Carbon fiber spinning oil with low surface tension and preparation method thereof

Abstract

The invention discloses a carbon fiber spinning oil agent with low surface tension and a preparation method thereof. The oiling agent is prepared from the following components in parts by weight: 100 parts of an amino modified epoxy silicone oil composition, 20-40 parts of an emulsifier and 2-5 parts of an antistatic agent. The oiling agent is prepared by mixing the components and carrying out a phase inversion emulsification method. The carbon fiber spinning oil agent is an emulsion with the particle size of 50-200 nm, the surface tension of the oil agent is smaller than or equal to 30 mN / m, and the carbon fiber spinning oil agent has the advantages of being small in emulsion particle size, low in surface tension and good in wettability and can effectively improve the permeation and spreading capacity of the oil agent on the surface of a carbon fiber precursor, achieve monofilament protection uniformity of the precursor and improve the performance stability of the carbon fiber.

Description

Technical Field

[0001] The invention relates to a carbon fiber spinning oil with low surface tension and a preparation method thereof, belonging to the technical field of high-performance carbon fiber preparation. Background Art

[0002] Oil is an important auxiliary agent in the production process of carbon fiber. It plays a key role in improving the performance and quality of carbon fiber. It can prevent fiber adhesion, reduce friction, protect fiber filaments from damage, and help to obtain homogeneous pre-oxidized filaments. The oil needs to form a uniform film on the surface of the carbon fiber precursor to play a role in homogenization and protection. Currently, the particle size of oil on the market is generally above 200nm, and the surface tension of the emulsion is above 35mN / m. In actual production applications, there are still problems such as insufficient wettability resulting in poor oil uniformity on the fiber surface, and the generation of filaments and hair on the carbon fiber precursor. Summary of the invention

[0003] The purpose of the present invention is to provide a carbon fiber spinning oil with low surface tension and a preparation method thereof. The present invention uses a hydrophilic amino-modified compound to modify epoxy silicone oil, and then mixes and emulsifies with an emulsifier and an antistatic agent to form a carbon fiber spinning oil with low surface tension.

[0004] The technical solution for achieving the purpose of the present invention is as follows:

[0005] A carbon fiber spinning oil with low surface tension comprises, by weight, 100 parts of an amino-modified epoxy silicone oil composition, 20 to 40 parts of an emulsifier and 2 to 5 parts of an antistatic agent; the amino-modified epoxy silicone oil composition is prepared by the following steps: epoxy silicone oil, an amino-modified compound and a catalyst are stirred and mixed at a mass ratio of 100:30 to 50:2 to 5 at 50 to 60°C for 2±0.5h, then the temperature is raised to 80 to 100°C, and the reaction is continued for 10±1h to obtain the amino-modified epoxy silicone oil composition, the amino-modified compound is selected from one or more of diethanolamine and polyetheramine, and the catalyst is a boron trifluoride ether complex.

[0006] Furthermore, the epoxy value of the epoxy silicone oil is 0.10 to 0.25 mol / 100g.

[0007] Furthermore, the emulsifier is an emulsifier commonly used in carbon fiber spinning oil, and is selected from one or more of fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether and castor oil polyoxyethylene ether.

[0008] Furthermore, the antistatic agent is one commonly used in carbon fiber spinning oil, and is selected from one or more of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and N,N-dihydroxyethyl octadecylamine.

[0009] The specific steps of the preparation method of the above-mentioned carbon fiber spinning oil with low surface tension are as follows: after the amino-modified epoxy silicone oil composition, emulsifier and antistatic agent are stirred and evenly mixed according to the ratio, water is added through the phase inversion emulsification method to obtain an emulsion with a particle size distribution of 50 to 200 nm and a surface tension of ≤30 mN / m.

[0010] Compared with the prior art, the present invention has the following advantages:

[0011] The present invention adopts highly hydrophilic amino-modified compounds to modify epoxy silicone oil to prepare carbon fiber precursor oil agent, which has the characteristics of small emulsion particle size, low surface tension and good wettability, can effectively improve the oil agent's ability to penetrate and spread on the surface of carbon fiber precursor, achieve the uniformity of single-filament protection of the precursor, and improve the performance stability of the carbon fiber. DETAILED DESCRIPTION

[0012] The content and technical solutions of the present invention are further described below in conjunction with specific embodiments, but should not be construed as limiting the present invention. Without departing from the concept of the present invention, simple modifications or replacements made to the method, steps or conditions of the present invention all fall within the scope of the present invention.

[0013] The raw materials and reagents used in the following examples and comparative examples can all be purchased commercially.

