Composite FDY oiling agent and preparation method thereof

Abstract

The invention provides a composite FDY oil agent and a preparation method thereof.The preparation method comprises the steps that an HLB regulator and water are mixed, heated and stirred, and a first mixture is obtained; adding an emulsifier, a bundling agent, an antistatic agent and a smoothing agent into the first mixture, mixing, preserving heat and stirring to obtain a second mixture; cooling the second mixture to room temperature, adjusting the pH value to 6.5-7.5, and filtering to obtain the composite FDY oiling agent; wherein the HLB regulator is porous silicon dioxide loaded with glyceride ethoxylate, and the surface of the porous silicon dioxide is coated with ethyl cellulose. The composite FDY oil agent disclosed by the invention can keep the stability of an HLB (Hydrophile-Lipophile Balance) value under a high-temperature condition, and is relatively good in environment-friendly degree.

Description

Technical Field

[0001] The present application relates to the technical field of chemical materials, and in particular to a composite FDY oil agent and a preparation method thereof. Background Art

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

[0003] Polyester products primarily include POY (pre-oriented yarn), FDY (fully drawn yarn), and DTY (draw textured yarn). FDY polyester fiber is characterized by its simultaneous high-speed stretching (>4000 m / min) and heat setting during the spinning process. Its molecular chains are highly oriented and crystallized, allowing for direct production of finished yarn. As a result, FDY polyester fiber boasts a smooth surface, high gloss, and dimensional stability, making it particularly suitable for linings or silk-like fabrics.

[0004] Existing FDY spin finishes typically use nonionic surfactants (such as glycerol ethoxylates and fatty alcohol polyoxyethylene ethers (AEOs)) as their core component. Their hydrophilicity relies on hydrogen bonds formed between polyoxyethylene chains (EO chains) and water. As the spinning process progresses, the temperature of the FDY spin finish gradually increases, intensifying the thermal motion of water molecules and evaporating water from the finish. This disrupts the hydrogen bonds between the EO chains and water molecules, resulting in a decrease in the FDY spin finish's hydrophilicity. Furthermore, when the spinning temperature exceeds the cloud point, the nonionic surfactant transforms from a transparent solution to a milky, turbid liquid, and the HLB value drops dramatically.

[0005] The decrease in the HLB value of FDY spinning oil at high temperatures weakens its emulsifying ability and leads to a tendency for oil-water phase separation. This problem can cause fluctuations in the friction coefficient of FDY fibers and the risk of fiber lint and breakage. Existing research results show that when the temperature of FDY spinning oil increases from 40°C to 100°C, its HLB value decreases by 15% to 20%, while the dynamic friction coefficient of FDY fibers increases by 0.05 to 0.08.

[0006] How to avoid the HLB value fluctuation of 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 solved by the present application is how to provide an FDY spinning oil with a relatively stable HLB value under high temperature conditions.

[0008] To solve at least one of the above problems, the present application provides a method for preparing a composite FDY oil agent, the preparation method comprising: S100, mixing an HLB regulator and water, stirring, and heating to 55° C. to 65° C. to obtain a first mixture; S200, adding an emulsifier, a sizing agent, an antistatic agent, and a smoothing agent to the first mixture, mixing and stirring while maintaining the temperature to obtain a second mixture; S300, after the second mixture is cooled to room temperature, the pH value is adjusted to 6.5 to 7.5, and filtered to obtain a composite FDY oil; The HLB regulator is porous silica loaded with glycerol ethoxylate and coated with ethyl cellulose.

[0009] In the above technical solution, the mass ratio of HLB regulator: water: emulsifier: sizing agent: antistatic agent: smoothing agent is (6-8): (12-16): (28-30): (2-4): (8-10): (36-40).

[0010] In the above technical solution, the emulsifier includes at least one of Tween and Span or a combination thereof; the sizing agent includes at least one of oleic acid diethanolamide and oleic acid triethanolamine or a combination thereof; the antistatic agent includes at least one of isomeric tridecyl phosphate potassium salt and dodecyl phosphate potassium salt or a combination thereof; and the smoothing agent includes at least one of pentaerythritol, fatty acid isopropyl ester, mineral oil, animal oil and vegetable oil or a combination thereof.

