Supported quaternary ammonium salt catalysts, their preparation and use

Abstract

The application provides a supported quaternary ammonium salt catalyst and its preparation and application, characterized in that a quaternary ammonium salt is used as an active component and chloromethylated polystyrene resin (CMPS) is used as a carrier. The catalyst is applied to catalyze synthesis of adipoyl chloride from adipic acid, and the yield of the adipoyl chloride is greater than or equal to 98.4%. The supported quaternary ammonium salt catalyst prepared by the method has the advantages of high activity, low use cost, easy separation and the like, and has a good industrial application prospect.

Description

Technical Field

[0001] This invention relates to a catalyst, its preparation and application, and more particularly to a supported quaternary ammonium salt catalyst, its preparation and application in catalyzing the synthesis of adipic acid from adipic acid. Background Technology

[0002] Adipic acid chloride is an organic compound with the chemical formula C6H8Cl2O2, which is a colorless to pale yellow liquid. Adipic acid chloride has various applications as an organic intermediate. For example, it can be combined with functional groups on the surface of diamond films to form a covalent adsorption layer; interfacial polycondensation between hexamethylenediamine and diacyl chloride is a new method for producing nylon 66; symmetrical divalent molecules have been studied for the treatment of various diseases, such as the use of magnetite triblock copolymers loaded with temozolomide (TMZ) synthesized with the participation of adipic acid chloride for drug delivery; in recent years, branched macromolecules or coupling agents prepared with adipic acid chloride have been used to bind typical one-dimensional carbon nanotubes to the surface of carbon fibers to form a "flexible-rigid" multi-scale reinforcing structure, which is an effective method to improve the interfacial properties of carbon fiber reinforced composites; the reaction of adipic acid chloride with N,N-hexane-1,6-diyl-bisbenzamide can produce muscarinic receptors that can cross the blood-brain barrier, and these receptors can be used to affect the binding of agonists and antagonists to the orthomeric sites of receptor proteins; compared with the harsh reaction conditions of direct esterification, the use of adipic acid chloride can esterify mono- or disubstituted phenols under phase-transfer catalysis to obtain monoesters or diesters, and achieve higher product yields.

[0003] Traditional methods for preparing adipic acid chloride mostly involve reacting adipic acid with acyl chloride reagents, solvents, and catalysts. The main process flow is as follows: the raw materials react to obtain the product directly, which is then purified to obtain the final product. As early as 1933, thionyl chloride was used as an acyl chloride reagent to prepare adipic acid chloride; in the decades that followed, thionyl chloride was also used to prepare adipic acid chloride. The literature "Green Preparation Process of Adipic Acid Chloride [J], Chemical Industry Times, 2022, 36(08)" reported that the optimal process conditions for the adipic acid acyl chloride reaction were: m(adipic acid chloride):m(trichlorotoluene):m(zinc chloride) = 1:2:0.06, reacting at 70 °C for 4 h, with a product yield of 96.8%.

[0004] Based on existing technologies, the production process of adipic acid chloride involves complex post-reaction treatment of the DMF catalyst and zinc chloride, and the catalyst cannot be reused, resulting in high operating costs and hindering industrial production. Therefore, it is necessary to design and develop catalysts that are more conducive to industrial production to save costs and protect the environment. Summary of the Invention

[0005] One object of the present invention is to provide a supported quaternary ammonium salt catalyst, another object of the present invention is to provide a method for preparing the above-mentioned catalyst, and yet another object of the present invention is to provide the application of the above-mentioned catalyst in the production process of adipic acid chloride.

[0006] The technical solution of the present invention is: a supported quaternary ammonium salt catalyst, characterized in that the quaternary ammonium salt is used as the active component and chloromethylated polystyrene resin (CMPS) is used as the support, and the mass ratio of the active component quaternary ammonium salt to the support CMPS is 1:(2~4).

[0007] This invention also provides a method for preparing the above-mentioned supported quaternary ammonium salt catalyst, the specific steps of which are as follows:

[0008] (1) Preparation of active components: Weigh 3-bromopropylamine hydrobromide and tertiary amine compounds, add them to water and mix and stir. Obtain solid by vacuum distillation. Dissolve the solid in aqueous solution, adjust the pH to 9-10 with alkaline aqueous solution, remove water by vacuum distillation, and obtain the active component quaternary ammonium salt.

