A composite emulsifier for spinning oil and a preparation method thereof

Abstract

This invention belongs to the field of emulsifier preparation technology, specifically relating to a composite emulsifier for spinning oils and its preparation method. A hybrid particle dispersion is obtained by using raw materials including castor oil / silica-alumina hybrid particles, acrylamide monomers, quaternary ammonium salt cationic monomers, and temperature-sensitive monomers. The composite emulsifier is obtained by high-speed shearing using raw materials including sodium alginate, potassium citrate, the hybrid particle dispersion, and alkyl glycosides. It exhibits good centrifugal stability and room temperature stability, excellent heat resistance, and low foaming properties.

Description

Technical Field

[0001] This invention belongs to the field of emulsifier preparation technology, specifically relating to a composite emulsifier for spinning oils and its preparation method. Background Technology

[0002] During the spinning process of chemical fibers, the high-speed friction between the fibers and metal components such as the guide and winding device generates a large amount of static electricity, leading to fiber loosening, fuzzing, and breakage, and severely affecting subsequent processing. To overcome this problem, spinning oils have emerged. Spinning oils are specialized chemicals applied to the fiber surface during spinning. Their core function is to form a uniform lubricating film on the fiber surface, imparting excellent smoothness, antistatic properties, bundle properties, and suitable frictional characteristics to the fiber, thereby ensuring the stable and efficient operation of the high-speed spinning process. Early spinning oils had relatively simple compositions, often using physical mixtures of mineral oil, animal and vegetable oils, and simple surfactants. Their performance was limited, especially in terms of heat resistance, emulsion stability, and functional synergy. With the popularization of advanced spinning technologies such as high-speed spinning, ultra-fine denier fibers, and profiled fibers, unprecedentedly stringent requirements have been placed on the comprehensive performance of spinning oils. Traditional single-component or simply compounded oil systems are no longer sufficient to meet these demands.

[0003] Chinese Patent Publication No. CN120967554A discloses a compound emulsifier for DTY oils and the DTY oil itself. The compound emulsifier is prepared by mixing raw materials including an antistatic agent, C12-14 fatty alcohol polyoxyethylene polyoxypropylene ether, fatty acid amide polyoxyethylene polyoxypropylene ether, and sorbitan fatty acid ester. It does not contain APEO and is a green and environmentally friendly surfactant with good biodegradability. No harmful byproducts are generated during production, and the production process is simple, easy to operate, and low in cost. Chinese Patent Publication No. CN116854927A discloses a method for synthesizing a low-foaming chemical fiber oil emulsifier. It is prepared by mixing raw materials including silane coupling agent-modified silica, low-carbon alcohols, ethylene oxide, and propylene oxide. The reaction process is stable, and due to the design of the reaction raw materials, proportions, and process, it can be produced using conventional equipment, greatly reducing the production input cost and significantly improving the emulsifying performance and stability of the product, making it widely applicable. However, existing composite emulsifiers produce a lot of foam, are prone to causing spinning entanglement, and have problems such as poor oil film adhesion and easy peeling. Therefore, there is an urgent need to develop a composite emulsifier with synergistic performance and environmental friendliness. Summary of the Invention

[0004] To address at least one of the above problems, the present invention provides a method for preparing a composite emulsifier for spinning oils, characterized by comprising the following steps: S100, using castor oil polyoxyethylene ether, Functionalized castor oil-based monomers were prepared from raw materials of caprolactone and glycidyl methacrylate. S200: An aluminum chelate solution is prepared using raw materials including aluminum isopropoxide and acetylacetone; an acidic silica sol is obtained by acidic hydrolysis using raw materials including tetraethyl orthosilicate and silane coupling agent; an O / W microemulsion is obtained by high-speed shear emulsification using raw materials including functionalized castor oil monomers and emulsifiers; the aluminum chelate solution and acidic silica sol are mixed and added to the O / W microemulsion to react and obtain castor oil / silica-aluminum hybrid particles; S300 uses raw materials including castor oil / silica-alumina hybrid particles, acrylamide monomers, quaternary ammonium salt cationic monomers, and temperature-sensitive monomers to obtain a hybrid particle dispersion through polymerization reaction; S400: The composite emulsifier is obtained by high-speed shearing using raw materials including sodium alginate, potassium citrate, hybrid particulate dispersion, and alkyl glycoside.

[0005] Further, step S100 specifically involves: adding castor oil polyoxyethylene ether to the reactor under an inert atmosphere, raising the temperature to 110-120°C, and adding the mixture while stirring. After reacting caprolactone and stannous octoate for 2-3 hours, the temperature was lowered to 90-100℃, and tetrabutylammonium salt was added. Then glycidyl methacrylate was added dropwise, and the reaction was maintained at 90-100℃ for 4-5 hours. After the reaction was completed, the functionalized castor oil-based monomer was obtained by vacuum distillation.

