CN116586094A - Catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, preparation method and application thereof - Google Patents
Catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, preparation method and application thereof Download PDFInfo
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- CN116586094A CN116586094A CN202310557592.6A CN202310557592A CN116586094A CN 116586094 A CN116586094 A CN 116586094A CN 202310557592 A CN202310557592 A CN 202310557592A CN 116586094 A CN116586094 A CN 116586094A
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- trifluoromethyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 239000002028 Biomass Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 14
- 150000002940 palladium Chemical class 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 10
- 244000105624 Arachis hypogaea Species 0.000 claims description 10
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 10
- 235000018262 Arachis monticola Nutrition 0.000 claims description 10
- 235000020232 peanut Nutrition 0.000 claims description 10
- 239000002019 doping agent Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 5
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 235000005822 corn Nutrition 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
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 18
- NDOOLCPFQSTTNC-UHFFFAOYSA-N 1,2-diphenyl-1-(trifluoromethyl)hydrazine Chemical compound FC(F)(F)N(NC1=CC=CC=C1)C1=CC=CC=C1 NDOOLCPFQSTTNC-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WHNAMGUAXHGCHH-UHFFFAOYSA-N 1-nitro-3-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC(C(F)(F)F)=C1 WHNAMGUAXHGCHH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000007522 mineralic acids Chemical class 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000006462 rearrangement reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- -1 (trifluoromethyl) diphenyl hydrazine methanol Chemical compound 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/54—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, a preparation method and application thereof. The method adopts the nitrogen doped biomass pyrolytic carbon carrier to load monoatomic Pd for catalytic synthesis of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, so that the product 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl has higher yield under the condition of lower active metal Pd load, and the use cost of the catalyst is reduced. The catalyst has longer service life, can be repeated for more than 30 times, can still ensure that the product has higher yield, and has good catalyst stability. And the biomass raw material has low cost and wide sources, and the prepared carrier has larger specific surface area and pore channel distribution, thereby being beneficial to saving the cost and improving the activity of the catalyst.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, a preparation method and application thereof.
Background
2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl is an excellent intermediate product of material chemical industry, is also one of important raw materials for synthesizing soluble polyimide, and because two trifluoromethyl groups at 2,2' -positions in the molecular structure generate torsion angles between two benzene rings of biphenyl to cause a non-planar structure due to the steric hindrance effect, the polyimide film material of diamine monomer taking TFDB as a core has a plurality of special properties, such as high solubility, light color, high thermal stability, good mechanical strength and good light transmittance. Therefore, research into a large-scale production method of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl has great industrial value.
The most studied method at present is to prepare 3,3 '-bis (trifluoromethyl) diphenyl hydrazine by rearrangement of 3,3' -bis (trifluoromethyl) diphenyl hydrazine, namely m-nitrobenzotrifluoride is taken as a raw material, and zinc powder or catalytic hydrogenation is carried out in alkali liquor. According to the synthesis method reported in Chinese patent CN101525294A, alcohol and arene are used as solvents, m-nitrobenzotrifluoride is reduced by Zn powder under the condition of inorganic alkaline water solution to prepare 3,3 '-bis (trifluoromethyl) diphenyl hydrazine, then the 3,3' -bis (trifluoromethyl) diphenyl hydrazine is rearranged by inorganic acid, the solvents are recovered by separating liquid, the water phase is neutralized, and the 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl is obtained by recrystallization. The industrial zinc powder has the problems of large zinc powder consumption, large solid waste amount of waste alkali liquid and zinc oxide and the like, so that the environmental protection cost is higher, the impurities are more, the yield is lower, and the industrial production is not facilitated. The method can solve the problem of large amount of wastewater generated by zinc powder reduction by using a palladium-carbon catalysis method, chinese patent CN109232273A uses m-nitrobenzotrifluoride as a raw material, uses a phase transfer catalyst, an auxiliary catalyst and Pd/C as a catalysis system in an inorganic alkaline water solution, uses aromatic hydrocarbon as a solvent to synthesize 3,3 '-bis (trifluoromethyl) diphenyl hydrazine through hydrogenation reaction, and performs rearrangement reaction on the 3,3' -bis (trifluoromethyl) diphenyl hydrazine under the condition of the inorganic acid water solution to obtain 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl.
