Low-silicon oil composition for pan-based carbon fiber, oil composition solution, and use thereof

Abstract

The application relates to the field of carbon fiber oiling agents, and discloses a low-silicon oiling agent composition for PAN-based carbon fibers, an oiling agent composition liquid and application thereof. The low-silicon oiling agent composition comprises polyamino-modified polysiloxane, fatty acid ester, surfactant and antistatic agent; wherein the polyamino-modified polysiloxane has a structure shown in formula (I), formula (I); in formula (I), R is an aminoalkyl group, x is an integer of 10-100, and y is an integer of 5-20; the fatty acid ester has a structure shown in formula (II), formula (II); in formula (II), R1 and R2 are each independently C1-C10 hydrocarbon groups, and n1 and n2 are each independently integers of 1-10. The low-silicon oiling agent composition of the application can effectively reduce the silicon content and the oiling agent ash content when used, reduce the silicon pollution in the carbon fiber production process, and better improve the smoothness of the fibers.

Description

Technical Field

[0001] This invention relates to the field of carbon fiber oiling technology, specifically to a low-silicone oiling composition for PAN-based carbon fibers, an oiling liquid mixture, and its application. Background Technology

[0002] Carbon fiber is a special fiber composed of carbon elements, with a carbon content of over 90%, and is a brittle material. During its production, differences in process details and material ratios can lead to certain quality defects, such as surface pores, deposits, scratches, and adhesion between monofilaments. These defects are difficult to eliminate in subsequent processing, resulting in a decrease in the mechanical properties of carbon fiber.

[0003] Carbon fiber oil is an essential additive in carbon fiber manufacturing and the most effective technology for suppressing the formation of surface defects in carbon fibers. Its main function is to solve some problems in the production and processing process, such as adjusting fiber friction characteristics, preventing or eliminating static electricity accumulation, imparting smooth and soft properties to fibers, improving fiber cohesion, protecting fibers from damage, reducing fuzz and breakage, and making the fibers adaptable to the requirements of spinning, stretching, pre-oxidation, and low-temperature carbonization processes.

[0004] Currently, silicon-based oils are the mainstream oils, with mature technology and widespread use by carbon fiber manufacturers both domestically and internationally. They are one of the main technical measures to prevent inherent and acquired defects on the surface. However, with in-depth research, it has been found that these oils pyrolyze into SiO2 and other volatiles in the pre-oxidation furnace at 200-300℃, causing dust and silicon contamination of the pre-oxidation furnace and its supporting systems. Simultaneously, the silicon compounds remaining inside the fibers also lead to a decrease in the tensile strength of the carbon fibers, seriously affecting the tensile strength of the carbon fibers and the stability of the production process. To prevent silicon contamination, researchers have begun to develop and use non-silicone oils and sugar-based oils to completely eliminate silicon contamination. However, non-silicone oils generally have poor heat resistance and are prone to producing fuzz and broken fibers during the pre-oxidation and carbonization stages, deteriorating the mechanical properties of the carbon fibers. Therefore, the focus of carbon fiber oil development is on appropriately reducing the silicon content without affecting fiber performance, forming low-silicone oils.

[0005] CN101326313B discloses an acrylonitrile-based fiber oiling agent for carbon fiber manufacturing, which contains ester compounds with more than three ester groups in the molecule and silicone compounds as essential components; CN103502519A discloses an acrylonitrile-based fiber bundle of carbon fiber precursors with an oiling agent composition attached, using amino-modified organosilicon and aromatic ester compounds with specific structures. In low-silicone oiling agents, the main method is to directly mix modified silicone oil, emulsifier, and heat-resistant organic ester compounds (such as pentaerythritol fatty acid ester, trimethylolpropane fatty acid ester, pyromellitic acid fatty alcohol ester, etc.), and then prepare an oiling agent emulsion through a diversion emulsification process. However, the oiling agent prepared by this method cannot be uniformly attached to the surface of the carbon fiber precursor fiber bundle (protocol), affecting the overall performance of the carbon fiber.

[0006] CN104910388B discloses a method for preparing low-silicone carbon fiber oil by co-modifying polyol fatty acid esters / polyethers using a hydrosilylation reaction: a heat-resistant ester containing C=C double bonds and a polyether are simultaneously attached to the side chain of a silicone oil to synthesize a co-modified silicone oil, which is then used as a key component to prepare a low-silicone carbon fiber oil. However, polyol fatty acid esters (such as trimethylolpropane allyl ether difatty acid ester) have large molecular structures, making the synthesis process relatively complicated and difficult to introduce in large quantities into modified silicone oils. Summary of the Invention

[0007] The purpose of this invention is to overcome the problem that existing silicone-based oils easily generate a large amount of silicon contamination during the oxidation and carbonization process, which contaminates the oxidation furnace and carbonization furnace, causing blockages, and also reduces the strength and modulus of the produced carbon fibers. This invention provides a low-silicone oil composition for PAN-based carbon fibers, an oil combination liquid, and its application.

