CN105332267B - A kind of enhanced CNT sizing agent in carbon fiber interface and preparation method thereof - Google Patents
A kind of enhanced CNT sizing agent in carbon fiber interface and preparation method thereof Download PDFInfo
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- CN105332267B CN105332267B CN201510790472.6A CN201510790472A CN105332267B CN 105332267 B CN105332267 B CN 105332267B CN 201510790472 A CN201510790472 A CN 201510790472A CN 105332267 B CN105332267 B CN 105332267B
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Abstract
The invention discloses enhanced CNT sizing agent in a kind of carbon fiber interface and preparation method thereof, it is made up of the component of following parts by weight：60 80 parts of water, 20 40 parts of epoxy resin, 0.01 6 parts of emulsifying agent, 0.002 1.2 parts of modified carbon nano-tube, wherein, the modified carbon nano-tube is the CNT of surface grafting epoxy-functional.CNT is mixed in strong acid solution, reaction obtains the CNT that carboxyl functional group is contained on surface, mixed liquor A is obtained after the CNT that carboxyl functional group is contained on obtained surface is mixed with solvent, mixed liquid B is obtained after epoxy resin is mixed with solvent, after mixed liquor A and mixed liquid B are mixed, after heating response, modified carbon nano-tube is obtained.Contain CNT in the sizing agent of the present invention, CNT draw ratio is high, improves the mechanical property for the composite for preparing shaping, using the core shell structure of CNT external sheath epoxy resin, can ensure that CNT is effectively adhered carbon fiber surface.
Description
Technical field
The invention belongs to carbon fiber sizing agent field, and in particular on a kind of enhanced CNT in carbon fiber interface
Starch agent and preparation method thereof.
Background technology
Carbon fiber is to be made by precursor by the physicochemical change of a series of complex such as pre-oxidation, charing, graphitization, is stretched
Long rate is low and more crisp, the effect such as stretched, friction during using, processing, it may appear that fluffing, loose etc. are now
As the performance of carbon fiber and the performance of carbon fiber product being had a strong impact on, so to be carried out in carbon fiber production at starching
Reason.The binding ability of carbon fiber and matrix resin after starching is handled can strengthen, but enhancing effect is limited.
The sizing agent used when starching is handled is broadly divided into solvent-borne type sizing agent and emulsion-type sizing agent, solvent-borne type starching
Agent is made up of host and organic solvent, and organic solvent is volatile, pollutes environment, influences the health of operator.On emulsion-type
Slurry agent is made up of host and water, environment-friendly without volatile phase.More carbon fiber is used at present with emulsion-type sizing agent master
To be made up of resin, surfactant, water, auxiliary agent etc., as the increase of storage time occurs that demulsification, precipitation, resin separate out
Phenomena such as, sizing agent is failed, and using the resin of single component, will not largely improve carbon fiber and matrix resin
Binding ability.So needing to develop a kind of stable performance now, and can enough largely improves carbon fiber and substrate combinating strength
New Sizing agent.
The content of the invention
In order to solve technical problem present in prior art, the invention provides a kind of enhanced carbon in carbon fiber interface
Nanotube sizing agent and preparation method thereof.
In order to solve the above technical problems, the concrete scheme of the present invention is：
Application of the CNT of surface grafting epoxy-functional in sizing agent is prepared.
The preparation method of the CNT of surface grafting epoxy-functional, comprises the following steps：
CNT is mixed in strong acid solution, reaction obtains the CNT that carboxyl functional group is contained on surface, will
To the surface CNT that contains carboxyl functional group mixed with solvent after obtain mixed liquor A, epoxy resin is mixed with solvent
After obtain mixed liquid B, after mixed liquor A and mixed liquid B are mixed, after heating response, obtain modified carbon nano-tube.
CNT has agglomeration in sticky system, so first to disperse in a solvent, epoxy resin is more viscous
It is thick, it is also desirable to now dissolved dilution in a solvent, by two kinds of materials it is all scattered after remix, to ensure CNT and asphalt mixtures modified by epoxy resin
The contact area of fat is bigger, so enable CNT preferably and epoxy resin react.If three is directly mixed, because
Epoxy resin is more sticky, and when being put into solvent, whole system is more sticky, and CNT is reunited, even if ring after stirring
Oxygen tree fat is dissolved in system, and CNT has produced reunion, and the contact area of epoxy resin is limited, and reaction can not fill
Point.
Preferably, the strong acid is (general for concentrated hydrochloric acid (common commercially available type mass concentration 36.5%, 11.9mol/L), the concentrated sulfuric acid
Lead to commercially available type mass concentration 98%, 18.4mol/L) or concentrated nitric acid (common commercially available type mass concentration 65%, 14.4mol/L) in
One or more mixtures.
