Cationic PU-polysiloxane copolymer, preparation method and hydrophilic softener

Abstract

The invention belongs to the field of textile after-finishing auxiliaries, and particularly relates to a cationic PU-polysiloxane copolymer, a preparation method and a hydrophilic softener. The average molecular weight of the cationic PU-polysiloxane copolymer is 7500-50000, and the cationic PU-polysiloxane copolymer is formed by polymerizing a tertiary amine-terminated PU prepolymer, epoxy-terminated polyether polysiloxane and epoxy chloropropane in a molar ratio of (1-1.6): 1: (0.5-4.4); wherein the tertiary amine-terminated PU prepolymer comprises a first structural unit, a second structural unit and a third structural unit in a quantity ratio of (2-6): (0.5-3): 1. All functional components are integrated in the structure of the cationic PU-polysiloxane copolymer in a chemical bonding mode, and the whole molecule is firmly anchored on the surface of the fiber through the strong adsorption capacity of quaternary ammonium salt cations and the film-forming property of PU.

Description

Technical Field

[0001] This application belongs to the field of textile finishing auxiliaries, and more specifically, relates to a cationic PU-polysiloxane copolymer, its preparation method, and a hydrophilic softener. Background Technology

[0002] This application relates to the field of textile finishing auxiliaries, and in particular to a method for preparing a durable hydrophilic silicone softener for nylon-spandex knitted fabrics.

[0003] Nylon-spandex knitted fabrics are widely used in swimwear, underwear, yoga wear, shirts, and other apparel due to their excellent elasticity and abrasion resistance. Because nylon and spandex fibers are rigid and have a stiff feel, they often require softening treatments to improve wearing comfort. The softeners used are mostly silicone softeners, aiming for a fluffy and soft feel. Due to the need for close contact with the skin and seamless processing of underwear, there are high requirements for the hydrophilicity and durability of the softener. While commercially available hydrophilic polyether-modified amino silicone oils and ternary block silicone oils can impart excellent softness to fabrics, the resulting fabrics have poor resilience, hydrophilicity, and hydrophilic durability. This leads to a decrease in the moisture-wicking function of clothing and a reduction in adhesive strength during seamless processing of underwear, affecting the quality of the textiles.

[0004] Polyurethane (PU) is increasingly being used in silicone oil modification due to its excellent mechanical properties and structural designability. By modifying organosilicon polymers with polyurethane, the advantages of both can be combined, giving fabrics multiple benefits, including a fluffy and soft hand feel, good elasticity, and wrinkle resistance. Simultaneously, the introduction of urea bonds or urethane bonds enhances the anchoring effect between softener molecules and fibers, thus providing fabrics with durable hydrophilicity and excellent hand feel, significantly improving textile quality. Patent CN104628990A discloses a reactive polyurethane-modified slip-elastic silicone oil preparation technology, which exhibits good slip-elasticity and wash resistance on cotton fabrics, but its insufficient hydrophilicity makes it unsuitable for softening nylon-spandex knitted fabrics. Patent CN111171267A discloses a method for preparing polyurethane-modified slip-elastic silicone oil, which imparts excellent elasticity, smoothness, and softness to various fabrics, but this technology does not consider improving the fabric's hydrophilicity.

[0005] In summary, although a series of advances have been made in polyurethane-modified silicone oil technology, there has been no progress in the research of silicone softeners that can simultaneously satisfy the requirements of hydrophilicity, long-lasting hydrophilicity, fluffy and soft hand feel, and excellent adhesive adhesion for nylon and sponge fabrics. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this application is to solve the problem of poor hydrophilic durability caused by the easy migration and shedding of existing hydrophilic silicone fabric softeners during placement or washing by optimizing the structure of the hydrophilic silicone fabric softener.

[0007] To achieve the above objectives, in a first aspect, this application provides a cationic PU-polysiloxane copolymer with an average molecular weight of 7,500 to 50,000, which is polymerized from a terminal tertiary amine PU prepolymer, a terminal epoxy polyether polysiloxane, and epichlorohydrin in a molar ratio of (1 to 1.6): 1: (0.5 to 4.4). The terminal tertiary amine PU prepolymer comprises a first structural unit, a second structural unit, and a third structural unit in a ratio of (2~6):(0.5~3):1; specifically, the first structural unit is -OC-NH-C6H 12 -NH-CO- or The second structural unit is -O-(EO)n-, and the third structural unit is ; The two ends of the terminal tert-amine PU prepolymer are Group end capping; The terminal epoxy polyether polysiloxane structure is as follows: Where u is 11~24 and v is 33~60; The epichlorohydrin structure is as follows: .

