High-temperature-resistant full-dull high-speed spinning POY oil and preparation method thereof

Abstract

This application relates to the field of textile auxiliary technology, and provides a high-temperature resistant, fully dull, high-speed spinning POY oil and its preparation method. The preparation method includes the following steps: S100, mixing a smoothing agent, an antistatic agent, a synergist, and an antioxidant, and then adding a penetrant to obtain an oil phase; S200, adding the additives to water and dispersing them to obtain an aqueous phase; S300, adding the oil phase to the aqueous phase and subjecting it to high-shear treatment to obtain an emulsion; S400, adjusting the viscosity and pH of the emulsion and filtering it to obtain the high-temperature resistant, fully dull, high-speed spinning POY oil; wherein, the antistatic agent is a modified polysiloxane antistatic agent. The modified polysiloxane antistatic agent used in this application has a stable structure and strong anti-migration properties, and can continuously exert its conductive effect under high-temperature environments. It has better thermal stability and durability than traditional small-molecule antistatic agents. Using a larger amount of antistatic agent can ensure the antistatic effect without affecting the stability of the system or changing the physical properties of the oil due to excessive addition.

Description

Technical Field

[0001] This application relates to the field of textile auxiliaries technology, and in particular to a high-temperature resistant, fully dull, high-speed spinning POY oiling agent and its preparation method. Background Technology

[0002] Pre-oriented polyester yarn (POY) is an important intermediate product of polyester filament, widely used in high-speed spinning and stretching processes. Especially in the fully dull high-speed spinning process, the large-area exposure of titanium dioxide (TiO2) particles on the fiber surface increases the coefficient of friction between fibers and between fibers and equipment, leading to increased fuzzing and breakage rates, thus placing higher demands on the performance of the spinning oil. Therefore, special spinning oils are required during the high-speed spinning process of POY to lubricate, bundle, and prevent static electricity in the fibers.

[0003] Existing POY oil systems are mostly composed of polyether-based smoothing agents, bundlers, and antistatic agents, with the antistatic components often being ionic surfactants such as organophosphate salts, sulfonates, and carboxylates. However, these antistatic agents generally suffer from the following problems: First, their thermal stability is generally insufficient, making them prone to thermal decomposition or migration during subsequent high-temperature stretching or heat setting processes. This not only leads to a decrease in film-forming performance but may also cause problems such as fumes and coking, making them unsuitable for the harsh conditions of high-speed spinning and subsequent heat treatment processes. Second, traditional antistatic agents are mostly small-molecule ionic substances with high migration and poor durability, easily precipitating out of the oil film or volatilizing, causing a rapid decline in the antistatic effect and affecting the long-term quality of the fiber. Furthermore, in the fully dull polyester system, TiO2, as a key dull filler, is prone to agglomeration and sedimentation of its nanoscale particles in the oiling agent, or to precipitation from the oil film after fiber forming, resulting in a "white powder" phenomenon, which seriously affects the product appearance and spinning continuity. Traditional oiling agents have limited ability to coat and disperse TiO2, making it difficult to ensure system stability and exacerbating the above problems.

[0004] Therefore, there is an urgent need to develop a high-temperature resistant, fully dull, high-speed spinning POY oil to meet the requirements of high-speed POY spinning. Summary of the Invention

[0005] In view of the above-mentioned shortcomings in the prior art, the purpose of this application is to provide a high-temperature resistant, fully dull, high-speed spinning POY oil and its preparation method.

[0006] To achieve the above-mentioned objectives, the technical solution adopted in this application is as follows: In a first aspect, embodiments of this application provide a method for preparing a high-temperature resistant, fully matte, high-speed spinning POY oiling agent, comprising the following steps: S100: After mixing the smoothing agent, antistatic agent, synergist and antioxidant, a penetrant is added to obtain the oil phase; S200: Add the additive to water and disperse to obtain an aqueous phase; S300: Add the oil phase to the aqueous phase and perform high-shear treatment to obtain an emulsion; S400, adjust the viscosity and pH of the emulsion, and filter it to obtain a high-temperature resistant, fully dull, high-speed spinning POY oiling agent; The antistatic agent is a modified polysiloxane antistatic agent.

[0007] In one optional embodiment, the method for preparing the modified polysiloxane antistatic agent includes: S110. Under an inert gas atmosphere, allyl bromide and a catalyst are added to hydrogen-containing silicone oil, and the mixture is stirred for the first time to obtain an intermediate. S120. The intermediate and 1-methylimidazole are added to the solvent and subjected to a second stirring treatment to obtain the modified polysiloxane antistatic agent.

[0008] In one alternative embodiment, the molar ratio of the hydrogen-containing silicone oil and allyl bromide is 1:(1.1-1.2); and / or the molar ratio of the intermediate to 1-methylimidazole is 1:(1-1.1).

[0009] In one optional embodiment, the temperature of the first stirring treatment is 60-80°C; and / or the time of the first stirring treatment is 4-6 hours; and / or the temperature of the second stirring treatment is 70-100°C; and / or the time of the second stirring treatment is 8-10 hours.

