CN106187783A - The application in the hydrogenation of aromatic nitro compound of the polyamic acid supported palladium nanocatalyst - Google Patents

The application in the hydrogenation of aromatic nitro compound of the polyamic acid supported palladium nanocatalyst Download PDF

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CN106187783A
CN106187783A CN201610514242.1A CN201610514242A CN106187783A CN 106187783 A CN106187783 A CN 106187783A CN 201610514242 A CN201610514242 A CN 201610514242A CN 106187783 A CN106187783 A CN 106187783A
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polyamic acid
palladium
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acid
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CN106187783B (en
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李衡峰
李俊
金鑫
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Central South University
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    • 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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Abstract

The present invention discloses the application in the hydrogenation of aromatic nitro compound of a kind of polyamic acid supported palladium nanocatalyst.Catalyst of the present invention comprises the Pd nano particle that particle diameter is less, dispersion is higher, and reaction system is in the diffusion of quasi-homodisperse state, beneficially reaction substrate and product；Catalyst carrier has the activation to reaction substrate of higher polarity, beneficially catalyst active center.The catalysis activity of catalyst is apparently higher than commercialization Pd/C catalyst.Catalyst has the water solublity that pH is sensitive, can realize well repeatedly reclaiming and repeat catalysis use.Catalytic reaction is normal temperature and pressure (H in aqueous phase2Implement under the conditions of), environment protecting and power-saving.

Description

Polyamic acid supported palladium nanocatalyst is in the hydrogenation of aromatic nitro compound Application
Technical field
The invention belongs to metal nano catalyst application, be specifically related to a kind of accurate homogeneous, recyclable and recycling Palladium nanocatalyst and application in the hydrogenation of aromatic nitro compound.
Background technology
The reduction reaction of aromatic nitro compound is an important reaction, because its aniline and its derivatives obtained is The chemical intermediate that one class is important.The method of reducing of aromatic nitro compound substantially can be divided into metering type reducing process and catalytic type also Former method.The reducing agent that metering type reducing process uses is mainly metal or the sulfide such as iron powder, glass putty, zinc powder, generally requires big Amount acid medium, the requirement to equipment is the highest, also can discharge substantial amounts of waste water and dregs, environment is caused severe contamination.Compare it Under, the reaction of catalytic type reducing process is simple, and environment friendly is high, and the especially catalytic hydrogenation process with hydrogen as reducing agent, at nitre Based compound reduction aspect increasingly comes into one's own.
The method for hydrogenation of current industrial nitro compound is divided into vapour phase hydrogenation method and liquid-phase hydrogenation method.Vapour phase hydrogenation technique Typically use activated carbon or oxide carried cuprio or palladium-based catalyst, need 200 300 DEG C of high temperature and the hydrogen of 1 3Mpa Pressure；Liquid-phase hydrogenation technique typically uses the nickel-base catalyst of tripolite loading, activated carbon supported palladio or platinum based catalyst, needs Want the hydrogen pressure that high temperature and 0.1 0.6Mpa in 90 200 DEG C are relatively low.On the whole, the industrial hydrogen chemical industry of current nitro compound Skill still suffers from shortcomings, as high in reaction temperature, hydrogen pressure high (gas phase process) and solvent not environmentally, (the liquid phase work such as inflammable Skill).Therefore, the synthesis technique developing active higher hydrogenation catalyst and mild condition, solvent green will be that this field is long-term Target.Owing to having higher catalysis activity, load type palladium catalyst is the most frequently used hydrogenation catalyst.Traditional is heterogeneous Pd/C catalyst is it is generally required to just have higher hydrogenation activity under the conditions of high pressure hydrogen.(Liquid phase Hydrogenation of nitrobenzene, Applied Catalysis A:General, 2015,499,66 76) the most several Year, the palladium nanocatalyst of quasi-homodisperse demonstrates the activity advantage become apparent from.Such as, F.A.Harraz et al. finds poly- The palladium nanocatalyst that ethylene glycol (PEG) loads is at normal temperature and pressure (H2Under the conditions of), the hydrogenation of p-nitrophenyl just has higher urging Change activity, need remain for machine solvent (ethanol) hydrotropy.(Palladium nanoparticles stabilized by polyethylene glycol:Efficient,recyclable catalyst for hydrogenation of Styrene and nitrobenzene, Journal of Catalysis, 2012,286,184 192)
Polyamic acid is a kind of containing a large amount of carboxyls with the macromolecule of amide groups active function groups, has both had adjustable water Dissolubility, has again stronger complexing to metal, and therefore polyamic acid aqueous solution is to prepare quasi-homodisperse metal in situ to receive The good medium system of rice corpuscles.(Synthesis of silver nanocubes with controlled size using water-soluble poly(amic acid)salt as the intermediate via a novel ion- Exchange self-assembly technique, Nanoscale, 2013,5,12,132 12135) additionally, polyamic acid is A kind of stimulating responsive macromolecule, its water solublity has significant pH sensitivity, can give metal nano catalyst more rich Functional (such as adjustable water dispersible and micro-reaction environment etc.) so that it is catalytic performance is more efficient and intelligent.(Poly (amic acid)salt-stabilized silver nanoparticles as efficient and recyclable quasi-homogeneous catalysts for the aqueous hydration of nitriles to amides, New Journal of Chemistry,2016,40(1),358–364)
Therefore, the palladium nanocatalyst of polyamic acid load is suitable under aqueous phase and temperate condition, shows efficient standard Homogeneous catalysis activity, and the recyclable of palladium nanocatalyst can be realized by pH sensitivity and reuse.Up to the present, The palladium nanocatalyst of polyamic acid load and apply and still do not have document to report in catalyst field.
