Supported catalyst, process for its preparation and use thereof

Abstract

The application discloses a supported catalyst and a preparation method and application thereof, and the raw material of the supported catalyst comprises a ruthenium carbene complex, alkyl aluminum and / or alkyl aluminum oxide, a phosphine-based siloxane compound and a silicon-aluminum type mesoporous molecular sieve; wherein the silicon-aluminum type mesoporous molecular sieve has a silicon-aluminum molar ratio of 25-30, a specific surface area of 550-850 m 2 / g, a relative crystallinity of 90-95%, a pore size of 2.5-3.5 nm and a pore volume of 0.80-1.0 cm 3 / g. The active sites of the supported catalyst are fully exposed, the loading amount of the ruthenium carbene complex is high, the metal ruthenium is not easy to fall off, and the preparation process is simple, so that the supported catalyst can effectively initiate a 1-hexene metathesis reaction.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a supported catalyst, its preparation method, and its application. Background Technology

[0002] Under the action of a metal catalyst, the carbon-carbon double bonds in olefins are broken and recombine to form new molecules. This process is called olefin metathesis, also known as olefin transposition reaction. Olefin metathesis can achieve the growth of organic molecule carbon chains and the construction of special cyclic molecules. According to the changes in the molecular skeleton during the reaction, it can be divided into five types: cross metathesis, ring-closing metathesis, ring-opening cross metathesis, ring-opening transposition polymerization, and transposition polymerization of acyclic dienes.

[0003] Carbene complexes are commonly used catalysts in olefin metathesis reactions. Grubbs catalysts contain ruthenium, while Schrock catalysts contain molybdenum or tungsten. Among them, ruthenium-catalyzed olefin metathesis reactions are a powerful method for constructing carbon-carbon double bonds and are widely used in the synthesis of polymers, natural products, and pharmaceuticals, demonstrating enormous application potential and a broad market prospect. The two commonly used ruthenium catalysts are Grubbs 2nd and Grubbs-Hoveyda 2nd. To obtain catalysts with high activity and high selectivity, researchers have attempted to modify Grubbs 2nd and Grubbs-Hoveyda 2nd and support them with solids. The supported catalysts are easier to separate from the reaction system after the catalytic reaction, which can effectively increase the number of times the catalytic reaction can be reused.

[0004] For example, US Patent Document US2003064884A1 discloses a method for immobilizing ruthenium carbene complexes onto a polymer support. The immobilized ruthenium complexes can be recycled in the cyclization metathesis of dienes. This method can be immobilized on soluble polymers such as PEG and used in aqueous media. However, this catalyst is difficult to effectively initiate the metathesis reaction of 1-hexene.

[0005] Chinese patent document CN104624232A discloses methods for immobilized carbene catalysts in polystyrene and in silica. However, the specific operation steps are cumbersome and demanding, and the loading of polymer-supported catalysts is low. The catalytic activity of heterogeneous catalysts is lower than that of homogeneous ruthenium complexes, mainly due to insufficient exposure of active sites and poor contact with substrates of polymer-supported catalysts.

[0006] US Patent document US2012165588A1 discloses a method for loading ruthenium-carbene complexes onto silica, wherein the ratio of hydroxyl groups on the silica surface to those on the N2 BET surface is less than 2 hydroxyl groups / nm. 2The chemical reaction proceeds continuously in the operating reactor. The ratio of hydroxyl groups on the used silica surface to that on the N2 BET surface is adjusted by heat treatment of the silica to ensure that the molar ratio of hydroxyl groups to ruthenium carbene complex on the silica surface is at least 5. This supported catalyst can be used for olefin metathesis reactions. However, due to the small specific surface area and low loading of amorphous silica, the metal leaching is relatively high, resulting in a high ruthenium content in the product and causing product contamination. Summary of the Invention

[0007] In view of this, the present invention provides a supported catalyst, its preparation method and application, to solve the problems of insufficient exposure of active sites, low loading, easy ruthenium metal falling off and dissolving into the reaction product and causing ruthenium contamination, complex preparation process and difficulty in effectively initiating the 1-hexene metathesis reaction in the prior art.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] A supported catalyst, wherein the raw materials for the supported catalyst include:

[0010] (1) Ruthenium carbene complexes;

[0011] (2) Alkyl aluminum and / or alkyl aluminum oxane;

[0012] (3) Phosphosiloxane compounds;

[0013] (4) Silicate-alumina type mesoporous molecular sieve;

[0014] The silica-alumina mesoporous molecular sieve has a silica-alumina molar ratio of 25–30 and a specific surface area of ​​550–850 m². 2 / g, relative crystallinity 90%–95%, pore size 2.5–3.5 nm, pore volume 0.80–1.0 cm³ 3 / g.