[0008] To achieve the above objectives, the first aspect of the present invention provides a low-silicone oiling composition for PAN-based carbon fibers, the low-silicone oiling composition comprising a polyamino-modified polysiloxane, a fatty acid ester, a surfactant, and an antistatic agent.

[0009] The polyamino-modified polysiloxane has the structure shown in formula (I).

[0010]

[0011] In formula (I), R is an aminoalkyl group, x is an integer from 10 to 100, and y is an integer from 5 to 20;

[0012] The fatty acid ester has the structure shown in formula (II).

[0013]

[0014] In formula (II), R1 and R2 are each independently C1-C10 hydrocarbon groups, and n1 and n2 are each independently integers from 1 to 10.

[0015] Preferably, the surfactant comprises a polyol ester and a compound having the structure shown in formula (III).

[0016]

[0017] In formula (III), R3 is a C10-C20 alkyl group, and n3 is an integer from 4 to 10.

[0018] A second aspect of the present invention provides an oil-based liquid composition comprising a low-silicone oil composition and water.

[0019] Preferably, the low-silicone oil composition comprises 10-30% by weight in the oil mixture.

[0020] A third aspect of the present invention provides the application of the above-mentioned low-silicone oiling composition or oiling liquid in the production of PAN-based carbon fiber.

[0021] Compared with existing technologies, under the action of surfactants, the low-silicone oiling composition of the present invention, through the synergistic effect of the polyamino-modified polysiloxane with the structure shown in formula (I) and the fatty acid ester with the structure shown in formula (II), can effectively reduce silicon content and oiling ash content during use, reduce silicon pollution in the carbon fiber production process, and improve fiber smoothness. Furthermore, the use of this low-silicone oiling composition or oiling containing this low-silicone oiling composition in the production of PAN-based carbon fibers can effectively improve the strength, modulus, and other main mechanical properties of PAN-based carbon fibers, resulting in a significant improvement. Detailed Implementation

[0022] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0023] The first aspect of the present invention provides a low-silicone oiling composition for PAN-based carbon fibers, the low-silicone oiling composition comprising a polyamino-modified polysiloxane, a fatty acid ester, a surfactant, and an antistatic agent;

[0024] The polyamino-modified polysiloxane has the structure shown in formula (I).

[0025]

[0026] In formula (I), R is an aminoalkyl group, x is an integer from 10 to 100, and y is an integer from 5 to 20;

[0027] The fatty acid ester has the structure shown in formula (II).

[0028]

[0029] In formula (II), R1 and R2 are each independently C1-C10 hydrocarbon groups, and n1 and n2 are each independently integers from 1 to 10.

[0030] The inventors discovered that, under the action of surfactants, the low-silicone oiling composition of the present invention can effectively reduce silicon content and oiling ash content, and reduce silicon pollution in the carbon fiber production process, while also improving fiber smoothness. Furthermore, the use of this low-silicone oiling composition or oiling containing this low-silicone oiling composition in the production of PAN-based carbon fibers can effectively improve the strength, modulus, and other main mechanical properties of PAN-based carbon fibers, resulting in a significant improvement.

[0031] In this invention, it is understood that the polyamino-modified polysiloxane having the structure shown in formula (I) is a polysiloxane chain molecule with terminal amino groups at both ends. In formula (I), R comes from a group on a silane coupling agent.

[0032] In some embodiments of the present invention, the preparation method of the polyamino-modified polysiloxane with the structure shown in formula (I) includes: copolymerizing octamethylcyclotetrasiloxane, an amino-terminated end-capping agent, and an amino polysiloxane coupling agent as raw materials under the action of a catalyst, wherein the amino-terminated end-capping agent is 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane.

[0033] In this invention, there are no restrictions on the choice of catalyst. Any catalyst capable of enabling copolymerization is suitable for the preparation of polyamino-modified polysiloxanes, including but not limited to KOH.

[0034] Specifically, in some embodiments of the present invention, the preparation method of the polyamino-modified polysiloxane with the structure shown in formula (I) includes: adding octamethylcyclotetrasiloxane, an amino-terminated end-capping agent, an amino polysiloxane coupling agent, and a catalyst to a reaction vessel, introducing nitrogen gas, reacting at a certain temperature for a period of time, and then evacuating for a period of time to obtain the polyamino-modified polysiloxane with the structure shown in formula (I). Those skilled in the art can control the amount of octamethylcyclotetrasiloxane, an amino-terminated end-capping agent, an amino polysiloxane coupling agent, and a catalyst, as well as the reaction time, reaction temperature, and evacuation time, according to the required number of x and y in formula (I). Therefore, the preparation method of the polyamino-modified polysiloxane with the structure shown in formula (I) will not be elaborated further in this invention.

