Composite fdy oil and preparation method thereof

Abstract

The application provides a composite FDY oil agent and a preparation method thereof. The preparation method comprises the following steps: mixing and heating and stirring an HLB regulator and water to obtain a first mixture; adding an emulsifier, a clustering agent, an antistatic agent and a smoothing agent into the first mixture, mixing and heat-insulating stirring to obtain a second mixture; adjusting the pH value to 6.5-7.5, filtering and cooling the second mixture to room temperature to obtain the composite FDY oil agent; wherein the HLB regulator is porous silicon dioxide loaded with glyceride ethoxylate and coated with ethyl cellulose. The composite FDY oil agent can keep the stability of the HLB value under high-temperature conditions, and has good environmental friendliness.

Description

Technical Field

[0001] This application relates to the technical field of chemical materials, and more specifically, to a composite FDY oil agent and its preparation method. Background Technology

[0002] Polyester is a fiber made from purified terephthalic acid (PTA) or dimethyl terephthalate (DMT) and ethylene glycol (MEG) through esterification or transesterification and then polycondensation. PET is then spun and post-processed to produce fibers.

[0003] Polyester products mainly include POY (pre-oriented yarn), FDY (fully drawn yarn), and DTY (drawn textured yarn). Among them, FDY polyester fiber is characterized by high-speed drawing (>4000m / min) and heat setting in one step during the spinning process. The molecular chains of FDY polyester fiber are highly oriented and crystallized, directly producing finished yarn. Therefore, FDY polyester fiber has a smooth surface, high gloss, and dimensional stability, making it particularly suitable for making linings or imitation silk fabrics.

[0004] Existing FDY spinning oils typically use nonionic surfactants (such as glyceryl ester ethoxylates, fatty alcohol polyoxyethylene ethers (AEOs), etc.) as their core components. Their hydrophilicity depends on the hydrogen bonds formed between the polyoxyethylene chain (EO chain) and water. As the spinning process progresses, the temperature of the FDY spinning oil gradually increases, intensifying the thermal motion of water molecules. This causes water to evaporate from the oil, disrupting the hydrogen bonds between the EO chain and water molecules, leading to a decrease in the hydrophilicity of the FDY spinning oil. Furthermore, when the spinning temperature exceeds the cloud point, the nonionic surfactant changes from a transparent solution to a milky white turbid liquid, at which point the HLB value drops sharply.

[0005] The decrease in HLB value of FDY spinning oil under high-temperature conditions leads to a weakening of its emulsifying ability and a tendency for oil-water phase separation. This problem causes fluctuations in the coefficient of friction of FDY fibers and increases the risk of fuzzing and breakage. Existing research indicates that when the temperature of the FDY spinning oil increases from 40℃ to 100℃, its HLB value decreases by 15% to 20%, while the dynamic coefficient of friction of FDY fibers increases by 0.05 to 0.08.

[0006] How to avoid HLB value fluctuations in FDY spinning oil under high temperature conditions is one of the technical problems that urgently need to be solved by those skilled in the art. Summary of the Invention

[0007] One of the problems addressed in this application is how to provide an FDY spinning oil that can maintain a relatively stable HLB value under high temperature conditions.

[0008] To solve at least one of the above problems, this application provides a method for preparing a composite FDY oil, the method comprising:

[0009] S100: Mix HLB modifier and water, stir and heat to 55°C to 65°C to obtain a first mixture;

[0010] S200: Add emulsifier, clustering agent, antistatic agent and smoothing agent to the first mixture, mix and keep warm while stirring to obtain the second mixture;

[0011] S300, after the second mixture cools to room temperature, adjust the pH value to 6.5 to 7.5, filter, and obtain the composite FDY oil agent;

[0012] The HLB modifier is a porous silica loaded with glyceryl ester ethoxylate and coated with ethyl cellulose.

[0013] In the above technical solution, by mass ratio, HLB modifier: water: emulsifier: clustering agent: antistatic agent: smoothing agent = (6-8): (12-16): (28-30): (2-4): (8-10): (36-40).

[0014] In the above technical solution, the emulsifier includes at least one or a combination of Tween and Span; the cleaving agent includes at least one or a combination of oleic acid diethanolamide and oleic acid triethanolamine; the antistatic agent includes at least one or a combination of isotridecyl phosphate potassium salt and dodecyltetradecyl phosphate potassium salt; and the smoothing agent includes at least one or a combination of pentaerythritol, fatty acid isopropyl ester, mineral oil, animal oil and vegetable oil.

[0015] In the above technical solution, the emulsifiers include Tween 40 and Span 80 in a mass ratio of (4-5):1, and the HLB value of the emulsifiers is 13 to 14.

