CN109423006A - A kind of preparation method of graphene composite epoxy resin - Google Patents
A kind of preparation method of graphene composite epoxy resin Download PDFInfo
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- CN109423006A CN109423006A CN201710571825.2A CN201710571825A CN109423006A CN 109423006 A CN109423006 A CN 109423006A CN 201710571825 A CN201710571825 A CN 201710571825A CN 109423006 A CN109423006 A CN 109423006A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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Abstract
The present invention provides a kind of preparation methods of graphene composite epoxy resin, include the following steps, after first mixing graphene organic dispersion, epoxy resin and organic solvent, obtain precursor solution；Then after precursor solution above-mentioned steps obtained is ground and is ultrasonically treated, mixed solution is obtained；After the mixed solution that finally above-mentioned steps are obtained carries out high-temperature vacuum revolving, graphene composite epoxy resin is obtained.The present invention rotates the mode matched only with grinding, ultrasonic treatment and high-temperature vacuum, in conjunction with specific composite steps, only by the compound method of physics, so that graphite is dilute with epoxy resin good combination, in microcosmic upper realization layer upon layer, the smooth arrangement of graphene film is realized on the graphene modified epoxy membrane structure of macroscopic view, the orientation of graphene film and film two-dimensional are equally oriented, the stratiform for realizing graphene is orderly distributed, and has reached the order of resinae high molecular material three-level assembling.
Description
Technical field
The invention belongs to resin material technical field more particularly to a kind of preparation methods of graphene composite epoxy resin.
Background technique
Epoxy resin is the organic compound referred in molecule containing two or more epoxy groups, epoxy resin
Molecular structure be by strand contain active epoxy group characterized by, epoxy group can be located at strand end,
Centre or circlewise structure.It can be cross-linked to form with a plurality of types of curing agent due to containing active epoxy group in molecular structure
Insoluble tridimensional network, the high-molecular compound containing epoxy group is referred to as epoxy resin in all molecular structures.Solidification
Epoxy resin afterwards has good physics, chemical property, it has excellent bonding to the surface of metal and nonmetallic materials
Intensity, dielectric properties are good, and deformation retract rate is small, and product size stability is good, and hardness is high, and flexibility is preferable, to alkali and big portion
Point solvent-stable, thus be widely used in national defence, each department of national economy is poured, impregnates, lamination material, bonding agent and painting
The purposes such as material.But common epoxy resin weatherability is bad, solar radiation is long to be possible to powder phenomenon-tion occur；Dicoration compared with
Difference, gloss are not easy to keep；More demanding to construction environment, curing at low temperatures is slow, and effect is bad；Many kinds need high temperature solid
Change, the investment of equipment is larger.Therefore, the project compound and resin material field of epoxy resin often paid close attention to.
Graphene (Graphene) is a kind of new material of individual layer laminated structure being made of carbon atom.It is one kind by carbon
Atom forms the flat film that hexangle type is in honeycomb lattice, the two-dimensional material of only one carbon atom thickness with sp2 hybridized orbit.
Graphene is to enter most thin material and most tough material in application field at present, also has huge theoretical specific surface area,
Physicochemical properties are stablized, and good structural stability can be kept under high working voltage and high current fast charging and discharging, excellent
Electric conductivity etc. so that graphene and its derivative be in energy storage material, environmental project is widely used in terms of sensing sensitive,
Referred to as " dark fund " or " king of new material ".
And the powerful active force exactly between the intensity and carbon atom of the superelevation that have of graphite alkenes material, it makes it possible to
It is widely used among novel high-strength composite material as additive.Graphene modified epoxy is exactly one of them, is changed
Graphene composite epoxy resin is corrosion-resistant after property, and the performances such as weatherability, shock resistance significantly improve.But easily due to graphene
Reunite, and the graphite alkenes material specific surface area such as graphene and its derivative is larger, there is stronger Van der Waals each other and make
Firmly, reunite and wrapping phenomena be obvious, prevent it from stable dispersion, also be easy to reunite again after dispersion to be difficult to open together,
So graphene is difficult to evenly dispersed in the epoxy and arrangement, cause the performance of graphene composite epoxy resin also not enough
Ideal, because of this, graphene and resin material are compound logical in the prior art to avoid the unstable of graphite alkenes material
It is all often that graphene is added in the resins synthesis stage to carry out compound, but such technique not only complex process, at high cost, Er Qie
Graphene is added in the polymerization stage of resin, and uncertain factor is too many, influences each other, it is difficult to control, while prepare composite material
Used in the process of organic solvent it is more, environment is unfriendly, does not meet the theory of current Green Development.
Therefore, a kind of preparation method of more optimal graphene composite epoxy resin how is found, graphene is improved and exists
Epoxy resin evenly dispersed and arrangement, it has also become many production firms and a line in the industry apply research staff urgently to be resolved
Major issue.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of preparation side of graphene composite epoxy resin
Method, the preparation method of graphene composite epoxy resin provided by the invention, the graphene that can make are uniformly distributed in resin, real
The smooth arrangement of existing graphene film, and simple process is easily operated, it is environment friendly and pollution-free, it is suitble to large-scale industrial production.
