M-POPs catalyst, preparation method and application of M-POPs catalyst in catalyzing alpha, beta-unsaturated aldehyde to generate unsaturated alcohol
By using porous organic polymers loaded with metals as M-POPs catalysts, the selectivity and stability problems of existing catalysts are solved, and efficient and low-cost unsaturated alcohol production is achieved, which is suitable for industrial production.
Patent Information
- Application Number
- CN202410380897.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-31
- Publication Date
- 2025-09-30
AI Technical Summary
Existing non-precious metal catalysts have low selectivity and low yield in the process of catalyzing α,β-unsaturated aldehydes to produce unsaturated alcohols. In addition, traditional catalysts have poor stability and are difficult to recycle.
The M-POPs catalyst uses porous organic polymers (POPs) to load metals. The metals are loaded onto the porous organic polymers through covalent bonds, ionic bonds or coordination effects, and the transfer hydrogenation reaction is used to catalyze the conversion of α,β-unsaturated aldehydes to unsaturated alcohols under mild conditions.
The unsaturated alcohols were generated with high selectivity and high yield. The catalyst was easy to prepare, inexpensive and stable, and suitable for industrial production.
Smart Images
Figure CN120714698A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of functional material preparation, and more specifically, relates to an M-POPs catalyst, a preparation method and an application thereof in catalyzing α,β-unsaturated aldehydes to generate unsaturated alcohols. Background Art
[0002] Products from the selective hydrogenation of α,β-unsaturated aldehydes are highly valuable fine chemicals widely used in cosmetics, flavors and fragrances, and pharmaceuticals. Among various α,β-unsaturated aldehydes, cinnamaldehyde (CAL) is an important and representative template reactant. Its main products, cinnamyl alcohol (COL) and hydrocinnamaldehyde (HCAL), are widely used in the production of pharmaceutical intermediates, perfumes, and fragrances. HCAL has also been reported as an important intermediate in HIV treatment (Chem. Eng. J. 2018, 351, 995-1005).
[0003] Industrially, aluminum isopropoxide is commonly used as a catalyst for the hydrogenation of CAL to produce COL at 70-80°C. However, the yield of COL using this catalyst is only approximately 73%, indicating limited catalytic performance. Therefore, researchers are committed to designing and developing novel catalysts that can achieve high yields of the target product without the addition of any acid or base co-catalysts.
[0004] Precious metal catalysts such as platinum (Pt) and palladium (Pd) are widely used in the selective hydrogenation of CALs due to their high catalytic activity. Typically, platinum, gold (Au), and iridium (Ir) catalysts are used for the catalytic hydrogenation of C=O bonds to produce COLs, while palladium is used for the catalytic hydrogenation of C=C bonds to produce HCALs. However, given the high cost of precious metals, researchers are looking for non-precious metal materials as alternative catalysts. Non-precious metals such as cobalt (Co), nickel (Ni), and copper (Cu) are highly efficient hydrogenation catalysts and have been used in the catalytic hydrogenation reduction of various α,β-unsaturated aldehydes, offering significant advantages in reducing costs.
[0005] Cobalt (Co), as a transition metal element, can act as an independent catalyst to catalyze the hydrogenation reaction during the hydrogenation of CAL. Liu et al. reported a Co@CN-900 catalyst derived from metal organic frameworks (MOFs) that can efficiently catalyze the selective hydrogenation of CAL to produce COL. The yield of COL was as high as 99% after 48 hours of reaction at 80°C. In addition, the researchers also carried out the selective hydrogenation of other α,β-unsaturated aldehydes on Co@CN-900, and the selectivity of the corresponding unsaturated alcohols was higher than 80%. However, due to the relatively low activity of cobalt, the reaction efficiency is low and the reaction time is long. In order to obtain a higher yield, a higher H2 pressure or a longer reaction time is required (Materials Chemistry Frontiers. 2017, 1(10), 2005-2012.).
