A waterproofing agent and its preparation method and application

Abstract

The present invention provides a waterproofing agent and a preparation method and application thereof. According to the waterproofing agent of the present invention, the raw materials for preparation include organosilicon, polyglycol, diisocyanate, organotin catalyst, chain extender, neutralizer, solvent and end-capping agent. After being applied to a fabric, the waterproofing agent can react and crosslink inside and on the surface of the fabric to form a thin film with excellent water resistance, stain resistance and organic solvent resistance. The present invention also provides a preparation method and application of the waterproofing agent.

Description

Technical Field

[0001] The invention belongs to the technical field of textiles, and in particular relates to a waterproofing agent and a preparation method and application thereof. Background Art

[0002] In the field of textile waterproofing, the most widely used waterproofing agents are mainly fluorocarbon waterproofing agents. According to relevant research results, fluorocarbon waterproofing agents contain organic fluorine chemicals such as perfluorooctane sulfonyl compounds (PFOS) and perfluorooctanoic acid (PFOA) during production and use, which are potentially harmful to the ecological environment and human health, such as bioaccumulation and toxicity. With the continuous improvement of people's requirements for environmental protection, the application of fluorocarbon waterproofing agents has been restricted, and the development of their substitutes has become a trend. Since there is no effective way to solve the pollution problem of PFOS and PFOA, there is an urgent need for products that do not contain PFOS and PFOA to replace organic fluorine products, that is, fluorine-free waterproofing agents. Compared with fluorine-based waterproofing agents, fluorine-free waterproofing agents are not easy to deposit in organisms, are easy to degrade, and are harmless to the human body. They are safer and more environmentally friendly products. At present, fluorine-free waterproofing agents mainly include long-chain alkane waterproofing agents and silicone waterproofing agents.

[0003] Alkane long-chain waterproofing agents mainly include metal soap waterproofing agents, paraffin waterproofing agents, hydroxymethyl waterproofing agents, pyridine waterproofing agents, etc. Silicone waterproofing agents include silicone-modified polyurethane waterproofing agents. Traditional solvent-based polyurethane waterproofing agents usually use a large amount of organic volatile solvents to dissolve, dilute, and reduce viscosity in the later stage of their synthesis. This means that large-scale production will not only cause a sharp increase in the production costs of enterprises, but also may produce a large amount of toxic volatile organic compounds (VOCs) during use, thereby endangering the ecological environment and the health of front-line production workers. Compared with traditional solvent-based polyurethane, water-based polyurethane waterproofing agents use water as a dispersion medium. They are non-toxic and pollution-free when used, non-flammable, low in production cost, energy-saving, and can relatively completely retain the characteristics of solvent-based polyurethane. It is a very promising "green material".

[0004] Although water-based polyurethane waterproofing agents have the advantages of being environmentally friendly, having good film-forming properties, good toughness, wear resistance and strong adhesion, their applications are limited due to the low degree of cross-linking between molecular chains, the introduction of hydrophilic groups into the molecular chains, and the structural characteristics of the macromolecular chains of water-based polyurethane waterproofing agents. As a result, water-based polyurethane waterproofing agents have the disadvantages of being easily swellable in water after film formation, poor solvent resistance and weather resistance, poor thermal stability and weak mechanical strength. Summary of the invention

[0005] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the present invention provides a waterproofing agent which is not easy to swell in water, has good solvent resistance and weather resistance, good thermal stability and excellent mechanical strength.

[0006] The invention also provides a method for preparing the waterproofing agent.

[0007] The invention also provides an application of the waterproofing agent.

[0008] A first aspect of the present invention provides a waterproofing agent, wherein the raw materials for preparing the waterproofing agent include organic silicon, polyglycol, diisocyanate, organic tin catalyst, chain extender, neutralizer, solvent and end-capping agent.

[0009] One of the technical solutions of the present invention regarding the waterproofing agent has at least the following beneficial effects:

[0010] Combining silicone with ultra-low surface energy, flame retardancy, extremely low conductivity, high and low temperature resistance, hydrophobic and breathable with waterborne polyurethane, and copolymerizing and modifying the two is a way to overcome the defects of a single polymer. Modifying waterborne polyurethane with silicone can effectively achieve the complementary advantages of the two, thereby improving the hydrophobicity, thermal stability, chemical solvent resistance, etc. of waterborne polyurethane during film formation. Because the surface energy difference between the two is large, the surface energy of silicone is low, and the low surface energy component will gradually migrate to the outside of the high surface energy component, resulting in microphase separation between the two. When the modified polymer acts on the fabric, silicone will spontaneously migrate and enrich to the interface between the film and the air, thereby improving the water repellency of the fabric (increasing the water contact angle) and giving the fabric a soft and smooth feel. Therefore, silicone-modified waterborne polyurethane waterproofing agent products that are not troubled by environmental safety protection and do not contain PFOA and PFOS are of great significance to textile auxiliaries and even the textile industry.

[0011] After being applied to fabric, the waterproofing agent of the present invention can react and cross-link inside and on the surface of the fabric to form a thin film with excellent water resistance, stain resistance and organic solvent resistance.

[0012] The waterproofing agent of the present invention is prepared from raw materials:

[0013] Polyglycol can further enhance the strength and water penetration resistance of the waterproofing agent after film formation.

[0014] The waterproofing agent synthesized with diisocyanate as raw material has a film with high elasticity and excellent mechanical properties after application, and is not easy to yellow or age.

[0015] The chain extender can make the polymer macromolecular chain segment contain strong hydrophilic ionic groups, thereby improving the storage and use stability of the obtained waterproofing agent.

[0016] The neutralizer can effectively neutralize the carboxyl groups in the side chain groups of the polymer macromolecules to form salts, while making the pH value neutral and enhancing the stability of the reaction system.

[0017] When a blocking agent is used to block the unreacted isocyanate groups in the system, the reaction between the isocyanate groups and water in the subsequent water emulsification stage can be avoided, thereby enhancing the storage and use stability of the resulting waterproofing agent.

[0018] According to some embodiments of the present invention, the organosilicon includes at least one of amino organosilicon, silanol hydroxy organosilicon, hydroxyl polyether organosilicon, single-terminal hydroxyl organosilicon and bishydroxyl organosilicon.

[0019] According to some embodiments of the present invention, the organosilicon is a double-terminated dihydroxyl hydrocarbon organosilicon.

[0020] According to some embodiments of the present invention, the polyglycol includes at least one of polyether (ester) diols such as polyethylene oxide diol, polypropylene oxide diol, polytetramethylene glycol and polycarbonate diol.

[0021] According to some embodiments of the present invention, the polyglycol includes polyoxypropylene glycol and polytetramethylene glycol.

[0022] The polyglycol includes polyoxypropylene glycol and polytetrahydrofuran diol. The combination of polyoxypropylene glycol and polytetrahydrofuran diol can be used as the soft segment in the polymer macromolecular chain. By limiting the ratio of the two, the entanglement force of the molecular chains in the film-forming process is enhanced, the degree of hydrogen bonding between molecules is improved, the movement of the chain segments is hindered, the particles are tightly stacked in the film-forming process, and liquid water molecules are difficult to penetrate the film, so that the film formed after the prepared waterproofing agent is applied to the fabric and dried has excellent water-repellent and mechanical properties.

