Isocyanate composition, modified isocyanate, polyurethane resin and optical material

Abstract

The present invention provides an isocyanate composition, modified isocyanate, polyurethane resin and optical material, and the effective factor of the isocyanate composition is 3.90-5.70. The present invention has excellent reactivity through the design and control of the effective factor, and can be used for the preparation of resins such as high-performance polyurethane and polythiourethane, and will not have adverse phenomena such as gel during polymerization. Moreover, the isocyanate composition can effectively improve the yellowing resistance, stability and optical properties of products such as polyurethane and polythiourethane, so that the obtained polyurethane and polythiourethane will not produce white turbidity and opaque phenomenon. The optical material prepared with the isocyanate composition has a significantly reduced yellowness index and a significantly reduced optical deformation incidence rate, which effectively improves the optical properties of optical materials.

Description

Technical Field

[0001] The invention belongs to the technical field of isocyanate, and in particular relates to an isocyanate composition, a modified isocyanate, a polyurethane resin and an optical material. Background Art

[0002] Compared with inorganic optical materials such as glass, optical resin materials have the advantages of being light, not easy to break, not easy to crack, and easy to dye, and are widely used in the fields of eyeglass lenses, mobile phone lenses, lighting, lenses, prisms, electrical equipment, etc. Currently known optical resin materials include polycarbonate (PC), polymethyl methacrylate (acrylic, PMMA), polyallyl diglycol carbonate resin (PADC) and polythiourethane, among which polythiourethane has excellent comprehensive performance in terms of transparency, refractive index, impact resistance, dyeability and processability, and is one of the optical materials with the greatest development potential.

[0003] Polythiourethane is an important branch of polyurethane materials, which is obtained by polymerization reaction of polythiol compounds and polyiso(thio)cyanate compounds. For example, CN101155848A discloses a polythiourethane polymerizable composition, which includes the following components: (A) alicyclic isocyanate compounds, (B) aliphatic isocyanate compounds, (C) at least one of polythiol compounds having more than one sulfur bond in one molecule or polythiol compounds having more than one polysulfide bond in one molecule, (D) at least one of polyhydroxy compounds having more than two hydroxyl groups in one molecule, and / or hydroxythiol compounds having more than one hydroxyl group and more than one thiol group; the polythiourethane obtained by the polymerizable composition has good dyeability and strength. CN106414538A discloses a composition for preparing a transparent polythiourethane body, comprising a polyisocyanate component, a thiol component and optional auxiliary agents and additives; wherein the polyisocyanate component is prepared by gas phase phosgenation of aliphatic, cycloaliphatic, aromatic or aromatic aliphatic polyamines, and contains at least 0.005 weight % of at least one nitrile substance based on the polyisocyanate component, and the nitrile substance and the polyisocyanate are derived from the same polyamine; the polythiourethane lens prepared by the above composition has good transparency. CN108084386A discloses a polythiourethane resin composition for optical materials, which is obtained by heating and curing a composition comprising an organic zirconium bismuth alloy composite, an isocyanate compound and a thiol compound; wherein the organic zirconium bismuth alloy composite is used as a catalyst, which can improve the qualified rate in the industrialization process of lens products without losing the resin properties such as transparency, mechanical and heat resistance for plastic lens use.

[0004] The polythiourethane disclosed in the prior art mainly focuses on the transparency, mechanical properties, dyeability and heat resistance of the material. However, during the polymerization process of the polythiourethane material, the resin often becomes turbid and opaque, and the obtained polythiourethane has problems such as yellowing and optical deformation, resulting in unqualified quality of products such as lenses and lenses, which seriously limits the wide application of polythiourethane in optical components such as lenses and lenses.

[0005] Therefore, developing polythiourethane with better performance, especially reducing the yellowness index and optical deformation incidence of polythiourethane, is an urgent problem to be solved in the art. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide an isocyanate composition, a modified isocyanate, a polyurethane resin and an optical material. The isocyanate composition can effectively improve the yellowing resistance and stability of the polyurethane resin and polythiourethane through the design and control of effective factors, significantly reduce the yellowness index and optical deformation incidence of the optical material, and give it excellent optical properties.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an isocyanate composition, wherein the effectiveness factor of the isocyanate composition is 3.90-5.70.

[0009] The calculation formula of the effective factor is shown in Formula I:

[0010]

[0011] In formula I, E is the effective factor;

[0012] In formula I, A is the mass content of chlorine in the isocyanate composition;

[0013] In formula I, B is the mass content of chloroisocyanate in the isocyanate composition;

[0014] In Formula I, M Cl is the relative atomic mass of chlorine;

[0015] In Formula I, M B is the relative molecular mass of the chloroisocyanate.

[0016] The effective factor E of the isocyanate composition provided by the present invention is 3.90-5.70, for example, it can be 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 point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0017] In the present invention, the isocyanate composition includes a combination of isocyanate and chlorine-containing substances, so it is defined as a "composition"; the chlorine-containing substances include chlorinated isocyanates and substances corresponding to effective factors. The present invention, through the design and control of the effective factor, makes the isocyanate composition include a specific type of chlorine-containing substances at a specific content, so that it has excellent reactivity, can be used for the preparation of high-performance polyurethane, polythiourethane and other resins, and will not have adverse phenomena such as gel during the polymerization process; moreover, the isocyanate composition can effectively improve the yellowing resistance, stability and optical properties of polyurethane, polythiourethane and other resin products, so that the obtained polyurethane and polythiourethane will not appear turbid and opaque, and as an optical material, it has a low yellowness index and a low incidence of optical deformation, which effectively improves the optical quality of the optical material. If the effective factor is too high, the isocyanate composition is used to prepare polyurethane or polythiourethane, and gel will appear in the polymerization reaction; if the effective factor is too low, it will affect the yellowing resistance and optical properties of polyurethane and polythiourethane, resulting in a higher yellowing index of the optical material and an increased probability of optical deformation.

[0018] In the present invention, in Formula I for calculating the effective factor, A is the mass content of chlorine in the isocyanate composition, preferably obtained by X-ray fluorescence spectrometry (XRF) testing.

[0019] Preferably, in formula I for calculating the effective factor, B is the mass content of chloroisocyanate in the isocyanate composition, which is obtained by chromatography-mass spectrometry, preferably by gas chromatography-mass spectrometry (GCMS).

[0020] The present invention has been found in the research that the characterization method of chlorine content in isocyanate known in the prior art cannot accurately control the performance of isocyanate, and thus cannot effectively control the quality of polyurethane / polythiourethane, especially the yellowing resistance and optical properties. Specifically, the test method for total chlorine content in standard GB / T 12009.1-1989 is an oxygen bottle combustion method, which converts all chlorine (including bromine) in isocyanate into inorganic chlorine (including bromine) and then uses silver nitrate titration to characterize all chlorine content in isocyanate, and includes the bromine content in isocyanate. Standard GB / T 12009.2-2016 measures hydrolyzed chlorine, specifically chlorine released after isocyanate reacts with alcohol and water, which is the more active chlorine in isocyanate, and also includes the more active bromine. Some monochloroisocyanates can also hydrolyze a part. The chlorine (and part of the bromine) content measured by GB / T 12009.1-1989 or GB / T12009.2-2016 cannot accurately indicate the component information of isocyanate, and cannot effectively control the performance of isocyanate and polyurethane / polythiourethane.

