CN117487113A - Aqueous polyurethane emulsion and preparation method and application thereof - Google Patents

Aqueous polyurethane emulsion and preparation method and application thereof Download PDF

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Publication number
CN117487113A
CN117487113A CN202311548405.4A CN202311548405A CN117487113A CN 117487113 A CN117487113 A CN 117487113A CN 202311548405 A CN202311548405 A CN 202311548405A CN 117487113 A CN117487113 A CN 117487113A
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China
Prior art keywords
prepolymer
weight
aqueous polyurethane
polyurethane emulsion
parts
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CN202311548405.4A
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Chinese (zh)
Inventor
吴奎
蒋红梅
宋海峰
唐劲松
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Shanghai Huafon New Material Research & Development Technology Co ltd
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Shanghai Huafon New Material Research & Development Technology Co ltd
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Priority to CN202311548405.4A priority Critical patent/CN117487113A/en
Publication of CN117487113A publication Critical patent/CN117487113A/en
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    • C08G18/08—Processes
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    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
    • D06N3/148—(cyclo)aliphatic polyisocyanates

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Abstract

The invention provides a waterborne polyurethane emulsion and a preparation method and application thereof, wherein the raw materials of the waterborne polyurethane emulsion comprise a first prepolymer, a second prepolymer, hydroxyl diamine, a polyamine chain extender, dihydrazide and a neutralizing agent, the raw materials of the first prepolymer comprise a first polymeric polyol, a first isocyanate, hydroxyl epoxy resin, aminosilicone, a ketocarbonyl group-containing micromolecular alcohol and a first hydrophilic chain extender, and the raw materials of the second prepolymer comprise a second polymeric polyol, a second isocyanate, a polyol chain extender and a second hydrophilic chain extender; the first prepolymer and the second prepolymer with different hydrophilic contents are selected for matching, and the hydroxyl diamine, the polyamine chain extender and the dihydrazide are matched for chain extension, so that the crosslinking degree of polyurethane resin is effectively improved, and the aqueous polyurethane emulsion with excellent scratch resistance, heat resistance, weather resistance and mechanical strength is obtained.

Description

Aqueous polyurethane emulsion and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a waterborne polyurethane emulsion and a preparation method and application thereof.
Background
The aqueous polyurethane is widely applied to the fields of paint, adhesive, printing ink, synthetic leather and the like. At present, the relatively mature industrial production methods of the waterborne polyurethane are a prepolymer method and an acetone method; the acetone method is generally to prepare a prepolymer by the reaction of polyalcohol, polyisocyanate, micromolecular diol or diamine and the like, simultaneously add a large amount of acetone for dilution, dissolution and viscosity reduction, then neutralize and add water for dispersion, and then remove the acetone by distillation to prepare a water-based polyurethane product; the prepolymer method generally refers to preparing a prepolymer under the condition of no solvent or a small amount of solvent, wherein the prepolymer is basically not chain-extended, dispersing the prepolymer into an aqueous solution, and then chain-extending by using aliphatic amine or hydrazine to prepare the aqueous polyurethane product.
The acetone method needs to use a large amount of acetone as a solvent, consumes a large amount of energy in the synthesis and desolventizing recovery process, has low boiling point of the acetone, is easy to volatilize, has the recovery rate of more than 99 percent, and can cause a large amount of carbon emission and energy waste; the prepolymer method is difficult to emulsify due to high viscosity of the prepolymer, and cannot be widely popularized, and the prepared aqueous polyurethane resin has small molecular weight, basically does not contain a crosslinking structure and has a narrow application range.
At present, the common solution is to reduce the viscosity of the prepolymer by means of special isocyanate, special polyol, a small amount of high boiling point solvent, or dilution of acrylic active monomers, and the like so as to synthesize polyurethane dispersion, but the high crosslinking degree, high strength and excellent performance of the product cannot be synthesized due to the viscosity limitation of the prepolymer, and high-power emulsification equipment is required for production emulsification, so that the operation difficulty is high and the product stability is poor; meanwhile, based on the environmental protection and performance requirements, the preparation of the aqueous polyurethane dispersion with high crosslinking degree by adopting the prepolymer method is a necessary trend and is also an industrial difficulty.
Therefore, there is an urgent need to develop an aqueous polyurethane emulsion suitable for a prepolymer method to solve at least one of the above-mentioned technical problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the aqueous polyurethane emulsion, the preparation method and the application thereof, and the first prepolymer and the second prepolymer with different hydrophilic contents are selected to be matched as main preparation raw materials of the aqueous polyurethane emulsion, and the first prepolymer is used as a diluent, so that the viscosity of a system can be effectively reduced, and three raw materials of hydroxyl diamine, polyamine chain extender and dihydrazide are used for carrying out post chain extension, so that the crosslinking degree of polyurethane resin is greatly improved, and the aqueous polyurethane emulsion with excellent scratch resistance, heat resistance, weather resistance and mechanical strength is obtained.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an aqueous polyurethane emulsion, wherein the preparation raw materials of the aqueous polyurethane emulsion comprise a first prepolymer, a second prepolymer, hydroxyl diamine, a polyamine chain extender, a dihydrazide and a neutralizer;
the preparation raw materials of the first prepolymer comprise first polymeric polyol, first isocyanate, first hydrophilic chain extender, hydroxyl epoxy resin, aminosilicone and small molecule alcohol containing ketocarbonyl;
the preparation raw materials of the second prepolymer comprise second polymeric polyol, second isocyanate, second hydrophilic chain extender and polyol chain extender.
