CN106700071A - Preparation method of polycondensation type graphene/polyimide composite adhesive - Google Patents
Preparation method of polycondensation type graphene/polyimide composite adhesive Download PDFInfo
- Publication number
- CN106700071A CN106700071A CN201611011819.3A CN201611011819A CN106700071A CN 106700071 A CN106700071 A CN 106700071A CN 201611011819 A CN201611011819 A CN 201611011819A CN 106700071 A CN106700071 A CN 106700071A
- Authority
- CN
- China
- Prior art keywords
- preparation
- composite adhesive
- graphene
- polymer type
- condensation polymer
- 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
Links
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
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a polycondensation type graphene/polyimide composite adhesive. The preparation method comprises the following steps: carrying out ultrasonic dispersion on an amino functionally modified graphene oxide FGO solution, then respectively adding a diamine monomer 4,4'-diaminodiphenyl ether ODA and 2,2-bis[4-(4-aminophenoxy)phenyl]propane BAPP at 2-5DEG C, adding a solvent N-methyl pyrrolidone NMP, stirring for 30-40 minutes at constant temperature in nitrogen protective atmosphere, then adding 3,3',4,4'-benzophenonetetracarboxylic dianhydride BDTA, and continuously stirring for 8-10 hours at the constant temperature, thus obtaining the polycondensation type graphene/polyimide composite adhesive. The preparation method provided by the invention has the advantages that raw materials are available, price is low, no environmental pollution is produced, and green chemistry requirement is met, so that the preparation method can be popularized and applied.
Description
Technical field
The invention belongs to the preparation field of composite adhesive, more particularly to a kind of condensation polymer type Graphene/polyimides is combined
The preparation method of adhesive.
Background technology
Since polyimides (PI) material of commercialization is pushed out, PI is widely used research, especially in resistance to height
Warm macromolecular material research aspect has very strong real application research meaning.PI glue stick has excellent solvent stability
Energy, heat resistance, radiation-resistant property high, heatproof oxidation performance energy, the resistant to chemical etching, mechanics that smoke rate is low, nontoxic and excellent
Performance, these performances be other organic adhesion agents it is incomparable, thus as the optimal high-temperature resistance adhesive of combination property.
Can apply to Bonding Metal (such as copper, aluminium, titanium alloy, aluminium alloy and stainless steel), inorganic non-metallic (such as silicon chip, glass and
Diamond dust etc.) and polymeric material etc..With the fast development of Aeronautics and Astronautics technology, the heat resistance to adhesive has more
Requirement high.Further to adapt to this demand, researchers have carried out study on the modification to PI, it is composite modified become it is therein
Study hotspot.
The composite modified polyimides of inorganic nano-particle had both on the basis of polyimides inorganic matter high intensity,
The features such as high rigidity, high rigidity, this causes further to be expanded in inorganic nano particle modified polyimides performance.
The unique structure of Graphene creates its excellent optics, electricity, calorifics and mechanical property, and rapidly becomes research
Focus.Graphene nano particle is in terms of composite, solar cell, sensor, nanoelectronics, high-performance nano-electron device
The fields such as the quantum devices such as part, integrated circuit, field-effect transistor, high temperature resistant conductive material have a wide range of applications.By graphite
Alkene is combined to prepare Graphene/polyimides composite adhesive with PI glue stick, can give full play to the excellent of both materials
Performance.At the same time, the oxidation more preferable graphene oxide of peeling effect how is prepared, and how causes inorganic phase
Graphene disperses well in organic PI matrixes, is all larger problem.The degree of oxidation and amination of graphene oxide change
The dispersion effect of property effect and Graphene in PI matrixes can all badly influence final composite material combination property.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of system of condensation polymer type Graphene/polyimides composite adhesive
Preparation Method, the present invention has carried out further improvement on the basis of Hummers methods, and the method after Optimal improvements is successfully prepared
The oxidation more preferable graphene oxide of peeling effect.Then, amination modified, modified graphite oxide is carried out to graphene oxide
Alkene has more preferable dissolubility in NMP, and prepared composite material compositions are more uniform.Meanwhile, the amino of the upper other ends of FGO can
So that in the polymerisation for participating in PAA matrixes, FGO is combined in the form of chemical bond with PAA so that composite adhesive is more equal
Even, stabilization, calorifics, mechanical property are improved well.The composite adhesive prepared using situ aggregation method is effectively avoided
Graphene nano particle machinery causes the uneven problem of its dispersion in being mixed into polymeric matrix.Prepared composite adhesive
During stage elevated cure, dispersiveness of the graphene nano particle in polymeric matrix, this think of are not changed
Road also further expands Graphene or modified Graphene prepares the application prospect of composite with various polymeric matrixs,
It is cheap and raw materials materials are extensive, can promote the use of.
A kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive of the invention, including：
(1) by graphite oxide addition solvent, ultrasound, centrifugation removal centrifugation bottom of the tube do not obtain the oxidation stone fully peeled off
Ink, obtains the graphene oxide colloidal suspensions of homogeneous；Repeat the process repeatedly, hoard graphene oxide colloidal suspensions standby
With；
(2) under stirring condition, by 4,4'- diaminodiphenyl ethers (ODA) add graphene oxide colloidal suspensions in, 70
18~24h of stirring reaction under~80 DEG C of heating conditions, filtering and washing, centrifugal purification, freeze-drying obtains amino functional and is modified
Graphene oxide FGO；Wherein 4,4'- diaminodiphenyl ethers (ODA), the mass volume ratio of graphene oxide colloidal suspensions are
0.1-0.05g：100-150mL；Repeat the process repeatedly, hoard the modified graphene oxide of amino functional standby；
(3) the graphene oxide FGO solution that amino functional is modified, ultrasonic disperse, then in low temperature thermostat bath, control
Under the conditions of 2~5 DEG C of system, diamine monomer 4, double [4- (4- amino-benzene oxygens) benzene of 4'- diaminodiphenyl ethers ODA, 2,2- are separately added into
Base] propane BAPP, (reaction system solid content is 20~25%, according in reaction system to add solvent N-methyl pyrilidone NMP
Specific solid content value, adds the solvent NMP of corresponding volume), constant temperature stirring 30-40min, to be mixed under nitrogen atmosphere protection
After diamines fully dissolves, then 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides (BDTA) are repeatedly dividedly in some parts on a small quantity, continue constant temperature stirring
Prepare and obtain condensation polymer type Graphene/polyimides composite adhesive low temperature seal preservation in 8-10h, original position.
The preparation of graphite oxide is specially in step (1)：By dense H2SO4Solution and dense H3PO4Solution by volume 9.5：
0.5~8.5：1.5 stirring mixing, add graphite powder in the mix acid liquor of gained, continue to stir mixing, add KMnO4, stone
Ink powder and KMnO4Weight ratio be 1：4~1：7,10~30min is first stirred at room temperature, under oil bath controlled temperature conditions, keep system temperature
It is 40~45 DEG C to spend, and stirs 1.5~2h, and oil bath temperature then is increased into 90~95 DEG C again, continues to stir 1~1.5h, is added dropwise
The excessive KMnO of hydrogen peroxide solution reduction4, oxidized graphite mixed liquor is obtained, cleaning is then centrifuged for, dry, obtain graphite oxide.
The dense H2SO4The mass percentage concentration of solution be 98.0%~98.3% and dense H3PO4The quality percentage of solution
Concentration is 80%~85%.
In described 0.8~1.1g graphite is added in every 100mL mix acid liquors.
The mass percentage concentration of the hydrogen peroxide solution is 1%~6%.
The eccentric cleaning is specially：The watery hydrochloric acid for adding molar concentration to be 1~2mol/L in oxidized graphite mixed liquor is molten
Liquid, gained solid by centrifugation, cleaned and be centrifuged with deionized water, is then cleaned with ethanol and is centrifuged,
Cleaned with deionized water and be centrifuged again, gained solid is carried out into vacuum freeze drying, obtained graphite oxide (GO).
Preferably, before being cleaned and being centrifuged with ethanol, first will be cleaned and be centrifuged to gained with deionized water
Supernatant BaCl2Solution is detected without white precipitate, then is cleaned with deionized water and be centrifuged to the supernatant use of gained
AgNO3Solution is detected without white precipitate.
Preferably, gained solid is carried out into vacuum freeze drying condition is：Under conditions of below -60 DEG C, less than 12Pa,
16~24h of vacuum freeze drying.
The ratio of graphite oxide and solvent is 0.1~0.4g in the step (1)：100~400ml.
Ultrasound is in the step (1)：Ultrasonic cell disruptor 8~10min of ultrasound under 250~350W；It is centrifuged and is
10~15min is centrifuged under 2500~3000r/min.
Filtering and washing is in the step (2)：1-METHYLPYRROLIDONE NMP and deionized water filtering and washing are used respectively.
Preferably, vacuum freeze drying condition is in step (2)：Under conditions of below -60 DEG C, less than 12Pa, vacuum
16~24h of freeze-drying.
The ratio of FGO and solvent is in the modified graphene oxide FGO solution of amino functional in the step (3)
0.0765-0.3825g：10-15mL.
Modified graphene oxide FGO is shared in polyamic acid composite adhesive for step (3) amino functional
Mass percent is 0.1~15%.
Two kinds of amount ratios of diamine monomer material are n (ODA) in the step (3)：N (BAPP)=1：2, two kinds of diamines are total
The amount ratio of amount and dianhydride (BTDA) material of material is n (ODA+BAPP)：N (BTDA)=1：1~1.02.
Solvent in step (1), (3) is 1-METHYLPYRROLIDONE NMP.
In step (3) amount ratio of each material be FGO, ODA, BAPP, solvent, BTDA be 0.0765~0.3825g：
1.5g:6.15g:34~40ml:7.25~7.40g.
Measure standard GB/T/T7124-2008 according to adhesive tensile shear strength carries out the overlap joint of bonding piece and surveys
Examination, comprises the concrete steps that：By condensation polymer type Graphene/polyimides composite adhesive be applied to steel plate by bonding part, by two blocks of steel plates
Overlapped and fixed, then bonding piece is placed in vacuum drying chamber, carried out vacuum solidification.Its vacuum solidification technique is：Pressure
Power 24KPa, 40min is incubated at 90 DEG C, is warming up to 130 DEG C of insulation 1h, is warming up to 180 DEG C of insulation 1h, is warming up to 210 DEG C of insulations
1h, is warming up to 260 DEG C of insulation 40min, and when not having FGO to add in adhesive, bonding piece shear strength is about 9.2MPa, with
The difference of FGO additions, corresponding composite adhesive bonding piece shear strength can improve 3%~34%.
Preferably, in vacuum solidification technique, when vacuum drying oven is warmed up to the relevant temperature up in technique, persistently it is incubated the temperature
Corresponding time span is spent, next temperature value in subsequent design temperature to technique, then to be persistently incubated the temperature corresponding time long
Degree, is carried out successively according to curing process flow.