[0014] Example 1

[0015] (1) Preparation of an amino-modified epoxy silicone oil composition: 100 parts by mass of epoxy silicone oil, whose epoxy value is 0.10 mol / 100 g, 30 parts by mass of an amino-modified compound, which is diethanolamine, and 2 parts by mass of a catalyst, which is a boron trifluoride ether complex, are stirred and mixed at a temperature of 50° C. for 2 h, then the temperature is raised to 80° C. and the reaction is continued for 10 h to obtain an amino-modified epoxy silicone oil composition.

[0016] (2) Preparation of a carbon fiber spinning oil with low surface tension: 100 parts by weight of the above-mentioned amino-modified epoxy silicone oil composition, 20 parts by weight of an emulsifier, and 2 parts by weight of an antistatic agent, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, are mixed uniformly according to a proportion, and then water is added to obtain an amino-modified epoxy silicone oil emulsion by a phase inversion emulsification method. The particle size is 188 nm and the surface tension is 29.2 mN / m.

[0017] The evaluation results on the production line using the prepared oil agent are shown in Table 1. The oil content of the carbon fiber precursor is 0.85%, the precursor hair grade is 1.2 (divided into 1-5 grades, 1 is the best, 5 is the worst), the pre-oxidized silk skin chip rate is 4.3%, the carbon fiber tensile strength is 5137MPa, and the carbon fiber hair grade is 1.4 (divided into 1-5 grades, 1 is the best, 5 is the worst).

[0018] Example 2

[0019] (1) Preparation of an amino-modified epoxy silicone oil composition: 100 parts by mass of epoxy silicone oil, whose epoxy value is 0.20 mol / 100 g, 40 parts by mass of an amino-modified compound, which is a polyetheramine, and 3 parts by mass of a catalyst, are stirred and mixed at a temperature of 60° C. for 2 h, then the temperature is raised to 90° C. and the reaction is continued for 10 h to obtain an amino-modified epoxy silicone oil composition.

[0020] (2) Preparation of a carbon fiber spinning oil with low surface tension: 100 parts by mass of the above-mentioned amino-modified epoxy silicone oil composition, 30 parts by mass of an emulsifier, and 3 parts by mass of an antistatic agent, N,N-dihydroxyethyl octadecylamine, are mixed uniformly according to a proportion, and then water is added to obtain an amino-modified epoxy silicone oil emulsion by a phase inversion emulsification method. The particle size is 132 nm and the surface tension is 28.1 mN / m.

[0021] The evaluation results on the production line using the prepared oil agent are shown in Table 1. The oil content of the carbon fiber precursor is 0.91%, the precursor hair grade is 1.1 (divided into 1-5 grades, 1 is the best, 5 is the worst), the pre-oxidized yarn skin-core ratio is 3.8%, the carbon fiber tensile strength is 5211 MPa, and the carbon fiber hair grade is 1.3 (divided into 1-5 grades, 1 is the best, 5 is the worst).

[0022] Example 3

[0023] (1) Preparation of an amino-modified epoxy silicone oil composition: 100 parts by mass of epoxy silicone oil, whose epoxy value is 0.25 mol / 100 g, 50 parts by mass of an amino-modified compound, which is diethanolamine, and 5 parts by mass of a catalyst, which is boron trifluoride ether complex, are stirred and mixed at a temperature of 60° C. for 2 h, then the temperature is raised to 100° C. and the reaction is continued for 10 h to obtain an amino-modified epoxy silicone oil composition.

[0024] (2) Preparation of a carbon fiber spinning oil with low surface tension: 100 parts by weight of the above-mentioned amino-modified epoxy silicone oil composition, 40 parts by weight of castor oil polyoxyethylene ether as an emulsifier, and 5 parts by weight of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate as an antistatic agent are mixed uniformly according to the proportion, and then water is added to obtain an amino-modified epoxy silicone oil emulsion by a phase inversion emulsification method. The particle size is 78 nm and the surface tension is 27.5 mN / m.

[0025] The evaluation results on the production line using the prepared oil agent are shown in Table 1. The oil content of the carbon fiber precursor is 0.88%, the precursor hair grade is 1.1 (divided into 1-5 grades, 1 is the best, 5 is the worst), the pre-oxidized yarn skin-core ratio is 3.5%, the carbon fiber tensile strength is 5257 MPa, and the carbon fiber hair grade is 1.2 (divided into 1-5 grades, 1 is the best, 5 is the worst).

