Silver-based cluster composite material and application thereof in epoxy ring-opening catalytic reaction
The ring-opening reaction of styrene and alcohol by catalyzing the Ag32/AC catalyst, a silver group cluster composite material, solves the problems of harsh reaction conditions and low catalyst efficiency in the existing technology, and achieves a highly efficient and selective catalytic effect, which is suitable for industrial production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-24
- Publication Date
- 2026-07-10
AI Technical Summary
Existing ring-opening reactions of epoxy compounds require harsh reaction conditions and have low catalyst turnover rates or frequencies, which limits their industrial application.
Using the silver group cluster composite material Ag32/AC as a catalyst, Ag32 nanoclusters were loaded onto supercapacitor activated carbon through a simple preparation method to form the Ag32/AC catalyst, which was used to catalyze the ring-opening reaction of styrene and alcohol.
It achieves highly efficient and selective catalytic activity, with a catalytic yield of 98%, a reaction selectivity of 100%, few side reactions, mild conditions, and easy recycling, making it suitable for industrial applications.
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Figure CN122352364A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic catalysis, specifically relating to a silver group cluster composite material and its application in the ring-opening catalytic reaction of epoxy. Background Technology
[0002] Ring-opening reactions of epoxides are a key pathway for constructing carbon-oxygen and carbon-nitrogen bonds in organic synthesis. Styrene oxide, as an important epoxide derivative, produces β-alkoxyphenylethanol compounds, which are core raw materials for the synthesis of pharmaceutical intermediates, fine chemicals, and functional materials. They are widely used in drug synthesis, fragrance preparation, and the production of high-performance polymer materials.
[0003] Currently, the ring-opening reaction of epoxides with alcohols or amines has attracted widespread attention from researchers. Existing literature reports the use of Brønsted acid-base, Lewis acid-base (such as metal halides), transition metal salts, and their complexes as catalysts for the ring-opening reaction of epoxides. Although these catalytic systems can effectively activate epoxides to some extent, they still face many challenges in practical applications. For example, many reaction systems still require harsh reaction conditions, including high temperatures, long reaction times, or the use of excessive nucleophiles, and the catalyst turnover rate or frequency is low. These problems greatly limit the industrial application of such catalysts. Therefore, developing a simple, mild, green, and efficient silver-group cluster composite catalyst system for the ring-opening reaction of styrene oxidation has significant theoretical and practical value for promoting the green synthesis and industrial application of β-alkoxyphenylethanol fine chemicals. Summary of the Invention
[0004] To overcome the shortcomings of the existing technology, this invention provides a silver-group cluster composite material and its application in the ring-opening catalytic reaction of epoxy resin. The silver nanoclusters prepared by this invention are simple and exhibit excellent stability. This silver-group cluster composite catalyst demonstrates high catalytic activity in the ring-opening reaction of styrene and methanol, achieving a catalytic yield of up to 98% and a reaction selectivity of 100%. It can efficiently and directionally generate the target product 2-methoxy-2-phenylethanol, effectively suppressing side reactions, and the catalytic conditions are mild, with the catalyst easily recyclable.
[0005] The silver group cluster composite material of this invention is abbreviated as Ag. 32 / AC, where Ag 32 Indicates Ag 32 (dppp)4(CCR) 22 dppp = 1,3-bis(diphenylphosphine)propane, CCR = 4-tert-butylphenylacetylene, and AC represents supercapacitor activated carbon.
[0006] The preparation method of the silver group cluster composite material of the present invention includes the following steps:
[0007] Step 1: Dissolve AgSbF6 in ethanol, stir well, and then add it dropwise to a dichloromethane solution containing 4-tert-butylphenylacetylene and 1,3-bis(diphenylphosphine)propane. Stir vigorously until completely dissolved. Then, add triethylamine dropwise to the mixture, and the solution immediately changes from colorless to purple. Place the mixture at room temperature under 475 nm light for 24 hours. After the reaction is complete, remove the solvent by vacuum distillation. Dissolve the obtained solid in dichloromethane, centrifuge, discard the insoluble impurities at the bottom, and collect the supernatant. The collected filtrate is then subjected to rotary evaporation to obtain green Ag. 32 (dppp)4(CCR) 22 Nanoclusters, abbreviated as Ag 32 .
