CN109401202A - Class honeycomb sandwich construction graphene-epoxy resin composite material and preparation method thereof - Google Patents
Class honeycomb sandwich construction graphene-epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN109401202A CN109401202A CN201811325588.2A CN201811325588A CN109401202A CN 109401202 A CN109401202 A CN 109401202A CN 201811325588 A CN201811325588 A CN 201811325588A CN 109401202 A CN109401202 A CN 109401202A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
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- 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
- C09J11/08—Macromolecular additives
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
Abstract
The invention discloses type honeycomb sandwich construction graphene-epoxy resin composite materials and preparation method thereof, the preparation method is comprising steps of (1) prepares graphene oxide, and then graphene oxide is prepared into graphene, and be modified to graphene；(2) hybrid particle is added in modified graphene, and hybrid particle and modified graphene is compound；(3) it is further introduced into long flexible chain, obtains the modifier of graphite alkenes honeycomb；And the modifier of the graphite alkenes honeycomb obtained through the above steps is added in epoxy resin modification object by (4), obtain class honeycomb sandwich construction graphene-epoxy resin composite material, the preparation is conducive to graphene in the dispersion of resin matrix by chemical functional group's modification, graphene-epoxy resin composite material is prepared using fusion method, it avoids bringing environmental pollution using solvent method, and then is conducive to the characteristics of keeping polymer matrix composites to have high-modulus and high tenacity concurrently.
Description
Technical field
The present invention relates to field of compound material, especially with regard to a type honeycomb sandwich construction graphene-epoxy resin
Composite material and preparation method.
Background technique
Since epoxy resin-base composite material has the excellent spies such as intensity height, chemical corrosion resistance, the small, heat resistance of shrinking percentage
Point becomes one of indispensable basic material of industrial circle, additionally by the different curing agent of selection, toughener, functionality
Performance required for filler obtains epoxy resin, to greatly open up the application range of epoxy resin.But due to ring
Oxygen resin is more crisp, and fatigue durability, heat resistance, impact resistance are poor, is very restricted its application.It is main at present
Toughening approach be: the high viscoelastic rubber (CTBN, ATBN) of addition, thermoplastic resin (PES, PPS, PEI), inorganic nano
Particle (nanometer calcium carbonate, fumed silica), core shell rubbers etc..Rubber toughener is added, Tg machine resin matrix can be caused
Modulus decline；Thermoplastic resin, melt viscosity is big, and resin hybrid technique is poor；Inorganic nano-particle is light, easily hike up, reunite,
It is not easy to evenly spread in resin system.
Graphene, the Colloidal particles that a kind of carbon atom by sp2 hydridization is formed with hexagon periodic arrangement it is inorganic
Nanoscale twins material, thickness only have 0.335nm, and carrier moves when having many excellent properties such as quantum hall effect, room temperature
Shifting rate high (2 × 105cm2Vs), thermal coefficient are high (5300Wm-1K-1), large specific surface area (2360m2g-1),
The breaking strength of graphene reaches 125GPa, and Young's modulus reaches 1.0TPa.Graphene is now known most firm in the world
Material, it is considered to be the preferred material of reinforced resin composite materials property.
However since the stronger Van der Waals force between graphene layer makes it easy to cause to reunite, disperse in resin matrix uneven
It is even, the not biggish raising of mechanical property is caused, can be declined instead.In " In situ thermally reduced
It is pointed out in graphene oxide/epoxy composites:thermal and mechanical properties " document
Graphene modified epoxy is added, wherein casting matrix tensile strength drops to 46MPa from 70MPa.Other documents and materials " graphite
Alkene is modified to the influence of epoxy resin/carbon fiber tensile property of multi-filament ", " Graphene-based composite
materials”、“Preparation of graphene dispersions and graphene-polymer
composites in organic media”、“Effect of Pyrene Treatment on the Properties of
Graphene/Epoxy Nanocomposites " points out to improve graphene in the dispersibility of resin matrix, using acetone,
Ethyl alcohol, dimethylformamide, styrene, the organic solvents such as pyrene are dispersed, then are handled with ultrasonic wave.Due to organic solvent
Presence, be unfavorable for industrialized production and labourer's health protection.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
The purpose of the present invention is to provide a type honeycomb sandwich construction graphene-epoxy resin composite material and its preparations
Method is conducive to graphene in the dispersion of resin matrix by chemical functional group's modification, prepares graphene-ring using fusion method
Epoxy resin composite material avoids bringing environmental pollution using solvent method, and then is conducive to that polymer matrix composites is kept to have height concurrently
The characteristics of modulus and high tenacity.
To achieve the above object, the present invention provides a type honeycomb sandwich construction graphene-epoxy resin composite materials
Preparation method, the preparation method comprises the following steps: (1) graphene surface chemical functional group be grafted: prepare graphite oxide
Alkene, and then the graphene oxide is prepared into graphene, and be modified to the graphene；(2) graphene surface hydridization:
It will be by adding hybrid particle in step (1) modified graphene, and by the hybrid particle and the modified graphite
Alkene is compound, so that the hybrid particle adheres to or is wrapped in the surface of modified graphene () laminated structure, due to
Graphene is laminated structure, and 1~20 μm of diameter, hybrid particle diameter is 1~1000nm, while being deposited between graphene and hybrid particle
In stronger molecular force, hybrid particle is made to adhere to/be wrapped in the surface of the laminated structure of graphene；(3) long flexible chain
It is introduced into: further will introduce long flexible chain in the graphene after above-mentioned modification and surface hydridization, obtain graphite alkenes honeycomb
The modifier of structure；And polymer matrix composites are added in (4) class honeycomb graphene: will pass through the step (1)-(3)
The modifier of obtained graphite alkenes honeycomb is added in epoxy resin modification object to arrive class honeycomb sandwich construction graphite
Alkene-epoxy resin composite material.
In a preferred embodiment, in the step (1), the graphene oxide is by using improved
Hummer method prepares, under specific steps enter: natural flake graphite being taken to be added slowly with stirring the appearance of the dress concentrated sulfuric acid
In device, in 0 DEG C of ice bath environment, potassium permanganate is added and stirs 30~60min, is slow added into distilled water, is stirred 20
~30min pours into the H that mass percent is 2~7%2O2, filter while hot, then sufficiently washed with hydrochloric acid to solution ph and be
Property, filtering, vacuum drying obtain graphene oxide black powder.
In a preferred embodiment, in the step (1), the preparation step of the graphene is as follows: by the oxygen
Graphite alkene is transferred in Muffle furnace, is taken and is rapidly heated to 1000 DEG C or more, sharply expanded by heating divides graphene to be oxidized
At graphene.
In a preferred embodiment, in the step (1), the specific steps being modified to the graphene are such as
Under: modifier is added in high temperature Muffle furnace, grafting-OH ,-COOH and-NH are active on the surface of graphene in 700~1200 DEG C
Functional group (modified schematic diagram is as follows), to complete the modification to the graphene；Preferably, the modifier includes Malaysia
Acid anhydrides, ethylenediamine, sodium sulfonate and ammonia.
In a preferred embodiment, in the step (2), the hydridization grain that is added in the modified graphene
Son is nanoparticle；Preferably, the nanoparticle includes carbon nanotube, fumed silica, calcium carbonate and montmorillonite.
In a preferred embodiment, in the step (2), by the hybrid particle and the modified graphene
Compound specific steps are as follows: by hybrid particle physical absorption or chemical solution processing or mechanical oscillation stirring with it is described modified
Graphene mixing, to make the surface of the hybrid particle attachment or the laminated structure for being wrapped in the modified graphene.
In a preferred embodiment, in the step (3), introduce long flexible chain the step of it is as follows: will pass through above-mentioned
Graphene and long flexible chain after modified and surface hydridization are dissolved in organic solution, further add SOCl2And nitrogen, in 25
DEG C activation 3~6h, then filter, be vacuum-treated solvent, freeze-drying obtain the modifier of graphite alkenes honeycomb；It is preferred that
, one of the optional acetone of the organic solution, ethyl alcohol and n,N-Dimethylformamide.
In a preferred embodiment, in the step (3), the long flexible chain is selected from polyethers, polyester, poly- amino
Formic acid esters, poly- (methyl) acrylate, polybutadiene, polydialkysiloxane or hydrocarbon residue, long-chain oligomerization containing siloxanes
Object, monomer, aliphatic amine (D-2000 or NH40D), aromatic amine, heterocyclic amine, polyetheramine (D230) and polyurethane change
At least one of property object；When the long-chain oligomer selects long-chain amine modified, sufficiently long segment is needed, meets two primary
Most short atomic link between amine groups must include the diamines of at least 30 atom this requirement.
In a preferred embodiment, the step (4) specific steps are as follows: the step (1)-will be passed through
(3) modifier of the graphite alkenes honeycomb obtained is added in epoxy resin modification object, and further fiting chemical equivalent is matched
The curing agent of ratio is uniformly mixed to get the class honeycomb sandwich construction graphene-epoxy resin composite wood is arrived by mechanical stirring
Material；Such honeycomb sandwich construction graphene-epoxy resin composite material can be used as RTM note by resin viscosity, active adjusting
It penetrates with resin, vacuum importing resin, prepreg resin.
