CN110172175A - A kind of preparation method of porous polyimide conducing composite material - Google Patents
A kind of preparation method of porous polyimide conducing composite material Download PDFInfo
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- CN110172175A CN110172175A CN201910450201.4A CN201910450201A CN110172175A CN 110172175 A CN110172175 A CN 110172175A CN 201910450201 A CN201910450201 A CN 201910450201A CN 110172175 A CN110172175 A CN 110172175A
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention provides a kind of preparation method of porous polyimide conducing composite material, prepares composite polyamide acid dispersion liquid I and II using situ aggregation method；Composite polyamide acid dispersion liquid I is cast in mold, composite polyamide acid porous layer is prepared by the method for Thermal inactive；The surface for being cast in composite polyamide acid porous layer composite polyamide acid dispersion liquid II is formed into confining bed, obtains the polyamic acid composite material with double-layer structure；Polyamic acid composite material with double-layer structure is subjected to sequencing heating, the imidization of polyamic acid is realized, finally obtains porous polyimide conducing composite material；The present invention is using polyimides as matrix, a kind of porous light new function electromagnetic shielding composite material with double-layer structure is developed by conductive filler of carbon material, the characteristics of big specific density that traditional electromagnetic shielding material has, poor corrosion resistance can not only be improved and be difficult to the disadvantages of forming, but also impart its good heat resistance.
Description
Technical field
The present invention relates to a kind of preparation method of conducing composite material more particularly to a kind of porous polyimide conduction are compound
The preparation method of material, belongs to field of composite material preparation.
Background technique
With the development of society, new material is in many technologies such as aerospace, auto industry, medical instrument and architectural engineering
Field obtains development with rapid changepl. never-ending changes and improvements.Lightweight, functionalization and the environmental protection of material structure component propose more material
High requirement, polymer matrix composite have advantage outstanding as a kind of new material in terms of lightweight and functionalization.
Therefore, the various fields in life, polymer matrix composite have obtained extensive concern and application.Due to electronic information skill
The fast development of art, the Detection Techniques such as radar, infrared, laser are widely applied so that capture to target and positioning are increasingly accurate,
Therefore, electromangnetic spectrum becomes focus.In addition, Electromagnetic Wave Radiation on Human can also generate adverse effect, for example, it is cancer, white
The raising of the disease incidences such as blood disease and the increase of amount of electromagnetic radiation have certain relationship.Therefore, the electromagnetism of efficient and light weight is explored
Shielding composite achievees the purpose that microwave absorption and prevents electromagnetic shielding from polluting, it has also become there is an urgent need to solve for today's society
Certainly the problem of.
Summary of the invention
It is a kind of multifunctional integrated with electromagnetic shielding, heat-insulating flame-retardant, absorbing sound and lowering noise etc. the purpose of the invention is to provide
A kind of preparation method for the porous polyimide conducing composite material changed.
