WO2022115990A1 - 多异氰酸酯组合物及其制备方法和应用 - Google Patents

多异氰酸酯组合物及其制备方法和应用 Download PDF

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WO2022115990A1
WO2022115990A1 PCT/CN2020/133079 CN2020133079W WO2022115990A1 WO 2022115990 A1 WO2022115990 A1 WO 2022115990A1 CN 2020133079 W CN2020133079 W CN 2020133079W WO 2022115990 A1 WO2022115990 A1 WO 2022115990A1
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reaction
chlorine
diisocyanate
phosgene
ppm
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PCT/CN2020/133079
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English (en)
French (fr)
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俞勇
崔学磊
郭耀允
尚永华
韩金平
李文滨
刘德刚
黎源
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万华化学集团股份有限公司
万华化学（宁波）有限公司
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Priority to KR1020237015267A priority Critical patent/KR20230079440A/ko
Priority to JP2023524847A priority patent/JP2023549053A/ja
Priority to PCT/CN2020/133079 priority patent/WO2022115990A1/zh
Priority to EP20963839.4A priority patent/EP4219583A1/en
Priority to US18/253,868 priority patent/US20230374194A1/en
Publication of WO2022115990A1 publication Critical patent/WO2022115990A1/zh

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    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • 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
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings

Definitions

  • the present application relates to the technical field of polyurethane, in particular to a polyisocyanate composition and a preparation method and application thereof.
  • Polyurethane is one of the synthetic resins with excellent comprehensive properties. Due to its wide variety of synthetic monomers, mild, specific and controllable reaction conditions, large room for formula adjustment and microstructure characteristics of polymer materials, it can be widely used in coatings, adhesives, foamed plastics, synthetic fibers and elastomers , has become one of the essential materials for people's clothing, food, housing, and transportation; moreover, it has formed a multi-variety and multi-series material family, forming a complete polyurethane industrial system, which is the most important part of other resins. not available.
  • the reaction concentration in the local area of the reaction space may be too high, resulting in an excessively violent reaction, and a large amount of heat is released to promote the excessive reaction. If the reaction is locally out of control, it is also easy to cause the turbidity of the polyurethane synthetic emulsion, which will eventually lead to the failure of the polyurethane product.
  • CN110511163A discloses a method for preparing polyisocyanate by photochemical reaction and a method for preparing water-based polyurethane resin, and specifically discloses that the chlorine content in polyisocyanate will affect the yellowing resistance of water-based polyurethane resin, and may even directly lead to the occurrence of water-based polyurethane resin. At the same time, it may adversely affect the reactivity of some systems.
  • CN1064074A discloses a method for reducing the content of hydrolyzable chloride in toluene diisocyanate, especially its distillation residue.
  • the application specifically discloses that the content of hydrolyzable chloride in diisocyanate is too high, and its viscosity is unstable and inactive, so it needs to be It is treated to reduce its hydrolyzable chloride content to a level at which the residue is active and viscous stable.
  • One of the purposes of the present application is to provide a polyisocyanate composition, which can solve the problem of unstable reactivity in the prepolymerization stage and the chain extension stage that is easy to occur in the synthesis process of the polyurethane resin, and effectively improve the turbidity of the synthetic emulsion. In order to improve the light transmittance and yellowing resistance of polyurethane products.
  • the present application provides a polyisocyanate composition
  • the value of the mass content of alkaline hydrolyzed chlorine minus the mass content of hydrolyzed chlorine in the polyisocyanate composition is 0.1ppm-100ppm, such as 0.2ppm, 0.3ppm, 0.4ppm, 0.5ppm , 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm, 50ppm, 55ppm, 60ppm, 65ppm, 70ppm, 75ppm, 80ppm, 85ppm , 90ppm, 95ppm, 98ppm, etc.;
  • the mass content of the alkaline hydrolyzed chlorine is the mass content of the halogens dissociated under alkaline conditions and/or the halogens dissociated under temperature conditions above 100°C calculated from the relative atomic mass of chlorine atoms.
  • the calculation by the relative atomic mass of the chlorine atom in this application refers to: by measuring the amount or molar content of the dissociated halogen substance, no matter what kind of halogen it is, the relative atomic mass of the chlorine atom (35.45 g /mol) converted to mass or mass content.
  • a polyisocyanate composition containing the above-mentioned specific amount of alkali-hydrolyzed chlorine is provided.
  • the chlorine in the alkali-hydrolyzed chlorine will be dissociated, and the chlorine in the alkali-hydrolyzed chlorine will be dissociated.
  • the catalyst is poisoned to reduce the reactivity of the local overreaction area, thereby avoiding the turbidity of the polyurethane synthetic emulsion, thereby improving the light transmittance and yellowing resistance of the polyurethane product.
  • the value of the mass content of alkaline hydrolyzed chlorine minus the mass content of hydrolyzed chlorine in the polyisocyanate composition is 0.2 ppm-60 ppm, preferably 0.4 ppm-40 ppm.
  • the value of the mass content of alkaline hydrolyzed chlorine minus the mass content of hydrolyzed chlorine is further preferred, so that the turbidity of the polyurethane synthetic emulsion can be further improved, and the light transmittance and yellowing resistance of the product can be improved. . If the amount of alkali hydrolyzed chlorine is too low, the turbidity of the polyurethane synthetic emulsion will be aggravated, and the light transmittance of the polyurethane product will be reduced. Deteriorates the yellowing resistance.
  • the halogen includes any one or a combination of at least two of fluorine, chlorine, bromine or iodine.
  • the polyisocyanate composition includes a combination of polyisocyanate, alkali-hydrolyzed chlorine-based impurities, and hydrolyzed chlorine-based impurities.
  • the alkali-hydrolyzed chlorine impurities are substances that dissociate to obtain alkali-hydrolyzed chlorine
  • the hydrolyzed chlorine impurities are substances that are dissociated to obtain hydrolyzed chlorine.
  • one of the sources of chlorine-based impurities in alkaline hydrolysis is: in the process of phosgenation reaction, after an isocyanate group in the main product polyisocyanate is dropped, after the olefin structure is formed, in the phosgene In the chemical environment, it will be further combined with hydrogen chloride.
  • alkali-hydrolyzed chlorines For alkali-hydrolyzed chlorines, different control measures need to be taken for different sources.
  • the alkali-hydrolyzed chlorines in polyisocyanates are difficult to remove by conventional separation means, or require a lot of energy and material consumption Chlorine to be removed needs to be controlled at the source.
  • the polyisocyanate is a diisocyanate.
  • the polyisocyanate includes any one or a combination of at least two of alicyclic diisocyanate, aromatic diisocyanate or chain diisocyanate.
  • the polyisocyanates include dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-dimethyl isocyanate Isocyanate cyclohexane, 1,4-dimethyl isocyanate cyclohexane, tetramethylene diisocyanate, pentamethylene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), benzene diisocyanate Any one of isocyanate, naphthalene diisocyanate or cyclohexyl diisocyanate or a combination of at least two.
  • the polyisocyanate includes dicyclohexylmethane diisocyanate, and the alkali-hydrolyzed chlorine impurities include any one or a combination of at least two of the following compounds:
  • the X is F, Cl, Br or I.
  • the polyisocyanate includes isophorone diisocyanate, and the alkali-hydrolyzed chlorine impurities include any one or a combination of at least two of the following compounds:
  • the X is F, Cl, Br or I.
  • the polyisocyanate includes hexamethylene diisocyanate
  • the alkali-hydrolyzed chlorine impurities include any one or a combination of at least two of the following compounds:
  • the X is F, Cl, Br or I.
  • the polyisocyanate composition further includes an anti-aging aid.
  • the anti-aging auxiliary is added to enhance the storage stability of the polyisocyanate composition, prolong its shelf life, and facilitate the realization that during the process of preparing the polyurethane resin using the polyisocyanate composition of the present application, the color number of the polyisocyanate composition remains stable and is not easy to yellow.
  • the anti-aging adjuvant includes any one or at least two combinations of hindered phenol antioxidants, compounds containing sulfonamide groups or organic phosphites, preferably hindered phenol antioxidants, more preferably antioxidant 264 (for example, any one or a combination of at least two of the antioxidant 245 (for example, the German BASF company, Irganox 245) or the antioxidant 1076 (for example, the German BASF company, Irganox 1076).
  • the antioxidant 245 for example, the German BASF company, Irganox 245
  • the antioxidant 1076 for example, the German BASF company, Irganox 1076.
  • the mass content of the anti-aging aid in the polyisocyanate composition is 50-5000ppm, such as 100ppm, 500ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm, etc., preferably 100-1000ppm.
  • the raw materials for the preparation of the polyisocyanate composition include a combination of polyamine and phosgene-based raw materials.
  • the polyamine refers to a compound containing at least two (eg, 2, 3, 4, etc.) amino groups.
  • the total mass content of impurities having unsaturated olefin-based structure, secondary amine-based structure or hydroxyl-based structure in the polyamine is 0.1 ppm-400 ppm, such as 0.5 ppm, 1 ppm, 5 ppm, 10 ppm, 50 ppm, 100 ppm, 150 ppm , 200ppm, 250ppm, 300ppm, 350ppm, etc.
  • another source of alkali-hydrolyzed chlorine is: in the preparation process of the raw material polyamine, some of the components therein generate alkali-hydrolyzed chlorines during the subsequent process of phosgenation to prepare isocyanates, specifically
  • the structure includes but is not limited to the following situations: a) unsaturated olefin structure b) secondary amine structure c) hydroxyl structure, the material containing the above structure is generally difficult to separate from the raw material polyamine, in the phosgenation process, especially in the phosgenation process. It reacts with phosgene or hydrogen chloride during gas phase phosgenation to form alkaline hydrolyzed chlorines. Therefore, in terms of raw material polyamines, it is necessary to control the total amount of these kinds of substances, and in this application, it is recommended to control the total amount within 0.1 ppm-400 ppm.
  • the determination of the mass content of hydrolyzed chlorine is the prior art, including but not limited to the method provided in GB/T 37042-2018.
  • the mass content of alkaline hydrolyzed chlorine those skilled in the art can also test by conventional means, the application only exemplarily provides the following test methods, but is not limited to the following methods:
  • the alkaline hydrolyzed chlorine in the polyisocyanate is mainly chlorine that can be dissociated under alkaline conditions.
  • the alkali-hydrolyzable halogens are dissociated under the conditions, and the dissociated halogen ions form corresponding salts, and then the content is determined by potentiometric titration with silver nitrate standard solution.
  • the instruments used in the testing process are:
  • the reagents used in the testing process are:
  • Nitric acid solution nitric acid (GB626) and water are mixed by 1:3 volume;
  • test steps are as follows:
  • the alkaline hydrolysis chlorine is calculated by the following formula:
  • V-volume of silver nitrate standard solution consumed when titrating the sample mL
  • V 0 - volume of silver nitrate standard solution consumed when titrating blank mL
  • the second purpose of the present application is to provide a method for preparing the polyisocyanate composition according to one of the purposes. thing.
  • the polyamines include m-xylylenediamine, p-xylylenediamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, 1,4-butanediamine, 1,4-cyclohexanediamine, 6-Hexanediamine, 1,4-diaminocyclohexane, diaminodicyclohexylmethane (for example, industrial product H 12 MDA, which is a mixture of 4,4-diaminodicyclohexylmethane, 2,4-di mixtures of aminodicyclohexylmethane, 2,2-diaminodicyclohexylmethane, etc.), toluenediamine, methylenediphenylamine (eg, 2,2'-methylenediphenylamine, 4,4'-methylenediphenylamine Methyl diphenylamine), isophorone diamine, phenylenediamine,
  • the phosgene-based raw material is in excess.
  • the phosgene-based raw materials include any one or at least two combinations of phosgene, diphosgene, triphosgene, fluorophosgene or bromophosgene, preferably phosgene, diphosgene, triphosgene or fluorine One or at least two combinations of phosgene, more preferably phosgene and/or fluorophosgene.
  • the preparation method further comprises: post-processing the crude product obtained by the phosgene reaction.
  • the phosgenation reaction includes gas-phase phosgenation reaction, liquid-phase phosgenation reaction or salt-forming phosgenation reaction.
  • the phosgenation reaction of the present application can be carried out using process types known in the art. According to the method provided by the present application, in some examples, the phosgenation reaction is selected from gas phase phosgenation reaction, liquid phase phosgenation reaction or salt-forming phosgenation reaction. In different phosgenation reaction processes, different means need to be adopted to control the content of chlorine in alkaline hydrolysis.
  • the gas-phase phosgenation reaction comprises: gas-phase phosgenation reaction of polyamine gas stream and phosgene-based raw materials, the reaction product is mixed with a liquid inert medium and cooled to ⁇ 150°C, or, the reaction product is mixed with a liquid inert medium and The mixture of target isocyanate products is mixed and cooled to ⁇ 150°C, such as 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, etc., preferably 100°C -140°C to obtain crude isocyanate.
  • the reaction mixture gas since the temperature of the reaction mixture gas is relatively high and at the same time to control the generation of chlorine in alkaline hydrolysis, the reaction mixture gas is required to be absorbed and cooled by a liquid inert medium and/or a mixture of an inert medium and an isocyanate. ⁇ 150°C, in order to reduce the generation of chlorine in alkaline hydrolysis.
