CN106433129A - Graphene/SiO2 hybrid polyimide foam material and preparation method thereof - Google Patents

Graphene/SiO2 hybrid polyimide foam material and preparation method thereof Download PDF

Info

Publication number
CN106433129A
CN106433129A CN201610909702.0A CN201610909702A CN106433129A CN 106433129 A CN106433129 A CN 106433129A CN 201610909702 A CN201610909702 A CN 201610909702A CN 106433129 A CN106433129 A CN 106433129A
Authority
CN
China
Prior art keywords
graphene oxide
graphene
add
sio2
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610909702.0A
Other languages
Chinese (zh)
Other versions
CN106433129B (en
Inventor
齐锴亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi Polytechnic Institute
Original Assignee
Shaanxi Polytechnic Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi Polytechnic Institute filed Critical Shaanxi Polytechnic Institute
Priority to CN201610909702.0A priority Critical patent/CN106433129B/en
Publication of CN106433129A publication Critical patent/CN106433129A/en
Application granted granted Critical
Publication of CN106433129B publication Critical patent/CN106433129B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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

Landscapes

  • 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)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a graphene/SiO2 hybrid polyimide foam material and a preparation method thereof. The graphene/SiO2 hybrid polyimide foam material is prepared from modified graphene oxide, benzophenone tetracarboxylic acid dianhydride, diaminodiphenyl ether, 3-aminopropyltriethoxysilane and tetraethoxysilane through an amidation reaction and a sol-gel reaction. The modified graphene oxide is modified graphene oxide with the surface containing isocyanato. On the one hand, the prepared graphene/SiO2 hybrid polyimide foam material fully exerts the good enhancing effect of the graphene oxide and the good toughening effect of silicon dioxide, on the other hand, the defect that the graphene oxide and silicon dioxide are prone to cluster is overcome, SiO2 particles can be evenly distributed on graphene slice layers, the graphene slice layers are not easy to overlap, dispersity is obviously improved, and meanwhile the performance that polyimide is good in heat resistance, high in mechanical performance, high in fire resistance and the like is achieved.