[0021] As a preferred technical solution of the present invention, in the calculation of 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 value and the B value are obtained by accurate qualitative and quantitative analysis methods, so that the effective factor E accurately characterizes the polychlorinated substances and part of the hydrolyzed chlorine (excluding the hydrolyzed chlorine of monochloroisocyanate) in the isocyanate composition, corresponding to a more refined and clear chlorine content. This part of the chlorine content plays a key role in the activity of isocyanate and the performance of products such as polyurethane and polythiourethane, thereby achieving the performance regulation of the isocyanate composition, thereby improving the performance of the polyurethane and polythiourethane prepared therefrom, especially having a significant improvement effect on the optical properties (yellowing index, optical deformation) of the optical material.

[0022] Preferably, the isocyanate is a diisocyanate, and more preferably includes any one or a combination of at least two of xylylene diisocyanate (XDI), diisocyanate methylcyclohexane (H6XDI), and diisocyanate methylnorbornane (NBDI).

[0023] In the present invention, unless otherwise specified, the isocyanates listed include all isomers thereof. For example, the xylylene diisocyanate (XDI) is The diisocyanate methyl cyclohexane (H6XDI) is The diisocyanate methyl norbornane (NBDI) is

[0024] Preferably, the mass percentage of isocyanate in the isocyanate composition is ≥97%, for example, 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.

[0025] Preferably, the mass content of chlorine in the isocyanate composition (A value) is 2-1000ppm, for example, it can be 5ppm, 10ppm, 50ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, 500ppm, 550ppm, 600ppm, 650ppm, 700ppm, 750ppm, 800ppm, 850ppm, 900ppm or 950ppm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively enumerates the specific point values ​​included in the range, and 15-500ppm is further preferred.

[0026] In the present invention, "ppm" means parts per million, and 1 ppm means one part per million; the same expressions hereinafter have the same meaning.

[0027] Preferably, the substance corresponding to the effective factor includes any one or a combination of at least two of the following compounds: Here, R is a divalent group obtained by removing the NCO group in isocyanate.

[0028] Preferably, said R is selected from (isocyanate is XDI), (isocyanate is H6XDI), (isocyanate is NBDI) or a combination of at least two thereof; wherein the wavy line represents the connection site of the group.

[0029] Preferably, the chlorinated isocyanate is a compound in which one NCO group in isocyanate is replaced by chlorine.

[0030] Preferably, the chloroisocyanate comprises (chloromethyl benzyl isocyanate CBI, isocyanate is XDI), (chloromethyl isocyanate methyl cyclohexane CIC, isocyanate is H6XDI), (chloromethylisocyanatomethylnorbornane CNBI, isocyanate is NBDI) or a combination of at least two thereof.

[0031] Herein, the expression of a ring structure crossed by “—” indicates that the connection site is at any position on the ring structure that can form a bond.

[0032] Preferably, the mass content (B value) of chloroisocyanate in the isocyanate composition is 10-2000ppm, for example, it can be 20ppm, 50ppm, 100ppm, 300ppm, 500ppm, 700ppm, 900ppm, 1000ppm, 1100ppm, 1300ppm, 1500ppm, 1700ppm or 1900ppm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 80-1500ppm is further preferred.

[0033] It should be noted that, in the present invention, the substance corresponding to the effective factor, chloroisocyanate, can be produced as a by-product in the preparation process of isocyanate, or can be artificially added to obtain the required content.

[0034] In a second aspect, the present invention provides a method for preparing the isocyanate composition as described in the first aspect, the preparation method comprising: reacting an amine compound with phosgene to obtain the isocyanate composition.

[0035] Preferably, the preparation method comprises the following steps:

[0036] (1) reacting an amine compound with phosgene to obtain a reaction product;

[0037] (2) performing a removal treatment on the reaction product obtained in step (1) to obtain a crude product; the removal treatment includes a phosgene removal treatment and / or a solvent removal treatment;

[0038] (3) Separating and refining the crude product obtained in step (2) in sequence to obtain the isocyanate composition.

[0039] Preferably, the separation in step (3) obtains a heavy component and an intermediate; the mixture of the intermediate and the heavy component is refined to obtain the isocyanate composition; and the weight percentage of the heavy component in the mixture is 1-10%.

[0040] As a preferred technical solution of the present invention, the component to be refined is a mixture of the intermediate and a heavy component, and the mass percentage of the heavy component in the mixture is 1-10%, for example, it can be 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 2-10% is further preferred.

[0041] Preferably, the separated heavy component can be directly mixed with the intermediate product to obtain a mixture; or, the separated heavy component is a primary heavy component, and the primary heavy component is separated again to obtain a heavy component recovery material and a residual heavy component; the heavy component recovery material is mixed with the intermediate product to obtain the mixture; the mass percentage of the heavy component recovery material in the mixture is 1-10%.

[0042] In another preferred technical solution, the preparation method of the isocyanate composition comprises: mixing the isocyanate obtained by the carbamate cleavage method with the heavy component recovery material to obtain the isocyanate composition. Preferably, the mass percentage of the heavy component recovery material in the isocyanate composition is 1-10% (e.g., 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.), and more preferably 1-5%.

[0043] As a preferred technical solution of the present invention, the preparation method of the isocyanate composition is a phosgenation method, that is, an amine compound reacts with phosgene to generate an isocyanate; the amine compound includes a diamine and / or a diamine salt (for example, a diamine hydrochloride obtained by reacting a diamine with HCl).

[0044] Preferably, the method for reacting the amine compound with phosgene illustratively includes the following three categories: a method in which a diamine reacts with phosgene in a gas phase, also known as a gas phase phosgenation method; a method in which a diamine reacts with phosgene in a liquid phase, also known as a liquid phase phosgenation method; a method in which a diamine salt (such as diamine hydrochloride) reacts with phosgene in a solvent, also known as a diamine hydrochloride phosgenation method, and the diamine hydrochloride phosgenation method is further preferred.

[0045] Preferably, the amine compound in step (1) is diamine hydrochloride.

[0046] 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 to obtain the diamine hydrochloride. The slurry containing the diamine hydrochloride is actually obtained in the salt-forming process, and the slurry is directly used in the reaction with phosgene (isocyanate process).

[0047] Preferably, the salt-forming step specifically comprises: introducing hydrogen chloride gas into the reaction solvent, then adding an amine solution (including the reaction solvent and diamine), stirring and mixing, and performing a salt-forming reaction to obtain the diamine hydrochloride.

[0048] Preferably, the molar ratio of hydrogen chloride to diamine in the salt-forming step is (2-20):1, for example, it can be 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 (3-16):1.

[0049] Preferably, the mass percentage of the diamine in the amine solution is 1-50wt.%, for example, it can be 2wt.%, 5wt.%, 8wt.%, 10wt.%, 12wt.%, 15wt.%, 18wt.%, 20wt.%, 22wt.%, 25wt.%, 28wt.%, 30wt.%, 35wt.%, 40wt.%, 45wt.% or 48wt.%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively enumerates the specific point values ​​included in the range, and 3-30wt.% is further preferred.

[0050] Preferably, the temperature of the salt-forming reaction is 0-160°C, for example, it can be 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, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range. It is further preferred to be 10-150°C, and even more preferred to be 10-140°C.

[0051] Preferably, the salt-forming step is carried out under normal pressure or pressurized conditions.

[0052] Preferably, the pressure (gauge pressure) of the salt-forming process is 0.01-1.0 MPa G, for example, it can be 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, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively enumerates the specific point values ​​included in the range. It is further preferred to be 0.02-0.5 MPa G, and even more preferred to be 0.02-0.4 MPa G.