[0011] In the above technical solution, the emulsifier includes Tween 40 and Span 80 in a mass ratio of (4-5):1, and the HLB value of the emulsifier is 13 to 14.

[0012] In the above technical solution, the lubricant 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 of soybean oil, coconut oil, palm oil, rapeseed oil or a combination thereof.

[0013] In the above technical solution, glyceride ethoxylate is prepared by ethoxylation reaction using triglyceride and ethylene oxide as raw materials.

[0014] In the above technical solution, the preparation method of the HLB regulator includes: S10, using 3-aminopropyltriethoxysilane to perform silane modification on the porous silica to obtain modified porous silica; S20, mixing the glycerol ethoxylate and the modified porous silica in ethanol at a mass ratio of glycerol ethoxylate: modified porous silica: ethanol = (20-30): (16-20): 100, heating to 45° C. to 50° C. and maintaining the mixture under ultrasonic vibration for 3 to 4 hours to obtain a third mixture; S30, drying the third mixture, mixing it with the ethyl cellulose solution, and atomizing and drying it to obtain an HLB regulator.

[0015] In the above technical solution, the HLB regulator includes a first HLB regulator and a second HLB regulator; the first HLB regulator is a porous silica loaded with glycerol ethoxylate A and coated with ethyl cellulose a on the surface; the second HLB regulator is a porous silica loaded with glycerol ethoxylate B and coated with ethyl cellulose b on the surface; the molar ratios of triglyceride and ethylene oxide used in the preparation process of glycerol ethoxylate A and glycerol ethoxylate B are different; the ethoxy content and / or degree of substitution of ethyl cellulose a and ethyl cellulose b are different.

[0016] In the above technical solution, the mass ratio of the first HLB regulator to the second HLB regulator is 1:(2-3); the molar ratio of glycerol trioleate and ethylene oxide used in preparing glycerol ethoxylate A is 1:(60-65); the molar ratio of glycerol trioleate and ethylene oxide used in preparing glycerol 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.

[0017] The present application also provides a composite FDY oil, and the POY oil is obtained by using the preparation method of any of the above technical solutions.

[0018] Beneficial effects The preparation method of the composite FDY oil agent of the present application is to first mix the HLB regulator and water and stir and heat them to 55°C to 65°C to obtain a first mixture. Then, an emulsifier, a sizing agent, an antistatic agent and a smoothing agent are added to the first mixture, mixed and stirred while keeping warm 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 filtered to obtain a composite FDY oil agent. Among them, the HLB regulator used in the present application is porous silica loaded with glycerol ethoxylate and coated with ethyl cellulose on the surface. The pore structure of the porous silica can load glycerol ethoxylate. As the spinning process proceeds, under high temperature and high shear conditions, the ethyl cellulose dissolves and the glycerol ethoxylate in the porous silica is gradually released. Glyceryl ethoxylate can increase the HLB value of FDY oil to compensate for the decrease in HLB value of FDY oil caused by temperature increase, thereby allowing FDY oil to maintain a stable HLB value during the high-temperature spinning process and avoid a sudden drop in HLB value, which may lead to weakened emulsification ability and oil-water phase separation. DETAILED DESCRIPTION

[0019] In order to make the above-mentioned objects, features and advantages of the present application more obvious and easy to understand, the following is a detailed description of the specific embodiments of the present application.

[0020] Unless otherwise specified, the reagents and raw materials used in this application can be purchased through commercial channels. Experimental methods in the following examples where specific conditions are not specified were performed according to conventional methods and conditions, or selected according to the product specifications.

[0021] The present application provides a method for preparing a composite FDY oil agent, which comprises: S100, mixing an HLB regulator and water, stirring, and heating to 55° C. to 65° C. to obtain a first mixture; S200, adding an emulsifier, a sizing agent, an antistatic agent, and a smoothing agent to the first mixture, mixing and stirring while maintaining the temperature to obtain a second mixture; S300: After the second mixture is cooled to room temperature, the pH value is adjusted to 6.5 to 7.5, and filtered to obtain a composite FDY oil.

[0022] FDY oil is an indispensable auxiliary agent in chemical fiber production. It is mainly used to adjust the processing properties of the fiber, ensure the stability of FDY fiber during high-speed spinning, and improve the quality of the finished product.