[0016] In the above technical solution, the smoothing agent includes pentaerythritol, isopropyl fatty acid ester and vegetable oil in a mass ratio of 2:1:1; wherein the vegetable oil is at least one or a combination of soybean oil, coconut oil, palm oil and rapeseed oil.

[0017] In the above technical solution, the glycerol ester ethoxylate is prepared by ethoxylation reaction using triglycerides and ethylene oxide as raw materials.

[0018] The preparation method of the HLB regulator in the above technical solution includes:

[0019] S10. 3-Aminopropyltriethoxysilane is used to modify porous silica with silane to obtain modified porous silica.

[0020] S20. According to the mass ratio of glyceryl ester ethoxylate: modified porous silica: ethanol = (20-30): (16-20): 100, glyceryl ester ethoxylate and modified porous silica are mixed in ethanol, heated to 45°C to 50°C and kept at the temperature for 3 to 4 hours under ultrasonic vibration to obtain the third mixture.

[0021] S30. After drying the third mixture, it is mixed with an ethyl cellulose solution and atomized and dried to obtain an HLB modifier.

[0022] In the above technical solution, the HLB modifier includes a first HLB modifier and a second HLB modifier; the first HLB modifier is porous silica loaded with glyceryl ester ethoxylate A and coated with ethyl cellulose a; the second HLB modifier is porous silica loaded with glyceryl ester ethoxylate B and coated with ethyl cellulose b; the molar ratio of triglycerides and ethylene oxide used in the preparation process of glyceryl ester ethoxylate A and glyceryl ester ethoxylate B is different; the ethoxy content and / or degree of substitution of ethyl cellulose a and ethyl cellulose b are different.

[0023] In the above technical solution, the mass ratio of the first HLB modifier to the second HLB modifier is 1:(2-3); the molar ratio of triglyceride ester to ethylene oxide used in the preparation of glyceride ester ethoxylate A is 1:(60-65); the molar ratio of triglyceride ester to ethylene oxide used in the preparation of glyceride ester ethoxylate B is 1:(75-80); the ethoxy content of ethyl cellulose a is 44% to 45%, and the degree of substitution is 2.18 to 2.35; the ethoxy content of ethyl cellulose b is 46% to 48%, and the degree of substitution is 2.10 to 2.17.

[0024] This application also provides a composite FDY oiling agent, wherein the POY oiling agent is obtained by the preparation method of any of the above technical solutions.

[0025] Beneficial effects

[0026] The preparation method of the composite FDY oil agent of this application first involves mixing and stirring an HLB regulator and water, then heating the mixture to 55°C to 65°C to obtain a first mixture. Next, an emulsifier, a slub, an antistatic agent, and a smoothing agent are added to the first mixture, and the mixture is stirred while maintaining the temperature to obtain a second mixture. Finally, the second mixture is cooled to room temperature, the pH value is adjusted to 6.5 to 7.5, and the mixture is filtered to obtain the composite FDY oil agent. The HLB regulator used in this application is porous silica loaded with glyceryl ester ethoxylates and coated with ethyl cellulose. The porous structure of the silica allows for the loading of glyceryl ester ethoxylates. As the spinning process proceeds, under high temperature and high shear conditions, the ethyl cellulose dissolves, and the glyceryl ester ethoxylates within the porous silica are gradually released. Glyceryl ester ethoxylates can increase the HLB value of FDY oil to compensate for the decrease in HLB value caused by the increase in temperature. This allows the FDY oil to maintain a stable HLB value in the high-temperature spinning process and avoids the weakening of emulsification ability and oil-water phase separation caused by a sudden drop in HLB value. Detailed Implementation

[0027] To make the above-mentioned objectives, features and advantages of this application more apparent and understandable, a detailed description of specific embodiments of this application will be provided below.

[0028] Unless otherwise specified, all reagents and raw materials used in this application 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 per the product instructions.

[0029] This application provides a method for preparing a composite FDY oil, the method comprising:

[0030] S100: Mix HLB modifier and water, stir and heat to 55°C to 65°C to obtain a first mixture;

[0031] S200: Add emulsifier, clustering agent, antistatic agent and smoothing agent to the first mixture, mix and keep warm while stirring to obtain the second mixture;

[0032] S300. After the second mixture cools to room temperature, adjust the pH value to 6.5 to 7.5, filter, and obtain the composite FDY oil.

[0033] FDY oil is an indispensable auxiliary agent in the production of chemical fibers. It is mainly used to adjust the processing properties of fibers, ensure the stability of FDY fibers during high-speed spinning, and improve the quality of finished products.

