TEMPO-based compound supported catalyst, its production method and use

Abstract

The present invention provides a TEMPO compound supported catalyst, a method for producing the same and use thereof. The TEMPO compound supported catalyst uses a polymer resin as a support, the polymer resin including a polystyrene resin containing chloromethyl or bromomethyl, and the content of chloromethyl or bromomethyl in the polymer resin is 0.5 to 5.0 mmol g -1 The above polymer resin has a polystyrene skeleton and has a very low swelling degree in organic solvents, so in actual continuous production, the low swelling degree is advantageous for maintaining the rigidity of the resin, preventing softening due to expansion of the resin, mutual extrusion, and pressure increase (pressure accumulation) of the reactor, thereby preventing the resin from breaking, and the above resin has good resistance to oxidizing agents (such as sodium hypochlorite) and will not break or decompose after contact with the oxidizing agent, thereby ensuring the cycle life of the supported catalyst.

Description

[Technical field]

[0001] The present invention relates to the field of catalysis, specifically to a TEMPO-based compound supported catalyst, its preparation method and its use. [Background technology]

[0002] In the pharmaceutical industry and chemical synthesis, oxidation reactions are one of the most important reactions. When oxidizing the hydroxyl of alcohols, the oxidizing agents used can be divided into metal-based and non-metal-based oxidizing agents depending on whether they contain transition metal elements. A representative example of a metal-based oxidizing agent is a hexavalent chromium reagent such as PCC (pyridinium chlorochromate) or activated manganese dioxide. The main advantages of this reagent are that it is cheap, easy to obtain, has excellent selectivity, and can quantitatively oxidize primary alcohols to the corresponding aldehydes without producing carboxylic acids. However, the use of such oxidizing agents generates highly polluting heavy metal waste, and its detoxification treatment increases production costs.

[0003] Moreover, hexavalent chromium is a potent carcinogen, greatly limiting its use in the pharmaceutical industry. Nonmetallic oxidants typically include hypervalent iodine reagents (e.g., IBX and Dess-Martin oxidants), dimethylsulfoxide reagents (usually combined with reagents such as dicyclohexylcarbodiimide, oxalyl chloride, and sulfur trioxide), and nitric oxide free radical reagents (e.g., 2,2,6,6-tetramethylpiperidine oxide (TEMPO) or N-methylmorpholine oxide (NMO), usually used in combination with oxidants such as chlorosuccinimide (NCS) and sodium hypochlorite). Compared to metal oxidants, nonmetallic oxidants produce less heavy metal waste but are equally selective.

[0004] However, hypervalent iodine reagents are expensive because they are usually supplied in equimolar or greater equivalents, and the reagents themselves are prone to fire and explosion if improperly stored, increasing production costs and posing safety hazards.Dimethylsulfoxide-based reagents are reduced when used to dimethylsulfide, which is foul-smelling and toxic, and when used in combination with oxalyl chloride, produces carbon monoxide.

[0005] On the other hand, the oxidation reaction catalyzed by nitrogen oxide free radical reagents, especially TEMPO-based compounds, can use sodium hypochlorite, NCS, and even air as oxidants, and the toxicity of the by-products is relatively low, the handling is more convenient, and there is almost no environmental burden, so it is an environmentally friendly chemical reaction and has great advantages in the production of chemicals.

[0006] Currently, most of the catalytic oxidation examples of TEMPO compounds reported in the literature are batch reactions, in which TEMPO compounds are dissolved in a reaction solvent and used to participate in a homogeneous catalytic reaction. In actual production, such batch reactions often cause side reactions (e.g., over-oxidation of primary alcohols), and many problems often occur when the reaction scale is large.

[0007] In addition, because the price of the TEMPO compound itself is high, it is necessary to consider the cost and design a recovery step for the TEMPO compound after the reaction to prevent the loss of the TEMPO compound and to prevent product contamination. Because the oxidation reaction of alcohol is an exothermic reaction, the problem of heat dissipation in the reactor must be considered in the batch reaction, otherwise heat accumulation will become a safety hazard.

[0008] Compared with batch reactions, continuous reactions are more controllable and safer. In continuous reactions, TEMPO-based compounds can be immobilized on polymeric supports (e.g., resins) to catalyze the reaction, facilitating recovery and preventing contamination of the product.

[0009] Although several examples of TEMPO-based compound immobilized resins have been reported in the literature, in practical use, the resins often gradually swell or break down in organic solvents or oxidizing environments, causing clogging of the reactor and pressure buildup, which directly results in a significant decrease in the substrate conversion rate during catalyst recycling, and ultimately insufficient cycle numbers, limiting their practical application. Summary of the Invention [Problem to be solved by the invention]

[0010] The main object of the present invention is to provide a TEMPO compound supported catalyst, a preparation method thereof and use thereof, which solves the problem of the prior art that the TEMPO compound-immobilized resin is prone to swelling and breaking in practical use. [Means for solving the problem]

[0011] In order to achieve the above object, according to one aspect of the present invention, a polymer resin is used as a carrier, the polymer resin is a polystyrene resin containing chloromethyl or bromomethyl, and the content of the chloromethyl or bromomethyl in the polymer resin is 0.5 to 5.0 mmol g -1 is 、 A TEMPO-based compound supported catalyst for oxidation reactions is provided.

[0012] Furthermore, the polymer resin is one or more selected from the following grades: LX-B14 resin, LX-207 resin, LX-SS02 resin, LX-1000ME resin, and Merrifield chloromethylated resin.

[0013] Further, the TEMPO-based compound includes one or more of hydroxy-substituted TEMPO, amino-substituted TEMPO, and carbonyl-substituted TEMPO, preferably hydroxy-substituted TEMPO, and more preferably 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl.

