CN116078430A - Deep eutectic solvent and preparation method and application thereof - Google Patents

Deep eutectic solvent and preparation method and application thereof Download PDF

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CN116078430A
CN116078430A CN202310076878.2A CN202310076878A CN116078430A CN 116078430 A CN116078430 A CN 116078430A CN 202310076878 A CN202310076878 A CN 202310076878A CN 116078430 A CN116078430 A CN 116078430A
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eutectic solvent
deep eutectic
palladium
bis
acid
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刘殿华
宋建华
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East China University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J35/19—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/82—Metals of the platinum group
    • B01J2523/824—Palladium

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Abstract

The application provides a deep eutectic solvent, a preparation method and application thereof, wherein a hydrogen bond donor and a hydrogen bond acceptor are mixed and reacted to obtain the deep eutectic solvent. The application provides a preparation method of an acidic halogen-free deep eutectic solvent with controllable acidity, simple preparation and high reaction efficiency. The obtained deep eutectic solvent is applied to alkoxycarbonyl reaction of alkene and/or alkyne, and the acid halogen-free deep eutectic solvent is used as an acid promoter in a system, so that self-separation of the catalyst in the alkoxycarbonyl reaction of alkene and/or alkyne is realized, and the cost of catalyst separation is reduced. The use of an acidic halogen-free deep eutectic solvent retains more activity than a homogeneous system using a conventional acid promoter after isolation of the product than a conventional homogeneous reaction.

Description

Deep eutectic solvent and preparation method and application thereof
Technical Field
The application relates to the technical field of chemical processes, in particular to a deep eutectic solvent and a preparation method and application thereof.
Background
Palladium-catalyzed alkoxycarbonyl of alkenes and alkynes can synthesize esters with extremely high selectivity and 100% atomic efficiency, and are of great interest because of their green requirements in accordance with the modern industry. Since palladium-catalyzed alkoxycarbonylations are homogeneous, the catalyst formed in situ from the ligand, acid promoter and palladium salt is miscible with the product and difficult to separate. The traditional separation methods such as distillation and rectification require higher temperature when separating products with larger molecular weight, and the ligand has complex structure, is sensitive to temperature and is easy to cause catalyst deactivation at high temperature. Catalyst recovery is a problem that needs to be addressed in this homogeneous reaction, since many times the cost of the ligand is even more expensive than noble metals.
The conventional catalyst recovery method is carried with a catalyst, but the catalyst is subjected to higher catalyst leaching when being carried with the catalyst, and only part of the catalyst is recovered when being recovered, so that part of the catalyst remains in the product, and the effect is not ideal. And compared with a homogeneous catalyst, the traditional supported catalyst has larger loss of catalytic activity due to mass transfer limitation.
Therefore, it is necessary to develop a deep eutectic solvent with high stability to achieve homogeneous catalysis and heterogeneous separation of the catalytic system to facilitate catalyst recovery.
Disclosure of Invention
The application provides a deep eutectic solvent, a preparation method and application thereof, and solves the problems that a catalyst is difficult to recover and the activity is low after recovery in the prior alkene and/or alkyne alkoxycarbonyl reaction.
The preparation method of the deep eutectic solvent in the first embodiment of the application comprises the following steps: and mixing and reacting the hydrogen bond donor and the hydrogen bond acceptor to obtain the deep eutectic solvent.
Alternatively, in other embodiments of the present application, the hydrogen bond donor includes one or more of p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, 4-nitrobenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, formic acid, acetic acid, oxalic acid, propionic acid, or benzoic acid.
Alternatively, in other embodiments of the present application, the hydrogen bond acceptor comprises one or more of l-carnitine, urea, lidocaine, acetamide, benzamide, 4-aminotoluene-3-sulfonic acid, 4-picolinic acid, proline, 2-picolinic acid, N-beta-hydroxyethylpiperazine, or beta-alanine.
Alternatively, in other embodiments of the present application, the molar ratio of hydrogen bond donor to hydrogen bond acceptor is (0.2-5): 1.
Alternatively, in other embodiments of the present application, the temperature of the reaction is from 25 ℃ to 200 ℃.
Alternatively, in other embodiments of the present application, the reaction time is from 0.5h to 48h.
According to the deep eutectic solvent in the second embodiment of the present application, the deep eutectic solvent is prepared by the preparation method, and the pH value of the deep eutectic solvent is 0.5-7.0.
Alternatively, in other embodiments of the present application, the deep eutectic solvent is halogen-free.
The deep eutectic solvent prepared by the preparation method in the third embodiment of the application or the application of the deep eutectic solvent in the alkoxycarbonyl reaction of alkene and/or alkyne.
Alternatively, in other embodiments of the present application, the alkoxycarbonylating reaction includes:
mixing deep eutectic solvent, alcohols, palladium salt and ligand in an autoclave;
sealing the autoclave and introducing carbon monoxide to vent air from the autoclave;
heating the autoclave, introducing carbon monoxide, adding alkene and/or alkyne to react, and circulating and repeating the steps;
the autoclave was cooled to quench the reaction.
Alternatively, in other embodiments of the present application, the olefin comprises one or more of ethylene, propylene, butene, 1, 3-butadiene, 1-pentene, 2-methyl-1, 3-butadiene, 1-hexene, 1,2,3, 4-tetrahydrobenzene, heptene, vinylbenzene, or allylbenzene.
