A carbon fiber precursor oil agent free of silicon compounds, and its preparation method and application

Abstract

The present invention relates to a carbon fiber precursor oil agent that does not contain silicon compounds, a preparation method, and applications thereof. The components include oleic acid ester, acetylenic alcohol ester, polyoxyethylene ether derivative, emulsifier, antistatic agent, and defoaming agent. The oil agent of the present invention can impart excellent lubricity, heat resistance, and antistatic properties to the carbon fiber precursor, thereby ensuring that the carbon fiber obtained after pre-oxidation and carbonization of the precursor has excellent mechanical properties. The carbon fiber precursor oil agent of the present invention has a simple preparation process, excellent film-forming properties, heat resistance, and stability, can eliminate silicon powder contamination in the production process of polyacrylonitrile-based carbon fibers, extend the operating time of the carbon fiber production line, and reduce production costs.

Description

Technical Field

[0001] The invention belongs to the field of carbon fiber oils, and particularly relates to a carbon fiber precursor oil containing no silicon compounds, and a preparation method and application thereof. Background Art

[0002] Carbon fiber is a fiber material with excellent properties, including high strength, high modulus, thermal and corrosion resistance. It is widely used in aerospace, rail transportation, wind power generation, medical equipment, and leisure and entertainment. Polyacrylonitrile-based carbon fiber holds the largest market share due to its superior performance and relatively low price.

[0003] Carbon fiber oil is an important auxiliary agent used in the production of carbon fiber precursor, and plays an important role in the production of high-performance carbon fiber. Carbon fiber oil generates a uniform oil film on the surface of each monofilament. This oil film isolates the monofilaments from each other to prevent adhesion and doubling. Since the generated oil film is soft and self-lubricating, it can also prevent friction and wear between the tow and the roller during the production process. In the pre-oxidation process, it can prevent heat storage or overheating, which causes local thermal adhesion or hot doubling between the monofilaments, and has a certain help in forming homogenized fibers. During low-temperature carbonization, the oil film still has a protective effect on the fiber surface.

[0004] Currently, silicone-based lubricants are the most common lubricant for carbon fiber production due to their excellent performance and low price. However, silicone-based lubricants present several challenges. Thermal decomposition of the lubricant produces volatilized SiO2, which contributes to dust and silicon contamination in pre-oxidation and carbonization furnaces and associated equipment. Furthermore, the lubricant that penetrates the fiber, undergoing pre-oxidation and carbonization, forms silicon compounds that remain within the fiber, reducing carbon fiber strength. Consequently, the development of low-silicon or non-silicon lubricants has become a hot topic in lubricant development. Low-silicon lubricants reduce the proportion of silicon in the overall lubricant, thereby reducing dust and silicon contamination and ash content. While these lubricants mitigate the impact of silicone-based lubricants, silicon contamination still persists during carbon fiber production. Non-silicon lubricants, primarily composed of polyesters of long-chain fatty acids and polyols, and ethylene oxide adducts of long-chain fatty amides, fundamentally address the silicon contamination issue in carbon fiber production. Currently, patents for carbon fiber lubricants primarily focus on silicone-based and low-silicon lubricants. For example, Chinese patent CN112778527A uses polyol fatty acid ester, phenyl and polyether co-modified silicone oil as the main components to obtain a low-silicone oil for carbon fiber; Chinese patent CN114539530A introduces long carbon chain modification on the basis of the original amino silicone oil, using alkane amino modified silicone oil to improve its temperature resistance, lubricity and anti-roller sticking properties. At the same time, due to the introduction of long carbon chains, the proportion of silicone is reduced. The active ingredients in the oils of the above patents are all modified silicone oils, which will not only cause silicon contamination of production equipment, but also reduce the performance of carbon fiber. If non-silicon components are used to prepare the oil, the various problems caused by silicon contamination will be fundamentally solved. Summary of the Invention

[0005] In view of the defects of the prior art, the technical problem to be solved by the present invention is to provide a carbon fiber precursor oil agent that does not contain silicon compounds, and its preparation method and application. The oil agent has excellent lubricity, heat resistance and antistatic properties. At the same time, the use of the oil agent can eliminate silicon powder pollution in the carbon fiber production process and the silicide residue inside the carbon fiber.

