Silicone carbon fiber protective oil

Abstract

This invention discloses an organosilicon carbon fiber protective oil, relating to the field of novel ink technology. The organosilicon carbon fiber protective oil comprises the following components in parts by weight: 80-150 parts base silicone oil, 5-25 parts emulsifier, 3-15 parts rust and corrosion inhibitor, 0.1-10 parts thickener, 0.5-1.5 parts anti-aging agent, and 100-300 parts water. Traditional oils often focus on a single protective function (such as rust prevention or UV resistance), while this invention achieves a "three-in-one" protection of rust prevention, corrosion resistance, and aging resistance through molecular-level synergistic design, forming a dynamic self-healing barrier to resist long-term erosion in complex environments. Existing technologies often suffer from performance degradation due to emulsion stratification or component sedimentation. This invention uses a mild water-based process to construct a uniform emulsion system, which can be stably stored without high temperature and high pressure, significantly lowering the industrialization threshold.

Description

Technical Field

[0001] This invention relates to the field of novel ink technology, specifically to an organosilicon carbon fiber protective oil agent. Background Technology

[0002] Carbon fiber, as a novel material with high strength, high modulus, and low density, is widely used in aerospace, automotive, sporting goods, and many other fields. However, carbon fiber is susceptible to various external factors during use, such as friction, oxidation, ultraviolet radiation, and chemical corrosion, which can lead to a decline in its surface properties and affect its service life and application performance.

[0003] Traditional methods for protecting carbon fibers mainly focus on surface coating and composite material preparation. While surface coating can improve the protective performance of carbon fibers to some extent, it suffers from problems such as poor coating adhesion, easy peeling, and lack of durability. Composite material preparation requires complex pretreatment and molding processes for carbon fibers, and it is difficult to achieve all-round protection for carbon fibers.

[0004] Existing protective oils have several shortcomings. On the one hand, some oils have limited protective performance, making it difficult to simultaneously meet multiple protective needs such as rust prevention, corrosion resistance, and aging resistance. On the other hand, some oils have poor stability, easily exhibiting stratification and sedimentation during storage and use, affecting their effectiveness. Furthermore, the preparation processes of some oils are complex and costly, making large-scale industrial application difficult and potentially causing environmental pollution, which does not meet the requirements of sustainable development.

[0005] In view of the problems existing in the prior art, the present invention aims to provide an organosilicon carbon fiber protective oil agent, its preparation method and application, so as to overcome the defects in the prior art, provide an efficient, stable, environmentally friendly and easily industrialized solution for the protection of carbon fibers, meet the protection needs of carbon fibers in different application scenarios, extend their service life, and ensure the quality and performance of related products. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing technologies by providing an organosilicon carbon fiber protective oil with excellent rust prevention, corrosion resistance, and aging resistance, overcoming the defects of traditional protection methods, meeting the protection needs of carbon fibers in complex environments, and extending their service life.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: an organosilicon carbon fiber protective oil agent, comprising the following components in parts by weight: 80-150 parts of base silicone oil, 5-25 parts of emulsifier, 3-15 parts of rust and corrosion inhibitor, 0.1-10 parts of thickener, 0.5-1.5 parts of anti-aging agent, and 100-300 parts of water;

[0008] The anti-aging agent has the structure shown in Formula 1:

[0009]

[0010] R1 in Formula 1 is selected from: methyl, methoxy, phenyl, tert-butyl.

[0011] Furthermore, the base silicone oil is selected from polyether-modified polysiloxane.

[0012] Furthermore, the emulsifier is selected from N,N-di(hydroxyethyl)cocoamide.

[0013] Furthermore, the rust and corrosion inhibitor is selected from dicyclohexylamine.

[0014] Furthermore, the thickener is selected from sodium carboxymethyl cellulose.

