CN114181716B - Gas response type Pickering emulsifier, preparation method and application thereof in Suzuki reaction - Google Patents
Gas response type Pickering emulsifier, preparation method and application thereof in Suzuki reaction Download PDFInfo
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Abstract
A gas response Pickering emulsifier, a preparation method and application thereof in Suzuki reaction. Adding the prepared gas response type Pickering emulsifier into a system consisting of an inorganic alkali solution water phase and an oil phase and having different oil-water proportions, and emulsifying for 1-3 min by using a high-speed shearing machine in an ultrasonic manner to obtain Pickering emulsion; introducing CO into the Pickering emulsion at 5deg.C 2 Breaking emulsion drop, and introducing N at 50deg.C 2 The emulsion can be obtained after stirring by a high-speed shearing machine. The method has the advantages of effectively reducing interface mass transfer resistance and improving reaction interface area.
Description
Technical Field
The application belongs to the field of functional materials, relates to a colloid interface material, and particularly relates to a preparation method of a gas response Pickering emulsifier and application of the gas response Pickering emulsifier in a Suzuki (coupling) reaction.
Background
Palladium (Pd) catalyzed aryl boric acid and halogenated aromatic hydrocarbon are subjected to Suzuki cross coupling reaction to prepare biaryl compounds,is one of the most important organic unit reactions for constructing C-C bonds. However, the reaction faces large mass transfer resistance of the water-organic two-phase interface in practical application (Na is needed to be added in the reaction 2 CO 3 Or K 2 CO 3 And the like to promote the metal transfer process to occur and ensure the reaction to be carried out smoothly) and the catalytic reaction system is difficult to recycle rapidly. To solve this problem, the current research has been to take H 2 O/C 2 H 5 OH、H 2 O/DMF and H 2 Co-solvent systems such as O/DMAc assist mechanical agitation or add phase transfer agents to the system, however, the system faces the problem of complex product isolation and purification processes. Therefore, new materials and catalyst systems are developed to solve the problems of interfacial mass transfer and rapid reaction circulation in the Suzuki coupling reaction.
The Pickering emulsion interface catalytic reaction system (Pickering Interfacial Catalysis, PIC) constructed by stabilizing water-organic two phases by solid particles with special surface activity has the advantages of high activity, easy recovery of the catalyst and the like, and gradually becomes an effective strategy for reducing the mass transfer resistance of the water-organic two-phase interface. Pd/SiO was first prepared from Resasco et al 2010 (Crosssley S, faria J, shen M, resasco DE.solid nanoparticles that catalyze biofuel upgrade reactions at the water/oil interface.science 2010,327 (5961):68-72.) 2 Emulsion catalysts are used in hydrogenation reactions, and PIC systems have been rapidly developed over a decade, and are currently used in the synthesis and biocatalytic reactions of various fine chemicals.
Based on the urgent need of rapid green circulation of the catalytic system, scholars at home and abroad perform the exploring work of constructing a responsive Pickering emulsion catalytic system. For example, yang et al (Yang H, zhou T, zhang W. Astragy for separating and recycling solid catalysts based on the pH-triggered Pickering-email version.Angewandte Chemie International Edition 2013,52 (29): 7455-7459.) are based on SiO 2 The basic principle that the surface functionalized amino functional group can be protonated/deprotonated under the acid/alkali condition is designed and prepared into a carrier material with pH response property, which is used for the selective hydrogenation water-organic two-phase reaction of styrene, and realizes the catalytic system in acid/alkaliRapid cycling under conditions. Compared with other reported responsive emulsions (pH responsive, light responsive, temperature responsive, etc.), CO 2 Responsive emulsions have been first introduced by jessap et al (jessap PG, heldebrant DJ, li X, eckert CA, liotta cl. Reversible non-npolarar-to-polar solvent 2005,436 (7054):1102-1102.) because of their green, inexpensive availability, good biocompatibility, accumulation of salt-free solutions (NaCl due to pH adjustment, etc.). Thus CO is converted into 2 The responsive emulsion catalyst is used for water-organic two-phase reaction, the catalyst is not required to be filtered and recycled after the reaction is finished, and the quick green circulation of the reaction can be realized by directly demulsification, pouring of an organic phase and emulsification by adding of reactants, so that the catalyst has important application prospect.
