CN106582622A - Easy-recycling palladium-supporting modified montmorillonite catalyst preparation method and applications of easy-recycling palladium-supporting modified montmorillonite catalyst in Suzuki reaction - Google Patents
Easy-recycling palladium-supporting modified montmorillonite catalyst preparation method and applications of easy-recycling palladium-supporting modified montmorillonite catalyst in Suzuki reaction Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The present invention discloses an easy-recycling palladium-supporting modified montmorillonite catalyst preparation method and applications of the easy-recycling palladium-supporting modified montmorillonite catalyst in a Suzuki reaction. According to the preparation method, montmorillonite is modified, the palladium supporting amount is significantly improved, the method is simple, the required time is short (less than 5 h), and the method is suitable for industrial application. According to the present invention, the prepared palladium-supporting modified montmorillonite catalyst provides good catalysis performance for the Suzuki reaction, wherein the yields for the 17 substrates are more than 90%; and the palladium-supporting modified montmorillonite catalyst can be recovered through centrifugation or filtration and other methods so as to overcome the problem of the product pollution caused by the residual palladium due to the incapable recovery of the Suzuki reaction homogeneous palladium catalyst, the recovery process is simple, the control is easy, and the good application and promotion prospect is provided.
Description
Technical field
The invention belongs to catalysis material technical field, a kind of particularly load palladium modified montmorillonoid for being easy to recycle
The preparation method of catalyst and its application in Suzuki reactions.
Background technology
Since Suzuki and Miyaura et al. in 1979 are incorporated into preparation connection using boronic acid derivatives as nucleopilic reagent first
In the reaction of aromatic hydrocarbon, the Suzuki coupling reactions using palladium chtalyst organic boronic and aryl halides are designed, through nearly four
The development of 10 years, Suzuki reactions are gentle due to its reaction condition, have preferably compatibility, steric effect to various functional groups
Very little is affected, various substrates, the easily separated removing of by-product and low toxin is can be applicable to, it has also become biphenyl class chemical combination is built
One of thing, most important means of production medicine intermediate, by the C-C coupling reaction of palladium chtalyst some new senses are introduced
Group builds special molecular structure, is also the main path for designing and developing novel polymer material at present.
What Suzuki reactions were initially commonly used is the homogeneous catalysts such as palladium salt and palladium complex, although with dispersibility
Well, the advantages of high catalytic efficiency, excellent selectivity, but many parts are poisonous and unstable, and preparation process is complicated, and reaction condition is severe
Carve, and because catalyst reacts with reaction system in same phase, cause catalyst to separate difficult, expensive palladium can not be reclaimed
Utilize, the palladium of residual also can be polluted to product.Therefore, researcher is supported by catalyst, and preparation can be by simple mistake
Filter carrys out detached heterogeneous palladium catalyst.At present, many carriers such as mesoporous silicon, zeolite, material with carbon element, metal-oxide and polymer
The preparation of load type palladium catalyst has been applied to, but, all also there are some shortcomings in these materials, such as be mostly used in load
The porous polymer materials of palladium catalyst are required for specific process to synthesize, and preparation condition is harsh, and process is complicated, and some loaded articles are needed
Will successive reaction more than 48 hours in a nitrogen environment, this largely limits carrier material and moves towards practical application.Separately
Outward, due to the interaction between palladium and carrier material interface and insecure, can be because the loss of palladium cause catalysis after many secondary responses
Agent activity decrease is even inactivated, and has research to measure palladium stream after recycling seven times using porous polyimide loaded palladium catalyst
Lose 20%, reaction conversion ratio also drops to 82% from 98%, how the simple carrier material for preparing firm supported palladium
Become demand very urgent at present.
