CN100368078C - Nano Pd catalyst and its preparation and application - Google Patents
Nano Pd catalyst and its preparation and application Download PDFInfo
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- CN100368078C CN100368078C CNB2005100406694A CN200510040669A CN100368078C CN 100368078 C CN100368078 C CN 100368078C CN B2005100406694 A CNB2005100406694 A CN B2005100406694A CN 200510040669 A CN200510040669 A CN 200510040669A CN 100368078 C CN100368078 C CN 100368078C
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Abstract
The present invention relates to a nanometer palladium catalyst which is a polymer loading nanometer palladium catalyst prepared by means of the reaction of water-soluble inorganic palladium salt and water-soluble macromolecule in a low-carbon alcohol solvent at the temperature of 60 to 90 DEG C. The present invention has the advantages of simple preparation method, high activity and repeatable use. When the present invention is used for preparing a biphenyl compound, water can be used as a solvent, and organic alkali is replaced by inorganic alkali for synthesis. Therefore, technological processes are simplified, and more three wastes are avoided. The dosage of the catalyst is small, product purity is more than or equal to 99.5%, and yield is more than or equal to 95%.
Description
One, technical field
The present invention relates to Catalysts and its preparation method and application that a kind of organic synthesis is used, exactly be a kind of nano Pd catalyst and preparation method thereof and prepare application in the biphenyl compound in coupling reaction.
Two, background technology
Separate benzene nuclei compound is a kind of important organic intermediate, and it is widely used in the production field of many fine chemical products such as material, medicine, agricultural chemicals, daily-use chemical industry.Common synthetic method is with substituted benzene boric acid and to replace halogen (bromine and iodine) be raw material for benzene, under the catalysis of transition metal palladium complex in organic solvent such as triethylamine, diethylamine, oxolane, N, finish (Suzuki Coupling Suzuki coupling reaction) in the dinethylformamide, this method technical maturity, but in process of production Metal Palladium and part use and discharging etc. causes environmental pollution; And thereby the Metal Palladium clandestine meeting pollutes product and makes the product purification difficulty; Another drawback of this method is the use of a large amount of organic solvents in addition, needs to recycle, and has increased equipment investment and operating cost, and contaminated environment, and workers ' health is produced harm.Based on the shortcoming that exists in the above prior art, the utmost point is necessary technology is improved.
Three, summary of the invention
The object of the invention is: overcome above deficiency of the prior art, a kind of polymer loaded with nano palladium catalyst can be recycled is provided, need not any organic solvent, only in running water, realize substituted benzene boric acid and replace halogen (bromine/iodine) for the coupling of benzene, the technology of preparation separate benzene nuclei compound.
This nano Pd catalyst, be by water-soluble inorganic palladium salt in the low-carbon alcohols solvent and the polymer loaded with nano palladium catalyst for preparing is arranged under the water soluble polymer existence condition.Its essence is that the nanometer palladium is attached to being the nano Pd catalyst of carrier in other words with the water soluble polymer on the water soluble polymer.
The preparation method of this nano Pd catalyst is in the low-carbon alcohols solvent, adds water-soluble inorganic palladium salt and water soluble polymer, and stirring reaction is 1.5～3.5 hours under 60～90 ℃ of conditions, preferred 75～85 ℃ and 2～3 hours.Reaction finishes the back distillating recovering solvent, promptly gets polymer loaded with nano palladium catalyst.In the method, with regard to nascent state metal palladium black (nanometer palladium) average grain diameter 5～7nm.
Described solvent low-carbon alcohols comprises the monobasic or the polyalcohol of 1～4 carbon atom, as one or more mixed alcohols in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, propane diols, glycerine, butanols, isobutanol, the sec-butyl alcohol.Preferred alcohol, ethylene glycol and propyl alcohol.
Described water-soluble inorganic palladium salt is palladium bichloride, palladium, palladium nitrate.Water-soluble inorganic palladium salt just forms nascent state black nano palladium under uniform temperature in the low-carbon alcohols solvent, precipitation is separated out and attached on the high polymer simultaneously.
That described water soluble polymer comprises natural class or/and semi-synthetic class or/and the water soluble polymer of synthetic class.Preferably carboxymethyl cellulose or/and polyvinyl alcohol or/and polyethylene glycol oxide or/and polyvinylpyrrolidone.
