Isocyanate composition, modified isocyanate, polyurethane resin, and optical material

Abstract

An isocyanate composition, a modified isocyanate, a polyurethane resin, and an optical material are provided, and the isocyanate composition has an effective factor of 3.90 to 5.70. By designing and controlling the effective factors, it has excellent reactivity and can be used to prepare resins such as high-performance polyurethanes and polythiourethanes, without undesirable phenomena such as gel formation during polymerization. Furthermore, the isocyanate composition can effectively improve the yellowing resistance, stability, and optical properties of products such as polyurethanes and polythiourethanes, and the resulting polyurethanes and polythiourethanes do not become cloudy or opaque. Optical materials prepared with the isocyanate composition have significantly reduced yellowness index and significantly reduced incidence of optical deformation, effectively improving the optical properties of the optical materials.

Description

[Technical Field]

[0001] The present application relates to the field of isocyanate technology, such as isocyanate compositions, modified isocyanates, polyurethane resins, and optical materials. [Background technology]

[0002] Compared to inorganic optical materials such as glass, optical resin materials have advantages such as being lightweight, break-resistant, shatter-resistant, and easy to dye, and are widely used in fields such as eyeglass lenses, mobile phone lenses, lamps, lenses, prisms, and electrical equipment. Currently known optical resin materials include polycarbonate (PC), polymethyl methacrylate (acrylic, PMMA), polyallyl diethylene glycol carbonate resin (PADC), and polythiourethane, among which polythiourethane has excellent overall performance in terms of transparency, refractive index, impact resistance, dyeability, and processability, making it one of the optical materials with the greatest potential for development.

[0003] Polythiourethanes, an important category of polyurethane materials, are obtained by polymerization of polythiol compounds and polyiso(thio)cyanate compounds. For example, CN101155848A discloses a polythiourethane-based polymerizable composition containing (A) an alicyclic isocyanate compound, (B) an aliphatic isocyanate compound, (C) at least one of a polythiol compound having one or more sulfur bonds per molecule or a polythiol compound having one or more polysulfide bonds per molecule, and (D) at least one of a polyhydroxyl compound having two or more hydroxyl groups per molecule and / or a hydroxyl-sulfhydryl compound having one or more hydroxyl groups and one or more mercaptans. The polythiourethane obtained from this polymerizable composition has excellent dyeability and strength. CN106414538A discloses a composition for preparing a transparent polythiourethane body, comprising a polyisocyanate component, a mercaptan component, and optional auxiliary agents and additives, wherein the polyisocyanate component is prepared by gas-phase phosgenation of an aliphatic, alicyclic, aromatic, or araliphatic polyamine, and contains at least one nitrile-type substance based on at least 0.005% by weight of the polyisocyanate component, the nitrile-type substance being derived from the same polyamine as the polyisocyanate, and the polythiourethane lens prepared by the composition has good transparency. CN108084386A discloses a polythiourethane resin composition for optical materials obtained by heat curing a composition containing an organic zirconium-bismuth alloy compound, an isocyanate compound, and a mercaptan compound. Using the organic zirconium-bismuth alloy compound as a catalyst, the composition can increase the pass rate of industrialized lens products without compromising the resin's performance, such as transparency, mechanical properties, and heat resistance, when used as plastic lenses.

[0004] The polythiourethanes disclosed in the related arts mainly focus on the transparency, mechanical properties, dyeability, heat resistance, etc. of the material. However, during the polymerization of polythiourethane materials, the resin always becomes cloudy and opaque, and the obtained polythiourethanes have problems such as yellowing and optical deformation. As a result, the quality of products such as eyeglass lenses and lenses becomes unacceptable, and the wide application of polythiourethanes in optical components such as eyeglass lenses and lenses is severely limited.

[0005] Therefore, the development of polythiourethanes with better performance, especially the reduction of the yellowness index and the incidence of optical distortion of polythiourethanes, has become an urgent issue to be solved in this field. Summary of the Invention [Problem to be solved by the invention]

[0006] The following is a summary of the subject matter described in detail herein, which is not intended to limit the scope of protection of the claims.

[0007] The examples of the present application provide an isocyanate composition, a modified isocyanate, a polyurethane resin, and an optical material. By effectively designing and controlling factors, the isocyanate composition can effectively improve the yellowing resistance and stability of the polyurethane resin and polythiourethane, significantly reduce the yellowness index and the incidence of optical deformation of the optical material, and impart excellent optical properties. [Means for solving the problem]

[0008] In a first aspect, the present embodiments provide an isocyanate composition, wherein the isocyanate composition has an effectiveness factor of 3.90 to 5.70.

[0009] The formula for calculating the effectiveness factor is shown in Equation I.

number

[0010] In Formula I, E is an effectiveness factor, In Formula I, A is the mass content of chlorine in the isocyanate composition; In Formula I, B is the mass content of chlorinated isocyanate in the isocyanate composition; In Formula I, M Cl is the relative atomic mass of chlorine, In Formula I, M B is the relative molecular mass of the chlorinated isocyanate.

[0011] The effective factor E of the isocyanate composition provided by the present application is 3.90 to 5.70, and may be, for example, 4.00, 4.10, 4.30, 4.50, 4.70, 4.90, 5.00, 5.10, 5.20, 5.30, 5.40, 5.50, or 5.60, as well as specific point values ​​between the above-mentioned point values, and for the sake of space and brevity, the present application does not exhaustively list specific point values ​​included in the above range.

[0012] In the present application, the isocyanate composition is defined as a "composition" because it includes a combination of an isocyanate and a chlorine-containing substance, and the chlorine-containing substance includes a chlorinated isocyanate and a substance corresponding to an effective factor. By designing and controlling the effective factors, the present application has made the isocyanate composition contain a specific type of chlorine-containing substance at a specific content and have excellent reactivity. This can be used to prepare resins such as high-performance polyurethanes and polythiourethanes without undesirable phenomena such as gelation during polymerization. Furthermore, the isocyanate composition can effectively improve the yellowing resistance, stability, and optical properties of resin products such as polyurethanes and polythiourethanes. The resulting polyurethanes and polythiourethanes are free from cloudiness and opacity, and have low yellowness indexes and low rates of optical distortion as optical materials, effectively improving the optical quality of the optical materials. If the effective factor is too high, when the isocyanate composition is used to prepare polyurethane or polythiourethane, gelation will occur during the polymerization reaction; if the effective factor is too low, it will affect the yellowing resistance and optical properties of polyurethane, polythiourethane, and the yellowing index of the optical material will be high, and the probability of optical deformation will increase.

[0013] In the present application, in formula I for calculating the effectiveness factor, A is the mass content of chlorine in the isocyanate composition, preferably obtained by X-ray fluorescence (XRF) testing.

[0014] Preferably, in formula I for calculating the effectiveness factor, B is the mass content of chlorinated isocyanate in the isocyanate composition, which is obtained by chromatography-mass spectrometry testing, preferably by gas chromatography-mass spectrometry (GCMS) testing.

[0015] During development, the present application discovered that the methods for expressing the chlorine content in isocyanates known in the related art do not allow for accurate control of the isocyanate's properties, making it difficult to effectively control the quality of polyurethane / polythiourethane, particularly its yellowing resistance and optical properties. Specifically, the test method for total chlorine content in standard GB / T 12009.1-1989 uses the oxygen flask combustion method to convert all chlorine (including bromine) in the isocyanate into inorganic chlorine (including bromine), followed by titration with silver nitrate. The total chlorine content in the isocyanate is measured, including the bromine content in the isocyanate. Standard GB / T 12009.2-2016 measures hydrolytic chlorine, specifically the chlorine released after the reaction of isocyanate with alcohol and water, i.e., highly active chlorine in the isocyanate, which also includes highly active bromine. Some monochlorinated isocyanates may also be hydrolyzed. The chlorine (including some bromine) content measured according to GB / T 12009.1-1989 or GB / T 12009.2-2016 cannot accurately represent the composition of the isocyanate, making it impossible to effectively control the properties of the isocyanate and polyurethane / polythiourethane.

[0016] In the preferred technical solution of the present application, in calculating the effective factor E, A is the total chlorine content (excluding bromine) obtained by XRF testing, and B is the chlorinated isocyanate content obtained by chromatography-mass spectrometry testing. The A and B values ​​are obtained by precise qualitative and quantitative analytical tests, so that the effective factor E can accurately indicate the polychlorinated substances and a portion of the hydrolyzed chlorine (excluding the hydrolyzed chlorine of monochlorinated isocyanates) in the isocyanate composition, making the chlorine content more accurate and clear. This portion of the chlorine content plays an important role in the activity of isocyanates and the properties of products such as polyurethanes and polythiourethanes, thereby realizing the adjustment of the properties of the isocyanate composition and improving the properties of the polyurethanes and polythiourethanes prepared thereby, and in particular has a significant impact on the significant improvement of the optical properties (yellowing index, optical distortion) of optical materials.

