Special high-temperature-resistant antistatic oiling agent for polyphenylene sulfide spinning as well as preparation method and application thereof

Abstract

The invention discloses a special high-temperature-resistant antistatic oil agent for polyphenylene sulfide spinning as well as a preparation method and application thereof, and belongs to the technical field of chemical fiber oil agents. The oiling agent comprises a cluster dispersion formed in situ; the dispersoid is prepared by shearing and dispersing nano metal conductive particles and high-molecular polymer microspheres in high-temperature-resistant base oil consisting of tetrameric ricinoleate and nonylphenol polyoxyethylene ether at the rotating speed of 200-400rpm for 30 minutes under the conditions that the temperature is 70-80 DEG C and the absolute pressure is less than or equal to 0.05 MPa. The average hydrodynamic radius of the cluster dispersoid is 80-120nm, and the particle size increase amplitude is less than or equal to 15% after the cluster dispersoid is kept at the constant temperature of 260 DEG C for 30 minutes, so that the cluster dispersoid shows excellent high-temperature stability. The preparation method disclosed by the invention comprises three steps of oil phase construction, cluster in-situ formation and emulsifying and sizing. The oiling agent is particularly suitable for a high-temperature and high-speed spinning process of polyphenylene sulfide fibers at the spinning temperature of more than 300 DEG C and the channel temperature of 220-260 DEG C, and can effectively solve the problems of antistatic failure and oiling agent decomposition at high temperature.

Description

Technical Field

[0001] This invention belongs to the field of chemical fiber oiling technology, specifically relating to a high-temperature resistant and antistatic oiling agent for polyphenylene sulfide spinning, its preparation method, and its application. Background Technology

[0002] Polyphenylene sulfide (PPS) fiber holds an irreplaceable position in industrial textiles such as high-temperature filtration and environmental protection due to its excellent high-temperature resistance, chemical corrosion resistance, and superior mechanical strength. However, these excellent properties of PPS fiber also bring severe challenges to its spinning process. PPS resin has a melting point as high as 285℃, and its spinning process requires melting and extrusion at temperatures above 300℃, with the nascent fibers undergoing stretching and shaping in a tunnel at 220-260℃. Under these extreme high-temperature and dry conditions, conventional spinning oils have two major limitations: Firstly, it has insufficient heat resistance. Traditional oils based on mineral oil or ordinary synthetic esters are highly volatile and easily decompose under heat oxidation, causing the oil film on the fiber surface to break, resulting in a surge in fuzz and breakage rates. Furthermore, the decomposition products are prone to coking and carbonizing on equipment such as hot rollers, contaminating the spinning system and seriously affecting production continuity and product quality.

[0003] Secondly, the antistatic properties fail under high-temperature and dry conditions. PPS itself is an excellent insulator (volume resistivity > 10^15 Ω·cm), and the large amount of static charge generated by friction during high-speed spinning is difficult to dissipate. Traditional ionic surfactant-based antistatic agents (such as quaternary ammonium salts and alkyl sulfonates) generally rely on the "hygroscopic conductivity mechanism," that is, forming an ionic conductive layer on the fiber surface by absorbing ambient moisture. However, in the high-temperature and dry spinning tunnel, this mechanism completely fails, causing the fiber bundles to disperse and entangle due to electrostatic repulsion. This not only makes processing difficult but also easily attracts dust, affecting the cleanliness of the finished product.

[0004] In existing technologies, achieving high-temperature stability requires the use of oily components with stable molecular structures and high boiling points, while achieving antistatic properties often requires the introduction of polar or ionic components, the latter of which are difficult to maintain stability at high temperatures. For example, CN104032570A discloses a spinning oil that uses a cationic quaternary ammonium salt (dodecyltrimethylammonium chloride) as an antistatic agent. This component relies on a hygroscopic mechanism, and in the dry, high-temperature environment of PPS spinning, not only does its antistatic property fail, but it also undergoes thermal decomposition, leading to oil deterioration. Although CN119824580A introduces nano-antistatic components, it fails to solve the technical problem of long-term dispersion stability of nanoparticles in high-temperature oils. Nanoparticles are prone to agglomeration and sedimentation, leading to a rapid decline in antistatic performance under high-temperature processing conditions. At the same time, its formulation still contains antistatic components such as ethoxyamine hydrochloride, which are dependent on ambient humidity. Its antistatic performance is expected to decline significantly in the high-temperature, dry PPS spinning tunnel.

[0005] Therefore, there has long been a lack of a special oil agent in the field that can simultaneously meet the requirements of high-temperature long-term stability and long-term antistatic properties under the harsh conditions of PPS spinning. Summary of the Invention

[0006] The purpose of this invention is to provide a novel oil formulation that is suitable for the high-temperature conditions of PPS fiber production. Specifically, this invention provides a high-temperature resistant and antistatic oil for polyphenylene sulfide spinning, its preparation method, and its application.

