WO2024103321A1 - 一种异氰酸酯组合物、改性异氰酸酯、聚氨酯树脂和光学材料 - Google Patents

一种异氰酸酯组合物、改性异氰酸酯、聚氨酯树脂和光学材料 Download PDF

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WO2024103321A1
WO2024103321A1 PCT/CN2022/132417 CN2022132417W WO2024103321A1 WO 2024103321 A1 WO2024103321 A1 WO 2024103321A1 CN 2022132417 W CN2022132417 W CN 2022132417W WO 2024103321 A1 WO2024103321 A1 WO 2024103321A1
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isocyanate
bis
isocyanate composition
group
mercaptomethylthio
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PCT/CN2022/132417
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English (en)
French (fr)
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朱付林
姜腾飞
尚永华
李建峰
任一臻
郭耀允
王鹏飞
尹力
黎源
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万华化学集团股份有限公司
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Priority to PCT/CN2022/132417 priority Critical patent/WO2024103321A1/zh
Publication of WO2024103321A1 publication Critical patent/WO2024103321A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • Embodiments of the present application relate to the field of isocyanate technology, such as an isocyanate composition, a modified isocyanate, a polyurethane resin and an optical material.
  • optical resin materials 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.
  • 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.
  • Polythiourethane is an important branch of polyurethane materials, which is obtained by polymerization reaction of polythiol compounds and polyiso(thio)cyanate compounds.
  • 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% by 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.
  • the polythiourethane disclosed in the related art mainly focuses on the transparency, mechanical properties, dyeability and heat resistance of the 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.
  • the embodiments of the present application 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 impart excellent optical properties to the optical material.
  • an embodiment of the present application provides an isocyanate composition, wherein the effectiveness factor of the isocyanate composition is 3.90-5.70.
  • 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
  • MB is the relative molecular mass of the chloroisocyanate.
  • the effective factor E of the isocyanate composition provided in the present application 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 brevity, the present application no longer exhaustively lists the specific point values included in the said range.
  • 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.
  • This application uses the design and control of effective factors to make 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 polyurethanes, polythiourethanes 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.
  • 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.
  • A is the mass content of chlorine in the isocyanate composition, preferably obtained by X-ray fluorescence spectrometry (XRF) testing.
  • 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).
  • GCMS gas chromatography-mass spectrometry
  • the present application has found in the research that the characterization method of chlorine content in isocyanate known in the related 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.
  • the test method for total chlorine content in standard GB/T 12009.1-1989 is the 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 the chlorine released after isocyanate reacts with alcohol and water.
  • A is the total chlorine content (excluding bromine) obtained by XRF testing
  • 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, and then 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.
  • 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).
  • XDI xylylene diisocyanate
  • H6XDI diisocyanate methylcyclohexane
  • NBDI diisocyanate methylnorbornane
  • the isocyanates listed include all their isomers.
  • XDI xylene diisocyanate
  • H6XDI diisocyanate methyl cyclohexane
  • NBDI diisocyanate methyl norbornane
  • 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.
  • the mass content (A value) of chlorine in the isocyanate composition 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, this application no longer exhaustively lists the specific point values included in the range, and 15-500ppm is further preferred.
  • ppm means parts per million, and 1 ppm means one part per million; the same expressions used below have the same meaning.
  • the substance corresponding to the effective factor includes any one or a combination of at least two of the following compounds:
  • R is a divalent group obtained by removing the NCO group in isocyanate.
  • the 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.
  • the chlorinated isocyanate is a compound in which one NCO group in isocyanate is replaced by chlorine.
  • 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.
  • connection site is at any position on the ring structure that can form a bond.
  • 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, this application no longer exhaustively lists the specific point values included in the range, and 80-1500ppm is further preferred.
  • 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.
  • an embodiment of the present application 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.
  • the preparation method comprises the following steps:
  • the removal treatment includes a phosgene removal treatment and/or a solvent removal treatment
  • step (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; 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%.
  • 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 application no longer exhaustively lists the specific point values included in the range, and 2-10% is further preferred.
  • 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%.
  • 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.
  • 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%.
  • 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).
  • 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.
  • 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 diamine salt such as diamine
  • the amine compound in step (1) is diamine hydrochloride.
  • 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 diamine hydrochloride is actually obtained in the salt-forming process, and the slurry is directly used in the reaction with phosgene (isocyanate process).
  • 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.
  • 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.
  • 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, this application no longer exhaustively lists the specific point values included in the range, and 3-30wt.% is further preferred.
  • 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 brevity, this application 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.
  • the salt-forming step is carried out under normal pressure or pressurized conditions.
  • the pressure (gauge pressure) of the salt-forming process is 0.01-1.0 MPa G, for example, it may 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 brevity, this application no longer exhaustively lists the specific point values included in the range, and 0.02-0.5 MPa G is further preferred, and 0.02-0.4 MPa G is even more preferred.
  • 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.
  • 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.
  • 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 brevity, this application no longer exhaustively lists the specific points included in the range, and 100-170°C is further preferred, and 100-160°C is even more preferred.
  • 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 brevity, this application no longer exhaustively lists the specific point values included in the range, and 4-20 h is further preferred.
  • reaction in step (1) is carried out under normal pressure or pressurized conditions.
  • the pressure (gauge pressure) of the reaction in step (1) is 0-0.6 MPa G, for example, it may be 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 point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range, and 0.005-0.4 MPa G is further preferred, and 0.01-0.2 MPa G is further preferred.
  • the reaction (isocyanate formation process) in step (1) is a batch process or a continuous process, preferably a continuous process.
  • 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 number of reactors in the continuous process is not specifically limited in the present application, and illustratively, it can be 2, 3, 4, 5 or more.
  • 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.
  • a removal step a desolvation step and/or a phosgene removal step
  • 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
  • the reaction solvent comprises halogenated aromatic hydrocarbons, more preferably chlorobenzene and/or dichlorobenzene.
  • the dephosgene treatment in step (2) is carried out in a dephosgene tower.
  • the desolventizing treatment in step (2) is carried out in a desolventizing tower.
  • 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.
  • 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 brevity, this application no longer exhaustively lists the specific point values included in the range, and it is further preferably 0.1-2.5 kPa.
  • the separated heavy component contains chlorine-containing substances of many types and high content.
  • 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.
  • the heavy component mixed with the intermediate product can be directly back-mixed 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 mixed into the intermediate product.
  • the refining method is an industrial separation technology known in the art, illustratively including but not limited to: distillation, rectification, crystallization, etc.
  • the refining method is distillation.
  • the distillation is carried out in a distillation tower, and the distillation tower preferably comprises a plate distillation tower or a packed distillation tower.
  • 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 brevity, this application no longer exhaustively lists the specific point values included in the range, and 5-40 is further preferred.
  • 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 brevity, this application no longer exhaustively lists the specific point values included in the range, and it is further preferably 0.15-2.5 kPa.
  • 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 brevity, this application no longer exhaustively lists the specific point values included in the range, and it is further preferably 0.1-40.
  • the method for preparing the isocyanate composition comprises the following steps:
  • Salt-forming step diamine reacts with hydrogen chloride to form a salt to obtain diamine hydrochloride;
  • Phosgenation step reacting the diamine hydrochloride obtained in step (1) with phosgene to obtain a reaction product
  • Step (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;
  • step (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%;
  • Step (3c) Purification step: Purifying the mixture obtained in step (3b) to obtain the isocyanate composition.
  • the process diagram of the preparation method is shown in Figure 1, including 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 continuously in an autoclave.
  • 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 control of the effective factor is mainly achieved by the ratio of the heavy component to the intermediate.
  • the preparation method thereof is as follows:
  • 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.
  • XDA xylene diamine
  • 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.
  • 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.
  • 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.
  • 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%.
  • an XDI composition including XDI, CBI, and substances corresponding to the effective factors can be continuously manufactured.
  • an embodiment of the present application 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.
  • 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
  • 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.
  • 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.
  • 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).
  • 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.
  • a tertiary alcohol e.g., tert-butyl alcohol
  • a secondary amine e.g., dimethylamine, diethylamine, etc.
  • the modified isocyanate containing the group (d) urethane group can be obtained by reacting an isocyanate composition with a polyol component (for example, trimethylolpropane).
  • a polyol component for example, trimethylolpropane
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • an embodiment of the present application provides a polyurethane resin, which is formed by the reaction of an isocyanate substance with 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.
  • the active hydrogen group includes any one of hydroxyl, amino, and thiol, or a combination of at least two of them.
  • the substance containing active hydrogen groups includes any one of polyols, polyamines, and polythiols, or a combination of at least two of them.
  • the present application 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.
  • the optical material is polythiourethane;
  • the polythiol compound refers to a compound containing at least two thiol groups (sulfhydryl groups).
  • the optical material is applied to 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.
  • 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-dimercap
  • 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(mercaptoeth
  • 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.
  • 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,
  • 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(2-thioglycolate), 2-thioethyl ether bis(2-thioeth
  • the polythiol compound also includes heterocyclic compounds containing sulfur atoms other than thiol groups, such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole.
  • heterocyclic compounds containing sulfur atoms other than thiol groups such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole.
  • 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), hydroxy
  • 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-dithiacyclopentane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiacyclopentane, 2,2-bis(mercaptomethylthio)ethanethiol, 2-(4,5-dimercapto-2-thiapentyl)-1,3-dithiacyclopentane, 2,2-bis(mercaptomethyl)-1,3-dithiacyclopentane, 2,5-bis(4,4- Bis(mercaptomethylthio)-2-thiabutyl)-1,4-dithiane, 2,2-bis(mercaptomethyl)-1,
  • 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(((mercap
  • 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.
  • polythiol compound is not limited to the compounds listed above.
  • the compounds listed above may be used alone or in combination of at least two.
  • 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.
  • 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.
  • dialkyl tin halides such as dibutyltin dichloride and dimethyltin dichloride
  • dialkyl tin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctoate, and dibutyltin dilaurate.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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%
  • the transmittance of the optical material (polythiourethane) prepared with the NBDI composition is 85.89-86.85%.
  • 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
  • the glass transition temperature of the optical material (polythiourethane) prepared with the NBDI composition is 108.08-108.65°C.
  • the isocyanate composition provided in the embodiment of the present application, through the design and control of the effective factor, 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 products such as polyurethane, polythiourethane, etc., so that the obtained polyurethane and polythiourethane will not appear turbid and 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.
