High-temperature-resistant polyester oiling agent

Abstract

The invention belongs to the technical field of polyester filament yarn processing aids, and particularly relates to a high-temperature-resistant polyester oiling agent which comprises the following raw material components in parts by weight: 40-80 parts of a smoothing agent; 15-25 parts of an emulsifier; 5-10 parts of an antistatic agent; 8-15 parts of a bundling agent; 5-15 parts of modified porous inorganic antifriction particles; 0.5-6 parts of an additive; the high-temperature-resistant polyester oiling agent provided by the invention can keep good viscosity-temperature and viscosity-concentration characteristics of the oiling agent at high temperature, and the viscosity-temperature and viscosity-concentration characteristics of the oiling agent are stable.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyester filament processing aids, and particularly relates to a polyester oil agent with high temperature resistance. Background Art

[0002] Polyester is a lightweight synthetic fiber with characteristics such as high strength, good elasticity, wrinkle resistance, abrasion resistance, chemical corrosion resistance, low hygroscopicity, and good heat resistance, and is widely used in the textile industry. Polyester spinning oil agent is an indispensable aid in the process of polyester fiber processing. Its main function is to form a uniformly thick film on the surface of the polyester raw filament during the spinning process, effectively preventing or eliminating static electricity generated by friction, reducing the friction coefficient, and endowing the fiber with characteristics such as smoothness and softness, so that the fiber has appropriate bundling property, drawability, fiber splitting property, spinnability, antioxidant property, and heat resistance. According to the spinning speed, the polyester spinning process can be divided into a low-speed spinning process, a medium-speed spinning process, and a high-speed spinning process. Among them, the spinning speed of the low-speed spinning process is about 1000 - 1500 meters per minute, which is the earliest industrialized production process route. The process is mature, the equipment runs stably, but the production efficiency is low, and it has basically been phased out at present; the spinning speed of the medium-speed spinning process is about 1800 - 2500 meters per minute, such as the MOY-DY process, the MOY-DTY process, etc.; while the spinning speed of the high-speed spinning process can reach 3000 - 3600 meters per minute, which is the process with the highest production efficiency and the widest application at present, such as the POY-DTY process, the POY-TY process, the POY-DY process, etc.

[0003] So far, polyester is the synthetic fiber variety with the largest production capacity and the widest application in the world. In the output of the chemical fiber industry in China, the output of polyester accounts for more than 80% of the total output. However, due to the high speed and large friction in the medium and high speed spinning process of polyester, the quality and performance requirements for the oil agent are extremely high, and currently mainly rely on imports. At present, the technical difficulties in the production of high-performance polyester high-speed spinning oil agents in China are mainly reflected in: during the high-speed textile process, the oil agent needs to be able to flow quickly, uniformly coat and adhere to the fiber surface, which requires the polyester oil agent to have good ductility and flow ability, such as appropriate viscosity, good fluidity, good adhesion ability, etc. Compared with pure oil agents, emulsion-type oil agents have better ductility and lower cost, so they are more suitable for the lubrication of the medium and high speed textile process.

[0004] However, in existing spinning finishes, factors such as the temperature, concentration, pH, and raw material components of the finish can all have a certain impact on the viscosity-temperature and viscosity-concentration characteristics of emulsion-type finishes. The superposition of many factors ultimately leads to significant fluctuations in the viscosity of emulsion-type finishes during use, thereby affecting the smooth progress of the spinning process. Among them, the main reason for the instability of the viscosity-temperature and viscosity-concentration characteristics of emulsion-type finishes is that the finish is generally prepared as 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 finish on the fiber surface rapidly rises from room temperature, and the concentration continuously increases from about 10%. Such drastic changes in the temperature, water content, etc. of the emulsion-type finish will lead to a significant change in the viscosity of the emulsion-type finish. The phenomenon that the viscosity characteristics of this emulsion vary greatly with temperature or finish concentration is the instability of the viscosity-temperature and viscosity-concentration characteristics of the finish. The instability of the viscosity-temperature and viscosity-concentration characteristics of the finish not only causes an excessive fluctuation range of the finish viscosity during high-speed spinning but also leads to uneven oiling, resulting in obvious fluctuations in the tension of the fiber during the spinning process, easily causing phenomena such as hairiness and broken ends, and a large amount of coking on the heater, ultimately affecting the quality of the silk.

