Petroleum-based carbon black-containing high-thermal-conductivity rubber filler and preparation method thereof

Abstract

The invention discloses a high-thermal-conductivity rubber filler containing petroleum-based carbon black and a preparation method of the high-thermal-conductivity rubber filler. The high-thermal-conductivity rubber filler comprises the following raw materials: 20-80wt% of petroleum-based carbon black; 20 wt%-80 wt% of acetylene carbon black; 0.1 wt% to 5.0 wt% of a carbon nanotube; and 0.1 wt%-5.0 wt% of graphene. The invention also discloses a preparation method of the high-thermal-conductivity rubber filler containing the petroleum-based carbon black. The preparation method comprises the following steps: weighing the petroleum-based carbon black, the acetylene carbon black, the carbon nanotubes and the graphene in proportion, putting the weighed materials into a granulator, and granulating the materials into uniform small particles. The high-thermal-conductivity petroleum-based carbon black provided by the invention is high in thermal conductivity and good in dispersity, and the mechanical property of rubber is considered while the thermal conductivity requirement of a rubber material is met.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber fillers, and in particular to a high thermal conductivity rubber filler containing petroleum-based carbon black and a preparation method thereof. Background Art

[0002] Rubber, a widely used polymer material, requires a large amount of fillers during its preparation and processing to improve its mechanical properties, processing performance, and filling capacity. Currently, commonly used rubber fillers include carbon black and silica. Carbon black is an important filling and reinforcement material for rubber. In the technical field of specialty rubber products such as tire bladders, rubber compounds must have both high thermal conductivity and certain mechanical properties, which places higher demands on the performance of rubber fillers.

[0003] Traditional fillers for tire bladders primarily use acetylene black or coal tar-based carbon black. Acetylene black can meet the thermal conductivity requirements of tire bladders, but mechanical properties (such as tensile strength and modulus of elongation) are weak. Coal tar-based carbon black can meet the mechanical requirements of tire bladders, but its thermal conductivity is poor.

[0004] In the face of the above problems, the tire capsule rubber compound must have both high thermal conductivity and certain mechanical properties. Therefore, this application improves the performance of the rubber filler. The treated rubber filler can give the rubber compound higher thermal conductivity while meeting the mechanical properties of the rubber compound. Summary of the Invention

[0005] The present invention aims to provide a highly thermally conductive rubber filler containing petroleum-based carbon black and a method for preparing the same. The rubber filler is prepared by mixing and granulating petroleum-based carbon black, acetylene black, carbon nanotubes, and graphene. The filler imparts high thermal conductivity to the rubber compound while also meeting certain mechanical properties.

[0006] To achieve the above object, the present invention provides a high thermal conductivity rubber filler containing petroleum-based carbon black, wherein the rubber filler comprises the following components:

[0007] Petroleum-based carbon black 20wt%-80wt%

[0008] Acetylene black 20wt%-80wt%

[0009] Carbon nanotubes 0.1wt%-5wt%

[0010] Graphene 0.1wt%-5wt%;

[0011] Petroleum-based carbon black is furnace carbon black produced from petroleum-based composite raw material oil. The composition of the petroleum-based composite raw material oil, calculated by weight percentage, is asphaltene content less than 12wt%, carbon content greater than 90wt%, alkali metal content less than 200ppm, aromatic hydrocarbon content greater than 75wt%, of which the content of short side chain aromatic hydrocarbons with double or triple bonds is not less than 20wt%.

[0012] According to the embodiments of the present application, the petroleum-based raw material oil is a composite raw material oil of refining residue oil and ethylene tar, the proportion of ethylene tar in the composite raw material oil is not less than 10%, and the solid impurity content of the refining residue oil is less than 500 ppm.

[0013] According to the embodiments of the present application, the iodine absorption value of petroleum-based carbon black is greater than 80 g / kg, and the oil absorption value is greater than 85 10 -5 m 3 / kg.

[0014] According to the embodiment of the present application, the oil absorption value of acetylene carbon black is greater than 150 10 -5 m 3 / kg.

[0015] According to an embodiment of the present application, the carbon nanotube has a diameter of 5-20 nm and a length of 5-100 μm.

[0016] According to the embodiment of the present application, the graphene specific surface area is 50m 2 / g-1000m 2 / g.

[0017] Another aspect of the present application discloses a method for preparing the above-mentioned high thermal conductivity rubber filler containing petroleum-based carbon black, comprising the following steps:

[0018] S1: After weighing petroleum-based carbon black, acetylene black, carbon nanotubes, and graphene, put them into a stirring tank, stir at room temperature, at a stirring speed of 15-30 r / min, and for 10-30 min to mix them evenly;

[0019] S2: The material obtained in step S1 is fed into a granulator, and granulated into uniform fine particles at a speed of 5-20 r / min using a non-additive process;

[0020] S3: The rubber filler is packed after uniform granulation.

[0021] According to an embodiment of the present application, in step S2, uniform fine particles of 0.5-3 mm are obtained by the granulator.

[0022] The beneficial effects of the technical solution of the present invention compared with the prior art are:

[0023] 1. The present invention utilizes petroleum-based carbon black in combination with acetylene black, carbon nanotubes, and graphene as rubber fillers. This not only overcomes the defects of traditional tire bladder fillers that mainly use acetylene black or coal tar-based carbon black, and improves the mechanical properties and thermal conductivity of rubber; it also realizes the recycling of industrial petroleum waste, promotes efficiency improvement of metallurgical enterprises and cost reduction of the rubber products industry, and meets the current industrial development requirements of energy conservation, environmental protection, and circular economy.

[0024] 2. The composite rubber filler of the present invention is applied to rubber materials, which can improve the preparation method of rubber on the one hand, and can also improve the reactivity and dispersibility of the filler in the rubber matrix on the other hand, thereby improving the physical properties of the rubber.

[0025] 3. The preparation method of the present invention is simple and easy to operate, has high universality, and has high equipment versatility, and has good market application value in the rubber industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a flowchart of the steps of a method for preparing a high thermal conductivity rubber filler containing petroleum-based carbon black in an example of the present invention. DETAILED DESCRIPTION

[0027] The present invention will be further described below in conjunction with the accompanying drawings and specific examples. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0028] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0029] See Figure 1 As shown, a high thermal conductivity rubber filler containing petroleum-based carbon black is shown, and the rubber filler includes the following components:

[0030] Petroleum-based carbon black 20wt%-80wt%

[0031] Acetylene black 20wt%-80wt%

[0032] Carbon nanotubes 0.1wt%-5wt%

[0033] Graphene 0.1wt%-5wt%;

[0034] Petroleum-based carbon black is furnace carbon black produced from petroleum-based composite raw material oil. The composition of the petroleum-based composite raw material oil, calculated by weight percentage, is asphaltene content less than 12wt%, carbon content greater than 90wt%, alkali metal content less than 200ppm, aromatic hydrocarbon content greater than 75wt%, of which the content of short side chain aromatic hydrocarbons with double bonds or triple bonds is not less than 20wt%.

[0035] According to the embodiments of the present application, the iodine absorption value of petroleum-based carbon black is greater than 80 g / kg, and the oil absorption value is greater than 85 10 -5 m 3 / kg.

[0036] According to the embodiment of the present application, the oil absorption value of acetylene carbon black is greater than 150 10 -5 m 3 / kg.

[0037] According to an embodiment of the present application, the carbon nanotube has a diameter of 5-20 nm and a length of 5-100 μm.

[0038] According to the embodiment of the present application, the graphene specific surface area is 50m 2 / g-1000m 2 / g.

[0039] Another aspect of the present application discloses a method for preparing the above-mentioned high thermal conductivity rubber filler containing petroleum-based carbon black, comprising the following steps:

[0040] S1: Weigh the petroleum-based carbon black prepared in step S1, acetylene black, carbon nanotubes, and graphene, and put them into a stirring tank. Stir at room temperature, at a speed of 15-30 r / min, and for 10-30 min until they are evenly mixed.

[0041] S2: The material obtained in step S1 is fed into a granulator, and granulated into uniform fine particles of 0.5-3 mm at a speed of 5-20 r / min using a non-additive process;

[0042] S3: The rubber filler is packed after uniform granulation.

[0043] Example 1

[0044] The petroleum-based composite feedstock used is composed of 8wt% asphaltene, 93wt% carbon, 150ppm alkali metals, and 81wt% aromatics, including 45wt% short-chain aromatics with double or triple bonds. The petroleum-based raw material is a composite feedstock of refining residue oil and ethylene tar, with ethylene tar accounting for 15% of the composite feedstock and the refining residue oil containing 420ppm solid impurities.

[0045] Carbon black, iodine absorption value is 123g / kg, oil absorption value is 83 10 -5 m 3 / kg.

[0046] 1. A method for preparing a high thermal conductivity rubber filler containing the above-mentioned petroleum-based carbon black, comprising the following steps:

[0047] (1) Calculated by weight percentage for preparing rubber filler, the components used and their mass ratios are:

[0048] Petroleum-based carbon black 22wt%

[0049] Acetylene black 75wt%

[0050] Carbon nanotubes 0.5wt%

[0051] Graphene 2.5wt%;

[0052] The petroleum-based carbon black, acetylene black, carbon nanotubes and graphene were weighed according to the above proportions, and put into a stirring tank for mixing at room temperature, a stirring speed of 20 r / min, and a stirring time of 10 min to mix uniformly;

[0053] Among them, the iodine absorption value of petroleum-based carbon black raw materials is 85 g / kg and the oil absorption value is 105 10 -5 m 3 / kg; acetylene black oil absorption value is 155 10 -5 m 3 / kg; carbon nanotubes have a diameter of 8nm and a length of 10μm; graphene has a specific surface area of 350m 2 / g.

[0054] (2) The material obtained in the above step is fed into a granulator and rotated at a speed of 5 r / min to granulate into uniform fine particles of 0.5-3 mm;

[0055] (3) The rubber filler is packed after uniform granulation.

[0056] Example 2

[0057] The petroleum-based composite feedstock used is composed of 8wt% asphaltene, 93wt% carbon, 150ppm alkali metals, and 81wt% aromatics, including 45wt% short-chain aromatics with double or triple bonds. The petroleum-based raw material is a composite feedstock of refining residue oil and ethylene tar, with ethylene tar accounting for 20% of the composite feedstock and the refining residue oil containing 400ppm solid impurities.

[0058] 1. A method for preparing a high thermal conductivity rubber filler containing the above-mentioned petroleum-based carbon black, comprising the following steps:

[0059] (1) Calculated by weight percentage for preparing rubber filler, the components used and their mass ratios are:

[0060] Petroleum-based carbon black 50wt%

[0061] Acetylene black 47wt%

[0062] Carbon nanotubes 1wt%

[0063] Graphene 2wt%;

[0064] The petroleum-based carbon black, acetylene black, carbon nanotubes and graphene were weighed according to the above proportions, and then put into a stirring tank for mixing at room temperature, a stirring speed of 15 r / min, and a stirring time of 20 min to mix uniformly;

[0065] Among them, the iodine absorption value of petroleum-based carbon black raw materials is 123 g / kg, and the oil absorption value is 83 10 -5 m 3 / kg; acetylene black oil absorption value is 180 10 -5 m 3 / kg; carbon nanotubes have a diameter of 13nm and a length of 300μm; graphene has a specific surface area of 800m 2 / g.

[0066] (2) The material obtained in the above step is fed into a granulator and rotated at a speed of 20 r / min to granulate into uniform fine particles of 0.5-3 mm;

[0067] (3) The rubber filler is packed after uniform granulation.

[0068] Example 3

[0069] The petroleum-based composite feedstock used is composed of 9wt% asphaltene, 91wt% carbon, less than 60ppm alkali metal, and 83wt% aromatics, including 35wt% short side-chain aromatics with double or triple bonds. The petroleum-based composite feedstock is a composite of refining residue oil and ethylene tar, with ethylene tar accounting for 25% of the composite feedstock and the refining residue oil containing 480ppm solid impurities.

[0070] 1. A method for preparing a high thermal conductivity rubber filler containing the above-mentioned petroleum-based carbon black, comprising the following steps:

[0071] (1) Calculated by weight percentage for preparing rubber filler, the components used and their mass ratios are:

[0072] Petroleum-based carbon black 75wt%

[0073] Acetylene black 22wt%

[0074] Carbon nanotubes 2.5wt%

[0075] Graphene 0.5wt%;

[0076] The petroleum-based carbon black, acetylene black, carbon nanotubes and graphene were weighed according to the above proportions, and then put into a stirring tank for mixing at room temperature, a stirring speed of 30 r / min, and a stirring time of 30 min to mix uniformly;

[0077] Among them, the iodine absorption value of petroleum-based carbon black raw materials is 160 g / kg, and the oil absorption value is 115 10 -5 m 3 / kg; acetylene carbon black oil absorption value is 220 10 -5 m 3 / kg; carbon nanotubes have a diameter of 20nm and a length of 90μm; graphene has a specific surface area of 60m 2 / g.

[0078] (2) The material obtained in the above step is fed into a granulator and rotated at a speed of 10 r / min to granulate into uniform fine particles of 0.5-3 mm;

[0079] (3) The rubber filler is packed after uniform granulation.

[0080] The petroleum-based carbon black-containing rubber fillers obtained in Examples 1-3 were subjected to performance testing in accordance with "Carbon Black - Part 18: Identification Method in Natural Rubber (NR)" GB / T 3780.18-2017, including measurements of rubber thermal conductivity, 300% modulus of elongation, and tensile strength. Simultaneously, rubber containing coal tar-based carbon black as a filler, as Comparative Example 1, and rubber containing only acetylene carbon black as a filler, as Comparative Example 2, were also tested for rubber properties. The specific test results are shown in Table 1, along with the specific comparisons.

[0081] Table 1

[0082]

[0083] It can be seen that the rubber filler manufactured using the petroleum-based carbon black raw material of this application can simultaneously meet the requirements of the tire bladder for the thermal conductivity and mechanical properties of the rubber material. Its thermal conductivity is comparable to that of the rubber filler added with only acetylene carbon black, and its mechanical properties (tensile strength, tensile stress, etc.) are significantly better than those of the rubber filler added with only acetylene carbon black.

[0084] In summary, the technical solution of this application has the following beneficial effects:

[0085] 1. The present invention utilizes petroleum-based carbon black in combination with acetylene black, carbon nanotubes, and graphene as rubber fillers. This not only overcomes the defects of traditional tire bladder fillers that mainly use acetylene black or coal tar-based carbon black, and improves the mechanical properties and thermal conductivity of rubber; it also realizes the recycling of industrial petroleum waste, promotes efficiency improvement of metallurgical enterprises and cost reduction of the rubber products industry, and meets the current industrial development requirements of energy conservation, environmental protection, and circular economy.

[0086] 2. The composite rubber filler of the present invention is applied to rubber materials, which can improve the preparation method of rubber on the one hand, and can also improve the reactivity and dispersibility of the filler in the rubber matrix on the other hand, thereby improving the physical properties of the rubber.

[0087] 3. The preparation method of the present invention is simple and easy to operate, has high universality, and has high equipment versatility, and has good market application value in the rubber industry.

[0088] The above are only preferred embodiments of the present invention and do not limit the implementation mode and protection scope of the present invention. For those skilled in the art, it should be aware that all solutions obtained by equivalent substitutions and obvious changes made using the description and illustrations of the present invention should be included in the protection scope of the present invention.

Claims

1. A high thermal conductivity rubber filler containing petroleum-based carbon black, characterized in that: The rubber filler comprises the following components by weight: Petroleum-based carbon black 20wt%-80wt% Acetylene black 20wt%-80wt% Carbon nanotubes 0.1wt%-5wt% Graphene 0.1wt%-5wt%; The petroleum-based carbon black is a furnace carbon black produced using petroleum-based composite raw material oil as raw material. The petroleum-based composite raw material oil has the following composition by weight percentage: asphaltene content less than 12wt%, carbon content greater than 90wt%, alkali metal content less than 200ppm, aromatic hydrocarbon content greater than 75wt%, and short side chain aromatic hydrocarbon content with double bonds or triple bonds is not less than 20wt%.

2. The high thermal conductivity rubber filler containing petroleum-based carbon black according to claim 1, characterized in that: The petroleum-based carbon black has an iodine absorption value greater than 80 g / kg and an oil absorption value greater than 85 10 -5 m 3 / kg.

3. The high thermal conductivity rubber filler containing petroleum-based carbon black according to claim 1, characterized in that: The acetylene black oil absorption value is greater than 150 10 -5 m 3 / kg.

4. The high thermal conductivity rubber filler containing petroleum-based carbon black according to claim 1, characterized in that: The carbon nanotubes have a diameter of 5-20 nm and a length of 5-100 μm.

5. The high thermal conductivity rubber filler containing petroleum-based carbon black according to claim 1, characterized in that: The graphene specific surface area is 50m 2 / g-1000m 2 / g.

6. The high thermal conductivity rubber filler containing petroleum-based carbon black according to claim 1, characterized in that: The petroleum-based composite feedstock oil is a composite feedstock oil of refining residue oil and ethylene tar, wherein the proportion of ethylene tar in the composite feedstock oil is not less than 10%, and the solid impurity content of the refining residue oil is less than 500 ppm.

7. A method for preparing a high thermal conductivity rubber filler containing petroleum-based carbon black according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1: After weighing petroleum-based carbon black, acetylene black, carbon nanotubes, and graphene, put them into a stirring tank, stir at room temperature, at a stirring speed of 15-30 r / min, and for 10-30 min to mix them evenly; S2: The material obtained in step S1 is fed into a granulator, and granulated into uniform fine particles at a speed of 5-20 r / min using a non-additive process; S3: The rubber filler is packed after uniform granulation.

8. The method for preparing a high thermal conductive rubber filler according to claim 7, characterized in that: In step S2, uniform fine particles of 0.5-3 mm are obtained by the granulator.

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