CN110982105B - Ruthenium nanoparticle-loaded catalyst - Google Patents
Ruthenium nanoparticle-loaded catalyst Download PDFInfo
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- CN110982105B CN110982105B CN201911075331.0A CN201911075331A CN110982105B CN 110982105 B CN110982105 B CN 110982105B CN 201911075331 A CN201911075331 A CN 201911075331A CN 110982105 B CN110982105 B CN 110982105B
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- waste polystyrene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 43
- 239000004793 Polystyrene Substances 0.000 claims abstract description 39
- 229920002223 polystyrene Polymers 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 26
- 229920000620 organic polymer Polymers 0.000 claims abstract description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 239000012265 solid product Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- -1 aromatic amine compounds Chemical class 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 12
- 239000004033 plastic Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 8
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 2
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- ZESWUEBPRPGMTP-UHFFFAOYSA-N 4-nitrobenzamide Chemical compound NC(=O)C1=CC=C([N+]([O-])=O)C=C1 ZESWUEBPRPGMTP-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum 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
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention discloses a ruthenium nanoparticle-loaded catalyst, which is prepared by placing triphenylphosphine, waste polystyrene, dimethoxymethane, dichloroethane and a ferric trichloride catalyst into a reaction container, reacting for 5 hours at 45 ℃, and after the reaction is finished, heating in a water bath to 80 ℃ to continue reacting for 48 hours. Washing the obtained solid product with methanol, and drying to obtain the corresponding porous polymer. And placing the obtained porous organic polymer, ruthenium trichloride, sodium borohydride and water in a reaction container, stirring and reacting for 3 hours at room temperature, washing and filtering the obtained product with ethanol, and drying in a vacuum drying oven to obtain the porous polymer supported ruthenium nanoparticle catalyst. The catalyst is applied to nitro reduction of p-nitrobenzene and derivatives thereof, and is used for efficiently and environmentally synthesizing aromatic amine compounds.
Description
Technical Field
The invention relates to a catalyst loaded with ruthenium nanoparticles.
Background
Waste polystyrene contamination results from the large accumulation of polystyrene plastic in the environment, and this contamination has serious negative effects on wildlife, wildlife habitats, and humans. Furthermore, waste polystyrene in the environment represents a waste of resources and energy. Polystyrene is a major petroleum-based plastic product that is very difficult to degrade in the natural environment due to its high molecular weight and high structural stability. In addition, polystyrene may also release a mixture of Polycyclic Aromatic Hydrocarbons (PAH), which are considered hazardous due to their carcinogenic and mutagenic properties. Therefore, the accumulation of waste polystyrene has developed into an increasingly serious global problem, which harms the quality of water environment, environment and human health.
At present, the classical methods for treating waste PS include the following: (1) manufacturing a light building heat-insulating material; (2) preparing coating, adhesive, waterproof material, modified asphalt and the like; (3) depolymerizing and recovering styrene and preparing fuel oil and the like; (4) hot melt recycling or solvent recycling, etc. However, most of the products have the defects of low added value of downstream products, serious pollution in the recovery process, unobvious economic benefit and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a porous organic polymer based on waste polystyrene, a preparation method and application thereof, and solves the problems of treatment and reutilization of the waste polystyrene in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: provided is a method for preparing a porous organic polymer based on waste polystyrene, comprising the steps of:
1) collecting waste polystyrene in waste foam or waste plastic, putting triphenylphosphine, waste polystyrene, dimethoxymethane, dichloroethane and a ferric trichloride catalyst into a reaction container, reacting for 5 hours at 45 ℃, heating in a water bath to 80 ℃ after the reaction is finished, and continuing to react for 48 hours to obtain a solid product; the mass ratio of the triphenylphosphine to the waste polystyrene is (1-1.5): 1, the mass ratio of the waste polystyrene to the dimethoxymethane to the dichloroethane is 0.8-1.2: 2.5: 10;
2) Washing the obtained solid product with methanol, and performing suction filtration to obtain a tan solid;
3) drying the yellow brown solid obtained in the step 2) in a vacuum drying oven at 50 ℃ to obtain brown powdery solid, namely the porous organic polymer.
