WO2021185335A1 - 一种亲水性二异氰酸酯及其制备方法和应用 - Google Patents

一种亲水性二异氰酸酯及其制备方法和应用 Download PDF

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WO2021185335A1
WO2021185335A1 PCT/CN2021/081648 CN2021081648W WO2021185335A1 WO 2021185335 A1 WO2021185335 A1 WO 2021185335A1 CN 2021081648 W CN2021081648 W CN 2021081648W WO 2021185335 A1 WO2021185335 A1 WO 2021185335A1
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diisocyanate
hydrophilic
water
diol
polyurethane
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PCT/CN2021/081648
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English (en)
French (fr)
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刘晓鸿
周国豪
梁杰宏
何绍群
周建明
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佛山市精信汇明科技有限公司
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Publication of WO2021185335A1 publication Critical patent/WO2021185335A1/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
    • C07C309/02—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
    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
    • 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
    • C08G18/70—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
    • C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the invention belongs to the field of polyurethane, and specifically relates to a hydrophilic diisocyanate and a preparation method and application thereof.
  • the water-based polyurethane is to introduce hydrophilic groups into the hydrophobic polyurethane structure, how to introduce low-cost, non-toxic, odorless, and hydrophilic groups with good hydrophilic effect, and what simple and easy-to-use process methods to achieve without changing the original
  • the main performance of solvent-based products and waterborne polyurethane products without VOC emissions are the focus of continuous research in this field.
  • the hydrophilic agent with the better effect of changing polyurethane oil to water is sulfonate base, because sulfonate is a strong acid and strong base salt, which has strong hydrophilicity.
  • sulfonate is a strong acid and strong base salt, which has strong hydrophilicity.
  • the polyurethane dispersion is synthesized, the amount is less, and the dispersion is more stable.
  • Electrical double layer structure; due to the small amount of hydrophilic groups, it has little effect on the performance of polyurethane, so that the acid and alkali resistance, electrolyte resistance, mechanical stability, and compatibility of the polyurethane dispersion with additives, And the performance of the film can basically maintain the performance of the original solvent-based product.
  • Prior art CN107082860A discloses a small molecular diol with a molecular weight of 350-1000 containing sulfonic acid groups, which reacts with diisocyanate to prepare an aqueous polyurethane curing agent, and introduces the use of dicarboxysulfonate and dihydroxysulfonate
  • the preparation method for preparing small molecular diols containing sulfonic acid groups but the conversion conditions are relatively harsh in practical applications, and it is difficult for ordinary enterprises to master this technology.
  • the present invention has developed a hydrophilic diisocyanate containing sulfonate groups.
  • the object of the present invention is to provide a hydrophilic diisocyanate containing sulfonate groups and a preparation method and application thereof, using the hydrophilic diisocyanate containing sulfonate groups as the preparation of waterborne polyurethane
  • the hydrophilic raw material can simplify the oil-to-water preparation process, reduce the cost, and can maintain the main technical performance of the original solvent-based product.
  • the above-mentioned application refers to the application of the sulfonate-containing hydrophilic diisocyanate in the preparation of water-based polyurethane emulsions, water-based polyurethane curing agents, water-based polyurethane binders, water-based polyurethane coating agents, water-based polyurethane elastomers, and the like.
  • a hydrophilic diisocyanate comprising at least one structural unit containing the following general formula:
  • SO 3 M is a sulfonate group
  • M is K ion or Na ion or ammonium ion
  • n is 1-6.
  • a preparation method of hydrophilic diisocyanate includes the following steps:
  • the hydrophilic chain extender is divided into 3-10 parts, and then added in several times. After each part of the hydrophilic chain extender is added, the reaction is carried out at 50-60°C until the liquid in the kettle is transparent.
  • the fractional number of times is 3-10 times.
  • the molar ratio of the diisocyanate to the hydrophilic chain extender is (2-6):1.
  • the molar ratio of the diisocyanate to the hydrophilic chain extender is (3-4):1.
  • the hydrophilic diisocyanate of the present invention contains a certain proportion of diisocyanate monomers in addition to the sulfonate-based diisocyanate in the main chain structure, because only a certain proportion of hydrophilic groups is required for the preparation of waterborne polyurethane. If the group exists, the prepared prepolymer can be soluble in water, emulsified with water, or dispersible with water, so the hydrophilic diisocyanate of the present invention is designed with a certain proportion of hydrophilic groups.
  • the hydrophilic chain extender is a small molecule diol containing at least one sulfonate group or a small molecule diol containing an aminosulfonate group.
  • the sulfonate group-containing small molecule diol is sodium 1,2-dihydroxy-3-propanesulfonate, sodium 1,4-dihydroxybutane-2-sulfonate or small molecule sulfonic acid At least one of the salt diols.
  • the small molecule diol of the aminosulfonate base is sodium N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate.
  • the diisocyanate is at least one of MDI, HMDI, TDI, HDI, IPDI or XDI.
  • the small molecule sulfonate diol is an esterification product of a dicarboxysulfonate, a small molecule diol, and a small molecule dibasic acid, and the molecular weight is 350-3000.
  • the molecular weight of the small molecule sulfonate diol is 380-600.
  • the small molecule diol is a diol with a molecular weight of less than 300.
  • the small molecule diol is 3-methyl-1,5-pentanediol, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanediol, methyl propylene glycol, TCD tricyclic glycol, 1,3-propanediol, 1,4-dimethylolcyclohexane, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, diethyl Pentylene glycol, 1,2-propanediol, diethylene glycol, tetrahydrofurandiol, 1,6-hexanediol, trimethylpentanediol, butyl ethyl propylene glycol, 2,2-bis(4-hydroxybenzene) Base) at least one of propane, dipropylene glycol, tripropylene glycol, or ethyl hexylene glycol
  • the small molecule dibasic acid is a dibasic acid with a molecular weight of less than 300.
  • the small molecule dibasic acid is adipic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic anhydride, dimethyl terephthalate, succinic acid or glutaric acid. At least one of the acids.
  • the dicarboxysulfonate is at least one of sodium dicarboxysulfonate, potassium dicarboxysulfonate or ammonium dicarboxysulfonate.
  • the dicarboxysulfonate is 5-sodium isophthalic acid sulfonate.
  • the added amount of the co-solvent is 0-40% of the weight of the diisocyanate, and a hydrophilic diisocyanate with 100% solid content can be obtained.
  • the co-solvent is acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, tetrahydrofuran, dioxane or dimethyl At least one of carbamide.
  • a polyurethane emulsion is obtained by reacting the above-mentioned hydrophilic diisocyanate with a dihydroxy compound to obtain an aqueous polyurethane resin with hydroxyl groups at the end, and then adding water for high-speed emulsification and dispersion to obtain a polyurethane emulsion.
  • the dihydroxy compound is a polyester diol, a polyether diol, a polycaprolactone diol, a hydroxyl-terminated alkyd resin, a hydroxyl-terminated silicone resin, a polyacrylic resin with a hydroxyl group, or a small molecule dihydric alcohol. At least one of the alcohols.
  • the hydrophilic diisocyanate of the present invention reacts with dihydroxy compounds (polyester, polyether, small molecule glycol, etc.) to prepare water-based polyurethane resin with hydroxyl at the end, and then adds water for high-speed dispersion and emulsification to obtain polyurethane emulsion.
  • dihydroxy compounds polyyester, polyether, small molecule glycol, etc.
  • SO 3 M is a sulfonate group
  • M is K ion, Na ion or ammonium ion
  • n is a positive integer such as 1, 2, 3.
  • a waterborne polyurethane curing agent is prepared by reacting the above-mentioned hydrophilic diisocyanate and polyhydroxy compound.
  • the polyhydroxy compound is at least one of trimethylolpropane, glycerol, trimethylolethane, 1,2,6-hexanetriol or pentaerythritol.
  • the hydrophilic diisocyanate of the present invention reacts with a polyhydroxy compound to prepare a polyisocyanate prepolymer.
