Special spinning oil agent for superfine denier fibers and preparation method thereof

Abstract

The invention belongs to the technical field of spinning assistants, and particularly relates to a special spinning oil agent for superfine denier fibers and a preparation method thereof, the special spinning oil agent comprises the following raw materials by weight: 60-80 parts of a smoothing agent, 10-20 parts of an emulsifier, 5-10 parts of an antistatic agent, 5-15 parts of a bundling agent, and 3-5 parts of a porous activated carbon-based composite additive, the prepared spinning oil agent special for the superfine denier fibers is high in adhesive force on the surfaces of the fibers, the fluffing and end breaking phenomena caused by oil film falling of superfine denier fibers can be effectively relieved, and the spinning oil agent special for the superfine denier fibers is especially suitable for preparing the superfine denier fibers.

Description

Technical Field

[0001] The invention belongs to the technical field of spinning auxiliaries, and in particular relates to a special spinning oil for ultra-fine denier fibers and a preparation method thereof. Background Art

[0002] Ultrafine denier fiber, also known as ultrafine fiber, fine fiber or microfiber, is a very small fiber with a fineness (fineness) much lower than that of conventional fiber. There is no unified standard internationally for the specific definition of ultrafine denier fiber. The American PET Committee defines fibers with a single filament fineness (dpf) of 0.3 to 1.0 dtex as ultrafine fibers. The Dutch AKZO company believes that the upper limit of ultrafine fiber fineness is 0.3 dtex, and Japan calls fibers below 0.55 dtex ultrafine fibers. The Chemical Fiber Industry Company of the Ministry of Textile Industry of my country has made the following definition of ultrafine fibers: the dpf values ​​of various fibers are as follows: polyester filament 0.5 to 1.3 dtex; nylon filament 0.5 to 1.7 dtex; polypropylene filament 0.5 to 2.2 dtex; staple fiber 0.5 to 1.3 dtex.

[0003] As we all know, when the fiber monofilament fineness is reduced to a certain level, the fabric woven with this microfiber will show many unique characteristics: such as soft feel, high flexibility, soft luster, high water absorption, etc. Therefore, the research and development of ultra-fine fibers has been a hot technology studied by various countries in recent years. Many domestic scientific research institutions and production enterprises have invested a lot of manpower and material resources in the research and production of ultra-fine denier fibers. Ultra-fine denier fibers have very small bending stiffness due to their small diameter, and the fibers feel particularly soft. Ultra-fine denier fibers mainly have the following excellent properties:

[0004] 1. The specific surface area is large, so the coverage, fluffiness and warmth retention of ultrafine fiber fabrics are significantly improved;

[0005] 2. Due to its large specific surface area, ultrafine fibers come into contact with dust or oil more often, and oil has more opportunities to penetrate through the gaps between the fiber surfaces, so it has a very strong cleaning function;

[0006] 3. Ultra-high density fabrics made of ultra-fine denier fibers have gaps between the diameter of water droplets and the diameter of water vapor droplets, so ultra-fine denier fiber fabrics have excellent waterproof and vapor permeability effects;

[0007] 4. There are many tiny pores between the ultrafine fibers in the fabric, forming a capillary structure. If it is processed into a towel-like fabric that can be wetted by water, it has high water absorption;

[0008] 5. Ultrafine denier fiber has extremely fine fiber density, which greatly reduces the stiffness of the silk, making the fabric feel very soft. It can also increase the layered structure of the silk, increase the specific surface area and capillary effect, and make the reflected light inside the fiber more delicately distributed on the surface, giving it an elegant luster like silk and good moisture absorption and heat dissipation.

[0009] Therefore, ultrafine denier fibers are widely loved by the public and are mainly used to make high-end fashion, such as imitation silk, high-density waterproof and breathable outdoor clothing, underwear, artificial leather, high-grade pile fabrics, bedding, etc. In addition, ultrafine denier fibers can also be used to prepare filter materials, precision optical instrument lens cleaning cloths, surgical gowns, masks and other products.

[0010] However, the production technology of ultrafine denier fibers is relatively complex, requiring high-precision spinning equipment and advanced spinning technology. At present, synthetic fibers such as polyester and nylon are the main raw materials for the production of ultrafine denier fibers. The main production technologies of ultrafine fibers at present are: direct spinning, composite spinning and blended spinning. Compared with composite spinning and blended spinning, direct spinning has the advantages of simple production process, cost saving, stable quality and green environmental protection. However, it is still very difficult to produce ultrafine fibers by direct spinning. The main reasons are: the spinnability of the raw materials is poor, and ultrafine fibers have high requirements for cooling uniformity during the spinning process. In addition, in the spinning process of ultrafine denier fibers, due to the fineness of each single filament, its strength is small. During the drafting and winding process, it will pass through multiple drafting rollers and winding rollers, etc., which may cause the breakage of the single filaments and cause the fuzzing of ultrafine denier fibers. Therefore, the number of filaments and broken ends is also an important indicator affecting the operability of fiber textile processing. The main causes of fiber breakage and fiber breakage are the friction between the drafting roller, winding roller and other rollers. Under the premise of ensuring the smoothness of the drafting roller and other parts, if the oil is not firmly attached to the fiber surface, the oil on the fiber surface will be reduced during the drafting or winding process, thereby increasing the risk of breakage and fuzzing. Therefore, how to prepare a spinning oil for ultrafine denier fibers with strong surface adhesion has become one of the first problems to be solved in the current efficient production of ultrafine denier fibers. Summary of the invention

[0011] The purpose of the present invention is to provide a special spinning oil for ultrafine denier fibers and a preparation method thereof in order to improve the surface adhesion of the oil on the ultrafine denier fibers, reduce the number of filaments and broken ends produced during the spinning process of the ultrafine denier fibers, and improve the production efficiency and product quality of the ultrafine denier fibers.