[0009] (2) Preparation of supported quaternary ammonium salt catalyst: chloromethylated polystyrene resin (CMPS) was weighed and soaked in a solvent for a certain period of time. Then, the active component quaternary ammonium salt was weighed and added to it and stirred and heated to react. After the reaction was completed, the catalyst was filtered, washed and vacuum dried to obtain the supported quaternary ammonium salt catalyst.

[0010] In preferred step (1), the tertiary amine compound is one of trimethylamine, triethylamine, or tributylamine; the molar ratio of 3-bromopropylamine hydrobromide, the tertiary amine compound, and water is 1:(1~3):(5~15); the stirring time is 3~6 days; the solute in the alkaline aqueous solution is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, or lithium hydroxide, and the concentration of the alkaline aqueous solution is 0.05~0.2mol / L.

[0011] In preferred step (2), the solvent is one of toluene, tetrahydrofuran, dimethyl sulfoxide, or DMF; the soaking time is 12-36 h; the mass ratio of the active component quaternary ammonium salt, CMPS, and solvent is 1:(2-4):(15-25); the reaction temperature is 100-150 °C, the reaction time is 2-5 days; the vacuum drying temperature is 50-80 °C, and the drying time is 12-24 h.

[0012] This invention also provides the application of the above-mentioned supported quaternary ammonium salt catalyst in the catalytic synthesis of adipic acid from adipic acid. The method is characterized by sequentially adding the prepared catalyst, solvent, adipic acid, and chlorinating reagent to a container, stirring and heating to the reaction temperature to initiate the reaction, absorbing the tail gas with an alkaline aqueous solution, and after the reaction is completed and cooled, separating the catalyst by centrifugation, and obtaining a pale yellow, clear liquid as adipic acid chloride by vacuum distillation.

[0013] The preferred mass ratio of adipic acid, chlorination reagent, catalyst and solvent is 1:(3~5):(0.05~0.25):(2~5), the reaction temperature is 50~80 °C and the reaction time is 2~5 h.

[0014] Preferably, the chlorinating agent is one of thionyl chloride, solid phosgene, trichlorotoluene, phosphorus trichloride, or oxalyl chloride; the solute in the alkaline aqueous solution is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, or lithium hydroxide; the solvent is one of cyclohexane, tetrahydrofuran, toluene, or dichloroethane; and the concentration of the alkaline aqueous solution is 0.01~0.1 mol / L.

[0015] Compared with the prior art, the beneficial effects of the present invention are mainly reflected in:

[0016] (1) The method for synthesizing supported quaternary ammonium salt catalysts provided by the present invention has the advantages of simple equipment, convenient operation, mild conditions, and environmentally friendly process, which is conducive to large-scale production.

[0017] (2) The supported quaternary ammonium salt catalyst provided by this invention can be separated from the reactants by simple centrifugation during production. Compared with existing catalysts, it reduces post-processing energy and material consumption, which is beneficial for industrial production.

[0018] (3) The supported quaternary ammonium salt catalyst provided by the present invention is used to catalyze the synthesis of adipic acid and chlorinating reagent into adipic chloride, and has the advantage of high yield. Attached Figure Description

[0019] Figure 1 These are the FT-IR spectra of [TMPB-PS]Br prepared in Examples 1 to 3, where (a) is the FT-IR spectrum of [TMPB-PS]Br prepared in Example 1, (b) is the FT-IR spectrum of [TEPB-PS]Br prepared in Example 2, and (c) is the FT-IR spectrum of [TBPB-PS]Br prepared in Example 3. Detailed Implementation

[0020] The present invention will be described in more detail below with reference to the embodiments. These embodiments are merely descriptions of the best mode of implementation of the present invention and do not limit the scope of protection of the present invention in any way.

[0021] Example 1

[0022] Step 1: Preparation of the active component TMPB: Weigh 0.1 mol of 3-bromopropylamine hydrobromide and 0.1 mol of trimethylamine and add them to 5 mol of water. Mix and stir for 6 days. Obtain a white solid by vacuum distillation. Dissolve the solid in water and adjust the pH to 9-10 with 0.05 mol / L NaOH aqueous solution. Remove water by vacuum distillation to obtain the active component 3-trimethylammonium bromide (TMPB).

[0023] Step 2: Preparation of [TMPB-PS]Br catalyst: Weigh 1 g of chloromethylated polystyrene resin (CMPS) and soak it in 7.5 g of toluene for 36 h. Weigh 0.5 g of TMPB and add it to the solution. Heat to 100 °C and react for 5 days. After the reaction is complete, filter and wash the solution. Dry it under vacuum at 50 °C for 24 h to obtain the [TMPB-PS]Br catalyst.