[0010] In one alternative embodiment, the mass ratio of smoothing agent, antistatic agent, synergist, antioxidant and penetrant is 1:(0.1-0.2):(0.02-0.1):(0.006-0.015):(0.08-0.15); and / or the mass ratio of antistatic agent to additive is 1:(0.01-0.02).

[0011] In an alternative embodiment, the smoothing agent comprises smoothing agent A and smoothing agent B; the mass ratio of smoothing agent A to smoothing agent B is (2-6):1.

[0012] In one alternative embodiment, smoother A comprises polyethylene glycol or C12-C18 fatty acid; smoother B comprises C12-C18 fatty acid or ethylene oxide.

[0013] In an optional embodiment, in S300, the high-shear treatment speed is 2000-4000 rpm; and / or in S400, the viscosity of the emulsion is adjusted to 20-80 mPa·s; and / or in S400, the pH of the emulsion is adjusted to 6.8-7.2.

[0014] In one alternative embodiment, the additive comprises pretreated titanium dioxide; the pretreatment is a dispersion treatment of titanium dioxide in a polyether-modified siloxane.

[0015] Secondly, embodiments of this application provide a high-temperature resistant, fully dull, high-speed spinning POY oiling agent, which is prepared using any of the preparation methods described above.

[0016] The beneficial effects of this application include at least the following: (1) In this application, a modified polysiloxane antistatic agent is used. It has a stable structure and strong anti-migration properties. It can continuously exert a conductive effect in a high-temperature environment. It has better thermal stability and durability than traditional small molecule antistatic agents. Using more antistatic agents can ensure the antistatic effect without affecting the stability of the system or changing the physical properties of the oil due to excessive addition. (2) By grafting imidazole cationic groups into the polysiloxane backbone, this application retains the excellent thermal stability and flexibility of the siloxane segments and introduces highly polar and conductive cationic centers, so that the final product can still maintain good antistatic properties at high temperature and will not migrate, decompose or precipitate. Detailed Implementation

[0017] To make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are only for explaining this application, but the implementation of this application is not limited thereto.

[0018] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art to which this application pertains. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; the amounts of experimental reagents used are, unless otherwise specified, the amounts used in conventional experimental operations; and the experimental methods used are, unless otherwise specified, conventional methods.

[0019] The ionic antistatic agents commonly used in existing POY oiling systems have significant limitations. They exhibit poor thermal stability, easily decomposing and migrating during high-temperature processing, leading to coking and fumes. Furthermore, due to their predominantly small molecular structure, the antistatic components are prone to volatilization or precipitation, resulting in insufficient durability. In addition, in fully dull polyester systems, traditional oiling agents have limited ability to disperse and coat high-content TiO2 matting agents, easily causing particle agglomeration, sedimentation, and "white powder" precipitation, affecting spinning continuity and product appearance.

[0020] The embodiments of this application provide a high-temperature resistant, fully matte, high-speed spinning POY oil and its preparation method. By using a modified polysiloxane antistatic agent, the migration or precipitation of the antistatic agent is avoided, forming an antistatic coating film that remains stable at high temperatures. Furthermore, the modified polysiloxane antistatic agent has a large molecular weight, is resistant to evaporation and decomposition, and does not cause smoke or coking.

[0021] In a first aspect, embodiments of this application provide a method for preparing a high-temperature resistant, fully matte, high-speed spinning POY oiling agent, comprising the following steps: S100: After mixing the smoothing agent, antistatic agent, synergist and antioxidant, a penetrant is added to obtain the oil phase; S200: Add the additive to water and disperse to obtain an aqueous phase; S300: Add the oil phase to the aqueous phase and perform high-shear treatment to obtain an emulsion; S400, adjust the viscosity and pH of the emulsion, and filter it to obtain a high-temperature resistant, fully dull, high-speed spinning POY oiling agent; The antistatic agent is a modified polysiloxane antistatic agent.

[0022] Preferably, this application prioritizes the formation of components with high functionality and thermal stability into the oil phase, while dispersing easily agglomerated inorganic particles as additives in the aqueous phase. This creates a two-phase system with a clear interface and well-defined functions, effectively preventing instability or reactions caused by direct contact between components of different polarities. It also improves the dispersion uniformity of the additives, avoids agglomeration in the oil phase, optimizes subsequent emulsification efficiency, and forms a more stable water-in-oil structure. After pre-dispersion of both the oil and aqueous phases, high-shear emulsification is performed to ensure that all functional components are sufficiently homogeneous before entering the high-shear process. This avoids microphase separation due to inconsistent local component concentrations and facilitates the formation of emulsion particles with smaller particle sizes and more stable structures.