There is researcher using the unique layer structure of montmorillonite, huge specific surface area, good absorption property and ion
Exchange capacity, through it is appropriate it is modified can simply and efficiently load the silver that platinum family element is all with palladium, to methylene blue
Degraded serves good catalytic effect.But palladium is palladium belongs to the more inactive platinum group unit of chemical property in the race of period 5 VIII
Element, and alkalescence is significantly less than silver, easily hydrolyzes in ion exchange process, load in montmorillonite difficulty also above
Silver.How report is had no as the loaded catalyst of carrier material simple acquisition Suzuki reactions by the use of montmorillonite,
Therefore, a kind of preparation method of load palladium modified Montmorillonites for being easy to and recycling is developed and its in Suzuki reactions
Using very with practical value.
The content of the invention
It is an object of the invention to provide a kind of supported palladium and the load palladium for being easy to recycled for multiple times can be modified well
The preparation method of montmorillonite catalyst, and application of the load palladium modified Montmorillonites in Suzuki reactions is provided.
The technical solution used in the present invention is：
A kind of preparation method of the load palladium modified Montmorillonites for being easy to recycle, comprises the following steps：
(1) montmorillonite is dispersed in water, 50～70 DEG C of 0.5～2h of stirring are obtained concentration outstanding for 5～15g/L montmorillonites
Turbid liquid；
(2) 5～25g/L cystine acidic aqueous solution is mixed with montmorillonite suspension equal-volume obtained in step (1), pH
1.0～5.0,50～70 DEG C of 0.5～2h of stirring are adjusted to, cooling, filtration, washing are dried to constant weight, are ground to 100～300
Mesh, is obtained modified montmorillonoid；
(3) modified montmorillonoid obtained in step (2) is pressed the mass ratio of modified montmorillonoid and palladium ion in palladium salt aqueous solution
For (10～30):1 is added in palladium salt aqueous solution, and pH is adjusted to 1.0～5.0,50～70 DEG C of 0.5～1h of stirring, is subsequently placed at 150
React under the microwave power of～800W after 2～10min, cooling is filtered, washing is dried to constant weight, is ground to 100～300
Mesh, is obtained and carries palladium modified Montmorillonites.
Preferably, step (2) and the pH value described in step (3) are adjusted to 1.2～4.0.
Preferably, in step (3), microwave power is 225～750W.
Preferably, in step (3), the microwave reaction time is 2.5～5min.
Application of a kind of load palladium modified Montmorillonites for being easy to recycle in Suzuki reactions, including following step
Suddenly：
(1) a kind of load palladium modified Montmorillonites for being easy to recycle prepared using the method for claim 1, are added
In being added to Suzuki reaction systems；
(2) in Suzuki reaction systems, reaction substrate aryl bromide is 1 with aryl boric acid mol ratio:1～1.3, it is added
Aryl bromide is 1 with the mol ratio of alkali:1.9～2.1, solvent for use ethanol is 1 with the volume ratio of water:1, aryl bromide and ethanol
Molar ratio be 0.4～0.6mmol/mL, react in air atmosphere, reaction temperature be 40～80 DEG C, the response time 1～
4h；
(3) after reaction terminates, the described load palladium modified Montmorillonites of recycling step (1) add again after burning
To in the Suzuki reaction systems described in step (2), catalytic reaction is participated in.
Preferably, in step (3), cover de- using the described load palladium of the method recycling step (1) for filtering or being centrifuged is modified
Native catalyst.
Preferably, adding proportion the rubbing by its palladium consumption and reaction substrate aryl bromide of palladium modified Montmorillonites is carried
That ratio >=1:1000 additions.
Contain group R in the aryl bromide, the group R is 4-CHO, 4-COCH3、4-Cl、4-CN、4-NO2、2-CN
In one kind.
The aryl boric acid contains group R, and the group R is H, 2-CH3、4-CH3、2,4-CH3、2-OCH3、4-OCH3In
One kind.