[0023] According to some embodiments of the present invention, the diisocyanate includes at least one of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, trimethylhexane diisocyanate and diphenylmethane diisocyanate.

[0024] According to some embodiments of the present invention, the diisocyanate is isophorone diisocyanate.

[0025] According to some embodiments of the present invention, the organic tin catalyst includes at least one of stannous octoate, dibutyltin dilaurate and dibutyltin dioctoate.

[0026] According to some embodiments of the present invention, the chain extender includes a small molecule chain extender and a hydrophilic chain extender.

[0027] According to some embodiments of the present invention, the small molecule chain extender includes at least one of 1,2-propylene glycol, 1,4-butanediol, 1,6-ethylene glycol and trimethylolpropane.

[0028] According to some embodiments of the present invention, the small molecule chain extender is 1,4-butanediol.

[0029] According to some embodiments of the present invention, the hydrophilic chain extender is at least one of dimethylol propionic acid, dimethylol butyric acid and dihydroxy half ester.

[0030] According to some embodiments of the present invention, the hydrophilic chain extender is dimethylol propionic acid.

[0031] According to some embodiments of the present invention, the neutralizing agent includes at least one of aqueous ammonia, triethanolamine and triethylamine.

[0032] According to some embodiments of the invention, the neutralizing agent is triethylamine.

[0033] According to some embodiments of the present invention, the solvent includes at least one of acetone, butanone, isobutyl acetate, N,N-dimethylformamide and N,N-dimethylacetamide.

[0034] According to some embodiments of the present invention, the end-capping agent is at least one of lactam, sodium bisulfite, phenol and butanone oxime.

[0035] According to some embodiments of the present invention, the capping agent is butanone oxime.

[0036] According to some embodiments of the present invention, the raw materials for preparation include, by weight:

[0037] Silicone: 20 to 40 parts,

[0038] Polyglycol: 60 to 80 parts,

[0039] Diisocyanate: 21 to 50 parts,

[0040] Organic tin catalyst: 0.20 to 0.55 parts,

[0041] Chain extender: 8.5 to 4 parts,

[0042] Neutralizer: 6 to 10 parts,

[0043] Solvent: 10 to 25 parts,

[0044] Capping agent: 1.5 to 3.5 parts.

[0045] According to some embodiments of the present invention, the solid content of the waterproofing agent is 30-50%.

[0046] Within this solid content range, the waterproofing agent has good dispersion effect and strong stability in solvent water.

[0047] The second aspect of the present invention provides a method for preparing the waterproofing agent, comprising the following steps:

[0048] S1: in the presence of the organotin catalyst, adding the diisocyanate to the polydiol for prepolymerization to obtain a double-ended prepolymer containing isocyanate groups;

[0049] S2: adding the organosilicon to the double-ended isocyanate group-containing prepolymer for reaction, and then adding the chain extender dissolved in the solvent for chain extension reaction to obtain a chain extension mixture;

[0050] S3: adding the end-capping agent and the neutralizing agent to the chain extension mixture in sequence.

[0051] A technical solution in the method for preparing the waterproofing agent of the present invention has at least the following beneficial effects:

[0052] The method for preparing the waterproofing agent of the present invention has simple process, is environmentally friendly and energy-saving, does not require expensive equipment and complex process control, has undemanding reaction conditions, and is easy to produce.

[0053] The method for preparing the waterproofing agent of the present invention first uses polyglycol as the soft segment in the polymer macromolecular chain, so that the film formed after the prepared waterproofing agent is applied to fabric and dried has excellent water repellency and mechanical properties.

[0054] The method for preparing a waterproofing agent of the present invention introduces a double-terminal hydroxyl silicone with ultra-low surface energy into the soft segment of the macromolecular chain before adding a chain extender for chain extension reaction, thereby avoiding direct competition between the chain extender and the silicone in participating in the reaction with diisocyanate. Since the reaction activity of the isocyanate group is relatively less affected by the chain length, the access efficiency of the chain extender is low, and the distribution of the hydrophilic group in the chain extender in the chain segment is relatively uniform. In addition, as the amount of silicone added increases, the content of silicone on the surface of the film is higher, and it is difficult for water molecules to penetrate into the polymer macromolecular chain. At the same time, due to the extremely low polarity of silicone, silicone migrates and is enriched on the surface of the film, reducing the ability of water to wet the film, so that the fabric after being treated with the waterproofing agent has more excellent hydrophobicity, and at the same time has better stain resistance, weather resistance, aging resistance, and organic solvent resistance.

[0055] The method for preparing the waterproofing agent of the present invention is to introduce a blocking agent to block the excess incompletely reacted isocyanate groups in the reaction system after the chain extension reaction and before the neutralization reaction, so that the isocyanate groups lose their activity at room temperature and are prevented from being acted on by water or other hydrogen-containing active substances. When used, the isocyanate groups can be released by heating to a certain temperature, so that the isocyanate groups can be combined with components such as hydroxyl groups and amine groups on the fabric fibers, thereby forming a dense, complete and uniform highly hydrophobic film by cross-linking the inside and the surface of the fibers.

[0056] In the method for preparing a waterproofing agent of the present invention, the selected blocking agent has a lower deblocking temperature compared with a traditional blocking agent, and the deblocking temperature is slightly higher than the boiling point of water, so that the isocyanate group released again during deblocking will not react with the solvent water to generate a gel that affects the stability of the waterproofing agent; at the same time, the deblocking temperature is not too high, which can greatly reduce energy consumption when performing fabric finishing.

[0057] According to some embodiments of the present invention, in step S1, the prepolymerization temperature is controlled at 60°C to 90°C.

[0058] According to some embodiments of the present invention, in step S1, the prepolymerization reaction time is 1 h to 3 h.

[0059] According to some embodiments of the present invention, in step S2, the organosilicon is added to the double-ended isocyanate group-containing prepolymer for reaction, the organosilicon needs to be fully dissolved in the solvent, the reaction temperature is controlled at 65° C. to 85° C., and the modification reaction time is 1 h to 3 h.

[0060] According to some embodiments of the present invention, in step S2, the chain extender dissolved in the solvent is added to carry out a chain extension reaction, the small molecule chain extender and the hydrophilic chain extender must be fully dissolved in the solvent, the boiling point of the solvent should be in the selection range of 90°C to 160°C, the temperature of the chain extension reaction is controlled at 70°C to 90°C, and the chain extension time is 1h to 3h.

[0061] According to some embodiments of the present invention, in step S3, the degree of neutralization determined by the neutralizer should be controlled at 80% to 100%, the neutralization temperature should be controlled at 30° C. to 70° C., and the neutralization time should be 0.5 h to 2 h. In the present invention, the degree of neutralization determined by the neutralizer should not be too high, as excessive neutralization affects water resistance.