[0006] The present invention provides a carbon fiber precursor oil agent free of silicon compounds, comprising the following components in parts by mass:

[0007] 20-50 parts of oleate;

[0008] 20-30 parts of acetylenic alcohol esters;

[0009] 20-50 parts of polyoxyethylene ether derivatives;

[0010] 1 to 5 parts of emulsifier;

[0011] 1 to 5 parts of antistatic agent;

[0012] 1 to 5 parts of defoaming agent;

[0013] 100-200 parts of deionized water.

[0014] Preferably, the oleate includes one or more of polyethylene glycol oleate, pentaerythritol oleate, glycerol oleate, sorbitan monooleate, glycerol oleate, and trimethylolpropane trioleate.

[0015] Further preferably, the oleate is polyethylene glycol oleate and pentaerythritol oleate, with a mass ratio of 1:2 to 2:1.

[0016] Preferably, the structural formula of the acetylenic alcohol ester is as follows:

[0017] Where R is the remaining part of the organic acid after removing the carboxyl group (that is, the non-carboxyl part of the organic acid), R1, R2 are C1~C 10 wherein m and n are integers of 2 to 10.

[0018] The organic acid includes one or more of acetic acid, oxalic acid, benzoic acid, stearic acid, salicylic acid, lactic acid, adipic acid, and terephthalic acid.

[0019] Preferably, the acetylene alcohol ester is obtained by reacting raw materials containing organic acid and acetylene alcohol polyoxyethylene ether under certain temperature and catalyst conditions.

[0020] Preferably, the structural formula of the acetylenic alcohol polyoxyethylene ether is as follows:

[0021] ; Wherein R1, R2 are C1~C 10 wherein m and n are integers of 2 to 10.

[0022] Preferably, the organic acid includes one or more of acetic acid, oxalic acid, benzoic acid, stearic acid, salicylic acid, lactic acid, adipic acid, and terephthalic acid.

[0023] Preferably, the catalyst is concentrated sulfuric acid.

[0024] Preferably, the molar ratio of the organic acid to the acetylene alcohol polyoxyethylene ether is 1:(0.5-3).

[0025] Preferably, the reaction temperature is 120-150° C., and the reaction time is 3-5 h.

[0026] Preferably, the structural formula of the polyoxyethylene ether derivative is: RCONH-(CH2CH2O) n -H; wherein R is selected from C 10 ~C 20 wherein n is selected from an integer of 2 to 20, and R is preferably selected from C 17 ~C20 wherein n is an integer selected from 10 to 20.

[0027] Preferably, the polyoxyethylene ether derivative is obtained by ethoxylation of long-chain fatty amide with ethylene oxide.

[0028] Preferably, the emulsifier includes one or more of isomeric alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyvinyl alcohol, sodium dodecylbenzene sulfonate, and trihydroxymethane polyoxyethylene ether.

[0029] Preferably, the antistatic agent includes one or more of polyoxyethylene fatty alcohol phosphate, polyoxyethylene laurate, sorbitan fatty acid ester, and dodecyltrimethylammonium chloride.

[0030] Preferably, the defoaming agent includes one or more of ethylene glycol monostearate, isoamyl alcohol, diisobutyl carbinol, and trialkyl melamine.

[0031] The present invention provides a method for preparing a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following steps:

[0032] The components are weighed in parts by mass, and the components are evenly mixed to form an emulsion, thereby obtaining a carbon fiber precursor oil agent free of silicon compounds.

[0033] Preferably, the average particle size of the oil agent is 150 to 300 nm.

[0034] The present invention provides an application of a carbon fiber precursor oil agent free of silicon compounds in the preparation of polyacrylonitrile-based carbon fibers.

[0035] Beneficial effects

[0036] The oil of the present invention can impart excellent lubricity, flexibility, fiber separation, and heat resistance to carbon fiber precursors, effectively protecting the fibers and enhancing their performance. By using oleic acid esters, acetylenic alcohol esters, and polyoxyethylene ether derivatives as the main components of the oil, the oil of the present invention can address silicon powder contamination during carbon fiber production and improve the mechanical properties of the carbon fibers. DETAILED DESCRIPTION

[0037] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0038] The conditions for pre-oxidation and carbonization in the example are as follows:

[0039] Pre-oxidation was carried out in an air atmosphere, and the temperatures were kept at 240°C, 250°C, and 260°C for 15 min respectively; carbonization was carried out in a nitrogen atmosphere, and a gradient temperature increase method was adopted, in which the time for passing through the low-temperature carbonization zone (400°C, 500°C, 600°C, 700°C, 800°C) and the high-temperature carbonization zone (1000°C, 1100°C, 1200°C, 1300°C, 1400°C) was 2 min.

