CN116986584B - Preparation method of nitrogen, phosphorus and iron doped carbon material and application of nitrogen, phosphorus and iron doped carbon material in rubber - Google Patents
Preparation method of nitrogen, phosphorus and iron doped carbon material and application of nitrogen, phosphorus and iron doped carbon material in rubber Download PDFInfo
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- CN116986584B CN116986584B CN202311266289.7A CN202311266289A CN116986584B CN 116986584 B CN116986584 B CN 116986584B CN 202311266289 A CN202311266289 A CN 202311266289A CN 116986584 B CN116986584 B CN 116986584B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 122
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 74
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 61
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 50
- 239000011574 phosphorus Substances 0.000 title claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 49
- 229920001971 elastomer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 38
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000013067 intermediate product Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 229920001661 Chitosan Polymers 0.000 claims abstract description 20
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 16
- 239000011592 zinc chloride Substances 0.000 claims abstract description 16
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims abstract description 15
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 14
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 14
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 4
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 22
- 238000009826 distribution 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
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- -1 tetramethyl alcohol Chemical compound 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- 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
- 239000000047 product 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
- 229920005549 butyl rubber Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WPGBCELIUCBRKN-UHFFFAOYSA-L [hydroxy(oxido)phosphoryl] hydrogen phosphate;tetrabutylazanium Chemical compound OP(O)(=O)OP([O-])([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC WPGBCELIUCBRKN-UHFFFAOYSA-L 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a carbon material doped with nitrogen, phosphorus and iron and application of the carbon material in rubber, comprising the following steps of: A. the mass ratio is 3-7: 1-4: 1.5-5.3: 1.3 to 4.1: 2.1-6.4 of chitosan, diammonium hydrogen phosphate, (ethane-1, 2-diyl bis (phosphino)) tetramethanol, zinc chloride and potassium ferrate, and standing to obtain an intermediate product; B. and (3) under the air atmosphere, treating the intermediate product at 180-220 ℃ for 2-4 hours, then placing the intermediate product in an inert atmosphere for carbonization reaction, and cooling to room temperature to obtain the nitrogen, phosphorus and iron doped carbon material. The carbon material prepared by the method can effectively reinforce rubber.
Description
Technical Field
The invention relates to a preparation method of a carbon material doped with nitrogen, phosphorus and iron and application of the carbon material in rubber, and belongs to the technical field of carbon materials.
Background
Carbon is one of the most common elements 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, thereby allowing the formation of allotropes of widely differing structure and nature, e.g. zero-dimensionalCarbon black and fullerenes, one-dimensional carbon nanotubes and carbon nanofibers, two-dimensional graphene, and the like. From traditional carbon black to latest two-dimensional graphene, carbon materials have been widely applied to the fields of adsorbents, catalysts, fuel cells, electrode materials of secondary batteries, supercapacitors, composite materials, gas sensors, solar cells, various electronic devices and the like by virtue of unique and excellent mechanical, electrical, thermal and other properties.
The carbon material can be used as a filler to be added into rubber, can enhance the physical, thermal, electrical and gas/liquid barrier properties of the rubber, and can reduce the production cost of rubber products. At present, carbon materials commonly used in rubber are graphite, carbon black, graphene oxide, carbon fiber and carbon nano tube, but the carbon materials have a plurality of defects, and cannot fully exert the reinforcing effect, such as easy agglomeration in a rubber matrix and difficult good combination with the rubber matrix. 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, phosphorus and iron 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 method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. the mass ratio is 3-7: 1-4: 1.5-5.3: 1.3 to 4.1: 2.1-6.4 of chitosan, diammonium hydrogen phosphate, (ethane-1, 2-diyl bis (phosphino)) tetramethanol, zinc chloride and potassium ferrate, and standing to obtain an intermediate product;
B. and (3) under the air atmosphere, treating the intermediate product at 180-220 ℃ for 2-4 hours, then placing the intermediate product in an inert atmosphere for carbonization reaction, and cooling to room temperature to obtain the nitrogen, phosphorus and iron doped carbon material.
