CN115353461B - Core-shell structure polymerized ionic liquid catalytic hydrogenation reaction - Google Patents

Core-shell structure polymerized ionic liquid catalytic hydrogenation reaction Download PDF

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CN115353461B
CN115353461B CN202210845170.4A CN202210845170A CN115353461B CN 115353461 B CN115353461 B CN 115353461B CN 202210845170 A CN202210845170 A CN 202210845170A CN 115353461 B CN115353461 B CN 115353461B
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cpdb
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应安国
鲁小彤
李胜男
赵成瑶
刘玉静
刘中秋
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Anhui Zhonghuifa New Materials Co.,Ltd.
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Qufu Normal University
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    • B01J2231/60—Reduction reactions, e.g. hydrogenation
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    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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Abstract

The invention relates to a method for realizing unsaturated olefin hydrogenation by a high-efficiency and environment-friendly core-shell catalyst under a mild (room temperature) reaction condition. The method comprises the steps of taking a core-shell structured polymer ionic liquid hybridization nano-reactor (MIE@Pd/SiNP-CPDB) as a catalyst, taking water as a solvent, and carrying out hydrogenation reaction at room temperature and normal pressure to obtain corresponding alkane, wherein the catalytic effect of the catalyst is not greatly reduced after the catalyst is repeatedly used for 7 times. The core-shell catalyst with large surface area and good dispersibility can be rapidly recovered by centrifugation. The method has the advantages of simple operation, high yield, good reusability of the catalytic reaction system, mild reaction conditions and good green industrialized prospect.

