CN104179019A - A kind of preparation method of carbon fiber raw silk oil agent - Google Patents

Abstract

The invention relates to a preparation method of a carbon fiber precursor oiling agent, which comprises the following steps of taking a composite emulsifier and characteristic composite modified silicone oil according to the proportion of 1-4: 3-10 parts by weight of the mixture is put into a high-shear emulsifying machine and uniformly stirred, a composite auxiliary agent is added, a proper amount of deionized water is added dropwise, stirring and stirring time is 20-120 min, the pH value is adjusted to 3-10, and the obtained light blue, light yellow or white emulsion is the carbon fiber precursor oiling agent. The method has simple process operation and can be directly applied to an industrial production line. The oil agent prepared by the method has good permeability when in use, can improve the fiber bundling property, is high temperature resistant, has good process stability, can well protect the fiber in the whole pre-oxidation process and the initial stage of low-temperature carbonization, greatly reduces the phenomena of monofilament adhesion and doubling, reduces the surface defects of the fiber, and improves the performance of the carbon fiber.

Description

A kind of preparation method of carbon fiber raw silk oil agent

technical field

The invention relates to a preparation method of an oil agent, in particular to a preparation method of a carbon fiber raw silk oil agent.

Background technique

Carbon fiber has many advantages such as high strength, high modulus, high temperature resistance, acid and alkali corrosion resistance, etc., and is widely used in aerospace, civil engineering, new energy and other fields. At the same time, carbon fiber composite materials are being widely used in various industries. With the rapid development of economy and technology, the demand for carbon fiber will further increase.

High-quality carbon fiber precursors are the key to preparing high-quality carbon fibers, and the properties of the precursors directly determine the properties of the final carbon fibers. In the raw silk manufacturing process, the oiling process is an extremely important production process. High-quality oiling agents can solve the adhesion of the filaments during the spinning process; Thermal adhesion and thermal melting of filaments caused by overheating and surface defects of pre-oxidized fibers; reduction of fiber thermal melting and thermal adhesion caused by a large number of by-products in the low-temperature carbonization stage of 400-1500 ° C; at the same time, oil Film formation can reduce fuzzing, broken filaments and surface defects caused by friction between the tow and mechanical equipment.

Carbon fiber raw silk oil should have excellent high temperature resistance, antistatic performance, wetting and lubricating performance, clustering and anti-sticking performance, but carbon fiber raw silk oil with excellent performance is very rare in the domestic market, and even domestic carbon fiber raw silk There are very few manufacturers of silk finishing agents. At present, there are two types of carbon fiber oils that are most commonly used. One is based on long-chain fatty acid and polyol polyester and long-chain fatty amide ethylene oxide adduct as the main component, and the other is based on poly Dimethyl siloxane is a host-modified silicone oil agent. Silicone oils show advantages in heat resistance, lubricity, and anti-sticking properties. Silicone oils modified by different groups have different special properties. Amino-modified silicone oils have excellent film-forming and hydrophilic properties, epoxy-modified silicone oils have excellent heat resistance, and polyether-modified silicone oils have excellent self- emulsifying properties. A good carbon fiber precursor oil should be a multifunctional compound oil. The compound multifunctional oil with excellent preparation performance and good stability is a difficult problem that carbon fiber precursor oil needs to solve urgently.

Contents of the invention

The technical problem to be solved by the present invention is to provide a preparation method of a carbon fiber precursor oil agent with excellent preparation performance and good stability for the deficiencies of the prior art.

