CN105297448B - A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer - Google Patents
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer Download PDFInfo
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- CN105297448B CN105297448B CN201510861119.2A CN201510861119A CN105297448B CN 105297448 B CN105297448 B CN 105297448B CN 201510861119 A CN201510861119 A CN 201510861119A CN 105297448 B CN105297448 B CN 105297448B
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Abstract
The present invention provides a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, is made of the raw material of weight components：60 80 parts of water, 20 40 parts of nano-silicon dioxide modified epoxy resin, 0.01 6 parts of emulsifier.It is compared with common sizing agent, contain nano silicon dioxide in sizing agent prepared by the present invention, the grain size of nano silicon dioxide is small, and carbon fiber surface is present in after starching, the boundary strength of carbon fiber and resin matrix can be improved, the mechanical property for preparing molding composite is improved.
Description
Technical field
The invention belongs to carbon fiber sizing agent fields, and in particular to a kind of carbon fiber Wesy interface enhancement type nanometer titanium dioxide
Silicon modified epoxy resin sizing agent.
Background technology
Carbon fiber is made by the physicochemical change of a series of complex such as pre-oxidation, charing, graphitization by precursor, is stretched
Long rate is low and more crisp, the effects that wanting stretched during using, processing, rub, it may appear that fluffing, loose etc. are existing
As the performance of carbon fiber and the performance of carbon fiber product being seriously affected, so to be carried out at starching in carbon fiber production
Reason.Binding performance by starching treated carbon fiber and matrix resin can be enhanced, 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 type starching
Agent is made of host agent and organic solvent, and organic solvent is volatile, is polluted environment, is influenced the health of operator.On emulsion-type
Slurry agent is made of host agent and water, environmental-friendly without volatile phase.More carbon fiber Wesy emulsion-type sizing agent master is used at present
It to be made of resin, surfactant, water, auxiliary agent etc., as the increase of storage time will appear demulsification, precipitation, resin precipitation
Phenomena such as, so that sizing agent is failed, and using the resin of single component, will not largely improve carbon fiber and matrix resin
Binding performance.So needing to develop a kind of performance stabilization now, and it can largely improve carbon fiber and substrate combinating strength
New Sizing agent.
Chinese patent CN201510565786.6 discloses the sizing agent of hot mixing method preparation, wherein need to be heated to 150 DEG C
Nano silicon dioxide and epoxy resin is set to react above, but the composite material tensile strength prepared is poor.
Invention content
In order to solve the technical problems existing in the prior art, receive the present invention provides a kind of carbon fiber Wesy interface is enhanced
Rice silica sizing agent and preparation method thereof.
Nano silicon dioxide is amorphous white powder, and there are the hydroxyls of different bond styles in molecular structure surface
With a large amount of undersaturated residual bonds, the silica structure of stable state is also deviated from because of anoxic, molecular structure is in three-dimensional chain structure, this
Kind structure allows nano-silicon dioxide particle that bonding action occurs with certain groups on epoxy resin, to substantially improve
The hardness and strength of material, simultaneously because nanometer silicon dioxide particle is small-sized, when using suitable mode and asphalt mixtures modified by epoxy resin
Fat compound tense, nanometer silicon dioxide particle can be distributed in the gap of high score sub-key of epoxy resin, and be sent out with its electron cloud
Raw effect, space network is combined into the macromolecular of material, so that the silica/epoxide resin nano formed is multiple
Toughness, intensity, the ductility of condensation material all improve a lot, compared with general silica particle, nanometer titanium dioxide silicon grain
The noncoordinating atom of son, surface defect are more, and therefore, the possibility physically or chemically combined with polymer generation is big, this physics
Or chemical action is that the interface cohesion of nano-particle and epoxy resin-base greatly improves, to epoxy resin play enhancing,
The effect of toughening.Nano-silicon dioxide particle has the optical characteristics such as UV Absorption, infrared reflection simultaneously, so as to improve painting
The thermal stability and chemical stability of material.
