CN105233877A - Preparation method for porous spongy chitosan palladium-supported catalytic material - Google Patents
Preparation method for porous spongy chitosan palladium-supported catalytic material Download PDFInfo
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- CN105233877A CN105233877A CN201410281904.6A CN201410281904A CN105233877A CN 105233877 A CN105233877 A CN 105233877A CN 201410281904 A CN201410281904 A CN 201410281904A CN 105233877 A CN105233877 A CN 105233877A
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Abstract
The invention relates to a preparation method for a porous spongy chitosan palladium-supported catalytic material used for organic reaction catalysis, provides the porous spongy chitosan palladium-supported catalytic material used for organic reaction catalysis and a preparation method therefor. According to the catalytic material provided by the invention, chitosan is taken as a macromolecular carrier starting material, and palladium ions are directly utilized as a cross-linking agent to obtain a palladium cross-linked chitosan porous gel catalytic material; the obtained catalytic material has an open three-dimensional porous spongy structure, and has an porosity of 60-80%; and an active ingredient palladium is used as a cross-linking point of a gel network, and content (in mass percentage) of the active ingredient palladium is smaller than or equal to 1.5% of the weight of the catalytic material. The prepared material has good catalytic performance in an application of an organic coupling reaction, and can be repeatedly utilized by many times.
Description
technical field:
The present invention relates to the preparation method of the chitosan loaded palladium chtalyst material of a kind of porous spongy for organic reaction catalysis, belong to chemical catalyst fabricating technology field.
background technology:
Shitosan is considered to a kind of good boiomacromolecule carrier preparing carrier-borne transition metal catalysis material, and this mainly has benefited from having a large amount of amino and hydroxyl isopolarity group in its molecular structure, can form strong complexing with transition metal palladium plasma.From existing bibliographical information, shitosan is utilized to prepare in the preparation process of chitosan loaded palladium chtalyst material for carrier, absorption method is the transition metal mode of loading commonly used the most, its general process is, now shitosan is made the carrier solids of definite shape, then be immersed in transition metal ions as in palladium ion solution, realized the load of transition metal by the complexing of palladium ion and macromolecule matrix polar group.But this mode of loading is often by the impact of macromolecule aggregating state structure, and complexing is uneven; The chitosan loaded palladium tunica fibrosa obtained even needs by solvent rinse post processing to remove the comparatively weak palladium of some complexings.Another kind of not too conventional method is direct crosslinking method, namely under solution state, allows macromolecule and transition metal palladium ion carry out sufficient crosslinking and reacts and form gel, then make various forms of catalyst.But this method makes the viscosity of system rise because shitosan and transition metal form strong complexing very fast, and transition metal load capacity can not be too high, is not easy the heterogeneous catalysis material obtaining having suitable catalyst load capacity.
summary of the invention:
The object of the invention is for the deficiencies in the prior art, a kind of highly active shitosan palladium chtalyst material and preparation method thereof is provided.
Concrete, in the present invention, we carry out technological improvement to direct crosslinking method, the shitosan utilizing molecular weight medium is macromolecule carrier initiation material, with the chitosan solution of low concentration for starting soln, directly utilize transition metal palladium ion for crosslinking agent and no longer carry out additional chemical and be cross-linked, adopt gel solution the mode of the freeze drying film forming of tolerable high viscosity solution processing to realize the preparation of the chitosan loaded palladium chtalyst material of high activity porous spongy.
A first aspect of the present invention is to provide the chitosan loaded palladium chtalyst material of a kind of porous spongy for organic reaction catalysis, described catalysis material take shitosan as macromolecule carrier parent material, directly utilize palladium ion as crosslinking agent, obtain palladium cross-linked chitosan porous gel catalysis material, described catalysis material has open three-dimensional porous sponge shape structure, porosity 60-80%, active component palladium is the crosslinking points of gel network, and its mass percentage is less than or equal to catalysis material weight 1.5%.
Another aspect of the present invention is the preparation method of the chitosan loaded palladium chtalyst material of a kind of porous spongy, it is characterized in that comprising the following steps: (1) gets quantitative Chitosan powder, add the acetic acid solution of 2%, be made into the mixed solution that shitosan content (by weight) is 0.3-2%, leave standstill, deaeration, for subsequent use; (2) quantitative solid PdCl is got
2, adding distil water, then add NaCl, heating, stirring make it dissolve completely, Pd
2+concentration is 0.01-0.05mol/L; (3) under continuous stirring, in above-mentioned chitosan solution, Pd is dripped
2+solution, along with Pd
2+progressively adding of solution, solution viscosity raises gradually, until form gel; (4) this gel solution is cast in culture dish, be placed in low temperature refrigerator freezing, keep-20oC left and right 24h, (5) freezing gel solution is carried out freeze drying film forming by freeze drier, obtain palladium cross-linked chitosan porous gel catalysis material, through alkali immersion treatment with in and residual acid, finally wash oven dry, obtain final catalysis material.