As a preferred embodiment of the present invention, the mass ratio of chitosan, diammonium phosphate, (ethane-1, 2-diylbis (phosphino)) tetramethyl alcohol, zinc chloride and potassium ferrate in the step a is 5:2:2:2:3.
as a preferred embodiment of the invention, the ball milling step of the step A is specifically ball milling for 15-25min for 4-6min and repeating for 2-4 times.
As a preferred embodiment of the invention, the ball milling in the step A has the rotating speed of 450-550 r/min.
As a preferred embodiment of the present invention, the standing step is specifically standing for 50 to 70 minutes.
As a preferred embodiment of the present invention, in the step B, the carbonization reaction is performed at a temperature of 850-950 ℃ for a time of 2.5-3.5 hours.
As a preferred embodiment of the invention, the carbonization step B is to continuously introduce protective gas at a rate of 15-25 mL/min, firstly raise the temperature from room temperature to 300+/-10 ℃ at a rate of 1.2-1.7 ℃/min, then raise the temperature to 900+/-10 ℃ at a rate of 1.8-2.2 ℃/min, and then keep the temperature for 2.5-3.5 hours.
As a preferred embodiment of the invention, the viscosity of the chitosan is 200-400mPa.s.
Subject matter II
The application of the nitrogen, phosphorus and iron doped carbon material obtained by the preparation method provided by the technical subject one in the rubber field.
In some embodiments of the invention, the application is in the preparation of rubber 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, nitrogen, phosphorus, iron doped carbon materials, znO, stearic acid, an accelerator and sulfur; the accelerator is prepared from the following components in percentage by mass: 0.5:0.2:2:0.2 dibenzothiazyl Disulfide (DM), N-cyclohexyl-2-benzothiazole hypoxanthophyll amide (CZ), dimethylthiuram disulfide (TMTD), dimorpholine disulfide (DTDM) 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 carbon materials doped with nitrogen, phosphorus and iron into an internal mixer, carrying out one-stage mixing for 2min, adding 5kg of ZnO and 1kg of stearic acid together, keeping the mixing time for about 6min, and discharging glue after 90 s ℃ is reached; 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:
according to the preparation method of the carbon material, the components are matched and cooperated, and meanwhile, the 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 rubber can be effectively reinforced. 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.
In the invention, the potassium ferrate acts as an oxidant and a pore-forming agent, can directly oxidize amino into nitric acid groups at high temperature, prevents nitrogen atoms from being released, has the effect of fixing nitrogen, and improves the nitrogen content of the product; the potassium ferrate is decomposed to generate oxygen at high temperature, so that the material has an etching effect, the morphology of a product can be regulated and controlled, the porosity can be improved, and the specific surface area can be increased; potassium ferrate is also a good iron source, and can coordinate with (ethane-1, 2-diyl bis (phosphino)) tetramethanol, so that the effects of iron and phosphorus doping are achieved.
The diammonium hydrogen phosphate is decomposed and released into ammonia and water in an air atmosphere at high temperature, the ammonia and the water are excellent pore-forming agents, the specific surface area of the material can be increased, and the amino and phosphate radicals can generate hydrogen bonds with raw materials to promote the polymerization of the raw materials. In addition, diammonium phosphate is also a nitrogen source and a phosphorus source.
(ethane-1, 2-diylbis (phosphino)) tetramethyl alcohol is a phosphine ligand capable of coordinating with metals, serving as a metal locking function, and is also a phosphorus source; the hydroxyl of (ethane-1, 2-diyl bis (phosphino)) tetra-methanol can form bond with the hydroxyl and amino of chitosan, thus improving the yield of the product.
Drawings
FIG. 1 is a graph showing the particle size distribution of the carbon material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be clearly and completely described in connection with the following specific embodiments.
Each of the materials used in this example was commercially available, wherein chitosan was purchased from Shanghai Ala Biochemical technologies Co., ltd., CAS number: 9012-76-4, and viscosity was 200-400mPa.s.