Summary of the invention
It is an object of the invention to provide the hydrogenation at aromatic nitro compound of a kind of polyamic acid supported palladium nanocatalyst Application in reaction.The technical scheme that the present invention provides is:
In described polyamic acid supported palladium nanocatalyst molal quantity is polyamic acid carboxyl molal quantity the 0.1 20 of palladium Times, preferably 2 times.Wherein, the physical characteristic parameter of described polyamic acid supported palladium nanocatalyst is: Pd nano particle is class Spherical, mean diameter is 1 20nm；Chemical feature parameter is: Pd nano particle is zero-valent state, contains in polyamic acid molecular structure There are a large amount of carboxyl and amide groups.
The preparation method of described polyamic acid supported palladium nanocatalyst comprises the steps:
(1) water-soluble polyamic acid salt is dissolved in deionized water, is configured to the polyamide that concentration is 0.013-1.3wt% Acid salt aqueous solution；
(2) in polyamic acid saline solution, add the precursor solution of palladium, stir under room temperature, obtain palladium ion with The complex solution of polyamic acid；
(3) complex solution obtained in step (2) is reacted with sodium borohydride or hydrazine hydrate, obtain polyamic acid load Palladium nano-catalytic agent dispersing liquid；
(4) being 25 with the palladium nano dispersion fluid pH value obtained in acid-base modifier regulating step (3), polyamic acid loads Palladium nanocatalyst settle, by crossing cleaner liquid, remove various water-solubility impurity ions in dispersion liquid, the palladium collected Nanocatalyst precipitum rejoins in the acid-base modifier that pH value is 7 12 again and is heavily disperseed, and finally returns to The polyamic acid supported palladium nanocatalyst of quasi-homodisperse state.
Wherein, step (1) described water-soluble polyamic acid salt is by polyamic acid and amine (such as triethylamine, piperidines etc.), alcohol Amine (such as triethanolamine, N methyldiethanol amine, diethanolamine, ethanolamine etc.), quaternary ammonium bases are (such as Tetramethylammonium hydroxide Deng) reacting prepared, polyamic acid is obtained by polycondensation reaction well known to those skilled in the art, including any one or more of diamidogen The polyamic acid obtained with any one or more of dianhydride polycondensation.As diamidogen can be 4,4 '-diaminodiphenyl ether (ODA), Phenylenediamine (m-PDA), p-phenylenediamine (p-PDA) etc.；Dianhydride can be pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 '-benzophenone Tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-two methyl phenyl ethers anisole tetracarboxylic dianhydrides (ODPA) etc..
The precursor solution of step (2) described palladium is the one in the acid of chlorine palladium, chlorine palladium acid sodium, potassium chloropalladate aqueous solution.
During step (3) described complex solution reacts with sodium borohydride, the palladium ion in complex solution and sodium borohydride Mol ratio be 1:(0.5 20), preferably 1:(1 2), reaction temperature is-5 100 DEG C, preferably 0 DEG C, and the response time is 0.5 24h, preferably 2h.During described complex solution reacts with hydrazine hydrate, the palladium ion in complex solution and hydrazine hydrate Mol ratio is 1:(1 50), preferably 1:(5 10), reaction temperature is-5 100 DEG C, preferably 40 DEG C, and the response time is 0.5 24h, preferably 12h.
