WO2022257585A1 - 一种磺酸改性多异氰酸酯及其制备方法 - Google Patents

一种磺酸改性多异氰酸酯及其制备方法 Download PDF

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WO2022257585A1
WO2022257585A1 PCT/CN2022/085827 CN2022085827W WO2022257585A1 WO 2022257585 A1 WO2022257585 A1 WO 2022257585A1 CN 2022085827 W CN2022085827 W CN 2022085827W WO 2022257585 A1 WO2022257585 A1 WO 2022257585A1
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component
sulfonic acid
diisocyanate
polyisocyanate
modified polyisocyanate
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PCT/CN2022/085827
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English (en)
French (fr)
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尹逊迪
纪学顺
晋云全
王萃萃
沈如宝
曹玉阳
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万华化学集团股份有限公司
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Priority to US18/003,965 priority Critical patent/US20230257344A1/en
Priority to EP22809633.5A priority patent/EP4144780A4/en
Publication of WO2022257585A1 publication Critical patent/WO2022257585A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/25—Sulfonic acids having sulfo groups bound to carbon atoms of rings other than six-membered aromatic rings of a carbon skeleton
    • C07C309/26—Sulfonic acids having sulfo groups bound to carbon atoms of rings other than six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • C07C309/15—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton the nitrogen atom of at least one of the amino groups being part of any of the groups, X being a hetero atom, Y being any atom
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
    • 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
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the embodiment of the present application relates to the field of modified isocyanate, such as a kind of sulfonic acid hydrophilic modified polyisocyanate and its preparation method. Applications in the fields of agents, sealants, etc.
  • water-based coatings and adhesive compositions have become the best environmentally friendly substitutes for solvent-based coatings and adhesives.
  • hydrophilic components and the production process determine that its water resistance, solvent resistance, and heat resistance are poor, and the introduction of water-based isocyanate curing agents can effectively improve the resistance of water-based coatings and adhesives.
  • Water-based isocyanate curing agents can be divided into two categories according to the hydrophilic group, one is polyether modified isocyanate curing agent, and the other is sulfonic acid modified isocyanate curing agent.
  • polyether-modified isocyanate curing agent has been widely recognized in the market, in order to obtain good hydrophilicity, a large amount of polyether needs to be introduced.
  • the high polyether content brings the disadvantages of low effective isocyanate content and poor resistance. , these inherent disadvantages limit its application.
  • Sulfonic acid-modified isocyanate curing agents are more and more widely used because of their high functionality and easy dispersion.
  • Patent CN1190450C uses 3-(cyclohexylamino)-propanesulfonic acid and 2-(cyclohexylamino)-ethanesulfonic acid solid powder to prepare sulfonic acid-modified polyisocyanate, and the resulting modified polyisocyanate does not need high shear force to be able to Disperse evenly in water.
  • CN104448232B uses 4-(cyclohexylamino)-ethanesulfonic acid solid powder to prepare sulfonic acid-modified polyisocyanate, and also obtains sulfonic acid-modified polyisocyanate with excellent performance.
  • the embodiment of the present application provides a sulfonic acid-modified polyisocyanate and a preparation method thereof, which can effectively improve the shortcomings of the related sulfonic acid-modified isocyanate method, such as slow reaction rate, high product turbidity, and easy deepening of storage color, so that the reaction rate is relatively low. Fast, the product has low turbidity and good storage stability.
  • the embodiment of the present application provides a sulfonic acid-modified polyisocyanate, which is a reaction product obtained by a reaction comprising the following components:
  • R1 is cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-
  • One of tert-butylcyclohexyl, R2 is hydrogen or a saturated or unsaturated, linear or branched, aliphatic or alicyclic or aromatic organic group having 1 to 18 carbon atoms.
  • component b) is added in a mass of 5-150 parts, preferably 15-120 parts.
  • the molar ratio of component c) to component b) is 0.5 ⁇ 1.5:1.
  • the polyisocyanate component a) is an aliphatic, alicyclic, araliphatic and/or aromatic polyisocyanate or modified polyisocyanate with an average isocyanate functionality of 2.0-5.0 and an NCO content of 7.0-32.0 wt%.
  • One or more of the permanent polyisocyanates are included in the polyisocyanates.
  • the above-mentioned modified polyisocyanate may be a modified polyisocyanate containing uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure , they can be passed through one or more of simple aliphatic, alicyclic, aromatic and/or araliphatic diisocyanates, according to DE1670666A, DE1954093A,
  • Suitable diisocyanates for the preparation of the above-mentioned modified polyisocyanates containing uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures Isocyanates are those obtainable by phosgene processes or non-phosgene processes, for example any diisocyanate obtained by thermal decomposition of urethane.
  • the polyisocyanate is a diisocyanate having a molecular weight of 100-500, having aliphatic, alicyclic, aliphatic or aromatic linkages, such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene Methyl diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexyl diisocyanate Propane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'- and 2,4'- - diphenylmethane diisocyanate, tetramethyl
  • the polyisocyanate is based on one or more of 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (H 12 MDI).
