Anti-sticking agent for aramid fiber and preparation method of anti-sticking agent

Abstract

The invention relates to the technical field of fiber anti-sticking agents, in particular to an anti-sticking agent for aramid fibers and a preparation method of the anti-sticking agent for the aramid fibers, and the anti-sticking agent is prepared from 0.75 to 3 parts of fatty acid modified inorganic anti-sticking filler, 0.075 to 0.45 part of anionic surfactant, 0.075 to 0.45 part of nonionic surfactant and 96.1 to 99.1 parts of deionized water. The preparation method of the fatty acid modified inorganic anti-sticking filler comprises the following steps: adding a silane coupling agent into a mixed solvent of ethanol and water, fully hydrolyzing, adding an inorganic anti-sticking filler uniformly dispersed in n-butyl alcohol, and reacting to obtain a silane coupling agent grafted inorganic anti-sticking filler; and adding the silane coupling agent grafted inorganic anti-sticking filler, N, N-dicyclohexylcarbodiimide and fatty acid into dichloromethane, uniformly dispersing and reacting to obtain the fatty acid modified inorganic anti-sticking filler. The anti-sticking agent has better stability, and is beneficial to uniform adhesion on the surface of the aramid fiber.

Description

TECHNICAL FIELD

[0001] The present application relates to an anti-adhesion agent for aramid fibers and a preparation method thereof, and belongs to the technical field of fiber anti-adhesion agents. BACKGROUND

[0002] Aramid fibers can be mainly divided into para-aramid fibers and meta-aramid fibers, and the full name is "polyphenylene terephthalamide", which is Aramid fiber in English. It is a new type of high-tech synthetic fiber with excellent properties such as ultra-high strength, high modulus, high temperature resistance, acid and alkali resistance, light weight, etc. Its strength is 5-6 times that of steel wire, modulus is 2-3 times that of steel wire or glass fiber, and toughness is 2 times that of steel wire, and weight is only about 1 / 5 of steel wire. It does not decompose and melt at a temperature of 560℃. It has good insulation and anti-aging properties, and has a long service life. The discovery of aramid fiber is considered to be a very important historical process in the material field.

[0003] However, in order to obtain aramid fibers with high strength and high modulus and modified aramid fibers with more excellent performance, stretching needs to be carried out at high temperature, which causes the phenomenon of sticking and silk in the process of stretching of aramid fibers, which brings problems to the normal fiber production process and greatly affects the mechanical properties of the finished fiber, resulting in significant reduction of fiber strength, elongation and model indicators.

[0004] The fiber anti-adhesion agent is applied to the surface of the fiber, which can prevent the mutual adhesion between the fibers in the process of primary fiber preparation and subsequent hot drawing, and has an important influence on the processing of high-performance aramid fibers and the mechanical properties of finished fibers. Patent No. JP4782944B2 discloses an anti-adhesion agent prepared by dispersing talc, calcium carbonate, mica and other inorganic powders; patent application No. CN114232381A discloses an anti-adhesion agent for impregnation process prepared by mixing prepared silicone resin grafted talc, cactus ethanol solution, beeswax, emulsifier and pH adjuster; patent application No. US4525384A discloses an anti-adhesion agent for fibers by applying an aqueous dispersion containing inert inorganic materials (graphite, talc, silica, hydrophobic silica) on the surface of the fibers. The above dispersion has poor stability, and it is difficult to maintain the stability of the dispersion system during production, which causes uneven coating of the anti-adhesion agent on the surface of the fibers and affects the normal spinning of aramid fibers. SUMMARY

[0005] The present application provides an anti-adhesion agent for aramid fibers and a preparation method thereof, which has better stability, is beneficial to uniform adhesion on the surface of aramid fibers, and ensures smooth spinning of aramid fibers.

[0006] The technical scheme for solving the above technical problem is as follows: An anti-sticking agent for aramid fiber, according to weight parts, the anti-sticking agent comprises: 0.75-3 parts of fatty acid modified inorganic anti-sticking filler, 0.075-0.45 parts of anionic surfactant, 0.075-0.45 parts of non-ionic surfactant, 96.1-99.1 parts of deionized water. The inorganic anti-sticking filler is at least one of silica and talcum powder.

[0007] Based on the above technical scheme, the application can be further improved as follows: Further, the preparation method of the fatty acid modified inorganic anti-sticking filler is as follows: The silane coupling agent is added to a mixed solvent of ethanol and water for sufficient hydrolysis, then the inorganic anti-sticking filler uniformly dispersed in n-butanol is added, the temperature is controlled for reaction, and then the silane coupling agent grafted inorganic anti-sticking filler is obtained through solid-liquid separation; The silane coupling agent grafted inorganic anti-sticking filler, N,N-dicyclohexyl carbodiimide and fatty acid are added to dichloromethane for uniform dispersion and reaction, and finally the fatty acid modified inorganic anti-sticking filler is obtained through solid-liquid separation and drying.

[0008] Further, the mass ratio of the silane coupling agent, ethanol and water is 1:(9-10):(1-2); The mass ratio of the silane coupling agent and the inorganic anti-sticking filler is (5-10):(2-5); The mass ratio of the inorganic anti-sticking filler and n-butanol is (2-5):(50-80); The mass ratio of the silane coupling agent grafted inorganic anti-sticking filler, N,N-dicyclohexyl carbodiimide and fatty acid is 1:(1.0-1.2):(0.6-0.8).

[0009] Further, the fatty acid is C 14 -C 18 At least one of the fatty acids.

[0010] Further, the inorganic anti-sticking filler is added to n-butanol for uniform dispersion by ultrasonic treatment, the ultrasonic treatment time is 5-15 min, the ultrasonic power is 120-160 W, and the ultrasonic frequency is 30-60 kHz; The silane coupling agent grafted inorganic anti-sticking filler, N,N-dicyclohexyl carbodiimide and fatty acid are added to dichloromethane for ultrasonic treatment for 5-15 min, the ultrasonic power is 120-160 W, the ultrasonic frequency is 30-60 kHz, and then the reaction is completed by stirring at a speed of 100-200 r / min at room temperature for 24-48 h.

