CN115353706A - Permanent antistatic ABS composite material containing modified carbon nanotubes and preparation method and application thereof - Google Patents
Permanent antistatic ABS composite material containing modified carbon nanotubes and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 76
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 22
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- 238000001816 cooling Methods 0.000 claims description 12
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 76
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 47
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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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
- C08K9/10—Encapsulated 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/017—Additives being an antistatic agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention belongs to the field of antistatic materials, and discloses a permanent antistatic ABS composite material containing modified carbon nanotubes, and a preparation method and application thereof. The method comprises the following steps: adding the acidified carbon nano tube and hexadecyl trimethyl ammonium bromide into toluene, carrying out ultrasonic treatment, then adding aniline monomer and dodecyl benzene sulfonic acid, and then continuing ultrasonic treatment to obtain a mixed solution; adding an ammonium persulfate solution into the mixed solution, placing the mixed solution in a refrigerator for reaction, performing emulsion breaking, washing and suction filtration by using methanol after the reaction is finished, washing a filter cake by using deionized water, and drying to obtain carbon nanotube grafted polyaniline; blending the carbon nano tube-polyaniline product and the ABS raw material in a double-roller open mill, pressing the mixture by using a flat vulcanizing instrument, taking out the mixture, and cold-pressing the mixture at room temperature to obtain the permanent antistatic ABS composite material. The permanent antistatic ABS composite material can be well applied to the field of antistatic packaging or automobile industry.
Description
Technical Field
The invention belongs to the field of antistatic materials, and particularly relates to a permanent antistatic ABS composite material containing modified carbon nanotubes, and a preparation method and application thereof.
Background
ABS is a terpolymer of acrylonitrile-butadiene-styrene, and is a typical thermoplastic engineering plastic. ABS has excellent size stability, low temperature resistance, coloring property and processing flowability, can still show certain toughness at minus 40 ℃, and can be used in the temperature range of minus 40 ℃ to 100 ℃. However, static electricity generated in the ABS resin cannot be discharged in time due to high insulation property of the ABS resin itself, and when the static electricity is accumulated to a certain degree, an electric shock or a spark discharge may occur when rubbing with other materials or objects, and even serious, there is a risk of causing a serious accident such as a fire, an explosion, etc. Therefore, the ABS is required to be modified to prepare the ABS with antistatic property.
At present, three antistatic agents added into ABS resin are mainly surface active agent type antistatic agent, high molecular type antistatic agent and conductive filler type antistatic agent. Wherein the antistatic effect of the surfactant is not durable, and the high molecular type antistatic agent has the defect of reduced mechanical property caused by too much addition amount. Therefore, the ABS is mainly modified by carbon conductive substances in an antistatic way at present. The carbon-based conductive material mainly includes carbon black, graphite, and carbon fiber.
Carbon nanotubes are used in antistatic applications because of their large specific surface area, surface defects, and the like, which facilitate chemical modification of the carbon nanotubes. However, the surfaces of the carbon nanotubes are easily agglomerated due to the van der waals force of the carbon nanotubes, so that the carbon nanotubes and the ABS resin are not uniformly mixed in the mixing process, and the antistatic effect is poor.
Polyaniline (PANI) is a widely recognized feature due to its unique, controllable chemical and electrical properties. The polyaniline has flexible structure and wide adjustable performance, and has potential application prospect in many fields of battery electrodes, anticorrosion coating and the like. In addition, polyaniline has the highest environmental stability, and is recognized as the only conductive polymer that is stable in air.
Carbon nanotubes are generally used as conductive fillers in the prior art to improve the antistatic property of ABS resin, for example, chinese patent application with the application number of CN102268171A discloses a novel antistatic resin material and a preparation method thereof, the invention utilizes the mutual synergistic effect among carbon black, the carbon nanotubes and polyaniline to prepare ABS composite material by directly blending the carbon black, the carbon nanotubes and the polyaniline, so that the material is made into ABS composite materialThe antistatic material meets the antistatic requirement, but the mechanical property loss of the material is larger due to the higher content of the added carbon black. The invention discloses an antistatic ABS composite material and a preparation method thereof, wherein the Chinese patent application with the application number of CN 110615953A introduces ionic liquid as a compatilizer of ABS resin and carbon nano tubes, and 2-5 parts of carbon nano tube antistatic agent is added to ensure that the surface resistance of the material reaches 10 5 Omega, but the ionic liquid is expensive, and the cost of material preparation is increased.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention mainly aims to provide a preparation method of a permanent antistatic ABS composite material containing modified carbon nanotubes; the method can effectively improve the antistatic property of the ABS resin, improve the humidity stability of the ABS resin and reduce the loss of mechanical property.
