CN107513162A - A kind of preparation method of graphene/nylon 6 nano-composite - Google Patents
A kind of preparation method of graphene/nylon 6 nano-composite Download PDFInfo
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention relates to a kind of preparation method of graphene/nylon 6 nano-composite, this method carries out in-situ polymerization using the spherical graphene oxide of pleat and caprolactam and obtains graphene/nylon 6 composite material.During caprolactam monomer open loop polycondensation, the spherical graphene oxide of pleat is progressively dissociated into single-layer graphene oxide piece, and forms covalence graft with the molecule of nylon 6, while heat-treats graphene oxide.The mechanical performance, resistance to elevated temperatures, resistance to UV aging of nylon 6 can be obviously improved by only adding the spherical graphene oxide of a small amount of pleat, graphene dispersiveness in polymeric matrix is good, dosage is few, and final products machinability is good, can carry out industrializing more tow high speed spinnings.In addition preparation technology involved in the present invention is easy and effective, is adapted to industrialized VK pipes polymerization unit, is modified without equipment is closed to existing nylon 6/poly, is a kind of production technology of the great market competitiveness.
Description
Technical field
The invention belongs to nylon composite materials field, and in particular to a kind of to prepare low graphene addition using situ aggregation method
The preparation method of graphene/nylon 6 nano-composite of amount.
Background technology
The two-dimension single layer stratified material that graphene is made up of carbon atom.The owned high intensity of graphene (130GPa),
High thermal conductivity (5000W m‐1K‐1), high conductivity (108S m‐1) and the characteristic such as good barrier properties for gases, it is a kind of preferable
Laminar nano filler.Nylon 6 (polyamide 6) is the product that yield is maximum and most widely used in nylon engineering plastic, and it is integrated
Performance is good, cost-effective.It can apply to auto industry, electrical equipment industry, machinery industry, textile industry and domestic life material
Deng numerous areas.
Therefore, the Nylon Nanocomposite that is obtained in the system of nylon body 6 of being dispersed in of graphene uniform can be carried significantly
Many performances of nylon 6 are risen, such as hot property, mechanical property, anti-flammability, electric conductivity and barrier property, are received so as to improve nylon
The added value of nano composite material, it is the important development direction of nylon 6 material now.
The combination property of graphene/nylon 6 composite material depends on dispersiveness of (1) graphene in polymeric matrix,
(2) caking property between graphene and nylon interface, and the performance of (3) graphene itself, such as lateral dimension, the number of plies and oxidation
Degree.Wherein dispersiveness of the graphene in polymeric matrix decides the dosage of graphene and adding for final composite
Work.Graphene is easily reunited, if disperseing bad composite, not only elongation at break is low, and cannot be used for high speed spinning, because
Spinneret is easily blocked for graphene aggregate.The method for preparing graphene/nylon 6 nano-composite at present is broadly divided into two
Kind：(1) mechanical blending method, this method are that the melt of nylon 6 and graphene are carried out into mechanical blending with extruder or banbury etc.,
Although the composite of gained can have been lifted in some mechanical performances, this secondary operation mode not only consumes energy height,
Polymer molecular chain, which can also be destroyed, causes partial properties to decline.In addition dispersiveness of this method graphene in polymeric matrix
It is poor, and bad adhesion between graphene and polymer interface so that graphene usage amount is big, and enhancing effect is limited；(2) it is in situ poly-
Legal, this method is that graphene just is added into polymerization system to obtain nylon 6 composite material in polymerization stage, this method
Key remains to be well dispersed into polymeric matrix in graphene after in polymerization terminating, otherwise the properties of composite
Lifting will have a greatly reduced quality.Although carrying out in-situ polymerization with graphene oxide or graphite oxide utilizes its abundant oxygenated functional group energy
Enough ensure dispersiveness of the graphene in nylon 6 but because graphene oxide or graphite oxide defect are more, self performance is not good enough, multiple
The performance boost space of condensation material is limited.If carrying out in-situ polymerization as additive using graphene or reduced graphene, due to lacking
Bad dispersibility of few functional group graphene in polymerized monomer, greatly affected the dispersiveness of graphene in the polymer.Increase
The addition of big graphene greatly affected the mechanical performance and spinnability of polymer.
In addition, that is reported so far prepares graphite using graphene oxide dispersion and caprolactam progress in-situ polymerization
The method of alkene/nylon 6 composite material is all based on the preparation technology of batch reactor, contains substantial amounts of water in polymerization system.
And industrial nylon 6 produces most production lines and carries out continuous polymerization using VK pipes, have very to the moisture content of polymerization system
High requirement, the more serious lifting for suppressing molecular weight of water content, even results in and is difficult to polymerize, this big rule to graphene/nylon 6
Mould prepare and its it is unfavorable.Therefore, it is necessary to which the graphene oxide powder that obtains in polymerization system to disperse carries out composite
Preparation.
The content of the invention
Present invention aims to overcome that prior art is insufficient, there is provided a kind of preparation of graphene/nylon 6 nano-composite
Method.
The present invention is achieved by the following technical solutions：A kind of preparation side of graphene/nylon 6 nano-composite
Method, carry out according to the following steps：
(1) the single-layer graphene oxide dispersion liquid that size is 1~50 micron is dried by atomization drying method, obtains pleat ball
Shape graphene oxide, its carbon-to-oxygen ratio are 2.5~5；
(2) the spherical graphene oxide of the pleat of 0.01-3.5 mass parts and 1-3 mass parts deionized water are added into 100 mass parts
Caprolactam melt in, at 80 DEG C at a high speed (300~500rpm) stir and evenly mix to form dispersion liquid；
(3) graphene/nylon 6 nano-composite is prepared in intermittent reaction equipment or VK pipes：
Batch reactor：
Under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-1MPa
Lower reaction 2-4 hours；Then 4-6 hours are reacted under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
VK is managed：
By the continuous polymerization in VK pipes of above-mentioned dispersion liquid, polymerization temperature is 260 DEG C, polymerization time 20h, polymer is melted
The water cooled granulation of body obtains graphene/nylon 6 nano-composite.
Further, the temperature of step (1) described atomization drying is 130~160 DEG C.
The beneficial effects of the present invention are：(1) ordinary graphite alkene powder is mostly the graphene-structured that height stacks, and is added poly-
Single-layer graphene can not be dispersed into after zoarium system, or even secondary stacking can occur, reduces the overall performance of material.The present invention is first
The spherical graphene oxide microballoon of pleat is prepared by atomization drying method, this pleat spherical structure greatly reduces graphene oxide sheet
Between stacking effect, and by the carbon-to-oxygen ratio and the spherical graphene oxide of graphene oxide size pleat of reasonable selection at oneself
It can progressively deploy in lactams melt, dissociate, while thermal reduction occurs and forms individual layer sheet graphene.In whole polymerization process
The molecule of nylon 6 progressively grafts on graphenic surface, improves both compatibilities, has been remained in the case of high addition excellent
Different mechanical performance (such as toughness and spinnability), and it is excellent largely to play the enhancing, barrier, uvioresistant of graphene etc.
Gesture, and there is extremely low percolation threshold.(2) high quality monolayer graphene oxide is used to carry out in situ gather for raw material and caprolactam
Close obtained graphene/nylon 6 composite material.Got a promotion compared to the pure product each side combination property of nylon 6, such as mechanicalness
Energy, resistance to elevated temperatures, resistance to UV aging etc.；There is no loss material toughness simultaneously, polymer molecular weight is controllable, will not be with stone
Black alkene addition increases and reduced.Graphene is both a kind of nucleator in polymeric matrix, and a kind of nanometer reinforcer,
The effect such as ultraviolet protection is also functioned to simultaneously.(3) graphene dispersiveness in polymeric matrix is good, and graphene film lateral dimension
Greatly, therefore graphene dosage is few (being less than 0.5%), and final products machinability is good, can carry out industrializing more tow high-speed spinnings
Silk.(4) whole preparation technology is easy and effective, is modified without equipment is closed to existing nylon 6/poly, is a kind of great market competition
The production technology of power.Due to avoiding the addition of water, VK pipes can be used to carry out serialization polymerization.
Brief description of the drawings
Fig. 1 is the spherical graphene oxide electron scanning micrograph of pleat.
Fig. 2 is graphene oxide X-ray photoelectron spectroscopic analysis (XPS) analysis result, modified graphite used in the present invention
Alkene carbon-to-oxygen ratio is controllable between being 2.5 to 6.
Fig. 3 is graphene/nylon 6 composite material master batch.
Fig. 4 is that the silk obtained by graphene/nylon 6 composite material master batch carries out more tow high speed spinnings is rolled up.
Embodiment
Embodiment 1：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and graphene oxide chip size is 0.3~5 micron, and average-size is 1 micron, and carbon-to-oxygen ratio 5, moisture content is less than
0.1%；
(2) the spherical graphene oxide of the pleat of 3.5 mass parts and 2 mass parts deionized waters are added in oneself of 100 mass parts
In acid amides melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
High speed spinning is carried out with the material, obtains silk volume as shown in Figure 4.Due to higher graphene addition, the silk
Uvioresistant performance with height, and there is extremely low percolation threshold.
The performance of gained graphene/nylon 6 nano-composite sees attached list 1.
Embodiment 2：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the size of graphene oxide sheet is 1~20 micron, and average-size is 10 microns, carbon-to-oxygen ratio 4.2, moisture content
Less than 0.1%；
(2) by acyl in oneself of the spherical graphene oxide of the pleat of 2 mass parts and 2 mass parts deionized waters, 100 mass parts of addition
In amine melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 1.
Embodiment 3：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the size of graphene oxide sheet is 1~40 micron, and average-size is 20 microns, carbon-to-oxygen ratio 3.9, moisture content
Less than 0.1%；
(2) the spherical graphene oxide of the pleat of 0.5 mass parts and 2 mass parts deionized waters are added in oneself of 100 mass parts
In acid amides melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 1.
Embodiment 4：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 150 DEG C, and the size of graphene oxide sheet is 20~50 microns, and average-size is 40 microns, carbon-to-oxygen ratio 3, moisture content
Less than 0.1%；
(2) the spherical graphene oxide of the pleat of 0.2 mass parts and 1.5 mass parts deionized waters are added into oneself of 100 mass parts
In lactams melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 1.
Embodiment 5：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 160 DEG C, and the average-size of graphene oxide sheet is 50 microns, and carbon-to-oxygen ratio 2.5, moisture content is less than 0.1%；
(2) the spherical graphene oxide of the pleat of 0.01 mass parts and 1 mass parts deionized water are added in oneself of 100 mass parts
In acid amides melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 1.
Embodiment 6：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the size of graphene oxide sheet is 1~20 micron, and average-size is 15 microns, carbon-to-oxygen ratio 3.9, moisture content
Less than 0.1%；
(2) the spherical graphene oxide of the pleat of 0.005 mass parts and 1 mass parts deionized water are added into oneself of 100 mass parts
In lactams melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 2.
Embodiment 7：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the size of graphene oxide sheet is 1~20 micron, and average-size is 15 microns, carbon-to-oxygen ratio 3.9, moisture content
Less than 0.1%；
(2) by acyl in oneself of the spherical graphene oxide of the pleat of 4 mass parts and 3 mass parts deionized waters, 100 mass parts of addition
In amine melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 2.
Embodiment 8：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the size of graphene oxide sheet is 0.1~0.8 micron, and average-size is 0.5 micron, carbon-to-oxygen ratio 3.9, is contained
Water rate is less than 0.1%；
(2) the spherical graphene oxide of the pleat of 0.2 mass parts and 1 mass parts deionized water are added in oneself of 100 mass parts
In acid amides melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 2.
Embodiment 9：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the size of graphene oxide sheet is 80~120 microns, and average-size is 100 microns, carbon-to-oxygen ratio 3.9, is contained
Water rate is less than 0.1%；
(2) the spherical graphene oxide of the pleat of 0.2 mass parts and 2 mass parts deionized waters are added in oneself of 100 mass parts
In acid amides melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 2.
Embodiment 10：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the size of graphene oxide sheet is 0.1~0.8 micron, and average-size is 15 microns, carbon-to-oxygen ratio 1.7, is contained
Water rate is less than 0.1%；
(2) the spherical graphene oxide of the pleat of 0.2 mass parts and 2 mass parts deionized waters are added in oneself of 100 mass parts
In acid amides melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 2.
Embodiment 11：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the size of graphene oxide sheet is 0.1~0.8 micron, and average-size is 15 microns, carbon-to-oxygen ratio 6.5, is contained
Water rate is less than 0.1%；
(2) the spherical graphene oxide of the pleat of 0.2 mass parts and 2 mass parts deionized waters are added in oneself of 100 mass parts
In acid amides melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, in 0.5-
Reacted 3 hours under 1MPa；Then react 4 hours under vacuo, obtain polymer melt；Finally make polymer melt is water cooled
Grain obtains graphene/nylon 6 nano-composite.
The performance of gained graphene/nylon 6 nano-composite sees attached list 2.
In order to which system illustrates that present invention gained graphene/nylon 6 nano-composite is every compared to pure nylon 6 material comprehensive
The lifting effect of performance, by the mechanical performance, resistance to elevated temperatures, ultraviolet aging resistance of composite obtained by above-mentioned 1-5 embodiments
Subordinate list 1 can be listed in be contrasted.Subordinate list 2 compared for using obtained by the graphene beyond graphene technical parameter of the present invention
The performance of graphene/nylon 6 nano-composite (embodiment 6-11) and the composite (embodiment 3) obtained by more excellent formula.
Subordinate list 1
Subordinate list 2
Embodiment 12：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the average-size of graphene oxide sheet is 5 microns, and carbon-to-oxygen ratio 3.9, moisture content is less than 0.1%；
(2) the spherical graphene oxide of the pleat of 0.2 mass parts and 2 mass parts deionized waters are added in oneself of 100 mass parts
In acid amides melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) it is 260 DEG C by the continuous polymerization in VK pipes of above-mentioned dispersion liquid, polymerization temperature, polymerization time 20h, will polymerize
The water cooled granulation of thing melt obtains graphene/nylon 6 nano-composite.
Gained graphene/nylon 6 composite material has good performance.
Embodiment 13：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat, be atomized
Temperature is 130 DEG C, and the average-size of graphene oxide sheet is 3 microns, and carbon-to-oxygen ratio 2.5, moisture content is less than 0.1%；
(2) by acyl in oneself of the spherical graphene oxide of the pleat of 1 mass parts and 2 mass parts deionized waters, 100 mass parts of addition
In amine melt, (400rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) it is 260 DEG C by the continuous polymerization in VK pipes of above-mentioned dispersion liquid, polymerization temperature, polymerization time 20h, will polymerize
The water cooled granulation of thing melt obtains graphene/nylon 6 nano-composite.
Gained graphene/nylon 6 composite material has good performance.
Claims (2)
1. a kind of preparation method of graphene/nylon 6 nano-composite, it is characterised in that carry out according to the following steps：
(1) the single-layer graphene oxide dispersion liquid that size is 1~50 micron is dried by atomization drying method, obtains the spherical oxygen of pleat
Graphite alkene, its carbon-to-oxygen ratio are 2.5~5；
(2) the spherical graphene oxide of the pleat of 0.01-3.5 mass parts and 1-3 mass parts deionized water are added into oneself of 100 mass parts
In lactams melt, (300~500rpm) stirs and evenly mixs to form dispersion liquid at a high speed at 80 DEG C；
(3) graphene/nylon 6 nano-composite is prepared in intermittent reaction equipment or VK pipes：
Batch reactor：
Under nitrogen protection, above-mentioned dispersion liquid is added into batch condensation polymerization reactor, and is warming up to 250-270 DEG C, it is anti-under 0.5-1MPa
Answer 2-4 hours；Then 4-6 hours are reacted under vacuo, obtain polymer melt；Finally it is granulated polymer melt is water cooled
To graphene/nylon 6 nano-composite.
VK is managed：
By the continuous polymerization in VK pipes of above-mentioned dispersion liquid, polymerization temperature is 260 DEG C, polymerization time 20h, polymer melt is passed through
Water cooling is granulated to obtain graphene/nylon 6 nano-composite.
2. preparation method according to claim 1, it is characterised in that the temperature of step (1) described atomization drying be 130~
160℃。
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710718369.XA CN107513162A (en) | 2017-08-21 | 2017-08-21 | A kind of preparation method of graphene/nylon 6 nano-composite |
| RU2020100048A RU2746113C1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and method of production thereof |
| PCT/CN2018/077169 WO2019000985A1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method therefor |
| KR1020207002385A KR102284847B1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and its manufacturing method |
| JP2019571324A JP6963040B2 (en) | 2017-06-26 | 2018-02-26 | Method for manufacturing graphene composite material |
| EP18822649.2A EP3626758B1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method therefor |
| BR112019027930-0A BR112019027930B1 (en) | 2017-06-26 | 2018-02-26 | METHOD FOR PREPARING A GRAPHENOPOLYESTER NANOCOMPOSITE MATERIAL |
| US16/626,546 US11149129B2 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method thereof |
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| CN112920415B (en) * | 2021-01-11 | 2022-05-24 | 华南理工大学 | Amidated graphene/nylon 6 nanocomposite and preparation method thereof |
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