CN115260581B - Multifunctional graphene polyamide master batch and preparation method thereof - Google Patents
Multifunctional graphene polyamide master batch and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 97
- 239000004952 Polyamide Substances 0.000 title claims abstract description 85
- 229920002647 polyamide Polymers 0.000 title claims abstract description 85
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 66
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 40
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 33
- 239000011787 zinc oxide Substances 0.000 claims abstract description 33
- 239000002270 dispersing agent Substances 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 29
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000005303 weighing Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000523 sample Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K3/041—Carbon nanotubes
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- 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
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- 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
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention discloses a multifunctional graphene polyamide master batch and a preparation method thereof, wherein the multifunctional graphene polyamide master batch comprises the following raw materials in parts by weight: graphene oxide, modified polyamide, carbon nanotubes, montmorillonite, a dispersing agent and an antioxidant. According to the invention, the polyamide is modified by utilizing the nano zinc oxide and then blended with the graphene to prepare the master batch, so that the impact resistance and toughness of the master batch can be improved, the surface area is large compared with the dispersion of the nano zinc oxide, the contact area with a matrix is large, the surface active center is more, better interface combination with the matrix is realized, the compatibility is better, when the nano zinc oxide is subjected to external force, particles are not easy to separate from the matrix, and a plurality of micro deformation areas are generated in the master batch due to the interaction of an external force field, and a large amount of energy is absorbed, so that the enhancement and toughness effect can be achieved, the composite material has better mechanical property, and the crystallinity and barrier property of the polyamide composite material can be improved after montmorillonite is added.
Description
Technical Field
The invention relates to the technical field of polyamide, in particular to a multifunctional graphene polyamide master batch and a preparation method thereof.
Background
The master batch is a particle material prepared by firstly mixing and mixing various required auxiliary agents, fillers and a small amount of carrier resin in the plastic processing and forming process for convenience in operation, and metering, mixing, melting, extruding, granulating and other processing processes through equipment such as an extruder and the like, and is called a master batch. The master batch is a concentrate of various plastic additives, and the direct addition of the additives is not easy to disperse and has low use efficiency, so the master batch is often added in the form of master batch. Graphene is formed from sp 2 The hybridized carbon atoms are orderly arranged on a two-dimensional plane, the thickness is only one carbon atom diameter, the material is the thinnest and the hardest material in the current world, the structure is unique, the heat conductivity, the electrical conductivity, the stability and the huge specific surface area are good, one of the excellent choices for improving the characteristics of the composite material is realized, and the multifunctional graphene is widely applied; because ofIn this way, when graphene is used as a nano additive and the addition amount is low, the performance of the polymer material can be greatly enhanced.
However, due to strong van der Waals interaction force among particles of the graphene, the particles are easy to agglomerate, and when the graphene and the polymer are mixed to prepare master batches, the defect of agglomeration can reduce the toughness resistance of the graphene polyamide master batches.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a multifunctional graphene polyamide master batch and a preparation method thereof, and the problems to be solved by the invention are as follows: how to improve the toughness resistance of the graphene polyamide master batch.
In order to achieve the above purpose, the present invention provides the following technical solutions: the multifunctional graphene polyamide master batch comprises the following raw materials in parts by weight: 40-85 parts of graphene oxide, 20-50 parts of modified polyamide, 6-16 parts of carbon nano tube, 5-12 parts of montmorillonite, 1-3 parts of dispersing agent and 1-3 parts of antioxidant.
Further, the material comprises the following raw materials in parts by weight: 50-75 parts of graphene oxide, 30-50 parts of modified polyamide, 9-13 parts of carbon nano tube, 7-10 parts of montmorillonite, 1.5-2.5 parts of dispersing agent and 1.5-2.5 parts of antioxidant.
Further, the material comprises the following raw materials in parts by weight: 62 parts of graphene oxide, 65 parts of modified polyamide, 11 parts of carbon nano tube, 8.5 parts of montmorillonite, 2 parts of dispersing agent and 2 parts of antioxidant.
