Large-tow carbon fiber precursor water-based oiling agent and preparation method thereof

Abstract

The invention provides a large-tow carbon fiber precursor water-based oiling agent and a preparation method thereof, and belongs to the field of carbon fiber oiling agents. The oiling agent is prepared from the following raw materials in parts by weight: 70-80 parts of polyether / amino co-modified silicone oil, 10-20 parts of neopentyl polyol higher aliphatic ester, 0.1-3 parts of modified carbon nanoparticles, 50-100 parts of deionized water, 3-15 parts of an emulsifier and 2-8 parts of an antistatic agent, the prepared oiling agent adopts water as a solvent, so that the pollution to the environment is greatly reduced; gaps of large-tow carbon fibers can be filled so that the large-tow carbon fibers can be smooth and flat, the phenomena of adhesion, broken filaments, broken filaments and electrostatic adhesion are reduced, and the preparation method is simple and can be used for industrial production.

Description

Technical Field

[0001] The invention belongs to the field of carbon fiber oils, and in particular relates to a large-tow carbon fiber precursor water-based oil and a preparation method thereof. Background Art

[0002] Carbon fiber has excellent properties such as light weight, high specific strength, high specific modulus, high temperature resistance, corrosion resistance, wear resistance, fatigue resistance, electrical conductivity, and thermal conductivity. It is an indispensable new material in aerospace and other fields. With the expansion of carbon fiber production scale, the application scope has gradually expanded to wind power generation, automotive materials, sports equipment, textile machinery, transportation machinery, construction engineering and other civil fields. At present, the development of low-cost carbon fiber has become the development trend of the industry. Increasing the tow is an effective means to expand the single-line production capacity and reduce costs. Under the condition that small-tow carbon fiber and large-tow carbon fiber have been industrialized one after another, the development of giant tow carbon fiber of 100k and above and its related additives has attracted great attention from the industry.

[0003] At the beginning of the development of carbon fiber, large tow carbon fiber has always been in a low position in the market due to its performance disadvantages. With the development of technology, the problems existing in the field of large tow carbon fiber have been solved one by one, and the performance of large tow carbon fiber has gradually met the basic use needs, broadening the scope of use of carbon fiber. At the same time, due to the difficulty and high cost of small tow carbon fiber production, large tow carbon fiber has been favored and has shown broad application prospects.

[0004] However, there are still many problems with the large-tow carbon fiber currently produced. For example, in the preparation process, there are slow mass and heat transfer, easy heat storage and concentrated heat release during pre-oxidation, and even fire, and serious skin-core structure. In addition, due to the large tows and easy aggregation, the resin has poor wettability inside the large tow fiber bundles, and pores are easily generated between the tows, which is easy to cause defects such as enrichment and separation of the resin phase. In addition, during the unwinding process of large-tow carbon fiber, there will be hairy or even broken yarns, which will affect the preparation process of prepreg.

[0005] At present, there are still a series of problems with the large-tow carbon fiber oils used, such as insufficient coating ability for large-tow carbon fiber raw materials, inability to effectively transfer carbonization heat, insufficient filling ability for small gaps, and uneven carbon fiber produced later, and the appearance of lint and other problems; moreover, most of the oils currently use oil solvents, which have a certain impact on the environment. Summary of the invention

[0006] In view of this, the purpose of the present invention is to provide an aqueous oil agent for large-tow carbon fiber precursor and a preparation method thereof. The obtained oil agent is safe and environmentally friendly and can reduce the phenomena of adhesion, lint, broken wires and electrostatic adhesion of large-tow carbon fibers.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] In the first aspect, the present invention provides an aqueous oil agent for large-tow carbon fiber precursor, which is prepared from the following raw materials in parts by weight: 70-80 parts of polyether / amino co-modified silicone oil, 10-20 parts of neopentyl polyol higher fatty acid ester, 0.1-3 parts of modified carbon nanoparticles, 50-100 parts of deionized water, 3-15 parts of emulsifier, and 2-8 parts of antistatic agent.

[0009] Preferably, the preparation method of the polyether / amino co-modified silicone oil is:

[0010] In a nitrogen atmosphere, polymethyl hydrogen siloxane, propylene amine and a catalyst are mixed and subjected to a hydrothermal reaction at 70 to 90° C. for 1 to 1.5 hours to obtain amino hydrogen silicone oil;

[0011] The mass ratio of the polymethylhydrogensiloxane, acrylamine and catalyst is 9:0.5-3:0.01-0.5;

[0012] Mixing amino hydrogen silicone oil, allyl polyether and catalyst, heating to 65-75° C. in a nitrogen atmosphere, and reacting for 2-3 hours to obtain polyether / amino co-modified silicone oil;

[0013] The mass ratio of the amino hydrogen silicone oil, the allyl polyether and the catalyst is 5:5-8:0.01-0.5.