[0040] The test standards and characterization methods involved in the example are as follows:

[0041] The particle size of the oil emulsion was tested using a particle size analyzer; the thermal residual rate was tested using a thermogravimetric analyzer, and the residual rate at 300°C was taken for comparison; the mechanical properties were tested in accordance with the national standard GB / T 31290-2022.

[0042] The structural formula of the acetylenic alcohol ester in the example is:

[0043]

[0044] The structural formula of acetylenic alcohol polyoxyethylene ether:

[0045]

[0046] Polyoxyethylene ether derivative structural formula RCONH-(CH2CH2O) n -H.

[0047] Example 1

[0048] This embodiment provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0049] 20 parts of polyethylene glycol oleate;

[0050] 10 parts of pentaerythritol oleate;

[0051] 20 parts of acetylenic alcohol esters;

[0052] 40 parts of polyoxyethylene ether derivatives;

[0053] 5 parts of nonylphenol polyoxyethylene ether;

[0054] 3 parts of polyoxyethylene laurate;

[0055] 2 parts of isoamyl alcohol;

[0056] 150 parts of deionized water.

[0057] The preparation process of the alkynol ester is as follows:

[0058] Take 120g of benzoic acid and 120g of acetylene alcohol polyoxyethylene ether (R1, R2 are both C1 alkyl, m, n are both 2), and the catalyst concentrated sulfuric acid is 10% of the total reactant mass. React at 150℃ for 4h, neutralize with excess anhydrous sodium bicarbonate, and obtain acetylene alcohol ester after centrifugal purification.

[0059] The polyoxyethylene ether derivative is a product obtained by the ethoxylation reaction of long-chain fatty amide and ethylene oxide, wherein R is C 17 ~C 20 Alkyl, n is an integer between 10 and 20, in this example R is C 17 , n is 15.

[0060] The preparation process and performance testing of the raw silk oil are as follows:

[0061] The above components were mixed uniformly in proportion to obtain an emulsion with an average particle size of 194 nm. The emulsion had excellent stability and a thermal residual rate of 92% at 300°C.

[0062] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smooth, soft, hair-free and parallel carbon fiber precursor; the carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 5167MPa.

[0063] Example 2

[0064] This embodiment provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0065] 10 parts of polyethylene glycol oleate;

[0066] 20 parts of pentaerythritol oleate;

[0067] 20 parts of acetylenic alcohol esters;

[0068] 40 parts of polyoxyethylene ether derivatives;

[0069] 5 parts of nonylphenol polyoxyethylene ether;

[0070] 3 parts of polyoxyethylene laurate;

[0071] 2 parts of isoamyl alcohol;

[0072] 150 parts of deionized water.

[0073] Wherein, the acetylene alcohol ester and the polyoxyethylene ether derivative are the same as those in Example 1.

[0074] The preparation process and performance testing of the raw silk oil are as follows:

[0075] The above components were mixed evenly in proportion to obtain an emulsion with an average particle size of 214 nm. The emulsion had excellent stability and a thermal residual rate of 94% at 300°C.

[0076] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smooth, soft, hair-free and parallel carbon fiber precursor; the carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 5057MPa.

[0077] Example 3

[0078] This embodiment provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0079] 10 parts of polyethylene glycol oleate;

[0080] 10 parts of pentaerythritol oleate;

[0081] 20 parts of acetylenic alcohol esters;

[0082] 50 parts of polyoxyethylene ether derivatives;

[0083] 5 parts of nonylphenol polyoxyethylene ether;

[0084] 3 parts of polyoxyethylene laurate;

[0085] 2 parts of isoamyl alcohol;

[0086] 150 parts of deionized water.

[0087] Wherein, the acetylene alcohol ester and the polyoxyethylene ether derivative are the same as those in Example 1.

[0088] The preparation process and performance testing of the raw silk oil are as follows:

[0089] The above components were mixed uniformly according to the proportion to obtain an emulsion with an average particle size of 227 nm. The emulsion had excellent stability and a heat residual rate of 91% at 300°C.

