CN110452414A - A kind of preparation method of high starch breeding alkene enhancing bismaleimide resin based composites - Google Patents
A kind of preparation method of high starch breeding alkene enhancing bismaleimide resin based composites Download PDFInfo
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- CN110452414A CN110452414A CN201910785916.5A CN201910785916A CN110452414A CN 110452414 A CN110452414 A CN 110452414A CN 201910785916 A CN201910785916 A CN 201910785916A CN 110452414 A CN110452414 A CN 110452414A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/006—Using vacuum
Abstract
The invention discloses a kind of preparation methods of high starch breeding alkene enhancing bismaleimide resin based composites, three-dimensional graphene framework is prepared composite material sizing agent precursor by the method for priming by vacuum by the method, graphene polymer matrix composites slurry is prepared using the method for high-speed stirred ultrasonic wave added again, oriented graphite alkene reinforced resin based composites precursor is prepared by control temperature field and the field of force, prepares high dispersive graphene reinforced resin based composites finally by the cured method of pressurization gradient.The present invention solve existing method can not by graphene in resin matrix this problem of high orientation, improve resin matrix mechanical property, isotropic material is become into anisotropic material, extend the application range of composite material, the advantage of competition is strengthened, provides a kind of novel orientation preparation method to be nano-filled.
Description
Technical field
The invention belongs to material science and technology fields, are related to a kind of system of high starch breeding alkene reinforced resin based composites
Preparation Method.
Background technique
It stepped into for 21st century, aerospace has shown more vast potential for future development, the aviation of high level or superelevation level
Solar-system operation is more frequent, and effect will be far beyond science and technology field itself, to political, economical, military down to mankind society
Can live can all generate more extensive and more far-reaching influence.It is noted that great achievement acquired by aerospace cause, with boat
The development and breakthrough of empty space material technology are undivided.Material is basis and the guide of modern high technology and industry, very
It is the precondition that new and high technology makes a breakthrough in big degree.The total development trend of material be lighting, high intensity, high-modulus,
High temperature resistant, low cost, for the needs of modern high performance aircraft development, structure-function integration and intelligence are even more important
Materials direction.
Low-dimensional, nanosizing and Composite are to push New Aerospace Materials towards direction structure-function integration and intelligence
Energyization development and the important technology approach for realizing the transition of performance revolutionary character.Application of the graphene composite material in aerospace field
It is faced with important opportunity to develop.Currently, nanocomposite is still in laboratory and small lot production phase, with aviation
The increase of space industry demand and the development of nano carbon composite material technology itself, engineering with industrialization also will for its
Competitiveness is promoted in market to lay the foundation.But still challenging science and technology problem etc. is to be solved, nano-carbon material
Sight scale of receiving brings excellent performance for it, but also becomes the maximum difficult point of its engineer application, and general graphene is in resin matrix
In the middle at mixed and disorderly distribution, the characteristics of composite material exhibits go out isotropism, the component to certain particular/special requirements and device come in this way
It says, unnecessary waste and complexity will be will cause for the design of composite material.Therefore it is directed to this specific demand, needs to prepare
A kind of oriented graphite alkene composite material, performance go out anisotropy, and to meet the design requirement of specific demand component, promotion makes
With efficiency, cost is reduced, reduces the unnecessary waste of raw material.