Description

A kind of Graphene/SiO2Hybrid polyimide foamed materialss and preparation method thereof
Technical field
A kind of the present invention relates to field of compound material, in particular it relates to Graphene/SiO2 hybrid polyimide bubble Foam material and preparation method thereof.
Background technology
Polyimide foams are smokeless in a class fire, flame indiffusion, avirulence, no release poison combination property is Good light material.The polyimide material of foaming structure not only maintains the excellent heatproof of polyimides primary resin, fire-retardant etc. Performance, also has prominent wave transparent characteristic and the combination property such as light weight, flexible resilient be good, easy to use, can prepare winged Row device structure member, wing, internal weapon bays deceleration bearing plate, jet pipe collet, cabin fire-retardant heat insulation interlayer, pipe insulating layer, core heap The products such as radiant barrier, are widely used in the fields such as Aeronautics and Astronautics, bullet train, automobile, fan blade, nuclear power engineering.
Graphene is by the carbonaceous material of the bi-dimensional cellular shape lattice structure of the tightly packed one-tenth of monolayer carbon atom, has uniqueness Mechanics and electric property, show huge application potential in nanometer, electronics, energy storage material and field of compound material.Graphite One of purposes of alkene is exactly to prepare composite together with polymer, application in fluoropolymer resin based composites for the Graphene Increasingly attract widespread attention, and make some progress.Producing that such composite do not require nothing more than can be big Scale ground produces Graphene, also requires Graphene can be evenly distributed on matrix.But the dispersibility of Graphene is not good, must First Graphene modification must be improved with the compatibility and polymer monomer or polymer between.
Graphene oxide（GO）It is a kind of important derivatives of Graphene, its structure is similar with Graphene, relevant research knot Fruit shows：GO has quasi- two-dimensional layered structure, contains substantial amounts of active group between the lamella of Graphene（As hydroxyl, carboxyl Deng）.Due to the presence of hydroxyl and carboxyl, long-chain fat hydrocarbon, transition metal ionss, hydrophilic molecule and polymer etc. can pass through hydrogen Between the lamella of the effect insertion GO such as key, ionic bond, make GO fine dispersion in matrix resin.Meanwhile, the two of Graphene uniqueness Dimensional plane laminated structure and great specific surface area make Graphene become the ideal carrier of carrying inorganic nanoparticle, can pass through It is combined with the inorganic nano-particle of multiple different structures and property, to prepare novel inorganic nanoparticle Graphene hybrid, to carry Polymolecularity, can expand the application in more areas for the Graphene.
However, people not yet consider for Graphene, nano silicon, polyimides to be combined preparation hydridization foam material so far Material.
Content of the invention
The present invention is intended to provide a kind of new Graphene/SiO2 hybrid polyimide foamed materialss, described Graphene/SiO2 Hybrid polyimide foamed materialss one side can give full play to the good reinforced effects of graphene oxide and silicon dioxide is good Toughening effect, shortcoming that the two on the other hand can be overcome easily to reunite, enable SiO2 granule to be evenly distributed in graphene film On layer, between graphene sheet layer, it is difficult overlap, dispersibility is improved significantly, additionally, also having concurrently, polyimides are heat-resist, power Learn the performances such as performance is high, anti-flammability is strong.
Another object of the present invention is to providing the preparation side of described Graphene/SiO2 hybrid polyimide foamed materialss Method.
The goal of the invention of the present invention is achieved by the following technical programs.
A kind of modified graphene oxide, described modified graphene oxide contains the modified graphite oxide of isocyano for surface Alkene.