[0006] Further, the preparation method of the castor oil polyoxyethylene ether is as follows: castor oil and bimetallic cyanide catalyst are added to a closed reactor. Under an inert atmosphere, the mixture is stirred and heated to 120-130°C. After vacuum dehydration and degassing, the vacuum is closed, and the temperature is maintained at 135-140°C. Ethylene oxide is added to the mixture, and the feeding time is controlled at 5-6 hours. After the feeding is completed, the mixture is kept warm and stirred for 1-2 hours, and then the temperature is lowered to 80°C. Phosphoric acid is added, and the mixture is stirred for 30-40 minutes. The mixture is then filtered while hot to obtain a light yellow viscous liquid, which is the castor oil polyoxyethylene ether.

[0007] Furthermore, step S200 specifically includes the following steps: S210. Add aluminum isopropoxide to isopropanol, mix well, and then add acetylacetone dropwise. After the addition is complete, reflux and stir at 65-75℃ for 1.5-2.5h to obtain an aluminum chelate solution. S220. Add tetraethyl orthosilicate and silane coupling agent to isopropanol, mix well, and then add acidic aqueous solution dropwise. After the addition is complete, stir at room temperature for 3-4 hours to obtain acidic silica sol. S230. After mixing functionalized castor oil monomer and isopropanol evenly, add emulsifier and dilute nitric acid, raise the temperature to 40-50℃, and continuously process with a high-shear emulsifier for 10-15 minutes to obtain O / W type microemulsion. S240. After mixing the aluminum chelate solution with the acidic silica sol evenly, raise the temperature to 45-55℃ and add it dropwise to the O / W type microemulsion while keeping it warm and stirring. After the addition is complete, raise the temperature to 60-65℃ and stir for 20-30 minutes. After the reaction is complete, centrifuge and discard the supernatant. The precipitate is ultrasonically cleaned with a mixture of ethanol / acetone and repeated 2-3 times. After drying, castor oil / silica-alumina hybrid particles are obtained.

[0008] Further, step S300 specifically involves: adding castor oil / silica-alumina hybrid particles to deionized water, dispersing them evenly, then adding acrylamide monomers, quaternary ammonium salt cationic monomers, thermosensitive monomers, and crosslinking agents, stirring until completely dissolved, and then purging with nitrogen for 30-40 minutes to remove oxygen. The water bath is then heated to 60-70°C, and an initiator is quickly added. The mixture is stirred and reacted for 5-6 hours. After the reaction is completed, the mixture is cooled to room temperature to obtain a hybrid particle dispersion.

[0009] Furthermore, the quaternary ammonium salt cationic monomer is one or more of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, dimethyl diallyl ammonium chloride, and methacrylamidopropyltrimethylammonium chloride.

[0010] Furthermore, the temperature-sensitive monomer is one or more of N-isopropylacrylamide, N-n-propylacrylamide, and N,N-diethylacrylamide.

[0011] Further, step S400 specifically involves: adding deionized water to the reactor, turning on the high-speed shear dispersion emulsifier, adding sodium alginate powder, continuing high-speed shearing for 20-30 minutes after the addition is complete, adding potassium citrate, stirring until dissolved, measuring the pH of the system to be 6.5-7.5 with a pH meter, adding the hybrid particle dispersion while stirring, continuing stirring for 20-30 minutes after the addition is complete, adding alkyl glycosides, stirring for 10-20 minutes, and then obtaining the composite emulsifier after high-speed shearing for 4-6 minutes.

[0012] A composite emulsifier for spinning oils is prepared using the preparation method described in any of the above technical solutions.

[0013] The present invention has the following beneficial effects: By constructing a silicon-aluminum hybrid structure, functionalized castor oil molecules are firmly coated or grafted onto the surface and pores of the silicon-aluminum hybrid network, forming an organic-inorganic hybrid structure. This structure improves the temperature resistance of the emulsifier, effectively solving the problem of high-temperature instability in existing emulsifiers. Grafting quaternary ammonium salt cationic groups onto the surface of the hybrid particles allows for rapid capture of fiber surface charges through electrostatic adsorption, preventing electrostatic accumulation that leads to entanglement and breakage. The synergistic effect of alkyl glycosides and sodium alginate gives the emulsifier low-foaming properties, preventing spinning foam entanglement and making it suitable for the high hydrophilicity requirements of regenerated fibers. Detailed Implementation

[0014] The technical solutions in the embodiments of this application will be clearly and completely described below with reference to the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0015] Spinning oils are indispensable auxiliaries in the fiber spinning process. Their main function is to reduce the coefficient of friction between fibers and equipment, and between fibers themselves, thereby reducing static electricity, preventing fiber breakage and fuzzing, and improving fiber bundle properties and subsequent processing performance, directly affecting the quality and performance of the final fiber product. However, in existing technologies, some emulsifiers are modified with synthetic resins or inorganic particles, resulting in problems such as poor particle dispersibility. Therefore, this invention provides a method for preparing a composite emulsifier for spinning oils, comprising the following steps: S100, using castor oil polyoxyethylene ether, Functionalized castor oil-based monomers were prepared from raw materials of caprolactone and glycidyl methacrylate. S200: An aluminum chelate solution is prepared using raw materials including aluminum isopropoxide and acetylacetone; an acidic silica sol is obtained by acidic hydrolysis using raw materials including tetraethyl orthosilicate and silane coupling agent; an O / W microemulsion is obtained by high-speed shear emulsification using raw materials including functionalized castor oil monomer and emulsifier; the aluminum chelate solution and acidic silica sol are mixed and added dropwise to the O / W microemulsion to react and obtain castor oil / silica-aluminum hybrid particles; S300 uses raw materials including castor oil / silica-alumina hybrid particles, acrylamide monomers, quaternary ammonium salt cationic monomers, and temperature-sensitive monomers to obtain a hybrid particle dispersion through polymerization reaction; S400: The composite emulsifier is obtained by high-speed shearing using raw materials including sodium alginate, potassium citrate, hybrid particulate dispersion, and alkyl glycoside.

