Preparation method of 2, 2, 6, 6-tetramethyl-4-piperidylamine compound

Abstract

The invention relates to the technical field of chemical synthesis, in particular to a preparation method of a 2, 2, 6, 6-tetramethyl-4-piperidinamine compound, which comprises the following steps: adding 2, 2, 6, 6-tetramethyl-4-piperidinamine, a novel catalyst and a solvent into a reaction container, removing air in the reaction container, adding an amine compound, introducing hydrogen, and reacting for 5-6 hours to obtain a solid-liquid mixture; and separating the solid-liquid mixture, collecting a solid phase for later use, and carrying out rotary evaporation and distillation on a liquid phase to obtain the 2, 2, 6, 6-tetramethyl-4-piperidylamine compound. The yield of the obtained product is kept at 96% or above, the product has good thermal stability, the preparation process is simple, the preparation efficiency is improved, the catalyst is convenient to recycle, and the catalyst still has high activity and selectivity after being recycled for 10 times.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing 2,2,6,6-tetramethyl-4-piperidinamine compounds. Background Art

[0002] Piperidine derivatives have very important application value in the chemical industry and are widely used in additives, medicines, pesticides and other fields. Among them, piperidine amine compounds, as a class of amine compounds with steric hindrance effect, are important intermediates for synthesizing hindered amine light stabilizers. For example, 2,2,6,6-tetramethyl-4-piperidinamine can be used to synthesize N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)isophthalamide, UV-90 and other products, and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine can be used to synthesize hindered amine light stabilizers 119, 2020 and other products. The synthesized hindered amine light stabilizer can capture free radicals and has the advantages of high efficiency and non-toxicity. It can be used in large quantities in polymer films and fibers. Even in thicker products, it can effectively slow down the decomposition of polymer materials, has excellent protective properties, and achieves light stabilization effect. Therefore, it is particularly important to develop an efficient and environmentally friendly preparation method for 2,2,6,6-tetramethyl-4-piperidinamine compounds.

[0003] Patent CN113880752B discloses a method for preparing 2,2,6,6-tetramethyl-4-piperidinamine compounds, comprising the following steps: adding raw materials 2,2,6,6-tetramethylpiperidone, amine reactants and solvents into a reactor, stirring and pre-mixing at 10-50°C to form an imine intermediate, then adding a reducing agent at a certain temperature and pressure, and reacting for a certain time to obtain 2,2,6,6-tetramethyl-4-piperidinamine compounds. The invention uses a reducing agent instead of catalytic hydrogenation for reduction, and the yield can reach more than 92%, reducing the generation of by-products and making the operation safer, but the yield of the invention still needs to be improved.

[0004] Patent CN103804282B discloses a method for preparing 2,2,6,6-tetramethyl-4-piperidinamine, including the synthesis of 2,2,6,6-tetramethyl-4-piperidone and the hydrogenation reaction of 2,2,6,6-tetramethyl-4-piperidone; the invention improves the distillation purity and conversion rate of the product by optimizing the distillation, crystallization and hydrogenation reduction processes. The amine used in the invention is liquid ammonia, which may not be applicable to other amine compounds.

[0005] Therefore, there is an urgent need to develop a method for preparing 2,2,6,6-tetramethyl-4-piperidinamine compounds with high yield and high universality. Summary of the invention

[0006] In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a method for preparing 2,2,6,6-tetramethyl-4-piperidinamine compounds. The preparation method is simple, the product yield is maintained at more than 96% and has thermal stability, and the catalyst is easy to recover and can be recycled more than 10 times.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is:

[0008] The present invention provides a method for preparing a 2,2,6,6-tetramethyl-4-piperidinamine compound, comprising the following steps:

[0009] S1. Add 2,2,6,6-tetramethylpiperidone, a novel catalyst, and a solvent into a reaction container, remove the air in the reaction container, add an amine compound, and then introduce hydrogen to react for 5-6 hours to obtain a solid-liquid mixture;

[0010] S2, separating the solid-liquid mixture obtained in step S1, collecting the solid phase for later use, performing liquid phase extraction, collecting the organic phase, and distilling the organic phase to obtain 2,2,6,6-tetramethyl-4-piperidinamine compounds.