Step (4) described acid-base modifier is hydrochloric acid, acetic acid, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate or carbon Acid potassium.It is preferably acetic acid and sodium hydroxide.
In the present invention, the preparation principle of catalyst is as follows:
In polyamic acid saline solution, the preparation process of Pd nano particle mainly experiences 2 stages, as shown in Figure 6: (a) palladium Ion (Pd2+) and polyamic acid salt (PAAS) complexation, form palladium macromole (PAA Pd N) complex；(b) palladium-macromole network Compound is reduced agent reduction, and under the Stabilization of polyamic acid salt, and forming core and grow into Pd nano particle (PdNPs), from And obtain the palladium nanocatalyst (PdNPs PAAS) of polyamic acid load.The final size of Pd nano particle, shape and dispersion State is relevant with the kind of polyamic acid salt, the consumption of palladium presoma, the consumption of reducing agent, reduction reaction temperature etc..
It is anti-that polyamic acid supported palladium nanocatalyst of the present invention can be used for the catalytic hydrogenation to aromatic nitro compound Ying Zhong.This application comprises the following steps:
(1) joining in Schlenk pipe by PdNPs PAAS catalyst solution and aromatic nitro compound, Schlenk manages Connect H2Balloon, then uses oil pump evacuation, repeatedly replaces H2More than three times.Reaction solution is subsequently at room temperature, normal pressure H2Under the conditions of It is stirred vigorously reaction.For the substrate that indivedual water solublity are excessively poor, need to additionally add organic solvent hydrotropy the most miscible with water. Wherein, described reaction substrate aromatic nitro compound is Nitrobenzol, 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, 4-nitre Base aniline, 3-nitroaniline, 2-nitroaniline, 4-Methylnitrobenzene, 4-chloronitrobenzene, 4-Nitrobromobenzene, 4-nitro-acetophenone, 4- Nitrobenzaldehyde, 4-nitrobenzyl alcohol etc..The mole dosage of described palladium catalyst and reaction substrate is than for 1:(10 1000), excellent Elect 1:100 as.Cosolvent is ethanol, methanol, acetone, DMF, N,N-dimethylacetamide etc., preferably second Alcohol, methanol.Reaction temperature is-5 100 DEG C, preferably 25 DEG C.
(2) identical with catalyst preparation step (4), can be by heavy for the acid of palladium nanocatalyst after catalytic reaction completes Fall, it is achieved the recovery of palladium nanocatalyst, the palladium nanocatalyst of recovery heavily can disperse in alkaline aqueous solution, and under being used for One takes turns quasi-homogeneous catalysis.After reaction terminates, with the hydrochloric acid regulation reaction solution of 1M to pH～2, subsequently reaction solution is stood sheet Carve, after PdNPs PAAS catalyst settles completely, use and directly topple over or the side of low-speed centrifugal (5000rpm, 10min) Method, can separate clear liquid with dark catalyst easily.The PdNPs PAAS catalyst separated rejoins water In, adjust pH～8 by the NaOH solution of 1M, make catalyst heavily disperse, i.e. can be directly used for being catalyzed next time.
The present invention has a following superiority:
1) the palladium nanocatalyst prepared by the present invention has higher specific surface area, in quasi-homodisperse shape in water State, the beneficially diffusion of reaction substrate, intermediate product and product；Polyamic acid carrier has higher polarity, is conducive to Catalyst active center's activation to reaction substrate.
2) the palladium nanocatalyst prepared by the inventive method has pH sensitivity, can be effectively used for palladium nanocatalyst Purification, accurate homogeneous efficient catalytic, recycle and reuse.
3) the inventive method is mainly with water as solvent, and environmental pollution is little；Reaction condition is normal temperature and pressure, saves the energy.
Accompanying drawing explanation
Fig. 1: the TEM image of polyamic acid supported palladium nanocatalyst in the present invention.
Fig. 2: the XRD figure spectrum of polyamic acid supported palladium nanocatalyst in the present invention.
With BTDA/ODA based polyamide hydrochlorate as carrier in Fig. 3: embodiment 2, the presoma with chlorine palladium acid sodium as palladium, prepare The XPS Pd3d high resolution scanning collection of illustrative plates of Pd nano particle.
Fig. 4: under different solutions pH value, the Zeta potential of polyamic acid salt supported palladium nanoparticle is measured.
Fig. 5: polyamic acid supported palladium nanocatalyst and the reaction of commercialization Pd/C catalyst catalytic hydrogenation of nitrobenzene Kinetic curve.
Fig. 6: the preparation principle figure of polyamic acid salt supported palladium nanoparticle.