[0006] Nickel (Ni)-based catalysts have attracted widespread attention due to their low cost and moderate activity. Prakash et al. studied the performance of Ni / TiO2 catalysts and compared the effects of four different preparation methods on the performance of Ni / TiO2 catalysts (direct impregnation, urea precipitation, and chemical reduction, using hydrazine hydrate and glucose as reducing agents). The results showed that the Ni / TiO2-HH catalyst (using hydrazine hydrate and glucose as reducing agents) had the highest selectivity for COL, reaching 53.2%; however, compared with other catalysts, the selectivity of this catalyst was lower (Catal. Sci. Technol. 2015, 5(6), 3313-3321.).
[0007] Similar to cobalt-based catalysts, high reaction temperature and H2 pressure are necessary conditions for catalytic hydrogenation of copper (Cu)-based catalysts. However, the selectivity of the copper-based catalysts reported so far for the target product (COL or HCAL) is not high. Zheng et al. synthesized copper nanowires and applied them to the catalytic reaction of cinnamaldehyde (CAL), with a conversion rate of 45% and a selectivity of cinnamyl alcohol (COL) of 58%. However, the selectivity and yield of this catalyst for COL were not high (RSC Adv. 2014, 4(78), 41683-41689.).
[0008] To address the low selectivity and yield of traditional heterogeneous catalysts in the production of cinnamyl alcohol, Daniel et al. proposed a simple method for the selective transfer hydrogenation of CAL to COL using Cr(CO)6, W(CO)6, or Mo(CO)6 as catalysts and isopropanol, methanol, or ethanol as both solvents and transfer hydrogenation reagents. The Cr(CO)6-catalyzed transfer hydrogenation achieved a COL yield of 99% after 15 hours at 120°C. This catalyst not only demonstrated significant advantages in the selective carbonyl transfer hydrogenation of CAL but also possessed broad applicability. Furthermore, the transfer hydrogenation avoided the use of hydrogen, making the reaction safer. However, the catalyst's poor stability made it difficult to recycle, and its catalytic activity also needed to be improved (Journal of Catalysis. 2022, 413, 478-486).
[0009] Porous organic polymers (POPs) are porous polymer networks composed of rigid organic building blocks (such as aromatic rings) linked by covalent bonds. Due to their high stability, large surface area, and ease of functionalization, POPs have become a novel platform for material design and functional exploration. M-POPs catalysts are a class of materials in which metals are loaded onto POPs via covalent, ionic, or coordination bonds. Summary of the Invention
[0010] The purpose of the present invention is to overcome the deficiencies of the prior art and provide an M-POPs catalyst.
[0011] The second object of the present invention is to provide a method for preparing an M-POPs catalyst.
[0012] The third object of the present invention is to provide an application of an M-POPs catalyst in catalyzing α,β-unsaturated aldehydes to generate unsaturated alcohols.
[0013] The technical solution of the present invention is summarized as follows:
[0014] A method for preparing an M-POPs catalyst, characterized by comprising the following steps:
[0015] The porous organic polymer monomer, the metal carbonyl complex and the solvent are added into a reaction kettle, heated to 120-180° C., and reacted for 4-12 hours; the filter residue is obtained by filtration, washed, and dried to obtain the M-POPs catalyst.
[0016] The ratio of the porous organic polymer monomer, the metal carbonyl complex and the solvent is (1.64-8) g: (1.28-8.62) g: (30-70) ml.
[0017] The porous organic polymer monomers are at least two of melamine, m-phenylenediamine, p-phenylenediamine, benzidine, tetrakis(4-aminophenyl)methane, terephthalaldehyde, m-phthalaldehyde, trimesaldehyde and 1,3,6,8-tetrakis(4-formylphenyl)pyrene.
[0018] The metal carbonyl complex is at least one of iron pentacarbonyl, dicobalt octacarbonyl, nickel tetracarbonyl, chromium hexacarbonyl and molybdenum hexacarbonyl.
