Cationic antistatic POY oiling agent and preparation method thereof

Abstract

The invention provides a cationic antistatic POY (Polyester Pre-Oriented Yarn) oil agent and a preparation method thereof, and the preparation method comprises the following steps: preparing a water phase from raw materials including an emulsifier, a shear thickener and polyethylene glycol; the preparation method comprises the following steps: preparing an oil phase from raw materials including a smoothing agent, a cationic antistatic agent and a bundling agent; dropwise adding the oil phase into the water phase, and uniformly emulsifying to obtain a POY oiling agent; wherein the shear thickening agent is modified silicon dioxide nanoparticles which are respectively modified by a silane coupling agent KH-550 and an acrylic acid copolymer. The POY oiling agent provided by the invention adopts the cationic antistatic agent, so that the fibers can obtain long-term and better antistatic property, and the cost is low. The POY oil agent is also added with silicon dioxide, so that the POY oil agent can maintain the viscosity temperature under the conditions of high temperature and high shear force, and the POY oil agent is stable in emulsion system and not easy to precipitate.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical materials, and in particular, to a cationic antistatic POY spinning finish and a preparation method thereof. Background Art

[0002] Polyester is polyethylene terephthalate (PET) prepared from purified terephthalic acid (PTA) or dimethyl terephthalate (DMT) and ethylene glycol (MEG) through esterification or transesterification reactions followed by a polycondensation reaction, and then the PET is made into fibers through spinning and post-treatment.

[0003] There are mainly several types of polyester products, namely POY (pre-oriented yarn), FDY (fully drawn yarn), and DTY (drawn textured yarn). Among them, polyester POY pre-oriented yarn is partially oriented wound yarn obtained by a high-speed spinning process (spinning speed of 3000 m / min to 3600 m / min). Due to the high orientation degree, large elongation at break, and low crystallinity of polyester POY, and its characteristics such as stable structure and good post-processing performance, it has a high market share.

[0004] Since synthetic fibers do not have the natural gums and oil films possessed by natural fibers, they have poor hygroscopicity and are non-conductive. Therefore, during the spinning process, they are prone to generating static electricity due to continuous friction. It is necessary to use additives to prevent or eliminate the accumulation of static electricity, and at the same time endow the fibers with properties such as softness and smoothness to enable them to pass through the subsequent processes smoothly. Such additives are collectively referred to as fiber spinning finishes.

[0005] POY spinning finish is an indispensable chemical additive in the production process of polyester pre-oriented yarn. It is mainly used to improve the spinnability, antistatic property, smoothness, and subsequent processing performance of fibers. POY spinning finish is usually compounded from multiple functional components, and mainly includes the following components: smoothing agent, antistatic agent, emulsifier, bundling agent, and some modifying components. Silicon dioxide is a commonly used modifying component in POY spinning finish, and its functions include: improving the wear resistance of the spinning finish, achieving shear thickening, preventing the spinning finish from splashing, and sudden viscosity drop.

[0006] Specifically, most of the existing POY oils are water-in-oil emulsion-type polyester POY oils. Under the process conditions of high temperature and high-speed shearing, the viscosity of the POY oil will decrease, making it difficult to form a uniform oil film on the fiber surface, increasing the friction between the fiber and the equipment, and causing hairiness or breakage. The reason for the viscosity reduction of the POY oil is as follows: First, the molecular thermal motion is enhanced at high temperature, weakening the intermolecular forces (such as van der Waals forces and hydrogen bonds), resulting in increased fluidity and decreased viscosity of the oil; Second, high-speed shearing will break the emulsion droplets and destroy the emulsified state, leading to oil-water separation and a sudden drop in viscosity. Therefore, in order to control the viscosity stability of the emulsion-type polyester POY oil under the process conditions of high temperature and high-speed shearing, the existing technology usually adds silica that can achieve shear thickening to the POY oil to improve the spinning effect of the POY polyester fiber and avoid or reduce the occurrence of hairiness or breakage.

[0007] Regarding the antistatic agents in POY oil, their types include cationic antistatic agents, anionic antistatic agents, and nonionic antistatic agents. Among them, the most widely used cationic antistatic agent is the quaternary ammonium salt cationic antistatic agent, such as octadecyl dimethyl hydroxyethyl ammonium nitrate and octadecyl trimethyl ammonium chloride. The principle of the quaternary ammonium salt cationic antistatic agent is that the cationic group of the quaternary ammonium salt adsorbs on the negatively charged fiber surface and forms a conductive layer by combining with environmental water molecules through hydrophilic groups (such as hydroxyl groups and ether bonds), significantly reducing the surface resistance. The antistatic performance of the quaternary ammonium salt cationic antistatic agent is superior to that of most anionic or nonionic antistatic agents. It not only has the advantages of less dosage and low cost, but also has a strong electrostatic attraction to the fiber, is not easy to fall off, and is resistant to multiple washings, especially suitable for industrial fibers that require long-term antistatic properties.

[0008] Through the analysis of the existing technology, it can be known that by utilizing the shear thickening effect of silica, the viscosity stability of the POY oil under high temperature and high-shear conditions can be improved, and by using cationic antistatic agents, the antistatic effect can be improved and the fiber can obtain the property of long-term antistatic. However, if it is desired to endow the POY oil with the above two advantages at the same time, the following technical problems will be faced: The surface of silica has a net negative charge, its zeta potential is negative, and the electrostatic repulsion force between it and the cationic antistatic agent is weak. Therefore, the POY oil containing both silica and cationic antistatic agent is prone to flocculation or sedimentation. In other words, for the cationic antistatic POY oil, how to use silica to keep its viscosity stable under the process conditions of high temperature and high-speed shearing and make the emulsion system stable is a technical problem that needs to be solved by those skilled in the art. Summary of the Invention

[0009] One of the problems solved by the present invention is how to provide a cationic antistatic POY oil agent that can maintain stable viscosity and stable emulsion system under process conditions of high temperature and high-speed shearing.