Summary of the invention
The present invention provides one for the urgency studied above for anisotropic graphite alkene enhancing nanocomposite
The preparation method of kind high starch breeding alkene enhancing bismaleimide resin based composites.The present invention solves existing method can not be by graphite
Alkene this problem of high orientation in resin matrix, improves resin matrix mechanical property, and isotropic material is become each
Anisotropy material extends the application range of composite material, strengthens the advantage of competition, for it is nano-filled provide it is a kind of novel
Orientation preparation method.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of high starch breeding alkene enhancing bismaleimide resin based composites, includes the following steps:
Step 1: the preparation of graphene sponge:
Method one, the preparation that graphene sponge is carried out using the method for improving freeze-drying, the specific steps are as follows: will be scattered
Concentration is that the graphene aqueous solution of 5 ~ 20mg/ml is freezed under low temperature (0 DEG C or less), while being obtained using freeze-drying
Porous graphene sponge (density is 5 ~ 20mg/ml)；
Method two prepares graphene sponge using the method for reduction, the specific steps are as follows: by 5 ~ 30mg/ml graphene oxide water
Solution is freezed under low temperature (0 DEG C or less), while obtaining porous graphene oxide sponge (density using freeze-drying
For 5 ~ 30mg/ml)；Electronation for 24 hours is carried out at 70 ~ 90 DEG C of temperature using excessive hydrazine hydrate or in 200 ~ 1000 DEG C of heat
The method of reduction prepares graphene sponge；
Step 2: the preparation of graphene reinforced resin based composites precursor slurry:
Pure bismaleimide resin is drawn by the method for priming by vacuum by the graphene sponge prepared in step 1 using negative pressure method
In porous structure, the specific steps are as follows: utilize negative pressure method, it is 10 that graphene sponge, which is placed into viscosity,-3~10-1PaS's
In pure bismaleimide resin, baking oven is vacuumized (10 by vacuum pump4~105Pa), i.e. the method for priming by vacuum, by pure bismaleimide resin
It is drawn into the porous structure of graphene sponge, three-dimensional graphene framework is filled；
Graphene sponge resin to be perfused in advance passes through the side of stirring (800 ~ 2000r/min) ultrasonic wave added as precursor
It is uniformly mixed while method smashes the graphene three-dimensional framework that resin is perfused with pure bismaleimide resin matrix, the two mixed proportion root
It is prepared according to actual demand, obtains high dispersive graphene reinforced resin based composites precursor slurry；
Step 3: the preparation of oriented graphite alkene reinforced resin based composites precursor:
Control graphene reinforced resin based composites precursor slurry temperature field makes temperature lower than 0 DEG C, regulation graphene enhancing
The viscosity of polymer matrix composites precursor slurry in 1 ~ 10 PaS, under suitable viscosity by control the field of force (generally 50 ~
500MPa), oriented graphite alkene reinforced resin based composites precursor is prepared in the way of cold pressing；
Step 4: the preparation of oriented graphite alkene reinforced resin based composites:
The oriented graphite alkene reinforced resin based composites precursor prepared in step 3 is injected into mold, vacuum is carried out
De-bubble after the completion of solidification, finally prepares oriented graphite alkene enhancing tree by the control temperature field base field of force to meet solidifying requirements
Resin-based composite, in which: be cured as gradient solidification, gradient condition of cure is as follows: 160 ~ 180 DEG C of solidifications 2h, pressure 50MPa；
190 ~ 210 DEG C of solidifications, 1 hour pressure 50MPa；220 ~ 240 DEG C solidify 4 hours, and pressure 50MPa, 250 ~ 260 DEG C solidify 4 hours,
Pressure 50MPa.
Compared with the prior art, the present invention has the advantage that
1, the present invention uses the previously prepared graphene macroform of freeze-drying, is prepared by the method for vacuum auxiliary pouring and molding
Graphene reinforced resin based composites slurry.Oriented graphite alkene reinforced resin based composites key technology of preparing is captured, is solved
It has determined graphene orientation problem in resin matrix, has realized graphene high orientation in resin, obtain highly directional stone
Black alkene reinforced resin based composites.
2, the present invention realizes preparation and the regulating microstructure of graphene three-dimensional framework reinforcement, obtain density 5 ~
The controllable graphene sponge of 20mg/ml density.Oriented graphite alkene reinforced resin based composites are obtained, scanning proves that graphene exists
High orientation in resin matrix, while opposite resin matrix composite material mechanical property promotes 10 ~ 40% along orientation direction.
3, the present invention is by completely new preparation concept, using graphene three-dimensional framework as dispersion, using the side of priming by vacuum
Method and high-speed stirred ultrasonic wave added method prepare graphene reinforced resin based composites slurry, pass through control temperature field and the field of force
Oriented graphite alkene reinforced resin based composites precursor is prepared, oriented graphite alkene enhancing enhancing tree is obtained after pressurization gradient solidification
Resin-based composite is not only oriented graphene in resin matrix, while improving the mechanical property of composite material.