[0034] FDY oils are typically in the form of a water-oil emulsion, which mainly consists of an oil phase composed of a cohesive agent, an antistatic agent, and a smoothing agent. The oil phase and water form a homogeneous emulsion under the action of an emulsifier.

[0035] FDY fiber spinning speeds can reach 3000m / min to 6000m / min. During high-speed spinning, friction occurs between the fiber and equipment components such as the guide roller and draft roller, easily leading to problems such as fiber breakage and fuzzing. Smoothing agents typically constitute the largest proportion of FDY oils. Mineral oils, polyol esters, and other smoothing agents are used to form a lubricating film on the fiber surface to reduce the coefficient of friction and minimize fiber wear. In this application, the smoothing agent includes at least one or a combination of pentaerythritol, isopropyl fatty acid esters, mineral oil, animal oil, and vegetable oil. The vegetable oil can be soybean oil, coconut oil, palm oil, or rapeseed oil.

[0036] FDY fibers are prone to static electricity due to friction, leading to filament dispersion and tangling. The antistatic agent in FDY oil is used to conduct charge through an ionic conductivity mechanism, preventing static adsorption and fiber breakage. In this application, the antistatic agent includes at least one or a combination of potassium isotridecyl phosphate and potassium dodecyltetradecyl phosphate.

[0037] Bundling agents enable FDY fiber monofilaments to aggregate into bundles, preventing fraying and ensuring winding quality. In this application, the bundling agent includes at least one or a combination of oleic acid diethanolamide and oleic acid triethanolamine.

[0038] Emulsifiers are used to form stable emulsions of oils in water, facilitating uniform oiling. For FDY oils, nonionic emulsifiers such as fatty alcohol polyoxyethylene ethers and castor oil polyoxyethylene ethers can be used, as well as ionic emulsifiers such as fatty acid salts and quaternary ammonium salts. In this application, the emulsifier includes at least one or a combination of Tween and Span.

[0039] In addition to the main raw materials mentioned above, those skilled in the art may also add antioxidants such as phenolic esters or amines, wetting agents such as sodium dioctyl sulfosuccinate, and preservatives such as 2,2-dibromo-3-nitropropionic acid amide, as well as stabilizers such as long-chain fatty alcohols, coconut oil-modified alkyd resins, and triethanolamine to the FDY oil as needed.

[0040] In addition to the liquid component, FDY oils may also contain some nanoscale hard particles, thus forming a composite FDY oil that combines emulsion and inorganic particles. For example, the hard inorganic particles that can be added to FDY oils mainly include silicon dioxide, silicon carbide, silicon nitride, zirconium oxide, titanium oxide, ceramic or glass powders, etc.

[0041] Among these, the aforementioned inorganic particles can impart or improve specific physical or chemical properties of the oil and fibers. For example, silica, as a shear thickening particle, can increase the viscosity of FDY oil under high temperature and high shear conditions, preventing demulsification due to a sudden drop in viscosity. Silica, with its porous structure, can also load some regulators to release the performance regulators loaded in its porous structure at appropriate times, thereby adjusting and improving the performance of the FDY oil. Silicon carbide and silicon nitride have high thermal conductivity, which can improve the heat dissipation performance of fibers. Some ceramic particles with conductive properties (such as antimony-doped tin oxide ATO) can be used in conjunction with traditional antistatic agents to give fibers better antistatic capabilities. Nanoscale zirconium oxide in FDY oil can be embedded in the fiber surface during the spinning process, improving the surface hardness and scratch resistance of the fibers. Titanium oxide of different particle sizes can be used as a whitening agent, matting agent, photocatalyst, and UV inhibitor, respectively, to adjust the whiteness or gloss of fibers, impart photocatalytic antibacterial and bacteriostatic effects to fibers, or to produce UV-resistant fibers.

[0042] It is understood that this application prepares a composite FDY oiling agent with added porous silica particles. In addition to silica, those skilled in the art can also select one or more of the other inorganic particles mentioned above and add them to the FDY oiling agent of this application according to actual needs.

[0043] It is understandable that inorganic particles are prone to agglomeration and sedimentation, therefore their addition amount in FDY oil needs to be controlled. In this application, porous silica serves as a carrier for glycerol ester ethoxylates, and the two together constitute an HLB modifier. The HLB modifier's mass percentage in the FDY oil preferably does not exceed 8%.

[0044] In this application, by mass ratio, HLB modifier: water: emulsifier: clustering agent: antistatic agent: smoothing agent = (6-8): (12-16): (28-30): (2-4): (8-10): (36-40).