  • HDI 1,6-hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • H 12 MDI 4,4'-dicyclohexylmethane diisocyanate
  • the above-mentioned modified polyisocyanate containing uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure can be added anti- Oxygen, free radical scavengers, inhibitors and other additives.
  • the component b) is a sulfonic acid and/or a sulfonate with an amino function, preferably a sulfonic acid and/or a sulfonate with a secondary amino group.
  • component b) is a sulfonic acid organic compound with a secondary amino group with the following structure:
  • R is cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tert
  • One of butylcyclohexyl, R4 is a straight chain or branched aliphatic group with 2 to 6 carbon atoms.
  • the component b) can be partially or completely neutralized by the tertiary amine c) to form a salt before, during and/or after the reaction.
  • the tertiary amine is used on the one hand to neutralize the sulfonic acid/or sulfonate group in component b) to form a sulfonate, and on the other hand as a phase transfer catalyst for the reaction to catalyze the reaction of polyisocyanate and sulfamic acid.
  • the tertiary amine c) is an aliphatic and/or alicyclic substituted, acyclic and/or cyclic tertiary amine, which can be selected from trimethylamine, triethylamine, tripropylamine, N,N-dimethyl butyl amine, N,N-diethylmethylamine, N,N-diisopropylethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine, N-methyl One or more of quinoline, N-ethylquinoline and/or N-ethylmorpholine or other tertiary amines used to catalyze the reaction of isocyanate component and component b) in the art, preferably N,N -Dimethylcyclohexylamine.
  • the modified polyisocyanate can also be mixed with catalysts commonly used in polyurethane disciplines and tertiary amines c), such as other organometallic catalysts: tris(ethyl-acetate acetyl)aluminum, tin n-octylate, n-octanoic acid Zinc, tin(II) 2-ethyl-1-hexanoate, dibutyltin(IV) dichloride, dibutyltin(IV) diacetate, dibutyltin(IV) dilaurate, dioctyltin(IV) diacetate or A mixture of one or more of molybdenum glycolate.
  • catalysts commonly used in polyurethane disciplines and tertiary amines c such as other organometallic catalysts: tris(ethyl-acetate acetyl)aluminum, tin n-octylate, n-octa
  • the cyclohexylamine of the component d) is cyclohexylamine, cyclohexylmethylamine, p-methylcyclohexylamine, 2-methylcyclohexylamine, 2,3-dimethylcyclohexylamine, 3,3,5-Trimethylcyclohexylamine, 4-tert-butylcyclohexylamine, N-methylcyclohexylamine, N-methylcyclohexylmethylamine, N-methyl-p-methylcyclohexylamine, N -Methyl-2-methylcyclohexylamine, N-methyl-2,3-dimethylcyclohexylamine, N-methyl-3,3,5-trimethylcyclohexylamine, N-methyl -4-tert-butylcyclohexylamine, N-ethylcyclohexylamine, N-ethylcyclohexylmethylamine, N-ethyl-p-methylcyclohe
  • component d) is added in a mass of 0.05-2 parts, preferably 0.2-1.6 parts.
  • the applicant of the present application was surprised to find that when the content of the added component d) is controlled within a certain range, the compatibility between sulfamic acid and polyisocyanate can be effectively improved, the reaction rate is accelerated, and the turbidity of the obtained product is low. Good storage stability. If the amount of cyclohexylamine in component d) is too small, it cannot improve the compatibility between sulfamic acid and polyisocyanate. If the amount is too large, component b) reacts with polyisocyanate too quickly, and it is easy to form on the surface of component b) particles. The highly viscous surface prevents further dissolution and reaction with polyisocyanates.
  • the cyclohexylamine of the component d) contains organic R in the compound is the cyclohexylamine of the same group.
  • This application also relates to a preparation method of sulfonic acid modified polyisocyanate, in the presence of component c) tertiary amine, make component a) polyisocyanate component, component b), component d) at 70- Reaction at 110°C, in which component a) polyisocyanate can be added in one or more steps.
  • antioxidants can be added to reduce its color number.
  • the antioxidant can be compounds such as aromatic amines and hindered phenols that can eliminate free radicals and their derivatives, or antioxidants that can decompose hydroperoxides, including phosphorus- and sulfur-containing organic compounds, or their Compositions.
  • the reaction can be carried out in a solvent that is inert to the NCO reaction.
  • a solvent that is inert to the NCO reaction.
  • acetone butanone, ethyl cyclopentanone acetate, butyl acetate, N-ethylpyrrolidone, N-methylpyrrolidone, toluene, xylene, chlorobenzene, propylene glycol methyl ether acetate, 1-methoxypropane- In solvents such as 2-yl acetate, 3-methoxy-n-butyl acetate, aromatic compounds, dimethyl carbonate, diethyl carbonate, butyrolactone, caprolactone, and methyl caprolactone One or any mixture of many.
  • the present application also provides the use of the sulfonic acid hydrophilically modified polyisocyanate and the modified polyisocyanate prepared by the method of the present application as a crosslinking agent in water-dispersible two-component coatings and adhesives. It has light color, low turbidity, excellent room temperature storage stability and excellent water dispersion performance.
  • the present application also provides the use of a polyisocyanate hydrophilically modified with sulfamic acid as a starting component for the preparation of a blocked polyisocyanate which is water-dispersible or present in the form of a dispersion in water.
