Carbon fiber sizing composition and carbon fiber sizing

Abstract

This application provides a carbon fiber oiling composition and a carbon fiber oiling agent. The carbon fiber oiling composition provided in this application includes isomeric fatty alcohol alkoxylates, alkyl glycosides, fatty amine polyoxyethylene ethers, modified silicone oil with the structure shown in Formula 1, and an optional pH adjuster. The carbon fiber oiling agent provided in this application is uniform, stable, and has good heat resistance. When the carbon fiber oiling agent provided in this application is applied to carbon fiber production, the production process is smooth, without fuzz, broken fibers, or adhesion, and the resulting carbon fiber has excellent mechanical properties and can be used for the production of high-performance PAN-based carbon fibers.

Description

Technical Field

[0001] This application relates to a carbon fiber oiling composition and a carbon fiber oiling agent. Background Technology

[0002] Carbon fiber is a new type of fiber material with a carbon content of over 90%, possessing high strength and high modulus, and is hailed as the "king of new materials." However, carbon fiber also has defects. Among various defects, surface defects account for about 90% and are the main factor leading to its breakage. Carbon fiber oil is an indispensable key additive in the carbon fiber manufacturing process. It ensures the smooth progress of pre-oxidation and low-temperature carbonization, effectively reduces fuzz and broken fibers caused by friction, prevents monofilament adhesion, and thus improves the quality of carbon fiber.

[0003] Carbon fiber oils are mainly divided into two categories: non-silicone oils and silicone oils. Silicone oils have better performance, which can reduce the surface resistance of carbon fiber precursors, make the precursors smoother, and play a role in preventing adhesion, smoothing, and protecting the monofilaments from damage caused by byproducts during carbonization.

[0004] Organosilicon oils can be mainly divided into three types: amino-modified, epoxy-modified, and polyether-modified silicone oils. Amino-modified silicone oils impart appropriate smoothness and friction to the precursor yarn. As their content increases, the resistance and friction coefficient of the oil gradually decrease. Epoxy-modified silicone oils impart appropriate heat resistance and bundle properties to the precursor yarn. As their content increases, the heat resistance, bundle properties, and viscosity of the oil increase, while the resistivity and friction coefficient remain basically unchanged, and the wettability and stability decrease. Polyether-modified silicone oils can increase the wettability of the oil and promote the formation of a uniform emulsion between the oil and water, which enables smooth spinning, avoids phenomena such as fuzz and breakage, and is conducive to the formulation of a more stable emulsion, which is beneficial for long-term storage.

[0005] Currently, the main component of carbon fiber oils widely used by carbon fiber manufacturers at home and abroad is functionalized modified silicone oil, which is used in the form of water emulsion and contains appropriate emulsifiers and other additives, but the effect is not satisfactory. Summary of the Invention

[0006] The main technical problem addressed by this application is that existing carbon fiber oils do not provide sufficient protection for fibers during spinning and pre-oxidation stages. After oiling, the fibers exhibit poor cohesion and splitting properties, leading to issues such as fuzzing, fiber breakage, and adhesion during production, ultimately affecting the mechanical properties of the carbon fibers. To address this, this application provides a modified silicone oil, a carbon fiber oil composition including the modified silicone oil, and a carbon fiber oil.

[0007] In a first aspect, this application provides a modified silicone oil comprising the structure shown in Formula 1:

[0008]

[0009] In Formula 1, R1 is selected from polyether modifying groups, R2 is selected from amino modifying groups, and 0.01≤b / a≤0.2.

[0010] In some embodiments, R1 is selected from polyether modifying groups having 3-20 alkoxy groups, such as polyether modifying groups having 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 alkoxy groups. In some embodiments, R1 is selected from polyether modifying groups having 4-16 alkoxy groups.

[0011] In some embodiments, R1 is selected from -(OCH2CH2)nOH, and n is selected from an integer between 3 and 20, such as 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19. In some embodiments, n is selected from an integer between 4 and 16.