[0016] Specifically, step S100 involves adding castor oil polyoxyethylene ether to the reactor under a nitrogen atmosphere, raising the temperature to 110-120°C, and adding the mixture while stirring. After reacting caprolactone and stannous octoate for 2-3 hours, the temperature was lowered to 90-100℃, and tetrabutylammonium salt was added. Then glycidyl methacrylate was added dropwise, and the reaction was maintained at 90-100℃ for 4-5 hours. After the reaction was completed, the functionalized castor oil-based monomer was obtained by vacuum distillation.

[0017] In this step, castor oil polyoxyethylene ether, The mass ratio of caprolactone, stannous octanoate, tetrabutylammonium salt and glycidyl methacrylate is 100:20-35:0.15-0.3:0.8-1.5:12-20; the tetrabutylammonium salt is tetrabutylammonium bromide, and the dropping rate of glycidyl methacrylate is 2-5 g / min.

[0018] In this process, under the catalysis of stannous octoate, castor oil polyoxyethylene ether reacts with... Caprolactone undergoes ring-opening polymerization, introducing flexible hydrophobic segments of polycaprolactone into the molecular chain. Subsequently, under the catalysis of tetrabutylammonium bromide, it undergoes a ring-opening reaction with the epoxy group of glycidyl methacrylate, thereby introducing methacryloxy groups at the molecular ends. This effectively enhances the adhesion of the oil to the fiber surface and provides a foundation for subsequent reactions.

[0019] The preparation method of castor oil polyoxyethylene ether is as follows: castor oil and bimetallic cyanide catalyst are added to a closed reactor. Under a nitrogen atmosphere, the mixture is stirred and heated to 120-130°C. After vacuum dehydration and degassing for 20-30 minutes, the vacuum is closed, and the temperature is maintained at 135-140°C. Ethylene oxide is added to the mixture over a period of 5-6 hours. After the addition is complete, the mixture is kept warm and stirred for 1-2 hours, and then the temperature is lowered to 80°C. Phosphoric acid is added for neutralization, and the mixture is stirred for 30-40 minutes. The mixture is then filtered while hot to obtain a light yellow viscous liquid, which is castor oil polyoxyethylene ether.

[0020] In this step, the mass ratio of castor oil, bimetallic cyanide catalyst, ethylene oxide, and phosphoric acid is 100:0.2-0.5:250-320:0.3-0.8; the bimetallic cyanide catalyst is Zn3[Co(CN)6]2. During this process, under the action of the bimetallic cyanide catalyst, the ring-opening polymerization of ethylene oxide monomers is initiated, grafting onto castor oil molecules to form castor oil polyoxyethylene ether. Vacuum dehydration and degassing remove moisture from the system, ensuring the activity of the catalyst; neutralizing the catalyst with phosphoric acid terminates the polymerization reaction, preventing excessive polymerization of ethylene oxide that could lead to abnormal product viscosity, and simultaneously adjusting the product pH to ensure its subsequent reaction with... The reactivity of caprolactone and glycidyl methacrylate.

[0021] Specifically, step S200 includes the following steps: S210. Add aluminum isopropoxide to isopropanol, mix well, and then add acetylacetone dropwise. After the addition is complete, reflux and stir at 65-75℃ for 1.5-2.5h to obtain an aluminum chelate solution. S220. Add tetraethyl orthosilicate and silane coupling agent to isopropanol, mix well, and then add acidic aqueous solution dropwise. After the addition is complete, stir at room temperature for 3-4 hours to obtain acidic silica sol. S230. After mixing functionalized castor oil monomer and isopropanol evenly, add emulsifier and 2wt% dilute nitric acid, raise the temperature to 40-50℃, and use a high-shear emulsifier at a speed of 8000-10000rpm for 10-15min to obtain O / W type microemulsion. S240. After mixing the aluminum chelate solution with the acidic silica sol evenly, raise the temperature to 45-55℃ and add it dropwise to the O / W type microemulsion while keeping it warm and stirring. After the addition is complete, raise the temperature to 60-65℃ and stir for 20-30 minutes. After the reaction is complete, centrifuge and discard the supernatant. The precipitate is ultrasonically cleaned with a mixture of ethanol / acetone and repeated 2-3 times. After drying, castor oil / silica-alumina hybrid particles are obtained.

[0022] In step S210, the mass ratio of aluminum isopropoxide, acetylacetone, and isopropanol is 10:5-8:55-70. During this process, aluminum isopropoxide reacts with acetylacetone to form a stable coordinated aluminum chelate, which slows down the hydrolysis and condensation rate of the aluminum alkoxide. This prevents it from directly hydrolyzing to form aluminum hydroxide precipitate when mixed with silica sol in subsequent reactions, ensuring that aluminum ions can undergo a condensation reaction with silicic acid in the silica sol.