[0007] In a first aspect, the present invention provides a high-temperature resistant antistatic oiling agent for polyphenylene sulfide spinning, the oiling agent containing a cluster dispersion; the cluster dispersion is formed in situ by shearing and dispersing nano-metal conductive particles and polymer microspheres at 200-400 rpm for 30 minutes under conditions of 70℃~80℃ and absolute pressure ≤0.05 MPa in a high-temperature resistant base oil containing tetrameric castor oil ester and nonylphenol polyoxyethylene ether; the average hydrodynamic radius of the cluster dispersion is 80-120 nm, and its particle size increase is ≤15% after being kept at 260℃ for 30 minutes.

[0008] This invention utilizes an in-situ formed "cluster dispersion" with polymer microspheres as spatial separators. The polar functional groups (such as anhydride / carboxyl groups) on the surface of these microspheres are anchored to the surface of conductive nanoparticles through strong interactions, forming a physical barrier between the nanoparticles. This effectively prevents direct contact and sintering of the nanoparticles at temperatures of 260°C and above. Therefore, the stability of the cluster structure at high temperatures (manifested as a particle size increase of ≤15%) directly ensures the integrity of the conductive nanonetwork, a prerequisite for the sustained and efficient performance of antistatic properties in dry, high-temperature tunnel environments. Relying on this inherently stable, physically conductive electronic network, the antistatic performance is completely independent of environmental humidity. It is precisely because of the excellent stability of the cluster structure at high temperatures that this humidity-independent antistatic mechanism can be achieved and maintained under the extreme conditions required for PPS spinning (spinning temperatures above 300°C, dry tunnels at 220-260°C).

[0009] Preferably, the weight ratio of tetrameric castor oil ester to nonylphenol polyoxyethylene ether is (35-50):(10-15). The nonyl carbon chain in nonylphenol polyoxyethylene ether (such as NP-10) has good compatibility with tetrameric castor oil ester. The interfacial film strength and steric hindrance formed by tetrameric castor oil ester at specific temperatures are key to guiding the formation of stable clusters of nanoparticles and polymer microspheres. Tetrameric castor oil ester provides an extremely high boiling point to ensure non-volatility at high temperatures, while its moderate viscosity and polarity provide an ideal hydrodynamic environment for the dispersion and cluster formation of nanocomponents.

[0010] Preferably, the weight ratio of the nano-metal conductive particles to the polymer microspheres is (5-8):(3-5). In high-temperature oil systems, to ensure antistatic properties, the nanoparticles need to be close to each other and form electron tunneling pathways. However, excessively close nanoparticles are prone to sintering and agglomeration at high temperatures, which can destroy the conductive pathways. The aforementioned ratio ensures that the nanoparticles have a sufficient concentration in the oil, allowing them to form a continuous and dense electronic conductive network when spread on the fiber surface. At the same time, the microspheres can effectively insert into and isolate the nano-conductive particles, preventing them from direct contact and high-temperature sintering. In addition, the polar functional groups (such as anhydride groups) on their surface can anchor to the particle surface, enhancing dispersion stability and enabling the oil to stably exert its antistatic effect under high-temperature conditions.

[0011] Preferably, the nano-metal conductive particles are nano-silver / silicon dioxide composite particles, wherein the nano-silver particle size is ≤50nm and the specific surface area of ​​the silicon dioxide carrier is ≥200m². 2 / g. High conductivity guarantee: Nano-silver is one of the metals with the best known conductivity. A particle size ≤50 nm ensures that the nano-silver particles have an extremely high specific surface area, allowing for the formation of more conductive contact points per unit area on the fiber surface, thus constructing an extremely efficient electronic conductive network. Simultaneously, the small particle size of nano-silver facilitates its uniform dispersion in the oil phase and makes it easy to be encapsulated and stabilized by polymer microspheres. Larger particle sizes result in greater inertia, easy sedimentation, and difficulty in being effectively spatially blocked by microspheres, making them more prone to sintering at high temperatures. The high specific surface area of ​​silica provides the carrier with enormous surface energy, enabling it to firmly load and fix the nano-silver particles, preventing their migration. The high specific surface area of ​​the nano-metal conductive particles can generate stronger hydrogen bonds or chemical interactions with the anhydride groups on the surface of the polymer microspheres, greatly enhancing the cohesion and structural stability of the "cluster dispersion".

[0012] Preferably, the surface of the polymer microspheres contains at least one polar functional group selected from carboxyl, anhydride, sulfonic acid, phosphate, hydroxyl, amino, quaternary ammonium, or epoxy groups. The surface of the polymer microspheres contains polar functional groups capable of strongly interacting with the surface of the conductive nanoparticles. These polar functional groups can effectively anchor the conductive nanoparticles to the microsphere surface through hydrogen bonds, ion-dipole bonds, coordination bonds, and even covalent bonds.