  • FIG1 is a schematic flow diagram of a method for preparing an isocyanate composition in a specific embodiment of the present application
  • 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
  • 60 is a refining step.
  • Chromatographically pure CCl4 standard is used as Cl source, ethyl acetate is used as diluent, and X-rays generated by X-ray tube excite Cl element in the sample to produce characteristic X-ray fluorescence.
  • the intensity of characteristic X-ray fluorescence is linearly related to element concentration.
  • a standard curve is drawn, and the extrapolated value is the Cl content in the sample.
  • Carrier gas Helium
  • Carrier gas flow rate 1mL/min (constant flow rate)
  • SIM selected ion scanning mode (XDI selected ions are 160/126, H6XDI selected ions are 186/152, NBDI selected ions are 198/164)
  • Carrier gas flow rate 1mL/min (constant flow rate)
  • FIG1 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 shown in FIG1 , which specifically comprises the following steps:
  • Salt-forming process 800 parts by mass of chlorobenzene are charged into the salt-forming kettle, the salt-forming temperature in the salt-forming kettle is adjusted to 25°C, and the salt-forming pressure (gauge pressure) in the salt-forming kettle is adjusted to 0.04 MPa G.
  • HCl gas is 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-phenylenediamine) (the mass concentration of 1,3-XDA is 8.0 wt.%, and the solvent is chlorobenzene) is 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 is 4:1, thereby generating a slurry containing 1,3-XDA hydrochloride, and the slurry containing 1,3-XDA hydrochloride is transported to the phosgenation kettle.
  • 1,3-XDA 1,3-phenylenediamine
  • Phosgenation process convey a slurry containing 1,3-XDA hydrochloride into a phosgenation kettle, and continuously introduce phosgene 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
  • the residence time is 7 hours.
  • 1,3-XDA hydrochloride reacts with phosgene to generate 1,3-XDI, and a reaction product containing 1,3-XDI is obtained.
  • the reaction product obtained in the phosgenation process 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.
  • 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.
  • a short-path evaporator heavy component removal device
  • 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%.
  • the aforementioned mixture is continuously conveyed 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;
  • distillation conditions in the distillation tower are as follows:
  • the output of the distillation process is 96.2 parts by mass/h.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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).
  • 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 the heavy component (recovery material) in the mixture in the heavy component recovery process.
  • XDI was prepared as Comparative Example 7 by the method in Example 1 of the related technology 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.
  • H6XDI was prepared by the method of Example 1 of US005196572A, except that the raw material was replaced with 1,3-cyclohexane dimethylene dicarbamate 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.
  • 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.
  • An optical 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.
  • the specific preparation method of the optical material is as follows:
  • the polymerizable composition was degassed for 1 hour at a pressure of 600 Pa, and then filtered with a 3 ⁇ m 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.
  • the yellowness index of the lens is measured according to the method in the national standard GB/T 2409-1980;
  • 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:
  • 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.
  • the transmittance of the lens is tested according to GB/T 10810.3-2006 "Eyeglass lenses and related eyewear products Part 3: Transmittance specifications and measurement methods".
  • 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;
  • 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.
  • the present application 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%.
  • 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.
  • the present application uses the above-mentioned embodiments to illustrate the isocyanate composition, modified isocyanate, polyurethane resin and optical material of the present application, but the present application is not limited to the above-mentioned process steps, that is, it does not mean that the present application must rely on the above-mentioned process steps to be implemented.