Alternatively, in other embodiments of the present application, the alkyne includes one or more of acetylene, propyne, dimethyl acetylene, pentyne, hexyne, heptyne, ethynylbenzene, 1-phenyl-1-propyne, or 3-phenyl-1-propyne.
Alternatively, in other embodiments of the present application, the mass ratio of deep eutectic solvent to alcohol is (0.1-1.5): 1.
Alternatively, in other embodiments of the present application, the alcohol comprises one or more of methanol, ethanol, ethylene glycol, 1-propanol, 2-methylpropanol, 1,2, 3-glycerol, 1-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-butanol, 1-pentanol, 3-methyl-1-butanol, 2-dimethylpropanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, or 3-hexanol.
Alternatively, in other embodiments of the present application, the palladium salt comprises one or more of palladium acetate, palladium chloride, palladium bromide, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium (II) dichloride, palladium nitrite, palladium sulfate, ammonium tetrachloropalladate, potassium hexachloropalladate, palladium dichloride diammine, palladium tetra-ammine chloride, bis (triphenylphosphine) palladium (II) acetate, or trans-bis (benzonitrile) palladium (II) dichloride.
Alternatively, in other embodiments of the present application, the ligand comprises one or more of diphenyl-2-pyridinium phosphine, 1, 2-bis (di-t-butylphosphinomethyl) benzene, 1' -bis (diphenylphosphinomethyl) ferrocene, 1, 3-bis (diphenylphosphinomethyl) propane, 1, 2-bis (diphenylphosphinomethyl) benzene, bis [ (2-diphenylphosphino) phenyl ] ether, dimethylphenylphosphine, 1, 4-bis (diphenylphosphinomethyl) butane, tripropylphosphine, 1, 5-bis (diphenylphosphinomethyl) pentane, 1, 2-bis (diphenylphosphinomethyl) ethane, or diphenylcyclohexyl phosphine.
Alternatively, in other embodiments of the present application, the temperature of the autoclave is from 60 ℃ to 160 ℃ during the step of heating the autoclave.
The preparation method of the deep eutectic solvent has at least the following technical effects:
1) The deep eutectic solvent prepared by the method has controllable acidity and is used as an acid promoter in an alkene and/or alkyne alkoxycarbonyl reaction system. Due to the reactant alcohols and the main catalyst Pd 2+ The polarity is stronger, the polarity of the product esters is weaker, the alcohols with stronger polarity and the catalyst are enriched in the deep eutectic solvent phase with polarity in the reaction, and the esters with weaker polarity form a phase independently, so that the automatic separation of the catalyst can be realized, and the cost of separating the catalyst is reduced;
2) The deep eutectic solvent prepared by the method is applied to olefin and/or alkyne alkoxycarbonyl reaction, homogeneous catalysis is adopted, mass transfer limitation is avoided, catalytic activity is high, high-temperature separation is not needed for the catalyst, and catalyst deactivation is avoided;
3) The deep eutectic solvent has the advantages of simple preparation method and lower cost.
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In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram showing the relationship between the degree of phase separation at 80℃and time of the reaction system after 5 cycles in example 3 of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are within the scope of the protection of the present application, will be within the skill of the art without inventive effort. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application. In this application, unless otherwise indicated, terms of orientation such as "upper", "lower", "left" and "right" are generally used to refer to the directions of the drawings in which the device is actually used or in an operating state.
The embodiment of the application provides a deep eutectic solvent, and a preparation method and application thereof. The following will describe in detail. The following description of the embodiments is not intended to limit the preferred embodiments.
The embodiment of the application provides a preparation method of a deep eutectic solvent, which comprises the following steps: and mixing and reacting the hydrogen bond donor and the hydrogen bond acceptor to obtain the deep eutectic solvent. The preparation method of the deep eutectic solvent is simple, and the deep eutectic solvent can be prepared by simply carrying out constant-temperature water bath and stirring. The preparation method of the acid halogen-free deep eutectic solvent is simple, low in cost and controllable in acidity, is used for alkoxycarbonyl reaction of alkene and alkyne, realizes automatic separation of the catalyst after the reaction of the alkene and alkyne alkoxycarbonyl system, reduces the cost of catalyst separation, and slows down catalyst deactivation.
In some embodiments of the present application, the hydrogen bond donor includes one or more of p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, 4-nitrobenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, formic acid, acetic acid, oxalic acid, propionic acid, or benzoic acid.
In some embodiments of the present application, the hydrogen bond acceptor comprises one or more of l-carnitine, urea, lidocaine, acetamide, benzamide, 4-aminotoluene-3-sulfonic acid, 4-picolinic acid, proline, 2-picolinic acid, N-beta-hydroxyethylpiperazine, or beta-alanine.
In some embodiments of the present application, the molar ratio of hydrogen bond donor to hydrogen bond acceptor may be (0.2-5): 1, or may be (1-4): 1, and may be (1.05 to 2): 1. the deep eutectic solvent has controllable acidity, and can realize the regulation and control of the acidity by changing the mole ratio between the hydrogen bond donor and the hydrogen bond acceptor.
In some embodiments of the present application, the temperature of the reaction may be 25℃to 200℃or 50℃to 150℃or 80℃to 100 ℃.
In some embodiments of the present application, the reaction time may be 0.1 to 48 hours, may be 2 to 40 hours, and may be 10 to 30 hours.
