CN112457506A - Preparation method of graphene-polyethylene composite pipe - Google Patents
Preparation method of graphene-polyethylene composite pipe Download PDFInfo
- Publication number
- CN112457506A CN112457506A CN202011341689.6A CN202011341689A CN112457506A CN 112457506 A CN112457506 A CN 112457506A CN 202011341689 A CN202011341689 A CN 202011341689A CN 112457506 A CN112457506 A CN 112457506A
- Authority
- CN
- China
- Prior art keywords
- graphene
- polyethylene
- mixing
- dispersion liquid
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
-
- 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
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2323/36—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with nitrogen-containing compounds, e.g. by nitration
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention discloses a preparation method of a graphene polyethylene composite pipe, which comprises the following steps: 1: preparing modified polyethylene with cations on the surface; 2: stirring and mixing graphene, a solvent and a dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid to enable the two-dimensional size of the graphene to reach 10nm-1000nm, and dispersing to obtain a graphene dispersion liquid; 3: adding modified polyethylene and graphene dispersion liquid into a centrifugal mixer, carrying out centrifugal mixing at the temperature of 40-100 ℃, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating graphene on the surface of the modified polyethylene, and mixing to obtain composite granules; 4: and melting and extruding the composite granules to obtain the composite pipe. The invention can effectively combine graphene with excellent mechanical properties with polyethylene and can avoid the aggregation of graphene, thereby obtaining the composite material with better pressure resistance.
Description
Technical Field
The invention relates to the technical field of graphene composite materials, in particular to a preparation method of a graphene polyethylene composite pipe.
Background
The PE pipe is widely applied to various transportation occasions due to the unique advantages of the PE pipe, and the main types of the PE pipe comprise six main types, namely a PE water supply and drainage pipe, a PE gas pipe, a PE mining pipe, an agricultural pipe, an electric power pipe, a blow-off pipe and the like. The market of the PE pipe for water supply is about 400 million tons every year, and the PE pipe for the water supply pipe at present comprises a PE steel-plastic composite pipe (a plastic-lined steel-plastic composite pipe, a plastic-coated steel-plastic composite pipe and a steel wire framework plastic composite pipe), a polyethylene full-plastic pipe and the like. Wherein, the polyethylene plastic pipe can generate unstable water pressure and the like in water supply, so that how to improve the pressure resistance of the polyethylene plastic pipe has important significance.
Graphene has attracted much attention as a novel carbon material since its discovery in 2004. The material is a quasi-two-dimensional crystal material which is composed of sp2 hybridized carbon atoms and has the thickness of only a single atomic layer or a plurality of single atomic layers, and has excellent performances of high light transmittance, electric conductivity, thermal conductivity, high specific surface area, high strength, flexibility and the like. Graphene has an ultrahigh specific surface area as high as 2600m2/g, an ultrahigh strength 100 times that of steel, and good flexibility and extensibility, and theoretically, the strength of the PE pipe can be enhanced by adding graphene into the PE pipe, but a technology capable of effectively fusing the graphene and the PE pipe does not exist at present.
The document with publication number CN102585335A discloses a preparation method of a polyethylene/graphene conductive composite material, which comprises placing graphene oxide in a solvent of water and ethanol for ultrasonic dispersion, adding polyethylene powder, mechanically stirring to evaporate the solvent, vacuum drying to remove the residual solvent to obtain composite particles with a shell-core structure, wherein the polyethylene powder is coated with a layer of graphene oxide, reducing the composite particles by hydrazine hydrate, and hot pressing to obtain a sheet-like composite material with lower Yu-percolation threshold and higher conductivity. However, the method is only limited to the mode of mould pressing, so that the method cannot be used for preparing the pipe, and the mode of hydrazine hydrate is very harmful to the environment.
The document with publication number CN109503924A discloses a graphene composite material and a preparation method thereof, in the method, the graphene polyethylene composite material with antibacterial and certain mechanical properties can be obtained by stirring polyethylene, graphene, zinc stearate, chitosan, octyl trimethyl ammonium chloride, Chinese brake herb powder, sodium citrate, paprika powder and lauryl triethanolamine sulfate, and then extruding, but the mixing process of the method is complex and the introduced additives are more.
