CN114133665A - High-conductivity composite master batch containing carbon black and carbon nano tubes and preparation method thereof - Google Patents
High-conductivity composite master batch containing carbon black and carbon nano tubes and preparation method thereof Download PDFInfo
- Publication number
- CN114133665A CN114133665A CN202111537644.0A CN202111537644A CN114133665A CN 114133665 A CN114133665 A CN 114133665A CN 202111537644 A CN202111537644 A CN 202111537644A CN 114133665 A CN114133665 A CN 114133665A
- Authority
- CN
- China
- Prior art keywords
- carbon black
- carbon
- carbon nano
- master batch
- nano tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- 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
-
- 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
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
Abstract
The invention relates to the technical field of high polymer materials, and particularly discloses a high-conductivity composite master batch containing carbon black and carbon nanotubes and a preparation method thereof. The preparation method of the high-conductivity composite master batch containing the carbon black and the carbon nano tubes comprises the following steps: (1) uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid for grinding; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube; (2) mixing the mixture of the carbon black and the carbon nano tube with a dispersing agent and a high polymer material to obtain a mixed material; (3) and extruding and granulating the mixed material by a screw extruder to obtain the high-conductivity composite master batch containing the carbon black and the carbon nano tube. The high-conductivity composite master batch prepared by the method has excellent conductivity; in the high polymer material, only a small amount of the high-conductivity composite master batch can be added to realize excellent conductive effect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-conductivity composite master batch containing carbon black and carbon nano tubes and a preparation method thereof.
Background
Polyethylene, polyvinyl chloride, polypropylene or polystyrene are common high polymer materials; is widely applied to products such as electronic products, automobile parts, medical instruments, chemical containers, pipelines and the like. The volume resistivity of the high polymer material is high; therefore, static electricity is easily accumulated on the surface of the polymer material product; however, the accumulation of static electricity on plastic products can have a number of negative effects on the product. For example, static electricity can accumulate in plastics and attract dust, which can affect not only the appearance of the product, but also the performance of the electronic product. In particular, the electrostatic accumulation causes discharge, and in particular, accidents such as ignition and explosion occur. Therefore, it is necessary to remove static electricity from the polymer material.
At present, the common way is to add carbon black or conductive master batch of carbon nano tube into the high molecular material; however, after the existing conductive masterbatch is added into the polymer material, the carbon black or the carbon nanotube cannot be effectively dispersed into the polymer material. Therefore, to effectively reduce the volume resistivity of the polymer material, it is necessary to add a large amount of conductive material such as carbon black or carbon nanotubes. However, the price of the conductive material such as carbon black or carbon nanotube is high, and the addition of a large amount of carbon black or carbon nanotube inevitably increases the cost. Therefore, the development of the conductive master batch with high conductive effect has important significance for reducing the consumption of the carbon black or the carbon nano tube.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention provides a high-conductivity composite master batch containing carbon black and carbon nanotubes.
A preparation method of a high-conductivity composite master batch containing carbon black and carbon nano tubes comprises the following steps:
(1) uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid for grinding; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube;
(2) mixing the mixture of the carbon black and the carbon nano tube with a dispersing agent and a high polymer material to obtain a mixed material;
(3) and extruding and granulating the mixed material by a screw extruder to obtain the high-conductivity composite master batch containing the carbon black and the carbon nano tube.
The invention provides a novel preparation method of a high-conductivity composite master batch, which is prepared by taking carbon black and carbon nano tubes as raw materials, dispersing the raw materials in a dispersion liquid, and then adding a dispersing agent and a high polymer material for melt blending.
According to the invention, through two core steps of dispersing in the dispersion liquid and adding the dispersing agent, the conductivity of the prepared high-conductivity composite master batch is obviously higher than that of the high-conductivity composite master batch prepared by directly melting and blending carbon black, carbon nano tubes and a high polymer material.
Preferably, the dispersion described in step (1) comprises ethanol, vinyltriethoxysilane, and 3- (phenylamino) propyltrimethoxysilane.
