Method for synthesizing 3-hydroxypropionaldehyde by catalyzing acrolein
By using a sulfonic acid-based covalent organic framework catalyst, the problem of poor stability of sulfonic acid resin catalysts was solved, and a high-yield synthesis of 3-hydroxypropionaldehyde was achieved. The catalyst stability and activity were significantly improved, and it is easy to recycle and environmentally friendly.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- PETROCHINA CO LTD
- Filing Date
- 2024-11-15
- Publication Date
- 2026-05-15
AI Technical Summary
Existing sulfonic acid resin catalysts exhibit poor stability during the synthesis of 3-hydroxypropionaldehyde from acrolein, with sulfonic acid groups easily detaching, leading to reduced catalyst activity. Furthermore, traditional catalysts are prone to corroding equipment and contaminating the reaction system.
A sulfonic acid covalent organic framework (COF-SO3H) was used as a catalyst, with sulfonic acid groups linked to the covalent organic framework via covalent bonds. This catalyst was used to catalyze the synthesis of 3-hydroxypropionaldehyde from acrolein. A polymerization inhibitor was added to carry out the reaction in an aqueous system.
The catalyst's stability and catalytic activity were improved, with a yield of 3-hydroxypropanal reaching 85.2%. The catalyst is easy to recover and reuse, does not easily corrode equipment, and reduces the risk of pollution.
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Figure CN122036477A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for synthesizing 3-hydroxypropanal, and more specifically to a method for catalytically synthesizing 3-hydroxypropanal from acrolein. Background Technology
[0002] The catalytic hydration of acrolein can synthesize the important intermediate 3-hydroxypropanal, and the subsequent catalytic hydrogenation of 3-hydroxypropanal can synthesize 1,3-propanediol. The primary application of 1,3-propanediol is as a raw material for the synthesis of the novel polyester material 1,3-propanediol terephthalate (PTT). Acrolein is a key intermediate product of propylene oxidation in the petrochemical industry, and the efficient catalytic hydration synthesis of 3-hydroxypropanal from acrolein has significant practical application value.
[0003] Currently, the reported methods for catalytic hydration of acrolein are as follows: (1) Using liquid acid catalysts, such as inorganic or organic acids like sulfuric acid, phosphoric acid, and hydrochloric acid. However, these homogeneous liquid acid catalysts are prone to corroding equipment and contaminating the reaction system, and they can also cause acrolein to undergo condensation or polymerization reactions (Chemical Engineer, 2004, 106(7): 6-7). (2) Supported inorganic acid catalysts, where inorganic acids are supported on specific carrier surfaces, such as H3PO4 / γ-Al2O3, NaH2PO4 / γ-Al2O3, H3PO4 / TiO2, NaH2PO4 / TiO2, etc., which can also catalyze the hydration of acrolein to 3-hydroxypropionaldehyde in an aqueous system. The preparation method of this type of catalyst is simple, but in an aqueous system, the supported acid components are prone to detach from the carrier and be lost, resulting in a decrease in catalyst activity. (3) Zeolite molecular sieve catalysts: Zeolite molecular sieves are hydrates of crystalline aluminosilicate metal salts. After activation, water molecules are removed, and the remaining atoms form a cage-like structure. This cage-like structure is very beneficial for the catalysis of specific reactions. However, when zeolite molecular sieves are used to catalyze hydration reactions, the reaction conversion rate is very low, only about 50%, which greatly limits the large-scale application of this type of catalyst. (4) Resin catalysts: Sulfonic acid resin catalysts can be used to catalyze the hydration reaction of acrolein due to their good acidity. However, most sulfonic acid resin catalysts are polystyrene sulfonic acid type catalysts, in which the sulfonic acid groups are easily detached and lost, resulting in poor catalyst stability. Summary of the Invention
[0004] To address the problem of poor stability of sulfonic acid resin catalysts mentioned in the prior art, this invention provides a method for catalytic synthesis of 3-hydroxypropionaldehyde from acrolein. This method uses a sulfonic acid covalent organic framework (COF-SO3H) as a catalyst, wherein the sulfonic acid sites of the catalyst are covalently linked to the covalent organic framework, making them stable and not easily detached.