Further, the dispersing agent is one or more of polyethylene wax, polypropylene wax and ethylene-vinyl acetate copolymer wax.
Further, the antioxidant is one or more of N-phenyl-alpha-naphthylamine, alkyl phenothiazine and benzotriazole derivatives.
The invention also provides a preparation method of the multifunctional graphene polyamide master batch, which comprises the following specific preparation steps:
step one: weighing graphene oxide prepared by a Staudenmailer method, dispersing the graphene oxide in water by utilizing ultrasonic waves for 5-10min, and stirring the graphene oxide for 10-15 min to obtain a graphene oxide mixed solution for later use;
step two: adding carbon nanotubes into the reaction container in the first step, keeping the rotating speed at 300-350 r/min, and continuously stirring for 20-30 min to fully mix the carbon nanotubes with the graphene oxide mixed solution to obtain a mixture A for later use;
step three: the preparation process of the modified polyamide comprises the following steps: weighing silane coupling agent KH-560, completely dissolving in isopropanol, adding zinc oxide, mechanically stirring in a reactor at 75-110 ℃ for reaction for 3-7h, suction filtering, extracting with isoascorbate at 75-100 ℃ for 4-7h, and vacuum drying at 40-65 ℃ for 10-15h to obtain a surface modified zinc oxide sample I; mixing the dried polyamide with olefine acid according to the weight ratio of 1: uniformly mixing the materials according to the mass ratio of 0.7, putting the mixture into an HAKKE rheometer, wherein the processing temperature is 200-260 ℃, the rotor speed is 180-240rpm, the blending time is 5-10min, and melting and blending to obtain a second sample for later use; weighing the following components in percentage by mass: putting a zinc oxide sample I and a zinc oxide sample II of 45 into a HAKKE rheometer to be melt-blended to obtain modified polyamide for later use, wherein the processing temperature is 200-240 ℃, the rotor speed is 130-180 rpm, and the blending time is 10-18 min;
step four: weighing montmorillonite, putting the montmorillonite into a ball mill, and grinding to obtain montmorillonite powder for standby, wherein the particle size is larger than or equal to 300 meshes;
step five: fully and uniformly mixing the obtained mixture A, modified polyamide and montmorillonite powder in a reaction container containing an organic solvent under the conditions of ultrasonic dispersion and mechanical stirring, adding a dispersing agent and an antioxidant which are melted into a liquid state to obtain a mixture, continuously performing ultrasonic dispersion and mechanical stirring to ensure that the mixture is uniform, removing the organic solvent, putting the mixture into the reaction container, and controlling the reaction time to be 60-110 min and the reaction temperature to be 180-240 ℃; and adding the obtained mixture into an extruder to extrude into filaments, and cooling and granulating to obtain the multifunctional graphene polymer master batch.
Further, the mass ratio of the graphene oxide mixed solution to the carbon nanotubes in the second step is 1.5:6.2.
further, the mass ratio of the polyamide to the nano zinc oxide in the third step is 1: (5-10.2).
Further, the mass ratio of the mixture A, the modified polyamide, the montmorillonite powder, the dispersing agent and the antioxidant in the fifth step is 43: (51-63): 22:2.1:2.1.
further, the mass ratio of the organic solvent in the fifth step is 1: (1.3-2.1) N, N-dimethylformamide and toluene.
The invention has the technical effects and advantages that:
1. the multifunctional graphene polyamide master batch prepared by adopting the raw material formula disclosed by the invention is prepared by modifying polyamide by utilizing nano zinc oxide and then blending the modified polyamide with graphene, so that the impact resistance and toughness of the master batch can be improved, as compared with the dispersion of nano zinc oxide, the master batch has large surface area, large contact area with a matrix and multiple surface active centers, better interface combination with the matrix can be realized, the compatibility is better, particles are not easy to separate from the matrix when external force is applied, and because of the interaction of an external force field, a plurality of micro deformation areas are generated in the master batch, a great amount of energy is absorbed, thereby the reinforcing and toughening effects are achieved, the composite material has better mechanical properties, the crystallinity and barrier property of the polyamide composite material can be increased after the montmorillonite is added, and due to the unique laminar one-dimensional nano structure characteristic and morphological characteristic of the montmorillonite, the interlayer has designable reactivity, and the oversized specific surface area and the diameter/thickness ratio of the montmorillonite is up to more than 200, so that the performance of the added composite material is substantially improved.
