Polyurethane and polyether amine co-modified fiber finishing agent and preparation method thereof

Abstract

The invention relates to the technical field of textile auxiliaries, in particular to a polyurethane and polyether amine co-modified fiber finishing agent and a preparation method thereof. The invention relates to a preparation method of a polyurethane and polyether amine co-modified fiber finishing agent. The preparation method comprises the following steps: S1, preparing a polyurethane prepolymer; s2, preparation of polyurethane and polyether amine co-modified silicone oil; s3, preparing the polyurethane and polyether amine co-modified fiber finishing agent. Cloth finished by the polyurethane and polyether amine co-modified fiber finishing agent has the advantages of unique hand feeling, excellent hydrophilicity and air permeability and the like, and the market competitiveness and wearing comfort of the fabric are improved.

Description

Technical Field

[0001] The present application relates to the technical field of textile auxiliaries, and in particular to a polyurethane and polyetheramine co-modified fiber finishing agent and a preparation method thereof. Background Art

[0002] Silicone softeners are widely used as softening finishing agents for various types of textiles, and can give textiles excellent softness. In recent years, the preparation technology of ternary block silicone oils has become highly mature, and has become a new type of silicone softener product with very excellent comprehensive performance. However, it still cannot overcome the inherent shortcomings of single-structure polymers. Low mechanical strength, poor solvent resistance and poor surface adhesion are inherent defects brought about by the structure of silicone, and these shortcomings limit the application scope of silicone.

[0003] Polyurethane has many special properties, such as good mechanical properties, strong flexibility, good weather resistance and strong adhesion. Through polyurethane modified silicone, the advantages of polyurethane and silicone can be combined to overcome the shortcomings of a single type of high molecular polymer, while retaining the good softness of silicone softener and having the excellent performance of polyurethane. Up to now, more and more scientific researchers have conducted relevant research on polyurethane modified silicone, and the performance of polyurethane modified silicone is becoming more and more excellent. He Jiefang et al. (He Jiefang, Lei Wenwen, Chen Kun, et al. Preparation of elastic silicone oil and its application in cotton fabric finishing [J]. Silk, 2018, 55(09): 33-39.) used isophorone diisocyanate, polypropylene glycol, 4,4'-methylenebis(3-chloro-2,6-diethylaniline) and polyoxypropylene triol as reaction raw materials to synthesize polyurethane prepolymer, which was then polymerized with double-terminated amino polysiloxane and the isocyanate group at the end of the molecular chain was blocked with methyl ethyl ketone oxime to prepare an elastic silicone oil. The fabric has good softness after finishing. Meng Lingxi et al. (Meng Lingxi. Synthesis and Application of New Polyurethane Modified Block Polyether Amino Silicone Oil [J]. Organic Silicone Materials, 2020, 34(06): 29-34.) used polyethylene glycol PEG400 and isophorone diisocyanate to synthesize a cationic polyurethane (PUAN) intermediate, which was then compounded with polyetheramine HE1000 as a raw material and then reacted with terminal epoxy silicone oil to obtain block polyether amino silicone oil PU-Si-A, which showed good softness, smoothness, elasticity, fluffiness and softness when used for Roman cloth and coral fleece finishing. The above study introduced hydrophilic polyether segments into polyurethane, which improved the hydrophilicity of modified silicone in fabric finishing to a certain extent, but it was still insufficient in terms of hand feel, especially smoothness, and could not meet the ever-changing market demand. Summary of the invention

[0004] In order to solve the above technical problems, the present application provides a polyurethane and polyetheramine co-modified fiber finishing agent and a preparation method thereof. The polyurethane and polyetheramine co-modified fiber finishing agent of the present application simultaneously introduces polyurethane and polyetheramine into its structure, and its structure is regular and controllable. Not only hydrophilic polyether segments and a large number of active amino groups are introduced into its main chain, but also the quaternary ammonium salt structure formed by some amino groups further enhances the cationicity. In addition, carbamate and benzene ring structures are introduced into its main chain through polyurethane, so that the rigidity of its molecular chain is enhanced, and the soft and smooth feel of the polyurethane and polyetheramine co-modified fiber finishing agent is further enhanced. The fabric treated with the polyurethane and polyetheramine co-modified fiber finishing agent of the present application has excellent hydrophilicity and feel. In addition, the preparation method of the present application is simple, the raw materials are easily available, the overall production cycle is suitable, and it is easy to promote in industry.