  • a polyhydroxy compound By designing NCO/OH ⁇ 2, a waterborne polyurethane curing agent can be prepared.
  • the chemical reaction formula B is as follows:
  • SO 3 M is a sulfonate group, and M is K ion or Na ion or ammonium ion.
  • the hydrophilic diisocyanate makes the manufacture of water-based polyurethane easy, whether it is preparing water-based polyurethane emulsions with hydroxyl groups at the end or curing water-based polyurethanes with polyisocyanate groups at the end. It can directly replace part of the diisocyanate with the hydrophilic diisocyanate, and react with the hydrogen-containing compound, so that the polyurethane structure of the product is equipped with a hydrophilic sulfonate group, thereby changing the polyurethane prepolymer. It is hydrophilic, soluble in water, emulsified or dispersible in water, and prepares a variety of water-based polyurethane products.
  • a blocked water-based polyisocyanate curing agent is prepared by reacting the above-mentioned water-based polyurethane curing agent with a blocking agent.
  • the water-based polyurethane curing agent is a polyisocyanate prepolymer prepared by the reaction of the hydrophilic diisocyanate and the polyhydroxy compound of the present invention.
  • the blocking agent is a hydrogen-containing compound.
  • the blocking agent is methanol, ethanol, isopropanol, tert-butanol, propylene glycol monomethyl ether, methyl ethyl ketoxime, acetoxime, methyl isobutyl oxime, imidazole, 2-methylpyrazole, 3, 5-dimethylpyrazole, 3-methyl-5-ethylpyrazole, 3-ethyl-5-propylpyrazole, acetylacetone, ethyl acetoacetate, ⁇ -caprolactam, phenol or catechol At least one of them.
  • hydrophilic diisocyanate in the preparation of water-based polyurethane coatings, water-based polyurethane adhesives, water-based polyurethane binders, water-based leather finishing agents, water-based fabric finishing agents or water-based ink binders.
  • the waterborne polyurethane emulsion with hydroxyl at the end and the waterborne polyurethane curing agent with polyisocyanate at the end prepared by the present invention can be combined into a two-component waterborne polyurethane coating and waterborne polyurethane adhesive, with polyisocyanate at the end.
  • the acid radical water-based polyurethane curing agent and the hydroxyl-containing water-based resin can be combined into a water-based polyurethane binder, a water-based leather finishing agent, a water-based fabric finishing agent, or a water-based ink binder.
  • the sulfonate group in the hydrophilic diisocyanate structure of the present invention is a strong acid and strong base salt, which has very good hydrophilicity. Chemical reaction characteristics; and the use of the hydrophilic diisocyanate of the present invention to prepare waterborne polyurethane changes the existing process and greatly simplifies the operation.
  • the method for preparing the hydrophilic diisocyanate is simple and can be mass-produced.
  • the hydrophilic diisocyanate is directly used to prepare the aqueous polyurethane, which can reduce the cost and is beneficial to the popularization and application of the polyurethane oil to water.
  • the hydrophilic diisocyanate product of the present invention has stable performance. Due to the stable nature of the sulfonate, the hydrophilic diisocyanate produced by the diisocyanate modified by the sulfonate group still has a stable structure. The storage experiment proves that different types of products have a storage period of more than half a year and can be used as hydrophilic Raw materials for diisocyanate are sold.
  • the method of changing oil to water is simple.
  • the hydrophilic diisocyanate of the present invention is used to replace part of the diisocyanate to prepare waterborne polyurethane, it is only necessary to design the molar ratio of the reactants according to the product performance, and the technical method for producing solvent-based polyurethane that is already familiar to those skilled in the art can produce Water-soluble, emulsifiable or water-dispersible polyurethane products; what's more, hydrophilic diisocyanate can be directly added to the solvent-based polyisocyanate prepolymer (polyurethane curing agent) to change the polyisocyanate prepolymer It is hydrophilic, and then mixed with polyurethane resin emulsion, acrylic resin emulsion, alkyd resin emulsion, etc., as a cross-linking agent of these resin emulsions, to achieve the purpose of quickly changing polyurethane oil to water.
  • the stability of oil-to-water production is good.
  • the invention can prepare aliphatic, alicyclic or aromatic hydrophilic diisocyanates, so that the properties of different types of diisocyanates can be effectively utilized.
  • the prior art mainly uses aliphatic or alicyclic diisocyanates to prepare polyurethane emulsions, because aromatic diisocyanates have high activity and difficult preparation techniques.
  • dimethylol carboxylic acid is used to prepare waterborne polyurethane resin, HDI or IPDI is generally used.
  • dimethylol carboxylic acid is a trifunctional compound, it is easy to produce gel during the production process, and the quality is unstable, especially for industrialization. Large-scale production, a little carelessness will cause a burst.
  • the hydrophilic diisocyanate is bifunctional and directly reacts with the dihydroxy prepolymer, the production process is easy to control, the operation is simple, and the product quality is stable.
  • the hydrophilic diisocyanate of the present invention can be made into 100% solid content, no VOC emission, and further prepared into an organic solvent-free waterborne polyurethane product.
  • the hydrophilic diisocyanate of the present invention can be used to prepare water-based polyurethane emulsions, water-based polyurethane curing agents, and other water-based polyurethanes, and can be further prepared into two-component water-based polyurethane adhesives, water-based polyurethane coatings, and other water-based polyurethane products. Solvent-based polyurethane is modified into water-based polyurethane.
  • SO 3 M is a sulfonate group
  • M is K ion or Na ion or ammonium ion
  • n is 1-6.
  • a preparation method of hydrophilic diisocyanate includes the following steps:
  • hydrophilic chain extender is divided into 3-10 parts, and then added in several times. After each part of the hydrophilic chain extender is added, it must be reacted at 50-60°C until the liquid in the kettle is transparent.
  • the molar ratio of the reaction materials is diisocyanate: hydrophilic chain extender (3-4):1.
  • the above-mentioned hydrophilic chain extender is a small molecule diol containing at least one sulfonate group-containing small molecule diol or an amine sulfonate group.
  • the above-mentioned small molecule diols containing sulfonate groups are sodium 1,2-dihydroxy-3-propanesulfonate, sodium 1,4-dihydroxybutane-2-sulfonate or small molecule sulfonate diols At least one of them.
  • the above-mentioned small molecular diol containing amine sulfonate group is sodium N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate.
  • the aforementioned diisocyanate is at least one of MDI, HMDI, TDI, HDI, IPDI, or XDI.
  • the above-mentioned small molecule sulfonate diol is the product of the esterification reaction of dicarboxysulfonate, small molecule diol and small molecule dibasic acid, and the molecular weight is 380-600.
  • the above-mentioned dicarboxysulfonate is 5-sodium isophthalic acid sulfonate.
  • the above-mentioned small-molecular diols are diols with a molecular weight of less than 300; further, the above-mentioned small-molecular diols are 3-methyl-1,5-pentanediol, neopentyl glycol, ethylene glycol, and diethylene glycol.
  • Glycol cyclohexanediol, methyl propylene glycol, TCD tricyclic diol, 1,3-propanediol, 1,4-dimethylolcyclohexane, 1,4-butanediol, 1,3-butanedi Alcohol, 1,5-pentanediol, diethylpentanediol, 1,2-propanediol, diethylene glycol, tetrahydrofurandiol, 1,6-hexanediol, trimethylpentanediol, butyl ethyl At least one of propylene glycol, 2,2-bis(4-hydroxyphenyl)propane, dipropylene glycol, tripropylene glycol, or ethyl hexanediol.
  • the small molecular dibasic acid is a dibasic acid with a molecular weight of less than 300; further, the small molecular dibasic acid is adipic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic anhydride, and terephthalic acid. At least one of dimethyl dicarboxylate, succinic acid or glutaric acid.
  • the addition amount of the above cosolvent is 0-40% of the weight of the diisocyanate, and the cosolvent is acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, tetrahydrofuran , At least one of dioxane or dimethylformamide.