However, how to provide a device with the function of converting CO 2 Or other gas responsive emulsions and can be used in Suzuki cross-coupling reactions, no relevant report is currently available.
Disclosure of Invention
The application aims at the defects of the prior art, and provides a gas response type Pickering emulsifier which can effectively reduce interface mass transfer resistance and improve reaction interface area.
In order to solve the technical problems, the application adopts the following technical scheme: a gas-responsive Pickering emulsifier having gas-responsive properties formed from tertiary amine-modified Graphene Oxide (GO).
The tertiary amine modified graphene oxide is prepared by an improved Hummers method; this is due to the use of NaNO by the conventional Hummers method 3 As one of the oxidants, toxic gases are generated. In view of the above, the method is improved, and GO with rich functional groups and easier regulation of surface chemical properties is prepared by a greener method.
More specifically, the specific process for preparing GO by the improved Hummers method is as follows: mixing graphite powder with H 3 PO 4 Adding into concentrated H 2 SO 4 Placing the mixture in an ice-water bath for stirring until graphite powder and H are obtained 3 PO 4 Fully dissolveAfter the decomposition, the KMnO which is ground in advance is adopted 4 Adding the powder into the system at a constant speed; transferring the reaction solution into a water bath, slowly adding deionized water into the reaction solution, continuously stirring, transferring the solution into a hot water bath, stirring again, adding deionized water and frozen hydrogen peroxide into the system after the reaction is finished to remove the unreacted and complete KMnO4, obtaining a GO solution, standing and centrifuging the product to obtain a neutral GO dispersion, and freeze-drying the GO dispersion for later use.
Preferably, the preparation process of the emulsifier formed by tertiary amine modified Graphene Oxide (GO) comprises the following steps: the preparation process comprises the following steps: dispersing graphene oxide in NaOH solution, adding a tertiary amine compound modifier into the graphene oxide, modifying GO, and treating for 2-4 hours at 65-75 ℃; and (3) centrifuging, freezing and drying the treated sample in vacuum to obtain the Pickering emulsifier with the gas response.
Further, the mass ratio of GO to NaOH is 1:10-11; the mass ratio of the tertiary amine compound to the graphite oxide is 0.2-0.5: 1.
preferably, the tertiary amine compound modifier is one of N, N-dimethyl ethylenediamine, N-diethyl ethylenediamine, 3-dimethyl aminopropylamine, 3-diethyl aminopropylamine, 4-dimethyl aminoputylamine and 4-diethyl aminoputylamine.
The application also provides a preparation method of the gas response type Pickering emulsion, which comprises the following steps: adding the prepared gas response type Pickering emulsifier into a system consisting of an inorganic alkali solution water phase and an oil phase and having different oil-water proportions, and emulsifying for 1-3 min by using a high-speed shearing machine in an ultrasonic manner to obtain the Pickering emulsion.
Preferably, the type of Pickering emulsion is O/W type (oil-in-water type), and the volume fraction of the emulsion is 50% -100%.
Preferably, the oil phase: the volume ratio of the water phase is 1-3:1.
Preferably, the mass/total solution volume of the solid material in the Pickering emulsion is 0.25-3.0 mg/mL.
Further, introducing CO into the Pickering emulsion at 5 DEG C 2 Breaking emulsion drop, and introducing N at 50deg.C 2 The emulsion can be obtained after stirring by a high-speed shearing machine.
