阅读说明：本技术 一种可反应性水性聚氨酯的制备方法 (Preparation method of reactive waterborne polyurethane ) 是由 廖学明 王朝旭 贾佩萱 李革 廖显成 罗运 于 2020-12-09 设计创作，主要内容包括：本发明提供一种可反应性水性聚氨酯的制备方法,首先将低聚物多元醇、催化剂和亲水性单体加入盛有离子液体的反应容器,在70-90℃下搅拌混合均匀；之后降温至室温,加入芳香族二异氰酸酯反应0.5-1小时,升温至60-80℃保温反应2-4小时；之后加入扩链剂反应1-2小时,再加入封端剂反应1-2小时；之后降温至30-40℃,加入有机碱中和至弱碱性。之后滴加去离子水,搅拌分散；最后滴加含封闭型固化剂的水溶液,搅拌混合0.5-1小时,得到一种可反应性水性聚氨酯。本发明有效地解决了材料的VOC排放问题,实现了材料合成的“可控聚合”及产品的“高固低粘”之目标。所制得的材料经外交联反应形成梯形或网络结构,使其具有优异的热稳定性及力学性能。(The invention provides a preparation method of reactive waterborne polyurethane, which comprises the steps of firstly adding oligomer polyalcohol, a catalyst and a hydrophilic monomer into a reaction vessel containing ionic liquid, and stirring and mixing uniformly at 70-90 ℃; then cooling to room temperature, adding aromatic diisocyanate to react for 0.5-1 hour, heating to 60-80 ℃, and keeping the temperature to react for 2-4 hours; then adding a chain extender to react for 1-2 hours, and then adding an end capping agent to react for 1-2 hours; then cooling to 30-40 ℃, and adding organic alkali to neutralize to alkalescence. Then, deionized water is dripped, and stirring and dispersing are carried out; finally, dropping the aqueous solution containing the blocked curing agent, stirring and mixing for 0.5-1 hour to obtain the reactive waterborne polyurethane. The invention effectively solves the VOC emission problem of the material, and realizes the purposes of controllable polymerization of material synthesis and high solid content and low viscosity of the product. The prepared material forms a ladder-shaped or network structure through external crosslinking reaction, so that the material has excellent thermal stability and mechanical property.)

1. A preparation method of reactive waterborne polyurethane is characterized by comprising the following steps:

step 1, adding an organic tin catalyst, a hydrophilic monomer and oligomer polyol into a reaction vessel containing ionic liquid, and stirring and mixing uniformly at 70-90 ℃;

step 2, cooling the temperature of the reaction system to room temperature, adding aromatic diisocyanate, stirring at room temperature, and carrying out prepolymerization reaction for 1-2 hours;

step 3, heating to 60-80 ℃, and reacting for 3-5 hours in a heat preservation way;

step 4, reducing the temperature of the reaction system to 30-40 ℃, adding a chain extender with low relative molecular mass for chain extension reaction, and keeping the temperature for reaction for 1-3 hours;

step 5, heating to 50-70 ℃, adding an active monomer with the functionality of not less than 2 as an end capping agent for end capping reaction, and keeping the temperature for 1-2 hours;

step 6, cooling to 30-50 ℃, adding an organic base neutralizing agent for neutralization reaction for 0.5-1 hour, and maintaining the pH value between 7 and 9;

step 7, heating to 50-70 ℃, dropwise adding purified water, and strongly dispersing to obtain the polyurethane aqueous dispersion terminated by the active functional group;

and 8, cooling to room temperature, and adding an aqueous solution containing a closed curing agent to obtain the reactive waterborne polyurethane.