Correspondingly, the embodiment of the application also provides a deep eutectic solvent, wherein the deep eutectic solvent is prepared by the preparation method, and the pH value of the deep eutectic solvent can be 0.5-7.0, 1.0-6.0, or 2.0-5.0. The deep eutectic solvent is a two-component or three-component deep eutectic mixture formed by combining hydrogen bond acceptors and hydrogen bond donors in a stoichiometric ratio, and the solidifying point of the deep eutectic solvent is obviously lower than the melting point of pure substances of each component.
In some embodiments of the present application, the deep eutectic solvent is halogen-free. The acid deep eutectic solvents commonly used at present contain halogen, and high concentration of halogen can corrode equipment and poison catalysts used in alkoxycarbonyl reactions. The deep eutectic solvent prepared by the method does not contain halogen, reduces the loss of equipment, and does not cause catalyst poisoning.
The embodiment of the application also provides a deep eutectic solvent prepared by the preparation method or application of the deep eutectic solvent in the alkoxycarbonyl reaction of alkene and/or alkyne.
In some embodiments of the present application, the alkoxycarbonylating reaction includes:
mixing deep eutectic solvent, alcohols, palladium salt and ligand in an autoclave;
sealing the autoclave and introducing carbon monoxide to vent air from the autoclave;
heating the autoclave, introducing carbon monoxide, adding alkene and/or alkyne to react, and circulating and repeating the steps;
the autoclave was cooled to quench the reaction.
The palladium-catalyzed catalysts for the alkoxycarbonyl of olefins and alkynes include palladium salts, ligands and acid promoters. The acid promoter is usually a strong acid having a weak coordination ability such as p-toluenesulfonic acid or methanesulfonic acid. The main catalyst is palladium salt, and the main function of the ligand in a palladium-catalyzed alkene and alkyne alkoxycarbonyl system is to stabilize the catalyst, regulate steric hindrance and charge density and realize the enhancement of the catalyst activity. The main function of the acid promoter is to generate the reaction intermediate Pd-H species. Since palladium-catalyzed alkoxycarbonylations are homogeneous, the catalyst formed in situ from the ligand, acid promoter and palladium salt is miscible with the product and difficult to separate. Compared with the traditional recovery mode, the deep eutectic solvent has the advantages that the synthesis steps are few, the raw materials are low-cost chemicals, the acidity can be freely regulated and controlled, and compared with the traditional catalyst recovery mode, the deep eutectic solvent has certain advantages, and the simple separation of the catalyst can be realized while the characteristics of homogeneous catalysis and high activity are maintained.
In some embodiments of the present application, the olefin comprises one or more of ethylene, propylene, butene, 1, 3-butadiene, 1-pentene, 2-methyl-1, 3-butadiene, 1-hexene, 1,2,3, 4-tetrahydrobenzene, heptene, vinylbenzene, or allylbenzene.
In some embodiments of the present application, the alkyne includes one or more of acetylene, propyne, dimethyl acetylene, pentyne, hexyne, heptyne, ethynylbenzene, 1-phenyl-1-propyne, or 3-phenyl-1-propyne.
In some embodiments of the present application, the mass ratio of the deep eutectic solvent to the alcohol may be (0.1-1.5): 1, or may be (0.3-1.3): 1, may be (0.5 to 1): 1.
in some embodiments of the present application, the alcohol comprises one or more of methanol, ethanol, ethylene glycol, 1-propanol, 2-methylpropanol, 1,2, 3-glycerol, 1-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-butanol, 1-pentanol, 3-methyl-1-butanol, 2-dimethylpropanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, or 3-hexanol.
In some embodiments of the present application, the palladium salt comprises one or more of palladium acetate, palladium chloride, palladium bromide, bis dibenzylideneacetone palladium, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium (II) dichloride, palladium nitrite, palladium sulfate, ammonium tetrachloropalladate, potassium hexachloropalladate, dichlorodiammine palladium, tetraamminepalladium chloride, bis (triphenylphosphine) palladium (II) acetate, or trans-bis (benzonitrile) dichloropalladium (II).
In some embodiments of the present application, the ligand comprises one or more of diphenyl-2-pyridinium phosphine, 1, 2-bis (di-t-butylphosphinomethyl) benzene, 1' -bis (diphenylphosphinomethyl) ferrocene, 1, 3-bis (diphenylphosphinomethyl) propane, 1, 2-bis (diphenylphosphinomethyl) benzene, bis [ (2-diphenylphosphinomethyl) phenyl ] ether, dimethylphenylphosphine, 1, 4-bis (diphenylphosphinomethyl) butane, tripropylphosphine, 1, 5-bis (diphenylphosphinomethyl) pentane, 1, 2-bis (diphenylphosphinomethyl) ethane, or diphenylcyclohexyl phosphine.
In some embodiments of the present application, the temperature of the autoclave during the heating step may be from 60 ℃ to 160 ℃, or from 80 ℃ to 150 ℃, or from 100 ℃ to 130 ℃.
In particular, the step of the alkoxycarbonyl reaction comprises:
1) Mixing the acid halogen-free deep eutectic solvent and alcohol with the mass ratio of (0.1-1.5) 1 in an autoclave, and adding palladium salt and ligand;
2) Sealing the autoclave, introducing carbon monoxide to 0.1-6.0 MPa, stirring for 1-30 min, discharging gas, and repeating the operation twice to discharge the air in the autoclave;
3) After the temperature is programmed to 60-160 ℃, introducing alkene, alkyne and carbon monoxide in a molar ratio of (0.1-10): 1, starting the reaction after the total pressure reaches 0.1-8.0 MPa, and recording the experimental conversion rate and selectivity after the reaction time is reached, and recording as cycle 1; repeating the step 3) to finish the reaction;
4) The reaction was quenched by rapid cooling with heating off, the autoclave temperature was cooled to room temperature, the remaining gas in the autoclave was vented, and the body was opened to collect the product and analyzed using gas chromatography.