[0015] Optionally, the ruthenium carbene complex is selected from Grubbs-type catalysts, Hoveyda-Grubbs-type catalysts, or (PCy3)2Cl2Ru=CHCH2OPh. The Grubbs-type catalyst can be selected from Grubbs 1, Grubbs 2, or their derivatives, preferably Grubbs 1 or Grubbs 2, with the following specific structure:

[0016]

[0017] The Hoveyda-Grubbs type catalyst can be selected from Hoveyda-Grubbs 1, Grubbs-Hoveyda 2 or their derivatives, with Grubbs-Hoveyda 1 or Grubbs-Hoveyda 2 being preferred. The specific structure is as follows:

[0018]

[0019] In this context, Ru represents metallic ruthenium(II), and PCy3 represents tricyclohexylphosphine.

[0020] Optionally, the alkylaluminum is selected from trialkylaluminum, preferably at least one of trimethylaluminum, triethylaluminum, and triisobutylaluminum;

[0021] The alkylaluminoxane is selected from at least one of methylaluminoxane (MAO), isobutylaluminoxane, trimethylaluminoxane, triethylaluminoxane, and triisobutylaluminoxane.

[0022] Optionally, the phosphonosiloxane compound is selected from at least one of 2-(diphenylphosphine)ethyltriethoxysilane, diethylphosphine ethyltriethoxysilane, 2-(diphenylphosphine)phenyltriethoxysilane, and 2-(diphenylphosphine)phenyltriphenoxysilane.

[0023] The present invention also provides a method for preparing the above-mentioned supported catalyst, comprising the following steps:

[0024] Activated silica-alumina mesoporous molecular sieve: In an inert gas atmosphere, the calcined silica-alumina mesoporous molecular sieve is reacted with alkylaluminum and / or alkylaluminoxane in toluene. After the reaction is completed, the sieve is washed (preferably with toluene) and vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve (stored in an anhydrous and oxygen-free environment).

[0025] Supported catalyst precursor: In an inert gas atmosphere, the activated silica-alumina type mesoporous molecular sieve is mixed with n-hexane to form a suspension, and then a phosphosiloxane compound is added to react (preferably under reflux, at about 70°C). After the reaction is completed, the free silicide is removed to obtain the supported catalyst precursor.

[0026] Supported catalyst: In an inert gas atmosphere, the supported catalyst precursor is reacted with the ruthenium carbene complex in n-hexane. After the reaction is completed, the catalyst is separated (preferably filtered), washed (preferably washed with n-hexane), and vacuum dried to obtain the supported catalyst.

[0027] The mass ratio of the calcined silica-alumina mesoporous molecular sieve to the alkylaluminum and / or alkylaluminoxane is 1:0.02 to 1:0.06.

[0028] The mass ratio of the activated silica-alumina type mesoporous molecular sieve to the phosphosiloxane compound is 1:0.13-0.20;

[0029] The mass ratio of the activated silica-alumina type mesoporous molecular sieve to the ruthenium carbene complex is 1:0.12 to 0.20.

[0030] The amount of solvent used in the entire preparation process is not specifically limited, as long as it can dissolve or disperse the solvent.

[0031] Optionally, the inert gas may be selected from argon, nitrogen, etc.

[0032] Optionally, the reaction temperature of the activated silica-alumina mesoporous molecular sieve preparation step is 60℃~100℃, and the time is 3~4 hours.

[0033] Optionally, in the preparation step of the supported catalyst precursor, a Soxhlet extractor is used to remove free silicides. Preferably, the extraction solution is a mixed solvent of diethyl ether and n-hexane with a volume ratio of 1:1 to 3, and the extraction time is 3 to 5 hours.

[0034] The reaction time for the preparation step of the supported catalyst precursor is 1 to 3 hours.

[0035] Optionally, the reaction temperature of the preparation step of the supported catalyst is 20-30°C, and the reaction time is 1-5 hours.