[0017] Preferably, the isocyanate is a diisocyanate, and more preferably, further comprises any one or a combination of at least two of metaxylylene diisocyanate (XDI), bis(isocyanatomethyl)cyclohexane (H6XDI), and bis(isocyanatomethyl)norbornane (NBDI).

[0018] In this application, unless otherwise stated, the recited isocyanates include all isomers thereof, for example, metaxylylene diisocyanate (XDI) is [ka] and the bis(isocyanatomethyl)cyclohexane (H6XDI) is [ka] and the bis(isocyanatomethyl)norbornane (NBDI) is [ka] is.

[0019] Preferably, the weight percent content of isocyanate in the isocyanate composition is ≧97%, such as 97.5%, 98%, 98.5%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, 99.92%, 99.95%, 99.98%, 99.99%, etc.

[0020] Preferably, the chlorine mass content (A value) in the isocyanate composition is 2 to 1000 ppm, such as 5 ppm, 10 ppm, 50 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, or 950 ppm, and specific values ​​between the above values. For the sake of space and brevity, the present application does not exhaustively list specific values ​​included in the above range, and more preferably, the A value is 15 to 500 ppm.

[0021] In this application, "ppm" means parts per million, 1 ppm means one part per million, and hereinafter the same expressions have the same meaning.

[0022] Preferably, the substance corresponding to the effective factor is: [ka] wherein R is a divalent group obtained by removing an NCO group in an isocyanate.

[0023] Preferably, R is [ka] (Isocyanate becomes XDI), [ka] (Isocyanate becomes H6XDI), [ka] (Isocyanate becomes NBDI) or a combination of at least two of them, where the wavy line represents the attachment point of the group.

[0024] Preferably, the chlorinated isocyanates are compounds obtained by substitution of one NCO group in an isocyanate by chlorine.

[0025] Preferably, the chlorinated isocyanate is [ka] (chloromethylbenzyl isocyanate CBI, isocyanate is XDI), [ka] (chloromethylisocyanatomethylcyclohexane CIC, isocyanate is H6XDI), [ka] (chloromethyl isocyanatomethyl norbornane CNBI, isocyanate is NBDI) or a combination of at least two thereof.

[0026] As used herein, the term "-" delimits a ring structure and indicates a point of attachment at any available position on the ring structure.

[0027] Preferably, the mass content (B value) of the chlorinated isocyanate in the isocyanate composition is 10 to 2000 ppm, such as 20 ppm, 50 ppm, 100 ppm, 300 ppm, 500 ppm, 700 ppm, 900 ppm, 1000 ppm, 1 to 100 ppm, 1300 ppm, 1500 ppm, 1700 ppm, or 1900 ppm, and specific values ​​between the above values. For the sake of space and brevity, the present application does not exhaustively list specific values ​​included in the above range, and more preferably, it is 80 to 1500 ppm.

[0028] In the present application, the substance corresponding to the effective factor, chlorinated isocyanate, may be produced as a by-product in the process of preparing isocyanate, or may be artificially added to obtain a desired content.

[0029] In a second aspect, an embodiment of the present application provides a method for preparing the isocyanate composition according to the first aspect, the method comprising reacting an amine compound with phosgene gas to obtain the isocyanate composition.

[0030] Preferably, the preparation method comprises: (1) a step of reacting an amine compound with phosgene gas to obtain a reaction product; (2) a step of removing the reaction product obtained in the step (1) to obtain a crude product, the removal step including a phosgene gas removal step and / or a solvent removal step; (3) A step of sequentially separating and purifying the crude product obtained in step (2) to obtain the isocyanate composition.

[0031] Preferably, in step (3), the separation results in a heavy component and an intermediate, and the mixture of the intermediate and the heavy component is purified to obtain the isocyanate composition, and the mass percent content of the heavy component in the mixture is 1 to 10%.

[0032] In the preferred technical solution of the present application, the component to be refined is a mixture of the intermediate and a heavy component, and the mass percentage content of the heavy component in the mixture is 1-10%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, and may be a specific value between the above-mentioned values. For the sake of space and brevity, the present application does not exhaustively list the specific value included in the above range, and more preferably, it is 2-10%.

[0033] Preferably, the heavy component obtained by the separation is directly mixed with the intermediate to obtain a mixture; or the heavy component obtained by the separation is used as a first heavy component, and the first heavy component is separated again to obtain a heavy component recovery material and a residual heavy component, and the heavy component recovery material is mixed with the intermediate to obtain the mixture, and the mass percentage content of the heavy component recovery material in the mixture is 1 to 10%.

[0034] In another preferred technical solution, the method for preparing the isocyanate composition includes mixing the isocyanate obtained by carbamate decomposition with the heavy component recovery material to obtain the isocyanate composition. Preferably, the mass percentage content of the heavy component recovery material in the isocyanate composition is 1-10% (e.g., 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%), more preferably 1-5%.

[0035] As a preferred technical solution of the present application, the method for preparing the isocyanate composition is a phosgenation method, i.e., an amine compound is reacted with phosgene gas to produce an isocyanate, and the amine compound includes a diamine and / or a diamine salt (e.g., a diamine hydrochloride obtained by reacting a diamine with HCl).

[0036] Preferably, the method for reacting the amine compound with phosgene gas includes, for example, three types of methods: a method for reacting a diamine with phosgene gas in a gas phase, also called a gas-phase phosgenation method; a method for reacting a diamine with phosgene gas in a liquid phase, also called a liquid-phase phosgenation method; and a method for reacting a diamine salt (e.g., diamine hydrochloride) with phosgene gas in a solvent, also called a diamine hydrochloride phosgenation method. The diamine hydrochloride phosgenation method is more preferred.

[0037] Preferably, the amine compound described in step (1) is a diamine hydrochloride.

[0038] Preferably, the diamine hydrochloride is prepared by a salt-forming process, which comprises reacting a diamine with hydrogen chloride in the presence of a reaction solvent to form a salt, and the salt-forming process actually produces a diamine hydrochloride-containing slurry, which is then directly used in the reaction with phosgene gas (isocyanation process).

[0039] Preferably, the salt-forming step specifically includes passing hydrogen chloride gas through a reaction solvent, adding an amine solution (containing the reaction solvent and the diamine), stirring and mixing, and subjecting the mixture to a salt-forming reaction to obtain the diamine hydrochloride.

[0040] Preferably, in the salt-forming step, the molar ratio of hydrogen chloride to diamine is (2 to 20):1, and may be, for example, 2.5:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, or 18:1, and more preferably (3 to 16):1.

[0041] Preferably, the mass percent content of the diamine in the amine solution is 1 to 50 wt.%, for example, 2 wt.%, 5 wt.%, 8 wt.%, 10 wt.%, 12 wt.%, 15 wt.%, 18 wt.%, 20 wt.%, 22 wt.%, 25 wt.%, 28 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, or 48 wt.%, and specific point values ​​between the above point values ​​are also possible. For the sake of space and brevity, the present application does not exhaustively list specific point values ​​included in the above range, and more preferably, it is 3 to 30 wt.%.

[0042] Preferably, the temperature of the salt-forming reaction is 0 to 160°C, for example, 5°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 80°C, 100°C, 110°C, 130°C, or 150°C, and may be a specific point value between the above points. For the sake of space and brevity, the present application does not exhaustively list specific points included in the above range, and the temperature is more preferably 10 to 150°C, and even more preferably 10 to 140°C.

[0043] Preferably, the salt formation step is carried out under atmospheric or pressurized conditions.

[0044] Preferably, the pressure (gauge pressure) in the salt-forming step is 0.01 to 10 MPa G, and may be, for example, 0.03 MPa G, 0.05 MPa G, 0.08 MPa G, 0.1 MPa G, 0.2 MPa G, 0.3 MPa G, 0.4 MPa G, 0.5 MPa G, 0.6 MPa G, 0.7 MPa G, 0.8 MPa G, or 0.9 MPa G, or a specific point value between the above-mentioned points; for the sake of space and brevity, the present application does not exhaustively list specific point values ​​included in the above range, and the pressure is more preferably 0.02 to 0.5 MPa G, and even more preferably 0.02 to 0.4 MPa G.

