CN114181716A - Gas response type Pickering emulsifier, preparation method and application in Suzuki reaction - Google Patents
Gas response type Pickering emulsifier, preparation method and application in Suzuki reaction Download PDFInfo
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Abstract
A gas response type Pickering emulsifier, a preparation method and application in Suzuki reaction. Is via a tertiary amineAdding the prepared gas response type Pickering emulsifier into a system composed of an inorganic alkaline solution water phase and an oil phase and having different oil-water ratios, and emulsifying for 1-3 min by using a high-speed shearing machine through ultrasound to obtain a Pickering emulsion; introducing CO into the obtained Pickering emulsion at the temperature of 5 DEG C2Breaking emulsion drop, introducing N at 50 deg.C2And emulsion can be obtained again after stirring by a high-speed shearing machine. The method has the advantages of effectively reducing the interface mass transfer resistance and improving the reaction interface area.
Description
Technical Field
The invention belongs to the field of functional materials, relates to a colloid interface material, and particularly relates to a preparation method of a gas response type Pickering emulsifier and application of the gas response type Pickering emulsifier in Suzuki (coupling) reaction.
Background
Palladium (Pd) catalyzes aryl boric acid and halogenated aromatic hydrocarbon to carry out Suzuki cross-coupling reaction to prepare biaryl compounds, and the method is one of the most important organic unit reactions for constructing C-C bonds. However, the reaction has large mass transfer resistance (Na is required to be added in the reaction) facing a water-organic two-phase interface in practical application2CO3Or K2CO3And the like, promote the metal transfer process to occur, 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 mostly adopts H2O/C2H5OH、H2O/DMF and H2Co-solvent systems such as O/DMAc and the like assist mechanical stirring or add phase transfer agents into the systems, however, the systems face the problem that the product separation and purification processes are complicated. Therefore, a new material and a catalytic system are developed to solve the problems of interfacial mass transfer and rapid reaction circulation in the Suzuki coupling reaction.
A Pickering emulsion interface catalytic reaction system (PIC) constructed by stabilizing water-organic two phases by solid particles with special surface activity gradually becomes an effective strategy for reducing mass transfer resistance of the water-organic two-phase interface due to the advantages of high activity, easy recovery of a catalyst and the like. Pd/SiO was first introduced into Resasco et al (Crossley S, Faria J, Shen M, Resasco DE. solid nanoparticles present at catalyst biological reagents at the water/oil interface. science 2010,327(5961):68-72.)2Emulsion catalysts are used for hydrogenation reactions, and PIC systems have been used for synthesis and biocatalysis reactions of various fine chemicals for over ten years.
Based on the urgent need of quick green circulation of a catalytic system, researchers at home and abroad explore the construction of a responsive Pickering emulsion catalytic system. For example, Yang et al (Yang H, Zhou T, Zhang W.mapping for separating and recycling dissolved catalysts based on the pH-triggered Pickering-interaction, Angewandte chemistry International Edition 2013,52(29):7455-2The basic principle that the surface functionalized amino functional group can be protonated/deprotonated under acid/alkali conditions is that a carrier material with pH response property is designed and prepared, and the carrier material is used for selective hydrogen-water-organic two-phase reaction of styrene, so that the rapid circulation of a catalytic system under the acid/alkali conditions is realized. Compared with other reported responsive emulsions (pH responsive type, light responsive type, temperature responsive type and the like), CO2The responsive emulsion has the advantages of green color, low price, easy availability, good biocompatibility, no salt solution accumulation (NaCl and the like due to pH adjustment) and the like, and is attracted by Jespop et al (Jespop PG, Heldebrant DJ, Li X, Eckert CA, Liotta CL. reversible non-polar-to-polar solvent. Nature 2005,436(7054): 1102-. Thus CO is converted into2The response type emulsion catalyst is used for water-organic two-phase reaction, the step of filtering and recovering the catalyst is not needed after the reaction is finished, and the quick green circulation of the reaction can be realized by directly demulsifying, pouring the organic phase and adding reactants for emulsification, so that the response type emulsion catalyst has important application prospect.