[0023] In step S220, the mass ratio of tetraethyl orthosilicate, silane coupling agent, isopropanol, and acidic aqueous solution is 20:2-5:36-48:8-12; the silane coupling agent is KH-570; the acidic aqueous solution is obtained by slowly injecting concentrated nitric acid along a glass rod into a mixture of deionized water and isopropanol, and stirring until homogeneous. During this process, tetraethyl orthosilicate and the silane coupling agent KH-570 partially hydrolyze under acidic conditions, generating a silica sol containing silanol groups and vinyl groups; the acidic conditions favor hydrolysis and inhibit condensation, forming a sol with low cross-linking degree and good stability.

[0024] In step S230, the mass ratio of functionalized castor oil monomer, isopropanol, emulsifier, and dilute nitric acid is 12-25:25-40:3-6:15-30; the emulsifier is OP-10. In this process, using functionalized castor oil monomer and isopropanol as the oil phase, under the action of emulsifier OP-10, uniformly sized nanoscale O / W microemulsion droplets are formed through high-speed shearing.

[0025] In step S240, the mass ratio of the aluminum chelate solution, acidic silica sol, and O / W microemulsion is 3-4:3.5-4.5:12-15. During this process, after the aluminum chelate solution is mixed with the acidic silica sol, the aluminum chelate slowly hydrolyzes under acidic conditions, releasing Al. 3+ Al 3+ The castor oil undergoes a condensation reaction with the silanol groups generated by the hydrolysis of tetraethyl orthosilicate in silica sol, forming a stable Si-O-Al structure through chemical bonding, thus constructing a silicon-aluminum hybrid structure. This reaction allows functionalized castor oil molecules to be firmly coated or grafted onto the surface and pores of the silicon-aluminum hybrid network, forming an organic-inorganic hybrid structure.

[0026] Specifically, step S300 involves adding castor oil / silica-alumina hybrid particles to deionized water, dispersing them evenly, then adding acrylamide monomers, quaternary ammonium salt cationic monomers, thermosensitive monomers, and crosslinking agents. The mixture is stirred until completely dissolved, and nitrogen gas is introduced to remove oxygen for 30-40 minutes. The water bath temperature is raised to 60-70°C, and an initiator is quickly added. The mixture is stirred and reacted for 5-6 hours. After the reaction is completed, the mixture is cooled to room temperature to obtain a hybrid particle dispersion.

[0027] In this step, the mass ratio of deionized water, castor oil / silica-alumina hybrid particles, acrylamide monomers, quaternary ammonium salt cationic monomers, and thermosensitive monomers is 100:3-8:14-25:8-15:5-10; the acrylamide monomer is acrylamide; the quaternary ammonium salt cationic monomer is one or more of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, dimethyl diallyl ammonium chloride, and methacrylamidopropyltrimethylammonium chloride; the thermosensitive monomer is one or more of N-isopropylacrylamide, N-n-propylacrylamide, and N,N-diethylacrylamide; and the crosslinking agent is N,N / -One or more of methylene bisacrylamide, polyethylene glycol diacrylate, and trimethylolpropane triacrylate.

[0028] In this process, using water as a medium, the vinyl groups on the surface of castor oil / silica-alumina hybrid particles undergo a free radical copolymerization reaction with water-soluble acrylamide, quaternary ammonium salt cationic monomers, thermosensitive monomers, and crosslinking agents under the action of an initiator. The polymer chains are chemically bonded to the particle surface through KH-570 double bonds and simultaneously crosslink to form a three-dimensional network shell. Acrylamide provides hydrophilicity and film-forming properties, while the quaternary ammonium salt monomers impart antistatic properties and the ability to adsorb onto negatively charged fiber surfaces. The thermosensitive monomers give the polymer shell a low critical dissolution temperature, causing hydrophobic shrinkage at high spinning temperatures, resulting in tighter adhesion to the fiber. During room-temperature washing, it hydrophilically swells and is easily washed away.

[0029] Specifically, step S400 involves: adding deionized water to the reactor, turning on the high-speed shear dispersion emulsifier, adding sodium alginate powder, continuing high-speed shearing for 20-30 minutes after the addition is complete, adding potassium citrate, stirring until dissolved, measuring the pH of the system to be 6.5-7.5 with a pH meter, adding the hybrid particle dispersion while stirring, continuing stirring for 20-30 minutes after the addition is complete, adding alkyl glycosides, stirring for 10-20 minutes, and then obtaining the composite emulsifier after high-speed shearing for 4-6 minutes.

[0030] In this step, the mass ratio of deionized water, sodium alginate powder, potassium citrate, hybrid particle dispersion, and alkyl glycoside is 100:1.2-2:0.3-0.6:25-40:5-10; the alkyl glycoside is one or more of decyl glucoside, lauryl glucoside, and APG0814. During this process, sodium alginate, as a natural anionic polysaccharide, has a high viscosity in its aqueous solution, which enhances the stability of the emulsion and imparts a certain degree of moisturizing properties to the oil. Potassium citrate can adjust the pH of the system and chelate any metal ions that may be present, improving stability; alkyl glycoside, as a nonionic surfactant, has a good synergistic effect with the hybrid particles and sodium alginate, further reducing surface tension and ensuring that the emulsifier can quickly spread on the fiber surface to form a uniform oil film.