[0011] In some embodiments, the amine compound is liquid ammonia or n-butylamine.

[0012] In some embodiments, the solvent is one or more of methanol, isopropanol, and dioxane.

[0013] Preferably, the solvent is dioxane.

[0014] The present invention preferably uses dioxane as the reaction solvent. On the one hand, dioxane has strong solubility and is miscible with water and most organic solvents. On the other hand, dioxane has a high boiling point and can reduce solvent volatilization during the reaction, thereby reducing production costs. In addition, dioxane can reduce the surface tension of the reaction system, allowing the catalyst to be quickly penetrated and accelerating the reaction rate.

[0015] In some embodiments, the molar ratio of the 2,2,6,6-tetramethylpiperidone to the amine compound is 1:(2-3).

[0016] In some embodiments, the mass ratio of the novel catalyst to the total mass of 2,2,6,6-tetramethylpiperidone and the amine compound added is (0.02-0.03):1.

[0017] In some embodiments, the temperature of the hydrogen introduced in step S1 is 55-65° C. and the pressure is 1-3 MPa.

[0018] In some embodiments, the method for preparing the novel catalyst comprises the following steps:

[0019] (1) adding copper acetate, lanthanum nitrate and ammonium bromide to octadecylamine, stirring at room temperature for 30-40 minutes, then adding calcium hydride and stirring for 30-40 minutes, then reacting at 155-165° C. for 15-17 hours, cooling to room temperature, washing and drying to obtain CuLaCa nanomaterials;

[0020] (2) Add cobalt nitrate, nickel nitrate and 2-methylimidazole to methanol and stir at room temperature for 30-40 minutes to obtain a mixed solution; add the CuLaCa nanomaterial obtained in step (1) to methanol and ultrasonicate for 10-20 minutes at an ultrasonic power of 80-100W, then add it to the obtained mixed solution, continue stirring for 2-3 hours, centrifuge, wash and dry, calcine at 790-810°C for 2.5-3.5 hours in a 3-5% H2 / N2 (V / V) atmosphere, then soak in 0.4-0.6 mol / L sulfuric acid for 12-15 hours, filter, wash, dry and grind to obtain a new catalyst.

[0021] At present, 2,2,6,6-tetramethyl-4-piperidinamine compounds are usually prepared by catalytic hydrogenation amination reduction, and the commonly used catalysts are skeleton nickel, skeleton cobalt, etc., and the byproduct 2,2,6,6-tetramethyl-4-piperidinol is inevitably generated during the reaction, and the process of recycling and reusing the catalyst is relatively cumbersome. The present invention first obtains CuLaCa nanomaterials by a solvothermal method using copper acetate, lanthanum nitrate and calcium hydride, and then by Co 2+ 、Ni 2+ The catalyst comprises copper, lanthanum, calcium, cobalt and nickel and has a porous structure. The catalyst has high selectivity, simple recycling and can be recycled for many times. The possible reason is that the cobalt atoms in the outer layer of the catalyst can weaken the ability of nickel to activate carbonyl groups, reduce the generation of by-products and improve the yield of products. The catalytic selectivity is further improved under the synergistic effect of the copper atoms in the pore structure. The lanthanum atoms can increase the adsorption force between the reactants and the catalyst, reduce the activation energy of the reaction and shorten the reaction time. The calcium atoms can absorb the water molecules generated in the reaction process, increase the pH of the reaction system and generate hydrogen, further promote the reaction to proceed in the forward direction and improve the reaction rate. In addition, the catalyst can be reused after simple washing and drying after use, which is convenient to operate.

[0022] In some embodiments, the mass ratio of copper acetate, lanthanum nitrate, and calcium hydride in step (1) is 1:(0.6-0.8):(0.9-0.11).