[0005] In the prior art, those skilled in the art have provided many technical solutions to improve the viscosity-temperature and viscosity-concentration characteristics of the finish. However, they mostly focus on the modification of the oil-phase components, hoping to obtain a finish with more stable viscosity-temperature and viscosity-concentration characteristics by improving the performance of the oil-phase components. In addition, considering that in lubrication systems, such as lubricants and emulsion-type finishes, cellulose, polyethylene glycol, polyvinyl alcohol, etc. are often used as viscosity regulators to adjust the viscosity and adhesion of the lubrication system, and these viscosity regulators mostly have the following characteristics: an increase in temperature will accelerate the thermal movement of the viscosity regulator molecules, reducing the intermolecular interaction force, thereby decreasing the viscosity of the finish; a decrease in water content will enhance the intermolecular interaction of the viscosity regulator molecules, resulting in an increase in the viscosity of the finish. For most emulsion-type finishes, compared with the increase in the viscosity of the finish caused by the decrease in water content, since the initial viscosity of the emulsion-type finish during use is relatively low and the water content is relatively high, such as usually up to about 90%, but the spinning speed of the fiber during the spinning process is extremely fast, resulting in strong shear and friction on the finish, and the temperature rises extremely fast. At the same time, the viscosity of the finish decreases more significantly with the increase in temperature. Therefore, the viscosity of the finish is more sensitive to the decrease in viscosity caused by the increase in the temperature of the finish. Coupled with the obvious shear-thinning performance of these viscosity regulators, this causes problems such as uneven oiling at low temperatures and high viscosities in the initial stage of spinning and splashing at high temperatures and low viscosities in the middle and later stages of spinning. Therefore, the prior art has also tried to improve the stability of the viscosity-temperature and viscosity-concentration characteristics of the finish through the slow release of the viscosity regulator. However, the effects are not ideal. Therefore, providing a polyester spinning finish with high temperature resistance and better viscosity-temperature and viscosity-concentration stability at high temperatures is one of the technical problems that those skilled in the art urgently need to solve. Summary of the Invention

[0006] The object of the present invention is to provide a polyester sizing agent with high temperature resistance for solving the problem of unstable viscosity-temperature and viscosity-concentration characteristics of the existing sizing agent.

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

[0008]

[0009] Further, 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, then add 0.3-0.8% of a modifier based on the amount of the low-polymerization-degree polyvinyl alcohol and 0.1-0.5% of a surfactant based on the amount of the low-polymerization-degree polyvinyl alcohol. After dispersing evenly, heat the mixture to 60-90 °C, react for 0.5-1.5 h under stirring, and then perform defoaming treatment 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 wait until the low-polymerization-degree polyvinyl alcohol is dissolved, then heat the solution to 50-80 °C, and then add 0.05-0.1% of a crosslinking agent based on the amount of the low-polymerization-degree polyvinyl alcohol. React for 30-60 min under low-speed stirring to obtain mixture B;

[0012] S3. Mix mixture A and mixture B according to a weight ratio of (5-8):(2-4), and then the modified polyvinyl alcohol aqueous solution can be obtained.

[0013] Further, 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] Further, the crosslinking agent is selected from one or more of oxalic acid, glyoxal, malonic acid, malondialdehyde, succinic acid, and succinaldehyde.

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

[0016] S4. After mixing mixture A and mixture B according to the set weight ratio, first stir the obtained mixture in a water bath at 50-80 °C for 5-10 min at a low speed, then add 0.1-0.3 part by weight of cellulose to the mixture and further stir until the cellulose is completely dissolved. Then place the obtained mixture in a low-temperature environment of -30 to -10 °C and freeze it until it is completely solidified, and then thaw it naturally at room temperature. After that, freeze and thaw it 3-5 times repeatedly, and then the modified polyvinyl alcohol aqueous solution can be obtained.

[0017] Further, the cellulose is selected from one or more of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose, and the cellulose is a short-chain low-polymerization cellulose with a degree of polymerization of 100 to 300.

[0018] Further, the smoothing agent includes 50 to 60 wt% of polyether and 40 to 50 wt% of mineral oil.

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

[0020] Disperse 3 to 5 parts by weight of seaweed extract into 50 to 100 parts by weight of an alkaline solution, stir until evenly mixed, then disperse 5 to 10 parts by weight of porous inorganic anti-friction particles into this alkaline solution, react at 30 to 50 °C with stirring for 5 to 10 min, then let it stand at room temperature for 10 to 30 min, and after filtration and drying, the modified porous inorganic anti-friction particles are obtained.

[0021] Further, the particle size of the porous inorganic anti-friction particles is ≤100 um, and the porous inorganic anti-friction particles are aluminosilicate porous materials.

[0022] Further, the preparation process of the high-temperature-resistant polyester finishing agent includes the steps of:

[0023] First, disperse the formulated amount of modified porous inorganic anti-friction particles into the smoothing agent, stir thoroughly until evenly dispersed, then add an antistatic agent, a bundling agent, and an emulsifier, and stir evenly to obtain an oil-phase solution;

[0024] Mix the oil-phase solution with an aqueous solution of modified polyvinyl alcohol, and after homogenization and emulsification, obtain the high-temperature-resistant polyester finishing agent.

