High-heat-stability, antistatic and wear-resistant polyester fdy oil and its preparation method

Abstract

The present application belongs to the technical field of spinning aids, and particularly relates to a polyester FDY oil agent with high thermal stability, antistatic property and wear resistance and a preparation method thereof, which comprises the following steps: putting smoothing agent, bundling agent, antistatic agent and emulsifier into a reaction kettle according to mass ratio, heating to 35-60 DEG C, keeping warm for 30-60 min under stirring, cooling to below 23 DEG C, then putting in composite anti-wear and friction-reducing agent, stirring uniformly to obtain the polyester FDY oil agent; wherein the preparation process of the composite anti-wear and friction-reducing agent comprises the following steps: (I) preparing nano-porous titanium dioxide TiO2; (II) filling inorganic hydrated salt phase change materials into the pores of the nano-porous titanium dioxide TiO2 to obtain TiO2 / IHSPCM; (III) grafting poly-N-isopropyl acrylamide on the surface of TiO2 / IHSPCM to obtain TiO2 / IHSPCM@PNIPAM; (IV) coating conductive polymer and amphiphilic branched polymer onto the outer surface of TiO2 / IHSPCM@PNIPAM to obtain the composite anti-wear and friction-reducing agent; the polyester FDY oil agent has good thermal stability, antistatic property and wear resistance.

Description

Technical Field

[0001] This invention belongs to the field of spinning auxiliaries technology, and particularly relates to a polyester FDY oil agent with high thermal stability, antistatic properties and abrasion resistance, and its preparation method. Background Technology

[0002] Polyester is a fiber-forming polymer, polyethylene terephthalate (PET), produced from purified terephthalic acid (PTA) or dimethyl terephthalate (DMT) and ethylene glycol (MEG) through esterification or transesterification followed by polycondensation. PET is then spun and post-processed to create fibers. It is currently the world's largest-volume and most widely used synthetic fiber. However, because synthetic fibers lack the natural gums and oil films found in natural fibers, oiling agents must be used during spinning to reduce fuzz and breakage during high-speed spinning, thereby lowering costs, saving energy, and improving product quality.

[0003] The spinning process generates high temperatures, leading to changes in the viscosity of the oil, decreased film-forming properties, and even coking. To mitigate the adverse effects of high temperatures on the oil, those skilled in the art have explored adding phase change materials (PCMs) to spinning oils. These PCMs utilize the endothermic phase change of the PCMs to improve the temperature rise and decreased lubrication performance during spinning. Generally, due to the ease with which PCMs undergo phase changes and their poor compatibility with oil components, they are often added to the oil in the form of microcapsules. This approach optimizes the high-temperature resistance of the oil and also utilizes the "ball bearing" effect of the PCM microcapsules during lubrication to reduce fiber friction and improve the oil's wear resistance.

[0004] Currently, the structures of phase change microcapsules added to spinning oils mainly fall into two categories: one is the adsorption type, which uses a porous material filled with phase change material as the inner core and a polymer or other material as the outer shell. The advantages of this type of phase change microcapsule are high impact strength and good wear resistance, but it suffers from a low content of phase change material. The other type is the encapsulated type, which uses a phase change material as the inner core and an inorganic precipitate or polymer as the outer shell. In contrast to the adsorption type, the advantages of this type are high content of phase change material and good temperature regulation effect. However, due to the lack of internal support, the encapsulated type has low impact strength and poor wear resistance, and is prone to breakage during use.

[0005] To develop a phase change microcapsule more suitable for spinning oils and improve their thermal stability and abrasion resistance, the applicant previously filed a patent application with publication number CN119041058B entitled "FDY Oil for Direct Oiling from Crude Oil and its Preparation Method." This patent application disclosed a spinning oil containing modified encapsulated phase change microcapsules. The microcapsule has a paraffin core and a film layer formed by polyurethane, graphite, and nano-silica as its outer shell. This paraffin-core encapsulated phase change microcapsule has a high content of phase change material. Simultaneously, the paraffin is protected by encapsulation with silica, and the use of polyurethane and silica composites results in a more uniform and dense wall material, while also improving compatibility with the organic phase. Test results also show that this phase change microcapsule using an organic / inorganic composite material as its outer shell can stably operate in the oil. The oil prepared by the fixed dispersion exhibits stable performance, low friction coefficient, and good lubrication effect after long-term use. However, this phase change microcapsule still suffers from the inherent disadvantages of encapsulated phase change microcapsules, and its impact strength and wear resistance still need to be improved. The oil prepared by this method is suitable for ordinary FDY spinning (winding speed 4000~6000m / min), but for ultra-high-speed FDY spinning (winding speed ≥6000~8000m / min), the rapidly increasing pressure at the oiling point will generate continuous high pressure on the oil coating. The large difference in linear speed between adjacent guide rollers (up to 300~600m / min), high fiber impact frequency (>30kHz) and strong vibration, and high friction surface sliding speed are all changes in the operating environment. As a result, the phase change microcapsules in the oil are prone to rupture and cannot be used as an oil for ultra-high-speed FDY spinning.

[0006] Furthermore, during ultra-high-speed FDY spinning, the contact frequency between the filament bundle and the guiding device, cooling airflow, and upstream and downstream rollers increases significantly. Frictional heat generation and electron transfer effects are pronounced, and a large amount of static charge easily accumulates on the filament bundle surface. In a high-static environment, the filament bundles tend to repel each other, leading to uneven dispersion of monofilaments and the formation of "filament bundling" or "cohesion." This also causes filament bundle misalignment, localized shrinkage, and increases the rate of filament breakage, fuzzing, and end breakage. Therefore, improving the antistatic ability of the spinning oil is also crucial for ultra-high-speed FDY spinning.

[0007] In view of this, the present invention provides a polyester FDY oiling composition with high thermal stability, antistatic properties and abrasion resistance suitable for ultra-high speed FDY spinning. Summary of the Invention

[0008] The purpose of this invention is to address the aforementioned technical problems by providing a polyester FDY oil agent with high thermal stability, antistatic properties, and abrasion resistance, as well as its preparation method.

[0009] In view of this, the present invention provides a method for preparing a polyester FDY oiling agent with high thermal stability, antistatic properties, and abrasion resistance, the preparation method comprising:

[0010] S100, according to the mass ratio, add 60-90 parts of smoothing agent, 5-12 parts of bridging agent, 6-15 parts of antistatic agent, and 22-27 parts of emulsifier into the reaction vessel;

[0011] S200, the reactor is heated to 35~60℃, kept at this temperature for 30~60min under stirring, then cooled to below 23℃, and then 15~25 parts of composite anti-wear and friction reducing agent are added. After stirring for 20~30min, the polyester FDY oil is obtained.

[0012] The preparation process of the composite anti-wear and friction-reducing agent is as follows:

[0013] (I) Preparation of nanoporous titanium dioxide (TiO2);

[0014] (II) Inorganic hydrated salt phase change material is filled into the pores of nanoporous titanium dioxide TiO2 obtained in step (I) to obtain TiO2 / IHSPCM;

[0015] (III) Grafting poly-N-isopropylacrylamide onto the surface of TiO2 / IHSPCM yields TiO2 / IHSPCM@PNIPAM;

[0016] (IV) The conductive polymer and the amphiphilic branched polymer are coated onto the outer surface of TiO2 / IHSPCM@PNIPAM to obtain the composite anti-wear and friction reducing agent.

