High-temperature stable polyether smoothing agent for spinning and preparation method thereof

Abstract

The application belongs to the technical field of smooth agent preparation, and particularly relates to a high-temperature stable polyether smooth agent for spinning and a preparation method thereof. The raw materials including bisphenol A, an alkali catalyst, 1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropene are used to prepare a crude polyether; the raw materials including the crude polyether, deionized water, an acidic substance, an adsorbent, alkyl isocyanate and an organic tin catalyst are used to prepare a modified polyether; the raw materials including the modified polyether, a nano silicon-based hybrid additive and a hindered phenol antioxidant are used to obtain the polyether smooth agent through shearing emulsification; by introducing 1,2-epoxy-3,3,3-trifluoropropene into a polyether main chain, the chemical stability of the polyether main chain can be greatly enhanced by using the extremely high bond energy of C-F bond and the strong electronegativity and shielding effect of fluorine atoms. By using long-chain alkyl isocyanate to modify the terminal of the polyether into a urethane, the coking and yellowing phenomena under high temperature are effectively inhibited.

Description

Technical Field

[0001] This invention belongs to the field of smoothing agent preparation technology, specifically relating to a high-temperature stable polyether smoothing agent for spinning and its preparation method. Background Technology

[0002] With the rapid development of the chemical fiber industry towards high speed and high precision, the requirements for the performance of oiling agents in chemical fiber spinning processes are becoming increasingly stringent. The hot roller temperatures in modern high-speed spinning processes often reach as high as 200℃. Polyether molecules contain a large number of ether bonds, making them highly susceptible to thermal oxidative degradation under high temperature and oxygen conditions. This degradation reaction not only causes drastic fluctuations in the viscosity of the oiling agent, resulting in the loss of its original smoothing properties, but also produces small-molecule volatiles, leading to severe "smoke" at the production site. Furthermore, during high-temperature degradation, polyether generates peroxides and acidic substances, further inducing polymerization or cross-linking reactions, forming tar-like coking deposits on the surface of the hot rollers. These coking deposits are not only difficult to clean, but also damage the fiber filaments, causing breakage or fuzzing, severely affecting the physical and mechanical properties of the fibers. In addition, degradation products are often accompanied by a darkening of color, causing yellowing of the fiber filaments and reducing the sensory indicators and dyeing uniformity of the finished fibers.

[0003] Chinese Patent No. CN118345636B discloses a low-foaming yarn smoother and its preparation method. The smoother is prepared by mixing and emulsifying raw materials including block polyether siloxane, a deproteinized modified linseed gum composition, and deionized water. The block polyether siloxane can adsorb and penetrate into the yarn fibers, making the yarn surface smooth and soft, and improving weavability. The combined action of the deproteinized modified linseed gum composition and the block polyether siloxane adsorbs onto the yarn fiber surface to form an adsorption film, creating a three-dimensional network-like lubricating structure on the yarn surface, resulting in better smoothing performance and stability. Chinese Patent No. CN112127149B discloses a hydrophilic smoothing agent for packaged yarn with small layer difference and its preparation method. It is prepared by mixing and emulsifying raw materials such as Fischer-Tropsch oxidized wax, low melting point wax, synthetic wax, softener, emulsifier, sodium hydroxide or potassium hydroxide, cationic regulator and water. When used for smoothing packaged yarn, it can effectively reduce the dynamic friction coefficient of the yarn, improve its sewing performance, and provide packaged yarn with a good smooth hand feel, excellent hydrophilicity and very small layer difference. The preparation method is simple and easy to industrialize.

[0004] While existing technologies typically add antioxidants to polyethers to improve thermal stability, these antioxidants are prone to thermal decomposition and volatilization along with the oil under high-temperature conditions, leading to a rapid loss of protective efficacy. Therefore, developing a polyether lubricant with extremely high thermal stability, low volatility, and excellent lubrication properties has become a key technical challenge that urgently needs to be addressed in the preparation of high-performance fibers and the improvement of high-speed spinning production efficiency. Summary of the Invention

[0005] To address at least one of the above problems, the present invention provides a method for preparing a high-temperature stable polyether smoothing agent for spinning, comprising the following steps: S100: Crude polyether is prepared using raw materials including bisphenol A, an alkaline catalyst, 1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane. S200: Modified polyether is prepared using raw materials including crude polyether, deionized water, acidic substances, adsorbent, alkyl isocyanate, and organotin catalyst. S300, using raw materials including benzotriazole, ethyl acetate, nonionic surfactant, tetraethyl orthosilicate, and silane coupling agent, prepares nano-silicon-based hybrid additives; The polyether smoothing agent is obtained by shearing and emulsifying raw materials including S400, modified polyether, nano-silicon-based hybrid additives, and hindered phenolic antioxidants.