[0012] In view of this, the present invention provides a method for preparing a special spinning oil for ultrafine denier fibers, comprising the following raw materials in parts by weight: 60 to 80 parts of a smoothing agent, 10 to 20 parts of an emulsifier, 5 to 10 parts of an antistatic agent, 5 to 15 parts of a sizing agent, and 3 to 5 parts of a porous activated carbon-based composite additive.

[0013] Furthermore, the lubricant is a mixture of mineral oil, polyether, dimethyl silicone oil and hydroxy silicone oil, and the mass ratio of mineral oil, polyether, dimethyl silicone oil and hydroxy silicone oil in the lubricant is (4-7): (3-5): (0.5-1): (1-3).

[0014] Furthermore, at 25°C, the kinematic viscosity of the mineral oil is 20 to 60 mm 2 / s; the kinematic viscosity of the polyether is 50 to 300 mm 2 / s, the kinematic viscosity of the dimethyl silicone oil is 0.5-5mm 2 / s, the hydroxy silicone oil comprises a high-viscosity hydroxy silicone oil and a low-viscosity hydroxy silicone oil in a mass ratio of (0.5-2): (5-8), and the viscosity of the high-viscosity hydroxy silicone oil is 1000-30000mm 2 / s, the viscosity of the low-viscosity hydroxy silicone oil is 100-500 mm 2 / s.

[0015] Furthermore, the porous activated carbon-based composite additive includes porous activated carbon and an auxiliary agent filled in the porous activated carbon, wherein the auxiliary agent includes a catalyst and alkoxysilane in a mass ratio of (1-3): (5-10).

[0016] Furthermore, the mass ratio of the porous activated carbon to the auxiliary agent filled in the porous activated carbon is (5-10): (1-2).

[0017] Furthermore, the alkoxysilane is selected from one or more of methyltrimethoxysilane, tetramethoxysilane and tetraethoxysilane.

[0018] Furthermore, the preparation process of the porous activated carbon-based composite additive is as follows:

[0019] First, the catalyst and alkoxysilane are mixed evenly, and then the mixed solution of the catalyst and alkoxysilane is sprayed onto the porous activated carbon. After standing for 1 to 3 hours to allow the porous activated carbon to be fully infiltrated, porous carbon particles adsorbed with the catalyst and alkoxysilane are obtained, which are the porous activated carbon-based composite additive.

[0020] Furthermore, the outer side of the porous activated carbon-based composite additive is coated with a polymer compound capsule wall that is insoluble in the oil phase. The preparation process of the porous activated carbon-based composite additive is as follows:

[0021] First, the catalyst and alkoxysilane are mixed evenly, and then the mixed solution of the catalyst and alkoxysilane is sprayed onto the porous activated carbon, and allowed to stand for 1 to 3 hours to fully infiltrate the porous activated carbon, thereby obtaining porous carbon particles adsorbing the catalyst and alkoxysilane;

[0022] Chitosan and gelatin are respectively added with water to prepare an aqueous solution with a concentration of 1 to 5 wt %, and a cross-linking agent is added with a solvent to prepare a cross-linking agent solution with a concentration of 1 to 3 wt %;

[0023] The porous carbon particles are then placed in a fluidized bed, and the compressed air valve at the bottom of the fluidized bed is started to disperse and suspend the porous carbon particles in the fluidized bed. Thereafter, an aqueous solution of chitosan, an aqueous solution of gelatin, and a cross-linking agent solution are sprayed into the fluidized bed through different atomizing nozzles. Under the high temperature in the fluidized bed, chitosan and gelatin are cross-linked to form a polymer compound capsule wall coating the surface of the porous carbon particles.

[0024] Furthermore, after the porous activated carbon-based composite additive is prepared, the porous activated carbon-based composite additive may be post-processed, and the post-processing process includes:

[0025] First, in a fluidized bed, the compressed air valve at the bottom of the fluidized bed is started to disperse and suspend the porous activated carbon-based composite additive particles in the fluidized bed, and then an ethanol atomized liquid is sprayed onto the surface of the porous activated carbon-based composite additive, and then the reactor is sealed, and after reacting at 80 to 100° C. for 10 to 20 minutes, an atomized liquid of a silane coupling agent is sprayed onto the surface of the porous activated carbon-based composite additive, and then the reactor is sealed again, and after reacting at 50 to 80° C. for 30 to 60 minutes, a porous activated carbon-based composite additive after modification is obtained.

[0026] Furthermore, the preparation method of the special spinning oil for ultrafine denier fibers is as follows:

[0027] First, a smoothing agent is prepared according to a weight ratio, and the smoothing agent and the porous activated carbon-based composite additive are placed in an oven at 60 to 90° C. and dried for 5 to 10 hours;

[0028] Then, the formulated amount of smoothing agent and porous activated carbon-based composite additive are added to the reactor, and the temperature of the reactor is maintained at 30-50°C under vacuum. After stirring for 20-30 minutes, the formulated amount of emulsifier, antistatic agent and sizing agent are slowly added. Then, the temperature of the reactor is maintained at 30-50°C under vacuum, and after stirring for 30-90 minutes, a special spinning oil for ultrafine denier fibers is obtained.

[0029] The beneficial effects of the present invention are:

[0030] The special spinning oil for ultrafine denier fibers prepared by the present invention has strong adhesion on the fiber surface, can effectively alleviate the fuzzing and breakage phenomena of ultrafine denier fibers caused by oil film shedding, and is particularly suitable for the preparation of ultrafine denier fibers. DETAILED DESCRIPTION

[0031] The technical solutions in this application will be described clearly below in conjunction with the specific embodiments in this application. Obviously, the described embodiments are part of the embodiments of this application, rather than all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments in this application belong to the scope of protection of this application.

[0032] In the description of the present application, it should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. The techniques, methods and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but in appropriate cases, the techniques, methods and devices should be considered as part of the authorization specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values.

