An organic electrolyte for matching (poly) dicyclopentadiene and a carbon fiber surface treatment method

Abstract

The present application relates to a kind of organic electrolyte and carbon fiber surface treatment method matched with (poly) dicyclopentadiene use, belong to carbon fiber processing technical field.The present application provides a kind of organic electrolyte of rich olefinic group matched with (poly) dicyclopentadiene use, and special electrolyte is designed, more, more reactive olefinic functional group can be introduced on carbon fiber surface by electrochemical reaction, and it provides more abundant site by coupling with sizing agent through click chemistry reaction in sizing process.The carbon fiber surface treatment method of the present application is simple to operate, energy saving and environmental protection, low to equipment requirement, interface reinforcing effect is good, can realize sizing agent batch production, can realize special carbon fiber batch production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of carbon fiber processing, and particularly relates to an organic electrolyte matched with (poly) dicyclopentadiene and a carbon fiber surface treatment method. BACKGROUND

[0002] Polydicyclopentadiene (PDCPD) has the advantages of low moisture absorption, high strength, impact resistance and environmental protection, and the resin matrix viscosity thereof can be as low as 0.1 Pa·s, so it is a composite resin matrix with excellent forming ability. However, when the reinforcing body of the polydicyclopentadiene matrix is carbon fiber (CF), the interface bonding ability is poor because the interface energy of the two is low and there is a lack of effective interaction, and the interface shear strength (IFSS) is as low as 13 MPa (the IFSS of CF and epoxy resin under the same conditions is about 60 MPa), so the interface energy absorption is a short board factor that restricts the application of CF reinforced PDCPD resin matrix composites.

[0003] To solve the above technical problems, the prior art patent with publication number CN114478887A first uses supercritical swelling treatment, and then uses a silane coupling agent (4-(4-aminophenyl)benzonitrile triethanol siloxane) to treat carbon fibers, but the whole process is complex, especially the supercritical swelling treatment process cannot be applied to continuous production of carbon fibers. The patent with publication number TW202138643A acidifies and acylates carbon fibers, and then grafts norbornene through esterification, but the acylation and esterification processes require anhydrous oxygen, so they are not suitable for continuous production of carbon fibers. The patent with publication number CN110387115A washes carbon fibers and then uses a silane coupling agent KH570 for treatment, but the washing process cannot introduce functional groups on the surface of carbon fibers that can interact with silane coupling agents or PDCPD. The patent with publication number CN113400683A uses a secondary infusion method to prepare a composite material, but the secondary infusion process cannot introduce functional groups on the surface of carbon fibers that can interact with silane coupling agents or PDCPD. The patent with publication number CN116003943A improves the interaction with fibers by introducing an epoxy resin into the DCPD resin, but this loses the advantages of PDCPD, such as low moisture absorption, high strength, and impact resistance. The patents with publication numbers CN106366300A, CN106749949A, CN106749947A, CN106589250A, CN104448084A, and CN102827318A all use a silane coupling agent (such as KH570) to modify glass fibers to improve their interfacial bonding and ability with PDCPD, but the surface of glass fibers is rich in hydroxyl groups that can interact with silane coupling agents through chemical bonds, which is a characteristic that carbon fibers do not have. In addition, the amino, hydroxyl, and epoxy functional groups provided by conventional silane coupling agents cannot produce strong interactions with PDCPD, and there is no difference in interface performance improvement. KH570 can provide an aliphatic vinyl functional group, but the cross-linking mechanism of DPCD is ring-opening metathesis polymerization, which is different from the aliphatic vinyl functional group, so the chemical bond ability of KH570 and DCPD is limited, which leads to limited interface improvement ability. The patent with publication number CN116063823A uses a norbornene-based silane coupling agent to treat CF, and norbornene has the same cross-linking mechanism as DCPD, which is ring-opening metathesis polymerization, but it still fails to improve the bonding of the silane coupling agent with CF. SUMMARY

[0004] The present application solves the technical problems in the prior art and provides an organic electrolyte matched with (poly)dicyclopentadiene and a carbon fiber surface treatment method, which does not require harsh conditions such as anhydrous oxygen, can be applied to continuous production of carbon fibers, has chemical bond interaction between the coupling agent and the surface of carbon fibers, has chemical bond interaction between the coupling agent and PDCPD on the surface of carbon fibers, and has efficient and easy-to-construct chemical bond interaction.

[0005] To solve the above technical problems, the technical scheme of the present application is as follows:

[0006] An organic electrolyte for matching (poly) dicyclopentadiene, having the following structure:

[0007]

[0008] R is one of the following structures, or one of the branched derivatives of the following structures, or one of the hyperbranched derivatives of the following structures; n is any integer between 0 and 5 (including 0 and 5);

[0009] -H, -Ph.

[0010] In the above technical scheme, preferably, the organic electrolyte is obtained by reacting an olefin derivative of aniline, a nitrite tetrafluoroborate, an anti-crosslinking agent, and acetonitrile or toluene, and the synthesis reaction formula is as follows:

[0011]

[0012] A carbon fiber surface treatment method, comprising the following steps:

[0013] The carbon fiber surface treatment method is divided into two stages;

[0014] Stage ①: carbon fiber surface enrichment of olefins:

[0015] After carbonization, the carbon fiber is subjected to surface electrochemical treatment;

[0016] The electrochemical treatment process is: the carbon fiber is the cathode, and the electrolyte required for electrochemical reduction includes an organic electrolyte and a supporting electrolyte;

[0017] The organic electrolyte is obtained by reacting an olefin derivative of aniline, a nitrite tetrafluoroborate, an anti-crosslinking agent, and acetonitrile or toluene, and the synthesis reaction formula is as follows:

[0018]

[0019] R is one of the following structures, or one of the branched derivatives of the following structures, or one of the hyperbranched derivatives of the following structures; n is any integer between 0 and 5 (including 0 and 5);

[0020] -H, -Ph

[0021] Stage ②: sizing of carbon fiber:

[0022] The electrochemically treated carbon fiber is subjected to sizing treatment;

[0023] The sizing agent required for the sizing treatment of carbon fibers includes a coupling agent, which is referred to as component 1, and a film-forming agent, which is referred to as component 2;

[0024] The sizing agent is synthesized by a two-step method from dicyclopentadiene and a sulfide compound, and after filtration, the reaction system is directly used to configure a solution type or emulsion type sizing agent;

[0025] The structural formula of the dicyclopentadiene is as follows:

[0026]

[0027] The structural formula of the sulfide compound is as follows:

[0028]

[0029] The three R1 groups are the same or different, are one of the following structures, or are one of branched derivatives of the following structures, or are one of hyperbranched derivatives of the following structures, and at least one of the three R1 groups is not a hydrogen atom; n1 is any integer between 0 and 5 (including 0 and 5);

[0030] -H,

[0031] The component 1 is a mixture of the following substances:

[0032]

[0033] The three R2 groups are the same or different, are one of the following structures, or are one of branched derivatives of the following structures, or are one of hyperbranched derivatives of the following structures, and at least one of the three R2 groups is not a hydrogen atom; n2 is any integer between 0 and 5 (including 0 and 5);

[0034] -H,

[0035] The component 2 is a mixture of the following substances:

[0036]

[0037] The sizing agent further includes a coupling catalyst, which is referred to as component 3.

[0038] In the above technical solution, preferably, the electrolyte configuration method required for electrochemical reduction is as follows: the anti-crosslinking agent is dissolved in acetonitrile or toluene, then the olefin derivative of aniline is completely dissolved in the acetonitrile or toluene solution of the anti-crosslinking agent, then the saturated nitrite tetrafluoroborate solution is slowly dropped into the above solution, the reaction is carried out for 15 min, and finally the supporting electrolyte is dissolved in the reaction system to obtain the electrolyte required for electrochemical reduction;

[0039] The electrolyte required for electrochemical reduction: organic electrolyte molar concentration 1-10 mM; supporting electrolyte molar concentration 1-3 mM; anti-crosslinking agent molar concentration 0.01-0.1 mM;

[0040] The supporting electrolyte is tetrabutylammonium tetrafluoroborate;

[0041] The anti-crosslinking agent is phenol, catechol, 2,4-dinitrophenol, 2,6-dinitro-p-cresol or 2,6-di-tert-butyl-4-benzal-cyclohexa-2,5-dienone;

[0042] The potential difference of the electrochemical reaction is 0.5 V;

[0043] The molar ratio of component 1 to component 2 in the sizing agent component is 1:0.8-1:5.

[0044] In the above technical solution, preferably, in the first step reaction for obtaining the sizing agent:

[0045] The molar ratio of the reactants dicyclopentadiene and sulfide compound is 2:1-5:1;

[0046] The solvent is toluene, and the concentration of dicyclopentadiene is 0.1-2.0 mol / L;

[0047] The catalyst 1 is aluminum chloride, aluminum bromide, trifluoroacetic acid or methanesulfonic acid;

[0048] The reaction temperature is 60-200℃, and the synthesis reaction time is 2-7 h.