[0006] Further, step S100 specifically involves: adding bisphenol A and an alkaline catalyst sequentially to the reactor, heating to 105-115℃, circulating and dehydrating under vacuum for 1-2 hours, purging with nitrogen 3-5 times, maintaining the temperature at 110±5℃, controlling the pressure at 0.2-0.3MPa, slowly adding a mixed monomer containing 1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane, and maintaining the temperature for 2-3 hours after the addition is complete to obtain crude polyether.

[0007] Furthermore, the mixed monomers are composed of 1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane in a mass ratio of 12-18:70-82:8-12.

[0008] Further, step S200 specifically involves: adding deionized water to the crude polyether to hydrolyze the alkaline catalyst, then adding an acidic substance for neutralization, then adding an adsorbent and stirring thoroughly for 1-2 hours, followed by heating to 100-110℃ for vacuum dehydration, followed by fine filtration and cooling to 80-90℃, then adding alkyl isocyanate and organotin catalyst in sequence, and reacting for 4-5 hours to obtain the modified polyether.

[0009] Further, the acidic substance is phosphoric acid or glacial acetic acid; the adsorbent is synthetic magnesium silicate; and the organotin is one or more of di-n-butyltin dilaurate, stannous octoate, di-n-octyltin dilaurate, and dimethyltin dithioacetate.

[0010] Further, step S300 includes the following steps: S310. Add benzotriazole to ethyl acetate and stir in a constant temperature water bath at 40-45℃ until completely dissolved to obtain a mixture. Slowly pour the mixture into deionized water containing nonionic surfactants, pre-emulsify it for 5-8 minutes using a high-speed shear machine, and then ultrasonically disperse it for 15-20 minutes under ice-water bath conditions to obtain a nanoemulsion. S320. Add tetraethyl orthosilicate to the nanoemulsion, adjust the pH of the system to 9.5-10.5, and stir continuously at 35-40℃ for 24-28h. After the reaction is completed, remove the solvent by vacuum distillation at 50-55℃, then lower the temperature to 35-40℃, add silane coupling agent and stir for 4-5h to obtain nano-silicon-based hybrid additive.

[0011] Furthermore, the nonionic surfactant is one or more of Tween-80, AEO-9, polyether F-127, and PVA-1788.

[0012] Furthermore, the silane coupling agent is one or more of KH-550, KH-560, and KH570.

[0013] Further, step S400 specifically involves mixing the modified polyether, the nano-silicon-based hybrid additive, and the hindered phenolic antioxidant, and then shearing and emulsifying them at 60-65°C to obtain the polyether smoothing agent.

[0014] A high-temperature stable polyether smoothing agent for spinning is prepared by the preparation method of a high-temperature stable polyether smoothing agent for spinning as described in any of the above technical solutions.

[0015] The present invention has the following beneficial effects: This invention significantly enhances the chemical stability of the polyether backbone by introducing 1,2-epoxy-3,3,3-trifluoropropane into the polyether backbone, utilizing the extremely high bond energy of the CF bond and the strong electronegativity and shielding effect of fluorine atoms. In existing technologies, the hydroxyl groups at the ends of polyethers are prone to degradation and the generation of acidic byproducts at high temperatures. This invention modifies the polyether ends with urethane esterification using long-chain alkyl isocyanates, converting the reactive hydroxyl groups into chemically stable urethane groups, thus interrupting the induction pathway of thermal degradation and effectively inhibiting coking and yellowing at high temperatures. Furthermore, this invention introduces a nano-silica-based hybrid additive, physically encapsulating benzotriazole antioxidants through a silica shell, forming a microcapsule structure at the microscopic level. This structure effectively prevents the rapid sublimation and oxidative deactivation of small-molecule antioxidants at high temperatures, enabling the smoothing agent to maintain its antioxidant properties for extended periods at high temperatures. Detailed Implementation

[0016] 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.

[0017] Polyether smoothing agents are the core component of chemical fiber spinning oils, imparting good bundled properties, smoothness, and antistatic properties to the fibers, ensuring smooth spinning. With continuously increasing spinning speeds, the friction between the fiber bundle and the guide generates a large amount of heat, resulting in a high working environment for the oil. Traditional polyether smoothing agents are prone to oxidation and chain scission at high temperatures, leading to a significant decrease in oil viscosity and lubrication failure. Therefore, this invention provides a method for preparing a high-temperature stable polyether smoothing agent for spinning, comprising the following steps: S100: Crude polyether is prepared using raw materials including bisphenol A, an alkaline catalyst, 1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane. S200: Modified polyether is prepared using raw materials including crude polyether, deionized water, acidic substances, adsorbent, alkyl isocyanate, and organotin catalyst. S300, using raw materials including benzotriazole, ethyl acetate, nonionic surfactant, tetraethyl orthosilicate, and silane coupling agent, prepares nano-silicon-based hybrid additives; The polyether smoothing agent is obtained by shearing and emulsifying raw materials including S400, modified polyether, nano-silicon-based hybrid additives, and hindered phenolic antioxidants.