[0005] In the first aspect, the present application provides a method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent, using the following technical scheme: A method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent comprises the following steps: S1. Preparation of polyurethane prepolymer: polyethylene glycol and dihydroxyethyl terephthalate are dissolved in a first solvent, and the mixture is placed in a constant pressure dropping funnel to obtain a mixture for standby use; isophorone diisocyanate is dissolved in the first solvent and a small amount of catalyst is added, the mixture is heated to 40-50°C after being stirred evenly, and the mixture is added dropwise through a constant pressure dropping funnel to carry out polymerization reaction, the dropping time is 30-90min, and the mixture is stirred at 50-80°C for 2-8h. During the reaction, nitrogen protection is performed to generate an NCO-terminated prepolymer; then a tertiary amine end-capping agent N,N-dimethylethanolamine is added, the mixture is stirred at 50-70°C for 2-6h, the first solvent is removed by vacuum distillation, and then an appropriate amount of a second solvent is added for dilution to obtain a polyurethane prepolymer; the specific reaction process is as follows: Step 1: Synthesis of NCO-terminated prepolymer: 3OCN-R-NCO+HO-R1-OH+HO-R2-OH→OCN-RNHCOOR1OOCNHRNHCOOR2OOCNHR-NCO Step 2: Synthesis of polyurethane prepolymer: OCN-RNHCOOR1OOCNHRNHCOOR2OOCNHR-NCO+2HOCH2CH2N(CH3)2→(CH3)2NCH2CH2OOCNH-RNHCOOR1OOCNHRNHCOOR2OOCNHRNHCOOCH2CH2N(CH3)2; where R is -C 10 H 18 -, R1 is -(C2H4O) a-, a is an integer of 0-20, and R2 is -C2H4OOC-C6H6-COOC2H4-); S2, the polyurethane prepolymer, the terminal primary amine polyether and the terminal epoxy silicone oil prepared in step S1 are mixed evenly in the second solvent, and an acidic catalyst is added to carry out a polymerization reaction, and the reaction is stirred at 78-110° C. for 10-30 hours, and then the second solvent is removed by vacuum to obtain polyurethane and polyetheramine co-modified silicone oil; the reaction formula is as follows: R3-(CH3)2SiO[(CH3)2SiO] m Si(CH3)2-R3+(CH3)2NCH2CH2OOCNH-RNHCOOR1OOCNHRNHCOOR2OOCNHRNHCOOCH2CH2N(CH3)2+H2N-R4-NH2→-{(CH3)2N + CH2CH2OOCNHRNHCOOR1OOCNHRNHCOOR2OOCNHRNHCOOCH2CH2N + (CH3)2-CH2CH2(OH)CH2O-(CH3)2SiO[(CH3)2SiO] m Si(CH3)2-OCH2CH2(OH)CH2-HN-R4-NH} t - Wherein, R3 is -OCH2CHOCH2, R4 is -CH(CH3)CH2(C3H6O) p -(C2H4O) q -, p and q are both integers of 0-20, 30≤m≤130, t is an integer of 1-4; S3, adding an emulsifier to the polyurethane and polyetheramine co-modified silicone oil obtained in step S2 for emulsification to obtain a polyurethane and polyetheramine co-modified fiber finishing agent.

