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

Abstract

The present disclosure provides a high heat-resistant carbon fiber oil agent and a preparing method thereof. The high heat-resistant carbon fiber oil agent consists of the follow components by weight percentage: 25% to 35% of modified silicone oil, 5% to 10% of surfactant, 55% to 70% of pure water, and 1% to 3% of other auxiliaries; where 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.

Description

[0001] The present disclosure is based on and claims the priority to Chinese Patent Application No. 202310866559.1, titled "HIGH HEAT-RESISTANT CARBON FIBER OIL AGENT AND PREPARING METHOD THEREOF" and filed on July 14, 2023, which is incorporated herein by reference in its entirety.Technical Field

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

[0003] Polyacrylonitrile (PAN)-based carbon fiber is widely used in national defense and military industry, aerospace, wind power generation and other fields due to its excellent properties such as light weight, high specific strength, high specific modulus, high temperature resistance and corrosion resistance. Carbon fiber oil agent is an essential and important auxiliary agent in the production process. The carbon fiber oil agent provides effective protection for the fiber during the spinning stage, the pre-oxidation stage and the low-temperature carbonization stage. High-quality oil agent is the key to producing high-quality carbon fiber.

[0004] At present, most development of the carbon fiber oil agent focuses on the spinning process, and the protective effect on the subsequent carbonization of the precursor is weak. Therefore, it is particularly important to design and develop an oil agent that matches both the spinning processability and the carbonization processability.Summary

[0005] The following is the summary of the present disclosure. This summary is not intended to limit the protection scope defined by the claims.

[0006] The present disclosure provides a high heat-resistant carbon fiber oil agent and a preparing method thereof.

[0007] A first aspect of the present disclosure provides a high heat-resistant carbon fiber oil agent, consisting of the follow components by weight percentage: 25% to 35% of modified silicone oil, 5% to 10% of surfactant, 55% to 70% of pure water, and 1% to 3% of other auxiliaries; where 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.

[0008] According to some embodiments of the present disclosure, the high heat-resistant carbon fiber oil agent consists of the follow components by weight percentage: 25% to 35% of the modified silicone oil, 5% of the surfactant, 58% to 68% of the pure water, and 2% of the other auxiliaries.

[0009] 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 auxiliaries are antistatic agent, defoaming agent and organic solvent, the antistatic agent is polyethylene glycol fatty acid ester, polyoxyethylene laurate, dodecyl trimethyl ammonium 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.

[0010] According to some embodiments of the present disclosure, the surfactant is C13 isomeric alcohol polyoxyethylene ether.

[0011] According to some embodiments of the present disclosure, the modified silicone oil, based on the total weight of 100%, is composed of 60% to 70% of the amino-modified silicone oil, 20% to 25% of the polyether-modified silicone oil and 15% to 20% of the phenyl-modified silicone oil.

[0012] 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 a viscosity of the phenyl-modified silicon oil is 50 cSt to 5000 cSt.

[0013] 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 the phenyl-modified silicon oil is 500 cSt to 2500 cSt.

[0014] According to some embodiments of the present disclosure, the phenyl-modified silicone oil is one or more of vinyl terminated phenyl silicone oil, phenyl hydrogen-containing silicone oil or hydroxy terminated phenyl silicone oil.

[0015] According to some embodiments of the present disclosure, the phenyl-modified silicone oil is vinyl terminated phenyl silicone oil or hydroxy terminated phenyl silicone oil.

[0016] According to some embodiments of the present disclosure, the amino-modified silicone oil is one or more of terminal amino-modified silicon oil and quaternized modified silicone oil, and a molecular weight of the amino-modified silicon oil is 5000 g / mol to 50000 g / mol.

[0017] According to some embodiments of the present disclosure, the amino-modified silicone oil is quaternized modified silicone oil, a molecular weight of the amino-modified silicon oil is 10000 g / mol to 30000 g / mol.

[0018] According to some embodiments of the present disclosure, a molecular weight of the polyether-modified silicone oil is 1000 g / mol to 20000 g / mol.

[0019] According to some embodiments of the present disclosure, a molecular weight of the polyether-modified silicone oil is 5000 g / mol to 10000 g / mol.

[0020] A second aspect of the present disclosure provides a method for preparing the high heat-resistant carbon fiber oil agent according to the first aspect, including: stirring and mixing amino-modified silicone oil, polyether-modified silicone oil, phenyl-modified silicone oil and surfactant according to a proportion; adding a preset percentage of pure water under stirring, until a phase transition is completed; adding a remaining percentage of the pure water and other auxiliaries; standing to obtain the carbon fiber oil agent, where a pH of the carbon fiber oil agent is 4 to 6, and a solid content of the carbon fiber oil agent is 30% to 40%.