Further, the aqueous phase of the application is Na 2 CO 3 ，NaHCO 3 、K 2 CO 3 、KHCO 3 、NaOH、KOH、 Cs 2 CO 3 、K 3 PO 4 、Na 3 PO 4 、CH 3 COOK、Li 2 CO 3 One of the inorganic alkaline solutions, the oil phase is one of toluene, alkane or ionic liquid and other water-insoluble organic matters; inorganic base is used as an auxiliary agent.
Furthermore, the oil-water ratio system of the application also contains tetra (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) As a catalyst.
Further, the oil phase is one of halogenated benzene or halogenated benzene derivatives and one of phenylboronic acid or phenylboronic acid derivatives, and is used as reactants.
Further, the halogenated benzene comprises one of chlorobenzene, bromobenzene and iodobenzene, and the halogenated benzene derivative comprises one of p-nitrobromobenzene, p-methyl bromobenzene, p-hydroxy bromobenzene, 4-methoxyiodobenzene, 4-formyliodobenzene, 4-methyl iodobenzene, p-nitroiodobenzene, p-hydroxy iodobenzene and bromonaphthalene.
Further, the phenylboronic acid derivative comprises one of 4-methoxyphenylboronic acid, 4-formylphenylboronic acid, 2-methoxyphenylboronic acid, 2-methylphenylboronic acid and 4-methylphenylboronic acid.
Furthermore, the molar ratio of the halogenated benzene or the derivative thereof to the phenylboronic acid or the derivative thereof is 1.5-2:1, the temperature of the Suzuki coupling reaction is 65-95 ℃, and the reaction time is 2-8 hours.
The application also provides application of the GO modified by the tertiary amine as a particle emulsifier of an oil-in-water (O/W) Pickering emulsion. Compared with the traditional granular emulsifying agent such as inorganic particles, the emulsion formed by the emulsifying agent has larger interfacial area (80-180 m 2 /g) and smaller droplet (29-50 μm) size. Due to the large boundaryThe contact area between the reactant and the catalyst is increased in the reaction system with smaller surface area and smaller emulsion droplet size, so that the mass transfer resistance is effectively reduced, the reaction efficiency is improved, and the reaction is more facilitated. .
The application also provides application of Pickering emulsion taking the GO modified by the tertiary amine as a particle emulsifier in the Suzuki reaction, wherein the product conversion rate in the Suzuki reaction is more than 99%.
The application has the advantages and beneficial effects that:
1. the application provides a Pickering emulsifier which can be applied to a Suzuki reaction for the first time, wherein the emulsifier is tertiary amine modified Graphene Oxide (GO) prepared by adopting a one-step method, and the emulsifier is applied to the Suzuki reaction; the Pickering emulsifier has CO 2 /N 2 The responsiveness is suitable for various oil-water systems and Suzuki coupled reaction systems, and has good stabilizing effect on emulsion under alkaline conditions.
2. According to the application, GO is used as a basic structural unit for the first time, a Pickering emulsifier capable of forming a high emulsion interface area is constructed, and a novel method is provided for solving the problem of interface mass transfer in the Suzuki coupling reaction. Can be obtained by simple CO after the reaction is completed 2 The gas is introduced to realize the rapid separation of oil water and products, so that the separation efficiency of the products is greatly improved, the separation difficulty of the products is reduced, and the emulsion formed by the emulsifier is basically unchanged in performance after being recycled for a plurality of times.
3. Compared with the traditional granular emulsifying agent such as inorganic particles, the emulsion formed by the emulsifying agent has larger interfacial area (80-180 m 2 /g) and smaller droplet (29-50 μm) size. The contact area between the reactant and the catalyst is increased due to the reaction system with larger interface area and smaller emulsion droplet size, so that the mass transfer resistance is effectively reduced, the reaction efficiency is improved, and the reaction is more facilitated.
Drawings
FIG. 1 is a graph of the cyclic response of the Pickering emulsion breaking/emulsifying in example 7.
FIG. 2 is a digital photograph of Pickering emulsions formed at different oil-to-water ratios in example 8.