[0049] In the above technical solution, preferably, in the second step reaction for obtaining the sizing agent:

[0050] The catalyst 2 is Raney Ni;

[0051] The reaction temperature is 40-60℃;

[0052] The reaction time is 10-15 h;

[0053] The reaction system pressure is 0.1-0.2 MPa.

[0054] In the above technical solution, preferably, when component 3 requires high-temperature initiation or light initiation, one-step or two-step sizing of the carbon fiber surface treatment method is adopted, or emulsion sizing or solution sizing is adopted; when component 3 requires room temperature initiation, two-step emulsion sizing of the carbon fiber surface treatment method is adopted.

[0055] In the above technical solution, further preferably, component 3 is dibenzoyl peroxide and dimethylphenylamine, or is azobis isobutyronitrile, or is dibenzoyl peroxide, or is benzoin methyl ether, or is benzophenone and azobis isobutyronitrile.

[0056] In the above technical solution, preferably, when component 3 is azobis isobutyronitrile, dibenzoyl peroxide, benzoin methyl ether, or is benzophenone and azobis isobutyronitrile, a one-step emulsion sizing or one-step solution sizing method is used for carbon fiber surface treatment;

[0057] The above one-step emulsion sizing method for carbon fiber surface treatment specifically includes the following steps:

[0058] a. The mixture of component 1 and component 2 is configured as an emulsion, denoted as emulsion 1;

[0059] b. Component 3 is configured as an emulsion, denoted as emulsion 2;

[0060] c. Emulsion 1, emulsion 2, antistatic agent, lubricant, and deionized water are configured as an emulsion sizing agent in a mass ratio of 5-20:0.5-10:0.1-0.5:0.2-0.8:balance, the balance being the mass of deionized water, the total mass being 100 mass parts;

[0061] d. When component 3 is azobis isobutyronitrile or dibenzoyl peroxide, the carbon fiber is sized, dried at 100-150°C, and then wound; when component 3 is benzoin methyl ether or is benzophenone and azobis isobutyronitrile, the carbon fiber is first sized, then treated with ultraviolet light, dried at 100-150°C, and then wound;

[0062] The above one-step solution sizing method for carbon fiber surface treatment specifically includes the following steps:

[0063] a. Component 1+component 2 (without solvent), component 3, antistatic agent, lubricant, and organic solvent are configured as a solution sizing agent in a mass ratio of 1-2:0.01-0.1:0.1-0.5:0.2-0.8:balance, the balance being the mass of organic solvent, the total mass being 100 mass parts; further preferably, the organic solvent is acetonitrile or toluene;

[0064] b. When component 3 is azobis isobutyronitrile or dibenzoyl peroxide, the carbon fiber is sized, dried at 120-150°C, and then wound; when component 3 is benzoin methyl ether or is benzophenone and azobis isobutyronitrile, the carbon fiber is first sized, then treated with ultraviolet light, dried at 120-150°C, and then wound.

[0065] In the above technical solution, preferably, when component 3 is dibenzoyl peroxide and dimethylphenylamine, or azobis isobutyronitrile, or dibenzoyl peroxide, or benzo pinacol, or benzophenone and azobis isobutyronitrile, the two-step emulsion sizing carbon fiber surface treatment method is adopted.

[0066] The two-step emulsion sizing carbon fiber surface treatment method specifically comprises the following steps:

[0067] a. The mixture of component 1 and component 2 is configured as an emulsion, denoted as emulsion 1;

[0068] b. Component 3 is configured as an emulsion, denoted as emulsion 2;

[0069] c. Emulsion 1, antistatic agent, lubricant and deionized water are configured as an emulsion sizing agent in a mass ratio of 5-20:0.1-0.5:0.2-0.8:balance, the balance being the mass of deionized water, the total mass being 100 mass parts;

[0070] d. The carbon fiber is first sized by emulsion 2, and after sizing, it is blown dry until no liquid drops fall; when component 3 is dibenzoyl peroxide and dimethylphenylamine, azobis isobutyronitrile or dibenzoyl peroxide, the carbon fiber is dried at 100-150 DEG C after sizing and then wound; when component 3 is benzo pinacol or benzophenone and azobis isobutyronitrile, the carbon fiber is first sized, then treated by ultraviolet light, and then dried at 100-150 DEG C after sizing and then wound.

[0071] The present application has the following advantages:

[0072] The present application provides a fulvene-rich organic electrolyte matched with (poly) dicyclopentadiene, and designs a special electrolyte, which can introduce more number and higher reactivity of olefin functional groups on the surface of carbon fiber through electrochemical reaction, and provide more abundant sites for coupling with sizing agent through click chemistry reaction in the sizing process.

[0073] The carbon fiber surface treatment method provided by the present application has the following advantages:

[0074] 1. The present application first uses a fulvene-rich organic electrolyte to introduce more number and higher reactivity of olefin functional groups on the surface of carbon fiber, which can be realized by using conventional carbon fiber production equipment (electrochemical oxidation tank), which is one of the outstanding features of the present application.

[0075] 2. A series of coupling agents containing mercapto group (one of the sizing agent components) is the second outstanding feature of the present application.

[0076] 3. The third prominent feature of this invention is the two-step process of simultaneously synthesizing a thiol-containing coupling agent and a film-forming agent (one of the components of the sizing agent) based on thiol protection and deprotection.

[0077] 4. The method of preparing a special sizing agent by applying the above-mentioned coupling agent and film-forming agent and treating the carbon fiber surface, which achieves in-situ chemical bonding with the carbon fiber surface during the sizing process, is the fourth prominent substantive feature of this invention.

[0078] 5. The mercapto-containing coupling agent used in the processing method of the present invention can interact with the surface of olefin-rich carbon fiber through click chemical reaction, with fast reaction rate and high reaction efficiency. Functional groups that can crosslink with DCPD can be introduced on the surface of carbon fiber through carbon-sulfur bonds during the sizing process, which is one of the significant advancements of the present invention.

[0079] 6. The coupling agent and film-forming agent used in this invention are synthesized simultaneously in two steps. After the first step reaction, there is no need for separation or solvent recovery. Only water washing is required to carry out the second step reaction. After the second step reaction, there is no need for separation or solvent recovery. Only filtration is required to prepare the sizing agent. This method has industrialization capabilities, low equipment requirements, and is environmentally friendly. This is the second significant advancement of this invention.

[0080] 7. The carbon fiber surface treatment method of the present invention does not require anhydrous and oxygen-free reaction conditions such as acidification, acyl chloride, and esterification, nor does it require high temperature and high pressure reaction conditions such as supercritical treatment. It can be achieved in an atmospheric environment using conventional carbon fiber production equipment, and has low requirements for equipment and personnel. This is the third significant improvement of the present invention.

[0081] 8. The carbon fiber surface treatment method of the present invention improves the IFSS by 50%-130% compared with commercially sized CF, which is the fourth significant advancement of the present invention. Attached Figure Description

[0082] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0083] Figure 1 This is a schematic diagram of the chemical structure of olefin derivative 1 of aniline.

[0084] Figure 2 This is a schematic diagram of the chemical structure of olefin derivative 2 of aniline.

[0085] Figure 3 This is a schematic diagram of the chemical structure of olefin derivative 3 of aniline.

[0086] Figure 4 This is a schematic diagram of the chemical structure of 4, an olefinic derivative of aniline.

[0087] Figure 5Chemical structural formula of olefin derivative 5 of aniline.

[0088] Figure 6 Chemical structural formula of olefin derivative 6 of aniline.

[0089] Figure 7 Chemical structural formula of olefin derivative 7 of aniline. DETAILED DESCRIPTION

[0090] The application idea of the present application is: in order to solve the technical problems existing in the prior art, it is necessary to construct an interface phase capable of producing chemical bond interaction with carbon fiber and DCPD, thus three interface enhancement strategies are produced, which can be divided into resin first, fiber second, simultaneous chemical bond production and fiber first, resin second according to the order of the production of chemical bonds by the interface phase and the two sides. The construction mode of resin first, fiber second needs to modify the whole resin matrix, which not only has a large cost, but also easily damages the advantages of the resin matrix itself; the strategy of simultaneous chemical bond production is usually realized in the processing process, and DCPD usually has low viscosity and is easy to dissolve the unstable interface phase in the preforming process; the strategy of CF first in resin can be realized through the sizing process, which is easy to operate and has low dependence on equipment and personnel, therefore, the present application adopts the following: first, an electrochemical oxidation tank is used to construct a large number of active functional groups on the surface of carbon fiber through electrochemical reaction, then a sizing agent coupling agent capable of efficiently reacting with the functional groups is synthesized, the coupling agent can introduce functional groups capable of producing covalent bond with DCPD through ring opening, and finally the chemical bond combination of carbon fiber-sizing agent-resin matrix is realized.