The present invention provides a kind of preparation methods of graphene composite epoxy resin, comprising the following steps:
A after) mixing graphene organic dispersion, epoxy resin and organic solvent, precursor solution is obtained；
B after) precursor solution for obtaining above-mentioned steps is ultrasonically treated, mixed solution is obtained；
C after) mixed solution for obtaining above-mentioned steps carries out high-temperature vacuum revolving, graphene composite epoxy resin is obtained.
Preferably, the mass fraction of the graphene organic dispersion is 0.1%~3%；
The dispersing agent of the graphene organic dispersion includes dimethylbenzene, n-butanol, acetone, dimethanol, toluene and N- first
One of base pyrrolidones is a variety of；
The mass ratio of the graphene and the epoxy resin is 0.5%~5%.
Preferably, the graphene includes single-layer graphene, bilayer graphene, multi-layer graphene, graphene oxide and answers
Close one of graphene or a variety of；
The epoxy resin includes bisphenol A type epoxy resin；
The organic solvent includes one in dimethylbenzene, n-butanol, acetone, dimethanol, toluene and N-Methyl pyrrolidone
Kind is a variety of；
The mass ratio of the epoxy resin and the organic solvent is (1~4): 1.
Preferably, the graphene organic dispersion is obtained after ultrasonic agitation by graphene slurry and dispersing agent；
The solid content of the graphene slurry is 0.5%~10%.
Preferably, the time of the ultrasonic agitation is 20~120min；
The frequency of the ultrasound is 20~80kHz；
The revolving speed of the stirring is 200~600r/min.
Preferably, the step A) specifically:
A1) epoxy resin and organic solvent are first mixed, obtain epoxy resin solution；
A2 it) again into the epoxy resin solution that above-mentioned steps obtain, is slowly added to graphene organic dispersion and ultrasound is stirred
It mixes, obtains precursor solution.
Preferably, the step A1) in, it is described to be mixed into ultrasonic agitation；
The time of the ultrasonic agitation is 20~120min；
The frequency of the ultrasound is 20~80kHz；
The revolving speed of the stirring is 200~900r/min.
Preferably, the step A2) in, it is described to be incorporated slowly as being added dropwise；
The time of the ultrasonic agitation is 20~120min；
The frequency of the ultrasound is 20~80kHz；
The revolving speed of the stirring is 200~900r/min.
Preferably, the step B) in, it is described to be ground to wet grinding；
The time of the grinding is 10~180min；The revolving speed of the grinding is 200~500r/s；
The ultrasonic treatment is ultrasonic agitation；
The time of the ultrasonic treatment is 20~120min；The frequency of the ultrasonic treatment is 20~80kHz；
The revolving speed of the stirring is 200~900r/min.
Preferably, the step C) in, the temperature of the high-temperature vacuum revolving is 40~90 DEG C；
The pressure of the high-temperature vacuum revolving is 20~200mbar；
The revolving speed of the high-temperature vacuum revolving is 20~70r/min.
The present invention provides a kind of preparation methods of graphene composite epoxy resin, include the following steps, first by graphite
After alkene organic dispersions, epoxy resin and organic solvent mixing, precursor solution is obtained；Then forerunner above-mentioned steps obtained
After liquid solution is ground and is ultrasonically treated, mixed solution is obtained；The mixed solution that finally above-mentioned steps are obtained carries out high temperature
After vacuum revolving, graphene composite epoxy resin is obtained.Compared with prior art, the present invention is difficult to for graphene in asphalt mixtures modified by epoxy resin
Evenly dispersed and arrangement in rouge, and be usually all compound in resins synthesis stage addition graphene progress in prior art, but deposit
In multiple technologies problem, and cumbersome defect not environmentally.
The present invention overcomes cannot make graphene equally distributed skill in resin only with physical method in existing idea
Art prejudice, while graphene microchip is also no longer limited on raw material, between multiple steps and parameter during the preparation process into
Row many experiments and creative exploration, creative is matched using grinding, ultrasonic treatment and high-temperature vacuum revolving, in conjunction with spy
Fixed composite steps, only by the compound method of physics, so that graphite is dilute with epoxy resin good combination, in microcosmic upper realization
Layer upon layer, it is evenly dispersed, and the smooth of graphene film can be realized on the graphene modified epoxy membrane structure of macroscopic view
Arrangement, the orientation of graphene film is equally oriented with film two-dimensional, and the stratiform for realizing graphene is orderly distributed, and has reached resinae
The order of high molecular material three-level assembling, to make graphene modified epoxy that there are many good physical chemistry
Can, closer to ideal combined state.Effective solution of the present invention conventional method prepares graphene modified epoxy, graphite
Seriously accumulation overlapping, is unevenly distributed, especially graphene cannot be orderly distributed in resin in resin between alkene lamella
Intrinsic problem, and present invention process is simply easily operated, low in cost to be easy to large-scale production and environment friendly and pollution-free, preparation
Graphene composite epoxy resin compact structure, have high insulating, can preferably protect metal body in fields such as coating
From corrosion.
