CN108654691A - A kind of preparation method of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material - Google Patents
A kind of preparation method of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material Download PDFInfo
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- CN108654691A CN108654691A CN201810436115.3A CN201810436115A CN108654691A CN 108654691 A CN108654691 A CN 108654691A CN 201810436115 A CN201810436115 A CN 201810436115A CN 108654691 A CN108654691 A CN 108654691A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
The present invention relates to a kind of preparation methods of the polyvinyl pyrrolidone modified montmorillonite load palladium chtalyst material for organic reaction heterogeneous catalysis, belong to chemical catalyst fabricating technology field.The present invention includes the following steps：（1）Prepare the acetum of polyvinylpyrrolidone；（2）Prepare chlorine palladium acid sodium solution；（3）Montmorillonite/polyvinylpyrrolidone intercalation synthesis mixed system is prepared by solution intercalation；（4）Prepare polyvinylpyrrolidone intercalation modifying montmorillonite load palladium catalyst.A kind of preparation method of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material of the present invention had both remained montmorillonite matrix excellent solvent resistance energy, high thermal stability and stronger Molecular Adsorption performance; polyvinylpyrrolidonemacromolecule macromolecule is had both again, and excellent comprehensive performance is shown in organic catalytic reaction to the good complexing power and dimensionally stable effect, catalysis material of palladium nano-particles active component.
Description
Technical field
It is negative that the present invention relates to a kind of polyvinylpyrrolidone intercalation modifying montmorillonites for organic reaction heterogeneous catalysis
The preparation method for carrying palladium chtalyst material, belongs to catalyst material fabricating technology field.
Background technology
Transition metal palladium chtalyst organometallic coupling reaction is widely used in organic synthesis field, and catalytic process mainly has
Homogeneous catalysis and heterogeneous catalysis.Heterogeneous catalysis has benefited from, and catalyst is easy to product separation, transition metal remains in the product
Less, catalyst repeats the advantages that utilizing and is increasingly paid attention to by industry.The one of the preparation method of heterogeneous catalysis material
As process, be to load to transition metal active component in suitable inert solid material to be achieved.Montmorillonite is due to inexpensive
It is easy to get, is to prepare one of important carrier material of transition metal-catalyzed material the advantages that with good stability and adsorptivity,
But not modified montmorillonite matrix lacks polar group, has the characteristics that hydrophilic and oleophobic, the compatibility with organic molecule
It is relatively low, it is also not satisfactory with the complexation strength of transition metal.It is de- due to covering when being directly carrier loaded transition metal with montmorillonite
Interaction between soil and transition metal is weaker, causes transition metal during organic reaction to be lost in comparatively fast, can only recycle
Using 2-3 times, repeatability is bad（ Dutta,D.;Dutta,D.K.Appl.Catal.A:Gen.2014,487,158-1640）.
Polyvinylpyrrolidone（PVP）It is the high-molecular compound made of n-vinyl pyrrolidone homopolymerization, polyethylene
Methylene on pyrrolidone molecule main chain and side group pyrrolidone ring is non-polar group, has lipophile, side group pyrrolidines
Lactams on ketone ring is highly polar group, has hydrophilic and polar group effect.Itself can not only be used for transition metal nanometer
The stabilizer of particle also can be directly used for the carrier of transition-metal catalyst, but polyvinylpyrrolidone has thermal stability
The shortcomings of not high, solvent resistance and insufficient mechanical strength stability, drop easy to aging in the organic solvent of long-time higher temperature
Solution, transition metal are lost in seriously, and heterogeneous catalysis material made of the direct carrying transition metal of polyvinylpyrrolidone is caused to exist
In application, its to recycle number not high（Only 3 times）（Guo, L. P.; Li, C.P.; Meng, Q. R.; Liang,
H. O.; Sun, W. Y.; Li, H.Q., Liu H. Appl. Surf. Sci. 2013, 283, 107-114）.
It is the important means for improving material comprehensive performance that Organic-inorganic composite, which is modified,.Under certain condition, expanded by molecule
It dissipates, the multilayer that polyvinylpyrrolidone extended chain molecule may be implemented in the silicate crystal interlayer of montmorillonite with layered form is inserted
Enter, with this composite material for carrier loaded palladium, the polyvinylpyrrolidone intercalation modifying illiteracy that can prepare excellent combination property is de-
Native load palladium catalysis material.