[0091] The present application is implemented in two steps: stage ① carbon fiber surface olefin enrichment: the implementation can be carried out by using the conventional equipment electrochemical oxidation tank in the carbon fiber production line. The present application first develops a special olefin enrichment organic electrolyte, and designs a special electrolyte, and through electrochemical reaction, more number and higher reactivity of olefin functional groups can be introduced on the surface of carbon fiber, which provides more abundant sites for coupling with the sizing agent through click chemistry reaction in the sizing process; stage ② carbon fiber sizing: the present application designs and develops a high-activity coupling agent, which can interact with the olefin functional groups constructed in stage ① through conditional click chemistry reaction, and at the same time, part of the double / triple cyclopentadiene structure is reserved, that is, the crosslinking ability with DCPD matrix is reserved. Based on this, the present application further optimizes the synthesis process of the coupling agent, so that the two most important components of the sizing agent, the coupling agent (component 1) and the film forming agent (component 2), are synthesized by a two-step method, and after the first step reaction (hereinafter referred to as reaction 1), no separation and solvent recovery are required, and only water washing treatment is required to carry out the second step reaction (hereinafter referred to as reaction 2). After the second step reaction, no separation and solvent recovery are required, and the reaction system can be directly used for preparing solution type or emulsion type sizing agent after filtration. Finally, the present application optimizes the introduction strategy of the coupling catalyst (component 3), which maximizes the reaction efficiency of carbon fiber and the sizing agent layer.

[0092] The present application is simple to operate, energy-saving and environment-friendly, has low requirements for equipment, good interface enhancement effect, can realize batch production of sizing agent, and can realize batch production of special carbon fiber.

[0093] The present application first provides an organic electrolyte matched with (poly) dicyclopentadiene, and the structural formula is as follows:

[0094]

[0095] In the formula, R is one of the following structures, or is one of branched derivatives of the following structures, or is one of hyperbranched derivatives of the following structures; n is any integer between 0 and 5 (including 0 and 5).

[0096] -H, -Ph.

[0097] Preferably, the organic electrolyte is obtained by reacting an olefin derivative of aniline, a nitrite tetrafluoroborate, an anti-crosslinking agent, and acetonitrile or toluene, and the synthesis reaction formula is as follows:

[0098]

[0099] The present application also provides a carbon fiber surface treatment method, which is realized by the following steps:

[0100] Stage ① carbon fiber surface olefin enrichment:

[0101] (1) The anti-crosslinking agent is dissolved in acetonitrile or toluene, and then the olefin derivative of aniline (reactant) is added and stirred until completely dissolved; the nitrosonium tetrafluoroborate (NOBF4) is dissolved in a minimum amount of acetonitrile or toluene, and then slowly dripped into the solution of the olefin derivative of aniline, and after 15 min of reaction, the supporting electrolyte is added to obtain the electrolyte required for electrochemical reduction, which is injected into the electrochemical oxidation tank for use.

[0102] The obtained electrolyte includes an organic electrolyte and a supporting electrolyte;

[0103] The organic electrolyte is obtained by reaction of the olefin derivative of aniline, nitrosonium tetrafluoroborate, anti-crosslinking agent, and acetonitrile or toluene, and the synthesis reaction formula is as follows:

[0104]

[0105] In the formula, R is one of the following structures, or is one of branched derivatives of the following structures, or is one of hyperbranched derivatives of the following structures; n is any integer between 0 and 5 (including 0 and 5);

[0106] -H, -Ph

[0107] (2) The carbon fiber primary filaments (i.e. original carbon fibers obtained by oxidation in an oxidation furnace) are introduced into the electrochemical oxidation tank as a cathode for electrochemical reduction reaction, with a potential difference of 0.5 V, and after reaction, water washing and drying, the carbon fibers are subjected to stage ② treatment.

[0108] Stage ② Sizing of carbon fibers:

[0109] The carbon fibers after electrochemical treatment are subjected to sizing treatment;

[0110] The sizing agent required for sizing treatment of carbon fibers includes a coupling agent, which is referred to as component 1, and a film-forming agent, which is referred to as component 2;

[0111] The sizing agent is synthesized by a two-step method from dicyclopentadiene and a thioether compound, and after filtration, the reaction system is directly used to prepare a solution type or emulsion type sizing agent;

[0112] The structure of the dicyclopentadiene is as follows:

[0113]

[0114] The structure of the thioether compound is as follows:

[0115]

[0116] wherein three R1groups are the same or different, and are one of the following structures, or are one of branched derivatives of the following structures, or are one of hyperbranched derivatives of the following structures, and at least one of the three R1is not a hydrogen atom; n1 is any integer between 0 and 5 (including 0 and 5) ;

[0117] -H,

[0118] The component 1 is a mixture of the following substances;

[0119]

[0120] wherein three R2groups are the same or different, and are one of the following structures, or are one of branched derivatives of the following structures, or are one of hyperbranched derivatives of the following structures, and at least one of the three R2is not a hydrogen atom; n2 is any integer between 0 and 5 (including 0 and 5) ;

[0121] -H,

[0122] The component 2 is a mixture of the following substances;

[0123]

[0124] The sizing agent further comprises a coupling catalyst, denoted as component 3;

[0125] The sizing agent is synthesized through a two-step reaction, and the synthesis reaction formula is as follows:

[0126]

[0127] In the synthesis reaction formula, the composition and chemical structure of the intermediate are as follows:

[0128]

[0129] The R1group is consistent with the foregoing definition, and will not be repeated here;

[0130] The sizing treatment specifically comprises the following steps:

[0131] (1) adding DCPD into a reaction kettle, sealing the reaction kettle, pumping nitrogen for 3 times, injecting an organic solvent, stirring to fully dissolve the DCPD, adding catalyst 1, stirring uniformly, dissolving a sulfide compound in the organic solvent, and dropping into the reaction kettle, heating to a specified temperature, cooling to room temperature after the reaction is completed, filtering out the residue, washing the filtrate with water for 3 times, and obtaining a mixed solution of the specific ratio of the intermediate and component 2 after separation;

[0132] (2) To the mixed solution of intermediate and component 2, a catalytic amount of Raney Ni catalyst 2 is added, hydrogen is introduced, the reactor is sealed, high pressure is maintained in the reactor, and heating is performed to convert the thioether functional group contained in the intermediate into a mercapto functional group. After the reaction is completed, the residue is filtered out to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as a stock solution). The synthesis reaction formula is shown in the above reaction formula;

[0133] (3) The stock solution can be diluted, and then component 3, an antistatic agent and a lubricant are added to be used as a one-step solution sizing agent. Alternatively, an emulsifier and deionized water are added to be configured as emulsion 1 for later use;

[0134] (4) Component 3 is dissolved in an organic solvent, an emulsifier and deionized water are added, and emulsion 2 is configured;

[0135] (5) According to different sizing methods, one-step solution sizing agent, one-step emulsion sizing agent or two-step emulsion sizing agent is configured respectively. Through one-step solution sizing, one-step emulsion sizing or two-step emulsion sizing, the surface modification of carbon fibers is realized, and the coupling agent can efficiently interact with CF to form chemical bonds during the sizing (including drying) process, while part of the double / triple cyclopentadiene structure is retained.

[0136] Preferably, the olefin content of the olefin derivative (reactant) of aniline in step (1) of stage ① above is greater than the amino content;

[0137] Further, the electrolyte required for electrochemical reduction in step (1) of stage ① above consists of: an organic electrolyte with a molar concentration of 1-10 mM; a supporting electrolyte with a molar concentration of 1-3 mM; and an anti-crosslinking agent with a molar concentration of 0.01-0.1 mM;

[0138] Further, the supporting electrolyte in step (1) of stage ① above is tetrabutylammonium tetrafluoroborate;

[0139] Further, the anti-crosslinking agent in step (1) of stage ① above is: phenol, o-dihydroxybenzene, 2,4-dinitrophenol, 2,6-dinitro-p-cresol or 2,6-di-tert-butyl-4-benzylidene cyclohexa-2,5-dienone;

[0140] Further, the molar ratio of the reactants double cyclopentadiene and thioether compound in step (1) of stage ② above is 2:1-5:1;

[0141] Further, the organic solvent used in step (1) of stage ② above is toluene, and the concentration of double cyclopentadiene is 0.1-2.0 mol / L, and further preferably 0.1-1.0 mol / L;

[0142] Further, the catalyst used in step (1) of stage ② above is aluminum chloride, aluminum bromide, trifluoroacetic acid or methanesulfonic acid;

[0143] Further, the temperature of the reaction of component 1 and component 2 in step (1) of stage ② above is 60-200℃;

[0144] Further, the time of the reaction of component 1 and component 2 in step (1) of stage ② above is 2-7h;

[0145] Further, the molar ratio of component 1 to component 2 in the raw solution in step (2) of stage ② above is 1:0.8-1:5; the catalyst 2 is Raney Ni; the reaction temperature is 40-60℃, the reaction time is 10-15h, and the reaction system pressure is 0.1-0.2MPa;

[0146] Further, the mass fraction of component 1+component 2 in the emulsion 1 configured in step (3) of stage ② above is 10%-20%;

[0147] Preferably, the oil-water ratio in the emulsion 1 configured in step (3) of stage ② above is 1:1-1:2;

[0148] Further, component 3 in step (4) of stage ② above is: dibenzoyl peroxide+dimethyl aniline, azobis isobutyronitrile, dibenzoyl peroxide, benzoin methyl ether, or benzophenone+azobis isobutyronitrile;

[0149] Further, the mass fraction of component 3 in the emulsion 2 configured in step (4) of stage ② above is 10%-20%;

[0150] Preferably, the oil-water ratio in the emulsion 2 configured in step (4) of stage ② above is 1:1-1:2;

[0151] Further, when component 3 is azobis isobutyronitrile, dibenzoyl peroxide, benzoin methyl ether, or benzophenone+azobis isobutyronitrile, the carbon fiber surface treatment method in step (5) of stage ② above can be one-step emulsion sizing, one-step solution sizing, or two-step emulsion sizing;

[0152] Further, when component 3 is dibenzoyl peroxide+dimethyl aniline, the carbon fiber surface treatment method in step (5) of stage ② above can only be two-step emulsion sizing;

[0153] Further, the one-step emulsion sizing carbon fiber surface treatment method in step (5) of stage ② above is specifically:

[0154] ①The emulsion 1, emulsion 2, antistatic agent, lubricant, and deionized water are configured into an emulsion-type sizing agent in a mass ratio of 5-20:0.5-10:0.1-0.5:0.2-0.8:balance (totaling 100);

[0155] When component 3 is azobisdimethylcyanamide or dibenzoyl peroxide, the carbon fiber is dried at 100-150°C after sizing and then wound; when component 3 is benzo pinacol or dibenzoyl peroxide + azobisdimethylcyanamide, the carbon fiber is first sized, then treated by ultraviolet rays, dried at 100-150°C and then wound.

