CN104120605B

CN104120605B - Emulsion pasting agent of a kind of carbon nano-tube modification and its preparation method and application

Info

Publication number: CN104120605B
Application number: CN201410338906.4A
Authority: CN
Inventors: 王荣国; 刘文博; 王杰; 杨帆; 矫维成; 徐忠海
Original assignee: Harbin Institute of Technology
Current assignee: Harbin Institute of Technology
Priority date: 2014-07-16
Filing date: 2014-07-16
Publication date: 2016-02-10
Anticipated expiration: 2034-07-16
Also published as: CN104120605A

Abstract

Emulsion pasting agent of a kind of carbon nano-tube modification and its preparation method and application, it relates to a kind of emulsion pasting agent and its preparation method and application.The object of the invention is to solve existing sizing agent expensive, to environment, after utilizing its Treatment of Carbon, the problem that composite material interface shear strength is not high.A kind of emulsion pasting agent of carbon nano-tube modification is prepared from by 0.001 part ~ 2 parts modified carbon nano-tubes, 50 parts ~ 55 parts epoxy resin latex systems, 0.001 part ~ 1 part surfactant and 45 parts ~ 50 parts deionized waters by weight.Preparation method: one, the preparation of epoxy resin latex system; Two, mix; Obtain the emulsion pasting agent of carbon nano-tube modification.Application process: by the solution tank of carbon fiber by the emulsion pasting agent containing carbon nano-tube modification, then frictioning process, then carry out cleaning and drying, obtain the carbon fiber that sizing agent is modified.The present invention can obtain a kind of emulsion pasting agent of carbon nano-tube modification.

Description

Emulsion pasting agent of a kind of carbon nano-tube modification and its preparation method and application

Technical field

The present invention relates to a kind of emulsion pasting agent and its preparation method and application.

Background technology

The series of advantages such as carbon fiber has that proportion is little, high strength, high-modulus, high temperature resistant, antifatigue, are widely used in the fields such as Aero-Space, civil construction, electronic product, Leisure Sport articles for use.But carbon fiber is highly brittle, in production and process, be easy under the effect of friction produce lousiness and single wire fracture, in being reduction of the intensity of carbon fiber.Meanwhile, lousiness hinders the abundant wetting fibre of resin, makes easily to produce hole in composite preparation process, thus reduces the mechanical property of composite.But utilize sizing agent starching carbon fiber, form layer protecting film, not only can reduce the wearing and tearing in process, avoid the formation of lousiness, the clean active surface after surface treatment can also be protected, prevent the absorption of dust in air and moisture.In addition, sizing agent can also increase the wettability of fiber and resin, and then improves the interface performance of composite.Sizing agent, as the interface transition layer of composite, effectively can make load be delivered on fiber by interface, inhibit crackle to produce in interface, and fiber and resin active force are strengthened.Therefore, starching process must be carried out to carbon fiber.

Carbon fiber sizing agent can be divided three classes: organic solvent type, water-soluble and water-based emulsion type sizing agent.In sizing agent, main slurry is resin, and the resin types preparing sizing agent is various, mainly contains vinyl alcohol, polyacrylic acid, epoxy resin, polyurethane resin, Effect of Organosilicon-modified Phenol-formaldehyde Resin, polyimides, polyimides etc.Organic solvent type sizing agent needs to consume a large amount of organic solvents, and price is higher and easy in environment.And water-based emulsion type sizing agent is a kind of water-base emulsion of " oil-in-water " structure, domain size distribution is all high with, stability.Meanwhile, the surfactant in emulsion method and auxiliary agent can improve the wettability of resin and fiber.

Summary of the invention

The object of the invention is to solve existing sizing agent expensive, to environment, after utilizing its Treatment of Carbon, the problem that composite material interface shear strength is not high, and emulsion pasting agent of a kind of carbon nano-tube modification and its preparation method and application is provided.

A kind of emulsion pasting agent of carbon nano-tube modification is prepared from by 0.001 part ~ 2 parts modified carbon nano-tubes, 50 parts ~ 55 parts epoxy resin latex systems, 0.001 part ~ 1 part surfactant and 45 parts ~ 50 parts deionized waters by weight.

A preparation method for the emulsion pasting agent of carbon nano-tube modification, specifically completes according to the following steps:

One, the preparation of epoxy resin latex system: low whipping speed is 1000rpm ~ 12000rpm and temperature is at 65 DEG C ~ 85 DEG C, epoxy resin is mixed with epoxy emulsifier for mixing and drips deionized water, decline to system viscosity, low whipping speed is under 1000rpm ~ 12000rpm, continue to stir 10min ~ 100min, then low whipping speed is under 300rpm ~ 3000rpm, add deionized water again, be 0.5% ~ 4% to system solid content, obtain epoxy emulsion, epoxy hardener is added again in epoxy emulsion, low whipping speed is under 300rpm ~ 3000rpm, stir 10min ~ 60min, obtain epoxy resin latex system,

The mass ratio of described epoxy resin and epoxy emulsifying agent is 1:(0.05 ~ 0.2); Described epoxy resin and the mass ratio of epoxy hardener are 1000:(1 ~ 10);

Described epoxy resin is 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl ester, bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-44, bisphenol A type epoxy resin E-42, bisphenol A type epoxy resin E-35, bisphenol A type epoxy resin E-20, bisphenol f type epoxy resin or novolac epoxy resin;

Described epoxy emulsifying agent is polyoxyethylene many rings phenyl ether sulfate 714-SF, polyoxyethylene many rings phenyl ether sulfate 707-SF, polyoxyethylene many rings phenyl ether sulfate 2607-SF, polyoxyethylene cumylphenyl ether CMP-6, polyoxyethylene cumylphenyl ether CMP-8, polyoxyethylene cumylphenyl ether CMP-11, Span60, Arlacel-65, Tween-85, Tween-20, sodium taurocholate, Carbon nano-tube dispersant TNWDIS, neopelex, lauryl sodium sulfate, TritonX-100, TritonX-102, TritonX-305, ethylene nonyl phenylate, polyethylene glycol cetyl ether, cetyl trimethyl ammonium tosylate, softex kw, polyoxyethylene ammonium salt, quaternary ammonium salt, imidazoline, a kind of or wherein several mixture in castor oil polyoxyethylene ether and Aethoxy Sklerol,

Described epoxy hardener is a kind of or wherein several mixture in Amino End Group polypropylene glycol D230, Amino End Group polypropylene glycol D400, aliphatic diamine, aromatic diamines, diethylenetriamine, triethylene tetramine and AB-HGF;

