obtaining a reaction mixture containing a xylene isocyanate compound, which will be described later. That is, the higher the purity of the amine compound, the lower the content of low boiling point compounds. do.
  • the amine compound may be included in an amount of 1 to 20% by weight based on the total solvent content. If the content of the amine compound exceeds 20% by weight, the stirring process during reaction is difficult, there is a risk that a large amount of the amine compound may precipitate, and the non-uniform reaction may affect the increase in the content of the low boiling point compound. Preferably, it may be included in 1 to 15% by weight or 5 to 15% by weight.
  • the temperature of the reaction is not particularly limited, but may be performed at 110°C to 160°C, and more preferably at 120°C to 140°C. If the reaction temperature exceeds 160°C, the concentration of by-products increases, and problems such as thermal decomposition of reactants and products may occur.
  • the temperature in the reactor is gradually raised to the above-mentioned range, and then phosgene is added. More preferably, the temperature in the reactor is adjusted to 110°C to 140°C after phosgene is added. It can be. The reactor temperature may preferably be adjusted to 120°C to 135°C.
  • the method of adding phosgene is not particularly limited.
  • it can be performed by simply mixing the amine salt compound and phosgene into one reactor, or by injecting phosgene into the reactor containing the amine salt compound through a mixing eductor, which is a mixing nozzle.
  • a mixing eductor which is a mixing nozzle.
  • it can be performed by injecting phosgene through a mixing emitter, which is preferable because the reaction time can be shorter and the impurity content can be reduced.
  • the time for the reaction is not particularly limited, but may be carried out for about 1 hour to 4 hours after the addition of phosgene is completed. Preferably, it may be performed for 1 hour to 3 hours.
  • a process of reducing the temperature in the reactor to 70°C to 80°C may be further performed.
  • a third step of preparing a xylene diisocyanate composition by removing the solvent and unreacted phosgene from the reaction mixture.
  • a xylene diisocyanate composition containing a xylene diisocyanate compound is prepared.
  • the third step may further include a purification process after removing the solvent and unreacted phosgene from the reaction mixture.
  • the method of performing the removal and purification process of the solvent and phosgene is not particularly limited, and methods commonly performed in the art may be applied.
  • unreacted phosgene and hydrogen chloride gas remaining in the reaction mixture can be removed through a nitrogen bubbling process, and solvents can be removed through a distillation process.
  • the purification process can be carried out by purifying through fractional distillation and thin-film distillation under reduced pressure, and in the case of fractional distillation, it can be carried out in a tray distillation column or a packed distillation column in the plant process.
  • the theoretical number of stages of the distillation column is 2 or more stages, preferably 5 or more stages. Preferably it is 50 stages or less and 40 stages or less.
  • the xylene diisocyanate composition prepared according to the salt formation reaction, phosgene reaction, and purification process described above contains a low boiling point compound of 1% or less based on the total content of the composition.
  • the low boiling point compound includes isocyanomethylbenzaldehyde and isocyanomethylbenznitrile.
  • the content range of the low boiling point compound is the GC area (%) measured according to gas chromatography (GC) analysis, and the specific measurement method will be described in more detail in the experimental examples described later.
  • the low boiling point compound is included in excess of 1%, additional impurities may be generated during subsequent polyisocyanate synthesis, and may affect the reaction rate by interfering with the activity of the catalyst. This affects the quality of the product.
  • the xylene diisocyanate composition adjusted to the appropriate content range as described above it is possible to manufacture high purity polyisocyanate without such problems, and these polyisocyanate compounds are used in optical products. When applied to, the defect rate can be significantly reduced and reproducibility can be improved.
  • the content of the low boiling point compound may preferably be 0.7% or less, 0.5% or less, or 0.3% or less based on the total content of the xylene diisocyanate composition.
  • the lower limit of the low boiling point compound is 0% or more, preferably 0.0001% or more, 0.0001% to 0.7%, or 0.001 to 0.5%, and is suitable for realizing the above-described effects in the above content range.
  • the isocyanomethylbenzaldehyde (IMBAl) may be included in an amount of 0.0001 to 0.15%, preferably 0.001 to 0.15%, or 0.0003 to 0.11%, based on the total content of the composition.