Preferably, the dosage of the CNT added in every liter of strong acid is 0.3-3g.
Preferably, the mass fraction of CNT is 0.1%-10% in the mixed liquor A；In mixed liquid B, epoxy resin
Mass fraction be 5%-50%, the volume ratio of mixed liquor A and mixed liquid B is 1:10-15:1.
Preferably, the heating-up temperature of the heating response is 40 DEG C -80 DEG C, and the reaction time is 1-10 hours.
Preferably, the solvent is one kind in toluene, acetone, ethanol or dimethyl sulfoxide (DMSO).
A kind of enhanced CNT sizing agent in carbon fiber interface, is made up of following components：Water, epoxy resin, emulsification
Agent, modified carbon nano-tube, wherein, the modified carbon nano-tube is the CNT of surface grafting epoxy-functional.
The purpose of grafted epoxy functional group be in order that CNT can be preferably and in sizing agent epoxy resin knot
Close, when sizing agent be coated in carbon fiber surface, carbon nano tube surface carries epoxy-functional, so can preferably and carbon fibre
The matrix for tieing up material combines, improve the binding ability of carbon fiber coated with sizing agent of the present invention and matrix resin with it is interface characteristics
Energy.
Preferably, the enhanced CNT sizing agent in carbon fiber interface, is made up of the component of following parts by weight：Water 60-
80 parts, epoxy resin 20-40 parts, emulsifying agent 0.01-6 parts, modified carbon nano-tube 0.002-1.2 parts, wherein, the carbon modified is received
Mitron is the CNT of surface grafting epoxy-functional.
Preferably, the enhanced CNT sizing agent in above-mentioned carbon fiber interface, is made up of the component of following parts by weight：Water
70-80 parts, epoxy resin 25-35 parts, emulsifying agent 0.125-5.25 parts, modified carbon nano-tube 0.0025-1.05 parts.
Preferably, the epoxy resin be diglycidyl ether type epoxy resin, glycidyl ester type epoxy resin, shrink it is sweet
One or more mixtures in oleyl amine type epoxy resin, cycloaliphatic epoxy resin or linear aliphatic race type epoxy resin.
Preferably, the emulsifying agent is AEO, APES, aliphatic acid polyethenoxy
Ester, aliphatic amine polyoxyethylene ether, alkylolamides APEO, Block polyoxyethylene-polyethenoxy ether, alkylolamides,
Alkyl poly glucoside, polyol ester, ammonia salt, quaternary ammonium salt, heterocyclic salt, carboxylate, sulfate, aliphatic alcohol sulfate, sulfuric acid
One or more mixtures in carburetion, sulfonate, alkylnaphthalene sulfonate, alkylbenzenesulfonate or alkylsulfonate.
The preparation method of the above-mentioned enhanced CNT sizing agent in carbon fiber interface, comprises the following steps：Match somebody with somebody by above-mentioned
Than modified carbon nano-tube is distributed in epoxy resin, then adds emulsifying agent in the epoxy, heats and stirs and mixed
Liquid is closed, water is then instilled in mixed liquor, after water adds, stirring, obtains interface enhancement CNT sizing agent；Above-mentioned water
Addition is divided into two processes, the first process：Water is slowly added dropwise as in epoxy resin composition, rate of addition 1-1000ml/h,
(content of this stage water is less, forms water-in-oil emulsion)；Second process：(with the progressively instillation of dampening, the content of water is progressively
Increase), when mixed liquor is mutated into milky, foring emulsion oil-in-water, (now water is as continuous phase, epoxy resin and changes
Property CNT be dispersed phase, after mutation increase water rate of addition, and enter the second process layer), the rate of addition of water
It is changed into 0.1-10L/h.Using first at a slow speed be added dropwise can make water droplet it is more tiny it is scattered in the epoxy, when from Water-In-Oil turn
When becoming oil-in-water, the particle diameter of dispersed phase can be made smaller, the emulsion of formation is more stable.
Preferably, the scattered method in the epoxy of the modified carbon nano-tube disperses 0.5-5h for ultrasonic wave；It is or logical
Cross colloid mill, ball mill or high speed agitator mechanical agitation and disperse 0.5-5h.
Application of the above-mentioned enhanced CNT sizing agent in carbon fiber interface in carbon fiber production.
Beneficial effects of the present invention are：
Compared with common sizing agent, the carbon nanometer containing surface grafting epoxy-functional in sizing agent prepared by the present invention
Pipe, the draw ratio of the modified carbon nano-tube is high, is present in carbon fiber surface after starching, it is possible to increase carbon fiber and resin matrix
Boundary strength, the mechanical property for the composite for preparing shaping is improved, CNT external sheath epoxy is used in sizing agent
The core shell structure of resin, it can ensure that CNT is effectively attached to carbon fiber surface；
Epoxy resin in the modified carbon nano-tube and sizing agent combines, and effectively increases the stability of sizing agent, effectively
The generation for phenomena such as preventing sizing agent demulsification, precipitation and resin to separate out, effectively increase the performance of carbon fiber.Carbon nanometer
Guan Shang grafted epoxies functional group, when sizing agent is coated on carbon fiber, epoxy-functional can make carbon fibre material and matrix
The combination of resin, improve the binding ability and interface performance of carbon fiber and matrix resin coated with sizing agent of the present invention.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of enhanced CNT sizing agent in carbon fiber interface, specific preparation method are as follows：
It is in the hydrochloric acid solution that mass fraction is 36.5% that 900mg CNTs are poured into concentration, and hydrochloric acid solution volume is
3L, after stirring 10 hours, the hydrochloric acid solution containing CNT is filtered, washed, surface is dried to obtain and contains carboxyl official
The modified carbon nano-tube that can be rolled into a ball, weighs 900mg modified carbon nano-tubes, pours into 8.1g toluene, obtains CNT-toluene mixing
Liquid.27g bisphenol A-type E51 epoxy resin is poured into 27g toluene and stirred.Modified carbon nano-tube-toluene mixture liquid is fallen
Enter in epoxy-toluene solution, heating stirring 10 hours, heating-up temperature is 65 DEG C, then filters mixed liquor, washs, vacuum is done
It is dry, obtain the modified carbon nano-tube that surface carries epoxy-functional.
Take 900mg to carry the modified carbon nano-tube of epoxy-functional, be scattered in 30g bisphenol A-type E51 epoxy resin, add
For heat to 60 DEG C, ultrasonic disperse simultaneously stirs 30min.
After obtaining the epoxy resin containing modified carbon nano-tube, 4.5g emulsifying agent sp80 are added, heats and stirs, then
Be slowly dropped into water, form water-in-oil emulsion, continue that water is added dropwise, when water droplet plus it is a certain amount of when form emulsion oil-in-water, it
The rate of addition of water is improved afterwards, and total amount of water is 45g, after waiting water droplet to add entirely, high-speed stirred 0.5-5 hours, obtains interface
Enhanced CNT sizing agent.
Embodiment 2
A kind of enhanced CNT sizing agent in carbon fiber interface, specific preparation method are as follows：
450mg CNTs are poured into commercially available concentrated sulfuric acid solution (common commercially available type mass concentration 98%, 18.4mol/L)
In, concentrated sulfuric acid solution volume is 3L, after stirring 10 hours, by the sulfuric acid solution containing CNT by filtering, washing, dry
The modified carbon nano-tube that carboxyl functional group is contained on surface is obtained, weighs 450mg modified carbon nano-tubes, pours into 6g acetone, obtains
CNT-acetone mixture.5g bisphenol A-type E51 epoxy resin is poured into 27g acetone and stirred.Carbon modified is received
Mitron-acetone mixture is poured into epoxy-acetone soln, heating stirring 5 hours, and heating-up temperature is 65 DEG C, then by mixed liquor
Filtering, washing, vacuum drying, obtain the modified carbon nano-tube that surface carries epoxy-functional.
Take 450mg to carry the modified carbon nano-tube of epoxy-functional, be scattered in 20g bisphenol A-type E51 epoxy resin, add
For heat to 60 DEG C, ultrasonic disperse simultaneously stirs 30min.
After obtaining the epoxy resin containing modified carbon nano-tube, 1.5g emulsifying agent sp80 are added, heats and stirs, then
Be slowly dropped into water, form water-in-oil emulsion, continue that water is added dropwise, when water droplet plus it is a certain amount of when form emulsion oil-in-water, it
The rate of addition of water is improved afterwards, and total amount of water is 45g, after waiting water droplet to add entirely, high-speed stirred 4 hours, obtains interface enhancing
Type CNT sizing agent.
Embodiment 3
900mg CNTs are poured into concentrated nitric acid (common commercially available type mass concentration 65%, 14.4mol/L), concentrated nitric acid
Liquor capacity is 0.3L, after stirring 2 hours, the salpeter solution containing CNT is filtered, wash, is dried to obtain surface
Modified carbon nano-tube containing carboxyl functional group, 900mg modified carbon nano-tubes are weighed, poured into 20g ethanol, obtain carbon nanometer
Pipe-alcohol mixeding liquid.27g bisphenol A-type E51 epoxy resin is poured into 27g ethanol and stirred.By modified carbon nano-tube-
Alcohol mixeding liquid is poured into epoxy-ethanol solution, heating stirring 1 hour, and heating-up temperature is 65 DEG C, then filter mixed liquor,
Washing, vacuum drying, obtain the modified carbon nano-tube that surface carries epoxy-functional.
Take 900mg to carry the modified carbon nano-tube of epoxy-functional, be scattered in 30g bisphenol A-type E51 epoxy resin, add
For heat to 60 DEG C, ultrasonic disperse simultaneously stirs 30min.
After obtaining the epoxy resin containing modified carbon nano-tube, 4.5g emulsifying agent sp80 are added, heats and stirs, then
Be slowly dropped into water, form water-in-oil emulsion, continue that water is added dropwise, when water droplet plus it is a certain amount of when form emulsion oil-in-water, it
The rate of addition of water is improved afterwards, and total amount of water is 45g, after waiting water droplet to add entirely, high-speed stirred 5 hours, obtains interface enhancing
Type CNT sizing agent.
Although the above-mentioned embodiment to the present invention is described, the limitation not to invention protection domain,
One of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art need not pay
The various modifications or deformation that creative work can be made are still within the scope of the present invention.
Claims (4)
- A kind of 1. preparation method of the enhanced CNT sizing agent in carbon fiber interface, it is characterised in that：Sizing agent is made up of following components：Water 60-80 parts, epoxy resin 20-40 parts, emulsifying agent 0.01-6 parts, modified carbon nano tube Pipe 0.002-1.2 parts, wherein, the modified carbon nano-tube is the CNT of surface grafting epoxy-functional；The preparation method of the CNT of the surface grafting epoxy-functional, comprises the following steps：CNT is mixed in In strong acid solution, reaction obtains the CNT that carboxyl functional group is contained on surface, and obtained surface is contained into carboxyl functional group CNT obtains mixed liquor A after being mixed with solvent, and mixed liquid B is obtained after epoxy resin is mixed with solvent, by mixed liquor A and After mixed liquid B mixing, after heating response, modified carbon nano-tube is obtained；The strong acid is one or more mixtures in concentrated hydrochloric acid, the concentrated sulfuric acid or concentrated nitric acid；The carbon added in every liter of strong acid The dosage of nanotube is 0.3-3g；The mass fraction of CNT is 0.1%-10% in the mixed liquor A；In mixed liquid B, epoxy The mass fraction of resin is 5%-50%, and the volume ratio of mixed liquor A and mixed liquid B is 1:10-15:1；The preparation method of sizing agent, comprises the following steps：Matched more than, modified carbon nano-tube be distributed in epoxy resin, Then emulsifying agent is added in the epoxy, is heated and is stirred to obtain mixed liquor, water is then instilled in mixed liquor, water adds Afterwards, stir, obtain interface enhancement CNT sizing agent；The addition of above-mentioned water is divided into two processes, the first process：Water is slow It is added dropwise in such as epoxy resin composition, rate of addition 1-1000ml/h；Second process：When the color change of mixed liquor is into milky white After color, the rate of addition of water is 0.1-10L/h.
- 2. the preparation method of the enhanced CNT sizing agent in carbon fiber interface according to claim 1, its feature exist In：The epoxy resin is diglycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine epoxy tree One or more mixtures in fat, cycloaliphatic epoxy resin or linear aliphatic race type epoxy resin.
- 3. the preparation method of the enhanced CNT sizing agent in carbon fiber interface according to claim 1, its feature exist In：The emulsifying agent is AEO, APES, polyoxyethylene carboxylate, fatty amine polyoxy Vinethene, alkylolamides APEO, Block polyoxyethylene-polyethenoxy ether, alkylolamides, alkyl polydextrose Glycosides, polyol ester, quaternary ammonium salt, aliphatic alcohol sulfate, sulfated oil, alkylnaphthalene sulfonate, alkylbenzenesulfonate or alkyl sulfonic acid One or more mixtures in salt.
- 4. the preparation method of the enhanced CNT sizing agent in carbon fiber interface according to claim 1, its feature exist In：The scattered method in the epoxy of the modified carbon nano-tube disperses 0.5-5h for ultrasonic wave；Or pass through colloid mill, ball milling Machine or high speed agitator mechanical agitation disperse 0.5-5h.
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| CN108976711A (en) * | 2018-07-02 | 2018-12-11 | 中国民航大学 | Carbon nanotube-carbon fiber mixing reinforced epoxy composite material preparation method |
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| CN102212967A (en) * | 2011-04-06 | 2011-10-12 | 东华大学 | Carbon fiber emulsion sizing agent improved by carbon nano tube and preparation method of carbon fiber emulsion sizing agent |
| CN104120605B (en) * | 2014-07-16 | 2016-02-10 | 哈尔滨工业大学 | Emulsion pasting agent of a kind of carbon nano-tube modification and its preparation method and application |
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