Detailed description of the invention
Fig. 1 is the pictorial diagram of gained graphene three-dimensional framework in 2 step 1 of embodiment；
Fig. 2 is gained oriented graphite alkene reinforced resin based composites precursor pictorial diagram in 2 step 3 of embodiment；
Fig. 3 is the microcosmic scanned photograph of gained oriented graphite alkene reinforced resin based composites in 2 step 4 of embodiment；
Fig. 4 is the mechanical property photo of gained oriented graphite alkene reinforced resin based composites in 2 step 4 of embodiment.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawing, and however, it is not limited to this, all to this
Inventive technique scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered
Within the protection scope of the present invention.
Specific embodiment 1: present embodiments provide for one kind can be used for preparing high starch breeding alkene enhancing bismaleimide resin
Three-dimensional graphene framework is prepared composite wood slurry by the method for priming by vacuum by the preparation method of based composites, the method
Expect precursor, then graphene polymer matrix composites slurry is prepared using the method for high-speed stirred ultrasonic wave added, passes through control temperature
Field and the field of force are spent to prepare oriented graphite alkene reinforced resin based composites precursor, finally by the pressurization cured method of gradient
Prepare high dispersive graphene reinforced resin based composites.Specifically comprise the following steps:
Step 1: the preparation of graphene sponge:
Method one, the preparation that graphene sponge is carried out using the method for improving freeze-drying, the specific steps are as follows: will be scattered
Concentration is that the graphene aqueous solution of 5 ~ 20mg/ml is freezed under low temperature (0 DEG C or less), while being obtained using freeze-drying
Porous graphene sponge (density is 5 ~ 20mg/ml)；
Method two prepares graphene sponge using the method for reduction, the specific steps are as follows: by 5 ~ 30mg/ml graphene oxide water
Solution is freezed under low temperature (0 DEG C or less), while obtaining porous graphene oxide sponge (density using freeze-drying
For 5 ~ 30mg/ml)；Electronation for 24 hours is carried out at 70 ~ 90 DEG C of temperature using excessive hydrazine hydrate or in 200 ~ 1000 DEG C of heat
The method of reduction prepares graphene sponge；
Step 2: the preparation of graphene reinforced resin based composites precursor slurry:
Resin is drawn by the method for priming by vacuum by the porous knot of the graphene sponge prepared in step 1 using negative pressure method
In structure, the specific steps are as follows: utilize negative pressure method, it is 10 that graphene sponge, which is placed into viscosity,-3~10-1The resin of PaS is worked as
In, baking oven is vacuumized (10 by vacuum pump4~105Pa), i.e. the method for priming by vacuum, is drawn into graphene sponge for resin
In porous structure；
Graphene sponge resin to be perfused in advance passes through the side of stirring (800 ~ 2000r/min) ultrasonic wave added as precursor
It is uniformly mixed while method smashes the graphene three-dimensional framework that resin is perfused with pure bismaleimide resin matrix, obtains high dispersive graphite
Alkene reinforced resin based composites precursor slurry；
Step 3: the preparation of oriented graphite alkene reinforced resin based composites precursor:
Control graphene reinforced resin based composites precursor slurry temperature field makes temperature lower than 0 DEG C, regulation graphene enhancing
The viscosity of polymer matrix composites precursor slurry in 1 ~ 10 PaS, under suitable viscosity by control the field of force (generally 50 ~
500MPa), oriented graphite alkene reinforced resin based composites precursor is prepared in the way of cold pressing；
Step 4: the preparation of oriented graphite alkene reinforced resin based composites:
The oriented graphite alkene reinforced resin based composites precursor prepared in step 3 is injected into mold, vacuum is carried out
De-bubble after the completion of solidification, finally prepares oriented graphite alkene enhancing tree by the control temperature field base field of force to meet solidifying requirements
Resin-based composite, in which: be cured as gradient solidification, gradient condition of cure is as follows: 160 ~ 180 DEG C of solidifications 2h, pressure 50MPa；
190 ~ 210 DEG C solidify 1 hour, pressure 50MPa；220 ~ 240 DEG C solidify 4 hours, and pressure 50MPa, 250 ~ 260 DEG C solidify 4 hours,
