CN111040426A - Nano zinc oxide modified waterborne polyurethane emulsion and preparation method thereof - Google Patents
Nano zinc oxide modified waterborne polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN111040426A CN111040426A CN201911376105.6A CN201911376105A CN111040426A CN 111040426 A CN111040426 A CN 111040426A CN 201911376105 A CN201911376105 A CN 201911376105A CN 111040426 A CN111040426 A CN 111040426A
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- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention discloses a nano zinc oxide modified waterborne polyurethane emulsion and a preparation method thereof, relating to the technical field of polymer synthetic materials and comprising the following raw materials in parts by weight: 50-150 parts of polyether polyol, 50-150 parts of polyester polyol, 6-10 parts of micromolecular polyol chain extender, 30-100 parts of diisocyanate, 1-3 parts of carboxylic acid type hydrophilic chain extender, 8-25 parts of sulfonic acid type hydrophilic chain extender, 10-20 parts of silane modified nano zinc oxide, 0.1-0.5 part of organic metal catalyst, 1.5-4 parts of neutralizer, 50-200 parts of organic solvent and 300 parts of deionized water; the preparation method comprises prepolymerization, chain extension, dispersion and chain extension. The proportion of the carboxylic acid type hydrophilic chain extender and the sulfonic acid type hydrophilic chain extender is reasonably proportioned, the using amount is controlled, and the prepared waterborne polyurethane has high solid content; and silane modified nano zinc oxide is added in the growth stage of the waterborne polyurethane chain, so that the heat resistance, the water resistance, the mechanical property and other properties of the waterborne polyurethane chain are effectively improved.
Description
Technical Field
The invention relates to the technical field of polymer synthetic materials, in particular to a nano zinc oxide modified waterborne polyurethane emulsion and a preparation method thereof.
Background
Waterborne Polyurethanes (WPU) are dispersions of polyurethane dispersed in water, also known as water-based polyurethanes. Compared with the traditional organic solvent type polyurethane, the preparation method does not need to add a large amount of organic solvent in the preparation process, and has the advantages of low cost, environmental protection, simple production and the like. The waterborne polyurethane has good physical and mechanical properties and wear resistance, is widely applied to the fields of wood coatings, leather, adhesives and the like, and still needs to be further improved in heat resistance, water resistance and solvent resistance. In addition, the solid content of the existing waterborne polyurethane is generally 25-40%, the drying speed is slow, and the transportation cost is high. Therefore, it is becoming more and more important how to obtain high-solid content aqueous polyurethane with excellent properties.
In the aqueous polyurethane, the anionic type is widely applied, and the anionic group is introduced into the polyurethane chain, so that the polyurethane chain has enough hydrophilicity to be dispersed in water to form stable emulsion. The commonly used anionic groups are mainly of the carboxylate type and the sulfonate type. The preparation of the aqueous polyurethane emulsion with high solid content by methods such as molecular design, production process and the like is a field which is researched more at present, and the stability and the film-forming property of the emulsion are required to be ensured.
The nanometer zinc oxide belongs to semiconductor material, and has the advantages of good chemical stability, strong ultraviolet absorption capacity, thermal property, antistatic property and the like. However, the nano zinc oxide is easy to agglomerate in the polymer and has poor compatibility, so that the application of the nano zinc oxide in the polymer is limited. Therefore, the waterborne polyurethane emulsion with high solid content is prepared by an effective and proper method, and the nano zinc oxide is modified and introduced into the synthesis of waterborne polyurethane, so that the nano zinc oxide is connected with polyurethane molecules through chemical bonds, the performance of the polymer composite material is improved, and the prepared polymer material with excellent performance has good market application prospect.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the nano zinc oxide modified waterborne polyurethane emulsion and the preparation method thereof, and the prepared waterborne polyurethane has high solid content and excellent heat resistance, water resistance, mechanical properties and the like.
The invention provides a nano zinc oxide modified waterborne polyurethane emulsion which comprises the following raw materials in parts by weight: 50-150 parts of polyether polyol, 50-150 parts of polyester polyol, 6-10 parts of micromolecular polyol chain extender, 30-100 parts of diisocyanate, 1-3 parts of carboxylic acid type hydrophilic chain extender, 8-25 parts of sulfonic acid type hydrophilic chain extender, 10-20 parts of silane modified nano zinc oxide, 0.1-0.5 part of organic metal catalyst, 1.5-4 parts of neutralizer, 50-200 parts of organic solvent and 300 parts of deionized water.