The object of the present invention is achieved like this:
A kind of preparation method of porous polyimide conducing composite material, includes the following steps:
Step 1: composite polyamide acid dispersion liquid I and II are prepared using situ aggregation method；
Step 2: composite polyamide acid dispersion liquid I is cast in mold, is prepared by the method for Thermal inactive compound
Polyamic acid porous layer；The surface for being cast in composite polyamide acid porous layer composite polyamide acid dispersion liquid II is formed into closing
Layer, 60~90 DEG C of 4~12h of vacuum drying obtain the polyamic acid composite material with double-layer structure；
Step 3: the polyamic acid composite material with double-layer structure is subjected to sequencing heating, realizes polyamic acid
Imidization, finally obtaining upper layer is confining bed, and lower layer is that the porous polyimide with coralliform empty structure porous layer is conductive
Composite material
The invention also includes features some in this way:
1. the volume ratio of the composite polyamide acid dispersion liquid I and composite polyamide acid dispersion liquid II is 1~15: 1；
2. composite polyamide acid dispersion liquid I's the preparation method comprises the following steps: respectively by pore-foaming agent, conductive filler under normal temperature and pressure
It is dispersed in solvent, sequentially adds diamines, dianhydride monomer, the volume of the pore-foaming agent and solvent under inert gas protection
Than being 1: 1~10；Reaction temperature be 20~30 DEG C, the reaction time be 3~for 24 hours, obtain solid content be 10%~20% polyamides
Amino acid dispersion liquid I；
3. composite polyamide acid dispersion liquid II's the preparation method comprises the following steps: being dispersed in conductive filler under normal temperature and pressure
In solvent, diamines, dianhydride monomer are sequentially added under inert gas protection, reaction temperature is 20~30 DEG C, the reaction time is 3~
24 h obtain the composite polyamide acid dispersion liquid II that solid content is 10%~20%；
4. the diamines, dianhydride monomer molar ratio are 1: 1.01~1.1；The conductive filler and monomer weight ratio be 1~
20: 100；The monomer is diamine monomer, dianhydride monomer quality sum；
5. the process of described programization heating is 100 DEG C of 1~2h of constant temperature；120 DEG C of 1~2h of constant temperature；180 DEG C of constant temperature 1~2
h；300 DEG C of 0.5~1h of constant temperature；
6. the conductive filler is one of modified graphene oxide, graphene, carbon black and multi-walled carbon nanotube or more
Kind；The pore-foaming agent is dibutyl phthalate and/or polyethylene glycol；
7. the diamine monomer is 4,4'- diaminodiphenyl ether, 4,4'- diaminodiphenylmethane, p-phenylenediamine and isophthalic
One of diamines is a variety of；The dianhydride monomer is 3,3', 4,4'- benzophenone tetracid dianhydride, bisphenol A dianhydride and 4,4'- connection
One of phenylate dianhydride is a variety of；
8. the solvent be n,N-dimethylacetamide, n,N-Dimethylformamide or N-Methyl pyrrolidone, it is described lazy
Property gas be nitrogen or argon gas.
Compared with prior art, the beneficial effects of the present invention are:
The present invention develops a kind of with the porous of double-layer structure using polyimides as matrix using carbon material as conductive filler
Light new function electromagnetic shielding composite material, can not only improve specific density that traditional electromagnetic shielding material has it is big,
The characteristics of poor corrosion resistance is with being difficult to the disadvantages of forming, and imparting its good heat resistance.
Detailed description of the invention
The SEM figure for the porous polyimide conducing composite material closing layer surface that Fig. 1 a embodiment of the present invention 3 is prepared
Piece；
The section for the porous polyimide conducing composite material double-layer structure that Fig. 1 b embodiment of the present invention 3 is prepared
SEM picture；
The SEM on the surface for the porous polyimide conducing composite material porous layer that Fig. 1 c embodiment of the present invention 3 is prepared
Picture face；
Fig. 2 is the coralliform hole of the porous polyimide conducing composite material porous layer prepared for the embodiment of the present invention 1
The section the SEM picture of structure.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing.