[0024] Figure 1 (a) is the FT-IR spectrum of [TMPB-PS]Br prepared in Example 1; the positive characteristic peak is at 1265 cm⁻¹. -1 The disappearance of the CH stretching vibration in -CH2Cl, representing the catalyst, indicates that the chloromethyl group has been completely reacted; the negative characteristic peak is at 1475 cm⁻¹. -1 The appearance of the CH stretching vibration in quaternary ammonium salt CH3, with a negative characteristic peak at 1688 cm⁻¹. -1 Represents the bending and stretching vibrations of NH, with a negative characteristic peak at 1100 cm⁻¹. -1 and 3360 cm -1 The peak represents the OH stretching vibration of the hydroxyl group, and the infrared spectrum results confirm the successful preparation of the catalyst [TMPB-PS]Br.

[0025] Example 2

[0026] Step 1: Preparation of the active component TEPB: Weigh 0.15 mol of 3-bromopropylamine hydrobromide and 0.3 mol of triethylamine and add them to 8 mol of water. Mix and stir for 4 days. Obtain a white solid by vacuum distillation. Dissolve the solid in water and adjust the pH to 9-10 with 0.1 mol / L Ca(OH)2 aqueous solution. Remove water by vacuum distillation to obtain the product 3-triethylammonium bromide (TEPB).

[0027] Step 2: Preparation of [TEPB-PS]Br catalyst: Weigh 1.5 g of chloromethylated polystyrene resin (CMPS) and soak it in 10 g of tetrahydrofuran for 24 h. Weigh 0.5 g of TEAB and add it to the solution. Heat to 120 °C and react for 4 days. After the reaction is complete, filter and wash the solution. Dry it under vacuum at 70 °C for 20 h to obtain the [TEPB-PS]Br catalyst.

[0028] Figure 1(b) is the FT-IR spectrum of [TEPB-PS]Br prepared in Example 2; the positive characteristic peak is at 1265 cm⁻¹. -1 The disappearance of the CH stretching vibration in -CH2Cl, representing the catalyst, indicates that the chloromethyl group has been completely reacted; the negative characteristic peak is at 1473 cm⁻¹. -1 The appearance of the CH stretching vibration, representing quaternary ammonium salt CH3, with a negative characteristic peak at 1688 cm⁻¹. -1 Represents the bending and stretching vibrations of NH, 3390 cm -1 The peak represents the NH stretching vibration of the amino group. The infrared spectrum results confirm the successful preparation of the catalyst [TEPB-PS]Br.

[0029] Example 3

[0030] Step 1: Preparation of active component TBPB: Weigh 0.1 mol 3-bromopropylamine hydrobromide and 0.3 mol tributylamine and add them to 15 mol water. Mix and stir for 3 days. Obtain a white solid by vacuum distillation. Dissolve the solid in water and adjust the pH to 9-10 with 0.2 mol / L KOH aqueous solution. Remove water by vacuum distillation to obtain the product 3-tributylammonium bromide (TBPB).

[0031] Step 2: Preparation of [TBPB-PS]Br catalyst: Weigh 2 g of chloromethylated polystyrene resin (CMPS) and soak it in 12.5 g of DMF for 28 h. Weigh 0.5 g of TBPB and add it to the solution. Heat to 150 °C and react for 2 days. After the reaction is complete, filter and wash the solution. Dry it under vacuum at 80 °C for 12 h to obtain the [TBPB-PS]Br catalyst.

[0032] Figure 1 (c) is the FT-IR spectrum of [TBPB-PS]Br prepared in Example 3; the positive characteristic peak at 1265 cm⁻¹ represents the disappearance of the CH stretching vibration of -CH₂Cl in the catalyst, indicating that the chloromethyl group has been completely reacted, and the negative characteristic peak at 1475 cm⁻¹ represents the FT-IR spectrum of [TBPB-PS]Br prepared in Example 3. -1 The presence of the CH stretching vibration, representing the quaternary ammonium salt CH3, is observed. Due to the presence of trace amounts of water, a 1620 cm⁻¹ vibration is present. -1 and 3410 cm -1 Characteristic peaks and infrared spectral results confirm the successful preparation of the catalyst [TBPB-PS]Br.

[0033] Example 4

[0034] Step 1: Preparation of the active component TMPB: Weigh 0.2 mol of 3-bromopropylamine hydrobromide and 0.4 mol of trimethylamine and add them to 10 mol of water. Mix and stir for 5 days. Obtain a white solid by vacuum distillation. Dissolve the solid in water and adjust the pH to 9-10 with 0.05 mol / L LiOH aqueous solution. Remove water by vacuum distillation to obtain the product 3-trimethylammonium bromide (TMPB).