[0025] The beneficial effect of the present invention is that the high-temperature-resistant polyester finishing agent provided by the present invention can maintain good viscosity-temperature and viscosity-concentration characteristics of the finishing agent stable at high temperatures. Specific Embodiments

[0026] Next, the technical solutions in the present application will be clearly described in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art belong to the scope protected by the present application.

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

[0028] A high-temperature resistant polyester finishing 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 regulators, 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% of polyether and 40-50 wt% of mineral oil.

[0033] As some examples of the present invention, the emulsifier is selected from one or more of fatty alcohol polyoxyethylene ethers, polyoxyethylene cholesterol ethers, fatty acid polyethylene glycol esters, stearates, 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, secondary alkyl sulfonate, dodecyldimethylamine oxide, etc.

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

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

[0037] Disperse 3 to 5 parts by weight of seaweed extract into 50 to 100 parts by weight of an alkaline solution. After stirring until evenly mixed, disperse 5 to 10 parts by weight of porous inorganic anti-friction particles into this alkaline solution. React at 30 to 50 °C with stirring for 5 to 10 minutes, then let it stand at room temperature for 10 to 30 minutes. After filtration and drying, the modified porous inorganic anti-friction particles are obtained.

[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 particle size of the porous inorganic anti-friction particles is ≤100 um.

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

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

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

[0043] Preferably, the content of alginic acid in the seaweed extract should be not less than 15 wt%.

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

[0045] S1, Mix 3 to 5 parts by weight of low-polymerization-degree polyvinyl alcohol and 30 to 50 parts by weight of deionized water. After stirring until the low-polymerization-degree polyvinyl alcohol is dissolved, add 0.3 to 0.8% of a modifier based on the amount of the low-polymerization-degree polyvinyl alcohol and 0.1 to 0.5% of a surfactant based on the amount of the low-polymerization-degree polyvinyl alcohol. After dispersing evenly, heat the mixture to 60 to 90 °C and react with stirring for 0.5 to 1.5 h. After defoaming treatment, obtain mixture A;

[0046] S2, Mix 2 to 4 parts by weight of low-polymerization-degree polyvinyl alcohol and 50 to 80 parts by weight of deionized water. Stir and wait until the low-polymerization-degree polyvinyl alcohol is dissolved, then heat the solution to 50 to 80 °C, and then add 0.05 to 0.1% of a cross-linking agent based on the amount of the low-polymerization-degree polyvinyl alcohol. React at low speed with stirring for 30 to 60 minutes to obtain mixture B;

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

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

[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, succinaldehyde, etc.

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

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

[0053] S4. After mixing the mixture A and the mixture B according to a set weight ratio, first stir the mixture in a water bath at a temperature of 50 to 80 °C at a low speed for 5 to 10 minutes, then add 0.1 to 0.3 parts by weight of cellulose to the mixture and further stir until the cellulose is completely dissolved. Then, place the obtained mixture in a low-temperature environment of -30 to -10 °C and freeze it until it is completely solidified, and then thaw it naturally at room temperature. After that, freeze and thaw it 3 to 5 times repeatedly to obtain the modified polyvinyl alcohol aqueous solution.

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

[0055] Preferably, the cellulose is selected from one or more of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.

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

[0057] Preferably, the cellulose is a short-chain low-degree-of-polymerization 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 cellulose containing a large number of hydroxyl groups such as hydroxyethyl cellulose and hydroxypropyl cellulose, 0.5 to 1% of the surfactant sodium dodecyl sulfate can be added synchronously with the amount of cellulose used.

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

[0060] First, disperse the formulated amount of modified porous inorganic anti-friction particles into the smoothing agent. After fully stirring until evenly dispersed, add the antistatic agent, bundling agent, and emulsifier, and stir evenly to obtain an oil-phase solution;

[0061] Mix the oil-phase solution with the aqueous solution of modified polyvinyl alcohol, and then homogenize and emulsify to obtain the high-temperature resistant polyester spinning finish of the present invention.

[0062] Generally, the viscosity-temperature and viscosity-concentration characteristics of a spinning finish include viscosity-temperature characteristics and viscosity-concentration characteristics. The viscosity-temperature characteristics refer to the relationship between the viscosity of the spinning finish and temperature. For a spinning finish, the viscosity-temperature characteristics are an important performance index. The smaller the change in the viscosity of the spinning finish with temperature, the better the viscosity-temperature characteristics of the finish. In addition, the viscosity-concentration characteristics refer to the relationship between the viscosity of the spinning finish and concentration. The concentration of the spinning finish has a direct impact on its viscosity. Generally, the higher the concentration, the greater the viscosity.