In order to solve the above technical problems, the concrete scheme of the present invention is：
The silica modified epoxy resin sizing agent of a kind of carbon fiber Wesy interface enhancement type nanometer, by weight components
Raw material forms：60-80 parts of water, nano-silicon dioxide modified epoxy resin 20-40 parts, 0.01-6 parts of emulsifier.
It is that nano silicon dioxide is scattered in epoxy resin in the present invention, is physical modification, (heating can shadow without heating
Ring the tensile strength of the composite material formed) because having used solvent during dispersion, need to remove solvent, receive
Rice silica and epoxy resin mixing in the solution, and it is evenly dispersed after, using the method for vacuum distillation by solvent under reduced pressure
It is distilled off, obtains nano-silicon dioxide modified epoxy resin.
Preferably, it is made of the raw material of weight components：60-70 parts of water, nano-silicon dioxide modified epoxy resin 20-
30 parts, 0.01-3 parts of emulsifier.
Preferably, it is made of the raw material of weight components：70-80 parts of water, nano-silicon dioxide modified epoxy resin 30-
40 parts, 3-6 parts of emulsifier.
Preferably, the emulsifier is fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, aliphatic acid polyethenoxy
Ester, 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, sulfuric acid
One or more mixtures in carburetion, sulfonate, alkylnaphthalene sulfonate, alkylbenzene sulfonate or alkylsulfonate.
Preferably, the nano-silicon dioxide modified epoxy resin is prepared with the following method：First epoxy resin is dissolved in
In solvent, then, nano silicon dioxide is added under stirring condition, after mixing, is evaporated under reduced pressure to get nano silicon dioxide
Modified epoxy.
The dispersing method of nano silicon dioxide can be divided into two class of Physical and chemical method, and physical dispersion method mainly has mechanical force
Dispersion and ultrasonic wave dispersion.Mechanical force dispersion carries out particle using mechanical stress mainly by high-speed stirred and high speed ball milling
Surface activation changes the crystal structure on its surface, so that molecular grating is subjected to displacement, interior energy increase etc., surface has been carried out to it and has been changed
Property.
More specifically, epoxy resin to be dissolved in solvent and stir, the mass ratio of epoxy resin and solvent is 10：1~1:
100, after stirring evenly, as being slowly added to nano silicon dioxide in epoxy resin/solvent mixed liquor, nano silicon dioxide is added
The mass ratio of quality and epoxy resin is 1:10~1:1000, it is stirred when nano silicon dioxide is added, after stirring evenly, to receiving
Rice silica/epoxy resin/solvent, is evaporated under reduced pressure, and solvent is distilled and is removed, nano-silicon dioxide modified epoxy is obtained
Resin.
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 grain size of the nano silicon dioxide is 1~100nm.The sized particles of nano silicon dioxide are small, grain size
In 1~100nm, large specific surface area has agglomeration in sticky system, so epoxy resin is first dissolved in solvent
In, its viscosity is reduced, then nano silicon dioxide is added in the epoxy resin containing solvent again.If three is directly mixed,
Because epoxy resin is more sticky, when being put into solvent, whole system is more sticky, and nano silicon dioxide is reunited, even if
Epoxy resin is dissolved in system after stirring, and nano silicon dioxide has generated reunion, good again can not be scattered in epoxy
In resin.It to be slowly added when nano silicon dioxide is added, and need to become the addition of stirring side, avoid being added at one time excessive
Nano silicon dioxide because being added at one time excessive nano silicon dioxide, be easy to make nano silicon dioxide generate reunite it is existing
As.
Preferably, the solvent is acetone, toluene, dimethyl sulfoxide (DMSO), methanol or ethylene glycol.
Preferably, the nano silicon dioxide, epoxy resin, solvent mass ratio be 1:10~1000：1~100000.
