Antistatic environment-friendly polyester DTY twisting oil agent and production process thereof

Abstract

The invention discloses an antistatic environment-friendly polyester DTY (Draw Textured Yarn) twisting oil agent and a production process thereof, and belongs to the technical field of textile assistants. The invention relates to an antistatic environment-friendly polyester DTY twisting oil agent and a production process thereof. The oil agent comprises a vegetable oil-based modified fatty acid ester main agent, a biodegradable PEG-PPG lubricant, a natural source conductive modifier, surface modified nano zinc oxide, an imidazolium ionic liquid antistatic agent, an APEO-free glycoside emulsifier, a stabilizer and deionized water. The process comprises the steps of esterification synthesis of a main agent, surface modification treatment of a water-soluble conductive agent and nano zinc oxide, and multi-phase emulsification preparation. The obtained oiling agent has excellent conductivity and antistatic performance, low friction, good storage stability and good eco-friendliness, and can be widely applied to an environment-friendly chemical fiber twisting lubricating system.

Description

Technical Field

[0001] This invention relates to the field of textile auxiliaries technology, and more specifically, to an antistatic and environmentally friendly polyester DTY twisting oil and its production process. Background Technology

[0002] Polyester textured filament (DTY) is a widely used chemical fiber material in the textile industry. It has advantages such as high strength, good elasticity and excellent dyeability, and is widely used in clothing, home textiles and industrial textiles. In the twisting process of DTY, twisting oil is usually applied in order to give the fiber good friction lubrication, antistatic, hydrophilic, film-forming and thermal stability properties. Existing commercial polyester DTY twisting oils are mostly mineral oil or its emulsions, supplemented by polyether lubricants and conventional quaternary ammonium salt antistatic agents, but they still have the following shortcomings: (1) Traditional mineral oil main agents have poor biodegradability and pose an environmental burden; (2) Petrochemical emulsifiers such as non-alkoxyphenol (APEO) are controversial for their toxicity, which is not conducive to the development of the green textile industry; (3) The antistatic performance decays quickly and it is difficult to meet the conductivity safety requirements under complex working conditions such as high-speed twisting and high-temperature false twisting.

[0003] In recent years, with the widespread adoption of green manufacturing and sustainable development concepts in textile chemicals, the development of environmentally friendly lubricants based on natural oils, bio-based or natural polymer conductive additives, and low-toxicity biodegradable emulsion systems has become a research hotspot. Some studies have attempted to introduce castor oil, chitosan, and glycoside emulsifiers into oil systems, but a mature industrial system has not yet been established in terms of stability, conductivity persistence, and emulsion microstructure control. Many related published patents fail to simultaneously address the comprehensive performance characteristics of lubrication, antistatic properties, environmental friendliness, biodegradability, and structural stability.

[0004] Therefore, there is an urgent need to develop a novel antistatic and environmentally friendly polyester DTY twisting oil system based on the synergistic effect of plant oils, natural modifiers and functional nanomaterials, to construct a green oil product with self-dispersing, self-stabilizing, low volatility and strong antistatic properties, and to develop an industrially scalable production process to meet the comprehensive requirements of future functional fiber processing for high-performance spinning auxiliaries. Summary of the Invention

[0005] The purpose of this invention is to provide an antistatic and environmentally friendly polyester DTY twisting oil and its production process. It has excellent conductivity and antistatic properties, low friction, good storage stability and good eco-friendliness, and can be widely used in environmentally friendly chemical fiber twisting lubrication systems.

[0006] An antistatic and environmentally friendly polyester DTY twisting oil, the oil comprising the following components in parts by weight: (1) Vegetable oil-based modified fatty acid ester main agent, 100 parts; (2) Biodegradable block lubricant, 57-85 parts; (3) Natural source conductive modifier, 14-28 parts; (4) Surface-modified nano zinc oxide, 1-6 parts; (5) Imidazole ionic liquid antistatic agent, 10-24 parts; (6) No APEO-type glycoside emulsifier, 14-25 parts; (7) Stabilizer, 1-4 parts; (8) Deionized water, 57-85 parts.

[0007] Preferably, the preparation steps of the vegetable oil-based modified fatty acid ester main agent are as follows: castor oil and glycerol are preheated to 35-45°C, and the solid acid catalyst Amberlyst-15 is dried under vacuum at 95-115°C for 100-140 minutes to remove adsorbed moisture. Castor oil, glycerol, and solid acid catalyst Amberlyst-15 are added to the reaction vessel in a ratio of 500mL:100-120mL:16-22g. The mixture is placed in a nitrogen atmosphere and stirred at 130-150°C for 4-6 hours. The temperature is then lowered to 70-90°C, and the solid acid catalyst Amberlyst-15 is removed by filtration. The filtrate is transferred to a rotary evaporator, and residual glycerol and light by-products are removed at 70-90°C and -0.06--0.1MPa to obtain the vegetable oil-based modified fatty acid ester main agent.

[0008] Preferably, the biodegradable block lubricant is a polyethylene glycol-polypropylene glycol (PEG-PPG) block copolymer with a molecular weight of 1500 to 3500.