The preparation raw materials of the aqueous polyurethane emulsion provided by the invention comprise a first prepolymer, a second prepolymer, hydroxyl diamine, a polyamine chain extender, dihydrazide and a neutralizer, wherein the first prepolymer and the second prepolymer have different hydrophilic contents, the preparation raw materials of the first prepolymer comprise first polymerized polyol, first isocyanate, hydroxyl epoxy resin, aminosilicone, small molecular alcohol containing ketocarbonyl and first hydrophilic chain extender, the hydroxyl epoxy resin, aminosilicone and small molecular alcohol containing ketocarbonyl in the preparation raw materials can be used as end-capping agents, so that the first prepolymer is a polyurethane prepolymer capped by ketocarbonyl, siloxane and epoxy together, and meanwhile, the preparation raw materials are matched, so that the first prepolymer also has the characteristics of low molecular weight, low viscosity and post-crosslinking, and further can be used as a diluent, and the viscosity of the second prepolymer can be effectively reduced after the first prepolymer and the second prepolymer are mixed; secondly, after the first prepolymer and the second prepolymer are mixed, three raw materials of hydroxyl diamine, polyamine chain extender and dihydrazide are added as chain extender, and hydroxyl, hydrazine group and amine group can be introduced into a molecular chain segment of the second prepolymer, so that siloxane and hydroxyl in the emulsion are crosslinked in a micelle under the condition of heat preservation and heating, and ketone carbonyl and hydrazine group and amino group can be subjected to crosslinking reaction in the film forming and drying process of the emulsion, and further the crosslinking degree of polyurethane resin can be greatly improved, and the aqueous polyurethane emulsion with excellent wear resistance, heat resistance, weather resistance and mechanical strength is obtained;
specifically, the analysis is as follows:
(1) For the crosslinking reaction of siloxane and hydroxyl, in the conventional acetone aqueous polyurethane synthesis method, aminosilicone is generally added in a prepolymerization stage and dispersed to form an aqueous polyurethane dispersion, and the aqueous polyurethane dispersion is subjected to hydrolysis to generate silicon hydroxyl and rapid condensation to form crosslinking in the drying film forming process, but the method has the defects that the siloxane in the aqueous polyurethane dispersion cannot stably exist in an emulsion containing acetone, moisture is extremely easy to swell into the micelle to cause hydrolysis failure of the siloxane, and the emulsion is easy to gel and has poor storage stability; according to the invention, amino siloxane is added into the preparation raw material of the first prepolymer, and hydroxyl diamine is added into the preparation raw material of the first prepolymer to carry out chain extension on the second prepolymer, so that siloxane and hydroxyl are respectively introduced into the first prepolymer and the second prepolymer, and meanwhile, the content of hydrophilic groups in the first prepolymer is lower than that of the second prepolymer, so that the first prepolymer is wrapped in a micelle after the first prepolymer and the second prepolymer are mixed and emulsified, the siloxane groups can be effectively prevented from being hydrolyzed when meeting water, and the hydroxyl groups in the siloxane in the first prepolymer and the hydroxyl groups in the second prepolymer can be subjected to crosslinking reaction in the micelle after the emulsification and the hydroxyl groups are heated, so that the storage stability of the polyurethane emulsion is not influenced, and the obtained polyurethane emulsion has excellent storage stability, excellent wear resistance, heat resistance, weather resistance and mechanical strength;
wherein, the reaction formula of the siloxane and the hydroxyl groups in the cross-linking reaction is as follows: r is R 1 -Si-(OR) 3 +H 2 N-R’→R 1 -Si-(OR’) 3 +3R-OH, because methanol or ethanol is produced after the siloxane reaction, the reaction end point can be determined by monitoring the content of methanol or ethanol;
(2) For the cross-linking reaction of the ketone carbonyl and the hydrazine, adding small molecular alcohol containing the ketone carbonyl into the preparation raw material of the first prepolymer, introducing binary hydrazine as a rear chain extender, further introducing the ketone carbonyl into the first prepolymer, introducing the hydrazine group into the molecular chain segment of the second prepolymer, and carrying out cross-linking reaction on the ketone carbonyl and the hydrazine group at room temperature under weak acidity condition, namely, in the process of drying the polyurethane emulsion, the polyurethane emulsion gradually presents weak acidity along with volatilization of moisture and a neutralizing agent, and the ketone carbonyl and the hydrazine group can carry out cross-linking reaction to form self-crosslinking resin;
wherein, the structural formula of the cross-linking reaction of the ketone carbonyl and the hydrazine is specifically shown as follows:
(3) For the crosslinking reaction of epoxy groups and amine groups, hydroxyl epoxy resin is added into the preparation raw material of the first prepolymer, and can be crosslinked with the residual amine groups in the second prepolymer in the film forming and drying processes;
in summary, the three crosslinking systems are introduced into the prepolymer method, so that the viscosity of the prepolymer can be reduced, the aqueous polyurethane emulsion with high crosslinking degree can be prepared, and the application range of the prepolymer method is effectively widened.
The "polyamine chain extender" in the present invention refers to an amine chain extender having a functionality of not less than 2 except for the hydroxyl diamine; the "polyol chain extender" refers to an alcohol chain extender having a functionality of not less than 2.
Preferably, the preparation raw materials of the aqueous polyurethane emulsion comprise the following components in parts by weight:
wherein the first prepolymer may be 120 parts by weight, 140 parts by weight, 160 parts by weight, 180 parts by weight, 205 parts by weight, 210 parts by weight, 215 parts by weight, 220 parts by weight, 225 parts by weight, 230 parts by weight, 235 parts by weight, 240 parts by weight, 245 parts by weight, or the like.
The second prepolymer may be 300 parts by weight, 500 parts by weight, 800 parts by weight, 1000 parts by weight, 1300 parts by weight, 1500 parts by weight, 1700 parts by weight, 1900 parts by weight, or the like.
The hydroxyl diamine may be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, or the like.
The polyamine chain extender may be 0.5, 1, 1.5, 2, 2.5, 4, 6, 8, 10, 12, 14, etc. parts by weight.
