Carbon fiber oiling agent having high heat resistance, and preparation method therefor

Abstract

Provided in the present disclosure are a carbon fiber oiling agent having high heat resistance, and a preparation method therefor. The carbon fiber oiling agent having high heat resistance is composed of the following components in percentage by weight: 25% to 35% of modified silicone oil, 5% to 10% of a surfactant, 55% to 70% of pure water, and 1% to 3% of other auxiliaries, wherein on the basis of a total weight being 100%, the modified silicone oil is composed of 50% to 70% of amino modified silicone oil, 20% to 30% of polyether modified silicone oil, and 10% to 20% of phenyl modified silicone oil.

Description

High heat-resistant carbon fiber oil and preparation method thereof

[0001] The present disclosure is based on the Chinese patent application with application number 202310866559.1, application date July 14, 2023, and application name “High heat-resistant carbon fiber oil agent and preparation method thereof”, and claims the priority of the Chinese patent application. The entire content of the Chinese patent application is hereby introduced into the present disclosure as a reference. Technical Field

[0002] The present disclosure relates to, but is not limited to, a high-heat-resistant carbon fiber oil and a preparation method thereof. Background Art

[0003] Polyacrylonitrile (PAN)-based carbon fibers are widely used in defense, aerospace, wind power, and other fields due to their lightweight, high specific strength, high specific modulus, high temperature resistance, and corrosion resistance. Carbon fiber lubricants are essential additives in the production process, effectively protecting the fibers during spinning, pre-oxidation, and low-temperature carbonization. High-quality lubricants are crucial for producing high-quality carbon fibers.

[0004] Currently, most carbon fiber oil development focuses on the spinning process, but has little protection for the subsequent carbonization of the raw yarn. Therefore, it is particularly important to design and develop an oil that matches both the spinning process and the carbonization process.

[0005] Summary of the Invention

[0006] The following is an overview of the subject matter described in detail in this disclosure. This overview is not intended to limit the scope of the claims.

[0007] The present disclosure provides a high heat-resistant carbon fiber oil and a preparation method thereof.

[0008] A first aspect of the present disclosure provides a high heat-resistant carbon fiber oil, which is composed of the following components by weight:

[0009] 25% to 35% modified silicone oil, 5% to 10% surfactant, 55% to 70% pure water, and 1% to 3% other additives; the modified silicone oil, based on a total weight of 100%, is composed of 50% to 70% amino-modified silicone oil, 20% to 30% polyether-modified silicone oil, and 10% to 20% phenyl-modified silicone oil.

[0010] According to some embodiments of the present disclosure, the high heat-resistant carbon fiber oil agent is composed of the following ingredients by weight: 25% to 35% modified silicone oil, 5% surfactant, 58% to 68% pure water, and 2% other additives.

[0011] According to some embodiments of the present disclosure, the surfactant is one or more of C10-C13 isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether; the other auxiliary agents are antistatic agents, defoaming agents and organic solvents, the antistatic agent is polyethylene glycol fatty acid ester, polyoxyethylene laurate, dodecyltrimethylammonium chloride or sorbitan fatty acid ester, the defoaming agent is fatty alcohol polyoxyethylene ether, isopentanol, diisobutyl carbinol or modified polymethylsiloxane type defoaming agent, and the organic solvent is isopropyl alcohol, ethylene glycol monobutyl ether, glycerol or acetic acid.

[0012] According to some embodiments of the present disclosure, the surfactant is C13 isomeric alcohol polyoxyethylene ether.

[0013] According to some embodiments of the present disclosure, the modified silicone oil is composed of 60% to 70% amino-modified silicone oil, 20% to 25% polyether-modified silicone oil and 15% to 20% phenyl-modified silicone oil based on 100% total weight.

[0014] According to some embodiments of the present disclosure, the phenyl-modified silicone oil is a low-phenyl-modified silicone oil with a phenyl molar content of 5% to 10% or a medium-phenyl-modified silicone oil with a phenyl molar content of 20% to 25%, and its viscosity is 50 cSt to 5000 cSt.

[0015] According to some embodiments of the present disclosure, the phenyl-modified silicone oil is a low-phenyl-modified silicone oil with a phenyl molar content of 5% to 10%, and a viscosity of 500 cSt to 2500 cSt.