  • Those skilled in the art should understand that any improvement to the present application, equivalent replacement of the raw materials selected in the present application, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

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Abstract

一种异氰酸酯组合物、改性异氰酸酯、聚氨酯树脂和光学材料，所述异氰酸酯组合物的有效因子为3.90‑5.70。通过有效因子的设计和控制，使其具有优良的反应活性，能够用于高性能聚氨酯、聚硫氨酯等树脂的制备，不会在聚合过程中出现凝胶等不良现象。而且，所述异氰酸酯组合物能够有效提升聚氨酯、聚硫氨酯等产品的耐黄变性、稳定性和光学性能，使得到的聚氨酯、聚硫氨酯不会产生白浊、不透明的现象。以所述异氰酸酯组合物制备的光学材料具有显著降低的黄度指数和显著降低的光学形变发生率，有效提升了光学材料的光学性质。

Description

一种异氰酸酯组合物、改性异氰酸酯、聚氨酯树脂和光学材料 技术领域
本申请实施例涉及异氰酸酯技术领域，例如一种异氰酸酯组合物、改性异氰酸酯、聚氨酯树脂和光学材料。
背景技术
与玻璃等无机光学材料相比，光学树脂材料具有质轻、不易折断、不易破裂、易染等优点，被广泛用于眼镜镜片、手机镜头、灯饰、透镜、棱镜、电器设备等领域。目前已知的光学树脂材料包括聚碳酸酯(PC)、聚甲基丙烯酸甲酯(亚克力，PMMA)、聚烯丙基二甘醇碳酸酯树脂(PADC)和聚硫氨酯等，其中，聚硫氨酯在透明度、折射率、耐冲击性、染色性和加工性等方面具有优异的综合表现，是最具发展潜力的光学材料之一。
聚硫氨酯属于聚氨酯材料的重要分支，其采用多硫醇化合物和多异(硫)氰酸酯化合物聚合反应得到。例如CN101155848A公开了聚硫氨酯类聚合性组合物，包括如下组分：(A)脂环式异氰酸酯化合物，(B)脂肪族异氰酸酯化合物，(C)1分子中具有1个以上硫键的多硫醇化合物或1分子中具有1个以上多硫键的多硫醇化合物中的至少一种，(D)1分子中具有2个以上羟基的多羟基化合物，和/或，具有1个以上羟基且具有1个以上硫醇基的羟基巯基化合物中的至少一种；该聚合物性组合物得到的聚硫氨酯具有较好的染色性和强度。CN106414538A公开了一种用于制备透明的聚硫氨酯体的组合物，包括多异氰酸酯组分、硫醇组分以及任选的辅助剂和添加剂；其中，所述多异氰酸酯组分通过脂族的、环脂族的、芳族的或芳脂族的多胺的气相光气化而制备，其包含基于多异氰酸酯组分的至少0.005重量％的至少一种腈类物质，该腈类物质与多异氰酸酯源自于相同的多胺；通过前述组合物制备得到的聚硫氨酯镜片具有较好的透明度。CN108084386A公开了一种光学材料用聚硫氨酯树脂组合物，通过将包含有机锆铋合金复合物、异氰酸酯类化合物、硫醇类化合物的组合物加热固化而得到；其中，有机锆铋合金复合物作为催化剂，能够实现在不损失塑料透镜用途的透明性、机械和耐热等树脂性能前提下，提高透镜产品产业化过程中的合格率。
相关技术公开的聚硫氨酯主要聚焦于材料的透明度、机械性能、染色性和耐热性等，然而，在聚硫氨酯材料的聚合过程中，常常会出现树脂白浊、不透明的现象，而且得到的聚硫氨酯存在黄变、光学形变等问题，造成镜片、透镜等产品的质量不合格，严重限制了聚硫氨酯在镜片、透镜等光学部件中的广泛应用。
因此，开发性能更加优异的聚硫氨酯，尤其是降低聚硫氨酯的黄度指数和光学形变发生率，是本领域亟待解决的问题。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请实施例提供一种异氰酸酯组合物、改性异氰酸酯、聚氨酯树脂和光学材料，所述异氰酸酯组合物通过有效因子的设计和控制，能够有效改善聚氨酯树脂和聚硫氨酯的耐黄变性和稳定性，显著降低了光学材料的黄度指数和光学形变发生率，赋予其优异的光学性能。
第一方面，本申请实施例提供一种异氰酸酯组合物，所述异氰酸酯组合物的有效因子为3.90-5.70。
所述有效因子的计算公式如式I所示：
Figure PCTCN2022132417-appb-000001
式I中，E为有效因子；
式I中，A为所述异氰酸酯组合物中氯的质量含量；
式I中，B为所述异氰酸酯组合物中氯代异氰酸酯的质量含量；
式I中，M Cl为氯的相对原子质量；
式I中，M B为所述氯代异氰酸酯的相对分子质量。
本申请提供的异氰酸酯组合物的有效因子E为3.90-5.70，例如可以为4.00、4.10、4.30、4.50、4.70、4.90、5.00、5.10、5.20、5.30、5.40、5.50或5.60，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
本申请中，所述异氰酸酯组合物包括异氰酸酯和含氯物质的组合，故将其定义为“组合物”；所述含氯物质包括氯代异氰酸酯和有效因子对应的物质。本申请通过有效因子的设计和控制，使所述异氰酸酯组合物包括特定含量的特定种类的含氯物质，使其具有优良的反应活性，能够用于高性能聚氨酯、聚硫氨酯等树脂的制备，且不会在聚合过程中出现凝胶等不良现象；而且，所述异氰酸酯组合物能够有效提升聚氨酯、聚硫氨酯等树脂产品的耐黄变性、稳定性和光学性能，使得到的聚氨酯、聚硫氨酯不会出现白浊、不透明的现象，而且作为光学材料具有低的黄度指数和低的光学形变发生率，有效提升了光学材料的光学品质。如果有效因子过高，则异氰酸酯组合物用于制备聚氨酯或聚硫氨酯，会在聚合反应中出现凝胶的现象；如果有效因子过低，则会影响聚氨酯、聚硫氨酯的耐黄变性和光学性能，导致光学材料的黄变指数较高，光学形变的发生几率增大。
本申请中，计算有效因子的式I中，A为所述异氰酸酯组合物中氯的质量含量，优选通过X射线荧光光谱分析(XRF)测试得到。
优选地，计算有效因子的式I中，B为所述异氰酸酯组合物中氯代异氰酸酯的质量含量，通过色谱-质谱法测试得到，优选通过气相色谱-质谱法(GCMS)测试得到。
本申请在研究中发现，相关技术已知的异氰酸酯中氯含量的表征方法无法精准控制异氰酸酯的性能，从而不能对聚氨酯/聚硫氨酯的品质、尤其是耐黄变性和光学性能进行有效控制。具体地，标准GB/T 12009.1-1989中总氯含量的测试方法为氧瓶燃烧法，将异氰酸酯中所有氯(还包括溴)转化为无机氯(还包括溴)后再采用硝酸银滴定，表征的是异氰酸酯中所有 的氯含量，而且包括了异氰酸酯中溴的含量。标准GB/T 12009.2-2016测定的是水解氯，具体为异氰酸酯与醇和水反应后释放出来的氯，是异氰酸酯中活性较高的氯，也包括活性较高的溴，部分单氯代异氰酸酯也能水解一部分。以GB/T 12009.1-1989或GB/T 12009.2-2016测定的氯(还包括一部分溴)含量并不能精确表示出异氰酸酯的组分信息，也就不能对异氰酸酯及聚氨酯/聚硫氨酯的性能进行有效控制。
作为本申请的优选技术方案，所述有效因子E的计算中，A为XRF测试得到总氯含量(不含溴)，B为采用色谱质谱法测试得到的氯代异氰酸酯含量，A值和B值以精确的定性和定量分析方法测试得到，从而使所述有效因子E精确表征了异氰酸酯组合物中多氯代物以及部分的水解氯(不包含单氯代异氰酸酯的水解氯)，对应更加精细、明确的氯含量，该部分氯含量对异氰酸酯的活性以及聚氨酯、聚硫氨酯等产品的性能具有关键作用，从而实现了对异氰酸酯组合物的性能调控，进而改善了通过其制备的聚氨酯、聚硫氨酯的性能，尤其对光学材料的光学性能(黄变指数、光学变形)具有明显的提升效果。
优选地，所述异氰酸酯为二异氰酸酯，进一步优选包括苯二亚甲基二异氰酸酯(XDI)、双异氰酸酯甲酯基环己烷(H6XDI)、双异氰酸酯甲酯基降冰片烷(NBDI)中的任意一种或至少两种的组合。
本申请中，如无特殊说明，列举的异氰酸酯包括其所有的异构体，例如，所述苯二亚甲基二异氰酸酯(XDI)为
Figure PCTCN2022132417-appb-000002
所述双异氰酸酯甲酯基环己烷(H6XDI)为
Figure PCTCN2022132417-appb-000003
所述双异氰酸酯甲酯基降冰片烷(NBDI)为
Figure PCTCN2022132417-appb-000004
优选地，所述异氰酸酯组合物中异氰酸酯的质量百分含量≥97％，例如为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％等。
优选地，所述异氰酸酯组合物中氯的质量含量(A值)为2-1000ppm，例如可以为5ppm、10ppm、50ppm、100ppm、150ppm、200ppm、250ppm、300ppm、350ppm、400ppm、450ppm、500ppm、550ppm、600ppm、650ppm、700ppm、750ppm、800ppm、850ppm、900ppm或950ppm，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选15-500ppm。
本申请中，“ppm”为百万分比率，1ppm表示百万分之一；下文涉及相同的表述时，均具有相同的含义。
优选地，所述有效因子对应的物质包括如下化合物中的任意一种或至少两种的组合：
Figure PCTCN2022132417-appb-000005
其中，R为异氰酸酯中的NCO基团被去除得到的二价基团。
优选地，所述R选自
Figure PCTCN2022132417-appb-000006
(异氰酸酯为XDI)、
Figure PCTCN2022132417-appb-000007
(异氰酸酯为H6XDI)、
Figure PCTCN2022132417-appb-000008
(异氰酸酯为NBDI)中的任意一种或至少两种的组合；其中，波浪线代表基团的连接位点。
优选地，所述氯代异氰酸酯为异氰酸酯中的一个NCO基团被氯替代得到的化合物。
优选地，所述氯代异氰酸酯包括
Figure PCTCN2022132417-appb-000009
(氯甲基苄基异氰酸酯CBI，异氰酸酯为XDI)、
Figure PCTCN2022132417-appb-000010
