High-temperature-resistant polyester oil

Abstract

This invention belongs to the technical field of polyester filament processing aids, and particularly relates to a high-temperature resistant polyester oiling agent. By weight, it comprises the following raw material components: 40-80 parts of smoothing agent; 15-25 parts of emulsifier; 5-10 parts of antistatic agent; 8-15 parts of bundler; 5-15 parts of modified porous inorganic friction-reducing particles; 0.5-6 parts of additives; and 60-100 parts of modified polyvinyl alcohol aqueous solution. The high-temperature resistant polyester oiling agent provided by this invention maintains good stability of viscosity-temperature-viscosity-concentration characteristics at high temperatures.

Description

Technical Field

[0001] This invention belongs to the field of polyester filament processing aids technology, and particularly relates to a high-temperature resistant polyester oiling agent. Background Technology

[0002] Polyester is a lightweight synthetic fiber with high strength, good elasticity, wrinkle resistance, abrasion resistance, chemical corrosion resistance, low moisture absorption, and good heat resistance, making it widely used in the textile industry. Polyester spinning oil is an indispensable auxiliary agent in the processing of polyester fibers. Its main function is to form a uniformly thick film on the surface of the polyester filament during spinning, effectively preventing or eliminating static electricity generated by friction, reducing the coefficient of friction, and imparting smoothness and softness to the fiber. This also gives the fiber appropriate bundle properties, stretchability, fiber splitting ability, spinnability, oxidation resistance, and heat resistance. Based on spinning speed, polyester spinning processes can be divided into low-speed spinning, medium-speed spinning, and high-speed spinning. Low-speed spinning, with a spinning speed of approximately 1000–1500 meters per minute, was the earliest industrialized process. It is a mature technology with stable equipment operation, but its production efficiency is low, and it has been largely phased out. Medium-speed spinning, with a spinning speed of approximately 1800–2500 meters per minute, includes processes such as MOY-DY and MOY-DTY. High-speed spinning, with a spinning speed of 3000–3600 meters per minute, is currently the most efficient and widely used process, including processes such as POY-DTY, POY-TY, and POY-DY.

[0003] Currently, polyester is the world's largest-capacity and most widely used synthetic fiber, accounting for over 80% of my country's total chemical fiber production. However, due to the high speed and friction of medium-to-high-speed polyester spinning processes, the quality and performance requirements for lubricants are extremely high, and currently, China mainly relies on imports. The current technical challenges in producing high-performance polyester high-speed spinning lubricants in my country lie primarily in the following: during high-speed spinning, the lubricant needs to flow rapidly, uniformly coat and adhere to the fiber surface. This requires polyester lubricants to possess good extensibility and flowability, such as appropriate viscosity, good fluidity, and good adhesion. Compared to pure oil lubricants, emulsion-type lubricants have better extensibility and lower cost, making them more suitable for lubrication in medium-to-high-speed spinning processes.

[0004] However, in existing spinning oils, the viscosity-temperature and viscosity-concentration characteristics of emulsion-type oils are affected by factors such as temperature, concentration, pH, and raw material composition. The combination of these factors ultimately leads to significant fluctuations in the viscosity of emulsion-type oils during use, which in turn affects the smooth progress of the spinning process. One of the main reasons affecting the stability of the viscosity-temperature-viscosity-concentration characteristics of emulsion-type oils is that the oil is generally formulated into an emulsion for use during oiling, while spinning is carried out at high temperatures. During the spinning process, as the emulsion is continuously heated and water evaporates, the temperature of the oil on the fiber surface rises rapidly from room temperature, and the concentration increases continuously from about 10%. This drastic change in the temperature and water content of the emulsion-type oil leads to a significant change in the viscosity of the emulsion-type oil. This phenomenon of large fluctuations in emulsion viscosity characteristics with temperature or oil concentration is called the instability of the viscosity-temperature-viscosity-concentration characteristics of the oil. In addition to causing excessive fluctuations in the viscosity of the oil during high-speed spinning, the instability of the viscosity-temperature-viscosity-concentration characteristics of the oil can also cause uneven oiling, resulting in significant tension fluctuations in the fiber during spinning, which can easily cause fuzzing, breakage, and other phenomena. It also leads to a large amount of coking on the heater, ultimately affecting the quality of the yarn.

