Conductive black master batch material based on carbon nanotubes and preparation method of conductive black master batch material
By preparing conductive black masterbatch materials for carbon nanotubes and modified molecular sieve catalysts, the problem of traditional carbon black damage to mechanical properties is solved, and the conductivity and tensile strength of high-performance conductive plastics are improved.
Patent Information
- Application Number
- CN202510613527.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-13
- Publication Date
- 2025-07-25
AI Technical Summary
The addition of carbon black in traditional black masterbatches damages the mechanical properties of the plastic matrix and increases the difficulty of processing, which cannot meet the needs of high-performance conductive plastics.
Carbon nanotubes, dispersants, wax carriers and antioxidants are used as raw materials to prepare carbon nanotubes by specific methods, and modified molecular sieves are used as catalysts to prepare conductive black masterbatch materials.
The modified plastics prepared have good electrical conductivity and tensile strength to meet the application needs of high-performance conductive plastics.
Smart Images
Figure BDA0005400325790000061
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of polymer material preparation, and specifically relates to a conductive black masterbatch material based on carbon nanotubes and a preparation method thereof. Background Art
[0002] Conductive plastics are a new type of functional material made by adding conductive fillers to insulating polymers, which combine the advantages of plastics and the conductive properties of metals. Due to their characteristics such as light weight, easy processing and excellent mechanical properties, conductive plastics are widely used in fields such as electronics and electrical appliances, automobile manufacturing, and aerospace. With the development of technology and the increasing requirements for environmental protection, the market demand for high-performance conductive plastics is increasing day by day.
[0003] As a common type of masterbatch, black masterbatch occupies an important position in the field of plastic coloring. Traditional black masterbatch mainly uses carbon black as a pigment, which not only imparts black color to the product but also provides certain conductivity. However, carbon black has some inherent defects. For example, the addition of carbon black will not only damage the mechanical properties of the plastic matrix but also increase the processing difficulty. Therefore, exploring new conductive fillers has become one of the key research directions. Summary of the Invention
[0004] In order to overcome at least one of the technical problems existing in the prior art, the present invention provides a conductive black masterbatch material based on carbon nanotubes and a preparation method thereof.
[0005] The technical solution of the present invention is as follows:
[0006] The present invention first provides a conductive black masterbatch material based on carbon nanotubes, which comprises the following raw material components in parts by weight: 80-100 parts of carbon nanotubes; 8-20 parts of dispersant; 5-20 parts of wax carrier; 5-15 parts of antioxidant.
[0007] Preferably, the conductive black masterbatch material based on carbon nanotubes comprises the following raw material components in parts by weight: 85-92 parts of carbon nanotubes; 8-15 parts of dispersant; 8-15 parts of wax carrier; 8-15 parts of antioxidant.
[0008] Most preferably, the conductive black masterbatch material based on carbon nanotubes is characterized in that it comprises the following raw material components in parts by weight: 90 parts of carbon nanotubes; 10 parts of dispersant; 10 parts of wax carrier; 10 parts of antioxidant.
[0009] Preferably, the carbon nanotubes are prepared by the following method:
[0010] S11. Take a carbon source, crush it to obtain a carbon source powder;
[0011] S12. The carbon source powder and the catalyst are added to a ball mill and mixed uniformly to obtain a carbon source-catalyst mixture;
[0012] S13. Place the carbon source-catalyst mixture into a tubular furnace and perform heat treatment in an inert gas atmosphere; after the heat treatment, the carbon nanotubes are obtained.
[0013] The inventors have found in their research that adding carbon nanotubes prepared by the above-mentioned new method of the present invention to the conductive black masterbatch material can make the prepared modified plastic have better conductive properties.
[0014] Preferably, the carbon source in step S11 is selected from paraffin, polypropylene or polyethylene.
[0015] Preferably, the weight ratio of the carbon source powder to the catalyst in step S12 is 100:3-8.
[0016] Most preferably, the weight ratio of the carbon source powder to the catalyst in step S2 is 100:5.
[0017] Preferably, the heat treatment in step S13 specifically refers to heat treatment at 700-800° C. for 2-4 hours.
[0018] Preferably, the catalyst is selected from molecular sieves.
[0019] The molecular sieve is molecular sieve HZSM-5.
