CN107163519B - High-strength and droplet-resistant graphene/PET composite board and preparation method thereof - Google Patents
High-strength and droplet-resistant graphene/PET composite board and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength molten drop resistant graphene/PET composite board and a preparation method thereof. The graphene/PET composite board is prepared by melting and extruding a graphene/PET nano composite material, wherein the graphene/PET nano composite material is obtained by adding fold-spherical graphene oxide and a catalyst into a PET precursor and carrying out in-situ polycondensation. 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 after a small amount of graphene is added, the anti-dripping property, the yield strength and the high-temperature yield strength of the composite board are all obviously improved. The preparation process is simple and effective, and the obtained composite material has excellent performance and can be used in the fields of building materials, refractory materials, heating kitchenware and the like.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a high-strength molten drop resistant graphene/PET composite board and a preparation method thereof.
Background
Polyethylene terephthalate (PET) has high mechanical strength, rigidity and hardness, good sliding property and wear resistance, good electrical insulation, very good creep resistance, dimensional stability (superior to POM) and physiological inertia (suitable for contacting with food). The weather resistance and the chemical resistance stability are good, the water absorption is low, and the paint is weak acid and organic solvent resistant, but is not hot water soaking resistant and alkali resistant. However, in the face of the rapid development of society, people put forward many new requirements on the mechanical property, thermal property and electrical property of PET, and 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 human society.
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 low cost performance of conventional reinforcing materials, and are not suitable for large-scale popularization.
Graphene is one of the most interesting new materials in the new century, and has a wide application prospect in many fields due to its ultrahigh specific surface area, excellent mechanical properties, high electrical conductivity, high thermal conductivity and high barrier property. In the field of composite materials, a small amount of graphene is added, so that multiple 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 composite board 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 composite board is characterized by comprising the following steps: uniformly mixing 100 parts by weight of graphene/PET nano composite material and 0-10 parts by weight of auxiliary agent, and performing melt extrusion to obtain the high-temperature-resistant and anti-dripping graphene/PET composite board.
Furthermore, the auxiliary agent is composed of one or more of antioxidant, inorganic filler, toughening agent and gloss improving auxiliary agent according to any proportion. The melt extrusion temperature is 230-260 ℃, the screw rotation speed is 30-90rpm, and the traction speed is 0.15-6 m/min.
Further, the graphene/PET nanocomposite material is prepared by 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 0.02 part by weight 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: (1) a small amount of folded spherical graphene oxide microspheres and a PET precursor are added for in-situ polymerization, so that the yield strength and the elastic modulus of the PET plate can be remarkably improved, and the yield strength under a high-temperature condition is also improved. The reason is that the added pleating-spherical graphene oxide microspheres can be gradually unfolded and dissociated into flaky 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, and the compatibility of the two is improved. The lower stacking greatly reduces the addition amount of graphene, so that the method has high cost performance. (2) The graphene oxide is added after esterification, so that the influence on the first esterification process is avoided. For the polymerization process, the introduction of the graphene oxide polymerization process has no obvious influence, so that the method is more reasonable in the actual production process, higher in efficiency and lower in cost. (3) The addition of the graphene reduces the dropping speed of the board during combustion, and improves the anti-dripping performance of the material. (4) The conductivity of the composite board is obviously improved under the condition of high addition amount, and the composite board can be used as an antistatic material.
Drawings
Fig. 1 is an SEM image of pleated spherical graphene oxide prepared by example 1 of the present invention.
Fig. 2 is a photograph of a graphene/PET composite prepared by example 1 of the present invention.
Detailed Description
The method for preparing the graphene/PET composite board 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 0.02 part by weight 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; (4) uniformly mixing 100 parts by weight of graphene/PET nano composite material and 0-10 parts by weight of auxiliary agent, and performing melt extrusion to obtain the high-temperature-resistant and anti-dripping graphene/PET composite board. The auxiliary agent is composed of one or more of antioxidant, inorganic filler, flexibilizer and gloss improving auxiliary agent according to any proportion. The melt extrusion temperature is 230-260 ℃, the screw rotation speed is 30-90rpm, and the traction speed is 0.15-6 m/min.
Heat distortion temperature was measured according to GB/T1634.1-2004. The tensile yield strength and modulus are measured according to GB/T1040.1-2006. The flame retardancy test was carried out according to the UL94 horizontal vertical burning test method.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part 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/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.2 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
Through the steps, the graphene/PET composite board is obtained, as shown in FIG. 1. The SEM image of the obtained pleated graphene oxide is shown in fig. 2. Specific properties of the composite sheet are shown in tables 1 and 2.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part 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/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.2 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
The graphene/PET composite board is obtained through the steps, and the specific properties are shown in tables 1 and 2.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 weight part of pleated spherical graphene oxide obtained in the step (1) and 0.018 weight part 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 revolutions per minute, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.2 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
The graphene/PET composite board is obtained through the steps, and the specific properties are shown in tables 1 and 2.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 weight part of pleated spherical graphene oxide obtained in the step (1) and 0.018 weight part 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 revolutions per minute, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.4 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
The graphene/PET composite board is obtained through the steps, and the specific properties are shown in tables 1 and 2.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass 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 0.018 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 revolutions per minute, 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.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.3 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
The graphene/PET composite board is obtained through the steps, and the specific properties are shown in tables 1 and 2.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 5.85 parts by mass of pleated spherical graphene oxide obtained in the step (1) and 0.018 part by mass 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 revolutions per minute, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET composite board.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.5 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
The graphene/PET composite board is obtained through the steps, and the specific properties are shown in tables 1 and 2.
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 tables 1 and 2.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part 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/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.2 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
The graphene/PET composite board is obtained through the steps, and the specific properties are shown in tables 1 and 2.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part 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/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.2 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
The graphene/PET composite board is obtained through the steps, and the specific properties are shown in tables 1 and 2.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (2) adding 0.117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part 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/min, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET nano composite material.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.2 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
The graphene/PET composite board is obtained through the steps, and the specific properties are shown in tables 1 and 2.
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 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 9.36 parts by mass of pleated spherical graphene oxide obtained in the step (1) and 0.018 part by mass 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 revolutions per minute, then heating to 285 ℃, vacuumizing, reacting until the system does not release heat, and performing water-cooling granulation to obtain the graphene/PET composite board.
(4) Uniformly mixing 100 parts by mass of the graphene/PET nano composite material and 0.2 part by mass of an antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 240 ℃, the screw speed was 70rpm, and the drawing speed was 4 m/min.
The graphene/PET composite board is obtained through the steps, and the specific properties are shown in tables 1 and 2.
TABLE 1 example specific parameters
TABLE 2 specific 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 examples 1, 2, 5, 6 and 5 shows that the addition amount of graphene oxide is increased, the mechanical property of the material is improved, the droplet velocity is greatly reduced, and the conductivity is greatly improved. After adding too much graphene oxide, although the flame retardancy and the electrical conductivity can be further improved, the mechanical properties of the material are reduced because too much graphene is stacked, which reduces the reinforcing effect and makes the material brittle (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 20-30 microns, and the carbon-oxygen ratio is 5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 0.0117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part 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 water-cooling and granulating to obtain the graphene/PET composite membrane.
(4) Uniformly mixing 100 parts by mass of graphene/PET nano composite material and 10 parts by mass of antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 230 ℃, the screw speed was 30rpm, and the drawing speed was 0.15 m/min.
The graphene/PET composite board obtained through the steps has good performance.
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 130 ℃, the size of a graphene oxide sheet is 20-30 microns, and the carbon-oxygen ratio is 5;
(2) fully mixing and stirring 100 parts by mass of terephthalic acid, 53 parts by mass of ethylene glycol and 0.02 part by mass of sodium acetate, and carrying out esterification reaction at 250 ℃ until no water is generated;
(3) and (3) adding 0.0117 mass part of pleated spherical graphene oxide obtained in the step (1) and 0.018 mass part 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 water-cooling and granulating to obtain the graphene/PET composite membrane.
(4) Uniformly mixing 100 parts by mass of graphene/PET nano composite material and 10 parts by mass of antioxidant, and carrying out melt extrusion to obtain the graphene/PET composite board. The extrusion temperature was 260 ℃, the screw speed was 90rpm, and the drawing speed was 6 m/min.
The graphene/PET composite board obtained through the steps has good performance.
Claims (8)
1. A preparation method of a high-strength and droplet-resistant graphene/PET composite board is characterized by comprising the following steps: uniformly mixing 100 parts by weight of graphene/PET nano composite material and 0-10 parts by weight of auxiliary agent, and performing melt extrusion to obtain a high-temperature-resistant and anti-dripping graphene/PET composite plate;
the graphene/PET nano composite material is prepared by 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 0.02 part by weight of sodium acetate at 250 parts by weightoC, 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 method according to claim 1, wherein the temperature of the atomization drying in the step (1) is 130-200%oC。
3. The method according to claim 1, wherein the stirring speed in the step (3) is 140 to 200 rpm.
4. 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.
5. 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.
6. 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.
7. The method according to claim 1, wherein the auxiliary agent is composed of one or more of an antioxidant, an inorganic filler, a toughening agent and a gloss improving auxiliary agent according to any proportion; the melt extrusion temperature is 230-260 ℃, the screw rotation speed is 30-90rpm, and the traction speed is 0.15-6 m/min.
8. The high-strength and droplet-resistant graphene/PET composite board obtained by the preparation method of claim 1 is characterized by being obtained by carrying out co-melt extrusion on 100 parts by mass of graphene/PET nano composite material and 0-10 parts by mass of auxiliary agent; the graphene/PET nano composite material consists of a single-layer graphene sheet and PET, wherein the surface of the graphene sheet is connected with PET molecules through a covalent bond.
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| BR112019027930-0A BR112019027930B1 (en) | 2017-06-26 | 2018-02-26 | METHOD FOR PREPARING A GRAPHENOPOLYESTER NANOCOMPOSITE MATERIAL |
| PCT/CN2018/077169 WO2019000985A1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method therefor |
| RU2020100048A RU2746113C1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and method of production thereof |
| 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 |
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| CN112225205B (en) * | 2020-09-09 | 2022-07-26 | 宁波益德新材料有限公司 | Preparation method of graphene and graphene/PET composite material |
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| CN105017511A (en) * | 2015-08-20 | 2015-11-04 | 浙江万凯新材料有限公司 | Preparation method of oxidized graphene modified PET (polyethylene terephthalate) material |
| CN105540573A (en) * | 2016-01-27 | 2016-05-04 | 浙江碳谷上希材料科技有限公司 | High-solubility multi-fold dry-state graphene oxide microsphere and preparation method thereof |
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| CN105017511A (en) * | 2015-08-20 | 2015-11-04 | 浙江万凯新材料有限公司 | Preparation method of oxidized graphene modified PET (polyethylene terephthalate) material |
| CN105540573A (en) * | 2016-01-27 | 2016-05-04 | 浙江碳谷上希材料科技有限公司 | High-solubility multi-fold dry-state graphene oxide microsphere and preparation method thereof |
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