The technical problem to be solved by the present invention is achieved through the following technical solutions. The present invention is a preparation method of carbon fiber precursor oil, which is characterized in that the steps are as follows:

Take the composite emulsifier and the characteristic composite modified silicone oil, put them into the high shear emulsifier according to the weight ratio of 1~4:3~10, stir evenly, add the composite additive with a mass percentage of 1~2%, and then drop it Add an appropriate amount of deionized water, control the stirring speed to 1500-10000r/min, the stirring time to 20-120min, adjust the pH value to 3-10, and the obtained light blue, light yellow or white emulsion is the carbon fiber precursor oil;

The composite emulsifier is composed of at least two emulsifiers as follows: isomerized alcohol polyoxyethylene ether type nonionic surfactant, alkylphenol polyoxyethylene ether type nonionic surfactant, fatty alcohol polyoxyethylene ether type nonionic surfactant, Oxyethylene ether type nonionic surfactant, polyoxyethylene sorbitan ester type nonionic surfactant, alkyl alcohol amide type nonionic surfactant, C10~C18 linear alcohol ether type nonionic surfactant; During preparation, put at least two emulsifiers above in a container, heat up to 40-90°C, stir evenly and cool to room temperature to obtain a milky white or light yellow composite emulsifier;

The characteristic composite modified silicone oil is made of at least two kinds of raw materials: 30-80 parts of amino-modified polydimethylsiloxane, 10-60 parts of polyether-modified polydimethylsiloxane, 10~50 parts of epoxy modified polydimethylsiloxane, 10~20 parts of vinyl modified polydimethylsiloxane;

The composite additives are compounded by at least one raw material in the following groups A and B respectively; the raw materials in group A are trihydroxyethylmethyl quaternary ammonium methyl sulfate, dodecyl trimethyl chloride Ammonium, isotridecanyl ether phosphate methyl ester salt, polyoxyethylene laurate; Group B raw materials are modified polymethylsiloxane type defoamer, fatty alcohol polyoxyethylene ether, isoamyl alcohol, tributyl phosphate ester.

In the preparation method of the carbon fiber precursor oil agent of the present invention, the raw material amino-modified polydimethylsiloxane in the described characteristic composite modified silicone oil has the following characteristics:

Part of the side chain of dimethyl silicon with a methyl group at the end is substituted by chemical formula (I) or chemical formula (II)

-CH ₂ -NH-CH ₂ -CH ₂ -NH ₂ (I)

R- _NH2 (II).

In the preparation method of the carbon fiber precursor oil agent according to the present invention, the raw material polyether modified polydimethylsiloxane in the characteristic composite modified silicone oil has the following characteristics:

Part of the side chain of dimethyl silicon with a methyl group at the end is substituted by chemical formula (I) or chemical formula (II)

-CH ₂ (OCH ₂ -CH ₂ ) _10~15 OCH ₃ (Ⅰ)

-CH ₂ -NH (CH ₂ -CH ₂ ) _10~15 OCOCH ₃ (Ⅱ).

In the preparation method of the carbon fiber precursor oil agent of the present invention, the raw material epoxy-modified polydimethylsiloxane in the characteristic composite modified silicone oil has the following characteristics:

Part of the side chain or terminal methyl group of dimethyl silicon with a methyl group is substituted by formula (I), formula (II) or formula (III)

(I) (Ⅱ) (Ⅲ).

In the preparation method of carbon fiber precursor oil agent of the present invention,

In the preparation method of the carbon fiber precursor oil agent of the present invention, the viscosity of the amino-modified silicone oil at 25°C is 10-6000 mm ² /s, and the ammonia value is 0.3-1.0; the epoxy-modified The viscosity of the silicone oil at 25°C is 50-10000 mm ² /s, and the epoxy equivalent value is 0.001-0.25; the viscosity of the polyether-modified silicone oil at 25°C is 300-1500 mm ² /s. The modification amount of the ether group is 0.001-0.8; the viscosity of the vinyl-modified silicone oil at 25°C is 100-6000 mm ² /s, and the modification amount of the vinyl group is 0.001-0.5.

Use of the carbon fiber precursor oil prepared by the preparation method described in any one of the above in small tow and large tow carbon fiber precursor oils.

When the oil agent prepared by the present invention is suitable for the precursor fibers of different tows, the use concentration can be adjusted by adding water as required, and the addition of water has no influence on the performance of the oil agent itself.

The present invention is also applicable to the carbon fiber precursor composite oil obtained by emulsifying the single component of the modified silicone oil and then compounding according to the above method.