[0023] Preferably, in step S100, the smoothing agent, antistatic agent, synergist, and antioxidant are mixed, and then a penetrant is added to form an oil phase. These components are mostly non-polar or weakly polar polymers with strong oleophilic properties, making them easier to distribute evenly in the oil phase. The antistatic agent uses a modified polysiloxane structure, which effectively avoids the drawbacks of traditional phosphate ester or sulfonate antistatic agents, such as easy decomposition, inactivation, and migration at high temperatures. Antioxidants such as BHT can inhibit the high-temperature oxidation reaction of the oil agent. The synergist enhances the film-forming properties and stability of the antistatic agent, while the subsequent addition of the penetrant avoids its adverse effects on the emulsion formation process, improving the spreadability and adhesion of the final oil agent on the fiber. The mass ratio of smoothing agent, antistatic agent, synergist, antioxidant, and penetrant is 1:(0.1-0.2):(0.02-0.1):(0.006-0.015):(0.08-0.15). The smoothing agent, as the main component, occupies the majority of the oil formulation. Its main function is to provide effective lubrication between the fiber and equipment, reduce fiber breakage and equipment wear, and improve spinning stability and fiber surface quality. Therefore, a relatively large amount of smoothing agent is added to provide a basic support for the overall oil film formation and lubrication system. The antistatic agent is mainly used to solve problems such as flyaways and adhesion caused by static electricity accumulation during high-speed spinning. In this application, a modified polysiloxane antistatic agent is used, which has a stable structure, strong anti-migration properties, and can continuously exert its conductive effect at high temperatures. It has better thermal stability and durability than traditional small-molecule antistatic agents. Using a larger amount of antistatic agent can ensure the antistatic effect without affecting the system stability or changing the physical properties of the oil due to excessive addition. The main function of the synergist is to improve the uniformity of the distribution of the antistatic agent in the oil film and the stability of film formation. Synergists enhance the anchoring effect of ionic groups on the fiber surface, thereby improving the durability of antistatic agents. Synergists are usually oligomers with polar or cationic structures. Appropriate use can significantly enhance the retention rate and functionality of antistatic components during high-speed drawing. Although the amount of antioxidant is extremely small, its role is crucial. Due to the instantaneous temperature of the fiber surface in high-speed spinning processes reaching 240-260°C, oils are prone to oxidative degradation, leading to performance loss or impurity deposition. Therefore, by adding highly efficient phenolic or amine antioxidants, high-temperature oxidation of oils can be effectively inhibited, extending storage and service life, and maintaining the stability of the system's appearance and continuous function. Penetrants are mainly used to improve the spreadability and adhesion of oils on the fiber surface, ensuring the formation of a uniform and continuous lubricating film during spraying, avoiding local dry spraying or accumulation. Penetrants are usually nonionic polyether surfactants. Their good emulsifying and wetting properties make them an indispensable auxiliary agent in oil systems. Using the above-mentioned amount of penetrant can balance emulsion stability and film formation continuity, improving the consistency of spinning quality.

[0024] Furthermore, in the POY oiling system for high-speed, fully dull spinning, using a single smoothing agent typically fails to simultaneously meet performance standards across multiple dimensions, including thermal stability, lubrication durability, wetting speed, and spray uniformity. This is because, in the complex environment of high-speed, fully dull spinning, a single smoothing agent cannot cope with the combined forces generated by high temperature, high speed, and multiple interfacial contacts, easily leading to problems such as poor film formation, film detachment, and filament breakage, severely impacting fiber quality and production efficiency. Therefore, the smoothing agent includes smoothing agent A and smoothing agent B. Smoothing agent A, as the main agent, primarily uses polyethylene glycol (PEG) or C12-C18 fatty acids, which possess excellent lubricity and thermal stability. During high-speed spinning, smoothing agent A can form a dense and flexible lubricating film between the fiber and the equipment surface, effectively reducing the coefficient of friction, minimizing fuzzing and breakage, and improving spinning stability. PEG, with its flexible chain structure and hydrophilicity, can distribute evenly on the fiber surface, providing durable lubrication, while fatty acids help enhance fiber surface lubrication. Wetting properties are optimized to improve the spreadability of the lubricant. Smoothing agent B, as an auxiliary agent, is generally selected from condensates of C12-C18 fatty acids or ethylene oxide (EO) structures. This aims to enhance the affinity and film adhesion between the lubricant and the fiber surface. The ethylene oxide structure possesses excellent polarity regulation capabilities, improving the adhesion and stability of the lubricating film under high-speed stretching conditions, thus contributing to rapid film formation and long-lasting durability. Furthermore, smoothing agent B promotes the emulsification stability of the emulsion, resulting in finer and more uniform emulsion particle size, improving storage stability and spray consistency. The mass ratio of smoothing agent A to smoothing agent B is (2-6):1, constructing a smoothing agent with smoothing agent A forming the main lubrication structure and smoothing agent B finely adjusting wettability and adhesion. This provides a stable lubricating film at high temperatures while enhancing emulsion stability and process compatibility. It avoids the disadvantages of single fatty acid-type smoothing agents being easily oxidized and decomposed, and overcomes the problem of insufficient lubrication persistence of single polyether-type smoothing agents.