The present invention passes through to introduce isocyano in surface of graphene oxide, enables modified graphene oxide in organic solvent In stably disperse, due to the presence of modified graphene oxide surface-NCO group, modified graphene oxide can be used for further Preparation contains Graphene or the polymer nanocomposites of other functional groups.
The preparation method of described modified graphene oxide, comprises the steps：
S1. 10 ± 1g graphite powder and 3.5 ± 0.5g sodium nitrate are dissolved in dense H2SO4, supersound process reaction at 0～5 DEG C 0.5～1.5h；
S2. add 40 ± 2gKMnO4, react 1～3h in 0～10 DEG C, then adjust the temperature to 32～40 DEG C, sonic oscillation reaction 20 ～60min；
S3. S2 gained mixed liquor is added in deionized water, 70～100 DEG C of temperature control, mechanical agitation 20～60min；
S4. add deionized water stopped reaction, add volume fraction be 30% hydrogen peroxide, continue reaction to no gas produce；
S5. the mixed acid solution using H2O, H2O2, H2SO4 three purifies to S4 resulting solution, is redispersed in distilled water, ultrasonic Vibration 20～60min, centrifugation, extract GO aqueous solution；
S6. air-dry, obtain anhydrous graphene oxide layer, and be ground into powder；
S7. claim 200 ± 10mgS6 graphene oxide obtaining, be added to dimethylformamide（DMF）In, supersound process 20～ After 60min, add 4.8～7.2g diisocyanate, supersound process 20～60min, add 2～3 catalyst dibutyltin cinnamic acids two Butyl tin（DBTDL）, 50 ± 5 DEG C of insulation 48～60h；
S8. washing with acetone S7 resulting solution, centrifugation are used, product is dried, and acquires modified graphene oxide.
Preferably, described S2 is to add 40gKMnO4, reacts 1.5h in 4 DEG C, then adjusts the temperature to 38 DEG C, ultrasonic reaction 30min.
Preferably, described S3 is to add in the deionized water of 500mL by S2 gained mixed liquor, then 90～100 DEG C of temperature control, Mechanical agitation 30～60min.
Preferably, described S5 is to be H2O with mass ratio:H2O2:H2SO4=l:0.23:0.26 mixed acid solution is to S4 institute Purified solution 15 times, low-speed centrifugal washing removes excessive acid and by-product, then will divide in neutral graphite oxide after washing Dissipate in distilled water, sonic oscillation peels off 40min, by high speed gradient centrifugation in 2500r min-1It is centrifuged 30min under rotating speed Extract GO aqueous solution.
Preferably, diisocyanate described in S7. is toluene di-isocyanate(TDI)（TDI）And/or isoflurane chalcone diisocyanate （IPDI）.
Preferably, described S8. is the washing with acetone S7 resulting solution with 3 times of volumes, 3000r min-1Centrifugation, repeats to grasp Make 4 times, product puts into vacuum drying oven normal temperature drying 48h, acquires modified graphene oxide.
A kind of Graphene/SiO2 hybrid polyimide foamed materialss, its preparing raw material includes following calculating by weight Component：
Benzophenone tetracarboxylic dianhydride（BTDA）30～35 parts；
Diaminodiphenyl ether（ODA）19～21 parts；
5～40 parts of methanol；
0.01 ~ 0.1 part of 3- aminopropyl triethoxysilane；
Tetraethyl orthosilicate（TEOS）6～20 parts；
10～20 parts of modified graphene oxide.
Graphene/SiO2 hybrid material is a kind of preferable resin extender of excellent performance, in this foamed materialss, oxygen The potentiation of graphite alkene is notable, and the toughening effect of silicon dioxide projects, and Graphene/SiO2 hybrid material is on the one hand comprehensive The advantage of the two, the on the other hand three-dimensional with its uniqueness " rivet " structure, activeness and quietness effect has obtained greatly playing. Meanwhile, silicon dioxide has the excellent properties such as high fluidity, low-expansion coefficient, high fillibility, low stress, is indispensable excellent Matter inorganic filler.This hybrid material one side can give full play to Graphene and the performance advantage of SiO2 itself, on the other hand The shortcoming that the two is easily reunited can be overcome, SiO2 granule is evenly distributed on graphene sheet layer, its special " rivet " structure Make to be difficult overlap between graphene sheet layer, dispersibility is improved significantly.