[0008] Preferably, the average molecular weight of the terminal tertiary amine PU prepolymer is 1400~5200.

[0009] Secondly, this application also provides a method for preparing the above-mentioned cationic PU-polysiloxane copolymer: under the action of an acidic catalyst, the second total material undergoes a nucleophilic addition reaction between tertiary amine groups and epoxy groups in a second solvent, and copolymerizes to obtain the cationic PU-polysiloxane copolymer; the second total material includes a terminal tertiary amine PU prepolymer, a terminal epoxy polyether polysiloxane, and epichlorohydrin in a molar ratio of (1~1.6):1: (0.5~4.4), and the second solvent is one or more of isopropanol, diethylene glycol butyl ether, dipropylene glycol butyl ether, or dipropylene glycol.

[0010] Preferably, the acidic catalyst for the nucleophilic addition reaction is formic acid, acetic acid, or lauric acid, and the molar ratio of the acidic catalyst to the terminal tertiary amine PU prepolymer is (3~6):1.

[0011] Preferably, the mass ratio of the second solvent to the second total material is (0.7~1.5):1.

[0012] Thirdly, this application also provides a tertiary amine PU prepolymer for the preparation of the above-mentioned cationic PU-polysiloxane copolymer.

[0013] Preferably, the terminal tertiary amine PU prepolymer is prepared by the following method: a first total material is uniformly dissolved in a first solvent, an addition reaction of isocyanate groups and hydroxyl groups occurs, and then N,N-dimethylpropanediamine is added to obtain the terminal tertiary amine PU prepolymer; the first total material includes a diisocyanate, polyethylene glycol and N-methyldiethanolamine in a molar ratio of (2~6):(0.5~3):1, wherein the molar ratio of N,N-dimethylpropanediamine to N-methyldiethanolamine is (1~4):1, and the first solvent is acetone, butanone or ethyl acetate.

[0014] As a further preferred embodiment, the catalyst for the addition reaction of the isocyanate group and the hydroxyl group is stannous octoate or organic bismuth, and the concentration of the catalyst for the addition reaction of the isocyanate group and the hydroxyl group is 500 ppm to 2000 ppm.

[0015] Fourthly, this application also provides a hydrophilic softener comprising the aforementioned cationic PU-polysiloxane copolymer.

[0016] Preferably, it also includes a nonionic emulsifier, acetic acid and water, and the mass ratio of cationic PU-polysiloxane copolymer, nonionic emulsifier, acetic acid and water is 1:(0.2~0.5):(0.02~0.04):(3~5).

[0017] Compared with the prior art, this application has the following advantages: 1. The tertiary amine-terminated PU prepolymer contains polyurethane segments (PU), and the terminal epoxy polyether polysiloxane contains polysiloxane segments (Si). The tertiary amine-terminated PU prepolymer undergoes nucleophilic addition with terminal epoxy polyether polysiloxane / epoxychloropropane to form a quaternary ammonium salt cationic structure (QAS), as well as polyether segments (PE) contained in the tertiary amine-terminated PU prepolymer or terminal epoxy polyether polysiloxane. These four functional components are chemically bonded into the structure of the hydrophilic silicone softener. The strong adsorption of QAS and the film-forming properties of PU contribute to this effect. The chemical bonding structure anchors the entire molecule (including the hydrophilic PE segments) more firmly to the fiber surface, avoiding the problem of easy migration and shedding of simple mixed components during placement or washing. Through its internal synergistic mechanism, this design successfully overcomes the technical bottleneck of traditional softeners in achieving a balance between hydrophilicity, softness, and durability, ultimately achieving durable hydrophilicity, excellent softness, and resilience, providing a high-performance solution for high-end functional fabrics (especially nylon, spandex, and their blended fabrics). 2. This application utilizes tertiary amine-terminated polyurethane (PU) prepolymer as a base, which is then subjected to a quaternization reaction with epoxy polyether polysiloxane and epichlorohydrin. Through covalent bonding, PU segments are combined with polysiloxane segments, and simultaneously, strongly hydrophilic and positively charged quaternary ammonium salt groups are introduced. This differs from methods that involve physically mixing hydrophilic agents or simply modifying with hydrophilic groups. Using this innovative process, a hydrophilic silicone softener that combines durable hydrophilicity, excellent softness, and resilience was successfully prepared. 3. This application reacts diisocyanate with polyethylene glycol and N-methyldiethanolamine to obtain a tertiary amine-terminated PU prepolymer. In its key steps, N-methyldiethanolamine is used as a chain extender and a tertiary amine compound is used as a capping agent. Reactive tertiary amine groups are introduced into the molecule at specific positions inside and at both ends through N-methyldiethanolamine and N,N-dimethylpropanediamine. This step provides key active sites for subsequent block copolymerization and quaternary ammonium salting reactions, and also avoids the drawback of the difficulty in stabilizing NCO-terminated prepolymers in conventional synthesis methods. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of this application clearer, this application will be further described in detail. It should be understood that the specific embodiments described herein are only for explaining this application and are not intended to limit this application.