The dihydrazide includes 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, 21 parts by weight, 23 parts by weight, or the like.
The neutralizing agent may be 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, or the like.
Preferably, the viscosity of the first prepolymer is less than 5000cps, for example 4500cps, 4000cps, 3500cps, 3000cps, 2500cps, 2000cps, 1500cps, 1000cps, 500cps, 300cps, 200cps or 100cps, etc., and the test condition of the viscosity is 3# rotor, 30rpm at 25 ℃.
Preferably, the number average molecular weight of the first prepolymer is 2500 to 15000, for example 3000, 5000, 7000, 9000, 11000 or 13000, etc.
Preferably, the first prepolymer comprises the following components in parts by weight:
wherein the first polymeric polyol may be 130 parts by weight, 135 parts by weight, 140 parts by weight, 145 parts by weight, 150 parts by weight, 155 parts by weight, 160 parts by weight, 165 parts by weight, 170 parts by weight, 175 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, or the like.
The first isocyanate may be 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, or the like.
The hydroxyl epoxy resin may be 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, or the like.
The aminosilicone may be 2, 4, 6, 8, 10, 12, 14, 16, 18, etc. parts by weight.
The small molecular alcohol containing the ketocarbonyl group can be 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight or 18 parts by weight, and the like.
The first hydrophilic chain extender may be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, or the like.
Preferably, the preparation raw materials of the second prepolymer comprise the following components in parts by weight:
wherein the second polymeric polyol may be 200 parts by weight, 220 parts by weight, 240 parts by weight, 260 parts by weight, 280 parts by weight, 300 parts by weight, 320 parts by weight, 340 parts by weight, 400 parts by weight, 500 parts by weight, 600 parts by weight, 700 parts by weight, 800 parts by weight, 900 parts by weight, or the like.
The second isocyanate may be 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, or the like.
The polyol chain extender may be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, or the like.
The second hydrophilic chain extender may be 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, etc. parts by weight.
The mass of the first hydrophilic chain extender is 75% lower than that of the second hydrophilic chain extender.
Preferably, the first and second polymeric polyols each independently have a number average molecular weight of 500 to 4000, such as 1000, 1500, 2000, 2500, 3000 or 3500, etc.
Preferably, the first and second polymeric polyols each independently comprise any one or a combination of at least two of polytetrahydrofuran ether glycol, polypropylene oxide/ethylene oxide ether glycol, polycarbonate glycol, polycaprolactone glycol, neopentyl glycol polyadipate glycol, polyhexamethylene adipate glycol, or polybutylene adipate glycol.
Preferably, the first isocyanate and the second isocyanate each independently comprise any one or a combination of at least two of 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane-4, 4-diisocyanate (MDI), hexamethylene diisocyanate, dicyclohexylmethane diisocyanate (HMDI) or Toluene Diisocyanate (TDI), and further preferably any one or a combination of at least two of isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or diphenylmethane-4, 4-diisocyanate.
Preferably, the first hydrophilic chain extender and the second hydrophilic chain extender each independently comprise Dimethylolpropane (DMPA) and/or Dimethylolbutane (DMBA).
Preferably, the hydroxyl epoxy resin comprises any one or a combination of at least two of epoxy resin E-44, epoxy resin E-12 or epoxy resin E-51.
Preferably, the aminosilicone comprises gamma-aminopropyl trimethoxysilane (KH 540) and/or gamma-aminopropyl triethoxysilane (KH 550).
The invention further preferably discloses gamma-aminopropyl trimethoxy silane (with the trade name of KH 540), wherein amino groups react with isocyanate to be grafted on polyurethane chain segments, and methoxy silane can react and crosslink with hydroxyl groups at 60-70 ℃.
Preferably, the small molecule alcohol containing ketocarbonyl group comprises any one or at least two of 5-hydroxy-2, 5-dimethyl-3-hexanone, 4-hydroxy-3, 3-dimethyl cyclohexanone or 5-hydroxy-2-hexanone, and further preferably 4-hydroxy-3, 3-dimethyl cyclohexanone and/or 5-hydroxy-2-hexanone.
Preferably, the polyol chain extender comprises any one or a combination of at least two of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol, neopentyl glycol, hexanediol or 3-methyl-1, 5-pentanediol.
Preferably, the preparation raw materials of the first prepolymer and the second prepolymer also comprise a catalyst.
Preferably, the catalyst may be selected from BICAT 8118, a leading chemical company in the United states.
Preferably, the catalyst is added in an amount of 0.02 to 0.2%, for example, 0.04%, 0.06%, 0.08%, 0.1%, 0.12%, 0.14%, 0.16% or 0.18% based on 100% of the solid content of the aqueous polyurethane emulsion.
Preferably, the hydroxy diamine comprises hydroxy ethylenediamine.
Preferably, the polyamine chain extender comprises any one or a combination of at least two of ethylenediamine, isophorone diamine, diethylenetriamine or triethylenetetramine.
Preferably, the dihydrazide comprises hydrazine hydrate and/or adipic acid dihydrazide.
Preferably, the neutralizing agent comprises triethylamine and/or N, N-dimethylethanolamine.
Preferably, the preparation raw materials of the aqueous polyurethane emulsion further comprise water.
Preferably, the aqueous polyurethane emulsion has a solids content of 30 to 50%, for example 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46% or 48%, etc.
In a second aspect, the present invention provides a method for preparing the aqueous polyurethane emulsion according to the first aspect, the method comprising the steps of:
(1) Reacting a first polymeric polyol, a first isocyanate and a first hydrophilic chain extender, adding hydroxy epoxy resin and small molecular alcohol containing ketocarbonyl groups for reaction, adding optional catalyst for reaction, and finally adding aminosilicone for reaction to obtain a first prepolymer;
reacting the second polymeric polyol with a second isocyanate, adding a second hydrophilic chain extender, a polyol chain extender and optionally a catalyst, and reacting to obtain a second prepolymer;
(2) Mixing the first prepolymer and the second prepolymer obtained in the step (1), adding a neutralizing agent for mixing, adding water for dispersing, and finally adding hydroxyl diamine, polyamine chain extender and dihydrazide for chain extension, and carrying out heat preservation reaction to obtain the aqueous polyurethane emulsion.