The present invention has carried out further improvement on the basis of Hummers methods, successfully prepares oxidation peeling effect more
Good graphene oxide.Then, carry out amination modified, modified graphene oxide to graphene oxide has more in NMP
Good dissolubility, while during the amino of the other end can participate in the polymerisation of PAA matrixes on FGO, FGO is with the shape of chemical bond
Formula is combined with PAA so that composite adhesive is more uniform, stabilization, and calorifics, mechanical property are improved well.
Beneficial effect
1st, the present invention carries out Strong oxdiative using mix acid liquor to graphite, while instead of NaNO3Use, after Optimal improvements
Method prepared by graphene oxide have preferably oxidation peeling effect, meanwhile, experimentation has effectively avoided poison gas
The discharge of body；
2nd, the present invention in it is amination modified after graphene oxide have more preferable dissolution dispersity in NMP, it is prepared
Composite material compositions are more uniform；
3rd, the composite adhesive prepared using situ aggregation method in the present invention effectively avoids inorganic nano-particle machinery
The problem for causing its dispersion uneven is mixed into polymeric matrix；
4th, raw materials materials of the present invention are extensive, cheap.There is no an environmental pollution, the requirement of composite green chemistry,
Can promote the use of；
5th, the composite adhesive for being obtained by the present invention during stage elevated cure, the oxidation stone of functionalization and modification
Black alkene meeting automatic heating is reduced to the Graphene or Graphene of functionalization and modification, and its dispersion in polymeric matrix is not changed
Property, this thinking also further expands Graphene or modified Graphene and prepares composite with various polymeric matrixs
Application prospect.
Brief description of the drawings
Fig. 1 is the XRD piece of the graphene oxide (GO) of preparation in graphite (GP) and embodiment (1)；Illustration is according to cloth
Glug formula 2dsin θ=n λ, the interlamellar spacing d values for calculating, are computed obtaining, dGP=0.346, dGO=0.837；
Fig. 2 is the thermogravimetric curve figure of the PI glue film for adding FGO mass fractions to be 1.2% and 0%；
Fig. 3 is the Raman pictures of graphene oxide GO (b) of preparation in graphite GP (a) and embodiment (2)；
Fig. 4 is TEM picture of the graphene oxide of preparation in embodiment (3) under low power (a) and high power resolution ratio (b)；
Fig. 5 is the stage elevated cure flow chart of composite adhesive.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood 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, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
(1) oxidation of graphite powder：
By the dense H that 85ml mass fractions are 98%2SO4Solution and 15ml mass fractions are 80% dense H3PO4Solution successively adds
Enter volume be 250ml round-bottomed flask in, with mixer with rotating speed be 300rpm carry out mechanical agitation mix 5min, in gained
1g graphite powders are added in mix acid liquor, and (crystalline flake graphite, granularity≤30 μm, accounting >=95%), continuation is stirred by 300rpm of rotating speed
Mix well mixed to system, by 5g KMnO4Divide and be repeatedly slowly added in above-mentioned solution on a small quantity, be that 350rpm is stirred with rotating speed
30min；Under oil bath controlled temperature conditions, 40 DEG C of stirring reaction 2h are warming up to 90 DEG C of stirring reaction 1.5h.Then, quality point is added dropwise
Number is the excessive KMnO of 4.5% dilute hydrogen peroxide solution reduction4, obtain oxidized graphite mixed liquor；The preparation of described hydrogen peroxide
Method is that the H that 16ml mass fractions are 30% is added in the beaker for filling 100ml deionized waters2O2Solution, glass bar stirring is equal
It is even.
(2) eccentric cleaning of graphene oxide and drying：
It is the dilute hydrochloric acid solution of 1.5mol/L that molar concentration is added in described oxidized graphite mixed liquor, is with rotating speed
Be centrifuged and with deionized water be cleaned multiple times gained solid and be that 8000rpm is centrifuged to institute with rotating speed by 8000rpm
The supernatant BaCl of 0.02mol/L2Solution detect without white precipitate, then be cleaned multiple times with deionized water and with turn
The AgNO of the 0.02mol/L of the supernatant to gained is centrifuged for 8000rpm for speed3Solution detection then uses ethanol without white precipitate
Carry out three times cleaning and with rotating speed be 8500rpm centrifugation, then cleaned with deionized water and with rotating speed be 8500rpm centrifugation point
From.Then, under conditions of -70 DEG C, 14Pa, vacuum freeze drying 23h obtains dry graphene oxide.
(3) aminofunctional of graphene oxide is modified：
0.1g graphite oxides are weighed in beaker, is added in 100ml solvent N-methyl pyrilidones (NMP), with ultrasound
Ripple cell disruptor ultrasound 8min under 250W.Then 10min removal centrifugation bottom of the tube is centrifuged under 2500r/min to be filled
Divide the graphite oxide peeled off, obtain the graphene oxide colloidal suspensions of homogeneous.Added in 250ml three neck round bottom flask above-mentioned
Graphene oxide colloidal suspensions 100ml, adds 4, the 4'- diaminodiphenyl ethers (ODA) of 0.1g under stirring condition, add at 70 DEG C
Stirring reaction 18h under heat condition.NMP and deionized water filtering and washing, centrifugal purification are then used respectively, are obtained through vacuum freeze drying
To the graphene oxide (FGO) that amino functional is modified.