[0019] In the description of this application, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means two or more, unless otherwise explicitly specified.

[0020] Furthermore, throughout this specification, references to "an embodiment"; "an embodiment," "an example," or similar language indicate that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of this application. Therefore, the appearance of the phrase "in one embodiment;" throughout this specification, and similar language, may, but not necessarily, refer to the same embodiment.

[0021] This application provides a cationic PU-polysiloxane copolymer, its preparation method, and a hydrophilic softener. The cationic PU-polysiloxane copolymer and the hydrophilic softener achieve a balance between durable hydrophilicity and softness through the synergistic effect of polyurethane segments, quaternary ammonium salt cationic structures, polysiloxane segments, and polyether segments, significantly improving the elasticity of the fabric. The preparation method of the cationic PU-polysiloxane copolymer hydrophilic softener includes the following steps: S1: The first total material is uniformly dissolved in the first solvent. Under the catalysis of the first catalyst, an addition reaction of isocyanate groups and hydroxyl groups occurs. Then, N,N-dimethylpropylenediamine is added to obtain the terminal tertiary amine PU prepolymer. The first total material includes diisocyanate, polyethylene glycol and N-methyldiethanolamine in a molar ratio of (2~6):(0.5~3):1. The first solvent is acetone, butanone or ethyl acetate.

[0022] The diisocyanate is OCN-C6H. 12 -NCO or Preferred (i.e., isophorone diisocyanate, IPDI); polyethylene glycol is HO-(EO). n -H, with an average molecular weight of 600~2000, i.e., n is 13~45; N-methyldiethanolamine is N,N-dimethylpropanediamine is .

[0023] The mass ratio of the first solvent to the first total material is (0.4~2.3):1, preferably 1:1; the first catalyst is stannous octoate or organic bismuth, preferably stannous octoate, and the amount used is 500 ppm to 2000 ppm, preferably 1000 ppm; the molar ratio of diisocyanate, polyethylene glycol, N-methyldiethanolamine and N,N-dimethylpropanediamine is (2~6):(0.5~3):1:(1~4); the temperature of the addition reaction of isocyanate group and hydroxyl group is 40℃~60℃, preferably 56℃~57℃, and the reaction time is 4 h to 6 h.

[0024] The obtained tertiary amine-terminated PU prepolymers have an average molecular weight of 1400–5200; both ends are... The structure is terminally capped and contains a first structural unit (isocyanate hard segment), a second structural unit (polyethylene glycol soft segment), and a third structural unit (tertiary amine chain extender segment) in a ratio of (2~6):(0.5~3):1; specifically, the first structural unit is -OC-NH-C6H. 12 -NH-CO- or The second structural unit is -O-(EO)n-, and the third structural unit is... .