[0033] It should be noted that, in the present application, the terms "comprise", "include" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, an element defined by the sentence "comprises one..." does not exclude the presence of other identical elements in the process, method, article or device including the element. In addition, it should be noted that the scope of the method and device in the embodiment of the present application is not limited to performing functions in the order shown or discussed, and may also include performing functions in a substantially simultaneous manner or in reverse order according to the functions involved, for example, the described method may be performed in an order different from that described, and various steps may also be added, omitted, or combined. In addition, the features described with reference to certain examples may be combined in other examples.

[0034] A method for preparing a special spinning oil for ultrafine denier fibers. The special spinning oil for ultrafine denier fibers comprises the following raw materials in parts by weight: 60 to 80 parts of a smoothing agent, 10 to 20 parts of an emulsifier, 5 to 10 parts of an antistatic agent, 5 to 15 parts of a bundling agent, and 3 to 5 parts of a porous activated carbon-based composite additive.

[0035] Furthermore, the lubricant is a mixture of mineral oil, polyether, dimethyl silicone oil and hydroxy silicone oil.

[0036] Preferably, the mass ratio of mineral oil, polyether, dimethyl silicone oil and hydroxy silicone oil in the lubricant is (4-7): (3-5): (0.5-1): (1-3).

[0037] Preferably, at 25°C, the kinematic viscosity of the mineral oil is 20 to 60 mm 2 / s; the kinematic viscosity of the polyether is 50 to 300 mm 2 / s, the kinematic viscosity of the dimethyl silicone oil is 0.5-5mm 2 / s.

[0038] Preferably, the hydroxy silicone oil comprises a high-viscosity hydroxy silicone oil and a low-viscosity hydroxy silicone oil in a mass ratio of (0.5-2): (5-8), and the viscosity of the high-viscosity hydroxy silicone oil is 1000-30000 mm 2 / s, the viscosity of the low-viscosity hydroxy silicone oil is 100-500 mm 2 / s.

[0039] 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, stearic acid ester, and oleic acid polyoxyethylene ester.

[0040] As some examples of the present invention, the antistatic agent is selected from one or more of alkyl phosphate ester salts, alkyl sulfonate ester salts, alkyl sulfate ester salts, isomeric tridecyl alcohol ether phosphate esters, and lauryl alcohol polyoxyethylene ether.

[0041] As some examples of the present invention, the sizing agent is selected from one or more of fatty acid triethanolamine salt, polyethylene glycol oleate, lauryl polyoxyethylene ether, polyoxyethylene polyoxypropylene ether, sulfated castor oil, and castor oil polyoxyethylene ether.

[0042] As some preferred examples of the present invention, the ultrafine fiber-specific spinning oil further includes: 2 to 5 parts by weight of nano-silicon dioxide.

[0043] Furthermore, the porous activated carbon-based composite additive includes porous activated carbon and an auxiliary agent filled in the porous activated carbon, wherein the auxiliary agent includes a catalyst and alkoxysilane in a mass ratio of (1-3): (5-10).

[0044] Preferably, the mass ratio of the porous activated carbon to the auxiliary agent filled in the porous activated carbon is (5-10):(1-2).

[0045] As some examples of the present invention, the catalyst is selected from TE, CTDP-138S, KR-138S, ETDOP-212S, KR-212S, tetraisopropyl titanate, GBA, One or more of 726.

[0046] As some examples of the present invention, the alkoxysilane is selected from one or more of methyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane.

[0047] As some examples of the present invention, the preparation process of the porous activated carbon-based composite additive is as follows:

[0048] First, the catalyst and alkoxysilane are mixed evenly, and then the mixed solution of the catalyst and alkoxysilane is sprayed onto the porous activated carbon. After standing for 1 to 3 hours to allow the porous activated carbon to be fully infiltrated, porous carbon particles adsorbed with the catalyst and alkoxysilane are obtained, which are the porous activated carbon-based composite additive.

[0049] Furthermore, the outer side of the porous activated carbon-based composite additive is coated with a polymer compound capsule wall that is insoluble in the oil phase.

[0050] As some examples of the present invention, the polymer compound capsule wall outside the porous activated carbon-based composite additive is prepared by gelatin, carboxymethyl cellulose, chitosan, etc.

[0051] As a preferred example of the present invention, the preparation process of the porous activated carbon-based composite additive is as follows:

[0052] First, the catalyst and alkoxysilane are mixed evenly, and then the mixed solution of the catalyst and alkoxysilane is sprayed onto the porous activated carbon, and allowed to stand for 1 to 3 hours to fully infiltrate the porous activated carbon, thereby obtaining porous carbon particles adsorbing the catalyst and alkoxysilane;

[0053] Chitosan and gelatin are respectively added with water to prepare an aqueous solution with a concentration of 1 to 5 wt %, and a cross-linking agent is added with a solvent to prepare a cross-linking agent solution with a concentration of 1 to 3 wt %;

[0054] The porous carbon particles are then placed in a fluidized bed, and the compressed air valve at the bottom of the fluidized bed is started to disperse and suspend the porous carbon particles in the fluidized bed. Thereafter, an aqueous solution of chitosan, an aqueous solution of gelatin, and a cross-linking agent solution are sprayed into the fluidized bed through different atomizing nozzles. Under the high temperature in the fluidized bed, chitosan and gelatin are cross-linked to form a polymer compound capsule wall coating the surface of the porous carbon particles.

[0055] As some examples of the present invention, when preparing the chitosan and gelatin aqueous solution, in order to promote the solubility of chitosan and gelatin, a small amount of co-solvent, such as acidic or alkaline substances, can be added to the solution to promote their dissolution.

[0056] As some examples of the present invention, the cross-linking agent is selected from one or more of 3-methoxy-4-hydroxybenzaldehyde, glutaraldehyde, and geniposide.

