CN105297448A - Interface-enhanced nano silicon dioxide-modified epoxy resin sizing agent for carbon fiber - Google Patents
Interface-enhanced nano silicon dioxide-modified epoxy resin sizing agent for carbon fiber Download PDFInfo
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Abstract
The invention provides an interface-enhanced nano silicon dioxide-modified epoxy resin sizing agent for carbon fiber. The sizing agent is prepared from the following raw materials in parts by weight; 60-80 parts of water, 20-40 parts of nano silicon dioxide-modified epoxy resin and 0.01-6 parts of emulsifier. Compared with a common sizing agent, the sizing agent prepared in the invention contains nano silicon dioxide, the particle size of the nano silicon dioxide is small, and the nano silicon dioxide exists on the surface of the carbon fiber after sizing and can improve the interface strength of the carbon fiber and a resin substrate and improve the mechanical property of a prepared and molded composite material.
Description
Technical field
The invention belongs to carbon fiber sizing agent field, be specifically related to the silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer.
Background technology
Carbon fiber is obtained by the physicochemical change of precursor through series of complexes such as pre-oxidation, charing, graphitizations, percentage elongation is low and more crisp, the effect such as stretched, friction using, in the process of processing, there will be fluffing, the phenomenon such as loose, have a strong impact on the serviceability of carbon fiber and the performance of carbon fiber product, so starching process will be carried out in carbon fiber is produced.Carbon fiber after starching process and the binding ability of matrix resin can strengthen to some extent, but strengthen limited efficiency.
The sizing agent used when starching process is mainly divided into solvent-borne type sizing agent and emulsion-type sizing agent, and solvent-borne type sizing agent is made up of host and organic solvent, and organic solvent is volatile, contaminated environment, affects the healthy of operator.Emulsion-type sizing agent is made up of host and water, does not have volatile phase, environmental friendliness.The more carbon fiber emulsion-type sizing agent of current use is primarily of formations such as resin, surfactant, water, auxiliary agents, increase along with memory time there will be the phenomenons such as breakdown of emulsion, precipitation, resin precipitation, sizing agent was lost efficacy, and use the resin of single component, the binding ability of carbon fiber and matrix resin can not be improved largely.So need now to develop a kind of stable performance, the New Sizing agent of carbon fiber and substrate combinating strength can be improved again largely.
Chinese patent CN201510565786.6 discloses sizing agent prepared by hot mixing method, wherein, need be heated to more than 150 DEG C and nano silicon and epoxy resin are reacted, but the composite TENSILE STRENGTH of preparation is poor.
Summary of the invention
In order to solve the technical problem existed in prior art, the invention provides a kind of carbon fiber interface enhancement type nanometer silica sizing agent and preparation method thereof.
Nano silicon is unbodied white powder, the hydroxyl of different bond styles and a large amount of undersaturated residual bond is there is in its molecular structure surface, also has the silica structure that deviate from stable state because of anoxic, molecular structure is three-dimensional chain structure, this structure makes some group on nano-silicon dioxide particle and epoxy resin bonding action can occur, thus greatly improve hardness and the intensity of material, small-sized simultaneously due to nanometer silicon dioxide particle, when the suitable mode of employing and epoxy resin compound tense, nanometer silicon dioxide particle can be distributed in the space of macromolecule key of epoxy resin, and have an effect with its electron cloud, with the large molecular juction compound stereoscopic network structure of material, thus make the toughness of the silica/epoxy resin nano composites formed, intensity, ductility all improves a lot, compared with general silica particle, the non-coordinated atom of nano-silicon dioxide particle, blemish is many, therefore, with polymer generation physics or chemically combined possibility large, this physics or chemical action are that the interface cohesion of nano particle and epoxy resin-base improves greatly, thus enhancing is played to epoxy resin, toughness reinforcing effect.Nano-silicon dioxide particle has the optical characteristics such as UV Absorption, infrared reflection simultaneously, thus improves heat endurance and the chemical stability of coating.