[0009] Preferably, the preparation steps of the natural source conductive modifier are as follows: Deionized water solvent, glacial acetic acid, and chitosan are added to a reaction vessel and magnetically stirred for 200–280 minutes. The pH of the solution is adjusted to 6.0–6.4 using 1 mol / L sodium hydroxide solution. 2,3-epoxypropyltrimethylammonium chloride is slowly added dropwise while stirring, with a ratio of 400–600 mL: 4–6 mL: 10 g: 32–48 mL. The temperature is raised to 60–80°C, and the reaction is stirred for 5–7 hours. After cooling to room temperature, the reaction solution is slowly poured into 500 mL of anhydrous ethanol and vigorously stirred to form a flocculent precipitate. The precipitate is washed three times with ethanol and twice with deionized water until the washings are free of chloride ions. The precipitate is filtered out and vacuum dried to obtain the natural source conductive modifier.

[0010] Preferably, the preparation steps of the surface-modified nano zinc oxide are as follows: anhydrous ethanol solvent and nano zinc oxide are added to a reaction vessel, ultrasonically dispersed evenly, and oil acid and polyglycerol ester are slowly dropped in while stirring. The ratio of the four components is 160-240 mL: 100 g: 4.5-6.7 mL: 8-12 g. The temperature is raised to 45-65°C, and the reaction is stirred for 100-140 minutes. The mixture is cooled to room temperature, filtered, and washed twice each with ethanol and deionized water before vacuum drying to obtain surface-modified nano zinc oxide.

[0011] Preferably, the preparation steps of the imidazole ionic liquid antistatic agent are as follows: 1-methylimidazole is added to a reaction vessel, followed by slow addition of chloroethane. The temperature is raised to 70-90°C, and the mixture is stirred for 10-14 hours. The temperature is then lowered to 0-4°C, and concentrated sulfuric acid with a mass fraction of 98% is slowly added dropwise. The ratio of the three components is 100g:70-106g:42.6-63.8mL. The temperature is maintained at a low temperature to control the exothermic reaction. The temperature is then raised to 30-50°C, and the mixture is stirred for 200-280 minutes. The mixture is washed clean with anhydrous diethyl ether and vacuum dried to obtain the imidazole ionic liquid antistatic agent.

[0012] Preferably, the APEO-free glycoside emulsifier is a mixture of APG-1214 and cocamidopropyl betaine in a mass ratio of 3:1.

[0013] Preferably, the stabilizer is a mixture of PVP-K30 and PEG-6000 in a mass ratio of 2:1.

[0014] A production process for an antistatic and environmentally friendly polyester DTY twisting oil includes the following steps: S1. Preparation of vegetable oil-based modified fatty acid ester main agent, natural source conductive modifier, surface modified nano zinc oxide, and imidazole ionic liquid antistatic agent; S2. Add vegetable oil-based modified fatty acid ester main agent, biodegradable block lubricant, and imidazole ionic liquid antistatic agent to the reaction vessel according to the mixing direction, and stir at 35-55℃ for 20-40 minutes to form a homogeneous base oil phase system. S3. Weigh the natural source conductive modifier according to the formula, prepare a 6-10 wt% deionized water solution, slowly add it dropwise to the base oil phase system in step S2, stir for 20-30 minutes, then add APEO-free glycoside emulsifier and deionized water according to the formula, stir evenly at 25-45℃ to form the initial emulsion state. S4. Weigh the surface-modified nano zinc oxide according to the formula, and ultrasonically disperse it with deionized water, anhydrous ethanol and PEG-7 glycerol cocoate to form a dispersion. The formula ratio of the four is 1g:4g:2g:1g. Then add it to the pre-emulsion system in step S3 and emulsify it using a high-shear emulsifier. S5. Add the stabilizer to the system in step S4 according to the formula, and adjust the pH of the system to 6.5-7.5 using a 1% sodium hydroxide solution. S6. Filter the emulsion system in step S5 through a 200-mesh stainless steel filter to remove large particulate impurities, cool to room temperature, and allow to stand to defoam, to obtain an antistatic and environmentally friendly polyester DTY twisting oil.

[0015] Preferably, the high-shear emulsifier operates at a speed of 8000–10000 rpm and has an emulsification time of 10–18 minutes.

[0016] Compared with the prior art, the advantages of this invention are: (1) Excellent green and environmentally friendly properties and strong sustainability This invention uses vegetable oil-based modified fatty acid esters obtained by esterification of castor oil and glycerol as the main agent, completely replacing traditional petrochemical-based mineral oils. Combined with APEO-free glycoside emulsifiers, PEG-PPG block lubricants, and biodegradable stabilizers, it constructs a fully bio-based or green component system, significantly improving the renewability and biodegradability of the oil. The biodegradability of the oil exceeds 75% within 28 days, meeting the OECD 301 standard and satisfying the safety requirements of green textile chemicals.

[0017] (2) Surface-modified nano zinc oxide has an advanced structure and multiple functions. Oleic acid and polyglycerol esters are used to modify the surface of nano zinc oxide. Through the formation of coordination bonds, hydrogen bonds and electrostatic interactions between hydroxyl groups and the zinc oxide surface, a stable "inorganic core / organic shell" structure is constructed, which has both dispersion stability and antistatic function, and synergistically enhances the conductivity and dispersibility of oil agents.

