CN116812915B - Nitrogen-nickel-copper doped carbon material and preparation method and application thereof - Google Patents
Nitrogen-nickel-copper doped carbon material and preparation method and application thereof Download PDFInfo
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- CN116812915B CN116812915B CN202310818792.2A CN202310818792A CN116812915B CN 116812915 B CN116812915 B CN 116812915B CN 202310818792 A CN202310818792 A CN 202310818792A CN 116812915 B CN116812915 B CN 116812915B
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- -1 Nitrogen-nickel-copper Chemical compound 0.000 title claims abstract description 58
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 54
- 239000005060 rubber Substances 0.000 claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 26
- 238000003763 carbonization Methods 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical group [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical group [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 5
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 4
- BKAFBBWDHTZFSB-UHFFFAOYSA-N 2-(3-methyl-2h-imidazol-1-yl)ethanol Chemical compound CN1CN(CCO)C=C1 BKAFBBWDHTZFSB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 4
- 229920002101 Chitin Polymers 0.000 claims description 4
- NHEULQMXMXIOJY-UHFFFAOYSA-N Cl[PH2]=O Chemical compound Cl[PH2]=O NHEULQMXMXIOJY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- AQKOHYMKBUOXEB-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-(16-methylheptadecanoyloxy)oxolan-2-yl]-2-(16-methylheptadecanoyloxy)ethyl] 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCC(C)C)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCC(C)C AQKOHYMKBUOXEB-RYNSOKOISA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- WYLQARGYFXBZMD-UHFFFAOYSA-N n-[chloro(dimethylamino)phosphoryl]-n-methylmethanamine Chemical compound CN(C)P(Cl)(=O)N(C)C WYLQARGYFXBZMD-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- YLNSNVGRSIOCEU-UHFFFAOYSA-N oxiran-2-ylmethyl butanoate Chemical compound CCCC(=O)OCC1CO1 YLNSNVGRSIOCEU-UHFFFAOYSA-N 0.000 claims description 4
- 229920001277 pectin Polymers 0.000 claims description 4
- 235000010987 pectin Nutrition 0.000 claims description 4
- 239000001814 pectin Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- VEWFZHAHZPVQES-UHFFFAOYSA-N boron;n,n-diethylethanamine Chemical compound [B].CCN(CC)CC VEWFZHAHZPVQES-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000012744 reinforcing agent Substances 0.000 abstract description 15
- 239000000654 additive Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229920005549 butyl rubber Polymers 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 230000032683 aging 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
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- CGTGVSBVWWZIDT-UHFFFAOYSA-N isoquinolin-6-yl(trimethyl)stannane Chemical compound C1=NC=CC2=CC([Sn](C)(C)C)=CC=C21 CGTGVSBVWWZIDT-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- JPVRJMGCWMBVMY-UHFFFAOYSA-N methylcarbamothioylsulfanyl n-methylcarbamodithioate Chemical compound CNC(=S)SSC(=S)NC JPVRJMGCWMBVMY-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of rubber additives, and discloses a nitrogen-nickel-copper doped carbon material, and a preparation method and application thereof. The preparation method comprises the following steps: (1) Mixing a carbon source, a nitrogen source, a hydroxyl activating catalyst, a cross-linking agent, a pore-forming agent and water, and performing hydrothermal reaction to obtain semi-solid gel; (2) Mixing the semisolid gel, a copper source, a nickel source and water, and performing hydrothermal reaction to obtain gel; (3) And sequentially performing freeze drying and carbonization on the gel to obtain the nitrogen-nickel-copper doped carbon material. The rubber water stop belt prepared by taking the nitrogen-nickel-copper doped carbon material as the rubber reinforcing agent has excellent mechanical property and weather resistance, and can meet the application of rubber products with higher requirements.
Description
Technical Field
The invention relates to the technical field of rubber additives, in particular to a nitrogen-nickel-copper doped carbon material, and a preparation method and application thereof.