Description

Core-shell structure polymerized ionic liquid catalytic hydrogenation reaction
Technical Field
The invention relates to a method for preparing corresponding saturated alkane by catalyzing hydrogenation reaction of unsaturated alkene with water as solvent at normal temperature and normal pressure by a high-efficiency pollution-free core-shell structure polymeric ionic liquid nano reactor.
Background
In recent years, in order to realize sustainable development, realization of environmentally friendly organic synthesis has become an urgent issue, and is an important content of green chemistry. The traditional organic synthesis usually uses an organic solvent as a medium, so that the environment is polluted. Many methods for substituting the conventional organic solvents, such as solvent-free reaction, reaction using water as a medium, reaction using supercritical fluid as a solvent, reaction using fluorine two-phase system as a medium, reaction using room temperature ionic liquid as a solvent, etc., have been studied by chemists of various countries. The method can replace the traditional organic solvent, reduce pollution, and also can change and improve the selectivity and conversion rate of the reaction or make the separation and purification and other processes easier to carry out because the method provides a new molecular environment for the reaction molecules. Organic synthesis reactions that are relatively solvent-free or water-mediated should be preferred under otherwise similar conditions because of the minimal cost of solvents.
However, most water-catalyzed reactions still suffer from low reaction efficiency due to the extremely high mass transfer resistance caused by the incompatibility of water and organics. Core-shell structural materials are a good alternative to solve the above problems, because their cores and shells can be selectively functionalized and the catalytically active sites can be separated. The improved St method is adopted to prepare hydrophobic silica microspheres rich in alkane, then the microspheres loaded with Pd nano particles after ammoniation are used as core materials, and a layer of hydrophilic ionic liquid is assembled on the surfaces of the microspheres through reversible addition-fragmentation chain transfer grafting (RAFT) polymerization, so that the core-shell structure polymer ionic liquid hybridization catalyst is synthesized. The prepared nano catalyst with the core-shell structure not only shows good dispersibility in a solvent, but also can adsorb the hydrophobic part of an organic matrix, so that the nano composite material has excellent hydrogenation catalytic performance. The technology provides a broad prospect for the preparation of the supported noble metal core-shell catalyst and the catalytic performance thereof.
Disclosure of Invention
The invention aims to solve the technical problem of replacing the traditional method for preparing saturated alkane compounds by catalytic hydrogenation reaction of a catalyst, provides an environment-friendly and efficient recyclable core-shell polymerization ionic liquid catalyst, and overcomes the defect of large mass transfer resistance of a multiphase interface under normal temperature and normal pressure by taking water as a solvent to realize hydrogenation reaction.
According to the present invention, the method for producing a saturated alkane compound by hydrogenation of an unsaturated alkene compound with hydrogen gas comprises: taking a core-shell structure polymerization ionic liquid nano-reactor as a catalyst, taking water as a solvent at normal temperature and normal pressure, and reacting unsaturated olefins with hydrogen for 10-60 min to obtain corresponding saturated alkane compounds; wherein the catalyst is shown in fig. 2.
Wherein the volume of deionized water is 5 mL.
Wherein the dosage of the catalyst is 10-20 mg.
Wherein the amount of the unsaturated olefins is 1 mmol.
Wherein the hydrogenation reaction condition of the catalyst is normal temperature and normal pressure.
Wherein the unsaturated olefins are cinnamyl alcohol, cinnamyl aldehyde, cinnamyl nitrile, 2-nitrocinnamyl aldehyde, styrene, 4-vinylbenzyl chloride, 4-ethylstyrene, phenylacetylene, allyl benzene, 4-methylphenylacetylene, 4-methylstyrene, butyl acrylate and 4-bromo-1-butene.
After the reaction is finished, separating the catalyst from the product by centrifugation, pouring out supernatant to obtain the product, and drying MIE@Pd/SiNP-CPDB at 60 ℃ in vacuum for 10 h for repeated use, wherein the reaction effect is not obviously reduced.
The method for catalyzing unsaturated olefin hydrogenation reaction by utilizing the core-shell structure polymeric ionic liquid nano-reactor provided by the invention is realized by the following ways:
the preparation process of the core-shell structure polymeric ionic liquid nano-reactor used in the invention comprises the following steps:
triethylene glycol monomethyl ether (1.2 eq) and 4-toluenesulfonyl chloride (1 eq) were dissolved in methylene chloride, triethylamine (1.5 eq) was added dropwise under ice water bath and stirred overnight at room temperature, and the pure product was separated by silica gel column chromatography to give a yellow oily liquid. Dissolving equimolar amount of yellow oily liquid, 1-vinylimidazole and potassium carbonate in ultra-dry acetonitrile under nitrogen protection of 60% o C reaction 24 h. After the reaction is finished, cooling to room temperature, filtering and precipitating, extracting and removing impurities by using ethyl acetate, and then distilling under reduced pressure to obtain a product MIE ILs, wherein the ionic liquid is shown in figure 3.
The St amber process prepares hydrophobic silica microspheres rich in alkane, dispersing 0.3. 0.3 g microspheres in anhydrous toluene, adding 0.6 mmol of 3-aminopropyl triethoxysilane, refluxing 24. 24 h at 110 ℃, centrifuging the product, and vacuum drying at 70 ℃. To SiNP-NH 2 (1.0 g) was dispersed in dry THF (30 mL), then activated RAFT reagent (CPDB-NHS, 0.18 g,0.47 mmol) was added and stirred at room temperature for 24 h. After the completion of the reaction, the reaction mixture was separated by centrifugation, and washed with ethanol to obtain Sinp-CPDB. Extracting template agent in SiNP-CPDB with ethanol under reflux twice, removing, and collecting template agent in Pd (OAc) 2 65 Adding above 1.0g synthetic SiNP-CPDB into toluene solution, stirring for 2 h, adding NaBH 4 (120 mg) and methanol (2 mL), washing with ethanol and drying to obtain Pd/SiNP-CPDB catalyst. Finally, methanol (15 mL), MIE-ILS (0.42 g,1.0 mmol), CPDB (10 mg) and AIBN (0.03 g,0.24 mmol) were added to a 50 mL Schlenk tube. The Schlenk tube was replaced with nitrogen 3 times in an ice bath, stirred at 70℃for 12 h, and finally the reaction mixture was separated by centrifugation, washed twice with methanol and dried under vacuum at 60℃for 24 h to give nMIE@Pd/SiNP-CPDB (n represents different molar addition of ILs).
The preparation process of saturated alkane products comprises the following steps:
to the reaction flask were added MIE@Pd/SiNP-CPDB (20 mg), styrene (2 mmol), water (5 mL). Wherein the consumption of the styrene is 1 mmol, the catalyst consumption is 10-20 mg, water is used as a solvent, and the reaction is carried out for 10-60 min at normal temperature and normal pressure. After the reaction is finished, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product, wherein the product is detected by using a gas chromatograph-mass spectrometer. After the catalyst has been washed with methanol, it is passed through 60 o And C, drying in vacuum to 10 h, wherein the catalyst is reused for 7 times for the next batch of reaction, and the reaction yield is not obviously reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure.
FIG. 1 is a flow chart of the preparation of the core-shell polymeric ionic liquid nanoreactor according to one embodiment of the invention.
FIG. 2 is a diagram of the catalyst MIE@Pd/SiNP-CPDB in an embodiment of the present invention.
FIG. 3 is a schematic illustration of the ionic liquid monomer MIE ILs, in accordance with one embodiment of the present invention.
Detailed Description
The following detailed description of the preferred embodiments of the invention will provide those skilled in the art with a better understanding of the advantages and features of the invention, so as to make the scope of the invention more clearly and clearly defined.
Example 1
MIE@Pd/SiNP-CPDB (20 mg), cinnamyl alcohol (1 mmol) and water (5 mL) were added to a reaction tube and H was introduced 2 And (3) reacting for 20 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after mixing well, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 92.31%.
Example 2
MIE@Pd/SiNP-CPDB (20 mg), cinnamaldehyde (1 mmol) and water (5 mL) were added to the reaction tube,introducing H 2 And (3) reacting for 60 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after uniform mixing, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 52.44%.
Example 3
MIE@Pd/SiNP-CPDB (20 mg), 2-nitrocinnamaldehyde (1 mmol) and water (5 mL) were added to a reaction tube and H was introduced 2 And (3) reacting for 60 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
Taking a product 1 mg, placing the product into a 2 mL sample tube, fixing the volume to 2 mL by using normal hexane, uniformly mixing, and detecting by using a gas chromatography-mass spectrometer to obtain the conversion rate of 78.90%.
Example 4
MIE@Pd/SiNP-CPDB (20 mg), cinnamonitrile (1 mmol) and water (5 mL) were added to a reaction tube and H was introduced 2 And (3) reacting for 60 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after mixing well, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 50.20%.
Example 5
MIE@Pd/SiNP-CPDB (20 mg), styrene (1 mmol) and water (5 mL) were added to a reaction tube and H was introduced 2 And (3) reacting for 10 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
Taking a product 1 mg, placing the product into a 2 mL sample tube, fixing the volume to 2 mL by using normal hexane, uniformly mixing, and detecting by using a gas chromatography-mass spectrometer to obtain the conversion rate of 100%.
Example 6
MIE@Pd/SiNP-CPDB (10 mg), styrene (1 mmol) and water (5 mL) were added to a reaction tube and H was introduced 2 And (3) reacting for 20 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after uniform mixing, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 60.70%.
Example 7
MIE@Pd/SiNP-CPDB (20 mg), 4-methylstyrene (1 mmol) and water (5 mL) were added to the reaction tube and H was introduced 2 And (3) reacting for 15 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
Taking a product 1 mg, placing the product into a 2 mL sample tube, fixing the volume to 2 mL by using normal hexane, uniformly mixing, and detecting by using a gas chromatography-mass spectrometer to obtain the conversion rate of 100%.
Example 8
MIE@Pd/SiNP-CPDB (20 mg), 4-ethylstyrene (1 mmol) and water (5 mL) were added to the reaction tube and H was introduced 2 And (3) reacting for 20 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after uniform mixing, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 97.51%.
Example 9
MIE@Pd/SiNP-CPDB (20 mg), allyl benzene (1 mmol) and water (5 mL) were added to a reaction tube and H was introduced 2 And (3) reacting for 20 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after uniform mixing, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 96.28%.
Example 10
MIE@Pd/SiNP-CPDB (20 mg), 4-vinylbenzyl chloride (1 mmol) and water (5 mL) were added to the reaction tube and H was introduced 2 And (3) reacting for 20 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after uniform mixing, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 100%.
Example 11
MIE@Pd/SiNP-CPDB (20 mg), 4-methylphenylacetylene (1 mmol) and water (5 mL) were added to the reaction tube and H was introduced 2 And (3) reacting for 15 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after uniform mixing, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 97.75%.
Example 12
MIE@Pd/SiNP-CPDB (20 mg), phenylacetylene (1 mmol) and water (5 mL) were added to a reaction tube and H was introduced 2 And (3) reacting for 20 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after uniform mixing, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 91.03%.
Example 13
MIE@Pd/SiNP-CPDB (20 mg), butyl acrylate (1 mmol) and water (5 mL) were added to a reaction tube and H was introduced 2 And (3) reacting for 15 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after uniform mixing, it was detected by a gas chromatograph-mass spectrometer to determine that the conversion was 95.42%.
Example 14
MIE@Pd/SiNP-CPDB (20 mg), 4-bromo-1-butene (1 mmol) and water (5 mL) were added to the reaction tube and H was introduced 2 And (3) reacting for 10 min, separating the catalyst from the product by centrifugation, and pouring out clear liquid to obtain the product.
The product 1 mg was taken and placed in a 2 mL sample tube, the volume was fixed to 2 mL with n-hexane, and after uniform mixing, it was detected by a gas chromatograph-mass spectrometer, and the conversion was found to be 98.94%.
Example 15
MIE@Pd/SiNP-CPDB (20 mg), styrene (1 mmol) and water (5 mL) were added to a reaction tube and H was introduced 2 Reacting for 10 min, separating the catalyst and the product by centrifugationPouring out the clear liquid to obtain the product.
Taking a product 1 mg, placing the product into a 2 mL sample tube, fixing the volume to 2 mL by using normal hexane, detecting by using a gas chromatograph-mass spectrometer after uniform mixing, and repeatedly using MIE@Pd/SiNP-CPDB for 7 times, wherein good catalytic efficiency is still reserved, and the specific is shown in a table 1.
Table 1 catalyst performance test table
Number of times Temperature (. Degree. C.) Reaction time (min) Conversion (%)
1 25 10 100
2 25 10 99.78
3 25 10 99.75
4 25 10 98.64
5 25 10 97.98
6 25 10 96.15
7 25 10 95.25
It should be noted that the foregoing summary and the detailed description are intended to demonstrate practical applications of the technical solution provided by the present invention, and should not be construed as limiting the scope of the present invention. Various modifications, equivalent alterations, or improvements will occur to those skilled in the art, and are within the spirit and principles of the invention. The scope of the invention is defined by the appended claims.

Claims (8)

1. The method for preparing the corresponding alkane by hydrogenating the unsaturated olefin is characterized by comprising the steps of taking a core-shell structure polymer ionic liquid hybridization nano reactor as a catalyst, taking water as a solvent, and carrying out hydrogenation reaction at room temperature and normal pressure to obtain the corresponding alkane, wherein the preparation method of the catalyst comprises the following steps:
preparation of ionic liquid: dissolving triethylene glycol monomethyl ether and 4-toluenesulfonyl chloride in dichloromethane, dropwise adding triethylamine under ice water bath, stirring at room temperature overnight, and separating a pure product by silica gel column chromatography to obtain yellow oily liquid; an equimolar amount of a yellow oily liquid, 1-vinylimidazole and potassium carbonate were dissolved in ultra-dry acetonitrile and under nitrogen blanket 60 o C, reacting 24 and h, cooling to room temperature after the reaction is finished, filtering and precipitating,removing impurities through ethyl acetate extraction, and then performing reduced pressure distillation to obtain ionic liquid MIE ILs;
preparation of the nanoreactor: dispersing hydrophobic silicon dioxide microsphere rich in alkane prepared by St amber method in anhydrous toluene, adding 3-aminopropyl triethoxysilane, refluxing at 110deg.C 24 h, centrifuging the product, and vacuum drying at 70deg.C to obtain SiNP-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the To SiNP-NH 2 Dispersing in dry tetrahydrofuran, adding activated RAFT reagent CPDB-NHS, stirring at room temperature for 24-h, separating the reaction mixture by a centrifugal method after the reaction is finished, and washing with ethanol to obtain SiNP-CPDB; extracting template agent in SiNP-CPDB with ethanol under reflux twice, adding the above synthetic SiNP-CPDB into toluene solution containing palladium acetate, stirring for 2 h, and adding NaBH 4 Washing and drying the mixture with methanol to obtain Pd/SiNP-CPDB; finally, methanol, MIE ILs, RAFT reagent and AIBN were added to the Schlenk tube, and the Schlenk tube was replaced with nitrogen 3 times in an ice-water bath and stirred at 70 ℃ for 12 h, and finally the reaction mixture was separated by centrifugation, washed twice with methanol, and dried under vacuum at 60 ℃ for 24 h to obtain the final nanoreactor nmie@pd/SiNP-CPDB.
2. The process of claim 1, wherein the olefin is added in an amount of 1 mmol.
3. The method of claim 1, wherein the MIE@Pd/SiNP-CPDB is added in an amount of 10-20 mg.
4. A process according to claim 1, 2 or 3, wherein the olefin is one of cinnamyl alcohol, cinnamyl aldehyde, cinnamyl nitrile, 2-nitrocinnamyl aldehyde, styrene, 4-vinylbenzyl chloride, 4-ethylstyrene, phenylacetylene, allylbenzene, 4-methylphenylacetylene, 4-methylstyrene, butyl acrylate, 4-bromo-1-butene.
5. The method of claim 1, wherein the hydrogenation solvent is deionized water.
6. The method of claim 1, wherein the hydrogenation reaction temperature is room temperature.
7. The method of claim 1, wherein the hydrogenation reaction time is 10 to 60 minutes.
8. The method of claim 1, wherein after the reaction is completed, the catalyst and the product are separated by centrifugation, and the supernatant is poured out to obtain the product.
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