[0021] Compared with the prior art, the present disclosure has the following advantages: The high heat-resistant carbon fiber oil agent provided in the embodiments of the present disclosure introduces phenyl-modified silicone oil into the carbon fiber oil agent system with amino-polyether modified silicone oil as the main component, which can improve the heat resistance of the oil agent and effectively solve the embrittlement or breakage problem of silicone oil after 300°C in the pre-oxidation stage, so that the carbon fiber oil agent can still provide good protection for the fiber in the later stage of pre-oxidation process and the low-temperature carbonization process. At the same time, it also solves the problem of roller sticking of amino-polyether silicone oil agent during the precursor production process. In addition, the high heat-resistant carbon fiber oil agent has good spinning processability and carbonization processability, which can meet the preparation needs of high-performance carbon fibers in different processes.

[0022] Other aspects will become apparent upon reading and understanding the drawings and detailed description.Brief Description of the Drawings

[0023] The accompanying drawings incorporated into the specification and constituting a part of the specification illustrate the embodiments of the present disclosure, and are used together with the description to explain the principles of the embodiments of the present disclosure. In these accompanying drawings, similar reference numerals represent similar elements. The accompanying drawings in the following description illustrate some rather than all of the embodiments of the present disclosure. Those skilled in the art may obtain other accompanying drawings based on these accompanying drawings without creative efforts.

[0024] FIG. 1 is thermal gravimetric curves of oil agents prepared in Embodiment 1 and Comparative Embodiment 1 under a simulated carbonization atmosphere according to an exemplary embodiment.Detailed Description

[0025] The technical solutions in the embodiments of the present disclosure will be described clearly and completely with reference to the drawings in the embodiments of the present disclosure. Apparently, the embodiments to be described are only some but not all of the embodiments of the present disclosure. All other embodiments obtained on the basis of the embodiments in the present disclosure by those skilled in the art without paying any creative effort shall fall into the protection scope of the present disclosure. It is to be noted that, without conflict, the embodiments of the present disclosure and the features in the embodiments can be arbitrarily combined with each other.

[0026] The raw materials and reagents used in the following embodiments can be purchased commercially.Embodiment 1

[0027] Take 15 parts by weight of quaternized modified silicone oil with a molecular weight of 20000g / mol, 9 parts by weight of polyether-modified silicone oil with a molecular weight of 5000g / mol, 6 parts by weight of vinyl terminated phenyl silicone oil with a phenyl molar content of 5% and a viscosity of 500cSt, 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 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 the 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 agent with a pH of 4 to 6 and a solid content of about 35% is obtained.Embodiment 2

[0028] Take 17.5 parts by weight of terminal amino-modified silicone oil with a molecular weight of 50000 g / mol, 5 parts by weight of polyether-modified silicone oil with a molecular weight of 1000 g / mol, 2.5 parts by weight of hydroxyl terminated phenyl silicone oil with a phenyl molar content of 5% and a viscosity of 2500 cSt, and 5 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether, and stir evenly until fully mixed. Add 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 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 agent with a pH of 4 to 6 and a solid content of about 30% is obtained.Embodiment 3

[0029] Take 21 parts by weight of quaternized modified silicone oil with a molecular weight of 50000g / mol, 8 parts by weight of polyether-modified silicone oil with a molecular weight of 5000g / mol, 6 parts by weight of vinyl terminated phenyl silicone oil with a phenyl molar content of 10% and a viscosity of 2500cSt, 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 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 58 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 agent with a pH of 4 to 6 and a solid content of about 40% is obtained.Embodiment 4

[0030] Take 15 parts by weight of quaternized modified silicone oil with a molecular weight of 20000g / mol, 9 parts by weight of polyether-modified silicone oil with a molecular weight of 5000g / mol, 6 parts by weight of vinyl terminated phenyl silicone oil with a phenyl molar content of 20% and a viscosity of 500cSt, 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 transition is completed, 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 in total. After standing for 10 minutes, a carbon fiber oil agent with a pH of 4 to 6 and a solid content of about 35% is obtained.Embodiment 5

[0031] Take 15 parts by weight of quaternized modified silicone oil with a molecular weight of 20000g / mol, 9 parts by weight of polyether-modified silicone oil with a molecular weight of 5000g / mol, 6 parts by weight of vinyl terminated phenyl silicone oil with a phenyl molar content of 25% and a viscosity of 2500cSt, 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 transition is completed, 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 in total. After standing for 10 minutes, a carbon fiber oil agent with a pH of 4 to 6 and a solid content of about 35% is obtained.Comparative Embodiment 1