Background
The rubber reinforcing agent is an additive capable of improving the mechanical properties of rubber such as wear resistance, tear resistance, tensile strength and the like. For synthetic rubber and natural rubber, the mechanical properties such as tensile strength, abrasion resistance and the like are very low, and the application is difficult. Therefore, reinforcement with a rubber reinforcing agent is required. The common rubber reinforcing agents include carbon black, white carbon black, reinforcing resin, fly ash and the like. Among them, carbon black is a rubber reinforcing agent commonly used in the art. Since carbon black easily pollutes the environment, most of the conventional rubber reinforcing agents are reinforcing resins, fly ash and the like.
However, the existing rubber reinforcing agent has low bonding strength with rubber, so that the rubber reinforcing agent is unevenly dispersed in a rubber system, the mechanical property of the rubber is not improved, the property of the rubber is reduced, and the rubber is easy to crack. And the existing rubber reinforcing agent has poor reinforcing effect, so that the application range of the rubber is greatly limited. Therefore, there is a need in the art to develop a rubber reinforcing agent that can significantly improve the mechanical properties of rubber and disperse uniformly in rubber systems.
Disclosure of Invention
The invention provides a nitrogen-nickel-copper doped carbon material, and a preparation method and application thereof, so as to solve the problems that the existing rubber reinforcing agent has poor reinforcing effect and cannot be uniformly dispersed in rubber.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a nitrogen-nickel-copper doped carbon material, which comprises the following steps:
(1) Mixing a carbon source, a nitrogen source, a hydroxyl activating catalyst, a cross-linking agent, a pore-forming agent and water, and performing hydrothermal reaction to obtain semi-solid gel;
(2) Mixing the semisolid gel, a copper source, a nickel source and water, and performing hydrothermal reaction to obtain gel;
(3) And sequentially performing freeze drying and carbonization on the gel to obtain the nitrogen-nickel-copper doped carbon material.
Preferably, in the step (1), the carbon source is one or more of pectin, chitin and lignin; the nitrogen source is one or more of dicyandiamide, 1-butyl-3-methylimidazole dicyandiamide salt, dicyandiamide sodium, 1- (2-hydroxyethyl) -3-methylimidazole dicyandiamide and cyanamide; the hydroxyl activating catalyst is one or more of bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride, bis (dimethylamino) phosphoryl chloride and 2-cyanoethyl hypochloro hypochlorite; the cross-linking agent is one or more of triglycidyl isocyanurate, sorbitan triisostearate and glycidyl butyrate; the pore-forming agent is one or more of triethylamine, melamine, diethylamine, triethylamine hydrochloride and triethylamine-borane.
Preferably, in the step (1), the mass ratio of the carbon source, the nitrogen source, the hydroxyl activating catalyst, the cross-linking agent, the pore-forming agent and the water is 3-4: 1-2: 0.5 to 1.5:0.5 to 1.5:1.5 to 3:20 to 35.
Preferably, in the step (1), the temperature of the hydrothermal reaction is 70-90 ℃, and the time of the hydrothermal reaction is 10-14 hours.
Preferably, in the step (2), the copper source is copper acetylacetonate and/or copper nitrate; the nickel source is nickel acetylacetonate and/or nickel nitrate; the mass ratio of the semi-solid gel to the copper source to the nickel source to the water is 3-4: 0.5 to 1.8:0.5 to 1.5:6 to 10.
Preferably, in the step (2), the mixing temperature is 25-40 ℃ and the mixing time is 20-40 min; the temperature of the hydrothermal reaction is 100-110 ℃, and the time of the hydrothermal reaction is 7-9 h.
Preferably, in the step (3), the freeze-drying temperature is-20 to-10 ℃, and the freeze-drying time is 0.5 to 1.5 hours.
Preferably, in the step (3), the carbonization is performed under a protective gas, wherein the protective gas is nitrogen, hydrogen or argon; the carbonization temperature is 700-900 ℃, the carbonization time is 1-3 h, and the carbonization heating rate is 10-20 ℃/min.