2. The process for preparing a reactive waterborne polyurethane as specified in claim 1 wherein: the raw materials and the auxiliary agents used in the preparation method are calculated according to the weight percentage (wt.%), and the contents of the components are as follows:

3. such asThe process for preparing a reactive waterborne polyurethane of claim 1, wherein: the ionic liquid is organic molten salt which is liquid at room temperature or near room temperature; the organic molten salt is composed of organic cations and organic or inorganic anions: cations include 1, 3-dihydrocarbylimidazoles, alkylammonium, alkylphosphorous, and alkylpyridines; the anion comprises ALCl₄ ^-、BF₄ ^-、PF₆ ^-、NO₃ ^-、ClO₄ ^-、CF₃COO^-、CF₃SO₃ ^-、CH₃COO^-。

4. The process for preparing a reactive waterborne polyurethane as specified in claim 1 wherein: in the step 1, the oligomer polyol is a monomer subjected to dehydration pretreatment before use, the dehydration treatment temperature is 100-140 ℃, the vacuum degree is 0.098-0.1MPa, and the time is 1-3 hours.

5. The process for preparing a reactive waterborne polyurethane as specified in claim 1 wherein: the oligomer polyol is any one or mixture of more of phthalic anhydride polyester polyol, polycaprolactone polyol and polylactic acid polyol with the number average molecular weight of 500-2000.

6. The process for preparing a reactive waterborne polyurethane as specified in claim 1 wherein: the hydrophilic group in the molecular structure of the hydrophilic monomer comprises carboxyl and hydroxyl.

7. The process for preparing a reactive waterborne polyurethane as specified in claim 1 wherein: the aromatic diisocyanate comprises any one or a mixture of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and 4, 4' -diphenylmethane diisocyanate.

8. The process for preparing a reactive waterborne polyurethane as specified in claim 1 wherein: the organic tin catalyst is any one or a mixture of two of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfur) and dibutyltin diacetate.

9. The process for preparing a reactive waterborne polyurethane as specified in claim 1 wherein: the chain extender is a small molecular diol, including but not limited to any one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol or diethanolamine; the end-capping reagent is any one of glycerol, pentaerythritol, trimethylolpropane, epoxypropanol, diethanolamine and triethanolamine; the closed curing agent is a compound which can be dissociated into isocyanate dimer or trimer at high temperature and can perform external crosslinking reaction with the terminal hydroxyl group or active hydrogen-containing group of the polyurethane prepolymer; the organic alkali neutralizer is amine compound, such as one of Triethylamine (TEA), diethanolamine or triethanolamine.

10. A reactive waterborne polyurethane characterized by: the prepolymer of the reactive waterborne polyurethane prepared by the preparation method of any one of claims 1 to 9 has the following general structural formula:

in the above structural formula, the thick solid line represents the hard segment, the wavy line represents the soft segment,andare both end-capping functional groups containing one or more hydroxyl groups,is composed ofAndany one of the above-mentioned (a) and (b),also is thatAndwherein A is H or OH, B is also H or OH, R₁Is C or N.

Technical Field

The invention belongs to the field of high polymer materials, relates to a preparation technology of polyurethane, and particularly relates to a preparation method of reactive waterborne polyurethane.

Background

With the development of modern industry, environmental pollution/climate change has become one of the major problems of global concern. Strict limit standards are set by countries in the world for the emission of Volatile Organic Compounds (VOCs) of chemical products. China has begun to pay consumption taxes for solvent-based chemical products to promote industry transformation or upgrading. In the field of polymer materials, the conversion of polymer material systems using organic materials as solvents to aqueous systems is an important development. Therefore, the research on the environment-friendly polymer material using water as a solvent has become a hot point of research.

Polyurethane is used as a polymer material with wide application, and research and application development in China have been in history for many years. However, in practical application, the characteristics of requiring the polyurethane material to be completely waterborne and having high solid content and low viscosity (high solid content and low viscosity) are still the difficulties of current product development; in addition, compared with solvent type polyurethane materials, the polymerization technology of the waterborne polyurethane material is not mature, the comprehensive performance of the material is still quite different, and the method of activity controllable polymerization is expected to greatly improve the comprehensive performance of the material. However, the activity-controllable polymerization belongs to the advanced research field of polymer science, and the difficulty of the polymerization technology is not the same. However, it is very important to explore the waterborne polyurethane materials with controllable activity, high solid content and low viscosity and environment-friendly property, which not only has important research significance and practical value, but also can generate great economic benefit.