[0031] Preparation Example 1 The preparation method of castor oil polyoxyethylene ether is as follows: 100g castor oil and 0.3g Zn3[Co(CN)6]2 catalyst are added to a closed reactor. Under a nitrogen atmosphere, the mixture is stirred and heated to 125℃. After vacuum dehydration and degassing for 25min, the vacuum is turned off and the temperature is maintained at 140℃. 280g ethylene oxide is added to the mixture over a period of 6h. After the addition is complete, the mixture is kept warm and stirred for 2h. The temperature is then lowered to 80℃, and 0.5g phosphoric acid is added for neutralization. After stirring for 35min, the mixture is filtered while hot to obtain a light yellow viscous liquid, which is castor oil polyoxyethylene ether.

[0032] Preparation Example 2 This preparation example differs from Preparation Example 1 in the following ways: In the preparation of castor oil polyoxyethylene ether, 100g castor oil and 0.2g Zn3[Co(CN)6]2 catalyst are added, the temperature is raised to 120℃, and after vacuum dehydration and degassing, the temperature is maintained at 135℃. 250g ethylene oxide is added. After the addition is completed, the temperature is kept warm and stirred for 1 hour, then the temperature is lowered to 80℃, 0.3g phosphoric acid is added for neutralization, and the mixture is filtered while hot after stirring to obtain the final product.

[0033] Preparation Example 3 This preparation example differs from Preparation Example 1 in the following ways: In the preparation of castor oil polyoxyethylene ether, 100g castor oil and 0.5g Zn3[Co(CN)6]2 catalyst are added, the temperature is raised to 125℃, and after vacuum dehydration and degassing, the temperature is maintained at 140℃. 320g ethylene oxide is added. After the addition is completed, the temperature is kept warm and stirred for 2 hours, then the temperature is lowered to 80℃, 0.8g phosphoric acid is added for neutralization, and the mixture is filtered while hot after stirring to obtain the final product.

[0034] Example 1 S1. Under a nitrogen atmosphere, 100g of the castor oil polyoxyethylene ether prepared in Example 1 was added to the reactor, the temperature was raised to 115°C, and the mixture was added while stirring. Caprolactone and 0.2 g stannous octoate were reacted for 3 h, and then the temperature was lowered to 90 °C. 1 g tetrabutylammonium salt was added, followed by the dropwise addition of 15 g glycidyl methacrylate at a rate of 3 g / min. After the addition was completed, the mixture was kept at 100 °C for 5 h. After the reaction was completed, the mixture was vacuum distilled at 95 °C and -0.098 MPa for 1 h to remove unreacted monomers, yielding functionalized castor oil-based monomers. S2. Add 10g of aluminum isopropoxide to 60g of isopropanol, mix well, and then add 6g of acetylacetone dropwise. After the addition is complete, reflux and stir at 70℃ for 2h to obtain an aluminum chelate solution. Add 20g of tetraethyl orthosilicate and 3g of KH-570 to 40g of isopropanol, mix well, and then add an acidic aqueous solution (0.4g concentrated nitric acid + 5.3g deionized water + 4.5g isopropanol). After the addition is complete, stir at room temperature for 3.5h to obtain an acidic silica sol. Mix 20g of functionalized castor oil monomer and 30g of isopropanol well, then add 4g of emulsifier OP-10 and 20g of 2wt% dilute nitric acid. The acid was heated to 45°C and emulsified at 9000 rpm for 12 min using a high-shear emulsifier to obtain an O / W microemulsion. 3.5 g of aluminum chelate solution was mixed with 4 g of acidic silica sol and the mixture was heated to 50°C and added dropwise to 13 g of O / W microemulsion under stirring. After the addition was complete, the temperature was increased to 65°C and the mixture was stirred for 25 min. After the reaction was completed, the supernatant was discarded by centrifugation. The precipitate was ultrasonically cleaned with a 1:1 ethanol / acetone mixture and repeated 3 times. The precipitate was dried at 45°C for 4 h to obtain castor oil / silica-alumina hybrid particles. S3. Add 5g of castor oil / silica-alumina hybrid particles to 100g of deionized water, disperse evenly, and then add 20g of acrylamide, 10g of methacryloyloxyethyltrimethylammonium chloride, 7g of N-isopropylacrylamide, and 0.3g of N,N / Methylenebisacrylamide was stirred until completely dissolved and nitrogen gas was introduced to remove oxygen for 35 min. The mixture was then heated to 65°C in a water bath, and an aqueous solution of ammonium persulfate (0.3 g of ammonium persulfate dissolved in 5 mL of deionized water) was quickly added. The mixture was stirred and reacted for 5.5 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a hybrid particle dispersion. S4. Add 100g of deionized water to the reactor, turn on the high-speed shear dispersion emulsifier (8000rpm), and slowly add 1.5g of sodium alginate powder. After the addition is complete, continue high-speed shearing for 25min. Then add 0.4g of potassium citrate and stir until dissolved. Use a pH meter to measure the pH of the system to be 6.5-7.5. Add 30g of hybrid particle dispersion while stirring at 400rpm. After the addition is complete, continue stirring for 25min. Add 7g of decyl glucoside and stir for 15min. Then, shear at 3500rpm for 5min to obtain the composite emulsifier.