The invention also aims to provide a permanent antistatic ABS composite material containing the modified carbon nano tube prepared by the preparation method.
The invention further aims to provide application of the permanent antistatic ABS composite material containing the modified carbon nano tube.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a permanent antistatic ABS composite material containing modified carbon nanotubes comprises the following operation steps:
(1) Placing the carbon nano tube in mixed acid of concentrated nitric acid and concentrated sulfuric acid, carrying out ultrasonic treatment for 5-6h, cooling, diluting with deionized water, carrying out suction filtration, and washing a filter cake with distilled water to obtain an acidified carbon nano tube;
(2) Adding an acidified carbon nano tube and Cetyl Trimethyl Ammonium Bromide (CTAB) into toluene, carrying out ultrasonic treatment, then adding an aniline monomer and dodecylbenzene sulfonic acid, and then continuing ultrasonic treatment to obtain a mixed solution; adding Ammonium Persulfate (APS) into deionized water to prepare an ammonium persulfate solution; adding an ammonium persulfate solution into the mixed solution, uniformly stirring, placing in a refrigerator for reaction, performing emulsion breaking, washing and suction filtration by using methanol after the reaction is finished, washing a filter cake by using deionized water, and drying to obtain a carbon nano tube-polyaniline product;
(3) Blending the carbon nano tube-polyaniline product and the ABS raw material in a double-roller open mill, pressing the mixture by using a flat vulcanizing instrument, taking out the mixture, and cold-pressing the mixture at room temperature to obtain the permanent antistatic ABS composite material.
In the mixed acid of the concentrated nitric acid and the concentrated sulfuric acid in the step (1), the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 25: 75; the ultrasonic time is 5-6h.
The molar ratio of the hexadecyl trimethyl ammonium bromide to the aniline monomer to the ammonium persulfate to the dodecylbenzene sulfonic acid in the step (2) is 0.7; the mass ratio of the acidified carbon nanotubes to the aniline monomer is 1:5-1; the ultrasonic treatment time is 5min; the time for stirring uniformly is 5min; the reaction time was 24h.
In the step (3), the dosage of the carbon nano tube-polyaniline product is 1-4% of the mass of the ABS raw material, the blending temperature is 180 ℃, and the blending time is 15min; the temperature of the pressing plate is 180 ℃, and the pressing time is 10-15min; the cold pressing time is 0-10min, and cooling circulating water is used for 0-5min during the cold pressing period.
The permanent antistatic ABS composite material containing the modified carbon nano tube is prepared by the preparation method.
The permanent antistatic ABS composite material containing the modified carbon nano tube can be applied to the fields of antistatic packaging or automobile industry and the like.
The principle of the invention is as follows:
aiming at the problem that carbon nano tubes are easy to agglomerate in ABS resin so as to reduce the antistatic effect of the ABS resin, the invention wraps polyaniline on the surfaces of the carbon nano tubes by utilizing the pi-pi action between the polyaniline and the carbon nano tubes, thereby achieving the purpose of reducing the agglomeration of the carbon nano tubes. The preparation method comprises the steps of firstly carboxylating carbon nanotubes, then amidating the carbon nanotubes by using an ethylenediamine one-step amide method, and finally preparing a CNT/polyaniline nano material by adopting an emulsion polymerization method, wherein the carbon nanotubes are grafted with amino carbon nanotubes, so that the carbon nanotubes and polyaniline can be better grafted together through chemical bond action, an aniline monomer can be firstly dispersed in an emulsion environment and adsorbed on the surfaces of the carbon nanotubes, and then polymerization is carried out, so that the polyaniline is more uniformly coated on the surfaces of the carbon nanotubes, the agglomeration of the carbon nanotubes is further reduced, and meanwhile, the polyaniline is a conductive polymer and can not hinder the transfer of charges while being coated on the surfaces of the carbon nanotubes, so that the antistatic effect of the ABS resin is improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention prepares a permanent antistatic ABS material modified by carbon nano tubes, and the material has a permanent antistatic effect.
