Modified silicone oil oiling agent with comb-shaped structure as well as preparation method and application of modified silicone oil oiling agent

Abstract

The invention provides a modified silicone oil agent with a comb-shaped structure as well as a preparation method and application thereof, the oil agent comprises an amino modified silicone oil emulsion and an epoxy modified silicone oil emulsion, and the mass ratio of the amino modified silicone oil emulsion to the epoxy modified silicone oil emulsion is 1: (0.5-1.5); the amino modified silicone oil emulsion and the epoxy group-containing modified silicone oil emulsion have comb-shaped structures, main chains of the amino modified silicone oil and the epoxy group-containing modified silicone oil are acrylate polymers, and branch chains are amino short silane chains or epoxy group-containing short silane chains; the preparation method of the oiling agent comprises the following steps: respectively preparing amino short-chain silicone oil and epoxy group-containing short-chain silicone oil, and then respectively synthesizing amino modified silicone oil emulsion and epoxy group-containing modified silicone oil emulsion. The acrylate polymer is introduced, the content of organic silicon is reduced, the viscosity of the oiling agent is small, carbon fibers are conveniently oiled, a protective film is formed on the fibers, friction and abrasion between the fibers are prevented, and therefore the surface defects of the carbon fibers are reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of spinning oils, and in particular relates to a comb-shaped structure modified silicone oil and a preparation method and application thereof. Background Art

[0002] Carbon fiber is usually used to prepare reinforcing materials for high-performance composite materials. It has extremely high strength and extremely high modulus. With its unique advantages, it is widely used in aerospace, transportation, military and new energy fields. Carbon fiber precursor oil is an indispensable auxiliary agent in the preparation of high-performance carbon fiber. In the process of carbon fiber preparation, the oil has a very important influence on the quality of carbon fiber. Therefore, the application of high-performance carbon fiber oil can ensure the smooth production of carbon fiber and prepare high-performance carbon fiber.

[0003] Carbon fiber preparation often uses polyacrylonitrile-based carbon fiber precursor, and an oiling process is usually carried out during production. The oil forms a film on the surface of the monofilament, which can prevent the monofilaments from sticking and twisting, and can also reduce the friction and wear between the fiber surface and the roller, effectively reducing the defects on the fiber surface, thereby improving the performance of the carbon fiber. At present, most of the carbon fiber precursor oils are silicone oils, especially modified oils based on polydimethylsiloxane, which have the advantages of good heat resistance, low surface tension and self-lubrication, and are widely used in actual production. However, there are often some problems in its application: for example, during the carbonization and graphitization process of carbon fiber silicone oil, the residual oil may be converted into silicon-based ceramics. Although these hard and brittle ceramics are in trace amounts, they greatly affect the mechanical properties of carbon fiber. Therefore, less silicon or no silicon is a development direction of high-performance carbon fiber oils; for another example, the viscosity of current carbon fiber silicone oils is often too high to quickly coat polyacrylonitrile-based carbon fiber precursors and form a protective film on the fiber filaments, which cannot prevent friction and wear between filaments, thereby reducing surface defects of carbon fiber and improving the retention of fibers at high temperatures, etc. Summary of the invention

[0004] In response to the above technical problems, the present invention provides a comb-shaped structure modified silicone oil agent and a preparation method and application thereof. The silicone oil agent provided by the present invention has a comb-shaped structure, a main chain is an acrylate structure chain, and a side chain is a short silane chain containing an epoxy group or an amino group, which reduces the silicone content and makes the viscosity of the oil agent smaller, making it convenient to oil the carbon fiber, forming a protective film on the fiber filaments, preventing friction and wear between the filaments, thereby reducing surface defects of the carbon fiber.