  • the step of gas phase phosgenation comprises: 1) gasifying polyamines to form a polyamine gas stream containing polyamine droplets; 2) removing polyamines contained in the polyamine gas stream amine droplets to obtain a polyamine gas stream substantially free of polyamine droplets; 3) carrying out a gas phase phosgenation reaction between the polyamine gas stream substantially free of polyamine droplets and phosgene-based raw materials, and the reaction product is inert with a liquid state A medium (eg, aromatic solvent) is mixed and rapidly cooled to 100-140°C in a gas jet absorber, or the reaction product is mixed with a mixture of liquid inert medium and target isocyanate product and rapidly cooled to 100°C in a gas jet absorber -140°C to obtain crude isocyanate.
  • a medium eg, aromatic solvent
  • a heater is used to remove the polyamine droplets contained in the polyamine gas stream; for example, the specific structure of the heater used can refer to the corresponding content disclosed in the patent application CN105214568A.
  • the temperature of the gas phase phosgenation reaction is, for example, 200-550°C (eg, 250°C, 300°C, 320°C, 380°C, 420°C, 500°C), preferably 250-400°C; the reaction pressure is 0.01-1MPa ( For example, 0.05MPa, 0.08MPa, 0.2MPa, 0.5MPa, 0.8MPa), preferably 0.03-0.3MPa.
  • the mixed gas (reaction product) after the reaction of the phosgene-based raw material with the polyamine can be absorbed and cooled with a liquid inert medium (e.g., aromatic solvent) and/or a mixture of the inert medium and isocyanate.
  • a liquid inert medium e.g., aromatic solvent
  • the liquid-phase phosgene reaction includes: firstly performing a cold reaction between the polyamine solution and phosgene-based raw materials at 0-100° C., and then performing a thermal reaction at 60-180° C. The cold reaction and the thermal reaction are combined. Total residence time ⁇ 7h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, etc.
  • the total residence time of the cold reaction and the heat reaction is controlled within 7h, so that the generation of alkaline hydrolysis chlorine can be controlled.
  • the liquid phase phosgenation reaction can be found in patent application CN103319372A.
  • the liquid phase phosgenation reaction is carried out in two steps: 1) cold reaction, the temperature is 0-100°C, preferably 40-70°C; the pressure is 0.1-1MPa absolute; the polyamine is mixed with an aromatic solvent (can be selected from one or more of chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, p-dichlorobenzene and chlorotoluene) and react with superstoichiometric phosgene raw materials after mixing them into a solution.
  • the residence time can be 2-120 min, preferably 5-45 min.
  • the temperature is 60-180 °C, preferably 110-165 °C, more preferably 120-150 °C; pressure is absolute pressure 0.1-1MPa; with chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, p-dichlorobenzene
  • chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, p-dichlorobenzene One or more of benzene and chlorotoluene are used as solvents to react with superstoichiometric phosgene raw materials, and the reaction residence time can be 0.5-5h.
  • the total residence time of the cold reaction and the heat reaction is ⁇ 7h.
  • the salt-forming phosgenation reaction comprises: performing a salt-forming reaction with hydrogen chloride and/or carbon dioxide and a polyamine in an inert solvent, and then performing a phosgenation reaction with phosgene-based raw materials; the salt-forming reaction and phosgenation
  • the total residence time of the reaction is ⁇ 7h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, etc.
  • the total residence time of the salt-forming reaction and the phosgenation reaction is controlled within 7 hours, so that the generation of alkaline hydrolysis chlorine can be controlled.
  • the phosgenation reaction can also be carried out in hydrogen chloride and/or carbon dioxide, that is, salt-forming phosgenation reaction, for details, please refer to patent applications CN105218422A and CN 107337615A.
  • the step of the salt-forming phosgenation reaction is: 1) hydrogen chloride and/or carbon dioxide and a polyamine are subjected to a salt-forming reaction in an inert solvent, and the molar equivalent ratio of the hydrogen chloride to the amino group in the polyamine is 1- 2.5:1, preferably 1.2-2:1, the molar equivalent ratio of the carbon dioxide to the amino group in the polyamine is 0.5-5:1, preferably 0.6-3:1, and the mass ratio of the inert solvent to the polyamine is 25- 5:1, preferably 20-5:1; the temperature of the salt-forming reaction is 0-50°C, preferably 5-30°C, and the pressure is 0.1-1MPa absolute pressure, preferably 0.2-0.5MPa absolute pressure; reaction residence time 1-15min,
  • step 1) salt-forming reaction
  • the obtained reaction solution of hydrochloride or carbonate enters step 2) to carry out phosgenation reaction with phosgene raw materials
  • the reaction temperature is 100-170°C, preferably 110-165°C, More preferably 120-150°C
  • the reaction pressure is 0.1-1MPa absolute pressure, preferably 0.2-0.5MPa absolute pressure
  • the reaction with superstoichiometric phosgene-based raw materials the reaction residence time can be 1-8h.
  • the inert solvent is selected from one or more of chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, p-dichlorobenzene and chlorotoluene.
  • the total residence time in step 1) and step 2) is less than or equal to 7h.
  • the reaction solution can be filtered and subsequently separated as required.
  • a rectifying tower or a stripping tower is usually used to remove by-product hydrogen chloride and excess phosgene-based raw materials in the reaction solution, and the phosgene-based raw materials can be transported back to the reaction system for recycling after being refined;
  • a rectifying tower is used to remove the solvent in the reaction solution, and the solvent can be sent back to the reaction system for recycling after being refined; a crude polyisocyanate composition stream substantially free of solvent is obtained by separation.
  • the crude polyisocyanate composition stream is separated and refined by a scraped-plane evaporator or a rectifying tower, and the non-volatile components (tar) and low-boiling light components are removed to obtain the corresponding polyisocyanate composition.
  • the third object of the present application is to provide a polyurethane resin, the preparation raw materials of the polyurethane resin include the combination of the polyisocyanate composition described in one of the objects and a compound containing an active hydrogen group.
  • the polyurethane resin is the reaction product of the polyisocyanate component in the polyisocyanate composition and the compound containing an active hydrogen group.
  • the polyurethane resin provided by the present application has low turbidity of the emulsion obtained in the synthesis process, high light transmittance of the polyurethane product, and good yellowing resistance and heat resistance.
  • the compound containing an active hydrogen group includes a polyol compound and/or an amine compound.
  • the polyol compound is a compound having at least two hydroxyl groups.
  • the molecular weight of the polyol compound is 400-20,000, such as 800, 1,000, 2,000, 5,000, 8,000, 10,000, 15,000, 18,000, and the like.
  • the hydroxyl value of the polyol compound is 10mg KOH/g-1500mg KOH/g, such as 20mg KOH/g, 30mg KOH/g, 40mg KOH/g, 50mg KOH/g, 100mg KOH/g, 200mg KOH/g, 500mg KOH/g, 800mg KOH/g, 1000mg KOH/g, 1200mg KOH/g, 1400mg KOH/g, etc.
  • the hydroxyl value of the polyol component can be determined by analysis according to the method A-phthalic anhydride method in the GB/T 12008.3-2019 standard.
  • the functionality of the polyol compound is 2-8, such as 3, 4, 5, 6, 7, and the like.
  • the polyol compound includes any one or a combination of at least two of polyether polyol, polyester polyol, polyolefin polyol, epoxy resin or bio-based polyol.
  • the polyether polyol includes polyoxyethylene polyol, polyoxypropylene polyol, polymer polyol, polyurea polyol, polytetrahydrofuran and its copolyether glycol, polytrimethylene glycol or aromatic Any one or a combination of at least two of the polyether polyols.
  • the polyester polyol includes any one or a combination of at least two of adipic acid-based polyester diol, aromatic polyester polyol, polycaprolactone polyol or polycarbonate diol.
  • the adipic acid-based polyester diol includes polyethylene adipate diol, polytrimethylene adipate diol, polybutylene adipate diol or polyadipate diol Any one or a combination of at least two of the alcohol ester diethylene glycol.
  • the aromatic polyester polyol comprises polyethylene phthalate diol, 1,6-hexanediol phthalate diol or neopentyl phthalate Any one or a combination of at least two of the alcohol ester diols.
  • the polycaprolactone polyol includes polycaprolactone diol and/or polycaprolactone triol.
  • the polycarbonate diol includes any one or a combination of at least two of polyethylene carbonate diol, poly-1,6-hexanediol carbonate or polybutylene carbonate diol.
  • the polyolefin polyol comprises hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated epoxidized polybutadiene resin, hydroxyl-terminated polybutadiene-acrylonitrile or polystyrene polyol Any one or a combination of at least two of the alcohols.
  • the epoxy resin includes any one or a combination of at least two of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin or aliphatic epoxy resin.
  • the bio-based polyols include any of castor oil and its derivative polyols, soybean oil polyols, palm oil polyols, rosin ester polyols, fatty acid dimer diols, fish oil polyols or lignin polyols one or a combination of at least two.
  • the raw materials for the preparation of the polyurethane resin further include a catalyst and/or a chain extender.
  • the chain extender comprises a multifunctional alcohol compound (eg, its functionality is 2, 3, 4, 5) and/or a multifunctional amine compound (eg, its functionality is 2, 3, 4, 5), preferably ethylene glycol, diethylene glycol (diethylene glycol), 1,2-propanediol, dipropylene glycol, 1,4-butanediol (1,4-butanediol, BDO), 1,6-Hexanediol (HD), Trimethylolpropane (TMP), Castor Oil, Ethylenediamine (EDA), Hydrazine, Hexanediamine, Isophoronediamine, Methylpentanediamine, Dimethicone Any one or a combination of at least two of ethylenetriamine or triethylenetetramine.
  • a multifunctional alcohol compound eg, its functionality is 2, 3, 4, 5
  • a multifunctional amine compound eg, its functionality is 2, 3, 4, 5
  • ethylene glycol ethylene glycol
  • the chain extender used is a hydrophilic chain extender, preferably dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA), 1,4-butanediol-2- Sodium sulfonate, diethanolamine, triethanolamine, N-methyldiethanolamine (MDEA), N-ethyldiethanolamine (EDEA), N-propyldiethanolamine (PDEA), N-butyldiethanolamine (BDEA), Any one or a combination of at least two of dimethylethanolamine, bis(2-hydroxyethyl)aniline (BHBA), bis(2-hydroxypropyl)aniline (BHPA) and N-methyldiethanolamine (MDEA) .
  • DMPA dimethylol propionic acid
  • DMBA dimethylol butyric acid
  • 1,4-butanediol-2- Sodium sulfonate diethanolamine, triethanolamine, N-methyldiethanolamine (MDEA), N-ethyld
  • the polyurethane resin can be manufactured by using the process routes known in the art, such as the one-step method and the prepolymer method.
  • the prepolymer method is preferably used for polymerization.
  • the one-step method is a preparation method in which the raw materials required for polyisocyanate (eg, alicyclic diisocyanate composition), polyol, catalyst, chain extender and the like are uniformly mixed at one time, and cast molding.
  • polyisocyanate eg, alicyclic diisocyanate composition
  • polyol e.g, polyol
  • catalyst e.g., chain extender and the like
  • the prepolymer method is to react with a polyol and a slightly excess polyisocyanate (such as a cycloaliphatic diisocyanate composition) to synthesize a polyurethane prepolymer terminated with isocyanate groups at both ends, and then combine the prepolymer with a catalyst. , and the chain extender is further reacted, cured and casted to obtain a polyurethane elastomer material.
  • a slightly excess polyisocyanate such as a cycloaliphatic diisocyanate composition
  • the preparation of the polyurethane resin by a prepolymer method includes the following steps:
  • the formulation of raw materials used in the prepolymer method described in the present application includes the following raw materials in parts by mass: 50-500 parts, preferably 100-400 parts of polyisocyanate composition; 100 parts of polyol; 50 parts of chain extender -500 parts, preferably 50-400 parts; 0.005-1 part of catalyst, preferably 0.01-0.5 part.
  • the chain extender can be a conventional chain extender in the art.
  • the chain extender described in the present application may be a bifunctional compound or a trifunctional compound and above, and the bifunctional compound may include, for example, 1,4-butanediol, ethylene glycol, diethylene glycol Alcohols, 1,6-hexanediol and other glycols, such as 3,3'-dichloro-4,4'-diphenylmethanediamine (MOCA), 3,5-diethyltoluenediamine (DETDA ) and other diamines, ethanolamine, etc., and compounds with trifunctional groups and above include glycerol, trimethylolpropane, pentaerythritol; the present application is preferably 1,4-butanediol and/or 3,3'-dichloro-4 , 4'-Diphenylmethanediamine.
  • MOCA 3,3'-dichloro-4,4'-diphenylmethanediamine
  • the content of isocyanate groups in the prepared isocyanate-terminated prepolymer can be analyzed by titration using the method specified in the GB/T 12009.4-1989 standard.
  • the amount of the chain extender can be calculated with reference to the method provided in the patent application CN110982038A; in this application, the chain extension coefficient of the chain extender is preferably 0.8-1.1, more preferably 0.9-1.0.
  • the catalyst for the prepolymer method is generally an organotin compound, such as stannous octoate, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin bis(dodecyl sulfide), for example.
  • organotin compound such as stannous octoate, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin bis(dodecyl sulfide), for example.
  • the process route of the present application is preferably dibutyltin dilaurate.
  • additives in the industry such as plasticizers, defoaming agents, flame retardants, dehydrating agents, antioxidants, can be further added in appropriate proportions , UV absorber, anti-hydrolysis agent, weather-resistant stabilizer, etc.
  • the fourth object of the present application is to provide an application of the polyurethane resin described in the third object, which is used in polyurethane elastomers, polyurethane optical materials, polyurethane coating materials (such as coatings, adhesives) or polyurethane foams It is preferably used in the preparation of polyurethane elastomers.
  • the present application provides a polyisocyanate composition containing a specific amount of alkali-hydrolyzed chlorine.