According to the method, hydrogen is used as a reducing agent, pd/C is used as a catalyst, pd loading is high, pd removal is serious after the reaction is repeated for several times, so that the catalyst is abandoned and cannot be reused, and a Pd noble metal catalyst belongs to rare resources, is high in price, and is high in cost and unsuitable for industrial production.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a catalyst of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl with high activity, long service life, low loading capacity and cost advantage and a preparation method thereof.
The catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl takes nitrogen-doped biomass pyrolytic carbon as a carrier, and metal monoatomic Pd is dispersed in the carrier; the metal monoatomic Pd accounts for 0.01 to 1wt%, preferably 0.01 to 0.2wt%, and more preferably 0.08 to 0.2wt% of the catalyst.
According to one embodiment of the invention, the nitrogen doping amount in the catalyst is 1-5% wt.
According to an embodiment of the present invention, the precursor of the biomass pyrolytic carbon is a biomass, preferably one or more of peanut shell, coconut shell, cotton shell and corn cob.
According to one embodiment of the invention, the catalyst takes biomass, palladium salt and nitrogen doping agent as raw materials and is prepared by a one-pot method.
The second object of the present invention is to provide a preparation method of the above catalyst, which specifically comprises the following steps:
(1) Placing biomass and nitrogen doping agent in palladium salt solution, and soaking;
(2) Filtering, drying and calcining under inert atmosphere to obtain the catalyst.
According to one embodiment of the present invention, the nitrogen dopant is one or more of urea, melamine, and amino acids.
According to one embodiment of the present invention, the palladium salt is one or more of palladium chloride, palladium acetate and palladium nitrate.
According to an embodiment of the present invention, the solvent of the palladium salt solution is one or more of methanol, ethanol, water and DMF; the concentration of the palladium salt solution is 1-10wt%.
According to one embodiment of the invention, the soaking temperature is 10-50 ℃ and the soaking time is 1-10 h.
According to one embodiment of the invention, the calcination temperature is 300-1000 ℃, preferably 700-900 ℃; the calcination time is 2-8h.
According to one embodiment of the invention, the inert atmosphere is nitrogen or argon.
The third object of the invention is to provide the application of the catalyst or the catalyst prepared by the preparation method in the synthesis of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl.
According to one embodiment of the present invention, the above synthesis method comprises the steps of:
s1, dissolving m-nitro benzotrifluoride in an organic solvent, adding the catalyst into the organic solvent, placing the catalyst in a high-pressure reactor, adding an inorganic alkali aqueous solution, and introducing H 2 Reacted to H 2 Stopping when no longer absorbed, and preparing the 3,3' -bis (trifluoromethyl) diphenyl hydrazine;
s2, under the protection of nitrogen, 3' -bis (trifluoromethyl) diphenyl hydrazine is taken as a raw material, and a rearrangement reaction is carried out under the action of inorganic acid, so that 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl is prepared.
The reaction scheme is as follows:
according to one embodiment of the invention, in step S1, the reaction temperature is 10-100deg.C, preferably 50-70deg.C; the pressure of the reaction is 0.1-1Mpa, preferably 0.3-0.6Mpa.
According to an embodiment of the present invention, in step S1, the organic solvent is one or more of methanol, ethanol, DMF, preferably methanol.
According to one embodiment of the present invention, in step S2, the inorganic acid is hydrochloric acid or sulfuric acid.
The beneficial effects are that:
according to the invention, the nitrogen-doped biomass pyrolytic carbon carrier is used for loading single-atom Pd to catalyze and synthesize the 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, so that the 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl product has higher yield (the first yield is higher than 68%) under the condition of lower active metal Pd loading (lower than 1wt percent and even lower than 0.2wt percent), and the use cost of the catalyst is reduced. The catalyst has longer service life, can ensure that the product has higher yield (higher than 64 percent) after being repeated for more than 30 times, and has good catalyst stability. And the biomass raw material has low cost and wide sources, and the prepared carrier has larger specific surface area and pore channel distribution, thereby being beneficial to saving the cost and improving the activity of the catalyst.
Drawings
FIG. 1 a is a TEM representation of peanut shell pyrolytic carbon in the catalyst prepared in preparation example 1;
FIG. 1 b is a TEM characterization of monatomic palladium in the catalyst prepared in preparation example 1;
FIG. 2 is a spherical aberration electron microscope image of a single-atom palladium-supported peanut shell pyrolytic carbon catalyst in the catalyst prepared in preparation example 1;
FIG. 3 is an XRD pattern of a single-atom palladium-supported peanut shell pyrolytic carbon catalyst in the catalyst prepared in preparation example 1.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure. It should also be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the invention, since various insubstantial modifications and adaptations of the invention to those skilled in the art based on the foregoing disclosure are intended to be within the scope of the invention and the specific process parameters and the like set forth below are merely one example of a suitable range within which one skilled in the art would choose from the description herein without being limited to the specific values set forth below.
The invention provides a catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, which takes nitrogen-doped biomass pyrolytic carbon as a carrier, and metal monoatomic Pd is dispersed in the carrier; the metal monoatomic Pd accounts for 0.01 to 1wt%, preferably 0.01 to 0.2wt%, further preferably 0.08 to 0.2wt%, and specifically may be 0.08wt%, 0.09wt%, 0.10wt%, 0.11wt%, 0.12wt%, 0.13wt%, 0.14wt%, 0.15wt%, 0.16wt%, 0.17wt%, 0.18wt%, 0.19wt% and 0.20wt% of the catalyst.
According to one embodiment of the invention, the nitrogen doping level in the above-mentioned catalyst is 1-5% wt, preferably 3-5% wt.
According to an embodiment of the present invention, the precursor of the biomass pyrolytic carbon is a biomass, preferably one or more of peanut shell, coconut shell, cotton shell and corn cob.
According to one embodiment of the invention, the catalyst takes biomass, palladium salt and nitrogen doping agent as raw materials and is prepared by a one-pot method.
The second object of the present invention is to provide a preparation method of the above catalyst, which specifically comprises the following steps:
(1) Placing biomass and nitrogen doping agent in palladium salt solution, and soaking;
(2) Filtering, drying and calcining under inert atmosphere to obtain the catalyst.
According to one embodiment of the present invention, the nitrogen dopant is one or more of urea, melamine, thiourea and amino acid.
According to one embodiment of the present invention, the palladium salt is one or more of palladium chloride, palladium acetate and palladium nitrate.
According to an embodiment of the present invention, the solvent of the palladium salt solution is one or more of methanol, ethanol, water and DMF; the concentration of the palladium salt solution is 1-10wt%.
According to one embodiment of the invention, the soaking temperature is 10-50 ℃ and the soaking time is 1-10 h.
According to one embodiment of the invention, the calcination temperature is 300-1000 ℃, preferably 700-900 ℃; the calcination time is 2-8h.
According to one embodiment of the invention, the inert atmosphere is nitrogen or argon.
The third object of the invention is to provide the application of the catalyst or the catalyst prepared by the preparation method in the synthesis of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl.
According to one embodiment of the present invention, the above synthesis method comprises the steps of:
s1, dissolving m-nitro benzotrifluoride in an organic solvent, adding the catalyst into the organic solvent, placing the catalyst in a high-pressure reactor, adding an inorganic alkali aqueous solution, and introducing H 2 Reacted to H 2 Stopping when no longer absorbed, and preparing the 3,3' -bis (trifluoromethyl) diphenyl hydrazine;
s2, under the protection of nitrogen, 3' -bis (trifluoromethyl) diphenyl hydrazine is taken as a raw material, and a rearrangement reaction is carried out under the action of inorganic acid, so that 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl is prepared.
According to one embodiment of the invention, in step S1, the reaction temperature is 10-100deg.C, preferably 50-70deg.C; the pressure of the reaction is 0.1-1Mpa, preferably 0.3-0.6Mpa.
According to an embodiment of the present invention, in step S1, the organic solvent is one or more of methanol, ethanol, DMF, preferably methanol.
According to one embodiment of the present invention, in step S2, the inorganic acid is hydrochloric acid or sulfuric acid.
The present invention is further illustrated by the following examples, but the present invention is not limited thereto, and the apparatus and reagents used in the examples of the present disclosure are those commonly used by those skilled in the art unless otherwise specified.
Preparation example 1
Preparing active component palladium chloride into 5wt% methanol solution, placing peanut shell and urea into the palladium chloride solution, soaking at 25 ℃ for 6 hours, filtering, drying, and calcining at 700 ℃ for 5 hours in an argon atmosphere to obtain Pd-N-C-1 monoatomic catalyst; the mass fraction of the active component of Pd in the catalyst is 0.08wt%, and the doping amount of N is as follows: 5wt%. The catalyst is characterized, and the characterization analysis shows that the carrier has rich pore channel structure, the atomic palladium is uniformly dispersed on the carrier, the palladium atoms can be well supported, and a stable coordination environment is provided for the palladium atoms.
FIG. 1 a is a TEM representation of peanut shell pyrolytic carbon in the catalyst prepared in preparation example 1;
FIG. 1 b is a TEM characterization of monatomic palladium in the catalyst prepared in preparation example 1;
FIG. 2 is a spherical aberration electron microscope image of a single-atom palladium-supported peanut shell pyrolytic carbon catalyst in the catalyst prepared in preparation example 1;
FIG. 3 is an XRD pattern of a single-atom palladium-supported peanut shell pyrolytic carbon catalyst in the catalyst prepared in preparation example 1.
Preparation example 2
Preparing active palladium nitrate into a 5wt% aqueous solution, placing coconut shells and melamine into the palladium nitrate solution, soaking at 25 ℃ for 6 hours, filtering, drying, and calcining at 900 ℃ for 5 hours in a nitrogen atmosphere to obtain a Pd-N-C-2 monoatomic catalyst; the mass fraction of the active component of Pd in the catalyst is 0.12wt%, and the doping amount of N is as follows: 3wt%.
Preparation example 3
Preparing active component palladium acetate into a 5wt% solution, placing cotton shell and urea into the palladium acetate solution, soaking at 25 ℃ for 6 hours, filtering, drying, and calcining at 800 ℃ for 5 hours in nitrogen atmosphere to obtain Pd-N-C-3 monoatomic catalyst; the mass fraction of the active component of Pd in the catalyst is 0.13wt%, and the doping amount of N is as follows: 4wt%.
Preparation example 4
Preparing active component palladium chloride into 5%wt solution, placing cotton shell and urea into the salt, soaking at 25 ℃ for 6 hours, filtering, drying, and calcining at 800 ℃ for 5 hours in nitrogen atmosphere to obtain Pd-N-C-4 monoatomic catalyst; the mass fraction of the active component of Pd in the catalyst is 0.09wt%, and the doping amount of N is as follows: 3wt%.
Preparation example 5
Preparing active component palladium chloride into a 5wt% solution, placing corn cobs and amino acid into the palladium chloride solution, soaking at 25 ℃ for 6 hours, filtering, drying, and calcining at 800 ℃ for 5 hours in a nitrogen atmosphere to obtain Pd-N-C-5 monoatomic catalyst; the mass fraction of the active component of Pd in the catalyst is 0.10wt%, and the doping amount of N is as follows: 4wt%.
Example 1
In a 1000mL autoclave, 43.8g (0.225 mol) of m-nitrobenzotrifluoride was dissolved in 100.0mL of methanol, 1g of a single-atom catalyst Pd-N-C-1, 13.7g of a 40% aqueous sodium hydroxide solution was added thereto, and H was introduced 2 Pressurizing to 0.4MPa and 65 ℃, and carrying out vigorous stirring reaction for 2.5 hours until hydrogen is not absorbed any more, stopping stirring reaction, filtering and recovering the monoatomic catalyst Pd-N-C-1 to obtain 42g of 3,3' -bis (trifluoromethyl) diphenyl hydrazine methanol solution with the GC content of 99.5 percent.
Under the protection of nitrogen, 120 g of 30wt% hydrochloric acid solution is added into a 1000m L three-neck flask, stirring is started, all 42g of 3,3' -bis (trifluoromethyl) diphenyl hydrazine-containing methanol solution obtained in the process is dripped at 20 ℃ to react for 3h, standing and sampling are used for high-efficiency liquid chromatographic analysis, 25wt% Na OH solution is prepared for neutralization until p H is 9-10 after the reaction is finished, a large amount of light yellow solid is precipitated in the solution, the solution is filtered, washed by clear water and recrystallized by ethanol, and a white crystal product 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl is obtained, and the yield is 68.8wt%.
Examples 2 to 5
Other conditions were the same as in example 1 except that the catalysts prepared in preparation examples 2 to 5 were used in this order, and specific parameters and results are shown in Table 1.
Comparative example 1
Other conditions were the same as in example 1 except that the catalyst added was Pd-C-D1 as prepared in comparative example 1, and specific parameters and results are shown in Table 1.
Comparative example 2
Other conditions were the same as in example 1 except that the catalyst added was a commercially available palladium on carbon catalyst having a Pd loading of 5% by weight, and specific parameters and results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the catalyst prepared by the present invention has a greatly improved yield compared to the catalyst without nitrogen doping. Compared with the palladium-carbon catalyst of the corresponding technology, the catalyst has higher catalytic activity and service life under the condition of lower active metal palladium loading.
The procedure of examples 1-5 was repeated and the same catalysts Pd-N-C-1 through Pd-N-C-5 were reused 30 times, and the resulting yield structures are summarized in Table 2:
TABLE 2
It can be seen from Table 2 that the catalyst of the present invention has a low loading (mass fraction of 0.01 to 1%) and can be repeated more than 30 times with a high productivity.
Claims (10)
1. The catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl is characterized in that nitrogen-doped biomass pyrolytic carbon is used as a carrier, and metal monoatomic Pd is dispersed in the carrier; the metal monoatomic Pd accounts for 0.01 to 1wt%, preferably 0.01 to 0.2wt%, and more preferably 0.08 to 0.2wt% of the catalyst.
2. The catalyst of claim 1 wherein the nitrogen doping level in the catalyst is 1-5% wt.
3. The catalyst of claim 1, wherein the precursor of biomass pyrolytic carbon is biomass, preferably one or more of peanut shell, coconut shell, cotton shell, corn cob.
4. A catalyst according to any one of claims 1-3, characterized in that the catalyst is prepared from biomass, palladium salts, nitrogen dopants by a one-pot process.
5. The method for preparing the catalyst according to any one of claims 1 to 4, comprising the following steps:
(1) Placing biomass and nitrogen doping agent in palladium salt solution, and soaking;
(2) Filtering, drying and calcining under inert atmosphere to obtain the catalyst.
6. The method according to claim 5, wherein the nitrogen dopant is one or more of urea, melamine, and amino acid.
7. The method according to claim 5, wherein the palladium salt is one or more of palladium chloride, palladium acetate and palladium nitrate.
8. The preparation method according to claim 5, wherein the calcination temperature is 300-1000 ℃, preferably 700-900 ℃; the calcination time is 2-8h.
9. The method of claim 5, wherein the inert atmosphere is nitrogen or argon.
10. Use of the catalyst according to any one of claims 1 to 4 or the catalyst prepared by the method according to any one of claims 5 to 9 for the synthesis of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl.
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