[0025] Furthermore, the preparation method of the modified polysiloxane antistatic agent includes: S110. Under an inert gas atmosphere, allyl bromide and a catalyst are added to hydrogen-containing silicone oil, and the mixture is stirred for the first time to obtain an intermediate. S120. The intermediate and 1-methylimidazole are added to the solvent and subjected to a second stirring treatment to obtain the modified polysiloxane antistatic agent.

[0026] Preferably, this application grafts imidazole cationic groups into the polysiloxane backbone, which retains the excellent thermal stability and flexibility of the siloxane segments while introducing highly polar and conductive cationic centers. This allows the final product to maintain good antistatic properties at high temperatures without migrating, decomposing, or precipitating. Compared to traditional phosphate ester, sulfonate, or quaternary ammonium salt small molecule antistatic agents, this antistatic agent exhibits significant advantages in temperature resistance and service life.

[0027] Preferably, in step S110, allyl bromide is added to hydrogen-containing silicone oil under an inert gas atmosphere, and an addition reaction is carried out with the aid of a catalyst, preferably a Karstedt catalyst, to obtain an intermediate containing a brominated alkyl side chain. This step utilizes the Si-H bond in the hydrogen-containing silicone oil molecule to react with the carbon-carbon double bond of the allyl group, introducing an active haloalkyl group to provide a site for the subsequent quaternization reaction. The temperature of the first stirring treatment is 60-80℃, and the time is 4-6 hours, which can ensure high addition efficiency, few side reactions, and maximize the preservation of the silicone oil main chain structure and performance. The molar ratio of hydrogen-containing silicone oil to allyl bromide is 1:(1.1-1.2). A moderate excess of allyl bromide helps to improve the conversion rate of the reaction and avoid unreacted sites in the hydrogen-containing silicone oil, thereby obtaining an intermediate with a uniform structure. Furthermore, controlling the molar ratio within this range can effectively avoid side reactions, chain crosslinking, or system instability caused by a large excess of allyl bromide. While ensuring the reactivity and structural controllability of the intermediate, it is also beneficial to the subsequent grafting reaction.

[0028] Preferably, in step S120, the intermediate is mixed with 1-methylimidazole in a solvent such as ethanol or DMF, and subjected to a second stirring treatment at 70-100°C for 8-10 hours to undergo a quaternization reaction, generating an imidazole salt-grafted polysiloxane antistatic agent. This reaction is a nucleophilic substitution reaction between a haloalkane and an imidazole ring, which can be completed efficiently under mild conditions, forming a stable imidazole cationic structure. The molar ratio of the intermediate to 1-methylimidazole is 1:(1-1.1), which can further promote the reaction towards complete conversion, ensuring that each reactive site can be efficiently grafted with an imidazole cation. This helps to reduce the presence of ungrafted side chains, improve the structural consistency and performance stability of the final antistatic agent, and, by controlling the amount of 1-methylimidazole within the above range, avoids excessive residual free imidazole, thus preventing it from affecting the pH value of the emulsion, the stability of the oil system, or the risk of volatilization in high-temperature applications.

[0029] Preferably, in step S200, the additive is dispersed in water to form an aqueous phase. The additive is usually titanium dioxide (TiO2). TiO2 is a strongly polar inorganic particle that is prone to agglomeration in oil. Therefore, it is advisable to disperse it in the aqueous phase before mixing it with the oil phase. The preferred additive is pretreated titanium dioxide. Pretreatment involves dispersing titanium dioxide in polyether-modified siloxane. Polyether-modified siloxane possesses a unique amphiphilic structure, with the polyether segments providing excellent hydrophilicity and the siloxane skeleton imparting excellent compatibility with oily components. During dispersion, the polyether-modified siloxane forms a flexible coating layer on the surface of TiO2 particles, reducing surface energy between particles and effectively preventing agglomeration, thereby significantly improving dispersion stability and particle uniformity. This pretreatment enhances the compatibility of TiO2 with the entire oil system. Pretreated TiO2 particles exhibit better wetting and stability at the oil and water phase interface, preventing emulsion stratification, particle migration, or sedimentation, thus improving the overall uniformity and storage stability of the oil. Furthermore, the polyether-modified siloxane itself possesses good thermal stability, and its synergistic structure with TiO2 also helps improve the high-temperature resistance of the oil system, reducing thermal decomposition or performance loss during high-speed spinning. Pretreatment also regulates the overall matting effect. Polyether-modified siloxane buffers the optical reflection and scattering on the TiO2 particle surface to a certain extent, preventing excessively strong reflective spots or discoloration from forming on the fiber surface, resulting in a softer and more uniform matting effect in the final fiber. The mass ratio of antistatic agent to additive is 1:(0.01-0.02), ensuring excellent antistatic and high-temperature performance of the oil while fully utilizing the auxiliary role of titanium dioxide without adversely affecting the overall emulsion structure and spinning application. Preferably, 0.5-2 wt.% of a bundler by weight of the high-temperature resistant, fully matting, high-speed spinning POY oil is added to the aqueous phase to improve system stability and fiber consistency.