The preparation method of described Graphene/SiO2 hybrid polyimide foamed materialss, comprises the steps：
M1. BTDA is added in methanol, is heated at reflux 1.5～2.5h at 70 ± 5 DEG C, is subsequently added diaminodiphenyl ether, Continue to be heated at reflux 1.5～2.5h at 70 ± 5 DEG C；Add 3- aminopropyl triethoxysilane, continue reaction 1～1.5h；
M2. add modified graphene oxide, continue reaction 1～1.5h, add TEOS, continue reaction 20～60min, obtain stone The precursor solution of black alkene/SiO2 hybrid polyimide foamed materialss；
M3. precursor solution described in M2 is heated, remove excess of solvent, using pulverizer, the presoma after drying is polished simultaneously Sieve, obtain the precursor powder of uniform particle sizes；
M4. precursor powder is put into from molding jig, in microwave oven, simultaneously the prepared Graphene/SiO2 of imidizate is miscellaneous for foaming Change Polyimide foams.
Compared with prior art, the present invention has the advantages that：
（1）Graphene oxide is prepared using ultrasonic wave added Hummer body method, the method mainly contains low temperature, middle temperature, high temperature 3 The stage of reaction, fully, completely, pyroreaction hydrolysis thoroughly, can obtain interlamellar spacing to low-temp reaction intercalation for middle temperature reaction depth oxidation Larger graphite oxide, the larger graphite oxide of this interlamellar spacing is conducive to the insertion interlayer such as other molecules, atom to form oxidation Graphite intercalation compounds；
（2）The surface modification to graphene oxide for the diisocyanate, beneficial to graphene oxide dispersion in the base with strengthen stone Chemical bonds are had between black alkene and SiO2, polyimides；
（3）Under conditions of no extraneous water adds, occur with TEOS by using the water that presoma is deviate from during hot acid imide Hydrolysis-condensation reacts so that the hydrolysis-condensation reaction of TEOS and the hot imide reaction of presoma are carried out simultaneously, thus real Existing sol-gel process prepares Graphene/SiO2Polyimide foams；
（4）Using microwave heating foam process, due to PEAS precursor powder, in microwave heating process, heating rate is fast, therefore Shorten heat conduction time, thus reducing the loss of foaming agent in precursor powder, the foam cell structure of preparation is more Uniformly, foam structure is stable.
Brief description
Fig. 1 is the structure chart of graphene oxide.
Fig. 2 is toluene di-isocyanate(TDI) intercalation modifying graphite oxide alkene reaction schematic diagram.
Specific embodiment
With reference to embodiment, the present invention is further described, the raw material that following examples are used is common city Sell product.
Embodiment 1
S1. 10g crystalline graphite powder and 3.5g sodium nitrate are dissolved in the dense H2SO4 of 200mL, dense H2SO4 is placed in advance in 1000mL's In there-necked flask, ice bath is cooled to 0 DEG C, supersound process reacts 1h；
S2. add 40gKMnO4, react 1.5h in 4 DEG C, then adjust the temperature to 38 DEG C, ultrasonic reaction 30min；
S3. S2 gained mixed liquor is added in the deionized water of 500mL, then 95 DEG C of temperature control, mechanical agitation 30min；
S4. add 600mL deionized water stopped reaction, be subsequently adding 30mL volume fraction be 30% hydrogen peroxide, continue anti- Should produce to no gas；
S5. use H2O:H2O2:H2SO4=l:0.23:0.26 mixed acid solution purifies 15 times to S4 resulting solution, low-speed centrifugal Washing removes excessive acid and by-product, then is scattered in after washing in distilled water in neutral graphite oxide, and sonic oscillation is shelled From 40min, by high speed gradient centrifugation in 2500r min-1Under rotating speed, centrifugation 30min extracts GO aqueous solution；
S6. room temperature air-dries 12h, obtains anhydrous graphene oxide layer, and is ground into powder；
S7. claim the graphene oxide that obtains of 200mg S6, be added in the DMF that 100mL is processed through molecular sieve dehydration, ultrasonic place After reason 20～60min, add the TDI of 5g, supersound process 30min, add 3 catalyst DBTDL, 50 DEG C of insulation 48h；
