CN106378192A - Modified montmorillonite-loaded palladium-copper catalytic material used for catalysis of organic coupling reaction - Google Patents
Modified montmorillonite-loaded palladium-copper catalytic material used for catalysis of organic coupling reaction Download PDFInfo
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- CN106378192A CN106378192A CN201610658453.2A CN201610658453A CN106378192A CN 106378192 A CN106378192 A CN 106378192A CN 201610658453 A CN201610658453 A CN 201610658453A CN 106378192 A CN106378192 A CN 106378192A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4266—Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0269—Complexes comprising ligands derived from the natural chiral pool or otherwise having a characteristic structure or geometry
- B01J2531/0272—Complexes comprising ligands derived from the natural chiral pool or otherwise having a characteristic structure or geometry derived from carbohydrates, including e.g. tartrates or DIOP
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
Abstract
The invention relates to a preparation method for a modified montmorillonite-loaded palladium-copper catalytic material used for catalysis of an organic reaction, belonging to the technical field of preparation technology for chemical catalysts. According to the invention, chitosan high polymer is used for effective intercalation and modification of montmorillonite, and the active components consisting of palladium and copper are uniformly dispersed among the layers of montmorillonite through complexation action with an intercalator, i.e., chitosan. When applied to Sonogashira reactions, the modified montmorillonite-loaded palladium-copper bimetallic heterogeneous catalytic material prepared in the invention has obviously higher catalytic activity and stability compared with heterogeneous catalytic materials only loaded with palladium or copper metal.
Description
Technical field
The present invention relates to a kind of modified montmorillonoid supported palladium for organometallic coupling reaction catalysis, copper bi-metal catalysis material
Preparation method, belong to the technical field of chemical catalyst preparation technology.
Background technology
It is the available strategy building organic molecular carbon carbon three key skeleton that Sonogashira is coupled, you can with by better simply
Individually catalysis completes it is also possible to be catalyzed by bimetallic catalyst palladium metal catalyst.Comparatively single-metal reforming catalyst has
The reaction process simplifying, be also easier to hold course of reaction, but under certain reaction condition, monometallic palladium chtalyst material
Catalysis activity is relatively low, now, just embodies the advantage of bimetallic catalytic material.
Recently many researchs find（Bonnamour,J.；Piedrafita,M.；Bolm,C.Adv.Synth. Catal.2010,
352,1577.）, much so-called " monometallic catalyst system and catalyzing " often comes from other metal impurities of trace.Bolm group is directed to
This phenomenon has carried out substantial amounts of experiment, proposes the key that trace metal is catalytic reaction, and the bimetallic of such catalytic process is worked in coordination with
Effect is particularly likely that the origin of catalysis activity.（Thome,I.；Nijs,A.；Bolm, C.Chem.Soc.Rev.2012,41,
979.）.Exactly because so, under the same reaction conditions, bimetallic catalytic material often will have more than monometallic catalysis material
High catalysis activity and yield.Such as, M ü slehiddino lu etc.（Müslehiddinoğlu, J.；Li, J.；
Tummala,S.；Deshpande,R.Org Process Res Dev,2010,14:890）Have developed Pd Cu/C to replace
The chiral ketone of Raney-Ni catalysis and α-phenylethylamine selective hydrogenation, Comparatively speaking, are made using Pd Cu/C catalyst ratio
Yield with Pd/C catalyst is high by 20%.
Content of the invention
The invention provides a kind of modified montmorillonoid supported palladium for organometallic coupling reaction catalysis, copper catalysis material, profit
With chitosan intercalation modified montmorillonoid composite as catalyst carrier, pay(useful) load palladium, copper bi-metal are made new non-equal
Phase catalysis material is simultaneously applied to Sonogashira reaction.Macromolecule is modified to the intercalation synthesis of montmorillonite, has both remained shitosan
The good complexing power to transition metal for the macromolecule, have concurrently again the larger specific surface area of montmorillonite matrix, high thermal stability and
The advantages of stronger Molecular Adsorption performance.Modified montmorillonoid load in Sonogashira reactive applications, prepared by the present invention
Palladium, copper bi-metal heterogeneous catalysis material have considerably higher catalysis to live than supported palladium or the single metal heterogeneous catalysis material of copper
Property and stability.