[0035] Example 2 This embodiment differs from Embodiment 1 in the following ways: In step S1, 100g of castor oil polyoxyethylene ether is added to the reactor, the temperature is raised to 120°C, and the mixture is added while stirring. Caprolactone and 0.3 g stannous octoate were reacted for 3 h, and then the temperature was lowered to 100 °C. 1.5 g tetrabutylammonium salt was added to the mixture, followed by the addition of 20 g glycidyl methacrylate at a rate of 5 g / min. After the addition was completed, the mixture was kept at 100 °C for 5 h. After the reaction was completed, the functionalized castor oil-based monomer was obtained by vacuum distillation. In step S2, 10g of aluminum isopropoxide was added to 70g of isopropanol, mixed thoroughly, and then 8g of acetylacetone was added dropwise. After the addition was complete, the mixture was refluxed and stirred at 75°C for 2.5h to obtain an aluminum chelate solution. 20g of tetraethyl orthosilicate and 5g of KH-570 were added to 48g of isopropanol, mixed thoroughly, and then an acidic aqueous solution (0.5g concentrated nitric acid + 5.5g deionized water + 6g isopropanol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 4h to obtain an acidic silica sol. 25g of functionalized castor oil monomer and 40g of isopropanol were mixed thoroughly and then added... 6g of emulsifier OP-10 and 30g of 2wt% dilute nitric acid were heated to 50℃ and emulsified at 10000rpm for 15min using a high-shear emulsifier to obtain an O / W microemulsion. 4g of aluminum chelate solution and 4.5g of acidic silica sol were mixed evenly, and the mixture was heated to 55℃ and added dropwise to 15g of the O / W microemulsion under stirring. After the addition was complete, the temperature was increased to 65℃ and stirred for 30min. After the reaction was completed, the mixture was centrifuged, ultrasonically cleaned, and dried to obtain castor oil / aluminum silica hybrid particles. In step S3, 8g of castor oil / silica-alumina hybrid particles are added to 100g of deionized water and dispersed evenly. Then, 25g of acrylamide, 15g of methacryloyloxyethyltrimethylammonium chloride, 10g of N-isopropylacrylamide, and 0.4g of N,N / Methylenebisacrylamide was stirred until completely dissolved and nitrogen gas was introduced to remove oxygen for 40 min. The mixture was heated to 70°C in a water bath and ammonium persulfate aqueous solution (0.4 g of ammonium persulfate dissolved in 6 mL of deionized water) was quickly added. The mixture was stirred and reacted for 6 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a hybrid particle dispersion. In step S4, 100g of deionized water was added to the reactor, and a high-speed shear dispersion emulsifier (8000rpm) was turned on. 2g of sodium alginate powder was slowly added to the reactor. After the addition was completed, high-speed shearing was continued for 30min. Then, 0.6g of potassium citrate was added and stirred until dissolved. The pH of the system was measured to be 6.5-7.5 using a pH meter. 40g of hybrid particle dispersion was added to the reactor while stirring at 400rpm. After the addition was completed, stirring was continued for 30min. 10g of decyl glucoside was added and stirred for 20min. Then, high-speed shearing was performed at 3500rpm for 6min to obtain the composite emulsifier.

[0036] Example 3 This embodiment differs from Embodiment 1 in the following ways: In step S1, 100g of castor oil polyoxyethylene ether is added to the reactor, the temperature is raised to 110°C, and the mixture is added while stirring. Caprolactone and 0.15 g stannous octoate were reacted for 3 h, and then the temperature was lowered to 90 °C. 0.8 g tetrabutylammonium salt was added, followed by the addition of 12 g glycidyl methacrylate at a rate of 3 g / min. After the addition was completed, the reaction was kept at 90 °C for 4 h. After the reaction was completed, the functionalized castor oil-based monomer was obtained by vacuum distillation. In step S2, 10g of aluminum isopropoxide was added to 55g of isopropanol, mixed thoroughly, and then 5g of acetylacetone was added dropwise. After the addition was complete, the mixture was refluxed and stirred at 65°C for 1.5h to obtain an aluminum chelate solution. 20g of tetraethyl orthosilicate and 2g of KH-570 were added to 36g of isopropanol, mixed thoroughly, and then an acidic aqueous solution (0.2g concentrated nitric acid + 4g deionized water + 3.5g isopropanol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 3h to obtain an acidic silica sol. 12g of functionalized castor oil monomer and 25g of isopropanol were mixed thoroughly, and then... Add 3g of emulsifier OP-10 and 15g of 2wt% dilute nitric acid, raise the temperature to 40℃, and use a high-shear emulsifier at 8000rpm for 10min to obtain an O / W microemulsion; mix 3g of aluminum chelate solution with 3.5g of acidic silica sol evenly, raise the temperature to 45℃, and add it dropwise to 12g of O / W microemulsion under the condition of keeping warm and stirring. After the addition is completed, raise the temperature to 60℃ and stir for 20min. After the reaction is completed, centrifuge, ultrasonically clean and dry to obtain castor oil / silica-alumina hybrid particles; In step S3, 3g of castor oil / silica-alumina hybrid particles are added to 100g of deionized water and dispersed evenly. Then, 14g of acrylamide, 8g of methacryloyloxyethyltrimethylammonium chloride, 5g of N-isopropylacrylamide, and 0.2g of N,N / Methylenebisacrylamide was stirred until completely dissolved and nitrogen gas was introduced to remove oxygen for 40 min. The mixture was heated to 70°C in a water bath and ammonium persulfate aqueous solution (0.2 g of ammonium persulfate dissolved in 3 mL of deionized water) was quickly added. The mixture was stirred and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a hybrid particle dispersion. In step S4, 100g of deionized water was added to the reactor, and a high-speed shear dispersion emulsifier (8000rpm) was turned on. 1.2g of sodium alginate powder was slowly added to the reactor. After the addition was completed, high-speed shearing was continued for 20min. Then, 0.3g of potassium citrate was added and stirred until dissolved. The pH of the system was measured to be 6.5-7.5 using a pH meter. 25g of hybrid particle dispersion was added to the reactor while stirring at 400rpm. After the addition was completed, stirring was continued for 20min. 5g of decyl glucoside was added and stirred for 10min. Then, high-speed shearing was performed at 3500rpm for 4min to obtain the composite emulsifier.