Further research by the inventor shows that the composition of the dispersion liquid has important influence on the conductivity of the prepared high-conductivity composite master batch; research shows that the high-conductivity composite master batch prepared by adding the carbon black and the carbon nano tube into the dispersion liquid containing the ethanol, the vinyl triethoxysilane and the 3- (phenylamino) propyl trimethoxysilane for grinding has far better conductivity than the high-conductivity composite master batch prepared by adding the carbon black and the carbon nano tube into the dispersion liquid with other components for grinding.
Preferably, the volume ratio of the ethanol to the vinyltriethoxysilane to the 3- (phenylamino) propyltrimethoxysilane in the dispersion is 100: 4-6: 1-3.
Most preferably, the volume ratio of ethanol, vinyltriethoxysilane, and 3- (phenylamino) propyltrimethoxysilane in the dispersion is 100:5: 2.
Preferably, the dispersant in the step (2) is prepared by the following method: adding phenyl maleic anhydride into a reaction kettle, adding an organic solvent, stirring for dissolving, adding laurylamine and phenethylamine, and reacting in an inert gas atmosphere; after the reaction is finished, concentrating to remove the organic solvent to obtain the dispersing agent.
Further research by the inventor shows that the dispersing agent also has important influence on the conductivity of the prepared high-conductivity composite master batch; however, the conventional dispersing agent is difficult to further greatly improve the conductivity of the high-conductivity composite master batch; the inventor researches in a large number of experiments to find that when the dispersing agent prepared by taking the phenyl maleic anhydride, the laurylamine and the phenylethylamine as raw materials is adopted, the conductivity of the high-conductivity composite master batch can be further greatly improved; and the improvement degree of the conductive performance of the high-conductivity composite master batch is far higher than that of the conventional dispersing agent.
Preferably, the dosage ratio of the phenyl maleic anhydride to the organic solvent to the laurylamine to the phenylethylamine is 150-200 g, 500-1000 mL, 80-100 g, and 50-70 g.
Most preferably, the ratio of the amount of phenyl maleic anhydride to the organic solvent and laurylamine and phenylethylamine is 180g:900mL:90g:60 g.
Preferably, the specific conditions of the reaction in the inert gas atmosphere are: reacting for 6-12 h at 100-150 ℃ in a nitrogen atmosphere.
Most preferably, the specific conditions of the reaction in an inert gas atmosphere are: the reaction was carried out for 8h at 120 ℃ in a nitrogen atmosphere.
Preferably, the using amount ratio of the carbon black, the carbon nanotubes and the dispersion liquid in the step (1) is 1-3 g: 5-30 mL.
Most preferably, the amount ratio of the carbon black to the carbon nanotubes and the dispersion in step (1) is 2g:1g:10 mL.
Preferably, the weight ratio of the mixture of the carbon black and the carbon nanotubes, the dispersant and the polymer material in the step (3) is 1: 0.1-0.3: 1-3.
Most preferably, the weight ratio of the carbon black and carbon nanotube mixture, the dispersant and the polymeric material is 1:0.2: 2.
Preferably, the polymer material is polyethylene, polypropylene or polystyrene.
The invention also provides the high-conductivity composite master batch containing carbon black and the carbon nano tube, which is prepared by the preparation method.
Has the advantages that: the invention provides a brand-new preparation method of a high-conductivity composite master batch, which takes carbon black and carbon nano tubes as raw materials, and the raw materials are placed into dispersion liquid for dispersion, and then a dispersing agent and a high polymer material are added for melt blending to prepare the high-conductivity composite master batch; the high-conductivity composite master batch prepared by the method has excellent conductivity; in the high polymer material, only a small amount of the high-conductivity composite master batch can be added to realize excellent conductive effect.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
The polypropylene adopted in the following embodiment is the polypropylene with the grade of B8101 produced by Yanshan petrochemical production; the adopted carbon nano tube adopts a multi-wall carbon nano tube, and the multi-wall carbon nano tube adopts the multi-wall carbon nano tube with the mark of CNT106, which is produced by Beijing German island gold science and technology limited; other raw materials without marked sources are all products which can be purchased by the technicians in the field through conventional purchasing approaches; the source of the above-mentioned raw materials does not limit the scope of the present invention.