  • the chlorine in the alkali-hydrolyzed chlorine will dissociate and cause poison to the catalyst, so as to reduce the The reactivity of the local over-reaction area can avoid the turbidity of the polyurethane synthetic emulsion, thereby improving the light transmittance and yellowing resistance of the polyurethane product.
  • the present embodiment provides a kind of polyisocyanate composition, and its preparation method is as follows:
  • hexamethylenediamine (HDA) was vaporized and heated to 355°C, under the protection of nitrogen, and the gaseous phosgene heated to 355°C via respective
  • the feed pipe of the phosgene is continuously added to the reactor for phosgenation reaction; the pressure of the reaction is an absolute pressure of 0.05MPa, and the temperature of the reaction is 360°C; wherein, the feed amount of HDA is 800Kg/h, and the feed of gaseous phosgene is 800Kg/h.
  • the amount is 3000Kg/h; the mixed gas obtained after the reaction is cooled to 100 °C rapidly (the contact time is about 10s) by using the o-dichlorobenzene solution through the gas jet absorption device to obtain a solution containing the products HDI, phosgene and o-dichlorobenzene the crude product;
  • reaction tail gas After the reaction tail gas enters the tail gas absorption tower, it is absorbed by ortho-dichlorobenzene solution at -35°C to obtain phosgene-containing ortho-dichlorobenzene solution.
  • step b) the crude product obtained in step a) is processed to remove phosgene and o-dichlorobenzene solution, and in the crude product, o-dichlorobenzene solution and excess phosgene are removed at 168° C. and absolute pressure 0.1 MPa, and are separated to obtain HDI crude product without phosgene and ortho-dichlorobenzene solution containing phosgene;
  • step a) obtain the ortho-dichlorobenzene solution containing phosgene after the reaction tail gas is absorbed, and the obtained ortho-dichlorobenzene solution containing phosgene after the removal process with step b) enters the rectifying tower to carry out phosgene and ortho-dichlorobenzene
  • the separation of the solution is carried out under the conditions that the pressure is an absolute pressure of 0.125 MPa, the temperature at the bottom of the column is 155 °C, and the temperature at the top of the column is 15 °C, to obtain phosgene with a purity of 98% and o-dichloride with a phosgene content of less than 0.001%.
  • benzene solution, isolated phosgene and o-dichlorobenzene solution all return to step a) for recycling;
  • step d) Purify the phosgene-free HDI crude product obtained in step b) by means of rectification to obtain HDI (hexamethylene diisocyanate) product at an absolute pressure of 0.5KPa and a distillation range of 135-140°C.
  • HDI hexamethylene diisocyanate
  • the total content of the unsaturated olefin structure, secondary amine structure and hydroxyl structure in the hexanediamine used was 200 ppm.
  • the yield of the obtained HDI product was 97%, and the purity of the product was 99.75%.
  • the obtained product has a hydrolysis chlorine of 25 ppm, an alkaline hydrolysis chlorine content of 30 ppm, and the difference between the alkaline hydrolysis chlorine and the hydrolysis chlorine is 5 ppm.
  • the present embodiment also provides a kind of polyurethane resin, and its preparation method is as follows:
  • the turbidity test for the prepolymer emulsion was 0.42 NTU.
  • step (2) The polyurethane prepolymer obtained in step (1), 82 parts of 1,4-butanediol (BASF company, used after dewatering at 102° C. and absolute pressure of 200Pa for 2.5 hours) and 0.1 part of dilaurin Dibutyltin acid (Dabco T-12 from American Air Chemicals) was placed in a pouring machine, heated to 45°C, decompressed to an absolute pressure of 1KPa to remove air bubbles for 0.5 hours, mixed evenly, and poured into a mold that had been preheated to 75°C, Heating and curing for 4 hours to obtain polyurethane resin.
  • BASF company used after dewatering at 102° C. and absolute pressure of 200Pa for 2.5 hours
  • dilaurin Dibutyltin acid Dabco T-12 from American Air Chemicals
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 97.5%.
  • the prepared polyurethane resin was placed in an oven at 80° C. and baked for 12 hours to obtain a dry polyurethane product.
  • the color difference ⁇ E is 0.45 (the lower the value, the better the performance).
  • the data shows that the polyurethane resin provided in this example has good resistance to yellowing.
  • the present embodiment provides a kind of polyisocyanate composition, and its preparation method is as follows:
  • step a) adopts liquid phase phosgenation reaction, and adopts the following steps to carry out with reference to the reactor disclosed in patent application CN103319372A:
  • H 12 MDA 4,4'-diaminodicyclohexylmethane
  • the total residence time of the reaction in the cold and hot phosgenation reaction stages is 6 hours and 5 minutes;
  • reaction tail gas After the reaction tail gas enters the tail gas absorption tower, it is absorbed by ortho-dichlorobenzene solution at -30°C to obtain phosgene-containing ortho-dichlorobenzene solution.
  • step b) the reaction solution obtained in step a) is subjected to the treatment of removing phosgene and o-dichlorobenzene solution, and the o-dichlorobenzene solution and excess phosgene in the reaction solution are removed at 155° C. and absolute pressure 0.05MPa to obtain no H 12 MDI crude product containing phosgene and o-dichlorobenzene solution containing phosgene;
  • the residence time of the phosgene-containing o-dichlorobenzene solution at 155°C was controlled to be 1h.
  • step c) obtain the ortho-dichlorobenzene solution containing phosgene after the reaction tail gas is absorbed in the step a), and enter the rectifying tower with the ortho-dichlorobenzene solution containing phosgene obtained in the removal process in step b) to carry out phosgene and ortho-dichlorobenzene
  • the separation process is carried out under the conditions that the pressure is an absolute pressure of 0.125MPa, the temperature at the bottom of the tower is 145°C, and the temperature at the top of the tower is 15°C to obtain phosgene with a purity of 98% and o-dichlorobenzene with a phosgene content of less than 0.001%.
  • the solution, the separated phosgene and the o-dichlorobenzene solution are all returned to step a) for recycling.
  • step d) purify the crude product of H 12 MDI without phosgene obtained in step b) by means of rectification, and obtain H 12 MDI (dicyclohexylmethane di isocyanate) products.
  • the total content of unsaturated olefin structure, secondary amine structure, and hydroxyl structure in the used H 12 MDA was 270 ppm.
  • the yield of the obtained H12MDI product was 96%, and the purity of the product was 99.8%.
  • the hydrolyzed chlorine of the obtained product is 5ppm, the alkali-hydrolyzed chlorine content is 7ppm, and the difference between the alkali-hydrolyzed chlorine and the hydrolyzed chlorine is 2ppm.
  • the present embodiment also provides a kind of polyurethane resin, and its preparation method is as follows:
  • the turbidity test of the prepolymer emulsion was 0.25 NTU.
  • step (2) The polyurethane prepolymer obtained in step (1) was used to prepare a polyurethane resin according to the method of Example 1, and the color difference ⁇ E was tested, and the result was 0.31.
  • the data show that the polyurethane resin provided in this example has good resistance to yellowing.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 95.5%.
  • the present embodiment provides a kind of polyisocyanate composition, and its preparation method is as follows:
  • step a) adopts the salt-forming phosgenation reaction, and the following steps are used in the tank reactor disclosed in the embodiment 1 of the reference patent application CN105218422A:
  • step 2) the IPDA hydrochloride slurry obtained in step 1) is transferred to the photochemical reactor, which has a phosgene air inlet pipe, a gas-phase condensation reflux and stirring; the photochemical reactor is heated up, and stirring is turned on simultaneously, After the temperature reaches 60 °C, feed phosgene, the phosgene feed rate is 50mol/min, the reaction temperature is 145 °C, and the phosgene feeding is stopped after the clarification of the reaction solution to obtain the product containing IPDI, phosgene and o-dichlorobenzene. Salt-forming photochemical reaction solution (crude product);
  • the salt formation reaction is 0.5h, the photochemical reaction is 6h, and the total residence time of the salt formation reaction and the photochemical reaction stage is 6.5 hours;
  • reaction tail gas After the reaction tail gas enters the tail gas absorption tower, it is absorbed by ortho-dichlorobenzene solution at -30°C to obtain phosgene-containing ortho-dichlorobenzene solution.
  • step b) the reaction solution obtained in step a) is subjected to the treatment of removing phosgene and o-dichlorobenzene solution, and the o-dichlorobenzene solution and excess phosgene in the reaction solution are removed at 145° C. and absolute pressure 0.04MPa to obtain no IPDI crude product containing phosgene and phosgene-containing o-dichlorobenzene solution.
  • step c) the ortho-dichlorobenzene solution containing phosgene obtained after the reaction tail gas is absorbed in step a), and the ortho-dichlorobenzene solution containing phosgene obtained in step b) degassing process enters the rectifying tower to carry out phosgene and ortho-dichlorobenzene Separation of benzene; the separation process is carried out under the conditions that the pressure is an absolute pressure of 0.125MPa, the temperature at the bottom of the tower is 165°C, and the temperature at the top of the tower is 15°C, to obtain phosgene with a purity of 98% and o-dichlorine with a phosgene content of less than 0.001%.
  • the benzene solution, the separated phosgene and the o-dichlorobenzene solution are all returned to step a) for recycling.
  • step d) Purify the IPDI crude product without phosgene obtained in step b) by means of rectification, and obtain IPDI (isophorone diisocyanate) product under absolute pressure of 0.5KPa and a distillation range of 140-150°C.
  • the total content of unsaturated olefin structure, secondary amine structure, and hydroxyl structure in the used IPDA was 170 ppm.
  • the yield of the obtained IPDI product was 97.6%, and the purity of the product was 99.85%.
  • the obtained product had a hydrolysis chlorine of 35 ppm, an alkaline hydrolysis chlorine content of 41 ppm, and the difference between the alkaline hydrolysis chlorine and the hydrolysis chlorine was 6 ppm.
  • the present embodiment also provides a kind of polyurethane resin, and its preparation method is as follows:
  • the turbidity test of the prepolymer emulsion was 0.32 NTU.
  • step (2) The polyurethane prepolymer obtained in step (1) was used to prepare a polyurethane resin according to the method of Example 1, and the color difference ⁇ E was tested, and the result was 0.22.
  • the data shows that the polyurethane resin provided in this example has good resistance to yellowing .
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 96.7%.
  • the present embodiment provides a kind of polyisocyanate composition, and its preparation method is as follows:
  • Example 1 of patent application CN105214568A the diamine IPDA was gasified and heated to 355°C, under the protection of nitrogen, with gaseous phosgene heated to 355°C via respective feeds
  • the tube is continuously added to the reactor to carry out phosgenation reaction; the pressure of the reaction is 0.05MPa absolute pressure, and the temperature of the reaction is 360°C; wherein, the feeding amount of IPDA is 800Kg/h, and the feeding amount of gaseous phosgene is 3000Kg /h; the mixed gas obtained after the reaction is cooled rapidly (contact time is about 10s) to 105° C. by using a chlorobenzene solution through a gas jet absorption device to obtain a crude product containing the product IPDI, phosgene and chlorobenzene solution;
  • reaction tail gas After the reaction tail gas enters the tail gas absorption tower, it is absorbed by a chlorobenzene solution at -25°C to obtain a chlorobenzene solution containing phosgene.
  • step b) the crude product obtained in step a) is processed to remove phosgene and chlorobenzene solvent, and in the crude product, chlorobenzene and excess phosgene are removed at 168° C. under an absolute pressure of 0.1 MPa to obtain IPDI without phosgene Crude product and phosgene-containing chlorobenzene solution.
  • step a) obtain the chlorobenzene solution containing phosgene after the reaction tail gas is absorbed, and enter the rectifying tower with the chlorobenzene solution containing phosgene obtained in the removal process of step b) to carry out the separation of phosgene and chlorobenzene solution; the separation process is at The pressure is an absolute pressure of 0.125MPa, the temperature at the bottom of the tower is 155°C, and the temperature at the top of the tower is 15°C. All chlorobenzene solutions are returned to step a) for recycling.
  • step d) purify the IPDI crude product without phosgene obtained in step b) by means of rectification, and obtain IPDI (isophorone diisocyanate) product under absolute pressure 0.5KPa, 140-150 °C distillation range .
  • the total content of unsaturated olefin structure, secondary amine structure, and hydroxyl structure in the used IPDA was 170 ppm.
  • the yield of the obtained IPDI product was 97.5%, and the purity of the product was 99.85%.
  • the obtained product had hydrolysis chlorine of 17 ppm, alkali hydrolysis chlorine content of 22 ppm, and the difference between alkaline hydrolysis chlorine and hydrolysis chlorine was 5 ppm.
  • the present embodiment also provides a kind of polyurethane resin, and its preparation method is as follows:
  • the turbidity test of the prepolymer emulsion was 0.19 NTU.
  • step (2) The polyurethane prepolymer obtained in step (1) is used to prepare a polyurethane resin according to the method of Example 1, and the color difference ⁇ E test is carried out. The result is 0.21.
  • the data shows that the polyurethane resin provided in this example has good resistance to yellowing. .
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 94.9%.
  • the present embodiment provides a polyisocyanate composition, the preparation method of which differs from that of Example 1 only in that the total content of the unsaturated olefin structure, secondary amine structure and hydroxyl structure in the hexamethylene diamine used is 50 ppm, and the remaining operations The steps and conditions are the same as in Example 1.
  • the yield of the obtained HDI product was 97%, and the purity of the product was 99.75%.
  • the hydrolyzed chlorine of the obtained product was 25 ppm, the content of alkaline hydrolyzed chlorine was 25.4 ppm, and the difference between alkaline hydrolyzed chlorine and hydrolyzed chlorine was 0.4 ppm.
