A synthesis method for preparing inhibitor 706 using a macroporous sulfonic acid resin catalyst supported on metallic aluminum

Abstract

The present invention provides a synthesis method for preparing 706 polymerization inhibitor by using a macroporous sulfonic acid resin catalyst supported on metallic aluminum, comprising the following steps: soaking the macroporous sulfonic acid resin in an aqueous ammonia solution with four times the volume and stirring, then filtering and drying the mixture to obtain an ammoniated sample; putting an aluminum salt into deionized water and stirring to obtain salt solutions with different molar concentrations, dropping the prepared aluminum salt solution onto the ammoniated sample to completely wet the ammoniated sample, and drying to obtain a macroporous sulfonic acid resin catalyst supported on metallic aluminum; then sequentially adding 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide and dimethyl sebacate into a reaction kettle, adding the macroporous sulfonic acid resin catalyst supported on metallic aluminum for reaction to obtain the product 706 polymerization inhibitor; the synthesis method of the macroporous sulfonic acid resin catalyst supported on metallic aluminum synthesized by the present invention is simple, has high catalytic reaction activity, and has high reaction selectivity in the synthesis of 706 polymerization inhibitor.

Description

Technical Field

[0001] The present invention belongs to the technical fields of catalyst preparation and chemical synthesis, and particularly relates to a synthesis method for preparing 706 polymerization inhibitor by using a macroporous sulfonic acid resin catalyst supported on metallic aluminum. Background Art

[0002] The chemical name of 706 polymerization inhibitor is bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate nitroxide radical. It is a new type of highly efficient and widely used free radical polymerization inhibitor with high polymerization inhibition efficiency and good polymerization inhibition effects in both aerobic and anaerobic environments. It has a relatively high boiling point and molecular weight, and can better resist negative pressure evaporation. Macroporous sulfonic acid resin is a new type of strong acidic solid acid catalyst used to replace concentrated sulfuric acid or p-toluenesulfonic acid in organic synthesis reactions. As a catalyst, it is widely used in fields such as petrochemical industry and fine chemical industry, solving problems such as equipment corrosion, large amounts of neutralization wastewater discharge, and catalyst recovery caused by using concentrated sulfuric acid or p-toluenesulfonic acid as catalysts in the past. Summary of the Invention

[0003] To solve the above problems, the present invention discloses a synthesis method for preparing 706 polymerization inhibitor by using a macroporous sulfonic acid resin catalyst supported on metallic aluminum.

[0004] To achieve the above object, the technical solution of the present invention is as follows:

[0005] A synthesis method for preparing 706 polymerization inhibitor by using a macroporous sulfonic acid resin catalyst supported on metallic aluminum, comprising the following steps:

[0006] Add 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide radical and dimethyl sebacate into a reaction kettle in sequence, then add the macroporous sulfonic acid resin catalyst supported on metallic aluminum, and react at a temperature of 150-200 °C for 6-12 h to obtain the product 706 polymerization inhibitor.

[0007] The synthesis route of the reaction of the present invention is:

[0008] .

[0009] Furthermore, the mass ratio of the macroporous sulfonic acid resin catalyst supported on metallic aluminum to dimethyl sebacate is 1:40-100, and the molar ratio of dimethyl sebacate to 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide radical is 1:1.2-1:2.5.

[0010] The preparation method of the macroporous sulfonic acid resin catalyst supported on metallic aluminum comprises the following steps:

[0011] Step (1): Stir and soak the macroporous sulfonic acid resin in an aqueous ammonia solution with a four-fold volume for at least 2 h, and then filter and dry the mixture to obtain the ammoniated sample;

[0012] Step (2): Put the aluminum salt into deionized water and stir until dissolved to obtain an aluminum salt solution;

[0013] Step (3): Drop the aluminum salt solution obtained in Step (2) onto the ammoniated sample obtained in Step (1) to completely wet the ammoniated sample, and dry it at a certain temperature to obtain the metal aluminum-loaded macroporous sulfonic acid resin catalyst.

[0014] Further, the aqueous ammonia solution in Step (1) is any one or more of ammonia water, ethylamine, ethylenediamine, and propylamine aqueous solution.

[0015] Further, the mass fraction of the aqueous ammonia solution in Step (1) is 10% - 25%.

[0016] Further, the macroporous sulfonic acid resin in Step (1) is Amberlyst 15 sulfonic acid resin.

[0017] Further, the aluminum salt in Step (2) includes any one or more of aluminum nitrate nonahydrate, aluminum sulfate octadecahydrate, and anhydrous aluminum trichloride.