[0018] Specifically, step S100 involves: adding bisphenol A and an alkaline catalyst sequentially to the reactor, heating to 105-115℃, and circulating dehydration under vacuum (pressure ≤ -0.098MPa) for 1-2 hours. After dehydration, the vacuum system is shut off, and nitrogen is introduced into the reactor for replacement 3-5 times. After replacement, the temperature is maintained at 110±5℃ and the pressure is controlled at 0.2-0.3MPa. A mixed monomer containing 1,2-epoxybutane, propylene oxide, and 1,2-epoxy-3,3,3-trifluoropropane is slowly added dropwise. After the addition is completed, the temperature is maintained at 110±5℃ and the pressure at 0.2-0.3MPa, and the mixture is kept warm and matured for 2-3 hours. The mixture is then cooled and discharged to obtain crude polyether.

[0019] In this step, the alkaline catalyst is sodium hydroxide, potassium hydroxide, or sodium methoxide; the mass ratio of bisphenol A, alkaline catalyst, and mixed monomers is 100:0.8-1.5:800-1000; the mixed monomers are composed of 1,2-epoxybutane, propylene oxide, and 1,2-epoxy-3,3,3-trifluoropropane in a mass ratio of 12-18:70-82:8-12, preferably 1,2-epoxybutane, propylene oxide, and 1,2-epoxy-3,3,3-trifluoropropane in a mass ratio of 15:75:10.

[0020] In this process, bisphenol A undergoes a ring-opening copolymerization reaction with 1,2-epoxybutane, propylene oxide, and 1,2-epoxy-3,3,3-trifluoropropane under the action of an alkaline catalyst. Bisphenol A, as an initiator, has a strong structural rigidity, which can increase the glass transition temperature of the polyether; the addition of the alkaline catalyst ensures initiation efficiency; the addition of 1,2-epoxybutane provides hydrophilicity and emulsification; propylene oxide, as the main component in the mixed monomers, provides good solubility and smoothness; the addition of 1,2-epoxy-3,3,3-trifluoropropane, due to the extremely strong electronegativity and hydrophobicity of fluorine atoms, can form a hydrophobic protective film on the surface of the polyether molecular chain, which not only improves the high-temperature resistance of the polyether but also enhances its lubrication effect, reducing friction between fibers and equipment.

[0021] Specifically, step S200 involves adding deionized water to the crude polyether to hydrolyze the alkaline catalyst, then adding an acidic substance for neutralization until the pH of the system is 6.5-7.5. Next, an adsorbent is added and stirred thoroughly for 1-2 hours. The mixture is then heated to 100-110°C and vacuum dehydrated for 1-2 hours. After fine filtration through a precision filter (0.22 μm filtration accuracy), the temperature is lowered to 80-90°C. Alkyl isocyanate and organotin catalyst are added sequentially, and the reaction is carried out for 4-5 hours. The NCO value in the system is monitored and reduced to below 0.1%, yielding the modified polyether.

[0022] In this step, the acidic substance is phosphoric acid or glacial acetic acid, preferably phosphoric acid; the adsorbent is synthetic magnesium silicate with a particle size of 100-200 mesh; and the alkyl isocyanate is C 12 -C 22 The linear alkyl isocyanate is preferred; preferably one or more of hexadecyl isocyanate, octadecyl isocyanate, and docosyl isocyanate, more preferably octadecyl isocyanate. The organotin is one or more of di-n-butyltin dilaurate, stannous octanoate, di-n-octyltin dilaurate, and dimethyltin dithioacetate isooctyl ester. The mass ratio of crude polyether, deionized water, adsorbent, alkyl isocyanate, and organotin catalyst is 100:6-10:2-5:6-10:0.05-0.08.

[0023] In this process, the crude polyether has active hydroxyl groups at its end, which react with the isocyanate groups of alkyl isocyanates under the catalysis of an organotin catalyst to form urethane bonds. The introduction of long-chain alkyl groups can enhance the hydrophobicity of the polyether and its compatibility with fibers, while the formation of urethane bonds can improve the rigidity and high-temperature stability of the polyether molecular chain.

