A water-based modified polyurethane dull oil with wear resistance and explosion resistance and its preparation method

Abstract

The present invention relates to the technical field of dull oil, and discloses a wear-resistant and explosion-proof waterborne modified polyurethane dull oil and a preparation method thereof. In the present invention, γ-glycidoxypropyltrimethoxysilane is successively reacted with silicon dioxide and tributyl phosphate to obtain a silicon-phosphorus-containing polyol, and then it is reacted with toluene-2,4-diisocyanate under the catalytic reaction of dibutyltin dilaurate to obtain a silicon-phosphorus-containing terminal isocyanate prepolymer. First, polycaprolactone, dimethylolpropionic acid, etc. are reacted with the silicon-phosphorus-containing terminal isocyanate prepolymer to obtain a polyurethane oligomer, and then it is reacted with polyaspartate to obtain a waterborne polyurethane polyurea emulsion. Finally, a defoaming agent, a diluent, etc. are added to a linear waterborne polyurethane emulsion and the waterborne polyurethane polyurea emulsion, and stirred and dispersed to obtain a polyurethane dull oil. The polyurethane dull oil prepared by the present invention has excellent wear resistance, explosion resistance and flame retardancy.

Description

Technical Field

[0001] The present invention relates to the technical field of dull oil, and specifically to a wear-resistant and explosion-resistant wire water-based modified polyurethane dull oil and a preparation method thereof. Background Art

[0002] With the improvement of people's living standards and aesthetic awareness, water-based matte coatings are deeply favored by people for their simple, elegant, and beautiful characteristics. Therefore, the research on water-based matte coatings is one of the research hotspots of researchers. Polyurethane materials have excellent mechanical properties, wear resistance, chemical resistance and other characteristics, and are widely used in the fields of national defense, textiles, medical treatment, transportation, etc.

[0003] For example, the patent with the authorization announcement number CN105176365B discloses a high-tolerance water-based matte topcoat for plastic films and a preparation method thereof. The invention is prepared from a water-based matte resin, a defoaming agent, a leveling agent, a cross-linking agent, etc., and has the advantages of environmental protection, wear resistance, high viscosity, etc., but does not improve the flame retardant performance and explosion resistance performance of the water-based matte topcoat.

[0004] For example, the patent with the application publication number CN113999586A discloses a weather-resistant water-based polyurethane matte varnish. The invention is prepared from a PUA emulsion, a flame retardant, a wetting and dispersing agent, etc. The prepared polyurethane matte varnish has the characteristics of flame retardancy, wear resistance, good flexibility, etc., but does not improve its explosion resistance performance. Summary of the Invention

[0005] (I) Technical Problems to be Solved

[0006] Aiming at the deficiencies of the prior art, the present invention provides a wear-resistant and explosion-resistant wire water-based modified polyurethane dull oil and a preparation method thereof. The prepared polyurethane dull oil has excellent wear resistance, explosion resistance, and flame retardant effects.

[0007] (II) Technical Solutions

[0008] A wear-resistant and explosion-resistant wire water-based modified polyurethane dull oil is made from the following raw materials in parts by weight: 3-6 parts of defoaming agent, 3-8 parts of wetting and dispersing agent, 2-6 parts of surfactant, 1-2 parts of leveling agent, 8-15 parts of diluent, 100 parts of linear water-based polyurethane emulsion, and 60-100 parts of water-based polyurethane polyurea emulsion.

[0009] Preferably, the preparation method is: adding a defoaming agent, a wetting and dispersing agent, a surfactant, a leveling agent, and a diluent to deionized water, stirring and dispersing, and then adding a linear water-based polyurethane emulsion and a water-based polyurethane polyurea emulsion thereto, and stirring and dispersing to obtain polyurethane dull oil.

[0010] Preferably, the preparation method of the water-based polyurethane polyurea emulsion is as follows:

[0011] (1) Add silica to a flask containing ethyl acetate solvent, stir to disperse, then add γ-glycidoxypropyltrimethoxysilane thereto, heat to 60 - 80 °C, and stir for reaction for 8 - 15 h. After the reaction is completed, perform suction filtration, wash with ethyl acetate, and dry to obtain Intermediate 1.