[0011] Further, the reaction temperature for preparing the silane coupling agent grafted inorganic anti-adhesion filler is 80-90 DEG C, and the reaction time is 6-8h.

[0012] Further, the mass ratio of the fatty acid modified inorganic anti-adhesion filler to the anionic surfactant is (5-10):1.

[0013] Further, the anionic surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, and sodium di-sec-octyl sulfosuccinate.

[0014] Further, the non-ionic surfactant is at least one of fatty alcohol polyoxyethylene ether, BYK-190, Tween 80, nonylphenol polyoxyethylene ether, and fatty acid methyl ester ethoxylate.

[0015] The application further discloses a preparation method of the anti-adhesion agent for aramid fibers. The fatty acid modified inorganic anti-adhesion filler, the anionic surfactant, the non-ionic surfactant, and deionized water with a mass fraction of 54%-75% of the formula components are uniformly mixed, and a dispersion liquid is obtained after grinding treatment.

[0016] The application has the following beneficial effects: The anti-adhesion agent for aramid fibers has better stability, the fatty acid modified inorganic anti-adhesion filler can effectively increase the spacing between the inorganic anti-adhesion filler particles in the anti-adhesion agent, the anionic surfactant can form a double electric layer structure on the surface of the nano particles, and the non-ionic surfactant can increase the steric hindrance between the particles, which is not conducive to the agglomeration and sedimentation between the particles.

[0017] The anti-adhesion agent can be uniformly attached to the surface of the aramid fibers, the modified silicon dioxide particles can effectively cover the surface of the fibers to play a role in spacing the fibers, the phenomenon of sticking and clustering of the aramid fibers during the spinning process is avoided, and the smooth spinning of the aramid fibers is ensured. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 A microscopic image of the coating of the anti-adhesion agent of Example 5 on the surface of the fibers (application example 5); Figure 2 A microscopic image of the coating of the anti-adhesion agent of Example 6 on the surface of the fibers (application example 9); Figure 3Micrograph of the fiber surface coating case (application example 13) of the anti-sticking agent of example 7; Figure 4 Micrograph of the fiber surface coating case (application example 17) of the anti-sticking agent of example 8. DETAILED DESCRIPTION

[0019] The present application can be implemented in many different ways than described herein, and those skilled in the art can make similar improvements without departing from the spirit of the present application, so the present application is not limited by the disclosed specific embodiments.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terms used are only for the description of specific embodiments and are not intended to limit the present application.

[0021] An anti-sticking agent for aramid fiber, the anti-sticking agent comprises, in parts by weight: 0.75-3 parts of fatty acid modified inorganic anti-sticking filler, 0.075-0.45 parts of anionic surfactant, 0.075-0.45 parts of non-ionic surfactant, 96.1-99.1 parts of deionized water; The inorganic anti-sticking filler is at least one of silica and talc powder.

[0022] Specifically, the preparation method of the fatty acid modified inorganic anti-sticking filler is: The silane coupling agent is added to a mixed solvent of ethanol and water, and stirred at a speed of 200 r / min for 15-30 min to make the silane coupling agent fully hydrolyzed; the inorganic anti-sticking filler is added to n-butanol for ultrasonic treatment and dispersion; after mixing the above two solutions, the temperature is controlled for reaction, and after the reaction is completed, centrifugation is performed at a speed of 8000-12000 r / min for 10-15 min, and the precipitate is washed and dried to obtain the inorganic anti-sticking filler grafted with the silane coupling agent; The inorganic anti-sticking filler grafted with the silane coupling agent, N,N-dicyclohexyl carbodiimide (DCC), and fatty acid are added to dichloromethane for dispersion and reaction, and finally solid-liquid separation and drying are performed to obtain the fatty acid modified inorganic anti-sticking filler.

[0023] Specifically, the mass ratio of the silane coupling agent, ethanol and water is 1: (9-10): (1-2); The mass ratio of the silane coupling agent and the inorganic anti-sticking filler is (5-10): (2-5); The mass ratio of the inorganic anti-sticking filler and n-butanol is (2-5): (50-80); The mass ratio of the silane coupling agent grafted inorganic anti-adhesion filler, N,N-dicyclohexyl carbodiimide and fatty acid is 1:(1.0-1.2):(0.6-0.8). The mass ratio of the silane coupling agent grafted inorganic anti-adhesion filler and dichloromethane is (2-5):(100-150).

[0024] More specifically, the silane coupling agent used in the embodiment of the present application is KH550.

[0025] The silicon dioxide used in the embodiment of the present application is purchased from Shanghai Maikelin Biochemical Technology Co., Ltd., and the CAS number is 60676-86-0; the talc powder used in the embodiment of the present application is purchased from Shanghai Maikelin Biochemical Technology Co., Ltd., and the CAS number is 14807-96-6.

[0026] Specifically, the fatty acid is C 14 -C 18 at least one of fatty acids.

[0027] More specifically, the fatty acid is at least one of tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid.

[0028] Specifically, the inorganic anti-adhesion filler is added into n-butanol and uniformly dispersed by ultrasonic treatment, the ultrasonic treatment time is 5-15 min, the ultrasonic power is 120-160 W, and the ultrasonic frequency is 30-60 kHz. The silane coupling agent grafted inorganic anti-adhesion filler, N,N-dicyclohexyl carbodiimide and fatty acid are added into dichloromethane, ultrasonic treatment is performed for 5-15 min, the ultrasonic power is 120-160 W, the ultrasonic frequency is 30-60 kHz, then stirring is performed at a speed of 100-200 r / min at room temperature for 24-48 h to complete the reaction. Centrifugation is performed at a speed of 8000-12000 r / min for 10-15 min, the precipitate is taken and washed and dried to obtain the silane coupling agent grafted inorganic anti-adhesion filler.

[0029] Specifically, the reaction temperature for preparing the silane coupling agent grafted inorganic anti-adhesion filler is 80-90℃, and the reaction time is 6-8 h.

[0030] Specifically, the mass ratio of the fatty acid modified inorganic anti-adhesion filler and the anionic surfactant is (5-10):1.

[0031] Specifically, the anionic surfactant is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and sodium di-sec-octyl maleate sulfonate.

[0032] Specifically, the non-ionic surfactant is at least one of fatty alcohol polyoxyethylene ether, BYK-190, Tween 80, nonylphenol polyoxyethylene ether, and fatty acid methyl ester ethoxylate.

[0033] The application further discloses a preparation method of the anti-sticking agent for aramid fibers. The fatty acid modified inorganic anti-sticking filler, the anionic surfactant, the non-ionic surfactant and 54%-75% of deionized water of the formula component are mixed, and are uniformly stirred at a rotating speed of 100-200 r / min, and are ground by a grinder at 2000-2500 r / min for 4-6 h to obtain a long-term stable dispersion liquid; when used, the remaining deionized water required by the formula component is added into the dispersion liquid to obtain the anti-sticking agent.

[0034] More specifically, the storage temperature of the dispersion liquid is greater than or equal to 15 DEG C, so as to prevent the agglomeration of the silica or talc particles and affect the use.

[0035] I. Preparation example of the anti-sticking agent for aramid fibers Example 1 A preparation method of an anti-sticking agent for aramid fibers is as follows: (1) Preparation of the fatty acid modified inorganic anti-sticking filler: The silane coupling agent is added into a mixed solvent of ethanol and water, and is stirred at a rotating speed of 200 r / min for 30 min to make the silane coupling agent fully hydrolyzed; the inorganic anti-sticking filler, i.e., silica, is added into n-butanol and is uniformly dispersed by ultrasonic treatment; after the above two solutions are mixed, the temperature is controlled to perform a reaction, and then the silane coupling agent grafted silica is obtained through solid-liquid separation. The silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide and tetradecanoic acid (CAS: 544-63-8) are added into dichloromethane, are uniformly dispersed by ultrasonic treatment and are reacted, and finally are centrifuged, and the precipitate is washed and dried to obtain tetradecanoic acid modified silica.

[0036] The mass ratio of the silane coupling agent, ethanol and water is 1:10:1. The mass ratio of the silane coupling agent and the silica is 5:2. The mass ratio of the silica and the n-butanol is 2:50. The mass ratio of the silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide and tetradecanoic acid is 1:1:0.6. The mass ratio of the silane coupling agent grafted silica and dichloromethane is 2:100.

[0037] The silica is added into n-butanol and uniformly dispersed by ultrasonic treatment, the ultrasonic treatment time is 15 min, the ultrasonic power is 120 W, and the ultrasonic frequency is 30 kHz; The silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide and fatty acid are added into dichloromethane, ultrasonic treatment is performed for 15 min, the ultrasonic power is 120 W, the ultrasonic frequency is 30 kHz, and then the reaction is completed by stirring at a speed of 200 r / min for 24 h at room temperature.

[0038] (2) Preparation of the anti-adhesive agent: According to the weight parts, the formula of the anti-adhesive agent comprises 3 parts of tetradecanoic acid modified silica, 0.45 parts of anionic surfactant, 0.45 parts of non-ionic surfactant and 96.1 parts of deionized water.

[0039] The anionic surfactant is sodium dodecyl benzene sulfonate, and the non-ionic surfactant is fatty acid methyl ester ethoxylate.

[0040] The preparation method of the anti-adhesive agent is as follows: tetradecanoic acid modified silica, anionic surfactant, non-ionic surfactant and 75% of the formula component deionized water are mixed, uniformly stirred at a speed of 200 r / min, and ground by a grinder at a speed of 2500 r / min for 5 h to obtain a long-term stable dispersion liquid. When used, 25% of the formula component deionized water is added to the dispersion liquid to obtain the anti-adhesive agent.

[0041] Example 2 Preparation of an anti-adhesive agent for aramid fiber: (1) Preparation of fatty acid modified inorganic anti-adhesive filler: The silane coupling agent is added into a mixed solvent of ethanol and water, and stirred at a speed of 200 r / min for 30 min to hydrolyze the silane coupling agent sufficiently; the inorganic anti-adhesive filler silica is added into n-butanol and uniformly dispersed by ultrasonic treatment; after the above two solutions are mixed, the reaction is performed by controlling the temperature, and then solid-liquid separation is performed to obtain the silane coupling agent grafted silica; The silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide and pentadecanoic acid (CAS: 1002-84-2) are added into dichloromethane, uniformly dispersed by ultrasonic treatment and reacted, and finally centrifuged, washed and dried to obtain pentadecanoic acid modified silica.

[0042] The mass ratio of the silane coupling agent, ethanol and water is 1:10:1; The mass ratio of the silane coupling agent and the silica is 5:2; The mass ratio of the silica and n-butanol is 2:50; The mass ratio of the silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide and pentadecanoic acid is 1:1:0.6. The mass ratio of the silane coupling agent grafted silica and dichloromethane is 2:100.

[0043] The silica is uniformly dispersed in n-butanol by ultrasonic treatment, the ultrasonic treatment time is 15 min, the ultrasonic power is 120 W, and the ultrasonic frequency is 30 kHz. The silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide and fatty acid are added to dichloromethane, ultrasonic treatment is performed for 15 min, the ultrasonic power is 120 W, the ultrasonic frequency is 30 kHz, then stirring is performed at room temperature at a speed of 200 r / min for 24 h to complete the reaction.

[0044] (2) Preparation of the anti-adhesive agent: According to the weight fraction, the formula of the anti-adhesive agent comprises 3 parts of pentadecanoic acid modified silica, 0.45 parts of anionic surfactant, 0.45 parts of non-ionic surfactant, and 96.1 parts of deionized water.

[0045] The anionic surfactant is sodium dodecyl sulfate, and the non-ionic surfactant is fatty alcohol polyoxyethylene ether.

[0046] The preparation method of the anti-adhesive agent is as follows: pentadecanoic acid modified silica, anionic surfactant, non-ionic surfactant, and 75% of the formula component deionized water are mixed, uniformly stirred at a speed of 200 r / min, and ground by a grinder at a speed of 2500 r / min for 5 h to obtain a long-term stable dispersion liquid. When used, 25% of the formula component deionized water is added to the dispersion liquid to obtain the anti-adhesive agent.

[0047] Example 3 Preparation of an anti-adhesive agent for aramid fiber: (1) Preparation of fatty acid modified inorganic anti-adhesive filler: The silane coupling agent is added to a mixed solvent of ethanol and water, and stirred at a speed of 200 r / min for 30 min to hydrolyze the silane coupling agent sufficiently; the inorganic anti-adhesive filler silica is uniformly dispersed in n-butanol by ultrasonic treatment; after the two solutions are mixed, the temperature is controlled to react, and then solid-liquid separation is performed to obtain the silane coupling agent grafted silica; The silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide and hexadecanoic acid (CAS: 57-10-3) are added to dichloromethane, uniformly dispersed by ultrasonic treatment and reacted, and finally centrifuged, washed and dried to obtain hexadecanoic acid modified silica.

[0048] The mass ratio of the silane coupling agent, ethanol and water is 1:10:1. The mass ratio of the silane coupling agent and the silicon dioxide is 5:2. The mass ratio of the silicon dioxide and the n-butanol is 2:50. The mass ratio of the silane coupling agent grafted silicon dioxide, N,N-dicyclohexyl carbodiimide and hexadecanoic acid is 1:1:0.6. The mass ratio of the silane coupling agent grafted silicon dioxide and dichloromethane is 2:100.

[0049] The silicon dioxide is added into the n-butanol and uniformly dispersed by ultrasonic treatment, the ultrasonic treatment time is 15 min, the ultrasonic power is 120 W and the ultrasonic frequency is 30 kHz; The silane coupling agent grafted silicon dioxide, N,N-dicyclohexyl carbodiimide and fatty acid are added into the dichloromethane, ultrasonic treatment is performed for 15 min, the ultrasonic power is 120 W and the ultrasonic frequency is 30 kHz, then the reaction is completed by stirring at a speed of 200 r / min for 24 h at room temperature.

[0050] (2) Preparation of the anti-adhesive agent: According to the weight fraction, the formula of the anti-adhesive agent comprises 3 parts of hexadecanoic acid modified silicon dioxide, 0.45 parts of anionic surfactant, 0.45 parts of non-ionic surfactant and 96.1 parts of deionized water.

[0051] The anionic surfactant is sodium fatty alcohol polyoxyethylene ether sulfate and the non-ionic surfactant is BYK-190.

[0052] The preparation method of the anti-adhesive agent is as follows: the hexadecanoic acid modified silicon dioxide, the anionic surfactant, the non-ionic surfactant and 75% of the deionized water of the formula component are mixed, uniformly stirred at a speed of 200 r / min, ground by a grinder at a speed of 2500 r / min for 5 h to obtain a long-term stable dispersion liquid, and when used, 25% of the deionized water of the formula component is added into the dispersion liquid to obtain the anti-adhesive agent.

[0053] Example 4 Preparation of an anti-adhesive agent for aramid fiber: (1) Preparation of fatty acid modified inorganic anti-adhesive filler: The silane coupling agent is added into a mixed solvent of ethanol and water, stirred at a speed of 200 r / min for 30 min to hydrolyze the silane coupling agent sufficiently; the inorganic anti-adhesive filler silicon dioxide is added into n-butanol and uniformly dispersed by ultrasonic treatment; after the above two solutions are mixed, the reaction is performed by controlling the temperature, and then the silane coupling agent grafted silicon dioxide is obtained by solid-liquid separation. The silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide, heptadecanoic acid (CAS: 506-12-7) are added into dichloromethane, uniformly dispersed by ultrasonic treatment and reacted, and finally centrifuged, washed and dried to obtain heptadecanoic acid modified silica.

[0054] The mass ratio of the silane coupling agent, ethanol and water is 1:10:1. The mass ratio of the silane coupling agent and the silica is 5:2. The mass ratio of the silica and n-butanol is 2:50. The mass ratio of the silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide and heptadecanoic acid is 1:1:0.6. The mass ratio of the silane coupling agent grafted silica and dichloromethane is 2:100.

[0055] The silica is added into n-butanol and uniformly dispersed by ultrasonic treatment, the ultrasonic treatment time is 15 min, the ultrasonic power is 120 W, and the ultrasonic frequency is 30 kHz. The silane coupling agent grafted silica, N,N-dicyclohexyl carbodiimide and fatty acid are added into dichloromethane, ultrasonic treatment is performed for 15 min, the ultrasonic power is 120 W, the ultrasonic frequency is 30 kHz, and then the reaction is completed by stirring at a speed of 200 r / min for 24 h at room temperature.

[0056] (2) Preparation of the anti-adhesive agent: According to the weight fraction, the formula of the anti-adhesive agent comprises 3 parts of heptadecanoic acid modified silica, 0.45 parts of anionic surfactant, 0.45 parts of non-ionic surfactant and 96.1 parts of deionized water.

[0057] The anionic surfactant is sodium dimethylhexyl sulfonate, and the non-ionic surfactant is nonylphenol polyoxyethylene ether.

[0058] The preparation method of the anti-adhesive agent is as follows: the heptadecanoic acid modified silica, the anionic surfactant, the non-ionic surfactant and 75% of the deionized water of the formula component are mixed, uniformly stirred at a speed of 200 r / min, and ground by a grinder at a speed of 2500 r / min for 5 h to obtain a long-term stable dispersion liquid. When used, 25% of the deionized water of the formula component is added into the dispersion liquid to obtain the anti-adhesive agent.

[0059] Example 5 Preparation of an anti-adhesive agent for aramid fiber: (1) Preparation of fatty acid modified inorganic anti-adhesive filler: The silane coupling agent is added into a mixed solvent of ethanol and water, and stirred at a rotation speed of 200 r / min for 30 min to make the silane coupling agent fully hydrolyzed; the inorganic anti-adhesion filler, i.e., silica, is added into n-butanol and uniformly dispersed by ultrasonic treatment; the above two solutions are mixed, and then reacted under temperature control, and then subjected to solid-liquid separation to obtain the silica grafted with the silane coupling agent; The silica grafted with the silane coupling agent, N,N-dicyclohexyl carbodiimide, and octadecanoic acid (CAS: 57-11-4) are added into dichloromethane, uniformly dispersed by ultrasonic treatment, and then reacted, and finally subjected to centrifugation, washing of the precipitate, and drying to obtain the octadecanoic acid modified silica.

[0060] The mass ratio of the silane coupling agent, ethanol, and water is 1:10:1. The mass ratio of the silane coupling agent and the silica is 5:2. The mass ratio of the silica and n-butanol is 2:50. The mass ratio of the silica grafted with the silane coupling agent, N,N-dicyclohexyl carbodiimide, and octadecanoic acid is 1:1:0.6. The mass ratio of the silica grafted with the silane coupling agent and dichloromethane is 2:100.

[0061] The silica is added into n-butanol and uniformly dispersed by ultrasonic treatment, the ultrasonic treatment time is 15 min, the ultrasonic power is 120 W, and the ultrasonic frequency is 30 kHz. The silica grafted with the silane coupling agent, N,N-dicyclohexyl carbodiimide, and fatty acid are added into dichloromethane, ultrasonic treatment is performed for 15 min, the ultrasonic power is 120 W, the ultrasonic frequency is 30 kHz, and then the reaction is completed by stirring at a speed of 200 r / min for 24 h at room temperature.

[0062] (2) Preparation of the anti-adhesion agent: According to the weight fraction, the formula of the anti-adhesion agent comprises 3 parts of octadecanoic acid modified silica, 0.45 parts of anionic surfactant, 0.45 parts of non-ionic surfactant, and 96.1 parts of deionized water.

[0063] The anionic surfactant is sodium dodecyl benzene sulfonate, and the non-ionic surfactant is fatty acid methyl ester ethoxylate.

[0064] The preparation method of the anti-adhesion agent is as follows: the octadecanoic acid modified silica, the anionic surfactant, the non-ionic surfactant, and 75% of the deionized water of the formula component are mixed, uniformly stirred at a rotation speed of 200 r / min, and then ground by a grinder at 2500 r / min for 5 h to obtain a long-term stable dispersion liquid. When used, 25% of the deionized water of the formula component is added into the dispersion liquid to obtain the anti-adhesion agent.

[0065] Example 6 Preparation of an anti-sticking agent for aramid fibers: (1) Preparation of a fatty acid modified inorganic anti-sticking filler: The same as Example 5.

[0066] (2) Preparation of an anti-sticking agent: The formulation of the anti-sticking agent comprises, by weight: 2.5 parts of octadecanoic acid modified silicon dioxide, 0.37 parts of anionic surfactant, 0.37 parts of non-ionic surfactant, and 96.76 parts of deionized water.

[0067] The anionic surfactant is sodium dodecyl benzene sulfonate, and the non-ionic surfactant is fatty acid methyl ester ethoxylate.

[0068] The preparation method of the anti-sticking agent is as follows: the fatty acid modified inorganic anti-sticking filler, the anionic surfactant, the non-ionic surfactant, and 65% of the deionized water of the formulation component are mixed, stirred uniformly at a speed of 200 r / min, and ground by a grinder at a speed of 2500 r / min for 5 h to obtain a long-term stable dispersion liquid. When used, 35% of the deionized water of the formulation component is added to the dispersion liquid to obtain the anti-sticking agent.

[0069] Example 7 Preparation of an anti-sticking agent for aramid fibers: (1) Preparation of a fatty acid modified inorganic anti-sticking filler: The same as Example 5.

[0070] (2) Preparation of an anti-sticking agent: The formulation of the anti-sticking agent comprises, by weight: 1.0 part of octadecanoic acid modified silicon dioxide, 0.15 part of anionic surfactant, 0.15 part of non-ionic surfactant, and 98.7 parts of deionized water.

[0071] The anionic surfactant is sodium dodecyl benzene sulfonate, and the non-ionic surfactant is fatty acid methyl ester ethoxylate.

[0072] The preparation method of the anti-sticking agent is as follows: the fatty acid modified inorganic anti-sticking filler, the anionic surfactant, the non-ionic surfactant, and 70% of the deionized water of the formulation component are mixed, stirred uniformly at a speed of 200 r / min, and ground by a grinder at a speed of 2500 r / min for 5 h to obtain a long-term stable dispersion liquid. When used, 30% of the deionized water of the formulation component is added to the dispersion liquid to obtain the anti-sticking agent.

[0073] Example 8 Preparation of an anti-sticking agent for aramid fibers: (1) Preparation of a fatty acid modified inorganic anti-sticking filler: The same as Example 5.

[0074] (2) Preparation of the anti-sticking agent: The formula of the anti-sticking agent comprises, by weight: 0.75 parts of octadecanoic acid modified silicon dioxide, 0.075 parts of anionic surfactant, 0.075 parts of non-ionic surfactant, and 99.1 parts of deionized water.

[0075] The anionic surfactant is sodium dodecyl benzene sulfonate, and the non-ionic surfactant is fatty acid methyl ester ethoxylate.

[0076] The preparation method of the anti-sticking agent is: mixing the fatty acid modified inorganic anti-sticking filler, the anionic surfactant, the non-ionic surfactant, and 54% of the deionized water of the formula component, stirring uniformly at a speed of 200 r / min, and grinding for 5 h at 2500 r / min using a grinder to obtain a long-term stable dispersion liquid. When in use, 46% of the deionized water of the formula component is added to the dispersion liquid to obtain the anti-sticking agent.

[0077] Example 9 Preparation of an anti-sticking agent for aramid fiber: (1) Preparation of a fatty acid modified inorganic anti-sticking filler: The silane coupling agent is added to a mixed solvent of ethanol and water, and stirred at a speed of 200 r / min for 30 min to make the silane coupling agent fully hydrolyzed. The inorganic anti-sticking filler talc powder is added to n-butanol and uniformly dispersed by ultrasonic treatment. After mixing the above two solutions, the temperature is controlled for reaction, and then solid-liquid separation is performed to obtain talc powder grafted with silane coupling agent. The talc powder grafted with silane coupling agent, N,N-dicyclohexyl carbodiimide, and octadecanoic acid are added to dichloromethane, uniformly dispersed by ultrasonic treatment, and reacted. Finally, the precipitate is obtained by centrifugation, washing, and drying to obtain octadecanoic acid modified talc powder.

[0078] The mass ratio of the silane coupling agent, ethanol, and water is 1:9:2. The mass ratio of the silane coupling agent and talc powder is 10:5. The mass ratio of talc powder and n-butanol is 5:80. The mass ratio of the talc powder grafted with silane coupling agent, N,N-dicyclohexyl carbodiimide, and octadecanoic acid is 1:1.2:0.8. The mass ratio of the talc powder grafted with silane coupling agent and dichloromethane is 5:150.

[0079] The talc powder is added to n-butanol and uniformly dispersed by ultrasonic treatment. The ultrasonic treatment time is 5 min, the ultrasonic power is 160 W, and the ultrasonic frequency is 60 kHz. The silane coupling agent grafted talc powder, N, N-dicyclohexyl carbodiimide, fatty acid were added into dichloromethane, and ultrasonic treatment was performed for 5 min at an ultrasonic power of 160 W and an ultrasonic frequency of 60 kHz, and then the reaction was completed by stirring at a speed of 100 r / min for 48 h at room temperature.

[0080] (2) Preparation of the anti-adhesion agent: According to the weight fraction, the formula of the anti-adhesion agent comprises 3 parts of octadecanoic acid modified talc powder, 0.45 parts of anionic surfactant, 0.45 parts of non-ionic surfactant, and 96.1 parts of deionized water.

[0081] The anionic surfactant is sodium dodecyl benzene sulfonate, and the non-ionic surfactant is fatty acid methyl ester ethoxylate.

[0082] The preparation method of the anti-adhesion agent is as follows: the octadecanoic acid modified talc powder, the anionic surfactant, the non-ionic surfactant, and 75% of the deionized water of the formula component are mixed and uniformly stirred at a speed of 200 r / min, and then a grinder is used to grind at 2500 r / min for 5 h to obtain a long-term stable dispersion liquid. When used, 25% of the deionized water of the formula component is added into the dispersion liquid to obtain the anti-adhesion agent.

[0083] Comparative Example 1 The anti-adhesion agent was prepared by the same method as that of Example 5, except that in the present comparative example 1, the silica was directly used to prepare the anti-adhesion agent without fatty acid modification.

[0084] Comparative Example 2 The anti-adhesion agent was prepared by the same method as that of Example 5, except that in the present comparative example 2, the proportion of the octadecanoic acid modified silica was increased.

[0085] According to the weight fraction, the formula of the anti-adhesion agent in the present comparative example 2 comprises 5 parts of octadecanoic acid modified silica, 0.45 parts of anionic surfactant, 0.45 parts of non-ionic surfactant, and 94.1 parts of deionized water.

[0086] Comparative Example 3 The anti-adhesion agent was prepared by the same method as that of Example 5, except that in the present comparative example 3, the mass ratio of the octadecanoic acid modified silica and the anionic surfactant was 15:1 (not within the proportion range defined in the present application, i.e., the proportion of the anionic surfactant was relatively small).

[0087] According to the weight fraction, the formula of the anti-adhesion agent in the present comparative example 2 comprises 5 parts of octadecanoic acid modified silica, 0.45 parts of anionic surfactant, 0.45 parts of non-ionic surfactant, and 94.1 parts of deionized water.

[0088] Comparative Example 4 The anti-sticking agent was prepared by the same method as in Example 5, except that the amount of non-ionic surfactant was reduced in Comparative Example 4.

[0089] The anti-sticking agent in Comparative Example 2 was prepared according to the following formulation: 3 parts of octadecanoic acid-modified silica, 0.45 parts of anionic surfactant, 0.05 parts of non-ionic surfactant, and 96.5 parts of deionized water.

[0090] Comparative Example 5 The anti-sticking agent was prepared by the same method as in Example 5, except that the amount of non-ionic surfactant was increased in Comparative Example 5.

[0091] The anti-sticking agent in Comparative Example 2 was prepared according to the following formulation: 3 parts of octadecanoic acid-modified silica, 0.45 parts of anionic surfactant, 0.05 parts of non-ionic surfactant, and 96.5 parts of deionized water.

[0092] Comparative Example 6 The anti-sticking agent was prepared by the same method as in Example 5, except that the mass ratio of silane coupling agent, ethanol, and water was 1:10:0.5 (i.e., the amount of water was reduced) when preparing the silane coupling agent-grafted silica in Comparative Example 6.

[0093] Comparative Example 7 The anti-sticking agent was prepared by the same method as in Example 5, except that the mass ratio of silane coupling agent, ethanol, and water was 1:10:3 (i.e., the amount of water was increased) when preparing the silane coupling agent-grafted silica in Comparative Example 7.

[0094] Comparative Example 8 The anti-sticking agent was prepared by the same method as in Example 8, except that the reaction temperature was 60°C (lower than the temperature defined in the present application) when preparing the silane coupling agent-grafted inorganic anti-sticking filler in Comparative Example 8.

[0095] II. Performance Test 1. Surface contact angle test: Different fatty acid-modified silicas were spread on glass slides, and water droplets were placed on the glass slides. The contact angle of water on the surface of the film was measured using a contact angle meter. The test conditions required that the static contact angle of water on the surface of different samples be tested continuously for three times, and the average value of the three points was used. The test results are shown in Table 1.

[0096] Table 1 Surface contact angle test results

[0097] From the above table 1 data can be seen: with the increase of the number of carbon atoms of fatty acid, the contact angle between water and modified silica is gradually increasing, indicating that the greater the number of carbon atoms of fatty acid, the better the hydrophobicity of modified silica.

[0098] The silica particles have a large specific surface area, the surface contains hydroxyl groups, have good physical and chemical properties, and the pollution to the environment is small. Since the unmodified silica has good hydrophilicity and is easy to agglomerate and settle in water, it is difficult to maintain stability for a long time, so the fatty acid is used to modify it in the present application, which reduces the difficulty of use. In addition, talc has good physical and chemical properties such as lubricity, fire resistance, acid resistance, insulation, high melting point, chemical inertness, good hiding power, softness, good gloss, strong adsorption, etc. Since the crystal structure of talc is lamellar, it has a tendency to easily split into scales and special lubricity.

[0099] 2. Stability test: The anti-sticking agent prepared in the above examples and comparative examples was placed in a 15 mL glass bottle, and the time of stratification of the anti-sticking agent was observed at a temperature of 25°C, a humidity of 40%, and a pressure of 1.013 MPa. The test results are shown in Table 2. In Table 2, "none" means that stratification was not observed, and "stratification" means that stratification was observed (d in Table 2 represents "day"; / means that stratification occurred, and no subsequent experiment was performed).

[0100] Table 2 Stability test results

[0101] From the above table 2 data can be seen that the anti-sticking agent prepared by the preparation method of the present application in examples 1-9 has good stability. In the anti-sticking agent of the present application, the inorganic anti-sticking filler is modified by fatty acid, which introduces a long carbon chain to the surface of the inorganic anti-sticking filler, increasing the distance between particles. The addition of anionic surfactant forms a double-layer structure on the surface of the nanoparticles. The nonionic surfactant increases the steric hindrance between particles, which is not conducive to the agglomeration and settling of particles, thereby enhancing the stability of the dispersion. In addition, the increase of solid content can effectively increase the viscosity of the dispersion, and enhance the uniformity and stability of the dispersion. In summary, the anti-sticking agent of the present application can maintain stability for a long time.

[0102] From the comparison of the results of comparative example 1 and example 5, it can be seen that if the silica is not modified by fatty acid, the stability of the anti-sticking agent is greatly reduced.

[0103] From the comparison of the results of Comparative Example 2 and Example 5, it can be seen that if the amount of fatty acid-modified silica is too much, the stability of the anti-tacking agent decreases, because the increase in the amount of modified silica increases the probability and frequency of particle-particle collisions, which more easily leads to particle agglomeration.

[0104] From the comparison of the results of Comparative Example 3 and Example 5, it can be seen that if the proportion of anionic surfactant in the mass ratio of octadecanoic acid-modified silica and anionic surfactant is relatively small, the stability of the anti-tacking agent decreases, because the addition of anionic surfactant forms a double-layer structure on the surface of the nanoparticles (fatty acid-modified inorganic anti-tacking filler), thereby avoiding the problem of sedimentation of the fatty acid-modified inorganic anti-tacking filler, and if the proportion of anionic surfactant is too small, the stability of the anti-tacking agent is affected.

[0105] From the comparison of the results of Comparative Example 4 and Example 5, it can be seen that if the amount of nonionic surfactant is reduced, the stability of the anti-tacking agent decreases, because nonionic surfactant is beneficial to increasing the steric hindrance between particles and is not conducive to the agglomeration and sedimentation between particles, thereby enhancing the stability of the anti-tacking agent.

[0106] From the comparison of the results of Comparative Example 5 and Example 5, it can be seen that if the amount of nonionic surfactant is increased, the stability of the anti-tacking agent does not appear to be significantly affected, but when the anti-tacking agent is applied in fibers, smoke appears during the hot stretching process of the fibers, causing environmental pollution, affecting the performance of the fibers, and increasing the use cost.

[0107] From the comparison of the results of Comparative Example 6 and Example 5, it can be seen that if the amount of water is reduced when preparing the silane coupling agent grafted silica, the hydrolysis of the silane coupling agent is not complete, which reduces the grafting amount on the surface of the silica, thereby reducing the stability of the anti-tacking agent and causing it to easily settle.

[0108] From the comparison of the results of Comparative Example 7 and Example 5, it can be seen that if the amount of water is increased when preparing the silane coupling agent grafted silica, the water and n-butanol separate during the subsequent modification process of the silica, which prevents the silica from fully contacting the silane coupling agent and prevents the reaction from being complete.

[0109] From the comparison of the results of Comparative Example 8 and Example 5, it can be seen that if the reaction temperature is reduced when preparing the silane coupling agent grafted silica, the stability of the anti-tacking agent decreases, because the lower temperature causes the reaction of the silane coupling agent with the surface hydroxyl groups of the silica to be incomplete, which reduces the surface grafting rate.

[0110] 3. Fiber coating application effect test: The application effect of the anti-adhesive agent is tested by post-drawing experiment of the fiber. The fiber used in the application effect test of the fiber coating is para-aramid fiber or modified para-aramid fiber. The structure of the aramid fiber includes at least one of the following two structures, but is not limited to the following two structures: .

[0111] The para-aramid fiber is used in the application effect test of the fiber coating.

[0112] The degree of adhesion (f) can be used to judge the situation of the fiber after post-drawing. Specifically, the degree of adhesion (f) can be calculated according to the following formula: f=N / n; N: the total number of filaments in the bundle; n: the number of filaments that can be separated after heat drawing. The larger the f value, the more serious the situation of the fiber after heat drawing.

[0113] Blank Example 1 A method for preparing a finished fiber, comprising the following steps: the number of spinneret holes is 100, i.e. the number of bundle roots is 100, the surface of the nascent fiber is not coated with an anti-adhesive agent, and after water washing and drying, the nascent fiber is drawn by 8 times at 400 DEG C.

[0114] Blank Example 2 A method for preparing a finished fiber, comprising the following steps: the number of spinneret holes is 100, i.e. the number of bundle roots is 100, the surface of the nascent fiber is not coated with an anti-adhesive agent, and after water washing and drying, the nascent fiber is drawn by 10 times at 450 DEG C.

[0115] Blank Example 3 A method for preparing a finished fiber, comprising the following steps: the number of spinneret holes is 200, i.e. the number of bundle roots is 200, the surface of the nascent fiber is not coated with an anti-adhesive agent, and after water washing and drying, the nascent fiber is drawn by 8 times at 400 DEG C.

[0116] Blank Example 4 A method for preparing a finished fiber, comprising the following steps: the number of spinneret holes is 200, i.e. the number of bundle roots is 200, the surface of the nascent fiber is not coated with an anti-adhesive agent, and after water washing and drying, the nascent fiber is drawn by 10 times at 450 DEG C.

[0117] Application Examples 1-4 The finished fibers are prepared by the methods of Blank Example 1-Blank Example 4 in turn, respectively. However, in each application example, the surface of the nascent fiber is coated with the anti-adhesive agent prepared in Embodiment 1.

[0118] Application Examples 5-8 The finished fibers are prepared by the methods of Blank Example 1-Blank Example 4 in turn, respectively. However, in each application example, the surface of the nascent fiber is coated with the anti-adhesive agent prepared in Embodiment 5.

[0119] Application Example 9~Application Example 12 The finished yarns were prepared by the methods of Blank Example 1~Blank Example 4 in turn respectively, except that the surface of the nascent yarn was coated with the anti-adhesion agent prepared in Embodiment 6 in each application example.

[0120] Application Example 13~Application Example 16 The finished yarns were prepared by the methods of Blank Example 1~Blank Example 4 in turn respectively, except that the surface of the nascent yarn was coated with the anti-adhesion agent prepared in Embodiment 7 in each application example.

[0121] Application Example 17~Application Example 20 The finished yarns were prepared by the methods of Blank Example 1~Blank Example 4 in turn respectively, except that the surface of the nascent yarn was coated with the anti-adhesion agent prepared in Embodiment 8 in each application example.

[0122] Application Example 21~Application Example 24 The finished yarns were prepared by the methods of Blank Example 1~Blank Example 4 in turn respectively, except that the surface of the nascent yarn was coated with the anti-adhesion agent prepared in Embodiment 9 in each application example.

[0123] The conditions of the fibers in the above application blank examples and application examples are as shown in Table 3.

[0124] Table 3 Test results of fiber coating application effect

[0125] As can be seen from the above table data: the anti-adhesion agent described in the application coated on the fiber can effectively reduce the problem of yarn sticking, and reduce the problem of yarn breakage, which is conducive to the smooth spinning of aramid fiber.

[0126] In the process of fiber stretching and drying, the fibers coated with four different mass fractions of modified silica anti-adhesion agent did not appear the phenomenon of yarn sticking and yarning, and the yarns were smooth and uniform. Figures 1-4 It can be seen that: the modified silica particles can effectively and uniformly cover the surface of the fiber, and play the role of spacing the fibers.

[0127] The technical features of the above embodiments can be combined arbitrarily, and in order to make the description simple, all possible combinations of the technical features in the above embodiments are not exhaustively listed, however, as long as the combination of the technical features does not exist contradictory, it should be considered as the scope of the present application.

[0128] For those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application, and the protection scope of the present application is subject to the appended claims.

Claims

1. An anti-sticking agent for aramid fibers, characterized in that, The anti-sticking agent comprises, by weight, 0.75-3 parts of fatty acid modified inorganic anti-sticking filler, 0.075-0.45 parts of anionic surfactant, 0.075-0.45 parts of nonionic surfactant, and 96.1-99.1 parts of deionized water; The inorganic anti-sticking filler is at least one of silica and talc.

2. The anti-sticking agent for aramid fibers according to claim 1, characterized in that, The preparation method of the fatty acid modified inorganic anti-sticking filler is as follows: The silane coupling agent is added to a mixed solvent of ethanol and water for complete hydrolysis, and then an inorganic anti-sticking filler that is uniformly dispersed in n-butanol is added. The reaction is carried out under controlled temperature, and then the inorganic anti-sticking filler grafted with silane coupling agent is obtained by solid-liquid separation. Inorganic anti-sticking filler grafted with silane coupling agent, N,N-dicyclohexylcarbodiimide, and fatty acid were added to dichloromethane, dispersed evenly, and reacted. Finally, fatty acid-modified inorganic anti-sticking filler was obtained by solid-liquid separation and drying.

3. The anti-sticking agent for aramid fibers according to claim 2, characterized in that, The mass ratio of silane coupling agent, ethanol and water is 1:(9-10):(1-2); The mass ratio of silane coupling agent to inorganic anti-sticking filler is (5-10):(2-5); The mass ratio of inorganic anti-sticking filler to n-butanol is (2-5):(50-80); The mass ratio of the silane coupling agent-grafted inorganic anti-sticking filler, N,N-dicyclohexylcarbodiimide, and fatty acid is 1:(1.0-1.2):(0.6-0.8).

4. The anti-sticking agent for aramid fibers according to claim 2, characterized in that, The fatty acid is C. 14 -C 18 At least one of the fatty acids.

5. The anti-sticking agent for aramid fibers according to claim 2, characterized in that, The inorganic anti-adhesion filler was added to n-butanol and uniformly dispersed by ultrasonic treatment. The ultrasonic treatment time was 5-15 min, the ultrasonic power was 120-160 W, and the ultrasonic frequency was 30-60 kHz.

6. The anti-sticking agent for aramid fibers according to claim 2, characterized in that, The reaction temperature for preparing silane coupling agent-grafted inorganic anti-adhesion fillers is 80-90℃, and the reaction time is 6-8h. Inorganic anti-adhesion filler grafted with silane coupling agent, N,N-dicyclohexylcarbodiimide, and fatty acid are added to dichloromethane and ultrasonically treated for 5-15 min at an ultrasonic power of 120-160 W and an ultrasonic frequency of 30-60 kHz. The reaction is then completed by stirring at 100-200 r / min at room temperature for 24-48 h.

7. The anti-sticking agent for aramid fibers according to claim 1, characterized in that, The mass ratio of the fatty acid-modified inorganic anti-sticking filler to the anionic surfactant is (5-10):

1.

8. The anti-sticking agent for aramid fibers according to claim 1, characterized in that, The anionic surfactant is at least one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, and sodium dioctyl maleate sulfonate.

9. The anti-sticking agent for aramid fibers according to claim 1, characterized in that, The nonionic surfactant is at least one of fatty alcohol polyoxyethylene ether, BYK-190, Tween 80, nonylphenol polyoxyethylene ether, and fatty acid methyl ester ethoxylate.

10. A method for preparing an anti-adhesive agent for aramid fibers according to any one of claims 1-9, characterized in that, The preparation method is as follows: A dispersion is obtained by uniformly mixing fatty acid modified inorganic anti-sticking filler, anionic surfactant, nonionic surfactant, and 54%-75% of deionized water by mass of the formulation components, followed by grinding. When using, the remaining deionized water required by the formulation components is added to the dispersion according to the concentration required to obtain the anti-sticking agent.

Images