[0006] By adopting the above technical scheme, the polyurethane and polyetheramine co-modified silicone oil of the present application embeds carbamate and benzene ring structures on the silicone oil main chain through polymerization reaction, which, as a hard segment, plays a role in supporting the silicone oil main chain, thereby enhancing the mechanical properties of the silicone emulsion, thereby enhancing the mechanical properties of the cloth treated with the polyurethane and polyetheramine co-modified fiber finishing agent prepared by the present application, and can be applied to cotton and its blended fibers to make the cloth have strong slipperiness and elasticity. The polyether structure on the polyurethane and polyetheramine co-modified silicone oil of the present application cooperates with the silicone main chain as a soft segment to enhance the softness of the cloth. By adjusting the ratio of the polyurethane prepolymer and the polyetheramine in the technical scheme of the present application, the ratio of the soft and hard segments on the final modified silicone oil is adjusted, so that the cloth treated with the polyurethane and polyetheramine co-modified fiber finishing agent prepared by the present application has excellent softness. It is worth mentioning that the benzene ring structure introduced into the structure of the polyurethane and polyetheramine co-modified silicone oil prepared in this application makes the finished fabric have a smooth style similar to chemical fiber, and the finishing style is unique. In step S1, a mixed solution of polyethylene glycol and dihydroxyethyl terephthalate is added dropwise to isophorone diisocyanate through a constant pressure dropping funnel, first forming an active isocyanate-terminated structure, and then the capping agent N,N-dimethylethanolamine is added dropwise, and the dropping time is controlled at 30-90 minutes, and finally a tertiary amine-terminated polyurethane prepolymer is formed.

[0007] Preferably, the first solvent is one or a combination of ethyl acetate, dimethylformamide, acetone and tetrahydrofuran; the second solvent is one or a combination of ethylene glycol butyl ether, diethylene glycol butyl ether, isopropanol and dipropylene glycol methyl ether.

[0008] Preferably, in step S1, the molar ratio of isophorone diisocyanate, polyethylene glycol and bis(hydroxyethyl) terephthalate is 3:1:1.

[0009] Preferably, in step S1, the catalyst is an organic tin catalyst, and the organic tin catalyst is dibutyltin dilaurate; the polyethylene glycol is a polyethylene glycol with a molecular weight of less than 2000, preferably PEG200 or PEG400.

[0010] Preferably, in step S1, the molar ratio of N,N-dimethylethanolamine to isophorone diisocyanate is 2:3.

[0011] Preferably, in step S1, the mass of the first solvent is 20%-70% of the total mass of isophorone diisocyanate, polyethylene glycol and bis(hydroxyethyl) terephthalate.

[0012] Preferably, in step S2, the molar ratio of the terminal epoxy silicone oil to the total amount of the polyurethane prepolymer and the terminal primary amino polyether is 1.5-2:1; Preferably, in step S2, the molar ratio of the polyurethane prepolymer to the terminal primary amine polyether is 1:1-2.

[0013] By adopting the above technical scheme, by adjusting the molar ratio of polyurethane prepolymer and terminal primary amino polyether, the ratio of soft and hard segments on the modified fiber finishing agent finally prepared can be adjusted. The soft segment is mainly provided by the polyether structure, and the hard segment is provided by the carbamate and benzene ring structure introduced by the polyurethane. The appropriate ratio of soft and hard segments can make the finished fabric have excellent softness and mechanical properties. As a hydrophilic segment, the increase in the content of terminal primary amino polyether helps to improve the hydrophilicity of the finishing agent. This is very important for maintaining the air permeability of the fabric itself, and it is also beneficial to improve the comfort of the fabric. By introducing polyurethane and polyetheramine co-modified silicone oil, the finished fabric can have a smooth feel similar to chemical fiber and a unique style. In short, by adjusting the molar ratio of polyurethane prepolymer and terminal primary amino polyether, the performance of the modified fiber finishing agent can be optimized, so that it has excellent softness and unique feel while maintaining good hydrophilicity. This modified fiber finishing agent is suitable for the treatment of cotton and its blended fibers, and can significantly improve the quality and use experience of the fabric.

[0014] Preferably, in step S2, the acidic catalyst is one or a combination of lauric acid, acetic acid, and hydrochloric acid; and the molar ratio of the polyurethane prepolymer to the acidic catalyst is 1:0.9-1.2.

[0015] Preferably, in step S3, the emulsifier is a mixed emulsifier, which is compounded from two to four fatty alcohol polyoxyethylene ethers with different HLB values, and the HLB value of the fatty alcohol polyoxyethylene ether is 5-12, represented by the following general formula: R5-O-(CH2CH2O)nH, wherein R5 is a C12-18 hydrocarbon group, and n is an integer of 5-10.

[0016] In a second aspect, the present application provides a polyurethane and polyetheramine co-modified fiber finishing agent, which adopts the following technical solution: As a general technical concept, the present application also provides the above-mentioned polyurethane and polyetheramine co-modified fiber finishing agent, which is prepared by the preparation method of the above-mentioned polyurethane and polyetheramine co-modified fiber finishing agent.