[0019] The solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 1,4-dioxane, tetrahydrofuran, p-xylene and chlorobenzene.
[0020] The M-POPs catalyst prepared by the above preparation method.
[0021] The application of M-POPs catalyst in catalyzing α,β-unsaturated aldehydes to generate unsaturated alcohols includes the following steps:
[0022] The M-POPs catalyst, α,β-unsaturated aldehyde and an alcohol solvent as a transfer hydrogen source are added to an autoclave; the reaction is carried out at 80-180° C. for 4-8 hours; the filtrate is filtered, and the filtrate is concentrated and purified to obtain an unsaturated alcohol.
[0023] The α,β-unsaturated aldehyde is cinnamaldehyde, crotonaldehyde, 2,4-hexadienal, furfural or citral.
[0024] The alcohol solvent used as the hydrogen source for transfer hydrogenation is at least one of methanol, ethanol, isopropanol and n-butanol.
[0025] The unsaturated alcohol is cinnamyl alcohol, crotyl alcohol, 2,4-hexadienol, furfuryl alcohol or nerol.
[0026] The purification method is at least one of recrystallization, column chromatography and distillation.
[0027] Advantages of the present invention:
[0028] (1) The M-POPs catalyst of the present invention is easy to prepare, inexpensive, and easy to recycle; it has good catalytic activity and stability for the selective transfer hydrogenation of α,β-unsaturated aldehydes; the preparation conditions are mild, the equipment requirements are low, and it is suitable for industrial production.
[0029] (2) The M-POPs catalyst of the present invention has mild catalytic conditions, is green and efficient, simple to operate and low in cost, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 This is the infrared (IR) spectrum of the M-POPs-1 catalyst prepared in Example 1.
[0031] Figure 2 These are transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) photos of the M-POPs-1 catalyst prepared in Example 1.
[0032] Figure 3 These are scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS) photographs of the M-POPs-1 catalyst prepared in Example 1.
[0033] Figure 4 This is the X-ray diffraction (XRD) spectrum of the M-POPs-1 catalyst prepared in Example 1.
[0034] Figure 5 X-ray photoelectron (XPS) spectra of the M-POPs-1 catalyst prepared in Example 1, where (a) is the high-resolution XPS spectrum of Cr2p, (b) is the high-resolution XPS spectrum of N1s, and (c) is the full XPS spectrum of Cr-SNW. DETAILED DESCRIPTION
[0035] The present invention will be further described below with reference to specific embodiments.
[0036] The following examples may help those skilled in the art better understand the present invention. However, the contents described in the examples are only used to illustrate the present invention and should not and will not limit the present invention in any way.
[0037] Example 1
[0038] The preparation method of the M-POPs-1 catalyst comprises the following steps:
[0039] 0.64 g of melamine, 1.00 g of terephthalaldehyde and 4.40 g of chromium hexacarbonyl were dissolved in 25.0 ml of N-methylpyrrolidone and 5.0 ml of tetrahydrofuran, added to a 150 ml reactor, heated to 160 ° C and reacted for 6 hours; the filter residue was filtered and washed with N, N-dimethylformamide, tetrahydrofuran and acetone three times respectively, and dried to obtain black granular catalyst M-POPs-1 (see Figure 1 、 Figure 2 、 Figure 3 、 Figure 4 and Figure 5 ).
[0040] Example 2
[0041] The preparation method of the M-POPs-2 catalyst comprises the following steps:
[0042] 2.90 g of tetrakis(4-aminophenyl)methane, 2.00 g of isophthalaldehyde, and 4.64 g of molybdenum hexacarbonyl were dissolved in 40 ml of N,N-dimethylformamide and 10.0 ml of 1,4-dioxane, added to a 150 ml reactor, and heated to 160°C for 6 h. The residue was filtered, washed three times each with N,N-dimethylformamide, tetrahydrofuran, and acetone, and dried to obtain the M-POPs-2 catalyst.