[0023] FDY oil is usually in the form of a water-oil emulsion, which mainly includes an oil phase composed of a sizing agent, an antistatic agent and a smoothing agent. The oil phase and water form a homogeneous emulsion under the action of an emulsifier.

[0024] The spinning speed of FDY fiber can reach 3000m / min to 6000m / min. During the high-speed spinning process, the fiber rubs against equipment components such as the yarn guide and drafting roller, which can easily lead to problems such as broken ends and lint. Smoothing agents usually account for the largest proportion of components in FDY oil. Smoothing agents such as mineral oil and polyol ester are used to form a lubricating film on the fiber surface to reduce the friction coefficient and reduce fiber wear. In this application, the smoothing agent includes at least one of pentaerythritol, isopropyl fatty acid ester, mineral oil, animal oil and vegetable oil, or a combination thereof. Among them, the vegetable oil can be soybean oil, coconut oil, palm oil, or rapeseed oil.

[0025] FDY fibers are susceptible to static electricity generated by friction, leading to filament dispersion and entanglement. Antistatic agents in FDY finishes are used to conduct charge through ionic conduction, preventing static adsorption and fiber breakage. In this application, the antistatic agent includes at least one of isomeric potassium tridecyl phosphate and potassium dodecyl phosphate, or a combination thereof.

[0026] The bundling agent can make the filaments of the FDY fiber gather into bundles, avoid loose fibers, and ensure the quality of winding and molding. In the present application, the bundling agent includes at least one of oleic acid diethanolamide and oleic acid triethanolamine or a combination thereof.

[0027] Emulsifiers are used to form a stable emulsion of the oil in water, facilitating uniform application. For FDY oil, 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 of Tween and Span, or a combination thereof.

[0028] In addition to the above main raw materials, 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-nitrilopropionamide, as well as stabilizers such as long-chain fatty alcohols, coconut oil-modified alkyd resins, and triethanol to the FDY oil according to actual needs.

[0029] In addition to the liquid component, FDY oil can also contain nanoscale hard particles, forming a composite FDY oil composed of an emulsion and inorganic particles. Examples of hard inorganic particles that can be added to FDY oil include silicon dioxide, silicon carbide, silicon nitride, zirconium oxide, titanium oxide, ceramic, or glass powders.

[0030] The aforementioned inorganic particles can impart or improve specific physical or chemical properties to the oil and fiber. For example, silica, as a shear-thickening particle, can increase the viscosity of FDY oil under high temperature and high shear conditions, preventing sudden viscosity drops that could lead to demulsification. The porous structure of silica can also load modifiers, releasing these modifiers from its porous structure at the appropriate time to adjust and improve the properties of the FDY oil. Silicon carbide and silicon nitride have high thermal conductivity, improving the heat dissipation of fibers. Conductive ceramic particles (such as antimony-doped tin oxide (ATO)) can be used in conjunction with traditional antistatic agents to impart enhanced antistatic properties to fibers. Nano-sized zirconium oxide in FDY oil can be embedded in the fiber surface during the spinning process, improving surface hardness and scratch resistance. Titanium oxide of varying particle sizes can be used as a brightener, matting agent, photocatalyst, and UV inhibitor, respectively, to adjust the whiteness or gloss of fibers, impart photocatalytic and antibacterial properties, or create UV-resistant fibers.

[0031] It is understood that the present invention prepares a composite FDY oil containing porous silica particles. In addition to silica, those skilled in the art may also select one or more of the other inorganic particles mentioned above and add them to the FDY oil of the present invention, depending on actual needs.

[0032] As is understandable, inorganic particles tend to aggregate and settle, so their addition to the FDY oil needs to be controlled. In this application, porous silica serves as a carrier for the glyceride ethoxylate, and the two together constitute the HLB modifier. The mass percentage of this HLB modifier in the FDY oil is preferably no more than 8%.

[0033] In the present application, the mass ratio of HLB regulator: water: emulsifier: sizing agent: antistatic agent: smoothing agent is (6-8): (12-16): (28-30): (2-4): (8-10): (36-40).