[0005] In the prior art, those skilled in the art have provided many technical solutions to improve the viscosity-temperature-viscosity-thickness characteristics of oils. However, they mostly focus on the modification of the oil phase components, hoping to obtain oils with more stable viscosity-temperature-viscosity-thickness characteristics by improving the performance of the oil phase components. In addition, considering that in lubrication systems, such as lubricants and emulsion oils, cellulose, polyethylene glycol, polyvinyl alcohol, etc. are often used as viscosity modifiers to adjust the viscosity and adhesion of the lubrication system, these viscosity modifiers often have the following characteristics: increased temperature will accelerate the thermal motion of viscosity modifier molecules, reduce the intermolecular interaction force, thereby reducing the viscosity of the oil; decreased water content will enhance the intermolecular interaction of viscosity modifier molecules, leading to an increase in the viscosity of the oil. For most emulsion-type oils, compared to the increase in viscosity due to a decrease in water content, emulsion-type oils have a relatively low initial viscosity and a high water content, typically around 90%. However, the spinning speed of fibers during the spinning process is extremely fast, resulting in strong shearing and friction on the oil, causing a rapid temperature rise. Simultaneously, the viscosity decreases more significantly with increasing temperature. Therefore, the viscosity of the oil is more sensitive to the viscosity reduction caused by temperature increases. Coupled with the significant shear-thinning properties of these viscosity modifiers, this leads to problems such as low initial spinning temperature and high viscosity, easily causing uneven oiling, and high temperature and low viscosity in the middle and later stages of spinning, easily causing splashing. Therefore, existing technologies have attempted to improve the viscosity-temperature-viscosity-concentration stability of the oil through the slow release of viscosity modifiers. However, the results have not been ideal. Therefore, providing a high-temperature resistant polyester spinning oil with better viscosity-temperature-viscosity-concentration stability at high temperatures is one of the technical problems that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0006] The purpose of this invention is to address the problem of unstable viscosity-temperature and viscosity-concentration characteristics of the aforementioned spinning oils by providing a high-temperature resistant polyester oil.

[0007] In view of this, the present invention provides a high-temperature resistant polyester oiling agent, which comprises the following raw material components by weight:

[0008]

[0009] Furthermore, the preparation process of the modified polyvinyl alcohol aqueous solution includes the following steps:

[0010] S1, mix 3-5 parts by weight of low-polymerization degree polyvinyl alcohol and 30-50 parts by weight of deionized water, stir until the low-polymerization degree polyvinyl alcohol is dissolved, add 0.3-0.8% of modifier and 0.1-0.5% of surfactant of low-polymerization degree polyvinyl alcohol, disperse evenly, heat the mixture to 60-90℃, react with stirring for 0.5-1.5h, and then degas to obtain mixture A;

[0011] S2, mix 2-4 parts by weight of low-polymerization degree polyvinyl alcohol and 50-80 parts by weight of deionized water, stir, and after the low-polymerization degree polyvinyl alcohol dissolves, heat the solution to 50-80°C, then add 0.05-0.1% of crosslinking agent of low-polymerization degree polyvinyl alcohol, and react for 30-60 minutes under low-speed stirring to obtain mixture B;

[0012] S3, after mixing the mixture A and the mixture B in a weight ratio of (5-8):(2-4), the modified polyvinyl alcohol aqueous solution is obtained.

[0013] Furthermore, the modifier is selected from one or more of zinc chloride, calcium chloride, zinc sulfate, and nickel sulfate, and the surfactant is sodium dodecyl sulfate.

[0014] Furthermore, the crosslinking agent is selected from one or more of oxalic acid, glyoxal, malonic acid, malondialdehyde, succinic acid, and succinaldehyde.

[0015] Furthermore, the preparation process of the modified polyvinyl alcohol aqueous solution also includes the following steps:

[0016] S4. After mixing mixture A and mixture B according to the set weight ratio, the resulting mixture is first stirred at low speed for 5 to 10 minutes in a water bath at a temperature of 50 to 80°C. Then, 0.1 to 0.3 parts by weight of cellulose is added to the mixture and stirred further until the cellulose is completely dissolved. The resulting mixture is then frozen at a low temperature of -30 to -10°C until it is completely solidified. After that, it is thawed naturally at room temperature. After repeated freezing and thawing 3 to 5 times, the modified polyvinyl alcohol aqueous solution is obtained.

[0017] Furthermore, the cellulose is selected from one or more of methylcellulose, ethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose, and the cellulose is a short-chain, low-polymerization-degree cellulose with a degree of polymerization of 100 to 300.

[0018] Furthermore, the smoothing agent comprises 50-60 wt% polyether and 40-50 wt% mineral oil.

[0019] Furthermore, the preparation process of the modified porous inorganic friction-reducing particles is as follows:

[0020] Disperse 3-5 parts by weight of seaweed extract into 50-100 parts by weight of alkaline solution, stir until uniformly mixed, then disperse 5-10 parts by weight of porous inorganic friction-reducing particles into the alkaline solution, react at 30-50°C with stirring for 5-10 minutes, then let stand at room temperature for 10-30 minutes, filter and dry to obtain modified porous inorganic friction-reducing particles.

[0021] Furthermore, the porous inorganic friction-reducing particles have a particle size ≤100µm, and the porous inorganic friction-reducing particles are aluminosilicate porous materials.

[0022] Furthermore, the preparation process of the high-temperature resistant polyester oil agent includes the following steps:

[0023] First, the modified porous inorganic friction-reducing particles of the formula amount are dispersed in the smoothing agent and stirred thoroughly until uniformly dispersed. Then, the antistatic agent, the slubbing agent and the emulsifier are added and stirred evenly to obtain the oil phase solution.

[0024] After mixing the oil phase solution with a modified polyvinyl alcohol aqueous solution, a high-temperature resistant polyester oil agent is obtained by homogenization and emulsification.

[0025] The beneficial effects of the present invention are: the high-temperature resistant polyester oil provided by the present invention can maintain good oil viscosity-temperature viscosity-concentration characteristics at high temperatures. Detailed Implementation

[0026] The technical solutions of this application will be clearly described below with reference to the embodiments thereof. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application are within the scope of protection of this application.