[0013] More preferably, the polymer microspheres are polymer microspheres whose surface contains at least one of carboxyl groups, acid anhydride groups, sulfonic acid groups, or phosphate ester groups.

[0014] More preferably, the polymer microspheres are polyvinyl chloride-grafted maleic anhydride microspheres with a maleic anhydride grafting rate ≥5wt%. During the in-situ formation of the clusters, the maleic anhydride groups can be partially hydrolyzed into carboxyl groups, thereby generating strong hydrogen bonds and ion-dipole interactions with the hydroxyl groups on the surface of the nano-silver / silica composite particles.

[0015] In one specific embodiment, the oil comprises, by weight percentage, the following components: 35wt.%-50wt.% tetrameric castor oil ester; 5wt.%-8wt.% nano-silver / silica composite particles; 3wt.%-5wt.% polyvinyl chloride grafted maleic anhydride microspheres; 10wt.%-15wt.% nonylphenol polyoxyethylene ether; 4wt.%-6wt.% fatty alcohol polyoxyethylene ether; 3wt.%-5wt.% high-temperature resistant additive; 15wt.%-27wt.% lubricant; 1wt.%-2.5wt.% antioxidant; 0.2wt.%-0.5wt.% pH adjuster; and the balance being deionized water.

[0016] The high-temperature resistant additive preferably includes triphenyl phosphate and calcium stearate; the lubricant is selected from at least one of lauryl oleate and polyethylene glycol monomethyl ether methacrylate; and the antioxidant is selected from liquid polymeric phenolic ester antioxidants.

[0017] Secondly, the present invention provides a method for preparing the above-mentioned oil, comprising the following steps: S1. Oil phase construction: Tetrameric castor oil ester, nonylphenol polyoxyethylene ether and high-temperature resistant additives are stirred and mixed for 30 minutes at 70-80℃ and absolute pressure ≤0.05 MPa to form a homogeneous oil phase; S2. In-situ cluster formation: Under the conditions of maintaining 70-80℃ and absolute pressure ≤0.05 MPa, nano-metal conductive particles and polymer microspheres are added to the homogeneous oil phase obtained in S1. The mixture is stirred and mixed for 30 minutes at a shear rate of 200-400 rpm to fully disperse the nano-metal conductive particles and polymer microspheres and form a cluster dispersion with an average hydrodynamic radius of 80-120 nm. S3, Emulsification and Shaping: Cool the product obtained in S2 to below 40°C, add fatty alcohol polyoxyethylene ether, pH adjuster and deionized water, and emulsify for 60 minutes under normal pressure to obtain the finished oil.

[0018] Thirdly, the present invention provides the application of the above-mentioned high-temperature resistant antistatic oil agent for polyphenylene sulfide spinning in the high-temperature and high-speed spinning process of polyphenylene sulfide fiber, wherein the spinning temperature exceeds 300°C and the tunnel temperature is 220-260°C.

[0019] The beneficial effects of this invention are as follows: 1. This invention enables the antistatic component to form a "cluster dispersion" with high-temperature stability in situ in a specific base oil through specific process parameters. This structure can effectively prevent the high-temperature agglomeration and sintering of nanoparticles, ensuring that the antistatic performance remains efficient and durable in the high-temperature and dry spinning tunnel. 3. The oiling agent of this invention is designed specifically for the harsh working conditions of PPS spinning. The high-temperature resistant base oil, antistatic components, and high-temperature resistant additives work synergistically through optimal selection and precise proportioning to ensure the thermal oxidation stability and functional integrity of the oiling agent in extreme environments above 300°C. This effectively prevents the oiling agent from decomposing and coking, significantly reduces fuzz and breakage rates, and can significantly improve product quality and production efficiency. It is suitable for the large-scale and stable production of high-end PPS fibers. Detailed Implementation

[0020] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to specific embodiments. The following embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0021] [Testing Methods and Standards] In the following embodiments and comparative examples, the performance testing methods are as follows: High-temperature stability: Thermogravimetric analysis (TGA) was used to determine the mass loss rate of the oil when it was heated from room temperature to 260°C at a certain heating rate and held at that temperature for 30 minutes under a nitrogen atmosphere.

[0022] Antistatic properties: The volume resistivity (Ω·cm) of PPS short fibers (51 mm in length) after coating with oil was measured using a high resistivity meter at a temperature of 25 ℃ and a humidity of 50%RH.

[0023] Fiber spinnability: Spinning was carried out on a small experimental spinning machine at a spinning temperature of 300 ℃ and a tunnel temperature of 240 ℃ for 4 hours. The phenomena of fuzz and breakage were observed and recorded.

[0024] Dynamic light scattering (DLS) analysis: Take the mixture sample obtained in step S2 and dilute it to 0.5 mg / mL with tetrameric ricinoleate. Measure the hydrodynamic radius of the diluted sample using a DLS instrument (Anton Paar Litesizer 500) at 25°C. Measure each sample at least three times and take the average value as the initial particle size (D0). Record the polydispersity index (PDI) calculated by the DLS instrument. A PDI < 0.3 indicates uniform distribution of micelle particles.