[0024] Step S300 includes the following steps: S310. Add benzotriazole to ethyl acetate and stir in a constant temperature water bath at 40-45℃ until completely dissolved to obtain a mixture. Slowly pour the mixture into deionized water containing a nonionic surfactant and pre-emulsify it for 5-8 minutes with a high-speed shear machine at a shear rate of 8000-10000 r / min. Then, ultrasonically disperse it for 15-20 minutes under ice-water bath conditions to obtain a nanoemulsion. S320. Add tetraethyl orthosilicate to the nanoemulsion, adjust the pH of the system to 9.5-10.5 with 25% ammonia, stir continuously at 35-40℃ for 24-28h, after the reaction is complete, raise the temperature to 50-55℃, remove the solvent by vacuum distillation under vacuum of -0.07 to -0.08MPa, then lower the temperature to 35-40℃, add silane coupling agent, and stir at 200-400r / min for 4-5h to obtain nano-silicon-based hybrid additive.

[0025] In this step, the nonionic surfactant is one or more of Tween-80, AEO-9, polyether F-127, and PVA-1788; the silane coupling agent is one or more of KH-550, KH-560, and KH570. The mass ratio of benzotriazole, ethyl acetate, nonionic surfactant, and deionized water is 4-7:15-25:1-3:35-50; the mass ratio of nanoemulsion, tetraethyl orthosilicate, and silane coupling agent is 50-60:8-15:1-2.

[0026] In step S310, benzotriazole, a hydrophobic substance, is difficult to disperse directly in water. Nonionic surfactants, possessing both hydrophilic and lipophilic groups, can form micelles in water. Benzotriazole, as the lipophilic component, is encapsulated within the micelles. Through high-speed shearing and ultrasonic dispersion, the micelles are broken down into nano-sized droplets, forming a stable nanoemulsion. This effectively solves the problems of poor water solubility and incompatibility with subsequent raw materials associated with benzotriazole. In step S320, tetraethyl orthosilicate undergoes hydrolysis under alkaline conditions, condensing to form a nano-silica network structure. Benzotriazole nanodroplets are encapsulated within this network structure, forming a nano-silicon-based hybrid system. The addition of a silane coupling agent effectively improves the compatibility between inorganic SiO2 and the organic polyether matrix, preventing nanoparticle aggregation.

[0027] Specifically, step S400 involves mixing modified polyether, nano-silicon-based hybrid additive, and hindered phenolic antioxidant, and then shearing and emulsifying them at 60-65°C to obtain the polyether smoothing agent.

[0028] In this step, the hindered phenolic antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1135, and antioxidant 1330. The mass ratio of modified polyether, nano-silicon-based hybrid additive, and hindered phenolic antioxidant is 85-92:6-10:1.2-1.8.

[0029] In this process, modified polyether, nano-hybrid additives, and hindered phenolic antioxidants are mixed under heating and high-speed shearing. The modified polyether provides basic heat resistance and lubricity, the nano-additives provide sustained-release protection at high temperatures, and the hindered phenolic antioxidants further inhibit the oxidative decomposition of the product at high temperatures, synergistically enhancing the high-temperature stability of the product with the antioxidant effect of benzotriazole in step S300. The shear emulsification process ensures that the nano-silicon-based hybrid additives are uniformly dispersed in the modified polyether, preventing agglomeration and ensuring they fully exert their high-temperature resistance and wear resistance properties. Simultaneously, it gives the product good emulsification stability, facilitating uniform adhesion to the fiber surface during spinning.