In order to solve above technical problem, concrete scheme of the present invention is:
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, is made up of the raw material of weight components: water 60-80 part, nano-silicon dioxide modified epoxy resin 20-40 part, emulsifying agent 0.01-6 part.
That nano silicon is scattered in epoxy resin in the present invention, it is physical modification, without the need to heating (heating can affect the TENSILE STRENGTH of the composite of formation), because employ solvent in the process of dispersion, need removal of solvents, nano silicon and epoxy resin mixing in the solution, and dispersed after, adopt the method for decompression distillation to be distilled away by solvent under reduced pressure, obtain nano-silicon dioxide modified epoxy resin.
Preferably, be made up of the raw material of weight components: water 60-70 part, nano-silicon dioxide modified epoxy resin 20-30 part, emulsifying agent 0.01-3 part.
Preferably, be made up of the raw material of weight components: water 70-80 part, nano-silicon dioxide modified epoxy resin 30-40 part, emulsifying agent 3-6 part.
Preferably, described emulsifying agent is one or more the mixture in fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether, alkylolamides polyoxyethylene ether, Block polyoxyethylene-polyethenoxy ether, alkylolamides, alkyl poly glucoside, polyol ester, ammonia salt, quaternary ammonium salt, heterocyclic salt, carboxylate, sulfate, aliphatic alcohol sulfate, sulfated oil, sulfonate, alkylnaphthalene sulfonate, alkylbenzenesulfonate or alkylsulfonate.
Preferably, described nano-silicon dioxide modified epoxy resin is adopted and is prepared with the following method: be first dissolved in solvent by epoxy resin, then, nano silicon is added under stirring condition, after mixing, decompression distillation, obtains nano-silicon dioxide modified epoxy resin.
The process for dispersing of nano silicon can be divided into Physical and chemical method two class, and physical dispersion method mainly contains mechanical force dispersion and ultrasonic wave dispersion.Mechanical force dispersion is main by high-speed stirred and high speed ball milling, utilizes mechanical stress to carry out surface activation to particle, changes the crystal structure on its surface, molecular grating is subjected to displacement, interiorly to increase, carry out surface modification to it.
More specifically, epoxy resin to be dissolved in solvent and to stir, the mass ratio of epoxy resin and solvent is 10:1 ~ 1:100, after stirring, slowly nano silicon is added as in epoxy resin/solvent liquid, the mass ratio of the quality and epoxy resin that add nano silicon is 1:10 ~ 1:1000, stir while add nano silicon limit, after stirring, to nano silicon/epoxy resin/solvent, carry out decompression distillation, solvent distillation is removed, obtains nano-silicon dioxide modified epoxy resin.
Preferably, described epoxy resin is one or more the mixture in diglycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, cycloaliphatic epoxy resin or linear aliphatic race type epoxy resin.
Preferably, the particle diameter of described nano silicon is 1 ~ 100nm.The sized particles of nano silicon is little, and particle diameter is at 1 ~ 100nm, and specific area is large, agglomeration is had in thickness system, so will first epoxy resin be dissolved in a solvent, reduce its viscosity, and then nano silicon is added in the epoxy resin containing solvent.If three is directly mixed, because epoxy resin comparatively thickness, the whole system comparatively thickness when putting into solvent, reuniting appears in nano silicon, even if epoxy resin is dissolved in system after stirring, nano silicon produces reunion, can not well again be scattered in epoxy resin.To add slowly when adding nano silicon, and need to become and stir limit and add, avoid disposablely adding too much nano silicon, add too much nano silicon because disposable, easily make nano silicon produce agglomeration.
Preferably, described solvent is acetone, toluene, dimethyl sulfoxide (DMSO), methyl alcohol or ethylene glycol.
Preferably, the mass ratio of described nano silicon, epoxy resin, solvent is 1:10 ~ 1000:1 ~ 100000.