[0010] To solve at least one of the above problems, the present invention provides a preparation method of a cationic antistatic POY oil agent, and the preparation method includes: S100: Prepare an aqueous phase using raw materials including an emulsifier, a shear thickening agent, and polyethylene glycol; S200: Prepare an oil phase using raw materials including a smoothing agent, a cationic antistatic agent, and a bundling agent; S300: Drop the oil phase into the aqueous phase and emulsify evenly to obtain the POY oil agent; Among them, the shear thickening agent is silica nanoparticles respectively modified by a silane coupling agent KH-550 and an acrylic copolymer.

[0011] In the above technical solution, the modification method using the silane coupling agent KH-550 is as follows: S10: Prepare silica sol using an organosilicon source; S20: Drop the silane coupling agent KH-550 into the silica sol and stir; S30: Age the silica sol to obtain silica gel; S40: Perform hydrothermal treatment on the silica gel to obtain silica nanoparticles modified by the silane coupling agent KH-550.

[0012] In the above technical solution, S10 specifically includes: S1: After mixing water and ethanol evenly, add an organosilicon source and continue to mix evenly to obtain a first mixture; S2: Adjust the pH value of the first mixture to 3 to 4 and stir for 0.5 h to 1 h to obtain a silicon hydrolysis solution.

[0013] S3: Adjust the pH value of the silicon hydrolysis solution to 8 to 10 and stir again for 2 h to 3 h to obtain silica sol.

[0014] In the above technical solution, in S1, by mass, the organosilicon source: water: ethanol = (4 - 8): (30 - 40): 100.

[0015] In the above technical solution, S20 specifically includes: S121: According to the dosage of the organosilicon source in S10, weigh the silane coupling agent KH-550 and disperse it evenly in ethanol to prepare a coupling agent solution; S122: Drop the coupling agent solution into the silica sol and stir evenly simultaneously.

[0016] In the above technical solution, in S121, by mass ratio, silane coupling agent KH-550: organosilicon source = (0.004 - 0.008):1; and / or in S121, the concentration of the coupling agent solution is 10wt% to 15wt%.

[0017] In the above technical solution, S30 specifically includes: soaking the silica sol in absolute ethanol for 24h to 48h for aging to obtain silica gel.

[0018] In the above technical solution, S40 specifically includes: subjecting the silica gel to hydrothermal treatment for 1.5h to 2h under a pressure condition of 2Mpa to 3.5Mpa and a temperature condition of 160°C to 180°C under closed conditions, separating the solid matter, washing, and drying to obtain silica nanoparticles modified with silane coupling agent KH-550.

[0019] In the above technical solution, the method of modification with acrylic copolymer is: mixing the silica nanoparticles modified with silane coupling agent KH-550 with an organic substance including acrylic monomer and / or acrylate monomer, and obtaining silica nanoparticles modified with acrylic copolymer through polymerization reaction under the action of an initiator.

[0020] The present invention also provides a cationic antistatic POY finish, and the POY finish is obtained by using the preparation method of any of the above technical solutions.

[0021] Beneficial effects First of all, the polyester POY finish of the present invention includes a shear thickening agent in the form of silica nanoparticles. Under the high shear conditions of POY spinning, the shear thickening agent can form a temporary "cluster structure" in the dispersion medium to hinder fluid flow, thereby increasing the viscosity of the POY finish.

[0022] Secondly, the shear thickening agent has been modified with acrylic copolymer. At low temperatures, the acrylic copolymer can absorb shear energy through deformation and prevent the silica from rubbing against each other, delaying the triggering of the thickening phenomenon. After the temperature exceeds 160°C, due to the accelerated dissolution and thermal decomposition of the acrylic copolymer, the mutual friction, van der Waals force, and hydrogen bond interaction of the silica nanoparticles are increased, so that the shear thickening agent gradually triggers the shear thickening effect above 160°C, thereby regulating the viscosity of the POY finish under high temperature and high shear force conditions and balancing the sudden drop in viscosity of the POY finish caused by the thermal decomposition of the oil phase and the intensified molecular movement.

[0023] In addition, the coating treatment of the acrylic copolymer can reduce the surface energy of the silica nanoparticles and improve their dispersion stability. Under the conditions of high temperature and high shear force, as the dissolution and thermal decomposition rates of the acrylic copolymer increase, the silica nanoparticles gradually begin to come into contact with and rub against each other. In the prior art, since the zeta potential on the surface of silica is negative and the electrostatic repulsive force between silica and the cationic antistatic agent is weak, after contacting the cationic antistatic agent, silica is prone to flocculation or sedimentation due to electrostatic interaction with the cationic antistatic agent. In order to avoid the electrostatic adsorption between silica and the cationic antistatic agent during the shear thickening process, before coating and modifying silica with the acrylic copolymer, the present invention also modifies silica with the silane coupling agent KH-550 to adjust the zeta potential on the surface of silica and enhance the electrostatic repulsive force between silica and the cationic antistatic agent. Thus, after the coating layer of the acrylic copolymer on the surface of silica dissolves and / or thermally decomposes, when the silica with a higher zeta potential comes into contact and rubs against each other, it can still maintain a relatively high electrostatic repulsive force with the cationic antistatic agent in the POY oil agent, so that silica can maintain the stability of the emulsion system and avoid demulsification during the process of playing the viscosity regulation role under the process conditions of high temperature and high-speed shear.