  • This embodiment also provides a polyurethane resin, the preparation method of which is the same as that of Embodiment 1.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer is 0.10 NTU; the obtained polyurethane resin is tested for the color difference ⁇ E, and the result is 0.09.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 98.5%.
  • the present embodiment provides a polyisocyanate composition, the preparation method of which differs from that in Example 1 only in that, in step (a), the mixed gas obtained after the reaction is rapidly (contacted by a gas jet absorption device) using an o-dichlorobenzene solution. The time is about 10s) and cooled to 120°C, and the rest of the operation steps and conditions are the same as those in Example 1.
  • the yield of the obtained HDI product was 97%, and the purity of the product was 99.8%.
  • the obtained product had a hydrolysis chlorine of 23 ppm, an alkaline hydrolysis chlorine content of 63 ppm, and the difference between the alkaline hydrolysis chlorine and the hydrolysis chlorine was 40 ppm.
  • This embodiment also provides a polyurethane resin, the preparation method of which is the same as that of Embodiment 1.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer was 0.11 NTU; the obtained polyurethane resin was tested for the color difference ⁇ E, and the result was 0.10.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 98.4%.
  • This example provides a polyisocyanate composition, the preparation method of which is different from Example 2 only in that the total content of the unsaturated olefin structure, secondary amine structure, and hydroxyl structure in the used H 12 MDA is 120 ppm, and the rest of the operations The steps and conditions are the same as in Example 2.
  • the yield of the obtained HDI product was 96.2%, and the purity of the product was 99.8%.
  • the hydrolyzed chlorine of the obtained product was 4.1 ppm, the content of alkaline hydrolyzed chlorine was 4.3 ppm, and the difference between alkaline hydrolyzed chlorine and hydrolyzed chlorine was 0.2 ppm.
  • This embodiment also provides a polyurethane resin, the preparation method of which is the same as that of Embodiment 2.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer was 0.14 NTU; the obtained polyurethane resin was tested for the color difference ⁇ E, and the result was 0.15.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 96.2%.
  • the present embodiment provides a polyisocyanate composition, the preparation method of which differs from that of Example 2 only in that the total residence time of the reaction in the cold and hot phosgenation reaction stages is 6 hours, wherein the cold reaction is 5 minutes, and the hot reaction is 5 hours. 55 minutes, the rest of the operation steps and conditions are the same as in Example 2.
  • the yield of the obtained H 12 MDI product was 96%, and the purity of the product was 99.8%.
  • the obtained product has a hydrolysis chlorine of 5 ppm, an alkaline hydrolysis chlorine content of 65 ppm, and the difference between the alkaline hydrolysis chlorine and the hydrolysis chlorine is 60 ppm.
  • This embodiment also provides a polyurethane resin, the preparation method of which is the same as that of Embodiment 2.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer is 0.15NTU; the obtained polyurethane resin is tested for the color difference ⁇ E, and the result is 0.15.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 96.0%.
  • This example provides a polyisocyanate composition, the preparation method of which is different from Example 3 only in that the total content of the unsaturated olefin structure, secondary amine structure and hydroxyl structure in the IPDA used is 180 ppm, and the remaining operation steps and The conditions are all the same as in Example 3.
  • the yield of the obtained IPDI product was 97.5%, and the purity of the product was 99.85%.
  • the obtained product had hydrolysis chlorine of 17 ppm, alkali hydrolysis chlorine content of 22 ppm, and the difference between alkaline hydrolysis chlorine and hydrolysis chlorine was 5 ppm.
  • the yield of the obtained IPDA product was 97.6%, and the purity of the product was 99.87%.
  • the hydrolyzed chlorine of the obtained product was 17.4 ppm, the content of alkaline hydrolyzed chlorine was 17.5 ppm, and the difference between alkaline hydrolyzed chlorine and hydrolyzed chlorine was 0.1 ppm.
  • This embodiment also provides a polyurethane resin, the preparation method of which is the same as that of embodiment 3.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer was 0.19 NTU; the obtained polyurethane resin was tested for the color difference ⁇ E, and the result was 0.18.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 94.0%.
  • the present embodiment provides a polyisocyanate composition, the preparation method of which differs from that in Example 3 only in that the total residence time of the salt-forming reaction and the photochemical reaction stage is 6 hours, wherein the salt-forming reaction is 0.5 h, and the photochemical reaction is 0.5 h.
  • the reaction was carried out for 5.5h, and the remaining operation steps and conditions were the same as those in Example 3.
  • the yield of the obtained HDI product was 97.5%, and the purity of the product was 99.88%.
  • the obtained product had a hydrolysis chlorine of 17 ppm, an alkaline hydrolysis chlorine content of 117 ppm, and the difference between the alkaline hydrolysis chlorine and the hydrolysis chlorine was 100 ppm.
  • This embodiment also provides a polyurethane resin, the preparation method of which is the same as that of embodiment 3.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer was 0.19 NTU; the obtained polyurethane resin was tested for the color difference ⁇ E, and the result was 0.20.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 94.8%.
  • This comparative example provides a kind of polyisocyanate composition, and the difference between its preparation method and embodiment 1 is only that, in step a), adopt o-dichlorobenzene solution to pass through gas jet absorption device to react the mixed gas obtained after the reaction ( The contact time is about 10s) and cooled to 175°C, and the rest of the operation steps and conditions are the same as those in Example 1.
  • the yield of the obtained HDI product was 97%, and the purity of the product was 99.74%.
  • the obtained product had a hydrolysis chlorine of 23 ppm, an alkaline hydrolysis chlorine content of 170 ppm, and the difference between the alkaline hydrolysis chlorine and the hydrolysis chlorine was 147 ppm.
  • This comparative example also provides a polyurethane resin, the preparation method of which is the same as that of Example 1.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer was 1.7 NTU; the obtained polyurethane resin was tested for the color difference ⁇ E, and the result was 1.5.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 81.5%.