The preparation method of the silica modified epoxy resin sizing agent of above-mentioned carbon fiber interface enhancement type nanometer, comprise the steps: by said ratio, emulsifying agent is added in nano-silicon dioxide modified epoxy resin, heat and stir and obtain mixed liquor, then in mixed liquor, water is instilled, after water adds, stir, obtain the silica modified epoxy resin sizing agent of interface enhancement type nanometer; Adding of above-mentioned water is divided into two processes, the first process: water is slowly added dropwise in nano-silicon dioxide modified epoxy resin composition, and rate of addition is 1-1000ml/h, (content of this stage water is less, forms water-in-oil emulsion); Second process: (along with the progressively instillation of water, the content of water progressively increases), when mixed liquor is mutated into oyster white, (now water is as continuous phase to define emulsion oil-in-water, nano-silicon dioxide modified epoxy resin is decentralized photo, when increasing the rate of addition of water after sudden change, namely enter the second process), the rate of addition of water becomes 0.1-10L/h.Adopting first to drip at a slow speed to make dispersion that water droplet is more tiny in the epoxy, and when being transformed into oil-in-water from Water-In-Oil, the particle diameter of decentralized photo can be made less, and the emulsion of formation is more stable.
Described sizing agent can be used in carbon fiber production.
Beneficial effect of the present invention is:
Compare with common sizing agent, containing nano silicon in sizing agent prepared by the present invention, the particle diameter of nano silicon is little, is present in carbon fiber surface after starching, the boundary strength of carbon fiber and resin matrix can be improved, improve the mechanical property of the shaping composite of preparation.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
Embodiment 1
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, concrete preparation method is as follows:
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, stir after 1 hour, epoxy resin dissolves in acetone equably, 3g nano silicon adds in epoxy resin/acetone soln slowly, adds while stirring, adds rear continuation stirring 2 hours, after being uniformly dispersed, decompression distillation is carried out to mixed liquor, acetone is distilled away, obtain nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, get the nano-silicon dioxide modified epoxy resin of 30g, add 3.5g emulsifying agent sp60 wherein, heat and stir, then slowly instill water, form water-in-oil emulsion, continue to drip water, by the time emulsion oil-in-water is formed when water droplet adds a certain amount of, improve the rate of addition of water afterwards, total amount of water is 45g, waits for that water droplet adds completely, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 2
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, concrete preparation method is as follows:
30g glycidic amine type AG80 epoxy resin is added in 150g toluene, stir after 1.5 hours, epoxy resin is dissolved in toluene equably, 0.03g nano silicon is added in epoxy resin/toluene solution slowly, adds while stirring, add rear continuation stirring 2.5 hours, after being uniformly dispersed, decompression distillation is carried out to mixed liquor, toluene distillation is gone out, obtain nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, get the nano-silicon dioxide modified epoxy resin of 30g, add 2.0g emulsifying agent TW60 wherein, heat and stir, then slowly instill water, form water-in-oil emulsion, continue to drip water, by the time emulsion oil-in-water is formed when water droplet adds a certain amount of, improve the rate of addition of water afterwards, total amount of water is 40g, waits for that water droplet adds completely, high-speed stirred 5 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.。
Embodiment 3
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, concrete preparation method is as follows:
30g732# epoxy resin is added in 300g acetone, stir after 1 hour, epoxy resin is dissolved in dimethyl sulfoxide (DMSO) equably, 3g nano silicon adds in epoxy resin/acetone soln slowly, adds while stirring, adds rear continuation stirring 2 hours, after being uniformly dispersed, decompression distillation is carried out to mixed liquor, acetone is distilled away, obtain nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, get the nano-silicon dioxide modified epoxy resin of 30g, add 3.5g emulsifying agent sp60 wherein, heat and stir, then slowly instill water, form water-in-oil emulsion, continue to drip water, by the time emulsion oil-in-water is formed when water droplet adds a certain amount of, improve the rate of addition of water afterwards, total amount of water is 45g, waits for that water droplet adds completely, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 4
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, concrete preparation method is as follows:
30gERL-4221 epoxy resin is added in 300g acetone, stir after 1 hour, epoxy resin is dissolved in equably, in methyl alcohol, 3g nano silicon adds in epoxy resin/acetone soln slowly, adds while stirring, adds rear continuation stirring 2 hours, after being uniformly dispersed, decompression distillation is carried out to mixed liquor, acetone is distilled away, obtain nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, get the nano-silicon dioxide modified epoxy resin of 30g, add 3.5g emulsifying agent sp60 wherein, heat and stir, then slowly instill water, form water-in-oil emulsion, continue to drip water, by the time emulsion oil-in-water is formed when water droplet adds a certain amount of, improve the rate of addition of water afterwards, total amount of water is 45g, waits for that water droplet adds completely, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 5