[0053] Preferably, step (1) specifically comprises: introducing phosgene into diamine hydrochloride (slurry) to carry out a reaction to obtain a reaction product, namely a reaction solution containing diisocyanate.

[0054] Preferably, the molar ratio of phosgene to diamine hydrochloride is (4-50):1, for example, it can be 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 (5-40):1, and even more preferably (5-30):1.

[0055] Preferably, the reaction temperature in step (1) is 80-180°C, for example, it can be 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C or 170°C, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively enumerates the specific points included in the range, and 100-170°C is further preferred, and 100-160°C is even more preferred.

[0056] Preferably, the reaction time of step (1) is 2-25 h, for example, it can be 3 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h or 24 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively enumerates the specific point values ​​included in the range, and 4-20 h is further preferred.

[0057] Preferably, the reaction in step (1) is carried out under normal pressure or pressurized conditions.

[0058] Preferably, the pressure (gauge pressure) of the reaction in step (1) is 0-0.6 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, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively enumerates the specific points included in the range, and 0.005-0.4 MPa G is further preferred, and 0.01-0.2 MPa G is even more preferred.

[0059] Preferably, the reaction (isocyanate formation process) in step (1) is a batch process or a continuous process, preferably a continuous process.

[0060] The continuous process is that the slurry (diamine hydrochloride) generated in the salt-forming process (salting kettle) is continuously transported from the stirring tank to a reactor different from the salt-forming kettle, the diamine hydrochloride is reacted with phosgene in the reactor, and the obtained reaction product (reaction liquid containing diisocyanate) is continuously taken out from the reactor. The present invention does not specifically limit the number of reactors in the continuous process, and illustratively, it can be 2, 3, 4, 5 or more.

[0061] The reaction product obtained in step (1) may be subjected to a removal step (a desolvation step and / or a phosgene removal step) and a separation and purification step as necessary.

[0062] Preferably, the reaction solvent is an organic solvent, illustratively including but 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, aromatic carboxylic acid esters such as methyl salicylate, dimethyl phthalate, dibutyl phthalate, and methyl benzoate, etc.; the reaction solvent can be used alone or in combination of at least two.

[0063] Preferably, the reaction solvent comprises halogenated aromatic hydrocarbons, more preferably chlorobenzene and / or dichlorobenzene.

[0064] Preferably, the dephosgene treatment in step (2) is carried out in a dephosgene tower.

[0065] Preferably, the desolventizing treatment in step (2) is carried out in a desolventizing tower.

[0066] Preferably, the separation in step (3) separates the intermediate product (light component) from the heavy component to remove the heavy component; the separation device illustratively includes but is not limited to: a short-path evaporator and a distillation tower.

[0067] Preferably, the operating pressure of the short-path evaporator is 0.05-4 kPa, for example, it may be 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, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and it is further preferably 0.1-2.5 kPa.

[0068] As a preferred technical solution of the present invention, the separated heavy component contains chlorine-containing substances of many types and high contents. By adding the separated heavy component into the separated intermediate product (light component) in a certain proportion to obtain a mixture, and then refining the mixture, the types and contents of chlorine-containing substances in the product can be effectively regulated, so that the effective factor of the isocyanate composition is 3.90-5.70.

[0069] Preferably, the mass percentage of the heavy component (heavy component recycling material) in the mixture is 1-10%, more preferably 2-10%, so that the effective factor of the isocyanate composition is 3.90-5.70. If the amount of the heavy component (heavy component recycling material) added is too little, the effective factor is too high, and the isocyanate composition is used to prepare polyurethane / polythiourethane, which is prone to gelation and other undesirable phenomena; if the amount of the heavy component (heavy component recycling material) added is too high, resulting in a low effective factor, the isocyanate composition contains more impurities, affecting the color change resistance (yellowing) and stability of the polyurethane / polythiourethane, resulting in poor optical properties of the optical material.

[0070] Preferably, the heavy component mixed with the intermediate product can be directly back-blended into the intermediate product, or can be recycled and separated by a heavy component removal device to obtain a heavy component recovery material, which is then blended into the intermediate product.

[0071] Preferably, the refining method is an industrial separation technology known in the art, illustratively including but not limited to: distillation, rectification, crystallization, etc.

[0072] Preferably, the refining method is distillation.

[0073] Preferably, the distillation is carried out in a distillation tower, and the distillation tower preferably comprises a plate distillation tower or a packed distillation tower.

[0074] Preferably, the number of theoretical plates of the distillation tower is 2-60, for example, it can be 3, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, 52, 52, 55 or 58, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 5-40 is further preferred.

[0075] Preferably, the top pressure of the distillation tower is 0.1-4 kPa, for example, it can be 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, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and it is further preferably 0.15-2.5 kPa.

[0076] Preferably, the top reflux ratio of the distillation tower is 0.01-60, for example, it can be 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, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and it is further preferably 0.1-40.

[0077] In a preferred technical solution of the present invention, the method for preparing the isocyanate composition comprises the following steps:

[0078] (1a) Salt-forming step: diamine reacts with hydrogen chloride to form a salt to obtain diamine hydrochloride;

[0079] (1) Phosgenation step: reacting the diamine hydrochloride obtained in step (1) with phosgene to obtain a reaction product;

[0080] (2) Removal process: the reaction product obtained in step (1) is subjected to a removal treatment to obtain a crude product; the removal treatment includes a phosgene removal treatment and / or a solvent removal treatment;

[0081] (3a) Separation step: Separating the crude product obtained in step (2) to obtain a heavy component and an intermediate product (light component);

[0082] (3b) a heavy component recovery step: mixing the intermediate product obtained in step (3a) with the heavy component to obtain a mixture; the weight percentage of the heavy component in the mixture is 1-10%; or, performing a secondary separation on the heavy component obtained in step (3a) to obtain a heavy component recovery material and a residual heavy component; mixing the heavy component recovery material with the intermediate product to obtain a mixture; the weight percentage of the heavy component recovery material in the mixture is 1-10%;

[0083] (3c) Purification step: Purifying the mixture obtained in step (3b) to obtain the isocyanate composition.

[0084] For example, the process flow diagram of the preparation method is as follows Figure 1 As shown, it includes a salt-forming step 10, a phosgenation step 20, a removal step 30, a separation step 40, a heavy component recovery step 50, and a refining step 60. The salt-forming step and the phosgenation step can be implemented in an intermittent manner or a continuous manner, and the continuous manner is carried out in a kettle. The effective factor of the isocyanate composition is adjusted by appropriately adjusting the mixing ratio of the heavy component and the intermediate, the supply ratio of phosgene, the reaction temperature, the reaction pressure, the average residence time, the reflux ratio of the distillation tower, etc., and the effective factor is mainly controlled by the ratio of the heavy component to the intermediate.

[0085] Specifically, taking the XDI composition as an example, the preparation method thereof is as follows:

[0086] (1a) Salt-forming step: A kettle reaction is adopted, which can be a single kettle or two kettles; first, a reaction solvent is charged into the salt-forming kettle; then, hydrogen chloride and xylene diamine (XDA) are added to the salt-forming kettle in the above-mentioned ratio of hydrogen chloride to diamine; while the interior of the salt-forming kettle is maintained at the above-mentioned salt-forming temperature and pressure, hydrogen chloride and amine solution are stirred and mixed by a stirring blade, thereby obtaining XDA hydrochloride; while hydrogen chloride gas and amine solution are continuously supplied to the salt-forming kettle, a slurry containing XDA hydrochloride is continuously taken out from the salt-forming kettle and transported to the phosgenation step.