Two, mix: under be 600W ~ 800W and frequency being 40kHz ~ 120kHz at power, by weight 0.001 part ~ 2 parts modified carbon nano-tubes and 0.001 part ~ 1 part surfactant are joined in 45 parts ~ 50 parts deionized waters, ultrasonication 0.1h ~ 1h, obtain dispersion liquid, then under be 200W ~ 400W and frequency being 10kHz ~ 30kHz at power, dispersion liquid is mixed and ultrasonic 0.1h ~ 2h with 50 parts ~ 55 parts epoxy resin latex systems, namely obtains the emulsion pasting agent of carbon nano-tube modification;

Modified carbon nano-tube described in step 2 is carboxylic carbon nano-tube, amination CNT or hydroxylating CNT;

Wherein, the preparation method of described carboxylic carbon nano-tube completes according to the following steps:

CNT is impregnated in Strong oxdiative solution, be 400W ~ 800W at power, frequency is process 0.2h ~ 2h in the Ultrasound Instrument of 20kHz ~ 120kHz, then be react 3h ~ 12h in the water-bath of 40 DEG C ~ 95 DEG C in temperature, add deionized water dilution again, be cooled to room temperature suction filtration, obtain filter residue, filter residue spend deionized water and suction filtration until the PH of cleaning solution is 7, finally the filter residue after washing is put into the dry 2h ~ 12h of vacuum drying oven that temperature is 80 DEG C ~ 140 DEG C, namely obtain carboxylic carbon nano-tube; Described Strong oxdiative solution to be mass fraction be 68% ~ 75% red fuming nitric acid (RFNA), mass fraction be 30% ~ 40% hydrogen peroxide, Strong oxdiative solution A or Strong oxdiative solution B; Wherein said Strong oxdiative solution A to be mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the mixed solution of the red fuming nitric acid (RFNA) of 68% ~ 75%, and in Strong oxdiative solution A mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the volume ratio of the red fuming nitric acid (RFNA) of 68% ~ 75% be 1:(0.2 ~ 1); Described Strong oxdiative solution B to be mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the mixed solution of the hydrogen peroxide of 30% ~ 40%, and in Strong oxdiative solution B mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the volume ratio of the hydrogen peroxide of 30% ~ 40% be 1:(1 ~ 10); The quality of described CNT and the volume ratio of Strong oxdiative solution are 1g:(100mL ~ 1000mL); Described CNT is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes; Described carbon nanotube diameter is 0.8nm ~ 100nm, and length is 0.5um ~ 50um;

The preparation method of described amination CNT completes according to the following steps:

1., the preparation of carboxylic carbon nano-tube: CNT is impregnated in Strong oxdiative solution, be 400W ~ 800W at power, frequency is process 0.2h ~ 2h in the Ultrasound Instrument of 20kHz ~ 120kHz, then be react 3h ~ 12h in the water-bath of 40 DEG C ~ 95 DEG C in temperature, add deionized water dilution again, be cooled to room temperature suction filtration, obtain filter residue, filter residue spend deionized water and suction filtration until the PH of cleaning solution is 7, finally the filter residue after washing is put into the dry 2h ~ 12h of vacuum drying oven that temperature is 80 DEG C ~ 140 DEG C, namely obtain carboxylic carbon nano-tube;

Step 1. described in Strong oxdiative solution to be mass fraction be 68% ~ 75% red fuming nitric acid (RFNA), mass fraction be 30% ~ 40% hydrogen peroxide, Strong oxdiative solution A or Strong oxdiative solution B; Wherein said Strong oxdiative solution A to be mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the mixed solution of the red fuming nitric acid (RFNA) of 68% ~ 75%, and in Strong oxdiative solution A mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the volume ratio of the red fuming nitric acid (RFNA) of 68% ~ 75% be 1:(0.2 ~ 1); Described Strong oxdiative solution B to be mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the mixed solution of the hydrogen peroxide of 30% ~ 40%, and in Strong oxdiative solution B mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the volume ratio of the hydrogen peroxide of 30% ~ 40% be 1:(1 ~ 10);

Step 1. described in the quality of CNT and the volume ratio of Strong oxdiative solution be 1g:(100mL ~ 1000mL);

Step 1. described in CNT be Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes; Described carbon nanotube diameter is 0.8nm ~ 100nm, and length is 0.5um ~ 50um;

2., the preparation of amination CNT: carboxylic carbon nano-tube step 1. obtained grinds to form carboxylic carbon nano-tube powder, then carboxylic carbon nano-tube powder and catalyst are joined in organic solvent, be 400W ~ 800W at power, frequency is broken ultrasonic 0.2h ~ 2h under the condition of 20kHz ~ 120kHz, then in reaction system, amine is added, after stirring 0.1h ~ 1h, be 200W ~ 400W at power, frequency is 10kHz ~ 30kHz, temperature is react 3h ~ 12h in the Ultrasound Instrument of 20 DEG C ~ 60 DEG C, with the centrifugal 10min ~ 60min of the centrifugal speed of 3000r/min ~ 15000r/min after reaction terminates, be precipitated thing, sediment organic solvent A is dissolved, be cooled to room temperature suction filtration, obtain filter residue, by filter residue with organic solvent A washing and suction filtration 3 ~ 5 times, be be placed in the dry 2h ~ 12h of vacuum drying oven under the condition of 80 DEG C ~ 140 DEG C again in temperature by the filter residue after washing, obtain amination CNT,

Step 2. described in catalyst be 2-(7-azo BTA)-N, N, N', the mixture of N'-tetramethylurea hexafluorophosphoric acid ester and DIPEA, wherein 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester is 1:(1 ~ 10 with the ratio of the amount of substance of DIPEA);

Step 2. described in organic solvent be methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, carrene, chloroform, 1,2-dichloroethanes, acetone, methyl ethyl ketone, cyclohexanone, methyl iso-butyl ketone (MIBK), normal heptane, n-hexane, cyclohexane, benzene,toluene,xylene, ethylo benzene, oxolane, diethyl ether, 1,2-dimethoxy-ethane, N, a kind of or wherein several mixture in dinethylformamide, DMA, METHYLPYRROLIDONE and hexamethyl phosphoramide;

Step 2. described in organic solvent A be methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, carrene, chloroform, 1,2-dichloroethanes, acetone, methyl ethyl ketone, cyclohexanone, methyl iso-butyl ketone (MIBK), normal heptane, n-hexane, cyclohexane, benzene,toluene,xylene, ethylo benzene, oxolane, diethyl ether, 1,2-dimethoxy-ethane, N, a kind of or wherein several mixture in dinethylformamide, DMA, METHYLPYRROLIDONE and hexamethyl phosphoramide;

Step 2. described in amine be a kind of or wherein several mixture in aliphatic diamine, aromatic diamines, diethylenetriamine, triethylene tetramine, polymine, polyamidoamine dendrimer;