[0036] Optionally, the preparation method of the supported catalyst further includes a step of calcining the silica-alumina molecular sieve; preferably, the calcination temperature of the silica-alumina mesoporous molecular sieve is 130-150°C, and the time is 4-6 hours.

[0037] The present invention also provides the application of the above-mentioned supported catalyst or the supported catalyst prepared by the above-mentioned method in the catalytic metathesis reaction of 1-hexene, preferably in the application in the preparation of 5-decene from the metathesis reaction of 1-hexene.

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] Beneficial Effect 1: The supported catalyst provided by this invention uses a silica-alumina type mesoporous molecular sieve support with specific physicochemical properties and a mesoporous structure to support ruthenium carbene complexes (especially Grubbs 2 catalyst, (PCy3)2Cl2Ru=CHCH2OPh). This makes the pore size of the silica-alumina type mesoporous molecular sieve conducive to the entry of 1-hexene into the pores and its contact with the active sites of the catalyst. The high BET area is conducive to the high dispersion of the active sites. Combined with alkylalumina and / or alkylaluminoxanes and phosphine siloxane compounds, the loading of ruthenium carbene complexes is high, the active sites are fully exposed, and the metallic ruthenium is not easily detached.

[0040] Beneficial Effect 2: The method for preparing the supported catalyst provided by this invention uses an inert inorganic compound, aluminosilicate mesoporous molecular sieve with a mesoporous structure, as a support. First, the support is activated with alkylaluminum and / or alkylaluminoxanes. Then, a ruthenium carbene complex is attached to the support using a phosphine siloxane compound. Considering the physicochemical properties of the support and the limited amounts of each raw material, the resulting catalyst has fully exposed active sites, a high loading of the ruthenium carbene complex, and minimal ruthenium detachment. Furthermore, the preparation process is simple. If the order of adding the raw materials is changed during the preparation process, the loading of the ruthenium carbene complex in the supported catalyst will be significantly reduced, resulting in fewer and unevenly dispersed active sites, making it difficult to effectively initiate the 1-hexene metathesis reaction.

[0041] Beneficial Effect 3: The supported catalyst provided by this invention, or the supported catalyst prepared by the method thereof, exhibits a 1-hexene conversion rate greater than 50% and no byproducts when used in the metathesis reaction of 1-hexene, with a selectivity of 5-decene greater than 99.8%. Furthermore, after the metathesis reaction of 1-hexene is completed, the supported catalyst and product are easily separated (the supported catalyst can be removed by direct filtration, and the remaining product can be used to obtain 5-decene using vacuum distillation equipment commonly used in the art). The separated supported catalyst can be reused more than five times with virtually no byproducts, significantly improving economic efficiency. Detailed Implementation

[0042] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0043] For any experimental steps or conditions not specified in the examples and comparative examples, the procedures or conditions described in the literature in this field can be followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0044] In the following embodiments and comparative examples, the silicon-to-aluminum molar ratio is 25–30, and the specific surface area is 550–850 m². 2 / g, relative crystallinity 90%–95%, pore size 2.5–3.5 nm, pore volume 0.80–1.0 cm³. 3 / g of silica-alumina type mesoporous molecular sieve.

[0045] Example 1

[0046] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 130°C for 5.5 hours under argon protection. 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, followed by 4 g of 10 wt% methylaluminoxane (MAO) toluene solution. The mixture was reacted at 100°C for 4 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was then stored in an anhydrous and oxygen-free environment for later use.

[0047] Under argon protection, 7.5 g of the above activated silica-alumina mesoporous molecular sieve was suspended in 100 mL of hexane solvent, and then 1.24 g of 2-(diphenylphosphine)ethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 1 hour until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0048] Under argon protection, 0.92 g of ruthenium carbene complex (PCy3)2Cl2Ru=CHCH2OPh and 100 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 30 °C for 1 hour. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0049] Example 2

[0050] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 150°C for 4 hours under argon protection. 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, followed by 2 g of 10 wt% methylaluminoxane (MAO) toluene solution. The mixture was reacted at 100°C for 3 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was then stored in an anhydrous and oxygen-free environment for later use.