[0087] (1) Phosgenation step: adopting a tank reaction, three or four tanks continuously, the XDA hydrochloride is continuously fed to the phosgenation reactor, and phosgene is continuously introduced into the top of each of the first phosgenation reactor, the second phosgenation reactor and the third phosgenation reactor in the above-mentioned supply ratio by inserting a tube; then, while the inside of the phosgenation reactor is maintained at the above-mentioned reaction temperature and reaction pressure, the slurry and phosgene are stirred and mixed. Thus, the XDA hydrochloride reacts with phosgene to produce XDI as the main component, and CBI and other intermediates are produced as by-products to obtain a reaction liquid.

[0088] In this way, the salt-forming step and the phosgenation step are continuously performed.

[0089] (2) Removal process: A phosgene removal tower and a solvent removal tower are used to continuously transport the reaction liquid to the middle of the phosgene removal tower. Phosgene and hydrogen chloride are removed from the reaction liquid through the phosgene removal tower; then the solvent is removed from the reaction liquid through the solvent removal tower to obtain a crude XDI product.

[0090] (3a) Separation process: The crude XDI product is separated by a short-path evaporator to remove the heavy components, thereby obtaining an intermediate product and a primary heavy component.

[0091] (3b) Heavy component recovery process: The first-stage heavy component is recovered through a short-path evaporator to obtain a heavy component recovery material and a second-stage heavy component, which can be recovered in a single or cyclic manner; the heavy component recovery material is mixed with the intermediate product to obtain a mixture that enters a refining process; the mass percentage of the heavy component recovery material in the mixture is 1-10%.

[0092] (3c) Purification step: The above mixture is continuously conveyed to a distillation tower; then, under the above-mentioned distillation conditions (tower bottom temperature, tower top temperature, tower top pressure, tower bottom reflux ratio, tower top reflux ratio, residence time), low boiling points are distilled off from the intermediate product, and the XDI composition is collected from the lower middle part of the tower.

[0093] Thus, an XDI composition including XDI, CBI, and substances corresponding to the effective factors can be continuously manufactured.

[0094] In a third aspect, the present invention provides a modified isocyanate, wherein the modified isocyanate is obtained by modifying the isocyanate composition as described in the first aspect; the modified isocyanate comprises any one or a combination of at least two of the groups (a)-(i): (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazinedione group, (g) allophanate group, (h) uretonimine group, and (i) carbodiimide group.

[0095] Those skilled in the art can modify the aforementioned isocyanate composition using known methods as needed to obtain the modified isocyanate; the modified isocyanate is suitably used as a polyisocyanate component and a substance containing an active hydrogen group as a raw material for a polyurethane resin or a polythiourethane resin.

[0096] Specifically, the modified isocyanate containing the group (a) isocyanurate group is a trimer of isocyanate, which can be obtained, for example, by reacting an isocyanate composition in the presence of a known isocyanurate catalyst to isocyanurate the isocyanate therein.

[0097] The modified isocyanate containing the group (b) uretdione group can be obtained by heating the isocyanate composition at about 90-200° C. or reacting it in the presence of a known uretdione catalyst to uretdione the isocyanate (eg, dimerize it).

[0098] The modified isocyanate containing the group (c) biuret group can be obtained by reacting an isocyanate composition with, for example, water, a tertiary alcohol (e.g., tert-butyl alcohol), a secondary amine (e.g., dimethylamine, diethylamine, etc.), and then further reacting the composition in the presence of a known biuret catalyst.

[0099] The modified isocyanate containing the group (d) urethane group can be obtained by reacting an isocyanate composition with a polyol component (for example, trimethylolpropane).

[0100] The modified isocyanate containing the group (e) urea group can be obtained by reacting an isocyanate composition with water, a polyamine component (described later), and the like.

[0101] The modified isocyanate containing the group (f) iminooxadiazinedione group is an asymmetric trimer of isocyanate, and can be obtained by reacting an isocyanate composition in the presence of a known iminooxadiazinedione catalyst to subject the isocyanate to iminooxadiazinedione (eg, trimerization).

[0102] The modified isocyanate containing the group (g) an allophanate group can be obtained by reacting an isocyanate composition with an alcohol and then further reacting the same in the presence of a known allophanation catalyst.

[0103] The modified isocyanate containing the group (h) uretonimine group can be obtained by reacting an isocyanate composition in the presence of a known carbodiimide catalyst to form a carbodiimide group and then adding isocyanate to the carbodiimide group.

[0104] The modified isocyanate containing the group (i) carbodiimide group can be obtained by reacting an isocyanate composition in the presence of a known carbodiimidization catalyst.

[0105] It should be noted that the modified isocyanate may contain at least one of the above groups (a)-(i), or may contain at least two. Such a modified isocyanate may be generated by appropriately using the above reactions in combination. In addition, the modified isocyanate may be used alone or in combination of two or more.

[0106] In a fourth aspect, the present invention provides a polyurethane resin, which is formed by the reaction of an isocyanate substance and a substance containing an active hydrogen group; the isocyanate substance includes at least one of the isocyanate composition described in the first aspect and the modified isocyanate described in the third aspect.

[0107] Preferably, the active hydrogen group includes any one of a hydroxyl group, an amino group, and a thiol group, or a combination of at least two of them.

[0108] Preferably, the substance containing active hydrogen groups includes any one of polyols, polyamines, and polythiols, or a combination of at least two of them.

[0109] In a fifth aspect, the present invention provides an optical material, which is formed by polymerization of an isocyanate substance and a polythiol compound; the isocyanate substance includes at least one of the isocyanate composition described in the first aspect and the modified isocyanate described in the third aspect.

[0110] In the present invention, the optical material is polythiourethane; the polythiol compound refers to a compound containing at least two thiol groups (mercapto groups).

[0111] Preferably, the optical material is applied to 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, automobile lampshade materials, transparent roofing materials, lens materials of electronic devices (mobile phones or tablet computers), etc.

[0112] Preferably, the polythiol compound includes methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetriol, 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(mercaptomethyl)cyclohexane, bis(2-mercaptoethyl)thiomalate, 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-2 ...2-propanol (2-mer Aliphatic polythiol compounds such as mercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) 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 tetrakis(mercaptomethyl)methane.

[0113] Preferably, the polythiol compound further comprises 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2 ,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di(p-mercaptophenyl)pentane and other aromatic polythiol compounds.

[0114] Preferably, the polythiol compound also includes 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, and their alkylated products, etc., which contain sulfur atoms in addition to mercapto groups.

[0115] Preferably, the polythiol compound further comprises bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)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-mercaptopropyl)ethane, 1,3-Bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9 -trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptoethylthiomethyl)methane Aliphatic polythiol compounds containing sulfur atoms other than mercapto groups, such as bis(mercaptopropyl) sulfide, bis(1,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) disulfide, and bis(mercaptopropyl) disulfide, and their esters of mercaptoacetic acid and mercaptopropionic acid.