Step 2. described in carboxylic carbon nano-tube powder and the mass ratio of catalyst be 1:(0.1 ~ 0.5);

Step 2. described in the quality of carboxylic carbon nano-tube powder be 1g:(50mL ~ 1000mL with the ratio of the volume of organic solvent);

Step 2. described in carboxylic carbon nano-tube powder and the mass ratio of amine be 1:(100 ~ 1000);

The preparation method of described hydroxylating CNT specifically completes according to the following steps:

(1), the preparation of carboxylic carbon nano-tube: CNT is impregnated in Strong oxdiative solution, be 400W ~ 800W at power, frequency is process 0.2h ~ 2h in the Ultrasound Instrument of 20kHz ~ 120kHz, then be react 3h ~ 12h in the water-bath of 40 DEG C ~ 95 DEG C in temperature, add deionized water dilution again, be cooled to room temperature suction filtration, obtain filter residue, filter residue spend deionized water and suction filtration until the PH of cleaning solution is 7, finally the filter residue after washing is put into the dry 2h ~ 12h of vacuum drying oven that temperature is 80 DEG C ~ 140 DEG C, namely obtain carboxylic carbon nano-tube;

Strong oxdiative solution described in step (1) to be mass fraction be 68% ~ 75% red fuming nitric acid (RFNA), mass fraction be 30% ~ 40% hydrogen peroxide, Strong oxdiative solution A or Strong oxdiative solution B; Wherein said Strong oxdiative solution A to be mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the mixed solution of the red fuming nitric acid (RFNA) of 68% ~ 75%, and in Strong oxdiative solution A mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the volume ratio of the red fuming nitric acid (RFNA) of 68% ~ 75% be 1:(0.2 ~ 1); Described Strong oxdiative solution B to be mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the mixed solution of the hydrogen peroxide of 30% ~ 40%, and in Strong oxdiative solution B mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the volume ratio of the hydrogen peroxide of 30% ~ 40% be 1:(1 ~ 10);

The quality of the CNT described in step (1) and the volume ratio of Strong oxdiative solution are 1g:(100mL ~ 1000mL);

CNT described in step (1) is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes; Described carbon nanotube diameter is 0.8nm ~ 100nm, and length is 0.5um ~ 50um;

(2), the preparation of hydroxylating CNT: 1., join in organic solvent by carboxylic carbon nano-tube and catalyst, under be 400W ~ 800W and frequency being 20kHz ~ 120kHz at power, broken ultrasonic 0.2h ~ 2h, obtains CNT mixed liquor;

Described carboxylic carbon nano-tube and the mass ratio of catalyst are 1:(0.1 ~ 0.5); Described carboxylic carbon nano-tube and the mass ratio of organic solvent are 1:(10 ~ 100); Described catalyst is 2-(7-azo BTA)-N, N, N', the mixture of N'-tetramethylurea hexafluorophosphoric acid ester and DIPEA, described 2-(7-azo BTA)-N, N, the mass ratio of N', N'-tetramethylurea hexafluorophosphoric acid ester and DIPEA is 1:(1 ~ 10); Described organic solvent is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, carrene, chloroform, 1,2-dichloroethanes, acetone, methyl ethyl ketone, cyclohexanone, methyl iso-butyl ketone (MIBK), normal heptane, n-hexane, cyclohexane, benzene,toluene,xylene, ethylo benzene, oxolane, diethyl ether, 1,2-dimethoxy-ethane, N, a kind of or wherein several mixture in dinethylformamide, DMA, METHYLPYRROLIDONE and hexamethyl phosphoramide;

2., by 3-aminopropyl triethoxysilane join in the mixed liquid of second alcohol and water and be hydrolyzed 1h ~ 48h, obtain 3-aminopropyl triethoxysilane hydrolyzate; Described 3-aminopropyl triethoxysilane and the mass ratio of ethanol are 1:(1 ~ 10); The mass ratio of described second alcohol and water is 1:(0.1 ~ 1);

3., CNT mixed liquor is mixed with 3-aminopropyl triethoxysilane hydrolyzate, temperature be 20 DEG C ~ 60 DEG C, power be 200W ~ 400W and frequency is react 3h ~ 12h in the Ultrasound Instrument of 10kHz ~ 30kHz, again reacted solution is carried out centrifugal, and with methyl alcohol, suction filtration is washed 3 times ~ 8 times to sediment, then the sediment after washing is put into the dry 2h ~ 12h of vacuum drying oven that temperature is 80 DEG C ~ 140 DEG C, obtain hydroxylating CNT; The mass ratio of described CNT mixed liquor and 3-aminopropyl triethoxysilane hydrolyzate is 1:(0.1 ~ 1).

Advantage of the present invention:

One, the present invention is by carrying out carboxylated, amination or hydroxylating process to CNT, make carbon nano tube surface with active function groups, add surfactant again, in conjunction with under ultrasonic condition, CNT dispersiveness in deionized water can be improved significantly;

Two, the present invention has synthesized a kind of aqueous epoxy resin emulsion system, and this system particle diameter is 300nm ~ 600nm, highly stable;

Three, the CNT of modification is prepared into the aqueous solution, and it is blended with epoxy emulsion system, thus synthesized the emulsion pasting agent of carbon nano-tube modification, the particle diameter of this sizing agent is less, particle diameter is 400nm ~ 700nm, the emulsion pasting agent starching carbon fiber of the carbon nano-tube modification utilizing the present invention to prepare, the monofilament loops epoxy resin composite material of preparation, compared with unsized carbon fibre composite, its interface shear strength improves 23.60 ~ 91.45%.

The present invention can obtain a kind of emulsion pasting agent of carbon nano-tube modification.

Detailed description of the invention

Detailed description of the invention one: present embodiment is that a kind of emulsion pasting agent of carbon nano-tube modification is prepared from by 0.001 part ~ 2 parts modified carbon nano-tubes, 50 parts ~ 55 parts epoxy resin latex systems, 0.001 part ~ 1 part surfactant and 45 parts ~ 50 parts deionized waters by weight.

The advantage of present embodiment:

One, present embodiment is by carrying out carboxylated, amination or hydroxylating process to CNT, make carbon nano tube surface with active function groups, add surfactant again, in conjunction with under ultrasonic condition, CNT dispersiveness in deionized water can be improved significantly;

Two, present embodiment has synthesized a kind of aqueous epoxy resin emulsion system, and this system particle diameter is 300nm ~ 600nm, highly stable;

Three, the CNT of modification is prepared into the aqueous solution, and it is blended with epoxy emulsion system, thus synthesized the emulsion pasting agent of carbon nano-tube modification, the particle diameter of this sizing agent is less, particle diameter is 400nm ~ 700nm, the emulsion pasting agent starching carbon fiber of the carbon nano-tube modification utilizing present embodiment to prepare, the monofilament loops epoxy resin composite material of preparation, compared with unsized carbon fibre composite, its interface shear strength improves 23.60 ~ 91.45%.