[0012] In some implementations, b / a is 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, or any value between them. In some implementations, 0.05 ≤ b / a ≤ 0.15.

[0013] In some implementations, 'a' is selected from an integer between 50 and 200, such as 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or any value between them. In some implementations, 'a' is selected from an integer between 60 and 120.

[0014] In some implementations, b is selected from an integer between 1 and 20, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19. In some implementations, b is selected from an integer between 3 and 15.

[0015] In some embodiments, R2 is selected from monoaminoalkyl and diaminoalkyl groups having 2 to 8 carbon atoms, for example 3, 4, 5, 6 or 7. In some embodiments, R2 is selected from -(CH2)mNH2, -(CH2)m1NH(CH2)m2NH2, where m, m1 and m2 are each independently selected from integers between 2 and 8, and 2 ≤ m1 + m2 ≤ 8.

[0016] In some embodiments, m is 3, 4, 5, 6, or 7. In some embodiments, m1 is 3, 4, 5, 6, or 7. In some embodiments, m2 is 3, 4, 5, 6, or 7.

[0017] In some embodiments, the viscosity of the modified silicone oil is 300cp-3000cp, for example, 500cp, 700cp, 900cp, 1000cp, 1100cp, 1300cp, 1500cp, 1700cp, 1900cp, 2000cp, 2100cp, 2300cp, 2500cp, 2700cp, or 2900cp.

[0018] Secondly, this application provides a carbon fiber oiling composition comprising isomeric fatty alcohol alkoxylates, alkyl glycosides, fatty amine polyoxyethylene ethers, modified silicone oil, and optionally a pH adjuster, wherein...

[0019] The modified silicone oil comprises the structure shown in Formula 1:

[0020]

[0021] In Formula 1, R1 is selected from polyether modifying groups, R2 is selected from amino modifying groups, and 0.01≤b / a≤0.2.

[0022] In some embodiments, R1 is selected from polyether modifying groups having 3-20 alkoxy groups, such as polyether modifying groups having 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 alkoxy groups. In some embodiments, R1 is selected from polyether modifying groups having 4-16 alkoxy groups.

[0023] In some embodiments, R1 is selected from -(OCH2CH2)nOH, and n is selected from an integer between 3 and 20, such as 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19. In some embodiments, n is selected from an integer between 4 and 16.

[0024] The carbon fiber oiling composition provided in this application includes amino polyether co-modified silicone oil as shown in Formula 1. On the one hand, the end-group polyether modification has good hydrophilicity, which can improve the emulsification performance and make the final oil-in-water emulsion have good stability. On the other hand, the addition of alkyl glycosides is conducive to cross-linking reaction with amino polyether co-modified silicone oil, thereby improving the heat resistance of the oiling agent.

[0025] In some implementations, b / a is 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, or any value between them. In some implementations, 0.05 ≤ b / a ≤ 0.15.

[0026] In some implementations, 'a' is selected from an integer between 50 and 200, such as 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or any value between them. In some implementations, 'a' is selected from an integer between 60 and 120.

[0027] In some implementations, b is selected from an integer between 1 and 20, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19. In some implementations, b is selected from an integer between 3 and 15.

[0028] In some embodiments, R2 is selected from monoaminoalkyl and diaminoalkyl groups having 2 to 8 carbon atoms, for example 3, 4, 5, 6 or 7. In some embodiments, R2 is selected from -(CH2)mNH2, -(CH2)m1NH(CH2)m2NH2, where m, m1 and m2 are each independently selected from integers between 2 and 8, and 2 ≤ m1 + m2 ≤ 8.

[0029] In some embodiments, m is 3, 4, 5, 6, or 7. In some embodiments, m1 is 3, 4, 5, 6, or 7. In some embodiments, m2 is 3, 4, 5, 6, or 7.