  • This comparative example provides a polyisocyanate composition, and the difference between its preparation method and Example 2 is that in step a), the residence time of the cold reaction is 30min, the residence time of the hot reaction is 8h, and the cold and hot phosgenation The total residence time of the reaction in the reaction stage is 8.5 hours, and all the other operation steps and conditions are the same as in Example 2;
  • the yield of the obtained H 12 MDI product was 96.2%, and the purity of the product was 99.81%.
  • the obtained product had hydrolyzed chlorine of 3 ppm, alkali hydrolyzed chlorine content of 170 ppm, and the difference between alkaline hydrolyzed chlorine and hydrolyzed chlorine was 167 ppm.
  • This comparative example also provides a polyurethane resin, the preparation method of which is the same as that of Example 2.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer was 1.9 NTU; the obtained polyurethane resin was tested for the color difference ⁇ E, and the result was 1.7.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 79.1%.
  • This comparative example provides a polyisocyanate composition, the preparation method of which differs from Example 3 only in that in step a), the total residence time of the reaction in the salt-forming reaction and the photochemical reaction stage is 9.5 hours, and the remaining operation steps and conditions All are the same as Example 3.
  • the yield of the obtained IPDI product was 97.4%, and the purity of the product was 99.86%.
  • the obtained product had a hydrolysis chlorine of 25 ppm, an alkaline hydrolysis chlorine content of 131 ppm, and the difference between the alkaline hydrolysis chlorine and the hydrolysis chlorine was 106 ppm.
  • This comparative example also provides a polyurethane resin, the preparation method of which is the same as that of Example 3.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer was 0.67 NTU; the obtained polyurethane resin was tested for the color difference ⁇ E, and the result was 1.9.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 85.5%.
  • This comparative example provides a polyisocyanate composition, the preparation method of which differs from Example 4 only in that the total content of the unsaturated olefin structure, secondary amine structure and hydroxyl structure in the IPDA used is 0.2 ppm, and the remaining operation steps and conditions are the same as in Example 4.
  • the yield of the obtained IPDI product was 97.4%, and the purity of the product was 99.85%.
  • the obtained product had a hydrolysis chlorine of 21 ppm, an alkaline hydrolysis chlorine content of 21 ppm, and the difference between the alkaline hydrolysis chlorine and the hydrolysis chlorine was 0 ppm.
  • This comparative example also provides a polyurethane resin, the preparation method of which is the same as that of Example 4.
  • the turbidity of the emulsion obtained by the synthesis of the polyurethane prepolymer was 0.75 NTU; the obtained polyurethane resin was tested for the color difference ⁇ E, and the result was 2.7.
  • the obtained polyurethane product was tested for light transmittance according to the method provided by GB/T 2410-2008, and the result was 73.2%.
  • Example 1 By comparing Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, Example 3 with Comparative Example 3, Example 4 with Comparative Example 4, it can be known that the product provided by the present application contains a specific amount (the difference from hydrolyzed chlorine is 0.1 ppm) -100ppm) of the alkali-hydrolyzed chlorine polyisocyanate composition can effectively avoid the turbidity of the polyurethane synthetic emulsion, thereby improving the light transmittance and yellowing resistance of the polyurethane product.

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Abstract

多异氰酸酯组合物及其制备方法和应用，所述多异氰酸酯组合物中碱解氯的质量含量减去水解氯的质量含量的数值为0.1ppm-100ppm；所述碱解氯的质量含量为在碱性条件下解离出来的卤素和/或在100℃以上的温度条件下解离出来的卤素以氯原子的相对原子质量计算得到的质量含量。含有特定量的碱解氯的多异氰酸酯组合物，在反应局部出现失控时导致局部剧烈放热时，碱解氯中的氯会解离出来，对催化剂产生毒害，以降低局部过度反应区域的反应活性，从而避免聚氨酯合成乳液的浑浊，进而提高了聚氨酯产品的透光率和耐黄变性能。

Description

[根据细则37.2由ISA制定的发明名称]　多异氰酸酯组合物及其制备方法和应用 技术领域
本申请涉及聚氨酯技术领域，尤其涉及一种多异氰酸酯组合物及其制备方法和应用。
背景技术
聚氨酯是综合性能优秀的合成树脂之一。由于其合成单体品种多、反应条件温和、专一、可控，且配方调整余地大及其高分子材料的微观结构特点，可广泛用于涂料、黏合剂、泡沫塑料、合成纤维以及弹性体，已成为人们衣、食、住、行必不可少的材料之一；而且，其本身就已经形成了一个多品种、多系列的材料家族，形成了完整的聚氨酯工业体系，这是其它树脂所不具备的。
在大规模聚氨酯生产过程中，由于设备本身的缺陷或者混合效果的不佳，有可能会导致反应空间内局部区域的反应浓度过高而导致反应过度剧烈，释放出大量的热量促进反应过度进行导致反应局部失控，也容易导致聚氨酯合成乳液的浑浊，最终导致聚氨酯制品的不合格。
在现行的行业标准中，已经明确了多异氰酸酯中的水解氯类杂质对下游聚氨酯行业的影响，比如在六亚甲基二异氰酸酯的国家标准GB/T 37042-2018中明确提出要将水解氯控制在100ppm以内，再比如专利CN103319372A中提出控制原料中的醇类杂质、专利CN109761855A中提出控制原料胺中的仲胺的含量，其目的都是为了降低产品中的水解氯的含量。
CN110511163A公开了一种光化反应制备多异氰酸酯的方法以及制备水性聚氨酯树脂的方法，具体公开了多异氰酸酯中的氯含量会影响水性聚氨酯树脂的耐黄变性能，甚至可能直接导致水性聚氨酯树脂的发黄，同时有可能会 对部分体系的反应活性产生不利的影响。
CN1064074A公开了一种降低甲苯二异氰酸酯，特别是其蒸馏残渣中可水解氯化物含量的方法，该申请具体公开了二异氰酸酯中可水解氯化物含量太高，其粘性不稳定且不具活性，因此需处理而将其可水解氯化物含量降到残渣具有活性和粘性稳定性的水平。
因此，本领域亟待研究进一步提高聚氨酯产品质量的方案。
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。
本申请的目的之一在于提供一种多异氰酸酯组合物，所述多异氰酸酯组合物能够解决聚氨酯树脂合成过程中容易出现的预聚阶段及扩链阶段反应活性不稳定的问题，有效改善合成乳液浑浊的情况，从而提高聚氨酯产品的透光率和耐黄变性能。
为达此目的，本申请采用以下技术方案：
本申请提供一种多异氰酸酯组合物，所述多异氰酸酯组合物中碱解氯的质量含量减去水解氯的质量含量的数值为0.1ppm-100ppm，例如0.2ppm、0.3ppm、0.4ppm、0.5ppm、1ppm、2ppm、3ppm、4ppm、5ppm、6ppm、7ppm、8ppm、9ppm、10ppm、15ppm、20ppm、25ppm、30ppm、35ppm、40ppm、45ppm、50ppm、55ppm、60ppm、65ppm、70ppm、75ppm、80ppm、85ppm、90ppm、95ppm、98ppm等；
所述碱解氯的质量含量为在碱性条件下解离出来的卤素和/或在100℃以上的温度条件下解离出来的卤素以氯原子的相对原子质量计算得到的质量含量。
本申请所述多异氰酸酯组合物中除了包含多异氰酸酯，还包括杂质，因此 称为组合物，其中多异氰酸酯指的是含有至少两个(例如2个、3个、4个等)异氰酸酯基(O＝C＝N-)的异氰酸酯。本申请中，水解氯的概念属于本领域公知常识。
本申请中所述以氯原子的相对原子质量计算指的是：测量得到解离下来的卤素的物质的量或摩尔含量，无论其具体为何种卤素，均以氯原子的相对原子质量(35.45g/mol)换算得到质量或质量含量。示例性地，解离下来的卤素为溴，物质的量为1mol，则碱解氯的质量为1mol×35.45g/mol＝35.45g，除以多异氰酸酯组合物的总质量即为碱解氯的质量含量。
由于下游聚氨酯制备过程中由于配方的不同，聚氨酯合成过程的酸碱性环境及反应温度条件也不尽相同，多异氰酸酯组合物中的碱解氯类杂质往往能在聚氨酯合成过程中解离出氯。
经过本发明人研究发现，提供了一种含有上述特定量的碱解氯的多异氰酸酯组合物，在反应局部出现失控时导致局部剧烈放热时，碱解氯中的氯会解离出来，对催化剂产生毒害，以降低局部过度反应区域的反应活性，从而避免聚氨酯合成乳液的浑浊，进而提高了聚氨酯产品的透光率和耐黄变性能。
但是，当碱解氯量高于一定量的时候，这些在碱性条件下解离出来的氯在抑制完局部的过度反应后会进一步向外扩散，对正常反应区域的催化剂产生毒害，导致反应活性的不稳定，进而导致合成过程的热控制出现问题，导致聚氨酯合成的乳液浑浊，对聚氨酯制品产生不利的影响，导致透光率降低，还会导致耐黄变性能变差。
优选地，所述多异氰酸酯组合物中碱解氯的质量含量减去水解氯的质量含量的数值为0.2ppm-60ppm，优选0.4ppm-40ppm。
在本申请的优选技术方案中，进一步优选了碱解氯的质量含量减去水解氯 的质量含量的数值，从而能够进一步改善聚氨酯合成乳液的浑浊问题，提高产品的透光率和耐黄变性能。碱解氯量过低，聚氨酯合成乳液的浑浊问题加重，聚氨酯产品的透光率降低，碱解氯量过高，不仅会导致合成乳液的浑浊问题加重、聚氨酯产品的透光率降低，还会使耐黄变性能变差。
优选地，所述卤素包括氟、氯、溴或碘中的任意一种或至少两种组合。
优选地，所述多异氰酸酯组合物包括多异氰酸酯、碱解氯类杂质和水解氯类杂质的组合。所述碱解氯类杂质即为解离得到碱解氯的物质，水解氯类杂质即为解离得到水解氯的物质。
根据本申请的发明人研究，发现碱解氯类杂质的来源之一为：在光气化反应过程中，主产品多异氰酸酯中的一个异氰酸根掉落后形成的烯烃结构后，在光气化环境下，会进一步与氯化氢结合所得。
对于碱解氯类，对于其不同的来源，需要采取不同的控制措施，在本申请中，多异氰酸酯中的碱解氯类为通过常规分离手段难以去除的，或者需要花费很大的能耗物耗来去除的氯类，需要从源头上予以控制。
优选地，所述多异氰酸酯为二异氰酸酯。
优选地，所述多异氰酸酯包括脂环族二异氰酸酯、芳香族二异氰酸酯或链状二异氰酸酯中的任意一种或至少两种组合。