Example 1 preparation of highly conductive composite masterbatch containing carbon black and carbon nanotubes
(1) Uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid to grind for 2 hours; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube; wherein the dosage ratio of the carbon black to the carbon nano tube to the dispersion liquid is 2g:1g:10 mL;
(2) mixing the mixture of the carbon black and the carbon nano tube with a dispersant and polypropylene to obtain a mixed material; wherein the weight ratio of the mixture of the carbon black and the carbon nano tube, the dispersant and the polypropylene is 1:0.2: 2;
(3) extruding and granulating the mixed material by a double-screw extruder to obtain the high-conductivity composite master batch containing the carbon black and the carbon nano tube;
wherein the dispersion liquid in the step (1) is composed of ethanol, vinyl triethoxysilane and 3- (phenylamino) propyl trimethoxysilane according to the volume ratio of 100:5: 2;
the dispersing agent in the step (2) is prepared by the following method: adding phenyl maleic anhydride into a reaction kettle, adding toluene, stirring for dissolving, adding laurylamine and phenethylamine, and reacting for 8 hours at 120 ℃ in a nitrogen atmosphere; after the reaction is finished, concentrating to remove the organic solvent to obtain the dispersing agent; wherein the dosage ratio of the phenyl maleic anhydride to the toluene to the laurylamine to the phenylethylamine is 180g:900mL:90g:60 g.
Example 2 preparation of highly conductive composite masterbatch containing carbon black and carbon nanotubes
(1) Uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid to grind for 1 h; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube; wherein the dosage ratio of the carbon black to the carbon nano tube to the dispersion liquid is 3g:1g:20 mL;
(2) mixing the mixture of the carbon black and the carbon nano tube with a dispersant and polypropylene to obtain a mixed material; wherein the weight ratio of the mixture of the carbon black and the carbon nano tube, the dispersant and the polypropylene is 1:0.1: 2;
(3) extruding and granulating the mixed material by a double-screw extruder to obtain the high-conductivity composite master batch containing the carbon black and the carbon nano tube;
wherein the dispersion liquid in the step (1) is composed of ethanol, vinyl triethoxysilane and 3- (phenylamino) propyl trimethoxysilane according to the volume ratio of 100:4: 3;
the dispersing agent in the step (2) is prepared by the following method: adding phenyl maleic anhydride into a reaction kettle, adding toluene, stirring for dissolving, adding laurylamine and phenethylamine, and reacting for 10 hours at 110 ℃ in a nitrogen atmosphere; after the reaction is finished, concentrating to remove the organic solvent to obtain the dispersing agent; wherein the dosage ratio of the phenyl maleic anhydride to the toluene to the laurylamine to the phenylethylamine is 150g:800mL:50g:50 g.
Example 3 preparation of highly conductive composite masterbatch containing carbon black and carbon nanotubes
(1) Uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid to grind for 1 h; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube; wherein the dosage ratio of the carbon black to the carbon nano tube to the dispersion liquid is 1g:3g:20 mL;
(2) mixing the mixture of the carbon black and the carbon nano tube with a dispersant and polypropylene to obtain a mixed material; wherein the weight ratio of the mixture of the carbon black and the carbon nano tube, the dispersant and the polypropylene is 1:0.3: 2;
(3) extruding and granulating the mixed material by a double-screw extruder to obtain the high-conductivity composite master batch containing the carbon black and the carbon nano tube;
wherein the dispersion liquid in the step (1) is composed of ethanol, vinyl triethoxysilane and 3- (phenylamino) propyl trimethoxysilane according to the volume ratio of 100:6: 1;
the dispersing agent in the step (2) is prepared by the following method: adding phenyl maleic anhydride into a reaction kettle, adding toluene, stirring for dissolving, adding laurylamine and phenethylamine, and reacting for 6 hours at 140 ℃ in a nitrogen atmosphere; after the reaction is finished, concentrating to remove the organic solvent to obtain the dispersing agent; wherein the dosage ratio of the phenyl maleic anhydride to the toluene to the laurylamine to the phenylethylamine is 200g:1000mL:80g:70 g.