  • the isocyanomethylbenznitrile (IMBN) may be included in an amount of 0.0001 to 0.1%, preferably 0.0003 to 0.1%, or 0.0008 to 0.06%, based on the total content of the composition.
  • the low boiling point compound may further include chloromethylbenzyl isocyanate (CMBI).
  • CMBI chloromethylbenzyl isocyanate
  • the chloromethylbenzyl isocyanate may be included in an amount of 0.01 to 0.2%, preferably 0.05 to 0.15%, based on the total content of the composition.
  • a polymerizable composition comprising at least one of i) a polyfunctional thiol-based compound and ii) a polyfunctional episulfide-based compound.
  • the polymerizable composition may include the isocyanate composition, the polyfunctional thiol-based compound, and the polyfunctional episulfide-based compound in a mixed state or in a separated state. That is, in the polymerizable composition, the isocyanate composition and the polyfunctional thiol-based compound or polyfunctional episulfide-based compound may be blended in contact with each other, or may be separated so as not to contact each other.
  • the multifunctional thiol-based compound may be a compound containing two or more thiol (Thio, -SH) groups in the molecule, and may have an aliphatic, alicyclic, or aromatic skeleton.
  • the multifunctional episulfide-based compound may be a compound containing two or more episulfides, that is, a thioepoxy group, in the molecule, and may have an aliphatic, alicyclic, or aromatic skeleton.
  • the multifunctional thiol-based compound is 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,7-bis(mercapto methyl)-3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-trithiaoundecan-1,11-dithiol, Bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-3,6-dithioctane-1,8-dithiol, 2,3-bis(2-mercaptoethylthio)propane-1-thiol , 2,2-bis(mercaptomethyl)propane-1,3-dithiol, 2-(2-mercaptoethylthio)propane-1,3-dithiol, 2-(2,3-bis(2- Mercaptoethylthio)propylthio)e
  • the multifunctional episulfide-based compound is bis( ⁇ -epithiopropylthio)methane, 1,2-bis( ⁇ -epithiopropylthio)ethane, 1,3-bis( ⁇ -epithiopropyl) thio)propane, 1,2-bis( ⁇ -epithiopropylthio)propane, 1-( ⁇ -epithiopropylthio)-2-( ⁇ -epithiopropylthiomethyl)propane, 1,4-bis( ⁇ -Epitiopropylthio)butane, 1,3-bis( ⁇ -epithiopropylthio)butane, 1-( ⁇ -epithiopropylthio)-3-( ⁇ -epithiopropylthiomethyl)butane, 1,5 -bis( ⁇ -epithiopropylthio)pentane, 1-( ⁇ -epithiopropylthio)
  • the molar ratio of (thio group + episulfide group) to isocyanate group may be about 0.5 to about 1.5, or about 0.8 to about 1.2, or about 0.9 to about 1.1, but the present invention does not necessarily include this. It is not limited.
  • the polymerizable composition may further include additives such as mold release agents, heat stabilizers, UV stabilizers, pigments, urethane reaction catalysts, etc. in appropriate amounts.
  • additives such as mold release agents, heat stabilizers, UV stabilizers, pigments, urethane reaction catalysts, etc. in appropriate amounts.
  • the mold release agent is a type of surfactant component, for example, a fluorine-based nonionic surfactant containing a perfluoroalkyl group; Silicone-based nonionic surfactant containing a dimethylpolysiloxane group; and quaternary ammonium salts such as trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, and diethylcyclohexadodecyl ammonium salt.
  • quaternary ammonium salts such as trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, and diethylcyclohexadodecyl ammonium salt.
  • the heat stabilizer may be, for example, a metal fatty acid salt-based, phosphorus-based, lead-based, or organotin-based compound. These may be used alone or in combination of two or more.
  • the UV stabilizer may be, for example, a benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, or oxanilide-based compound.
  • Examples of the dye include fluorescent whitening agents, fluorescent pigments, and inorganic pigments.