[0026] Comparative Example 1

[0027] (1) Preparation of an amino-modified epoxy silicone oil composition: 100 parts by mass of epoxy silicone oil, whose epoxy value is 0.10 mol / 100 g, 30 parts by mass of an amino-modified compound, which is diethanolamine, and 2 parts by mass of a catalyst, which is a boron trifluoride ether complex, are stirred and mixed at a temperature of 50° C. for 2 h, then the temperature is raised to 80° C. and the reaction is continued for 10 h to obtain an amino-modified epoxy silicone oil composition.

[0028] (2) Preparation of carbon fiber spinning oil: 100 parts by weight of the above-mentioned amino-modified epoxy silicone oil composition, 10 parts by weight of emulsifier fatty alcohol polyoxyethylene ether, and 0 parts by weight of antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are mixed according to the ratio, and then water is added to obtain an amino-modified epoxy silicone oil emulsion by a phase inversion emulsification method. The particle size is 345 nm and the surface tension is 32.3 mN / m.

[0029] The evaluation results of the production line using the prepared oil are shown in Table 1. The oil content of the carbon fiber precursor is 0.81%, the hairiness of the precursor is 2.3 (divided into 1-5 levels, 1 is the best, 5 is the worst), the pre-oxidized fiber skin chip rate is 8.9%, the tensile strength of the carbon fiber is 4873MPa, and the hairiness of the carbon fiber is 2.0 (divided into 1-5 levels, 1 is the best, 5 is the worst). Compared with Example 1, the reduction in the emulsifier content leads to an increase in the particle size and surface tension of the emulsion, a deterioration in the uniformity of the precursor oiling, an increase in the hairiness of the precursor and the carbon fiber, and a decrease in the carbonization strength.

[0030] Comparative Example 2

[0031] (1) Preparation of an amino-modified epoxy silicone oil composition: 100 parts by mass of epoxy silicone oil, whose epoxy value is 0.10 mol / 100 g, 30 parts by mass of an amino-modified compound, which is diethanolamine, and 2 parts by mass of a catalyst, which is a boron trifluoride ether complex, are stirred and mixed at a temperature of 50° C. for 2 h, then the temperature is raised to 80° C. and the reaction is continued for 10 h to obtain an amino-modified epoxy silicone oil composition.

[0032] (2) Preparation of carbon fiber spinning oil: 100 parts by weight of the above-mentioned amino-modified epoxy silicone oil composition, 50 parts by weight of emulsifier fatty alcohol polyoxyethylene ether, and 10 parts by weight of antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are mixed according to the ratio, and then water is added to obtain an amino-modified epoxy silicone oil emulsion by a phase inversion emulsification method. The particle size is 57 nm and the surface tension is 26.8 mN / m.

[0033] The evaluation results of the oil preparation production line are shown in Table 1. The oil content of the carbon fiber precursor is 0.82%, the precursor hair grade is 2.0 (divided into 1-5 grades, 1 is the best, 5 is the worst), the pre-oxidation silk skin chip rate is 10.7%, the carbon fiber tensile strength is 4776MPa, and the carbon fiber hair grade is 2.1 (divided into 1-5 grades, 1 is the best, 5 is the worst). Compared with Example 1, the emulsifier content and antistatic agent content in the oil preparation are too much, resulting in a decrease in the heat resistance of the oil preparation, insufficient heat resistance protection during carbonization, and an increase in the pre-oxidation silk skin core rate, resulting in a decrease in carbon fiber strength and an increase in hair.

[0034] Comparative Example 3

[0035] Preparation of unmodified conventional epoxy silicone oil emulsion: use 100 parts by mass of epoxy silicone oil with an epoxy value of 0.10 mol / 100g, 20 parts by mass of emulsifier fatty alcohol polyoxyethylene ether, and 2 parts by mass of antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate. After stirring and mixing the above components according to the ratio, water is added to obtain ordinary epoxy silicone oil emulsion through phase inversion emulsification method. The particle size is 482nm and the surface tension is 36.1mN / m.

[0036] The evaluation results of the production line using the prepared oil agent are shown in Table 1. The oil content of the carbon fiber precursor is 0.83%, the precursor hair grade is 2.5 (divided into 1-5 grades, 1 is the best, 5 is the worst), the pre-oxidized silk skin and core rate is 9.5%, the carbon fiber tensile strength is 4840MPa, and the carbon fiber hair grade is 2.3 (divided into 1-5 grades, 1 is the best, 5 is the worst). Compared with Example 1, the amino modification of epoxy silicone oil was not performed, and the hair grade of the prepared precursor was significantly increased, indicating that the protective effect of the oil agent on the surface of the precursor was significantly reduced, and the uniformity of the oil protection of the fiber was deteriorated; at the same time, it caused insufficient homogeneous pre-oxidation in the carbonization stage, increased skin-core rate, decreased carbon fiber strength, and increased hair grade.

