CN111423343B - Hydrophilic diisocyanate and preparation method and application thereof - Google Patents
Hydrophilic diisocyanate and preparation method and application thereof Download PDFInfo
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- CN111423343B CN111423343B CN202010201220.6A CN202010201220A CN111423343B CN 111423343 B CN111423343 B CN 111423343B CN 202010201220 A CN202010201220 A CN 202010201220A CN 111423343 B CN111423343 B CN 111423343B
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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
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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
- C07C309/13—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
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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
- C08G18/70—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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
Abstract
The invention belongs to the field of polyurethane, and provides hydrophilic diisocyanate which comprises at least one structural unit containing the following general formula:
in the formula: SO (SO)3M is a sulfonate group, M is a K ion or a Na ion or an ammonium ion; n is 1 to 6; the hydrophilic diisocyanate is formed by reacting at least one hydrophilic chain extender with a diisocyanate. The sulfonate group in the structure of the hydrophilic diisocyanate is strong acid strong alkali salt, has good hydrophilicity, and the isocyanate groups at two ends retain the performance of the original diisocyanate, so the hydrophilic diisocyanate has the chemical reaction characteristic of the diisocyanate; the preparation of the waterborne polyurethane by using the hydrophilic diisocyanate changes the prior process method and greatly simplifies the operation.
Description
Technical Field
The invention belongs to the field of polyurethane, and particularly relates to hydrophilic diisocyanate and a preparation method and application thereof.
Background
The limit of environmental regulations on the discharge amount of Volatile Organic Compounds (VOCs) in chemical products promotes the development and application of waterborne polyurethane products, but some bottleneck technical problems still remain to be solved, such as: the hydrophilic raw materials required by the polyurethane hydration are too few in variety, the hydrophilic raw materials of the amino sulfonate are expensive, the hydrophilic raw materials of the dimethylolcarboxylic acid can react with isocyanate only by being dissolved by a special solvent, the processing technology is complex and the like, and the transformation of a polyurethane product of related enterprises from a solvent type to the hydration (changing oil into water) is restricted.
The water-based polyurethane is a water-based polyurethane product which is characterized in that hydrophilic groups are introduced into a hydrophobic polyurethane structure, and how to introduce hydrophilic groups with low price, no toxicity, no odor and good hydrophilic effect is achieved by adopting a simple and easy technological method, so that the main performance of the original solvent-based product is not changed, and no VOC is discharged, which is the key point of continuous research in the field.
The hydrophilic agent with better water changing effect of the polyurethane oil is sulfonate base at present, because sulfonate belongs to strong acid and strong alkali salt, the hydrophilic agent has stronger hydrophilicity, the using amount is less when the polyurethane dispersoid is synthesized, and the dispersoid has a more stable double electric layer structure; because the hydrophilic group consumption is small, the influence on the performance of polyurethane is small, so that the performance of the original solvent-based product can be basically maintained by the acid and alkali resistance, electrolyte resistance, mechanical stability, intermiscibility with an auxiliary agent, adhesive film performance and the like of the polyurethane dispersion. However, the prior art has not been studied on sulfonate-based hydrophilic agents, mainly because the alkyl sulfonate has only an external emulsification function, the monohydroxy sulfonate cannot extend the chain of isocyanate, and the good modification effect is the micromolecule dihydroxyl amino sulfonate and the dihydroxyl sulfonate, but the two are expensive, so that the cost of changing oil into water is greatly increased, the fat solubility is poor, and more high-boiling polar solvents need to be added, so that the residual amount of the organic solvent of the product is high, and the popularization is difficult. The prior art CN107082860A discloses a micromolecule diol with molecular weight of 350-1000-containing sulfonic acid group, which reacts with diisocyanate to prepare an aqueous polyurethane curing agent, and introduces a preparation method for preparing the micromolecule diol containing the sulfonic acid group by using dicarboxyl sulfonate and dihydroxy sulfonate, but the conversion conditions are harsh in practical application, and the technology is difficult to master by common enterprises. Because the dicarboxyl sulfonate is convenient in raw material source, low in price, nontoxic and tasteless, if the dicarboxyl sulfonate can be used as a popularization raw material for changing polyurethane oil into water, the water-based process of polyurethane is certainly accelerated.
Accordingly, the present inventors have developed a hydrophilic diisocyanate containing a sulfonate group.
Disclosure of Invention
In order to make up the defects of the prior art, the invention aims to provide the hydrophilic diisocyanate containing the sulfonate group and the preparation method and application thereof.
The application refers to the application of the sulfonate group-containing hydrophilic diisocyanate in the aspects of preparing aqueous polyurethane emulsion, aqueous polyurethane curing agent, aqueous polyurethane binder, aqueous polyurethane finishing agent, aqueous polyurethane elastomer and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydrophilic diisocyanate comprising at least one structural unit having the formula:
in the formula: SO (SO)3M is sulfonate group, M is K ion or Na ion or ammonium ion, and n is 1-6.
A preparation method of hydrophilic diisocyanate comprises the following steps:
adding diisocyanate and cosolvent into a reaction kettle, starting a stirrer, heating to 30-80 ℃, adding the hydrophilic chain extender in several times, reacting at 50-60 ℃ for 0.5-3 hours after adding the hydrophilic chain extender each time until the hydrophilic chain extender is added in the last time, reacting at 50-60 ℃ for 0.5-3 hours, heating to 60-80 ℃ again for 6-20 hours, cooling and discharging to obtain the hydrophilic diisocyanate.
Preferably, the hydrophilic chain extender is divided into 3-10 parts and added for several times, and after each part of the hydrophilic chain extender is added, the reaction is carried out at 50-60 ℃ until the liquid in the kettle is transparent.
Preferably, the fraction is 3 to 10 times.