However, how to provide a catalyst with a function of converting CO into CO2Or other gas response type emulsion can be used in Suzuki cross-coupling reaction, and no relevant report is available at present.
Disclosure of Invention
Aiming at the defects in the prior art, the gas response type Pickering emulsifier is provided, and can effectively reduce the interface mass transfer resistance and improve the reaction interface area.
In order to solve the technical problem, the technical scheme adopted by the application is as follows: a gas-responsive Pickering emulsifier has gas-responsive properties and is formed by Graphene Oxide (GO) modified by tertiary amine.
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 method3As one of the oxidizing agents, toxic gas is generated. In view of this, the present application improves the method, and prepares GO with abundant functional groups and more easily controllable surface chemistry through a more green means.
More specifically, the specific process for preparing GO by the improved Hummers method is as follows: mixing graphite powder with H3PO4Is added to the concentrated H2SO4In the preparation method, the graphite powder and H are placed in an ice-water bath and stirred until the graphite powder and H are mixed3PO4After fully dissolving, pre-ground KMnO4Adding the powder into the system at a constant speed; and then 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, adding deionized water and frozen hydrogen peroxide into a system after the reaction is finished to remove incompletely reacted KMnO4 to obtain a GO solution, standing and centrifuging the product to obtain a neutral GO dispersion liquid, and freeze-drying the dispersion liquid for later use.
Preferably, the preparation process of the emulsifier formed by the tertiary amine modified Graphene Oxide (GO) is as follows: the preparation process comprises the following steps: dispersing graphene oxide in a NaOH solution, adding a tertiary amine compound modifier into the NaOH solution to modify GO, and treating for 2-4h at 65-75 ℃; and centrifuging, freezing and drying the treated sample in vacuum to obtain the gas response type Pickering emulsifier.
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 described herein is one of N, N-dimethylethylenediamine, N-diethylethylenediamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 4-dimethylaminobutylamine, and 4-diethylaminobutylamine.
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 composed of an inorganic alkaline solution water phase and an oil phase and having different oil-water ratios, and emulsifying for 1-3 min by using a high-speed shearing machine through ultrasound to obtain the Pickering emulsion.
Preferably, the 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 of the solid material/the volume of the total solution in the Pickering emulsion is 0.25-3.0 mg/mL.
Further, the obtained Pickering emulsion was passed through CO at 5 deg.C2Breaking the emulsion drop, and introducing N at 50 deg.C2And emulsion can be obtained again after stirring by a high-speed shearing machine.
Further, the aqueous phase described herein is Na2CO3，NaHCO3、K2CO3、KHCO3、NaOH、KOH、 Cs2CO3、K3PO4、Na3PO4、CH3COOK、Li2CO3And the oil phase is one of organic matters which are not mutually soluble with water, such as toluene, alkane or ionic liquid; inorganic base is used as an auxiliary agent.
Further, the oil-water ratio system also contains tetrakis (triphenylphosphine) palladium (Pd [ P (C) ]6H5)3]4) As a catalyst.
Further, the oil phase described herein is one of a halogenated benzene or a halogenated benzene derivative and one of phenylboronic acid or a phenylboronic acid derivative as reactants.
Furthermore, the halogenated benzene comprises one of chlorobenzene, bromobenzene and iodobenzene, and the halogenated benzene derivative comprises one of p-nitrobromobenzene, p-methylbromobenzene, p-hydroxybromobenzene, 4-methoxy iodobenzene, 4-formyl iodobenzene, 4-methyl iodobenzene, p-nitroiodobenzene, p-hydroxyiodobenzene and bromonaphthalene.