[0043] Example 3
[0044] The preparation method of the M-POPs-3 catalyst comprises the following steps:
[0045] 3.6 g of benzidine, 2 g of m-phenylenediamine, 2.4 g of trimesaldehyde, and 4.86 g of iron pentacarbonyl were dissolved in 60.0 ml of 1,3-dimethyl-2-imidazolidinone and 10.0 ml of chlorobenzene, added to a 150 ml reactor, and heated to 120°C for 12 hours. The residue was filtered and washed three times with N,N-dimethylformamide, tetrahydrofuran, and acetone, respectively, and dried to obtain the M-POPs-3 catalyst.
[0046] Example 4
[0047] The preparation method of the M-POPs-4 catalyst comprises the following steps:
[0048] 1.20 g of m-phenylenediamine, 3.46 g of 1,3,6,8-tetrakis(4-formylphenyl)pyrene, and 1.28 g of nickel tetracarbonyl were dissolved in 30.0 ml of N,N-dimethylacetamide, added to a 150 ml reactor, and heated to 170°C for 6 h. The residue was filtered and washed three times each with N,N-dimethylformamide, tetrahydrofuran, and acetone, and then dried to obtain the M-POPs-4 catalyst.
[0049] Example 5
[0050] The preparation method of the M-POPs-5 catalyst comprises the following steps:
[0051] 2.0 g of p-phenylenediamine, 2.20 g of trimesaldehyde, 4.32 g of dicobalt octacarbonyl, and 4.3 g of chromium hexacarbonyl were dissolved in 35.0 ml of dimethyl sulfoxide and 10.0 ml of p-xylene, added to a 150 ml reactor, heated to 180°C and reacted for 4 h; the residue was filtered, washed three times with N,N-dimethylformamide, tetrahydrofuran, and acetone, and dried to obtain the M-POPs-5 catalyst.
[0052] Example 6
[0053] The application of the M-POPs-1 catalyst in catalyzing the production of α,β-unsaturated aldehydes into α,β-unsaturated alcohols comprises the following steps:
[0054] 10.0 mg of the M-POPs-1 catalyst prepared in Example 1, 1.0 ml of cinnamaldehyde, and 4.0 ml of isopropanol (an alcohol solvent serving as a transfer hydrogen source) were added to a 20 ml autoclave; the reaction was carried out at 120° C. for 6 h. The mixture was filtered, the filtrate was concentrated, and purified by recrystallization to obtain cinnamyl alcohol with a conversion of 97.7% and a selectivity of 97.9%.
[0055] Example 7
[0056] The application of the M-POPs-2 catalyst in catalyzing the production of α,β-unsaturated aldehydes into α,β-unsaturated alcohols comprises the following steps:
[0057] 20.0 mg of the M-POPs-2 catalyst prepared in Example 2, 2.0 ml of crotonaldehyde, and 8.0 ml of methanol (an alcohol solvent serving as a source of transfer hydrogenation) were added to a 50 ml autoclave; the reaction was carried out at 100° C. for 8 h. The mixture was filtered, the filtrate was concentrated, and purified by column chromatography to obtain crotyl alcohol with a conversion rate of 88.1% and a selectivity of 80.8%.
[0058] Example 8
[0059] The application of the M-POPs-3 catalyst in catalyzing the production of α,β-unsaturated aldehydes into α,β-unsaturated alcohols comprises the following steps:
[0060] 40.0 mg of the M-POPs-3 catalyst prepared in Example 3, 4.0 ml of citral, and 16.0 ml of ethanol (an alcohol solvent serving as a transfer hydrogen source) were added to a 50 ml autoclave; the reaction was carried out at 120° C. for 6 h. The mixture was filtered, the filtrate was concentrated, and purified by distillation to obtain nerol with a conversion rate of 95.5% and a selectivity of 72.2%.