[0030] In some embodiments, the viscosity of the modified silicone oil is 300cp-3000cp, for example, 500cp, 700cp, 900cp, 1000cp, 1100cp, 1300cp, 1500cp, 1700cp, 1900cp, 2000cp, 2100cp, 2300cp, 2500cp, 2700cp, or 2900cp.

[0031] In some embodiments, the alkyl glycoside content is 3%-25% by mass, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or any value between therewith, based on the mass of the composition. In some embodiments, the alkyl glycoside content is 5%-20% by mass.

[0032] In some embodiments, the mass ratio of the modified silicone oil to the alkyl glycoside is (1-10):1, for example, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, or any value between them. In some embodiments, the mass ratio of the modified silicone oil to the alkyl glycoside is (3-8):1.

[0033] In some embodiments, the alkyl glycoside is selected from one or more glycosides consisting of an aliphatic group, preferably an alkyl group, having 6-20 carbon atoms, and 1-3 glycosides.

[0034] In some embodiments, the alkyl glycoside is selected from one or more of C6-C20 alkyl glucoside and C6-C20 alkyl maltose.

[0035] In some embodiments, the alkyl glycoside is selected from one or more of C8-C18 alkyl glucosides. In some embodiments, the alkyl glycoside is selected from one or more of C10-C16 alkyl glucosides.

[0036] In some embodiments, the alkyl glycoside is selected from one or more of C8-C18 alkyl maltodextrins. In some embodiments, the alkyl glycoside is selected from one or more of C10-C16 alkyl maltodextrins.

[0037] In some embodiments, the alkyl glycoside is selected from one or more of n-octyl glucoside, dodecyl glucoside, tetradecyl glucoside, hexadecyl glucoside, n-eicosyl glucoside, and dodecyl-β-D-maltodextrin.

[0038] In some embodiments, the modified silicone oil has a mass content of 40%-70% based on the mass of the composition, for example, 41%, 43%, 45%, 47%, 49%, 50%, 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67%, 69%, or any value between therewith. In some embodiments, the modified silicone oil has a mass content of 50%-65%.

[0039] In some embodiments, the mass content of the isomeric fatty alcohol alkoxylate is 5%-20% based on the mass of the composition, for example, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or any value between therewith. In some embodiments, the mass content of the isomeric fatty alcohol alkoxylate is 10%-15%.

[0040] In some embodiments, the fatty amine polyoxyethylene ether has a mass content of 5%-20% based on the mass of the composition, for example, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or any value between therewith. In some embodiments, the fatty amine polyoxyethylene ether has a mass content of 10%-15%.

[0041] In some embodiments, the pH adjuster has a mass content of 0.01%-2% based on the mass of the composition, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or any value between them. In some embodiments, the pH adjuster has a mass content of 0.1%-1%.

[0042] In some embodiments, the carbon fiber oiling composition comprises, by weight, the following components:

[0043] 5-20 parts of isomeric fatty alcohol alkoxylates;

[0044] Alkyl glycosides, 5-20 parts;

[0045] 5-20 parts of fatty amine polyoxyethylene ether;

[0046] pH adjuster 0.01-2 parts;

[0047] 40-70 parts of the modified silicone oil shown in Formula 1.

[0048] In some embodiments, the isomeric fatty alcohol alkoxylate is 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or any value between them.

[0049] In some embodiments, the alkyl glycoside is 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or any value between them.

[0050] In some embodiments, the fatty amine polyoxyethylene ether is 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or any value between them.

[0051] In some embodiments, the pH adjuster is 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, or any value between them.

[0052] In some embodiments, the modified silicone oil shown in Formula 1 is 41 parts, 43 parts, 45 parts, 47 parts, 49 parts, 50 parts, 51 parts, 53 parts, 55 parts, 57 parts, 59 parts, 60 parts, 61 parts, 63 parts, 65 parts, 67 parts, 69 parts, or any value between them.

[0053] In some embodiments, the isomeric fatty alcohol alkoxylate is selected from one or more fatty alcohol alkoxylates having 8-16 carbon atoms, for example, 9, 10, 11, 12, 13, 14 or 15.