A kind of preparation method of polyimides conducing composite material, (1) are contained pore-foaming agent using situ aggregation method preparation, are led
The composite polyamide acid dispersion liquid I (CPAA-I) of electric filler, CPAA-I is cast in mold.Pass through the method for Thermal inactive
Prepare composite polyamide acid porous layer.(2) the composite polyamide acid dispersion liquid containing conductive filler is prepared using situ aggregation method
II (CPAA-II), the ratio that the volume ratio according to CPAA-I and CPAA-II is 1~15: 1, is cast in step 1 for CPAA-II
The surface of obtained composite polyamide acid porous layer.60~90 DEG C of 4~12h of vacuum drying, in composite polyamide acid porous layer table
Face forms confining bed, obtains the polyamic acid composite material with double-layer structure.(3) polyamic acid with double-layer structure is answered
Condensation material carries out sequencing heating, realizes the imidization of polyamic acid, the porous polyimide conduction for preparing double-layer structure is compound
Material.Pore-foaming agent, conductive filler: being dispersed in solvent by the preparation method of the CPAA-I respectively under normal temperature and pressure,
Sequentially adding diamines, dianhydride monomer under inert gas shielding, reaction temperature is 20~30 DEG C, the reaction time is 3~for 24 hours.Pore
The volume ratio of agent and solvent is 1: 1~10；Diamines, dianhydride monomer molar ratio are 1: 1.01~1.1；Polyamic acid solution solid content
It is 10%~20%；Conductive filler and monomer (diamine monomer, dianhydride monomer quality sum) mass ratio are 1~20: 100.It is described
Conductive filler: being dispersed in solvent by the preparation method of CPAA-II under normal temperature and pressure, successively adds under inert gas protection
Entering diamines, dianhydride monomer, reaction temperature is 20~30 DEG C, the reaction time is 3~for 24 hours.Diamines, dianhydride monomer molar ratio are 1:
1.01~1.1；Polyamic acid solution solid content is 10%~20%；Conductive filler and monomer (diamine monomer, dianhydride monomer quality
The sum of) mass ratio be 1~20: 100；The Thermal inactive method be carry out vacuum heating treatment, treatment temperature be 60 DEG C~
90 DEG C, the processing time is 6~12h.Sequencing temperature-rise period is 100 DEG C of 1~2h of constant temperature；120 DEG C of 1~2h of constant temperature；180 DEG C of constant temperature
1~2h；300 DEG C of 0.5~1h of constant temperature.The pore-foaming agent is dibutyl phthalate (DBP), one in polyethylene glycol (PEG)
Kind or two kinds.The solvent is n,N-dimethylacetamide (DMAc), n,N-Dimethylformamide (DMF), N- crassitude
One of ketone (NMP)；State conductive filler be one of modified graphene oxide, graphene, carbon black, multi-walled carbon nanotube or
It is a variety of；The inert gas is one of nitrogen or argon gas.The diamine monomer is 4,4'- diaminodiphenyl ether
(ODA), one of 4,4'- diaminodiphenylmethane (MDA), p-phenylenediamine, m-phenylene diamine (MPD) or a variety of, dianhydride monomer 3,
One of 3', 4,4'- benzophenone tetracid dianhydride (BTDA), bisphenol A dianhydride (BPADA), 4,4'- biphenyl ether dianhydride (ODPA)
Or it is a variety of；There is the porous polyimide conducing composite material of double-layer structure electromagnetic shielding with higher to absorb efficiency；It is a kind of more
Hole polyimides conducing composite material has double-layer structure, and lower layer is the porous layer with coralliform hole configurations, and upper layer is envelope
Close layer.
Polyimides of the present invention is due to its every excellent properties by the basis material as numerous composite materials: first, gather
Acid imide material so that polyimides has excellent high temperature resistance, and is considered as heat resistance most because of its design feature
For excellent one of polymer material, while there is good resistance to low temperature again.Second, due to five yuan of acyls in polyimides
The presence of imide ring includes the presence of the phenyl ring in aromatic polyimide, so that interaction force between polyimide molecule chain
It is very big, therefore it is made to have excellent mechanical property.Third, polyimides itself are used as a kind of lower high score of the coefficient of expansion
Sub- material substantially increases its dimensional stability in use.4th, polyimides has good resistant to chemical etching
Performance can use under some more special environment.Therefore, select polyimides that can make as the matrix of the composite material
The functionalized design of the composite material is more diversified, and assigns the composite material excellent properties.Carbon system filler due to
The advantages that its density is small, corrosion-resistant and electric conductivity is stablized, is important conductive filler.These carbon materials not only have low close
Degree, light feature, and there is high aspect ratio, and effective conductive mesh can be formed in polymer matrix composite
Network, to assign their ideal electricity and shielding properties.