The preparation method of the silica modified epoxy resin sizing agent of above-mentioned carbon fiber Wesy interface enhancement type nanometer, including such as
Lower step：By said ratio, emulsifier is added in nano-silicon dioxide modified epoxy resin, heat and stirs to get mixing
Then liquid instills water in mixed liquor, after water adds, stirring obtains the silica modified epoxy resin of interface enhancement type nanometer
Sizing agent；The addition of above-mentioned water is divided into two processes, the first process：Water is slowly added dropwise into nano-silicon dioxide modified epoxy resin
In mixture, rate of addition 1-1000ml/h, (content of this stage water is less, forms water-in-oil emulsion)；Second process：
(with the gradually instillation of dampening, the content of water is stepped up), when mixed liquor is mutated into milky, forms emulsion oil-in-water
(water is dispersed phase as continuous phase, nano-silicon dioxide modified epoxy resin at this time, increases the rate of addition of water after mutation,
Enter the second process), the rate of addition of water becomes 0.1-10L/h.Water droplet can be made more tiny using being first added dropwise at a slow speed
Dispersion in the epoxy, when being transformed into oil-in-water from Water-In-Oil, can make the grain size smaller of dispersed phase, the lotion of formation is more
Add stabilization.
The sizing agent can be used in carbon fiber production.
Beneficial effects of the present invention are：
It is compared with common sizing agent, nano silicon dioxide, nano silicon dioxide is contained in sizing agent prepared by the present invention
Grain size it is small, carbon fiber surface is present in after starching, the boundary strength of carbon fiber and resin matrix can be improved, raising is prepared into
The mechanical property of the composite of type.
Specific implementation mode
The invention will be further described With reference to embodiment.
Embodiment 1
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, specific preparation method is such as
Under：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin equably dissolves
In acetone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue after addition
Stirring 2 hours, after being uniformly dispersed, is evaporated under reduced pressure mixed liquor, acetone is distilled off, and obtains nanometer titanium dioxide modification
Epoxy resin.
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Enter 3.5g emulsifier sp60, heat and stir, be then slowly dropped into water, form water-in-oil emulsion, continues that water is added dropwise, wait until
Emulsion oil-in-water is formed when water droplet adds a certain amount of, improves the rate of addition of water later, and total amount of water is 45g, and water droplet is waited for add
After completely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 2
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, specific preparation method is such as
Under：
30g glycidic amine type AG80 epoxy resin is added in 150g toluene, after stirring 1.5 hours, epoxy resin is equal
It is dissolved in toluene evenly, 0.03g nano silicon dioxides is slowly added in epoxy resin/toluene solution, add while stirring
Enter, continues stirring 2.5 hours after addition, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, toluene distillation is gone out, is obtained
To nanometer titanium dioxide modified epoxy.
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Enter 2.0g emulsifier TW60, heat and stir, be then slowly dropped into water, form water-in-oil emulsion, continues that water is added dropwise, wait until
Emulsion oil-in-water is formed when water droplet adds a certain amount of, improves the rate of addition of water later, and total amount of water is 40g, and water droplet is waited for add
After completely, high-speed stirred 5 hours obtains nano-silicon dioxide modified epoxy resin sizing agent..
Embodiment 3
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, specific preparation method is such as
Under：
30g 732# epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in diformazan
In base sulfoxide, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue after addition
Stirring 2 hours, after being uniformly dispersed, is evaporated under reduced pressure mixed liquor, acetone is distilled off, and obtains nanometer titanium dioxide modification
Epoxy resin.
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Enter 3.5g emulsifier sp60, heat and stir, be then slowly dropped into water, form water-in-oil emulsion, continues that water is added dropwise, wait until
Emulsion oil-in-water is formed when water droplet adds a certain amount of, improves the rate of addition of water later, and total amount of water is 45g, and water droplet is waited for add
After completely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 4
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, specific preparation method is such as
Under：
30g ERL-4221 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin equably dissolves
In, methanol, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue after addition
Stirring 2 hours, after being uniformly dispersed, is evaporated under reduced pressure mixed liquor, acetone is distilled off, and obtains nanometer titanium dioxide modification
Epoxy resin.