  • the urethane reaction catalyst includes, for example, dialkyl tin halide-based compounds such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylate compounds such as dimethyltin diacetate, dibutyltin dioctanoate, and dibutyltin dilaurate; Dialkyl tin dialkoxide-based compounds such as dibutyltin dibutoxide and dioctyltin dibutoxide; dialkyltin dithioalkoxide-based compounds such as dibutyltin di(thiobutoxide); dialkyl tin oxide-based compounds such as di(2-ethylhexyl)tin oxide, dioctyltin oxide, and bis(butoxydibutyltin) oxide; Dialkyl tin sulfide-based compounds, etc. may be used individually or in combination of two or more types.
  • an optical article comprising a polythiourethane polymer prepared from the polymerizable composition is provided.
  • the optical article may be an optical lens, for example, a spectacle lens, a camera lens, a plastic lens, a prism, etc.
  • a method for producing a polyisocyanate composition is provided by applying the method for producing the xylene diisocyanate composition.
  • the method for producing a polyisocyanate composition according to an embodiment of the invention is,
  • a first step of obtaining an amine salt compound by reacting an amine compound with hydrogen chloride in a solvent at 20°C to 90°C and normal pressure;
  • a third step of preparing a xylene diisocyanate composition by removing the solvent and unreacted phosgene from the reaction mixture;
  • the contents of the first step, second step, and third step may be equally applied to the method for producing the above-described xylene diisocyanate composition.
  • the solvent is one selected from the group consisting of chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene. or more, the purity of the amine compound is 99.0% or more, and the xylene diisocyanate composition contains a low boiling point compound of 1% or less based on the total content of the composition.
  • the low boiling point compound includes isocyanomethylbenzaldehyde and isocyanomethylbenznitrile.
  • Step 4 it includes a fourth step of synthesizing a polyisocyanate compound by polymerizing the xylene diisocyanate composition by mixing it with a polyhydric alcohol.
  • the isocyanate compound contained in the composition is of high purity, and the low boiling point compound in the composition satisfies 1% or less, thereby significantly reducing the generation of by-products in the polymerization step.
  • the polyhydric alcohol is a compound containing 2 or more hydroxy groups in one molecule, specifically, 2 or more, or 3 or more, 8 or less, or 4 or less hydroxy groups in the molecule. It may be a compound.
  • ethylene glycol diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2-methyl-2,3-butanediol, Dihydric alcohols such as 1,6-hexanediol, 1,2-hexanediol, etc.; Trihydric alcohols such as glycerol, trimethylolethane, and trimethylolpropane (TMP); tetrahydric alcohols such as diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.; Pentahydric alcohols such as L-arabinitol, ribitol, and xylitol; Hexahydric alcohols such as D-glucitol, D-mannitol, and galactitol, and heptahydric alcohol
  • the polymerization reaction consists of a urethanization reaction (or addition polymerization reaction) between an isocyanate compound and a hydroxy group in a polyhydric alcohol.
  • the amount of the polyhydric alcohol in consideration of the physical properties to be implemented in the polyisocyanate produced, such as urethanization reaction with an isocyanate compound and viscosity, and the use of the polymer.
  • the polyhydric alcohol may be added in an amount such that the molar ratio of the hydroxy group in the polyhydric alcohol to 1 mole of the isocyanate group of the isocyanate compound is 0.05 or more, or 0.15 or more, and 1 or less, or 0.8 or less.
  • the viscosity of the produced polymer may decrease due to the excess isocyanate group, and as a result, there is a risk that the processability may decrease. Additionally, if the molar ratio of hydroxy groups to isocyanate groups exceeds 1, there is a risk that the discoloration prevention effect may be reduced due to excess hydroxy groups.
  • the polymerization reaction may be performed under normal pressure conditions and an inert gas atmosphere such as nitrogen or argon.
  • the polymerization reaction is performed at a temperature range of 40°C or higher, or 60°C or higher, and 100°C or lower or 80°C or lower, so that the reaction rate can be easily controlled without concern about discoloration, and reaction efficiency can also be increased. It is desirable.
  • the polymerization reaction may be performed under catalyst-free conditions, or may be performed in the presence of a catalyst that usually promotes the urethanization reaction, such as tin-based or amine-based.