Preferably, the polyether polyol has a functionality of 2-3 and a molecular weight of 2000-; preferably, the polyester polyol has a functionality of 2 and a molecular weight of 2000.
Preferably, the diisocyanate is any one or more of 4,4' -diphenylmethane diisocyanate MDI-100 and 2, 4-diphenylmethane diisocyanate MDI-50, toluene diisocyanate and isophorone diisocyanate.
Preferably, the chain extender of the small-molecular polyol is any one of neopentyl glycol, trimethylolpropane and 1, 4-butanediol;
preferably, the carboxylic acid type hydrophilic chain extender is any one of dimethylolbutyric acid and dimethylolpropionic acid;
preferably, the sulfonic acid type hydrophilic chain extender is any one of ethylene diamino ethane sulfonic acid sodium, diaminobutane sulfonic acid and diaminobenzene sulfonate.
Preferably, the organic metal catalyst is any one of stannous octoate, dibutyltin dilaurate and lead octoate;
preferably, the neutralizing agent is triethylamine;
preferably, the organic solvent is any one of acetone, butanone and N, N-dimethylformamide.
Preferably, the silane modified nano zinc oxide is prepared as follows: adding the dried nano zinc oxide and the silane coupling agent into absolute ethyl alcohol, performing ultrasonic dispersion, stirring for reaction, filtering, washing and drying to obtain the zinc oxide/silane coupling agent composite material.
Preferably, the silane modified nano zinc oxide is prepared as follows: drying the nano zinc oxide in an oven at 120 ℃ for 2-3h, adding a silane coupling agent into absolute ethyl alcohol, and ultrasonically dispersing for 1h, wherein the mass ratio of the nano zinc oxide to the silane coupling agent to the absolute ethyl alcohol is 1-3: 1: 100, then stirring and reacting for 2 hours at the constant temperature of 60 ℃, filtering, washing for more than 3 times by using absolute ethyl alcohol, and drying for 3 hours at the temperature of 80 ℃ in an oven to obtain the product.
Preferably, the silane coupling agent is any one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane and N- (β -chloroethyl) -gamma-aminopropyltrimethoxysilane, and the nano-zinc oxide is rod-shaped nano-zinc oxide with the particle size of 30-60 nm.
The invention also provides a preparation method of the nano zinc oxide modified waterborne polyurethane emulsion, which comprises the following steps:
s1, prepolymerization: adding polyether polyol and polyester polyol into a reaction container for vacuum dehydration treatment, then sequentially adding a micromolecular polyol chain extender and part of diisocyanate, and carrying out heat preservation reaction for 2 hours at the temperature of 80-85 ℃;
s2, chain extension: adding a carboxylic acid type hydrophilic chain extender and a proper amount of organic solvent into a reaction system of S1, reacting for 2 hours at the temperature of 80-85 ℃, then adding the rest diisocyanate, dropwise adding an organic metal catalyst, and continuing to react for 3-4 hours at the temperature of 80-85 ℃; cooling to 30-40 ℃, adding part of sulfonic acid type hydrophilic chain extender and a proper amount of organic solvent, and continuing to react for 10-20 min;
s3, dispersing and chain extending: and (2) at 30-40 ℃, dropwise adding a neutralizer into the reaction system of S2 for neutralization treatment for 30min, simultaneously adding the rest organic solvent, then dissolving the rest sulfonic acid type hydrophilic chain extender into deionized water, adding the solution into the reaction system under high-speed shearing force, dispersing for 30min, adding silane modified nano zinc oxide, stirring for 30min, and removing the organic solvent by reduced pressure distillation to obtain the high-solid-content waterborne polyurethane emulsion.
Preferably, the mass percentage of the sulfonic acid type hydrophilic chain extender in S2 and S3 is 10-20: 80-90.
Compared with the prior art, the effective effects of the invention are embodied in the following aspects:
1. according to the invention, the proportion of the carboxylic acid type hydrophilic chain extender and the sulfonic acid type hydrophilic chain extender is reasonably proportioned, and the using amount is controlled, so that the polyurethane has good dispersing capacity in water, the high-solid-content aqueous polyurethane emulsion can be prepared, the solid content can reach 55-65%, and the emulsion has good stability.