[0024] Finally, it should be noted that the present invention prepares silica on the nanoscale by the sol-gel method, and before the silica forms a sol and becomes a gel, the silica is modified with the silane coupling agent KH-550. Since silica has not formed a three-dimensional network before gelation, in the sol state, the silane coupling agent KH-550 can more uniformly form chemical bond bridges with silica to increase the zeta potential of silica. Detailed implementation manners

[0025] In order to make the above objects, features, and advantages of the present invention more obvious and understandable, the following detailed description of the specific embodiments of the present invention is provided.

[0026] Unless otherwise specified, the reagents and raw materials used in the present invention can be purchased through commercial channels. The experimental methods without specific conditions noted in the following examples are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0027] The POY oil agent is mainly used in the spinning production process of POY polyester. It is an essential auxiliary agent in the POY polyester spinning process, used to ensure that the POY fiber has good smoothness, bundling property, and antistatic property. Due to the high spinning speed and high spinning temperature of POY polyester, the POY oil agent must be able to maintain stable performance under the conditions of high temperature and high shear force.

[0028] For the oil agent of water-in-oil emulsion type polyester POY commonly used in the prior art, its viscosity will decrease under the process conditions of high temperature and high-speed shearing. The decrease in viscosity makes it difficult for the oil agent to form a uniform oil film on the fiber surface, increases the friction between the fiber and the equipment, and causes hairiness or breakage.

[0029] In order to control the viscosity of the water-in-oil emulsion type polyester POY oil agent to remain stable under the process conditions of high temperature and high-speed shearing, the present invention adds nano-silica to the POY oil agent as a shear thickening agent.

[0030] In addition, the present invention uses a cationic antistatic agent in the POY oil agent. Compared with anionic and non-ionic antistatic agents, the cationic antistatic agent has better antistatic effect and low cost. And the cationic antistatic agent is not easy to fall off and is resistant to multiple washes, especially suitable for industrial POY fibers that require long-term antistatic performance.

[0031] Since the pH value of the POY oil agent is close to neutral, the nano-silica shows the property of negative zeta potential in it. Therefore, the nano-silica is prone to electrostatic adsorption with the cationic antistatic agent, resulting in demulsification and precipitation.

[0032] To avoid the above problems, the present invention modifies the silica nanoparticles so that the silica nanoparticles can not only play a shear thickening role under high temperature conditions, but also remain uniformly dispersed in the POY oil agent containing the cationic antistatic agent, avoiding demulsification of the POY oil agent at high temperature.

[0033] The preparation method of the cationic antistatic POY oil agent of the present invention includes: S100. Using raw materials including an emulsifier, a shear thickening agent and polyethylene glycol, prepare an aqueous phase; S200. Using raw materials including a smoothing agent, a cationic antistatic agent, and a bundling agent, prepare an oil phase; S300. Drop the oil phase into the aqueous phase and emulsify it evenly to obtain the POY oil agent; Among them, the shear thickening agent is silica nanoparticles respectively modified by silane coupling agent KH-550 and acrylic copolymer.

[0034] In some embodiments of the present invention, S100 specifically includes: mixing the emulsifier, the shear thickening agent and polyethylene glycol evenly in water according to the mass ratio of emulsifier: shear thickening agent: polyethylene glycol: water = (14-18):(2-4):(6-8):(20-22) to prepare the aqueous phase.

[0035] In some embodiments of the present invention, S200 specifically includes: mixing a leveling agent, a cationic antistatic agent, and a bundling agent evenly according to a mass ratio of leveling agent: cationic antistatic agent: bundling agent = (34 - 40):(8 - 10):(6 - 8) to prepare an oil phase.

[0036] In some embodiments of the present invention, S300 specifically includes: dropping the oil phase heated to 65°C to 75°C into the water phase heated to 65°C to 75°C according to a mass ratio of oil phase: water phase = (90 - 110):100, adjusting the pH value to neutral, and performing ultrasonic emulsification evenly to obtain a POY oil agent.

[0037] For components such as leveling agents, emulsifiers, antistatic agents, and bundling agents, those skilled in the art can select and adjust their specific types according to actual needs. It should be noted that in order to be compatible with the cationic antistatic agent, cationic or nonionic emulsifiers, leveling agents, and bundling agents need to be used. In particular, cationic antistatic agents are strictly prohibited from being mixed with anionic surfactants such as sodium dodecylbenzenesulfonate (SDS) to avoid destroying the uniformity of the oil agent.

[0038] It can be understood that in order to improve the thermal stability of the cationic antistatic agent, graphene, carbon nanotubes, or other heat stabilizers can be added to the POY oil agent. Those skilled in the art know the addition method and addition amount of adding heat stabilizers to the POY oil agent in order to improve the thermal stability of the cationic antistatic agent.

[0039] Exemplarily, the cationic antistatic agent of the present invention can be octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate or octadecyl trimethyl ammonium chloride. Exemplarily, the leveling agent of the present invention can be pentaerythritol oleate. Exemplarily, the emulsifier of the present invention can be isomeric tridecanol polyoxyethylene ether or Tween series emulsifiers. Exemplarily, the bundling agent of the present invention can be cationized polyacrylic acid (such as PCA - 5) or polyoxyethylene castor oil (such as EL - 40) or quaternary ammonium salt modified cellulose.