[0025] S2: The second total material undergoes a nucleophilic addition reaction between tertiary amine groups and epoxy groups in the second solvent under the action of an acidic catalyst, copolymerizing to obtain a cationic PU-polysiloxane copolymer with an average molecular weight of 7500~50000; the second total material includes a terminal tertiary amine PU prepolymer, a terminal epoxy polyether polysiloxane, and epichlorohydrin in a molar ratio of (1~1.6):1:(0.5~4.4), and the second solvent is isopropanol, diethylene glycol butyl ether, dipropylene glycol butyl ether, or dipropylene glycol; wherein the terminal tertiary amine PU prepolymer is the terminal tertiary amine PU prepolymer obtained in step S1, and the terminal epoxy polyether polysiloxane has the following structure: Where u is 11~24 and v is 33~60; the structure of epichlorohydrin is In one embodiment, u=22, v=54.

[0026] The mass ratio of the second solvent to the second total material is (0.7~1.5):1, preferably 1.5:1; the acidic catalyst is formic acid, acetic acid, or lauric acid, preferably acetic acid; wherein, the molar ratio of the acidic catalyst to the terminal tertiary amine PU prepolymer is (3~6):1; the temperature of the nucleophilic addition reaction in step S2 is 60℃~80℃, preferably 78℃; the reaction time of the nucleophilic addition reaction is 12 h~36 h, preferably 24 h.

[0027] By weight, 1 part of the above-mentioned cationic PU-polysiloxane copolymer, 0.2 to 0.5 parts of nonionic emulsifier, 0.02 to 0.04 parts of acetic acid, and 3 to 5 parts of deionized water are mixed and prepared by emulsification to obtain a cationic PU-polysiloxane copolymer hydrophilic softener; in one embodiment, the mass of the nonionic emulsifier is preferably 25% of the cationic PU-polysiloxane copolymer, and the nonionic emulsifier is preferably fatty alcohol polyoxyethylene ether (AEO-6).

[0028] The following is an example.

[0029] Example 1 Step 1: Under nitrogen protection, add 100.0 g (0.10 mol) of dehydrated PEG1000, 3.9 g (0.033 mol) of N-methyldiethanolamine, 44.4 g (0.20 mol) of IPDI and 162 g of acetone to a 500 mL dry four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel. Start stirring, add 0.16 g of stannous octoate, and reflux at 57 °C for 3 h. The temperature was lowered to below 10°C using water below 10°C. 13.6 g (0.13 mol) of N,N-dimethylpropanediamine was added via a dropping funnel over 10 min. After addition, the mixture was stirred for 1 h. After the reaction was complete, vacuum and heating were applied. Acetone was removed under vacuum at 60°C–70°C and -0.04–-0.08 MPa until completely dry, yielding 161.9 g of terminal tertiary amine PU prepolymer (B1) with an ammonia value of 1.03 mmol / g. The molar ratio of PEG1000, N-methyldiethanolamine, IPDI, and N,N-dimethylpropanediamine was 1:0.33:2:1.3, and the average molecular weight of B1 was approximately 2440. Using bromophenol blue as an indicator and isopropanol as a solvent, the hydrochloric acid standard solution was titrated with the terminal tertiary amine PU prepolymer solution until the solution turned yellow. The ammonia value was then directly measured, yielding a result of 1.03 mmol / g.

[0030] Step 2: Add 100.0g (41mmol) B1, 205.0g (34.2mmol) terminal epoxy polyether polysiloxane (average molecular weight 6000, epoxy value 0.33mmol / g), 7.4g (123.3mmol) acetic acid, and 312g isopropanol to a 1000mL dry four-necked flask equipped with a stirrer, thermometer, and reflux condenser. Start stirring and heat to 78℃~80℃, maintain the temperature for 24h, cool down to below 50℃, add 3.3g (35.4mmol) epichlorohydrin, heat to 78℃~80℃, react for 3h. After the reaction is complete, turn on the vacuum and heat, and remove isopropanol under vacuum at 70℃~80℃ and -0.04 to -0.08MPa until completely dry, to obtain 315g cationic PU-polysiloxane copolymer (C1). B1, the molar ratio of terminal epoxy polyether polysiloxane and epichlorohydrin is approximately 1.2:1:1.04.

[0031] Step 3: Add 100g C1, 25g fatty alcohol polyoxyethylene ether AEO-6, and 3.0g acetic acid to a 1000ml plastic cup equipped with a high-speed dispersion disc. Start stirring and adjust the speed to 200rpm~300rpm. After stirring for 30 minutes, add 400g of deionized water in four portions to obtain 528g of a translucent emulsion with a blue sheen and a solid content of 24.2%. The mass ratio of C1, AEO-6, acetic acid, and deionized water is 1:0.25:0.03:4.