Preferably, the molar ratio of the diisocyanate to the hydrophilic chain extender is (2-6): 1.
more preferably, the molar ratio of the diisocyanate to the hydrophilic chain extender is (3-4): 1.
according to the molar ratio of the reaction materials, the following components are obtained: the hydrophilic diisocyanate contains a certain proportion of diisocyanate monomers besides the sulfonate group-containing diisocyanate in the main chain structure, and the prepared prepolymer is soluble in water or emulsifiable with water or dispersible with water as long as a certain proportion of hydrophilic groups exist during the preparation of the waterborne polyurethane, so that a certain proportion of hydrophilic groups are designed in the hydrophilic diisocyanate.
Preferably, the hydrophilic chain extender is a small molecule diol comprising at least one sulfonate group or an amine sulfonate group.
Preferably, the sulfonate group-containing small molecule diol is at least one of 1, 2-dihydroxy-3-propane sodium sulfonate, 1, 4-dihydroxy butane-2-sodium sulfonate or small molecule sulfonate diol.
Preferably, the small molecule diol of the amino sulfonate group is sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate.
Preferably, the diisocyanate is at least one of MDI, HMDI, TDI, HDI, IPDI or XDI.
Preferably, the micromolecular sulfonate dihydric alcohol is a product obtained by esterification reaction of dicarboxyl sulfonate, micromolecular dihydric alcohol and micromolecular dibasic acid, and the molecular weight is 350-3000.
More preferably, the molecular weight of the small-molecule sulfonate diol is 380-600.
Preferably, the small molecule diol is a diol with a molecular weight of less than 300.
More preferably, the small molecule diol is at least one of 3-methyl-1, 5-pentanediol, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanediol, methylpropanediol, TCD tricyclo glycol, 1, 3-propanediol, 1, 4-dimethylolcyclohexane, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, diethylpentanediol, 1, 2-propanediol, diethylene glycol, tetrahydrofuran diol, 1, 6-hexanediol, trimethylpentanediol, butylethylpropanediol, 2-bis (4-hydroxyphenyl) propane, dipropylene glycol, tripropylene glycol, or ethylhexanediol.
Preferably, the small molecule diacid is diacid with molecular weight less than 300.
More preferably, the small molecule diacid is at least one of adipic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic anhydride, dimethyl terephthalate, succinic acid, or glutaric acid.
Preferably, the dicarboxyl sulfonate is at least one of a dicarboxyl sulfonic acid sodium salt, a dicarboxyl sulfonic acid potassium salt, or a dicarboxyl sulfonic acid ammonium salt.
More preferably, the dicarboxy sulfonate is sodium 5-sulfoisophthalate.
Preferably, the cosolvent is added in an amount of 0-40% by weight of the diisocyanate, to obtain a 100% solids content of the hydrophilic diisocyanate.
More preferably, the cosolvent is at least one of acetone, butanone, ethyl acetate, butyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, tetrahydrofuran, dioxane, or dimethylformamide.
A polyurethane emulsion is prepared by reacting the hydrophilic diisocyanate with dihydroxy compounds to obtain aqueous polyurethane resin with hydroxyl at the end, and then adding water to emulsify and disperse at high speed to obtain the polyurethane emulsion.
Preferably, the dihydroxy compound is at least one of polyester diol, polyether diol, polycaprolactone diol, hydroxyl-terminated alkyd resin, hydroxyl-terminated silicone resin, polyacrylic resin with hydroxyl groups or small molecular diol.
The hydrophilic diisocyanate reacts with dihydroxy compounds (polyester, polyether, micromolecular dihydric alcohol and the like) to prepare aqueous polyurethane resin with hydroxyl at the end, water is added for high-speed dispersion and emulsification to obtain polyurethane emulsion, products with different molecular weights can be prepared by designing OH/NCO to be more than 1, and the chemical reaction formula A is as follows:
in the formula: SO (SO)3M is sulfonate group, M is K ion or Na ion or ammonium ion, and n is positive integer of 1,2, 3, etc.
The water-based polyurethane curing agent is prepared by reacting the hydrophilic diisocyanate with a polyhydroxy compound.
Preferably, the polyol is at least one of trimethylolpropane, glycerol, trimethylolethane, 1,2, 6-hexanetriol, or pentaerythritol.
The hydrophilic diisocyanate and the polyhydroxy compound are reacted to prepare the polyisocyanate prepolymer, and the water-based polyurethane curing agent can be prepared by designing NCO/OH ≧ 2, and the chemical reaction formula B is as follows:
in the formula: SO (SO)3M is a sulfonate group, M is a K ion or a Na ion or an ammonium ion.
As can be seen from the above chemical reaction formulas A and B: the hydrophilic diisocyanate facilitates the preparation of the waterborne polyurethane, and the hydrophilic diisocyanate can directly replace part of diisocyanate to react with a hydrogen-containing compound to enable the polyurethane structure of the product to carry hydrophilic sulfonate groups, so that the polyurethane prepolymer becomes hydrophilic and can be dissolved in water or emulsified or dispersed, and various waterborne polyurethane products can be prepared.
The closed water-base polyisocyanate curing agent is prepared by the reaction of the water-base polyurethane curing agent and a closing agent.
Preferably, the aqueous polyurethane curing agent is a polyisocyanate prepolymer prepared by reacting the hydrophilic diisocyanate of the present invention with a polyol.
Preferably, the blocking agent is a hydrogen-containing compound.
More preferably, the blocking agent is at least one of 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, epsilon-caprolactam, phenol or catechol.
An application of hydrophilic diisocyanate in preparing water-based polyurethane coating, water-based polyurethane adhesive, water-based polyurethane binder, water-based leather finishing agent, water-based fabric finishing agent or water-based ink binder.
Preferably, the aqueous polyurethane emulsion with hydroxyl at the end and the aqueous polyurethane curing agent with polyisocyanate at the end can be combined into a two-component aqueous polyurethane coating and an aqueous polyurethane adhesive, and the aqueous polyurethane curing agent with polyisocyanate at the end and the aqueous resin with hydroxyl can be combined into an aqueous polyurethane binder, an aqueous leather finishing agent, an aqueous fabric finishing agent or an aqueous ink binder and the like.
