An immobilized metal catalyst prepared by macroporous adsorption resin and preparation method thereof

Abstract

A low-cost immobilized metal catalyst and its preparation method, wherein the immobilized carrier used is a non-polar macroporous adsorption resin, a weakly polar macroporous adsorption resin, a medium polar macroporous adsorption resin, or a polar macroporous adsorption resin; the metal used is vanadium, iron, ruthenium, rhodium, palladium, iridium, platinum, or cobalt ion; the immobilization method used is an adsorption immobilization process; and the reaction interface of the prepared immobilized metal catalyst is as high as 250-1100m 2 / g and has good compatibility with bio-enzyme catalysts, making it particularly suitable for use as an in situ racemization catalyst in combination with enzymes for dynamic kinetic resolution to produce chirally pure products. Furthermore, the catalyst's simple preparation process and low cost have promising commercial prospects.

Description

Technical Field

[0001] The present invention relates to an immobilized metal catalyst and a preparation method thereof, in particular to an immobilized metal catalyst prepared by macroporous adsorption resin and a preparation method thereof. Background Art

[0002] Chiral molecules such as chiral alcohols, amines and their esters are important intermediates for the synthesis of chiral drugs, many natural products and fine chemicals. They are also important chiral auxiliaries in asymmetric synthesis. They are widely used in medicine, pesticides and other fields and are in great demand.

[0003] Traditional methods for preparing chiral alcohols and amines primarily involve kinetic resolution (KR) of racemic alcohols and amines and asymmetric reduction of chiral precursors. Enzyme-catalyzed KR is a widely used method, but its maximum theoretical yield is only 50%, significantly increasing its production cost. Asymmetric reduction methods can yield chiral alcohols and amines with a maximum theoretical yield of 100%, but the chiral precursors used are often difficult to obtain or expensive. In contrast, racemic alcohols and amines are more readily available. Consequently, dynamic kinetic resolution (DKR) has garnered increasing attention and become a hot topic for preparing chiral products. DKR couples kinetic resolution with an in situ racemization reaction, achieving theoretical yields of up to 100% using racemic alcohols and amines as starting materials. Compared to KR, DKR is more economical and environmentally friendly, making it one of the most important methods for preparing chiral alcohols. In recent years, DKR methods using various racemization catalysts coupled to lipases have been successfully applied to the synthesis of aromatic chiral secondary alcohols, achieving promising results. The key to an efficient and low-cost enzyme-metal DKR system is that: (1) the in situ racemization metal catalyst is compatible with the resolution catalyst enzyme; (2) both the metal racemization catalyst and the enzyme have a large reaction interface; (3) the in situ racemization metal catalyst constituting the DKR system should be as cheap as possible to facilitate industrial production. In contrast, many existing in situ racemization noble metal complex catalysts are expensive, which greatly increases production costs; and (4) the enzyme has high stereoselectivity.

[0004] The existing DKR method still has many shortcomings: such as the compatibility of chemical racemization catalysts and enzymes, the dispersibility of chemical catalysts and enzymes in organic solvents, the high price of precious metal complex catalysts, the poor matching of racemization and enzyme-catalyzed reactions, the expensive catalyst raw materials, the complex preparation process, and the harsh operating conditions.

[0005] To dissolve metals or precious metals in organic solvents, they are typically prepared as organically soluble metal complexes. The complex and costly preparation of these complexes leads to high prices for these catalysts. While precious metal complexes can address solubility and dispersibility issues, they also present compatibility issues between chemical racemization catalysts and biological enzymes, with dissolved metal complexes severely inhibiting enzyme activity. Consequently, DKR faces significant challenges: the conflict between compatibility and dispersibility between different catalysts, as well as the complex and costly preparation of metal complexes.

[0006] To address the conflict between compatibility and dispersibility between different catalysts, as well as the complex and high-cost processes for preparing metal complexes, the present invention proposes an innovative technical solution: using immobilized metals and immobilized lipases to form a DKR system. The advantages of this solution are: first, both the immobilized metals and immobilized lipases have a large reaction interface in organic solvents, resulting in excellent dispersibility. Second, because the enzyme and the metal or its salt are located on separate immobilization supports, the metal or its salt and the enzyme do not come into contact with each other, and thus do not inhibit the enzyme's reactivity, resulting in excellent compatibility. In organic solvents, if free enzymes are used, the enzyme powder aggregates, resulting in a very small reaction interface and low catalytic activity. However, using immobilized enzymes effectively disperses the enzymes, significantly increasing the reaction interface. This solution significantly outperforms existing technologies, not only resolving the compatibility issue between metal racemization catalysts and biological enzymes but also significantly increasing the reaction interface of the chemical racemization catalyst. Since the metal racemization catalysts are immobilized on the support in a molecular state, the amount of metal used is minimal, and this, particularly for precious metals, significantly reduces costs. Therefore, this technical solution is expected to be applicable to a variety of precious metals, such as ruthenium, palladium, and rhodium. In the immobilized metal-immobilized enzyme DKR system, the enzyme and metal are isolated from each other, and both the immobilized metal and the immobilized enzyme share a large reaction interface. The dual immobilization of a chemical catalyst and enzyme significantly improves the reaction efficiency of the co-catalytic system and is expected to become a new hotspot in DKR. Immobilization using an inexpensive and easy-to-use macroporous adsorption resin carrier is suitable for green mass production.

[0007] Obtaining an efficient and cost-effective DKR reaction system is crucial for preparing chiral products through DKR reactions. Addressing this challenge requires the preparation of low-cost immobilized metal racemization catalysts. This invention aims to utilize macroporous adsorption resins to prepare immobilized metal catalysts, resulting in low-cost, large reaction interface, and highly enzyme-compatible in situ racemization catalysts. Summary of the Invention

[0008] The purpose of the present invention is to provide a cheap immobilized metal catalyst and its preparation method, which can be used as an in-situ racemization catalyst in the DKR system. The characteristics of the present invention are: a simple adsorption immobilization process is adopted, and a cheap macroporous adsorption resin is used as a carrier to prepare a reaction interface of up to 250-1100m 2 / g, an immobilized metal catalyst with good compatibility with biological enzyme catalysts. Moreover, the catalyst has a simple preparation process, low cost, and good commercial prospects.

[0009] The metals used in the present invention include, but are not limited to, vanadium, iron, ruthenium, rhodium, palladium, iridium, platinum, and cobalt.

[0010] The macroporous adsorption resin supports used in the present invention come in four types: non-polar, weakly polar, moderately polar, and strongly polar. Support polarity influences the reaction microenvironment, and different reactions may require different polar environments. Therefore, it is important to produce immobilized metal in-situ racemization catalysts with varying polarity to meet diverse needs.

[0011] The present invention adopts an adsorption immobilization method to fix the metal catalyst on a macroporous adsorption resin carrier.

[0012] Taking vanadyl oxalate as an example, the adsorption process is as follows: the concentration of the vanadyl oxalate solution is 0.25-1.25M (mol / L), the solution volume is 500-1000mL, it is placed in a stirred container, 100-400g of macroporous adsorption resin is added, the macroporous adsorption resin used is NKA-9 type macroporous adsorption resin, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing the vanadyl oxalate is placed in a 50°C oven and dried for 5 hours to obtain 121.2-151.3g of immobilized vanadyl oxalate catalyst.

[0013] Detection method: Take 0.1g of immobilized vanadyl oxalate catalyst, add appropriate amount of water, add one drop of concentrated sulfuric acid, and titrate with potassium permanganate solution of calibrated concentration. The amount of vanadyl oxalate adsorbed per gram of resin is measured to be 0.21-0.56g, which is converted to a mass content of vanadyl oxalate in each gram of immobilized vanadyl oxalate catalyst of 17.36%-35.9%.

[0014] Principle of potassium permanganate titration:

[0015] 10VOC2O4+2KMnO4+2H2O=5(VO2)2C2O4+K2C2O4+2MnC2O4+2H2C2O4

[0016] The molar amount of vanadyl oxalate adsorbed per gram of resin = concentration of potassium permanganate * volume of potassium permanganate consumed * 5 * 160 / 1000 / amount of immobilized vanadyl oxalate catalyst added.

[0017] For other metals, the adsorption amount can be determined by using the corresponding conventional detection method. DETAILED DESCRIPTION

[0018] The following are examples of the present invention, which are intended only to illustrate the present invention and are not to be construed as limiting the present invention.

[0019] Example 1 Preparation of immobilized vanadyl oxalate catalyst using polar macroporous adsorption resin

[0020] The macroporous adsorption resin used is NKA-9, and its indicators are as follows:

[0021] Indicator Name Indicator

[0022] Model NKA-9

[0023] Polarity

[0024] Average pore size 15.5-16.5 nm

[0025] Pore ​​volume 1.00-1.04ml / g

[0026] Particle size 0.3-1.25mm≥90%

[0027] Moisture 65-75%

[0028] Apparent density 0.50-0.54g / ml

[0029] Skeleton density 1.16-1.20g / ml

[0030] Wet true density 1.00-1.05g / ml

[0031] Wet apparent density 0.66-0.71g / ml

[0032] Specific surface area 250-290m² / g

[0033] The adsorption process is as follows: the concentration of the adsorption vanadyl oxalate solution used is 0.25-1.25M (mol / L), the solution volume is 500-1000mL, it is placed in a stirred container, 100-400g of macroporous adsorption resin is added, and it is stirred at room temperature for 1 hour. After filtering, the macroporous adsorption resin after adsorbing the vanadyl oxalate is placed in a 50°C oven and dried for 5 hours to obtain 121.2-151.3g of immobilized vanadyl oxalate catalyst.

[0034] Take 0.1g of immobilized vanadyl oxalate catalyst, add appropriate amount of water, add one drop of concentrated sulfuric acid, and titrate with potassium permanganate solution of calibrated concentration. The amount of vanadyl oxalate adsorbed per gram of resin is measured to be 0.21-0.56g, which is converted to a mass content of vanadyl oxalate in each gram of immobilized vanadyl oxalate catalyst of 17.36%-35.9%.

[0035] Example 2 Preparation of immobilized vanadyl oxalate catalyst using non-polar macroporous adsorption resin

[0036] The macroporous adsorption resin used is X-5, and its various indicators are as follows:

[0037] Indicator Name Indicator

[0038] Model X-5

[0039] Polar Non-polar

[0040] Appearance: milky white opaque spherical particles

[0041] Particle size range (mm) 0.3-1.25

[0042] Water content (%) 56-66

[0043] Wet true density (g / ml) 1.02-1.07

[0044] Wet apparent density (g / ml) 0.61-0.70

[0045] Specific surface area (m 2 / g) 500-600

[0046] Apparent density (g / ml) 0.44-0.48

[0047] Skeletal density (g / ml) 1.03-1.07

[0048] Average pore size (nm) 29-30

[0049] Porosity (%) 50-60

[0050] Pore ​​volume (ml / g) 1.20-1.24

[0051] The adsorption process is as follows: the concentration of the vanadyl oxalate solution used for adsorption is 0.25-1.25M (mol / L), the solution volume is 500-1000mL, it is placed in a stirred container, 100-400g of macroporous adsorption resin is added, and the mixture is stirred at room temperature for 1 hour. The mixture is filtered, and the macroporous adsorption resin after adsorbing the vanadyl oxalate is placed in a 50°C oven and dried for 5 hours to obtain 122.3-152.4g of immobilized vanadyl oxalate catalyst. The amount of vanadyl oxalate adsorbed per gram of resin is measured to be 0.223-0.524g.

[0052] Example 3 Preparation of immobilized vanadyl oxalate catalyst using weakly polar macroporous adsorption resin

[0053] The macroporous adsorption resin used is AB-8, and its various indicators are as follows: Name Indicators

[0054] Indicator Name Indicator

[0055] Model AB-8

[0056] Polarity Weak polarity

[0057] Appearance: milky white opaque spherical particles

[0058] Particle size range (mm) 0.3-1.25

[0059] Water content (%) 60-70

[0060] Wet true density (g / ml) 1.02-1.05

[0061] Wet apparent density (g / ml) 0.62-0.72

[0062] Specific surface area (m 2 / g) 450-530

[0063] Apparent density (g / ml)-

[0064] Skeletal density (g / ml) 1.02-1.08

[0065] Average pore size (nm) 13-14

[0066] Porosity (%) 42-46

[0067] Pore ​​volume (ml / g) 0.73-0.77

[0068] The adsorption process is as follows: the concentration of the adsorption vanadyl oxalate solution used is 0.25-1.25M (mol / L), the solution volume is 500-1000mL, it is placed in a stirred container, 100-400g of macroporous adsorption resin is added, and the mixture is stirred at room temperature for 1 hour. The mixture is filtered, and the macroporous adsorption resin after adsorbing the vanadyl oxalate is placed in a 50°C oven and dried for 5 hours to obtain 121.3-151.6g of immobilized vanadyl oxalate catalyst. The amount of vanadyl oxalate adsorbed per gram of resin is measured to be 0.213-0.516g.

[0069] Example 4 Preparation of immobilized vanadyl oxalate catalyst using medium-polarity macroporous adsorption resin

[0070] The macroporous adsorption resin used is DM301, and its various indicators are as follows: Name Indicators

[0071] Indicator Name Indicator Parameters

[0072] Model DM301

[0073] Polarity in polarity

[0074] Moisture content 65-75%

[0075] Particle size range 0.3-1.25 mm≥90%

[0076] Average pore size 14-17 nm

[0077] Pore ​​volume 0.7-0.9ml / g

[0078] Porosity 42-46%

[0079] Apparent density 0.64-0.68g / ml

[0080] Skeletal density 1.39-1.43g / ml

[0081] Wet true density 1.15-1.19g / ml

[0082] Wet apparent density 0.65-0.70g / ml

[0083] Specific surface area ≥330 m² / g

[0084] Adsorption capacity ≥40mg / g (phenol / dry basis)

[0085] The adsorption process is as follows: the concentration of the adsorption vanadyl oxalate solution used is 0.25-1.25M (mol / L), the solution volume is 500-1000mL, it is placed in a stirred container, 100-400g of macroporous adsorption resin is added, and the mixture is stirred at room temperature for 1 hour. The mixture is filtered, and the macroporous adsorption resin after adsorbing the vanadyl oxalate is placed in a 50°C oven and dried for 5 hours to obtain 122.8-152.9g of immobilized vanadyl oxalate catalyst. The amount of vanadyl oxalate adsorbed per gram of resin is measured to be 0.228-0.529g.

[0086] Example 5 Preparation of immobilized vanadyl sulfate catalyst using non-polar macroporous adsorption resin

[0087] The macroporous adsorption resin used is DM101, and its various indicators are as follows: Name Indicators

[0088] Indicator Name Indicator Parameters

[0089] Model DM101

[0090] Polar Non-polar

[0091] Appearance: milky white opaque spherical particles

[0092] Particle size range (mm) 0.3-1.25

[0093] Water content (%) 65-75

[0094] Wet true density (g / ml) 1.15-1.19g / ml

[0095] Wet apparent density (g / ml) 0.65-0.70g / ml

[0096] Specific surface area (m 2 / g) 600-700

[0097] Apparent density (g / ml) 0.32-0.36g / ml

[0098] Skeletal density (g / ml) 0.81-0.85g / ml

[0099] Average pore size (nm): 9-11nm

[0100] Porosity (%) 68-72%

[0101] Pore ​​volume (ml / g) 1.50-1.70ml / g

[0102] Specific surface area 550-600 m² / g

[0103] Adsorption capacity ≥45mg / g (phenol / dry basis)

[0104] The adsorption process is as follows: the concentration of the adsorption vanadyl sulfate solution used is 0.25-1.25M (mol / L), the solution volume is 500-1000mL, it is placed in a stirred container, 100-400g of macroporous adsorption resin is added, and the mixture is stirred at room temperature for 1 hour. The mixture is filtered, and the macroporous adsorption resin after adsorbing the vanadyl sulfate is placed in a 50°C oven and dried for 5 hours to obtain 124.1-153.9g of immobilized vanadyl sulfate catalyst. The amount of vanadyl sulfate adsorbed per gram of resin is measured to be 0.241-0.539g.

[0105] Example 6 Preparation of immobilized cobalt sulfate catalyst using non-polar macroporous adsorption resin

[0106] The macroporous adsorption resin used is H103, and its various indicators are as follows: Name Indicator

[0107] Indicator Name Indicator Parameters

[0108] Model H103

[0109] Polar Non-polar

[0110] Average pore size 8.4-9.4 nm

[0111] Pore ​​volume 1.08-1.12ml / g

[0112] Particle size 0.3-1.25mm≥90%

[0113] Moisture 45-50%

[0114] Apparent density 0.53-0.57 g / ml

[0115] Skeleton density 1.20-1.24g / ml

[0116] Wet true density 1.05-1.10g / ml

[0117] Wet apparent density 0.65-0.75g / ml

[0118] Specific surface area 900-1100 m² / g

[0119] The adsorption process is as follows: a cobalt sulfate solution with a concentration of 0.25-1.25M (mol / L) and a solution volume of 500-1000mL is placed in a stirred container, 100-400g of a macroporous adsorption resin is added, and the mixture is stirred at room temperature for 1 hour and filtered. The macroporous adsorption resin after adsorption of cobalt sulfate is placed in a 50°C oven and dried for 5 hours to obtain 123.1-150.6g of an immobilized cobalt sulfate catalyst. The amount of cobalt sulfate adsorbed per gram of resin is measured to be 0.231-0.506g.

[0120] Example 7 Preparation of immobilized ruthenium sulfate catalyst using polar macroporous adsorption resin

[0121] The macroporous adsorption resin used is NKA-9. The adsorption process is as follows: the concentration of the adsorption ruthenium sulfate solution used is 0.15-0.75M (mol / L), the solution volume is 500-1000mL, placed in a stirred container, 100-400g of the macroporous adsorption resin is added, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing ruthenium sulfate is placed in a 50°C oven and dried for 5 hours to obtain 124.2-161.6g of immobilized ruthenium sulfate catalyst. The amount of ruthenium sulfate adsorbed per gram of resin is measured to be 0.245-0.618g.

[0122] Example 8 Preparation of immobilized ruthenium sulfate catalyst using weakly polar macroporous adsorption resin

[0123] The macroporous adsorption resin used is AB-8, and the adsorption process is as follows: the concentration of the adsorption ruthenium sulfate solution used is 0.15-0.75M (mol / L), the solution volume is 500-1000mL, placed in a stirred container, 100-400g of the macroporous adsorption resin is added, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing ruthenium sulfate is placed in a 50°C oven and dried for 5 hours to obtain 123.4-162.5g of immobilized ruthenium sulfate catalyst, and the amount of ruthenium sulfate adsorbed per gram of resin is measured to be 0.232-0.611g.

[0124] Example 9 Preparation of immobilized rhodium sulfate catalyst using non-polar macroporous adsorption resin

[0125] The macroporous adsorption resin used is X-5, and the adsorption process is as follows: the concentration of the rhodium sulfate solution used for adsorption is 0.25-1.0M (mol / L), the solution volume is 500-1000mL, it is placed in a stirred container, 100-400g of macroporous adsorption resin is added, the macroporous adsorption resin used is X-5 type macroporous adsorption resin, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing rhodium sulfate is placed in a 50°C oven and dried for 5 hours to obtain 128.6-151.3g of immobilized rhodium sulfate catalyst, and the amount of rhodium sulfate adsorbed per gram of resin is measured to be 0.274-0.509g.

[0126] Example 10 Preparation of immobilized rhodium sulfate catalyst using medium-polarity macroporous adsorption resin

[0127] The macroporous adsorption resin used is DM301, and the adsorption process is as follows: the concentration of the rhodium sulfate solution used for adsorption is 0.25-1.0M (mol / L), the solution volume is 500-1000mL, it is placed in a stirred container, 100-400g of the macroporous adsorption resin is added, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing rhodium sulfate is placed in a 50°C oven and dried for 5 hours to obtain 129.7-150.2g of immobilized rhodium sulfate catalyst, and the rhodium sulfate adsorbed per gram of resin is measured to be 0.282-0.515g.

[0128] Example 11 Preparation of Immobilized Rhodium Catalyst (Weakly Polar Carrier) Using Weakly Polar Macroporous Adsorption Resin

[0129] The macroporous adsorption resin used is AB-8, the macroporous adsorption resin used is DM301, and the adsorption process is as follows: the rhodium sulfate solution used for adsorption has a concentration of 0.25-1.0M (mol / L) and a solution volume of 500-1000mL, is placed in a stirred container, 100-400g of macroporous adsorption resin is added, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing rhodium sulfate is placed in a 50°C oven and dried for 5 hours to obtain 130.7-153.2g of immobilized rhodium sulfate catalyst, and the amount of rhodium sulfate adsorbed per gram of resin is measured to be 0.312-0.535g.

[0130] Example 12 Preparation of Immobilized Palladium Sulfate Catalyst (Medium Polarity Support) Using Medium Polarity Macroporous Adsorption Resin

[0131] The macroporous adsorption resin used is DM301, and the adsorption process is as follows: the palladium sulfate solution used for adsorption has a concentration of 0.15-1.0M (mol / L) and a solution volume of 500-1000mL, is placed in a stirred container, 100-400g of the macroporous adsorption resin is added, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing palladium sulfate is placed in a 50°C oven and dried for 5 hours to obtain 118.2-161.8g of immobilized palladium sulfate catalyst, and the amount of palladium sulfate adsorbed per gram of resin is measured to be 0.119.6-0.623g.

[0132] Example 13 Preparation of Immobilized Palladium Sulfate Catalyst (Non-polar Support) Using Non-polar Macroporous Adsorption Resin

[0133] The macroporous adsorption resin used is DM101, and its various indicators are as follows: Name Indicators

[0134] The macroporous adsorption resin used is DM101, and the adsorption process is as follows: the palladium sulfate solution used for adsorption has a concentration of 0.15-1.0M (mol / L) and a solution volume of 500-1000mL, which is placed in a stirred container, 100-400g of the macroporous adsorption resin is added, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing palladium sulfate is placed in a 50°C oven and dried for 5 hours to obtain 120.2-166.8g of immobilized palladium sulfate catalyst, and the amount of palladium sulfate adsorbed per gram of resin is measured to be 0.121.1-0.671g.

[0135] Example 14 Preparation of Immobilized Polysaccharide Iron Complex Catalyst (Medium Polarity Support) Using Medium Polarity Macroporous Adsorption Resin

[0136] The macroporous adsorption resin used is DM301, and the adsorption process is as follows: the polysaccharide iron complex solution used for adsorption has a concentration of 40-200 g / L and a solution volume of 500-1000 mL. It is placed in a stirred container, 100-400 g of macroporous adsorption resin is added, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing the polysaccharide iron complex is placed in a 50°C oven and dried for 5 hours to obtain 121.1-158.6 g of immobilized polysaccharide iron complex catalyst, and the polysaccharide iron complex adsorbed per gram of resin is measured to be 0.227-0.162 g.

[0137] Example 15 Preparation of immobilized polysaccharide iron complex catalyst (non-polar support) using non-polar macroporous adsorption resin

[0138] The macroporous adsorption resin used is HPD100, and its various indicators are as follows: Name Indicator

[0139] Indicator Name Indicator Parameters

[0140] Model HPD100

[0141] Polar Non-polar

[0142] Average pore size 8.5-9 nm

[0143] Pore ​​volume 1.35-1.65ml / g

[0144] Particle size 0.3-1.25mm≥90%

[0145] Moisture 65-75%

[0146] Wet true density 1.03-1.07g / ml

[0147] Wet apparent density 0.68-0.75 g / ml

[0148] Specific surface area ≥650 m² / g

[0149] The macroporous adsorption resin used is HPD100, and the adsorption process is as follows: the polysaccharide iron complex solution used for adsorption has a concentration of 40-200 g / L and a solution volume of 500-1000 mL, is placed in a stirred container, 100-400 g of macroporous adsorption resin is added, stirred at room temperature for 1 hour, filtered, and the macroporous adsorption resin after adsorbing the polysaccharide iron complex is placed in a 50°C oven and dried for 5 hours to obtain 123.1-163.6 g of immobilized polysaccharide iron complex catalyst, and the polysaccharide iron complex adsorbed per gram of resin is measured to be 0.237-0.165 g.

[0150] Example 16 Preparation of (R)-3-chloro-1-phenylpropanol by DKR reaction

[0151] A DKR reaction was conducted using the immobilized vanadyl oxalate catalyst prepared in Example 3 as an in situ racemization catalyst and commercially available immobilized Candida antarctica lipase B (CALB) as a resolution catalyst. Racemic 3-chloro-1-phenylpropanol was used as the substrate and isopropenyl acetate was used as the acyl donor. The reaction conditions were: a 4 ml reaction volume, a 3-chloro-1-phenylpropanol concentration of 0.125 mmol / mL, an isopropenyl acetate concentration of 0.0625 mmol / mL, 0.3 g of immobilized CALB, and 0.03 g of immobilized vanadyl oxalate. The reaction temperature was 50°C, and the reaction time was 42-52 hours to produce (R)-3-chloro-1-phenylpropanol. The enantiomeric excess (ee) and conversion were determined by high-performance liquid chromatography (HPLC) using a chiral column. The mobile phase consisted of n-hexane:isopropanol (8.5:1.5), with detection at 254 nm, a column oven temperature of 35°C, a flow rate of 0.6 mL / min, and a 20 µL injection volume. The experimental results showed product conversions of 92-97% and product ee of 91-93%.

Claims

1. A macroporous adsorption resin immobilized metal catalyst, characterized in that The immobilized metal catalyst reaction interface is as high as 250-1100m 2 / g, and has good compatibility with biological enzyme catalysts; the immobilized metal catalyst comprises: (1) a macroporous adsorption resin as an immobilization carrier, wherein the macroporous adsorption resin is selected from non-polar macroporous adsorption resin, weak polar macroporous adsorption resin, medium polar macroporous adsorption resin and polar macroporous adsorption resin; and (2) a metal compound having catalytic racemization reaction activity, which is immobilized on the macroporous adsorption resin by physical adsorption; wherein the metal compound is vanadyl oxalate, vanadyl sulfate, cobalt sulfate, ruthenium sulfate, rhodium sulfate, palladium sulfate, polysaccharide iron complex; the operation process of the physical adsorption is: placing the macroporous adsorption resin in a salt solution of the metal with a concentration of 0.15-1.25 mol / L, stirring at room temperature for 1 hour, filtering, and placing the adsorbed macroporous adsorption resin in a 50°C oven to dry, thereby obtaining the immobilized metal catalyst; the immobilized metal catalyst is used to catalyze the in situ racemization reaction of the substrate during the chemical-enzymatic dynamic kinetic resolution process.