CN109206848A - A kind of epoxy prepreg and preparation method thereof - Google Patents
A kind of epoxy prepreg and preparation method thereof Download PDFInfo
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- CN109206848A CN109206848A CN201710523601.4A CN201710523601A CN109206848A CN 109206848 A CN109206848 A CN 109206848A CN 201710523601 A CN201710523601 A CN 201710523601A CN 109206848 A CN109206848 A CN 109206848A
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/04—Carbon
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
Abstract
The present invention provides a kind of epoxy prepreg and preparation method thereof, which includes: epoxy resin: 40~70 parts；Reduced graphene: 1~5 part；Fire retardant: 6~10 parts；And curing agent: 10~40 parts.By the present invention in that with reduced graphene, so that the epoxy prepreg of preparation has excellent mechanical property, flame retardant property and high temperature resistance, it can be applied to the numerous areas such as space shuttle wing and fuselage, radome, space flight heat-barrier material, civil aircraft internal material, naval vessel surfacing and construction timber.
Description
Technical field
The present invention relates to Material Fields, more particularly, to a kind of epoxy prepreg and preparation method thereof.
Background technique
Common resin has phenolic resin, epoxy resin, bimaleimide resin and cyanate ester resin in composite material
Deng, wherein epoxy resin has excellent adhesion energy, wear-resisting property, mechanical property, electrical insulation capability, chemical stabilization because of it
Performance and be widely used.But epoxy resin has easy burning, (especially impact is strong for high temperature resistance and mechanical property
Degree) difference disadvantage.
Prepreg is the intermediate materials of composite material preparation process, and it is compound that the superiority and inferiority of quality directly influences final product
The quality of material.Based on environmental requirement, the method for improving epoxy group prepreg flame retardant property at present is to be added in the epoxy
The fire retardant of addition type or response type.A kind of addition phosphorus nitrogen reactive flame retardant raising epoxy resin is disclosed in the prior art
Method so that laminate prepared by prepreg have excellent electric property and flame retardant property, can be used for preparing track
Road plate and other associated electrical materials；In addition, a kind of manufacturing method of high-melting-point fire retardant is also disclosed in the prior art, by it
It is added in epoxy resin, prepared prepreg has excellent dielectric properties and flame retardant property, can be used for printed circuit board
Preparation.
However, although the above method improves the flame retardant property of prepreg, but the high temperature resistance and mechanical property of prepreg
Can be poor, to limit the application of prepreg.
Summary of the invention
In order to overcome the above problem, the present invention uses reduction degree to fill out for 40%~60% reduced graphene as nanometer
Material, by the dispersion of easy volatile solvent, so that the reduced graphene with high temperature resistant, high strength is dispersed in asphalt mixtures modified by epoxy resin
In rouge, and by the additive amount of control reduced graphene, the heat-resisting quantity and mechanical property of epoxy resin are effectively increased, this
Outside, reduced graphene can be used as barrier, the propagation of trap heat and the entrance of oxygen in the epoxy, to improve material
Flame retardant property.
The present invention provides a kind of epoxy prepregs, according to parts by weight, comprising:
Epoxy resin: 40~70 parts；Reduced graphene: 1~5 part；Fire retardant: 6~10 parts；And curing agent: 10~40
Part.
In above-mentioned epoxy prepreg, the reduction degree of the reduced graphene is 40%~60%.
In above-mentioned epoxy prepreg, the fire retardant includes one in ammonium polyphosphate, zinc borate and aluminium hydroxide
Kind is a variety of.
In above-mentioned epoxy prepreg, the curing agent includes one of m-phenylene diamine (MPD), polymercaptan and polyamide
Or it is a variety of.
The present invention also provides a kind of methods for preparing epoxy prepreg, comprising the following steps:
Reduced graphene is added in solvent, reduced graphene dispersion liquid is formed；Described go back is added in the epoxy
Former graphene dispersing solution evaporates the solvent, adds fire retardant, curing agent, forms modified flame-retardant epoxy resin；And by institute
It states modified flame-retardant epoxy resin and is coated to fiber or fabric surface, squeeze, heating, winding, obtain the epoxy prepreg.