[0008] Step 2: Add 3mg Ag 32 Dissolve in 5 mL of dichloromethane, stir to disperse evenly, then add 97 mg of activated carbon, stir thoroughly at room temperature for 3 hours, centrifuge to collect the precipitate, wash the precipitate with ethanol at least 3 times, and dry under vacuum at 50 °C to obtain Ag. 32 / AC composite catalyst, with a loading of 3 wt% (as Ag) 32 (Total mass meter of nanoclusters).
[0009] The activated carbon is supercapacitor activated carbon.
[0010] The present invention relates to the application of silver group cluster composite materials in the catalytic oxidation of styrene and the ring-opening reaction of alcohols.
[0011] The catalytic reaction includes the following steps:
[0012] Add styrene oxide (0.1842 mmol, 21 µL), 1.5 mL of alcohol, and 100 mg of Ag to Schlenk tubes, respectively. 32 / AC catalyst. The reaction was carried out in an inert gas atmosphere and stirred at 40°C for 30-45 minutes. At the end of the reaction, propylbenzene was added as an internal standard, followed by extraction of organic matter with ethyl acetate. The mixture was then diluted to a certain concentration and the yield of the target product was determined by gas chromatography (GC).
[0013] The alcohol is an alkyl alcohol R-OH. R is selected from C1-C10 straight-chain or branched alkyl groups.
[0014] The synthesis route is shown below:
[0015]
[0016] Compared with the prior art, the beneficial effects of the present invention are reflected in:
[0017] 1. Compared with cobalt, zinc and nickel complex catalysts, the silver group cluster composite catalyst of the present invention is basically non-toxic. As a highly efficient heterogeneous catalyst, it has a high specific surface area and excellent selectivity, ensuring high product purity and high atom economy of the reaction.
[0018] 2. The silver group cluster composite catalyst of the present invention exhibits high catalytic activity in the ring-opening reaction of styrene and methanol oxidation, with a catalytic yield of 98%, providing a reference for the selection of catalysts for subsequent epoxide ring-opening reactions.
[0019] 3. The experimental process of this invention is simple and easy to carry out, and the cost is low, making it highly applicable.
[0020] 4. The catalytic system described in this invention has mild reaction conditions, does not require high temperature and high pressure, or strong acid and alkali environments, and can be carried out under mild heating conditions, making it highly operable; the reaction selectivity reaches 100%, and it can efficiently and directionally generate the target product 2-methoxy-2-phenylethanol, effectively suppressing the occurrence of side reactions. Attached Figure Description
[0021] Figure 1 This is a flowchart illustrating the preparation of the silver group cluster composite catalyst according to the present invention.
[0022] Figure 2 Preparation of Ag for this invention 32 Single-crystal structure diagram of nanoclusters. Yellow and blue represent Ag atoms, magenta represents P atoms, and gray represents C atoms.
[0023] Figure 3 This is a transmission electron microscope (TEM) image of the silver group cluster composite catalyst prepared in this invention.
[0024] Figure 4 A comparison of the catalytic yields of the ring-opening reactions of styrene and methanol catalyzed by different supported silver group cluster composite catalysts prepared in this invention.
[0025] Figure 5 The hydrogen NMR spectrum of 2-methoxy-2-phenylethanol obtained by the ring-opening reaction of styrene and methanol catalyzed by the silver group cluster composite catalyst prepared in this invention.
[0026] Figure 6 The graph shows a comparison of the yields of the silver group cluster composite catalyst prepared in this invention for catalyzing the ring-opening reaction of styrene with different alcohol substrates to produce the corresponding β-alkoxyphenylethanol products. Detailed Implementation
[0027] The technical solution of the present invention will be further explained and illustrated below through specific embodiments.