The following description is made with reference to specific embodiments.
Example 1,
The embodiment provides a preparation method of deep eutectic solvent and an alkoxycarbonyl reaction of olefin, which comprises the following specific steps:
the preparation method of the deep eutectic solvent in the embodiment comprises the following steps:
l-carnitine (0.0372 mol,6 g) and p-toluenesulfonic acid monohydrate (0.0372 mol,7.12 g) in a molar ratio of 1:1 were mixed in a flask, and the mixture was stirred for 4h at 90℃in a thermostatic water bath. And obtaining the transparent liquid acid halogen-free deep eutectic solvent No. 1.
Use of acid halogen-free deep eutectic solvent No. 1 for the alkoxycarbonyl synthesis of propyl propionate from ethylene and carbon monoxide and n-propanol, comprising the steps of:
1) N-propanol (8.04 g,10 ml), palladium acetate (0.0133 mmol,3.0 mg), 1, 2-bis (di-t-butylphosphinomethyl) benzene (0.0534 mmol,21.0 mg) and acid halogen-free deep eutectic solvent No. 1 (70 wt%,5.6 g) were charged into a 50ml autoclave equipped with a tetrafluoroethylene liner;
2) Sealing and introducing carbon monoxide to 0.5MPa, vigorously stirring for 5min, discharging gas, and repeating for two times to discharge air in the autoclave;
3) The kettle was warmed to 100℃and a mixture of ethylene (0.0196 mol,0.549 g) and carbon monoxide (0.0196 mol,0.549 g) in a molar ratio of 1:1 was introduced to 2.0MPa, the timing was started and the reaction pressure was recorded after 2h, recorded as cycle 1; after the cycle 1 is finished, introducing mixed gas of 2.0MPa, and recording the reaction pressure after 2 hours, wherein the reaction pressure is recorded as cycle 2; the same steps are cycled through operation until cycle 5;
4) Taking out the autoclave, rapidly cooling to room temperature, discharging residual gas in the autoclave, opening the autoclave body, collecting the product, and carrying out chromatographic analysis to obtain the cycle 1 conversion rate of 72%, and the propyl propionate selectivity of more than 99%.
EXAMPLE 2,
The embodiment provides a preparation method of deep eutectic solvent and an alkoxycarbonyl reaction of olefin, which comprises the following specific steps:
the preparation method of the deep eutectic solvent in the embodiment comprises the following steps:
l-carnitine (0.0372 mol,6 g) and p-toluenesulfonic acid monohydrate (0.0744 mol,14.15 g) in a molar ratio of 1:2 were mixed in a flask and stirred for 2h in a constant temperature water bath at 80℃to give a transparent liquid No. 2 acid halogen-free deep eutectic solvent.
Use of acid halogen-free deep eutectic solvent No. 2 for the alkoxycarbonyl synthesis of propyl propionate from ethylene and carbon monoxide and n-propanol, comprising the steps of:
1) N-propanol (8.04 g,10 ml), palladium acetate (0.0133 mmol,3.0 mg), 1, 2-bis (di-t-butylphosphinomethyl) benzene (0.0534 mmol,21.0 mg) and No. 2 acid halogen-free deep eutectic solvent (70 wt%,5.6 g) were charged into a 50ml autoclave equipped with a tetrafluoroethylene liner;
2) Sealing and introducing carbon monoxide to 0.5MPa, vigorously stirring for 5min, discharging gas, and repeating for two times to discharge air in the autoclave;
3) The kettle was warmed to 80℃and a mixture of ethylene (0.0196 mol,0.549 g) and carbon monoxide (0.0196 mol,0.549 g) in a molar ratio of 1:1 was introduced to 2.0MPa, the timing was started and the reaction pressure was recorded after 2h, recorded as cycle 1; after the cycle 1 is finished, introducing mixed gas of 2.0MPa, and recording the reaction pressure after 2 hours, wherein the reaction pressure is recorded as cycle 2; the same steps are cycled through operation until cycle 5;
4) Taking out the autoclave, rapidly cooling to room temperature, discharging residual gas in the autoclave, opening the autoclave body, collecting the product, and carrying out chromatographic analysis to obtain the cycle 1 conversion rate of 78%, wherein the propyl propionate selectivity is 98%.
EXAMPLE 3,
The embodiment provides a preparation method of deep eutectic solvent and an alkoxycarbonyl reaction of olefin, which comprises the following specific steps:
the preparation method of the deep eutectic solvent in the embodiment comprises the following steps:
l-carnitine (0.0372 mol,6 g) and p-toluenesulfonic acid monohydrate (0.0391 mol,7.43 g) in a molar ratio of 1:1.05 were mixed in a flask and stirred for 2h at 80℃in a constant temperature water bath to give a transparent liquid No. 3 acid halogen-free deep eutectic solvent at room temperature.