[0018] (3) Excellent and long-lasting antistatic properties By introducing a composite system of chitosan quaternary ammonium salt, a natural conductive material, and imidazole ionic liquid, a conductive pathway is effectively constructed. This is further enhanced by surface-modified nano-zinc oxide to improve charge conduction and dissipation, thus creating a dual-mechanism conductive network system. The surface resistivity of the resulting oil is controlled at 10 Ω·cm. 7 ~10 9 Ω imparts excellent and long-term stable antistatic properties to the oil, making it suitable for complex working conditions such as high-speed twisting and high-temperature false twisting.

[0019] (4) Strong lubricity and fiber affinity Biodegradable PEG-PPG block copolymers and vegetable oils work synergistically to lubricate, forming a continuous and dense oil film with excellent fiber affinity. This significantly reduces friction between the yarn and the guide, keeping the coefficient of friction below 0.20, thus improving yarn quality and guide stability.

[0020] (5) High structural stability and excellent emulsion performance Multiple stabilization mechanisms were constructed, including an APG-1214+betaine APEO-free emulsification system, a PVP-K30+PEG-6000 stabilizer, and a high-efficiency high-shear dispersion process, which effectively improved the storage stability and thermodynamic stability of the emulsion. The oil formulation showed no obvious stratification, sedimentation, or precipitation within 6 months of storage at room temperature, and the system compatibility and physical stability were significantly better than traditional oil formulations.

[0021] (6) The production process is green and simple. All components are reacted using mild, low-toxicity, solvent-free or green solvents. The production process does not involve highly corrosive or highly polluting intermediates, and the overall process is highly controllable and energy-efficient. Detailed Implementation

[0022] Example 1: S1.1 Preparation of vegetable oil-based modified fatty acid ester main agent: Castor oil and glycerol were preheated to 35°C. Solid acid catalyst Amberlyst-15 was dried under vacuum at 95°C for 100 minutes to remove adsorbed moisture. 500 mL of castor oil, 100 mL of glycerol, and 16 g of solid acid catalyst Amberlyst-15 were added to the reaction vessel. The vessel was placed in a nitrogen atmosphere and stirred at 130°C for 4 hours. The temperature was lowered to 70°C, and the solid acid catalyst Amberlyst-15 was removed by filtration. The filtrate was transferred to a rotary evaporator and the residual glycerol and light by-products were removed at 70°C and -0.06 MPa to obtain the vegetable oil-based modified fatty acid ester main agent. S1.2 Preparation of natural source conductive modifier: Add 400mL of deionized water solvent, 4mL of glacial acetic acid, and 10g of chitosan to the reaction vessel, stir magnetically for 200 minutes, adjust the pH of the solution to 6.4 using 1mol / L sodium hydroxide solution, slowly add 32mL of 2,3-epoxypropyltrimethylammonium chloride while stirring, heat to 60℃, stir for 5h, cool to room temperature, slowly pour the reaction solution into 500mL of anhydrous ethanol, stir vigorously to form flocculent precipitate, wash 3 times with ethanol and 2 times with deionized water until the washing solution is free of chloride ions, filter out the precipitate, vacuum dry to obtain natural source conductive modifier; S1.3 Preparation of surface-modified nano zinc oxide: Add 160 mL of anhydrous ethanol solvent and 100 g of nano zinc oxide to the reaction vessel, disperse evenly by ultrasonication, slowly add 4.5 mL of oleic acid and 8 g of polyglycerol ester while stirring, heat to 45 °C, stir and react for 100 minutes, cool to room temperature, filter and separate, wash twice with ethanol and deionized water respectively, and vacuum dry to obtain surface-modified nano zinc oxide; S1.4 Preparation of imidazole ionic liquid antistatic agent: Add 100g of 1-methylimidazolium to the reaction vessel, slowly add 70g of chloroethane, heat to 70℃, stir and react for 10h, cool to 0℃, slowly add 42.6mL of 98% concentrated sulfuric acid, maintain low temperature to control exothermic reaction, heat to 30℃, stir and react for 200 minutes, wash clean with anhydrous diethyl ether and vacuum dry to obtain imidazole ionic liquid antistatic agent; S2. Add 100 parts of vegetable oil-based modified fatty acid ester main agent, 57 parts of biodegradable block lubricant polyethylene glycol-polypropylene glycol (PEG-PPG) block copolymer, and 10 parts of imidazole ionic liquid antistatic agent to the reaction vessel according to the mixing direction. Stir at 35°C for 20 minutes to form a homogeneous base oil phase system. S3. Weigh 14 parts of natural source conductive modifier according to the formula, prepare a 6wt% deionized water solution, slowly add it dropwise to the base oil phase system in step S2, stir for 20 minutes, then add 14 parts of a mixture of APG-1214 (mass ratio 3:1) and cocamidopropyl betaine, and 57 parts of deionized water according to the formula, stir evenly at 25℃ to form the initial emulsion state; S4. Weigh 1 part of surface-modified nano zinc oxide according to the formula, and ultrasonically disperse it with 4 parts of deionized water, 2 parts of anhydrous ethanol and 1 part of PEG-7 glycerol cocoate to form a dispersion. Then add it to the primary emulsion system in step S3 and emulsify it for 10 minutes using a high-shear emulsifier at a speed of 8000 rpm. S5. Add 1 part of a mixture of PVP-K30 and PEG-6000 (mass ratio of stabilizer 2:1) to the system in step S4 according to the formula, and adjust the pH of the system to 6.5 using 1% sodium hydroxide solution. S6. Filter the emulsion system in step S5 through a 200-mesh stainless steel filter to remove large particulate impurities, cool to room temperature, and allow to stand to defoam, to obtain an antistatic and environmentally friendly polyester DTY twisting oil.