(氯甲基异氰酸甲酯基环己烷CIC，异氰酸酯为H6XDI)、
Figure PCTCN2022132417-appb-000011
(氯甲基异氰酸甲酯基降冰片烷CNBI，异氰酸酯为NBDI)中的任意一种或至少两种的组合。
本文中，“—”划过的环结构的表达方式，表示连接位点于该环结构上任意能够成键的位置。
优选地，所述异氰酸酯组合物中氯代异氰酸酯的质量含量(B值)为10-2000ppm，例如可以为20ppm、50ppm、100ppm、300ppm、500ppm、700ppm、900ppm、1000ppm、1100ppm、1300ppm、1500ppm、1700ppm或1900ppm，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选80-1500ppm。
需要说明的是，本申请中，所述有效因子对应的物质、氯代异氰酸酯可以在异氰酸酯的制备过程中作为副产物而产生，也可以人为添加以获得所要求的含量。
第二方面，本申请实施例提供一种如第一方面所述的异氰酸酯组合物的制备方法，所述制备方法包括：胺类化合物与光气进行反应，得到所述异氰酸酯组合物。
优选地，所述制备方法包括如下步骤：
(1)胺类化合物与光气进行反应，得到反应产物；
(2)对步骤(1)得到的反应产物进行脱除处理，得到粗品；所述脱除处理包括脱光气处理和/或脱溶剂处理；
(3)将步骤(2)得到的粗品依次进行分离和精制，得到所述异氰酸酯组合物。
优选地，步骤(3)所述分离得到重组分和中间品；将所述中间品和重组分的混合物进行精制，得到所述异氰酸酯组合物；所述混合物中重组分的质量百分含量为1-10％。
作为本申请的优选技术方案，进行精制的组分为所述中间品和重组分的混合物，且所述混合物中重组分的质量百分含量为1-10％，例如可以为2％、3％、4％、5％、6％、7％、8％或9％，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选2-10％。
优选地，所述分离得到的重组分可直接与中间品混合，得到混合物；或，所述分离得到的重组分为一级重组分，所述一级重组分再次分离得到重组分回收料和残余重组分；所述重组分回收料与中间品混合，得到所述混合物；所述混合物中重组分回收料的质量百分含量为1-10％。
在另一优选技术方案中，所述异氰酸酯组合物的制备方法包括：将氨基甲酸酯裂解法得到的异氰酸酯与所述重组分回收料混合，得到所述异氰酸酯组合物。优选地，所述异氰酸酯组合物中重组分回收料的质量百分含量为1-10％(例如2％、3％、4％、5％、6％、7％、8％或9％等)，进一步优选1-5％。
作为本申请的优选技术方案，所述异氰酸酯组合物的制备方法为光气化法，即胺类化合物与光气进行反应，生成异氰酸酯；所述胺类化合物包括二胺和/或二胺盐(例如二胺与HCl反应得到的二胺盐酸盐)。
优选地，所述胺类化合物与光气进行反应的方法示例性地包括如下三类：二胺与光气在气相中反应的方法，又称气相光气化法；二胺与光气在液相中反应的方法，又称液相光气化法；二胺盐(例如二胺盐酸盐)与光气在溶剂中反应的方法，又称二胺盐酸盐的光气化法，进一步优选二胺盐酸盐的光气化法。
优选地，步骤(1)所述胺类化合物为二胺盐酸盐。
优选地，所述二胺盐酸盐通过成盐工序制备得到，所述成盐工序包括：在反应溶剂的存在下，使二胺与氯化氢进行成盐反应，得到所述二胺盐酸盐。成盐工序实际得到的为含有二胺盐酸盐的浆料，该浆料直接应用于与光气的反应(异氰酸酯化工序)中。
优选地，所述成盐工序具体包括：向反应溶剂中通入氯化氢气体，然后加入胺溶液(包括反应溶剂和二胺)，搅拌混合，进行成盐反应，得到所述二胺盐酸盐。
优选地，所述成盐工序中氯化氢与二胺的摩尔比为(2-20):1，例如可以为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或18:1等，进一步优选(3-16):1。
优选地，所述胺溶液中的二胺的质量百分含量为1-50wt.％，例如可以为2wt.％、5wt.％、8wt.％、10wt.％、12wt.％、15wt.％、18wt.％、20wt.％、22wt.％、25wt.％、28wt.％、30wt.％、35wt.％、40wt.％、45wt.％或48wt.％，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选3-30wt.％。
优选地，所述成盐反应的温度为0-160℃，例如可以为5℃、10℃、20℃、30℃、40℃、50℃、60℃、80℃、100℃、110℃、130℃或150℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选10-150℃，更进一步优选10-140℃。
优选地，所述成盐工序在常压或加压的条件下进行。
优选地，所述成盐工序的压力(表压)为0.01-1.0MPa G，例如可以为0.03MPa G、0.05MPa G、0.08MPa G、0.1MPa G、0.2MPa G、0.3MPa G、0.4MPa G、0.5MPa G、0.6MPa G、0.7MPa G、0.8MPa G或0.9MPa G，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选0.02-0.5MPa G，更进一步优选0.02-0.4MPa G。
优选地，步骤(1)具体包括：向二胺盐酸盐(浆料)中通入光气，进行反应，得到反应产物，即含有二异氰酸酯的反应液。
优选地，所述光气与二胺盐酸盐的摩尔比为(4-50):1，例如可以为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或48:1等，进一步优选(5-40):1，更进一步优选(5-30):1。
优选地，步骤(1)所述反应的温度为80-180℃，例如可以为90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃或170℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选100-170℃，更进一步优选100-160℃。
优选地，步骤(1)所述反应的时间为2-25h，例如可以为3h、4h、6h、8h、10h、12h、14h、16h、18h、20h、22h或24h，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选4-20h。
优选地，步骤(1)所述反应在常压或加压的条件下进行。
优选地，步骤(1)所述反应的压力(表压)为0-0.6MPa G，例如可以为0.0005MPa G、0.001MPa G、0.003MPa G、0.01MPa G、0.02MPa G、0.03MPa G、0.05MPa G、0.07MPa G、0.09MPa G、0.1MPa G、0.2MPa G、0.3MPa G、0.4MPa G或0.5MPa G，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选0.005-0.4MPa G，更进一步优选0.01-0.2MPa G。
优选地，步骤(1)所述反应(异氰酸酯化工序)为间歇工序或连续工序，优选连续工序。
其中，所述连续工序即为在成盐工序(成盐釜)中生成的浆料(二胺盐酸盐)从搅拌槽连续地输送至与成盐釜不同的反应釜中，在反应釜中使二胺盐酸盐与光气反应，并且，将得到的反应产物(含有二异氰酸酯的反应液)连续地从反应釜中取出。本申请对于连续工序的反应釜的个数不做具体限定，示例性地，可以为2个、3个、4个、5个或更多。
根据需要，可以对步骤(1)得到的反应产物实施脱除工序(脱溶剂工序和/或脱光气工序)和分离精制工序。
优选地，所述反应溶剂为有机溶剂，示例性地包括但不限于：例如苯、甲苯、二甲苯等芳香族烃类，例如辛烷、癸烷等脂肪族烃类，环己烷、甲基环己烷、乙基环己烷等脂环族烃类，例如氯甲苯、氯苯、二氯苯、二溴苯、三氯苯等卤代芳香族烃类，例如硝基苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N'-二甲基咪唑啉酮等含氮化合物类，例如二丁基醚、乙二醇二甲基醚、乙二醇二乙基醚等醚类，例如庚酮、二异丁基酮、甲基异丁基酮、甲基乙基酮等酮类，例如乙酸乙酯、乙酸丁酯、乙酸戊酯、乙酸乙氧基乙酯等脂肪酸酯类，例如水杨酸甲酯、邻苯二甲酸二甲酯、邻苯二甲酸二丁酯、苯甲酸甲酯等芳香族羧酸酯类等；反应溶剂可以单独使用，或者为至少两种的组合。
优选地，所述反应溶剂包括卤代芳香族烃类，进一步优选氯苯和/或二氯苯。
优选地，步骤(2)所述脱光气处理在脱光气塔中进行。
优选地，步骤(2)所述脱溶剂处理在脱溶剂塔中进行。
优选地，步骤(3)所述分离将中间品(轻组分)和重组分进行分离，实现重组分的脱除；所述分离的装置示例性地包括但不限于：短程蒸发器、蒸馏塔。
优选地，所述短程蒸发器的操作压力为0.05-4kPa，例如可以为0.08kPa、0.1kPa、0.3kPa、0.5kPa、0.8kPa、1kPa、1.2kPa、1.5kPa、1.8kPa、2kPa、2.2kPa、2.5kPa、2.8kPa、3kPa、3.2kPa、3.5kPa或3.8kPa，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选为0.1-2.5kPa。
作为本申请的优选技术方案，所述分离得到的重组分中包含种类多、含量较高的含氯物质，通过将分离得到的重组分以一定的比例掺入分离得到的中间品(轻组分)中得到混合物，再将所述混合物进行精制，能够有效调控产物中的含氯物质的种类和含量，使所述异氰酸酯组合物的有效因子为3.90-5.70。
优选地，所述混合物中重组分(重组分回收料)的质量百分含量为1-10％，进一步优选2-10％，使所述异氰酸酯组合物的有效因子为3.90-5.70。如果重组分(重组分回收料)的掺入量过少，则有效因子偏高，所述异氰酸酯组合物用于制备聚氨酯/聚硫氨酯，容易发生凝胶等不良现象；如果重组分(重组分回收料)的掺入量过高，导致有效因子低，所述异氰酸酯组合物中含有较多的杂质，影响聚氨酯/聚硫氨酯的耐变色(黄变)性能和稳定性，导致光学材料的光学性能不佳。
优选地，与中间品混合的所述重组分可通过直接回掺入中间品，或可经过脱重组分设备循环分离后得到重组分回收料，再将其掺入中间品中。
优选地，所述精制的方法为本领域已知的工业分离技术，示例性地包括但不限于：蒸馏、精馏、晶析等。
优选地，所述精制的方法为精馏。
优选地，所述精馏在精馏塔中进行，所述精馏塔优选包括板式精馏塔或填充式精馏塔。