[0016] According to some embodiments of the present disclosure, the phenyl-modified silicone oil is selected from one or more of vinyl-terminated phenyl silicone oil, phenyl hydrogen-containing silicone oil and hydroxyl-terminated phenyl silicone oil.

[0017] According to some embodiments of the present disclosure, the phenyl-modified silicone oil is vinyl-terminated phenyl silicone oil or hydroxyl-terminated phenyl silicone oil.

[0018] According to some embodiments of the present disclosure, the amino-modified silicone oil is one or more of terminal amino-modified and quaternary ammonium-modified silicone oils, and has a molecular weight of 5000 g / mol to 50000 g / mol.

[0019] According to some embodiments of the present disclosure, the amino-modified silicone oil is a quaternized ammonium-modified silicone oil with a molecular weight of 10,000 g / mol to 30,000 g / mol.

[0020] According to some embodiments of the present disclosure, the molecular weight of the polyether-modified silicone oil is 1000 g / mol to 20000 g / mol.

[0021] According to some embodiments of the present disclosure, the molecular weight of the polyether-modified silicone oil is 5000 g / mol to 10000 g / mol.

[0022] The second aspect of the present disclosure provides a method for preparing the above-mentioned high heat-resistant carbon fiber oil, which is as follows:

[0023] According to the proportion, amino-modified silicone oil, polyether-modified silicone oil, phenyl-modified silicone oil and surfactant are stirred and mixed, and a preset percentage of pure water is added while stirring until the phase transition is completed. Then, the remaining pure water and other additives are added. After standing, a carbon fiber oil with a pH of 4 to 6 and a solid content of 30% to 40% is obtained.

[0024] Compared with the prior art, the present disclosure has the following advantages:

[0025] The high-heat-resistant carbon fiber oil provided by the embodiments of the present disclosure introduces phenyl-modified silicone oil into the carbon fiber oil system with amino-polyether modified silicone oil as the main component, which can improve the heat resistance of the oil and effectively solve the embrittlement or breakage problem of silicone oil after 300°C in the pre-oxidation stage, so that the fiber can still play a good protective role in the late pre-oxidation and low-temperature carbonization process. At the same time, it also solves the problem of amino-polyether silicone oil sticking to the roller during the raw silk production process. In addition, the high-heat-resistant carbon fiber oil has good spinning and carbonization processability, and can meet the preparation needs of high-performance carbon fibers in different processes.

[0026] Still other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The accompanying drawings, which are incorporated into and constitute a part of the specification, illustrate embodiments of the present disclosure and, together with the description, are used to explain the principles of the embodiments of the present disclosure. In these drawings, similar reference numerals are used to represent similar elements. The drawings described below are some embodiments of the present disclosure, not all embodiments. For those skilled in the art, other drawings can be derived from these drawings without inventive effort.

[0028] FIG1 is a thermogravimetric curve of the oil prepared in Example 1 and Comparative Example 1 under a simulated carbonization atmosphere according to an exemplary embodiment. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present disclosure to clearly and completely describe the technical solutions in the disclosed embodiments. Obviously, the described embodiments are part of the embodiments of the present disclosure, rather than all of the embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by those skilled in the art without making creative work are within the scope of protection of the present disclosure. It should be noted that, in the absence of conflict, the embodiments in the present disclosure and the features in the embodiments can be arbitrarily combined with each other.

[0030] In the following examples, the raw materials and reagents used can be purchased commercially.

[0031] Example 1

[0032] Take 15 parts by weight of quaternary ammonium modified silicone oil with a molecular weight of 20,000 g / mol, 9 parts by weight of polyether modified silicone oil with a molecular weight of 5,000 g / mol, 6 parts by weight of vinyl-terminated phenyl silicone oil with a phenyl molar content of 5% and a viscosity of 500 cSt, and 5 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether, and stir evenly until fully mixed. Add an appropriate amount of pure water in batches under high-speed stirring until the phase inversion is completed, and then add the remaining pure water, antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid. The total weight of pure water is 63 parts by weight, and the antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid are 2 parts by weight. After standing for 10 minutes, a carbon fiber oil with a pH of 4 to 6 and a solid content of about 35% is obtained.