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, concrete preparation method is as follows:
30gUVR-6100 epoxy resin is added in 300g acetone, stir after 1 hour, epoxy resin is dissolved in ethylene glycol equably, 3g nano silicon adds in epoxy resin/acetone soln slowly, adds while stirring, adds rear continuation stirring 2 hours, after being uniformly dispersed, decompression distillation is carried out to mixed liquor, acetone is distilled away, obtain nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, get the nano-silicon dioxide modified epoxy resin of 30g, add 3.5g emulsifying agent sp80 wherein, heat and stir, then slowly instill water, form water-in-oil emulsion, continue to drip water, by the time emulsion oil-in-water is formed when water droplet adds a certain amount of, improve the rate of addition of water afterwards, total amount of water is 45g, waits for that water droplet adds completely, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 6
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, concrete preparation method is as follows:
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, stir after 1 hour, epoxy resin dissolves in acetone equably, 3g nano silicon adds in epoxy resin/acetone soln slowly, adds while stirring, adds rear continuation stirring 2 hours, after being uniformly dispersed, decompression distillation is carried out to mixed liquor, acetone is distilled away, obtain nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, get the nano-silicon dioxide modified epoxy resin of 30g, add 3.5g emulsifying agent TW-60 wherein, heat and stir, then slowly instill water, form water-in-oil emulsion, continue to drip water, by the time emulsion oil-in-water is formed when water droplet adds a certain amount of, improve the rate of addition of water afterwards, total amount of water is 45g, waits for that water droplet adds completely, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 7
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, concrete preparation method is as follows:
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, stir after 1 hour, epoxy resin dissolves in acetone equably, 3g nano silicon adds in epoxy resin/acetone soln slowly, adds while stirring, adds rear continuation stirring 2 hours, after being uniformly dispersed, decompression distillation is carried out to mixed liquor, acetone is distilled away, obtain nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, get the nano-silicon dioxide modified epoxy resin of 30g, add No. 100,3.5g agriculture breast wherein, heat and stir, then slowly instill water, form water-in-oil emulsion, continue to drip water, by the time emulsion oil-in-water is formed when water droplet adds a certain amount of, improve the rate of addition of water afterwards, total amount of water is 45g, waits for that water droplet adds completely, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 8
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, concrete preparation method is as follows:
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, stir after 1 hour, epoxy resin dissolves in acetone equably, 3g nano silicon adds in epoxy resin/acetone soln slowly, adds while stirring, adds rear continuation stirring 2 hours, after being uniformly dispersed, decompression distillation is carried out to mixed liquor, acetone is distilled away, obtain nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, get the nano-silicon dioxide modified epoxy resin of 30g, add pungent No. 10 of 3.5g phosphorus wherein, heat and stir, then slowly instill water, form water-in-oil emulsion, continue to drip water, by the time emulsion oil-in-water is formed when water droplet adds a certain amount of, improve the rate of addition of water afterwards, total amount of water is 45g, waits for that water droplet adds completely, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 9
The silica modified epoxy resin sizing agent of a kind of carbon fiber interface enhancement type nanometer, concrete preparation method is as follows:
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, stir after 1 hour, epoxy resin dissolves in acetone equably, 3g nano silicon adds in epoxy resin/acetone soln slowly, adds while stirring, adds rear continuation stirring 2 hours, after being uniformly dispersed, decompression distillation is carried out to mixed liquor, acetone is distilled away, obtain nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, get the nano-silicon dioxide modified epoxy resin of 30g, add pungent No. 10 of 3.5g phosphorus wherein, heat and stir, then slowly instill water, form water-in-oil emulsion, continue to drip water, by the time emulsion oil-in-water is formed when water droplet adds a certain amount of, improve the rate of addition of water afterwards, total amount of water is 45g, waits for that water droplet adds completely, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Comparative example 1
(1) by weight, the bisphenol A type epoxy resin of 1 part is dissolved in the alcohol solvent of 5 parts, be stirred to epoxy resin 60 DEG C of heating to dissolve completely, then slowly drip the diglycolamine solution of 0.5 part with the speed of 3/min, rapid stirring obtains the epoxy resin of modification.