[0045] Preferably, in this application, the HLB modifier:water:emulsifier:binder:antistatic agent:smoothing agent = 6:14:28:2:10:40 by mass ratio. The emulsifier has an HLB value of 13 to 14 and includes Tween 40 and Span 80 in a mass ratio of (4-5):1. The binder is triethanolamine oleate. The antistatic agent is potassium isotridecyl phosphate. The smoothing agent includes pentaerythritol, isopropyl fatty acid, and coconut oil in a mass ratio of 2:1:1.

[0046] It should be noted that the selection of the HLB value of the emulsifier and the compounding strategy are crucial to the emulsion stability, oiling uniformity, and fiber spinnability of the oiling agent. FDY oiling agents need to form a stable oil-in-water (O / W) emulsion system; therefore, the HLB value of the emulsifier should be biased towards the hydrophilic side. The optimal HLB range for O / W emulsions is 8 to 18. Tween-type emulsifiers, due to their strong hydrophilicity (HLB>10), are commonly used in FDY oiling agents. Furthermore, a single Tween type is insufficient to meet the comprehensive requirements of the FDY oiling agent system; the compounding method of the emulsifier is also key to improving spinning performance. This application uses a compound of Tween 40 and Span 80 at a mass ratio of (4-5):1 as the emulsifier to effectively prevent emulsion stratification.

[0047] Specifically, Tween 40 has an HLB value of approximately 15.6, while Span 80 has an HLB value of approximately 4.3. At a mass ratio of 4:1, the HLB value of the emulsifier formulated with Tween 40 and Span 80 is approximately 13.3. At a mass ratio of 5:1, the HLB value of the emulsifier formulated with Tween 40 and Span 80 is approximately 13.7. Emulsifiers with HLB values ​​between 13 and 14 conform to the optimal HLB range for O / W emulsions. Furthermore, Tween is an ethoxylated derivative of Span, and the two have similar structures and synergistic molecular structures, resulting in a more ordered interfacial arrangement after formulation. The combination of Tween 40 and Span 80 with varying HLB values ​​can cover a wider HLB range and form a dense interfacial film, improving emulsion stability and emulsifying effect.

[0048] For Tween and Span emulsifiers, their hydrophilicity depends on the hydrogen bonds formed between the polyethylene oxide (PEO) chains and water. As the temperature of the emulsifier increases, these hydrogen bonds break, reducing hydrophilicity and lowering the HLB value. In particular, when the spinning temperature exceeds 100°C, the HLB value of the oil decreases significantly, and the emulsion changes from clear to cloudy when the temperature reaches the emulsifier's cloud point. For Tween emulsifiers, which have an HLB value of around 14 to 16 at 25°C, the HLB value drops to 10 to 12 when the temperature rises to 120°C. Once the HLB value drops sharply, FDY oils will experience stratification, leading to more frequent coking and spinneret clogging in the equipment. It will also increase the fiber's coefficient of friction, resulting in increased fuzz and breakage rates.

[0049] Therefore, this application adds an HLB modifier to the FDY oil. The HLB modifier used in this application is porous silica loaded with glyceryl ester ethoxylates and coated with ethyl cellulose. The porous silica serves as a carrier for the glyceryl ester ethoxylates, encapsulating them. Ethyl cellulose acts as a protective film layer, controlling the timing of the sustained release of the glyceryl ester ethoxylates.

[0050] Before introducing the preparation method of the HLB regulator, the inventive concept of this application will first be described. In its prior application, CN117702312B, the applicant researched a regulator using porous silica as a carrier. CN117702312B discloses a viscosity-temperature-viscosity-concentration slow-release regulator using porous silica as a carrier, cellulose such as carboxymethyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose as viscosity modifiers, and ethyl cellulose as a coating film. It is added to polyester POY oils to balance the problem of viscosity reduction caused by temperature increases.

[0051] Based on relevant research on porous silica supports, the applicant discovered that porous silica can serve as a carrier for HLB-regulating components, thereby controlling the HLB value of the oil by slowly releasing the HLB-regulating components into it, thus maintaining the stability of the HLB value during use. To control the timing of the slow-release of the regulating components, the performance of the coating layer can be adjusted by regulating the composition and ratio of the raw materials, as well as the preparation process parameters, so that the dissolution or decomposition conditions of the coating layer match the desired release timing of the regulating components.

[0052] To effectively and promptly compensate for HLB value fluctuations in FDY oil, this application has conducted a series of studies on the selection of functional components in the HLB regulator, the preparation method of the porous silica carrier, and the raw materials and proportions of the coating layer. The preparation process of the HLB regulator used in this application will be described below.

[0053] This application focuses on utilizing the characteristics of porous silica, which can support regulators, and ethyl cellulose, which can coat porous silica and allow the regulators to be gradually released within a temperature range of 100°C to 120°C. Porous silica is used as a carrier for glycerol ester ethoxylates, and ethyl cellulose is used as the coating material to prepare an HLB regulator capable of slowly releasing glycerol ester ethoxylates. The glycerol ester ethoxylates are prepared from triglycerides and ethylene oxide via an ethoxylation reaction.