[0020] Preferably, the molecular sieve is a modified molecular sieve;
[0021] The modified molecular sieve is prepared by the following method:
[0022] S21. The molecular sieve is added to water and ultrasonically dispersed to obtain a molecular sieve dispersion;
[0023] S22. Add metal chloride and sodium hydroxide to the dispersion, stir for 3 to 8 hours, and then filter and separate the solid;
[0024] S23. The solid is placed in a tubular furnace and calcined in an air atmosphere; after the calcination, the calcined solid is taken to obtain the modified molecular sieve.
[0025] The inventors found in further research that carbon nanotubes prepared using the modified molecular sieve prepared by the above-mentioned new method of the present invention as a catalyst can significantly improve the tensile strength of modified plastics added with the conductive black masterbatch material of the present invention, compared with carbon nanotubes prepared using unmodified molecular sieves as a catalyst.
[0026] Preferably, in step S21, the weight ratio of molecular sieve to water is 1:5-10.
[0027] Most preferably, the weight ratio of the molecular sieve to water in step S21 is 1:7.
[0028] Preferably, the weight ratio of the dispersion liquid to the metal chloride and sodium hydroxide in step S22 is 100:10 - 15:15 - 20.
[0029] Most preferably, the weight ratio of the dispersion liquid to the metal chloride and sodium hydroxide in step S22 is 100:13:15.
[0030] Preferably, the metal chloride described in step S22 is selected from aluminum chloride or cobalt chloride.
[0031] Further preferably, the metal chloride described in step S22 is composed of aluminum chloride and cobalt chloride.
[0032] Preferably, the weight ratio of aluminum chloride to cobalt chloride is 2 - 4:1 - 3.
[0033] Most preferably, the weight ratio of aluminum chloride to cobalt chloride is 3:2.
[0034] The inventor further found in the research that in the preparation step S22 of the modified molecular sieve, the modified molecular sieve obtained by simultaneously using aluminum chloride and cobalt chloride for modification can further greatly improve the tensile strength of the modified plastic added with the conductive black masterbatch material of the present invention; the degree of improvement of the tensile strength of the modified plastic added with the conductive black masterbatch material of the present invention is much higher than that of the modified molecular sieve obtained by using only aluminum chloride or only cobalt chloride for modification. In the preparation step S22 of the modified molecular sieve, the modified molecular sieve obtained by simultaneously using aluminum chloride and cobalt chloride for modification can synergistically improve the tensile strength of the modified plastic added with the conductive black masterbatch material of the present invention.
[0035] Preferably, the calcination treatment in step S23 specifically refers to calcining at 800 - 1000 °C for 3 - 6 h.
[0036] Most preferably, the calcination treatment in step S23 specifically refers to calcining at 950 °C for 4 h.
[0037] Preferably, the inert gas atmosphere in step S23 specifically refers to a nitrogen atmosphere.
[0038] Preferably, the dispersant is selected from stearic acid or polyvinylpyrrolidone.
[0039] Preferably, the wax carrier is selected from one or a mixture of polyethylene wax (PE wax), paraffin wax, and EVA wax.
[0040] Preferably, the antioxidant is selected from antioxidant 1010 or antioxidant 168.
[0041] The present invention also provides a preparation method of a conductive black masterbatch material based on carbon nanotubes, which comprises the following steps:
[0042] Put carbon nanotubes, a dispersant, a wax carrier and an antioxidant into a kneader for melt blending, and then transfer them to a pelletizer. After compaction and granulation, the conductive black masterbatch material based on carbon nanotubes is obtained.
[0043] Beneficial effects: The present invention provides a brand-new conductive black masterbatch material based on carbon nanotubes; research shows that by using the conductive black masterbatch material based on carbon nanotubes of the present invention, the prepared modified plastic can have good conductive performance; at the same time, it also has good tensile strength; it has important application value. Specific embodiments
[0044] The following specific embodiments are used to further explain the present invention, but the embodiments do not limit the present invention in any form.
[0045] In the following embodiments, the polypropylene resin used is polypropylene with the brand V30G from Sinopec; for the remaining raw materials whose sources are not specified, they are all conventional raw materials that those skilled in the art can obtain through regular purchasing channels.
[0046] Example 1 Preparation of a conductive black masterbatch material based on carbon nanotubes
[0047] Composition by weight of raw materials: 90 parts of carbon nanotubes; 10 parts of dispersant (stearic acid); 10 parts of wax carrier (polyethylene wax); 10 parts of antioxidant (antioxidant 1010);
[0048] The carbon nanotubes are prepared by the following method:
[0049] S11. Take a carbon source, and after pulverization, obtain a carbon source powder; the carbon source is polypropylene resin;
[0050] S12. Add the carbon source powder and a catalyst to a ball mill for ball milling and mixing evenly to obtain a carbon source-catalyst mixture; the weight ratio of the carbon source powder to the catalyst is 100:5; the catalyst is molecular sieve HZSM-5;
[0051] S13. Put the carbon source-catalyst mixture into a tubular furnace, and carry out heat treatment at 750 °C for 3 h in a nitrogen atmosphere; after the heat treatment is completed, the carbon nanotubes are obtained.
[0052] Preparation method: Put carbon nanotubes, a dispersant, a wax carrier and an antioxidant into a kneader for melt blending, and then transfer them to a pelletizer. After compaction and granulation, the conductive black masterbatch material based on carbon nanotubes is obtained.
[0053] Preparation of Carbon Nanotube-based Conductive Black Masterbatch Material in Example 2
[0054] Raw material weight composition: 90 parts of carbon nanotubes; 10 parts of dispersant (stearic acid); 10 parts of wax carrier (polyethylene wax); 10 parts of antioxidant (antioxidant 1010);
[0055] The carbon nanotubes are prepared by the following method:
[0056] S11. Take a carbon source, crush it to obtain a carbon source powder; the carbon source is polypropylene resin;
[0057] S12. Add the carbon source powder and the catalyst to a ball mill and ball mill and mix evenly to obtain a carbon source-catalyst mixture; the weight ratio of the carbon source powder to the catalyst is 100:5; the catalyst is a modified molecular sieve;
[0058] S13. Put the carbon source-catalyst mixture into a tube furnace, and perform heat treatment at 750 °C for 3 h in a nitrogen atmosphere; after the heat treatment is completed, the carbon nanotubes are obtained.
[0059] The modified molecular sieve is prepared by the following method:
[0060] S21. Add molecular sieve HZSM-5 to water, and ultrasonically disperse to obtain a molecular sieve dispersion; among them, the weight ratio of the molecular sieve to water is 1:7;
[0061] S22. Add metal chloride and sodium hydroxide to the dispersion, stir for 6 h and then filter to separate the solid; among them, the weight ratio of the dispersion to the metal chloride and sodium hydroxide is 100:13:15; the metal chloride is aluminum chloride;
[0062] S23. Put the solid into a tube furnace, and calcine at 950 °C for 4 h in an air atmosphere; after the calcination is completed, take the calcined solid to obtain the modified molecular sieve.
[0063] Preparation method: Put the carbon nanotubes, dispersant, wax carrier and antioxidant into a mixer and melt-blend, and then transfer to a pelletizer and compact and pelletize to obtain the carbon nanotube-based conductive black masterbatch material.
[0064] Preparation of Carbon Nanotube-based Conductive Black Masterbatch Material in Example 3
[0065] Raw material weight composition: 90 parts of carbon nanotubes; 10 parts of dispersant (stearic acid); 10 parts of wax carrier (polyethylene wax); 10 parts of antioxidant (antioxidant 1010);
[0066] The carbon nanotubes are prepared by the following method:
[0067] S11. Take a carbon source, crush it to obtain carbon source powder; the carbon source is polypropylene resin;
[0068] S12. Add the carbon source powder and the catalyst to a ball mill, and ball mill and mix them evenly to obtain a carbon source-catalyst mixture; the weight ratio of the carbon source powder to the catalyst is 100:5; the catalyst is a modified molecular sieve;
[0069] S13. Put the carbon source-catalyst mixture into a tubular furnace, and perform heat treatment at 750 °C for 3 h in a nitrogen atmosphere; after the heat treatment is completed, the carbon nanotubes are obtained.
[0070] The modified molecular sieve is prepared by the following method:
[0071] S21. Add molecular sieve HZSM-5 to water, and ultrasonically disperse it to obtain a molecular sieve dispersion; among them, the weight ratio of the molecular sieve to water is 1:7;
[0072] S22. Add metal chloride and sodium hydroxide to the dispersion, stir for 6 h, and then filter and separate the solid; among them, the weight ratio of the dispersion to the metal chloride and sodium hydroxide is 100:13:15; the metal chloride is cobalt chloride;
[0073] S23. Put the solid into a tubular furnace, and calcine it at 950 °C for 4 h in an air atmosphere; after the calcination is completed, take the calcined solid to obtain the modified molecular sieve.
[0074] Preparation method: Put the carbon nanotubes, dispersant, wax carrier and antioxidant into a mixer and melt-blend them, and then transfer them to a pelletizer to obtain the carbon nanotube-based conductive black masterbatch material after compaction and granulation.
[0075] Example 4 Preparation of Carbon Nanotube-Based Conductive Black Masterbatch Material
[0076] Composition of raw materials by weight: 90 parts of carbon nanotubes; 10 parts of dispersant (stearic acid); 10 parts of wax carrier (polyethylene wax); 10 parts of antioxidant (antioxidant 1010);
[0077] The carbon nanotubes are prepared by the following method:
[0078] S11. Take a carbon source, crush it to obtain carbon source powder; the carbon source is polypropylene resin;
[0079] S12. Add the carbon source powder and the catalyst to a ball mill, and ball mill and mix them evenly to obtain a carbon source-catalyst mixture; the weight ratio of the carbon source powder to the catalyst is 100:5; the catalyst is a modified molecular sieve;
[0080] S13. Place the carbon source-catalyst mixture into a tubular furnace and conduct heat treatment at 750 °C for 3 h in a nitrogen atmosphere; after the heat treatment is completed, the carbon nanotubes are obtained.
[0081] The modified molecular sieve is prepared by the following method:
[0082] S21. Add molecular sieve HZSM-5 into water and obtain a molecular sieve dispersion after ultrasonic dispersion; wherein, the weight ratio of the molecular sieve to water is 1:7.
[0083] S22. Add metal chloride and sodium hydroxide into the dispersion, stir for 6 h and then filter to separate the solid; wherein, the weight ratio of the dispersion to the metal chloride and sodium hydroxide is 100:13:15; the metal chloride is composed of aluminum chloride and cobalt chloride with a weight ratio of 3:2.
[0084] S23. Place the solid into a tubular furnace and calcine at 950 °C for 4 h in an air atmosphere; after the calcination is completed, take the calcined solid to obtain the modified molecular sieve.
[0085] Preparation method: Put carbon nanotubes, dispersant, wax carrier and antioxidant into a mixer and melt-blend them, and then transfer them to a granulator to obtain the carbon nanotube-based conductive black masterbatch material after compaction and granulation.
[0086] Add the carbon nanotube-based conductive black masterbatch materials prepared in Examples 1 to 4 to polypropylene resin at an addition amount of 10 wt% to obtain test samples 1 to 4, and prepare modified polypropylene resin; and test the surface resistance and tensile strength of the modified polypropylene resin, and the test results are shown in Table 1.
[0087] Table 1. Performance test of the carbon nanotube-based conductive black masterbatch material of the present invention
[0088]
[0089] It can be seen from the experimental results in Table 1 that the surface resistivity of test samples 1 to 4 has reached 10 4 ; this shows that: by using the carbon nanotube-based conductive black masterbatch material of the present invention, the prepared modified plastic can have good electrical conductivity.
[0090] It can be seen from the experimental results in Table 1 that the surface resistivity of test samples 2 to 4 is significantly lower than that of test sample 1; this shows that: the carbon nanotubes prepared by using the modified molecular sieve prepared by the above new method of the present invention as a catalyst can significantly improve the electrical conductivity of the modified plastic added with the conductive black masterbatch material of the present invention compared with the carbon nanotubes prepared by using the unmodified molecular sieve as a catalyst.
[0091] It can be seen from the experimental results in Table 1 that the tensile strength of samples 2 to 4 is significantly or even substantially higher than that of sample 1; this indicates that the carbon nanotubes prepared using the modified molecular sieve prepared by the above-mentioned new method of the present invention as a catalyst can significantly or even substantially improve the tensile strength of the modified plastic to which the conductive black masterbatch material of the present invention is added, compared with the carbon nanotubes prepared using the unmodified molecular sieve as a catalyst.
[0092] From the experimental results in Table 1, it can be seen that the tensile strength of the sample 4 to be tested is much higher than that of the sample 1 to be tested; it is also much higher than that of the samples 2 and 3 to be tested; this shows that: in the preparation step S22 of the modified molecular sieve, the modified molecular sieve obtained by simultaneously modifying with aluminum chloride and cobalt chloride can further significantly improve the tensile strength of the modified plastic to which the conductive black masterbatch material of the present invention is added; the degree of improvement in the tensile strength of the modified plastic to which the conductive black masterbatch material of the present invention is added is much higher than the modified molecular sieve obtained by modifying with aluminum chloride alone or cobalt chloride alone. In the preparation step S22 of the modified molecular sieve, the modified molecular sieve obtained by simultaneously modifying with aluminum chloride and cobalt chloride can synergistically improve the tensile strength of the modified plastic to which the conductive black masterbatch material of the present invention is added.
Claims
1. A conductive black masterbatch material based on carbon nanotubes, characterized in that, The raw material components comprise the following parts by weight: 80 - 100 parts of carbon nanotubes; 8 - 20 parts of dispersant; 5 - 20 parts of wax carrier; 5 - 15 parts of antioxidant.
2. The carbon nanotube-based electrically conductive black masterbatch material according to claim 1, wherein The raw material components comprise the following parts by weight: 85 - 92 parts of carbon nanotubes; 8 - 15 parts of dispersant; 8 - 15 parts of wax carrier; 8 - 15 parts of antioxidant; Most preferably, the carbon nanotube - based conductive masterbatch material is characterized in that the raw material components comprise the following parts by weight: 90 parts of carbon nanotubes; 10 parts of dispersant; 10 parts of wax carrier; 10 parts of antioxidant.
3. The carbon nanotube-based electrically conductive black masterbatch material according to claim 1, characterized in that, The carbon nanotubes are prepared by the following method: S11. Take a carbon source, and obtain a carbon source powder after pulverization. S12. Add the carbon source powder and a catalyst into a ball mill and ball - mill and mix them evenly to obtain a carbon source - catalyst mixture. S13. Put the carbon source - catalyst mixture into a tubular furnace and conduct heat treatment in an inert gas atmosphere; after the heat treatment is completed, the carbon nanotubes are obtained.
4. The carbon nanotube-based electrically conductive black masterbatch material according to claim 3, wherein The carbon source described in step S11 is selected from paraffin, polypropylene or polyethylene.
5. The carbon nanotube-based electrically conductive black masterbatch material according to claim 3, characterized in that, The weight ratio of the carbon source powder to the catalyst in step S12 is 100:3 - 8; Most preferably, the weight ratio of the carbon source powder to the catalyst in step S2 is 100:
5.
6. The carbon nanotube-based electrically conductive black masterbatch material according to claim 3, wherein, The heat treatment in step S13 specifically refers to heat treatment at 700 - 800 °C for 2 - 4 h.
7. The carbon nanotube-based electrically conductive black masterbatch material according to claim 5, wherein The catalyst is selected from molecular sieve (HZSM - 5).
8. The carbon nanotube-based electrically conductive black masterbatch material according to claim 7, characterized in that, The molecular sieve is a modified molecular sieve; The modified molecular sieve is prepared by the following method: S21. Add the molecular sieve into water and obtain a molecular sieve dispersion after ultrasonic dispersion. S22. Add metal chloride and sodium hydroxide into the dispersion, stir for 3 - 8 h and then filter to separate the solid. S23. Put the solid into a tubular furnace and conduct calcination treatment in an air atmosphere; after the calcination is completed, take the calcined solid to obtain the modified molecular sieve.
9. The carbon nanotube-based electrically conductive black masterbatch material according to claim 8, characterized in that, The metal chloride described in step S22 is selected from aluminum chloride or cobalt chloride.
10. The preparation method of the carbon nanotube-based electrically conductive black masterbatch material according to any one of Rights Enterprises 1 to 9, characterized in that, It comprises the following steps: Put the carbon nanotubes, dispersant, wax carrier and antioxidant into a mixer and conduct melt - blending, and then transfer them to a pelletizer, and obtain the carbon nanotube - based conductive masterbatch material after compaction and pelletization.