[0034] Preferably, in this application, the mass ratio of HLB modifier: water: emulsifier: sizing agent: antistatic agent: smoothing agent is 6:14:28:2:10:40. 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 sizing agent is triethanolamine oleate. The antistatic agent is potassium isotridecyl phosphate. The smoothing agent includes pentaerythritol, isopropyl fatty acid ester, and coconut oil in a mass ratio of 2:1:1.

[0035] It should be noted that the selection of the HLB value of the emulsifier and the compounding strategy are crucial to the emulsification stability, oiling uniformity, and fiber spinnability of the oil. FDY oil needs to form a stable oil-in-water (O / W) emulsion system, so 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 emulsifiers are commonly used for FDY oils due to their strong hydrophilicity (HLB>10). In addition, a single Tween type is difficult to meet the comprehensive requirements of the FDY oil system. The compounding method of the emulsifier is also the key to improving spinning performance. This application uses a compound of Tween 40 and Span 80 in a mass ratio of (4-5):1 as an emulsifier, the purpose of which is to effectively prevent emulsion stratification.

[0036] Specifically, the HLB value of Tween 40 is approximately 15.6, and the HLB value of Span 80 is approximately 4.3. When the mass ratio is 4:1, the HLB value of the emulsifier of Tween 40 and Span 80 is approximately 13.3. When the mass ratio is 5:1, the HLB value of the emulsifier of Tween 40 and Span 80 is approximately 13.7. Emulsifiers with HLB values between 13 and 14 meet the optimal HLB range for O / W emulsions. In addition, Tween is an ethoxylated derivative of Span, and the two have similar structures and synergistic molecular structures, resulting in a more orderly interface arrangement after compounding. The combination of Tween 40 and Span 80 with high and low HLB values can cover a wider HLB range and form a dense interfacial film, thereby improving the stability and emulsification effect of the emulsion.

[0037] For emulsifiers like Tween and Span, their hydrophilicity relies on hydrogen bonds formed between polyoxyethylene (PEO) chains and water. When the emulsifier's temperature rises, its hydrogen bonds break, its hydrophilicity weakens, and its HLB value decreases. In particular, when the spinning temperature exceeds 100°C, the oil's HLB value drops significantly. When the temperature reaches the emulsifier's cloud point, the emulsion turns from clear to turbid. For Tween emulsifiers, which have an HLB value of approximately 14 to 16 at 25°C, this value drops to 10 to 12 at 120°C. A sudden drop in the HLB value can cause FDY oils to stratify, making equipment more susceptible to coking and spinneret blockage. It can also increase the fiber's friction coefficient, resulting in increased fiber lint and breakage rates.

[0038] To this end, the present application adds an HLB modifier to the FDY oil. The HLB modifier employed in this application is porous silica loaded with glyceride ethoxylate and coated with ethyl cellulose. The porous silica acts as a carrier for the glyceride ethoxylate, encapsulating it. The ethyl cellulose acts as a protective film to control the timing of its sustained release.

[0039] Before introducing the preparation method of the HLB modifier, we first introduce the inventive concept of this application. In its prior application, granted with publication number CN117702312B, the applicant studied modifiers using porous silica as a carrier. CN117702312B discloses a sustained-release viscosity-temperature-viscosity modifier using porous silica as a carrier, a cellulose such as carboxymethyl cellulose, hydroxypropyl methyl cellulose, or hydroxyethyl cellulose as a viscosity modifier, and ethyl cellulose as a coating. This modifier is added to polyester POY finishes to compensate for the decrease in finish viscosity caused by rising temperatures.

[0040] Based on research on porous silica supports, the applicant discovered that porous silica can serve as a carrier for modifiers, loading HLB-modifying components. This allows for the controlled release of HLB-modifying components into the oil, thereby controlling the HLB value of the oil and maintaining a stable HLB value during use. To control the timing of the controlled release of the modifier, the coating layer's properties can be adjusted by adjusting the coating layer's raw material composition, ratio, and manufacturing process parameters, aligning the coating layer's dissolution or decomposition conditions with the desired release timing of the modifier.

[0041] To ensure timely and effective compensation for HLB fluctuations in the FDY oil, this application has conducted a series of studies on the selection of functional components in the HLB modifier, the preparation method of the porous silica carrier, and the raw materials and ratios of the coating layer. The preparation process of the HLB modifier used in this application is described below.