Comparative example 1 preparation of conductive composite masterbatch
(1) Uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid to grind for 2 hours; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube; wherein the dosage ratio of the carbon black to the carbon nano tube to the dispersion liquid is 2g:1g:10 mL;
(2) mixing the mixture of carbon black and carbon nano tubes with polypropylene to obtain a mixed material; wherein the weight ratio of the carbon black to the mixture of carbon nanotubes to the polypropylene is 1: 2;
(3) extruding and granulating the mixed material by a double-screw extruder to obtain the high-conductivity composite master batch containing the carbon black and the carbon nano tube;
wherein the dispersion liquid in the step (1) is composed of ethanol, vinyl triethoxysilane and 3- (phenylamino) propyl trimethoxysilane according to the volume ratio of 100:5: 2.
Comparative example 1 differs from examples 1, 4 and 5 in that no dispersant was added in step (2) of comparative example 2; while examples 1, 4 and 5 were supplemented with different dispersants.
Comparative example 2 preparation of conductive composite masterbatch
(1) Uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid to grind for 2 hours; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube; wherein the dosage ratio of the carbon black to the carbon nano tube to the dispersion liquid is 2g:1g:10 mL;
(2) mixing the mixture of the carbon black and the carbon nano tube with a dispersant and polypropylene to obtain a mixed material; wherein the weight ratio of the mixture of the carbon black and the carbon nano tube, the dispersant and the polypropylene is 1:0.2: 2;
(3) extruding and granulating the mixed material by a double-screw extruder to obtain the high-conductivity composite master batch containing the carbon black and the carbon nano tube;
wherein the dispersion liquid in the step (1) is composed of ethanol, vinyl triethoxysilane and 3- (phenylamino) propyl trimethoxysilane according to the volume ratio of 100:5: 2;
the dispersing agent in the step (2) is prepared by the following method: adding phenyl maleic anhydride into a reaction kettle, adding toluene, stirring for dissolving, adding laurylamine, and reacting at 120 ℃ for 8 hours in a nitrogen atmosphere; after the reaction is finished, concentrating to remove the organic solvent to obtain the dispersing agent; wherein the dosage ratio of the phenyl maleic anhydride to the toluene and the laurylamine is 180g, 900mL and 150 g.
The difference between the comparative example 2 and the example 1 is that the dispersant adopted in the step (2) of the comparative example 2 is prepared only by taking the phenyl maleic anhydride and the laurylamine as raw materials; the dispersant described in example 1 was prepared from phenyl maleic anhydride, laurylamine and phenylethylamine.
Comparative example 3 preparation of conductive composite masterbatch
(1) Uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid to grind for 2 hours; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube; wherein the dosage ratio of the carbon black to the carbon nano tube to the dispersion liquid is 2g:1g:10 mL;
(2) mixing the mixture of the carbon black and the carbon nano tube with a dispersant and polypropylene to obtain a mixed material; wherein the weight ratio of the mixture of the carbon black and the carbon nano tube, the dispersant and the polypropylene is 1:0.2: 2;
(3) extruding and granulating the mixed material by a double-screw extruder to obtain the high-conductivity composite master batch containing the carbon black and the carbon nano tube;
wherein the dispersion liquid in the step (1) is composed of ethanol, vinyl triethoxysilane and 3- (phenylamino) propyl trimethoxysilane according to the volume ratio of 100:5: 2;
the dispersing agent in the step (2) is prepared by the following method: adding phenyl maleic anhydride into a reaction kettle, adding toluene, stirring for dissolving, and adding phenylethylamine to react for 8 hours at 120 ℃ in a nitrogen atmosphere; after the reaction is finished, concentrating to remove the organic solvent to obtain the dispersing agent; wherein the dosage ratio of the phenyl maleic anhydride to the toluene and the phenethylamine is 180g, 900mL and 150 g.