[0005] This invention is achieved through the following technical solution: This invention provides a method for catalytically synthesizing 3-hydroxypropional from acrolein. Using acrolein as a raw material, a sulfonic acid-based covalent organic framework as a catalyst, and adding water and a polymerization inhibitor, the reaction is carried out under heating conditions to obtain 3-hydroxypropional. The structural formula of the sulfonic acid-based covalent organic framework is as follows: .
[0006] Preferably, in the method for catalytic synthesis of 3-hydroxypropional from acrolein, the amount of the sulfonic acid covalent organic framework is 10wt%-50wt% of acrolein.
[0007] Preferably, in the method for catalytic synthesis of 3-hydroxypropional from acrolein, the polymerization inhibitor is one of 4-methoxyphenol, hydroquinone, ZJ-701, and phenothiazine.
[0008] Furthermore, in the method for catalyzing the synthesis of 3-hydroxypropional from acrolein, the polymerization inhibitor is hydroquinone.
[0009] Preferably, in the method for catalytic synthesis of 3-hydroxypropional from acrolein, the reaction temperature is 50-80℃ and the reaction time is 6-48h.
[0010] Preferably, in the method for catalytic synthesis of 3-hydroxypropionaldehyde from acrolein, the amount of polymerization inhibitor used is 1wt%-5wt% of acrolein.
[0011] Preferably, in the method for catalytic synthesis of 3-hydroxypropionaldehyde from acrolein, the preparation method of the sulfonic acid-based covalent organic framework is as follows: using 2,4,6-trihydroxy-1,3,5-benzenetriformaldehyde and p-phenylenediamine sulfonic acid as raw materials, the reaction is carried out under the catalysis of trifluoroacetic acid, and the resulting product is washed and dried to obtain the sulfonic acid-based covalent organic framework.
[0012] Furthermore, in the preparation method of the sulfonic acid covalent organic framework, the molar ratio of 2,4,6-trihydroxy-1,3,5-benzenetriformaldehyde, p-phenylenediamine sulfonic acid and trifluoroacetic acid is 2:3:(0.01-0.02).
[0013] Furthermore, the preparation method of the sulfonic acid-based covalent organic framework involves a reaction temperature of 100-110℃ and a reaction time of 60-80 seconds.
[0014] Furthermore, in the preparation method of the sulfonic acid covalent organic framework, the temperature of the detergent during product washing is 80-120℃.
[0015] Compared with the prior art, the present invention has the following beneficial effects: In the synthesis method of 3-hydroxypropionaldehyde of this invention, a sulfonic acid covalent organic framework is used as a catalyst. This sulfonic acid covalent organic framework has strongly acidic sulfonic acid sites. Under the catalytic action of these sites, the carbon-carbon double bond of acrolein undergoes a hydration addition reaction to generate 3-hydroxypropionaldehyde. The sulfonic acid sites on the sulfonic acid covalent organic framework catalyst are covalently linked to the covalent organic framework, making them stable and resistant to detachment. This effectively solves the problems of easy detachment of acidic sites and poor catalyst stability in existing sulfonic acid resin catalysts. After 10 cycles of use, the yield of 3-hydroxypropionaldehyde catalyzing the hydration reaction of acrolein can still reach 85.2%. Furthermore, the sulfonic acid covalent organic framework catalyst of this invention has a mesoporous structure, which facilitates the diffusion and mass transfer of reactant molecules, thereby improving the catalytic effect. The sulfonic acid-based covalent organic framework catalyst used in this invention has high catalytic activity and high product yield. Moreover, the sulfonic acid-based covalent organic framework catalyst is a solid powder acidic catalyst, which is different from liquid acid catalysts in catalytic hydration reactions. It is not easy to corrode equipment, will not remain in the hydration products, the catalyst and the reaction system are easy to separate, and it can be recycled, which is economical and environmentally friendly. Attached Figure Description
[0016] 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 some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0017] Figure 1 Infrared spectrum (a) and X-ray powder diffraction pattern (b) of the catalyst prepared in Example 1 of this invention.