For reaching above-mentioned purpose, the present invention is achieved by the following technical solutions：
A kind of modified montmorillonoid supported palladium for organometallic coupling reaction catalysis, copper catalysis material, described catalysis material has Jie
Pore structure and layer structure, active component palladium, copper is uniformly dispersed in described catalysis material system, active component palladium, copper
Weight/mass percentage composition is the 0-3% of carrier.
Described catalysis material passes through following steps and is obtained：
（1）Take quantitative Chitosan powder, the acetic acid solution adding mass fraction to be 2%, being made into shitosan weight content is 0.5-5%
Mixed solution, standing, deaeration, standby；
（2）Take quantitative solid palladium bichloride, plus distilled water, add sodium chloride, heating, stirring make it be completely dissolved, Pd2+Concentration
For 0.01-0.1mol/L；
（3）Take quantitative solid copper chloride, plus distilled water, stirring makes it be completely dissolved, Cu2+Concentration is 0.01-0.1mol/L；
（4）Take 1g-5g montmorillonite, add distilled water, heating, after stirring, chitosan solution is poured in montmorillonite suspension
Continue 4-12 hour of stirring；
（5）Under continuous stirring, in above-mentioned montmorillonite shitosan system, drip Pd2+Solution and Cu2+Solution, with Pd2+Molten
Liquid and Cu2+Being gradually added of solution, system viscosity gradually rises, and accelerates speed and continues to stir several hours；
（6）By above-mentioned montmorillonite/shitosan/palladium/copper system deionized water centrifuge washing to neutral, obtain after drying a few hours
Final catalysis material.
Described step（1）In shitosan molecular weight be 50,000-20 ten thousand, deacetylation be 70%-98%.
Described step（3）Montmorillonite be cationic montmorillonite, original soil specific surface area is in 2-5m2/g；Palladium ion and copper
The addition of ion is the 0-3% of carrier.
Described step（6）Centrifuge washing in order to remove unnecessary acetic acid and residual chlorion, in case to catalytic reaction shadow
Ring.
The present invention is used for the modified montmorillonoid supported palladium of organometallic coupling reaction catalysis, copper catalysis material has beneficial effect as follows
Really：
1st, preparation process is simple, equipment requirement is low.
2nd, the carrier of heterogeneous catalysis material is macromolecule modified montmorillonite, and shitosan macromolecule changes to the compound of montmorillonite
Property, both remain the good complexing power to transition metal for the shitosan macromolecule, have the larger specific surface of montmorillonite matrix again concurrently
The advantages of long-pending, higher heat endurance and stronger Molecular Adsorption performance.
3rd, catalysis material can play bimetallic concerted catalysis effect in catalysis organometallic coupling reaction.
4th, the specific surface area of catalysis material is 10-20 times of original montmorillonoid soil, is easy to filter from reactant liquor and divides after reaction
From, stable physical property, can reuse repeatedly.
5th, reactant liquor is isolated after reactor, post processing that need not be numerous and diverse, if catalyst is simply cleaned, dry
After dry, rejoin reaction raw materials and can start new reaction.
Brief description
Fig. 1 is the outward appearance photo of the catalysis material prepared by the present invention；
Fig. 2 is the catalysis material preparation technology flow chart of the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
Embodiment 1
The present invention is used for the modified montmorillonoid supported palladium of organometallic coupling reaction catalysis, copper catalysis material, comprises the following steps：
1st, the preparation of shitosan weak solution：Take pharmaceutical grade Chitosan powder（Molecular weight 100,000, deacetylation is 95%）0.5g, molten
300ml acetum in 2% is made into mixed solution, forms homogeneous phase solution, standing and defoaming 2h within continuously stirred 2 hours.