[0040] It can be understood that the polyester POY oil agent of the present invention includes a shear thickening agent and polyethylene glycol. Polyethylene glycol serves as a dispersion medium for the shear thickening agent to improve the dispersion stability of the shear thickening agent. Preferably, polyethylene glycol with a higher molecular weight can be used. Polyethylene glycol with a higher molecular weight has relatively good thermal stability due to its longer molecular chain, and its thermal decomposition temperature is usually higher than 300°C, and can even reach about 400°C. The polyethylene glycol used in the examples of the present invention is PEG - 20000. It can be understood that Polyethylene glycol with a high molecular weight still has good water solubility, but its dissolution rate is relatively slow. Therefore, higher - speed stirring conditions and longer stirring time can be adopted during the preparation of the water phase to ensure complete dissolution.

[0041] Shear Thickening is a non-Newtonian fluid behavior, referring to the phenomenon that the viscosity of a material increases when it is subjected to high shear stress or shear rate. Its mechanism is related to the interaction of particles in the dispersion system. Shear thickening particles are generally silica particles. At low shear rates, the shear thickening particles are dispersed in polar or non-polar liquid media and flow freely, and the system exhibits low viscosity. When the shear rate exceeds the critical value, the frictional force or collision frequency between particles increases, resulting in the formation of temporary "cluster structures" by the particles, which hinders fluid flow, thus increasing the viscosity. In addition, at high shear rates, the hydrodynamic forces between the shear thickening particles dominate and cause the particles to be closely arranged, and this phenomenon will also increase the flow resistance.

[0042] In the textile field, liquids or colloids containing shear thickening particles are usually used to soak textiles to prepare protective equipment such as knee pads, elbow pads, helmets, bulletproof vests, etc. Shear thickening materials can also be used in the fields of automotive manufacturing, aerospace, building materials, etc., to absorb energy during collisions, or to improve the impact resistance and shock absorption performance of products.

[0043] The present invention is committed to using silica shear thickening particles, combined with other components such as smoothing agents, antistatic agents, bundling agents, emulsifiers, etc., to prepare a stable oil-in-water emulsion, which is used as a POY spinning finish, in order to utilize the shear thickening phenomenon to control the viscosity of the POY finish under high temperature and high shear force conditions, and to avoid significant viscosity changes during the use of the POY finish.

[0044] During polyester spinning, the shear rate when the polyester melt passes through the spinneret holes is usually controlled at 1×10 4 s -1 to 3×10 4 s -1 , and the temperature of polyester spinning exceeds 200 °C. The actual temperature of the POY finish during the spinning process is close to the melt temperature. The higher the temperature, the more the shear thickening particles are required to play their shear thickening role. Therefore, how to control the shear thickening particles in the POY finish to play a role under higher temperature conditions is one of the key problems to be solved by the present invention.

[0045] Regarding how to regulate the viscosity of the POY finish during the spinning process to keep it stable, the applicant conducted relevant research in its prior application with the authorized announcement number CN117702312B. In this prior application, nano-silica was prepared in a porous form. In addition to its own shear thickening property, silica mainly serves as a carrier for cellulose-based viscosity regulators, which are loaded with some cellulose reagents capable of achieving viscosity regulation (such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose). The mechanism for achieving viscosity regulation in this prior application is to control the slow release of the viscosity regulator. When the viscosity regulator in the porous structure of nano-silica is released, it can increase the viscosity of the finish. The condition for the release of this viscosity regulator is that the ethyl cellulose coating on the surface of the porous nano-silica gradually dissolves with the increase in temperature and frictional action. Limited by the dissolution characteristics of ethyl cellulose, this prior application can control the viscosity of the POY finish to remain stable at a temperature of about 100°C. However, as mentioned above, the spinning temperature of the POY finish can reach above 200°C, and the thermal stability of cellulose-based viscosity regulators and the coating film layer is relatively low. How to maintain the viscosity stability of the POY finish at high temperatures remains a problem difficult to solve in the prior art.

[0046] Therefore, the present invention adjusts the coating modification method for nano-silica particles. Compared with the prior art that uses ethyl cellulose to coat nano-silica, the present invention improves through research on the coating composition and preparation process.

[0047] The present invention uses acrylic acid monomers and / or acrylate monomers as raw materials. Under the action of an initiator, through a polymerization reaction, an acrylic copolymer film layer is coated on the surface of nano-silica particles. The present invention utilizes the characteristics that the acrylic copolymer remains stable below 160°C, and its dissolution accelerates and thermal decomposition occurs above 160°C, and uses the acrylic copolymer to coat and modify the silica shear thickening particles. The acrylic copolymer has good film-forming properties and can form a uniform and dense film material on the surface of the silica particles to limit the mutual contact and friction of the silica particles. After the temperature condition exceeds 160°C, the coating layer on the surface of the silica shear thickening particles begins to gradually decompose, thereby making the nano-silica gradually become in closer contact and more intense friction. Thus, by using its shear thickening effect, the viscosity of the aqueous phase in the POY finish gradually increases, and further balances the problem of the viscosity reduction of the finish caused by the increase in temperature and high shear force. Even, the present invention can make the POY finish maintain viscosity stability under the use condition of 200°C.

[0048] The method of modifying with an acrylic copolymer is as follows: Mix silica nanoparticles modified with silane coupling agent KH-550 with an organic substance including acrylic monomers and / or acrylate monomers, and under the action of an initiator, obtain silica nanoparticles modified with an acrylic copolymer through a polymerization reaction.

[0049] It should be noted that the present invention focuses on explaining the preparation process of a shear thickening agent that can keep the viscosity of the POY oil agent stable under high-temperature conditions. Those skilled in the art are capable of combining the shear thickening agent prepared by the present invention with other existing shear thickening agents or viscosity-temperature and viscosity-concentration regulators according to actual needs (for example, combining the present invention with the applicant's prior application CN117702312B) to obtain a POY oil agent that can maintain viscosity-temperature at about 100°C and at multiple temperature stages above 100°C.