[0033] Example 2

[0034] Take 17.5 parts by weight of amino-modified silicone oil with a molecular weight of 50,000 g / mol, 5 parts by weight of polyether-modified silicone oil with a molecular weight of 1,000 g / mol, 2.5 parts by weight of hydroxyl-terminated phenyl silicone oil with a phenyl molar content of 5% and a viscosity of 2,500 cSt, and 5 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether, and stir evenly until fully mixed. Add an appropriate amount of pure water in batches under high-speed stirring until the phase transition is complete, and then add the remaining pure water, antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid. The total weight of pure water is 68 parts by weight, and the antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid are 2 parts by weight in total. After standing for 10 minutes, a carbon fiber oil with a pH of 4 to 6 and a solid content of about 30% is obtained.

[0035] Example 3

[0036] Take 21 parts by weight of quaternary ammonium modified silicone oil with a molecular weight of 50,000 g / mol, 8 parts by weight of polyether modified silicone oil with a molecular weight of 5,000 g / mol, 6 parts by weight of vinyl-terminated phenyl silicone oil with a phenyl molar content of 10% and a viscosity of 2,500 cSt, and 5 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether and stir evenly until fully mixed. Add an appropriate amount of pure water in batches under high-speed stirring until the phase transition is complete, and then add the remaining pure water, antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid. The total weight of pure water is 58 parts by weight, and the antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid are 2 parts by weight. After standing for 10 minutes, a carbon fiber oil with a pH of 4 to 6 and a solid content of about 40% is obtained.

[0037] Example 4

[0038] Take 15 parts by weight of quaternary ammonium modified silicone oil with a molecular weight of 20,000 g / mol, 9 parts by weight of polyether modified silicone oil with a molecular weight of 5,000 g / mol, 6 parts by weight of vinyl-terminated phenyl silicone oil with a phenyl molar content of 20% and a viscosity of 500 cSt, and 5 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether, and stir evenly until fully mixed. Add an appropriate amount of pure water in batches under high-speed stirring until the phase transition is completed, and then add the remaining pure water, antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid. The total weight of pure water is 62 parts by weight, and the antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid are 2 parts by weight. After standing for 10 minutes, a carbon fiber oil with a pH of 4 to 6 and a solid content of about 35% is obtained.

[0039] Example 5

[0040] Take 15 parts by weight of quaternary ammonium modified silicone oil with a molecular weight of 20,000 g / mol, 9 parts by weight of polyether modified silicone oil with a molecular weight of 5,000 g / mol, 6 parts by weight of vinyl-terminated phenyl silicone oil with a phenyl molar content of 25% and a viscosity of 2,500 cSt, and 5 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether and stir evenly until fully mixed. Add an appropriate amount of pure water in batches under high-speed stirring until the phase transition is complete, and then add the remaining pure water, antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid. The total weight of pure water is 62 parts by weight, and the antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid are 2 parts by weight. After standing for 10 minutes, a carbon fiber oil with a pH of 4 to 6 and a solid content of about 35% is obtained.

[0041] Comparative Example 1

[0042] Take 25 parts by weight of quaternary ammonium modified silicone oil with a molecular weight of 20,000 g / mol, 5 parts by weight of polyether modified silicone oil with a molecular weight of 5,000 g / mol, and 5 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether, stir evenly until fully mixed, add appropriate amount of pure water in batches under high-speed stirring until the phase inversion is completed, and then add the remaining pure water, antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid. The total weight of pure water is 63 parts by weight, and the antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid are 2 parts by weight in total. After standing for 10 minutes, a carbon fiber oil with a pH of 4 to 6 and a solid content of about 35% is obtained.

[0043] Comparative Example 2

[0044] Take 5 parts by weight of quaternary ammonium modified silicone oil with a molecular weight of 20,000 g / mol, 5 parts by weight of polyether modified silicone oil with a molecular weight of 5,000 g / mol, 20 parts by weight of vinyl-terminated phenyl silicone oil with a phenyl molar content of 5% and a viscosity of 500 cSt, and 5 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether, and stir evenly until fully mixed. Add an appropriate amount of pure water in batches under high-speed stirring until the phase transition is complete, and then add the remaining pure water, antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid. The total weight of pure water is 63 parts by weight, and the antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid are 2 parts by weight in total. After standing for 10 minutes, a carbon fiber oil with a pH of 4 to 6 and a solid content of about 40% is obtained.