Detailed Description
The following examples are only preferred embodiments of the present application and are not intended to limit the present application in any way. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Example 1
Preparation of GO-based Pickering emulsifier modified by tertiary amine
Preparation of GO: preparation of 5g graphite powder and 2.85. 2.85g H 3 PO 4 It was added to 130mL of concentrated H 2 SO 4 Placing the mixture in an ice-water bath, stirring for 2H until the graphite powder and H are mixed 3 PO 4 After sufficient dissolution, 15g KMnO was previously ground 4 Slowly adding the powder into the system (3 h is completed at a constant speed, and the temperature of the reaction system is maintained at 0-5 ℃). The reaction solution was transferred to a 35℃water bath, and 230mL of deionized water was slowly added thereto, followed by stirring for 1 hour. The stirred solution was transferred to a 98 ℃ water bath for another 30min, after which the solution was transferred to room temperature and 400mL deionized water was added. After the reaction is completed, adding frozen 10mL of hydrogen peroxide into the solution to remove the unreacted KMnO 4 After addition of 50mL of HCl, the mixture was stirred at room temperature for 1h. The product is kept stand, centrifuged to be neutral, and then freeze-dried for standby.
Preparation of N, N-dimethylethylenediamine modified GO: 10mL of the GO solution prepared above was taken, deionized water was added to a volume of 90mL, naOH was added thereto and stirred for 15min, then N, N-dimethylethylenediamine (NCCN (C) C) was added thereto, and stirred for 0.5h. And continuously stirring the mixed solution for 2 hours, washing the product with deionized water after the reaction is finished, centrifuging to be neutral, freeze-drying for 24 hours, and grinding for later use, namely GO-NCCN.
Example 2
Preparation of GO-based Pickering emulsifier modified by tertiary amine
Preparation of GO: as in example 1.
Preparation of N, N-diethyl ethylenediamine modified GO: 60mL of the prepared GO solution is taken, 0.68g of NaOH is added into the GO solution, after stirring for 15min, 2.24mL of N, N-diethyl ethylenediamine (DEEDA) is added into the GO solution, stirring is carried out for 30min, the mixed solution is stirred for 2h at a certain temperature, and after the reaction is finished, deionized water is used for washing for a plurality of times. The product was freeze-dried and ground for further use, designated as GO-DEED.
Example 3
Preparation of 3-dimethylaminopropylamine modified GO: 120mL of the prepared GO solution is taken, 0.68g of NaOH is added into the solution, after stirring for 30min, 3.85mL of 3-Dimethylaminopropylamine (DMAPA) is added into the solution, stirring is carried out for 30min, the mixed solution is stirred for 2h at a certain temperature, and after the reaction is finished, deionized water is used for washing for a plurality of times. The product was freeze-dried and ground for further use, designated GO-DMAP.
Example 4
Preparation of 3-diethylaminopropylamine modified GO: 40mL of the prepared GO solution is taken, 0.53g of NaOH is added into the solution, the solution is stirred for 30min, 1.75mL of 3-Diethylaminopropylamine (DEAPA) is added into the solution, the solution is stirred for 30min, the mixed solution is stirred for 2h at a certain temperature, and deionized water is used for washing for a plurality of times after the reaction is finished. The product was freeze-dried and ground for further use, designated GO-DEAP.
Example 5
Preparation of 4-dimethylaminobutylamine modified GO: 5mL of the GO solution prepared in example 1 was taken, deionized water was added to a constant volume of 40mL, 0.43g of NaOH was added thereto and stirred for 15min, and 1.75mL of 4-dimethylaminobutylamine was added thereto and stirred for 30min. And continuously stirring the mixed solution for 2 hours at a certain temperature, washing the product with deionized water after the reaction is finished, centrifuging to be neutral, freeze-drying for 24 hours, and grinding for later use, and marking as GO-NNDB.
