CN116332157B - Preparation method of nitrogen-metal doped carbon material and application of nitrogen-metal doped carbon material in rubber - Google Patents
Preparation method of nitrogen-metal doped carbon material and application of nitrogen-metal doped carbon material in rubber Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 229920001971 elastomer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 64
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 58
- 239000007864 aqueous solution Substances 0.000 claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 32
- 239000000725 suspension Substances 0.000 claims abstract description 32
- 238000003763 carbonization Methods 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 23
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000000985 reactive dye Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 claims abstract description 8
- 235000013305 food Nutrition 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 14
- 235000010413 sodium alginate Nutrition 0.000 claims description 14
- 229940005550 sodium alginate Drugs 0.000 claims description 14
- 239000000661 sodium alginate Substances 0.000 claims description 14
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 11
- 229920002101 Chitin Polymers 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 4
- CEZCCHQBSQPRMU-UHFFFAOYSA-L chembl174821 Chemical compound [Na+].[Na+].COC1=CC(S([O-])(=O)=O)=C(C)C=C1N=NC1=C(O)C=CC2=CC(S([O-])(=O)=O)=CC=C12 CEZCCHQBSQPRMU-UHFFFAOYSA-L 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 238000009826 distribution Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000004073 vulcanization Methods 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 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
- 150000001408 amides Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 4
- 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 4
- JPVRJMGCWMBVMY-UHFFFAOYSA-N methylcarbamothioylsulfanyl n-methylcarbamodithioate Chemical compound CNC(=S)SSC(=S)NC JPVRJMGCWMBVMY-UHFFFAOYSA-N 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
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 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
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 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
- 229910014570 C—OH Inorganic materials 0.000 description 1
- XYQGTTDSDCKKFV-UHFFFAOYSA-N [O].[N].[Cu] Chemical compound [O].[N].[Cu] XYQGTTDSDCKKFV-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical group N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000013522 chelant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction 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
- 238000009396 hybridization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- -1 znO Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a nitrogen-metal doped carbon material and application thereof in rubber, comprising the following steps: A. adding a polyethyleneimine aqueous solution, a carbon source, glutaraldehyde, a reactive dye and metal salt into a potassium hydroxide aqueous solution, adjusting the pH to 7-12, and stirring at 30-40 ℃ to obtain a suspension; B. repeatedly ball-milling the suspension for 4-6 times, wherein each time of ball milling is carried out for 35-45min, and standing for 0.5-1h after each time of ball milling is finished, thus obtaining a solid intermediate; C. placing the solid intermediate in inert atmosphere for carbonization reaction, and cooling to room temperature to obtain a nitrogen-metal doped carbon material; the reactive dye is one or the combination of any two or more of automobile blue F3GA, acid orange 7 and food magenta 40. The carbon material prepared by the method can effectively reinforce rubber.
Description
Technical Field
The invention relates to a preparation method of a nitrogen-metal doped carbon material and application of the nitrogen-metal doped carbon material 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, thus allotropes with very different structures and properties, such as zero-dimensional carbon black and fullerene, one-dimensional carbon nanotubes and carbon nanofibers, two-dimensional graphene, and the like, can be formed. 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. The rubber water stop is used as an anti-seepage material in concrete joints between the building and the water and soil structures, and the strength of rubber, including hardness, tensile strength and tearing degree, can influence the whole shock resistance and service life of the bridge structure.
Therefore, it is very necessary to develop a carbon material having a good reinforcing effect.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a nitrogen-metal doped carbon material capable of effectively reinforcing the mechanical properties of rubber, and provides a preparation method and application thereof in rubber.