  • Suitable blocking agents are, for example, diethyl malonate, ethyl acetoacetate, 3,5-dimethylpyrazole, imidazole, ⁇ -caprolactam, etc. or mixtures of these blocking agents.
  • the sulfonic acid-modified polyisocyanate of the present application in addition to being used as a two-component coating and adhesive as a cross-linking component, can also be used as a cross-linking agent for fabric finishing , printing paint binder, and used to crosslink other aqueous dispersions or as an auxiliary agent for moistening treatment of paper.
  • Sulfamic acid b1 2-cyclohexylaminoethanesulfonic acid, purchased from Aladdin reagents, purity ⁇ 99%
  • Sulfamic acid b2 3-cyclohexylaminopropanesulfonic acid, purchased from Bailingwei Reagents, with a purity of 99%
  • Sulfamic acid b3 4-cyclohexylaminobutanesulfonic acid, react with cyclohexylamine and 1,4-butane sultone at a molar ratio of 3:1 at 80°C for 6h in a dioxane solvent, collect Solid, washed with acetone until white.
  • Sulfamic acid b4 3-p-methylcyclohexylaminopropanesulfonic acid, in dioxane solvent, with p-methylcyclohexylamine and 1,4-butane sultone in a molar ratio of 3:1 After reacting at 80°C for 6h, the solid was collected and washed with acetone until white.
  • Tertiary amine c1 N,N-dimethylcyclohexylamine, purchased from Bailingwei reagent, purity 99%
  • Tertiary amine c2 N-ethylmorpholine, purchased from Bailingwei reagent, purity 99%
  • Primary amine d1 cyclohexylamine, purchased from Bailingwei Reagents, with a purity of 99%
  • Primary amine d2 4-methylcyclohexylamine, purchased from Bailingwei Reagents, with a purity of 95%
  • Primary amine d3 cyclohexylmethylamine, purchased from Bailingwei Reagents, with a purity of 98%
  • Secondary amine d4 N-methylcyclohexylamine, purchased from Bailingwei Reagents, with a purity of 98%
  • Secondary amine d5 N-ethylcyclohexylamine, purchased from Bailingwei Reagents, with a purity of 99%
  • NCO test standard GB/T 12009.4-2016
  • Viscosity test standard Brookfield LV 63#/3rpm, 25°C
  • Color number test standard use 723C visible spectrophotometer, use Hazen ruler to measure
  • Turbidity test standard measured by HACH 2100Q Portable Turbidimeter, the unit is NTU.
  • Example 4 The main difference between this embodiment and Example 4 is that the amount of cyclohexylamine d1 added is 0.75g, and the polyisocyanate modified with sulfamic acid with the following characteristic data is obtained:
  • Example 4 The main difference between this embodiment and Example 4 is that the amount of cyclohexylamine d1 added is 0.60 g, and the polyisocyanate modified with sulfamic acid with the following characteristic data is obtained:
  • Example 4 The main difference between this embodiment and Example 4 is that the quality of the cyclohexylamine d1 added is 0.10g, and the polyisocyanate modified with sulfamic acid with the following characteristic data is obtained:
  • NCO content 20.59wt%

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

本文公布一种磺酸改性多异氰酸酯及其制备方法，通过控制原料中环己基胺组分的含量，促进氨基磺酸与多异氰酸酯反应速率加快，从而使制备得到得产品具有颜色浅、浊度低的优点，且存储稳定性好。

Description

一种磺酸改性多异氰酸酯及其制备方法 技术领域
本申请实施例涉及改性异氰酸酯领域，例如一种磺酸亲水改性多异氰酸酯及其制备方法，本申请实施例还涉及所制备的磺酸亲水改性多异氰酸酯在涂覆剂、粘合剂、密封剂等领域中的应用。
背景技术
随着日益增加的环保压力，水性涂料、粘合剂组合物成为了溶剂型涂料、粘合剂的最佳环保替代品。但亲水组分的引入以及生产工艺决定其耐水性、耐溶剂性、耐热性能较差，而水性异氰酸酯固化剂的引入能够有效改善水性涂料、粘合剂的耐性。
水性异氰酸酯固化剂根据亲水基团可分为两类，一类是聚醚改性的异氰酸酯固化剂，另外一类则是磺酸改性的异氰酸酯固化剂。其中聚醚改性的异氰酸酯固化剂虽然获得了广泛的市场认可，但为了获得好的亲水性需要引入大量的聚醚，高聚醚含量为其带来了有效异氰酸酯含量低以及耐性差的缺点，这些固有的缺点限制了它的应用。磺酸改性的异氰酸酯固化剂因具有官能度高易于分散等优点其应用也越来越广泛。
专利CN1190450C使用3-(环己基氨基)-丙磺酸和2-(环己基氨基)-乙磺酸固体粉末制备磺酸改性多异氰酸酯，所得改性的多异氰酸酯不需要高剪切力就能够在水中均匀分散。CN104448232B使用4-(环己基氨基)-乙磺酸固体粉末制备磺酸改性多异氰酸酯，同样获得了性能优异的磺酸改性多异氰酸酯。但是相关技术中采用固体磺酸化合物改性异氰酸酯固化剂的方法存在一定的缺陷：首先固体粉末磺酸与异氰酸酯的相容性差，界面反应导致反应时间长、产品颜色深；其次，未完全反应的固体粉末会引起产品浊度高且随着存储时间的延长颜色加深。
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磺酸改性多异氰酸酯及其制备方法，可以有效改善相关的磺酸改性异氰酸酯方法中反应速率慢、产品浊度高、储存颜色易加深的缺点，使得反应速率较快，产品浊度低，储存稳定性好。
本申请实施例提供一种磺酸改性多异氰酸酯，所述磺酸改性多异氰酸酯是采用包含以下组分的反应得到的反应产物：
a)至少一种多异氰酸酯组分；
b)至少一种带有一个以上磺酸和/或磺酸根基团的有机化合物，且该化合物含有至少一个巯基、伯氨基或仲氨基；
c)至少一种叔胺；
d)至少一种具有以下结构的环己基胺：
Figure PCTCN2022085827-appb-000001
其中，中R1是环己基、环己甲基、对甲基环己基、2-甲基环己基、2,3-二甲基环己基、3,3,5-三甲基环己基、4-叔丁基环己基中的一种，R2是氢或具有1至18个碳原子的饱和或不饱和、直链或支化、脂族或脂环族或芳族有机基团。
优选的，以组分a)的质量为1000份计，组分b)加入的质量为5～150份，优选15-120份。
优选的，组分c)与组分b)的摩尔比为0.5～1.5：1。优选的，所述多异氰酸酯组分a)为平均异氰酸酯官能度为2.0-5.0，NCO含量为7.0-32.0wt％的脂族、脂环族、芳脂族和/或芳族的多异氰酸酯或改性多异氰酸酯中的一种或多种。
上述的改性多异氰酸酯可以是含有脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、亚氨基噁二嗪二酮和/或噁二嗪三酮结构的改性多异氰酸酯，它们可通过简单的脂肪族、脂环族、芳香族和/或芳脂族的二异氰酸酯中的一种或多种，可按照DE1670666A，DE1954093A，
DE2414413A，DE2452532A，DE2641380A，DE3700209A，DE3900053A、DE3928503A、EP0336205A、EP0339396A以及EP0798299A等专利中的方法改性制备；
用于制备上述含有脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、亚氨基噁二嗪二酮和/或噁二嗪三酮结构的改性多异氰酸酯的适合的二异氰酸酯是那些可以用光气法或者非光气法得到的，例如由氨基甲酸乙酯热分解得到的任何二异氰酸酯。
优选的，所述多异氰酸酯是分子量在100-500、具有脂肪性、脂环性、芳脂性或者芳香性键接的二异氰酸酯，例如四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、4,4'-二环己基丙烷二异氰酸酯、1,4-苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,2'-和2,4'-二苯基甲烷二异氰酸酯、四甲基二甲苯基二异氰酸酯和对苯二甲基二异氰酸酯或这些二异氰酸酯的混合物。