优选地，所述精馏塔的理论塔板数为2-60，例如可以为3、5、8、10、12、15、18、20、22、25、28、30、32、35、38、40、42、45、48、52、52、55或58，以及上述点值之间的具 体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选为5-40。
优选地，所述精馏塔的塔顶压力为0.1-4kPa，例如可以为0.2kPa、0.5kPa、0.8kPa、1kPa、1.2kPa、1.5kPa、1.8kPa、2kPa、2.2kPa、2.5kPa、2.8kPa、3kPa、3.2kPa、3.5kPa或3.8kPa，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选为0.15-2.5kPa。
优选地，所述精馏塔的塔顶回流比为0.01-60，例如可以为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或58，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选为0.1-40。
在本申请的一个优选技术方案中，所述异氰酸酯组合物的制备方法包括如下步骤：
(1a)成盐工序：二胺与氯化氢进行成盐反应，得到二胺盐酸盐；
(1)光气化工序：步骤(1)得到的二胺盐酸盐与光气进行反应，得到反应产物；
(2)脱除工序：对步骤(1)得到的反应产物进行脱除处理，得到粗品；所述脱除处理包括脱光气处理和/或脱溶剂处理；
(3a)分离工序：将步骤(2)得到的粗品进行分离，得到重组分和中间品(轻组分)；
(3b)重组分回收工序：将步骤(3a)得到的中间品和重组分混合，得到混合物；所述混合物中重组分的质量百分含量为1-10％；或，将步骤(3a)得到的重组分进行二次分离，得到重组分回收料和残余重组分；将所述重组分回收料与中间品混合，得到混合物；所述混合物中重组分回收料的质量百分含量为1-10％；
(3c)精制工序：将步骤(3b)得到的混合物进行精制，得到所述异氰酸酯组合物。
示例性地，所述制备方法的流程示意图如图1所示，包括成盐工序10，光气化工序20，脱除工序30，分离工序40，重组分回收工序50，精制工序60。其中，成盐工序和光气化工序可通过间歇方式或连续方式实施，连续方式通过釜式连续进行。通过适当调节重组分与中间品的混合比例、光气的供给比例、反应温度、反应压力、平均滞留时间、精馏塔的回流比等来调节异氰酸酯组合物的有效因子，主要通过重组分与中间品的比例实现有效因子的控制。
具体地，以XDI组合物为例，其制备方法如下：
(1a)成盐工序：采用釜式反应，可以单釜或者两釜；首先在成盐釜中装入反应溶剂；而后，以上述的氯化氢和二胺的比例向成盐釜加入氯化氢和苯二亚甲基二胺(XDA)；在将成盐釜的内部维持为上述的成盐温度及压力的同时，通过搅拌叶片将氯化氢和胺溶液搅拌混合，由此得到XDA盐酸盐；一边向成盐釜中连续地供给氯化氢气体和胺溶液，一边将包含XDA盐酸盐的浆料从成盐釜中连续地取出，输送至光气化工序。
(1)光气化工序：采用釜式反应，三釜或四釜连续，向将上述XDA盐酸盐连续地输送至光气化反应釜，以上述的供给比例，向光气化一釜、光气化二釜及光气化三釜的各自的顶部以插入管的方式连续地通入光气；而后，一边将光气化釜的内部维持为上述的反应温度及 反应压力，一边将浆料及光气搅拌混合。由此，XDA盐酸盐与碳酰氯进行反应，作为主成分而生成XDI，作为副产物而生成CBI和其他中间体，得到反应液。
由此，连续地实施成盐工序及光气化工序。
(2)脱除工序：采用脱光气塔和脱溶剂塔进行，向脱光气塔的塔中部位连续地输送上述反应液。通过脱光气塔，将反应液进行光气和氯化氢等脱除；然后通过脱溶剂塔将反应液中溶剂脱除，得到XDI粗品。
(3a)分离工序：采用短程蒸发器将上述XDI粗品进行分离，脱除重组分，得到中间品和一级重组分。
(3b)重组分回收工序：一级重组分经过短程蒸发器进行回收，得到重组分回收料和二级重组分，可单次或循环进行回收；重组分回收料与中间品混合得到的混合物进入精制工序；所述混合物中重组分回收料的质量百分含量为1-10％。
(3c)精制工序：向精馏塔的塔中连续地输送上述混合物；而后，在前述精馏的条件(塔底温度、塔顶温度、塔顶压力、塔底回流比、塔顶回流比、停留时间)下，将低沸物从中间品中馏去，从塔中部偏下采出XDI组合物。
由此，可连续地制造包括XDI、CBI以及有效因子对应的物质的XDI组合物。
第三方面，本申请实施例提供一种改性异氰酸酯，所述改性异氰酸酯通过如第一方面所述的异氰酸酯组合物改性得到；所述改性异氰酸酯包含基团(a)-(i)中的任意一种或至少两种的组合：(a)异氰脲酸酯基，(b)脲二酮基，(c)缩二脲基，(d)氨基甲酸酯基，(e)脲基，(f)亚氨基噁二嗪二酮基，(g)脲基甲酸酯基，(h)脲酮亚胺基，(i)碳二亚胺基。
本领域技术人员可以根据需要利用已知的方法对前述异氰酸酯组合物进行改性，得到所述改性异氰酸酯；所述改性异氰酸酯作为多异氰酸酯成分和含活性氢基团的物质作为聚氨酯树脂、聚硫氨酯树脂的原料而被合适地利用。
具体地，包含所述基团(a)异氰脲酸酯基的改性异氰酸酯即为异氰酸酯的三聚物，示例性地，其可通过在已知的异氰脲酸酯化催化剂的存在下使异氰酸酯组合物反应、使其中的异氰酸酯进行异氰脲酸酯化而得到。
包含所述基团(b)脲二酮基的改性异氰酸酯可通过于90-200℃左右对异氰酸酯组合物进行加热的方法、或在已知的脲二酮化催化剂的存在下使其反应、使异氰酸酯进行脲二酮化(例如二聚化)而得到。
包含所述基团(c)缩二脲基的改性异氰酸酯可通过在使异氰酸酯组合物与例如水、叔醇(例如叔丁醇等)、仲胺(例如二甲基胺、二乙基胺等)等反应后在已知的缩二脲化催化剂的存在下进一步使其反应而得到。
包含所述基团(d)氨基甲酸酯基的改性异氰酸酯可通过异氰酸酯组合物与多元醇成分(例如三羟甲基丙烷等)的反应而得到。
包含所述基团(e)脲基的改性异氰酸酯可通过异氰酸酯组合物与水、多胺成分(后述)等的反应而得到。
包含所述基团(f)亚氨基噁二嗪二酮基的改性异氰酸酯即为异氰酸酯的非对称性三聚体，可通过在已知的亚氨基噁二嗪二酮化催化剂的存在下使异氰酸酯组合物反应、使异氰酸酯进行亚氨基噁二嗪二酮化(例如三聚化)而得到。
包含所述基团(g)脲基甲酸酯基的改性异氰酸酯可通过在使异氰酸酯组合物与醇反应后、在已知的脲基甲酸酯化催化剂的存在下进一步使其反应而得到。
包含所述基团(h)脲酮亚胺基的改性异氰酸酯可通过在已知的碳二亚胺化催化剂的存在下使异氰酸酯组合物反应形成碳二亚胺基后、向该碳二亚胺基加成异氰酸酯而得到。
包含所述基团(i)碳二亚胺基的改性异氰酸酯可通过在已知的碳二亚胺化催化剂的存在下使异氰酸酯组合物反应而得到。
需要说明的是，所述改性异氰酸酯包含上述基团(a)-(i)中的至少1种即可，也可含有至少2种。这样的改性异氰酸酯可通过适当地并用上述的反应而生成。另外，改性异氰酸酯可以单独使用或并用2种以上。
第四方面，本申请实施例提供一种聚氨酯树脂，所述聚氨酯树脂通过异氰酸酯类物质与含活性氢基团的物质反应而成；所述异氰酸酯类物质包括如第一方面所述的异氰酸酯组合物、如第三方面所述的改性异氰酸酯中的至少一种。
优选地，所述活性氢基团包括羟基、氨基、巯基中的任意一种或至少两种的组合。
优选地，所述含活性氢基团的物质包括多元醇、多元胺、多硫醇中的任意一种或至少两种的组合。
第五方面，本申请提供一种光学材料，所述光学材料通过异氰酸酯类物质与多硫醇化合物聚合而成；所述异氰酸酯类物质包括如第一方面所述的异氰酸酯组合物、如第三方面所述的改性异氰酸酯中的至少一种。
本申请中，所述光学材料为聚硫氨酯；所述多硫醇化合物指是含有至少两个硫醇基团(巯基)的化合物。
优选地，所述光学材料应用于镜片、透镜、棱镜、灯罩材料、透明包装材料、透明建筑材料或电子产品中；具体而言，所述光学材料应用于镜片、塑料透镜、棱镜、汽车灯罩材料、透明屋顶材料、电子设备(手机或平板电脑)的镜头材料等。
优选地，所述多硫醇化合物包括甲二硫醇、1,2-乙二硫醇、1,1-丙二硫醇、1,2-丙二硫醇、1,3-丙二硫醇、2,2-丙二硫醇、1,6-己二硫醇、1,2,3-丙三硫醇、1,1-环己二硫醇、1,2-环己二硫醇、2,2-二甲基丙烷-1,3-二硫醇、3,4-二甲氧基丁烷-1,2-二硫醇、2-甲基环己烷-2,3-二硫醇、1,1-双(巯基甲基)环己烷、硫代苹果酸双(2-巯基乙基酯)、2,3-二巯基-1-丙醇(2-巯基乙酸酯)、2,3-二巯基-1-丙醇(3-巯基丙酸酯)、二甘醇双(2-巯基乙酸酯)、二甘醇双(3-巯基丙酸酯)、1,2-二巯基丙基甲基醚、2,3-二巯基丙基甲基醚、2,2-双(巯基甲基)-1，3-丙烷二硫醇、双(2-巯基乙基)醚、乙二醇双(2-巯基乙酸酯)、乙二醇双(3-巯基丙酸酯)、三羟甲基丙烷双(2-巯基乙酸酯)、三羟甲基丙烷双(3-巯基丙酸酯)、季戊四醇四(2-巯基乙酸酯)、季戊四醇四(3-巯基丙酸酯)、四(巯基甲基)甲烷等脂肪族多硫醇化合物。
优选地，所述多硫醇化合物还包括1,2-二巯基苯、1,3-二巯基苯、1,4-二巯基苯、1,2-双(巯基甲基)苯、1,3-双(巯基甲基)苯、1,4-双(巯基甲基)苯、1,2-双(巯基乙基)苯、1,3-双(巯基乙基)苯、1,4-双(巯基乙基)苯、1,2,3-三巯基苯、1,2,4-三巯基苯、1,3,5-三巯基苯、1,2,3-三(巯基甲基)苯、1,2,4-三(巯基甲基)苯、1,3,5-三(巯基甲基)苯、1,2,3-三(巯基乙基)苯、1,2,4-三(巯基乙基)苯、1,3,5-三(巯基乙基)苯、2,5-甲苯二硫醇、3,4-甲苯二硫醇、1,3-二(对甲氧基苯基)丙烷-2,2-二硫醇、1,3-二苯基丙烷-2,2-二硫醇、苯基甲烷-1,1-二硫醇、2,4-二(对巯基苯基)戊烷等芳香族多硫醇化合物。
优选地，所述多硫醇化合物还包括1,2-双(巯基乙硫基)苯、1,3-双(巯基乙硫基)苯、1,4-双(巯基乙硫基)苯、1,2,3-三(巯基甲硫基)苯、1,2,4-三(巯基甲硫基)苯、1,3,5-三(巯基甲硫基)苯、1,2,3-三(巯基乙硫基)苯、1,2,4-三(巯基乙硫基)苯、1,3,5-三(巯基乙硫基)苯等、及它们的烷基化物等除巯基以外含有硫原子的芳香族多硫醇化合物。
