CN106750290A - A kind of method that in-situ polymerization prepares polyimides Graphene composite aerogel - Google Patents
A kind of method that in-situ polymerization prepares polyimides Graphene composite aerogel Download PDFInfo
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- CN106750290A CN106750290A CN201611007875.XA CN201611007875A CN106750290A CN 106750290 A CN106750290 A CN 106750290A CN 201611007875 A CN201611007875 A CN 201611007875A CN 106750290 A CN106750290 A CN 106750290A
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- graphene oxide
- polyamic acid
- graphene
- diamine
- aerogel
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 239000004964 aerogel Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000004642 Polyimide Substances 0.000 title abstract description 16
- 229920001721 polyimide Polymers 0.000 title abstract description 16
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 19
- 150000004985 diamines Chemical class 0.000 claims abstract description 15
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003980 solgel method Methods 0.000 claims abstract description 3
- 239000004952 Polyamide Substances 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 238000000859 sublimation Methods 0.000 claims description 4
- 230000008022 sublimation Effects 0.000 claims description 4
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 claims 1
- 238000011938 amidation process Methods 0.000 abstract description 3
- 238000007710 freezing Methods 0.000 abstract description 3
- 230000008014 freezing Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004575 stone Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- -1 benzene tetramethyl Acid anhydrides Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- 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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to composite aerogel technical field, and in particular to a kind of in-situ polymerization prepares polyimides Graphene aerogel composite and preparation method thereof.Composite aerogel of the invention, its raw material composition includes：One or more binary acid anhydride, one or more diamine, one or more graphene oxide.Its preparation method includes：The preparation of graphene oxide dispersion；In-situ polymerization prepares polyamic acid graphene oxide solution；Freeze-drying prepares polyamic acid graphene oxide filiform；Polyamic acid graphene oxide gel is prepared by sol-gel process；Polyamic acid graphite oxide aerogel is prepared by freezing dry process；Polyamic acid graphene aerogel is prepared by hot Asia amidation process.The method that polyimides composite aerogel is prepared in the present invention is simple and easy to apply, and prepared composite aerogel microscopic appearance is homogeneous.Additionally, prepared polyimide-based composite aerogel has excellent heat resistance.
Description
Technical field
The invention belongs to the technical field of composite aerogel, and in particular to a kind of in-situ polymerization prepares polyimides-graphite
The method of alkene composite aerogel.
Background technology
Polymer aerogel is porous gel class material of the class with natural or synthetic macromolecule as matrix, with it is low into
The characteristics such as sheet, easy-formation, high porosity, low-density, lower thermal conductivity.Thus, polymer aerogel is gradually in heat-insulated, sound insulation and Jie
It is used as matrix material in electric material.However, polymer aerogel generally existing poor mechanical property, thermal stability are poor, inflammable etc.
Problem.To find out its cause, mainly being caused by polymeric matrix poor mechanical property and heat decomposition temperature are low.
Polyimides, as a kind of engineering plastics, is a kind of preferable with good mechanical property and heat endurance
Polymer aerogel matrix material.But polyimide aerogels need addition crosslinking agent in preparation process and shrink tight to solve it
The problem of weight.However, most of crosslinking agent is not yet commercialized and expensive, its application is limited.
The content of the invention
Crosslinking agent the present invention be directed to be used in current polyimide aerogels preparation process is expensive, using limited
Problem, propose one kind with Graphene as crosslinking agent, the method that in-situ polymerization prepares polyimides-Graphene composite aerogel.
The present invention provides the preparation method that a kind of in-situ polymerization prepares polyimides-Graphene composite aerogel, its raw material
Composition includes one or more binary acid anhydride, wherein one or more diamine, one or more graphene oxide, binary acid anhydride and two
The mol ratio of first amine is 1.2:1-1:1, Graphene is 0.2 with the mass ratio of binary acid anhydride and diamine:100-2:100, preparation
Concretely comprise the following steps：
（1）Diamine is dissolved in polar solvent, ultrasonic disperse obtains diamine solution；
（2）Graphene oxide is scattered in diamine solution, ultrasonic disperse, the diamine-graphene oxide stablized point
Dispersion liquid；
（3）Binary acid anhydride is added in diamine-graphene oxide dispersion, is stirred in ice-water bath, obtain polyamic acid-oxygen
Graphite alkene solution；
（4）By in polyamic acid-graphene oxide solution precipitating to frozen water, freezed in freeze drier after being freezed in refrigerator
Dry, obtain polyamic acid-graphene oxide filiform；
（5）Polyamic acid after drying-graphene oxide filiform is scattered in deionized water, ultrasound, stirring obtain polyamide
Acid-graphene oxide dispersion；
（6）Polyamic acid-graphene oxide dispersion is placed into a period of time, by sol-gel process, polyamide is obtained
Acid-graphene oxide gel；
（7）After polyamic acid-graphene oxide gel is freezed as solid in liquid nitrogen, the freeze-drying in freeze drier,
Obtain polyamic acid-graphite oxide aerogel；
（8）Hot Asia amidatioon is carried out to polyamic acid-graphite oxide aerogel in nitrogen atmosphere, polyamides is prepared sub-
Amine-Graphene composite aerogel.