  • the average molecular weight and NCO% of the hydrophilic diisocyanate of the present invention can be obtained through calculation or testing.
  • a polyurethane emulsion is prepared by reacting a hydrophilic diisocyanate with a dihydroxy compound to prepare a water-based polyurethane resin with hydroxyl at the end, and then adding water to emulsify and disperse at a high speed to obtain a polyurethane emulsion.
  • the specific preparation method of the above polyurethane emulsion is as follows: Add the vacuum dehydrated dihydroxy compound and co-solvent into the reactor, stir evenly, heat up to 60°C, add hydrophilic diisocyanate and catalyst, and heat up to 70°C-100°C. After chain reaction for 6-15 hours, a polyurethane prepolymer with a hydroxyl main chain structure containing sulfonate groups at the end is obtained, and water is added for high-speed emulsification and dispersion, and the auxiliary solvent is removed to obtain a hydroxyl-terminated waterborne polyurethane emulsion.
  • the dihydroxy compound is polyester diol, polyether diol, polycaprolactone diol, hydroxyl-terminated alkyd resin, hydroxyl-terminated silicone resin, polyacrylic resin with hydroxyl or small molecule glycol At least one of.
  • the waterborne polyurethane curing agent of the present invention is prepared by reacting hydrophilic diisocyanates with polyhydroxy compounds to prepare waterborne polyurethane prepolymers (waterborne polyurethane curing agents) with polyisocyanate groups on the ends.
  • the specific preparation method is as follows:
  • the above-mentioned polyhydroxy compound is at least one of trimethylolpropane, glycerol, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, polyester polyol, or polyether polyol.
  • a blocked water-based polyisocyanate curing agent is prepared by reacting a polyisocyanate prepolymer with a sulfonate group in the main chain structure and a blocking agent.
  • the above blocking agents are methanol, ethanol, isopropanol, tert-butanol, propylene glycol monomethyl ether, methyl ethyl ketoxime, acetoxime, methyl isobutyl oxime, imidazole, 2-methylpyrazole, 3,5-dimethyl At least one of pyrazole, 3-methyl-5-ethylpyrazole, 3-ethyl-5-propylpyrazole, acetylacetone, ethyl acetoacetate, ⁇ -caprolactam, phenol or catechol .
  • hydrophilic diisocyanate in the preparation of water-based polyurethane coatings, water-based polyurethane adhesives, water-based polyurethane binders, water-based leather finishing agents, water-based fabric finishing agents or water-based ink binders.
  • the water-based polyurethane emulsion with hydroxyl at the end and the water-based polyurethane curing agent with polyisocyanate at the end prepared by the present invention can be combined into a two-component water-based polyurethane coating and water-based polyurethane adhesive, and the water-based polyisocyanate at the end
  • the polyurethane curing agent and the hydroxyl-containing water-based resin can be combined into a water-based polyurethane binder, a water-based leather finishing agent, a water-based fabric finishing agent or a water-based ink binder.
  • NCO content is carried out in accordance with the Ministry of Chemical Industry standard "Determination of Isocyanate Group Content in HG/T2409-92 Polyurethane Prepolymer".
  • a preparation method of hydrophilic diisocyanate includes the following steps:
  • hydrophilic chain extender small molecule sulfonate diol
  • the temperature in the kettle is controlled at 160-190°C.
  • the water output reaches the theoretical value, the water will continue to be discharged for 1 hour; turn on the vacuum pump to gradually increase the vacuum
  • the temperature is above 0.097MPa, the residual alcohol is removed, the temperature is lowered to 70°C, and the material is discharged to obtain a light yellow transparent small molecule sulfonate diol. Sampling, the solid content of the product was 99.8%, and the number average molecular weight was 420.
  • hydrophilic diisocyanate hydrophilic MDI
  • the hydrophilic MDI has a viscosity of 5600mPa.s/25°C, an NCO% of 16.0%, and a storage period of 6 months.
  • hydrophilic diisocyanate hydrophilic diisocyanate
  • the viscosity of the hydrophilic TDI is 3600mPa.s/25°C
  • the NCO% is 17.8%
  • the storage period is 6 months.
  • hydrophilic diisocyanate hydrophilic HDI-TDI mixture
  • the viscosity of the hydrophilic HDI-TDI mixture is 4200mPa.s/25°C
  • the NCO% is 23.0%
  • the storage period is 6 months.
  • hydrophilic diisocyanate hydrophilic HDI
  • the viscosity of the hydrophilic HDI is 1500mPa.s/25°C
  • the NCO% is 21.1%
  • the storage period is 6 months.
  • hydrophilic diisocyanate hydrophilic diisocyanate (hydrophilic IPDI containing sulfamate group) includes the following steps:
  • the hydrophilic IPDI has a viscosity of 2100mPa.s/25°C, an NCO% of 16.3%, and a storage period of 6 months.
  • the preparation of an IPDI type waterborne polyurethane curing agent includes the following steps:
  • the appearance of the water-based curing agent is a light yellow transparent viscous liquid, the solid content is 70%, and the viscosity is 2200mpa.s (25°C) and the NCO content is 9.4%.
  • the preparation of an MDI type water-based closed polyurethane curing agent includes the following steps:
  • the appearance of the curing agent was detected to be a light yellow transparent viscous liquid with a solid content of 75% and a viscosity of 3500 mPa ⁇ s (25° C.).
  • the preparation of a TDI type waterborne polyurethane curing agent includes the following steps:
  • a preparation method of a solvent-based TDI curing agent includes the following steps:
  • the curing agent has a light yellow transparent viscous liquid with a solid content of 75%, a viscosity of 2800 mPa ⁇ s (25° C.), and an NCO% of 13.0%.
  • the method for preparing the water-based polyurethane curing agent from the hydrophilic diisocyanate of the present invention is basically the same as the method for preparing the solvent-based polyurethane curing agent.
  • the preparation of an aqueous polyurethane resin emulsion includes the following steps:
  • a preparation method of waterborne polyurethane resin emulsion includes the following steps:
  • a preparation method of waterborne polyurethane resin emulsion includes the following steps:
  • a preparation method of polyurethane emulsion includes the following steps:
  • acetone In order to reduce the viscosity of the system, 15mL of acetone can be added to dilute. After the reaction is complete, the temperature is lowered to 40° C., 25 mL of distilled water is added, and the emulsification is carried out for 30 min under strong shearing force. The acetone is evaporated under reduced pressure to obtain a polyurethane emulsion with a solid content of about 50% and a translucent appearance.
  • a preparation method of IPDI-HDI hybrid waterborne polyurethane curing agent includes the following steps:
  • the preparation of a two-component waterborne polyurethane coating includes the following steps:
  • Inspection method gloss (60°) according to GB9754-2007, hardness according to GB1730-79, impact strength according to GB/T 2571-1995, adhesion according to GB1720-89, flexibility according to GB1731-79 standard, water resistance according to GB/T1733 -1993.
  • the operation method is very simple, basically with the production of solvents.
  • the method of polyurethane products is similar, and the water solubility of the products is very good. If the water-based resin with hydroxyl at the end is emulsified, only a little stirring (no high-speed dispersion is necessary) can be made into a milky white and blue-blue emulsion. It is also very simple to mix the water-based curing agent with isocyanate and the water-based resin emulsion. You can mix the two directly, or you can add water to disperse the curing agent before mixing.
  • the above application examples can be further combined into a water-based two-component polyurethane coating, a water-based two-component polyurethane adhesive, a water-based polyurethane leather finishing agent, a water-based polyurethane fabric sizing agent, etc., and the applications are very wide.