[0062] According to some embodiments of the present invention, the method further comprises adding an appropriate amount of water to the product after step S3.

[0063] According to some embodiments of the present invention, the amount of water added is 130 to 150 parts by weight based on the total weight of the waterproofing agent.

[0064] The third aspect of the present invention provides use of the waterproofing agent in the preparation of textiles.

[0065] A technical solution of the present invention regarding the application of a waterproofing agent in the preparation of textiles has at least the following beneficial effects:

[0066] After being applied to fabric, the waterproofing agent of the present invention can react and cross-link with the surface of the fabric to form a thin film with excellent water resistance, stain resistance and organic solvent resistance, thereby improving the water resistance, stain resistance and hand feel of the fabric. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 This is a comparison chart of the waterproof effect test of the fabric after being finished with the waterproof agent prepared in Example 1.

[0068] Figure 2 This is a comparison chart of the waterproof effect test of the fabric after being finished with the waterproof agent prepared in Example 3.

[0069] Figure 3 This is a comparison chart of the waterproof effect test of the fabric after being finished with the waterproof agent prepared in Example 5.

[0070] Figure 4 This is an enlarged view of the waterproof effect test of the fabric after being finished with the waterproof agent prepared in Example 5.

[0071] Figure 5 This is a comparison chart of the waterproof effect test of the fabric after being finished with the waterproof agent prepared in Example 6.

[0072] Figure 6 This is an enlarged view of the waterproof effect test of the fabric after being finished with the waterproof agent prepared in Example 6. DETAILED DESCRIPTION

[0073] The following are specific embodiments of the present invention, and the technical solutions of the present invention are further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0074] In some embodiments of the present invention, the present invention provides a waterproofing agent, the preparation raw materials of which include organosilicon, polydiol, diisocyanate, organotin catalyst, chain extender, neutralizer, solvent and end-capping agent.

[0075] It can be understood that combining silicone with ultra-low surface energy, flame retardancy, extremely low conductivity, high and low temperature resistance, hydrophobic and breathable with waterborne polyurethane, and copolymerizing and modifying the two, is a way to overcome the defects of a single polymer. Modifying waterborne polyurethane with silicone can effectively achieve the complementary advantages of the two, thereby improving the hydrophobicity, thermal stability, chemical solvent resistance, etc. of waterborne polyurethane during film formation. Because the surface energy difference between the two is large, the surface energy of silicone is low, and the low surface energy component will gradually migrate to the outside of the high surface energy component, resulting in microphase separation between the two. When the modified polymer acts on the fabric, silicone will spontaneously migrate and enrich to the interface between the film and the air, thereby improving the water repellency of the fabric (increasing the water contact angle), while giving the fabric a soft and smooth feel. Therefore, silicone-modified waterborne polyurethane waterproofing agent products that are not troubled by environmental safety protection and do not contain PFOA and PFOS are of great significance to textile auxiliaries and even the textile industry.

[0076] Specifically, after being applied to fabric, the waterproofing agent of the present invention can react and cross-link with the surface of the fabric to form a thin film with excellent water resistance, stain resistance and organic solvent resistance.

[0077] The waterproofing agent of the present invention is prepared from raw materials:

[0078] Polyglycol can further enhance the strength and water penetration resistance of the waterproofing agent after film formation.

[0079] The waterproofing agent synthesized with diisocyanate as raw material has a film with high elasticity and excellent mechanical properties after application, and is not easy to yellow or age.

[0080] The chain extender can make the polymer macromolecular chain segment contain strong hydrophilic ionic groups, thereby improving the storage and use stability of the obtained waterproofing agent.

[0081] The neutralizer can effectively neutralize the carboxyl groups in the side chain groups of the polymer macromolecules to form salts, while making the pH value neutral and enhancing the stability of the reaction system.

[0082] When a blocking agent is used to block the unreacted isocyanate groups in the system, the reaction between the isocyanate groups and water in the subsequent water emulsification stage can be avoided, thereby enhancing the storage and use stability of the resulting waterproofing agent.

[0083] In some embodiments of the present invention, the organosilicon includes at least one of amino organosilicon, silanol hydroxy organosilicon, hydroxyl polyether organosilicon, single-terminal hydroxyl organosilicon and bis-hydroxyl organosilicon.

[0084] In some embodiments of the present invention, the organosilicon is a double-terminated bis-hydroxyl hydrocarbon organosilicon.

[0085] In some embodiments of the present invention, the polyglycol includes at least one of polyether (ester) diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and polycarbonate glycol.

[0086] In some embodiments of the present invention, the polyglycol includes polyoxypropylene glycol and polytetramethylene glycol.

[0087] The polyglycol includes polyoxypropylene glycol and polytetrahydrofuran diol. The combination of polyoxypropylene glycol and polytetrahydrofuran diol can be used as the soft segment in the polymer macromolecular chain. By limiting the ratio of the two, the entanglement force of the molecular chains in the film-forming process is enhanced, the degree of hydrogen bonding between molecules is improved, the movement of the chain segments is hindered, the particles are tightly stacked in the film-forming process, and liquid water molecules are difficult to penetrate the film, so that the film formed after the prepared waterproofing agent is applied to the fabric and dried has excellent water-repellent and mechanical properties.

[0088] In some embodiments of the present invention, the diisocyanate includes at least one of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, trimethylhexane diisocyanate, and diphenylmethane diisocyanate.

[0089] In some embodiments of the present invention, the diisocyanate is isophorone diisocyanate.

[0090] In some embodiments of the present invention, the organotin catalyst includes at least one of stannous octoate, dibutyltin dilaurate, and dibutyltin dioctoate.

[0091] In some embodiments of the present invention, the chain extender includes a small molecule chain extender and a hydrophilic chain extender.

[0092] In some embodiments of the present invention, the small molecule chain extender includes at least one of 1,2-propylene glycol, 1,4-butanediol, 1,6-ethylene glycol and trimethylolpropane.

[0093] In some embodiments of the present invention, the small molecule chain extender is 1,4-butanediol.

[0094] In some embodiments of the present invention, the hydrophilic chain extender is at least one of dimethylol propionic acid, dimethylol butyric acid, and dihydroxy half ester.

[0095] In some embodiments of the present invention, the hydrophilic chain extender is dimethylol propionic acid.

[0096] In some embodiments of the present invention, the neutralizing agent includes at least one of aqueous ammonia, triethanolamine and triethylamine.

[0097] In some embodiments of the present invention, the neutralizing agent is triethylamine.

[0098] In some embodiments of the present invention, the solvent includes at least one of acetone, butanone, isobutyl acetate, N,N-dimethylformamide and N,N-dimethylacetamide.

[0099] In some embodiments of the present invention, the end-capping agent is at least one of lactam, sodium bisulfite, phenol and butanone oxime.

[0100] In some embodiments of the present invention, the capping agent is butanone oxime.