[0017] In summary, the beneficial technical effects of this application are: 1. Unique feel and style: By introducing carbamate and benzene ring structure into the polyurethane and polyetheramine co-modified fiber finishing agent, cotton fabrics are given a smooth feel similar to chemical fibers, making the fabric style unique and improving the market competitiveness of the fabric.

[0018] 2. Excellent hydrophilicity and air permeability: Since the hydrophilic polyether and quaternary ammonium salt structure are embedded in the main chain, the finished fabric has excellent hydrophilicity, while maintaining the air permeability of the fabric itself, improving the wearing comfort of the fabric.

[0019] 3. The preparation method is simple and the raw materials are readily available: The preparation method of the polyurethane and polyetheramine co-modified fiber finishing agent of the present application is simple, the raw materials are readily available, the overall production cycle is suitable, and it is easy to promote in industry, which is conducive to reducing production costs and improving production efficiency.

[0020] 4. Enhance the mechanical properties of fabrics: By embedding carbamate and benzene ring structures into the main chain of silicone oil, the mechanical properties of silicone emulsion are enhanced, thereby enhancing the mechanical properties of fabrics finished with polyurethane and polyetheramine co-modified silicone emulsion produced by this technical solution, making the fabrics have stronger smoothness and elasticity.

[0021] 5. Softness adjustment: By adjusting the ratio of the polyurethane prepolymer and the polyetheramine in the technical solution of the present application, the ratio of the soft and hard segments on the modified fiber finishing agent finally produced can be adjusted, so that the fabric treated with the polyurethane and polyetheramine co-modified fiber finishing agent prepared by the present application has excellent softness. DETAILED DESCRIPTION

[0022] The embodiments of the present application will be described in detail below in conjunction with the examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0023] In the following examples and comparative examples, the material feeding amounts are calculated by mass, and 1 part is 10g.

[0024] Example 1 S1: 200 parts of isophorone diisocyanate, 120 parts of acetone and 0.1 parts of dibutyltin dilaurate are added to a reaction kettle equipped with a thermometer, a stirrer and a condenser reflux, the temperature is raised to 40°C, and nitrogen is introduced, 120 parts of polyethylene glycol (molecular weight 400) and 76.2 parts of bis(hydroxyethyl terephthalate) are dissolved in 150 parts of acetone, and the mixture is slowly added dropwise to the reaction kettle through a constant pressure dropping funnel for 30 minutes. After keeping the temperature for 2 hours, the temperature is raised to 70°C, 53.5 parts of N,N-dimethylethanolamine are added dropwise for 60 minutes. After the addition is completed, the reaction is kept warm for 2 hours. No characteristic peak of isocyanate is detected by infrared detection. After removing acetone by vacuum distillation, 300 parts of ethylene glycol butyl ether are added for dilution. After cooling to room temperature, the polyurethane prepolymer with a solid content of 63% is obtained; S2: 14.4 parts of the obtained polyurethane prepolymer, 19.8 parts of terminal primary amine polyether (molecular weight 900), 100 parts of terminal epoxy silicone oil (number average molecular weight 6000) and 132 parts of ethylene glycol butyl ether are added into a reaction kettle equipped with a thermometer, a stirrer and a condenser reflux, 1.3 parts of glacial acetic acid are added, nitrogen is introduced and the temperature is raised to 78°C. After the reaction is kept warm for 30 hours, the introduction of nitrogen is stopped, about 100 parts of isopropanol are distilled off under reduced pressure, and the temperature is lowered to below 40°C to obtain a polyurethane and polyetheramine co-modified silicone oil with a solid content of 82%.

[0025] S3: Take 50 parts of the above-mentioned polyurethane and polyetheramine co-modified silicone oil, 5 parts of isomeric decanol polyoxyethylene ether and 3 parts of isomeric tridecanol polyoxyethylene ether and add them into an emulsifier, start emulsification mixing, add 0.7 parts of glacial acetic acid, and then slowly add 134 parts of deionized water for phase inversion emulsification to obtain a polyurethane and polyetheramine co-modified fiber finishing agent with a solid content of 25%.