In a preferred embodiment of the present invention, the waste polystyrene has the structural formula
In a preferred embodiment of the present invention, in the step 1), the reaction vessel is set to a condensing reflux condition.
In a preferred embodiment of the present invention, in the step 2), the excess methanol is used to perform washing at least 3 times until the impurities are removed.
In a preferred embodiment of the present invention, the synthetic route is as follows:
the second technical scheme adopted by the invention for solving the technical problems is as follows: provides a porous organic polymer based on waste polystyrene, which is prepared by the method and has the structural formula
The third technical scheme adopted by the invention for solving the technical problems is as follows: provides an application of a porous organic polymer based on waste polystyrene.
In a preferred embodiment of the present invention, ruthenium nanoparticles are loaded on the porous organic polymer based on waste polystyrene, so as to prepare a ruthenium nanoparticle-loaded catalyst.
In a preferred embodiment of the present invention, a method for preparing a ruthenium nanoparticle-supported catalyst comprises the following steps:
1) placing the porous organic polymer based on the waste polystyrene, ruthenium trichloride, sodium borohydride and water in a reaction container, and stirring and reacting for 3 hours at room temperature; wherein the dosage ratio of the porous organic polymer, the ruthenium trichloride, the sodium borohydride and the water is 2.5-5 g: 1 g: 1 g: 0.05-0.1L;
2) washing the product obtained in the step 1) with ethanol and filtering;
3) drying the product obtained in the step 2) in a vacuum drying oven at 50 ℃ to obtain a gray black powdery solid;
in a preferred embodiment of the present invention, the catalyst is used for the nitro reduction of p-nitrobenzene and derivatives thereof to synthesize aromatic amine compounds.
Compared with the background technology, the technical scheme has the following advantages:
1. the waste polystyrene used in the scheme has wide sources, can utilize waste plastics or waste foams polluting the environment to achieve the purpose of waste utilization, and can effectively treat the environmental pollution problem of the waste polystyrene;
2. the scheme utilizes the waste plastic-based porous organic polymer as the ruthenium nano particles loaded on the carrier of the heterogeneous catalyst to prepare the heterogeneous catalyst with high efficiency, wide substrate range, short reaction time, simple and convenient post-treatment and high product yield, and applies the heterogeneous catalyst to the synthesis of aromatic amino compounds, so that the catalytic system in the nitro reduction reaction has the advantages of wide substrate range, short reaction time (only 10-120 min), simple and convenient post-treatment, high product yield (up to 97 percent), repeated use of the catalyst and the like, and has obvious economic benefit.
Drawings
FIG. 1 is a schematic diagram of a metal nanoparticle reduction process;
FIG. 2 shows PS (polystyrene) and PPh 3 (triphenylphosphine) and POP (ethylene polymer graft polyether polyol);
FIG. 3 is a schematic diagram of the catalyst structure.
Detailed Description
Example 1
The porous organic polymer based on waste polystyrene has the structural formula
The preparation method comprises the following steps:
1) collecting waste polystyrene in waste foam or waste plastic, wherein the structural formula of the polystyrene is shown in the specification
Placing triphenylphosphine, waste polystyrene, dimethoxymethane, dichloroethane and a ferric trichloride catalyst into a reaction container, reacting for 5 hours at 45 ℃, heating in a water bath to 80 ℃ after the reaction is finished, and continuing to react for 48 hours to obtain a solid product; because the boiling point of dimethoxymethane is low, the reaction vessel is set with a condensation reflux condition;
the mass ratio of the triphenylphosphine to the waste polystyrene is (1-1.5): 1, the mass ratio of the waste polystyrene to the dimethoxymethane to the dichloroethane is 1: 2.5: 10;
2) washing the obtained solid product with excessive methanol for 3 times, wherein the dosage of each time is 30mL, and performing suction filtration to obtain a tan solid;
3) Drying the yellow brown solid obtained in the step 2) in a vacuum drying oven at 50 ℃ to obtain brown powdery solid, namely the porous organic polymer.