In order to solve the problems, the invention adopts the following technical scheme:
subject 1
A preparation method of a nitrogen-metal doped carbon material comprises the following steps:
A. adding a polyethyleneimine aqueous solution, a carbon source, glutaraldehyde, a reactive dye and metal salt into a potassium hydroxide aqueous solution, adjusting the pH to 7-12, and stirring at 30-40 ℃ to obtain a suspension;
B. repeatedly ball-milling the suspension for 4-6 times, wherein each time of ball milling is carried out for 35-45min, and standing for 0.5-1h after each time of ball milling is finished, thus obtaining a solid intermediate;
C. placing the solid intermediate in inert atmosphere for carbonization reaction, and cooling to room temperature to obtain a nitrogen-metal doped carbon material;
the mass ratio range of the polyethyleneimine aqueous solution, the carbon source, the glutaraldehyde, the reactive dye, the metal salt and the potassium hydroxide aqueous solution is 7-12:2.1-4.0:27-33:1.2-3.5:3.0-5.1:100;
the reactive dye is one or the combination of any two or more of automobile blue F3GA, acid orange 7 and food magenta 40.
In some embodiments of the invention, the stirring rate in step A is 100-200 revolutions per minute and stirring is performed for 3-5 hours.
In some embodiments of the invention, in the step a, the mass concentration of the polyethyleneimine aqueous solution is 40%, and the mass concentration of the potassium hydroxide aqueous solution is 20-57%.
In some embodiments of the invention, in the step a, the carbon source is one or a combination of any two or more of chitin, chitosan and sodium alginate.
In some embodiments of the invention, in the step a, the reactive dye is in a mass ratio of 1: acid orange 7 and food red 40 of 1.
In some embodiments of the invention, in the step a, the metal salt is one or a combination of any two or more of nickel acetylacetonate, copper acetylacetonate and cobalt acetylacetonate.
In some embodiments of the present invention, in the step B, the product obtained after final standing is dried in an oven with a drying temperature of 80-100 ℃ for 4.5-5.5 hours; the rotation speed of the ball milling is 450-650 rpm.
In some embodiments of the invention, in said step C, the temperature of the carbonization reaction is 700-900 ℃ for 1-3 hours.
In some embodiments of the invention, the mass ratio of the aqueous polyethyleneimine solution, carbon source, glutaraldehyde, reactive dye, metal salt and aqueous potassium hydroxide solution is 10:3:30:2:4:100.
subject matter II
The nitrogen-metal doped carbon material obtained by the preparation method provided by the technical subject one is applied to the rubber field.
In some embodiments of the invention, the application is in the preparation of rubber waterstops.
In some embodiments of the invention, the rubber water stop comprises raw materials in a mass ratio of 100:40:5:1:1:2, butyl rubber, nitrogen-metal doped carbon material, znO, stearic acid, 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) and 2-mercaptobenzothiazole (M).
The preparation process of the rubber water stop belt comprises the following steps: putting 100kg of butyl rubber into an internal mixer for rubber breaking, plasticating for 30s, and lifting bolts; adding 40kg of nitrogen-metal doped carbon material into an internal mixer, carrying out one-stage mixing for 2min, then adding 5kg of ZnO and 1kg of stearic acid together, keeping the mixing time for about 6 min, and discharging glue after 90 s ℃ at the temperature of about 140 ℃; then adjusting the roll gap of an open mill, pouring the adhesive for 3 times, then discharging the sheet, and cooling to room temperature;
mixing 2kg of sulfur and 1kg of accelerator on an open mill, carrying out two-stage mixing, carrying out thin-pass, carrying out triangular wrapping and rolling for three times, and discharging tablets; putting the rubber compound into a mold for vulcanization molding to obtain rubber, wherein the vulcanization temperature is 145 ℃, the vulcanization time is 180s, and the vulcanization pressure is 10MPa; 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).
The beneficial effects of adopting above-mentioned technical scheme to produce lie in:
in the preparation method of the carbon material, the components are matched and cooperated, and simultaneously metal elements are doped, so that the dispersity of the carbon material is improved, the carbon material can be fully contacted with rubber after being applied to the rubber, agglomeration is effectively avoided, and the specific surface area 642-967 m of the nitrogen-metal doped carbon material prepared by the preparation method of the invention 2 Per g, pore volume 18-44cm 3 And/g. The rubber water stop belt prepared from the carbon material prepared by the method disclosed by the invention meets the standard of Q/CR 562.2-2017 of the section 2 of railway tunnel waterproof and drainage material, namely the water stop belt through tests.