[0030] Example 1 S1. Add 100 parts by weight of bisphenol A and 1.2 parts by weight of alkaline catalyst KOH sequentially to the reactor, heat to 110℃, evacuate to -0.098MPa, and circulate for dehydration for 1.5h. After dehydration, turn off the vacuum system and purge the reactor with nitrogen gas for replacement. Replace the gas 5 times. After replacement, maintain the temperature at 110℃ and the pressure at 0.25MPa, and slowly add 700 parts by weight of mixed monomers (1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane mixed in a mass ratio of 15:75:10). After the addition is complete, maintain the temperature at 110℃ and the pressure at 0.25MPa, and keep it warm for 2.5h. Cool down to 65℃ and discharge to obtain crude polyether. S2. Add 8 parts by weight of deionized water to 100 parts by weight of crude polyether to hydrolyze the alkaline catalyst. Then slowly add 85% phosphoric acid to neutralize the system until the pH reaches 7.0. Then add 3.5 parts by weight of synthetic magnesium silicate and stir thoroughly for 1.5 hours. Then raise the temperature to 105°C and dehydrate under vacuum for 1.5 hours. After fine filtration through a precision filter (filtration accuracy of 0.22 μm), cool down to 85°C and add 8.5 parts by weight of octadecyl isocyanate and 0.065 parts by weight of stannous octoate in sequence. React for 4.5 hours. Monitor the NCO value in the system to decrease to below 0.1% to obtain the modified polyether. S3. Add 6 parts by weight of benzotriazole to 22 parts by weight of ethyl acetate, stir in a constant temperature water bath at 45°C until completely dissolved to obtain a mixture, slowly pour it into deionized water containing Tween-80 (2.5 parts by weight of Tween-80 and 45 parts by weight of deionized water), pre-emulsify with a high-speed shear machine at a shear rate of 10000 r / min for 6.5 min, and then ultrasonically disperse in an ice-water bath for 20 min to obtain a nanoemulsion; S4. Add 12 parts by weight of tetraethyl orthosilicate to 65 parts by weight of nanoemulsion, adjust the pH of the system to 10 with 25% ammonia water, stir continuously at 40°C for 26 h, after the reaction is completed, raise the temperature to 55°C, remove the solvent by vacuum distillation under vacuum of -0.08 MPa, then lower the temperature to 40°C, add 1.6 parts by weight of KH-550, stir at 300 r / min for 5 h to obtain nano-silicon-based hybrid additive; S5. Mix 90 parts by weight of modified polyether, 8 parts by weight of nano-silicon-based hybrid additive, and 1.6 parts by weight of antioxidant 1010, and then shear emulsify at 4000 r / min for 30 min at 65°C to obtain polyether smoothing agent.

[0031] Example 2 This embodiment differs from Embodiment 1 in the following ways: In step S1, 100 parts by weight of bisphenol A and 0.8 parts by weight of alkaline catalyst KOH are added sequentially to the reactor, the temperature is raised to 105°C, the vacuum is drawn to -0.098 MPa, the reactor is circulated for dehydration for 1 hour, and after nitrogen purging, the temperature is maintained at 105°C and the pressure is controlled at 0.2 MPa. 600 parts by weight of mixed monomers (1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane mixed in a mass ratio of 12:70:8) are slowly added dropwise. After the addition is completed, the temperature is maintained at 105°C and the pressure at 0.2 MPa, and the reactor is kept warm and matured for 2 hours. The reactor is then cooled and discharged to obtain crude polyether.

[0032] In step S2, 6 parts by weight of deionized water were added to 100 parts by weight of crude polyether, and 85% phosphoric acid was added until the pH of the system was 7.0. Then, 2 parts by weight of synthetic magnesium silicate were added and stirred thoroughly for 1 hour. Subsequently, the temperature was raised to 100°C and vacuum dehydrated for 1 hour. After fine filtration, the temperature was lowered to 80°C, and 6 parts by weight of octadecyl isocyanate and 0.05 parts by weight of stannous octoate were added sequentially. The reaction was carried out for 4 hours, and the NCO value in the system was monitored to decrease to below 0.1%, thus obtaining the modified polyether.

[0033] In step S3, 4 parts by weight of benzotriazole are added to 15 parts by weight of ethyl acetate and stirred in a constant temperature water bath at 40°C until completely dissolved to obtain a mixture. This mixture is then slowly poured into deionized water containing Tween-80 (1 part by weight of Tween-80 and 35 parts by weight of deionized water are mixed). After pre-emulsification for 5 minutes at a high-speed shear rate of 8000 r / min, the mixture is ultrasonically dispersed for 15 minutes under ice-water bath conditions to obtain a nanoemulsion.

[0034] In step S4, 8 parts by weight of tetraethyl orthosilicate were added to 50 parts by weight of nanoemulsion, and the pH of the system was adjusted to 10 with 25% ammonia. The mixture was stirred continuously at 35°C for 24 hours. After the reaction was completed, the temperature was raised to 50°C, and the solvent was removed by vacuum distillation at a vacuum degree of -0.07 MPa. Then the temperature was lowered to 35°C, 1 part by weight of KH-550 was added, and the mixture was stirred at low speed for 4 hours to obtain the nano-silicon-based hybrid additive.

[0035] In step S5, 85 parts by weight of modified polyether, 6 parts by weight of nano-silicon-based hybrid additive, and 1.2 parts by weight of antioxidant 1010 are mixed and then sheared and emulsified at 65°C to obtain polyether smoothing agent.