The present invention is prepared for composite polyamide acid dispersion liquid CPAA-I and CPAA-II by situ aggregation method, by CPAA-I
It is cast in mold, polyamic acid porous layer is prepared using thermally induced phase separation.CPAA-II is cast in the surface of porous layer,
Heating removal solvent forms confining bed in porous layer surface, assigns the characteristic of the polyamic acid conducing composite material double-layer structure,
The imidization of polyamic acid is realized by sequencing temperature-rise period, preparing has the porous polyimide conduction of double-layer structure compound
Material.The present invention has the porous composite wood of double-layer structure using carbon material as conductive filler preparation using polyimides as matrix
Material has good electromagnetic shielding performance, and has the characteristics that light, heat resistance and durability are good, in electromagnetic shielding field
It has a good application prospect, especially has in the multifunctional alls demand such as electromagnetic shielding, heat-insulating flame-retardant, absorbing sound and lowering noise field
Apparent advantage also has application potential in electrochemical field.
Embodiment 1:
1, the preparation method for the composite polyamide acid porous layer that conductive filler content is 8%: according to pore under normal temperature and pressure
The ratio that agent DBP and solvent DMAc volume ratio are 1: 4.2 measures 6ml DBP, 25ml DMAc in two mouth flask, uniformly divides
It dissipates.The ratio for being 1:1.01 according to diamine monomer ODA and dianhydride monomer BPADA molar ratio, weighs 1.139g ODA and 2.99g
BPADA.It is weighed according to the ratio that conductive filler and monomer (diamine monomer, dianhydride monomer quality sum) mass ratio are 8.7:100
0.36g conductive filler (modified graphene oxide=multi-walled carbon nanotube=0.18g).By conductive filler be dispersed in DBP and
In the dispersion liquid of DMAc, ODA, BPADA monomer being sequentially added under nitrogen protection, reacts 4h at 25 DEG C, obtaining solid content is
15% composite polyamide acid dispersion liquid I-8% (CPAA-I-8%).CPAA-I-8% is cast in mold, at 80 DEG C
Under the conditions of constant temperature 12h, obtain conductive filler content be 8% composite polyamide acid porous layer.
2, it the preparation method for the composite polyamide acid double-layer structure that conductive filler content is 8%: is measured under normal temperature and pressure
25ml DMAc is in two mouth flask.The ratio for being 1:1.01 according to diamine monomer ODA and dianhydride monomer BPADA molar ratio, weighs
1.139g ODA and 2.99g BPADA.It is according to conductive filler and monomer (diamine monomer, dianhydride monomer quality sum) mass ratio
The ratio of 8.7:100 weighs 0.36g conductive filler (modified graphene oxide=multi-walled carbon nanotube=0.18g).Conduction is filled out
Material is dispersed in the dispersion liquid of DBP and DMAc, is sequentially added ODA, BPADA monomer under nitrogen protection, is reacted at 25 DEG C
4h obtains the composite polyamide acid dispersion liquid II-8% (CPAA- II -8%) that solid content is 15%.According to CPAA-I-8% with
CPAA-II-8%, is cast in the surface of porous layer prepared by step 1,80 by the ratio that CPAA-II-8% volume ratio is 3: 1
Constant temperature 6h under conditions of DEG C obtains the polyamic acid composite material with double-layer structure that conductive filler content is 8%.
3, the polyamic acid composite material with double-layer structure for preparing step 2 is according to 100 DEG C of constant temperature 2h；120 DEG C of perseverances
Warm 2h；180 DEG C of constant temperature 1h；The sequencing temperature-rise period of 300 DEG C of constant temperature 0.5h completes hot imidization.Conductive filler is obtained through demoulding
The porous polyimide conducing composite material with double-layer structure that content is 8%.
The porous layer thickness of the porous polyimide conducing composite material is 1.5mm, confining bed 0.5mm, integral thickness
For 2 mm, density 0.8217g/cm3, glass transition temperature is 214.13 DEG C, and the Residual carbon at 800 DEG C is 50%.
Electromagnetic shielding performance test is carried out using porous polyimide conducing composite material of the X-band waveguide method to the double-layer structure,
The result shows that the reflection loss efficiency of the porous polyimide conducing composite material is 0~-26dB in 8~12GHz.