Based on this, proposing the present invention.
Invention content
The object of the present invention is to provide a kind of systems of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material
Preparation Method, using montmorillonite as matrix, polyvinylpyrrolidone serves as intercalation modifying agent and transition metal complex agent, polyethylene pyrrole
Pyrrolidone and montmorillonite are combined closely as the advantages of transition-metal catalyst carrier, are changed by the intercalation synthesis of the two
Property, then complexes ira situ transition metal palladium ion, novel polyethylene pyrrolidones intercalation modifying montmorillonite load palladium chtalyst material is made
Material；Catalysis material obtained had both remained montmorillonite matrix excellent solvent resistance energy, high thermal stability and stronger molecule and had inhaled
The advantages that attached performance, and polyvinylpyrrolidonemacromolecule macromolecule is had both to the good complexing power of transition metal, received to transition metal
Rice corpuscles has the characteristics of being acted on compared with stiff stability, and excellent comprehensive performance is shown in organic catalytic reaction.
In order to achieve the above objectives, the present invention is achieved by the following technical solutions：
1, a kind of preparation method of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material, includes the following steps：
（1）It is stirred at room temperature under state, it is system in 1-2wt% dilute acetic acid solutions that polyvinylpyrrolidone, which is dissolved in weight percent,
Standby polyvinylpyrrolidone dilute acetic acid solution, it is spare；
（2）It is stirred at room temperature under state, it is to prepare chlorine palladium acid sodium water in 2% sodium-chloride water solution that palladium bichloride, which is dissolved in mass fraction,
Solution, it is spare；
（3）Under 50 °C of -60 °C of heating water bath states, montmorillonite is dispersed in water, magnetic agitation 2h, it is suspended to prepare montmorillonite
Liquid takes step（1）Obtained polyvinylpyrrolidone dilute acetic acid solution is slowly added in montmorillonite suspension, persistently stirs 12h,
So that the abundant intercalation of polyvinylpyrrolidonemolecules molecules is entered between cheating engaging layer, it is multiple to obtain montmorillonite/polyvinylpyrrolidone intercalation
Close suspension；
（4）Under continuous stirring, to step（3）In obtained montmorillonite/polyvinylpyrrolidone intercalation synthesis suspension, it is added dropwise
Step（2）Obtained chlorine palladium acid sodium solution continues to be stored at room temperature after stirring 12h, then be washed with deionized water high speed centrifugation, done
It is dry, then spent glycol reduction activation, 60 °C dry, and obtain using the montmorillonite of polyvinylpyrrolidone intercalation modifying as the load of carrier
Type palladium chtalyst material；
The step（1）In, polyvinylpyrrolidone weight content is 0.5-1.2.
The step（2）In, palladium bichloride accounts for a concentration of 0.3-0.6% of chlorine palladium acid sodium aqueous solution.
The step（3）In, the weight percent of montmorillonite and water is 1.8-2.1wt%.
The step（3）In, the mass ratio of montmorillonite and polyvinylpyrrolidone is 4/1-3/2；
The step（4）In, the mass ratio of montmorillonite/polyvinylpyrrolidone intercalation synthesis suspension and chlorine palladium acid sodium solution is
（405-406）：4.