[0018] Figure 2 The nitrogen adsorption-desorption curve (a) and pore size distribution curve (b) of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 of this invention. Detailed Implementation
[0019] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.
[0020] It should be noted that the process equipment or apparatus not specifically mentioned in the following embodiments are all conventional equipment or apparatus in the art.
[0021] It should be noted that the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or apparatus that includes a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to these processes, methods, products, or apparatuses. Furthermore, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not intended to limit the order of the method steps or define the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.
[0022] The structural formula of the sulfonic acid-based covalent organic framework of the present invention is shown below: .
[0024] The sulfonic acid covalent organic framework described in this invention has a strong acidic sulfonic acid site and can be used as a solid acid catalyst for catalyzing the hydration of acrolein to synthesize 3-hydroxypropional.
[0025] The method for preparing the sulfonic acid-based covalent organic framework of the present invention includes: using 2,4,6-trihydroxy-1,3,5-benzenetriformaldehyde and p-phenylenediamine sulfonic acid as raw materials, reacting them under the catalysis of trifluoroacetic acid, and washing and drying the resulting product to obtain the sulfonic acid-based covalent organic framework.
[0026] The role of adding trifluoroacetic acid is to promote the aldehyde-amine condensation of 2,4,6-trihydroxy-1,3,5-benzenetriformaldehyde and p-phenylenediamine sulfonic acid. Under the catalysis of trifluoroacetic acid, the two undergo an aldehyde-amine condensation reaction to generate a sulfonic acid covalent organic framework.
[0027] In the preparation method of the sulfonic acid covalent organic framework of the present invention, the molar ratio of 2,4,6-trihydroxy-1,3,5-benzenetriformaldehyde, p-phenylenediamine sulfonic acid, and trifluoroacetic acid is 2:3:(0.01-0.02); the reaction temperature is 100-130℃, and the reaction time is 60-80h.
[0028] In the preparation method of the sulfonic acid covalent organic framework of the present invention, the temperature of the detergent during product washing is 80-120℃.
[0029] The present invention provides a method for catalytically synthesizing 3-hydroxypropional from acrolein. Using acrolein as a raw material, the sulfonic acid-based covalent organic framework prepared above as a catalyst, and a polymerization inhibitor, the method catalyzes the hydration of acrolein to 3-hydroxypropional in an aqueous system. The reaction formula is as follows: .
[0030] In the method for catalytic synthesis of 3-hydroxypropanal from acrolein in this invention, water is used as both a solvent and a reactant. Under the catalytic action of the strongly acidic sulfonic acid group sites of the sulfonic acid covalent organic framework, the carbon-carbon double bond of acrolein undergoes a hydration addition reaction to generate 3-hydroxypropanal.
[0031] In the method for catalytic synthesis of 3-hydroxypropional from acrolein of the present invention, the reaction time is 6-48 h, preferably 6-12 h, and more preferably 8-12 h. The amount of the sulfonic acid covalent organic framework is 10 wt%-50 wt% of acrolein, more preferably 10 wt%. The catalytic hydration reaction temperature is 50-80 °C, more preferably 70 °C.
[0032] The polymerization inhibitor used in this invention is one of 4-methoxyphenol, hydroquinone, ZJ-701, and phenothiazine, with hydroquinone being preferred. The amount of the polymerization inhibitor is 1 wt%-5 wt% of acrolein, preferably 5 wt%.
[0033] This invention uses a sulfonic acid-based covalent organic framework material as a catalyst to catalyze the hydration of acrolein to synthesize 3-hydroxypropionaldehyde. The catalyst is a solid catalyst with sulfonic acid groups firmly covalently linked to the covalent organic framework. The catalyst is easy to recover and can be reused multiple times. The sulfonic acid groups have good covalent linkage stability and are not easily detached during the catalytic reaction.