[0054] Specifically, the preparation methods of HLB modifiers include:

[0055] S10. 3-Aminopropyltriethoxysilane is used to modify porous silica with silane to obtain modified porous silica.

[0056] S20. According to the mass ratio of glyceryl ester ethoxylate: modified porous silica: ethanol = (20-30): (16-20): 100, glyceryl ester ethoxylate and modified porous silica are mixed in ethanol, heated to 45°C to 50°C and kept at the temperature for 3 to 4 hours under ultrasonic vibration to obtain the third mixture.

[0057] S30. After drying the third mixture, it is mixed with an ethyl cellulose solution and atomized and dried to obtain an HLB modifier.

[0058] The purpose of silane modification of porous silica with 3-aminopropyltriethoxysilane is to introduce amino groups onto the silica surface to further promote the loading of glycerol ester ethoxylates. Specifically, S10 includes:

[0059] S11. Heat-treat porous silica at a temperature of 300°C to 350°C for 2 to 3 hours to obtain activated porous silica.

[0060] S12. According to the mass ratio of 3-aminopropyltriethoxysilane: porous silica: anhydrous toluene = (4-8): (2-6): 100, first mix 3-aminopropyltriethoxysilane and anhydrous toluene evenly, then add the dried porous silica, and heat and reflux at 100°C for 6 to 8 hours under an inert atmosphere.

[0061] S13. After the reaction is complete, the mixture is cooled, the solids are separated, washed, and dried to obtain modified porous silica.

[0062] In order to remove residual 3-aminopropyltriethoxysilane, it is preferable to first wash with anhydrous toluene 2 to 3 times, then wash with anhydrous ethanol or acetone 2 to 3 times, and finally wash with deionized water.

[0063] Because silane modification introduces amino groups onto the surface of porous silica, and these amino groups can form hydrogen bonds with the ester or hydroxyl groups of glycerol ester ethoxylates, S20 allows glycerol ester ethoxylates to be loaded into the pores of the porous silica modified with 3-aminopropyltriethoxysilane.

[0064] Temperature conditions of 45°C to 50°C can reduce liquid viscosity, and ultrasonic oscillation can enhance molecular motion, thereby improving diffusion efficiency. The preferred power for ultrasonic oscillation is 400W to 500W. It is understood that after ultrasonic oscillation, cooling, separation of the solids, and washing are necessary to obtain the solid third mixture. To remove residual glycerol ester ethoxylates, washing with ice-cold ethanol below 4°C is preferred.

[0065] To improve loading efficiency and control the slow release of glycerol ester ethoxylates at a reasonable rate, avoiding excessively rapid diffusion, this application preferably uses porous silica with an average pore size of 10 nm to 30 nm. This pore size ensures that the pores of the porous silica can accommodate glycerol ester ethoxylate molecules while limiting their slow release at a reasonable rate. Thus, glycerol ester ethoxylates are loaded onto the porous silica through a combination of pore-filling physical adsorption and hydrogen-bonded chemical bonding, and can be dynamically released with the oil system at high temperatures, thereby compensating for the HLB value loss caused by hydrogen bond breaking in the oil.

[0066] It should be noted that, in order to avoid unnecessary release of glyceryl ester ethoxylates at low temperatures, the present invention further coats the porous silica loaded with glyceryl ester ethoxylates with ethyl cellulose in step S30.

[0067] It is understood that the drying of the third mixture can be carried out by hot air drying or infrared drying. After drying, it is preferable to purge with nitrogen for about 1 hour to remove residual solvent from the pores. After drying the third mixture, ethyl cellulose and ethyl acetate can be mixed at a mass ratio of 4-6:100, heated to 40°C to 45°C, and stirred evenly to prepare an ethyl cellulose solution. The third mixture is then immersed in the ethyl cellulose solution at a mass ratio of 15-20:100 under reduced pressure of -0.2 MPa to -0.1 MPa for 20 to 30 minutes, separated by filtration, and then atomized and dried at a temperature of 50°C to 60°C to obtain the HLB modifier.

[0068] Preferably, the HLB modifier of this application includes a first HLB modifier and a second HLB modifier; the mass ratio of the first HLB modifier to the second HLB modifier is 1:(2-3). The first HLB modifier is porous silica loaded with glyceryl ester ethoxylate A; the second HLB modifier is porous silica loaded with glyceryl ester ethoxylate B. The molar ratios of triglycerides and ethylene oxide used in the preparation of glyceryl ester ethoxylate A and glyceryl ester ethoxylate B are different. Specifically, the molar ratio of triglyceride ester to ethylene oxide used in the preparation of glyceryl ester ethoxylate A is 1:(60-65); the molar ratio of triglyceride ester to ethylene oxide used in the preparation of glyceryl ester ethoxylate B is 1:(75-80).

