Reactive polyurethane emulsifier and preparation method thereof

Abstract

The invention relates to the technical field of emulsifiers, and discloses a reactive polyurethane emulsifier and a preparation method thereof. According to the preparation method disclosed by the invention, a cationic polyurethane prepolymer is terminated by using fluorine-containing triazinyl modified polyoxyethylene ether, so that the reactive polyurethane emulsifier is obtained. The fluorine element is introduced into the polymer emulsifier, so that the hydrophobic acting force of the hydrophobic end is enhanced, the polymer emulsifier is more tightly adsorbed on an oil-water interface, and the emulsifying property of the emulsifier is improved; the triazinyl can form a synergistic effect with an emulsifier molecular chain segment through pi-pi accumulation or hydrogen bonds, compact molecular arrangement is formed on an oil-water interface, and the rigid structure of the triazinyl is beneficial to maintaining the mechanical strength of an interface film, so that the emulsifying capacity of the emulsifier is improved; silicon-oxygen bonds in silane groups can improve the adsorption stability of emulsifier molecules on an oil-water interface, so that the emulsifying performance is improved; quaternary ammonium salt groups can be adsorbed on an oil-water interface with negative charges through electrostatic interaction, so that the interfacial tension is reduced, and the emulsifying capacity is further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of emulsifiers, and specifically relates to a reactive polyurethane emulsifier and a preparation method thereof. Background Art

[0002] Traditional emulsion polymerization requires the use of emulsifiers. Since traditional emulsifiers are only adsorbed on the surface of polymers by physical means, during the process of emulsion drying into a film, small-molecule emulsifiers are desorbed and migrated to the surface of the latex film along with the convective evaporation of water, which has many adverse effects on the performance of the product, such as foaming, bonding strength, water resistance, cold resistance, and peel strength reduction. Since reactive emulsifiers can fix the emulsifier on the surface of latex particles through covalent bonding rather than physical adsorption, it can not only overcome the adverse effects caused by the residue of traditional emulsifiers in polymers, but also improve the stability of latex, and enhance the water resistance, radiation resistance, heat resistance and other properties of polymers, and has been widely used in many industries such as coatings, textile printing and dyeing, and oil extraction. CN115926105A discloses a reactive polyurethane anionic-nonionic emulsifier and its preparation method and application. The invention has simple process, high efficiency, stable quality, low cost, and is green and environmentally friendly. However, the interfacial adsorption ability, stability and shear resistance of its emulsifier are not high, which affects the emulsifying performance of the emulsifier. Summary of the Invention

[0003] (I) Technical Problems to be Solved Aiming at the deficiencies of the prior art, the present invention provides a reactive polyurethane emulsifier and a preparation method thereof. The reactive polyurethane emulsifier prepared by the present invention improves the interfacial adsorption ability, stability and shear resistance of the emulsifier, and has good emulsifying performance.

[0004] (II) Technical Solutions To achieve the above object, the present invention provides the following technical solution: A preparation method of a reactive polyurethane emulsifier, the preparation method of the reactive polyurethane emulsifier is: under nitrogen protection, add 9.8 - 10.2 g of isophorone diisocyanate and 7.9 - 8 g of silane quaternary ammonium salt to a reactor, stir and mix, add dibutyltin dilaurate catalyst thereto, heat up to 80 - 85 °C and react for 4.5 - 5.5 h to obtain a cationic polyurethane prepolymer, cool down to 72 - 76 °C, add 3.7 - 4 g of fluorinated triazine-based modified polyoxyethylene ether thereto, continue to react for 1 - 1.5 h, after the reaction ends, add petroleum ether for precipitation and then filter, and dry in vacuum to obtain the reactive polyurethane emulsifier.

[0005] Preferably, the mass of the dibutyltin dilaurate catalyst accounts for 0.03% - 0.04% of the total mass of the reactants.

[0006] Preferably, the preparation method of the silane quaternary ammonium salt is as follows: Add 5.8 - 6.1 g of N-methyldiethanolamine to 70 - 90 mL of anhydrous ethanol solvent, stir to dissolve, add 10.2 - 10.6 g of 3-chloropropyltrimethoxysilane dropwise thereto. After the dropping is completed, raise the temperature to 74 - 80 °C and reflux for 12 - 16 h. After the reaction is completed, remove the solvent by rotary evaporation to obtain the silane quaternary ammonium salt.