The ionic liquid is organic molten salt consisting of anions and cations and has important application value. The document, "research progress of ionic liquid modified polyurethane" (Zhongchengfei, rubber and plastic technology and equipment) and the like research the case of ionic liquid used for modifying polyurethane, but the prior art takes the ionic liquid as a reactant to modify and participate in the synthesis of polyurethane, and no precedent for using the ionic liquid as a reaction medium is disclosed yet, and based on the problems, the invention provides a preparation method of reactive waterborne polyurethane by using the ionic liquid as the reaction medium.

Disclosure of Invention

The invention aims to provide reactive waterborne polyurethane and a preparation method thereof. The reaction takes the ionic liquid as a reaction medium and water as a solvent as a dispersion medium, and the synthesized polyurethane material is environment-friendly; the polyurethane prepolymer with the end capped by the active functional group and the closed curing agent can coexist under certain conditions, so that high-solid-content low-viscosity polymer resin can be obtained, and the application and the processing molding are facilitated; after application and construction, the closed curing agent is deblocked at a certain temperature, and the blocked curing agent and a blocking group of the polyurethane prepolymer are subjected to external crosslinking reaction to form a high-density crosslinked network structure, so that the controllable polymerization of the waterborne polyurethane material is realized.

The waterborne polyurethane material has good film forming property, and the comprehensive properties (such as water resistance, solvent resistance, wear resistance, scratch resistance, high temperature resistance, hardness, strength and the like) of the film are obviously and greatly improved, so that the material has practical application value. The reactive waterborne polyurethane can be used as a high-end coating and packaging material to be applied to the fields of electronic devices, medical instruments, biological medicines and the like.

The preparation method of the invention mainly solves the defects of the existing synthesis process and product performance of the waterborne polyurethane: 1) compared with the traditional solvent method, the method takes the ionic liquid as a reaction medium, and the synthesis process is environment-friendly; 2) the pure water is used as a dispersion medium, the system does not contain organic volatile matters such as cosolvent or film-forming additive and the like, the discharge amount of VOC approaches zero, and the product is green and environment-friendly; 3) reactive active functional groups are introduced in the aspect of molecular structure design, and a certain amount of closed curing agent is added to perform external crosslinking reaction to obtain a high-density crosslinked network structure, so that the mechanical property of the material is greatly improved, and the controllable polymerization of the waterborne polyurethane material is realized; 4) the method can obtain the polyurethane aqueous dispersion with high solid content and low viscosity, and is beneficial to processing, forming, application and construction.

The preparation method of the reactive waterborne polyurethane specifically comprises the following steps:

step 1, adding an organic tin catalyst, a hydrophilic monomer and oligomer polyol into a reaction vessel containing ionic liquid, and stirring and mixing uniformly at 70-90 ℃;

step 2, cooling the temperature of the reaction system to room temperature, adding aromatic diisocyanate, stirring at room temperature, and carrying out prepolymerization reaction for 1-2 hours;

step 3, heating to 60-80 ℃, and reacting for 3-5 hours in a heat preservation manner;

step 4, reducing the temperature of the reaction system to 30-40 ℃, adding a chain extender with low relative molecular mass for chain extension reaction, and keeping the temperature for reaction for 1-3 hours;

step 5, heating to 50-70 ℃, adding an active monomer with the functionality of not less than 2 as an end capping agent for end capping reaction, and keeping the temperature for 1-2 hours;

step 6, cooling to 30-50 ℃, adding organic base for neutralization reaction for 0.5-1 hour, and maintaining the pH value between 7 and 9;

step 7, heating to 50-70 ℃, dropwise adding purified water, and strongly dispersing to obtain the polyurethane aqueous dispersion terminated by the active functional group;

and 8, cooling to room temperature, and adding an aqueous solution containing a closed curing agent to obtain the reactive waterborne polyurethane.