Present embodiment can obtain a kind of emulsion pasting agent of carbon nano-tube modification.

Detailed description of the invention two: present embodiment and detailed description of the invention one difference are: modified carbon nano-tube is carboxylic carbon nano-tube, amination CNT or hydroxylating CNT.Other are identical with detailed description of the invention one.

Detailed description of the invention three: present embodiment and detailed description of the invention two difference are: the preparation method of carboxylic carbon nano-tube completes according to the following steps: be impregnated into by CNT in Strong oxdiative solution, be 400W ~ 800W at power, frequency is process 0.2h ~ 2h in the Ultrasound Instrument of 20kHz ~ 120kHz, then be react 3h ~ 12h in the water-bath of 40 DEG C ~ 95 DEG C in temperature, add deionized water dilution again, be cooled to room temperature suction filtration, obtain filter residue, filter residue spend deionized water and suction filtration until the PH of cleaning solution is 7, finally the filter residue after washing is put into the dry 2h ~ 12h of vacuum drying oven that temperature is 80 DEG C ~ 140 DEG C, namely carboxylic carbon nano-tube is obtained,

Described Strong oxdiative solution to be mass fraction be 68% ~ 75% red fuming nitric acid (RFNA), mass fraction be 30% ~ 40% hydrogen peroxide, Strong oxdiative solution A or Strong oxdiative solution B; Wherein said Strong oxdiative solution A to be mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the mixed solution of the red fuming nitric acid (RFNA) of 68% ~ 75%, and in Strong oxdiative solution A mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the volume ratio of the red fuming nitric acid (RFNA) of 68% ~ 75% be 1:(0.2 ~ 1); Described Strong oxdiative solution B to be mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the mixed solution of the hydrogen peroxide of 30% ~ 40%, and in Strong oxdiative solution B mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the volume ratio of the hydrogen peroxide of 30% ~ 40% be 1:(1 ~ 10);

The quality of described CNT and the volume ratio of Strong oxdiative solution are 1g:(100mL ~ 1000mL);

Described CNT is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes; Described carbon nanotube diameter is 0.8nm ~ 100nm, and length is 0.5um ~ 50um.Other are identical with detailed description of the invention two.

Detailed description of the invention four: present embodiment and detailed description of the invention two or three difference are: the preparation method of amination CNT completes according to the following steps:

One, the preparation of carboxylic carbon nano-tube: CNT is impregnated in Strong oxdiative solution, be 400W ~ 800W at power, frequency is process 0.2h ~ 2h in the Ultrasound Instrument of 20kHz ~ 120kHz, then be react 3h ~ 12h in the water-bath of 40 DEG C ~ 95 DEG C in temperature, add deionized water dilution again, be cooled to room temperature suction filtration, obtain filter residue, filter residue spend deionized water and suction filtration until the PH of cleaning solution is 7, finally the filter residue after washing is put into the dry 2h ~ 12h of vacuum drying oven that temperature is 80 DEG C ~ 140 DEG C, namely obtain carboxylic carbon nano-tube;

Strong oxdiative solution described in step one to be mass fraction be 68% ~ 75% red fuming nitric acid (RFNA), mass fraction be 30% ~ 40% hydrogen peroxide, Strong oxdiative solution A or Strong oxdiative solution B; Wherein said Strong oxdiative solution A to be mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the mixed solution of the red fuming nitric acid (RFNA) of 68% ~ 75%, and in Strong oxdiative solution A mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the volume ratio of the red fuming nitric acid (RFNA) of 68% ~ 75% be 1:(0.2 ~ 1); Described Strong oxdiative solution B to be mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the mixed solution of the hydrogen peroxide of 30% ~ 40%, and in Strong oxdiative solution B mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the volume ratio of the hydrogen peroxide of 30% ~ 40% be 1:(1 ~ 10);

The quality of CNT described in step one and the volume ratio of Strong oxdiative solution are 1g:(100mL ~ 1000mL);

CNT described in step one is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes; Described carbon nanotube diameter is 0.8nm ~ 100nm, and length is 0.5um ~ 50um;

Two, the preparation of amination CNT: carboxylic carbon nano-tube step one obtained grinds to form carboxylic carbon nano-tube powder, then carboxylic carbon nano-tube powder and catalyst are joined in organic solvent, be 400W ~ 800W at power, frequency is broken ultrasonic 0.2h ~ 2h under the condition of 20kHz ~ 120kHz, then in reaction system, amine is added, after stirring 0.1h ~ 1h, be 200W ~ 400W at power, frequency is 10kHz ~ 30kHz, temperature is react 3h ~ 12h in the Ultrasound Instrument of 20 DEG C ~ 60 DEG C, with the centrifugal 10min ~ 60min of the centrifugal speed of 3000r/min ~ 15000r/min after reaction terminates, be precipitated thing, sediment organic solvent A is dissolved, be cooled to room temperature suction filtration, obtain filter residue, by filter residue with organic solvent A washing and suction filtration 3 ~ 5 times, be be placed in the dry 2h ~ 12h of vacuum drying oven under the condition of 80 DEG C ~ 140 DEG C again in temperature by the filter residue after washing, obtain amination CNT,

Catalyst described in step 2 is 2-(7-azo BTA)-N, N, N', the mixture of N'-tetramethylurea hexafluorophosphoric acid ester and DIPEA, wherein 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester is 1:(1 ~ 10 with the ratio of the amount of substance of DIPEA);

Organic solvent described in step 2 is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, carrene, chloroform, 1,2-dichloroethanes, acetone, methyl ethyl ketone, cyclohexanone, methyl iso-butyl ketone (MIBK), normal heptane, n-hexane, cyclohexane, benzene,toluene,xylene, ethylo benzene, oxolane, diethyl ether, 1,2-dimethoxy-ethane, N, a kind of or wherein several mixture in dinethylformamide, DMA, METHYLPYRROLIDONE and hexamethyl phosphoramide;

Organic solvent A described in step 2 is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, carrene, chloroform, 1,2-dichloroethanes, acetone, methyl ethyl ketone, cyclohexanone, methyl iso-butyl ketone (MIBK), normal heptane, n-hexane, cyclohexane, benzene,toluene,xylene, ethylo benzene, oxolane, diethyl ether, 1,2-dimethoxy-ethane, N, a kind of or wherein several mixture in dinethylformamide, DMA, METHYLPYRROLIDONE and hexamethyl phosphoramide;

Amine described in step 2 is a kind of or wherein several mixture in aliphatic diamine, aromatic diamines, diethylenetriamine, triethylene tetramine, polymine and polyamidoamine dendrimer;

The mass ratio of the carboxylic carbon nano-tube powder described in step 2 and catalyst is 1:(0.1 ~ 0.5);

The quality of carboxylic carbon nano-tube powder described in step 2 is 1g:(50mL ~ 1000mL with the ratio of the volume of organic solvent);

The mass ratio of the carboxylic carbon nano-tube powder described in step 2 and amine is 1:(100 ~ 1000).Other are identical with detailed description of the invention two or three.