[0156] Further, the carbon fiber surface treatment method by one-step solution sizing in step (5) of stage 2 above is as follows:

[0157] 1. Component 1 + component 2 (without solvent), component 3, antistatic agent, lubricant and organic solvent are configured into a solution type sizing agent in a mass ratio of 1-2:0.01-0.1:0.1-0.5:0.2-0.8:balance (total 100);

[0158] When component 3 is azobisdimethylcyanamide or dibenzoyl peroxide, the carbon fiber is dried at 120-150°C after sizing and then wound; when component 3 is benzo pinacol or dibenzoyl peroxide + azobisdimethylcyanamide, the carbon fiber is first sized, then treated by ultraviolet rays, dried at 120-150°C and then wound.

[0159] Further, the carbon fiber surface treatment method by two-step emulsion sizing in step (5) of stage 2 above is as follows:

[0160] 1. Emulsion 1, antistatic agent, lubricant and deionized water are configured into an emulsion type sizing agent in a mass ratio of 5-20:0.1-0.5:0.2-0.8:balance (total 100);

[0161] 2. The carbon fiber is first sized by emulsion 2, then blown dry until no liquid drops fall, and then sized by the emulsion obtained in 1. When component 3 is dibenzoyl peroxide + dimethyl aniline, azobisdimethylcyanamide or dibenzoyl peroxide, the carbon fiber is dried at 100-150°C after sizing and then wound; when component 3 is benzo pinacol or dibenzoyl peroxide + azobisdimethylcyanamide, the carbon fiber is first sized, then treated by ultraviolet rays, dried at 100-150°C and then wound.

[0162] The specific embodiments of the present application are described in further detail below in conjunction with examples. The following examples are used to illustrate the present application but are not used to limit the scope of the present application.

[0163] The catalyst used in the following examples is used in a catalytic amount according to the conventional amount in the art, and the antistatic agent, lubricant and emulsifier used are agents that can achieve their functions, and the present application does not have special limitations on their respective types.

[0164] Example 1:

[0165] Stage 1:

[0166] (1) Dissolve 0.01 mM phenol in toluene, then add 1 mM aniline olefin derivative 1 (chemical structure shown as Figure 1

[0167] (2) Carbon fiber nascent filaments (i.e. original carbon fibers obtained by oxidation in an oxidation furnace) are introduced into the electrochemical oxidation tank as cathodes for electrochemical reaction, with a potential difference of 0.5 V. After reaction, the carbon fibers are washed with water and dried, and then subjected to stage ② treatment.

[0168] Stage ②:

[0169] (1) In a reaction kettle, add 132.2 g of DCPD, seal the reaction kettle, and pump nitrogen 3 times. Then inject 7 L of toluene and stir to dissolve the DCPD. Add a catalytic amount of aluminum chloride and stir until uniform. Dissolve 62.1 g of benzyl sulfide in 3 L of toluene and add it dropwise to the reaction kettle. Heat to 60°C and react for 2 h. After the reaction is complete, cool to room temperature. Filter out the residue, wash the filtrate with water 3 times, and separate the layers to obtain a mixed solution of the intermediate and component 2 with a molar ratio of 1:0.8.

[0170] (2) Add a catalytic amount of Raney Ni catalyst to the mixed solution of the intermediate and component 2, and introduce hydrogen gas. Seal the reaction kettle and maintain the pressure inside the reaction kettle at 0.1 MPa. Heat to 40°C and react for 10 h to convert the sulfide functional groups in the intermediate to mercapto functional groups. After the reaction is complete, filter out the residue to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as the original solution).

[0171] (3) After dilution of the original solution, add azobis isobutyronitrile, antistatic agent, and lubricant to prepare a one-step solution sizing agent. Component 1 + component 2 (without solvent), azobis isobutyronitrile, antistatic agent, lubricant, and toluene are prepared in a mass ratio of 1:0.01:0.1:0.2:balance (total 100) to prepare a solution-type sizing agent.

[0172] (4) After sizing, the carbon fibers are dried at 120°C and wound up.

[0173] (5) The IFSS of the sized carbon fibers and PDCPD is 18 MPa, and the IFSS of commercial sized CF and PDCDP is 12 MPa.

[0174] Example 2:

[0175] Stage ①:

[0176] ​(1) 0.1 mM catechol was dissolved in toluene, 10 mM aniline olefin derivative 2 (chemical structure as shown in Figure 2

[0177] (2) The carbon fiber nascent yarn (i.e. the original carbon fiber obtained by oxidation in an oxidation furnace) was introduced into the electrochemical oxidation tank as a cathode for electrochemical reaction, with a potential difference of 0.5 V. After reaction, water washing and drying, the carbon fiber was subjected to stage ② treatment.

[0178] Stage ②:

[0179] (1) 2644 g of DCPD was added to a reaction kettle, the reaction kettle was sealed, and nitrogen was pumped out for 3 times. 7 L of toluene was injected, and the DCPD was fully dissolved by stirring. A catalytic amount of aluminum bromide was added and stirred uniformly. 552 g of benzyl methyl sulfide was dissolved in 3 L of toluene and added dropwise into the reaction kettle. The temperature was raised to 200°C, and the reaction was carried out for 7 h. After the reaction was completed, the temperature was lowered to room temperature. The residue was removed by filtration, and the filtrate was washed with water three times. After separation, a mixed solution of the intermediate and component 2 with a molar ratio of 1:5 was obtained.

[0180] (2) A catalytic amount of Raney Ni catalyst was added to the mixed solution of the intermediate and component 2, and hydrogen was introduced. The reaction kettle was sealed, and the pressure inside the reaction kettle was maintained at 0.2 MPa. The temperature was raised to 60°C, and the reaction was carried out for 15 h to convert the sulfide functional group in the intermediate to a mercapto functional group. After the reaction was completed, the residue was removed by filtration to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as the original solution).

[0181] (3) After dilution of the original solution, dibenzoyl peroxide, antistatic agent and lubricant were added to prepare a one-step solution sizing agent. Component 1 + component 2 (without solvent), dibenzoyl peroxide, antistatic agent, lubricant and toluene were prepared in a mass ratio of 2:0.1:0.5:0.8:balance (total 100) to prepare a solution type sizing agent.

[0182] (4) After sizing, the carbon fiber was dried at 150°C and wound up.

[0183] (5) The IFSS of the sized carbon fiber and PDCPD was 27.6 MPa, and the IFSS of the commercial sized CF and PDCDP was 12 MPa.

[0184] Example 3:

[0185] Stage ①:

[0186] ​(1) 0.1 mM 2,4-dinitrophenol was dissolved in toluene, 10 mM aniline olefin derivative 3 (chemical structure as shown in Figure 3 ) was added, and stirred until completely dissolved; 10 mM nitroso tetrafluoroborate was dissolved in a minimum amount of toluene, and then slowly dripped into the above aniline olefin derivative 3 solution, after 15 min of reaction, 3 mM tetrabutylammonium tetrafluoroborate was added to obtain the electrolyte required for electrochemical reduction, and the electrolyte required for electrochemical reduction was injected into the electrochemical oxidation tank for use.

[0187] (2) The carbon fiber nascent yarn (i.e. the original carbon fiber obtained by oxidation in an oxidation furnace) was introduced into the electrochemical oxidation tank as a cathode for electrochemical reaction, the potential difference was 0.5 V, after reaction, water washing and drying, the process of stage ② was carried out.