优选的，多异氰酸酯为基于1,6-己二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)和4,4’-二环己基甲烷二异氰酸酯(H 12MDI)中的一种或多种的具有异氰脲酸酯基团的改性多异氰酸酯。
上述含有脲二酮、异氰脲酸酯、脲基甲酸酯、缩二脲、亚氨基噁二嗪二酮和/或噁二嗪三酮结构的改性多异氰酸酯在制备过程中可添加抗氧剂、自由基清除剂、抑制剂等助剂。
优选的，所述组分b)是带有氨基官能团的磺酸和/或磺酸盐，优选带有仲氨基的磺酸和/或磺酸盐。
进一步的，组分b)为带有仲氨基的磺酸有机化合物具有如下结构：
Figure PCTCN2022085827-appb-000002
其中R 3为环己基、环己甲基、对甲基环己基、2-甲基环己基、2,3-二甲基环己基、3,3,5-三甲基环己基、4-叔丁基环己基中的一种，R 4为是具有2至6个碳原子的直链或支化脂族基团。
所述组分b)在反应前、反应中和/或反应后可被叔胺c)部分或全部中和成盐。所述叔胺一方面用来中和组分b)中的磺酸/或磺酸根基团，形成磺酸盐，另一方面作为反应的相转移催化剂来催化多异氰酸酯和氨基磺酸的反应。
所述的叔胺c)为脂肪族和/或脂环族取代的、非环状和/或环状的叔胺，可选自三甲胺、三乙胺、三丙胺、N,N-二甲基丁基胺、N,N-二乙基甲基胺、N,N-二异丙基乙基胺、N,N-二甲基环己基胺、N-甲基哌啶、N-甲基喹啉、N-乙基喹啉和/或N-乙基吗啉或本领域其他用于催化异氰酸酯组分与组分b)反应的叔胺中的一种或多种，优选为N,N-二甲基环己基胺。
优选的，所述改性多异氰酸酯中还可以加入聚氨酯学科中通常使用的催化剂与叔胺c)混合使用，比如其他有机金属催化剂：三(乙基-乙酸乙酰)铝、正辛酸锡、正辛酸锌、2-乙基-1-己酸锡(Ⅱ)、二氯化二丁基锡(Ⅳ)、二乙酸二丁基锡(Ⅳ)、二月桂酸二丁基锡(Ⅳ)、二乙酸二辛基锡(Ⅳ)或者乙醇酸钼中的一种或多种的混合物。
优选的，所述组分d)的环己基胺为环己胺、环己甲基胺、对甲基环己胺、2-甲基环己胺、2,3-二甲基环己胺、3,3,5-三甲基环己胺、4-叔丁基环己胺、N-甲基环己胺、N-甲基环己甲基胺、N-甲基对甲基环己胺、N-甲基-2-甲基环己胺、N-甲基-2,3-二甲基环己胺、N-甲基-3,3,5-三甲基环己胺、N-甲基-4-叔丁基环己胺、N-乙基环己胺、N-乙基环己甲基胺、N-乙基对甲基环己胺、N-乙基-2-甲基环己胺、N-乙基-2,3-二甲基环己胺、N-乙基-3,3,5-三甲基环己胺、N-乙基-4-叔丁基环己胺中的一种或多种。
优选的，以组分a)的质量为1000份计，组分d)的加入的质量为0.05-2份，优选0.2-1.6份。本申请申请人惊喜的发现，当加入组分d)的含量控制在一定范围内时，可以有效改善氨基磺酸与多异氰酸酯的相容性，加快反应速率，且得到的产品浊度较低，储存稳定性好。组分d)的环己基胺用量太少无法起到改善氨基磺酸与多异氰酸酯相容性的作用，用量太多组分b)与多异氰酸酯反应太快，容易在组分b)颗粒表面形成高黏表层阻止其进一步溶解与多异氰酸酯反应。
为了更好的增加氨基磺酸与多异氰酸酯相容性，加快反应速率，获得颜色浅、浊度低的产品，优选的，所述组分d)的环己基胺含有与组分b)的有机化合物中的R 3相同基团的环己基胺。
本申请还涉及到一种磺酸改性多异氰酸酯的制备方法，在组分c)叔胺的存在下，使组分a)多异氰酸酯组分、组分b)、组分d)在70-110℃条件下反应，其中组分a)多异氰酸酯可一步或多步投入。在制备过程中，可加入抗氧剂降低其色号。所述抗氧剂可以是能消除自由基的芳香胺和受阻酚等化合物及其衍生物，也可以是能分解氢过氧化物的抗氧剂有含磷和含硫的有机化合物，或者是它们的组合物。
在本申请所述的方法中，该反应可选择在NCO反应惰性的溶剂中进行。例如丙酮、丁酮、环戊酮乙酸乙酯、乙酸丁酯、N-乙基吡咯烷酮、N-甲基吡咯烷酮、甲苯、二甲苯、氯苯、丙二醇甲醚醋酸酯、1-甲氧基丙-2-基乙酸酯、3-甲氧基-正丁基乙酸酯、芳香化合物、碳酸二甲酯、碳酸二乙酯、丁内酯、己内酯以及甲基己内酯等溶剂中的一种或者任意多种的混合物。
本申请还提供所述的磺酸亲水改性的多异氰酸酯以及采用本申请方法制备的改性多异氰酸酯作为交联剂用在水分散性双组份涂料、粘合剂中的用途。其颜色浅、浊度低、具有优异的常温储存稳定性和优异的水分散性能。
本申请还提供氨基磺酸亲水改性的多异氰酸酯作为起始组分在制备水分散性或在水中以分散体形式存在的封闭多异氰酸酯中的用途。适合的封闭剂有例如丙二酸二乙酯、乙酰乙酸乙酯、3,5-二甲基吡唑、咪唑、ε-己内酰胺等或者这些封闭剂的混合物。
本申请的磺酸改性的多异氰酸酯，除了用作双组份的涂料和粘合剂作为交联成分以外，本申请的氨基磺酸改性的多异氰酸酯还可以作为交联剂用于织物整理、印花涂料粘合剂、以及用来交联其他水分散体或者作为助剂对纸张进行增湿处理。
本申请通过将环己基胺引入到多异氰酸酯中，增大了多异氰酸酯与带有至少一个磺酸和/或磺酸根基团的有机化合物的相容性，使反应速率加快，在大大增加生产效率的同时获得了颜色浅、浊度低的磺酸亲水改性多异氰酸酯产品。
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
下面结合实施例对本申请作进一步的说明，需要说明的是，实施例并不构成对本申请要求保护范围的限制。
多异氰酸酯a1(万华化学
Figure PCTCN2022085827-appb-000003
HT-100，基于HDI的多异氰酸酯，NCO＝21.7-22.2wt％)；