[0012] (2) Add tributyl phosphate and phosphoric acid to the flask, control the temperature at 80 - 90 °C, stir evenly, then add Intermediate 1 thereto, heat to 95 - 120 °C, and stir for reaction for 4 - 10 h. After the reaction is completed, cool to room temperature, wash with acetone, and dry to obtain a silicon-phosphorus polyol.

[0013] (3) Add toluene-2,4-diisocyanate, silicon-phosphorus polyol, and dibutyltin dilaurate to a flask containing acetone solvent, heat to 60 - 80 °C, and stir for reaction for 5 - 10 h. After the reaction is completed, cool to room temperature, and rotary evaporate to remove the solvent to obtain a silicon-phosphorus terminal isocyanate prepolymer.

[0014] (4) Add polycaprolactone, dimethylolpropionic acid, and 1,4-cyclohexanedimethanol to a flask, perform vacuum dehydration, then add the silicon-phosphorus terminal isocyanate prepolymer thereto, stir for reaction at 50 - 80 °C for 2 - 6 h, then add polyaspartate ester thereto, continue the reaction for 30 - 80 min, then add triethylamine for neutralization for 30 - 60 min, and add ethylenediamine for chain extension for 20 - 50 min. After the reaction is completed, obtain an aqueous polyurethane-polyurea emulsion.

[0015] Preferably, in the step (1), the mass ratio of silica to γ-glycidoxypropyltrimethoxysilane is 1:8 - 10.

[0016] Preferably, in the step (2), the mass ratio of tributyl phosphate, phosphoric acid, and Intermediate 1 is 1:0.2 - 0.25:0.3 - 0.42.

[0017] Preferably, in the step (3), the ratio of toluene-2,4-diisocyanate, silicon-phosphorus polyol, and dibutyltin dilaurate is 0.5 - 0.8:1:0.003 - 0.005.

[0018] Preferably, in the step (4), the mass ratio of polycaprolactone, dimethylolpropionic acid, 1,4-cyclohexanedimethanol, silicon-phosphorus terminal isocyanate prepolymer, polyaspartate ester, triethylamine, and ethylenediamine is 1:0.1 - 0.18:0.08 - 0.14:1.2 - 3.4:0.8 - 1.6:0.1 - 0.15:0.02 - 0.1.

[0019] Preferably, in the step (4), the vacuum dehydration temperature is 100-110 °C, the pressure is -0.08 to -0.05 MPa, and the time is 1-3 h.

[0020] (III) Beneficial technical effects

[0021] In the present invention, γ-glycidoxypropyltrimethoxysilane is successively reacted with silicon dioxide and tributyl phosphate to obtain a silicon-phosphorus polyol, and then it is reacted with toluene-2,4-diisocyanate under the catalytic reaction of dibutyltin dilaurate to obtain a silicon-phosphorus terminal isocyanate prepolymer. First, polycaprolactone, dimethylolpropionic acid, etc. are reacted with the silicon-phosphorus terminal isocyanate prepolymer to obtain a polyurethane oligomer, and then it is reacted with polyaspartate to obtain an aqueous polyurethane-polyurea emulsion. Finally, a defoaming agent, a diluent, etc. are added to the linear aqueous polyurethane emulsion and the aqueous polyurethane-polyurea emulsion, and stirred and dispersed to obtain a polyurethane dull oil.

[0022] The polyurethane dull oil prepared in the present invention contains silicon dioxide, and silicon dioxide can be used as a matting agent to reduce the gloss of the polyurethane dull oil. However, silicon dioxide has a large surface energy and is extremely easy to agglomerate. In the present invention, it is reacted with an organic substance, which can not only achieve the purpose of dispersing silicon dioxide, but also improve the matting and dulling effects.