2nd, the preparation of palladium ion solution：Weigh 0.3g palladium bichloride, plus 100ml distilled water, then plus 5g sodium chloride in conical flask
In, heating, stirring make it be completely dissolved formation Na2PdCl4Solution.
3rd, the preparation of copper ion solution：Weigh 0.230g copper chloride, plus 100ml distilled water, stirring makes it be completely dissolved shape
Become [Cu (H2O)4]2+Solution.
4th, the preparation of chitosan intercalation montmorillonite load palladium chtalyst material：Take 2g montmorillonite, add distilled water, heating, stir
After mixing uniformly, chitosan solution is poured into and in montmorillonite suspension, continue stirring 4-12 hour.Under continuous stirring, to above-mentioned illiteracy
In de- soil cursting glycan system, drip Pd2+Solution and Cu2+Solution, continues stirring 4-12 hour.By this montmorillonite/shitosan/palladium/
Copper system centrifuge washing, to neutral, obtains final catalysis material after drying a few hours.
Application examples
Modified montmorillonoid supported palladium obtained by above-described embodiment, copper bi-metal catalysis material are carried out being catalyzed Sonogashira
The application experiment of reaction, its process and result are as described below：
Modified montmorillonoid supported palladium, copper bi-metal catalysis material catalysis halogenated aryl hydrocarbon and phenylacetylene class compound
Sonogashira coupling reaction：
By test, in following reaction condition：Iodobenzene 1mmol, phenylacetylene 1.2mmol, catalysis material 1.00g（Palladium content is
0.0040mmol, copper content is 0.0040mmol）, Na2CO31.5 mmol, triphenyl phosphorus 0.008g, reaction dissolvent（Water：Second two
Diethylene glycol dimethyl ether=1:4 volume ratios）, react 12h, reaction result at 80 DEG C：The yield of coupled product is 95%；Catalyst reuses
3 times, the yield of coupled product, all more than 80%, shows that this catalyst is functional in Sonogashira reaction, more stable.
As a comparison, same reaction conditions, modified montmorillonoid supported palladium monometallic catalysis material is applied to same reactant
System, yield is less than 80%；Modified montmorillonoid supported copper monometallic catalysis material is applied to same reaction system, does not react, is no coupled
Product.
The present invention realizes palladium, copper bi-metal pay(useful) load using the complexing of shitosan and transition metal ions；Made
Standby modified montmorillonoid supported palladium, copper bi-metal heterogeneous catalysis material are than single supported palladium or copper metal heterogeneous catalysis material
There are considerably higher catalysis activity and stability.
Above-described embodiment is only used for illustrating the inventive concept of the present invention, rather than the restriction to rights protection of the present invention,
All changes that using this design, the present invention is carried out with unsubstantiality, all should fall into protection scope of the present invention.
Claims (5)
1. a kind of modified montmorillonoid supported palladium for organometallic coupling reaction catalysis, copper catalysis material it is characterised in that：Described urge
Change material and there is meso-hole structure and layer structure, active component palladium, copper are uniformly dispersed in described catalysis material system, activity
Component palladium, the weight/mass percentage composition of copper are the 0-3% of carrier.
2. it is used for modified montmorillonoid supported palladium, the copper catalysis material of organometallic coupling reaction catalysis, its feature as claimed in claim 1
It is that described catalysis material passes through following steps and is obtained：
（1）Take quantitative Chitosan powder, the acetic acid solution adding mass fraction to be 2%, being made into shitosan weight content is 0.5-5%
Mixed solution, standing, deaeration, standby；
（2）Take quantitative solid palladium bichloride, plus distilled water, add sodium chloride, heating, stirring make it be completely dissolved, Pd2+Concentration is
0.01-0.1mol/L；
（3）Take quantitative solid copper chloride, plus distilled water, stirring makes it be completely dissolved, Cu2+Concentration is 0.01-0.1mol/L；
（4）Take 1g-5g montmorillonite, add distilled water, heating, after stirring, chitosan solution is poured in montmorillonite suspension
Continue 4-12 hour of stirring；
（5）Under continuous stirring, in above-mentioned montmorillonite/shitosan system, drip Pd2+Solution and Cu2+Solution, with Pd2+Molten
Liquid and Cu2+Being gradually added of solution, system viscosity gradually rises, and accelerates speed and continues to stir several hours；
（6）By above-mentioned montmorillonite/shitosan/palladium/copper system deionized water centrifuge washing to neutral, obtain after drying a few hours
Final catalysis material.