The raw materials and the auxiliary agents for each reaction are calculated by weight (wt.%), and the contents of the components are as follows:

the invention relates to a preparation method of reactive waterborne polyurethane, wherein the ionic liquid is organic molten salt which is liquid at room temperature or near room temperature;

the ionic liquid is composed of organic cations and organic or inorganic anions: cations include 1, 3-dihydrocarbylimidazole, alkylammonium, alkylphosphorus, alkylpyridine, and the like; the anion comprises ALCl₄ ^-、BF₄ ^-、PF₆ ^-、NO₃ ^-、ClO₄ ^-、CF₃COO^-、CF₃SO₃ ^-、CH₃COO^-And the like.

Compared with the traditional organic solvent, the ionic liquid has the following advantages: nearly has no vapor pressure, is non-volatile, non-combustible and non-explosive; secondly, the melting point is low, the temperature range of the liquid state is wide, and the thermal stability and the chemical stability are good; dissolving a large amount of organic matters and inorganic matters; fourthly, the catalyst is easy to recycle and can be recycled. Based on the characteristics, the ionic liquid can be used as a green solvent for polymer synthesis, and has positive practical significance for solving the discharge problem of VOCs. The reactive waterborne polyurethane material is synthesized by adopting the ionic liquid as a reaction medium, and the synthesis process is green, environment-friendly and environment-friendly.

In the step 1, the oligomer polyol needs to be dehydrated before use, the dehydration temperature is 100-140 ℃, the vacuum degree is 0.098-0.1MPa, and the dehydration time is 1-3 hours.

The oligomer polyol comprises any one or a mixture of more of phthalic anhydride polyester Polyol (PABG), polyester polyol (EGBG), polycaprolactone Polyol (PCL) and polylactic acid Polyol (PLA) with the number average molecular weight in the range of 500-2000.

The hydrophilic monomer is a compound with a molecular structure containing hydrophilic groups such as carboxyl, hydroxyl, sulfonate and the like. Including but not limited to any one or more of dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), sodium 1, 3-propanediol sulfonate, sodium 1, 4-butanediol sulfonate, and sodium diaminosulfonate.

In the step 2, the temperature of the reaction system is reduced to room temperature, aromatic diisocyanate is added, stirring is carried out at room temperature, and prepolymerization reaction is carried out for 1-2 hours.

The aromatic diisocyanate includes, but is not limited to, any one or more of 2, 4-toluene diisocyanate (2, 4-TDI), 2, 6-toluene diisocyanate (2, 6-TDI), and 4, 4' -diphenylmethane diisocyanate (MDI).

Adding an organic tin catalyst in the step 3, stirring and mixing uniformly, and then heating to 60-80 ℃ for reaction for 3-5 hours in a heat preservation way;

the organic tin catalyst comprises one or a mixture of two of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfur) and dibutyltin diacetate.

Step 4, adding a chain extender with low relative molecular mass, and reacting for 1-3 hours in a heat preservation manner;

the chain extender is a small molecule dihydric alcohol, including but not limited to any one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol or diethanolamine.

In the step 5, adding a blocking agent (the functionality is more than or equal to 2), and carrying out heat preservation reaction for 1-2 hours;

the end-capping reagent is a substance capable of reacting with an isocyanate (-NCO) end group of the polyurethane prepolymer.

The end-capping reagent is a compound which still contains active functional groups after reacting with-NCO groups, and the functionality is more than or equal to 2.

The reactive functional groups generally include any one or more of hydroxyl, carboxyl, amino, and epoxy groups. .

The blocking agent includes, but is not limited to, one of glycerol (glycerin), pentaerythritol, trimethylolpropane, epoxypropanol, diethanolamine, triethanolamine.