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Enter 3.5g emulsifier sp60, heat and stir, be then slowly dropped into water, form water-in-oil emulsion, continues that water is added dropwise, wait until
Emulsion oil-in-water is formed when water droplet adds a certain amount of, improves the rate of addition of water later, and total amount of water is 45g, and water droplet is waited for add
After completely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 5
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, specific preparation method is such as
Under：
30g UVR-6100 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in
In ethylene glycol, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue after addition
Stirring 2 hours, after being uniformly dispersed, is evaporated under reduced pressure mixed liquor, acetone is distilled off, and obtains nanometer titanium dioxide modification
Epoxy resin.
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Enter 3.5g emulsifier sp80, heat and stir, be then slowly dropped into water, form water-in-oil emulsion, continues that water is added dropwise, wait until
Emulsion oil-in-water is formed when water droplet adds a certain amount of, improves the rate of addition of water later, and total amount of water is 45g, and water droplet is waited for add
After completely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 6
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, specific preparation method is such as
Under：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin equably dissolves
In acetone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue after addition
Stirring 2 hours, after being uniformly dispersed, is evaporated under reduced pressure mixed liquor, acetone is distilled off, and obtains nanometer titanium dioxide modification
Epoxy resin.
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Enter 3.5g emulsifier TW-60, heat and stir, be then slowly dropped into water, form water-in-oil emulsion, continues that water is added dropwise, etc.
To water droplet plus it is a certain amount of when form emulsion oil-in-water, later improve water rate of addition, total amount of water be 45g, wait for water droplet
After adding entirely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 7
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, specific preparation method is such as
Under：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin equably dissolves
In acetone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue after addition
Stirring 2 hours, after being uniformly dispersed, is evaporated under reduced pressure mixed liquor, acetone is distilled off, and obtains nanometer titanium dioxide modification
Epoxy resin.
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Enter 3.5g agriculture breasts 100, heat and stir, be then slowly dropped into water, form water-in-oil emulsion, continues that water is added dropwise, wait until
Emulsion oil-in-water is formed when water droplet adds a certain amount of, improves the rate of addition of water later, and total amount of water is 45g, and water droplet is waited for add
After completely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 8
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, specific preparation method is such as
Under：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin equably dissolves
In acetone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue after addition
Stirring 2 hours, after being uniformly dispersed, is evaporated under reduced pressure mixed liquor, acetone is distilled off, and obtains nanometer titanium dioxide modification
Epoxy resin.
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Enter pungent No. 10 of 3.5g phosphorus, heat and stir, be then slowly dropped into water, form water-in-oil emulsion, continues that water, Deng Daoshui is added dropwise
Emulsion oil-in-water is formed when being added dropwise a certain amount of, improves the rate of addition of water later, and total amount of water is 45g, and water droplet is waited for add
Quan Hou, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Embodiment 9
A kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, specific preparation method is such as
Under：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin equably dissolves
In acetone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue after addition
Stirring 2 hours, after being uniformly dispersed, is evaporated under reduced pressure mixed liquor, acetone is distilled off, and obtains nanometer titanium dioxide modification
Epoxy resin.
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Enter pungent No. 10 of 3.5g phosphorus, heat and stir, be then slowly dropped into water, form water-in-oil emulsion, continues that water, Deng Daoshui is added dropwise
Emulsion oil-in-water is formed when being added dropwise a certain amount of, improves the rate of addition of water later, and total amount of water is 45g, and water droplet is waited for add
Quan Hou, high-speed stirred 4 hours, obtains nano-silicon dioxide modified epoxy resin sizing agent.
Comparative example 1
(1) by weight, 1 part of bisphenol A type epoxy resin is dissolved in 5 parts of alcohol solvent, is stirred in 60 DEG C of heating
It mixes to epoxy resin and is completely dissolved, 0.5 part of diglycolamine solution is then slowly added dropwise with the rate of 3 drops/min, quickly stir
Obtain modified epoxy resin.
(2) by weight, by the step of 1 part (1) prepare modification epoxy resin in ethyl alcohol remove, with 10 drop/
0.3 part of glacial acetic acid is added dropwise in min, and constant temperature stirs 2h at 25 DEG C, obtains aqueous epoxy resins.