[0014] The viscosity of the polyether / amino co-modified silicone oil at 40°C is 100-500 mm 2 / s.

[0015] By adopting the above technical scheme, amino and polyether modified silicone oils can form chemical bonds or physical entanglements with the surface of carbon fibers through their active groups, thereby improving the interfacial bonding force between carbon fibers and resin matrix, which is helpful to improve the mechanical properties of composite materials; the dispersion and bundling properties of carbon fiber precursors can be improved, and good dispersion and bundling properties can reduce the entanglement between fiber bundles, thereby reducing the hair rate during processing, reducing the friction between fibers and between fibers and processing equipment, thereby reducing wear and broken fibers; polyether / amino co-modified silicone oil has good thermal stability, and can maintain its performance unchanged in the high temperature stage of the carbon fiber preparation process, prevent the oil from decomposing or burning, and thus protect the fiber from thermal damage; polyether modification helps to improve the self-emulsification of silicone oil, so that the oil forms a uniform emulsion in the water phase.

[0016] Preferably, the viscosity of the neopentyl polyol higher fatty acid at 40°C is 20-40 mm 2 / s.

[0017] Preferably, the preparation method of the modified carbon nanoparticles is:

[0018] Carbon nanoparticles, hydrogen peroxide, nitric acid and sulfuric acid are mixed and carboxylated at 70°C, and then triethanolamine is added and reacted at 65°C for 3 hours to obtain modified carbon nanoparticles. By adopting the above technical scheme, the present invention can fill the gaps generated when preparing large-tow carbon fibers with modified carbon nanoparticles, and carbonize them to make them firmly bonded in the gaps, and the carbon nanoparticles modified by quaternary ammonium salts have high temperature stability to reduce the generation of side effects.

[0019] Preferably, the particle size of the modified carbon nanoparticles is 10-100 nm.

[0020] Preferably, the emulsifier is one or more of a cationic surfactant, an anionic surfactant, a nonionic surfactant and an amphoteric surfactant.

[0021] Preferably, the nonionic emulsifier is polysorbate or polyvinyl pyrrolidone;

[0022] The anionic surfactants are sodium dodecyl sulfate and sodium lauryl sulfate;

[0023] Examples of cationic surfactants include lauryl trimethyl ammonium chloride, oleyl methyl ethyl ammonium ethyl sulfate, and polyoxyethylene laurylamine lactate;

[0024] The amphoteric surfactants are stearyl dimethyl betaine and lauryl dihydroxyethyl betaine.

[0025] Preferably, the antistatic agent is one or more of stearyl trimethyl ammonium chloride, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, and dodecyl hydroxypropyl dihydroxyethyl methyl ammonium sulfate.

[0026] The present invention also provides a method for preparing the above-mentioned large-tow carbon fiber precursor aqueous oil agent, comprising the following steps:

[0027] (1) weighing the raw materials according to the weight parts;

[0028] (2) mixing polyether / amino co-modified silicone oil, neopentyl polyol higher fatty acid ester, and modified carbon nanoparticles uniformly and performing ultrasonic dispersion treatment to obtain component A;

[0029] (3) Component A, deionized water, an emulsifier, and an antistatic agent are emulsified to obtain an aqueous oil solution for large-tow carbon fiber precursor with a particle size of 0.01 to 0.5 μm.

[0030] Preferably, the power of the ultrasonic dispersion is 500-1000 W, and the time is 5-10 min.

[0031] Contains at least the following beneficial technical effects:

[0032] 1) The large-tow carbon fiber oil prepared by the present invention uses water as a solvent, which greatly reduces the pollution to the environment.

[0033] 2) The oil prepared by the present invention can enhance the strength of carbon fiber, fill the gaps of large-tow carbon fiber to make it smooth and flat, and reduce the phenomenon of adhesion, hairy fibers, broken fibers, and electrostatic adhesion.

[0034] 3) The preparation method of the oil prepared by the present invention is simple and can be used for industrial production. DETAILED DESCRIPTION

[0035] The technical solution of the present invention is further illustrated by the following examples.

[0036] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0037] It is obvious to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the main idea or essential features of the present invention. Therefore, the embodiments should be regarded as exemplary and non-limiting from any point of view, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims are included in the present invention, and any mark in the claims should not be regarded as limiting the claims involved.

[0038] In addition, it should be understood that although this specification is described according to the implementation modes, not every implementation mode includes only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation modes that can be understood by those skilled in the art. These other implementation modes are also covered within the protection scope of the present invention.