[0037] Example 4 This embodiment differs from Embodiment 1 in the following ways: In step S3, the quaternary ammonium salt cationic monomer is dimethyl diallyl ammonium chloride; the thermosensitive monomer is N,N-diethylacrylamide; in step S4, the alkyl glycoside is obtained by mixing decyl glucoside and lauryl glucoside in a mass ratio of 1:1.

[0038] Comparative Example 1 Compared with Example 1, in this comparative example, step S2 is omitted in the preparation process, and the functionalized castor oil-based monomer prepared in step S1 is directly used in the preparation of step S3. That is, in the preparation process of step S3, the castor oil / silicon-aluminum hybrid particles are replaced with functionalized castor oil-based monomers, and the rest is the same as in Example 1.

[0039] Comparative Example 2 Compared with Example 1, in this comparative example, step S1 is omitted in the preparation process. In step S2, the functionalized castor oil monomer is replaced with castor oil polyoxyethylene ether, and the rest is the same as in Example 1.

[0040] Comparative Example 3 Compared with Example 1, this comparative example does not add a temperature-sensitive monomer in the preparation process of step S3, while the rest is the same as in Example 1.

[0041] Comparative Example 4 Compared with Example 1, this comparative example does not add quaternary ammonium salt cationic monomers in the preparation process of step S3, while the rest is the same as in Example 1.

[0042] Comparative Example 5 Compared with Example 1, this comparative example does not add sodium alginate powder in step S4, but the rest is the same as in Example 1.

[0043] Related tests: The products prepared in each embodiment and comparative example were subjected to relevant performance tests: Centrifugation stability test: Take 10 mL of the prepared composite emulsifier sample and place it in a centrifuge tube. Centrifuge continuously at 5000 rpm for 30 min using a high-speed centrifuge. Observe whether layering, precipitation or oil separation occurs in the tube after centrifugation.

[0044] Room temperature stability: The prepared composite emulsifier was allowed to stand at 45℃ for 96 hours, and the stratification rate was measured (stratification rate = volume of lower sediment / total volume of emulsion × 100%).

[0045] Heat resistance test: Accurately weigh 2.0g of sample and place it in a clean petri dish. Heat in a constant temperature oven at 220℃ for 2 hours. After cooling, weigh the sample and calculate the percentage of mass loss.

[0046] Thermosensitive response test: The hybrid particle dispersion was prepared into a 1wt% aqueous solution, and the transmittance (500nm) at different temperatures (20℃-50℃) was measured using a UV-Vis spectrophotometer; the temperature at which the transmittance drops to 50% of the initial value was defined as the lower eutectic critical temperature (LCST). If the transmittance does not change significantly with increasing temperature, it is considered to have no thermosensitive characteristics.

[0047] Foam characteristics: The foam height of a 0.5% composite emulsifier aqueous solution was measured using a Roche foam analyzer after stirring for 5 minutes to characterize the amount of foam.

[0048] The test data is shown in Table 1.

[0049] Table 1 Relevant performance test results The test results above show that the overall performance of each embodiment is better than that of the comparative examples. They have good centrifugal stability and room temperature stability, excellent heat resistance and low foaming performance. In addition, each embodiment shows obvious temperature-sensitive characteristics (33-35℃), which helps the oil spread and adhere to the fiber surface.

[0050] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0051] Although embodiments of this application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of this application, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A process for the preparation of a complex emulsifier for spin finishes, characterized in that, Includes the following steps: S100, using a castor oil polyoxyethylene ether, Caprolactone, glycidyl methacrylate raw materials, functional castor oil-based monomer is prepared; S200: An aluminum chelate solution is prepared using raw materials including aluminum isopropoxide and acetylacetone; an acidic silica sol is obtained by acidic hydrolysis using raw materials including tetraethyl orthosilicate and silane coupling agent; an O / W microemulsion is obtained by high-speed shear emulsification using raw materials including functionalized castor oil monomers and emulsifiers; the aluminum chelate solution and acidic silica sol are mixed and added to the O / W microemulsion to react and obtain castor oil / silica-aluminum hybrid particles; S300 uses raw materials including castor oil / silica-alumina hybrid particles, acrylamide monomers, quaternary ammonium salt cationic monomers, and temperature-sensitive monomers to obtain a hybrid particle dispersion through polymerization reaction; S400: The composite emulsifier is obtained by high-speed shearing using raw materials including sodium alginate, potassium citrate, hybrid particulate dispersion, and alkyl glycoside.