The conversion of the isocyanate group (-NCO) was determined by titration according to the method of "determination of the content of isocyanate group in polyurethane prepolymer" HG-T2409-1992, and the end of the blocking reaction was indicated when the-NCO content reached the theoretical value, to obtain a polyurethane resin blocked with a reactive functional group.

In the step 6, adding organic base to neutralize and react for 0.5-1 hour, and maintaining the pH value between 7 and 9;

the organic alkali neutralizer is an amine compound, such as one of Triethylamine (TEA), diethanolamine or triethanolamine;

and performing neutralization reaction for 0.5-1 hour to obtain the polyurethane resin containing the ammonium carboxylate structure.

And 7, heating to 50-70 ℃, dropwise adding purified water, and strongly dispersing to obtain the polyurethane aqueous dispersion terminated by the active functional group.

The temperature of the reaction system is increased to 50-70 ℃, so that the solubility of the polyurethane resin can be increased.

When the pure water is dripped, the pure water is stirred and dispersed with strong force, because the polymer is turned over during the process, namely, the hydrophilic ammonium carboxylate groups are turned over outwards and fully contacted with the water; the lipophilic/hydrophobic polyurethane backbone or side chain turns inward and curls into clusters away from the aqueous phase. Thereby forming a spherical micelle structure of oil-in-water (O/W).

The strong dispersion is because the viscosity of the resin increases during the phase inversion, and the resistance to dispersion increases accordingly.

The strong dispersion aims to obtain a dispersion with micelle particle size distribution of 10-50nm and blue light and has a Tyndall effect.

And 8, adding a closed curing agent to obtain a reactive waterborne polyurethane material.

The closed curing agent is a compound which can be dissociated into isocyanate dimer or trimer at high temperature and can perform external crosslinking reaction with terminal hydroxyl or active hydrogen of the polyurethane prepolymer. Through the external crosslinking reaction with the prepolymer, a crosslinked network structure is generated.

The active hydrogen-containing compound includes alcohols, phenols, lactams, beta-dicarbonyl compounds, oximes, pyrazole or sodium bisulfite and the like.

The reactive waterborne polyurethane material prepared by the method is an aqueous dispersion with blue light, the particle size is 10-50nm, and the distribution is narrow.

The reactive waterborne polyurethane can be used as a high-end coating material or a packaging material and widely applied to the fields of electronic appliances, medical instruments, biomedicine, fabrics, printing and packaging and the like.

The invention also provides a reactive waterborne polyurethane prepared by any one of the methods, and the structural general formula of the prepared reactive waterborne polyurethane prepolymer is as follows:

in the above structural formula, the thick solid line represents the hard segment, the wavy line represents the soft segment,andare both end-capping functional groups containing one or more hydroxyl groups,is composed ofAndany one of the above-mentioned (a) and (b),also is thatAndwherein A is H or OH, B is also H or OH, R₁Is C or N.

The advantages of the invention are mainly reflected in that:

according to the preparation method of the reactive waterborne polyurethane, ionic liquid is used as a reaction medium in a polymerization process, and compared with a traditional acetone method, the synthesis process is environment-friendly;

according to the preparation method of the reactive waterborne polyurethane, the synthesized polymer system takes the purified water as a dispersion medium, and compared with the traditional solvent-based polyurethane material, the system does not contain organic solvents, cosolvents, film-forming aids and other toxic and harmful organic volatile matters, so that the problem of discharge of VOCs is scientifically solved, and the product is green and environment-friendly;

according to the preparation method of the reactive waterborne polyurethane, reactive active functional groups are introduced in the aspect of polyurethane molecular structure design, and can generate external crosslinking reaction with a closed curing agent under a certain condition to obtain a high-density crosslinked network structure, so that the mechanical property of the material is greatly improved;

according to the preparation method of the reactive waterborne polyurethane, disclosed by the invention, the polyurethane prepolymer terminated by the active functional group and the closed curing agent coexist in the same system to obtain the single-component aqueous dispersion, so that the controllable polymerization of the waterborne polyurethane is realized, and the application construction is facilitated;

the preparation method of the reactive waterborne polyurethane can obtain the polyurethane aqueous dispersion with high solid content and low viscosity, and is beneficial to processing, forming, application and construction.