[0017] Furthermore, step (I) includes:

[0018] First, take 500-800 parts by weight of deionized water, and add 50-100 parts by weight of oxalic acid and 200-300 parts by weight of anhydrous ethanol dropwise to the deionized water while stirring. After stirring until the mixture is homogeneous, slowly add 5-10 parts by weight of tetrabutyl titanate to the mixture. After stirring until homogeneous, place the mixture under a pressure of 0.5-1 MPa and a temperature of 150-200℃ for 3-5 hours. After the reaction is completed, centrifuge, wash and dry the precipitate to obtain nanoporous titanium dioxide TiO2.

[0019] Furthermore, step (I) also includes:

[0020] Nanoporous titanium dioxide (TiO2) was dispersed in deionized water and slurried to prepare a dispersion with a TiO2 content of 200-400 g / L. Then, a certain amount of sodium silicate solution was added to the dispersion, wherein the amount of sodium silicate solution added was 0.1-0.3 wt% based on SiO2 / TiO2. After stirring evenly, the mixture was heated to 50-70℃, and tin sulfate, antimony sulfate solution, and sodium hexametaphosphate were added to prepare a mixed system with a tin sulfate content of 30-50 g / L, an antimony sulfate content of 50-80 g / L, and a sodium hexametaphosphate content of 0.2-0.5 g / L. After being kept at this temperature and matured for 0.5-1.5 h, the mixture was filtered and dried to obtain conductive nanoporous titanium dioxide (TiO2).

[0021] Furthermore, step (II) includes:

[0022] Inorganic hydrated salt phase change material was dispersed in deionized water and heated to dissolve the phase change material, forming a liquid saturated solution of inorganic hydrated salt phase change material. Then, nanoporous titanium dioxide (TiO2) was placed in a sealed container, and a vacuum was drawn to a pressure of 0.03~0.06 MPa. The liquid saturated solution of inorganic hydrated salt phase change material was slowly added while stirring. After the addition was complete, stirring was continued for 5~10 min. Then, the vacuum was slowly released to atmospheric pressure, and the mixture was allowed to stand and impregnate at atmospheric pressure for 30~60 min. Finally, it was cooled to room temperature and filtered to obtain TiO2 / IHSPCM material.

[0023] Furthermore, the inorganic hydrated salt phase change material is selected from one or more of sodium sulfate-10 hydrate, magnesium sulfate-7 hydrate, calcium chloride-6 hydrate, and sodium thiosulfate-5 hydrate.

[0024] Furthermore, step (III) includes:

[0025] The TiO2 / IHSPCM material prepared in step (II) is dispersed in an organic solvent to form a dispersion A with a TiO2 / IHSPCM content of 5~10wt%. Then, N-isopropylacrylamide and an azo initiator are added to the dispersion A and stirred evenly. The mixture is then reacted in a constant temperature water bath at 60~80℃ for 1~2h under nitrogen protection and stirring to obtain the surface-grafted poly(N-isopropylacrylamide) material TiO2 / IHSPCM@PNIPAM.

[0026] Furthermore, the amount of N-isopropylacrylamide added is 0.1 to 0.3 times the weight of the TiO2 / IHSPCM material, and the amount of azo initiator added is 3 to 6% of the weight of N-isopropylacrylamide.

[0027] Furthermore, step (IV) includes:

[0028] The TiO2 / IHSPCM@PNIPAM material obtained in step (III) is dispersed in an aqueous solution of pyrrole to obtain dispersion A. The branched polymer is dispersed in an organic solvent, stirred, and dissolved to obtain a solution B of the branched polymer. In addition, an inorganic peroxide initiator is dispersed in water to form dispersion C. Triethylamine is dispersed in water to form a solution D of triethylamine. An antistatic agent is dispersed in water to form a solution E of the antistatic agent.

[0029] Then proceed with step one: slowly add dispersion A and dispersion C dropwise to solution E simultaneously, and stir and polymerize at below 25°C for 6-10 hours. After that, filter and wash the resulting mixture.

[0030] Then, proceed to step two: disperse the obtained solid into solution D, and add triethylamine aqueous solution dropwise to the above solution B while stirring, add an appropriate amount of crosslinking agent, react for 30-60 minutes, filter and wash to prepare the composite anti-wear and friction reducing agent.

[0031] Furthermore, in step (IV), the conductive polymer is polypyrrole, and the amphiphilic branched polymer includes a main chain and side chains, wherein the side chains are hydrophilic polymer side chains.

[0032] In addition, the present invention also provides a polyester FDY oiling agent prepared by the above-described method for preparing polyester FDY oiling agent.

[0033] The beneficial effects of this invention are:

[0034] 1. The composite anti-wear and friction-reducing agent of the present invention uses nanoporous titanium dioxide (TiO2) loaded with inorganic hydrated salt phase change material as the inner core, a water-absorbing poly(N-isopropylacrylamide) layer grafted onto the outer surface of the inner core as the intermediate buffer layer, and a composite layer of conductive polymer and amphiphilic branched polymer as the outer shell layer. It has the characteristics of high temperature resistance, antistatic properties, high strength, good dispersibility, and good anti-wear and friction-reducing properties.

[0035] 2. This invention uses inorganic hydrated salt phase change materials to replace organic phase change materials such as paraffin. The high latent heat of phase change, high efficiency of heat transfer, and rapid heat absorption of inorganic hydrated salt phase change materials improve the problem of poor heat absorption regulation effect caused by the low content of phase change materials in traditional adsorption-type phase change microcapsules with paraffin as the phase change material.

[0036] 3. In this invention, nanoporous titanium dioxide (TiO2) is selected as the carrier for inorganic hydrated salt phase change materials. Compared with other inorganic porous carriers, such as SiO2, nanoporous titanium dioxide has suitable strength and impact resistance, and can also be easily processed into conductive materials through ion doping and other methods, which greatly improves the conductivity and antistatic properties of the composite anti-wear and friction reducing agent.

[0037] 4. This invention selects PNIPAM polymer as the intermediate buffer layer. The intermediate PNIPAM layer has temperature-sensitive response characteristics. At low temperatures, it absorbs water and expands to form a soft hydrogel-like buffer layer. At high temperatures, it hydrophobically collapses, making the outer coating structure of titanium dioxide more compact and dense, shortening the heat transfer path, and improving the wear resistance and friction reduction performance of the composite anti-wear and friction reducing agent. More importantly, this temperature-dependent intermediate buffer layer can adaptively mitigate the risk of structural damage caused by severe impact and high-frequency vibration during ultra-high-speed FDY spinning under different conditions.

[0038] 5. The present invention selects a composite layer of conductive polymer and amphiphilic branched polymer as the outer shell layer, so that the prepared composite anti-wear and friction reducing agent has the advantages of good dispersion stability, antistatic properties, high strength and good anti-wear and friction reducing properties. Detailed Implementation

[0039] The technical solutions in the embodiments of this application will be clearly described below with reference to specific examples. Obviously, the described embodiments are only some, not all, of the embodiments in this application. All other embodiments obtained by those skilled in the art based on the embodiments in this application are within the scope of protection of this application.

[0040] In the description of this application, it should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments according to this application. For ease of description, techniques, methods, and devices known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques, methods, and devices should be considered part of the specification.

[0041] Unless otherwise specified, all reagents and raw materials used in this invention are commercially available. Experimental methods in the following examples that do not specify particular conditions should be performed according to conventional methods and conditions, or as selected in the product instructions.

[0042] It should be noted that, in this application, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes that element. Furthermore, it should be noted that the scope of the methods and apparatuses in the embodiments of this application is not limited to performing functions in the order shown or discussed, but may also include performing functions substantially simultaneously or in the reverse order, depending on the functions involved. For example, the described methods may be performed in a different order than described, and various steps may be added, omitted, or combined. Additionally, features described with reference to certain examples may be combined in other examples.

[0043] A method for preparing a polyester FDY oiling agent with high thermal stability, antistatic properties, and abrasion resistance, comprising the following steps:

[0044] S100, according to the mass ratio, add 60-90 parts of smoothing agent, 5-12 parts of bridging agent, 6-15 parts of antistatic agent, and 22-27 parts of emulsifier into the reaction vessel;

[0045] S200: Heat the reactor to 35-60°C, keep it at that temperature for 30-60 minutes with stirring, then cool it down to below 23°C. Then add 15-25 parts of the composite anti-wear and friction reducing agent, and continue stirring for 20-30 minutes to obtain the polyester FDY oil.

[0046] In this invention, the smoothing agent, the slub, the antistatic agent and the emulsifier are first mixed at high temperature to promote rapid and uniform mixing of the components. Then, the mixture is cooled and a composite anti-wear and friction reducing agent is added. The mixture is stirred at low temperature. After the composite anti-wear and friction reducing agent is mixed evenly with the remaining components, the polyester FDY oil with high thermal stability, antistatic properties and wear resistance described in this invention can be obtained.

[0047] Before providing a detailed description of the preparation process of the composite anti-wear and friction-reducing agent in this invention, we will first explain and describe the other raw materials used in the preparation process of FDY oil.

[0048] Smoothing agent: In the FDY oil of the present invention, the smoothing agent is mainly used to improve the smoothness of the filament bundle, making the surface of the filament bundle smoother and more delicate. It also helps to reduce the coefficient of friction between the filament bundles, thereby reducing the entanglement and knotting of the filament bundles during the production process. Exemplarily, the smoothing agent used in the present invention is selected from at least one of polyether smoothing agents, organosilicon smoothing agents (such as polydimethylsiloxane, modified silicone oil), higher fatty acid esters, white oil, mineral oil, vegetable oil, isoparaffins, and ester-silicone complexes.

[0049] Preferably, the smoothing agent contains at least 30 wt% of a polyether-based smoothing agent.

[0050] Bundling agent: In the FDY oiling agent of the present invention, the bundling agent, as a chemical auxiliary agent used in the processing of fiber materials, mainly functions to improve the cohesion between fibers, enabling the fibers to be bundled together, thereby increasing the load-bearing capacity and tensile strength of the fibers. Exemplarily, the bundling agent used in the present invention is selected from at least one of castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether, fatty acid diethanolamide, lauroyl diethanolamine, coconut oil diethanolamide, triethanolamine oleate, polyethylene glycol oleate, and polyethylene glycol laurate.

[0051] Antistatic agent: In the FDY oil of this invention, the antistatic agent is a chemical substance that can increase the conductivity of an object's surface and prevent the accumulation of static electricity. Its main function is to increase the conductivity of the material surface, allowing static charge to dissipate in a timely manner and preventing static electricity from affecting production. Exemplarily, the antistatic agent used in this invention is selected from at least one of lauryl polyoxyethylene ether, sodium secondary alkyl sulfonate, alkyl alcohol phosphate, alkyl alcohol sulfonate, alkyl alcohol sulfate, alkyl alcohol ether sulfate salt, and alkyl alcohol ether carboxylate.

[0052] Emulsifier: In the FDY oil formulation of this invention, the emulsifier is a surfactant containing both hydrophilic and lipophilic groups in its molecule. Its main function is to reduce the interfacial tension of the components in the mixture, forming a more robust film or electric double layer on the surface of the microdroplets, preventing the microdroplets from agglomerating, thereby maintaining a uniform emulsion. Exemplarily, the emulsifier used in this invention is selected from at least one of sorbitan fatty acid ester, polyethylene glycol fatty acid ester, castor oil polyoxyethylene ether, cashew phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether, and sodium lauryl ether sulfate.

[0053] Preferably, the emulsifier includes 30-50 wt% cashew phenol polyoxyethylene ether.

[0054] It should be noted that those skilled in the art are capable of selecting and adjusting the specific raw materials and their component contents of the smoothing agent, clustering agent, antistatic agent, and emulsifier according to actual needs. The selection of the above raw materials and their components in this invention is a preferred scheme adapted to the composite anti-wear and friction-reducing agent of this invention. The preparation process of the composite anti-wear and friction-reducing agent of this invention will be described in detail below.

[0055] The composite anti-wear and friction-reducing agent of this invention uses nanoporous titanium dioxide (TiO2) loaded with inorganic hydrated salt phase change material as the inner core, a water-absorbing poly(N-isopropylacrylamide) layer grafted onto the outer surface of the inner core as the intermediate buffer layer, and a composite layer of conductive polymer and amphiphilic branched polymer as the outer shell layer. It has the characteristics of high temperature resistance, antistatic properties, high strength, good dispersibility, and good anti-wear and friction-reducing properties.

[0056] The preparation process of the composite anti-wear and friction-reducing agent is as follows:

[0057] (I) Preparation of nanoporous titanium dioxide (TiO2);

[0058] (II) Inorganic hydrated salt phase change material is filled into the pores of nanoporous titanium dioxide TiO2 obtained in step (I) to obtain TiO2 / IHSPCM;

[0059] (III) Grafting poly-N-isopropylacrylamide onto the surface of TiO2 / IHSPCM yields TiO2 / IHSPCM@PNIPAM;

[0060] (IV) The conductive polymer and the amphiphilic branched polymer are coated onto the outer surface of TiO2 / IHSPCM@PNIPAM to obtain the composite anti-wear and friction reducing agent.

[0061] As is known, inorganic hydrated salt phase change materials refer to inorganic salts containing water of crystallization. During heat absorption or release, they undergo phase change through the binding or release of this water of crystallization, thereby achieving energy storage or temperature control. Inorganic hydrated salt phase change materials are characterized by high latent heat of phase change, the ability to release / absorb a large amount of heat per unit mass of the material, high energy storage efficiency, low cost, and abundant resources. More importantly, the common phase change temperatures of inorganic hydrated salt phase change materials are 20–160°C, which is well-suited to the temperature regulation requirements of spinning oils. Furthermore, compared to organic phase change materials, such as paraffin wax, inorganic hydrated salt phase change materials have higher thermal conductivity, higher thermal transfer efficiency, and faster heat absorption rates, making them particularly suitable for environments requiring rapid temperature regulation through phase change heat absorption, such as the high-speed and ultra-high-speed spinning processes described in this application.

[0062] To address the shortcomings of traditional adsorption-type phase change microcapsules, such as low phase change material content and poor heat absorption, this invention uses inorganic hydrated salt phase change materials to replace organic phase change materials like paraffin. The high latent heat of phase change, efficient heat transfer, and rapid heat absorption of inorganic hydrated salt phase change materials improve the poor heat absorption regulation caused by the low phase change material content in traditional adsorption-type phase change microcapsules using paraffin as the phase change material.

[0063] Based on this, the present invention selects nanoporous titanium dioxide (TiO2) as the carrier for inorganic hydrated salt phase change materials. Compared with other inorganic porous carriers, such as SiO2, nanoporous titanium dioxide not only has suitable strength and impact resistance, but can also be easily processed into conductive materials through ion doping and other methods, which greatly improves the conductivity and antistatic properties of the composite anti-wear and friction reducing agent.

[0064] As some examples of the present invention, the resistance of nanoporous titanium dioxide (TiO2) can be reduced and its conductivity improved by doping it with metals, non-metals, or other methods.

[0065] Furthermore, step (I) includes:

[0066] First, take 500-800 parts by weight of deionized water, and add 50-100 parts by weight of oxalic acid and 200-300 parts by weight of anhydrous ethanol dropwise to the deionized water while stirring. After stirring until the mixture is homogeneous, slowly add 5-10 parts by weight of tetrabutyl titanate to the mixture. After stirring until homogeneous, place the mixture under a pressure of 0.5-1 MPa and a temperature of 150-200℃ for 3-5 hours. After the reaction is completed, centrifuge, wash and dry the precipitate to obtain nanoporous titanium dioxide TiO2.

[0067] As some examples of the present invention, nanoporous titanium dioxide (TiO2) can be doped in the following manner to improve its conductivity. Specifically, step (I) includes:

[0068] First, take 500-800 parts by weight of deionized water, and add 50-100 parts by weight of oxalic acid and 200-300 parts by weight of anhydrous ethanol dropwise to the deionized water while stirring. After stirring until the mixture is homogeneous, slowly add 5-10 parts by weight of tetrabutyl titanate to the mixture. After stirring until homogeneous, place it under a pressure of 0.5-1 MPa and a temperature of 150-200℃ for 3-5 hours. After the reaction is completed, centrifuge and wash the precipitate to obtain nanoporous titanium dioxide TiO2.

[0069] Nanoporous titanium dioxide (TiO2) was dispersed in deionized water and slurried to prepare a dispersion with a TiO2 content of 200-400 g / L. Then, a certain amount of sodium silicate solution was added to the dispersion, wherein the amount of sodium silicate solution added was 0.1-0.3 wt% based on SiO2 / TiO2. After stirring evenly, the mixture was heated to 50-70℃, and tin sulfate, antimony sulfate solution, and sodium hexametaphosphate were added to prepare a mixed system with a tin sulfate content of 30-50 g / L, an antimony sulfate content of 50-80 g / L, and a sodium hexametaphosphate content of 0.2-0.5 g / L. After being kept at this temperature and matured for 0.5-1.5 h, the mixture was filtered and dried to obtain conductive nanoporous titanium dioxide (TiO2).

[0070] In the conductive modification process of nanoporous titanium dioxide (TiO2), the addition of sodium silicate aims to deposit silica particles on the surface of the nanoporous TiO2, stabilizing its structure and preventing agglomeration and collapse. Simultaneously, the deposited silica particles exhibit strong surface compatibility, not only improving the surface chemical environment of the nanoporous TiO2 and enhancing the uniformity and binding force of subsequent tin and antimony doping, but also providing an interfacial transition zone for the multilayer structure of subsequent phase change microcapsules, thus improving the integrity of the outer structure. Furthermore, silica particles can also act as nucleating agents in inorganic hydrated salt phase change materials, promoting nucleation and crystallization.

[0071] Based on this, in step (II), inorganic hydrated salt phase change material is filled into the pores of nanoporous titanium dioxide TiO2 by negative pressure impregnation adsorption to obtain TiO2 / IHSPCM.

[0072] Furthermore, the inorganic hydrated salt phase change material is a solid-liquid phase change material.

[0073] Preferably, the inorganic hydrated salt phase change material is selected from one or more of sodium sulfate-10 hydrate, magnesium sulfate-7 hydrate, calcium chloride-6 hydrate, and sodium thiosulfate-5 hydrate.

[0074] More preferably, the inorganic hydrated salt material can be improved by combining existing technologies, such as adding nucleating agents, thickeners, sugar alcohols, solid amines, etc., to optimize the crystallization ability of the inorganic hydrated salt material, inhibit liquid phase separation, reduce material flow, and adjust the phase transition temperature.

[0075] It should be noted that those skilled in the art are capable of selecting and adjusting the specific composition of inorganic hydrated salt materials according to actual needs and in combination with existing technologies, and this invention will not elaborate on this further.

[0076] Specifically, step (II) includes:

[0077] Inorganic hydrated salt phase change material was dispersed in deionized water and heated to dissolve it, forming a liquid saturated solution of inorganic hydrated salt phase change material. Then, nanoporous titanium dioxide (TiO2) was placed in a sealed container, and a vacuum was drawn to a pressure of 0.03~0.06 MPa. The liquid saturated solution of inorganic hydrated salt phase change material was slowly added while stirring. After the addition was complete, stirring was continued for 5~10 min. Then, the vacuum was slowly released to atmospheric pressure, and the mixture was allowed to stand and impregnate for 30~60 min under atmospheric pressure. After cooling to room temperature, the mixture was filtered, and excess water was removed at a low temperature below 25°C to obtain TiO2 / IHSPCM material.

[0078] Preferably, the amount of liquid saturated solution of the inorganic hydrated salt phase change material added is 5 to 10 times the weight of nanoporous titanium dioxide (TiO2).

[0079] As some examples of the present invention, in step (II), the process of removing excess moisture at low temperature specifically involves placing the filtered TiO2 / IHSPCM material in a low-temperature environment below 25°C, spreading it evenly, and then letting it stand and dry for 1 to 2 days.

[0080] After obtaining the inner core of the phase change microcapsule, this invention further utilizes poly-N-isopropylacrylamide grafted onto the surface of TiO2 / IHSPCM to form an intermediate buffer layer. The specific operation process is as follows:

[0081] Step (III): The TiO2 / IHSPCM material prepared in step (II) is dispersed in an organic solvent to form a dispersion A with a TiO2 / IHSPCM content of 5~10wt%. Then, N-isopropylacrylamide and an azo initiator are added to the dispersion A. The amount of N-isopropylacrylamide added is 0.1~0.3 times the weight of the TiO2 / IHSPCM material, and the amount of the azo initiator added is 3~6% of the weight of N-isopropylacrylamide. After stirring evenly, the mixture is reacted in a constant temperature water bath at 60~80℃ for 1~2h under nitrogen protection and stirring to obtain the surface-grafted poly(N-isopropylacrylamide) material TiO2 / IHSPCM@PNIPAM.

[0082] As some examples of the present invention, the organic solvent is anhydrous ethanol.

[0083] As is known, poly(N-isopropylacrylamide) (PNIPAM) contains hydrophilic amide groups and hydrophobic isopropyl groups in its structure, exhibiting "hydrophilic-hydrophobic responsiveness". It has obvious temperature-sensitive phase transition characteristics. In water below the LCST (lower critical dissolution temperature, generally around 31~33℃), PNIPAM can hydrophilically absorb water and swell to form a hydrogel structure. Above the LCST, the LCST hydrophobically collapses and shrinks due to water displacement, showing obvious volume changes.

[0084] For the composite anti-wear and friction reducing agent in this invention, since the poly-N-isopropylacrylamide layer is coated on the surface of the TiO2 / IHSPCM inner core, during the preparation of the composite anti-wear and friction reducing agent, the PNIPAM polymer on the surface of TiO2 / IHSPCM@PNIPAM will be able to absorb water and swell, forming a soft intermediate buffer layer around the inner core formed by TiO2 / IHSPCM. When the temperature is below LCST, the hydrogel formed by the water absorption and swelling of PNIPAM is filled with water, forming a soft and tough "cushion layer", which can provide vibration damping and protection for the inner TiO2 / IHSPCM inner core, preventing the inner core from breaking under strong impact and effectively buffering external impact and friction. At high temperatures, the PNIPAM polymer undergoes hydrophobic collapse, especially under the salting-out effect of the inorganic hydrated salts adsorbed in the TiO2 / IHSPCM core. The PNIPAM polymer near the core will first undergo hydrophobic collapse, squeezing out the water inside and forming a dense network structure. Subsequently, since the pores in TiO2 have been filled by the adsorption of inorganic hydrated salts, and the water permeability of the dense network structure formed by the PNIPAM polymer is extremely low, it can achieve a strong barrier effect. The water released after the PNIPAM collapses is difficult to penetrate back into the internal pores of the nanoporous titanium dioxide TiO2 filled with phase change material. It mainly remains between the PNIPAM layer in the composite anti-wear and friction reducing agent and the outer shell. On the one hand, it acts as a liquid high-efficiency heat transfer medium between the outer shell and the core, promoting heat transfer to the inorganic hydrated salt phase change material and promoting the phase change heat absorption. On the other hand, the PNIPAM polymer layer and water layer filled between the core and the outer shell can also play a role in vibration reduction and protection of the core. Meanwhile, some of the water released after the PNIPAM collapses is discharged through the tiny pores in the outer shell layer formed by the conductive polymer and the amphiphilic polymer, permeating into the outside and being released into the oil matrix. This reduces the thickness of the intermediate buffer layer and shortens the heat transfer distance, while preventing a large amount of water from being retained and causing the microcapsule structure to expand and rupture.