Fig. 7: the catalytic applications schematic diagram of polyamic acid salt supported palladium nanoparticle.
The hydrogenation of Fig. 8: p-nitrophenyl repeats to be catalyzed the TEM figure of polyamic acid salt supported palladium nanoparticle after 6 times Picture.
Detailed description of the invention
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.
The raw material used in the embodiment of the present invention is commercially available.
Embodiment 1
The PMDA/ODA based polyamide triethylenetetraminehexaacetic acid amine salt dry silk taking 0.1g is dissolved in 80mL deionized water, after stirring and dissolving, Adding the chlorine palladium acid sodium solution that 10mL concentration is 0.01M, after stirring, be cooled to 0 DEG C, adding 10mL concentration is 0.01M's Sodium borohydride solution, continues stirring 2 hours, obtains the palladium nanocatalyst of polyamic acid salt load, for the quasi-homogeneous phase solution of black, 100mL altogether.
Embodiment 2
The BTDA/ODA based polyamide triethylenetetraminehexaacetic acid alcohol amine salt dry silk taking 0.1g is dissolved in 80mL deionized water, stirring and dissolving After, add the chlorine palladium acid sodium solution that 10mL concentration is 0.01M, after stirring, be warming up to 40 DEG C, rapidly joining 10mL concentration is The hydrazine hydrate solution of 0.1M, continues stirring 12 hours, obtains the palladium nanocatalyst of polyamic acid salt load, accurate homogeneous for black Solution, altogether 100mL.
The catalytically active assessment of embodiment 3 pure water middle polyamic acid salt supported palladium nanocatalyst mutually
The polyamic acid salt supported palladium nanocatalyst obtained by above-described embodiment 1 is used for aromatic nitro compound (nitro Benzene, 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, 4-nitroaniline, 3-nitroaniline, 2-nitroaniline, 4-nitro first Benzene, 4-nitro-acetophenone) quasi-homogeneous catalytic hydrogenation, it specifically comprises the following steps that
0.2mmol nitro compound and 2mL polyamic acid salt supported palladium nano-catalytic agent solution are joined Schlenk pipe In.Schlenk pipe connects H2Balloon, then uses oil pump evacuation, repeatedly replaces H2More than three times.Reaction solution subsequently room temperature, Normal pressure H2Under the conditions of be stirred vigorously reaction.For monitoring extent of reaction, each timing sampling～30 μ L, repeatedly extract by ethyl acetate After, merging organic facies, by gas chromatogram, it is analyzed, its result is as shown in table 1.
In order to contrast the activity of polyamic acid salt supported palladium nanocatalyst and commercialization Pd/C catalyst, at the same terms Lower employing same operation method, with the hydrogenation of commercialization Pd/C catalyst Nitrobenzol, the kinetics of catalytic reaction is bent Line comparison diagram is as shown in Figure 5.
The table 1 pure water middle PdNPs-PAAS catalyst catalytic hydrogenation result to aromatic nitro compound mutually
Reaction condition: 0.2mmol substrate, 1mol% palladium catalyst, 2mL water, 1bar H2, 25 DEG C.
The catalytically active assessment of polyamic acid salt supported palladium nanocatalyst in embodiment 4 water and alcohol mixed solvent
The polyamic acid salt supported palladium nanocatalyst obtained by above-described embodiment 1 is used for aromatic nitro compound (4-nitre Base chlorobenzene, 4-Nitrobromobenzene, 4-nitrobenzaldehyde, 4-nitrobenzyl alcohol) quasi-homogeneous catalytic hydrogenation, its concrete steps are such as Under:
0.2mmol nitro compound, 2mL polyamic acid salt supported palladium nano-catalytic agent solution and 1mL ethanol are joined In Schlenk pipe.Schlenk pipe connects H2Balloon, then uses oil pump evacuation, repeatedly replaces H2More than three times.Reaction solution with After at room temperature, normal pressure H2Under the conditions of be stirred vigorously reaction.For monitoring extent of reaction, each timing sampling～30 μ L, use acetic acid second After ester repeatedly extracts, merging organic facies, be analyzed it by gas chromatogram, its result is as shown in table 2.
The PdNPs-PAAS catalyst catalytic hydrogenation result to aromatic nitro compound in table 2 water and alcohol mixed solvent
Reaction condition: 0.2mmol substrate, 1mol% palladium catalyst, 2mL water and 1mL ethanol, 1bar H2, 25 DEG C.