In the preparation method, in the step (1), first polymeric polyol, first isocyanate and first hydrophilic chain extender are reacted, then hydroxyl epoxy resin and small molecular alcohol containing ketocarbonyl are adopted as chain extender to carry out partial end capping, and finally aminosilicone is added to carry out complete end capping, so that a first prepolymer is obtained; reacting a second polymer polyol with a second isocyanate and a second hydrophilic chain extender, and adopting small molecular alcohols to carry out chain extension to obtain a second prepolymer; in the step (2), the first prepolymer and the second prepolymer obtained in the step (1) are mixed firstly, the overall viscosity of the prepolymer is reduced, then water is added for emulsification and dispersion, and three of hydroxyl diamine, polyamine chain extender and dihydrazide are added for post-chain extension, after the post-chain extension is completed, heat preservation reaction is carried out to promote the crosslinking reaction of siloxane in the first prepolymer and hydroxyl in the second prepolymer, and the reaction end point is determined by testing the content of methanol/ethanol, so that the aqueous polyurethane emulsion with different crosslinking degrees can be prepared.
Preferably, the pH of the emulsion after the chain extension in step (2) is 7.5 to 11, e.g. 8, 8.5, 9, 9.5, 10 or 10.5, etc.
Preferably, the temperature of the incubation reaction is 50 to 70 ℃, for example 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, or the like.
Preferably, the incubation time is not less than 2 hours, such as 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, or 2.9 hours, etc.
As a preferable technical scheme of the invention, the preparation method of the aqueous polyurethane emulsion comprises the following steps:
(1) Uniformly mixing the first polymeric polyol and the first isocyanate at 50-60 ℃ (such as 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃ or 59 ℃ and the like), heating to 80-90 ℃ (such as 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃ or 89 ℃ and the like) to react so that the-NCO content of the system is not higher than 6%, cooling to 60-80 ℃ (such as 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃ or 78 ℃ and the like), adding hydroxy epoxy resin, small molecular alcohol containing ketocarbonyl and the first hydrophilic chain extender to react for 2-3 hours (such as 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours or 2.9 hours and the like), adding optional catalyst to continue the reaction for 2-3 hours (such as 2.1 hours, 2.2 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 ℃, 2.8 hours, 76 ℃ or 78 ℃ and the like), and then adding the pre-amino group into the system for a reaction for not more than 32 minutes (such as 28-32 minutes, 32 minutes and the like, the pre-reaction for example, the reaction for 28-32 minutes and the second hydrophilic chain extender is not higher than 32 minutes (such as 2.36 minutes, 30 minutes and the first hydrophilic chain extender);
reacting the second polymeric polyol and the second isocyanate at 80-90 ℃ (e.g., 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ or the like) until the-NCO content of the system is not higher than 18%, cooling to 70-80 ℃ (e.g., 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ or the like), adding a second hydrophilic chain extender, a polyol chain extender and optionally a catalyst, and reacting for 2-3 hours (e.g., 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or the like), and determining that the-NCO content of the system is less than 11%, thereby obtaining a second prepolymer;
(2) Mixing the first prepolymer obtained in the step (1) with the second prepolymer at a temperature of not higher than 40 ℃ (such as 38 ℃, 36 ℃, 34 ℃, 32 ℃ or 30 ℃), adding a neutralizing agent for mixing, adding water for emulsification and dispersion, finally adding hydroxyl diamine, a polyamine chain extender and dihydrazide for chain extension, wherein the pH value of the emulsion after chain extension is 7.5-11 (such as 8, 8.5, 9, 9.5, 10 or 10.5), and finally carrying out heat preservation reaction at 50-70 ℃ for not lower than 2 hours to obtain the aqueous polyurethane emulsion.