[0018] Further, the molar concentration of the aluminum salt in Step (2) is 0.5 mol / L - 5 mol / L.

[0019] Further, in Step (3), the solid-liquid ratio of the ammoniated sample to the aluminum salt solution is 0.2 - 2:1.

[0020] Further, the drying temperature in Step (3) is 40°C - 80°C.

[0021] The beneficial effects of the present invention are as follows:

[0022] (1) The metal aluminum-loaded macroporous sulfonic acid resin catalyst was first synthesized by the impregnation method, and the synthesis method is simple;

[0023] (2) The metal aluminum-loaded macroporous sulfonic acid resin catalyst is composed of nanoparticles with smaller sizes, and the spherical morphology (see Figure 1 shown) provides more active sites, which is beneficial to improving the reaction activity;

[0024] (3) Innovatively use the metal aluminum-loaded macroporous sulfonic acid resin catalyst as the catalyst for synthesizing the 706 polymerization inhibitor. This solid catalyst has high activity, can be reused, has good repeatability, and still maintains high activity and selectivity after being repeated 25 times. Description of the Drawings

[0025] Figure 1 Scanning electron microscope photograph of the Amberlyst 15 sulfonic acid resin impregnated with ammonia and then with aluminum nitrate nonahydrate synthesized in Example 1 of the present invention.

[0026] Figure 2 FT-IR spectrum of the Amberlyst 15 sulfonic acid resin impregnated with ammonia and then with aluminum nitrate nonahydrate synthesized in Example 1 of the present invention. Specific implementation manners

[0027] The present invention will be further illustrated below in conjunction with the accompanying drawings and specific implementation manners. It should be understood that the following specific implementation manners are only used to illustrate the present invention and not to limit the scope of the present invention.

[0028] The manufacturers and models of the compounds used in the following examples are shown below; other chemical reagents used, unless otherwise specified, are obtained through conventional commercial channels:

[0029]

[0030] Example 1

[0031] (1) Weigh 40 g of Amberlyst 15 sulfonic acid resin, put it into 160 ml of ammonia water with a mass fraction of 25%, stir for 1 h and then let it stand for 1 h. After that, filter and dry the mixture to obtain the ammoniated sample.

[0032] (2) Weigh 0.1 mol of aluminum nitrate nonahydrate and put it into 40 ml of deionized water, stir until dissolved to obtain an aluminum salt solution with a molar concentration of 2.5 mol / L.

[0033] (3) Drop the prepared aluminum salt solution onto the ammoniated Amberlyst 15 sulfonic acid resin, dry at 60 °C, repeatedly drop and dry until all the aluminum salt solution is dropped, and the required catalyst is obtained. The obtained catalyst is numbered CAT-1.

[0034] (4) Add dimethyl sebacate (14.0 g, 0.060 mol), 2,2,6,6-tetramethyl-4-hydroxypiperidine 1-oxyl (24.1 g, 0.14 mol) and 0.28 g of CAT-1 into a 100 mL four-necked flask equipped with a nitrogen protection and distillation device, heat up to 190 °C for reaction, continuously distill out the methanol generated during the reaction. After 8 h, the reaction ends, distill out the excessive 1,2,2,6,6-pentamethylpiperidinol in the reaction. The reaction system is washed with 90 °C hot water (50 mL × 2), and the residual water in the product is distilled off to obtain 28.31 g of orange-red solid, which is the 706 inhibitor, and the yield is 92.4%.

[0035] Example 2

[0036] (1) Weigh 40 g of Amberlyst 15 sulfonic acid resin and put it into 160 ml of ammonia water with a mass fraction of 25%. Stir for 1 h and then let it stand for 1 h. After that, filter and dry the mixture to obtain the ammoniated sample;

[0037] (2) Weigh 0.1 mol of aluminum sulfate octadecahydrate and put it into 40 ml of deionized water. Stir until it dissolves to obtain an aluminum salt solution with a molar concentration of 2.5 mol / L;

[0038] (3) Drop the prepared aluminum salt solution onto the ammoniated Amberlyst 15 sulfonic acid resin, dry at 60 °C, and repeatedly drop and dry until all the aluminum salt solution is dropped. Then the required catalyst is obtained, and the obtained catalyst is numbered CAT-2;

[0039] (4) Add dimethyl sebacate (14.0 g, 0.060 mol), 2,2,6,6-tetramethyl-4-hydroxypiperidine 1-oxyl (20.7 g, 0.12 mol) and 0.32 g of CAT-2 into a 100 mL four-necked flask equipped with a nitrogen protection and distillation device. Heat up to 180 °C for reaction, and continuously distill out the methanol generated during the reaction. After 8 h, the reaction ends, and the excessive 1,2,2,6,6-pentamethylpiperidinol in the reaction is distilled out. The reaction system is washed with 90 °C hot water (50 mL×2), and the residual moisture in the product is distilled off to obtain 27.67 g of orange-red solid, which is the 706 polymerization inhibitor, and the yield is 90.3%.