The difference between the comparative example 3 and the example 1 is that the dispersant adopted in the step (2) of the comparative example 3 is prepared only by taking phenyl maleic anhydride and phenethylamine as raw materials; the dispersant described in example 1 was prepared from phenyl maleic anhydride, laurylamine and phenylethylamine.
Comparative example 4 preparation of conductive composite masterbatch
(1) Uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid to grind for 2 hours; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube; wherein the dosage ratio of the carbon black to the carbon nano tube to the dispersion liquid is 2g:1g:10 mL;
(2) mixing the mixture of the carbon black and the carbon nano tube with a dispersant and polypropylene to obtain a mixed material; wherein the weight ratio of the mixture of the carbon black and the carbon nano tube, the dispersant and the polypropylene is 1:0.2: 2;
(3) extruding and granulating the mixed material by a double-screw extruder to obtain the conductive composite master batch;
wherein the dispersion liquid in the step (1) is composed of ethanol, vinyl triethoxysilane and 3- (phenylamino) propyl trimethoxysilane according to the volume ratio of 100:5: 2;
the dispersing agent in the step (2) is calcium stearate.
Comparative example 4 differs from example 1 in that comparative example 4 employs a conventional dispersant calcium stearate; and example 1 uses a dispersant prepared from phenyl maleic anhydride, laurylamine and phenylethylamine as raw materials.
Comparative example 5 preparation of conductive composite masterbatch
(1) Uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid to grind for 2 hours; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube; wherein the dosage ratio of the carbon black to the carbon nano tube to the dispersion liquid is 2g:1g:10 mL;
(2) mixing the mixture of the carbon black and the carbon nano tube with a dispersant and polypropylene to obtain a mixed material; wherein the weight ratio of the mixture of the carbon black and the carbon nano tube, the dispersant and the polypropylene is 1:0.2: 2;
(3) extruding and granulating the mixed material by a double-screw extruder to obtain the conductive composite master batch;
wherein the dispersion liquid in the step (1) is composed of ethanol, vinyl triethoxysilane and 3- (phenylamino) propyl trimethoxysilane according to the volume ratio of 100:5: 2;
the dispersant in the step (2) is ethylene bis stearamide.
Example 5 differs from example 1 in that example 5 employs a conventional dispersant ethylene bis stearamide; and example 1 uses a dispersant prepared from phenyl maleic anhydride, laurylamine and phenylethylamine as raw materials.
Experimental example 1
Adding the high-conductivity composite master batch containing carbon black and carbon nanotubes prepared in the embodiments 1-3 and the conductive composite master batch prepared in the proportions 1-5 into polypropylene according to the addition amount of 3%, and then extruding the mixture by a double-screw extruder to obtain the antistatic polypropylene.
Preparing the antistatic polypropylene into a sample strip according to the requirements of GB/T1410-2006 and testing the volume resistivity of the sample strip; the test results are shown in table 1, wherein the smaller the volume resistivity is, the better the conductivity of the high-conductivity composite master batch is.
TABLE 1 volume resistivity test results for antistatic polypropylene
Volume resistivity | |
Polypropylene added with high-conductivity composite master batch containing carbon black and carbon nano tubes in example 1 | 3.5x106Ω·cm |
Polypropylene added with high-conductivity composite master batch containing carbon black and carbon nano tubes in example 2 | 8.8x106Ω·cm |
Polypropylene added with high-conductivity composite master batch containing carbon black and carbon nano tubes in example 3 | 7.1x106Ω·cm |
Polypropylene added with conductive composite master batch of comparative example 1 | 2.4x1010Ω·cm |
Polypropylene added with conductive composite master batch of comparative example 2 | 1.4x109Ω·cm |
Polypropylene added with conductive composite master batch of comparative example 3 | 2.1x109Ω·cm |
Polypropylene added with comparative example 4 conductive composite master batch | 5.3x109Ω·cm |
Polypropylene added with conductive composite master batch of comparative example 5 | 3.8x109Ω·cm |
As can be seen from the experimental data in Table 1, the polypropylene added with the highly conductive composite masterbatch containing carbon black and carbon nanotubes in the embodiments 1-3 is only added with 1% of carbon black and carbon nanotubes, and the volume resistivity thereof reaches 106Omega cm; has excellent antistatic performance.