[0069] Glyceryl ester ethoxylates can be prepared by a catalytic reaction of glyceryl trioleate and ethylene oxide (EO). Their molecular structure has glycerol as the core backbone, with hydrophilic polyoxyethylene (PEO) segments attached to three alkyl chains, forming a three-arm structure. The purpose of controlling the molar ratio of glyceryl trioleate and ethylene oxide in this application is to regulate the HLB values ​​of glyceryl ester ethoxylate A and glyceryl ester ethoxylate B by controlling the EO addition number. This allows the HLB regulator to better match the actual HLB value fluctuations of the oil under high-temperature conditions, thus compensating for the HLB value of the oil.

[0070] Preferably, the ethoxy content of the ethyl cellulose used in preparing the second HLB regulator is higher than that of the ethyl cellulose used in preparing the first HLB regulator; and / or the degree of substitution (DS) of the ethyl cellulose used in preparing the second HLB regulator is higher than that of the ethyl cellulose used in preparing the first HLB regulator.

[0071] More preferably, the ethoxylated content of the ethyl cellulose used in preparing the second HLB regulator is 46% to 48%, and the ethoxylated content of the ethyl cellulose used in preparing the first HLB regulator is 44% to 45%; and / or the degree of substitution of the ethyl cellulose used in preparing the second HLB regulator is 2.18 to 2.35, and the degree of substitution of the ethyl cellulose used in preparing the first HLB regulator is 2.10 to 2.17.

[0072] A first HLB regulator, coated with ethyl cellulose with a lower ethoxy content / degree of substitution, can be released at a relatively lower temperature before the second HLB regulator, thus allowing glyceryl ester ethoxylate A, with a relatively lower HLB value, to be released into the oil first. As the temperature continues to rise, the second HLB regulator, coated with ethyl cellulose with a higher ethoxy content / degree of substitution, is subsequently released, thus allowing glyceryl ester ethoxylate B, with a relatively higher HLB value, to also be released into the oil. The two HLB regulators work together to stabilize the HLB value of the oil over a wider temperature range.

[0073] Example 1

[0074] In this embodiment, a series of glycerol ester ethoxylate samples were prepared. The raw material ratios and process parameters are listed in Table 1, and the preparation methods are as follows.

[0075] Dehydrated triglycerides (acid value ≤ 1 mg KOH / g, moisture ≤ 0.05%) were added to a reactor, along with 0.5% (by weight) of magnesium-aluminum composite metal oxide as a catalyst. The air was replaced with nitrogen three times (oxygen content ≤ 50 ppm). The reactor was heated to 135°C (heating rate 2°C / min), stirred (300 rpm), and dehydrated under vacuum for 1 hour. Vacuum was then applied and ethylene oxide (purity ≥ 99.8%, moisture ≤ 50 ppm) was introduced. The reactor was heated to 155°C (heating rate 1.5°C / min), and the reaction continued for the first reaction time. The temperature was then lowered to 80°C and neutralized to approximately pH 6.5 with 0.5 wt% citric acid aqueous solution. Vacuum devolatilization was performed to remove unreacted ethylene oxide (residual EO ≤ 100 ppm). The mixture was then filtered through diatomaceous earth (pore size 0.5 μm to 1 μm) to remove salt, yielding glycerides ethoxylate samples 1 to 4.

[0076] Table 1

[0077]

[0078] Example 2

[0079] In this embodiment, a series of HLB regulator samples were prepared. The raw material ratios and process parameters are listed in Table 2, and the preparation methods are as follows.