[0028] Example 1: Ag32 (dppp)4(CCR) 22 Preparation of nanoclusters
[0029] At room temperature, 32 mg (0.1 mmol) of AgSbF6 was dissolved in 2 mL of ethanol. This solution was then added dropwise to a 2 mL solution of dichloromethane containing 18 μL (0.1 mmol) of 4-tert-butylphenylacetylene and 41 mg (0.1 mmol) of 1,3-bis(diphenylphosphine)propane. After vigorous stirring until complete dissolution, 14 μL of triethylamine was added dropwise. The solution immediately changed from colorless to purple. The solution was then placed at room temperature and reacted under 475 nm light for 24 hours. After the reaction was complete, the reaction solvent was removed by vacuum distillation. The solid was then dissolved in 2 mL of dichloromethane, centrifuged, and the insoluble impurities at the bottom were discarded. The supernatant was collected and subjected to rotary evaporation to obtain green Ag. 32 (dppp)4(CCR) 22 Nanoclusters.
[0030] Example 2: Silver group cluster composite catalyst Ag 32 Preparation of / AC
[0031] 3 mg Ag 32 Nanoclusters were dissolved in 5 mL of dichloromethane solvent, then 97 mg of activated carbon was added to the solution and stirred at room temperature for 3 hours. The reaction solution was centrifuged, the precipitate was collected, and the solution changed from green to colorless, confirming the presence of Ag. 32 Successful loading was achieved on activated carbon. The collected precipitate was dried at room temperature for 5 hours to obtain the silver group cluster composite catalyst Ag. 32 / AC, with a load of 3 wt%.
[0032] Example 3: Ag 32 / AC catalytic oxidation of styrene and the ring-opening reaction of methanol (also known as Ag) 32 -5)
[0033] Weigh 100 mg Ag using a 10 ml Schlenk tube. 32 The AC catalyst was placed in a tube, and 21 µL (0.1842 mmol) of styrene oxide and 1.5 mL of methanol were added. The tube was sealed with a rubber stopper, evacuated, and a nitrogen balloon was attached. The Schlenk tube was then placed on a stirrer at 40 °C for 45 min. At the end of the reaction, the balloon was removed, and 25.7 μL of propylbenzene was added as an internal standard. Ethyl acetate was then added to extract the organic matter. After dilution to a certain concentration, the solution was filtered through a membrane and transferred to a gas chromatography bottle. The product yield (98%) was analyzed by gas chromatography.
[0034] Example 4: Activated carbon catalytic oxidation of styrene and methanol ring-opening reaction (without Ag) 32 (cluster)
[0035] Using a 10 mL Schlenk tube, weigh 100 mg of activated carbon catalyst and add 21 µL (0.1842 mmol) of styrene oxide and 1.5 mL of methanol. Seal the tube with a rubber stopper, evacuate the system, attach a nitrogen balloon, and then place the Schlenk tube on a 40 °C stirrer for 45 min. At the end of the reaction, remove the balloon and add 25.7 μL of propylbenzene as an internal standard. Extract the organic matter with ethyl acetate, dilute to a certain concentration, filter through a membrane, and transfer the liquid to a gas chromatograph. Analyze the product yield (7%) using gas chromatography.
[0036] Example 5: Ag 32 / AC catalytic oxidation of styrene and methanol ring-opening reaction (different supported types, same loading amount)
[0037] Weigh out 100 mg of Ag using four 10 ml Schlenk tubes. 32 Multi-walled carbon nanotubes (Ag) 32 -1), 100mgAg 32 Short multi-walled carbon nanotubes (Ag) 32 -2), 100 mgAg 32 / Graphene oxide (Ag) 32 -3), 100 mgAg 32 Hydroxyapatite (Ag) 32 -4) The catalyst was placed in the tube, and 21 µL (0.1842 mmol) of styrene oxide and 1.5 mL of methanol were added. The tube was sealed with a rubber stopper, the system was evacuated, a nitrogen balloon was attached, and the Schlenk tube was placed on a 40°C stirrer for 45 min. At the end of the reaction, the balloon was removed, and 25.7 μL of propylbenzene was added as an internal standard. Ethyl acetate was then added to extract the organic matter. After diluting to a certain concentration, the liquid was filtered through a membrane and placed in a gas chromatography bottle. The product yields were analyzed by gas chromatography (17%, 35%, 13%, and 2%, respectively).