[0023] The polyurethane dull oil prepared in the present invention contains a polyurethane-polyurea structure, which has good compatibility with linear polyurethane. In addition, there are relatively strong urea bonds between the polyurea molecules to form a hard segment chain. The urea bond is connected by a hydrogen bond. Under the action of an external high-frequency impact load, the polyurea molecular chain segments move, and the hydrogen bond breaks to absorb a large amount of energy. When the shock wave is offset, the interaction between the molecular chain segments stops, and a new set of hydrogen bonds is formed inside. The polyurea structure will also continuously release and absorb energy through the continuous movement, breakage, and recombination of hydrogen bonds to achieve the purpose of explosion resistance.

[0024] The polyurethane dull oil prepared in the present invention contains a polyurethane-polyurea structure. The polyurethane structure contained therein is a wear-resistant structure, and the siloxane structure and silicon dioxide in it have relatively high bond energy silicon-oxygen-silicon bonds, which can absorb more energy when subjected to external impact, further improving the wear resistance of the polyurethane dull oil.

[0025] The polyurethane matte oil prepared by the present invention contains phosphorus and silicon elements. When the material is heated, the phosphorus element contained therein can generate acidic substances such as phosphoric acid and metaphosphoric acid. These substances have strong dehydrating properties and can promote the dehydration of the material to form carbon, forming a dense carbon layer on the surface of the substrate. When the silicon element contained therein is heated, it can form a glassy substance on the surface of the material, isolating the material from the transfer of substances and energy from the outside world, and further improving the flame retardancy of the material. The polyurethane matte oil prepared by the present invention has excellent wear resistance, explosion resistance, and flame retardancy. Description of the Drawings

[0026] Figure 1 is the preparation route of the silicon-containing phosphorus polyol. Detailed Embodiments

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art belong to the scope of protection of the present invention.

[0028] The preparation method of the linear aqueous polyurethane emulsion is as follows: 5.9 g of polycarbonate diol is taken in a flask and vacuum dehydrated at 120 °C. Then, 1.7 g of toluene-2,4-diisocyanate and 0.007 g of dibutyltin dilaurate are added thereto. At 80 °C, the mixture is stirred and reacted for 30 min. Then, a mixed solution of dimethylolpropionic acid / N-methylpyrrolidone is added thereto, and the reaction is continued for 3 h. After cooling to room temperature, 1 g of triethylamine is added thereto and neutralized for 30 min to obtain a linear aqueous polyurethane emulsion. Example 1

[0029] (1) 3 g of silicon dioxide is added to a flask containing ethyl acetate solvent and stirred to disperse. Then, 30 g of γ-glycidoxypropyltrimethoxysilane is added thereto, and the temperature is raised to 70 °C and stirred and reacted for 12 h. After the reaction is completed, suction filtration is carried out, washed with ethyl acetate, and dried to obtain Intermediate 1.

[0030] (2) 20 g of tributyl phosphate and 4.2 g of phosphoric acid are added to the flask, the temperature is controlled at 85 °C and stirred evenly. Then, 8.4 g of Intermediate 1 is added thereto, and the temperature is raised to 110 °C and stirred and reacted for 8 h. After the reaction is completed, it is cooled to room temperature, washed with acetone, and dried to obtain the silicon-containing phosphorus polyol.

[0031] (3) Add 15 g of toluene-2,4-diisocyanate, 30 g of silicon-phosphorus polyol, and 0.25 g of dibutyltin dilaurate into a flask containing acetone solvent, heat up to 70 °C, stir and react for 8 h. After the reaction is completed, cool to room temperature and remove the solvent by rotary evaporation to obtain a silicon-phosphorus terminal isocyanate prepolymer.

[0032] (4) Add 40 g of polycaprolactone, 5 g of dimethylolpropionic acid, and 4 g of 2-1,4-cyclohexanedimethanol into a flask, dehydrate under vacuum. The vacuum dehydration temperature is 110 °C, the pressure is -0.05 MPa, and the time is 2 h. Then add 50 g of the silicon-phosphorus terminal isocyanate prepolymer into it, stir and react at 70 °C for 6 h. Then add 60 g of polyaspartate into it and continue to react for 60 min. Then add 5 g of triethylamine to neutralize for 40 min and 3.2 g of ethylenediamine to chain-extend for 30 min. After the reaction is completed, a waterborne polyurethane-polyurea emulsion is obtained.

[0033] (5) Add 4 g of defoamer W0506, 5 g of wetting and dispersing agent YF-98, 4 g of surfactant F-105, 1.5 g of leveling agent BYK358, and 12 g of 692 reactive diluent into deionized water, stir and disperse. Then add 100 g of linear waterborne polyurethane emulsion and 60 g of waterborne polyurethane-polyurea emulsion into it and stir and disperse to obtain a polyurethane matte oil. Example 2

[0034] (1) Add 3 g of silica into a flask containing ethyl acetate solvent, stir and disperse. Then add 25 g of γ-glycidoxypropyltrimethoxysilane into it, heat up to 70 °C and stir and react for 10 h. After the reaction is completed, filter by suction, wash with ethyl acetate, and dry to obtain Intermediate 1.

[0035] (2) Add 20 g of tributyl phosphate and 4 g of phosphoric acid into the flask, control the temperature at 90 °C, stir evenly. Then add 8 g of Intermediate 1 into it, heat up to 120 °C and stir and react for 8 h. After the reaction is completed, cool to room temperature, wash with acetone, and dry to obtain a silicon-phosphorus polyol.

[0036] (3) Add 15 g of toluene-2,4-diisocyanate, 30 g of silicon-phosphorus polyol, and 0.15 g of dibutyltin dilaurate into a flask containing acetone solvent, heat up to 70 °C, stir and react for 5 h. After the reaction is completed, cool to room temperature and remove the solvent by rotary evaporation to obtain a silicon-phosphorus terminal isocyanate prepolymer.

[0037] (4) Add 40 g of polycaprolactone, 6 g of dimethylolpropionic acid, and 4 g of 2-1,4-cyclohexanedimethanol into a flask, and conduct vacuum dehydration. The temperature of the vacuum dehydration is 110 °C, the pressure is -0.06 MPa, and the time is 3 h. Then add 120 g of a silicon-phosphorus-terminated isocyanate prepolymer thereto, and stir and react at 60 °C for 5 h. Then add 60 g of polyaspartate thereto, and continue to react for 40 min. Then add 5 g of triethylamine to conduct neutralization for 60 min, and 3 g of ethylenediamine to conduct chain extension for 50 min. After the reaction is completed, an aqueous polyurethane-polyurea emulsion is obtained.

[0038] (5) Add 6 g of defoamer W0506, 7 g of wetting and dispersing agent YF-98, 4 g of surfactant F-105, 1.4 g of leveling agent BYK358, and 10 g of 692 reactive diluent into deionized water, stir and disperse. Then add 100 g of linear aqueous polyurethane emulsion and 70 g of aqueous polyurethane-polyurea emulsion thereto, stir and disperse to obtain a polyurethane matte oil. Example 3

[0039] (1) Add 3 g of silica to a flask containing ethyl acetate solvent, stir and disperse. Then add 28 g of γ-glycidoxypropyltrimethoxysilane thereto, heat up to 70 °C, and stir and react for 12 h. After the reaction is completed, conduct suction filtration, wash with ethyl acetate, and dry to obtain Intermediate 1.

[0040] (2) Add 20 g of tributyl phosphate and 4.5 g of phosphoric acid to the flask, control the temperature at 80 °C, stir evenly. Then add 7 g of Intermediate 1 thereto, heat up to 100 °C, and stir and react for 10 h. After the reaction is completed, cool to room temperature, wash with acetone, and dry to obtain a silicon-phosphorus-containing polyol.

[0041] (3) Add 15 g of toluene-2,4-diisocyanate, 30 g of silicon-phosphorus-containing polyol, and 0.2 g of dibutyltin dilaurate to a flask containing acetone solvent, heat up to 70 °C, and stir and react for 10 h. After the reaction is completed, cool to room temperature, and remove the solvent by rotary evaporation to obtain a silicon-phosphorus-terminated isocyanate prepolymer.

[0042] (4) Add 40 g of polycaprolactone, 6 g of dimethylolpropionic acid, and 4 g of 2-1,4-cyclohexanedimethanol into a flask, and conduct vacuum dehydration. The temperature of the vacuum dehydration is 110 °C, the pressure is -0.05 MPa, and the time is 2 h. Then add 100 g of a silicon-phosphorus-terminated isocyanate prepolymer thereto, and stir and react at 60 °C for 6 h. Then add 50 g of polyaspartate thereto, and continue to react for 80 min. Then add 4 g of triethylamine to conduct neutralization for 60 min, and 0.8 g of ethylenediamine to conduct chain extension for 40 min. After the reaction is completed, an aqueous polyurethane-polyurea emulsion is obtained.

[0043] (5) Add 3 g of defoamer W0506, 7 g of wetting and dispersing agent YF-98, 5 g of surfactant F-105, 1.5 g of leveling agent BYK358, and 12 g of 692 reactive diluent to deionized water, stir and disperse, then add 100 g of linear waterborne polyurethane emulsion and 80 g of waterborne polyurethane-polyurea emulsion thereto, stir and disperse to obtain polyurethane matte oil. Example 4

[0044] (1) Add 3 g of silicon dioxide to a flask containing ethyl acetate solvent, stir and disperse, then add 30 g of γ-glycidoxypropyltrimethoxysilane thereto, raise the temperature to 70 °C, stir and react for 12 h. After the reaction is completed, filter by suction, wash with ethyl acetate, and dry to obtain Intermediate 1.

[0045] (2) Add 20 g of tributyl phosphate and 4.5 g of phosphoric acid to the flask, control the temperature at 80 °C, stir evenly, then add 8 g of Intermediate 1 thereto, raise the temperature to 100 °C, stir and react for 10 h. After the reaction is completed, cool to room temperature, wash with acetone, and dry to obtain silicon-phosphorus polyol.

[0046] (3) Add 24 g of toluene-2,4-diisocyanate, 30 g of silicon-phosphorus polyol, and 0.13 g of dibutyltin dilaurate to a flask containing acetone solvent, raise the temperature to 80 °C, stir and react for 7 h. After the reaction is completed, cool to room temperature, and rotary evaporate to remove the solvent to obtain silicon-phosphorus terminal isocyanate prepolymer.

[0047] (4) Add 40 g of polycaprolactone, 4 g of dimethylolpropionic acid, and 5 g of 2-1,4-cyclohexanedimethanol to the flask, dehydrate under vacuum. The vacuum dehydration temperature is 100 °C, the pressure is -0.07 MPa, and the time is 2 h. Then add 120 g of silicon-phosphorus terminal isocyanate prepolymer thereto, stir and react at 70 °C for 5 h, then add 50 g of polyaspartate thereto, continue to react for 80 min, then add 4 g of triethylamine for neutralization for 40 min and 2 g of ethylenediamine for chain extension for 40 min. After the reaction is completed, obtain waterborne polyurethane-polyurea emulsion.

[0048] (5) Add 5 g of defoamer W0506, 7 g of wetting and dispersing agent YF-98, g of surfactant F-105, 2 g of leveling agent BYK358, and 12 g of 692 reactive diluent to deionized water, stir and disperse, then add 100 g of linear waterborne polyurethane emulsion and 90 g of waterborne polyurethane-polyurea emulsion thereto, stir and disperse to obtain polyurethane matte oil. Example 5

[0049] (1) Add 3 g of silica to a flask containing ethyl acetate solvent, stir to disperse, then add 25 g of γ-glycidoxypropyltrimethoxysilane thereto, heat up to 70 °C, and stir and react for 14 h. After the reaction is completed, perform suction filtration, wash with ethyl acetate, and dry to obtain Intermediate 1.

[0050] (2) Add 20 g of tributyl phosphate and 4.2 g of phosphoric acid to the flask, control the temperature at 80 °C, stir evenly, then add 7 g of Intermediate 1 thereto, heat up to 110 °C, and stir and react for 8 h. After the reaction is completed, cool to room temperature, wash with acetone, and dry to obtain a silicon-phosphorus polyol.