Preferably:
The molecular weight ranges of the raw materials of chitosan used in described step (1): 50,000-20 ten thousand, deacetylation scope: 70%-98%.
Preferred, the molecular weight ranges of the raw materials of chitosan used in described step (1): 100,000, deacetylation scope: 95%.
The direct cross-linked chitosan molecule of transition metal palladium ion is utilized and without the need to additional chemical crosslinking Treatment, the addition of palladium ion is the 0-1.5% of vehicle weight in described step (3);
Utilize the chitosan complex palladium gel of freeze drier to sharp freezing to carry out freeze drying film forming in described step (5), in gel, solvent water molecules directly distils from solid and becomes gas and go out, and forms spongy three-dimensional porous material.
Compared with prior art, tool has the following advantages the chitosan loaded palladium chtalyst material of the porous spongy that the inventive method provides:
(1) preparation technology is simple, and equipment requirement is low.
(2) with the direct cross-linked chitosan molecule of transition metal palladium ion and without the need to additional chemical crosslinking Treatment, change the addition of shitosan initial solution concentration, transition metal palladium metal ion, the regulation and control to catalysis material performance (comprising pore structure, mechanical property etc.) can be realized.
(3) catalysis material has higher porosity, and palladium is the activated centre of material and the crosslinking points of material, is easy to isolated by filtration from reactant liquor after reaction.
(4) after reactant liquor being isolated reactor, without the need to numerous and diverse post processing, as long as simply to clean catalyst, after drying, rejoin reaction raw materials and can start new reaction.
accompanying drawing illustrates:
fig. 1for preparation technology's flow chart of catalysis material in the embodiment of the present invention 1.
fig. 2the outward appearance photo of the catalysis material prepared by the embodiment of the present invention 1.
detailed description of the invention:
The present invention is further illustrated below in conjunction with detailed description of the invention.
The preparation of embodiment 1 catalysis material
In the present embodiment, preparation technology's flow chart of catalysis material as shown in Figure 1, specifically comprises the following steps:
1, the preparation of shitosan weak solution: get pharmaceutical grade Chitosan powder (molecular weight 100,000, deacetylation is 95%) 1g, the 300ml acetum being dissolved in 2% is made into mixed solution, Keep agitation forms homogeneous phase solution, standing and defoaming 2h in 2 hours.
2, the preparation of the direct cross-linked chitosan gel of palladium ion: take 0.3g palladium bichloride, add 100ml distilled water, then add 5g sodium chloride in conical flask, heating, stirring make it dissolve completely and form Na
2pdCl
4solution; Appropriate Na is pipetted with pipette
2pdCl
4solution, under magnetic stirring, is dropwise added drop-wise in the above-mentioned shitosan weak solution of 100ml, when infusion volume is about 5ml, occurs critical gel point to system.
3, the preparation of porous spongy chitosan loaded palladium chtalyst material: be poured in culture dish by above-mentioned gel solution, the refrigerating chamber being placed in subzero 20oC freezes 24h; Then, take out the gel freezed, in FD-1A-50 type freeze drier, carry out freeze drying, obtain the chitosan loaded palladium chtalyst material of light yellow porous spongy; With residual acid in 1% sodium hydroxide solution and in removing material, with water rinse in neutral, dry, obtain final catalysis material.Fig. 2 is the outward appearance photo of catalysis material prepared in the present embodiment.
application example 1
The chitosan loaded palladium chtalyst material of porous spongy obtained by embodiment 1 is carried out to the application experiment of catalysis Heck reaction, its process and result as described below:
The Heck coupling reaction of porous spongy chitosan loaded palladium chtalyst material catalyzes halogenated aryl hydrocarbon and acrylic ester compound:
By test, at following reaction condition: iodobenzene 1mmol, butyl acrylate 2mmol, catalysis material 0.013g(palladium content is 0.0012mmol), KOAc7.5mmol, reaction dissolvent DMSO(or DMF) 3ml+ ethylene glycol 0.2ml, react 3h at 110oC, the productive rate of result butyl cinnamate is 97%; Catalyst reuses 6 times, and the productive rate of butyl cinnamate, all more than 80%, shows that this catalyst is functional, more stable in Heck reaction.
application example 2
The chitosan loaded palladium chtalyst material of porous spongy obtained by embodiment 1 is carried out to the application experiment of catalysis Sonogashira reaction, its process and result as described below:
The Sonogashira coupling reaction of porous spongy chitosan loaded palladium chtalyst material catalyzes halogenated aryl hydrocarbon and phenylacetylene compounds:
By test, at following reaction condition: iodobenzene 1mmol, phenylacetylene 1.2mmol, catalysis material 0.065g(palladium content is 0.006mmol), KOAc7.5mmol, reaction dissolvent DMSO(or DMF) 3ml+ ethylene glycol 0.2ml, react 6h at 110oC, the productive rate of result coupled product is 98%; Catalyst reuses 4 times, and coupling yield, all more than 80%, shows that this catalyst is functional, more stable in Sonogashira reaction.
Claims (6)
1. the chitosan loaded palladium chtalyst material of porous spongy, it is characterized in that, described catalysis material take shitosan as macromolecule carrier parent material, directly utilize palladium ion as crosslinking agent, obtain palladium cross-linked chitosan porous gel catalysis material, described catalysis material has open three-dimensional porous sponge shape structure, porosity 60-80%, active component palladium is the crosslinking points of gel network, and its mass percentage is less than or equal to 1.5% of catalysis material.
2. the preparation method of the chitosan loaded palladium chtalyst material of porous spongy a kind of as claimed in claim 1, it is characterized in that, comprise the following steps: (1) takes Chitosan powder in proportion, add the acetic acid solution of 2%, be made into the mixed solution that shitosan weight ratio is 0.5-4%, leave standstill, deaeration, for subsequent use; (2) take solid palladium chloride in proportion, adding distil water, then add sodium chloride, heating, stirring make it dissolve completely, Pd
2+concentration is 0.01-0.05mol/L; (3) under continuous stirring, in aforementioned chitosan solution, Pd is dripped
2+solution, until form gel; (4) gel solution obtained is cast in culture dish, be placed in low temperature refrigerator freezing, keep-20oC left and right 24h, (5) freezing gel solution is carried out freeze-drying film forming by freeze drier, obtain palladium cross-linked chitosan porous gel catalysis material, through alkali immersion treatment with in and residual acid, washing dry, obtain final catalysis material.
3. the preparation method of the chitosan loaded palladium chtalyst material of porous spongy according to claim 2, is characterized in that, the molecular weight ranges of shitosan: 50,000-20 ten thousand.
4. the preparation method of the chitosan loaded palladium chtalyst material of porous spongy according to claim 3, is characterized in that, the molecular weight ranges of shitosan: 100,000.
5. the preparation method of the chitosan loaded palladium chtalyst material of porous spongy according to claim 2, is characterized in that, the deacetylation scope of the shitosan used: 70%-98%.
6. the preparation method of the chitosan loaded palladium chtalyst material of porous spongy according to claim 2, is characterized in that, the deacetylation scope of the shitosan used: 95%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179452A (en) * | 2016-07-29 | 2016-12-07 | 绍兴文理学院 | A kind of preparation method of porous nitrogenous charcoal load palladium catalysis material |
| CN109364921A (en) * | 2018-10-31 | 2019-02-22 | 浙江理工大学 | A kind of catalyst for normal temperature and pressure catalysis Suzuki coupling reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030195277A1 (en) * | 1997-08-08 | 2003-10-16 | Risen William M. | Printing medium comprising aerogel materials |
| CN102019204A (en) * | 2010-11-19 | 2011-04-20 | 绍兴文理学院 | Chitosan-based porous microsphere load palladium catalyst, preparation method and application thereof |
-
2014
- 2014-06-23 CN CN201410281904.6A patent/CN105233877A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030195277A1 (en) * | 1997-08-08 | 2003-10-16 | Risen William M. | Printing medium comprising aerogel materials |
| CN102019204A (en) * | 2010-11-19 | 2011-04-20 | 绍兴文理学院 | Chitosan-based porous microsphere load palladium catalyst, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| MINFENG ZENG ET.AL.: "Novel macroporous palladium cation crosslinked chitosanmembranes for heterogeneous catalysis application", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179452A (en) * | 2016-07-29 | 2016-12-07 | 绍兴文理学院 | A kind of preparation method of porous nitrogenous charcoal load palladium catalysis material |
| CN106179452B (en) * | 2016-07-29 | 2018-10-23 | 绍兴文理学院 | A kind of preparation method of porous nitrogenous charcoal load palladium catalysis material |
| CN109364921A (en) * | 2018-10-31 | 2019-02-22 | 浙江理工大学 | A kind of catalyst for normal temperature and pressure catalysis Suzuki coupling reaction |
| CN109364921B (en) * | 2018-10-31 | 2021-07-13 | 浙江理工大学 | Catalyst for catalyzing Suzuki coupling reaction at normal temperature and pressure |
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