The synthesis route of the porous organic polymer of this example is as follows:
as shown in FIG. 2, it can be seen that in PPh 3 1584cm in -1 And 1432cm -1 1601cm in POP -1 And 1451cm -1 The position is a skeleton vibration absorption peak on an aromatic ring; in PPh 3 1477cm in (1) -1 1492cm of POP -1 The strong absorption peak is the stretching vibration peak of the C-P bond; PPh 3 The vibration peak of the effect of P and benzene ring is 1090cm -1 To 1130cm -1 Where it may be covered by the in-plane bending vibration absorption peak of the C-H bond. At 750cm -1 The absorption band at (a) may be a C-H out-of-plane bending vibration, indicating that triphenylphosphine and polystyrene are successfully bridged together by P, and also that triphenylphosphine ligands are successfully incorporated into the polymer backbone.
Example 2
Example 2 a ruthenium nanoparticle-supported catalyst was prepared, comprising the steps of:
1) placing the porous organic polymer prepared in the example 1, ruthenium trichloride, sodium borohydride and water in a reaction container, stirring and reacting for 3 hours at room temperature, wherein the reduction process of the metal nanoparticles in the step is shown in figure 1;
wherein the mass ratio of the added porous organic polymer to the added ruthenium trichloride to the added sodium borohydride is (2.5-5): 1: 1, the amount of water is not required to be excessive, and 500mg of polymer, 100mg of ruthenium trichloride, 100mg of sodium borohydride and 10mL are preferred;
2) Washing the product obtained in the step 1) with a small amount of excessive ethanol for multiple times to remove impurities as much as possible;
3) and (3) drying the product obtained in the step (2) in a vacuum drying oven at 50 ℃ to obtain a gray black powdery solid, namely the catalyst loaded with the ruthenium nano particles, wherein the structure of the catalyst is shown in figure 3.
Example 3
This example uses the catalyst prepared in example 2 to perform the reduction of p-nitrotoluene to prepare p-aminotoluene:
adding 3mmol of p-nitrotoluene, 3mmol of sodium borohydride, 20mg of catalyst and 15mL of deionized water into a 25mL round-bottom reaction bottle, placing the reaction bottle in a water bath at 40 ℃ and reacting for 1 h. Extracting the obtained product with ethyl acetate for three times, washing the organic phase with water once, centrifuging with a centrifuge to obtain a pure organic phase, performing rotary evaporation at 50 ℃ to obtain a solid product, and performing column chromatography purification to obtain 314mg of a target product, wherein the yield is 97%.
Compared with the traditional synthesis method, the method has the advantages of low cost and easy obtainment of the catalyst, high catalytic activity, small corrosion to reaction equipment, short reaction time and the like. The infrared and nuclear magnetic characterization of the compound is as follows: FT-IR (KBr) v 3379,3314,3201,3001,1627,1514,1304,1265,1128,831,726cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ6.60(s,4H),3.35(s,4H).
Example 4
This example used the catalyst prepared in example 2 to prepare p-aminophenol by reduction of p-nitrophenol:
Adding 3mmol of p-nitrotoluene, 3mmol of sodium borohydride, 20mg of catalyst and 15mL of deionized water into a 25mL round-bottom reaction bottle, placing the reaction bottle in a water bath at 40 ℃ and reacting for 1 h. Extracting the obtained product with ethyl acetate for three times, washing the organic phase with water once, centrifuging with a centrifuge to obtain a pure organic phase, performing rotary evaporation at 50 ℃ to obtain a solid product, and performing column chromatography purification to obtain 288mg of the target product with the yield of 88%.