2. According to the invention, nano zinc oxide modified by a silane coupling agent is introduced into waterborne polyurethane, silane modified nano zinc oxide is added in the chain growth stage of the waterborne polyurethane, so that the molecular chain of the polyurethane is further increased, inorganic components and organic components are effectively linked, the compatibility of nanoparticles in a polymer is enhanced, and the polyurethane is subjected to double modification of silane and zinc oxide, so that the polyurethane has excellent heat resistance, water resistance, mechanical properties and other properties. Compared with the method of adding silane modified nano zinc oxide in the prepolymerization stage, the method is added in the chain extension stage after emulsification and dispersion are completed, and more nano zinc oxide particles are grafted on the surface of the polyurethane reticular macromolecular chain, so that the water resistance and heat resistance of the polyurethane are better.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a nano zinc oxide modified waterborne polyurethane emulsion comprises the following steps:
s1, prepolymerization: adding 100 parts of polyether glycol 2000 and 80 parts of polyester glycol 2000 into a three-neck flask provided with a stirrer and a thermometer, heating to 100 ℃, carrying out vacuum dehydration for 2 hours, cooling to 80 ℃, sequentially adding 6 parts of micromolecular polyol chain extender trimethylolpropane and 10 parts of toluene diisocyanate, and carrying out heat preservation reaction for 2 hours at 80 ℃;
s2, chain extension: adding 1.3 parts of carboxylic acid type hydrophilic chain extender dimethylolpropionic acid and 15 parts of organic solvent butanone into a reaction system of S1, reacting for 2 hours at 80 ℃, adding 50 parts of toluene diisocyanate, dropwise adding 0.3 part of organic metal catalyst dibutyltin dilaurate, and continuing to react for 3.5 hours at 80 ℃; cooling to 30 ℃, adding 2 parts of sulfonic acid type hydrophilic chain extender ethylene diamine ethyl sodium sulfonate and 10 parts of organic solvent butanone, and continuing to react for 15 min;
s3, dispersing and chain extending: at 30 ℃, 1.5 parts of triethylamine is dripped into a reaction system of S2 for neutralization treatment for 30min, 80 parts of organic solvent butanone is added at the same time, then 8 parts of sulfonic acid type hydrophilic chain extender ethylenediamine ethyl sodium sulfonate is dissolved in 181 parts of deionized water, the mixture is added into the reaction system under high-speed shearing force, the dispersion is carried out for 30min, 14 parts of silane modified nano zinc oxide is added, the mixture is stirred for 30min, and the organic solvent is removed by reduced pressure distillation, so as to prepare a waterborne polyurethane emulsion with the solid content of 60%;
the preparation method of the silane modified nano zinc oxide comprises the following steps: drying the nano zinc oxide in a drying oven at 120 ℃ for 2.5h, adding a silane coupling agent gamma-aminopropyltriethoxysilane into absolute ethyl alcohol, and ultrasonically dispersing for 1h, wherein the mass ratio of the nano zinc oxide to the silane coupling agent to the absolute ethyl alcohol is 2: 1: 100, then stirring and reacting for 2 hours at the constant temperature of 60 ℃, filtering, washing for more than 3 times by using absolute ethyl alcohol, and drying for 3 hours at the temperature of 80 ℃ in an oven to obtain the product.