[0005] To achieve the above object, the technical solution of the present invention is:

[0006] The first aspect of the present invention provides a comb-shaped structure modified silicone oil agent, comprising an amino-modified silicone oil emulsion and an epoxy-modified silicone oil emulsion, wherein the mass ratio of the amino-modified silicone oil emulsion to the epoxy-modified silicone oil emulsion is 1:0.5-1.5;

[0007] The structures of amino-modified silicone oil emulsion and epoxy-modified silicone oil emulsion are both comb-shaped, wherein the main chain of the amino-modified silicone oil is an acrylate polymer, and the side chain is an amino short silane chain; the main chain of the epoxy-modified silicone oil is an acrylate polymer, and the side chain is an epoxy short silane chain;

[0008] The preparation method of the oil agent is: firstly, amino short-chain silicone oil and epoxy-containing short-chain silicone oil are prepared respectively, and then amino-modified silicone oil emulsion and epoxy-containing modified silicone oil emulsion are synthesized respectively.

[0009] Based on the same inventive concept, the second aspect of the present invention provides a method for preparing the comb-shaped structure-modified silicone oil agent as described above, comprising the following steps:

[0010] S1: preparing amino-modified silicone oil emulsion, further comprising: S101: preparing amino short-chain silicone oil; S102: synthesizing amino-modified silicone oil emulsion;

[0011] S2: preparing epoxy-modified silicone oil emulsion, further comprising: S201: preparing epoxy-containing short-chain silicone oil; S202: synthesizing epoxy-modified silicone oil emulsion;

[0012] S3: Amino-modified silicone oil emulsion and epoxy-modified silicone oil emulsion are compounded according to the ratio.

[0013] Preferably, the step S101 is specifically:

[0014] Taking the sum of the weight percentages of all raw material components as 100%, the raw materials used and their weight percentages are as follows:

[0015]

[0016]

[0017] Firstly, a strong alkaline catalyst is dissolved in deionized water, and then added together with 1 / 3 of octamethylcyclotetrasiloxane linear body, a silane coupling agent with a double bond, and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane into a reaction device equipped with a stirrer, a reflux condenser, and a thermometer. After stirring evenly, the mixture is reacted at a temperature of 90 to 110° C. for 2 to 3 hours, and then the remaining octamethylcyclotetrasiloxane linear body and 1 / 3 of the end-capping agent are added dropwise, and the reaction is continued for 3 to 6 hours. The remaining end-capping agent is then added and reacted for 1 to 2 hours, and a uniform translucent viscous liquid is obtained after cooling.

[0018] Preferably, the step S102 is specifically:

[0019] Adding acrylate monomer, chain transfer agent dodecyl mercaptan, mixed emulsifier consisting of anionic emulsifier and nonionic emulsifier, and deionized water to the amino-containing short-chain silicone oil in step S101, mixing evenly, and emulsifying with a high-pressure homogenizer to obtain a stable pre-emulsion;

[0020] 0.1-2% of ammonium persulfate by weight of the acrylate monomer is dissolved in deionized water to obtain an initiator solution; then, in an inert atmosphere, 1 / 5 of the pre-emulsion is stirred and heated to 65-85° C., 1 / 5 of the initiator solution is added, and after reacting for 0.5-1 hour, the remaining pre-emulsion and the remaining initiator solution are respectively added dropwise, and the reaction is continued for 5-8 hours. After cooling, an amino-modified silicone oil emulsion is obtained.

[0021] Preferably, the mass ratio of the acrylate monomer, the amino-containing short-chain silicone oil in step S101, the chain transfer agent dodecyl mercaptan, the mixed emulsifier, and deionized water is 100:50-150:0.3-3:3-15:300-600.

[0022] Preferably, the step S201 specifically includes:

[0023] Taking the sum of the weight percentages of all raw material components as 100%, the raw materials used and their weight percentages are as follows:

[0024]

[0025]

[0026] Firstly, a strong alkaline catalyst is dissolved in deionized water, and then added together with 1 / 3 of octamethylcyclotetrasiloxane linear body, a silane coupling agent with a double bond, and 3-[(2,3)-epoxypropyloxy]propylmethyldimethoxysilane into a reaction device equipped with a stirrer, a reflux condenser, and a thermometer. After stirring evenly, the mixture is reacted at a temperature of 90 to 110° C. for 2 to 3 hours, and then the remaining octamethylcyclotetrasiloxane linear body and 1 / 3 of the end-capping agent are added dropwise, and the reaction is continued for 3 to 6 hours. The remaining end-capping agent is then added and reacted for 1 to 2 hours. After cooling, a uniform translucent viscous liquid is obtained.

