WO2018036423A1 - 基于三维石墨烯改性的塑料复合材料及其制备 - Google Patents

基于三维石墨烯改性的塑料复合材料及其制备 Download PDF

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WO2018036423A1
WO2018036423A1 PCT/CN2017/098064 CN2017098064W WO2018036423A1 WO 2018036423 A1 WO2018036423 A1 WO 2018036423A1 CN 2017098064 W CN2017098064 W CN 2017098064W WO 2018036423 A1 WO2018036423 A1 WO 2018036423A1
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graphene
dimensional graphene
dimensional
oxidation
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段曦东
赵涛楠
毛志浩
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广东纳路纳米科技有限公司
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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
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • 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
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature

Definitions

  • the invention relates to the technical field of materials, in particular to a plastic composite material based on three-dimensional graphene modification and preparation thereof.
  • thermal conductive materials have been unable to meet the needs of certain special occasions, such as those used in chemical production and wastewater treatment.
  • Heat exchangers require both materials to be thermally conductive and chemically resistant.
  • High-power tubes are used in electronic circuits, and insulated parts are required at the bottom.
  • the resources of non-ferrous metals are tight, and it is necessary to develop a heat-conducting material that can replace metal aluminum and copper.
  • thermal conductive plastics Due to its stable chemical properties, light weight and firmness, excellent mechanical and fatigue resistance, good processing performance and low price, thermal conductive plastics have been widely used in industrial production and have gradually become a new role in the field of heat conduction.
  • pure plastic is generally incapable, because plastic is mostly a poor conductor of heat, and the thermal conductivity is usually only 0.2 W/(m ⁇ K).
  • Conductive plastics have the density of plastics, and have the electrical conductivity of metals and the processability of plastics. In addition, they have electrochemical properties that are lacking in metals and plastics for antistatic, electromagnetic shielding, color display, microwave absorption and electrochemistry. And other fields. Conductive plastics can generally be divided into structural and composite types. Structural conductive plastics are plastics that are electrically conductive or chemically modified. Because of the high production cost and high process difficulty of this type of plastic, there is still no such Mass production; composite conductive plastic refers to a plastic that has been electrically modified, and is generally made of a resin as a matrix, and is filled with a filler having excellent electrical conductivity and other additives.
  • the composite conductive plastic has more advantages in research and application than the structural conductive plastic because of its light weight, easy molding, low total cost and adjustable electrical conductivity in a wide range, and many varieties have been industrially produced.
  • conventional composite conductive plastics are guided
  • the amount of electric filler added is insufficient to meet the processing needs of high-end electrical equipment, but the addition of a large amount of conductive filler will cause a decrease in mechanical properties and limit its large-scale use in precision electrical components.
  • the three-dimensional graphene-modified plastic composite material of the present invention comprises a plastic substrate having a mass percentage of 95% to 99.9% and a 0.1%-5% three-dimensional graphene.
  • the plastic substrate comprises PA, PE, PP, PVC, POM, PC, PMMA, ABS, PS, PPS, nylon 66, EP, PF, PTFE, PVDF, PPA, PEEK, HDPE, LCP, PVA, One of PE-RT and TPE.
  • the three-dimensional graphene has a three-dimensional interconnected porous network of submicron to several micrometers.
  • Step 1) preparing graphene oxide by a modified Hummers method
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in the step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1-2 mg/ml, and then transferred to a reaction vessel at 160-200 ° C for 20-24 hours, washed with water. , obtaining a three-dimensional reduced graphene oxide hydrogel, freeze-dried;
  • Step 3) The three-dimensional graphene and the plastic substrate prepared in the step 2) are mixed in a high-speed mixer for 2-15 min, and then blended and granulated by adding a twin-screw extruder, and the temperature of the extruder is set at 170-280 ° C. A three-dimensional graphene-modified plastic composite material is obtained.
  • the improved Hummers method produces graphene oxide, including pre-oxidation and oxidation and stripping
  • the pre-oxidation is: mixing 1 part of natural graphite, 3-10 parts of concentrated sulfuric acid, 0.5-0.9 parts of K 2 S 2 O 8 and P 2 O 5 to 80 ° C, reacting for 6 h, using super Purified pure water to neutral to obtain pre-oxidized graphite;
  • the oxidation is: at 0 ° C, the pre-oxidized graphite is mixed with 6-20 parts of concentrated sulfuric acid, and gradually added 1-3 parts of KMnO 4 under stirring, in the process controlling the mixture temperature below 20 ° C;
  • the mixture was heated to 35 ° C, and after stirring for 2 h, 20-50 parts of ultrapure water was added, stirring was continued for 15 min, and then the reaction was terminated by adding 40-150 parts of ultrapure water; then, 2 parts of 30% H 2 O 2 was added , and the mixture was added.
  • the mixture was washed with 10% HCl to remove excess metal ions, and the resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral;
  • Three-dimensional graphene has a self-supporting structure, unique properties such as flexibility, porosity, and high active surface area, and is easy to be in close contact with the substrate, and has good dispersibility in the resin;
  • Three-dimensional graphene has excellent electrical conductivity, thermal conductivity and mechanical properties, and can greatly improve the electrical conductivity, thermal conductivity and mechanical properties of plastic products without affecting other properties;
  • the invention has simple preparation process, low production cost, no environmental pollution, and is easy to realize large-scale industrial production.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation mixing 1 part of natural graphite, 3 parts of concentrated sulfuric acid, 0.5 part of K 2 S 2 O 8 and P 2 O 5 to 80 ° C, reacting for 6 h, and washing with ultrapure water until neutral Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 6 parts of concentrated sulfuric acid at 0 ° C, and 1 part of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 20 parts of ultrapure water was added, stirring was continued for 15 min, and the reaction was completed by adding 40 parts of ultrapure water.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated for 30 min with a 400 W cell pulverizer, and the supernatant was centrifuged at 13,000 rpm, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in the step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1 mg/ml, and then transferred to a reaction vessel at 160 ° C for 20 hours, and washed with water to obtain a three-dimensional reduced graphite oxide.
