CN109135169A - The production method of graphene and aramid fiber mixing enhancing phenolic resin plate - Google Patents
The production method of graphene and aramid fiber mixing enhancing phenolic resin plate Download PDFInfo
- Publication number
- CN109135169A CN109135169A CN201810754231.XA CN201810754231A CN109135169A CN 109135169 A CN109135169 A CN 109135169A CN 201810754231 A CN201810754231 A CN 201810754231A CN 109135169 A CN109135169 A CN 109135169A
- Authority
- CN
- China
- Prior art keywords
- graphene
- phenolic resin
- plate
- aramid fiber
- production method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The production method of graphene and aramid fiber mixing enhancing phenolic resin plate, comprising the following steps: weigh graphene powder and be added in acetone soln, be prepared into suspension；Poly(aryl ether ketone), epoxy resin, phenolic resin are mixed and heated to be added in suspension after melting according to the weight of 1:1:8 and form graphene phenolic-resin complex liquid；It is put into graphene phenolic-resin complex liquid sufficiently infiltration after aramid fiber processing is dry and forms slurry；Slurry is poured into board making mold；Plate is formed after gel, solidification and curing three phases；Loading force and change in resistance curve are measured using digital resistance instrument, completes plate pressure sensing calibration measurement.The present invention using graphene change in resistance under pressure characteristic, produce can with electrified regulation, it is sensitive to pressure change and can real-time monitoring glass fibre-reinforced phenolic resin plate.The plate made keep its density it is small, intensity is high under the premise of, modulus is bigger, and wearability is stronger.
Description
Technical field
The invention belongs to polymer-based nanos and aramid fiber technical field, and in particular to one kind has heating and stress sense
Know the production method of the graphene and aramid fiber mixing enhancing phenolic resin plate of function.
Background technique
Aramid fiber has the excellent performances such as superhigh intensity, high-modulus, high temperature resistant, acid and alkali-resistance, light weight, wherein specific stiffness
It is 5-6 times of steel, modulus is 2-3 times of steel wire and glass fibre, and toughness is 2 times of steel wire, and density is only the 1/5 of steel wire
Left and right.In national defence, aerospace, automotive light weight technology etc. have irreplaceable role.
Phenolic resin is by artificial synthesized a kind of high molecular polymer.Urea formaldehyde is strangled in the processing and forming of product, by
In its good heat resistance, cost of material is low, there is preferable economic benefit compared with other raw materials.After epoxy-modified, phenol
The performance of urea formaldehyde further increases.
Aramid fiber enhancing phenolic resin composite plate is one of current most widely used composite material, is had close
The advantages that small, intensity is high is spent, designability is strong, is to be widely used in the important composite wood of one of national economy and national defense construction
Flitch material.But the composite panel electric conductivity is poor, is unable to electrified regulation, using being subject to certain restrictions in cold climate.Plate
The load being subject to cannot be from perceiving, and there are hidden danger for safety under specific condition.
Graphene is as a kind of nano-carbon material, and the electron mobility of graphene is more than 15000 cm at normal temperature2/ (V
S), resistivity about 10-6Cm is the smallest material of current resistivity；Graphene has excellent thermal conductivity,
Thermal coefficient may be up to 5300W/mK, be much higher than carbon nanotube and diamond.Graphene had both had high-intensitive, high-elastic mould and strong
The mechanical properties such as toughness, and there are the functional performances such as excellent thermally conductive, conductive, electromagnetism and assign the increasing of phenolic resin base aramid fiber
Strong composite material function/intelligent behaviour.With the sharp fall of graphene price, graphene is applied to field of compound material
Undoubtedly there is major application prospect.
Summary of the invention
The present invention provides a kind of keeping before its density is small, intensity is high to solve shortcoming in the prior art
Put, can electrified regulation, perceive plate pressure change graphene and aramid fiber mixing enhancing phenolic resin plate system
Make method.