[0050] Before coating and modifying the silica nanoparticles with an acrylic copolymer, the silica nanoparticles used in the present invention have also been modified with silane coupling agent KH-550. Silane coupling agent KH-�50 is γ-aminopropyltriethoxysilane. Silane coupling agent KH-550 can adjust the zeta potential on the surface of the silica nanoparticles and enhance the electrostatic repulsion between the silica and the cationic antistatic agent. Thus, after the acrylic copolymer coating layer on the silica surface dissolves and / or thermally decomposes, the silica with a higher zeta potential can still maintain a relatively high electrostatic repulsion with the cationic antistatic agent in the POY oil agent when in contact and friction with each other, enabling the silica to maintain the stability of the emulsion system and avoid demulsification during the process of playing a viscosity-regulating role under high-temperature and high-speed shearing process conditions.

[0051] Preferably, the present invention prepares silica on the nanoscale by the sol-gel method, and before the silica forms a sol and becomes a gel, modifies the silica with silane coupling agent KH-550. Since the silica has not yet formed a three-dimensional network before gelation, in the sol state, silane coupling agent KH-550 can more uniformly form a chemical bond bridge with the silica to increase the zeta potential of the silica.

[0052] Specifically, in the present invention, the method of modifying with silane coupling agent KH-550 is as follows: S10. Prepare a silica sol using an organosilicon source; S20. Drop silane coupling agent KH-550 into the silica sol and stir; S30. Age the silica sol to obtain a silica gel; S40. Hydrothermally treat the silica gel to obtain silica nanoparticles modified with silane coupling agent KH-550.

[0053] Among them, the organosilicon source can be tetraethyl orthosilicate or methyl decanoate. In order to achieve the uniform mixing of silane coupling agent KH-550 and silica sol, before dropping silane coupling agent KH-550, silane coupling agent KH-550 can be first dissolved and dispersed evenly in an organic solvent.

[0054] Preferably, S10 specifically includes: S1. After uniformly mixing water and ethanol, add the organosilicon source and continue to mix evenly to obtain a first mixture; S2. Adjust the pH value of the first mixture to 3 to 4 and stir for 0.5 h to 1 h to obtain a silicon hydrolysis solution.

[0055] S3. Adjust the pH value of the silicon hydrolysis solution to 8 to 10 and stir again for 2 h to 3 h to obtain silica sol.

[0056] It can be understood that the organosilicon source undergoes hydrolysis in a solution of water and ethanol in a specific ratio under acidic conditions and forms silica sol under the action of an alkaline catalyst. Among them, the acidic regulator can be an aqueous solution of citric acid, acetic acid or dilute hydrochloric acid. The alkaline regulator can be an aqueous solution of sodium hydroxide or potassium hydroxide.

[0057] Preferably, in S1, by mass ratio, organosilicon source: water: ethanol = (4 - 8): (30 - 40): 100.

[0058] In the present invention, S20 specifically includes: S121. According to the dosage of the organosilicon source in S10, weigh silane coupling agent KH-550 and disperse it evenly in ethanol to prepare a coupling agent solution; S122. Drop the coupling agent solution into the silica sol and stir evenly simultaneously.

[0059] Preferably, in S121, by mass ratio, silane coupling agent KH-550: organosilicon source = (0.004 - 0.008): 1. In S121, the concentration of the coupling agent solution is 10 wt% to 15 wt%.

[0060] After obtaining the silica sol, it is necessary to age it into a gel. In the present invention, S30 specifically includes: soaking the silica sol in absolute ethanol for 24 h to 48 h for aging to obtain silica gel.

[0061] In the present invention, S40 specifically includes: subjecting silica gel to hydrothermal treatment for 1.5 h to 2 h under a pressure condition of 2 Mpa to 3.5 Mpa and a temperature condition of 160 °C to 180 °C in a closed condition, separating the solid matter, washing, and drying to obtain silica nanoparticles modified with silane coupling agent KH-550.

[0062] After solving the technical problem of how to control the shear thickening particles in the POY oil agent to play a role under higher temperature conditions and maintain the stability of the emulsion, how to broaden the working temperature range in which the shear thickening particles play a thickening role is another key problem to be solved by the present invention.

[0063] In some embodiments of the present invention, the shear thickening agent includes a first shear thickening agent and a second shear thickening agent. Both the first shear thickening agent and the second shear thickening agent are modified with silane coupling agent KH-550 through S10 to S40. The difference between the first shear thickening agent and the second shear thickening agent is that after being modified with silane coupling agent KH-550, the first shear thickening agent is further modified with a first acrylic copolymer, and the second shear thickening agent is further modified with a second acrylic copolymer.

[0064] By separately treating with the first acrylic copolymer and the second acrylic copolymer, silica nanoparticles that release shear thickening effects under different temperature conditions can be obtained. Mixing and using these two kinds of silica nanoparticles can broaden the working temperature range in which the shear thickening particles play a thickening role. Preferably, in the shear thickening agent, by mass ratio, the first shear thickening agent: the second shear thickening agent = (150 - 200):100.