[0035] In some preferred embodiments of the present invention, x is an integer from 50 to 100, for example, 50, 80, or 100, and y is an integer from 5 to 15; more preferably, x is an integer from 80 to 100. By employing the aforementioned embodiments, phenomena such as entanglement with the spinning roller during carbon fiber spinning can be better prevented, thereby increasing the mechanical properties of the carbon fiber.

[0036] In this invention, the C1-C10 hydrocarbon group refers to a straight-chain hydrocarbon group or a branched hydrocarbon group with a total number of carbon atoms of 1-10. It can be a C1-C10 alkane group, such as a straight-chain alkane group or a branched alkane group of C1, C3, C5, C7, C9 or C10; or it can be a C2-C10 olefin group, such as a straight-chain olefin group or a branched olefin group of C2, C4, C6, C8 or C10.

[0037] In some preferred embodiments of the present invention, in formula (II), R1 and R2 are each independently a C1-C5 hydrocarbon group, such as -CH3, -CH=CH2, or -C(CH3)=CH2; more preferably, they are C2-C3 hydrocarbon groups. By employing the aforementioned embodiments, the synergistic effect between the components of the low-silicone oil composition can be better increased. While increasing the stability of the composition, it can also improve the maintenance of the flexibility of carbon fibers to a greater extent when using the low-silicone oil composition, and better control the retention of cohesive force.

[0038] In this invention, n1 and n2 are each independently an integer from 1 to 10, for example, 1, 2, 3, 4, 6, 8, 9, or 10; in some preferred embodiments of this invention, in formula (II), n1 and n2 are each independently an integer from 4 to 6. By employing the aforementioned embodiments, it is possible to ensure that the fatty acid ester possesses good heat resistance, emulsifying properties, and suitable viscosity, and to better achieve synergistic effects with polyamino polysiloxanes under the action of surfactants, ensuring a smooth PAN-based carbon fiber production process and resulting in carbon fibers with excellent mechanical properties.

[0039] In some preferred embodiments of the present invention, the low-silicone oiling agent composition comprises, by weight, 20-40 parts of polyamino-modified polysiloxane, 20-45 parts of fatty acid ester, 9-30 parts of surfactant, and 10-30 parts of antistatic agent. Using the aforementioned embodiments, the compositions can achieve better synergistic effects, effectively reducing silicon content and oiling agent ash content, thus reducing silicon pollution during carbon fiber production. Furthermore, using this low-silicone oiling agent composition or an oiling agent containing this low-silicone oiling agent composition during the production of PAN-based carbon fibers can effectively improve the strength, modulus, and other major mechanical properties of PAN-based carbon fibers.

[0040] In this invention, the HLB value is obtained using the Griffin formula.

[0041] In some embodiments of the present invention, the surfactant has an HLB value of 7-11, for example, 7, 8, 8.7, 8.9, 9, 9.4, 9.7, 10, or 11. The aforementioned embodiments improve the stability of the oil containing the low-silicone oil composition.

[0042] In this invention, it is understood that the HLB value of the surfactant refers to the overall HLB value of the surfactant. That is, when multiple different types of surfactants are mixed and used, the HLB value refers to the HLB value of the mixture of multiple different types of surfactants.

[0043] In some embodiments of the present invention, the surfactant comprises a polyol ester and a compound having the structure shown in formula (III).

[0044]

[0045] In formula (III), R3 is a C10-C20 alkyl group, and n3 is an integer from 4 to 10. By employing the aforementioned embodiments, the interaction between the polyamino-modified polysiloxane and fatty acid esters can be better promoted, reducing the silicon content of the low-silicone oil composition during application. This allows the low-silicone oil composition or oil containing the low-silicone oil composition to adhere more uniformly to the surface of the PAN carbon fiber precursor, thereby increasing the overall performance of the carbon fiber.

[0046] In this invention, C10-C20 alkyl refers to a monovalent straight-chain alkyl or branched alkyl with 10-20 carbon atoms; in some preferred embodiments of this invention, R3 is a C12-C16 alkyl and n3 is an integer of 6-8. The aforementioned embodiments enable better synergistic interaction between the compositions.

[0047] In some preferred embodiments of the present invention, the weight ratio of the polyol ester to the compound with the structure shown in formula (III) is 1:(0.1-10); more preferably 1:(0.2-5); and even more preferably 1:(0.5-2). By employing the foregoing embodiments, the low-silicone oil composition can be uniformly and stably distributed on the surface of the carbon fiber precursor during application.

[0048] In this invention, the HLB values ​​of the polyol ester and the compound with the structure shown in formula (III) are not limited, as long as the purpose of this invention can be achieved. In some preferred embodiments, the HLB value of the polyol ester is 4-9, for example, 4, 4.7, 5, 5.5, 6, 6.7, 8.6, or 9; in some preferred embodiments, the HLB value of the compound with the structure shown in formula (III) is 8-13, for example, 8, 9, 10.7, 11.1, 12, 12.3, or 13. Using the aforementioned embodiments, the synergistic effect between the components in the low-silicone oil composition can be better increased.