In order to solve the above technical problems, the present invention adopts the following technical scheme: graphene and aramid fiber mixing enhancing phenol
The production method of urea formaldehyde plate, comprising the following steps:
(1), graphene is formed into graphene powder after machine is hydride modified；
(2), the graphene powder for weighing constant weight is added portionwise in acetone soln, then places it in Ultrasound Instrument to mixed
Solution ultrasonic treatment is closed, finely dispersed suspension is prepared into；
(3), poly(aryl ether ketone), epoxy resin, phenolic resin are weighed according to the weight ratio of 1:1:8 spare；
(4), load weighted poly(aryl ether ketone) is mixed with epoxy resin, mixture is melted to obtain to performed polymer at a certain temperature, so
Performed polymer is broken into powder with pulverizer afterwards, and passes through the dusting cover of 80 mesh；With blender by performed polymer powder and the phenol weighed
Urea formaldehyde is mixed to form phenolic resin blend, is heated to softening temperature or more, and phenolic resin blend is made to be in melt-flow
State；
(5), the phenolic resin blend of melting is added in suspension, is quickly stirred again after being mixed slowly using blender to mixed
It closes uniformly, forms graphene phenolic-resin complex liquid；
(6), using supercritical CO2Modified aramid fiber respectively cleans aramid fiber 12 hours through acetone, deionized water, in
After being dried at 110 DEG C, it is put into microwave plasma CVD device reaction chamber, reaction chamber is vacuumized, makes its vacuum
Degree is less than 10Pa, then passes to discharge gas and vacuumizes, and purifies the gas in reaction chamber three times repeatedly；It keeps in reaction chamber
Discharge gas pressure is 40~50 Pa, and plasma treatment is carried out under 70W electric energy；Treated, and aramid fiber is put into graphene
Sufficiently infiltration forms slurry in phenolic resin complex liquid；
(7), positive electrode and negative electrode are embedded in the diagonal position of board making die inside wall respectively, reserve connecting terminal；
(8) slurry in step (6) is poured into board making mold, bubble is discharged using vibratory drilling method, it is thick until reaching design
Degree；
(9), slurry successively forms plate, positive electrode after gel, solidification and curing three phases in board making mold
It adheres on plate with negative electrode and is integrally demoulded with plate；
(10), plate is placed after a certain period of time, according to certain method for supporting, plate is loaded using center loaded method
Pressure, positive electrode and negative electrode connect digital resistance instrument, and digital resistance instrument measures loading force and change in resistance curve, complete
Plate pressure sensing calibration measurement.
The weight of graphene powder in step (2) is the 0.3% of the phenolic resin blend weight melted in step (4).
Using method addition graphene is first mixed in step (1), graphene uses multi-layer graphene, the rule of multi-layer graphene raw material
Lattice are diameter < 2 μm, with a thickness of 1-5nm, specific surface area 500m2/ g, density 2-2.25g/ml, thermal coefficient > 3000w/m
K, electric conductivity > 107S/m。
The softening point of the phenolic resin blend of melting is at 70 °C and following.
Graphene phenolic-resin complex liquid in step (4) can also be prepared with reduction method；
Reduction method prepares graphene phenolic-resin complex liquid process are as follows:
Graphene oxide is prepared using Hummers method is improved；3g graphite powder and 1g sodium nitrate are added equipped with the 69 mL concentrated sulfuric acids
In three-necked flask, it is slowly added to 12g potassium permanganate under stirring in ice-water bath, in 10 DEG C or less reaction 1h；35 DEG C or so are warming up to,
Continue to stir 2h；120 mL deionized waters are slowly added to, system temperature is made to be increased to 95 DEG C or so, maintain 30 min, are added big
Distilled water dilution is measured, 30%H is poured into2O2It generates to no bubble, filters while hot, and washed with the HCl solution that volume ratio is 1: 10
Filter cake, using BaCl2Detection, until without SO in filtrate4, it is dried to obtain graphite oxide；Graphite oxide is soluble in water, and ultrasound makes
Be completely dispersed；Obtain graphene oxide；
50 phenolic resin and 25g propylene glycol monomethyl ether are added in three-necked flask, 80 DEG C is warming up to, is slowly added dropwise under stirring
10.5g diethanol amine reacts 2h；Then 60 DEG C are cooled to, 20% acetum reaction 30min is added dropwise, is then slowly added into steaming
The quick stirring and emulsifying of distilled water obtains cationic unsaturation lotion；
It adds graphene oxide into Phenolic resin emulsion, stirs ultrasound 1h, keep the temperature 3h at 60 DEG C, then proceed to ultrasound
30min, filtering obtain graphene oxide/phenolic resin and dispersion liquid are blended.