[0038] Example 6: Ag 32 / AC catalytic oxidation of styrene and methanol ring-opening reaction (different reaction times)
[0039] Weigh 100 mg Ag using four 10 ml Schlenk tubes. 32The AC catalyst was placed in a tube, and 21 µL (0.1842 mmol) of styrene oxide and 1.5 mL of methanol were added. The tube was sealed with a rubber stopper, and the system was evacuated. A nitrogen balloon was attached, and the Schlenk tube was placed on a stirrer at 40 °C for 0.5 h, 1 h, 1.5 h, and 2 h, respectively. At the end of the reaction, the balloon was removed, and 25.7 μL of propylbenzene was added as an internal standard. Ethyl acetate was then added to extract the organic matter. After dilution to a certain concentration, the liquid was filtered through a membrane and placed in a gas chromatography bottle. The product yields were analyzed by gas chromatography (94%, 99%, 99%, 99%, respectively).
[0040] Example 7: Ag 32 / AC catalytic oxidation of styrene and methanol ring-opening reaction (at different reaction temperatures)
[0041] Weigh 100 mg Ag using three 10 ml Schlenk tubes. 32 The AC catalyst was placed in a tube, and 21 µL (0.1842 mmol) of styrene oxide and 1.5 mL of methanol were added. The tube was sealed with a rubber stopper, and the system was evacuated. A nitrogen balloon was attached, and the Schlenk tube was placed on a stirrer at 20°C, 30°C, and 50°C for 45 min, respectively. At the end of the reaction, the balloon was removed, and 25.7 μL of propylbenzene was added as an internal standard. Ethyl acetate was then added to extract the organic matter. After dilution to a certain concentration, the liquid was filtered through a membrane and placed in a gas chromatography bottle. The product yields were analyzed by gas chromatography (49%, 70%, and 97%, respectively).
[0042] Example 8: Ag 32 / AC-catalyzed synthesis of 2-ethoxy-2-phenylethanol
[0043] Weigh 100 mg Ag using a 10 ml Schlenk tube. 32 The AC catalyst was placed in a tube, and 21 µL (0.1842 mmol) of styrene oxide and 720 μL of ethanol were added. The tube was sealed with a rubber stopper, evacuated, and a nitrogen balloon was attached. The Schlenk tube was then placed on a stirrer at 40 °C for 4 h. At the end of the reaction, the balloon was removed, and 25.7 μL of propylbenzene was added as an internal standard. Ethyl acetate was then added to extract the organic matter. After diluting to a certain concentration, the liquid was filtered through a membrane and placed in a gas chromatography bottle. The product yield (96%) was analyzed by gas chromatography.
[0044] Example 9: Ag 32 / AC-catalyzed synthesis of 2-isopropoxy-2-phenylethanol
[0045] Weigh 100 mg Ag using a 10 ml Schlenk tube. 32The AC catalyst was placed in a tube, and 21 µL (0.1842 mmol) of styrene oxide and 945 μL of isopropanol were added. The tube was sealed with a rubber stopper, evacuated, and a nitrogen balloon was attached. The Schlenk tube was then placed on a stirrer at 40 °C and reacted for 4 h. At the end of the reaction, the balloon was removed, and 25.7 μL of propylbenzene was added as an internal standard. Ethyl acetate was then added to extract the organic matter. After diluting to a certain concentration, the liquid was filtered through a membrane and placed in a gas chromatograph. The product yield (92%) was analyzed by gas chromatography.