[0090] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smooth, soft, hair-free and parallel carbon fiber precursor; the carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 4983MPa.

[0091] Example 4

[0092] This embodiment provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0093] 30 parts of polyethylene glycol oleate;

[0094] 20 parts of pentaerythritol oleate;

[0095] 20 parts of acetylenic alcohol esters;

[0096] 20 parts of polyoxyethylene ether derivatives;

[0097] 5 parts of nonylphenol polyoxyethylene ether;

[0098] 3 parts of polyoxyethylene laurate;

[0099] 2 parts of isoamyl alcohol;

[0100] 150 parts of deionized water.

[0101] Wherein, the acetylene alcohol ester and the polyoxyethylene ether derivative are the same as those in Example 1.

[0102] The preparation process and performance testing of the raw silk oil are as follows:

[0103] The above components were mixed uniformly in proportion to obtain an emulsion with an average particle size of 239 nm. The emulsion had excellent stability and a heat residual rate of 94% at 300°C.

[0104] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smooth, soft, hair-free and parallel carbon fiber precursor; the carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 4927MPa.

[0105] Example 5

[0106] This embodiment provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0107] 10 parts of polyethylene glycol oleate;

[0108] 10 parts of pentaerythritol oleate;

[0109] 30 parts of acetylenic alcohol esters;

[0110] 40 parts of polyoxyethylene ether derivatives;

[0111] 5 parts of nonylphenol polyoxyethylene ether;

[0112] 3 parts of polyoxyethylene laurate;

[0113] 2 parts of isoamyl alcohol;

[0114] 150 parts of deionized water.

[0115] Wherein, the acetylene alcohol ester and the polyoxyethylene ether derivative are the same as those in Example 1.

[0116] The preparation process and performance testing of the raw silk oil are as follows:

[0117] The above components were mixed evenly in proportion to obtain an emulsion with an average particle size of 204 nm. The emulsion had excellent stability and a thermal residual rate of 90% at 300°C.

[0118] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smooth, soft, hair-free and parallel carbon fiber precursor; the carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 4895MPa.

[0119] Comparative Example 1

[0120] This comparative example provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0121] 30 parts of polyethylene glycol oleate;

[0122] 40 parts of pentaerythritol oleate;

[0123] 20 parts of acetylenic alcohol esters;

[0124] 5 parts of nonylphenol polyoxyethylene ether;

[0125] 3 parts of polyoxyethylene laurate;

[0126] 2 parts of isoamyl alcohol;

[0127] 150 parts of deionized water.

[0128] Wherein, the acetylene alcohol ester is the same as that in Example 1.

[0129] The preparation process and performance testing of the raw silk oil are as follows:

[0130] The above components were mixed uniformly in proportion to obtain an emulsion with an average particle size of 346 nm. The emulsion had poor stability and a thermal residual rate of 96% at 300°C.

[0131] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smooth, soft, hairy and parallel carbon fiber precursor. The carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 4059 MPa.

[0132] Comparative Example 2

[0133] This comparative example provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0134] 40 parts of acetylenic alcohol esters;

[0135] 50 parts of polyoxyethylene ether derivatives;

[0136] 5 parts of nonylphenol polyoxyethylene ether;

[0137] 3 parts of polyoxyethylene laurate;

[0138] 2 parts of isoamyl alcohol;

[0139] 150 parts of deionized water.

[0140] Wherein, the acetylene alcohol ester and the polyoxyethylene ether derivative are the same as those in Example 1.

[0141] The preparation process and performance testing of the raw silk oil are as follows:

[0142] The above components were mixed evenly in proportion to obtain an emulsion with an average particle size of 247 nm. The emulsion had excellent stability and a thermal residual rate of 81% at 300°C.

[0143] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smooth, soft, hair-free and parallel carbon fiber precursor. The carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 3679MPa.

[0144] Comparative Example 3

[0145] This comparative example provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0146] 30 parts of polyethylene glycol oleate;

[0147] 40 parts of pentaerythritol oleate;

[0148] 40 parts of polyoxyethylene ether derivatives;

[0149] 5 parts of nonylphenol polyoxyethylene ether;

[0150] 3 parts of polyoxyethylene laurate;

[0151] 2 parts of isoamyl alcohol;

[0152] 150 parts of deionized water.