The invention also provides the nitrogen-nickel-copper doped carbon material prepared by the preparation method of the nitrogen-nickel-copper doped carbon material.
The invention also provides application of the nitrogen-nickel-copper doped carbon material as a rubber reinforcing agent in a rubber water stop.
Compared with the prior art, the invention has the following beneficial effects:
the surface of the nitrogen-nickel-copper doped carbon material contains abundant active groups and pore structures, so that the mechanical properties of rubber can be obviously improved; the existence of active groups (carboxyl, ester groups, halogen and the like) can enable the nitrogen-nickel-copper doped carbon material to react with the rubber to be tightly combined, so that the nitrogen-nickel-copper doped carbon material is uniformly distributed in the rubber, and the addition of a coupling agent is omitted; meanwhile, the doping of nitrogen, nickel and copper can improve the heat conductivity of the rubber, reduce the influence of the environment on the rubber performance and improve the weather resistance of the rubber.
Detailed Description
The invention provides a preparation method of a nitrogen-nickel-copper doped carbon material, which comprises the following steps:
(1) Mixing a carbon source, a nitrogen source, a hydroxyl activating catalyst, a cross-linking agent, a pore-forming agent and water, and performing hydrothermal reaction to obtain semi-solid gel;
(2) Mixing the semisolid gel, a copper source, a nickel source and water, and performing hydrothermal reaction to obtain gel;
(3) And sequentially performing freeze drying and carbonization on the gel to obtain the nitrogen-nickel-copper doped carbon material.
In step (1) of the present invention, the carbon source is preferably one or more of pectin, chitin and lignin; the nitrogen source is preferably one or more of dicyandiamide, 1-butyl-3-methylimidazole dicyandiamide salt, dicyandiamide sodium, 1- (2-hydroxyethyl) -3-methylimidazole dicyandiamide and cyanamide; the hydroxyl activating catalyst is preferably one or more of bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride, bis (dimethylamino) phosphoryl chloride and 2-cyanoethyl hypochlorohypochlorite; the cross-linking agent is preferably one or more of triglycidyl isocyanurate, sorbitan triisostearate and glycidyl butyrate; the pore-forming agent is preferably one or more of triethylamine, melamine, diethylamine, triethylamine hydrochloride and triethylamine-borane.
In the step (1) of the present invention, the mass ratio of the carbon source, the nitrogen source, the hydroxyl activating catalyst, the crosslinking agent, the pore-forming agent and the water is preferably 3 to 4: 1-2: 0.5 to 1.5:0.5 to 1.5:1.5 to 3:20 to 35, more preferably 3.2 to 3.8:1.5 to 1.7:1 to 1.2:0.8 to 1:2 to 2.5:25 to 30.
In the step (1) of the present invention, the temperature of the hydrothermal reaction is preferably 70 to 90 ℃, and more preferably 80 to 85 ℃; the hydrothermal reaction time is preferably 10 to 14 hours, more preferably 12 to 13 hours.
In step (2) of the present invention, the copper source is preferably copper acetylacetonate and/or copper nitrate; the nickel source is preferably nickel acetylacetonate and/or nickel nitrate; the mass ratio of the semisolid gel to the copper source to the nickel source to the water is preferably 3-4: 0.5 to 1.8:0.5 to 1.5:6 to 10, more preferably 3.2 to 3.5:1 to 1.5:1 to 1.2: 8-9.
In step (2) of the present invention, the temperature of the mixing is preferably 25 to 40 ℃, and more preferably 30 to 35 ℃; the mixing time is preferably 20 to 40 minutes, more preferably 30 to 35 minutes; the mixing is performed under stirring, and the stirring speed is preferably 500 to 800r/min, more preferably 600 to 700r/min.
In the step (2) of the present invention, the temperature of the hydrothermal reaction is preferably 100 to 110 ℃, and more preferably 105 to 108 ℃; the hydrothermal reaction time is preferably 7 to 9 hours, more preferably 8 to 8.5 hours.