[0023] Example 2: S1.1 Preparation of vegetable oil-based modified fatty acid ester main agent: Castor oil and glycerol were preheated to 37.5℃ respectively. Solid acid catalyst Amberlyst-15 was dried at 100℃ under vacuum for 110 minutes to remove adsorbed moisture. 500mL castor oil, 105mL glycerol and 17.5g solid acid catalyst Amberlyst-15 were added to the reaction vessel and placed in a nitrogen atmosphere. The reaction was stirred at 135℃ for 4.5h. The temperature was lowered to 75℃, and the solid acid catalyst Amberlyst-15 was removed by filtration. The filtrate was transferred to a rotary evaporator and the residual glycerol and light by-products were removed at 75℃ and -0.07MPa to obtain the vegetable oil-based modified fatty acid ester main agent. S1.2 Preparation of natural source conductive modifier: Add 450mL of deionized water solvent, 4.5mL of glacial acetic acid, and 10g of chitosan to the reaction vessel, stir magnetically for 220 minutes, adjust the pH of the solution to 6.3 using 1mol / L sodium hydroxide solution, slowly add 36mL of 2,3-epoxypropyltrimethylammonium chloride while stirring, heat to 65℃, stir for 5.5h, cool to room temperature, slowly pour the reaction solution into 500mL of anhydrous ethanol, stir vigorously to form flocculent precipitate, wash 3 times with ethanol and 2 times with deionized water until the washing solution is free of chloride ions, filter out the precipitate, vacuum dry to obtain natural source conductive modifier; S1.3 Preparation of surface-modified nano zinc oxide: Add 180 mL of anhydrous ethanol solvent and 100 g of nano zinc oxide to the reaction vessel, disperse evenly by ultrasonication, slowly add 5.05 mL of oleic acid and 9 g of polyglycerol ester while stirring, heat to 50 °C, stir and react for 110 minutes, cool to room temperature, filter and separate, wash twice with ethanol and twice with deionized water, and vacuum dry to obtain surface-modified nano zinc oxide; S1.4 Preparation of imidazole ionic liquid antistatic agent: Add 100g of 1-methylimidazolium to the reaction vessel, slowly add 79g of chloroethane, heat to 75℃, stir and react for 11h, cool to 1℃, slowly add 47.9mL of 98% concentrated sulfuric acid, maintain low temperature to control exothermic reaction, heat to 35℃, stir and react for 220 minutes, wash clean with anhydrous diethyl ether and vacuum dry to obtain imidazole ionic liquid antistatic agent; S2. Add 100 parts of vegetable oil-based modified fatty acid ester main agent, 64 parts of biodegradable block lubricant polyethylene glycol-polypropylene glycol (PEG-PPG) block copolymer, and 13.5 parts of imidazole ionic liquid antistatic agent to the reaction vessel according to the mixing direction. Stir at 40°C for 25 minutes to form a homogeneous base oil phase system. S3. Weigh 17.5 parts of natural source conductive modifier according to the formula, prepare a 7wt% deionized water solution, slowly add it dropwise to the base oil phase system in step S2, stir for 22.5 minutes, then add 16.75 parts of a mixture of APG-1214 (mass ratio 3:1) and cocamidopropyl betaine, and 64 parts of deionized water according to the formula, stir evenly at 30℃ to form the initial emulsion state; S4. Weigh 2.25 parts of surface-modified nano zinc oxide according to the formula, and ultrasonically disperse it with 9 parts of deionized water, 4.5 parts of anhydrous ethanol and 2.25 parts of PEG-7 glycerol cocoate to form a dispersion. Then add it to the primary emulsion system in step S3 and emulsify it for 12 minutes using a high-shear emulsifier at a speed of 8500 rpm. S5. Add 1.75 parts of a mixture of PVP-K30 and PEG-6000 with a stabilizer mass ratio of 2:1 to the system in step S4 according to the formula, and adjust the pH of the system to 6.75 using a 1% sodium hydroxide solution. S6. Filter the emulsion system in step S5 through a 200-mesh stainless steel filter to remove large particulate impurities, cool to room temperature, and allow to stand to defoam, to obtain an antistatic and environmentally friendly polyester DTY twisting oil.