[0054] In some embodiments, the isomeric fatty alcohol alkoxylate is selected from one or more of isomeric tridecyl alcohol alkoxylate and isomeric decaol alkoxylate.

[0055] In some embodiments, the ethoxy addition number in the alkoxy group is 2-8, for example 3, 4, 5, 6 or 7, and the propoxy addition number is 0-4, for example 1, 2 or 3.

[0056] In some embodiments, the fatty amine polyoxyethylene ether is selected from one or more fatty amine polyoxyethylene ethers composed of a fatty amine having 6-18 carbon atoms, such as 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, and two polyoxyethylene ether segments with 2-12 ethoxy addition numbers.

[0057] In some embodiments, the number of additions of the two ethoxy groups are 3, 4, 5, 6, 7, 8, 9, 10, or 11.

[0058] In some embodiments, the fatty amine polyoxyethylene ether is selected from dodecylamine polyoxyethylene ether, wherein the total number of ethoxy groups is 6-20, for example 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19.

[0059] In some embodiments, the pH adjuster is selected from one or more inorganic or organic acids.

[0060] In some embodiments, the inorganic acid is selected from one or more of hydrochloric acid, phosphoric acid, and sulfuric acid.

[0061] In some embodiments, the organic acid is selected from one or more of carboxylic acids and organic sulfonic acids, such as acetic acid and / or trifluoromethanesulfonic acid.

[0062] Thirdly, this application provides a carbon fiber oiling agent comprising the composition described in the first aspect and water.

[0063] In some embodiments, the carbon fiber oil contains 10%-30% by mass, for example 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or any value between them.

[0064] In some embodiments, the effective concentration of the oil is diluted with deionized water to 1%-5%, for example, 2%, 3% or 4%.

[0065] Fourthly, the present invention provides a method for preparing the carbon fiber oil agent described in the third aspect, which includes mixing the composition described in the second aspect with water under stirring conditions.

[0066] In some embodiments, the preparation method includes: placing the composition described in the second aspect in a stirring vessel, slowly adding water in the required proportion under high-speed stirring, and continuing stirring, preferably for 0.5-2 hours after completion; and further homogenizing the carbon fiber oil obtained by high-speed stirring using a high-pressure homogenizer.

[0067] In some embodiments, the stirring speed is 500-3000 r / min, for example 1000 r / min, 1500 r / min, 2000 r / min or 2500 r / min.

[0068] In some implementations, the water addition time is controlled between 0.5 and 5 hours, for example, 1 hour, 2 hours, 3 hours, or 4 hours.

[0069] In some embodiments, the high-pressure homogenizer operates at a pressure of 1-150 MPa, for example, 10 MPa, 30 MPa, 50 MPa, 70 MPa, 90 MPa, 100 MPa, 110 MPa or 130 MPa.

[0070] Fifthly, this application provides the application of the modified silicone oil described in the first aspect, or the carbon fiber oiling composition described in the second aspect, or the carbon fiber oiling agent described in the third aspect, or the carbon fiber oiling agent prepared by the preparation method described in the fourth aspect, in the preparation of carbon fibers.

[0071] In some embodiments, the carbon fiber is selected from PAN-based carbon fibers.

[0072] The beneficial effects of this application are:

[0073] The carbon fiber oiling agent provided in this application is uniform, stable, and has good heat resistance. When the carbon fiber oiling agent provided in this application is applied to carbon fiber production, the production process is smooth, without any fuzz, broken fibers, or adhesion, and the resulting carbon fiber has excellent mechanical properties and can be used for the production of high-performance PAN-based carbon fiber. Detailed Implementation

[0074] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of this application. Furthermore, descriptions of well-known structures and technologies are omitted in the following description to avoid unnecessarily obscuring the concepts of this disclosure. Such structures and technologies have also been described in numerous publications.

[0075] The present application will be described in detail below through examples and comparative examples.

[0076] Unless otherwise specified, "%" in this application indicates the percentage content by mass.