[0063] During the spinning process, the viscosity-temperature and viscosity-concentration characteristics of the spinning finish have important effects on the quality of the fiber, the stability of spinning, and the production efficiency. Appropriate viscosity-temperature and viscosity-concentration characteristics can ensure that the finish adheres evenly to the fiber surface, providing sufficient lubrication and bundling effects for the fiber, thereby improving the quality of the fiber.

[0064] Currently, the viscosity regulators used in spinning finishes are mostly high molecular polymers such as cellulose, polyethylene glycol, and polyvinyl alcohol. Since there are a large number of hydrogen bonds in the aqueous solution systems of these substances, for example, the molecular chain of polyvinyl alcohol has a relatively strict linear regular structure, and the hydroxyl groups on the monomer units cause there to be three types of hydrogen bonds in its aqueous solution system: intramolecular hydrogen bonds, intermolecular hydrogen bonds, and hydrogen bonds between polyvinyl alcohol and water molecules. These hydrogen bond interactions greatly affect the conformation of polymer macromolecules and the rheological behavior of polyvinyl alcohol solutions, and thus affect the fluidity, viscosity, adhesion, and other properties of polyvinyl alcohol solutions. Especially for spinning finishes, since the temperature of the fiber and the finish is relatively low, the concentration is relatively high, and the shear rate is relatively low during the oiling process, the common problems of current polyester high-speed spinning finishes are as follows: emulsion-type finishes have a high viscosity at low temperatures, resulting in uneven oiling; at high temperatures, the viscosity is low, and the finish on the fiber will splash onto the hot roller under the action of centrifugal force, and it is easy to form coke-like substances after long-term heating. In the light case, it affects the heat conduction efficiency of the heater, resulting in uneven stretching of the filament bundle; in the severe case, it increases the number of flyings and breaks, affecting production.

[0065] On this basis, the present invention proposes a new emulsion-type spinning finish using an improved aqueous solution of modified polyvinyl alcohol as a viscosity regulator, which has the following characteristics:

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

[0067] (2) However, the ability of polyvinyl alcohol with low degree of polymerization to enhance the viscosity of the oil agent is slightly lower. If the addition amount of polyvinyl alcohol with low degree of polymerization is too large, it will exacerbate the hydrogen bond interaction between polyvinyl alcohol molecules and between polyvinyl alcohol and water molecules, resulting in an increased sensitivity of the rheological behavior of the polyvinyl alcohol aqueous solution to changes in temperature and concentration, and a decrease in the stability of the viscosity-temperature and viscosity-concentration characteristics of the oil agent; to alleviate the obvious change in the viscosity of the oil agent caused by polyvinyl alcohol with low degree of polymerization when the temperature of the oil agent is high and the water content decreases, therefore, in the present invention, a small amount of modifier and surfactant are used to destroy and weaken the hydrogen bond interaction in a part of the polyvinyl alcohol with low degree of polymerization, so as to change the rheological behavior of the polyvinyl alcohol aqueous solution by sacrificing a part of the hydrogen bond interaction and reducing the viscosity of the polyvinyl alcohol aqueous solution with the same concentration, especially reducing its initial viscosity at low shear rates, and obtaining a polyvinyl alcohol aqueous solution with slightly reduced viscosity but reduced sensitivity to changes in temperature and concentration, thereby improving the viscosity-temperature and viscosity-concentration characteristics of the prepared spinning oil agent.

[0068] (3) On the basis of feature (2), in order to reduce the dosage of polyvinyl alcohol and further improve the viscosity-temperature and viscosity-concentration characteristics of the spinning oil agent, especially to improve the ability of the oil agent to quickly spread on the fiber surface and uniformly adhere to the fiber surface during high-speed spinning, in the present invention, another part of the polyvinyl alcohol with low degree of polymerization is micro-crosslinked to form small network fragment structures, and the same is mixed with the polyvinyl alcohol solution treated with the modifier and surfactant, and finally an oil agent with good fluidity, appropriate viscosity and strong adhesion at low temperature is obtained, so that the oil agent can quickly and uniformly coat the fiber surface to meet the requirements of high-speed spinning.