[0025] Undiluted original dispersion samples were placed in a high-temperature reactor or thermogravimetric analysis (TGA) furnace and heated to 260°C at a rate of 5°C / min under nitrogen protection, held at that temperature for 30 minutes, and then allowed to cool naturally to room temperature. The high-temperature treated samples were diluted to 0.5 mg / mL with tetrameric castor oil ester, and the hydrodynamic radius (D1) was measured again using DLS. The particle size growth rate α (%) was calculated as (D1 - D0) / D0 × 100%. Three batches of samples were prepared and tested independently, and the average particle size growth rate was calculated.

[0026] [Raw Material Specifications and Sources] The following list consists of the components required to carry out this invention: Tetrameric ricinoleate: Purity > 99%, Croda TOF4; Nonylphenol polyoxyethylene ether: NP-10, active ingredient content >99%; Nano silver / silicon dioxide composite particles: Brand R-SiAg-95, powder, in-situ reduced Ag on the surface of SiO2 microspheres (core-shell type), Ag loading 5wt.%, SiO2 core particle size about 200nm, Ag nanoparticle size 5-20nm, from Xi'an Ruixi Biotechnology Co., Ltd. Brand Q-SiAg, powder, mesoporous SiO2 encapsulated silver nanoparticles (mSiO2@Ag), Ag content 3 wt.%, mesoporous SiO2 particle size 80–120 nm, pore size 2–10 nm; Ag core particle size 10 nm, from Xi’an Qiyue Biotechnology Co., Ltd. Polyvinyl chloride grafted maleic anhydride microspheres: particle size 1-5μm (aggregate size), maleic anhydride grafting rate >5%, custom synthesis; Lauryl oleate: 95% purity, from Amole; Polyethylene glycol monomethyl ether methacrylate: CAS26915-72-0, item number 447951, from Sigma-Aldrich; Liquid high molecular weight phenolic ester antioxidant: active ingredient content >95%, BASF Irganox® L135; Triphenyl phosphate (TPP): Purity >99%, Lanxess Disflamoll TP (Germany); Calcium stearate: Purity >99%; Fatty alcohol polyoxyethylene ether: HLB value 13.3, Dow Chemical Tergitol® 15-S-9; Glacial acetic acid: purity >99.8%, GR grade, sourced from Sinopharm Group; Deionized water: conductivity <10μS / cm, self-made laboratory-grade pure water system (Millipore Milli-Q®).

[0027] It should be noted that the commercial sources of the raw materials listed above are only to demonstrate the availability of the raw materials and do not constitute a unique limitation on a specific brand. Any similar product that meets the above technical specifications can be used to implement this invention.

[0028] [Example 1] This embodiment provides a high-temperature resistant and antistatic oiling agent for polyphenylene sulfide spinning. By weight percentage, its composition is: 40.0% tetrameric castor oil ester, 10.0% nonylphenol polyoxyethylene ether, 5.0% nano-silver / silica composite particles (brand name R-SiAg-95), 4.0% polyvinyl chloride grafted maleic anhydride microspheres, 15.0% lauryl oleate, 7.0% polyethylene glycol monomethyl ether methacrylate, 1.5% liquid high molecular weight phenolic ester antioxidant, 2.5% triphenyl phosphate, 1.0% calcium stearate, 5.0% fatty alcohol polyoxyethylene ether, 0.3% glacial acetic acid, and deionized water to 100%.

[0029] Preparation method: S1. Oil phase construction: Tetrameric castor oil ester, nonylphenol polyoxyethylene ether, triphenyl phosphate, and calcium stearate were added to the reactor and stirred at 200 rpm for 30 minutes under the conditions of 75±5 ℃ and vacuum degree -0.09 MPa (gauge pressure) to form a homogeneous oil phase.

[0030] S2. In-situ formation of cluster dispersion: While maintaining temperature and vacuum conditions, add nano-silver / silica composite particles and polyvinyl chloride-grafted maleic anhydride microspheres to the oil phase obtained in step S1. Increase the stirring speed to 400 rpm and continue stirring for 30 minutes. Under these conditions, the nano-silver / silica composite particles and polyvinyl chloride-grafted maleic anhydride microspheres are co-dispersed, forming a cluster dispersion in situ.

[0031] S3. Emulsification and Shaping: Cool the mixture obtained in step 2 to below 40°C, add lauryl oleate, polyethylene glycol monomethyl ether methacrylate, liquid high molecular weight phenolic ester antioxidant, fatty alcohol polyoxyethylene ether, and glacial acetic acid, and stir at 500 rpm for 60 minutes under normal pressure. Then slowly add a measured amount of deionized water, emulsify for 60 minutes, and filter to obtain the finished oil.