[0027] Preferably, the step 202 specifically includes:

[0028] Adding acrylate monomer, chain transfer agent dodecyl mercaptan, mixed emulsifier consisting of anionic emulsifier and nonionic emulsifier, and deionized water to the epoxy-containing short-chain silicone oil in step 201, mixing evenly, and emulsifying with a high-pressure homogenizer to obtain a stable pre-emulsion;

[0029] 0.1-2% of ammonium persulfate by weight of the acrylate monomer is dissolved in deionized water to obtain an initiator solution; then, in an inert atmosphere, 1 / 5 of the pre-emulsion is stirred and heated to 65-85° C., 1 / 5 of the initiator solution is added, and after reacting for 0.5-1 hour, the remaining pre-emulsion and the remaining initiator solution are respectively added dropwise, and the reaction is continued for 5-8 hours. After cooling, an epoxy-modified silicone oil emulsion is obtained.

[0030] Preferably, the mass ratio of the acrylate monomer, the epoxy-containing short-chain silicone oil in step S201, the chain transfer agent dodecyl mercaptan, the mixed emulsifier and water is 100:50-150:0.3-3:3-15:300-600.

[0031] Preferably, the silane coupling agent with a double bond includes at least one of methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, vinylmethyldimethoxysilane or vinylmethyldiethoxysilane;

[0032] The end-capping agent is hexamethyldisiloxane or pentamethyldisiloxane;

[0033] The strong alkaline catalyst is any one of potassium hydroxide, sodium hydroxide or tetramethylammonium hydroxide or a mixed catalyst of any of the above.

[0034] Preferably, the anionic emulsifier and the nonionic emulsifier in the mixed emulsifier are prepared in a mass ratio of 1:0.5 to 1.5;

[0035] The anionic emulsifier is sodium dodecyl sulfate or sodium dodecylbenzene sulfonate, and the nonionic emulsifier is fatty alcohol polyoxyethylene ether or nonylphenol polyoxyethylene ether.

[0036] Preferably, the acrylic acid ester monomer includes at least one of butyl acrylate, isooctyl acrylate, butyl methacrylate, methyl methacrylate, isobutyl acrylate, isooctyl methacrylate or ethyl acrylate.

[0037] The third aspect also provides the use of the above-mentioned comb-shaped structure modified silicone oil agent in carbon fiber production.

[0038] Due to the adoption of the above technical solution, the present invention has the following advantages and positive effects compared with the prior art:

[0039] (1) The oil provided by the present invention includes amino-modified silicone oil and epoxy-modified silicone oil, and the chemical structure of the amino-modified silicone oil and the epoxy-modified silicone oil is a comb-shaped structure, wherein the main chain is an acrylate structure chain, and the side chains are short silane chains containing epoxy groups or amino groups. The short side chain structure can make the oil have low viscosity and good rheological properties when used, and can quickly wet the surface of carbon fiber precursor to quickly coat the fiber and form a protective film on the fiber to prevent friction and wear between the fibers, thereby reducing surface defects of the carbon fiber, and at the same time have good fiber separation and are not easy to stick.

[0040] (2) The oil of the present invention includes amino-modified silicone oil and epoxy-modified silicone oil compounded in proportion, and the two can synergistically improve the application performance of the oil product. Although the oil has a small molecular weight and low viscosity when used at room temperature, the epoxy groups on the two modified silicone oils will react chemically with the amino groups at high temperatures, and the adjacent amino-modified silicone oils and epoxy-modified silicone oils will be chemically connected, forming a super-large molecular oil network coated on the fiber surface, better protecting the carbon fiber precursor and further improving the product performance of the carbon fiber.