[0026] Example 2 S1: 200 parts of isophorone diisocyanate, 170 parts of tetrahydrofuran and 0.1 parts of dibutyltin dilaurate are added to a reaction kettle equipped with a thermometer, a stirrer and a condenser reflux, the temperature is raised to 50°C, and nitrogen is introduced, 120 parts of polyethylene glycol (molecular weight 400) and 76.2 parts of bis(hydroxyethyl) terephthalate are dissolved in 150 parts of tetrahydrofuran, and the mixture is slowly added dropwise to the reaction kettle through a constant pressure dropping funnel for 60 minutes. After keeping the temperature for 3 hours, the temperature is raised to 55°C, 53.5 parts of N,N-dimethylethanolamine are added dropwise for 90 minutes. After the addition is completed, the reaction is kept warm for 6 hours. No characteristic peak of isocyanate is detected by infrared detection. After removing tetrahydrofuran by vacuum distillation, 300 parts of dipropylene glycol methyl ether are added for dilution. After cooling to room temperature, the polyurethane prepolymer with a solid content of 60% is obtained; S2: 14.4 parts of the obtained polyurethane prepolymer, 19.8 parts of terminal primary amine polyether (molecular weight 900), 100 parts of terminal epoxy silicone oil (number average molecular weight 6000) and 132 parts of dipropylene glycol methyl ether were added into a reaction kettle equipped with a thermometer, a stirrer and a condenser reflux, 1.3 parts of glacial acetic acid were added, nitrogen was introduced and the temperature was raised to 110°C. After the reaction was kept warm for 10 hours, the introduction of nitrogen was stopped, about 100 parts of isopropanol was distilled off under reduced pressure, and the temperature was lowered to below 40°C to obtain a polyurethane and polyetheramine co-modified silicone oil with a solid content of 79%.

[0027] S3: Take 50 parts of the above-mentioned polyurethane and polyetheramine co-modified silicone oil, 5 parts of isomeric decanol polyoxyethylene ether and 3 parts of isomeric tridecanol polyoxyethylene ether and add them into an emulsifier, start emulsification mixing, add 0.7 parts of glacial acetic acid, and then slowly add 134 parts of deionized water for phase inversion emulsification to obtain a polyurethane and polyetheramine co-modified fiber finishing agent with a solid content of 25%.

[0028] Example 3 S1: 200 parts of isophorone diisocyanate, 150 parts of ethyl acetate and 0.1 parts of dibutyltin dilaurate are added to a reaction kettle equipped with a thermometer, a stirrer and a condenser reflux, the temperature is raised to 45°C, and nitrogen is introduced, 120 parts of polyethylene glycol (molecular weight 400) and 76.2 parts of dihydroxyethyl terephthalate are dissolved in 150 parts of ethyl acetate, and the mixture is slowly added dropwise to the reaction kettle through a constant pressure dropping funnel for 60 minutes. After keeping the temperature for 3 hours, the temperature is raised to 63°C, 53.5 parts of N,N-dimethylethanolamine are added dropwise for 60 minutes. After the addition is completed, the reaction is kept warm for 2 hours. No characteristic peak of isocyanate is detected by infrared detection. After removing ethyl acetate by vacuum distillation, 300 parts of isopropanol are added for dilution. After cooling to room temperature, the polyurethane prepolymer with a solid content of 60% is obtained; S2: 14.4 parts of the obtained polyurethane prepolymer, 19.8 parts of terminal primary amine polyether (molecular weight 900), 100 parts of terminal epoxy silicone oil (number average molecular weight 6000) and 132 parts of isopropanol are added to a reaction kettle equipped with a thermometer, a stirrer and a condenser reflux, 1.3 parts of glacial acetic acid are added, nitrogen is introduced and the temperature is raised to 83°C. After the reaction is kept warm for 15 hours, the introduction of nitrogen is stopped, about 100 parts of isopropanol are distilled off under reduced pressure, and then the temperature is lowered to below 40°C to obtain a polyurethane and polyetheramine co-modified silicone oil with a solid content of 80%.