[0049] In this invention, the type of polyol ester is not limited. Any polyol ester that can achieve the purpose of this invention is applicable to the system of this invention. In some embodiments, the polyol ester includes one or more of the following: sorbitan monostearate, sorbitan monopalmitate, polyethylene glycol (8) monolaurate, dehydrated sorbitan monolaurate, dehydrated sorbitan tristearate, polyethylene glycol (32) distearate, trimethylolpropane monoacrylate didecanoate, and dipentaerythritol monoacrylate pentadecanoate.

[0050] In this invention, the advantages of the invention are illustrated by dehydrated sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate in the embodiments of the invention, but the invention is not limited thereto.

[0051] In some preferred embodiments of the present invention, the aminoalkyl group is selected from -C3H6NH2, -C3H6NHC2H4NH2, or -C3H6NC2H6. By employing the aforementioned embodiments, the ash content of the low-silicone oiling composition can be reduced during application, silicon contamination during carbon fiber production can be decreased, and the mechanical properties of PAN-based fibers can be improved.

[0052] In this invention, it is understood that -C3H6NH2, -C3H6NHC2H4NH2, or -C3H6NC2H6 come from different amino polysiloxane coupling agents. For example, when the aminoalkyl group is -C3H6NH2, the amino polysiloxane coupling agent used to prepare the polyamino modified polysiloxane is γ-aminopropylmethyldiethoxysilane coupling agent; when the aminoalkyl group is -C3H6NHC2H4NH2, the amino polysiloxane coupling agent used to prepare the polyamino modified polysiloxane is N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane; and when the aminoalkyl group is -C3H6NC2H6, the amino polysiloxane coupling agent used to prepare the polyamino modified polysiloxane is N,N-dimethyl-3-aminopropylmethyldimethoxysilane.

[0053] In this invention, the type of antistatic agent is not limited. Any antistatic agent that can achieve the purpose of this invention is applicable to the system of this invention. In some embodiments, the antistatic agent is selected from one or more of stearoyltrimethylammonium chloride, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, (3-lauramidopropyltrimethylammonium) methyl sulfate and dodecyl hydroxypropyl dihydroxyethyl methyl ammonium sulfate.

[0054] In this invention, dodecyl hydroxypropyl dihydroxyethyl methyl ammonium sulfate and octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are used as examples to illustrate the advantages of this invention, but this invention is not limited thereto.

[0055] In this invention, the low-silicone oil composition has good compatibility with each other and may also contain other components commonly used in the art. In some preferred embodiments, in order to further increase the stability of the low-silicone oil composition liquid containing the low-silicone oil composition, the low-silicone oil composition further includes 0.01-0.1 parts by weight of a pH adjuster.

[0056] In this invention, the type of pH adjuster is not limited. In some embodiments, the pH adjuster is an acid, including but not limited to one or more of acetic acid, sulfuric acid, oxalic acid and hydrochloric acid.

[0057] A second aspect of the present invention provides an oil-based liquid composition comprising a low-silicone oil composition and water.

[0058] In some preferred embodiments of the present invention, the weight content of the low-silicone oil composition in the oil mixture is 10-30%, for example, 10%, 20% or 30%.

[0059] In some preferred embodiments of the present invention, the average particle size of the oil-based liquid mixture is 180-200 nm, for example, 180 nm, 185 nm, 190 nm, 195 nm or 200 nm.

[0060] In some preferred embodiments of the present invention, the silicon content in the oil mixture is 1.2-1.6%, for example 1.2%, 1.3%, 1.4%, 1.5% or 1.6%.

[0061] In this invention, the preparation process of the oil-based liquid is not particularly limited; it is sufficient to mix the low-silicone oil composition with water until homogeneous, that is, to mix each component of the low-silicone oil composition with water until homogeneous. The mixing can be performed by first mixing the components of the low-silicone oil composition, then slowly adding water over a certain period of time, followed by stirring and shearing; alternatively, water can be added during the mixing process of the components of the low-silicone oil composition.

[0062] The slow addition of water within a certain period of time refers to the continuous or intermittent addition of water within a certain period of time, as long as the water is added completely within that period of time. Those skilled in the art can add water slowly according to the degree of mixing, but this invention will not elaborate on this further.

[0063] In this invention, there are no restrictions on other mixing conditions during the preparation of the oil-based liquid mixture. For example, mixing can be carried out under heating, ultrasonic, or stirring-shear conditions, as long as it improves the uniformity of the oil-based liquid mixture. In the preparation method of this invention, the mixing is preferably carried out at 40-60°C and normal pressure, with a preferred stirring rate of 100-500 r / min and a shear rate of 1000-10000 r / min.