[0034] Example 1 The specific method for preparing the sulfonic acid group covalent organic framework of the catalyst is as follows: 0.42 g of 2,4,6-trihydroxy-1,3,5-benzenetrialdehyde, 0.56 g of p-phenylenediamine sulfonic acid, and 1.15 mg of trifluoroacetic acid catalyst were placed in a three-necked flask. The reaction system was stirred vigorously in a sand bath at 120 °C for 72 h to obtain a yellow polymer. Subsequently, the product was collected by filtration and washed with DMF at 100 °C. Finally, the mixture was placed in a vacuum drying oven for 24 h to obtain a sulfonic acid-based covalent organic framework catalyst.
[0035]
[0036] Example 2 The specific method for preparing the sulfonic acid group covalent organic framework of the catalyst is as follows: 0.42 g of 2,4,6-trihydroxy-1,3,5-benzenetrialdehyde, 0.56 g of p-phenylenediamine sulfonic acid, and 1.15 mg of trifluoroacetic acid catalyst were placed in a three-necked flask. The reaction system was vigorously stirred in a sand bath at 110 °C for 80 h to obtain a yellow polymer. Subsequently, the product was collected by filtration and washed with DMF at 80 °C. Finally, the product was placed in a vacuum drying oven for 24 h to obtain a sulfonic acid-based covalent organic framework catalyst.
[0037] Example 3 The specific method for preparing the sulfonic acid group covalent organic framework of the catalyst is as follows: 0.42 g of 2,4,6-trihydroxy-1,3,5-benzenetrialdehyde, 0.56 g of p-phenylenediamine sulfonic acid, and 2.30 mg of trifluoroacetic acid catalyst were placed in a three-necked flask. The reaction system was stirred vigorously in a sand bath at 130 °C for 60 h to obtain a yellow polymer. Subsequently, the product was collected by filtration and washed with DMF at 120 °C. Finally, the mixture was placed in a vacuum drying oven for 24 h to obtain a sulfonic acid-based covalent organic framework catalyst.
[0038] Example 4 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor 4-methoxyphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 77.6%. The reaction results are shown in Table 1 below.
[0039] Example 5 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 88.1%. The reaction results are shown in Table 1 below.
[0040] Example 6 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of polymerization inhibitor ZJ701 are added to a reactor. The reaction is carried out at 70 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 80.1%. The reaction results are shown in Table 1 below.
[0041] Example 7 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor thiophenezine are added to a reactor. The reaction is carried out at 70 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 81.7%. The reaction results are shown in Table 1 below.
[0042] Example 8 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.025 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 74.3%. The reaction results are shown in Table 1 below.
[0043] Example 9 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.1 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional during the reaction are determined by gas chromatography, and the result is 75.5%. The reaction results are shown in Table 1 below.
[0044] Example 10 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 50 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 58.5%. The reaction results are shown in Table 1 below.
[0045] Example 11 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 60 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional during the reaction are determined by gas chromatography, and the result is 72.9%. The reaction results are shown in Table 1 below.
[0046] Example 12 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 80 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 77.2%. The reaction results are shown in Table 1 below.
[0047] Example 13 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 10 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 78.5%. The reaction results are shown in Table 1 below.
[0048] Example 14 A method for catalytic synthesis of 3-hydroxypropanal from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 8 h. The conversion rate of acrolein and the yield of 3-hydroxypropanal during the reaction are determined by gas chromatography, and the result is 67.4%. The reaction results are shown in Table 1 below.
[0049] Example 15 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 6 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 59.6%. The reaction results are shown in Table 1 below.
[0050] Example 16 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 0.25 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 48 h. The conversion rate of acrolein and the yield of 3-hydroxypropional during the reaction are determined by gas chromatography, and the result is 72.9%. The reaction results are shown in Table 1 below.