[0007] Preferably, the preparation method of the fluorinated triazine group-modified polyoxyethylene ether includes the following steps: (1) Add 16 - 18 mL of acetone and 9 - 12 mL of deionized water as solvents to the reactor. At 0 - 4 °C, add 5.5 - 5.6 g of cyanuric chloride and stir to dissolve. Dissolve 6.8 - 7.2 g of octafluoropentanol in 15 - 20 mL of acetone solvent, and simultaneously add it dropwise to the cyanuric chloride solution together with 11.6 - 12.2 g of sodium hydroxide solution. The dropping time is 1.5 - 2 h. After the dropping is completed, continue the reaction for 2 - 3 h. After the reaction is completed, wash and dry in vacuum to obtain Intermediate 1; (2) Add 3.7 - 3.9 g of Intermediate 1 to 40 - 50 mL of anhydrous acetonitrile solvent, stir to dissolve, raise the temperature to 42 - 48 °C, add 0.9 - 1.2 g of 2-aminopent-4-en-1-ol thereto, and use 1.1 - 1.3 g of acid-binding agent to maintain the pH at neutral. React at a constant temperature for 6 - 8 h. After the reaction is completed, remove the solvent by rotary evaporation, wash and dry in vacuum to obtain the fluorinated triazine group-modified initiator; (3) Add 2.5 - 3 g of the fluorinated triazine group-modified initiator and 0.02 - 0.04 g of catalyst to the autoclave, start stirring and evacuate. After purging with nitrogen, raise the temperature to 70 - 80 °C and dehydrate in vacuum for 40 - 60 min, then raise the temperature to 110 - 120 °C. Add 2.1 - 2.3 g of ethylene oxide dropwise thereto, cure at 150 - 160 °C and reaction pressure for 25 - 35 min, cool to 95 - 100 °C and bubble to remove gas for 1 - 1.5 h, then cool to 70 - 80 °C, add 0.03 - 0.05 g of acetic acid to adjust the pH to neutral to obtain the fluorinated triazine group-modified polyoxyethylene ether.

[0008] Preferably, the mass fraction of the sodium hydroxide solution in step (1) is 9% - 10%.

[0009] Preferably, the acid-binding agent in step (2) is triethylamine.

[0010] Preferably, the catalyst in step (3) is potassium hydroxide.

[0011] Preferably, the reaction pressure in step (3) is 0 - 0.4 MPa.

[0012] The present invention provides a reactive polyurethane emulsifier prepared by the preparation method as described above.

[0013] (III) Beneficial technical effects In the present invention, a cationic polyurethane prepolymer is capped with a fluorinated triazine group-modified polyoxyethylene ether to obtain a reactive polyurethane emulsifier.

[0014] Fluorine atoms have extremely high electronegativity and strong hydrophobicity. After introducing fluorine elements into the polymer emulsifier, the hydrophobic interaction of its hydrophobic end can be significantly enhanced, enabling it to adsorb more tightly on the oil-water interface. This strong adsorption ability can effectively prevent the aggregation of emulsion droplets and improve the emulsification performance of the emulsifier; the triazine group can form a synergistic effect with the molecular chain segments of the emulsifier through π-π stacking or hydrogen bonding, forming a dense molecular arrangement at the oil-water interface to prevent droplet aggregation, and the rigid structure of the triazine group helps to maintain the mechanical strength of the interfacial film and enhance the shear resistance and long-term stability of the emulsion, thereby improving the emulsification ability of the emulsifier; the silicon-oxygen bond in the silyl group has high bond energy and chemical inertness, which can enhance the adsorption stability of the emulsifier molecules at the oil-water interface and further improve the emulsification performance; the cationic group of the quaternary ammonium salt can be adsorbed on the negatively charged oil-water interface through electrostatic interaction, reducing the interfacial tension and further improving the emulsification ability of the emulsifier. Description of the drawings

[0015] Figure 1 is the synthesis reaction formula of the fluorinated triazine group-modified initiator.

[0016] Figure 2 is the synthesis reaction formula of the fluorinated triazine group-modified polyoxyethylene ether.

[0017] Figure 3 is the synthesis reaction formula of the cationic polyurethane prepolymer.