[0035] Step 2: Preparation of [TMPB-PS]Br catalyst: Weigh 1.8 g of chloromethylated polystyrene resin (CMPS) and soak it in 9 g of toluene for 24 h. Weigh 0.5 g of TMPB and add it to the solution. Heat to 140 °C and react for 3 days. After the reaction is complete, filter and wash the solution. Dry it under vacuum at 60 °C for 16 h to obtain the [TMPB-PS]Br catalyst.

[0036] Example 5

[0037] Step 1: Preparation of the active component TBPB: Weigh 0.15 mol of 3-bromopropylamine hydrobromide and 0.35 mol of tributylamine and add them to 6 mol of water. Mix and stir for 4 days. Obtain a white solid by vacuum distillation. Dissolve the solid in water and adjust the pH to 9-10 with 0.15 mol / L NaOH aqueous solution. Remove water by vacuum distillation to obtain the product 3-tributylammonium bromide (TBPB).

[0038] Step 2: Preparation of [TBPB-PS]Br catalyst: Weigh 1.6 g of chloromethylated polystyrene resin (CMPS) and soak it in 8 g of toluene for 20 h. Weigh 0.5 g of TBPB and add it to the solution. Heat to 120 °C and react for 4 days. After the reaction is complete, filter and wash the solution. Dry it under vacuum at 60 °C for 20 h to obtain the [TBPB-PS]Br catalyst.

[0039] The synthesis of adipic acid chloride from adipic acid was catalyzed by a supported quaternary ammonium salt catalyst.

[0040] Application Example 1

[0041] 1 g of adipic acid, 3 g of thionyl chloride, 0.05 g of [TMPB-PS]Br (Example 1), and 2 g of cyclohexane were weighed and added to a 100 mL three-necked flask. The stirring speed was adjusted to 400 r / min, and the temperature was raised to 50 °C to start the reaction. The reaction was carried out for 5 h. The tail gas was absorbed by 0.01 mol / L sodium hydroxide solution. After the reaction was completed and cooled, the catalyst was separated by centrifugation. The product weight was 1.233 g, and the yield was 98.5%.

[0042] Application Example 2

[0043] 1 g of adipic acid, 3.5 g of trichlorotoluene, 0.1 g of [TEPB-PS]Br (Example 2), and 4 g of toluene were weighed and added to a 100 mL three-necked flask. The stirring speed was adjusted to 400 r / min, and the temperature was raised to 60 °C to start the reaction. The reaction was carried out for 3.5 h. The tail gas was absorbed by 0.03 mol / L potassium hydroxide solution. After the reaction was completed and cooled, the catalyst was separated by centrifugation. The product weight was 1.238 g, and the yield was 98.9%.

[0044] Application Example 3

[0045] 1 g of adipic acid, 5 g of oxaloyl chloride, 0.2 g of [TBPB-PS]Br (Example 3), and 5 g of tetrahydrofuran were weighed and added to a 100 mL three-necked flask. The stirring speed was adjusted to 400 r / min, and the temperature was raised to 80 °C to start the reaction. The reaction was carried out for 2 h. The tail gas was absorbed by 0.1 mol / L calcium hydroxide solution. After the reaction was completed and cooled, the catalyst was separated by centrifugation. The product weight was 1.241 g, and the yield was 99.2%.

[0046] Application Example 4

[0047] 1 g of adipic acid, 4 g of solid phosgene, 0.15 g of [TMPB-PS]Br (Example 4), and 4 g of dichloroethane were weighed and added to a 100 mL three-necked flask. The stirring speed was adjusted to 400 r / min, and the temperature was raised to 70 °C to start the reaction. The reaction was carried out for 3 h. The tail gas was absorbed by 0.08 mol / L lithium hydroxide solution. After the reaction was completed and cooled, the catalyst was separated by centrifugation. The product was distilled under reduced pressure to obtain a pale yellow clear liquid, which was adipic acid chloride. The product weight was 1.235 g, and the yield was 98.7%.