优选地，所述多硫醇化合物还包括双(巯基甲基)硫醚、双(巯基甲基)二硫醚、双(巯基乙基)硫醚、双(巯基乙基)二硫醚、双(巯基丙基)硫醚、双(巯基甲硫基)甲烷、双(2-巯基乙硫基)甲烷、双(3-巯基丙硫基)甲烷、1,2-双(巯基甲硫基)乙烷、1,2-双(2-巯基乙硫基)乙烷、1,2-双(3-巯基丙基)乙烷、1,3-双(巯基甲硫基)丙烷、1,3-双(2-巯基乙硫基)丙烷、1,3-双(3-巯基丙硫基)丙烷、1,2,3-三(巯基甲硫基)丙烷、1,2,3-三(2-巯基乙硫基)丙烷、1,2,3-三(3-巯基丙硫基)丙烷、1,2-双((2-巯基乙基)硫代)-3-巯基丙烷、4,8-二巯基甲基-1,11-二巯基-3,6,9-三硫杂十一烷、4,7-二巯基甲基-1,11-二巯基-3,6,9-三硫杂十一烷、5,7-二巯基甲基-1,11-二巯基-3,6,9-三硫杂十一烷、双(巯基甲基)-3,6,9-三硫杂-1,11-十一烷二硫醇、四(巯基甲硫基甲基)甲烷、四(2-巯基乙硫基甲基)甲烷、四(3-巯基丙硫基甲基)甲烷、双(2,3-二巯基丙基)硫醚、双(1,3-二巯基丙基)硫醚、2,5-二巯基-1,4-二噻烷、2,5-二巯基甲基-1,4-二噻烷、2,5-二巯基甲基-2,5-二甲基-1,4-二噻烷、双(巯基甲基)二硫醚、双(巯基乙基)二硫醚、双(巯基丙基)二硫醚等除巯基以外含有硫原子的脂肪族多硫醇化合物、及它们的巯基乙酸及巯基丙酸的酯。
优选地，所述多硫醇化合物还包括羟甲基硫醚双(2-巯基乙酸酯)、羟甲基硫醚双(3-巯基丙酸酯)、羟乙基硫醚双(2-巯基乙酸酯)、羟乙基硫醚双(3-巯基丙酸酯)、羟丙基硫醚双(2-巯基乙酸酯)、羟丙基硫醚双(3-巯基丙酸酯)、羟甲基二硫醚双(2-巯基乙酸酯)、羟甲基二硫醚双(3-巯基丙酸酯)、羟乙基二硫醚双(2-巯基乙酸酯)、羟乙基二硫醚双(3-巯基丙酸酯)、羟丙基二硫醚双(2-巯基乙酸酯)、羟丙基二硫醚双(3-巯基丙酸酯)、2-巯基乙基醚双(2-巯基乙酸酯)、2-巯基乙基醚双(3-巯基丙酸酯)、1,4-二噻烷-2,5-二醇双(2-巯基乙酸酯)、1,4-二噻烷-2,5-二醇双(3-巯基丙酸酯)、亚硫基二乙酸双(2-巯基乙酸酯)、硫代二丙酸双(2-巯基乙酸酯)、4,4-硫代二丁酸双(2-巯基乙酸酯)、亚二硫基二乙酸双(2-巯基乙酸酯)、二硫代二丙酸双(2-巯基乙酸酯)、4,4-二硫代二丁酸双(2-巯基乙酸酯)、亚硫基二乙酸双(2,3-二巯基丙基酯)、硫代二丙酸双(2,3-二巯基丙基酯)、亚二硫基二乙酸双(2,3-二巯基丙基酯)、二硫代二丙酸双(2,3-二巯基丙基酯)等其他的除巯基以外含有硫原子和酯键的脂肪族多硫醇化合物。
优选地，所述多硫醇化合物还包括3,4-噻吩二硫醇、2,5-二巯基-1,3,4-硫杂二唑等除巯基 以外含有硫原子的杂环化合物。
优选地，所述多硫醇化合物还包括2-巯基乙醇、3-巯基-1,2-丙二醇、甘油二(巯基乙酸酯)、1-羟基-4-巯基环己烷、2,4-二巯基苯酚、2-巯基氢醌、4-巯基苯酚、3,4-二巯基-2-丙醇、1,3-二巯基-2-丙醇、2,3-二巯基-1-丙醇、1,2-二巯基-1,3-丁二醇、季戊四醇三(3-巯基丙酸酯)、季戊四醇单(3-巯基丙酸酯)、季戊四醇双(3-巯基丙酸酯)、季戊四醇三(巯基乙酸酯)、二季戊四醇五(3-巯基丙酸酯)、羟甲基-三(巯基乙硫基甲基)甲烷、1-羟基乙硫基-3-巯基乙硫基苯等除巯基以外含有羟基的化合物。
优选地，所述多硫醇化合物还包括1,1,3,3-四(巯基甲硫基)丙烷、1,1,2,2-四(巯基甲硫基)乙烷、4,6-双(巯基甲硫基)-1,3-二硫杂环己烷、1,1,5,5-四(巯基甲硫基)-3-硫杂戊烷、1,1,6,6-四(巯基甲硫基)-3,4-二硫杂己烷、2,2-双(巯基甲硫基)乙硫醇、2-(4,5-二巯基-2-硫杂戊基)-1,3-二硫杂环戊烷、2,2-双(巯基甲基)-1,3-二硫杂环戊烷、2,5-双(4,4-双(巯基甲硫基)-2-硫杂丁基)-1,4-二噻烷、2,2-双(巯基甲硫基)-1,3-丙烷二硫醇、3-巯基甲硫基-1,7-二巯基-2,6-二硫杂庚烷、3,6-双(巯基甲硫基)-1,9-二巯基-2,5,8-三硫杂壬烷、4,6-双(巯基甲硫基)-1,9-二巯基-2,5,8-三硫杂壬烷、3-巯基甲硫基-1,6-二巯基-2,5-二硫杂己烷、2-(2,2-双(巯基甲硫基)乙基)-1,3-二硫杂环丁烷、1,1,9,9-四(巯基甲硫基)-5-(3,3-双(巯基甲硫基)-1-硫杂丙基)3,7-二硫杂壬烷、三(2,2-双(巯基甲硫基)乙基)甲烷、三(4,4-双(巯基甲硫基)-2-硫杂丁基)甲烷、四(2,2-双(巯基甲硫基)乙基)甲烷、四(4,4-双(巯基甲硫基)-2-硫杂丁基)甲烷、3,5,9,11-四(巯基甲硫基)-1,13-二巯基-2,6,8,12-四硫杂十三烷、3,5,9,11,15,17-六(巯基甲硫基)-1,19-二巯基-2,6,8,12,14,18-六硫杂十九烷、9-(2,2-双(巯基甲硫基)乙基)-3,5,13,15-四(巯基甲硫基)-1,17-二巯基-2,6,8,10,12,16-六硫杂十七烷、3,4,8,9-四(巯基甲硫基)-1,11-二巯基-2,5,7,10-四硫杂十一烷、3,4,8,9,13,14-六(巯基甲硫基)-1,16-二巯基-2,5,7,10,12,15-六硫杂十六烷、8-(双(巯基甲硫基)甲基)-3,4,12,13-四(巯基甲硫基)1,15-二巯基-2,5,7,9,11,14-六硫杂十五烷、4,6-双(3,5-双(巯基甲硫基)-7-巯基-2,6-二硫杂庚硫基)-1,3-二噻烷、4-(3,5-双(巯基甲硫基)-7-巯基-2,6-二硫杂庚硫基)-6-巯基甲硫基-1,3-二噻烷、1,1-双(4-(6-巯基甲硫基)-1,3-二噻烷基硫基)-3,3-双(巯基甲硫基)丙烷、1,3-双(4-(6-巯基甲硫基)-1,3-二噻烷基硫基)-1,3-双(巯基甲硫基)丙烷、1-(4-(6-巯基甲硫基)-1,3-二噻烷基硫基)-3-(2,2-双(巯基甲硫基)乙基)-7,9-双(巯基甲硫基)-2,4,6,10-四硫杂十一烷、1-(4-(6-巯基甲硫基)-1，3-二噻烷基硫基)-3-(2-(1,3-二硫杂环丁基))甲基-7,9-双(巯基甲硫基)-2,4,6,10-四硫杂十一烷、1,5-双(4-(6-巯基甲硫基)-1,3-二噻烷基硫基)-3-(2-(1,3-二硫杂环丁基))甲基-2,4-二硫杂戊烷、4,6-双(3-(2-(1,3-二硫杂环丁基))甲基-5-巯基-2,4-二硫杂戊硫基)-1,3-二噻烷、4,6-双(4-(6-巯基甲硫基)-1,3-二噻烷基硫基)-1,3-二噻烷、4-(4-(6-巯基甲硫基)-1,3-二噻烷基硫基)-6-(4-(6-巯基甲硫基)-1,3-二噻烷基硫基)-1,3-二噻烷、3-(2-(1,3-二硫杂环丁基))甲基-7,9-双(巯基甲硫基)-1,11-二巯基-2,4,6,10-四硫杂十一烷、9-(2-(1,3-二硫杂环丁基))甲基-3,5,13,15-四(巯基甲硫基)-1,17-二巯基-2,6,8,10,12,16-六硫杂十七烷、3-(2-(1,3-二硫杂环丁基))甲基-7,9,13,15-四(巯基甲硫基)-1,17-二巯基-2,4,6,10,12,16-六硫杂十七烷、3,7-双(2-(1,3-二硫杂环丁基))甲基-1,9-二巯基-2,4,6,8-四硫杂 壬烷、4-(3,4,8,9-四(巯基甲硫基)-11-巯基-2,5,7,10-四硫杂十一烷基)-5-巯基甲硫基-1,3-二硫杂环戊烷、4,5-双(3,4-双(巯基甲硫基)-6-巯基-2,5-二硫杂己硫基)-1,3-二硫杂环戊烷、4-(3,4-双(巯基甲硫基)-6-巯基-2,5-二硫杂己硫基)-5-巯基甲硫基-1,3-二硫杂环戊烷、4-(3-双(巯基甲硫基)甲基-5,6-双(巯基甲硫基)-8-巯基-2,4,7-三硫杂辛基)-5-巯基甲硫基-1,3-二硫杂环戊烷、2-(双(3,4-双(巯基甲硫基)-6-巯基-2,5-二硫杂己硫基)甲基)-1,3-二硫杂环丁烷、2-(3,4-双(巯基甲硫基)-6-巯基-2,5-二硫杂己硫基)巯基甲硫基甲基-1,3-二硫杂环丁烷、2-(3,4,8,9-四(巯基甲硫基)-11-巯基-2,5,7,10-四硫杂十一烷硫基)巯基甲硫基甲基-1,3-二硫杂环丁烷、2-(3-双(巯基甲硫基)甲基-5,6-双(巯基甲硫基)-8-巯基-2,4,7-三硫杂辛基)巯基甲硫基甲基-1,3-二硫杂环丁烷、4,5-双(1-(2-(1,3-二硫杂环丁基))-3-巯基-2-硫杂丙硫基)-1,3-二硫杂环戊烷、4-(1-(2-(1,3-二硫杂环丁基))-3-巯基-2-硫杂丙硫基)-5-(1,2-双(巯基甲硫基)-4-巯基-3-硫杂丁硫基)-1,3-二硫杂环戊烷、2-(双(4-(5-巯基甲硫基-1,3-二硫戊环基)硫代))甲基-1、3-二硫杂环丁烷、4-(4-(5-巯基甲硫基-1,3-二硫戊环基)硫代)-5-(1-(2-(1,3-二硫杂环丁基))-3-巯基-2-硫杂丙硫基)-1,3-二硫杂环戊烷、以及它们的寡聚物等具有二硫缩醛(dithioacetal)或二硫缩酮(dithioketal)骨架的化合物。
优选地，所述多硫醇化合物还包括三(巯基甲硫基)甲烷、三(巯基乙硫基)甲烷、1,1,5,5-四(巯基甲硫基)-2,4-二硫杂戊烷、双(4,4-双(巯基甲硫基)-1,3-二硫杂丁基)(巯基甲硫基)甲烷、三(4,4-双(巯基甲硫基)-1,3-二硫杂丁基)甲烷、2,4,6-三(巯基甲硫基)-1,3,5-三硫杂环己烷、2,4-双(巯基甲硫基)-1,3,5-三硫杂环己烷、1,1,3,3-四(巯基甲硫基)-2-硫杂丙烷、双(巯基甲基)甲硫基-1,3,5-三硫杂环己烷、三((4-巯基甲基-2,5-二硫杂环己基-1-基)甲硫基)甲烷、2,4-双(巯基甲硫基)-1,3-二硫杂环戊烷、2-巯基乙硫基-4-巯基甲基-1,3-二硫杂环戊烷、2-(2,3-二巯基丙硫基)-1,3-二硫杂环戊烷、4-巯基甲基-2-(2,3-二巯基丙硫基)-1,3-二硫杂环戊烷、4-巯基甲基-2-(1,3-二巯基-2-丙硫基)-1,3-二硫杂环戊烷、三(2,2-双(巯基甲硫基)-1-硫杂乙基)甲烷、三(3,3-双(巯基甲硫基)-2-硫杂丙基)甲烷、三(4,4-双(巯基甲硫基)-3-硫杂丁基)甲烷、2,4,6-三(3,3-双(巯基甲硫基)-2-硫杂丙基)-1,3,5-三硫杂环己烷、四(3,3-双(巯基甲硫基)-2-硫杂丙基)甲烷等，以及它们的寡聚物等具有三硫代原甲酸酯骨架的化合物。
优选地，所述多硫醇化合物还包括3,3'-二(巯基甲硫基)-1,5-二巯基-2,4-二硫杂戊烷、2,2'-二(巯基甲硫基)-1,3-二硫杂环戊烷、2,7-二(巯基甲基)-1,4,5,9-四硫杂螺[4,4]壬烷、3,9-二巯基-1,5,7,11-四硫杂螺[5,5]十一烷、以及它们的寡聚物等具有四硫代原碳酸酯骨架的化合物等。
需要说明的是，所述多硫醇化合物并不限定于以上举出的各化合物。另外，以上举出的各化合物可以单独使用，也可以为至少2种的组合。
优选地，所述多硫醇化合物包括1,2-双((2-巯基乙基)硫代)-3-巯基丙烷、双(巯基甲基)-3,6,9-三硫杂-1,11-十一烷二硫醇、季戊四醇四(3-巯基丙酸酯)、1,1,3,3-四(巯基甲硫基)丙烷或2-巯基乙醇中的至少一种。