(2) According to the invention, polyaniline is coated on the carbon nano tube by an emulsion polymerization method to prepare a modified carbon nano tube raw material, and then the ABS resin and the modified carbon nano tube are blended, so that the possibility of carbon nano tube agglomeration is reduced, the using amount of the carbon nano tube is reduced, and the mechanical property of the ABS composite material is kept basically unchanged.
(3) The carbon nano tube has low addition amount, low corresponding material cost and good mechanical property of the composite material, and compared with the manufacturing process in the prior art, the preparation method of the invention is simpler and has high product yield.
Drawings
FIG. 1 is a graph showing the results of resistance property tests of ABS composites obtained in examples and comparative examples, in which black filled colors represent comparative examples 1, 3, 4 and 5 in which composites were prepared using virgin carbon nanotubes, and unfilled colors represent examples 1, 6, 7 and 8 in which composites were prepared using modified carbon nanotubes.
FIG. 2 is a graph showing the results of resistance tests before and after moisture absorption of ABS composites obtained in examples and comparative examples, wherein bar 1 represents a blank ABS resin sample, bar 2 represents comparative example 3, bar 3 represents comparative example 4, bar 4 represents comparative example 5, bar 5 represents comparative example 1, bar 6 represents example 6, bar 7 represents example 7, bar 8 represents example 8, and bar 9 represents example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
The acidified carbon nanotubes were prepared as follows: putting 0.01g of carbon nano tube into a flask containing 75ml of concentrated sulfuric acid, carrying out ultrasonic treatment for 5min, measuring 25ml of concentrated nitric acid, adding the concentrated nitric acid into the carbon nano tube mixed solution, putting the flask into an oil bath kettle at 60 ℃, carrying out reaction for 5h, pouring the liquid in the flask into 1L of deionized water for dilution after the reaction is finished, cooling to room temperature, carrying out suction filtration, washing a filter cake with distilled water, putting the washed filter cake into a drying blower at 60 ℃, and drying for 24h to obtain an acidified carbon nano tube for later use;
CNT-PANI was prepared as follows: 0.1g of the acidified carbon nanotube prepared as described above and 2.73g of cetyltrimethylammonium bromide (CTAB) were added to 30ml of toluene, and after 5 minutes of ultrasonication, 1g of aniline monomer and 3.52g of dodecylbenzenesulfonic acid were added, and ultrasonication was continued for 5 minutes to obtain a mixed solution. 2.46g Ammonium Persulfate (APS) was added to 10ml deionized water to prepare an ammonium persulfate solution. And adding an ammonium persulfate solution into the mixed solution, stirring for 5min, and placing in a refrigerator for reaction for 24h. And after the reaction is finished, demulsifying, washing and filtering by using methanol, washing a filter cake by using deionized water to obtain a product, and drying the washed product in a forced air drying oven for 24 hours to obtain a carbon nano tube-polyaniline product (CNT-PANI).
Preparation of CNT-PANI/ABS composite: adding 0.68g of carbon nano tube-polyaniline product and 17g of ABS resin into an open mill for blending at the temperature of 180 ℃ for 15min, then adding the mixture into a press plate vulcanizer for pressing plates at the temperature of 180 ℃ for 15min, then directly taking out the press plate vulcanizer, and placing the press plate vulcanizer at room temperature for cold pressing for 10min to finally obtain the permanent antistatic ABS composite material containing the modified carbon nano tubes, namely the CNT-PANI/ABS composite material for subsequent use.
Example 2
The acidified carbon nanotubes were prepared as follows: putting 0.01g of carbon nano tube into a flask containing 75ml of concentrated sulfuric acid, carrying out ultrasonic treatment for 5min, measuring 25ml of concentrated nitric acid, adding the concentrated nitric acid into the carbon nano tube mixed solution, putting the flask into an oil bath kettle at 60 ℃, reacting for 6h, pouring the liquid in the flask into 1L of deionized water for dilution after the reaction is finished, cooling to room temperature, carrying out suction filtration, washing a filter cake with distilled water, and drying the washed filter cake in a drying blower at 60 ℃ for 24h to obtain an acidified carbon nano tube for later use;
CNT-PANI was prepared as follows: 0.1g of the acidified carbon nanotube prepared as described above and 2.73g of cetyltrimethylammonium bromide (CTAB) were added to 30ml of toluene, and after 5 minutes of ultrasonication, 1g of aniline monomer and 3.52g of dodecylbenzenesulfonic acid were added, and ultrasonication was continued for 5 minutes to obtain a mixed solution. 2.46g Ammonium Persulfate (APS) was added to 10ml deionized water to prepare an ammonium persulfate solution. And adding an ammonium persulfate solution into the mixed solution, stirring for 5min, and placing in a refrigerator for reaction for 24h. And after the reaction is finished, demulsifying, washing and filtering by using methanol, washing a filter cake by using deionized water to obtain a product, and drying the washed product in a forced air drying oven for 24 hours to obtain a carbon nano tube-polyaniline product (CNT-PANI).