[0018] Figure 4 is the synthesis reaction formula of the reactive polyurethane emulsifier. Detailed implementation manners

[0019] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Apparently, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0020] To better understand the above technical solutions, the above technical solutions will be described in detail below in conjunction with the accompanying drawings of the specification and specific embodiments. Example 1

[0021] (1) Add 16 mL of acetone and 9 mL of deionized water into the reactor as solvents. At 0 °C, add 5.5 g of cyanuric chloride and stir to dissolve it. Dissolve 6.8 g of octafluoropentanol in 15 mL of acetone solvent, and simultaneously drip it and 11.6 g of sodium hydroxide solution with a mass fraction of 9% into the cyanuric chloride solution. The dripping time is 1.5 h. After the dripping is completed, continue the reaction for 2 h. After the reaction ends, wash and dry it under vacuum to obtain Intermediate 1; (2) Add 3.7 g of Intermediate 1 into 40 mL of anhydrous acetonitrile solvent, stir to dissolve it, heat up to 42 °C, add 0.9 g of 2-aminopent-4-en-1-ol into it, and use 1.1 g of triethylamine as an acid-binding agent to maintain the pH at neutral. React at a constant temperature for 6 h. After the reaction ends, remove the solvent by rotary evaporation, wash and dry it under vacuum to obtain a fluorine-containing triazine-based modified initiator; (3) Add 2.5 g of the fluorine-containing triazine-based modified initiator and 0.02 g of potassium hydroxide catalyst into the autoclave. Start stirring and evacuate the air. After purging with nitrogen, heat up to 70 °C and dehydrate under vacuum for 40 min, then heat up to 110 °C. Drip 2.1 g of ethylene oxide into it. Cure at 150 °C and 0 MPa for 25 min. Cool down to 95 °C and bubble to remove gas for 1 h, then cool down to 70 °C. Add 0.03 g of acetic acid to adjust the pH to neutral to obtain a fluorine-containing triazine-based modified polyoxyethylene ether; (4) Add 5.8 g of N-methyldiethanolamine into 70 mL of anhydrous ethanol solvent, stir to dissolve it, and drip 10.2 g of 3-chloropropyltrimethoxysilane into it. After the dripping is completed, heat up to 74 °C and reflux for 12 h. After the reaction ends, remove the solvent by rotary evaporation to obtain a quaternary ammonium salt of silane; (5) Under nitrogen protection, add 9.8 g of isophorone diisocyanate and 7.9 g of the quaternary ammonium salt of silane into the reactor, stir and mix them, and add dibutyltin dilaurate catalyst into it. The mass of the dibutyltin dilaurate catalyst accounts for 0.03% of the total mass of the reactants. Heat up to 80 °C and react for 4.5 h to obtain a cationic polyurethane prepolymer. Cool down to 72 °C, add 3.7 g of the fluorine-containing triazine-based modified polyoxyethylene ether into it, and continue the reaction for 1 h. After the reaction ends, add petroleum ether to precipitate and then filter, and dry it under vacuum to obtain a reactive polyurethane emulsifier. Example 2

