CN106512992B - A kind of Polyaniline-Supported palladium synthetic method reducing tenor - Google Patents
A kind of Polyaniline-Supported palladium synthetic method reducing tenor Download PDFInfo
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- CN106512992B CN106512992B CN201610928893.5A CN201610928893A CN106512992B CN 106512992 B CN106512992 B CN 106512992B CN 201610928893 A CN201610928893 A CN 201610928893A CN 106512992 B CN106512992 B CN 106512992B
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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Abstract
A kind of Polyaniline-Supported palladium synthetic method reducing tenor, is related to the synthesis technical field of metallic catalyst.Aniline or derivatives thereof and palladium salt and tributyl phenethyl ammonium fluoride are dissolved in hydrochloric acid, after the hydrogen peroxide that concentration is 30% is added, pH is adjusted to neutral, is precipitated after standing, i.e. the Polyaniline-Supported palladium of low-metal content.The present invention is using Polyaniline and its derivative and palladium salt as raw material, and tributyl phenethyl ammonium fluoride, hydrochloric acid are auxiliary agent, hydrogen peroxide is oxidant, and synthesis reduces the Polyaniline-Supported palladium of tenor.Present invention reaction is simple, raw material is easy to get, solid waste is few, tenor is low, environmentally protective, is suitble to large-scale production.
Description
Technical field
The present invention relates to the synthesis technical fields of metallic catalyst.
Background technique
Metallic catalyst have many advantages, such as dosage it is low, it is active it is high, when using without ligand.Therefore, nanogold is developed
Metal catalyst is one of the forward position direction of materials chemistry and catalytic chemistry development.This case researcher is dedicated to developing nano metal
Catalyst is developed by aoxidizing aniline polymerization in the presence of palladium salt, preparing Polyaniline-Supported using air as oxidant recently
The method of palladium.The catalyst can be catalyzed a variety of coupling reactions, as Suzuki reaction, Heck reaction, Sonogashira reaction,
Ulmann reaction etc..
However, required tenor is higher in previous work, every polymerization 465.9mg aniline, it is necessary to use 22 mg
Palladium chloride.Therefore, in follow-up study, attempting research reduces tenor polymerization aniline and its derivatives synthesized polyaniline catalysis
The method of agent.Palladium content is briefly, however reduced, aniline can not polymerize.
Summary of the invention
The object of the present invention is to provide a kind of Polyaniline-Supported palladium synthetic methods for reducing tenor.
The technical scheme is that: aniline or derivatives thereof and palladium salt and tributyl phenethyl ammonium fluoride are dissolved in salt
In acid, after the hydrogen peroxide that concentration is 30% is added, pH is adjusted to neutral, is precipitated after standing, i.e. the polyphenyl of low-metal content
Amine supported palladium.
For the present invention using Polyaniline and its derivative and palladium salt as raw material, tributyl phenethyl ammonium fluoride, hydrochloric acid are auxiliary agent, mistake
Hydrogen oxide is oxidant, and synthesis reduces the Polyaniline-Supported palladium of tenor.Compared with previous method, the present invention reacts letter
List, raw material is easy to get, solid waste is few, tenor is low, environmentally protective, is suitble to large-scale production.
The present invention is reducing palladium content simultaneously, additionally it is possible to so that aniline and its derivatives polymerize, and the polyaniline prepared
The method of loaded palladium catalyst holding higher catalytic activity.The raw material cleaning that this method uses, does not generate waste, reduces metal
After content, resource has been saved, has improved the utilization efficiency of catalyst, to be conducive to be mass produced.
Further, aniline of the present invention or derivatives thereof be aniline, open-chain crown ether, P-nethoxyaniline, to chlorine
Non-substituted or substituted one of the aromatic amine such as aniline, para-fluoroaniline, wherein because its cost is minimum, preferred aniline.
The palladium salt is one of palladium salts such as palladium chloride, palladium acetate, palladium nitrate, wherein because its cost is minimum, preferred chlorine
Change palladium.
The aniline and its derivatives and the mass ratio of palladium salt are 500~400:1, and preferably 450:1 is prepared under this ratio
Catalyst activity is best.