(4) preparation of composite adhesive：
The FGO of 0.0765g is added in three neck round bottom flask, ultrasonic disperse 10min is dissolved with 10ml NMP, then,
In low temperature thermostat bath, under the conditions of 2 DEG C of temperature control, by the double [4- (4- of 1.5g (0.0075mol) ODA and 6.15g (0.015mol) 2,2-
Amino-benzene oxygen) phenyl] two kinds of diamine monomers of propane (BAPP) are separately added into there-necked flask, add 34~40ml solvent NMP,
In N2Constant temperature stirring 30min under the protection of atmosphere, after diamines to be mixed fully dissolves, being then repeatedly dividedly in some parts total amount on a small quantity is
7.25g (0.0225mol) BTDA, continues constant temperature stirring reaction 8h, and composite adhesive is prepared in original position, and low temperature seal is preserved.
(5) the stage elevated cure of composite adhesive bonding piece and composite adhesive film：
Synthetically prepared composite adhesive is directly used in adhesive glue, and the quilt that appropriate composite adhesive is applied to steel plate is taken with spoon
Bonding part, takes another block of steel plate and is overlapped and fixed.Adhesive topple over uniformly with glass plate on, (scrape the edge of a knife with No. 5 scrapers
Thickness 0.5mm) uniform force application scrapes tacky film.Bonding piece and the glass plate for scraping tacky film are placed in vacuum drying chamber, are pressed
Vacuum solidification is carried out according to following technique：Pressure 24KPa, 40min is incubated at 90 DEG C, is warming up to 130 DEG C of insulation 1h, is warming up to 180
DEG C insulation 1h, be warming up to 210 DEG C insulation 1h, be warming up to 260 DEG C insulation 40min.
Accompanying drawing 1 is the XRD of the graphene oxide (GO) of preparation in graphite (GP) and embodiment 1.It can be seen that graphite exists
26.4 ° have a sharp diffraction maximum, and distance is equal between illustrating graphite flake layer, and with very regular structure.Graphite is through oxygen
Change after peeling off, the characteristic peak for reacting GO (001) plane occurs at 10.6 ° in the graphite oxide powder for obtaining, while near 25 °
The Bao Feng for not having disperse is present, and illustrates that HGO oxidations are very abundant.According to bragg's formula 2dsin θ=n λ, it is computed obtaining, dGP=
0.346, dGO=0.837.
Accompanying drawing 2 is the thermogravimetric curve figure of the PI glue film for adding FGO mass fractions to be 1.2% and 0%.Can be seen by figure
Go out, before 500 DEG C, two kinds of glued membranes illustrate composite adhesive after ladder-elevating temperature curing process all without obvious thermal weight loss
Imidization is abundant, and two kinds of glued membranes have good heat-resistant stability.When FGO incorporations are zero, the thermal decomposition of pure PI glue film
Temperature at 500 DEG C, when it is 1.2% to add FGO mass fractions, the heat decomposition temperature of compound cutan at 553 DEG C, with pure PI glue film
10.6% is improve compared to heat resisting temperature.The use heat resisting temperature of adhesive is significantly improved.
Measure standard GB/T/T7124-2008 according to adhesive tensile shear strength carries out composite adhesive bonding piece
Tensile strength testing, the shear strength average of pure PI reaches 9.5MPa, and the shear strength average of compound adhesive bonding piece reaches in this example
To 11.8MPa, compared to raising 24.2%.
Embodiment 2
(1) oxidation of graphite powder：
By the dense H that 90ml mass fractions are 98%2SO4Solution and 10ml mass fractions are 81% dense H3PO4Solution successively adds
Enter volume be 250ml round-bottomed flask in, with mixer with rotating speed be 310rpm carry out mechanical agitation mix 5min, in gained
1g graphite powders are added in mix acid liquor, and (crystalline flake graphite, granularity≤30 μm, accounting >=95%), continuation is stirred by 300rpm of rotating speed
Mix well mixed to system, by 6g KMnO4Divide and be repeatedly slowly added in above-mentioned solution on a small quantity, be that 350rpm is stirred with rotating speed
25min；Under oil bath controlled temperature conditions, 40 DEG C of stirring reaction 2h are warming up to 90 DEG C of stirring reaction 1.5h.Then, quality point is added dropwise
Number is the excessive KMnO of 4.5% dilute hydrogen peroxide solution reduction4, obtain oxidized graphite mixed liquor；The preparation of described hydrogen peroxide
Method is that the H that 16ml mass fractions are 30% is added in the beaker for filling 100ml deionized waters2O2Solution, glass bar stirring is equal
It is even.
(2) eccentric cleaning of graphene oxide and drying：
It is the dilute hydrochloric acid solution of 1.5mol/L that molar concentration is added in described oxidized graphite mixed liquor, is with rotating speed
Be centrifuged and with deionized water be cleaned multiple times gained solid and be that 8000rpm is centrifuged to institute with rotating speed by 8000rpm
The supernatant BaCl of 0.02mol/L2Solution detect without white precipitate, then be cleaned multiple times with deionized water and with turn
The AgNO of the 0.02mol/L of the supernatant to gained is centrifuged for 8000rpm for speed3Solution detection then uses ethanol without white precipitate
Carry out three times cleaning and with rotating speed be 8300rpm centrifugation, then cleaned with deionized water and with rotating speed be 8500rpm centrifugation point
From.Then, under conditions of -70 DEG C, 14Pa, vacuum freeze drying 23h obtains dry graphene oxide.