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Abstract

本发明属于聚氨酯领域，本发明提供一种亲水性二异氰酸酯，其包含至少一种含有如下通式（I）的结构单元：式中：SO3M为磺酸盐基团，M为K离子或Na离子或铵离子；n为1-6；所述亲水性二异氰酸酯是由至少一种亲水扩链剂与二异氰酸酯反应而生成。本发明的亲水性二异氰酸酯结构中的磺酸盐基是强酸强碱盐，具有很好的亲水性，两端头的异氰酸酯基保留了原二异氰酸酯的性能，因此具有二异氰酸酯的化学反应特性；且使用本发明亲水性二异氰酸酯制备水性聚氨酯改变了现有的工艺方法，极大地简化了操作。

Description

一种亲水性二异氰酸酯及其制备方法和应用 技术领域
本发明属于聚氨酯领域，具体涉及一种亲水性二异氰酸酯及其制备方法和应用。
背景技术
环保法规对化工产品中挥发性有机化合物(VOCs)排放量的限制，促进了水性聚氨酯产品的开发及应用，但仍存在一些瓶颈性技术问题尚待解决，比如：聚氨酯水性化所需的亲水性原料品种太少，胺基磺酸盐类亲水性原料价格昂贵，二羟甲基羧酸类亲水性原料需用特殊溶剂溶解才能与异氰酸酯反应，以及加工工艺复杂等问题，制约了相关企业聚氨酯产品由溶剂型向水性化(油改水)的转型。
聚氨酯的水性化就是在疏水的聚氨酯结构中引进亲水基团，怎样引进价格低廉、无毒无味、亲水效果好的亲水基团，采取什么简便易行的工艺方法，达到既不改变原溶剂型产品的主要性能，又无VOC排放的水性聚氨酯产品是本领域持续研究的重点。
目前聚氨酯油改水效果比较好的亲水剂是磺酸盐基，因为磺酸盐属于强酸强碱盐，具有较强的亲水性，合成聚氨酯分散体时用量较少，分散体具有更稳定的“双电层”结构；由于亲水基团用量少，因而对聚氨酯性能影响小，以至于聚氨酯分散体的耐酸碱性、耐电解质性、机械稳定性、与助剂的相溶性，以及胶膜性能等基本能保持原溶剂型产品的性能。但是，现有技术对磺酸盐基亲水剂的研究还不够成熟，主要原因是烷基磺酸盐只具外乳化功能，单羟基磺酸盐不能对异氰酸酯进行扩链，改性效果比较好的是小分子双羟基胺基磺酸盐和双羟基磺酸盐，但这两者不仅价格昂贵，使油改水成本大幅上升，而且脂溶性差，需要加入较多的高沸点极性溶剂，导致产品有机溶剂残留量高，难以推广。现有技术CN107082860A公开了一种分子量为350-1000含磺酸基团的小分子二元醇，其与二异氰酸酯反应制备水性聚氨酯固化剂，介绍了以二羧基磺酸盐和二羟基磺酸盐制备含磺酸基团的小分子二元醇的制备方法，但在实际应用中转化条件比较苛刻，一般企业难以掌握此技术。由于二羧基磺酸盐原料来源方便，价格便宜，无毒无味，若能将其作为聚氨酯油改水的推广性原料，必将大大加快聚氨酯水性化步伐。
因此，本发明研发了一种含有磺酸盐基的亲水性二异氰酸酯。
发明内容
为了弥补现有技术的不足，本发明目的是提供一种含有磺酸盐基的亲水性二异氰酸酯及其制备方法和应用，用该含有磺酸盐基的亲水性二异氰酸酯作为制备水性聚氨酯的亲水性原料，能简化油改水制备工艺，降低成本，并能保持原溶剂型产品的主要技术性能。
上述应用是指含磺酸盐基亲水性二异氰酸酯在制备水性聚氨酯乳液、水性聚氨酯固化剂、水性聚氨酯连接料、水性聚氨酯涂饰剂、水性聚氨酯弹性体等方面的应用。
为了实现上述目的，本发明采用以下技术方案：
一种亲水性二异氰酸酯，其包含至少一种含有如下通式的结构单元：
Figure PCTCN2021081648-appb-000001
式中：SO 3M为磺酸盐基团，M为K离子或Na离子或铵离子，n为1-6。
一种亲水性二异氰酸酯的制备方法，包括以下步骤：
在反应釜内，加入二异氰酸酯和助溶剂，开启搅拌器，升温至30℃-80℃，分数次加入亲水扩链剂，每次加入亲水扩链剂后都要在50℃-60℃反应0.5-3小时，直至最后一次加入亲水扩链剂，在50℃-60℃反应0.5-3小时后，再升温至60℃-80℃反应6-20小时，降温出料，得亲水性二异氰酸酯。
优选地，将亲水扩链剂分成3-10份，再分数次加入，每加入一份亲水扩链剂后都要在50～60℃反应至釜内液体透明。
优选地，所述分数次为3-10次。
优选地，所述二异氰酸酯和亲水扩链剂的摩尔比为(2-6)：1。
更优选地，所述二异氰酸酯和亲水扩链剂的摩尔比为(3-4)：1。
根据反应物料摩尔比得知：本发明亲水性二异氰酸酯中除了主链结构含有磺酸盐基二异氰酸酯外，还有一定比例二异氰酸酯单体，因为制备水性聚氨酯时只要有一定比例亲水基团存在，则制备的预聚物就可溶于水或用水可乳化或用水可分散，所以本发明亲水性二异氰酸酯设计了一定比例的亲水基团。
优选地，所述亲水扩链剂为至少包含一种磺酸盐基的小分子二元醇或胺基磺酸盐基的小分子二元醇。
优选地，所述含磺酸盐基的小分子二元醇为1,2-二羟基-3-丙磺酸钠、1,4-二羟基丁烷-2-磺酸钠或小分子磺酸盐二元醇中的至少一种。
优选地，所述胺基磺酸盐基的小分子二元醇为N,N-二(2-羟乙基)-2-氨基乙磺酸钠。
优选地，所述二异氰酸酯为MDI、HMDI、TDI、HDI、IPDI或XDI中的至少一种。
优选地，所述小分子磺酸盐二元醇为二羧基磺酸盐与小分子二元醇、小分子二元酸经酯化反应的生成物，分子量为350～3000。
更优选地，所述小分子磺酸盐二元醇的分子量为380～600。
优选地，所述小分子二元醇为分子量小于300的二元醇。
更优选地，所述小分子二元醇为3-甲基-1,5-戊二醇、新戊二醇、乙二醇、一缩二乙二醇、环己二醇、甲基丙二醇、TCD三环二醇、1,3-丙二醇、1,4-二羟甲基环己烷、1,4-丁二醇、1,3-丁二醇、1,5-戊二醇、二乙基戊二醇、1,2-丙二醇、二甘醇、四氢呋喃二醇、1,6-己二醇、三甲基戊二醇、丁基乙基丙二醇、2,2-二(4-羟基苯基)丙烷、一缩二丙二醇、三丙二醇或乙基己二醇中的至少一种。
优选地，所述小分子二元酸为分子量小于300的二元酸。
更优选地，所述小分子二元酸为己二酸、癸二酸、对苯二甲酸、间苯二甲酸、邻苯二甲酸酐、对苯二甲酸二甲酯、丁二酸或戊二酸中的至少一种。
优选地，所述二羧基磺酸盐为二羧基磺酸钠盐、二羧基磺酸钾盐或二羧基磺酸铵中的至少一种。
更优选地，所述二羧基磺酸盐为间苯二甲酸-5-磺酸钠。
优选地，所述助溶剂的加入量为二异氰酸酯重量的0-40％，可以得到100％固含量的亲水性二异氰酸酯。
更优选地，所述助溶剂为丙酮、丁酮、醋酸乙酯、醋酸丁酯、环己酮、丙二醇单甲醚醋酸酯、N-甲基吡咯烷酮、四氢呋喃、二氧杂环己烷或二甲基甲酰胺中的至少一种。
一种聚氨酯乳液，是由上述亲水性二异氰酸酯与二羟基化合物反应，得到端头带羟基的水性聚氨酯树脂，再加水高速乳化分散，即得聚氨酯乳液。
优选地，所述二羟基化合物为聚酯二元醇、聚醚二元醇、聚己内酯二醇、端羟基醇酸树脂、端羟基有机硅树脂、带羟基的聚丙烯酸树脂或小分子二元醇中的至少一种。