[0023] In some embodiments, the mass ratio of cobalt nitrate, nickel nitrate, 2-methylimidazole and methanol in step (2) is (0.009-0.011):(0.02-0.03):(0.05-0.07):1.

[0024] The present invention limits the mass ratio of copper acetate, lanthanum nitrate and calcium hydride and the mass ratio of cobalt nitrate, nickel nitrate, 2-methylimidazole and methanol, so that, on the one hand, the ability of nickel to activate carbonyl groups is weakened while the reaction rate is not reduced, and on the other hand, the pH value of the reaction system is prevented from being too high to affect the generation of imine groups. In addition, by limiting the mass ratio of each substance, the stability of the catalyst can be enhanced and the durability of the catalyst can be improved.

[0025] In some embodiments, the mass ratio of the mixed solution to the CuLaCa nanomaterial in step (2) is (30-40):1.

[0026] The invention limits the mass ratio of the mixed solution and the CuLaCa nano material so that the CuLaCa nano material is coated and still has a suitable specific surface area, so that the reactant can achieve a higher conversion rate and a higher yield in a shorter time.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] 1. The present invention limits the ratio between 2,2,6,6-tetramethylpiperidone, amine compounds and catalysts, so that the reaction can occur without high temperature and high pressure, and at the same time, the generation of by-products can be reduced, and the conversion rate and product yield can be improved.

[0029] 2. The present invention first obtains CuLaCa nanomaterials by a solvothermal method using copper acetate, lanthanum nitrate and calcium hydride, and then by Co 2+ 、Ni 2+ Through coordination and self-assembly with 2-methylimidazole, a stable framework and porous structure are formed, and the CuLaCa nanomaterial is further coated to obtain a catalyst containing copper, lanthanum, calcium, cobalt, and nickel, with a porous structure, high selectivity, simple recycling, and can be recycled many times.

[0030] 3. The present invention limits the ratio between the substances in the catalyst, which, on the one hand, weakens the ability of nickel to activate the carbonyl group without reducing the reaction rate, and on the other hand, avoids the excessive pH of the reaction system affecting the formation of the imine group. In addition, by limiting the mass ratio of each substance, the stability of the catalyst can be enhanced and the durability of the catalyst can be improved. DETAILED DESCRIPTION

[0031] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples and comparative examples are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0032] In order to facilitate those skilled in the art to implement the present invention, some raw materials and manufacturers of the embodiments and comparative examples are described as follows: the compounds and related reagents used in the present invention can be purchased from the market.

[0033] Preparation Example 1

[0034] The preparation method of the novel catalyst-1 comprises the following steps:

[0035] (1) 1 g of copper acetate, 0.7 g of lanthanum nitrate and 1.1 g of ammonium bromide were added to 30 ml of octadecylamine, stirred at room temperature for 35 min, then 1 g of calcium hydride was added and stirred for 35 min, then reacted at 160° C. for 16 h, cooled to room temperature, washed and dried to obtain CuLaCa nanomaterials;

[0036] (2) Add 1 g of cobalt nitrate, 2.5 g of nickel nitrate and 6 g of 2-methylimidazole to 100 g of anhydrous methanol and stir at room temperature for 35 min to obtain a mixed solution; add 1 g of the CuLaCa nanomaterial obtained in step (1) to 25 g of anhydrous methanol and ultrasonicate for 15 min at an ultrasonic power of 90 W, then add the mixture to 35 g of the obtained mixed solution and continue stirring for 2.5 h. After centrifugation, washing and drying, calcining at 800° C. for 3 h in a 4% H2 / N2 (V / V) atmosphere, then soaking in 0.5 mol / L sulfuric acid for 13 h, filtering, washing, drying and grinding to obtain the novel catalyst-1.

[0037] Preparation Example 2

[0038] The preparation method of the novel catalyst-2 is the same as that of Preparation Example 1, except that the amount of lanthanum nitrate added in step (1) is 1 g.

[0039] Preparation Example 3

[0040] The preparation method of the novel catalyst-3 is the same as that of Preparation Example 1, except that the amount of cobalt nitrate added in step (2) is 1.4 g.