This nano Pd catalyst is mainly used in the preparation biphenyl compound, comprise each unit process of coupling reaction, separation and purifying, it is characterized in that with water being solvent, under water soluble carbonate or bicarbonate existence condition, halogeno-benzene and substituted benzene boric acid is in 60～100 ℃ of stirring reactions 1～6 hour, preferred 75～85 ℃ of reactions 2～4 hours.Catalyst consumption is 0.2～0.8% (molar percentage) of reactant, preferred 0.4～0.6% (molar percentage).Reaction is cooled to room temperature after finishing, and standing demix is isolated organic facies (crude product), washes the back purifying with water and promptly gets pure product polymer loaded with nano palladium catalyst.Product purity 〉=99.5% (HPLC mensuration), yield 〉=95%.
Described carbonate or bicarbonate are sodium salt or sylvite or ammonium salt etc., preferred sylvite.
This catalyst is with respect to palladium complex catalyst, and preparation is simple, and active high, particularly reusable, evidence is used repeatedly and still do not reduced activity 20 times.
This catalyst is used to prepare biphenyl compound, and coupling reaction can be finished in water, has fundamentally got rid of organic solvent, can replace expensive organic base triethylamine with cheap inorganic base simultaneously, and cost of material is reduced significantly.On technology, not only reacting balance is easy to control, and the separation after the reaction end is easier, has particularly omitted solvent recovery, has simplified technology, has also eliminated potential safety hazard, avoids producing more three-waste pollution environment.This catalyst activity height, consumption is few, resulting product purity height, yield is also high.
Four, description of drawings
It shown in the accompanying drawing transmission electron microscope picture (Philips Tecnai 200 apparatus measures) of polymer loaded with nano palladium.
Five, the specific embodiment
(1), Preparation of catalysts
1, getting the adding of 300～500ml ethanol takes back in the reaction bulb of flow condenser, stir and add 17.7g palladium bichloride and 32.3g polyvinyl alcohol down, heat up in dissolving back, 80 ℃ of reactions 2 hours, and nascent state black nano palladium powder (average grain diameter 5nm) precipitation is separated out and attached on the polyvinyl alcohol.Reaction boils off ethanol after finishing, and can obtain polyvinyl alcohol loaded with nano palladium catalyst.
2, get ethylene glycol 300～500ml, palladium nitrate 23g, sodium alginate 37g, 75 ℃, 3 hours, other were operated with embodiment 1.
3, get ethanol, propyl alcohol mixed alcohol 300～500ml, palladium 22.4g, carboxymethyl cellulose 32.6g, 85 ℃, 2 hours, other were operated with embodiment 1.
4, get propyl alcohol 300～500ml, palladium bichloride 17.7g, polyethylene glycol oxide 32.3g, 80 ℃, 2 hours, other were operated with embodiment 1.
(2), the preparation of biphenol compound
Be example with preparation to first biphenyl now, non-limiting examples is described below:
5, the 6L running water is added in the reactor, stir add this catalyst 50g (containing palladium black 10.6g, 0.1mol) down and wait the iodobenzene of mole (20ml), to toluene boric acid and potash, intensification, 80 ℃ were reacted 3～4 hours.Reaction finishes the back cooling, and standing demix under the room temperature divides the phase of anhydrating, and reclaims and uses.Organic facies washes twice with water and obtains crude product to first biphenyl, is further purified, and promptly gets pure product to first biphenyl 3.30Kg, yield 98.2%, product purity 〉=99% (HPLC mensuration).Product fusing point: 46～47 ℃;
1HNMR (250MHz, CDCl
3): δ=7.58-7.21 (m, 9H), 2.37 (s, 3H);
13CNMR (62.5MHz, CDCl
3): δ=141.2,138.4,137.0,129.5,128.7,127.0,20.1; MS:m/z (%)=168 (M
+, 100), 152 (24), 139 (7), 128 (6), 115 (15), 91 (5).
6, got catalyst 60g (containing palladium black 10.6Kg, 0.1mol) 75 ℃, 3 hours, surplus with embodiment 5, get pure product to first biphenyl 3.25Kg, yield 96.7%, product purity 〉=99% (HPLC mensuration).Product physics and spectroscopy data are the same.