[0042] This application aims to utilize the characteristics of porous silica that can load the regulator and ethyl cellulose that can coat the porous silica and gradually release the regulator within the porous silica within a temperature range of 100°C to 120°C. By using porous silica as a carrier for glyceride ethoxylate and ethyl cellulose as a coating material, an HLB regulator capable of sustained release of glyceride ethoxylate is prepared. The glyceride ethoxylate is prepared from triglycerides and ethylene oxide through an ethoxylation reaction.

[0043] Specifically, the preparation method of the HLB regulator includes: S10, using 3-aminopropyltriethoxysilane to perform silane modification on the porous silica to obtain modified porous silica; S20, mixing the glycerol ethoxylate and the modified porous silica in ethanol at a mass ratio of glycerol ethoxylate: modified porous silica: ethanol = (20-30): (16-20): 100, heating to 45° C. to 50° C. and maintaining the mixture under ultrasonic vibration for 3 to 4 hours to obtain a third mixture; S30, drying the third mixture, mixing it with the ethyl cellulose solution, and atomizing and drying it to obtain an HLB regulator.

[0044] The purpose of silane modification of porous silica with 3-aminopropyltriethoxysilane is to introduce amino groups on the silica surface to further promote the loading of glycerol ethoxylate. Specifically, S10 comprises: S11, heat-treating the porous silica at a temperature of 300° C. to 350° C. for 2 to 3 hours to obtain activated porous silica; S12. First, 3-aminopropyltriethoxysilane and anhydrous toluene are uniformly mixed in a mass ratio of 3-aminopropyltriethoxysilane: porous silica: anhydrous toluene = (4-8): (2-6): 100, and then the dried porous silica is added. The mixture is heated under reflux at 100° C. under an inert atmosphere for 6 to 8 hours. S13. After the reaction is completed, the temperature is lowered, the solid matter is separated, washed, and dried to obtain modified porous silica.

[0045] In order to wash away the residual 3-aminopropyltriethoxysilane, it is preferred 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.

[0046] Since the silane modification treatment introduces amino groups on the surface of the porous silica, and the amino groups can form hydrogen bonds with the ester groups or hydroxyl groups of the glycerol ethoxylate, the glycerol ethoxylate can be loaded into the pores of the porous silica modified with 3-aminopropyltriethoxysilane through S20.

[0047] A temperature of 45°C to 50°C can reduce liquid viscosity, and ultrasonic vibration can enhance molecular motion, thereby improving diffusion efficiency. The power of ultrasonic vibration is preferably 400W to 500W. It is understood that after ultrasonic vibration, cooling, solid separation, and washing are required to obtain the solid third mixture. To wash away residual glyceride ethoxylates, icy ethanol below 4°C is preferably used for washing.

[0048] In order to improve load efficiency and control glyceride ethoxylate to release at a reasonable speed, avoid it from spreading too rapidly, the application preferably adopts porous silica with an average pore size of 10nm to 30nm. The above-mentioned pore size can ensure that glyceride ethoxylate molecules can be accommodated in the pore of porous silica, and can also limit glyceride ethoxylate to release at a reasonable speed. Thus, glyceride ethoxylate is filled with physical adsorption by the pore, and the dual action of hydrogen bond chemical bonding, is loaded on porous silica, can dynamically release with the oil agent system at high temperature, thus compensating the HLB value of oil agent because of hydrogen bond fracture loss.

[0049] It should be noted that, in order to avoid unnecessary release of glyceride ethoxylate at low temperature, the present invention further coats the porous silica loaded with glyceride ethoxylate with ethyl cellulose in S30.

[0050] It is understood that the third mixture can be dried using hot air drying or infrared drying. After drying, it is preferably purged with nitrogen for approximately 1 hour to remove any residual solvent from the pores. After drying the third mixture, ethyl cellulose and ethyl acetate can be mixed in a mass ratio of ethyl cellulose:ethyl acetate = (4-6):100, heated to 40°C to 45°C, and stirred to prepare an ethyl cellulose solution. The third mixture is then immersed in the ethyl cellulose solution at a pressure of -0.2 MPa to -0.1 MPa for 20 to 30 minutes, at a mass ratio of third mixture:ethyl cellulose solution = (15-20):100. The third mixture is then separated by filtration and spray dried at 50°C to 60°C to obtain an HLB modifier.