[0036] Example 3 This embodiment differs from Embodiment 1 in the following ways: In step S1, 100 parts by weight of bisphenol A and 1.5 parts by weight of alkaline catalyst KOH are added sequentially to the reactor, the temperature is raised to 115°C, the vacuum is drawn to -0.098 MPa, the reactor is circulated for dehydration for 2 hours, and after nitrogen purging, the temperature is maintained at 115°C and the pressure is controlled at 0.3 MPa. 800 parts by weight of mixed monomers (1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane mixed in a mass ratio of 18:82:12) are slowly added dropwise. After the addition is completed, the temperature is maintained at 115°C and the pressure at 0.3 MPa, and the reactor is kept warm and matured for 3 hours. The reactor is then cooled and discharged to obtain crude polyether.

[0037] In step S2, 10 parts by weight of deionized water were added to 100 parts by weight of crude polyether, and 85% phosphoric acid was added until the pH of the system was 7.0. Then, 5 parts by weight of synthetic magnesium silicate were added and stirred thoroughly for 2 hours. Subsequently, the temperature was raised to 110°C and vacuum dehydrated for 2 hours. After fine filtration, the temperature was lowered to 90°C, and 10 parts by weight of octadecyl isocyanate and 0.08 parts by weight of stannous octoate were added sequentially. The reaction was carried out for 5 hours, and the NCO value in the system was monitored to decrease to below 0.1%, thus obtaining the modified polyether.

[0038] In step S3, 7 parts by weight of benzotriazole are added to 25 parts by weight of ethyl acetate and stirred in a constant temperature water bath at 45°C until completely dissolved to obtain a mixture. This mixture is then slowly poured into deionized water containing Tween-80 (3 parts by weight of Tween-80 and 50 parts by weight of deionized water). After pre-emulsification for 8 minutes using a high-speed shear machine at a shear rate of 10000 r / min, the mixture is ultrasonically dispersed for 20 minutes under ice-water bath conditions to obtain a nanoemulsion.

[0039] In step S4, 15 parts by weight of tetraethyl orthosilicate were added to 60 parts by weight of nanoemulsion, and the pH of the system was adjusted to 10 with 25% ammonia. The mixture was stirred continuously at 40°C for 28 hours. After the reaction was completed, the temperature was raised to 55°C, and the solvent was removed by vacuum distillation at a vacuum degree of -0.08 MPa. Then the temperature was lowered to 40°C, 2 parts by weight of KH-550 were added, and the mixture was stirred at low speed for 5 hours to obtain the nano-silicon-based hybrid additive.

[0040] In step S5, 92 parts by weight of modified polyether, 10 parts by weight of nano-silicon-based hybrid additive, and 1.8 parts by weight of antioxidant 1010 are mixed and then sheared and emulsified at 65°C to obtain a polyether smoothing agent.

[0041] Example 4 This embodiment differs from Embodiment 1 in the following ways: In step S1, 100 parts by weight of bisphenol A and 1 part by weight of alkaline catalyst KOH are added sequentially to the reactor. After vacuum circulation dehydration and nitrogen purging, 650 parts by weight of mixed monomers (1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane mixed in a mass ratio of 13:72:9) are slowly added dropwise. After the addition is completed, the mixture is cooled and discharged to obtain crude polyether.

[0042] In step S2, 7 parts by weight of deionized water are added to 100 parts by weight of crude polyether to adjust the pH of the system to 7.0. Then, 2.5 parts by weight of synthetic magnesium silicate are added. After fine filtration and cooling, 7 parts by weight of octadecyl isocyanate and 0.06 parts by weight of stannous octoate are added in sequence to obtain modified polyether.

[0043] In step S3, 5.5 parts by weight of benzotriazole are added to 18 parts by weight of ethyl acetate and stirred until completely dissolved to obtain a mixture. The mixture is then slowly poured into deionized water containing Tween-80 (1.2 parts by weight of Tween-80 and 40 parts by weight of deionized water are mixed). After pre-emulsification by a high-speed shear machine, the mixture is ultrasonically dispersed under ice-water bath conditions to obtain a nanoemulsion.

[0044] In step S4, 9 parts by weight of tetraethyl orthosilicate are added to 52 parts by weight of nanoemulsion, and the pH of the system is adjusted to 10 with 25% ammonia. After the reaction is completed, the solvent is removed by vacuum distillation, and then the temperature is lowered and 1.2 parts by weight of KH-550 is added to obtain nano-silicon-based hybrid additive.

[0045] In step S5, 88 parts by weight of modified polyether, 7 parts by weight of nano-silicon-based hybrid additive, and 1.4 parts by weight of antioxidant 1010 are mixed and then sheared and emulsified to obtain a polyether smoothing agent.

[0046] Comparative Example 1 Compared with Example 1, in this comparative example, 1,2-epoxy-3,3,3-trifluoropropane was not added during the preparation process in step S1, the mass ratio of 1,2-epoxybutane to propylene oxide was 15:85, and the rest was the same as in Example 1.