Detailed description of the invention five: present embodiment and detailed description of the invention two to four difference are: the preparation method of hydroxylating CNT specifically completes according to the following steps:

Strong oxdiative solution described in step one to be mass fraction be 68% ~ 75% red fuming nitric acid (RFNA), mass fraction be 30% ~ 40% hydrogen peroxide, Strong oxdiative solution A or Strong oxdiative solution B; Wherein said Strong oxdiative solution A to be mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the mixed solution of the red fuming nitric acid (RFNA) of 68% ~ 75%; In Strong oxdiative solution A mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the volume ratio of the red fuming nitric acid (RFNA) of 68% ~ 75% be 1:(0.2 ~ 1); Described Strong oxdiative solution B to be mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the mixed solution of the hydrogen peroxide of 30% ~ 40%; In Strong oxdiative solution B mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the volume ratio of the hydrogen peroxide of 30% ~ 40% be 1:(1 ~ 10);

Two, the preparation of hydroxylating CNT: 1., carboxylic carbon nano-tube and catalyst are joined in organic solvent, under be 400W ~ 800W and frequency being 20kHz ~ 120kHz at power, broken ultrasonic 0.2h ~ 2h, obtains CNT mixed liquor;

3., CNT mixed liquor is mixed with 3-aminopropyl triethoxysilane hydrolyzate, temperature be 20 DEG C ~ 60 DEG C, power be 200W ~ 400W and frequency is react 3h ~ 12h in the Ultrasound Instrument of 10kHz ~ 30kHz, again reacted solution is carried out centrifugal, and with methyl alcohol, suction filtration is washed 3 times ~ 8 times to sediment, then the sediment after washing is put into the dry 2h ~ 12h of vacuum drying oven that temperature is 80 DEG C ~ 140 DEG C, obtain hydroxylating CNT; The mass ratio of described CNT mixed liquor and 3-aminopropyl triethoxysilane hydrolyzate is 1:(0.1 ~ 1).Other are identical with detailed description of the invention two to four.

Detailed description of the invention six: present embodiment and detailed description of the invention one difference are: described epoxy resin latex system is prepared according to the following steps: low whipping speed is 1000rpm ~ 12000rpm and temperature is at 65 DEG C ~ 85 DEG C, epoxy resin is mixed with epoxy emulsifier for mixing and drips deionized water, decline to system viscosity, low whipping speed is under 1000rpm ~ 12000rpm, continue to stir 10min ~ 100min, then low whipping speed is under 300rpm ~ 3000rpm, add deionized water again, be 0.5% ~ 4% to system solid content, obtain epoxy emulsion, epoxy hardener is added again in epoxy emulsion, low whipping speed is under 300rpm ~ 3000rpm, stir 10min ~ 60min, obtain epoxy resin latex system,

Described epoxy hardener is a kind of or wherein several mixture in Amino End Group polypropylene glycol D230, Amino End Group polypropylene glycol D400, aliphatic diamine, aromatic diamines, diethylenetriamine, triethylene tetramine and AB-HGF.Other steps are identical with detailed description of the invention one.

Polyoxyethylene many rings phenyl ether sulfate 714-SF described in present embodiment, polyoxyethylene many rings phenyl ether sulfate 707-SF, polyoxyethylene many rings phenyl ether sulfate 2607-SF, polyoxyethylene cumylphenyl ether CMP-6, polyoxyethylene cumylphenyl ether CMP-8, polyoxyethylene cumylphenyl ether CMP-11 are that Japanese emulsifying agent Co., Ltd. produces;

Carbon nano-tube dispersant TNWDIS described in present embodiment is produced by Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences;

TritonX-100, TritonX-102TritonX-305 described in present embodiment are all produced by Jiangsu Hai'an Petrochemical Plant;

AB-HGF described in present embodiment is produced by Zhejiang Anbang New Material Development Co., Ltd..

Detailed description of the invention seven: present embodiment and detailed description of the invention one difference are: described surfactant is polyoxyethylene many rings phenyl ether sulfate 714-SF, polyoxyethylene many rings phenyl ether sulfate 707-SF, polyoxyethylene many rings phenyl ether sulfate 2607-SF, polyoxyethylene cumylphenyl ether CMP-6, polyoxyethylene cumylphenyl ether CMP-8, polyoxyethylene cumylphenyl ether CMP-11, Span60, Arlacel-65, Tween-85, Tween-20, sodium taurocholate, Carbon nano-tube dispersant TNWDIS, neopelex, lauryl sodium sulfate, TritonX-100, TritonX-102, TritonX-305, ethylene nonyl phenylate, polyethylene glycol cetyl ether, cetyl trimethyl ammonium tosylate, softex kw, polyoxyethylene ammonium salt, quaternary ammonium salt, imidazoline, a kind of or wherein several mixture in castor oil polyoxyethylene ether and Aethoxy Sklerol.Other steps are identical with detailed description of the invention one.

TritonX-100, TritonX-102TritonX-305 described in present embodiment are all produced by Jiangsu Hai'an Petrochemical Plant.

Detailed description of the invention eight: present embodiment is that a kind of preparation method of emulsion pasting agent of carbon nano-tube modification specifically completes according to the following steps:

AB-HGF described in present embodiment is produced by Zhejiang Anbang New Material Development Co., Ltd.;

The advantage of present embodiment:

Detailed description of the invention nine: the difference of present embodiment and detailed description of the invention eight is: the surfactant described in step 2 is polyoxyethylene many rings phenyl ether sulfate 714-SF, polyoxyethylene many rings phenyl ether sulfate 707-SF, polyoxyethylene many rings phenyl ether sulfate 2607-SF, polyoxyethylene cumylphenyl ether CMP-6, polyoxyethylene cumylphenyl ether CMP-8, polyoxyethylene cumylphenyl ether CMP-11, Span60, Arlacel-65, Tween-85, Tween-20, sodium taurocholate, Carbon nano-tube dispersant TNWDIS, neopelex, lauryl sodium sulfate, TritonX-100, TritonX-102, TritonX-305, ethylene nonyl phenylate, polyethylene glycol cetyl ether, cetyl trimethyl ammonium tosylate, softex kw, polyoxyethylene ammonium salt, quaternary ammonium salt, imidazoline, a kind of or wherein several mixture in castor oil polyoxyethylene ether and Aethoxy Sklerol.Other steps are identical with detailed description of the invention eight.