(3) aminofunctional of graphene oxide is modified：
0.2g graphite oxides are weighed in beaker, is added in 200ml solvent N-methyl pyrilidones (NMP), with ultrasound
Ripple cell disruptor ultrasound 8min under 250W.Then 10min removal centrifugation bottom of the tube is centrifuged under 2500r/min to be filled
Divide the graphite oxide peeled off, obtain the graphene oxide colloidal suspensions of homogeneous.Added in 250ml three neck round bottom flask above-mentioned
Graphene oxide colloidal suspensions 100ml, adds 4, the 4'- diaminodiphenyl ethers (ODA) of 0.1g under stirring condition, add at 70 DEG C
Stirring reaction 18h under heat condition.NMP and deionized water filtering and washing, centrifugal purification are then used respectively, are obtained through vacuum freeze drying
To the graphene oxide (FGO) that amino functional is modified.
(4) preparation of composite adhesive：
The FGO of 0.0765g is added in three neck round bottom flask, ultrasonic disperse 10min is dissolved with 10ml NMP, then,
In low temperature thermostat bath, under the conditions of 2 DEG C of temperature control, by the double [4- (4- of 1.5g (0.0075mol) ODA and 6.15g (0.015mol) 2,2-
Amino-benzene oxygen) phenyl] two kinds of diamine monomers of propane (BAPP) are separately added into there-necked flask, add 34~40ml solvent NMP,
In N2Constant temperature stirring 30min under the protection of atmosphere, after diamines to be mixed fully dissolves, being then repeatedly dividedly in some parts total amount on a small quantity is
7.25g (0.0225mol) BTDA, continues constant temperature stirring reaction 8h, and composite adhesive is prepared in original position, and low temperature seal is preserved.
(5) the stage elevated cure of composite adhesive bonding piece：
Synthetically prepared composite adhesive is directly used in adhesive glue, and the quilt that appropriate composite adhesive is applied to steel plate is taken with spoon
Bonding part, takes another block of steel plate and is overlapped and fixed.Bonding piece is placed in vacuum drying chamber, is carried out very according to following technique
Sky solidification：Pressure 24KPa, 40min is incubated at 90 DEG C, is warming up to 130 DEG C of insulation 1h, is warming up to 180 DEG C of insulation 1h, is warming up to
210 DEG C of insulation 1h, are warming up to 260 DEG C of insulation 40min.
Accompanying drawing 3 is the Raman pictures of the graphite oxide (GO) of preparation in graphite (GP) and embodiment 2.The laser of graphite draws
The G peaks of graceful spectrum are located at 1592cm-1Place, G peaks are due to sp in carbocyclic ring or long-chain2Atom pair extensional motion is produced.Graphite laser
The D peaks of Raman spectrum are located at 1352cm-1Place, D peaks are because fault of construction or unordered induction double resonance Raman scattering are produced.Graphite
After oxidized stripping, original crystal structure is destroyed, and is also generated while a large amount of polar functional groups are aoxidized out a large amount of
Fault of construction, therefore graphene oxide is in 1352cm-1There is obvious D peaks, I in placeD/IGBe worth is 1.12.
Measure standard GB/T/T7124-2008 according to adhesive tensile shear strength carries out composite adhesive bonding piece
Tensile strength testing, the shear strength average of pure PI reaches 9.7MPa, and the shear strength average of compound adhesive bonding piece reaches in this example
To 12.6MPa, compared to raising 29.8%.
Embodiment 3
(1) oxidation of graphite powder：
By the dense H that 91ml mass fractions are 98%2SO4Solution and 9ml mass fractions are 82% dense H3PO4Solution successively adds
Enter volume be 250ml round-bottomed flask in, with mixer with rotating speed be 310rpm carry out mechanical agitation mix 5min, in gained
1.5g graphite powders are added in mix acid liquor, and (crystalline flake graphite, granularity≤30 μm, accounting >=95%), continue with rotating speed as 300rpm
Stirring is well mixed to system, by 7g KMnO4Divide and be repeatedly slowly added in above-mentioned solution on a small quantity, be that 350rpm is stirred with rotating speed
25min；Under oil bath controlled temperature conditions, 40 DEG C of stirring reaction 2h are warming up to 90 DEG C of stirring reaction 1.5h.Then, quality point is added dropwise
Number is the excessive KMnO of 3% dilute hydrogen peroxide solution reduction4, obtain oxidized graphite mixed liquor；The preparation side of described hydrogen peroxide
Method is：The H that 10ml mass fractions are 30% is added in the beaker for filling 100ml deionized waters2O2Solution, glass bar stirring is equal
It is even.
(2) eccentric cleaning of graphene oxide and drying：
It is the dilute hydrochloric acid solution of 1.5mol/L that molar concentration is added in described oxidized graphite mixed liquor, is with rotating speed
Be centrifuged and with deionized water be cleaned multiple times gained solid and be that 8000rpm is centrifuged to institute with rotating speed by 8000rpm
The supernatant BaCl of 0.02mol/L2Solution detect without white precipitate, then be cleaned multiple times with deionized water and with turn
The AgNO of the 0.02mol/L of the supernatant to gained is centrifuged for 8000rpm for speed3Solution detection then uses ethanol without white precipitate
Carry out three times cleaning and with rotating speed be 8300rpm centrifugation, then cleaned with deionized water and with rotating speed be 8500rpm centrifugation point
From.Then, under conditions of -70 DEG C, 14Pa, vacuum freeze drying 24h obtains dry graphene oxide.
(3) aminofunctional of graphene oxide is modified：
0.3g graphite oxides are weighed in beaker, is added in 300ml solvent N-methyl pyrilidones (NMP), with ultrasound
Ripple cell disruptor ultrasound 10min under 250W.Then 12min removal centrifugation bottom of the tube is centrifuged under 2500r/min not obtain
The graphite oxide fully peeled off, obtains the graphene oxide colloidal suspensions of homogeneous.Added in 250ml three neck round bottom flask
Graphene oxide colloidal suspensions 100ml is stated, 4, the 4'- diaminodiphenyl ethers (ODA) of 0.1g is added under stirring condition, at 70 DEG C
Stirring reaction 18h under heating condition.NMP and deionized water filtering and washing, centrifugal purification are then used respectively, through vacuum freeze drying
Obtain the modified graphene oxide (FGO) of amino functional.