The weight for the aramid fiber being added in step (6) accounts for 30%-the 50% of graphene phenolic-resin complex liquid weight.
Gel, solidification and the detailed process of curing in step (8) are as follows:
Gel: gel time is a part of curing time, and after mixing, resin/curing agent mixture is still liquid and can
To work and be suitble to application；In order to guarantee reliably to be bonded, all construction and positioning work should be done within the curing operation time
It is good；
Solidification: mixture initially enters solidification phase, and at this moment it starts gel or " mutation "；At this moment unsaturation is not prolonged
Work is possible, will also lose viscosity；In this stage any interference cannot be carried out to it；It will become soft gel as hard rubber
Object, you with thumb will press it is dynamic it；
Curing: cure stage mixture is local solidification, the phenolic resin newly used still can with its chemical bonds, therefore should
Untreated surface still can be bonded or be reacted；Anyway, close to cured mixture, these abilities are reducing；No
Saturated mixture reaches solidification and becomes solids stages, at this moment can be sanded and integer；At this moment with thumb pressed it is motionless it, at this moment
There are about 90% end reaction intensity for phenolic resin, therefore can remove fixed clip, place it and maintain several days at room temperature
It is set to continue to solidify.
Center loaded method in step (9) specifically: multistage loadings are carried out to practical maximum to plate plane position of form center
Load；By sheet material measurement under by different load actions the variation of voltage and current calculate resistivity, utilize digital resistance instrument survey
It measures loading force and change in resistance curve calculates actual loading, while the security situation of plate is monitored.
The epoxide number of epoxy resin is 0.5 in step (3), the technical parameter of phenolic resin are as follows: free phenol is less than
1.5%, solid content about 50%, amount of flow 60mm, room temperature viscosity 300Pa.s.
By adopting the above technical scheme, method for supporting is set according to the actual support condition of test plate, different practical branch
Stay part uses different method for supporting.Such as: simply supported on four sides, opposite side freely-supported, arbitrary loading, opposite side are clamped.
Since graphene partial size is very small and is powder, the present invention is added multi-layer graphene using method is first mixed, is not easy in this way
It is adsorbed on stirring vessel and stirring blade and causes damages.The present invention improves phenolic resin base virtue using a certain amount of graphene is added
Synthetic fibre fibrous plate conduction and voltage-dependent characteristic, adapt to plate heating requirements under specified conditions, while can pass through real-time measurement resistance
Rate variation perception plate stress condition.
Although aramid fiber additional amount is bigger, composite material strength is higher, and aramid fiber additional amount is bigger, composite wood
The brittleness of material is also bigger.The effect of aramid fiber: aramid fiber is a kind of inorganic non-metallic material haveing excellent performance, heat resistance
By force, corrosion resistance is good, high mechanical strength, tensile strength are big.Tensile strength is 6.3~6.9g/d in normal conditions, moistens shape
5.4~5.8g/d of state, density 2.54g/cm3, aramid fiber are used as a kind of reinforcing material in the composite material.