2. The multifunctional graphene polyamide master batch prepared by the raw material formula disclosed by the invention is prepared by mixing the tubular carbon nanotubes and the flaky graphene oxide, and then preparing the master batch with polyamide, so that the conductivity of the master batch can be enhanced, and compared with a conductive network formed by zero-dimensional point connection between the individual carbon nanotubes and between the graphene, the tubular carbon nanotubes in the hybrid filler have a bridging effect on the connection of the flaky graphene, and the formed one-dimensional line connection can obviously increase the interface contact area, so that the hybrid nano filler has a synergistic enhancement effect on the conductivity of the polyamide composite material.
Detailed Description
The invention is further described below in connection with specific embodiments.
Example 1
The multifunctional graphene polyamide master batch of the embodiment comprises the following raw materials in parts by weight: 40 parts of graphene oxide, 20 parts of modified polyamide, 6 parts of carbon nano tube, 5 parts of montmorillonite, 1 part of dispersing agent and 1 part of antioxidant.
The dispersing agent is polyethylene wax.
The antioxidant is N-phenyl-alpha-naphthylamine.
The preparation method comprises the following specific steps:
step one: weighing graphene oxide prepared by a Staudenmailer method, dispersing the graphene oxide in water for 8min by utilizing ultrasonic waves, and stirring the graphene oxide for 12min to obtain a graphene oxide mixed solution for later use;
step two: adding carbon nanotubes into the reaction container in the first step, keeping the rotating speed at 320 revolutions per minute, and continuously stirring for 25 minutes to fully mix the carbon nanotubes with the graphene oxide mixed solution to obtain a mixture A for later use;
step three: the preparation process of the modified polyamide comprises the following steps: weighing silane coupling agent KH-560, completely dissolving in isopropanol, adding zinc oxide, mechanically stirring at 90 ℃ in a reactor for reaction for 5 hours, carrying out suction filtration, extracting with isoascorbate at 80 ℃ for 5 hours, and carrying out vacuum drying at 50 ℃ for 12 hours to obtain a surface modified zinc oxide sample I; mixing the dried polyamide with olefine acid according to the weight ratio of 1: uniformly mixing the materials according to the mass ratio of 0.7, putting the mixture into an HAKKE rheometer, wherein the processing temperature is 220 ℃, the rotor speed is 200rpm, the mixing time is 8min, and carrying out melt mixing to obtain a second sample for later use; weighing the following components in percentage by mass: putting a first zinc oxide sample and a second zinc oxide sample of 45 into a HAKKE rheometer, and carrying out melt blending to obtain modified polyamide for later use, wherein the processing temperature is 20 ℃, the rotor speed is 150rpm, and the blending time is 15min;
step four: weighing montmorillonite, putting the montmorillonite into a ball mill, and grinding to obtain montmorillonite powder for standby, wherein the particle size is larger than or equal to 300 meshes;
step five: fully and uniformly mixing the obtained mixture A, modified polyamide and montmorillonite powder in a reaction container containing an organic solvent under the conditions of ultrasonic dispersion and mechanical stirring, adding a dispersing agent and an antioxidant which are melted into a liquid state to obtain a mixture, continuously performing ultrasonic dispersion and mechanical stirring to ensure that the mixture is uniform, removing the organic solvent, putting the mixture into the reaction container, and controlling the reaction time to be 80 minutes, wherein the reaction temperature is 200 ℃; and adding the obtained mixture into an extruder to extrude into filaments, and cooling and granulating to obtain the multifunctional graphene polymer master batch.