In the above-mentioned methods, the reduced graphene is prepared by the following method:
Sulfuric acid, nitric acid mixed liquor in graphene is added, add potassium permanganate, react, solution is poured into ice later
In water, hydrogen peroxide is added in stirring, until solution colour is glassy yellow；Centrifugation, obtained solid ethyl alcohol, hydrochloric acid and distilled water
Washing, it is dry, obtain graphene oxide；And restore the graphene oxide, form the reduced graphene.
In the above-mentioned methods, the graphene oxide is restored into 1~3h under 200~300 DEG C of vacuum condition.
In the above-mentioned methods, the reduction degree of the reduced graphene is 40%~60%.
In the above-mentioned methods, the solvent includes one of ethyl alcohol, isopropanol and normal propyl alcohol or a variety of.
In the above-mentioned methods, the fire retardant includes one of ammonium polyphosphate, zinc borate and aluminium hydroxide or a variety of.
In the above-mentioned methods, the curing agent includes one of m-phenylene diamine (MPD), polymercaptan and polyamide or a variety of.
In the above-mentioned methods, according to parts by weight, it is added described in 1~5 part in 40~70 parts of the epoxy resin
Reduced graphene, 6~10 parts of the fire retardant and 10~40 parts of the curing agent.
The present invention is and volatile molten by the way that reduced graphene to be dispersed in by the reduction degree of control graphene oxide
It in agent, adds in resin and is dispersed, be evenly dispersed in reduced graphene in epoxy resin, improving epoxy resin prepolymer
The high temperature resistance and mechanical property of prepreg are improved while leaching material anti-flammability.
In the present invention, the reduction degree of reduced graphene should control between 40%~60%, and reduction degree is too low, reduction
Graphene oxygen-containing group is more, and thermal stability is poor, and cannot improve resins fire retardant performance；Reduction degree is too high, the graphite of reduction
Alkene oxygen-containing group is very little, is easy to reunite between graphene, and poor with the interface interaction power of resin, to influence the mechanics of prepreg
The promotion of performance.The present invention by under vacuum conditions control reduction temperature be 200~300 DEG C, and the recovery time be 1~
3h, so that graphene reduction degree is controlled, so that the epoxy prepreg of preparation has while with good flame retardant property
There are preferable high temperature resistance and mechanical property.
Detailed description of the invention
Fig. 1 is epoxy prepreg preparation flow figure (1- creel；2- steeping vat；3- roller；4- drying glue furnace；5- temperature control is opened
It closes；6- fan；7- receive silk machine；8- adjustable DC power supply).
Specific embodiment
The following examples can make those skilled in the art that the present invention be more fully understood, but not limit in any way
The present invention.
The present invention controls the reduction degree of graphene between 40%~60% by aoxidizing and restore to graphene,
The preparation of the reduced graphene the following steps are included:
300~400mL concentrated sulfuric acid (mass fraction 98%), 20~60mL nitric acid mixed liquor in be added 2~5g stone
Black alkene, then 15~20g potassium permanganate is slowly added to the speed of 0.5mL/min~1mL/min, 50~70 DEG C of 10~14h of reaction,
The solution after reaction is poured slowly into 300~500mL ice water with the speed of 0.5mL/min~1mL/min later, 800~
1000r/min quickly stirs 10~20min, and hydrogen peroxide is added, until solution colour is glassy yellow；
It is centrifuged again, obtained solid ethyl alcohol, hydrochloric acid (mass fraction is lower than 20% dilute hydrochloric acid) and distillation washing
It washs 3~5 times, obtains brown solid, by the brown solid in -5 DEG C~-15 DEG C of at a temperature of 5~8h of freeze-drying, aoxidized
Graphene；And
Graphene oxide is restored into 1~3h in 200~300 DEG C of vacuum drying oven, controls reduction degree 40%~60%
Between, form reduced graphene.