[0069] (4) Further, to address the defect that the oil agent has a reduced viscosity and is prone to splashing at high temperatures during high-speed spinning, the present invention also adds cellulose and surfactant to the mixed system obtained by mixing mixture A and mixture B, so as to reduce the number of hydrogen bonds in the system through the action of the negatively charged hydrophilic groups on the surfactant with the hydroxyl groups on the cellulose and polyvinyl alcohol molecular chains, inhibit the hydrogen bond interaction between short-chain cellulose and polyvinyl alcohol molecules, improve the adhesion of the oil agent and stabilize the viscosity-temperature and viscosity-concentration characteristics of the oil agent. At the same time, the viscosity of the oil agent at high temperatures is improved by using the high molecular polymer formed by the cross-linking interaction between cellulose and modified porous inorganic anti-friction particles.

[0070] (5) The interaction process between cellulose and the modified porous inorganic anti-friction particles is described as follows: First, during the preparation of the modified porous inorganic anti-friction particles, substances such as alginic acid in the seaweed liquid extract can react with the silicon-aluminum compounds in the porous inorganic anti-friction particles to form alginic acid silicon-aluminum compounds. During the spinning process, the modified porous inorganic anti-friction particles will be able to diffuse from the oil phase to the water phase under the action of friction, etc., and then the alginic acid silicon-aluminum compounds attached thereto can gradually cross-link with substances such as cellulose in the water phase during use to form a high molecular polymer, thereby improving the problems of the oil agent during high-speed spinning, especially in the middle and late stages of spinning, such as the rapid increase in the temperature of the oil agent, the aggravation of shear thinning, the resulting decrease in the viscosity of the oil agent, and easy splashing.

[0071] (6) In addition, the modified porous inorganic anti-friction particles described in the present invention can not only play a slow-release role but also play an anti-friction role.

[0072] The high-temperature resistant polyester oil agent of the present invention is illustrated by the following specific examples:

[0073] Example 1

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

[0075] Disperse 4 parts by weight of seaweed extract into 80 parts by weight of a sodium hydroxide alkaline solution with a concentration of 3 wt%, wherein the content of alginic acid in the seaweed extract is 18 wt%; after stirring until evenly mixed, disperse 8 parts by weight of porous attapulgite particles into the alkaline solution, react at 40 °C with stirring for 10 min, then let it stand at room temperature for 20 min, and after filtration and drying, the modified porous inorganic anti-friction particles are obtained.

[0076] Example 2

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

[0078] Disperse 3 parts by weight of seaweed extract into 50 parts by weight of a sodium hydroxide alkaline solution with a concentration of 1 wt%, wherein the content of alginic acid in the seaweed extract is 16 wt%; after stirring until evenly mixed, disperse 10 parts by weight of porous zeolite particles into the alkaline solution, react at 50 °C with stirring for 8 min, then let it stand at room temperature for 10 min, and after filtration and drying, the modified porous inorganic anti-friction particles are 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, then add 0.5% of the modifier nickel sulfate based on the amount of low-polymerization-degree polyvinyl alcohol and 0.3% of sodium dodecyl sulfate based on the amount of low-polymerization-degree polyvinyl alcohol. After dispersing evenly, heat the mixture to 70 °C, react for 1 h under stirring, and then perform degassing treatment 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 wait until the low-polymerization-degree polyvinyl alcohol is dissolved, then heat the solution to 60 °C, and then add 0.06% of the crosslinking agent glyoxal based on the amount of low-polymerization-degree polyvinyl alcohol. React for 50 min under low-speed stirring to obtain mixture B;

[0083] S3. Mix the mixture A and mixture B according to a weight ratio of 6:3 to obtain the modified polyvinyl alcohol aqueous solution.

[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, then add 0.3% of the modifier calcium chloride based on the amount of low-polymerization-degree polyvinyl alcohol and 0.5% of sodium dodecyl sulfate based on the amount of low-polymerization-degree polyvinyl alcohol. After dispersing evenly, heat the mixture to 90 °C, react for 0.5 h under stirring, and then perform degassing treatment 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 wait until the low-polymerization-degree polyvinyl alcohol is dissolved, then heat the solution to 80 °C, and then add 0.1% of the crosslinking agent oxalic acid based on the amount of low-polymerization-degree polyvinyl alcohol. React for 30 min under low-speed stirring to obtain mixture B;

[0088] S3. Mix the mixture A and mixture B according to a weight ratio of 5:4 to obtain the modified polyvinyl alcohol aqueous solution.

[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, then add 0.8% of the modifier calcium chloride based on the amount of low-polymerization-degree polyvinyl alcohol and 0.1% of sodium dodecyl sulfate based on the amount of low-polymerization-degree polyvinyl alcohol. After dispersing evenly, heat the mixture to 60 °C, react for 1.5 h under stirring, and then perform degassing treatment to obtain mixture A;

[0092] S2, 2 parts by weight of low-polymerization degree polyvinyl alcohol and 80 parts by weight of deionized water are mixed, stirred, and after the low-polymerization degree polyvinyl alcohol is dissolved, the solution is heated to 50° C., and then 0.05% of the low-polymerization degree polyvinyl alcohol is added with oxalic acid as a cross-linking agent, and the mixture is reacted for 60 minutes under low-speed stirring to obtain a mixed solution B;

[0093] S3, mixing the mixed solution A and the mixed solution B in a weight ratio of 8:2 to obtain the modified polyvinyl alcohol aqueous solution.

[0094] Example 6

[0095] Preparation of modified polyvinyl alcohol aqueous solution:

[0096] The only difference between it and the above-mentioned Example 3 is that after the mixed solution A and the mixed solution B are mixed in a weight ratio of 6:3, the mixed solution is first stirred at a low speed for 5 minutes in a water bath at a temperature of 80°C, and then 0.2 parts by weight of hydroxypropyl cellulose and 0.7% of the surfactant sodium dodecyl sulfate are added to the mixed solution, and the mixture is further stirred until the cellulose is completely dissolved. The obtained mixed solution is then placed in a low temperature environment of -15°C and frozen until it is completely solidified, and then thawed naturally at room temperature. After repeated freezing and thawing 4 times, the modified polyvinyl alcohol aqueous solution is obtained.

[0097] Embodiments 7 to 13

[0098] Preparation of high temperature resistant polyester oil:

[0099] Firstly, the modified porous inorganic anti-friction particles of the formula amount are dispersed in the smoothing agent, and after being fully stirred until the dispersion is uniform, an antistatic agent, a sizing agent and an emulsifier are added, and after being stirred uniformly, an oil phase solution is obtained;

[0100] The oil phase solution is mixed with the modified polyvinyl alcohol aqueous solution, and then homogenized and emulsified to obtain the high temperature resistant polyester oil agent of the present invention.

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

[0102] Table 1 Raw material ratio of polyester oil

[0103]

[0104] Among them, the smoothing agents used in Examples 7 to 8 are: 50 wt% polyether + 40 wt% mineral oil + 10 wt% vegetable oil; the emulsifier is a mixture of stearic acid ester, fatty alcohol polyoxyethylene ether, and polyoxyethylene cholesterol ether; the antistatic agent is a mixture of alkyl phosphate salt and lauryl alcohol polyoxyethylene ether; the bundling agent is a mixture of fatty acid triethanolamine salt, castor oil polyoxyethylene ether, and polyethylene glycol laurate; the modified porous inorganic anti-friction particles are the modified porous inorganic anti-friction particles prepared in Example 1 above; the additive is a mixture of defoamer and dispersant; the modified polyvinyl alcohol aqueous solution is the modified polyvinyl alcohol aqueous solution prepared in Example 3 above;

[0105] The smoothing agents used in Examples 9 - 10 are: 60 wt% polyether + 40 wt% mineral oil; the emulsifier is a mixture of fatty acid polyethylene glycol ester, stearic acid ester, and sodium oleate; the antistatic agent is a mixture of alkyl phosphate salt, alkyl sulfonate salt, and lauryl alcohol polyoxyethylene ether; the bundling agent is a mixture of sulfated castor oil and castor oil polyoxyethylene ether; the modified porous inorganic anti-friction particles are the modified porous inorganic anti-friction particles prepared in Example 2 above; the additive is a mixture of defoamer, dispersant, pH regulator, and wetting penetrant; the modified polyvinyl alcohol aqueous solution is the modified polyvinyl alcohol aqueous solution prepared in Example 4 above;

[0106] The smoothing agents used in Examples 11 - 12 are: 60 wt% polyether + 40 wt% mineral oil; the emulsifier is a mixture of potassium oleate, oleic acid polyoxyethylene ester, and polyoxyethylene cholesterol ether; the antistatic agent is a mixture of alkyl sulfonate salt, alkyl sulfate salt, alkyl quaternary ammonium salt, and fatty alcohol polyoxyethylene ether phosphate salt; the bundling agent is a mixture of lauryl polyoxyethylene ether, polyoxyethylene polyoxypropylene ether, and ricinoleic acid polyoxyethylene ester; the modified porous inorganic anti-friction particles are the modified porous inorganic anti-friction particles prepared in Example 2 above; the additive is a mixture of defoamer, dispersant, pH regulator, wetting penetrant, and antioxidant; the modified polyvinyl alcohol aqueous solution is the modified polyvinyl alcohol aqueous solution prepared in Example 5 above;

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

[0108] Comparative Example 1

[0109] The difference between it and the above Example 13 is that porous attapulgite without being modified by seaweed extract is used as the porous inorganic anti-friction particles to prepare polyester finishing oil.