Pressure 50MPa.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: in step 1, the graphene
The concentration of aqueous solution is 5 ~ 10mg/ml；The concentration of graphene oxide water solution is 5 ~ 20mg/ml.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: in step 1, describedization
Learning the temperature that reduction hydrazine hydrate uses is 90 DEG C, the use of the time is for 24 hours；Heat-treating temperature is 600 ~ 800 DEG C.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: in step 2, institute
The viscosity for stating resin is 10-3~10-2Pa·S。
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: in step 3, institute
Stating speed of agitator is 1000 ~ 1500r/min.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: in step 3, institute
The viscosity of graphene reinforced resin based composites slurry is stated in 1 ~ 5 PaS；The field of force is 50 ~ 300MPa.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: in step 4, institute
State gradient condition of cure are as follows: 170 ~ 180 DEG C of solidifications 2h, pressure 50MPa；200 ~ 210 DEG C solidify 1 hour, pressure 50MPa；230~
240 DEG C solidify 4 hours, pressure 50MPa；250 DEG C solidify 4 hours, pressure 50MPa.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment 1
In the present embodiment, the method for preparing high starch breeding alkene enhancing bismaleimide resin based composites is realized according to the following steps:
Step 1: the preparation of graphene sponge:
Method one, the preparation that graphene sponge is carried out using the method for improving freeze-drying, the specific steps are as follows: will be scattered
Concentration is that the graphene aqueous solution of 10mg/ml is freezed under low temperature (0 DEG C or less), while it is more to utilize freeze-drying to obtain
The graphene sponge (density 10mg/ml) in hole；
Method two prepares graphene sponge using the method for reduction, the specific steps are as follows: 10mg/ml graphene oxide is water-soluble
Liquid is freezed under low temperature (0 DEG C or less), while using freeze-drying obtaining porous graphene oxide sponge (density is
10mg/ml)；The method system for carrying out electronation for 24 hours at 90 DEG C of temperature using excessive hydrazine hydrate or being heat-treated at 700 DEG C
Standby graphene sponge out；
Step 2: the preparation of graphene reinforced resin based composites precursor slurry:
Resin is drawn by the method for priming by vacuum by the porous knot of the graphene sponge prepared in step 1 using negative pressure method
In structure, the specific steps are as follows: utilize negative pressure method, it is 10 that graphene sponge, which is placed into viscosity,-1In the resin of PaS, lead to
It crosses vacuum pump and baking oven is vacuumized (104~105Pa), i.e. the method for priming by vacuum, is drawn into the porous of graphene sponge for resin
In structure；
Graphene sponge resin to be perfused in advance passes through the side of stirring (800 ~ 2000r/min) ultrasonic wave added as precursor
It is uniformly mixed while method smashes the graphene three-dimensional framework that resin is perfused with pure bismaleimide resin matrix, obtains high dispersive graphite
Alkene reinforced resin based composites precursor slurry；
Step 3: the preparation of oriented graphite alkene reinforced resin based composites precursor:
Control graphene reinforced resin based composites precursor slurry temperature field makes temperature lower than 0 DEG C, regulation graphene enhancing
The viscosity of polymer matrix composites precursor slurry is in 10 PaS, under suitable viscosity (generally by the control field of force
500MPa), oriented graphite alkene reinforced resin based composites precursor is prepared in the way of cold pressing；
Step 4: the preparation of oriented graphite alkene reinforced resin based composites:
The oriented graphite alkene reinforced resin based composites precursor prepared in step 3 is injected into mold, vacuum is carried out
De-bubble after the completion of solidification, finally prepares oriented graphite alkene enhancing tree by the control temperature field base field of force to meet solidifying requirements
Resin-based composite, in which: be cured as gradient solidification, gradient condition of cure is as follows: 180 DEG C of solidifications 2h, pressure 50MPa；210℃
Solidification 1 hour, pressure 50MPa；240 DEG C solidify 4 hours, and pressure 50MPa, 260 DEG C solidify 4 hours, pressure 50MPa.