[0051] (3) Add 20 g of toluene-2,4-diisocyanate, 30 g of the silicon-phosphorus polyol, and 0.15 g of dibutyltin dilaurate to a flask containing acetone solvent, heat up to 70 °C, and stir and react for 8 h. After the reaction is completed, cool to room temperature, and rotary evaporate to remove the solvent to obtain a silicon-phosphorus terminal isocyanate prepolymer.

[0052] (4) Add 40 g of polycaprolactone, 7 g of dimethylolpropionic acid, and 4 g of 2-1,4-cyclohexanedimethanol to the flask, perform vacuum dehydration. The vacuum dehydration temperature is 110 °C, the pressure is -0.08 MPa, and the time is 2.4 h. Then add 120 g of the silicon-phosphorus terminal isocyanate prepolymer thereto, stir and react at 50 °C for 3 h. Then add 60 g of polyaspartate thereto, continue to react for 80 min. Then add 4 g of triethylamine for neutralization for 40 min, and 3 g of ethylenediamine for chain extension for 20 - 50 min. After the reaction is completed, obtain an aqueous polyurethane-polyurea emulsion.

[0053] (5) Add 6 g of defoamer W0506, 3 g of wetting and dispersing agent YF-98, 5 g of surfactant F-105, 1.5 g of leveling agent BYK358, and 10 g of 692 reactive diluent to deionized water, stir to disperse, then add 100 g of linear aqueous polyurethane emulsion and 100 g of aqueous polyurethane-polyurea emulsion thereto, stir to disperse to obtain a polyurethane matte oil.

[0054] Comparative Example 1

[0055] Add 4 g of defoamer W0506, 5 g of wetting and dispersing agent YF-98, 4 g of surfactant F-105, 1.5 g of leveling agent BYK358, and 12 g of 692 reactive diluent to deionized water, stir to disperse, then add 100 g of linear aqueous polyurethane emulsion thereto, stir to disperse to obtain a polyurethane matte oil.

[0056] Add a nitrogen pyridine crosslinking agent to the polyurethane matte oil, mix evenly, apply it on the surface of black patent leather, and dry it at room temperature for 24 h and then in an oven at 100 °C for 10 h in sequence, and then conduct tests.

[0057] Low-temperature flexing test: Place the material at -20 °C and flex it repeatedly 30,000 times, and observe whether the coating cracks.

[0058] Scratch resistance test: Rub the surface of the coating vigorously with a cotton cloth 30 times, and observe the change of the coating.

[0059] Low-temperature flex resistance Scratch resistance Example 1 Slight cracking Excellent Example 2 No cracking Excellent Example 3 No cracking Excellent Example 4 No cracking Excellent Example 5 No cracking Excellent Comparative Example 1 Cracking Poor

[0060] As can be seen from the table, the low-temperature flexing resistance and scratch resistance of Examples 1-5 are better than those of Comparative Example 1. Therefore, the polyurethane matte oil prepared by the present invention has excellent wear resistance.

[0061] Use a limiting oxygen index tester to test the limiting oxygen index of the material.

[0062] Use a Shore hardness tester to test the hardness of the material.

[0063] Oxygen index (%) Hardness (HA) Example 1 24.9 21 Example 2 26.8 29 Example 3 29.1 34 Example 4 30.2 45 Example 5 31.4 42 Comparative Example 1 21.4 15

[0064] As can be seen from the table, the oxygen index of Examples 1-5 is larger than that of Comparative Example 1, and its flame retardant effect is better than that of Comparative Example 1. Therefore, the polyurethane matte oil prepared by the present invention has good flame retardant performance. The greater the hardness, the stronger the ability to resist deformation caused by external pressure and the stronger the explosion resistance. As can be seen from the table, the polyurethane matte oil prepared by the present invention has good explosion resistance.

[0065] The above description shows the main features, basic principles, and advantages of the present invention. For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments or examples, and without departing from the spirit or basic features of the present invention, the present invention can be implemented in other specific forms. Therefore, the above embodiments or examples should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be regarded as limiting the claims involved.