[0051] Under argon protection, 7.5 g of the above-mentioned activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.19 g of 2-(diphenylphosphine)ethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 1 hour until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0052] Under argon protection, 0.92 g of Grubbs 2-generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 3 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0053] Example 3

[0054] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 130°C for 4 hours under argon protection. 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, followed by 6 g of 10 wt% methylaluminoxane (MAO) toluene solution. The mixture was reacted at 80°C for 4 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was then stored in an anhydrous and oxygen-free environment for later use.

[0055] Under argon protection, 7.5 g of the above activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 0.98 g of diethylphosphinoethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 2 hours until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:3, and the extraction time was 5 h) to obtain the supported catalyst precursor.

[0056] Under argon protection, 1.27 g of Grubbs 2-generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 2 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0057] Example 4

[0058] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 150°C for 4 hours under argon protection. 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, followed by 5 g of 10 wt% methylaluminoxane (MAO) toluene solution. The mixture was reacted at 100°C for 4 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was then stored in an anhydrous and oxygen-free environment for later use.

[0059] Under argon protection, 7.5 g of the above-mentioned activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.15 g of 2-(diphenylphosphino)phenyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 3 hours until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0060] Under argon protection, 0.968 g of Grubbs 2-generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 1 hour, filtered under argon protection, and the solid was washed with n-hexane and then vacuum dried to obtain the supported catalyst.

[0061] Example 5

[0062] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 140°C for 4 hours under argon protection. 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, followed by 3 g of 10 wt% methylaluminoxane (MAO) toluene solution. The mixture was reacted at 100°C for 4 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was then stored in an anhydrous and oxygen-free environment for later use.

[0063] Under argon protection, 7.5 g of the above-mentioned activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.4 g of 2-(diphenylphosphino)phenyltriphenoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 2 hours until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0064] Under argon protection, 0.9216 g of Grubbs 2-generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 3 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0065] Example 6

[0066] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 130°C for 4 hours under argon protection. 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, followed by 2 g of 10 wt% methylaluminoxane (MAO) toluene solution. The mixture was reacted at 90°C for 4 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was then stored in an anhydrous and oxygen-free environment for later use.

[0067] Under argon protection, 7.5 g of the above-mentioned activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.04 g of 2-(diphenylphosphine)ethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 1 hour until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0068] Under argon protection, 1.5 g of Grubbs 2nd generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 2 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0069] Example 7

[0070] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 150°C for 4 hours. Under argon protection, 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, and then 2 g of 10 wt% trimethylaluminum toluene solution was added. The reaction was carried out at 60°C for 4 hours until the reaction was completed. After washing with toluene several times, the sieve was vacuum dried to obtain activated silica-alumina mesoporous molecular sieve, which was stored in an anhydrous and oxygen-free environment for later use.

[0071] Under argon protection, 7.5 g of the above-mentioned activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.10 g of 2-(diphenylphosphino)phenyltriphenoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 2 hours until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:2, and the extraction time was 5 h) to obtain the supported catalyst precursor.

[0072] Under argon protection, 0.978 g of Grubbs 2-generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 3 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0073] Example 8

[0074] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 130°C for 4 hours under argon protection. 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, followed by 2 g of 10 wt% triethylaluminum toluene solution. The mixture was reacted at 60°C for 4 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was then stored in an anhydrous and oxygen-free environment for later use.

[0075] Under argon protection, 7.5 g of the above-mentioned activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.15 g of diethylphosphinoethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 1 hour until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0076] Under argon protection, 0.922 g of Grubbs 2-generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 5 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0077] Comparative Example 1

[0078] This comparative example is similar to Example 6, except that the amount of Grubbs 2nd generation ruthenium carbene complex used is different. The specific experimental steps are as follows:

[0079] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 130°C for 4 hours under argon protection. 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, followed by 2 g of 10 wt% methylaluminoxane (MAO) toluene solution. The mixture was reacted at 90°C for 4 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was then stored in an anhydrous and oxygen-free environment for later use.

[0080] Under argon protection, 7.5 g of the above-mentioned activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.04 g of 2-(diphenylphosphine)ethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 1 hour until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0081] Under argon protection, 1.6216 g of Grubbs 2-generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 2 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0082] Comparative Example 2

[0083] This comparative example is similar to Example 6, except that the amount of methylaluminoxane used is different. The specific experimental steps are as follows:

[0084] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 130°C for 4 hours under argon protection. 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, followed by 7 g of 10 wt% methylaluminoxane (MAO) toluene solution. The mixture was reacted at 90°C for 4 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was then stored in an anhydrous and oxygen-free environment for later use.

[0085] Under argon protection, 7.5 g of the above-mentioned activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.04 g of 2-(diphenylphosphine)ethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 1 hour until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0086] Under argon protection, 1.5 g of Grubbs 2nd generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 2 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0087] Comparative Example 3

[0088] This comparative example is similar to Example 6, except that the amount of 2-(diphenylphosphine)ethyltriethoxysilane used is different. The specific experimental steps are as follows:

[0089] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 130°C for 4 hours. Under argon protection, 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, and then 2 g of 10 wt% methylaluminoxane (MAO) toluene solution was added. The mixture was reacted at 90°C for 4 hours until the reaction was completed. After washing with toluene several times, the mixture was vacuum dried to obtain the activated silica-alumina mesoporous molecular sieve, which was stored in an anhydrous and oxygen-free environment for later use.

[0090] Under argon protection, 7.5 g of the calcined silica-alumina mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.76 g of 2-(diphenylphosphine)ethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 1 hour until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0091] Under argon protection, 1.5 g of Grubbs 2nd generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 2 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0092] Comparative Example 4

[0093] This comparative example is similar to Example 6, except that a different silica-alumina type mesoporous molecular sieve is used. The specific experimental steps are as follows:

[0094] MCM-41 molecular sieve (silicon-aluminum molar ratio 60-65, specific surface area 450-750 m² / g, relative crystallinity 90-95%, pore size 2.5-3.5 nm, pore volume 0.80-1.0 cm³) was used. 3 (g) was placed in a vacuum oven and calcined at 130℃ for 4 hours. Under argon protection, 10g of the calcined MCM-41 molecular sieve was added to 200ml of toluene, and then 2g of 10wt% methylaluminoxane (MAO) toluene solution was added. The reaction was carried out at 90℃ for 4 hours until the reaction was completed. After washing with toluene several times, the sieve was vacuum dried to obtain activated MCM-41 molecular sieve, which was stored in an anhydrous and oxygen-free environment for later use.

[0095] Under argon protection, 7.5 g of the above activated MCM-41 molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.04 g of 2-(diphenylphosphine)ethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 1 hour until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0096] Under argon protection, 1.5 g of Grubbs 2nd generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 2 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0097] Comparative Example 5

[0098] This comparative example is similar to Example 6, except that diethylaluminum chloride is used instead of the 10wt% methylaluminoxane (MAO) toluene solution in this comparative example. The specific experimental steps are as follows:

[0099] The silica-alumina mesoporous molecular sieve was placed in a vacuum oven and calcined at 130°C for 4 hours. Under argon protection, 10 g of the calcined silica-alumina mesoporous molecular sieve was added to 200 mL of toluene, and then 0.2 g of diethylaluminum chloride was added. The reaction was carried out at 90°C for 4 hours until the reaction was completed. After washing with toluene several times, the sieve was vacuum dried to obtain activated silica-alumina mesoporous molecular sieve, which was stored in an anhydrous and oxygen-free environment for later use.

[0100] Under argon protection, 7.5 g of the above-mentioned activated silica-alumina type mesoporous molecular sieve was suspended in 148.4 mL of hexane solvent, and then 1.04 g of 2-(diphenylphosphine)ethyltriethoxysilane was added. After mixing, the mixture was stirred at a reflux temperature of about 70 °C for 1 hour until the reaction was completed. The free silicon compounds were removed by Soxhlet extractor (the extractant was a mixed solvent of diethyl ether and hexane in a volume ratio of 1:1, and the extraction time was 3 h) to obtain the supported catalyst precursor.

[0101] Under argon protection, 1.5 g of Grubbs 2nd generation ruthenium carbene complex and 148.4 mL of n-hexane solution were added to the above-mentioned supported catalyst precursor. After mixing, the mixture was stirred at 25 °C for 2 hours. The mixture was then filtered under argon protection. The solid was washed with n-hexane and then dried under vacuum to obtain the supported catalyst.