[0085] Furthermore, the intermediate buffer layer formed by PNIPAM polymer in this invention not only provides shock protection for the inner core, but also isolates and seals the inorganic hydrated salts inside, reducing the possibility of leakage.

[0086] Thus, by setting the poly-N-isopropylacrylamide layer, a certain space is reserved between the hard inner core and the hard outer shell layer, and a buffer medium is filled in to form a functional buffer structure. Ultimately, the buffer medium absorbs external impact energy, alleviates the direct collision between the hard inner core and the outer shell layer, improves the impact resistance of the composite anti-wear and friction reducing agent, and extends the service life and application range of the composite anti-wear and friction reducing agent.

[0087] In addition, this intermediate buffer layer, which is mainly formed by adsorbed water, is not only easy to prepare and simple to operate, but also has a greater heat transfer capacity than most inorganic materials and polymers. Therefore, it is beneficial to quickly transfer heat to the phase change material in the core.

[0088] After preparing the poly(N-isopropylacrylamide) intermediate buffer layer, the present invention prepares the outer shell layer of the composite anti-wear and friction-reducing agent by the following method:

[0089] Step (IV): Disperse the TiO2 / IHSPCM@PNIPAM material obtained in step (III) in an aqueous solution of pyrrole to obtain dispersion A. Disperse the branched polymer in an organic solvent, stir and dissolve it to obtain solution B of the branched polymer. In addition, disperse the inorganic peroxide initiator in water to form dispersion C. Disperse triethylamine in water to form solution D of triethylamine. Disperse the antistatic agent in water to form solution E of the antistatic agent. Set aside for later use.

[0090] Then proceed with step one: slowly add dispersion A and dispersion C dropwise to solution E simultaneously, and stir and polymerize at below 25°C for 6-10 hours. After that, filter and wash the resulting mixture.

[0091] Then, proceed to step two: disperse the obtained solids into solution D, and add triethylamine aqueous solution dropwise to the above solution B while stirring. Add an appropriate amount of crosslinking agent, and after solution assembly and chemical crosslinking reaction for 30-60 minutes, filter and wash to prepare the composite anti-wear and friction reducing agent.

[0092] In the preparation of the outer shell layer of the composite anti-wear and friction-reducing agent, the amount of pyrrole added is 0.1 to 0.3 times the weight of the TiO2 / IHSPCM@PNIPAM material, and the content of pyrrole in the aqueous solution of pyrrole is 5 to 13 wt%; the amount of inorganic peroxide initiator added is 0.1 to 0.3 times the amount of pyrrole added, preferably, the inorganic peroxide initiator is ammonium persulfate.

[0093] Furthermore, the amount of branched polymer added is 0.2 to 0.4 times the weight of TiO2 / IHSPCM@PNIPAM material, and the concentration of the branched polymer solution B is 10 to 20 wt%.

[0094] As some examples of the present invention, the crosslinking agent is 1,10-diiododecane, and the amount of the crosslinking agent added is 0.3 to 0.5 times the weight of the branched polymer.

[0095] Preferably, the concentration of the triethylamine aqueous solution is 1~2 mol / L, and the amount of triethylamine aqueous solution added is 40~60 times the weight of the branched polymer.

[0096] As examples of the present invention, the antistatic agent is selected from one or more of quaternary ammonium salt antistatic agents, polyether antistatic agents, ester antistatic agents, etc. The amount of the antistatic agent added is 0.1 to 0.2 times the weight of the TiO2 / IHSPCM@PNIPAM material, and the concentration of the antistatic agent in solution E is 5 to 10 wt%.

[0097] Preferably, before performing the above operation one, the pH value of the antistatic agent solution E can be adjusted to below 6 using an acidic solution such as hydrochloric acid.

[0098] As a preferred example of the present invention, in step (IV), operations one and two can be divided into 2 to 3 segments according to the reaction time, and one segment of operations one and two can be performed alternately. Taking 3 segments as an example, the specific process is as follows:

[0099] First, all the TiO2 / IHSPCM@PNIPAM materials can be dispersed in 1 / 3 of an aqueous solution of pyrrole to obtain dispersion A. Then, dispersion A and 1 / 3 of dispersion C are simultaneously added dropwise to 1 / 3 of solution E, and the mixture is stirred and polymerized at below 25°C for 2-3 hours. After that, the resulting mixture is filtered and washed. This is the first step in operation one.

[0100] The resulting mixture was then filtered and washed. The resulting solid was dispersed into 1 / 3 of solution D. Triethylamine aqueous solution was then added dropwise to 1 / 3 of solution B under stirring. 1 / 3 of the crosslinking agent was added. After solution assembly and chemical crosslinking reaction for 10-20 minutes, the mixture was filtered and washed to obtain the solid. This is the first part of operation two.

[0101] The obtained solid was then dispersed again in a 1 / 3 pyrrole aqueous solution to obtain dispersion A, and the second part of operation one was performed in the same manner as the first part, followed by the second part of operation two.

[0102] By repeating the above operations one and two alternately three times, the alternation of operations one and two can be completed.

[0103] Preferably, in step (IV), the conductive polymer is polypyrrole.

[0104] Preferably, the amphiphilic branched polymer includes a main chain and side chains, wherein the side chains are hydrophilic polymer side chains, and the side chains are branched onto the main chain.

[0105] As some examples of the present invention, the main chain is a diblock copolymer, wherein one block is a polymer chain capable of forming a multi-arm bonded structure, and the other block is a polymer chain constituting a chemically cross-linked structure.

[0106] As some examples of the present invention, the polymer chains constituting the multi-arm bonded structure are glycidyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, etc., and the polymer chains constituting the chemical crosslinking structure are poly(N,N-diethylaminomethyl methacrylate).

[0107] As some examples of the present invention, the main chain of the amphiphilic branched polymer can be prepared by free radical polymerization, controlled free radical polymerization or anionic polymerization.

[0108] Preferably, the polymer chain constituting the multi-arm bonded structure is polyglycidyl acrylate, wherein the degree of polymerization of the polyglycidyl acrylate is 20-30, and the degree of polymerization of the poly(N,N-diethylaminomethacrylate) is 30-50.

[0109] As some examples of the present invention, the side chains of the diblock copolymer are composed of one or more of polyethylene glycol, polyvinyl alcohol, and polyethylene glycol monomethyl ether, preferably polyethylene glycol.

[0110] In addition, unless otherwise specified, "parts" in this invention generally refers to parts by weight.

[0111] The composite anti-wear and friction-reducing agent prepared by the method described in this invention has a core-shell structure. It consists of porous inorganic particles filled with phase change material as the inner core and a conductive outer shell formed by a composite polymer material. Furthermore, the outer surface of the porous inorganic particles is grafted with poly(N-isopropylacrylamide), and the poly(N-isopropylacrylamide) absorbs water to form a soft intermediate buffer layer. This composite anti-wear and friction-reducing agent has the following characteristics:

[0112] First, the core of the composite anti-wear and friction reducing agent provided by the present invention is a titanium dioxide-based nanoporous structure, which has high mechanical strength and rigid support, and can effectively avoid the problems of lack of support, poor impact resistance and easy breakage of traditional encapsulated phase change microcapsules.

[0113] Second, after filling with hydrated salt phase change materials, the high latent heat of phase change of inorganic hydrated salts is used to enhance the heat absorption capacity. At the same time, the dense network structure formed by the hydrophobic shrinkage and collapse of the poly-N-isopropylacrylamide layer at high temperature is used to encapsulate and block the phase change material, thereby reducing the risk of leakage of the phase change material.

[0114] Third, the intermediate PNIPAM layer has temperature-sensitive response characteristics. At low temperatures, it absorbs water and expands to form a soft hydrogel-like buffer layer, while at high temperatures, it hydrophobically collapses, making the outer coating structure of titanium dioxide more compact and dense, improving the heat transfer path, and enhancing the wear resistance and friction reduction performance of the composite anti-wear and friction-reducing agent. More importantly, this changing intermediate buffer layer can mitigate the risk of structural damage caused by severe impacts and high-frequency vibrations during ultra-high-speed FDY spinning under different conditions.

[0115] Fourth, the inner core uses conductive titanium dioxide as the matrix material and is coated with conductive polymer material on the outer layer. At the same time, antistatic additives are introduced into the outer shell, which can effectively improve the antistatic performance of composite anti-wear and friction reducing agent and FDY oil, alleviate static electricity accumulation on the surface of the fiber bundle, improve the problems of "coupling", "cohesion" and fiber misalignment in high static environment, and improve the quality of finished fiber and production stability.

[0116] Fifth, the amphiphilic branched polymer shell has both hydrophilic and lipophilic end groups, which is beneficial to the synergistic effect of the composite anti-wear and friction reducing agent and traditional oil components, and can also improve the dispersion stability of the composite anti-wear and friction reducing agent in the oil.

[0117] In summary, the composite anti-wear and friction reducing agent of this invention combines wear resistance, thermal stability, antistatic properties, and adaptive buffering capacity, breaking through the limitations of traditional single-coating or adsorption-type microcapsules. It is suitable for the harsh ultra-high-speed FDY spinning environment and has broad application prospects in the production of high-strength, low-failure-rate fibers.

[0118] The following specific examples illustrate the high thermal stability, antistatic properties, and abrasion resistance of the polyester FDY oiling agent and its preparation method described in this invention:

[0119] Example 1

[0120] Preparation of composite anti-wear and friction-reducing agent sample 1:

[0121] (I) First, take 1 kg of deionized water and add 150 mg of oxalic acid and 500 mg of anhydrous ethanol dropwise to the deionized water while stirring. After stirring until the mixture is homogeneous, slowly add 20 mg of tetrabutyl titanate to the mixture. After stirring until homogeneous, place it under a pressure of 0.5 MPa and a temperature of 200 °C for 4 h to react. After the reaction is completed, centrifuge, wash and dry the precipitate to obtain nanoporous titanium dioxide TiO2.

[0122] (II) The inorganic hydrated salt phase change material is dispersed in deionized water and heated to dissolve it, forming a liquid saturated solution of the inorganic hydrated salt phase change material for later use. Then, 3g of nanoporous titanium dioxide (TiO2) is placed in a sealed container and the pressure inside the container is evacuated to 0.03MPa. Under stirring, 30g of the liquid saturated solution of the inorganic hydrated salt phase change material is slowly added. After the addition is complete, stirring is continued for 5min. Then, the vacuum is slowly released to atmospheric pressure and the mixture is allowed to stand and soak for 60min under atmospheric pressure. Then, it is cooled to room temperature, filtered, and dried at low temperature to obtain TiO2@LPCM material. The inorganic hydrated salt phase change material includes 30wt% sodium sulfate-10 hydrate, 65wt% magnesium sulfate-7 hydrate, and 5wt% sorbitol.

[0123] (III) Disperse 5g of the TiO2 / IHSPCM material prepared in step (II) into 120mL of anhydrous ethanol to form dispersion A with a TiO2 / IHSPCM content of 5wt%. Then, add 0.5g of N-isopropylacrylamide and 15mg of azo initiator to dispersion A, stir evenly, and react in a constant temperature water bath at 80℃ for 1h under nitrogen protection and stirring to obtain TiO2 / IHSPCM@PNIPAM material with surface grafted polyN-isopropylacrylamide.

[0124] (IV) Disperse 5g of the TiO2 / IHSPCM@PNIPAM material obtained in step (III) in 10mL of a 5wt% pyrrole aqueous solution to obtain dispersion A. Disperse 1g of the branched polymer in an organic solvent, stir and dissolve it to obtain a 10wt% solution B of the branched polymer. In addition, disperse 0.05g of an inorganic peroxide initiator in water to form dispersion C. Disperse triethylamine in water to form a 60mL solution D of 1mol / L triethylamine. Disperse 0.5g of an antistatic agent in 10mL of water to form a solution E of the antistatic agent for later use.

[0125] Then proceed with operation one: slowly add dispersion A and dispersion C dropwise to solution E simultaneously, and stir and polymerize at below 25°C for 8 hours. After that, filter and wash the resulting mixture.

[0126] Then, proceed to step two: disperse the obtained solid into solution D, and add triethylamine aqueous solution dropwise to the above solution B under stirring, add 0.3g of crosslinking agent, react at room temperature for 60min, filter and wash to prepare the composite anti-wear and friction reducing agent.

[0127] Example 2

[0128] Preparation of composite anti-wear and friction-reducing agent sample 2:

[0129] (I) First, take 1 kg of deionized water and add 180 mg of oxalic acid and 600 mg of anhydrous ethanol dropwise to the deionized water while stirring. After stirring until the mixture is homogeneous, slowly add 20 mg of tetrabutyl titanate to the mixture. After stirring until homogeneous, place it under a pressure of 0.9 MPa and a temperature of 150 °C for 5 h. After the reaction is completed, centrifuge, wash and dry the precipitate to obtain nanoporous titanium dioxide TiO2.

[0130] (II) The inorganic hydrated salt phase change material is dispersed in deionized water and heated to dissolve it, forming a liquid saturated solution of the inorganic hydrated salt phase change material for later use. Then, 3g of nanoporous titanium dioxide (TiO2) is placed in a sealed container and the pressure inside the container is evacuated to 0.05MPa. Under stirring, 20g of the liquid saturated solution of the inorganic hydrated salt phase change material is slowly added. After the addition is complete, stirring is continued for 10min. Then, the vacuum is slowly released to atmospheric pressure and the material is allowed to stand and soak under atmospheric pressure for 50min. Then, it is cooled to room temperature, filtered, and dried at low temperature to obtain TiO2@LPCM material. The inorganic hydrated salt phase change material includes 30wt% sodium sulfate-10 hydrate, 65wt% magnesium sulfate-7 hydrate, and 5wt% sorbitol.

[0131] (III) Disperse 5g of the TiO2 / IHSPCM material prepared in step (II) into 120mL of anhydrous ethanol to form dispersion A with a TiO2 / IHSPCM content of 5wt%. Then, add 1g of N-isopropylacrylamide and 50mg of azo initiator to dispersion A, stir evenly, and react in a constant temperature water bath at 60℃ for 2h under nitrogen protection and stirring to obtain TiO2 / IHSPCM@PNIPAM material with surface grafted polyN-isopropylacrylamide.

[0132] (IV) Disperse 5g of the TiO2 / IHSPCM@PNIPAM material obtained in step (III) in 10mL of a 5wt% pyrrole aqueous solution to obtain dispersion A. Disperse 2g of the branched polymer in an organic solvent, stir and dissolve it to obtain a 10wt% solution B of the branched polymer. In addition, disperse 0.15g of an inorganic peroxide initiator in water to form dispersion C. Disperse triethylamine in water to form a 100mL solution D of 1mol / L triethylamine. Disperse 0.5g of an antistatic agent in 10mL of water to form a solution E of the antistatic agent for later use.

[0133] Then proceed with operation one: slowly add dispersion A and dispersion C dropwise to solution E simultaneously, and stir and polymerize at below 25°C for 6 hours. After that, filter and wash the resulting mixture.

[0134] Then, proceed to step two: disperse the obtained solid into solution D, and add triethylamine aqueous solution dropwise to the above solution B while stirring, add 1g of crosslinking agent, react at room temperature for 30 minutes, filter and wash to prepare the composite anti-wear and friction reducing agent.

[0135] Example 3

[0136] Preparation of composite anti-wear and friction-reducing agent sample 3:

[0137] The only difference between this and Example 1 above is that, after obtaining nanoporous titanium dioxide (TiO2), the nanoporous titanium dioxide (TiO2) was further subjected to conductive modification treatment according to the following process:

[0138] Nanoporous titanium dioxide (TiO2) was dispersed in deionized water and slurried to prepare a dispersion with a TiO2 content of 300 g / L. Then, a certain amount of sodium silicate solution was added to the dispersion, wherein the amount of sodium silicate solution added was 0.2% based on the SiO2 / TiO2 ratio. After stirring evenly, the mixture was heated to 70°C, and tin sulfate, antimony sulfate solution, and sodium hexametaphosphate were added to prepare a mixed system with a tin sulfate content of 40 g / L, an antimony sulfate content of 60 g / L, and a sodium hexametaphosphate content of 0.3 g / L. After being kept at this temperature and allowed to mature for 1 hour, the mixture was filtered and dried to obtain conductive nanoporous titanium dioxide (TiO2).

[0139] Example 4

[0140] Preparation of composite anti-wear and friction-reducing agent sample 4:

[0141] The only difference between this and Embodiment 1 is that in step (IV), operation one and operation two are performed alternately in three segments, the specific process of which is as follows:

[0142] First, all the TiO2 / IHSPCM@PNIPAM materials can be dispersed in 1 / 3 of an aqueous solution of pyrrole to obtain dispersion A. Then, dispersion A and 1 / 3 of dispersion C are simultaneously added dropwise to 1 / 3 of solution E, and the mixture is stirred and polymerized at below 25°C for 2.5 h. After that, the resulting mixture is filtered and washed. This is the first step in operation one.

[0143] The resulting mixture was then filtered and washed. The resulting solid was dispersed into 1 / 3 of solution D. Triethylamine aqueous solution was then added dropwise to 1 / 3 of solution B under stirring, and 1 / 3 of crosslinking agent was added. After 20 minutes of solution assembly and chemical crosslinking reaction, the mixture was filtered and washed to obtain the solid. This is the first part of operation two.

[0144] The obtained solid was then dispersed again in a 1 / 3 pyrrole aqueous solution to obtain dispersion A, and the second part of operation one was performed in the same manner as the first part, followed by the second part of operation two.

[0145] By repeating the above steps one and two three times in a cyclical manner, the composite anti-wear and friction-reducing agent sample 3 can be obtained.

[0146] Comparative Example 1

[0147] Preparation of composite anti-wear and friction-reducing agent sample 5:

[0148] The only difference between this and Example 1 is that step (II) is omitted, and step (IV) is performed directly after the TiO2 / IHSPCM material is prepared.

[0149] Experimental Example 1

[0150] First, the composite anti-wear and friction reducing agent samples 1-5 were weighed at room temperature of 23℃, and the particle size of the composite anti-wear and friction reducing agent samples 1-5 was detected to obtain their weight and particle size in the initial state.

[0151] The prepared composite anti-wear and friction reducing agent samples 1-5 were placed in an oven at 80℃ and dried for 2 hours. Then, the composite anti-wear and friction reducing agent samples 1-5 were weighed and the particle size of the composite anti-wear and friction reducing agent samples 1-5 was detected to obtain their weight and particle size after hydrophobic collapse of PNIPAM polymer at a temperature higher than LCST.

[0152] Then, the dried composite anti-wear and friction reducing agent samples 1-5 were placed together in a constant temperature and humidity chamber at 23℃ and 90%RH to absorb water for 2 hours. After that, the composite anti-wear and friction reducing agent samples 1-5 were weighed and the particle size of the composite anti-wear and friction reducing agent samples 1-5 was detected to obtain their weight and particle size after PNIPAM polymer absorbs water and swells at a temperature below LCST.

[0153] The test results are detailed in Table 1 below:

[0154]

[0155] Based on the above test results, compared with the initial state, the weight and particle size of composite anti-wear and friction reducing agent samples 1-4 all decreased significantly, while the weight and particle size of composite anti-wear and friction reducing agent sample 5 changed relatively little. Compared with the weight and particle size of the composite anti-wear and friction reducing agent after the hydrophobic collapse of PNIPAM polymer at a temperature higher than LCST, the weight and particle size of composite anti-wear and friction reducing agent samples 1-4 after the PNIPAM polymer absorbed water and swelled at a temperature lower than LCST showed a significant rebound. This indicates that the intermediate buffer layer formed by PNIPAM polymer in the composite anti-wear and friction reducing agent provided by the present invention has the ability to form a soft and tough "cushion layer" after absorbing water and swelling at a temperature lower than LCST. At the same time, at a temperature higher than LCST, PNIPAM polymer can lose water and collapse, shortening and optimizing the heat transfer path, and at the same time, it can play a role in vibration reduction and protection of the inner core.

[0156] Example 6

[0157] Preparation of polyester FDY oil samples 1-5:

[0158] This embodiment prepared a series of FDY oil samples 1 to 5. The raw material components used in the preparation process of the FDY oil are detailed in Table 2 below, and the specific preparation process is as follows:

[0159] Based on the sources of phase change wear-resistant agents in Table 2, and according to the mass ratio of smoother: clustering agent: antistatic agent: emulsifier: composite wear-resistant and friction-reducing agent = 80:10:10:25:20, 60wt% of polyether smoother + 40% of mineral oil smoother, coconut oil diethanolamide clustering agent, lauryl alcohol polyoxyethylene ether antistatic agent, and 50wt% of cashew phenol polyoxyethylene ether + 50wt% of castor oil polyoxyethylene ether emulsifier were added to the reaction vessel.

[0160] The reaction vessel is heated to 45°C and kept at that temperature for 50 minutes with stirring. Then, it is cooled to below 23°C. The composite anti-wear and friction reducing agent is then added and stirred for 30 minutes to obtain the polyester FDY oil.

[0161]

[0162] Example 7

[0163] Preparation of polyester FDY oil sample 6:

[0164] To make a horizontal comparison of the performance of composite anti-wear and friction reducing agents, we took the phase change wear-resistant agent sample 1 from Example 1 of the applicant's earlier patent application with publication (announcement) number CN119041058B, and prepared the oil sample 6 according to the polyester FDY oil sample preparation method in Example 6 above.