[0030] Preferably, in step S300, the oil phase is added to the aqueous phase and subjected to high-shear emulsification at 55-65°C for 15-30 minutes. This forms a stable emulsion system with uniform particle size, ensuring that antistatic agents, lubricants, and other components are fully dispersed with additives, enhancing the film-forming properties of the oil and its adhesion to the fiber surface, thus improving both antistatic and lubricating effects. Simultaneously, controlling the particle size helps improve spray atomization and fiber surface uniformity. The high-shear treatment speed is 2000-4000 rpm, which not only fully emulsifies the oil and aqueous phases to form a stable emulsion with small and uniform particle size, but also ensures that the heat-sensitive functional components are not damaged, thus facilitating the production of high-performance POY-specific oil products with consistent quality and reliable performance.

[0031] Preferably, in step S400, the viscosity of the emulsion is adjusted by adding water to ensure both good fluidity and a certain film thickness. Adjusting the emulsion viscosity to 20-80 mPa·s facilitates stable operation of the spraying system. During high-speed spinning, the oil needs to be atomized and evenly coated onto the fiber surface through nozzles. If the viscosity is too high, it will cause nozzle clogging or poor delivery; if the viscosity is too low, the oil film will be too thin, easily leading to problems such as sagging and insufficient lubrication. Therefore, controlling the viscosity within the above range not only helps form a continuous and dense lubricating layer on the fiber surface, improving antistatic and anti-broken fiber effects, but also enhances the structural stability of the emulsion, preventing oil droplet aggregation or phase separation, especially for particulate additives such as titanium dioxide. The dispersion stability of the agent plays a positive role; pH adjustment is used to maintain system stability and avoid emulsion demulsification or component degradation caused by acid and alkali. The pH of the emulsion is adjusted to 6.8-7.2 to protect the chemical stability of various functional components in the oil system. Modified polysiloxane antistatic agents, smoothing agents, etc. are prone to hydrolysis, degradation or dissociation under acidic or alkaline conditions, affecting their performance. The pretreated titanium dioxide particles rely on the polyether-modified siloxane coating on the surface to form a stable dispersion system. If the pH deviates from this range, the surface charge may change, leading to adsorption aggregation, sedimentation and other adverse phenomena between particles. Finally, microporous filtration is used to remove large particles and impurities to prevent nozzle clogging and improve spinning continuity and oil quality consistency.

[0032] Secondly, embodiments of this application provide a high-temperature resistant, fully dull, high-speed spinning POY oiling agent, which is prepared using any of the preparation methods described above.

[0033] Example 1

[0034] This embodiment provides a method for preparing a high-temperature resistant, fully matte, high-speed spinning POY oiling agent, comprising the following steps: S100: After mixing the smoothing agent, antistatic agent, synergist and antioxidant in a mass ratio of 1:0.1:0.02:0.006:0.08, a penetrant is added to obtain the oil phase; S200. Add the additive to water and disperse it to obtain an aqueous phase. The mass ratio of the additive to the antistatic agent is 0.01:1. S300. Add the oil phase to the aqueous phase and perform high shear treatment at 55℃ and 2000rpm for 15min to obtain an emulsion. S400, add water to adjust the viscosity of the emulsion to 20 mPa·s, adjust the pH to 6.8, and then filter to obtain a high-temperature resistant, fully matte, high-speed spinning POY oiling agent; The antistatic agent is a modified polysiloxane antistatic agent; the smoothing agent includes smoothing agent A and smoothing agent B, where smoothing agent A is PEG and smoothing agent B is C12 fatty acid, and the mass ratio of smoothing agent A to smoothing agent B is 2:1; the additive is pretreated titanium dioxide; the pretreatment involves dispersing titanium dioxide in polyether-modified siloxane.

[0035] Example 2

[0036] This embodiment provides a method for preparing a high-temperature resistant, fully matte, high-speed spinning POY oiling agent, comprising the following steps: S100: Mix the smoothing agent, antistatic agent, synergist and antioxidant in a mass ratio of 1:0.2:0.1:0.015:0.15, and then add the penetrant to obtain the oil phase; S200. Add the additive to water and disperse it to obtain an aqueous phase. The mass ratio of the additive to the antistatic agent is 0.02:1. S300. Add the oil phase to the aqueous phase and subject it to high shear treatment at 65℃ and 4000rpm for 30min to obtain an emulsion. S400, add water to adjust the viscosity of the emulsion to 80 mPa·s, adjust the pH to 7.2, and then filter to obtain a high-temperature resistant, fully dull, high-speed spinning POY oiling agent; The antistatic agent is a modified polysiloxane antistatic agent, and its preparation method includes the following steps: S110. Under an inert gas atmosphere, allyl bromine and catalyst are added to hydrogen-containing silicone oil at a molar ratio of 1:1.1, and the mixture is stirred at 60°C for 4 hours to obtain an intermediate. S120. The intermediate and 1-methylimidazole are added to a solvent at a molar ratio of 1:1. The mixture is stirred at 70°C for 8 hours to obtain a modified polysiloxane antistatic agent. The smoothing agent includes smoothing agent A and smoothing agent B. Smoothing agent A is a C12 fatty acid, and smoothing agent B is EO. The mass ratio of smoothing agent A to smoothing agent B is 6:1. The additive is pretreated titanium dioxide. The pretreatment is to add titanium dioxide to polyether-modified siloxane for dispersion treatment.