Preparation of CNT-PANI/ABS composite: adding 0.68g of carbon nano tube-polyaniline product and 17g of ABS resin into an open mill for blending at the temperature of 180 ℃ for 15min, then adding the mixture into a press plate vulcanizer for pressing plates at the temperature of 180 ℃ for 15min, then directly taking out the press plate vulcanizer, and placing the press plate vulcanizer at room temperature for cold pressing for 10min to finally obtain the permanent antistatic ABS composite material containing the modified carbon nano tubes, namely the CNT-PANI/ABS composite material for subsequent use.
Example 3
The acidified carbon nanotubes were prepared as follows: placing 0.01g of carbon nano tube in a flask containing 75ml of concentrated sulfuric acid, carrying out ultrasonic treatment for 5min, measuring 25ml of concentrated nitric acid, adding the concentrated nitric acid into the carbon nano tube mixed solution, placing the flask in an oil bath kettle at 60 ℃, carrying out reaction for 5h, pouring the liquid in the flask into 1L of deionized water for dilution after the reaction is finished, cooling to room temperature, carrying out suction filtration, washing a filter cake with distilled water, placing the washed filter cake in a drying blower at 60 ℃ for drying for 24h, and obtaining an acidified carbon nano tube for later use;
CNT-PANI was prepared as follows: 0.1g of the acidified carbon nanotube prepared as described above and 1.73g of cetyltrimethylammonium bromide (CTAB) were added to 30ml of toluene, and after 5 minutes of ultrasonication, 0.5g of aniline monomer and 1.76g of dodecylbenzenesulfonic acid were added, and ultrasonication was continued for 5 minutes to obtain a mixed solution. Ammonium Persulfate (APS), 1.23g, was added to 10ml of deionized water to prepare an ammonium persulfate solution. And adding an ammonium persulfate solution into the mixed solution, stirring for 5min, and placing in a refrigerator for reaction for 24h. And after the reaction is finished, demulsifying, washing and filtering by using methanol, washing a filter cake by using deionized water to obtain a product, and drying the washed product in a forced air drying oven for 24 hours to obtain a carbon nano tube-polyaniline product (CNT-PANI).
Preparation of CNT-PANI/ABS composite: adding 0.68g of carbon nano tube-polyaniline product and 17g of ABS resin into an open mill for blending at the temperature of 180 ℃ for 15min, then adding the mixture into a press plate vulcanizer for pressing plates at the temperature of 180 ℃ for 15min, then directly taking out the press plate vulcanizer, and placing the press plate vulcanizer at room temperature for cold pressing for 10min to finally obtain the permanent antistatic ABS composite material containing the modified carbon nano tubes, namely the CNT-PANI/ABS composite material for subsequent use.
Example 4
The acidified carbon nanotubes were prepared as follows: putting 0.01g of carbon nano tube into a flask containing 75ml of concentrated sulfuric acid, carrying out ultrasonic treatment for 5min, measuring 25ml of concentrated nitric acid, adding the concentrated nitric acid into the carbon nano tube mixed solution, putting the flask into an oil bath kettle at 60 ℃, reacting for 6h, pouring the liquid in the flask into 1L of deionized water for dilution after the reaction is finished, cooling to room temperature, carrying out suction filtration, washing a filter cake with distilled water, and drying the washed filter cake in a drying blower at 60 ℃ for 24h to obtain an acidified carbon nano tube for later use;
CNT-PANI was prepared as follows: 0.1g of the acidified carbon nanotube prepared as described above and 2.73g of cetyltrimethylammonium bromide (CTAB) were added to 30ml of toluene, and after 5 minutes of ultrasonication, 1g of aniline monomer and 3.52g of dodecylbenzenesulfonic acid were added, and ultrasonication was continued for 5 minutes to obtain a mixed solution. 2.46g of Ammonium Persulfate (APS) was added to 10ml of a 1M hydrochloric acid solution to prepare an ammonium persulfate solution. And adding an ammonium persulfate solution into the mixed solution, stirring for 5min, and placing in a refrigerator for reaction for 24h. And after the reaction is finished, demulsifying, washing and filtering by using methanol, washing a filter cake by using deionized water to obtain a product, and drying the washed product in a forced air drying oven for 24 hours to obtain a carbon nano tube-polyaniline product (CNT-PANI).