[0064] A third aspect of the present invention provides the application of the above-mentioned low-silicone oiling composition or oiling liquid in the production of PAN-based carbon fiber.

[0065] In this invention, there are no particular limitations on the application conditions of the oiling agent combination liquid. Those skilled in the art can use it as needed when it is used in the production of PAN-based carbon fiber, for example, by diluting it with water to the required mass concentration, generally 1-3%, and using a two-stage oiling process.

[0066] The present invention will be described in detail below through embodiments. In the following embodiments,

[0067] The test methods involved in the following embodiments and comparative examples are as follows:

[0068] Dilute the oil-based combination solution with water to a mass concentration of 2% for later use;

[0069] Production of PAN-based carbon fiber: Washed polyacrylonitrile precursor fibers are first oiled using a combination of oiling agents at a concentration of 2% at room temperature (25°C). Excess oil is extruded by extrusion rollers and then dried and densified at 75°C for 40 seconds. A second oiling process is then performed, also using a combination of oiling agents at a concentration of 2% at room temperature. The precursor fibers from the second oiling process are then extruded again and dried and densified at 120°C for 40 seconds. The resulting fibers are then steam-drawn at a pressure of 0.2 MPa and a draw ratio of 2. The fibers are then steam-heat-set and finally wound to obtain high-performance polyacrylonitrile precursor fibers. Finally, the fibers are heat-stabilized in an air-atmosphere furnace at 250°C for 60 minutes, with a total draw of 2%, yielding heat-stabilized fibers. The obtained heat-stabilized fibers were subjected to low-temperature carbonization and high-temperature carbonization treatments in nitrogen. The low-temperature carbonization temperature was 600℃, the heat treatment time was 4 min, and the stretching was 3%. The high-temperature carbonization temperature was 1500℃, the heat treatment time was 2 min, and the stretching was -3%, to obtain polyacrylonitrile (PAN) based carbon fibers.

[0070] 1. Stability time test of oil-based liquid mixture

[0071] Test method: Static stability was determined at 25℃. The oil-based mixture was stirred for 1 hour to ensure homogeneity, then allowed to stand for 1 hour, and the time required for the emulsion to separate into layers was observed. The longer the time required for separation, the more stable the emulsion.

[0072] 2. Average particle size test of oil-based liquid mixture

[0073] The determination was performed using a Mastersizer 2000 laser particle size analyzer (UK). Open the file by selecting "File" in the initial interface menu. Then, replace the deionized water in the beaker located on the lower left of the accessory, filling it to approximately 800 mL. Press the green button on the front of the accessory to start the pump. At this point, select "Manual (M)" under "Measurement" in the menu bar. You can observe the background of the instrument's automatic testing. If the background reading is less than 80 (ideally less than 40), the sample cell is considered clean (otherwise, replace the water in the beaker and repeatedly clean the sample cell). In the measurement display interface, select "Document" in the menu bar, enter the sample information, set the file name, and select "Water" as the dispersant. Press "Start" in the menu bar. The instrument will automatically detect the background. According to the prompts in the lower left corner of the operation interface, add the oil-based combination solution sample and ensure the instrument's solubility is between 10-20%. Click "Test Sample," and the instrument will automatically provide the results.

[0074] 3. Silicon content test of oil-based liquid mixture

[0075] X-ray fluorescence spectrometry was used for detection.

[0076] 4. Methods for determining the ash content of carbon fiber

[0077] Accurately weigh approximately 1.0000g of PAN-based carbon fiber into a crucible, place it in a muffle furnace at 750℃ for 4 hours, cool and weigh, and calculate the residual ash content; Ash content = mass of PAN-based carbon fiber after calcination / mass of PAN-based carbon fiber before calcination * 100%.

[0078] 5. Mechanical property testing of PAN-based carbon fiber

[0079] The carbon fiber strength and carbon fiber modulus of PAN-based carbon fiber were determined according to the national standard GB-T3362-2005.

[0080] In the following examples, the structure of the polyamino-modified polysiloxane is as follows:

[0081]

[0082] The structure of fatty acid esters is as follows:

[0083]

[0084] The structure of the compound represented by formula (III) is as follows:

[0085]

[0086] Example 1

[0087] Based on 100 parts by weight, 30 parts of polyamino-modified polysiloxane (R is -C3H6NHC2H4NH2, x is 80, y is 10), 30 parts of fatty acid ester (R1 is -CH=CH2, R2 is -CH=CH2, n1 is 4, n2 is 4; the fatty acid ester name is bisphenol A polyoxyethylene ether (4) diacrylate, abbreviated as EO4-BPADA), and a compound with the structure shown in formula (III) (R3 is -C 12 H 25 A low-silicone oil composition consisting of 15 parts of a linear chain (n3 = 6, abbreviated as C12E6, HLB value 10.7), 15 parts of a polyol ester (sorbitan monopalmitate, brand name Span-40, HLB value 6.7), 9.9 parts of an antistatic agent (dodecyl hydroxypropyl dihydroxyethyl methyl ammonium sulfate, abbreviated as SH-105), and 0.1 parts of a pH adjuster (acetic acid) was stirred thoroughly at 50°C for 3 hours. During stirring, the required mass of water was slowly added at a stirring rate of 300 r / min. After the water was added, the mixture was stirred and sheared thoroughly for 3 hours at a shear rate of 5000 r / min to ensure uniform mixing of the low-silicone oil composition with the water. Finally, an oil composition liquid with a low-silicone oil composition content of 20 wt% was prepared.