[0051] Preferably, the HLB modifier of the present application comprises 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 glyceride ethoxylate A, and the second HLB modifier is porous silica loaded with glyceride ethoxylate B. Glyceride ethoxylate A and glyceride ethoxylate B utilize different molar ratios of triglyceride to ethylene oxide during preparation. For example, the molar ratio of triolein to ethylene oxide used in the preparation of glyceride ethoxylate A is 1:(60-65), while the molar ratio of triolein to ethylene oxide used in the preparation of glyceride ethoxylate B is 1:(75-80).

[0052] Glyceride ethoxylates can be produced by the catalytic reaction of glycerol trioleate and ethylene oxide (EO). Their molecular structure consists of a glycerol core skeleton with three alkyl chains connected to hydrophilic polyoxyethylene (PEO) segments, forming a three-arm structure. The purpose of controlling the molar ratio of glycerol trioleate to ethylene oxide in this application is to regulate the HLB values of glycerol ethoxylate A and glycerol ethoxylate B by controlling the EO adduct number. This allows the HLB regulator to compensate for the HLB value of the oil under high temperature conditions, more closely matching the actual HLB value fluctuations of the oil.

[0053] Preferably, the ethoxy content of the ethyl cellulose used to prepare the second HLB adjuster is higher than the ethoxy content of the ethyl cellulose used to prepare the first HLB adjuster; and / or the degree of substitution (DS) of the ethyl cellulose used to prepare the second HLB adjuster is higher than the degree of substitution of the ethyl cellulose used to prepare the first HLB adjuster.

[0054] Further preferably, the ethoxy content of the ethyl cellulose used to prepare the second HLB regulator is 46% to 48%, and the ethoxy content of the ethyl cellulose used to prepare the first HLB regulator is 44% to 45%; and / or the degree of substitution of the ethyl cellulose used to prepare the second HLB regulator is 2.18 to 2.35, and the degree of substitution of the ethyl cellulose used to prepare the first HLB regulator is 2.10 to 2.17.

[0055] The first HLB adjuster, coated with ethyl cellulose having a lower ethoxy content and degree of substitution, can be controlled-released before the second HLB adjuster at relatively low temperatures, thereby releasing glyceride ethoxylate A, which has a relatively low HLB value, into the oil first. As the temperature continues to rise, the second HLB adjuster, coated with ethyl cellulose having a higher ethoxy content and degree of substitution, is subsequently controlled-released, thereby also releasing glyceride ethoxylate B, which has a relatively higher HLB value, into the oil. The two HLB adjusters work together to stabilize the HLB value of the oil over a wider temperature range.

[0056] Example 1 In this example, a series of glycerol ethoxylate samples were prepared. The raw material ratios and process parameters are listed in Table 1. The preparation method is as follows.

[0057] Dehydrated triolein (acid value ≤1 mg KOH / g, moisture ≤0.05%) was placed in a reactor, and a magnesium-aluminum composite metal oxide (0.5% by weight of triolein) was added 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) with stirring (300 rpm). Vacuum dehydration was performed for 1 h, followed by evacuation and the introduction of ethylene oxide (purity ≥99.8%, moisture ≤50 ppm). The reactor was then heated to 155°C (heating rate 1.5°C / min) for the first reaction time, then cooled to 80°C and neutralized with 0.5 wt% aqueous citric acid to a pH of approximately 6.5. 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 to 1 μm) to remove salts, yielding glyceride ethoxylate samples 1 to 4.

[0058] Table 1 Example 2 In this example, a series of HLB regulator samples were prepared. The raw material ratios and process parameters are listed in Table 2. The preparation method is as follows.