[0024] Example 3: S1.1 Preparation of vegetable oil-based modified fatty acid ester main agent: Castor oil and glycerol were preheated to 40℃ respectively. Solid acid catalyst Amberlyst-15 was dried at 105℃ under vacuum for 120 minutes to remove adsorbed moisture. 500mL castor oil, 110mL glycerol and 19g solid acid catalyst Amberlyst-15 were added to the reaction vessel and placed in a nitrogen atmosphere. The reaction was stirred at 140℃ for 5h. The temperature was lowered to 80℃, and the solid acid catalyst Amberlyst-15 was removed by filtration. The filtrate was transferred to a rotary evaporator and the residual glycerol and light by-products were removed at 80℃ and -0.08MPa to obtain the vegetable oil-based modified fatty acid ester main agent. S1.2 Preparation of natural source conductive modifier: Add 500mL of deionized water solvent, 5mL of glacial acetic acid, and 10g of chitosan to the reaction vessel, stir magnetically for 240 minutes, adjust the pH of the solution to 6.2 using 1mol / L sodium hydroxide solution, slowly add 40mL of 2,3-epoxypropyltrimethylammonium chloride while stirring, heat to 70℃, stir for 6h, cool to room temperature, slowly pour the reaction solution into 500mL of anhydrous ethanol, stir vigorously to form flocculent precipitate, wash 3 times with ethanol and 2 times with deionized water until the washing solution is free of chloride ions, filter out the precipitate, vacuum dry to obtain natural source conductive modifier; S1.3 Preparation of surface-modified nano zinc oxide: Add 200 mL of anhydrous ethanol solvent and 100 g of nano zinc oxide to the reaction vessel, disperse evenly by ultrasonication, slowly add 5.6 mL of oleic acid and 10 g of polyglycerol ester while stirring, heat to 55 °C, stir and react for 120 minutes, cool to room temperature, filter and separate, wash twice with ethanol and deionized water respectively, and vacuum dry to obtain surface-modified nano zinc oxide; S1.4 Preparation of imidazole ionic liquid antistatic agent: Add 100g of 1-methylimidazolium to the reaction vessel, slowly add 88g of chloroethane, heat to 80℃, stir and react for 12h, cool to 2℃, slowly add 53.2mL of 98% concentrated sulfuric acid, maintain low temperature to control exothermic reaction, heat to 40℃, stir and react for 240 minutes, wash clean with anhydrous diethyl ether and vacuum dry to obtain imidazole ionic liquid antistatic agent; S2. Add 100 parts of vegetable oil-based modified fatty acid ester main agent, 71 parts of biodegradable block lubricant polyethylene glycol-polypropylene glycol (PEG-PPG) block copolymer, and 17 parts of imidazole ionic liquid antistatic agent to the reaction vessel according to the mixing direction. Stir at 45°C for 30 minutes to form a homogeneous base oil phase system. S3. Weigh 21 parts of natural source conductive modifier according to the formula, prepare an 8wt% deionized water solution, slowly add it dropwise to the base oil phase system in step S2, stir for 25 minutes, then add 19.5 parts of a mixture of APG-1214 (mass ratio 3:1) and cocamidopropyl betaine, and 71 parts of deionized water according to the formula, stir evenly at 35℃ to form the initial emulsion state; S4. Weigh 3.5 parts of surface-modified nano zinc oxide according to the formula, and ultrasonically disperse it with 14 parts of deionized water, 7 parts of anhydrous ethanol and 3.5 parts of PEG-7 glycerol cocoate to form a dispersion. Then add it to the primary emulsion system in step S3 and emulsify it for 14 minutes using a high-shear emulsifier at a speed of 9000 rpm. S5. Add 2.5 parts of a mixture of PVP-K30 and PEG-6000 with a stabilizer mass ratio of 2:1 to the system in step S4 according to the formula, and adjust the pH of the system to 7 using a 1% sodium hydroxide solution. S6. Filter the emulsion system in step S5 through a 200-mesh stainless steel filter to remove large particulate impurities, cool to room temperature, and allow to stand to defoam, to obtain an antistatic and environmentally friendly polyester DTY twisting oil.