[0014] Furthermore, the TEMPO compound is supported on the polymer resin in the form of a covalent bond.

[0015] In order to achieve the above object, according to one aspect of the present invention, there is provided a method for producing the above catalyst, comprising the step of catalyzing a substitution reaction between a polymer resin and a TEMPO compound in an organic solvent using a phase transfer catalyst to obtain a catalyst.

[0016] Furthermore, the amount of the TEMPO compound used is 4 mmol to 12 mmol / 1 g (dry weight of polymer resin) relative to the amount of the polymer resin used, and the substitution reaction temperature is preferably 50 to 90° C. and the substitution reaction time is 2 to 3 days.

[0017] Further, the phase transfer catalyst is a tetrabutyl quaternary ammonium compound, preferably the tetrabutyl quaternary ammonium compound is one or more selected from tetrabutyl ammonium hydroxide, tetrabutyl ammonium fluoride, tetrabutyl ammonium chloride, and tetrabutyl ammonium bromide; preferably, an aqueous inorganic alkali solution is added during the reaction, preferably the aqueous inorganic alkali solution is one or more selected from a sodium hydroxide solution and a potassium hydroxide solution; preferably, the molar ratio of the tetrabutyl quaternary ammonium compound to the inorganic alkali is 1:50 to 1:400; preferably, the concentration of the aqueous inorganic alkali solution is 2 to 4 mol L -1 It is.

[0018] Furthermore, the organic solvent is one or more selected from toluene, chlorobenzene, and nitrobenzene.

[0019] In addition, the preparation method further includes the steps of washing and drying the catalyst, and preferably, ethanol is used as a washing liquid for washing.

[0020] Furthermore, drying is performed using a blower oven or an infrared lamp, the drying temperature is 60 to 100°C, and the drying time is 6 to 24 hours.

[0021] According to another aspect of the present invention, there is provided a use of the above-mentioned TEMPO compound-supported catalyst, which comprises using the catalyst in a catalytic oxidation reaction, and preferably, the oxidation reaction is an oxidation reaction using an alcohol as a substrate.

[0022] Further, the use includes catalyzing a continuous oxidation reaction of alcohol using a catalyst, preferably including continuously feeding an alcohol-containing substrate raw material and an oxidation liquid into a continuous reactor to oxidize the alcohol in the alcohol-containing substrate raw material, the continuous reactor being filled with a catalyst, the oxidation liquid being a PBS buffer solution containing sodium hypochlorite, the concentration of sodium hypochlorite in the oxidation liquid being 0.35-0.80 mol / L, the concentration of alcohol in the alcohol-containing substrate raw material being 0.10-0.40 mol / L, preferably the flow rate of the alcohol-containing substrate raw material being 0.13-1.00 g / min, and preferably the flow rate of the oxidation liquid being 0.15-1.20 g / min.

[0023] Furthermore, said alcohol is a primary or secondary alcohol, preferably benzyl alcohol, 1-phenylethyl alcohol, n-hexanol, cyclohexanol, p-nitrobenzyl alcohol.

[0024] Furthermore, the concentration of sodium hypochlorite in the oxidation liquid is 0.50 to 0.60 mol / L, the concentration of alcohol in the alcohol-containing substrate raw material is 0.10 to 0.30 mol / L, preferably the flow rate of the alcohol-containing substrate raw material is 0.20 to 0.52 g / min, and preferably the flow rate of the oxidation liquid is 0.30 to 0.60 g / min.

[0025] Furthermore, the retention time of the alcohol-containing substrate raw material in the continuous reactor is 30 to 60 minutes. Effect of the Invention

[0026] According to the technical solution of the present invention, the TEMPO compound supported catalyst in the present application is formed by supporting a TEMPO compound on a polymer carrier to form a heterogeneous catalyst, which is easy to recover, prevents contamination of the product, and can be reused without significant loss of activity. It can also be loaded into a continuous reactor for continuous chemical production, which greatly saves material and labor costs, improves heat transfer conditions, enhances safety, and reduces the generation and discharge of waste materials.

[0027] In this application, commercially available porous polymeric resin carriers with polystyrene skeletons, such as LX-B14, LX-207, LX-SS02, LX-1000ME, Merrifield chloromethylated resin, are selected. In particular, the above resins have a very low swelling degree in organic solvents. In practical continuous production, a low swelling degree is advantageous for maintaining the rigidity of the resin, preventing softening due to expansion of the resin, mutual extrusion, and pressure increase (pressure accumulation) in the reactor, thereby preventing the resin from breaking.

[0028] In addition, the polystyrene backbone of the resin is relatively stable in an oxidizing environment, has good resistance to oxidizing agents (e.g., sodium hypochlorite), and will not break or decompose after contact with the oxidizing agent. Furthermore, these polymeric resin supports have the advantages of large specific surface area, high strength, and low cost, making them suitable for large-scale industrial applications and long cycle life. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] In addition, the embodiments and features of the embodiments of the present application may be combined with each other without causing any contradiction.

[0030] As analyzed in the Background of the Invention, the TEMPO compound-immobilized resin in the prior art has problems in that it is easily swollen and broken in practical use. To solve these problems, the present application provides a TEMPO compound-supported catalyst, its preparation method and its use.