Advantageous effects
1. The sulfonate group in the structure of the hydrophilic diisocyanate is strong acid strong alkali salt, has good hydrophilicity, and the isocyanate groups at two ends retain the performance of the original diisocyanate, so the hydrophilic diisocyanate has the chemical reaction characteristic of the diisocyanate; the preparation of the waterborne polyurethane by using the hydrophilic diisocyanate changes the prior process method and greatly simplifies the operation. The method for preparing the hydrophilic diisocyanate is simple, can be used for batch production, can directly use the hydrophilic diisocyanate to prepare the waterborne polyurethane, can reduce the cost, and is favorable for popularization and application of changing polyurethane oil into water.
2. The hydrophilic diisocyanate product of the present invention has stable performance. Because the property of the sulfonate is stable, the hydrophilic diisocyanate generated after the diisocyanate is modified by the sulfonate group still has a stable structure, and the storage experiment proves that: different types of products have more than half a year of storage period and can be sold as hydrophilic diisocyanate raw materials.
3. The variety is many. According to different compositions and proportions of the prepared raw materials, a series of hydrophilic diisocyanates with different types can be prepared, and each product has specific NCO%, viscosity and storage period, so that a user can select a variety with a proper type according to the performance of a specific waterborne polyurethane product.
4. The method for changing oil into water is simple. When the hydrophilic diisocyanate of the invention is used for replacing partial diisocyanate to prepare the waterborne polyurethane, the polyurethane product which is soluble, emulsifiable or water dispersible in water can be produced by designing the molar ratio of reactants according to the product performance and using the process method for producing the solvent type polyurethane which is familiar to the technical personnel in the field; furthermore, the hydrophilic diisocyanate can be directly added into the solvent type polyisocyanate prepolymer (polyurethane curing agent) to make the polyisocyanate prepolymer hydrophilic, and then the hydrophilic diisocyanate is mixed with polyurethane resin emulsion, acrylic resin emulsion, alkyd resin emulsion and the like to be used as a cross-linking agent of the resin emulsions, so that the aim of quickly changing the water of the polyurethane oil is fulfilled.
5. The production stability of changing oil into water is good. The invention can prepare aliphatic, alicyclic or aromatic hydrophilic diisocyanate, so that the performances of different types of diisocyanate can be effectively utilized. In the prior art, the polyurethane emulsion is mainly prepared from aliphatic or alicyclic diisocyanate, and the preparation technology is difficult because the activity of the aromatic diisocyanate is high. For example: when the dimethylolcarboxylic acid is used for preparing the aqueous polyurethane resin, HDI or IPDI is generally adopted, because the dimethylolcarboxylic acid is a trifunctional compound, gel is easily generated in the production process, the quality is unstable, and particularly, the explosion polymerization is generated in industrial mass production by carelessness. When the invention is used for preparing the waterborne polyurethane resin, the hydrophilic diisocyanate has two functionality degrees and directly reacts with the dihydroxy prepolymer, the production process is easy to control, the operation is simple, and the product quality is stable.
6. The environmental protection is good. The hydrophilic diisocyanate can be prepared into a waterborne polyurethane product with 100% solid content and no VOC emission, and can be further prepared into an organic solvent-free waterborne polyurethane product.
7. The application range is wide. The hydrophilic diisocyanate can be used for preparing aqueous polyurethane emulsion, aqueous polyurethane curing agent and other aqueous polyurethane, can be further prepared into two-component aqueous polyurethane adhesive, aqueous polyurethane coating and other aqueous polyurethane products, and can be used for conveniently modifying solvent type polyurethane into aqueous polyurethane.
Detailed Description
A hydrophilic diisocyanate comprising at least one structural unit having the formula:
in the formula: SO (SO)3M is sulfonate group, M is K ion or Na ion or ammonium ion, and n is 1-6.
A preparation method of hydrophilic diisocyanate comprises the following steps:
adding diisocyanate and cosolvent into a reaction kettle, starting a stirrer, heating to 30-80 ℃, adding the hydrophilic chain extender in several times, reacting at 50-60 ℃ for 0.5-3 hours after adding the hydrophilic chain extender each time until the hydrophilic chain extender is added in the last time, reacting at 50-60 ℃ for 0.5-3 hours, heating to 60-80 ℃ again for 6-20 hours, cooling and discharging to obtain the hydrophilic diisocyanate.
The hydrophilic chain extender is divided into 3-10 parts and added for several times, and after each part of the hydrophilic chain extender is added, the reaction is carried out at 50-60 ℃ until the liquid in the kettle is transparent.
The molar ratio of the reaction materials is diisocyanate: the hydrophilic chain extender is (3-4): 1.
the hydrophilic chain extender is a small molecule diol containing at least one sulfonate group-containing small molecule diol or an amine sulfonate group-containing small molecule diol.
The micromolecular dihydric alcohol containing sulfonate group is at least one of 1, 2-dihydroxy-3-propanesulfonic acid sodium salt, 1, 4-dihydroxy butane-2-sulfonic acid sodium salt or micromolecular sulfonate dihydric alcohol.
The micromolecule dihydric alcohol containing the amidosulfate group is N, N-di (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt.
The diisocyanate is at least one of MDI, HMDI, TDI, HDI, IPDI and XDI.
The micromolecular sulfonate dihydric alcohol is a product obtained by esterification reaction of dicarboxyl sulfonate, micromolecular dihydric alcohol and micromolecular dibasic acid, and the molecular weight of the micromolecular sulfonate dihydric alcohol is 380-600.
The dicarboxyl sulfonate is 5-sodium m-phthalate sulfonate.
The micromolecular dihydric alcohol is dihydric alcohol with the molecular weight less than 300; further, the small molecule diol is at least one of 3-methyl-1, 5-pentanediol, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanediol, methylpropanediol, TCD tricyclo glycol, 1, 3-propanediol, 1, 4-dimethylolcyclohexane, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, diethylpentanediol, 1, 2-propanediol, diethylene glycol, tetrahydrofuran diol, 1, 6-hexanediol, trimethylpentanediol, butylethylpropanediol, 2-bis (4-hydroxyphenyl) propane, dipropylene glycol, tripropylene glycol, or ethylhexanediol.