In a third aspect, the invention provides the use of an aqueous polyurethane emulsion according to the first aspect for the preparation of a coating, adhesive, ink or synthetic leather.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation raw materials of the aqueous polyurethane emulsion provided by the invention do not contain organic solvents, and the preparation process does not use the organic solvents, thus the aqueous polyurethane emulsion belongs to a completely environment-friendly product;
(2) The aqueous polyurethane emulsion provided by the invention is prepared by limiting preparation raw materials comprising a first prepolymer, a second prepolymer, hydroxyl diamine, a polyamine chain extender, a dihydrazide and a neutralizing agent, and further limiting the preparation raw materials of the first prepolymer to comprise a first polymeric polyol, a first isocyanate, a hydroxyl epoxy resin, aminosilicone, a small molecular alcohol containing a ketocarbonyl group and a first hydrophilic chain extender, and the preparation raw materials of the second prepolymer to comprise a second polymeric polyol, a second isocyanate, a polyol chain extender and a second hydrophilic chain extender; three crosslinking reaction volumes of ketone-hydrazine reaction, amine-epoxy reaction and siloxane-hydroxyl reaction are introduced into the system, so that the viscosity of a prepolymer can be reduced, the obtained aqueous polyurethane emulsion has higher crosslinking degree, and the compactness, wear resistance, heat resistance, weather resistance and mechanical strength of the polyurethane emulsion after film formation are improved;
(3) The preparation method of the aqueous polyurethane emulsion provided by the invention belongs to a prepolymer method, and uses aminosilane, epoxy and ketocarbonyl alcohol to end, so that the molecular weight of the prepolymer is effectively reduced, the technical problems of high synthesis viscosity, poor raw material adaptability and difficult dispersion of the conventional prepolymer method are solved, the stability of the aqueous polyurethane in the synthesis reaction process is improved, and the application range of the prepolymer method is enlarged.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The preparation method of the aqueous polyurethane emulsion comprises the following steps:
(1) 170g of polytetrahydrofuran ether glycol (with the number average molecular weight of 2000) and 2.6g of DMPA are put into a glass reaction kettle together, the temperature of the reaction kettle is raised to 55 ℃, 13g of HDI and 19.5g of IPDI are added and stirred uniformly, the reaction temperature is controlled to be 85 ℃, and the-NCO content of a test system after 3 hours of reaction is less than 2.5%; cooling the system to 65 ℃, adding 11g of hydroxy epoxy resin E-44 and 10.5g of 4-hydroxy-3, 3-dimethylcyclohexanone, carrying out heat preservation reaction for 2.5h, adding 0.4g of catalyst (BICAT 8118 of advanced chemical company in the United states), carrying out heat preservation for 2.5h, and determining that the-NCO content of the system is less than 1%; cooling the system to below 40 ℃, adding 10g of KH540 for reaction for 30min to obtain a first prepolymer with the viscosity of 120cps at 25 ℃;
160g of polybutylene adipate glycol (with the number average molecular weight of 2000) and 160g of neopentyl glycol adipate glycol (with the number average molecular weight of 2000) are put into another reaction kettle to be mixed, stirred uniformly at 55 ℃, 50g of TDI and 30g of MDI are added, the reaction temperature is controlled at 85 ℃, the reaction is carried out for 3 hours, and the-NCO content of a test system is less than 5.1%; cooling the system to 75 ℃, adding 6.8g of DMPA, 5g of 1, 4-butanediol and 0.77g of catalyst (BICAT 8118 of advanced chemical Co., USA), keeping the temperature for 2.5h, determining that the NCO content of the system is less than 3.0%, and stopping heating to obtain a second prepolymer;
(2) Cooling the reaction kettle of the second prepolymer to below 40 ℃, mixing the first prepolymer obtained in the step (1) with the second prepolymer obtained in the step (1), adding 7.08g of triethylamine to mix after mixing, adding 667g of deionized water to carry out high-speed emulsification and dispersion, finally adding 10g of hydroxyethyl ethylenediamine, 1.5g of ethylenediamine and 12g of adipic dihydrazide to carry out chain extension, keeping the pH value of the emulsion at 8.2 after chain extension, carrying out heat preservation reaction for 2 hours at 60 ℃, and cooling to normal temperature to obtain the 50% solid aqueous polyurethane emulsion.
Example 2
The preparation method of the aqueous polyurethane emulsion comprises the following steps:
(1) Putting 100g of polypropylene oxide ether glycol (with the number average molecular weight of 2000) and 65g of polyhexamethylene adipate glycol (with the number average molecular weight of 2000) into a glass reaction kettle together, heating the reaction kettle to 55 ℃, stirring uniformly, adding 14g of HMDI, 40g of IPDI and 11.2g of DMPA, controlling the reaction temperature to 85 ℃, and reacting for 3 hours, wherein the-NCO content of a test system is less than 2.5%; cooling the system to 70 ℃, adding 11g of hydroxyl epoxy resin E-51 and 10g of 5-hydroxy-2-hexanone, carrying out heat preservation reaction for 2.5 hours, adding 0.4g of catalyst (BICAT 8118 of advanced chemical company in the United states), carrying out heat preservation for 2.5 hours, and measuring that the-NCO content of the system is less than 0.1%; cooling the system to below 40 ℃, adding 10g of KH550 to react for 30min to obtain a first prepolymer with the viscosity of 1000cps at 25 ℃;
100g of polytetrahydrofuran ether glycol (with the number average molecular weight of 2000) and 40g of polycarbonate diol (with the number average molecular weight of 2000) are put into another reaction kettle, uniformly stirred at 55 ℃, 90g of TDI and 15g of MDI are added, the reaction temperature is controlled to be 80 ℃, the reaction is carried out for 3 hours, and the-NCO content of a test system is less than 17.4%; cooling the system to 60 ℃, adding 21.3g of DMPA, 0.5g of 1, 4-butanediol and 0.3g of catalyst (BICAT 8118 of advanced chemical Co., USA), carrying out heat preservation reaction for 2.5h, measuring the NCO content of the system to be less than 10.7%, and stopping heating to obtain a second prepolymer;
(2) Cooling the reaction kettle of the second prepolymer to below 40 ℃, mixing the first prepolymer obtained in the step (1) with the second prepolymer obtained in the step (1), adding 31.3g of triethylamine to mix after mixing, adding 800g of deionized water to carry out high-speed emulsification and dispersion, finally adding 6g of hydroxyethyl ethylenediamine, 8.6g of ethylenediamine and 6.6g of hydrazine hydrate to carry out chain extension, keeping the pH value of the emulsion at 9.5 after chain extension, carrying out heat preservation reaction for 3 hours at 50 ℃, and reducing the temperature to normal temperature to obtain the aqueous polyurethane emulsion with 40% of solid content.