In the present invention, the hydrothermal reaction is carried out in a reaction vessel, and the feed amount of the reaction vessel is preferably 2/3 of the volume of the reaction vessel.
In the step (3) of the present invention, the temperature of the freeze-drying is preferably-20 to-10 ℃, and more preferably-18 to-12 ℃; the time for freeze-drying is preferably 0.5 to 1.5 hours, more preferably 1 hour.
In step (3) of the present invention, the carbonization is performed under a shielding gas, preferably nitrogen, hydrogen or argon; the carbonization temperature is preferably 700-900 ℃, and more preferably 800-850 ℃; the carbonization time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours; the heating rate of carbonization is preferably 10 to 20℃per minute, more preferably 13 to 16℃per minute.
In step (3) of the present invention, before obtaining the nitrogen-nickel-copper doped carbon material, the carbonized product is air-cooled to room temperature.
In the invention, the pore-forming agent can also activate amino and provide nitrogen source, enrich the pore structure of the obtained nitrogen-nickel-copper doped carbon material, provide more active groups, improve the uniformity of the dispersion of the nitrogen-nickel-copper doped carbon material in a rubber system, and further improve the mechanical properties of the obtained rubber water stop; the copper source is used as a cross-linking agent and a curing accelerator, and the nickel source is used as a polymerization catalyst, so that the cross-linking curing degree of the obtained nitrogen-nickel-copper doped carbon material is further improved, the pore structure is optimized, and the dispersing uniformity degree of the nitrogen-nickel-copper doped carbon material in rubber is improved; the doping of nitrogen, nickel and copper can improve the heat conductivity of rubber, reduce the influence of the environment on the rubber performance, and further improve the weather resistance of the obtained rubber water stop.
The invention also provides the nitrogen-nickel-copper doped carbon material prepared by the preparation method of the nitrogen-nickel-copper doped carbon material.
The invention also provides application of the nitrogen-nickel-copper doped carbon material as a rubber reinforcing agent in a rubber water stop.
In the invention, the specific steps of the application of the nitrogen-nickel-copper doped carbon material as a rubber reinforcing agent in a rubber water stop belt are as follows: mixing butyl rubber, a nitrogen-nickel-copper doped carbon material, zinc oxide, stearic acid, an accelerator and sulfur, and sequentially carrying out mixing, thin-pass, sheet feeding and vulcanization molding to obtain the rubber water stop.
In the invention, the mass ratio of the butyl rubber, the nitrogen-nickel-copper doped carbon material, the zinc oxide, the stearic acid, the accelerator and the sulfur is preferably 90-110: 30-50: 2 to 5:0.5 to 2:0.5 to 2:1 to 3, more preferably 100 to 105: 35-40: 3-4: 1 to 1.5:1 to 1.5:1.5 to 2; the accelerator is preferably prepared from the following components in percentage by mass of 1-2: 0.2 to 0.8:0.1 to 0.4:1 to 2.5:0.1 to 0.4 of dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, dimethyl diphenyl thiuram disulfide, 4' -dithiodimorpholine and 2-mercaptobenzothiazole, and more preferably, the weight ratio is 1.2 to 1.8:0.3 to 0.5:0.2 to 0.3:2 to 2.3:0.2 to 0.3 of dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, dimethyl diphenyl thiuram disulfide, 4' -dithiodimorpholine and 2-mercaptobenzothiazole.
In the present invention, the kneading temperature is preferably 130 to 150 ℃, and more preferably 135 to 145 ℃; the kneading time is preferably 2 to 6 minutes, more preferably 3 to 4 minutes; the roll gap of the thin pass is preferably 0.5-1 mm, and more preferably 0.6-0.8 mm; the roll temperature of the thin pass is preferably less than or equal to 60 ℃, and more preferably less than or equal to 50 ℃; before the sheet is removed, the product obtained by the sheet passing is subjected to triangular packing and rolling treatment in sequence; the number of times of the triangular bag and the winding is independently preferably 2-4 times, and more preferably 3 times; the pressure of the vulcanization molding is preferably 9 to 11MPa, more preferably 10MPa; the temperature of vulcanization molding is preferably 140 to 150 ℃, and more preferably 142 to 145 ℃; the vulcanization molding time is preferably 160 to 200 seconds, more preferably 170 to 180 seconds.