The mass ratio of the graphene oxide mixed solution to the carbon nano tube in the second step is 1.5:6.2.
the mass ratio of the polyamide to the nano zinc oxide in the third step is 1:7.
the mass ratio of the mixture A, the modified polyamide, the montmorillonite powder, the dispersing agent and the antioxidant in the fifth step is 43:52:22:2.1:2.1.
the mass ratio of the organic solvent in the fifth step is 1: 1.5N, N-dimethylformamide and toluene.
Example 2
Unlike example 1, the multifunctional graphene polyamide masterbatch of this example comprises the following raw materials in parts by weight: 62 parts of graphene oxide, 65 parts of modified polyamide, 11 parts of carbon nano tube, 8.5 parts of montmorillonite, 2 parts of dispersing agent and 2 parts of antioxidant.
Example 3
Different from examples 1-2, the multifunctional graphene polyamide masterbatch of the present embodiment comprises the following raw materials in parts by weight: 85 parts of graphene oxide, 50 parts of modified polyamide, 16 parts of carbon nano tube, 12 parts of montmorillonite, 3 parts of dispersing agent and 3 parts of antioxidant.
Example 4
The multifunctional graphene polyamide master batch of the embodiment comprises the following raw materials in parts by weight: 40 parts of graphene oxide, 20 parts of modified polyamide, 6 parts of carbon nano tube, 5 parts of montmorillonite, 1 part of dispersing agent and 1 part of antioxidant.
The dispersing agent is polyethylene wax.
The antioxidant is N-phenyl-alpha-naphthylamine.
The preparation method comprises the following specific steps:
step one: weighing graphene oxide prepared by a Staudenmailer method, dispersing the graphene oxide in water for 8min by utilizing ultrasonic waves, and stirring the graphene oxide for 12min to obtain a graphene oxide mixed solution for later use;
step two: the preparation process of the modified polyamide comprises the following steps: weighing silane coupling agent KH-560, completely dissolving in isopropanol, adding zinc oxide, mechanically stirring at 90 ℃ in a reactor for reaction for 5 hours, carrying out suction filtration, extracting with isoascorbate at 80 ℃ for 5 hours, and carrying out vacuum drying at 50 ℃ for 12 hours to obtain a surface modified zinc oxide sample I; mixing the dried polyamide with olefine acid according to the weight ratio of 1: uniformly mixing the materials according to the mass ratio of 0.7, putting the mixture into an HAKKE rheometer, wherein the processing temperature is 220 ℃, the rotor speed is 200rpm, the mixing time is 8min, and carrying out melt mixing to obtain a second sample for later use; weighing the following components in percentage by mass: putting a first zinc oxide sample and a second zinc oxide sample of 45 into a HAKKE rheometer, and carrying out melt blending to obtain modified polyamide for later use, wherein the processing temperature is 20 ℃, the rotor speed is 150rpm, and the blending time is 15min;
step three: weighing montmorillonite, putting the montmorillonite into a ball mill, and grinding to obtain montmorillonite powder for standby, wherein the particle size is larger than or equal to 300 meshes;
step four: fully and uniformly mixing the graphene oxide mixed solution, the modified polyamide and the montmorillonite powder in a reaction container containing an organic solvent under ultrasonic dispersion and mechanical stirring, adding a dispersing agent and an antioxidant which are melted into a liquid state to obtain a mixture, continuously performing ultrasonic dispersion and mechanical stirring to ensure that the mixture is uniform, removing the organic solvent, and then putting the mixture into a reaction kettle, wherein the reaction time is controlled to be 80 minutes; and adding the obtained mixture into an extruder to extrude into filaments, and cooling and granulating to obtain the multifunctional graphene polymer master batch.
The mass ratio of the polyamide to the nano zinc oxide in the second step is 1:7.
the mass ratio of the graphene oxide mixed solution, the modified polyamide, the montmorillonite powder, the dispersing agent and the antioxidant in the fourth step is 43:52:22:2.1:2.1.
the mass ratio of the organic solvent in the fourth step is 1: 1.5N, N-dimethylformamide and toluene.