[0102] Experimental Example

[0103] The supported catalysts prepared in each example and comparative example were subjected to the metathesis reaction of 1-hexene under the following conditions:

[0104] 7.5 g of supported catalyst was mixed with 100 g of 1-hexene and 223 mL of dichloromethane. The mixture was then reacted at 50 °C for 3 hours under argon protection. The supported catalyst was removed by filtration. The remaining product was first measured to a volume V (mL) using a graduated cylinder. The product was diluted N times with ethyl acetate and analyzed by gas chromatography-mass spectrometry (GC-MS). Standard curves for 5-decene and 1-hexene were plotted using the external standard method and compared with the gas chromatogram of the product. The concentrations of 5-decene (C1) and 1-hexene (C2) in the product were calculated. The presence of impurity peaks in the gas chromatogram was used to determine the presence of byproducts. The following formula was used for calculation:

[0105] The yield of 5-decene in the product = C1 × N × V;

[0106] Mass of unreacted 1-hexene = C² × N × V;

[0107] The mass of 1-hexene that participated in the reaction = the total mass of 1-hexene - the mass of unreacted 1-hexene;

[0108] Conversion rate of 1-hexene = (mass of 1-hexene participating in the reaction / total mass of 1-hexene) × 100%;

[0109] Theoretical yield of 5-decene = mass of 1-hexene participating in the reaction ÷ 84 ÷ 2 × 140;

[0110] Selectivity for 5-decene = (5-decene yield in product / theoretical yield of 5-decene) × 100%;

[0111] The mass of the by-product = theoretical yield of 5-decene - yield of 5-decene in the product.

[0112] Table 1

[0113] serial number 5-Decanene yield / gram 1-Hexene conversion rate / % 5-Decanene Selectivity / % Amount of by-products / gram Example 1 42.3540 50.83 99.99 none Example 2 44.2455 53.10 99.99 none Example 3 49.9283 59.92 99.99 none Example 4 48.5167 58.29 99.88 none Example 5 45.2615 54.39 99.86 none Example 6 58.3691 70.05 99.99 none Example 7 51.3115 61.58 99.99 none Example 8 48.1973 57.86 99.96 none Comparative Example 1 24.9047 47.37 63.09 14.5702 Comparative Example 2 33.9380 42.56 95.69 1.5286 Comparative Example 3 47.6358 64.12 89.15 5.7975 Comparative Example 4 43.9032 64.28 81.96 9.6634 Comparative Example 5 20.7420 38.74 64.25 11.5413

[0114] As can be seen from the data in the table above, the supported catalyst provided by this invention, by preferentially using alkylaluminum and / or alkylaluminoxane to activate the silica-alumina type mesoporous molecular sieve support with specific physicochemical properties, and then loading the ruthenium carbene complex onto the activated support via phosphosiloxane compound, combined with controlling the amount of each material, can achieve the effect of no byproducts in the metathesis of 1-hexene and high selectivity for 5-decene. This indicates that the supported catalyst provided by this invention has sufficient exposure of active sites, high loading, and the metal ruthenium is not easily detached, and can effectively initiate the metathesis reaction of 1-hexene.

[0115] After the metathesis reaction was completed as described above, the supported catalyst of Example 7 obtained by filtration was subjected to metathesis reaction again under the conditions described above (the filtered catalyst does not require additional treatment and can be reused directly), and was reused five times. The specific results are shown in the table below.

[0116] Table 2

[0117] serial number 5-Decanene yield / gram 1-Hexene conversion rate / % 5-Decanene Selectivity / % Amount of by-products / gram first 51.3115 61.58 99.99 none The second 45.1121 54.14 99.99 none The third 35.2631 42.32 99.99 none Fourth 31.0158 37.26 99.89 none Fifth 23.6536 28.39 99.98 none

[0118] As can be seen from the data in the table above, although the conversion rate of 1-hexene decreases with the number of repeated uses of the supported catalyst provided by this invention, it can still maintain high selectivity for 5-decene and produce virtually no byproducts.