[0045] Comparative Example 3

[0046] Take 20 parts by weight of quaternary ammonium modified silicone oil with a molecular weight of 20,000 g / mol, 5 parts by weight of polyether modified silicone oil with a molecular weight of 5,000 g / mol, 5 parts by weight of vinyl-terminated phenyl silicone oil with a phenyl molar content of 40% and a viscosity of 500 cSt, and 5 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether, and stir evenly until fully mixed. Add an appropriate amount of pure water in batches under high-speed stirring until the phase transition is complete, and then add the remaining pure water and antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid. The total weight of pure water is 63 parts by weight, and the antistatic agent polyoxyethylene laurate, defoaming agent modified polymethylsiloxane and acetic acid are 2 parts by weight. After standing for 10 minutes, a carbon fiber oil with a pH of 4 to 6 and a solid content of about 35% is obtained.

[0047] The properties of the carbon fiber oils obtained in the examples and comparative examples and the results of production line evaluation are shown in Table 1.

[0048] Table 1

[0049] The difference between the Examples and Comparative Example 1 lies in the introduction of phenyl-modified silicone oil into the modified silicone oil. The heat resistance of the oils in each Example was significantly improved, and their fiber processability and carbon filament strength were superior to those of Comparative Example 1. The difference between Examples 4 and 5 and Example 1 lies in the variation in the phenyl molar content of the phenyl-modified silicone oil. As the phenyl molar content increases, the oil stability decreases, and the fiber processability and carbon filament strength begin to deteriorate. Comparative Examples 2 and 3 differ from Example 1 in their high phenyl-modified silicone oil content and high phenyl molar content, respectively. The oil emulsions in these Examples exhibited extremely poor stability. Although the precursor was successfully prepared in the spinning stage, frequent fiber breakage occurred during the carbonization stage.

[0050] In summary, the exemplary embodiments of the present disclosure introduce phenyl-modified silicone oil into a carbon fiber oil system primarily composed of amino-polyether modified silicone oil, thereby improving the oil's heat resistance and ensuring better protection of the fiber during subsequent oxidation and carbonization processes. This also addresses the roller-sticking issue associated with the original silicone oil system. The disclosed embodiments provide a highly heat-resistant carbon fiber oil, and by optimizing the content and molar content of the phenyl-modified silicone oil, the ash content of the carbon fiber is kept below control standards, allowing the carbon fiber to continue to play a significant role in the subsequent use of the composite material.

[0051] The various embodiments or implementation methods in this specification are described in a progressive manner. Each embodiment focuses on the differences from other embodiments, and the same or similar parts between the various embodiments can be referenced to each other.

[0052] In the description of this specification, reference to the terms "embodiment", "exemplary embodiment", "some embodiments", "illustrative embodiment", "example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present disclosure.

[0053] In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any suitable manner in any one or more embodiments or examples.

[0054] In the description of the present disclosure, it should be noted that the terms "center", "up", "down", "left", "right", "vertical", "horizontal", "inside", "outside", etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings. They are only for the convenience of describing the present disclosure and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, they cannot be understood as limitations on the present disclosure.

[0055] It is to be understood that the terms "first", "second", etc. used in the present disclosure can be used to describe various structures in the present disclosure, but these structures are not limited by these terms. These terms are only used to distinguish a first structure from another structure.

[0056] In one or more of the accompanying drawings, identical elements are denoted by similar reference numerals. For clarity, many parts in the accompanying drawings are not drawn to scale. In addition, certain well-known parts may not be shown. For simplicity, a structure obtained after several steps may be depicted in a single figure. Many specific details of the present disclosure, such as device structure, materials, dimensions, processing techniques, and technologies, are described below to facilitate a clearer understanding of the present disclosure. However, as will be appreciated by those skilled in the art, the present disclosure may be practiced without following these specific details.

[0057] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present disclosure, rather than to limit them. Although the present disclosure has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present disclosure. Industrial Applicability

[0058] The high-heat-resistant carbon fiber oil provided by the embodiments of the present disclosure introduces phenyl-modified silicone oil into the carbon fiber oil system with amino-polyether modified silicone oil as the main component, which can improve the heat resistance of the oil and effectively solve the embrittlement or breakage problem of silicone oil after 300°C in the pre-oxidation stage, so that the fiber can still play a good protective role in the late pre-oxidation and low-temperature carbonization process. At the same time, it also solves the problem of amino-polyether silicone oil sticking to the roller during the raw silk production process. In addition, the high-heat-resistant carbon fiber oil has good spinning and carbonization processability, and can meet the preparation needs of high-performance carbon fibers in different processes.

Claims

1. High heat-resistant carbon fiber oil, wherein: By weight percentage, it is composed of the following ingredients: 25% to 35% of modified silicone oil, 5% to 10% of surfactant, 55% to 70% of pure water, and 1% to 3% of other additives; the modified silicone oil, based on a total weight of 100%, is composed of 50% to 70% of amino-modified silicone oil, 20% to 30% of polyether-modified silicone oil and 10% to 20% of phenyl-modified silicone oil.

2. The highly heat-resistant carbon fiber lubricant according to claim 1, wherein Calculated by weight percentage, it is composed of the following ingredients: 25% to 35% of modified silicone oil, 5% of surfactant, 58% to 68% of pure water, and 2% of other additives.

3. The highly heat-resistant carbon fiber oil according to claim 1, wherein The surfactant is one or more of C10-C13 isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether; the other auxiliary agents are antistatic agent, defoaming agent and organic solvent, the antistatic agent is polyethylene glycol fatty acid ester, polyoxyethylene laurate, dodecyltrimethylammonium chloride or sorbitan fatty acid ester, the defoaming agent is fatty alcohol polyoxyethylene ether, isopentanol, diisobutyl carbinol or modified polymethylsiloxane type defoaming agent, and the organic solvent is isopropanol, ethylene glycol monobutyl ether, glycerol or acetic acid.

4. The highly heat-resistant carbon fiber lubricant according to claim 1, wherein The modified silicone oil is composed of 60% to 70% amino-modified silicone oil, 20% to 25% polyether-modified silicone oil and 15% to 20% phenyl-modified silicone oil based on 100% of the total weight.

5. The highly heat-resistant carbon fiber lubricant according to claim 1, wherein The phenyl-modified silicone oil is a low-phenyl-modified silicone oil with a phenyl molar content of 5% to 10% or a medium-phenyl-modified silicone oil with a phenyl molar content of 20% to 25%, and has a viscosity of 50 cSt to 5000 cSt.

6. The highly heat-resistant carbon fiber oil according to claim 1, wherein The phenyl-modified silicone oil is a low-phenyl-modified silicone oil with a phenyl molar content of 5% to 10% and a viscosity of 500 cSt to 2500 cSt.

7. The highly heat-resistant carbon fiber lubricant according to claim 1, wherein The phenyl-modified silicone oil is selected from one or more of vinyl-terminated phenyl silicone oil, phenyl hydrogen-containing silicone oil and hydroxyl-terminated phenyl silicone oil.

8. The highly heat-resistant carbon fiber oil according to claim 1, wherein The amino-modified silicone oil is one or more of terminal amino-modified and quaternary ammonium-modified silicone oils, and has a molecular weight of 5000 g / mol to 50000 g / mol; the molecular weight of the polyether-modified silicone oil is 1000 g / mol to 20000 g / mol.

9. The highly heat-resistant carbon fiber lubricant according to claim 1, wherein The amino-modified silicone oil is a quaternary ammonium-modified silicone oil with a molecular weight of 10,000 g / mol to 30,000 g / mol; the polyether-modified silicone oil has a molecular weight of 5,000 g / mol to 10,000 g / mol.

10. The method for preparing a highly heat-resistant carbon fiber oil according to any one of claims 1 to 9, wherein: The details are as follows: According to the proportion, amino-modified silicone oil, polyether-modified silicone oil, phenyl-modified silicone oil and surfactant are stirred and mixed, and a preset percentage of pure water is added under stirring until the phase transition is completed. Then, the remaining pure water and other additives are added. After standing, a carbon fiber oil with a pH of 4 to 6 and a solid content of 30% to 40% is obtained.

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