(3) based on parts by volume, after 1 part of ethyl orthosilicate and 10- parts of ethyl alcohol are stirred evenly, PH is adjusted to 8 weak base
8 parts of ethanol water is slowly added dropwise in property, heating stirring, and constant temperature is stirred to react, and cooled to room temperature obtains the nanometer of 50nm
Silicon dioxide gel.
(4) by weight, distilled water will be slowly added in the aqueous epoxy resins of (2) preparation the step of 20 parts to be diluted to
5% aqueous epoxy resins solution, being heated to 90 DEG C makes aqueous epoxy resins activate, and 1 part of step (3) preparation is then added
Nano silicon dioxide sol is heated to 150 DEG C and is stirred to react, obtains nano-silicon dioxide modified aqueous epoxy resins, finally
3 parts of aromatic amine curing agent, 0.5 part of aromatic amine antioxidant is added, is uniformly mixing to obtain the nanometer for carbon fiber
Aqueous epoxy resins sizing agent.
Comparative example 2
(1) by weight, 1 part of bisphenol A type epoxy resin is dissolved in 8 parts of alcohol solvent, is stirred in 70 DEG C of heating
It mixes to epoxy resin and is completely dissolved, 0.9 part of diglycolamine solution is then slowly added dropwise with the rate of 5 drops/min, quickly stir
Obtain modified epoxy resin.
(2) by weight, by the step of 1 part (1) prepare modification epoxy resin in ethyl alcohol remove, with 15 drop/
0.7 part of glacial acetic acid is added dropwise in min, and constant temperature stirs 3h at 30 DEG C, obtains aqueous epoxy resins.
(3) based on parts by volume, after 1 part of ethyl orthosilicate and 13 parts of ethyl alcohol are stirred evenly, PH is adjusted to 9 weak base
10 parts of ethanol water is slowly added dropwise in property, heating stirring, and constant temperature is stirred to react, and cooled to room temperature obtains receiving for 100nm
Rice silicon dioxide gel.
(4) by weight, distilled water will be slowly added in the aqueous epoxy resins of (2) preparation the step of 40 parts to be diluted to
8% aqueous epoxy resins solution, being heated to 100 DEG C makes aqueous epoxy resins activate, and is then added prepared by step (3) 8 parts
Nano silicon dioxide sol, be heated to 160 DEG C and be stirred to react, obtain nano-silicon dioxide modified aqueous epoxy resins, most
8 parts of aromatic amine curing agent, 3 parts of aromatic amine antioxidant and 30 parts of isopropanol are added afterwards, is uniformly mixing to obtain use
In the nanometer waterborne epoxy resin sizing agent of carbon fiber.
Comparative example 3
Difference from example 1 is that nano silicon dioxide is scattered under the conditions of ultrasonic agitation in epoxy resin.
Comparative example 4
With the difference of embodiment 1, nano silicon dioxide in the presence of dispersants, is scattered in epoxy resin.
Slurry viscose-based carbon fiber starching is gone using the sizing agent of above-described embodiment and comparative example, the impregnation time is 60s, dry
Moisture is removed to get to carbon fibre composite.
Test to obtain carbon fiber in above-described embodiment and comparative example according to the analysis of test methods of tensile strength of carbon fibers
Tensile strength is listed in following table.