[0065] In some embodiments of the present invention, the preparation method for preparing the first shear thickening agent by modifying with the first acrylic copolymer includes: S410: Mix Tween 60 and silica nanoparticles in water according to the mass ratio of Tween 60: silica nanoparticles: water = (2 - 4):(15 - 25):100 to obtain a first suspension; S420: Under the condition of an ice-water bath, mix azobisisobutyronitrile, methacrylic acid, methyl methacrylate, and butyl acrylate in ethyl acetate according to the mass ratio of azobisisobutyronitrile: methacrylic acid: methyl methacrylate: butyl acrylate: ethyl acetate = (0.2 - 0.4):(6 - 8):(4 - 6):(16 - 20):100 to obtain a first mixed monomer; S430. Under the condition that the first mixed monomer is in an ice-water bath, the first suspension is added dropwise into the first mixed monomer at a mass ratio of the first suspension: the first mixed monomer = (40 - 60):100 and stirred synchronously. After the addition is completed, ultrasonic emulsification is carried out, and it is heated to a temperature condition of 62°C to 68°C under a protective atmosphere and kept reacting for 20 min to 1 h; S440. After the reaction is completed, it is cooled to room temperature and left to stand. The precipitate is separated, washed, and dried to obtain the first shear thickening agent.

[0066] In some embodiments of the present invention, the preparation method for obtaining the second shear thickening agent by modifying with a second acrylic copolymer includes: S510. Tween 60, silicon dioxide nanoparticles, and water are mixed in water at a mass ratio of Tween 60: silicon dioxide nanoparticles: water = (2 - 4):(15 - 25):100 to obtain a second suspension; S520. Under the condition of an ice-water bath, azobisisobutyronitrile, pentamethyldiethylenetriamine, polyethersulfone, methyl methacrylate, butyl acrylate, and dichloromethane are mixed in dichloromethane at a mass ratio of azobisisobutyronitrile: pentamethyldiethylenetriamine: polyethersulfone: methyl methacrylate: butyl acrylate: dichloromethane = (0.2 - 0.4):(0.04 - 0.08):(4 - 6):(16 - 20):(4 - 8):100 to obtain a second mixed monomer; S530. Under the condition that the second mixed monomer is in an ice-water bath, the second suspension is added dropwise into the second mixed monomer at a mass ratio of the second suspension: the second mixed monomer = (40 - 60):100 and stirred synchronously. After the addition is completed, ultrasonic emulsification is carried out, and it is heated to a temperature condition of 62°C to 68°C under a protective atmosphere and kept reacting for 20 min to 1 h; S540. After the reaction is completed, it is cooled to room temperature and left to stand. The precipitate is separated, washed, and dried to obtain the second shear thickening agent.

[0067] Among them, the silicon dioxide nanoparticles used in S410 and S510 have been modified with a silane coupling agent KH-550. The ice-water bath conditions used in S420 and S520 of the present invention are 0° to 5°. The azobisisobutyronitrile used in S420 and S520 of the present invention is an initiator. The ethyl acetate and dichloromethane used in S420 and S520 of the present invention are reaction media. The other acrylic acid or acrylate raw materials used in S420 and S520 of the present invention are monomer raw materials. The pentamethyldiethylenetriamine (PMDETA) used in S520 of the present invention is a chelating agent, and the polyethersulfone used in S520 of the present invention is used to increase the thermal decomposition temperature of the acrylic copolymer.

[0068] When formulating the first mixed monomer in the present invention, the proportion of butyl acrylate is relatively high, and the proportion of methyl methacrylate is relatively low. When formulating the second mixed monomer in the present invention, the proportion of butyl acrylate is relatively low, the proportion of methyl methacrylate is relatively high, and polyethersulfone is added. The ester side chain of methyl methacrylate is methyl, the molecular chain has strong rigidity, a relatively high glass transition temperature, and a relatively high thermal decomposition temperature. The ester side chain of butyl acrylate is a long-chain butyl group, the molecular chain is flexible, the glass transition temperature is relatively low, and the thermal decomposition temperature is relatively low. Coupled with the use of polyethersulfone, the present invention can coat two acrylic copolymers with different thermal decomposition temperatures on the surface of silica nanoparticles, and then by adjusting the addition ratio of the first shear thickening agent and the second shear thickening agent, the POY oil agent can maintain stable viscosity in a wider temperature range.

[0069] Example 1 In this example, a silica nanoparticle sample 1 was prepared, and its preparation process is as follows.

[0070] S1. According to the mass ratio of tetraethyl orthosilicate: water: ethanol = 6:33:100, after mixing water and ethanol evenly in a beaker, add tetraethyl orthosilicate and continue to mix evenly. Dropwise add citric acid to adjust the pH value to 4, stir at a speed of 200 rpm for 1 h, then dropwise add 6 wt% sodium hydroxide aqueous solution to adjust the pH value to 9 and stir again at a speed of 200 rpm for 2 h to obtain silica sol. S2. According to the mass ratio of silane coupling agent KH-550: tetraethyl orthosilicate = 0.005:1, based on the amount of tetraethyl orthosilicate in S1, weigh the silane coupling agent KH-550 and disperse it evenly in ethanol to prepare a 10 wt% coupling agent solution. Drop the coupling agent solution into the silica sol and stir evenly at a speed of 60 rpm simultaneously to obtain a silica sol mixed with the silane coupling agent KH-550. S3. Immerse the silica sol mixed with the silane coupling agent KH-550 in sufficient absolute ethanol for 24 h for aging to obtain silica gel; wherein, change the absolute ethanol every 6 h. S4. Feed the silica gel into a reaction kettle, introduce nitrogen to displace air. Under closed conditions, heat up and pressurize, and carry out isothermal and isobaric hydrothermal treatment for 2 h under the pressure condition of 2.4 Mpa and the temperature condition of 165 °C. After the hydrothermal treatment, cool down and release the pressure, stand still and cool to room temperature, separate the solid matter and wash and dry to obtain the silica nanoparticle sample 1 modified by the silane coupling agent KH-550.

[0071] Comparative Example 1 In this example, a silica nanoparticle sample 2 was prepared, and its preparation process is as follows.