[0032] Take 25 parts by weight of quaternized modified silicone oil with a molecular weight of 20000g / mol, 5 parts by weight of polyether-modified silicone oil with a molecular weight of 5000g / 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 transition is completed, 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 agent with a pH of 4 to 6 and a solid content of about 35% is obtained.Comparative Embodiment 2

[0033] Take 5 parts by weight of quaternized modified silicone oil with a molecular weight of 20000g / mol, 5 parts by weight of polyether-modified silicone oil with a molecular weight of 5000g / mol, 20 parts by weight of vinyl terminated phenyl silicone oil with a phenyl molar content of 5% and a viscosity of 500cSt, 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 transition is completed, 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 agent with a pH of 4 to 6 and a solid content of about 40% is obtained.Comparative Embodiment 3

[0034] Take 20 parts by weight of quaternized modified silicone oil with a molecular weight of 20000g / mol, 5 parts by weight of polyether-modified silicone oil with a molecular weight of 5000g / mol, 5 parts by weight of vinyl terminated phenyl silicone oil with a phenyl molar content of 40% and a viscosity of 500cSt, 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 transition is completed, 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 in total. After standing for 10 minutes, a carbon fiber oil agent with a pH of 4 to 6 and a solid content of about 35% is obtained.

[0035] The properties of the carbon fiber oil agent obtained in each embodiment and comparative embodiment and the results of production line evaluation are shown in Table 1. Table 1NameCharacteristics of oil agent emulsionFiber propertiesStability300°C survival rate / %450°C survival rate / %Precursor gradeCarbon fiber strength / MPaCarbon fiber gradeash content / %Embodiment 1Stable69.864.8Excellent5238Excellent0.052Embodiment 2Stable68.262.1Excellent5199Excellent0.045Embodiment 3Relatively stable72.765.8Excellent5057Good0.068Embodiment 4Relatively stable73.465.5Good4988Good0.086Embodiment 5Stable70.362.4Good5345Excellent0.051Comparative Embodiment 1Stratified62.052.9Good5009Good0.037Comparative Embodiment 2Easy to stratify79.669.3Bad / / / Comparative Embodiment 3Extremely easy to stratify81.268.1Bad / / /

[0036] The difference between the embodiments and the comparative embodiment 1 is that phenyl-modified silicone oil is introduced into the modified silicone oil. The heat resistance of the oil agent in each embodiment is significantly improved, and the fiber processability and carbon fiber strength are better than those in Comparative Embodiment 1. The difference between Embodiments 4 and 5 and Embodiment 1 is the change in the phenyl molar content of the phenyl-modified silicone oil. As the phenyl molar content increases, the stability of the oil agent decreases, and the fiber processability and carbon fiber strength begin to deteriorate. The difference between Comparative Embodiments 2 and 3 and Embodiment 1 is the high phenyl-modified silicone oil content and the high phenyl molar content, respectively. The stability of the oil agent emulsion is extremely poor. Although the preparation of the precursor can be completed in the spinning stage, the fiber breakage phenomenon frequently occurs in the carbonization stage.

[0037] In summary, the exemplary embodiments of the present disclosure introduces phenyl-modified silicone oil into the carbon fiber oil agent system with amino-polyether modified silicone oil as the main component, which not only improves the heat resistance of the oil agent and ensures that the fiber can be better protected during the subsequent oxidation process and carbonization process, but also solves the problem of roller sticking of original silicone oil system. The embodiments of the present disclosure provide a high heat-resistant carbon fiber oil agent, and by optimizing the content of phenyl-modified silicone oil, the phenyl molar content, etc., the ash content of the carbon fiber is kept below the control standard, so that the carbon fiber can still play a greater role in the subsequent use of the composite material.

[0038] Various embodiments or implementations in this specification have been described progressively, and each embodiment focuses on the differences from other embodiments, so the same and similar parts of the embodiments may refer to each other.

[0039] In the description of this specification, the description with reference to terms "an embodiment", "an exemplary embodiment", "some embodiments", "an illustrative implementation" or "an example" means that specific features, structures, materials or characteristics described with reference to an implementation or example are included in at least one implementation or example of the present disclosure.

[0040] In this specification, the schematic expressions of the terms do not necessarily refer to the same implementation or example. In addition, the described specific features, structures, materials or characteristics may be combined in any one or more implementations or examples in a proper way.