S8. with the washing with acetone S7 resulting solution of 3 times of volumes, 3000r min-1Centrifugation, repetitive operation 4 times, product is put into very Empty drying baker normal temperature drying 48h, acquires modified graphene oxide.
Embodiment 2
S1. 10g graphite powder and 3.5g sodium nitrate are dissolved in the dense H2SO4 of 200mL, supersound process reaction 1.5h at 0 DEG C；
S2. add 40gKMnO4, react 2h in 5 DEG C, then adjust the temperature to 35 DEG C, sonic oscillation reacts 60min；
S3. S2 gained mixed liquor is added in the deionized water of 500mL, then 90 DEG C of temperature control, mechanical agitation 60min；
S4. add 600mL deionized water stopped reaction, be subsequently adding 30mL volume fraction be 30% hydrogen peroxide, continue anti- Should produce to no gas；
S5. use H2O:H2O2:H2SO4=l:0.23:0.26 mixed acid solution purifies 15 times to S5 resulting solution, is redispersed in In distilled water, sonic oscillation 60min, centrifugation, extract GO aqueous solution；
S6. room temperature air-dries 12h, obtains anhydrous graphene oxide layer, and is ground into powder；
S7. claim the graphene oxide that obtains of 200mg S6, be added in the DMF that 100mL is processed through molecular sieve dehydration, ultrasonic place After reason 60min, add 6.4gIPDI, supersound process 60min, add 3 catalyst DBTDL, 50 DEG C of insulation 48h；
S8. washing with acetone S7 resulting solution, centrifugation, repetitive operation 5 times are used, product is dried, and acquires modified graphene oxide.
Embodiment 3
M1. 32.2gBTDA is added in 15mg methanol, is heated at reflux 2h at 70 DEG C, is subsequently added 19.8gODA, 70 Continue to be heated at reflux 2h at DEG C, be then added dropwise over 0.025g 3- aminopropyl triethoxysilane, continue reaction 1h；
M2. add the modified graphene oxide prepared by 10mg embodiment 1, continue reaction 1h, add 6.5mgTEOS, continue anti- Answer 30min, obtain the precursor solution of Graphene/SiO2 hybrid polyimide foamed materialss；
M3. precursor solution described in M2 is heated, remove excess of solvent, using pulverizer, the presoma after drying is polished simultaneously Sieve, obtain the precursor powder of uniform particle sizes；
M4. precursor powder is put into from molding jig, in microwave oven, simultaneously the prepared Graphene/SiO2 of imidizate is miscellaneous for foaming Change Polyimide foams.
Embodiment 4
M1. 32.2gBTDA is added in 15mg methanol, is heated at reflux 1.5h at 75 DEG C, is subsequently added 19.8gODA, Continue to be heated at reflux 1.5h at 75 DEG C, be then added dropwise over 0.025g 3- aminopropyl triethoxysilane, continue reaction 1.5h；
M2. add the modified graphene oxide prepared by 10mg embodiment 2, continue reaction 1.5h, add 13mgTEOS, continue Reaction 30min, obtains the precursor solution of Graphene/SiO2 hybrid polyimide foamed materialss；
M3. precursor solution described in M2 is heated, remove excess of solvent, using pulverizer, the presoma after drying is polished simultaneously Sieve, obtain the precursor powder of uniform particle sizes；
M4. precursor powder is put into from molding jig, in microwave oven, simultaneously the prepared Graphene/SiO2 of imidizate is miscellaneous for foaming Change Polyimide foams.
Embodiment 5
M1. 30gBTDA is added in 18mg methanol, is heated at reflux 2h at 70 DEG C, is subsequently added 19gODA, at 70 DEG C Continue to be heated at reflux 2h, be then added dropwise over 0.01g 3- aminopropyl triethoxysilane, continue reaction 1h；
M2. add the modified graphene oxide prepared by 15mg embodiment 1, continue reaction 1h, add 6.5mgTEOS, continue anti- Answer 30min, obtain the precursor solution of Graphene/SiO2 hybrid polyimide foamed materialss；
M3. precursor solution described in M2 is heated, remove excess of solvent, using pulverizer, the presoma after drying is polished simultaneously Sieve, obtain the precursor powder of uniform particle sizes；
M4. precursor powder is put into from molding jig, in microwave oven, simultaneously the prepared Graphene/SiO2 of imidizate is miscellaneous for foaming Change Polyimide foams.
Embodiment 6
M1. 30gBTDA is added in 18mg methanol, is heated at reflux 2h at 70 DEG C, is subsequently added 19gODA, at 70 DEG C Continue to be heated at reflux 2h, be then added dropwise over 0.01g 3- aminopropyl triethoxysilane, continue reaction 1.5h；