[0110] Comparative Example 2

[0111] The difference from the above-mentioned Embodiment 13 is that the modified polyvinyl alcohol aqueous solution used does not contain cellulose and surfactant sodium dodecyl sulfate. When preparing the modified polyvinyl alcohol aqueous solution, after mixing the mixture A and the mixture B according to the weight ratio, the mixture is first stirred at a low speed for 5 minutes in a water bath at a temperature of 80 °C, and then the obtained mixture is placed in a low-temperature environment of -15 °C and frozen until completely solidified, and then naturally thawed at room temperature. After that, it is repeatedly frozen and thawed 4 times to obtain the modified polyvinyl alcohol aqueous solution.

[0112] Comparative Example 3

[0113] The difference from the above-mentioned Embodiment 13 is that the modified polyvinyl alcohol aqueous solution used does not contain surfactant sodium dodecyl sulfate while adding cellulose.

[0114] Comparative Example 4

[0115] The difference from the above-mentioned Embodiment 13 is that the modified polyvinyl alcohol aqueous solution used is not subjected to repeated freezing-thawing treatment. When preparing the modified polyvinyl alcohol aqueous solution, after mixing the mixture A and the mixture B according to the weight ratio, the mixture is first stirred at a low speed for 5 minutes in a water bath at a temperature of 80 °C, and then 0.2 parts by weight of hydroxypropyl cellulose and 0.7% of the amount of cellulose surfactant sodium dodecyl sulfate are added to the mixture and further stirred until the cellulose is completely dissolved to obtain the modified polyvinyl alcohol aqueous solution.

[0116] Comparative Example 5

[0117] The difference from the above-mentioned Embodiment 7 is that the mixture A in the modified polyvinyl alcohol aqueous solution used is not modified. When preparing the mixture A, 4 parts by weight of low-polymerization-degree polyvinyl alcohol and 40 parts by weight of deionized water are mixed, stirred until the low-polymerization-degree polyvinyl alcohol is dissolved, and then defoamed to obtain the mixture A.

[0118] Comparative Example 6

[0119] The difference from the above-mentioned Embodiment 7 is that the mixture B in the modified polyvinyl alcohol aqueous solution used is not crosslinked and modified. When preparing the mixture B, 3 parts by weight of low-polymerization-degree polyvinyl alcohol and 60 parts by weight of deionized water are mixed, stirred until the low-polymerization-degree polyvinyl alcohol is dissolved, and then defoamed to obtain the mixture B.

[0120] Comparative Example 7

[0121] The difference from the above-mentioned Embodiment 7 is that the modified polyvinyl alcohol aqueous solution used only contains 40 parts by weight of the mixture A.

[0122] Test Example 1

[0123] (1) Detection of oil agent physical properties:

[0124] After adding water and mixing the polyester finishing agent prepared in the above Examples 7 to 13, an emulsion with a finishing agent content of 15% was prepared, and the pH value, surface tension, room temperature stability (25 °C, 7 d), and high temperature stability (80 °C, 8 h) were detected.

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

[0126] Table 2 Physical Property Detection of Finishing Agent

[0127]

[0128] (2) Detection of the performance of the finishing agent viscosity varying with temperature and concentration:

[0129] The viscosity of the prepared emulsion-type finishing agent varying with temperature and water content was detected multiple times. The specific process was as follows:

[0130] The finishing agents prepared in the above Examples 7 to 13 and Comparative Examples 1 to 7 were added with water and then formulated into an emulsion with a finishing agent content of 15%. It was placed in a covered container with a weight measuring device, heated, and stirred at a speed of 800 rpm. The heating power was controlled so that the solution gradually increased in temperature to 100 °C at a rate of 5 - 10 °C / min, and then kept warm at 100 °C. During the heating and stirring process, when heated to the set temperature (such as 50 °C), the container lid was opened to accelerate water evaporation. After the water loss rate of the solution reached the set value (such as 3%), the container lid was covered, and the emulsion temperature was heated to the next set temperature (such as 75 °C). Then the container lid was opened again to accelerate water evaporation. After the water loss rate of the solution reached the set value (such as 5%), the container lid was covered again. This was repeated to obtain emulsions with different temperatures and concentrations, and the water loss rate (assuming that the weight evaporated during the heating process of the emulsion was all water weight, then the water loss rate = evaporation weight loss / initial weight) and viscosity (cP) of the emulsions in different states were recorded and detected. The results are shown in Table 3 below:

[0131] Table 3 Viscosity Stability Detection of Finishing Agent

[0132]

[0133]

[0134] (3) Spinning performance test:

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

[0136] Table 4 Spinning Performance Test Results

[0137]

[0138]

[0139] The embodiments of the present application have been described above in combination with the embodiments. Without conflict, the embodiments and the features in the embodiments in the present application can be combined with each other. The present application is not limited to the above specific implementation manners. The above specific implementation manners are merely illustrative rather than restrictive. Under the inspiration of the present application, those of ordinary skill in the art can also make many forms without departing from the purpose of the present application and the scope protected by the claims, and all of them fall within the protection scope of the present application.