Production method of the present invention is simple and easy, using the characteristic of graphene change in resistance under pressure, produces
Can with electrified regulation, it is sensitive to pressure change and can real-time monitoring aramid fiber enhance phenolic resin plate.It makes
Plate keep its density it is small, intensity is high under the premise of, modulus is bigger, and wearability is stronger.After tested, based on the stone of phenolic resin
Black alkene+aramid fiber reinforced composite heating declines 80 times with the resistance of force sensing function plate is answered.Thermal coefficient improves 40%, pressure
Quick coefficient reaches 100 or more.
Specific embodiment
The production method of graphene of the invention and aramid fiber mixing enhancing phenolic resin plate, comprising the following steps:
(1), graphene is formed into graphene powder after machine is hydride modified；
(2), the graphene powder for weighing constant weight is added portionwise in acetone soln, then places it in Ultrasound Instrument to mixed
Solution ultrasonic treatment is closed, finely dispersed suspension is prepared into；
(3), poly(aryl ether ketone), epoxy resin, phenolic resin are weighed according to the weight ratio of 1:1:8 spare；
(4), load weighted poly(aryl ether ketone) is mixed with epoxy resin, mixture is melted to obtain to performed polymer at a certain temperature, so
Performed polymer is broken into powder with pulverizer afterwards, and passes through the dusting cover of 80 mesh；With blender by performed polymer powder and the phenol weighed
Urea formaldehyde is mixed to form phenolic resin blend, is heated to softening temperature or more, and phenolic resin blend is made to be in melt-flow
State；
(5), the phenolic resin blend of melting is added in suspension, is quickly stirred again after being mixed slowly using blender to mixed
It closes uniformly, forms graphene phenolic-resin complex liquid；
(6), using supercritical CO2Modified aramid fiber respectively cleans aramid fiber 12 hours through acetone, deionized water, in
After being dried at 110 DEG C, it is put into microwave plasma CVD device reaction chamber, reaction chamber is vacuumized, makes its vacuum
Degree is less than 10Pa, then passes to discharge gas and vacuumizes, and purifies the gas in reaction chamber three times repeatedly；It keeps in reaction chamber
Discharge gas pressure is 40~50 Pa, and plasma treatment is carried out under 70W electric energy；Treated, and aramid fiber is put into graphene
Sufficiently infiltration forms slurry in phenolic resin complex liquid；
(7), positive electrode and negative electrode are embedded in the diagonal position of board making die inside wall respectively, reserve connecting terminal；
(8) slurry in step (6) is poured into board making mold, bubble is discharged using vibratory drilling method, it is thick until reaching design
Degree；
(9), slurry successively forms plate, positive electrode after gel, solidification and curing three phases in board making mold
It adheres on plate with negative electrode and is integrally demoulded with plate；
(10), plate is placed after a certain period of time, according to certain method for supporting, plate is loaded using center loaded method
Pressure, positive electrode and negative electrode connect digital resistance instrument, and digital resistance instrument measures loading force and change in resistance curve, complete
Plate pressure sensing calibration measurement.
The weight of graphene powder in step (2) is the 0.3% of the phenolic resin blend weight melted in step (4).
Using method addition graphene is first mixed in step (1), graphene uses multi-layer graphene, the rule of multi-layer graphene raw material
Lattice are diameter < 2 μm, with a thickness of 1-5nm, specific surface area 500m2/ g, density 2-2.25g/ml, thermal coefficient > 3000w/m
K, electric conductivity > 107S/m。
The softening point of the phenolic resin blend of melting is at 70 °C and following.