Detailed description of the invention ten: present embodiment is that a kind of application of emulsion pasting agent of carbon nano-tube modification is carried out by the following method: the emulsion pasting agent of carbon nano-tube modification is placed in solution tank, then be that carbon fiber is passed through solution tank by 0.1m/s ~ 10m/s with speed, frictioning process again, then be that 0.1m/s ~ 10m/s is by being equipped with the rinse bath of absolute ethyl alcohol with speed, obtain the carbon fiber after processing, finally the carbon fiber after process is placed in the dry 1min ~ 10min of vacuum drying oven that temperature is 110 DEG C ~ 150 DEG C, obtains the carbon fiber that sizing agent is modified.

The advantage of present embodiment:

Adopt following verification experimental verification beneficial effect of the present invention:

Test one: a kind of preparation method of emulsion pasting agent of carbon nano-tube modification, specifically completes according to the following steps:

One, the preparation of epoxy resin latex system: low whipping speed is 10000rpm and temperature is at 70 DEG C, epoxy resin is mixed with epoxy emulsifier for mixing and drips deionized water, decline to system viscosity, low whipping speed is under 10000rpm, continue to stir 60min, then low whipping speed is under 1000rpm, add deionized water again, be 2% to system solid content, obtain epoxy emulsion, then add epoxy hardener in epoxy emulsion, low whipping speed is under 1000rpm, stir 30min, obtain epoxy resin latex system;

The mass ratio of described epoxy resin and epoxy emulsifying agent is 1:0.14; Described epoxy resin and the mass ratio of epoxy hardener are 1000:5;

Described epoxy resin is 4,5-7-oxa-bicyclo[4.1.0-1,2-dioctyl phthalate 2-glycidyl ester;

Described epoxy emulsifying agent is the polyoxyethylene cumylphenyl ether CMP-6 that Japanese emulsifying agent Co., Ltd. produces;

Described epoxy hardener is the AB-HGF that Zhejiang Anbang New Material Development Co., Ltd. produces;

Two, mix: under be 800W and frequency being 40kHz at power, by weight 0.5 part of modified carbon nano-tube and 0.5 part of surfactant are joined in 49 parts of deionized waters, ultrasonication 1h, obtain dispersion liquid, then under be 240W and frequency being 20kHz at power, dispersion liquid is mixed and ultrasonic 0.5h with 50 parts of epoxy resin latex systems, namely obtains the emulsion pasting agent of carbon nano-tube modification;

Modified carbon nano-tube described in step 2 is carboxylic carbon nano-tube; The preparation method of described carboxylic carbon nano-tube completes according to the following steps:

CNT is impregnated in Strong oxdiative solution, be 800W at power, frequency is process 1h in the Ultrasound Instrument of 40kHz, then be react 5h in the water-bath of 90 DEG C in temperature, then add deionized water dilution, be cooled to room temperature suction filtration, obtain filter residue, filter residue spend deionized water and suction filtration until the PH of cleaning solution is 7, finally by washing after filter residue put into the dry 3h of vacuum drying oven that temperature is 120 DEG C, namely obtain carboxylic carbon nano-tube;

Described Strong oxdiative solution to be mass fraction be 98% the concentrated sulfuric acid and mass fraction be the mixed solution of the red fuming nitric acid (RFNA) of 70%; Strong oxdiative liquid quality fraction be 98% the concentrated sulfuric acid and mass fraction be the volume ratio of the red fuming nitric acid (RFNA) of 70% be 3:1;

Described CNT is multi-walled carbon nano-tubes; Described carbon nanotube diameter is 10nm ~ 20nm, and length is 0.5um ~ 2um; The quality of described CNT and the volume ratio of Strong oxdiative solution are 1g:500mL.

The emulsion pasting agent of carbon nano-tube modification is placed in solution tank, then be that carbon fiber is passed through solution tank by 0.5m/s with speed, frictioning process again, then be that 0.5m/s is by being equipped with the rinse bath of absolute ethyl alcohol with speed, obtain the carbon fiber after processing, finally the carbon fiber after process is placed in the dry 5min of vacuum drying oven that temperature is 140 DEG C, obtains the carbon fiber that sizing agent is modified;

Described carbon fiber is T700 carbon fiber.

The fibre reinforced TDE-85 epoxy resin composite material interface shear strength adopting micro-unsticking method modified to sizing agent measures, and interface shear strength is 62.56MPa; And unsized fibre reinforced TDE-85 epoxy resin composite material, interface shear strength is 45.80MPa; Use the emulsion pasting agent of this test carbon nano-tube modification to carry out starching to carbon fiber, then strengthen TDE-85 epoxy resin composite material, relative to unsized fibre reinforced TDE-85 epoxy resin composite material, interface shear strength improves 36.6%.

A kind of aqueous epoxy resin emulsion system has been synthesized in this test, and this system particle diameter is 300nm ~ 600nm, highly stable;

The CNT of modification is prepared into the aqueous solution by this test, and blended with epoxy emulsion system, thus has synthesized the emulsion pasting agent of carbon nano-tube modification, and the particle diameter of this sizing agent is less, and particle diameter is 400nm ~ 700nm.

Test two: a kind of preparation method of emulsion pasting agent of carbon nano-tube modification, specifically completes according to the following steps:

Modified carbon nano-tube described in step 2 is amination CNT;

The preparation method of amination CNT completes according to the following steps:

1., the preparation of carboxylic carbon nano-tube: CNT is impregnated in Strong oxdiative solution, be 800W at power, frequency is process 1h in the Ultrasound Instrument of 40kHz, then be react 5h in the water-bath of 90 DEG C in temperature, then add deionized water dilution, be cooled to room temperature suction filtration, obtain filter residue, filter residue spend deionized water and suction filtration until the PH of cleaning solution is 7, finally by washing after filter residue put into the dry 3h of vacuum drying oven that temperature is 120 DEG C, namely obtain carboxylic carbon nano-tube;

2., the preparation of amination CNT: carboxylic carbon nano-tube step 1. obtained grinds to form carboxylic carbon nano-tube powder, then carboxylic carbon nano-tube powder and catalyst are joined in organic solvent, be 800W at power, frequency is broken ultrasonic 1h under the condition of 40kHz, then in reaction system, amine is added, after stirring 0.5h, be 240W at power, frequency is 20kHz, temperature is react 5h in the Ultrasound Instrument of 50 DEG C, with the centrifugal 60min of the centrifugal speed of 9000r/min after reaction terminates, be precipitated thing, sediment organic solvent A is dissolved, be cooled to room temperature suction filtration, obtain filter residue, by filter residue with organic solvent A washing and suction filtration 4 times, be be placed in the dry 5h of vacuum drying oven under the condition of 100 DEG C again in temperature by the filter residue after washing, obtain amination CNT,

Step 2. described in catalyst be 2-(7-azo BTA)-N, N, N', the mixture of N'-tetramethylurea hexafluorophosphoric acid ester and DIPEA, wherein 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester is 1:3 with the ratio of the amount of substance of DIPEA;

Step 2. described in organic solvent be DMF;

Step 2. described in organic solvent A be methyl alcohol;

Step 2. described in amine be weight average molecular weight be 600 polymines;

Step 2. described in carboxylic carbon nano-tube powder and the mass ratio of catalyst be 1:0.2;

Step 2. described in the quality of carboxylic carbon nano-tube powder be 1g:100mL with the ratio of the volume of organic solvent;

Step 2. described in carboxylic carbon nano-tube powder and the mass ratio of amine be 1:200.

The emulsion pasting agent of the carbon nano-tube modification this test prepared is placed in solution tank, then be that carbon fiber is passed through solution tank by 0.5m/s with speed, frictioning process again, then be that 0.5m/s is by being equipped with the rinse bath of absolute ethyl alcohol with speed, obtain the carbon fiber after processing, finally the carbon fiber after process is placed in the dry 5min of vacuum drying oven that temperature is 140 DEG C, obtains the carbon fiber that sizing agent is modified;

Described carbon fiber is T700 carbon fiber.

The fibre reinforced TDE-85 epoxy resin composite material interface shear strength adopting micro-unsticking method modified to sizing agent measures, and interface shear strength is 88.94MPa; And unsized fibre reinforced TDE-85 epoxy resin composite material, interface shear strength is 45.80MPa; Use the emulsion pasting agent of this test carbon nano-tube modification to carry out starching to carbon fiber, then strengthen TDE-85 epoxy resin composite material, relative to unsized fibre reinforced TDE-85 epoxy resin composite material, interface shear strength improves 91.45%.

Test three: a kind of preparation method of emulsion pasting agent of carbon nano-tube modification, specifically completes according to the following steps:

Modified carbon nano-tube described in step 2 is hydroxylating CNT;

The preparation method of hydroxylating CNT completes according to the following steps:

(1), the preparation of carboxylic carbon nano-tube: CNT is impregnated in Strong oxdiative solution, be 800W at power, frequency is process 1h in the Ultrasound Instrument of 40kHz, then be react 5h in the water-bath of 90 DEG C in temperature, then add deionized water dilution, be cooled to room temperature suction filtration, obtain filter residue, filter residue spend deionized water and suction filtration until the PH of cleaning solution is 7, finally by washing after filter residue put into the dry 3h of vacuum drying oven that temperature is 120 DEG C, namely obtain carboxylic carbon nano-tube;

(2), the preparation of hydroxylating CNT: 1., join in organic solvent by carboxylic carbon nano-tube and catalyst, under be 800W and frequency being 40kHz at power, broken ultrasonic 0.5h, obtains CNT mixed liquor;

Described carboxylic carbon nano-tube and the mass ratio of catalyst are 1:0.16; Described carboxylic carbon nano-tube and the mass ratio of organic solvent are 1:100; Described catalyst is 2-(7-azo BTA)-N, N, N', the mixture of N'-tetramethylurea hexafluorophosphoric acid ester and DIPEA, described 2-(7-azo BTA)-N, N, the mass ratio of N', N'-tetramethylurea hexafluorophosphoric acid ester and DIPEA is 1:1; Described organic solvent is DMF;

2., by 3-aminopropyl triethoxysilane join in the mixed liquid of second alcohol and water and be hydrolyzed 12h, obtain 3-aminopropyl triethoxysilane hydrolyzate; Described 3-aminopropyl triethoxysilane and the mass ratio of ethanol are 1:2; The mass ratio of described second alcohol and water is 1:0.5;

3., CNT mixed liquor is mixed with 3-aminopropyl triethoxysilane hydrolyzate, temperature be 50 DEG C, power be 240W and frequency is react 5h in the Ultrasound Instrument of 20kHz, again reacted solution is carried out centrifugal, and with methyl alcohol, suction filtration is washed 4 times to sediment, then the sediment after washing is put into the dry 3h of vacuum drying oven that temperature is 120 DEG C, obtain hydroxylating CNT; The mass ratio of described CNT mixed liquor and 3-aminopropyl triethoxysilane hydrolyzate is 1:0.2;

Described carbon fiber is T700 carbon fiber.

The fibre reinforced TDE-85 epoxy resin composite material interface shear strength adopting micro-unsticking method modified to sizing agent measures, and interface shear strength is 73.1MPa; And unsized fibre reinforced TDE-85 epoxy resin composite material, interface shear strength is 45.80MPa; Use the emulsion pasting agent of this test carbon nano-tube modification to carry out starching to carbon fiber, then strengthen TDE-85 epoxy resin composite material, relative to unsized fibre reinforced TDE-85 epoxy resin composite material, interface shear strength improves 59.6%.

Claims

1. an emulsion pasting agent for carbon nano-tube modification, is characterized in that a kind of emulsion pasting agent of carbon nano-tube modification is prepared from by 0.001 part ~ 2 parts modified carbon nano-tubes, 50 parts ~ 55 parts epoxy resin latex systems, 0.001 part ~ 1 part surfactant and 45 parts ~ 50 parts deionized waters by weight;

Described modified carbon nano-tube is carboxylic carbon nano-tube, amination CNT or hydroxylating CNT;

The preparation method of described carboxylic carbon nano-tube completes according to the following steps: be impregnated into by CNT in Strong oxdiative solution, be 400W ~ 800W at power, frequency is process 0.2h ~ 2h in the Ultrasound Instrument of 20kHz ~ 120kHz, then be react 3h ~ 12h in the water-bath of 40 DEG C ~ 95 DEG C in temperature, add deionized water dilution again, be cooled to room temperature suction filtration, obtain filter residue, filter residue spend deionized water and suction filtration until the pH of cleaning solution is 7, finally the filter residue after washing is put into the dry 2h ~ 12h of vacuum drying oven that temperature is 80 DEG C ~ 140 DEG C, namely carboxylic carbon nano-tube is obtained,

Described CNT is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes; Described carbon nanotube diameter is 0.8nm ~ 100nm, and length is 0.5um ~ 50um;

Step 2. described in amine be a kind of or wherein several mixture in aliphatic diamine, aromatic diamines, diethylenetriamine, triethylene tetramine, polymine and polyamidoamine dendrimer;