本发明亲水性二异氰酸酯与二羟基化合物(聚酯、聚醚、小分子二元醇等)反应制备端头带羟基的水性聚氨酯树脂，再加水高速分散乳化，得到聚氨酯乳液，通过设计OH/NCO>1，可以制得不同分子量的产品，其化学反应式A如下：
Figure PCTCN2021081648-appb-000002
式中：SO 3M为磺酸盐基团，M为K离子或Na离子或铵离子，n为1、2、3等正整数。
一种水性聚氨酯固化剂，是由上述亲水性二异氰酸酯与多羟基化合物反应制得。
优选地，所述多羟基化合物为三羟甲基丙烷、丙三醇、三羟甲基乙烷、1,2,6-己三醇或季戊四醇中的至少一种。
本发明亲水性二异氰酸酯与多羟基化合物反应制备多异氰酸酯预聚物，通过设计NCO/OH≧2，可以制得水性聚氨酯固化剂，其化学反应式B如下：
Figure PCTCN2021081648-appb-000003
式中：SO 3M为磺酸盐基团，M为K离子或Na离子或铵离子。
从上述化学反应式A和B可以看出：亲水性二异氰酸酯使得水性聚氨酯的制造变得容易，无论是制备端头带羟基的水性聚氨酯乳液，还是端头带多异氰酸根的水性聚氨酯固化剂，都可以直接将亲水性二异氰酸酯代替部分二异氰酸酯，与含氢化合物反应，使生成物的聚氨基甲酸酯结构带上亲水性磺酸盐基团，从而使聚氨酯预聚体变得亲水，可溶于水或水可乳化或水可分散，制备出多种水性聚氨酯产品。
一种封闭型水性多异氰酸酯固化剂，是由上述水性聚氨酯固化剂与封闭剂反应制得。
优选地，所述水性聚氨酯固化剂是本发明亲水性二异氰酸酯与多羟基化合物反应制备的多异氰酸酯预聚物。
优选地，所述封闭剂为含氢化合物。
更优选地，所述封闭剂为甲醇、乙醇、异丙醇、叔丁醇、丙二醇单甲醚、甲乙酮肟、丙酮肟、甲基异丁基肟、咪唑、2-甲基吡唑、3,5-二甲基吡唑、3-甲基-5-乙基吡唑、3-乙基-5-丙基吡唑、乙酰丙酮、乙酰乙酸乙酯、ε-己内酰胺、苯酚或邻苯二酚中的至少一种。
一种亲水性二异氰酸酯在制备水性聚氨酯涂料、水性聚氨酯黏合剂、水性聚氨酯连接料、水性皮革涂饰剂、水性织物整理剂或水性油墨连接料中的应用。
优选地，以本发明制备的端头带羟基的水性聚氨酯乳液与端头带多异氰酸根的水性聚氨酯固化剂可组合成双组份水性聚氨酯涂料和水性聚氨酯黏合剂，端头带多异氰酸根的水性聚氨酯固化剂与含羟基的水性树脂可组合成水性聚氨酯连接料、水性皮革涂饰剂、水性织物整理剂或水性油墨连接料等。
有益效果
1.本发明的亲水性二异氰酸酯结构中的磺酸盐基是强酸强碱盐，具有很好的亲水性，两端头的异氰酸酯基保留了原二异氰酸酯的性能，因此具有二异氰酸酯的化学反应特性；且使用本发明亲水性二异氰酸酯制备水性聚氨酯改变了现有的工艺方法，极大地简化了操作。本发明制备亲水性二异氰酸酯的方法简单，可批量化生产，直接使用亲水性二异氰酸酯制备水性聚氨酯，可降低成本，并有利于聚氨酯油改水的推广应用。
2.本发明的亲水性二异氰酸酯产品性能稳定。由于磺酸盐的性质稳定，二异氰酸酯经磺酸盐基改性后生成的亲水性二异氰酸酯仍然具有稳定的结构，经贮存实验证明：不同型号产品有半年以上贮存期，可作为亲水性二异氰酸酯原料出售。
3.品种多。根据制备原材料的组成及配比不同，可以制成一系列不同型号的亲水性二异氰酸酯，每种产品具有特定的NCO％、粘度和贮存期，因此用户可以根据具体水性聚氨酯产品的性能选择合适型号的品种。
4、油改水方法简便。以本发明亲水性二异氰酸酯代替部分二异氰酸酯制备水性聚氨酯时，只需按照产品性能设计反应物的摩尔比，用本领域技术人员已经熟悉的生产溶剂型聚氨酯的工艺方法，就能生产出在水中可溶、可乳化或者可水分散的聚氨酯产品；更有甚者，还可以将亲水性二异氰酸酯直接加入溶剂型多异氰酸酯预聚物(聚氨酯固化剂)中，使多异氰酸酯预聚物变得亲水，再与聚氨酯树脂乳液、丙烯酸树脂乳液、醇酸树脂乳液等混合，作为这些树脂乳液的交联剂，达到快速实现聚氨酯油改水目的。
5、油改水生产稳定性好。本发明可以制备出脂肪族、脂环族或芳香族的亲水性二异氰酸酯，使不同类型二异氰酸酯的性能都能得到有效利用。现有技术制备聚氨酯乳液主要采用脂肪族或脂环族二异氰酸酯，因为芳香族二异氰酸酯的活性高，制备技术难度大。例如：用二羟甲基羧酸制备水性聚氨酯树脂时，一般采用HDI或IPDI，因为二羟甲基羧酸是三官能度化合物，生产过程中极易产生凝胶，质量不稳定，特别是工业化大生产，稍有不慎就会产生爆聚。用本发明制备水性聚氨酯树脂时，亲水性二异氰酸酯是两官能度，直接与二羟基预聚物反应，生产过程容易控制，操作简单，产品质量稳定。
6、环保性好。本发明亲水性二异氰酸酯可以做成100％固含量，无VOC排放，进一步制备成无有机溶剂的水性聚氨酯产品。
7、应用范围广。本发明亲水性二异氰酸酯可用于制备水性聚氨酯乳液、水性聚氨酯固化剂、以及其他水性聚氨酯，并可进一步制备成双组份水性聚氨酯胶粘剂、水性聚氨酯涂料、以及其他水性聚氨酯产品，非常方便地将溶剂型聚氨酯改性成水性聚氨酯。
具体实施方式
一种亲水性二异氰酸酯，该亲水性二异氰酸酯包含至少一种含有如下通式的结构单元：
Figure PCTCN2021081648-appb-000004
式中：SO 3M为磺酸盐基团，M为K离子或Na离子或铵离子，n为1-6。
一种亲水性二异氰酸酯的制备方法，包括以下步骤：
在反应釜内，加入二异氰酸酯和助溶剂，开启搅拌器，升温至30℃-80℃，分数次加入亲水扩链剂，每次加入亲水扩链剂后都要在50℃-60℃反应0.5-3小时，直至最后一次加入亲水扩链剂，在50℃-60℃反应0.5-3小时后，再升温至60℃-80℃反应6-20小时，降温出料，得亲水性二异氰酸酯。
上述亲水扩链剂是分成3-10份，再分数次加入的，每加入一份亲水扩链剂后都要在50-60℃反应至釜内液体透明。
反应物料的摩尔比为二异氰酸酯：亲水扩链剂为(3-4)：1。
上述亲水扩链剂是至少包含一个含磺酸盐基的小分子二元醇或胺基磺酸盐基的小分子二元醇。
上述含磺酸盐基的小分子二元醇为1,2-二羟基-3-丙磺酸钠、1,4-二羟基丁烷-2-磺酸钠或小分子磺酸盐二元醇中的至少一种。
上述含胺基磺酸盐基的小分子二元醇为N,N-二(2-羟乙基)-2-氨基乙磺酸钠。
上述二异氰酸酯为MDI、HMDI、TDI、HDI、IPDI或XDI中的至少一种。
上述小分子磺酸盐二元醇为二羧基磺酸盐与小分子二元醇、小分子二元酸经酯化反应的生成物，分子量为380～600。
上述二羧基磺酸盐为间苯二甲酸-5-磺酸钠。
上述小分子二元醇为分子量小于300的二元醇；进一步，上述小分子二元醇为3-甲基-1,5-戊二醇、新戊二醇、乙二醇、一缩二乙二醇、环己二醇、甲基丙二醇、TCD三环二醇、1,3-丙二醇、1,4-二羟甲基环己烷、1,4-丁二醇、1,3-丁二醇、1,5-戊二醇、二乙基戊二醇、1,2-丙二醇、二甘醇、四氢呋喃二醇、1,6-己二醇、三甲基戊二醇、丁基乙基丙二醇、2,2-二(4-羟基苯基)丙烷、一缩二丙二醇、三丙二醇或乙基己二醇中的至少一种。
上述小分子二元酸为分子量小于300的二元酸；进一步，上述小分子二元酸为己二酸、癸二酸、对苯二甲酸、间苯二甲酸、邻苯二甲酸酐、对苯二甲酸二甲酯、丁二酸或戊二酸中的至少一种。
上述助溶剂的加入量为二异氰酸酯重量的0-40％，助溶剂为丙酮、丁酮、醋酸乙酯、醋酸丁酯、环己酮、丙二醇单甲醚醋酸酯、N-甲基吡咯烷酮、四氢呋喃、二氧杂环己烷或二甲基甲酰胺中的至少一种。
本发明亲水性二异氰酸酯的平均分子量大小、NCO％都可以通过计算或测试得出。
一种聚氨酯乳液，将亲水性二异氰酸酯与二羟基化合物反应，制得端头带羟基的水性聚氨酯树脂，再加水高速乳化分散，即得聚氨酯乳液。
上述聚氨酯乳液具体制备方法如下：在反应釜内，加入经真空脱水的二羟基化合物及助溶剂，搅拌均匀，升温至60℃，加入亲水性二异氰酸酯和催化剂，升温至70℃-100℃扩链反应6-15小时，得端头带羟基主链结构含有磺酸盐基的聚氨酯预聚物，再加水高速乳化分散，脱除助溶剂，得端羟基水性聚氨酯乳液。
所述二羟基化合物为聚酯二元醇、聚醚二元醇、聚己内酯二醇、端羟基醇酸树脂、端羟基有机硅树脂、带羟基的聚丙烯酸树脂或小分子二元醇中的至少一种。
本发明的一种水性聚氨酯固化剂，是由亲水性二异氰酸酯与多羟基化合物反应，制得端头带多异氰酸根的水性聚氨酯预聚物(水性聚氨酯固化剂)，具体制备方法如下：
在反应釜内，加入亲水性二异氰酸酯及助溶剂，搅拌均匀，加入经真空脱水的多羟基化合物，在室温下搅拌0.5-2小时，升温至50-100℃反应2-10小时，得主链结构含有磺酸盐基的多异氰酸酯预聚物，脱除助溶剂，得水性聚氨酯固化剂。
上述多羟基化合物为三羟甲基丙烷、丙三醇、三羟甲基乙烷、1,2,6-己三醇、季戊四醇、聚酯多元醇或聚醚多元醇中的至少一种。
一种封闭型水性多异氰酸酯固化剂，是由主链结构含有磺酸盐基的多异氰酸酯预聚物与封闭剂反应制得。
上述封闭剂为甲醇、乙醇、异丙醇、叔丁醇、丙二醇单甲醚、甲乙酮肟、丙酮肟、甲基异丁基肟、咪唑、2-甲基吡唑、3,5-二甲基吡唑、3-甲基-5-乙基吡唑、3-乙基-5-丙基吡唑、乙酰丙酮、乙酰乙酸乙酯、ε-己内酰胺、苯酚或邻苯二酚中的至少一种。
一种亲水性二异氰酸酯在制备水性聚氨酯涂料、水性聚氨酯黏合剂、水性聚氨酯连接料、水性皮革涂饰剂、水性织物整理剂或水性油墨连接料中的应用。
以本发明制备的端头带羟基的水性聚氨酯乳液与端头带多异氰酸根的水性聚氨酯固化剂可组合成双组份水性聚氨酯涂料和水性聚氨酯黏合剂，端头带多异氰酸根的水性聚氨酯固化剂与含羟基的水性树脂可组合成水性聚氨酯连接料、水性皮革涂饰剂、水性织物整理剂或水性油墨连接料。
以下通过具体的实施例对本发明的内容作进一步详细的说明。
以下实施例中：
1、检测粘度按国标《GB/T2794-1995胶粘剂粘度的测定》进行。
2、检测NCO含量按化工部标准《HG/T2409-92聚氨酯预聚体中异氰酸酯基含量的测定》进行。
3、检测分子量采用GPC凝胶色谱法。
4、检测羟值按化工部标准《HG/T2709-95树脂值的测定》进行。
实施例1
一种亲水性二异氰酸酯的制备方法，包括以下步骤：
a)制备亲水扩链剂(小分子磺酸盐二元醇)
在装有分馏装置的反应瓶内，加入150g二甘醇、780g1,4-丁二醇、260g去离子水、2.4g亚磷酸三苯酯，开启搅拌器，升温至95℃，加入400g间苯二甲酸-5-磺酸钠，在90-95℃溶解2小时；加入360g己二酸，在90-95℃搅拌至全部溶解后，通入氮气，开始酯化反应，升高釜内温度，控制冷凝管顶部出水口温度90-99℃，随着酯化反应的进行，釜内温度控制在160-190℃，当出水量达到理论值，再继续出水1小时；开启真空泵，逐渐提高真空度至 0.097MPa以上，脱除残醇，降温至70℃，出料，得浅黄色透明的小分子磺酸盐二元醇。取样，检测产物的固含量为99.8％、数均分子量为420。
b)制备亲水性二异氰酸酯(亲水性IPDI)
在三口反应瓶内，加入300g(2.699当量)IPDI，开启搅拌器，升温至55℃，将步骤a)制得的含磺酸盐基的小分子二元醇420g(0.675当量)分三次加入，每次加入后反应0.5小时，直至全部加完，反应1小时后，升温至60-70℃，反应8小时后每隔1小时取样测NCO含量，当NCO下降趋于稳定时，降温出料，得固含量为100％的含磺酸盐基的IPDI。经检测亲水性IPDI的粘度为4200mPa·s(25℃)，NCO％为19.1％，贮存期为6个月。
实施例2
制备亲水性二异氰酸酯(亲水性MDI)，包括以下步骤：
在反应瓶内，加入200g(1.6当量)MDI和67g丙酮，开启搅拌器，升温至30℃，取实施例1步骤a)制得的亲水扩链剂67.2g(0.32当量)分四次加入，每次加入后反应0.5小时，直至全部加完，反应1小时后，升温至50℃反应2小时，再升至60℃，反应5小时后每隔0.5小时取样测NCO含量，当NCO下降趋于稳定时，降温出料，得固含量为80％的含磺酸盐基的MDI。
经检测亲水性MDI的粘度5600mPa.s/25℃，NCO％为16.0％，贮存期为6个月。
实施例3
制备亲水性二异氰酸酯(亲水性TDI)，包括以下步骤：
在反应瓶内，加入200g(2.299当量)TDI，开启搅拌器，升温至30℃，取实施例1步骤a)制得的亲水扩链剂160g(0.766当量)分六次加入，每次加入后反应0.5小时，直至全部加完，反应1小时后，升温至50℃反应2小时，升至60℃反应5小时后每隔0.5小时取样测NCO含量，当NCO下降趋于稳定时，降温出料，得固含量为100％的含磺酸盐基的TDI。
经检测亲水性TDI的粘度为3600mPa.s/25℃，NCO％为17.8％，贮存期为6个月。
实施例4
制备亲水性二异氰酸酯(亲水性HDI-TDI混合物)，包括以下步骤：
在反应瓶内，加入200g(2.38当量)HDI，开启搅拌器，升温至50℃，取实施例1步骤a)制得的亲水扩链剂130g(0.618当量)分四次加入，每次加完后反应1小时，直至全部加完反应1小时；再加入8gTDI(0.092当量)，反应1小时；升温至50～60℃反应2小时，65～75℃反应10小时后每隔1小时取样测NCO含量，当NCO下降趋于稳定时，降温出料，得固含量为100％的含磺酸盐基的HDI-TDI混合液。
经检测亲水性HDI-TDI混合物的粘度4200mPa.s/25℃，NCO％为23.0％，贮存期为6个月。
实施例5
制备亲水性二异氰酸酯(亲水性HDI)，包括以下步骤：
在反应瓶内，加入200g(2.38当量)HDI和75g丙酮，开启搅拌器，升温至50℃，取实施例1步骤a)制得的亲水扩链剂100g(0.476当量)分四次加入，每次加完后反应1小时，直至全部加完反应1小时；升温至50～60℃反应2小时，60～70℃反应10小时后每隔1小时取样测NCO含量，当NCO下降趋于稳定时，降温出料，得固含量为80％的含磺酸盐基的HDI。
经检测亲水性HDI的粘度1500mPa.s/25℃，NCO％为21.1％，贮存期为6个月。
实施例6
制备亲水性二异氰酸酯(含氨基磺酸盐基亲水性IPDI)，包括以下步骤：
在三口反应瓶内，加入200g(1.799当量)IPDI和85g丙酮，开启搅拌器，升温至50℃，将53g(0.4498当量)N，N-二(2-羟乙基)-2-氨基乙磺酸钠(BES-Na)分成五份，分五次加入，每加进一份BES-Na都要使其溶解完全并反应1小时后，再加入下一份BES-Na，直至加完全部BES-Na，溶解反应1小时；再升温至50℃-60℃反应2小时，60℃-70℃反应8小时后每隔1小时取样测NCO含量，当NCO下降趋于稳定时，降温出料，得固含量为75％的含氨基磺酸盐基的IPDI。
经检测亲水性IPDI的粘度2100mPa.s/25℃，NCO％为16.3％，贮存期为6个月。
应用实施例1
一种IPDI型水性聚氨酯固化剂的制备，包括以下步骤：
在三口烧瓶中，加入100g(0.457当量)实施例1制得的亲水性IPDI和27g丙二醇单甲醚醋酸酯，开启搅拌器，滴加10克(0.228当量)三羟甲基丙烷与20克丙酮组成的混合液，2小时滴完，在80～90℃保温反应8小时，再升至90℃～100℃保温反应4小时；降温至60℃，再加入200g(0.571当量)IPDI三聚体(固含量为70％，NCO％为12％)，在50℃-55℃反应3小时后取样测NCO下降趋于稳定时，出料，得357gIPDI型水性聚氨酯固化剂。
经检测该水性固化剂的外观为浅黄色透明粘稠液体，固含量为70％，粘度为2200mpa.s(25℃)NCO含量为9.4％。
应用实施例2
一种MDI型水性封闭型聚氨酯固化剂的制备，包括以下步骤：
a)在三口烧瓶中，加入200g(0.7619当量)实施例2制得的亲水性MDI、80g(0.64当量)MDI和20g丙二醇单甲醚醋酸酯，搅拌均匀，滴加31克(0.7当量)三羟甲基丙烷与30克丙酮组成的混合液，2小时滴完，在70℃～80℃保温反应3小时，再升至80℃～90℃保温反应2小时后测反应物的NCO含量，当NCO下降趋于稳定时停止反应；
b)降温至50℃，分三次加入70g甲乙酮肟，控制加料温度在50～55℃，2小时加完，在60℃～70℃反应1小时，75℃～80℃反应3小时，降温出料，得到封闭型(MDI型)水性多异氰酸酯固化剂。
经检测该固化剂外观为浅黄色透明粘稠液体，固含量为75％，粘度为3500mPa·s(25℃)。
应用实施例3
一种TDI型水性聚氨酯固化剂的制备，包括以下步骤：
a)在三口烧瓶中，加入200g(0.847当量)实施例3制得的亲水性TDI、100g(1.149当量)TDI和64g丙酮，搅拌均匀，滴加42g(0.996当量)三羟甲基丙烷与50g丙酮组成的混合液，2小时滴完，在60℃-85℃保温反应8小时后测反应物的NCO含量，当NCO下降趋于稳定时停止反应；
b)将物料转入残留单体分离装置中，脱除残留TDI单体，降至70℃，加入114g丙酮，搅匀出料，得水性TDI固化剂。经检测该固化剂外观为浅黄色透明粘稠液体，固含量为75％，粘度为2500mPa·s(25℃)，NCO％为9.1％。
对比实施例1(溶剂型TDI固化剂的经典方法)
一种溶剂型TDI固化剂的制备方法，包括以下步骤：
a)在三口烧瓶中，加入200g(2.298当量)TDI和33g醋酸乙酯，搅拌均匀，滴加50g(1.149当量)三羟甲基丙烷与50g醋酸乙酯组成的混合液，2小时滴完，在60℃-85℃保温反应8小时后测反应物的NCO含量，当NCO下降趋于稳定时停止反应；
b)将物料转入残留单体分离装置，脱除残留TDI单体，降至70℃，加入83g醋酸乙酯，搅匀出料，得溶剂型TDI固化剂。经检测该固化剂外观为浅黄色透明粘稠液体，固含量为75％，粘度为2800mPa·s(25℃)，NCO％为13.0％。
从上述应用实施例3和对比实施例1可以看出，本发明亲水性二异氰酸酯制备水性聚氨酯固化剂的方法与制备溶剂型聚氨酯固化剂的方法基本相同。
应用实施例4
1、一种水性聚氨酯树脂乳液的制备，包括以下步骤：
a)在反应瓶内，加入200g(0.1996当量)聚己二酸-乙二醇-1,4-丁二醇酯二醇、60g丙酮、30g(0.1663当量)实施4得到的亲水性HDI-TDI混合物、0.5g二丁基月桂酸锡，搅拌 均匀，升温至60℃-80℃，反应6小时后开始测羟值，后面每隔一小时测一次羟值，当羟值趋于基本不变时反应结束，得含磺酸盐基的聚氨酯预聚体；
b)将240g去离子水分四次向反应瓶内缓慢加入，以1000-2000转/分搅拌，进行乳化20～30min，然后升温至60℃真空脱除丙酮，制得固含量为50％的含磺酸盐基的聚氨酯乳液。经检测该乳液呈乳白色微蓝光，羟值为4.0mgKOH/g。
应用实施例5
一种水性聚氨酯树脂乳液的制备方法，包括以下步骤：
a)在反应瓶内，加入200g(0.1996当量)聚邻苯二甲酸-己二酸-新戊二醇-已二醇酯二醇、50g丙酮、30.7g(0.1535当量)实施5得到的亲水性HDI、0.5g二丁基月桂酸锡，搅拌均匀，升温至60℃-80℃，反应8小时后开始测羟值，此后每隔一小时测一次羟值，当羟值趋于基本不变时反应结束，得含磺酸盐基的聚氨酯预聚体；
b)将224g去离子水分四次向反应瓶内缓慢加入，以1000～2000转/分搅拌，进行乳化20～30min，然后升温至60℃真空脱除丙酮，制得固含量为50％的含磺酸盐基的聚氨酯乳液。经检测该乳液呈乳白色微蓝光，羟值为5.6mgKOH/g。
应用实施例6
一种水性聚氨酯树脂乳液的制备方法，包括以下步骤：
a)在反应瓶内，加入200g(0.1996当量)聚己内酯二醇、67g丙酮、35.5g(0.1376当量)实施6得到的胺基磺酸盐型亲水性IPDI、0.5g二丁基月桂酸锡，搅拌均匀，升温至60℃-80℃，反应6小时后开始测羟值，后面每隔一小时测一次羟值，当羟值趋于基本不变时反应结束，得含胺基磺酸盐基的聚氨酯预聚体；
b)将226g去离子水分四次向反应瓶内加入，以1000～2000转/分搅拌，进行乳化20min，然后升温至60℃真空脱除丙酮，得固含量为50.2％的含胺基磺酸盐基的聚氨酯乳液。
经检测该乳液呈乳白色微蓝光，羟值为7.6mgKOH/g。
对比实施例2(CN102585149A的实施例1)
一种聚氨酯乳液的制备方法，包括以下步骤：