优选地，所述多异氰酸酯包括二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、间苯二甲基异氰酸酯、对苯二甲基异氰酸酯、1,3-二甲基异氰酸酯环己烷、1,4-二甲基异氰酸酯环己烷、四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、苯二异氰酸酯、萘二异氰酸酯或环己基二异氰酸酯中的任意一种或至少两种组合。
优选地，多异氰酸酯包括二环己基甲烷二异氰酸酯，所述碱解氯类杂质包括如下化合物中的任意一种或至少两种组合：
Figure PCTCN2020133079-appb-000001
所述X为F、Cl、Br或I。
优选地，所述多异氰酸酯包括异佛尔酮二异氰酸酯，所述碱解氯类杂质包括如下化合物中的任意一种或至少两种组合：
Figure PCTCN2020133079-appb-000002
所述X为F、Cl、Br或I。
优选地，所述多异氰酸酯包括六亚甲基二异氰酸酯，所述碱解氯类杂质包括如下化合物中的任意一种或至少两种组合：
Figure PCTCN2020133079-appb-000003
所述X为F、Cl、Br或I。
优选地，所述多异氰酸酯组合物中还包括防老化助剂。添加防老化助剂以增强多异氰酸酯组合物的储存稳定性，延长其保质期，并利于实现使用本申请所述多异氰酸酯组合物制备聚氨酯树脂过程中，多异氰酸酯组合物色号保持稳定，不易黄变。
优选地，所述防老化助剂包括受阻酚抗氧化剂、含有磺酰胺基的化合物或有机亚磷酸酯中的任意一种或至少两种组合，优选受阻酚抗氧化剂，进一步优选抗氧剂264(例如，美国Eastman化学公司，Tenox BHT)、抗氧剂245(例如，德国BASF公司，Irganox 245)或抗氧剂1076(例如，德国BASF公司，Irganox1076)中的任意一种或至少两种组合。
优选地，所述多异氰酸酯组合物中防老化助剂的质量含量为50-5000ppm，例如100ppm、500ppm、1000ppm、1500ppm、2000ppm、2500ppm、3000ppm、3500ppm、4000ppm、4500ppm等，优选100-1000ppm。
优选地，所述多异氰酸酯组合物的制备原料包括多胺和光气类原料的组合。本申请中，所述多胺指的是至少含有两个(例如2个、3个、4个等)氨基的化合物。
优选地，所述多胺中具有不饱和烯烃类结构、仲胺类结构或羟基类结构的杂质的总质量含量为0.1ppm-400ppm，例如0.5ppm、1ppm、5ppm、10ppm、50ppm、100ppm、150ppm、200ppm、250ppm、300ppm、350ppm等。
根据本申请的发明人研究，碱解氯的另一个来源为：在原料多胺的制备过程中，其中的某些组分在后续的光气化制备异氰酸酯的过程中产生碱解氯类，具体的结构包含但不限于下列情况：a)不饱和烯烃结构b)仲胺类结构c)羟基类结构，含有上述结构的物质一般与原料多胺难以分离，在光气化过程中，尤其是在气相光气化过程中与光气或者氯化氢反应，从而形成碱解氯类。因此，在原料多胺方面，需要对这些种类物质的总量进行控制，在本申请中，建议将总量控制在0.1ppm-400ppm。
本申请中，水解氯的质量含量的测定为现有技术，包括但不限于GB/T 37042-2018中所提供的方法。关于碱解氯的质量含量，本领域技术人员也可以 通过常规手段进行测试，本申请仅示例性地提供如下测试方法，但不限于如下方法：
该方法的测试原理是：多异氰酸酯中碱解氯主要为可以在碱性条件下解离下来的氯，首先通过乙醇和多异氰酸酯反应，将多异氰酸酯中的异氰酸根反应掉，然后在碱性条件下将可碱解的卤素解离下来，解离下来的卤素离子形成相应的盐，再以硝酸银标准溶液用电位滴定法测定其含量。
测试过程所用的仪器有：
(a)电位滴定仪；
(b)复合银电极；
(c)电磁搅拌器；
(d)恒温水浴：80℃；
(e)一般实验器具。
测试过程用的试剂有：
(a)水：经离子交换树脂处理的水；
(b)丙酮(AR)；
(c)硝酸溶液：硝酸(GB626)和水按1:3体积混合；
(d)氯化钠标准溶液：1mL相当于1mg，采用GB601中规定的方法制备；
(e)硝酸银标准溶液：C(AgNO 3)＝0.05mol/L，采用GB601中规定的方法制备与标定；
(f)乙醇(AR)；
(g)氢氧化钠标准溶液(2mol/L)：称取80g氢氧化钠(GB629)加水溶解并稀释至1000mL。
仅示例性地，具体测试步骤如下：
(a)取10g-15g(准确至0.1mg)试样于300mL烧杯中，装入转子，加入30mL丙酮，待样品完全溶解后再加入50mL乙醇溶液，放入60℃恒温水浴中进行充分反应；
(b)反应30min后，加入100mL的NaOH溶液，继续于60℃恒温水浴上反应50min；
(c)取下烧杯，放在冰水浴中冷却至10℃以下；
(d)准确加入2mL氯化钠标准溶液于烧杯中，再加1:3的硝酸溶液20mL；进行电位滴定，以所得曲线的拐点为终点，记录所消耗硝酸银标准溶液的体积；
(e)同时做空白试验。
碱解氯按下式计算：
Figure PCTCN2020133079-appb-000004
式中：Cl-水解氯百分含量(以氯计)，ppm；
V-滴定试样时消耗的硝酸银标准溶液的体积，mL；
V 0-滴定空白时消耗的硝酸银标准溶液的体积，mL；
C-硝酸银标准溶液的实际浓度，mol/L；
m-试样的质量，g；
0.03546-与1.00mL硝酸银标准溶液[C(AgNO 3)＝1.000mol/L]相当的，以克表示的氯原子的质量，单位为g/mol。
本申请的目的之二在于提供一种目的之一所述的多异氰酸酯组合物的制备方法，所述制备方法包括：采用多胺与光气类原料进行光气化反应，得到所述多异氰酸酯组合物。
优选地，所述多胺包括间苯二甲胺、对苯二甲胺、1,3-环己二甲胺、1,4-环 己二甲胺、1,4-丁二胺、1,6-己二胺、1,4-二氨基环己烷、二氨基二环己基甲烷(例如，工业品H 12MDA，其是包含4,4-二氨基二环己基甲烷、2,4-二氨基二环己基甲烷、2,2-二氨基二环己基甲烷等的混合物)、甲苯二胺、亚甲基二苯胺(例如，2,2'-亚甲基二苯胺、4,4'-亚甲基二苯胺)、异佛尔酮二胺、苯二胺、萘二胺、1,8-辛二胺、1,10-癸二胺、1,12-二氨基十二烷、1,5-戊二胺、环己烷二胺、甲基环己烷二胺、四甲基对苯二胺或二甲基联苯二胺中的任意一种或至少两种组合，优选间苯二甲胺、对苯二甲胺、1,3-环己二甲胺、1,4-环己二甲胺、1,4-丁二胺、1,6-己二胺、1,4-二氨基环己烷、二氨基二环己基甲烷(例如，工业品H 12MDA，其是包含4,4-二氨基二环己基甲烷、2,4-二氨基二环己基甲烷、2,2-二氨基二环己基甲烷等的混合物)、异佛尔酮二胺、1,8-辛二胺、1,10-癸二胺、1,12-二氨基十二烷、1,5-戊二胺、环己烷二胺、甲基环己烷二胺、四甲基对苯二胺、二甲基联苯二胺、1,6-己二胺、二氨基二环己基甲烷、甲苯二胺、苯二胺或萘二胺中的任意一种或至少两种组合。
优选地，所述光气类原料过量。
优选地，所述光气类原料包括光气、二光气、三光气、氟光气或溴光气中的任意一种或至少两种组合，优选光气、二光气、三光气或氟光气中的一种或至少两种组合，更优选光气和/或氟光气。
优选地，所述制备方法还包括：对所述光气反应得到的粗产物进行后处理。
优选地，所述光气化反应包括气相光气化反应、液相光气化反应或成盐光气化反应。
本申请的光气化反应可以采用本领域已知的工艺种类进行。根据本申请提供的方法，一些示例中，所述光气化反应选自气相光气化反应、液相光气化反应或者成盐光气化反应。在不同的光气化反应工艺中，需要采取不同的手段进 行碱解氯含量的控制。
优选地，所述气相光气化反应包括：多胺气流与光气类原料进行气相光气化反应，反应产物与液态惰性介质混合并冷却至≤150℃，或者，反应产物与液态惰性介质和目标异氰酸酯产物的混合物混合并冷却至≤150℃，例如50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃等，优选100-140℃，获得异氰酸酯粗品。
在本申请的优选技术方案中，由于反应混合气体温度较高，同时为控制碱解氯的产生，因此要求反应混合气体被液态惰性介质和/或惰性介质与异氰酸酯的混合物进行吸收冷却后的温度≤150℃，以减少碱解氯的产生量。
示例性地，所述气相光气化反应具体可参见专利申请CN102260194A、CN105214568A。在一些实施方式中，气相光气化反应的步骤包括：1)将多胺气化形成多胺气流，该多胺气流中含有多胺液滴；2)除去所述多胺气流中含有的多胺液滴，得到基本不含多胺液滴的多胺气流；3)将所述基本不含多胺液滴的多胺气流与光气类原料进行气相光气化反应，反应产物与液态惰性介质(例如，芳香族溶剂)混合并在气体喷射吸收装置中快速冷却至100-140℃，或者，反应产物与液态惰性介质和目标异氰酸酯产物的混合物混合并在气体喷射吸收装置中快速冷却至100-140℃，获得异氰酸酯粗品。同时，采用加热器除去多胺气流中含有的多胺液滴；例如，所用加热器的具体结构可以参见专利申请CN105214568A公开的相应内容。气相光气化反应的温度例如为200-550℃(如，250℃、300℃、320℃、380℃、420℃、500℃)，优选为250-400℃；反应的压力为0.01-1MPa(如，0.05MPa、0.08MPa、0.2MPa、0.5MPa、0.8MPa)，优选为0.03-0.3MPa。在一些具体的方式中，光气类原料与多胺反应后的混合气体(反应产物)可以用一种液态惰性介质(例如，芳香族溶剂)和/或惰性介质与异氰 酸酯的混合物进行吸收冷却。
优选地，所述液相光气反应包括：多胺溶液与光气类原料先在0-100℃下进行冷反应，再在60-180℃下进行热反应，所述冷反应和热反应的总停留时间≤7h，例如1h、2h、3h、4h、5h、6h、7h等。
在本申请的优选技术方案中，将冷反应和热反应的总停留时间控制在7h以内，可以控制碱解氯的产生。
示例性地，所述液相光气化反应具体可参见专利申请CN103319372A。在一些实施方式中，液相光气化反应分两步进行：1)冷反应，温度为0-100℃，优选40-70℃；压力为绝压0.1-1MPa；将多胺与芳香族溶剂(可选自氯苯、间二氯苯、邻二氯苯、对二氯苯和氯甲苯中的一种或多种)混合配制成溶液后与超化学计量的光气类原料进行反应，反应停留时间可以为2-120min，优选5-45min。2)热反应，温度为60-180℃，优选110-165℃，更优选120-150℃；压力为绝压0.1-1MPa；以氯苯、间二氯苯、邻二氯苯、对二氯苯和氯甲苯中的一种或多种为溶剂，与超化学计量的光气类原料进行反应，反应停留时间可以为0.5-5h。在液相光气化过程中，为控制碱解氯的产生，冷反应和热反应的总停留时间≤7h。
优选地，所述成盐光气化反应包括：氯化氢和/或二氧化碳与多胺在惰性溶剂中进行成盐反应，再与光气类原料进行光气化反应；所述成盐反应和光气化反应的总停留时间≤7h，例如1h、2h、3h、4h、5h、6h、7h等。
在本申请的优选技术方案中，将成盐反应和光气化反应的总停留时间控制在7h以内，可以控制碱解氯的产生。
示例性地，所述的光气化反应还可以在氯化氢和/或二氧化碳中进行，即，成盐光气化反应，具体可参见专利申请CN105218422A、CN 107337615A。在一些实施方式中，成盐光气化反应的步骤为：1)氯化氢和/或二氧化碳与多胺在惰 性溶剂中进行成盐反应，所述氯化氢与多胺中氨基的摩尔当量比为1-2.5:1，优选为1.2-2:1，所述二氧化碳与多胺中氨基的摩尔当量比为0.5-5:1，优选为0.6-3:1，惰性溶剂与多胺的质量比为25-5:1，优选为20-5:1；成盐反应的温度为0-50℃，优选为5-30℃，压力为绝压0.1-1MPa，优选为绝压0.2-0.5MPa；反应停留时间为1-15min，优选为5-10min。经过步骤1)成盐反应后，所得盐酸盐或碳酸盐的反应液进入步骤2)与光气类原料进行光气化反应；反应温度为100-170℃，优选为110-165℃，更优选120-150℃；反应压力为绝压0.1-1MPa，优选为绝压0.2-0.5MPa；与超化学计量的光气类原料进行反应，其反应停留时间可以为1-8h。其中的惰性溶剂选自氯苯、间二氯苯、邻二氯苯、对二氯苯和氯甲苯中的一种或多种。在成盐光气化过程中，为控制碱解氯的产生，在步骤1)和步骤2)的总停留时间≤7h。
不论采用液相、成盐或者气相光气化法工艺，反应结束后，根据需要，可对反应液进行过滤及后续的分离。根据本领域公知的技术，通常采用精馏塔或汽提塔对反应液中的副产氯化氢、过量光气类原料进行脱除，光气类原料经过精制后可以输送回反应系统进行回收利用；采用精馏塔对反应液中的溶剂进行脱除，溶剂经过精制后可以输送回反应系统进行回收利用；通过分离得到基本不含溶剂的粗多异氰酸酯组合物料流。采用刮板蒸发器或精馏塔对粗多异氰酸酯组合物料流进行分离精制，将不挥发组分(焦油)和低沸点轻组分杂质脱除，获得相应的多异氰酸酯组合物。
本申请的目的之三在于提供一种聚氨酯树脂，所述聚氨酯树脂的制备原料包括目的之一所述的多异氰酸酯组合物和含有活泼氢基团的化合物的组合。
本申请中聚氨酯树脂为多异氰酸酯组合物中的多异氰酸酯成分与含有活泼氢基团的化合物的反应产物。本申请提供的聚氨酯树脂在合成过程中得到的乳 液浊度低，聚氨酯制品的透光率较高，且耐黄变性能和耐热性较好。
优选地，所述含有活泼氢基团的化合物包括多元醇类化合物和/或胺类化合物。所述多元醇类化合物为具有至少两个羟基的化合物。
优选地，所述多元醇类化合物的分子量为400-20000，例如800、1000、2000、5000、8000、10000、15000、18000等。
优选地，所述多元醇类化合物的羟值为10mg KOH/g-1500mg KOH/g，例如20mg KOH/g、30mg KOH/g、40mg KOH/g、50mg KOH/g、100mg KOH/g、200mg KOH/g、500mg KOH/g、800mg KOH/g、1000mg KOH/g、1200mg KOH/g、1400mg KOH/g等。多元醇成分的羟值可由按照GB/T 12008.3-2019标准中的方法A-邻苯二甲酸酐法进行分析确定。
优选地，所述多元醇类化合物的官能度为2-8，例如3、4、5、6、7等。
优选地，所述多元醇类化合物包括聚醚多元醇、聚酯多元醇、聚烯烃多元醇、环氧树脂或生物基多元醇中的任意一种或至少两种组合。
优选地，所述聚醚多元醇包括聚氧化乙烯多元醇、聚氧化丙烯多元醇、聚合物多元醇、聚脲多元醇、聚四氢呋喃及其共聚醚二醇、聚三亚甲基二醇或芳香族聚醚多元醇中的任意一种或至少两种组合。
优选地，所述聚酯多元醇包括己二酸系聚酯二醇、芳香族聚酯多元醇、聚己内酯多元醇或聚碳酸酯二元醇中的任意一种或至少两种组合。
优选地，所述己二酸系聚酯二醇包括聚己二酸乙二醇酯二醇、聚己二酸丙二醇酯二醇、聚己二酸丁二醇酯二醇或聚己二酸二醇酯二甘醇中的任意一种或至少两种组合。
优选地，所述芳香族聚酯多元醇包括聚邻苯二甲酸一缩二乙二醇酯二醇、邻苯二甲酸-1,6-己二醇酯二醇或邻苯二甲酸新戊二醇酯二醇中的任意一种或至 少两种组合。
优选地，所述聚己内酯多元醇包括聚己内酯二元醇和/或聚己内酯三元醇。
优选地，所述聚碳酸酯二醇包括聚碳酸亚己酯二醇、聚碳酸-1,6-己二醇酯二醇或聚碳酸亚丁酯二醇中的任意一种或至少两种组合。
优选地，所述聚烯烃多元醇包括端羟基聚丁二烯、端羟基氢化聚丁二烯、端羟基环氧化聚丁二烯树脂、端羟基聚丁二烯-丙烯腈或聚苯乙烯多元醇中的任意一种或至少两种组合。
优选地，所述环氧树脂包括双酚A环氧树脂、双酚F环氧树脂、酚醛环氧树脂或脂肪族环氧树脂中的任意一种或至少两种组合。
优选地，生物基多元醇包括蓖麻油及其衍生物多元醇、大豆油多元醇、棕榈油多元醇、松香酯多元醇、脂肪酸二聚体二醇、鱼油多元醇或木质素多元醇中的任意一种或至少两种组合。
优选地，所述聚氨酯树脂的制备原料还包括催化剂和/或扩链剂。
优选地，所述扩链剂包括多官能度醇类化合物(例如，其官能度为2、3、4、5)和/或多官能度胺类化合物(例如，其官能度为2、3、4、5)，优选乙二醇、一缩二乙二醇(二甘醇)、1,2-丙二醇、一缩二丙二醇、1,4-丁二醇(1,4-butanediol,BDO)、1,6-己二醇(HD)、三羟甲基丙烷(TMP)、蓖麻油、乙二胺(EDA)、肼、己二胺、异佛尔酮二胺、甲基戊二胺、二亚乙基三胺或三乙烯四胺中的任意一种或至少两种组合。