During solution intercalation, the solvent molecule between polyvinylpyrrolidonemolecules molecules and cheating engaging layer exchanges, into
The interlayer for entering cationic montmorillonite, in order to utmostly interact with the formation of montmorillonite silicate surfaces hydroxyl, polyethylene
Between pyrrolidone molecule is inserted into cheating engaging layer in the form of stretching chain configuration stratiform, multilaminar polyethylene pyrrolidone molecule is inserted
Enter to make the interlamellar spacing of montmorillonite to greatly increase, transition metal ions is exchanged by cation and gathering between insertion cheating engaging layer
Load is realized in the complexing of vinylpyrrolidone molecule direct in-situ, obtains having excellent synthesis after centrifugation, washing, drying, activation
The polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material Pd@MMT/PVP of performance, in organometallic coupling reaction application
In have good comprehensive performance.
The polyvinylpyrrolidone is the intercalator of montmorillonite, and the network that polyvinylpyrrolidone is transition metal palladium
Mixture.
A kind of preparation method of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material of the present invention was both protected
The advantages that having stayed montmorillonite matrix excellent solvent resistance energy, high thermal stability and stronger Molecular Adsorption performance, and have both poly-
Vinylpyrrolidone macromolecule is to the good complexing power and dimensionally stable effect of palladium nano-particles active component, Pd nano particle
It is securely mixed in the interlayer of montmorillonite and polyvinylpyrrolidonemolecules molecules, catalysis material shows excellent in organic catalytic reaction
Comprehensive performance.
The preparation method of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material of the present invention has and has as follows
Beneficial effect：
1, preparation process is simple, and equipment requirement is low；
2, the advantages of macromolecule carrier and inorganic carrier, is preferably combined together, has both remained polyvinylpyrrolidone high score
Son to the good complexing power of transition metal, and have both montmorillonite matrix excellent solvent resistance energy, higher thermal stability and compared with
The advantages that strong Molecular Adsorption performance.
3, be inserted into cheating engaging layer between the polyvinylpyrrolidonemolecules molecules number of plies number, with cheating engaging layer spacing after intercalation
Size can carry out modulation by adjusting the mass ratio of montmorillonite and polyvinylpyrrolidone.Montmorillonite is through the poly- second of multilayer
After the effective intercalation modifying of alkene pyrrolidone molecule, the excellent carriers of palladium metal can be become.The Pd@MMT/PVP catalysis materials of preparation
In, transition metal nanoparticles are mixed in the interlayer of montmorillonite and polyvinylpyrrolidonemolecules molecules, and have stronger interaction,
Excellent catalytic activity and stability are shown in reactive applications..
4, after reaction solution being isolated reactor, it is not necessarily to complicated post-processing, as long as to catalyst simply clean, doing
After dry, new reaction can be started by rejoining reaction raw materials.
Description of the drawings
Fig. 1 is the X-ray powder diffraction figure of Pd@MMT/PVP made from the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope schematic diagram of Pd@MMT/PVP made from the embodiment of the present invention 1.
Specific implementation mode
With reference to example, the invention will be further described, and the present invention is not limited to following embodiments.