The experimental results showed that the acidproof, alkali resistance using paint film that graphene composite epoxy resin prepared by the present invention is made into
Ordinary epoxy resin can be significantly better than, mechanical property is also significantly better than ordinary epoxy resin.
Detailed description of the invention
Fig. 1 is the process flow diagram of the embodiment of the present invention 1；
Fig. 2 is after the graphene composite epoxy resin of preparation of the embodiment of the present invention solidifies and after ordinary epoxy resin solidification
Appearance photo comparison；
Fig. 3 is the stereoscan photograph of graphene composite epoxy resin prepared by the embodiment of the present invention 1；
Fig. 4 is the stereoscan photograph of the blank epoxy resin with the trade mark in proportion.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, present invention preferably employs analyze pure or resin material or
The conventional purity that field of graphene uses.
The present invention provides a kind of preparation methods of graphene composite epoxy resin, comprising the following steps:
A after) mixing graphene organic dispersion, epoxy resin and organic solvent, precursor solution is obtained；
B after) precursor solution for obtaining above-mentioned steps is ground and is ultrasonically treated, mixed solution is obtained；
C after) mixed solution for obtaining above-mentioned steps carries out high-temperature vacuum revolving, graphene composite epoxy resin is obtained.
After the present invention first mixes graphene organic dispersion, epoxy resin and organic solvent, precursor solution is obtained.
The graphene organic dispersion is not particularly limited in the present invention, with graphene well known to those skilled in the art
Organic dispersions, can conventionally prepare or commercially available purchase, those skilled in the art can be according to realities
The border condition of production, product requirement and quality control are selected and are adjusted.
The present invention concentration of the graphene organic dispersion is not particularly limited the present invention, with this field skill
The concentration of graphene organic dispersion known to art personnel, those skilled in the art can be according to practical conditions, production
Product require and quality control is selected and adjusted, and the present invention is to further increase the uniformity and performance of subsequent product, institute
The mass fraction for stating graphene organic dispersion is preferably 0.1%~3%, and more preferably 0.5%~2.5%, most preferably 1%
~2%.
The source of the graphene organic dispersion is not particularly limited in the present invention, with well known to those skilled in the art
The usual sources of graphene organic dispersion, can conventionally prepare or commercially available purchase, this field skill
Art personnel can control according to practical condition, product requirement and quality and select and adjust, and the present invention is further
The uniformity and performance of subsequent product are improved, the graphene organic dispersion is preferably stirred by graphene and dispersing agent by ultrasound
It obtains after mixing, is more preferably obtained after ultrasonic agitation by graphene slurry and dispersing agent.
The graphene is not particularly limited in the present invention, can be with graphene well known to those skilled in the art
It conventionally prepares or commercially available purchase, those skilled in the art can be according to practical condition, product requirement
And quality control is selected and is adjusted, the present invention is to further increase the uniformity and performance of subsequent product, the graphite
Alkene preferably refers to sensu lato graphene, preferably includes single-layer graphene, bilayer graphene, multi-layer graphene, graphene oxide
With one of composite graphite alkene or a variety of, more preferably single-layer graphene, bilayer graphene, multi-layer graphene, graphite oxide
Alkene or composite graphite alkene, most preferably mono-layer graphite is dilute, bilayer graphene or the graphene less than ten layers, is specifically as follows Europe
Platinum company also can satisfy requirement from the graphene produced, other type graphenes.In addition, graphene of the present invention can also be with
For graphene microchip, that is, it is more than or equal to ten layers of graphene.The present invention limits smaller, range to the form of the graphene raw material
It is wider, it can adapt to the graphene of diversified forms on the market, such as graphene powder, graphene slurry, graphene dispersing solution.
The source of the graphene or graphene slurry is not particularly limited in the present invention, known to those skilled in the art
Graphene or graphene slurry usual sources, can conventionally prepare or commercially available purchase, ability
Field technique personnel can according to practical condition, product requirement and quality control select and adjust, the present invention be into
One step improves the uniformity and performance of subsequent product, the graphene slurry that the graphene slurry can be standby for Shandong Europe platinum corporation
Material.
The concentration of the graphene slurry is not particularly limited in the present invention, with graphene well known to those skilled in the art
The normal concentration of slurry, can conventionally prepare or commercially available purchase, those skilled in the art can roots
It is selected and is adjusted according to the control of practical condition, product requirement and quality, the present invention is to further increase subsequent product
Uniformity and performance, the solid content of the graphene slurry is preferably 0.5%~10%, more preferably 1%~9%, it is more excellent
It is selected as 3%~7%, more preferably 4%~6%.
The dispersing agent is not particularly limited in the present invention, with well known to those skilled in the art for dispersed graphite alkene
Dispersing agent, those skilled in the art can according to practical condition, product requirement and quality control select and
Adjustment, the present invention is to further increase the uniformity and performance of subsequent product, and the solvent of the graphene organic dispersion is preferred
Including one of dimethylbenzene, n-butanol, acetone, dimethanol, toluene and N-Methyl pyrrolidone or a variety of, more preferably diformazan
Benzene, n-butanol, acetone, dimethanol, toluene or N-Methyl pyrrolidone, most preferably dimethylbenzene or n-butanol.