[0041] In the description of the present disclosure, it should be understood that the orientation or position relationship indicated by terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" and the like is an orientation or position relationship illustrated on the basis of the drawings, and is only for describing the present disclosure and simplifying the description, rather than indicating or implying that the specified device or element must have a particular direction and be constructed and operated in a particular direction. Therefore, the terms cannot be interpreted as limitations to the present disclosure.

[0042] It should be understood that the terms such as "first" and "second" used in the present disclosure can be used in the present disclosure to describe various structures, but these structures are not limited by these terms. The terms are only used to distinguish a first structure from another structure.

[0043] Throughout one or more drawings, the same elements are denoted by similar reference numerals. For clarity, many parts in the drawings are not drawn to scale. In addition, some known parts may not be shown. For simplicity, the structures obtained after several steps can be described in one drawing. Many specific details of the present disclosure are described hereinafter, for example, the structures, materials, sizes, processing processes and technologies of the devices, in order to understand the present disclosure more clearly. As will be understood by those skilled in the art, the present disclosure may be implemented without these specific details.

[0044] Finally, it is to be noted that the foregoing embodiments are only used for describing the technical solutions of the present disclosure, rather than limiting the present disclosure. Although the present disclosure has been described in detail by the foregoing embodiments, a person of ordinary skill in the art should understood that modifications can still be made to the technical solutions recorded in the foregoing embodiments or equipment replacements can be made to some or all of the technical features, and these modifications or replacements do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions in the embodiments of the present disclosure.Industrial Applicability

[0045] The high heat-resistant carbon fiber oil agent provided in the embodiments of the present disclosure introduces phenyl-modified silicone oil into the carbon fiber oil agent system with amino-polyether modified silicone oil as the main component, which can improve the heat resistance of the oil agent and effectively solve the embrittlement or breakage problem of silicone oil after 300°C in the pre-oxidation stage, so that the carbon fiber oil agent can still provide good protection for the fiber in the later stage of pre-oxidation process and the low-temperature carbonization process. At the same time, it also solves the problem of roller sticking of amino-polyether silicone oil agent during the precursor production process. In addition, the high heat-resistant carbon fiber oil agent has good spinning processability and carbonization processability, which can meet the preparation needs of high-performance carbon fibers in different processes.

Claims

1. A high heat-resistant carbon fiber oil agent, consisting of the follow components by weight percentage: 25% to 35% of modified silicone oil, 5% to 10% of surfactant, 55% to 70% of pure water, and 1% to 3% of other auxiliaries; wherein 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 high heat-resistant carbon fiber oil agent according to claim 1, consisting of the follow components by weight percentage: 25% to 35% of the modified silicone oil, 5% of the surfactant, 58% to 68% of the pure water, and 2% of the other auxiliaries.

3. The high heat-resistant carbon fiber oil agent 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 auxiliaries are antistatic agent, defoaming agent and organic solvent, the antistatic agent is polyethylene glycol fatty acid ester, polyoxyethylene laurate, dodecyl trimethyl ammonium 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 high heat-resistant carbon fiber oil agent according to claim 1, wherein the modified silicone oil, based on the total weight of 100%, is composed of 60% to 70% of the amino-modified silicone oil, 20% to 25% of the polyether-modified silicone oil and 15% to 20% of the phenyl-modified silicone oil.

5. The high heat-resistant carbon fiber oil agent 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 a viscosity of the phenyl-modified silicon oil is 50 cSt to 5000 cSt.

6. The high heat-resistant carbon fiber oil agent 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 the phenyl-modified silicon oil is 500 cSt to 2500 cSt.

7. The high heat-resistant carbon fiber oil agent according to claim 1, wherein the phenyl-modified silicone oil is one or more of vinyl terminated phenyl silicone oil, phenyl hydrogen-containing silicone oil or hydroxy terminated phenyl silicone oil.

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

9. The high heat-resistant carbon fiber oil agent according to claim 1, wherein the amino-modified silicone oil is quaternized modified silicone oil, a molecular weight of the amino-modified silicon oil is 10000 g / mol to 30000 g / mol; and a molecular weight of the polyether-modified silicone oil is 5000 g / mol to 10000 g / mol.

10. A method for preparing the high heat-resistant carbon fiber oil agent according to any one of claims 1 to 9, comprising: stirring and mixing amino-modified silicone oil, polyether-modified silicone oil, phenyl-modified silicone oil and surfactant according to a proportion; adding a preset percentage of pure water under stirring, until a phase transition is completed; adding a remaining percentage of the pure water and other auxiliaries; standing to obtain the carbon fiber oil agent, wherein a pH of the carbon fiber oil agent is 4 to 6, and a solid content of the carbon fiber oil agent is 30% to 40%.

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