Embodiment 2:
1, the preparation method for the composite polyamide acid porous layer that conductive filler content is 10%: according to pore under normal temperature and pressure
The ratio that agent DBP and solvent DMAc volume ratio are 1: 4.2 measures 6ml DBP, 25ml DMAc in two mouth flask, uniformly divides
It dissipates.The ratio for being 1:1.01 according to diamine monomer ODA and dianhydride monomer BPADA molar ratio, weighs 1.139g ODA and 2.99g
BPADA.It is weighed according to the ratio that conductive filler and monomer (diamine monomer, dianhydride monomer quality sum) mass ratio are 11:100
0.459g conductive filler (modified graphene oxide=multi-walled carbon nanotube=0.2295g).Conductive filler is dispersed in
In the dispersion liquid of DBP and DMAc, ODA, BPADA monomer are sequentially added under nitrogen protection, 4h is reacted at 25 DEG C, obtains solid content
For 15% composite polyamide acid dispersion liquid I-10% (CPAA-I-10%).CPAA-I-10% is cast in mold, 80
Constant temperature 12h under conditions of DEG C obtains the composite polyamide acid porous layer that conductive filler content is 10%.
2, it the preparation method for the composite polyamide acid double-layer structure that conductive filler content is 10%: is measured under normal temperature and pressure
25ml DMAc is in two mouth flask.The ratio for being 1:1.01 according to diamine monomer ODA and dianhydride monomer BPADA molar ratio, weighs
1.139g ODA and 2.99g BPADA.It is according to conductive filler and monomer (diamine monomer, dianhydride monomer quality sum) mass ratio
The ratio of 11:100 weighs 0.459g conductive filler (modified graphene oxide=multi-walled carbon nanotube=0.2295g).It will be conductive
Uniform filling is scattered in the dispersion liquid of DBP and DMAc, sequentially adds ODA, BPADA monomer under nitrogen protection, anti-at 25 DEG C
4h is answered, the composite polyamide acid dispersion liquid II-10% (CPAA- II -10%) that solid content is 15% is obtained.According to CPAA-I-
10% with CPAA-II-10% volume ratio be 3: 1 ratio, CPAA-II-10% is cast in the table of porous layer prepared by step 1
Face, constant temperature 6h under conditions of 80 DEG C obtain the polyamic acid composite wood with double-layer structure that conductive filler content is 10%
Material.
3, the polyamic acid composite material with double-layer structure for preparing step 2 is according to 100 DEG C of constant temperature 2h；120 DEG C of perseverances
Warm 2h；180 DEG C of constant temperature 1h；The sequencing temperature-rise period of 300 DEG C of constant temperature 0.5h completes hot imidization.Conductive filler is obtained through demoulding
The porous polyimide conducing composite material with double-layer structure that content is 10%.
The porous layer thickness of the porous polyimide conducing composite material is 1.5mm, confining bed 0.5mm, integral thickness
For the porous polyimide conducing composite material of 2 mm, density 0.7837g/cm3, glass transition temperature 220.91
DEG C, Residual carbon at 800 DEG C is up to 55%.It is compound using porous polyimide conduction of the X-band waveguide method to the double-layer structure
Material carry out electromagnet shield effect test, the result shows that in 8-12GHz the porous polyimide conducing composite material it is anti-
Penetrating loss efficiency is 0~-36dB.
Embodiment 3:
1, the preparation method for the composite polyamide acid porous layer that conductive filler content is 12%: according to pore under normal temperature and pressure
The ratio that agent DBP and solvent DMAc volume ratio are 1: 4.2 measures 6ml DBP, 25ml DMAc in two mouth flask, uniformly divides
It dissipates.The ratio for being 1:1.01 according to diamine monomer ODA and dianhydride monomer BPADA molar ratio, weighs 1.139g ODA and 2.99g
BPADA.It is weighed according to the ratio that conductive filler and monomer (diamine monomer, dianhydride monomer quality sum) mass ratio are 13.6:100
0.563g conductive filler (modified graphene oxide=multi-walled carbon nanotube=0.2815g).Conductive filler is dispersed in DBP
In the dispersion liquid of DMAc, ODA, BPADA monomer being sequentially added under nitrogen protection, reacts 4h at 25 DEG C, obtaining solid content is
15% composite polyamide acid dispersion liquid I-12% (CPAA-I-12%).CPAA-I-12% is cast in mold, at 80 DEG C
Under conditions of constant temperature 12h, obtain conductive filler content be 12% composite polyamide acid porous layer.
2, it the preparation method for the composite polyamide acid double-layer structure that conductive filler content is 12%: is measured under normal temperature and pressure
25ml DMAc is in two mouth flask.The ratio for being 1:1.01 according to diamine monomer ODA and dianhydride monomer BPADA molar ratio, weighs
1.139g ODA and 2.99g BPADA.It is according to conductive filler and monomer (diamine monomer, dianhydride monomer quality sum) mass ratio
The ratio of 13.6:100 weighs 0.563g conductive filler (modified graphene oxide=multi-walled carbon nanotube=0.2815g).It will lead
Electric uniform filling is scattered in the dispersion liquid of DBP and DMAc, sequentially adds ODA, BPADA monomer under nitrogen protection, at 25 DEG C
4h is reacted, the composite polyamide acid dispersion liquid II-12% (CPAA- II -12%) that solid content is 15% is obtained.According to CPAA-I-
12% with CPAA-II-12% volume ratio be 3: 1 ratio, CPAA-II-12% is cast in the table of porous layer prepared by step 1
Face, constant temperature 6h under conditions of 80 DEG C obtain the polyamic acid composite wood with double-layer structure that conductive filler content is 12%
Material.
3, the polyamic acid composite material with double-layer structure for preparing step 2 is according to 100 DEG C of constant temperature 2h；120 DEG C of perseverances
Warm 2h；180 DEG C of constant temperature 1h；The sequencing temperature-rise period of 300 DEG C of constant temperature 0.5h completes hot imidization.Conductive filler is obtained through demoulding
The porous polyimide conducing composite material with double-layer structure that content is 12%.
The porous layer of the porous polyimide conducing composite material is 1.5mm, confining bed 0.5mm, integral thickness 2mm
Porous polyimide conducing composite material, density 0.5576g/cm3, glass transition temperature is 223.15 DEG C, at 800 DEG C
Under Residual carbon be up to 59%.It is carried out using porous polyimide conducing composite material of the X-band waveguide method to the double-layer structure
Electromagnet shield effect test, the result shows that the reflection loss of the porous polyimide conducing composite material is imitated in 8~12GHz
It can be 0~-44dB.
In summary: the present invention provides a kind of porous polyimide conducing composite material preparation method and its electromagnetic shieldings
Function.Porous polyimide conducing composite material of the present invention has double-layer structure, and bottom is porous layer, and top is confining bed.It is logical
Situ aggregation method composite polyamide acid dispersion liquid I of the preparation containing conductive filler, pore-foaming agent is crossed, is prepared using thermally induced phase separation poly-
Amic acid porous layer；By in composite polyamide acid dispersion liquid II of the porous layer upper containing conductive filler, and be heat-treated make it is molten
Agent volatilization forms confining bed on porous layer top；It is heated up by sequencing and realizes the imidization of polyamic acid, prepare porous polyamides
Imines conducing composite material.Top closed layer completely cuts off extraneous steam in use and pollutes the intrusion of particle, and it is more to improve this
Hole composite material service life.Bottom porous layer has coralliform hole configurations, and porous structure assigns the composite material lightweight
The characteristics of.The porous polyimide composite material preparation is simple and convenient to operate, and has designability.There is electricity for preparation
The lightweight conductive porous polymer based composites of the multifunctional alls such as magnetic screen, heat-insulating flame-retardant, absorbing sound and lowering noise provide one
The new thinking of kind.
Claims (10)
1. a kind of preparation method of porous polyimide conducing composite material, characterized in that include the following steps:
Step 1: composite polyamide acid dispersion liquid I and II are prepared using situ aggregation method；
Step 2: composite polyamide acid dispersion liquid I is cast in mold, compound polyamides is prepared by the method for Thermal inactive
Amino acid porous layer；By composite polyamide acid dispersion liquid II be cast in composite polyamide acid porous layer surface formed confining bed, 60
~90 DEG C of 4~12h of vacuum drying, obtain the polyamic acid composite material with double-layer structure；
Step 3: the polyamic acid composite material with double-layer structure is subjected to sequencing heating, realizes the imines of polyamic acid
Change, finally obtaining upper layer is confining bed, and lower layer is that the porous polyimide conduction with coralliform empty structure porous layer is compound
Material.