The time of the ultrasonic agitation is not particularly limited in the present invention, with ultrasonic agitation well known to those skilled in the art
Time, those skilled in the art can according to practical condition, product requirement and quality control select and
Adjustment, the present invention is to further increase the uniformity and performance of subsequent product, optimized process flow, the time of the ultrasonic agitation
Preferably 20~120min, more preferably 40~100min, more preferably 60~80min.
The supersonic frequency of the ultrasonic agitation is not particularly limited in the present invention, with ultrasound well known to those skilled in the art
Frequency, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust
Whole, the present invention is to further increase the uniformity and performance of subsequent product, and the frequency of optimized process flow, the ultrasound is preferably
20~80kHz, more preferably 30~70kHz, most preferably 40~60kHz.
The speed of agitator of the ultrasonic agitation is not particularly limited in the present invention, with stirring well known to those skilled in the art
Revolving speed, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust
Whole, the present invention is to further increase the uniformity and performance of subsequent product, and the revolving speed of optimized process flow, the speed of agitator is excellent
It is selected as 200~600r/min, more preferably 300~500r/min, most preferably 350~450r/min.
The epoxy resin is not particularly limited in the present invention, with epoxy resin well known to those skilled in the art,
It can conventionally prepare or commercially available purchase, epoxy resin of the present invention preferably include bisphenol A type epoxy resin,
It is more specifically preferably E-51 bisphenol A type epoxy resin and/or 601 bisphenol A type epoxy resins, most preferably E-51 bisphenol-A type ring
Oxygen resin or 601 bisphenol A type epoxy resins.
The ratio of the graphene organic dispersion and epoxy resin is not particularly limited in the present invention, those skilled in the art
Member can control according to practical condition, product requirement and quality and be selected and be adjusted, and the present invention is to further increase
The mass ratio of the uniformity and performance of subsequent product, the graphene organic dispersion and the epoxy resin is preferably 0.5%
~5%, more preferably 1%~4.5%, more preferably 1.5%~4%, most preferably 2%~3.5%.
The organic solvent is not particularly limited in the present invention, is with conventional organic solvent well known to those skilled in the art
Can, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust, this hair
Bright is to further increase the uniformity and performance of subsequent product, the organic solvent preferably include dimethylbenzene, n-butanol, acetone,
One of dimethanol, toluene and N-Methyl pyrrolidone are a variety of, more preferably dimethylbenzene, n-butanol, acetone, dimethanol,
Toluene or N-Methyl pyrrolidone, most preferably dimethylbenzene or n-butanol.
The additional amount of the organic solvent is not particularly limited in the present invention, is added with routine well known to those skilled in the art
Enter amount, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust
Whole, the mass ratio of epoxy resin of the present invention and the organic solvent is preferably (3~5): 1, more preferably (3.3~4.8):
1, most preferably (3.5~4.5): 1.
The present invention is to further increase the uniformity and performance of subsequent product, optimized process flow, complete process process, institute
State step A) it is particularly preferred as:
A1) epoxy resin and organic solvent are first mixed, obtain epoxy resin solution；
A2 it) again into the epoxy resin solution that above-mentioned steps obtain, is slowly added to graphene organic dispersion and ultrasound is stirred
It mixes, obtains precursor solution.
The concrete mode first mixed is not particularly limited in the present invention, with mixing side well known to those skilled in the art
Formula, those skilled in the art can require according to practical condition, activation and quality control is selected and adjusted,
The present invention is to further increase the uniformity and performance of subsequent product, and optimized process flow is described first to mix, i.e., the described step
A1) mode mixed is preferably stirred by ultrasonic.
The time of the ultrasonic agitation is not particularly limited in the present invention, with ultrasonic agitation well known to those skilled in the art
Time, those skilled in the art can according to practical condition, product requirement and quality control select and
Adjustment, the present invention is to further increase the uniformity and performance of subsequent product, optimized process flow, the time of the ultrasonic agitation
Preferably 20~120min, more preferably 40~100min, more preferably 60~80min.
The supersonic frequency of the ultrasonic agitation is not particularly limited in the present invention, with ultrasound well known to those skilled in the art
Frequency, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust
Whole, the present invention is to further increase the uniformity and performance of subsequent product, and the frequency of optimized process flow, the ultrasound is preferably
20~80kHz, more preferably 30~70kHz, most preferably 40~60kHz.
The speed of agitator of the ultrasonic agitation is not particularly limited in the present invention, with stirring well known to those skilled in the art
Revolving speed, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust
Whole, the present invention is to further increase the uniformity and performance of subsequent product, and the revolving speed of optimized process flow, the speed of agitator is excellent
It is selected as 200~900r/min, more preferably 300~800r/min, more preferably 400~700r/min, most preferably 500~
600r/min。
The concrete mode being slowly added to is not particularly limited in the present invention, with well known to those skilled in the art slow
The usual manner of addition, those skilled in the art can according to practical condition, activation require and quality control into
Row selection and adjustment, the present invention is to further increase the uniformity and performance of subsequent product, optimized process flow, described slowly to add
The mode entered is preferably added dropwise.
