Use of porous polymer catalysts in catalyzing ring-opening reactions of epoxides

Abstract

The application belongs to the technical field of solid phase catalysis, and discloses application of a porous polymer catalyst in catalyzing an epoxy ring-opening reaction. The porous polymer catalyst is prepared by the following method: (1) trihelium is dissolved in a solvent together with a Lewis acid, and through reaction I, washing, refluxing, filtering and drying, a hypercrosslinked self-porous polymer is obtained; (2) the hypercrosslinked self-porous polymer obtained in step (1) is dispersed in concentrated sulfuric acid, and through reaction II, a sulfonated multifunctional hypercrosslinked self-porous polymer, i.e. the porous polymer catalyst, is obtained. The polymer catalyst provided by the application is rich in porous structure, can efficiently catalyze the synthesis of an epoxy ring-opening reaction under simple catalytic conditions, and can realize a conversion rate close to 100% under a small amount of catalyst, a short reaction time and a low temperature, and has high industrial application value.

Description

Technical Field

[0001] This invention belongs to the field of solid-phase catalysis technology, and particularly relates to a catalyst for catalyzing the ring-opening reaction of epoxy resins. Background Technology

[0002] β-Alkoxyl, as a key organic intermediate containing both hydroxyl and alkoxy groups, holds irreplaceable core value in strategic fields such as pharmaceutical synthesis, new material development, and fine chemicals. In the pharmaceutical field, it forms the core framework of active molecules in antibacterial drugs, antitumor agents, and cardiovascular drugs; in the new materials field, it can be used to prepare high-performance polyurethanes, environmentally friendly coatings, and biodegradable plastics; and in the fine chemicals field, it is a core raw material for specialty surfactants and food additives. The ring-opening reaction of epoxides, as the most direct and efficient core route for the preparation of β-alkoxyl, directly determines the production quality, cost, and environmental impact of β-alkoxyl due to its reaction efficiency, selectivity, and environmental friendliness. It serves as a crucial bridge connecting basic chemical raw materials and high-value-added products, and breakthroughs in this technology play a decisive role in the upgrading of related industries.

[0003] Currently, the synthesis of β-alkoxyl alcohols mainly relies on catalytic reactions. However, existing catalytic systems face numerous technical bottlenecks in terms of activity, stability, environmental friendliness, and industrial applicability. In traditional homogeneous catalytic systems, strong acid catalysts, such as concentrated sulfuric acid and hydrochloric acid, while exhibiting high activity, suffer from problems such as strong equipment corrosion, difficulty in product separation, and large wastewater discharge, failing to meet the requirements of green production. In contrast, porous materials, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), possess advantages such as high specific surface area, controllable pores, and excellent catalytic activity, showing great potential in heterogeneous catalysis. However, these materials also suffer from poor structural stability, the risk of metal residue, high synthesis costs (due to expensive ligands), and limited mass transfer efficiency, hindering their large-scale practical application in organic synthesis. In 2025, Mahdiyeh-Sadat Hosseini's team reported a bifunctional heterogeneous acid catalyst based on MIL-88B(Fe). The MIL-88B(Fe) / SA catalyst constructed a catalytic system with both Lewis and Brønsted acid sites. In a model reaction of styrene oxide and methanol, a 95% substrate conversion was achieved with a catalyst dosage of 12.5 wt% at 60 °C for 1.5 h, exhibiting 100% selectivity for the target product 2-methoxy-2-phenylethanol. Furthermore, the catalytic activity showed no significant decline after six cycles. However, the catalyst exhibited insufficient specific surface area and mass transfer efficiency (BET specific surface area was only 92 m²). 2The high cost of preparation (requiring expensive solvents such as DMF and large amounts of aminosulfonic acid) and insufficient mechanical strength (difficult to adapt to continuous flow devices such as fixed beds and microchannel reactors) have limited the industrial continuous production application of this technology (CrystEngComm, 2025, 27, 2729-2738).