The tributyl phenethyl ammonium fluoride and the mass ratio of palladium salt are 0.8~1.6:1, preferably 1.2:1, under this ratio
It is best to prepare catalyst activity.
The concentration of hydrochloric acid is 0.5~2 mol/L, and preferably 1.0 mol/L prepare catalyst activity most under this ratio
It is good.
The palladium salt is palladium chloride, and the amount ratio of the palladium chloride and hydrochloric acid solution is 1mg: 200mL；The palladium chloride with
The amount ratio of hydrogen peroxide is 1mg: 1mL.Be experimentally verified that: it is best to prepare catalyst activity under this ratio.
Specific embodiment
The following examples illustrate the present invention in more detail, rather than limitation of the invention further.Implement
Example 1:
1, preparation reduces the Polyaniline-Supported palladium synthetic method of tenor: by 1mg palladium chloride, 450mg aniline, 1.2mg
Tributyl phenethyl ammonium fluoride is dissolved in the hydrochloric acid that 200mL concentration is 1mol/L, and it is dense that commercially available 30% mass of 1mL is added after stirring
The hydrogenperoxide steam generator of degree.Adjust pH with 1mol/L sodium hydrate aqueous solution after mixing evenly has after standing 24 hours to neutrality
Precipitating generates, and filtering, precipitating is washed with deionized water, the Polyaniline-Supported palladium of the low-metal content after drying.
2, the catalyst is used for the Suzuki coupling reaction of iodobenzene and phenyl boric acid, examines its catalytic activity: iodobenzene
(1.0mmol), phenyl boric acid (1.0 mmol) and potassium carbonate (2.0mmol), Polyaniline-Supported palladium catalyst (12 mg) is in 4mL second
In alcohol, lower 100 DEG C of nitrogen protection are heated 48 hours, after reaction by column chromatography for separation, obtain 147.8 mg of biphenyl, yield
96%。
Embodiment 2: other conditions examine different substituted anilines to do the catalyst activity of carrier preparation, experiment with embodiment 1
As a result it see the table below 1.
From the above results, aniline, open-chain crown ether, P-nethoxyaniline, parachloroanilinum, para-fluoroaniline can be used
It is reacted etc. one of non-substituted or substituted aromatic amine as aniline and its derivatives of the invention.When being with aniline
Carrier, not only cheaply, and catalytic activity is best.
Embodiment 3: other conditions examine the catalyst activity of different palladium salt preparations with embodiment 1, and experimental result see the table below
2。
From the above results, the present invention can be realized using palladium chloride, palladium acetate, palladium nitrate as palladium salt, wherein with chlorination
Palladium is palladium source, and not only cheaply, and catalytic activity is best.
Embodiment 4: for other conditions with embodiment 1, the catalyst for examining the mass ratio of different aniline and palladium chloride to prepare is living
Property, experimental result is shown in the following table 3.
From the above results, the catalytic activity of the mass ratio 450:1 of aniline and palladium chloride preparation is best.
Embodiment 5: other conditions examine the mass ratio system of different tributyl phenethyl ammonium fluorides and palladium salt with embodiment 1
Standby catalyst activity, experimental result is shown in the following table 4.
From the above results, the catalytic activity of the mass ratio 1.2:1 of tributyl phenethyl ammonium fluoride and palladium chloride preparation
Most preferably.
Embodiment 6: other conditions examine the catalyst activity of various concentration hydrochloric acid preparation with embodiment 1, experimental result is shown in
The following table 5.
From the above results, the catalytic activity of concentration of hydrochloric acid 1mol/L preparation is best.
Embodiment 7: other conditions examine urging for the usage ratio of different palladium chlorides and hydrochloric acid solution preparation with embodiment 1
Agent activity, experimental result is shown in the following table 6.
From the above results, the catalytic activity prepared when the usage ratio of palladium chloride and hydrochloric acid solution is 0.005g/L is most
It is good.
Embodiment 8: other conditions examine urging for the usage ratio of different palladium chlorides and hydrogen peroxide preparation with embodiment 1
Agent activity, experimental result is shown in the following table 7.