[0039] It should also be understood that the specific embodiments described above are only used to explain the present invention, and the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, can make equivalent replacements or changes based on the technical solutions and inventive concepts of the present invention, which should be covered by the protection scope of the present invention / invention.

[0040] The preparation methods of the polyether / amino co-modified silicone oil and modified carbon nanoparticles used in the following examples are as follows:

[0041] Polyether / amino co-modified silicone oil:

[0042] In a nitrogen atmosphere, polymethyl hydrogen siloxane, allylamine and chloroplatinic acid hexahydrate are mixed and subjected to a hydrothermal reaction at 80° C. for 1 hour to obtain amino hydrogen silicone oil; wherein the mass ratio of polymethyl hydrogen siloxane, allylamine and chloroplatinic acid hexahydrate is 9:1:0.1;

[0043] Amino hydrogen silicone oil, allyl polyether and hexahydrate chloroplatinic acid are mixed and heated to 70°C under a nitrogen atmosphere and reacted for 2.5 hours to obtain polyether / amino co-modified silicone oil; wherein the mass ratio of amino hydrogen silicone oil, allyl polyether and hexahydrate chloroplatinic acid is 5:6:0.1; and the molecular weight of allyl polyether is 1200.

[0044] Modified carbon nanoparticles: Carbon nanoparticles, hydrogen peroxide, nitric acid and sulfuric acid are mixed and carboxylated at 70°C, and then triethanolamine is added and reacted at 65°C for 3 hours to obtain modified carbon nanoparticles.

[0045] Example 1

[0046] This embodiment provides a method for preparing a biological agent for removing arsenic and antimony:

[0047] S1. Weigh 75 parts of polyether / amino co-modified silicone oil, 15 parts of neopentyl polyol higher fatty acid ester, 1 part of modified carbon nanoparticles, 70 parts of deionized water, 5 parts of emulsifier, and 3 parts of antistatic agent by weight; the viscosity of the polyether / amino co-modified silicone oil at 40°C is 285mm 2 / s; the viscosity of neopentyl polyol higher fatty acid at 40°C is 36 mm 2 / s; the particle size of the modified carbon nanoparticles is 30nm; the emulsifier is stearyl dimethyl betaine; the antistatic agent is stearyl trimethyl ammonium chloride;

[0048] S2. The polyether / amino co-modified silicone oil, neopentyl polyol higher fatty acid ester, and modified carbon nanoparticles were uniformly mixed and ultrasonically dispersed at 800 W for 8 min to obtain component A;

[0049] Component A, deionized water, an emulsifier and an antistatic agent are emulsified to obtain an aqueous oil solution for large-tow carbon fiber precursor with a particle size of 0.1 μm.

[0050] Example 2

[0051] This embodiment provides a method for preparing a biological agent for removing arsenic and antimony:

[0052] S1. Weigh 70 parts of polyether / amino co-modified silicone oil, 10 parts of neopentyl polyol higher fatty acid ester, 0.1 parts of modified carbon nanoparticles, 50 parts of deionized water, 3 parts of emulsifier, and 2 parts of antistatic agent by weight; the viscosity of the polyether / amino co-modified silicone oil at 40°C is 100 mm 2 / s; the viscosity of neopentyl polyol higher fatty acid at 40°C is 20 mm 2 / s; the particle size of the modified carbon nanoparticles is 10nm; the emulsifier is polysorbate; the antistatic agent is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate;

[0053] S2. The polyether / amino co-modified silicone oil, neopentyl polyol higher fatty acid ester, and modified carbon nanoparticles were uniformly mixed and ultrasonically dispersed at 500 W for 5 min to obtain component A;

[0054] Component A, deionized water, an emulsifier and an antistatic agent are emulsified to obtain an aqueous oil solution for large-tow carbon fiber precursor with a particle size of 0.01 μm.

[0055] Example 3

[0056] This embodiment provides a method for preparing a biological agent for removing arsenic and antimony:

[0057] S1. Weigh 80 parts of polyether / amino co-modified silicone oil, 20 parts of neopentyl polyol higher fatty acid ester, 3 parts of modified carbon nanoparticles, 100 parts of deionized water, 15 parts of emulsifier, and 8 parts of antistatic agent by weight; the viscosity of the polyether / amino co-modified silicone oil at 40°C is 500mm 2 / s; the viscosity of neopentyl polyol higher fatty acid at 40°C is 40mm 2 / s; the particle size of the modified carbon nanoparticles is 100 nm; the emulsifier is sodium dodecyl sulfate;

[0058] S2. The polyether / amino co-modified silicone oil, neopentyl polyol higher fatty acid ester, and modified carbon nanoparticles were uniformly mixed and ultrasonically dispersed at 1000 W for 10 min to obtain component A;

[0059] Component A, deionized water, an emulsifier and an antistatic agent are emulsified to obtain an aqueous oil solution for large-tow carbon fiber precursor with a particle size of 0.5 μm.

[0060] Comparative Example 1

[0061] The preparation method of this comparative example is the same as that of Example 1, except that no modified carbon nanoparticles are added.

[0062] Comparative Example 2

[0063] The preparation method of this comparative example is the same as that of Example 1, except that the polyether / amino co-modified silicone oil is replaced by polyether-modified silicone oil.

[0064] Experimental example

[0065] 48K large-tow carbon fibers were prepared respectively using the oils prepared in Examples 1-3 of the present invention and Comparative Examples 1-2, and the performance of the prepared carbon fibers was tested.

[0066] Table 1

[0067]

[0068] The oil obtained in the embodiment of the present invention can optimize the performance of large-tow carbon fiber, significantly enhance its strength by filling the porosity, and reduce defects such as fuzz to improve the quality.

[0069] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A water-based oil agent for large-tow carbon fiber precursor, characterized in that: The invention is prepared from the following raw materials in parts by weight: 70-80 parts of polyether / amino co-modified silicone oil, 10-20 parts of neopentyl polyol higher fatty acid ester, 0.1-3 parts of modified carbon nanoparticles, 50-100 parts of deionized water, 3-15 parts of emulsifier and 2-8 parts of antistatic agent.

2. The aqueous oil agent for large-tow carbon fiber precursor according to claim 1, characterized in that: The preparation method of the polyether / amino co-modified silicone oil is: In a nitrogen atmosphere, polymethyl hydrogen siloxane, propylene amine and a catalyst are mixed and subjected to a hydrothermal reaction at 70 to 90° C. for 1 to 1.5 hours to obtain amino hydrogen silicone oil; The mass ratio of the polymethylhydrogensiloxane, acrylamine and catalyst is 9:0.5-3:0.01-0.5; The amino hydrogen silicone oil, allyl polyether and catalyst are mixed and heated to 65-75° C. in a nitrogen atmosphere for 2-3 hours to obtain polyether / amino co-modified silicone oil; The mass ratio of the amino hydrogen silicone oil, the allyl polyether and the catalyst is 5:5-8:0.01-0.

5.

3. The aqueous oil agent for large-tow carbon fiber precursor according to claim 1, characterized in that: The viscosity of the neopentyl polyol higher fatty acid at 40° C. is 20 to 40 mm 2 / s.

4. The aqueous oil agent for large-tow carbon fiber precursor according to claim 1, characterized in that: The preparation method of the modified carbon nanoparticles is: Carbon nanoparticles, hydrogen peroxide, nitric acid and sulfuric acid were mixed and carboxylated at 70°C, and then triethanolamine was added and reacted at 65°C for 3 hours to obtain modified carbon nanoparticles.

5. The aqueous oil agent for large-tow carbon fiber precursor according to claim 5, characterized in that: The particle size of the modified carbon nanoparticles is 10-100 nm.

6. The aqueous oil agent for large-tow carbon fiber precursor according to claim 1, characterized in that: The emulsifier is one or more of a cationic surfactant, an anionic surfactant, a nonionic surfactant and an amphoteric surfactant.

7. The aqueous oil agent for large-tow carbon fiber precursor according to claim 6, characterized in that: The nonionic emulsifier is polysorbate or polyvinyl pyrrolidone; The anionic surfactants are sodium dodecyl sulfate and sodium lauryl sulfate; Examples of cationic surfactants include lauryl trimethyl ammonium chloride, oleyl methyl ethyl ammonium ethyl sulfate, and polyoxyethylene laurylamine lactate; The amphoteric surfactants are stearyl dimethyl betaine and lauryl dihydroxyethyl betaine.

8. The aqueous oil agent for large-tow carbon fiber precursor according to claim 1, characterized in that: The antistatic agent is one or more of stearyl trimethyl ammonium chloride, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, and dodecyl hydroxypropyl dihydroxyethyl methyl ammonium sulfate.

9. The method for preparing the aqueous oil agent for large-tow carbon fiber precursor according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) weighing the raw materials according to the weight parts; (2) mixing polyether / amino co-modified silicone oil, neopentyl polyol higher fatty acid ester, and modified carbon nanoparticles uniformly and performing ultrasonic dispersion treatment to obtain component A; (3) Component A, deionized water, an emulsifier, and an antistatic agent are emulsified to obtain an aqueous oil solution for large-tow carbon fiber precursor with a particle size of 0.01 to 0.5 μm.

10. The preparation method according to claim 9, characterized in that: The power of the ultrasonic dispersion is 500-1000W, and the time is 5-10 minutes.

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