2. the preparation method of porous polyimide conducing composite material according to claim 1, characterized in that described compound
The volume ratio of polyamic acid dispersion liquid I and composite polyamide acid dispersion liquid II is 1~15: 1.
3. the preparation method of porous polyimide conducing composite material according to claim 1, characterized in that described compound
Polyamic acid dispersion liquid I's the preparation method comprises the following steps: pore-foaming agent, conductive filler are dispersed in solvent respectively under normal temperature and pressure,
Sequentially add diamines, dianhydride monomer under inert gas protection, the volume ratio of the pore-foaming agent and solvent is 1: 1~10；Reaction
Temperature be 20~30 DEG C, the reaction time be 3~for 24 hours, obtain solid content be 10%~20% polyamic acid dispersion liquid I.
4. the preparation method of porous polyimide conducing composite material according to claim 1, characterized in that described compound
Polyamic acid dispersion liquid II's the preparation method comprises the following steps: conductive filler is dispersed in solvent under normal temperature and pressure, in inert gas
Sequentially adding diamines, dianhydride monomer under protection, reaction temperature is 20~30 DEG C, the reaction time is 3~for 24 hours, obtaining solid content is
10%~20% composite polyamide acid dispersion liquid II.
5. the preparation method of porous polyimide conducing composite material according to claim 3 or 4, characterized in that described
Diamines, dianhydride monomer molar ratio are 1: 1.01~1.1；The conductive filler and monomer weight ratio are 1~20: 100；The monomer
For diamine monomer, dianhydride monomer quality sum.
6. the preparation method of porous polyimide conducing composite material described in -4 according to claim 1, characterized in that the journey
The process of sequenceization heating is 100 DEG C of 1~2h of constant temperature；120 DEG C of 1~2h of constant temperature；180 DEG C of 1~2h of constant temperature；300 DEG C of constant temperature 0.5~
1h。
7. the preparation method of porous polyimide conducing composite material according to claim 5, characterized in that described program
The process for changing heating is 100 DEG C of 1~2h of constant temperature；120 DEG C of 1~2h of constant temperature；180 DEG C of 1~2h of constant temperature；300 DEG C of 0.5~1h of constant temperature.
8. according to the preparation method of porous polyimide conducing composite material described in claim 3,4 or 7, characterized in that institute
Stating conductive filler is one of modified graphene oxide, graphene, carbon black and multi-walled carbon nanotube or a variety of；The pore-foaming agent
For dibutyl phthalate and/or polyethylene glycol.
9. according to the preparation method of porous polyimide conducing composite material described in claim 3,4 or 7, characterized in that institute
Stating diamine monomer is one of 4,4'- diaminodiphenyl ether, 4,4'- diaminodiphenylmethane, p-phenylenediamine and m-phenylene diamine (MPD)
Or it is a variety of；The dianhydride monomer is 3,3', in 4,4'- benzophenone tetracid dianhydride, bisphenol A dianhydride and 4,4'- biphenyl ether dianhydride
It is one or more.
10. according to the preparation method of porous polyimide conducing composite material described in claim 3,4 or 7, characterized in that institute
Stating solvent is n,N-dimethylacetamide, n,N-Dimethylformamide or N-Methyl pyrrolidone, and the inert gas is nitrogen
Or argon gas.
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| CN113185834A (en) * | 2021-04-22 | 2021-07-30 | 陕西工业职业技术学院 | Preparation method of polymer-based carbon nano composite microporous electromagnetic shielding material |
| CN113231043A (en) * | 2021-05-06 | 2021-08-10 | 哈尔滨工程大学 | Oximato multi-layer polyimide microsphere adsorption material and preparation method thereof |
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