Preparation of CNT-PANI/ABS composite: adding 0.68g of carbon nanotube-polyaniline product and 17g of ABS resin into an open mill for blending at the temperature of 180 ℃ for 15min, adding the mixture into a vulcanizing press for pressing, wherein the pressing temperature is 180 ℃ and the pressing time is 15min, directly taking the mixture out of the vulcanizing press, and cold-pressing the mixture at room temperature for 10min to finally obtain the permanent antistatic ABS composite material containing the modified carbon nanotube, namely the CNT-PANI/ABS composite material for subsequent use.
Example 5
The acidified carbon nanotubes were prepared as follows: putting 0.01g of carbon nano tube into a flask containing 75ml of concentrated sulfuric acid, carrying out ultrasonic treatment for 5min, measuring 25ml of concentrated nitric acid, adding the concentrated nitric acid into the carbon nano tube mixed solution, putting the flask into an oil bath kettle at 60 ℃, reacting for 6h, pouring the liquid in the flask into 1L of deionized water for dilution after the reaction is finished, cooling to room temperature, carrying out suction filtration, washing a filter cake with distilled water, and drying the washed filter cake in a drying blower at 60 ℃ for 24h to obtain an acidified carbon nano tube for later use;
CNT-PANI was prepared as follows: 0.1g of the acidified carbon nanotube prepared above and 2.73g of cetyltrimethylammonium bromide (CTAB) were added to 30ml of toluene, and after 5 minutes of sonication, 1g of aniline monomer and 3.52g of dodecylbenzenesulfonic acid were added to the above mixture and further sonicated for 5 minutes. 2.46g of Ammonium Persulfate (APS) was added to 10ml of a 1M hydrochloric acid solution to prepare an ammonium persulfate solution. And adding an ammonium persulfate solution into the mixed solution, stirring for 5min, and placing in a refrigerator for reaction for 24h. And after the reaction is finished, demulsifying, washing and suction-filtering by using methanol, washing a filter cake by using a 1M hydrochloric acid solution to obtain a product, and drying the washed product in a forced air drying oven for 24 hours to obtain a carbon nano tube-polyaniline product (CNT-PANI).
Preparation of CNT-PANI/ABS composite: adding 0.68g of carbon nanotube-polyaniline product and 17g of ABS resin into an open mill for blending at the temperature of 180 ℃ for 15min, adding the mixture into a vulcanizing press for pressing, wherein the pressing temperature is 180 ℃ and the pressing time is 15min, directly taking the mixture out of the vulcanizing press, and cold-pressing the mixture at room temperature for 10min to finally obtain the permanent antistatic ABS composite material containing the modified carbon nanotube, namely the CNT-PANI/ABS composite material for subsequent use.
Example 6
Example 6 is the same as example 1 except that 0.17g of carbon nanotube-grafted polyaniline and 17g of ABS resin were added to an open mill and blended at 180 ℃ for 15min.
Example 7
Example 7 is the same as example 1 except that 0.34g of carbon nanotube-grafted polyaniline and 17g of ABS resin were added to an open mill and blended at 180 ℃ for 15min.
Example 8
Example 8 is the same as example 1 except that 0.51g of carbon nanotube-grafted polyaniline and 17g of ABS resin were added to an open mill and blended at 180 ℃ for 15min.