[0041] (3) The oil provided by the present invention includes amino-modified silicone oil and epoxy-modified silicone oil, and the chemical structure of amino-modified silicone oil and epoxy-modified silicone oil is a comb-shaped structure, wherein the main chain is an acrylate structure chain, and the side chain is a short silane chain containing epoxy or amino groups, respectively. The oil introduces an acrylate polymer, which can reduce the silicon content in the oil, and the silane chain is well dispersed in the molecular structure of the oil. Reducing the silicon content can avoid residue on the carbon fiber, and then avoid the silicon remaining on the carbon fiber to generate silicon oxide, silicon nitride and other substances ("silicon-based ceramics") under high-temperature carbonization conditions, thereby avoiding reducing the tensile strength of the carbon fiber; the oil with low silicon content has low pollution to the carbon fiber and carbonization equipment, which helps to keep the equipment clean and run efficiently, and reduce the frequency and cost of maintenance and cleaning; the oil with low silicon content can improve the quality of carbon fiber precursor, such as reducing the amount of hairiness and improving the bundling, which helps to improve the performance and appearance quality of the final product; the use of low-silicon oil can also reduce dependence on imported products, thereby reducing production costs.

[0042] At the same time, the present invention introduces acrylic polymer and non-ionic emulsifier into the oil agent, which will be cracked into small molecules such as CO2 and H2O that are easy to remove during the high-temperature carbonization and graphitization process of carbon fiber, which is beneficial to improve the mechanical properties of carbon fiber and reduce and avoid carbon fiber structural defects caused by the formation of "silicon-based ceramics" in carbon fiber.

[0043] (4) The preparation method of the carbon fiber oil provided by the present invention can obtain an amino-modified silicone oil emulsion with a comb-shaped structure and an epoxy-modified silicone oil emulsion. DETAILED DESCRIPTION

[0044] The following is a further detailed description of a comb-shaped structure modified silicone oil agent and its preparation method and application proposed by the present invention in conjunction with specific embodiments. The advantages and features of the present invention will become more clear according to the following description.

[0045] Example 1

[0046] S1: preparing an amino-modified silicone oil emulsion, further comprising:

[0047] S101: Preparation of amino short-chain silicone oil

[0048] 0.6 g of tetramethylammonium hydroxide was dissolved in 6 g of deionized water, and then added together with 19.1 g of octamethylcyclotetrasiloxane linear body, 18 g of methacryloxypropylmethyldimethoxysilane, and 18 g of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane into a reaction device equipped with a stirrer, a reflux condenser, and a thermometer. After stirring evenly, the mixture was reacted at 100° C. for 2.5 hours, and then 38.3 g of octamethylcyclotetrasiloxane linear body and 0.4 g of hexamethyldisiloxane were added dropwise, and the reaction was continued for 4.5 hours. Then, 0.8 g of hexamethyldisiloxane was added and the reaction was continued for 1.5 hours. After cooling, a uniform translucent viscous liquid was obtained.

[0049] S102: Synthetic amino modified silicone oil emulsion

[0050] Weigh 50g of butyl acrylate, 50g of isooctyl acrylate, 0.2g of dodecyl mercaptan, 5g of sodium lauryl sulfate, 6g of fatty alcohol polyoxyethylene ether and 250g of water, add them to the above-mentioned amino-containing short-chain silicone oil, mix evenly, and obtain a stable pre-emulsion after emulsification by a high-pressure homogenizer; at the same time, dissolve 1.1g of ammonium persulfate in 50g of deionized water to obtain an initiator solution; then in an inert atmosphere, stir and heat 1 / 5 of the pre-emulsion to 80°C, add 1 / 5 of the initiator solution, react for 0.5 hour, then drop the remaining pre-emulsion and the remaining initiator solution respectively, continue to react for 6 hours, and obtain an amino-modified silicone oil emulsion after cooling.