7, get catalyst 55g (containing palladium black 10.6g 0.1mol), 85 ℃, 2 hours, surplus with embodiment 5, must be to first biphenyl 3.20Kg, yield 95.2%, product purity 〉=99% (HPLC mensuration).Product physics and spectroscopy data are the same.
Claims (10)
1. nano Pd catalyst is characterized in that: what prepared in water soluble polymer and low-carbon alcohols by water-soluble inorganic palladium salt is the polymer loaded with nano palladium catalyst of carrier with the water soluble polymer.
2. preparation method by the described nano Pd catalyst of claim 1 is characterized in that: in the low-carbon alcohols solvent, add water-soluble inorganic palladium salt and water soluble polymer stirring reaction 1.5～3.5 hours under 60～90 ℃ of conditions.
3. preparation method according to claim 2 is characterized in that: reaction condition is 75～85 ℃, 2～3 hours.
4. according to claim 2 or 3 described preparation methods, it is characterized in that: described low-carbon alcohols comprises that the monohydric alcohol of 1～4 carbon atom is or/and polyalcohol.
5. preparation method according to claim 4 is characterized in that: described low-carbon alcohols be ethanol or/and ethylene glycol or/and propyl alcohol.
6. according to claim 2 or 3 described preparation methods, it is characterized in that: that described water soluble polymer comprises natural class or/and semi-synthetic class or/and the water soluble polymer of synthetic class.
7. preparation method according to claim 6 is characterized in that: described water soluble polymer be carboxymethyl cellulose or/and polyvinyl alcohol or/and polyethylene glycol oxide or/and polyvinylpyrrolidone.
8. one kind by the described Application of Catalyst of claim 1, be to be used for preparing biphenyl compound, comprise coupling reaction, separation and purifying, it is characterized in that: coupling reaction with water be solvent, halogeno-benzene and substituted benzene boric acid under the water soluble carbonate existence condition in 60～100 ℃ the reaction 1～6 hour, catalyst amount is 0.2～0.8% (molar percentage) of reactant.
9. according to the preparation method of right 8 described biphenyl compounds, it is characterized in that: reaction condition is 75～85 ℃, 2～4 hours.
10. according to Claim 8 or 9 described preparation methods, it is characterized in that: catalyst amount is 0.4～0.6% (molar percentage) of reactant.
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| CN100368078C true CN100368078C (en) | 2008-02-13 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497041B (en) * | 2009-02-12 | 2010-11-03 | 凯瑞化工有限责任公司 | Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization |
| CN102351620A (en) * | 2011-08-09 | 2012-02-15 | 太原理工大学 | Method for preparing biphenyl compound through catalyzing Suzuki coupling reaction by nanometer palladium catalyst |
| CN102267848A (en) * | 2011-08-09 | 2011-12-07 | 太原理工大学 | Method for synthesizing biphenol compound by catalyzing Suzuki coupling reaction with nanometer palladium catalyst |
| CN104785792B (en) * | 2014-12-31 | 2017-03-15 | 武汉纺织大学 | A kind of green synthesis method of Technique of Nano Pd carboxymethyl cellulose complex |
| CN106964403B (en) * | 2017-04-12 | 2019-10-22 | 苏州至善化学有限公司 | A kind of Magnetic phenyl phosphine palladium composite catalyst and its application |
| CN110394190B (en) * | 2019-07-09 | 2022-04-01 | 上海应用技术大学 | Nitrogen-rich triazine-based calix [4] arene polymer supported palladium catalyst, and preparation method and application thereof |
| CN116196977A (en) * | 2023-03-05 | 2023-06-02 | 福建医科大学附属第二医院 | Platinum nanometer laccase with performance superior to that of natural laccase |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064477A (en) * | 1991-03-04 | 1992-09-16 | 中国科学院大连化学物理研究所 | Oxo process for organic acid with halohydrocarbon under normal pressure |
| WO2004024323A1 (en) * | 2002-09-13 | 2004-03-25 | Wako Pure Chemical Industries, Ltd. | Palladium catalyst composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064477A (en) * | 1991-03-04 | 1992-09-16 | 中国科学院大连化学物理研究所 | Oxo process for organic acid with halohydrocarbon under normal pressure |
| WO2004024323A1 (en) * | 2002-09-13 | 2004-03-25 | Wako Pure Chemical Industries, Ltd. | Palladium catalyst composition |
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