  • a catalyst that usually promotes the urethanization reaction, such as tin-based or amine-based.
  • additional catalyst may be added when the polyhydric alcohol is added to the monomer composition.
  • the progress of the polymerization reaction can be predicted by measuring the concentration of isocyanate groups in the polymerization reaction product or measuring the refractive index using the n-dibutyl amine method using a secondary titration device.
  • the isocyanate group in the polymerization reaction product is This is carried out until the concentration reaches the calculated value of the isocyanate group remaining after reaction with the polyhydric alcohol.
  • the polyisocyanate prepared as above can be produced into polyurethane through reaction with polyol, and by using the polyisocyanate according to the present invention, precise control of the physical properties of polyurethane products is possible.
  • the polyisocyanate specifically includes a urethane bond formed by reacting some or all of the isocyanate groups of the isocyanate compound in the reaction mixture obtained in the above-described phosgenation reaction with the hydroxy group of the polyhydric alcohol.
  • the present invention contains a high-purity xylene diisocyanate compound in the reaction mixture, and in particular, high-purity polyisocyanate can be produced in high yield with a low boiling point compound content of 1% by weight or less, and a product without discoloration and white cloudiness can be manufactured. can do. More preferably, it may be 0.7% or less, 0.5% or less, or 0.3% or less based on the total content of the composition.
  • the lower limit of the low boiling point compound is 0% or more, preferably 0.0001% or more, 0.0001% to 0.7%, or 0.001 to 0.5%.
  • the content range of the low boiling point compound is the GC area (%) measured according to gas chromatography (GC) analysis, and the specific measurement method will be described in more detail in the experimental examples described later.
  • stabilizers and unreacted diisocyanates that did not participate in the polymerization reaction may be present in the product obtained as a result of the polymerization reaction.
  • the method for producing a polyisocyanate composition according to an embodiment of the invention may optionally further include the step of purifying the resulting product after completion of the polymerization reaction to remove unreacted diisocyanate.
  • the purification process can be performed by conventional purification methods such as distillation and solvent extraction, and in the present invention, it can be performed by distillation purification methods such as thin film distillation in terms of excellent removal efficiency of unreacted polyisocyanate.
  • the distillation purification process may be performed under a pressure of 0.001 kPa or more, 1 kPa or less, or 0.5 kPa or less.
  • the distillation purification process may be performed at a temperature of 70°C or higher, or 90°C or higher, and 200°C or lower, or 180°C or lower. If the temperature is less than 70°C, there is a risk that distillation and purification efficiency may decrease, and if it exceeds 200°C, there is a risk that the polyisocyanate may be denatured due to the high temperature.
  • the content of unreacted diisocyanate in the polyisocyanate composition can be lowered, and the lower the content, the greater the stability of the composition, which is preferable.
  • composition prepared according to the method for producing the polyisocyanate composition is provided.
  • the polyisocyanate composition may further include a diluting solvent, and thus exhibits appropriate applicability, making it easy to apply to products.
  • ethyl acetate may be used as a diluting solvent.
  • the isocyanate group content (NCO%) in the composition may be included such that the solid content is 75% by weight.
  • NCO% can be determined by neutralizing the isocyanate group with excess 2N amine and then back titrating with 1N hydrochloric acid.
  • the content of unreacted diisocyanate remaining based on the total weight of solids in the polyisocyanate composition is 1% by weight or less, or 0.5% by weight or less, or 0.3% by weight or less, which significantly reduces the content of unreacted diisocyanate compared to the prior art. It can exhibit excellent stability.
  • the polyisocyanate composition may, if necessary, further include additives such as an internal mold release agent, ultraviolet absorber, polymerization initiator, heat stabilizer, color corrector, chain extender, crosslinker, light stabilizer, filler, etc., and the content thereof may vary depending on the polymer. It can be appropriately determined within a range that does not impair the coloring and discoloration inhibition properties of the composition.
  • additives such as an internal mold release agent, ultraviolet absorber, polymerization initiator, heat stabilizer, color corrector, chain extender, crosslinker, light stabilizer, filler, etc.