The document with publication number CN109851975A discloses a graphene composite material and a preparation method thereof, in which graphene, a silane coupling agent, polypropylene, low-density polyethylene, SEBS, oils, an antioxidant, and the like are used as raw materials, and the composite material is prepared by a melt blending method. However, the method does not carry out any modification and dispersion design on the graphene, and only relies on the dispersion of the screw to the graphene, so that the problem of graphene dispersion is difficult to solve in a real sense.
The document with publication number CN106117949B discloses a high-density polyethylene resin-based nanocomposite and a preparation method thereof, in the method, a composite material with good mechanical properties and thermal properties is prepared by melt blending modified graphene oxide, carbon nanotubes and maleic anhydride grafted high-density polyethylene, but the acidification modification of graphene/carbon nanotubes is complicated and is not suitable for industrialization, and the graphene is hardly well dispersed by adopting a melt blending mode.
The document with publication number CN109181069A discloses a graphene oxide reinforced polyethylene composite material and a preparation method thereof, and the method can prepare a graphene polyethylene composite material with better toughness by using a parallel electric field to orient active groups on graphene oxide. The publication No. CN107446231A discloses a polyethylene composite material jointly modified by graphene, carbon nano tubes and fullerene and a preparation method thereof, and the method utilizes the synergistic effect of three fillers of graphene, carbon nano tubes and fullerene to prepare the polyethylene conductive composite material. However, both methods do not concern about simultaneous enhancement and toughening of graphene, and the simultaneous enhancement and toughening can only be realized by realizing good dispersion of graphene in polyethylene, and the graphene is hardly dispersed and recovered to the nano structure by using a simple screw shearing force in a real sense.
Based on the above, in the prior art, effective dispersion of graphene is not considered when preparing the graphene polyethylene composite material, and the mixing or modification manner is complex. In addition, the above prior art also fails to effectively combine the excellent mechanical properties of graphene, such as high strength and flexibility, into the polyethylene component, so that the pressure resistance of the composite material prepared therefrom is poor.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provides a preparation method of a graphene-polyethylene composite pipe.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a graphene polyethylene composite pipe is characterized by comprising the following steps:
step 1: modified polyethylene
Adding a modifier with cations into ethanol to form a modified solution, adding the modified solution into polyethylene under a stirring state, mixing, and drying to obtain modified polyethylene with cations on the surface;
step 2: preparation of the Dispersion
Stirring and mixing graphene, a solvent and a dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid to enable the two-dimensional size of the graphene to reach 10nm-1000nm, and dispersing to obtain a graphene dispersion liquid;
and step 3: electrostatic self-assembly
Adding modified polyethylene and graphene dispersion liquid into a centrifugal mixer, carrying out centrifugal mixing at the temperature of 40-100 ℃, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating graphene on the surface of the modified polyethylene, and mixing to obtain composite granules;
and 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
The specific method of the step 1 comprises the following steps: adding polyethylene into a stirrer with a heating function, adding the modifying liquid into the stirrer in a spraying mode under the conditions that the rotating speed is 100-400r/min and the temperature is 60-100 ℃, mixing with the polyethylene, and continuously keeping the rotating speed and the temperature for 10-30min after the modifying liquid is completely added to obtain the modified polyethylene with the surface having cations.
In the step 1, the mass percentage concentration of the ethanol is 95%, the mass percentage concentration of the modifier in the modifying liquid is 1-10%, and the mass ratio of the modifier to the polyethylene is 0.1-3: 100.
in the step 1, the modifier is a cationic surfactant with long-chain alkyl or a small/high molecular substance with amino groups.
The cationic surfactant with long-chain alkyl is one or more of cetyl ammonium bromide, 3-aminopropyl trimethoxy silane, quaternary ammonium salt with alkyl, quaternary ammonium salt containing hetero atoms, quaternary ammonium salt containing benzene rings and quaternary ammonium salt containing heterocycles according to any proportion.
In the step 2, the graphene is graphene oxide or graphene nanosheets, the two-dimensional size of the graphene is less than 1um, the solvent is one or a plurality of water, an organic solvent and isopropanol which are mixed in any proportion, and the dispersant is a high-molecular polymer containing benzene rings, double bonds or triple bonds.
In the step 2, the mass percentage concentration of the graphene dispersion liquid is 0.01-2%.