The micromolecular dibasic acid is dibasic acid with the molecular weight less than 300; further, the small molecule dibasic acid is at least one of adipic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic anhydride, dimethyl terephthalate, succinic acid, and glutaric acid.
The addition amount of the cosolvent is 0-40% of the weight of the diisocyanate, and the cosolvent is at least one of acetone, butanone, ethyl acetate, butyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, tetrahydrofuran, dioxane or dimethylformamide.
The average molecular weight and NCO% of the hydrophilic diisocyanate can be calculated or tested.
A polyurethane emulsion is prepared through reaction between hydrophilic diisocyanate and dihydroxy compound to obtain the aqueous polyurethane resin with hydroxy end, and high-speed emulsifying.
The preparation method of the polyurethane emulsion comprises the following steps: adding the dihydroxy compound and the cosolvent which are dehydrated in vacuum into a reaction kettle, stirring uniformly, heating to 60 ℃, adding hydrophilic diisocyanate and a catalyst, heating to 70-100 ℃, performing chain extension reaction for 6-15 hours to obtain a polyurethane prepolymer with a hydroxyl main chain structure at the end and containing sulfonate, adding water, emulsifying and dispersing at high speed, and removing the cosolvent to obtain the hydroxyl-terminated waterborne polyurethane emulsion.
The dihydroxy compound is at least one of polyester diol, polyether diol, polycaprolactone diol, hydroxyl-terminated alkyd resin, hydroxyl-terminated organic silicon resin, polyacrylic resin with hydroxyl or micromolecular diol.
The invention relates to a waterborne polyurethane curing agent, which is a waterborne polyurethane prepolymer (waterborne polyurethane curing agent) with a terminal band containing polyisocyanate prepared by reacting hydrophilic diisocyanate with a polyhydroxy compound, and the preparation method comprises the following steps:
adding hydrophilic diisocyanate and cosolvent into a reaction kettle, stirring uniformly, adding the polyol dehydrated in vacuum, stirring for 0.5-2 hours at room temperature, heating to 50-100 ℃ and reacting for 2-10 hours to obtain polyisocyanate prepolymer with a main chain structure containing sulfonate groups, and removing the cosolvent to obtain the waterborne polyurethane curing agent.
The 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 a main chain structure with a blocking agent.
The sealing agent is at least one of methanol, ethanol, isopropanol, tert-butanol, propylene glycol monomethyl ether, methyl ethyl ketoxime, acetone oxime, methyl isobutyl oxime, imidazole, 2-methylpyrazole, 3, 5-dimethylpyrazole, 3-methyl-5-ethylpyrazole, 3-ethyl-5-propylpyrazole, acetylacetone, ethyl acetoacetate, epsilon-caprolactam, phenol or catechol.
An application of hydrophilic diisocyanate in preparing water-based polyurethane coating, water-based polyurethane adhesive, water-based polyurethane binder, water-based leather finishing agent, water-based fabric finishing agent or water-based ink binder.
The waterborne polyurethane emulsion with hydroxyl at the end and the waterborne polyurethane curing agent with the polyisocyanate at the end can be combined into a two-component waterborne polyurethane coating and a waterborne polyurethane adhesive, and the waterborne polyurethane curing agent with the polyisocyanate at the end and the waterborne resin with the hydroxyl can be combined into a waterborne polyurethane binder, a waterborne leather finishing agent, a waterborne fabric finishing agent or a waterborne ink binder.
The present invention will be described in further detail with reference to specific examples.
In the following examples:
1. the viscosity was measured according to the national Standard GB/T2794-1995 determination of the viscosity of the adhesive.
2. The NCO content was measured according to the Standard of chemical industry "determination of isocyanate group content in HG/T2409-92 polyurethane prepolymer".
3. Molecular weight was measured by GPC gel chromatography.
4. The hydroxyl value was measured according to the Standard of chemical industry "determination of resin value of HG/T2709-95".
Example 1
A preparation method of hydrophilic diisocyanate comprises the following steps:
a) preparation of hydrophilic chain extender (Small molecule sulfonate diol)
Adding 150g of diethylene glycol, 780g of 1, 4-butanediol, 260g of deionized water and 2.4g of triphenyl phosphite into a reaction bottle provided with a fractionating device, starting a stirrer, heating to 95 ℃, adding 400g of isophthalic acid-5-sodium sulfonate, and dissolving for 2 hours at 90-95 ℃; adding 360g of adipic acid, stirring at 90-95 ℃ until all adipic acid is dissolved, introducing nitrogen, starting esterification reaction, raising the temperature in the kettle, controlling the temperature of a water outlet at the top of the condensing tube to be 90-99 ℃, controlling the temperature in the kettle to be 190 ℃ along with the esterification reaction, and continuing to discharge water for 1 hour when the water yield reaches a theoretical value; and starting a vacuum pump, gradually increasing the vacuum degree to be more than 0.097MPa, removing residual alcohol, cooling to 70 ℃, and discharging to obtain the light yellow transparent micromolecular sulfonate dihydric alcohol. The solid content of the product was 99.8% and the number average molecular weight was 420.
b) Preparation of hydrophilic diisocyanate (hydrophilic IPDI)
Adding 300g (2.699 equivalent) IPDI into a three-mouth reaction bottle, starting a stirrer, heating to 55 ℃, adding 420g (0.675 equivalent) of the micromolecule dihydric alcohol containing sulfonate group prepared in the step a) for three times, reacting for 0.5 hour after each addition until all the small molecule dihydric alcohol is added, after the reaction is finished for 1 hour, heating to 60-70 ℃, sampling every 1 hour after the reaction is carried out for 8 hours to measure the NCO content, and when the NCO content is reduced to be stable, cooling and discharging to obtain the IPDI containing sulfonate group with the solid content of 100%. The viscosity of the hydrophilic IPDI was found to be 4200 mPas (25 ℃ C.), 19.1% NCO and 6 months of pot life.