(2) by weight, the ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, and drips the glacial acetic acid of 0.3 part with 10/min, and at 25 DEG C, constant temperature stirs 2h, obtains aqueous epoxy resins.
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 10-part, regulates PH to 8 alkalescent, add thermal agitation, the ethanol water of slow dropping 8 parts, constant temperature stirring reaction, naturally cools to the nano silicon dioxide sol that room temperature obtains 50nm.
(4) by weight, the aqueous epoxy resins solution of distilled water diluting to 5% is slowly added in the aqueous epoxy resins that the steps of 20 parts (2) are prepared, being heated to 90 DEG C makes aqueous epoxy resins activate, then the nano silicon dioxide sol of prepared by step (3) 1 part is added, be heated to 150 DEG C of stirring reactions, obtain nano-silicon dioxide modified aqueous epoxy resins, finally add the aromatic amine curing agent of 3 parts, the aromatic amine antioxidant of 0.5 part, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
Comparative example 2
(1) by weight, the bisphenol A type epoxy resin of 1 part is dissolved in the alcohol solvent of 8 parts, be stirred to epoxy resin 70 DEG C of heating to dissolve completely, then slowly drip the diglycolamine solution of 0.9 part with the speed of 5/min, rapid stirring obtains the epoxy resin of modification.
(2) by weight, the ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, and drips the glacial acetic acid of 0.7 part with 15/min, and at 30 DEG C, constant temperature stirs 3h, obtains aqueous epoxy resins.
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 13 parts, regulates PH to 9 alkalescent, add thermal agitation, the ethanol water of slow dropping 10 parts, constant temperature stirring reaction, naturally cools to the nano silicon dioxide sol that room temperature obtains 100nm.
(4) by weight, the aqueous epoxy resins solution of distilled water diluting to 8% is slowly added in the aqueous epoxy resins that the steps of 40 parts (2) are prepared, being heated to 100 DEG C makes aqueous epoxy resins activate, then the nano silicon dioxide sol of prepared by step (3) 8 parts is added, be heated to 160 DEG C of stirring reactions, obtain nano-silicon dioxide modified aqueous epoxy resins, finally add the aromatic amine curing agent of 8 parts, the isopropyl alcohol of the aromatic amine antioxidant of 3 parts and 30 parts, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
Comparative example 3
Be with the difference of embodiment 1, nano silicon is scattered in epoxy resin under ultrasonic agitation condition.
Comparative example 4
With the difference of embodiment 1, nano silicon in the presence of dispersants, is scattered in epoxy resin.
Adopt the sizing agent of above-described embodiment and comparative example to go the starching of slurry viscose-based carbon fiber, the impregnation time is 60s, and dry removing moisture, namely obtains carbon fibre composite.
Obtain the tensile strength of carbon fiber in above-described embodiment and comparative example according to the analysis of test methods test of tensile strength of carbon fibers, be listed in following table.
After testing, the rate of sizing result of the rate of sizing of carbon fiber interface enhancement type nanometer silica modified epoxy resin sizing agent prepared of embodiment 1-7 and the nano-silicon dioxide modified epoxy resin solvent-borne type sizing agent of comparative example 1,2 is as follows:
Although above-mentioned combination is described the specific embodiment of the present invention; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. the silica modified epoxy resin sizing agent of carbon fiber interface enhancement type nanometer, is characterized in that, be made up of the raw material of weight components: water 60-80 part, nano-silicon dioxide modified epoxy resin 20-40 part, emulsifying agent 0.01-6 part.