[0029] S3: Take 50 parts of the above-mentioned polyurethane and polyetheramine co-modified silicone oil, 5 parts of isomeric decanol polyoxyethylene ether and 3 parts of isomeric tridecanol polyoxyethylene ether and add them into an emulsifier, start emulsification mixing, add 0.7 parts of glacial acetic acid, and then slowly add 134 parts of deionized water for phase inversion emulsification to obtain a polyurethane and polyetheramine co-modified fiber finishing agent with a solid content of 25%.

[0030] The difference between Example 4 and Comparative Examples 1 and 2 and Example 3 is that the molar ratio of the total amount of the epoxy silicone oil to the polyurethane prepolymer and the primary amino-terminated polyether in step S2 is different, and the specific amounts are shown in Table 1: Table 1, Example 4 and Comparative Examples 1 and 2 The difference between Example 5 and Comparative Examples 3 and 4 and Example 3 is that the ratio of the amount of the polyurethane prepolymer to the terminal primary amino group polyether in step S2 is different, and the specific amount is shown in Table 2: Table 2: Formula dosage of Example 5 and Comparative Examples 3 and 4 project Polyurethane prepolymer (parts) Primary amino-terminated polyether (parts) Molar Ratio Example 3 14.4 19.8 1:2 Example 5 14.4 9.9 1:1 Comparative Example 3 11.5 19.8 1:2.5 Comparative Example 4 28.8 9.9 2:1 Comparative Example 5 is pure water, which serves as a blank control group.

[0031] Comparative Example 6 is a commercially available block silicone oil emulsion.

[0032] Comparative Example 7 is a commercially available polyurethane silicone oil emulsion.

[0033] Performance Testing The polyurethane and polyetheramine co-modified fiber finishing agents prepared in Examples 3 to 5 and Comparative Examples 1 to 4 and the samples of Comparative Examples 5 to 7 were respectively applied to cotton woven fabrics, with a dosage of 15 g / L and a rolling rate of 70%. The process flow is as follows: the finishing process is: liquid preparation → one immersion and one rolling → baking (170°C × 90s) → regain 1h → evaluation.

[0034] Application performance testing: ① Hand feel evaluation: Evaluate by touching with your hands, using a 1-5 point evaluation method, with 1 point being the worst and 5 points being the best. 5 people evaluate at the same time and take the average value. Evaluation includes: softness and smoothness.

[0035] ② The hydrophilicity of a fabric is defined by measuring the time it takes for a drop of water to be completely absorbed by the fabric in seconds.

[0036] ③ Fabric washing procedure: Fabric washing is carried out in accordance with AATCC 135-2018t standard, and tumble dried after washing 10 times.

[0037] The test results are shown in Table 3.

[0038] Table 3 Performance test results Analyzing the data in Table 1, we can see that: 1) According to the data of Example 3 and Comparative Examples 5, 6, and 7, the hydrophilicity of the fabric treated with the polyurethane and polyetheramine co-modified fiber finishing agent prepared by the present application is significantly improved compared with the two commercially available softeners, both in terms of initial hydrophilicity and hydrophilicity after multiple washings. At the same time, the feel of the fabric is not significantly reduced compared with the fabric treated with the commercially available softener, indicating that the polyurethane and polyetheramine co-modified fiber finishing agent prepared by the present application not only meets the commercial requirements, but also significantly improves the hydrophilicity of the fabric.

[0039] 2) It can be seen from the data of Examples 3, 4 and Comparative Examples 1 and 2 that by changing the molar ratio of the total feed amount of the terminal epoxy silicone oil to the polyurethane prepolymer and the terminal primary amino polyether, the hydrophilicity and feel of the fabric change greatly. Therefore, in order to keep the hydrophilicity and feel of the fabric in a relatively excellent range, the molar ratio of the total feed amount of the terminal epoxy silicone oil to the polyurethane prepolymer and the terminal primary amino polyether of the present application is (1.5-2):1.

[0040] 3) It can be seen from the data of Examples 3, 5 and Comparative Examples 3, 4 that when the molar ratio of the polyurethane prepolymer to the terminal primary amine polyether is 1:1-2, the hydrophilicity and feel of the fabric treated with the polyurethane and polyetheramine co-modified fiber finishing agent prepared in the present application are maintained in a relatively high range.