Example 3
(1) 360g of polypropylene oxide ether glycol (with the number average molecular weight of 3000) is put into a glass reaction kettle, the glass reaction kettle is heated to 60 ℃ and stirred uniformly, 15g of HDI, 15g of IPDI and 2g of DMPA are added, the reaction temperature is controlled to be 90 ℃, the reaction is carried out for 3 hours, and the-NCO content of a test system is less than 3.69%; cooling the system to 60 ℃, adding 1.1g of hydroxyl epoxy resin E-44 and 5g of 4-hydroxy-3, 3-dimethylcyclohexanone, reacting for 3 hours at a temperature, adding 0.4g of catalyst (BICAT 8118 of advanced chemical Co., USA), reacting for 2.5 hours at a temperature, and determining that the-NCO content of the system is less than 0.1%; cooling the system to below 40 ℃, adding 2g of KH540 for reaction for 30min to obtain a first prepolymer with the viscosity of 500cps at 25 ℃;
600g of polybutylene adipate glycol (with the number average molecular weight of 4000) is put into another reaction kettle, uniformly stirred at 55 ℃, 27g of IPDI and 30g of HDI are added, the reaction temperature is controlled to be 90 ℃, the reaction is carried out for 3 hours, and the-NCO content of a test system is less than 1.9%; cooling the system to 80 ℃, adding 10g of DMPA, 1g of 1, 4-butanediol and 0.77g of catalyst (BICAT 8118 of advanced chemical Co., USA), keeping the temperature for 2.5 hours, determining that the NCO content of the system is less than 0.1%, and stopping heating to obtain a second prepolymer;
(2) Cooling the reaction kettle of the second prepolymer to below 40 ℃, mixing the first prepolymer obtained in the step (1) with the second prepolymer obtained in the step (1), adding 13.5g of triethylamine to mix after mixing, adding 1058g of deionized water to carry out high-speed emulsification and dispersion, finally adding 1g of hydroxyethyl ethylenediamine, 1.5g of ethylenediamine and 5g of adipic dihydrazide to carry out chain extension, keeping the pH value of the emulsion at 8.7 after chain extension, carrying out heat preservation reaction for 2 hours at 50 ℃, and reducing the temperature to normal temperature to obtain the aqueous polyurethane emulsion with 50% of solid content.
Example 4
(1) 150g of polytetrahydrofuran ether glycol (with the number average molecular weight of 2000) is put into a glass reaction kettle, the reaction kettle is heated to 60 ℃ and stirred uniformly, 12g of HDI, 27g of IPDI and 2.6g of DMPA are added, the reaction temperature is controlled to be 80 ℃, the reaction is carried out for 3 hours, and the-NCO content of a test system is less than 5.2%; cooling the system to 60 ℃, adding 20g of hydroxyl epoxy resin E-44 and 15g of 5-hydroxy-2, 5-dimethyl-3-hexanone, carrying out heat preservation reaction for 3 hours, adding 0.2g of catalyst (BICAT 8118 of advanced chemical company in the United states), carrying out heat preservation for 2.5 hours, and determining that the-NCO content of the system is less than 1.7%; cooling the system to below 40 ℃, adding 20g of KH550 to react for 30min to obtain a first prepolymer with the viscosity of 300cps at 25 ℃;
adding 300g of polybutylene adipate glycol (with the number average molecular weight of 2000) into a reaction kettle, mixing, uniformly stirring at 55 ℃, adding 69g of TDI and 15g of HDI, controlling the reaction temperature to 90 ℃, and reacting for 3 hours, wherein the-NCO content of a test system is less than 6.7%; cooling the system to 80 ℃, adding 8g of DMPA, 4g of 1, 6-hexanediol and 0.8g of catalyst (BICAT 8118 of advanced chemical Co., USA), keeping the temperature for 2.5 hours, determining that the NCO content of the system is less than 4.5%, and stopping heating to obtain a second prepolymer;
(2) Cooling the reaction kettle of the second prepolymer to below 40 ℃, mixing the first prepolymer obtained in the step (1) with the second prepolymer obtained in the step (1), adding 7.8g of triethylamine to mix after mixing, adding 655g of deionized water to carry out high-speed emulsification and dispersion, finally adding 10g of hydroxyethyl ethylenediamine, 2g of isophorone diamine and 15g of adipic dihydrazide to carry out chain extension, keeping the pH value of the emulsion at 8.9 after chain extension, carrying out heat preservation reaction for 2 hours at 50 ℃, and reducing the temperature to normal temperature to obtain the 50% solid aqueous polyurethane emulsion.
Example 5
(1) 150g of polytetrahydrofuran ether glycol (with the number average molecular weight of 4000) is put into a glass reaction kettle, the reaction kettle is heated to 60 ℃ and stirred uniformly, 12g of HDI, 12g of IPDI and 2.6g of DMPA are added, the reaction temperature is controlled to be 80 ℃, the reaction is carried out for 3 hours, and the-NCO content of a test system is less than 2.44%; cooling the system to 60 ℃, adding 1.1g of hydroxyl epoxy resin E-44 and 8g of 5-hydroxy-2, 5-dimethyl-3-hexanone, carrying out heat preservation reaction for 3 hours, adding 0.2g of catalyst (BICAT 8118 of advanced chemical company in the United states), carrying out heat preservation for 2.5 hours, determining that the-NCO content of the system is less than 0.1%, cooling to below 40 ℃, adding 2g of KH540, and reacting for 30 minutes to obtain a first prepolymer with the viscosity of 1200cps at 25 ℃;
adding 300g of polybutylene adipate glycol (with the number average molecular weight of 2000) into a reaction kettle, mixing, uniformly stirring at 55 ℃, adding 43g of TDI and 18g of HDI, controlling the reaction temperature to 90 ℃, and reacting for 3 hours, wherein the-NCO content of a test system is less than 3.9%; cooling the system to 80 ℃, adding 8.5g of DMPA, 4g of 1, 3-propanediol and 0.6g of catalyst (BICAT 8118 of advanced chemical Co., USA), keeping the temperature for 2.5h, determining that the NCO content of the system is less than 1.19%, and stopping heating to obtain a second prepolymer;
(2) Cooling a reaction kettle of a second prepolymer to below 40 ℃, mixing the first prepolymer obtained in the step (1) with the second prepolymer obtained in the step (1), adding 8.1g of triethylamine to mix after mixing, adding 560g of deionized water to carry out high-speed emulsification and dispersion, finally adding 1g of hydroxyethyl ethylenediamine, 2g of diethylenetriamine and 5g of adipic dihydrazide to carry out chain extension, keeping the pH value of the emulsion at 9.5 after chain extension, carrying out heat preservation reaction for 2 hours at 50 ℃, and reducing the temperature to normal temperature to obtain the aqueous polyurethane emulsion with 50% of solid content.