The present embodiment uses the previously prepared graphene macroform of freeze-drying, passes through the method for vacuum auxiliary pouring and molding
Prepare graphene reinforced resin based composites slurry.Capture oriented graphite alkene reinforced resin based composites key preparation skill
Art solves graphene orientation problem in resin matrix, realizes graphene high orientation in resin, obtains highly directional
Graphene reinforced resin based composites.The present embodiment realizes the preparation and microstructure of graphene three-dimensional framework reinforcement
Regulation obtains the density graphene sponge controllable in 10mg/ml density.The present embodiment obtains oriented graphite alkene reinforced resin base
Composite material, scanning prove graphene high orientation in resin matrix, while opposite resin matrix composite material mechanical property
10% can be promoted along orientation direction.
Embodiment 2:
In the present embodiment, the method for preparing high starch breeding alkene enhancing bismaleimide resin based composites is realized according to the following steps:
Step 1: the preparation of graphene sponge:
Method one, the preparation that graphene sponge is carried out using the method for improving freeze-drying, the specific steps are as follows: will be scattered
Concentration is that the graphene aqueous solution of 20mg/ml is freezed under low temperature (0 DEG C or less), while it is more to utilize freeze-drying to obtain
The graphene sponge (density 20mg/ml) in hole；
Method two prepares graphene sponge using the method for reduction, the specific steps are as follows: 20mg/ml graphene oxide is water-soluble
Liquid is freezed under low temperature (0 DEG C or less), while using freeze-drying obtaining porous graphene oxide sponge (density is
20mg/ml)；The method for carrying out electronation for 24 hours at 90 DEG C of temperature using excessive hydrazine hydrate or being heat-treated at 1000 DEG C
Prepare graphene sponge；
Step 2: the preparation of graphene reinforced resin based composites precursor slurry:
Resin is drawn by the method for priming by vacuum by the porous knot of the graphene sponge prepared in step 1 using negative pressure method
In structure, the specific steps are as follows: utilize negative pressure method, it is 10 that graphene sponge, which is placed into viscosity,-2In the resin of PaS, lead to
It crosses vacuum pump and baking oven is vacuumized (105Pa), i.e. resin, is drawn into the porous structure of graphene sponge by the method for priming by vacuum
In the middle；
Graphene sponge resin to be perfused in advance is incited somebody to action as precursor by the method for stirring (1500r/min) ultrasonic wave added
The graphene three-dimensional framework of perfusion resin is uniformly mixed while smashing with pure bismaleimide resin matrix, is obtained high dispersive graphene and is increased
Strong polymer matrix composites precursor slurry；
Step 3: the preparation of oriented graphite alkene reinforced resin based composites precursor:
Control graphene reinforced resin based composites precursor slurry temperature field makes temperature lower than 0 DEG C, regulation graphene enhancing
The viscosity of polymer matrix composites precursor slurry is in 10 PaS, under suitable viscosity (generally by the control field of force
500MPa), oriented graphite alkene reinforced resin based composites precursor is prepared in the way of cold pressing；
Step 4: the preparation of oriented graphite alkene reinforced resin based composites:
The oriented graphite alkene reinforced resin based composites precursor prepared in step 3 is injected into mold, vacuum is carried out
De-bubble after the completion of solidification, finally prepares oriented graphite alkene enhancing tree by the control temperature field base field of force to meet solidifying requirements
Resin-based composite, in which: be cured as gradient solidification, gradient condition of cure is as follows: 160 DEG C of solidifications 2h, pressure 50MPa；190℃
Solidification 1 hour, pressure 50MPa；220 DEG C solidify 4 hours, and pressure 50MPa, 250 DEG C solidify 4 hours, pressure 50MPa.