多异氰酸酯a2(拜耳NZ1，基于HDI和IPDI的多异氰酸酯，NCO＝20wt％)
氨基磺酸b1：2-环己胺基乙磺酸，购买自阿拉丁试剂，纯度≥99％
氨基磺酸b2：3-环己胺基丙磺酸，购买自百灵威试剂，纯度99％
氨基磺酸b3：4-环己胺基丁磺酸，在二氧六环溶剂中，用环己胺和1,4-丁磺酸内酯以摩尔比3:1在80℃反应6h，收集固体，用丙酮洗涤至白色。
氨基磺酸b4：3-对甲基环己胺基丙磺酸，在二氧六环溶剂中，用对甲基环己胺和1,4-丁磺酸内酯以摩尔比3:1在80℃反应6h，收集固体，用丙酮洗涤至白色。
叔胺c1：N,N-二甲基环己胺，购买自百灵威试剂，纯度99％
叔胺c2：N-乙基吗啉，购买自百灵威试剂，纯度99％
伯胺d1：环己胺，购买自百灵威试剂，纯度99％
伯胺d2：4-甲基环己胺，购买自百灵威试剂，纯度95％
伯胺d3：环己甲胺，购买自百灵威试剂，纯度98％
仲胺d4：N-甲基环己胺，购买自百灵威试剂，纯度98％
仲胺d5：N-乙基环己胺，购买自百灵威试剂，纯度99％
测试方法：
1.NCO测试标准：GB/T 12009.4-2016
2.粘度测试标准：Brookfield LV 63#/3rpm,25℃
3.色号测试标准：使用723C型可见分光光度计，采用Hazen标尺测量
4.浊度测试标准：使用HACH 2100Q Portable Turbidimeter测量，单位NTU。
实施例1
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中，50℃，200rpm搅拌下将0.32g环己基胺d1(0.003mol)滴加到380g多异氰酸酯a1中，反应10min后，将17.39g(0.084mol)氨基磺酸b1和10.67g(0.084mol)叔胺c1加入到反应体系中，混合均匀，加热到80℃反应3h，停止反应，经325目滤网过滤，冷却至室温，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.5wt％
平均NCO官能度：3.39
粘度(25℃)：5600mPa·s
SO3-含量：1.65wt％
色号：6
浊度：0.2
实施例2
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中，将将17.39g(0.084mol)氨基磺酸b1和6.4g(0.042mol)叔胺c1加入到380g多异氰酸酯a1中，200rpm搅拌混合均匀并加热到80℃，逐滴将0.6g(0.006mol)环己基胺d1加入到反应体系中并反应3h，停止反应，经325目滤网过滤，冷却至室温，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.59wt％
平均NCO官能度：3.39
粘度(25℃)：5500mPa·s
SO3-含量：1.66wt％
色号：4
浊度：0
实施例3
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中，将将17.39g(0.084mol)氨基磺酸b1和16g(0.126mol)叔胺c1加入到380g多异氰酸酯a1中，200rpm搅拌混合均匀并加热到80℃，逐滴将0.08g(0.001mol)环己基胺d1加入到反应体系中并反应4h，停止反应，经325目滤网过滤，冷却至室温，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.40wt％
平均NCO官能度：3.40
粘度(25℃)：5500mPa·s
SO3-含量：1.63wt％
色号：14
浊度：0.6
实施例4
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中，将将18.57g(0.084mol)氨基磺酸b2和10.67g(0.084mol)叔胺c1加入到380g多异氰酸酯a1中，200rpm搅拌混合均匀并加热到80℃，逐滴将0.32g(0.003mol)环己基胺d1加入到反应体系中并反应3h，停止反应，冷却至室温，经325目滤网过滤，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.35wt％
平均NCO官能度：3.39
粘度(25℃)：5800mPa·s
SO3-含量：1.64wt％
色号：4
浊度：0.2
实施例5
本实施例与实施例4的主要区别之处在于，加入的环己基胺d1的量为0.75g，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.39wt％
平均NCO官能度：3.39
粘度(25℃)：5600mPa·s
SO3-含量：1.64wt％
色号：26
浊度：1.3
实施例6
本实施例与实施例4的主要区别之处在于，加入的环己基胺d1的量为0.60g，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.45wt％
平均NCO官能度：3.39
粘度(25℃)：6000mPa·s
SO3-含量：1.64wt％
色号：9
浊度：0.2
实施例7
本实施例与实施例4的主要区别之处在于，加入的环己基胺d1的质量为0.10g，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.48wt％
平均NCO官能度：3.40
粘度(25℃)：5600mPa·s
SO3-含量：1.64wt％
色号：15
浊度：0.8
实施例8
本实施例与实施例4的主要区别之处在于，加入的环己基胺d1的质量为0.02g得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.44wt％