[0004] In recent years, driven by the "carbon peaking and carbon neutrality" strategy, the low-carbon transformation of the chemical industry has become an inevitable trend. Green catalysis technology, as a core support, must meet the core requirements of high activity, high selectivity, recyclability, and environmental friendliness. Against this backdrop, industrial continuous flow catalysis technology, due to its advantages such as controllable reaction, efficient mass transfer, and low emissions, has become an ideal model for large-scale green production. The adaptability of the catalyst for continuous flow is the core of technology implementation. This requires epoxide ring-opening reaction catalysts to meet multiple conditions: first, excellent mechanical strength and structural stability to resist fluid impact and avoid pipeline blockage; second, reasonable control of the pore structure to reduce mass transfer resistance; third, long-term stable catalysis to ensure continuous production; and fourth, easy immobilization to adapt to fixed-bed and microchannel reactors. However, existing catalysts suffer from insufficient mechanical strength and are prone to deactivation during continuous operation. Therefore, developing catalysts adapted for continuous flow can not only improve the production efficiency and quality of β-alkoxyl alcohols and reduce carbon emissions, but also provide a reference for the continuous green production of other intermediates in the chemical industry, promote the industry's low-carbon transformation, and provide technical support for the implementation of the dual-carbon strategy. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention proposes the application of a porous polymer catalyst in the catalytic ring-opening reaction of epoxy resins.

[0006] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0007] A method for preparing a porous polymer catalyst, comprising the following steps:

[0008] (1) The trimelline monomer and Lewis acid were dissolved in a solvent and mixed evenly in an ice-water bath. After reaction I, the mixture was washed, refluxed, filtered, and dried to obtain a hypercrosslinked self-porous polymer (THCPIM) with the following structural formula:

[0009] .

[0010] (2) The hypercrosslinked self-porous polymer obtained in step (1) was dispersed in concentrated sulfuric acid and subjected to reaction II. After the reaction was completed, the polymer was washed, refluxed, filtered, and dried to obtain STHCPIM, a sulfonated multifunctional hypercrosslinked self-porous polymer based on tripterene, i.e., a porous polymer catalyst. Its structural formula is as follows:

[0011] .

[0012] In step (1) above, the molar ratio of tripterene to Lewis acid is 1:10-20, and the concentration of tripterene is 0.1-0.5 mmol / mL.

[0013] Furthermore, in step (1) above, the Lewis acid is selected from anhydrous aluminum trichloride or anhydrous ferric trichloride, and the solvent is any one of dichloromethane, chloroform and 1,2-dichloroethane. To improve the yield, the above-mentioned ultra-dry solvent, such as ultra-dry dichloromethane, can be added. The temperature of reaction I is from room temperature (RT) to 60°C, and the time is 0.1-48 h.

[0014] In step (2) above, 0.05-0.5 g of hypercrosslinked self-porous polymer is added to every 1 mL of concentrated sulfuric acid; the temperature of reaction II is from room temperature (RT) to 80°C, and the time is 0.1-48 h.

[0015] Porous polymer catalysts were prepared using the above-described method. These catalysts are composed of C, H, S, and O elements and possess a porous structure, including ultrapores (0.5-0.7 nm), micropores (0.7-2 nm), and mesopores (2-5 nm), with a specific surface area ≥200 m². 2 / g, the content of sulfonate groups in the sulfonated porous catalyst is ≥10%.

[0016] The above-mentioned porous polymer catalysts are used in the catalytic ring-opening reaction of epoxy resins.

[0017] A method for catalyzing the ring-opening reaction of an epoxy group using a porous polymer catalyst includes the following steps: A porous polymer catalyst, an epoxide, and an alcohol are subjected to reaction III, followed by solid-liquid separation, and solvent evaporation to obtain the ring-opening product. The alcohol can be used as both a solvent and a reactant. In practice, other solvents besides alcohol can also be added.

[0018] Furthermore, based on epoxide, each 0.1-5 mmol of epoxide requires 5-50 mg of porous polymer catalyst and 1-5 mL of alcohol.

[0019] The epoxide is at least one of at least one selected from styrene oxide, trans-2,3-diphenylethylene oxide, cyclohexane oxide, 2,7-dichlorofluorene-4-ethylene oxide, propynyl glycidyl ether, glycidyl ether oxide, cyclohexane oxide, and 2-(chloromethyl)ethylene oxide. The alcohol solvent is at least one selected from methanol, ethanol, n-propanol, and isopropanol. Reaction III is carried out at temperatures ranging from room temperature to 98°C for 0.1–12 h.

[0020] A method for catalyzing the ring-opening reaction of epoxides using a porous polymer catalyst in a continuous flow catalytic system comprises the following steps: filling a microreactor with the porous polymer catalyst prepared according to this invention; continuously pumping a reactant solution containing epoxide and alcohol through a reaction column; and evaporating the solvent to obtain the ring-opening product. Specifically, based on epoxide, 400-600 mg of microporous polymer catalyst is required for every 48 mmol of epoxide; the concentration of the reactant solution is 0.05-0.2 mol / L, and the flow rate of the reactant solution is 0.05-0.1 mL / min.

[0021] Furthermore, the aforementioned epoxides include, but are not limited to, at least one of styrene oxide, trans-2,3-diphenyl ethylene oxide, cyclohexane oxide, 2,7-dichlorofluorene-4-ethylene oxide, propynyl glycidyl ether, glycidyl ether oxide, cyclohexane oxide, and 2-(chloromethyl)ethylene oxide. Solvents include, but are not limited to, methanol, ethanol, and dichloromethane.

[0022] The beneficial effects of this invention are:

[0023] (1) The sulfonated multifunctional hypercrosslinked self-porous polymer catalyst based on tripterene provided by the present invention is prepared by one-pot method using inexpensive and readily available tripterene as raw material, forming a three-dimensional network porous structure hypercrosslinked polymer material with low preparation cost and simple post-processing; and is chemically stable due to covalent bond linkage.

[0024] (2) The polymer catalyst provided by this invention is rich in porous structure and can efficiently catalyze the ring-opening of epoxides and the green synthesis of biodiesel under simple catalytic conditions. With a small amount of catalyst, a short reaction time and a low temperature, a conversion rate of nearly 100% can be achieved.

[0025] (3) Compared with traditional processes, it avoids environmental pollution, equipment corrosion and metal use. It has the advantages of mild conditions, simple operation, high reaction yield, recyclable catalyst, less waste, low cost and environmental friendliness, and is suitable for industrial production applications. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This invention provides a synthetic route for the sulfonated multifunctional hypercrosslinked self-porous polymer based on tripterene.

[0028] Figure 2 The images show the FTIR spectra of the products prepared in Examples 1-3 of this invention.

[0029] Figure 3 The N2 isothermal adsorption-desorption curves were obtained by BET testing of the products prepared in Examples 1-3 of this invention.

[0030] Figure 4 The TGA images are of the products prepared in Examples 1-3 of this invention.

[0031] Figure 5 These are SEM images of the products prepared in Examples 1-3 of this invention.

[0032] Figure 6 The pore size distribution diagrams are obtained by BET testing of the products prepared in Examples 1-3 of this invention.

[0033] Figure 7 The degree of sulfonation of the STHCPIM materials prepared in Examples 1-3 of this invention.

[0034] Figure 8 To compare the catalytic effect of catalyst STHCPIM-3 through a hot filtration experiment.

[0035] Figure 9 The results of the cyclic recovery experiment are presented to test the stability of the catalyst STHCPIM-3 of this invention.

[0036] Figure 10 This is a diagram of a continuous flow catalytic device demonstrating the catalytic effect of the STHCPIM-3 catalyst of this invention.

[0037] Figure 11 This is a diagram showing the continuous flow catalytic effect of the catalyst STHCPIM-3 of this invention. Detailed Implementation

[0038] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] Example 1

[0040] The preparation method of the porous polymer catalyst in this embodiment is shown in the following synthetic route diagram. Figure 1 As shown, the specific steps are as follows:

[0041] (1) A Friedel-Crafts alkylation reaction was performed. Under ice-water bath conditions, an ultra-dry dichloromethane solution (45 mL) containing anhydrous aluminum trichloride (9.5 g, 71 mmol) was added to a 250 mL flask equipped with a magnetic stir bar. Then, an ultra-dry dichloromethane solution (15 mL) containing triptene (1.5 g, 6 mmol) was added dropwise and mixed thoroughly. After returning to room temperature, the reaction was stirred at 60 °C for 24 h. After cooling to room temperature, the reaction was quenched in an ice-water solution of hydrochloric acid. After filtration, the product was washed twice with water, ethanol, and chloroform, respectively, and then heated under reflux twice in chloroform and ethanol, respectively. After filtration, the resulting solid was vacuum dried at 120 °C for 12 h to obtain a brown powder, namely the hypercrosslinked self-contained microporous polymer (THCPIM, 4.7 g, 100%).