Example 2
A preparation method of a nano zinc oxide modified waterborne polyurethane emulsion comprises the following steps:
s1, prepolymerization: adding 90 parts of polyether glycol 3000 and 90 parts of polyester glycol 2000 into a three-neck flask provided with a stirrer and a thermometer, heating to 100 ℃, carrying out vacuum dehydration for 2 hours, cooling to 80 ℃, sequentially adding 8 parts of micromolecular polyol chain extender neopentyl glycol and 10 parts of toluene diisocyanate, and carrying out heat preservation reaction for 2 hours at 85 ℃;
s2, chain extension: adding 2 parts of carboxylic acid type hydrophilic chain extender dimethylolpropionic acid and 18 parts of organic solvent acetone into a reaction system of S1, reacting for 2 hours at 85 ℃, then adding 60 parts of MDI-50, dropwise adding 0.3 part of organic metal catalyst stannous octoate, and continuing to react for 3.5 hours at 85 ℃; cooling to 40 ℃, adding 3 parts of sulfonic acid type hydrophilic chain extender diaminobutanesulfonic acid and 30 parts of organic solvent acetone, and continuing to react for 20 min;
s3, dispersing and chain extending: at 40 ℃,4 parts of triethylamine is added into a reaction system of S2 dropwise for neutralization treatment for 30min, 120 parts of organic solvent acetone is added simultaneously, then 12 parts of sulfonic acid type hydrophilic chain extender diaminobutanesulfonic acid is dissolved in 168 parts of deionized water, the mixture is added into the reaction system under high-speed shearing force, the dispersion is carried out for 30min, 10 parts of silane modified nano zinc oxide is added, the mixture is stirred for 30min, and the organic solvent is removed through reduced pressure distillation, so that the aqueous polyurethane emulsion with the solid content of 65% is prepared;
the preparation method of the silane modified nano zinc oxide comprises the following steps: drying the nano zinc oxide in a drying oven at 120 ℃ for 3h, adding a silane coupling agent gamma-aminopropyl trimethoxy silane into absolute ethyl alcohol, and ultrasonically dispersing for 1h, wherein the mass ratio of the nano zinc oxide to the silane coupling agent to the absolute ethyl alcohol is 2.5: 1: 100, then stirring and reacting for 2 hours at the constant temperature of 60 ℃, filtering, washing for more than 3 times by using absolute ethyl alcohol, and drying for 3 hours at the temperature of 80 ℃ in an oven to obtain the product.
Example 3
A preparation method of a nano zinc oxide modified waterborne polyurethane emulsion comprises the following steps:
s1, prepolymerization: adding 150 parts of 5000 polyether glycol and 50 parts of 2000 polyester glycol into a three-neck flask provided with a stirrer and a thermometer, heating to 100 ℃, carrying out vacuum dehydration for 2 hours, cooling to 80 ℃, sequentially adding 6 parts of small molecular polyol chain extender 1, 4-butanediol and 10 parts of isophorone diisocyanate, and carrying out heat preservation reaction for 2 hours at 80 ℃;
s2, chain extension: adding 3 parts of carboxylic acid type hydrophilic chain extender dimethylolbutyric acid and 20 parts of organic solvent N, N-dimethylformamide into a reaction system of S1, reacting for 2 hours at 80 ℃, then adding 60 parts of isophorone diisocyanate, dropwise adding 0.5 part of organic metal catalyst lead octoate, and continuing to react for 3 hours at 80 ℃; cooling to 30 ℃, adding 4 parts of sulfonic acid type hydrophilic chain extender diaminobenzene sulfonate and 10 parts of organic solvent N, N-dimethylformamide, and continuing to react for 10 min;
s3, dispersing and chain extending: at 30 ℃, 2.5 parts of triethylamine is added into a reaction system of S2 dropwise for neutralization treatment for 30min, 150 parts of organic solvent N, N-dimethylformamide is added at the same time, then 16 parts of sulfonic acid type hydrophilic chain extender diaminobenzene sulfonate is dissolved in 250 parts of deionized water, the mixture is added into the reaction system under high-speed shearing force, dispersed for 30min, then 20 parts of silane modified nano zinc oxide is added, stirred for 30min, and the organic solvent is removed by reduced pressure distillation, so that the aqueous polyurethane emulsion with the solid content of 60% is prepared;
the silane modified nano zinc oxide is prepared by drying nano zinc oxide in an oven at 120 ℃ for 2h, adding a silane coupling agent N- (β -chloroethyl) -gamma-aminopropyltrimethoxysilane into absolute ethyl alcohol, and ultrasonically dispersing for 1h, wherein the mass ratio of the nano zinc oxide to the silane coupling agent to the absolute ethyl alcohol is 1: 1: 100, stirring and reacting at the constant temperature of 60 ℃ for 2h, filtering, washing with the absolute ethyl alcohol for more than 3 times, and drying in the oven at 80 ℃ for 3h to obtain the silane modified nano zinc oxide.