Example 6
An aqueous polyurethane emulsion differing from example 1 only in that KH550 was used instead of KH540, and other materials, amounts and preparation methods were the same as in example 1.
Comparative example 1
An aqueous polyurethane emulsion, the preparation method of which comprises: 450g of polybutylene adipate glycol (with the number average molecular weight of 3000) is put into a reaction kettle to be mixed, the mixture is stirred uniformly at 55 ℃, 27g of IPDI and 30g of HDI are added, the reaction temperature is controlled at 85 ℃, after 3 hours of reaction, the test-NCO content is less than 2.49%, the temperature is reduced to 70 ℃, 10g of DMPA and 1g of 1, 4-butanediol are put into the reaction kettle, after 2.5 hours of heat preservation, 0.6g of catalyst (BICAT 8118 of advanced chemical company in the United states) is added, after 2.5 hours of heat preservation, the test-NCO content is less than 1.1%, the heating is stopped, the reaction kettle is cooled to below 40 ℃, the test viscosity is 9000cps (at 25 ℃), 7.5g of triethylamine is put into the reaction kettle, after uniform mixing, 514g of deionized water is added for high-speed dispersion, and after 2.5g of ethylenediamine is put into the reaction kettle for chain extension, the 50% solid aqueous polyurethane emulsion can be prepared.
Comparative example 2
An aqueous polyurethane emulsion differing from example 1 only in that hydroxyethyl ethylenediamine was not added in step (2), and other substances, amounts and preparation methods were the same as in example 1.
Comparative example 3
An aqueous polyurethane emulsion differing from example 1 only in that ethylenediamine was not added in step (2), and other materials, amounts and preparation methods were the same as in example 1.
Comparative example 4
An aqueous polyurethane emulsion differing from example 1 only in that adipic acid dihydrazide was not added in step (2), and other substances, amounts and preparation methods were the same as in example 1.
Comparative example 5
An aqueous polyurethane emulsion differing from example 1 only in that no hydroxy epoxy resin E-44 was added in step (1), and other substances, amounts and preparation methods were the same as in example 1.
Comparative example 6
An aqueous polyurethane emulsion differing from example 1 only in that 4-hydroxy-3, 3-dimethylcyclohexanone was not added in step (1), and other substances, amounts and preparation methods were the same as in example 1.
Performance test:
1. testing of aqueous polyurethane emulsions
(1) Appearance of emulsion: directly observing;
(2) Viscosity: a 3# rotor, 30 revolutions test at 25 ℃ using a rotational viscometer;
(3) Degree of crosslinking: refers to the percentage of the total mass of the cross-linking agent (hydroxy epoxy resin, aminosilicone and small molecule alcohol containing ketocarbonyl group) to the total amount of polyurethane solids;
2. test of aqueous polyurethane film:
100g of aqueous polyurethane emulsion is thickened to a viscosity of about 5000cps (25 ℃ C.) by a thickener (commercial product), defoamed by a washing machine for 30min, scraped and coated with about 0.2mm on release paper, and dried by a drying oven at about 100 ℃ for 10min to obtain an aqueous polyurethane film;
(4) Mechanical strength: testing according to a testing method provided by national standard GB/T1040-92 plastic tensile property testing method;
(5) Heat resistance: cutting the prepared aqueous polyurethane adhesive film into square pieces with the length of 2 multiplied by 2cm, placing the square pieces in ovens with different temperatures, baking for 15 minutes, and observing the temperature at which the transparency and the appearance of the coating change;
(6) Ethanol rub resistance: after dipping the ethanol solution by using a specific brush, wiping the prepared aqueous polyurethane film back and forth until the adhesive film is damaged, and recording the wiping times.
The aqueous polyurethane emulsions provided in examples 1 to 6 and comparative examples 1 to 6 were tested according to the above test methods, and the test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen that:
(1) The aqueous polyurethane emulsion provided in examples 1-6 has a solid content of 50%, a viscosity of 108-300 cps, a crosslinking degree of 1.0-8.3%, and the further prepared aqueous polyurethane film has a mechanical strength of 14-32 MPa, a heat-resistant temperature of up to 120-170 ℃ and an ethanol wiping resistance of up to 40-200 times;
(2) Compared with example 1, the aqueous polyurethane emulsion provided in comparative example 1 has no cross-linked structure, so that the mechanical strength, the heat-resistant temperature and the ethanol scratch resistance of the polyurethane film are poor; the raw materials for preparing the aqueous polyurethane emulsion provided in the comparative example 2 do not contain hydroxyl ethylenediamine, and further lack siloxane and hydroxyl to crosslink, so that the density is low, and therefore the scratch resistance and the heat-resistant temperature after the aqueous polyurethane emulsion is prepared into a polyurethane film are obviously reduced, and the mechanical strength is slightly reduced; the aqueous polyurethane emulsion provided in comparative example 3 and comparative example 5 has no amine-epoxy crosslinking structure, so that the scratch resistance and mechanical strength after the polyurethane film is prepared are greatly reduced, and the heat resistance is slightly reduced; the aqueous polyurethane emulsions provided in comparative examples 4 and 6 do not contain a ketone-hydrazine crosslinked structure, so that the heat resistance temperature and mechanical strength after the polyurethane film is formed are greatly reduced;
in summary, it can be seen that only when the polyurethane contains three cross-linked structures of amine-epoxy, ketone-hydrazine and siloxane-hydroxyl, the further polyurethane film can have the effects of high mechanical strength, high heat resistance and high scratch resistance.