[0022] (1) Add 18 mL of acetone and 12 mL of deionized water into the reactor as solvents. At 4 °C, add 5.6 g of cyanuric chloride and stir to dissolve it. Dissolve 7.2 g of octafluoropentanol in 20 mL of acetone solvent, and simultaneously drip it and 12.2 g of sodium hydroxide solution with a mass fraction of 10% into the cyanuric chloride solution. The dripping time is 2 h. After the dripping is completed, continue the reaction for 3 h. After the reaction ends, wash and dry it under vacuum to obtain Intermediate 1; (2) Add 3.9 g of intermediate 1 to 50 mL of anhydrous acetonitrile solvent, stir and dissolve, heat to 48 ° C, add 1.2 g of 2-aminopent-4-en-1-ol, use 1.3 g of triethylamine acid binder to maintain the pH at neutral, and react at constant temperature for 8 h. After the reaction is completed, remove the solvent by rotary evaporation, wash and vacuum dry to obtain a fluorine-containing triazine modified initiator; (3) 3 g of fluorinated triazine modified initiator and 0.04 g of potassium hydroxide catalyst were added to the autoclave, stirred and vacuumed, and after nitrogen replacement, the temperature was raised to 80 ° C for vacuum dehydration for 60 min, then raised to 120 ° C, 2.3 g of ethylene oxide was added dropwise thereto, and aged at 160 ° C and 0.4 MPa for 35 min, cooled to 100 ° C and bubbled for degassing for 1.5 h, and then cooled to 80 ° C, and 0.05 g of acetic acid was added to adjust the pH to neutral to obtain fluorinated triazine modified polyoxyethylene ether; (4) Add 6.1 g of N-methyldiethanolamine to 90 mL of anhydrous ethanol solvent, stir to dissolve, and add 10.6 g of 3-chloropropyltrimethoxysilane dropwise thereto. After the addition is complete, heat to 80 ° C and reflux for 16 hours. After the reaction is completed, remove the solvent by rotary evaporation to obtain a silane quaternary ammonium salt; (5) Under nitrogen protection, 10.2 g of isophorone diisocyanate and 8 g of silane quaternary ammonium salt were added to the reactor, stirred and mixed, and dibutyltin dilaurate catalyst was added thereto, wherein the mass of dibutyltin dilaurate catalyst accounted for 0.04% of the total mass of the reactants. The temperature was raised to 85 ° C and reacted for 5.5 h to obtain a cationic polyurethane prepolymer. The temperature was lowered to 76 ° C, and 4 g of fluorine-containing triazine-modified polyoxyethylene ether was added thereto. The reaction was continued for 1.5 h. After the reaction was completed, petroleum ether was added to precipitate, filtered, and vacuum dried to obtain a reactive polyurethane emulsifier. Example 3

[0023] (1) Add 17 mL of acetone and 10.5 mL of deionized water as solvents to the reactor. At 2°C, add 5.55 g of cyanuric chloride and stir to dissolve. Dissolve 7 g of octafluoropentanol in 17.5 mL of acetone solvent and add 11.9 g of 9.5% sodium hydroxide solution dropwise to the cyanuric chloride solution. The addition time is 1.8 h. After the addition is completed, continue the reaction for 2.5 h. After the reaction is completed, wash and vacuum dry to obtain intermediate 1. (2) Add 3.8 g of intermediate 1 to 45 mL of anhydrous acetonitrile solvent, stir and dissolve, heat to 45 ° C, add 1.05 g of 2-aminopent-4-en-1-ol, use 1.2 g of triethylamine as an acid binder to maintain the pH at neutral, and react at constant temperature for 7 h. After the reaction is completed, remove the solvent by rotary evaporation, wash and vacuum dry to obtain a fluorine-containing triazine modified initiator; (3) Add 2.75 g of fluorinated triazine-based modifier initiator and 0.03 g of potassium hydroxide catalyst into an autoclave. Start stirring and evacuate the air. After purging with nitrogen, heat up to 75 °C and dehydrate under vacuum for 50 min. Then heat up to 115 °C and dropwise add 2.2 g of ethylene oxide. Cure at 155 °C and 0.2 MPa for 30 min. Cool down to 98 °C and bubble off gas for 1.2 h. Then cool down to 75 °C and add 0.04 g of acetic acid to adjust the pH to neutral to obtain fluorinated triazine-based modified polyoxyethylene ether; (4) Add 5.95 g of N-methyldiethanolamine into 80 mL of anhydrous ethanol solvent and stir to dissolve. Dropwise add 10.4 g of 3-chloropropyltrimethoxysilane. After the addition is complete, heat up to 77 °C and reflux for 14 h. After the reaction is completed, remove the solvent by rotary evaporation to obtain quaternary ammonium silane salt; (5) Under nitrogen protection, add 10 g of isophorone diisocyanate and 7.95 g of quaternary ammonium silane salt into a reactor and stir to mix. Add dibutyltin dilaurate catalyst, and the mass of dibutyltin dilaurate catalyst accounts for 0.035% of the total mass of the reactants. Heat up to 82 °C and react for 5 h to obtain cationic polyurethane prepolymer. Cool down to 74 °C and add 3.85 g of fluorinated triazine-based modified polyoxyethylene ether and continue to react for 1.2 h. After the reaction is completed, precipitate with petroleum ether, filter, and dry in vacuum to obtain reactive polyurethane emulsifier. Example 4