[0153] Wherein, the polyoxyethylene ether derivative is the same as that in Example 1.

[0154] The above components were mixed uniformly in proportion to obtain an emulsion with an average particle size of 235 nm. The emulsion had excellent stability and a thermal residual rate of 95% at 300°C.

[0155] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain a relatively rough, soft, hairy and parallel carbon fiber precursor. The carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 3428MPa.

[0156] Comparative Example 4

[0157] This comparative example provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0158] 20 parts of polyethylene glycol oleate;

[0159] 10 parts of pentaerythritol oleate;

[0160] 20 parts of acetylenic alcohol esters;

[0161] 40 parts of polyoxyethylene ether derivatives;

[0162] 5 parts of nonylphenol polyoxyethylene ether;

[0163] 3 parts of polyoxyethylene laurate;

[0164] 2 parts of isoamyl alcohol;

[0165] 150 parts of deionized water.

[0166] The acetylene alcohol ester is prepared by reacting adipic acid and acetylene alcohol polyoxyethylene ether (R1 and R2 are both C1 alkyl, m and n are both 2), and the specific steps are the same as those in Example 1.

[0167] Wherein, the polyoxyethylene ether derivative is the same as that in Example 1.

[0168] The preparation process and performance testing of the raw silk oil are as follows:

[0169] The above components were mixed evenly in proportion to obtain an emulsion with an average particle size of 217 nm. The emulsion had excellent stability and a thermal residual rate of 92% at 300°C.

[0170] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smooth, soft, hair-free and parallel carbon fiber precursor. The carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 5037MPa.

[0171] Comparative Example 5

[0172] This comparative example provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0173] 20 parts of polyethylene glycol oleate;

[0174] 10 parts of pentaerythritol oleate;

[0175] 20 parts of acetylenic alcohol esters;

[0176] 40 parts of polyoxyethylene ether derivatives;

[0177] 5 parts of nonylphenol polyoxyethylene ether;

[0178] 3 parts of polyoxyethylene laurate;

[0179] 2 parts of isoamyl alcohol;

[0180] 150 parts of deionized water.

[0181] The acetylene alcohol ester is prepared by reacting benzoic acid and acetylene alcohol polyoxyethylene ether (R1 is a C3 alkyl group, R2 is a C5 alkyl group, m is 3, and n is 4), and the specific steps are the same as those in Example 1.

[0182] Wherein, the polyoxyethylene ether derivative is the same as that in Example 1.

[0183] The preparation process and performance testing of the raw silk oil are as follows:

[0184] The above components were mixed evenly in proportion to obtain an emulsion with an average particle size of 226 nm. The emulsion had excellent stability and a thermal residual rate of 93% at 300°C.

[0185] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smooth, soft, hair-free and parallel carbon fiber precursor. The carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 4997MPa.

[0186] Comparative Example 6

[0187] This comparative example provides a carbon fiber precursor oil agent that does not contain silicon compounds, comprising the following components in parts by mass:

[0188] 20 parts of polyethylene glycol oleate;

[0189] 10 parts of pentaerythritol oleate;

[0190] 20 parts of acetylenic alcohol esters;

[0191] 40 parts of polyoxyethylene ether derivatives;

[0192] 5 parts of nonylphenol polyoxyethylene ether;

[0193] 3 parts of polyoxyethylene laurate;

[0194] 2 parts of isoamyl alcohol;

[0195] 150 parts of deionized water.

[0196] Wherein, the acetylene alcohol ester is the same as that in Example 1.

[0197] Among them, polyoxyethylene ether derivatives are products obtained by ethoxylation reaction of long-chain fatty amides and ethylene oxide, where R is C 10 ~C 17 Alkyl, n is an integer between 2 and 10, in this example R is C 12 , n is 5.

[0198] The preparation process and performance testing of the raw silk oil are as follows:

[0199] The above components were mixed uniformly in proportion to obtain an emulsion with an average particle size of 579 nm. The emulsion had poor stability and a thermal residual rate of 90% at 300°C.

[0200] When preparing T700 grade carbon fiber precursor, the oil agent is used to obtain smoother, softer, hairier and more parallel carbon fiber precursor. The carbon fiber obtained after pre-oxidation and carbonization treatment has a tensile strength of 3894 MPa.

[0201] In summary, the present invention uses oleic acid esters, acetylenic alcohol esters and polyoxyethylene ether derivatives as the main components of the oil, and adds emulsifiers, antistatic agents and defoaming agents to form a carbon fiber precursor oil that does not contain silicon compounds.

[0202] From Examples 1 to 5, it can be seen that the carbon fiber precursor oil of the present invention has excellent performance, can protect the fiber and improve the performance of the carbon fiber; from the data of Comparative Examples 1 to 5 and Comparative Examples 1 to 3, it can be seen that the oil prepared by using oleic acid ester, acetylene alcohol ester and polyoxyethylene ether derivative has excellent heat resistance and stability, and the obtained carbon fiber precursor has excellent smoothness; from the data of Comparative Examples 1 to 5 and Comparative Examples 4 to 5, it can be seen that the performance of the oil does not change significantly when using different organic acids and acetylene alcohol polyoxyethylene ethers; from the data of Comparative Examples 1 to 5 and Comparative Example 6, it can be seen that the R of the polyoxyethylene ether derivative is C 17 ~C 20 When the alkyl group and n are integers between 10 and 20, the performance of the oil is better. The present invention proposes a novel carbon fiber precursor oil that does not contain silicon compounds, which is of great significance for eliminating silicon powder pollution in the carbon fiber production process and improving the performance of the carbon fiber.

Claims

1. A carbon fiber precursor oil agent free of silicon compounds, characterized in that: By mass, the components include: The oleate ester includes one or more of polyethylene glycol oleate, pentaerythritol oleate, glycerol oleate, sorbitan monooleate, glycerol oleate, and trimethylolpropane trioleate; The structural formula of the polyoxyethylene ether derivative is: RCONH-(CH2CH2O) n -H; wherein R is selected from C 10 ~C 20 An alkyl group, wherein n is selected from an integer of 2 to 20; The average particle size of the oil is 150 to 300 nm; The structural formula of the alkynol ester is as follows: Wherein R is the remaining part after removing the carboxyl group of the organic acid, R1, R2 are C1~C 10 The alkyl group of m and n is an integer of 2 to 10; the alkynol ester is obtained by reacting a raw material containing an organic acid and an alkynol polyoxyethylene ether under catalyst conditions; The structural formula of the alkynol polyoxyethylene ether is as follows: HO-H2C- m (OH2C)-O-R1--C≡C-R2-O-(CH2O) n -CH2-OH; wherein R1, R2 are C1~C 10 wherein m and n are integers of 2 to 10.

2. The carbon fiber precursor oil containing no silicon compounds according to claim 1, characterized in that: The organic acid includes one or more of acetic acid, oxalic acid, benzoic acid, stearic acid, salicylic acid, lactic acid, adipic acid, and terephthalic acid; and the catalyst is concentrated sulfuric acid.

3. The carbon fiber precursor oil containing no silicon compounds according to claim 1, characterized in that: The molar ratio of the organic acid to the acetylene alcohol polyoxyethylene ether is 1:(0.5-3); the reaction temperature is 120-150° C., and the reaction time is 3-5 hours.

4. The carbon fiber precursor oil containing no silicon compounds according to claim 1, characterized in that The emulsifier includes one or more of isomeric alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyvinyl alcohol, sodium dodecylbenzene sulfonate, and trihydroxymethane polyoxyethylene ether; The antistatic agent includes one or more of polyoxyethylene fatty alcohol phosphate, polyoxyethylene laurate, sorbitan fatty acid ester, and dodecyltrimethylammonium chloride; The defoaming agent includes one or more of ethylene glycol monostearate, isoamyl alcohol, diisobutyl carbinol, and trialkyl melamine.

5. The method for preparing the silicon-free carbon fiber precursor oil according to any one of claims 1 to 4, comprising the following steps: The components are weighed in parts by mass, and the components are evenly mixed to form an emulsion, thereby obtaining a carbon fiber precursor oil agent that does not contain silicon compounds; wherein the average particle size of the oil agent is 150 to 300 nm.

6. Use of the carbon fiber precursor oil agent containing no silicon compounds according to any one of claims 1 to 4 in the preparation of polyacrylonitrile-based carbon fibers.

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