The glutaraldehyde is a crosslinking complexing agent of a carbon source, the crosslinking reaction of the carbon source with hydroxyl and glutaraldehyde belongs to etherification crosslinking, and the aldehyde group of the glutaraldehyde as a crosslinking agent is crosslinked with the hydroxyl of the carbon source to form an ether bond so as to promote the polymerization of the carbon source.
The carbon source structure contains a large amount of hydroxyl or amino groups, which can chelate metal ions and adsorb dye molecules.
Polyethyleneimine contains a large number of amino groups and imino groups as a crosslinking agent and a complexing agent, can be combined with a carbon source through hydrogen bonds, and can complex metal ions in cooperation with the carbon source.
Drawings
FIG. 1 is a graph showing the particle size distribution of a carbon material prepared in example 3 of the present invention;
FIG. 2 is an XPS chart of oxygen in the carbon material prepared in example 3 of the present invention; wherein a represents an oxygen profile in O-c=o, and B represents an oxygen profile in C-OH/C-O-C;
FIG. 3 is an XPS chart of nitrogen of the carbon material prepared in example 3 of the present invention; wherein A represents a graphite nitrogen spectrum, B represents a pyrrole nitrogen spectrum, and C represents a pyridine nitrogen spectrum;
FIG. 4 is an XPS chart of copper as a carbon material prepared in example 3 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.
Each of the materials used in this example is commercially available.
Aqueous polyethylenimine solution, manufacturer: shanghai Ala Biochemical technology Co., ltd., M.W. 600,99%, CAS number 9002-98-6;
chitin: the manufacturer: shanghai Ala Biochemical technology Co., ltd., CAS number 1398-61-4;
chitosan: the deacetylation degree is more than or equal to 95 percent, the viscosity is 100-200 mpa.s, and the manufacturer: shanghai Ala Biochemical technology Co., ltd., CAS number 9012-76-4;
sodium alginate: viscosity 200+ -20 mpa.s, manufacturer: shanghai Ala Biochemical technology Co., ltd., CAS number 9005-38-3;
automobile Polish F3GA: CAS number 84166-13-2, manufacturer: shanghai Ala Biochemical technology Co., ltd;
food fuchsin 40: CAS number 25956-17-6, manufacturer: shanghai Ala Biochemical technology Co., ltd.
Example 1
A. 12g of a 40% by mass concentration polyethyleneimine aqueous solution, 4g of chitin, 33g of glutaraldehyde, 3.5g of steam-branded F3GA, 5.1g of nickel acetylacetonate and 100g of a 57% by mass concentration potassium hydroxide aqueous solution are added into a 250 ml flask, the pH is adjusted to 12, and the mixture is stirred for 4 hours under the conditions of 30 ℃ and stirring speed of 100 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 4 times at a ball milling rotating speed of 650 revolutions per minute, ball milling for 45 minutes each time, standing for 0.5h after ball milling, and placing a product obtained after final standing into an oven with a drying temperature of 80 ℃ for 5.5h to dry to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 701 and 701 m 2 And/g, pore size distribution of 27-44nm.
Example 2
A. 7g of a 40% by mass concentration polyethyleneimine aqueous solution, 2.1g of chitosan, 27g of glutaraldehyde, 1.2g of acid orange 7, 3.0g of cobalt acetylacetonate and 100g of a 20% by mass concentration potassium hydroxide aqueous solution are added into a 250 ml flask, the pH is regulated to 7.1, and the mixture is stirred for 3 hours at a temperature of 40 ℃ and a stirring rate of 200 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 6 times at the ball milling rotating speed of 450 r/min and for 35min each time, standing for 1h after each ball milling, and placing the finally-standing product into an oven with the drying temperature of 100 ℃ for 4.5h to dry to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 700 ℃ at the speed of 5 ℃/min and the temperature is kept for 3 hours, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 642 m 2 And/g, pore size distribution of 25-30nm.
