Nitrogen and phosphorus doped porous carbon modifier as well as preparation method and application thereof
By preparing nitrogen-phosphorus doped porous carbon modifiers, the problem of poor dispersion of existing carbon materials in rubber is solved, and the wear resistance and performance improvement of rubber is achieved.
Patent Information
- Application Number
- CN202510401840.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-01
- Publication Date
- 2025-06-27
AI Technical Summary
Existing carbon materials are prone to agglomeration and precipitation in rubber, resulting in poor dispersion and affecting the wear resistance and performance of rubber.
A nitrogen-phosphorus doped porous carbon modifier is used. The modifier is prepared by specific component ratios and preparation methods, including the mixing, drying, polymerization and carbonization of raw materials such as polyaspartic acid, magnesium sulfate, polyvinylpyrrolidone and melamine phosphate to form nitrogen-phosphorus doped porous carbon with a porous structure.
Effectively strengthen the rubber, improve its wear resistance, avoid agglomeration and precipitation, and improve the dispersion and performance of carbon materials in rubber.
Smart Images
Figure CN120208198A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of carbon materials, and relates to a nitrogen and phosphorus doped porous carbon modifier, a preparation method thereof, and an application thereof. Background Art
[0002] Carbon materials have been widely used in the fields of adsorbents, catalysts, fuel cells, electrode materials for secondary batteries, supercapacitors, composite materials, gas sensors, solar cells, and various electronic devices due to their unique and excellent mechanical, electrical, and thermal properties.
[0003] Carbon materials can be added to rubber as fillers, which can enhance the physical, thermal, electrical, and gas / liquid barrier properties of rubber, and can reduce the production cost of rubber products. Currently, the carbon materials commonly used in rubber are graphite, carbon black, graphene, graphene oxide, carbon fiber, and carbon nanotube. However, these carbon materials also have many defects and cannot fully play their due reinforcing role. For example, they are prone to agglomeration in the rubber matrix and are not easily combined with the rubber matrix well.
[0004] To improve the wear resistance of rubber, conventional techniques mostly use adding carbon black or inorganic nanoparticles (such as silica and carbon nanotubes) to the matrix as reinforcing phases. However, the surface of carbon black particles has high adsorption properties and is prone to interact with rubber molecules. At the same time, the polar repulsion between carbon black particles leads to easy agglomeration and precipitation of carbon black in rubber. To improve the dispersion of carbon black in rubber, a dispersant usually needs to be added during the preparation of rubber, and the carbon black particles are evenly dispersed in the rubber matrix through physical or chemical actions. In addition, the filling effect of carbon black will also affect the properties of rubber materials, including their dynamic mechanical properties and heat generation. At the same time, due to the large specific surface area and high surface energy of nanoparticles, they are prone to agglomeration in the rubber matrix, forming stress concentration points, which instead accelerate wear.
[0005] In summary, it is of great significance to develop a carbon material that can improve the wear resistance of rubber. Summary of the Invention
[0006] The present invention provides a nitrogen and phosphorus doped porous carbon modifier, a preparation method thereof, and an application thereof. The porous carbon modifier can effectively reinforce rubber and improve the wear resistance of rubber.
[0007] The technical solution of the present invention is realized as follows: A preparation method of a nitrogen and phosphorus doped porous carbon modifier includes the following steps: mixing raw materials with water, stirring, and drying to obtain a mixture; wherein the raw materials include polyaspartic acid, magnesium sulfate, polyvinylpyrrolidone, and melamine phosphate with a mass ratio of 3-7:4-6:4-6:3-7. Keep the mixture at 280 - 320 °C for 8 - 16 h, and then cool it to room temperature to obtain the polymer; carbonize the polymer in an inert gas atmosphere for 1.5 - 3 h to obtain the nitrogen and phosphorus doped porous carbon modifier; the carbonization temperature is 850 - 1000 °C.
[0008] Preferably, the raw materials include polyaspartic acid, magnesium sulfate, polyvinylpyrrolidone and melamine phosphate in a mass ratio of 3 - 7:5:4 - 6:5.
[0009] Preferably, the molecular weight of the polyvinylpyrrolidone is 40000, and the molecular weight of the polyaspartic acid is 1000 - 4000.
[0010] Preferably, the water temperature is 75 - 90 °C; the stirring speed is 80 - 120 rpm, and the stirring time is 2.5 - 3.5 h.
[0011] Preferably, the dosage relationship between the raw materials and water is 20 g:180 - 250 mL.
[0012] Preferably, the drying temperature is 75 - 90 °C, and the drying time is 20 - 30 h.
[0013] Preferably, the mixture is kept at 300 °C for 12 h to obtain the polymer.
[0014] Preferably, the carbonization temperature is 900 °C; the heating rate of the polymer from room temperature to the carbonization temperature is 3 - 6 °C / min.