平均NCO官能度：3.40
粘度(25℃)：5700mPa·s
SO3-含量：1.64wt％
色号：25
浊度：1.1
实施例9
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中，将18.57g(0.084mol)氨基磺酸b2和10.67g(0.084mol)叔胺c1加入到380g多异氰酸酯a1中，200rpm搅拌混合均匀并加热到80℃，逐滴将0.42g环己基胺d5加入到反应体系中并反应3h，停止反应，经325目滤网过滤，冷却至室温，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.48wt％
平均NCO官能度：3.39
粘度(25℃)：5600mPa·s
SO3-含量：1.64wt％
色号：9
浊度：0.2
实施例10
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中，将18.57g(0.084mol)氨基磺酸b2和9.66g(0.084mol)叔胺c2加入到380g多异氰酸酯a1中，200rpm搅拌混合均匀并加热到80℃，逐滴将0.37g环己基胺d2加入到反应体系中并反应3h，停止反应，经325目滤网过滤，冷却至室温，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.5wt％
平均NCO官能度：3.39
粘度(25℃)：6000mPa·s
SO3-含量：1.64wt％
色号：7
浊度：0.2
实施例11
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中，将19.75g(0.084mol)氨基磺酸b3和10.67g(0.084mol)叔胺c1加入到380g多异氰酸酯a2中，200rpm搅拌混合均匀并加热到80℃，逐滴将0.38g环己基胺d3加入到反应体系中并反应5h，停止反应，经325目滤网过滤，冷却至室温，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：17.54wt％
平均NCO官能度：3.24
粘度(25℃)：5100mPa·s
SO3-含量：1.64wt％
色号：11
浊度：0.3
实施例12
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中，将9.28g(0.042mol)氨基磺酸b2和5.33g(0.042mol)叔胺c1加入到380g多异氰酸酯a1中，200rpm搅拌混合均匀并加热到80℃，逐滴将0.4g环己基胺d4加入到反应体系中并反应3h，停止反应，经325目滤网过滤，冷却至室温，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：20.59wt％
平均NCO官能度：3.47
粘度(25℃)：3800mPa·s
SO3-含量：0.85wt％
色号：4
浊度：0.1
实施例13
在装有机械搅拌器、回流管、温度计和氮气进出口的四口圆底烧瓶中，将37.12g(0.17mol)氨基磺酸b2和21.33g(0.17mol)叔胺c1加入到380g多异氰酸酯a1中，200rpm搅拌混合均匀并加热到80℃，逐滴将0.32g(0.003mol)环己基胺d1加入到反应体系中并反应4h，停止反应，经325目滤网过滤，冷却至室温，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：17.20wt％
平均NCO官能度：3.24
粘度(25℃)：7700mPa·s
SO3-含量：3.06wt％
色号：17
浊度：0.7
对比例1
本对比例与实施例4的主要区别之处在于，所述环己基胺d1的加入量为0.01g，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.50wt％
平均NCO官能度：3.4
粘度(25℃)：5900mPa·s
SO3-含量：1.64wt％
色号：61
浊度：4.7
对比例2
本对比例与实施例4的主要区别之处在于，制备过程中不加入环己基胺d1，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.44wt％
平均NCO官能度：3.4
粘度(25℃)：5300mPa·s
SO3-含量：1.64wt％
色号：82
浊度：7.2
对比例3
本对比例与实施例4的主要区别之处在于，加入的环己基胺d1的量为0.85g，得到了具有以下特征数据的氨基磺酸改性的多异氰酸酯：
固体含量：100％
NCO含量：19.31wt％
平均NCO官能度：3.38
粘度(25℃)：6400mPa·s
SO3-含量：1.64wt％
色号：96
浊度：12
由实施例1-13以及对比例1-2可看出，在体系中引入少量环己基胺可提升氨基磺酸与多异氰酸酯的反应速率，获得颜色浅、浊度低的磺酸亲水改性多异氰酸酯，由对比例1、3可看出，引入的伯胺过量或过少均无法起到较好的作用，无法获得颜色浅/浊度低的产品。
存储稳定性测试：将200g所制备的氨基磺酸改性的多异氰酸酯装入250ml铝瓶(使用前在100℃烘箱热烘1h)中，用氮气吹扫30s后放入50℃烘箱中储存，30天后测试NCO含量、粘度、色号变化，具体数据如下表所示：
表1储存稳定性测试数据
Figure PCTCN2022085827-appb-000004
由实施例1-13以及对比例1-3可看出，在本申请所述含量的环己基胺存在条件下所制备得到的磺酸亲水改性多异氰酸酯色号更低、储存稳定性更好，经热储后颜色变化不明显。