[0032] Example 2 Step 1: Under nitrogen protection, add 100.0g (0.10mol) of dehydrated PEG1000, 6.0g (0.05mol) of N-methyldiethanolamine, 44.4g (0.20mol) of IPDI and 161g of acetone to a 500mL dry four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel. Start stirring, add 0.16g of stannous octoate, and reflux at 57℃ for 3 hours. Cool to below 10℃ with water below 10℃, and add 10.2g (0.10mol) of... N,N-Dimethylpropanediamine was added via a dropping funnel over 10 minutes. After addition, the reaction was stirred for 1 hour. After the reaction was complete, vacuum and heating were applied, and acetone was removed under vacuum at 60℃~70℃ and -0.04 to -0.08 MPa until completely dry, yielding 160.5 g of terminal tertiary amine PU prepolymer (B2) with an amine value of 0.93 mmol / g. The molar ratio of PEG1000, N-methyldiethanolamine, IPDI, and N,N-dimethylpropanediamine was 1:0.5:2:1, and the average molecular weight of B2 was approximately 3230. Using bromophenol blue as an indicator and isopropanol as a solvent, the hydrochloric acid standard solution was titrated with the terminal tertiary amine PU prepolymer solution until the solution turned yellow. The amine value was then directly measured, and the result was 0.93 mmol / g.

[0033] Step 2: Add 132.3g (41mmol) B2, 205.0g (34.2mmol) terminal epoxy polyether polysiloxane (average molecular weight 6000, epoxy value 0.33mmol / g), 8.9g (147.6mmol) acetic acid, and 346g isopropanol to a 1000mL dry four-necked flask equipped with a stirrer, thermometer, and reflux condenser. Start stirring and heat to 78℃~80℃, maintain the temperature for 24h, cool down to below 50℃, add 5.1g (55.4mmol) epichlorohydrin, heat to 78℃~80℃, react for 3h. After the reaction is complete, turn on the vacuum and heat, and remove isopropanol under vacuum at 70℃~80℃ and -0.04 to -0.08MPa until completely dry, to obtain 351g cationic PU-polysiloxane copolymer (C2). B2, the molar ratio of terminal epoxy polyether polysiloxane and epichlorohydrin is approximately 1.2:1:1.6.

[0034] Step 3: Add 100g C2, 25g fatty alcohol polyoxyethylene ether AEO-6, and 3.0g acetic acid to a 1000ml plastic cup equipped with a high-speed dispersion disc. Start stirring and adjust the speed to 200rpm~300rpm. After stirring for 30 minutes, add 400g of deionized water in four portions to obtain 528g of a translucent emulsion with a blue sheen and a solid content of 24.2%. The mass ratio of C2, AEO-6, acetic acid, and deionized water is 1:0.25:0.03:4.

[0035] Example 3 Step 1: Under nitrogen protection, add 60.0 g (0.10 mol) of dehydrated PEG600, 6.0 g (0.05 mol) of N-methyldiethanolamine, 44.4 g (0.20 mol) of IPDI and 121 g of acetone to a 500 mL dry four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel. Start stirring, add 0.12 g of stannous octoate, and reflux at 57 °C for 3 h. Cool to below 10 °C with water below 10 °C, and add 10.2 g (0.10 mol) of... N,N-Dimethylpropanediamine was added via a dropping funnel over 10 minutes. After addition, the reaction was stirred for 1 hour. After the reaction was complete, vacuum and heating were applied, and acetone was removed under vacuum at 60℃~70℃ and -0.04 to -0.08 MPa until completely dry, yielding 120.2 g of terminal tertiary amine PU prepolymer (B3) with an amine value of 1.24 mmol / g. The molar ratio of PEG600, N-methyldiethanolamine, IPDI, and N,N-dimethylpropanediamine was 1:0.5:2:1, and the average molecular weight of B3 was approximately 2420. Using bromophenol blue as an indicator and isopropanol as a solvent, the hydrochloric acid standard solution was titrated with the terminal tertiary amine PU prepolymer solution until the solution turned yellow. The amine value was then directly measured, and the result was 1.24 mmol / g.