Compared with the prior art, the method of the invention has simple process operation and can be directly applied to industrial production lines. The oil prepared by the method of the present invention has strong permeability and good lubricity when used, can improve fiber bundles, can form a film on the surface of monofilaments, has high temperature resistance, and good process stability, and can be used during the entire preoxidation process and In the early stage of low-temperature carbonization, the fibers are well protected, the phenomenon of monofilament adhesion and parallel filaments is greatly reduced, the surface defects of fibers are reduced, and the performance of carbon fibers is improved.

Detailed ways

The specific technical solutions of the present invention are further described below, so that those skilled in the art can further understand the present invention, without limiting their rights.

Embodiment 1, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

Use the compound of alkylphenol polyoxyethylene ether type nonionic surfactant and fatty alcohol polyoxyethylene ether type nonionic surfactant as the compound emulsifier, put the compound emulsifier in the container, raise the temperature to 60°C, and stir After uniformity, cool to room temperature to obtain a milky white or light yellow composite emulsifier. Take the composite emulsifier and 60 parts of amino-modified polydimethylsiloxane (25°C viscosity is 100 mm ² /s, ammonia value is 0.6, modified group group chemical formula (Ⅰ)) and 40 parts of polyether modified polydimethylsiloxane (viscosity at 25°C is 1500mm ² /s, modification amount 0.5) compound modified silicone oil is put into high shear according to the weight ratio of 3:10 Stir evenly in the emulsifier, add 1% compound additive composed of isotridecyl phosphate methyl ester salt and fatty alcohol polyoxyethylene ether, and then add deionized water dropwise to it to control The stirring speed is 3000r/min, stirring for 60min, adjusting the pH value to 8, and the obtained light yellow or white emulsion is the raw silk oil agent.

Embodiment 2, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

Use C13 linear alcohol ether type nonionic surfactant and fatty alcohol polyoxyethylene ether type nonionic surfactant compound as compound emulsifier, put the compound emulsifier in the container, raise the temperature to 60°C, and stir well Cool to room temperature to obtain a milky white or light yellow composite emulsifier, take the composite emulsifier and 60 parts of amino-modified polydimethylsiloxane (the viscosity at 25°C is 100 mm ² /s, the ammonia value is 0.6, and the chemical formula of the modified group is (I)) and 40 parts of polyether-modified polydimethylsiloxane (viscosity at 25°C is 1500mm ² /s, modification amount 0.5) composite modified silicone oil into the high-shear emulsifier according to the weight ratio of 3:10 Stir evenly in the medium, add a compound additive composed of 1% isotridecyl ether phosphate methyl ester salt and fatty alcohol polyoxyethylene ether 1:1, and then add deionized water dropwise to it, and control the stirring speed to 3000r/min, stirring for 60min, adjusting the pH value to 7, the obtained light yellow or white emulsion is the raw silk oil.

Embodiment 3, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

Use C13 linear alcohol ether type nonionic surfactant and fatty alcohol polyoxyethylene ether type nonionic surfactant compound as compound emulsifier, put the compound emulsifier in the container, raise the temperature to 60°C, and stir well Cool to room temperature to obtain a milky white or light yellow composite emulsifier, take the composite emulsifier and 50 parts of amino-modified polydimethylsiloxane (the viscosity at 25°C is 100 mm ² /s, the ammonia value is 0.6, and the chemical formula of the modified group is (I)), 30 parts of polyether-modified polydimethylsiloxane (viscosity at 25°C is 1500mm ² /s, modification amount 0.5), 20 parts of epoxy-modified polydimethylsiloxane (25°C When the viscosity is 3000mm ² /s, the epoxy equivalent value is 0.15, the chemical formula of the modified group (I)) the compound modified silicone oil is put into the high shear emulsifier according to the weight ratio of 3:10 and stirred evenly. 1% isotridecyl ether phosphate methyl ester salt and fatty alcohol polyoxyethylene ether 1:1 compound additive, then add deionized water dropwise to it, control the stirring speed to 3000r/min, stir for 60min, Adjust the pH value to 7, and the obtained light yellow or white emulsion is the original silk oil agent.