[0024] (1) Add 16 mL of acetone and 9 mL of deionized water into a reactor as solvents. At 0 °C, add 5.5 g of cyanuric chloride and stir to dissolve. Dissolve 6.8 g of octafluoropentanol in 15 mL of acetone solvent and simultaneously dropwise add it and 11.6 g of 9% sodium hydroxide solution into the cyanuric chloride solution. The dropping time is 1.5 h. After the addition is complete, continue to react for 2 h. After the reaction is completed, wash and dry in vacuum to obtain Intermediate 1; (2) Add 3.7 g of Intermediate 1 into 40 mL of anhydrous acetonitrile solvent and stir to dissolve. Heat up to 42 °C and add 0.9 g of 2-aminopent-4-en-1-ol. Use 1.1 g of triethylamine as an acid-binding agent to maintain the pH at neutral and react at a constant temperature for 6 h. After the reaction is completed, remove the solvent by rotary evaporation, wash and dry in vacuum to obtain fluorinated triazine-based modifier initiator; (3) Add 3 g of fluorinated triazine-based modifier initiator and 0.04 g of potassium hydroxide catalyst into an autoclave. Start stirring and evacuate the air. After purging with nitrogen, heat up to 80 °C for vacuum dehydration for 60 min, then heat up to 120 °C. Dropwise add 2.3 g of ethylene oxide into it. Cure at 160 °C and 0.4 MPa for 35 min. Cool down to 100 °C and carry out bubbling degassing for 1.5 h, then cool down to 80 °C. Add 0.05 g of acetic acid to adjust the pH to neutral to obtain fluorinated triazine-based modified polyoxyethylene ether; (4) Add 6.1 g of N-methyldiethanolamine into 90 mL of anhydrous ethanol solvent and stir to dissolve. Dropwise add 10.6 g of 3-chloropropyltrimethoxysilane into it. After the addition is completed, heat up to 80 °C and reflux for 16 h. After the reaction is completed, remove the solvent by rotary evaporation to obtain quaternary ammonium salt of silane; (5) Under nitrogen protection, add 10 g of isophorone diisocyanate and 7.95 g of quaternary ammonium salt of silane into a reactor, stir and mix. Add dibutyltin dilaurate catalyst into it, and the mass of dibutyltin dilaurate catalyst accounts for 0.035% of the total mass of the reactants. Heat up to 82 °C and react for 5 h to obtain cationic polyurethane prepolymer. Cool down to 74 °C, add 3.85 g of fluorinated triazine-based modified polyoxyethylene ether into it, and continue to react for 1.2 h. After the reaction is completed, precipitate with petroleum ether, filter, and dry in vacuum to obtain reactive polyurethane emulsifier. Example 5

[0025] (1) Add 18 mL of acetone and 12 mL of deionized water into a reactor as solvents. At 4 °C, add 5.6 g of cyanuric chloride into it and stir to dissolve. Dissolve 7.2 g of octafluoropentanol in 20 mL of acetone solvent and simultaneously dropwise add it and 12.2 g of 10% sodium hydroxide solution into the cyanuric chloride solution. The dropping time is 2 h. After the addition is completed, continue to react for 3 h. After the reaction is completed, wash and dry in vacuum to obtain Intermediate 1; (2) Add 3.9 g of Intermediate 1 into 50 mL of anhydrous acetonitrile solvent and stir to dissolve. Heat up to 48 °C, add 1.2 g of 2-aminopent-4-en-1-ol into it, and use 1.3 g of triethylamine as an acid-binding agent to maintain the pH at neutral. React at a constant temperature for 8 h. After the reaction is completed, remove the solvent by rotary evaporation, wash and dry in vacuum to obtain fluorinated triazine-based modifier initiator; (3) Add 2.75 g of fluorinated triazine-based modifier initiator and 0.03 g of potassium hydroxide catalyst into an autoclave. Start stirring and evacuate the air. After purging with nitrogen, heat up to 75 °C and dehydrate under vacuum for 50 min. Then heat up to 115 °C and dropwise add 2.2 g of ethylene oxide. Cure at 155 °C and 0.2 MPa for 30 min. Cool down to 98 °C and bubble off gas for 1.2 h. Then cool down to 75 °C and add 0.04 g of acetic acid to adjust the pH to neutral to obtain fluorinated triazine-based modified polyoxyethylene ether; (4) Add 5.95 g of N-methyldiethanolamine into 80 mL of anhydrous ethanol solvent and stir to dissolve. Dropwise add 10.4 g of 3-chloropropyltrimethoxysilane. After dropping, heat up to 77 °C and reflux for 14 h. After the reaction, remove the solvent by rotary evaporation to obtain quaternary ammonium salt of silane; (5) Under nitrogen protection, add 9.8 g of isophorone diisocyanate and 7.9 g of quaternary ammonium salt of silane into a reactor and stir to mix. Add dibutyltin dilaurate catalyst, and the mass of dibutyltin dilaurate catalyst accounts for 0.03% of the total mass of the reactants. Heat up to 80 °C and react for 4.5 h to obtain cationic polyurethane prepolymer. Cool down to 72 °C and add 3.7 g of fluorinated triazine-based modified polyoxyethylene ether and continue to react for 1 h. After the reaction, precipitate with petroleum ether, filter, and dry in vacuum to obtain reactive polyurethane emulsifier.

[0026] Comparative Example 1 Compared with Example 1, the difference in this comparative example is that the quaternary ammonium salt of silane is not contained in step (5).

[0027] Comparative Example 2 Compared with Example 1, the difference in this comparative example is that the fluorinated triazine-based modified polyoxyethylene ether is not contained in step (5).

[0028] Dilute the emulsifiers in Examples 1 - 5 and Comparative Examples 1 - 2 with water to a mass fraction of 8%. Add 10 g of methyl methacrylate / styrene into 10 ml of the diluted emulsifier solution under stirring. After adding, continue to stir for 5 min. Pour the obtained monomer emulsion into a graduated cylinder and let it stand for 24 h, then measure the water separation. The test results are shown in Table 1.

[0029] Table 1: Emulsification performance test.

[0030] Item Water separation amount (methyl methacrylate) / mL Water separation amount (styrene) / mL Example 1 0.5 2.5 Example 2 0.7 2.8 Example 3 0.6 2.6 Example 4 0.5 2.5 Example 5 0.6 2.7 Comparative Example 1 2.2 4.0 Comparative Example 2 3.1 5.4 As can be seen from Table 1, the emulsifiers in Examples 1 - 5 of the present invention have lower water separation and better emulsification performance compared with the emulsifiers in Comparative Examples 1 - 2.

[0031] Add 80 g of distilled water and 0.05 g of sodium bisulfite into a flask, purge with nitrogen and stir for 0.5 h, then heat up to 45 °C, and dropwise add 10 g of vinyl acetate monomer dissolved with 0.03 g of emulsifiers in Examples 1-5 and Comparative Examples 1-2, and simultaneously dropwise add 10 g of ammonium persulfate solution with a mass concentration of 5 kg / cm 3 . After the dropping is completed, keep the temperature for 4 h and then cool down to 25 °C, and use a BZY-1 type automatic surface tension meter to measure the surface tension of the emulsion. The test results are shown in Table 2.

[0032] Table 2: Polymerization performance test.

[0033] Item Surface tension of the emulsion after polymerization (mN / m) Example 1 62.5 Example 2 61.4 Example 3 62.3 Example 4 60.8 Example 5 61.7 Comparative Example 1 59.6 Comparative Example 2 42.8 As can be seen from Table 2, the emulsions prepared with the emulsifiers in Examples 1-5 and Comparative Example 1 of the present invention have higher surface tension compared to the emulsion prepared with the emulsifier in Comparative Example 2. This is because the polyurethane emulsifier in Comparative Example 2 is not capped and has no reactive double bonds at the end, and there is physical adsorption on the latex particles and the emulsion surface. While the emulsifiers in Examples 1-5 and Comparative Example 1 have reactive double bonds at the end, copolymerize with the monomers during the polymerization process, and are bonded to the latex particles by chemical bonds. The emulsifier molecules will no longer be able to desorb from the latex particle surface, thus increasing the surface tension of the emulsion.

[0034] It should be noted that in this article, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device. Without further limitation, an element defined by the statement "including one..." does not exclude the existence of another identical element in the process, method, article or device including the said element.

[0035] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A preparation method of a reactive polyurethane emulsifier, characterized in that The preparation method of the reactive polyurethane emulsifier is as follows: Under nitrogen protection, 9.8 - 10.2 g of isophorone diisocyanate and 7.9 - 8 g of silane quaternary ammonium salt are added to a reactor, stirred and mixed, and dibutyltin dilaurate catalyst is added thereto. The temperature is raised to 80 - 85 °C and reacted for 4.5 - 5.5 h to obtain a cationic polyurethane prepolymer. The temperature is lowered to 72 - 76 °C, and 3.7 - 4 g of fluorine-containing triazine-based modified polyoxyethylene ether is added thereto, and the reaction is continued for 1 - 1.5 h. After the reaction is completed, petroleum ether is added for precipitation and then filtered, and vacuum dried to obtain the reactive polyurethane emulsifier; The preparation method of the silane quaternary ammonium salt is as follows: 5.8 - 6.1 g of N-methyldiethanolamine is added to 70 - 90 mL of anhydrous ethanol solvent, stirred and dissolved, and 10.2 - 10.6 g of 3-chloropropyltrimethoxysilane is added dropwise thereto. After the dropwise addition is completed, the temperature is raised to 74 - 80 °C and refluxed for 12 - 16 h. After the reaction is completed, the solvent is removed by rotary evaporation to obtain the silane quaternary ammonium salt; The preparation method of the fluorine-containing triazine-based modified polyoxyethylene ether includes the following steps: (1) 16 - 18 mL of acetone and 9 - 12 mL of deionized water are added to a reactor as solvents. At 0 - 4 °C, 5.5 - 5.6 g of cyanuric chloride is added thereto and stirred to dissolve. 6.8 - 7.2 g of octafluoropentanol is dissolved in 15 - 20 mL of acetone solvent and simultaneously added dropwise to the cyanuric chloride solution with 11.6 - 12.2 g of sodium hydroxide solution. The dropwise addition time is 1.5 - 2 h. After the dropwise addition is completed, the reaction is continued for 2 - 3 h. After the reaction is completed, it is washed and vacuum dried to obtain Intermediate 1; (2) 3.7 - 3.9 g of Intermediate 1 is added to 40 - 50 mL of anhydrous acetonitrile solvent, stirred and dissolved, the temperature is raised to 42 - 48 °C, 0.9 - 1.2 g of 2-aminopent-4-en-1-ol is added thereto, and the pH is maintained at neutral with 1.1 - 1.3 g of acid-binding agent. The reaction is carried out at a constant temperature for 6 - 8 h. After the reaction is completed, the solvent is removed by rotary evaporation, washed and vacuum dried to obtain the fluorine-containing triazine-based modified initiator; (3) 2.5 - 3 g of the fluorine-containing triazine-based modified initiator and 0.02 - 0.04 g of catalyst are added to an autoclave. Stirring is started and the air is evacuated. After nitrogen replacement, the temperature is raised to 70 - 80 °C for vacuum dehydration for 40 - 60 min, then the temperature is raised to 110 - 120 °C, and 2.1 - 2.3 g of ethylene oxide is added dropwise thereto. It is cured at 150 - 160 °C and reaction pressure for 25 - 35 min. The temperature is lowered to 95 - 100 °C for bubbling and degassing for 1 - 1.5 h, then the temperature is lowered to 70 - 80 °C, and 0.03 - 0.05 g of acetic acid is added to adjust the pH to neutral to obtain the fluorine-containing triazine-based modified polyoxyethylene ether.

2. The preparation method of the reactive polyurethane emulsifier according to claim 1, characterized in that, The mass of the dibutyltin dilaurate catalyst accounts for 0.03% - 0.04% of the total mass of the reactants.

3. The preparation method of the reactive polyurethane emulsifier according to claim 1, characterized in that, In the step (1), the mass fraction of the sodium hydroxide solution is 9% - 10%.

4. The preparation method of the reactive polyurethane emulsifier according to claim 1, characterized in that, In the step (2), the acid-binding agent is triethylamine.

5. The preparation method of the reactive polyurethane emulsifier according to claim 1, characterized in that, In the step (3), the catalyst is potassium hydroxide.

6. The preparation method of the reactive polyurethane emulsifier according to claim 1, characterized in that, The reaction pressure in the step (3) is 0 - 0.4 MPa.

7. A reactive polyurethane emulsifier prepared by the preparation method according to any one of claims 1 - 6.

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