[0080] Porous silica (average pore size 20 nm) was placed in a muffle furnace and heat-treated at 300 °C for 2 hours under nitrogen protection, followed by natural cooling to obtain activated porous silica. Using a mass ratio of 3-aminopropyltriethoxysilane:porous silica:anhydrous toluene = 4:6:100, 3-aminopropyltriethoxysilane and anhydrous toluene were first added to a three-necked flask, mixed, and magnetically stirred until homogeneous. Then, dried porous silica was added, and nitrogen was introduced to replace the air. The mixture was heated in an oil bath to 100 °C and refluxed for 6 hours. After the reaction, the mixture was cooled to room temperature, the solids were separated by filtration, washed sequentially with anhydrous toluene, anhydrous ethanol, and deionized water, and dried under vacuum at 60 °C to obtain modified porous silica. According to the mass ratio of glyceryl ester ethoxylate: modified porous silica: ethanol = 20:20:100, glyceryl ester ethoxylate and modified porous silica were mixed in ethanol, heated to 45°C, and kept at this temperature for 3 hours under ultrasonic vibration at 400W. After ultrasonic vibration, the mixture was cooled to room temperature, the solids were separated by vacuum filtration, washed twice with ice-cold ethanol below 4°C, dried infrared at 60°C, and purged with nitrogen for 1 hour to obtain modified porous silica loaded with glyceryl ester ethoxylate. According to the mass ratio of ethyl cellulose: ethyl acetate = 5:100, ethyl cellulose and ethyl acetate were mixed, heated to 45°C, and stirred until homogeneous to prepare an ethyl cellulose solution. Modified porous silica loaded with glyceryl ester ethoxylates and ethyl cellulose solution were impregnated in ethyl cellulose solution under reduced pressure for 20 min at a mass ratio of 20:100. The modified porous silica loaded with glyceryl ester ethoxylates was then filtered and separated. The filter cake was transferred to a spray dryer for atomization drying (inlet temperature 60℃, outlet temperature 35℃, atomization pressure 0.5 MPa) to obtain HLB regulator samples 1 to 6.

[0081] Table 2

[0082]

[0083] Example 3

[0084] In this embodiment, a series of FDY oil samples were prepared. The raw material ratios and process parameters are listed in Table 3, and the preparation methods are as follows.

[0085] According to the mass ratio of HLB modifier:water:Tween 40:Span 80:triethanolamine oleate:potassium isotridecyl phosphate:pentaerythritol:isopropyl fatty acid:coconut oil =6:14:23:5:2:10:20:10:10, the HLB modifier and water were first mixed and heated to 60°C, and stirred at 200 rpm for 10 min to obtain an aqueous phase. Then, Tween 40, Span 80, triethanolamine oleate, potassium isotridecyl phosphate, pentaerythritol, isopropyl fatty acid, and coconut oil were added to the aqueous phase and mixed and kept warm, and stirred at 800 rpm for 30 min to obtain an emulsion. After the emulsion cooled to room temperature, the pH was adjusted to 7 with a buffer solution of citric acid and triethanolamine, and filtered to obtain FDY oil samples 1 to 9.

[0086] Table 3

[0087]

[0088] HLB stability test

[0089] FDY oil samples 1 to 9 were prepared into 10% aqueous solutions by adding water. Based on the Griffin method, emulsification tests were conducted at different test temperatures using the variable-temperature Griffin method. By comparing the HLB values ​​of the standard oil required to form a stable emulsion, the HLB values ​​of FDY oil samples 1 to 9 at different test temperatures were obtained.

[0090] Generally, the HLB value of FDY oil samples decreases as the test temperature increases. However, for the FDY oil sample provided in this application, because it contains an HLB modifier, when the test temperature rises to a certain level, the ethyl fiber membrane begins to dissolve, and the glycerol ester ethoxylates in the pores of the porous silica begin to be released, causing the HLB value of the FDY oil sample to rebound. Similarly, when the glycerol ester ethoxylates in the pores of the porous silica are completely released and the temperature continues to rise, the HLB value of the FDY oil sample decreases.

[0091] Since the variable-temperature Griffin method cannot obtain test results under linear and continuous temperature changes, this application, considering testing efficiency and cost, performs a sampling test every 3°C increase starting from 90°C. If the HLB value obtained in the (N+1)th test is higher than the HLB value obtained in the Nth test, the temperature corresponding to the (N+1)th test is recorded as the inflection point of the HLB value's rise. Similarly, after the inflection point appears, if the HLB value obtained in the (M+1)th test is lower than the HLB value obtained in the Mth test, the temperature corresponding to the (M+1)th test is recorded as the inflection point of the HLB value's fall.

[0092] Table 4 lists the HLB value recovery inflection point temperature and the decline inflection point temperature for FDY oil samples 1 to 9, as well as the difference between the decline inflection point and the recovery inflection point. According to the test results in Table 4, all FDY oil samples in this application showed an HLB value recovery at high temperatures. Among them, the recovery inflection points of FDY oil samples 1, 4, 7, 8, and 9 were relatively low, while the recovery inflection points of FDY oil samples 3 and 6 were the highest. FDY oil sample 9 had the highest decline inflection point, and the decline inflection points of FDY oil samples 5 and 8 were also relatively high, while the decline inflection point of FDY oil sample 1 was the lowest. The difference between the decline inflection point and the recovery inflection point of FDY oil samples 9 and 8 was relatively large, indicating that FDY oil samples 9 and 8 could maintain stable HLB values ​​over a relatively large temperature range. The reason for the above phenomenon is that both FDY oil samples 9 and 8 used a combination of two HLB modifiers. Furthermore, the HLB modifiers contained in FDY oil samples 9 and 8 were glyceryl ester ethoxylates with a higher molar ratio of triglyceride to ethylene oxide, and ethyl cellulose with a higher degree of substitution. The glyceryl ester ethoxylates with a higher molar ratio of triglyceride to ethylene oxide can regulate the HLB value of the oil to a greater extent, and the ethyl cellulose with a higher degree of substitution dissolves more slowly. This results in a higher inflection point for the decrease in HLB value in FDY oil samples 9 and 8.