Embodiment 4, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

Use C13 linear alcohol ether type nonionic surfactant and fatty alcohol polyoxyethylene ether type nonionic surfactant compound as compound emulsifier, put the compound emulsifier in the container, raise the temperature to 60°C, and stir well Cool to room temperature to obtain a milky white or light yellow composite emulsifier, take the composite emulsifier and 50 parts of amino-modified polydimethylsiloxane (the viscosity at 25°C is 100 mm ² /s, the ammonia value is 0.6, and the chemical formula of the modified group is (I)), 20 parts of polyether-modified polydimethylsiloxane (viscosity at 25°C is 1500mm ² /s, modification amount 0.5), 20 parts of epoxy-modified polydimethylsiloxane (25°C The viscosity is 3000mm ² /s, the epoxy equivalent value is 0.15, the chemical formula of the modified group (I)), 10 parts of vinyl modified polydimethylsiloxane (viscosity at 25°C is 5000 mm ² /s, the vinyl modification amount is 0.1) the compound modified silicone oil is put into the high shear emulsifier according to the weight ratio of 3:10 and stirred evenly, and the percentage content of 1% isotridecyl ether phosphate methyl ester salt is added and fatty alcohol polyoxyethylene ether 1:1 compound additive, then add deionized water dropwise to it, control the stirring speed at 3000r/min, stir for 60min, adjust the pH value to 9, the obtained light yellow or white emulsion is For raw silk oil.

Embodiment 5, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

Use C13 linear alcohol ether type nonionic surfactant and fatty alcohol polyoxyethylene ether type nonionic surfactant compound as compound emulsifier, put the compound emulsifier in the container, raise the temperature to 60°C, and stir well Cool to room temperature to obtain a milky white or light yellow composite emulsifier, take the composite emulsifier and 50 parts of amino-modified polydimethylsiloxane (the viscosity at 25°C is 100 mm ² /s, the ammonia value is 0.6, and the chemical formula of the modified group is (I)), 20 parts of polyether-modified polydimethylsiloxane (viscosity at 25°C is 1500mm ² /s, modification amount 0.5), 20 parts of epoxy-modified polydimethylsiloxane (25°C The viscosity is 3000mm ² /s, the epoxy equivalent value is 0.15, the chemical formula of the modified group (I)), 10 parts of vinyl modified polydimethylsiloxane (viscosity at 25°C is 5000 mm ² /s, the vinyl modification amount is 0.1) the compound modified silicone oil is put into the high shear emulsifier according to the weight ratio of 3:10 and stirred evenly, and the percentage content of 1% trihydroxyethylmethyl quaternary ammonium sulfuric acid is added Methyl ester salt and modified polymethylsiloxane type defoamer composed of a 1:1 compound additive, and then drop deionized water into it, control the stirring speed at 3000r/min, stir for 60min, and adjust the pH value to 7. The obtained light yellow or white emulsion is the original silk oil agent.

Embodiment 6, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

Use the compound of C13 linear alcohol ether type nonionic surfactant, fatty alcohol polyoxyethylene ether type nonionic surfactant, isomerized alcohol polyoxyethylene ether type nonionic surfactant as compound emulsifier, and compound Put the emulsifier in a container, raise the temperature to 60°C, stir evenly, and cool to room temperature to obtain a milky white or light yellow composite emulsifier. Take the composite emulsifier and 50 parts of amino-modified polydimethylsiloxane (viscosity at 25°C is 100mm ² /s, ammonia value 0.6, modified group chemical formula (I)), 20 parts of polyether modified polydimethylsiloxane (viscosity at 25°C is 1500mm ² /s, modification amount 0.5), 20 1 part of epoxy-modified polydimethylsiloxane (viscosity at 25°C is 3000 mm ² /s, epoxy equivalent value is 0.15, chemical formula of modifying group (I)), 10 parts of vinyl-modified polydimethylsiloxane The composite modified silicone oil of methyl siloxane (viscosity at 25°C is 5000 mm ² /s, vinyl modification amount is 0.1) is put into a high shear emulsifier according to the weight ratio of 2:9 and stirred evenly, adding A 1:1 composite additive composed of 1% trishydroxyethylmethyl quaternary ammonium methyl sulfate and modified polymethylsiloxane type defoamer, and then drop deionized water into it, Control the stirring speed to 3500r/min, stir for 60min, adjust the pH value to 7, and the obtained light yellow or white emulsion is the raw silk oil agent.