Graphene phenolic-resin complex liquid in step (4) can also be prepared with reduction method；
Reduction method prepares graphene phenolic-resin complex liquid process are as follows:
Graphene oxide is prepared using Hummers method is improved；3g graphite powder and 1g sodium nitrate are added equipped with the 69 mL concentrated sulfuric acids
In three-necked flask, it is slowly added to 12g potassium permanganate under stirring in ice-water bath, in 10 DEG C or less reaction 1h；35 DEG C or so are warming up to,
Continue to stir 2h；120 mL deionized waters are slowly added to, system temperature is made to be increased to 95 DEG C or so, maintain 30 min, are added big
Distilled water dilution is measured, 30%H is poured into2O2It generates to no bubble, filters while hot, and washed with the HCl solution that volume ratio is 1: 10
Filter cake, using BaCl2Detection, until without SO in filtrate4, it is dried to obtain graphite oxide；Graphite oxide is soluble in water, and ultrasound makes
Be completely dispersed；Obtain graphene oxide；
50 phenolic resin and 25g propylene glycol monomethyl ether are added in three-necked flask, 80 DEG C is warming up to, is slowly added dropwise under stirring
10.5g diethanol amine reacts 2h；Then 60 DEG C are cooled to, 20% acetum reaction 30min is added dropwise, is then slowly added into steaming
The quick stirring and emulsifying of distilled water obtains cationic unsaturation lotion；
It adds graphene oxide into Phenolic resin emulsion, stirs ultrasound 1h, keep the temperature 3h at 60 DEG C, then proceed to ultrasound
30min, filtering obtain graphene oxide/phenolic resin and dispersion liquid are blended.
The weight for the aramid fiber being added in step (6) accounts for 30%-the 50% of graphene phenolic-resin complex liquid weight.
Gel, solidification and the detailed process of curing in step (8) are as follows:
Gel: gel time is a part of curing time, and after mixing, resin/curing agent mixture is still liquid and can
To work and be suitble to application；In order to guarantee reliably to be bonded, all construction and positioning work should be done within the curing operation time
It is good；
Solidification: mixture initially enters solidification phase, and at this moment it starts gel or " mutation "；At this moment unsaturation is not prolonged
Work is possible, will also lose viscosity；In this stage any interference cannot be carried out to it；It will become soft gel as hard rubber
Object, you with thumb will press it is dynamic it；
Curing: cure stage mixture is local solidification, the phenolic resin newly used still can with its chemical bonds, therefore should
Untreated surface still can be bonded or be reacted；Anyway, close to cured mixture, these abilities are reducing；No
Saturated mixture reaches solidification and becomes solids stages, at this moment can be sanded and integer；At this moment with thumb pressed it is motionless it, at this moment
There are about 90% end reaction intensity for phenolic resin, therefore can remove fixed clip, place it and maintain several days at room temperature
It is set to continue to solidify.
Center loaded method in step (9) specifically: multistage loadings are carried out to practical maximum to plate plane position of form center
Load；By sheet material measurement under by different load actions the variation of voltage and current calculate resistivity, utilize digital resistance instrument survey
It measures loading force and change in resistance curve calculates actual loading, while the security situation of plate is monitored.
The epoxide number of epoxy resin is 0.5 in step (3), the technical parameter of phenolic resin are as follows: free phenol is less than
1.5%, solid content about 50%, amount of flow 60mm, room temperature viscosity 300Pa.s.
The present embodiment not makes any form of restriction shape of the invention, material, structure etc., all according to this hair
Bright technical spirit any simple modification, equivalent change and modification to the above embodiments, belong to the technology of the present invention side
The protection scope of case.