(4) preparation of composite adhesive：
The FGO of 0.0765g is added in three neck round bottom flask, ultrasonic disperse 10min is dissolved with 10ml NMP, then,
In low temperature thermostat bath, under the conditions of 2 DEG C of temperature control, by the double [4- (4- of 1.5g (0.0075mol) ODA and 6.15g (0.015mol) 2,2-
Amino-benzene oxygen) phenyl] two kinds of diamine monomers of propane (BAPP) are separately added into there-necked flask, add 34~40ml solvent NMP,
In N2Constant temperature stirring 30min under the protection of atmosphere, after diamines to be mixed fully dissolves, being then repeatedly dividedly in some parts total amount on a small quantity is
7.32g (0.0227mol) BTDA, continues constant temperature stirring reaction 9h, and composite adhesive is prepared in original position, and low temperature seal is preserved.
(5) the stage elevated cure of composite adhesive bonding piece：
Synthetically prepared composite adhesive is directly used in adhesive glue, and the quilt that appropriate composite adhesive is applied to steel plate is taken with spoon
Bonding part, takes another block of steel plate and is overlapped and fixed.Bonding piece is placed in vacuum drying chamber, is carried out very according to following technique
Sky solidification：Pressure 24KPa, 40min is incubated at 90 DEG C, is warming up to 130 DEG C of insulation 1h, is warming up to 180 DEG C of insulation 1h, is warming up to
210 DEG C of insulation 1h, are warming up to 260 DEG C of insulation 40min.
Accompanying drawing 4 is TEM picture of the graphene oxide of preparation in embodiment (3) under low power and high power resolution ratio.GO quilts
Oxidation obtains very thin layered graphite oxide alkene after peeling off, transparent such as tulle, and surface undulation bending is in accordion.For thin layer
Graphene oxide, this accordion can be good at drop low-surface-energy improve stability.
Measure standard GB/T/T7124-2008 according to adhesive tensile shear strength carries out composite adhesive bonding piece
Tensile strength testing, the shear strength average of pure PI reaches 9.9MPa, and the shear strength average of compound adhesive bonding piece reaches in this example
To 11.3MPa, compared to raising 14.1%.
Embodiment 4
(1) oxidation of graphite powder：
By the dense H that 92ml mass fractions are 98%2SO4Solution and 8ml mass fractions are 81% dense H3PO4Solution successively adds
Enter volume be 250ml round-bottomed flask in, with mixer with rotating speed be 310rpm carry out mechanical agitation mix 5min, in gained
2g graphite powders are added in mix acid liquor, and (crystalline flake graphite, granularity≤30 μm, accounting >=95%), continuation is stirred by 300rpm of rotating speed
Mix well mixed to system, by 10g KMnO4Divide and be repeatedly slowly added in above-mentioned solution on a small quantity, be that 350rpm is stirred with rotating speed
25min；Under oil bath controlled temperature conditions, 40 DEG C of stirring reaction 2h are warming up to 90 DEG C of stirring reaction 1.5h.Then, quality point is added dropwise
Number is the excessive KMnO of 3.5% dilute hydrogen peroxide solution reduction4, obtain oxidized graphite mixed liquor；The preparation of described hydrogen peroxide
Method is：The H that 12ml mass fractions are 30% is added in the beaker for filling 100ml deionized waters2O2Solution, glass bar stirring
Uniformly.
(2) eccentric cleaning of graphene oxide and drying：
It is the dilute hydrochloric acid solution of 1.5mol/L that molar concentration is added in described oxidized graphite mixed liquor, is with rotating speed
Be centrifuged and with deionized water be cleaned multiple times gained solid and be that 8000rpm is centrifuged to institute with rotating speed by 8000rpm
The supernatant BaCl of 0.02mol/L2Solution detect without white precipitate, then be cleaned multiple times with deionized water and with turn
The AgNO of the 0.02mol/L of the supernatant to gained is centrifuged for 8000rpm for speed3Solution detection then uses ethanol without white precipitate
Carry out three times cleaning and with rotating speed be 8300rpm centrifugation, then cleaned with deionized water and with rotating speed be 8400rpm centrifugation point
From.Then, under conditions of -70 DEG C, 14Pa, vacuum freeze drying 24h obtains dry graphene oxide.
(3) aminofunctional of graphene oxide is modified：
0.2g graphite oxides are weighed in beaker, is added in 200ml solvent N-methyl pyrilidones (NMP), with ultrasound
Ripple cell disruptor ultrasound 9min under 250W.Then 12min removal centrifugation bottom of the tube is centrifuged under 2500r/min to be filled
Divide the graphite oxide peeled off, obtain the graphene oxide colloidal suspensions of homogeneous.Added in 250ml three neck round bottom flask above-mentioned
Graphene oxide colloidal suspensions 100ml, adds 4, the 4'- diaminodiphenyl ethers (ODA) of 0.1g under stirring condition, add at 70 DEG C
Stirring reaction 18h under heat condition.NMP and deionized water filtering and washing, centrifugal purification are then used respectively, are obtained through vacuum freeze drying
To the graphene oxide (FGO) that amino functional is modified.
