CN115583647B - Preparation method of oxygen, nitrogen and metal co-doped carbon material and application of oxygen, nitrogen and metal co-doped carbon material in rubber - Google Patents
Preparation method of oxygen, nitrogen and metal co-doped carbon material and application of oxygen, nitrogen and metal co-doped carbon material in rubber Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 74
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 44
- 229920001971 elastomer Polymers 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000001301 oxygen Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007787 solid Substances 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 31
- 230000001681 protective effect Effects 0.000 claims abstract description 27
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 29
- 238000010000 carbonizing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000004073 vulcanization Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JPVRJMGCWMBVMY-UHFFFAOYSA-N methylcarbamothioylsulfanyl n-methylcarbamodithioate Chemical compound CNC(=S)SSC(=S)NC JPVRJMGCWMBVMY-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZSXGLVDWWRXATF-UHFFFAOYSA-N N,N-dimethylformamide dimethyl acetal Chemical compound COC(OC)N(C)C ZSXGLVDWWRXATF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- -1 znO Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of an oxygen, nitrogen and metal co-doped carbon material and application thereof in rubber, which comprises the following steps: s1: mixing polysuccinimide and metal salt, dissolving in N, N-dimethylformamide, stirring, adding ethylenediamine, stirring to gel, standing, cleaning, suction filtering, and freeze drying to obtain solid; s2: the solid obtained in the step S1 is carbonized for 1-3 hours at 700-900 ℃ in the atmosphere of protective gas, and cooled to room temperature to obtain the carbon material.
Description
Technical Field
The invention relates to a preparation method of an oxygen, nitrogen and metal co-doped carbon material and application thereof in rubber, and belongs to the technical field of carbon materials.
Background
Carbon is one of the most common elements in natural distribution, and is separated from the atoms by sp 3 Hybridized to form a single bond, also in sp 3 And sp hybridization to form stable double and triple bonds, due toThe method can form allotropes with very different structures and properties, such as zero-dimensional carbon black and fullerene, one-dimensional carbon nano tube and carbon nano fiber, two-dimensional graphene and the like. From traditional carbon black to latest two-dimensional graphene, carbon materials have been widely applied to the fields of adsorbents, catalysts, fuel cells, electrode materials of secondary batteries, supercapacitors, composite materials, gas sensors, solar cells, various electronic devices and the like by virtue of unique and excellent mechanical, electrical, thermal and other properties.
The carbon material can be used as a filler to be added into rubber, can enhance the physical, thermal, electrical and gas/liquid barrier properties of the rubber, and can reduce the production cost of rubber products. At present, carbon materials commonly used in rubber are graphite, carbon black, graphene oxide, carbon fiber and carbon nano tube, but the carbon materials have a plurality of defects, and cannot fully exert the reinforcing effect, such as easy agglomeration in a rubber matrix and difficult good combination with the rubber matrix.
In view of the above, it is desirable to devise a method for improving the performance of carbon materials to meet the rubber reinforcement requirements.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of an oxygen, nitrogen and metal co-doped carbon material capable of effectively reinforcing the mechanical properties of rubber.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
subject 1
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: mixing polysuccinimide and metal salt, dissolving in N, N-dimethylformamide, stirring, adding ethylenediamine, stirring to gel, standing, cleaning, suction filtering, and freeze drying to obtain solid;
s2: carbonizing the solid obtained in the step S1 for 1-3 hours at 700-900 ℃ in a protective gas atmosphere, and cooling to room temperature to obtain the carbon material.
In some embodiments of the invention, the mass ratio of polysuccinimide, metal salt, N-dimethylformamide and ethylenediamine is 1:0.3-1.6: 2-5:0.5-1.5.
In some embodiments of the invention, the mass ratio of polysuccinimide, metal salt, N-dimethylformamide and ethylenediamine is 1:0.3:5:1.25.
in some embodiments of the invention, the metal salt is selected from CdN 2 O 6 .4H 2 O、Na 2 SnO 3 ·3H 2 O、CuSO 4 ·5H 2 O、PbCO 3 One or a combination of any two or more of them.
In some embodiments of the invention, the metal salt is CdN in a mass ratio of 1:1 2 O 6 .4H 2 O and Na 2 SnO 3 ·3H 2 O。
In some embodiments of the invention, in step S2, the shielding gas is continuously introduced at a rate of 15 to 40 mL/min.
In some embodiments of the present invention, in the step S2, the temperature is raised from room temperature to 280 to 320 ℃ at a rate of 1.2 to 1.8 ℃/min, then raised to 700 to 900 ℃ at a rate of 2 to 2.2 ℃/min, then maintained for 1 to 3 hours, then lowered to 500 ℃ at a rate of 5 ℃/min, and finally naturally lowered to room temperature, thereby obtaining the carbon material.
In some embodiments of the invention, in step S2, ethylenediamine is added at a rate of 3-6mL/min.
Subject matter II
The application of the oxygen, nitrogen and metal co-doped carbon material obtained by the preparation method provided by the technical subject one in the rubber field.
In some embodiments of the invention, the application is in the preparation of rubber mounts.
In some embodiments of the invention, the rubber support comprises the following raw materials in mass ratio of 100:40:5:1:1:2, the natural rubber, oxygen, nitrogen and metal are co-doped with carbon materials, znO, stearic acid, an accelerator and sulfur; the accelerator is prepared from the following components in percentage by mass: 0.5:0.2:2:0.2 dibenzothiazyl Disulfide (DM), N-cyclohexyl-2-benzothiazole hypoxanthophyll amide (CZ), dimethylthiuram disulfide (TMTD), dimorpholine disulfide (DTDM), 2-mercaptobenzothiazole (M).
The preparation process of the rubber support comprises the following steps: placing 100g of natural rubber into an internal mixer for plasticating for 30s, and lifting bolts; adding 40g of oxygen, nitrogen and metal co-doped carbon material into an internal mixer, and mixing until a torque curve area is stable; adding 5g ZnO and 1g stearic acid together, maintaining the temperature of the materials at 140 ℃ by adjusting the torque value, and discharging glue after 90 s; the mixing time is maintained for 6 min; plasticating and discharging sheets in an open mill, cooling to room temperature, adding a vulcanization system in the open mill again, mixing 2g of sulfur and 1g of accelerator into a film, and then wrapping and rolling three times respectively, discharging sheets to prepare a rubber compound; and (3) putting the rubber compound into a mold for vulcanization molding to obtain the rubber, wherein the vulcanization temperature is 145 ℃ and the vulcanization time is 180s.
The beneficial effects of adopting above-mentioned technical scheme to produce lie in:
in the method provided by the invention, polysuccinimide and N, N-dimethylformamide are matched, metal elements are doped at the same time, and the prepared oxygen, nitrogen and metal co-doped carbon material has a specific surface area of 200-600 m 2 Per gram, nitrogen content 0.25-1.5. 1.5 at%, oxygen content 5-18at%, and particle size distribution 2-35 nm. The carbon material prepared by the method is used for preparing rubber, the mechanical property test of the rubber is carried out, the hardness (IRHD) is 62-65, the tensile strength is 23MPa, the stretch-break elongation is 635%, the constant compression set (70 ℃ multiplied by 24 h) is 11%, the adhesive peel strength of the rubber and a steel plate is 16KN/m, the adhesive peel strength of the rubber and a tetrafluoro plate is 12KN/m, the hardness is changed by 2-8, the tensile strength is changed by-3 to-13%, the stretch-break elongation is changed by-8 to-19, and the ozone aging resistance (25 pphm,20% elongation and 40 ℃ multiplied by 96 h) is free of cracks.
Wherein, the polysuccinimide and the N, N-dimethylformamide cooperate, and the prepared carbon material is applied to rubber, so that the mechanical property of the rubber is improved; cdN (CdN) 2 O 6 .4H 2 O and Na 2 SnO 3 ·3H 2 The carbon material is prepared by O collaborative doping, so that the tensile strength and the stretch-break elongation of the rubber are further improved; doping of carbon materials with metalsAnd nitrogen, the thermal conductivity of the rubber is improved, and the ageing resistance of the rubber is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the desorption of nitrogen from a carbon material according to example 1 of the present invention;
FIG. 2 is an XPS chart of nitrogen of an electrode carbon material according to example 1 of the present invention;
FIG. 3 is an XPS chart of oxygen for an electrode carbon material according to example 1 of the present invention;
FIG. 4 is a graph showing the particle size distribution of the carbon material of example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be clearly and completely described in connection with the following specific embodiments.
Polysuccinimide, model P303994, molecular weight 7000-8000, available from Ala Ding Huaxue reagent; cuSO 4 ·5H 2 O, molecular weight 249.69, purchased from Aba Ding Huaxue reagent;
Na 2 SnO 3 ·3H 2 o, molecular weight 266.73, purchased from ala Ding Huaxue reagent;
CdN 2 O 6 .4H 2 o, molecular weight 308.48, purchased from ala Ding Huaxue reagent;
PbCO 3 molecular weight 267.21, available from the aara Ding Huaxue reagent;
n, N-dimethylformamide, molecular weight 73.09, available from ala Ding Huaxue reagent;
ethylenediamine, molecular weight 78.12, available from attorney Ding Huaxue reagent.
Example 1
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 20g of polysuccinimide, 6g of CdN 2 O 6 .4H 2 O is mixed and dissolved in 100g of N, N-dimethylformamide, 25g of ethylenediamine is added dropwise after the mixture is fully stirred at room temperature until the mixture is dissolved, the dripping rate is 5mL/min, the mixture is stirred to be gel-like semi-solid, the gel-like semi-solid is kept stand at room temperature for 12 hours, and then the gel-like semi-solid is obtained by washing, suction filtration and freeze drying with deionized water;
s2: continuously introducing protective gas into the solid obtained in the step S1 at a rate of 30mL/min under the nitrogen atmosphere of the protective gas, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 600m 2 /g, nitrogen content: 1.5 at%, oxygen content 18-at%, and particle size distribution 2-35 nm.
Performing nitrogen adsorption and desorption performance test on the prepared carbon material, as shown in figure 1; the characterization of the composition of nitrogen and oxygen of the prepared carbon material is respectively shown in fig. 2 and 3, and it can be seen that the carbon material is successfully doped with nitrogen and oxygen elements; the particle size distribution analysis was performed on the prepared carbon material, as shown in fig. 4.
Example 2
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 20g polysuccinimide, 6g Na 2 SnO 3 ·3H 2 O is mixed and dissolved in 100g of N, N-dimethylformamide, 25g of ethylenediamine is added dropwise after the mixture is fully stirred at room temperature until the mixture is dissolved, the dripping rate is 5mL/min, the mixture is stirred to be gel-like semi-solid, the gel-like semi-solid is kept stand at room temperature for 12 hours, and then the gel-like semi-solid is obtained by washing, suction filtration and freeze drying with deionized water;
s2: continuously introducing protective gas into the solid obtained in the step S1 at a rate of 30mL/min under the nitrogen atmosphere of the protective gas, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 460 m 2 /g, nitrogen content: 0.89 at%, oxygen content 15at%, and particle size distribution 10-33 nm.
Example 3
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 20g polysuccinimide, 3g CdN 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 O is mixed and dissolved in 100g of N, N-dimethylformamide, 25g of ethylenediamine is added dropwise after the mixture is fully stirred at room temperature until the mixture is dissolved, the dripping rate is 5mL/min, the mixture is stirred to be gel-like semi-solid, the gel-like semi-solid is kept stand at room temperature for 12 hours, and then the gel-like semi-solid is obtained by washing, suction filtration and freeze drying with deionized water;
s2: continuously introducing protective gas into the solid obtained in the step S1 at a rate of 30mL/min under the nitrogen atmosphere of the protective gas, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 360 m 2 /g, nitrogen content: 0.75at%, oxygen content: 12at%, particle size distribution 7-23 nm.
Example 4
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 20g polysuccinimide, 32g PbCO 3 Mixing, dissolving in 80 g of N, N-dimethylformamide, fully stirring at room temperature until the mixture is dissolved, dropwise adding 10g of ethylenediamine with the dropwise adding rate of 3mL/min, stirring to gel-like semi-solid, standing at room temperature for 12 hours, washing with deionized water, filtering, and freeze-drying for 24 hours to obtain a solid;
s2: continuously introducing protective gas into the solid obtained in the step S1 at a speed of 40mL/min under the nitrogen atmosphere of the protective gas, firstly heating to 320 ℃ from room temperature at a speed of 1.2 ℃/min, then heating to 900 ℃ at a speed of 2 ℃/min, carbonizing for 1 hour, then cooling to 500 ℃ at a speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 200 m 2 /g, nitrogen content: 0.25 at%, oxygen content 5at%, and particle size distribution 9-30 nm.
Example 5
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 20g of polysuccinimide and 20g of CuSO 4 ·5H 2 O is mixed and dissolved in 40g of N, N-dimethylformamide, 30g of ethylenediamine is added dropwise after the mixture is fully stirred at room temperature until the mixture is dissolved, the dripping rate is 6mL/min, the mixture is stirred to be gel-like semi-solid, the gel-like semi-solid is kept stand at room temperature for 12 hours, and then the gel-like semi-solid is obtained by washing, suction filtration and freeze drying with deionized water;
s2: continuously introducing protective gas into the solid obtained in the step S1 at a speed of 15mL/min under the nitrogen atmosphere of the protective gas, firstly heating to 280 ℃ from room temperature at a speed of 1.8 ℃/min, then heating to 700 ℃ at a speed of 2.2 ℃/min, carbonizing for 3 hours, then cooling to 500 ℃ at a speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 230 m 2 /g, nitrogen content: 1.0 at%, oxygen content 11at%, and particle size distribution 3-25 nm.
Effect example 1
The carbon materials prepared in examples 1 to 5 were used to prepare rubber mount samples 1 to 5 by the following method:
the preparation method of the rubber support comprises the following steps:
placing 100g of natural rubber into an internal mixer for plasticating for 30s, and lifting bolts; adding 40g of oxygen, nitrogen and metal co-doped carbon material into an internal mixer, and mixing until a torque curve area is stable; adding 5g ZnO and 1g stearic acid together, maintaining the temperature of the materials at 140 ℃ by adjusting the torque value, and discharging glue after 90 s; the mixing time is maintained for 6 min; plasticating and discharging sheets in an open mill, cooling to room temperature, adding a vulcanization system in the open mill again, mixing 2g of sulfur and 1g of accelerator into a film, and then wrapping and rolling three times respectively, discharging sheets to prepare a rubber compound; and (3) putting the rubber compound into a mold for vulcanization molding to obtain the rubber, wherein the vulcanization temperature is 145 ℃ and the vulcanization time is 180s. Wherein the mass ratio of the accelerator is 1:0.5:0.2:2:0.2 dibenzothiazyl Disulfide (DM), N-cyclohexyl-2-benzothiazole hypoxanthophyll amide (CZ), dimethylthiuram disulfide (TMTD), dimorpholine disulfide (DTDM), 2-mercaptobenzothiazole (M).
According to GB JT/T4-2019, performance detection tests are carried out on the obtained rubber support, and the results are shown in the following table 1:
TABLE 1 Properties of samples of rubber supports prepared in examples 1-5
Comparative example 1
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 3g of CdN 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 O is mixed and dissolved in 120g of N, N-dimethylformamide, 25g of ethylenediamine is added dropwise after the mixture is fully stirred at room temperature until the mixture is dissolved, the dripping rate is 5mL/min, the mixture is stirred to be gel-like semi-solid, the gel-like semi-solid is kept stand at room temperature for 12 hours, and then the gel-like semi-solid is obtained by washing, suction filtration and freeze drying with deionized water;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (S1) at a rate of 30mL/min under the protective gas atmosphere, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
Comparative example 2
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 120g of polysuccinimide and 3g of CdN 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 O mixing, dripping 25g ethylenediamine with a dripping rate of 5mL/min, stirring to gel semisolid, and standing at room temperatureWashing with deionized water after 12 hours, filtering, and freeze-drying for 24 hours to obtain solid;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (S1) at a rate of 30mL/min under the protective gas atmosphere, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
Comparative example 3
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: dissolving 20g of polysuccinimide in 100g of N, N-dimethylformamide, fully stirring at room temperature until the polysuccinimide is dissolved, then dropwise adding 25g of ethylenediamine with the dropwise adding rate of 5mL/min, stirring until the polysuccinimide is gel-like semi-solid, standing at room temperature for 12 hours, washing with deionized water, filtering, and freeze-drying for 24 hours to obtain a solid;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (S1) at a rate of 30mL/min under the protective gas atmosphere, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
Comparative example 4 a method for preparing an oxygen, nitrogen and metal co-doped carbon material comprising the steps of:
s1: 20g of polymaleimide and 3g of CdN are reacted 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 O is mixed and dissolved in 100g of N, N-dimethylformamide, 25g of ethylenediamine is added dropwise after the mixture is fully stirred at room temperature until the mixture is dissolved, the dripping rate is 5mL/min, the mixture is stirred to be gel-like semi-solid, the gel-like semi-solid is kept stand at room temperature for 12 hours, and then the gel-like semi-solid is obtained by washing, suction filtration and freeze drying with deionized water;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (S1) at a rate of 30mL/min under the protective gas atmosphere, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
Comparative example 5a method for preparing an oxygen, nitrogen and metal co-doped carbon material comprising the steps of:
s1: 20g of succinimide and 3g of CdN are added 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 O is mixed and dissolved in 100g of N, N-dimethylformamide, 25g of ethylenediamine is added dropwise after the mixture is fully stirred at room temperature until the mixture is dissolved, the dripping rate is 5mL/min, the mixture is stirred to be gel-like semi-solid, the gel-like semi-solid is kept stand at room temperature for 12 hours, and then the gel-like semi-solid is obtained by washing, suction filtration and freeze drying with deionized water;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (S1) at a rate of 30mL/min under the protective gas atmosphere, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
Comparative example 6
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 20g polysuccinimide, 3g CdN 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 O is mixed and dissolved in 100g of N, N-dimethylformamide dimethyl acetal, 25g of ethylenediamine is added dropwise after the mixture is fully stirred at room temperature until the mixture is dissolved, the dripping rate is 5mL/min, the mixture is stirred to gel semi-solid, the mixture is kept stand at room temperature for 12 hours, and then the mixture is washed, filtered and freeze-dried by deionized water for 24 hours to obtain solid;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (S1) at a rate of 30mL/min under the protective gas atmosphere, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
Comparative example 7
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 20g polysuccinimide, 3g CdN 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 O is mixed, dissolved in 100g of N, N-dimethylformamide, fully stirred at room temperature until the N, N-ethylethylenediamine is dissolved, 25g of N-ethylethylenediamine is dropwise added at the rate of 5mL/min, stirred to gel-like semi-solid, kept stand at room temperature for 12 hours, washed with deionized water, filtered by suction, and freeze-dried for 24 hours to obtain solid;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (S1) at a rate of 30mL/min under the protective gas atmosphere, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 800 ℃ at a rate of 2.1 ℃/min, carbonizing for 2 hours, then cooling to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the carbon material.
Effect example 2
The carbon materials prepared in comparative examples 1 to 7 were used to prepare rubber mount comparative samples 1 to 7 by the following method:
the preparation method of the rubber support comprises the following steps:
placing 100g of natural rubber into an internal mixer for plasticating for 30s, and lifting bolts; adding 40g of oxygen, nitrogen and metal co-doped carbon material into an internal mixer, and mixing until a torque curve area is stable; adding 5g ZnO and 1g stearic acid together, maintaining the temperature of the materials at 140 ℃ by adjusting the torque value, and discharging glue after 90 s; the mixing time is maintained for 6 min; plasticating and discharging sheets in an open mill, cooling to room temperature, adding a vulcanization system in the open mill again, mixing 2g of sulfur and 1g of accelerator into a film, and then wrapping and rolling three times respectively, discharging sheets to prepare a rubber compound; and (3) putting the rubber compound into a mold for vulcanization molding to obtain the rubber, wherein the vulcanization temperature is 145 ℃ and the vulcanization time is 180s. Wherein the mass ratio of the accelerator is 1:0.5:0.2:2:0.2 dibenzothiazyl Disulfide (DM), N-cyclohexyl-2-benzothiazole hypoxanthophyll amide (CZ), dimethylthiuram disulfide (TMTD), dimorpholine disulfide (DTDM), 2-mercaptobenzothiazole (M).
According to GB JT/T4-2019, performance detection tests are carried out on the obtained rubber support, and the results are shown in the following table 2:
TABLE 2
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The preparation method of the oxygen, nitrogen and metal co-doped carbon material is characterized by comprising the following steps of:
s1: mixing polysuccinimide and metal salt, dissolving in N, N-dimethylformamide, stirring, adding ethylenediamine, stirring to gel, standing, cleaning, suction filtering, and freeze drying to obtain solid;
s2: carbonizing the solid obtained in the step S1 for 1-3 hours at 700-900 ℃ in a protective gas atmosphere, and cooling to room temperature to obtain a carbon material;
the mass ratio of the polysuccinimide to the metal salt to the N, N-dimethylformamide to the ethylenediamine is 1:0.3-1.6:2-5:0.5-1.5;
the metal salt is CdN with the mass ratio of 1:1 2 O 6 ·4H 2 O and Na 2 SnO 3 ·3H 2 O；
The molecular weight of the polysuccinimide is 7000-8000.
2. The method for preparing the oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein the mass ratio of polysuccinimide, metal salt, N-dimethylformamide and ethylenediamine is 1:0.3:5:1.25.
3. the method for producing an oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein in the step S2, a shielding gas is continuously introduced at a rate of 15 to 40 mL/min.
4. The method for preparing oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein in the step S2, the temperature is raised to 280-320 ℃ from room temperature at a rate of 1.2-1.8 ℃/min, then the temperature is raised to 700-900 ℃ at a rate of 2-2.2 ℃/min, the temperature is kept for 1-3 hours, then the temperature is lowered to 500 ℃ at a rate of 5 ℃/min, and finally the temperature is naturally lowered to room temperature, so as to obtain the carbon material.
5. The method for preparing an oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein in the step S1, ethylenediamine is added at a rate of 3-6mL/min.
6. Use of an oxygen, nitrogen and metal co-doped carbon material obtained by the preparation method according to any one of claims 1 to 5 in the rubber field.
7. The method according to claim 6, wherein the rubber support is prepared.
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| CN109110759A (en) * | 2018-11-07 | 2019-01-01 | 河南师范大学 | A kind of preparation method of nitrogen, boron codope porous carbon materials |
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| WO2022015888A2 (en) * | 2020-07-14 | 2022-01-20 | The Research Foundation For The State University Of New York | Porous carbon materials, nanoparticles, methods of making same, and uses thereof |
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| CN109110759A (en) * | 2018-11-07 | 2019-01-01 | 河南师范大学 | A kind of preparation method of nitrogen, boron codope porous carbon materials |
| WO2022015888A2 (en) * | 2020-07-14 | 2022-01-20 | The Research Foundation For The State University Of New York | Porous carbon materials, nanoparticles, methods of making same, and uses thereof |
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