[0047] Comparative Example 2 This comparative example differs from Example 1 in the following ways: In step S2, 8 parts by weight of deionized water are added to 100 parts by weight of crude polyether to hydrolyze the alkaline catalyst. Then, 85% phosphoric acid is slowly added for neutralization until the pH of the system is 7.0. Then, 3.5 parts by weight of synthetic magnesium silicate are added and stirred thoroughly for 1.5 hours. The temperature is then raised to 105°C and vacuum dehydrated for 1.5 hours. After fine filtration through a precision filter (filtration accuracy of 0.22 μm), the temperature is lowered to obtain the modified polyether.

[0048] The rest are the same as in Example 1.

[0049] Comparative Example 3 Compared with Example 1, this comparative example omits steps S3 and S4. In step S5, the nano-silicon-based hybrid additive is replaced with an equal amount of benzotriazole. All other steps are the same as in Example 1.

[0050] Comparative Example 4 Compared with Example 1, this comparative example does not add nano-silicon-based hybrid additives during the preparation process in step S5, while all other steps are the same as in Example 1.

[0051] Comparative Example 5 Compared with Example 1, in this comparative example, the modified polyether was replaced with a commercially available polyether in step S5, while the rest was the same as in Example 1.

[0052] Comparative Example 6 Compared with Example 1, this comparative example does not add hindered phenolic antioxidants during the preparation process in step S5, while all other steps are the same as in Example 1.

[0053] Related tests Stability testing: A thermogravimetric analyzer (model TGA-Q500) was used. Approximately 10 mg of sample was weighed and placed in an alumina crucible under a nitrogen atmosphere (flow rate: 60 mL / min). The heating program was as follows: heating from room temperature to 500 °C at a heating rate of 20 °C / min. The temperature at which the sample mass loss reached 5% was recorded as T. 5% .

[0054] High-temperature volatile matter test: Take a clean, constant-weight aluminum pan, add 5.0±0.1g of sample, and weigh accurately. Place the aluminum pan in a constant-temperature forced-air drying oven at 220±1℃ and heat continuously for 4 hours. Remove and cool to room temperature in a desiccator before weighing. The volatile matter W is calculated using the formula: W=[(m1-m2) / (m1-m0)]×100%; where m0 is the mass of the aluminum pan, m1 is the total mass of the sample and aluminum pan before heating, and m2 is the total mass after heating.

[0055] Anti-yellowing test: Using a fully automatic colorimeter (model: UltraScan PRO), the yellowness index (YI) of the samples before and after high-temperature heating under the above (high-temperature volatile matter test conditions) was tested, and the yellowness difference before and after heating, ∆YI=YI, was calculated. after -YI before .

[0056] Dynamic friction coefficient test The samples prepared in each embodiment and comparative example were formulated into a 10% (w / w) deionized water emulsion. Polyester filament (150D / 48F) was used as the substrate, and oiling was performed by impregnation and extrusion to ensure an oiling rate of 1.0 ± 0.1%. The oiled yarn was dried at 105°C for 2 hours, and then allowed to stand for 24 hours in a constant temperature and humidity environment of 20°C and 65%RH. Test conditions: Under constant temperature and humidity conditions of 20°C and 65%RH, a dynamic friction coefficient tester was used as the testing instrument. Using a winch method, the oiled yarn was wound at a 180° angle around a stainless steel guide roller with a diameter of 6 mm and a surface finish Ra ≤ 0.2 μm. The yarn speed was set to 120 m / min, and the pretension was 20 cN. The dynamic friction coefficient μ between the yarn and the stainless steel guide roller was measured.

[0057] Emulsion stability test Pour 10% emulsion into a 10mL centrifuge tube, place it in a centrifuge, and centrifuge at 4000 rpm for 15 minutes. Observe whether the emulsion shows layering, oil separation, or precipitation. If there are no abnormalities, record it as "qualified".

[0058] The test results are shown in Table 1.

[0059] Table 1 Relevant performance test results The test results above show that the overall performance of the samples prepared in each embodiment is superior to that of the comparative examples. A comparison of the test data from Example 1 and Comparative Example 1 (without 1,2-epoxy-3,3,3-trifluoropropane) indicates that the introduction of trifluoroepoxypropane can effectively improve T... 5% This demonstrates that the introduction of CF bonds can enhance the chemical bonding strength of the polyether backbone. A comparison of test data from Example 1 and Comparative Example 2 (without octadecyl isocyanate) shows that the sample without alkyl isocyanate modification exhibits greater yellowing, indicating that end-hydroxyl capping can prevent oxidation chain initiation and improve stability. A comparison of test data from Example 1 and Comparative Example 3 (with the nano-silicon-based hybrid additive replaced by an equal amount of benzotriazole) shows that directly adding benzotriazole not only results in high volatility but also poor emulsion stability.