  • the above-described polyisocyanate composition can be used in a wide range of fields due to its excellent physical properties, and among these, the polyisocyanate composition can be used as an adhesive or adhesive due to its excellent adhesive/adhesive strength.
  • the phosgene reaction product was analyzed using GC.
  • the GC used for analysis was HP-6890, and detection was performed using FID.
  • the column used was DB-17 (30m * 0.25mm * 0. 5 ⁇ m), the carrier gas was nitrogen (1.0mL/min), the injection volume was 1 ⁇ l, and the oven temperature was 80°C -> 5°C/min -> 160°C (8 min). ) -> 20°C/min -> 280°C (18 min).
  • IMBAl detection method SIM (monitoring ions: m/z 161, 132)
  • CMBI detection method SIM (monitoring ions: m/z 181, 146)
  • IMBAl detection method SIM (monitoring ions: m/z 158, 116)
  • a reaction mixture containing an isocyanate compound was prepared according to Preparation Example 3 (m- was purified to obtain a xylene diisocyanate composition containing an isocyanate compound.
  • the xylene diisocyanate composition containing the isocyanate compound (meta-xylene diisocyanate) prepared above was added to the flask under a nitrogen atmosphere. While the temperature of the flask was raised to 70°C and maintained, 26.7 g of trimethylolpropane (TMP) as a polyhydric alcohol was added dropwise. Thereafter, the reaction temperature was maintained at 70°C until the isocyanate group concentration in the flask reached the calculated value of 33%.
  • TMP trimethylolpropane
  • Example 1 a polyisocyanate composition was obtained in the same manner except that m-XDA was changed to 8 wt%.
  • Example 1 a polyisocyanate composition was obtained in the same manner except that m-XDA was changed to 5 wt%.
  • Example 1 an isocyanate compound and a polyisocyanate composition were obtained in the same manner as Example 1, except that m-XDA with a purity of 99.83% was purified to 99.97%.
  • Example 4 a polyisocyanate composition was obtained in the same manner except that m-XDA was changed to 8 wt%.
  • Example 4 a polyisocyanate composition was obtained in the same manner except that m-XDA was changed to 5 wt%.
  • a polyisocyanate composition was obtained in the same manner as in Example 1, except that m-XDA with a purity of 98.0% was used.
  • a polyisocyanate composition was obtained in the same manner as in Example 1, except that n-amyl acetate was used as the solvent.
  • Example 1 a polyisocyanate composition was obtained in the same manner as in Example 1, except that the temperature was changed from 0.5 to 1.02 kgf/cm 2 at room temperature during the salt formation reaction.
  • Example 1 the reaction was carried out by heating the reactor to a temperature of about 120°C during the salt formation reaction. As a result, the amount of evaporation of Accordingly, an isocyanate composition could not be obtained.
  • Example 1 a polyisocyanate composition was obtained in the same manner as in Example 1, except that the temperature of the reactor was cooled to about 15 ⁇ 1° C. during the salt formation reaction.
  • the GC used for analysis was HP-6890, and detection was performed using FID.
  • the column used was DB-17 (30m * 0.25mm * 0.5 ⁇ m), the carrier gas was nitrogen (1.0mL/min), the injection volume was 1 ⁇ l, and the oven temperature was 80°C -> 5°C/min -> 160°C (8 min) - > 20°C/min -> 280°C (18 min).
  • polyisocyanate compositions prepared in the examples and comparative examples were measured for chromaticity, NCO content, residual XDI content, and white turbidity according to the methods described below, and the results are shown in Table 2.
  • This mixed solution was filtered through a 1 ⁇ m PTFE filter and then injected into a mold consisting of a glass mold and tape.
  • This mold was placed in an oven and the temperature was gradually raised from 10°C to 120°C, and polymerization reaction was performed for 20 hours. After completion of polymerization, the mold was taken out of the oven and released to obtain a plastic lens. The obtained plastic lens was annealed at 120°C for 6 hours to prepare a final optical lens sample.
  • the degree of white clouding was evaluated with the naked eye under various light source conditions according to the following evaluation criteria, and the results are shown in Table 2.
  • L.H Light Haze
  • V.H Vol.H (Visual Haze): Haze observed under both fluorescent and zirconium lamps
  • Example 1 99.83 0.18 6 0.11 0.13 0.06 0.30 C 14
  • Example 2 99.83 0.07 5 0.09 0.10 0.04 0.23 C 9
  • Example 3 99.83 0.19 4 0.08 0.06 0.02 0.16 C 6
  • Example 4 99.97 0.10 6 0.03 0.11 0.004 0.144 C 7
  • Example 5 99.98 0.08 6 0.009 0.067 0.0009 0.0769 C 6
  • Example 6 99.98 0.07 5 0.003 0.05 0.0008 0.0538 C 6 Comparative Example 1 99.83 - - 0.23 2.12 0.11 2.46 V.H.I.
  • a high-purity xylene diisocyanate compound can be manufactured in high yield through a simple manufacturing process that adjusts the purity of the reaction composition and at the same time controls the content range of specific low-boiling compounds in the by-products. I was able to.
  • process efficiency was increased in the subsequent phosgene reaction, making it possible to produce high purity xylene diisocyanate.
  • the optical lens using this material achieved excellent transparency compared to the comparative example.
  • the chromaticity according to the APHA method showed a low value even after the polyisocyanate composition was manufactured using the xylene diisocyanate prepared according to the above method.

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Abstract

La présente invention concerne une technologie relative à : une composition de diisocyanate de xylène dans laquelle la quantité d'un composé à bas point d'ébullition est gérée ; ainsi qu'un procédé de préparation de ladite composition, selon lequel, lors de la production de diisocyanate de xylène à l'aide de phosgène, le contrôle de la pureté d'un composé amine et l'ajustement de la plage de quantités d'un composé à bas point d'ébullition dans des réactifs permettent de préparer un composé diisocyanate de xylène de haute pureté avec un rendement élevé.
PCT/KR2023/018490 2022-11-16 2023-11-16 Composition de diisocyanate de xylène et son procédé de préparation WO2024106985A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050012670A (ko) * 2003-07-25 2005-02-02 바이엘 머티리얼사이언스 아게 4,4'-메틸렌디페닐 디이소시아네이트 및2,4'-메틸렌디페닐 디이소시아네이트를 높은 함량으로갖는 디페닐메탄계 디이소시아네이트와폴리이소시아네이트의 혼합물의 제조 방법
KR20180104330A (ko) * 2016-04-11 2018-09-20 미쓰이 가가쿠 가부시키가이샤 자일릴렌 다이아이소사이아네이트 조성물, 수지 및 중합성 조성물
KR20190029446A (ko) * 2017-09-11 2019-03-20 한화케미칼 주식회사 지방족 이소시아네이트의 제조방법
KR20210100572A (ko) * 2019-03-21 2021-08-17 케이에스랩(주) 비염소화 유도체를 포함하는 이소시아네이트 화합물의 제조 방법 및 이들의 조성물
KR20220078316A (ko) * 2020-12-03 2022-06-10 에스케이씨 주식회사 자일릴렌디이소시아네이트 조성물 및 이를 포함하는 중합성 조성물

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050012670A (ko) * 2003-07-25 2005-02-02 바이엘 머티리얼사이언스 아게 4,4'-메틸렌디페닐 디이소시아네이트 및2,4'-메틸렌디페닐 디이소시아네이트를 높은 함량으로갖는 디페닐메탄계 디이소시아네이트와폴리이소시아네이트의 혼합물의 제조 방법
KR20180104330A (ko) * 2016-04-11 2018-09-20 미쓰이 가가쿠 가부시키가이샤 자일릴렌 다이아이소사이아네이트 조성물, 수지 및 중합성 조성물
KR20190029446A (ko) * 2017-09-11 2019-03-20 한화케미칼 주식회사 지방족 이소시아네이트의 제조방법
KR20210100572A (ko) * 2019-03-21 2021-08-17 케이에스랩(주) 비염소화 유도체를 포함하는 이소시아네이트 화합물의 제조 방법 및 이들의 조성물
KR20220078316A (ko) * 2020-12-03 2022-06-10 에스케이씨 주식회사 자일릴렌디이소시아네이트 조성물 및 이를 포함하는 중합성 조성물

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