  • Step 3 Mixing 3% graphene with a mass percentage of 0.5% and PET substrate with a mass percentage of 99.5% in a high-speed mixer for 2 min, and then adding a twin-screw extruder for blending and granulating, and extruding
  • the outlet temperature was set at 260 ° C to produce a three-dimensional graphene/PET composite with high electrical and thermal conductivity.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by weight of natural graphite, 4 parts of concentrated sulfuric acid, 0.6 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 7 parts of concentrated sulfuric acid at 0 ° C, and 1.5 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 25 parts of ultrapure water was added, stirring was continued for 15 min, and the reaction was completed by adding 50 parts of ultrapure water.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.5 mg/ml, and then transferred to a reaction vessel at 180 ° C for 20 h, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3) mixing the 1% by mass of the three-dimensional graphene prepared in the step 2) and the 99% by mass plastic substrate PS in a high-speed mixer for 4 minutes, and then adding the twin-screw extruder to blend and granulate.
  • the extruder temperature was set at 180 ° C to produce a highly conductive and thermally conductive three-dimensional graphene/PS composite.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by weight of natural graphite, 5 parts of concentrated sulfuric acid, 0.7 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in the step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.8 mg/ml, and then transferred to a reaction vessel at 180 ° C for 24 hours, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3 Mixing 1.5% by mass of the three-dimensional graphene and 98.5% by mass of the plastic substrate HDPE in a high-speed mixer for 6 minutes, and then adding the twin-screw extruder to blend and granulate, and extruding
  • the outlet temperature was set at 180 ° C to produce a three-dimensional graphene/HDPE composite with high electrical and thermal conductivity.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by weight of natural graphite, 6 parts of concentrated sulfuric acid, 0.8 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 hours, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 9 parts of concentrated sulfuric acid at 0 ° C, and 1.5 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 35 parts of ultrapure water was added, stirring was continued for 15 min, and the reaction was completed by adding 60 parts of ultrapure water.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 180 ° C for 24 hours, and washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3) The 2% graphene and the mass percentage obtained by the step 2) are 2% by mass 98% of the plastic substrate PA6 was mixed in a high-speed mixer for 8 minutes, and then blended and granulated by adding a twin-screw extruder. The temperature of the extruder was set at 260 ° C to obtain a three-dimensional graphene/PA6 composite material with high electrical and thermal conductivity. .
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by mass of natural graphite, 7 parts of concentrated sulfuric acid, 0.8 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 10 parts of concentrated sulfuric acid at 0 ° C, and 2 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 40 parts of ultrapure water was added, stirring was continued for 15 min, and the reaction was completed by adding 70 parts of ultrapure water.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in the step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 200 ° C for 20 hours, and washed with water to obtain a three-dimensional reduced graphite oxide.
  • Step 3) Mixing the 3% by weight of the three-dimensional graphene prepared in the step 2) and the plastic substrate PP having a mass percentage of 97% in a high-speed mixer for 12 minutes, and then adding the twin-screw extruder to blend and granulate, and extruding
  • the outlet temperature was set at 180 ° C to produce a three-dimensional graphene/PP composite with high electrical and thermal conductivity.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation Mix 1 part of natural graphite, 8 parts of concentrated sulfuric acid, 0.8 parts of K 2 S 2 O 8 and P 2 O 5 to 80 ° C, react for 6 h, and wash with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 12 parts of concentrated sulfuric acid at 0 ° C, and 2 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 50 parts of ultrapure water was added, stirring was continued for 15 min, and the reaction was completed by adding 90 parts of ultrapure water.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated for 30 min with a 400 W cell pulverizer, and the supernatant was centrifuged at 13,000 rpm, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in the step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 200 ° C for 20 hours, and washed with water to obtain a three-dimensional reduced graphite oxide.
  • Step 3) Mixing 4% by mass of the three-dimensional graphene prepared in the step 2) and the plastic substrate ABS having a mass percentage of 96% in a high-speed mixer for 16 minutes, and then adding the twin-screw extruder to blend and granulate, and extruding
  • the outlet temperature was set at 200 ° C to obtain a highly conductive and thermally conductive three-dimensional graphene/ABS composite.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by weight of natural graphite, 10 parts of concentrated sulfuric acid, 0.9 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 16 parts of concentrated sulfuric acid at 0 ° C, and 3 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 50 parts of ultrapure water was added, stirring was continued for 15 min, and the reaction was completed by adding 120 parts of ultrapure water.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 200 ° C for 24 hours, and washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3) Mixing the 3% by weight of the three-dimensional graphene prepared in the step 2) and the plastic substrate PPS having a mass percentage of 95% in a high-speed mixer for 20 minutes, and then adding the twin-screw extruder to blend and granulate, and extruding
  • the outlet temperature was set at 280 ° C to produce a highly conductive and thermally conductive three-dimensional graphene/PPS composite.
  • Comparative Examples 1, 2, 3, and 4 are commercially available PET, PS, HDPE, and PA6, respectively, which were purchased from Dongguan Longchuang Plastic Co., Ltd.
  • Table 1 shows the performance parameters of the three-dimensional graphene-modified plastic composite material prepared in Example 17 and Comparative Example 1-4 plastic substrate:
  • the preparation method of the present invention can greatly improve the electrical conductivity, thermal conductivity and mechanical strength of the plastic.

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Abstract

一种基于三维石墨烯改性的塑料复合材料，包括质量百分含量为95％-99.9％的塑料基材和0.1％-5％三维石墨烯。三维石墨烯是二维石墨烯片的三维结构组装体，不但具有石墨烯优异的导电、导热和力学性能，还具有柔韧性、多孔性、高活性表面积等独特的性质，能够与基体材料紧密接触，使得三维石墨烯在塑料基材中可以均匀分布，增强了塑料制品的导电性、导热性和机械性能。

Description

基于三维石墨烯改性的塑料复合材料及其制备 技术领域
本发明涉及材料技术领域，具体涉及一种基于三维石墨烯改性的塑料复合材料及其制备。
背景技术
随着工业生产和科学技术的发展，人们对导热材料综合性能的要求也越来越高，传统的金属、陶瓷等材料已无法满足某些特殊场合的需求，如化工生产和废水处理中使用的热交换器，既需要材料具有导热能力，又要求其耐化学腐蚀；在电子电路中使用大功率管，其底部就需要绝缘的散热器件。另外有色金属资源紧张，有必要开发一种可代替金属铝、铜的导热材料。导热塑料由于具有稳定的化学性质、质轻且坚固、优良的力学及抗疲劳性能、良好的加工性能、低廉的价格，在工业生产中得到大量的应用，逐渐成为导热领域的新角色。但作为导热材料，纯的塑料一般是不能胜任的，因为塑料大多是热的不良导体，通常热传导率只有0.2W/(m·K)。
导电塑料具有塑料的密度，同时具有金属的导电性和塑料的可加工性，此外还具备金属和塑料所欠缺的电化学性能，以应用于抗静电、电磁屏蔽、彩色显示、微波吸收及电化学等领域。导电塑料一般可分为结构型和复合型，结构型导电塑料是本身具有导电性或经化学改性后具有导电性的塑料，由于这一类塑料的生产成本高、工艺难度大，至今尚无大量生产；复合型导电塑料是指经物理改性后具有导电性的塑料，一般以某种树脂为基体，加入具有优异导电性能的填料及其他添加剂复合而成。复合型导电塑料因具有重量轻、易成型、总成本低并且可以在较宽范围内调节导电性能等优点，使其较结构型导电塑料的研究和应用更为成熟，不少品种已工业化生产。但常规复合型导电塑料由于导 电填料添加量不足，无法满足高端电气设备加工需要，但添加大量导电填料，又会造成机械性能降低，限制其在精密电器元件中的大规模使用。
发明内容
有鉴于此，有必要针对上述的问题，提供一种既具有良好的导电性，又具有优异导热性能，且方便机械加工的基于三维石墨烯改性的塑料复合材料及其制备。
为实现上述目的，本发明采取以下的技术方案：
本发明的基于三维石墨烯改性的塑料复合材料，包括质量百分含量为95％-99.9％的塑料基材和0.1％-5％三维石墨烯。
进一步的，所述塑料基材包括PA、PE、PP、PVC、POM、PC、PMMA、ABS、PS、PPS、尼龙66、EP、PF、PTFE、PVDF、PPA、PEEK、HDPE、LCP、PVA、PE-RT、TPE中的一种。
进一步的，所述的三维石墨烯具有亚微米至数微米的三维连通多孔网络。
一种基于三维石墨烯改性的塑料复合材料的制备，包括：
步骤1)通过改进的Hummers方法制备氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1-2mg/ml，之后转移到反应釜中160-200℃反应20-24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将步骤2)制得的三维石墨烯和塑料基材在高速搅拌机中混合2-15min，再加入双螺杆挤出机中共混造粒，挤出机温度设定在170-280℃，制得三维石墨烯改性的塑料复合材料。
进一步的，所述改进的Hummers方法制备氧化石墨烯，包括预氧化和氧化和剥离；
所述预氧化为：将质量份为1份的天然石墨、3-10份浓硫酸、0.5-0.9份的 K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨；
所述氧化为：0℃下，将预氧化石墨与6-20份的浓硫酸混合，在搅拌下逐渐加入1-3份的KMnO4，在此过程中控制混合物温度在20℃以下；再将混合物升温至35℃，搅拌2h后，加入20-50份超纯水，继续搅拌15min，昀后加入40-150份超纯水结束反应；接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子，得到的沉淀用超纯水反复离心清洗至溶液呈中性；
剥离：为了剥离氧化石墨，得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯。
本发明的有益效果为：
(1)三维石墨烯具有自支撑结构，柔韧性、多孔性、高活性表面积等独特的性质，易与基体紧密接触，在树脂中有良好的分散性；
(2)三维石墨烯具有优异的导电性能、导热性能和力学性能，能大幅度提高塑料制品的导电性、导热性和机械性能而其他性能不受影响；
(3)本发明制备工艺简单、生产成本低、无环境污染，易于实现大规模的工业化生产。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案作进一步清楚、完整地描述。需要说明的是，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、3份浓硫酸、0.5份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与6份的浓硫酸混合，在搅拌下逐渐加入1份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入20份超纯水，继续搅拌15min，昀后加入40份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1mg/ml，之后转移到反应釜中160℃反应20h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将步骤2)制得的质量百分比为0.5％的三维石墨烯和质量百分比为99.5％的塑料基材PET在高速搅拌机中混合2min，再加入双螺杆挤出机中共混造粒，挤出机温度设定在260℃，制得高导电导热性的三维石墨烯/PET复合材料。
实施例2
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、4份浓硫酸、0.6份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与7份的浓硫酸混合，在搅拌下逐渐加入1.5份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入25份超纯水，继续搅拌15min，昀后加入50份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1.5mg/ml，之后转移到反应釜中180℃反应20h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将将步骤2)制得的质量百分比为1％的三维石墨烯和质量百分比为99％的塑料基材PS在高速搅拌机中混合4min，再加入双螺杆挤出机中共混造粒，挤出机温度设定在180℃，制得高导电导热性的三维石墨烯/PS复合材料。
实施例3
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、5份浓硫酸、0.7份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将氧化石墨与8份的浓硫酸混合，在搅拌下逐渐加入2份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入30份超纯水，继续搅拌15min，昀后加入60份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min， 13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1.8mg/ml，之后转移到反应釜中180℃反应24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将步骤2)制得的质量百分比为1.5％的三维石墨烯和质量百分比为98.5％的塑料基材HDPE在高速搅拌机中混合6min，再加入双螺杆挤出机中共混造粒，挤出机温度设定在180℃，制得高导电导热性的三维石墨烯/HDPE复合材料。
实施例4
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、6份浓硫酸、0.8份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与9份的浓硫酸混合，在搅拌下逐渐加入1.5份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入35份超纯水，继续搅拌15min，昀后加入60份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为2mg/ml，之后转移到反应釜中180℃反应24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将步骤2)制得的质量百分比为2％的三维石墨烯和质量百分比为 98％的塑料基材PA6在高速搅拌机中混合8min，再加入双螺杆挤出机中共混造粒，挤出机温度设定在260℃，制得高导电导热性的三维石墨烯/PA6复合材料。
实施例5
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、7份浓硫酸、0.8份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与10份的浓硫酸混合，在搅拌下逐渐加入2份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入40份超纯水，继续搅拌15min，昀后加入70份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为2mg/ml，之后转移到反应釜中200℃反应20h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将步骤2)制得的质量百分比为3％的三维石墨烯和质量百分比为97％的塑料基材PP在高速搅拌机中混合12min，再加入双螺杆挤出机中共混造粒，挤出机温度设定在180℃，制得高导电导热性的三维石墨烯/PP复合材料。
实施例6
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、8份浓硫酸、0.8份的K2S2O8及P2O5 混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与12份的浓硫酸混合，在搅拌下逐渐加入2份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入50份超纯水，继续搅拌15min，昀后加入90份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为2mg/ml，之后转移到反应釜中200℃反应20h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将步骤2)制得的质量百分比为4％的三维石墨烯和质量百分比为96％的塑料基材ABS在高速搅拌机中混合16min，再加入双螺杆挤出机中共混造粒，挤出机温度设定在200℃，制得高导电导热性的三维石墨烯/ABS复合材料。
实施例7
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、10份浓硫酸、0.9份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与16份的浓硫酸混合，在搅拌下逐渐加入3份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入50份超纯水，继续搅拌15min，昀后加入120份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为2mg/ml，之后转移到反应釜中200℃反应24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将步骤2)制得的质量百分比为5％的三维石墨烯和质量百分比为95％的塑料基材PPS在高速搅拌机中混合20min，再加入双螺杆挤出机中共混造粒，挤出机温度设定在280℃，制得高导电导热性的三维石墨烯/PPS复合材料。
对比例1、2、3、4分别为市售的PET、PS、HDPE、PA6，购自东莞龙创塑胶有限公司。
表1中为测定实施例17中所制备得到的三维石墨烯改性的塑料复合材料及对比例1-4塑料基材的性能参数：
表1各实施例材料的性能数据
Figure PCTCN2017098064-appb-000001
从上表可知，本发明的制备方法可以大幅度提高塑料的导电、导热性能和机械强度。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (5)

  1. 一种基于三维石墨烯改性的塑料复合材料，其特征在于，包括质量百分含量为95％-99.9％的塑料基材和0.1％-5％三维石墨烯。
  2. 根据权利要求1所述的一种基于三维石墨烯改性的塑料复合材料，其特征在于，所述塑料基材包括PA、PE、PP、PVC、POM、PC、PMMA、ABS、PS、PPS、尼龙66、EP、PF、PTFE、PVDF、PPA、PEEK、HDPE、LCP、PVA、PE-RT、TPE中的一种。
  3. 根据权利要求1所述的一种基于三维石墨烯改性的塑料复合材料，其特征在于，所述的三维石墨烯具有亚微米至数微米的三维连通多孔网络。
  4. 一种权利要求1所述的基于三维石墨烯改性的塑料复合材料的制备方法，其特征在于，包括：
    步骤1)通过改进的Hummers方法制备氧化石墨烯；
    步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1-2mg/ml，之后转移到反应釜中160-200℃反应20-24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
    步骤3)将步骤2)制得的三维石墨烯和塑料基材在高速搅拌机中混合2-15min，再加入双螺杆挤出机中共混造粒，挤出机温度设定在170-280℃，制得三维石墨烯改性的塑料复合材料。
  5. 根据权利要求4所述的基于三维石墨烯改性的塑料复合材料的制备方法，其特征在于，所述改进的Hummers方法制备氧化石墨烯，包括预氧化和氧化和剥离；
    所述预氧化为：将质量份为1份的天然石墨、3-10份浓硫酸、0.5-0.9份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨；
    所述氧化为：0℃下，将氧化石墨与6-20份的浓硫酸混合，在搅拌下逐渐 加入1-3份的KMnO4，在此过程中控制混合物温度在20℃以下；再将混合物升温至35℃，搅拌2h后，加入20-50份超纯水，继续搅拌15min，昀后加入40-150份超纯水结束反应；接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子，得到的沉淀用超纯水反复离心清洗至溶液呈中性；
    剥离：为了剥离氧化石墨，得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯。
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