[0048] Application Example 5

[0049] 1 g of adipic acid, 3.5 g of phosphorus trichloride, 0.25 g of [TBPB-PS]Br (Example 5), and 3.5 g of tetrahydrofuran were weighed and added to a 100 mL three-necked flask. The stirring speed was adjusted to 400 r / min, and the temperature was raised to 65 °C to start the reaction. The reaction was carried out for 4.5 h. The tail gas was absorbed by 0.06 mol / L sodium hydroxide solution. After the reaction was completed and cooled, the catalyst was separated by centrifugation. The product was distilled under reduced pressure to obtain a pale yellow clear liquid, which was adipic acid chloride. The product weight was 1.231 g, and the yield was 98.4%.

[0050] The results of the application example experiment are shown in Table 1.

[0051] Table 1. Experimental Results of Application Examples

[0052] Application examples catalyst Adipic acid chloride: chlorination reagent: catalyst Temperature, time Yield (%) Application Example 1 [TMPB-PS]Br 1：3：0.05 50 °C, 5 h 98.5 Application Example 2 [TEPB-PS]Br 1：3.5：0.1 60 °C, 3.5 h 98.9 Application Example 3 [TBPB-PS]Br 1：5：0.2 80 °C, 2 h 99.2 Application Example 4 [TMPB-PS]Br 1：4：0.15 70 °C, 3 h 98.7 Application Example 5 [TBPB-PS]Br 1：3.5：0.25 65 °C, 4.5 h 98.4

Claims

1. A supported quaternary ammonium salt catalyst, characterized in that... Using quaternary ammonium salt as the active component and chloromethylated polystyrene resin (CMPS) as the carrier, with a mass ratio of quaternary ammonium salt to CMPS of 1:(2~4), the following method was used to prepare the product, with the specific steps as follows: (1) Preparation of active components: Weigh 3-bromopropylamine hydrobromide and tertiary amine compounds, add them to water and mix and stir. Obtain solid by vacuum distillation. Dissolve the solid in aqueous solution, adjust the pH to 9-10 with alkaline aqueous solution, remove water by vacuum distillation, and obtain the active component quaternary ammonium salt. (2) Preparation of supported quaternary ammonium salt catalyst: chloromethylated polystyrene resin (CMPS) was weighed and soaked in a solvent for a certain period of time. Then, the active component quaternary ammonium salt was weighed and added to it and stirred and heated to react. After the reaction was completed, the catalyst was filtered, washed and vacuum dried to obtain the supported quaternary ammonium salt catalyst.

2. The supported quaternary ammonium salt catalyst according to claim 1, characterized in that... In step (1), the tertiary amine compound is one of trimethylamine, triethylamine or tributylamine; the molar ratio of 3-bromopropylamine hydrobromide, tertiary amine compound and water is 1:(1~3):(5~15); the stirring time is 3~6 days; the solute of the alkaline aqueous solution is one of sodium hydroxide, potassium hydroxide, calcium hydroxide or lithium hydroxide, and the concentration of the alkaline aqueous solution is 0.05~0.2mol / L.

3. The supported quaternary ammonium salt catalyst according to claim 1, characterized in that... In step (2), the solvent is one of toluene, tetrahydrofuran, dimethyl sulfoxide or DMF; the soaking time is 12~36 h; the mass ratio of the active component quaternary ammonium salt, CMPS to the solvent is 1:(2~4):(15~25); the reaction temperature is 100~150 °C, the reaction time is 2~5 days; the vacuum drying temperature is 50~80 °C, and the drying time is 12~24 h.

4. The application of the supported quaternary ammonium salt catalyst as described in claim 1 in the catalytic synthesis of adipic acid from adipic acid.

5. The application according to claim 4, characterized in that... The prepared catalyst, solvent, adipic acid, and chlorinating reagent were added sequentially to a container. After stirring and heating to the reaction temperature, the reaction began. The tail gas was absorbed by an alkaline aqueous solution. After the reaction was completed and cooled, the catalyst was separated by centrifugation. The pale yellow clear liquid obtained by vacuum distillation was adipic acid chloride.

6. The application according to claim 5, characterized in that... The mass ratio of adipic acid, chlorination reagent, catalyst and solvent is 1:(3~5):(0.05~0.25):(2~5), the reaction temperature is 50~80 °C, and the reaction time is 2~5 h.

7. The application according to claim 5, characterized in that... The chlorinating agent is one of thionyl chloride, solid phosgene, trichlorotoluene, phosphorus trichloride, or oxalyl chloride; the solute in the alkaline aqueous solution is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, or lithium hydroxide; the solvent is one of cyclohexane, tetrahydrofuran, toluene, or dichloroethane; and the concentration of the alkaline aqueous solution is 0.01~0.1 mol / L.

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