From the above results, the catalytic activity prepared when 1.0 g/L of usage ratio of palladium chloride and hydrogen peroxide is best.
Claims (6)
1. a kind of Polyaniline-Supported palladium synthetic method for reducing tenor, it is characterised in that: by aniline or derivatives thereof and palladium
Salt and tributyl phenethyl ammonium fluoride are dissolved in hydrochloric acid, described aniline or derivatives thereof, tributyl phenethyl ammonium fluoride with
The mass ratio that feeds intake of palladium salt is 450: 1.2: 1, after the hydrogen peroxide that concentration is 30 wt% is added, adjusts pH to neutral, after standing
It is precipitated, i.e. the Polyaniline-Supported palladium of low-metal content.
2. reducing the Polyaniline-Supported palladium synthetic method of tenor according to claim 1, it is characterised in that: the aniline
Or derivatives thereof for aniline, open-chain crown ether, P-nethoxyaniline, parachloroanilinum, any one in para-fluoroaniline.
3. reducing the Polyaniline-Supported palladium synthetic method of tenor according to claim 1, it is characterised in that: the palladium salt
For one of palladium chloride, palladium acetate, palladium nitrate.
4. reducing the Polyaniline-Supported palladium synthetic method of tenor according to claim 1, it is characterised in that: the hydrochloric acid
Concentration is 0.5~2 mol/L.
5. reducing the Polyaniline-Supported palladium synthetic method of tenor according to claim 4, it is characterised in that: the hydrochloric acid
Concentration is 1.0 mol/L.
6. reducing the Polyaniline-Supported palladium synthetic method of tenor according to claim 3, it is characterised in that: the palladium salt
For palladium chloride, the amount ratio of the palladium chloride and hydrochloric acid is 1mg: 200mL；The amount ratio of the palladium chloride and hydrogen peroxide is
1mg∶1mL。
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| CN109513460B (en) * | 2018-11-20 | 2021-06-29 | 扬州大学 | Synthesis method of beta-carotene degradation catalyst |
| CN109438281B (en) * | 2018-12-05 | 2021-04-30 | 扬州大学 | Preparation method of heterogeneous free radical scavenging agent |
| CN109659576B (en) * | 2019-01-31 | 2020-12-08 | 浙江大学 | Micro-nano battery catalyst, preparation method and application |
| CN109926090B (en) * | 2019-03-13 | 2021-09-28 | 扬州大学 | Catalyst for synthesizing imatinib and preparation method thereof |
| CN110961151B (en) * | 2019-11-15 | 2022-08-12 | 扬州大学 | Ruthenium-copper bimetallic catalyst, preparation method and application thereof |
| CN113956231A (en) * | 2021-09-27 | 2022-01-21 | 哈尔滨工业大学（深圳） | Preparation method of biaryl compound based on continuous flow reactor |
| CN113877628B (en) * | 2021-09-27 | 2024-03-12 | 哈尔滨工业大学（深圳） | Polyaniline-loaded noble metal catalyst, continuous flow reactor and device |
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| CN101724151A (en) * | 2009-12-07 | 2010-06-09 | 北京化工大学 | Method for preparing polyaniline by using hydrogen peroxide as oxidizing agent |
| CN104341254A (en) * | 2014-10-28 | 2015-02-11 | 扬州大学 | Method for synthesizing polysubstituted olefins |
| CN105061759A (en) * | 2015-08-03 | 2015-11-18 | 安徽理工大学 | Preparation method for Pd / PANI nano composite material |
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2016
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| CN101724151A (en) * | 2009-12-07 | 2010-06-09 | 北京化工大学 | Method for preparing polyaniline by using hydrogen peroxide as oxidizing agent |
| CN104341254A (en) * | 2014-10-28 | 2015-02-11 | 扬州大学 | Method for synthesizing polysubstituted olefins |
| CN105061759A (en) * | 2015-08-03 | 2015-11-18 | 安徽理工大学 | Preparation method for Pd / PANI nano composite material |
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