Example 3
A. 10g of a polyethyleneimine aqueous solution with the mass concentration of 40%, 3.0g of sodium alginate, 30g of glutaraldehyde, 2g of fuchsin 40, 4g of copper acetylacetonate and 100g of a potassium hydroxide aqueous solution with the concentration of 30% are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours at 35 ℃ under the condition of stirring speed of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 967 m 2 And/g, the particle size distribution is 18-20nm.
The particle size distribution analysis was performed on the prepared carbon material, as shown in fig. 1. The composition characterization of oxygen, nitrogen and copper of the prepared carbon material is respectively shown in fig. 2, 3 and 4, and it can be seen that the carbon material is successfully doped with the nitrogen-oxygen-copper element.
Example 4
A. 10g of a polyethyleneimine aqueous solution with the mass concentration of 40%, 3.0g of sodium alginate, 30g of glutaraldehyde, 2g of acid orange 7, 4g of copper acetylacetonate and 100g of a potassium hydroxide aqueous solution with the concentration of 30% are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours at 35 ℃ under the condition of stirring speed of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 890 m 2 And/g, particle size distribution of 19-25nm.
Example 5
A. 10g of a 40% by mass concentration polyethyleneimine aqueous solution, 3.0g of sodium alginate, 30g of glutaraldehyde, 1g of fuchsin 40, 1g of acid orange 7, 4g of copper acetylacetonate and 100g of a 30% by mass concentration potassium hydroxide aqueous solution are added into a 250 ml flask, the pH is adjusted to 8.0, and the mixture is stirred for 5 hours at 35 ℃ and a stirring rate of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 735 m 2 And/g, particle size distribution of 25-41nm.
Effect example 1
The nitrogen-metal doped carbon materials prepared in examples 1 to 5 were used to prepare rubber water stop samples 1 to 5 by the following method:
putting 100kg of butyl rubber into an internal mixer for rubber breaking, plasticating for 30s, and lifting bolts; adding 40kg of nitrogen-metal doped carbon material into an internal mixer, carrying out one-stage mixing for 2min, then adding 5kg of ZnO and 1kg of stearic acid together, keeping the mixing time for about 6 min, and discharging glue after 90 s ℃ at the temperature of about 140 ℃; then adjusting the roll gap of an open mill, pouring the adhesive for 3 times, then discharging the sheet, and cooling to room temperature;
mixing 2kg of sulfur and 1kg of accelerator on an open mill, carrying out two-stage mixing, carrying out thin-pass, carrying out triangular wrapping and rolling for three times, and discharging tablets; putting the rubber compound into a mold for vulcanization molding to obtain rubber, wherein the vulcanization temperature is 145 ℃, the vulcanization time is 180s, and the vulcanization pressure is 10MPa; 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) and 2-mercaptobenzothiazole (M).
The performance of the obtained rubber water stop rubber compound was tested according to the standard Q/CR 562.2-2017 (railway Tunnel waterproof and drainage Material part 2: water stop), and the results are shown in Table 1 below:
TABLE 1
Comparative example 1
A. 10g of a polyethyleneimine aqueous solution with a mass concentration of 40%, 3.0g of sodium alginate, 2g of food fuchsin 40, 4g of copper acetylacetonate and 100g of a potassium hydroxide aqueous solution with a concentration of 30% are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours under the conditions of 35 ℃ and a stirring rate of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 413 m 2 And/g, particle size distribution is 33-58nm.
Comparative example 2
A. 3.0g of sodium alginate, 30g of glutaraldehyde, 2g of fuchsin 40, 4g of copper acetylacetonate and 100g of 30% potassium hydroxide aqueous solution are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours at 35 ℃ and a stirring rate of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 506m 2 And/g, particle size distribution of 32-59nm.