[0051] S2: preparing an epoxy-modified silicone oil emulsion, further comprising:

[0052] S201: Preparation of short-chain silicone oil containing epoxy groups

[0053] 0.7 g of tetramethylammonium hydroxide was dissolved in 4.3 g of deionized water, and then added together with 16.7 g of octamethylcyclotetrasiloxane linear body, 20 g of methacryloxypropylmethyldimethoxysilane, and 20 g of 3-[(2,3)-epoxypropyloxy]propylmethyldimethoxysilane into a reaction device equipped with a stirrer, a reflux condenser, and a thermometer. After stirring evenly, the mixture was reacted at 110° C. for 2 hours, and then 33.4 g of octamethylcyclotetrasiloxane linear body and 0.7 g of hexamethyldisiloxane were added dropwise, and the reaction was continued for 4 hours. 1.3 g of hexamethyldisiloxane was added and reacted for 1 hour. After cooling, a uniform translucent viscous liquid was obtained, which was the synthesized epoxy-containing short-chain silicone oil.

[0054] S202: Synthetic epoxy-modified silicone oil emulsion

[0055] Weigh 60g of isooctyl acrylate, 60g of butyl methacrylate, 2.2g of dodecyl mercaptan, 6.5g of sodium dodecyl sulfate, 4.5g of nonylphenol polyoxyethylene ether and 300g of water, add them to the above-mentioned epoxy-containing short-chain silicone oil, mix evenly, and obtain a stable pre-emulsion after emulsification by a high-pressure homogenizer; at the same time, dissolve 1.6g of ammonium persulfate in 50g of deionized water to obtain an initiator solution; then in an inert atmosphere, stir and heat 1 / 5 of the pre-emulsion to 80°C, add 1 / 5 of the initiator solution, react for 0.5 hour, then drop the remaining pre-emulsion and the remaining initiator solution respectively, continue to react for 7 hours, and obtain an epoxy-modified silicone oil emulsion after cooling.

[0056] S3: 1 kg of amino-modified silicone oil emulsion and 0.8 kg of epoxy-modified silicone oil emulsion are placed in a container and stirred evenly to obtain a modified silicone oil agent with a comb-shaped structure.

[0057] Example 2

[0058] S1-S2 in this embodiment are the same as those in Example 1, except for step S3. In step S3 of this embodiment, 1 kg of amino-modified silicone oil emulsion and 1.4 kg of epoxy-modified silicone oil emulsion are put into a container, and after stirring evenly, a modified silicone oil agent with a comb-shaped structure is obtained.

[0059] Example 3

[0060] S1: preparing an amino-modified silicone oil emulsion, further comprising:

[0061] S101: Preparation of amino short-chain silicone oil

[0062] 0.6 g of potassium hydroxide was dissolved in 6 g of deionized water, and then added together with 17.1 g of octamethylcyclotetrasiloxane linear body, 18 g of vinylmethyldimethoxysilane, and 19 g of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane into a reaction device equipped with a stirrer, a reflux condenser, and a thermometer. After stirring evenly, the mixture was reacted at 95° C. for 3 hours, and then 34.3 g of octamethylcyclotetrasiloxane linear body and 1 g of hexamethyldisiloxane were added dropwise, and the reaction was continued for 5 hours. Then, 2 g of hexamethyldisiloxane was added and reacted for 1.5 hours. After cooling, a uniform translucent viscous liquid was obtained.

[0063] S102: Synthetic amino modified silicone oil emulsion

[0064] Weigh 80g of butyl acrylate, 2g of dodecyl mercaptan, 4.5g of sodium lauryl sulfate, 6.5g of fatty alcohol polyoxyethylene ether and 300g of water, add them to the above-mentioned amino-containing short-chain silicone oil, mix evenly, and obtain a stable pre-emulsion after emulsification by a high-pressure homogenizer; at the same time, dissolve 0.2g of ammonium persulfate in 50g of deionized water to obtain an initiator solution; then in an inert atmosphere, stir and heat 1 / 5 of the pre-emulsion to 75°C, add 1 / 5 of the initiator solution, react for 1 hour, then drop the remaining pre-emulsion and the remaining initiator solution respectively, continue to react for 8 hours, and obtain an amino-modified silicone oil emulsion after cooling.