Claims (9)
1. the production method of graphene and aramid fiber mixing enhancing phenolic resin plate, it is characterised in that: the following steps are included:
(1), graphene is formed into graphene powder after machine is hydride modified；
(2), the graphene powder for weighing constant weight is added portionwise in acetone soln, then places it in Ultrasound Instrument to mixed
Solution ultrasonic treatment is closed, finely dispersed suspension is prepared into；
(3), poly(aryl ether ketone), epoxy resin, phenolic resin are weighed according to the weight ratio of 1:1:8 spare；
(4), load weighted poly(aryl ether ketone) is mixed with epoxy resin, mixture is melted to obtain to performed polymer at a certain temperature, so
Performed polymer is broken into powder with pulverizer afterwards, and passes through the dusting cover of 80 mesh；With blender by performed polymer powder and the phenol weighed
Urea formaldehyde is mixed to form phenolic resin blend, is heated to softening temperature or more, and phenolic resin blend is made to be in melt-flow
State；
(5), the phenolic resin blend of melting is added in suspension, is quickly stirred again after being mixed slowly using blender to mixed
It closes uniformly, forms graphene phenolic-resin complex liquid；
(6), using supercritical CO2Modified aramid fiber respectively cleans aramid fiber 12 hours through acetone, deionized water, in
After being dried at 110 DEG C, it is put into microwave plasma CVD device reaction chamber, reaction chamber is vacuumized, makes its vacuum
Degree is less than 10Pa, then passes to discharge gas and vacuumizes, and purifies the gas in reaction chamber three times repeatedly；It keeps in reaction chamber
Discharge gas pressure is 40~50 Pa, and plasma treatment is carried out under 70W electric energy；Treated, and aramid fiber is put into graphene
Sufficiently infiltration forms slurry in phenolic resin complex liquid；
(7), positive electrode and negative electrode are embedded in the diagonal position of board making die inside wall respectively, reserve connecting terminal；
(8) slurry in step (6) is poured into board making mold, bubble is discharged using vibratory drilling method, it is thick until reaching design
Degree；
(9), slurry successively forms plate, positive electrode after gel, solidification and curing three phases in board making mold
It adheres on plate with negative electrode and is integrally demoulded with plate；
(10), plate is placed after a certain period of time, according to certain method for supporting, plate is loaded using center loaded method
Pressure, positive electrode and negative electrode connect digital resistance instrument, and digital resistance instrument measures loading force and change in resistance curve, complete
Plate pressure sensing calibration measurement.
2. the production method of graphene according to claim 1 and aramid fiber mixing enhancing phenolic resin plate, special
Sign is: the weight of the graphene powder in step (2) is the 0.3% of the phenolic resin blend weight melted in step (4).
3. the production method of graphene according to claim 1 and aramid fiber mixing enhancing phenolic resin plate, special
Sign is: using method addition graphene is first mixed in step (1), graphene uses multi-layer graphene, the rule of multi-layer graphene raw material
Lattice are diameter < 2 μm, with a thickness of 1-5nm, specific surface area 500m2/ g, density 2-2.25g/ml, thermal coefficient > 3000w/m
K, electric conductivity > 107S/m。
4. the production method of graphene according to claim 2 and aramid fiber mixing enhancing phenolic resin plate, special
Sign is: the softening point of the phenolic resin blend of melting is at 70 °C and following.
5. the production method of graphene according to claim 1 and aramid fiber mixing enhancing phenolic resin plate, special
Sign is: the graphene phenolic-resin complex liquid in step (4) can also be prepared with reduction method；
Reduction method prepares graphene phenolic-resin complex liquid process are as follows:
Graphene oxide is prepared using Hummers method is improved；3g graphite powder and 1g sodium nitrate are added equipped with the 69 mL concentrated sulfuric acids
In three-necked flask, it is slowly added to 12g potassium permanganate under stirring in ice-water bath, in 10 DEG C or less reaction 1h；35 DEG C or so are warming up to,
Continue to stir 2h；120 mL deionized waters are slowly added to, system temperature is made to be increased to 95 DEG C or so, maintain 30 min, are added big
Distilled water dilution is measured, 30%H is poured into2O2It generates to no bubble, filters while hot, and washed with the HCl solution that volume ratio is 1: 10
Filter cake, using BaCl2Detection, until without SO in filtrate4, it is dried to obtain graphite oxide；Graphite oxide is soluble in water, and ultrasound makes
Be completely dispersed；Obtain graphene oxide；
50 phenolic resin and 25g propylene glycol monomethyl ether are added in three-necked flask, 80 DEG C is warming up to, is slowly added dropwise under stirring
10.5g diethanol amine reacts 2h；Then 60 DEG C are cooled to, 20% acetum reaction 30min is added dropwise, is then slowly added into steaming
The quick stirring and emulsifying of distilled water obtains cationic unsaturation lotion；
It adds graphene oxide into Phenolic resin emulsion, stirs ultrasound 1h, keep the temperature 3h at 60 DEG C, then proceed to ultrasound
30min, filtering obtain graphene oxide/phenolic resin and dispersion liquid are blended.