[0059] Porous silica (average pore size 20 nm) was placed in a muffle furnace and heat treated at 300°C for 2 hours under nitrogen. The activated porous silica was then cooled naturally to obtain the activated porous silica. 3-Aminopropyltriethoxysilane and anhydrous toluene were first added to a three-necked flask in a mass ratio of 4:6:100. The mixture was mixed and magnetically stirred until uniform. The dried porous silica was then added, and the air was replaced by nitrogen. 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 in a vacuum oven at 60°C to obtain the modified porous silica. Glyceride ethoxylate and modified porous silica were mixed in ethanol at a mass ratio of 20:20:100, heated to 45°C, and ultrasonically shaken at 400 W for 3 hours. After ultrasonic shaking, the mixture was cooled to room temperature, filtered to separate the solids, washed twice with ice-cold ethanol below 4°C, dried at 60°C, and purged with nitrogen for 1 hour to obtain modified porous silica loaded with glyceride ethoxylate. Ethyl cellulose and ethyl acetate were mixed at a mass ratio of 5:100, heated to 45°C, and stirred to prepare an ethyl cellulose solution. The modified porous silica loaded with glycerol ethoxylate was immersed in the ethyl cellulose solution under reduced pressure at a pressure of -0.1 MPa for 20 min in a mass ratio of modified porous silica loaded with glycerol ethoxylate: ethyl cellulose solution = 20:100. The modified porous silica loaded with glycerol ethoxylate was then separated by filtration, and the filter cake was transferred to a spray dryer for atomization drying (inlet temperature 60°C, outlet temperature 35°C, atomization pressure 0.5 MPa) to obtain HLB regulator samples 1 to 6.

[0060] Table 2 Example 3 In this example, a series of FDY oil samples were prepared. The raw material ratios and process parameters are listed in Table 3. The preparation method is as follows.

[0061] The HLB adjuster and water were first mixed in a mass ratio of 6:14:23:5:2:10:20:10:10 for HLB adjuster: water: Tween 40: Span 80: triethanolamine oleate: potassium tridecanol phosphate: pentaerythritol: isopropyl fatty acid ester: coconut oil. The mixture was heated to 60°C and stirred at 200 rpm for 10 minutes to obtain an aqueous phase. Tween 40, Span 80, triethanolamine oleate, potassium tridecanol phosphate, pentaerythritol, isopropyl fatty acid ester, and coconut oil were then added to the aqueous phase. The mixture was then kept warm and stirred at 800 rpm for 30 minutes 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. The mixture was then filtered to obtain FDY oil samples 1 to 9.

[0062] Table 3 HLB stability test FDY oil samples 1 to 9 were each added with water to prepare aqueous solutions with a 10% oil concentration. Emulsification tests were conducted at different test temperatures using the variable temperature Griffin method, based on the Griffin method. The HLB values of FDY oil samples 1 to 9 at different test temperatures were determined by comparing the HLB values of the standard oils required to form stable emulsions.

[0063] Generally speaking, the HLB value of an FDY oil sample decreases as the test temperature increases. For the FDY oil sample provided herein, since it contains an HLB modifier, when the test temperature rises to a certain level, the ethyl fiber membrane begins to dissolve, releasing the glyceride ethoxylate from the pores of the porous silica, and the HLB value of the FDY oil sample rebounds. Similarly, when the glyceride ethoxylate from the pores of the porous silica is completely slowly released and the temperature continues to rise, the HLB value of the FDY oil sample decreases.

[0064] Among them, since the variable temperature Griffin method cannot achieve the test results under the condition of linear continuous temperature change, this application takes into account the test efficiency and cost, starting from 90°C, a sampling test is performed every time the temperature increases by 3°C. Once the test result shows that the HLB value obtained in the N+1th test is higher than the HLB value obtained in the Nth test, the temperature corresponding to the N+1th test is recorded as the recovery inflection point of the HLB value. Similarly, after the recovery inflection point appears, once the test result shows that the HLB value obtained in the M+1th test is lower than the HLB value obtained in the Mth test, the temperature corresponding to the M+1th test is recorded as the falling inflection point of the HLB value.

[0065] Table 4 lists the HLB value recovery and decline inflection point temperatures for FDY oil samples 1 to 9, as well as the difference between the decline and rise inflection points. The test results in Table 4 indicate that all FDY oil samples in this application experienced an increase in HLB values at high temperatures. Among them, FDY oil samples 1, 4, 7, 8, and 9 had relatively low recovery inflection points, while FDY oil samples 3 and 6 had the highest rise inflection points. FDY oil sample 9 had the highest decline inflection point, while FDY oil samples 5 and 8 also had relatively high decline inflection points. FDY oil sample 1 had the lowest decline inflection point. The difference between the decline and rise inflection points for FDY oil samples 9 and 8 was relatively large, indicating that FDY oil samples 9 and 8 can maintain a stable HLB value over a relatively wide temperature range. The reason for this phenomenon is that FDY oil samples 9 and 8 both utilize a combination of two HLB modifiers. Furthermore, these HLB modifiers are glycerol ethoxylates with a higher molar ratio of triolein to ethylene oxide, and ethyl cellulose with a higher degree of substitution. The higher molar ratio of triolein to ethylene oxide significantly adjusts the HLB value of the oil, while the more substituted ethyl cellulose dissolves more slowly. This results in a higher inflection point in the HLB values of FDY oil samples 9 and 8.