[0015] Furthermore, the anti-aging agent is selected from any one of the compounds shown in the following structures:

[0016]

[0017] A method for preparing an organosilicon carbon fiber protective oil agent includes the following steps:

[0018] S1. Add the water, anti-aging agent and thickener to the reaction system and stir until uniform and free of particles;

[0019] S2. Add the emulsifier and stir until homogeneous;

[0020] S3. Add the base silicone oil dropwise and stir until homogeneous;

[0021] S4. Add the rust and corrosion inhibitor, filter, and obtain an organosilicon carbon fiber protective oil.

[0022] Furthermore, S2 is performed at 40-50°C.

[0023] Furthermore, S1 is performed at 50-75°C.

[0024] An organosilicon carbon fiber protective oil agent is used in the field of carbon fiber protective ink.

[0025] An organosilicon carbon fiber protective oil can be used as a carbon fiber continuous and discontinuous fiber reinforced composite material.

[0026] The anti-aging agent described in this invention contains imino groups, alkyl chains, heteroconjugated aromatic ring structures, and silane bonds. These structures work together to enable the anti-aging agent to exert highly efficient protective performance in organosilicon carbon fiber protective oils, including anti-oxidation, anti-UV aging, and enhanced oil stability. Imino groups, as strong hydrogen bond donors, form a hydrogen bond network with polar groups on the carbon fiber surface, enhancing the adhesion of the oil to the fiber, reducing the risk of oil detachment, and ensuring long-term protection. Alkyl chains provide hydrophobic properties, forming a physical barrier that prevents water molecules and corrosive ions from contacting the carbon fiber surface, reducing the risk of hydrolysis and electrochemical corrosion. Heteroconjugated structures (such as phenyl or cyano groups in R1) form a conjugated π-electron system, effectively absorbing UV radiation (290-400nm) and converting it into heat energy dissipation, preventing UV-induced carbon fiber chain breakage. Silane bonds constitute the molecular skeleton, imparting high flexibility and thermal stability (temperature resistance up to 200℃ and above). In the oil, it is compatible with the base silicone oil, forming a continuous film layer that protects the carbon fiber from mechanical friction and thermal stress.

[0027] The organosilicon carbon fiber protective oil of this invention constructs a "three-dimensional protective network" through the synergistic effect of multiple components, including base silicone oil, emulsifier, rust and corrosion inhibitor, thickener, anti-aging agent, and water. The chemical synergy (intermolecular hydrogen bonds and hydrophobic interactions form a continuous protective film to isolate moisture, corrosive ions, and ultraviolet radiation) and physical synergy (the emulsifier and thickener stabilize the emulsion structure and adjust viscosity to ensure uniform oil coverage) jointly overcome the limitations of traditional oils in terms of limited protective performance, poor stability, complex preparation processes, high costs, and environmental impact. Specifically, the base silicone oil provides flexibility and thermal stability as the matrix, and works synergistically with rust inhibitors, corrosion inhibitors, and anti-aging agents to form a physical barrier and chemical protective film; the emulsifier promotes uniform dispersion of the emulsion at 40-50℃; the rust inhibitor neutralizes the acidic environment and forms a hydrogen bond network with the imino groups of the anti-aging agent, enhancing adhesion; the thickener forms a gel network at 50-75℃ to prevent component sedimentation; the anti-aging agent, through its unique structure (as shown in Formula 1), in which the imino groups enhance the adhesion of carbon fibers, the alkyl chains provide a hydrophobic barrier to block moisture, the heteroconjugated aromatic ring structure absorbs 290-400nm ultraviolet light and converts it into heat energy, and the silane bonds ensure flexibility and compatibility with the base silicone oil, achieving high-efficiency protection with low dosage; water, as an environmentally friendly solvent, supports mild preparation (carried out in steps S1-S4 at 50-75℃) and adjusts the viscosity of the system. This synergistic effect simultaneously enhances protective performance (covering rust prevention, corrosion resistance, and anti-aging requirements, such as UV absorption), stability (emulsifiers and thickeners prevent stratification and sedimentation), process simplification (reduced energy consumption and complexity), cost advantages (low-volume design and environmentally friendly formulation), and environmental sustainability (water-based reduces volatile organic pollutants, and components are highly biodegradable), thereby extending the service life in carbon fiber protection applications.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] 1. Comprehensive improvement in protective performance: Traditional oils often focus on a single protective function (such as rust prevention or UV protection), while this invention achieves "three-in-one" protection of rust prevention, corrosion resistance and aging resistance through molecular-level synergistic design, forming a dynamic self-healing barrier to resist long-term erosion in complex environments.