在水性聚氨酯领域中，采用的扩链剂为亲水性扩链剂，优选二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)、1,4-丁二醇-2-磺酸钠、二乙醇胺、三乙醇胺、N-甲基二乙醇胺(MDEA)、N-乙基二乙醇胺(EDEA)、N-丙基二乙醇胺(PDEA)、N-丁基二乙醇胺(BDEA)、二甲基乙醇胺、双(2-羟乙基)苯胺(BHBA)、 双(2-羟丙基)苯胺(BHPA)和N-甲基二乙醇胺(MDEA)中的任意一种或至少两种组合。
本申请中，所述聚氨酯树脂可利用本领域公知的例如一步法和预聚体法等工艺路线制造，本申请优选利用预聚体法进行聚合制造。
示例性地，一步法是将多异氰酸酯(例如脂环族二异氰酸酯组合物)、多元醇、催化剂、扩链剂等所需的原料一次均匀混合，浇注成型的制备方法。
示例性地，预聚体法是用多元醇和稍过量的多异氰酸酯(例如脂环族二异氰酸酯组合物)反应，合成两端为异氰酸酯基封端的聚氨酯预聚体，然后再将预聚体与催化剂、扩链剂进一步反应固化浇注成型，获得聚氨酯弹性体材料。
在本申请的一个具体实施方式中，采用预聚体法制备所述聚氨酯树脂，包括如下步骤：
1)通过将所述多元醇和过量的所述脂环族二异氰酸酯组合物进行预聚合反应制备两端为异氰酸酯基封端的聚氨酯预聚体；优选地，所述预聚合反应温度为60-120℃，优选80-100℃，反应时间为1-6h，优选2-4h；
2)将所述聚氨酯预聚体与催化剂和扩链剂混合，经浇筑固化，获得所述聚氨酯树脂；优选地，所述浇筑固化在温度50-100℃下进行，优选60-80℃，固化时间为1-10h，优选3-6h。
一些实施方案中，本申请所述预聚体法所用原料配方中，包括如下质量份的各原料：多异氰酸酯组合物50-500份，优选100-400份；多元醇100份；扩链剂50-500份，优选50-400份；催化剂0.005-1份，优选0.01-0.5份。
扩链剂可以采用本领域的常规扩链剂。例如一些实施方案中，本申请所述扩链剂可以为双官能团化合物或三官能团及以上的化合物，双官能团化合物可举出如1,4-丁二醇、乙二醇、一缩二乙二醇、1,6-己二醇等二元醇，如3,3’-二氯 -4,4’-二苯基甲烷二胺(MOCA)、3,5-二乙基甲苯二胺(DETDA)等二元胺，乙醇胺等，三官能团及以上的化合物可举出如甘油、三羟甲基丙烷、季戊四醇；本申请优选1,4-丁二醇和/或3,3’-二氯-4,4’-二苯基甲烷二胺。
本申请制备聚氨酯树脂过程中，制备的端异氰酸酯预聚体中异氰酸酯基的含量可以使用GB/T 12009.4-1989标准规定的方法进行滴定分析。
扩链剂的用量可参考专利申请CN110982038A中所提供的方法进行计算；本申请优选扩链剂的扩链系数为0.8-1.1，更优选0.9-1.0。
作为预聚体法的催化剂一般为有机锡化合物，可举出如辛酸亚锡、二丁基二氯化锡、二月桂酸二丁基锡、二乙酸二丁基锡、二(十二烷基硫)二丁基锡中一种或多种，本申请的工艺路线优选二月桂酸二丁基锡。
需要说明的是，在制造本申请的聚氨酯树脂时，根据具体用途需要，可以按照适当的比例进一步添加行业内公知的添加剂，例如增塑剂、消泡剂、阻燃剂、脱水剂、抗氧化剂、紫外线吸收剂、防水解剂、耐气候稳定剂等。
本申请的目的之四在于提供一种目的之三所述的聚氨酯树脂的应用，所述聚氨酯树脂用于聚氨酯弹性体、聚氨酯光学材料、聚氨酯涂覆材料(例如涂料、胶黏剂)或聚氨酯泡沫的制备，优选用于聚氨酯弹性体的制备。
相对于现有技术，本申请具有以下有益效果：
本申请提供了一种含有特定量的碱解氯的多异氰酸酯组合物，在反应局部出现失控时导致局部剧烈放热时，碱解氯中的氯会解离出来，对催化剂产生毒害，以降低局部过度反应区域的反应活性，从而避免聚氨酯合成乳液的浑浊，进而提高了聚氨酯产品的透光率和耐黄变性能。
在阅读并理解了详细描述后，可以明白其他方面。
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。
实施例1
本实施例提供一种多异氰酸酯组合物，其制备方法如下：
a)采用专利申请CN105214568A的实施例1中公开的加热器，将己二胺(HDA)进行气化并加热到355℃，在氮气的保护下，与被加热到355℃的气态光气经由各自的进料管连续地加入反应器中进行光气化反应；反应的压力为绝压0.05MPa，反应的温度为360℃；其中，HDA的进料量为800Kg/h，气态光气的进料量为3000Kg/h；采用邻二氯苯溶液经过气体喷射吸收装置将反应后所得的混合气体快速(接触时间为10s左右)冷却至100℃，得到含有产物HDI、光气和邻二氯苯溶液的粗产物；
反应尾气进入尾气吸收塔后用-35℃的邻二氯苯溶液吸收，得到含光气的邻二氯苯溶液。
b)将步骤a)得到的粗产物进行脱除光气和邻二氯苯溶液的处理，粗产物中邻二氯苯溶液和过量的光气在168℃、绝对压力0.1MPa下去除，分离得到不含有光气的HDI粗产品和含光气的邻二氯苯溶液；
c)步骤a)反应尾气吸收后得到含光气的邻二氯苯溶液，与步骤b)脱除过程后所得含光气的邻二氯苯溶液进入精馏塔进行光气和邻二氯苯溶液的分离；分离过程在压力为绝压0.125MPa、塔底温度为155℃、塔顶温度为15℃的条件下进行，得到纯度为98％的光气和光气含量＜0.001％的邻二氯苯溶液，分离出的光气和邻二氯苯溶液均返回到步骤a)中进行循环使用；
d)将步骤b)中得到的不含有光气的HDI粗产品通过精馏的方式进行提纯，在绝压0.5KPa、135-140℃馏程下得到HDI(六亚甲基二异氰酸酯)产品。
所用己二胺中的不饱和烯烃结构、仲胺类结构、羟基类结构含量的总和为200ppm。
所得HDI产品的产率为97％，产品的纯度99.75％。所得产品水解氯为25ppm，碱解氯含量为30ppm，碱解氯与水解氯差值为5ppm。
本实施例还提供一种聚氨酯树脂，其制备方法如下：
(1)聚氨酯预聚体的制备
称取相对分子质量为1000的聚氧化丙烯二醇，羟值110mg KOH/g，官能度2(上海高桥石油化工公司，聚醚多元醇GE-210)100份，边搅拌边加热至110℃，减压至绝压200Pa除水2.5小时，降温至60℃，加入168份的上述异氰酸酯合成过程中生产的HDI。升温至80℃，反应120min，得到蓝色透明聚氨酯预聚体乳液。
对预聚体乳液进行浊度测试结果为0.42NTU。
(2)将步骤(1)得到的聚氨酯预聚体、82份的1,4-丁二醇(BASF公司，于102℃、绝压200Pa下除水2.5小时后使用)和0.1份的二月桂酸二丁基锡(美国空气化工Dabco T-12)置于浇注机中，分别加热至45℃，减压至绝压1KPa除气泡0.5小时，混合均匀，浇注到已预热至75℃的模具中，加热固化4h，得到聚氨酯树脂。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为97.5％。
将制得的聚氨酯树脂放入80℃烘箱中，烘烤12h，得到干燥的聚氨酯制品。用色差仪(爱丽色X-Rite528型)测试所得聚氨酯制品的色值b，再将聚氨酯膜放入150℃烘箱中烘烤0.5h，用色差仪测试烘烤后树脂膜的色值b并测试色差△E为0.45(数值越低表明性能越优秀)，数据显示本实施例提供的聚氨酯树脂 具有良好的耐黄变性能。
实施例2
本实施例提供一种多异氰酸酯组合物，其制备方法如下：
步骤a)的光气化反应采用液相光气化反应，参照专利申请CN103319372A公开的反应釜中采用如下步骤进行：
1)冷反应：将4,4’-二氨基二环己基甲烷(H 12MDA)以邻二氯苯为溶剂配置成质量含量为15％的溶液，并预热到40℃，与-5℃的液态光气同时通入到含有邻二氯苯溶液的反应釜中进行液相光气化反应；其中，H 12MDA的进料量为400Kg/h，冷反应光气的进料量为1500kg/h，冷反应温度控制在60℃，停留时间为5min；
2)热反应：温度控制在155℃、且停留时间为6h，在邻二氯苯溶液和过量光气存在下进行反应，得到含有产物H 12MDI、光气和邻二氯苯溶液的反应液(粗产物)；
冷、热光气化反应阶段的反应总停留时间为6小时5分钟；
反应尾气进入尾气吸收塔后用-30℃的邻二氯苯溶液吸收，得到含光气的邻二氯苯溶液。
b)将步骤a)得到的反应液进行脱除光气和邻二氯苯溶液的处理，反应液中邻二氯苯溶液和过量的光气在155℃、绝对压力0.05MPa下去除，得到不含有光气的H 12MDI粗产品和含光气的邻二氯苯溶液；
脱除过程中，控制含光气的邻二氯苯溶液在155℃下的停留时间为1h。
c)步骤a)中反应尾气吸收后得到含光气的邻二氯苯溶液，与步骤b)脱除过程所得含光气的邻二氯苯溶液进入精馏塔进行光气和邻二氯苯的分离；分离过程在压力为绝压0.125MPa、塔底温度为145℃，塔顶温度为15℃的条件下进 行，得到纯度为98％的光气和光气含量＜0.001％的邻二氯苯溶液，分离出的光气和邻二氯苯溶液均返回到步骤a)中进行循环使用。
d)将步骤b)中得到的不含有光气的H 12MDI粗产品通过精馏的方式进行提纯，在绝压0.5KPa、150-160℃馏程下得到H 12MDI(二环己基甲烷二异氰酸酯)产品。
所用H 12MDA中的不饱和烯烃结构、仲胺类结构、羟基类结构含量的总和为270ppm。
所得H12MDI产品的产率为96％，产品的纯度99.8％。所得产品水解氯为5ppm，碱解氯含量为7ppm，碱解氯与水解氯差值为2ppm。
本实施例还提供一种聚氨酯树脂，其制备方法如下：
(1)聚氨酯预聚体的制备
称取相对分子质量为1000的聚氧化丙烯二醇，羟值110mg KOH/g，官能度2(上海高桥石油化工公司，聚醚多元醇GE-210)100份，边搅拌边加热至110℃，减压至绝压200Pa除水2.5小时，降温至60℃，加入262份的上述异氰酸酯合成过程中生产的H 12MDI。升温至85℃，反应100min，得到蓝色透明聚氨酯预聚体乳液。
对预聚体乳液进行浊度测试结果为0.25NTU。
(2)将步骤(1)得到的聚氨酯预聚体按照实施例1的方法制备聚氨酯树脂并进行色差△E测试，结果为0.31。数据显示本实施例提供的聚氨酯树脂具有良好的耐黄变性能。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为95.5％。
实施例3
本实施例提供一种多异氰酸酯组合物，其制备方法如下：
步骤a)的光气化反应采用成盐光气化反应，参考专利申请CN105218422A的实施例1中公开的釜式反应器中采用如下步骤进行：
1)在成盐反应釜中预先加入1000Kg邻二氯苯作为反应溶剂，开启循环泵及搅拌，氯化氢压缩气体通过预混合器以50mol/min的速度进入反应器，搅拌15min后，将异佛尔酮二胺(IPDA)与邻二氯苯的混合液通过原料预热器升温至30℃，以335Kg/h的流速与氯化氢气体充分接触后成盐反应；采用外循环冷却水进行冷却，移走部分反应热，循环液流量在5m 3/h左右，反应液温度维持在30-45℃，进料1h后，停止IPDA与邻二氯苯的混合液进料，继续通入HCl气体30min。
2)将步骤1)得到的IPDA盐酸盐浆料转移至光化反应釜中，此光化反应釜具有光气进气管、气相冷凝回流和搅拌；将光化反应釜升温，同时开启搅拌，待温度达到60℃后通入光气，光气进料速度为50mol/min，反应温度145℃，待反应液澄清后停止光气进料，得到含有产物IPDI、光气和邻二氯苯的成盐光化反应液(粗产物)；
成盐反应0.5h、光化反应6h，成盐反应和光化反应阶段的反应总停留时间为6.5小时；
反应尾气进入尾气吸收塔后用-30℃的邻二氯苯溶液吸收，得到含光气的邻二氯苯溶液。
b)将步骤a)得到的反应液进行脱除光气和邻二氯苯溶液的处理，反应液中邻二氯苯溶液和过量的光气在145℃、绝对压力0.04MPa下去除，得到不含有光气的IPDI粗产品和含光气的邻二氯苯溶液。
c)步骤a)中反应尾气吸收后所得含光气的邻二氯苯溶液，与步骤b)脱除 气过程所得含光气的邻二氯苯溶液进入精馏塔进行光气和邻二氯苯的分离；分离过程在压力为绝压0.125MPa、塔底温度为165℃，塔顶温度为15℃的条件下进行，得到纯度为98％的光气和光气含量＜0.001％的邻二氯苯溶液，分离出的光气和邻二氯苯溶液均返回到步骤a)中进行循环使用。
d)将步骤b)中得到的不含有光气的IPDI粗产品通过精馏的方式进行提纯，在绝压0.5KPa、140-150℃馏程下得到IPDI(异佛尔酮二异氰酸酯)产品。
所用IPDA中的不饱和烯烃结构、仲胺类结构、羟基类结构含量的总和为170ppm。
所得IPDI产品的产率为97.6％，产品的纯度99.85％。所得产品水解氯为35ppm，碱解氯含量为41ppm，碱解氯与水解氯差值为6ppm。
本实施例还提供一种聚氨酯树脂，其制备方法如下：
(1)聚氨酯预聚体的制备
称取相对分子质量为1000的聚氧化丙烯二醇，羟值110mg KOH/g，官能度2(上海高桥石油化工公司，聚醚多元醇GE-210)100份，边搅拌边加热至110℃，减压至绝压200Pa除水2.5小时，降温至60℃，加入222份的上述异氰酸酯合成过程中生产的H 12MDI。升温至85℃，反应150min，得到蓝色透明聚氨酯预聚体乳液。
对预聚体乳液进行浊度测试结果为0.32NTU。
(2)将步骤(1)得到的聚氨酯预聚体按照实施例1的方法制备聚氨酯树脂并进行色差△E测试，结果为0.22，数据显示本实施例提供的聚氨酯树脂具有良好的耐黄变性能。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为96.7％。
实施例4
本实施例提供一种多异氰酸酯组合物，其制备方法如下：
a)采用专利申请CN105214568A的实施例1中公开的加热器，将二胺IPDA进行气化并加热到355℃，在氮气的保护下，与被加热到355℃的气态光气经由各自的进料管连续地加入反应器中进行光气化反应；反应的压力为绝压0.05MPa，反应的温度为360℃；其中，IPDA的进料量为800Kg/h，气态光气的进料量为3000Kg/h；采用氯苯溶液经过气体喷射吸收装置将反应后所得的混合气体快速(接触时间为10s左右)冷却至105℃，得到含有产物IPDI、光气和氯苯溶液的粗产物；
反应尾气进入尾气吸收塔后用-25℃的氯苯溶液吸收，得到含光气的氯苯溶液。
b)将步骤a)得到的粗产物进行脱除光气和氯苯溶剂的处理，粗产物中氯苯和过量的光气在168℃、绝对压力0.1MPa下去除，得到不含有光气的IPDI粗产品和含光气的氯苯溶液。
c)步骤a)反应尾气吸收后得到含光气的氯苯溶液，与步骤b)脱除过程所得含光气的氯苯溶液进入精馏塔进行光气和氯苯溶液的分离；分离过程在压力为绝压0.125MPa、塔底温度为155℃，塔顶温度为15℃的条件下进行，得到纯度为98％的光气和光气含量＜0.001％的氯苯溶液，分离出的光气和氯苯溶液均返回到步骤a)中进行循环使用。
d)将步骤b)中得到的不含有光气的IPDI粗产品进行通过精馏的方式进行提纯，在绝压0.5KPa、140-150℃馏程下得到IPDI(异佛尔酮二异氰酸酯)产品。
所用IPDA中的不饱和烯烃结构、仲胺类结构、羟基类结构含量的总和为 170ppm。
所得IPDI产品的产率为97.5％，产品的纯度99.85％。所得产品水解氯为17ppm，碱解氯含量为22ppm，碱解氯与水解氯差值为5ppm。
本实施例还提供一种聚氨酯树脂，其制备方法如下：
(1)聚氨酯预聚体的制备
称取相对分子质量为1000的聚氧化丙烯二醇，羟值110mg KOH/g，官能度2(上海高桥石油化工公司，聚醚多元醇GE-210)100份，边搅拌边加热至110℃，减压至绝压200Pa除水2.5小时，降温至60℃，加入222份的上述异氰酸酯合成过程中生产的IPDI。升温至85℃，反应150min，得到蓝色透明聚氨酯预聚体乳液。
对预聚体乳液进行浊度测试结果为0.19NTU。
(2)将步骤(1)得到的聚氨酯预聚体按照实施例1的方法制备聚氨酯树脂并进行色差△E测试，结果为0.21，数据显示本实施例提供的聚氨酯树脂具有良好的耐黄变性能。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为94.9％。
实施例5
本实施例提供一种多异氰酸酯组合物，其制备方法与实施例1的区别仅在于，所用己二胺中的不饱和烯烃结构、仲胺类结构、羟基类结构含量的总和为50ppm，其余操作步骤和条件均与实施例1相同。
所得HDI产品的产率为97％，产品的纯度99.75％。所得产品水解氯为25ppm，碱解氯含量为25.4ppm，碱解氯与水解氯差值为0.4ppm。
本实施例还提供一种聚氨酯树脂，其制备方法与实施例1相同。
聚氨酯预聚体合成得到的乳液浊度为0.10NTU；将制得的聚氨酯树脂进行色差△E测试，结果为0.09。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为98.5％。
实施例6
本实施例提供一种多异氰酸酯组合物，其制备方法与实施例1的区别仅在于，步骤(a)中，采用邻二氯苯溶液经过气体喷射吸收装置将反应后所得的混合气体快速(接触时间为10s左右)冷却至120℃，其余操作步骤和条件均与实施例1相同。
所得HDI产品的产率为97％，产品的纯度99.8％。所得产品水解氯为23ppm，碱解氯含量为63ppm，碱解氯与水解氯差值为40ppm。
本实施例还提供一种聚氨酯树脂，其制备方法与实施例1相同。
聚氨酯预聚体合成得到的乳液浊度为0.11NTU；将制得的聚氨酯树脂进行色差△E测试，结果为0.10。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为98.4％。
实施例7
本实施例提供一种多异氰酸酯组合物，其制备方法与实施例2的区别仅在于，所用H 12MDA中的不饱和烯烃结构、仲胺类结构、羟基类结构含量的总和为120ppm，其余操作步骤和条件均与实施例2相同。
所得HDI产品的产率为96.2％，产品的纯度99.8％。所得产品水解氯为4.1ppm，碱解氯含量为4.3ppm，碱解氯与水解氯差值为0.2ppm。
本实施例还提供一种聚氨酯树脂，其制备方法与实施例2相同。
聚氨酯预聚体合成得到的乳液浊度为0.14NTU；将制得的聚氨酯树脂进行色差△E测试，结果为0.15。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为96.2％。
实施例8
本实施例提供一种多异氰酸酯组合物，其制备方法与实施例2的区别仅在于，冷、热光气化反应阶段的反应总停留时间为6小时，其中，冷反应5min，热反应5小时55分钟，其余操作步骤和条件均与实施例2相同。
所得H 12MDI产品的产率为96％，产品的纯度99.8％。所得产品水解氯为5ppm，碱解氯含量为65ppm，碱解氯与水解氯差值为60ppm。
本实施例还提供一种聚氨酯树脂，其制备方法与实施例2相同。
聚氨酯预聚体合成得到的乳液浊度为0.15NTU；将制得的聚氨酯树脂进行色差△E测试，结果为0.15。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为96.0％。
实施例9
本实施例提供一种多异氰酸酯组合物，其制备方法与实施例3的区别仅在于，所用IPDA中的不饱和烯烃结构、仲胺类结构、羟基类结构含量的总和为180ppm，其余操作步骤和条件均与实施例3相同。
所得IPDI产品的产率为97.5％，产品的纯度99.85％。所得产品水解氯为17ppm，碱解氯含量为22ppm，碱解氯与水解氯差值为5ppm。
所得IPDA产品的产率为97.6％，产品的纯度99.87％。所得产品水解氯为17.4ppm，碱解氯含量为17.5ppm，碱解氯与水解氯差值为0.1ppm。
本实施例还提供一种聚氨酯树脂，其制备方法与实施例3相同。
聚氨酯预聚体合成得到的乳液浊度为0.19NTU；将制得的聚氨酯树脂进行色差△E测试，结果为0.18。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为94.0％。
实施例10
本实施例提供一种多异氰酸酯组合物，其制备方法与实施例3的区别仅在于，成盐反应、光化反应阶段的反应总停留时间为6小时，其中，成盐反应0.5h，光化反应5.5h，其余操作步骤和条件均与实施例3相同。
所得HDI产品的产率为97.5％，产品的纯度99.88％。所得产品水解氯为17ppm，碱解氯含量为117ppm，碱解氯与水解氯差值为100ppm。
本实施例还提供一种聚氨酯树脂，其制备方法与实施例3相同。
聚氨酯预聚体合成得到的乳液浊度为0.19NTU；将制得的聚氨酯树脂进行色差△E测试，结果为0.20。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为94.8％。
对比例1
本对比例提供一种多异氰酸酯组合物，其制备方法与实施例1的不同之处仅在于，步骤a)中，采用邻二氯苯溶液经过气体喷射吸收装置将反应后所得的混合气体快速(接触时间为10s左右)冷却至175℃，其余操作步骤和条件均与实施例1相同。
所得HDI产品的产率为97％，产品的纯度99.74％。所得产品水解氯为23ppm，碱解氯含量为170ppm，碱解氯与水解氯差值为147ppm。
本对比例还提供一种聚氨酯树脂，其制备方法与实施例1相同。
聚氨酯预聚体合成得到的乳液浊度为1.7NTU；将制得的聚氨酯树脂进行色差△E测试，结果为1.5。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为81.5％。
对比例2
本对比例提供一种多异氰酸酯组合物，其制备方法与实施例2的区别仅在于，步骤a)中，冷反应的停留时间为30min，热反应的停留时间为8h，冷、热光气化反应阶段的反应总停留时间为8.5小时，其余操作步骤和条件均与实施例2相同；
所得H 12MDI产品的产率为96.2％，产品的纯度99.81％。所得产品水解氯为3ppm，碱解氯含量为170ppm，碱解氯与水解氯差值为167ppm。
本对比例还提供一种聚氨酯树脂，其制备方法与实施例2相同。
聚氨酯预聚体合成得到的乳液浊度为1.9NTU；将制得的聚氨酯树脂进行色差△E测试，结果为1.7。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为79.1％。
对比例3
本对比例提供一种多异氰酸酯组合物，其制备方法与实施例3的区别仅在于，步骤a)中，成盐反应、光化反应阶段的反应总停留时间为9.5小时，其余操作步骤和条件均与实施例3相同。
所得IPDI产品的产率为97.4％，产品的纯度99.86％。所得产品水解氯为25ppm，碱解氯含量为131ppm，碱解氯与水解氯差值为106ppm。
本对比例还提供一种聚氨酯树脂，其制备方法与实施例3相同。
聚氨酯预聚体合成得到的乳液浊度为0.67NTU；将制得的聚氨酯树脂进行色差△E测试，结果为1.9。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为85.5％。
对比例4
本对比例提供一种多异氰酸酯组合物，其制备方法与实施例4的区别仅在于，所用IPDA中的不饱和烯烃结构、仲胺类结构、羟基类结构含量的总和为0.2ppm，其余操作步骤和条件均与实施例4相同。
所得IPDI产品的产率为97.4％，产品的纯度99.85％。所得产品水解氯为21ppm，碱解氯含量为21ppm，碱解氯与水解氯差值为0ppm。
本对比例还提供一种聚氨酯树脂，其制备方法与实施例4相同。
聚氨酯预聚体合成得到的乳液浊度为0.75NTU；将制得的聚氨酯树脂进行色差△E测试，结果为2.7。
将得到的聚氨酯制品按照GB/T 2410-2008所提供的方法进行透光率测试，结果为73.2％。
通过对比实施例1和对比例1、实施例2和对比例2、实施例3和对比例3、实施例4和对比例4可知，本申请提供的含有特定量(与水解氯差为0.1ppm-100ppm)的碱解氯的多异氰酸酯组合物能够有效避免聚氨酯合成乳液的浑浊，从而提高了聚氨酯产品的透光率和耐黄变性能。
通过对比实施例1、5-10可知，当多异氰酸酯组合物中碱解氯的质量含量减去水解氯的质量含量的数值为0.2ppm-60ppm时(实施例1、5-8)，能够进一步改善聚氨酯合成乳液的浑浊问题，提高产品的透光率和耐黄变性能，差值在4 ppm-40ppm范围内(实施例1、5-6)效果更优。

Claims (10)

  1. 一种多异氰酸酯组合物，其中，碱解氯的质量含量减去水解氯的质量含量的数值为0.1ppm-100ppm；
    所述碱解氯的质量含量为在碱性条件下解离出来的卤素和/或在100℃以上的温度条件下解离出来的卤素以氯原子的相对原子质量计算得到的质量含量。
  2. 根据权利要求1所述的多异氰酸酯组合物，其中，碱解氯的质量含量减去水解氯的质量含量的数值为0.2ppm-60ppm，优选0.4ppm-40ppm。
  3. 根据权利要求1或2所述的多异氰酸酯组合物，其包括多异氰酸酯、碱解氯类杂质和水解氯类杂质的组合；
    优选地，所述多异氰酸酯为二异氰酸酯；
    优选地，所述多异氰酸酯包括脂环族二异氰酸酯、芳香族二异氰酸酯或链状二异氰酸酯中的任意一种或至少两种组合；
    优选地，所述多异氰酸酯包括二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、间苯二甲基异氰酸酯、对苯二甲基异氰酸酯、1,3-二甲基异氰酸酯环己烷、1,4-二甲基异氰酸酯环己烷、四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二异氰酸酯、萘二异氰酸酯或环己基二异氰酸酯中的任意一种或至少两种组合。
  4. 根据权利要求1-3中任一项所述的多异氰酸酯组合物，其制备原料包括多胺和光气类原料的组合；
    优选地，所述多胺中具有不饱和烯烃类结构、仲胺类结构或羟基类结构的杂质的总质量含量为0.1ppm-400ppm。
  5. 一种根据权利要求1-4中任一项所述的多异氰酸酯组合物的制备方法，其包括：采用多胺与光气类原料进行光气化反应，得到所述多异氰酸酯组合物。
  6. 根据权利要求5所述的制备方法，其中，所述光气化反应包括气相光气 化反应、液相光气化反应或成盐光气化反应；
    优选地，所述气相光气化反应包括：多胺气流与光气类原料进行气相光气化反应，反应产物与液态惰性介质混合并冷却至≤150℃，或者，反应产物与液态惰性介质和目标异氰酸酯产物的混合物混合并冷却至≤150℃，优选100-140℃；
    优选地，所述液相光气反应包括：多胺溶液与光气类原料先在0-100℃下进行冷反应，再在60-180℃下进行热反应，所述冷反应和热反应的总停留时间≤7h；
    优选地，所述成盐光气化反应包括：氯化氢和/或二氧化碳与多胺在惰性溶剂中进行成盐反应，再与光气类原料进行光气化反应；所述成盐反应和光气化反应的总停留时间≤7h。
  7. 一种聚氨酯树脂，其制备原料包括权利要求1-4中任一项所述的多异氰酸酯组合物和含有活泼氢基团的化合物的组合。
  8. 根据权利要求7所述的聚氨酯树脂，其中，所述含有活泼氢基团的化合物包括多元醇类化合物和/或胺类化合物；
    优选地，所述多元醇类化合物的分子量为400-20000；
    优选地，所述多元醇类化合物的羟值为10mg KOH/g-1500mg KOH/g；
    优选地，所述多元醇类化合物的官能度为2-8。
  9. 根据权利要求7或8所述的聚氨酯树脂，其制备原料还包括催化剂和/或扩链剂。
  10. 一种权利要求7-9中任一项所述的聚氨酯树脂的应用，其中，所述聚氨酯树脂用于聚氨酯弹性体、聚氨酯光学材料、聚氨酯涂覆材料或聚氨酯泡沫的制备，优选用于聚氨酯弹性体的制备。
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04145059A (ja) * 1990-10-08 1992-05-19 Mitsui Toatsu Chem Inc 芳香族イソシアナートの製造方法
CN1064074A (zh) 1991-01-28 1992-09-02 陶氏化学公司 降低甲苯二异氰酸酯中可水解氯化物含量的方法
JP2004027160A (ja) * 2002-06-28 2004-01-29 Mitsui Takeda Chemicals Inc メチレン架橋ポリフェニレンポリイソシアネートの製造方法
CN1827593A (zh) * 2005-02-28 2006-09-06 北京金源化学集团有限公司 应用固体光气制备多异氰酸酯的方法
CN102260194A (zh) 2005-08-04 2011-11-30 巴斯夫欧洲公司 生产二异氰酸酯的方法
CN103319372A (zh) 2012-03-19 2013-09-25 万华化学集团股份有限公司 一种制备浅色二环己基甲烷二异氰酸酯的方法
CN105214568A (zh) 2014-06-10 2016-01-06 万华化学集团股份有限公司 一种加热器、该加热器的用途和应用该加热器制备异氰酸酯的方法
CN105218422A (zh) 2015-10-16 2016-01-06 万华化学集团股份有限公司 一种异氰酸酯的制备方法
CN107337615A (zh) 2016-08-09 2017-11-10 万华化学集团股份有限公司 一种异氰酸酯的制备方法
CN109761855A (zh) 2018-12-20 2019-05-17 万华化学集团股份有限公司 一种制备异佛尔酮二异氰酸酯的方法
CN110511163A (zh) 2019-09-02 2019-11-29 万华化学集团股份有限公司 光化反应制备多异氰酸酯的方法以及制备水性聚氨酯树脂的方法
CN110982038A (zh) 2019-12-27 2020-04-10 万华化学（宁波）有限公司 一种聚氨酯树脂及其制备方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04145059A (ja) * 1990-10-08 1992-05-19 Mitsui Toatsu Chem Inc 芳香族イソシアナートの製造方法
CN1064074A (zh) 1991-01-28 1992-09-02 陶氏化学公司 降低甲苯二异氰酸酯中可水解氯化物含量的方法
JP2004027160A (ja) * 2002-06-28 2004-01-29 Mitsui Takeda Chemicals Inc メチレン架橋ポリフェニレンポリイソシアネートの製造方法
CN1827593A (zh) * 2005-02-28 2006-09-06 北京金源化学集团有限公司 应用固体光气制备多异氰酸酯的方法
CN102260194A (zh) 2005-08-04 2011-11-30 巴斯夫欧洲公司 生产二异氰酸酯的方法
CN103319372A (zh) 2012-03-19 2013-09-25 万华化学集团股份有限公司 一种制备浅色二环己基甲烷二异氰酸酯的方法
CN105214568A (zh) 2014-06-10 2016-01-06 万华化学集团股份有限公司 一种加热器、该加热器的用途和应用该加热器制备异氰酸酯的方法
CN105218422A (zh) 2015-10-16 2016-01-06 万华化学集团股份有限公司 一种异氰酸酯的制备方法
CN107337615A (zh) 2016-08-09 2017-11-10 万华化学集团股份有限公司 一种异氰酸酯的制备方法
CN109761855A (zh) 2018-12-20 2019-05-17 万华化学集团股份有限公司 一种制备异佛尔酮二异氰酸酯的方法
CN110511163A (zh) 2019-09-02 2019-11-29 万华化学集团股份有限公司 光化反应制备多异氰酸酯的方法以及制备水性聚氨酯树脂的方法
CN110982038A (zh) 2019-12-27 2020-04-10 万华化学（宁波）有限公司 一种聚氨酯树脂及其制备方法

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