CN107325268B - graphene/PET (polyethylene terephthalate) nano composite material and preparation method thereof - Google Patents
graphene/PET (polyethylene terephthalate) nano composite material and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention discloses a graphene/PET nano composite material and a preparation method thereof, wherein pleated spherical graphene oxide and a catalyst are added into a PET precursor, the pleated spherical graphene oxide is highly dispersed and gradually dissociated into single-layer graphene oxide sheets while a polycondensation reaction is carried out, partial esterified molecules can react with hydroxyl and carboxyl on the surfaces of the graphene oxide sheets to form chemical bonds, and meanwhile, the graphene oxide is subjected to thermal reduction, so that the composite material consisting of PET and the graphene sheets with the PET grafted on the surfaces is finally obtained. The method avoids the stacking of the graphene oxide in the esterification stage, greatly saves the cost and improves the production efficiency. The obtained graphene has good dispersibility in a polymer matrix, and the formation of a covalent bond between the two materials effectively improves the mechanical property, the conductivity and other properties of the system. The preparation process is simple and effective, the cost can be effectively saved, and the obtained composite material has excellent performance and can be used for preparing high-performance polyester fabrics.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a graphene/PET nano composite material and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is an important polymer material, and occupies a very large proportion in daily life of people, such as disposable water bottles, packaging materials, automobile plastics and the like, and PET is spun to obtain polyester commonly used in clothes, so that PET is widely used in our lives. If the performance of PET can be further improved or new performance is given, the application range of PET can be further widened, and more convenience can be brought to the human society. In recent years, researchers have upgraded the performance of PET by means of controlling the molecular structure of PET, carrying out copolymerization, introducing reinforcing phases for compounding, designing microstructures such as islands, and controlling crystallization behavior, and have attracted attention.
The introduction of the reinforcing material is a method which can realize rapid large-scale production and high cost performance, and the conventional reinforcing material comprises a metal material (nano wires and nano particles), an inorganic filler (montmorillonite, titanium dioxide, silicon dioxide, boron nitride and the like) and a carbon material (carbon black, graphite and the like). The conventional reinforcing material has two defects, on one hand, a satisfactory effect can be obtained only by needing a very high addition amount, but the high addition amount is accompanied with the reduction of other performances, so that the comprehensive improvement of the performances is difficult to realize, and on the other hand, the reinforcing effect is often single and cannot improve a plurality of performances simultaneously. These problems lead to unsatisfactory performance-to-cost ratios of conventional reinforcing materials.
Graphene is a two-dimensional material with atomic thickness, and has ultrahigh specific surface area, excellent mechanical properties, high electrical conductivity, high thermal conductivity and high barrier property. And a small amount of graphene is added, so that various properties of the material can be improved, and the material has ultrahigh cost performance, so that the material is widely researched in the aspect of composite materials. However, graphene is easy to agglomerate, and a graphite stacking structure is formed again, so that the reinforcing effect is reduced. Although the dispersion of graphene and the reduction of stacking of graphene can be promoted by adding a dispersant and performing a surface modification, these methods increase the cost of graphene and introduce new components. Patent 201510514154.7 "preparation method of graphene oxide modified PET material" adopts adding graphene oxide into graphene oxide aqueous solution before esterification, on one hand, the addition of water will affect esterification and polycondensation, and on the other hand, graphene oxide is reduced in the esterification stage, which may result in stacking and performance reduction. Patent 201280033203, X polyethylene terephthalate-graphene nanocomposite adds graphene nanosheets to a PET polymerization system, the addition amount of multi-layer graphene is high (2-15%), and due to the absence of functional groups, graphene can be stacked secondarily in the polymerization process to form incompatible defect points. Patent 201610111707.9 "PET-based graphene composite material, its preparation method and aerostat" firstly modifies graphene oxide with ethylene glycol, then esterifies or transesterifies with PET monomer, and finally polycondenses to obtain the composite material, although the compatibility of graphene and PET polymerization system is improved by modification, and the graphene and PET are covalently grafted, in the esterification process, graphene oxide still inevitably stacks, and the preparation process is complex, the cost of the whole production is high, and it is not suitable for actual production.
Disclosure of Invention
The invention aims to provide a graphene/PET nano composite material and a preparation method thereof aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a preparation method of a graphene/PET nano composite material is characterized by comprising the following steps:
(1) drying the single-layer graphene oxide dispersion liquid with the size of 1-50 microns by an atomization drying method to obtain folded spherical graphene oxide with the carbon-oxygen ratio of 2.5-5;
(2) fully mixing and stirring 100 parts by weight of terephthalic acid, 48-67 parts by weight of ethylene glycol and 0.02g of sodium acetate, and carrying out esterification reaction at 250 ℃;
(3) and (3) adding 0.0117-5.85 parts by weight of pleated spherical graphene oxide obtained in the step (1) and 0.018 parts by weight of catalyst into the esterification product obtained in the step (2), keeping the temperature, stirring for 1-3 hours, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
Further, the atomization drying temperature in the step (1) is 130-200 ℃.
Further, the stirring speed in the step (3) is 140-200 r/min.
Further, the catalyst in the step (3) is an antimony-based catalyst, and comprises antimony oxide, inorganic salt and organic compound.
Further, the catalyst in the step (3) is a titanium-based catalyst, and comprises titanium oxide, inorganic salt and organic compound.
Further, the catalyst in the step (3) is a germanium-based catalyst, and comprises germanium oxide, inorganic salt and organic compound.
The invention has the beneficial effects that: according to the preparation method, firstly, the fold-spherical graphene oxide microspheres are prepared by using an atomization drying method, the fold-spherical graphene oxide microspheres can be gradually unfolded and dissociated into flake-shaped graphene oxide in the esterified PET oligomer through reasonably selecting the carbon-oxygen ratio and the size of the graphene oxide, and hydroxyl and carboxyl on the surface of the graphene oxide react with PET molecules in a system in the PET polymerization process, so that a PET molecular chain is grafted on the surface of the graphene, the compatibility of the PET molecular chain and the graphene oxide is improved, and the improvement of the mechanical property, the conductivity and other properties is facilitated. Add the oxidation graphite alkene after esterifying, avoided the influence to first step esterification process, it is more reasonable in actual production process, efficiency is higher, and the cost is lower, has also avoided oxidation graphite alkene to take place to pile up at the esterification stage simultaneously and has formed the aggregate. As for the whole PET polymerization, no substance is introduced except the fold-spherical graphene oxide, and the dosages of terephthalic acid, ethylene glycol, esterification catalyst and polycondensation catalyst are all according to the pure PET polymerization process, so that the influence of the introduction of the graphene on the process and equipment is reduced to the maximum extent, and the method has wide application prospect. The obtained graphene/PET composite material has excellent mechanical property and conductivity, and can be used for preparing functionalized polyester fibers.
Drawings
Fig. 1 is a photograph of a graphene/PET nanocomposite prepared by example 1 of the present invention.
Fig. 2 is an SEM image of pleated spherical graphene oxide prepared by example 1 of the present invention.
Detailed Description
The method for preparing the graphene/PET nano composite material comprises the following steps:
(1) and drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain the folded spherical graphene oxide. The atomization drying temperature is 130-200 ℃. The folded spherical graphene oxide is composed of single-layer folded graphene oxide sheets, the size of each graphene oxide sheet is 1-50 micrometers, and the carbon-oxygen ratio is 2.5-5; (2) fully mixing and stirring 100 parts by weight of terephthalic acid, 48-67 parts by weight of ethylene glycol and 0.02g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated; (3) and (3) adding 0.0117-5.85 parts by weight of pleated spherical graphene oxide obtained in the step (1) and 0.018 parts by weight of catalyst into the esterification product obtained in the step (2), keeping the temperature, stirring for 1-3 hours, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material. The stirring speed is 140-200 rpm. The catalyst is an antimony catalyst, and comprises antimony oxide, inorganic salt and organic compound. The catalyst is a titanium catalyst and comprises antimony oxide, inorganic salt and organic compounds. The catalyst is an antimony catalyst and comprises germanium oxide, inorganic salt and organic compounds.
The present invention is described in detail by the following embodiments, which are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential changes and modifications made by the person skilled in the art according to the above disclosure are within the scope of the present invention.
Example 1:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 1-3 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 1000g of phthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 1.17g of fold-spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and is shown in figure 1. The SEM image of the obtained pleated graphene oxide is shown in fig. 2. Specific properties of the composite material are shown in table 1.
Example 2:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 10-15 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of ethylene glycol, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 1.17g of fold-spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and the specific properties are shown in Table 1.
Example 3:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 40-45 micrometers, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 1.17 parts by weight of pleated spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and the specific properties are shown in Table 1.
Example 4:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 160 ℃, the size of graphene oxide sheets is 10-15 microns, and the carbon-oxygen ratio is 5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 1.17g of fold-spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and the specific properties are shown in Table 1.
Example 5:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 10-15 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 11.7g of pleated spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and the specific properties are shown in Table 1.
Example 6:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 10-15 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 58.5g of pleated spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and the specific properties are shown in Table 1.
Comparative example 1:
PET was prepared according to the method of example 1, except that no pleated spherical graphene oxide was added during the preparation. The properties are shown in Table 1.
Comparative example 2:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 0.3-0.7 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 1.17g of fold-spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and the specific properties are shown in Table 1.
Comparative example 3:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 70-80 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 1.17g of fold-spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and the specific properties are shown in Table 1.
Comparative example 4:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 220 ℃, the size of graphene oxide sheets is 10-15 microns, and the carbon-oxygen ratio is 10;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 1.17 parts by weight of pleated spherical graphene oxide obtained in the step (1) and 0.18 part by weight of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and the specific properties are shown in Table 1.
Comparative example 5:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 130 ℃, the size of graphene oxide sheets is 10-15 microns, and the carbon-oxygen ratio is 2.5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 93.6g of pleating-spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 2 hours at the stirring speed of 160 r/m, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
The graphene/PET nanocomposite is obtained through the steps, and the specific properties are shown in Table 1.
TABLE 1 specific parameters and Properties of the examples
Analysis of comparative example 1, comparative example 2, example 1, example 2, example 3 and comparative example 3 shows that selecting an appropriate size range of graphene oxide results in a composite material with optimal performance, while maintaining the carbon to oxygen ratio and the amount of graphene oxide added. The graphene oxide of comparative example 2 is too small in size and cannot be used as an effective reinforcing material per se, while the graphene oxide of comparative example 3 is too large in size and cannot be effectively unfolded into sheet-shaped graphene oxide after being added into a polymerization system, and only can be used as a pleated spherical filler to reinforce a composite material, so that the tensile strength and modulus increase is small, and the elongation at break is slightly reduced. And in the size range of 1-50 microns, the graphene oxide can more effectively play a role in enhancing along with the increase of the size.
Analysis of comparative examples 1, 2, 4 and 4 shows that the carbon-oxygen ratio is increased, the composite material has better performance, because the carbon-oxygen ratio is increased, the graphene has fewer defects and has better performance, and the composite material has better performance. However, the carbon-oxygen ratio cannot be too high, otherwise, the bonding force between graphene oxide sheets is too strong, the graphene oxide sheets do not spread during polymerization, and the elongation at break cannot be effectively enhanced, even greatly reduced (comparative example 4).
Analysis on comparative example 1, example 2, example 5, example 6, and comparative example 5 shows that the addition amount of graphene oxide is increased, the mechanical properties of the material are improved, and the conductivity is greatly improved. After adding too much graphene oxide, although the conductivity could be further improved, the mechanical properties of the material were reduced because too much graphene was stacked, reducing the reinforcing effect (comparative example 5).
Example 7:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 200 ℃, the size of graphene oxide sheets is 40-50 microns, and the carbon-oxygen ratio is 5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 58.5g of pleated spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 3 hours at the stirring speed of 140 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material. Through testing, the obtained graphene/PET nano composite material has good mechanical property and electrical property.
Example 8:
(1) drying the single-layer graphene oxide dispersion liquid by an atomization drying method to obtain graphene oxide microspheres, wherein the atomization temperature is 200 ℃, the size of graphene oxide sheets is 40-50 microns, and the carbon-oxygen ratio is 5;
(2) fully mixing and stirring 1000g of terephthalic acid, 530g of ethylene glycol and 0.2g of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 0.117g of pleated spherical graphene oxide obtained in the step (1) and 0.18g of ethylene glycol antimony into the esterification product obtained in the step (2), keeping the temperature and stirring for 1h at the stirring speed of 200 r/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material. Through testing, the obtained graphene/PET nano composite material has good mechanical property and electrical property.
Claims (7)
1. A preparation method of a graphene/PET nano composite material is characterized by comprising the following steps:
(1) drying the single-layer graphene oxide dispersion liquid with the size of 1-50 microns by an atomization drying method to obtain folded spherical graphene oxide with the carbon-oxygen ratio of 2.5-5;
(2) 100 parts by weight ofFully mixing and stirring terephthalic acid, 48-67 parts by weight of ethylene glycol and 0.02 part by weight of sodium acetate at 250%oC, carrying out esterification reaction;
(3) adding 0.0117-5.85 parts by weight of pleated graphene oxide obtained in the step (1) and 0.018 part by weight of catalyst into the esterification product obtained in the step (2), keeping the temperature, stirring for 1-3 hours, and then heating to 285 deg.CoAnd C, vacuumizing, reacting until the system does not release heat, and performing water cooling and grain cutting to obtain the graphene/PET nano composite material.
2. The graphene/PET nanocomposite material prepared by the method according to claim 1, which consists of a single-layer graphene sheet and PET, wherein the surface of the graphene sheet is connected with PET molecules through covalent bonds.
3. The method according to claim 1, wherein the temperature of the atomization drying in the step (1) is 130-200%oC。
4. The method according to claim 1, wherein the stirring speed in the step (3) is 140 to 200 rpm.
5. The method according to claim 1, wherein the catalyst in the step (3) is an antimony-based catalyst comprising antimony oxide, inorganic salt and organic compound.
6. The method according to claim 1, wherein the catalyst in the step (3) is a titanium-based catalyst comprising an oxide of titanium, an inorganic salt and an organic compound.
7. The method according to claim 1, wherein the catalyst in the step (3) is a germanium-based catalyst comprising an oxide of germanium, an inorganic salt and an organic compound.
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CN201710494501.3A CN107325268B (en) | 2017-06-26 | 2017-06-26 | graphene/PET (polyethylene terephthalate) nano composite material and preparation method thereof |
KR1020207002385A KR102284847B1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and its manufacturing method |
RU2020100048A RU2746113C1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and method of production thereof |
EP18822649.2A EP3626758B1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method therefor |
JP2019571324A JP6963040B2 (en) | 2017-06-26 | 2018-02-26 | Method for manufacturing graphene composite material |
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 |
PCT/CN2018/077169 WO2019000985A1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method therefor |
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CN108641314A (en) * | 2018-04-11 | 2018-10-12 | 杭州牛墨科技有限公司 | One kind is based on few layer graphene heat conduction functional graphene/PET composite membranes and preparation method thereof |
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