High exchange capacity porous crosslinked benzyl alcohol resin metal salt beta-h elimination promoter, method of making and use thereof
By preparing a porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter with high exchange capacity, the problems of low exchange capacity and insufficient basicity in the prior art are solved, realizing a highly efficient catalytic reaction of ethylene with carbon dioxide carboxylation, which is suitable for industrial production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-12-09
- Publication Date
- 2026-06-09
AI Technical Summary
Existing β-H elimination promoters have low exchange capacity, insufficient basicity, and are difficult to separate, resulting in low reaction efficiency and high energy consumption, which makes it difficult to meet industrial needs.
A method for preparing porous cross-linked benzyl alcohol resin metal salt β-H elimination promoters was adopted. Through the polymerization reaction of potassium persulfate, hydroxyethyl cellulose, 4-(vinylphenyl)methanol and divinylbenzene, combined with sodium hydride treatment, a porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter with high exchange capacity was prepared for catalyzing the carboxylation reaction of ethylene and carbon dioxide.
This method improves the exchange capacity and basicity of the metal salt β-H elimination promoter in porous crosslinked benzyl alcohol resin, reduces the amount of reaction additive, simplifies the separation process, reduces energy consumption, and is suitable for high-temperature reaction conditions, showing good prospects for industrial application.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of β-H elimination promoter technology, specifically to a porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter with high exchange capacity, its preparation method, and its application. Background Technology
[0002] In the 1980s, Burkhart first reported the carboxylation reaction of carbon dioxide with alkenes. Using carbon dioxide and styrene as raw materials, he demonstrated that carbon dioxide could be activated to generate nickel propionate lactone intermediates under the action of a nickel complex. By controlling the reaction temperature, phenylpropionic acid or cinnamic acid products could be generated. Building on this, more and more researchers have studied the catalytic carboxylation of unsaturated hydrocarbons with carbon dioxide. Carbon dioxide carboxylation reactions can be widely used to prepare bulk and fine chemicals, as well as intermediates in organic synthesis. In recent years, palladium and nickel-catalyzed reactions of alkenes and alkynes with carbon dioxide have received considerable attention among different catalytically active metals. Some reactions have been used to prepare a series of important industrial products. For example, valuable α,β-unsaturated carboxylic acids and their derivatives can be directly obtained via carbon dioxide carboxylation reactions. The carboxylation reaction of carbon dioxide with ethylene can directly synthesize acrylic acid, which can then be further processed through esterification to obtain various acrylate compounds.
[0003] The carboxylation reaction of carbon dioxide with ethylene is a direct reaction between ethylene and carbon dioxide catalyzed by a metal catalyst. The reaction mechanism is that after the metal catalyst activates carbon dioxide, it reacts with ethylene to generate a metal lactone ring intermediate of propionate. This intermediate can be hydrolyzed or undergo β-H elimination reaction under heating or acid-base conditions. At the same time, the metal catalyst leaves and re-enters the next catalytic cycle, finally yielding acrylic acid or propionic acid compounds.
[0004] From a reaction mechanism perspective, the promoter in the β-H elimination step plays a crucial role in the reaction process. Currently, most β-H elimination promoters are metal salts of acids or alcohols. When using tert-butanol metal salts as β-H elimination promoters for carbon dioxide carboxylation reactions, the reaction yield can reach over 70%. However, the amount of potassium tert-butoxide added is usually 200-1000 times that of the catalyst, generating a large amount of waste liquid. Furthermore, the unreacted tert-butanol metal salt and potassium acrylate product are difficult to separate, leading to increased separation energy consumption. Chevron Philips Chemicals has developed polyvinylphenol or phenolic resin metal salts (CN108368017A, CN111032609A) as supported β-H elimination promoters to replace tert-butanol metal salts for the carboxylation reaction of carbon dioxide and ethylene. Although these supported β-H elimination promoters are easy to separate, their basicity is weaker than that of alcohol metal salts, resulting in lower reaction efficiency. Recently, the Qilu Petrochemical Company Research Institute developed a porous cross-linked benzyl alcohol resin sodium salt β-H elimination promoter using porous cross-linked chloromethylated resin as raw material. This significantly improved the basicity of the promoter. However, the highest sodium salt content was only 4.9 mmol / g, requiring a large amount to be added during the reaction. Based on a catalyst-to-β-H elimination promoter molar ratio of 1:300, adding 0.1 mmol of catalyst required the addition of 6.1 g of benzyl alcohol resin sodium salt β-H elimination promoter. Therefore, developing a benzyl alcohol resin sodium salt β-H elimination promoter with high exchange capacity is of great significance in addressing these issues. Summary of the Invention
[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter with high exchange capacity, its preparation method and application. The prepared porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter has the advantages of high metal salt content, strong alkalinity and easy separation, and is an additive with great prospects for industrial application.