[0088] Among them, the HLB value of the polyol ester as a surfactant after being mixed with the compound with the structure shown in formula (III) is 8.7.

[0089] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0090] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0091] Example 2

[0092] The method according to Example 1 differs in that,

[0093] Fatty acid ester (R1 is -C(CH3)=CH2, R2 is -C(CH3)=CH2, n1 is 6, n2 is 6; the fatty acid ester name is bisphenol A polyoxyethylene ether (6) dimethacrylate).

[0094] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0095] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0096] Example 3

[0097] The method according to Example 1 differs in that,

[0098] Polyamino-modified polysiloxane (R = -C3H6NH2, x = 100, y = 10).

[0099] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0100] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0101] Example 4

[0102] The method according to Example 1 differs in that,

[0103] Compounds with the structure shown in formula (III) (R3 is -C) 16 H33 Straight chain, n3 is 8, abbreviated as C16E8, HLB value is 11.1);

[0104] Among them, the HLB value of the polyol ester mixed with the compound with the structure shown in formula (III) as a surfactant is 8.9.

[0105] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0106] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0107] Example 5

[0108] The method according to Example 1 differs in that,

[0109] Polyol ester (sorbitan monolaurate, brand name Span-20, HLB value 8.6)

[0110] Among them, the HLB value of the polyol ester as a surfactant after being mixed with the compound with the structure shown in formula (III) is 9.7.

[0111] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0112] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0113] Example 6

[0114] The method according to Example 1 differs in that,

[0115] Polyol ester (sorbitan monostearate, grade Span-60, HLB value 4.7)

[0116] Among them, the HLB value of the polyol ester as a surfactant after being mixed with the compound with the structure shown in formula (III) is 7.9.

[0117] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0118] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0119] Example 7

[0120] The method according to Example 1 differs in that,

[0121] Antistatic agent (octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, abbreviated as SN).

[0122] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0123] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0124] Example 8

[0125] The method according to Example 1 differs in that,

[0126] The low-silicone oil composition comprises, by weight, 25 parts of polyamino-modified polysiloxane, 45 parts of fatty acid ester, 10 parts of compound with the structure shown in formula (III), 10 parts of polyol ester, 9.9 parts of antistatic agent, and 0.1 parts of pH adjuster.

[0127] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0128] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0129] Example 9

[0130] The method according to Example 1 differs in that,

[0131] The low-silicone oil composition comprises, by weight, 30 parts of polyamino-modified polysiloxane, 30 parts of fatty acid ester, 20 parts of compound with the structure shown in formula (III), 10 parts of polyol ester, 9.9 parts of antistatic agent, and 0.1 parts of pH adjuster.

[0132] Among them, the HLB value of the polyol ester as a surfactant after being mixed with the compound with the structure shown in formula (III) is 9.4.

[0133] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0134] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0135] Example 10

[0136] The method according to Example 1 differs in that,

[0137] The low-silicone oil composition comprises, by weight, 20 parts of polyamino-modified polysiloxane, 25 parts of fatty acid ester, 10 parts of compound with the structure shown in formula (III), 15 parts of polyol ester, 29.9 parts of antistatic agent, and 0.1 parts of pH adjuster.

[0138] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0139] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0140] Example 11

[0141] The method according to Example 1 differs in that,

[0142] The low-silicone oil composition comprises, by weight, 30 parts of polyamino-modified polysiloxane, 30 parts of fatty acid ester, 0.6 parts of compound with the structure shown in formula (III), 29.4 parts of polyol ester, 9.9 parts of antistatic agent, and 0.1 parts of pH adjuster.

[0143] Among them, the HLB value of the polyol ester as a surfactant after being mixed with the compound with the structure shown in formula (III) is 6.78.

[0144] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment exhibit fuzziness and adhesion.

[0145] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0146] Example 12

[0147] The method according to Example 1 differs in that,

[0148] The low-silicone oil composition comprises, by weight, 30 parts of polyamino-modified polysiloxane, 30 parts of fatty acid ester, 29.4 parts of compound with the structure shown in formula (III), 0.6 parts of polyol ester, 9.9 parts of antistatic agent, and 0.1 parts of pH adjuster.

[0149] The HLB value of the polyol ester mixed with the compound with the structure shown in formula (III) as a surfactant is 10.62.