6. the production method of graphene according to claim 1 and aramid fiber mixing enhancing phenolic resin plate, special
Sign is: the weight for the aramid fiber being added in step (6) accounts for 30%-the 50% of graphene phenolic-resin complex liquid weight.
7. the production method of graphene according to claim 1 and aramid fiber mixing enhancing phenolic resin plate, special
Sign is: gel, solidification and the detailed process of curing in step (8) are as follows:
Gel: gel time is a part of curing time, and after mixing, resin/curing agent mixture is still liquid and can
To work and be suitble to application；In order to guarantee reliably to be bonded, all construction and positioning work should be done within the curing operation time
It is good；
Solidification: mixture initially enters solidification phase, and at this moment it starts gel or " mutation "；At this moment unsaturation is not prolonged
Work is possible, will also lose viscosity；In this stage any interference cannot be carried out to it；It will become soft gel as hard rubber
Object, you with thumb will press it is dynamic it；
Curing: cure stage mixture is local solidification, the phenolic resin newly used still can with its chemical bonds, therefore should
Untreated surface still can be bonded or be reacted；Anyway, close to cured mixture, these abilities are reducing；No
Saturated mixture reaches solidification and becomes solids stages, at this moment can be sanded and integer；At this moment with thumb pressed it is motionless it, at this moment
There are about 90% end reaction intensity for phenolic resin, therefore can remove fixed clip, place it and maintain several days at room temperature
It is set to continue to solidify.
8. the production method of graphene according to claim 1 and aramid fiber mixing enhancing phenolic resin plate, special
Sign is: the center loaded method in step (9) specifically: carries out multistage loadings to practical maximum lotus to plate plane position of form center
It carries；By sheet material measurement under by different load actions the variation of voltage and current calculate resistivity, utilize digital resistance instrument measurement
Loading force and change in resistance curve calculate actual loading out, while being monitored to the security situation of plate.
9. the production method of graphene according to claim 1 and aramid fiber mixing enhancing phenolic resin plate, special
Sign is: the epoxide number of epoxy resin is 0.5 in step (3), the technical parameter of phenolic resin are as follows: free phenol is less than
1.5%, solid content about 50%, amount of flow 60mm, room temperature viscosity 300Pa.s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810754231.XA CN109135169A (en) | 2018-07-11 | 2018-07-11 | The production method of graphene and aramid fiber mixing enhancing phenolic resin plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810754231.XA CN109135169A (en) | 2018-07-11 | 2018-07-11 | The production method of graphene and aramid fiber mixing enhancing phenolic resin plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109135169A true CN109135169A (en) | 2019-01-04 |
Family
ID=64800374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810754231.XA Pending CN109135169A (en) | 2018-07-11 | 2018-07-11 | The production method of graphene and aramid fiber mixing enhancing phenolic resin plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109135169A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372036A (en) * | 2021-06-24 | 2021-09-10 | 湖北嘉辐达节能科技股份有限公司 | Glass wool composite material for airplane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693678A (en) * | 2015-03-12 | 2015-06-10 | 中国科学院长春应用化学研究所 | Phenolic resin-based composite material containing graphene and preparation method thereof |
| CN105802142A (en) * | 2016-05-06 | 2016-07-27 | 金思宇 | Graphene modified fiber reinforced resin-based composite material and preparation method thereof |