[0188] Stage ②:

[0189] (1) 2644 g of DCPD was added to a reaction kettle, the reaction kettle was closed, nitrogen was pumped out for 3 times, 7 L of toluene was injected, and DCPD was fully dissolved by stirring; a catalytic amount of trifluoroacetic acid was added and stirred uniformly; 608 g of (2-phenylethyl) methyl sulfide was dissolved in 3 L of toluene and added dropwise to the reaction kettle; the temperature was raised to 180℃, and the reaction was carried out for 5 h, then the temperature was lowered to room temperature; the residue was filtered out, the filtrate was washed with water for 3 times, and after separation, a mixed solution of intermediate and component 2 with a molar ratio of 1:5 was obtained;

[0190] (2) A catalytic amount of Raney Ni catalyst was added to the mixed solution of intermediate and component 2, hydrogen was introduced, the reaction kettle was sealed, the pressure in the reaction kettle was maintained at 0.2 MPa, and heated to 60℃ for 15 h to convert the sulfide functional group in the intermediate to a mercapto functional group, after the reaction was completed, the residue was filtered out to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as the original solution);

[0191] (3) Toluene was added to dilute the original solution to a mass fraction of 20% of component 1 + component 2, deionized water and emulsifier were added in an equal volume of the organic solution, and under the action of stirring, emulsion 1 was configured (the oil-water ratio in emulsion 1 was 1:1, and the mass fraction of component 1 + component 2 was 10%);

[0192] (4) Bismuth methyl ether was dissolved in toluene (mass fraction of 20%), deionized water and emulsifier were added in an equal volume of the organic solution, and under the action of stirring, emulsion 2 was configured (the oil-water ratio in emulsion 2 was 1:1, and the mass fraction of component 1 + component 2 was 10%);

[0193] (5) Emulsion 1, emulsion 2, antistatic agent, lubricant and deionized water were configured into one-step emulsion sizing agent in a mass ratio of 5:0.5:0.1:0.2:balance (totaling 100);

[0194] (6) Carbon fiber prepared by step (4) is treated by UV after one-step emulsion sizing agent, and finally dried at 130°C and wound up;

[0195] (7) The IFSS of carbon fiber after sizing with PDCPD is 25 MPa, and the IFSS of commercial sized CF with PDCPD is 12 MPa.

[0196] Example 4:

[0197] Stage ①:

[0198] (1) 0.1 mM 2,6-dinitro-p-cresol is dissolved in toluene, 10 mM aniline olefin derivative 4 (chemical structure is shown as Figure 4 ) is added, and stirred until completely dissolved; 10 mM nitrous tetrafluoroborate is dissolved in a minimum amount of toluene, and then slowly dripped into the aniline olefin derivative 4 solution, and after 15 min of reaction, 3 mM tetrabutylammonium tetrafluoroborate is added to obtain the electrolyte required for electrochemical reduction. The electrolyte required for electrochemical reduction is injected into the electrochemical oxidation tank for use.

[0199] (2) Carbon fiber nascent filaments (i.e. original carbon fiber obtained by oxidation in an oxidation furnace) are introduced into the electrochemical oxidation tank as a cathode for electrochemical reaction, with a potential difference of 0.5 V. After reaction, water washing and drying, stage ② treatment is performed.

[0200] Stage ②:

[0201] (1) 2644 g of DCPD is added to a reaction kettle, the reaction kettle is closed, nitrogen is pumped out for 3 times, 7 L of toluene is injected, and stirring is performed to dissolve the DCPD completely; a catalytic amount of methanesulfonic acid is added and stirred uniformly; 664 g of (3-phenylbutyl) methyl sulfide is dissolved in 3 L of toluene and added dropwise to the reaction kettle; the temperature is raised to 180°C, and reaction is performed for 5 h, after which the temperature is lowered to room temperature; the residue is removed by filtration, the filtrate is washed with water for 3 times, and after separation, a mixed solution of intermediate and component 2 with a molar ratio of 1:5 is obtained;

[0202] (2) A catalytic amount of Raney Ni catalyst is added to the mixed solution of intermediate and component 2, hydrogen is introduced, the reaction kettle is sealed, the pressure in the reaction kettle is maintained at 0.2 MPa, and heating is performed to 60°C for 15 h to convert the sulfide functional group in the intermediate to a mercapto functional group. After the reaction is completed, the residue is removed by filtration to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as a stock solution);

[0203] (3) Add toluene to dilute the stock solution to a mass fraction of 60% of component 1 + component 2, add deionized water and emulsifier in an amount of 2 times the volume of the organic solution, and emulsify under stirring. Configure the foregoing emulsion, antistatic agent, lubricant, and deionized water in a mass ratio of 20:0.5:0.8: the balance (totaling 100) to form emulsion 1;

[0204] (4) Dissolve benzoin dimethyl ether in toluene (mass fraction of 60%), add deionized water and emulsifier in an amount of 2 times the volume of the organic solution, and configure under stirring to form emulsion 2 (the oil-water ratio in emulsion 2 is 1:2, and the mass fraction of component 1 + component 2 is 20%);

[0205] (5) After the carbon fiber is sized with emulsion 1, blow dry until no liquid drops fall, then size with emulsion 2, then use ultraviolet light treatment, and finally dry at 130°C and wind up;

[0206] (6) The IFSS of the sized carbon fiber with PDCPD is 22 MPa, and the IFSS of the commercial sized CF with PDCPD is 12 MPa.

[0207] Example 5:

[0208] Stage ①:

[0209] (1) Dissolve 0.1 mM 2,6-di-tert-butyl-4-benzylidene cyclohexa-2,5-dienone in toluene, then add 10 mM of aniline olefin derivative 5 (the chemical structure is shown as Figure 5 Slowly drop 10 mM nitroso tetrafluoroborate into the foregoing aniline olefin derivative 5 solution, and after 15 min of reaction, add 3 mM tetrabutylammonium tetrafluoroborate to obtain the electrolyte required for electrochemical reduction. Pour the electrolyte required for electrochemical reduction into an electrochemical oxidation tank for standby use.

[0210] (2) Introduce carbon fiber nascent filaments (i.e., original carbon fibers obtained by oxidation in an oxidation furnace) as a cathode into an electrochemical oxidation tank for electrochemical reaction at a potential difference of 0.5 V. After reaction, wash with water and dry, then perform stage ② processing.

[0211] Stage ②:

[0212] (1) Add 2644 g of DCPD to a reaction kettle, evacuate and fill with nitrogen 3 times, inject 7 L of toluene, and stir to dissolve the DCPD; add a catalytic amount of methanesulfonic acid and stir uniformly; dissolve 720 g of (4-phenyl-n-butyl) methyl sulfide in 3 L of toluene and drop into the reaction kettle; heat to 180°C and react for 5 h, then cool to room temperature; filter out the residue, wash the filtrate with water 3 times, and after separation, obtain a mixed solution of the intermediate and component 2 in a molar ratio of 1:5;

[0213] (2) To the mixed solution of intermediate and component 2, a catalytic amount of Raney Ni catalyst is added, hydrogen is introduced, the reactor is sealed, the pressure in the reactor is maintained at 0.2 MPa, and the reactor is heated to 60°C for 15 h to convert the thioether functional group contained in the intermediate into a mercapto functional group. After the reaction is completed, the residue is filtered out to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as a stock solution).

[0214] (3) The stock solution is diluted to a mass fraction of 60% of component 1 + component 2 by adding toluene, deionized water in an amount of 2 times the volume of the organic solution, and an emulsifier, and emulsified under stirring. The aforementioned emulsion, antistatic agent, lubricant, and deionized water are configured in a mass ratio of 20:0.5:0.8: the balance (totaling 100) to form emulsion 1.

[0215] (4) Oxidized dibenzoyl + dimethyl aniline in a molar ratio of 1:1 is dissolved in toluene (mass fraction of 60%), deionized water in an amount of 2 times the volume of the organic solution, and an emulsifier are added, and emulsion 2 is configured under stirring (the oil-water ratio in emulsion 2 is 1:2, and the mass fraction of component 1 + component 2 is 20%);

[0216] (5) After the carbon fiber is sized with emulsion 1 and dried to remove liquid droplets, it is sized with emulsion 2, then treated with ultraviolet light, and finally dried at 130°C and wound up.

[0217] (6) The IFSS of the sized carbon fiber and PDCPD is 23 MPa, and the IFSS of the commercial sized CF and PDCDP is 12 MPa.

[0218] Example 6:

[0219] Stage ①:

[0220] (1) 0.1 mM 2,6-di-tert-butyl-4-benzylidene cyclohex-2,5-dienone is dissolved in toluene, 10 mM aniline olefin derivative 6 (the chemical structure is shown in Figure 6 ) is added, and stirring is performed until complete dissolution. 10 mM nitroso tetrafluoroborate is dissolved in a minimum amount of toluene, and then slowly added dropwise into the aniline olefin derivative 6 solution. After 15 min of reaction, 3 mM tetrabutylammonium tetrafluoroborate is added to obtain the electrolyte required for electrochemical reduction. The electrolyte required for electrochemical reduction is injected into the electrochemical oxidation tank for use.

[0221] (2) Carbon fiber nascent filaments (i.e. original carbon fibers obtained by oxidation in an oxidation furnace) are introduced into the electrochemical oxidation tank as cathodes for electrochemical reaction, and the potential difference is 0.5 V. After reaction, water washing and drying are performed, and then stage ② processing is performed.