Fig. 1 is the pictorial diagram of gained graphene sponge in the present embodiment step 1, as shown in Figure 1, gained graphene sponge
Three-dimensional framework surfacing；Fig. 2 is that gained graphene reinforced resin based composites precursor is in kind in the present embodiment step 3
Figure, as shown in Figure 2, gained graphene reinforced resin based composites precursor is smooth through multiple fold surface；Fig. 3 is this implementation
The microcosmic scanned photograph of gained oriented graphite alkene reinforced resin based composites in example step 4, from the figure 3, it may be seen that graphene is being set
It is oriented in aliphatic radical body；Fig. 4 is the mechanical property of gained oriented graphite alkene reinforced resin based composites in the present embodiment step 4
Energy photo, as shown in Figure 4, mechanical property promotes 30%.
The present embodiment uses the previously prepared graphene macroform of freeze-drying, passes through the method for vacuum auxiliary pouring and molding
Prepare graphene reinforced resin based composites slurry.Capture oriented graphite alkene reinforced resin based composites key preparation skill
Art solves graphene orientation problem in resin matrix, realizes graphene high orientation in resin, obtains highly directional
Graphene reinforced resin based composites.The present embodiment realizes the preparation and microstructure of graphene three-dimensional framework reinforcement
Regulation obtains the density graphene sponge controllable in 20mg/ml density.The present embodiment obtains oriented graphite alkene reinforced resin base
Composite material, scanning prove graphene high orientation in resin matrix, while opposite resin matrix composite material mechanical property
30% can be promoted along orientation direction.
Embodiment 3:
In the present embodiment, the method for preparing high starch breeding alkene enhancing bismaleimide resin based composites is realized according to the following steps:
Step 1: the preparation of graphene sponge:
Method one, the preparation that graphene sponge is carried out using the method for improving freeze-drying, the specific steps are as follows: will be scattered
Concentration is that the graphene aqueous solution of 10mg/ml is freezed under low temperature (0 DEG C or less), while it is more to utilize freeze-drying to obtain
The graphene sponge (density 10mg/ml) in hole；
Method two prepares graphene sponge using the method for reduction, the specific steps are as follows: 10mg/ml graphene oxide is water-soluble
Liquid is freezed under low temperature (0 DEG C or less), while using freeze-drying obtaining porous graphene oxide sponge (density is
10mg/ml)；The method system for carrying out electronation for 24 hours at 90 DEG C of temperature using excessive hydrazine hydrate or being heat-treated at 800 DEG C
Standby graphene sponge out；
Step 2: the preparation of graphene reinforced resin based composites precursor slurry:
Resin is drawn by the method for priming by vacuum by the porous knot of the graphene sponge prepared in step 1 using negative pressure method
In structure, the specific steps are as follows: utilize negative pressure method, it is 10 that graphene sponge, which is placed into viscosity,-1In the resin of PaS, lead to
It crosses vacuum pump and baking oven is vacuumized (105Pa), i.e. resin, is drawn into the porous structure of graphene sponge by the method for priming by vacuum
In the middle；
Graphene sponge resin to be perfused in advance is incited somebody to action as precursor by the method for stirring (2000r/min) ultrasonic wave added
The graphene three-dimensional framework of perfusion resin is uniformly mixed while smashing with pure bismaleimide resin matrix, is obtained high dispersive graphene and is increased
Strong polymer matrix composites precursor slurry；
Step 3: the preparation of oriented graphite alkene reinforced resin based composites precursor:
Control graphene reinforced resin based composites precursor slurry temperature field makes temperature lower than 0 DEG C, regulation graphene enhancing
The viscosity of polymer matrix composites precursor slurry is in 10 PaS, under suitable viscosity (generally by the control field of force
400MPa), oriented graphite alkene reinforced resin based composites precursor is prepared in the way of cold pressing；
Step 4: the preparation of oriented graphite alkene reinforced resin based composites:
The oriented graphite alkene reinforced resin based composites precursor prepared in step 3 is injected into mold, vacuum is carried out
De-bubble after the completion of solidification, finally prepares oriented graphite alkene enhancing tree by the control temperature field base field of force to meet solidifying requirements
Resin-based composite, in which: be cured as gradient solidification, gradient condition of cure is as follows: 180 DEG C of solidifications 2h, pressure 50MPa； 210
DEG C solidification 1 hour, pressure 50MPa；240 DEG C solidify 4 hours, and pressure 50MPa, 260 DEG C solidify 4 hours, pressure 50MPa.