| WO2017173258A1 (en) * | 2016-04-01 | 2017-10-05 | Arkema Inc. | 3-d printed fluoropolymer structures |
-
2018
- 2018-07-11 CN CN201810754231.XA patent/CN109135169A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693678A (en) * | 2015-03-12 | 2015-06-10 | 中国科学院长春应用化学研究所 | Phenolic resin-based composite material containing graphene and preparation method thereof |
| WO2017173258A1 (en) * | 2016-04-01 | 2017-10-05 | Arkema Inc. | 3-d printed fluoropolymer structures |
| CN105802142A (en) * | 2016-05-06 | 2016-07-27 | 金思宇 | Graphene modified fiber reinforced resin-based composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 朱美芳 等: "《中国战略性新兴产业—新材料 高性能纤维》", 30 November 2017, 中国铁道出版社 * |
| 李登新 等: "《NOx催化氧化吸收技术与系统》", 31 August 2017, 中国环境出版社 * |
| 陈建剑 等: "石墨烯改性对环氧树脂／碳纤维复丝拉伸性能的影响", 《合成纤维工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372036A (en) * | 2021-06-24 | 2021-09-10 | 湖北嘉辐达节能科技股份有限公司 | Glass wool composite material for airplane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108676326A (en) | Graphene based on epoxy resin and glass fiber reinforcement plank | |
| CN109265909A (en) | The board making and stress determination method of basalt fibre enhancing phenolic resin | |
| CN109206840A (en) | The production and stress measuring method of glass fibre-reinforced phenolic resin plate | |
| Huan et al. | High performance epoxy composites prepared using recycled short carbon fiber with enhanced dispersibility and interfacial bonding through polydopamine surface-modification | |
| CN109265917A (en) | Basalt fibre reinforced epoxy board making and stress measuring method | |
| CN109111694A (en) | The production and stress measuring method of glass fiber reinforced epoxy resin plate | |
| Ren et al. | Modification on glass fiber surface and their improved properties of fiber-reinforced composites via enhanced interfacial properties | |
| CN107057283B (en) | A kind of carbon fiber enhancement resin base composite material and preparation method thereof | |
| CN109111695A (en) | The production method of graphene and aramid fiber mixing reinforced epoxy plate | |
| CN109228076A (en) | The plate forming and stress determination method of carbon fiber reinforced phenol formaldehyde resin | |
| CN109203500A (en) | The plate forming and stress determination method of carbon-fibre reinforced epoxy resin | |
| CN105778424B (en) | A kind of carbon nanotube, carbon fiber modified synergic epoxy resin composite material and preparation method thereof | |
| CN104231624A (en) | Modified cyanate resin heat-conducting composite material and preparation method thereof | |
| CN102532951A (en) | Method for toughening epoxy resin by adopting modified wollastonite | |
| CN105622929A (en) | Casting nylon/graphene nanocomposite material and preparation method thereof | |
| CN116640457B (en) | Modified asphalt for waterproof coiled material and preparation method thereof | |
| CN109206905A (en) | A kind of graphene bismaleimide resin composite material and preparation method thereof | |
| CN109181210A (en) | The plate forming and stress determination method of boron fibre enhancing phenolic resin | |
| CN108997708A (en) | Para-aramid fiber enhances phenolic resin board making and stress measuring method | |
| CN109135169A (en) | The production method of graphene and aramid fiber mixing enhancing phenolic resin plate | |
| CN109161157A (en) | Para-aramid fiber reinforced epoxy board making and stress measuring method | |
| CN103923462A (en) | Preparation method of modified PBO [poly(p-phenylene benzobisoxazole)] fiber prepreg | |
| CN109262924A (en) | The board making and stress determination method of basalt fibre enhancing unsaturated-resin | |
| CN108707310A (en) | With heating and making and the stress assay method of answering force sensing function plank | |
| CN109776830B (en) | Preparation method of polyurethane/carboxymethyl chitosan/polyaniline conductive film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190104 |