Example 5
The multifunctional graphene polyamide master batch of the embodiment comprises the following raw materials in parts by weight: 40 parts of graphene oxide, 20 parts of polyamide, 6 parts of carbon nano tube, 5 parts of montmorillonite, 1 part of dispersing agent and 1 part of antioxidant.
The dispersing agent is one or more of polyethylene wax, polypropylene wax and ethylene-vinyl acetate copolymer wax.
The antioxidant is one or more of N-phenyl-alpha-naphthylamine, alkyl phenothiazine and benzotriazole derivatives.
The preparation method comprises the following specific steps:
step one: weighing graphene oxide prepared by a Staudenmailer method, dispersing the graphene oxide in water for 8min by utilizing ultrasonic waves, and stirring the graphene oxide for 12min to obtain a graphene oxide mixed solution for later use;
step two: adding carbon nanotubes into the reaction container in the first step, keeping the rotating speed at 320 revolutions per minute, and continuously stirring for 25 minutes to fully mix the carbon nanotubes with the graphene oxide mixed solution to obtain a mixture A for later use;
step three: fully and uniformly mixing the obtained mixture A and polyamide in a reaction container containing an organic solvent under the conditions of ultrasonic dispersion and mechanical stirring, adding a dispersing agent and an antioxidant which are melted into a liquid state to obtain a mixture, continuously performing ultrasonic dispersion and mechanical stirring to ensure that the mixture is uniform, removing the organic solvent, and then putting the mixture into the reaction container, wherein the reaction time is controlled to be 80 min; and adding the obtained mixture into an extruder to extrude into filaments, and cooling and granulating to obtain the multifunctional graphene polymer master batch.
The mass ratio of the graphene oxide mixed solution to the carbon nano tube in the second step is 1.5:6.2.
the mass ratio of the mixture A to the polyamide to the dispersing agent to the antioxidant in the step three is 43:52:2.1:2.1.
the mass ratio of the organic solvent in the third step is 1: 1.5N, N-dimethylformamide and toluene.
Comparative example:
the graphene polyamide master batch of the comparative example comprises the following raw materials in parts by weight: 40 parts of graphene oxide, 20 parts of modified polyamide, 6 parts of carbon nano tube, 5 parts of montmorillonite, 1 part of dispersing agent and 1 part of antioxidant.
The dispersing agent is polyethylene wax.
The antioxidant is N-phenyl-alpha-naphthylamine.
The preparation method comprises the following steps:
step one: weighing graphene oxide in a reaction container, dispersing the graphene oxide in water by utilizing ultrasonic waves for 8min, and stirring the graphene oxide for 12min to obtain a graphene oxide mixed solution for later use;
step two: weighing polyamide for later use:
step two: adding the graphene oxide mixed solution and polyamide into a reaction vessel to fully and uniformly mix the graphene oxide mixed solution and polyamide, then adding a dispersing agent and an antioxidant which are melted into a liquid state to obtain a mixture, continuously performing ultrasonic dispersion and mechanical stirring to ensure that the mixture becomes uniform, removing an organic solvent, then putting the mixture into a reaction kettle, and controlling the reaction time to be 80min, wherein the reaction temperature is 200 ℃; and adding the obtained mixture into an extruder to extrude into filaments, and cooling and granulating to obtain the multifunctional graphene polymer master batch.
The sources of the raw materials in the above examples and comparative examples are: the graphene oxide is JK-R0801, the polyamide is Siemens Aldrich (Shanghai) trade company, the carbon nanotube is 02395-250G, the carbon nanotube is C12125-250mg, the silane coupling agent KH-560 is 0002, the isopropanol is W292907-8KG-K, the zinc oxide is 96479-100G, the oleic acid is 201-177-9, the montmorillonite is S42017-100G, and the dispersant is NNO, jin Jinle.
The multifunctional graphene polymer master batches prepared in the above examples 1 to 5 are respectively used as an experiment group 1, an experiment group 2, an experiment group 3, an experiment group 4 and an experiment group 5, the graphene polyamide master batches produced in the comparative examples are selected as a control group, the selected functional graphene polymer master batches are tested for impact strength, breaking elongation, tensile strength, crystallinity and conductivity (the impact strength is tested and recorded according to GB/T16421-1996 standard, the tensile property is tested and recorded according to GB/T1043-93 standard, the crystallinity is tested and recorded by a Perkkin-Elmer type scanning calorimeter, the conductivity is measured and recorded by a 4200-SCS type four-probe conductivity tester produced by Ji-House-Lei Co., U.S., and the test results are shown in Table 1.
Table 1 test results
As can be seen from Table 1, the multifunctional graphene polymer master batch produced by the method has better impact resistance, toughness, crystallinity and conductivity, the conductivity is reduced compared with the comparative example 1 without adding carbon nanotubes, the impact resistance, toughness and crystallinity are reduced compared with the comparative example 1 without adding modified polyamide and montmorillonite, the impact resistance and toughness are improved by modifying the polyamide by using nano zinc oxide and then blending the modified polyamide with graphene to prepare master batch, the impact resistance and toughness of the master batch can be improved, that is, the surface area is large compared with the dispersion of nano zinc oxide, the contact area with a substrate is large, the surface active center is large, better interface bonding is available between the master batch and the substrate, the compatibility is better, particles are not easy to separate from the substrate when the master batch is stressed by external force, and a plurality of micro deformation areas are generated in the master batch due to the interaction of external force fields to absorb a large amount of energy, therefore, the reinforcing and toughening effects can be achieved, the composite material has better mechanical properties, after montmorillonite is added, the crystallinity and the barrier property of the polyamide composite material can be increased, as the montmorillonite has unique lamellar one-dimensional nano structure characteristics and morphological characteristics, the interlayer has designable reactivity, the oversized specific surface area and the diameter/thickness ratio of more than 200 are realized, the performance of the composite material added with the montmorillonite can be substantially improved, the tubular carbon nano tube and the lamellar graphene oxide are mixed and then are prepared into master batches with polyamide, the conductivity of the composite material can be enhanced, compared with a conductive network formed by connecting the independent carbon nano tubes and the graphene at zero dimension points, the tubular carbon nano tube in the hybridized filler has bridging effect on the lamellar graphene, the formed one-dimensional linear connection can obviously increase the interface contact area, thereby causing the hybrid nanofiller to produce a synergistic effect on the electrical conductivity of the polyamide composite material.
Claims (6)
1. Multifunctional graphene polyamide master batch is characterized in that: the material comprises the following raw materials in parts by weight: 40-85 parts of graphene oxide, 20-50 parts of modified polyamide, 6-16 parts of carbon nanotubes, 5-12 parts of montmorillonite, 1-3 parts of dispersing agent and 1-3 parts of antioxidant; the dispersing agent is one or more of polyethylene wax, polypropylene wax and ethylene-vinyl acetate copolymer wax; the antioxidant is one or more of N-phenyl-alpha-naphthylamine, alkyl phenothiazine and benzotriazole derivatives;
the preparation process of the modified polyamide comprises the following steps: weighing silane coupling agent KH-560, completely dissolving in isopropanol, adding nano zinc oxide, mechanically stirring in a reactor at 75-110 ℃ for reaction for 3-7h, suction filtering, extracting with isoascorbate at 75-100 ℃ for 4-7h, and vacuum drying at 40-65 ℃ for 10-15h to obtain a surface modified nano zinc oxide sample I; uniformly mixing the dried polyamide and the olefine acid, putting the mixture into a HAKKE rheometer, wherein the processing temperature is 200-260 ℃, the rotor speed is 180-240rpm, the blending time is 5-10min, and melting and blending to obtain a second sample for later use; weighing a first nano zinc oxide sample and a second nano zinc oxide sample, putting the first nano zinc oxide sample and the second nano zinc oxide sample into a HAKKE rheometer, and carrying out melt blending to obtain modified polyamide for later use, wherein the processing temperature is 200-240 ℃, the rotor speed is 130-180 rpm, and the blending time is 10-18 min;
the mass ratio of the polyamide to the nano zinc oxide is 1: (5-10.2).
2. The multifunctional graphene polyamide masterbatch according to claim 1, characterized in that: the material comprises the following raw materials in parts by weight: 50-75 parts of graphene oxide, 30-50 parts of modified polyamide, 9-13 parts of carbon nanotubes, 7-10 parts of montmorillonite, 1.5-2.5 parts of dispersing agent and 1.5-2.5 parts of antioxidant.
3. The preparation method of the multifunctional graphene polyamide masterbatch according to claim 1 or 2, which is characterized in that: the preparation method comprises the following specific steps:
step one: weighing graphene oxide prepared by a Staudenmailer method, dispersing the graphene oxide in water by utilizing ultrasonic waves for 5-10min, and stirring the graphene oxide for 10-15 min to obtain a graphene oxide mixed solution for later use;
step two: adding carbon nanotubes into the reaction container in the first step, keeping the rotating speed at 300-350 r/min, and continuously stirring for 20-30 min to fully mix the carbon nanotubes with the graphene oxide mixed solution to obtain a mixture A for later use;
step three: the preparation process of the modified polyamide comprises the following steps: weighing silane coupling agent KH-560, completely dissolving in isopropanol, adding nano zinc oxide, mechanically stirring in a reactor at 75-110 ℃ for reaction for 3-7h, suction filtering, extracting with isoascorbate at 75-100 ℃ for 4-7h, and vacuum drying at 40-65 ℃ for 10-15h to obtain a surface modified nano zinc oxide sample I; uniformly mixing the dried polyamide and the olefine acid, putting the mixture into a HAKKE rheometer, wherein the processing temperature is 200-260 ℃, the rotor speed is 180-240rpm, the blending time is 5-10min, and melting and blending to obtain a second sample for later use; weighing a first nano zinc oxide sample and a second nano zinc oxide sample, putting the first nano zinc oxide sample and the second nano zinc oxide sample into a HAKKE rheometer, and carrying out melt blending to obtain modified polyamide for later use, wherein the processing temperature is 200-240 ℃, the rotor speed is 130-180 rpm, and the blending time is 10-18 min;
step four: weighing montmorillonite, and grinding in a ball mill to obtain montmorillonite powder with the particle size of not less than 300 meshes for standby;
step five: fully and uniformly mixing the obtained mixture A, modified polyamide and montmorillonite powder in a reaction vessel containing an organic solvent under ultrasonic dispersion and mechanical stirring, adding a dispersing agent and an antioxidant which are melted into a liquid state to obtain a mixture, continuously performing ultrasonic dispersion and mechanical stirring to uniformly mix the mixture, removing the organic solvent, putting the mixture into the reaction vessel, and controlling the reaction time to be 60-110 min, wherein the reaction temperature is 180-240 ℃; and adding the obtained mixture into an extruder to extrude into filaments, and cooling and granulating to obtain the multifunctional graphene polyamide master batch.
4. The method for preparing the multifunctional graphene polyamide masterbatch according to claim 3, which is characterized in that: the mass ratio of the graphene oxide mixed solution to the carbon nano tube in the second step is 1.5:6.2.
5. the method for preparing the multifunctional graphene polyamide masterbatch according to claim 3, which is characterized in that: the mass ratio of the mixture A, the modified polyamide, the montmorillonite powder, the dispersing agent and the antioxidant in the fifth step is 43: (51-63): 22:2.1:2.1.
6. the method for preparing the multifunctional graphene polyamide masterbatch according to claim 3, which is characterized in that: the mass ratio of the organic solvent in the fifth step is 1: (1.3-2.1) N, N-dimethylformamide and toluene.
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