[0031] In a representative embodiment of the present application, a polymer resin is used as a carrier, and the polymer resin is a polystyrene resin containing chloromethyl or bromomethyl, and the content of chloromethyl or bromomethyl in the polymer resin is 0.5 to 5.0 mmol g -1 and 、 Preferably, the content of chloromethyl or bromomethyl is 0.6 to 4.1 mmol g -1 The present invention provides a supported TEMPO-based compound catalyst for oxidation reactions,

[0032] The TEMPO-based compound supported catalyst in the present application is a heterogeneous catalyst formed by supporting a TEMPO-based compound on a polymer carrier, which is easy to recover, prevents contamination of the product, and can be reused without significant loss of activity, and can also be filled into a continuous reactor for continuous chemical production, which greatly reduces material and labor costs, improves heat transfer conditions, improves safety, and reduces waste generation and discharge. The polymer resin in the present application has a polystyrene skeleton and the above-mentioned content of chloromethyl or bromomethyl, so that it has a very low swelling degree in organic solvents, and in actual continuous production, a low swelling degree is advantageous for maintaining the rigidity of the resin, preventing softening due to expansion of the resin, mutual extrusion, and pressure rise (pressure accumulation) in the reactor, thereby preventing the resin from breaking.

[0033] In addition, the polystyrene skeleton of the polymer resin is relatively stable in an oxidizing environment, has good resistance to oxidizing agents (e.g., sodium hypochlorite), and will not break or decompose after contact with the oxidizing agent. Furthermore, the polymer resin carrier has the advantages of large specific surface area, high strength, and low cost, making it suitable for large-scale industrial applications and long cycle life.

[0034] In some embodiments, the polymeric resin support is preferably one or more selected from Xi'an Lanxiao Technology Co., Ltd. LX-B14, Xi'an Lanxiao Technology Co., Ltd. LX-207, Xi'an Lanxiao Technology Co., Ltd. LX-SS02, LX-1000ME, and Merrifield chloromethylated resin, and more preferably, the polymeric resin support is Xi'an Lanxiao Technology Co., Ltd. LX-B14. These functionalized resins are highly reactive, easy to modify, and inexpensive.

[0035] The bromomethyl content in LX-B14 manufactured by Xi'an Lanxiao Technology Co., Ltd. is 3.5 mmol g -1 The bromomethyl content in Xi'an Lanxiao Technology Co., Ltd.'s LX-207 is 4.1 mmol g -1 The chloromethyl content in Xi'an Lanxiao Technology Co., Ltd.'s LX-SS02 is 1.2 mmol g -1 The chloromethyl content in LX-1000ME is 0.6 mmol g -1 and the chloromethyl content in the Merrifield chloromethylated resin is 1.4 mmol g -1 As a result of experiments and explorations by the present inventors, LX-B14 has high reusability and catalytic activity.

[0036] In some embodiments, the present application selects a commercially available TEMPO-based compound, which includes one or more of hydroxy-substituted TEMPO, amino-substituted TEMPO, and carbonyl-substituted TEMPO. For cost savings and ease of modification, the TEMPO-based compound is preferably a hydroxy-substituted TEMPO.

[0037] The above polymer resins all have benzyl halo groups, and therefore can react with the TEMPO compound to form a covalent bond by utilizing the high activity of the benzyl halo groups. In some embodiments, the TEMPO compound is supported on the polymer resin in the form of a covalent bond, and the bond between the TEMPO compound and the polymer resin is stronger through the covalent bond.

[0038] In another exemplary embodiment of the present application, there is provided a method for preparing the above catalyst, comprising the steps of catalyzing a substitution reaction between a polymeric resin and a TEMPO-based compound in an organic solvent using a phase transfer catalyst to obtain a catalyst.

[0039] The preparation method adopted in the present application is simple, the raw materials are readily available, and the cost is low. The TEMPO-based compound-supported catalyst prepared in the present application is a heterogeneous catalyst formed by covalently bonding a TEMPO-based compound on a polymer support, which not only eliminates the need for a catalyst recovery step and prevents product contamination, but also allows the catalyst to be fed into a coil reactor for continuous chemical production, thus greatly reducing material and labor costs, improving heat transfer conditions, improving safety, and reducing waste generation and emissions.

[0040] In this application, commercially available porous polymeric resin carriers with polystyrene skeleton, such as LX-B14, LX-207, LX-SS02, LX-1000ME, Merrifield chloromethylated resin, are selected, and the above resins have very low swelling degree in organic solvents. In practical continuous production, low swelling degree is advantageous for maintaining the rigidity of the resin, preventing softening due to expansion of the resin, mutual extrusion, and pressure rise (pressure accumulation) in the reactor, thereby preventing the resin from breaking.

[0041] In addition, the polystyrene backbone is relatively stable in an oxidizing environment, has good resistance to oxidizing agents (e.g., sodium hypochlorite), and will not break or decompose after contact with the oxidizing agent. Furthermore, these polymeric resin supports have the advantages of large specific surface area, high strength, and low cost, making them suitable for large-scale industrial applications.

[0042] To complete the reaction, in some embodiments, the amount of the TEMPO compound used is 4 mmol to 12 mmol / g (dry weight resin) of the polymer resin, the temperature of the substitution reaction is 50 to 90° C., and the time of the substitution reaction is 2 to 3 days.

[0043] In some embodiments, a phase transfer catalyst is added during the reaction to promote the progress of the reaction, and the phase transfer catalyst includes various tetrabutyl quaternary ammonium compounds, and is preferably one or more of tetrabutyl ammonium hydroxide, tetrabutyl ammonium fluoride, tetrabutyl ammonium chloride, and tetrabutyl ammonium bromide. An aqueous inorganic alkali solution is added during the reaction to create an alkaline environment, and the aqueous inorganic alkali solution is preferably one or more selected from a sodium hydroxide solution and a potassium hydroxide solution. Since inorganic alkali can only be dissolved in solvents such as water and ethanol, and side reactions are likely to occur when ethanol is used as the solvent, inorganic alkali is preferably used.

[0044] At this time, the phase transfer catalyst reacts with the inorganic alkali to produce tetrabutylammonium hydroxide, which has a certain degree of solubility in both organic solvents and water, and can transport hydroxide ions to the organic phase to promote the reaction, and can transport the halogen ions and hydrogen ions produced by the reaction to the aqueous phase. At this time, the TEMPO-based compound substitutes the halogen in the haloalkyl of the polymer resin to form a covalent bond with the polymer resin, and the hydroxide ions in the inorganic alkali aqueous solution can neutralize the halogen ions and hydrogen ions transported to the aqueous phase.

[0045] Further, the molar ratio of the tetrabutylammonium compound to the inorganic alkali is preferably 1:50 to 1:400, more preferably 1:100, and the concentration of the aqueous inorganic alkali solution is preferably 2 to 4 mol L. -1 Preferably, the concentration of the inorganic alkaline aqueous solution is 3 mol L -1 , thereby providing sufficient hydroxide ions for both to enter the organic phase and improve the efficiency of the reaction.

[0046] The type of organic solvent is not particularly limited, as long as it is incompatible with water, can dissolve the TEMPO compound, and has a boiling point of its own or a boiling point of its azeotrope with water higher than the reaction temperature. The organic solvent is one or more selected from toluene, chlorobenzene, and nitrobenzene. In order to save costs, the organic solvent is preferably toluene, and the concentration of the TEMPO compound in the organic solvent is preferably 0.3 mol L -1 It is.

[0047] In the above reaction process, in addition to the formation of a chemical bond between the TEMPO compound and the polymer resin, other products are also produced. Therefore, in order to remove impurities in the catalyst and facilitate subsequent use, the preparation method further includes a step of washing and drying the catalyst, and preferably, ethanol is used as a washing liquid for washing.

[0048] In order to avoid the structure of the catalyst being destroyed due to an excessively high temperature during drying, the drying is preferably performed using a blower oven or an infrared lamp, the drying temperature is 60 to 100°C, and the drying time is 6 to 24 hours.

[0049] Another exemplary embodiment of the present application provides a use of the catalyst, which comprises using the catalyst in a catalytic oxidation reaction, preferably the oxidation reaction is an oxidation reaction of an alcohol as a substrate.

[0050] The TEMPO-based compound supported catalyst in the present application is used in catalytic oxidation reactions, and can catalyze the substrate alcohol in continuous chemical reactions to stably convert it into aldehydes and ketones, and the polymer resin support after the reaction maintains its integrity and does not break or decompose even after long-term use. Meanwhile, by supporting the TEMPO-based compound on the polymer resin, it is possible to avoid the mixing of the TEMPO-based compound with the product system, thereby reducing the subsequent processing work, lowering costs, and improving safety.

[0051] Compared with batch reactions, continuous reactions are more controllable and safer. A TEMPO-based compound-supported catalyst can be used in the continuous reaction, which is easy to recover and prevents the catalyst from contaminating the product.

[0052] In some embodiments, the use of the present application includes catalyzing a continuous oxidation reaction of alcohol using the TEMPO-based compound supported catalyst, preferably including continuously feeding an alcohol-containing substrate feedstock and an oxidation liquid into a continuous reactor to oxidize the alcohol in the alcohol-containing substrate feedstock, the continuous reactor being filled with the catalyst, the oxidation liquid being a PBS buffer solution containing sodium hypochlorite, the concentration of sodium hypochlorite in the oxidation liquid being 0.35-0.80 mol / L, the concentration of alcohol in the alcohol-containing substrate feedstock being 0.10-0.40 mol / L, preferably the flow rate of the alcohol-containing substrate feedstock being 0.13-1.00 g / min, and preferably the flow rate of the oxidation liquid being 0.15-1.20 g / min.

[0053] The alcohol of the present application is not particularly limited, and in some embodiments, the alcohol is a primary alcohol or a secondary alcohol, preferably benzyl alcohol, 1-phenylethyl alcohol, n-hexanol, cyclohexanol, or p-nitrobenzyl alcohol.

[0054] The oxidizing liquid is an oxidizing liquid commonly used by those skilled in the art. In some embodiments, the oxidizing liquid is a PBS buffer solution containing sodium hypochlorite. In a continuous chemical reaction, the substrate (the alcohol of the present application) constantly enters the TEMPO-based compound-supported catalyst, so the concentration of the sodium hypochlorite solution determines the amount of oxidizing agent that contacts the substrate at any given time. Thus, controlling the concentration of the alcohol, the concentration of sodium hypochlorite, and the flow rate of the alcohol-containing substrate raw material and the flow rate of the oxidizing liquid allows for adjustment of the oxidizing agent that contacts the substrate.

[0055] As a result of research by the present inventors, it has been found that the concentration of sodium hypochlorite in the oxidizing solution is preferably 0.50 to 0.60 mol / L. If the concentration is below this range, the conversion rate of the substrate decreases, and if the concentration is above this range, the oxidizing agent becomes excessive, side reactions are more likely to occur, and costs increase.

[0056] In some embodiments, the alcohol-containing substrate feedstock and the oxidation liquid are pumped by a reciprocating pump into a continuous reactor, for example, the continuous reactor includes one or more cylindrical continuous reaction columns connected in series, more specifically, for example, two cylindrical continuous reaction columns connected in series, and the cylindrical continuous reaction columns can have a length of 25 to 100 cm and a diameter of 5 to 10 cm.