After testing, the silica modified epoxy resin starching of carbon fiber Wesy interface enhancement type nanometer that prepared by embodiment 1-7
The following institute of rate of sizing result of the rate of sizing of agent and the nano-silicon dioxide modified epoxy resin solvent-borne type sizing agent of comparative example 1,2
Show：
Although the above-mentioned specific implementation mode in conjunction with to the present invention is described, not to the scope of the present invention
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art do not need
Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (9)
1. a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, which is characterized in that specific system
Preparation Method is as follows：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in third
In ketone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue stirring 2 after addition
Hour, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, acetone is distilled off, obtains nano-silicon dioxide modified ring
Oxygen resin；
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
3.5g emulsifier sp60, heat and stir to get mixed liquor, and water is then instilled in mixed liquor, and after water adds, stirring obtains boundary
The silica modified epoxy resin sizing agent of face enhancement type nanometer；The addition of above-mentioned water is divided into two processes, the first process：Water is slow
Slowly it is added dropwise in nano-silicon dioxide modified epoxy resin composition, rate of addition 1-1000mL/h, the content of this stage water
It is less, form water-in-oil emulsion；Second process：With the gradually instillation of dampening, the content of water is stepped up, when mixed liquor is mutated
When at milky, emulsion oil-in-water is formd, for water as continuous phase, nano-silicon dioxide modified epoxy resin is dispersion at this time
Phase increases the rate of addition of water after mutation, that is, enters the second process, and the rate of addition of water becomes 0.1-10L/h, total amount of water
For 45g, after waiting for water droplet to add entirely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent；
The grain size of the nano silicon dioxide is in 1 ~ 100nm.
2. a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, which is characterized in that specific system
Preparation Method is as follows：
30g glycidic amine type AG80 epoxy resin is added in 150g toluene, after stirring 1.5 hours, epoxy resin is equably
It is dissolved in toluene, 0.03g nano silicon dioxides is slowly added in epoxy resin/toluene solution, are added while stirring, are added
Continue stirring 2.5 hours after entering, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, toluene distillation is gone out, obtains nanometer
Silica modified epoxy resin；
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
2.0g emulsifier TW60, heat and stir to get mixed liquor, and water is then instilled in mixed liquor, and after water adds, stirring obtains boundary
The silica modified epoxy resin sizing agent of face enhancement type nanometer；The addition of above-mentioned water is divided into two processes, the first process：Water is slow
Slowly it is added dropwise in nano-silicon dioxide modified epoxy resin composition, rate of addition 1-1000mL/h, the content of this stage water
It is less, form water-in-oil emulsion；Second process：With the gradually instillation of dampening, the content of water is stepped up, when mixed liquor is mutated
When at milky, emulsion oil-in-water is formd, for water as continuous phase, nano-silicon dioxide modified epoxy resin is dispersion at this time
Phase increases the rate of addition of water after mutation, that is, enters the second process, and the rate of addition of water becomes 0.1-10L/h, total amount of water
For 40g, after waiting for water droplet to add entirely, high-speed stirred 5 hours obtains nano-silicon dioxide modified epoxy resin sizing agent；
The grain size of the nano silicon dioxide is in 1 ~ 100nm.
3. a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, which is characterized in that specific system
Preparation Method is as follows：
30g 732# epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in dimethyl Asia
In sulfone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue stirring 2 after addition
Hour, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, acetone is distilled off, obtains nano-silicon dioxide modified ring
Oxygen resin；
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
3.5g emulsifier sp60, heat and stir to get mixed liquor, and water is then instilled in mixed liquor, and after water adds, stirring obtains boundary
The silica modified epoxy resin sizing agent of face enhancement type nanometer；The addition of above-mentioned water is divided into two processes, the first process：Water is slow
Slowly it is added dropwise in nano-silicon dioxide modified epoxy resin composition, rate of addition 1-1000mL/h, the content of this stage water
It is less, form water-in-oil emulsion；Second process：With the gradually instillation of dampening, the content of water is stepped up, when mixed liquor is mutated
When at milky, emulsion oil-in-water is formd, for water as continuous phase, nano-silicon dioxide modified epoxy resin is dispersion at this time
Phase increases the rate of addition of water after mutation, that is, enters the second process, and the rate of addition of water becomes 0.1-10L/h, total amount of water
For 45g, after waiting for water droplet to add entirely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent；
The grain size of the nano silicon dioxide is in 1 ~ 100nm.