[0077] Production of PAN-based carbon fiber: Washed polyacrylonitrile precursor fibers undergo a first oiling process using a carbon fiber spinning oil with a concentration of 2% at room temperature (25°C). Excess oil is extruded by extrusion rollers and then enters a first drying and densification process at 75°C for 40 seconds. A second oiling process is then performed using the same carbon fiber spinning oil with a concentration of 2% at room temperature. The precursor fibers leaving the second oiling process are then extruded again and undergo a second drying and densification process at 120°C for 40 seconds. The resulting precursor fibers are then steam-drawn at a pressure of 0.2 MPa and a draw ratio of 2. Finally, the fibers are steam-heat-set and wound to obtain high-performance polyacrylonitrile precursor fibers.

[0078] Polyacrylonitrile precursor fibers were heat-stabilized in an air-atmosphere furnace at 250°C for 60 minutes, with a total draw of 2%, to obtain heat-stabilized fibers. The obtained heat-stabilized fibers were then subjected to low-temperature and high-temperature carbonization in nitrogen atmosphere. The low-temperature carbonization temperature was 600°C for 4 minutes, with a draw of 3%; the high-temperature carbonization temperature was 1500°C for 2 minutes, with a draw of 3%, to obtain polyacrylonitrile (PAN)-based carbon fibers.

[0079] The mechanical properties of polyacrylonitrile carbon fiber were tested in accordance with the national standard GB-T3362-2005.

[0080] Example 1

[0081] Raw material: Amino polyether modified silicone oil 1 [R1=-(OCH2CH2) 10 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12] 60 parts, isomeric tridecyl alcohol polyoxyethylene ether 3 (3 represents the number of ethylene oxide additions is 3) 15 parts, dodecylamine polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 15 parts, dodecyl glucoside 9 parts, glacial acetic acid 1 part.

[0082] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0083] The above-mentioned oiling agent was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, fiber breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and free of fuzz. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.97 GPa, and the tensile modulus was 245 GPa.

[0084] Example 2

[0085] Raw material: Amino polyether modified silicone oil 1 [R1=-(OCH2CH2) 10 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12] 60 parts, isomeric tridecyl alcohol polyoxyethylene ether 3 (3 represents the number of ethylene oxide additions is 3) 15 parts, dodecylamine polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 15 parts, hexadecyl glucoside 9 parts, glacial acetic acid 1 part.

[0086] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0087] The above-mentioned oiling agent was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, fiber breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and free of fuzz. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.95 GPa, and the tensile modulus was 241 GPa.

[0088] Example 3

[0089] Raw material: Amino polyether modified silicone oil 1 [R1=-(OCH2CH2) 10 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12] 60 parts, isomeric tridecyl alcohol polyoxyethylene ether 3 (3 represents the number of ethylene oxide additions is 3) 15 parts, dodecylamine polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 15 parts, dodecyl-β-D-maltodextrin 9 parts, glacial acetic acid 1 part.

[0090] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0091] The above-mentioned oiling agent was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and fuzz-free. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.90 GPa, and the tensile modulus was 239 GPa.

[0092] Example 4

[0093] Raw material: Amino polyether modified silicone oil 2 [R1=-(OCH2CH2) 10OH, R2=-CH2CH2CH2NHCH2CH2NH2, a=100, b=8, b / a=0.08] 60 parts, isomeric tridecyl alcohol polyoxyethylene ether 3 (3 represents the number of ethylene oxide additions is 3) 15 parts, dodecylamine polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 15 parts, dodecyl glucoside 9 parts, glacial acetic acid 1 part.

[0094] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0095] The above-mentioned oiling agent was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, fiber breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and free of fuzz. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.88 GPa, and the tensile modulus was 246 GPa.