Embodiment 7, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

Use the compound of C13 linear alcohol ether type nonionic surfactant, fatty alcohol polyoxyethylene ether type nonionic surfactant, isomerized alcohol polyoxyethylene ether type nonionic surfactant as compound emulsifier, and compound Put the emulsifier in a container, raise the temperature to 60°C, stir evenly, and cool to room temperature to obtain a milky white or light yellow composite emulsifier. Take the composite emulsifier and 60 parts of amino-modified polydimethylsiloxane (the viscosity at 25°C is 100mm ² /s, ammonia value 0.6, modified group chemical formula (I)), 15 parts of polyether modified polydimethylsiloxane (viscosity at 25°C is 1500mm ² /s, modification amount 0.5), 15 1 part of epoxy-modified polydimethylsiloxane (viscosity at 25°C is 3000 mm ² /s, epoxy equivalent value is 0.15, chemical formula of modifying group (I)), 10 parts of vinyl-modified polydimethylsiloxane The composite modified silicone oil of methyl siloxane (viscosity at 25°C is 5000 mm ² /s, vinyl modification amount is 0.1) is put into a high shear emulsifier according to the weight ratio of 2:9 and stirred evenly, adding A 1:1 composite additive composed of 1% trishydroxyethylmethyl quaternary ammonium methyl sulfate and modified polymethylsiloxane type defoamer, and then drop deionized water into it, Control the stirring speed to 3000r/min, stir for 60min, adjust the pH value to 7, and the obtained light yellow or white emulsion is the raw silk oil agent.

Embodiment 8, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

Use the compound of C13 linear alcohol ether type nonionic surfactant, fatty alcohol polyoxyethylene ether type nonionic surfactant, isomerized alcohol polyoxyethylene ether type nonionic surfactant as compound emulsifier, and compound Put the emulsifier in a container, raise the temperature to 60°C, stir evenly, and cool to room temperature to obtain a milky white or light yellow composite emulsifier. Take the composite emulsifier and 60 parts of amino-modified polydimethylsiloxane (the viscosity at 25°C is 3000mm ² /s, ammonia value 0.3), 15 parts of polyether-modified polydimethylsiloxane (viscosity at 25°C is 1500mm ² /s, modification amount 0.5), 15 parts of epoxy-modified polydimethylsiloxane Siloxane (viscosity at 25°C is 3000mm ² /s, epoxy equivalent value is 0.15, modification group chemical formula (I)), 10 parts of vinyl modified polydimethylsiloxane (at 25°C The viscosity is 5000 mm ² /s, the modification amount of vinyl group is 0.1) the composite modified silicone oil is put into the high shear emulsifier according to the weight ratio of 2:9 and stirred evenly, and the percentage content of 1% trihydroxyethyl ether is added Methyl quaternary ammonium methyl sulfate salt, modified polymethylsiloxane type defoamer, and tributyl phosphate are compound additives of 2:1:1, and deionized water is added dropwise to it, and the stirring is controlled The speed is 3500r/min, stirring for 60min, adjusting the pH value to 8, and the obtained light yellow or white emulsion is the raw silk oil.