[0041] Preparation Example 4

[0042] The preparation method of the novel catalyst-4 is the same as that of Preparation Example 1, except that the amount of nickel nitrate added in step (2) is 4 g.

[0043] Preparation Example 5

[0044] The preparation method of the novel catalyst-5 is the same as that of Preparation Example 1, except that the amount of the mixed liquid added in step (2) is 45 g.

[0045] The specific surface area of ​​the novel catalyst obtained in Preparation Examples 1-5 was tested using an IQ specific surface and porosity analyzer, and its specific surface area was calculated using Brunauer-Emmett-Teller. The test results are shown in Table 1.

[0046] Table 1

[0047] Group <![CDATA[S BET (m 2 / g)]]> Preparation Example 1 512 Preparation Example 2 491 Preparation Example 3 529 Preparation Example 4 541 Preparation Example 5 684

[0048] It can be seen from the data in Table 1 that the new catalyst has a larger specific surface area, indicating that the new catalyst with a porous structure has been successfully prepared.

[0049] Example 1

[0050] A method for preparing N-butyl-2,2,6,6-tetramethyl-4-piperidinamine comprises the following steps:

[0051] S1. Add 1.85 g of 2,2,6,6-tetramethylpiperidone, 0.092 g of novel catalyst-1, and 50 ml of dioxane into a reaction container, remove the air in the reaction container, add 1.83 g of n-butylamine, and then introduce hydrogen at a temperature of 60° C. and a pressure of 2 MPa. React for 5.5 h to obtain a solid-liquid mixture.

[0052] S2. The solid-liquid mixture obtained in step S1 is subjected to solid-liquid separation, the solid phase is collected for standby use, liquid phase extraction is performed, the organic phase is collected and combined, 2 g of anhydrous sodium sulfate is added, dried, filtered, and distilled to obtain N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.

[0053] Example 2

[0054] A method for preparing N-butyl-2,2,6,6-tetramethyl-4-piperidinamine comprises the following steps:

[0055] S1. Add 1.85 g of 2,2,6,6-tetramethylpiperidone, 0.67 g of novel catalyst-1, and 50 ml of dioxane into a reaction container, remove the air in the reaction container, add 1.5 g of n-butylamine, and then introduce hydrogen at a temperature of 55° C. and a pressure of 1 MPa. React for 6 h to obtain a solid-liquid mixture.

[0056] S2, performing solid-liquid separation on the solid-liquid mixture obtained in step S1, collecting the solid phase for later use, liquid extraction, collecting and combining the organic phases, drying over anhydrous sodium sulfate, filtering, and distilling to obtain N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.

[0057] Example 3

[0058] A method for preparing N-butyl-2,2,6,6-tetramethyl-4-piperidinamine comprises the following steps:

[0059] S1. Add 1.85 g of 2,2,6,6-tetramethylpiperidone, 0.12 g of novel catalyst-1, and 50 ml of dioxane into a reaction container, remove the air in the reaction container, add 2.19 g of n-butylamine, and then introduce hydrogen at a temperature of 65° C. and a pressure of 3 MPa. React for 5 h to obtain a solid-liquid mixture.

[0060] S2, performing solid-liquid separation on the solid-liquid mixture obtained in step S1, collecting the solid phase for later use, liquid extraction, collecting and merging the organic phases, drying over anhydrous sodium sulfate, filtering, distilling, and collecting fractions to obtain N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.

[0061] Example 4

[0062] A method for preparing 2,2,6,6-tetramethyl-4-piperidinamine comprises the following steps:

[0063] S1. Add 1.85 g of 2,2,6,6-tetramethylpiperidone, 0.057 g of novel catalyst-1, and 50 ml of dioxane into a reaction container, remove the air in the reaction container, add 0.43 g of liquid ammonia, and then introduce hydrogen at a temperature of 60° C. and a pressure of 2 MPa. React for 5.5 h to obtain a solid-liquid mixture.