[0222] Stage ②:

[0223] (1) In a reaction kettle, 2644g DCPD was added, the reaction kettle was closed, nitrogen was pumped in for 3 times, 7L toluene was injected, and DCPD was fully dissolved by stirring; catalytic amount of methanesulfonic acid was added and stirred uniformly; 776g (5-phenyl-n-pentyl) methyl sulfide was dissolved in 3L toluene and added dropwise into the reaction kettle; the temperature was raised to 180℃, and the reaction was carried out for 5h, and then the temperature was lowered to room temperature; the residue was removed by filtration, the filtrate was washed with water for 3 times, and a mixed solution of intermediate and component 2 with a molar ratio of 1:5 was obtained after separation;

[0224] (2) A catalytic amount of Raney Ni catalyst was added to the mixed solution of intermediate and component 2, hydrogen was introduced, the reaction kettle was sealed, the pressure in the reaction kettle was maintained at 0.2MPa, and the temperature was raised to 60℃ for 15h to convert the thioether functional group contained in the intermediate into a mercapto functional group; after the reaction was completed, the residue was removed by filtration to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as a stock solution);

[0225] (3) The stock solution was diluted to a mass fraction of 60% of component 1 + component 2 by adding toluene, deionized water and emulsifier in an amount of 2 times the volume of the organic solution, and emulsified under stirring. The aforementioned emulsion, antistatic agent, lubricant and deionized water were configured in a mass ratio of 20:0.5:0.8: the balance (totaling 100) to form emulsion 1;

[0226] (4) Benzophenone oxide + azobis isobutyronitrile with a molar ratio of 1:1 was dissolved in toluene (mass fraction of 60%), deionized water and emulsifier in an amount of 2 times the volume of the organic solution were added, and emulsion 2 was configured under stirring (the oil-water ratio in emulsion 2 was 1:2, and the mass fraction of component 1 + component 2 was 20%);

[0227] (5) After the carbon fiber was sized with emulsion 1 and dried without liquid droplets, it was sized with emulsion 2, then treated with ultraviolet rays, and finally dried at 130℃ and wound up;

[0228] (6) The IFSS of the sized carbon fiber and PDCPD was 23MPa, and the IFSS of the commercial sized CF and PDCDP was 12MPa.

[0229] Example 7:

[0230] Stage ①:

[0231] (1) 0.1mM 2,6-di-tert-butyl-4-benzylidene cyclohex-2,5-dienone was dissolved in toluene, and 10mM aniline was added to the olefin derivative 7 (chemical structure as shown in Figure 7The solution of the aniline olefin derivative 7 is prepared by dissolving 10 g of the aniline olefin derivative 7 in 100 mL of toluene, stirring until completely dissolved; 10 mM nitroso tetrafluoroboric acid is dissolved in a minimum amount of toluene, then slowly added dropwise into the solution of the aniline olefin derivative 7, after 15 min of reaction, 3 mM tetrabutylammonium tetrafluoroborate is added to obtain the electrolyte required for electrochemical reduction, and the electrolyte required for electrochemical reduction is injected into the electrochemical oxidation tank for use.

[0232] (2) The carbon fiber nascent filaments (i.e. the original carbon fibers obtained by oxidation in the oxidation furnace) are introduced into the electrochemical oxidation tank as the cathode for electrochemical reaction, the potential difference is 0.5 V, after reaction, water washing and drying, the stage ② treatment is carried out.

[0233] Stage ②:

[0234] (1) 2644 g of DCPD is added to the reaction kettle, the reaction kettle is sealed, nitrogen is pumped out for 3 times, 7 L of toluene is injected, and the DCPD is fully dissolved by stirring; a catalytic amount of trifluoroacetic acid is added and stirred uniformly; 864 g of 1,3,5-tris (methylthio) benzene is dissolved in 3 L of toluene and added dropwise into the reaction kettle; the temperature is raised to 180℃, and the reaction is carried out for 5 h, then the temperature is lowered to room temperature after the reaction is completed; the residue is filtered out, the filtrate is washed with water for 3 times, and after separation, a mixed solution of component 1 and component 2 with a molar ratio of 1:5 (hereinafter referred to as the original solution) is obtained;

[0235] (2) A catalytic amount of Raney Ni catalyst is added to the mixed solution of the intermediate and component 2, hydrogen is introduced, the reaction kettle is sealed, the pressure in the reaction kettle is maintained at 0.2 MPa, heated to 60℃ and reacted for 15 h, so that the thioether functional group contained in the intermediate is converted into a mercapto functional group, after the reaction is completed, the residue is filtered out to obtain a mixed solution of the intermediate and component 2;

[0236] (3) The original solution is diluted to 20% of the mass fraction of component 1 + component 2 by adding toluene, and an equal volume of deionized water and emulsifier is added to prepare emulsion 1 (the oil-water ratio in emulsion 1 is 1:1, and the mass fraction of component 1 + component 2 is 10%);

[0237] (4) The benzoin dimethyl ether is dissolved in toluene (the mass fraction is 20%), and an equal volume of deionized water and emulsifier is added to prepare emulsion 2 (the oil-water ratio in emulsion 2 is 1:1, and the mass fraction of component 1 + component 2 is 10%);

[0238] (5) The emulsion 1, emulsion 2, antistatic agent, lubricant and deionized water are configured in a mass ratio of 5:0.5:0.1:0.2:the rest (a total of 100) to prepare a one-step emulsion sizing agent;

[0239] (6) The carbon fiber is treated with the one-step emulsion sizing agent prepared in step (4) and then treated with ultraviolet light, and finally dried at 130℃ and wound up;

[0240] (7) The IFSS of carbon fiber after sizing with PDCPD is 23 MPa, and the IFSS of commercial sized CF with PDCPD is 12 MPa.

[0241] Example 8:

[0242] Stage ①:

[0243] (1) 0.1 mM 2,6-di-tert-butyl-4-benzylidene cyclohex-2,5-dienone was dissolved in toluene, 10 mM aniline olefin derivative 7 (chemical structure shown as Figure 7 ) was added, and stirred until completely dissolved; 10 mM nitroso tetrafluoroborate was dissolved in a minimum amount of toluene, and then slowly added dropwise into the aniline olefin derivative 7 solution, and after 15 min, 3 mM tetrabutylammonium tetrafluoroborate was added to obtain the electrolyte required for electrochemical reduction. The electrolyte required for electrochemical reduction was injected into the electrochemical oxidation tank for use.

[0244] (2) Carbon fiber nascent filaments (i.e. original carbon fibers obtained by oxidation in an oxidation furnace) were introduced into the electrochemical oxidation tank as a cathode for electrochemical reaction, with a potential difference of 0.5 V. After reaction, water washing and drying, stage ② processing was performed.

[0245] Stage ②:

[0246] (1) 2644 g DCPD was added to a reaction kettle, the reaction kettle was sealed, nitrogen was pumped out for 3 times, 7 L toluene was injected, and stirring was performed to dissolve the DCPD completely; a catalytic amount of trifluoroacetic acid was added, and stirring was performed until uniform; 664 g phenyl tert-butyl sulfide was dissolved in 3 L toluene, and was added dropwise into the reaction kettle; the temperature was raised to 180°C, and reaction was performed for 5 h, after which the temperature was lowered to room temperature; the residue was removed by filtration, the filtrate was washed with water for 3 times, and after separation, a mixed solution of intermediate and component 2 with a molar ratio of 1:5 was obtained;

[0247] (2) A catalytic amount of Raney Ni catalyst was added to the mixed solution of intermediate and component 2, hydrogen was introduced, the reaction kettle was sealed, the pressure inside the reaction kettle was maintained at 0.2 MPa, and heating was performed to 60°C for 15 h, so that the sulfide functional group contained in the intermediate was converted into a mercapto functional group. After the reaction was completed, the residue was removed by filtration to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as a stock solution);

[0248] (3) Toluene was added to dilute the stock solution to a mass fraction of component 1 + component 2 of 20%, deionized water and an emulsifier were added in an equal volume to the organic solution, and under the action of stirring, emulsion 1 was configured (the oil-water ratio in emulsion 1 was 1:1, and the mass fraction of component 1 + component 2 was 10%);

[0249] (4) Dissolve the bismuthyl methyl ether in toluene (20% by mass), add deionized water and emulsifier in equal volume of the organic solution, and prepare emulsion 2 (emulsion 2, oil-water ratio is 1:1, the mass fraction of component 1 + component 2 is 10%) under stirring;

[0250] (5) Emulsion 1, emulsion 2, antistatic agent, lubricant and deionized water are prepared into one-step emulsion sizing agent in a mass ratio of 5:0.5:0.1:0.2:balance (total 100);

[0251] (6) After the carbon fiber is treated by the one-step emulsion sizing agent prepared in step (4), it is treated by ultraviolet rays, and finally dried at 130°C and wound up;

[0252] (7) The IFSS of the sized carbon fiber and PDCPD is 23 MPa, and the IFSS of the commercial sized CF and PDCPD is 12 MPa.