[0025] Example 4: S1.1 Preparation of vegetable oil-based modified fatty acid ester main agent: Castor oil and glycerol were preheated to 40℃ respectively. Solid acid catalyst Amberlyst-15 was dried at 110℃ under vacuum for 130 minutes to remove adsorbed moisture. 500mL castor oil, 115mL glycerol and 20.5g solid acid catalyst Amberlyst-15 were added to the reaction vessel and placed in a nitrogen atmosphere. The reaction was stirred at 145℃ for 5.5h. The temperature was then lowered to 85℃, and the solid acid catalyst Amberlyst-15 was removed by filtration. The filtrate was transferred to a rotary evaporator and the residual glycerol and light by-products were removed at 85℃ and -0.09MPa to obtain the vegetable oil-based modified fatty acid ester main agent. S1.2 Preparation of natural source conductive modifier: Add 550 mL of deionized water solvent, 5.5 mL of glacial acetic acid, and 10 g of chitosan to the reaction vessel, stir magnetically for 260 minutes, adjust the pH of the solution to 6.1 using 1 mol / L sodium hydroxide solution, slowly add 44 mL of 2,3-epoxypropyltrimethylammonium chloride while stirring, heat to 75 °C, stir for 6.5 h, cool to room temperature, slowly pour the reaction solution into 500 mL of anhydrous ethanol, stir vigorously to form flocculent precipitate, wash 3 times with ethanol and 2 times with deionized water until the washing solution is free of chloride ions, filter out the precipitate, vacuum dry to obtain natural source conductive modifier; S1.3 Preparation of surface-modified nano zinc oxide: Add 220 mL of anhydrous ethanol solvent and 100 g of nano zinc oxide to the reaction vessel, disperse evenly by ultrasonication, slowly add 6.15 mL of oleic acid and 11 g of polyglycerol ester while stirring, heat to 60 °C, stir and react for 130 minutes, cool to room temperature, filter and separate, wash twice with ethanol and deionized water respectively, and vacuum dry to obtain surface-modified nano zinc oxide; S1.4 Preparation of imidazole ionic liquid antistatic agent: Add 100g of 1-methylimidazolium to the reaction vessel, slowly add 97g of chloroethane, heat to 85℃, stir and react for 13h, cool to 3℃, slowly add 58.5mL of 98% concentrated sulfuric acid, maintain low temperature to control exothermic reaction, heat to 45℃, stir and react for 260 minutes, wash clean with anhydrous diethyl ether and vacuum dry to obtain imidazole ionic liquid antistatic agent; S2. Add 100 parts of vegetable oil-based modified fatty acid ester main agent, 78 parts of biodegradable block lubricant polyethylene glycol-polypropylene glycol (PEG-PPG) block copolymer, and 20.5 parts of imidazole ionic liquid antistatic agent to the reaction vessel according to the mixing direction. Stir at 50°C for 35 minutes to form a homogeneous base oil phase system. S3. Weigh 24.5 parts of natural source conductive modifier according to the formula, prepare a 9wt% deionized water solution, slowly add it dropwise to the base oil phase system in step S2, stir for 27.5 minutes, then add 22.25 parts of a mixture of APG-1214 (mass ratio 3:1) and cocamidopropyl betaine, and 78 parts of deionized water according to the formula, stir evenly at 40℃ to form the initial emulsion state; S4. Weigh 4.75 parts of surface-modified nano zinc oxide according to the formula, and ultrasonically disperse it with 19 parts of deionized water, 9.5 parts of anhydrous ethanol and 4.75 parts of PEG-7 glycerol cocoate to form a dispersion. Then add it to the primary emulsion system in step S3 and emulsify it for 16 minutes using a high-shear emulsifier at a speed of 9500 rpm. S5. Add 3.25 parts of a mixture of PVP-K30 and PEG-6000 in a stabilizer mass ratio of 2:1 to the system in step S4 according to the formula, and adjust the pH of the system to 7.25 using a 1% sodium hydroxide solution. S6. Filter the emulsion system in step S5 through a 200-mesh stainless steel filter to remove large particulate impurities, cool to room temperature, and allow to stand to defoam, to obtain an antistatic and environmentally friendly polyester DTY twisting oil.

[0026] Example 5: S1.1 Preparation of vegetable oil-based modified fatty acid ester main agent: Castor oil and glycerol were preheated to 45℃ respectively. Solid acid catalyst Amberlyst-15 was dried at 115℃ under vacuum for 140 minutes to remove adsorbed moisture. 500mL castor oil, 120mL glycerol and 22g solid acid catalyst Amberlyst-15 were added to the reaction vessel and placed in a nitrogen atmosphere. The reaction was stirred at 150℃ for 6h. The temperature was lowered to 90℃, and the solid acid catalyst Amberlyst-15 was removed by filtration. The filtrate was transferred to a rotary evaporator and the residual glycerol and light by-products were removed at 90℃ and -0.1MPa to obtain the vegetable oil-based modified fatty acid ester main agent. S1.2 Preparation of natural source conductive modifier: Add 600mL of deionized water solvent, 6mL of glacial acetic acid, and 10g of chitosan to the reaction vessel, stir magnetically for 280 minutes, adjust the pH of the solution to 6.0 using 1mol / L sodium hydroxide solution, slowly add 48mL of 2,3-epoxypropyltrimethylammonium chloride while stirring, heat to 80℃, stir for 7h, cool to room temperature, slowly pour the reaction solution into 500mL of anhydrous ethanol, stir vigorously to form flocculent precipitate, wash 3 times with ethanol and 2 times with deionized water until the washing solution is free of chloride ions, filter out the precipitate, vacuum dry to obtain natural source conductive modifier; S1.3 Preparation of surface-modified nano zinc oxide: Add 240 mL of anhydrous ethanol solvent and 100 g of nano zinc oxide to the reaction vessel, disperse it evenly by ultrasonication, slowly add 6.7 mL of oleic acid and 12 g of polyglycerol ester while stirring, heat to 65 °C, stir and react for 140 minutes, cool to room temperature, filter and separate, wash twice with ethanol and deionized water respectively, and vacuum dry to obtain surface-modified nano zinc oxide; S1.4 Preparation of imidazole ionic liquid antistatic agent: Add 100g of 1-methylimidazolium to the reaction vessel, slowly add 106g of chloroethane, heat to 90℃, stir and react for 14h, cool to 4℃, slowly add 63.8mL of 98% concentrated sulfuric acid, maintain low temperature to control exothermic reaction, heat to 50℃, stir and react for 280 minutes, wash clean with anhydrous diethyl ether and vacuum dry to obtain imidazole ionic liquid antistatic agent; S2. Add 100 parts of vegetable oil-based modified fatty acid ester main agent, 85 parts of biodegradable block lubricant polyethylene glycol-polypropylene glycol (PEG-PPG) block copolymer, and 24 parts of imidazole ionic liquid antistatic agent to the reaction vessel according to the mixing direction. Stir at 55°C for 40 minutes to form a homogeneous base oil phase system. S3. Weigh 28 parts of natural source conductive modifier according to the formula, prepare a 10wt% deionized water solution, slowly add it dropwise to the base oil phase system in step S2, stir for 30 minutes, then add 25 parts of a mixture of APG-1214 (mass ratio 3:1) and cocamidopropyl betaine, and 85 parts of deionized water according to the formula, stir evenly at 45℃ to form the initial emulsion state; S4. Weigh 6 parts of surface-modified nano zinc oxide according to the formula, and ultrasonically disperse it with 24 parts of deionized water, 12 parts of anhydrous ethanol and 6 parts of PEG-7 glycerol cocoate to form a dispersion. Then add it to the primary emulsion system in step S3 and emulsify it for 18 minutes using a high-shear emulsifier at a speed of 10,000 rpm. S5. Add 4 parts of a mixture of PVP-K30 and PEG-6000 in a stabilizer mass ratio of 2:1 to the system in step S4 according to the formula, and adjust the pH of the system to 7.5 using a 1% sodium hydroxide solution. S6. Filter the emulsion system in step S5 through a 200-mesh stainless steel filter to remove large particulate impurities, cool to room temperature, and allow to stand to defoam, to obtain an antistatic and environmentally friendly polyester DTY twisting oil.