Preferably, the aryl bromide is p-bromobenzaldehyde, and aryl boric acid is phenylboric acid, and alkali is K2CO3。
The invention has the beneficial effects as follows：
(1) present invention is modified to montmorillonite using cystine and is loaded under the conditions of pH is for 1.2～4.0 so as to
Loading to the palladium ion of modified montmorillonoid interlayer has good combination, carries palladium amount and is improved to 0.55wt% by 0.41wt%, and
Catalysis Suzuki reaction yields are more than 90%；
(2) the load palladium modified Montmorillonites preparation process for being easy to recycle of the invention is gentle, in normal temperature and pressure
Can complete under air conditionses, required time short (＜ 5 hours) is simple to operate, is suitable to industrial applications；
(3) the load palladium modified Montmorillonites for being easy to recycle prepared by the present invention have good to Suzuki reactions
Catalytic performance, be 1 in the mol ratio of palladium consumption and substrate:When 1000 17 kinds of substrates are obtained for the yield more than 90%；
(4) the load palladium modified Montmorillonites for being easy to recycle prepared by the present invention can be by centrifugation or filtration
Complete to reclaim etc. mode, wherein the catalyst recycling being recovered by filtration better (at least reusable edible 7 times), overcomes
Suzuki reactions homogeneous palladium catalysts can not be reclaimed, and the problem that the palladium of residual can be polluted to product, recovery process is simple, be held
It is easy to control, with good application and promotion prospect；
(5) preparation process of the load palladium modified Montmorillonites for being easy to recycle of the invention is discharged without " three wastes ",
And " green " catalysis material of category environment-friendly type.
Description of the drawings
Fig. 1：Carry the XPS figures of palladium modified Montmorillonites；
Fig. 2：The XRD figure of the load palladium modified Montmorillonites after brand-new and reaction once, wherein a is that brand-new load palladium is modified
Montmorillonite catalyst, b is to carry out the load palladium modified Montmorillonites after a catalytic reaction；
Fig. 3：The TEM figures of the load palladium modified Montmorillonites after reaction once.
Specific embodiment
With reference to specific embodiment, present invention is expanded on further.
Embodiment 1
The preparation process for carrying palladium modified Montmorillonites for being easy to recycle is as follows：
(1) 1g sodium-based montmorillonites (Na-MMT) and 100mL deionized waters are added in beaker, 1h is stirred at 60 DEG C, made
Obtain montmorillonite suspension；
(2) cystine of 1.9g and the deionized water of 100mL are added in another beaker, at 60 DEG C 0.1mol/L is added
HCl, cystine acidic aqueous solution is obtained；
(3) by montmorillonite suspension obtained in step (1) and cystine acidic aqueous solution obtained in step (2), pH is adjusted
It is worth for 2.0, at 60 DEG C 1h is stirred, be cooled to room temperature, after Medium speed filter paper sucking filtration, adds appropriate distilled water wash, subsequent 60
DEG C dry to constant weight, be ground to 200 mesh, obtain final product modified montmorillonoid (MMT)；
(4) MMT that 0.5g steps (3) are obtained is added in the palladium chloride aqueous solution of 10mL0.025mol/L, adjusts pH
It is worth for 2.0, at 60 DEG C 30min is stirred, be uniformly dispersed, in being placed in microwave generator, under 375W power 5min is reacted, is cooled to
Room temperature, after Medium speed filter paper sucking filtration, adds appropriate distilled water wash, and subsequent 60 DEG C dry to constant weight, are ground to 200 mesh, obtain
Palladium modified Montmorillonites are carried, Pd@MMT are designated as.
The performance characterization of the Pd@MMT that above-mentioned steps are prepared is as follows：
Fig. 1 is the XPS figures for carrying palladium modified Montmorillonites, it can be seen that palladium has successfully been supported on modified montmorillonoid
On.
Fig. 2 is brand-new and the XRD figure for carrying out the load palladium modified Montmorillonites after a catalytic reaction, and wherein a is new
System carries palladium modified Montmorillonites, and b is to carry out the load palladium modified Montmorillonites after a catalytic reaction, it can be seen that
B samples do not go out in 41.2 ° and 46.4 ° of diffraction maximums occurred in that respectively corresponding to the face of palladium crystal 111 and 200 faces, but a samples
It is existing, illustrate that the palladium ion being supported in catalytic reaction on modified montmorillonoid has been reduced into zeroth order simple substance palladium.
The TEM figures of the load palladium modified Montmorillonites after Fig. 3 reactions once, it can be seen that the list of a large amount of black particle shapes
Matter palladium, its size uniform is well dispersed.
Using the MMT of unmodified montmorillonite alternative steps (4), ICP measures palladium load capacity comparing result such as table 1 below institute
Show, it is seen that cystine acid modification montmorillonite (MMT) can effectively improve palladium load capacity.
The unmodified montmorillonite of table 1 and modified montmorillonoid load the correction data of palladium content
| Montmorillonite species | Load palladium content (wt%) |
| Unmodified montmorillonite | 0.41 |
| Modified montmorillonoid | 0.55 |
The Pd@MMT prepared using above-mentioned steps are tested the Suzuki reacting catalytic performances of different substrates,
The addition of Pd@MMT is 0.02g, and reaction condition is aryl bromide (1.0mmol), aryl boric acid (1.2mmol), K2CO3
(2.0mmol)、EtOH:H2O=2mL:2mL, air atmosphere, 65 DEG C of reaction temperature, response time 3h, reaction equation is as follows：
Yield data is as shown in table 2, it can be seen that the load palladium modified Montmorillonites pair prepared with the method for the present invention
Various substrates have good catalytic effect, and for yield during wherein 17 kinds of substrates 90% has been exceeded.
Table 2 carries the catalytic performance test that palladium modified Montmorillonites are reacted Suzuki
| Sequence number | R1 | R2 | Yield (%) |
| 1 | 4-CHO | H | 99 |
| 2 | 4-CHO | 2-CH3 | 89 |
| 3 | 4-CHO | 4-CH3 | 97 |
| 4 | 4-CHO | 2,4-CH3 | 96 |
| 5 | 4-CHO | 2-OCH3 | 97 |
| 6 | 4-COCH3 | H | 99 |
| 7 | 4-COCH3 | 2-CH3 | 85 |
| 8 | 4-COCH3 | 2,4-CH3 | 90 |
| 9 | 4-COCH3 | 2-OCH3 | 96 |
| 10 | 4-COCH3 | 4-OCH3 | 99 |
| 11 | 4-Cl | H | 99 |
| 12 | 4-Cl | 2-CH3 | 79 |
| 13 | 4-Cl | 4-CH3 | 94 |
| 14 | 4-Cl | 2,4-CH3 | 95 |
| 15 | 4-Cl | 2-OCH3 | 96 |
| 16 | 4-Cl | 4-OCH3 | 99 |
| 17 | 4-CN | H | 99 |
| 18 | 4-CN | 2-CH3 | 93 |
| 19 | 4-NO2 | H | 99 |
| 20 | 2-CN | H | 99 |
Embodiment 2
Change the power of microwave reaction and time in embodiment 1, other steps are constant, and obtained Pd@MMT are used for into benzene boron
The Suzuki reactions of acid and p-bromobenzaldehyde carry out catalysis activity test, and reaction condition is 1mmol p-bromobenzaldehydes, 1.2mmol
Phenylboric acid, 2mmol potassium carbonate, EtOH:H2O=2mL:2mL, 0.02g Pd@MMT, reaction temperature is 65 DEG C, and the response time is
3h。
Catalytic reaction yield data as shown in table 3, in same microwave power, when reacted between it is longer when, Suzuki is anti-
The yield answered is also higher；And at the identical response time, the yield of Suzuki reactions increases with the increase of microwave power
After reduce, under the response time of 375W and 5min, the Pd@MMT catalytic effect highests for obtaining.
The different microwave of table 3 and the catalytic performance that gained load palladium modified Montmorillonites are reacted Suzuki under the time
| Microwave power (W) | Response time (min) | Yield (%) |
| 225 | 2.5 | 95 |
| 375 | 2.5 | 97 |
| 750 | 2.5 | 92 |
| 225 | 5 | 97 |
| 375 | 5 | >99 |
| 750 | 5 | 94 |
Embodiment 3
Change the pH value adjusted in the step of embodiment 1 (3), (4), pH is respectively 1.2,2.0,2.5,3.0,4.0,5.0, will
Obtained Pd@MMT carry out the catalysis activity test described in same embodiment 2, and reaction condition and substrate consumption are constant.
As shown in table 4, the modified montmorillonoid prepared between 1.2～4.0 in pH is used to load catalytic reaction yield data
Catalytic effect is preferable during palladium, and yield is above 90%, and the catalytic effect of wherein pH2.0 and pH2.5 is optimal.
Gained modified montmorillonoid is carried after palladium to the catalytic performance of Suzuki reactions under the different pH condition of table 4
| PH value | Yield (%) |
| 1.2 | 96 |
| 2.0 | >99 |
| 2.5 | >99 |
| 3.0 | 93 |
| 4.0 | 90 |
| 5.0 | 83 |
Embodiment 4
The Pd@MMT preparation methoies of the present embodiment are carried out the Pd@MMT of different amounts described in same embodiment 2 with embodiment 1
Catalysis activity test, reaction condition and substrate consumption it is constant.
Gained yield data as shown in table 5, understands, when palladium consumption and substrate bromo with reference to the load palladium amount data that ICP is measured
The mol ratio of aromatic hydrocarbons is only 1:More than 99% yield is can reach when 1000, illustrates to carry palladium modified Montmorillonites pair
Suzuki reactions have very high catalytic effect.
Table 5 carries impact of the palladium modified Montmorillonites consumption to Suzuki reaction yields
Embodiment 5
The Pd@MMT preparation methoies of the present embodiment are centrifuged Pd@MMT by 4000r/min or with ashless with embodiment 1
The catalysis activity that the method circulation of recovery is burned after filter paper sucking filtration to be carried out described in same embodiment 2 is tested, and reaction condition and substrate are used
Amount is constant.
Gained yield data is as shown in table 6, it can be seen that after the catalyst that centrifugation is reclaimed recycles 4 times, single yield
It is less than 90%, it is more likely that huge centrifugal force causes the aggregation of palladium nanoparticles when being centrifugation, causes particle diameter to increase, and urges
Changing activity reduces；And the catalyst being recovered by filtration yield Jing after circulating 7 times remains above 90%, good reusability is shown
Energy.
Table 6 carries the circulation catalytic performance test of palladium modified Montmorillonites
| Cycle-index | Centrifugation recovery/yield (%) | / yield (%) is recovered by filtration |
| 1 | >99 | >99 |
| 2 | 99 | >99 |
| 3 | 99 | >99 |
| 4 | 90 | 96 |
| 5 | 50 | 95 |
| 6 | 30 | 92 |
| 7 | - | 90 |
Claims (10)
1. a kind of preparation method of the load palladium modified Montmorillonites for being easy to recycle, comprises the following steps：
（1）Montmorillonite is dispersed in water, 50～70 DEG C of 0.5～2 h of stirring, it is that 5～15g/L montmorillonites are suspended that concentration is obtained
Liquid；
（2）By 5～25g/L cystine acidic aqueous solution and step（1）Obtained montmorillonite suspension equal-volume mixing, pH is adjusted to
1.0～5.0,50～70 DEG C of 0.5～2h of stirring, cooling, filtration, washing are dried to constant weight, are ground to 100～300 mesh, are made
Obtain modified montmorillonoid；
（3）By step（2）Obtained modified montmorillonoid is with the mass ratio of palladium ion in palladium salt aqueous solution by modified montmorillonoid（10
～30）:1 is added in palladium salt aqueous solution, and pH is adjusted to 1.0～5.0,50～70 DEG C of 0.5～1h of stirring, is subsequently placed at 150～800
React under the microwave power of W after 2～10 min, cooling is filtered, washing is dried to constant weight, is ground to 100～300 mesh, is made
Palladium modified Montmorillonites must be carried.
2. it is according to claim 1 it is a kind of be easy to recycle load palladium modified Montmorillonites preparation method, its
It is characterised by：Step（2）And step（3）Described pH value is adjusted to 1.2～4.0.
3. it is according to claim 1 it is a kind of be easy to recycle load palladium modified Montmorillonites preparation method, its
It is characterised by：Step（3）In, microwave power is 225～750W.
4. it is according to claim 1 it is a kind of be easy to recycle load palladium modified Montmorillonites preparation method, its
It is characterised by：Step（3）In, the microwave reaction time is 2.5～5 min.
5. application of a kind of load palladium modified Montmorillonites for being easy to recycle in Suzuki reactions, including following step
Suddenly：
（1）A kind of load palladium modified Montmorillonites for being easy to recycle prepared using the method for claim 1, are added to
In Suzuki reaction systems；
（2）In Suzuki reaction systems, reaction substrate aryl bromide is 1 with aryl boric acid mol ratio:1～1.3, added bromo
Aromatic hydrocarbons is 1 with the mol ratio of alkali:1.9～2.1, solvent for use ethanol is 1 with the volume ratio of water:1, the body of aryl bromide and ethanol
Product mol ratio is 0.4～0.6 mmol/mL, is reacted in air atmosphere, and reaction temperature is 40～80 DEG C, 1～4h of response time；
（3）After reaction terminates, recycling step（1）Described load palladium modified Montmorillonites, be again added to after burning step
Suddenly（2）In described Suzuki reaction systems, catalytic reaction is participated in.
6. a kind of load palladium modified Montmorillonites for being easy to recycle according to claim 5 are in Suzuki reactions
Application, it is characterised in that：Step（3）In, using the method recycling step for filtering or be centrifuged（1）Described load palladium modified cover
De- soil catalyst.
7. a kind of load palladium modified Montmorillonites for being easy to recycle according to claim 5 are in Suzuki reactions
Application, it is characterised in that：The adding proportion of palladium modified Montmorillonites is carried by its palladium consumption and reaction substrate aryl bromide
Mol ratio >=1:1000 additions.
8. a kind of load palladium modified Montmorillonites for being easy to recycle according to claim 5 are in Suzuki reactions
Application, it is characterised in that：Contain group R in the aryl bromide, the group R is 4-CHO, 4-COCH3、4-Cl、4-CN、
4-NO2、One kind in 2-CN.
9. a kind of load palladium modified Montmorillonites for being easy to recycle according to claim 5 are in Suzuki reactions
Application, it is characterised in that：The aryl boric acid contains group R, and the group R is H, 2-CH3、4- CH3、2,4-CH3、2-
OCH3、4-OCH3In one kind.
10. a kind of load palladium modified Montmorillonites for being easy to recycle according to claim 5 react in Suzuki
In application, it is characterised in that：The aryl bromide is p-bromobenzaldehyde, and aryl boric acid is phenylboric acid, and alkali is K2CO3。
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| CN112679949A (en) * | 2019-10-18 | 2021-04-20 | 南京理工大学 | Conductive conjugated microporous polymer and preparation method thereof |
| CN111359660A (en) * | 2020-04-10 | 2020-07-03 | 蚌埠学院 | Method for preparing palladium-loaded polyimide nanosheet by microwave ionothermal method and application of palladium-loaded polyimide nanosheet in catalytic degradation of printing and dyeing wastewater |
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