[0150] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment exhibit fuzziness and adhesion.

[0151] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0152] Example 13

[0153] The method of Example 1 is followed, except that compounds with the structure shown in Formula (III) are not used;

[0154] Based on 100 parts by weight, 15 parts of polyol ester A (polyoxyethylene sorbitan tristearate, brand name Tween-65, HLB value 10.5) and 15 parts of polyol ester B (diethylene glycol monolaurate, HLB value 6.5) were used as surfactants.

[0155] Among them, the HLB value of the mixture of polyol ester A and polyol ester B as a surfactant is 8.5.

[0156] The spinning process of producing PAN-based carbon fiber using the oil-based liquid mixture of this embodiment has issues with fuzzing and adhesion.

[0157] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0158] Example 14

[0159] The method according to Example 1 differs in that,

[0160] The polyol ester (sorbitan monopalmitate, brand name Span-40, HLB value 6.7) was replaced with C12E6, i.e., the weight of C12E6 was 30 parts; C12E6 as a surfactant has an HLB value of 10.7.

[0161] The spinning process of producing PAN-based carbon fiber using the oil-based liquid mixture of this embodiment has issues with fuzzing and adhesion.

[0162] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0163] Example 15

[0164] The method according to Example 1 differs in that,

[0165] C12E6 was replaced with polyol ester, i.e., the weight of polyol ester was 30 parts; the HLB value of polyol ester as a surfactant was 6.7.

[0166] The spinning process of producing PAN-based carbon fiber using the oil-based liquid mixture of this embodiment has issues with fuzzing and adhesion.

[0167] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0168] Comparative Example 1

[0169] Based on 100 parts by weight, 20 parts of bisamine-modified polydimethylsiloxane KF861 (viscosity 3500 cp, amino equivalent 2000), 5 parts of bisamine-modified polydimethylsiloxane KF8002 (viscosity 1100 cp, amino equivalent 1700), 25 parts of monoamine-modified polydimethylsiloxane KF864 (viscosity 1700 cp, amino equivalent 3800), 20 parts of polyether-modified polydimethylsiloxane KF353 (viscosity 430 cp, HLB=10), and 10 parts of epoxy-modified polydimethylsiloxane KF... An oil composition consisting of 10 parts of 102 (viscosity 4000cp, epoxy equivalent 3600), 10 parts of antistatic agent (dialkylhydroxypropyl dihydroxyethylmethyl methyl ammonium sulfate, abbreviated as SH-105), 6 parts of isomeric tridecyl alcohol polyoxyethylene ether 6 (abbreviated as E-1306, HLB value 11.4), and 4 parts of alkylphenol polyoxyethylene ether 4 (abbreviated as OP-4, HLB value 8.6) was stirred evenly at room temperature. Deionized water was slowly added and mixed evenly to finally prepare an oil composition liquid with an oil composition content of 20wt%.

[0170] Among them, the HLB value of the surfactant when combined with isomeric tridecyl alcohol polyoxyethylene ether 6 and alkylphenol polyoxyethylene ether 4 is 10.28.

[0171] The PAN-based carbon fibers produced using the oil-based liquid mixture of this embodiment are smooth, soft, and free of fuzz and adhesion.

[0172] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0173] Comparative Example 2

[0174] The method according to Example 1 differs in that,

[0175] The polyamino-modified polydimethylsiloxane of Example 1 was replaced with diamino-modified polydimethylsiloxane KF861 (viscosity 3500cp, amino equivalent 2000).

[0176] The spinning process of producing PAN-based carbon fiber using the oil-based liquid mixture of this embodiment exhibits significant fuzzing and adhesion.

[0177] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0178] Comparative Example 3

[0179] The method according to Example 1 differs in that,

[0180] Based on 100 parts by weight, 15 parts of bis(amino)-modified polydimethylsiloxane KF861 (viscosity 3500 cp, amino equivalent 2000) and 15 parts of mono(amino)-modified polydimethylsiloxane KF864 (viscosity 1700 cp, amino equivalent 3800) were used to replace the poly(amino)-modified polysiloxane in Example 1, with all other conditions remaining unchanged.

[0181] The spinning process of producing PAN-based carbon fiber using the oil-based liquid mixture of this embodiment has issues with fuzzing and adhesion.

[0182] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0183] Comparative Example 4

[0184] The method according to Example 1 differs in that,

[0185] Polyamino-modified polysiloxane (R is C3H6NHC2H4NH2, x is 200, y is 20).

[0186] The spinning process of producing PAN-based carbon fiber using the oil-based liquid mixture of this embodiment has issues with fuzzing and adhesion.

[0187] Table 1 shows the stabilization time, particle size, and silicon content of the oil-based liquid mixture in this embodiment, as well as the carbon fiber ash content, carbon fiber strength, and carbon fiber modulus of the PAN-based carbon fiber produced using the oil-based liquid mixture in this embodiment.