[0037] Example 3

[0038] This embodiment provides a method for preparing a high-temperature resistant, fully matte, high-speed spinning POY oiling agent, comprising the following steps: S100: After mixing the smoothing agent, antistatic agent, synergist, and antioxidant in a mass ratio of 1:0.1:0.1:0.01:0.1, a penetrant is added to obtain the oil phase. S200. Add the additive to water and disperse to obtain an aqueous phase. The mass ratio of the additive to the antistatic agent is 0.02:1. Then add 0.5 wt.% of the high-temperature resistant, fully dull, high-speed spinning POY oil agent as a bridging agent and continue to disperse evenly. S300: Add the oil phase to the aqueous phase and subject it to high shear treatment at 60℃ and 3000rpm for 25min to obtain an emulsion. S400, add water to adjust the viscosity of the emulsion to 60 mPa·s, adjust the pH to 7.0, and then filter to obtain a high-temperature resistant, fully matte, high-speed spinning POY oiling agent; The antistatic agent is a modified polysiloxane antistatic agent, and its preparation method includes the following steps: S110. Under an inert gas atmosphere, allyl bromine and catalyst are added to hydrogen-containing silicone oil at a molar ratio of 1:1.2, and the mixture is stirred at 80°C for 6 hours to obtain an intermediate. S120. The intermediate and 1-methylimidazole are added to a solvent at a molar ratio of 1:1.1. The mixture is then subjected to a second stirring treatment at 100°C for 10 hours to obtain a modified polysiloxane antistatic agent. The smoothing agent includes smoothing agent A and smoothing agent B, where smoothing agent A is a C18 fatty acid and smoothing agent B is a C18 fatty acid, with a mass ratio of smoothing agent A to smoothing agent B of 4:1; the additive is pretreated titanium dioxide; the pretreatment involves dispersing titanium dioxide in polyether-modified siloxane.

[0039] Example 4

[0040] This embodiment provides a method for preparing a high-temperature resistant, fully matte, high-speed spinning POY oiling agent, comprising the following steps: S100: After mixing the smoothing agent, antistatic agent, synergist, and antioxidant in a mass ratio of 1:0.1:0.1:0.01:0.1, a penetrant is added to obtain the oil phase. S200. Add the additive to water and disperse to obtain an aqueous phase. The mass ratio of the additive to the antistatic agent is 0.02:1. Then add 0.5 wt.% of the high-temperature resistant, fully dull, high-speed spinning POY oil agent as a bridging agent and continue to disperse evenly. S300: Add the oil phase to the aqueous phase and subject it to high shear treatment at 60℃ and 3000rpm for 25min to obtain an emulsion. S400, add water to adjust the viscosity of the emulsion to 60 mPa·s, adjust the pH to 7.0, and then filter to obtain a high-temperature resistant, fully matte, high-speed spinning POY oiling agent; The antistatic agent is a modified polysiloxane antistatic agent, and its preparation method includes the following steps: S110. Under an inert gas atmosphere, allyl bromine and catalyst are added to hydrogen-containing silicone oil at a molar ratio of 1:1.2, and the mixture is stirred at 75°C for 5 hours to obtain an intermediate. S120. The intermediate and 1-methylimidazole are added to a solvent at a molar ratio of 1:1.1. The mixture is stirred at 90°C for 9 hours to obtain a modified polysiloxane antistatic agent. The smoothing agent includes smoothing agent A and smoothing agent B. Smoothing agent A is a C12 fatty acid and smoothing agent B is a C18 fatty acid. The mass ratio of smoothing agent A to smoothing agent B is 4:1. The additive is pretreated titanium dioxide. The pretreatment is to add titanium dioxide to polyether-modified siloxane for dispersion treatment.

[0041] Comparative Example 1 This comparative example provides a method for preparing a fully matte high-speed spinning POY oiling agent. The difference from Example 1 is that a quaternary ammonium salt antistatic agent is used, the additive is raw titanium dioxide, and no pretreatment is performed.

[0042] Comparative Example 2 This comparative example provides a method for preparing a fully matte high-speed spinning POY oiling agent. The difference from Example 1 is that the additive is raw titanium dioxide without pretreatment.

[0043] Comparative Example 3 This comparative example provides a method for preparing a fully dull high-speed spinning POY oiling agent. The difference from Example 1 is that a quaternary ammonium salt antistatic agent is used.

[0044] This application has undergone multiple experiments, and some of the test results are presented here for reference to further describe the invention in detail. The following is a detailed description in conjunction with specific embodiments.