The reactive waterborne polyurethane can be used as a high-end coating material or a packaging material and widely applied to the fields of electronic and electric appliances, medical instruments, biomedicine, fabrics, printing and packaging and the like.

Drawings

FIG. 1 is a schematic diagram of a reaction scheme for synthesizing a reactive aqueous polyurethane, in which a thick solid line represents a hard segment of a molecular chain, a wavy line represents a soft segment of the molecular chain,is a terminal functional group containing one or more hydroxyl groups, R isOrR' is-CH₂CH₂-or-CH₂CH₂CH₂CH₂-。

FIG. 2 is a schematic diagram of the structure of the product of example 1.

FIG. 3 is a schematic diagram of the structure of the product of example 2.

FIG. 4 is a schematic diagram of the structure of the product of example 3.

FIG. 5 is a schematic diagram of the structure of the product of example 4.

FIG. 6 is a schematic diagram of the structure of the product of example 5.

Detailed Description

To further illustrate the present technology, the following detailed description is presented in conjunction with specific examples, including but not limited to the following examples.

Example 1

A process for the preparation of reactive aqueous polyurethanes, wherein the components are, in parts by weight (wt.%):

the preparation method of the reactive waterborne polyurethane comprises the following steps: adding 60g of oligomer polyol (PCL-1000), 0.6g of organic tin catalyst (dibutyltin dilaurate) and 6g of hydrophilic monomer (DMPA) into a reaction vessel containing 30g of ionic liquid, and stirring and mixing uniformly at 70-90 ℃; cooling the reaction system to room temperature, adding 33g of aromatic diisocyanate (2, 4-TDI), stirring at room temperature, and carrying out prepolymerization reaction for 1-2 hours; then heating to 60-80 ℃ and reacting for 3-5 hours in a heat preservation way; reducing the temperature of a reaction system to 30-40 ℃, adding 6g of chain extender (ethylene glycol) with low relative molecular mass, and keeping the temperature for reaction for 1-3 hours; heating to 50-70 ℃, adding 6g of end-capping reagent (glycerol), and reacting for 1-2 hours under heat preservation; cooling to 30-50 deg.C, adding 4.5g organic base (TEA) to neutralize for 0.5-1 hr, and maintaining pH at 7-9; heating to 50-70 ℃, dropwise adding 195g of purified water, and strongly dispersing to obtain the polyurethane aqueous dispersion terminated by the active functional group; and cooling to room temperature, and adding 9g of closed curing agent to obtain the reactive waterborne polyurethane.

Table 1 example 1 material performance test results:

test items	Test method	Test results
			Appearance of the product	Observation method	Translucent band blueOptical dispersion
Solid content (%)	GB1725-79 2004	25
			pH value	GB/T23769-2009	8
Adhesion force	GB/T 1720-1979(89)	≤1
			Hardness of	GB/T 1720-1979(89)	≥H
Viscosity of the oil	(coating 4 cup at 25 ℃ C.)	17 +/-1 second
			Particle size	Dynamic light scattering method	10-50nm
Morphology of	Scanning Electron Microscopy (SEM)	Spherical shape