[0093] Table 4

[0094]

[0095] This is not a limitation. Any person skilled in the art may make various alterations and modifications without departing from the spirit and scope of this application; therefore, the scope of protection of this application shall be determined by the scope defined in the claims.

Claims

1. A method for preparing a composite FDY oil agent, characterized in that, The preparation method includes: S100: Mix HLB modifier and water, stir and heat to 55°C to 65°C to obtain a first mixture; S200: Add emulsifier, clustering agent, antistatic agent and smoothing agent to the first mixture, mix and keep warm while stirring to obtain a second mixture; S300. After the second mixture cools to room temperature, adjust the pH value to 6.5 to 7.5, filter, and obtain the composite FDY oil agent; The HLB modifier is a porous silica loaded with glyceryl ester ethoxylate and coated with ethyl cellulose. The preparation method of the HLB regulator includes: S10. The porous silica is modified with 3-aminopropyltriethoxysilane to obtain modified porous silica. S20. According to the mass ratio of glyceryl ester ethoxylate: modified porous silica: ethanol = (20-30): (16-20): 100, the glyceryl ester ethoxylate and the modified porous silica are mixed in the ethanol, heated to 45°C to 50°C and kept at the temperature for 3 to 4 hours under ultrasonic vibration to obtain a third mixture. S30. After drying the third mixture, it is mixed with an ethyl cellulose solution and then atomized and dried to obtain the HLB regulator. The HLB modifier includes a first HLB modifier and a second HLB modifier; the first HLB modifier is a porous silica loaded with glyceryl ester ethoxylate A and coated with ethyl cellulose a; the second HLB modifier is a porous silica loaded with glyceryl ester ethoxylate B and coated with ethyl cellulose b; the glyceryl ester ethoxylate is prepared by ethoxylation reaction using triglycerides and ethylene oxide as raw materials; the molar ratio of triglycerides and ethylene oxide used in the preparation of glyceryl ester ethoxylate A and glyceryl ester ethoxylate B is different; the ethoxy content and / or degree of substitution of ethyl cellulose a and ethyl cellulose b are different.

2. The preparation method according to claim 1, characterized in that, By mass ratio, HLB modifier: water: emulsifier: clustering agent: antistatic agent: smoothing agent = (6-8): (12-16): (28-30): (2-4): (8-10): (36-40).

3. The preparation method according to claim 1, characterized in that, The emulsifier includes at least one or a combination of Tween and Span; The slugging agent includes at least one or a combination of diethanolamide oleate and triethanolamine oleate. The antistatic agent includes at least one or a combination of potassium isotridecyl phosphate and potassium dodecyltetradecyl phosphate. The smoothing agent includes at least one or a combination of pentaerythritol, isopropyl fatty acid esters, mineral oil, animal oil, and vegetable oil.

4. The preparation method according to claim 3, characterized in that, The emulsifier comprises Tween 40 and Span 80 in a mass ratio of (4-5):1, and the emulsifier has an HLB value of 13 to 14.

5. The preparation method according to claim 3, characterized in that, The smoothing agent comprises pentaerythritol, isopropyl fatty acid ester, and vegetable oil in a mass ratio of 2:1:1; wherein the vegetable oil is at least one or a combination of soybean oil, coconut oil, palm oil, and rapeseed oil.

6. The preparation method according to claim 1, characterized in that, The mass ratio of the first HLB modifier to the second HLB modifier is 1:(2-3); The molar ratio of glycerol trioleate and ethylene oxide used to prepare the glycerol ester ethoxylate A is 1:(60-65). The molar ratio of glycerol trioleate and ethylene oxide used to prepare the glycerol ester ethoxylate B is 1:(75-80). The ethoxylated content of ethyl cellulose a is 44% to 45%, and the degree of substitution is 2.18 to 2.35; The ethoxy content of ethyl cellulose b is 46% to 48%, and the degree of substitution is 2.10 to 2.

17.

7. A composite FDY oil agent, characterized in that, The composite FDY oil is obtained by the preparation method described in any one of claims 1 to 6.

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