[0032] Performance characterization test results: DLS testing was performed on the mixture obtained in step S2. The initial average hydrodynamic radius of the resulting cluster dispersion was 100±5 nm, and the polydispersity index (PDI) was 0.20. After heat treatment at 260℃ for 30 minutes, the particle size increased by 10.1%, demonstrating the excellent high-temperature stability of this structure. The oiling agent exhibited a thermogravimetric loss rate of 0.45% at 260℃, showing excellent high-temperature resistance. After treatment with this oiling agent, the volume resistivity of the PPS fiber was 7.8×10^7 Ω·cm, indicating its excellent antistatic properties. Continuous spinning tests were conducted at a spinning temperature of 300℃ and a tunnel temperature of 240℃. No fuzzing or breakage occurred within 4 hours, the fiber bundles showed good cohesion, and there was no electrostatic dispersion, fully verifying the good compatibility of this oiling agent with the high-temperature, high-speed spinning process of PPS fibers.

[0033] [Example 2] This embodiment provides a high-temperature resistant and antistatic oiling agent for polyphenylene sulfide spinning. By weight percentage, its composition is: 35% tetrameric castor oil ester, 15% nonylphenol polyoxyethylene ether, 5.5% nano-silver / silica composite particles (brand name R-SiAg-95), 3.5% polyvinyl chloride grafted maleic anhydride microspheres, 18.0% lauryl oleate, 9.0% polyethylene glycol monomethyl ether methacrylate, 1.0% liquid high molecular weight phenolic ester antioxidant, 2.0% triphenyl phosphate, 1.0% calcium stearate, 4.5% fatty alcohol polyoxyethylene ether, 0.2% glacial acetic acid, and deionized water to 100%. The preparation steps are the same as in Example 1.

[0034] DLS analysis confirmed that the initial average hydrodynamic radius of the cluster dispersion was 105±6 nm, the polydispersity index (PDI) was 0.22, and the particle size increase after high-temperature treatment at 260℃ was 12.2%. These results indicate that a stable cluster dispersion can still be formed under this formulation, and it exhibits good high-temperature stability. The thermogravimetric loss rate of the oil at 260℃ was 0.48%, demonstrating excellent high-temperature resistance. After treatment with this oil, the volume resistivity of the PPS fibers was 8.5 × 10⁻⁶. 7 The Ω·cm indicates that it still has good antistatic properties. Continuous spinning tests were conducted at a spinning temperature of 300℃ and a tunnel temperature of 240℃. No obvious fuzz or breakage was observed within 4 hours, and the processing was smooth, proving that the formulation scheme is also effective and suitable for the high-temperature production conditions of PPS fibers.

[0035] [Example 3] This embodiment provides a high-temperature resistant and antistatic oiling agent for polyphenylene sulfide spinning. By weight percentage, its composition is: 45% tetrameric castor oil ester, 12% nonylphenol polyoxyethylene ether, 7.5% nano-silver / silica composite particles (brand name R-SiAg-95), 4.5% polyvinyl chloride grafted maleic anhydride microspheres, 12.0% lauryl oleate, 6.0% polyethylene glycol monomethyl ether methacrylate, 2.0% liquid high molecular weight phenolic ester antioxidant, 3.0% triphenyl phosphate, 1.0% calcium stearate, 5.5% fatty alcohol polyoxyethylene ether, 0.3% glacial acetic acid, and deionized water to 100%. The preparation steps are the same as in Example 1.

[0036] DLS analysis confirmed that the initial average hydrodynamic radius of the cluster dispersion was 95±4 nm, the polydispersity index (PDI) was 0.18, and the particle size increase after high-temperature treatment at 260℃ was 8.7%. The cluster dispersion formed under this formulation had smaller particle size and better high-temperature stability. The thermogravimetric loss rate of the oil at 260℃ was 0.41%, demonstrating excellent high-temperature resistance. After treatment with this oil, the volume resistivity of PPS fibers was 5.2×10⁻⁶. 7The fiber exhibits excellent overall performance at Ω·cm. Continuous spinning tests were conducted at a spinning temperature of 300℃ and a tunnel temperature of 240℃. Within 4 hours, the performance remained stable, the fiber quality was excellent, and it is fully adapted to the high-temperature production conditions of PPS fibers.

[0037] [Example 4] Example 4 is based on Example 1, with the only difference being that the nano-silver / silica composite particles used are Q-SiAg (Xi'an Qiyue Biotechnology). The preparation steps are the same as in Example 1.

[0038] DLS analysis confirmed that the initial average hydrodynamic radius of the cluster dispersion was 110±7 nm, the polydispersity index (PDI) was 0.25, and the particle size increase after high-temperature treatment at 260℃ was 14.5%. The results indicate that high-temperature stable cluster dispersions conforming to the characteristics of this invention can still be successfully formed using similar raw materials that meet the requirements. The thermogravimetric loss rate of the oil at 260℃ was 0.48%; after oil treatment, the volume resistivity of PPS fibers was 1.0×10⁻⁶. 8 Ω·cm. After 4 hours of continuous spinning, there were no fuzzy or broken fibers, the fiber bundles were well-coordinated, and there was no static electricity.

[0039] [Example 5] This embodiment is based on Example 1, except that the vacuum conditions of steps S1 (oil phase construction) and S2 (in-situ cluster formation) in the preparation method are adjusted from -0.09 MPa to -0.05 MPa (gauge pressure). The rest of the formulation, raw materials and process parameters are exactly the same as those in Example 4.

[0040] Preparation method: S1. Oil phase construction: Tetrameric castor oil ester, nonylphenol polyoxyethylene ether, triphenyl phosphate, and calcium stearate were added to the reactor and stirred at 200 rpm for 30 minutes under the conditions of 80±5 ℃ and vacuum degree of -0.05 MPa (gauge pressure) to form a homogeneous oil phase.

[0041] S2, In-situ formation of cluster dispersion: Maintaining a vacuum of -0.05 MPa and temperature conditions, add nano-silver / silica composite particles (brand name Q-SiAg) and polyvinyl chloride-grafted maleic anhydride microspheres to the oil phase obtained in S1, increase the stirring speed to 400 rpm, and continue stirring for 30 minutes.

[0042] S3, Emulsification and Shaping: Same as Example 4.

[0043] Performance characterization and test results: DLS analysis confirmed that cluster dispersions could still be successfully formed under a vacuum of -0.05 MPa. The initial average hydrodynamic radius was 112±8 nm, and the polydispersity index (PDI) was 0.27. After heat treatment at 260℃ for 30 minutes, the particle size increased by 14.8%. The thermogravimetric loss rate of the oil at 260℃ was 0.50%. The volume resistivity of the treated PPS fibers was 1.1×10^8 Ω·cm. After continuous spinning at a spinning temperature of 300℃ and a tunnel temperature of 240℃ for 4 hours, no fuzzing or breakage occurred, the fiber bundles showed good cohesion, and there was no electrostatic dispersion. This example demonstrates that, under the critical conditions of the vacuum range (≤-0.05 MPa) described in this invention, cluster dispersions with good high-temperature stability can still be successfully guided to form. The resulting oil's high-temperature resistance, antistatic properties, and spinnability all meet the stringent requirements of high-temperature, high-speed spinning of PPS fibers.

[0044] [Compare with Example 1] This comparative example is based on Example 4, except that the stirring rate in steps S1, S2 and S3 is adjusted to 1200 rpm, while the other conditions remain unchanged.

[0045] Performance test results: In step S2, the excessively high shear rate led to strong mechanical impact, disrupting the structure of the "cluster dispersion." DLS testing showed that the initial average hydrodynamic radius was only 45±15 nm, and the polydispersity index (PDI) was as high as 0.45, indicating that the system was a fragmented, non-uniform dispersion rather than a homogeneous and stable cluster. After heat treatment at 260℃, the particle size increased by as much as 28.5%. The oil's thermogravimetric loss rate was 0.52%, and the volume resistivity of the PPS fibers fluctuated greatly (5.6×10^8~4.2×10^10 Ω·cm). During spinning, the filament bundles diverged, and the breakage rate increased significantly.

[0046] [Compare with Example 2] This comparative example is based on Example 4, the difference being that the vacuum degree in steps S1 and S2 is set to -0.04 MPa (i.e., the absolute pressure is about 0.06 MPa), while the other conditions remain unchanged.

[0047] Performance test results: Due to insufficient vacuum, the system contained high levels of residual oxygen and moisture. DLS testing showed an initial average hydrodynamic radius of 125±12 nm, a PDI of 0.31, and increased dispersion inhomogeneity. After heat treatment at 260℃, the nano-silver particles severely agglomerated due to oxidation and high-temperature sintering, with a particle size increase of 22.3%. The oil's thermogravimetric loss rate increased to 0.75%, and the PPS fiber volume resistivity rose to 5.8×10^9 Ω·cm. One hour after spinning, yarn breakage began to occur, and slight coking occurred on the hot rollers.

[0048] [Compare with Example 3] This comparative example is based on Example 4, the difference being that steps S1 and S2 are performed at atmospheric pressure (0.1 MPa), while the other conditions remain unchanged.

[0049] Performance test results: When heated and stirred in air, the nano-silver particles were severely oxidized by oxygen, losing their metallic conductivity and undergoing irreversible aggregation. Stable cluster dispersions could not be formed, and visible precipitation was observed after step S2. Effective DLS testing could not be performed. The oil's thermogravimetric loss rate was as high as 1.2%, and the PPS fiber volume resistivity was >1×10^13 Ω·cm (insulation state). Spinning could not proceed normally, static electricity was severe, and the fiber bundles could not be wound.

[0050] [Compare with Example 4] This comparative example is based on Example 4, the difference being that all raw materials (oil phase, antistatic component, aqueous phase component, etc.) are added to the reactor at one time and stirred at 400 rpm for 2 hours at room temperature and pressure.

[0051] Performance test results: This process is completely unable to guide the formation of "cluster dispersions". Nanoparticles and microspheres exhibit severe agglomeration and sedimentation. The final product is non-uniform, and the DLS test fails. The oil has a high thermogravimetric loss rate and poor antistatic properties (PPS fiber volume resistivity > 1 × 10^11 Ω·cm).

[0052] [Compare with Example 5] This comparative example is based on Example 4, except that: dimeric ricinoleate (99.9% purity, Ziyi Chemical) is used in an equal amount instead of tetrameric ricinoleate, while the other conditions remain unchanged.

[0053] Performance test results: Due to the small molecular weight and low boiling point of the dimer, it volatilizes violently at high temperatures. The oil agent exhibits a thermogravimetric loss rate as high as 7.5% at 260℃. Unable to form a stable oil film, PPS fibers frequently experience fuzzing and breakage during spinning due to lubrication failure. Although initial clustering is possible, the antistatic properties rapidly decline due to carrier failure.

[0054] [Compare with Example 6] This comparative example is based on Example 4, except that: hexameric ricinoleate (99.9% purity, Ziyi Chemical) is used in an equal amount instead of tetrameric ricinoleate, while the other conditions remain unchanged.

[0055] Performance test results: The excessively high viscosity of the hexamer severely hindered the diffusion and self-assembly of nanoparticles. DLS showed that the initial cluster particle size was too large (initial average hydrodynamic radius > 200 nm) and unevenly distributed (PDI > 0.4). Poor flowability at high temperatures and uneven spreading of the oil on the fiber surface resulted in poor antistatic properties (volume resistivity 3.5 × 10^9 Ω·cm) and poor spinnability.

[0056] [Compare with Example 7] This comparative example is based on Example 4, except that an equal amount of tetrameric castor oil ester is used instead of nonylphenol polyoxyethylene ether, while the other conditions remain unchanged.

[0057] Performance test results: The oil phase lacks the necessary interfacial activity and polarity, failing to effectively wet and disperse nanoparticles and microspheres, and even less able to drive the formation of cluster structures. Nanoparticles rapidly aggregate and settle, and the antistatic component separates from the system. The final product completely fails in antistatic properties (volume resistivity > 1 × 10^13 Ω·cm).

[0058] [Compare with Example 8] This comparative example is based on Example 4, except that nonylphenol polyoxyethylene ether is replaced with an equal amount of octylphenol polyoxyethylene ether (OP-10), while the other conditions remain unchanged.

[0059] Performance test results: Due to the change in carbon chain length, the hydrophilic-lipophilic balance (HLB value) changes, resulting in interfacial behavior in the oil phase that differs from nonylphenol polyoxyethylene ether. The formed "cluster dispersion" has an initially loose structure (PDI=0.35), significantly reduced high-temperature stability, and a particle size increase of 20.1% after treatment at 260℃. The durability of antistatic properties deteriorates, resistivity increases in the later stages of spinning, and the breakage rate increases.

[0060] [Compare with Example 9] This comparative example is based on Example 4, the difference being that: an equal amount of nano-silver / silica composite particles are used instead of polyvinyl chloride-grafted maleic anhydride microspheres, that is, the system does not contain polymer microspheres, but only nano-silver / silica composite particles, while the other conditions remain unchanged.

[0061] Performance test results: Due to the complete absence of the steric stabilization and interfacial anchoring effect provided by the polyvinyl chloride-grafted maleic anhydride microspheres in the system, the nano-silver / silica composite particles could not form a stable "cluster dispersion" under the high temperature and shear conditions of step S2, but instead tended to aggregate directly. DLS testing showed that the initial system was a non-uniform polydisperse system with a large and widely distributed average hydrodynamic radius (PDI>0.5). After heat treatment at 260℃, the nanoparticles underwent severe sintering due to lack of protection, resulting in a sharp increase in particle size that could not be accurately measured. The thermal weight loss rate of the oil increased to 0.70%. The volume resistivity of the PPS fiber was initially acceptable (~5.0×10^8Ω·cm), but it increased rapidly with the extension of the spinning time, exceeding 1×10^10Ω·cm after 30 minutes, indicating that the antistatic properties could not be sustained. The fuzz and breakage rate increased significantly in the later stages of spinning. The results indicate that without the spatial barrier and stabilizing effect of polymer microspheres, nano-conductive particles alone cannot maintain a stable conductive network at high temperatures.

[0062] [Compare with Example 10] This comparative example is based on Example 4, except that an equal amount of pure silver nanoparticles are used instead of silver nanoparticles / silicon dioxide composite particles, while the other conditions remain unchanged.