[0065] S2: preparing epoxy-modified silicone oil emulsion, further comprising: S201: preparing epoxy-containing short-chain silicone oil

[0066] 5 g of 0.6 g of potassium hydroxide was dissolved in deionized water, and then added together with 17.8 g of octamethylcyclotetrasiloxane linear body, 18 g of vinylmethyldimethoxysilane, and 18 g of 3-[(2,3)-epoxypropyloxy]propylmethyldimethoxysilane into a reaction device equipped with a stirrer, a reflux condenser, and a thermometer. After stirring evenly, the mixture was reacted at 105° C. for 2.5 hours, and then 35.5 g of octamethylcyclotetrasiloxane linear body and 0.8 g of hexamethyldisiloxane were added dropwise, and the reaction was continued for 4.5 hours. Then, 1.6 g of hexamethyldisiloxane was added and the reaction was continued for 1.5 hours. After cooling, a uniform translucent viscous liquid was obtained.

[0067] S202: Synthetic epoxy-modified silicone oil emulsion

[0068] Weigh 30g of butyl acrylate, 50g of isooctyl acrylate, 20g of butyl methacrylate, 2.5g of dodecyl mercaptan, 5g of sodium dodecyl sulfate, 7g of nonylphenol polyoxyethylene ether and 300g of water, add them to the above-mentioned epoxy-containing short-chain silicone oil, mix evenly, and obtain a stable pre-emulsion after emulsification by a high-pressure homogenizer; at the same time, dissolve 1.4g of ammonium persulfate in 50g of deionized water to obtain an initiator solution; then in an inert atmosphere, stir and heat 1 / 5 of the pre-emulsion to 80°C, add 1 / 5 of the initiator solution, react for 1 hour, then drop the remaining pre-emulsion and the remaining initiator solution respectively, continue to react for 6 hours, and obtain the epoxy-containing modified silicone oil after cooling.

[0069] S3: 1 kg of amino-modified silicone oil emulsion and 1 kg of epoxy-modified silicone oil emulsion are placed in a container and stirred evenly to obtain a modified silicone oil agent with a comb-shaped structure.

[0070] Example 4

[0071] S1-S2 in this embodiment are the same as those in Example 3, except for step S3. In step S3 of this embodiment, 1 kg of amino-modified silicone oil emulsion and 0.8 kg of epoxy-modified silicone oil emulsion are put into a container, and after stirring evenly, a modified silicone oil agent with a comb-shaped structure is obtained.

[0072] Comparative Example 1

[0073] The comparative example is the same as step S1 of Example 1, and the oil agent contains only amino-modified silicone oil emulsion.

[0074] Comparative Example 2

[0075] This comparative example is the same as step S2 of Example 1, and the oil agent contains only epoxy-modified silicone oil emulsion.

[0076] Table 1 shows the data of the use process of the modified silicone oil agent with a comb-shaped structure prepared in Examples 1-4 and a commercially available product (silicone oil agent).

[0077]

[0078] It can be seen from Table 1 that the main chains of the oils prepared in the examples are all acrylate polymers, and the side chains are short silane chains containing epoxy groups or amino groups. The acrylate polymers are introduced into the oils, which reduces the silicone content and the proportion of silicone, thereby reducing "silicon dust".

[0079] Table 2 lists the performance comparison of the modified silicone oil agents with comb-shaped structures prepared in Examples 1-4 and commercially available products (silicone oil agents):

[0080]

[0081] It can be seen from Table 2 that compared with Comparative Examples 1 and 2, the embodiment shows that the amino-modified silicone oil and the epoxy-modified silicone oil compounded in proportion can synergistically improve the application performance of the oil product, and the obtained carbon fiber is burr-free and has high strength.