优选地，所述光学材料的制备中，所述聚合在聚合催化剂的存在下进行，所述聚合催化剂优选为有机锡类化合物，示例性地包括但不限于：二丁基二氯化锡、二甲基二氯化锡等二 烷基卤化锡类；二甲基二乙酸锡、二丁基二辛酸锡、二丁基二月桂酸锡等二烷基二羧酸锡类。
另外，根据目的，所述光学材料的制备原料还包括可选地助剂，所述助剂示例性地包括但不限于：扩链剂、交联剂、光稳定剂、紫外线吸收剂、抗氧化剂、油溶染料、填充剂、脱模剂中的任意一种或至少两种的组合物。
优选地，由聚硫氨酯类树脂形成的光学材料通常采用注塑聚合制造。具体而言，将多硫醇化合物和异氰酸酯类物质混合，可选地加入合适的助剂。必要时采用适当的方法将此混合物(聚合性组合物)脱泡后，注入光学材料用注塑模中，通常将其缓缓地从低温加热至高温，使其聚合。然后，经脱模得到光学材料。
优选地，所述聚合的温度为80-200℃，例如可以为90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃等。
优选地，所述聚合的时间为1-24h，例如可以为2h、4h、6h、8h、10h、11h、12h、14h、16h、18h、20h、22h或23h等。
作为本申请的优选技术方案，所述异氰酸酯组合物用于光学材料聚硫氨酯的制备，能够使光学材料具有优异的透明度、颜色稳定性、耐黄变性，显著降低了光学材料的光学形变发生率(≤1％，0-1％)；具体地，以XDI组合物制备的光学材料的黄度指数YI≤1.60，以H6XDI组合物、NBDI组合物制备的光学材料的YI≤1.50。
作为本申请的优选技术方案，以XDI组合物制备的光学材料(聚硫氨酯)的透射比为83.95-84.10％，以H6XDI组合物制备的光学材料(聚硫氨酯)的透射比≥86.0％，以NBDI组合物制备的光学材料(聚硫氨酯)的透射比为85.89-86.85％。
作为本申请的优选技术方案，以XDI组合物制备的光学材料(聚硫氨酯)的玻璃化转变温度(Tg)为84.56-85.67℃，以H6XDI组合物制备的光学材料(聚硫氨酯)的玻璃化转变温度为89.08-89.67℃，以NBDI组合物制备的光学材料(聚硫氨酯)的玻璃化转变温度为108.08-108.65℃。
相对于相关技术，本申请实施例具有以下有益效果：
本申请实施例提供的异氰酸酯组合物中，通过有效因子的设计和控制，使其具有优良的反应活性，能够用于高性能聚氨酯、聚硫氨酯等树脂的制备，不会在聚合过程中出现凝胶等不良现象。而且，所述异氰酸酯组合物能够有效提升聚氨酯、聚硫氨酯等产品的耐黄变性、稳定性和光学性能，使得到的聚氨酯、聚硫氨酯不会出现白浊、不透明的现象。以所述异氰酸酯组合物制备的光学材料的玻璃化转变温度高，耐热性好，具有显著降低的黄度指数和显著降低的光学形变发生率，透射比高，从而有效提升了光学材料的光学性质。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1为本申请一个具体实施方式中所述异氰酸酯组合物的制备方法的流程示意图；
其中，10-成盐工序，20-光气化工序，30-脱除工序，40-分离工序，50-重组分回收工序，60-精制工序。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
本申请中组分和性能的测试方法如下：
1、异氰酸酯组合物中氯的质量含量(A值)的测定：XRF测试
仪器：能量色散型X射线荧光光谱(ED-XRF)，型号：MERAK-LE II；
方法：标准加入法
原理及操作：色谱纯的CCl 4标准品为Cl源，乙酸乙酯为稀释剂，通过X射线光管产生的X射线激发样品中Cl元素，产生特征X射线荧光，特征X射线荧光强度与元素浓度呈线性关系，绘制标准曲线，外推值即为样品中Cl元素含量。
2、异氰酸酯组合物中氯代异氰酸酯的质量含量(B值)的测定：GCMS测试
在下述的条件下利用气相色谱-质谱法进行分析，本文中的含量为归一化含量。
分析仪器：Agilent 5977B GCMS
色谱柱：DB-5色谱柱，规格为30m×0.25mm×0.25μm
柱箱温度：50℃保持2min，以5mL/min的速度升温至80℃，再以15mL/min的速度升温至280℃，保持10min
分离比：不分流
进样口温度：280℃
检测温度：300℃
载气：氦气
载气流量：1mL/min(恒定流量)
进样量：1μL
检测方法：SIM选择离子扫描模式(XDI选择离子为160/126，H6XDI选择离子为186/152，NBDI选择离子为198/164)
3、异氰酸酯组合物中异氰酸酯的质量百分含量的测定：气相色谱测试
在下述的条件下利用气相色谱进行分析，本文中的含量为归一化含量。
分析仪器：Agilent 7890B GC
色谱柱：DB-5色谱柱，规格为30m×0.25mm×0.25μm
柱箱温度：60℃保持1min，以10℃/min的速度升温至300℃，保持5min
分离比：30:1
进样口温度：280℃
检测温度：320℃
载气：氮气
载气流量：1mL/min(恒定流量)
进样量：1μL
检测器：FID
本申请以下具体实施方式中，如无特别说明，“份”及“％”是以质量为基准。
实施例1
一种XDI组合物及其制备方法，所述XDI组合物的有效因子E为4.70，其制备方法的流程示意图如图1所示，具体包括如下步骤：
成盐工序：将800质量份氯苯装入成盐釜中，将成盐釜内的成盐温度调节为25℃，将成盐釜内的成盐压力(表压)调节为0.04MPa G。以85.8质量份/h的速率向成盐釜连续地吹入HCl气体，并且，以1000质量份/h的速率向成盐釜连续地装入1,3-XDA(1,3-苯二亚甲基二胺)的胺溶液(1,3-XDA的质量浓度为8.0wt.％，溶剂为氯苯)，使HCl与1,3-XDA的摩尔比为4:1，由此生成包含1,3-XDA盐酸盐的浆料，并向光气化釜中输送包含1,3-XDA盐酸盐的浆料。
光气化工序：向光气化釜中输送包含1,3-XDA盐酸盐的浆料，以581.5质量份/h的速率向光气化釜连续地通入光气，釜内的反应温度为145℃，反应压力(表压)为0.2MPa G，光气与1,3-XDA盐酸盐的摩尔比为10:1，停留时间为7h，由此，使1,3-XDA盐酸盐与光气反应，生成1,3-XDI，得到包含1,3-XDI的反应产物。
脱除工序：将光气化工序得到的反应产物向脱光气塔和脱溶剂塔中连续地输送，分别进行脱光气处理和脱溶剂处理，由此，制备得到1,3-XDI粗品108质量份。
分离工序：粗品连续向短程蒸发器(脱重组分器)输送，得到脱除重组分的中间品99.7质量份和一级重组分6.3质量份。
重组分回收工序：一级重组分连续向二级短程蒸发器输送得到重组分回收料2.03质量份和残余重组分4.27质量份。以速率为99.7质量份/h的中间品与速率为2.03质量份/h的重组分回收料进行混合得到混合物，即所述混合物中重组分回收料的质量百分含量为2％。
精制工序：向精馏塔中连续地输送前述混合物。对于精馏塔而言，填充有相当于理论塔板数为25的填充物，然后在精馏塔中，从塔顶脱除轻组分，从塔中采出XDI组合物，得到目标产物；
精馏塔中的精馏条件如下所示：
塔底温度：145-150℃
塔顶温度：100-120℃
塔顶压力：0-50PaA
停留时间：2-4h
塔顶回流比：10
精馏工序的采出量：96.2质量份/h。
由此，得到所述XDI组合物，其中1,3-XDI的质量含量＞99％，氯的质量含量(A值)为108ppm，CBI的质量含量(B值)为450ppm，有效因子E为4.70。
实施例2-5，比较例1-2
一种XDI组合物及其制备方法，所述XDI组合物的有效因子E分别如表1所示，其制备方法的流程与实施例1相同，区别仅在于部分工艺参数不同，具体示于表1中(表1中未示出的工艺/参数与实施例1完全相同)。表1中，“HCl比例”表示成盐工序中以1,3-XDA为1mol计，所述HCl的摩尔量；“光气比例”表示光气化工序中以1,3-XDA盐酸盐为1mol计，所述光气的摩尔量；“重组分回收料比例”表示重组分回收工序中，所述混合物中重组分(回收料)的质量百分含量。
表1
Figure PCTCN2022132417-appb-000012
Figure PCTCN2022132417-appb-000013
实施例6-10，比较例3-4
一种H6XDI组合物及其制备方法，所述H6XDI组合物的有效因子E分别如表2所示，其制备方法的流程与实施例1相同，区别仅在于，将成盐工序的1,3-XDA替换为1,3-H6XDA，且进料量保持一致，均为1000质量份/h的1,3-H6XDA(1,3-环己基二甲胺)的胺溶液(质量浓度为8.0wt.％，溶剂为氯苯)。有部分工艺参数不同，具体示于表2中(表2中未示出的工艺/参数与实施例1完全相同)。表2中，“HCl比例”表示成盐工序中以1,3-H6XDA为1mol计，所述HCl的摩尔量；“光气比例”表示光气化工序中以1,3-H6XDA盐酸盐为1mol计，所述光气的摩尔量；“重组分回收料比例”表示重组分回收工序中，所述混合物中重组分(回收料)的质量百分含量。
表2
Figure PCTCN2022132417-appb-000014
Figure PCTCN2022132417-appb-000015
实施例11-15，比较例5-6
一种NBDI组合物及其制备方法，所述NBDI组合物的有效因子E分别如表3所示，其制备方法的流程与实施例1相同，区别仅在于，将成盐工序的1,3-XDA替换为NBDA，且进料量保持一致，均为1000质量份/h的1,3-NBDA(降冰片烷二甲胺)的胺溶液(质量浓度为8.0wt.％，溶剂为氯苯)。有部分工艺参数不同，具体示于表3中(表3中未示出的工艺/参数与实施例1完全相同)。表3中，“HCl比例”表示成盐工序中以NBDA为1mol计，所述HCl的摩尔量；“光气比例”表示光气化工序中以NBDA盐酸盐为1mol计，所述光气的摩尔量；“重组分回收料比例”表示重组分回收工序中，所述混合物中重组分(回收料)的质量百分含量。
表3
Figure PCTCN2022132417-appb-000016
Figure PCTCN2022132417-appb-000017
实施例16-18及比较例7-9
采用相关技术US005196572A的实施例1中的方法制备XDI作为比较例7，此比较例为热裂解法制备XDI，产品中不含氯，也就不含有效因子；将实施例1中的重组分回收料以4％的比例添加至该产品中(即得到的混合物中重组分的质量百分含量为4％)，得到实施例16。