In the invention, the specific steps of mixing the butyl rubber, the nitrogen-nickel-copper doped carbon material, the zinc oxide, the stearic acid, the accelerator and the sulfur are as follows: the butyl rubber is plasticated and plug extracted sequentially, a nitrogen-nickel-copper doped carbon material is added for primary banburying, zinc oxide and stearic acid are added for secondary banburying, glue pouring and sheet discharging sequentially, and then sulfur and an accelerator are added.
In the present invention, the roll gap of the mastication is preferably 2 to 3mm, more preferably 2.5 to 2.8mm; the roll temperature of plasticating is preferably less than or equal to 45 ℃, and more preferably less than or equal to 40 ℃; the plasticating time is preferably 20 to 40 seconds, more preferably 25 to 30 seconds; the temperature of the lifting bolt is preferably 130-150 ℃, and more preferably 135-145 ℃.
In the invention, the temperature of the first banburying and the second banburying is independently preferably 130-150 ℃, and more preferably 135-145 ℃; the time of the first banburying is preferably 2-6 min, and more preferably 3-4 min; the time for the second internal mixing is preferably 80 to 100 seconds, more preferably 90 to 95 seconds.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Pectin, dicyandiamide, bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride, triglycidyl isocyanurate, triethylamine and water in a ratio of 4:2:1:1:2:20, keeping the feeding amount to be 2/3 of the volume of the reaction kettle, and heating to 80 ℃ by utilizing microwaves to perform hydrothermal reaction for 12 hours to obtain semi-solid gel; the mass ratio is 4:1:1:8, stirring and mixing the semi-solid gel, copper acetylacetonate, nickel acetylacetonate and water at the temperature of 35 ℃ at the rotating speed of 600r/min for 30min, placing the mixture obtained by mixing into a reaction kettle, keeping the feeding amount to be 2/3 of the volume of the reaction kettle, and heating to 100 ℃ by utilizing microwaves to perform hydrothermal reaction for 8h to obtain gel; and freeze-drying the gel at the temperature of minus 20 ℃ for 1h, then placing the freeze-dried product into a carbonization furnace, heating to 700 ℃ at the heating rate of 15 ℃/min under the protection of nitrogen, preserving heat for 2h, and taking out the product and air-cooling to the room temperature to obtain the nitrogen-nickel-copper doped carbon material.
The specific surface area of the nitrogen-nickel-copper doped carbon material obtained in this example was 721m 2 And/g, the particle size distribution is 10-20 nm.
Example 2
Chitin, 1-butyl-3-methylimidazole dicyandiamide salt, 2-cyanoethyl hypochlorohypochlorite, glycidyl butyrate, melamine and water in a ratio of 3.5:1.8:0.8:1.5:2.8:25, keeping the feeding amount to be 2/3 of the volume of the reaction kettle, and heating to 75 ℃ by utilizing microwaves to perform hydrothermal reaction for 12 hours to obtain semi-solid gel; the mass ratio is 3.5:1.5:0.8:10, stirring and mixing the semi-solid gel, copper nitrate, nickel acetylacetonate and water at the temperature of 25 ℃ at the rotating speed of 650r/min for 40min, placing the mixture obtained by mixing into a reaction kettle, keeping the feeding amount to be 2/3 of the volume of the reaction kettle, and heating to the temperature of 110 ℃ by utilizing microwaves to perform hydrothermal reaction for 8h to obtain gel; and freeze-drying the gel at the temperature of minus 15 ℃ for 1h, then placing the freeze-dried product into a carbonization furnace, heating to the temperature of 850 ℃ at the heating rate of 12 ℃/min under the protection of argon, preserving heat for 2.5h, and taking out the product and air-cooling to the room temperature to obtain the nitrogen-nickel-copper doped carbon material.