[0119] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A supported catalyst characterized in that, The raw materials for the supported catalyst include: (1) Ruthenium carbene complexes; (2) Alkyl aluminum and / or alkyl aluminum oxane; (3) Phosphosiloxane compounds; (4) Silicate-alumina type mesoporous molecular sieve; The silica-alumina mesoporous molecular sieve has a silica-alumina molar ratio of 25–30 and a specific surface area of ​​550–850 m². 2 / g, with a relative crystallinity of 90%–95%, a pore size of 2.5–3.5 nm, and a pore volume of 0.80–1.0 cm³. 3 / g; The method for preparing the supported catalyst includes the following steps: Activated silica-alumina mesoporous molecular sieve: In an inert gas atmosphere, the calcined silica-alumina mesoporous molecular sieve is reacted with alkylaluminum and / or alkylaluminoxane in toluene. After the reaction is completed, the sieve is washed and dried to obtain the activated silica-alumina mesoporous molecular sieve. Supported catalyst precursor: In an inert gas atmosphere, the activated silica-alumina type mesoporous molecular sieve and phosphine-based siloxane compound are reacted in n-hexane. After the reaction is completed, the free silicide is removed to obtain the supported catalyst precursor. Supported catalyst: In an inert gas atmosphere, the supported catalyst precursor is reacted with the ruthenium carbene complex in n-hexane. After the reaction is completed, the catalyst is obtained by separation, washing and drying. The mass ratio of the calcined silica-alumina mesoporous molecular sieve to the alkylaluminum and / or alkylaluminoxane is 1:0.02 to 1:0.

06. The mass ratio of the activated silica-alumina type mesoporous molecular sieve to the phosphosiloxane compound is 1:0.13-0.20; The mass ratio of the activated silica-alumina type mesoporous molecular sieve to the ruthenium carbene complex is 1:0.12 to 0.

20.

2. The supported catalyst of claim 1, wherein The ruthenium carbene complex is selected from Grubbs-type catalysts, Hoveyda-Grubbs-type catalysts, or (PCy3)2Cl2Ru=CHCH2OPh.

3. The supported catalyst of claim 1, wherein the metal oxide support is selected from the group consisting of alumina, silica, titania, zirconia, ceria, and mixtures thereof. The alkylaluminum is selected from trialkylaluminum; The alkylaluminoxane is selected from at least one of methylaluminoxane, isobutylaluminoxane, trimethylaluminoxane, triethylaluminoxane, and triisobutylaluminoxane.

4. The supported catalyst of claim 1, wherein the metal oxide support is selected from the group consisting of alumina, silica, titania, zirconia, ceria, and mixtures thereof. The phosphonosiloxane compound is selected from at least one of 2-(diphenylphosphine)ethyltriethoxysilane, diethylphosphine ethyltriethoxysilane, 2-(diphenylphosphine)phenyltriethoxysilane, and 2-(diphenylphosphine)phenyltriphenoxysilane.

5. The supported catalyst of claim 3, wherein the metal oxide is selected from the group consisting of alumina, silica, titania, zirconia, ceria, and mixtures thereof. The alkylaluminum is selected from at least one of trimethylaluminum, triethylaluminum, and triisobutylaluminum.

6. The supported catalyst of claim 1, wherein the metal oxide support is selected from the group consisting of alumina, silica, titania, zirconia, ceria, and mixtures thereof. The reaction temperature of the calcined silica-alumina mesoporous molecular sieve with the alkylaluminum and / or alkylaluminoxane is 60℃~100℃, and the reaction time is 3~4 hours.

7. The supported catalyst as described in claim 1, characterized in that, In the preparation step of the supported catalyst precursor, a Soxhlet extractor is used to remove free silicides; The reaction time for the preparation step of the supported catalyst precursor is 1 to 3 hours.

8. The supported catalyst of claim 1, wherein, The reaction temperature for the preparation step of the supported catalyst is 20–30°C, and the reaction time is 1–5 hours.

9. The supported catalyst of claim 1, wherein, It also includes the step of calcining the silicon-aluminum molecular sieve.

10. The supported catalyst of claim 7, wherein the metal oxide is selected from the group consisting of alumina, silica, titania, zirconia, ceria, and mixtures thereof. The extraction solution used was a mixed solvent of diethyl ether and n-hexane with a volume ratio of 1:1 to 3, and the extraction time was 3 to 5 hours.

11. The supported catalyst of claim 9, wherein the metal oxide is selected from the group consisting of alumina, silica, titania, zirconia, ceria, and mixtures thereof. The calcination temperature of the silica-alumina type mesoporous molecular sieve is 130-150℃, and the calcination time is 4-6 hours.

12. The use of the supported catalyst according to any one of claims 1-11 in the catalytic metathesis reaction of 1-hexene.

13. The use according to claim 12, wherein the compound is ###0002### Application of the supported catalyst in the preparation of 5-decene from the metathesis reaction of 1-hexene.

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