Claims (15)

  1. 一种磺酸改性多异氰酸酯，其中，所述磺酸改性多异氰酸酯是采用包含以下组分的反应得到的反应产物：
    a)至少一种多异氰酸酯组分；
    b)至少一种带有一个以上磺酸和/或磺酸根基团的有机化合物，且该化合物含有至少一个巯基、伯氨基或仲氨基；
    c)至少一种叔胺；
    d)至少一种具有以下结构的环己基胺：
    Figure PCTCN2022085827-appb-100001
    其中，中R 1是环己基、环己甲基、对甲基环己基、2-甲基环己基、2,3-二甲基环己基、3,3,5-三甲基环己基、4-叔丁基环己基中的一种，R 2是氢或具有1至18个碳原子的饱和或不饱和、直链或支化、脂族或脂环族或芳族有机基团。
  2. 根据权利要求1所述的磺酸改性多异氰酸酯，其中，以组分a)的质量为1000份计，组分b)加入的质量为5～150份，优选15-120份。
  3. 根据权利要求1所述的磺酸改性多异氰酸酯，其中，组分c)与组分b)的摩尔比为0.5～1.5：1。
  4. 根据权利要求1所述的磺酸改性多异氰酸酯，其中，所述多异氰酸酯组分a)为平均异氰酸酯官能度为2.0-5.0，NCO含量为7.0-32.0wt％的脂族、脂环族、芳脂族和/或芳族的多异氰酸酯或改性多异氰酸酯中的一种或多种。
  5. 根据权利要求1所述的磺酸改性多异氰酸酯，其中，所述多异氰酸酯组分是分子量在100-500、具有脂肪性、脂环性、芳脂性或者芳香性键接的二异氰酸酯，优选四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、4,4'-二环己基丙烷二异氰酸酯、1,4-苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,2'-和2,4'-二苯基甲烷二异氰酸酯、四甲基二甲苯基二异氰酸酯和对苯二甲基二异氰酸酯或这些二异氰酸酯的混合物；
    优选的，多异氰酸酯组分为基于1,6-己二异氰酸酯、异佛尔酮二异氰酸酯和4,4’-二环己基甲烷二异氰酸酯中的一种或多种的具有异氰脲酸酯基团的改性多异氰酸酯。
  6. 根据权利要求1所述的磺酸改性多异氰酸酯，其中，所述组分b)是带有氨基官能团的 磺酸和/或磺酸盐，优选带有仲氨基的磺酸和/或磺酸盐。
  7. 根据权利要求6所述的磺酸改性多异氰酸酯，其中，组分b)为带有仲氨基的磺酸有机化合物具有如下结构：
    Figure PCTCN2022085827-appb-100002
    其中R 3为环己基、环己甲基、对甲基环己基、2-甲基环己基、2,3-二甲基环己基、3,3,5-三甲基环己基、4-叔丁基环己基中的一种，R 4为是具有2至6个碳原子的直链或支化脂族基团。
  8. 根据权利要求1-7任一项所述的磺酸改性多异氰酸酯，其中，所述的叔胺c)为脂肪族和/或脂环族取代的、非环状和/或环状的叔胺，可选自三甲胺、三乙胺、三丙胺、N,N-二甲基丁基胺、N,N-二乙基甲基胺、N,N-二异丙基乙基胺、N,N-二甲基环己基胺、N-甲基哌啶、N-甲基喹啉、N-乙基喹啉和/或N-乙基吗啉中的一种或多种，优选为N,N-二甲基环己基胺。
  9. 根据权利要求1-8任一项所述的磺酸改性多异氰酸酯，其中，所述改性多异氰酸酯中还可以加入聚氨酯学科中通常使用的催化剂与叔胺c)混合使用，比如其他有机金属催化剂：三(乙基-乙酸乙酰)铝、正辛酸锡、正辛酸锌、2-乙基-1-己酸锡(Ⅱ)、二氯化二丁基锡(Ⅳ)、二乙酸二丁基锡(Ⅳ)、二月桂酸二丁基锡(Ⅳ)、二乙酸二辛基锡(Ⅳ)或者乙醇酸钼中的一种或多种的混合物。
  10. 根据权利要求1-8任一项所述的磺酸改性多异氰酸酯，其中，所述组分d)的环己基胺为环己胺、环己甲基胺、对甲基环己胺、2-甲基环己胺、2,3-二甲基环己胺、3,3,5-三甲基环己胺、4-叔丁基环己胺、N-甲基环己胺、N-甲基环己甲基胺、N-甲基对甲基环己胺、N-甲基-2-甲基环己胺、N-甲基-2,3-二甲基环己胺、N-甲基-3,3,5-三甲基环己胺、N-甲基-4-叔丁基环己胺、N-乙基环己胺、N-乙基环己甲基胺、N-乙基对甲基环己胺、N-乙基-2-甲基环己胺、N-乙基-2,3-二甲基环己胺、N-乙基-3,3,5-三甲基环己胺、N-乙基-4-叔丁基环己胺中的一种或多种；
    优选的，以组分a)的质量为1000份计，组分d)的加入的质量为0.05-2份，优选0.2-1.6份；
    优选的，所述组分d)的环己基胺含有与组分b)的有机化合物中的R 3相同基团的环己基胺。
  11. 根据权利要求1-10任一项所述的磺酸改性多异氰酸酯的制备方法，其中，在组分c)叔胺的存在下，使组分a)多异氰酸酯组分、组分b)、组分d)在70-110℃条件下反应，其中组分a)多异氰酸酯可一步或多步投入。
  12. 根据权利要求11所述的制备方法，其中，所述制备方法中，还可加入抗氧剂。
  13. 根据权利要求9所述的制备方法，其中，所述抗氧剂是能消除自由基的芳香胺和受阻酚类化合物及其衍生物或能分解氢过氧化物的抗氧剂有含磷和含硫的有机化合物，或者是它们的组合物。
  14. 根据权利要求11所述的制备方法，其中，该反应可选择在NCO反应惰性的溶剂中进行。
  15. 根据权利要求11所述的制备方法，其中，所述NCO反应惰性的溶剂包括丙酮、丁酮、环戊酮乙酸乙酯、乙酸丁酯、N-乙基吡咯烷酮、N-甲基吡咯烷酮、甲苯、二甲苯、氯苯、丙二醇甲醚醋酸酯、1-甲氧基丙-2-基乙酸酯、3-甲氧基-正丁基乙酸酯、芳香化合物、碳酸二甲酯、碳酸二乙酯、丁内酯、己内酯以及甲基己内酯溶剂中的一种或者任意多种的混合物。
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