[0046] Example 10: Ag 32 / AC-catalyzed synthesis of 2-butoxy-2-phenylethanol
[0047] Weigh 100 mg Ag using a 10 ml Schlenk tube. 32 The AC catalyst was placed in a tube, and 21 µL (0.1842 mmol) of styrene oxide and 1.129 mL of n-butanol were added. The tube was sealed with a rubber stopper, evacuated, and a nitrogen balloon was attached. The Schlenk tube was then placed on a stirrer at 40 °C for 4 h. At the end of the reaction, the balloon was removed, and 25.7 μL of propylbenzene was added as an internal standard. Ethyl acetate was then added to extract the organic matter. After dilution to a certain concentration, the solution was filtered through a membrane and transferred to a gas chromatography bottle. The product yield (86%) was analyzed by gas chromatography.
[0048] Example 11: Ag 32 / AC-catalyzed synthesis of 2-octyloxy-2-phenylethanol
[0049] Weigh 100 mg Ag using a 10 ml Schlenk tube. 32 The AC catalyst was placed in a tube, and 21 µL (0.1842 mmol) of styrene oxide and 1.943 mL of n-octanol were added. The tube was capped with a rubber stopper, the system was evacuated, a nitrogen balloon was attached, and the Schlenk tube was placed on a stirrer at 40 °C for 4 h. At the end of the reaction, the balloon was removed, and 25.7 μL of propylbenzene was added as an internal standard. Ethyl acetate was then added to extract the organic matter, and the solution was diluted to a certain concentration, filtered through a membrane, and the liquid was transferred to a gas chromatography bottle. The product yield (84%) was analyzed by gas chromatography.
Claims
1. A silver group cluster composite material, characterized in that: The silver group cluster composite material is abbreviated as Ag. 32 / AC, where Ag 32 Indicates Ag 32 (dppp)4(CCR) 22 dppp = 1,3-bis(diphenylphosphine)propane, CCR = 4-tert-butylphenylacetylene, and AC represents supercapacitor activated carbon.
2. The method for preparing the silver group cluster composite material according to claim 1, characterized in that... Includes the following steps: Step 1: Dissolve AgSbF6 in ethanol, stir well, and then add it dropwise to a dichloromethane solution containing 4-tert-butylphenylacetylene and 1,3-bis(diphenylphosphine)propane, stirring until completely dissolved. Then, add triethylamine dropwise to the mixture; the solution immediately changes from colorless to purple. Place the mixture at room temperature under 475 nm light for 24 hours. After the reaction, remove the solvent by vacuum distillation. Dissolve the resulting solid in dichloromethane, centrifuge, discard the insoluble impurities at the bottom, and collect the supernatant. The collected filtrate is then subjected to rotary evaporation to obtain green Ag. 32 (dppp)4(CCR) 22 Nanoclusters, abbreviated as Ag 32 ; Step 2: Add Ag 32 Dissolve in dichloromethane, stir to disperse evenly, add activated carbon, stir thoroughly at room temperature, centrifuge to collect the precipitate, wash the precipitate with ethanol, and vacuum dry to obtain Ag. 32 / AC composite catalyst.
3. The preparation method according to claim 2, characterized in that: The Ag 32 Ag in AC composite catalyst 32 The loading of nanoclusters was 3 wt%.
4. The preparation method according to claim 2, characterized in that: The activated carbon is supercapacitor activated carbon.
5. The application of the silver group cluster composite material of claim 1 in the catalytic oxidation of styrene and the ring-opening reaction of alcohols.
6. The application according to claim 5, characterized in that: In an inert gas atmosphere, a ring-opening reaction is carried out using styrene oxide and alcohols as reactants and the silver group cluster composite material as a catalyst. The alcohol is an alkyl alcohol R-OH, wherein R is selected from C1-C10 straight-chain or branched alkyl groups; The synthesis route is shown below: 。 7. The application according to claim 6, characterized in that: The reaction temperature is 40℃ and the reaction time is 30-45 min.