Embodiment 5
The polyamic acid salt supported palladium nanocatalyst obtained by above-described embodiment 1 is used for the quasi-homogeneous catalysis hydrogen of Nitrobenzol Change reaction, investigate the repeat performance of catalyst, specifically comprise the following steps that
0.2mmol Nitrobenzol and 2mL polyamic acid salt supported palladium nano-catalytic agent solution are joined in Schlenk pipe. Schlenk pipe connects H2Balloon, then uses oil pump evacuation, repeatedly replaces H2More than three times.Reaction solution subsequently in room temperature, often Pressure H2Under the conditions of be stirred vigorously reaction.After reaction 5h, with the hydrochloric acid regulation reaction solution of 1M to pH～2, subsequently by reaction solution Stand a moment, after PdNPs PAAS catalyst settles completely, use and directly topple over or low-speed centrifugal (5000rpm, 10min) Method, can easily clear liquid be separated with catalyst solid.The PdNPs PAAS catalyst separated rejoins In 2mL water, with the NaOH solution of 1M adjust pH to～8, make catalyst heavily disperse, i.e. can be directly used for being catalyzed next time.(result is shown in Table 3)
The repetition catalytic effect of table 3 polyamic acid salt supported palladium nanocatalyst catalysis nitrobenzene reaction
Reaction condition: 0.2mmol Nitrobenzol, 1mol% palladium catalyst, 2mL water, 1bar H2, 25 DEG C.

Claims (9)

1. polyamic acid supported palladium nanocatalyst application in the hydrogenation of aromatic nitro compound.
Apply the most as claimed in claim 1, it is characterised in that in described polyamic acid supported palladium nanocatalyst palladium mole Number is 0.1 20 times of polyamic acid carboxyl molal quantity.
Apply the most as claimed in claim 1, it is characterised in that in described polyamic acid supported palladium nanocatalyst palladium mole Number is 2 times of polyamic acid carboxyl molal quantity.
Apply the most as claimed in claim 1, it is characterised in that the physical features of described polyamic acid supported palladium nanocatalyst Parameter is: Pd nano particle is near-spherical, and mean diameter is 1 20nm；Chemical feature parameter is: Pd nano particle is zeroth order State.
5. the application described in claim 1, it is characterised in that the preparation method bag of described polyamic acid supported palladium nanocatalyst Include following steps:
(1) water-soluble polyamic acid salt is dissolved in deionized water, is configured to the polyamic acid salt that concentration is 0.013-1.3wt% Aqueous solution；
(2) in polyamic acid saline solution, add the precursor solution of palladium, stir under room temperature, obtain palladium ion and polyamides The complex solution of amino acid；
(3) complex solution obtained in step (2) is reacted with sodium borohydride or hydrazine hydrate, obtain the palladium of polyamic acid load Nano-catalytic agent dispersing liquid；
(4) it is 25 with the palladium nano dispersion fluid pH value obtained in acid-base modifier regulating step (3), the palladium of polyamic acid load Nanocatalyst settles, and by crossing cleaner liquid, removes various water-solubility impurity ions in dispersion liquid, the palladium nanometer collected Catalyst sedimentation thing rejoins in the acid-base modifier that pH value is 7 12 again and is heavily disperseed,
And finally return to the polyamic acid supported palladium nanocatalyst of quasi-homodisperse state.
6. method as claimed in claim 5, it is characterised in that step (1) described water-soluble polyamic acid salt is by polyamic acid Prepare with amine, alcamines, the reaction of quaternary ammonium bases.
7. method as claimed in claim 6, it is characterised in that the precursor solution of step (2) described palladium is the acid of chlorine palladium, chlorine palladium One in acid sodium, potassium chloropalladate aqueous solution.
8. method as claimed in claim 7, it is characterised in that step (3) described complex solution and sodium borohydride or hydration In hydrazine reaction, the mol ratio of the palladium ion in complex solution and sodium borohydride is respectively 1:(0.5 20), reaction temperature is- 5 100 DEG C, the response time is 0.5 24h；Palladium ion during described complex solution reacts with hydrazine hydrate, in complex solution It is 1:(1 50 with the mol ratio of hydrazine hydrate), reaction temperature is-5 100 DEG C, and the response time is 0.5 24h.
9. method as claimed in claim 8, it is characterised in that step (4) described acid-base modifier is hydrochloric acid, acetic acid, three second Amine, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
CN201610514242.1A 2016-07-01 2016-07-01 Application of the polyamic acid supported palladium nanocatalyst in the hydrogenation of aromatic nitro compound Expired - Fee Related CN106187783B (en)

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