[0015] The present invention also provides a nitrogen and phosphorus doped porous carbon modifier obtained by the preparation method as described above.
[0016] The present invention also provides an application of the nitrogen and phosphorus doped porous carbon modifier obtained by the preparation method as described above in rubber or the negative electrode material of a battery.
[0017] Preferably, in the preparation method of the rubber, the addition amount of the nitrogen and phosphorus doped porous carbon modifier is 1 - 10 wt% of the rubber raw material.
[0018] The working principle and beneficial effects of the present invention are as follows: 1. In the carbon material preparation method provided by the present invention, each component acts in a synergistic mechanism to obtain nitrogen and phosphorus doped porous carbon. This porous carbon can be applied to rubber additives and the negative electrode material of a battery. After being used as a rubber additive, this porous carbon can effectively reinforce the rubber and improve the wear resistance of the rubber.
[0019] 2. The preparation method of the present invention is simple, avoiding complex steps and reducing costs. Description of the Drawings
[0020] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.
[0021] Figure 1 SEM image of the porous carbon modifier prepared in Example 1 of the present invention.
[0022] Figure 2 XPS spectrum of phosphorus element of the porous carbon modifier prepared in Example 1 of the present invention.
[0023] Figure 3 XPS spectrum of nitrogen element of the porous carbon modifier prepared in Example 1 of the present invention. Specific Embodiments
[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.
[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the description of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention.
[0026] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be construed as limiting the protection scope of the present invention. The production processes, experimental methods or detection methods involved in the embodiments of the present invention are all conventional methods in the prior art unless otherwise specified, and their names and / or abbreviations are all conventional names in the art, which are very clear and definite in the relevant application fields, and those skilled in the art can understand the conventional process steps according to the names and apply the corresponding equipment and implement them under conventional conditions or conditions recommended by the manufacturer.
[0027] There are no special restrictions on the sources of various instruments, equipment, raw materials or reagents used in the embodiments of the present invention. They are all conventional products that can be obtained through regular commercial channels, and can also be prepared according to the conventional methods well-known to those skilled in the art.
[0028] In the following examples and comparative examples, the specifications of polyvinylpyrrolidone are M.W. 40000, and the specifications of polyaspartic acid are M.W. 4000.
[0029] Example 1 A preparation method of a nitrogen and phosphorus co-doped porous carbon modifier, comprising the following steps: Dissolve 5 g of polyaspartic acid, 5 g of magnesium sulfate, 5 g of polyvinylpyrrolidone, and 5 g of melamine phosphate (CAS No. 20208-95-1) in 200 ml of hot water at a water temperature of 80 °C and a stirring speed of 100 rpm. After magnetic stirring for 3 h, place it in an oven and dry it at 80 °C for 24 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 300 °C for 12 h. Cool it to room temperature to obtain a brown polymer. Place the above polymer in a nitrogen atmosphere furnace and heat it to 900 °C at a heating rate of 5 °C / min for carbonization for 2 h to obtain a nitrogen and phosphorus doped porous carbon modifier.
[0030] As Figure 1 shown, it can be clearly seen that the nitrogen and phosphorus doped porous carbon modifier has a porous structure; as Figure 2 shown, a phosphorus signal peak can be seen, indicating that phosphorus elements have been successfully doped into the porous carbon of the present invention; as Figure 3 shown, a nitrogen signal peak can be seen, indicating that nitrogen elements have been successfully doped into the porous carbon of the present invention.
[0031] Example 2 A preparation method of a nitrogen and phosphorus doped porous carbon modifier includes the following steps: Dissolve 3 g of polyaspartic acid, 6 g of magnesium sulfate, 4 g of polyvinylpyrrolidone, and 7 g of melamine phosphate in 220 ml of hot water at a water temperature of 85 °C and a stirring speed of 80 rpm. After magnetic stirring for 3 h, place it in an oven and dry it at 85 °C for 20 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 320 °C for 10 h. Cool it to room temperature to obtain a brown polymer. Place the above polymer in a nitrogen atmosphere furnace and heat it to 850 °C at a heating rate of 6 °C / min for carbonization for 3 h to obtain a nitrogen and phosphorus doped porous carbon modifier.
[0032] Example 3 A preparation method of a nitrogen and phosphorus doped porous carbon modifier includes the following steps: Dissolve 7 g of polyaspartic acid, 4 g of magnesium sulfate, 6 g of polyvinylpyrrolidone, and 3 g of melamine phosphate in 250 ml of hot water at a water temperature of 90 °C and a stirring speed of 120 rpm. After magnetic stirring for 3 h, place it in an oven and dry it at 90 °C for 24 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 280 °C for 16 h. Cool it to room temperature to obtain a brown polymer. Place the above polymer in a nitrogen atmosphere furnace and heat it to 1000 °C at a heating rate of 3 °C / min for carbonization for 1.5 h to obtain a nitrogen and phosphorus doped porous carbon modifier.
[0033] Example 4 A preparation method of a nitrogen and phosphorus doped porous carbon modifier includes the following steps: Dissolve 6 g of polyaspartic acid, 5 g of magnesium sulfate, 5 g of polyvinylpyrrolidone, and 6 g of melamine phosphate into 180 ml of hot water at a water temperature of 75 °C, with a stirring speed of 100 rpm. After magnetic stirring for 3 h, place it in an oven and dry it at 80 °C for 30 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 300 °C for 12 h, then cool it to room temperature to obtain a brown polymer. Place the above polymer in a nitrogen atmosphere furnace and heat it to 900 °C at a heating rate of 5 °C / min for carbonization for 2 h to obtain a nitrogen and phosphorus doped porous carbon modifier.
[0034] Comparative Example 1 A method for preparing a carbon material, comprising the following steps: Dissolve 5 g of polyaspartic acid, 5 g of magnesium sulfate, and 5 g of polyvinylpyrrolidone into 200 ml of hot water at a water temperature of 80 °C. After magnetic stirring for 3 h, place it in an oven and dry it at 80 °C for 24 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 300 °C for 12 h, then cool it to room temperature to obtain a polymer. Place the above polymer in a nitrogen atmosphere furnace and carbonize it at 900 °C for 2 h to obtain a carbon material.
[0035] Comparative Example 2 A method for preparing a carbon material, comprising the following steps: Dissolve 5 g of polyaspartic acid, 5 g of magnesium sulfate, 5 g of polyvinylpyrrolidone, and 3.66 g of sodium phosphate into 200 ml of hot water at a water temperature of 80 °C. After magnetic stirring for 3 h, place it in an oven and dry it at 80 °C for 24 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 300 °C for 12 h, then cool it to room temperature to obtain a polymer. Place the above polymer in a nitrogen atmosphere furnace and carbonize it at 900 °C for 2 h to obtain a carbon material.
[0036] Comparative Example 3 A method for preparing a carbon material, comprising the following steps: Dissolve 5 g of polyaspartic acid, 5 g of magnesium sulfate, 5 g of polyvinylpyrrolidone, and 2.82 g of melamine into 200 ml of hot water at a water temperature of 80 °C. After magnetic stirring for 3 h, place it in an oven and dry it at 80 °C for 24 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 300 °C for 12 h, then cool it to room temperature to obtain a polymer. Place the above polymer in a nitrogen atmosphere furnace and carbonize it at 900 °C for 2 h to obtain a carbon material.
[0037] Comparative Example 4 A method for preparing a carbon material, comprising the following steps: Dissolve 5 g of polyaspartic acid, 5 g of polyvinylpyrrolidone, and 5 g of melamine phosphate in 200 ml of hot water at a water temperature of 80 °C. Stir magnetically for 3 h and then place in an oven. Dry at 80 °C for 24 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 300 °C for 12 h. Cool to room temperature to obtain a polymer. Place the above polymer in a nitrogen atmosphere furnace and carbonize it at 900 °C for 2 h to obtain a carbon material.
[0038] Comparative Example 5 A method for preparing a carbon material, comprising the following steps: Dissolve 5 g of polyaspartic acid, 5 g of magnesium sulfate, and 5 g of melamine phosphate in 200 ml of hot water at a water temperature of 80 °C. Stir magnetically for 3 h and then place in an oven. Dry at 80 °C for 24 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 300 °C for 12 h. Cool to room temperature to obtain a polymer. Place the above polymer in a nitrogen atmosphere furnace and carbonize it at 900 °C for 2 h to obtain a carbon material.
[0039] Comparative Example 6 A method for preparing a carbon material, comprising the following steps: Dissolve 5 g of polyaspartic acid, 5 g of magnesium sulfate, 5 g of polyvinylpyrrolidone, and 5 g of melamine phosphate in 200 ml of hot water at a water temperature of 80 °C. Stir magnetically for 3 h and then place in an oven. Dry at 80 °C for 24 h, remove the water, and cool to room temperature to obtain a mixture; Place the above mixture in a nitrogen atmosphere furnace and carbonize it at 900 °C for 2 h to obtain a carbon material.
[0040] Comparative Example 7 A method for preparing a carbon material, comprising the following steps: Dissolve 5 g of polyaspartic acid, 5 g of magnesium sulfate, 5 g of polyvinylpyrrolidone, 2.20 g of phosphoric acid, and 2.82 g of melamine in 200 ml of hot water at a water temperature of 80 °C. The stirring speed is 100 rpm. Stir magnetically for 3 h and then place in an oven. Dry at 80 °C for 24 h to remove the water and obtain a mixture; Place the above mixture in a muffle furnace and keep it at 300 °C for 12 h. Cool to room temperature to obtain a brown polymer. Place the above polymer in a nitrogen atmosphere furnace and heat it to 900 °C at a heating rate of 5 °C / min and carbonize it for 2 h to obtain a carbon material.
[0041] Application Example Prepare rubber bearings from the nitrogen and phosphorus doped porous carbon modifiers prepared in Examples 1-4 and Comparative Examples 1-7 by the following method: Place natural rubber in an internal mixer, then add a certain amount of nitrogen and phosphorus doped porous carbon modifier, plasticize at 140 °C for 15 minutes, cut and knead back and forth three times on the internal mixer, and then inject it into a bearing mold to cool to obtain a rubber bearing. Specimens 1-4 correspond to the porous carbon additives prepared in Examples 1-4, and the addition amounts of the porous carbon additives are 5wt%, 10wt%, 7wt%, and 8wt% of the rubber raw material respectively; Comparative Specimens 1-7 correspond to the carbon materials prepared in Comparative Examples 1-7, and the addition amount of the carbon materials is 5wt% of the rubber raw material. The natural rubber was purchased from Shanghai Ruixun High Polymer Materials Co., Ltd., whole latex (product number: SCRWF).
[0042] Test: (1)Test the specific surface area (m 2 / g), micropore ratio (%), and pore diameter (nm) of the porous carbon materials prepared in Examples 1-4 and Comparative Examples 1-7. The results are shown in Table 1 below.
[0043] (2)Detect the friction performance (wear rate) of the above-obtained rubber bearings according to the standard of the skateboard line wear test method in Appendix B of JT / T901-2014: The indoor temperature is 21 °C, and a compressed air refrigerated dryer is used to control the indoor humidity at 40%-50%. Circulating flowing alcohol is introduced into the stainless steel sliding layer to control the temperature of the rubber bearing and the stainless steel plate at 21 °C. This test is carried out on a wear testing machine. The specimens are installed by the method of "inserting four and exposing three", the friction sliding speed is 15mm / s, the compressive stress is uniformly taken as 45MPa, and a sine wave loading is adopted, and the unilateral sliding distance is 10mm. The results are as follows in Table 1.
[0044] Table 1 The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for preparing a nitrogen-phosphorus doped porous carbon modifier, characterized in that: The method comprises the following steps: mixing raw materials with water, stirring, and drying to obtain a mixture; wherein the raw materials comprise polyaspartic acid, magnesium sulfate, polyvinyl pyrrolidone, and melamine phosphate in a mass ratio of 3-7:4-6:4-6:3-7; The mixture is kept at 280-320°C for 8-16 hours to obtain a polymer; the polymer is carbonized in an inert gas atmosphere for 1.5-3 hours to obtain a nitrogen-phosphorus doped porous carbon modifier; wherein the carbonization temperature is 850-1000°C.
2. The method for preparing a nitrogen and phosphorus doped porous carbon modifier according to claim 1, characterized in that: The raw materials include polyaspartic acid, magnesium sulfate, polyvinyl pyrrolidone and melamine phosphate in a mass ratio of 3-7:5:4-6:
5.
3. The method for preparing a nitrogen and phosphorus doped porous carbon modifier according to claim 1, characterized in that: The molecular weight of the polyvinyl pyrrolidone is 40,000, and the molecular weight of the polyaspartic acid is 1,000-4,000.
4. The method for preparing a nitrogen and phosphorus doped porous carbon modifier according to claim 1, characterized in that: The water temperature is 75-90°C; the stirring speed is 80-120rpm, and the stirring time is 2.5-3.5h.
5. The method for preparing a nitrogen and phosphorus doped porous carbon modifier according to claim 1, characterized in that: The dosage of the raw material and water is 20g:180-250mL.
6. The method for preparing a nitrogen and phosphorus doped porous carbon modifier according to claim 1, characterized in that: The drying temperature is 75-90° C. and the drying time is 20-30 hours.
7. The method for preparing a nitrogen and phosphorus doped porous carbon modifier according to claim 1, characterized in that: The carbonization temperature is shown to be 900°C; the heating rate of the polymer to the carbonization temperature is 3-6°C / min.
8. A nitrogen and phosphorus doped porous carbon modifier obtained by the preparation method according to any one of claims 1 to 7.
9. Use of the nitrogen and phosphorus doped porous carbon modifier obtained by the preparation method according to any one of claims 1 to 7 in rubber or battery negative electrode materials.
10. The use according to claim 9, characterized in that: In the rubber preparation method, the amount of the nitrogen and phosphorus doped porous carbon modifier added is 1-10wt% of the rubber raw material.