[0006] The technical solution of this invention is as follows:
[0007] In a first aspect, the present invention provides a method for preparing a high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter, comprising the following steps:
[0008] S1 dissolves potassium persulfate and hydroxyethyl cellulose in water, adds 4-(vinylphenyl)methanol monomer and divinylbenzene crosslinking agent, and reacts at 70-85℃ for 10-12h under a nitrogen atmosphere; after the reaction is completed, the reaction system is filtered, the resulting white solid is washed with water and ethanol, and then dried to obtain milky white polymerized microspheres;
[0009] S2 adds anhydrous tetrahydrofuran to milky white polymerized microspheres, then adds sodium hydride in batches, and heats to 60-80℃ to react for 8-10 hours;
[0010] After the S3 reaction is completed, the temperature is cooled to room temperature and the polymerized microspheres are filtered. The polymerized microspheres are washed with methanol, tetrahydrofuran and n-hexane respectively. The washed polymerized microspheres are dried to obtain a porous crosslinked benzyl alcohol resin sodium salt β-H elimination accelerator.
[0011] Preferably, in step S1, the molar ratio of 4-(vinylphenyl)methanol to divinylbenzene is (5-8):1; preferably, in step S1, the molar ratio of 4-(vinylphenyl)methanol to divinylbenzene is (6-7):1.
[0012] Preferably, in step S1, the amount of potassium persulfate added is 2-5%, and the amount of hydroxyethyl cellulose added is 0.5-1%; preferably, the amount of potassium persulfate added is 3.5-5%.
[0013] Preferably, in step S2, the molar ratio of sodium hydride to 4-(vinylphenyl)methanol is 1-1.5:1.
[0014] Preferably, in step S3, the average particle size of the porous cross-linked benzyl alcohol resin sodium salt β-H elimination accelerator is 0.3-0.6 mm, and the average pore radius of the porous cross-linked benzyl alcohol resin sodium salt β-H elimination accelerator is...
[0015] Preferably, in step S1, the drying temperature is 80-100℃ and the drying time is 6-8h; in step S3, the drying temperature is 80-100℃ and the drying time is 2-5h.
[0016] Secondly, the present invention provides a porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter with high exchange capacity prepared by the above preparation method, with the following structural formula:
[0017]
[0018] n = 500 - 2000.
[0019] Thirdly, the present invention provides the application of the above-mentioned porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter with high exchange capacity, in which ethylene and carbon dioxide react to produce acrylic acid under the catalysis of a catalyst composed of nickel compound, phosphine ligand and porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter.
[0020] Preferably, nickel compounds, phosphine ligands, and porous cross-linked benzyl alcohol resin metal salt β-H elimination promoters are added to the reactor, sealed, and then an appropriate amount of carbon dioxide with a mass purity of 90-100% is introduced. Then, the reactor is filled with ethylene to a specified pressure to carry out the reaction, wherein the mass purity of ethylene is 90-100%. This reaction is a heterogeneous reaction carried out in a batch reactor.
[0021] Preferably, the nickel compound is bis-(1,5-cyclooctadiene)nickel; the phosphine ligand is a bidentate phosphine ligand, preferably 1,2-bis(di-tert-butylphosphine)ethane, 1,3-bis(dicyclohexylphosphine)propane, or 1,4-bis(dicyclohexylphosphine)butane; the molar ratio of the nickel compound, the phosphine ligand, and the porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter is 1:(1-2.5):(200-800); preferably, the molar ratio of the nickel compound, the phosphine ligand, and the porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter is 1:1.5:(300-600).