In a preferred embodiment, the epoxy resin modification object, which is chosen, has difunctional epoxy, trifunctional
At least one of epoxy resin modification object of epoxy, four-functional group epoxy and multifunction group epoxy；The curing agent is selected from
At least one of aliphatic amine, aromatic amine, anhydride and tertiary amine.
Compared with prior art, class honeycomb sandwich construction graphene-epoxy resin composite material according to the present invention and its
Preparation method has the following beneficial effects:
The preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material according to the present invention passes through chemistry
Functional group modification is conducive to the dispersion in resin matrix, prepares graphene-epoxy resin composite material using fusion method, avoids adopting
The influence of environmental pollution, health is brought with solvent method；Class honeycomb sandwich construction (panel-sandwich-panel) can be sent out simultaneously
The characteristic of graphene laminated structure high-modulus and middle flexible group high tenacity is waved, and then is conducive to keep polymer matrix composites
The characteristics of having high-modulus and high tenacity concurrently.
Detailed description of the invention
Fig. 1 is hybrid particle/graphene-structured schematic diagram according to an embodiment of the present invention；
Fig. 2 is hybrid particle/graphene SEM figure according to an embodiment of the present invention；
Fig. 3 is graphene interlayers structure according to an embodiment of the present invention；
Fig. 4 is graphite alkenes honeycomb sandwich construction according to an embodiment of the present invention.
Main appended drawing reference explanation:
1- graphene laminated structure, 2- adhesive (long flexible chain), 3- core material (hybrid particle of cladding).
Specific embodiment
With reference to the accompanying drawing, specific embodiments of the present invention will be described in detail, it is to be understood that guarantor of the invention
Shield range is not limited by the specific implementation.
Unless otherwise explicitly stated, otherwise in entire disclosure and claims, term " includes " or its change
Changing such as "comprising" or " including " etc. will be understood to comprise stated element or component, and not exclude other members
Part or other component parts.
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples, it is unless otherwise specified, commercially commercially available.
Embodiment 1
Natural flake graphite 2g is taken to be added slowly with stirring in the container of the dress concentrated sulfuric acid, in 0 DEG C of ice bath environment,
Potassium permanganate is added and stirs 30min, is slow added into distilled water, is stirred 20min, pour into the H of 2wt%2O2It is sufficiently stirred,
Mixing time is 30min, and observation solution colour filters mixed solution to yellow while hot, then is sufficiently washed with hydrochloric acid to solution
PH value is neutrality, and filtering, vacuum drying obtain graphene oxide black powder, graphene oxide and maleic anhydride mixed
It closes, is put into togerther 20s in 1000 DEG C of high temperature furnace, cooling obtains the modified graphene of surface luminous energy group, then adds 0.01g
Fumed silica, is transferred to high-speed dispersion equipment, and revolving speed uses 2500 turns/min, incorporation time 3min to will transfer to reaction
In bottle, the SOCl of 20mL is added2With the DMF of 2mL, flow back in 70 DEG C for 24 hours, by SOCl unreacted in above-mentioned product2Decompression is evacuated to
Constant weight, then be slowly added into product the D-2000 that 1g is added into flask for anhydrous DMF, after gained mixed liquor ultrasonic disperse in
72h is reacted in 120 DEG C of oil baths, filters, be dried to obtain modified graphene, 100:0.5 in mass ratio (resin/graphite alkene) will
Modified graphene is added in E-51 epoxy resin, is heated 60 DEG C, is dispersed by mechanical stirring, is uniformly mixed miscellaneous without black particle
It after matter, is added CTBN (liquid rubber), continuess to mix 20min, be eventually adding T31 room temperature curing agent, prepare the modified room of graphene
Warm curing agent adhesive.
Embodiment 2
Natural flake graphite 1g is taken to be added slowly with stirring in the container of the dress concentrated sulfuric acid, in 0 DEG C of ice bath environment,
Potassium permanganate is added and stirs 45min, is slow added into distilled water, is stirred 20min, pour into the H of 2wt%2O2It is sufficiently stirred,
Mixing time is 30min, and observation solution colour filters mixed solution to yellow while hot, then is sufficiently washed with hydrochloric acid to solution
PH value is neutrality, and filtering, vacuum drying obtain graphene oxide black powder, graphene oxide are put into 800 DEG C of high temperature furnace
Interior 20s, obtains the graphene of single layer, then adds 0.01g fumed silica, is transferred to high-speed dispersion equipment, and revolving speed uses
2500 turns/min, the SOCl of 20mL is added in incorporation time 3min2With the DMF of 2mL, flow back in 70 DEG C for 24 hours, by above-mentioned product
In unreacted SOCl2Decompression is evacuated to constant weight, then is slowly added into product the D-2000 that 1g is added into flask for anhydrous DMF,
72h is reacted in 120 DEG C of oil baths after gained mixed liquor ultrasonic disperse, filters, be dried to obtain modified graphene, by modified graphite
Alkene is added in AFG-90 epoxy resin, is dispersed by mechanical stirring, after being uniformly mixed without black particle impurity, is added 5 parts
CTBN (liquid rubber) is stirred 20min at 80 DEG C, is cooled to 65 DEG C and is eventually adding 5 parts of dicyandiamides and 3 parts of UR-300, stirring
20min, preparation are suitable for the modified Medium Temperature Curing Heat-resisting type ring epoxy resin system of graphene of introducing technology.
Embodiment 3
Natural flake graphite 0.1g is taken to be added slowly with stirring in the container of the dress concentrated sulfuric acid, in 0 DEG C of ice bath environment
In, potassium permanganate is added and stirs 45min, is slow added into distilled water, is stirred 20min, pour into the H of 2wt%2O2Sufficiently stir
It mixes, mixing time 30min, observation solution colour filters mixed solution to yellow while hot, then is sufficiently washed with hydrochloric acid to molten
Liquid pH value is neutrality, and filtering, vacuum drying obtain graphene oxide black powder, graphene and sodium sulfonate are put into 1000 DEG C
10s in high temperature furnace, cooling obtain table functional group modification graphene, then add 0.01g fumed silica, are transferred to high speed point
It is casually arranged with standby, revolving speed uses 3000 turns/min, and the SOCl of 20mL is added in incorporation time 1min2With the DMF of 2mL, flow back in 70 DEG C
For 24 hours, by SOCl unreacted in above-mentioned product2Decompression is evacuated to constant weight, then is slowly added to anhydrous DMF into product and adds into flask
Enter the polyetheramine (D230) of 5g, reacts 72h in 120 DEG C of oil baths after gained mixed liquor ultrasonic disperse, filter, be dried to obtain modification
Graphene, obtained graphene will 100:1.5 in mass ratio (resin/graphite alkene), modified graphene is added to AG-80 ring
In oxygen resin, dispersed by mechanical stirring, after being uniformly mixed without black particle impurity, 10 parts of PEK-C (thermoplastic toughenings are added
Agent), 20min is mixed by high speed dispersion, is eventually adding DDS high-temperature curing agent, stirs 20min, it is raw that preparation is suitable for prepreg
The modified hot setting heat-resistance type epoxy resin system of the graphene of production. art.
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining specific principle of the invention and its actually answering
With so that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes of the invention and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. the preparation method of a type honeycomb sandwich construction graphene-epoxy resin composite material, which is characterized in that the preparation
Method the following steps are included:
(1) graphene surface chemical functional group is grafted: preparing graphene oxide, and then the graphene oxide is prepared into graphite
Alkene, and the graphene is modified；
(2) graphene surface hydridization: will be by adding hybrid particle in step (1) modified graphene, and by the hydridization
Particle and the modified graphene are compound, so that the hybrid particle adheres to or be wrapped in modified graphene
The surface of laminated structure；
(3) long flexible chain is introduced into: further long flexible chain will be introduced in the graphene after above-mentioned modification and surface hydridization,
Obtain the modifier of graphite alkenes honeycomb；And
(4) polymer matrix composites: the graphite alkenes that will be obtained by the step (1)-(3) are added in class honeycomb graphene
The modifier of honeycomb is added in epoxy resin modification object to get multiple to class honeycomb sandwich construction graphene-epoxy resin
Condensation material.
2. the preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material as described in claim 1, feature
It is, in the step (1), the graphene oxide is prepared by using improved Hummer method, specific steps
Under entering:
It takes natural flake graphite to be added slowly with stirring in the container of the dress concentrated sulfuric acid, in 0 DEG C of ice bath environment, is added high
Potassium manganate stirs 30~60min, is slow added into distilled water, is stirred 20~30min, and pouring into mass percent is 2~7%
H2O2, filter while hot, then sufficiently washed with hydrochloric acid to solution ph be it is neutral, filtering, that vacuum drying obtains graphene oxide is black
Color powder.