[0116] Preferably, the polythiol compound further comprises hydroxymethyl sulfide bis(2-thioglycolate), hydroxymethyl sulfide bis(3-thiopropionate), hydroxyethyl sulfide bis(2-thioglycolate), hydroxyethyl sulfide bis(3-thiopropionate), hydroxypropyl sulfide bis(2-thioglycolate), hydroxypropyl sulfide bis(3-thiopropionate), hydroxymethyl disulfide bis(2-thioglycolate), hydroxymethyl disulfide bis(3-thiopropionate), hydroxyethyl disulfide bis(2-thioglycolate), hydroxyethyl disulfide bis(3-thiopropionate), hydroxypropyl disulfide bis(2-thioglycolate), hydroxypropyl disulfide bis(3-thiopropionate), 2-thioethyl ether bis(2-thioglycolate), 2-thioethyl ether bis(3-thiopropionate), 1,4-dithiane- Aliphatic polythiol compounds containing sulfur atoms and ester bonds other than mercapto groups such as 2,5-diol bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate), bis(2-mercaptoacetate) of thiodiacetic acid, bis(2-mercaptoacetate) of thiodipropionic acid, bis(2-mercaptoacetate) of 4,4-thiodibutyric acid, bis(2-mercaptoacetate) of dithiodiacetic acid, bis(2-mercaptoacetate) of dithiodipropionic acid, bis(2-mercaptoacetate) of 4,4-dithiodibutyric acid, bis(2-mercaptoacetate) of thiodiacetic acid, bis(2,3-dimercaptopropyl ester) of thiodipropionic acid, bis(2,3-dimercaptopropyl ester) of dithiodiacetic acid, and bis(2,3-dimercaptopropyl ester) of dithiodipropionic acid.

[0117] Preferably, the polythiol compound further includes a heterocyclic compound containing a sulfur atom other than a thiol group, such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole.

[0118] Preferably, the polythiol compound also includes 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol di(thioglycolate), 1-hydroxy-4-mercaptocyclohexane, 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 tris(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tris(thioglycolate), dipentaerythritol penta(3-mercaptopropionate), hydroxymethyl-tris(mercaptoethylthiomethyl)methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene and other compounds containing hydroxyl groups in addition to mercapto groups.

[0119] Preferably, the polythiol compound further comprises 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiacyclohexane, 2,2-bis(mercaptomethylthio)ethanethiol, 2-(4,5-dimercapto-2-thiapentyl)-1,3-dithiacyclohexane, 2,2-bis(mercaptomethyl)-1,3-dithiacyclohexane, 2,5-bis(4,4-bis(mercaptomethylthio)-2-thiabutyl)-1,4-dithiane, 2,2-bis(mercaptomethylthio)-1,3 -Propanedithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 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-2,5-dithiahexane , 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclobutane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane , tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexa(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10- Tetrathiaundecane, 3,4,8,9,13,14-hexa(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-(bis(mercaptomethylthio)methyl)-3,4,12,13-tetra(mercaptomethylthio)1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis(3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio)-1,3-dithiane, 4-(3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio)-6-mercaptomethylthio-1,3-dithiane, 1,1-bis(4-(6-mercaptomethylthio)-1,3-dithianylthio)-3,3-bis(mercaptomethylthio)propane, 1,3-bis(4-(6-mercaptomethylthio)-1,3-dithianylthio)-1,3-bis(mercaptomethylthio)propane, 1-(4-(6-mercaptomethylthio)-1,3-dithianylthio)-3-(2,2-bis(mercaptomethylthio)ethyl)-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1-(4-(6-mercaptomethylthio)-1,3-dithianylthio)-3-(2-(1,3-dithianyl))methyl-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1,5-bis(4-(6-mercaptomethylthio)-1,3-dithianylthio)-3-(2-(1 ,3-dithiyl))methyl-2,4-dithiolane, 4,6-bis(3-(2-(1,3-dithiyl))methyl-5-mercapto-2,4-dithiolanethio)-1,3-dithiane, 4,6-bis(4-(6-mercaptomethylthio)-1,3-dithianethio)-1,3-dithiane, 4-(4-(6-mercaptomethylthio)-1,3-dithianethio)-6-(4-(6-mercaptomethylthio)-1,3-dithianethio)-1,3-dithiane, 3-(2-(1,3-dithiyl))methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-(2-(1,3-dithiyl))methyl-5-mercapto-2,4-dithiolanethio)-1,3-dithiane 3-(2-(1,3-dithiacyclobutyl))methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,7-bis(2-(1,3-dithiacyclobutyl))methyl-1,9-dimercapto-2,4,6,8-tetrathianonane, 4-(3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl)-5-mercaptomethylthio-1,3-dithiacyclopentane, 4,5-bis(3, 4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio)-1,3-dithiolane, 4-(3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio)-5-mercaptomethylthio-1,3-dithiolane, 4-(3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto -2,4,7-trithiaoctyl)-5-mercaptomethylthio-1,3-dithiolane, 2-(bis(3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio)methyl)-1,3-dithiolane, 2-(3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio)methyl-1,3-dithiolane,3-dithietane, 2-(3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio)mercaptomethylthiomethyl-1,3-dithietane, 2-(3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl)mercaptomethylthiomethyl-1,3-dithietane, 4,5-bis(1-(2-(1,3-dithietanyl))-3-mercapto-2-thiapropylthio)-1,3-dithiolane, 4-(1-(2-(1,3-dithietanyl))-3-mercapto-2-thiapropylthio)-1,3-dithiolane Compounds having a dithioacetal or dithioketal skeleton, such as 2-(4-(5-mercaptomethylthio-1,3-dithiolanyl)thio)-5-(1-(2-(1,3-dithiolanyl))-3-mercapto-2-thiopropylthio)-1,3-dithiolane, and oligomers thereof.

[0120] Preferably, the polythiol compound further comprises tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane, 1,1,5,5-tetra(mercaptomethylthio)-2,4-dithiapentane, bis(4,4-bis(mercaptomethylthio)-1,3-dithiabutyl)(mercaptomethylthio)methane, tris(4,4-bis(mercaptomethylthio)-1,3-dithiabutyl)methane, 2,4,6-tris(mercaptomethylthio)-1 ,3,5-trithiacyclohexane, 2,4-bis(mercaptomethylthio)-1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis(mercaptomethylthio)-2-thiacyclopropane, bis(mercaptomethyl)methylthio-1,3,5-trithiacyclohexane, tris((4-mercaptomethyl-2,5-dithiacyclohexyl-1-yl)methylthio)methane, 2,4-bis(mercaptomethylthio)-1,3-dithiacyclopentane, 2- Mercaptoethylthio-4-mercaptomethyl-1,3-dithiolane, 2-(2,3-dimercaptopropylthio)-1,3-dithiolane, 4-mercaptomethyl-2-(2,3-dimercaptopropylthio)-1,3-dithiolane, 4-mercaptomethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiolane, tris(2,2-bis(mercaptomethylthio)-1-thiaethyl)methane , tris(3,3-bis(mercaptomethylthio)-2-thiazole)methane, tris(4,4-bis(mercaptomethylthio)-3-thiazole)methane, 2,4,6-tris(3,3-bis(mercaptomethylthio)-2-thiazole)-1,3,5-trithiacyclohexane, tetrakis(3,3-bis(mercaptomethylthio)-2-thiazole)methane, and oligomers thereof having a trithioorthoformate skeleton.