(4) preparation of composite adhesive：
The FGO of 0.0765g is added in three neck round bottom flask, ultrasonic disperse 10min is dissolved with 10ml NMP, then,
In low temperature thermostat bath, under the conditions of 2 DEG C of temperature control, by the double [4- (4- of 1.5g (0.0075mol) ODA and 6.15g (0.015mol) 2,2-
Amino-benzene oxygen) phenyl] two kinds of diamine monomers of propane (BAPP) are separately added into there-necked flask, add 34~40ml solvent NMP,
In N2Constant temperature stirring 30min under the protection of atmosphere, after diamines to be mixed fully dissolves, being then repeatedly dividedly in some parts total amount on a small quantity is
7.38g (0.0229mol) BTDA, continues constant temperature stirring reaction 10h, and composite adhesive is prepared in original position, and low temperature seal is preserved.
(5) the stage elevated cure of composite adhesive bonding piece：
Synthetically prepared composite adhesive is directly used in adhesive glue, and the quilt that appropriate composite adhesive is applied to steel plate is taken with spoon
Bonding part, takes another block of steel plate and is overlapped and fixed.Bonding piece is placed in vacuum drying chamber, is carried out very according to following technique
Sky solidification：Pressure 24KPa, 40min is incubated at 90 DEG C, is warming up to 130 DEG C of insulation 1h, is warming up to 180 DEG C of insulation 1h, is warming up to
210 DEG C of insulation 1h, are warming up to 260 DEG C of insulation 40min.
Measure standard GB/T/T7124-2008 according to adhesive tensile shear strength carries out composite adhesive bonding piece
Tensile strength testing, the shear strength average of pure PI reaches 9.5MPa, and the shear strength average of compound adhesive bonding piece reaches in this example
To 11.3MPa, compared to raising 18.9%.
Claims (10)
1. a kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive, including：
(1) by graphite oxide addition solvent, ultrasound, centrifugation obtain graphene oxide colloidal suspensions；
(2) under stirring condition, by 4,4'- diaminodiphenyl ethers ODA add graphene oxide colloidal suspensions in, at 70~80 DEG C
Under the conditions of 18~24h of stirring reaction, filtering and washing, centrifugal purification, freeze-drying obtains the modified graphite oxide of amino functional
Alkene FGO；Wherein 4,4'- diaminodiphenyl ethers ODA, the mass volume ratio of graphene oxide colloidal suspensions are 0.1-0.05g：
100-150mL；
(3) the graphene oxide FGO solution that amino functional is modified, ultrasonic disperse then under the conditions of 2~5 DEG C, adds respectively
Enter diamine monomer 4, double [4- (4- amino-benzene oxygens) phenyl] the propane BAPP of 4'- diaminodiphenyl ethers ODA, 2,2- add solvent
1-METHYLPYRROLIDONE NMP, constant temperature stirring 30-40min, adds 3,3', 4,4'- benzophenone tetracids under nitrogen atmosphere protection
Dianhydride BDTA, continues constant temperature stirring 8-10h, obtains final product condensation polymer type Graphene/polyamic acid composite adhesive.
2. a kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive according to claim 1, its feature
It is：The preparation of graphite oxide is specially in step (1)：By dense H2SO4Solution and dense H3PO4Solution by volume 9.5：0.5~
8.5：1.5 stirring mixing, add graphite in the mix acid liquor of gained, continue to stir mixing, add KMnO4, graphite and
KMnO4Weight ratio be 1：4~1：7,10~30min is first stirred at room temperature, under oil bath controlled temperature conditions, it is 40 to keep system temperature
~45 DEG C, 1.5~2h is stirred, oil bath temperature is then increased to 90~95 DEG C again, continue to stir 1~1.5h, hydrogen peroxide is added dropwise
The excessive KMnO of solution reduction4, oxidized graphite mixed liquor is obtained, cleaning is then centrifuged for, dry, obtain graphite oxide.
3. a kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive according to claim 1, its feature
It is：The ratio of graphite oxide and solvent is 0.1~0.4g in the step (1)：100~400ml.
4. a kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive according to claim 1, its feature
It is：Ultrasound is in the step (1)：Ultrasonic cell disruptor 8~10min of ultrasound under 250~350W；Centrifugation be
10~15min is centrifuged under 2500~3000r/min.
5. a kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive according to claim 1, its feature
It is：Filtering and washing is in the step (2)：1-METHYLPYRROLIDONE NMP and deionized water filtering and washing are used respectively.
6. a kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive according to claim 1, its feature
It is：The ratio of FGO and solvent is 0.0765- in the modified graphene oxide FGO solution of amino functional in the step (3)
0.3825g：10-15mL.
7. a kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive according to claim 1, its feature
It is：The modified graphene oxide FGO of amino functional shared in polyamic acid composite adhesive matter in the step (3)
Amount percentage is 0.1~15%.
8. a kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive according to claim 1, its feature
It is：Two kinds of amount ratios of diamine monomer material are n (ODA) in the step (3)：N (BAPP)=1：2, two kinds of total things of diamines
The amount ratio of amount and dianhydride (BTDA) material of matter is n (ODA+BAPP)：N (BTDA)=1：1~1.02.
9. a kind of preparation method of condensation polymer type Graphene/polyimides composite adhesive according to claim 1, its feature
It is：Solvent in step (1), (3) is 1-METHYLPYRROLIDONE NMP.