Example 4
A preparation method of a nano zinc oxide modified waterborne polyurethane emulsion comprises the following steps:
s1, prepolymerization: adding 5000 parts of polyether glycol and 150 parts of polyester glycol 2000 into a three-neck flask provided with a stirrer and a thermometer, heating to 100 ℃, carrying out vacuum dehydration for 2 hours, cooling to 80 ℃, sequentially adding 10 parts of micromolecular polyol chain extender 1, 4-butanediol and 30 parts of isophorone diisocyanate, and carrying out heat preservation reaction for 2 hours at 85 ℃;
s2, chain extension: adding 3 parts of carboxylic acid type hydrophilic chain extender dimethylolpropionic acid and 20 parts of organic solvent N, N-dimethylformamide into a reaction system of S1, reacting for 2 hours at 85 ℃, then adding 70 parts of isophorone diisocyanate, dropwise adding 0.5 part of organic metal catalyst lead caprylate, and continuing to react for 4 hours at 85 ℃; cooling to 40 ℃, adding 4 parts of sulfonic acid type hydrophilic chain extender diaminobenzene sulfonate and 10 parts of organic solvent N, N-dimethylformamide, and continuing to react for 20 min;
s3, dispersing and chain extending: at 40 ℃, 2.3 parts of triethylamine is dripped into a reaction system of S2 for neutralization treatment for 30min, 120 parts of organic solvent N, N-dimethylformamide is added at the same time, then 20 parts of sulfonic acid type hydrophilic chain extender diaminobenzene sulfonate is dissolved in 250 parts of deionized water, the solution is added into the reaction system under high-speed shearing force, the dispersion is carried out for 30min, 20 parts of silane modified nano zinc oxide is added, the stirring is carried out for 30min, the organic solvent is removed by reduced pressure distillation, and the aqueous polyurethane emulsion with the solid content of 60% is prepared;
the silane modified nano zinc oxide is prepared by drying nano zinc oxide in an oven at 120 ℃ for 3 hours, adding a silane coupling agent N- (β -chloroethyl) -gamma-aminopropyltrimethoxysilane into absolute ethyl alcohol, and ultrasonically dispersing for 1 hour, wherein the mass ratio of the nano zinc oxide to the silane coupling agent to the absolute ethyl alcohol is 3: 1: 100, stirring and reacting for 2 hours at a constant temperature of 60 ℃, filtering, washing for more than 3 times by using the absolute ethyl alcohol, and drying in the oven at 80 ℃ for 3 hours to obtain the silane modified nano zinc oxide.
Comparative example
Compared with the example 1, the raw materials and the weight of the raw materials are the same as those of the example 1, the difference is only that the silane modified nano zinc oxide is added together with the polyether polyol in the S1 prepolymerization stage in the preparation method, and other steps are the same.
The modified aqueous polyurethane emulsions obtained in examples 1 to 4 of the present invention and comparative example were tested for their properties.
And (3) testing items: a. water resistance: coating the emulsion on a tetrafluoro plate, forming a film for 48 hours at the room temperature of 25 ℃, and continuously drying for 12 hours in a drying oven at the temperature of 60 ℃. The coating film was cut into 5cm × 5cm samples, weighed (W1), soaked in distilled water for 24 hours, taken out, surface water was removed by suction with filter paper, and weighed (W2). The water absorption calculation formula is as follows: water absorption was (W2-W1)/W1 × 100%.
b. Tensile strength: testing according to GB/T1040-92.
The test results are shown in Table 1.
TABLE 1 data for performance testing in examples 1-4 and comparative examples
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Tensile strength/MPa | 9 | 11 | 10 | 13 | 8 |
| Water resistance | 5.5％ | 6.9％ | 6.6％ | 5.7％ | 9.8％ |
As can be seen from Table 1, the modified aqueous polyurethane emulsions obtained in examples 1 to 4 of the present invention are significantly superior to the comparative examples in both tensile strength and water resistance. The tensile strength in example 1 was increased by 12.5% compared to the comparative example.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The nano zinc oxide modified waterborne polyurethane emulsion is characterized by comprising the following raw materials in parts by weight: 50-150 parts of polyether polyol, 50-150 parts of polyester polyol, 6-10 parts of micromolecular polyol chain extender, 30-100 parts of diisocyanate, 1-3 parts of carboxylic acid type hydrophilic chain extender, 8-25 parts of sulfonic acid type hydrophilic chain extender, 10-20 parts of silane modified nano zinc oxide, 0.1-0.5 part of organic metal catalyst, 1.5-4 parts of neutralizer, 50-200 parts of organic solvent and 300 parts of deionized water.
2. The nano zinc oxide modified waterborne polyurethane emulsion as claimed in claim 1, wherein the polyether polyol has a functionality of 2-3 and a molecular weight of 2000-; preferably, the polyester polyol has a functionality of 2 and a molecular weight of 2000.