[0045] Performance testing Thermal stability test: A thermogravimetric analyzer was used to test approximately 10 mg of sample under a nitrogen atmosphere at a heating rate of 10 °C / min. The temperatures corresponding to 5% and 10% mass loss and the maximum heat loss rate within the range of 30-600 °C were recorded. The test results are shown in Table 1.

[0046] Table 1 As shown in Table 1, the thermal decomposition temperatures of Examples 1-4 are all higher than those of Comparative Examples 1-3, indicating that the modified polysiloxane antistatic agent and the pretreated titanium dioxide additive used in the high-temperature resistant, fully dull, high-speed spinning POY oil described in this application enable the oil to maintain structural stability in a higher temperature range, making it more suitable for subsequent high-temperature stretching and heat setting environments. Compared with Comparative Example 1, Comparative Example 2 has a higher thermal decomposition temperature, indicating that using a modified polysiloxane antistatic agent to replace the quaternary ammonium salt antistatic agent can significantly improve the system's resistance to thermal decomposition.

[0047] Thermal aging test: The oils of Examples 1-4 and Comparative Examples 1-3 were coated into films and dried at low temperature. 1g of each dry film sample was placed in an oven at 150℃ for 4h and then placed in a desiccator to cool to room temperature for 30min. The weight was then weighed and the thermal weight loss rate was calculated. Coking tendency test: Take 1.0 mL of the oil sample from Examples 1-4 and Comparative Examples 1-3 respectively and drop it onto the center of a 304 steel sheet (50 mm × 20 mm × 1 mm) after ultrasonic cleaning. Spread it out to a diameter of about 20-25 mm, put it in an oven at 220℃ for 3 min, take it out and cool it to 25℃, and perform weighing and visual evaluation. The amount of coking in the weighing evaluation = M1 - M0, where M0 is the mass of the steel sheet before heating and M1 is the mass after heating and cooling. The visual evaluation is divided into 0-5 levels: 0 No residue, 1 Slight yellowing, 2 Thin film, 3 Obvious browning, 4 Dark brown char spots, 5 Large black char, hard and brittle. The results are shown in Table 2.

[0048] Table 2 As can be seen from Table 2, the thermal weight loss rate and coking amount of Examples 1-4 are all less than those of Comparative Examples 1-3, indicating that the high-temperature resistant, fully dull, high-speed spinning POY oiling agent described in this application not only has good heat resistance, but is also less prone to carbon deposits and coking residues at high temperatures, which is beneficial to reducing smoke, carbon deposit pollution and coking risk.

[0049] Antistatic performance retention test before and after high temperature: The oils of Examples 1-4 and Comparative Examples 1-3 were applied to POY yarns and then heat-treated. The resistance before and after aging was measured and the logarithmic difference was calculated. The results are shown in Table 3.

[0050] Table 3 As shown in Table 3, the Δlog of Examples 1-4 and Comparative Example 2... 10 (Rs) is small, and the resistance R after aging is small. s Still in 10 7 -10 8The magnitude of the difference indicates that the modified polysiloxane antistatic agent is less prone to decomposition and migration at high temperatures, and the conductive pathway is more stable, indicating improved heat resistance due to the use of the modified polysiloxane antistatic agent; while the resistance and Δlog of Comparative Examples 1 and 3 before and after aging... 10 (Rs) indicates that traditional antistatic agents are prone to failure and migration at high temperatures.

[0051] Emulsion stability test: Take 100 mL of the oil emulsions from Examples 1-4 and Comparative Examples 1-3 respectively, put them into a transparent graduated cylinder, seal it, and place it in a constant temperature incubator at 60℃ for 7 days. Record whether stratification, oil floating, and flocculation occur.

[0052] Table 4 Among them, the oil floating grade is: 0 none, 1 a small amount of oil droplets or oil mist, 2 obvious oil layer or oil droplets, 3 continuous oil layer; the flocculation grade is: 0 none, 1 a small amount of flocculent matter, 2 obvious flocculent clumps, 3 a large amount of flocculation accompanied by sedimentation.

[0053] As can be seen from Table 4, no stratification, oil floating, or flocculation occurred in Examples 1-4. In Comparative Example 3, the titanium dioxide was pretreated, so the oil floating and flocculation phenomena were reduced compared to Comparative Example 1. This indicates that the oil emulsion of the present invention has excellent thermal storage stability and can effectively reduce stratification and sedimentation during high-temperature use.

[0054] Heat resistance test of POY after oiling and heat treatment: Take POY tows from the same batch, dilute the oil to 15wt.% solid content according to the actual oil concentration, spray oil, with an oiling rate of 0.8wt.%, place in a 200℃ hot box for 3 minutes, wipe the fiber surface with black paper, weigh the paper weight gain, which is the white powder precipitation quality. The oil spots on the fiber are evaluated by visual evaluation, and the yellowing ΔE is tested by a colorimeter. The test results are shown in Table 5.