[0072] S1. Mix water and ethanol evenly according to the mass ratio of ethyl silicate: water: ethanol = 6:33:100. After that, add ethyl silicate and continue to mix evenly. Dropwise add citric acid to adjust the pH value to 4, stir for 1 h, then dropwise add sodium hydroxide aqueous solution to adjust the pH value to 9 and stir again for 2 h to obtain silica sol. S2. Immerse the silica sol in sufficient absolute ethanol for 24 h for aging to obtain silica gel; wherein, replace the absolute ethanol every 6 h. S3. Feed the silica gel into a reaction kettle, introduce nitrogen to displace air. Under closed conditions, heat up and pressurize. Carry out heat treatment under pressure and heat preservation for 2 h under the pressure condition of 2.4 Mpa and the temperature condition of 165 °C. After the heat treatment under pressure and heat preservation is completed, cool down and release the pressure, stand still and cool to room temperature, separate the solid matter, wash and dry to obtain the silica nanoparticle sample 2 modified by silane coupling agent KH-550.

[0073] Example 2 In this example, shear thickening agent sample 1 was prepared, and its preparation process is as follows.

[0074] S1. Mix Tween 60 and water evenly in a beaker according to the mass ratio of Tween 60: silica nanoparticles: water = 2:15:100. Then add silica nanoparticle sample 1 and ultrasonically disperse it at a power of 200 W for 10 min to obtain the first suspension. S2. According to the mass ratio of azobisisobutyronitrile: methacrylic acid: methyl methacrylate: butyl acrylate: ethyl acetate = 0.2:8:4:20:100, first put ethyl acetate into a beaker, and under the condition of an ice-water bath, cool it down to below 4 °C. Then add methacrylic acid, methyl methacrylate and butyl acrylate to the beaker, mix and stir evenly, and then add azobisisobutyronitrile and stir evenly again to obtain the first mixed monomer. S3. Under the condition that the first mixed monomer is in an ice-water bath and below 4 °C, according to the mass ratio of the first suspension: the first mixed monomer = 40:100, use a dropper to dropwise add the first suspension into the beaker containing the first mixed monomer and stir magnetically synchronously. Among them, every time the first suspension is taken, gently stir the first suspension with a dropper to ensure uniform sampling. After the dropping is completed, ultrasonically emulsify the mixture in the beaker at a power of 600 W for more than 30 min to ensure uniform emulsification. Then transfer the mixture in the beaker to a three-necked flask, displace the air with nitrogen, and heat the three-necked flask to a temperature condition of 65 °C and keep it warm for reaction for 35 min. S4. After the reaction is completed, cool the three-necked flask to room temperature and stand still for about 2 h, centrifuge and separate the precipitate, wash and dry the precipitate to obtain shear thickening agent sample 1.

[0075] Example 3 In this example, a shear thickening agent sample 2 was prepared, and its preparation process is as follows.

[0076] S1. According to the mass ratio of Tween 60:silica nanoparticles:water = 2:15:100, mix Tween 60 and water evenly in a beaker, then add silica nanoparticle sample 1, and ultrasonically disperse it at a power of 200 W for 10 min to obtain a second suspension; S2. According to the mass ratio of azobisisobutyronitrile:penta-methyldiethylenetriamine:polyethersulfone:methyl methacrylate:butyl acrylate:dichloromethane = 0.2:0.04:4:20:6:100, first put dichloromethane into a beaker, and under the condition of an ice-water bath, cool it to below 4°C, then add penta-methyldiethylenetriamine, polyethersulfone, methyl methacrylate and butyl acrylate to the beaker. After mixing and stirring evenly, add azobisisobutyronitrile and stir evenly again to obtain a second mixed monomer; S3. Under the condition that the second mixed monomer is in an ice-water bath and below 4°C, according to the mass ratio of the second suspension:the second mixed monomer = 50:100, use a dropper to drop the second suspension into the beaker containing the second mixed monomer and stir magnetically synchronously. Among them, each time the second suspension is taken, gently stir the second suspension with a dropper to ensure uniform sampling. After dropping, ultrasonically emulsify the mixture in the beaker at a power of 500 W for more than 30 min to ensure uniform emulsification. Then transfer the mixture in the beaker to a three-necked flask. After replacing the air with nitrogen, heat the three-necked flask to a temperature of 65°C and keep it warm for 1 h; S4. After the reaction is completed, cool the three-necked flask to room temperature and let it stand for about 2 h, centrifuge to separate the precipitate, wash and dry the precipitate to obtain the shear thickening agent sample 2.

[0077] Comparative Example 2 In this example, a shear thickening agent sample 3 was prepared, and its preparation process is the same as that of Example 1, except that the silica nanoparticles added in S1 are silica nanoparticle sample 2.

[0078] Example 4 In this example, a series of POY finish samples 1 to 4 were prepared, and their preparation processes are as follows.

[0079] S1. According to the mass ratio of Tween 60:shear thickening agent:polyethylene glycol:water = 15:4:6:20, mix Tween 60, shear thickening agent and polyethylene glycol evenly in a beaker, then add water and ultrasonically disperse it at a power of 500 W for 40 min to prepare an aqueous phase; S2. Mix pentaerythritol oleate, octadecyl dimethyl hydroxyethyl ammonium nitrate, and polyoxyethylene castor oil in a beaker and stir evenly according to the mass ratio of pentaerythritol oleate: octadecyl dimethyl hydroxyethyl ammonium nitrate: polyoxyethylene castor oil = 40:8:7 to prepare the oil phase. S3. Heat the oil phase and the aqueous phase to 70 °C respectively according to the mass ratio of oil phase: aqueous phase = 1:1. Then, drop the oil phase into the aqueous phase while stirring synchronously. After dropping, adjust the pH value to neutral and ultrasonically emulsify evenly at a power of 600 W to obtain the POY oil agent.