[0066] Table 4 Any person skilled in the art may make various changes and modifications without departing from the spirit and scope of this application, so the scope of protection of this application shall be based on the scope defined by the claims.

Claims

1. A method for preparing a composite FDY oil agent, characterized in that: The preparation method comprises: S100, mixing an HLB regulator and water, stirring, and heating to 55° C. to 65° C. to obtain a first mixture; S200, adding an emulsifier, a sizing agent, an antistatic agent, and a smoothing agent to the first mixture, mixing and stirring while maintaining the temperature to obtain a second mixture; S300, after the second mixture is cooled to room temperature, the pH value is adjusted to 6.5 to 7.5, and filtered to obtain the composite FDY oil; Wherein, the HLB regulator is porous silica loaded with glyceride ethoxylate and coated with ethyl cellulose on the surface.

2. The preparation method according to claim 1, characterized in that By mass ratio, HLB regulator: water: emulsifier: sizing 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 of Tween and Spam or a combination thereof; The bundling agent comprises at least one of oleic acid diethanolamide and oleic acid triethanolamine or a combination thereof; The antistatic agent comprises at least one of isomeric tridecanol potassium phosphate and lauryl tetradecanol potassium phosphate or a combination thereof; The smoothing agent includes at least one of pentaerythritol, isopropyl fatty acid ester, mineral oil, animal oil and vegetable oil, or a combination thereof.

4. The preparation method according to claim 3, characterized in that The emulsifier includes Tween 40 and Span 80 in a mass ratio of (4-5):1, and the HLB value of the emulsifier is 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 of soybean oil, coconut oil, palm oil and rapeseed oil or a combination thereof.

6. The preparation method according to any one of claims 1 to 5, characterized in that The glyceride ethoxylate is prepared by ethoxylation reaction using triglyceride and ethylene oxide as raw materials.

7. The preparation method according to claim 6, characterized in that The preparation method of the HLB regulator comprises: S10, using 3-aminopropyltriethoxysilane to perform silane modification on the porous silica to obtain modified porous silica; S20, mixing the glycerol ethoxylate and the modified porous silica in the ethanol at a mass ratio of glycerol ethoxylate: modified porous silica: ethanol = (20-30): (16-20): 100, heating to 45° C. to 50° C. and maintaining the temperature under ultrasonic vibration for 3 to 4 hours to obtain a third mixture; S30, drying the third mixture, mixing it with an ethyl cellulose solution, and atomizing and drying it to obtain the HLB regulator.

8. The preparation method according to claim 7, characterized in that The HLB regulator includes a first HLB regulator and a second HLB regulator; the first HLB regulator is a porous silica loaded with glyceride ethoxylate A and coated with ethyl cellulose a on the surface; the second HLB regulator is a porous silica loaded with glyceride ethoxylate B and coated with ethyl cellulose b on the surface; the glyceride ethoxylate A and the glyceride ethoxylate B use different molar ratios of triglyceride and ethylene oxide during the preparation process; the ethyl cellulose a and the ethyl cellulose b have different ethoxy content and / or degree of substitution.

9. The preparation method according to claim 8, characterized in that The mass ratio of the first HLB regulator to the second HLB regulator is 1:(2-3); The molar ratio of glycerol trioleate and ethylene oxide used in preparing the glyceride ethoxylate A is 1:(60-65); The molar ratio of glycerol trioleate and ethylene oxide used in preparing the glyceride ethoxylate B is 1:(75-80); Ethylcellulose a has an ethoxy content of 44% to 45% and a degree of substitution of 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.

10. A composite FDY oil, characterized in that: The composite FDY oil is obtained by the preparation method according to any one of claims 1 to 9.

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