Example 2
Preparation of a hydrophilic diisocyanate (hydrophilic MDI) comprising the steps of:
200g (1.6 equivalent) of MDI and 67g of acetone are added into a reaction bottle, a stirrer is started, the temperature is raised to 30 ℃, 67.2g (0.32 equivalent) of the hydrophilic chain extender prepared in the step a) of the embodiment 1 is added in four times, the reaction is carried out for 0.5 hour after each addition until all the hydrophilic chain extender is added, the temperature is raised to 50 ℃ after the reaction is carried out for 1 hour, the reaction is carried out for 2 hours, the temperature is raised to 60 ℃, the NCO content is measured by sampling every 0.5 hour after the reaction is carried out for 5 hours, and when the NCO is reduced to be stable, the temperature is reduced and the materials are discharged, so that the MDI containing sulfonate group with the solid content of.
The viscosity of the hydrophilic MDI was measured to be 5600mPa.s/25 ℃, NCO% 16.0%, and the shelf life 6 months.
Example 3
Preparation of a hydrophilic diisocyanate (hydrophilic TDI) comprising the following steps:
200g (2.299 equivalent) of TDI is added into a reaction bottle, a stirrer is started, the temperature is raised to 30 ℃, 160g (0.766 equivalent) of the hydrophilic chain extender prepared in the step a) of the embodiment 1 is added for six times, the reaction is carried out for 0.5 hour after each addition until all the TDI is added, the temperature is raised to 50 ℃ after the reaction is carried out for 1 hour, the reaction is carried out for 2 hours after the reaction is carried out for 5 hours after the temperature is raised to 60 ℃, the NCO content is measured by sampling every 0.5 hour after the reaction is carried out for 5 hours, and when the NCO is reduced and tends to be stable, the temperature is reduced and discharging is carried out, so that the TDI.
The viscosity of the hydrophilic TDI was 3600mPa.s/25 ℃, the NCO% was 17.8% and the storage period was 6 months.
Example 4
Preparation of a hydrophilic diisocyanate (hydrophilic HDI-TDI mixture) comprising the following steps:
200g (2.38 equivalents) of HDI are added into a reaction flask, a stirrer is started, the temperature is raised to 50 ℃, 130g (0.618 equivalent) of the hydrophilic chain extender prepared in the step a) of the example 1 is added into the reaction flask in four times, and the reaction is carried out for 1 hour after each addition until all the addition is finished and the reaction is carried out for 1 hour; then 8g of TDI (0.092 equivalent) was added and reacted for 1 hour; heating to 50-60 ℃ for reaction for 2 hours, sampling every 1 hour after reacting for 10 hours at 65-75 ℃ to measure the NCO content, and cooling and discharging when the NCO content is reduced and tends to be stable to obtain the HDI-TDI mixed liquid containing sulfonate base with the solid content of 100%.
The viscosity of the hydrophilic HDI-TDI mixture was determined to be 4200mPa.s/25 ℃, 23.0% NCO, and 6 months of storage life.
Example 5
Preparation of hydrophilic diisocyanate (hydrophilic HDI) comprising the following steps:
200g (2.38 equivalents) of HDI and 75g of acetone are added into a reaction flask, a stirrer is started, the temperature is raised to 50 ℃, 100g (0.476 equivalent) of the hydrophilic chain extender prepared in the step a) of the example 1 is added into the reaction flask in four times, and the reaction is carried out for 1 hour after each addition until the reaction is completely finished for 1 hour; heating to 50-60 ℃ for reacting for 2 hours, sampling every 1 hour after reacting for 10 hours at 60-70 ℃ to measure the NCO content, and cooling and discharging when the NCO content is reduced and tends to be stable to obtain the HDI containing sulfonate group with the solid content of 80%.
The viscosity of the hydrophilic HDI was determined to be 1500mPa.s/25 ℃, NCO% to be 21.1%, and the pot life to be 6 months.
Example 6
Preparation of a hydrophilic diisocyanate (hydrophilic IPDI containing aminosulfonate groups) comprising the steps of:
adding 200g (1.799 equivalents) of IPDI and 85g of acetone into a three-neck reaction bottle, starting a stirrer, heating to 50 ℃, dividing 53g (0.4498 equivalents) of sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate (BES-Na) into five parts, adding the BES-Na into the reaction bottle in five times, completely dissolving the BES-Na into the solution in each part of BES-Na, reacting the solution for 1 hour, and then adding the next part of BES-Na into the reaction bottle until all BES-Na is added, and dissolving and reacting the solution for 1 hour; and then heating to 50-60 ℃ for reaction for 2 hours, sampling every 1 hour after reacting for 8 hours at 60-70 ℃ to measure the NCO content, and when the NCO content is reduced to be stable, cooling and discharging to obtain IPDI containing aminosulfonate group with the solid content of 75%.
The viscosity of the hydrophilic IPDI was determined to be 2100mPa.s/25 ℃, NCO% 16.3% and the pot life 6 months.
Application example 1
The preparation method of the IPDI type waterborne polyurethane curing agent comprises the following steps:
adding 100g (0.457 equivalent) of the hydrophilic IPDI prepared in the example 1 and 27g of propylene glycol monomethyl ether acetate into a three-neck flask, starting a stirrer, dropwise adding a mixed solution consisting of 10g (0.228 equivalent) of trimethylolpropane and 20g of acetone for 2 hours, reacting for 8 hours at the temperature of 80-90 ℃, and then heating to the temperature of 90-100 ℃ for 4 hours; cooling to 60 ℃, adding 200g (0.571 equivalent) of IPDI trimer (the solid content is 70 percent, and the NCO percent is 12 percent), reacting for 3 hours at 50-55 ℃, sampling and measuring when the NCO is reduced to be stable, discharging to obtain 357g of IPDI type waterborne polyurethane curing agent.
The aqueous curing agent was determined to be a pale yellow, clear, viscous liquid with a solids content of 70% and a viscosity of 2200mpa.s (25 ℃) with an NCO content of 9.4%.