[0055] Table 5 The oil stain grades are as follows: 0 No stains; 1 Slight; 2 Small amount of scattered spots; 3 Obvious spots and streaks; 4 Large area of ​​oil stains; 5 Severe oil stains with adhesions and hard spots.

[0056] As shown in Table 5, after oiling in Examples 1-4, no TiO2 migration and precipitation occurred on the fiber surface after heat treatment, nor did any appearance defects caused by local accumulation or uneven spreading of the oil film occur. This indicates that the emulsion structure and film-forming state of the oil system are very stable under high temperature conditions, effectively avoiding common problems such as white powder, bright spots, and wet spots in fully matte systems. At the same time, the yellowing ΔE of the examples is at a low level and fluctuates very little, indicating that the oil is not prone to oxidative cracking or side reactions to generate colored substances at high temperatures, demonstrating good thermochemical stability and antioxidant capacity. In contrast, Comparative Examples 1-3 all showed obvious powder precipitation and oil spots, and the yellowing was significantly aggravated, reflecting insufficient high-temperature stability. Comparative Example 1 had the highest amount of powder precipitation and an oil spot grade of 4, as well as the highest yellowing ΔE, indicating that not only did a large amount of TiO2 precipitate after heat treatment, but the oil film also became severely unstable. There may be problems such as particle agglomeration and sedimentation, interfacial film damage, or migration and volatilization of small molecule components, resulting in obvious defects on the fiber surface accompanied by strong yellowing. Comparative Example 2 showed some improvement, indicating that its formulation or dispersion was more stable than that of Comparative Example 1, but significant TiO2 migration and uneven oil film still existed. Comparative Example 3 showed a further reduction in powder precipitation, but the oil spot grade remained at 3 and the yellowing ΔE actually increased, indicating that although particle precipitation was alleviated, the adhesion stability or antioxidant capacity of the oil film at high temperatures was still insufficient, resulting in the failure to simultaneously improve appearance defects and severe yellowing. The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application, and should all be included within the protection scope of this application.

Claims

1. A method for preparing a high-temperature resistant, fully matte, high-speed spinning POY oiling agent, characterized in that, Includes the following steps: S100: After mixing the smoothing agent, antistatic agent, synergist and antioxidant, a penetrant is added to obtain the oil phase; S200: Add the additive to water and disperse to obtain an aqueous phase; S300: The oil phase is added to the aqueous phase and subjected to high-shear treatment to obtain an emulsion; S400: Adjust the viscosity and pH of the emulsion, and perform filtration to obtain the high-temperature resistant, fully dull, high-speed spinning POY oil agent; The antistatic agent is a modified polysiloxane antistatic agent.

2. The preparation method according to claim 1, characterized in that, The preparation method of the modified polysiloxane antistatic agent includes: S110. Under an inert gas atmosphere, allyl bromide and a catalyst are added to hydrogen-containing silicone oil, and the mixture is stirred for the first time to obtain an intermediate. S120. The intermediate and 1-methylimidazole are added to the solvent and subjected to a second stirring treatment to obtain the modified polysiloxane antistatic agent.

3. The preparation method according to claim 2, characterized in that, The molar ratio of the hydrogen-containing silicone oil to the allyl bromide is 1:(1.1-1.2); and / or The molar ratio of the intermediate to the 1-methylimidazole is 1:(1-1.1).

4. The preparation method according to claim 2, characterized in that, The temperature of the first stirring treatment is 60-80℃; and / or The first stirring treatment time is 4-6 hours; and / or The temperature of the second stirring treatment is 70-100℃; and / or The second stirring treatment takes 8-10 hours.

5. The preparation method according to claim 1, characterized in that, The mass ratio of the smoothing agent, the antistatic agent, the synergist, the antioxidant, and the penetrant is 1:(0.1-0.2):(0.02-0.1):(0.006-0.015):(0.08-0.15); and / or The mass ratio of the antistatic agent to the additive is 1:(0.01-0.02).

6. The preparation method according to claim 5, characterized in that, The smoothing agent includes smoothing agent A and smoothing agent B; The mass ratio of the smoothing agent A to the smoothing agent B is (2-6):

1.

7. The preparation method according to claim 6, characterized in that, The smoothing agent A includes polyethylene glycol or C12-C18 fatty acids; The smoothing agent B comprises C12-C18 fatty acids or ethylene oxide.

8. The preparation method according to claim 1, characterized in that, In step S300, the rotational speed of the high-shear treatment is 2000-4000 rpm; and / or In step S400, the viscosity of the emulsion is adjusted to 20-80 mPa·s; and / or In step S400, the pH of the emulsion is adjusted to 6.8-7.

2.

9. The preparation method according to claim 1, characterized in that, The additive includes pretreated titanium dioxide; The pretreatment involves dispersing the titanium dioxide in a polyether-modified siloxane.

10. A high-temperature resistant, fully matte, high-speed spinning POY oiling agent, characterized in that, The high-temperature resistant, fully matte, high-speed spinning POY oiling agent is prepared using the preparation method described in any one of claims 1-9.

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