[0027] It should be noted that, in this application, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes that element.

[0028] A high-temperature resistant polyester oiling agent, by weight, comprises the following raw material components:

[0029]

[0030] As some examples of the present invention, the additive is selected from one or more of defoamers, dispersants, preservatives, wetting and penetrating agents, antioxidants, pH adjusters, etc.

[0031] As some examples of the present invention, the smoothing agent is selected from one or more of polyol esters, polyethers, fatty acid esters, vegetable oils, mineral oils, etc.

[0032] Preferably, the smoothing agent comprises 50-60 wt% polyether and 40-50 wt% mineral oil.

[0033] As some examples of the present invention, the emulsifier is selected from one or more of fatty alcohol polyoxyethylene ether, polyoxyethylene cholesterol ether, fatty acid polyethylene glycol ester, stearate, sodium oleate, potassium oleate, polyoxyethylene oleate, polyoxyethylene laurate, sodium lauryl ether sulfate, etc.

[0034] As some examples of the present invention, the antistatic agent is selected from one or more of alkyl phosphate salts, alkyl sulfonate salts, alkyl sulfate salts, alkyl quaternary ammonium salts, fatty alcohol polyoxyethylene ether phosphate salts, lauryl alcohol polyoxyethylene ether, sodium secondary alkyl sulfonate, dodecyl dimethylamine oxide, etc.

[0035] As some examples of the present invention, the bridging agent is selected from one or more of the following: fatty acid triethanolamine salt, polyethylene glycol oleate, polyethylene glycol laurate, lauryl polyoxyethylene ether, polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ester, sulfated castor oil, castor oil polyoxyethylene ether, coconut oil fatty acid diethanolamide, etc.

[0036] Furthermore, the preparation process of the modified porous inorganic friction-reducing particles is as follows:

[0037] Disperse 3-5 parts by weight of seaweed extract into 50-100 parts by weight of alkaline solution, stir until uniformly mixed, then disperse 5-10 parts by weight of porous inorganic friction-reducing particles into the alkaline solution, react at 30-50°C with stirring for 5-10 minutes, then let stand at room temperature for 10-30 minutes, filter and dry to obtain modified porous inorganic friction-reducing particles.

[0038] As some examples of the present invention, the alkaline solution is selected from one or more of sodium hydroxide, potassium hydroxide solution, etc., and the concentration of the alkaline solution is 1 to 5 wt%.

[0039] Preferably, the porous inorganic friction-reducing particles have a particle size ≤100µm.

[0040] More preferably, the particle size of the porous inorganic friction-reducing particles is ≤10µm.

[0041] As some examples of the present invention, the porous inorganic friction-reducing particles are selected from one or more of porous attapulgite, porous zeolite, porous ceramics, porous composite materials, etc.

[0042] Preferably, the porous inorganic friction-reducing particles are aluminosilicate porous materials.

[0043] Preferably, the alginic acid content in the seaweed extract should be no less than 15 wt%.

[0044] Furthermore, the preparation process of the modified polyvinyl alcohol aqueous solution includes the following steps:

[0045] S1, mix 3-5 parts by weight of low-polymerization degree polyvinyl alcohol and 30-50 parts by weight of deionized water, stir until the low-polymerization degree polyvinyl alcohol is dissolved, add 0.3-0.8% of modifier and 0.1-0.5% of surfactant of low-polymerization degree polyvinyl alcohol, disperse evenly, heat the mixture to 60-90℃, react with stirring for 0.5-1.5h, and then degas to obtain mixture A;

[0046] S2, mix 2-4 parts by weight of low-polymerization degree polyvinyl alcohol and 50-80 parts by weight of deionized water, stir, and after the low-polymerization degree polyvinyl alcohol dissolves, heat the solution to 50-80°C, then add 0.05-0.1% of crosslinking agent of low-polymerization degree polyvinyl alcohol, and react for 30-60 minutes under low-speed stirring to obtain mixture B;

[0047] S3, after mixing the mixture A and the mixture B in a weight ratio of (5-8):(2-4), the modified polyvinyl alcohol aqueous solution is obtained.

[0048] As some examples of the present invention, the modifier is selected from one or more metal salts such as zinc chloride, calcium chloride, zinc sulfate, and nickel sulfate.

[0049] As some examples of the present invention, the surfactant is sodium dodecyl sulfate.

[0050] As some examples of the present invention, the crosslinking agent is selected from one or more of oxalic acid, glyoxal, malonic acid, malondialdehyde, succinic acid, succinic acid, and succinic acid.

[0051] It should be noted that the degree of polymerization of the low-polymerization polyvinyl alcohol described in this invention is about 300 to 1000, and the degree of hydrolysis is about 78 to 90%.

[0052] In some other embodiments of the present invention, the preparation process of the modified polyvinyl alcohol aqueous solution further includes the following steps:

[0053] S4. After mixing mixture A and mixture B according to the set weight ratio, the mixture is first stirred at low speed for 5 to 10 minutes in a water bath at a temperature of 50 to 80°C. Then, 0.1 to 0.3 parts by weight of cellulose is added to the mixture and stirred further until the cellulose is completely dissolved. The resulting mixture is then frozen at a low temperature of -30 to -10°C until it is completely solidified. After that, it is thawed naturally at room temperature. After repeated freezing and thawing 3 to 5 times, the modified polyvinyl alcohol aqueous solution is obtained.