[0057] As some examples of the present invention, the solvent of the cross-linking agent is one or more of methanol, ethanol, ether, and chloroform.

[0058] Preferably, when the porous activated carbon-based composite additive is prepared by a spray method, the particle size of the porous activated carbon-based composite additive can be controlled to be ≤100um by controlling parameters such as the particle size of the porous activated carbon, the spray rate, the spray pressure, the droplet size and the gas-liquid ratio, the nozzle aperture, and the temperature in the fluidized bed.

[0059] Preferably, when preparing the porous activated carbon-based composite additive, the mass ratio of the chitosan, gelatin and the porous carbon particles adsorbed with the catalyst and alkoxysilane is (0.5-1): (0.5-1): (5-10).

[0060] Preferably, when preparing the porous activated carbon-based composite additive, the temperature in the fluidized bed is controlled to be 50-80° C., and the atomization spraying time is 20-60 min.

[0061] As a preferred example of the present invention, the specific surface area of ​​the porous activated carbon is greater than 800 m 2 / g.

[0062] As some examples of the present invention, the porous activated carbon can be obtained by purchasing commercial products or by making it yourself.

[0063] As a preferred example of the present invention, the preparation process of the porous activated carbon is as follows:

[0064] (1) Wash the biomass material, such as shells, wood, straw, etc., place it in a reactor, add water, and heat it at 150-250°C for 3-5 hours, wherein the amount of water added is 5-10 times that of the biomass material;

[0065] (2) placing the biomass material treated in step (1) at -30 to -10°C to completely freeze and solidify it;

[0066] (3) placing the biomass material treated in step (2) in a carbonization furnace, heating it to 300-700° C. under an inert atmosphere, and taking it out after keeping it warm for 3-6 hours;

[0067] (4) Grind and sieve the obtained biomass carbon to obtain biomass carbon powder.

[0068] Furthermore, after the porous activated carbon-based composite additive is prepared, the porous activated carbon-based composite additive may be post-processed. Specifically, the post-processing process includes:

[0069] First, in a fluidized bed, the compressed air valve at the bottom of the fluidized bed is started to disperse and suspend the porous activated carbon-based composite additive particles in the fluidized bed, and then an ethanol atomized liquid is sprayed onto the surface of the porous activated carbon-based composite additive, and then the reactor is sealed, and after reacting at 80 to 100° C. for 10 to 20 minutes, an atomized liquid of a silane coupling agent is sprayed onto the surface of the porous activated carbon-based composite additive, and then the reactor is sealed again, and after reacting at 50 to 80° C. for 30 to 60 minutes, a porous activated carbon-based composite additive after modification is obtained.

[0070] Preferably, the added amount of the ethanol atomized liquid is 10-30% of the weight of the porous activated carbon-based composite additive particles.

[0071] Preferably, the silane coupling agent atomized liquid is an alcohol solution of the silane coupling agent, and the content of the silane coupling agent in the silane coupling agent is 5 to 30 wt %.

[0072] Preferably, the added amount of the silane coupling agent is 5% to 10% of the weight of the porous activated carbon-based composite additive particles.

[0073] As some examples of the present invention, the silane coupling agent is selected from one or more of A-171, A-172, KH-560, KH-550, KH-580, and KH-602.

[0074] Furthermore, the preparation method of the special spinning oil for ultrafine denier fibers is as follows:

[0075] First, a smoothing agent is prepared according to a weight ratio, and the smoothing agent and the porous activated carbon-based composite additive are placed in an oven at 60 to 90° C. and dried for 5 to 10 hours;

[0076] Then, the formulated amount of smoothing agent and porous activated carbon-based composite additive are added to the reactor, and the temperature of the reactor is maintained at 30-50°C under vacuum. After stirring for 20-30 minutes, the formulated amount of emulsifier, antistatic agent and sizing agent are slowly added. Then, the temperature of the reactor is maintained at 30-50°C under vacuum, and after stirring for 30-90 minutes, a special spinning oil for ultrafine denier fibers is obtained.

[0077] The working principle of the special spinning oil for ultrafine denier fibers and the preparation method thereof according to the present invention is described in detail below:

[0078] In the spinning oil for ultrafine denier fibers described in the present invention, the added porous activated carbon-based composite additive contains a catalyst and an alkoxysilane. After the oil is emulsified by adding water, the catalyst and alkoxysilane filled and adsorbed in the porous activated carbon are gradually released. The alkoxysilane released into the water phase can be hydrolyzed quickly. Taking tetramethoxysilane as an example, the reaction process is described as follows:

[0079] When tetramethoxysilane encounters water, it will undergo a hydrolysis reaction. The hydrolysis reaction is a step-by-step substitution process, where the methoxy group (-OCH3) in tetramethoxysilane is replaced by a hydroxyl group (-OH) to generate silanol (Si(OH)4) and methanol (CH3OH). The reaction process is as follows:

[0080] Si(OCH3)4+4H2O→Si(OH)4+4CH3OH;

[0081] Afterwards, under the action of a catalyst, the silanol generated by hydrolysis undergoes a condensation reaction with the hydroxy silicone oil in the smoothing agent to generate a cross-linked polymer of the hydroxy silicone oil, and the process is as follows:

[0082] Si(OH)4+HO-PDMS-OH→Si-O-PDMS-O-Si;

[0083] During the cross-linking process, the molecular structure of hydroxy silicone oil will be reorganized to form a complex network structure. On the one hand, this network structure can make the oil agent adhere to the fiber surface better, thereby improving the adhesion of the oil agent to the fiber surface; on the other hand, it will cause a slight change in the surface morphology of the material and increase the roughness of the fiber surface. The increase in surface roughness provides more contact points between the fiber and the oil agent, thereby enhancing the mechanical locking effect between the fiber and the oil agent, and ultimately improving the adhesion of the oil agent to the fiber surface. At the same time, the complex network structure gives the cross-linked hydroxy silicone oil a certain elasticity, allowing it to better adapt to the slight fluctuations and deformations of the fiber surface. This elasticity helps to reduce the friction and resistance of the fiber during movement and improve lubrication performance.