The present embodiment uses the previously prepared graphene macroform of freeze-drying, passes through the method for vacuum auxiliary pouring and molding
Prepare graphene reinforced resin based composites slurry.Capture oriented graphite alkene reinforced resin based composites key preparation skill
Art solves graphene orientation problem in resin matrix, realizes graphene high orientation in resin, obtains highly directional
Graphene reinforced resin based composites.The present embodiment realizes the preparation and microstructure of graphene three-dimensional framework reinforcement
Regulation obtains the density graphene sponge controllable in 10mg/ml density.The present embodiment obtains oriented graphite alkene reinforced resin base
Composite material, scanning prove graphene high orientation in resin matrix, while opposite resin matrix composite material mechanical property
10% can be promoted along orientation direction.
Embodiment 4:
In the present embodiment, the method for preparing high starch breeding alkene enhancing bismaleimide resin based composites is realized according to the following steps:
Step 1: the preparation of graphene sponge:
Method one, the preparation that graphene sponge is carried out using the method for improving freeze-drying, the specific steps are as follows: will be scattered
Concentration is that the graphene aqueous solution of 8mg/ml is freezed under low temperature (0 DEG C or less), while it is more to utilize freeze-drying to obtain
The graphene sponge (density 8mg/ml) in hole；
Method two prepares graphene sponge using the method for reduction, the specific steps are as follows: by 8mg/ml graphene oxide water solution
It is freezed under low temperature (0 DEG C or less), while using freeze-drying obtaining porous graphene oxide sponge (density is
8mg/ml)；The method system for carrying out electronation for 24 hours at 90 DEG C of temperature using excessive hydrazine hydrate or being heat-treated at 700 DEG C
Standby graphene sponge out；
Step 2: the preparation of graphene reinforced resin based composites precursor slurry:
Resin is drawn by the method for priming by vacuum by the porous knot of the graphene sponge prepared in step 1 using negative pressure method
In structure, the specific steps are as follows: utilize negative pressure method, it is 10 that graphene sponge, which is placed into viscosity,-1In the resin of PaS, lead to
It crosses vacuum pump and baking oven is vacuumized (105Pa), i.e. resin, is drawn into the porous structure of graphene sponge by the method for priming by vacuum
In the middle；
Graphene sponge resin to be perfused in advance is incited somebody to action as precursor by the method for stirring (1800r/min) ultrasonic wave added
The graphene three-dimensional framework of perfusion resin is uniformly mixed while smashing with pure bismaleimide resin matrix, is obtained high dispersive graphene and is increased
Strong polymer matrix composites precursor slurry；
Step 3: the preparation of oriented graphite alkene reinforced resin based composites precursor:
Control graphene reinforced resin based composites precursor slurry temperature field makes temperature lower than 0 DEG C, regulation graphene enhancing
The viscosity of polymer matrix composites precursor slurry is in 10 PaS, under suitable viscosity (generally by the control field of force
500MPa), oriented graphite alkene reinforced resin based composites precursor is prepared in the way of cold pressing；
Step 4: the preparation of oriented graphite alkene reinforced resin based composites:
The oriented graphite alkene reinforced resin based composites precursor prepared in step 3 is injected into mold, vacuum is carried out
De-bubble after the completion of solidification, finally prepares oriented graphite alkene enhancing tree by the control temperature field base field of force to meet solidifying requirements
Resin-based composite, in which: be cured as gradient solidification, gradient condition of cure is as follows: 180 DEG C of solidifications 2h, pressure 50MPa；200
DEG C solidification 1 hour, pressure 50MPa；240 DEG C solidify 4 hours, and pressure 50MPa, 250 DEG C solidify 4 hours, pressure 50MPa.