[0101] In some embodiments of the present invention, the raw materials for preparation include, by weight:

[0102] Silicone: 20 to 40 parts,

[0103] Polyglycol: 60 to 80 parts,

[0104] Diisocyanate: 21 to 50 parts,

[0105] Organic tin catalyst: 0.20 to 0.55 parts,

[0106] Chain extender: 8.5 to 22 parts,

[0107] Neutralizer: 6 to 10 parts,

[0108] Solvent: 10 to 25 parts,

[0109] Capping agent: 1.5 to 3.5 parts.

[0110] In some embodiments of the present invention, the sum of the mass fractions of the organosilicon and the polyglycol is 100.

[0111] In some embodiments of the present invention, the solid content of the waterproofing agent is 30-50%.

[0112] Within this solid content range, the waterproofing agent has good dispersion effect and strong stability in solvent water.

[0113] In some other embodiments of the present invention, the present invention provides a method for preparing a waterproofing agent, comprising the following steps:

[0114] S1: In the presence of an organic tin catalyst, diisocyanate is added to polydiol for prepolymerization to obtain a prepolymer containing isocyanate groups at both ends;

[0115] S2: adding silicone to the double-ended prepolymer containing isocyanate groups to carry out a reaction, and then adding a chain extender dissolved in a solvent to carry out a chain extension reaction to obtain a chain extension mixture;

[0116] S3: adding a capping agent and a neutralizing agent to the chain extension mixture in sequence.

[0117] It can be understood that the method for preparing a waterproofing agent of the present invention has a simple process, is environmentally friendly and energy-saving, does not require expensive equipment and complex process control, has undemanding reaction conditions, and is easy to produce.

[0118] It should be noted that the method for preparing the waterproofing agent of the present invention first uses polyglycol as the soft segment in the polymer macromolecular chain, so that the film formed after the prepared waterproofing agent is applied to the fabric and dried has excellent water repellent properties and mechanical properties.

[0119] Furthermore, in the method for preparing the waterproofing agent of the present invention, before adding the chain extender for chain extension reaction, the double-terminal hydroxyl silicone with ultra-low surface energy is introduced into the soft segment of the macromolecular chain, thereby avoiding direct competition between the chain extender and the silicone in participating in the reaction with the diisocyanate. Since the reactivity of the isocyanate group is relatively less affected by the chain length, the access efficiency of the chain extender is low, and the distribution of the hydrophilic group in the chain extender in the chain segment is relatively uniform. In addition, as the amount of silicone added increases, the content of silicone on the surface of the film is higher, and it is difficult for water molecules to penetrate into the polymer macromolecular chain. At the same time, due to the extremely low polarity of silicone, silicone migrates and is enriched on the surface of the film, reducing the ability of water to wet the film, so that the fabric after being treated with the waterproofing agent has better hydrophobicity, and at the same time has better stain resistance, weather resistance, aging resistance, and organic solvent resistance.

[0120] The method for preparing the waterproofing agent of the present invention is to introduce a blocking agent to block the excess incompletely reacted isocyanate groups in the reaction system after the chain extension reaction and before the neutralization reaction, so that the isocyanate groups lose their activity at room temperature and are prevented from being acted on by water or other hydrogen-containing active substances. When used, the isocyanate groups can be released by heating to a certain temperature, so that the isocyanate groups can be combined with components such as hydroxyl groups and amine groups on the fabric fibers, thereby forming a dense, complete and uniform highly hydrophobic film by cross-linking the inside and the surface of the fibers.

[0121] In the method for preparing a waterproofing agent of the present invention, the selected blocking agent has a lower deblocking temperature compared with a traditional blocking agent, and the deblocking temperature is slightly higher than the boiling point of water, so that the isocyanate group released again during deblocking will not react with the solvent water to generate a gel that affects the stability of the waterproofing agent; at the same time, the deblocking temperature is not too high, which can greatly reduce energy consumption when performing fabric finishing.

[0122] In some embodiments of the present invention, in step S1, the prepolymerization temperature is controlled at 60°C to 90°C.

[0123] In some embodiments of the present invention, in step S1, the prepolymerization reaction time is 1 h to 3 h.

[0124] In some embodiments of the present invention, in step S2, silicone is added to the double-ended isocyanate group-containing prepolymer for reaction, the silicone needs to be fully dissolved in the solvent, the reaction temperature is controlled at 65° C. to 85° C., and the modification reaction time is 1 h to 3 h.

[0125] In some embodiments of the present invention, in step S2, a chain extender dissolved in a solvent is added to carry out a chain extension reaction. Both the small molecule chain extender and the hydrophilic chain extender need to be fully dissolved in the solvent. The boiling point of the solvent should be in the selection range of 90°C to 160°C. The temperature of the chain extension reaction is controlled at 70°C to 90°C, and the chain extension time is 1h to 3h.

[0126] In some embodiments of the present invention, in step S3, the degree of neutralization determined by the neutralizer should be controlled at 80% to 100%, the neutralization temperature should be controlled at 30° C. to 70° C., and the neutralization time should be 0.5 h to 2 h. In the present invention, the degree of neutralization determined by the neutralizer should not be too high, as excessive neutralization affects water resistance.

[0127] In some embodiments of the present invention, the preparation method further comprises adding an appropriate amount of water to the product after step S3.

[0128] In some embodiments of the present invention, the amount of water added is 130 to 150 parts by weight based on the total weight of the waterproofing agent.

[0129] In some embodiments of the present invention, the preparation method of the waterproofing agent may be:

[0130] (1) Weigh the raw materials according to the ratio;

[0131] (2) adding the polyglycol weighed in (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet, and performing a decompression distillation dehydration treatment at 115±5° C. to obtain anhydrous polyglycol;

[0132] (3) adding diisocyanate to the anhydrous polydiol (2) in the presence of a catalyst, stirring the mixture in a water bath to obtain a prepolymer containing isocyanate groups at both ends after a prepolymerization reaction;

[0133] (4) adding the organosilicon weighed in (1) to the prepolymer (3), stirring the mixture evenly in a water bath, and performing a modification reaction to obtain a preliminary modified mixture;

[0134] (5) slowly adding the small molecule chain extender and the hydrophilic chain extender weighed in (1) and completely dissolved in the solvent to the preliminary modified mixture (4), stirring the mixture evenly in a water bath, and performing a chain extension reaction to obtain a chain extension mixture;

[0135] (6) adding the end-capping agent weighed in (1) to the chain extension mixture (5), stirring the mixture evenly in a water bath to obtain an end-capping modified mixture;

[0136] (7) adding the neutralizing agent weighed in (1) dropwise to the blocked modified mixture (6), and stirring the mixture in a water bath to obtain a neutralized modified mixture;

[0137] (8) Add the pure water weighed in (1) to the modified mixture ionized in (7), stir evenly, and obtain an environmentally friendly fluorine-free silicone modified water-based polyurethane waterproofing agent.

[0138] In some other embodiments of the present invention, the present invention provides use of the waterproofing agent in the preparation of textiles.

[0139] It is easy to understand that the waterproofing agent of the present invention, after being applied to the fabric, can react and cross-link with the surface of the fabric to form a thin film with excellent water resistance, stain resistance and organic solvent resistance, thereby improving the water resistance, stain resistance and feel of the fabric.

[0140] The technical solution of the present invention will be better understood with reference to specific embodiments below.

[0141] Example 1

[0142] This embodiment prepares a waterproofing agent, specifically:

[0143] (1) Weigh the following raw materials according to their mass fractions:

[0144] 40 parts of polyoxypropylene glycol, 30 parts of polytetramethylene glycol and 30 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0) in total 100 parts, 40 parts of isophorone diisocyanate, 0.4 parts of organic tin catalyst stannous octoate, 6 parts of 1,4-butanediol, 8 parts of dimethylol propionic acid, 6.5 parts of triethylamine, 27 parts of organic solvent isobutyl acetate, 2 parts of lactam, and 134 parts of pure water;

[0145] (2) adding the polyglycol weighed in (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet, and performing a decompression distillation dehydration treatment at 115±5° C. to obtain anhydrous polyglycol;

[0146] (3) adding the isophorone diisocyanate weighed in (1) to the anhydrous polyglycol mixture in the presence of dibutyltin dilaurate, stirring the mixture in a water bath, and performing a prepolymerization reaction under a nitrogen atmosphere to obtain a prepolymer containing isocyanate groups at both ends; wherein the prepolymerization reaction temperature is controlled at 80° C., and the prepolymerization reaction time is 1.5 h;

[0147] (4) adding the double-terminal hydroxyl polyether silicone weighed in (1) to the prepolymer containing double-terminal isocyanate groups, stirring evenly in a water bath for modification reaction to obtain a preliminary modified mixture; wherein the silicone needs to be fully dissolved in the solvent, the modification reaction temperature is controlled at 70° C., and the modification reaction time is 1 hour;

[0148] (5) slowly adding the 1,4-butanediol and dimethylol propionic acid weighed in (1) and completely dissolved in the solvent to the preliminary modified mixture, stirring evenly in a water bath, and performing a chain extension reaction to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 70° C., and the chain extension time is 2 h;

[0149] (6) adding the lactam weighed in (1) to the chain extension mixture, stirring evenly in a water bath to obtain an end-capping modified mixture;

[0150] (7) adding the weighed triethylamine to the modified mixture and dropping it into the end-capped modified mixture, stirring evenly in a water bath to obtain a neutralized modified mixture; the degree of neutralization determined by triethylamine should be controlled at 95%, the neutralization temperature should be controlled at 35° C., and the neutralization time should be controlled at 0.5 h.

[0151] (8) adding weighed pure water droplets to the ionized modified mixture and stirring evenly to obtain an environmentally friendly fluorine-free organosilicon-modified waterborne polyurethane waterproofing agent; wherein the stirring time is 0.5 h and the solid content of the waterproofing agent is 35%.

[0152] Example 2

[0153] This embodiment prepares a waterproofing agent, specifically:

[0154] (1) Weigh the following raw materials according to their mass fractions:

[0155] 100 parts in total of 60 parts of polyoxypropylene glycol and 40 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 43.5 parts of isophorone diisocyanate, 0.4 parts of organotin catalyst stannous octoate, 6.5 parts of 1,4-butanediol, 8.5 parts of dimethylol propionic acid, 7.5 parts of triethylamine, 29 parts of organic solvent acetone, 3 parts of butanone oxime, and 137.5 parts of pure water;

[0156] (2) adding the polyglycol weighed in (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet, and performing a decompression distillation dehydration treatment at 115±5° C. to obtain anhydrous polyglycol;

[0157] (3) adding the isophorone diisocyanate weighed in (1) to the anhydrous polyglycol mixture in the presence of stannous octoate, stirring the mixture in a water bath, and performing a prepolymerization reaction under a nitrogen atmosphere to obtain a prepolymer containing isocyanate groups at both ends; wherein the prepolymerization reaction temperature is controlled at 85° C., and the prepolymerization reaction time is 2 h;

[0158] (4) adding the double-terminal hydroxyl polyether silicone weighed in (1) to the prepolymer containing double-terminal isocyanate groups, stirring evenly in a water bath for modification reaction to obtain a preliminary modified mixture; wherein the silicone needs to be fully dissolved in the solvent, the modification reaction temperature is controlled at 75° C., and the modification reaction time is 1.5 h;

[0159] (5) slowly adding the 1,4-butanediol and dimethylol propionic acid weighed in (1) and completely dissolved in the solvent to the preliminary modified mixture, stirring evenly in a water bath, and performing a chain extension reaction to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 70° C., and the chain extension time is 2.5 h;

[0160] (6) adding the butanone oxime weighed in (1) to the chain extension mixture, stirring evenly in a water bath to obtain an end-capping modified mixture;

[0161] (7) adding the weighed triethylamine to the modified mixture and dropping it into the end-capped modified mixture, stirring evenly in a water bath to obtain a neutralized modified mixture; the degree of neutralization determined by triethylamine should be controlled at 100%, the neutralization temperature should be controlled at 35° C., and the neutralization time should be controlled at 0.5 h.

[0162] (8) adding weighed pure water droplets to the ionized modified mixture and stirring evenly to obtain an environmentally friendly fluorine-free organosilicon-modified waterborne polyurethane waterproofing agent; wherein the stirring time is 0.5 h and the solid content of the waterproofing agent is 40%.

[0163] Example 3

[0164] This embodiment prepares a waterproofing agent, specifically:

[0165] (1) Weigh the following raw materials according to their mass fractions:

[0166] 100 parts in total of 75 parts of polyoxypropylene glycol and 25 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 46 parts of isophorone diisocyanate, 0.4 parts of organic tin catalyst stannous octoate, 7.5 parts of 1,4-butanediol, 10 parts of dimethylol propionic acid, 7.5 parts of triethylamine, 31 parts of organic solvent acetone, 3 parts of butanone oxime, and 135.5 parts of pure water;

[0167] (2) adding the polyglycol weighed in (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet, and performing a decompression distillation dehydration treatment at 115±5° C. to obtain anhydrous polyglycol;

[0168] (3) adding the isophorone diisocyanate weighed in (1) to the anhydrous polyglycol mixture in the presence of stannous octoate, stirring the mixture in a water bath, and performing a prepolymerization reaction under a nitrogen atmosphere to obtain a prepolymer containing isocyanate groups at both ends; wherein the prepolymerization reaction temperature is controlled at 80° C., and the prepolymerization reaction time is 1.5 h;

[0169] (4) adding the double-terminal hydroxyl polyether silicone weighed in (1) to the prepolymer containing double-terminal isocyanate groups, stirring evenly in a water bath for modification reaction to obtain a preliminary modified mixture; wherein the silicone needs to be fully dissolved in the solvent, the modification reaction temperature is controlled at 70° C., and the modification reaction time is 1.5 h;

[0170] (5) slowly adding the 1,4-butanediol and dimethylol propionic acid weighed in (1) and completely dissolved in the solvent to the preliminary modified mixture, stirring evenly in a water bath, and performing a chain extension reaction to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 70° C., and the chain extension time is 2 h;

[0171] (6) adding the dimethylolpropionic acid weighed in (1) to the chain extension mixture, stirring evenly in a water bath to obtain an end-capping modified mixture;

[0172] (7) adding the weighed triethylamine to the modified mixture and dropping it into the end-capped modified mixture, stirring evenly in a water bath to obtain a neutralized modified mixture; the degree of neutralization determined by triethylamine should be controlled at 90%, the neutralization temperature should be controlled at 35° C., and the neutralization time should be controlled at 0.5 h.

[0173] (8) adding weighed pure water droplets to the ionized modified mixture and stirring evenly to obtain an environmentally friendly fluorine-free organosilicon-modified waterborne polyurethane waterproofing agent; wherein the stirring time is 0.5 h and the solid content of the waterproofing agent is 35%.

[0174] Example 4

[0175] This embodiment prepares a waterproofing agent, specifically:

[0176] (1) Weigh the following raw materials according to their mass fractions:

[0177] 100 parts in total of 30 parts of polycarbonate diol, 30 parts of polytetramethylene glycol and 40 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 44 parts of isophorone diisocyanate, 0.4 parts of organotin catalyst stannous octoate, 6.5 parts of 1,4-butanediol, 9 parts of dimethylol propionic acid, 7.5 parts of triethylamine, 29 parts of organic solvent isobutyl acetate, 2 parts of sodium bisulfite, and 140 parts of pure water;

[0178] (2) adding the polyglycol weighed in (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet, and performing a decompression distillation dehydration treatment at 115±5° C. to obtain anhydrous polyglycol;

[0179] (3) adding the isophorone diisocyanate weighed in (1) to the anhydrous polyglycol mixture in the presence of stannous octoate, stirring the mixture in a water bath, and performing a prepolymerization reaction under a nitrogen atmosphere to obtain a prepolymer containing isocyanate groups at both ends; wherein the prepolymerization reaction temperature is controlled at 85° C., and the prepolymerization reaction time is 2 h;

[0180] (4) adding the double-terminal hydroxyl polyether silicone weighed in (1) to the prepolymer containing double-terminal isocyanate groups, stirring evenly in a water bath for modification reaction to obtain a preliminary modified mixture; wherein the silicone needs to be fully dissolved in the solvent, the modification reaction temperature is controlled at 75° C., and the modification reaction time is 1.5 h;

[0181] (5) slowly adding the 1,4-butanediol and dimethylol propionic acid weighed in (1) and completely dissolved in the solvent to the preliminary modified mixture, stirring evenly in a water bath, and performing a chain extension reaction to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 70° C., and the chain extension time is 2.5 h;

[0182] (6) adding the sodium bisulfite weighed in (1) to the chain extension mixture, stirring evenly in a water bath to obtain an end-capping modification mixture;

[0183] (7) adding the weighed triethylamine to the modified mixture and dropping it into the end-capped modified mixture, stirring evenly in a water bath to obtain a neutralized modified mixture; the degree of neutralization determined by triethylamine should be controlled at 95%, the neutralization temperature should be controlled at 35° C., and the neutralization time should be controlled at 0.5 h.

[0184] (8) adding weighed pure water droplets to the ionized modified mixture and stirring evenly to obtain an environmentally friendly fluorine-free organosilicon-modified waterborne polyurethane waterproofing agent; wherein the stirring time is 0.5 h and the solid content of the waterproofing agent is 45%.

[0185] Example 5

[0186] This embodiment prepares a waterproofing agent, specifically:

[0187] (1) Weigh the following raw materials according to their mass fractions:

[0188] 100 parts in total of 35 parts of polycarbonate diol, 35 parts of polytetramethylene glycol and 30 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 50 parts of isophorone diisocyanate, 0.5 parts of organotin catalyst stannous octoate, 10.5 parts of 1,4-butanediol, 9.5 parts of dimethylol propionic acid, 7.5 parts of triethylamine, 31 parts of organic solvent acetone, 2 parts of butanone oxime, and 147 parts of pure water;

[0189] (2) adding the polyglycol weighed in (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet, and performing a decompression distillation dehydration treatment at 115±5° C. to obtain anhydrous polyglycol;

[0190] (3) adding the isophorone diisocyanate weighed in (1) to the anhydrous polyglycol mixture in the presence of stannous octoate, stirring the mixture in a water bath, and performing a prepolymerization reaction under a nitrogen atmosphere to obtain a prepolymer containing isocyanate groups at both ends; wherein the prepolymerization reaction temperature is controlled at 80° C., and the prepolymerization reaction time is 2 h;

[0191] (4) adding the double-terminal hydroxyl polyether silicone weighed in (1) to the prepolymer containing double-terminal isocyanate groups, stirring evenly in a water bath for modification reaction to obtain a preliminary modified mixture; wherein the silicone needs to be fully dissolved in the solvent, the modification reaction temperature is controlled at 70° C., and the modification reaction time is 1.5 h;

[0192] (5) slowly adding the 1,4-butanediol and dimethylol propionic acid weighed in (1) and completely dissolved in the solvent to the preliminary modified mixture, stirring evenly in a water bath, and performing a chain extension reaction to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 80° C., and the chain extension time is 2 h;

[0193] (6) adding the butanone oxime weighed in (1) to the chain extension mixture, stirring evenly in a water bath to obtain an end-capping modified mixture;

[0194] (7) adding the weighed triethylamine to the modified mixture and dropping it into the end-capped modified mixture, stirring evenly in a water bath to obtain a neutralized modified mixture; the degree of neutralization determined by triethylamine should be controlled at 85%, the neutralization temperature should be controlled at 40° C., and the neutralization time should be controlled at 0.5 h.

[0195] (8) adding weighed pure water droplets to the ionized modified mixture and stirring evenly to obtain an environmentally friendly fluorine-free organosilicon-modified waterborne polyurethane waterproofing agent; wherein the stirring time is 0.5 h and the solid content of the waterproofing agent is 30%.

[0196] Example 6

[0197] This embodiment prepares a waterproofing agent, specifically:

[0198] (1) 100 parts in total of 40 parts of polycarbonate diol, 25 parts of polytetramethylene glycol and 35 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 42 parts of isophorone diisocyanate, 0.4 parts of organotin catalyst stannous octoate, 7 parts of 1,4-butanediol, 11 parts of dihydroxymethyl propionic acid, 9 parts of triethylamine, 35 parts of organic solvent butanone, 2 parts of sodium bisulfite, and 149 parts of pure water;

[0199] (2) adding the polyglycol weighed in (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet, and performing a decompression distillation dehydration treatment at 115±5° C. to obtain anhydrous polyglycol;

[0200] (3) adding the isophorone diisocyanate weighed in (1) to the anhydrous polyglycol mixture in the presence of stannous octoate, stirring the mixture in a water bath, and performing a prepolymerization reaction under a nitrogen atmosphere to obtain a prepolymer containing isocyanate groups at both ends; wherein the prepolymerization reaction temperature is controlled at 80° C., and the prepolymerization reaction time is 1.5 h;

[0201] (4) adding the double-terminal hydroxyl polyether silicone weighed in (1) to the prepolymer containing double-terminal isocyanate groups, stirring evenly in a water bath for modification reaction to obtain a preliminary modified mixture; wherein the silicone needs to be fully dissolved in the solvent, the modification reaction temperature is controlled at 80° C., and the modification reaction time is 1 hour;

[0202] (5) slowly adding the 1,4-butanediol and dimethylol propionic acid weighed in (1) and completely dissolved in the solvent to the preliminary modified mixture, stirring evenly in a water bath, and performing a chain extension reaction to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 75° C., and the chain extension time is 2 h;

[0203] (6) adding the sodium bisulfite weighed in (1) to the chain extension mixture, stirring evenly in a water bath to obtain an end-capping modification mixture;

[0204] (7) The weighed triethylamine is added to the modified mixture and added dropwise to the end-capped modified mixture, and the mixture is stirred evenly in a water bath to obtain a neutralized modified mixture; the degree of neutralization determined by the triethylamine should be controlled at 80%, the neutralization temperature should be controlled at 35° C., and the neutralization time should be controlled at 1 hour.

[0205] (8) adding weighed pure water droplets to the ionized modified mixture and stirring evenly to obtain an environmentally friendly fluorine-free organosilicon-modified waterborne polyurethane waterproofing agent; wherein the stirring time is 0.5 h and the solid content of the waterproofing agent is 30%.

[0206] Example 7

[0207] This embodiment prepares a waterproofing agent, specifically:

[0208] (1) Weigh the following raw materials according to their mass fractions:

[0209] 40 parts of polycarbonate diol, 25 parts of polytetramethylene glycol and 35 parts of silanol hydroxy silicone (CAS No.: 70131-67-8) in total 100 parts, 48 ​​parts of isophorone diisocyanate, 0.45 parts of dibutyltin dilaurate, 11 parts of 1,4-butanediol, 11 parts of dimethylolpropionic acid, 9 parts of triethylamine, 23 parts of organic solvent isobutyl acetate, 2 parts of butanone oxime, and 145 parts of pure water;

[0210] (2) adding the polyglycol weighed in (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet, and performing a decompression distillation dehydration treatment at 115±5° C. to obtain anhydrous polyglycol;

[0211] (3) adding the isophorone diisocyanate weighed in (1) to the anhydrous polyglycol mixture in the presence of an organic tin catalyst dibutyltin dilaurate, stirring the mixture in a water bath, and performing a prepolymerization reaction under a nitrogen atmosphere to obtain a prepolymer containing isocyanate groups at both ends; wherein the prepolymerization reaction temperature is controlled at 80° C., and the prepolymerization reaction time is 2.5 h;

[0212] (4) adding the single-terminal dihydroxyl hydrocarbon silicone weighed in (1) to the prepolymer containing a diisocyanate group, stirring evenly in a water bath for modification reaction to obtain a preliminary modified mixture; wherein the silicone needs to be fully dissolved in the solvent, the modification reaction temperature is controlled at 70° C., and the modification reaction time is 2.5 h;

[0213] (5) slowly adding the 1,4-butanediol and dimethylol propionic acid weighed in (1) and completely dissolved in the solvent to the preliminary modified mixture, stirring evenly in a water bath, and performing a chain extension reaction to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 80° C., and the chain extension time is 2 h;

[0214] (6) adding the butanone oxime weighed in (1) to the chain extension mixture, stirring evenly in a water bath to obtain an end-capping modified mixture;

[0215] (7) adding the weighed triethylamine to the modified mixture and dropping it into the end-capped modified mixture, stirring evenly in a water bath to obtain a neutralized modified mixture; the degree of neutralization determined by triethylamine should be controlled at 85%, the neutralization temperature should be controlled at 40° C., and the neutralization time should be controlled at 0.5 h.

[0216] (8) adding weighed pure water droplets to the ionized modified mixture and stirring evenly to obtain an environmentally friendly fluorine-free organosilicon-modified waterborne polyurethane waterproofing agent; wherein the stirring time is 0.5 h and the solid content of the waterproofing agent is 33%.

[0217] Example 8

[0218] This embodiment prepares a waterproofing agent, specifically:

[0219] (1) Weigh the following raw materials according to their mass fractions:

[0220] 60 parts of polytetramethylene glycol and 40 parts of amino silicone (CAS: 71750-79-3) in total 100 parts, 46 parts of isophorone diisocyanate, 0.55 parts of organic tin catalyst dibutyl tin dilaurate, 4 parts of 1,4-butanediol, 11 parts of dimethylol propionic acid, 8 parts of triethylamine, 21 parts of organic solvent N,N-dimethylformamide, 2 parts of butanone oxime, 150 parts of pure water;

[0221] (2) adding the polyglycol weighed in (1) into a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet, and performing a decompression distillation dehydration treatment at 115±5° C. to obtain anhydrous polyglycol;

[0222] (3) adding the isophorone diisocyanate weighed in (1) to the anhydrous polyglycol mixture in the presence of dibutyltin dilaurate, stirring the mixture in a water bath, and performing a prepolymerization reaction under a nitrogen atmosphere to obtain a prepolymer containing isocyanate groups at both ends; wherein the prepolymerization reaction temperature is controlled at 80° C., and the prepolymerization reaction time is 2.5 h;

[0223] (4) adding the double-terminal amino silicone weighed in (1) to the prepolymer containing double-terminal isocyanate groups, stirring evenly in a water bath for modification reaction to obtain a preliminary modified mixture; wherein the silicone needs to be fully dissolved in the solvent, the modification reaction temperature is controlled at 0-5°C, and the modification reaction time is 3 hours;

[0224] (5) slowly adding the 1,4-butanediol and dimethylol propionic acid weighed in (1) and completely dissolved in the solvent to the preliminary modified mixture, stirring evenly in a water bath, and performing a chain extension reaction to obtain a chain extension mixture; wherein the chain extension reaction temperature is controlled at 78° C., and the chain extension time is 2.5 h;

[0225] (6) adding the butanone oxime weighed in (1) to the chain extension mixture, stirring evenly in a water bath to obtain an end-capping modified mixture;

[0226] (7) adding the weighed triethylamine to the modified mixture and dropping it into the end-capped modified mixture, stirring evenly in a water bath to obtain a neutralized modified mixture; the degree of neutralization determined by triethylamine should be controlled at 85%, the neutralization temperature should be controlled at 37° C., and the neutralization time should be controlled at 0.5 h.

[0227] (8) adding weighed pure water droplets to the ionized modified mixture and stirring evenly to obtain an environmentally friendly fluorine-free organosilicon-modified waterborne polyurethane waterproofing agent; wherein the stirring time is 0.5 h and the solid content of the waterproofing agent is 31%.

[0228] About the waterproof application of the product:

[0229] The waterproofing agent prepared by the present invention can be applied to various fabrics such as natural fibers, synthetic fibers, artificial fibers, etc. The waterproof finishing method can be coating, dipping, spraying, padding or a combination of methods.

[0230] Specific method: The fabric is immersed in the obtained waterproofing agent emulsion for 5 minutes, then immersed and rolled twice, and then pre-baked at 105°C for 90 seconds, and finally baked at 135°C for 5 minutes to obtain a waterproofing agent film fabric with cross-linked film inside and outside the fiber.

[0231] Figure 1 This is a comparison chart of the waterproof effect test of the fabric after being treated with the waterproof agent prepared in Example 1. Figure 1 It can be seen that the water droplets of the untreated fabric have completely penetrated into the fabric at the 3rd minute of the test, the water on the fabric has further evaporated and decreased at the 10th minute of the test, and the water on the fabric has completely penetrated into the fabric and evaporated at the 30th minute of the test; while for the fabric treated with the obtained waterproofing agent, the water droplets still cannot penetrate into the fabric at the 30th minute of the test, which indicates that after the fabric is treated with the waterproofing agent prepared in Example 1, the film formed has excellent water repellency, and the treated fabric has excellent water permeability resistance.

[0232] Figure 2 This is a comparison chart of the waterproof effect test of the fabric after being treated with the waterproof agent prepared in Example 3. Figure 2 It can be seen that the water droplets have completely penetrated into the untreated fabric at the 3rd minute of the test; while the water droplets failed to penetrate into the fabric after the fabric was treated with the obtained waterproofing agent at the 10th minute of the test, which indicates that after the fabric is treated with the waterproofing agent prepared in Example 3, the film formed has excellent water repellency, and the treated fabric has excellent water permeability resistance.

[0233] Figure 3 This is a comparison chart of the waterproof effect test of the fabric after being treated with the waterproof agent prepared in Example 5. Figure 3 It can be seen that the water droplets have completely penetrated into the unfinished fabric at the 150th second of the test; while the water droplets still failed to penetrate into the fabric after the fabric was treated with the obtained waterproofing agent at the 20th minute of the test, which indicates that after the fabric is treated with the waterproofing agent prepared in Example 5, the film formed has excellent water repellency, and the treated fabric has excellent water permeability resistance.

[0234] Figure 4 This is an enlarged picture of the waterproof effect test of the fabric after being treated with the waterproof agent prepared in Example 5. Figure 4It can be clearly seen that when water drops are dropped on the finished fabric, no matter from a 30° downward angle or from a horizontal angle, the water drops do not run flat, and the water drops can maintain a relatively "round" state, which indicates that the fabric finished with the waterproofing agent obtained by the present invention has excellent water-repellent properties.

[0235] Figure 5 This is a comparison chart of the waterproof effect test of the fabric after being treated with the waterproof agent prepared in Example 6. Figure 5 It can be seen that at the beginning of the test, the water droplets completely penetrated into the unfinished fabric; while at the 20th minute of the test, the water droplets still failed to penetrate into the fabric after the fabric was treated with the obtained waterproofing agent, which indicates that after the fabric was treated with the waterproofing agent prepared in Example 6, the film formed has excellent water repellency, and the treated fabric has excellent water permeability resistance.

[0236] Figure 6 This is an enlarged picture of the waterproof effect test of the fabric after being treated with the waterproof agent prepared in Example 6. Figure 6 It can be clearly seen that when water drops are dropped on the finished fabric, the water drops are not observed to flow flat, and the water drops can maintain a relatively "round" state, which indicates that the fabric finished with the waterproofing agent obtained by the present invention has excellent water-repellent properties.

[0237] The above are only preferred embodiments of the present invention. It should be pointed out that ordinary technical workers in this technical field can make several improvements and modifications without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

[0238] The present invention has been described in detail above in conjunction with the embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge scope of ordinary technicians in the relevant technical field without departing from the purpose of the present invention.

Claims

1. Application of a waterproofing agent in the preparation of textiles, characterized in that: The method is as follows: the fabric is immersed in a waterproofing agent for 5 minutes, then immersed and rolled twice, then pre-baked at 105°C for 90 seconds, and finally baked at 135°C for 5 minutes, so as to obtain a waterproofing agent film fabric with cross-linked film inside and outside the fiber; The raw materials for preparing the waterproofing agent include: Silicone: 20 to 40 parts, Polyglycol: 60 to 80 parts, Diisocyanate: 21 to 50 parts, Organic tin catalyst: 0.20 to 0.55 parts, Chain extender: 8.5 to 22 parts, Neutralizer: 6 to 10 parts, Solvent: 10 to 25 parts, Capping agent: 1.5 to 3.5 parts; The polyglycol comprises at least one of polyethylene oxide glycol, polypropylene oxide glycol, polytetramethylene glycol and polycarbonate glycol, or the polyglycol is a mixture of polypropylene oxide glycol and polytetramethylene glycol; The waterproofing agent is prepared by the following method: S1: in the presence of the organotin catalyst, adding the diisocyanate to the polydiol for prepolymerization to obtain a double-ended prepolymer containing isocyanate groups; S2: adding the organosilicon to the double-ended isocyanate group-containing prepolymer for reaction, and then adding the chain extender dissolved in the solvent for chain extension reaction to obtain a chain extension mixture; S3: adding the end-capping agent and the neutralizing agent to the chain extension mixture in sequence; In step S1, the prepolymerization temperature is controlled at 60°C to 90°C, and the prepolymerization time is 1h to 3h; In step S2, the organosilicon is added to the double-ended isocyanate group-containing prepolymer for reaction, the reaction temperature is controlled at 65°C to 85°C, and the reaction time of adding the organosilicon for modification reaction is 1h to 3h; the boiling point of the solvent is 90°C to 160°C, the temperature of the chain extension reaction is controlled at 70°C to 90°C, and the chain extension time is 1h to 3h; In step S3, the degree of neutralization is controlled at 80% to 100%, the neutralization temperature is controlled at 30° C. to 70° C., and the neutralization time is controlled at 0.5 h to 2 h.

2. The use according to claim 1, characterized in that: The organosilicon includes at least one of amino organosilicon, silanol hydroxy organosilicon, hydroxyl polyether organosilicon, single-terminal hydroxyl organosilicon and dihydroxyl organosilicon.

3. The use according to claim 1, characterized in that: The organic tin catalyst includes at least one of stannous octoate, dibutyltin dilaurate and dibutyltin dioctoate.

4. The use according to claim 1, characterized in that: The chain extender includes a small molecule chain extender and a hydrophilic chain extender.

5. The use according to claim 4, characterized in that: The small molecule chain extender includes at least one of 1,2-propylene glycol, 1,4-butanediol, 1,6-ethylene glycol and trimethylolpropane.

6. The use according to claim 4, characterized in that: The hydrophilic chain extender is at least one of dimethylol propionic acid, dimethylol butyric acid and dihydroxy half ester.

7. The use according to claim 1, characterized in that: The end-capping agent is at least one of lactam, sodium bisulfite, phenol and butanone oxime.

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