[0027] Performance testing Surface resistivity test The oils obtained in Examples 1-5 were uniformly coated onto the surface of a polyester film (100 μm thick) and dried at room temperature for 24 hours to form a conductive film with a sample thickness of approximately 50 μm. The film was sandwiched between two electrodes, and a voltage of 100 V was applied. The testing equipment was a TH2684A digital high-resistivity meter with a standard flat electrode (φ50 mm). The test results are shown in the table below: Friction coefficient test The oils obtained in Examples 1-5 were uniformly sprayed onto polyester DTY fiber samples. After drying at a constant temperature, they were used for friction testing. A standard weight was placed in contact with the test surface of the fiber cloth, the slider was pulled, and the static / dynamic friction force was recorded. The coefficient of friction (u) was automatically calculated. Load: 200g, speed: 150mm / min, test distance: 100mm, testing equipment: MXD-01 coefficient of friction meter. The test results are shown in the table below: Biodegradation rate test The oil obtained in Examples 1-5 was diluted to 500 mg / L as a test solution. Activated sludge was added to the test bottle, followed by the sample, and the BOD measurement system was connected. The culture temperature was set to 25°C, and the oxygen consumption was continuously monitored for 28 days. The test equipment consisted of a BOD analyzer and an anaerobic fermentation bottle. The test results are shown in the table below: Storage stability test The oils obtained in Examples 1-5 were sealed and stored at 25°C, 40°C, and 4°C, respectively. Precipitation, stratification, or turbidity were observed every 15 days. After stirring for 10 minutes, it was observed whether a homogeneous emulsion state was restored, and the duration of stable state was recorded. The table below shows the test results: Detection of nano zinc oxide dispersed particle size and emulsion particle size 0.01 mL of the oil obtained in Examples 1-5 was diluted 200 times with deionized water, placed in the sample cell, and measured in the dark. The average particle size was read. The testing equipment was a Malvern Zetasizer Nano ZS90 particle size analyzer. The test results are shown in the table below:

Claims

1. An antistatic and environmentally friendly polyester DTY twisting oil, characterized in that, The oil comprises the following components in parts by weight: (1) Vegetable oil-based modified fatty acid ester main agent, 100 parts; (2) Biodegradable block lubricant, 57-85 parts; (3) Natural source conductive modifier, 14-28 parts; (4) Surface-modified nano zinc oxide, 1-6 parts; (5) Imidazole ionic liquid antistatic agent, 10-24 parts; (6) No APEO-type glycoside emulsifier, 14-25 parts; (7) Stabilizer, 1-4 parts; (8) Deionized water, 57-85 parts.

2. The antistatic and environmentally friendly polyester DTY twisting oil agent according to claim 1, characterized in that: The preparation steps of the vegetable oil-based modified fatty acid ester main agent are as follows: castor oil and glycerol are preheated to 35-45℃ respectively, and the solid acid catalyst Amberlyst-15 is dried under vacuum at 95-115℃ for 100-140 minutes to remove adsorbed moisture. Castor oil, glycerol, and solid acid catalyst Amberlyst-15 are added to the reaction vessel in a ratio of 500mL:100-120mL:16-22g. The mixture is placed in a nitrogen atmosphere and stirred at 130-150℃ for 4-6 hours. The temperature is then lowered to 70-90℃, and the solid acid catalyst Amberlyst-15 is removed by filtration. The filtrate is transferred to a rotary evaporator and the residual glycerol and light by-products are removed at 70-90℃ and -0.06--0.1MPa to obtain the vegetable oil-based modified fatty acid ester main agent.