3. it is used for modified montmorillonoid supported palladium, the copper catalysis material of organometallic coupling reaction catalysis, its feature as claimed in claim 2
It is：Described step（1）In shitosan molecular weight be 50,000-20 ten thousand, deacetylation be 70%-98%.
4. it is used for modified montmorillonoid supported palladium, the copper catalysis material of organometallic coupling reaction catalysis, its feature as claimed in claim 2
It is：Described step（3）Montmorillonite be cationic montmorillonite, original soil specific surface area is in 2-5m2/g；Palladium ion and copper ion
Addition be carrier 0-3%.
5. it is used for modified montmorillonoid supported palladium, the copper catalysis material of organometallic coupling reaction catalysis, its feature as claimed in claim 2
It is：Described step（6）Centrifuge washing in order to remove unnecessary acetic acid and residual chlorion, in case having affected on catalytic reaction.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610658453.2A CN106378192A (en) | 2016-08-12 | 2016-08-12 | Modified montmorillonite-loaded palladium-copper catalytic material used for catalysis of organic coupling reaction |
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| CN201610658453.2A CN106378192A (en) | 2016-08-12 | 2016-08-12 | Modified montmorillonite-loaded palladium-copper catalytic material used for catalysis of organic coupling reaction |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1663990A (en) * | 2005-03-11 | 2005-09-07 | 华东理工大学 | Chitosan/montmorillonite nano composite materials and method for preparing same |
| CN1709572A (en) * | 2005-04-29 | 2005-12-21 | 四川大学 | Aryl halide to olefin arylation carrying bimetallic catalyst, and its preparing method |
| EP2716605A1 (en) * | 2011-06-03 | 2014-04-09 | Nanobiomatters Research & Development, S.L. | Nanocomposite materials based on metal oxides having multi-functional properties |
| CN103877995A (en) * | 2014-03-31 | 2014-06-25 | 陕西师范大学 | Montmorillonite-loaded nano Pd/Cu catalyst and in-situ one-pot preparation and application thereof |
| CN104531667A (en) * | 2014-12-10 | 2015-04-22 | 中国海洋大学 | Preparation method of polyphenol oxidase immobilizing carrier |
-
2016
- 2016-08-12 CN CN201610658453.2A patent/CN106378192A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1663990A (en) * | 2005-03-11 | 2005-09-07 | 华东理工大学 | Chitosan/montmorillonite nano composite materials and method for preparing same |
| CN1709572A (en) * | 2005-04-29 | 2005-12-21 | 四川大学 | Aryl halide to olefin arylation carrying bimetallic catalyst, and its preparing method |
| EP2716605A1 (en) * | 2011-06-03 | 2014-04-09 | Nanobiomatters Research & Development, S.L. | Nanocomposite materials based on metal oxides having multi-functional properties |
| CN103877995A (en) * | 2014-03-31 | 2014-06-25 | 陕西师范大学 | Montmorillonite-loaded nano Pd/Cu catalyst and in-situ one-pot preparation and application thereof |
| CN104531667A (en) * | 2014-12-10 | 2015-04-22 | 中国海洋大学 | Preparation method of polyphenol oxidase immobilizing carrier |
Non-Patent Citations (2)
| Title |
|---|
| 徐伟: ""蒙脱土负载Pd/Cu 双金属纳米微粒催化Sonogashira偶联反应"", 《有机化学》 * |
| 袁侠: ""壳聚糖改性蒙脱土负载钯非均相催化材料的微观结构与性能研究"", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
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