Example 2

According to the preparation method of the reactive waterborne polyurethane, the raw materials and the auxiliary agents are calculated according to the weight percentage (wt.%):

the preparation method of the reactive waterborne polyurethane comprises the following steps: adding 60g of oligomer polyol (PABG-1000), 0.5 g of organic tin catalyst (stannous octoate) and 8g of hydrophilic monomer (DMBA) into a reaction vessel containing 24g of ionic liquid, and stirring and mixing uniformly at 70-90 ℃; cooling the reaction system to room temperature, adding 40g of aromatic diisocyanate (2, 6-TDI), stirring at room temperature, and carrying out prepolymerization reaction for 1-2 hours; then heating to 60-80 ℃ and reacting for 3-4 hours in a heat preservation way; reducing the temperature of the reaction system to 40 ℃, adding 4g of chain extender (1, 4-butanediol), and reacting for 1-2 hours under the condition of heat preservation; heating the reaction system to 50-60 ℃, adding 12g of end-capping reagent (TMP), and reacting for 1-2 hours under heat preservation; cooling to 30 deg.C, adding 4g organic base (TEA) to neutralize for 0.5-1 hr, and maintaining pH at 8-9; heating to 50-70 ℃, dropwise adding 240g of purified water, and strongly dispersing to obtain the polyurethane aqueous dispersion terminated by the active functional group; and cooling to room temperature, and adding 10g of closed curing agent to obtain the reactive waterborne polyurethane.

Table 2 example 2 material performance test results:

test items	Test method	Test results
			Appearance of the product	Observation method	Translucent with blue lightDispersion product
Solid content (%)	GB1725-79 2004	34
			pH value	GB/T23769-2009	7.5-
Adhesion force	GB/T 1720-1979(89)	≤1
			Hardness of	GB/T 1720-1979(89)	≥H
Viscosity of the oil	(coating 4 cup at 25 ℃ C.)	20 +/-1 second
			Particle size	Dynamic light scattering method	10-30nm
Morphology of	Scanning Electron Microscopy (SEM)	Spherical shape

Example 3

The raw materials and the auxiliary agents for each reaction are calculated by weight (wt.%), and the contents of the components are as follows:

the preparation method of the reactive waterborne polyurethane comprises the following steps: adding 77.2g of oligomer polyol (PLA-1000), 0.4g of organic tin catalyst [ dibutyltin bis (dodecyl sulfur) and 5.2g of hydrophilic monomer (1, 3-propylene glycol sodium sulfonate) into a reaction vessel containing 28g of ionic liquid, and uniformly stirring and mixing at 70-90 ℃; cooling the temperature of the reaction system to room temperature, adding 34g of aromatic diisocyanate (MDI), stirring at room temperature, and carrying out prepolymerization reaction for 1 hour; then adding the mixture, stirring and mixing the mixture evenly, and then heating the mixture to 70 ℃ for reaction for 4 hours in a heat preservation way; reducing the temperature of the reaction system to 40 ℃, adding 6g of chain extender (diethanolamine) with low relative molecular mass, and keeping the temperature for reaction for 1 hour; heating to 60 ℃, adding 6g of end-capping reagent (pentaerythritol), and reacting for 2 hours under the condition of heat preservation; cooling to 30 ℃, adding 4g of organic base (diethanolamine) for neutralization reaction for 0.5 hour, and maintaining the pH value between 7 and 8; heating to 60 ℃, dropwise adding 232g of purified water, and strongly dispersing to obtain the polyurethane aqueous dispersion terminated by the active functional group; and cooling to room temperature, and adding 6g of closed curing agent to obtain the reactive waterborne polyurethane.

Table 3 example 3 material performance test results:

test items	Test method	Test results
			Appearance of the product	Observation method	Translucent blue dispersion
Solid content (%)	GB1725-79 2004	35
			pH value	GB/T23769-2009	7-8
Adhesion force	GB/T 1720-1979(89)	≤1
			Hardness of	GB/T 1720-1979(89)	≥H
Viscosity of the oil	(coating 4 cup at 25 ℃ C.)	22 +/-1 second
			Particle size	Dynamic light scattering method	30-50nm
Morphology of	Scanning Electron Microscopy (SEM)	Spherical shape

Example 4

The raw materials and the auxiliary agents for each reaction are calculated by weight (wt.%), and the contents of the components are as follows:

the preparation method of the reactive waterborne polyurethane comprises the following steps: adding 64g of oligomer polyol mixture (EGBG-1000), 1.2g of organotin catalyst (dibutyltin acetate) and 6.8g of hydrophilic monomer (1, 4-butanediol sodium sulfonate) into a reaction vessel containing 32g of ionic liquid, and stirring and mixing uniformly at 70-90 ℃; cooling the temperature of the reaction system to room temperature, adding 42.4g of aromatic diisocyanate (MDI), stirring at room temperature, and carrying out prepolymerization reaction for 1 hour; then heating to 60 ℃ and reacting for 5 hours in a heat preservation way; reducing the temperature of the reaction system to 40 ℃, adding 2.4g of chain extender (1, 3-propylene glycol) with low relative molecular mass, and keeping the temperature for reaction for 2 hours; heating to 70 ℃, adding 4.8g of end-capping reagent (triethanolamine), and reacting for 2 hours under the condition of heat preservation; cooling to 30 deg.C, adding 4g organic base (triethanolamine) to neutralize for 1 hr, and maintaining pH at 7.5-8; heating to 60 ℃, dropwise adding 240g of purified water, and strongly dispersing to obtain the polyurethane aqueous dispersion terminated by the active functional group; and cooling to room temperature, and adding 2.4g of a closed curing agent to obtain the reactive waterborne polyurethane.

Table 4 example 4 material performance test results:

test items	Test method	Test results
			Appearance of the product	Observation method	Translucent blue dispersion
Solid content (%)	GB1725-79 2004	32
			pH value	GB/T23769-2009	7.5-8
Adhesion force	GB/T 1720-1979(89)	≤1
			Hardness of	GB/T 1720-1979(89)	≥H
Viscosity of the oil	(coating 4 cup at 25 ℃ C.)	20 +/-1 second
			Particle size	Dynamic light scattering method	10-50nm
Morphology of	Scanning Electron Microscopy (SEM)	Spherical shape

Example 5

The raw materials and the auxiliary agents for each reaction are calculated by weight (wt.%), and the contents of the components are as follows:

the preparation method of the reactive waterborne polyurethane comprises the following steps: adding 63.2g of oligomer polyol (BGBG-2000), 1g of organic tin catalyst (dibutyltin dilaurate) and 8g of hydrophilic monomer (sodium diaminosulfonate) into a reaction vessel containing 40g of ionic liquid, and stirring and mixing uniformly at 70-90 ℃; cooling the reaction system to room temperature, adding 56g of aromatic diisocyanate (20% of 2, 4-TDI, 80% of 2, 6-TDI), stirring at room temperature, and carrying out prepolymerization reaction for 1 hour; then heating to 80 ℃ and reacting for 4 hours in a heat preservation way; the temperature of the reaction system was lowered to 50 ℃ and 12.8g of a blocking agent (M) was added_Glycerol:M_{Epoxypropanol}1:1), and keeping the temperature for 2 hours; cooling to 30 deg.C, adding 4.5g organic base (TEA) to neutralize for 1 hr, and maintaining pH at 8-9; heating to 60 ℃, dropwise adding 200g of purified water, and strongly dispersing to obtain the polyurethane aqueous dispersion terminated by the active functional group; and cooling to room temperature, and adding 12g of closed curing agent to obtain the reactive waterborne polyurethane.

Table 5 example 5 material performance test results:

test items	Test method	Test results
			Appearance of the product	Observation method	Translucent blue dispersion
Solid content (%)	GB1725-79 2004	40
			pH value	GB/T23769-2009	8-9
Adhesion force	GB/T 1720-1979(89)	≤1
			Hardness of	GB/T 1720-1979(89)	≥H
Viscosity of the oil	(coating 4 cup at 25 ℃ C.)	18 +/-1 second
			Particle size	Dynamic light scattering method	10-50nm
Morphology of	Scanning Electron Microscopy (SEM)	Spherical shape

The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.