[0051] Example 17 A method for catalytic synthesis of 3-hydroxypropanal from acrolein is disclosed, the specific method being as follows: 0.5 g of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 above, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of the polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 48 h. The conversion rate of acrolein and the yield of 3-hydroxypropanal during the reaction are determined by gas chromatography, and the result is 73.9%. The reaction results are shown in Table 1 below.
[0052] Comparative Example 1 A method for catalytic synthesis of 3-hydroxypropional from acrolein is disclosed, the specific method being as follows: 1 g of commercially available Amberlyst-15 sulfonic acid catalyst, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropional are determined by gas chromatography, and the result is 43.1%. The reaction results are shown in Table 1 below.
[0053] Comparative Example 2 A method for catalytic synthesis of 3-hydroxypropanal from acrolein is disclosed, the specific method being as follows: 1 g of commercially available sulfonic acid XT-92 catalyst, 1.15 mL of acrolein, 8.85 mL of solvent water, and 0.05 g of polymerization inhibitor p-diphenol are added to a reactor. The reaction is carried out at 70 °C with stirring for 12 h. The conversion rate of acrolein and the yield of 3-hydroxypropanal during the reaction are determined by gas chromatography, and the result is 29.4%. The reaction results are shown in Table 1 below.
[0054] Figure 1 Infrared spectrum (a) and X-ray powder diffraction pattern (b) of the catalyst prepared in Example 1 of this invention. Figure 1 As can be seen in (a), the prepared sulfonic acid-based covalent organic framework catalyst has abundant sulfonic acid catalytic sites, which can catalyze the hydration addition reaction of the carbon-carbon double bond in acrolein to generate 3-hydroxypropanal. Figure 1 As can be seen from (b), the prepared sulfonic acid-based covalent organic framework catalyst has an amorphous powder structure. Figure 2 The nitrogen adsorption-desorption curve (a) and pore size distribution curve (b) of the sulfonic acid-based covalent organic framework catalyst prepared in Example 1 of this invention are shown. Figure 2 As can be seen from (a), the prepared sulfonic acid-based covalent organic framework catalyst has a mesoporous structure. From... Figure 2 (b) It can be seen that the average pore size distribution of the prepared sulfonic acid-based covalent organic framework catalyst is 2 nm.
[0055] Table 1 Reaction conditions and product yields of the embodiments of the present invention
[0056] As shown in Table 1, the catalytic synthesis of 3-hydroxypropanal was achieved in all embodiments of the present invention. Specifically, regarding the polymerization inhibitor, compared with 4-methoxyphenol, ZJ701, and phenothiazine, under the same conditions, the yield of 3-hydroxypropanal was highest when hydroquinone was used as the polymerization inhibitor. This is because the phenolic hydroxyl groups of hydroquinone can effectively prevent the self-polymerization of acrolein. Furthermore, when hydroquinone was used, the yield of 3-hydroxypropanal was highest when the ratio of sulfonic acid covalent organic framework, acrolein, and hydroquinone was 0.1 g:1.15 mL:0.05 g. It can also be seen that within the reaction temperature range of 50-80℃, the yield of 3-hydroxypropanal first increased and then decreased with increasing temperature, reaching its highest at 70℃. Regarding the reaction time, the yield of 3-hydroxypropanal gradually increased with increasing reaction time, reaching its highest at 12 h. Regarding the catalyst dosage, it can be seen that the highest yield of 3-hydroxypropionaldehyde was achieved when the ratio of sulfonic acid covalent organic framework, acrolein, and hydroquinone was 0.1 g:1.15 mL:0.05 g. Increasing the amount of sulfonic acid covalent organic framework catalyst resulted in a decrease in product yield. This is because excessive catalyst concentration increases the degree of self-polymerization of acrolein in the acidic system, leading to a decrease in the yield of the hydrated product. These results demonstrate that the present invention achieves a high-conversion catalytic synthesis of 3-hydroxypropionaldehyde.