[0036] Step 2: Add 99.2g (41mmol) B3, 205.0g (34.2mmol) terminal epoxy polyether polysiloxane (average molecular weight 6000, epoxy value 0.33mmol / g), 8.9g (147.6mmol) acetic acid, and 313g isopropanol to a 1000mL dry four-necked flask equipped with a stirrer, thermometer, and reflux condenser. Start stirring and heat to 78℃~80℃, maintain the temperature for 24h, cool down to below 50℃, add 5.1g (55.4mmol) epichlorohydrin, heat to 78℃~80℃, react for 3h. After the reaction is complete, turn on the vacuum and heat, and remove isopropanol under vacuum at 70℃~80℃ and -0.04 to -0.08MPa until completely dry, to obtain 318g cationic PU-polysiloxane copolymer (C3). B3, the molar ratio of terminal epoxy polyether polysiloxane and epichlorohydrin is approximately 1.2:1:1.6.

[0037] Step 3: Add 100g C3, 25g fatty alcohol polyoxyethylene ether AEO-6, and 3.0g acetic acid to a 1000ml plastic cup equipped with a high-speed dispersion disc. Start stirring and adjust the speed to 200rpm~300rpm. After stirring for 30 minutes, add 400g of deionized water in four portions to obtain 528g of a translucent emulsion with a blue sheen and a solid content of 24.2%. The mass ratio of C2, AEO-6, acetic acid, and deionized water is 1:0.25:0.03:4.

[0038] Experimental results verification The molecular weight of the products obtained in Examples 1-3 was determined by GPC (gel permeation chromatography); it was verified that the molecular weight of the cationic PU-polysiloxane copolymers prepared in the examples was in the range of 7500 to 50000.

[0039] The carbonyl group, a characteristic functional group of the urethane bond, in the molecular structure of the products obtained in Examples 1-3 was determined using infrared spectroscopy; the values ​​for 1717-1719 cm⁻¹ were found to be 1717-1719 cm⁻¹. -1 There is a distinct characteristic peak at this location.

[0040] The emulsions prepared in Examples 1-3 and commercially available hydrophilic silicone oil were applied to nylon-spandex knitted fabrics at a dosage of 20 g / L. The application process was as follows: solution preparation → dip-and-roll (pressure 3 kgf / m2) → setting (160℃ × 1.0 min) → moisture regain evaluation. Then, hand feel evaluation and hydrophilicity test were performed, and the results are shown in Table 1.

[0041] Hand feel evaluation: The evaluation is conducted by touch, using a blank original fabric as a reference. A rating system of 1-5 points is used, with higher scores indicating better hand feel. Five professionals score simultaneously, and the average value is taken. Hand feel primarily considers softness, bulkiness, and resilience. Resilience is judged based on the fabric's wrinkle recovery angle. The wrinkle recovery test method refers to GB / T 3819-1997. Three test samples are taken in each of the warp and weft directions, and the average value is taken. The sum of the warp and weft wrinkle recovery angles is recorded as the fabric's wrinkle recovery angle. A larger wrinkle recovery angle indicates better resilience.

[0042] Hydrophilicity test: The test is conducted according to the standard AATCC 79-2010 "Water Absorption of Textiles", with the unit being seconds (s). The shorter the time, the better the hydrophilicity.

[0043] Table 1 Performance Evaluation Table of Different Softeners

[0044] The data in Table 1 show that, compared with commercially available hydrophilic silicone oils, the embodiments of this application have a better hand feel and better instantaneous and long-lasting hydrophilicity on nylon-spandex knitted fabrics.

[0045] Following the same steps as in Example 2, IPDI was replaced with the same molar amount of OCN-C6H. 12 -NCO, it was verified that the PU-polysiloxane copolymer and hydrophilic silicone oil obtained in the final preparation still have similar properties to those in Examples 1-3.

[0046] Following the same steps as in Example 2, the mass of IPDI was adjusted between 22.2g and 66.6g, or the mass of polyethylene glycol was adjusted between 25g and 150g, or PEG1000 was replaced with PEG600 or PEG2000, or the mass of N,N-dimethylpropylenediamine was adjusted between 5.1g and 20.4g. It was verified that the PU-polysiloxane copolymer and hydrophilic silicone oil finally prepared still had similar properties to those in Examples 1-3.