[0037] Comparative Example 4

[0038] (1) Preparation of an amino-modified epoxy silicone oil composition: 100 parts by mass of epoxy silicone oil, whose epoxy value is 0.10 mol / 100 g, 30 parts by mass of ethylenediamine, which is an amino-modified compound, and 2 parts by mass of boron trifluoride ether complex, which is a catalyst, are stirred and mixed at a temperature of 50° C. for 2 h, then the temperature is raised to 80° C. and the reaction is continued for 10 h to obtain an amino-modified epoxy silicone oil composition.

[0039] (2) Preparation of carbon fiber spinning oil: 100 parts by weight of the above-mentioned amino-modified epoxy silicone oil composition, 25 parts by weight of emulsifier fatty alcohol polyoxyethylene ether, and 2 parts by weight of antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are mixed according to the ratio, and then water is added to obtain an amino-modified epoxy silicone oil emulsion by a phase inversion emulsification method. The particle size is 257 nm and the surface tension is 31.8 mN / m.

[0040] The evaluation results of the oil preparation production line are shown in Table 1. The oil content of the carbon fiber precursor is 0.74%, the precursor hairiness level is 2.1 (divided into 1-5 levels, 1 is the best, 5 is the worst), the pre-oxidized fiber skin chip rate is 8.4%, the carbon fiber tensile strength is 4921MPa, and the carbon fiber hairiness level is 2.0 (divided into 1-5 levels, 1 is the best, 5 is the worst). Compared with Example 1, the surface tension and particle size of the prepared oil preparation are increased by replacing the amino-modified compound diethanolamine with ethylenediamine, and the wettability is deteriorated, resulting in an increase in the precursor and carbon fiber hairiness, and the carbonization strength is also reduced.

[0041] Comparative Example 5

[0042] (1) Preparation of an amino-modified epoxy silicone oil composition: 100 parts by mass of epoxy silicone oil, whose epoxy value is 0.10 mol / 100 g, 30 parts by mass of amino-modified compound, and 0 parts by mass of catalyst, boron trifluoride ether complex, are stirred and mixed at a temperature of 50° C. for 2 h, then the temperature is raised to 80° C. and the reaction is continued for 10 h to obtain an amino-modified epoxy silicone oil composition.

[0043] (2) Preparation of carbon fiber spinning oil: 100 parts by weight of the above-mentioned amino-modified epoxy silicone oil composition, 30 parts by weight of emulsifier fatty alcohol polyoxyethylene ether, and 2 parts by weight of antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are mixed according to the ratio, and then water is added to obtain an amino-modified epoxy silicone oil emulsion by a phase inversion emulsification method. The particle size is 411 nm and the surface tension is 34.5 mN / m.

[0044] The evaluation results of the oil preparation production line are shown in Table 1. The oil content of the carbon fiber precursor is 0.77%, the precursor hair grade is 2.3 (divided into 1-5 grades, 1 is the best, 5 is the worst), the pre-oxidized fiber skin chip rate is 9.2%, the carbon fiber tensile strength is 4892MPa, and the carbon fiber hair grade is 2.1 (divided into 1-5 grades, 1 is the best, 5 is the worst). Compared with Example 1, the catalyst boron trifluoride ether complex is removed in the synthesis of the amino-modified epoxy silicone oil composition, and the particle size of the obtained oil preparation emulsion increases, the surface tension increases, the wettability deteriorates, the protective effect of the oil preparation deteriorates, and the performance of the carbon fiber decreases.

[0045] Comparative Example 6

[0046] (1) Preparation of an amino-modified epoxy silicone oil composition: 100 parts by mass of epoxy silicone oil, whose epoxy value is 0.10 mol / 100 g, 30 parts by mass of amino-modified compound, and 2 parts by mass of catalyst, dibutyltin dilaurate, are stirred and mixed at a temperature of 50° C. for 2 h, then the temperature is raised to 80° C. and the reaction is continued for 10 h to obtain an amino-modified epoxy silicone oil composition.

[0047] (2) Preparation of carbon fiber spinning oil: 100 parts by weight of the above-mentioned amino-modified epoxy silicone oil composition, 20 parts by weight of emulsifier fatty alcohol polyoxyethylene ether, and 2 parts by weight of antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are mixed according to the ratio, and then water is added to obtain an amino-modified epoxy silicone oil emulsion by a phase inversion emulsification method. The particle size is 345 nm and the surface tension is 33.1 mN / m.