It can also be seen from the experimental data in table 1 that the polypropylene added with the highly conductive composite masterbatch containing carbon black and carbon nanotubes in examples 1-3 has a volume resistivity much smaller than that of the polypropylene added with the conductive composite masterbatch in comparative example 1, and also much smaller than that of the polypropylene added with the conductive composite masterbatch in comparative examples 4 and 5; this indicates that: the dispersing agent has important influence on the conductivity of the prepared high-conductivity composite master batch; however, the conventional dispersing agent is difficult to further greatly improve the conductivity of the high-conductivity composite master batch; when the dispersing agent prepared by taking the phenyl maleic anhydride, the laurylamine and the phenylethylamine as raw materials is adopted, the conductivity of the high-conductivity composite master batch can be further greatly improved; and the improvement degree of the conductive performance of the high-conductivity composite master batch is far higher than that of the conventional dispersing agent.
As can be seen from the experimental data in Table 1, the volume resistivity of the polypropylene added with the conductive composite master batches of the comparative examples 2 and 3 is not greatly reduced compared with the polypropylene added with the conductive composite master batch of the comparative example 1, and the reduction range is far smaller than that of the polypropylene added with the high-conductivity composite master batch containing carbon black and carbon nano tubes prepared in the example 1; this indicates that: the dispersing agent prepared by the raw materials is not randomly selected, so that the conductive performance of the conductive composite master batch can be further greatly improved; the conductive performance of the conductive composite master batch can be greatly improved only by adding the dispersing agent prepared by taking the phenyl maleic anhydride, the laurylamine and the phenylethylamine as raw materials.
Claims (10)
1. A preparation method of a high-conductivity composite master batch containing carbon black and carbon nano tubes is characterized by comprising the following steps:
(1) uniformly mixing carbon black and carbon nano tubes, and then adding dispersion liquid for grinding; taking out the carbon black and the carbon nano tube after grinding, and drying to obtain a mixture of the carbon black and the carbon nano tube;
(2) mixing the mixture of the carbon black and the carbon nano tube with a dispersing agent and a high polymer material to obtain a mixed material;
(3) and extruding and granulating the mixed material by a screw extruder to obtain the high-conductivity composite master batch containing the carbon black and the carbon nano tube.
2. The method for preparing the highly conductive composite masterbatch containing carbon black and carbon nanotubes as claimed in claim 1, wherein the dispersion liquid in the step (1) comprises ethanol, vinyltriethoxysilane, and 3- (phenylamino) propyltrimethoxysilane.
3. The preparation method of the highly conductive composite masterbatch containing carbon black and carbon nanotubes according to claim 2, wherein the volume ratio of ethanol, vinyltriethoxysilane and 3- (phenylamino) propyltrimethoxysilane in the dispersion is 100: 4-6: 1-3;
most preferably, the volume ratio of ethanol, vinyltriethoxysilane, and 3- (phenylamino) propyltrimethoxysilane in the dispersion is 100:5: 2.
4. The method for preparing the highly conductive composite masterbatch containing carbon black and carbon nanotubes as claimed in claim 1, wherein the dispersant in step (2) is prepared by the following method: adding phenyl maleic anhydride into a reaction kettle, adding an organic solvent, stirring for dissolving, adding laurylamine and phenethylamine, and reacting in an inert gas atmosphere; after the reaction is finished, concentrating to remove the organic solvent to obtain the dispersing agent.