Example 9
The acidified carbon nanotubes were prepared as follows: putting 0.01g of carbon nano tube into a flask containing 75ml of concentrated sulfuric acid, carrying out ultrasonic treatment for 5min, measuring 25ml of concentrated nitric acid, adding the concentrated nitric acid into the carbon nano tube mixed solution, putting the flask into an oil bath kettle at 60 ℃, carrying out reaction for 5h, pouring the liquid in the flask into 1L of deionized water for dilution after the reaction is finished, cooling to room temperature, carrying out suction filtration, washing a filter cake with distilled water, putting the washed filter cake into a drying blower at 60 ℃, and drying for 24h to obtain an acidified carbon nano tube for later use;
CNT-PANI was prepared as follows: 0.1g of the acidified carbon nanotube prepared as described above and 2.73g of cetyltrimethylammonium bromide (CTAB) were added to 30ml of toluene, and after 5 minutes of ultrasonication, 1g of aniline monomer and 3.52g of dodecylbenzenesulfonic acid were added, and ultrasonication was continued for 5 minutes to obtain a mixed solution. 2.46g Ammonium Persulfate (APS) was added to 10ml deionized water to prepare an ammonium persulfate solution. And adding an ammonium persulfate solution into the mixed solution, stirring for 5min, and placing in a refrigerator for reaction for 24h. And after the reaction is finished, demulsifying, washing and filtering by using methanol, washing a filter cake by using deionized water to obtain a product, and drying the washed product in a forced air drying oven for 24 hours to obtain a carbon nano tube-polyaniline product (CNT-PANI).
Preparation of CNT-PANI/ABS composite: adding 0.68g of carbon nano tube-polyaniline product and 17g of ABS resin into an open mill for blending at the temperature of 180 ℃ for 15min, then adding the mixture into a press vulcanizer for pressing plates at the temperature of 180 ℃ for 15min, then cooling the plates to 150 ℃ by using cooling circulating water, continuously pressing the plates for 10min, and then placing the plates at room temperature for cold pressing for 5min to finally obtain the CNT-PANI/ABS composite material for subsequent use.
Comparative example 1
0.1g of carbon nanotube and 2.73g of cetyltrimethylammonium bromide (CTAB) were added to 30ml of toluene, and after 5 minutes of ultrasonication, 1g of aniline monomer and 3.52g of dodecylbenzenesulfonic acid were added, and ultrasonication was continued for 5 minutes to obtain a mixed solution. 2.46g Ammonium Persulfate (APS) was added to 10ml deionized water to prepare an ammonium persulfate solution. And adding an ammonium persulfate solution into the mixed solution, stirring for 5min, and placing in a refrigerator for reaction for 24h. And after the reaction is finished, demulsifying, washing and filtering by using methanol, washing the filter cake by using deionized water to obtain a product, and drying the washed product in a forced air drying oven for 24 hours to obtain the original carbon nano tube-polyaniline product.
And adding 0.68g of the obtained original carbon nanotube-polyaniline product and 17g of ABS resin into an open mill for blending at the blending temperature of 180 ℃ for 15min, then adding the mixture into a flat vulcanizing instrument for pressing, wherein the pressing temperature is 180 ℃ and the pressing time is 15min, then directly taking the mixture out of the flat vulcanizing instrument, and placing the mixture at room temperature for cold pressing for 10min to finally obtain the ABS composite material containing the carbon nanotube for subsequent use.
Comparative example 2
Comparative example 2 is the same as comparative example 1 except that 0.1g of carbon nanotubes and 1.73g of cetyltrimethylammonium bromide (CTAB) were added to 30ml of toluene, and after 5 minutes of sonication, 0.5g of aniline monomer and 1.76g of dodecylbenzenesulfonic acid were added, and sonication was continued for 5 minutes.
Comparative example 3
Comparative example 3 differs from comparative example 1 in that: 0.17g of the original carbon nanotube-polyaniline product and 17g of ABS resin are added into an open mill for blending, the blending temperature is 180 ℃, and the blending time is 15min.
Comparative example 4
Comparative example 4 differs from comparative example 1 in that: 0.34g of original carbon nano tube-polyaniline product and 17g of ABS resin are added into an open mill for blending, the blending temperature is 180 ℃, and the blending time is 15min.
Comparative example 5
Comparative example 5 differs from comparative example 1 in that: 0.51g of the original carbon nano tube-polyaniline product and 17g of ABS resin are added into an open mill for blending, the blending temperature is 180 ℃, and the blending time is 15min.
The composite materials obtained in examples 1, 6, 7 and 8 and comparative examples 1, 3, 4 and 5 above were subjected to resistance performance tests, and the results are shown in FIG. 1, and the surface resistance was measured with reference to the GBT 1410-2006 standard. It is known that when the surface resistance reaches 10 10 Or less than 10 10 As can be seen from fig. 1, the ABS composite material prepared in example 1 of the present invention satisfies the antistatic requirement when the modified carbon nanotube content is 4%, compared to the original carbon nanotube/ABS composite material prepared in the comparative example, which has a surface resistance of 10 at 4% 11 The antistatic requirement cannot be met. Therefore, the modified carbon nanotube-polyaniline/ABS composite material can meet the antistatic requirement when the amount of the modified carbon nanotube-polyaniline filler is 4% of the mass of the ABS raw material, wherein the optimal amount is in example 1. The carbon nanotube composites obtained in examples 1, 6, 7 and 8 and comparative examples 1, 3, 4 and 5 above were subjected to environmental humidity stabilityThe surface resistance values of the samples before and after moisture absorption were measured by placing the samples in a constant temperature and humidity chamber with the humidity of 80% and the temperature of 30 ℃ for 1 day, and the results are shown in fig. 2, the resistance values of the blank ABS resin samples, the samples of examples 1, 6, 7, and 8, and the samples of comparative examples 1, 3, 4, and 5 were increased before and after moisture absorption, and the surface resistance values after moisture absorption did not meet the antistatic requirements, and only the resistance value of example 1 did not change much before and after moisture absorption and the antistatic requirements of the antistatic material were met, so the modified carbon nanotube-polyaniline/ABS composite material had relatively good environmental humidity stability when the amount of the modified carbon nanotube-polyaniline filler was 4% of the mass of the ABS resin.
In summary, when the amount of the modified carbon nanotube-polyaniline filler is 4% by mass of the ABS resin, the surface resistance of the obtained composite material can meet the antistatic requirement of the antistatic material, and meanwhile, because the content of the carbon nanotube in the filler is only about 9% of the raw material, that is, the content of the carbon nanotube in the modified carbon nanotube-polyaniline/ABS resin composite material is only 0.35%, compared with comparative example 1, the modified carbon nanotube-polyaniline/ABS resin composite material greatly reduces the usage amount of the carbon nanotube, and improves the antistatic performance and the environmental humidity stability.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of a permanent antistatic ABS composite material containing modified carbon nanotubes is characterized by comprising the following operation steps:
(1) Placing the carbon nano tube in mixed acid of concentrated nitric acid and concentrated sulfuric acid, performing ultrasonic treatment, cooling, diluting with deionized water, performing suction filtration, and washing a filter cake with distilled water to obtain an acidified carbon nano tube;
(2) Adding the acidified carbon nano tube and hexadecyl trimethyl ammonium bromide into toluene, carrying out ultrasonic treatment, then adding aniline monomer and dodecyl benzene sulfonic acid, and then continuing ultrasonic treatment to obtain a mixed solution; adding ammonium persulfate into deionized water to prepare an ammonium persulfate solution; adding an ammonium persulfate solution into the mixed solution, uniformly stirring, placing in a refrigerator for reaction, performing emulsion breaking, washing and suction filtration by using methanol after the reaction is finished, washing a filter cake by using deionized water, and drying to obtain a carbon nano tube-polyaniline product;
(3) Blending the carbon nano tube-polyaniline product and the ABS raw material in a double-roller open mill, pressing the mixture by using a flat vulcanizing instrument, taking out the mixture, and cold-pressing the mixture at room temperature to obtain the permanent antistatic ABS composite material.
2. The method of claim 1, wherein: in the mixed acid of the concentrated nitric acid and the concentrated sulfuric acid in the step (1), the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid is 25: 75; the ultrasonic time is 5-6h.
3. The method of claim 1, wherein: the molar ratio of the hexadecyl trimethyl ammonium bromide to the aniline monomer to the ammonium persulfate to the dodecylbenzene sulfonic acid in the step (2) is 0.7; the mass ratio of the acidified carbon nanotubes to the aniline monomers is 1:5-1; the ultrasonic treatment time is 5min; the time for stirring evenly is 5min; the reaction time was 24h.
4. The method of claim 1, wherein: the amount of the carbon nano tube-polyaniline product in the step (3) is 1-4% of the mass of the ABS raw material; the blending temperature is 180 ℃ and the blending time is 15min; the temperature of the pressing plate is 180 ℃, and the pressing time is 10-15min; the cold pressing time is 0-10min, and cooling circulating water is used for 0-5min during the cold pressing period.
5. A permanent antistatic ABS composite material containing modified carbon nanotubes prepared by the preparation method of any one of claims 1 to 4.
6. Use of the permanent antistatic ABS composite containing modified carbon nanotubes of claim 5 in the field of antistatic packaging or automotive industry.
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