The present invention is to the step A2) in, the time of the ultrasonic agitation is not particularly limited, with those skilled in the art
The time of well known ultrasonic agitation, those skilled in the art can be according to practical condition, product requirement and quality
Control is selected and is adjusted, and the present invention is to further increase the uniformity and performance of subsequent product, and optimized process flow is described
The time of ultrasonic agitation is preferably 20~120min, more preferably 40~100min, more preferably 60~80min.
The present invention states step A2 to described) in, the supersonic frequency of the ultrasonic agitation is not particularly limited, with this field skill
Supersonic frequency known to art personnel, those skilled in the art can be according to practical condition, product requirement and quality
Control is selected and is adjusted, and the present invention is to further increase the uniformity and performance of subsequent product, and optimized process flow is described
The frequency of ultrasound is preferably 20~80kHz, more preferably 30~70kHz, most preferably 40~60kHz.
The present invention is to the step A2) in, the speed of agitator of the ultrasonic agitation is not particularly limited, with art technology
Speed of agitator known to personnel, those skilled in the art can be according to practical condition, product requirement and quality controls
System is selected and is adjusted, and the present invention is to further increase the uniformity and performance of subsequent product, and optimized process flow is described to stir
The revolving speed for mixing revolving speed is preferably 200~900r/min, more preferably 300~800r/min, more preferably 400~700r/min,
Most preferably 500~600r/min.
After the precursor solution that the present invention then obtains above-mentioned steps grinds and is ultrasonically treated, obtain mixing molten
Liquid.
The concrete mode of the grinding is not particularly limited in the present invention, and those skilled in the art can be according to actual production
Situation, activation require and quality control selected and adjusted, the present invention be further increase subsequent product uniformity and
Performance is preferably realized evenly dispersed and combination, the concrete mode of the grinding of graphene and epoxy resin is preferably wet
Method grinding, more preferably wet ball grinding.
The present invention is to the step B) in, the time of the grinding is not particularly limited, known to those skilled in the art
Grinding time, those skilled in the art can according to practical condition, product requirement and quality control carry out
Selection and adjustment, the present invention is to further increase the uniformity and performance of subsequent product, is preferably realized graphene and epoxy
The evenly dispersed and combination of resin, the time of the grinding is preferably 10~180min, more preferably 30~160min, more preferably
For 50~140min, most preferably 70~120min, it is specifically as follows 30min.
The present invention states step B to described) in, the revolving speed of the grinding is not particularly limited, ripe with those skilled in the art
The grinding revolving speed known, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, the present invention is to further increase the uniformity and performance of subsequent product, is preferably realized graphene and epoxy
The evenly dispersed and combination of resin, the revolving speed of the grinding is preferably 200~500r/s, and more preferably 250~450r/s is optimal
It is selected as 300~400r/s.
The concrete mode of the ultrasonic treatment is not particularly limited in the present invention, and those skilled in the art can be according to reality
The condition of production, activation require and quality control is selected and adjusted, and the present invention is further increase subsequent product uniform
Property and performance, optimized process flow, the concrete mode of the ultrasonic treatment be preferably stirred by ultrasonic.
The present invention is to the step B) in, the time of the ultrasonic treatment is not particularly limited, with those skilled in the art
The time of well known ultrasonic treatment, those skilled in the art can be according to practical condition, product requirement and quality
Control is selected and is adjusted, and the present invention is to further increase the uniformity and performance of subsequent product, and optimized process flow is described
The time of ultrasonic treatment is preferably 20~120min, more preferably 40~100min, more preferably 60~80min.
The present invention states step B to described) in, the supersonic frequency of the ultrasonic treatment is not particularly limited, with this field skill
Supersonic frequency known to art personnel, those skilled in the art can be according to practical condition, product requirement and quality
Control is selected and is adjusted, and the present invention is to further increase the uniformity and performance of subsequent product, and optimized process flow is described
The frequency of ultrasonic treatment is preferably 20~80kHz, more preferably 30~70kHz, most preferably 40~60kHz.
The present invention is to the step B) in, the speed of agitator of the ultrasonic agitation is not particularly limited, with art technology
Speed of agitator known to personnel, those skilled in the art can be according to practical condition, product requirement and quality controls
System is selected and is adjusted, and the present invention is to further increase the uniformity and performance of subsequent product, and optimized process flow is described to stir
The revolving speed for mixing revolving speed is preferably 200~900r/min, more preferably 300~800r/min, more preferably 400~700r/min,
Most preferably 500~600r/min.
After the mixed solution that the present invention finally obtains above-mentioned steps carries out high-temperature vacuum revolving, graphene complex loop is obtained
Oxygen resin.
High-temperature vacuum revolving of the present invention under given conditions, can be improved evaporation effect and performance.