Embodiment 1
（1）Weigh 1g polyvinylpyrrolidones（K30, molecular weight 40000）, it is added in 200 grams of 2wt% spirit of vinegars, is made into poly- second
The dilute acetic acid solution that alkene pyrrolidone weight content is 0.5%, it is spare；
（2）0.15g solid palladium chlorides are weighed, are dissolved in 50 gram of 2% sodium chloride solution, chlorine palladium acid sodium solution is made into, it is spare；
（3）4g sodium form cation montmorillonites are weighed, 200mL distilled water is added, 50 °C of heating water baths are mixing uniformly to form 2% illiteracy
De- soil suspension, then step（1）Obtained polyvinylpyrrolidone dilute acetic acid solution is slowly added in montmorillonite suspension, after
Continuous stirring 12 hours, makes the abundant intercalation of PVP molecules enter MMT interlayers, obtains MMT/PVP mixing suspensions；
（4）Under continuous stirring, to step（3）In obtained MMT/PVP mixing suspensions, 4 grams of steps are added dropwise（2）Obtain chlorine palladium
Acid sodium solution continues to be stored at room temperature after stirring 12h, then be washed with deionized water high speed centrifugation, dry, then spent glycol reduction
Activation, 60 °C of drying, obtains the load type palladium catalysis material Pd@using the montmorillonite of polyvinylpyrrolidone intercalation modifying as carrier
MMT/PVP。
Application Example 1
Physical property table is carried out to the polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material obtained by above-described embodiment 1
The application experiment reacted with catalysis Heck is levied, process and result are as described below：
（1）Such as Fig. 1, for X-ray powder diffraction the results show that the interlamellar spacing of MMT/PVP carriers is 2.09nm, consideration MMT original soils are brilliant
Lamellar spacing 0.96nm and PVP molecular layers thick about 0.5nm illustrate that 2 layers of PVP molecules enter MMT interlayers, interlamellar spacing after supported palladium
It is increased slightly to 2.48 nm, illustrates that palladium component enters MMT interlayers；As the transmission electron microscope results of Fig. 2, Pd@MMT/PVP show
Most of palladium Active components distributions are acted synergistically with MMT wafer layers and stablized immobilized by PVP molecular layers in the interlayer of MMT.
（2）Polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material is catalyzed halogenated aryl hydrocarbon and esters of acrylic acid
The Heck coupling reactions of compound：
By experiment, in following reaction condition：Iodobenzene 1mmol, butyl acrylate 2mmol, the catalysis material that embodiment 1 obtains
0.18g (about 3 μm of ol of palladium content), potassium acetate 3 mmol, reaction dissolvent DMSO（Or DMF）5ml+ ethylene glycol 0.2ml, at 110 °
C reacts 5h, and as a result the yield of butyl cinnamate is 94%；After the completion of the catalysis material reaction of embodiment 1, it is separated by filtration, uses ethyl alcohol
Washing 3 times, drying re-use the catalysis reaction for carrying out equal conditions, and product yield 95% can continue to repeat to apply mechanically, the 10th
Secondary reaction yield 67% shows this catalyst excellent combination property in Heck reactions.
Embodiment 2
（1）Weigh 1.8g polyvinylpyrrolidones（K30, molecular weight 40000）, it is added in 200 grams of 2wt% spirit of vinegars, is made into poly-
The dilute acetic acid solution that vinylpyrrolidone weight content is 0.9%, it is spare；
（2）0.3g solid palladium chlorides are weighed, are dissolved in 50 gram of 2% sodium chloride solution, chlorine palladium acid sodium solution is made into, it is spare；
（3）4.2g sodium form cation montmorillonites are weighed, 200mL distilled water is added, 50 °C of heating water baths are mixing uniformly to form
2.1% montmorillonite suspension, then step（1）It is suspended that obtained polyvinylpyrrolidone dilute acetic acid solution is slowly added to montmorillonite
In liquid, continues stirring 12 hours, so that the abundant intercalation of PVP molecules is entered MMT interlayers, obtain MMT/PVP mixing suspensions；
（4）Under continuous stirring, to step（3）In obtained MMT/PVP mixing suspensions, 4 grams of steps are added dropwise（2）Obtain chlorine palladium
Acid sodium solution continues to be stored at room temperature after stirring 12h, then be washed with deionized water high speed centrifugation, dry, then spent glycol reduction
Activation, 60 °C of drying, obtains the load type palladium catalysis material Pd@using the montmorillonite of polyvinylpyrrolidone intercalation modifying as carrier
MMT/PVP。
Application Example 2
Physical property table is carried out to the polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material obtained by above-described embodiment 2
The application experiment reacted with catalysis Heck is levied, process and result are as described below：
（1）X-ray powder diffraction the results show that MMT/PVP carriers interlamellar spacing be 2.51nm, illustrate about 3 layers of PVP molecules into
Enter MMT interlayers, after Pd@MMT/PVP catalysis materials are made in supported palladium, active palladium component is cooperateed with by PVP molecular layers with MMT wafer layers
It acts on and stablizes immobilized.
（2）Polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material is catalyzed halogenated aryl hydrocarbon and esters of acrylic acid
The Heck coupling reactions of compound：
By experiment, in following reaction condition：Iodobenzene 1mmol, butyl acrylate 2mmol, the catalysis material that embodiment 2 obtains
0.18g (about 6 μm of ol of palladium content), potassium acetate 3 mmol, reaction dissolvent DMSO（Or DMF）5ml+ ethylene glycol 0.2ml, at 110 °
C reacts 5h, and as a result the yield of butyl cinnamate is 98%；After the completion of the catalysis material reaction of embodiment 2, it is separated by filtration, uses ethyl alcohol
Washing 3 times, drying re-use the catalysis reaction for carrying out equal conditions, and the reaction yield that repetition applies mechanically the 10th time is higher than
70%。
Embodiment 3
（1）Weigh 1.2 g polyvinylpyrrolidones（K30, molecular weight 40000）, it is added in 100 grams of 2wt% spirit of vinegars, is made into
The dilute acetic acid solution that polyvinylpyrrolidone weight content is 1.2%, it is spare；
（2）0.15g solid palladium chlorides are weighed, are dissolved in 50 gram of 2% sodium chloride solution, chlorine palladium acid sodium solution is made into, it is spare；
（3）1.8g sodium form cation montmorillonites are weighed, 100mL distilled water is added, 50 °C of heating water baths are mixing uniformly to form
1.8% montmorillonite suspension, then step（1）It is suspended that obtained polyvinylpyrrolidone dilute acetic acid solution is slowly added to montmorillonite
In liquid, continues stirring 12 hours, so that the abundant intercalation of PVP molecules is entered MMT interlayers, obtain MMT/PVP mixing suspensions；
（4）Under continuous stirring, to step（3）In obtained MMT/PVP mixing suspensions, 2 grams of steps are added dropwise（2）Obtain chlorine palladium
Acid sodium solution continues to be stored at room temperature after stirring 12h, then be washed with deionized water high speed centrifugation, dry, then spent glycol reduction
Activation, 60 °C of drying, obtains the load type palladium catalysis material Pd@using the montmorillonite of polyvinylpyrrolidone intercalation modifying as carrier
MMT/PVP。
Application Example 3
Physical property table is carried out to the polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material obtained by above-described embodiment 3
The application experiment reacted with catalysis Heck is levied, process and result are as described below：
（1）X-ray powder diffraction the results show that MMT/PVP carriers interlamellar spacing be 3.10nm, illustrate about 4 layers of PVP molecules into
Enter MMT interlayers, after Pd@MMT/PVP catalysis materials are made in supported palladium, active palladium component is cooperateed with by PVP molecular layers with MMT wafer layers
It acts on and stablizes immobilized.
（2）Polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material is catalyzed halogenated aryl hydrocarbon and esters of acrylic acid
The Heck coupling reactions of compound：
By experiment, in following reaction condition：Iodobenzene 1mmol, butyl acrylate 2mmol, the catalysis material that embodiment 3 obtains
0.18g (about 3 μm of ol of palladium content), potassium acetate 3 mmol, reaction dissolvent DMSO（Or DMF）5ml+ ethylene glycol 0.2ml, at 110 °
C reacts 5h, and as a result the yield of butyl cinnamate is 92%；After the completion of the catalysis material reaction of embodiment 3, it is separated by filtration, uses ethyl alcohol
Washing 3 times, drying re-use the catalysis reaction for carrying out equal conditions, and the reaction yield that repetition applies mechanically the 10th time is higher than
60%。。
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 for carrying out unsubstantiality to the present invention using this design, should all fall into protection scope of the present invention.
Claims (6)
1. a kind of preparation method of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material, it is characterised in that including
Following steps：
（1）It is stirred at room temperature under state, it is system in 1-2wt% dilute acetic acid solutions that polyvinylpyrrolidone, which is dissolved in weight percent,
Standby polyvinylpyrrolidone dilute acetic acid solution, it is spare；
（2）It is stirred at room temperature under state, it is to prepare chlorine palladium acid sodium water in 2% sodium-chloride water solution that palladium bichloride, which is dissolved in mass fraction,
Solution, it is spare；
（3）Under 50 °C of -60 °C of heating water bath states, montmorillonite is dispersed in water, magnetic agitation 2h, it is suspended to prepare montmorillonite
Liquid takes step（1）Obtained polyvinylpyrrolidone dilute acetic acid solution is slowly added in montmorillonite suspension, persistently stirs 12h,
So that the abundant intercalation of polyvinylpyrrolidonemolecules molecules is entered between cheating engaging layer, it is multiple to obtain montmorillonite/polyvinylpyrrolidone intercalation
Close suspension；
（4）Under continuous stirring, to step（3）In obtained montmorillonite/polyvinylpyrrolidone intercalation synthesis suspension, it is added dropwise
Step（2）Obtained chlorine palladium acid sodium solution continues to be stored at room temperature after stirring 12h, then be washed with deionized water high speed centrifugation, done
It is dry, then spent glycol reduction activation, 60 °C dry, and obtain using the montmorillonite of polyvinylpyrrolidone intercalation modifying as the load of carrier
Type palladium chtalyst material.
2. a kind of preparation side of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material as described in claim 1
Method, it is characterised in that：The step（1）In, polyvinylpyrrolidone weight content is 0.5-1.2.
3. a kind of preparation side of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material as described in claim 1
Method, it is characterised in that：The step（2）In, palladium bichloride accounts for a concentration of 0.3-0.6% of chlorine palladium acid sodium aqueous solution.
4. a kind of preparation side of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material as described in claim 1
Method, it is characterised in that：The step（3）In, the weight percent of montmorillonite and water is 1.8-2.1wt%.
5. a kind of preparation side of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material as described in claim 1
Method, it is characterised in that：The step（3）In, the mass ratio of montmorillonite and polyvinylpyrrolidone is 4/1-3/2.
6. a kind of preparation side of polyvinylpyrrolidone intercalation modifying montmorillonite load palladium chtalyst material as described in claim 1
Method, it is characterised in that：The step（4）In, montmorillonite/polyvinylpyrrolidone intercalation synthesis suspension and chlorine palladium acid sodium solution
Mass ratio be（405-406）：4.
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| CN110591442A (en) * | 2019-09-12 | 2019-12-20 | 浙江工业大学之江学院 | Preparation method of water-based thickening agent |
| CN114656731A (en) * | 2022-04-25 | 2022-06-24 | 广东中讯通讯设备实业有限公司 | High-rigidity PVC (polyvinyl chloride) power conduit and preparation method thereof |
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| CN107349930A (en) * | 2017-07-19 | 2017-11-17 | 盐城锦明药业有限公司 | A kind of platinum attapulgite clay nano supported catalyst and its preparation method and application |
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| CN106345529A (en) * | 2016-07-29 | 2017-01-25 | 绍兴文理学院 | Method for preparing palladium catalytic materials supported by chitosan-modified montmorillonite |
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| CN114656731A (en) * | 2022-04-25 | 2022-06-24 | 广东中讯通讯设备实业有限公司 | High-rigidity PVC (polyvinyl chloride) power conduit and preparation method thereof |
| CN114656731B (en) * | 2022-04-25 | 2022-09-20 | 广东中讯通讯设备实业有限公司 | High-rigidity PVC (polyvinyl chloride) power conduit and preparation method thereof |
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