Furthermore, 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 an application of the tertiary amine modified GO as a particle emulsifier of an oil-in-water (O/W) Pickering emulsion. Compared with the traditional particle emulsifier such as inorganic particles and the like, the emulsion formed by the emulsifier has larger unit mass interfacial area (80-180 m)2/g) and smaller emulsion droplet (29-50 μm) size. Because the reaction system has larger interface area and smaller emulsion drop size, the contact area between reactants and the catalyst is increased, thereby effectively reducing mass transfer resistance and improving reaction efficiency, and being more beneficial to the reaction. .
The application also provides application of the Pickering emulsion taking the tertiary amine modified GO as the particle emulsifier in the Suzuki reaction, and the product conversion rate is more than 99% when the Pickering emulsion is applied to the Suzuki reaction.
The application has the advantages and beneficial effects that:
1. the application provides a Pickering emulsifier capable of being applied to Suzuki reaction for the first time, the emulsifier is tertiary amine modified Graphene Oxide (GO) prepared by a one-step method, and the emulsifier is applied to Suzuki reaction, and the preparation method is simple, easy to operate and high in economy; the prepared Pickering emulsifier has CO2/N2The emulsion has responsiveness, is suitable for various oil-water systems and Suzuki coupling reaction systems, and has good stabilizing effect on the emulsion under the alkaline condition.
2. The application takes GO as a basic structural unit for the first time, constructs the Pickering emulsifying agent capable of forming a high emulsion interface area, and provides a new method for solving the problem of interface mass transfer in the Suzuki coupling reaction. After the reaction is finished, simple CO can be used2Gas is introduced to realize the rapid separation of oil, water and products, the separation efficiency of the products is greatly improved, the separation difficulty of the products is reduced, and the emulsifier is recycled for many times to form emulsionThe performance is substantially unchanged.
3. Compared with the traditional inorganic particle and other particle emulsifying agents, the emulsion formed by the emulsifying agent has larger unit mass interface area (80-180 m)2/g) and smaller emulsion droplet (29-50 μm) size. Because the reaction system has larger interface area and smaller emulsion drop size, the contact area between reactants and the catalyst is increased, thereby effectively reducing mass transfer resistance and improving reaction efficiency, and being more beneficial to the reaction.
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 in example 8 at different oil-water ratios.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
Preparation of tertiary amine modified GO-based Pickering emulsifier
Preparation of GO: 5g of graphite powder and 2.85g H were prepared3PO4This was added to 130mL of concentrated H2SO4In the method, the graphite powder is placed in an ice-water bath and stirred for 2 hours until the graphite powder and H3PO4After fully dissolving, pre-ground 15g KMnO4Slowly adding the powder into the system (after 3h of uniform addition, 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 added slowly and stirring continued for 1 h. The solution after stirring for 1h was transferred to a 98 ℃ water bath and stirred again for 30min, after which the solution was transferred to room temperature and 400mL of deionized water was added thereto. After the reaction is completed, adding frozen 10mL hydrogen peroxide into the solution to remove the unreacted KMnO4After addition of 50mL of HCl, the reaction mixture was cooled to room temperatureStirring for 1 h. Standing the product, centrifuging to neutrality, and freeze drying.
Preparation of N, N-dimethylethylenediamine modified GO: taking 10mL of the GO solution prepared above, adding deionized water to a constant volume of 90mL, adding NaOH into the solution, stirring for 15min, adding N, N-dimethylethylenediamine (NCCN (C)) C into the solution, and stirring for 0.5 h. And continuously stirring the mixed solution for 2h, washing the product with deionized water after the reaction is finished, centrifuging to be neutral, and grinding for later use after freeze drying for 24h, wherein the product is marked as GO-NCCN.
Example 2
Preparation of tertiary amine modified GO-based Pickering emulsifier
Preparation of GO: as in example 1.
Preparation of N, N-diethylethylenediamine modified GO: taking 60mL of prepared GO solution, adding 0.68g of NaOH into the GO solution, stirring for 15min, adding 2.24mL of N, N-diethylethylenediamine (DEEDA), stirring for 30min, stirring the mixed solution for 2h at a certain temperature, and washing with deionized water for several times after the reaction is finished. The product was freeze dried and ground for use as GO-ded.