Embodiment 9, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

Use the compound of C13 linear alcohol ether type nonionic surfactant, fatty alcohol polyoxyethylene ether type nonionic surfactant, isomerized alcohol polyoxyethylene ether type nonionic surfactant as compound emulsifier, and compound Put the emulsifier in a container, raise the temperature to 60°C, stir evenly, and cool to room temperature to obtain a milky white or light yellow composite emulsifier. Take the composite emulsifier and 60 parts of amino-modified polydimethylsiloxane (the viscosity at 25°C is 5000mm ² /s, ammonia value 0.8, modified group chemical formula (I)), 15 parts of polyether modified polydimethylsiloxane (viscosity at 25°C is 500mm ² /s, modification amount 0.3), 15 1 part of epoxy-modified polydimethylsiloxane (viscosity at 25°C is 6000 mm ² /s, epoxy equivalent value is 0.1, chemical formula of modifying group (I)), 10 parts of vinyl-modified polydimethylsiloxane The composite modified silicone oil of methyl siloxane (viscosity at 25°C is 3000 mm ² /s, vinyl modification amount is 0.15) is put into the high shear emulsifier according to the weight ratio of 1:4 and stirred evenly, adding A 1:1 composite additive composed of 1.5% trishydroxyethylmethyl quaternary ammonium methyl sulfate and modified polymethylsiloxane type defoamer, and then add deionized water dropwise to it, Control the stirring speed to 3500r/min, stir for 80min, adjust the pH value to 7, and the obtained light yellow or white emulsion is the raw silk oil agent.

Embodiment 10, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

In embodiment 9, emulsifying agent adopts polyoxyethylene sorbitan ester type nonionic surfactant, C13 linear alcohol ether type nonionic surfactant, fatty alcohol polyoxyethylene ether type nonionic surfactant, isomer The compound of alcohol polyoxyethylene ether type nonionic surfactant is used as a compound emulsifier; the compounding aid is changed to isotridecyl ether phosphate methyl ester salt, polyoxyethylene laurate, and modified polymethylsiloxane Alkane type defoamer and fatty alcohol polyoxyethylene ether are mixed and compounded in equal proportions, and the percentage added is 1%.

Embodiment 11, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

In Example 6, 20 parts of epoxy-modified polydimethylsiloxane (the viscosity at 25°C is 1500 mm ² /s, the epoxy equivalent value is 0.1, and the chemical formula of the modifying group is (II)), and the remaining characteristics constant.

Embodiment 12, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

In Example 7, 15 parts of epoxy-modified polydimethylsiloxane (viscosity at 25°C is 1500 mm ² /s, epoxy equivalent value is 0.1, chemical formula of the modifying group (II)), and other characteristics constant.

Embodiment 13, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

In Example 8, 15 parts of epoxy-modified polydimethylsiloxane (viscosity at 25°C is 1500 mm ² /s, epoxy equivalent value is 0.1, chemical formula of the modifying group (II)), and other characteristics constant.

Embodiment 14, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

In Example 9, 15 parts of epoxy-modified polydimethylsiloxane (viscosity at 25°C is 2000 mm ² /s, epoxy equivalent value is 0.2, chemical formula of the modifying group (II)), and other characteristics constant.

Embodiment 15, a kind of preparation method of carbon fiber precursor oil agent, its steps are as follows:

In Example 7, 60 parts of amino-modified polydimethylsiloxane (viscosity at 25°C is 180 mm ² /s, ammonia value is 0.5, chemical formula of the modifying group (II)), 15 parts of epoxy-modified polydimethylsiloxane Methyl siloxane (viscosity at 25°C is 1500 mm ² /s, epoxy equivalent value is 0.1, chemical formula of modifying group (II)), and other characteristics remain unchanged.

comparative example. Using a single purchase of an amino-modified silicone oil, the obtained raw silk is pre-oxidized and carbonized.

The corresponding numbers of emulsifiers and auxiliary agents are shown in Attached Table 1. The use of the oil obtained in each example and the mechanical properties of the carbon fiber obtained after pre-oxidation and carbonization of the oil obtained from the oil are shown in Attached Table 2. The specific implementation plans of each example are shown in Attached table 3.