2. The method for preparing a composite emulsifier for spinning oil according to claim 1, characterized in that, Step S100 is specifically: under inert atmosphere, castor oil polyoxyethylene ether is added into the reactor, the temperature is raised to 110-120℃, under stirring state, the following are added Caprolactone and stannous octoate, after reaction for 2-3h, the temperature is lowered to 90-100℃, tetrabutylammonium salt is added into it, then glycidyl methacrylate is added dropwise, and it is incubated at 90-100℃ for 4-5h, after the reaction is completed, functionalized castor oil-based monomer is obtained by vacuum distillation.

3. A process for the preparation of a complex emulsifier for spin finish according to claim 1, characterized in that, The preparation method of castor oil polyoxyethylene ether is as follows: castor oil and bimetallic cyanide catalyst are added to a closed reactor. Under an inert atmosphere, the mixture is stirred and heated to 120-130°C. After vacuum dehydration and degassing, the vacuum is closed, and the temperature is maintained at 135-140°C. Ethylene oxide is added to the mixture, and the feeding time is controlled at 5-6 hours. After the feeding is completed, the mixture is kept warm and stirred for 1-2 hours, and then the temperature is lowered to 80°C. Phosphoric acid is added, and the mixture is stirred for 30-40 minutes. The mixture is then filtered while hot to obtain a light yellow viscous liquid, which is castor oil polyoxyethylene ether.

4. The method for preparing a composite emulsifier for spinning oil according to claim 1, characterized in that, Step S200 specifically includes the following steps: S210. Add aluminum isopropoxide to isopropanol, mix well, and then add acetylacetone dropwise. After the addition is complete, reflux and stir at 65-75℃ for 1.5-2.5h to obtain an aluminum chelate solution. S220. Add tetraethyl orthosilicate and silane coupling agent to isopropanol, mix well, and then add acidic aqueous solution dropwise. After the addition is complete, stir at room temperature for 3-4 hours to obtain acidic silica sol. S230. After mixing functionalized castor oil monomer and isopropanol evenly, add emulsifier and dilute nitric acid, raise the temperature to 40-50℃, and continuously process with a high-shear emulsifier for 10-15 minutes to obtain O / W type microemulsion. S240. After mixing the aluminum chelate solution with the acidic silica sol evenly, raise the temperature to 45-55℃ and add it dropwise to the O / W type microemulsion while keeping it warm and stirring. After the addition is complete, raise the temperature to 60-65℃ and stir for 20-30 minutes. After the reaction is complete, centrifuge and discard the supernatant. The precipitate is ultrasonically cleaned with a mixture of ethanol / acetone and repeated 2-3 times. After drying, castor oil / silica-alumina hybrid particles are obtained.

5. The method for preparing a composite emulsifier for spinning oil according to claim 1, characterized in that, Step S300 is as follows: Castor oil / silica-alumina hybrid particles are added to deionized water and dispersed evenly. Acrylamide monomers, quaternary ammonium salt cationic monomers, thermosensitive monomers and crosslinking agents are added to the mixture. The mixture is stirred until completely dissolved and nitrogen gas is introduced to remove oxygen for 30-40 minutes. The water bath temperature is raised to 60-70°C, and the initiator is added quickly. The mixture is stirred and reacted for 5-6 hours. After the reaction is completed, the mixture is cooled to room temperature to obtain a hybrid particle dispersion.

6. A process for the preparation of a complex emulsifier for spin finish according to claim 5, characterized in that, The quaternary ammonium salt cationic monomer is one or more of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, dimethyl diallyl ammonium chloride, and methacrylamidopropyltrimethylammonium chloride.

7. A process for the preparation of a complex emulsifier for spin finish according to claim 5, characterized in that, The temperature-sensitive monomer is one or more of N-isopropylacrylamide, N-n-propylacrylamide, and N,N-diethylacrylamide.

8. A process for the preparation of a complex emulsifier for spin finish according to claim 1, characterized in that, Step S400 is as follows: Deionized water is added to the reactor, a high-speed shear dispersion emulsifier is turned on, and sodium alginate powder is added. After the addition is completed, high-speed shearing is continued for 20-30 minutes. Potassium citrate is then added and stirred until dissolved. The pH of the system is measured to be 6.5-7.5 using a pH meter. Hybrid particle dispersion is added while stirring. After the addition is completed, stirring is continued for 20-30 minutes. Alkyl glycoside is added and stirred for 10-20 minutes. Then, after high-speed shearing for 4-6 minutes, the composite emulsifier is obtained.

9. A complex emulsifier for spin finish, characterized by, It is prepared by the preparation method described in any one of claims 1-8.

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