In the step 2, the pre-dispersion liquid is subjected to dispersion treatment in a manner including, but not limited to, shearing, homogenizing, sanding and ball milling.
In the step 3, the mass ratio of the modified polyethylene to the graphene dispersion liquid is 100: 1-30, and the mixing rate is 400-.
The invention has the advantages that:
1. in the preparation method, step 1 can obtain modified polyethylene with cations on the surface, step 2 can enable graphene to be better dispersed, and step 3 is that the graphene is negatively charged, and the polyethylene is modified and then positively charged, so that the positive charges and the negative charges can be mutually attracted, thereby forming electrostatic self-assembly. Compared with physical adsorption in the CN102585335A document, the graphene can be stably combined with polyethylene under the action of positive charges by adopting an electrostatic self-assembly mode, the intrinsic mechanical property of the graphene is utilized to the maximum extent, and the stability after combination is better. Meanwhile, the graphene can be dispersed in the dispersion liquid without agglomeration, and the excellent characteristics of the graphene are ensured. Compared with other documents, the method disclosed by the invention not only avoids the technical problems caused by simply dispersing the graphene by using a melt blending mode, but also avoids the technical problems of complex mixing or modification mode and the like, simultaneously optimizes the preparation process, reduces the damage to the environment, and ensures the excellent dispersing performance and the good water pressure resistance of the graphene in a system.
2. The invention limits specific rotating speed and temperature when modifying polyethylene, and has the advantages that polyethylene materials can be effectively combined with modifying liquid, and finally all polyethylene surfaces are provided with cations.
3. The mass percent concentration of ethanol is set to 95%, the mass percent concentration of a modifier in a modifying solution is set to 1-10%, and the mass ratio of the modifier to polyethylene is set to 0.1-3: 100, which has the advantage of enabling the modifier to be fully hydrolyzed.
4. The invention excludes the cationic surfactant with long-chain alkyl or the small/high molecular substance with amino group as the modifier, and has the advantage of enabling the surface of the polyethylene material to have positive charges, thereby facilitating the electrostatic self-assembly of the subsequent process.
5. The cationic surfactant is one or more of cetyl ammonium bromide, 3-aminopropyl trimethoxy silane, quaternary ammonium salt with alkyl group, quaternary ammonium salt containing hetero atom, quaternary ammonium salt containing benzene ring and quaternary ammonium salt containing heterocycle, and has the advantages of positive charge on the surface of polyethylene material and non-covalent action on polyethylene to form excellent contact.
6. The invention adopts the high molecular polymer containing benzene ring, double bond or triple bond as the dispersant, and can play an excellent dispersing role in graphene
7. According to the invention, the graphene dispersion liquid with the mass percentage concentration of 0.01-2% is used, so that the polyethylene material can be effectively coated on the premise of less usage amount of graphene.
Detailed Description
The invention provides a graphene polyethylene composite pipe, which comprises the following steps:
step 1: modified polyethylene
Firstly, adding a modifier with cations into 95 mass percent ethanol for mixing to obtain a modified solution with the modifier mass percent of 1-10% for later use.
Wherein the modifier with cation is cationic surfactant with long chain alkyl or small/high molecular substance with amino group. The cationic surfactant with long-chain alkyl group is one or more of cetyl ammonium bromide, 3-aminopropyl trimethoxy silane, quaternary ammonium salt with alkyl group, quaternary ammonium salt containing hetero atom, quaternary ammonium salt containing benzene ring and quaternary ammonium salt containing heterocycle according to any proportion.
Secondly, adding the polyethylene granules or powder into a stirrer with a heating function, setting the rotating speed of the stirrer to be 100-400r/min and the temperature to be 60-100 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 0.1-3: and 100, after the modified liquid is completely added, continuously keeping the rotating speed and the temperature for 10-30min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersant, wherein the graphene is oxidized graphene or graphene nanosheets with two-dimensional size smaller than 1um, the solvent is one or a plurality of water, an organic solvent and isopropanol which are mixed according to any proportion, and the dispersant is a high-molecular polymer containing benzene rings, double bonds or triple bonds.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 10nm-1000nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 0.01-2% after dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: adding 1-30 mass percent of the mixture into a centrifugal mixer, centrifugally mixing at the temperature of 40-100 ℃ and the speed of 400-3000r/min, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating the graphene on the surface of the modified polyethylene, and mixing to obtain the composite granules.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, 3-aminopropyltrimethoxysilane is adopted as a modifier, the 3-aminopropyltrimethoxysilane is added into 95 percent ethanol by mass for mixing, and a modified solution with the modifier of 1 percent by mass is obtained after mixing for later use.