[0084] Furthermore, during use, the hydroxyl groups in the hydroxyl silicone oil molecules can also chemically bond with the hydroxyl groups or other active groups on the fiber surface to form a strong connection. This chemical bonding further enhances the adhesion of the oil to the fiber surface.

[0085] In addition, hydroxy silicone oil itself has the characteristic of low surface tension, which enables it to form a uniform film on the fiber surface, reducing friction and wear between fibers. The cross-linked hydroxy silicone oil can still maintain this characteristic, and may even further reduce the surface tension due to the formation of a network structure, ensuring the ability of the oil to spread into a film on the fiber surface and its lubricating properties.

[0086] In this way, the adhesion ability of the oil agent of the present invention on the fiber surface is improved, thereby improving the film-forming ability of the oil agent, and ultimately promoting the improvement of the strength of the oil film formed on the fiber surface, reducing the number of filaments and broken ends.

[0087] However, the hydrolysis reaction of alkoxysilane proceeds relatively quickly. At the same time, the increase in temperature during shearing, emulsification and oiling can further promote the hydrolysis of alkoxysilane, which may eventually lead to the cross-linking reaction being difficult to control. In order to prevent the poor oiling of the oil agent due to the rapid hydrolysis of alkoxysilane and the rapid cross-linking with hydroxy silicone oil, in the oil agent of the present invention, it is better to control the hydrolysis of alkoxysilane and the condensation cross-linking reaction of hydroxy silicone oil after oiling. In this way, the viscosity of the oil agent before oiling can be reduced, and the ability of the oil agent to quickly spread on the fiber surface during oiling can be improved. After oiling, the adhesion of the oil film on the fiber surface is improved through the hydrolysis of alkoxysilane and the condensation cross-linking of hydroxy silicone oil. In addition, alkoxysilane can also be hydrolyzed with the help of water vapor in the air, which increases the difficulty of packaging and storage of the oil agent of the present invention. Therefore, the present invention coats the surface of the porous activated carbon particles carrying the catalyst and alkoxysilane with a polymer compound capsule wall that is insoluble in the oil phase. In this way, before the oil agent is emulsified by adding water, the catalyst and alkoxysilane will be coated by the polymer compound capsule wall and isolated in the porous activated carbon base.

[0088] Before use, when the oil is emulsified by adding water, since the polymer compound capsule wall contains a large number of hydrophilic groups such as amino, hydroxyl, carboxyl, etc., the porous activated carbon-based composite additive particles can migrate to the water phase and disperse in the water phase during emulsification.

[0089] On this basis, the present invention also uses ethanol atomization liquid and silane coupling agent to modify the surface of the porous activated carbon-based composite additive, which can introduce polar and non-polar groups on the surface of the porous activated carbon-based composite additive, so that the porous activated carbon-based composite additive particles can not only be stably dispersed in the oil phase, but also can migrate well to the water phase during emulsification.

[0090] When in use, under the action of high temperature and high-speed friction after oiling, the polymer compound capsule wall on the surface of the porous activated carbon-based composite additive breaks or dissolves in the water phase, gradually releasing the catalyst and alkoxysilane therein, and improving the adhesion of the oil agent to the fiber surface through rapid hydrolysis and condensation cross-linking processes.

[0091] In addition, in the spinning oil, in order to maintain the stability of the oil, the integrity of the oil film, ensure the good lubrication ability of the oil, and the smooth progress of the subsequent processing steps, volatile substances are generally avoided when preparing the oil. However, in the present invention, a very small amount of ultra-low viscosity dimethyl silicone oil is added to the oil, which has excellent volatility. When oiling, the dimethyl silicone oil can volatilize quickly to give the oil film a unique tension, while increasing the strength of the oil film, improving the fiber bundling ability, smoothing the unevenness of the fiber surface, reducing the friction between the fiber and the roller, and further reducing the generation of fuzz and broken ends.

[0092] The following is an example of the special spinning oil for ultrafine denier fibers and the preparation method thereof according to the present invention:

[0093] Example 1

[0094] Preparation of porous activated carbon-based composite additives:

[0095] 1 part by weight of the catalyst After TE and 5 parts by weight of methyltrimethoxysilane are evenly mixed, the obtained mixed solution of catalyst and alkoxysilane is sprayed onto 30 parts by weight of porous activated carbon, and after standing for 1 hour to allow it to fully infiltrate the porous activated carbon, porous carbon particles adsorbing the catalyst and alkoxysilane are obtained, namely, porous activated carbon-based composite additives.

[0096] Example 2

[0097] Preparation of porous activated carbon-based composite additives:

[0098] After 2 parts by weight of tetraisopropyl titanate catalyst and 8 parts by weight of tetramethoxysilane are uniformly mixed, the obtained mixed solution of the catalyst and alkoxysilane is sprayed onto 60 parts by weight of porous activated carbon, and the mixture is allowed to stand for 3 hours to fully infiltrate the porous activated carbon, thereby obtaining porous carbon particles adsorbing the catalyst and alkoxysilane;

[0099] Then, chitosan and gelatin are respectively added with water to prepare an aqueous solution with a concentration of 3 wt %, and a cross-linking agent 3-methoxy-4-hydroxybenzaldehyde is added with an ethanol solvent to prepare a cross-linking agent solution with a concentration of 1 wt %;

[0100] Then, the porous carbon particles are placed in a fluidized bed, and the compressed air valve at the bottom of the fluidized bed is started to disperse and suspend the porous carbon particles in the fluidized bed. Then, the chitosan aqueous solution, the gelatin aqueous solution and the cross-linking agent solution are sprayed into the fluidized bed through different atomizing nozzles. Under the high temperature in the fluidized bed, chitosan and gelatin are cross-linked to form a polymer compound capsule wall coated on the surface of the porous carbon particles. The temperature in the fluidized bed is 60° C., and the atomizing spraying time is 30 min.