[0060] 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.

[0061] 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 method for preparing a high-temperature stable polyether smoothing agent for spinning, characterized in that, Includes the following steps: S100: Crude polyether is prepared using raw materials including bisphenol A, an alkaline catalyst, 1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane. S200: Modified polyether is prepared using raw materials including crude polyether, deionized water, acidic substances, adsorbent, alkyl isocyanate, and organotin catalyst. S300, using raw materials including benzotriazole, ethyl acetate, nonionic surfactant, tetraethyl orthosilicate, and silane coupling agent, prepares nano-silicon-based hybrid additives; The polyether smoothing agent is obtained by shearing and emulsifying raw materials including S400, modified polyether, nano-silicon-based hybrid additives, and hindered phenolic antioxidants.

2. The method for preparing a high-temperature stable polyether smoothing agent for spinning according to claim 1, characterized in that, Step S100 is as follows: Bisphenol A and an alkaline catalyst are added sequentially to the reactor, the temperature is raised to 105-115℃, and the reactor is circulated for dehydration under vacuum for 1-2 hours. After nitrogen purging 3-5 times, the temperature is maintained at 110±5℃ and the pressure is controlled at 0.2-0.3MPa. A mixed monomer containing 1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane is slowly added dropwise. After the addition is completed, the mixture is kept at the temperature for 2-3 hours to obtain crude polyether.

3. The method for preparing a high-temperature stable polyether smoothing agent for spinning according to claim 2, characterized in that, The mixed monomers are composed of 1,2-epoxybutane, propylene oxide and 1,2-epoxy-3,3,3-trifluoropropane in a mass ratio of 12-18:70-82:8-12.

4. The method for preparing a high-temperature stable polyether smoothing agent for spinning according to claim 1, characterized in that, Step S200 is as follows: Deionized water is added to the crude polyether to hydrolyze the alkaline catalyst, then an acidic substance is added for neutralization, followed by the addition of an adsorbent and stirring thoroughly for 1-2 hours. Subsequently, the temperature is raised to 100-110℃ for vacuum dehydration, followed by fine filtration and cooling to 80-90℃. Alkyl isocyanate and organotin catalyst are added sequentially, and the reaction is carried out for 4-5 hours to obtain the modified polyether.

5. The method for preparing a high-temperature stable polyether smoothing agent for spinning according to claim 4, characterized in that, The acidic substance is phosphoric acid or glacial acetic acid; the adsorbent is synthetic magnesium silicate; the organotin is one or more of di-n-butyltin dilaurate, stannous octoate, di-n-octyltin dilaurate, and dimethyltin dithioacetate.

6. The method for preparing a high-temperature stable polyether smoothing agent for spinning according to claim 1, characterized in that, Step S300 includes the following steps: S310. Add benzotriazole to ethyl acetate and stir in a constant temperature water bath at 40-45℃ until completely dissolved to obtain a mixture. Slowly pour the mixture into deionized water containing nonionic surfactants, pre-emulsify it for 5-8 minutes using a high-speed shear machine, and then ultrasonically disperse it for 15-20 minutes under ice-water bath conditions to obtain a nanoemulsion. S320. Add tetraethyl orthosilicate to the nanoemulsion, adjust the pH of the system to 9.5-10.5, and stir continuously at 35-40℃ for 24-28h. After the reaction is completed, remove the solvent by vacuum distillation at 50-55℃, then lower the temperature to 35-40℃, add silane coupling agent and stir for 4-5h to obtain nano-silicon-based hybrid additive.

7. The method for preparing a high-temperature stable polyether smoothing agent for spinning according to claim 6, characterized in that, The nonionic surfactant is one or more of Tween-80, AEO-9, polyether F-127, and PVA-1788.

8. The method for preparing a high-temperature stable polyether smoothing agent for spinning according to claim 6, characterized in that, The silane coupling agent is one or more of KH-550, KH-560, and KH570.

9. The method for preparing a high-temperature stable polyether smoothing agent for spinning according to claim 1, characterized in that, Step S400 specifically involves mixing the modified polyether, nano-silicon-based hybrid additive, and hindered phenolic antioxidant, and then shearing and emulsifying them at 60-65°C to obtain the polyether smoothing agent.

10. A high-temperature stable polyether smoothing agent for spinning, characterized in that, It is prepared by the method for preparing a high-temperature stable polyether smoothing agent for spinning as described in any one of claims 1-9.

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