[0041] The above embodiments are only used to explain the technical solutions of the present application rather than to limit them. Although the above embodiments provide a specific description of the present application, relevant technical personnel should understand that the specific implementation methods of the present application can still be modified or replaced by equivalents, and any modifications and equivalent replacements that do not depart from the spirit and scope of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent, characterized in that: The following steps are involved: S1. Preparation of polyurethane prepolymer: dissolving polyethylene glycol and dihydroxyethyl terephthalate in a first solvent, placing the mixture in a constant pressure dropping funnel to obtain a mixture for later use; dissolving isophorone diisocyanate in the first solvent and adding a small amount of catalyst, stirring evenly and heating to 40-50° C., dropping the mixture through a constant pressure dropping funnel to carry out polymerization reaction, the dropping time is 30-90 min, stirring and reacting at 50-80° C. for 2-8 h, performing nitrogen protection during the reaction to generate an NCO-terminated prepolymer; then adding a tertiary amine end-capping agent N,N-dimethylethanolamine, stirring at 50-70° C. for 2-6 h, removing the first solvent by reduced pressure distillation, and adding an appropriate amount of a second solvent to dilute to obtain a polyurethane prepolymer; S2, the polyurethane prepolymer, the terminal primary amine polyether and the terminal epoxy silicone oil prepared in step S1 are mixed evenly in a second solvent, and an acidic catalyst is added to carry out a polymerization reaction. The reaction is stirred at 78-110° C. for 10-30 hours, and then the second solvent is removed by vacuum to obtain a polyurethane and polyetheramine co-modified silicone oil; S3, adding an emulsifier to the polyurethane and polyetheramine co-modified silicone oil obtained in step S2 for emulsification to obtain a polyurethane and polyetheramine co-modified fiber finishing agent.

2. The method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent according to claim 1, characterized in that: The first solvent is one or a combination of ethyl acetate, dimethylformamide, acetone and tetrahydrofuran; the second solvent is one or a combination of ethylene glycol butyl ether, diethylene glycol butyl ether, isopropanol and dipropylene glycol methyl ether.

3. The method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent according to claim 1, characterized in that: In step S1, the molar ratio of isophorone diisocyanate, polyethylene glycol and bis(hydroxyethyl) terephthalate is 3:1:

1.

4. The method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent according to claim 1, characterized in that: In step S1, the catalyst is an organic tin catalyst, and the organic tin catalyst is dibutyltin dilaurate; the polyethylene glycol is a polyethylene glycol with a molecular weight of less than 2000, preferably PEG200 or PEG400.

5. The method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent according to claim 1, characterized in that: In step S1, the molar ratio of N,N-dimethylethanolamine to isophorone diisocyanate is 2:

3.

6. The method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent according to claim 1, characterized in that: In step S1, the mass of the first solvent is 20%-70% of the total mass of isophorone diisocyanate, polyethylene glycol and bis(hydroxyethyl) terephthalate.

7. The method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent according to claim 1, characterized in that: In step S2, the molar ratio of the terminal epoxy silicone oil to the total amount of the polyurethane prepolymer and the terminal primary amine polyether is 1.5-2:1; the molar ratio of the polyurethane prepolymer to the terminal primary amine polyether is 1:1-2.

8. The method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent according to claim 1, characterized in that: In step S2, the acidic catalyst is one or a combination of lauric acid, acetic acid, and hydrochloric acid; and the molar ratio of the polyurethane prepolymer to the acidic catalyst is 1:0.9-1.

2.

9. The method for preparing a polyurethane and polyetheramine co-modified fiber finishing agent according to claim 1, characterized in that: In step S3, the emulsifier is a mixed emulsifier, which is compounded from two to four fatty alcohol polyoxyethylene ethers with different HLB values. The HLB value of the fatty alcohol polyoxyethylene ether is 5-12, represented by the following general formula: R5-O-(CH2CH2O)nH, wherein R5 is a C12-18 hydrocarbon group, and n is an integer of 5-10.

10. A polyurethane and polyetheramine co-modified fiber finishing agent, characterized in that: The polyurethane and polyetheramine co-modified fiber finishing agent is prepared by the preparation method of the polyurethane and polyetheramine co-modified fiber finishing agent according to any one of claims 1 to 9.

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