[0066] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A waterborne modified polyurethane dull oil for wear-resistant and explosion-proof wire, characterized in that It is made from the following raw materials in parts by weight: 3 - 6 parts of defoamer, 3 - 8 parts of wetting and dispersing agent, 2 - 6 parts of surfactant, 1 - 2 parts of leveling agent, 8 - 15 parts of diluent, 100 parts of linear aqueous polyurethane emulsion, 60 - 100 parts of aqueous polyurethane polyurea emulsion; The preparation method of the aqueous polyurethane polyurea emulsion is as follows: (1) Add silica to a flask containing ethyl acetate solvent, stir and disperse, then add γ - glycidoxypropyltrimethoxysilane to it, heat up to 60 - 80 °C, stir and react for 8 - 15 h. After the reaction is completed, filter by suction, wash with ethyl acetate, and dry to obtain Intermediate 1; (2) Add tributyl phosphate and phosphoric acid to the flask, control the temperature at 80 - 90 °C, stir evenly, then add Intermediate 1 to it, heat up to 95 - 120 °C, stir and react for 4 - 10 h. After the reaction is completed, cool to room temperature, wash with acetone, and dry to obtain silicon - phosphorus polyol; (3) Add toluene - 2,4 - diisocyanate, silicon - phosphorus polyol, and dibutyltin dilaurate to a flask containing acetone solvent, heat up to 60 - 80 °C, stir and react for 5 - 10 h. After the reaction is completed, cool to room temperature, and rotary evaporate to remove the solvent to obtain a silicon - phosphorus - terminated isocyanate prepolymer; (4) Add polycaprolactone, dimethylolpropionic acid, 1,4 - cyclohexanedimethanol to the flask, dehydrate under vacuum, then add the silicon - phosphorus - terminated isocyanate prepolymer to it, stir and react at 50 - 80 °C for 2 - 6 h, then add polyaspartate ester to it, continue to react for 30 - 80 min, then add triethylamine for neutralization for 30 - 60 min, and ethylenediamine for chain extension for 20 - 50 min. After the reaction is completed, an aqueous polyurethane polyurea emulsion is obtained.

2. A preparation method of the waterborne modified polyurethane dull oil for wear-resistant and explosion-proof wire as described in claim 1, characterized in that, Its preparation method is: Add defoamer, wetting and dispersing agent, surfactant, leveling agent, and diluent to deionized water, stir and disperse, then add linear aqueous polyurethane emulsion and aqueous polyurethane polyurea emulsion to it, stir and disperse to obtain polyurethane matte oil.

3. The preparation method of the waterborne modified polyurethane dull oil for wear-resistant and explosion-proof wire according to claim 2, characterized in that, In the step (1), the mass ratio of silica to γ - glycidoxypropyltrimethoxysilane is 1:8 - 10.

4. The preparation method of the waterborne modified polyurethane dull oil for wear-resistant and explosion-proof wires according to claim 2, characterized in that, In the step (2), the mass ratio of tributyl phosphate, phosphoric acid, and Intermediate 1 is 1:0.2 - 0.25:0.3 - 0.

42.

5. The preparation method of the waterborne modified polyurethane dull oil for wear-resistant and explosion-proof wire according to claim 2, characterized in that, In the step (3), the ratio of toluene - 2,4 - diisocyanate, silicon - phosphorus polyol, and dibutyltin dilaurate is 0.5 - 0.8:1:0.003 - 0.

005.

6. The preparation method of the waterborne modified polyurethane dull oil for wear-resistant and explosion-proof wire according to claim 2, characterized in that, In the step (4), the mass ratio of polycaprolactone, dimethylolpropionic acid, 1,4 - cyclohexanedimethanol, silicon - phosphorus - terminated isocyanate prepolymer, polyaspartate ester, triethylamine, and ethylenediamine is 1:0.1 - 0.18:0.08 - 0.14:1.2 - 3.4:0.8 - 1.6:0.1 - 0.15:0.02 - 0.

1.

7. The preparation method of the waterborne modified polyurethane dull oil for wear-resistant and explosion-proof wires according to claim 2, characterized in that, In the step (4), the vacuum dehydration temperature is 100 - 110 °C, the pressure is - 0.08 to - 0.05 MPa, and the time is 1 - 3 h.

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