Further, step（1）Middle diamine is 4,4 '-diaminodiphenyl ether, p-phenylenediamine, four (4- aminophenyls) first
Alkane, 1,3,5- triamido phenyl benzene or three (4- aminophenyls) amine.
Further, step（1）Middle polar solvent is DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE or N, N- diformazan
Base formamide.
Further, step（2）Middle ultrasonic time is 2-4 h.
Further, step（3）Middle binary acid anhydride be pyromellitic dianhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides or 3,
3', 4,4'- bibenzene tetracarboxylic dianhydride.
Further, step（3）Middle mixing time is 1-6 h, and stir speed (S.S.) is 150-400 r/min.
Further, step（4）Middle sublimation drying is 24-72 h.
Further, step（5）The concentration of middle polyamic acid-graphene oxide solution is 4-15%.
Further, step（6）The middle sol-gel time is 6 ~ 12 h.
Further, step（7）Middle sublimation drying is 12-72 h.
Further, step（8）Described in heat Asia amidation process be：Resulting polyamide acidic group is combined airsetting
Glue is placed in tube furnace and 300 DEG C, insulation 1-5 h is warmed up in nitrogen atmosphere.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of polyimide aerogels PI in the present invention.
Fig. 2 is polyimide-based composite aerogel PI in the present inventionODA-PMDAThe scanning electron microscope (SEM) photograph of-G-0.5%.
Fig. 3 is polyimide-based composite aerogel PI in the present inventionODA-PMDAThe scanning electron microscope (SEM) photograph of-G-1%.
Fig. 4 is polyimide-based composite aerogel PI in the present inventionODA-PMDAThe scanning electron microscope (SEM) photograph of-G-2%.
Fig. 5 is polyimide-based composite aerogel PI in the present inventionPPDA-PMDAThe scanning electron microscope (SEM) photograph of-G-1%.
Fig. 6 is polyimide-based composite aerogel PI in the present inventionPPDA-BPDAThe scanning electron microscope (SEM) photograph of-G-1%.
Fig. 7 is polyimide-based composite aerogel PI in the present inventionODA-BPDAThe scanning electron microscope (SEM) photograph of-G-1%.
Specific embodiment
With reference to instantiation, the present invention is described in further detail, it should be appreciated that these embodiments are merely to illustrate
The present invention rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, this area
Technical staff can make various changes or modification to the present invention, and these equivalent form of values equally fall within the application appended claims
Limited range.
Embodiment 1
The present embodiment is comprised the steps of：
Can be withN ,N- dimethylacetylamide is solvent, 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride are monomer in ice
Condensation polymerization reaction is carried out in water-bath, polyamic acid filiform is prepared.Detailed process is as follows：At room temperature, first by 8 g（0.04
mol）4,4 '-diaminodiphenyl ether is substantially soluble in 95 gN ,N- dimethylacetylamide, by solution clarification, loses particle and is defined.
It is then slowly added into 8.85 g（0.046 mol）Pyromellitic dianhydride, 2 h are stirred during reaction then is moved into ice-water bath.Then
Add and prepare the polyamic acid solution that solid content is 15% with 0.04 mol triethylamines, the continuation h of stirring reaction about 2.By institute
The polyamic acid solution sealing preserve of preparation, standing is poured slowly into frozen water two days later, scrubbed, freezing, and water is obtained after drying
Soluble polyamide acid filiform is standby.