Claims

1. A high temperature resistant polyester oil agent, characterized in that: By weight, it includes the following raw material components:

2. The high temperature resistant polyester oil according to claim 1, characterized in that: The preparation process of the modified polyvinyl alcohol aqueous solution comprises the following steps: S1, 3-5 parts by weight of low-polymerization degree polyvinyl alcohol and 30-50 parts by weight of deionized water are mixed, stirred until the low-polymerization degree polyvinyl alcohol is dissolved, and then 0.3-0.8% of a modifier for the low-polymerization degree polyvinyl alcohol and 0.1-0.5% of a surfactant for the low-polymerization degree polyvinyl alcohol are added, and after uniform dispersion, the mixed solution is heated to 60-90° C., reacted for 0.5-1.5 hours under stirring, and subjected to degassing treatment to obtain a mixed solution A; S2, 2 to 4 parts by weight of low-polymerization degree polyvinyl alcohol and 50 to 80 parts by weight of deionized water are mixed, stirred, and after the low-polymerization degree polyvinyl alcohol is dissolved, the solution is heated to 50 to 80° C., and then a cross-linking agent in an amount of 0.05 to 0.1% of the low-polymerization degree polyvinyl alcohol is added, and the mixture is reacted for 30 to 60 minutes under low-speed stirring to obtain a mixed solution B; S3, mixing the mixed solution A and the mixed solution B in a weight ratio of (5-8):(2-4) to obtain the modified polyvinyl alcohol aqueous solution.

3. The high temperature resistant polyester oil according to claim 2, characterized in that: 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.

4. The high temperature resistant polyester oil according to claim 2, characterized in that: The cross-linking agent is selected from one or more of oxalic acid, glyoxal, malonic acid, malondialdehyde, succinic acid, and succinaldehyde.

5. The high temperature resistant polyester oil according to claim 2, characterized in that: The preparation process of the modified polyvinyl alcohol aqueous solution also includes the steps of: S4, after the mixed solution A and the mixed solution B are mixed according to the set weight ratio, the obtained mixed solution is first stirred at a low speed for 5 to 10 minutes in a water bath at a temperature of 50 to 80°C, and then 0.1 to 0.3 parts by weight of cellulose is added to the mixed solution, and further stirred until the cellulose is completely dissolved. The obtained mixed solution is then placed in a low temperature environment of -30 to -10°C and frozen until it is completely solidified, and then thawed naturally at room temperature. After repeated freezing and thawing for 3 to 5 times, the modified polyvinyl alcohol aqueous solution is obtained.

6. The high temperature resistant polyester oil according to claim 5, characterized in that: The cellulose is selected from one or more of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, and the cellulose is a short-chain low-polymerization cellulose with a polymerization degree of 100 to 300.

7. The high temperature resistant polyester oil according to claim 1, characterized in that: The lubricant comprises 50-60 wt % of polyether and 40-50 wt % of mineral oil.

8. The high temperature resistant polyester oil according to claim 1, characterized in that: The preparation process of the modified porous inorganic friction-reducing particles is as follows: 3 to 5 parts by weight of seaweed extract are dispersed in 50 to 100 parts by weight of an alkaline solution, stirred until uniformly mixed, and then 5 to 10 parts by weight of porous inorganic friction-reducing particles are dispersed in the alkaline solution, reacted at 30 to 50° C. with stirring for 5 to 10 minutes, then allowed to stand at room temperature for 10 to 30 minutes, filtered, and dried to obtain modified porous inorganic friction-reducing particles.

9. The high temperature resistant polyester oil according to claim 8, characterized in that: The particle size of the porous inorganic anti-friction particles is ≤100 um, and the porous inorganic anti-friction particles are porous aluminosilicate materials.

10. The high temperature resistant polyester oil agent according to claim 3, characterized in that: The preparation process of the high temperature resistant polyester oil comprises the following steps: Firstly, the modified porous inorganic anti-friction particles of the formula amount are dispersed in the smoothing agent, and after being fully stirred until the dispersion is uniform, an antistatic agent, a sizing agent and an emulsifier are added, and after being stirred uniformly, an oil phase solution is obtained; The oil phase solution is mixed with the modified polyvinyl alcohol aqueous solution, and then homogenized and emulsified to obtain a high temperature resistant polyester oil agent.

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