[0096] Example 5

[0097] Raw material: Amino polyether modified silicone oil 3 [R1=-(OCH2CH2)6OH,R2=-CH2CH2CH2NH2,a=100,b=10,b / a=0.10]60 parts, isomeric tridecyl alcohol polyoxyethylene ether 3 (3 represents the number of ethylene oxide additions is 3) 15 parts, dodecylamine polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 15 parts, dodecyl glucoside 9 parts, glacial acetic acid 1 part.

[0098] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0099] The above-mentioned oiling agent was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, fiber breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and free of fuzz. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.91 GPa, and the tensile modulus was 239 GPa.

[0100] Example 6

[0101] Raw material: Amino polyether modified silicone oil 1 [R1=-(OCH2CH2) 10 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12] 60 parts, isomeric tridecyl alcohol polyoxyethylene ether 6 (6 represents the number of ethylene oxide additions is 6) 15 parts, dodecylamine polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 15 parts, dodecyl glucoside 9 parts, glacial acetic acid 1 part.

[0102] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 50 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0103] The above-mentioned oiling agent was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, fiber breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and free of fuzz. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.93 GPa, and the tensile modulus was 240 GPa.

[0104] Example 7

[0105] Raw material: Amino polyether modified silicone oil 1 [R1=-(OCH2CH2) 10 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12] 60 parts, isomeric tridecyl alcohol polyoxyethylene ether 3 (3 represents the number of ethylene oxide additions is 3) 15 parts, dodecylamine polyoxyethylene ether 16 (16 represents the total number of ethylene oxide additions is 16) 15 parts, dodecyl glucoside 9 parts, glacial acetic acid 1 part.

[0106] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0107] The above-mentioned oiling agent was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, fiber breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and free of fuzz. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.86 GPa, and the tensile modulus was 242 GPa.

[0108] Example 8

[0109] Raw material: Amino polyether modified silicone oil 1 [R1=-(OCH2CH2) 10 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12, viscosity 1000cp] 60 parts, isomeric tridecyl alcohol polyoxyethylene ether 3 (3 represents the number of ethylene oxide additions is 3) 10 parts, dodecylamine polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 10 parts, dodecyl glucoside 19.9 parts, glacial acetic acid 0.1 parts.

[0110] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0111] The above-mentioned oiling agent was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, fiber breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and free of fuzz. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.95 GPa, and the tensile modulus was 249 GPa.

[0112] Example 9

[0113] The only difference from Example 1 is that amino polyether modified silicone oil 4 is used. [R1=-(OCH2CH2)3OH,R2=-CH2CH2CH2NH2,a=100,b=12,b / a=0.12] Replacement amino polyether modified silicone oil 1.

[0114] The obtained oil was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and fuzz-free. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.81 GPa, and the tensile modulus was 236 GPa.

[0115] Example 10

[0116] The only difference from Example 1 is that amino polyether modified silicone oil 5 [R1=-(OCH2CH2) 15 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12] Replacement amino polyether modified silicone oil 1.

[0117] The obtained oil was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and fuzz-free. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.70 GPa, and the tensile modulus was 235 GPa.

[0118] Example 11

[0119] The only difference from Example 1 is that amino polyether modified silicone oil 6 is used. [R1=-(OCH2CH2) 20 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12] Replacement amino polyether modified silicone oil 1.

[0120] The obtained oil was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and fuzz-free. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.52 GPa, and the tensile modulus was 233 GPa.

[0121] Example 12

[0122] The only difference from Example 1 is that 9 parts of n-octyl glucoside are used instead of 9 parts of dodecyl glucoside.

[0123] The obtained oil was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and fuzz-free. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.73 GPa, and the tensile modulus was 242 GPa.

[0124] Example 13

[0125] The only difference from Example 1 is that 9 parts of n-eicosyl glucoside are used instead of 9 parts of dodecyl glucoside.

[0126] The obtained oil was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and fuzz-free. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.64 GPa, and the tensile modulus was 239 GPa.