3. the preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material as described in claim 1, feature
It is, in the step (1), the preparation step of the graphene is as follows:
The graphene oxide is transferred in Muffle furnace, takes and is rapidly heated to 1000 DEG C or more, graphene to be oxidized is sharply
Expanded by heating splits into graphene.
4. the preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material as described in claim 1, feature
It is, in the step (1), is modified that specific step is as follows to the graphene:
Modifier is added in high temperature Muffle furnace, grafting-OH ,-COOH and-NH are living on the surface of graphene in 700~1200 DEG C
Property functional group, to complete modification to the graphene；Preferably, the modifier includes maleic anhydride, ethylenediamine, sulfonic acid
Sodium and ammonia.
5. the preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material as described in claim 1, feature
It is, in the step (2), the hybrid particle added in the modified graphene is nanoparticle；Preferably, described
Nanoparticle includes carbon nanotube, fumed silica, calcium carbonate and montmorillonite.
6. the preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material as described in claim 1, feature
It is, in the step (2), by the hybrid particle and the compound specific steps of the modified graphene are as follows: by hydridization
Particle physics absorption or chemical solution processing or mechanical oscillation stirring are mixed with the modified graphene, to make described miscellaneous
Change particle attachment or is wrapped in the surface of the laminated structure of the modified graphene.
7. the preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material as described in claim 1, feature
Be, in the step (3), introduce long flexible chain the step of it is as follows:
Graphene after above-mentioned modification and surface hydridization is dissolved in organic solution with long flexible chain, is further added
SOCl2And then nitrogen filters in 25 DEG C of 3~6h of activation, is vacuum-treated solvent, freeze-drying obtains graphite alkenes honeycomb knot
The modifier of structure；Preferably, one of the optional acetone of the organic solution, ethyl alcohol and n,N-Dimethylformamide.
8. the preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material as described in claim 1, feature
Be, in the step (3), the long flexible chain selected from polyethers, polyester, polyurethanes, poly- (methyl) acrylate,
Polybutadiene, polydialkysiloxane or hydrocarbon residue, long-chain oligomer, monomer, aliphatic amine, aromatic series containing siloxanes
At least one of amine, heterocyclic amine, polyetheramine and polyurethane-modified object.
9. the preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material as described in claim 1, feature
Be, the step (4) specific steps are as follows: will be by graphite alkenes honeycomb knot that the step (1)-(3) obtain
The modifier of structure is added in epoxy resin modification object, and the curing agent of further fiting chemical equivalent proportion passes through mechanical stirring
It is uniformly mixed to get the class honeycomb sandwich construction graphene-epoxy resin composite material is arrived.
10. the preparation method of class honeycomb sandwich construction graphene-epoxy resin composite material as claimed in claim 9, special
Sign is, the epoxy resin modification object is chosen with difunctional epoxy, trifunctional epoxy, four-functional group epoxy and more
At least one of epoxy resin modification object of functional group's epoxy；The curing agent is selected from aliphatic amine, aromatic amine, acid
At least one of anhydride and tertiary amine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110699026A (en) * | 2019-10-22 | 2020-01-17 | 亿铖达（深圳）新材料有限公司 | Flexible epoxy pouring sealant |
| CN110964366A (en) * | 2019-12-26 | 2020-04-07 | 哈尔滨奥晶云科技有限公司 | Carbon-series conductive filler in water-based conductive electrostatic coating and preparation method thereof |
| CN113372863A (en) * | 2021-06-22 | 2021-09-10 | 深圳市汇海鑫科技有限公司 | High-thermal-conductivity and high-electric-conductivity organic adhesive and preparation method thereof |
| CN114656750A (en) * | 2021-12-31 | 2022-06-24 | 华侨大学 | Outdoor epoxy resin-based anti-ultraviolet aging insulating material, preparation method and application |
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2018
- 2018-11-08 CN CN201811325588.2A patent/CN109401202A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110699026A (en) * | 2019-10-22 | 2020-01-17 | 亿铖达（深圳）新材料有限公司 | Flexible epoxy pouring sealant |
| CN110964366A (en) * | 2019-12-26 | 2020-04-07 | 哈尔滨奥晶云科技有限公司 | Carbon-series conductive filler in water-based conductive electrostatic coating and preparation method thereof |
| CN113372863A (en) * | 2021-06-22 | 2021-09-10 | 深圳市汇海鑫科技有限公司 | High-thermal-conductivity and high-electric-conductivity organic adhesive and preparation method thereof |
| CN114656750A (en) * | 2021-12-31 | 2022-06-24 | 华侨大学 | Outdoor epoxy resin-based anti-ultraviolet aging insulating material, preparation method and application |
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