[0022] Preferably, the reaction temperature is 140-160℃ and the reaction time is 8-24h; preferably, the reaction temperature is 140-150℃ and the reaction time is 14-20h.
[0023] In this invention, the TON of the carbon dioxide carboxylation reaction is calculated as: the number of moles of sodium acrylate produced by the reaction / the number of moles of catalyst (i.e., nickel compound and phosphine ligand) added.
[0024] Compared with the prior art, the present invention has the following advantages:
[0025] 1. Compared with existing porous cross-linked benzyl alcohol resin sodium salts, the porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter prepared in this invention has an exchange capacity of not less than 5.1 mmol / g and a maximum of 6.5 mmol / g, and the amount added during the reaction is further reduced. Moreover, the porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter has the characteristic of high temperature resistance and can be used at reaction temperatures above 140°C.
[0026] 2. The porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter of the present invention is more basic than sodium phenolate and has a faster reaction efficiency. Furthermore, using the porous cross-linked benzyl alcohol resin sodium salt of the present invention as a β-H elimination promoter facilitates separation from the reactants and products, reducing separation energy consumption. Therefore, the porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter prepared by the present invention has advantages such as high metal salt content, strong basicity, and easy separation, making it a promising additive for industrial application. Detailed Implementation
[0027] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention.
[0028] Example 1
[0029] The preparation method of the porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter in this embodiment includes the following steps:
[0030] In a 250 mL three-necked round-bottom flask, potassium persulfate (440 mg, 1.6 mmol), 100 mg hydroxyethyl cellulose, and 150 mL deionized water were added sequentially, while bubbling under nitrogen and stirring for 20 min. Then, 4-(vinylphenyl)methanol (10.7 g, 80 mmol) and divinylbenzene (1.73 g, 13.3 mmol) were added, and the reaction was carried out at 70 °C for 10 h under a nitrogen atmosphere. After the reaction was completed, the reaction system was filtered, and the resulting white solid was washed with deionized water and ethanol, and then dried in a vacuum drying oven at 80 °C for 8 h to obtain milky white polymerized microspheres.
[0031] S2. Pour the prepared milky white polymerized microspheres into a 250 mL three-necked flask, add 150 mL of anhydrous tetrahydrofuran, and slowly add sodium hydride (3.2 g, 80 mmol) into the three-necked flask in 6 batches. Heat to 60 °C and react for 8 h.
[0032] After the S3 reaction was completed, the temperature was cooled to room temperature and the polymerized pellets were filtered. The polymerized pellets were washed three times each with methanol, tetrahydrofuran and n-hexane. The washed polymerized pellets were placed in a vacuum drying oven and dried at 80°C for 5 hours to obtain a porous crosslinked benzyl alcohol resin sodium salt β-H elimination promoter with a benzyl alcohol sodium content of 5.7 mmol / g and a conversion rate of 81%.
[0033] Example 2
[0034] The preparation method of the porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter in this embodiment includes the following steps:
[0035] In a 250 mL three-necked round-bottom flask, potassium persulfate (440 mg, 1.6 mmol), 100 mg hydroxyethyl cellulose, and 150 mL deionized water were added sequentially, while simultaneously bubbling with nitrogen and stirring for 20 min. Then, 4-(vinylphenyl)methanol (10.7 g, 80 mmol) and divinylbenzene (1.73 g, 13.3 mmol) were added, and the mixture was reacted at 85 °C for 12 h under a nitrogen atmosphere. After the reaction was completed, the reaction system was filtered, and the resulting white solid was washed with deionized water and ethanol, and then dried in a vacuum drying oven at 80 °C for 8 h to obtain milky white polymerized microspheres.
[0036] S2. Pour the prepared milky white polymerized microspheres into a 250 mL three-necked flask, add 150 mL of anhydrous tetrahydrofuran, and slowly add sodium hydride (3.2 g, 80 mmol) in 6 batches into the three-necked flask. Heat to 80 °C and react for 8 h.
[0037] After the S3 reaction was completed, the temperature was cooled to room temperature and the polymerized pellets were filtered. The polymerized pellets were washed three times each with methanol, tetrahydrofuran and n-hexane. The washed polymerized pellets were placed in a vacuum drying oven and dried at 80°C for 5 hours to obtain a porous crosslinked benzyl alcohol resin sodium salt β-H elimination promoter with a benzyl alcohol sodium content of 5.7 mmol / g and a conversion rate of 90%.
[0038] Example 3
[0039] The preparation method of the porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter in this embodiment includes the following steps:
[0040] In a 250 mL three-necked round-bottom flask, potassium persulfate (622 mg, 2.26 mmol), 100 mg hydroxyethyl cellulose, and 150 mL deionized water were added sequentially, while simultaneously bubbling with nitrogen and stirring for 20 min. Then, 4-(vinylphenyl)methanol (10.7 g, 80 mmol) and divinylbenzene (1.73 g, 13.3 mmol) were added, and the mixture was reacted at 85 °C for 12 h under a nitrogen atmosphere. After the reaction was completed, the reaction system was filtered, and the resulting white solid was washed with deionized water and ethanol, and then dried in a vacuum drying oven at 80 °C for 8 h to obtain milky white polymerized microspheres.
[0041] S2. The obtained milky white polymerized microspheres were poured into a 250 mL three-necked flask, and 150 mL of anhydrous tetrahydrofuran was added at the same time. Sodium hydride (3.2 g, 80 mmol) was slowly added to the three-necked flask in 6 batches, and the temperature was raised to 80 °C and reacted for 10 h.
[0042] After the S3 reaction was completed, the temperature was cooled to room temperature and the polymerized pellets were filtered. The polymerized pellets were washed three times each with methanol, tetrahydrofuran and n-hexane. The washed polymerized pellets were placed in a vacuum drying oven and dried at 80°C for 5 hours to obtain a porous crosslinked benzyl alcohol resin sodium salt β-H elimination promoter with a benzyl alcohol sodium content of 5.5 mmol / g and a conversion rate of 87%.
[0043] Example 4
[0044] The preparation method of the porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter in this embodiment includes the following steps:
[0045] In a 250 mL three-necked round-bottom flask, potassium persulfate (260 mg, 0.96 mmol), 100 mg hydroxyethyl cellulose, and 150 mL deionized water were added sequentially, while simultaneously bubbling with nitrogen and stirring for 20 min. Then, 4-(vinylphenyl)methanol (10.7 g, 80 mmol) and divinylbenzene (1.73 g, 13.3 mmol) were added, and the mixture was reacted at 85 °C for 12 h under a nitrogen atmosphere. After the reaction was completed, the reaction system was filtered, and the resulting white solid was washed with deionized water and ethanol, and then dried in a vacuum drying oven at 80 °C for 8 h to obtain milky white polymerized microspheres.
[0046] S2. Pour the obtained milky white polymerized microspheres into a 250 mL three-necked flask, add 150 mL of anhydrous tetrahydrofuran, and slowly add sodium hydride (4.8 g, 120 mmol) into the three-necked flask in 6 batches. Heat to 80 °C and react for 10 h.
[0047] After the S3 reaction was completed, the temperature was cooled to room temperature and the polymerized pellets were filtered. The polymerized pellets were washed three times each with methanol, tetrahydrofuran and n-hexane. The washed polymerized pellets were placed in a vacuum drying oven and dried at 80°C for 5 hours to obtain a porous crosslinked benzyl alcohol resin sodium salt β-H elimination promoter with a benzyl alcohol sodium content of 5.1 mmol / g and a conversion rate of 81%.
[0048] Example 5
[0049] The preparation method of the porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter in this embodiment includes the following steps:
[0050] In a 250 mL three-necked round-bottom flask, potassium persulfate (497 mg, 1.81 mmol), 100 mg hydroxyethyl cellulose, and 150 mL deionized water were added sequentially, while simultaneously bubbling with nitrogen and stirring for 20 min. Then, 4-(vinylphenyl)methanol (12.48 g, 93.1 mmol) and divinylbenzene (1.73 g, 13.3 mmol) were added, and the mixture was reacted at 85 °C for 12 h under a nitrogen atmosphere. After the reaction was completed, the reaction system was filtered, and the resulting white solid was washed with deionized water and ethanol, and then dried in a vacuum drying oven at 80 °C for 8 h to obtain milky white polymerized microspheres.
[0051] S2. The obtained milky white polymerized microspheres were poured into a 250 mL three-necked flask, and 150 mL of anhydrous tetrahydrofuran was added at the same time. Sodium hydride (3.72 g, 93.1 mmol) was slowly added to the three-necked flask in 6 batches, and the temperature was raised to 70 °C and reacted for 9 h.
[0052] After the S3 reaction was completed, the temperature was cooled to room temperature and the polymerized pellets were filtered. The polymerized pellets were washed three times each with methanol, tetrahydrofuran and n-hexane. The washed polymerized pellets were placed in a vacuum drying oven and dried at 80°C for 5 hours to obtain a porous crosslinked benzyl alcohol resin sodium salt β-H elimination promoter with a benzyl alcohol sodium content of 6.5 mmol / g and a conversion rate of 95%.
[0053] Examples 6-13
[0054] In a 150 mL high-pressure reactor, under nitrogen protection, 0.1 mmol of bis-(1,5-cyclooctadiene)nickel (Ni(COD)2), 0.1 mmol of bisphosphine ligand, 30 mmol of β-H elimination promoter, and 60 mL of solvent were added sequentially. The reactor was sealed, and the gas inside was replaced with carbon dioxide three times. Carbon dioxide was then introduced until the reactor pressure reached 1 MPa, followed by the introduction of ethylene until the reactor pressure reached 5 MPa. The temperature was slowly increased to 140 °C under temperature control, and the reaction was carried out for 8 hours. After cooling to room temperature, the reactor was removed, the β-H elimination promoter was filtered, and the resulting liquid was analyzed. The raw materials and reaction parameters for Examples 6-13 are shown in Table 1.
[0055] Table 1. Raw materials and reaction-related parameters for Examples 6-13
[0056]
[0057] Examples 14-17
[0058] In a 150 mL high-pressure reactor, 0.1 mmol of bis-(1,5-cyclooctadiene)nickel, 1,2-bis(di-tert-butylphosphine)ethane, a β-H elimination promoter, and 60 mL of chlorobenzene were added sequentially. The reactor was sealed, and after purging with carbon dioxide three times, carbon dioxide was added until the reactor pressure reached 1 MPa. Ethylene was then added until the reactor pressure reached 5 MPa. The temperature was slowly increased to 140 °C under temperature control, and the reaction was carried out for 8 hours. After cooling to room temperature, the reactor was removed, the β-H elimination promoter was filtered, and the resulting liquid was analyzed. The raw materials and reaction parameters for Examples 14-17 are shown in Table 2.
[0059] Table 2. Raw materials and reaction-related parameters for Examples 14-17
[0060]
[0061]
[0062] Examples 18-21
[0063] In a 150 mL high-pressure reactor, under nitrogen protection, 0.1 mmol of bis-(1,5-cyclooctadiene)nickel, 0.15 mmol of 1,2-bis(di-tert-butylphosphine)ethane, 30 mmol of β-H elimination promoter, and 60 mL of chlorobenzene were added sequentially. The reactor was sealed, and after purging with carbon dioxide three times, carbon dioxide was added until the reactor pressure reached 1 MPa. Ethylene was then added until the gas pressure inside the reactor reached 5 MPa. The temperature was slowly increased to the set temperature and the reaction time was set using a temperature controller. After the reaction was completed, the reactor was cooled to room temperature, removed from the reactor, and the β-H elimination promoter was filtered. The resulting liquid was analyzed. The raw materials and reaction parameters for Examples 18-21 are shown in Table 3.
[0064] Table 3. Raw materials and reaction-related parameters for Examples 18-21
[0065]
[0066] Comparative Examples 1-3
[0067] In a 150 mL high-pressure reactor, 0.1 mmol of bis-(1,5-cyclooctadiene)nickel, 0.15 mmol of 1,2-bis(di-tert-butylphosphine)ethane, 30 mmol of β-H elimination promoter, and 60 mL of chlorobenzene were added sequentially. The reactor was sealed, and after purging with carbon dioxide three times, carbon dioxide was added until the reactor pressure reached 1 MPa. Ethylene was then added until the reactor pressure reached 5 MPa. The temperature was slowly increased to 140 °C under temperature control, and the reaction was carried out for 14 h. After cooling to room temperature, the reactor was removed, and the resulting liquid was analyzed. The raw materials and relevant reaction parameters for Comparative Examples 1-3 are shown in Table 4.
[0068] Table 4. Raw materials and reaction-related parameters for Comparative Examples 1-3
[0069]
[0070] Compared with the three β-H elimination promoters used in Comparative Examples 1-3, the sodium alkoxide β-H elimination promoter of the porous crosslinked benzyl alcohol resin of the present invention has a high exchange capacity of sodium alkoxide and a stronger basicity than that of general sodium carboxylate and sodium phenolate. After the reaction, the resin microspheres can be separated from the water-soluble sodium acrylate product by simple vacuum filtration. The used resin microspheres can be reacted with sodium hydride to produce sodium alkoxide β-H elimination promoter again, which has good recycling performance.
Claims
1. A method for preparing a high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter, characterized in that, Includes the following steps: S1 dissolves potassium persulfate and hydroxyethyl cellulose in water, adds 4-(vinylphenyl)methanol monomer and divinylbenzene crosslinking agent, and reacts at 70-85℃ for 10-12h under a nitrogen atmosphere; after the reaction is completed, the reaction system is filtered, the resulting white solid is washed with water and ethanol, and then dried to obtain milky white polymerized microspheres; S2 adds anhydrous tetrahydrofuran to milky white polymerized microspheres, then adds sodium hydride in batches, and heats to 60-80℃ to react for 8-10 hours; After the S3 reaction is completed, the temperature is cooled to room temperature and the polymerized microspheres are filtered. The polymerized microspheres are washed with methanol, tetrahydrofuran and n-hexane respectively. The washed polymerized microspheres are dried to obtain a porous crosslinked benzyl alcohol resin sodium salt β-H elimination accelerator.
2. The method for preparing the high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter as described in claim 1, characterized in that, In step S1, the molar ratio of 4-(vinylphenyl)methanol to divinylbenzene is (5-8):1; preferably, in step S1, the molar ratio of 4-(vinylphenyl)methanol to divinylbenzene is (6-7):
1.
3. The method for preparing the high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter as described in claim 1, characterized in that, In step S1, the amount of potassium persulfate added is 2-5%, and the amount of hydroxyethyl cellulose added is 0.5-1%; preferably, the amount of potassium persulfate added is 3.5-5%.
4. The method for preparing the high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter as described in claim 1, characterized in that, In step S2, the molar ratio of sodium hydride to 4-(vinylphenyl)methanol is 1-1.5:
1.
5. The method for preparing the high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter as described in claim 1, characterized in that, In step S3, the average particle size of the porous cross-linked benzyl alcohol resin sodium salt β-H elimination accelerator is 0.3-0.6 mm, and the average pore radius of the porous cross-linked benzyl alcohol resin sodium salt β-H elimination accelerator is...
6. The method for preparing the high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter as described in claim 1, characterized in that, In step S1, the drying temperature is 80-100℃ and the drying time is 6-8h; in step S3, the drying temperature is 80-100℃ and the drying time is 2-5h.
7. A porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter with high exchange capacity prepared by the preparation method according to any one of claims 1-6.
8. The application of the high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter as described in claim 7, characterized in that, Ethylene and carbon dioxide react to form acrylic acid under the catalysis of a catalyst composed of nickel compounds, phosphine ligands, and a porous cross-linked benzyl alcohol resin metal salt β-H elimination promoter.
9. The application of the high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter as described in claim 8, characterized in that, The nickel compound is bis-(1,5-cyclooctadiene)nickel; the phosphine ligand is a bidentate phosphine ligand, preferably 1,2-bis(di-tert-butylphosphine)ethane, 1,3-bis(dicyclohexylphosphine)propane, or 1,4-bis(dicyclohexylphosphine)butane; the molar ratio of the nickel compound, the phosphine ligand, and the porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter is 1:(1-2.5):(200-800); preferably, the molar ratio of the nickel compound, the phosphine ligand, and the porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter is 1:1.5:(300-600).
10. The application of the high-exchange-capacity porous crosslinked benzyl alcohol resin metal salt β-H elimination promoter as described in claim 8, characterized in that, The reaction temperature is 140-160℃ and the reaction time is 8-24h; preferably, the reaction temperature is 140-150℃ and the reaction time is 14-20h.