[0127] Example 14

[0128] The only difference from Example 1 is that:

[0129] 1.62 parts of amino polyether modified silicone oil;

[0130] 3 15 parts of isomeric tridecyl alcohol polyoxyethylene ether;

[0131] 10-15 parts of dodecylamine polyoxyethylene ether;

[0132] 7 parts of dodecyl glucoside;

[0133] 1 part glacial acetic acid.

[0134] The obtained oil was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and fuzz-free. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.61 GPa, and the tensile modulus was 236 GPa.

[0135] Example 15

[0136] The only difference from Example 1 is that:

[0137]

[0138] The obtained oil was formulated to a 2% concentration for fiber oiling evaluation. No fuzzing, breakage, or adhesion occurred during the production process, and the resulting fibers were smooth, soft, and fuzz-free. The tensile strength of the obtained polyacrylonitrile carbon fiber multifilament was 4.57 GPa, and the tensile modulus was 235 GPa.

[0139] Comparative Example 1

[0140] Raw material: Amino polyether modified silicone oil 1 [R1=-(OCH2CH2) 10 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12] 60 parts, isomeric tridecyl alcohol polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 20 parts, dodecylamine polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 19 parts, glacial acetic acid 1 part.

[0141] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0142] The above-mentioned oiling agent was prepared to a concentration of 2% for fiber oiling evaluation. The resulting fibers showed some fuzziness and adhesion. The strength of the obtained polyacrylonitrile carbon fiber multifilament was 3.57 GPa and the tensile modulus was 193 GPa.

[0143] Comparative Example 2

[0144] Raw material: Amino-modified silicone oil 1 [R1=CH3, R2=-CH2CH2CH2NH2, a=100, b=8, b / a=0.08] 60 parts, 10 parts of isomeric tridecyl alcohol polyoxyethylene ether (10 represents the total number of ethylene oxide additions of 10) 15 parts, 10 parts of dodecylamine polyoxyethylene ether (10 represents the total number of ethylene oxide additions of 10) 15 parts, glucose 9 parts, glacial acetic acid 1 part.

[0145] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0146] The above-mentioned oiling agent was prepared to a concentration of 2% for fiber oiling evaluation. The resulting fibers showed some fuzziness and adhesion. The strength of the obtained polyacrylonitrile carbon fiber multifilament was 3.72 GPa and the tensile modulus was 208 GPa.

[0147] Comparative Example 3

[0148] Raw material: Amino polyether modified silicone oil 1 [R1=-(OCH2CH2) 10 OH, R2=-CH2CH2CH2NH2, a=100, b=12, b / a=0.12, viscosity 1000cp] 60 parts, isomeric tridecyl alcohol polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 15 parts, dodecylamine polyoxyethylene ether 10 (10 represents the total number of ethylene oxide additions is 10) 15 parts, α-methyl glucoside 9 parts, glacial acetic acid 1 part.

[0149] Accurately add the above active ingredients to the mixing vessel, turn on the high-speed stirrer, and select a stirring speed of 1200 r / min. Slowly add the required proportion of deionized water over 3 hours to prepare an oil agent with an effective concentration of 20%, and continue stirring for 1 hour after completion. Then immediately use a high-pressure homogenizer to further homogenize the oil agent obtained from high-speed stirring to obtain a carbon fiber oil agent. Select a homogenization pressure of 100 MPa and a homogenizer flow rate of 5 L / h. The obtained carbon fiber spinning oil agent is uniform and stable.

[0150] The above-mentioned oiling agent was prepared to a concentration of 2% for fiber oiling evaluation. The resulting fibers showed some fuzziness and adhesion. The strength of the obtained polyacrylonitrile carbon fiber multifilament was 3.79 GPa and the tensile modulus was 215 GPa.

[0151] The preferred embodiments of this application have been described in detail above; however, this application is not limited thereto. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, including combining various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in this application and are all within the protection scope of this application.