[0057] Comparative Example 1 used a sulfonic acid Amberlyst-15 catalyst, which is a polystyrene resin with sulfonic acid groups. As shown in Table 1, the sulfonic acid-based covalent organic framework catalyst of Example 5 exhibits higher catalytic activity for acrolein hydration than the sulfonic acid Amberlyst-15 catalyst, indicating that the sulfonic acid-based covalent organic framework catalyst of this invention has superior catalytic hydration activity. Similarly, the sulfonic acid-based XT-92 catalyst used in Comparative Example 2 also shows significantly lower catalytic activity than the sulfonic acid-based covalent organic framework catalyst of Example 5.
[0058] Cyclic experiments were conducted according to Example 5, which showed the best yield of 3-hydroxypropanal. After 10 cycles, the sulfonic acid-based covalent organic framework catalyst still achieved a yield of 85.2% for the hydration of acrolein. In contrast, after 10 cycles, the yield of 3-hydroxypropanal catalyzed by the sulfonic acid Amberlyst-15 catalyst decreased to 30.5%, and the yield of 3-hydroxypropanal catalyzed by the sulfonic acid-based XT-92 catalyst decreased to 21.2%. This demonstrates that the sulfonic acid-based covalent organic framework catalyst of the present invention exhibits excellent cyclic stability, and its stability is significantly improved compared to the sulfonic acid Amberlyst-15 and sulfonic acid-based XT-92 catalysts.
[0059] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A method for catalytic synthesis of 3-hydroxypropional from acrolein, characterized in that, Using acrolein as a raw material, a sulfonic acid covalent organic framework as a catalyst, and with the addition of water and a polymerization inhibitor, a reaction is carried out under heating conditions to obtain 3-hydroxypropional; wherein the structural formula of the sulfonic acid covalent organic framework is as follows: 。 2. The method for catalytic synthesis of 3-hydroxypropional from acrolein according to claim 1, characterized in that, The amount of the sulfonic acid covalent organic framework used is 10wt%-50wt% of acrolein.
3. The method for catalytic synthesis of 3-hydroxypropional from acrolein according to claim 1, characterized in that, The polymerization inhibitor is one of 4-methoxyphenol, hydroquinone, ZJ-701, and phenothiazine.
4. The method for catalytic synthesis of 3-hydroxypropional from acrolein according to claim 3, characterized in that, The polymerization inhibitor is hydroquinone.
5. The method for catalytic synthesis of 3-hydroxypropional from acrolein according to claim 1, characterized in that, The reaction temperature is 50-80℃, and the reaction time is 6-48h.
6. The method for catalytic synthesis of 3-hydroxypropional from acrolein according to claim 1, characterized in that, The amount of polymerization inhibitor used is 1wt%-5wt% of acrolein.
7. The method for catalytic synthesis of 3-hydroxypropional from acrolein according to claim 1, characterized in that, The method for preparing the sulfonic acid-based covalent organic framework is as follows: 2,4,6-trihydroxy-1,3,5-benzenetriformaldehyde and p-phenylenediamine sulfonic acid are used as raw materials, and the reaction is carried out under the catalysis of trifluoroacetic acid. The resulting product is washed and dried to obtain the sulfonic acid-based covalent organic framework.
8. The method for catalytic synthesis of 3-hydroxypropional from acrolein according to claim 7, characterized in that, The molar ratio of 2,4,6-trihydroxy-1,3,5-benzyltricarboxaldehyde, p-phenylenediamine sulfonic acid, and trifluoroacetic acid is 2:3:(0.01-0.02).
9. The method for catalytic synthesis of 3-hydroxypropional from acrolein according to claim 7, characterized in that, In the preparation method of the sulfonic acid covalent organic framework, the reaction temperature is 100-110℃ and the time is 60-80 seconds.
10. The method for catalytic synthesis of 3-hydroxypropional from acrolein according to claim 7, characterized in that, In the preparation method of the sulfonic acid covalent organic framework, the temperature of the detergent during product washing is 80-120℃.