Attached Table 1 Corresponding Numbers of Emulsifiers and Auxiliaries

Attached Table 2 The performance of the oil agent in the example and the mechanical properties of the obtained carbon fiber

Attached Table 3 Examples of specific implementation plans

Claims (6)

1. a preparation method for carbon fibre precursor finish, is characterized in that, its step is as follows:

Get the composite modified silicone oil of compound emulsifying agent and feature, according to the weight ratio of 1～4:3～10, drop in high-shear emulsion machine and stir, the composite assistant that adds quality percentage composition 1～2%, drip wherein again appropriate amount of deionized water, control mixing speed is 1500～10000r/min, mixing time is 20～120min, regulates pH value to 3～10, and light blue, the faint yellow or white emulsion of gained is carbon fibre precursor finish;

Described compound emulsifying agent is to be composited by following at least 2 kinds of emulsifying agents: isomery alcohol Polyoxyethylene Ether Nonionic Surfactant, alkylphenol polyoxyethylene type non-ionic surface active agent, fatty alcohol-polyoxyethylene ether type non-ionic surface active agent, polyoxyethylene sorbitan ester type non-ionic surface active agent, alkylolamides type non-ionic surface active agent, C10 ~ C18 straight chain alcohol ether type non-ionic surface active agent; During preparation, above-mentioned at least 2 kinds of emulsifying agents are placed in container, are warming up to 40 ~ 90 ℃, after stirring, be cooled to room temperature, obtain oyster white or faint yellow compound emulsifying agent;

The composite modified silicone oil of described feature is made by following at least 2 kinds of raw materials: 30 ~ 80 parts of amino modified dimethyl silicone polymers, 10 ~ 60 parts of polyether-modified dimethyl silicone polymers, 10 ~ 50 parts of epoxide modified dimethyl silicone polymers, 10 ~ 20 parts of vinyl modified dimethyl silicone polymers;

Described composite assistant respectively in following A group and B group at least a kind of raw material be composited; A group raw material is trihydroxyethyl methyl quaternary ammonium Methylsulfate salt, Dodecyl trimethyl ammonium chloride, different tridecanol ether phosphoric acid methyl esters salt, polyoxyethylene laurate; B group raw material is modification polymethyl siloxane type defoamer, fatty alcohol-polyoxyethylene ether, isoamyl alcohol, tributyl phosphate.

2. the preparation method of carbon fibre precursor finish according to claim 1, is characterized in that, the amino modified dimethyl silicone polymer of the composite modified silicone oil Raw of described feature possesses following characteristics:

A part of side chain that end has the dimethyl-silicon of methyl is replaced by chemical formula (I) or chemical formula (II)

-CH ₂-NH-CH ₂-CH ₂-NH ₂（Ⅰ）

R-NH ₂ （Ⅱ）。

3. the preparation method of carbon fibre precursor finish according to claim 1, is characterized in that, the polyether-modified dimethyl silicone polymer of the composite modified silicone oil Raw of feature possesses following characteristics:

A part of side chain that end has the dimethyl-silicon of methyl is replaced by chemical formula (I) or chemical formula (II)

-CH ₂（OCH ₂-CH ₂） _10~15OCH ₃（Ⅰ）

-CH ₂-NH（CH ₂-CH ₂） _10~15OCOCH ₃ （Ⅱ）。

4. the preparation method of carbon fibre precursor finish according to claim 1, is characterized in that, the epoxide modified dimethyl silicone polymer of the composite modified silicone oil Raw of feature possesses following characteristics:

A part of side chain or terminal methyl group that end has the dimethyl-silicon of methyl are replaced by chemical formula (I), chemical formula (II) or chemical formula (III)

（Ⅰ） （Ⅱ） （Ⅲ）。

5. the preparation method of carbon fibre precursor finish according to claim 1, is characterized in that, the viscosity of described amino-modified silicone oil in the time of 25 ℃ is 10 ~ 6000mm ²/ s, ammonia value is 0.3 ~ 1.0; The viscosity of described epoxide modified silicone oil in the time of 25 ℃ is 50 ~ 10000 mm ²/ s, epoxide equivalent value is 0.001 ~ 0.25; The viscosity of described polyether modified silicon oil in the time of 25 ℃ is 300 ~ 1500 mm ²/ s, the modification amount of polyether group is 0.001 ~ 0.8; The viscosity of described vinyl modified silicone oil in the time of 25 ℃ is 100 ~ 6000 mm ²/ s, the modification amount of vinyl is 0.001 ~ 0.5.

6. the carbon fibre precursor finish that described in claim 1-5 any one, preparation method makes is at little tow, the purposes in the former silk oiling agent of large-tow carbon fiber.