[0040] Example 3

[0041] (1) Weigh 40 g of Amberlyst 15 sulfonic acid resin and put it into 160 ml of ammonia water with a mass fraction of 25%. Stir for 1 h and then let it stand for 1 h. After that, filter and dry the mixture to obtain the ammoniated sample;

[0042] (2) Weigh 0.1 mol of anhydrous aluminum trichloride and put it into 40 ml of deionized water. Stir until it dissolves to obtain an aluminum salt solution with a molar concentration of 2.5 mol / L;

[0043] (3) Drop the prepared aluminum salt solution onto the ammoniated Amberlyst 15 sulfonic acid resin, dry at 60 °C, and repeatedly drop and dry until all the aluminum salt solution is dropped. Then the required catalyst is obtained, and the obtained catalyst is numbered CAT-3.

[0044] (4) Add dimethyl sebacate (14.0 g, 0.060 mol), 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide (24.8 g, 0.144 mol) and 0.30 g of CAT-3 into a 100 mL four-necked flask equipped with a nitrogen protection and distillation device. Heat up to 150 °C for reaction, and continuously distill out the methanol generated during the reaction. After 10 h, the reaction ends, and the excess 1,2,2,6,6-pentamethylpiperidinol in the reaction is distilled out. The reaction system is washed with 90 °C hot water (50 mL × 2), and the residual water in the product is distilled off to obtain 28.28 g of an orange-red solid, which is the 706 inhibitor, with a yield of 92.3%.

[0045] Example 4

[0046] (1) Weigh 40 g of Amberlyst 15 sulfonic acid resin, put it into 160 ml of 25% ammonia water by mass fraction, stir for 1 h and then let it stand for 1 h. Then filter and dry the mixture to obtain the ammoniated sample;

[0047] (2) Weigh 0.5 mol of aluminum nitrate nonahydrate, put it into 40 ml of deionized water, stir until dissolved to obtain an aluminum salt solution with a molar concentration of 2.5 mol / L;

[0048] (3) Drop the prepared aluminum salt solution onto the ammoniated Amberlyst 15 sulfonic acid resin, dry at 60 °C, repeatedly drop and dry until all the aluminum salt solution is dropped, and the required catalyst is obtained. The obtained catalyst is numbered CAT-4.

[0049] (4) Add dimethyl sebacate (28.0 g, 0.120 mol), 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide (41.4 g, 0.24 mol) and 0.60 g of CAT-4 into a 100 mL four-necked flask equipped with a nitrogen protection and distillation device. Heat up to 200 °C for reaction, and continuously distill out the methanol generated during the reaction. After 10 h, the reaction ends, and the excess 1,2,2,6,6-pentamethylpiperidinol in the reaction is distilled out. The reaction system is washed with 90 °C hot water (50 mL × 2), and the residual water in the product is distilled off to obtain 55.10 g of an orange-red solid, which is the 706 inhibitor, with a yield of 89.9%.

[0050] Example 5

[0051] (1) Weigh 40 g of Amberlyst 15 sulfonic acid resin, put it into 160 ml of 25% ammonia water by mass fraction, stir for 1 h and then let it stand for 1 h. Then filter and dry the mixture to obtain the ammoniated sample;

[0052] (2) Weigh 0.5 mol of aluminum nitrate nonahydrate, put it into 40 ml of deionized water, stir until dissolved, and obtain an aluminum salt solution with a molar concentration of 2.5 mol / L;

[0053] (3) Drop the prepared aluminum salt solution onto the ammoniated Amberlyst 15 sulfonic acid resin, dry it at 80 °C, repeatedly drop and dry until all the aluminum salt solution is dropped, and the required catalyst is obtained. The obtained catalyst is numbered CAT-5.