Example 6
Preparation of 4-diethylaminobutylamine-modified GO 5mL of the GO solution prepared in example 1 was taken, deionized water was added to a constant volume of 40mL, 0.68g NaOH was added thereto and stirred for 15min, then 1.75mL 4-diethylaminobutylamine was added thereto and stirred for 30min. And continuously stirring the mixed solution for 2 hours at a certain temperature, washing the product with deionized water after the reaction is finished, centrifuging to be neutral, freeze-drying for 24 hours, and grinding for later use, and marking as GO-NNDD.
Example 7
Emulsion circulation step
Forming an emulsion: different tertiary amine modified GO with the mass concentration of 4wt% is taken as an emulsifying agent, the GO is placed in a mixed system of oil and inorganic alkali solution with a certain volume, the mixed system is subjected to ultrasonic treatment for a period of time, and is emulsified at room temperature by a high-speed shearing machine, wherein the volume fraction of an oil phase is controlled between 50% and 70% (see the liquid state in the first two bottles in the attached figure 1).
Demulsification: introducing CO into the emulsion at low temperature 2 With CO being introduced 2 With the time, the emulsion droplet diameter of the emulsion gradually increases (see the liquid state in the 2 nd and 3 rd bottles in the figure 1). Continue to maintain CO 2 The emulsion breaks away from the oil-water interface, and the emulsion breaks (see the liquid state in the 4 th and 5 th bottles in the figure 1 specifically) to obtain Pickering emulsion with in-situ cyclic response, wherein CO 2 The charging time is 15 min-2 h.
Again forming an emulsion: continuously introducing N into the demulsified emulsion 2 After a period of time, the emulsion is emulsified again by a high-speed shearing machine to form stable emulsion, the emulsion can be reversibly circulated for at least five times, and the particle size of the formed emulsion is kept unchanged. From the results of FIG. 1 it is demonstrated that the emulsion formed from tertiary amine modified GO as emulsifier has CO 2 /N 2 Responsiveness.
Example 8
Influence of oil-water ratio on emulsion properties:
in order to investigate the influence of the oil-water ratio on the emulsion performance, the oil was set up separately: the water ratio was 1:1, 2:1, and 3:1, with the emulsifier set at 0.75mg/mL. As can be seen from fig. 2, the emulsion ratio of the emulsion formed increases with the increase in the oil-water ratio at the same emulsifier concentration.
Example 9
Effect of emulsifier concentration on emulsion Properties
To investigate the effect of emulsifier concentration on the formation of the emulsion, a concentration gradient of 0.25-3.0 mg/mL of solid material mass/total solution volume was designed, and the emulsion was prepared as described in example 7, wherein the oil phase volume fractions were 67%. As the concentration of the emulsion increases, the particle size of the emulsion drops continuously becomes smaller, as the concentration of the emulsifier increases, the emulsion emulsification rate increases, and when the concentration of the emulsifier reaches a certain degree, the emulsion emulsification rate reaches 100% and does not increase.
Example 10
GO-DMAP stabilized Pickering emulsion breaking/re-emulsion forming
The milk-forming, demulsification and re-milk-forming were carried out in the same manner as in example 7. CO is introduced after the emulsion is formed 2 After 30min, the milk breaking phenomenon occurs, and CO is continuously introduced 2 For 30min, the emulsion is basically broken, and then N is introduced into the emulsion 2 After 1h, the emulsification rate reaches 90% of the original emulsification rate after emulsification by a high-speed shearing machine.
Example 11
GO-NNDB stabilized Pickering emulsion breaking/re-emulsion forming
The milk-forming, demulsification and re-milk-forming were carried out in the same manner as in example 7. CO is introduced after the emulsion is formed 2 After 20min, the milk breaking phenomenon occurs, and CO is continuously introduced 2 For 40min, the emulsion is basically broken, and then N is introduced into the emulsion 2 After 1h, the emulsification rate reaches 100% of the original emulsification rate by using a high-speed shearing machine.
Application examples
Example 12
0.036g of the GO-NCCN emulsifier of example 1 was charged into a three-necked flask containing 4mL of an inorganic base solution, 8mL of toluene and a specified amount of phenylboronic acid and iodobenzene. And (3) after ultrasonic treatment for 1h, emulsifying for 1-3 min by a high-speed shearing machine to obtain Pickering emulsion.
In the obtained O/W Pickering emulsion, the volume fraction of the oil phase is 67%, and the formed emulsion drops are uniformly distributed and have an average particle size of 31 mu m.
CO 2 Application of responsive Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3 hours at the temperature of 100 ℃. After the reaction, the mixture is left for a period of time, the supernatant is taken to pass through a needle filter, and the filtered solution is placed in a chromatographic bottle for preservation. The product content in the sample was determined using a gas chromatograph. The final yield was >99%.
Example 13
0.036g of the GO-DEED emulsifier of example 2 was charged into a three-necked flask containing 4mL of an inorganic base solution, 8mL of toluene, and a certain amount of phenylboronic acid and 4-methoxyiodobenzene. And (3) after ultrasonic treatment for 1h, emulsifying for 1-3 min by a high-speed shearing machine to obtain Pickering emulsion.
In the obtained oil-in-water Pickering emulsion, the volume fraction of the oil phase was 67%, the emulsion droplets were uniformly distributed and the average particle size of the emulsion droplets was 42. Mu.m.
CO 2 Application of responsive Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3 hours at the temperature of 100 ℃. After the reaction, the mixture is left for a period of time, the supernatant is taken to pass through a needle filter, and the filtered solution is placed in a chromatographic bottle for preservation. The product content in the sample was determined using a gas chromatograph. The final yield reached 95%.
Example 14
0.036g of the GO-DMAP emulsifier of example 3 was charged into a three-necked flask containing 3mL of an inorganic base solution, 9mL of toluene, and a certain amount of 4-methylphenylboronic acid and iodobenzene. And (3) after ultrasonic treatment for 1h, emulsifying for 1-3 min by a high-speed shearing machine to obtain Pickering emulsion.
In the obtained oil-in-water Pickering emulsion, the volume fraction of the oil phase was 75%, the emulsion droplets were uniformly distributed and the average particle size of the emulsion droplets was 38. Mu.m.
CO 2 Application of responsive Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3 hours at the temperature of 100 ℃. After the reaction, the mixture is left for a period of time, the supernatant is taken to pass through a needle filter, and the filtered solution is placed in a chromatographic bottle for preservation. The product content in the sample was determined using a gas chromatograph. The final yield reached 97%.
Example 15
0.036g of the GO-DEAP emulsifier of example 4 was charged into a three-necked flask equipped with 5mL of an inorganic base solution, 7mL of toluene, and a certain amount of 4-methylphenylboronic acid and 4-methoxyiodobenzene. And (3) after ultrasonic treatment for 2 hours, emulsifying for 1-3 minutes by a high-speed shearing machine to obtain Pickering emulsion.
In the obtained oil-in-water Pickering emulsion, the volume fraction of the oil phase was 58%, the emulsion droplets were uniformly distributed and the average particle diameter of the emulsion droplets was 41. Mu.m.
CO 2 Application of responsive Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3 hours at the temperature of 100 ℃. After the reaction, the mixture is left for a period of time, the supernatant is taken to pass through a needle filter, and the filtered solution is placed in a chromatographic bottle for preservation. The product content in the sample was determined using a gas chromatograph. The final yield reached 90%.
Example 16
0.036g of GO-NNDB emulsifier of example 5 was taken and added to a three-necked flask containing 6mL of an inorganic base solution, 6mL of toluene, and a certain amount of 4-formylphenylboronic acid and iodobenzene; and (3) after ultrasonic treatment for 1h, emulsifying for 1-3 min by a high-speed shearing machine to obtain Pickering emulsion.
In the obtained oil-in-water Pickering emulsion, the volume fraction of the oil phase was 50%, the emulsion droplets were uniformly distributed and the average particle size of the emulsion droplets was 36. Mu.m.
CO 2 Application of responsive Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3 hours at the temperature of 100 ℃. After the reaction, the mixture is left for a period of time, the supernatant is taken to pass through a needle filter, and the filtered solution is placed in a chromatographic bottle for preservation. The product content in the sample was determined using a gas chromatograph. The final yield reached 92%.
Example 17
0.036g of GO-NNDD emulsifier of example 6 was charged into a three-necked flask containing 4mL of an inorganic base solution, 8mL of toluene, and a certain amount of 4-methoxyphenylboronic acid and iodobenzene. And (3) after ultrasonic treatment for 1h, emulsifying for 1-3 min by a high-speed shearing machine to obtain Pickering emulsion.
In the obtained oil-in-water Pickering emulsion, the volume fraction of the oil phase was 67%, the emulsion droplets were uniformly distributed and the average particle diameter of the emulsion droplets was 45. Mu.m.
CO 2 Application of responsive Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3 hours at the temperature of 100 ℃. After the reaction, the mixture is left for a period of time, the supernatant is taken to pass through a needle filter, and the filtered solution is placed in a chromatographic bottle for preservation. The product content in the sample was determined using a gas chromatograph. The final yield reached 87%.
Example 18
Emulsion thermal stability
Since most catalytic reactions are carried out at very temperatures, the thermal stability of the emulsion is one of the important indicators for evaluating the performance of the emulsifier. Based on the above, the thermal stability of the emulsion formed by the emulsifier is examined, the emulsion drop can still be kept intact at a higher temperature, and the emulsion drop does not undergo massive coalescence and fragmentation at a higher temperature, so that the prepared emulsifier has better emulsion thermal stability, which provides possibility for the catalytic reaction applied at a higher temperature.
Example 19
Influence of alkali species on the reaction
The influence of different kinds of alkali on the reaction is investigated in this experimental example, and the results obtained by applying different kinds of alkali are shown in table 1, and the specific experimental steps are as follows: the reaction temperature conditions are not changed, only the alkali type is changed, and the alkali and Na are not added respectively 2 CO 3 、K 2 CO 3 、NEt 3 、K 3 PO 4 And Cs 2 CO 3 Six sets of experiments have found that the base species have a large impact on the reaction.
The details are shown in the following table 1:
TABLE 1 influence of alkali species on Suzuki reaction results
[a]Determined by gas chromatography。
Example 20
Influence of substrate species on the reaction
In addition, the reaction influence of different types of substrates on the reaction is explored in the examples of the patent, and the following table 2 shows that the reaction yield is greatly influenced by the types of the substrates as the reaction difficulty of different substrates under the same condition is obviously different by only changing the substrates under the condition of controlling other conditions.
Table 2 shows the effect of the substrate species on the Suzuki reaction
Claims (9)
1. A preparation method of a gas response type Pickering emulsion is characterized by comprising the following steps: adding the prepared gas response Pickering emulsifier into a system consisting of an inorganic alkaline solution water phase and an oil phase and having different oil-water proportions, and emulsifying for 1-3 min by using a high-speed shearing machine in an ultrasonic manner to obtain Pickering emulsion; introducing CO into the Pickering emulsion at 5deg.C 2 Breaking emulsion drop, and introducing N at 50deg.C 2 The emulsion can be obtained again after the high-speed shearing machine is stirred; the saidThe gas response type Pickering emulsifier is an emulsifier formed by oxidized graphene modified by tertiary amine; the Pickering emulsion taking the GO modified by tertiary amine as the particle emulsifier is applied to the Suzuki reaction.
2. The method for preparing the gas response type Pickering emulsion according to claim 1, which is characterized in that: the graphene oxide is prepared by adopting an improved Hummers method; the specific process for preparing GO by the Hummers method comprises the following steps: mixing graphite powder with H 3 PO 4 Adding into concentrated H 2 SO 4 Placing the mixture in an ice-water bath for stirring until graphite powder and H are obtained 3 PO 4 After being fully dissolved, the KMnO which is ground in advance 4 Adding the powder into the system at a constant speed; transferring the reaction solution into a water bath, slowly adding deionized water into the water bath, continuously stirring, transferring the solution into a hot water bath, stirring again, and adding deionized water and frozen hydrogen peroxide into the system after the reaction to remove the unreacted KMnO 4 Obtaining GO solution, standing and centrifuging the product to obtain neutral GO dispersion liquid, and freeze-drying for later use.
3. The method for preparing the gas response type Pickering emulsion according to claim 2, which is characterized in that: the preparation process of the emulsifier comprises the following steps: dispersing graphene oxide in NaOH solution, and adding a tertiary amine compound modifier into the solution, wherein the mass ratio of the tertiary amine compound to the graphite oxide is 0.2-0.5: 1, a step of; modifying GO, and treating for 2-4h at 65-75 ℃; and (3) centrifuging, freezing and drying the treated sample in vacuum to obtain the gas response type Pickering emulsifier.
4. A method for preparing a gas responsive Pickering emulsion according to claim 3, wherein: the gas of the gas response type Pickering emulsifier is CO 2 Or N 2 The method comprises the steps of carrying out a first treatment on the surface of the The tertiary amine compound modifier is N, N-dimethyl ethylenediamine, N-diethyl ethylenediamine, 3-dimethyl aminopropylamine, 3-diethyl aminopropylamine, 4-dimethyl ethylenediamineAnd one of the amino butylamine and 4-diethylaminobutylamine.
5. The method for preparing the gas response type Pickering emulsion according to claim 1, which is characterized in that: the Pickering emulsion is of O/W type, and the volume fraction of the emulsion is 50% -100%.
6. The method for preparing the gas response type Pickering emulsion according to claim 1, which is characterized in that: the oil phase comprises the following components: the volume ratio of the water phase is 1-3:1, and the mass of the solid material in the Pickering emulsion/the total solution volume is 0.25-3.0 mg/mL.
7. The method for preparing the gas response type Pickering emulsion according to claim 1, which is characterized in that: the water phase is Na 2 CO 3 ，NaHCO 3 、K 2 CO 3 、KHCO 3 、NaOH、KOH、Cs 2 CO 3 、K 3 PO 4 、Na 3 PO 4 、CH 3 COOK、Li 2 CO 3 One of the formed inorganic alkali solutions, wherein the oil phase is one of toluene, alkane or ionic liquid and other water-insoluble organic matters, and the inorganic alkali is used as an auxiliary agent; the oil phase is one of halogenated benzene or halogenated benzene derivatives and one of phenylboronic acid or phenylboronic acid derivatives, and is used as a reactant; the oil-water ratio system also contains tetra (triphenylphosphine) palladium as a catalyst.
8. The method for preparing the gas response type Pickering emulsion according to claim 7, which is characterized in that: the halogenated benzene comprises one of chlorobenzene, bromobenzene and iodobenzene, and the halogenated benzene derivative comprises one of p-nitrobromobenzene, p-methyl bromobenzene, p-hydroxy bromobenzene, 4-methoxy iodobenzene, 4-formyl iodobenzene, 4-methyl iodobenzene, p-nitro iodobenzene, p-hydroxy iodobenzene and bromonaphthalene; the phenylboronic acid derivative comprises one of 4-methoxyphenylboronic acid, 4-formylphenylboronic acid, 2-methoxyphenylboronic acid, 2-methylphenylboronic acid and 4-methylphenylboronic acid.
9. The method for preparing the gas response type Pickering emulsion according to claim 8, which is characterized in that: the molar ratio of the halogenated benzene or the derivative thereof to the phenylboronic acid or the derivative thereof is 1.5-2:1, the temperature of the Suzuki coupling reaction is 65-95 ℃, and the reaction time is 2-8 h.
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