3. The nano zinc oxide modified aqueous polyurethane emulsion according to claim 1 or 2, wherein the diisocyanate is any one or more of 4,4' -diphenylmethane diisocyanate MDI-100 and 2, 4-diphenylmethane diisocyanate MDI-50, toluene diisocyanate, isophorone diisocyanate.
4. The nano zinc oxide modified waterborne polyurethane emulsion of any one of claims 1 to 3, wherein the small molecule polyol chain extender is any one of neopentyl glycol, trimethylolpropane and 1, 4-butanediol;
preferably, the carboxylic acid type hydrophilic chain extender is any one of dimethylolbutyric acid and dimethylolpropionic acid;
preferably, the sulfonic acid type hydrophilic chain extender is any one of ethylene diamino ethane sulfonic acid sodium, diaminobutane sulfonic acid and diaminobenzene sulfonate.
5. The nano zinc oxide modified aqueous polyurethane emulsion according to any one of claims 1 to 4, wherein the organic metal catalyst is any one of stannous octoate, dibutyltin dilaurate and lead octoate;
preferably, the neutralizing agent is triethylamine;
preferably, the organic solvent is any one of acetone, butanone and N, N-dimethylformamide.
6. The nano zinc oxide modified waterborne polyurethane emulsion of any one of claims 1 to 5, wherein the silane modified nano zinc oxide is prepared by: adding the dried nano zinc oxide and the silane coupling agent into absolute ethyl alcohol, performing ultrasonic dispersion, stirring for reaction, filtering, washing and drying to obtain the zinc oxide/silane coupling agent composite material.
7. The nano zinc oxide modified waterborne polyurethane emulsion of claim 6, wherein the silane modified nano zinc oxide is prepared by: drying the nano zinc oxide in an oven at 120 ℃ for 2-3h, adding a silane coupling agent into absolute ethyl alcohol, and ultrasonically dispersing for 1h, wherein the mass ratio of the nano zinc oxide to the silane coupling agent to the absolute ethyl alcohol is 1-3: 1: 100, then stirring and reacting for 2 hours at the constant temperature of 60 ℃, filtering, washing for more than 3 times by using absolute ethyl alcohol, and drying for 3 hours at the temperature of 80 ℃ in an oven to obtain the product.
8. The nano-zinc oxide modified waterborne polyurethane emulsion as claimed in claim 6 or 7, wherein the silane coupling agent is any one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane and N- (β -chloroethyl) -gamma-aminopropyltrimethoxysilane, preferably, the nano-zinc oxide is rod-shaped nano-zinc oxide, and the particle size is 30-60 nm.
9. The preparation method of the nano zinc oxide modified waterborne polyurethane emulsion based on any one of claims 1 to 8 is characterized by comprising the following steps:
s1, prepolymerization: adding polyether polyol and polyester polyol into a reaction container for vacuum dehydration treatment, then sequentially adding a micromolecular polyol chain extender and part of diisocyanate, and carrying out heat preservation reaction for 2 hours at the temperature of 80-85 ℃;
s2, chain extension: adding a carboxylic acid type hydrophilic chain extender and a proper amount of organic solvent into a reaction system of S1, reacting for 2 hours at the temperature of 80-85 ℃, then adding the rest diisocyanate, dropwise adding an organic metal catalyst, and continuing to react for 3-4 hours at the temperature of 80-85 ℃; cooling to 30-40 ℃, adding part of sulfonic acid type hydrophilic chain extender and a proper amount of organic solvent, and continuing to react for 10-20 min;
s3, dispersing and chain extending: and (2) at 30-40 ℃, dropwise adding a neutralizer into the reaction system of S2 for neutralization treatment for 30min, simultaneously adding the rest organic solvent, then dissolving the rest sulfonic acid type hydrophilic chain extender into deionized water, adding the solution into the reaction system under high-speed shearing force, dispersing for 30min, adding silane modified nano zinc oxide, stirring for 30min, and removing the organic solvent by reduced pressure distillation to obtain the high-solid-content waterborne polyurethane emulsion.
10. The preparation method of the nano zinc oxide modified waterborne polyurethane emulsion as claimed in claim 9, wherein the mass percentages of the sulfonic acid type hydrophilic chain extenders in S2 and S3 are 10-20: 80-90.
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