[0042] The structural properties of the THCPIM prepared above were characterized by FTIR (2968 cm⁻¹). -1 2921 cm -1 1675 cm -1 1612 cm -1 1439 cm -1 1086 cm -1 894 cm -1 , Figure 2 Tests showed that THCPIM was successfully synthesized; N2 isothermal adsorption-desorption experiments showed that THCPIM has a high specific surface area (1514 m²). 2 / g, Figure 3 TGA test results show that THCPIM has good thermal stability. Figure 4 SEM testing showed that THCPIM has a microsphere structure of 2-8 µm. Figure 5 THCPIM possesses a hierarchical porous structure: ultramicropores (0.5-0.7 nm), micropores (0.7-2 nm), and mesopores (2-5 nm). Figure 6 ).

[0043] (2) Using the sulfonation reaction, dry THCPIM (1 g) and concentrated sulfuric acid (20 mL) were added to a 100 mL round-bottom flask and stirred at room temperature for 1 h. The mixture was then quenched in ice water, filtered, washed with water until neutral, washed three times with methanol, and then heated under reflux in methanol twice. After filtration, the resulting solid was dried at 80 °C for 12 h to obtain STHCPIM-1 (1.5 g, 69%), which is a porous polymer catalyst.

[0044] The structural properties of the STHCPIM-1 prepared above were characterized by FTIR (3400 cm⁻¹). -1 2968 cm -1 1668 cm -11603 cm -1 1175 cm -1 1040 cm -1 619 cm -1 , Figure 2 Tests showed that STHCPIM-1 was successfully synthesized; N2 isothermal adsorption-desorption experiments showed that STHCPIM-1 has a high specific surface area (1043 m²). 2 / g, Figure 3 TGA test results show that STHCPIM-1 has good thermal stability. Figure 4 SEM testing showed that the sulfonation reaction did not affect the morphology of the porous polymer; STHCPIM-1 exhibited a microsphere structure of 2-8 µm. Figure 5 STHCPIM-1 has a hierarchical porous structure: ultramicropores (0.5-0.7 nm) and micropores (0.7-2 nm). Figure 6 The sulfonation degree of STHCPIM-1 was determined to be 40% by titration. Figure 7 ).

[0045] Example 2

[0046] The specific steps for preparing the porous polymer catalyst in this embodiment are as follows:

[0047] (1) A Friedel-Crafts alkylation reaction was performed. Under ice-water bath conditions, an ultra-dry dichloromethane solution (45 mL) containing anhydrous aluminum trichloride (9.5 g, 71 mmol) was added to a 250 mL flask equipped with a magnetic stir bar. Then, an ultra-dry dichloromethane solution (15 mL) containing triptene (1.5 g, 6 mmol) was added dropwise and mixed thoroughly. After returning to room temperature, the reaction was stirred at 60 °C for 24 h. After cooling to room temperature, the reaction was quenched in an ice-water solution of hydrochloric acid. After filtration, the product was washed twice with water, ethanol, and chloroform, respectively, and then heated under reflux twice in chloroform and ethanol, respectively. After filtration, the resulting solid was vacuum dried at 120 °C for 12 h to obtain a brown powder, namely the hypercrosslinked self-contained microporous polymer (THCPIM, 4.7 g, 100%).

[0048] (2) Using the sulfonation reaction, dry THCPIM (1 g) and concentrated sulfuric acid (20 mL) were added to a 100 mL round-bottom flask and stirred at 60 °C for 1 h. The mixture was then quenched in ice water, filtered, washed with water until neutral, washed three times with methanol, and then heated under reflux in methanol twice. After filtration, the resulting solid was dried at 80 °C for 12 h to obtain STHCPIM-2 (1.2 g, 57%), which is a porous polymer catalyst.