[0165] Performance testing:

[0166] The performance parameters of FDY oil samples 1-6 are shown in Table 3 below. The dynamic friction coefficient and oil application rate were obtained after using FDY oil samples 1-6 at the same spinning position for 15 and 25 days, respectively, with spinning speeds of 4800 m / min and 65000 m / min, a spinning oil emulsion concentration of 10 wt%, and a GR2 temperature of 135℃.

[0167] The method for detecting smoke emission is as follows: weigh 10 grams of sample into a 50 ml beaker, place the beaker in an electric heating mantle for continuous heating, and observe the amount of smoke emitted.

[0168] The method for detecting coking properties is as follows: 1.0 ml of sample is dropped onto a steel sheet, the steel sheet is placed in an oven at 220°C and heated for 3 minutes, and the coking properties of the sample are observed after cooling to 25°C.

[0169] The method for detecting the loss on volatilization is as follows: take 2 grams of sample and place it in a 50 ml beaker. Place the beaker in an oven at 200°C and heat it for 2 hours. Cool it to 25°C, weigh it, and calculate the amount of volatilization of the sample.

[0170] The method for detecting the open flash point shall be in accordance with GB / T3536.

[0171] The conductivity was tested by adding oil sample 1 to deionized water to prepare an emulsion with an oil content of 90 wt%, and then testing it according to GB / T11007.

[0172]

[0173] The test results above show that the FDY oil obtained by the technical solution of the present invention has stable performance, good antistatic properties, low friction coefficient, and longer-lasting lubrication effect after long-term use. It also has a longer service life under high temperature conditions and stable performance under ultra-high speed spinning conditions.

[0174] The embodiments of this application have been described above. Unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other. This application is not limited to the specific implementation methods described above. The specific implementation methods described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of this application without departing from the spirit and scope of the claims, and all of these forms are within the protection scope of this application.

Claims

1. A process for preparing a high-heat-stability, antistatic, and wear-resistant polyester FDY oil agent, characterized in that, The preparation method includes: S100, according to the mass ratio, add 60-90 parts of smoothing agent, 5-12 parts of bridging agent, 6-15 parts of antistatic agent, and 22-27 parts of emulsifier into the reaction vessel; S200, the reactor is heated to 35~60℃, kept at this temperature for 30~60min under stirring, then cooled to below 23℃, and then 15~25 parts of composite anti-wear and friction reducing agent are added. After stirring for 20~30min, the polyester FDY oil is obtained. The preparation process of the composite anti-wear and friction-reducing agent is as follows: (I) Preparation of nanoporous titanium dioxide (TiO2); (II) Inorganic hydrated salt phase change material is filled into the pores of nanoporous titanium dioxide TiO2 obtained in step (I) to obtain TiO2 / IHSPCM; (III) Grafting poly-N-isopropylacrylamide onto the surface of TiO2 / IHSPCM yields TiO2 / IHSPCM@PNIPAM; (IV) The conductive polymer and the amphiphilic branched polymer are coated onto the outer surface of TiO2 / IHSPCM@PNIPAM to obtain the composite anti-wear and friction reducing agent; Step (II) includes: Inorganic hydrated salt phase change material was dispersed in deionized water and heated to dissolve the phase change material, forming a liquid saturated solution of inorganic hydrated salt phase change material. Then, nanoporous titanium dioxide (TiO2) was placed in a sealed container, and a vacuum was drawn to a pressure of 0.03~0.06 MPa. The liquid saturated solution of inorganic hydrated salt phase change material was slowly added while stirring. After the addition was complete, stirring was continued for 5~10 min. Then, the vacuum was slowly released to atmospheric pressure, and the material was allowed to stand and impregnate for 30~60 min under atmospheric pressure. Finally, it was cooled to room temperature and filtered to obtain TiO2 / IHSPCM material. Step (III) includes: The TiO2 / IHSPCM material prepared in step (II) is dispersed in an organic solvent to form a dispersion A with a TiO2 / IHSPCM content of 5~10wt%. Then, N-isopropylacrylamide and an azo initiator are added to the dispersion A and stirred evenly. The mixture is then reacted in a constant temperature water bath at 60~80℃ for 1~2h under nitrogen protection and stirring to obtain the surface-grafted poly(N-isopropylacrylamide) material TiO2 / IHSPCM@PNIPAM. Step (IV) includes: The TiO2 / IHSPCM@PNIPAM material obtained in step (III) is dispersed in an aqueous solution of pyrrole to obtain dispersion A. The branched polymer is dispersed in an organic solvent, stirred, and dissolved to obtain a solution B of the branched polymer. In addition, an inorganic peroxide initiator is dispersed in water to form dispersion C. Triethylamine is dispersed in water to form a solution D of triethylamine. An antistatic agent is dispersed in water to form a solution E of the antistatic agent. Then proceed with step one: slowly add dispersion A and dispersion C dropwise to solution E simultaneously, and stir and polymerize at below 25°C for 6-10 hours. After that, filter and wash the resulting mixture. Then, proceed to step two: disperse the obtained solid into solution D, and add triethylamine aqueous solution dropwise to the above solution B while stirring, add an appropriate amount of crosslinking agent, react for 30-60 minutes, filter and wash to prepare the composite anti-wear and friction reducing agent.

2. The method of preparing polyester FDY oil agent according to claim 1, characterized in that, Step (I) includes: First, take 500-800 parts by weight of deionized water, and add 50-100 parts by weight of oxalic acid and 200-300 parts by weight of anhydrous ethanol dropwise to the deionized water while stirring. After stirring until the mixture is homogeneous, slowly add 5-10 parts by weight of tetrabutyl titanate to the mixture. After stirring until homogeneous, place the mixture under a pressure of 0.5-1 MPa and a temperature of 150-200℃ for 3-5 hours. After the reaction is completed, centrifuge, wash and dry the precipitate to obtain nanoporous titanium dioxide TiO2.

3. The method of preparing polyester FDY oil agent according to claim 2, characterized in that, Step (I) further includes: Nanoporous titanium dioxide (TiO2) was dispersed in deionized water and slurried to prepare a dispersion with a TiO2 content of 200-400 g / L. Then, a certain amount of sodium silicate solution was added to the dispersion, wherein the amount of sodium silicate solution added was 0.1-0.3 wt% based on SiO2 / TiO2. After stirring evenly, the mixture was heated to 50-70℃, and tin sulfate, antimony sulfate solution, and sodium hexametaphosphate were added to prepare a mixed system with a tin sulfate content of 30-50 g / L, an antimony sulfate content of 50-80 g / L, and a sodium hexametaphosphate content of 0.2-0.5 g / L. After being kept at this temperature and matured for 0.5-1.5 h, the mixture was filtered and dried to obtain conductive nanoporous titanium dioxide (TiO2).

4. The method of preparing polyester FDY oil agent according to claim 1, characterized in that, The inorganic hydrated salt phase change material is selected from one or more of sodium sulfate-10 hydrate, magnesium sulfate-7 hydrate, calcium chloride-6 hydrate, and sodium thiosulfate-5 hydrate.

5. The method of preparing polyester FDY oil agent according to claim 1, characterized in that, The amount of N-isopropylacrylamide added is 0.1 to 0.3 times the weight of TiO2 / IHSPCM material, and the amount of azo initiator added is 3 to 6% of the weight of N-isopropylacrylamide.

6. The method of preparing polyester FDY oil agent according to claim 1, characterized in that, In step (IV), the conductive polymer is polypyrrole, and the amphiphilic branched polymer includes a main chain and side chains, wherein the side chains are hydrophilic polymer side chains.

7. The polyester FDY oiling agent prepared according to the preparation method of any one of claims 1-6.

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