Comparative example 3
A. 10g of a polyethyleneimine aqueous solution with the mass concentration of 40%, 3.0g of sodium alginate, 30g of glutaraldehyde, 4g of copper acetylacetonate and 100g of a potassium hydroxide aqueous solution with the concentration of 30% are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours under the conditions of 35 ℃ and the stirring rate of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 437m 2 And/g, particle size distribution of 27-49nm.
Comparative example 4
A. 10g of a polyethyleneimine aqueous solution with a mass concentration of 40%, 3.0g of sodium alginate, 30g of glutaraldehyde, 2g of fuchsin 40, 4g of copper acetylacetonate and 100g of water are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours under the conditions of 35 ℃ and a stirring rate of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 519m 2 And/g, the particle size distribution is 22-60nm.
Comparative example 5
A. 10g of a polyethyleneimine aqueous solution with the mass concentration of 40%, 3.0g of sodium alginate, 30g of glutaraldehyde, 2g of fuchsin 40, 4g of copper acetylacetonate and 100g of a potassium hydroxide aqueous solution with the concentration of 15% are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours at 35 ℃ under the condition of stirring speed of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 582 m 2 And/g, particle size distribution of 23-57nm.
Comparative example 6
A. 10g of a polyethyleneimine aqueous solution with the mass concentration of 40%, 3.0g of sodium alginate, 30g of glutaraldehyde, 2g of fuchsin 40, 4g of copper acetylacetonate and 100g of a potassium hydroxide aqueous solution with the concentration of 60% are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours at 35 ℃ under the condition of stirring speed of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 554m 2 And/g, the particle size distribution is 20-46nm.
Comparative example 7
A. 10g of a polyethyleneimine aqueous solution with a mass concentration of 40%, 3.0g of sodium alginate, 30g of glutaraldehyde, 2g of food fuchsin 40 and 100g of a potassium hydroxide aqueous solution with a concentration of 30% are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours at 35 ℃ under the condition of stirring speed of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 600m 2 And/g, particle size distribution of 21-51nm.
Comparative example 8
A. 10g of polyethyleneimine water solution with the mass concentration of 40%, 3.0g of sodium alginate, 30g of glutaraldehyde and 100g of potassium hydroxide water solution with the concentration of 30% are added into a 250 ml flask, the pH is regulated to 8.0, and the mixture is stirred for 5 hours under the conditions of 35 ℃ and the stirring rate of 150 revolutions per minute to obtain a suspension;
B. placing the suspension into a ball milling tank of a high-energy ball mill, repeatedly ball milling for 5 times at a ball milling rotating speed of 500 revolutions per minute and for 40 minutes each time, standing for 0.5h after each ball milling, and placing a product obtained after the last standing into an oven with a drying temperature of 90 ℃ for 5h to be dried to obtain a solid intermediate;
C. the solid intermediate is placed in an inert atmosphere for carbonization reaction, the specific carbonization step is that the temperature is firstly increased to 210 ℃ from the room temperature at the speed of 2 ℃/min, the temperature is kept at 210 ℃ for 1 hour, the temperature is increased to 900 ℃ at the speed of 5 ℃/min and the temperature is kept for 1 hour, the temperature is reduced to 500 ℃ at the speed of 7 ℃/min, the temperature is naturally reduced to the room temperature, and finally the nitrogen-metal doped carbon material is obtained by washing to be neutral by using 1M hydrochloric acid aqueous solution.
The parameters of the prepared carbon material are as follows: specific surface area 320 m 2 And/g, particle size distribution is 24-78nm.