[0045] Preferably, step (1) specifically comprises passing phosgene gas through a diamine hydrochloride (slurry) to react with it, thereby obtaining a reaction product, that is, a diisocyanate-containing reaction liquid.

[0046] Preferably, the molar ratio of the phosgene gas to the diamine hydrochloride is (4 to 50):1, and may be, for example, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1, 20:1, 22:1, 25:1, 28:1, 30:1, 32:1, 35:1, 38:1, 40:1, 42:1, 45:1, or 48:1, more preferably (5 to 40):1, and even more preferably (5 to 30):1.

[0047] Preferably, the temperature of the reaction described in step (1) is 80 to 180°C, for example, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, or 170°C, and may be a specific point value between the above points, and for the sake of space and brevity, the present application does not exhaustively list specific point values ​​included in the above range, and more preferably, it is 100 to 170°C, and even more preferably, it is 100 to 160°C.

[0048] Preferably, the reaction time described in step (1) is 2 to 25 hours, for example, 3 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, or 24 hours, and may be any specific time point between the above-mentioned time points. For the sake of space and brevity, the present application does not exhaustively list any specific time points included in the above range, and more preferably, it is 4 to 20 hours.

[0049] Preferably, the reaction described in step (1) is carried out under atmospheric or elevated pressure conditions.

[0050] Preferably, the pressure (gauge pressure) of the reaction described in step (1) is 0 to 0.6 MPa G, for example, 0.0005 MPa G, 0.001 MPa G, 0.003 MPa G, 0.01 MPa G, 0.02 MPa G, 0.03 MPa G, 0.05 MPa G, 0.07 MPa G, 0.09 MPa G, 0.1 MPa G, 0.2 MPa G, 0.3 MPa G, 0.4 MPa G, or 0.5 MPa G, and may be a specific point value between the above-mentioned point values. For the sake of space and brevity, the present application does not exhaustively list specific point values ​​included in the above range, and more preferably, it is 0.005 to 0.4 MPa G, and even more preferably, it is 0.01 to 0.2 MPa G.

[0051] Preferably, the reaction described in step (1) (isocyanation step) is an intermittent step or a continuous step, and preferably a continuous step.

[0052] Here, the continuous process is a process in which the slurry (diamine hydrochloride) produced in the salt formation process (salt formation kettle) is continuously fed from a stirring tank to a reaction kettle other than the salt formation kettle, the diamine hydrochloride is reacted with phosgene gas in the reaction kettle, and the resulting reaction product (diisocyanate-containing reaction liquid) is continuously removed from the reaction kettle. The number of reaction kettle used in the continuous process is not specifically limited in the present application, and may be, for example, 2, 3, 4, 5, or more.

[0053] The reaction product obtained in step (1) can be subjected to a removal step (solvent removal step and / or phosgene gas removal step) and a separation and purification step, if necessary.

[0054] Preferably, the reaction solvent is an organic solvent, and examples thereof include, but are not limited to, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as octane and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane; halogenated aromatic hydrocarbons such as chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, and trichlorobenzene; nitrogen-containing compounds such as nitrobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N'-dimethylimidazolidinone; ethers such as dibutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; ketones such as heptanone, diisobutyl ketone, methyl isobutyl ketone, and methyl ethyl ketone; fatty acid esters such as ethyl acetate, butyl acetate, amyl acetate, and ethoxyethyl acetate; and aromatic carboxylic acid esters such as methyl salicylate, dimethyl phthalate, dibutyl phthalate, and methyl benzoate. The reaction solvents may be used alone or in combination of at least two.

[0055] Preferably, the reaction solvent comprises a halogenated aromatic hydrocarbon, more preferably chlorobenzene and / or dichlorobenzene.

[0056] Preferably, the phosgene gas removal treatment described in step (2) is carried out in a phosgene gas removal column.

[0057] Preferably, the solvent removal treatment described in step (2) is carried out in a solvent removal tower.

[0058] Preferably, the separation described in step (3) separates the intermediate (light component) from the heavy component, thereby achieving removal of the heavy component. Examples of the apparatus for the separation include, but are not limited to, a short-distance evaporator and a distillation column.

[0059] Preferably, the operating pressure of the short-distance evaporator is 0.05 to 4 KPa, for example, 0.08 KPa, 0.1 KPa, 0.3 KPa, 0.5 KPa, 0.8 KPa, 1 KPa, 1.2 KPa, 1.5 KPa, 1.8 KPa, 2 KPa, 2.2 KPa, 2.5 KPa, 2.8 KPa, 3 KPa, 3.2 KPa, 3.5 KPa, or 3.8 KPa, and may be any specific point value between the above points. For the sake of space and brevity, the present application does not exhaustively list the specific point values ​​included in the above range, and more preferably, it is 0.1 to 2.5 KPa.

[0060] In the preferred technical solution of the present application, the heavy component obtained by the separation contains various types of chlorine-containing substances with a high content, and the heavy component obtained by the separation is mixed with the intermediate (light component) obtained by the separation in a certain ratio to obtain a mixture, and then the mixture is purified, so that the types and contents of chlorine-containing substances in the product can be effectively adjusted, and the effective factor of the isocyanate composition can be 3.90 to 5.70.

[0061] Preferably, the mass percent content of the heavy component (heavy component recovery material) in the mixture is 1-10%, more preferably 2-10%, thereby achieving an effectiveness factor of the isocyanate composition of 3.90-5.70. If the amount of heavy component (heavy component recovery material) mixed in is too low, the effectiveness factor will be high, and undesirable phenomena such as gelation will easily occur when the isocyanate composition is used to prepare polyurethane / polythiourethane. If the amount of heavy component (heavy component recovery material) mixed in is too high, the effectiveness factor will be low, and the isocyanate composition will contain a large number of impurities, which will affect the colorfastness (yellowing) and stability of the polyurethane / polythiourethane and deteriorate the optical properties of the optical material.

[0062] Preferably, the heavy components to be mixed with the intermediate may be directly mixed with the intermediate, or may be obtained by cycle separation using a heavy component removal device, and then mixed with the intermediate.

[0063] Preferably, the purification method is an industrial separation technique known in the art, illustratively including, but not limited to, distillation, rectification, crystallization, and the like.

[0064] Preferably, the method of purification is rectification.

[0065] Preferably, the rectification is carried out in a rectification column, which preferably comprises a tray column or a packed column.

[0066] Preferably, the number of theoretical stages of the rectification column is 2 to 60, for example, 3, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, 52, 52, 55, or 58, and may be any specific stage value between the above-mentioned stages. For the sake of space and brevity, the present application does not exhaustively list the specific stage values ​​included in the above range, and more preferably, it is 5 to 40.

[0067] Preferably, the pressure at the top of the rectification column is 0.1 to 4 KPa, for example, 0.2 KPa, 0.5 KPa, 0.8 KPa, 1 KPa, 1.2 KPa, 1.5 KPa, 1.8 KPa, 2 KPa, 2.2 KPa, 2.5 KPa, 2.8 KPa, 3 KPa, 3.2 KPa, 3.5 KPa, or 3.8 KPa, and may be any specific value between the above-mentioned values. For the sake of space and brevity, the present application does not exhaustively list the specific values ​​included in the above range, and more preferably, it is 0.15 to 2.5 KPa.

[0068] Preferably, the top reflux ratio of the rectification column is 0.01 to 60, for example, 0.05, 0.1, 0.5, 1, 3, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, 50, 52, 55, or 58, and may be any specific value between the above-mentioned values. For the sake of space and brevity, the present application does not exhaustively list the specific values ​​included in the above range, and more preferably, it is 0.1 to 40.

[0069] In one preferred technical solution of the present application, the method for preparing the isocyanate composition includes steps (1a) to (3c): (1a) In the salt formation step, a diamine is subjected to a salt formation reaction with hydrogen chloride to obtain a diamine hydrochloride; (1) In the phosgenation step, the diamine hydrochloride obtained in step (1) is reacted with phosgene gas to obtain a reaction product; (2) In the removal step, the reaction product obtained in the step (1) is subjected to a removal treatment to obtain a crude product, and the removal treatment includes a phosgene gas removal treatment and / or a solvent removal treatment; (3a) In the separation step, the crude product obtained in step (2) is separated to obtain a heavy component and an intermediate (light component), (3b) In the heavy component recovery step, the intermediate obtained in step (3a) is mixed with the heavy component to obtain a mixture, and the mass percentage content of the heavy component in the mixture is 1-10%; or the heavy component obtained in step (3a) is subjected to secondary separation to obtain a heavy component recovery material and a residual heavy component, and the heavy component recovery material is mixed with the intermediate to obtain a mixture, and the mass percentage content of the heavy component recovery material in the mixture is 1-10%; In the purification step (3c), the mixture obtained in step (3b) is purified to obtain the isocyanate composition.