[0030] 2. Stability and process breakthrough: Existing technologies often suffer from performance degradation due to emulsion stratification or component sedimentation. This invention uses a mild water-based process to construct a uniform emulsion system, which can be stably stored without high temperature and high pressure, greatly reducing the threshold for industrialization.

[0031] 3. Balancing environmental protection and cost: Traditional solutions rely on high-cost or polluting components (such as organic solvents). This invention reduces the amount of key additives by precise compounding and reduces VOC emissions by using water as a carrier, thus taking into account both long-term performance and the needs of green production. Attached Figure Description

[0032] Figure 1 This is the NMR spectrum of the anti-aging agent 1 described in this invention. Detailed Implementation

[0033] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] Preparation Example 1

[0035] Synthesis of Anti-aging Agent 1:

[0036] first step:

[0037]

[0038] Under a nitrogen atmosphere, 15 g of raw material 1, 19.09 g of raw material 2, 21.02 g of potassium carbonate, 0.27 g of target carbon, 1.0 g of triphenylphosphine, and 200 g of toluene were added to the reaction system. After stirring until homogeneous, the mixture was heated to 110 °C and refluxed for 12 h. After the reaction was completed, the temperature was slightly lowered, the mixture was filtered using silica gel cake, dried by rotary evaporation, and subjected to silica gel column chromatography using a mixture of petroleum ether and ethyl acetate as eluent. After drying by rotary evaporation, 19.96 g of intermediate 1 was obtained.

[0039] Intermediate 1 mass spectrometry (M / Z-MS+H) + ): 326.

[0040] Step Two:

[0041]

[0042] Under a nitrogen atmosphere, 19.96 g of intermediate 1, 28.65 g of raw material 3, 32.66 g of potassium phosphate trihydrate, 0.07 g of pyridine-2-carboxylic acid, 0.58 g of CuI, and 300 g of DMSO were added to the reaction system, and the mixture was heated to 85 °C and reacted for 16 h. The temperature of the reaction system was then lowered to room temperature, and the reaction mixture was extracted with ammonia solution and methyl tert-butyl ether. The organic phase was washed three times with saturated NaCl solution, and the combined organic phases were evaporated to dryness and purified by silica gel column chromatography. A mixed solution of petroleum ether and ethyl acetate was used as the eluent, and the solution was evaporated to dryness to obtain 27.61 g of anti-aging agent 1.

[0043] Final product structure identification: Anti-aging agent 1 mass spectrometry (M / Z-MS+H) + ): 634; MRI results Figure 1 .

[0044] Preparation Examples 2-4

[0045] Preparation Examples 2-4 sequentially prepared anti-aging agents 2-4, following the preparation method of Preparation Example 1, except that raw material 1 was replaced, while the rest remained the same as in Preparation Example 1. Specific structures of raw material 1, anti-aging agents 2-4, and mass spectrometry (M / Z-MS+H) are described. + The data is shown in Table 1.

[0046] Table 1.

[0047]

[0048]

[0049] Example 1

[0050] Preparation of an organosilicon carbon fiber protective oil:

[0051] 1. Raw material composition and dosage:

[0052] Base silicone oil: polyether-modified polysiloxane (purchased from Anhui Aiyota Silicone Oil Co., Ltd., polyether-modified polysiloxane 13190), 120 parts;

[0053] Emulsifier: N,N-di(hydroxyethyl)cocoamide, 15 parts;

[0054] Rust and corrosion inhibitor: dicyclohexylamine, 9 parts;

[0055] Thickener: Sodium carboxymethyl cellulose, 5 parts;

[0056] Anti-aging agent: Anti-aging agent 1 (anti-aging agent 1 prepared in preparation example 1), 1 part

[0057] Water: 200 servings.