M2. add the modified graphene oxide prepared by 15mg embodiment 1, continue reaction 1h, add 13mgTEOS, continue anti- Answer 30min, obtain the precursor solution of Graphene/SiO2 hybrid polyimide foamed materialss；
M3. precursor solution described in M2 is heated, remove excess of solvent, using pulverizer, the presoma after drying is polished simultaneously Sieve, obtain the precursor powder of uniform particle sizes；
M4. precursor powder is put into from molding jig, in microwave oven, simultaneously the prepared Graphene/SiO2 of imidizate is miscellaneous for foaming Change Polyimide foams.
Embodiment 7
M1. 35gBTDA is added in 18mg methanol, is heated at reflux 2h at 70 DEG C, is subsequently added 21gODA, at 70 DEG C Continue to be heated at reflux 2h, be then added dropwise over 0.1g 3- aminopropyl triethoxysilane, continue reaction 1h；
M2. add the modified graphene oxide prepared by 20mg embodiment 1, continue reaction 1h, add 6.5mgTEOS, continue anti- Answer 30min, obtain the precursor solution of Graphene/SiO2 hybrid polyimide foamed materialss；
M3. precursor solution described in M2 is heated, remove excess of solvent, using pulverizer, the presoma after drying is polished simultaneously Sieve, obtain the precursor powder of uniform particle sizes；
M4. precursor powder is put into from molding jig, in microwave oven, simultaneously the prepared Graphene/SiO2 of imidizate is miscellaneous for foaming Change Polyimide foams.
Embodiment 8
M1. 35gBTDA is added in 18mg methanol, is heated at reflux 1.5h at 75 DEG C, is subsequently added 21gODA, at 75 DEG C Under continue to be heated at reflux 1.5h, be then added dropwise over 0.1g 3- aminopropyl triethoxysilane, continue reaction 1.5h；
M2. add the modified graphene oxide prepared by 20mg embodiment 2, continue reaction 1.5h, add 19.5mgTEOS, continue Continuous reaction 30min, obtains the precursor solution of Graphene/SiO2 hybrid polyimide foamed materialss；
M3. precursor solution described in M2 is heated, remove excess of solvent, using pulverizer, the presoma after drying is polished simultaneously Sieve, obtain the precursor powder of uniform particle sizes；
M4. precursor powder is put into from molding jig, in microwave oven, simultaneously the prepared Graphene/SiO2 of imidizate is miscellaneous for foaming Change Polyimide foams.
Comparative example 1
M1. 32.2gBTDA is added in 15mg methanol, is heated at reflux 2h at 70 DEG C, is subsequently added 19.8gODA, at 70 DEG C Under continue to be heated at reflux 2h, be then added dropwise over 0.025g 3- aminopropyl triethoxysilane, continue reaction 1h；
M2. add 6.5mgTEOS, continue reaction 30min, obtain the precursor solution of SiO2/ Polyimide foams；
M3. precursor solution described in M2 is heated, remove excess of solvent, the presoma after being dried using pulverizer is polished and mistake Sieve, obtains the precursor powder of uniform particle sizes；
M4. precursor powder is put into from molding jig, foaming the prepared SiO2/ polyimides of imidizate in microwave oven Foamed materialss.
Investigate Graphene/SiO2 hybrid polyimide foamed materialss prepared by embodiment 3～8 and comparative example 1 SiO2/ gathers The limited oxygen index of acid imide foam material and mechanical property, its detection project and testing result are as shown in table 1.
Table 1 embodiment and comparative example testing result
Detection project Limited oxygen index Impact strength/（KJ/m2） Tensile strength/（MPa） Compressive strength（MPa）
Examination criteria ASTM D-2863-00 GB 1943-2008 GB/T 6344-2008 GB/T 8813-2008
Embodiment 3 53% 15.6 2.54 2.91
Embodiment 4 47% 14.9 2.49 2.84
Embodiment 5 52% 16.8 2.51 2.69
Embodiment 6 51% 15.2 2.59 2.72
Embodiment 7 46% 14.5 2.47 2.78
Embodiment 8 48% 15.7 2.53 2.80
Comparative example 1 35% 10.3 1.89 1.94
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not be therefore And it is interpreted as the restriction to the scope of the claims of the present invention, as long as the technical side being obtained in the form of equivalent or equivalent transformation Case, all should be included within the protection domain of the claims in the present invention.