30 mL deionized waters are taken, adds 2 g polyamic acids filiforms and 1 g triethylamines, ultrasonic 1 h to stir 0.5 h, make
Polyamic acid dissolves and is uniformly dispersed, and obtains the polyamic acid aqueous solution.Triethylamine can be coated on the terminal carboxyl group of polyamic acid
In functional group, polyamic acid is set to be soluble in deionized water.It is then transferred in mould, and ultrasonic 0.5 h, then by mould
The h of precooling 5 in 4 DEG C or so of refrigerator is transferred to, is placed into and make in liquid nitrogen its quick freeze for solid, then in 10 ~ 20 Pa
The h of freeze-drying 48 under vacuum, obtains polyamic acid aeroge.
Resulting polyamic acid aeroge is placed in tube furnace, heating schedule, i.e. room temperature are controlled in nitrogen atmosphere
To 100 DEG C of 30 min of intensification, 1 h is incubated；100 DEG C to 200 DEG C, heat up 30 min, is incubated 1 h；200 DEG C to 300 DEG C,
Heat up 30 min, is incubated 1 h, you can obtain polyimide aerogels, be designated as PI.
Embodiment 2
WithN ,N- dimethylacetylamide is solvent, 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride are monomer, in-situ polymerization
Prepare polyimides-Graphene composite aerogel that Graphene content is 0.5%.Detailed process is as follows：At room temperature, first by 8 g
（0.04 mol）4,4 '-diaminodiphenyl ether is substantially soluble in 95 gN ,N- dimethylacetylamide, with solution clarification, loses
Grain is defined.Add 0.08 g graphene oxides, ultrasonic 2 h.It is then slowly added into 8.85 g（0.046 mol）Equal benzene tetramethyl
Acid anhydrides, 2 h are stirred during reaction then is moved into ice-water bath.It is subsequently adding and 0.04 mol triethylamines, continuation stirring reaction about 2
H, prepares polyamic acid-graphene oxide solution.By prepared polyamic acid-graphene oxide solution sealing preserve,
Standing is poured slowly into frozen water two days later, scrubbed, freezing, and it is thread to obtain water-soluble polyamic acid-graphene oxide after drying
Thing is standby.
Take 30 mL deionized waters, add 2 g polyamic acids-graphene oxide filiform and 1 g triethylamines, ultrasonic 1 h,
0.5 h is stirred, polyamic acid-graphene oxide is dissolved and is uniformly dispersed, obtain polyamic acid-graphene oxide water solution.
Triethylamine can be coated on the terminal carboxyl function of polyamic acid, polyamic acid is soluble in deionized water.Then by it
It is transferred in mould, and ultrasonic 0.5 h, mould is then transferred to the h of precooling 5 in 4 DEG C or so of refrigerator, in places into liquid nitrogen
Make its quick freeze for solid, then the h of freeze-drying 48 under 10 ~ 20 Pa vacuums, obtain polyester-polyamide acid-oxidation stone
Black alkene aeroge.
Sub- amidation process prepares polyimides-Graphene composite aerogel with embodiment 1, is designated as PIODA-PMDA-
G-0.5%。
Embodiment 3
WithN ,N- dimethylacetylamide is solvent, 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride are monomer, in-situ polymerization
Prepare polyimides-Graphene composite aerogel that Graphene content is 1%.In-situ polymerization is prepared into polyamic acid-graphite oxide
The content of graphene oxide increases to 1% during alkene filiform, and remaining step is with embodiment 2.Prepare polyimides-stone
Black alkene composite aerogel, is designated as PIODA-PMDA-G-1%。
Embodiment 4
WithN ,N- dimethylacetylamide is solvent, 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride are monomer, in-situ polymerization
Prepare polyimides-Graphene composite aerogel that Graphene content is 2%.In-situ polymerization is prepared into polyamic acid-graphite oxide
The content of graphene oxide increases to 2% during alkene filiform, and remaining step is with embodiment 2.Prepare polyimides-stone
Black alkene composite aerogel, is designated as PIODA-PMDA-G-2%。
Embodiment 5
WithN ,N- dimethylacetylamide is solvent, and p-phenylenediamine and pyromellitic dianhydride are monomer, and in-situ polymerization prepares graphite
Alkene content is 1% polyimides-Graphene composite aerogel.In-situ polymerization is prepared into polyamic acid-graphene oxide filiform
During diamine monomer be changed into p-phenylenediamine, remaining step is with embodiment 2.Prepare the compound airsetting of polyimides-Graphene
Glue, is designated as PIPPDA-PMDA-G-1%。
Embodiment 6
WithN ,N- dimethylacetylamide is solvent, and p-phenylenediamine and 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides are monomer, in situ
Polymerization prepares polyimides-Graphene composite aerogel that Graphene content is 1%.In-situ polymerization is prepared into polyamic acid-oxidation
Dianhydride monomer is changed into 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides during Graphene filiform, and remaining step is with embodiment 2.Prepare
Polyimides-Graphene composite aerogel is obtained, PI is designated asPPDA-BPDA-G-1%。
Embodiment 7
WithN ,N- dimethylacetylamide is solvent, 4,4 '-diaminodiphenyl ether and 3,3', and 4,4'- bibenzene tetracarboxylic dianhydrides are
Monomer, in-situ polymerization prepares polyimides-Graphene composite aerogel that Graphene content is 1%.In-situ polymerization is prepared into polyamides
Dianhydride monomer is changed into 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides during amino acid-graphene oxide filiform, and remaining step is with real
Apply example 2.Polyimides-Graphene composite aerogel is prepared, PI is designated asODA-BPDA-G-1%。
The composition and performance of polyimides-Graphene composite aerogel prepared by above-described embodiment are shown in Table 1.