4. a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, which is characterized in that specific system
Preparation Method is as follows：
30g ERL-4221 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in, first
In alcohol, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue stirring 2 after addition
Hour, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, acetone is distilled off, obtains nano-silicon dioxide modified ring
Oxygen resin；
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
3.5g emulsifier sp60, heat and stir to get mixed liquor, and water is then instilled in mixed liquor, and after water adds, stirring obtains boundary
The silica modified epoxy resin sizing agent of face enhancement type nanometer；The addition of above-mentioned water is divided into two processes, the first process：Water is slow
Slowly it is added dropwise in nano-silicon dioxide modified epoxy resin composition, rate of addition 1-1000mL/h, the content of this stage water
It is less, form water-in-oil emulsion；Second process：With the gradually instillation of dampening, the content of water is stepped up, when mixed liquor is mutated
When at milky, emulsion oil-in-water is formd, for water as continuous phase, nano-silicon dioxide modified epoxy resin is dispersion at this time
Phase increases the rate of addition of water after mutation, that is, enters the second process, and the rate of addition of water becomes 0.1-10L/h, total amount of water
For 45g, after waiting for water droplet to add entirely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent；
The grain size of the nano silicon dioxide is in 1 ~ 100nm.
5. a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, which is characterized in that specific system
Preparation Method is as follows：
30g UVR-6100 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in second two
In alcohol, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue stirring 2 after addition
Hour, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, acetone is distilled off, obtains nano-silicon dioxide modified ring
Oxygen resin；
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
3.5g emulsifier sp80, heat and stir to get mixed liquor, and water is then instilled in mixed liquor, and after water adds, stirring obtains boundary
The silica modified epoxy resin sizing agent of face enhancement type nanometer；The addition of above-mentioned water is divided into two processes, the first process：Water is slow
Slowly it is added dropwise in nano-silicon dioxide modified epoxy resin composition, rate of addition 1-1000mL/h, the content of this stage water
It is less, form water-in-oil emulsion；Second process：With the gradually instillation of dampening, the content of water is stepped up, when mixed liquor is mutated
When at milky, emulsion oil-in-water is formd, for water as continuous phase, nano-silicon dioxide modified epoxy resin is dispersion at this time
Phase increases the rate of addition of water after mutation, that is, enters the second process, and the rate of addition of water becomes 0.1-10L/h, total amount of water
For 45g, after waiting for water droplet to add entirely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent；
The grain size of the nano silicon dioxide is in 1 ~ 100nm.
6. a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, which is characterized in that specific system
Preparation Method is as follows：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in third
In ketone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue stirring 2 after addition
Hour, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, acetone is distilled off, obtains nano-silicon dioxide modified ring
Oxygen resin；
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
3.5g emulsifier TW-60, heat and stir to get mixed liquor, and water is then instilled in mixed liquor, and after water adds, stirring obtains
The silica modified epoxy resin sizing agent of interface enhancement type nanometer；The addition of above-mentioned water is divided into two processes, the first process：Water
It is slowly added dropwise in nano-silicon dioxide modified epoxy resin composition, rate of addition 1-1000mL/h, this stage water contains
Measure less, formation water-in-oil emulsion；Second process：With the gradually instillation of dampening, the content of water is stepped up, when mixed liquor is prominent
When becoming milky, emulsion oil-in-water is formd, water is point as continuous phase, nano-silicon dioxide modified epoxy resin at this time
Dephasing increases the rate of addition of water after mutation, that is, enters the second process, and the rate of addition of water becomes 0.1-10L/h, Zong Jiashui
Amount is 45g, and after waiting for water droplet to add entirely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent；
The grain size of the nano silicon dioxide is in 1 ~ 100nm.