[0049] The structural properties of the obtained STHCPIM-2 were characterized by FTIR (3400 cm⁻¹).-1 2968 cm -1 1668 cm -1 1603cm -1 1175 cm -1 1040 cm -1 619 cm -1 , Figure 2 Tests showed that STHCPIM-2 was successfully synthesized; N2 isothermal adsorption-desorption experiments showed that STHCPIM-2 has a high specific surface area (1173 m²). 2 / g, Figure 3 TGA test results show that STHCPIM-2 has good thermal stability. Figure 4 SEM testing showed that the sulfonation reaction did not affect the morphology of the porous polymer; STHCPIM-2 exhibited a microsphere structure of 2-8 µm. Figure 5 STHCPIM-2 has a hierarchical porous structure: ultramicropores (0.5-0.7 nm) and micropores (0.7-2 nm). Figure 6 The sulfonation degree of STHCPIM-2 was determined to be 49% by titration. Figure 7 ).

[0050] Example 3

[0051] The specific steps for preparing the porous polymer catalyst in this embodiment are as follows:

[0052] (1) A Friedel-Crafts alkylation reaction was performed. Under ice-water bath conditions, an ultra-dry dichloromethane solution (45 mL) containing anhydrous aluminum trichloride (9.5 g, 71 mmol) was added to a 250 mL flask equipped with a magnetic stir bar. Then, an ultra-dry dichloromethane solution (15 mL) containing triptene (1.5 g, 6 mmol) was added dropwise and mixed thoroughly. After returning to room temperature, the reaction was stirred at 60 °C for 24 h. After cooling to room temperature, the reaction was quenched in an ice-water solution of hydrochloric acid. After filtration, the product was washed twice with water, ethanol, and chloroform, respectively, and then heated under reflux twice in chloroform and ethanol, respectively. After filtration, the resulting solid was vacuum dried at 120 °C for 12 h to obtain a brown powder, namely the hypercrosslinked self-contained microporous polymer (THCPIM, 4.7 g, 100%).

[0053] (2) Using the sulfonation reaction, dry THCPIM (1 g) and concentrated sulfuric acid (20 mL) were added to a 100 mL round-bottom flask and stirred at 60 °C for 24 h. Then the reaction was quenched in ice water, filtered, washed with water until neutral, washed three times with methanol, and then heated under reflux in methanol twice. After filtration, the obtained solid was dried at 80 °C for 12 h to obtain STHCPIM-3 (1.6 g, 72%), which is a porous polymer catalyst.

[0054] The structural properties of the obtained STHCPIM-3 were characterized by FTIR (3400 cm⁻¹). -1 2968 cm -1 1668 cm -1 1603cm -1 1175 cm -1 1040 cm -1 619 cm -1 , Figure 2 Tests showed that STHCPIM-3 was successfully synthesized; N2 isothermal adsorption-desorption experiments showed that STHCPIM-3 has a high specific surface area (886 m²). 2 / g, Figure 3 TGA test results show that STHCPIM-3 has good thermal stability. Figure 4 SEM testing showed that the sulfonation reaction did not affect the morphology of the porous polymer; STHCPIM-3 exhibited a microsphere structure of 2-8 µm. Figure 5 STHCPIM-3 has a hierarchical porous structure: ultramicropores (0.5-0.7 nm) and micropores (0.7-2 nm). Figure 6 The sulfonation degree of STHCPIM-3 was determined to be 64% by titration. Figure 7 ).

[0055] Example 4

[0056] The specific steps for preparing the porous polymer catalyst in this embodiment are as follows:

[0057] (1) A Friedel-Crafts alkylation reaction was performed. Under ice-water bath conditions, 15 mL of ultra-dry dichloromethane solution containing anhydrous aluminum trichloride (120 mmol) was added to a 250 mL flask equipped with a magnetic stir bar. Then, 15 mL of ultra-dry dichloromethane solution containing triptene (1.5 g, 6 mmol) was added dropwise and mixed thoroughly. After returning to room temperature, the reaction was stirred at room temperature for 48 h. After the reaction was completed, the mixture was quenched in an ice-water solution of hydrochloric acid. After filtration, the mixture was washed twice with water, ethanol, and chloroform, respectively, and then heated under reflux twice in chloroform and ethanol, respectively. After filtration, the obtained solid was vacuum dried at 120 °C for 12 h to obtain a brown powder, namely the hypercrosslinked self-porous polymer (THCPIM).

[0058] (2) Using the sulfonation reaction, dry THCPIM (5 g) and concentrated sulfuric acid (20 mL) were added to a 100 mL round-bottom flask and stirred at 80 °C for 0.1 h. Then the reaction was quenched in ice water, filtered, washed with water until neutral, washed three times with methanol, and then heated under reflux in methanol twice. After filtration, the obtained solid was dried at 80 °C for 12 h to obtain STHCPIM-4, which is a porous polymer catalyst.

[0059] Example 5

[0060] The specific steps for preparing the porous polymer catalyst in this embodiment are as follows:

[0061] (1) A Friedel-Crafts alkylation reaction was performed. Under ice-water bath conditions, an ultra-dry dichloromethane solution (7 mL) containing anhydrous aluminum trichloride (10 mmol) was added to a 250 mL flask equipped with a magnetic stir bar. Then, an ultra-dry dichloromethane solution (5 mL) containing triptene (1.5 g, 6 mmol) was added dropwise and mixed thoroughly. After returning to room temperature, the reaction was stirred at 40 °C for 0.1 h. After cooling to room temperature, the reaction was quenched in an ice-water solution of hydrochloric acid. After filtration, the product was washed twice with water, ethanol, and chloroform, respectively, and then heated under reflux twice in chloroform and ethanol, respectively. After filtration, the resulting solid was vacuum dried at 120 °C for 12 h to obtain a brown powder, namely the hypercrosslinked self-porous polymer (THCPIM).

[0062] (2) Using the sulfonation reaction, dry THCPIM (10 g) and concentrated sulfuric acid (20 mL) were added to a 100 mL round-bottom flask and stirred at room temperature for 48 h. Then the reaction was quenched in ice water, filtered, washed with water until neutral, washed three times with methanol, heated and refluxed twice in methanol, filtered, and the resulting solid was dried at 80 °C for 12 h to obtain STHCPIM-5, which is a porous polymer catalyst.

[0063] Application examples

[0064] I. The porous polymer catalyst STHCPIM-3 prepared in Example 3 of this invention was subjected to performance testing. The epoxy ring-opening reaction process is as follows:

[0065] .

[0066] The specific test examples and results are as follows:

[0067] Application Example 1

[0068] A mixture of styrene oxide (1 mmol), catalyst STHCPIM-3 (10 mg), and methanol (2.5 mL) was placed in a 10 mL round-bottom flask; the mixture was then stirred at room temperature for 0.5 h, and the reaction solution was filtered through...1 H-NMR analysis data are shown in Table 1.

[0069] Application Example 2

[0070] A mixture of styrene oxide (1 mmol), catalyst STHCPIM-3 (10 mg), and ethanol (2.5 mL) was placed in a 10 mL round-bottom flask; the mixture was then stirred at room temperature for 0.5 h, and the reaction solution was filtered through... 1 H-NMR analysis data are shown in Table 1.

[0071] Application Example 3

[0072] A mixture of styrene oxide (1 mmol), catalyst STHCPIM-3 (50 mg), and n-propanol (2.5 mL) was placed in a 10 mL round-bottom flask; the mixture was then stirred at room temperature for 1 h, and the reaction solution was filtered through... 1 H-NMR analysis data are shown in Table 1.

[0073] Application Example 4

[0074] A mixture of styrene oxide (1 mmol), catalyst STHCPIM-3 (50 mg), and isopropanol (2.5 mL) was placed in a 10 mL round-bottom flask; the mixture was then stirred at room temperature for 1 h, and the reaction solution was filtered through... 1 H-NMR analysis data are shown in Table 1.

[0075] Application Example 5

[0076] A mixture of trans-2,3-diphenylethylene oxide (1 mmol), catalyst STHCPIM-3 (5 mg), and methanol (2.5 mL) was placed in a 10 mL round-bottom flask. The mixture was then stirred at 60 °C for 0.5 h. The reaction solution was filtered and passed through... 1 H-NMR analysis data are shown in Table 1.

[0077] Application Example 6

[0078] A mixture of 2,7-dichlorofluorene-4-epoxyethylene (1 mmol), catalyst STHCPIM-3 (5 mg), and methanol (2.5 mL) was placed in a 10 mL round-bottom flask. The mixture was then stirred at 60 °C for 5 h. The reaction solution was filtered and passed through... 1 H-NMR analysis data are shown in Table 1.

[0079] Application Example 7

[0080] A mixture of propynyl glycidyl ether (1 mmol), catalyst STHCPIM-3 (15 mg), and methanol (2.5 mL) was placed in a 10 mL round-bottom flask; the mixture was then stirred at 60 °C for 12 h, and the reaction solution was filtered through... 1 H-NMR analysis data are shown in Table 1.

[0081] Application Example 8

[0082] In a 10 mL round-bottom flask, glycidyl phenyl ether (1 mmol), catalyst STHCPIM-3 (15 mg), and methanol (2.5 mL) were added to obtain a mixture; the mixture was then stirred at 60 °C for 12 h, and the reaction solution was filtered and passed through... 1 H-NMR analysis data are shown in Table 1.

[0083] Application Example 9

[0084] A mixture of cyclohexane oxide (5 mmol), catalyst STHCPIM-3 (50 mg), and methanol (5 mL) was placed in a 10 mL round-bottom flask; the mixture was then stirred at 98 °C for 0.1 h to obtain the epoxy ring-opening product.

[0085] Application Example 10

[0086] 2-(chloromethyl)ethylene oxide (0.1 mmol), catalyst STHCPIM-3 (5 mg), and methanol (5 mL) were placed in a 10 mL round-bottom flask to obtain a mixture; the mixture was then stirred at 98 °C for 0.1 h to obtain the epoxide ring-opening product.

[0087] Application Example 11

[0088] In a 10 mL round-bottom flask, cyclohexane oxide (3 mmol), catalyst STHCPIM-3 (5 mg), and methanol (1 mL) were added to obtain a mixture; the mixture was then stirred at 98 °C for 0.1 h to obtain the epoxide ring-opening product.

[0089] Table 1

[0090]

[0091] As can be seen from Table 1, the catalyst provided by this invention has high catalytic activity. Styrene and methanol can be completely converted at room temperature using only 10 mg of catalyst STHCPIM-3 in 0.5 h. Furthermore, the macromolecular epoxide trans-2,3-diphenyl ethylene oxide can also be completely converted at 60 °C using only 5 mg of catalyst STHCPIM-3 in 0.5 h.

[0092] II. Thermal filtration experiment of STHCPIM-3, a sulfonated multifunctional hypercrosslinked microporous polymer catalyst based on tripterene:

[0093] The catalyst (STHCPIM-3, 5 mg), styrene oxide (1.0 mmol), and methanol (2.5 mL) were used in a stirred reaction at room temperature. After 10 min, the catalyst in the control group was removed by filtration, and the resulting clear solution was reacted for another 180 min. Figure 8 As shown, in the control group, after removing the catalyst, the conversion rate of styrene oxide no longer increased with time, indicating that there were no free acidic substances in the system and the catalytic reaction could not continue. However, in the experimental group, with the STHCPIM-3 catalyst retained, the conversion rate of styrene oxide continued to increase with reaction time, reaching 84.28% at 180 min.

[0094] III. The recycling of STHCPIM-3, a sulfonated multifunctional hypercrosslinked microporous polymer catalyst based on tripterene, is carried out through the following steps:

[0095] 1 mmol of styrene oxide was mixed with 2.5 mL of methanol and added to a round-bottom flask, followed by the addition of 10 mg of catalyst STHCPIM-3. The reaction mixture was stirred at room temperature for 0.5 h. After the reaction was complete, the mixture was analyzed by HPLC. The catalyst was recovered from the reaction system through a 0.45 μm microporous membrane, washed twice with methanol, dried in a vacuum oven, and then reused. Figure 9 As shown, the sulfonated multifunctional hypercrosslinked microporous polymer catalyst STHCPIM-3 based on tripterene can achieve 6 cycles of catalysis without significant loss of catalytic efficiency, indicating that the sulfonated multifunctional hypercrosslinked microporous polymer catalyst based on tripterene can be recycled multiple times and has good cycle stability.

[0096] IV. The continuous flow catalytic reaction of STHCPIM-3, a sulfonated multifunctional hypercrosslinked microporous polymer catalyst based on tripterene, is carried out in the following steps:

[0097] A 3 mL affinity chromatography column was placed at the bottom with a column sieve plate. STHCPIM-3 powder (0.4-0.6 g) was loaded into the column, and a column sieve plate was placed on top. A methanol solution containing 0.2 mol / L phenylene oxide was injected into the column containing the STHCPIM-3 catalyst at a flow rate of 0.1 mL / min using a micro-injection pump. Figure 10 During the reaction, samples were collected every 4 hours, and their components were analyzed by HPLC. After flow completion, the column was washed with 10 mL of methanol to remove residual reactants and products. The collected solution was then subjected to rotary evaporation to remove the solvent, and the resulting product was weighed to calculate the yield.

[0098] Continuous flow catalysis experimental results show that ( Figure 11 During continuous operation for 40 hours, the complete conversion of styrene oxide was achieved, producing the target ring-opening product with a yield of up to 90%, demonstrating that STHCPIM-3 has stable and efficient catalytic performance in continuous reaction systems.

[0099] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. The application of porous polymer catalysts in the catalytic ring-opening reaction of epoxy resins, characterized in that, The porous polymer catalyst is prepared as follows: (1) Dissolve triterpenes and Lewis acid in a solvent, react I, wash, reflux, filter and dry to obtain a hypercrosslinked porous polymer; (2) The super-crosslinked self-porous polymer obtained in step (1) is dispersed in concentrated sulfuric acid and reaction II is carried out to obtain sulfonated multifunctional super-crosslinked self-porous polymer, i.e., porous polymer catalyst.

2. The application of the porous polymer catalyst according to claim 1 in the catalytic ring-opening reaction of epoxy resin, characterized in that, In step (1), the molar ratio of triptene to Lewis acid is 1:10-20, and the concentration of triptene is 0.1-0.5 mmol / mL.

3. The application of the porous polymer catalyst according to claim 1 or 2 in the catalytic ring-opening reaction of epoxy resin, characterized in that, In step (1), the Lewis acid is selected from anhydrous aluminum trichloride or anhydrous ferric trichloride, and the solvent is any one of dichloromethane, chloroform and 1,2-dichloroethane; the temperature of reaction I is room temperature to 60°C, and the time is 0.1-48 h.

4. The application of the porous polymer catalyst according to claim 3 in the catalytic ring-opening reaction of epoxy resin, characterized in that, In step (2), 0.05-0.5 g of hypercrosslinked self-porous polymer is added to every 1 mL of concentrated sulfuric acid. The temperature of reaction II is from room temperature to 80°C, and the time is 0.1-48 h. The raw material in the catalytic epoxy ring-opening reaction is epoxide.

5. The application of the porous polymer catalyst according to claim 4 in the catalytic ring-opening reaction of epoxy resin, characterized in that, The epoxide is at least one selected from styrene oxide, trans-2,3-diphenyl ethylene oxide, cyclohexane oxide, 2,7-dichlorofluorene-4-ethylene oxide, propynyl glycidyl ether, propyl phenyl ether, cyclohexane oxide, and 2-(chloromethyl)ethylene oxide.

6. A method for catalyzing the ring-opening reaction of epoxy resin using a porous polymer catalyst, characterized in that, The steps are as follows: The porous polymer catalyst prepared by the method described in claim 1 is reacted with an epoxide and an alcohol to obtain a ring-opening product.

7. The method for catalyzing the ring-opening reaction of epoxy resin using a porous polymer catalyst according to claim 6, characterized in that, Based on epoxide, each 0.1-5 mmol of epoxide requires 5-50 mg of microporous polymer catalyst and 1-5 mL of alcohol.

8. The method for catalyzing the ring-opening reaction of epoxy resin using a porous polymer catalyst according to claim 7, characterized in that, The alcohol is at least one of methanol, ethanol, n-propanol, and isopropanol.

9. The method for catalyzing the ring-opening reaction of epoxy resin using a porous polymer catalyst according to claim 8, characterized in that, The temperature of reaction III is from room temperature to 98°C, and the time is 0.1-12 h.

10. A method for catalyzing the ring-opening reaction of epoxy resins using a porous polymer catalyst in a continuous flow catalytic system, characterized in that, The steps are as follows: The porous polymer catalyst prepared by the method described in claim 1 is placed in a reactor, and a reactant solution containing epoxide and alcohol is continuously pumped in and flows through a reaction column. After evaporating the solvent, the ring-opening product is obtained.

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