[0047] Following the same steps as in Example 2, the mass of B2 was adjusted between 110.2g and 176.4g, or the mass of epichlorohydrin was adjusted between 1.6g and 14g. It was verified that the PU-polysiloxane copolymer and hydrophilic silicone oil obtained in the final preparation still had similar properties to those in Examples 1-3.

[0048] Those skilled in the art will readily understand that the above are merely preferred embodiments of this application and are not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the scope of protection of this application.

Claims

1. A cationic PU-polysiloxane copolymer, characterized in that, It has an average molecular weight of 7,500 to 50,000 and is polymerized from terminal tertiary amine PU prepolymer, terminal epoxy polyether polysiloxane and epichlorohydrin in a molar ratio of (1 to 1.6): 1: (0.5 to 4.4). The terminal tertiary amine PU prepolymer comprises a first structural unit, a second structural unit, and a third structural unit in a ratio of (2~6):(0.5~3):1; specifically, the first structural unit is -OC-NH-C6H 12 -NH-CO- or The second structural unit is -O-(EO). n - The third structural unit is ; The two ends of the terminal tert-amine PU prepolymer are Group end capping; The terminal epoxy polyether polysiloxane structure is as follows: Where u is 11~24 and v is 33~60; The epichlorohydrin structure is as follows: .

2. The cationic PU-polysiloxane copolymer as described in claim 1, characterized in that, The average molecular weight of the terminal tertiary amine PU prepolymer is 1400~5200.

3. The method for preparing the cationic PU-polysiloxane copolymer according to claim 1 or 2, characterized in that, Under the action of an acidic catalyst, the second total material undergoes a nucleophilic addition reaction between tertiary amine groups and epoxy groups in the second solvent, and copolymerizes to obtain the cationic PU-polysiloxane copolymer; the second total material includes a terminal tertiary amine PU prepolymer, a terminal epoxy polyether polysiloxane, and epichlorohydrin in a molar ratio of (1~1.6):1: (0.5~4.4), and the second solvent is one or more of isopropanol, diethylene glycol butyl ether, dipropylene glycol butyl ether, or dipropylene glycol.

4. The preparation method according to claim 3, characterized in that, The acidic catalyst for the nucleophilic addition reaction is formic acid, acetic acid, or lauric acid, and the molar ratio of the acidic catalyst to the terminal tertiary amine PU prepolymer is (3~6):

1.

5. The preparation method according to claim 3, characterized in that, The mass ratio of the second solvent to the second total material is (0.7~1.5):

1.

6. A terminal tertiary amine polyurethane prepolymer, characterized in that, Used for the preparation of the cationic PU-polysiloxane copolymer according to any one of claims 3-5.

7. The tertiary amine PU prepolymer as described in claim 6, characterized in that, The prepolymer is prepared by the following method: a first total material is uniformly dissolved in a first solvent, and an addition reaction of isocyanate groups and hydroxyl groups occurs. Then, N,N-dimethylpropanediamine is added to obtain the terminal tertiary amine PU prepolymer. The first total material includes a diisocyanate, polyethylene glycol, and N-methyldiethanolamine in a molar ratio of (2~6):(0.5~3):1, wherein the molar ratio of N,N-dimethylpropanediamine to N-methyldiethanolamine is (1~4):1, and the first solvent is acetone, butanone, or ethyl acetate.

8. The tertiary amine PU prepolymer according to claim 7, characterized in that, The catalyst for the addition reaction of the isocyanate group and the hydroxyl group is stannous octoate or organic bismuth, and the concentration of the catalyst for the addition reaction of the isocyanate group and the hydroxyl group is 500 ppm to 2000 ppm.

9. A hydrophilic softener, characterized in that, The cationic PU-polysiloxane copolymer, including 1 or 2.

10. The hydrophilic softener as described in claim 9, characterized in that, It also includes nonionic emulsifier, acetic acid and water, with the mass ratio of cationic PU-polysiloxane copolymer, nonionic emulsifier, acetic acid and water being 1:(0.2~0.5):(0.02~0.04):(3~5).

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