After obtaining the reduced graphene that reduction degree is 40%~60%, is dispersed by using easy volatile solvent, make to restore
Disperse to graphene uniform in the epoxy, be prepared into epoxy prepreg using the reduced graphene, this is pre- improving
The high temperature resistance and mechanical property of the prepreg, the preparation of epoxy prepreg are improved while soaking the flame retardant property of material
The following steps are included:
1~5g reduced graphene was added in solvent (amount of solvent can disperse reduced graphene), 200~
20~30min of 20~30min of 300r/min mechanical stirring and ultrasonic disperse forms reduced graphene dispersion liquid；Wherein, solvent
Including one of ethyl alcohol, isopropanol and normal propyl alcohol or a variety of；
It is added above-mentioned reduced graphene dispersion liquid in 40~70g epoxy resin, 200~300r/min mechanical stirring 20~
20~30min of 30min and ultrasonic disperse evaporates solvent, adds 6~10g fire retardant, 10~40g curing agent, 200~
20~30min of 20~30min of 300r/min mechanical stirring and ultrasonic disperse forms modified flame-retardant epoxy resin；Fire retardant packet
One of ammonium polyphosphate, zinc borate and aluminium hydroxide or a variety of are included, curing agent includes in m-phenylene diamine (MPD), polymercaptan and polyamide
It is one or more；And
Modified flame-retardant epoxy resin is coated to fiber or fabric surface, is squeezed by compression roller, fiber or fabric are removed
The modified flame-retardant epoxy resin of surface residual obtains epoxy prepreg with 100~200 DEG C of temperature heating 1-2h, windings；
The epoxy prepreg is put into mold, solidifies 3~10min in 200~300 DEG C of vacuum drying oven, measures vertical combustion
Burn grade, thermal decomposition temperature and impact strength；Fiber or fabric include carbon cloth, aramid fabric, quartz fabric, one in glass-fiber-fabric
Kind is a variety of.
Embodiment 1
The 300mL concentrated sulfuric acid (mass fraction 98%), 20mL nitric acid mixed liquor in be added 4g graphene, be slowly added to
Solution after reaction, is poured slowly into 300mL ice water later, quickly stirs 15min by 18g potassium permanganate, 50 DEG C of reaction 14h,
Hydrogen peroxide is added, until solution colour is glassy yellow；It is centrifuged again, obtained solid ethyl alcohol, (mass fraction is lower than hydrochloric acid
20% dilute hydrochloric acid) and distillation water washing 3 times, brown solid is obtained, which is freeze-dried, graphite oxide is obtained
Alkene；By graphene oxide in 250 DEG C of vacuum drying oven reductase 12 h, obtain reduction graphite of the reduction degree between 50%~60%
Alkene；
3g reduced graphene is added in ethyl alcohol, mechanical stirring and ultrasonic disperse, forms reduced graphene dispersion liquid；Again
Reduced graphene dispersion liquid is added in 50g epoxy resin, mechanical stirring and ultrasonic disperse, ethanol evaporation, it is poly- to add 8g
Ammonium phosphate fire retardant, 20g m-phenylene diamine (MPD) curing agent, mechanical stirring and ultrasonic disperse form modified flame-retardant epoxy resin；
Modified flame-retardant epoxy resin is applied to carbon cloth surface, is squeezed by compression roller, carbon cloth surface is removed
Remaining modified flame-retardant epoxy resin heats 1h with 100 DEG C of temperature, and winding obtains epoxy prepreg；By epoxy resin
Prepreg is put into mold, solidifies 5min, measurement vertical combustion grade, thermal decomposition temperature and punching in 250 DEG C of vacuum drying oven
Hit intensity.
Embodiment 2
The 300mL concentrated sulfuric acid (mass fraction 98%), 20mL nitric acid mixed liquor in be added 2g graphene, be slowly added to
Solution after reaction, is poured slowly into 300mL ice water later, quickly stirs 10min by 15g potassium permanganate, 50 DEG C of reaction 14h,
Hydrogen peroxide is added, until solution colour is glassy yellow；It is centrifuged again, obtained solid ethyl alcohol, (mass fraction is lower than hydrochloric acid
20% dilute hydrochloric acid) and distillation water washing 3 times, brown solid is obtained, which is freeze-dried, graphite oxide is obtained
Alkene；Graphene oxide is restored into 1h in 200 DEG C of vacuum drying oven, obtains reduction graphite of the reduction degree between 40%~45%
Alkene；
1g reduced graphene is added in the mixed liquor of isopropanol and normal propyl alcohol, mechanical stirring and ultrasonic disperse, is formed
Reduced graphene dispersion liquid；Reduced graphene dispersion liquid is added in 40g epoxy resin again, mechanical stirring and ultrasonic disperse,
The mixed liquor for evaporating isopropanol and normal propyl alcohol, adds 6g zinc borate flame retardant, 10g Polymercaptan curing agent, mechanical stirring and super
Sound dispersion, forms modified flame-retardant epoxy resin；
Modified flame-retardant epoxy resin is applied to aramid fabric surface, is squeezed by compression roller, aramid fabric surface residual is removed
Modified flame-retardant epoxy resin, 2h is heated with 100 DEG C of temperature, winding obtains epoxy prepreg；By the epoxy resin prepolymer
Leaching material is put into mold, solidifies 10min, measurement vertical combustion grade, thermal decomposition temperature and impact in 200 DEG C of vacuum drying oven
Intensity.