The infrared and nuclear magnetic characterization of the compound is as follows: FT-IR (KBr) v 3342,3287,3026,2965,2916,2807,2680,2588,2486,1610,1057,1471,1386,1259,1234,1161,1088,967,821,742,706,524cm -1 ； 1 HNMR(400MHz,CDCl 3 )δ6.70(d,J＝8.3Hz,2H),6.63(d,J＝8.4Hz,2H),4.26(s,1H),3.44(s,2H).
Example 5
This example used the catalyst prepared in example 2 to prepare o-aminophenol by reduction of o-nitrophenol:
adding 3mmol of p-nitrotoluene, 3mmol of sodium borohydride, 20mg of catalyst and 15mL of deionized water into a 25mL round-bottom reaction bottle, placing the reaction bottle in a water bath at 40 ℃ and reacting for 1 h. Extracting the obtained product with ethyl acetate for three times, washing the organic phase with water once, centrifuging with a centrifuge to obtain a pure organic phase, performing rotary evaporation at 50 ℃ to obtain a solid product, and performing column chromatography purification to obtain 301mg of a target product with the yield of 92%.
The infrared and nuclear magnetic characterization of the compound is as follows: FT-IR (KBr) v 3377,3305,3054,3018,2958,2893,2839,2755,2713,2654,2588,1602,1513,1470,1404,1267,1213,1142,1083,1028,903,842,741cm -1 ； 1 HNMR(400MHz,CDCl 3 )δ6.87-6.66(m,4H),4.76(s,1H),3.64(s,2H).
Example 6
This example uses the catalyst prepared in example 2 to prepare anthranilamide by reduction of p-nitrobenzamide:
adding 3mmol of p-nitrotoluene, 3mmol of sodium borohydride, 20mg of catalyst and 15mL of deionized water into a 25mL round-bottom reaction bottle, placing the reaction bottle in a water bath at 40 ℃ and reacting for 1 h. Extracting the obtained product with ethyl acetate for three times, washing the organic phase with water once, centrifuging with a centrifuge to obtain a pure organic phase, performing rotary evaporation at 50 ℃ to obtain a solid product, and performing column chromatography purification to obtain 388mg of target product with the yield of 95%.
The infrared and nuclear magnetic characterization of the compound is as follows: FT-IR (KBr) v 3470,3387,3209,3104,2923,2866,1622,1519,1457,1380,1291,1271cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ6.99(d,J＝8.1Hz,2H),6.64(d,J＝8.2Hz,2H),3.55(s,2H),2.27(s,3H).
Example 7
In this example, o-chloroaniline was prepared by reducing o-chloronitrobenzene using the catalyst prepared in example 2:
adding 3mmol of p-nitrotoluene, 3mmol of sodium borohydride, 20mg of catalyst and 15mL of deionized water into a 25mL round-bottom reaction bottle, placing the reaction bottle in a water bath at 40 ℃ and reacting for 1 h. Extracting the obtained product with ethyl acetate for three times, washing the organic phase with water once, centrifuging with a centrifuge to obtain a pure organic phase, performing rotary evaporation at 50 ℃ to obtain a solid product, and performing column chromatography purification to obtain 347mg of the target product with the yield of 91%.
The infrared and nuclear magnetic characterization of the compound is as follows: FT-IR (KBr) v 3464,3382,3193,1618,1495,1290,1184,1085,1004,823,642cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ7.21-7.02(m,2H),6.70-6.57(m,2H),3.67(s,2H).
Example 8
This example uses the catalyst prepared in example 2 to prepare m-chloroaniline by reduction of m-chloronitrobenzene:
adding 3mmol of m-chloronitrobenzene, 3mmol of sodium borohydride, 20mg of catalyst and 15mL of deionized water into a 25mL round bottom reaction bottle, placing the reaction bottle in water bath at 40 ℃ and reacting for 1 h. Extracting the obtained product with ethyl acetate for three times, washing the organic phase with water once, centrifuging with a centrifuge to obtain a pure organic phase, performing rotary evaporation at 50 ℃ to obtain a solid product, and performing column chromatography purification to obtain 329mg of a target product, wherein the yield is 86%.