[0054] (4) Add dimethyl sebacate (14.0 g, 0.060 mol), 2,2,6,6-tetramethyl-4-hydroxypiperidine 1-oxyl (25.8 g, 0.15 mol) and 0.28 g of CAT-5 into a 100 mL four-necked flask equipped with a nitrogen protection and distillation device, heat up to 190 °C for reaction, continuously distill out the methanol generated during the reaction, and after 6 h, the reaction ends. Distill out the excessive 1,2,2,6,6-pentamethylpiperidinol in the reaction. The reaction system is washed with 90 °C hot water (50 mL×2), and the residual water in the product is distilled off to obtain 28.52 g of orange-red solid, which is the 706 polymerization inhibitor, and the yield is 93.1%.

[0055] Example 6

[0056] (1) Weigh 40 g of Amberlyst 15 sulfonic acid resin, put it into 160 ml of an aqueous solution of ethylenediamine with a mass fraction of 10%, stir for 1 h and then stand for 1 h, and then filter and dry the mixture to obtain the ammoniated sample;

[0057] (2) Weigh 0.1 mol of aluminum nitrate nonahydrate and put it into 40 ml of deionized water, stir until dissolved, and obtain an aluminum salt solution with a molar concentration of 2.5 mol / L;

[0058] (3) Drop the prepared aluminum salt solution onto the ammoniated Amberlyst 15 sulfonic acid resin, dry it at 60 °C, repeatedly drop and dry until all the aluminum salt solution is dropped, and the required catalyst is obtained. The obtained catalyst is numbered CAT-6;

[0059] (4) Add dimethyl sebacate (14.0 g, 0.060 mol), 2,2,6,6-tetramethyl-4-hydroxypiperidine 1-oxyl (20.7 g, 0.12 mol), and 0.35 g of CAT-6 into a 100 mL four-necked flask equipped with a nitrogen protection and distillation device. Heat the mixture to 190 °C for reaction, and continuously distill out the methanol generated during the reaction. After 6 h, the reaction ends, and the excess 1,2,2,6,6-pentamethylpiperidinol in the reaction is distilled out. Wash the reaction system with 90 °C hot water (50 mL × 2), and distill off the residual water in the product to obtain 27.09 g of orange-red solid, with a yield of 88.4%.

[0060] Comparative Example 1

[0061] The purpose is to compare with Example 1 to illustrate the effect of the ammoniation treatment step on the catalyst activity.

[0062] (1) Weigh 40 g of Amberlyst 15 sulfonic acid resin, put it into 160 ml of deionized water, stir for 1 h and then let it stand for 1 h. Then filter and dry the mixture to obtain the ammoniated sample;

[0063] (2) Weigh 0.1 mol of aluminum nitrate nonahydrate and put it into 40 ml of deionized water, stir until dissolved to obtain an aluminum salt solution with a molar concentration of 2.5 mol / L;

[0064] (3) Drop the prepared aluminum salt solution onto the ammoniated Amberlyst 15 sulfonic acid resin, dry at 60 °C, and repeatedly drop and dry until all the aluminum salt solution is dropped, then the required catalyst is obtained. The obtained catalyst is numbered CAT-7;

[0065] (4) Add dimethyl sebacate (14.0 g, 0.060 mol), 2,2,6,6-tetramethyl-4-hydroxypiperidine 1-oxyl (24.1 g, 0.14 mol), and 0.28 g of CAT-7 into a 100 mL four-necked flask equipped with a nitrogen protection and distillation device. Heat the mixture to 190 °C for reaction, and continuously distill out the methanol generated during the reaction. After 8 h, the reaction ends, and the excess 1,2,2,6,6-pentamethylpiperidinol in the reaction is distilled out. Wash the reaction system with 90 °C hot water (50 mL × 2), and distill off the residual water in the product to obtain 19.55 g of orange-red solid, which is the 706 inhibitor, with a yield of 63.8%.

[0066] Comparative Example 2

[0067] The purpose is to compare with Example 1 to illustrate the effect of the impregnation step on the catalytic activity.

[0068] (1) Weigh 40 g of Amberlyst 15 sulfonic acid resin and put it into 160 ml of ammonia water with a mass fraction of 25%. Stir for 1 h and then let it stand for 1 h. After that, filter and dry the mixture to obtain the ammoniated sample.

[0069] (2) Weigh 0.1 mol of aluminum nitrate nonahydrate and put it into 40 ml of deionized water. Stir until it dissolves to obtain an aluminum salt solution with a molar concentration of 2.5 mol / L.

[0070] (3) Drop all the prepared aluminum salt solution onto the ammoniated Amberlyst 15 sulfonic acid resin and dry it at 60 °C to obtain the required catalyst. The obtained catalyst is numbered CAT-8.