Secondly, adding polyethylene into a stirrer with a heating function, setting the rotating speed of the stirrer to be 100r/min and the temperature to be 60 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with the polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 0.1: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 10min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersing agent, wherein the graphene is oxidized graphene with the two-dimensional size smaller than 1um, the solvent is water, and the dispersing agent is a high molecular polymer containing benzene rings.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 10nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 0.01% after the dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: adding the mixture into a centrifugal mixer according to the mass ratio of 1, centrifugally mixing at the temperature of 40 ℃ and the speed of 400r/min, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating the graphene on the surface of the modified polyethylene, and mixing to obtain the composite granules.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 2
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, cetyl ammonium bromide is used as a modifier, the cetyl ammonium bromide is added into ethanol with the mass percentage concentration of 95% for mixing, and a modifying solution with the mass percentage concentration of 10% of the modifier is obtained after mixing for later use.
Secondly, adding polyethylene into a stirrer with a heating function, setting the rotating speed of the stirrer to be 400r/min and the temperature to be 100 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with the polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 3: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 30min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersant, wherein the graphene is a graphene nanosheet with a two-dimensional size smaller than 1um, the solvent is an organic solvent, and the dispersant is a high-molecular polymer containing double bonds.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 1000nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 2% after dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: adding 30 mass percent of the mixture into a centrifugal mixer, centrifugally mixing at the temperature of 100 ℃ and the speed of 3000r/min, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating the graphene on the surface of the modified polyethylene, and mixing to obtain the composite granules.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 3
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, 3-aminopropyltrimethoxysilane is adopted as a modifier, the 3-aminopropyltrimethoxysilane is added into 95 percent ethanol by mass for mixing, and a modifying solution with 5 percent of the modifier by mass is obtained after mixing for later use.
Secondly, adding polyethylene into a stirrer with a heating function, setting the rotating speed of the stirrer to be 250r/min and the temperature to be 80 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with the polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 1.5: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 20min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersant, wherein the graphene is graphene oxide with a two-dimensional size smaller than 1um, the solvent is isopropanol, and the dispersant is a high-molecular polymer containing triple bonds.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 500nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 1% after dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: 15, and centrifugally mixing at the temperature of 70 ℃ and the speed of 2000r/min, wherein the modified polyethylene and the graphene dispersion liquid are subjected to electrostatic self-assembly in the mixing process, the graphene is uniformly coated on the surface of the modified polyethylene, and the composite granules are obtained after mixing.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 4
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, a mixture of hexadecyl ammonium bromide and 3-aminopropyl trimethoxy silane is used as a modifier, the mixture of hexadecyl ammonium bromide and 3-aminopropyl trimethoxy silane is added into ethanol with the mass percentage concentration of 95% for mixing, and a modifying solution with the mass percentage concentration of 3% of the modifier is obtained after mixing for later use.
Secondly, adding polyethylene into a stirrer with a heating function, setting the rotating speed of the stirrer to be 18r/min and the temperature to be 70 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with the polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 0.5: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 15min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersing agent, wherein the graphene is a graphene nanosheet with a two-dimensional size smaller than 1um, the solvent is isopropanol, and the dispersing agent is a high-molecular polymer containing a benzene ring.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 100nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 0.05% after the dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: 10, and centrifugally mixing at the temperature of 55 ℃ and the speed of 1000r/min, wherein the modified polyethylene and the graphene dispersion liquid are subjected to electrostatic self-assembly in the mixing process, the graphene is uniformly coated on the surface of the modified polyethylene, and the composite granules are obtained after mixing.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 5
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, adopting quaternary ammonium salt with alkyl as a modifier, adding the quaternary ammonium salt with alkyl into 95% ethanol by mass percent, mixing, and obtaining a modifying solution with the modifier of 8% by mass percent for later use.
Secondly, adding polyethylene into a stirrer with a heating function, setting the rotating speed of the stirrer to be 300r/min and the temperature to be 90 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with the polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 3: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 30min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersant, wherein the graphene is graphene oxide with the two-dimensional size smaller than 1um, the solvent is water and an organic solvent which are mixed according to any proportion, and the dispersant is a high-molecular polymer containing double bonds.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 800nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 2% after dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: 18, and centrifugally mixing at 55 ℃ and 2200r/min, wherein the modified polyethylene and the graphene dispersion liquid are subjected to electrostatic self-assembly in the mixing process, the graphene is uniformly coated on the surface of the modified polyethylene, and the composite granules are obtained after mixing.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 6
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, quaternary ammonium salt containing heteroatoms is used as a modifier, the quaternary ammonium salt containing the heteroatoms is added into ethanol with the mass percentage concentration of 95% for mixing, and a modifying solution with the mass percentage concentration of 10% of the modifier is obtained after mixing for later use.
Secondly, adding polyethylene into a stirrer with a heating function, setting the rotating speed of the stirrer to be 150r/min and the temperature to be 70 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with the polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 2.5: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 20min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersing agent, wherein the graphene is oxidized graphene with the two-dimensional size smaller than 1um, the solvent is water and isopropanol which are mixed according to any proportion, and the dispersing agent is a high molecular polymer containing benzene rings.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 700nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 0.08% after the dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: adding 25 mass percent of the mixture into a centrifugal mixer, centrifugally mixing at the temperature of 100 ℃ and the speed of 3000r/min, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating the graphene on the surface of the modified polyethylene, and mixing to obtain the composite granules.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 7
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, quaternary ammonium salt containing benzene rings is used as a modifier, the quaternary ammonium salt containing benzene rings is added into ethanol with the mass percentage concentration of 95% for mixing, and a modifying solution with the mass percentage concentration of 10% of the modifier is obtained after mixing for later use.
Secondly, adding polyethylene into a stirrer with a heating function, setting the rotating speed of the stirrer to be 350r/min and the temperature to be 70 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with the polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 1: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 30min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersant, wherein the graphene is a graphene nanosheet with a two-dimensional size smaller than 1um, the solvent is an organic solvent and isopropanol which are mixed according to any proportion, and the dispersant is a high-molecular polymer containing double bonds.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 900nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 1% after dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: adding 25 mass percent of the mixture into a centrifugal mixer, centrifugally mixing at the temperature of 100 ℃ and the speed of 3000r/min, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating the graphene on the surface of the modified polyethylene, and mixing to obtain the composite granules.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 8
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, adopting quaternary ammonium salt containing heterocycle as a modifier, adding the quaternary ammonium salt containing heterocycle into ethanol with the mass percentage concentration of 95% for mixing, and obtaining a modified solution with the mass percentage concentration of 10% of the modifier after mixing for later use.
Secondly, adding polyethylene into a stirrer with a heating function, setting the rotating speed of the stirrer to be 100r/min and the temperature to be 60 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with the polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 0.1: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 10min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersant, wherein the graphene is graphene oxide with a two-dimensional size smaller than 1um, the solvent is an organic solvent, and the dispersant is a high-molecular polymer containing benzene rings.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 10nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 1% after dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: adding the mixture into a centrifugal mixer according to the mass ratio of 1, centrifugally mixing at the temperature of 40 ℃ and the speed of 600r/min, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating the graphene on the surface of the modified polyethylene, and mixing to obtain the composite granules.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 9
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, using a micromolecule substance with an amino group as a modifier, adding the micromolecule substance with the amino group into ethanol with the mass percentage concentration of 95% for mixing, and obtaining a modified solution with the mass percentage concentration of 6% of the modifier after mixing for later use.
Secondly, adding polyethylene granules or powder into a stirrer with a heating function, setting the rotating speed of the stirrer to be 100r/min and the temperature to be 70 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 0.1: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 20min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersing agent, wherein the graphene is oxidized graphene with the two-dimensional size smaller than 1um, the solvent is isopropanol, and the dispersing agent is a high molecular polymer containing benzene rings.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 1000nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 2% after dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: adding 30 mass percent of the mixture into a centrifugal mixer, centrifugally mixing at the temperature of 100 ℃ and the speed of 3000r/min, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating the graphene on the surface of the modified polyethylene, and mixing to obtain the composite granules.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 10
The embodiment provides a graphene polyethylene composite pipe, and a preparation method thereof comprises the following steps:
step 1: modified polyethylene
Firstly, a high molecular substance with amino groups is taken as a modifier, the high molecular substance with the amino groups is added into ethanol with the mass percentage concentration of 95% for mixing, and a modified solution with the mass percentage concentration of 5% of the modifier is obtained after mixing for later use.
Secondly, adding polyethylene granules or powder into a stirrer with a heating function, setting the rotating speed of the stirrer to be 400r/min and the temperature to be 100 ℃, adding the modifying liquid into the stirrer in a spraying mode under the condition to be mixed with polyethylene, wherein the mass ratio of the modifying agent to the polyethylene is 3: and 100, after the modified solution is completely added, continuously keeping the rotating speed and the temperature for 30min to dry the material, and drying to obtain the modified polyethylene with the surface having the cations.
Step 2: preparation of the Dispersion
Firstly, preparing graphene, a solvent and a dispersant, wherein the graphene is a graphene nanosheet with a two-dimensional size smaller than 1um, the solvent is an organic solvent, and the dispersant is a high-molecular polymer containing triple bonds.
And secondly, stirring and mixing the graphene, the solvent and the dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid in a shearing, homogenizing, sanding and ball milling mode to enable the two-dimensional size of the graphene to reach 800nm, and obtaining the graphene dispersion liquid with the mass percentage concentration of 2% after dispersion treatment.
And step 3: electrostatic self-assembly
Mixing modified polyethylene and graphene dispersion liquid according to the weight ratio of 100: adding 20 mass percent of the mixture into a centrifugal mixer, centrifugally mixing at the temperature of 60 ℃ and the speed of 1200r/min, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating the graphene on the surface of the modified polyethylene, and mixing to obtain the composite granules.
And 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
Example 11
The graphene polyethylene composite pipes described in the above embodiments 1 to 10 are subjected to performance detection, and the detection results are shown in table 1 below.
From the above, the product prepared by the invention has very excellent water pressure resistance, and compared with PE100 grade, the ring stiffness and the hydrostatic pressure resistance of the product are improved by more than 30%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (9)
1. A preparation method of a graphene polyethylene composite pipe is characterized by comprising the following steps:
step 1: modified polyethylene
Adding a modifier with cations into ethanol to form a modified solution, adding the modified solution into polyethylene under a stirring state, mixing, and drying to obtain modified polyethylene with cations on the surface;
step 2: preparation of the Dispersion
Stirring and mixing graphene, a solvent and a dispersing agent to form a graphene pre-dispersion liquid, dispersing the pre-dispersion liquid to enable the two-dimensional size of the graphene to reach 10nm-1000nm, and dispersing to obtain a graphene dispersion liquid;
and step 3: electrostatic self-assembly
Adding modified polyethylene and graphene dispersion liquid into a centrifugal mixer, carrying out centrifugal mixing at the temperature of 40-100 ℃, carrying out electrostatic self-assembly on the modified polyethylene and the graphene dispersion liquid in the mixing process, uniformly coating graphene on the surface of the modified polyethylene, and mixing to obtain composite granules;
and 4, step 4: pipe extrusion
And melting and extruding the composite granules to obtain the composite pipe.
2. The preparation method of the graphene polyethylene composite pipe material according to claim 1, characterized in that: the specific method of the step 1 comprises the following steps: adding polyethylene into a stirrer with a heating function, adding the modifying liquid into the stirrer in a spraying mode under the conditions that the rotating speed is 100-400r/min and the temperature is 60-100 ℃, mixing with the polyethylene, and continuously keeping the rotating speed and the temperature for 10-30min after the modifying liquid is completely added to obtain the modified polyethylene with the surface having cations.
3. The preparation method of the graphene polyethylene composite pipe material according to claim 1, characterized in that: in the step 1, the mass percentage concentration of the ethanol is 95%, the mass percentage concentration of the modifier in the modifying liquid is 1-10%, and the mass ratio of the modifier to the polyethylene is 0.1-3: 100.
4. the preparation method of the graphene polyethylene composite pipe material according to claim 1, characterized in that: in the step 1, the modifier is a cationic surfactant with long-chain alkyl or a small/high molecular substance with amino groups.
5. The preparation method of the graphene polyethylene composite pipe material according to claim 1, characterized in that: the cationic surfactant with long-chain alkyl is one or more of cetyl ammonium bromide, 3-aminopropyl trimethoxy silane, quaternary ammonium salt with alkyl, quaternary ammonium salt containing hetero atoms, quaternary ammonium salt containing benzene rings and quaternary ammonium salt containing heterocycles according to any proportion.
6. The preparation method of the graphene polyethylene composite pipe material according to claim 1, characterized in that: in the step 2, the graphene is graphene oxide or graphene nanosheets, the two-dimensional size of the graphene is less than 1um, the solvent is one or a plurality of water, an organic solvent and isopropanol which are mixed in any proportion, and the dispersant is a high-molecular polymer containing benzene rings, double bonds or triple bonds.
7. The preparation method of the graphene polyethylene composite pipe material according to claim 1, characterized in that: in the step 2, the mass percentage concentration of the graphene dispersion liquid is 0.01-2%.
8. The preparation method of the graphene polyethylene composite pipe material according to claim 1, characterized in that: in the step 2, the pre-dispersion liquid is subjected to dispersion treatment in a manner including, but not limited to, shearing, homogenizing, sanding and ball milling.
9. The preparation method of the graphene polyethylene composite pipe material according to claim 1, characterized in that: in the step 3, the mass ratio of the modified polyethylene to the graphene dispersion liquid is 100: 1-30, and the mixing rate is 400-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011341689.6A CN112457506A (en) | 2020-11-25 | 2020-11-25 | Preparation method of graphene-polyethylene composite pipe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011341689.6A CN112457506A (en) | 2020-11-25 | 2020-11-25 | Preparation method of graphene-polyethylene composite pipe |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112457506A true CN112457506A (en) | 2021-03-09 |
Family
ID=74808120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011341689.6A Pending CN112457506A (en) | 2020-11-25 | 2020-11-25 | Preparation method of graphene-polyethylene composite pipe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112457506A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999445A (en) * | 2021-10-20 | 2022-02-01 | 国网电力科学研究院有限公司 | Graphene/polyethylene composite material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130210955A1 (en) * | 2010-09-03 | 2013-08-15 | Nobuhiko Inui | Resin composite material and method for producing resin composite material |
| CN103333368A (en) * | 2013-07-19 | 2013-10-02 | 中物院成都科学技术发展中心 | Compound dispersing agent of carbon nanomaterial and method for preparing electric conduction polymeric composite thereof |
| CN104725695A (en) * | 2013-12-24 | 2015-06-24 | 唐山长虹塑料制品有限公司 | Ground source heat pump tube production technique and ground source heat pump tube |
| CN106366418A (en) * | 2016-09-12 | 2017-02-01 | 福州大学 | Method for modifying polyethylene film by loading nano-graphite onto graphene nanoribbon |
| CN106687512A (en) * | 2014-07-17 | 2017-05-17 | 凯诺斯私人有限公司 | Polymer resin composition and articles formed with the composition |
| CN107383518A (en) * | 2016-05-16 | 2017-11-24 | 中国石油天然气股份有限公司 | The preparation method of polyethylene-graphene complex |
| CN108779287A (en) * | 2016-01-15 | 2018-11-09 | 凯诺斯私人有限公司 | The method for preparing Polyethylene Nanocomposites |
| CN109608731A (en) * | 2017-11-16 | 2019-04-12 | 山东方大新材料科技有限公司 | A kind of graphene enhances mining polyethylene composition, particle, tubing and preparation method thereof |
| CN110591207A (en) * | 2019-10-28 | 2019-12-20 | 株洲时代新材料科技股份有限公司 | Ultrahigh molecular weight polyethylene/graphene oxide composite material and preparation method thereof |
-
2020
- 2020-11-25 CN CN202011341689.6A patent/CN112457506A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130210955A1 (en) * | 2010-09-03 | 2013-08-15 | Nobuhiko Inui | Resin composite material and method for producing resin composite material |
| CN103333368A (en) * | 2013-07-19 | 2013-10-02 | 中物院成都科学技术发展中心 | Compound dispersing agent of carbon nanomaterial and method for preparing electric conduction polymeric composite thereof |
| CN104725695A (en) * | 2013-12-24 | 2015-06-24 | 唐山长虹塑料制品有限公司 | Ground source heat pump tube production technique and ground source heat pump tube |
| CN106687512A (en) * | 2014-07-17 | 2017-05-17 | 凯诺斯私人有限公司 | Polymer resin composition and articles formed with the composition |
| CN108779287A (en) * | 2016-01-15 | 2018-11-09 | 凯诺斯私人有限公司 | The method for preparing Polyethylene Nanocomposites |
| CN107383518A (en) * | 2016-05-16 | 2017-11-24 | 中国石油天然气股份有限公司 | The preparation method of polyethylene-graphene complex |
| CN106366418A (en) * | 2016-09-12 | 2017-02-01 | 福州大学 | Method for modifying polyethylene film by loading nano-graphite onto graphene nanoribbon |
| CN109608731A (en) * | 2017-11-16 | 2019-04-12 | 山东方大新材料科技有限公司 | A kind of graphene enhances mining polyethylene composition, particle, tubing and preparation method thereof |
| CN110591207A (en) * | 2019-10-28 | 2019-12-20 | 株洲时代新材料科技股份有限公司 | Ultrahigh molecular weight polyethylene/graphene oxide composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 冉崇文，等: "石墨烯微片对管材专用聚乙烯性能的影响", 《合成树脂及塑料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999445A (en) * | 2021-10-20 | 2022-02-01 | 国网电力科学研究院有限公司 | Graphene/polyethylene composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103275524B (en) | Preparation method of graphene kaolin composite nanometer rubber fillers | |
| CN101781404B (en) | Method for preparing carbon nanotube static conductive coating on surface of EVA thin film | |
| CN107602987A (en) | The high molecular PTC composite and preparation method of a kind of graphene-containing and CNT | |
| WO2016041310A1 (en) | Waterproof and oxygen-insulation sealing film and preparation method and use thereof | |
| CN109206961A (en) | A kind of graphene conductive heat-conductive coating and preparation method thereof | |
| CN107353605B (en) | Multifunctional graphene/PET composite film and preparation method thereof | |
| CN101948612B (en) | Antistatic polyester and preparation method thereof | |
| CN104710661A (en) | carboxy terminated nitrile rubber/graphene nanocomposite and preparation method thereof | |
| CN109735064A (en) | A kind of conductive agglomerate and preparation method thereof | |
| CN108659457B (en) | Boron nitride coated sulfonated graphene-epoxy resin composite material and preparation method thereof | |
| WO2018045673A1 (en) | Method for modifying polyethylene film by loading nanographite onto graphene nanoribbon | |
| CN112457506A (en) | Preparation method of graphene-polyethylene composite pipe | |
| Wang et al. | A high-performance thermally conductive and electrically insulating silver@ siloxane/graphene/epoxy composites at low filler content: Fabrication, mechanism study of insulation and thermal conductivity enhancement | |
| CN106519390A (en) | Polyolefin graphene nanocomposite material, and preparation method thereof | |
| CN107069008A (en) | Silicon-carbon cathode material and preparation method thereof | |
| CN107815170A (en) | A kind of graphene coating masterbatch and preparation method | |
| CN110229473B (en) | PET (polyethylene terephthalate) nano composite material and preparation method thereof | |
| CN114031867A (en) | MXene-graphene-PVC composite material and preparation method thereof | |
| CN106752804B (en) | High temperature resistant, antistatic polyether ketone ketone powdery paints and preparation method thereof | |
| CN102850828A (en) | Active nano silica composition and preparation method thereof | |
| CN112391003A (en) | Special resin with antibacterial property for polyethylene pipe and preparation method thereof | |
| CN109321096A (en) | A kind of UV modified graphite alkene polymer and preparation method thereof | |
| CN112499622B (en) | Silicon dioxide and graphene composite powder material and preparation method and application thereof | |
| CN105482022B (en) | The method that in-situ suspension polymerization prepares EVA/ graphene composite materials | |
| CN112918030B (en) | Boron nitride film with plane orientation, preparation method thereof, boron nitride composite film containing boron nitride film, thermal interface material and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210309 |
|
| WD01 | Invention patent application deemed withdrawn after publication |