Claims

1. A carbon fiber oiling composition comprising an isomeric fatty alcohol alkoxylate, an alkyl glycoside, a fatty amine polyoxyethylene ether, a modified silicone oil, and an optional pH adjuster, wherein, The modified silicone oil comprises the structure shown in Formula 1: In Formula 1, R1 is selected from polyether modifying groups, R2 is selected from amino modifying groups, and 0.01≤b / a≤0.

2.

2. The composition according to claim 1, characterized in that, R1 is selected from polyether modifying groups having 3-20, preferably 4-16, alkoxy groups, preferably selected from -(OCH2CH2)nOH, where n is selected from an integer between 3 and 20, preferably an integer between 4 and 16.

3. The composition according to claim 1 or 2, characterized in that, 0.05 ≤ b / a ≤ 0.15; and / or a is an integer selected from 50-200, preferably an integer from 60-120; and / or b is selected from an integer between 1 and 20, preferably an integer between 3 and 15; and / or R2 is selected from monoaminoalkyl and diaminoalkyl groups having 2-8 carbon atoms, preferably from -(CH2)mNH2, -(CH2)m1NH(CH2)m2NH2, where m, m1, and m2 are each independently selected from integers between 2 and 8, and 2 ≤ m1 + m2 ≤ 8; and / or The viscosity of the modified silicone oil is 300cp-3000cp.

4. The composition according to any one of claims 1-3, characterized in that, Based on the mass of the composition, the alkyl glycoside content is 3%-25%, preferably 5%-20%.

5. The composition according to any one of claims 1-4, characterized in that, The mass ratio of the modified silicone oil to the alkyl glycoside is (1-10):1, preferably (3-8):

1.

6. The composition according to any one of claims 1-5, characterized in that, The alkyl glycoside is selected from one or more of an aliphatic group, preferably an alkyl group, having 6-20 carbon atoms, and 1-3 glycosides, preferably selected from one or more of C6-C20 alkyl glucoside and C6-C20 alkyl maltoside, more preferably selected from one or more of n-octyl glucoside, dodecyl glucoside, tetradecyl glucoside, hexadecyl glucoside, n-eicosyl glucoside, and dodecyl-β-D-maltoside.

7. The composition according to any one of claims 1-6, characterized in that, Based on the mass of the composition, the modified silicone oil has a mass content of 40%-70%, preferably 50%-65%; and / or The mass content of the isomeric fatty alcohol alkoxylate is 5%-20%, preferably 10%-15%; and / or The fatty amine polyoxyethylene ether has a mass content of 5%-20%, preferably 10%-15%; and / or The pH adjuster has a mass content of 0.01%-2%, preferably 0.1%-1%.

8. The composition according to any one of claims 1-7, characterized in that, The isomeric fatty alcohol alkoxylate is selected from one or more fatty alcohol alkoxylates having 8-16 carbon atoms, preferably from one or more isomeric tridecyl alcohol alkoxylates and isomeric decaol alkoxylates, and preferably the alkoxylate fragment has an ethoxy addition number of 2-8 and a propoxy addition number of 0-4; and / or The fatty amine polyoxyethylene ether is selected from one or more fatty amine polyoxyethylene ethers composed of a fatty amine with 6-18 carbon atoms and two polyoxyethylene ether segments with an ethoxy group number of 2-12, preferably selected from dodecylamine polyoxyethylene ether, wherein the total ethoxy group number is 6-20; and / or The pH adjuster is selected from one or more inorganic acids or organic acids. Preferably, the inorganic acid is selected from one or more hydrochloric acid, phosphoric acid and sulfuric acid. Preferably, the organic acid is selected from one or more carboxylic acids and organic sulfonic acids, such as acetic acid and / or trifluoromethanesulfonic acid.

9. A carbon fiber oiling agent comprising the composition of any one of claims 1-8 and water, preferably wherein the composition comprises 10%-30% by mass in the carbon fiber oiling agent.

10. The use of the carbon fiber oiling composition according to any one of claims 1-8 or the carbon fiber oiling agent according to claim 9 in the preparation of carbon fibers, especially PAN-based carbon fibers.

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