Step 2. described in the quality of carboxylic carbon nano-tube powder and the volume ratio 1g:(50mL ~ 1000mL of organic solvent);

Strong oxdiative solution described in step (1) to be mass fraction be 68% ~ 75% red fuming nitric acid (RFNA), mass fraction be 30% ~ 40% hydrogen peroxide, Strong oxdiative solution A or Strong oxdiative solution B; Wherein said Strong oxdiative solution A to be mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the mixed solution of the red fuming nitric acid (RFNA) of 68% ~ 75%; In Strong oxdiative solution A mass fraction be 95% ~ 98% the concentrated sulfuric acid and mass fraction be the volume ratio of the red fuming nitric acid (RFNA) of 68% ~ 75% be 1:(0.2 ~ 1); Described Strong oxdiative solution B to be mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the mixed solution of the hydrogen peroxide of 30% ~ 40%; In Strong oxdiative solution B mass fraction be 36% ~ 38% hydrochloric acid and mass fraction be the volume ratio of the hydrogen peroxide of 30% ~ 40% be 1:(1 ~ 10);

The quality of CNT described in step (1) and the volume ratio of Strong oxdiative solution are 1g:(100mL ~ 1000mL);

(2), the preparation of hydroxylating CNT: I, join in organic solvent by carboxylic carbon nano-tube and catalyst, under be 400W ~ 800W and frequency being 20kHz ~ 120kHz at power, broken ultrasonic 0.2h ~ 2h, obtains CNT mixed liquor;

II, 3-aminopropyl triethoxysilane is joined in the mixed liquid of second alcohol and water and be hydrolyzed 1h ~ 48h, obtain 3-aminopropyl triethoxysilane hydrolyzate; Described 3-aminopropyl triethoxysilane and the mass ratio of ethanol are 1:(1 ~ 10); The mass ratio of described second alcohol and water is 1:(0.1 ~ 1);

III, CNT mixed liquor is mixed with 3-aminopropyl triethoxysilane hydrolyzate, temperature be 20 DEG C ~ 60 DEG C, power be 200W ~ 400W and frequency is react 3h ~ 12h in the Ultrasound Instrument of 10kHz ~ 30kHz, again reacted solution is carried out centrifugal, and with methyl alcohol, suction filtration is washed 3 times ~ 8 times to sediment, then the sediment after washing is put into the dry 2h ~ 12h of vacuum drying oven that temperature is 80 DEG C ~ 140 DEG C, obtain hydroxylating CNT; The mass ratio of described CNT mixed liquor and 3-aminopropyl triethoxysilane hydrolyzate is 1:(0.1 ~ 1).

2. the emulsion pasting agent of a kind of carbon nano-tube modification according to claim 1, it is characterized in that described epoxy resin latex system is prepared according to the following steps: low whipping speed is 1000rpm ~ 12000rpm and temperature is at 65 DEG C ~ 85 DEG C, epoxy resin is mixed with epoxy emulsifier for mixing and drips deionized water, decline to system viscosity, low whipping speed is under 1000rpm ~ 12000rpm, continue to stir 10min ~ 100min, then low whipping speed is under 300rpm ~ 3000rpm, add deionized water again, be 0.5% ~ 4% to system solid content, obtain epoxy emulsion, epoxy hardener is added again in epoxy emulsion, low whipping speed is under 300rpm ~ 3000rpm, stir 10min ~ 60min, obtain epoxy resin latex system,

Described epoxy hardener is a kind of or wherein several mixture in Amino End Group polypropylene glycol D230, Amino End Group polypropylene glycol D400, aliphatic diamine, aromatic diamines, diethylenetriamine, triethylene tetramine and AB-HGF.

3. the emulsion pasting agent of a kind of carbon nano-tube modification according to claim 1, is characterized in that described surfactant is polyoxyethylene many rings phenyl ether sulfate 714-SF, polyoxyethylene many rings phenyl ether sulfate 707-SF, polyoxyethylene many rings phenyl ether sulfate 2607-SF, polyoxyethylene cumylphenyl ether CMP-6, polyoxyethylene cumylphenyl ether CMP-8, polyoxyethylene cumylphenyl ether CMP-11, Span60, Arlacel-65, Tween-85, Tween-20, sodium taurocholate, Carbon nano-tube dispersant TNWDIS, neopelex, lauryl sodium sulfate, TritonX-100, TritonX-102, TritonX-305, ethylene nonyl phenylate, polyethylene glycol cetyl ether, cetyl trimethyl ammonium tosylate, softex kw, polyoxyethylene ammonium salt, quaternary ammonium salt, imidazoline, a kind of or wherein several mixture in castor oil polyoxyethylene ether and Aethoxy Sklerol.

4. the preparation method of the emulsion pasting agent of a kind of carbon nano-tube modification as claimed in claim 1, is characterized in that what a kind of preparation method of emulsion pasting agent of carbon nano-tube modification specifically completed according to the following steps:

5. the preparation method of the emulsion pasting agent of a kind of carbon nano-tube modification according to claim 4, is characterized in that the surfactant described in step 2 is polyoxyethylene many rings phenyl ether sulfate 714-SF, polyoxyethylene many rings phenyl ether sulfate 707-SF, polyoxyethylene many rings phenyl ether sulfate 2607-SF, polyoxyethylene cumylphenyl ether CMP-6, polyoxyethylene cumylphenyl ether CMP-8, polyoxyethylene cumylphenyl ether CMP-11, Span60, Arlacel-65, Tween-85, Tween-20, sodium taurocholate, Carbon nano-tube dispersant TNWDIS, neopelex, lauryl sodium sulfate, TritonX-100, TritonX-102, TritonX-305, ethylene nonyl phenylate, polyethylene glycol cetyl ether, cetyl trimethyl ammonium tosylate, softex kw, polyoxyethylene ammonium salt, quaternary ammonium salt, imidazoline, a kind of or wherein several mixture in castor oil polyoxyethylene ether and Aethoxy Sklerol.

6. the application of the emulsion pasting agent of a kind of carbon nano-tube modification as claimed in claim 1, it is characterized in that a kind of application of emulsion pasting agent of carbon nano-tube modification is carried out by the following method: the emulsion pasting agent of carbon nano-tube modification is placed in solution tank, then be that carbon fiber is passed through solution tank by 0.1m/s ~ 10m/s with speed, frictioning process again, then be that 0.1m/s ~ 10m/s is by being equipped with the rinse bath of absolute ethyl alcohol with speed, obtain the carbon fiber after processing, finally the carbon fiber after process is placed in the dry 1min ~ 10min of vacuum drying oven that temperature is 110 DEG C ~ 150 DEG C, obtain the carbon fiber that sizing agent is modified.