Example 3
Preparation of 3-dimethylaminopropylamine modified GO: taking 120mL of prepared GO solution, adding 0.68g of NaOH into the GO solution, stirring for 30min, adding 3.85mL of 3-Dimethylaminopropylamine (DMAPA), stirring for 30min, stirring the mixed solution for 2h at a certain temperature, and washing with deionized water for several times after the reaction is finished. The product was freeze dried and ground for use and scored as GO-DMAP.
Example 4
Preparation of 3-diethylaminopropylamine modified GO: taking 40mL of prepared GO solution, adding 0.53g of NaOH into the GO solution, stirring for 30min, adding 1.75mL of 3-Diethylaminopropylamine (DEAPA), stirring for 30min, stirring the mixed solution for 2h at a certain temperature, and washing with deionized water for several times after the reaction is finished. The product was freeze dried and ground for use as 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 the solution to a constant volume of 40mL, 0.43g of NaOH was added thereto and stirred for 15min, and then 1.75mL of 4-dimethylaminobutylamine was added thereto and stirred for 30 min. And continuously stirring the mixed solution at a certain temperature for 2h, washing the product with deionized water after the reaction is finished, centrifuging to be neutral, and grinding for later use after freeze drying for 24h, wherein the product is marked as GO-NNDB.
Example 6
Preparation of 4-diethylaminobutylamine modified GO, taking 5mL of GO solution prepared in example 1, adding deionized water to a constant volume of 40mL, adding 0.68g of NaOH thereto, stirring for 15min, adding 1.75mL of 4-diethylaminobutylamine thereto, and stirring for 30 min. And continuously stirring the mixed solution at a certain temperature for 2h, washing the product with deionized water after the reaction is finished, centrifuging to be neutral, and grinding for later use after freeze drying for 24h, wherein the product is marked as GO-NNDD.
Example 7
Emulsion circulation step
Forming an emulsion: taking GO modified by different tertiary amines with the mass concentration of 4 wt% as an emulsifier, placing the GO in a mixed system of oil and inorganic alkali solution with a certain volume, carrying out ultrasonic treatment for a period of time, and then emulsifying the GO at room temperature by using 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).
Demulsifying: introducing CO into the formed emulsion at low temperature2With the introduction of CO2The emulsion droplet size gradually increases with time (see the liquid state in bottles 2 and 3 in figure 1). Continued maintenance of CO2The emulsifier is separated from the oil-water interface, and the emulsion is broken (see the liquid state in bottles 4 and 5 in the attached figure 1), so that the Pickering emulsion with in-situ cyclic response is obtained, wherein CO2The introducing time is 15 min-2 h.
Emulsion formation again: continuously introducing N into the emulsion2After a period of time, emulsifying again by using a high-speed shearing machine to form stable emulsion, and reversibly circulating for at least five times, wherein the particle size of the formed emulsion is kept unchanged. From the results in FIG. 1, it is illustrated that the emulsion formed with tertiary amine modified GO as an emulsifier has CO2/N2And (4) responsiveness.
Example 8
Influence of oil-water ratio on emulsion performance:
in order to explore the influence of the oil-water ratio on the performance of the emulsion, the following oil is respectively arranged: the water ratios were 1:1, 2:1, and 3:1, and the emulsifier was set at 0.75 mg/mL. As can be seen from fig. 2, the emulsification rate of the formed emulsion increases with increasing oil-water ratio at the same emulsifier concentration.
Example 9
Effect of emulsifier concentration on emulsion Properties
In order to investigate the influence of the emulsifier concentration on the formation of the emulsion, the design was performed according to a concentration gradient of 0.25-3.0 mg/mL for the mass of the solid material/the volume of the total solution, and the specific preparation method of the emulsion was as described in example 7, wherein the oil phase volume fractions were all 67%. The particle size of the emulsion drops is continuously reduced along with the increase of the concentration of the emulsion, the emulsion rate of the emulsion is increased along with the increase of the concentration of the emulsifier, and the emulsion rate of the emulsion reaches 100% and is not increased any more after the concentration of the emulsifier reaches a certain degree.
Example 10
Demulsification/re-emulsification of GO-DMAP stabilized Pickering emulsions
The manner of emulsifying, breaking and re-emulsifying was the same as in example 7. Introducing CO after emulsion formation2After 30min, the phenomenon of milk breaking occurs, and CO is continuously introduced2For 30min, the emulsion is basically broken, and then N is introduced into the emulsion2After 1h, the emulsifying rate reaches 90 percent after the emulsification by a high-speed shearing machine.
Example 11
GO-NNDB stabilized Pickering emulsion breaking/re-emulsifying
The manner of emulsifying, breaking and re-emulsifying was the same as in example 7. Introducing CO after emulsion formation2After 20min, the phenomenon of milk breaking occurs, and CO is continuously introduced240min, basically breaking the emulsion, and introducing N into the emulsion2After 1h, the emulsifying rate reaches 100 percent after the emulsification by a high-speed shearing machine.
Application examples
Example 12
0.036g of GO-NCCN emulsifier from example 1 was taken and added to a three-necked flask containing 4mL of inorganic base solution, 8mL of toluene and certain amounts of phenylboronic acid and iodobenzene. And (4) after ultrasonic treatment is carried out for 1 hour, emulsifying for 1-3 minutes by a high-speed shearing machine to obtain the Pickering emulsion.
In the obtained O/W type Pickering emulsion, the volume fraction of an oil phase is 67 percent, formed emulsion droplets are uniformly distributed, and the average particle size of the emulsion droplets is 31 mu m.
CO2Application of response type Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3h at the temperature of 100 ℃. After the reaction is finished, standing for a period of time, taking supernatant liquid to pass through a needle type filter, and placing the filtered solution in a chromatographic bottle for storage. 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 taken and added to a three-necked flask containing 4mL of an inorganic base solution, 8mL of toluene and certain amounts of phenylboronic acid and 4-methoxyiodobenzene. And (4) after ultrasonic treatment is carried out for 1 hour, emulsifying for 1-3 minutes by a high-speed shearing machine to obtain the Pickering emulsion.
The volume fraction of the oil phase in the oil-in-water Pickering emulsion obtained was 67%, and the formed emulsion droplets were uniformly distributed and had an average particle diameter of 42 μm.
CO2Application of response type Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3h at the temperature of 100 ℃. After the reaction is finished, standing for a period of time, taking supernatant liquid to pass through a needle type filter, and placing the filtered solution in a chromatographic bottle for storage. The product content in the sample was determined using a gas chromatograph. The final yield reached 95%.
Example 14
0.036g of GO-DMAP emulsifier from example 3 was charged into a three-necked flask containing 3mL of inorganic base solution, 9mL of toluene and certain amounts of 4-methylphenylboronic acid and iodobenzene. And (4) after ultrasonic treatment is carried out for 1 hour, emulsifying for 1-3 minutes by a high-speed shearing machine to obtain the Pickering emulsion.
The volume fraction of the oil phase in the obtained oil-in-water Pickering emulsion was 75%, and the formed emulsion droplets were uniformly distributed and had an average particle diameter of 38 μm.
CO2Application of response type Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3h at the temperature of 100 ℃. After the reaction is finished, standing for a period of time, taking supernatant liquid to pass through a needle type filter, and placing the filtered solution in a chromatographic bottle for storage. The product content in the sample was determined using a gas chromatograph. The final yield reached 97%.
Example 15
0.036g of GO-DEAP emulsifier from example 4 was taken and charged into a three-necked flask containing 5mL of an inorganic base solution, 7mL of toluene, and certain amounts of 4-methylphenylboronic acid and 4-methoxyiodobenzene. And (4) after ultrasonic treatment is carried out for 2 hours, emulsifying for 1-3 min by using a high-speed shearing machine to obtain the Pickering emulsion.
The volume fraction of the oil phase in the oil-in-water Pickering emulsion obtained was 58%, and the formed emulsion droplets were uniformly distributed and had an average particle diameter of 41 μm.
CO2Application of response type Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3h at the temperature of 100 ℃. After the reaction is finished, standing for a period of time, taking supernatant liquid to pass through a needle type filter, and placing the filtered solution in a chromatographic bottle for storage. The product content in the sample was determined using a gas chromatograph. The final yield reached 90%.
Example 16
0.036g of the GO-NNDB emulsifier of example 5 was taken and added to a three-necked flask containing 6mL of inorganic base solution, 6mL of toluene and certain amounts of 4-formylphenylboronic acid and iodobenzene; and (4) after ultrasonic treatment is carried out for 1 hour, emulsifying for 1-3 minutes by a high-speed shearing machine to obtain the Pickering emulsion.
The volume fraction of the oil phase in the obtained oil-in-water Pickering emulsion is 50%, the formed emulsion droplets are uniformly distributed, and the average particle size of the emulsion droplets is 36 mu m.
CO2Application of response type Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3h at the temperature of 100 ℃. After the reaction is finished, standing for a period of time, taking supernatant liquid to pass through a needle type filter, and placing the filtered solution in a chromatographic bottle for storage. 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 from example 6 was taken and added to a three-necked flask containing 4mL of inorganic base solution, 8mL of toluene and certain amounts of 4-methoxyphenylboronic acid and iodobenzene. And (4) after ultrasonic treatment is carried out for 1 hour, emulsifying for 1-3 minutes by a high-speed shearing machine to obtain the Pickering emulsion.
The volume fraction of the oil phase in the oil-in-water Pickering emulsion obtained was 67%, and the formed emulsion droplets were uniformly distributed and had an average particle diameter of 45 μm.
CO2Application of response type Pickering emulsion in Suzuki reaction
The prepared Pickering emulsion is placed in a 25mL three-neck flask and continuously reacted for 3h at the temperature of 100 ℃. After the reaction is finished, standing for a period of time, taking supernatant liquid to pass through a needle type filter, and placing the filtered solution in a chromatographic bottle for storage. 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 high temperatures, the thermal stability of the emulsion is one of the important indicators for the evaluation of the performance of the emulsifier. Based on this, the thermal stability of the emulsion formed by the emulsifier is inspected, the emulsion droplets can still keep complete at a higher temperature, and the emulsion droplets are not subjected to large-scale coalescence and crushing at the higher temperature, so that the prepared emulsifier has a better emulsion thermal stability property, and the possibility of applying the emulsifier to a catalytic reaction at the higher temperature is provided.
Example 19
Influence of the base species on the reaction
The experimental example explores the influence of different types of alkali on the reaction, and table 1 shows the results obtained by applying different types of alkali, and the specific experimental steps are as follows: only the type of alkali is changed without changing reactants and reaction temperature conditions, and alkali addition and Na addition are respectively carried out2CO3、K2CO3、NEt3、K3PO4And Cs2CO3Six experiments show that the type of the alkali has a large influence on the reaction.
The details are shown in table 1 below:
TABLE 1 results of the influence of the base species on the Suzuki reaction
[a]Determined by gas chromatography。
Example 20
Influence of substrate species on the reaction
In addition, the examples of this patent study the influence of different substrates on the reaction, and specifically see table 2 below, it can be seen from table 2 that, by changing only the substrates while controlling other conditions, the reaction difficulty of different substrates under the same conditions is significantly different, and the substrate type also has a great influence on the reaction yield.
Table 2 shows the results of the influence of the substrate species on the Suzuki reaction
Claims (12)
1. A gas response type Pickering emulsifier is characterized in that: the emulsifier is formed by graphene oxide modified by tertiary amine.
2. The gas-responsive Pickering emulsifier according to claim 1, wherein: the graphene oxide is prepared by adopting an improved Hummers method; the specific process for preparing GO by the Hummers method is as follows: mixing graphite powder with H3PO4Is added to the concentrated H2SO4In the preparation method, the graphite powder and H are placed in an ice-water bath and stirred until the graphite powder and H are mixed3PO4After fully dissolving, pre-ground KMnO4Adding the powder into the system at a constant speed; then 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 after the reaction is finished, adding deionized water and frozen hydrogen peroxide into the system to remove the incompletely reacted KMnO4And standing and centrifuging the product to obtain a neutral GO dispersion liquid, and freeze-drying the neutral GO dispersion liquid for later use.
3. A method for preparing a gas responsive Pickering emulsifier according to any one of claims 1-2, wherein: the preparation process comprises the following steps: dispersing graphene oxide in a NaOH solution, adding a tertiary amine compound modifier into the NaOH solution, wherein the mass ratio of the tertiary amine compound to the graphite oxide is (0.2-0.5): 1; modifying GO, and treating for 2-4h at 65-75 ℃; and centrifuging, freezing and drying the treated sample in vacuum to obtain the gas response type Pickering emulsifier.
4. The preparation method of the gas-responsive Pickering emulsifier according to claim 3, characterized in that: the gas of the gas response type Pickering emulsifier is CO2Or N2(ii) a Said tertiaryThe amine compound modifier is one of N, N-dimethylethylenediamine, N-diethylethylenediamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 4-dimethylaminobutylamine and 4-diethylaminobutylamine.
5. A preparation method of a gas response type Pickering emulsion is characterized by comprising the following steps: adding the prepared gas response type Pickering emulsifier into a system composed of an inorganic alkaline solution water phase and an oil phase and having different oil-water ratios, and emulsifying for 1-3 min by using a high-speed shearing machine through ultrasound to obtain a Pickering emulsion; introducing CO into the obtained Pickering emulsion at the temperature of 5 DEG C2Breaking emulsion drop, introducing N at 50 deg.C2And emulsion can be obtained again after stirring by a high-speed shearing machine.
6. The method for preparing a gas-responsive Pickering emulsion according to claim 5, wherein: the Pickering emulsion is O/W type, and the volume fraction of the emulsion is 50-100%.
7. The method for preparing a gas-responsive Pickering emulsion according to claim 5, wherein: the oil phase: the volume ratio of the water phase is 1-3:1, and the mass of the solid material/the volume of the total solution in the Pickering emulsion is 0.25-3.0 mg/mL.
8. The method for preparing a gas-responsive Pickering emulsion according to claim 5, wherein: the water phase is Na2CO3，NaHCO3、K2CO3、KHCO3、NaOH、KOH、Cs2CO3、K3PO4、Na3PO4、CH3COOK、Li2CO3One of the formed inorganic alkali solutions, wherein the oil phase is one of organic matters which are not mutually soluble with water, such as toluene, alkane or ionic liquid, 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 as reactants; said oilThe system of the water proportion also contains tetrakis (triphenylphosphine) palladium as a catalyst.
9. The method for preparing a gas-responsive Pickering emulsion according to claim 8, wherein: the halogenated benzene comprises one of chlorobenzene, bromobenzene and iodobenzene, and the halogenated benzene derivative comprises one of p-nitrobromobenzene, p-methylbromobenzene, p-hydroxy bromobenzene, 4-methoxy iodobenzene, 4-formyl iodobenzene, 4-methyl iodobenzene, p-nitroiodobenzene, 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.
10. The method for preparing a gas-responsive Pickering emulsion according to claim 9, wherein: 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.
11. Use of a tertiary amine modified GO as a particle emulsifier for an oil-in-water Pickering emulsion.
12. An application of Pickering emulsion taking GO modified by tertiary amine as a particle emulsifier in Suzuki reaction.
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