The infrared and nuclear magnetic characterization of the compound is as follows: FT-IR (KBr) v 3464,3362,3217,3047,2920,2852,1613,1485,1451,1298,1263,1164,1078,993,882,840,764,679cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ7.09(t,J＝8.0Hz,1H),6.76(ddd,J＝7.9,1.9,0.8Hz,1H),6.69(t,J＝2.1Hz,1H),6.57(ddd,J＝8.1,2.2,0.8Hz,1H),3.72(d,J＝26.7Hz,2H).
Example 9
This example used the catalyst prepared in example 2 to prepare aniline by nitrobenzene reduction:
adding 3mmol of p-nitrotoluene, 3mmol of sodium borohydride, 20mg of catalyst and 15mL of deionized water into a 25mL round-bottom reaction bottle, placing the reaction bottle in a water bath at 40 ℃ and reacting for 1 h. Extracting the obtained product with ethyl acetate for three times, washing the organic phase with water once, centrifuging with a centrifuge to obtain a pure organic phase, performing rotary evaporation at 50 ℃ to obtain a solid product, and performing column chromatography purification to obtain 265mg of a target product with the yield of 95%.
The infrared and nuclear magnetic characterization of the compound is as follows: FT-IR (KBr) v 3443,3345,3214,3076,3034,2927,1606,1500,1467,1271,1173,1026,994,879,749,692cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ7.35-7.16(m,2H),6.89-6.81(m,1H),6.79-6.72(m,2H),3.63(s,2H).
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (4)
1. A ruthenium nanoparticle-supported catalyst characterized by: the preparation method of the ruthenium nano-particle loaded on the porous organic polymer based on the waste polystyrene comprises the following steps:
firstly), placing porous organic polymer based on waste polystyrene, ruthenium trichloride, sodium borohydride and water in a reaction container, and stirring and reacting for 3 hours at room temperature; wherein the dosage ratio of the porous organic polymer, the ruthenium trichloride, the sodium borohydride and the water is 2.5-5 g: 1 g: 1 g: 0.05-0.1L; wherein the content of the first and second substances,
the preparation method of the porous organic polymer based on the waste polystyrene comprises the following steps:
1) collecting waste polystyrene in waste foam or waste plastic, putting triphenylphosphine, waste polystyrene, dimethoxymethane, dichloroethane and a ferric trichloride catalyst into a reaction container, reacting for 5 hours at 45 ℃, heating in a water bath to 80 ℃ after the reaction is finished, and continuing to react for 48 hours to obtain a solid product; the mass ratio of the triphenylphosphine to the waste polystyrene is (1-1.5): 1, the mass ratio of the waste polystyrene to the dimethoxymethane to the dichloroethane is 0.8-1.2: 2.5: 10; the reaction vessel is provided with a condensing reflux condition;
2) Washing the obtained solid product with methanol, and performing suction filtration to obtain a tan solid;
3) drying the tawny solid obtained in the step 2) in a vacuum drying oven at 50 ℃ to obtain brown powdery solid, namely the porous organic polymer;
secondly), washing the product obtained in the first step by using ethanol and carrying out suction filtration;
and thirdly) drying the product obtained in the step two) in a vacuum drying oven at 50 ℃ to obtain a gray black powdery solid.
2. The ruthenium nanoparticle-supported catalyst according to claim 1, wherein: the structural formula of the waste polystyrene is shown as
3. The ruthenium nanoparticle-supported catalyst according to claim 1, wherein: in the step 2), washing is carried out at least 3 times by using excessive methanol until impurities are removed.
4. The ruthenium nanoparticle-supported catalyst according to claim 1, wherein: the catalyst is used for carrying out nitro reduction on nitrobenzene and derivatives thereof to synthesize the aromatic amine compound.
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