The time that the present invention rotates the high-temperature vacuum is not particularly limited, and those skilled in the art can be according to reality
The condition of production, product requirement and quality control are selected and are adjusted, and the present invention is further increase subsequent product uniform
Property and performance, the temperature of optimized process flow, high-temperature vacuum revolving is preferably 40~90 DEG C, more preferably 50~80 DEG C,
More preferably 60~70 DEG C.
The pressure that the present invention rotates the high-temperature vacuum is not particularly limited, and those skilled in the art can be according to reality
The condition of production, product requirement and quality control are selected and are adjusted, and the present invention is further increase subsequent product uniform
Property and performance, the pressure of optimized process flow, high-temperature vacuum revolving is preferably 20~200mbar, more preferably 50~
170mbar, more preferably 80~150mbar, most preferably 100~130mbar.
The revolving speed that the present invention rotates the high-temperature vacuum is not particularly limited, and those skilled in the art can be according to reality
The condition of production, product requirement and quality control are selected and are adjusted, and the present invention is further increase subsequent product uniform
Property and performance, the revolving speed of optimized process flow, high-temperature vacuum revolving is preferably 20~70r/min, more preferably 30~
60r/min, more preferably 40~50r/min.
The present invention is to further increase the uniformity and performance of subsequent product, optimized process flow, complete process flow, institute
State high-temperature vacuum revolving after it is also preferable to include post-processing steps.
The specific steps of the post-processing are not particularly limited in the present invention, after routine well known to those skilled in the art
Processing step, those skilled in the art can require according to practical condition, activation and quality control selects
And adjustment, post-processing step of the present invention preferably include drying, are specifically as follows vacuum drying.
The vacuum drying actual conditions are not particularly limited in the present invention, and those skilled in the art can be according to reality
The condition of production, product requirement and quality control are selected and are adjusted, and vacuum drying temperature of the present invention is preferably 40
~90 DEG C, more preferably 50~80 DEG C, more preferably 60~70 DEG C.The vacuum drying time of the present invention is preferably 0.5~
3.5h, more preferably 1~3h, most preferably 1.5~2.5h.
Above-mentioned steps of the present invention provide a kind of preparation method of graphene composite epoxy resin, overcome in existing idea
Cannot make graphene equally distributed technology prejudice in resin only with physical method, multiple steps during the preparation process and
Many experiments and creative exploration are carried out between parameter, creative rotates phase using grinding, ultrasonic agitation and high-temperature vacuum
Cooperation is further refined by specific state modulator and step in conjunction with specific composite steps, compound only by physics
Method it is evenly dispersed in microcosmic upper realization layer upon layer so that graphite is dilute with epoxy resin good combination, and can be in macroscopic view
Graphene modified epoxy membrane structure on realize graphene film smooth arrangement, the orientation and film two-dimensional of graphene film
Equally oriented, the stratiform for realizing graphene is orderly distributed, and has reached the order of resinae high molecular material three-level assembling, from
And make graphene modified epoxy that there are many good physical and chemical performances, closer to ideal combined state.
Effective solution of the present invention conventional method prepares graphene modified epoxy, serious heap between graphene sheet layer
Product overlapping, is unevenly distributed in resin, the especially intrinsic problem that cannot orderly be distributed in resin of graphene, and this hair
The range of choice of bright widened raw graphite alkene overcomes and is only capable of in the prior art using graphene microchip as raw material, and
The defect of big additive amount cannot be used, while simple process is easily operated, it is low in cost to be easy to large-scale production, and environmental protection is without dirt
Dye, the graphene composite epoxy resin compact structure of preparation have high insulating, can preferably protect gold in fields such as coating
Belong to body from corrosion, also there is preferable mechanical property.
The experimental results showed that doing salt water resistance corrosion experiment in 90 DEG C of 10%NaCL solution, ordinary epoxy resin is in 60h
Left and right substrate is corroded, and graphene composite epoxy resin paint film prepared by the present invention substrate in 120h is still intact；This
The tensile strength for inventing the graphene modified epoxy resin composite of preparation can reach 69.7MPa.
In order to further illustrate the present invention, with reference to embodiments to a kind of graphene composite epoxy tree provided by the invention
The preparation method of rouge is described in detail, but it is to be understood that these embodiments are under the premise of the technical scheme of the present invention
Implemented, the detailed implementation method and specific operation process are given, only for further illustrate feature of the invention and
Advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
Weigh 40g epoxy resin 601,30g dimethylbenzene, 3g n-butanol makes to be uniformly mixed in the case where ultrasonic agitation, stirs
Revolving speed is mixed between 200~500, supersonic frequency 40kHz.
The graphene slurry 10g that solid content is 2% is weighed again, and ultrasonic agitation 30min after 30g n-butanol is added to keep graphene equal
It is even to be dispersed in n-butanol, between speed of agitator 200~500.Supersonic frequency is 40kHz.
Then scattered graphene solution is added drop-wise in 601 solution of epoxy resin in the case where ultrasonic agitation,
Obtain precursor solution.