Effect example 2
The nitrogen-metal doped carbon materials prepared in comparative examples 1 to 8 were used to prepare rubber water stop comparative samples 1 to 8 by the following method:
the preparation method of the rubber water stop belt comprises the following steps:
putting 100kg of butyl rubber into an internal mixer for rubber breaking, plasticating for 30s, and lifting bolts; adding 40kg of nitrogen-metal doped carbon material into an internal mixer, carrying out one-stage mixing for 2min, then adding 5kg of ZnO and 1kg of stearic acid together, keeping the mixing time for about 6 min, and discharging glue after 90 s ℃ at the temperature of about 140 ℃; then adjusting the roll gap of an open mill, pouring the adhesive for 3 times, then discharging the sheet, and cooling to room temperature;
mixing 2kg of sulfur and 1kg of accelerator on an open mill, carrying out two-stage mixing, carrying out thin-pass, carrying out triangular wrapping and rolling for three times, and discharging tablets; putting the rubber compound into a mold for vulcanization molding to obtain rubber, wherein the vulcanization temperature is 145 ℃, the vulcanization time is 180s, and the vulcanization pressure is 10MPa; 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) and 2-mercaptobenzothiazole (M).
The performance of the obtained rubber water stop rubber compound was tested according to the standard Q/CR 562.2-2017 (railway Tunnel waterproof and drainage Material part 2: water stop), and the results are shown in Table 2 below:
TABLE 2
Claims (8)
1. The preparation method of the nitrogen-metal doped carbon material is characterized by comprising the following steps of:
A. adding a polyethyleneimine aqueous solution, a carbon source, glutaraldehyde, a reactive dye and metal salt into a potassium hydroxide aqueous solution, adjusting the pH to 7-12, and stirring at 30-40 ℃ to obtain a suspension;
B. repeatedly ball-milling the suspension for 4-6 times, wherein each time of ball milling is carried out for 35-45min, and standing for 0.5-1h after each time of ball milling is finished, thus obtaining a solid intermediate;
C. placing the solid intermediate in inert atmosphere for carbonization reaction, and cooling to room temperature to obtain a nitrogen-metal doped carbon material; the nitrogen-metal doped carbon material is applied to the field of rubber;
the mass ratio range of the polyethyleneimine aqueous solution, the carbon source, the glutaraldehyde, the reactive dye, the metal salt and the potassium hydroxide aqueous solution is 7-12:2.1-4.0:27-33:1.2-3.5:3.0-5.1:100;
the mass concentration of the potassium hydroxide aqueous solution is 20-57%;
the metal salt is one or the combination of any two or more of nickel acetylacetonate, copper acetylacetonate and cobalt acetylacetonate;
the reactive dye is one or the combination of any two or more of the automobile blue F3GA, the acid orange 7 and the food magenta 40.
2. The method for preparing a nitrogen-metal doped carbon material according to claim 1, wherein in the step a, the mass concentration of the polyethyleneimine aqueous solution is 40%.
3. The method for preparing a nitrogen-metal doped carbon material according to claim 1, wherein in the step a, the carbon source is one or a combination of any two or more of chitin, chitosan and sodium alginate.
4. The method for preparing a nitrogen-metal doped carbon material according to claim 1, wherein in the step a, the reactive dye is in a mass ratio of 1: acid orange 7 and food red 40 of 1.
5. The method for preparing a nitrogen-metal doped carbon material according to claim 1, wherein in the step B, the product obtained after final standing is dried in an oven with a drying temperature of 80-100 ℃ for 4.5-5.5 hours; the rotation speed of the ball milling is 450-650 rpm.
6. The method for preparing a nitrogen-metal doped carbon material according to claim 1, wherein in the step C, the carbonization reaction is performed at a temperature of 700-900 ℃ for a time of 1-3 hours.
7. The method for preparing the nitrogen-metal doped carbon material according to claim 1, wherein the mass ratio of the polyethyleneimine aqueous solution to the carbon source to the glutaraldehyde to the reactive dye to the metal salt to the potassium hydroxide aqueous solution is 10:3:30:2:4:100.
8. use of the nitrogen-metal doped carbon material obtained by the preparation method according to claim 1, characterized in that the use is the preparation of a rubber water stop.
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