[0057] As a result of the research by the present inventors, it was found that the alcohol concentration in the alcohol-containing substrate raw material is 0.10 to 0.30 mol / L, preferably the flow rate of the alcohol-containing substrate raw material is 0.20 to 0.52 g / min, and preferably the flow rate of the oxidation liquid is 0.30 to 0.60 g / min. If the concentration of the substrate solution is too high or the flow rate of the substrate solution / oxidation liquid is too fast, the conversion rate decreases, and if the flow rate is too slow, there is a possibility of side reactions occurring, so an appropriate flow rate is selected.

[0058] In some embodiments, the retention time of the alcohol-containing substrate feed in the continuous reactor is 30-60 minutes.

[0059] Hereinafter, the present application will be described in more detail with reference to specific examples, which are not to be understood as limiting the scope of protection claimed by the present application.

[0060] Example 1 The method for producing the TEMPO compound supported catalyst is as follows. TIFF2025507805000001.tif24170

[0061] 15 g of wet LX-B14 resin spheres (measured moisture content 72%, actual dry weight approximately 4.2 g), 6.21 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hydroxy-substituted TEMPO), and 1.16 g of tetrabutylammonium bromide were added to a 500 mL four-neck flask. -1 120 mL of sodium hydroxide solution and 120 mL of toluene were added, a mechanical stirrer was attached, and the mixture was stirred at 250 rpm and heated at 70 °C for 3 days. The resulting resin was washed with ethanol until the washing liquid was no longer orange-yellow, baked at 80 °C for 16 h, and stored. The resulting TEMPO-based compound supported catalyst was named LX-B14-TEMPO.

[0062] Example 2 The procedure was the same as in Example 1, except that 11.5 g of wet LX-207 resin spheres (actual moisture content: 65%, actual dry weight: about 4.0 g) were prepared. The resulting TEMPO compound-supported catalyst was named LX-207-TEMPO.

[0063] Example 3 The procedure was the same as in Example 1, except that 7 g of wet LX-SS02 resin spheres (measured water content was 41%, actual dry weight was about 4.0 g) were prepared. The resulting TEMPO compound-supported catalyst was named LX-SS02-TEMPO.

[0064] Example 4 The procedure was the same as in Example 1, except that 7.2 g of wet LX-1000ME resin spheres (measured water content was 45%, actual dry weight was about 4.1 g) were prepared. The obtained TEMPO compound-supported catalyst was named LX-1000ME-TEMPO.

[0065] Example 5 The procedure was the same as in Example 1, except that 4 g of dried Merrifield chloromethylated resin spheres (supplier: Xi'an Lanxiao Technology New Materials Co., Ltd.) were prepared. The obtained TEMPO-based compound-supported catalyst was named Merrifield chloromethylated resin-TEMPO.

[0066] Example 6 15 g of wet LX-B14 resin spheres (measured moisture content 72%, actual dry weight approximately 4.2 g) and 6.21 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hydroxy-substituted TEMPO) were added to a 500 mL four-neck flask. 3 mol L -1 120 mL of sodium hydroxide solution, 2.33 g of 40% aqueous solution of tetrabutylammonium hydroxide, and 120 mL of toluene were added, and the mixture was stirred at 250 rpm with a mechanical stirrer and heated at 70 °C for 3 days. The resin obtained was washed with ethanol until the washing liquid was no longer orange-yellow, baked at 80 °C for 16 h, and stored. The obtained TEMPO-based compound supported catalyst was named LX-B14-TEMPO-2.

[0067] Example 7 Same as Example 1, except heated at 90°C for 3 days.

[0068] Example 8 Same as Example 1, except heated at 50°C for 3 days.

[0069] Example 9 Same as Example 1, except that 2.89 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hydroxy-substituted TEMPO) was added.

[0070] Example 10 Same as Example 1, except that 8.67 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hydroxy-substituted TEMPO) was added.

[0071] Example 11 Same as Example 1, except that 1.44 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hydroxy-substituted TEMPO) was added.

[0072] Example 12 Same as Example 1, except that 11.55 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hydroxy-substituted TEMPO) was added.

[0073] Example 13: Oxidation reaction catalyzed by LX-B14-TEMPO (batch reaction using benzyl alcohol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The mixture was diluted to 100 mL with phosphate buffer (PBS, pH = 7.0). For the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 100 μL of benzyl alcohol (template substrate) was added.

[0074] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution was added and gently shaken well. Finally, 150 mg of LX-B14-TEMPO-supported resin from Example 1 was added, the centrifuge tube was capped, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 1 below.

[0075] [Table 1]

[0076] Examples 14 to 19 Oxidation reaction catalyzed by the supported TEMPO compound catalysts prepared in Examples 7 to 12 (batch reaction using benzyl alcohol as a template substrate) The steps were the same as in Example 13, and the conversion rate of each reaction is shown in Table 2 below.

[0077] [Table 2]

[0078] Example 20: Oxidation reaction catalyzed by LX-B14-TEMPO (batch reaction using 1-phenylethyl alcohol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). During the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 120 μL of 1-phenylethyl alcohol (racemic, template substrate) was added.

[0079] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution was added and gently shaken well. Finally, 150 mg of LX-B14-TEMPO-supported resin of Example 1 was added, the centrifuge tube was capped, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 3 below.

[0080] [Table 3]

[0081] Example 21: Oxidation reaction catalyzed by LX-B14-TEMPO (batch reaction using n-hexanol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). During the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 125 μL of n-hexanol (template substrate) was added.

[0082] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution was added and gently shaken well. Finally, 150 mg of LX-B14-TEMPO-supported resin from Example 1 was added, the centrifuge tube was capped, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 4 below.

[0083] [Table 4]

[0084] Example 22: Oxidation reaction catalyzed by LX-B14-TEMPO (batch reaction using cyclohexanol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). During the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 105 μL of cyclohexanol (template substrate) was added.

[0085] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution was added and gently shaken well. Finally, 150 mg of the LX-B14-TEMPO compound-supported resin of Example 1 was added, the centrifuge tube was capped, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 5 below.

[0086] [Table 5]

[0087] Example 23: Oxidation reaction catalyzed by LX-B14-TEMPO (batch reaction using p-nitrobenzyl alcohol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). For the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 150 mg of p-nitrobenzyl alcohol (template substrate) was added.

[0088] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution was added and gently shaken well. Finally, 150 mg of the LX-B14-TEMPO compound-supported resin of Example 1 was added, the centrifuge tube was capped, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 6 below.

[0089] [Table 6]

[0090] Example 24: Oxidation reaction catalyzed by LX-207-TEMPO (batch reaction using benzyl alcohol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). During the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 100 μL of benzyl alcohol (template substrate) was added.

[0091] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution was added and gently shaken well. Finally, 150 mg of LX-207-TEMPO-supported resin from Example 2 was added, the centrifuge tube was capped, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 7 below.

[0092] [Table 7]

[0093] Example 25: Oxidation reaction catalyzed by LX-SS02-TEMPO (batch reaction using benzyl alcohol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). During the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 100 μL of benzyl alcohol (template substrate) was added.

[0094] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution was added and gently shaken well. Finally, 150 mg of LX-SS02-TEMPO-based compound TEMPO-based compound supported resin of Example 3 was added, the cap of the centrifuge tube was tightened, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 8 below.

[0095] [Table 8]

[0096] Example 26: Oxidation reaction catalyzed by LX-1000ME-TEMPO (batch reaction, benzyl alcohol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). During the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 100 μL of benzyl alcohol (template substrate) was added.

[0097] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution was added and gently shaken well. Finally, 150 mg of LX-1000ME-TEMPO-based compound TEMPO-based compound supported resin of Example 4 was added, the cap of the centrifuge tube was tightened, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 9 below.

[0098] [Table 9]

[0099] Example 27: Oxidation reaction catalyzed by Merrifield chloromethylated resin-TEMPO (batch reaction, benzyl alcohol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). During the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 100 μL of benzyl alcohol (template substrate) was added.

[0100] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution was added and gently shaken well. Finally, 150 mg of Merrifield chloromethylated resin-TEMPO compound-supported resin from Example 5 was added, the centrifuge tube was capped, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 10 below.

[0101] [Table 10]

[0102] Example 28: Oxidation reaction catalyzed by LX-B14-TEMPO-2 (batch reaction using benzyl alcohol as template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). During the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 100 μL of benzyl alcohol (template substrate) was added.

[0103] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution and shake gently. Finally, 150 mg of LX-B14-TEMPO-supported resin from Example 1 was added, the centrifuge tube was capped, and the tube was placed in an ice bath and shaken. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 11 below.

[0104] [Table 11]

[0105] Example 29: Oxidation reaction catalyzed by LX-B14-TEMPO (continuous chemical reaction using benzyl alcohol as a template substrate) Two kinds of raw material solutions are used in this continuous chemical reaction. Liquid A is a solution of benzyl alcohol in dichloromethane, with a concentration of benzyl alcohol of 0.2 mol L−1. -1 and solution B is 40 mL of commercially available sodium hypochlorite solution (approximately 10 wt%), diluted to 0.2 mol L -1 This is a buffered sodium hypochlorite solution diluted to 100 mL with PBS (pH = 7.0), and the concentration of sodium hypochlorite is approximately 0.53 mol L -1 It is.

[0106] The LX-B14-TEMPO-loaded resin from Example 1 was wetted with dichloromethane and packed into two cylindrical iron pipes with a diameter of 8 mm, and then both ends were sealed with fine metal mesh. Each iron pipe was 50 cm long. After packing the materials, the LX-B14-TEMPO resin catalyst in the iron pipes was dried with nitrogen gas and prepared for use.

[0107] During the experiment, a continuous chemical reaction system was constructed using two low- and medium-pressure reciprocating pumps and the aforementioned iron pipe column, the materials were mixed using a T-joint in front of the column, and the two columns were connected in series with a polytetrafluoroethylene tube and reacted at room temperature.

[0108] The flow rate of the reciprocating pump is 0.26 g min -1 , and 0.30g min for solution B -1 may be also possible.

[0109] After setting the flow rate, the reciprocating pump was started to supply the material. At this flow rate, after 90 minutes, the liquid began to be discharged from the outlet, from which it was estimated that the retention time of the material in the column was about 40 minutes. 4 hours after the material was supplied, the effluent was collected for 10 minutes, and the dichloromethane phase of this effluent was diluted and supplied to HPLC analysis. After the reaction was completed, the entire apparatus was rinsed with dichloromethane, and the dichloromethane remaining in the iron column was purged with nitrogen gas.

[0110] In this embodiment, the continuous reactor can continuously oxidize at least 1 mol of benzyl alcohol and convert it to benzaldehyde, and can maintain the conversion rate of the substrate at 90% or more. Note that the amount of LX-B14-TEMPO loaded in the reactor is only the amount used in a small trial scale. In actual production, more resin can be loaded into the coil reactor for catalytic oxidation of substrates on a kilogram scale or more.

[0111] Example 30 Solution A is a solution of benzyl alcohol in dichloromethane with a concentration of 0.1 mol L -1 This is different from Example 29.

[0112] Example 31 Solution A is a solution of benzyl alcohol in dichloromethane with a concentration of 0.4 mol L -1 This is different from Example 29.

[0113] Example 32 In the preparation method of solution B, 20 mL of commercially available sodium hypochlorite solution (approximately 10 wt%) was added to 0.2 mol L -1 Dilute to 100 mL with PBS (pH = 7.0) to make the sodium hypochlorite concentration approximately 0.35 mol L -1 This is different from Example 29.

[0114] Example 33 In the preparation method of solution B, 60 mL of commercially available sodium hypochlorite solution (approximately 10 wt%) was added to 0.2 mol L-1 Dilute to 100 mL with PBS (pH = 7.0) to make the concentration of sodium hypochlorite approximately 0.80 mol L -1 This is different from Example 29.

[0115] Example 34 The flow rate of the reciprocating pump is 0.13 g min -1 , and 0.15g min for solution B -1 This is different from Example 29.

[0116] Example 35 The flow rate of the reciprocating pump is 0.20 g min -1 , and 0.30g min for solution B -1 This is different from Example 29.

[0117] Example 36 The flow rate of the reciprocating pump is 0.52 g min -1 , and 0.60g min for solution B -1 This is different from Example 29.

[0118] Example 37 The flow rate of the reciprocating pump is 1.00 g min -1 , and 1.20 g min for solution B. -1 This is different from Example 29.

[0119] The conversion rates of the substrate in Examples 29 to 37 are shown in Table 12.

[0120] [Table 12]

[0121] Comparative Example 1: 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hydroxy-substituted TEMPO) Oxidation reaction catalyzed by TEMPO-based compounds (batch reaction using benzyl alcohol as a template substrate) First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0).

[0122] For the experiment, add 2.5 mL of dichloromethane to a 15 mL centrifuge tube, add 100 μL of benzyl alcohol (template substrate), shake well, add 3.75 mL of the above sodium hypochlorite stock solution, and then add 1 mol L -1 0.1 mL of sodium bromide solution was added and the mixture was gently shaken well.

[0123] Finally, 150 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hydroxy TEMPO compound) was added, the centrifuge tube was capped, and the tube was shaken in an ice bath. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The conversion rate was calculated to be 100%.

[0124] Comparative Example 2: Oxidation reaction catalyzed by chloromethylstyrene resin with low chloromethyl content (batch reaction with benzyl alcohol as template substrate) (1) Synthesis of resin with low chloromethyl content A 250 mL four-neck flask was immersed in an ice bath, and 10.0 g (11.93 mL) of dimethoxymethane, 2.8 g (2.36 mL) of concentrated hydrochloric acid, and 3.8 g of paraformaldehyde were added in sequence. 3.5 g (1.87 mL) of concentrated sulfuric acid was slowly dripped into the flask. After uniform stirring, 2.6 g of highly cross-linked styrene resin (cross-linking degree is about 75%) was added, and further stirred for 1 h, and 0.8 g of anhydrous zinc chloride and 10 mL of thionyl chloride were added. The system was carefully refluxed overnight at a temperature slightly lower than 40 °C. After overnight, the resin was filtered, washed with a large amount of ethanol and THF, baked, and the resin was named as DVB-st-Cl. Characterization showed that the chloromethyl content of the DVB-st-Cl resin was about 0.08 mmol / g.

[0125] (2) TEMPO loading on resin 0.5 g of dry DVB-st-Cl resin spheres, 0.62 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hydroxy-substituted TEMPO), and 0.12 g of tetrabutylammonium bromide were added to a 100 mL four-neck flask. -1 15 mL of sodium hydroxide solution and 15 mL of toluene were added, a mechanical stirrer was attached, and the mixture was stirred at 250 rpm and heated at 70 °C for 3 days. The resin obtained was washed with ethanol until the washing liquid was no longer orange-yellow, baked at 80 °C for 16 h, and stored. The obtained TEMPO-based compound supported catalyst was named DVB-st-Cl-TEMPO.

[0126] (3) Catalytic oxidation reaction First, prepare a stock solution of sodium hypochlorite for buffering, i.e., 40 mL of a commercial sodium hypochlorite solution (approximately 10 wt%) was diluted with 0.2 mol L -1 The solution was diluted to 100 mL with PBS (pH = 7.0). During the experiment, 2.5 mL of dichloromethane was added to a 15 mL centrifuge tube, and 100 μL of benzyl alcohol (template substrate) was added.

[0127] Shake well and add 3.75 mL of the above sodium hypochlorite stock solution, then add 1 mol L -1 0.1 mL of sodium bromide solution, gently shaken well.

[0128] Finally, 150 mg of the above DVB-st-Cl-TEMPO-supported resin was added, the centrifuge tube was capped, and the tube was shaken in an ice bath. After 1 h, an appropriate amount of the dichloromethane phase of the reaction system was taken, diluted with a solvent, and subjected to HPLC analysis. The resin after the reaction was washed with dichloromethane and recycled, and its catalytic activity was further measured. The conversion rate of each reaction is shown in Table 13 below.

[0129] [Table 13]

[0130] It is difficult to directly express the content of the TEMPO compound in the TEMPO compound supported catalyst. As a result of the study of the catalytic reaction kinetics of the LX-B14-TEMPO compound supported catalyst, the inventors found that the catalytic effect per 1 g of resin was 10 -4 This corresponds to a heterogeneous solution of TEMPO compounds in the order of mmol / L. Because the resin spheres are insoluble in the solvent and are a heterogeneous catalyst in solution, the catalytic behavior is significantly different from that of a homogeneous solution, so this data cannot be directly taken as the content of TEMPO compounds on the resin.