[0121] Preferably, the polythiol compound also includes 3,3'-bis(mercaptomethylthio)-1,5-dimercapto-2,4-dithiapentane, 2,2'-bis(mercaptomethylthio)-1,3-dithiacyclopentane, 2,7-bis(mercaptomethyl)-1,4,5,9-tetrathiaspiro[4,4]nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro[5,5]undecane, and oligomers thereof, and the like having a tetrathioorthocarbonate skeleton.

[0122] It should be noted that the polythiol compound is not limited to the compounds listed above. In addition, the compounds listed above may be used alone or in combination of at least two.

[0123] Preferably, the polythiol compound includes at least one of 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane or 2-mercaptoethanol.

[0124] Preferably, in the preparation of the optical material, the polymerization is carried out in the presence of a polymerization catalyst, and the polymerization catalyst is preferably an organic tin compound, illustratively including but not limited to: dialkyl tin halides such as dibutyltin dichloride and dimethyltin dichloride; dialkyl tin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctoate, and dibutyltin dilaurate.

[0125] In addition, depending on the purpose, the raw materials for preparing the optical material also include optional auxiliary agents, which exemplarily include but are not limited to: any one of chain extenders, cross-linking agents, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, and release agents, or a combination of at least two of them.

[0126] Preferably, the optical material formed of polythiourethane resin is usually manufactured by injection polymerization. Specifically, the polythiol compound and the isocyanate substance are mixed, and a suitable auxiliary agent is optionally added. If necessary, the mixture (polymerizable composition) is degassed by an appropriate method and then injected into an injection mold for the optical material, and is usually slowly heated from a low temperature to a high temperature to polymerize it. Then, the optical material is obtained by demolding.

[0127] Preferably, the polymerization temperature is 80-200°C, for example, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, etc.

[0128] Preferably, the polymerization time is 1-24 h, for example, it can be 2 h, 4 h, 6 h, 8 h, 10 h, 11 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h or 23 h.

[0129] As a preferred technical solution of the present invention, the isocyanate composition is used for the preparation of polythiourethane as an optical material, which can make the optical material have excellent transparency, color stability, and yellowing resistance, and significantly reduce the incidence of optical deformation of the optical material (≤1%, 0-1%); specifically, the yellowness index YI of the optical material prepared with the XDI composition is ≤1.60, and the YI of the optical material prepared with the H6XDI composition and the NBDI composition is ≤1.50.

[0130] As a preferred technical solution of the present invention, the transmittance of the optical material (polythiourethane) prepared with the XDI composition is 83.95-84.10%, the transmittance of the optical material (polythiourethane) prepared with the H6XDI composition is ≥86.0%, and the transmittance of the optical material (polythiourethane) prepared with the NBDI composition is 85.89-86.85%.

[0131] As a preferred technical solution of the present invention, the glass transition temperature (Tg) of the optical material (polythiourethane) prepared with the XDI composition is 84.56-85.67°C, the glass transition temperature of the optical material (polythiourethane) prepared with the H6XDI composition is 89.08-89.67°C, and the glass transition temperature of the optical material (polythiourethane) prepared with the NBDI composition is 108.08-108.65°C.

[0132] Compared with the prior art, the present invention has the following beneficial effects:

[0133] The isocyanate composition provided by the present invention has excellent reactivity through the design and control of effective factors, and can be used for the preparation of high-performance polyurethane, polythiourethane and other resins, and will not have adverse phenomena such as gel during the polymerization process. Moreover, the isocyanate composition can effectively improve the yellowing resistance, stability and optical properties of polyurethane, polythiourethane and other products, so that the obtained polyurethane and polythiourethane will not appear turbid or opaque. The optical material prepared by the isocyanate composition has a high glass transition temperature, good heat resistance, a significantly reduced yellowness index and a significantly reduced optical deformation incidence, and a high transmittance, thereby effectively improving the optical properties of the optical material. BRIEF DESCRIPTION OF THE DRAWINGS

[0134] Figure 1 It is a schematic flow diagram of a method for preparing the isocyanate composition in a specific embodiment of the present invention;

[0135] Among them, 10 is a salt-forming step, 20 is a phosgenation step, 30 is a removal step, 40 is a separation step, 50 is a heavy component recovery step, and 60 is a refining step. DETAILED DESCRIPTION

[0136] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0137] The test methods of components and properties in the present invention are as follows:

[0138] 1. Determination of the mass content of chlorine (A value) in isocyanate composition: XRF test

[0139] Instrument: Energy dispersive X-ray fluorescence spectrometer (ED-XRF), model: MERAK-LE II;

[0140] Method: Standard addition method

[0141] Principle and operation: Chromatographically pure CCl4 standard is used as the Cl source, ethyl acetate is used as the diluent, and the X-rays generated by the X-ray tube excite the Cl element in the sample to produce characteristic X-ray fluorescence. The intensity of the characteristic X-ray fluorescence is linearly related to the element concentration. A standard curve is drawn, and the extrapolated value is the Cl content in the sample.

[0142] 2. Determination of the mass content (B value) of chloroisocyanate in isocyanate composition: GCMS test

[0143] The analysis was performed by gas chromatography-mass spectrometry under the following conditions, and the content in this article is the normalized content.

[0144] Analytical instrument: Agilent 5977B GCMS

[0145] Chromatographic column: DB-5 chromatographic column, specification: 30m×0.25mm×0.25μm

[0146] Column box temperature: 50℃ for 2 min, then increase the temperature to 80℃ at a rate of 5 mL / min, then increase the temperature to 280℃ at a rate of 15 mL / min, and maintain for 10 min

[0147] Separation ratio: No split

[0148] Inlet temperature: 280°C

[0149] Detection temperature: 300℃

[0150] Carrier gas: Helium

[0151] Carrier gas flow rate: 1mL / min (constant flow rate)

[0152] Injection volume: 1 μL

[0153] Detection method: SIM selected ion scanning mode (XDI selected ions are 160 / 126, H6XDI selected ions are 186 / 152, NBDI selected ions are 198 / 164)

[0154] 3. Determination of mass percentage of isocyanate in isocyanate composition: gas chromatography test

[0155] The analysis was carried out by gas chromatography under the following conditions, and the contents in this article are normalized contents.

[0156] Analytical instrument: Agilent 7890B GC

[0157] Chromatographic column: DB-5 chromatographic column, specification: 30m×0.25mm×0.25μm

[0158] Column box temperature: 60℃ for 1 min, then increase the temperature to 300℃ at a rate of 10℃ / min and keep for 5 min

[0159] Separation ratio: 30:1

[0160] Inlet temperature: 280°C

[0161] Detection temperature: 320℃

[0162] Carrier gas: Nitrogen

[0163] Carrier gas flow rate: 1mL / min (constant flow rate)

[0164] Injection volume: 1 μL

[0165] Detector: FID

[0166] In the following specific embodiments of the present invention, unless otherwise specified, "parts" and "%" are based on mass.

[0167] Example 1

[0168] An XDI composition and a preparation method thereof, wherein the effective factor E of the XDI composition is 4.70, and the flow diagram of the preparation method thereof is as follows Figure 1 As shown, the specific steps include:

[0169] Salt-forming step: 800 parts by mass of chlorobenzene were charged into the salt-forming kettle, the salt-forming temperature in the salt-forming kettle was adjusted to 25° C., and the salt-forming pressure (gauge pressure) in the salt-forming kettle was adjusted to 0.04 MPa G. HCl gas was continuously blown into the salt-forming kettle at a rate of 85.8 parts by mass / h, and an amine solution of 1,3-XDA (1,3-xylenediamine) (the mass concentration of 1,3-XDA was 8.0 wt.%, and the solvent was chlorobenzene) was continuously charged into the salt-forming kettle at a rate of 1000 parts by mass / h, so that the molar ratio of HCl to 1,3-XDA was 4:1, thereby generating a slurry containing 1,3-XDA hydrochloride, and the slurry containing 1,3-XDA hydrochloride was transported to the phosgenation kettle.

[0170] Phosgenation process: a slurry containing 1,3-XDA hydrochloride is transported to a phosgenation kettle, and phosgene is continuously introduced into the phosgenation kettle at a rate of 581.5 parts by mass / h. The reaction temperature in the kettle is 145° C., the reaction pressure (gauge pressure) is 0.2 MPa G, the molar ratio of phosgene to 1,3-XDA hydrochloride is 10:1, and the residence time is 7 hours. Thus, 1,3-XDA hydrochloride reacts with phosgene to generate 1,3-XDI, thereby obtaining a reaction product containing 1,3-XDI.

[0171] Removal step: The reaction product obtained in the phosgenation step was continuously transferred to a phosgenation removal tower and a solvent removal tower to perform phosgenation treatment and solvent removal treatment, respectively, thereby preparing 108 parts by mass of a crude 1,3-XDI product.

[0172] Separation process: The crude product is continuously conveyed to a short-path evaporator (heavy component removal device) to obtain 99.7 parts by weight of an intermediate product from which the heavy components are removed and 6.3 parts by weight of a primary heavy component.

[0173] Heavies recovery process: The primary heavies are continuously transported to the secondary short-path evaporator to obtain 2.03 parts by mass of heavies recovery material and 4.27 parts by mass of residual heavies. The intermediate product at a rate of 99.7 parts by mass / h is mixed with the heavies recovery material at a rate of 2.03 parts by mass / h to obtain a mixture, that is, the mass percentage of the heavies recovery material in the mixture is 2%.

[0174] Refining process: continuously convey the aforementioned mixture to a distillation tower. The distillation tower is filled with fillers equivalent to 25 theoretical plates, and then in the distillation tower, light components are removed from the top of the tower, and the XDI composition is extracted from the tower to obtain the target product;

[0175] The distillation conditions in the distillation tower are as follows:

[0176] Tower bottom temperature: 145-150℃

[0177] Tower top temperature: 100-120℃

[0178] Tower top pressure: 0-50PaA

[0179] Duration: 2-4 hours

[0180] Top reflux ratio: 10

[0181] The output of the distillation process is 96.2 parts by mass / h.

[0182] Thus, the XDI composition is obtained, wherein the mass content of 1,3-XDI is greater than 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.

[0183] Example 2-5, Comparative Example 1-2

[0184] An XDI composition and a preparation method thereof, wherein the effective factors E of the XDI composition are shown in Table 1, and the process of the preparation method thereof is the same as that of Example 1, except that some process parameters are different, which are specifically shown in Table 1 (the processes / parameters not shown in Table 1 are exactly the same as those in Example 1). In Table 1, "HCl ratio" indicates the molar amount of HCl in the salt-forming process based on 1,3-XDA as 1 mol; "phosgene ratio" indicates the molar amount of phosgene in the phosgenation process based on 1,3-XDA hydrochloride as 1 mol; "heavy component recovery material ratio" indicates the mass percentage of the heavy component (recovery material) in the mixture in the heavy component recovery process.

[0185] Table 1

[0186]

[0187]

[0188] Examples 6-10, Comparative Examples 3-4

[0189] A H6XDI composition and a preparation method thereof, wherein the effective factor E of the H6XDI composition is shown in Table 2, and the process of the preparation method thereof is the same as that of Example 1, except that the 1,3-XDA in the salt-forming process is replaced by 1,3-H6XDA, and the feed amount is kept consistent, which is 1000 parts by mass / h of 1,3-H6XDA (1,3-cyclohexyldimethylamine) amine solution (mass concentration is 8.0wt.%, and the solvent is chlorobenzene). Some process parameters are different, which are specifically shown in Table 2 (the process / parameters not shown in Table 2 are exactly the same as those in Example 1). In Table 2, "HCl ratio" indicates the molar amount of HCl in the salt-forming process based on 1,3-H6XDA as 1 mol; "phosgene ratio" indicates the molar amount of phosgene in the phosgenation process based on 1,3-H6XDA hydrochloride as 1 mol; "heavy component recovery material ratio" indicates the mass percentage of heavy components (recovered materials) in the mixture in the heavy component recovery process.

[0190] Table 2

[0191]

[0192]

[0193] Examples 11-15, Comparative Examples 5-6

[0194] A NBDI composition and a preparation method thereof, wherein the effective factor E of the NBDI composition is shown in Table 3, and the preparation method thereof is the same as that of Example 1, except that 1,3-XDA in the salt-forming process is replaced by NBDA, and the feed amount is kept the same, which is 1000 parts by mass / h of 1,3-NBDA (norbornane dimethylamine) amine solution (mass concentration is 8.0wt.%, and the solvent is chlorobenzene). Some process parameters are different, which are specifically shown in Table 3 (the process / parameters not shown in Table 3 are exactly the same as those in Example 1). In Table 3, "HCl ratio" indicates the molar amount of HCl in the salt-forming process based on NBDA as 1 mol; "phosgene ratio" indicates the molar amount of phosgene in the phosgenation process based on NBDA hydrochloride as 1 mol; "heavy component recovery material ratio" indicates the mass percentage of heavy components (recovery materials) in the mixture in the heavy component recovery process.

[0195] Table 3

[0196]

[0197]

[0198] Examples 16-18 and Comparative Examples 7-9

[0199] XDI was prepared as Comparative Example 7 by the method in Example 1 of the prior art US005196572A. This comparative example is a thermal cracking method for preparing XDI. The product does not contain chlorine and thus does not contain effective factors. The heavy component recovery material in Example 1 was added to the product at a ratio of 4% (i.e., the mass percentage of the heavy component in the obtained mixture was 4%) to obtain Example 16.

[0200] H6XDI was prepared by the method of Example 1 of US005196572A, except that the raw material was replaced with 1,3-cyclohexane dimethylene dicarbamic acid dimethyl ester, and other reaction conditions remained unchanged, as 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 of the heavy component in the obtained mixture was 4%), to obtain Example 17.

[0201] NBDI was prepared by the method of Example 1 of US005196572A, except that the raw material was replaced with dimethyl norbornane dimethylene dicarbamate, as 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 percentage of the heavy component in the obtained mixture was 4%), to obtain Example 18.

[0202] Application Examples

[0203] An optical material, specifically a plastic lens material, is a polythiourethane resin formed by the polymerization of an isocyanate substance and a polythiol compound; the isocyanate substance is the isocyanate composition provided in Examples 1-18 and Comparative Examples 1-9, and the polythiol compound is 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane.

[0204] The specific preparation method of the optical material is as follows:

[0205] 0.001 parts by mass of dibutyltin dichloride, 0.07 parts by mass of internal mold release agent (ZELECUN, acidic phosphate, manufactured by Stepan), 0.05 parts by mass of ultraviolet absorber (Biosorb 583, manufactured by Sakai Chemical Industry Co., Ltd.), 36.4 parts by mass of XDI composition (Examples 1-5, 16, Comparative Examples 1-2, 7); 37.7 parts by mass of H6XDI composition (Examples 6-10, 17, Comparative Examples 3-4, 8), and 39.9 parts by mass of NBDI composition (Examples 11-15, 18, Comparative Examples 5-6, 9) were added to the flask. Then, the mixture was stirred at 25°C for 1 hour to fully dissolve the mixture, thereby obtaining a polyisocyanate component.

[0206] 33.6 parts by mass of 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane was added to the polyisocyanate component and mixed to prepare a polymerizable composition;

[0207] The polymerizable composition was degassed for 1 hour at a pressure of 600 Pa, and then filtered with a 3 μm PTFE filter and injected into a casting mold formed by a glass mold and a tape. The casting mold was placed in an oven and slowly heated from 10° C. to 120° C. for 18 hours of polymerization. After the polymerization was completed, the casting mold was taken out of the oven and demolded to obtain the optical material.

[0208] The performance test of the above optical materials is carried out as follows:

[0209] (1) Yellowness index (YI value) test

[0210] The yellowness index of the lens is measured according to the method in the national standard GB / T 2409-1980;

[0211] The optical material to be tested is made into a circular flat plastic lens with a thickness of 9 mm and a diameter of 75 mm. The three stimulus values ​​x, y, and z are measured using a spectrophotometer. The YI value is calculated using the following formula:

[0212]

[0213] The smaller the YI value, the better the hue of the plastic lens; the larger the YI value, the worse the hue.

[0214] (2) Test of optical deformation incidence

[0215] Optical distortion refers to the phenomenon that the refractive index of a part is different from that of the surrounding part due to the different composition of the material. In the present invention, 100 lenses (with the same specifications as the lenses in the YI value test) are visually observed under a high-pressure mercury lamp, and the lenses with streaks are determined to be lenses with optical distortion, and the optical distortion incidence is calculated, that is, the optical distortion incidence = 100% × the number of lenses with optical distortion / 100.

[0216] (3) Transmittance test

[0217] The transmittance of the lens is tested according to GB / T 10810.3-2006 "Spectacle lenses and related eyewear products Part 3: Transmittance specifications and measurement methods".

[0218] (4) Glass transition temperature (Tg) test

[0219] The glass transition temperature Tg was tested by differential scanning calorimetry (DSC), and each sample was tested 3 times in parallel to take the average value;

[0220] Glass transition temperature (Tg) test: using Mettler-Toledo high pressure differential scanning calorimeter (METTLER HPDSC 1), DSC test method: 30°C-300°C, temperature scanning, heating rate of 10°C / min, nitrogen atmosphere, nitrogen flow rate of 50mL / min.

[0221] The specific test results are shown in Table 4, Table 5 and Table 6:

[0222] Table 4

[0223]

[0224] Table 5

[0225]

[0226]

[0227] Table 6

[0228]

[0229] Combined with the above performance test data, it can be seen that the present invention controls the effective factor of the isocyanate composition within the range of 3.90-5.70, so that the prepared polythiourethane optical material has a lower yellowness index and optical deformation incidence, and the optical deformation incidence is 0-1%. Among them, the optical material prepared with the XDI composition has a yellowness index YI≤1.60, a YI of 1.41-1.60, a transmittance of 83.95-84.10%, and a Tg of 84.56-85.67°C; the optical material prepared with the H6XDI composition has a YI≤1.50, a YI of 1.31-1.50, a transmittance of 86.03-86.72%, and a Tg of 89.08-89.67°C; the optical material prepared with the NBDI composition has a YI≤1.50, a YI of 1.32-1.50, a transmittance of 85.89-86.85%, and a Tg of 108.08-108.65°C, and has both excellent optical properties and heat resistance.

[0230] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the isocyanate composition, modified isocyanate, polyurethane resin and optical material of the present invention, but the present invention is not limited to the above-mentioned process steps, that is, it does not mean that the present invention must rely on the above-mentioned process steps to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An isocyanate composition, characterized in that The effectiveness factor of the isocyanate composition is 3.90-5.70; The calculation formula of the effective factor is shown in Formula I: Among them, E is the effective factor; A is the mass content of chlorine in the isocyanate composition; B is the mass content of chloroisocyanate in the isocyanate composition; M Cl is the relative atomic mass of chlorine; M B is the relative molecular mass of the chloroisocyanate; The mass content of chlorine in the isocyanate composition is 2-1000ppm; The A is obtained by X-ray fluorescence spectroscopy analysis test; The mass content of chloroisocyanate in the isocyanate composition is 10-1900ppm; The isocyanate is a diisocyanate; The diisocyanate is any one of xylylene diisocyanate, diisocyanate methyl cyclohexane, and diisocyanate methyl norbornane; The chloroisocyanate is Any of the following: The substance corresponding to the effective factor includes any one or a combination of at least two of the following compounds: Here, R is a divalent group obtained by removing the NCO group in isocyanate.

2. The isocyanate composition according to claim 1, characterized in that The B was obtained by chromatography-mass spectrometry.

3. The isocyanate composition according to claim 2, characterized in that The B was obtained by gas chromatography-mass spectrometry.

4. The isocyanate composition according to claim 1, characterized in that The mass percentage of isocyanate in the isocyanate composition is ≥97%.

5. A method for preparing the isocyanate composition according to any one of claims 1 to 4, characterized in that: The preparation method comprises: reacting an amine compound with phosgene to obtain the isocyanate composition.

6. The preparation method according to claim 5, characterized in that: The preparation method comprises the following steps: (1) reacting an amine compound with phosgene to obtain a reaction product; (2) performing a removal treatment on the reaction product obtained in step (1) to obtain a crude product; the removal treatment includes a phosgene removal treatment and / or a solvent removal treatment; (3) separating and refining the crude product obtained in step (2) in sequence to obtain the isocyanate composition; The separation in step (3) obtains a heavy component and an intermediate product; the heavy component obtained by separation is a primary heavy component, and the primary heavy component is separated again to obtain a heavy component recovery material and a residual heavy component; the heavy component recovery material is mixed with the intermediate product to obtain the mixture; the mass percentage of the heavy component recovery material in the mixture is 1-10%, and the mixture is refined to obtain the isocyanate composition.

7. The preparation method according to claim 6, characterized in that: The refining method is distillation.

8. A modified isocyanate, characterized in that: The modified isocyanate is obtained by modifying the isocyanate composition according to any one of claims 1 to 5.

9. The modified isocyanate according to claim 8, characterized in that The modified isocyanate comprises any one or a combination of at least two of the groups (a)-(i): (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazinedione group, (g) allophanate group, (h) uretonimine group, and (i) carbodiimide group.

10. A polyurethane resin, characterized in that The polyurethane resin is formed by the reaction of an isocyanate substance and a substance containing an active hydrogen group; the isocyanate substance includes at least one of the isocyanate composition according to any one of claims 1 to 4 and the modified isocyanate according to claim 8 or 9.

11. An optical material, characterized in that: The optical material is formed by polymerization of an isocyanate substance and a polythiol compound; the isocyanate substance comprises at least one of the isocyanate composition according to any one of claims 1 to 4 and the modified isocyanate according to claim 8 or 9.

12. The optical material according to claim 11, characterized in that The polythiol compound includes at least one of 1,2-bis((2-mercaptoethyl)thio)-3-mercaptopropane, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane or 2-mercaptoethanol.

13. The optical material according to claim 11, characterized in that The optical material is applied to lenses, lampshade materials, transparent packaging materials, transparent building materials or electronic products.

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