Example 1
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. putting 5 g of chitosan, 2 g of diammonium hydrogen phosphate, 2 g of (ethane-1, 2-diyl-bis (phosphino)) tetramethanol, 2 g of zinc chloride and 3 g of potassium ferrate into a ball milling tank of a high-energy ball mill for ball milling three times, suspending for 5 minutes by rotating for 20 minutes at a rotating speed of 500 rpm for each ball milling, and finally standing for 1 hour to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 3 hours at 200 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 20mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 900 ℃ at a rate of 2.0 ℃/min, then maintaining for 3 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The prepared carbon material ginsengThe numbers are as follows: specific surface area 745 m 2 And/g, particle size distribution of 20-38nm.
The particle size distribution analysis was performed on the prepared carbon material, as shown in fig. 1.
Example 2
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. putting 3 g of chitosan, 4 g of diammonium hydrogen phosphate, 1.5 g of (ethane-1, 2-diyl-bis (phosphino)) tetramethanol, 4.1 g of zinc chloride and 2.1 g of potassium ferrate into a ball milling tank of a high-energy ball mill, ball milling for 2 times, suspending for 6min by rotating for 15min at a rotating speed of 550 rpm each time, and finally standing for 50 min to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 4 hours at 220 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a speed of 15mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a speed of 1.7 ℃/min, then heating to 950 ℃ at a speed of 1.8 ℃/min, then maintaining for 2.5 hours, and then cooling to the room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 737 m 2 And/g, particle size distribution 15-40nm.
Example 3
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. placing 7 g of chitosan, 1 g of diammonium hydrogen phosphate, 5.3 g of (ethane-1, 2-diyl bis (phosphino)) tetramethanol, 1.3 g of zinc chloride and 6.4 g of potassium ferrate into a ball milling tank of a high-energy ball mill for ball milling for 4 times, suspending for 4 minutes by rotating for 25 minutes at a rotating speed of 450 rpm for each time, and finally standing for 70 minutes to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 2 hours at 180 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 25mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.2 ℃/min, then heating to 850 ℃ at a rate of 2.2 ℃/min, then maintaining for 3.5 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 689 m 2 And/g, particle size distribution of 23-47nm.
Effect example 1
The carbon materials prepared in examples 1 to 3 were used to prepare rubber water stop samples 1 to 3 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 carbon materials doped with nitrogen, phosphorus and iron into an internal mixer, carrying out one-stage mixing for 2min, adding 5kg of ZnO and 1kg of stearic acid together, keeping the mixing time for about 6min, and discharging glue after 90 s ℃ is reached; 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 a rubber sample, 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 samples 1 to 3 obtained was tested according to the Q/CR 562.2-2017 standard of railway Tunnel waterproof and drainage Material part 2: waterstop, the results are shown in Table 1 below:
TABLE 1
Comparative example 1
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. putting 5 g of chitosan, 2 g of disodium hydrogen phosphate, 2 g of (ethane-1, 2-diyl-bis (phosphino)) tetramethanol, 2 g of zinc chloride and 3 g of potassium ferrate into a ball milling tank of a high-energy ball mill for ball milling three times, suspending for 5 minutes by rotating for 20 minutes at a rotating speed of 500 rpm for each ball milling, and finally standing for 1 hour to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 3 hours at 200 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 20mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 900 ℃ at a rate of 2.0 ℃/min, then maintaining for 3 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 433m 2 And/g, particle size distribution of 39-77nm.
Comparative example 2
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. putting 5 g of chitosan, 2 g of diammonium hydrogen citrate, 2 g of (ethane-1, 2-diyl-bis (phosphino)) tetramethanol, 2 g of zinc chloride and 3 g of potassium ferrate into a ball milling tank of a high-energy ball mill for ball milling three times, suspending for 5 minutes by rotating for 20 minutes at a rotating speed of 500 revolutions per minute each time, and finally standing for 1 hour to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 3 hours at 200 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 20mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 900 ℃ at a rate of 2.0 ℃/min, then maintaining for 3 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 490m 2 And/g, particle size distribution is 35-64nm.
Comparative example 3
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. putting 5 g of chitosan, 2 g of aluminum dihydrogen phosphate, 2 g of (ethane-1, 2-diyl-bis (phosphino)) tetramethanol, 2 g of zinc chloride and 3 g of potassium ferrate into a ball milling tank of a high-energy ball mill for ball milling three times, suspending for 5 minutes by rotating for 20 minutes at a rotating speed of 500 revolutions per minute each time, and finally standing for 1 hour to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 3 hours at 200 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 20mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 900 ℃ at a rate of 2.0 ℃/min, then maintaining for 3 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 512m 2 And/g, the particle size distribution is 28-81nm.
Comparative example 4
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. putting 5 g of chitosan, 2 g of di (tetrabutylammonium) pyrophosphate, 2 g of (ethane-1, 2-diyl-bis (phosphino)) tetramethanol, 2 g of zinc chloride and 3 g of potassium ferrate into a ball milling tank of a high-energy ball mill for ball milling three times, suspending for 5 minutes by rotating for 20 minutes at a rotating speed of 500 rpm for each ball milling, and finally standing for 1 hour to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 3 hours at 200 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 20mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 900 ℃ at a rate of 2.0 ℃/min, then maintaining for 3 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 525m 2 And/g, particle size distribution is 24-76nm.
Comparative example 5
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. putting 5 g of chitosan, 2 g of diammonium hydrogen phosphate, 2 g of 1, 2-bis (diethyl phosphorus) ethane, 2 g of zinc chloride and 3 g of potassium ferrate into a ball milling tank of a high-energy ball mill for three times of ball milling, suspending for 5 minutes by rotating for 20 minutes at a rotating speed of 500 revolutions per minute each time of ball milling, and finally standing for 1 hour to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 3 hours at 200 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 20mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 900 ℃ at a rate of 2.0 ℃/min, then maintaining for 3 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 676 m 2 And/g, the particle size distribution is 22-49nm.
Comparative example 6
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. putting 5 g of chitosan, 2 g of diammonium hydrogen phosphate, 2 g of bis (diethoxyphosphonyl) acetylene, 2 g of zinc chloride and 3 g of potassium ferrate into a ball milling tank of a high-energy ball mill for ball milling for three times, suspending for 5 minutes by rotating for 20 minutes at a rotating speed of 500 rpm each time, and finally standing for 1 hour to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 3 hours at 200 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 20mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 900 ℃ at a rate of 2.0 ℃/min, then maintaining for 3 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 659m 2 And/g, particle size distribution is 24-52nm.
Comparative example 7
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
placing 5 g of chitosan, 2 g of diammonium hydrogen phosphate, 2 g of tetraethyl ammonium tetrafluoroborate, 2 g of zinc chloride and 3 g of potassium ferrate into a ball milling tank of a high-energy ball mill for ball milling for three times, suspending for 5 minutes by rotating for 20 minutes at a rotating speed of 500 rpm for each ball milling, and finally standing for 1 hour to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 3 hours at 200 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 20mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 900 ℃ at a rate of 2.0 ℃/min, then maintaining for 3 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 585m 2 And/g, particle size distribution of 22-71nm.
Comparative example 8
A method for preparing a nitrogen, phosphorus and iron doped carbon material, which comprises the following steps:
A. placing 5 g of chitosan, 2 g of diammonium hydrogen phosphate, 2 g of tricyclohexylphosphine fluoroborate, 2 g of zinc chloride and 3 g of potassium ferrate into a ball milling tank of a high-energy ball mill for ball milling for three times, suspending for 5 minutes by rotating for 20 minutes at a rotating speed of 500 rpm for each ball milling, and finally standing for 1 hour to obtain an intermediate product;
B. and (3) placing the intermediate product in a carbonization furnace, treating for 3 hours at 200 ℃ in an air atmosphere, then performing carbonization reaction in a nitrogen atmosphere, continuously introducing nitrogen at a rate of 20mL/min in the carbonization reaction process, firstly heating to 300 ℃ from room temperature at a rate of 1.5 ℃/min, then heating to 900 ℃ at a rate of 2.0 ℃/min, then maintaining for 3 hours, and then cooling to room temperature to obtain the black nitrogen, phosphorus and iron doped carbon material.
The parameters of the prepared carbon material are as follows: specific surface area 591m 2 And/g, particle size distribution of 23-73nm.
Effect example 2
The nitrogen, phosphorus and iron 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 carbon materials doped with nitrogen, phosphorus and iron into an internal mixer, carrying out one-stage mixing for 2min, adding 5kg of ZnO and 1kg of stearic acid together, keeping the mixing time for about 6min, and discharging glue after 90 s ℃ is reached; 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 a rubber sample, 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 comparative samples 1 to 8 obtained according to the standard Q/CR 562.2 to 2017 section 2 of railway Tunnel waterproof and drainage Material: water stop tape was tested, the results are shown in Table 2 below:
TABLE 2
Claims (8)
1. A method for preparing a nitrogen, phosphorus and iron doped carbon material, which is characterized by comprising the following steps:
A. the mass ratio is 3-7: 1-4: 1.5-5.3: 1.3 to 4.1: 2.1-6.4 of chitosan, diammonium hydrogen phosphate, (ethane-1, 2-diyl bis (phosphino)) tetramethanol, zinc chloride and potassium ferrate, and standing to obtain an intermediate product;
B. under the air atmosphere, treating the intermediate product at 180-220 ℃ for 2-4 hours, then placing the intermediate product in an inert atmosphere for carbonization reaction, and cooling to room temperature to obtain a nitrogen, phosphorus and iron doped carbon material;
in the step B, protective gas is continuously introduced at the speed of 15-25 mL/min, the temperature is firstly increased to 300+/-10 ℃ from room temperature at the speed of 1.2-1.7 ℃/min, and then the temperature is increased to 900+/-10 ℃ at the speed of 1.8-2.2 ℃/min, and the temperature is kept for 2.5-3.5 hours.
2. The method for preparing the nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the mass ratio of chitosan, diammonium phosphate, (ethane-1, 2-diylbis (phosphino)) tetra-methanol, zinc chloride and potassium ferrate in the step a is 5:2:2:2:3.
3. the method for preparing the nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the ball milling step of the step A is performed for 15-25min, and is stopped for 4-6min, and repeated for 2-4 times.
4. The method for preparing the nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the ball milling speed of the step A is 450-550 rpm.
5. The method for preparing a nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the standing step is specifically standing for 50-70min.
6. The method for preparing a nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the viscosity of the chitosan is 200-400mpa.s.
7. Use of a nitrogen, phosphorus, iron doped carbon material obtained by the preparation method according to any one of claims 1-6 in the rubber field.
8. Use according to claim 7, of the nitrogen, phosphorus, iron doped carbon material for the preparation of rubber water stops.
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| FR2854890A1 (en) * | 2003-05-15 | 2004-11-19 | Rhodia Chimie Sa | Process for creation of a carbon-heteroatom bond by reaction of an unsaturated compound substituted by a parting group and a nucleophilic compound, useful in the preparation of agrochemical and pharmaceutical compounds |
| CN110615424A (en) * | 2019-10-25 | 2019-12-27 | 河北省科学院能源研究所 | Nitrogen-phosphorus doped porous carbon material and preparation method and application thereof |
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| CN116654895A (en) * | 2023-05-31 | 2023-08-29 | 青岛新泰和纳米科技有限公司 | Phosphorus-tin co-doped hard carbon negative electrode material and preparation method thereof |
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| FR2854890A1 (en) * | 2003-05-15 | 2004-11-19 | Rhodia Chimie Sa | Process for creation of a carbon-heteroatom bond by reaction of an unsaturated compound substituted by a parting group and a nucleophilic compound, useful in the preparation of agrochemical and pharmaceutical compounds |
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