[0188] Table 1

[0189]

[0190]

[0191] As can be seen from the results in Table 1, under the action of surfactant, the oil agent combination liquid of the present invention has a moderate oil agent particle size and good stability. The use of the polyamino-modified polysiloxane and fatty acid ester of the present invention can make the spinning of PAN-based carbon fiber smoother and increase the mechanical properties of carbon fiber. The synergistic effect between the compositions can not only effectively reduce the silicon content and increase the stability of the oil agent, but also reduce the ash content of the oil agent and reduce silicon pollution in the carbon fiber production process.

[0192] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A low-silicone oil composition for PAN-based carbon fibers, characterized in that, The low-silicone oil composition includes polyamino-modified polysiloxane, fatty acid ester, surfactant, and antistatic agent; The polyamino-modified polysiloxane has the structure shown in formula (I). Formula (I); In formula (I), R is an aminoalkyl group, x is an integer from 10 to 100, and y is an integer from 5 to 20; The fatty acid ester has the structure shown in formula (II). Formula (II); In formula (II), R1 and R2 are each independently C1-C10 hydrocarbon groups, and n1 and n2 are each independently integers from 1 to 10; The low-silicone oil composition comprises, by weight, 20-40 parts of polyamino-modified polysiloxane, 20-45 parts of fatty acid ester, 10-30 parts of surfactant and 9-30 parts of antistatic agent; The surfactant has an HLB value of 7-9.7; The surfactants include polyol esters and compounds having the structure shown in formula (III). Formula (III); In formula (III), R3 is a C10-C20 alkyl group, and n3 is an integer from 4 to 10; The weight ratio of the polyol ester to the compound with the structure shown in formula (III) is 1:(0.1-10).

2. The low-silicone oil composition according to claim 1, wherein, In equation (I), x is an integer from 50 to 100, and y is an integer from 5 to 15; and / or In formula (II), R1 and R2 are each independently a C1-C5 hydrocarbon group; In equation (II), n1 and n2 are each an integer between 4 and 6.

3. The low-silicone oil composition according to claim 2, wherein, In equation (I), x is an integer between 80 and 100, and y is an integer between 5 and 15.

4. The low-silicone oil composition according to claim 2, wherein, R1 and R2 are each independently C2-C3 hydrocarbon groups.

5. The low-silicone oil composition according to claim 1, wherein, In formula (III), R3 is a C12-C16 alkyl group, and n3 is an integer from 6 to 8.

6. The low-silicone oil composition according to claim 1, wherein, The weight ratio of the polyol ester to the compound with the structure shown in formula (III) is 1:(0.2-5).

7. The low-silicone oil composition according to claim 1, wherein, The weight ratio of the polyol ester and the compound with the structure shown in formula (III) is 1:(0.5-2); and / or The HLB value of the polyol ester is 4-9; and / or The HLB values ​​of compounds with the structure shown in formula (III) are 8-13.

8. The low-silicone oil composition according to claim 1, wherein, The polyol esters include one or more of sorbitan monostearate, sorbitan monopalmitate, polyethylene glycol (8) monolaurate, dehydrated sorbitan monolaurate, dehydrated sorbitan tristearate, polyethylene glycol (32) distearate, trimethylolpropane monoacrylate didecanoate, and dipentaerythritol monoacrylate pentadecanoate; and / or The aminoalkyl group is selected from -C3H6NH2, -C3H6NHC2H4NH2 or -C3H6NC2H6.

9. The low-silicone oil composition according to any one of claims 1-8, wherein, The antistatic agent is selected from one or more of stearoyltrimethylammonium chloride, octadecyl dimethylhydroxyethyl quaternary ammonium nitrate, (3-lauramidopropyltrimethylammonium) methyl sulfate, and dodecyl hydroxypropyl dihydroxyethyl methyl ammonium sulfate.

10. The low-silicone oil composition according to any one of claims 1-8, wherein, The low-silicone oil composition also includes 0.01-0.1 parts by weight of a pH adjuster.

11. The low-silicone oil composition according to claim 10, wherein, The pH adjuster is an acid.

12. The low-silicone oil composition according to claim 11, wherein, The acid includes one or more of acetic acid, sulfuric acid, oxalic acid, and hydrochloric acid.

13. An oiling composition comprising the low-silicone oiling composition according to any one of claims 1-12 and water.

14. The oil-based liquid mixture according to claim 13, wherein, In the oil-based liquid mixture, the low-silicone oil composition has a weight content of 10-30%; and / or The average particle size of the oil-based liquid mixture is 180-200 nm; and / or X-ray fluorescence spectrometry analysis showed that the silicon content in the oil-based mixture was 1.2-1.6% by mass.

15. The use of the low-silicone oiling composition according to any one of claims 1-2 or the oiling liquid according to claim 13 or 14 in the production of PAN-based carbon fiber.

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