[0070] Illustratively, the preparation method, the flow chart of which is shown in Figure 1, includes a salt formation step 10, a phosgenation step 20, a removal step 30, a separation step 40, a heavy component recovery step 50, and a purification step 60. The salt formation step and the phosgenation step can be carried out intermittently or continuously, and when carried out continuously, they are carried out continuously using a reactor. By appropriately adjusting the mixing ratio of the heavy component and the intermediate, the phosgene gas supply ratio, reaction temperature, reaction pressure, average residence time, reflux ratio of the rectification column, etc., the effective factors of the isocyanate composition can be adjusted, and effective factors can be controlled by the ratio of the heavy component and the intermediate.

[0071] Specifically, taking the XDI composition as an example, the preparation method is as follows.

[0072] (1a) In the salt formation step, a kettle reaction is used, and one or two kettle vessels can be used. First, the reaction solvent is placed in the salt formation kettle. Then, hydrogen chloride and metaxylylenediamine (XDA) are added to the salt formation kettle in the above-mentioned ratio of hydrogen chloride to diamine. While the inside of the salt formation kettle is maintained at the above-mentioned salt formation temperature and pressure, the hydrogen chloride and amine solution are stirred and mixed with a stirring blade to obtain XDA hydrochloride. While hydrogen chloride gas and the amine solution are continuously supplied to the salt formation kettle, the XDA hydrochloride-containing slurry is continuously removed from the salt formation kettle and subjected to the phosgenation step.

[0073] (1) In the phosgenation process, a kettle reaction is used, with three or four kettle reactors used in succession, and the above-mentioned XDA hydrochloride is continuously fed to the phosgenation reactor. Phosgene gas is continuously fed at the above-mentioned feed rate by inserting pipes into the tops of phosgenation reactor 1, phosgenation reactor 2, and phosgenation reactor 3. Thereafter, the slurry and phosgene gas are stirred and mixed while maintaining the above-mentioned reaction temperature and reaction pressure inside the phosgenation reactor. This causes XDA hydrochloride to react with carbonyl chloride to produce XDI as the main component, CBI and other intermediates as by-products, and a reaction liquid is obtained.

[0074] This allows the salt formation step and the phosgenation step to be carried out continuously.

[0075] (2) The removal step is carried out using a phosgene gas removal tower and a solvent removal tower, and the above reaction solution is continuously sent to the middle of the phosgene gas removal tower. The reaction solution is subjected to removal of phosgene gas and hydrogen chloride, etc. using the phosgene gas removal tower, and the solvent in the reaction solution is removed using the solvent removal tower to obtain a crude XDI product.

[0076] (3a) In the separation step, the above XDI crude product is separated using a short-distance evaporator to remove heavy components, and an intermediate and a primary heavy component are obtained.

[0077] (3b) In the heavy component recovery process, the primary heavy component is recovered using a short-distance evaporator, and recovered in one cycle or in a cycle to obtain a heavy component recovery material and a secondary heavy component. The heavy component recovery material and the intermediate are mixed to obtain a mixture, which is then subjected to a purification process, and the mass percentage content of the heavy component recovery material in the mixture is 1 to 10%.

[0078] (3c) In the purification step, the above mixture is continuously sent into the column of a rectification tower, and then, under the above-mentioned rectification conditions (column bottom temperature, column top temperature, column top pressure, column bottom reflux ratio, column top reflux ratio, residence time), low boiling points are distilled off from the intermediate, and the XDI composition is obtained from the lower part of the column below the middle.

[0079] This allows for the continuous production of XDI compositions containing XDI, CBI, and substances corresponding to effective factors.

[0080] In a third aspect, embodiments of the present application provide a modified isocyanate, the modified isocyanate being obtainable by modifying the isocyanate composition according to the first aspect, the modified isocyanate containing any one or a combination of at least two of (a) isocyanuronato, (b) uretdione, (c) biuret, (d) carbamate, (e) urea, (f) iminooxadiazinedione, (g) allophanate, (h) uretonimine, and (i) carbodiimide.

[0081] Those skilled in the art can modify the isocyanate composition described above using a known method as necessary to obtain the modified isocyanate. The modified isocyanate is suitably used as a polyisocyanate component, and the active hydrogen group-containing substance is suitably used as a raw material for polyurethane resins and polythiourethane resins.

[0082] Specifically, the modified isocyanate containing the (a) isocyanuronato is an isocyanate trimer, and can be obtained, for example, by reacting an isocyanate composition in the presence of a known isocyanuration catalyst to convert the isocyanate therein into an isocyanurate.

[0083] The (b) uretdione-containing modified isocyanate can be obtained by heating the isocyanate composition at about 90 to 200°C or by reacting in the presence of a known uretdione-forming catalyst to uretdioneize (e.g., dimerize) the isocyanate.

[0084] The (c) biuret-containing modified isocyanate can be obtained by reacting the isocyanate composition with, for example, water, a tertiary alcohol (e.g., tert-butanol), a secondary amine (e.g., dimethylamine, diethylamine), or the like, and then further reacting the resulting mixture in the presence of a known biuretization catalyst.

[0085] The (d) carbamate-containing modified isocyanate can be obtained by reacting an isocyanate composition with a polyol component (such as trimethylolpropane).

[0086] The (e) urea-containing modified isocyanate can be obtained by reacting an isocyanate composition with water, a polyamine component (described later), and the like.

[0087] The (f) modified isocyanate containing iminooxadiazinedione is an asymmetric trimer of isocyanate and can be obtained by reacting an isocyanate composition in the presence of a known iminooxadiazinedione-forming catalyst to convert the isocyanate into iminooxadiazinedione (e.g., trimerization).

[0088] The (g) allophanate-containing modified isocyanate can be obtained by reacting an isocyanate composition with an alcohol and then further reacting the resulting mixture in the presence of a known allophanate-forming catalyst.

[0089] The (h) uretonimine-containing modified isocyanate can be obtained by reacting an isocyanate composition in the presence of a known carbodiimide catalyst to form a carbodiimide, and then adding an isocyanate to the carbodiimide.

[0090] The (i) carbodiimide-containing modified isocyanate can be obtained by reacting an isocyanate composition in the presence of a known carbodiimide catalyst.

[0091] The modified isocyanate may contain at least one of the above (a)-(i), or may contain at least two of them. Such modified isocyanates can be produced by appropriately combining the above reactions. The modified isocyanates may be used alone or in combination of two or more.

[0092] In a fourth aspect, an embodiment of the present application provides a polyurethane resin, the polyurethane resin being produced by reacting an isocyanate-type substance with an active hydrogen group-containing substance, the isocyanate-type substance including at least one of the isocyanate composition described in the first aspect and the modified isocyanate described in the third aspect.

[0093] Preferably, the active hydrogen groups include any one or a combination of at least two of hydroxyl, amino, and sulfhydryl.

[0094] Preferably, the active hydrogen group-containing substance includes any one or a combination of at least two of a polyol, a polyamine, and a polythiol.

[0095] In a fifth aspect, the present application provides an optical material, the optical material being formed by polymerization of an isocyanate-type substance and a polythiol compound, the isocyanate-type substance including at least one of the isocyanate composition described in the first aspect and the modified isocyanate described in the third aspect.

[0096] In this application, the optical material is a polythiourethane, and the polythiol compound refers to a compound containing at least two mercaptan groups (sulfhydryls).

[0097] Preferably, the optical material is applied to eyeglass lenses, lenses, prisms, lampshade materials, transparent packaging materials, transparent building materials, or electronic products. Specifically, the optical material is applied to lenses, plastic lenses, prisms, automotive lampshade materials, transparent roofing materials, lens materials for electronic devices (mobile phones or tablet computers), etc.

[0098] Preferably, the polythiol compound is methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(sulfhydrylmethyl)cyclohexane, bis(2-mercaptoethyl)thiomalate, 2,3-dimercapto-1-propanol(2-mercaptoacetate), 2,3-dimercapto-1-propanol(3-mercaptopropionate), diethyleneglycol, These include aliphatic polythiol compounds such as bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(sulfhydrylmethyl)-1,3-propanedithiol, bis(2-sulfhydrylethyl)ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane bis(2-mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), and tetra(sulfhydrylmethyl)methane.

[0099] Preferably, the polythiol compound is 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(sulfhydrylmethyl)benzene, 1,3-bis(sulfhydrylmethyl)benzene, 1,4-bis(sulfhydrylmethyl)benzene, 1,2-bis(sulfhydrylethyl)benzene, 1,3-bis(sulfhydrylethyl)benzene, 1,4-bis(sulfhydrylethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tri(sulfhydrylmethyl)benzene Further included are aromatic polythiol compounds such as benzene, 1,2,4-tri(sulfhydrylmethyl)benzene, 1,3,5-tri(sulfhydrylmethyl)benzene, 1,2,3-tri(sulfhydrylethyl)benzene, 1,2,4-tri(sulfhydrylethyl)benzene, 1,3,5-tri(sulfhydrylethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-bis(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-bis(p-mercaptophenyl)pentane.

[0100] Preferably, the polythiol compound further includes aromatic polythiol compounds containing sulfur atoms other than sulfhydryls, such as 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tri(mercaptomethylthio)benzene, 1,2,4-tri(mercaptomethylthio)benzene, 1,3,5-tri(mercaptomethylthio)benzene, 1,2,3-tri(mercaptoethylthio)benzene, 1,2,4-tri(mercaptoethylthio)benzene, 1,3,5-tri(mercaptoethylthio)benzene, and the like, and alkylated products thereof.

[0101] Preferably, the polythiol compound is bis(sulfhydrylmethyl) sulfide, bis(sulfhydrylmethyl) disulfide, bis(sulfhydrylethyl) sulfide, bis(sulfhydrylethyl) disulfide, bis(mercaptopropyl) sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)methane, 1,2,3-Tri(mercaptomethylthio)propane, 1,2,3-Tri(2-mercaptoethylthio)propane, 1,2,3-Tri(3-mercaptopropylthio)propane, 1,2,3-Tri(mercaptomethylthio)propane, 1,2,3-Tri(2-mercaptoethylthio)propane, 1,2,3-Tri(3-mercaptopropylthio)propane, 1,2-Bis((2-sulfhydrylethyl)thio)-3-sulfhydrylpropane, 4,8-Dimercaptomethyl-1,11-dimercapto-3,6,9 -trithioundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, bis(sulfhydrylmethyl)-3,6,9-trithia-1,11-undecanedithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfite and thioglycolic and mercaptopropionic acid esters thereof.

[0102] Preferably, the polythiol compound is hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxypropyl sulfide bis(2-mercaptoacetate), hydroxypropyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide Hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxypropyl disulfide bis(2-mercaptoacetate), hydroxypropyl disulfide bis(3-mercaptopropionate), 2-sulfhydryl ethyl ether bis(2-mercaptoacetate), 2-sulfhydryl ethyl ether bis(2-mercaptoacetate), hydryl ethyl ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoacetate), thiodipropionic acid bis(2-mercaptoacetate), 4,4-thiodibutyric acid bis(2-mercaptoacetate), thiodiglycolic acid bis(2-mercaptoacetate), dithiodipropionic acid bis(2 Further included are other aliphatic polythiol compounds containing sulfur atoms other than sulfhydryl and ester bonds, such as 4,4-dithiodibutyric acid bis(2-mercaptoacetate), thiodiglycolic acid bis(2,3-dimercaptopropyl ester), thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodiglycolic acid bis(2,3-dimercaptopropyl ester), and dithiodipropionic acid bis(2,3-dimercaptopropyl ester).

[0103] Preferably, the polythiol compound further includes a heterocyclic compound containing a sulfur atom other than sulfhydryl, such as 3,4-thiophenedithiol or 2,5-dimercapto-1,3,4-thiadiazole.

[0104] Preferably, the polythiol compound is 2-mercaptoethanol, 3-sulfhydryl-1,2-propanediol, glycerin bis(mercaptoacetate), 1-hydroxyl-4-sulfhydrylcyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol, methylparaben ... Further included are compounds containing hydroxyls other than sulfhydryls, such as erythritol tri(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tri(mercaptoacetate), dipentaerythritol penta(3-mercaptopropionate), hydroxymethyl-tri(mercaptoethylthiomethyl)methane, and 1-hydroxyethylthio-3-mercaptoethylthiobenzene.

[0105] Preferably, the polythiol compound is 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiocyclohexane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiopentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiohexane, 2,2-bis(mercaptomethylthio)ethanethiol, 2-(4,5-dimercapto-2-thiopentyl)-1,3-dithiolane, 2,2 -Bis(sulfhydrylmethyl)-1,3-dithiolane, 2,5-bis(4,4-bis(mercaptomethylthio)-2-thiobutyl)-1,4-dithiane, 2,2-bis(mercaptomethylthio)-1,3-propanedithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithioheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 4,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto tri-2,5-dithiohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiopropyl)-3,7-dithianonane, tri(2,2-bis(mercaptomethylthio)ethyl)methane, tri(4,4-bis(mercaptomethylthio)-2-thiobutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiobutyl)methane 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiadecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathiadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathioheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-Dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiohexadecane, 8-(bis(mercaptomethylthio)methyl)-3,4,12,13-tetrakis(mercaptomethylthio)1,15-dimercapto-2,5,7,9,11,14-hexathiopentadecane, 4,6-bis(3,5-bis(mercaptomethylthio)-7-sulfhydryl-2,6-dithioheptanethio)-1,3-dithiane, 4 -(3,5-bis(mercaptomethylthio)-7-sulfhydryl-2,6-dithioheptanethio)-6-mercaptomethylthio-1,3-dithiane, 1,1-bis(4-(6-mercaptomethylthio)-1,3-dithianitio)-3,3-bis(mercaptomethylthio)propane, 1,3-bis(4-(6-mercaptomethylthio)-1,3-dithianitio)-1,3-bis(mercaptomethylthio)propane, 1-(4-(6-mercaptomethylthio)-1,3-dithianitio)-3-(2,2-bis(mercaptomethylthio)ethyl)-7,9-bithiane bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1-(4-(6-mercaptomethylthio)-1,3-dithiantiio)-3-(2-(1,3-dithietane))methyl-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1,5-bis(4-(6-mercaptomethylthio)-1,3-dithiantiio)-3-(2-(1,3-dithietane))methyl-2,4-dithiopentane, 4,6-bis(3-(2-(1,3-dithietane))methyl-5-sulfhydryl-2,4-dithiopentylthio)-1 ,3-dithiane, 4,6-bis(4-(6-mercaptomethylthio)-1,3-dithianitio)-1,3-dithiane, 4-(4-(6-mercaptomethylthio)-1,3-dithianitio)-6-(4-(6-mercaptomethylthio)-1,3-dithianitio)-1,3-dithiane, 3-(2-(1,3-dithiethane))methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-(2-(1,3-dithiethane))methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-Dimercapto-2,6,8,10,12,16-hexathioheptadecane, 3-(2-(1,3-dithietane))methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathioheptadecane, 3,7-bis(2-(1,3-dithietane))methyl-1,9-dimercapto-2,4,6,8-tetrathiononane, 4-(3,4,8,9-tetrakis(mercaptomethylthio)-11-sulfhydryl-2,5,7,10-tetrathiaundecane)-5-mercaptomethyl mercaptomethylthio-1,3-dithiolane, 4,5-bis(3,4-bis(mercaptomethylthio)-6-sulfhydryl-2,5-dithiohexylthio)-1,3-dithiolane, 4-(3,4-bis(mercaptomethylthio)-6-sulfhydryl-2,5-dithiohexylthio)-5-mercaptomethylthio-1,3-dithiolane, 4-(3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-sulfhydryl-2,4,7-trithiooctyl)-5-mercaptomethylthio-1,3-dithiolane, 2-(bis(3,4-bis( 2-(3,4-bis(mercaptomethylthio)-6-sulfhydryl-2,5-dithiohexylthio)mercaptomethylthiomethyl-1,3-dithietane, 2-(3,4,8,9-tetrakis(mercaptomethylthio)-11-sulfhydryl-2,5,7,10-tetrathiaundecanethylthio)mercaptomethylthiomethyl-1,3-dithietane, 2-(3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio) (O)-8-sulfhydryl-2,4,7-trithiooctyl)mercaptomethylthiomethyl-1,3-dithietane, 4,5-bis(1-(2-(1,3-dithietane))-3-sulfhydryl-2-thiopropylthio)-1,3-dithiolane, 4-(1-(2-(1,3-dithietane))-3-sulfhydryl-2-thiopropylthio)-5-(1,2-bis(mercaptomethylthio)-4-sulfhydryl-3-thiobutylthio)-1,3-dithiolane, 2-(bis(4-(5-mercaptomethylthio-1,3-dithiopentyl)thio))methyl-1,Further included are compounds having a dithioacetal or dithioketal skeleton, such as 3-dithietane, 4-(4-(5-mercaptomethylthio-1,3-dithiopentyl)thio)-5-(1-(2-(1,3-dithietane))-3-sulfhydryl-2-thiopropylthio)-1,3-dithiolane, and oligomers thereof.

[0106] Preferably, the polythiol compound is tri(mercaptomethylthio)methane, tri(mercaptoethylthio)methane, 1,1,5,5-tetrakis(mercaptomethylthio)-2,4-dithiopentane, bis(4,4-bis(mercaptomethylthio)-1,3-dithiobutyl)(mercaptomethylthio)methane, tri(4,4-bis(mercaptomethylthio)-1,3-dithiobutyl)methane, 2,4,6-tri(mercaptomethylthio)-1 ,3,5-trithiocyclohexane, 2,4-bis(mercaptomethylthio)-1,3,5-trithiocyclohexane, 1,1,3,3-tetrakis(mercaptomethylthio)-2-thiopropane, bis(sulfhydrylmethyl)methylthio-1,3,5-trithiocyclohexane, tri((4-sulfhydrylmethyl-2,5-dithiocyclohexan-1-yl)methylthio)methane, 2,4-bis(mercaptomethylthio)-1,3-dithiolane , 2-mercaptoethylthio-4-sulfhydrylmethyl-1,3-dithiolane, 2-(2,3-dimercaptopropylthio)-1,3-dithiolane, 4-sulfhydrylmethyl-2-(2,3-dimercaptopropylthio)-1,3-dithiolane, 4-sulfhydrylmethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiolane, tri(2,2-bis(mercaptomethylthio)-1-thioethyl)methane, tri(3,3-bis Further included are compounds having a trithioprotocarboxylic acid ester skeleton, such as 2,4,6-tri(3,3-bis(mercaptomethylthio)-2-thiopropyl)methane, tri(4,4-bis(mercaptomethylthio)-3-thiobutyl)methane, 2,4,6-tri(3,3-bis(mercaptomethylthio)-2-thiopropyl)-1,3,5-trithiocyclohexane, tetrakis(3,3-bis(mercaptomethylthio)-2-thiopropyl)methane, and oligomers thereof.

[0107] Preferably, the polythiol compound further includes a compound having a tetrathioprotocarbonate skeleton, such as 3,3′-bis(mercaptomethylthio)-1,5-dimercapto-2,4-dithiopentane, 2,2′-bis(mercaptomethylthio)-1,3-dithiolane, 2,7-bis(sulfhydrylmethyl)-1,4,5,9-tetrathiaspiro[4,4]nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro[5,5]undecane, and oligomers thereof.

[0108] The polythiol compound is not limited to the compounds listed above. Each of the compounds listed above may be used alone or in combination of at least two types.

[0109] Preferably, the polythiol compound includes at least one of 1,2-bis((2-sulfhydrylethyl)thio)-3-sulfhydrylpropane, bis(sulfhydrylmethyl)-3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, or 2-mercaptoethanol.

[0110] Preferably, in preparing the optical material, the polymerization is carried out in the presence of a polymerization catalyst, and the polymerization catalyst is preferably an organotin compound, examples of which include, but are not limited to, dialkyltin halides such as dibutyltin dichloride and dimethyltin dichloride, and dialkyltin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctanoate and dibutyltin dilaurate.

[0111] Furthermore, according to the purpose, the raw materials for preparing the optical material may further contain optional auxiliary agents, and the auxiliary agents may, for example, include any one or at least two compositions of a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye, a filler, and a mold release agent, but are not limited to these.

[0112] Preferably, optical materials formed from polythiourethane resins are typically produced by injection molding polymerization. Specifically, a polythiol compound and an isocyanate substance are mixed, and an appropriate auxiliary is selectively added. This mixture (polymerizable composition) is degassed as needed by an appropriate method, then injected into an injection mold and typically slowly heated from low to high temperatures to polymerize. The optical material is then obtained by demolding.

[0113] Preferably, the polymerization temperature is 80 to 200°C, and may be, for example, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, or 190°C.

[0114] Preferably, the polymerization time is 1 to 24 hours, and may be, for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 11 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, or 23 hours.

[0115] As a preferred technical solution of the present application, when the isocyanate composition is used to prepare an optical material polythiourethane, the optical material can have excellent transparency, color stability, and yellowing resistance, and the incidence of optical deformation of the optical material can be significantly reduced (≦1%, 0-1%). Specifically, the yellowness index YI of the optical material prepared with the XDI composition is ≦1.60, and the yellowness index YI of the optical material prepared with the H6XDI composition or NBDI composition is ≦1.50.

[0116] In the preferred technical solutions of the present application, the transmittance of the optical material (polythiourethane) prepared from the XDI composition is 83.95-84.10%, the transmittance of the optical material (polythiourethane) prepared from the H6XDI composition is ≧86.0%, and the transmittance of the optical material (polythiourethane) prepared from the NBDI composition is 85.89-86.85%.

[0117] In the preferred technical solution of the present application, the glass transition temperature (Tg) of the optical material (polythiourethane) prepared from the XDI composition is 84.56-85.67°C, the glass transition temperature of the optical material (polythiourethane) prepared from the H6XDI composition is 89.08-89.67°C, and the glass transition temperature of the optical material (polythiourethane) prepared from the NBDI composition is 108.08-108.65°C. [Effects of the Invention]

[0118] Compared with the related art, the embodiments of the present application have the following beneficial effects:

[0119] The isocyanate composition provided in the examples of the present application has excellent reactivity through the effective design and control of factors, and can be used to prepare resins such as high-performance polyurethanes and polythiourethanes, without undesirable phenomena such as gel formation during polymerization. Furthermore, the isocyanate composition can effectively improve the yellowing resistance, stability, and optical properties of products such as polyurethanes and polythiourethanes, and the resulting polyurethanes and polythiourethanes do not become cloudy or opaque. Optical materials prepared with the isocyanate composition have high glass transition temperatures, good heat resistance, significantly reduced yellowness index, significantly reduced incidence of optical deformation, and high transmittance, thereby effectively improving the optical properties of the optical materials.

[0120] Other aspects may become apparent after reading and understanding the accompanying drawings and detailed description. [Brief explanation of the drawings]

[0121] The accompanying drawings are used to provide a further understanding of the technical solutions in the present specification, constitute a part of the specification, and, together with the examples of the present application, are used to explain the technical solutions in the specification, but are not intended to limit the technical solutions in the specification. [Figure 1] 1 is a flow chart of a method for preparing an isocyanate composition according to one particular embodiment of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0122] The technical solutions of the present invention are further described below by specific embodiments. It is obvious to those skilled in the art that the described examples are merely assistances for understanding the present application, and should not be regarded as specific limitations of the present application.

[0123] The components and test methods for the properties in this application are as follows.

[0124] 1. Measurement of chlorine mass content (A value) in isocyanate composition: XRF test Equipment: Energy dispersive X-ray fluorescence analyzer (ED-XRF), model number: MERAK-LE II Method: Standard addition method Principle and operation: In chromatography, a pure CCl4 standard sample is used as the Cl source and ethyl acetate is used as the diluent. The Cl element in the sample is excited by X-rays generated from an X-ray phototube, generating characteristic fluorescent X-rays. The intensity of the characteristic fluorescent X-rays is linearly related to the concentration of the element. A standard curve is plotted, and the extrapolated value is used as the Cl element content in the sample.

[0125] 2. Measurement of the mass content (B value) of chlorinated isocyanates in isocyanate compositions: GCMS test Analysis was carried out using gas chromatography mass spectrometry under the following conditions, and the contents in this specification are normalized contents. Analyzer: Agilent 5977B GCMS Column: DB-5 column, specifications: 30 m x 0.25 mm x 0.25 μm. Column temperature: held at 50°C for 2 minutes, heated to 80°C at a rate of 5 mL / min, then heated to 280°C at a rate of 15 mL / min and held at that temperature for 10 minutes. Separation ratio: no shunt Sample injection port temperature: 280°C Detection temperature: 300℃ Carrier gas: Helium gas Carrier gas flow rate: 1 mL / min (constant flow rate) Sample injection volume: 1 μL Detection method: Selected ion monitoring (SIM) mode (XDI selected ions are 160 / 126, H6XDI selected ions are 186 / 152, and NBDI selected ions are 198 / 164).

[0126] 3. Measurement of mass percent content of isocyanate in isocyanate composition: Gas chromatographic test Analysis was carried out using a gas chromatograph under the following conditions, and the contents in this specification are normalized contents. Analyzer: Agilent 7890B GC Column: DB-5 column, specifications: 0 m x 0.25 mm x 0.25 μm. Column temperature: 60°C was maintained for 1 minute, and the temperature was increased to 300°C at a rate of 10°C / min and maintained for 5 minutes. Separation ratio: 30:1 Sample injection port temperature: 280°C Detection temperature: 320℃ Carrier gas: Nitrogen gas Carrier gas flow rate: 1 mL / min (constant flow rate) Sample injection volume: 1 μL Detector: FID

[0127] In the specific embodiments below in this application, "parts" and "%" are by weight unless otherwise stated.

[0128] Example 1

[0129] The effective factor E of the XDI composition is 4.70, and the flowchart of the preparation method thereof is shown in Figure 1. Specifically, the XDI composition and the preparation method thereof include the following steps:

[0130] In the salt formation step, 800 parts by mass of chlorobenzene was placed in the salt formation kettle, the salt formation temperature in the salt formation kettle was adjusted to 25°C, and the salt formation pressure (gauge pressure) in the salt formation kettle was adjusted to 0.04 MPa G. HCl gas was continuously blown into the salt formation kettle at a rate of 85.8 parts by mass / h, and simultaneously, an amine solution of 1,3-XDA (1,3-benzenedimethanamine) (1,3-XDA mass concentration 8.0 wt.%, solvent chlorobenzene) was continuously added to the salt formation kettle at a rate of 1,000 parts by mass / h, resulting in a molar ratio of HCl to 1,3-XDA of 4:1, thereby producing a slurry containing 1,3-XDA hydrochloride, which was then fed to the phosgenation kettle.

[0131] In the phosgenation step, a slurry containing 1,3-XDA hydrochloride is supplied to a phosgenation kettle, phosgene gas is continuously passed through the phosgenation kettle at a rate of 581.5 parts by mass / h, the reaction temperature in the kettle is set to 145°C, the reaction pressure (gauge pressure) is set to 0.2 MPa G, the molar ratio of phosgene gas to 1,3-XDA hydrochloride is set to 10:1, and the residence time is set to 7 hours, thereby reacting 1,3-XDA hydrochloride with phosgene gas to produce 1,3-XDI, and a reaction product containing 1,3-XDI is obtained.

[0132] In the removal step, the reaction product obtained in the phosgenation step was continuously sent to a phosgene gas removal tower and a solvent removal tower, where it was subjected to phosgene gas removal treatment and solvent removal treatment, thereby preparing 108 parts by mass of a 1,3-XDI crude product.

[0133] In the separation step, the crude product was continuously supplied to a short-distance evaporator (heavy component remover), and 99.7 parts by mass of an intermediate from which heavy components had been removed and 6.3 parts by mass of primary heavy components were obtained.

[0134] In the heavy component recovery process, the primary heavy component was continuously fed to a secondary short-distance evaporator to obtain 2.03 parts by mass of heavy component recovery material and 4.27 parts by mass of residual heavy component. The intermediate was mixed at a rate of 99.7 parts by mass / h with the heavy component recovery material at a rate of 2.03 parts by mass / h to obtain a mixture, i.e., the mass percentage content of the heavy component recovery material in the mixture was 2%.

[0135] In the purification process, the mixture is continuously sent to a fractionation column, which is packed with packings equivalent to 25 theoretical plates, and in the fractionation column, light components are removed from the top, and an XDI composition is obtained from the middle of the column, thereby obtaining the target product. The rectification conditions in the rectification column were as follows: Bottom temperature: 145~150℃ Tower top temperature: 100~120℃ Top pressure: 0~50PaA Residence time: 2~4h Top reflux ratio: 10 Amount obtained in the rectification process: 96.2 parts by mass / h. This results in the XDI composition, wherein the mass content of 1,3-XDI is >99%, the mass content of chlorine (A value) is 108 ppm, the mass content of CBI (B value) is 450 ppm and the effectiveness factor E is 4.70.

[0136] Examples 2 to 5, Comparative Examples 1 to 2 The XDI composition and its preparation method, in which the effective factor E of the XDI composition is shown in Table 1, are the same as those in Example 1 except for some method-related parameters, and the specific details are shown in Table 1 (methods / parameters not shown in Table 1 are completely the same as those in Example 1). In Table 1, "HCl ratio" represents the molar amount of HCl when 1,3-XDA is converted to 1 mol in the salt formation step, "phosgene gas ratio" represents the molar amount of phosgene gas when 1,3-XDA hydrochloride is converted to 1 mol in the phosgenation step, and "heavy component recovery material ratio" represents the mass percent content of heavy components (recovery material) in the mixture in the heavy component recovery step. [Table 1]

[0137] Examples 6 to 10, Comparative Examples 3 to 4 The H6XDI composition and its preparation method, whose effective factor E of the H6XDI composition is shown in Table 2, are the same as those in Example 1, except that 1,3-XDA in the salt formation step is replaced with 1,3-H6XDA, and the sample injection rate is uniformly set to 1,000 mass parts / h, using an amine solution of 1,3-H6XDA (1,3-cyclohexanedimethylamine) (mass concentration: 8.0 wt.%, solvent: chlorobenzene). Some method parameters are different from those in Example 1, and the specific details are shown in Table 2 (methods / parameters not shown in Table 2 are completely the same as those in Example 1). In Table 2, "HCl ratio" represents the molar amount of HCl when 1,3-H6XDA is converted to 1 mole in the salt formation step, "phosgene gas ratio" represents the molar amount of phosgene gas when 1,3-H6XDA hydrochloride is converted to 1 mole in the phosgenation step, and "heavy component recovery material ratio" represents the mass percentage content of heavy components (recovery material) in the mixture in the heavy component recovery step. [Table 2]

[0138] Examples 11 to 15, Comparative Examples 5 to 6 The effective factor E of the NBDI composition and a method for preparing the same are shown in Table 3. The preparation process is the same as that of Example 1, except that 1,3-XDA is replaced with NBDA in the salt formation step, and a 1,3-NBDA (norbornanedimethylamine) amine solution (mass concentration: 8.0 wt. %, solvent: chlorobenzene) is used, with the sample injection rate uniformly set at 1,000 parts by mass / h. Some method parameters differ from those of Example 1, and their specific details are shown in Table 3 (methods / parameters not shown in Table 3 are completely the same as those of Example 1). In Table 3, "HCl ratio" represents the molar amount of HCl when NBDA is converted to 1 mole in the salt formation step; "phosgene gas ratio" represents the molar amount of phosgene gas when NBDA hydrochloride is converted to 1 mole in the phosgenation step; and "heavy component recovery material ratio" represents the mass percent content of the heavy component (recovery material) in the mixture in the heavy component recovery step. [Table 3]

[0139] Examples 16 to 18 and Comparative Examples 7 to 9 The method of Example 1 of the related art US005196572A was used to prepare XDI as Comparative Example 7. In this comparative example, XDI was prepared by thermal decomposition, and the product did not contain chlorine or effective factors. The heavy component recovery material of Example 1 was added to the product at a ratio of 4% (i.e., the mass percentage content of heavy components in the resulting mixture was 4%) to obtain Example 16.

[0140] The method according to Example 1 of US005196572A was similarly employed to prepare H6XDI, with the other reaction conditions remaining unchanged, and the raw material was replaced with 1,3-cyclohexanedimethylenedicarbamic acid dimethyl ester, resulting in Comparative Example 8. The heavy component recovery material in Example 6 was added to the product at a ratio of 4% (i.e., the mass percentage content of heavy components in the resulting mixture was 4%), resulting in Example 17.

[0141] The method according to Example 1 of US005196572A was similarly employed to prepare NBDI, with the raw material being replaced with norbornanedimethylenedicarbamic acid dimethyl ester, resulting in Comparative Example 9. The heavy component recovery material in Example 11 was added to the product at a ratio of 4% (i.e., the mass percent content of heavy components in the resulting mixture was 4%), resulting in Example 18.

[0142] Application Examples

[0143] The optical material, specifically, a plastic lens material, is a polythiourethane resin produced by polymerizing an isocyanate-type substance and a polythiol compound. The isocyanate-type substance is an isocyanate composition provided by Examples 1 to 18 and Comparative Examples 1 to 9, respectively, and the polythiol compound is 1,2-bis((2-sulfhydrylethyl)thio)-3-sulfhydrylpropane.

[0144] The specific method for preparing the optical material is as follows. A flask was charged with 0.001 parts by weight of dibutyltin dichloride, 0.07 parts by weight of an internal mold release agent (Stepan, ZELECUN, acidic phosphate ester), 0.05 parts by weight of an ultraviolet absorber (Sakai Chemical Industry Co., Ltd., Biosorb 583), and 36.4 parts by weight of the XDI composition (Examples 1-5, 16, Comparative Examples 1-2, 7). The total weight was 37.7 parts by weight relative to the H6XDI composition (Examples 6-10, 17, Comparative Examples 3-4, 8), and 39.9 parts by weight relative to the NBDI composition (Examples 11-15, 18, Comparative Examples 5-6, 9). The mixture was then stirred at 25°C for 1 hour to fully dissolve the polyisocyanate component. 33.6 parts by mass of 1,2-bis((2-sulfhydrylethyl)thio)-3-sulfhydrylpropane was added to and mixed with the polyisocyanate component to prepare a polymerizable composition. The polymerizable composition was degassed under a pressure of 600 Pa for 1 hour, filtered through a 3 μm PTFE filter, and then poured into a mold formed by a glass mold and tape. The mold was placed in an oven, and the temperature was slowly raised from 10°C to 120°C, and polymerization was carried out for 18 hours. After polymerization was completed, the mold was removed from the oven and demolded to obtain the optical material.

[0145] The optical material was subjected to a property test as follows.

[0146] (1) Yellowness Index (YI value) test The yellowness index of the lens is measured according to the method of national standard GB / T 2409-1980, The optical material to be measured was made into a circular flat plastic lens with a thickness of 9 mm and a diameter of 75 mm. The tristimulus values ​​x, y, and z were measured using a spectrophotometer, and the YI value was calculated using the following formula.

number

[0147] (2) Testing the incidence of optical deformation Optical deformation is a phenomenon in which a local refractive index differs from the normal refractive index of the surrounding area due to differences in material composition, etc. In this application, 100 lenses (with the same specifications as those used in the YI value test) were visually observed under a high-pressure mercury lamp, and lenses in which stripes were observed were determined to have optical deformation, and the incidence of optical deformation, i.e., incidence of optical deformation = 100% × number of optically deformed lenses / 100, was calculated.

[0148] (3) Transmittance test The transmittance of the lenses was tested in accordance with GB / T 10810.3-2006 "Spectacle lenses and related spectacle products Part 3: Transmittance specifications and measurement methods."

[0149] (4) Glass transition temperature (Tg) test The glass transition temperature, Tg, was tested using differential scanning calorimetry (DSC), with each sample tested three times in parallel and the average value taken. For the glass transition temperature (Tg) test, a high-pressure differential scanning calorimeter (METTLER HPDSC 1) manufactured by Mettler Toledo was used. The DSC test method consisted of a temperature rise scan from 30°C to 300°C, with a temperature rise rate of 10°C / min, in a nitrogen gas atmosphere with a nitrogen gas flow rate of 50mL / min.

[0150] Specific test results are shown in Tables 4, 5, and 6. [Table 4] [Table 5] [Table 6]

[0151] As is clear from the above characteristic test data, by controlling the effective factor of the isocyanate composition in the range of 3.90 to 5.70, the polythiourethane optical material prepared in this application has a low yellowness index and a low incidence of optical deformation, with the incidence of optical deformation being 0 to 1%. However, the optical materials prepared using the XDI composition have a yellowness index YI≦1.60, a YI of 1.41 to 1.60, a transmittance of 83.95 to 84.10%, and a Tg of 84.56 to 85.67°C; the optical materials prepared using the H6XDI composition have a YI≦1.50, a YI of 1.31 to 1.50, a transmittance of 86.03 to 86.72%, and a Tg of 89.08 to 89.67°C; and the optical materials prepared using the NBDI composition have a YI≦1.50, a YI of 1.32 to 1.50, a transmittance of 85.89 to 86.85%, and a Tg of 108.08 to 108.65°C, thereby achieving both excellent optical properties and heat resistance.

[0152] Although the present application describes the isocyanate composition, modified isocyanate, polyurethane resin, and optical material according to the present application using the above examples, the applicant declares that the present application is not limited to the above methods and processes, i.e., does not mean that the present application must be carried out depending on the above methods and processes. It is obvious to those skilled in the art that any improvements to the present application, equivalent substitution of the raw materials selected in the present application, addition of auxiliary components, selection of specific methods, etc., are all intended to be included in the scope of protection and disclosure of the present application. [Explanation of symbols]

[0153] 10-Salt formation process 20-Phosgenation process 30-Removal process 40-Separation process 50-Heavy component recovery process 60-Purification process

Claims

1. an isocyanate composition, wherein the isocyanate composition has an effectiveness factor of 3.90 to 5.70; The formula for calculating the effectiveness factor is shown in Equation I: [Equation 1] where E is the effective factor, A is the mass content of chlorine in the isocyanate composition, B is the mass content of chlorinated isocyanate in the isocyanate composition, M Ｃｌ is the relative atomic mass of chlorine, M Ｂ is the relative molecular mass of said chlorinated isocyanate.

2. 2. The isocyanate composition of claim 1, wherein A is obtained by X-ray fluorescence analysis testing.

3. 3. The isocyanate composition according to claim 1 or 2, wherein B is obtained by a chromatography-mass spectrometry test, and more preferably by a gas chromatography-mass spectrometry test.

4. The isocyanate composition according to any one of claims 1 to 3, wherein the isocyanate is a diisocyanate and preferably includes any one or a combination of at least two of metaxylylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and bis(isocyanatomethyl)norbornane.

5. 5. The isocyanate composition according to any one of claims 1 to 4, wherein the weight percent content of isocyanate in the isocyanate composition is ≥ 97%.

6. The substance corresponding to the effective factor is 【Chemistry 4】 any one or a combination of at least two of where R is a divalent group obtained by removing an NCO group in an isocyanate, Preferably, R is 【Chemistry 11】 Any one or a combination of at least two selected from The isocyanate composition according to any one of claims 1 to 5, wherein the wavy lines represent attachment points of the groups.

7. The chlorinated isocyanate is a compound obtained by substituting one NCO group of an isocyanate with chlorine; Preferably, the chlorinated isocyanate is 【Chemistry 12】 The isocyanate composition according to any one of claims 1 to 6, comprising any one or a combination of at least two of:

8. A method for preparing the isocyanate composition according to any one of claims 1 to 7, comprising reacting an amine compound with phosgene gas to obtain the isocyanate composition.

9. a step (1) of reacting an amine compound with phosgene gas to obtain a reaction product; a step (2) of removing the reaction product obtained in the step (1) to obtain a crude product, the removal step including a phosgene gas removal treatment and / or a solvent removal treatment; and step (3) of sequentially separating and purifying the crude product obtained in step (2) to obtain the isocyanate composition.

10. 10. The method of claim 9, wherein the separation in step (3) obtains a heavy component and an intermediate, and the mixture of the intermediate and the heavy component is purified to obtain the isocyanate composition, and the weight percent content of the heavy component in the mixture is 1-10%.

11. 11. The method of claim 10, wherein the purification method is rectification.

12. A modified isocyanate, which is obtained by modifying the isocyanate composition according to any one of claims 1 to 7, The modified isocyanate contains any one or a combination of at least two of (a) isocyanuronato, (b) uretdione, (c) biuret, (d) carbamate, (e) urea, (f) iminooxadiazinedione, (g) allophanate, (h) uretonimine, and (i) carbodiimide.

13. A polyurethane resin, the polyurethane resin being produced by reacting an isocyanate-type substance with an active hydrogen group-containing substance, the isocyanate-type substance including at least one of the isocyanate composition according to any one of claims 1 to 7 and the modified isocyanate according to claim 12.

14. An optical material, the optical material being produced by polymerizing an isocyanate-type substance and a polythiol compound, the isocyanate-type substance including at least one of the isocyanate composition according to any one of claims 1 to 7 and the modified isocyanate according to claim 12; Preferably, the polythiol compound includes at least one of 1,2-bis((2-sulfhydrylethyl)thio)-3-sulfhydrylpropane, bis(sulfhydrylmethyl)-3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, or 2-mercaptoethanol.

15. 15. The optical material according to claim 14, wherein the optical material is applied to eyeglass lenses, lenses, prisms, lampshade materials, transparent packaging materials, transparent building materials, or electronic products.

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