[0253] Example 9:

[0254] Stage ①:

[0255] (1) Dissolve 0.1 mM 2,6-di-tert-butyl-4-benzylidene cyclohex-2,5-dienone in toluene, then add 10 mM aniline olefin derivative 7 (chemical structure as shown in Figure 7 ), stir until completely dissolved; dissolve 10 mM nitrite tetrafluoroborate in a minimum amount of toluene, then slowly drop into the aniline olefin derivative 7 solution, after 15 min of reaction, add 3 mM tetrabutylammonium tetrafluoroborate to obtain the electrolyte required for electrochemical reduction. The electrolyte required for electrochemical reduction is injected into the electrochemical oxidation tank for use.

[0256] (2) Carbon fiber nascent filaments (i.e. original carbon fibers obtained by oxidation in an oxidation furnace) are introduced into the electrochemical oxidation tank as cathodes for electrochemical reaction, with a potential difference of 0.5 V. After reaction, water washing and drying, stage ② treatment is performed.

[0257] Stage ②:

[0258] (1) In a reaction kettle, add 2644 g of DCPD, close the reaction kettle, evacuate nitrogen 3 times, inject 7 L of toluene, and stir to dissolve the DCPD completely; add a catalytic amount of trifluoroacetic acid and stir evenly; dissolve 664 g of phenyl tert-butyl sulfide in 3 L of toluene and add dropwise to the reaction kettle; heat to 180°C and react for 5 h, then cool to room temperature; filter out the residue, wash the filtrate with water three times, and separate the layers to obtain a mixed solution of intermediate and component 2 with a molar ratio of 1:5;

[0259] (2) To the mixed solution of intermediate and component 2, a catalytic amount of Raney Ni catalyst was added, hydrogen was introduced, the reactor was sealed, the pressure in the reactor was maintained at 0.2 MPa, and the reactor was heated to 60°C for 15 h to convert the thioether functional group contained in the intermediate to a mercapto functional group. After the reaction was completed, the residue was filtered out to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as the original solution).

[0260] (3) The original solution was diluted to 20% of the mass fraction of component 1 + component 2 by adding toluene, and an equal volume of deionized water and an emulsifier was added to prepare emulsion 1 (the oil-water ratio in emulsion 1 was 1:1, and the mass fraction of component 1 + component 2 was 10%) under stirring.

[0261] (4) Benzoin methyl ether was dissolved in toluene (mass fraction of 20%), and an equal volume of deionized water and an emulsifier was added to prepare emulsion 2 (the oil-water ratio in emulsion 2 was 1:1, and the mass fraction of component 1 + component 2 was 10%) under stirring.

[0262] (5) Emulsion 1, emulsion 2, antistatic agent, lubricant, and deionized water were mixed in a mass ratio of 5:0.5:0.1:0.2:balance (total 100) to prepare a one-step emulsion sizing agent.

[0263] (6) The carbon fiber was treated with the one-step emulsion sizing agent prepared in step (4) and then treated with ultraviolet light, and finally dried at 130°C and wound up.

[0264] (7) The IFSS of the sized carbon fiber and PDCPD was 23 MPa, and the IFSS of the commercial sized CF and PDCPD was 12 MPa.

[0265] Example 10:

[0266] Stage ①:

[0267] (1) 0.1 mM 2,6-di-tert-butyl-4-benzylidene cyclohexa-2,5-dienone was dissolved in toluene, and 10 mM aniline olefin derivative 7 (the chemical structure is shown in Figure 7 ) was added, and stirred until completely dissolved. 10 mM nitroso tetrafluoroborate was dissolved in a minimum amount of toluene, and then slowly added dropwise into the aniline olefin derivative 7 solution. After 15 min of reaction, 3 mM tetrabutylammonium tetrafluoroborate was added to obtain the electrolyte required for electrochemical reduction. The electrolyte required for electrochemical reduction was injected into the electrochemical oxidation tank for use.

[0268] (2) The carbon fiber nascent filament (i.e. the original carbon fiber obtained by oxidation in an oxidation furnace) was introduced into the electrochemical oxidation tank as a cathode for electrochemical reaction, and the potential difference was 0.5 V. After reaction, water washing and drying, stage ② treatment was carried out.

[0269] Stage 2:

[0270] (1) Add 2644g DCPD to a reaction kettle, seal the reaction kettle, pump nitrogen 3 times, inject 7L of toluene, stir to dissolve DCPD; add catalytic amount of trifluoroacetic acid, stir evenly; dissolve 664g of phenyl tert-butyl sulfide in 3L of toluene and add dropwise to the reaction kettle; heat to 180°C, react for 5h, and then cool to room temperature; filter out the residue, wash the filtrate with water 3 times, and after separation, obtain a mixed solution of molar ratio 1:5 of intermediate and component 2;

[0271] (2) Add catalytic amount of Raney Ni catalyst to the mixed solution of intermediate and component 2, introduce hydrogen, seal the reaction kettle, maintain the pressure in the reaction kettle at 0.2MPa, heat to 60°C and react for 15h to convert the sulfide functional group in the intermediate to a mercapto functional group, filter out the residue after the reaction is completed, and obtain a mixed solution of component 1 and component 2 (hereinafter referred to as the original solution);

[0272] (3) Dilute the original solution to 20% of the mass fraction of component 1 + component 2 by adding toluene, add deionized water and emulsifier in an equal volume of the organic solution, and under the action of stirring, configure into emulsion 1 (emulsion 1 has an oil-water ratio of 1:1 and a mass fraction of component 1 + component 2 of 10%);

[0273] (4) Dissolve benzoin dimethyl ether in toluene (mass fraction of 20%), add deionized water and emulsifier in an equal volume of the organic solution, and under the action of stirring, configure into emulsion 2 (emulsion 2 has an oil-water ratio of 1:1 and a mass fraction of component 1 + component 2 of 10%);

[0274] (5) Configure the emulsion 1, emulsion 2, antistatic agent, lubricant and deionized water into one-step emulsion sizing agent in a mass ratio of 5:0.5:0.1:0.2:balance (total 100);

[0275] (6) After the carbon fiber is treated with the one-step emulsion sizing agent prepared in step (4), it is treated with ultraviolet light, and finally dried at 130°C and wound up;

[0276] (7) The IFSS of the sized carbon fiber and PDCPD is 23MPa, and the IFSS of the commercial sized CF and PDCPD is 12MPa.

[0277] Example 11:

[0278] Stage 1:

[0279] (1) Dissolve 0.1mM 2,6-di-tert-butyl-4-benzylidene cyclohexa-2,5-dienone in toluene, then add 10mM aniline to the olefin derivative 7 (chemical structure as shown in ​The solution of the aniline olefin derivative 7 is stirred until complete dissolution; the 10 mM nitroso tetrafluoroboric acid is dissolved in a minimum amount of toluene and then slowly added dropwise to the solution of the aniline olefin derivative 7 described above; after 15 min of reaction, 3 mM tetrabutylammonium tetrafluoroborate is added to obtain the electrolyte required for the electrochemical reduction; the electrolyte required for the electrochemical reduction is injected into the electrochemical oxidation tank and is ready for use.

[0280] (2) The carbon fiber nascent filaments (i.e. the original carbon fibers obtained by oxidation in the oxidation furnace) are introduced into the electrochemical oxidation tank as the cathode to undergo electrochemical reaction, with a potential difference of 0.5 V; after the reaction, the carbon fibers are washed with water and dried, and then subjected to the process of stage ②.

[0281] Stage ②:

[0282] (1) 2644 g of DCPD is added to a reaction kettle, the reaction kettle is closed, nitrogen is pumped in and out for 3 times, 7 L of toluene is injected, and the DCPD is stirred to dissolve completely; a catalytic amount of trifluoroacetic acid is added and stirred uniformly; 944 g of (5-phenyl n-pentyl) tert-butyl sulfide is dissolved in 3 L of toluene and added dropwise to the reaction kettle; the temperature is raised to 180°C, and the reaction is carried out for 5 h; after the reaction is completed, the temperature is lowered to room temperature; the residue is filtered out, the filtrate is washed with water for 3 times, and after separation, a mixed solution of the intermediate and component 2 with a molar ratio of 1:5 is obtained;

[0283] (2) A catalytic amount of Raney Ni catalyst is added to the mixed solution of the intermediate and component 2, hydrogen is introduced, the reaction kettle is sealed, the pressure in the reaction kettle is maintained at 0.2 MPa, and the temperature is raised to 60°C to react for 15 h, so that the sulfide functional group contained in the intermediate is converted into a mercapto functional group; after the reaction is completed, the residue is filtered out to obtain a mixed solution of component 1 and component 2 (hereinafter referred to as the original solution);

[0284] (3) Toluene is added to dilute the original solution to a mass fraction of 20% of component 1 + component 2, deionized water and an emulsifier are added in an equal volume of the organic solution, and under the action of stirring, an emulsion 1 (the oil-water ratio in the emulsion 1 is 1:1, and the mass fraction of component 1 + component 2 is 10%) is configured;

[0285] (4) Benzoin dimethyl ether is dissolved in toluene (mass fraction of 20%), deionized water and an emulsifier are added in an equal volume of the organic solution, and under the action of stirring, an emulsion 2 (the oil-water ratio in the emulsion 2 is 1:1, and the mass fraction of component 1 + component 2 is 10%) is configured;

[0286] (5) The emulsion 1, the emulsion 2, the antistatic agent, the lubricant and the deionized water are configured into a one-step emulsion sizing agent in a mass ratio of 5:0.5:0.1:0.2:the rest (a total of 100);

[0287] (6) The carbon fibers are treated with the one-step emulsion sizing agent prepared in step (4) and then treated with ultraviolet light, and finally dried at 130°C and wound up;

[0288] (7) The IFSS of carbon fiber after sizing with PDCPD is 23 MPa, and the IFSS of commercial sized CF with PDCDP is 12 MPa.