[0061] Example 9
[0062] The application of the M-POPs-4 catalyst in catalyzing the production of α,β-unsaturated aldehydes into α,β-unsaturated alcohols comprises the following steps:
[0063] 80.0 mg of the M-POPs-4 catalyst prepared in Example 4, 8.0 ml of furfural, and 32.0 ml of n-butanol (an alcohol solvent serving as a hydrogen source for transfer hydrogenation) were added to a 100 ml autoclave; the reaction was carried out at 180° C. for 4 h. The mixture was filtered, the filtrate was concentrated, and purified by column chromatography to obtain furfuryl alcohol with a conversion of 97.3% and a selectivity of 74.5%.
[0064] Example 10
[0065] The application of the M-POPs-5 catalyst in catalyzing the production of α,β-unsaturated aldehydes into α,β-unsaturated alcohols comprises the following steps:
[0066] 100.0 mg of the M-POPs-5 catalyst prepared in Example 5, 10.0 ml of 2,4-hexadienal, 30.0 ml of isopropanol, and 10.0 ml of methanol (an alcohol solvent serving as a transfer hydrogen source) were added to a 100 ml autoclave; the reaction was carried out at 80° C. for 8 h; the mixture was filtered, the filtrate was concentrated, and purified by column chromatography to obtain 2,4-hexadienol with a conversion of 85.2% and a selectivity of 93.1%.
[0067] Table 1 Comparison of different examples catalyzing transfer hydrogenation of α,β-unsaturated aldehydes to produce unsaturated alcohols
[0068]
Claims
1. A method for preparing an M-POPs catalyst, characterized in that The steps include: The porous organic polymer monomer, the metal carbonyl complex and the solvent are added into a reaction kettle, heated to 120-180° C., and reacted for 4-12 hours; the filter residue is obtained by filtration, washed, and dried to obtain the M-POPs catalyst.
2. The preparation method according to claim 1, wherein The ratio of the porous organic polymer monomer, the metal carbonyl complex and the solvent is (1.64-8) g: (1.28-8.62) g: (30-70) ml.
3. The preparation method according to claim 1 or 2, characterized in that The porous organic polymer monomers are at least two of melamine, m-phenylenediamine, p-phenylenediamine, benzidine, tetrakis(4-aminophenyl)methane, terephthalaldehyde, m-phthalaldehyde, trimesaldehyde and 1,3,6,8-tetrakis(4-formylphenyl)pyrene.
4. The preparation method according to claim 1 or 2, characterized in that The metal carbonyl complex is at least one of iron pentacarbonyl, dicobalt octacarbonyl, nickel tetracarbonyl, chromium hexacarbonyl and molybdenum hexacarbonyl.
5. The preparation method according to claim 1 or 2, characterized in that The solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 1,4-dioxane, tetrahydrofuran, p-xylene and chlorobenzene.
6. The M-POPs catalyst prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the M-POPs catalyst according to claim 6 to catalyze α,β-unsaturated aldehydes to produce unsaturated alcohols, characterized in that The steps include: The M-POPs catalyst, α,β-unsaturated aldehyde and an alcohol solvent as a transfer hydrogen source are added to an autoclave; the reaction is carried out at 80-180° C. for 4-8 hours; the filtrate is filtered, and the filtrate is concentrated and purified to obtain an unsaturated alcohol.
8. The use according to claim 7, characterized in that The α,β-unsaturated aldehyde is cinnamaldehyde, crotonaldehyde, 2,4-hexadienal, furfural or citral.
9. The use according to claim 7, characterized in that The alcohol solvent used as the hydrogen source for transfer hydrogenation is at least one of methanol, ethanol, isopropanol and n-butanol.
10. The use according to claim 7, characterized in that The unsaturated alcohol is cinnamyl alcohol, crotyl alcohol, 2,4-hexadienol, furfuryl alcohol or nerol.