Embodiment 3
The 400mL concentrated sulfuric acid (mass fraction 98%), 60mL nitric acid mixed liquor in be added 5g graphene, be slowly added to
Solution after reaction, is poured slowly into 500mL ice water later, quickly stirs 20min by 20g potassium permanganate, 70 DEG C of reaction 10h,
Hydrogen peroxide is added, until solution colour is glassy yellow；It is centrifuged again, obtained solid ethyl alcohol, (mass fraction is lower than hydrochloric acid
20% dilute hydrochloric acid) and distillation water washing 5 times, brown solid is obtained, which is freeze-dried, graphite oxide is obtained
Alkene；Graphene oxide is restored into 3h in 300 DEG C of vacuum drying oven, obtains reduction graphite of the reduction degree between 55%~60%
Alkene；
5g reduced graphene is added in isopropanol, mechanical stirring and ultrasonic disperse, forms reduced graphene dispersion liquid；
Reduced graphene dispersion liquid is added in 70g epoxy resin again, mechanical stirring and ultrasonic disperse, evaporates isopropanol, add
10g aluminium hydroxide fire retardant, 40g polyamide curing agent, mechanical stirring and ultrasonic disperse form modified flame-retardant epoxy resin；
Modified flame-retardant epoxy resin is applied to quartz fabric surface, is squeezed by compression roller, quartz fabric surface residual is removed
Modified flame-retardant epoxy resin, 1h is heated with 200 DEG C of temperature, winding obtains epoxy prepreg；By the epoxy resin prepolymer
Leaching material is put into mold, solidifies 3min, measurement vertical combustion grade, thermal decomposition temperature and impact in 300 DEG C of vacuum drying oven
Intensity.
Embodiment 4
The 350mL concentrated sulfuric acid (mass fraction 98%), 40mL nitric acid mixed liquor in be added 5g graphene, be slowly added to
Solution after reaction, is poured slowly into 400mL ice water later, quickly stirs 15min by 18g potassium permanganate, 60 DEG C of reaction 12h,
Hydrogen peroxide is added, until solution colour is glassy yellow；It is centrifuged again, obtained solid ethyl alcohol, (mass fraction is lower than hydrochloric acid
20% dilute hydrochloric acid) and distillation water washing 4 times, brown solid is obtained, which is freeze-dried, graphite oxide is obtained
Alkene；Graphene oxide is restored into 1.5h in 260 DEG C of vacuum drying oven, obtains reduction stone of the reduction degree between 50%~55%
Black alkene；
2g reduced graphene is added in normal propyl alcohol, mechanical stirring and ultrasonic disperse, forms reduced graphene dispersion liquid；
Reduced graphene dispersion liquid is added in 60g epoxy resin again, mechanical stirring and ultrasonic disperse, evaporates normal propyl alcohol, add
3g ammonium polyphosphate and 5g zinc borate (fire retardant) and 30g m-phenylene diamine (MPD) curing agent, mechanical stirring and ultrasonic disperse are formed and are modified
Fire retarding epoxide resin；
Modified flame-retardant epoxy resin is applied to glass-fiber-fabric surface, is squeezed by compression roller, glass-fiber-fabric surface residual is removed
Modified flame-retardant epoxy resin, 1.5h is heated with 150 DEG C of temperature, winding obtains epoxy prepreg；By the epoxy resin
Prepreg is put into mold, solidifies 6min, measurement vertical combustion grade, thermal decomposition temperature and punching in 280 DEG C of vacuum drying oven
Hit intensity.
Embodiment 5
The 380mL concentrated sulfuric acid (mass fraction 98%), 50mL nitric acid mixed liquor in be added 5g graphene, be slowly added to
Solution after reaction, is poured slowly into 450mL ice water later, quickly stirs 15min by 20g potassium permanganate, 60 DEG C of reaction 12h,
Hydrogen peroxide is added, until solution colour is glassy yellow；It is centrifuged again, obtained solid ethyl alcohol, (mass fraction is lower than hydrochloric acid
20% dilute hydrochloric acid) and distillation water washing 3 times, brown solid is obtained, which is freeze-dried, graphite oxide is obtained
Alkene；By graphene oxide in 260 DEG C of vacuum drying oven reductase 12 h, obtain reduction graphite of the reduction degree between 50%~60%
Alkene；
5g reduced graphene is added in normal propyl alcohol, mechanical stirring and ultrasonic disperse, forms reduced graphene dispersion liquid；
Reduced graphene dispersion liquid is added in 70g epoxy resin again, mechanical stirring and ultrasonic disperse, evaporates normal propyl alcohol, add
8g aluminium hydroxide fire retardant, 35g Polymercaptan curing agent, mechanical stirring and ultrasonic disperse form modified flame-retardant epoxy resin；
Modified flame-retardant epoxy resin is applied to carbon cloth surface, is squeezed by compression roller, carbon cloth surface is removed
Remaining modified flame-retardant epoxy resin heats 1h with 200 DEG C of temperature, and winding obtains epoxy prepreg；By the asphalt mixtures modified by epoxy resin
Rouge prepreg is put into mold, solidifies 7min in 220 DEG C of vacuum drying oven, measurement vertical combustion grade, thermal decomposition temperature and
Impact strength.
Embodiment 6
The 300mL concentrated sulfuric acid (mass fraction 98%), 30mL nitric acid mixed liquor in be added 5g graphene, be slowly added to
Solution after reaction, is poured slowly into 400mL ice water later, quickly stirs 15min by 16g potassium permanganate, 60 DEG C of reaction 12h,
Hydrogen peroxide is added, until solution colour is glassy yellow；It is centrifuged again, obtained solid ethyl alcohol, (mass fraction is lower than hydrochloric acid
20% dilute hydrochloric acid) and distillation water washing 3 times, brown solid is obtained, which is freeze-dried, graphite oxide is obtained
Alkene；Graphene oxide is restored into 1h in 260 DEG C of vacuum drying oven, obtains reduction graphite of the reduction degree between 40%~45%
Alkene；
2g reduced graphene is added in normal propyl alcohol, mechanical stirring and ultrasonic disperse, forms reduced graphene dispersion liquid；
Reduced graphene dispersion liquid is added in 40g epoxy resin again, mechanical stirring and ultrasonic disperse, evaporates normal propyl alcohol, add
8g ammonium polyphosphate flame retardant and 12g m-phenylene diamine (MPD) and 10g polyamide (curing agent), mechanical stirring and ultrasonic disperse, formation change
Property fire retarding epoxide resin；
Modified flame-retardant epoxy resin is applied to glass-fiber-fabric surface, is squeezed by compression roller, glass-fiber-fabric surface residual is removed
Modified flame-retardant epoxy resin, 1.5h is heated with 200 DEG C of temperature, winding obtains epoxy prepreg；By the epoxy resin
Prepreg is put into mold, solidifies 5min, measurement vertical combustion grade, thermal decomposition temperature and punching in 150 DEG C of vacuum drying oven
Hit intensity.
Comparative example 1
It is same as Example 1, in addition to being not added with reduced graphene.
Comparative example 2
It is same as Example 2, in addition to being not added with reduced graphene.
Comparative example 3
It is same as Example 3, in addition to being not added with reduced graphene.
Comparative example 4
It is same as Example 4, in addition to being not added with reduced graphene.
Comparative example 5
It is same as Example 5, in addition to being not added with reduced graphene.
Comparative example 6
It is same as Example 6, in addition to being not added with reduced graphene.
Using the vertical combustion grade of the prepreg in method measurement Examples 1 to 6 commonly used in the art, measurement result
It see the table below 1:
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Vertical combustion grade | V-0 | V-0 | V-1 | V-0 | V-0 | V-0 |
Seen from table 1, the combustion rating for preparing prepreg by means of the present invention is in V-0 grade, less place mostly
In V-1 grade, there is preferable flame retardant property, this is because reduced graphene can be used as barrier in the epoxy, barrier
The propagation of heat and the entrance of oxygen, so that the flame retardant property of material is preferable.