[0131] As can be seen from the above description, the above embodiments of the present invention provide the following technical effects: The TEMPO-based compound supported catalyst in the present application is formed by covalently bonding a TEMPO-based compound on a polymer support to form a heterogeneous catalyst, which not only eliminates the need for a catalyst recovery step and prevents product contamination, but also allows the catalyst to be fed into a coil reactor for continuous chemical production, thereby greatly saving material and labor costs, improving heat transfer conditions, improving safety, and reducing waste generation and discharge.

[0132] In this application, commercially available porous polymeric resin supports with polystyrene skeletons, such as LX-B14, LX-207, LX-SS02, LX-1000ME, Merrifield chloromethylated resin, are selected, in particular, the above resins have a very low swelling degree in organic solvents, and in practical continuous production, the low swelling degree is advantageous for maintaining the rigidity of the resin, preventing softening due to expansion of the resin, mutual extrusion, and pressure increase (pressure accumulation) of the reactor and other phenomena, thereby preventing the resin from breaking. In addition, the polystyrene skeleton is relatively stable in an oxidizing environment, has good resistance to oxidizing agents (e.g., sodium hypochlorite), and will not break or decompose after contact with the oxidizing agent. In addition, these polymeric resin supports have the advantages of large specific surface area, high strength, and low cost, making them suitable for large-scale industrial applications and long cycle life.

[0133] The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Those skilled in the art can make various modifications and variations to the present invention. Any so-called amendments, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A polymer resin is used as a carrier, and the polymer resin is a polystyrene resin containing chloromethyl or bromomethyl, and the content of the chloromethyl or bromomethyl in the polymer resin is 0.5 to 5.0 mmol g -1 is 、 TEMPO-based compound supported catalyst for oxidation reactions.

2. The polymeric resin is one or more selected from the group consisting of LX-B14 resin, LX-207 resin, LX-SS02 resin, LX-1000ME resin, and Merrifield chloromethylated resin; The catalyst according to claim 1.

3. The TEMPO-based compound includes one or more of hydroxy-substituted TEMPO, amino-substituted TEMPO, and carbonyl-substituted TEMPO, and is preferably 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. The catalyst according to claim 1.

4. The TEMPO-based compound is supported on the polymer resin in the form of a covalent bond. The catalyst according to claim 1.

5. catalyzing a substitution reaction between a polymer resin and a TEMPO-based compound in an organic solvent using a phase transfer catalyst to obtain the catalyst; The method for producing the catalyst according to any one of claims 1 to 4.

6. The amount of the TEMPO compound used is 4 mmol to 12 mmol / 1 g (dry weight of polymer resin) based on the amount of the polymer resin used, and preferably, the temperature of the substitution reaction is 50 to 90° C., and the time of the substitution reaction is 2 to 3 days. The method according to claim 5 .

7. The phase transfer catalyst is a tetrabutyl quaternary ammonium compound, preferably the tetrabutyl ammonium compound is one or more selected from tetrabutyl ammonium hydroxide, tetrabutyl ammonium fluoride, tetrabutyl ammonium chloride, and tetrabutyl ammonium bromide; preferably, an aqueous inorganic alkali solution is added during the reaction, preferably the aqueous inorganic alkali solution is one or more selected from sodium hydroxide solution and potassium hydroxide solution; preferably, the molar ratio of the tetrabutyl quaternary ammonium compound to the inorganic alkali is 1:50 to 1:400; preferably, the concentration of the aqueous inorganic alkali solution is 2 to 4 mol L -1 That is, The method according to claim 6.

8. The organic solvent is one or more selected from toluene, chlorobenzene, and nitrobenzene; The method according to any one of claims 5 to 7.

9. The method further includes a step of washing and drying the catalyst, and preferably, ethanol is used as a washing liquid for the washing. The method according to any one of claims 5 to 7.

10. The drying is performed by drying with a blower oven or drying with an infrared lamp, and the drying temperature is preferably 60 to 100°C, and the drying time is preferably 6 to 24 hours. The method of claim 9.

11. The method includes using the catalyst in a catalytic oxidation reaction, and preferably, the oxidation reaction includes an oxidation reaction using an alcohol as a substrate. Use of the TEMPO-based compound supported catalyst according to any one of claims 1 to 4.

12. catalyzing a continuous oxidation reaction of the alcohol using the catalyst, preferably The method includes continuously feeding an alcohol-containing substrate raw material and an oxidation liquid into a continuous reactor to oxidize the alcohol in the alcohol-containing substrate raw material, the continuous reactor being filled with the catalyst, the oxidation liquid being a PBS buffer solution containing sodium hypochlorite, the concentration of the sodium hypochlorite in the oxidation liquid being 0.35-0.80 mol / L, the concentration of the alcohol in the alcohol-containing substrate raw material being 0.10-0.40 mol / L, preferably the flow rate of the alcohol-containing substrate raw material being 0.13-1.00 g / min, and preferably the flow rate of the oxidation liquid being 0.15-1.20 g / min.

12. The use according to claim 11.

13. The alcohol is a primary or secondary alcohol, preferably benzyl alcohol, 1-phenylethyl alcohol, n-hexanol, cyclohexanol, p-nitrobenzyl alcohol; 13. The use according to claim 11 or 12.

14. The concentration of the sodium hypochlorite in the oxidizing liquid is 0.50-0.60 mol / L, the concentration of the alcohol in the alcohol-containing substrate feedstock is 0.10-0.30 mol / L, preferably the flow rate of the alcohol-containing substrate feedstock is 0.20-0.52 g / min, and preferably the flow rate of the oxidizing liquid is 0.30-0.60 g / min; 13. The use according to claim 12.

15. The retention time of the alcohol-containing substrate raw material in the continuous reactor is 30 to 60 min.

13. The use according to claim 12.

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