[0063] Performance test results: Pure silver nanoparticles lack the stabilizing and isolating effect of the silica carrier, and irreversible severe agglomeration occurs at the high temperature of step S2. An effective conductive network cannot be formed, and the agglomerates lead to uneven oil distribution. The volume resistivity of PPS fibers reaches as high as 2.5 × 10^10 Ω·cm, with large fluctuations, indicating instability during the spinning process.

[0064] The comparative examples 1-10 above fully demonstrate that the specific process steps and parameters of the present invention (such as stepwise feeding, appropriate shear rate, and specific vacuum degree) and the specific components and their proportions are indispensable keys to forming a high-temperature stable "cluster dispersion" and achieving excellent comprehensive performance. Any deviation from the process or core components will lead to a significant decrease in system performance or even complete failure.

[0065] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A high-temperature resistant antistatic oiling agent for polyphenylene sulfide spinning, characterized in that: The oil contains clustered dispersions; The cluster dispersion is formed in situ by shearing and dispersing nano-metal conductive particles and polymer microspheres in a high-temperature resistant base oil containing tetrameric castor oil ester and nonylphenol polyoxyethylene ether for 30 minutes at a speed of 200-400 rpm under conditions of 70℃~80℃ and absolute pressure ≤0.05 MPa. The average hydrodynamic radius of the cluster dispersion is 80-120 nm, and its particle size increase is ≤15% after being kept at 260℃ for 30 minutes.

2. The high-temperature resistant antistatic oiling agent for polyphenylene sulfide spinning according to claim 1, characterized in that: The weight ratio of the tetrameric castor oil ester and nonylphenol polyoxyethylene ether is (35-50):(10-15).

3. The high-temperature resistant antistatic oiling agent for polyphenylene sulfide spinning according to claim 1, characterized in that: The weight ratio of the nano-metal conductive particles to the polymer microspheres is (5-8):(3-5).

4. The high-temperature resistant antistatic oiling agent for polyphenylene sulfide spinning according to claim 3, characterized in that: The nano-metal conductive particles are silver / silicon dioxide composite particles, wherein the diameter of the silver nanoparticles is ≤50 nm and the specific surface area of ​​the silicon dioxide carrier is ≥200 m². 2 / g.

5. The high-temperature resistant antistatic oiling agent for polyphenylene sulfide spinning according to claim 1, characterized in that: The polymer microspheres are polyvinyl chloride grafted maleic anhydride microspheres with a maleic anhydride grafting rate of ≥5 wt.%.

6. The high-temperature resistant and antistatic oiling agent for polyphenylene sulfide spinning according to claim 1, characterized in that, By weight percentage, it includes the following components: Tetrameric ricinoleate 35wt.%-50wt.%; Nano silver / silicon dioxide composite particles 5wt.%-8wt.%; PVC-grafted maleic anhydride microspheres 3wt.%-5wt.%; Nonylphenol polyoxyethylene ether 10wt.%-15wt.%; Fatty alcohol polyoxyethylene ether 4wt.%-6wt.%; High-temperature resistant additives 3wt.%-5wt.%; Lubricant 15wt.%-27wt.%; Antioxidant 1wt.%-2.5wt.% pH adjuster 0.2wt.%-0.5wt.%; The remainder is deionized water.

7. The high-temperature resistant antistatic oiling agent for polyphenylene sulfide spinning according to claim 6, characterized in that: The high-temperature resistant additives include triphenyl phosphate and calcium stearate.

8. A method for preparing a high-temperature resistant antistatic oiling agent for polyphenylene sulfide spinning as described in any one of claims 1-7, characterized in that, Includes the following steps: S1. Oil phase construction: Tetrameric castor oil ester, nonylphenol polyoxyethylene ether and high-temperature resistant additives are stirred and mixed for 30 minutes at 70-80℃ and absolute pressure ≤0.05 MPa to form a homogeneous oil phase; S2. In-situ cluster formation: Under the conditions of maintaining 70-80℃ and vacuum degree ≤0.05 MPa, nano-metal conductive particles and polymer microspheres are added to the homogeneous oil phase obtained in S1. The mixture is stirred and mixed for 30 minutes at a shear rate of 200-400 rpm to fully disperse the nano-metal conductive particles and polymer microspheres and form a cluster dispersion with an average hydrodynamic radius of 80-120 nm. S3, Emulsification and Shaping: Cool the product obtained in S2 to below 40°C, add fatty alcohol polyoxyethylene ether, pH adjuster and deionized water, and emulsify for 60 minutes under normal pressure to obtain the finished oil.

9. The application of the high-temperature resistant antistatic oil agent for polyphenylene sulfide spinning as described in any one of claims 1-7 in the high-temperature and high-speed spinning process of polyphenylene sulfide fibers, characterized in that, The spinning temperature exceeds 300℃, and the tunnel temperature is between 220-260℃.