[0058] 2. Preparation method:

[0059] S1. Add water (200 parts), anti-aging agent 1 (1 part) and thickener (sodium carboxymethyl cellulose, 5 parts) to the reactor, heat to 60°C, and stir (500 rpm) for 30 minutes until the system is uniform and free of particles.

[0060] S2. Lower the temperature to 45°C, add the emulsifier (N,N-di(hydroxyethyl)cocamide, 15 parts), and continue stirring for 20 minutes to ensure complete emulsification;

[0061] S3. Slowly add base silicone oil (polyether modified polysiloxane, 120 parts) while maintaining stirring (600 rpm). After the addition is complete, stir for 40 minutes to form a uniform emulsion.

[0062] S4. Add rust and corrosion inhibitor (dicyclohexylamine, 9 parts), stir for 15 minutes, filter through a 30-mesh filter to remove impurities, and obtain a clear and transparent organosilicon carbon fiber protective oil.

[0063] Examples 2-4

[0064] The preparation of an organosilicon carbon fiber protective oil agent is carried out by referring to the preparation method of Example 1, except that the anti-aging agent is replaced in sequence with the anti-aging agent 2-anti-aging agent 4 prepared in Preparation Examples 2-4, and the rest is the same as in Example 1.

[0065] Comparative Example 1

[0066] The preparation of an organosilicon carbon fiber protective oil agent is carried out according to the preparation method of Example 1, except that the anti-aging agent is replaced with comparative compound 1, and the rest is the same as in Example 1.

[0067] The structure of compound 1 is as follows: 6PPD rubber antioxidant, CAS: 793-24-8, is a commonly used antioxidant in industry.

[0068] Comparative Example 2

[0069] The preparation of an organosilicon carbon fiber protective oil agent is carried out according to the preparation method of Example 1, except that the anti-aging agent is replaced with comparative compound 2, and the rest is the same as in Example 1.

[0070] The structure of compound 2 is as follows:

[0071] Comparative Example 3

[0072] The preparation of an organosilicon carbon fiber protective oil agent is the same as in Example 1, except that the anti-aging agent is not added.

[0073] Comparative Example 4

[0074] The preparation of an organosilicon carbon fiber protective oil agent is carried out according to the preparation method of Example 1, except that the mass fraction of the rust inhibitor and corrosion inhibitor is replaced with 0.5 parts, and the rest is the same as in Example 1.

[0075] Comparative Example 5

[0076] The preparation of an organosilicon carbon fiber protective oil agent is carried out according to the preparation method of Example 1, except that the mass fraction of the base silicone oil is replaced with 70, and the rest remains the same as in Example 1.

[0077] Performance testing:

[0078] Test sample: A carbon fiber sample coated with an organosilicon carbon fiber protective oil prepared in the examples and comparative examples, measuring 10cm × 10cm, with a coating thickness of 0.5mm.

[0079] 1. Rust prevention performance test: According to the ASTM B117 salt spray test standard, the test sample was placed in a salt spray chamber (5% NaCl solution, temperature 35℃), and the time (in hours) for rust to appear was recorded. The data are shown in Table 2.

[0080] 2. Corrosion resistance test: The immersion corrosion method was used. The test sample was immersed in 0.5 mol / L sulfuric acid solution at 25℃ for 168 hours, and the weight loss rate (%) of carbon fiber was measured. The data are shown in Table 2.

[0081] 3. Anti-aging performance test: The sample was placed in a UV aging chamber (UVA-340 lamp, irradiance 0.89W / m²). 2 The rust prevention performance retention rate (%) and corrosion resistance performance retention rate (%) were tested at a temperature of 50℃ and a relative humidity of 60% for 500 hours. The data are shown in Table 2.

[0082] Table 2.

[0083]

[0084] The sample from the example is significantly superior to all comparative examples, demonstrating the core advantage of the organosilicon carbon fiber protective oil agent of this invention: the three-dimensional protective network synergistically constructed by the components can maintain performance stability for a long time. Specifically, this is manifested in three key trends:

[0085] ① Clearly defined protective performance levels: The embodiments show a clear advantage in initial rust prevention, corrosion resistance, and anti-aging durability. The protective efficacy is comprehensively improved with the introduction of the anti-aging agent of this invention and the complete combination of components.

[0086] ②The decisive role of anti-aging agents: Any substitution (such as industrial antioxidants), structural modification or complete removal of the anti-aging agent of the present invention in the comparative examples resulted in a precipitous drop in protective performance, highlighting the irreplaceable role of this component in resisting ultraviolet aging and maintaining long-term protection.

[0087] ③ Component integrity is crucial: Insufficient use of key components such as base silicone oil or rust inhibitor in the comparative ratio can trigger a chain reaction of collapse of the synergistic protection network, especially causing the material's performance to deteriorate more rapidly after aging, confirming the necessity of the core design principles emphasized in the document: "mild process to form stable emulsion" and "multi-component compounding for synergistic effect".

[0088] In summary, this invention, through molecular design (such as the heteroconjugated aromatic ring light-absorbing groups of anti-aging agents) and precise formulation (such as the optimization of the content of rust and corrosion inhibitors), forms a dynamic self-healing protective layer on the surface of carbon fibers, fundamentally blocking the penetration path of environmental corrosive factors, thereby achieving a leapfrog improvement in performance.

[0089] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A silicone carbon fiber protective oil agent characterized by, The product comprises the following components in parts by weight: 80-150 parts base silicone oil, 5-25 parts emulsifier, 3-15 parts rust and corrosion inhibitor, 0.1-10 parts thickener, 0.5-1.5 parts anti-aging agent, and 100-300 parts water. The anti-aging agent has the structure shown in Formula 1: R1 in Formula 1 is selected from: methyl, methoxy, phenyl, tert-butyl.

2. The silicone carbon fiber protective oil agent according to claim 1, characterized by, The base silicone oil is selected from polyether-modified polysiloxane.

3. The organosilicon carbon fiber protective oil agent according to claim 1, characterized in that, The emulsifier is selected from N,N-di(hydroxyethyl)cocoamide.

4. The organosilicon carbon fiber protective oil agent according to claim 1, characterized in that, The rust and corrosion inhibitor is selected from dicyclohexylamine.

5. The organosilicon carbon fiber protective oil agent according to claim 1, characterized in that, The thickener is selected from sodium hydroxymethyl cellulose.

6. The organosilicon carbon fiber protective oil agent according to claim 1, characterized in that, The anti-aging agent is selected from any one of the compounds shown in the following structures:

7. A method for preparing an organosilicon carbon fiber protective oil agent according to any one of claims 1-6, characterized in that, Includes the following steps: S1. Add the water, anti-aging agent and thickener to the reaction system and stir until uniform and free of particles; S2. Add the emulsifier and stir until homogeneous; S3. Add the base silicone oil dropwise and stir until homogeneous; S4. Add the rust and corrosion inhibitor, filter, and obtain an organosilicon carbon fiber protective oil.

8. The method for preparing an organosilicon carbon fiber protective oil agent according to claim 7, characterized in that, The S2 process is carried out at 40-50°C.

9. The method for preparing an organosilicon carbon fiber protective oil agent according to claim 7, characterized in that, The S1 process is carried out at 50-75°C.

10. The application of an organosilicon carbon fiber protective oil agent according to any one of claims 1-6 in the field of carbon fiber protective ink.

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