同样采用US005196572A的实施例1的方法制备H6XDI，将原料替换为1,3环己烷二亚甲基二氨基甲酸二甲酯，其他反应条件不变，作为比较例8；将实施例6中的重组分回收料以4％的比例添加至该产品中(即得到的混合物中重组分的质量百分含量为4％)，得到实施例17。
同样采用US005196572A的实施例1的方法制备NBDI，将原料替换为降冰片烷二亚甲基二氨基甲酸二甲酯，作为比较例9；将实施例11中重组分回收料以4％的比例添加至该产品中(即得到的混合物中重组分的质量百分含量为4％)，得到实施例18。
应用例
一种光学材料，具体为塑料透镜材料，是通过异氰酸酯类物质与多硫醇化合物聚合而成的聚硫氨酯树脂；所述异氰酸酯类物质分别为实施例1-18、比较例1-9提供的异氰酸酯组合物，所述多硫醇化合物为1,2-双((2-巯基乙基)硫代)-3-巯基丙烷。
所述光学材料的具体制备方法如下：
向烧瓶中装入二丁基二氯化锡0.001质量份、内部脱模剂(Stepan公司制，ZELECUN，酸性磷酸酯)0.07质量份、紫外线吸收剂(堺化学工业公司制，Biosorb 583)0.05质量份、XDI组合物36.4质量份(实施例1-5、16，比较例1-2、7)；对于H6XDI组合物的质量为37.7质量份(实施例6-10、17，比较例3-4、8)，对于NBDI组合物的质量为39.9质量份(实施例11-15、18，比较例5-6、9)。而后，在25℃下搅拌1h，使其充分溶解，得到多异氰酸酯成分；
向该多异氰酸酯成分中装入1,2-双((2-巯基乙基)硫代)-3-巯基丙烷33.6质量份并进行混合，制备聚合性组合物；
在600Pa压力下对该聚合性组合物进行1h的脱泡处理，然后用3μm的PTFE过滤器进行过滤后注入至由玻璃模具和胶带形成的铸模中。将该铸模置于烘箱中，从10℃缓缓升温至120℃，进行18h聚合。聚合结束后，将铸模从烘箱中取出，进行脱模，得到所述光学材料。
对前述光学材料进行性能测试，方法如下：
(1)黄度指数(YI值)的测试
根据国标GB/T 2409-1980中的方法测定透镜的黄度指数；
将待测的光学材料制成厚度为9mm、直径为75mm的圆形平板塑料透镜，使用分光光度计，测定三刺激值x、y、z；通过下式计算YI值：
Figure PCTCN2022132417-appb-000018
YI值越小，代表塑料透镜的色相越好；YI值越大，色相越不良。
(2)光学形变发生率的测试
光学形变是指由于材料的组成不同等原因导致局部与周围正常折射率不同的现象。本申请中，在高压汞灯下目视观察100片透镜(规格与YI值测试中的透镜规格相同)，确认有条纹状的透镜判定为有光学形变的透镜，计算光学形变发生率，即光学形变发生率＝100％×光学形变的透镜个数/100。
(3)透射比测试
根据GB/T 10810.3-2006《眼镜镜片及相关眼镜产品第3部分：透射比规范及测量方法》测试镜片的透射比。
(4)玻璃化转变温度(Tg)测试
利用差示扫描量热法(DSC法)测试玻璃化转变温度Tg，每个样品平行测试3次，取平均值；
玻璃化转变温度(Tg)测试：采用梅特勒-托利多公司的高压差示扫描量热仪(METTLER HPDSC 1)，DSC测试方法：30℃-300℃，升温扫描，升温速率为10℃/min，氮气氛围，氮气流量为50mL/min。
具体测试结果如表4、表5和表6所示：
表4
Figure PCTCN2022132417-appb-000019
表5
Figure PCTCN2022132417-appb-000020
Figure PCTCN2022132417-appb-000021
表6
Figure PCTCN2022132417-appb-000022
结合以上的性能测试数据可知，本申请通过将异氰酸酯组合物的有效因子控制在3.90-5.70范围内，使制备得到的聚硫氨酯光学材料具有较低的黄度指数和光学形变发生率，光学形变发生率为0-1％。其中，以XDI组合物制备的光学材料的黄度指数YI≤1.60，YI为 1.41-1.60，透射比为83.95-84.10％，Tg为84.56-85.67℃；以H6XDI组合物制备的光学材料的YI≤1.50，YI为1.31-1.50，透射比为86.03-86.72％，Tg为89.08-89.67℃；以NBDI组合物制备的光学材料的YI≤1.50，YI为1.32-1.50，透射比为85.89-86.85％，Tg为108.08-108.65℃，兼具优异的光学性能和耐热性。
申请人声明，本申请通过上述实施例来说明本申请的异氰酸酯组合物、改性异氰酸酯、聚氨酯树脂和光学材料，但本申请并不局限于上述工艺步骤，即不意味着本申请必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。

Claims (15)

  1. 一种异氰酸酯组合物，其中，所述异氰酸酯组合物的有效因子为3.90-5.70；
    所述有效因子的计算公式如式I所示：
    Figure PCTCN2022132417-appb-100001
    其中，E为有效因子；
    A为所述异氰酸酯组合物中氯的质量含量；
    B为所述异氰酸酯组合物中氯代异氰酸酯的质量含量；
    M Cl为氯的相对原子质量；
    M B为所述氯代异氰酸酯的相对分子质量。
  2. 根据权利要求1所述的异氰酸酯组合物，其中，所述A通过X射线荧光光谱分析测试得到。
  3. 根据权利要求1或2所述的异氰酸酯组合物，其中，所述B通过色谱-质谱法测试得到，进一步优选通过气相色谱-质谱法测试得到。
  4. 根据权利要求1-3任一项所述的异氰酸酯组合物，其中，所述异氰酸酯为二异氰酸酯，优选包括苯二亚甲基二异氰酸酯、双异氰酸酯甲酯基环己烷、双异氰酸酯甲酯基降冰片烷中的任意一种或至少两种的组合。
  5. 根据权利要求1-4任一项所述的异氰酸酯组合物，其中，所述异氰酸酯组合物中异氰酸酯的质量百分含量≥97％。
  6. 根据权利要求1-5任一项所述的异氰酸酯组合物，其中，所述有效因子对应的物质包括如下化合物中的任意一种或至少两种的组合：
    Figure PCTCN2022132417-appb-100002
    其中，R为异氰酸酯中的NCO基团被去除得到的二价基团；
    优选地，所述R选自
    Figure PCTCN2022132417-appb-100003
    中的任意一种或至少两种的组合；其中，波浪线代表基团的连接位点。
  7. 根据权利要求1-6任一项所述的异氰酸酯组合物，其中，所述氯代异氰酸酯为异氰酸酯中的一个NCO基团被氯替代得到的化合物；
    优选地，所述氯代异氰酸酯包括
    Figure PCTCN2022132417-appb-100004
    Figure PCTCN2022132417-appb-100005
    中的任意一种或至少两种的组合。
  8. 一种如权利要求1-7任一项所述的异氰酸酯组合物的制备方法，其包括：胺类化合物与光气进行反应，得到所述异氰酸酯组合物。
  9. 根据权利要求8所述的制备方法，其包括如下步骤：
    (1)胺类化合物与光气进行反应，得到反应产物；
    (2)对步骤(1)得到的反应产物进行脱除处理，得到粗品；所述脱除处理包括脱光气处理和/或脱溶剂处理；
    (3)将步骤(2)得到的粗品依次进行分离和精制，得到所述异氰酸酯组合物。
  10. 根据权利要求9所述的制备方法，其中，步骤(3)所述分离得到重组分和中间品；将所述中间品和重组分的混合物进行精制，得到所述异氰酸酯组合物；所述混合物中重组分的质量百分含量为1-10％。
  11. 根据权利要求10所述的制备方法，其中，所述精制的方法为精馏。
  12. 一种改性异氰酸酯，其中，所述改性异氰酸酯通过如权利要求1-7任一项所述的异氰酸酯组合物改性得到；
    所述改性异氰酸酯包含基团(a)-(i)中的任意一种或至少两种的组合：(a)异氰脲酸酯基，(b)脲二酮基，(c)缩二脲基，(d)氨基甲酸酯基，(e)脲基，(f)亚氨基噁二嗪二酮基，(g)脲基甲酸酯基，(h)脲酮亚胺基，(i)碳二亚胺基。
  13. 一种聚氨酯树脂，其中，所述聚氨酯树脂通过异氰酸酯类物质与含活性氢基团的物质反应而成；所述异氰酸酯类物质包括如权利要求1-7任一项所述的异氰酸酯组合物、如权利要求12所述的改性异氰酸酯中的至少一种。
  14. 一种光学材料，其中，所述光学材料通过异氰酸酯类物质与多硫醇化合物聚合而成；所述异氰酸酯类物质包括如权利要求1-7任一项所述的异氰酸酯组合物、如权利要求12所述的改性异氰酸酯中的至少一种；
    优选地，所述多硫醇化合物包括1,2-双((2-巯基乙基)硫代)-3-巯基丙烷、双(巯基甲基)-3,6,9-三硫杂-1,11-十一烷二硫醇、季戊四醇四(3-巯基丙酸酯)、1,1,3,3-四(巯基甲硫基)丙烷或2-巯基乙醇中的至少一种。
  15. 根据权利要求14所述的光学材料，其中，所述光学材料应用于镜片、透镜、棱镜、灯罩材料、透明包装材料、透明建筑材料或电子产品中。
PCT/CN2022/132417 2022-11-17 2022-11-17 一种异氰酸酯组合物、改性异氰酸酯、聚氨酯树脂和光学材料 WO2024103321A1 (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109153637A (zh) * 2017-04-10 2019-01-04 三井化学株式会社 苯二甲撑二异氰酸酯组合物、苯二甲撑二异氰酸酯改性物组合物、二液型树脂原料及树脂
CN112661930A (zh) * 2020-11-27 2021-04-16 万华化学集团股份有限公司 一种苯二亚甲基二异氰酸酯组合物及光学树脂
CN114031744A (zh) * 2021-11-29 2022-02-11 万华化学集团股份有限公司 双异氰酸酯甲酯基环己烷组合物、其改性物组合物及制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109153637A (zh) * 2017-04-10 2019-01-04 三井化学株式会社 苯二甲撑二异氰酸酯组合物、苯二甲撑二异氰酸酯改性物组合物、二液型树脂原料及树脂
CN112661930A (zh) * 2020-11-27 2021-04-16 万华化学集团股份有限公司 一种苯二亚甲基二异氰酸酯组合物及光学树脂
CN114031744A (zh) * 2021-11-29 2022-02-11 万华化学集团股份有限公司 双异氰酸酯甲酯基环己烷组合物、其改性物组合物及制备方法

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