Using initial point of the prepreg in method measurement Examples 1 to 6 commonly used in the art and comparative example 1~6
Solution temperature and impact strength, measurement result see the table below 2:
Table 2
As can be seen from Table 2, the prepreg prepared by addition reduced graphene and the prepreg phase for being not added with reduced graphene
Than thermal decomposition temperature improves 9.28% or more, and thermal shock strength improves 8% or more.
From embodiment 3 and comparative example 3 as can be seen that thermal decomposition temperature is up to 256 DEG C, compared to being not added with reduced graphene
215 DEG C of thermal decomposition temperature of prepreg, improve 19.07%, effectively increase the high temperature resistance of prepreg；In addition, punching
Hit intensity can be from the 30.6KJ/m for being not added with reduced graphene2It is increased to 35.9KJ/m2, 17.32% is improved, is effectively increased
The mechanical property of prepreg,
This is because the reduced graphene that reduction degree is 40%~60% has the superiority such as high temperature resistant and high strength
Can, by controlling the additive amount of reduced graphene, and keep reduced graphene evenly dispersed in the epoxy, so that preparation
The high temperature resistance and mechanical property of epoxy prepreg are increased substantially.
To sum up, prepreg prepared according to the methods of the invention has excellent mechanical property, flame retardant property and high temperature resistant
Performance can be applied to space shuttle wing and fuselage, radome, space flight heat-barrier material, civil aircraft internal material, naval vessel
The numerous areas such as surfacing and construction timber.
It will be understood by those skilled in the art that above embodiments are only exemplary embodiments, without departing substantially from spirit of the invention
In the case where range, a variety of variations can be carried out, replaced and changed.
Claims (12)
1. a kind of epoxy prepreg, which is characterized in that according to parts by weight, comprising:
Epoxy resin: 40~70 parts；
Reduced graphene: 1~5 part；
Fire retardant: 6~10 parts；And
Curing agent: 10~40 parts.
2. epoxy prepreg according to claim 1, which is characterized in that the reduction degree of the reduced graphene is
40%~60%.
3. epoxy prepreg according to claim 1, which is characterized in that the fire retardant includes ammonium polyphosphate, boron
One of sour zinc and aluminium hydroxide are a variety of.
4. epoxy prepreg according to claim 1, which is characterized in that the curing agent includes m-phenylene diamine (MPD), gathers
One of mercaptan and polyamide are a variety of.
5. a kind of method for preparing epoxy prepreg, which comprises the following steps:
Reduced graphene is added in solvent, reduced graphene dispersion liquid is formed；
The reduced graphene dispersion liquid is added in the epoxy, evaporates the solvent, adds fire retardant, curing agent, shape
At modified flame-retardant epoxy resin；And
The modified flame-retardant epoxy resin is coated to fiber or fabric surface, squeezes, heating, winding, obtains the asphalt mixtures modified by epoxy resin
Rouge prepreg.
6. according to the method described in claim 5, it is characterized in that, the reduced graphene is prepared by the following method:
Sulfuric acid, nitric acid mixed liquor in graphene is added, add potassium permanganate, react, solution is poured into ice water later,
Hydrogen peroxide is added in stirring, until solution colour is glassy yellow；
Centrifugation, obtained solid ethyl alcohol, hydrochloric acid and distillation water washing are dry, obtain graphene oxide；And
The graphene oxide is restored, the reduced graphene is formed.
7. according to the method described in claim 6, it is characterized in that, by the oxidation stone under 200~300 DEG C of vacuum condition
Black alkene restores 1~3h.
8. according to the method described in claim 5, it is characterized in that, the reduction degree of the reduced graphene is 40%~60%.
9. according to the method described in claim 5, it is characterized in that, the solvent includes in ethyl alcohol, isopropanol and normal propyl alcohol
It is one or more.
10. according to the method described in claim 5, it is characterized in that, the fire retardant includes ammonium polyphosphate, zinc borate and hydrogen-oxygen
Change one of aluminium or a variety of.
11. according to the method described in claim 5, it is characterized in that, the curing agent includes m-phenylene diamine (MPD), polymercaptan and polyamides
One of amine is a variety of.
12. according to the method described in claim 5, it is characterized in that, according to parts by weight, in 40~70 parts of the asphalt mixtures modified by epoxy resin
1~5 part of the reduced graphene, 6~10 parts of the fire retardant and 10~40 parts of the curing agent are added in rouge.
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