5. The preparation method of the highly conductive composite masterbatch containing carbon black and carbon nanotubes according to claim 4, wherein the dosage ratio of the phenyl maleic anhydride to the organic solvent to the laurylamine to the phenylethylamine is 150-200 g: 500-1000 mL: 80-100 g: 50-70 g;
most preferably, the ratio of the amount of phenyl maleic anhydride to the organic solvent and laurylamine and phenylethylamine is 180g:900mL:90g:60 g.
6. The method for preparing the highly conductive composite masterbatch containing carbon black and carbon nanotubes according to claim 5, wherein the specific reaction conditions in the inert gas atmosphere are as follows: reacting for 6-12 h at 100-150 ℃ in a nitrogen atmosphere;
most preferably, the specific conditions of the reaction in an inert gas atmosphere are: the reaction was carried out for 8h at 120 ℃ in a nitrogen atmosphere.
7. The preparation method of the highly conductive composite masterbatch containing carbon black and carbon nanotubes according to claim 1, wherein the amount ratio of the carbon black, the carbon nanotubes and the dispersion liquid in the step (1) is 1-3 g: 5-30 mL;
most preferably, the amount ratio of the carbon black to the carbon nanotubes and the dispersion in step (1) is 2g:1g:10 mL.
8. The method for preparing the highly conductive composite masterbatch containing carbon black and carbon nanotubes as claimed in claim 1, wherein the step (3) is performed by
The weight ratio of the mixture of the carbon black and the carbon nano tube, the dispersing agent and the high polymer material is 1: 0.1-0.3: 1-3;
most preferably, the weight ratio of the carbon black and carbon nanotube mixture, the dispersant and the polymeric material is 1:0.2: 2.
9. The method for preparing the highly conductive composite masterbatch containing carbon black and carbon nanotubes as claimed in claim 8, wherein the polymer material is polyethylene, polypropylene or polystyrene.
10. The high-conductivity composite master batch containing carbon black and carbon nanotubes, which is prepared by the preparation method of any one of claims 1 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111537644.0A CN114133665B (en) | 2021-12-15 | 2021-12-15 | High-conductivity composite master batch containing carbon black and carbon nano tubes and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111537644.0A CN114133665B (en) | 2021-12-15 | 2021-12-15 | High-conductivity composite master batch containing carbon black and carbon nano tubes and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114133665A true CN114133665A (en) | 2022-03-04 |
CN114133665B CN114133665B (en) | 2023-03-24 |
Family
ID=80382697
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111537644.0A Active CN114133665B (en) | 2021-12-15 | 2021-12-15 | High-conductivity composite master batch containing carbon black and carbon nano tubes and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114133665B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114854202A (en) * | 2022-06-07 | 2022-08-05 | 浙江柔灵科技有限公司 | Electrode material of silica gel filled with carbon black-carbon nanotube mixture and process thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080191176A1 (en) * | 2004-11-04 | 2008-08-14 | Norio Tobori | Conductive Masterbatch and Resin Composition Including the Same |
JP2016108524A (en) * | 2014-12-04 | 2016-06-20 | 東洋インキScホールディングス株式会社 | Conductive resin composition, conductive master batch, molded body, and production method of the same |
CN108250603A (en) * | 2018-01-19 | 2018-07-06 | 广州润锋科技有限公司 | Polystyrene carrier material that a kind of carbon nanotube conducting is modified and preparation method thereof |
CN110564113A (en) * | 2019-10-17 | 2019-12-13 | 重庆金美新材料科技有限公司 | Conductive master batch and preparation method thereof |
US20200106090A1 (en) * | 2018-09-28 | 2020-04-02 | Jiangsu Cnano Technology Co., Ltd. | Conductive Carbon Material Dispersing Agent and High-Conductivity Slurry for Lithium Battery |
CN112552581A (en) * | 2019-09-26 | 2021-03-26 | 合肥杰事杰新材料股份有限公司 | Conductive thermoplastic elastomer composite material and preparation method thereof |
-
2021