3. The antistatic and environmentally friendly polyester DTY twisting oil agent according to claim 1, characterized in that: The biodegradable block lubricant is a polyethylene glycol-polypropylene glycol (PEG-PPG) block copolymer with a molecular weight of 1500-3500.

4. The antistatic and environmentally friendly polyester DTY twisting oil agent according to claim 1, characterized in that: The preparation steps of the natural source conductive modifier are as follows: Deionized water solvent, glacial acetic acid, and chitosan are added to a reaction vessel and magnetically stirred for 200-280 minutes. The pH of the solution is adjusted to 6.0-6.4 using 1 mol / L sodium hydroxide solution. 2,3-epoxypropyltrimethylammonium chloride is slowly added dropwise while stirring. The ratio of the four components is 400-600 mL: 4-6 mL: 10 g: 32-48 mL. The temperature is raised to 60-80℃, and the reaction is stirred for 5-7 hours. After cooling to room temperature, the reaction solution is slowly poured into 500 mL of anhydrous ethanol and vigorously stirred to form a flocculent precipitate. The precipitate is washed three times with ethanol and twice with deionized water until the washing solution is free of chloride ions. The precipitate is filtered out and vacuum dried to obtain the natural source conductive modifier.

5. The antistatic and environmentally friendly polyester DTY twisting oil agent according to claim 1, characterized in that: The preparation steps of the surface-modified nano zinc oxide are as follows: anhydrous ethanol solvent and nano zinc oxide are added to the reaction vessel and ultrasonically dispersed evenly. Under stirring, oleic acid and polyglycerol ester are slowly added dropwise. The ratio of the four components is 160-240 mL: 100 g: 4.5-6.7 mL: 8-12 g. The temperature is raised to 45-65℃ and the reaction is stirred for 100-140 minutes. The mixture is cooled to room temperature, filtered, and washed twice with ethanol and twice with deionized water. The mixture is then vacuum dried to obtain the surface-modified nano zinc oxide.

6. The antistatic and environmentally friendly polyester DTY twisting oil agent according to claim 1, characterized in that: The preparation steps of the imidazole-based ionic liquid antistatic agent are as follows: 1-methylimidazole is added to the reaction vessel, followed by slow addition of chloroethane. The temperature is raised to 70-90°C, and the reaction is stirred for 10-14 hours. The temperature is then lowered to 0-4°C, and concentrated sulfuric acid with a mass fraction of 98% is slowly added dropwise. The ratio of the three components is 100g:70-106g:42.6-63.8mL. The temperature is maintained at a low temperature to control the exothermic reaction. The temperature is then raised to 30-50°C, and the reaction is stirred for 200-280 minutes. The mixture is washed clean with anhydrous diethyl ether and vacuum dried to obtain the imidazole-based ionic liquid antistatic agent.

7. The antistatic and environmentally friendly polyester DTY twisting oil agent according to claim 1, characterized in that: The APEO-free glycoside emulsifier is a mixture of APG-1214 and cocamidopropyl betaine in a mass ratio of 3:

1.

8. The antistatic and environmentally friendly polyester DTY twisting oil agent according to claim 1, characterized in that: The stabilizer is a mixture of PVP-K30 and PEG-6000 in a mass ratio of 2:

1.

9. A production process for an antistatic and environmentally friendly polyester DTY twisting oil, characterized in that, Includes the following steps: S1. Preparation of vegetable oil-based modified fatty acid ester main agent, natural source conductive modifier, surface modified nano zinc oxide, and imidazole ionic liquid antistatic agent; S2. Add vegetable oil-based modified fatty acid ester main agent, biodegradable block lubricant, and imidazole ionic liquid antistatic agent to the reaction vessel according to the mixing direction, and stir at 35-55℃ for 20-40 minutes to form a homogeneous base oil phase system. S3. Weigh the natural source conductive modifier according to the formula, prepare a 6-10 wt% deionized water solution, slowly add it dropwise to the base oil phase system in step S2, stir for 20-30 minutes, then add APEO-free glycoside emulsifier and deionized water according to the formula, stir evenly at 25-45℃ to form the initial emulsion state. S4. Weigh the surface-modified nano zinc oxide according to the formula, and ultrasonically disperse it with deionized water, anhydrous ethanol and PEG-7 glycerol cocoate to form a dispersion. The formula ratio of the four is 1g:4g:2g:1g. Then add it to the pre-emulsion system in step S3 and emulsify it using a high-shear emulsifier. S5. Add the stabilizer to the system in step S4 according to the formula, and adjust the pH of the system to 6.5-7.5 using a 1% sodium hydroxide solution. S6. Filter the emulsion system in step S5 through a 200-mesh stainless steel filter to remove large particulate impurities, cool to room temperature, and allow to stand to defoam, to obtain an antistatic and environmentally friendly polyester DTY twisting oil.

10. The production process of an antistatic and environmentally friendly polyester DTY twisting oil agent according to claim 9, characterized in that: The high-shear emulsifier operates at a speed of 8000–10000 rpm and has an emulsification time of 10–18 minutes.

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