Claims (9)

1. a kind of modified graphene oxide is it is characterised in that described modified graphene oxide contains changing of isocyano for surface Property graphene oxide.
2. the preparation method of modified graphene oxide described in claim 1 is it is characterised in that comprise the steps：
S1. 10 ± 1g graphite powder and 3.5 ± 0.5g sodium nitrate are dissolved in dense H2SO4, supersound process reaction at 0～5 DEG C 0.5～1.5h；
S2. add 40 ± 2gKMnO4, react 1～3h in 0～10 DEG C, then adjust the temperature to 32～40 DEG C, sonic oscillation reaction 20 ～60min；
S3. S2 gained mixed liquor is added in deionized water, 70～100 DEG C of temperature control, mechanical agitation 20～60min；
S4. add deionized water stopped reaction, add volume fraction be 30% hydrogen peroxide, continue reaction to no gas produce；
S5. the mixed acid solution using H2O, H2O2, H2SO4 three purifies to S4 resulting solution, is redispersed in distilled water, ultrasonic Vibration 20～60min, centrifugation, extract graphene oxide water solution；
S6. air-dry, obtain anhydrous graphene oxide layer, and be ground into powder；
S7. claim 200 ± 10mgS6 graphene oxide obtaining, be added in dimethylformamide, supersound process 20～60min Afterwards, add 5～6.5g diisocyanate, supersound process 20～60min, add 2～3 catalyst dibutyltin dilaurylate, 50 ± 5 DEG C of insulation 48～60h；
S8. washing with acetone S7 resulting solution, centrifugation are used, product is dried, and acquires modified graphene oxide.
3. preparation method, it is characterised in that described S2 is to add 40gKMnO4, is reacted in 4 DEG C according to claim 2 1.5h, then adjust the temperature to 38 DEG C, ultrasonic reaction 30min.
4. according to claim 2 preparation method it is characterised in that described S3 be by S2 gained mixed liquor add 500mL In deionized water, 90～100 DEG C of temperature control, mechanical agitation 30～60min.
5. according to claim 2 preparation method it is characterised in that described S5 is to be H2O with mass ratio:H2O2:H2SO4= l:0.23:0.26 mixed acid solution purifies 15 times to S4 resulting solution, and low-speed centrifugal washing removes excessive acid and by-product, It is scattered in after washing in distilled water in neutral graphite oxide, sonic oscillation peels off 40min, by high speed gradient centrifugation again In 2500r min-1Under rotating speed, centrifugation 30min extracts graphene oxide water solution.
6. according to claim 2 preparation method it is characterised in that diisocyanate described in S7. be toluene di-isocyanate(TDI) And/or isoflurane chalcone diisocyanate.
7. according to claim 2 preparation method it is characterised in that described S8. is the washing with acetone S7 gained with 3 times of volumes Solution, 3000r min-1Centrifugation, repetitive operation 4 times, product puts into vacuum drying oven normal temperature drying 48h, obtains modified oxidized stone Black alkene.
8. a kind of Graphene/SiO2 hybrid polyimide foamed materialss are it is characterised in that its preparing raw material is included as follows by weight The component that part calculates：
30～35 parts of benzophenone tetracarboxylic dianhydride；
19～21 parts of diaminodiphenyl ether；
5～40 parts of methanol；
0.01 ~ 0.1 part of 3- aminopropyl triethoxysilane；
6～20 parts of tetraethyl orthosilicate；
10～20 parts of modified graphene oxide described in claim 1.
9. the preparation method of Graphene described in claim 8/SiO2 hybrid polyimide foamed materialss is it is characterised in that include Following steps：
M1. benzophenone tetracarboxylic dianhydride is added in methanol, at 70 ± 5 DEG C, is heated at reflux 1.5～2.5h, subsequently add Enter diaminodiphenyl ether, continue to be heated at reflux 1.5～2.5h at 70 ± 5 DEG C, add 3- aminopropyl triethoxysilane, continue Reaction 1～1.5h；
M2. add modified graphene oxide, continue reaction 1～1.5h, add tetraethyl orthosilicate, continue reaction 20～60min, Obtain the precursor solution of Graphene/SiO2 hybrid polyimide foamed materialss；
M3. precursor solution described in M2 is heated, remove excess of solvent, using pulverizer, the presoma after drying is polished simultaneously Sieve, obtain the precursor powder of uniform particle sizes；
M4. precursor powder is put into from molding jig, in microwave oven, simultaneously the prepared Graphene/SiO2 of imidizate is miscellaneous for foaming Change Polyimide foams.
CN201610909702.0A 2016-10-19 2016-10-19 A kind of graphene/SiO2Hybrid polyimide foamed material and preparation method thereof Active CN106433129B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610909702.0A CN106433129B (en) 2016-10-19 2016-10-19 A kind of graphene/SiO2Hybrid polyimide foamed material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610909702.0A CN106433129B (en) 2016-10-19 2016-10-19 A kind of graphene/SiO2Hybrid polyimide foamed material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106433129A true CN106433129A (en) 2017-02-22
CN106433129B CN106433129B (en) 2019-04-30