The applicant states that the present invention is illustrated by the above examples as an aqueous polyurethane emulsion and a method for preparing the same and application thereof, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. The preparation raw materials of the aqueous polyurethane emulsion comprise a first prepolymer, a second prepolymer, hydroxyl diamine, a polyamine chain extender, a dihydrazide and a neutralizer;
the preparation raw materials of the first prepolymer comprise first polymeric polyol, first isocyanate, first hydrophilic chain extender, hydroxyl epoxy resin, aminosilicone and small molecule alcohol containing ketocarbonyl;
the preparation raw materials of the second prepolymer comprise second polymeric polyol, second isocyanate, second hydrophilic chain extender and polyol chain extender.
2. The aqueous polyurethane emulsion according to claim 1, wherein the preparation raw materials of the aqueous polyurethane emulsion comprise the following components in parts by weight:
3. the aqueous polyurethane emulsion according to claim 1 or 2, wherein the viscosity of the first prepolymer is not higher than 5000cps;
preferably, the number average molecular weight of the first prepolymer is 2500 to 15000;
preferably, the first prepolymer comprises the following components in parts by weight:
preferably, the preparation raw materials of the second prepolymer comprise the following components in parts by weight:
4. the aqueous polyurethane emulsion of any one of claims 1 to 3, wherein the first and second polymeric polyols each independently have a number average molecular weight of 500 to 4000;
preferably, the first and second polymeric polyols each independently comprise any one or a combination of at least two of polytetrahydrofuran ether glycol, polypropylene oxide/ethylene oxide ether glycol, polycarbonate glycol, polycaprolactone glycol, neopentyl glycol polyadipate glycol, polyhexamethylene adipate glycol, or polybutylene adipate glycol;
preferably, the first isocyanate and the second isocyanate each independently comprise any one or a combination of at least two of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane-4, 4-diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate or toluene diisocyanate, further preferably any one or a combination of at least two of isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or diphenylmethane-4, 4-diisocyanate;
preferably, the first hydrophilic chain extender and the second hydrophilic chain extender each independently comprise dimethylolpropane and/or dimethylolbutane;
preferably, the hydroxy epoxy resin comprises any one or a combination of at least two of hydroxy epoxy resin E-44, hydroxy epoxy resin E-12 or hydroxy epoxy resin E-51;
preferably, the aminosilicone comprises gamma-aminopropyl trimethoxysilane and/or gamma-aminopropyl triethoxysilane;
preferably, the small molecule alcohol containing ketocarbonyl group comprises any one or at least two of 5-hydroxy-2, 5-dimethyl-3-hexanone, 4-hydroxy-3, 3-dimethyl cyclohexanone or 5-hydroxy-2-hexanone, and further preferably 4-hydroxy-3, 3-dimethyl cyclohexanone and/or 5-hydroxy-2-hexanone;
preferably, the polyol chain extender comprises any one or a combination of at least two of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol, neopentyl glycol, hexanediol or 3-methyl-1, 5-pentanediol.
5. The aqueous polyurethane emulsion according to any one of claims 1 to 4, wherein the raw materials for preparing the first prepolymer and the second prepolymer each further comprise a catalyst;
preferably, the catalyst is added in an amount of 0.02 to 0.2% based on 100% of the solid content of the aqueous polyurethane emulsion.
6. The aqueous polyurethane emulsion of any one of claims 1-5, wherein the hydroxydiamine comprises hydroxyethylenediamine;
preferably, the polyamine chain extender comprises any one or a combination of at least two of ethylenediamine, isophorone diamine, diethylenetriamine or triethylenetetramine;
preferably, the dihydrazide comprises hydrazine hydrate and/or adipic acid dihydrazide;
preferably, the neutralizing agent comprises triethylamine and/or N, N-dimethylethanolamine.
7. The aqueous polyurethane emulsion according to any one of claims 1 to 6, wherein the raw materials for preparing the aqueous polyurethane emulsion further comprise water;
preferably, the solid content of the aqueous polyurethane emulsion is 30-50%.
8. A method for preparing the aqueous polyurethane emulsion according to any one of claims 1 to 7, comprising the steps of:
(1) Reacting a first polymeric polyol, a first isocyanate and a first hydrophilic chain extender, adding hydroxy epoxy resin and small molecular alcohol containing ketocarbonyl groups for reaction, adding optional catalyst for reaction, and finally adding aminosilicone for reaction to obtain a first prepolymer;
reacting the second polymeric polyol with a second isocyanate, adding a second hydrophilic chain extender, a polyol chain extender and optionally a catalyst, and reacting to obtain a second prepolymer;
(2) Mixing the first prepolymer and the second prepolymer obtained in the step (1), adding a neutralizing agent for mixing, adding water for emulsification and dispersion, and finally adding hydroxyl diamine, a polyamine chain extender and diamine for chain extension, and carrying out heat preservation reaction to obtain the aqueous polyurethane emulsion.
9. The method according to claim 8, wherein the pH of the emulsion after the completion of the chain extension in step (2) is 7.5 to 11;
preferably, the temperature of the heat preservation reaction in the step (2) is 50-70 ℃;
preferably, the incubation time of step (2) is not less than 2 hours.
10. Use of the aqueous polyurethane emulsion according to any one of claims 1 to 7 for the preparation of paints, adhesives, inks or synthetic leather.
CN202311548405.4A 2023-11-20 2023-11-20 Aqueous polyurethane emulsion and preparation method and application thereof Pending CN117487113A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118165216A (en) * 2024-03-27 2024-06-11 盛鼎高新材料有限公司 Preparation method of polyurethane emulsion

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118165216A (en) * 2024-03-27 2024-06-11 盛鼎高新材料有限公司 Preparation method of polyurethane emulsion

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