Above-mentioned steps are obtained into precursor solution again and carry out wet ball grinding, ball milling speed 300r/s, Ball-milling Time is
30min is then stirred by ultrasonic in 30min, obtains mixed solution.
Graphene epoxy resin mixed solution is handled by the method for revolving again to stop when solvent steams 95% or so
Spin-ended steaming, obtains preliminary composite.Revolving condition are as follows: vacuum degree 5mbar, temperature 70 C, revolving speed 60.
Finally by preliminary compound material in vacuum drying oven 25 DEG C dry 4~5 hours for solvent except dry, it is multiple to obtain graphene
Close epoxy resin 601.
It is the process flow diagram of the embodiment of the present invention 1 referring to Fig. 1, Fig. 1.
The graphene composite epoxy resin prepared to the embodiment of the present invention 1 detects.
Graphene composite epoxy resin 601 prepared by above-mentioned steps of the present invention, is solidified with polyamide-based curing agent,
Compound resin, curing agent and xylene mass ratio are as follows: 3.6:1:2.
Salt water resistance corrosion experiment is done in 90 DEG C of 10%NaCL solution, paint film substrate in 144h is still intact.
Referring to fig. 2, Fig. 2 be the embodiment of the present invention preparation graphene composite epoxy resin solidification after and ordinary epoxy resin
Appearance photo comparison after solidification.Wherein, the most right side is the appearance photo after ordinary epoxy resin solidifies.
As shown in Figure 2, graphene composite epoxy resin paint film is finer and close.
The graphene composite epoxy resin prepared to the embodiment of the present invention 1 characterizes.
It is the stereoscan photograph of graphene composite epoxy resin prepared by the embodiment of the present invention 1 referring to Fig. 3, Fig. 3.Referring to
Fig. 4, Fig. 4 are the stereoscan photograph of the blank epoxy resin with the trade mark in proportion.
As can be seen from figs. 3 and 4 the embodiment of the present invention 1 is only by the compound method of physics, so that graphite is dilute and epoxy resin
Good combination realizes graphene on the graphene modified epoxy membrane structure of macroscopic view in microcosmic upper realization layer upon layer
The orientation of the smooth arrangement of piece, graphene film is equally oriented with film two-dimensional, and the stratiform for realizing graphene is orderly distributed, and reaches
The order of resinae high molecular material three-level assembling.
Mechanics Performance Testing is carried out to graphene composite epoxy resin prepared by the embodiment of the present invention 1.
Specimen size is stretched according to Test method for tensile properties of resin casting body standard GB/T/T1040.2-2006
Intensity detection, tensile strength 60.3MPa.
Embodiment 2
Weigh 60g epoxy resin E-51,30g dimethylbenzene, 3g n-butanol makes to be uniformly mixed in the case where ultrasonic agitation, stir
Revolving speed is mixed between 200~500, supersonic frequency 40kHz.
The graphene slurry 50g that solid content is 10% is weighed again, and ultrasonic agitation 30min after 30g n-butanol is added to make graphene
It is dispersed in n-butanol, between speed of agitator 200~500.Supersonic frequency is 40kHz.
Then scattered graphene solution is added drop-wise in epoxy resin E-51 solution in the case where ultrasonic agitation,
Obtain precursor solution.
Above-mentioned steps are obtained into precursor solution again and carry out wet ball grinding, ball milling speed 400r/s, Ball-milling Time is
30min is then stirred by ultrasonic in 120min, obtains mixed solution.
Graphene epoxy resin mixed solution is handled by the method for revolving again to stop when solvent steams 95% or so
Spin-ended steaming, obtains preliminary composite.Revolving condition are as follows: vacuum degree 5mbar, temperature 70 C, revolving speed 60.
Again by preliminary compound material in vacuum drying oven 25 DEG C dry 4~5 hours for solvent except dry, it is compound to obtain graphene
Epoxy resin E-51.
Graphene composite epoxy resin E-51 prepared by above-mentioned steps of the present invention, is consolidated with polyamide-based curing agent
Change, compound resin, curing agent and xylene mass ratio are as follows: 4.1:1:2.
Salt water resistance corrosion experiment is done in 90 DEG C of 10%NaCL solution, paint film substrate in 120h is still intact.
Mechanics Performance Testing is carried out to graphene composite epoxy resin prepared by the embodiment of the present invention 2.
Specimen size is stretched according to Test method for tensile properties of resin casting body standard GB/T/T1040.2-2006
Intensity detection, tensile strength 69.7MPa.
Comparative example 1
1) the graphene slurry 2g that solid content is 5% is weighed, is added in 50ml acetone, ultrasonic power 0.8kW, ice-water bath
Ultrasonic disperse 1 hour, form the dispersion liquid of black even.
100g epoxy resin E-51 is added in the resulting graphene acetone soln of step 1), ice-water bath ultrasonic disperse 1 is small
When, ultrasonic power 0.8kW, after mixing, at 0.01MPa pressure and 40 DEG C, with the speed of 60r/min, vacuum revolving is removed
Remove solvent.