7. a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, which is characterized in that specific system
Preparation Method is as follows：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in third
In ketone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue stirring 2 after addition
Hour, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, acetone is distilled off, obtains nano-silicon dioxide modified ring
Oxygen resin；
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
3.5g agriculture breasts 100, heat and stir to get mixed liquor, and water is then instilled in mixed liquor, and after water adds, stirring obtains boundary
The silica modified epoxy resin sizing agent of face enhancement type nanometer；The addition of above-mentioned water is divided into two processes, the first process：Water is slow
Slowly it is added dropwise in nano-silicon dioxide modified epoxy resin composition, rate of addition 1-1000mL/h, the content of this stage water
It is less, form water-in-oil emulsion；Second process：With the gradually instillation of dampening, the content of water is stepped up, when mixed liquor is mutated
When at milky, emulsion oil-in-water is formd, for water as continuous phase, nano-silicon dioxide modified epoxy resin is dispersion at this time
Phase increases the rate of addition of water after mutation, that is, enters the second process, and the rate of addition of water becomes 0.1-10L/h, total amount of water
For 45g, after waiting for water droplet to add entirely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent；
The grain size of the nano silicon dioxide is in 1 ~ 100nm.
8. a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, which is characterized in that specific system
Preparation Method is as follows：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in third
In ketone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue stirring 2 after addition
Hour, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, acetone is distilled off, obtains nano-silicon dioxide modified ring
Oxygen resin；
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Pungent No. 10 of 3.5g phosphorus, heats and stirs to get mixed liquor, water is then instilled in mixed liquor, and after water adds, stirring obtains interface
The silica modified epoxy resin sizing agent of enhancement type nanometer；The addition of above-mentioned water is divided into two processes, the first process：Water is slow
Be added dropwise in nano-silicon dioxide modified epoxy resin composition, rate of addition 1-1000mL/h, the content of this stage water compared with
It is few, form water-in-oil emulsion；Second process：With the gradually instillation of dampening, the content of water is stepped up, when mixed liquor is mutated into
When milky, emulsion oil-in-water is formd, for water as continuous phase, nano-silicon dioxide modified epoxy resin is dispersion at this time
Phase increases the rate of addition of water after mutation, that is, enters the second process, and the rate of addition of water becomes 0.1-10L/h, total amount of water
For 45g, after waiting for water droplet to add entirely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent；
The grain size of the nano silicon dioxide is in 1 ~ 100nm.
9. a kind of silica modified epoxy resin sizing agent of carbon fiber Wesy interface enhancement type nanometer, which is characterized in that specific system
Preparation Method is as follows：
30g bisphenol A-type E51 epoxy resin is added in 300g acetone, after stirring 1 hour, epoxy resin is dissolves uniformly in third
In ketone, 3g nano silicon dioxides are slowly added in epoxy resin/acetone soln, are added while stirring, continue stirring 2 after addition
Hour, after being uniformly dispersed, mixed liquor is evaporated under reduced pressure, acetone is distilled off, obtains nano-silicon dioxide modified ring
Oxygen resin；
After obtaining nano-silicon dioxide modified epoxy resin, the nano-silicon dioxide modified epoxy resin of 30g is taken, is added wherein
Pungent No. 10 of 3.5g phosphorus, heats and stirs to get mixed liquor, water is then instilled in mixed liquor, and after water adds, stirring obtains interface
The silica modified epoxy resin sizing agent of enhancement type nanometer；The addition of above-mentioned water is divided into two processes, the first process：Water is slow
Be added dropwise in nano-silicon dioxide modified epoxy resin composition, rate of addition 1-1000mL/h, the content of this stage water compared with
It is few, form water-in-oil emulsion；Second process：With the gradually instillation of dampening, the content of water is stepped up, when mixed liquor is mutated into
When milky, emulsion oil-in-water is formd, for water as continuous phase, nano-silicon dioxide modified epoxy resin is dispersion at this time
Phase increases the rate of addition of water after mutation, that is, enters the second process, and the rate of addition of water becomes 0.1-10L/h, total amount of water
For 45g, after waiting for water droplet to add entirely, high-speed stirred 4 hours obtains nano-silicon dioxide modified epoxy resin sizing agent；
The grain size of the nano silicon dioxide is in 1 ~ 100nm.
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| CN106811966B (en) * | 2017-01-24 | 2019-05-14 | 哈尔滨工业大学 | A kind of method of acrylic amide aqueous solution grafting modified carbon fiber surface size agent |
| CN107033734B (en) * | 2017-04-07 | 2019-10-11 | 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 |
| 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 |
| 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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