The present embodiment uses the previously prepared graphene macroform of freeze-drying, passes through the method for vacuum auxiliary pouring and molding
Prepare graphene reinforced resin based composites slurry.Capture oriented graphite alkene reinforced resin based composites key preparation skill
Art solves graphene orientation problem in resin matrix, realizes graphene high orientation in resin, obtains highly directional
Graphene reinforced resin based composites.The present embodiment realizes the preparation and microstructure of graphene three-dimensional framework reinforcement
Regulation obtains the density graphene sponge controllable in 8mg/ml density.The present embodiment obtains oriented graphite alkene reinforced resin base
Composite material, scanning prove graphene high orientation in resin matrix, while opposite resin matrix composite material mechanical property
15% can be promoted along orientation direction.
Claims (7)
1. a kind of preparation method of high starch breeding alkene enhancing bismaleimide resin based composites, it is characterised in that the method includes
Following steps:
Step 1: the preparation of graphene reinforced resin based composites precursor slurry:
Pure bismaleimide resin is drawn by the method for priming by vacuum by the graphene sponge prepared in step 1 using negative pressure method
In porous structure；
The stone of resin will be perfused by the method for stirring ultrasonic wave added as precursor for graphene sponge resin to be perfused in advance
It is uniformly mixed while black alkene three-dimensional framework is smashed with pure bismaleimide resin matrix, it is compound to obtain high dispersive graphene reinforced resin base
Material precursor slurry；
Step 2: the preparation of oriented graphite alkene reinforced resin based composites precursor:
Control graphene reinforced resin based composites precursor slurry temperature field makes temperature lower than 0 DEG C, regulation graphene enhancing
The viscosity of polymer matrix composites precursor slurry, by the control field of force under suitable viscosity, utilizes cold pressing in 1 ~ 10 PaS
Mode prepare oriented graphite alkene reinforced resin based composites precursor；
Step 3: the preparation of oriented graphite alkene reinforced resin based composites:
Oriented graphite alkene reinforced resin based composites precursor is injected into mold, froth in vacuum is carried out, passes through control
The temperature field base field of force is to meet solidifying requirements, after the completion of solidification, finally prepares oriented graphite alkene reinforced resin based composites.
2. the preparation method of high starch breeding alkene enhancing bismaleimide resin based composites according to claim 1, feature
It is in the step 1, resin is drawn into graphene sponge porous structure to specific step is as follows: using negative pressure method,
It is 10 that graphene sponge, which is placed into viscosity,-3~10-1In the resin of PaS, baking oven is vacuumized 10 by vacuum pump4~
105Pa, the i.e. method of priming by vacuum, resin is drawn into the porous structure of graphene sponge.
3. the preparation method of high starch breeding alkene enhancing bismaleimide resin based composites according to claim 1 or 2, special
Sign be the graphene sponge the preparation method is as follows: using improve freeze-drying method carry out graphene sponge system
It is standby, the specific steps are as follows: to freeze the graphene aqueous solution that scattered concentration is 5 ~ 20mg/ml at low temperature, simultaneously
Porous graphene sponge is obtained using freeze-drying.
4. the preparation method of high starch breeding alkene enhancing bismaleimide resin based composites according to claim 1 or 2, special
Sign be the graphene sponge the preparation method is as follows: 5 ~ 30mg/ml graphene oxide water solution is carried out at low temperature cold
Freeze, while obtaining porous graphene oxide sponge using freeze-drying；Using excessive hydrazine hydrate at 70 ~ 90 DEG C of temperature
The method for carrying out electronation for 24 hours or heat-treating at 200 ~ 1000 DEG C prepares graphene sponge.
5. the preparation method of high starch breeding alkene enhancing bismaleimide resin based composites according to claim 1, feature
The revolving speed for being the stirring is 800 ~ 2000r/min.
6. the preparation method of high starch breeding alkene enhancing bismaleimide resin based composites according to claim 1, feature
It is that the field of force is 50 ~ 500MPa.
7. the preparation method of high starch breeding alkene enhancing bismaleimide resin based composites according to claim 1, feature
It is that the gradient that is cured as solidifies, gradient condition of cure is as follows: 160 ~ 180 DEG C of solidifications 2h, pressure 50MPa；190 ~ 210 DEG C solid
Change 1 hour pressure 50MPa；220 ~ 240 DEG C solidify 4 hours, and pressure 50MPa, 250 ~ 260 DEG C solidify 4 hours, pressure 50MPa.
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