[0289] Obviously, the above embodiments are merely exemplary and not intended to limit the embodiments. Based on the above description, one of ordinary skill in the art can make other different forms of changes or modifications. Here, it is not necessary and impossible to enumerate all the embodiments. The obvious changes or modifications derived therefrom are still within the protection scope of the present application.

Claims

1. An organic electrolyte, characterized by comprising: The structural formula is as follows: R is -H or -PH; n is an arbitrary integer between 1 and 5; and excluding R is H, n is 2, attached to organic electrolyte of ortho structure.

2. The method of claim 1, wherein the organic electrolyte is prepared by adding the electrolyte solvent to the electrolyte salt, and then adding the electrolyte additive. The organic electrolyte is obtained by reacting an olefin derivative of aniline, nitrous salt of tetrafluoroboric acid, anti-crosslinking agent, and acetonitrile or toluene, and the synthesis reaction formula is as follows:

3. A method for surface treatment of carbon fibers, characterized by, The method comprises the following steps: The carbon fiber surface treatment method is divided into two stages; Stage ①: carbon fiber surface olefin enrichment After carbonization, the carbon fiber is subjected to surface electrochemical treatment; The electrochemical treatment process is as follows: the carbon fiber is a cathode, and the electrolyte required for electrochemical reduction comprises an organic electrolyte and a supporting electrolyte; The organic electrolyte is obtained by reacting an olefin derivative of aniline, nitrous salt of tetrafluoroboric acid, anti-crosslinking agent, and acetonitrile or toluene, and the synthesis reaction formula is as follows: wherein R is -H or -PH; n is any integer between 1 and 5; and excluding R is H, n is 2, attached to organic electrolytes of vicinal structure; Stage ②: carbon fiber sizing The carbon fiber subjected to electrochemical treatment is subjected to sizing treatment; The sizing agent required for carbon fiber sizing treatment comprises a coupling agent and a film-forming agent, and the coupling agent is referred to as component 1 and the film-forming agent is referred to as component 2; The sizing agent is synthesized by a two-step method from dicyclopentadiene and a sulfide compound, and after filtration, the reaction system is directly used to configure a solution type or emulsion type sizing agent; the sizing agent is synthesized by a two-step reaction, and the synthesis reaction formula is as follows: The structural formula of the dicyclopentadiene is as follows: The structural formula of the sulfide compound is as follows: Three R1 groups are the same or different, are one of the following structures, and at least one of the three R1 groups is not a hydrogen atom; n1 is an arbitrary integer between 0 and 5; -H、 The component 1 is a mixture of the following substances: Three R2 groups are the same or different, are one of the following structures, and at least one of the three R2 groups is not a hydrogen atom; n2 is an arbitrary integer between 0 and 5; -H、 The component 2 is a mixture of the following substances; The sizing agent further comprises a coupling catalyst, which is referred to as component 3.

4. The carbon fiber surface treatment method according to claim 3, characterized by, The electrolyte preparation method required for electrochemical reduction is as follows: the anti-crosslinking agent is dissolved in acetonitrile or toluene, then the olefin derivative of aniline is completely dissolved in the anti-crosslinking agent acetonitrile or toluene solution, then the saturated nitrous salt of tetrafluoroboric acid solution is dropped into the above solution, the reaction is carried out for 15 min, and finally the supporting electrolyte is dissolved in the reaction system to obtain the electrolyte required for electrochemical reduction; In the electrolyte required for electrochemical reduction: the molar concentration of the organic electrolyte is 1-10 mM; The molar concentration of the supporting electrolyte is 1-3 mM; the molar concentration of the anti-crosslinking agent is 0.01-0.1 mM; The supporting electrolyte is tetrabutylammonium tetrafluoroborate; The anti-crosslinking agent is phenol, o-dihydroxybenzene, 2,4-dinitrophenol, 2,6-dinitro-p-cresol, or 2,6-di-tert-butyl-4-benzylidene cyclohex-2,5-dienone; The potential difference of the electrochemical reaction is 0.5 V; The molar ratio of component 1 to component 2 in the sizing agent component is 1:0.8-1:

5.

5. The carbon fiber surface treatment method according to claim 3, characterized by, In the first step of obtaining the sizing agent: The molar ratio of the reactants dicyclopentadiene and sulfide compound is 2:1-5:1; The solvent is toluene, and the concentration of dicyclopentadiene is 0.1-2.0 mol / L; The catalyst 1 is aluminum chloride, aluminum bromide, trifluoroacetic acid, or methanesulfonic acid; The reaction temperature is 60-200℃, and the synthesis reaction time is 2-7 h.

6. The carbon fiber surface treatment method according to claim 3, characterized by, The second step reaction for obtaining the sizing agent is as follows: The catalyst 2 is Raney Ni; The reaction temperature is 40-60℃; The reaction time is 10-15h; The reaction system pressure is 0.1-0.2MPa.

7. The carbon fiber surface treatment method according to any one of claims 3 to 6, characterized by, When the component 3 is high-temperature or light-induced, the one-step or two-step sizing method is used for the carbon fiber surface treatment, or the emulsion sizing or solution sizing method is used; when the component 3 is room-temperature induced, the two-step emulsion sizing method is used for the carbon fiber surface treatment.

8. The carbon fiber surface treatment method according to claim 7, characterized by, The component 3 is dibenzoyl peroxide and dimethyl aniline, or azobis isobutyronitrile, or dibenzoyl peroxide, or benzpinacol, or benzophenone and azobis isobutyronitrile.

9. The carbon fiber surface treatment method according to claim 7, characterized by, When the component 3 is azobis isobutyronitrile, dibenzoyl peroxide, benzpinacol, or benzophenone and azobis isobutyronitrile, the one-step emulsion sizing or one-step solution sizing method is used for the carbon fiber surface treatment; The one-step emulsion sizing method for the carbon fiber surface treatment specifically includes the following steps: a. The mixture of the component 1 and the component 2 is configured into an emulsion, which is recorded as emulsion 1; b. The component 3 is configured into an emulsion, which is recorded as emulsion 2; c. The emulsion 1, the emulsion 2, the antistatic agent, the lubricant, and deionized water are configured into an emulsion-type sizing agent in a mass ratio of 5-20:0.5-10:0.1-0.5:0.2-0.8:balance, the balance being the mass of deionized water, the total mass being 100 mass parts; d. When the component 3 is azobis isobutyronitrile or dibenzoyl peroxide, the carbon fiber is dried at 100-150℃ after sizing and then wound; when the component 3 is benzpinacol or benzophenone and azobis isobutyronitrile, the carbon fiber is first sized, then treated by ultraviolet light, and then dried at 100-150℃ after sizing and then wound. The one-step solution sizing method for the carbon fiber surface treatment specifically includes the following steps: a. The mixed solution of the component 1 and the component 2, the component 3, the antistatic agent, the lubricant, and the organic solvent are configured into a solution-type sizing agent in a mass ratio of 1-2:0.01-0.1:0.1-0.5:0.2-0.8:balance, the balance being the mass of the organic solvent, the total mass being 100 mass parts; 10. The carbon fiber surface treatment method according to claim 7, characterized by, b. When the component 3 is azobis isobutyronitrile or dibenzoyl peroxide, the carbon fiber is dried at 120-150℃ after sizing and then wound; when the component 3 is benzpinacol or benzophenone and azobis isobutyronitrile, the carbon fiber is first sized, then treated by ultraviolet light, and then dried at 120-150℃ after sizing and then wound. When the component 3 is dibenzoyl peroxide and dimethyl aniline, or azobis isobutyronitrile, or dibenzoyl peroxide, or benzpinacol, or benzophenone and azobis isobutyronitrile, the two-step emulsion sizing method is used for the carbon fiber surface treatment; The two-step emulsion sizing method for the carbon fiber surface treatment specifically includes the following steps: a. The mixture of the component 1 and the component 2 is configured into an emulsion, which is recorded as emulsion 1; b. The component 3 is configured into an emulsion, which is recorded as emulsion 2; c. The emulsion 1, antistatic agent, lubricant and deionized water are configured in a mass ratio of 5-20:0.1-0.5:0.2-0.8:balance, the balance being the mass of deionized water, the total of the mass parts being 100, to form an emulsion type sizing agent; d. The carbon fibers are first sized with the emulsion 2, dried until no liquid drops are dropped, sized with the emulsion obtained in step c, and wound after drying at 100-150°C when the component 3 is dibenzoyl peroxide and dimethylphenylamine, azobis isobutyronitrile or dibenzoyl peroxide; when the component 3 is benzo pinacol or benzophenone and azobis isobutyronitrile, the carbon fibers are first sized, treated with ultraviolet light, and then wound after drying at 100-150°C.

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