[0101] The mass ratio of the chitosan, gelatin and porous carbon particles adsorbed with the catalyst and alkoxysilane is 0.7:0.5:7.

[0102] Example 3

[0103] Preparation of porous activated carbon-based composite additives:

[0104] On the basis of the porous activated carbon-based composite additive prepared in Example 2, the porous activated carbon-based composite additive prepared in Example 2 was post-treated:

[0105] First, in a fluidized bed, the compressed air valve at the bottom of the fluidized bed is started to disperse and suspend the porous activated carbon-based composite additive particles in the fluidized bed, and then the ethanol atomized liquid is sprayed onto the surface of the porous activated carbon-based composite additive, and then the reactor is sealed, and after reacting at 90°C for 15 minutes, the silane coupling agent atomized liquid is sprayed onto the surface of the porous activated carbon-based composite additive, and then the reactor is sealed again, and after reacting at 60°C for 30 minutes, the modified porous activated carbon-based composite additive is obtained; wherein the amount of the ethanol atomized liquid added is 15% of the weight of the porous activated carbon-based composite additive particles, and the amount of the silane coupling agent added is 7% of the weight of the porous activated carbon-based composite additive particles. .

[0106] Example 4

[0107] Preparation of special spinning oil for ultra-fine fiber:

[0108] First, a smoothing agent is prepared according to a weight ratio, and the smoothing agent and the porous activated carbon-based composite additive are placed in an oven at 60° C. and dried for 10 hours; wherein the smoothing agent includes mineral oil, polyether, dimethyl silicone oil and hydroxy silicone oil in a mass ratio of 4:3:0.5:1, and the kinematic viscosity of the mineral oil is 30 mm at 25° C. 2 / s; the kinematic viscosity of the polyether is 100 mm 2 / s, the kinematic viscosity of the dimethyl silicone oil is 0.5 mm 2 / s; the hydroxy silicone oil comprises a high-viscosity hydroxy silicone oil and a low-viscosity hydroxy silicone oil in a mass ratio of 0.5:5, and the viscosity of the high-viscosity hydroxy silicone oil is 1000mm 2 / s, the viscosity of the low viscosity hydroxy silicone oil is 100mm 2 / s; the porous activated carbon-based composite additive is the porous activated carbon-based composite additive prepared in Example 1 above;

[0109] Then, the formulated amount of smoothing agent and porous activated carbon-based composite additive are added to the reactor, and the temperature of the reactor is maintained at 30°C under vacuum. After stirring for 30 minutes, the formulated amount of emulsifier, antistatic agent and sizing agent are slowly added, and then the temperature of the reactor is maintained at 30°C under vacuum. After stirring for 90 minutes, a special spinning oil for ultrafine denier fibers is obtained; wherein the emulsifier is a mixture of fatty alcohol polyoxyethylene ether and fatty acid polyethylene glycol ester, the antistatic agent is an alkyl phosphate ester salt, and the sizing agent is a mixture of fatty acid triethanolamine salt and polyethylene glycol oleate.

[0110] Example 5

[0111] Preparation of special spinning oil for ultra-fine fiber:

[0112] First, a smoothing agent is prepared according to a weight ratio, and the smoothing agent and the porous activated carbon-based composite additive are placed in an oven at 70°C and dried for 8 hours; wherein the smoothing agent includes mineral oil, polyether, dimethyl silicone oil and hydroxy silicone oil in a mass ratio of 5:4:0.8:2, and the kinematic viscosity of the mineral oil at 25°C is 50 mm 2 / s; the kinematic viscosity of the polyether is 200mm 2 / s, the kinematic viscosity of the dimethyl silicone oil is 3mm 2 / s; the hydroxy silicone oil comprises a high-viscosity hydroxy silicone oil and a low-viscosity hydroxy silicone oil in a mass ratio of 1:6, and the viscosity of the high-viscosity hydroxy silicone oil is 10000mm 2 / s, the viscosity of the low viscosity hydroxy silicone oil is 300mm 2 / s; the porous activated carbon-based composite additive is the porous activated carbon-based composite additive prepared in Example 2 above;

[0113] Then, the formulated amount of smoothing agent and porous activated carbon-based composite additive are added to the reactor, and the temperature of the reactor is maintained at 40°C under vacuum. After stirring for 20 minutes, the formulated amount of emulsifier, antistatic agent and sizing agent are slowly added, and then the temperature of the reactor is maintained at 40°C under vacuum. After stirring for 70 minutes, a special spinning oil for ultrafine denier fibers is obtained; wherein the emulsifier is a mixture of stearic acid ester and oleic acid polyoxyethylene ester, the antistatic agent is a mixture of alkyl sulfonate salt and lauryl alcohol polyoxyethylene ether, and the sizing agent is castor oil polyoxyethylene ether.

[0114] Example 6

[0115] Preparation of special spinning oil for ultra-fine fiber:

[0116] First, a smoothing agent is prepared according to a weight ratio, and the smoothing agent and the porous activated carbon-based composite additive are placed in an oven at 90° C. and dried for 5 hours; wherein the smoothing agent includes mineral oil, polyether, dimethyl silicone oil and hydroxy silicone oil in a mass ratio of 7:5:1:3, and at 25° C., the kinematic viscosity of the mineral oil is 60 mm 2 / s; the kinematic viscosity of the polyether is 300mm 2 / s, the kinematic viscosity of the dimethyl silicone oil is 5mm 2 / s; the hydroxy silicone oil comprises a high-viscosity hydroxy silicone oil and a low-viscosity hydroxy silicone oil in a mass ratio of 2:8, and the viscosity of the high-viscosity hydroxy silicone oil is 30000mm 2 / s, the viscosity of the low viscosity hydroxy silicone oil is 500mm 2 / s; the porous activated carbon-based composite additive is the porous activated carbon-based composite additive prepared in Example 3 above;

[0117] Then, the formulated amount of smoothing agent and porous activated carbon-based composite additive are added to the reactor, and the temperature of the reactor is maintained at 50°C under vacuum. After stirring for 25 minutes, the formulated amount of emulsifier, antistatic agent and sizing agent are slowly added, and then the temperature of the reactor is maintained at 50°C under vacuum. After stirring for 30 minutes, a special spinning oil for ultrafine denier fibers is obtained; wherein the emulsifier is a mixture of fatty acid polyethylene glycol esters and stearic acid esters, the antistatic agent is isomeric tridecyl alcohol ether phosphate, and the sizing agent is a mixture of lauryl polyoxyethylene ether and polyoxyethylene polyoxypropylene ether.

[0118] Example 7

[0119] Preparation of special spinning oil for ultra-fine fiber:

[0120] The only difference between it and the above-mentioned Example 6 is that the raw materials for preparing the oil further include 3 parts by weight of nano-silicon dioxide. When preparing the oil, the nano-silicon dioxide is added to the oil together with the emulsifier, the antistatic agent and the sizing agent.

[0121] In the above-mentioned Examples 4 to 7, the raw material ratios of the special spinning oil for ultrafine denier fibers are shown in Table 1 below:

[0122] Table 1 Raw material ratio of ultra-fine fiber special spinning oil

[0123] Smoothing agent Emulsifier Antistatic Agents Clustering Agents Porous activated carbon-based composite additives Example 4 60 10 5 5 3 Example 5 70 15 8 10 4 Example 6 80 20 10 15 5 Example 7 80 20 10 15 5

[0124] Comparative Example 1

[0125] Preparation of special spinning oil for ultra-fine fiber:

[0126] The only difference between it and the above-mentioned Example 5 is that the porous activated carbon-based composite additive prepared in the above-mentioned Example 2 is not added therein.

[0127] Comparative Example 2

[0128] Preparation of special spinning oil for ultra-fine fiber:

[0129] The only difference between the embodiment 5 and the above-mentioned embodiment 5 is that the lubricant used in the embodiment 5 does not include dimethyl silicone oil.

[0130] Comparative Example 3

[0131] Preparation of special spinning oil for ultra-fine fiber:

[0132] The only difference between it and the above-mentioned embodiment 5 is that the lubricant used therein does not include hydroxy silicone oil.

[0133] Comparative Example 4

[0134] Preparation of special spinning oil for ultra-fine fiber:

[0135] The difference between this embodiment and the above-mentioned embodiment 5 is that the dimethyl silicone oil in the lubricant used has a kinematic viscosity of 100 mm at 25°C. 2 / s.

[0136] Comparative Example 5

[0137] Preparation of special spinning oil for ultra-fine fiber:

[0138] The only difference between it and the above-mentioned Example 5 is that the preparation process of the porous activated carbon-based composite additive used therein is as follows: after 2 parts by weight of the catalyst tetraisopropyl titanate and 8 parts by weight of tetramethoxysilane are evenly mixed, the obtained mixed solution of the catalyst and alkoxysilane is sprayed onto 60 parts by weight of porous activated carbon, and after standing for 3 hours to fully infiltrate the porous activated carbon, porous carbon particles adsorbed with the catalyst and alkoxysilane are obtained, and the porous carbon particles adsorbed with the catalyst and alkoxysilane are used as porous activated carbon-based composite additives.

[0139] Performance Testing

[0140] The above Examples 4 to 7, the commercially available F1048 oil produced by Takemoto Co., Ltd. of Japan, and the special spinning oil for ultrafine denier fibers prepared in Comparative Examples 1 to 5 were subjected to physical and chemical property tests according to conventional detection methods in the art, and the pH, kinematic viscosity, effective content, room temperature stability (25°C, 7d), high temperature stability (80°C, 8h), surface tension and oil film strength of the 10% emulsion were measured. The results are shown in Table 2 below.

[0141] Table 2 Test results of the physicochemical properties of the oil

[0142]

[0143] Spinning performance test:

[0144] The above-mentioned Examples 4 to 7, the commercially available F1048 oil produced by Takemoto Co., Ltd. of Japan, and the special spinning oil for ultrafine denier fibers prepared in Comparative Examples 1 to 5 were used for spinning tests under the same conditions by direct spinning method, and the spinning process parameters were as follows: yarn material: polyester, oil concentration 10%, nozzle spraying oil, stretching heating temperature 115°C, stretching speed 2000m / min, stretching temperature 255°C, total drawing multiple 6.35, spinning temperature 305°C, spinning speed 530m / min, relaxation rate 6.5, heat setting temperature 260°C; the yarn fineness obtained after spinning was 0.83dtex, and the spinning performance was shown in Table 3 below:

[0145] Table 3 Spinning performance test results

[0146] sample Pass rate (%) Oiling rate (%) Number of wire breakages / day·spindle Example 4 85.3 0.76 16.6 Example 5 89.4 0.83 10.4 Example 6 91.2 0.86 10.5 Example 7 91.5 0.88 9.8 Comparative Example 1 72.3 0.71 23.5 Comparative Example 2 87.7 0.81 15.1 Comparative Example 3 79.5 0.72 21.8 Comparative Example 4 88.5 0.82 13.7 Comparative Example 5 86.1 0.81 12.3 F1048 86.8 0.85 18.5

[0147] The technical solution of the present application is described above in conjunction with specific embodiments. In the absence of conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present application is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Under the guidance of the present application, ordinary technicians in this field can also make many forms without departing from the purpose of the present application and the scope of protection of the claims, all of which are within the protection of the present application.

Claims

1. A method for preparing a spinning oil for ultra-fine denier fibers, characterized in that: The invention comprises the following raw materials in parts by weight: 60 to 80 parts of a smoothing agent, 10 to 20 parts of an emulsifier, 5 to 10 parts of an antistatic agent, 5 to 15 parts of a sizing agent, and 3 to 5 parts of a porous activated carbon-based composite additive, wherein the porous activated carbon-based composite additive comprises porous activated carbon and an auxiliary agent filled in the porous activated carbon, wherein the auxiliary agent comprises a catalyst and an alkoxysilane.

2. The method for preparing a special spinning oil for ultrafine fibers according to claim 1, characterized in that: The lubricant is a mixture of mineral oil, polyether, dimethyl silicone oil and hydroxy silicone oil, and the mass ratio of the mineral oil, polyether, dimethyl silicone oil and hydroxy silicone oil in the lubricant is (4-7): (3-5): (0.5-1): (1-3).

3. The method for preparing a special spinning oil for ultrafine fibers according to claim 2, characterized in that: At 25°C, the kinematic viscosity of the mineral oil is 20 to 60 mm 2 / s; the kinematic viscosity of the polyether is 50 to 300 mm 2 / s, the kinematic viscosity of the dimethyl silicone oil is 0.5-5mm 2 / s, the hydroxy silicone oil comprises a high-viscosity hydroxy silicone oil and a low-viscosity hydroxy silicone oil in a mass ratio of (0.5-2): (5-8), and the viscosity of the high-viscosity hydroxy silicone oil is 1000-30000mm 2 / s, the viscosity of the low-viscosity hydroxy silicone oil is 100-500 mm 2 / s.

4. The method for preparing a special spinning oil for ultrafine fibers according to claim 1, characterized in that: The mass ratio of the catalyst to the alkoxysilane is (1-3):(5-10).

5. The method for preparing a special spinning oil for ultrafine fibers according to claim 4, characterized in that: The mass ratio of the porous activated carbon to the auxiliary agent filled in the porous activated carbon is (5-10): (1-2).

6. The method for preparing a special spinning oil for ultrafine fibers according to claim 4 or 5, characterized in that: The alkoxysilane is selected from one or more of methyltrimethoxysilane, tetramethoxysilane and tetraethoxysilane.

7. The method for preparing a special spinning oil for ultrafine fibers according to claim 4, characterized in that: The preparation process of the porous activated carbon-based composite additive is as follows: First, the catalyst and alkoxysilane are mixed evenly, and then the mixed solution of the catalyst and alkoxysilane is sprayed onto the porous activated carbon. After standing for 1 to 3 hours to allow the porous activated carbon to be fully infiltrated, porous carbon particles adsorbed with the catalyst and alkoxysilane are obtained, which are the porous activated carbon-based composite additive.

8. The method for preparing a special spinning oil for ultrafine fibers according to claim 7, characterized in that: The outer side of the porous activated carbon-based composite additive is coated with a polymer compound capsule wall that is insoluble in the oil phase. The preparation process of the porous activated carbon-based composite additive is as follows: First, the catalyst and alkoxysilane are mixed evenly, and then the mixed solution of the catalyst and alkoxysilane is sprayed onto the porous activated carbon, and allowed to stand for 1 to 3 hours to fully infiltrate the porous activated carbon, thereby obtaining porous carbon particles adsorbing the catalyst and alkoxysilane; Chitosan and gelatin are respectively added with water to prepare an aqueous solution with a concentration of 1 to 5 wt %, and a cross-linking agent is added with a solvent to prepare a cross-linking agent solution with a concentration of 1 to 3 wt %; The porous carbon particles are then placed in a fluidized bed, and the compressed air valve at the bottom of the fluidized bed is started to disperse and suspend the porous carbon particles in the fluidized bed. Thereafter, an aqueous solution of chitosan, an aqueous solution of gelatin, and a cross-linking agent solution are sprayed into the fluidized bed through different atomizing nozzles. Under the high temperature in the fluidized bed, chitosan and gelatin are cross-linked to form a polymer compound capsule wall coating the surface of the porous carbon particles.

9. The method for preparing a special spinning oil for ultrafine fibers according to claim 8, characterized in that: After the porous activated carbon-based composite additive is prepared, the porous activated carbon-based composite additive may be post-processed, and the post-processing process includes: First, in a fluidized bed, the compressed air valve at the bottom of the fluidized bed is started to disperse and suspend the porous activated carbon-based composite additive particles in the fluidized bed, and then an ethanol atomized liquid is sprayed onto the surface of the porous activated carbon-based composite additive, and then the reactor is sealed, and after reacting at 80 to 100° C. for 10 to 20 minutes, an atomized liquid of a silane coupling agent is sprayed onto the surface of the porous activated carbon-based composite additive, and then the reactor is sealed again, and after reacting at 50 to 80° C. for 30 to 60 minutes, a porous activated carbon-based composite additive after modification is obtained.

10. The method for preparing a special spinning oil for ultra-fine fibers according to claim 1, characterized in that: The preparation method of the special spinning oil for ultrafine denier fiber is as follows: First, a smoothing agent is prepared according to a weight ratio, and the smoothing agent and the porous activated carbon-based composite additive are placed in an oven at 60 to 90° C. and dried for 5 to 10 hours; Then, the formulated amount of smoothing agent and porous activated carbon-based composite additive are added to the reactor, and the temperature of the reactor is maintained at 30-50°C under vacuum. After stirring for 20-30 minutes, the formulated amount of emulsifier, antistatic agent and sizing agent are slowly added. Then, the temperature of the reactor is maintained at 30-50°C under vacuum, and after stirring for 30-90 minutes, a special spinning oil for ultrafine denier fibers is obtained.

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