Application example 2
The preparation method of the MDI type waterborne blocked polyurethane curing agent comprises the following steps:
a) adding 200g (0.7619 equivalent) of the hydrophilic MDI prepared in the example 2, 80g (0.64 equivalent) of MDI and 20g of propylene glycol monomethyl ether acetate into a three-neck flask, uniformly stirring, dropwise adding a mixed solution consisting of 31 g (0.7 equivalent) of trimethylolpropane and 30g of acetone, dropwise adding the mixed solution after 2 hours, carrying out heat preservation reaction at 70-80 ℃ for 3 hours, raising the temperature to 80-90 ℃ for 2 hours, measuring the NCO content of reactants, and stopping the reaction when the NCO content is stable;
b) cooling to 50 ℃, adding 70g of methyl ethyl ketoxime for three times, controlling the feeding temperature to be 50-55 ℃, finishing the feeding after 2 hours, reacting for 1 hour at 60-70 ℃, reacting for 3 hours at 75-80 ℃, cooling and discharging to obtain the closed (MDI) water-based polyisocyanate curing agent.
The curing agent was determined to be a pale yellow transparent viscous liquid having a solids content of 75% and a viscosity of 3500 mPas (25 ℃).
Application example 3
The preparation method of the TDI type waterborne polyurethane curing agent comprises the following steps:
a) adding 200g (0.847 equivalent) of the hydrophilic TDI prepared in the example 3, 100g (1.149 equivalent) of the TDI and 64g of acetone into a three-neck flask, uniformly stirring, dropwise adding a mixed solution consisting of 42g (0.996 equivalent) of trimethylolpropane and 50g of acetone, dropwise adding the mixed solution after 2 hours, keeping the temperature at 60-85 ℃ for reaction for 8 hours, measuring the NCO content of a reactant, and stopping the reaction when the NCO is reduced to be stable;
b) transferring the materials into a residual monomer separation device, removing residual TDI monomer, cooling to 70 ℃, adding 114g of acetone, uniformly stirring and discharging to obtain the solvent type TDI curing agent. The curing agent was detected to be a pale yellow transparent viscous liquid in appearance, having a solid content of 75%, a viscosity of 2500 mPas (25 ℃), and an NCO% of 9.1%.
Comparative example 1 (classical method of solvent-based TDI curing agent)
A preparation method of a solvent-based TDI curing agent comprises the following steps:
a) adding 200g (2.298 equivalent) of TDI and 33g of ethyl acetate into a three-neck flask, uniformly stirring, dropwise adding a mixed solution consisting of 50g (1.149 equivalent) of trimethylolpropane and 50g of ethyl acetate, completing dropwise adding within 2 hours, keeping the temperature at 60-85 ℃ for reaction for 8 hours, measuring the NCO content of reactants, and stopping the reaction when the NCO content is reduced and tends to be stable;
b) transferring the materials into a residual monomer separation device, removing residual TDI monomer, cooling to 70 ℃, adding 83g of ethyl acetate, uniformly stirring and discharging to obtain the solvent type TDI curing agent. The curing agent was detected to be a pale yellow transparent viscous liquid in appearance, having a solid content of 75%, a viscosity of 2800 mPas (25 ℃), and an NCO% of 13.0%.
As can be seen from the above application example 3 and comparative example 1, the method for preparing the aqueous polyurethane curing agent from the hydrophilic diisocyanate of the present invention is substantially the same as the method for preparing the solvent type polyurethane curing agent.
Application example 4
1. The preparation method of the aqueous polyurethane resin emulsion comprises the following steps:
a) adding 200g (0.1996 equivalent) of poly adipic acid-ethylene glycol-1, 4-butanediol ester diol, 60g of acetone, 30g (0.1663 equivalent) of hydrophilic HDI-TDI mixture obtained by the step 4 and 0.5g of dibutyltin laurate into a reaction bottle, uniformly stirring, heating to 60-80 ℃, starting to measure a hydroxyl value after reacting for 6 hours, measuring the hydroxyl value every other hour, and finishing the reaction when the hydroxyl value is almost unchanged to obtain a sulfonate group-containing polyurethane prepolymer;
b) slowly adding 240g of deionized water into the reaction bottle for four times, stirring at 2000 revolutions per minute of 1000-. The emulsion is detected to be milk white and slightly blue light, and the hydroxyl value is 4.0 mgKOH/g.
Application example 5
A preparation method of aqueous polyurethane resin emulsion comprises the following steps:
a) adding 200g (0.1996 equivalent) of poly phthalic acid-adipic acid-neopentyl glycol-hexanediol ester diol, 50g of acetone, 30.7g (0.1535 equivalent) of hydrophilic HDI obtained in the step 5 and 0.5g of dibutyl tin laurate into a reaction bottle, uniformly stirring, heating to 60-80 ℃, starting measuring a hydroxyl value after reacting for 8 hours, measuring the hydroxyl value once every hour, and finishing the reaction when the hydroxyl value is almost unchanged to obtain a sulfonate group-containing polyurethane prepolymer;
b) and slowly adding 224g of deionized water into the reaction bottle for four times, stirring at 1000-2000 rpm, emulsifying for 20-30 min, heating to 60 ℃, and removing acetone in vacuum to obtain the sulfonate-containing polyurethane emulsion with the solid content of 50%. The emulsion is detected to be milk white and slightly blue light, and the hydroxyl value is 5.6 mgKOH/g.
Application example 6
A preparation method of aqueous polyurethane resin emulsion comprises the following steps:
a) adding 200g (0.1996 equivalent) of polycaprolactone diol, 67g of acetone, 35.5g (0.1376 equivalent) of aminosulfonate hydrophilic IPDI obtained by 6 implementation and 0.5g of dibutyltin laurate into a reaction bottle, uniformly stirring, heating to 60-80 ℃, starting to measure a hydroxyl value after 6 hours of reaction, measuring the hydroxyl value every other hour, and finishing the reaction when the hydroxyl value is basically unchanged to obtain the polyurethane prepolymer containing aminosulfonate;
b) 226g of deionized water is added into a reaction bottle for four times, stirred at 1000-2000 rpm, emulsified for 20min, and then heated to 60 ℃ to remove acetone in vacuum, so that the polyurethane emulsion containing the aminosulfonate with the solid content of 50.2% is obtained.
The emulsion is detected to be milk white and slightly blue light, and the hydroxyl value is 7.6 mgKOH/g.
COMPARATIVE EXAMPLE 2 (example 1 of CN 102585149A)
A preparation method of polyurethane emulsion comprises the following steps:
20g (0.01996 equiv.) of polybutylene adipate is added into a reaction bottle, the temperature is raised to 85 ℃, 7.6g (0.06837 equiv.) of IPDI and 0.2g of dibutyltin dilaurate are added for reaction for 1.5h, the temperature is lowered to 80 ℃, 0.64g (0.01432 equiv.) of 1, 4-butanediol is added for reaction for 1h, the temperature is lowered to 60 ℃, 1.44g (0.01224 equiv.) of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium (BES-Na) dissolved in 5mL of dimethyl sulfoxide is added for reaction for 3h, and 15mL of acetone can be added for dilution in order to reduce the system viscosity. And (3) cooling to 40 ℃ after full reaction, adding 25mL of distilled water, emulsifying for 30min by using strong shearing force, and evaporating to remove acetone under reduced pressure to obtain the polyurethane emulsion with solid content of about 50% and semitransparent appearance.
Description of the drawings: this comparative example 2 has a sum of OH equivalents of 0.04652 and an NCO equivalent of 0.06837, and it is clear that at the end of the reaction the product ends up in isocyanate groups, and that when emulsified with water there is a reaction of water with-NCO to form urea with evolution of CO2The reaction of (1).
From application example 6 and comparative example 2, it can be seen that: and (BES-Na) is also used as a hydrophilic group of the aqueous polyurethane emulsion, so that the method is simple and can keep more effective components.
Application example 7
A preparation method of an IPDI-HDI mixed type waterborne polyurethane curing agent comprises the following steps:
100g (0.4547 equivalent) of hydrophilic IPDI prepared in example 1 and 58g of acetone are added into a three-neck flask, the mixture is stirred uniformly, 10g (0.2273 equivalent) of a mixed solution composed of trimethylolpropane and 20g of acetone is dripped after 2 hours, the mixture is kept at 60-80 ℃ for 10 hours, 200g (1.095 equivalent) of HDI tripolymer (NCO percent is 23%) is added, and when NCO is reduced to be stable after 3 hours of reaction at 50-60 ℃, the mixture is sampled and tested, and then cooled and discharged, so that the IPDI-HDI mixed type waterborne polyurethane curing agent is obtained, and the appearance of the waterborne curing agent is light yellow transparent viscous liquid, the solid content is 80%, the viscosity is 2100mpa.s (25 ℃), and the NCO content is 14.3%.
Application example 8
The preparation method of the two-component waterborne polyurethane coating comprises the following steps:
a) 40g of the IPDI-HDI mixed waterborne polyurethane curing agent of the application example 7 is manually stirred and dissolved in 40g of water to prepare milky light blue emulsion for later use;
b) and (b) taking 300g of the aqueous polyurethane resin emulsion prepared in the embodiment 5, adding the milky light blue emulsion obtained in the step a), and uniformly stirring and mixing to obtain the two-component aqueous polyurethane coating.
The epoxy resin is made into a sample plate, cured for 48 hours at 50 ℃, and placed for 24 hours at room temperature, and then the performance of a test paint film is as follows: the paint film appearance (visual inspection) is flat and smooth; gloss (60 °): more than or equal to 90 percent; hardness: shore D52; impact strength: 50KJ/m2(ii) a Adhesion force: grade 1; flexibility: 1mm; the water resistance (72h) was not abnormal.
The detection method comprises the following steps: the gloss (60 ℃) is GB9754-2007, the hardness is GB1730-79, the impact strength is GB/T2571-1995, the adhesion is GB1720-89, the flexibility is GB1731-79 standard, and the water resistance is GB/T1733-1993.
From the above application examples and comparative examples, it can be seen that: the hydrophilic diisocyanate is used as a diisocyanate raw material, and no matter the hydrophilic diisocyanate is used for preparing a waterborne polyurethane emulsion or a waterborne polyurethane curing agent, the operation method is very simple, basically similar to the method for producing a solvent type polyurethane product, the water solubility of the product is very good, if the waterborne resin with hydroxyl at the end is emulsified, the milky blue-light emulsion can be prepared only by slightly stirring (high-speed dispersion is not needed), if the waterborne curing agent with isocyanate at the end is mixed with the waterborne resin emulsion, the waterborne curing agent and the waterborne resin emulsion are also very simple, the waterborne curing agent and the waterborne resin emulsion can be directly mixed, or the water is firstly added to disperse the curing agent and then mix.
The application embodiment 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 and the like, and the application range is very wide.
While the hydrophilic diisocyanates and their uses provided by the present invention have been described in detail above, the principles and embodiments of the present invention are illustrated herein using specific examples, which are provided only to facilitate an understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art.
Claims (7)
1. A hydrophilic diisocyanate comprising structural units of the general formula:
in the formula: SO (SO)3M is sulfonate group, M is K ion or Na ion or ammonium ion, n is 1-6; the hydrophilic diisocyanate is prepared by mixing diisocyanate and a hydrophilic chain extender for reaction; the molar ratio of the diisocyanate to the hydrophilic chain extender is (3-4): 1; the hydrophilic chain extender is a micromolecular dihydric alcohol at least containing a sulfonate group-containing micromolecular dihydric alcohol or an amino sulfonate group-containing micromolecular dihydric alcohol; the diisocyanate is at least one of MDI, HMDI, TDI, HDI, IPDI or XDI; the micromolecular dihydric alcohol containing sulfonate group is at least one of 1, 2-dihydroxy-3-propanesulfonic acid sodium salt, 1, 4-dihydroxy butane-2-sodium sulfonate or micromolecular sulfonate dihydric alcohol; the micromolecular sulfonate dihydric alcohol is prepared by esterification reaction of dicarboxyl sulfonate, micromolecular dihydric alcohol and micromolecular dibasic acid; the dicarboxyl sulfonate is at least one of dicarboxyl sodium sulfonate, dicarboxyl potassium sulfonate or dicarboxyl ammonium sulfonate; the molecular weight of the micromolecular sulfonate dihydric alcohol is 350-3000, the micromolecular dihydric alcohol is dihydric alcohol with the molecular weight of less than 300, and the micromolecular dibasic acid is dibasic acid with the molecular weight of less than 300; the amino sulfonate group micromolecule dihydric alcohol is N, N-di (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt;
the hydrophilic diisocyanate is prepared by the following specific preparation method:
adding diisocyanate and cosolvent into a reaction kettle, starting a stirrer, heating to 30-80 ℃, adding a hydrophilic chain extender in several times, reacting at 50-60 ℃ for 0.5-3 hours after adding the hydrophilic chain extender each time until the hydrophilic chain extender is added for the last time, reacting at 50-60 ℃ for 0.5-3 hours, heating to 60-80 ℃ again for 6-20 hours, and cooling and discharging when the NCO is reduced to be stable to obtain hydrophilic diisocyanate; wherein the hydrophilic chain extender is added for 3 to 10 times in a fractional manner, and the hydrophilic chain extender is added for multiple times, and the reaction is carried out at the temperature of between 50 and 60 ℃ until the liquid in the kettle is transparent after each part of the hydrophilic chain extender is added.
2. The method for preparing hydrophilic diisocyanate according to claim 1, comprising the steps of: adding diisocyanate and cosolvent into a reaction kettle, starting a stirrer, heating to 30-80 ℃, adding a hydrophilic chain extender in several times, reacting at 50-60 ℃ for 0.5-3 hours after adding the hydrophilic chain extender each time until the hydrophilic chain extender is added for the last time, reacting at 50-60 ℃ for 0.5-3 hours, heating to 60-80 ℃ again for 6-20 hours, and cooling and discharging when the NCO is reduced to be stable to obtain hydrophilic diisocyanate; wherein the hydrophilic chain extender is added for 3 to 10 times in a fractional manner, and then the hydrophilic chain extender is added for multiple times, and after each hydrophilic chain extender is added, the reaction is carried out at the temperature of between 50 and 60 ℃ until the liquid in the kettle is transparent;
the molar ratio of the diisocyanate to the hydrophilic chain extender is (3-4): 1; the diisocyanate is at least one of MDI, HMDI, TDI, HDI, IPDI or XDI; the hydrophilic chain extender is a micromolecule diol at least containing one sulfonate group-containing micromolecule diol or amino sulfonate group-containing micromolecule diol.
3. The method according to claim 2, wherein the cosolvent is added in an amount of 0-40% by weight based on the weight of the diisocyanate.
4. The polyurethane emulsion is characterized by being prepared by the following preparation method: reacting the hydrophilic diisocyanate of claim 1 with a dihydroxy compound to obtain an aqueous polyurethane resin with a hydroxyl group at the end, and adding water to emulsify and disperse to obtain a polyurethane emulsion; the dihydroxy compound is at least one of polyester diol, polyether diol, polycaprolactone diol, hydroxyl-terminated alkyd resin, hydroxyl-terminated organic silicon resin, polyacrylic resin with hydroxyl or diol with the molecular weight less than 300.
5. A water-based polyurethane curing agent, which is prepared by reacting the hydrophilic diisocyanate according to claim 1 with a polyol.
6. A blocked aqueous polyisocyanate curing agent, which is obtained by reacting the aqueous polyurethane curing agent of claim 5 with a blocking agent.
7. Use of the hydrophilic diisocyanate of claim 1 in the preparation of an aqueous polyurethane coating, an aqueous polyurethane adhesive, an aqueous polyurethane vehicle, an aqueous leather finishing agent, an aqueous textile finishing agent, or an aqueous ink vehicle.
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| CN112079752B (en) * | 2020-09-17 | 2022-11-08 | 陕西科技大学 | Hydroxysulfonic acid type hydrophilic chain extender, preparation method thereof, high-solid-content aqueous polyurethane prepared based on hydroxysulfonic acid type hydrophilic chain extender and preparation method of polyurethane |
| CN112745795B (en) * | 2020-12-28 | 2022-07-15 | 辽宁恒星精细化工有限公司 | Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method |
| CN114044875B (en) * | 2021-11-04 | 2023-05-26 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer and preparation method and application thereof |
| CN114634605B (en) * | 2022-03-07 | 2023-11-21 | 襄阳精信汇明科技股份有限公司 | Water-dispersible polyisocyanate curing agent and preparation method and application thereof |
| CN114736351A (en) * | 2022-05-10 | 2022-07-12 | 江苏富琪森新材料有限公司 | Blocked isocyanate curing agent, preparation method thereof and baking type coating |
| CN114907542A (en) * | 2022-06-06 | 2022-08-16 | 合肥科天水性科技有限责任公司 | Antibacterial anionic waterborne polyurethane resin and preparation method thereof |
| CN115433341B (en) * | 2022-09-08 | 2024-01-05 | 黎明化工研究设计院有限责任公司 | Hydrophilic polyurethane acrylate, hydrophilic trifunctional acrylate and preparation method and application thereof |
| CN115368538B (en) * | 2022-09-16 | 2023-12-26 | 四川亭江新材料股份有限公司 | Polyurethane leather fatting agent and preparation method thereof |
| CN115785367A (en) * | 2022-11-04 | 2023-03-14 | 佛山市精信汇明科技有限公司 | Preparation method and application of waterborne polyurethane resin emulsion without added organic solvent |
| CN115785881B (en) * | 2022-12-14 | 2024-03-12 | 佛山市精信汇明科技有限公司 | Water-based polyurethane adhesive for shoemaking and application thereof |
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| TW200932771A (en) * | 2008-01-25 | 2009-08-01 | Great Eastern Resins Ind Co Ltd | Improved process of preparing high performance waterborne aliphatic-aromatic mixed polyurethanes |
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| WO2021185335A1 (en) | 2021-09-23 |
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