The nitrogen-nickel-copper obtained in this exampleThe specific surface area of the doped carbon material is 718m 2 And/g, the particle size distribution is 8-15 nm.
Example 3
Lignin, 1- (2-hydroxyethyl) -3-methylimidazole dicyandiamide, bis (dimethylamino) phosphoryl chloride, PEG-160 sorbitan triisostearate, triethylamine hydrochloride and water were mixed at 3.8:1.2:1.2:1:1.8:35, keeping the feeding amount to be 2/3 of the volume of the reaction kettle, and heating to 85 ℃ by utilizing microwaves to perform hydrothermal reaction for 13 hours to obtain semi-solid gel; the mass ratio is 3.1:1:1.3:6, stirring and mixing the semisolid gel, the copper acetylacetonate, the nickel nitrate and the water at 38 ℃ at the rotating speed of 700r/min for 25min, placing the mixture obtained by mixing into a reaction kettle, keeping the feeding amount to be 2/3 of the volume of the reaction kettle, and heating to 100 ℃ by utilizing microwaves to perform hydrothermal reaction for 9h to obtain gel; and freeze-drying the gel at the temperature of minus 10 ℃ for 1h, then placing the freeze-dried product into a carbonization furnace, heating to 880 ℃ at the heating rate of 18 ℃/min under the protection of nitrogen, preserving heat for 2h, and taking out the product and air-cooling to the room temperature to obtain the nitrogen-nickel-copper doped carbon material.
The specific surface area of the nitrogen-nickel-copper doped carbon material obtained in this example was 701m 2 And/g, the particle size distribution is 15-23 nm.
As can be seen from examples 1 to 3, the nitrogen-nickel-copper doped carbon material obtained by the method has larger specific surface area, rich pore structure and more uniform particle size distribution.
The nitrogen-nickel-copper doped carbon materials obtained in examples 1 to 3 were prepared to obtain rubber water stop materials according to the following method, which were designated as samples 1 to 3, and the samples 1 to 3 were subjected to mechanical properties and aging resistance tests, with the following method and results:
the preparation method of the rubber water stop belt material comprises the following steps: 100kg of butyl rubber is put into an internal mixer to plasticate for 30s, the roll spacing is kept to be 2mm, the roll temperature is kept to be 45 ℃, the roll spacing is kept to be 2mm after plasticating is finished, and bolt extraction is carried out at 140 ℃; adding 40kg of nitrogen-nickel-copper doped carbon material into an internal mixer, carrying out primary internal mixing at 140 ℃ for 2min, adding 5kg of zinc oxide and 1kg of stearic acid into the internal mixer, carrying out secondary internal mixing at 140 ℃ for 90s, discharging glue after internal mixing is finished, pouring the glue for 3 times, then blanking, finally adding 2kg of sulfur and 1kg of accelerator (the accelerator is composed of dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, dimethyl thiuram disulfide, 4' -dithiodimorpholine and 2-mercaptobenzothiazole in a mass ratio of 1:0.5:0.2:2:0.2) into a sheet obtained by blanking on an open mill, carrying out milling for 4min at 140 ℃, and sequentially carrying out thinning (the roll spacing is 0.8mm, the roll temperature is 60 ℃), triangulating for 3 times, rolling for 3 times and blanking to obtain a rubber compound; and vulcanizing and molding the mixed rubber for 180 seconds at 145 ℃ and 10MPa, and cooling to room temperature to obtain the rubber water stop belt material.
And (3) performance detection: the hardness is detected according to the specification of GB/T531.1-2008; the tensile strength and elongation at break are detected according to the specification of GB/T528-2009; the tearing strength test is carried out according to a right-angle sample of GB/T529-2008; the heat-resistant air aging test is carried out according to the specification of GB/T3512-2001; ozone aging resistance test is carried out according to the specification of GB/T7762-2003; the brittle temperature is detected according to the specification of GB/T15256-1994; compression set detection was performed as specified in GB/T7759-1996; the adhesion of rubber to metal is carried out as specified in GB/T7760-2003. The results obtained are shown in Table 1.