[0064] S2. The solid-liquid mixture obtained in step S1 is subjected to solid-liquid separation, the solid phase is collected for standby use, liquid phase extraction is performed, the organic phase is collected and combined, 2 g of anhydrous sodium sulfate is added, dried, filtered, and distilled to obtain N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.

[0065] Example 5

[0066] A method for preparing N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, the specific implementation manner is the same as that of Example 1, except that in step S1, an equal amount of a new catalyst-1 is replaced by a new catalyst-2.

[0067] Example 6

[0068] A method for preparing N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, the specific implementation manner is the same as that of Example 1, except that in step S1, an equal amount of the new catalyst-1 is replaced by the new catalyst-3.

[0069] Example 7

[0070] A method for preparing N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, the specific implementation manner is the same as that of Example 1, except that in step S1, an equal amount of the new catalyst-1 is replaced by the new catalyst-4.

[0071] Example 8

[0072] A method for preparing N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, the specific implementation manner is the same as that of Example 1, except that in step S1, an equal amount of the new catalyst-1 is replaced by the new catalyst-5.

[0073] Comparative Example 1

[0074] A method for preparing N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, the specific implementation manner is the same as that of Example 1, except that in step S1, an equal amount of the new catalyst-1 is replaced by Raney nickel.

[0075] Performance Test:

[0076] 1. Yield and purity

[0077] The products of the above examples and comparative examples were quantitatively analyzed by gas chromatograph to obtain the purity; yield (%) = actual yield / theoretical yield × 100%.

[0078] 2. Thermal stability test

[0079] The products of the above embodiments and comparative examples were subjected to thermal stabilizer verification: 1 g of the product was taken to detect the chromaticity on a colorimeter, then allowed to stand at 50° C. for 4 h, taken out, and the chromaticity was detected again, and it was recorded whether the chromaticity increase was less than 10 Hazen.

[0080] The test results are shown in Table 2.

[0081] Table 2

[0082] Components purity% Yield % Less than 10 Hazen Example 1 99.6 97.6 yes Example 2 99.4 97.4 yes Example 3 99.5 97.3 yes Example 4 99.5 97.5 yes Example 5 99.1 97.1 yes Example 6 98.9 96.9 yes Example 7 98.2 97.0 yes Example 8 98.4 97.2 yes Comparative Example 1 97.8 97.1 no

[0083] By comparing the experimental data of Examples 1-4 in Table 2, it can be seen that after the reaction temperature, time, pressure and ratio are changed, 2,2,6,6-tetramethyl-4-piperidinamine compounds can maintain a high yield, purity and excellent thermal stability; by comparing Example 5 with Example 1, it can be seen that the increase in the amount of lanthanum nitrate in the new catalyst-2 may lead to an increase in catalyst activity, a decrease in selectivity, and a decrease in the purity of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; by comparing Example 6 with Example 1, it can be seen that the increase in the amount of cobalt nitrate in the new catalyst 3 may lead to a decrease in the reaction activity of the catalyst. The ratio of nickel nitrate to nitric acid is too large, resulting in a decrease in the yield of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; compared with Example 7 and Example 1, it can be seen that the increase in the amount of nickel nitrate in the new catalyst-4 may lead to an increase in the activity of the catalyst and a decrease in the selectivity, thereby resulting in a decrease in the purity of the product; compared with Example 1 and Example 8, it can be seen that the increase in the amount of the mixed liquid in the new catalyst-5 may lead to an increase in the specific surface area of ​​the catalyst, an increase in the catalytic comparative activity, a decrease in the selectivity, and a decrease in the purity of the product; compared with Example 1 and Comparative Example 1, it can be seen that the use of Raney nickel leads to an increase in by-products, a decrease in purity, and a decrease in thermal stability.

[0084] 3. Catalyst recyclability

[0085] After the catalyst was recycled 10 times, it was used in Example 1 and Example 4. The products of Example 1 and Example 4 were quantitatively analyzed by gas chromatography to obtain the purity. Yield (%) = actual yield / theoretical yield × 100%.

[0086] The test results are shown in Table 3.

[0087] Table 3

[0088] Group purity Yield Example 1 99.1％ 96.3％ Example 4 98.9％ 96.6％

[0089] From the data of Example 1 and Example 4 in Table 3, it can be seen that the catalyst still has good catalytic activity and maintains good selectivity after 10 cycles.

[0090] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of equivalent changes using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for preparing 2,2,6,6-tetramethyl-4-piperidinamine compounds, It is characterized in that The following steps are involved: S1. Add 2,2,6,6-tetramethylpiperidone, a novel catalyst, and a solvent into a reaction container, remove the air in the reaction container, add an amine compound, and then introduce hydrogen to react for 5-6 hours to obtain a solid-liquid mixture; S2, separating the solid-liquid mixture obtained in step S1, collecting the solid phase for later use, performing liquid phase extraction, collecting the organic phase, and distilling the organic phase to obtain 2,2,6,6-tetramethyl-4-piperidinamine compounds.

2. The method for preparing 2,2,6,6-tetramethyl-4-piperidinamine compounds according to claim 1, It is characterized in that The amine compound is liquid ammonia or n-butylamine.

3. A method for preparing a 2,2,6,6-tetramethyl-4-piperidinamine compound according to claim 1, It is characterized in that The solvent is one or more of methanol, isopropanol and dioxane.

4. A method for preparing a 2,2,6,6-tetramethyl-4-piperidinamine compound according to claim 1, It is characterized in that The molar ratio of the 2,2,6,6-tetramethylpiperidone to the amine compound is 1:(2-3).

5. A method for preparing a 2,2,6,6-tetramethyl-4-piperidinamine compound according to claim 1, It is characterized in that The mass ratio of the novel catalyst to the total mass of 2,2,6,6-tetramethylpiperidone and amine compounds added is (0.02-0.03):

1.

6. A method for preparing a 2,2,6,6-tetramethyl-4-piperidinamine compound according to claim 1, It is characterized in that The temperature of the hydrogen introduced in step S1 is 55-65° C. and the pressure is 1-3 MPa.

7. A method for preparing a 2,2,6,6-tetramethyl-4-piperidinamine compound according to claim 1, It is characterized in that The preparation method of the novel catalyst comprises the following steps: (1) adding copper acetate, lanthanum nitrate and ammonium bromide to octadecylamine, stirring at room temperature for 30-40 minutes, then adding calcium hydride and stirring for 30-40 minutes, then reacting at 155-165° C. for 15-17 hours, cooling to room temperature, washing and drying to obtain CuLaCa nanomaterials; (2) adding cobalt nitrate, nickel nitrate and 2-methylimidazole to methanol and stirring at room temperature for 30-40 minutes to obtain a mixed solution; adding the CuLaCa nanomaterial obtained in step (1) to methanol and ultrasonically treating for 10-20 minutes at an ultrasonic power of 80-100 W, and then adding the CuLaCa nanomaterial to the obtained mixed solution, stirring for 2-3 hours, centrifuging, washing and drying, and heating at 3-5% H 2 / N 2 Under (V / V) atmosphere, calcine at 790-810°C for 2.5-3.5h, then soak in 0.4-0.6mol / L sulfuric acid for 12-15h, filter, wash, dry and grind to obtain a new catalyst.

8. A method for preparing a 2,2,6,6-tetramethyl-4-piperidinamine compound according to claim 7, It is characterized in that In the step (1), the mass ratio of copper acetate, lanthanum nitrate and calcium hydride is 1:(0.6-0.8):(0.9-0.11).

9. A method for preparing 2,2,6,6-tetramethyl-4-piperidinamine compounds according to claim 7, It is characterized in that In the step (2), the mass ratio of cobalt nitrate, nickel nitrate, 2-methylimidazole and methanol is (0.009-0.011):(0.02-0.03):(0.05-0.07):

1.

10. A method for preparing a 2,2,6,6-tetramethyl-4-piperidinamine compound according to claim 9, It is characterized in that The mass ratio of the mixed solution to the CuLaCa nanomaterial in the step (2) is (30-40):1.