- 2021-12-15 CN CN202111537644.0A patent/CN114133665B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080191176A1 (en) * | 2004-11-04 | 2008-08-14 | Norio Tobori | Conductive Masterbatch and Resin Composition Including the Same |
JP2016108524A (en) * | 2014-12-04 | 2016-06-20 | 東洋インキScホールディングス株式会社 | Conductive resin composition, conductive master batch, molded body, and production method of the same |
CN108250603A (en) * | 2018-01-19 | 2018-07-06 | 广州润锋科技有限公司 | Polystyrene carrier material that a kind of carbon nanotube conducting is modified and preparation method thereof |
US20200106090A1 (en) * | 2018-09-28 | 2020-04-02 | Jiangsu Cnano Technology Co., Ltd. | Conductive Carbon Material Dispersing Agent and High-Conductivity Slurry for Lithium Battery |
CN112552581A (en) * | 2019-09-26 | 2021-03-26 | 合肥杰事杰新材料股份有限公司 | Conductive thermoplastic elastomer composite material and preparation method thereof |
CN110564113A (en) * | 2019-10-17 | 2019-12-13 | 重庆金美新材料科技有限公司 | Conductive master batch and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
于守武 著: "《高分子材料改性 原理及技术》", 31 May 2015, 知识产权出版社 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114854202A (en) * | 2022-06-07 | 2022-08-05 | 浙江柔灵科技有限公司 | Electrode material of silica gel filled with carbon black-carbon nanotube mixture and process thereof |
CN114854202B (en) * | 2022-06-07 | 2024-01-26 | 浙江柔灵科技有限公司 | Carbon black-carbon nano tube mixed silica gel filled electrode material and process thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114133665B (en) | 2023-03-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1543399B (en) | Coatings containing carbon nanotubes | |
US6168732B1 (en) | Electrically conductive polymeric materials and use thereof | |
US20100267883A1 (en) | Nanotube Polymer Composite Composition and Methods of Making | |
EP2818496B1 (en) | Production method for conductive resin composition, and conductive resin composition | |
US20140287176A1 (en) | Nanotube and finely milled carbon fiber polymer composite compositions and methods of making | |
CN102367310A (en) | Conductive carbon black modified PP material and preparation method thereof | |
TW200844154A (en) | Semiconductive resin composition | |
CN105315538A (en) | Regenerated polyethylene-graphene composite conducting material and preparation method thereof | |
CN114133665B (en) | High-conductivity composite master batch containing carbon black and carbon nano tubes and preparation method thereof | |
JP2003100147A (en) | Conductive material containing carbon nanotube and its manufacturing method | |
Simsek et al. | Temperature dependence of electrical conductivity in double-wall and multi-wall carbon nanotube/polyester nanocomposites | |
US9115271B2 (en) | Carbon nanotube powders and methods for manufacturing the same and composite materials | |
CN104603191B (en) | Thermoplastic polymer combined with carbon nano material and preparation method thereof | |
CN111761751A (en) | Preparation method and application of carbon-containing polyolefin master batch | |
Wang et al. | Preparation and properties of polysiloxane grafting multi‐walled carbon nanotubes/polycarbonate nanocomposites | |
CN111393744A (en) | TPE material with antibacterial conductivity and preparation method thereof | |
Afzal et al. | Review highlighting physical prospects of styrenic polymer and styrenic block copolymer reinforced with carbon nanotube | |
US20160297952A1 (en) | Polymer carbon nanotube composite | |
CN111073040A (en) | Preparation method of HGM-CNTs bonding substance and light antistatic polypropylene material | |
Li et al. | Covalent functionalization of multiwalled carbon nanotubes with super-hydrophobic property | |
CN112175363B (en) | Polyethylene terephthalate material containing carbon nano tube and preparation method thereof | |
CN109401057B (en) | Surface scratch-resistant polypropylene and preparation method thereof | |
CN110467775B (en) | Polypropylene composite material of spiral tube containing silicon oxide | |
CN108912645B (en) | Polycarbonate blending material with cold-resistant and conductive effects and preparation method thereof | |
Lee et al. | Preparation and properties of the highly porous poly (ethylene‐co‐vinyl alcohol)/multiwalled carbon nanotube nanocomposites prepared by a simple saponification method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |