CN115583647A - Preparation method of oxygen, nitrogen and metal co-doped carbon material and application of carbon material in rubber - Google Patents
Preparation method of oxygen, nitrogen and metal co-doped carbon material and application of 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 90
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 78
- 229920001971 elastomer Polymers 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000001301 oxygen Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000007787 solid Substances 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 230000001681 protective effect Effects 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010000 carbonizing Methods 0.000 claims abstract description 15
- 238000004108 freeze drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 13
- 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
- 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
- 239000000203 mixture Substances 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000000126 substance Substances 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
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 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
- 238000000967 suction filtration Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 230000008859 change Effects 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
- 238000005096 rolling process Methods 0.000 description 3
- 239000000829 suppository Substances 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
- 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
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000011159 matrix material Substances 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
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 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
- 238000002336 sorption--desorption 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
- 230000002195 synergetic effect Effects 0.000 description 1
- -1 znO Substances 0.000 description 1
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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
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- 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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- Engineering & Computer Science (AREA)
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- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
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- 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, and the preparation method comprises the following steps: s1: mixing polysuccinimide and metal salt, dissolving in N, N-dimethylformamide, stirring, adding ethylenediamine, stirring to form gel, standing, washing, filtering, and freeze drying to obtain solid; s2: and carbonizing the solid obtained in the step S1 at 700-900 ℃ for 1-3h in a protective gas atmosphere, and cooling 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 of the carbon material in rubber, and belongs to the technical field of carbon materials.
Background
Carbon is one of the most common elements distributed in nature except by sp 3 Hybridization to form a single bond, also in sp 3 And sp hybridization forms stable double bonds and triple bonds, so allotropes with different structures and properties can be formed, such as zero-dimensional carbon black and fullerene, one-dimensional carbon nano tubes and carbon nano fibers, two-dimensional graphene and the like. From traditional carbon black to the latest two-dimensional graphene, carbon materials have been widely applied to the fields of adsorbents, catalysts, electrode materials of fuel cells and secondary batteries, supercapacitors, composite materials, gas sensors, solar cells, various electronic devices and the like due to unique and excellent mechanical, electrical and thermal 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 fibers and carbon nanotubes, but the carbon materials also have many defects and cannot fully exert the due reinforcing effect, such as easy agglomeration in a rubber matrix and difficult good combination with the rubber matrix.
In view of this, a method capable of improving the performance of the carbon material is needed to meet the rubber reinforcement requirement.
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 property of rubber.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
subject of the technology 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 form gel, standing, washing, filtering, and freeze drying to obtain solid;
s2: and (3) carbonizing the solid obtained in the step (S1) at 700-900 ℃ for 1-3h 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 the polysuccinimide, the metal salt, the N, N-dimethylformamide and the ethylenediamine is 1:0.3-1.6: 2-5:0.5-1.5.
In some embodiments of the invention, the mass ratio of the polysuccinimide, the metal salt, the N, N-dimethylformamide and the 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 2 O 6 .4H 2 O and Na 2 SnO 3 ·3H 2 O。
In some embodiments of the present invention, in the step S2, the protective gas is continuously introduced at a rate of 15-40 mL/min.
In some embodiments of the invention, in step S2, the temperature is first raised from room temperature to 280-320 ℃ at a rate of 1.2-1.8 ℃/min, then raised to 700-900 ℃ at a rate of 2-2.2 ℃/min, then kept for 1-3 hours, then lowered to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooled to room temperature, so as to obtain the carbon material.
In some embodiments of the invention, the rate of ethylenediamine addition in step S2 is 3-6mL/min.
Subject matter two
The application of the carbon material codoped with oxygen, nitrogen and metal obtained by the preparation method provided by the technical subject I in the field of rubber.
In some embodiments of the invention, the application is the preparation of rubber mounts.
In some embodiments of the present invention, the raw materials of the rubber mount include 100:40:5:1:1:2, co-doping natural rubber, oxygen, nitrogen and metal with a carbon material, znO, stearic acid, an accelerant and sulfur; the mass ratio of the accelerant to the accelerator is 1:0.5:0.2:2:0.2 of dibenzothiazole Disulfide (DM), N-cyclohexyl-2-benzothiazolehypoxanthamide (CZ), dimethylthiuram disulfide (TMTD), dithiodimorpholine (DTDM), 2-mercaptobenzothiazole (M).
The preparation process of the rubber support comprises the following steps: plasticating 100g of natural rubber in an internal mixer for 30 seconds, and extracting a suppository; adding 40g of oxygen, nitrogen and metal co-doped carbon material into an internal mixer, mixing until a torque curve area is stable; adding 5g of ZnO and 1g of stearic acid together, maintaining the temperature of the material at 140 ℃ by adjusting the torque value, and discharging the glue after 90 s; the mixing time is kept for 6 min; plasticating and discharging 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 the rubber sheet, performing triangular wrapping and rolling for three times respectively, and discharging to obtain rubber compound; and putting the mixed rubber into a mold to be vulcanized and molded to obtain the rubber, wherein the vulcanization temperature is 145 ℃, and the vulcanization time is 180s.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
in the method provided by the invention, polysuccinimide and N, N-dimethylformamide are matched and metal elements are doped simultaneously, so that the prepared oxygen, nitrogen and metal co-doped carbon material has the specific surface area of 200-600 m 2 (g), nitrogen content is 0.25-1.5 at%, oxygen content is 5-18at%, and particle size distribution is 2-35 nm. Adopt the present inventionThe carbon material is prepared by the method, and the rubber is subjected to a rubber mechanical property test, wherein the hardness (IRHD) is 62 to 65, the tensile strength can reach 23MPa, the elongation at break can reach 635%, the constant compression permanent deformation (70 ℃ x 24 h) can reach 11%, the bonding peel strength of the rubber and a steel plate can reach 16KN/m, the bonding peel strength of the rubber and a tetrafluoro plate can reach 12KN/m, the hardness change is 2 to 8, the tensile strength change is-3 to-13%, the elongation at break change is-8 to-19, the ozone aging resistance (25pphm, 20% elongation, 40 ℃ x 96 h) is realized, and no crack exists.
The carbon material prepared by the synergy of polysuccinimide and N, N-dimethylformamide is applied to rubber, so that the mechanical property of the rubber is improved; cdn 2 O 6 .4H 2 O and Na 2 SnO 3 ·3H 2 The carbon material is prepared by the synergistic doping of O, so that the tensile strength and the elongation at break of the rubber are further improved; metal and nitrogen are doped in the carbon material, so that the heat 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 used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a nitrogen adsorption/desorption graph of a carbon material in example 1 of the present invention;
FIG. 2 is an XPS chart of nitrogen in the electrode carbon material according to example 1 of the present invention;
FIG. 3 is an XPS chart of oxygen in an electrode carbon material according to example 1 of the present invention;
FIG. 4 is a particle size distribution diagram of a carbon material in 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 following description of the present invention is given for clarity and completeness.
Polysuccinimide, model P303994, molecular weight 7000-8000, available from alatin chemicals; cuSO 4 ·5H 2 O, molecular weight 249.69, available from alatin chemicals;
Na 2 SnO 3 ·3H 2 o, molecular weight 266.73, available from aladine chemicals;
CdN 2 O 6 .4H 2 o, molecular weight 308.48, available from alatin chemicals;
PbCO 3 molecular weight 267.21, available from alatin chemicals;
n, N-dimethylformamide, molecular weight 73.09, available from alatin chemicals;
ethylene diamine, molecular weight 78.12, was purchased from alatin chemicals.
Example 1
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 20g of polysuccinimide and 6g of CdN 2 O 6 .4H 2 Mixing O, dissolving in 100g of N, N-dimethylformamide, fully stirring at room temperature until the mixture is dissolved, dropwise adding 25g of ethylenediamine at the dropwise adding rate of 5mL/min, stirring until a gelatinous semisolid is obtained, standing at room temperature for 12 hours, washing with deionized water, filtering, and freeze-drying for 24 hours to obtain a solid;
s2: and (2) continuously introducing protective gas into the solid obtained in the step (1) at the speed of 30mL/min in the protective gas nitrogen atmosphere, heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 800 ℃ at the speed of 2.1 ℃/min, then carbonizing for holding for 2 hours, then cooling to 500 ℃ at the 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 of 600m 2 Per g, nitrogen content: 1.5 at%, oxygen content 18at%, 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 composition characterization of nitrogen and oxygen of the prepared carbon material is respectively shown in the figure 2 and the figure 3, and the nitrogen and oxygen elements are successfully doped in the carbon material; the particle size distribution of the carbon material obtained was analyzed, 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 of polysuccinimide and 6g of Na 2 SnO 3 ·3H 2 Mixing O, dissolving in 100g of N, N-dimethylformamide, fully stirring at room temperature until the mixture is dissolved, dropwise adding 25g of ethylenediamine at the dropwise adding rate of 5mL/min, stirring until a gelatinous semisolid is obtained, 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 (1) at the speed of 30mL/min under the protective gas nitrogen atmosphere, heating the solid from room temperature to 300 ℃ at the speed of 1.5 ℃/min, then heating the solid to 800 ℃ at the speed of 2.1 ℃/min, carbonizing the solid for 2 hours, cooling the solid to 500 ℃ at the speed of 5 ℃/min, and finally naturally cooling the solid to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 460 m 2 Per 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 of polysuccinimide and 3g of CdN 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 Mixing O, dissolving in 100g of N, N-dimethylformamide, fully stirring at room temperature until the mixture is dissolved, dropwise adding 25g of ethylenediamine at the dropwise adding rate of 5mL/min, stirring until a gelatinous semisolid is obtained, 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 (1) at the speed of 30mL/min under the protective gas nitrogen atmosphere, heating the solid from room temperature to 300 ℃ at the speed of 1.5 ℃/min, then heating the solid to 800 ℃ at the speed of 2.1 ℃/min, carbonizing the solid for 2 hours, cooling the solid to 500 ℃ at the speed of 5 ℃/min, and finally naturally cooling the solid 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%, and the particle size distribution is 7-23 nm.
Example 4
The preparation method of the oxygen, nitrogen and metal co-doped carbon material comprises the following steps:
s1: 20g of polysuccinimide and 32g of PbCO were added 3 Mixing, dissolving in 80 g of N, N-dimethylformamide, stirring at room temperature to dissolve, adding 10g of ethylenediamine dropwise at a rate of 3mL/min, stirring to obtain gelatinous semisolid, standing at room temperature for 12 hours, washing with deionized water, filtering, and freeze-drying for 24 hours to obtain solid;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (1) at the speed of 40mL/min under the protective gas nitrogen atmosphere, heating the solid from room temperature to 320 ℃ at the speed of 1.2 ℃/min, then heating the solid to 900 ℃ at the speed of 2 ℃/min, carbonizing the solid for 1 hour, cooling the solid to 500 ℃ at the speed of 5 ℃/min, and finally naturally cooling the solid to room temperature to obtain the carbon material.
The parameters of the prepared carbon material are as follows: specific surface area of 200 m 2 Per 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 Mixing O, dissolving in 40g of N, N-dimethylformamide, fully stirring at room temperature until the mixture is dissolved, dropwise adding 30g of ethylenediamine at the dropping rate of 6mL/min, stirring until a gelatinous semisolid is obtained, 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 speed of 15mL/min under the protective gas nitrogen atmosphere, heating the solid from room temperature to 280 ℃ at a speed of 1.8 ℃/min, then heating the solid to 700 ℃ at a speed of 2.2 ℃/min, carbonizing the solid for 3 hours, cooling the solid to 500 ℃ at a speed of 5 ℃/min, and finally naturally cooling the solid 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%, particle size distribution3-25 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 methods:
the preparation method of the rubber support comprises the following steps:
plasticating 100g of natural rubber in an internal mixer for 30 seconds, and extracting a suppository; adding 40g of oxygen, nitrogen and metal co-doped carbon material into an internal mixer, mixing until a torque curve area is stable; adding 5g of ZnO and 1g of stearic acid together, and adjusting the torque value to maintain the temperature of the material at 140 ℃ for 90 s and then discharging the glue; the mixing time is kept for 6 min; plasticating and discharging 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 the rubber sheet, performing triangular wrapping and rolling for three times respectively, and discharging to obtain rubber compound; and putting the rubber compound into a mold to be vulcanized and molded 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 of dibenzothiazole Disulfide (DM), N-cyclohexyl-2-benzothiazolehypoxanthamide (CZ), dimethylthiuram disulfide (TMTD), dithiodimorpholine (DTDM), 2-mercaptobenzothiazole (M).
According to GB, JT/T4-2019, the obtained rubber support is subjected to a performance detection test, and the results are shown in the following table 1:
TABLE 1 Properties of rubber standoff samples 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 Mixing O, dissolving in 120g of N, N-dimethylformamide, fully stirring at room temperature until the mixture is dissolved, dropwise adding 25g of ethylenediamine at the dropwise adding rate of 5mL/min, stirring until a gelatinous semisolid is obtained, 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 (1) at the speed of 30mL/min in the protective gas atmosphere, heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 800 ℃ at the speed of 2.1 ℃/min, carbonizing for 2 hours, cooling to 500 ℃ at the speed 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 Mixing O, dropwise adding 25g of ethylenediamine at the speed of 5mL/min, stirring to obtain a gelatinous semisolid, 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 (1) at the speed of 30mL/min in the protective gas atmosphere, heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 800 ℃ at the speed of 2.1 ℃/min, carbonizing for 2 hours, cooling to 500 ℃ at the speed 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, dropwise adding 25g of ethylenediamine at the dropping rate of 5mL/min, stirring until a gelatinous semisolid is obtained, standing at room temperature for 12 hours, washing with deionized water, performing suction filtration, and freeze-drying for 24 hours to obtain a solid;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (1) at the speed of 30mL/min in the protective gas atmosphere, heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 800 ℃ at the speed of 2.1 ℃/min, carbonizing for 2 hours, cooling to 500 ℃ at the speed 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 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 Mixing O, dissolving in 100g of N, N-dimethylformamide, fully stirring at room temperature until the mixture is dissolved, dropwise adding 25g of ethylenediamine at the dropwise adding speed of 5mL/min, stirring until gelatinous semisolid, standing at room temperature for 12 hours, washing with deionized water, performing suction filtration, and freeze-drying for 24 hours to obtain a solid;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (1) at the speed of 30mL/min in the protective gas atmosphere, heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 800 ℃ at the speed of 2.1 ℃/min, carbonizing for 2 hours, cooling to 500 ℃ at the speed 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 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 Mixing O, dissolving in 100g of N, N-dimethylformamide, fully stirring at room temperature until the mixture is dissolved, dropwise adding 25g of ethylenediamine at the dropwise adding rate of 5mL/min, stirring until a gelatinous semisolid is obtained, 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 (1) at the speed of 30mL/min in the protective gas atmosphere, heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 800 ℃ at the speed of 2.1 ℃/min, carbonizing for 2 hours, cooling to 500 ℃ at the speed 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 of polysuccinimide and 3g of CdN 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 O, dissolving in 100g of N, N-dimethylformamide dimethyl acetal, stirring at room temperature, and adding 25g of ethylenediamine dropwise at a rate of5mL/min, stirring to form a gelatinous semisolid, standing at room temperature for 12 hours, washing with deionized water, performing suction filtration, and freeze-drying for 24 hours to obtain a solid;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (1) at the speed of 30mL/min in the protective gas atmosphere, heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 800 ℃ at the speed of 2.1 ℃/min, carbonizing for 2 hours, cooling to 500 ℃ at the speed 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 of polysuccinimide and 3g of CdN 2 O 6 .4H 2 O、3g Na 2 SnO 3 ·3H 2 Mixing O, dissolving in 100g of N, N-dimethylformamide, fully stirring at room temperature until the mixture is dissolved, dropwise adding 25g of N-ethyl ethylenediamine at the dropping speed of 5mL/min, stirring until a gelatinous semisolid is obtained, standing at room temperature for 12 hours, washing with deionized water, performing suction filtration, and freeze-drying for 24 hours to obtain a solid;
s2: and (3) continuously introducing protective gas into the solid obtained in the step (1) at the speed of 30mL/min in the protective gas atmosphere, heating to 300 ℃ from room temperature at the speed of 1.5 ℃/min, then heating to 800 ℃ at the speed of 2.1 ℃/min, carbonizing for 2 hours, cooling to 500 ℃ at the speed 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 methods:
the preparation method of the rubber support comprises the following steps:
plasticating 100g of natural rubber in an internal mixer for 30 seconds, and extracting a suppository; adding 40g of oxygen, nitrogen and metal co-doped carbon material into an internal mixer, mixing until a torque curve area is stable; adding 5g of ZnO and 1g of stearic acid together, maintaining the temperature of the material at 140 ℃ by adjusting the torque value, and discharging the glue after 90 s; the mixing time is kept for 6 min; plasticating and discharging 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 rubber sheet, performing triangular bag and rolling for three times respectively, and discharging to obtain rubber compound; and putting the mixed rubber into a mold to be vulcanized and molded 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 of dibenzothiazyl Disulfide (DM), N-cyclohexyl-2-benzothiazolesulfenamide (CZ), dimethylthiuram disulfide (TMTD), dithiodimorpholine (DTDM) and 2-mercaptobenzothiazole (M).
According to GB, JT/T4-2019, the obtained rubber support is subjected to a performance detection test, and the results are shown in the following table 2:
TABLE 2
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the oxygen, nitrogen and metal co-doped carbon material is characterized by comprising the following steps:
s1: mixing polysuccinimide and metal salt, dissolving in N, N-dimethylformamide, stirring, adding ethylenediamine, stirring to obtain gel, standing, washing, filtering, and freeze drying to obtain solid;
s2: and (3) carbonizing the solid obtained in the step (S1) at 700-900 ℃ for 1-3h in a protective gas atmosphere, and cooling to room temperature to obtain the carbon material.
2. The method for preparing an oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein the mass ratio of the polysuccinimide, the metal salt, the N, N-dimethylformamide and the ethylenediamine is 1.3-1.6: 2-5.
3. The method for preparing the oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein the mass ratio of the polysuccinimide, the metal salt, the N, N-dimethylformamide and the ethylenediamine is 1:0.3:5:1.25..
4. The method for preparing an oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein 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.
5. The preparation method of oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein the metal salt is CdN in a mass ratio of 1 2 O 6 .4H 2 O and Na 2 SnO 3 ·3H 2 O。
6. The method for preparing an oxygen, nitrogen and metal co-doped carbon material as claimed in claim 1, wherein in the step S2, the shielding gas is continuously introduced at a rate of 15-40 mL/min.
7. The method for preparing the oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein in the step S2, the temperature is raised from room temperature to 280-320 ℃ at a rate of 1.2-1.8 ℃/min, then raised to 700-900 ℃ at a rate of 2-2.2 ℃/min, then kept for 1-3 hours, then lowered to 500 ℃ at a rate of 5 ℃/min, and finally naturally cooled to room temperature, so as to obtain the carbon material.
8. The method for preparing an oxygen, nitrogen and metal co-doped carbon material according to claim 1, wherein the rate of adding ethylenediamine in step S2 is 3 to 6mL/min.
9. Application of the carbon material codoped with oxygen, nitrogen and metal obtained by the preparation method according to any one of claims 1 to 8 in the field of rubber.
10. Use according to claim 9 for the preparation of rubber bearings.
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