[0054] Preferably, the low-speed stirring speed in step S4 is 80-150 r / min.

[0055] Preferably, the cellulose is selected from one or more of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.

[0056] More preferably, the cellulose is selected from one or more of methylcellulose and ethylcellulose.

[0057] Preferably, the cellulose is a short-chain, low-polymerization-degree cellulose with a degree of polymerization of 100 to 300.

[0058] As some examples of the present invention, in step S4, when the added cellulose includes one or more of celluloses containing a large number of hydroxyl groups such as hydroxyethyl cellulose and hydroxypropyl cellulose, sodium dodecyl sulfate surfactant at 0.5-1% of the cellulose dosage can be added simultaneously.

[0059] Furthermore, the preparation process of the high-temperature resistant polyester oil agent includes the following steps:

[0060] First, the modified porous inorganic friction-reducing particles of the formula amount are dispersed in the smoothing agent and stirred thoroughly until uniformly dispersed. Then, the antistatic agent, the slubbing agent and the emulsifier are added and stirred evenly to obtain the oil phase solution.

[0061] The high-temperature resistant polyester oil agent of the present invention is obtained by mixing the oil phase solution with the modified polyvinyl alcohol aqueous solution, followed by homogenization and emulsification.

[0062] Generally, the viscosity-temperature and viscosity-concentration characteristics of spinning oils include viscosity-temperature characteristics and viscosity-concentration characteristics. Viscosity-temperature characteristics refer to the relationship between the viscosity of the spinning oil and temperature; this is an important performance indicator for spinning oils. The smaller the change in viscosity with temperature, the better the viscosity-temperature characteristics. Viscosity-concentration characteristics refer to the relationship between the viscosity of the spinning oil and its concentration; the concentration of the spinning oil directly affects its viscosity, and generally, the higher the concentration, the higher the viscosity.

[0063] During the spinning process, the viscosity-temperature and viscosity-concentration characteristics of the spinning oil have a significant impact on fiber quality, spinning stability, and production efficiency. Suitable viscosity-temperature and viscosity-concentration characteristics ensure uniform adhesion of the oil to the fiber surface, providing sufficient lubrication and bundling effect, thereby improving fiber quality.

[0064] Currently, the viscosity modifiers used in spinning oils are mostly high molecular polymers such as cellulose, polyethylene glycol, and polyvinyl alcohol. Because these substances have a large number of hydrogen bonds in their aqueous solutions, such as polyvinyl alcohol, whose molecular chain has a relatively strict linear regular structure, the hydroxyl groups on the monomer units cause three types of hydrogen bonds to exist in its aqueous solution: intramolecular hydrogen bonds, intermolecular hydrogen bonds, and hydrogen bonds between polyvinyl alcohol and water molecules. These hydrogen bond interactions greatly affect the conformation of the polymer macromolecules and the rheological behavior of polyvinyl alcohol solutions, thereby affecting the fluidity, viscosity, and adhesion of polyvinyl alcohol solutions. Especially for spinning oils, the temperature of both the fiber and the oil is low and the concentration is high when the oil is applied. Furthermore, the shear rate experienced during the oiling process is low. This leads to a common problem with current high-speed polyester spinning oils: emulsion-type oils have high viscosity at low temperatures, resulting in uneven oiling; at high temperatures, the viscosity is low, and the oil on the fiber will splash onto the hot roller under centrifugal force. Prolonged heating can easily lead to the formation of charred material. This can affect the heat transfer efficiency of the heater, resulting in uneven fiber stretching, or even increase fuzz and breakage, thus affecting production.

[0065] Based on this, the present invention proposes a novel emulsion-type spinning oil that uses an improved modified polyvinyl alcohol aqueous solution as a viscosity modifier, which has the following characteristics:

[0066] (1) Compared with polyvinyl alcohol with medium and high degree of polymerization, the low degree of polymerization polyvinyl alcohol used in this invention has a shorter molecular chain, fewer hydrogen bonds in the aqueous solution, lower viscosity, weaker shear thinning behavior, and its viscosity is less affected by concentration, temperature, etc. Using low degree of polymerization polyvinyl alcohol to prepare the modified polyvinyl alcohol aqueous solution can provide a viscosity modifier with more stable viscosity-temperature-viscosity-concentration properties compared with using medium and high degree of polymerization polyvinyl alcohol, thereby improving the viscosity-temperature-viscosity-concentration characteristics of the prepared spinning oil.

[0067] (2) However, the ability of low-polymerization degree polyvinyl alcohol to enhance the viscosity of the oil is slightly low. If the amount of low-polymerization degree polyvinyl alcohol added is too large, it will aggravate the hydrogen bonding between polyvinyl alcohol molecules and between polyvinyl alcohol and water molecules, which will increase the sensitivity of the rheological behavior of the polyvinyl alcohol aqueous solution to changes in temperature and concentration, and reduce the stability of the viscosity-temperature-viscosity-concentration characteristics of the oil. In order to alleviate the significant change in viscosity of the oil caused by low-polymerization degree polyvinyl alcohol when the oil temperature is high and the water content is low, this invention uses a small amount of modifier and surfactant to destroy and weaken the hydrogen bonding in a portion of the low-polymerization degree polyvinyl alcohol. By sacrificing a portion of the hydrogen bonding and reducing the viscosity of the polyvinyl alcohol aqueous solution of the same concentration, especially reducing its initial viscosity at low shear rate, the rheological behavior of the polyvinyl alcohol aqueous solution is changed. The viscosity is slightly reduced, but the sensitivity to changes in temperature and concentration is reduced, thereby improving the viscosity-temperature-viscosity-concentration characteristics of the prepared spinning oil.

[0068] (3) Based on feature (2), in order to reduce the amount of polyvinyl alcohol used and further improve the viscosity-temperature-viscosity-concentration characteristics of the spinning oil, especially to improve the ability of the oil to spread quickly on the fiber surface and adhere evenly to the fiber surface during high-speed spinning, this invention also treats another part of low-polymerization degree polyvinyl alcohol with micro-crosslinking to form a small network fragment structure, and mixes it with a polyvinyl alcohol solution treated with modifier and surfactant, and finally obtains an oil with good fluidity, suitable viscosity and strong adhesion at low temperature, so that the oil can be coated on the fiber surface more quickly and evenly, which meets the needs of high-speed spinning.

[0069] (4) Furthermore, in order to address the defects of oil agent viscosity reduction and easy splashing at high temperature during high-speed spinning, the present invention also adds cellulose and surfactant to the mixed system obtained by mixing mixture A and mixture B. By the interaction of the negatively charged hydrophilic groups on the surfactant with the hydroxyl groups on the molecular chains of cellulose and polyvinyl alcohol, the number of hydrogen bonds in the system is reduced, the hydrogen bonding between short-chain cellulose and polyvinyl alcohol molecules is inhibited, the adhesion of the oil agent is improved, and the viscosity-temperature viscosity-concentration characteristics of the oil agent are stabilized. At the same time, the high molecular polymer formed by the mutual cross-linking between cellulose and modified porous inorganic friction-reducing particles is used to improve the viscosity of the oil agent at high temperature.

[0070] (5) The interaction process between cellulose and modified porous inorganic friction-reducing particles is explained as follows: First, during the preparation of modified porous inorganic friction-reducing particles, substances such as alginic acid in the seaweed extract can react with the silica-alumina compounds in the porous inorganic friction-reducing particles to form alginate-silica-alumina compounds. During the spinning process, the modified porous inorganic friction-reducing particles can diffuse from the oil phase to the aqueous phase under the action of friction, etc., so that the alginate-silica-alumina compounds attached to them can gradually crosslink with substances such as cellulose in the aqueous phase to form a high molecular polymer during use, thereby improving the problem of oil agent viscosity decrease and easy splashing during high-speed spinning, especially in the middle and late stages of spinning, due to the rapid increase of oil agent temperature, the intensification of shear thinning effect.

[0071] (6) In addition, the modified porous inorganic friction-reducing particles of the present invention can also reduce friction in addition to their slow-release effect.

[0072] The following specific examples illustrate the high-temperature resistant polyester oiling agent of the present invention:

[0073] Example 1

[0074] Preparation of modified porous inorganic friction-reducing particles:

[0075] Four parts by weight of seaweed extract were dispersed in 80 parts by weight of a 3 wt% alkaline sodium hydroxide solution, wherein the seaweed extract contained 18 wt% alginic acid. After stirring until uniformly mixed, eight parts by weight of porous attapulgite particles were dispersed in the alkaline solution. The mixture was reacted at 40°C with stirring for 10 min, then allowed to stand at room temperature for 20 min. After filtration and drying, the modified porous inorganic friction-reducing particles were obtained.

[0076] Example 2

[0077] Preparation of modified porous inorganic friction-reducing particles:

[0078] Three parts by weight of seaweed extract were dispersed in 50 parts by weight of a 1 wt% alkaline sodium hydroxide solution, wherein the seaweed extract contained 16 wt% alginic acid. After stirring until uniformly mixed, 10 parts by weight of porous zeolite particles were dispersed in the alkaline solution. The mixture was reacted at 50°C with stirring for 8 minutes, then allowed to stand at room temperature for 10 minutes. After filtration and drying, modified porous inorganic friction-reducing particles were obtained.

[0079] Example 3

[0080] Preparation of modified polyvinyl alcohol aqueous solution:

[0081] S1, mix 4 parts by weight of low-polymerization degree polyvinyl alcohol and 40 parts by weight of deionized water, stir until the low-polymerization degree polyvinyl alcohol is dissolved, add 0.5% of the low-polymerization degree polyvinyl alcohol modifier nickel sulfate and 0.3% of the low-polymerization degree polyvinyl alcohol sodium dodecyl sulfate, disperse evenly, heat the mixture to 70°C, react for 1 hour under stirring, and then degas to obtain mixture A;

[0082] S2, mix 3 parts by weight of low-polymerization degree polyvinyl alcohol and 60 parts by weight of deionized water, stir, and after the low-polymerization degree polyvinyl alcohol dissolves, heat the solution to 60°C, then add 0.06% of the crosslinking agent glyoxal of low-polymerization degree polyvinyl alcohol, and react for 50 minutes under low-speed stirring to obtain mixture B.

[0083] S3, after mixing the mixture A and the mixture B at a weight ratio of 6:3, the modified polyvinyl alcohol aqueous solution is obtained.

[0084] Example 4

[0085] Preparation of modified polyvinyl alcohol aqueous solution:

[0086] S1, mix 5 parts by weight of low-polymerization degree polyvinyl alcohol and 30 parts by weight of deionized water, stir until the low-polymerization degree polyvinyl alcohol is dissolved, add 0.3% of the low-polymerization degree polyvinyl alcohol modifier calcium chloride and 0.5% of the low-polymerization degree polyvinyl alcohol sodium dodecyl sulfate, disperse evenly, heat the mixture to 90°C, react for 0.5 h under stirring, and then degas to obtain mixture A;

[0087] S2, mix 4 parts by weight of low-polymerization degree polyvinyl alcohol and 50 parts by weight of deionized water, stir, and after the low-polymerization degree polyvinyl alcohol dissolves, heat the solution to 80°C, then add 0.1% of the crosslinking agent oxalic acid of low-polymerization degree polyvinyl alcohol, and react for 30 minutes under low-speed stirring to obtain mixture B.

[0088] S3, after mixing the mixture A and the mixture B at a weight ratio of 5:4, the modified polyvinyl alcohol aqueous solution is obtained.

[0089] Example 5

[0090] Preparation of modified polyvinyl alcohol aqueous solution:

[0091] S1, mix 3 parts by weight of low-polymerization degree polyvinyl alcohol and 50 parts by weight of deionized water, stir until the low-polymerization degree polyvinyl alcohol is dissolved, add 0.8% of the low-polymerization degree polyvinyl alcohol modifier calcium chloride and 0.1% of the low-polymerization degree polyvinyl alcohol sodium dodecyl sulfate, disperse evenly, heat the mixture to 60°C, react for 1.5 hours under stirring, and then degas to obtain mixture A;

[0092] S2, mix 2 parts by weight of low-polymerization degree polyvinyl alcohol and 80 parts by weight of deionized water, stir, and after the low-polymerization degree polyvinyl alcohol dissolves, heat the solution to 50°C, then add 0.05% of the amount of low-polymerization degree polyvinyl alcohol as a crosslinking agent oxalic acid, and react for 60 minutes under low-speed stirring to obtain mixture B;

[0093] S3, after mixing the mixture A and the mixture B at a weight ratio of 8:2, the modified polyvinyl alcohol aqueous solution is obtained.

[0094] Example 6

[0095] Preparation of modified polyvinyl alcohol aqueous solution:

[0096] The difference between this and Example 3 above is only that: after mixing mixture A and mixture B at a weight ratio of 6:3, the mixture is first stirred at low speed for 5 minutes in a water bath at 80°C. Then, 0.2 parts by weight of hydroxypropyl cellulose and 0.7% of sodium dodecyl sulfate surfactant are added to the mixture, and the mixture is stirred further until the cellulose is completely dissolved. The resulting mixture is then frozen at -15°C until completely solidified, and then thawed naturally at room temperature. After repeated freezing and thawing four times, the modified polyvinyl alcohol aqueous solution is obtained.

[0097] Examples 7-13

[0098] Preparation of high-temperature resistant polyester oiling agent:

[0099] First, the modified porous inorganic friction-reducing particles of the formula amount are dispersed in the smoothing agent and stirred thoroughly until uniformly dispersed. Then, the antistatic agent, the slubbing agent and the emulsifier are added and stirred evenly to obtain the oil phase solution.

[0100] The high-temperature resistant polyester oil agent of the present invention is obtained by mixing the oil phase solution with the modified polyvinyl alcohol aqueous solution, followed by homogenization and emulsification.

[0101] The raw material ratios in Examples 7-13 are shown in Table 1 below:

[0102] Table 1 Raw material ratio of polyester oiling agent

[0103]

[0104] In Examples 7 and 8, the smoothing agent used was: 50 wt% polyether + 40 wt% mineral oil + 10 wt% vegetable oil; the emulsifier was a mixture of stearate, fatty alcohol polyoxyethylene ether, and polyoxyethylene cholesterol ether; the antistatic agent was a mixture of alkyl phosphate salt and lauryl alcohol polyoxyethylene ether; the cleaving agent was a mixture of fatty acid triethanolamine salt, castor oil polyoxyethylene ether, and polyethylene glycol laurate; the modified porous inorganic friction-reducing particles were the modified porous inorganic friction-reducing particles prepared in Example 1 above; the additives were a mixture of defoamer and dispersant; and the modified polyvinyl alcohol aqueous solution was the modified polyvinyl alcohol aqueous solution prepared in Example 3 above.

[0105] The smoothing agent used in Examples 9-10 was: 60 wt% polyether + 40 wt% mineral oil; the emulsifier was a mixture of fatty acid polyethylene glycol ester, stearate, and sodium oleate; the antistatic agent was a mixture of alkyl phosphate salt, alkyl sulfonate salt, and lauryl polyoxyethylene ether; the bridging agent was a mixture of sulfated castor oil and castor oil polyoxyethylene ether; the modified porous inorganic friction-reducing particles were the modified porous inorganic friction-reducing particles prepared in Example 2 above; the additives were a mixture of defoamer, dispersant, pH adjuster, and wetting and penetrating agent; and the modified polyvinyl alcohol aqueous solution was the modified polyvinyl alcohol aqueous solution prepared in Example 4 above.

[0106] The smoothing agent used in Examples 11-12 was: 60 wt% polyether + 40 wt% mineral oil; the emulsifier was a mixture of potassium oleate, polyoxyethylene oleate, and polyoxyethylene cholesterol ether; the antistatic agent was a mixture of alkyl sulfonate salts, alkyl sulfate salts, alkyl quaternary ammonium salts, and fatty alcohol polyoxyethylene ether phosphate salts; the cleaving agent was a mixture of lauryl polyoxyethylene ether, polyoxyethylene polyoxypropylene ether, and castor oil polyoxyethylene ether; the modified porous inorganic friction-reducing particles were the modified porous inorganic friction-reducing particles prepared in Example 2 above; the additives were a mixture of defoamer, dispersant, pH adjuster, wetting and penetrating agent, and antioxidant; and the modified polyvinyl alcohol aqueous solution was the modified polyvinyl alcohol aqueous solution prepared in Example 5 above.

[0107] The only difference between Example 13 and Example 7 above is that the modified polyvinyl alcohol aqueous solution used in Example 13 is the modified polyvinyl alcohol aqueous solution prepared in Example 6 above.

[0108] Comparative Example 1

[0109] The difference between this and Example 13 above is that porous attapulgite that has not been modified by seaweed extract is used as porous inorganic friction-reducing particles to prepare polyester oiling agent.

[0110] Comparative Example 2

[0111] The difference between this and Example 13 is that the modified polyvinyl alcohol aqueous solution used in this example does not contain cellulose and the surfactant sodium dodecyl sulfate. In preparing the modified polyvinyl alcohol aqueous solution, after mixing mixture A and mixture B in a weight ratio, the mixture is first stirred at low speed for 5 minutes in a water bath at 80°C. Then, the resulting mixture is placed in a low temperature environment of -15°C and frozen until completely solidified. After thawing naturally at room temperature, the process is repeated 4 times to obtain the modified polyvinyl alcohol aqueous solution.

[0112] Comparative Example 3

[0113] The difference between this and Example 13 is that the modified polyvinyl alcohol aqueous solution used in this example does not contain sodium dodecyl sulfate surfactant when cellulose is added.

[0114] Comparative Example 4

[0115] The difference between this and Example 13 is that the modified polyvinyl alcohol aqueous solution used here has not undergone repeated freeze-thaw treatment. In preparing the modified polyvinyl alcohol aqueous solution, after mixing mixture A and mixture B in a weight ratio, the mixture is first stirred at low speed for 5 minutes in a water bath at 80°C. Then, 0.2 parts by weight of hydroxypropyl cellulose and 0.7% of sodium dodecyl sulfate surfactant are added to the mixture, and the mixture is further stirred until the cellulose is completely dissolved to obtain the modified polyvinyl alcohol aqueous solution.

[0116] Comparative Example 5

[0117] The difference between this and Example 7 is that the mixture A in the modified polyvinyl alcohol aqueous solution used here is not modified. When preparing mixture A, 4 parts by weight of low degree of polymerization polyvinyl alcohol and 40 parts by weight of deionized water are mixed and stirred until the low degree of polymerization polyvinyl alcohol is dissolved. After degassing treatment, mixture A is obtained.

[0118] Comparative Example 6

[0119] The difference between this and Example 7 is that the modified polyvinyl alcohol aqueous solution used in this example has not undergone cross-linking modification treatment. When preparing the mixture B, 3 parts by weight of low degree of polymerization polyvinyl alcohol and 60 parts by weight of deionized water are mixed and stirred until the low degree of polymerization polyvinyl alcohol is dissolved. After degassing treatment, the mixture B is obtained.

[0120] Comparative Example 7

[0121] The difference between it and Example 7 above is that the modified polyvinyl alcohol aqueous solution used in it contains only 40 parts by weight of mixture A.

[0122] Experimental Example 1

[0123] (1) Oil property testing:

[0124] The polyester oil prepared in steps 7-13 above was mixed with water and then formulated into an emulsion with an oil content of 15%. The pH value, surface tension, room temperature stability (25℃, 7d), and high temperature stability (80℃, 8h) were then tested.

[0125] The test results are detailed in Table 2 below:

[0126] Table 2. Detection of physical properties of oils

[0127]

[0128] (2) Performance testing of oil viscosity as a function of temperature and concentration:

[0129] The viscosity of the prepared emulsion-type oil was tested multiple times as a function of temperature and water content. The specific process is as follows:

[0130] The oils prepared in Examples 7-13 and Comparative Examples 1-7 were mixed with water to form an emulsion with an oil content of 15%. This emulsion was placed in a covered container equipped with a weighing device and heated while stirring at 800 rpm. The heating power was controlled to gradually raise the temperature of the solution to 100°C at a rate of 5-10°C / min, and then maintained at 100°C. During heating and stirring, when the temperature reached the set temperature (e.g., 50°C), the container lid was opened to accelerate water evaporation. The process continued until the water loss rate of the solution reached the set value. After reaching a water loss rate of 3%, the container is closed, and the emulsion temperature is heated to the next set temperature (e.g., 75℃). Then, the container is opened again to accelerate water evaporation. Once the water loss rate of the solution reaches the set value (e.g., 5%), the container is closed again. This process is repeated to obtain emulsions at different temperatures and concentrations. The water loss rate (assuming that the weight of the emulsion evaporated during heating is the weight of water, then water loss rate = weight loss due to evaporation / initial weight) and viscosity (cP) of the emulsions under different conditions are recorded and measured. The results are shown in Table 3 below.

[0131] Table 3 Viscosity stability test of oils

[0132]

[0133]

[0134] (3) Spinning performance test:

[0135] The polyester oiling agents prepared in Examples 7-13 and Comparative Examples 1-7 were mixed with water to prepare an aqueous solution with an oiling agent content of 15% for spinning tests. The spinning specification was 135 tex / 72f, and the spinning speed was 3500 m / min. The test results are shown in Table 4 below:

[0136] Table 4 Results of spinning performance tests

[0137]

[0138]

[0139] The embodiments of this application have been described above in conjunction with the examples. Unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other. This application is not limited to the specific implementation methods described above. The specific implementation methods described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of this application without departing from the spirit and scope of the claims, and all of these forms are within the protection scope of this application.

Claims

1. A high-temperature resistant polyester oiling agent, characterized in that, By weight, it comprises the following raw material components: 40-80 parts of smoothing agent; 15-25 parts emulsifier; 5-10 parts of antistatic agent; 8-15 parts of clustering agent; 5-15 parts of modified porous inorganic friction-reducing particles; Additives: 0.5-6 parts; 60-100 parts of modified polyvinyl alcohol aqueous solution; The preparation process of the modified polyvinyl alcohol aqueous solution includes the following steps: S1, mix 3-5 parts by weight of low-polymerization degree polyvinyl alcohol and 30-50 parts by weight of deionized water, stir until the low-polymerization degree polyvinyl alcohol is dissolved, then add 0.3-0.8% of a modifier and 0.1-0.5% of a surfactant, disperse evenly, heat the mixture to 60-90°C, react with stirring for 0.5-1.5 hours, and then degas to obtain mixture A; the modifier is selected from one or more of zinc chloride, calcium chloride, zinc sulfate, and nickel sulfate, and the surfactant is sodium dodecyl sulfate; the degree of polymerization of the low-polymerization degree polyvinyl alcohol is 300-1000; S2, mix 2-4 parts by weight of low-polymerization degree polyvinyl alcohol and 50-80 parts by weight of deionized water, stir, and after the low-polymerization degree polyvinyl alcohol dissolves, heat the solution to 50-80°C, then add 0.05-0.1% of a crosslinking agent to the low-polymerization degree polyvinyl alcohol, and react under low-speed stirring for 30-60 minutes to obtain mixture B; the crosslinking agent is selected from one or more of oxalic acid, glyoxal, malonic acid, malondialdehyde, succinic acid, and succinic acid; the degree of polymerization of the low-polymerization degree polyvinyl alcohol is 300-1000; S3, mix the mixture A and the mixture B in a weight ratio of (5~8):(2~4); S4. After mixing mixture A and mixture B according to the set weight ratio, the resulting mixture is first stirred at low speed for 5-10 minutes in a water bath at a temperature of 50-80℃. Then, 0.1-0.3 parts by weight of cellulose is added to the mixture and stirred further until the cellulose is completely dissolved. The resulting mixture is then frozen in a low temperature environment of -30 to -10℃ until it is completely solidified. After that, it is thawed naturally at room temperature. After repeated freezing and thawing 3-5 times, the modified polyvinyl alcohol aqueous solution is obtained. The preparation process of the modified porous inorganic friction-reducing particles is as follows: Disperse 3-5 parts by weight of seaweed extract into 50-100 parts by weight of alkaline solution, stir until uniformly mixed, then disperse 5-10 parts by weight of porous inorganic friction-reducing particles into the alkaline solution, react at 30-50°C with stirring for 5-10 minutes, then let stand at room temperature for 10-30 minutes, filter and dry to obtain modified porous inorganic friction-reducing particles; the particle size of the porous inorganic friction-reducing particles is ≤100 μm, and the porous inorganic friction-reducing particles are aluminosilicate porous materials.

2. The high-temperature resistant polyester oiling agent according to claim 1, characterized in that, The cellulose is selected from one or more of methylcellulose, ethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose, and the cellulose is a short-chain, low-polymerization-degree cellulose with a degree of polymerization of 100 to 300.

3. The high-temperature resistant polyester oiling agent according to claim 1, characterized in that, The smoothing agent comprises 50-60 wt% polyether and 40-50 wt% mineral oil.

4. The high-temperature resistant polyester oiling agent according to claim 1, characterized in that, The preparation process of the high-temperature resistant polyester oil agent includes the following steps: First, the modified porous inorganic friction-reducing particles of the formula are dispersed in the smoothing agent and stirred thoroughly until uniformly dispersed. Then, antistatic agent, slugging agent and emulsifier are added and stirred evenly to obtain an oil phase solution. The oil phase solution is mixed with a modified polyvinyl alcohol aqueous solution and then homogenized and emulsified to obtain a high-temperature resistant polyester oiling agent.

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