[0082] Compared with commercially available silicone oil carbon fiber oil products, the oil prepared in the embodiment has low viscosity, good carbon fiber processability, and the obtained carbon fiber has high mechanical properties.

[0083] The above is a detailed description of the implementation of the present invention in conjunction with specific embodiments, but the present invention is not limited to the above implementation. Even if various changes are made to the present invention, if these changes fall within the scope of the claims of the present invention and their equivalents, they still fall within the protection scope of the present invention.

Claims

1. A comb-shaped structure modified silicone oil agent, characterized in that: It comprises amino-modified silicone oil emulsion and epoxy-modified silicone oil emulsion, wherein the mass ratio of the amino-modified silicone oil emulsion to the epoxy-modified silicone oil emulsion is 1:0.5-1.5; The structures of amino-modified silicone oil emulsion and epoxy-modified silicone oil emulsion are both comb-shaped, wherein the main chain of the amino-modified silicone oil is an acrylate polymer, and the side chain is an amino short silane chain; the main chain of the epoxy-modified silicone oil is an acrylate polymer, and the side chain is an epoxy short silane chain; The preparation method of the oil agent is: firstly, amino short-chain silicone oil and epoxy-containing short-chain silicone oil are prepared respectively, and then amino-modified silicone oil emulsion and epoxy-containing modified silicone oil emulsion are synthesized respectively.

2. A method for preparing the comb-shaped structure-modified silicone oil agent according to claim 1, characterized in that: The following steps are involved: S1: preparing amino-modified silicone oil emulsion, further comprising: S101: preparing amino short-chain silicone oil; S102: synthesizing amino-modified silicone oil emulsion; S2: preparing epoxy-modified silicone oil emulsion, further comprising: S201: preparing epoxy-containing short-chain silicone oil; S202: synthesizing epoxy-modified silicone oil emulsion; S3: Amino-modified silicone oil emulsion and epoxy-modified silicone oil emulsion are compounded according to the ratio.

3. The method for preparing the comb-shaped structure-modified silicone oil agent according to claim 2, characterized in that: The step S101 is specifically as follows: Taking the sum of the weight percentages of all raw material components as 100%, the raw materials used and their weight percentages are as follows: Firstly, a strong alkaline catalyst is dissolved in deionized water, and then added together with 1 / 3 of octamethylcyclotetrasiloxane linear body, a silane coupling agent with a double bond, and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane into a reaction device equipped with a stirrer, a reflux condenser, and a thermometer. After stirring evenly, the mixture is reacted at a temperature of 90 to 110° C. for 2 to 3 hours, and then the remaining octamethylcyclotetrasiloxane linear body and 1 / 3 of the end-capping agent are added dropwise, and the reaction is continued for 3 to 6 hours. The remaining end-capping agent is then added and reacted for 1 to 2 hours, and a uniform translucent viscous liquid is obtained after cooling.

4. The method for preparing the comb-shaped structure-modified silicone oil agent according to claim 2, characterized in that: The step S102 is specifically as follows: Adding acrylate monomer, chain transfer agent dodecyl mercaptan, mixed emulsifier consisting of anionic emulsifier and nonionic emulsifier, and deionized water to the amino-containing short-chain silicone oil in step S101, mixing evenly, and emulsifying with a high-pressure homogenizer to obtain a stable pre-emulsion; 0.1-2% of ammonium persulfate by weight of the acrylate monomer is dissolved in deionized water to obtain an initiator solution; then, in an inert atmosphere, 1 / 5 of the pre-emulsion is stirred and heated to 65-85° C., 1 / 5 of the initiator solution is added, and after reacting for 0.5-1 hour, the remaining pre-emulsion and the remaining initiator solution are respectively added dropwise, and the reaction is continued for 5-8 hours. After cooling, an amino-modified silicone oil emulsion is obtained.

5. The method for preparing the comb-shaped structure-modified silicone oil agent according to claim 4, characterized in that: The mass ratio of the acrylate monomer, the amino-containing short-chain silicone oil in step S101, the chain transfer agent dodecyl mercaptan, the mixed emulsifier, and deionized water is 100:50-150:0.3-3:3-15:300-600.

6. The method for preparing the comb-shaped structure-modified silicone oil agent according to claim 2, characterized in that: The step S201 specifically includes: Taking the sum of the weight percentages of all raw material components as 100%, the raw materials used and their weight percentages are as follows: Octamethylcyclotetrasiloxane linear 40~80% Silane coupling agent with double bond 10~25% Firstly, a strong alkaline catalyst is dissolved in deionized water, and then added together with 1 / 3 of octamethylcyclotetrasiloxane linear body, a silane coupling agent with a double bond, and 3-[(2,3)-epoxypropyloxy]propylmethyldimethoxysilane into a reaction device equipped with a stirrer, a reflux condenser, and a thermometer. After stirring evenly, the mixture is reacted at a temperature of 90 to 110° C. for 2 to 3 hours, and then the remaining octamethylcyclotetrasiloxane linear body and 1 / 3 of the end-capping agent are added dropwise, and the reaction is continued for 3 to 6 hours. The remaining end-capping agent is then added and reacted for 1 to 2 hours. After cooling, a uniform translucent viscous liquid is obtained.

7. The method for preparing the comb-shaped structure-modified silicone oil agent according to claim 2, characterized in that: The step 202 specifically includes: Adding acrylate monomer, chain transfer agent dodecyl mercaptan, mixed emulsifier consisting of anionic emulsifier and nonionic emulsifier, and deionized water to the epoxy-containing short-chain silicone oil in step 201, mixing evenly, and emulsifying with a high-pressure homogenizer to obtain a stable pre-emulsion; 0.1-2% of ammonium persulfate by weight of the acrylate monomer is dissolved in deionized water to obtain an initiator solution; then, in an inert atmosphere, 1 / 5 of the pre-emulsion is stirred and heated to 65-85° C., 1 / 5 of the initiator solution is added, and after reacting for 0.5-1 hour, the remaining pre-emulsion and the remaining initiator solution are respectively added dropwise, and the reaction is continued for 5-8 hours. After cooling, an epoxy-modified silicone oil emulsion is obtained.

8. The method for preparing the comb-shaped structure-modified silicone oil agent according to claim 7, characterized in that: The mass ratio of the acrylate monomer, the epoxy-containing short-chain silicone oil in step S201, the chain transfer agent dodecyl mercaptan, the mixed emulsifier and water is 100:50-150:0.3-3:3-15:300-600.

9. The method for preparing the comb-structure modified silicone oil agent according to claim 3 or 6, characterized in that: The silane coupling agent with double bonds includes at least one of methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, vinylmethyldimethoxysilane or vinylmethyldiethoxysilane; The end-capping agent is hexamethyldisiloxane or pentamethyldisiloxane; The strong alkaline catalyst is any one of potassium hydroxide, sodium hydroxide or tetramethylammonium hydroxide or a mixed catalyst of any of the above.

10. The method for preparing the comb-shaped structure-modified silicone oil agent according to claim 4 or 7, characterized in that: The anionic emulsifier and the nonionic emulsifier in the mixed emulsifier are prepared in a mass ratio of 1:0.5-1.5; The anionic emulsifier is sodium dodecyl sulfate or sodium dodecylbenzene sulfonate, and the nonionic emulsifier is fatty alcohol polyoxyethylene ether or nonylphenol polyoxyethylene ether.

11. The method for preparing the comb-structure modified silicone oil agent according to claim 4 or 7, characterized in that: The acrylic acid ester monomer includes at least one of butyl acrylate, isooctyl acrylate, butyl methacrylate, methyl methacrylate, isobutyl acrylate, isooctyl methacrylate or ethyl acrylate.

12. Use of the comb-shaped structure modified silicone oil agent according to claim 1 in carbon fiber production.

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