2. sizing agent as claimed in claim 1, is characterized in that, be made up of the raw material of weight components: water 60-70 part, nano-silicon dioxide modified epoxy resin 20-30 part, emulsifying agent 0.01-3 part.
3. sizing agent as claimed in claim 1, is characterized in that, be made up of the raw material of weight components: water 70-80 part, nano-silicon dioxide modified epoxy resin 30-40 part, emulsifying agent 3-6 part.
4. the sizing agent as described in any one of claim 1-3, it is characterized in that, described emulsifying agent is fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether, alkylolamides polyoxyethylene ether, Block polyoxyethylene-polyethenoxy ether, alkylolamides, alkyl poly glucoside, polyol ester, ammonia salt, quaternary ammonium salt, heterocyclic salt, carboxylate, sulfate, aliphatic alcohol sulfate, sulfated oil, sulfonate, alkylnaphthalene sulfonate, one or more mixture in alkylbenzenesulfonate or alkylsulfonate.
5. the sizing agent as described in any one of claim 1-3, it is characterized in that, described nano-silicon dioxide modified epoxy resin is adopted and is prepared with the following method: be first dissolved in solvent by epoxy resin, then, nano silicon is added under stirring condition, after mixing, decompression distillation, obtains nano-silicon dioxide modified epoxy resin.
6. sizing agent as claimed in claim 5, it is characterized in that, described epoxy resin is one or more the mixture in diglycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, cycloaliphatic epoxy resin or linear aliphatic race type epoxy resin.
7. sizing agent as claimed in claim 5, it is characterized in that, the particle diameter of described nano silicon is 1 ~ 100nm.
8. sizing agent as claimed in claim 5, it is characterized in that, described solvent is acetone, toluene, dimethyl sulfoxide (DMSO), methyl alcohol or ethylene glycol.
9. sizing agent as claimed in claim 5, it is characterized in that, the mass ratio of described nano silicon, epoxy resin, solvent is 1:10 ~ 1000:1 ~ 100000.
10. the preparation method of the arbitrary described sizing agent of claim 1-9, it is characterized in that, take each raw material, emulsifying agent is added in nano-silicon dioxide modified epoxy resin, heat and stir and obtain mixed liquor, then in mixed liquor, instill water, after water adds, stir, obtain the silica modified epoxy resin sizing agent of interface enhancement type nanometer.
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| CN107033734A (en) * | 2017-04-07 | 2017-08-11 | 国家纳米科学中心 | One kind can ceramic epoxy resin fireproof coating |
| CN107603152A (en) * | 2017-09-14 | 2018-01-19 | 苏州盱酋汽车科技有限公司 | A kind of lightweight carbon fiber/epoxy resin composite material and preparation method thereof |
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| CN106351008A (en) * | 2016-08-31 | 2017-01-25 | 成路凯尔服装（苏州）有限公司 | Cotton fabric yarn sizing process |
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| CN110158317A (en) * | 2019-05-30 | 2019-08-23 | 叶小文 | A kind of preparation method of high mating type carbon fiber epoxy sizing agent |
| CN114438790A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Modified epoxy resin sizing agent and preparation and application thereof |
| CN114438790B (en) * | 2020-10-30 | 2024-04-09 | 中国石油化工股份有限公司 | Modified epoxy resin sizing agent and preparation and application thereof |
| CN113897776A (en) * | 2021-11-29 | 2022-01-07 | 中复神鹰碳纤维股份有限公司 | Silicon titanium based modified sizing agent and preparation method thereof |
| CN116814157A (en) * | 2023-05-08 | 2023-09-29 | 徐州博创新型材料科技有限公司 | Preparation method of epoxy organic coating based on nano material |
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