Use of acid halogen-free deep eutectic solvent No. 3 for the alkoxycarbonyl synthesis of propyl propionate from ethylene and carbon monoxide and n-propanol, comprising the steps of:
1) N-propanol (8.04 g,10 ml), palladium acetate (0.0133 mmol,3.0 mg), 1, 2-bis (di-t-butylphosphinomethyl) benzene (0.0534 mmol,21.0 mg) and acid halogen-free deep eutectic solvent No. 3 (70 wt%,5.6 g) were charged into a 50ml autoclave equipped with a tetrafluoroethylene liner;
2) Sealing and introducing carbon monoxide to 0.5MPa, vigorously stirring for 5min, discharging gas, and repeating for two times to discharge air in the autoclave;
3) The kettle was warmed to 80℃and a mixture of ethylene (0.0196 mol,0.549 g) and carbon monoxide (0.0196 mol,0.549 g) in a molar ratio of 1:1 was introduced to 2.0MPa, the timing was started and the reaction pressure was recorded after 2h, recorded as cycle 1; after the cycle 1 is finished, introducing mixed gas of 2.0MPa, and recording the reaction pressure after 2 hours, wherein the reaction pressure is recorded as cycle 2; the same steps are cycled through operation until cycle 5;
4) Taking out the autoclave, rapidly cooling to room temperature, discharging residual gas in the autoclave, opening the autoclave body, collecting products, and carrying out chromatographic analysis to obtain the cycle 1 with the conversion rate of more than 99% and the propyl propionate with the selectivity of more than 99%.
The clear organic phase above the system after the reaction is completed is the product propyl propionate phase, and the deep eutectic solvent phase containing the catalyst is yellow below. The upper organic phase was poured into a flask to distill off the product, and then 9ml of n-propanol was added to wash the flask, after which this 9ml of n-propanol was added to the lower deep eutectic solvent phase. The above steps of scrubbing and reacting are repeated. The catalyst can maintain 80% conversion over 18 cycles with selectivity >99% and 18 cycles can be completed without significant activity reduction from example 3, indicating higher stability. And the deep eutectic solvent and the organic product phase can be rapidly separated under the reaction condition of 80 ℃ as shown in figure 1. Figure 1 shows the state of example 3 after 5 catalytic cycles, which separates into a clear transparent upper organic phase and a yellow catalyst-containing lower deep eutectic solvent phase. The palladium element concentrations in the upper and lower deep eutectic solvent phases were obtained using inductively coupled plasma emission spectrometry (ICP-OES) physicochemical characterization methods, as shown in table 1. Table 1 shows the palladium element content of the upper propyl propionate phase and the lower deep eutectic solvent phase formed after 5 catalytic cycles for example 3 as measured by ICP-OES. The palladium element is mainly enriched in the deep eutectic solvent phase at the lower layer, which shows that the catalyst separation can be effectively realized by adding the deep eutectic solvent.
TABLE 1
Palladium element concentration/ppm
Upper propyl propionate phase 3
Lower deep eutectic solvent phase 286
EXAMPLE 4,
The embodiment provides a preparation method of deep eutectic solvent and an alkoxycarbonyl reaction of olefin, which comprises the following specific steps:
the preparation method of the deep eutectic solvent in the embodiment comprises the following steps:
l-carnitine (0.0372 mol,6 g) and p-toluenesulfonic acid monohydrate (0.0391 mol,7.43 g) in a molar ratio of 1:1.05 were mixed in a flask and stirred for 8h at 80℃in a constant temperature water bath to give a transparent liquid No. 4 acid halogen-free deep eutectic solvent at room temperature.
Use of acid halogen-free deep eutectic solvent No. 4 for the alkoxycarbonyl synthesis of methyl propionate from ethylene and carbon monoxide and methanol, comprising the steps of:
1) Methanol (6.328 g,8 ml), palladium acetate (0.0133 mmol,3.0 mg), 1, 2-bis (di-t-butylphosphinomethyl) benzene (0.0534 mmol,21.0 mg) and acid No. 4 halogen-free deep eutectic solvent (70 wt%,4.4 g) were charged into a 50ml autoclave equipped with a tetrafluoroethylene liner;
2) Sealing and introducing carbon monoxide to 0.5MPa, vigorously stirring for 5min, discharging gas, and repeating for two times to discharge air in the autoclave;
3) The kettle was warmed to 120℃and a mixture of ethylene (0.0196 mol,0.549 g) and carbon monoxide (0.0196 mol,0.549 g) in a molar ratio of 1:1 was introduced to 2.0MPa, the timing was started and the reaction pressure was recorded after 0.5h, recorded as cycle 1; after the cycle 1 is finished, introducing mixed gas of 2.0MPa, and recording the reaction pressure after 2 hours, wherein the reaction pressure is recorded as cycle 2; the same steps are cycled through operation until cycle 7;
4) Taking out the autoclave, rapidly cooling to room temperature, discharging residual gas in the autoclave, opening the autoclave body, collecting the product, and performing chromatographic analysis to obtain the cycle 1 with the conversion rate of more than 99% and the methyl propionate selectivity of more than 99%.
EXAMPLE 5,
The embodiment provides a preparation method of deep eutectic solvent and an alkoxycarbonyl reaction of olefin, which comprises the following specific steps:
the preparation method of the deep eutectic solvent in the embodiment comprises the following steps:
l-carnitine (0.0372 mol,6 g) and p-toluenesulfonic acid monohydrate (0.0391 mol,7.43 g) in a molar ratio of 1:1.05 were mixed in a flask and stirred for 0.5h at 60℃in a constant temperature water bath to give a transparent liquid No. 5 acid halogen-free deep eutectic solvent at room temperature.
Use of acid halogen-free deep eutectic solvent No. 5 for the alkoxycarbonyl synthesis of ethyl propionate from ethylene and carbon monoxide and ethanol, comprising the steps of:
1) Ethanol (6.314 g,8 ml), palladium acetate (0.0133 mmol,3.0 mg), 1, 2-bis (di-t-butylphosphinomethyl) benzene (0.0534 mmol,21.0 mg) and acid halogen-free deep eutectic solvent No. 5 (70 wt%,4.4 g) were charged into a 50ml autoclave equipped with a tetrafluoroethylene liner;
2) Sealing and introducing carbon monoxide to 0.5MPa, vigorously stirring for 5min, discharging gas, and repeating for two times to discharge air in the autoclave;
3) The kettle was warmed to 120℃and a mixture of ethylene (0.0196 mol,0.549 g) and carbon monoxide (0.0196 mol,0.549 g) in a molar ratio of 1:1 was introduced to 2.0MPa, the timing was started and the reaction pressure was recorded after 2h, recorded as cycle 1; after the cycle 1 is finished, introducing mixed gas of 2.0MPa, and recording the reaction pressure after 2 hours, wherein the reaction pressure is recorded as cycle 2; the same steps are cyclically operated until cycle 4;
4) Taking out the autoclave, rapidly cooling to room temperature, discharging residual gas in the autoclave, opening the autoclave body, collecting products, and carrying out chromatographic analysis to obtain the cycle 1 with the conversion rate of more than 99% and the ethyl propionate selectivity of more than 99%.
EXAMPLE 6,
The embodiment provides a preparation method of deep eutectic solvent and an alkoxycarbonyl reaction of olefin, which comprises the following specific steps:
the preparation method of the deep eutectic solvent in the embodiment comprises the following steps:
l-carnitine (0.0372 mol,6 g) and p-toluenesulfonic acid monohydrate (0.0391 mol,7.43 g) in a molar ratio of 1:1.05 were mixed in a flask and stirred for 12h at a constant temperature water bath at 70℃to give a transparent liquid No. 6 acid halogen-free deep eutectic solvent at room temperature.
Use of acid halogen-free deep eutectic solvent No. 6 for the alkoxycarbonyl synthesis of n-butyl propionate from ethylene and carbon monoxide and n-butanol, comprising the steps of:
1) N-butanol (8.098 g,10 ml), palladium acetate (0.0133 mmol,3.0 mg), 1, 2-bis (di-t-butylphosphinomethyl) benzene (0.0534 mmol,21.0 mg) and No. 6 acid halogen-free deep eutectic solvent (70 wt%,5.7 g) were added to a 50ml autoclave equipped with a tetrafluoroethylene liner;
2) Sealing and introducing carbon monoxide to 0.5MPa, vigorously stirring for 5min, discharging gas, and repeating for two times to discharge air in the autoclave;
3) The kettle was warmed to 90℃and a mixture of ethylene (0.0196 mol,0.549 g) and carbon monoxide (0.0196 mol,0.549 g) in a molar ratio of 1:1 was introduced to 2.0MPa, the timing was started and the reaction pressure was recorded after 2h, recorded as cycle 1; after the cycle 1 is finished, introducing mixed gas of 2.0MPa, and recording the reaction pressure after 2 hours, wherein the reaction pressure is recorded as cycle 2; the same steps are cyclically operated until cycle 4;
4) Taking out the autoclave, rapidly cooling to room temperature, discharging residual gas in the autoclave, opening the autoclave body, collecting products, and carrying out chromatographic analysis to obtain the cycle 1 with the conversion rate of more than 99% and the butyl propionate selectivity of more than 99%.
Comparative example 1,
This comparative example provides an alkoxycarbonylating reaction of olefins. Use of commercially available p-toluenesulfonic acid for the alkoxycarbonyl synthesis of propyl propionate from ethylene and carbon monoxide and n-propanol, comprising the steps of:
1) N-propanol (8.04 g,10 ml), palladium acetate (0.0133 mmol,3.0 mg), 1, 2-bis (di-t-butylphosphinomethyl) benzene (0.0534 mmol,21.0 mg) and p-toluene sulfonic acid (0.2615 mmol,0.05 g) were charged into a 50ml autoclave equipped with a tetrafluoroethylene liner;
2) Sealing and introducing carbon monoxide to 0.5MPa, vigorously stirring for 5min, discharging gas, and repeating for two times to discharge air in the autoclave;
3) The kettle was warmed to 80℃and a mixture of ethylene (0.0196 mol,0.549 g) and carbon monoxide (0.0196 mol,0.549 g) in a molar ratio of 1:1 was introduced to 2.0MPa, the timing was started and the reaction pressure was recorded after 2h, recorded as cycle 1; after the cycle 1 is finished, introducing mixed gas of 2.0MPa, and recording the reaction pressure after 2 hours, wherein the reaction pressure is recorded as cycle 2; the same steps are cycled through operation until cycle 5;
4) Taking out the autoclave, rapidly cooling to room temperature, discharging residual gas in the autoclave, opening the autoclave body, collecting products, and carrying out chromatographic analysis to obtain the cycle 1 with the conversion rate of more than 99% and the propyl propionate with the selectivity of more than 99%.
After the end of cycle 5, the catalyst-containing product obtained was distilled, 10ml of propanol was added to the catalyst remaining after the distillation, and the reaction was carried out by repeating the above operation in an autoclave again. The reaction can maintain >80% conversion in the first 7 rounds, with the 8 th round beginning the conversion dropping sharply to 43%.
Comparative example 1 compared to example 3, the conversion drops sharply to 43% at the beginning of run 8, whereas example 3 can maintain 80% or more conversion over 18 cycles with a selectivity >99%. The deep eutectic solvent is used as an acid promoter, so that the catalyst can be kept to have higher catalytic activity and stability.
Comparative example 2,
The comparative example provides a process for preparing a deep eutectic solvent and an alkoxycarbonyl reaction of an olefin, comprising the following steps:
the preparation method of the deep eutectic solvent of the comparative example comprises the following steps:
choline chloride (0.0358 mol,5 g) in a molar ratio of 1:1.05 was mixed with p-toluenesulfonic acid monohydrate (0.0376 mol,7.15 g) in a flask. And stirring for 2 hours in a constant-temperature water bath at 80 ℃ to obtain transparent liquid type No. 7 acid halogen-free deep eutectic solvent at room temperature.
Use of the deep eutectic solvent No. 7 for the alkoxycarbonylation of ethylene with carbon monoxide and n-propanol to synthesize propyl propionate, comprising the steps of:
1) N-propanol (8.04 g,10 ml), palladium acetate (0.0133 mmol,3.0 mg), 1, 2-bis (di-t-butylphosphinomethyl) benzene (0.0534 mmol,21.0 mg) and acid halogen-free deep eutectic solvent No. 7 (70 wt%,5.6 g) were charged into a 50ml autoclave equipped with a tetrafluoroethylene liner;
2) Sealing and introducing carbon monoxide to 0.5MPa, vigorously stirring for 5min, discharging gas, and repeating for two times to discharge air in the autoclave;
3) The kettle was warmed to 80℃and a mixture of ethylene (0.0196 mol,0.549 g) and carbon monoxide (0.0196 mol,0.549 g) in a molar ratio of 1:1 was introduced to 2.0MPa, the timing was started and the reaction pressure was recorded after 2h, recorded as cycle 1; after the cycle 1 is finished, introducing mixed gas of 2.0MPa, and recording the reaction pressure after 2 hours, wherein the reaction pressure is recorded as cycle 2; the same steps are cycled through operation until cycle 5;
4) Taking out the autoclave, rapidly cooling to room temperature, discharging residual gas in the autoclave, opening the autoclave body, collecting products and carrying out chromatographic analysis to obtain the cycle 1 conversion rate of 0.
Comparing comparative example 2 with example 3, the halogen-free deep eutectic solvent can complete 18 cycles, while the halogen-containing deep eutectic solvent of comparative example 2 does not react, which indicates that the halogen-free deep eutectic solvent prepared by the preparation method of the present application improves the catalytic activity.
Comparative example 3,
The comparative example provides a process for preparing a deep eutectic solvent and an alkoxycarbonyl reaction of an olefin, comprising the following steps:
the preparation method of the deep eutectic solvent of the comparative example comprises the following steps:
l-carnitine (0.0372 mol,6 g) and benzoic acid (0.0391 mol,4.77 g) in a molar ratio of 1:1.05 were mixed in a flask. And stirring for 2 hours in a constant-temperature water bath at 80 ℃ to obtain transparent liquid No. 8 acid halogen-free deep eutectic solvent at room temperature.
Use of No. 8 deep eutectic solvent for the alkoxycarbonylation of ethylene with carbon monoxide and n-propanol to synthesize propyl propionate, comprising the steps of:
1) N-propanol (8.04 g,10 ml), palladium acetate (0.0133 mmol,3.0 mg), 1, 2-bis (di-t-butylphosphinomethyl) benzene (0.0534 mmol,21.0 mg) and acid halogen-free deep eutectic solvent No. 7 (70 wt%,5.6 g) were charged into a 50ml autoclave equipped with a tetrafluoroethylene liner;
2) Sealing and introducing carbon monoxide to 0.5MPa, vigorously stirring for 5min, discharging gas, and repeating for two times to discharge air in the autoclave;
3) The kettle was warmed to 80℃and a mixture of ethylene (0.0196 mol,0.549 g) and carbon monoxide (0.0196 mol,0.549 g) in a molar ratio of 1:1 was introduced to 2.0MPa, the timing was started and the reaction pressure was recorded after 2h, recorded as cycle 1; after the cycle 1 is finished, introducing mixed gas of 2.0MPa, and recording the reaction pressure after 2 hours, wherein the reaction pressure is recorded as cycle 2; the same steps are cycled through operation until cycle 5;
4) Taking out the autoclave, rapidly cooling to room temperature, discharging residual gas in the autoclave, opening the autoclave body, collecting the product, and carrying out chromatographic analysis to obtain the cycle 1 conversion rate of 5%.
Compared with the embodiment 3, the halogen-free deep eutectic solvent using p-toluenesulfonic acid as a hydrogen bond donor can complete 18 cycles, and the halogen-free deep eutectic solvent using benzoic acid as the hydrogen bond donor has extremely low reactivity, which indicates that the halogen-free deep eutectic solvent prepared by the preparation method of the application has reasonable design and improves the catalytic activity.
The application provides a preparation method of an acidic halogen-free deep eutectic solvent with controllable acidity, simple preparation and high reaction efficiency. The obtained deep eutectic solvent is applied to alkoxycarbonyl reaction of alkene and/or alkyne, and the acid halogen-free deep eutectic solvent is used as an acid promoter in a system, so that self-separation of the catalyst in the alkoxycarbonyl reaction of alkene and/or alkyne is realized, and the cost of catalyst separation is reduced. The acid halogen-free deep eutectic solvent retains more activity than the acid promoter in conventional homogeneous systems after isolation of the product compared to conventional homogeneous reactions.
The deep eutectic solvent, the preparation method and the application thereof provided by the application are described in detail, and specific examples are applied to illustrate the principle and the implementation of the application, and the description of the examples is only used for helping to understand the method and the core idea of the application; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.

Claims (14)

1. The preparation method of the deep eutectic solvent is characterized by comprising the following steps: and mixing and reacting the hydrogen bond donor and the hydrogen bond acceptor to obtain the deep eutectic solvent.
2. The method of preparing a deep eutectic solvent according to claim 1, wherein the hydrogen bond donor comprises one or more of p-toluene sulfonic acid, p-toluene sulfonic acid monohydrate, 4-nitrobenzene sulfonic acid, methyl sulfonic acid, trifluoromethyl sulfonic acid, formic acid, acetic acid, oxalic acid, propionic acid, or benzoic acid.
3. The method of preparing a deep eutectic solvent according to claim 1, wherein the hydrogen bond acceptor comprises one or more of l-carnitine, urea, lidocaine, acetamide, benzamide, 4-aminotoluene-3-sulfonic acid, 4-picolinic acid, proline, 2-picolinic acid, N- β -hydroxyethyl piperazine, or β -alanine.
4. The method of preparing a deep eutectic solvent according to claim 1, wherein the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is (0.2-5): 1.
5. The method of preparing a deep eutectic solvent according to claim 1, wherein the reaction temperature is 25 ℃ to 200 ℃.
6. The method for preparing a deep eutectic solvent according to claim 1, wherein the reaction time is 0.5 to 48 hours.
7. A deep eutectic solvent prepared by the method of any one of claims 1 to 6, wherein the pH of the deep eutectic solvent is 0.5 to 7.0.
8. The deep eutectic solvent of claim 7, wherein the deep eutectic solvent is halogen-free.
9. Use of the deep eutectic solvent prepared by the preparation method according to any one of claims 1 to 6 or the deep eutectic solvent according to any one of claims 7 to 8 in an alkoxycarbonyl reaction of olefins and/or alkynes.
10. The use according to claim 9, wherein the alkoxycarbonyl reaction comprises:
mixing the deep eutectic solvent, alcohols, palladium salt and ligand in an autoclave;
sealing the autoclave and introducing carbon monoxide to vent air from the autoclave;
heating the autoclave, introducing the carbon monoxide, and adding the alkene and/or alkyne to react;
the autoclave was cooled to quench the reaction.
11. The use according to claim 9, wherein the olefin comprises one or more of ethylene, propylene, butene, 1, 3-butadiene, 1-pentene, 2-methyl-1, 3-butadiene, 1-hexene, 1,2,3, 4-tetrahydrobenzene, heptene, vinylbenzene or allylbenzene; and/or the number of the groups of groups,
the alkyne comprises one or more of acetylene, propyne, dimethyl acetylene, pentyne, hexyne, heptyne, ethynylbenzene, 1-phenyl-1-propyne or 3-phenyl-1-propyne.
12. The use according to claim 10, wherein the mass ratio of the deep eutectic solvent to the alcohols is (0.1-1.5): 1.
13. The use according to claim 10, wherein the alcohol comprises one or more of methanol, ethanol, ethylene glycol, 1-propanol, 2-methylpropanol, 1,2, 3-glycerol, 1-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-butanol, 1-pentanol, 3-methyl-1-butanol, 2-dimethylpropanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol or 3-hexanol; and/or the number of the groups of groups,
the palladium salt comprises one or more of palladium acetate, palladium chloride, palladium bromide, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium (II) dichloride, palladium nitrite, palladium sulfate, ammonium tetrachloropalladate, potassium hexachloropalladate, dichlorodiammine palladium, tetraamine palladium chloride, bis (triphenylphosphine) palladium (II) acetate or trans-bis (benzonitrile) dichloropalladium (II); and/or the number of the groups of groups,
the ligand includes one or more of diphenyl-2-pyridinium phosphine, 1, 2-bis (di-t-butylphosphinomethyl) benzene, 1' -bis (diphenylphosphinomethyl) ferrocene, 1, 3-bis (diphenylphosphinomethyl) propane, 1, 2-bis (diphenylphosphinomethyl) benzene, bis [ (2-diphenylphosphinomethyl) phenyl ] ether, dimethylphenylphosphine, 1, 4-bis (diphenylphosphinomethyl) butane, tripropylphosphine, 1, 5-bis (diphenylphosphinomethyl) pentane, 1, 2-bis (diphenylphosphinomethyl) ethane or diphenylcyclohexyl phosphine.
14. Use according to claim 10, characterized in that in the step of heating the autoclave, the temperature of the heating is 60-160 ℃.
CN202310076878.2A 2023-01-16 2023-01-16 Deep eutectic solvent and preparation method and application thereof Pending CN116078430A (en)

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