Table 1 Properties of samples 1 to 3 prepared from the N-Nickel-copper doped carbon materials obtained in examples 1 to 3
As shown in Table 1, the nitrogen-nickel-copper doped carbon material obtained by the invention is used as a rubber reinforcing agent to prepare a rubber water stop belt with excellent mechanical properties and weather resistance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A method for preparing a nitrogen-nickel-copper doped carbon material, comprising the steps of:
(1) Mixing a carbon source, a nitrogen source, a hydroxyl activating catalyst, a cross-linking agent, a pore-forming agent and water, and performing hydrothermal reaction to obtain semi-solid gel;
(2) Mixing the semisolid gel, a copper source, a nickel source and water, and performing hydrothermal reaction to obtain gel;
(3) Sequentially performing freeze drying and carbonization on the gel to obtain a nitrogen-nickel-copper doped carbon material;
in the step (1), the carbon source is one or more of pectin, chitin and lignin; the nitrogen source is one or more of dicyandiamide, 1-butyl-3-methylimidazole dicyandiamide salt, dicyandiamide sodium, 1- (2-hydroxyethyl) -3-methylimidazole dicyandiamide and cyanamide; the hydroxyl activating catalyst is one or more of bis (2-oxo-3-oxazolidinyl) hypophosphorous acid chloride, bis (dimethylamino) phosphoryl chloride and 2-cyanoethyl hypochloro hypochlorite; the cross-linking agent is one or more of triglycidyl isocyanurate, sorbitan triisostearate and glycidyl butyrate; the pore-forming agent is one or more of triethylamine, melamine, diethylamine, triethylamine hydrochloride and triethylamine-borane;
in the step (1), the mass ratio of the carbon source, the nitrogen source, the hydroxyl activating catalyst, the cross-linking agent, the pore-forming agent and the water is 3-4: 1-2: 0.5 to 1.5:0.5 to 1.5:1.5 to 3: 20-35;
in the step (2), the mass ratio of the semi-solid gel to the copper source to the nickel source to the water is 3-4: 0.5 to 1.8:0.5 to 1.5:6 to 10.
2. The method for preparing a nitrogen-nickel-copper doped carbon material according to claim 1, wherein in the step (1), the hydrothermal reaction is performed at a temperature of 70 to 90 ℃ for a time of 10 to 14 hours.
3. The method of producing a nitrogen-nickel-copper doped carbon material according to claim 1 or 2, wherein in step (2), the copper source is copper acetylacetonate and/or copper nitrate; the nickel source is nickel acetylacetonate and/or nickel nitrate.
4. The method for preparing a nitrogen-nickel-copper doped carbon material according to claim 3, wherein in the step (2), the mixing temperature is 25-40 ℃ and the mixing time is 20-40 min; the temperature of the hydrothermal reaction is 100-110 ℃, and the time of the hydrothermal reaction is 7-9 h.
5. The method for producing a nitrogen-nickel-copper doped carbon material according to claim 1 or 4, wherein in the step (3), the freeze-drying temperature is-20 to-10 ℃, and the freeze-drying time is 0.5 to 1.5 hours.
6. The method for producing a nitrogen-nickel-copper doped carbon material according to claim 5, wherein in the step (3), the carbonization is performed under a protective gas, the protective gas being nitrogen, hydrogen or argon; the carbonization temperature is 700-900 ℃, the carbonization time is 1-3 h, and the carbonization heating rate is 10-20 ℃/min.
7. A nitrogen-nickel-copper doped carbon material produced by the production method of a nitrogen-nickel-copper doped carbon material according to any one of claims 1 to 6.
8. The use of the nitrogen-nickel-copper doped carbon material of claim 7 as a rubber reinforcement in a rubber water stop.
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