Family

ID=58175555

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610909702.0A Active CN106433129B (en) 2016-10-19 2016-10-19 A kind of graphene/SiO2Hybrid polyimide foamed material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106433129B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106832411A (en) * 2017-03-10 2017-06-13 张士兰 A kind of mesoporous fire-retardant graft grapheme material and preparation method thereof
CN107828211A (en) * 2017-11-15 2018-03-23 江苏亚宝绝缘材料股份有限公司 A kind of polymer of graphene compound polyimide resin and its preparation and application
CN112430309A (en) * 2020-11-23 2021-03-02 张茜茜 Phosphorus-containing graphene-SiO2Preparation method and application of modified polyurethane elastomer
CN115746696A (en) * 2022-09-29 2023-03-07 浙江中科玖源新材料有限公司 Polyimide paint for high-heat-resistance enameled wire and high-heat-resistance enameled wire

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103254400A (en) * 2013-05-20 2013-08-21 常州大学 Preparation method of graphene oxide/waterborne polyurethane nanometer composite material
CN103319892A (en) * 2013-07-12 2013-09-25 中国科学院长春应用化学研究所 Polyimide foamed composite and preparation method thereof
CN105037766A (en) * 2015-09-18 2015-11-11 哈尔滨理工大学 SiO2Preparation method of hollow sphere/graphene oxide/polyimide composite film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103254400A (en) * 2013-05-20 2013-08-21 常州大学 Preparation method of graphene oxide/waterborne polyurethane nanometer composite material
CN103319892A (en) * 2013-07-12 2013-09-25 中国科学院长春应用化学研究所 Polyimide foamed composite and preparation method thereof
CN105037766A (en) * 2015-09-18 2015-11-11 哈尔滨理工大学 SiO2Preparation method of hollow sphere/graphene oxide/polyimide composite film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李晓萱 等: "甲苯二异氰酸酯插层改性氧化石墨烯", 《化工新型材料》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106832411A (en) * 2017-03-10 2017-06-13 张士兰 A kind of mesoporous fire-retardant graft grapheme material and preparation method thereof
CN107828211A (en) * 2017-11-15 2018-03-23 江苏亚宝绝缘材料股份有限公司 A kind of polymer of graphene compound polyimide resin and its preparation and application
CN112430309A (en) * 2020-11-23 2021-03-02 张茜茜 Phosphorus-containing graphene-SiO2Preparation method and application of modified polyurethane elastomer
CN115746696A (en) * 2022-09-29 2023-03-07 浙江中科玖源新材料有限公司 Polyimide paint for high-heat-resistance enameled wire and high-heat-resistance enameled wire
CN115746696B (en) * 2022-09-29 2023-12-19 浙江中科玖源新材料有限公司 Polyimide paint for high-heat-resistance enameled wire and high-heat-resistance enameled wire

Also Published As

Publication number Publication date
CN106433129B (en) 2019-04-30

Similar Documents

Publication Publication Date Title
CN106433129A (en) Graphene/SiO2 hybrid polyimide foam material and preparation method thereof
Ni et al. Superior mechanical properties of epoxy composites reinforced by 3D interconnected graphene skeleton
An et al. Rod-like attapulgite/polyimide nanocomposites with simultaneously improved strength, toughness, thermal stability and related mechanisms
Wang et al. Preparation and properties of graphene oxide/polyimide composite films with low dielectric constant and ultrahigh strength via in situ polymerization
Hu et al. Enhanced thermal conductivity by constructing 3D-networks in poly (vinylidene fluoride) composites via positively charged hexagonal boron nitride and silica coated carbon nanotubes
Liu et al. Promoted ablation resistance of polydimethylsiloxane via crosslinking with multi-ethoxy POSS
CN103319892B (en) A kind of Polyimide foam composite material and preparation method thereof
CN104497577A (en) Method for improving heat resistance of organic silicon resin by use of nano-silica-graphene oxide hybrid composite particles
JP4112540B2 (en) Manufacturing method of spherical inorganic hollow powder.
CN106988114B (en) A kind of carbon fiber/silicon dioxide hybrid materials and preparation method thereof
Shen et al. Fabrication of microcellular polymer/graphene nanocomposite foams
Zhang et al. Rational design and fabrication of lightweight porous polyimide composites containing polyaniline modified graphene oxide and multiwalled carbon nanotube hybrid fillers for heat-resistant electromagnetic interference shielding
Zhang et al. Influence of addition of silica particles on reaction-induced phase separation and properties of epoxy/PEI blends
CN105331112A (en) Graphene-silicone rubber compound foam material and preparation method thereof
Chen et al. In situ random co-polycondensation for preparation of reduced graphene oxide/polyimide nanocomposites with amino-modified and chemically reduced graphene oxide
Li et al. Mechanically strong, thermal-insulated, and ultralow dielectric polyimide aerogels with adjustable crosslinking methods
Shepelev et al. Nanotechnology based thermosets
CN104893102A (en) Polypropylene resin-based nano composite material and preparation method thereof
CN113683818A (en) Core-shell structure modified boron nitride and preparation method thereof
CN106220821B (en) A kind of nano combined foam of multifunctional light and its preparation method and application
Kenig et al. Nanocomposite polymer adhesives: A critical review
Hsu et al. Preparation and studies on properties of porous epoxy composites containing microscale hollow epoxy spheres
Liu et al. Structural optimization of polyimide foam via composition with hyperbranched polymer modified fluorinated carbon nanotubes
Peng et al. Fabrication of low dielectric constant fluorinated poly (arylene ether nitrile) composites by cross-linking with metal-organic frameworks
CN111875342B (en) Nano aerogel building thermal insulation material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant