WO2017148198A1 - Pet-based graphene composite material and preparation method therefor, and aerostat - Google Patents

Pet-based graphene composite material and preparation method therefor, and aerostat Download PDF

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Publication number
WO2017148198A1
WO2017148198A1 PCT/CN2016/109113 CN2016109113W WO2017148198A1 WO 2017148198 A1 WO2017148198 A1 WO 2017148198A1 CN 2016109113 W CN2016109113 W CN 2016109113W WO 2017148198 A1 WO2017148198 A1 WO 2017148198A1
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ethylene glycol
pet
graphene oxide
preparation
composite material
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PCT/CN2016/109113
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French (fr)
Chinese (zh)
Inventor
刘若鹏
赵治亚
李雪
冯玉林
石玉元
刘列
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洛阳尖端技术研究院
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Publication of WO2017148198A1 publication Critical patent/WO2017148198A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64B—LIGHTER-THAN AIR AIRCRAFT
    • B64B1/00—Lighter-than-air aircraft
    • B64B1/06—Rigid airships; Semi-rigid airships
    • B64B1/14—Outer covering
    • 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
    • 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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • PET Polyethylene terephthalate
  • Graphite thin is a two-dimensional sheet-like material composed of a single layer of sp2 hybridized carbon atoms. Its special structure determines its peculiar electrical properties, excellent physical and mechanical properties, thermal properties and gases. Barrier performance is an ideal filler for electromagnetic shielding, antistatic, high strength and gas barrier polymer composites, and has broad application potential in the preparation of lightweight, low cost, high performance composite materials.
  • Graphene is the most mechanically strong material in the world.
  • the two-dimensional sheet-like defect-free graphene has impermeable properties to gas molecules. When graphene is uniformly dispersed in the polymer matrix, it can not only greatly increase the polymerization.
  • the strength of the material can increase the length of the gas diffusion path, reduce the gas permeability of the polymer material, and improve the gas barrier properties of the polymer material.
  • the interaction with the polymer is weak, which affects its various excellent properties. Therefore, the dispersion of graphene is the key to preparing the polymer-based graphene composite. solved problem.
  • a method for preparing a PET-based graphene nanocomposite is mainly through a melt blending method into a surface-modified graphene functional material.
  • Chinese Patent Application No. 201210549244.6 discloses the preparation of graphene-modified PET material by melt blending of amino graphene and PET; the Chinese patent application No. 2012800332 03.X discloses the use of graphene nanoparticles. The material was melt blended with PET chips to prepare a graphene-containing PET masterbatch.
  • the main object of the present invention is to provide a PET-based graphene composite material, a preparation method thereof and an aerostat to solve the problems in the prior art.
  • the dispersion of graphene oxide in a PET-based graphene composite material is poor. The problem.
  • a method for preparing a PET-based graphene composite material comprising: Step S1, ethylene glycol-modified graphene oxide and PET monomer
  • the esterification reaction or the transesterification reaction is carried out to obtain a primary product
  • the PET monomer is terephthalic acid and/or dimethyl terephthalate
  • step S2 the primary product is subjected to a polycondensation reaction to obtain a PET-based graphene composite material.
  • the above PET monomer is terephthalic acid
  • step S1 is carried out in a nitrogen or inert gas atmosphere and comprises: ethylene glycol-modified graphene oxide and terephthalic acid at 220 to 250.
  • the esterification reaction is carried out at a temperature of C and a pressure of 0 to 0.4 MPa to obtain an initial product, and the esterification reaction is continued for 2.5 to 3.5 hours.
  • the catalyst used for the esterification reaction is tetrapropylzirconium, antimony trioxide or lithium hydroxide. .
  • the weight percentage of the graphene oxide to the terephthalic acid in the ethylene glycol-modified graphene oxide is 0.5 to 5% ; the ethylene glycol modified graphene oxide in the ethylene glycol and the terephthalic acid
  • the above PET monomer is dimethyl terephthalate
  • step S1 is performed in a nitrogen or inert gas atmosphere and includes: modifying ethylene glycol-modified graphene oxide with dimethyl terephthalate 220 ⁇ 250.
  • the transesterification reaction is carried out at a temperature of 0 to 0.4 MPa to obtain a primary product, and the transesterification reaction is continued for 2.5 to 3.5 hours.
  • the catalyst used for the transesterification reaction is tetrabutyl titanate, magnesium acetate or titanium dioxide.
  • step S2 comprises: performing a polycondensation reaction of the primary product by a catalyst at a pressure of 260 to 280 ° C and a temperature of 0 to 600 Pa to obtain a PET-based graphene composite material.
  • step S2 includes: using a catalyst at a pressure of 265 to 275 ° C and a pressure of 100 to 600 Pa
  • the prepolymerization reaction is carried out for 30 to 90 minutes to obtain a prepolymerized product.
  • the prepolymerized product is subjected to a polycondensation reaction for 90 to 150 minutes to obtain a PET-based graphene composite. material.
  • the above catalyst is ethylene glycol ruthenium or antimony trioxide.
  • the above preparation method further includes a preparation process of ethylene glycol-modified graphene oxide, and the preparation process comprises the following steps: Step A: dissolving the stabilizer in ethylene glycol to form an ethylene glycol solution; Step B, The diol solution is mixed with graphene oxide to form ethylene glycol modified graphene oxide.
  • the power is 300-1000 W ultrasonic treatment for 0.5 ⁇ 2 h, so that the graphene oxide is dispersed in the ethylene glycol solution to form ethylene glycol-modified graphene oxide.
  • the graphene oxide has a peeling thickness of 0.5 to 6 nm and a length of 10 to 100 ⁇ m.
  • the weight percentage of the above stabilizer relative to the PET monomer is 0.3 to 0.7%, and the stabilizer is N-methylpyrrolidone or polyvinylpyrrolidone.
  • a PET-based graphene composite material prepared by the above-described preparation method, and a tensile strength of a PET-based graphene composite material of 7500
  • helium gas transmission rate 800 ⁇ 950ml/m2.day.0.1MPa.
  • an aerostat having a skin material, the skin material comprising a gas barrier layer, and the material forming the gas barrier layer comprises the above-described PET-based graphene Composite material.
  • the skin material comprises a weathering layer, a fiber layer and a gas barrier layer which are sequentially disposed, or a weathering layer, a gas barrier layer and a fiber layer which are sequentially disposed.
  • a PET-based graphene composite is provided.
  • the preparation method of the material comprises the following steps: Step S1, esterifying or transesterifying the ethylene glycol-modified graphene oxide with the PET monomer to obtain a primary product, and the PET monomer is terephthalic acid and/or Dimethyl phthalate; Step S2 , the primary product is subjected to a polycondensation reaction to obtain a PET-based graphene composite material.
  • the PET monomer is terephthalic acid
  • the step S1 is performed in a nitrogen or inert gas atmosphere and comprises: modifying ethylene glycol with graphene oxide and terephthalic acid
  • the esterification reaction is carried out at a temperature of 220 to 250 ° C and a pressure of 0 0.4 MPa to obtain an initial product, preferably an esterification reaction is carried out for 2.5 to 3.5 hours, and the catalyst used for the esterification reaction is tetrapropylzirconium or antimony trioxide or Lithium hydroxide.
  • ethylene glycol is esterified with terephthalic acid to form a basic unit of PET, in which graphene oxide is dispersed together with ethylene glycol into the basic unit of PET; nitrogen or inert gas atmosphere It is possible to effectively prevent the active group such as the hydroxyl group of the graphene oxide from being oxidized under the above reaction conditions.
  • the weight percentage of graphene oxide to ethylene terephthalate in the ethylene glycol modified graphene oxide is 0.5 to 5% ; ethylene glycol modified oxidation
  • the graphene oxide in the graphene oxide is incorporated into the product as much as possible to improve the dispersibility of the graphene oxide in the final PET-based graphene composite.
  • the PET monomer is dimethyl terephthalate
  • step S1 The reaction is carried out in a nitrogen or inert gas atmosphere and comprises: transesterifying the ethylene glycol modified graphene oxide with dimethyl terephthalate at a temperature of 220 to 250 ° C and a pressure of 0 to 0.4 MPa.
  • the initial product preferably has a transesterification reaction for 2.5 to 3.5 hours, and the catalyst used for the transesterification reaction is tetrabutyl titanate, magnesium acetate or titanium dioxide.
  • ethylene glycol is transesterified with terephthalic acid to form a basic unit of PET in which graphene oxide is dispersed together with ethylene glycol into the basic unit of PET.
  • the weight percentage of graphene oxide relative to dimethyl terephthalate in the ethylene glycol modified graphene oxide is 0.5 to 5% ;
  • the step S2 includes: using a catalyst to carry out a polycondensation reaction of the primary product at a pressure of 260 to 280 ° C and a temperature of 0 to 600 Pa to obtain a PET-based graphene composite. material.
  • the initial product is in a molten state, and the polycondensation is smoothly carried out by using a vacuum environment of 0 to 600 Pa; if the temperature is lower than 260 ° C, the reaction rate is slow, which is disadvantageous for increasing the reaction rate; if the temperature is higher than 280 ° C
  • the formed product may undergo thermal decomposition and reduce the yield of the final product.
  • T-based graphene composite uses a catalyst to increase the reaction rate, and the polycondensation reaction is divided into two processes of prepolymerization and polycondensation by controlling the reaction conditions, thereby improving the dispersibility of graphene in the PET-based graphene composite material, and optimizing on the other hand.
  • the strength properties of the obtained PET-based graphene composite material is not limited to, but not limited to, but not limited to, but not limited to increase the reaction rate, and the polycondensation reaction is divided into two processes of prepolymerization and polycondensation by controlling the reaction conditions, thereby improving the dispersibility of graphene in the PET-based graphene composite material, and optimizing on the other hand.
  • the strength properties of the obtained PET-based graphene composite material uses a catalyst to increase the reaction rate, and the polycondensation reaction is divided into two processes of prepolymerization and polycondensation by controlling the reaction conditions, thereby improving the dispersibility of graphene in the PET-based graphen
  • Catalysts useful in the present application include, but are not limited to, ruthenium-based catalysts, ruthenium-based catalysts, and titanium-based catalysts.
  • the above catalysts are ethylene glycol ruthenium or antimony trioxide.
  • the ethylene glycol modified graphene oxide used in the present application is on the one hand to utilize ethylene glycol and PE therein.
  • T monomer reacts, on the other hand, ethylene oxide is modified by graphene oxide to increase its content in organic solvents. Solubility, improving its dispersibility in PET-based graphene composite materials, therefore, ethylene glycol-modified graphene oxide in the prior art can be applied to the present application, and specific synthesis conditions thereof can be based on the technical solutions of the present application.
  • the preparation method further includes a preparation process of the ethylene glycol modified graphene oxide, and the preparation process comprises the following steps: Step A The stabilizer is dissolved in ethylene glycol to form an ethylene glycol solution; in step B, the ethylene glycol solution is mixed with graphene oxide to form ethylene glycol-modified graphene oxide.
  • a stabilizer ensures the dispersibility of graphene oxide in ethylene glycol, and the stabilizer can improve the thermal stability of the obtained PET-based graphene composite in the next polycondensation reaction.
  • step B is performed by using a power of 300 to 1000 W for 0.5 to 2 h so that the graphene oxide is dispersed in the ethylene glycol solution to form B. Glycol modified graphene oxide.
  • the graphene oxide has a peeling thickness of 0.5 to 6 nm and a length of 10 to 100 ⁇ m.
  • the graphene oxide having the above characteristics is mixed with ethylene glycol and has better dispersibility in ethylene glycol.
  • the weight percentage of the stabilizer to the PET monomer is 0.3 to 0.7%, and further preferably the stabilizer is N-methylpyrrolidone or polyvinylpyrrolidone.
  • a PET-based graphene composite material a PET-based graphene composite material prepared by the above preparation method, and a tensile strength of a PET-based graphene composite material are provided. It is 7500 ⁇ 12500MPa, and the helium permeability is 800 ⁇ 950ml/m2.day.0.1MPa.
  • the tensile strength of the PET-based graphene composite material obtained by the preparation method of the present application and the helium gas barrier ratio are significantly improved, and thus can be applied to various PET films, fibers and the like.
  • an aerostat is provided, the aerostat having a skin material
  • the skin material comprises a gas barrier layer
  • the material forming the gas barrier layer comprises the above-mentioned PET-based graphene composite material. Since the mechanical strength and the helium barrier property of the PET-based graphene composite material formed by the present application are significantly improved, the requirements for the PET products of the current aerostats can be satisfied.
  • the skin material includes a weathering layer, a fiber layer, and a gas barrier layer which are sequentially disposed, or includes a weathering layer, a gas barrier layer, and a fiber layer which are sequentially disposed.
  • the PET-based graphene composite material of the present application can be applied to the above gas barrier layer, for example, by stretching it into a film and then aluminizing to form a gas barrier layer, because of its excellent mechanical strength. Degree and resistance, so the layer can have a significant resistance even after enthalpy.
  • PTA terephthalic acid
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.4 MPa.
  • the polymerization vessel was heated to 220 ° C for esterification reaction for 3.5 hours, and the water produced by the reaction was collected to the theoretical volume. The esterification reaction is completed to obtain a preliminary product.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite. Discharge and slice to get 700g The PET-based graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 4 MPa, and the pressure in the polymerization vessel was increased to 220 ° C for esterification reaction for 2.5 hours, and the amount of water produced by the reaction was collected to the theoretical volume.
  • the esterification reaction is completed to obtain a preliminary product.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite. Discharge and slice to get 700g The PET-based graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite. Discharge and slice to get 700g PET The graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 260 ⁇ 270 °C, and the same pressure is vacuumed.
  • the pressure in the polymerization reactor is maintained at about 100 Pa for about 1.5 hours to obtain a prepolymer.
  • the high vacuum is maintained in the polymerization vessel at a pressure of 60 Pa. 2.5 hours, a PET-based graphene composite was obtained. Discharge and slice to get 700g The PET-based graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained.
  • the polymerization kettle is gradually heated to 270-280 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 300 Pa for 0.5 h to obtain a prepolymer; the high vacuum is maintained in the polymerization vessel at a pressure of 60 Pa, and the polymerization is carried out. 1.5 hours, a PET-based graphene composite material was obtained. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite. Discharge and slice to get 700g PET The graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • Formic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1)
  • Sb2O3 mechanical stirring
  • the air in the polymerization vessel was replaced with high-purity nitrogen for 4 times.
  • the pressure in the polymerization vessel was adjusted to 0.2 MPa, and the polymerization vessel was heated to 230 ° C for esterification for 3 hours, and the amount of water produced by the reaction was collected to the theoretical volume, that is, the esterification reaction was completed to obtain an initial product.
  • the polymerization kettle is gradually heated to 265 ⁇ 2 75 °C, and the same pressure is vacuumed.
  • the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer.
  • the high vacuum is maintained in the polymerization vessel at a pressure of 60 Pa. 2 small ⁇ , obtained PET-based graphene composite material.
  • the material was discharged and sliced to obtain 700 g of PET-based graphene composite material, and the composite material was sliced and extruded.
  • the film was formed into a film having a thickness of 70 ⁇ m by stretch molding.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • the pressure of the polymerization vessel was increased to 230 ° C for 3 hours, and the water produced by the reaction was collected to the theoretical volume, that is, the esterification reaction. Finished, the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • the polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • PTA terephthalic acid
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • Example 17 [0074] Weighing 5 g of N-methylpyrrolidone into 600 ml of ethylene glycol, stirring at room temperature until completely dissolved to form an ethylene glycol solution; adding 5 g of graphene oxide powder to the ethylene glycol solution, the graphene oxide powder Stripping thickness of 8nm, length of 120 ⁇ , ultrasonic treatment of 500W for 2h, to obtain a colloidal solution of ethylene glycol modified graphene oxide; adding oxidation in a 5L polymerizer with nitrogen inlet and outlet and mechanical stirring Graphene glycol colloidal solution and lOOg of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and high The nitrogen in the polymerization vessel was replaced by pure nitrogen, and the pressure in the polymerization vessel was changed to 0.2 MPa.
  • PTA terephthalic acid
  • the pressure of the polymerization vessel was increased to 230 ° C for 3 hours, and the water produced by the reaction was collected to the theoretical volume, that is, the esterification reaction. Finished, the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • the polymerization vessel was heated to 230 ° C for esterification for 3 hours, and the methanol formed by the reaction was collected. The amount of the theoretical volume, i.e., the transesterification reaction, is completed, and an initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • a colloidal solution of graphene oxide adding a graphene oxide ethylene glycol colloid solution and 1000 g of dimethyl terephthalate (DMT) to a 5 L polymerizer with nitrogen inlet and outlet and mechanical stirring (where The molar ratio of ethylene glycol to dimethyl terephthalate is 2.1: 1), 0.3g TiO2, mechanical stirring, and the air in the polymerization tank is replaced with high-purity nitrogen, and replaced 4 times to make the polymerization tank
  • the pressure was 0.2 M Pa, and the polymerization vessel was heated to 230 ° C for esterification for 3 hours.
  • the amount of methanol produced by the reaction was collected to the theoretical volume, that is, the transesterification reaction was completed, and the initial product was obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • the polymerization vessel was heated to 230 ° C for esterification for 3 hours, and the methanol formed by the reaction was collected. The amount of the theoretical volume, i.e., the transesterification reaction, is completed, and an initial product is obtained.
  • the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out.
  • Xiaoyan obtained a PET-based graphene composite.
  • the material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 ⁇ m.
  • Example 1 of Chinese Patent Application No. 201210549244.6 The O.lg amino functional group-containing graphene and 100 g of a PET pellet having a molecular weight of 20,000 were pulverized, and then placed in an internal mixer, and kneaded at 290 ° C for 2 hours, and the chips were extruded to obtain an amino graphene-modified PET material. Projection electron micrograph of aminographene modified PET material, graphene and PET isomorphic chemical bond linkage, improve the compatibility of graphene in PET material, make graphene uniformly dispersed in PET, can be applied to prepare new PET film , PET fiber or various PET products and other fields.
  • GG-3180 FGH 0.80 dl/g polyethylene terephthalate
  • oZpetTM Leading Synthetics
  • An xGnP-M-5 grade (99.5% carbon) sheet-peeled graphene nanosheet having an average diameter of 5 Pm was prepared from XG Sciences, Inc (East Lansing, MI) as a dry powder.
  • Graphene nanosheets (xGnP) and the obtained PET resins were mixed into PET-xGnP masterbatch pellets by Ovation Polymers (Medina, OH) using their ExTimaTM technology.
  • Graphene nanosheets are essentially hydrophobic; the effective dispersion of graphene is produced from oxygen and hydroxyl functional groups (formed due to exposure of the raw material carbon during sheet fracture) on their surface with PET polar groups interaction.
  • the masterbatch pellets obtained from the above process are used as raw materials for the injection molding process.
  • the PET control sample was extruded with a weight fraction of 15% PET-xGnp nanocomposite stretch strip at 250 °C - 260 °C, following ASTM D638 model specification (incorporated herein by reference).
  • the dispersibility of graphene oxide in the PET-based graphene composite material of the present application is remarkably superior to that of the comparative example. It can be seen from the comparison of the data in Table 1 that the tensile strength and the helium barrier effect of the PET-based graphene composite obtained in each of the examples of the present application are significantly better than the comparative examples, and by Embodiment 1, Example 10 It can be seen from the comparison with Example 11 that the amount of ethylene glycol and graphene oxide is controlled. The system plays a significant role in improving the tensile strength and the helium barrier effect of the PET-based graphene composite.

Abstract

The present invention provides a PET-based graphene composite material and preparation method therefor, and an aerostat. The preparation method comprises: step S1, enabling ethylene glycol-modified graphene oxide and a PET monomer to undergo an esterification reaction or transesterification to obtain a head product, wherein the PET monomer is terephthalic acid and/or dimethyl terephthalate; step S2, enabling the head product to undergo condensation polymerization to obtain a PET-based graphene composite material. Ethylene glycol-modified graphene oxide and a PET monomer undergo an in-situ polymerization reaction, and graphene oxide is dispersed during the reaction of the ethylene glycol and the PET monomer, so that the dispersibility of graphene in the PET-based graphene composite material is improved. Moreover, the preparation method directly uses the PET monomer as a raw material, has a simple process, a short preparation period, and low costs, and is suitable for large-scale industrial production; the prepared PET-based graphene composite material has an excellent gas barrier property and mechanical strength.

Description

说明书 发明名称: PET基石墨烯复合材料、 其制备方法及浮空器 技术领域  Description: Inventive name: PET-based graphene composite material, preparation method thereof and aerostat
[0001] 本发明涉及复合材料领域， 具体而言， 涉及一种 PET基石墨烯复合材料、 其制 备方法及浮空器。  [0001] The present invention relates to the field of composite materials, and in particular to a PET-based graphene composite material, a method of preparing the same, and an aerostat.
背景技术  Background technique
[0002] [0002]聚对苯二甲酸乙二酯 （PET) 是一种热塑性塑料， 具有刚性和强度大、 耐蠕变和尺寸稳定性好等优点， 广泛应用于纤维、 薄膜、 包装材料、 电子电器 、 医疗卫生、 建筑、 汽车、 气体阻隔材料等领域。  [0002] [0002] Polyethylene terephthalate (PET) is a thermoplastic, which has the advantages of rigidity and strength, creep resistance and dimensional stability, and is widely used in fibers, films, packaging materials, In the fields of electronics, health care, construction, automotive, gas barrier materials, etc.
[0003] 石墨稀是一种由单层 sp2杂化碳原子组成的蜂窝状结构的二维片状材料， 其特 殊的结构决定了它具有奇特的电学性能、 优异的物理机械、 热学性能以及气体 阻隔性能， 是电磁屏蔽、 抗静电、 高强度及气体阻隔聚合物复合材料的理想填 料， 在制备轻质、 低成本、 高性能复合材料方面具有广阔的应用潜力。 石墨烯 是目前世界上力学强度最高的材料， 同吋二维片状无缺陷的石墨烯对有所气体 分子都具有不可渗透性质； 当石墨烯均匀分散在聚合物基体中， 不仅可以大幅 提高聚合物材料的强度， 同吋可以增加气体扩散路径的长度， 降低聚合物材料 的透气性， 提高聚合物材料的气体阻隔性。 但由于结构完整的石墨烯在聚合物 中的分散性差， 与聚合物的相互结合作用弱， 影响了其各种优异性能的发挥， 因此石墨烯的分散是制备聚合物基石墨烯复合材料需要重点解决的问题。 [0003] Graphite thin is a two-dimensional sheet-like material composed of a single layer of sp2 hybridized carbon atoms. Its special structure determines its peculiar electrical properties, excellent physical and mechanical properties, thermal properties and gases. Barrier performance is an ideal filler for electromagnetic shielding, antistatic, high strength and gas barrier polymer composites, and has broad application potential in the preparation of lightweight, low cost, high performance composite materials. Graphene is the most mechanically strong material in the world. The two-dimensional sheet-like defect-free graphene has impermeable properties to gas molecules. When graphene is uniformly dispersed in the polymer matrix, it can not only greatly increase the polymerization. The strength of the material, the same can increase the length of the gas diffusion path, reduce the gas permeability of the polymer material, and improve the gas barrier properties of the polymer material. However, due to the poor dispersibility of the structurally intact graphene in the polymer, the interaction with the polymer is weak, which affects its various excellent properties. Therefore, the dispersion of graphene is the key to preparing the polymer-based graphene composite. solved problem.
技术问题  technical problem
[0004] 目前， 制备 PET基石墨烯纳米复合材料的方法主要是通过熔融共混法弓 I入经表 面修饰的石墨烯功能材料。 例如， 申请号为 201210549244.6的中国专利申请公幵 了将氨基石墨烯与 PET熔融共混制备石墨烯改性 PET材料； 申请号为 2012800332 03.X的中国专利申请公幵了通过将石墨烯纳米颗粒材料与 PET切片熔融共混制备 含石墨烯 PET母料。 目前的熔融共混法一般是先要经过石墨烯功能材料的制备， 包括氧化石墨烯的还原和表面修饰处理， PET树脂的合成， 再将表面修饰的石墨 烯粉末与 PET树脂切片在熔融状态下进行共混， 从而得到聚合物复合材料的方法 。 但是， 该方法无法解决石墨烯分散难的问题， 同吋工艺繁琐、 污染大、 能源 消耗大， 不利于大规模低成本、 无污染生产。 [0004] At present, a method for preparing a PET-based graphene nanocomposite is mainly through a melt blending method into a surface-modified graphene functional material. For example, Chinese Patent Application No. 201210549244.6 discloses the preparation of graphene-modified PET material by melt blending of amino graphene and PET; the Chinese patent application No. 2012800332 03.X discloses the use of graphene nanoparticles. The material was melt blended with PET chips to prepare a graphene-containing PET masterbatch. The current melt blending method generally involves the preparation of a graphene functional material, including reduction and surface modification of graphene oxide, synthesis of PET resin, and slicing surface-modified graphene powder and PET resin in a molten state. Method for blending to obtain a polymer composite . However, this method cannot solve the problem of difficulty in dispersing graphene, and the same process is cumbersome, polluting, and energy-consuming, which is not conducive to large-scale low-cost, pollution-free production.
问题的解决方案  Problem solution
技术解决方案  Technical solution
[0005] [0004]本发明的主要目的在于提供一种 PET基石墨烯复合材料、 其制备方法及 浮空器， 以解决现有技术中的问题 PET基石墨烯复合材料中氧化石墨烯分散性差 的问题。  [0004] The main object of the present invention is to provide a PET-based graphene composite material, a preparation method thereof and an aerostat to solve the problems in the prior art. The dispersion of graphene oxide in a PET-based graphene composite material is poor. The problem.
[0006] 为了实现上述目的， 根据本发明的一个方面， 提供了一种 PET基石墨烯复合材 料的制备方法， 该制备方法包括： 步骤 Sl， 使乙二醇修饰的氧化石墨烯与 PET单 体进行酯化反应或酯交换反应， 得到初产物， PET单体为对苯二甲酸和 /或对苯 二甲酸二甲酯； 步骤 S2， 使初产物进行缩聚反应得到 PET基石墨烯复合材料。 In order to achieve the above object, according to an aspect of the invention, a method for preparing a PET-based graphene composite material is provided, the preparation method comprising: Step S1, ethylene glycol-modified graphene oxide and PET monomer The esterification reaction or the transesterification reaction is carried out to obtain a primary product, and the PET monomer is terephthalic acid and/or dimethyl terephthalate; and in step S2 , the primary product is subjected to a polycondensation reaction to obtain a PET-based graphene composite material.
[0007] 进一步地， 上述 PET单体为对苯二甲酸， 步骤 S1在氮气或惰性气体气氛中进行 且包括： 使乙二醇修饰的氧化石墨烯与对苯二甲酸在 220~250。C的温度、 0~0.4M Pa的压强下进行酯化反应， 得到初产物， 酯化反应持续 2.5~3.5h， 酯化反应所用 的催化剂为四丙基锆、 三氧化二锑或氢氧化锂。  Further, the above PET monomer is terephthalic acid, and step S1 is carried out in a nitrogen or inert gas atmosphere and comprises: ethylene glycol-modified graphene oxide and terephthalic acid at 220 to 250. The esterification reaction is carried out at a temperature of C and a pressure of 0 to 0.4 MPa to obtain an initial product, and the esterification reaction is continued for 2.5 to 3.5 hours. The catalyst used for the esterification reaction is tetrapropylzirconium, antimony trioxide or lithium hydroxide. .
[0008] 进一步地， 上述乙二醇修饰的氧化石墨烯中氧化石墨烯相对于对苯二甲酸的重 量百分比为 0.5~5% ; 乙二醇修饰的氧化石墨烯中乙二醇与对苯二甲酸的摩尔比 为 1.5: 1-2.1: 1 = [0008] Further, the weight percentage of the graphene oxide to the terephthalic acid in the ethylene glycol-modified graphene oxide is 0.5 to 5% ; the ethylene glycol modified graphene oxide in the ethylene glycol and the terephthalic acid The molar ratio of formic acid is 1.5: 1-2.1: 1 =
[0009] 进一步地， 上述 PET单体为对苯二甲酸二甲酯， 步骤 S1在氮气或惰性气体气氛 中进行且包括： 使乙二醇修饰的氧化石墨烯与对苯二甲酸二甲酯在 220~250。C的 温度、 0~0.4MPa的压强下进行酯交换反应， 得到初产物， 酯交换反应持续 2.5~3. 5h， 酯交换反应所用的催化剂为钛酸四丁酯、 醋酸镁或二氧化钛。  [0009] Further, the above PET monomer is dimethyl terephthalate, and step S1 is performed in a nitrogen or inert gas atmosphere and includes: modifying ethylene glycol-modified graphene oxide with dimethyl terephthalate 220~250. The transesterification reaction is carried out at a temperature of 0 to 0.4 MPa to obtain a primary product, and the transesterification reaction is continued for 2.5 to 3.5 hours. The catalyst used for the transesterification reaction is tetrabutyl titanate, magnesium acetate or titanium dioxide.
[0010] 进一步地， 上述乙二醇修饰的氧化石墨烯中氧化石墨烯相对于对苯二甲酸二甲 酯的重量百分比为 0.5~5% ; 乙二醇修饰的氧化石墨烯中乙二醇与对苯二甲酸二 甲酯的摩尔比为 2.1 : 1-2.7: 1 = [0010] Further, the weight percentage of graphene oxide in the above ethylene glycol-modified graphene oxide relative to dimethyl terephthalate is 0.5 to 5% ; ethylene glycol in ethylene glycol modified graphene oxide and The molar ratio of dimethyl terephthalate is 2.1: 1-2.7: 1 =
[0011] 进一步地， 上述步骤 S2包括： 在 260~280°C、 0~600Pa的压强下， 利用催化剂使 初产物进行缩聚反应得到 PET基石墨烯复合材料。  [0011] Further, the above step S2 comprises: performing a polycondensation reaction of the primary product by a catalyst at a pressure of 260 to 280 ° C and a temperature of 0 to 600 Pa to obtain a PET-based graphene composite material.
[0012] 进一步地， 上述步骤 S2包括： 在 265~275°C、 100~600Pa的压强下， 利用催化剂 使初产物进行预聚反应 30~90min得到预聚产物； 在 265~275°C、 0~60Pa的压强下 ， 禾 1」用催化剂使预聚产物进行缩聚反应 90~150min得到 PET基石墨烯复合材料。 [0012] Further, the above step S2 includes: using a catalyst at a pressure of 265 to 275 ° C and a pressure of 100 to 600 Pa The prepolymerization reaction is carried out for 30 to 90 minutes to obtain a prepolymerized product. Under the pressure of 265 to 275 ° C and 0 to 60 Pa, the prepolymerized product is subjected to a polycondensation reaction for 90 to 150 minutes to obtain a PET-based graphene composite. material.
[0013] 进一步地， 上述催化剂为乙二醇锑或三氧化二锑。 Further, the above catalyst is ethylene glycol ruthenium or antimony trioxide.
[0014] 进一步地， 上述制备方法还包括乙二醇修饰的氧化石墨烯的制备过程， 制备过 程包括： 步骤 A， 将稳定剂溶解于乙二醇中形成乙二醇溶液； 步骤 B， 将乙二醇 溶液与氧化石墨烯混合形成乙二醇修饰的氧化石墨烯。  [0014] Further, the above preparation method further includes a preparation process of ethylene glycol-modified graphene oxide, and the preparation process comprises the following steps: Step A: dissolving the stabilizer in ethylene glycol to form an ethylene glycol solution; Step B, The diol solution is mixed with graphene oxide to form ethylene glycol modified graphene oxide.
[0015] 进一步地， 上述步骤 B利用功率为 300~1000W超声处理 0.5~2h使得氧化石墨烯 分散在乙二醇溶液中形成乙二醇修饰的氧化石墨烯。 [0015] Further, in the above step B, the power is 300-1000 W ultrasonic treatment for 0.5~2 h, so that the graphene oxide is dispersed in the ethylene glycol solution to form ethylene glycol-modified graphene oxide.
[0016] 进一步地， 上述氧化石墨烯的剥离厚度为 0.5~6nm， 长度为 10~100μηι。 [0016] Further, the graphene oxide has a peeling thickness of 0.5 to 6 nm and a length of 10 to 100 μm.
[0017] 进一步地， 上述稳定剂相对于 PET单体的重量百分比为 0.3~0.7%， 稳定剂为 N- 甲基吡咯烷酮或聚乙烯吡咯烷酮。 [0017] Further, the weight percentage of the above stabilizer relative to the PET monomer is 0.3 to 0.7%, and the stabilizer is N-methylpyrrolidone or polyvinylpyrrolidone.
[0018] 根据本发明的另一方面， 提供了一种 PET基石墨烯复合材料， 该 PET基石墨烯 复合材料为上述的制备方法制备而成， PET基石墨烯复合材料的拉伸强度为 7500[0018] According to another aspect of the present invention, there is provided a PET-based graphene composite material prepared by the above-described preparation method, and a tensile strength of a PET-based graphene composite material of 7500
~12500MPa， 氦气透过率为 800~950ml/m2.day.0.1MPa。 ~12500MPa, helium gas transmission rate is 800~950ml/m2.day.0.1MPa.
[0019] 根据本发明的另一方面， 提供了一种浮空器， 浮空器具有蒙皮材料， 该蒙皮材 料包括阻气层， 形成该阻气层的材料包括上述的 PET基石墨烯复合材料。 [0019] According to another aspect of the present invention, there is provided an aerostat having a skin material, the skin material comprising a gas barrier layer, and the material forming the gas barrier layer comprises the above-described PET-based graphene Composite material.
[0020] 进一步地， 蒙皮材料包括依次设置的耐候层、 纤维层和阻气层， 或包括依次设 置的耐候层、 阻气层和纤维层。 [0020] Further, the skin material comprises a weathering layer, a fiber layer and a gas barrier layer which are sequentially disposed, or a weathering layer, a gas barrier layer and a fiber layer which are sequentially disposed.
发明的有益效果  Advantageous effects of the invention
有益效果  Beneficial effect
[0021] 应用本发明的技术方案， 将乙二醇修饰的氧化石墨烯与 PET单体进行原位聚合 反应， 利用乙二醇与 PET单体进行反应的同吋将氧化石墨烯分散在其中， 进而改 善了石墨烯在 PET基石墨烯复合材料中的分散性。 且上述制备方法直接以 PET单 体为原料， 省去了现有技术 PET单体聚合的过程， 因此工艺简单、 制备周期短、 成本较低， 适用于大规模工艺化生产， 所制备的 PET基石墨烯复合材料具有优异 的气体阻隔性和机械强度。  [0021] Applying the technical scheme of the present invention, in-situ polymerization of ethylene glycol-modified graphene oxide and PET monomer, and dispersing graphene oxide therein by using the same reaction of ethylene glycol and PET monomer; Furthermore, the dispersibility of graphene in the PET-based graphene composite material is improved. Moreover, the above preparation method directly uses PET monomer as a raw material, and the process of polymerization of the prior art PET monomer is omitted, so the process is simple, the preparation cycle is short, and the cost is low, and is suitable for large-scale process production, and the prepared PET base. Graphene composites have excellent gas barrier properties and mechanical strength.
本发明的实施方式 [0022] [0008]需要说明的是， 在不冲突的情况下， 本申请中的实施例及实施例中的特 征可以相互组合。 下面将结合实施例来详细说明本发明。 Embodiments of the invention [0008] It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the embodiments.
[0023] 为了解决现有技术熔融共混法所形成的 PET基石墨烯复合材料中氧化石墨烯分 散性差的问题， 在本申请一种典型的实施方式中， 提供了一种 PET基石墨烯复合 材料的制备方法， 制备方法包括： 步骤 Sl， 使乙二醇修饰的氧化石墨烯与 PET单 体进行酯化反应或酯交换反应， 得到初产物， PET单体为对苯二甲酸和 /或对苯 二甲酸二甲酯； 步骤 S2， 使初产物进行缩聚反应得到 PET基石墨烯复合材料。 [0023] In order to solve the problem of poor dispersibility of graphene oxide in the PET-based graphene composite material formed by the prior art melt blending method, in an exemplary embodiment of the present application, a PET-based graphene composite is provided. The preparation method of the material comprises the following steps: Step S1, esterifying or transesterifying the ethylene glycol-modified graphene oxide with the PET monomer to obtain a primary product, and the PET monomer is terephthalic acid and/or Dimethyl phthalate; Step S2 , the primary product is subjected to a polycondensation reaction to obtain a PET-based graphene composite material.
[0024] 将乙二醇修饰的氧化石墨烯与 PET单体进行原位聚合反应， 利用乙二醇与 PET 单体进行反应的同吋将氧化石墨烯分散在其中， 进而改善了石墨烯在 PET基石墨 烯复合材料中的分散性。 且上述制备方法直接以 PET单体为原料， 省去了现有技 术 PET单体聚合的过程， 因此工艺简单、 制备周期短、 成本较低， 适用于大规模 工艺化生产， 所制备的 PET基石墨烯复合材料具有优异的气体阻隔性和机械强度  [0024] In-situ polymerization of ethylene glycol-modified graphene oxide with PET monomer, and the use of ethylene glycol and PET monomer to react with the same, dispersing graphene oxide therein, thereby improving graphene in PET Dispersibility in a graphene-based composite. Moreover, the above preparation method directly uses PET monomer as a raw material, and the process of polymerization of the prior art PET monomer is omitted, so the process is simple, the preparation cycle is short, and the cost is low, and is suitable for large-scale process production, and the prepared PET base. Graphene composites have excellent gas barrier properties and mechanical strength
[0025] 上述制备方法根据 PET单体的不同其反应条件有所不同。 在本申请一种优选的 实施例中， 上述 PET单体为对苯二甲酸， 上述步骤 S1在氮气或惰性气体气氛中进 行且包括： 使乙二醇修饰的氧化石墨烯与对苯二甲酸在 220~250°C的温度、 0 0.4 MPa的压强下进行酯化反应， 得到初产物， 优选酯化反应持续 2.5~3.5h， 酯化反 应所用的催化剂为四丙基锆、 三氧化二锑或氢氧化锂。 在上述条件下， 乙二醇 与对苯二甲酸发生酯化反应， 形成 PET的基本单元， 其中的氧化石墨烯随着乙二 醇一起分散至 PET的基本单元中； 其中的氮气或惰性气体气氛能够有效防止在上 述反应条件下， 氧化石墨烯的羟基等活性基团被氧化。 [0025] The above preparation method differs depending on the PET monomer. In a preferred embodiment of the present application, the PET monomer is terephthalic acid, and the step S1 is performed in a nitrogen or inert gas atmosphere and comprises: modifying ethylene glycol with graphene oxide and terephthalic acid The esterification reaction is carried out at a temperature of 220 to 250 ° C and a pressure of 0 0.4 MPa to obtain an initial product, preferably an esterification reaction is carried out for 2.5 to 3.5 hours, and the catalyst used for the esterification reaction is tetrapropylzirconium or antimony trioxide or Lithium hydroxide. Under the above conditions, ethylene glycol is esterified with terephthalic acid to form a basic unit of PET, in which graphene oxide is dispersed together with ethylene glycol into the basic unit of PET; nitrogen or inert gas atmosphere It is possible to effectively prevent the active group such as the hydroxyl group of the graphene oxide from being oxidized under the above reaction conditions.
[0026] 为了使尽可能多的氧化石墨烯进入 PET基本单元， 乙二醇修饰的氧化石墨烯中 氧化石墨烯相对于对苯二甲酸的重量百分比为 0.5~5%; 乙二醇修饰的氧化石墨 烯中乙二醇与对苯二甲酸的摩尔比为 1.5: 1-2.1:1= 乙二醇的用量相对于对苯二 甲酸的用量稍多， 因此在反应过程中能够将乙二醇修饰的氧化石墨烯中氧化石 墨烯尽可能地带入产物中， 提高氧化石墨烯在最终的 PET基石墨烯复合材料的分 散性。 [0026] In order to allow as much graphene oxide as possible to enter the PET base unit, the weight percentage of graphene oxide to ethylene terephthalate in the ethylene glycol modified graphene oxide is 0.5 to 5% ; ethylene glycol modified oxidation The molar ratio of ethylene glycol to terephthalic acid in graphene is 1.5: 1-2.1:1 = the amount of ethylene glycol is slightly more than that of terephthalic acid, so ethylene glycol can be modified during the reaction. The graphene oxide in the graphene oxide is incorporated into the product as much as possible to improve the dispersibility of the graphene oxide in the final PET-based graphene composite.
[0027] 在本申请另一种优选的实施例中， 上述 PET单体为对苯二甲酸二甲酯， 步骤 S1 在氮气或惰性气体气氛中进行且包括： 使乙二醇修饰的氧化石墨烯与对苯二甲 酸二甲酯在 220~250°C的温度、 0~0.4MPa的压强下进行酯交换反应， 得到初产物 ， 优选酯交换反应持续 2.5~3.5h， 酯交换反应所用的催化剂为钛酸四丁酯、 醋酸 镁或二氧化钛。 在上述条件下， 乙二醇与对苯二甲酸发生酯交换反应， 形成 PET 的基本单元， 其中的氧化石墨烯随着乙二醇一起分散至 PET的基本单元中。 [0027] In another preferred embodiment of the present application, the PET monomer is dimethyl terephthalate, step S1 The reaction is carried out in a nitrogen or inert gas atmosphere and comprises: transesterifying the ethylene glycol modified graphene oxide with dimethyl terephthalate at a temperature of 220 to 250 ° C and a pressure of 0 to 0.4 MPa. The initial product preferably has a transesterification reaction for 2.5 to 3.5 hours, and the catalyst used for the transesterification reaction is tetrabutyl titanate, magnesium acetate or titanium dioxide. Under the above conditions, ethylene glycol is transesterified with terephthalic acid to form a basic unit of PET in which graphene oxide is dispersed together with ethylene glycol into the basic unit of PET.
[0028] 同样， 为了使尽可能多的氧化石墨烯进入 PET基本单元， 优选乙二醇修饰的氧 化石墨烯中氧化石墨烯相对于对苯二甲酸二甲酯的重量百分比为 0.5~5%; 乙二 醇修饰的氧化石墨烯中乙二醇与对苯二甲酸二甲酯的摩尔比为 2.1 : 1-2.7:1= 乙 二醇的用量相对于对苯二甲酸二甲酯的用量稍多， 因此在反应过程中能够将乙 二醇修饰的氧化石墨烯中氧化石墨烯尽可能地带入产物中， 提高氧化石墨烯在 最终的 PET基石墨烯复合材料的分散性。 [0028] Similarly, in order to allow as much graphene oxide as possible to enter the PET base unit, it is preferred that the weight percentage of graphene oxide relative to dimethyl terephthalate in the ethylene glycol modified graphene oxide is 0.5 to 5% ; The molar ratio of ethylene glycol to dimethyl terephthalate in ethylene glycol modified graphene oxide is 2.1: 1-2.7:1 = the amount of ethylene glycol is slightly more than the amount of dimethyl terephthalate. Therefore, in the reaction process, the graphene oxide in the ethylene glycol-modified graphene oxide can be incorporated into the product as much as possible, and the dispersibility of the graphene oxide in the final PET-based graphene composite material is improved.
[0029] 为了使步骤 S1形成的初产物能够顺利进行缩聚， 优选上述步骤 S2包括： 在 260~ 280°C、 0~600Pa的压强下， 利用催化剂使初产物进行缩聚反应得到 PET基石墨烯 复合材料。 在上述温度下初产物处于熔融状态， 且利用 0~600Pa的真空环境使得 缩聚顺利进行； 如果温度低于 260°C， 使得反应速度较慢， 不利于提高反应速率 ； 如果温度高于 280°C， 所形成的产物有可能会发生热分解， 降低最终产物的收 率。  [0029] In order to enable the initial product formed in the step S1 to be smoothly polycondensed, it is preferable that the step S2 includes: using a catalyst to carry out a polycondensation reaction of the primary product at a pressure of 260 to 280 ° C and a temperature of 0 to 600 Pa to obtain a PET-based graphene composite. material. At the above temperature, the initial product is in a molten state, and the polycondensation is smoothly carried out by using a vacuum environment of 0 to 600 Pa; if the temperature is lower than 260 ° C, the reaction rate is slow, which is disadvantageous for increasing the reaction rate; if the temperature is higher than 280 ° C The formed product may undergo thermal decomposition and reduce the yield of the final product.
[0030] 在本申请又一种优选的实施例中， 上述步骤 S2包括： 在 265~275°C、 100~600Pa 的压强下， 利用催化剂使初产物进行预聚反应 30~90min得到预聚产物； 在 265~2 75°C、 0~60Pa的压强下， 利用催化剂使预聚产物进行缩聚反应 90~150min得到 PE [0030] In a further preferred embodiment of the present application, the step S2 includes: pre-polymerizing the initial product for 30 to 90 minutes using a catalyst at a pressure of 265 to 275 ° C and a pressure of 100 to 600 Pa to obtain a prepolymerized product. At a pressure of 265~2 75 °C and 0~60Pa, the prepolymerized product is subjected to polycondensation reaction for 90~150min to obtain PE.
T基石墨烯复合材料。 上述过程采用催化剂能够提高反应速率， 且通过控制反应 条件将缩聚反应分为预聚和缩聚两个过程进行， 一方面提高了石墨烯在 PET基石 墨烯复合材料中的分散性， 另一方面优化了所得到的 PET基石墨烯复合材料的强 度性能。 T-based graphene composite. The above process uses a catalyst to increase the reaction rate, and the polycondensation reaction is divided into two processes of prepolymerization and polycondensation by controlling the reaction conditions, thereby improving the dispersibility of graphene in the PET-based graphene composite material, and optimizing on the other hand. The strength properties of the obtained PET-based graphene composite material.
[0031] 可用于本申请的催化剂包括但不限于锑系催化剂、 锗系催化剂和钛系催化剂， 优选上述催化剂为乙二醇锑或三氧化二锑。  Catalysts useful in the present application include, but are not limited to, ruthenium-based catalysts, ruthenium-based catalysts, and titanium-based catalysts. Preferably, the above catalysts are ethylene glycol ruthenium or antimony trioxide.
[0032] 本申请所采用的乙二醇修饰的氧化石墨烯一方面是为了利用其中的乙二醇与 PE[0032] The ethylene glycol modified graphene oxide used in the present application is on the one hand to utilize ethylene glycol and PE therein.
T单体进行反应， 另一方面是利用乙二醇修饰氧化石墨烯增加其在有机溶剂中的 溶解性， 提高其在 PET基石墨烯复合材料中的分散性， 因此， 现有技术中的乙二 醇修饰的氧化石墨烯可以应用于本申请， 其具体的合成条件可以在本申请技术 方案基础上进行适当调整， 本申请为了提高乙二醇修饰的氧化石墨烯与 PET单体 的适应性， 优选上述制备方法还包括乙二醇修饰的氧化石墨烯的制备过程， 该 制备过程包括： 步骤 A， 将稳定剂溶解于乙二醇中形成乙二醇溶液； 步骤 B， 将 乙二醇溶液与氧化石墨烯混合形成乙二醇修饰的氧化石墨烯。 T monomer reacts, on the other hand, ethylene oxide is modified by graphene oxide to increase its content in organic solvents. Solubility, improving its dispersibility in PET-based graphene composite materials, therefore, ethylene glycol-modified graphene oxide in the prior art can be applied to the present application, and specific synthesis conditions thereof can be based on the technical solutions of the present application. In order to improve the adaptability of the ethylene glycol modified graphene oxide to the PET monomer, the preparation method further includes a preparation process of the ethylene glycol modified graphene oxide, and the preparation process comprises the following steps: Step A The stabilizer is dissolved in ethylene glycol to form an ethylene glycol solution; in step B, the ethylene glycol solution is mixed with graphene oxide to form ethylene glycol-modified graphene oxide.
[0033] 利用稳定剂保证了氧化石墨烯在乙二醇中的分散性， 且该稳定剂该可以在下一 步的缩聚反应中提高所得到的 PET基石墨烯复合材料的热稳定性。  [0033] The use of a stabilizer ensures the dispersibility of graphene oxide in ethylene glycol, and the stabilizer can improve the thermal stability of the obtained PET-based graphene composite in the next polycondensation reaction.
[0034] 为了进一步增加氧化石墨烯在乙二醇修饰的氧化石墨烯中的含量， 优选上述步 骤 B利用功率为 300~1000W超声处理 0.5~2h使得氧化石墨烯分散在乙二醇溶液中 形成乙二醇修饰的氧化石墨烯。  [0034] In order to further increase the content of graphene oxide in the ethylene glycol modified graphene oxide, it is preferred that the above step B is performed by using a power of 300 to 1000 W for 0.5 to 2 h so that the graphene oxide is dispersed in the ethylene glycol solution to form B. Glycol modified graphene oxide.
[0035] 进一步地， 优选上述氧化石墨烯的剥离厚度为 0.5~6nm， 长度为 10~100μηι。 具 有上述特点的氧化石墨烯与乙二醇进行混合吋， 在乙二醇中的分散性更好。  Further, it is preferable that the graphene oxide has a peeling thickness of 0.5 to 6 nm and a length of 10 to 100 μm. The graphene oxide having the above characteristics is mixed with ethylene glycol and has better dispersibility in ethylene glycol.
[0036] 为了使得稳定剂在缩聚过程中发挥稳定作用， 优选， 稳定剂相对于 PET单体的 重量百分比为 0.3~0.7%， 进一步优选稳定剂为 N-甲基吡咯烷酮或聚乙烯吡咯烷酮  [0036] In order to stabilize the stabilizer during the polycondensation, it is preferred that the weight percentage of the stabilizer to the PET monomer is 0.3 to 0.7%, and further preferably the stabilizer is N-methylpyrrolidone or polyvinylpyrrolidone.
[0037] 在本申请又一种典型的实施方式中， 提供了一种 PET基石墨烯复合材料， PET 基石墨烯复合材料上述的制备方法制备而成， PET基石墨烯复合材料的拉伸强度 为 7500~12500MPa， 氦气透过率为 800~950ml/m2.day.0.1MPa。 采用本申请制备 方法得到的 PET基石墨烯复合材料的拉伸强度和对氦气阻隔率均有明显的改善， 因此可以应用于各种 PET薄膜、 纤维等 PET制品中。 [0037] In another exemplary embodiment of the present application, a PET-based graphene composite material, a PET-based graphene composite material prepared by the above preparation method, and a tensile strength of a PET-based graphene composite material are provided. It is 7500~12500MPa, and the helium permeability is 800~950ml/m2.day.0.1MPa. The tensile strength of the PET-based graphene composite material obtained by the preparation method of the present application and the helium gas barrier ratio are significantly improved, and thus can be applied to various PET films, fibers and the like.
[0038] 在本申请又一种典型的实施方式中， 提供了一种浮空器， 浮空器具有蒙皮材料[0038] In another exemplary embodiment of the present application, an aerostat is provided, the aerostat having a skin material
， 该蒙皮材料包括阻气层， 形成该阻气层的材料包括上述的 PET基石墨烯复合材 料。 由于本申请所形成的 PET基石墨烯复合材料的机械强度和氦气阻隔性能均有 明显改善， 因此可以满足目前浮空器对 PET制品的要求。 The skin material comprises a gas barrier layer, and the material forming the gas barrier layer comprises the above-mentioned PET-based graphene composite material. Since the mechanical strength and the helium barrier property of the PET-based graphene composite material formed by the present application are significantly improved, the requirements for the PET products of the current aerostats can be satisfied.
[0039] 比如， 蒙皮材料包括依次设置的耐候层、 纤维层和阻气层， 或包括依次设置的 耐候层、 阻气层和纤维层。 可以将本申请的 PET基石墨烯复合材料应用于上述阻 气层中， 比如将其拉伸成膜后镀铝即可形成阻气层， 由于其具有优异的机械强 度和阻氦性能， 因此该层即使经过揉搓后仍能具有意义的阻氦能力。 [0039] For example, the skin material includes a weathering layer, a fiber layer, and a gas barrier layer which are sequentially disposed, or includes a weathering layer, a gas barrier layer, and a fiber layer which are sequentially disposed. The PET-based graphene composite material of the present application can be applied to the above gas barrier layer, for example, by stretching it into a film and then aluminizing to form a gas barrier layer, because of its excellent mechanical strength. Degree and resistance, so the layer can have a significant resistance even after enthalpy.
[0040] 以下将结合实施例和对比例， 进一步说明本发明的有益效果。  [0040] Advantageous effects of the present invention will be further described below in conjunction with the examples and comparative examples.
[0041] 实施例 1 Embodiment 1
[0042] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 1000g的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合 釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应 完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合 釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET 基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄 膜。  [0042] Weigh 5g of polyvinylpyrrolidone (PVP), add 600ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloid solution and 1000 g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3 g of Sb2O3, stirring mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0043] 实施例 2  Embodiment 2
[0044] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 1000g的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.4MPa， 将聚合 釜升温至 220°C进行酯化反应 3.5h， 收集反应生成的水到理论体积的量即酯化反 应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚 合釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强 在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι 的薄膜。 [0044] Weigh 5g of polyvinylpyrrolidone (PVP), add 600ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloid solution and 1000 g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3 g of Sb2O3, stirring mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.4 MPa. The polymerization vessel was heated to 220 ° C for esterification reaction for 3.5 hours, and the water produced by the reaction was collected to the theoretical volume. The esterification reaction is completed to obtain a preliminary product. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. Discharge and slice to get 700g The PET-based graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0045] 实施例 3 Embodiment 3
[0046] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0 MPa， 将聚合 釜升温至 220°C进行酯化反应 2.5h， 收集反应生成的水到理论体积的量即酯化反 应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚 合釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强 在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι 的薄膜。  [0046] Weigh 5g of polyvinylpyrrolidone (PVP), add 600ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 1000g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 4 MPa, and the pressure in the polymerization vessel was increased to 220 ° C for esterification reaction for 2.5 hours, and the amount of water produced by the reaction was collected to the theoretical volume. The esterification reaction is completed to obtain a preliminary product. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0047] 实施例 4  Embodiment 4
[0048] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 25g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 1000W的超声处理 2h， 得到乙 二醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜 中加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中 ， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同 吋用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚 合釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反 应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚 合釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强 在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι 的薄膜。 [0048] Weigh 5g of polyvinylpyrrolidone (PVP), add 600ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 25g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 1000 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is prepared by adding a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 1000g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. Discharge and slice to get 700g The PET-based graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0049] 实施例 5 Example 5
[0050] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 50g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 1000W的超声处理 2h， 得到乙 二醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜 中加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中 ， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同 吋用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚 合釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反 应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚 合釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强 在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι 的薄膜。  [0050] Weigh 5g of polyvinylpyrrolidone (PVP) into 600ml of ethylene glycol and stir at room temperature until completely dissolved to form an ethylene glycol solution; add 50g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 1000 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is prepared by adding a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 1000g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0051] 实施例 6  Example 6
[0052] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 840ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 2.1 : 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合 釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应 完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合 釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET 基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄 膜。 [0052] Weigh 5g of polyvinylpyrrolidone (PVP), add 840ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 100 g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 2.1:1), 0.3 g of Sb2O3, stirring mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. Discharge and slice to get 700g PET The graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0053] 实施例 7  Example 7
[0054] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 750ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.8 : 1) ， 0.3gSb2O3， 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合 釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应 完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合 釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET 基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄 膜。 [0054] Weigh 5g of polyvinylpyrrolidone (PVP), add 750ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. a graphene oxide ethylene glycol colloidal solution and 100 g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.8: 1), 0.3 g of Sb2O3, turbulent mechanical stirring, and The same air was used to replace the air in the polymerization vessel with high-purity nitrogen, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification for 3 hours, and the water produced by the reaction was collected to the theoretical volume. That is, the esterification reaction is completed, and a preliminary product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0055] 实施例 8  Example 8
[0056] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合 釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应 完成， 得到初产物。 然后， 将聚合釜逐渐升温至 260~270°C， 同吋抽真空， 聚合 釜内压强保持在 lOOPa左右预聚 1.5h得到预聚物； 幵启高真空保持聚合釜内压强 在 60Pa下， 聚合 2.5小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι 的薄膜。 [0056] Weigh 5g of polyvinylpyrrolidone (PVP), add 600ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 1000g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 260~270 °C, and the same pressure is vacuumed. The pressure in the polymerization reactor is maintained at about 100 Pa for about 1.5 hours to obtain a prepolymer. The high vacuum is maintained in the polymerization vessel at a pressure of 60 Pa. 2.5 hours, a PET-based graphene composite was obtained. Discharge and slice to get 700g The PET-based graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0057] 实施例 9 Example 9
[0058] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合 釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应 完成， 得到初产物。 然后， 将聚合釜逐渐升温至 270~280°C， 同吋抽真空， 聚合 釜内压强保持在 300Pa左右预聚 0.5h得到预聚物； 幵启高真空保持聚合釜内压强 在 60Pa下， 聚合 1.5小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι 的薄膜。  [0058] Weigh 5g of polyvinylpyrrolidone (PVP) into 600ml of ethylene glycol and stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 1000g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 270-280 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 300 Pa for 0.5 h to obtain a prepolymer; the high vacuum is maintained in the polymerization vessel at a pressure of 60 Pa, and the polymerization is carried out. 1.5 hours, a PET-based graphene composite material was obtained. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0059] 实施例 10  Example 10
[0060] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 75g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合 釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应 完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合 釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET 基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄 膜。 [0060] Weigh 5g of polyvinylpyrrolidone (PVP), add 600ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 75g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 1000g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. Discharge and slice to get 700g PET The graphene composite was sliced, and the composite section was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0061] 实施例 11  Example 11
[0062] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 1200ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 2.8: 1) ， 0.3gSb2O3， 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合 釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应 完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合 釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET 基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄 膜。  [0062] Weigh 5g of polyvinylpyrrolidone (PVP), add 1200ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 100 g of terephthalic acid (PTA) (wherein a molar ratio of ethylene glycol to terephthalic acid of 2.8:1), 0.3 g of Sb2O3, stirring mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0063] 实施例 12  Example 12
[0064] 称取 3g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 经功率为 500W 的超声处理 2h， 得到乙二醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口 和机械搅拌的 5L聚合釜中加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯 二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 ， 幵动机械搅拌， 并同吋用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜 内压强为 0.2MPa， 将聚合釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到 理论体积的量即酯化反应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~2 75°C， 同吋抽真空， 聚合釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高 真空保持聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出 料并切片， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向 拉伸成型制成厚 70μηι的薄膜。 [0064] Weigh 3g of polyvinylpyrrolidone (PVP) into 600ml of ethylene glycol and stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the power is 500W After sonication for 2h, a colloidal solution of ethylene glycol-modified graphene oxide was obtained; and the obtained graphene oxide ethylene glycol colloid solution and 100 g of terephthalic acid were added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. Formic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and the air in the polymerization vessel was replaced with high-purity nitrogen for 4 times. The pressure in the polymerization vessel was adjusted to 0.2 MPa, and the polymerization vessel was heated to 230 ° C for esterification for 3 hours, and the amount of water produced by the reaction was collected to the theoretical volume, that is, the esterification reaction was completed to obtain an initial product. Then, the polymerization kettle is gradually heated to 265~2 75 °C, and the same pressure is vacuumed. The pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer. The high vacuum is maintained in the polymerization vessel at a pressure of 60 Pa. 2 small 吋, obtained PET-based graphene composite material. The material was discharged and sliced to obtain 700 g of PET-based graphene composite material, and the composite material was sliced and extruded. The film was formed into a film having a thickness of 70 μm by stretch molding.
[0065] 实施例 13 Example 13
[0066] 称取 7g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合 釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应 完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合 釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET 基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄 膜。  [0066] Weigh 7g of polyvinylpyrrolidone (PVP), add 600ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 3 nm and a length of 50 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 1000g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0067] 实施例 14  Example 14
[0068] 称取 5gN-甲基吡咯烷酮加入 600ml的乙二醇中在室温下搅拌至完全溶解形成乙 二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯粉末的剥 离厚度为 3nm， 长度为 50μηι， 经功率为 500W的超声处理 2h， 得到乙二醇修饰的 氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中加入所制 得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与 对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋用高纯氮 气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应完成， 得 到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合釜内压强 保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET基石墨烯 复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄膜。 [0069] 实施例 15 [0068] Weighing 5 g of N-methylpyrrolidone into 600 ml of ethylene glycol, stirring at room temperature until completely dissolved to form an ethylene glycol solution; adding 5 g of graphene oxide powder to the ethylene glycol solution, the graphene oxide powder Stripping thickness of 3nm, length of 50μηι, ultrasonic treatment of 500W for 2h, to obtain a colloidal solution of ethylene glycol modified graphene oxide; adding oxidation in a 5L polymerizer with nitrogen inlet and outlet and mechanical agitation Graphene glycol colloidal solution and lOOg of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and high The nitrogen in the polymerization vessel was replaced by pure nitrogen, and the pressure in the polymerization vessel was changed to 0.2 MPa. The pressure of the polymerization vessel was increased to 230 ° C for 3 hours, and the water produced by the reaction was collected to the theoretical volume, that is, the esterification reaction. Finished, the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm. Example 15
[0070] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 6nm， 长度为 10μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋 用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合 釜升温至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应 完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合 釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET 基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄 膜。  [0070] Weigh 5g of polyvinylpyrrolidone (PVP) into 600ml of ethylene glycol and stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 6 nm and a length of 10 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 1000g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and the same The air in the polymerization vessel was replaced with high-purity nitrogen gas, and the pressure in the polymerization vessel was changed to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification reaction for 3 hours, and the water produced by the reaction was collected to a theoretical volume of the ester. The reaction is completed and the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0071] 实施例 16  Embodiment 16
[0072] 称取 5gN-甲基吡咯烷酮加入 600ml的乙二醇中在室温下搅拌至完全溶解形成乙 二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯粉末的剥 离厚度为 0.5nm， 长度为 100μηι， 经功率为 500W的超声处理 2h， 得到乙二醇修饰 的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中加入所 制得氧化石墨烯乙二醇胶体溶液和 1000g的对苯二甲酸 （PTA) (其中， 乙二醇 与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋用高纯 氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合釜升温 至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合釜内压 强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下 ， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET基石墨 烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄膜。  [0072] Weighing 5 g of N-methylpyrrolidone into 600 ml of ethylene glycol, stirring at room temperature until completely dissolved to form an ethylene glycol solution; adding 5 g of graphene oxide powder to the ethylene glycol solution, the graphene oxide powder The stripping thickness was 0.5 nm, the length was 100 μηι, and the ultrasonic treatment was performed for 500 h with a power of 500 W to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it was prepared by adding a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. Graphene oxide ethylene glycol colloidal solution and 1000g of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5: 1), 0.3g of Sb2O3, mechanical stirring, and the same High-purity nitrogen was used to replace the air in the polymerization vessel, and the pressure in the polymerization vessel was changed to 4 MPa. The pressure in the polymerization vessel was adjusted to 0.2 MPa. The polymerization vessel was heated to 230 ° C for esterification for 3 hours, and the water produced by the reaction was collected to the theoretical volume. The reaction is completed to obtain a preliminary product. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0073] 实施例 17 [0074] 称取 5gN-甲基吡咯烷酮加入 600ml的乙二醇中在室温下搅拌至完全溶解形成乙 二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯粉末的剥 离厚度为 8nm， 长度为 120μηι， 经功率为 500W的超声处理 2h， 得到乙二醇修饰 的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中加入所 制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸 （PTA) (其中， 乙二醇 与对苯二甲酸的摩尔比为 1.5: 1) ， 0.3gSb2O3 , 幵动机械搅拌， 并同吋用高纯 氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2MPa， 将聚合釜升温 至 230°C进行酯化反应 3h， 收集反应生成的水到理论体积的量即酯化反应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同吋抽真空， 聚合釜内压 强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持聚合釜内压强在 60Pa下 ， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片， 得到 700g PET基石墨 烯复合材料切片， 将复合材料切片经挤出双向拉伸成型制成厚 70μηι的薄膜。 Example 17 [0074] Weighing 5 g of N-methylpyrrolidone into 600 ml of ethylene glycol, stirring at room temperature until completely dissolved to form an ethylene glycol solution; adding 5 g of graphene oxide powder to the ethylene glycol solution, the graphene oxide powder Stripping thickness of 8nm, length of 120μηι, ultrasonic treatment of 500W for 2h, to obtain a colloidal solution of ethylene glycol modified graphene oxide; adding oxidation in a 5L polymerizer with nitrogen inlet and outlet and mechanical stirring Graphene glycol colloidal solution and lOOg of terephthalic acid (PTA) (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1), 0.3g of Sb2O3, mechanical stirring, and high The nitrogen in the polymerization vessel was replaced by pure nitrogen, and the pressure in the polymerization vessel was changed to 0.2 MPa. The pressure of the polymerization vessel was increased to 230 ° C for 3 hours, and the water produced by the reaction was collected to the theoretical volume, that is, the esterification reaction. Finished, the initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0075] 实施例 18  Example 18
[0076] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 720ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 6nm， 长度为 10μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 lOOOg的对苯二甲酸二甲酯 （DMT) ( 其中， 乙二醇与对苯二甲酸二甲酯的摩尔比为 2.5: 1) ， 0.3gTiO2， 幵动机械搅 拌， 并同吋用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2M Pa, 将聚合釜升温至 230°C进行酯化反应 3h， 收集反应生成的甲醇到理论体积的 量即酯交换反应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同 吋抽真空， 聚合釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持 聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片 ， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型 制成厚 70μηι的薄膜。  [0076] Weigh 5g of polyvinylpyrrolidone (PVP), add 720ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 6 nm and a length of 10 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloidal solution and 1000 g of dimethyl terephthalate (DMT) (wherein a molar ratio of ethylene glycol to dimethyl terephthalate is 2.5:1), 0.3 g of TiO2, tilting Mechanically stirred, and replaced the air in the polymerization vessel with high-purity nitrogen, and replaced it 4 times to make the pressure in the polymerization reactor 0.2M Pa. The polymerization vessel was heated to 230 ° C for esterification for 3 hours, and the methanol formed by the reaction was collected. The amount of the theoretical volume, i.e., the transesterification reaction, is completed, and an initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0077] 实施例 19  Example 19
[0078] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 600ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 6nm， 长度为 10μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 1000g的对苯二甲酸二甲酯 （DMT) ( 其中， 乙二醇与对苯二甲酸二甲酯的摩尔比为 2.1 : 1) ， 0.3gTiO2， 幵动机械搅 拌， 并同吋用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2M Pa, 将聚合釜升温至 230°C进行酯化反应 3h， 收集反应生成的甲醇到理论体积的 量即酯交换反应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同 吋抽真空， 聚合釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持 聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片 ， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型 制成厚 70μηι的薄膜。 [0078] Weigh 5g of polyvinylpyrrolidone (PVP) and add 600ml of ethylene glycol to stir at room temperature until completely dissolved The ethylene glycol solution is decomposed; 5 g of graphene oxide powder is added to the ethylene glycol solution, and the graphene oxide powder has a peeling thickness of 6 nm and a length of 10 μm, and is subjected to ultrasonic treatment for 500 hours at a power of 500 W to obtain ethylene glycol modification. a colloidal solution of graphene oxide; adding a graphene oxide ethylene glycol colloid solution and 1000 g of dimethyl terephthalate (DMT) to a 5 L polymerizer with nitrogen inlet and outlet and mechanical stirring (where The molar ratio of ethylene glycol to dimethyl terephthalate is 2.1: 1), 0.3g TiO2, mechanical stirring, and the air in the polymerization tank is replaced with high-purity nitrogen, and replaced 4 times to make the polymerization tank The pressure was 0.2 M Pa, and the polymerization vessel was heated to 230 ° C for esterification for 3 hours. The amount of methanol produced by the reaction was collected to the theoretical volume, that is, the transesterification reaction was completed, and the initial product was obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0079] 实施例 20 Example 20
[0080] 称取 5g聚乙烯吡咯烷酮 （PVP) 加入 770ml的乙二醇中在室温下搅拌至完全溶 解形成乙二醇溶液； 向该乙二醇溶液中加入 5g氧化石墨烯粉末， 该氧化石墨烯 粉末的剥离厚度为 6nm， 长度为 10μηι， 经功率为 500W的超声处理 2h， 得到乙二 醇修饰的氧化石墨烯的胶体溶液； 在带有氮气进出口和机械搅拌的 5L聚合釜中 加入所制得氧化石墨烯乙二醇胶体溶液和 1000g的对苯二甲酸二甲酯 （DMT) ( 其中， 乙二醇与对苯二甲酸二甲酯的摩尔比为 2.7: 1) ， 0.3gTiO2， 幵动机械搅 拌， 并同吋用高纯氮气置换聚合釜内的空气， 置换 4次， 使聚合釜内压强为 0.2M Pa, 将聚合釜升温至 230°C进行酯化反应 3h， 收集反应生成的甲醇到理论体积的 量即酯交换反应完成， 得到初产物。 然后， 将聚合釜逐渐升温至 265~275°C， 同 吋抽真空， 聚合釜内压强保持在 600Pa左右预聚 lh得到预聚物； 幵启高真空保持 聚合釜内压强在 60Pa下， 聚合 2小吋， 得到 PET基石墨烯复合材料。 出料并切片 ， 得到 700g PET基石墨烯复合材料切片， 将复合材料切片经挤出双向拉伸成型 制成厚 70μηι的薄膜。  [0080] Weigh 5g of polyvinylpyrrolidone (PVP), add 770ml of ethylene glycol, stir at room temperature until completely dissolved to form an ethylene glycol solution; add 5g of graphene oxide powder to the ethylene glycol solution, the graphene oxide The powder has a peeling thickness of 6 nm and a length of 10 μm, and is subjected to ultrasonic treatment at a power of 500 W for 2 hours to obtain a colloidal solution of ethylene glycol-modified graphene oxide; it is added to a 5 L polymerization vessel with nitrogen inlet and outlet and mechanical stirring. A graphene oxide ethylene glycol colloid solution and 1000 g of dimethyl terephthalate (DMT) (wherein a molar ratio of ethylene glycol to dimethyl terephthalate is 2.7:1), 0.3 g of TiO2, tilting Mechanically stirred, and replaced the air in the polymerization vessel with high-purity nitrogen, and replaced it 4 times to make the pressure in the polymerization reactor 0.2M Pa. The polymerization vessel was heated to 230 ° C for esterification for 3 hours, and the methanol formed by the reaction was collected. The amount of the theoretical volume, i.e., the transesterification reaction, is completed, and an initial product is obtained. Then, the polymerization kettle is gradually heated to 265-275 ° C, and the same pressure is vacuumed, and the pressure in the polymerization reactor is maintained at about 600 Pa for pre-polymerization for 1 hour to obtain a prepolymer; the high vacuum is maintained at a pressure of 60 Pa in the polymerization vessel, and polymerization is carried out. Xiaoyan, obtained a PET-based graphene composite. The material was discharged and sliced to obtain 700 g of a PET-based graphene composite material, and the composite material was subjected to extrusion biaxial stretching to form a film having a thickness of 70 μm.
[0081] 对比例 1  Comparative Example 1
[0082] 重复申请号为 201210549244.6的中国专利申请的实施例 1 [0083] 将 O.lg含有氨基官能团的石墨烯与 lOOg分子量 20000的 PET切片粉碎后加入密炼 机， 在 290°C密炼 2h,挤出切片， 获得氨基石墨烯改性 PET材料。 氨基石墨烯改性 PET材料的投射电子显微镜照片， 石墨烯与 PET同构化学键链接， 改善石墨烯在 PET材料中的相容性， 使得石墨烯在 PET中均匀分散， 可以应用于制备新型 PET 薄膜， PET纤维或各种 PET制品等领域。 [0082] Example 1 of Chinese Patent Application No. 201210549244.6 [0083] The O.lg amino functional group-containing graphene and 100 g of a PET pellet having a molecular weight of 20,000 were pulverized, and then placed in an internal mixer, and kneaded at 290 ° C for 2 hours, and the chips were extruded to obtain an amino graphene-modified PET material. Projection electron micrograph of aminographene modified PET material, graphene and PET isomorphic chemical bond linkage, improve the compatibility of graphene in PET material, make graphene uniformly dispersed in PET, can be applied to prepare new PET film , PET fiber or various PET products and other fields.
[0084] 对比例 2  Comparative Example 2
[0085] 重复申请号为 201280033203.X的中国专利申请的实施例：  [0085] An example of a Chinese patent application with the application number 201280033203.X is repeated:
[0086] 在一个示范中， 使用市售可得的被称作 oZpetTM的 0.80dl/g(I.V)聚对苯二甲酸乙 二酯 （GG-3180 FGH, Leading Synthetics,  [0086] In one example, a commercially available 0.80 dl/g (I.V) polyethylene terephthalate (GG-3180 FGH, Leading Synthetics, known as oZpetTM) is used.
澳大利亚） 。 平均直径为 5Pm的 xGnP-M-5级别 （99.5%碳） 片层剥离石墨烯纳米 片由 XG Sciences, Inc (East Lansing, MI)以干粉末制得。 石墨烯纳米片 （xGnP) 与所取得的 PET树脂通过 Ovation Polymers (Medina,OH)利用它们的 ExTimaTM技 术混合为 PET-xGnP母料丸粒。  Australia). An xGnP-M-5 grade (99.5% carbon) sheet-peeled graphene nanosheet having an average diameter of 5 Pm was prepared from XG Sciences, Inc (East Lansing, MI) as a dry powder. Graphene nanosheets (xGnP) and the obtained PET resins were mixed into PET-xGnP masterbatch pellets by Ovation Polymers (Medina, OH) using their ExTimaTM technology.
[0087] 石墨烯纳米片本质上是憎水的； 石墨烯的有效分散产生自氧与羟基官能团 （由 于在片状物断裂期间原料碳的暴露而形成） 在它们表面与 PET极性基团的相互作 用。 从上述过程获得的母料丸粒用作注塑过程的原料。 PET对照样品与增加重量 分数为 15%的 PET-xGnp纳米复合物拉伸条于 250°C-260°C温度下， 遵循 ASTM D638的型号规范 （通过引用在此并入） 注塑。  [0087] Graphene nanosheets are essentially hydrophobic; the effective dispersion of graphene is produced from oxygen and hydroxyl functional groups (formed due to exposure of the raw material carbon during sheet fracture) on their surface with PET polar groups interaction. The masterbatch pellets obtained from the above process are used as raw materials for the injection molding process. The PET control sample was extruded with a weight fraction of 15% PET-xGnp nanocomposite stretch strip at 250 °C - 260 °C, following ASTM D638 model specification (incorporated herein by reference).
[0088] 对实施例 1至 20和对比例 1至 2得到薄膜进行检测， 其中， 采用 GB/T13022-91塑 料薄膜拉伸试验方法检测上述薄膜的拉伸强度， 检测结果见表 1 ; 采用 GB/T10 38-2000检测上述薄膜的氦气透过率， 检测结果见表 1 ; 采用扫描电子显微镜方法 检测石墨烯在薄膜中的分散性， 检测结果见表 1。  [0088] The films obtained in Examples 1 to 20 and Comparative Examples 1 to 2 were tested, wherein the tensile strength of the film was measured by a tensile test method of GB/T13022-91 plastic film, and the test results are shown in Table 1; /T10 38-2000 The helium gas permeability of the above film was measured. The test results are shown in Table 1. The dispersibility of graphene in the film was examined by scanning electron microscopy. The test results are shown in Table 1.
[0089]
Figure imgf000019_0001
[0089]
Figure imgf000019_0001
由表 1看出， 本申请 PET基石墨烯复合材料中氧化石墨烯的分散性明显优于对比 例的分散性。 且由表 1中的数据对比可以看出， 本申请各实施例得到的 PET基石 墨烯复合材料的拉伸强度和氦气阻隔效果均明显优于对比例， 且通过实施例 1、 实施例 10和实施例 11的比较可以看出， 通过对乙二醇和氧化石墨烯用量进行控 制对改善 PET基石墨烯复合材料的拉伸强度和氦气阻隔效果起到明显的作用。 As seen from Table 1, the dispersibility of graphene oxide in the PET-based graphene composite material of the present application is remarkably superior to that of the comparative example. It can be seen from the comparison of the data in Table 1 that the tensile strength and the helium barrier effect of the PET-based graphene composite obtained in each of the examples of the present application are significantly better than the comparative examples, and by Embodiment 1, Example 10 It can be seen from the comparison with Example 11 that the amount of ethylene glycol and graphene oxide is controlled. The system plays a significant role in improving the tensile strength and the helium barrier effect of the PET-based graphene composite.
[0090] 从以上的描述中， 可以看出， 本发明上述的实施例实现了如下技术效果： 。 [0090] From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
[0091] 将乙二醇修饰的氧化石墨烯与 PET单体进行原位聚合反应， 利用乙二醇与 PET 单体进行反应的同吋将氧化石墨烯分散在其中， 进而改善了石墨烯在 PET基石墨 烯复合材料中的分散性。 且上述制备方法直接以 PET单体为原料， 省去了现有技 术 PET单体聚合的过程， 因此工艺简单、 制备周期短、 成本较低， 适用于大规模 工艺化生产， 所制备的 PET基石墨烯复合材料具有优异的气体阻隔性和机械强度 [0091] In-situ polymerization of ethylene glycol-modified graphene oxide with a PET monomer, and the use of ethylene glycol and a PET monomer to react with the same, dispersing graphene oxide therein, thereby improving graphene in PET Dispersibility in a graphene-based composite. Moreover, the above preparation method directly uses PET monomer as a raw material, and the process of polymerization of the prior art PET monomer is omitted, so the process is simple, the preparation cycle is short, and the cost is low, and is suitable for large-scale process production, and the prepared PET base. Graphene composites have excellent gas barrier properties and mechanical strength
[0092] 以上所述仅为本发明的优选实施例而已， 并不用于限制本发明， 对于本领域的 技术人员来说， 本发明可以有各种更改和变化。 凡在本发明的精神和原则之内 ， 所作的任何修改、 等同替换、 改进等， 均应包含在本发明的保护范围之内。 The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims

权利要求书 Claim
[权利要求 1] 一种 PET基石墨烯复合材料的制备方法， 其特征在于， 所述制备方法 包括：  [Claim 1] A method for preparing a PET-based graphene composite material, wherein the preparation method comprises:
步骤 S1， 使乙二醇修饰的氧化石墨烯与 PET单体进行酯化反应或酯交 换反应， 得到初产物， 所述 PET单体为对苯二甲酸和 /或对苯二甲酸二 甲酯；  Step S1, the ethylene glycol-modified graphene oxide is subjected to an esterification reaction or a transesterification reaction with a PET monomer to obtain a primary product, and the PET monomer is terephthalic acid and/or dimethyl terephthalate;
步骤 S2， 使所述初产物进行缩聚反应得到所述 PET基石墨烯复合材料 根据权利要求 1所述的制备方法， 其特征在于， 所述 PET单体为对苯 二甲酸， 所述步骤 S1在氮气或惰性气体气氛中进行且包括： 使乙二醇修饰的氧化石墨烯与所述对苯二甲酸在 220~250°C的温度、 0 ~0.4MPa的压强下进行所述酯化反应， 得到所述初产物， 所述酯化反 应持续 2.5~3.5h， 所述酯化反应所用的催化剂为四丙基锆、 三氧化二 锑或氢氧化锂。  Step S2, the preliminary product is subjected to a polycondensation reaction to obtain the PET-based graphene composite material. The preparation method according to claim 1, wherein the PET monomer is terephthalic acid, and the step S1 is Performing in a nitrogen or inert gas atmosphere and comprising: performing the esterification reaction between the ethylene glycol-modified graphene oxide and the terephthalic acid at a temperature of 220 to 250 ° C and a pressure of 0 to 0.4 MPa. The initial product, the esterification reaction lasts for 2.5 to 3.5 hours, and the catalyst used in the esterification reaction is tetrapropyl zirconium, antimony trioxide or lithium hydroxide.
根据权利要求 2所述的制备方法， 其特征在于， 所述乙二醇修饰的氧 化石墨烯中所述氧化石墨烯相对于所述对苯二甲酸的重量百分比为 0. 5-5%； 所述乙二醇修饰的氧化石墨烯中所述乙二醇与所述对苯二甲 酸的摩尔比为 1.5: 1-2.1:1 =  The 5% by weight of the weight percent of the graphene oxide relative to the terephthalic acid is 0. 5-5%; The ethylene glycol modified graphene oxide has a molar ratio of the ethylene glycol to the terephthalic acid of 1.5: 1-2.1:1 =
根据权利要求 1所述的制备方法， 其特征在于， 所述 PET单体为对苯 二甲酸二甲酯， 所述步骤 S1在氮气或惰性气体气氛中进行且包括： 使 乙二醇修饰的氧化石墨烯与所述对苯二甲酸二甲酯在 220~250。C的温 度、 0~0.4MPa的压强下进行酯交换反应， 得到所述初产物， 所述酯 交换反应持续 2.5~3.5h， 所述酯交换反应所用的催化剂为钛酸四丁酯 、 醋酸镁或二氧化钛。  The preparation method according to claim 1, wherein the PET monomer is dimethyl terephthalate, and the step S1 is performed in a nitrogen or inert gas atmosphere and comprises: oxidizing the ethylene glycol modified Graphene and the dimethyl terephthalate are in the range of 220 to 250. The transesterification reaction is carried out at a temperature of C and a pressure of 0 to 0.4 MPa to obtain the initial product. The transesterification reaction lasts for 2.5 to 3.5 hours, and the catalyst used for the transesterification reaction is tetrabutyl titanate or magnesium acetate. Or titanium dioxide.
根据权利要求 4所述的制备方法， 其特征在于， 所述乙二醇修饰的氧 化石墨烯中所述氧化石墨烯相对于所述对苯二甲酸二甲酯的重量百分 比为 0.5~5%; 所述乙二醇修饰的氧化石墨烯中所述乙二醇与所述对 苯二甲酸二甲酯的摩尔比为 2.1 : 1-2.7:1 = 根据权利要求 1所述的制备方法， 其特征在于， 所述步骤 S2包括： 在 260~280°C、 0~600Pa的压强下， 利用催化剂使所述初产物进行缩聚 反应得到所述 PET基石墨烯复合材料。 The method according to claim 4, wherein the weight percentage of the graphene oxide to the dimethyl terephthalate in the ethylene glycol modified graphene oxide is 0.5 to 5% ; The ethylene glycol modified graphene oxide has a molar ratio of the ethylene glycol to the dimethyl terephthalate of 2.1: 1-2.7:1 = The preparation method according to claim 1, wherein the step S2 comprises: performing a polycondensation reaction of the preliminary product with a catalyst at a pressure of 260 to 280 ° C and a temperature of 0 to 600 Pa to obtain the PET-based graphite. Aene composite.
根据权利要求 6所述的制备方法， 其特征在于， 所述步骤 S2包括： 在 265~275°C、 100~600Pa的压强下， 利用所述催化剂使所述初产物进 行预聚反应 30~90min得到预聚产物； The preparation method according to claim 6, wherein the step S2 comprises: pre-polymerizing the preliminary product by using the catalyst at a pressure of 265 to 275 ° C and a pressure of 100 to 600 Pa for 30 to 90 minutes. Obtaining a prepolymerized product;
在 265~275°C、 0~60Pa的压强下， 利用所述催化剂使所述预聚产物进 行缩聚反应 90~150min得到所述 PET基石墨烯复合材料。 The PET-based graphene composite material is obtained by subjecting the prepolymerized product to a polycondensation reaction at a pressure of 265 to 275 ° C and a temperature of 0 to 60 Pa for 90 to 150 minutes.
根据权利要求 6所述的制备方法， 其特征在于， 所述催化剂为乙二醇 锑或三氧化二锑。 The production method according to claim 6, wherein the catalyst is ethylene glycol ruthenium or antimony trioxide.
根据权利要求 1所述的制备方法， 其特征在于， 所述制备方法还包括 所述乙二醇修饰的氧化石墨烯的制备过程， 所述制备过程包括： 步骤 A， 将稳定剂溶解于乙二醇中形成乙二醇溶液； The preparation method according to claim 1, wherein the preparation method further comprises a preparation process of the ethylene glycol-modified graphene oxide, the preparation process comprising: Step A, dissolving the stabilizer in the second solution Forming an ethylene glycol solution in the alcohol;
步骤 B， 将所述乙二醇溶液与氧化石墨烯混合形成所述乙二醇修饰的 氧化石墨烯。 Step B, mixing the ethylene glycol solution with graphene oxide to form the ethylene glycol-modified graphene oxide.
根据权利要求 9所述的制备方法， 其特征在于， 所述步骤 B利用功率 为 300~1000W超声处理 0.5~2h使得所述氧化石墨烯分散在所述乙二醇 溶液中形成所述乙二醇修饰的氧化石墨烯。 The preparation method according to claim 9, wherein the step B is ultrasonically treated with a power of 300 to 1000 W for 0.5 to 2 h to disperse the graphene oxide in the ethylene glycol solution to form the ethylene glycol. Modified graphene oxide.
根据权利要求 9所述的制备方法， 其特征在于， 所述氧化石墨烯的剥 离厚度为 0.5~6nm， 长度为 10~100μηι。 The method according to claim 9, wherein the graphene oxide has a peeling thickness of 0.5 to 6 nm and a length of 10 to 100 μm.
根据权利要求 9所述的制备方法， 其特征在于， 所述稳定剂相对于所 述 PET单体的重量百分比为 0.3~0.7%， 所述稳定剂包括 N-甲基吡咯烷 酮或聚乙烯吡咯烷酮。 The preparation method according to claim 9, wherein the stabilizer is 0.3 to 0.7% by weight based on the PET monomer, and the stabilizer comprises N-methylpyrrolidone or polyvinylpyrrolidone.
一种 PET基石墨烯复合材料， 其特征在于， 所述 PET基石墨烯复合材 料为利用权利要求 1至 12中任一项所述的制备方法制备而成， 所述 PE T基石墨烯复合材料的拉伸强度为 7500~12500MPa， 氦气透过率为 800 ~950ml/m 2.day.0.1MPa。 A PET-based graphene composite material, which is prepared by the preparation method according to any one of claims 1 to 12, wherein the PE T-based graphene composite material is prepared. The tensile strength is 7500~12500MPa, and the helium permeability is 800 ~ 950ml/m 2 .day.0.1MPa.
一种浮空器， 所述浮空器具有蒙皮材料， 所述蒙皮材料包括阻气层， 其特征在于， 形成所述阻气层的材料包括权利要求 13所述的 PET基石 墨烯复合材料。 An aerostat having a skin material, the skin material comprising a gas barrier layer, It is characterized in that the material forming the gas barrier layer comprises the PET-based graphene composite material according to claim 13.
[权利要求 15] 根据权利要求 14所述的浮空器， 其特征在于， 所述蒙皮材料包括依次 设置的耐候层、 纤维层和所述阻气层， 或包括依次设置的耐候层、 所 述阻气层和纤维层。  [Claim 15] The aerostat according to claim 14, wherein the skin material comprises a weathering layer, a fiber layer, and a gas barrier layer, which are sequentially disposed, or includes a weathering layer, a chamber, which are sequentially disposed The gas barrier layer and the fiber layer are described.
PCT/CN2016/109113 2016-02-29 2016-12-09 Pet-based graphene composite material and preparation method therefor, and aerostat WO2017148198A1 (en)

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