The component and performance of the polyimide-based composite aerogel of table 1
。
Claims (10)
1. a kind of method that in-situ polymerization prepares polyimides-Graphene composite aerogel, it is characterised in that raw material includes：One
Kind or various binary acid anhydrides, one or more diamine, one or more graphene oxide, wherein binary acid anhydride and diamine mole
Than being 1.2:1-1:1, Graphene is 0.2 with the mass ratio of binary acid anhydride and diamine:100-2:100, preparation is concretely comprised the following steps：
（1）Diamine is dissolved in polar solvent, ultrasonic disperse obtains diamine solution；
（2）Graphene oxide is scattered in diamine solution, ultrasonic disperse, the diamine-graphene oxide stablized point
Dispersion liquid；
（3）Binary acid anhydride is added in diamine-graphene oxide dispersion, is stirred in ice-water bath, obtain polyamic acid-oxygen
Graphite alkene solution；
（4）By in polyamic acid-graphene oxide solution precipitating to frozen water, freezed in freeze drier after being freezed in refrigerator
Dry, obtain polyamic acid-graphene oxide filiform；
（5）Polyamic acid after drying-graphene oxide filiform is scattered in deionized water, ultrasound, stirring obtain polyamide
Acid-graphene oxide dispersion；
（6）Polyamic acid-graphene oxide dispersion is placed into a period of time, by sol-gel process, polyamide is obtained
Acid-graphene oxide gel；
（7）After polyamic acid-graphene oxide gel is freezed as solid in liquid nitrogen, the freeze-drying in freeze drier,
Obtain polyamic acid-graphite oxide aerogel；
（8）Hot Asia amidatioon is carried out to polyamic acid-graphite oxide aerogel in nitrogen atmosphere, polyamides is prepared sub-
Amine-Graphene composite aerogel.
2. method according to claim 1, it is characterised in that the diamine is 4,4 '-diaminodiphenyl ether, to benzene two
Amine, four (4- aminophenyls) methane, 1,3,5- triamido phenyl benzene or three (4- aminophenyls) amine；The binary acid anhydride is equal benzene four
Formic anhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides or 3,3', 4,4'- bibenzene tetracarboxylic dianhydride.
3. method according to claim 1 and 2, it is characterised in that step（1）Described in polar solvent be N, N- diformazans
Yl acetamide, 1-METHYLPYRROLIDONE or N,N-dimethylformamide；Step（2）Middle ultrasonic time is 2-4 h.
4. method according to claim 3, it is characterised in that step（3）Middle mixing time is 1-6 h, and stir speed (S.S.) is
150-400 r/min。
5. the method according to claim 1,2 or 4, it is characterised in that step（4）Middle sublimation drying is 24-72
h。
6. method according to claim 5, it is characterised in that step（5）Middle polyamic acid-graphene oxide solution it is dense
It is 4-15% to spend.
7. the method according to claim 1,2,4 or 6, it is characterised in that step（6）The middle sol-gel time is 6 ~ 12
h。
8. method according to claim 7, it is characterised in that step（7）Middle sublimation drying is 12-72 h.
9. the method according to claim 1,2,4,6 or 8, it is characterised in that step（8）Described in heat Asia amidatioon
Process is：Resulting polyamide acidic group composite aerogel is placed in tube furnace and 300 DEG C are warmed up in nitrogen atmosphere, protected
Warm 1-5 h.
10. polyimides-Graphene composite aerogel that a kind of method described by one of claim 1-9 is prepared.
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