3) 50g kymene 00 is added in the mixture through ultrasonic disperse obtained by step 2), high-speed stirred 30 minutes, turns
Fast 1500r/min.It is placed in vacuum drying oven, excludes bubble under the conditions of room temperature, 0.05MPa, until bubble-free is overflowed in mixture.
4) gained mixture in step 3) is poured slowly into mold, mold coats release agent in advance and passes through 70 DEG C in advance
Heat.It is put into baking oven and solidifies 3 hours for 60 DEG C, then cool to room temperature, graphene/epoxy resin composite material is obtained after demoulding.
(specimen size is according to casting resin for the graphene/epoxy resin composite material prepared to above-mentioned steps of the present invention
Erichsen test method standard GB/T/T1040.2-2006) carry out tensile strength detection, the results showed that, the present invention compares
The tensile strength of graphene modified epoxy resin composite prepared by example 1 is 49.7MPa.
A kind of preparation method of graphene composite epoxy resin provided by the invention is described in detail above, this
Apply that a specific example illustrates the principle and implementation of the invention in text, the explanation of above example is only intended to
It facilitates the understanding of the method and its core concept of the invention, including best mode, and but also any person skilled in the art
The present invention, including any device or system of manufacture and use can be practiced, and implements the method for any combination.It should be pointed out that
For those skilled in the art, without departing from the principle of the present invention, can also to the present invention into
Row some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.The invention patent is protected
The range of shield is defined by the claims, and may include those skilled in the art it is conceivable that other embodiments.If this
A little other embodiments have the structural element for being not different from claim character express, or if they include wanting with right
Equivalent structural elements of the character express asked without essence difference, then these other embodiments should also be included in the model of claim
In enclosing.
Claims (10)
1. a kind of preparation method of graphene composite epoxy resin, which comprises the following steps:
A after) mixing graphene organic dispersion, epoxy resin and organic solvent, precursor solution is obtained；
B after) precursor solution for obtaining above-mentioned steps is ground and is ultrasonically treated, mixed solution is obtained；
C after) mixed solution for obtaining above-mentioned steps carries out high-temperature vacuum revolving, graphene composite epoxy resin is obtained.
2. preparation method according to claim 1, which is characterized in that the mass fraction of the graphene organic dispersion is
0.1%~3%；
The dispersing agent of the graphene organic dispersion includes dimethylbenzene, n-butanol, acetone, dimethanol, toluene and N- methyl pyrrole
One of pyrrolidone is a variety of；
The mass ratio of the graphene and the epoxy resin is 0.5%~5%.
3. preparation method according to claim 1, which is characterized in that the graphene includes single-layer graphene, the double-deck stone
One of black alkene, multi-layer graphene, graphene oxide and composite graphite alkene are a variety of；
The epoxy resin includes bisphenol A type epoxy resin；
The organic solvent include one of dimethylbenzene, n-butanol, acetone, dimethanol, toluene and N-Methyl pyrrolidone or
It is a variety of；
The mass ratio of the epoxy resin and the organic solvent is (1~4): 1.
4. preparation method according to claim 1, which is characterized in that the graphene organic dispersion is by graphene slurry
It is obtained after ultrasonic agitation with dispersing agent；
The solid content of the graphene slurry is 0.5%~10%.
5. the preparation method according to claim 4, which is characterized in that the time of the ultrasonic agitation is 20~120min；
The frequency of the ultrasound is 20~80kHz；
The revolving speed of the stirring is 200~600r/min.
6. preparation method according to claim 1, which is characterized in that the step A) specifically:
A1) epoxy resin and organic solvent are first mixed, obtain epoxy resin solution；
A2 it) again into the epoxy resin solution that above-mentioned steps obtain, is slowly added to graphene organic dispersion and is stirred by ultrasonic, obtain
To precursor solution.
7. preparation method according to claim 6, which is characterized in that the step A1) in, the ultrasound that is mixed into is stirred
It mixes；
The time of the ultrasonic agitation is 20~120min；
The frequency of the ultrasound is 20~80kHz；
The revolving speed of the stirring is 200~900r/min.
8. preparation method according to claim 6, which is characterized in that the step A2) in, it is described to be incorporated slowly as dripping
Add；
The time of the ultrasonic agitation is 20~120min；
The frequency of the ultrasound is 20~80kHz；
The revolving speed of the stirring is 200~900r/min.
9. preparation method according to claim 1, which is characterized in that the step B) in, it is described to be ground to wet grinding；
The time of the grinding is 10~180min；The revolving speed of the grinding is 200~500r/s；
The ultrasonic treatment is ultrasonic agitation；
The time of the ultrasonic treatment is 20~120min；The frequency of the ultrasonic treatment is 20~80kHz；
The revolving speed of the stirring is 200~900r/min.
10. preparation method according to claim 1, which is characterized in that the step C) in, the high-temperature vacuum revolving
Temperature is 40~90 DEG C；
The pressure of the high-temperature vacuum revolving is 20~200mbar；
The revolving speed of the high-temperature vacuum revolving is 20~70r/min.
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