反应瓶内，加入20g(0.01996当量)聚己二酸丁二醇酯，升温至85℃，加入7.6g(0.06837当量)IPDI和0.2g二月桂酸二丁基锡反应1.5h，降温至80℃，加入0.64g(0.01432当量)1，4-丁二醇反应1h，再降温至60℃，加入1.44g(0.01224当量)已溶解在5ml二甲亚砜的N，N-二(2-羟乙基)-2-氨基乙磺酸钠(BES-Na)反应3h，为了降低体系粘度，可加入15mL丙酮稀释。反应充分后降温至40℃，加入蒸馏水25mL，用强剪切力乳化30min，减压蒸除丙酮，得固含量约为50％，外观半透明的聚氨酯乳液。
说明：该对比实施例2的OH当量之和为0.04652，NCO当量为0.06837，显然反应结束时产物端头是异氰酸根，当加水乳化时存在水与-NCO反应生成脲，同时放出CO 2的反应。
从应用实施例6和对比实施例2可以看出：同样用(BES-Na)作水性聚氨酯乳液的亲水基团，本发明方法既简单，又能较多地保留有效成份。
应用实施例7
一种IPDI-HDI混合型水性聚氨酯固化剂的制备方法，包括以下步骤：
在三口烧瓶内，加入100g(0.4547当量)实施例1制得的亲水性IPDI和58g丙酮，搅拌均匀，滴加10g(0.2273当量)三羟甲基丙烷与20g丙酮组成的混合液，2小时滴完，在60℃～80℃保温反应10小时，加入200g(1.095当量)HDI三聚体(NCO％为23％)，在50℃-60℃反应3小时后取样测NCO下降趋于稳定时，降温出料，得IPDI-HDI混合型水性聚氨酯固化剂，经检测该水性固化剂的外观为浅黄色透明粘稠液体，固含量为80％，粘度为2100mpa.s(25℃)，NCO含量14.3％。
应用实施例8
一种双组份水性聚氨酯涂料的制备，包括以下步骤：
a)将40g应用实施例7的IPDI-HDI混合型水性聚氨酯固化剂用手工搅拌溶于40g水中，制成乳白色微蓝光乳液，备用；
b)取300g实施例5制备的水性聚氨酯树脂乳液，加入步骤a)得到的乳白色微蓝光乳液，搅拌混合均匀，制得双组份水性聚氨酯涂料。
将其制成样板，在50℃固化48小时，室温放置24小时后，测试漆膜性能如下：漆膜外观(目测)平整光滑；光泽(60°)：≥90％；硬度：邵氏D52；冲击强度：50KJ/m 2；附着力：1级；柔韧性：1mm；耐水性(72h)无异常。
检验方法：光泽(60°)按GB9754-2007、硬度按GB1730-79、冲击强度按GB/T 2571-1995、附着力按GB1720-89、柔韧性按GB1731-79标准、耐水性按GB/T1733-1993。
从上述应用实施例和对比实施例可以看出：用本发明亲水性二异氰酸酯作为二异氰酸酯原料，无论是制备水性聚氨酯乳液，还是制备水性聚氨酯固化剂，操作方法都非常简单，基本与生产溶剂型聚氨酯产品的方法差不多，而且产品的水溶性都非常好，若将端头带羟基的水性树脂乳化只需稍加搅拌(不必高速分散)就能制成乳白色泛蓝光的乳液，若将端头带异氰酸根的水性固化剂与水性树脂乳液混合也非常简单，可直接将两者混合，也可先加水将固化剂分散后再混合。
上述应用实施例可进一步组合成水性双组份聚氨酯涂料、水性双组份聚氨酯胶粘剂、水性聚氨酯皮革涂饰剂、水性聚氨酯织物浆料等，用途非常广泛。
以上对本发明提供的亲水性二异氰酸酯及其应用进行了详细的介绍，本文中应用了具体实施例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想，包括最佳方式，并且也使得本领域的任何技术人员都能够实践本发明，包括制造和使用任何装置或系统，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。本发明专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。

Claims (10)

  1. 一种亲水性二异氰酸酯，其特征在于，所述亲水性二异氰酸酯包含如下通式的结构单元：
    Figure PCTCN2021081648-appb-100001
    式中：SO 3M为磺酸盐基团，M为K离子或Na离子或铵离子，n为1-6。
  2. 权利要求1所述的亲水性二异氰酸酯的制备方法，其特征在于，包括以下步骤：将二异氰酸酯与亲水扩链剂混合反应，得到亲水性二异氰酸酯。
  3. 根据权利要求2所述的制备方法，其特征在于，所述二异氰酸酯和所述亲水扩链剂的摩尔比为(2-6)：1；所述亲水扩链剂为至少包含一种含磺酸盐基的小分子二元醇或胺基磺酸盐基的小分子二元醇；所述二异氰酸酯为MDI、HMDI、TDI、HDI、IPDI或XDI中的至少一种。
  4. 根据权利要求2所述的制备方法，其特征在于，具体的步骤为：在反应釜内，加入二异氰酸酯和助溶剂，开启搅拌器，升温至30℃-80℃，分数次加入亲水扩链剂，每次加入亲水扩链剂后都要在50℃-60℃反应0.5-3小时，直至最后一次加入亲水扩链剂，在50℃-
    60℃反应0.5-3小时后，再升温至60℃-80℃反应6-20小时，降温出料，得到亲水性二异氰酸酯。
  5. 根据权利要求4所述的制备方法，其特征在于，所述助溶剂的加入量为二异氰酸酯重量的0-40％；所述含磺酸盐基的小分子二元醇为1,2-二羟基-3-丙磺酸钠、1,4-二羟基丁烷-2-磺酸钠或小分子磺酸盐二元醇中的至少一种；所述小分子磺酸盐二元醇为二羧基磺酸盐与小分子二元醇、小分子二元酸经酯化反应制得；所述二羧基磺酸盐为二羧基磺酸钠、二羧基磺酸钾或二羧基磺酸铵中的至少一种；所述小分子磺酸盐二元醇的分子量为350-3000，所述小分子二元醇为分子量小于300的二元醇，所述小分子二元酸为分子量小于300的二元酸。
  6. 根据权利要求4所述的制备方法，其特征在于，所述胺基磺酸盐基的小分子二元醇为N,N-二(2-羟乙基)-2-氨基乙磺酸钠。
  7. 一种聚氨酯乳液，其特征在于，是由如下的制备方法制得：将权利要求1所述的亲水性二异氰酸酯与二羟基化合物反应，得到端头带羟基的水性聚氨酯树脂，再加水乳化分散，制得聚氨酯乳液；所述二羟基化合物为聚酯二元醇、聚醚二元醇、聚己内酯二醇、端羟基醇 酸树脂、端羟基有机硅树脂、带羟基的聚丙烯酸树脂或分子量小于300的二元醇中的至少一种。
  8. 一种水性聚氨酯固化剂，其特征在于，是由权利要求1所述的亲水性二异氰酸酯与多羟基化合物反应制得。
  9. 一种封闭型水性多异氰酸酯固化剂，其特征在于，是由权利要求8所述的水性聚氨酯固化剂与封闭剂反应制得。
  10. 权利要求1所述的亲水性二异氰酸酯在制备水性聚氨酯涂料、水性聚氨酯黏合剂、水性聚氨酯连接料、水性皮革涂饰剂、水性织物整理剂或水性油墨连接料中的应用。
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