[0048] The evaluation results of the oil preparation production line are shown in Table 1. The oil content of the carbon fiber precursor is 0.82%, the precursor hair grade is 2.3 (divided into 1-5 grades, 1 is the best, 5 is the worst), the pre-oxidized fiber skin chip rate is 8.5%, the carbon fiber tensile strength is 4939MPa, and the carbon fiber hair grade is 2.1 (divided into 1-5 grades, 1 is the best, 5 is the worst). Compared with Example 1, the catalyst dibutyltin dilaurate is used to replace the boron trifluoride ether complex, the catalytic reaction effect is poor, and the performance of the obtained oil preparation is reduced.

[0049] Comparative Example 7

[0050] (1) Preparation of an amino-modified epoxy silicone oil composition: 100 parts by mass of epoxy silicone oil, whose epoxy value is 0.10 mol / 100 g, 60 parts by mass of amino-modified compound, which is diethanolamine, and 10 parts by mass of catalyst, which is boron trifluoride ether complex, are stirred and mixed at a temperature of 50° C. for 2 h, then the temperature is raised to 80° C. and the reaction is continued for 10 h to obtain an amino-modified epoxy silicone oil composition.

[0051] (2) Preparation of carbon fiber spinning oil: 100 parts by weight of the above-mentioned amino-modified epoxy silicone oil composition, 20 parts by weight of emulsifier fatty alcohol polyoxyethylene ether, and 2 parts by weight of antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are mixed according to the ratio, and then water is added to obtain an amino-modified epoxy silicone oil emulsion by a phase inversion emulsification method. The particle size is 45 nm and the surface tension is 23.5 mN / m.

[0052] The evaluation results of the production line using the prepared oil agent are shown in Table 1. The oil content of the carbon fiber precursor is 0.92%, the precursor hair grade is 1.3 (divided into 1-5 grades, 1 is the best, 5 is the worst), the pre-oxidation silk skin chip rate is 10.3%, the carbon fiber tensile strength is 4811MPa, and the carbon fiber hair grade is 1.8 (divided into 1-5 grades, 1 is the best, 5 is the worst). Compared with Example 1, the mass ratio of amino-modified compounds, catalysts and epoxy silicone oil is too high, resulting in a decrease in the mass proportion of the heat-resistant structure of silicone oil, a decrease in the heat resistance of the oil agent, insufficient heat resistance protection during the carbonization process of the oil agent, and an increase in the pre-oxidation silk skin core rate, which will also cause the carbon fiber strength to decrease and the hair to increase.

[0053]

[0054] In summary, the present invention uses a highly hydrophilic amino-modified compound to modify epoxy silicone oil to prepare a carbon fiber precursor oil agent, which has the characteristics of small emulsion particle size, low surface tension, and good wettability. It can effectively improve the oil agent's ability to penetrate and spread on the surface of the carbon fiber precursor, achieve uniform single-filament protection of the precursor, and improve the performance stability of the carbon fiber.

Claims

1. A carbon fiber spinning oil with low surface tension, characterized in that: The amino-modified epoxy silicone oil composition comprises 100 parts by weight, 20-40 parts by weight of an emulsifier and 2-5 parts by weight of an antistatic agent; the amino-modified epoxy silicone oil composition is prepared by the following steps: epoxy silicone oil, an amino-modified compound and a catalyst are stirred and mixed at a mass ratio of 100:30-50:2-5 at 50-60° C. for 2±0.5 h, then the temperature is raised to 80-100° C., and the reaction is continued for 10±1 h to obtain the amino-modified epoxy silicone oil composition, wherein the amino-modified compound is selected from one or more of diethanolamine and polyetheramine, and the catalyst is a boron trifluoride ether complex.

2. The carbon fiber spinning oil according to claim 1, characterized in that The epoxy value of epoxy silicone oil is 0.10~0.25 mol / 100g.

3. The carbon fiber spinning oil according to claim 1, characterized in that: The emulsifier is selected from at least one of fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether and castor oil polyoxyethylene ether.

4. The carbon fiber spinning oil according to claim 1, characterized in that: The antistatic agent is selected from at least one of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and N,N-dihydroxyethyl octadecylamine.

5. The method for preparing a carbon fiber spinning oil with low surface tension according to any one of claims 1 to 4, characterized in that: The specific steps are as follows: after uniformly mixing the amino-modified epoxy silicone oil composition, emulsifier and antistatic agent according to the proportion, water is added to obtain an emulsion with a particle size distribution of 50-200 nm and a surface tension of ≤30 mN / m through a phase inversion emulsification method.

Images