[0080] Among them, the shear thickening agent used in POY oil agent sample 1 is shear thickening agent sample 1, the shear thickening agent used in POY oil agent sample 2 is shear thickening agent sample 2, the shear thickening agent used in POY oil agent sample 3 is shear thickening agent sample 3, and the shear thickening agent used in POY oil agent sample 4 includes shear thickening agent sample 1 and shear thickening agent sample 2, and the mass addition ratio of the two is shear thickening agent sample 1: shear thickening agent sample 2 = 3:2.

[0081] Performance Test Heat the above POY oil agent samples 1 to 4 at a speed of 18 °C / min to 20 °C / min and stir at a speed of 1500 rpm to simulate the shear friction during use. During the heating and stirring process, detect the viscosity of POY oil agent samples 1 to 4. The test results are shown in Table 1. It can be seen from Table 1 that the initial viscosities of POY oil agent samples 1 to 4 sampled at 40 °C are about 72 cP. As the temperature rises, their viscosities gradually change. Among them, in the temperature range of 120 °C to 160 °C, the viscosities of POY oil agent samples 1 to 4 decrease significantly. At about 170 °C to 180 °C, the viscosities of POY oil agent samples 1, 3, and 4 show a more obvious rise. At 190 °C to 200 °C, the viscosities of POY oil agent samples 2 and 4 show a more obvious rise.

[0082] In addition, store the samples of POY oil agent samples 1 to 4 at 10 °C for 10 days and observe their appearance. No delamination and precipitation occur in POY oil agent samples 1 to 4. After cold storage, spin the fibers using the oil agents of POY oil agent samples 1 to 4, and no obvious hairiness and broken ends are found in the POY fibers.

[0083] Finally, store the samples of POY oil agent samples 1 to 4 at 45 °C and 80% RH for 10 days and observe their appearance. No delamination and precipitation occur in POY oil agent samples 1 to 4. After high-temperature storage, spin the fibers using the oil agents of POY oil agent samples 1 to 4. Slight hairiness and broken ends occur in the POY fibers using POY oil agent sample 3, and no obvious hairiness and broken ends are found in the POY fibers using the other samples.

[0084] Table 1 Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the scope defined by the claims.

Claims

1. A preparation method of a cationic antistatic POY finish, characterized in that, The preparation method includes: S100. Prepare an aqueous phase using raw materials including an emulsifier, a shear thickening agent, and polyethylene glycol; S200. Prepare an oil phase using raw materials including a smoothing agent, a cationic antistatic agent, and a bundling agent; S300. Drop the oil phase into the aqueous phase and emulsify evenly to obtain the POY finishing agent; Among them, the shear thickening agent is silica nanoparticles respectively modified by a silane coupling agent KH-550 and an acrylic copolymer.

2. The preparation method according to claim 1, characterized in that, The method of modification using the silane coupling agent KH-550 is as follows: S10. Prepare a silica sol using an organosilicon source; S20. Drop the silane coupling agent KH-550 into the silica sol and stir; S30. Age the silica sol to obtain a silica gel; S40. Perform hydrothermal treatment on the silica gel to obtain silica nanoparticles modified by the silane coupling agent KH-550.

3. The preparation method according to claim 2, characterized in that, S10 specifically includes: S1. After mixing water and ethanol evenly, add the organosilicon source and continue to mix evenly to obtain a first mixture; S2. Adjust the pH value of the first mixture to 3 to 4 and stir for 0.5 h to 1 h to obtain a silicon hydrolysis solution; S3. Adjust the pH value of the silicon hydrolysis solution to 8 to 10 and stir again for 2 h to 3 h to obtain the silica sol.

4. The preparation method according to claim 3, characterized in that, In S1, by mass ratio, organosilicon source: water: ethanol = (4 - 8): (30 - 40):

100.

5. The preparation method according to claim 2, characterized in that, S20 specifically includes: S121. Weigh the silane coupling agent KH-550 according to the dosage of the organosilicon source in S10, disperse it evenly in ethanol, and prepare a coupling agent solution; S122. Drop the coupling agent solution into the silica sol and stir evenly synchronously.

6. According to the preparation method described in claim 5, characterized in that, In S121, by mass ratio, silane coupling agent KH-550: organosilicon source = (0.004 - 0.008): 1; and / or In S121, the concentration of the coupling agent solution is 10 wt% to 15 wt%.

7. The preparation method according to claim 2, characterized in that, S30 specifically includes: Immerse the silica sol in absolute ethanol for 24 h to 48 h to perform the aging to obtain the silica gel.

8. The preparation method according to claim 2, wherein S40 specifically includes: Under closed conditions, perform hydrothermal treatment on the silica gel at a pressure of 2 Mpa to 3.5 Mpa and a temperature of 160 °C to 180 °C for 1.5 h to 2 h, separate the solids and wash and dry to obtain the silica nanoparticles modified by the silane coupling agent KH-550.

9. The preparation method according to any one of claims 1 to 8, characterized in that The method of modification using the acrylic copolymer is: Mix the silica nanoparticles modified by the silane coupling agent KH-550 with an organic substance including acrylic monomers and / or acrylate monomers, and under the action of an initiator, obtain silica nanoparticles modified by the acrylic copolymer through a polymerization reaction.

10. A cationic antistatic POY finish, characterized in that, The POY finishing agent is obtained by the preparation method described in any one of claims 1 to 9.

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