[0071] (4) Add dimethyl sebacate (14.0 g, 0.060 mol), 2,2,6,6-tetramethyl-4-hydroxypiperidine 1-oxyl (24.1 g, 0.14 mol) and 0.28 g of CAT-8 into a 100 mL four-necked flask equipped with a nitrogen protection and distillation device. Heat up to 190 °C for reaction and continuously distill out the methanol generated during the reaction. After 8 h, the reaction ends, and the excessive 1,2,2,6,6-pentamethylpiperidinol in the reaction is distilled out. Wash the reaction system with 90 °C hot water (50 mL × 2), and evaporate the residual water in the product to obtain 28.43 g of orange-red solid, which is the 706 polymerization inhibitor, and the yield is 92.8%.

[0072] It should be noted that the above content only illustrates the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. For those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements all fall within the protection scope of the claims of the present invention.

Claims

1. A synthetic method for preparing inhibitor 706 using a macroporous sulfonic acid resin catalyst supported on metallic aluminum, characterized in that, It includes the following steps: Add 2,2,6,6-tetramethyl-4-hydroxypiperidine 1-oxyl and dimethyl sebacate into the reaction kettle in sequence, then add the macroporous sulfonic acid resin catalyst supported by metallic aluminum, and react at a temperature of 150~200°C for 6~12h to obtain the product 706 polymerization inhibitor. The reaction route is as follows: ； The preparation method of the macroporous sulfonic acid resin catalyst supported by metallic aluminum includes the following steps: (1) Stir and soak the macroporous sulfonic acid resin with an aqueous ammonia solution four times its volume for at least 2h, then filter and dry the mixture to obtain the ammoniated sample; (2) Put the aluminum salt into deionized water and stir until dissolved to obtain an aluminum salt solution; (3) Drop the aluminum salt solution obtained in step (2) onto the ammoniated sample obtained in step (1) to completely wet the ammoniated sample, and dry it to obtain the macroporous sulfonic acid resin catalyst supported by metallic aluminum.

2. The synthesis method of preparing 706 polymerization inhibitor by using a macroporous sulfonic acid resin catalyst supported on metallic aluminum according to claim 1, characterized in that, The mass ratio of the macroporous sulfonic acid resin catalyst supported by metallic aluminum to the dimethyl sebacate is 1:40~100, and the molar ratio of the dimethyl sebacate to the 2,2,6,6-tetramethyl-4-hydroxypiperidine 1-oxyl is 1:1.2~1:2.

5.

3. The synthesis method of preparing 706 polymerization inhibitor using macroporous sulfonic acid resin catalyst supported by metallic aluminum according to claim 1, characterized in that, The macroporous sulfonic acid resin in step (1) is Amberlyst 15 sulfonic acid resin.

4. The synthesis method of preparing the 706 polymerization inhibitor by using the macroporous sulfonic acid type resin catalyst supported on metallic aluminum according to claim 1, characterized in that, The aqueous ammonia solution in step (1) is any one or more of ammonia water, ethylamine, ethylenediamine, and propylamine aqueous solution.

5. The synthesis method of preparing the 706 polymerization inhibitor by using the macroporous sulfonic acid resin catalyst supported on metallic aluminum according to claim 1, characterized in that, The mass fraction of the aqueous ammonia solution in step (1) is 10%~25%.

6. The synthesis method for preparing the 706 polymerization inhibitor using a macroporous sulfonic acid resin catalyst supported on metallic aluminum according to claim 1, characterized in that, The aluminum salt in step (2) includes any one or more of aluminum nitrate nonahydrate, aluminum sulfate octadecahydrate, and anhydrous aluminum trichloride.

7. The synthesis method of preparing 706 polymerization inhibitor by using macroporous sulfonic acid resin catalyst supported on metallic aluminum according to claim 1, characterized in that, The molar concentration of the aluminum salt in step (2) is 0.5mol / L~5mol / .

8. The synthesis method of preparing the 706 polymerization inhibitor by using the macroporous sulfonic acid type resin catalyst supported on metallic aluminum according to claim 1, characterized in that, The solid-liquid ratio of the ammoniated sample to the aluminum salt solution in step (3) is 0.2~2:

1.

9. The synthesis method for preparing the 706 polymerization inhibitor by using the macroporous sulfonic acid resin catalyst supported on metallic aluminum according to claim 1, wherein, The drying temperature in step (3) is 40°C~80°C.

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