10. the preparation method of a kind of condensation polymer type Graphene/polyimides composite adhesive according to claim 1, it is special
Levy and be：Condensation polymer type Graphene/polyimides composite adhesive that step (3) is obtained is directly used in adhesive glue：Will be compound gluing
Agent be applied to steel plate by bonding part, take another block of steel plate and overlapped and fixed, then bonding piece is placed in vacuum drying chamber,
Carry out vacuum solidification；Wherein vacuum solidification technique is specially：Pressure 24KPa, 40min is incubated at 90 DEG C, is warming up to 130 DEG C of insulations
1h, is warming up to 180 DEG C of insulation 1h, is warming up to 210 DEG C of insulation 1h, is warming up to 260 DEG C of insulation 40min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611011819.3A CN106700071B (en) | 2016-11-17 | 2016-11-17 | A kind of preparation method of condensation polymer type graphene/polyimides composite adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611011819.3A CN106700071B (en) | 2016-11-17 | 2016-11-17 | A kind of preparation method of condensation polymer type graphene/polyimides composite adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106700071A true CN106700071A (en) | 2017-05-24 |
| CN106700071B CN106700071B (en) | 2019-05-07 |
Family
ID=58939798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611011819.3A Active CN106700071B (en) | 2016-11-17 | 2016-11-17 | A kind of preparation method of condensation polymer type graphene/polyimides composite adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106700071B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880264A (en) * | 2017-12-06 | 2018-04-06 | 华南协同创新研究院 | A kind of graphene modified polyamide heat conduction PUR and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104164208A (en) * | 2014-08-13 | 2014-11-26 | 东华大学 | Preparation method of graphene/polyimide composite adhesive |
| CN105086447A (en) * | 2015-08-26 | 2015-11-25 | 苏州卓伟企业管理咨询有限公司 | Preparation method of modified graphene oxide/PI (polyimide) composite material |
| CN105482113A (en) * | 2014-10-02 | 2016-04-13 | 三星电子株式会社 | Composition for preparing polyimide-inorganic particle composite, polyimide-inorganic particle composite, article prepared therefrom and optical device |
-
2016
- 2016-11-17 CN CN201611011819.3A patent/CN106700071B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104164208A (en) * | 2014-08-13 | 2014-11-26 | 东华大学 | Preparation method of graphene/polyimide composite adhesive |
| CN105482113A (en) * | 2014-10-02 | 2016-04-13 | 三星电子株式会社 | Composition for preparing polyimide-inorganic particle composite, polyimide-inorganic particle composite, article prepared therefrom and optical device |
| CN105086447A (en) * | 2015-08-26 | 2015-11-25 | 苏州卓伟企业管理咨询有限公司 | Preparation method of modified graphene oxide/PI (polyimide) composite material |
Non-Patent Citations (2)
| Title |
|---|
| CHUNYAN WANG等: "Preparation of amino-functionalized graphene oxide/polyimidecomposite films with improved mechanical, thermal and hydrophobic properties", 《APPLIED SURFACE SCIENCE》 * |
| YONG QIAN等: "Decorating graphene sheets with Pt nanoparticles using sodium citrate as reductant", 《APPLIED SURFACE SCIENCE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880264A (en) * | 2017-12-06 | 2018-04-06 | 华南协同创新研究院 | A kind of graphene modified polyamide heat conduction PUR and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106700071B (en) | 2019-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105949512B (en) | Intercalation assembling boron nitride-graphene composite material, using and preparation method thereof | |
| CN105818504B (en) | A kind of polyimide composite film of one side Inverter fed motor and preparation method thereof | |
| CN107141726A (en) | Graphene conductive polymer composite, its preparation method and Electric radiant Heating Film therefrom | |
| CN109929129A (en) | A kind of carboxylic carbon nano-tube/polyimide composite film and preparation method thereof | |
| CN107180706A (en) | The preparation method and application of dyefunctionalized grapheme/polyaniline composite material | |
| CN106280440B (en) | A kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof | |
| CN112456484A (en) | Graphite heat-conducting film and preparation method thereof | |
| CN103923318B (en) | A kind of containing amino crosslinkable polyether sulphone and its production and use | |
| CN106084219B (en) | A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film | |
| CN106008974B (en) | A kind of preparation method of high hydrophobic fluorinated carbon nano-tube/polyimide composite material | |
| CN111378191A (en) | Graphene/polyimide heat conduction film and preparation method thereof | |
| CN109401314A (en) | A kind of preparation method of graphene/polyimide composite material | |
| CN102174236A (en) | Preparation method of polyvinylidene fluoride-based composite with high dielectric constant | |
| CN107433402B (en) | A kind of preparation method and applications of graphene-nano mattisolda | |
| CN105601919A (en) | Polyimide nanocomposite of naphthalene-containing structure and preparation method and application of polyimide nanocomposite | |
| CN106044760A (en) | Method for preparing graphene oxide | |
| CN101708829A (en) | Method for preparing yttria-stabilized zirconia powder | |
| CN107892784A (en) | A kind of polymer based nanocomposites and preparation method thereof | |
| CN108822317A (en) | A kind of preparation method of graphene polyimide heating film | |
| CN111995866A (en) | Low-dielectric polyimide composite film material and preparation method thereof | |
| CN105523552A (en) | Graphene compound conductive powder and preparation method thereof | |
| CN104530616A (en) | High dielectric property and low loss sheet-shaped barium titanate base/ polymer composite material and preparation method thereof | |
| CN103554909B (en) | Carbon nano tube compound material, its preparation method, prepreg and copper-clad base plate that polymer-silica is coated | |
| CN107955167A (en) | A kind of preparation method of high-performance polyimide titanium carbide nanosheet composite material | |
| CN108341929A (en) | A kind of Graphene epoxy resin composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |