Hindered amine light stabilizer 119 and preparation method thereof
By using a supported base catalyst and a precatalyst in the preparation process of the hindered amine light stabilizer 119, the reaction efficiency and selectivity are improved, and the problems of low catalytic efficiency and insufficient product yield in the prior art are solved, thereby achieving high efficiency and low energy The production method of consumption improves product quality.
Patent Information
- Application Number
- CN202411411237.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-10
- Publication Date
- 2025-01-10
AI Technical Summary
The method for preparing hindered amine light stabilizer 119 in the prior art has low catalytic efficiency, requires high temperature and high energy consumption, and insufficient selectivity and yield of four-substituted products, resulting in unsatisfactory reaction efficiency and product quality.
The reaction is carried out in different steps using a supported base catalyst and a precatalyst, reducing the reaction conditions, improving the reaction efficiency and selectivity, and the reaction is carried out through the reaction of the intermediate with N,N'-bis(3-aminopropyl)ethylenediamine and methyl The supported base catalyst and precatalyst are added during the fusion process to improve the reaction efficiency and yield.
The reaction efficiency and product selectivity are significantly improved, energy consumption and by-product generation are reduced, the purity and yield of the product are improved, the separation process is simplified, and it is suitable for the production of hindered amine light stabilizer 119.
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Abstract
Description
Technical Field
[0001] The present invention relates to the field of polymer material modification additives, and in particular to a hindered amine light stabilizer 119 and a preparation method thereof. Background Art
[0002] Light stabilizer is an additive for polymer products. It can shield or absorb ultraviolet energy, quench singlet oxygen and decompose hydroperoxide into inactive substances. It can eliminate or slow down the possibility of photochemical reaction of polymer under light radiation, prevent or delay the process of photoaging, and thus extend the service life of polymer products.
[0003] Hindered amine light stabilizers are highly effective additives for inhibiting the photo-oxidative degradation of polymer materials. Their light stabilization effect is 2-4 times that of traditional absorption-type light stabilizers. This type of substance has a good synergistic effect with ultraviolet absorbers and antioxidants, and has good compatibility with a variety of polymer materials. As the uses and effects of light stabilizers are gradually expanded and recognized, hindered amine light stabilizers with better performance are one of the main research directions.
[0004] Among them, hindered amine light stabilizer 119 is a monomeric high molecular weight hindered amine light stabilizer with excellent extraction resistance and migration resistance. Hindered amine light stabilizer 119 is particularly suitable for PP, PE, olefin copolymers and their blends with EPR, EPDM, ERR, PE, EVA, EAA, EVOH, filled PP and other materials. It can also be used for elastomers, styrene and α-methylstyrene materials and blends or alloys of these polymers with other materials, adhesives, hot melt adhesives, soft and hard PVC, polyurethane, polyamide, homopolymer and copolymer POM, PPE, PET, PBT blends, PMMA casting sheets, thermoplastic resins and UPE, PET, PA fibers, etc. It is precisely because light stabilizer 119 has such a rich application range and good effects that the product market prospects are extremely broad.
[0005] As a tetrasubstituted product, hindered amine light stabilizer 119 has a large steric hindrance during the preparation reaction, which requires a higher temperature and higher mass transfer requirements. In the prior art, xylene and water are mixed and a high temperature of 180°C and reaction conditions of 35 hours are required to meet the industrial requirements of tetrasubstituted selectivity and conversion rate.
[0006] In addition, the preparation method of hindered amine light stabilizer 119 in the prior art uses conventional catalysts, which not only leads to low catalytic efficiency and requires high energy consumption, but also has low selectivity for tetrasubstituted products in the reaction, and the final yield of the reaction still needs to be improved.
[0007] Therefore, there is an urgent need for a method for preparing hindered amine light stabilizer 119 that can not only improve the reaction catalytic efficiency but also have a high selectivity for tetrasubstituted products and can effectively improve the product yield. Summary of the invention
[0008] Purpose of the invention: In view of the defects of the prior art, the purpose of the present invention is to provide a hindered amine light stabilizer 119 and a preparation method thereof, which can not only improve the reaction catalytic efficiency but also have high selectivity for tetrasubstituted products and effectively improve the product yield.
[0009] Technical solution:
[0010] A method for preparing a hindered amine light stabilizer 119 comprises the following steps:
[0011] (1) In a reactor, add N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, cyanuric chloride, a base catalyst and an organic solvent, heat to 40-70° C. for reaction for 8-12 hours, and after the reaction, cool, separate, wash and dry to obtain intermediate I;
[0012] (2) In a reactor, add intermediate I, N,N'-di(3-aminopropyl)ethylenediamine, a supported base catalyst and an organic solvent, heat to 150-180°C and reflux for reaction for 8-16 hours, and after the reaction is completed, cool, separate, wash and dry to obtain intermediate II;
[0013] (3) adding a precatalyst, intermediate II, an aldehyde compound and deionized water into an autoclave, introducing nitrogen to replace the air, heating to 70-95° C. for reflux reaction for 8-12 hours, cooling, dehydrating, filtering and drying after the reaction to obtain the hindered amine light stabilizer 119;
[0014] The preparation process of the hindered amine light stabilizer 119 is as follows:
[0015]
[0016] in,
[0017] Furthermore, the organic solvent is selected from one of toluene, xylene, trimethylbenzene or C7-C9 alkane; the alkaline catalyst is selected from one of sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
[0018] Furthermore, in the step (1), the mass ratio of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to cyanuric chloride is 3-4:3.
[0019] Furthermore, in the step (2), the mass ratio of N,N'-di(3-aminopropyl)ethylenediamine, intermediate I and supported base catalyst is (0.3-0.5):(3.5-4.5):(0.1-0.2).
[0020] The invention adds a supported base catalyst during the reaction of the intermediate I with N,N'-di(3-aminopropyl)ethylenediamine. On the one hand, the reaction conditions can be reduced and the reaction efficiency can be improved, and the selectivity of the tetra-substitution reaction in the reaction process can be effectively improved, and the yields of the tetra-substitution product and the final product can be improved. On the other hand, the supported base catalyst is easier to separate and recover than a conventional homogeneous catalyst, and the separation difficulty can be effectively reduced, and the reaction efficiency can be improved.
[0021] Furthermore, the supported base catalyst in step (2) is prepared by the following steps: adding metal nitrate, template F127 and deionized water into a reactor, adding mesoporous silica after dissolution, stirring at 50-100 r / min for 4-6 hours, filtering, transferring to a muffle furnace and calcining at 500-600° C. for 6-8 hours to obtain the supported base catalyst.
[0022] The present invention prepares a supported base catalyst by using metal nitrate and mesoporous silica. The mesoporous silica can be evenly dispersed in the reaction system, thereby effectively increasing the contact area between the reactants and the catalyst during the reaction, further improving the reaction efficiency and the selectivity of the product, and reducing the generation of by-products. In addition, the supported base catalyst has excellent stability and can exert its catalytic function for a long time.
[0023] Furthermore, the metal nitrate is selected from one of sodium nitrate, calcium nitrate, copper nitrate, zinc nitrate or cerium nitrate; and the mass ratio of the metal nitrate to the mesoporous silica is 1:3-5.
[0024] Furthermore, the aldehyde compound is selected from one of formaldehyde and paraformaldehyde.
[0025] Furthermore, in the step (3), the mass ratio of the precatalyst, the intermediate II and the aldehyde compound is (0.1-0.2):(4-6):(1-2).
[0026] Furthermore, the precatalyst in step (3) is selected from one of bis(2-methylallyl)palladium chloride dimer and crotonylpalladium chloride dimer.
[0027] The present invention can further improve the reaction efficiency and the yield of the product by adding a pre-catalyst during the methylation reaction of the intermediate II, and can reduce the generation of side reactions and the production of impurities, thereby controlling the reaction energy consumption and increasing the reaction capacity, so that it can be widely used in the production process of the hindered amine light stabilizer 119.
[0028] The hindered amine light stabilizer 119 obtained by any of the above-mentioned preparation methods of the hindered amine light stabilizer 119.
[0029] Beneficial effects:
[0030] (1) In the hindered amine light stabilizer 119 and the preparation method thereof provided by the present invention, by adding a supported base catalyst during the reaction of intermediate I with N,N'-di(3-aminopropyl)ethylenediamine and adding a pre-catalyst during the methylation reaction of intermediate II, not only the reaction efficiency can be significantly improved, but also the selectivity of the tetrasubstituted product and the yield of the final reaction product can be effectively improved, thereby controlling the reaction energy consumption and improving the reaction capacity.
[0031] (2) In the preparation method of hindered amine light stabilizer 119 provided by the present invention, by adding a supported base catalyst during the reaction of intermediate I with N,N'-di(3-aminopropyl)ethylenediamine, on the one hand, not only can the reaction conditions be reduced and the reaction efficiency be improved, but also the selectivity of the tetrasubstitution reaction during the reaction process can be effectively improved, and the yield of the tetrasubstitution product and the final product can be increased; on the other hand, the supported base catalyst is easier to separate and recover than conventional homogeneous catalysts, which can effectively reduce the difficulty of separation and improve the reaction efficiency.
[0032] (3) In the preparation method of the hindered amine light stabilizer 119 provided by the present invention, a supported base catalyst is prepared by metal nitrate and mesoporous silica. The mesoporous silica can be evenly dispersed in the reaction system, which can effectively increase the contact area between the reactants and the catalyst during the reaction. It can not only effectively improve the reaction efficiency, but also significantly reduce the reaction temperature and shorten the reaction time. It can also further improve the reaction efficiency and product selectivity, reduce the generation of by-products, and improve product quality. At the same time, the supported base catalyst has excellent stability and can exert its catalytic function for a long time.
[0033] (4) In the preparation method of hindered amine light stabilizer 119 provided by the present invention, by adding a pre-catalyst during the methylation reaction of intermediate II, the reaction efficiency and the yield of the product can be further improved, and the generation of side reactions and impurities can be reduced, thereby controlling the reaction energy consumption and increasing the reaction capacity, so that it can be widely used in the production process of hindered amine light stabilizer 119.
[0034] (5) In the preparation method of the hindered amine light stabilizer 119 provided by the present invention, by adding a supported base catalyst and a pre-catalyst simultaneously during the amino condensation and methylation reaction processes, not only can the reaction efficiency of the single-step reaction process be improved respectively, but also after the amino condensation reaction is catalyzed by the supported base catalyst, the selectivity of the tetra-substitution reaction is high and the product purity is high, and the intermediate purification process can be omitted, so that the product can have a higher purity in the methylation process, and the catalytic ability of the pre-catalyst can be fully utilized, thereby significantly improving the overall reaction efficiency and the yield of the final product. DETAILED DESCRIPTION
[0035] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are examples of the present invention and are only used to illustrate the present invention, but are not used to limit the present invention. Without departing from the gist or scope of the present invention, other combinations and various improvements within the concept of the present invention may be carried out. Reagents and equipment in the present invention are conventional reagents and equipment in the art.
[0036] Preparation of supported base catalyst
[0037] The supported base catalyst was prepared by the following steps:
[0038] In the reactor, 1 g of sodium nitrate, 0.5 g of template F127 and 100 mL of deionized water were added, and after stirring to dissolve, 5 g of mesoporous silica was added. After stirring at 100 r / min for 6 hours, the mixture was filtered and transferred to a muffle furnace and calcined at 600° C. for 8 hours to obtain the supported base catalyst.
[0039] Example 1
[0040] The hindered amine light stabilizer 119 was prepared by the following steps:
[0041] (1) In a reactor, 4 g of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, 0.3 g of sodium hydroxide and 50 mL of xylene were added dropwise at 40° C. A mixed solution of 3 g of cyanuric chloride and 50 g of xylene was added dropwise. After the addition was completed, the mixture was heated to 60° C. and reacted for 8-12 hours. After the reaction was completed, the mixture was cooled, separated, washed and dried to obtain an intermediate I.
[0042] (2) In a reactor, 4 g of intermediate I, 0.4 g of N,N'-di(3-aminopropyl)ethylenediamine, 0.1 g of a supported base catalyst and 50 mL of xylene were added, and the mixture was heated to 160° C. and refluxed for reaction for 8-16 hours. After the reaction was completed, the intermediate II was obtained after cooling, separation, washing and drying.
[0043] (3) In an autoclave, 0.1 g of bis(2-methylallyl)palladium chloride dimer, 5 g of intermediate II, 2 g of polyformaldehyde and 10 mL of deionized water were added, nitrogen was introduced to replace the air, and the mixture was heated to 85° C. and refluxed for 8-12 hours. After the reaction was completed, the mixture was cooled, washed with water for dehydration, filtered and dried to obtain the hindered amine light stabilizer 119.
[0044] Example 2
[0045] The method is basically the same as Example 1, except that the sodium hydroxide in step (1) is replaced by an equal amount of sodium bicarbonate.
[0046] Example 3
[0047] The method is basically the same as Example 1, except that the bis(2-methylallyl)palladium chloride dimer in step (3) is replaced by an equal amount of crotonylpalladium chloride dimer.
[0048] Comparative Example 1
[0049] The method is basically the same as Example 1, except that the supported base catalyst in step (2) is replaced by an equal amount of sodium hydroxide; and the precatalyst in step (3) is replaced by an equal amount of Pd / C catalyst.
[0050] Comparative Example 2
[0051] The method is basically the same as Example 1, except that the supported base catalyst in step (2) is replaced by an equal amount of sodium hydroxide.
[0052] Comparative Example 3
[0053] The process is basically the same as Example 1, except that the pre-catalyst in step (3) is replaced by an equal amount of Pd / C catalyst.
[0054] Comparative Example 4
[0055] The hindered amine light stabilizer 119 was prepared by the following steps:
[0056] (1) In a reactor, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, sodium hydroxide and xylene are added dropwise to a mixture of cyanuric chloride and xylene at 40° C. After the addition is completed, the mixture is heated to 85° C. and reacted for 8-12 hours. After the reaction is completed, the mixture is cooled, separated, washed and dried to obtain an intermediate I;
[0057] (2) In a reactor, add intermediate I into a methylation synthesis kettle and heat it to 95° C., then add formaldehyde and formic acid dropwise, and complete the addition over 4 hours. Then, reflux and keep the reaction temperature for 8-16 hours. After the synthesis is completed, cool to 75° C., add a certain amount of 30% liquid alkali dropwise, stir for 2 hours, cool, and stand for 1 hour to remove the alkali water to obtain a methylation synthesis solution;
[0058] (3) The methylation synthesis liquid of step (2) is transferred into an autoclave, and a certain amount of tetramine and 30% liquid alkali are added by a pump. The feed port is closed, and the gas is replaced with nitrogen three times. The stirring is turned on to raise the autoclave temperature to 170°C, and the reaction is kept at this temperature for 24-36 hours. The temperature is then lowered to 80°C, and the alkali water is separated. The upper layer of the material is transferred to a dehydration autoclave, and the hindered amine light stabilizer 119 is obtained after dehydration, filtration, washing, and drying.
[0059] Performance Testing
[0060] Catalytic effect detection: The reaction temperature and the time when the reaction is completely completed in the amino condensation and methylation process in Examples 1-3 and Comparative Examples 1-4 were recorded respectively. The results are shown in the following table:
[0061] Amine condensation temperature (℃) Amine condensation time (h) Methylation temperature (℃) Methylation time (h) Example 1 160 10 85 8 Example 2 160 10 85 8 Example 3 160 10 85 8 Comparative Example 1 160 16 85 12 Comparative Example 2 160 16 85 10 Comparative Example 3 160 10 85 12 Comparative Example 4 170 30 95 14
[0062] According to the comparison of the test results of Examples 1-3 with Comparative Examples 1 and 4, it can be seen that the preparation method of the hindered amine light stabilizer 119 provided by the present invention has a better catalytic effect than the preparation method in the prior art, and can further reduce the temperature and reaction time of the amino condensation and methylation reactions, thereby significantly improving the reaction efficiency.
[0063] According to the comparison of the test results of Examples 1-3 with Comparative Examples 2 and 3, it can be seen that in the preparation method of hindered amine light stabilizer 119 provided by the present invention, by adding a supported base catalyst and a pre-catalyst during the amino condensation reaction and the methylation reaction, the reaction efficiency can be significantly improved, thereby controlling the reaction energy consumption and increasing the reaction capacity.
[0064] Selectivity and yield detection: The contents of disubstituted product, trisubstituted product and tetrasubstituted hindered amine light stabilizer 119 in the products of Examples 1-3 and Comparative Examples 1-3, as well as the yield of tetrasubstituted product based on N,N'-bis(3-aminopropyl)ethylenediamine were detected by HPLC.
[0065] Transmittance detection: Take 10g of the products of Examples 1-3 and Comparative Examples 1-4 respectively, add them to toluene to prepare a 10% solution, use toluene as a blank, and read the transmittance at 425nm on a spectrophotometer.
[0066] The test results are shown in the following table:
[0067]
[0068] According to the comparison of the test results of Examples 1-3 with Comparative Examples 1 and 4, it can be seen that the method for preparing the hindered amine light stabilizer 119 provided by the present invention can significantly improve the selectivity and yield of the preparation method by adding a supported base catalyst during the reaction of intermediate I with N,N'-di(3-aminopropyl)ethylenediamine and adding a pre-catalyst during the methylation reaction of intermediate II, thereby improving the quality of the product and being widely used in the field of preparation of hindered amine light stabilizer 119.
[0069] According to the comparison of the test results of Examples 1-3 and Comparative Example 2, the preparation method of hindered amine light stabilizer 119 provided by the present invention can significantly improve the selectivity of tetrasubstituted products in the preparation process and improve the yield of the preparation by adding a supported base catalyst.
[0070] According to the comparison of the test results of Examples 1-3 and Comparative Example 3, the preparation method of hindered amine light stabilizer 119 provided by the present invention can further improve the selectivity of tetrasubstituted products and the yield of the preparation reaction by adding a pre-catalyst during the methylation reaction of intermediate II.
[0071] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for preparing a hindered amine light stabilizer 119, characterized in that: The following steps are involved: (1) In a reactor, add N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, cyanuric chloride, a base catalyst and an organic solvent, heat to 40-70°C for reaction for 8-12 hours, and after the reaction is completed, cool, separate, wash and dry to obtain intermediate I; (2) In a reactor, add intermediate I, N,N'-di(3-aminopropyl)ethylenediamine, a supported base catalyst and an organic solvent, heat to 150-180°C and reflux for reaction for 8-16 hours. After the reaction is completed, cool, separate, wash and dry to obtain intermediate II; (3) adding a precatalyst, intermediate II, an aldehyde compound and deionized water into an autoclave, introducing nitrogen to replace the air, heating to 70-95° C. for reflux reaction for 8-12 hours, and cooling, dehydrating, filtering and drying after the reaction to obtain the hindered amine light stabilizer 119; The preparation process of the hindered amine light stabilizer 119 is as follows: ； in, .
2. The method for preparing the hindered amine light stabilizer 119 according to claim 1, characterized in that: The organic solvent is selected from one of toluene, xylene, trimethylbenzene or C7-C9 alkane; the alkaline catalyst is selected from one of sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
3. The method for preparing the hindered amine light stabilizer 119 according to claim 1, characterized in that: In the step (1), the mass ratio of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine to cyanuric chloride is 3-4:
3.
4. The method for preparing the hindered amine light stabilizer 119 according to claim 1, characterized in that: In the step (2), the mass ratio of N,N'-di(3-aminopropyl)ethylenediamine, intermediate I and supported base catalyst is (0.3-0.5):(3.5-4.5):(0.1-0.2).
5. The method for preparing the hindered amine light stabilizer 119 according to claim 1, characterized in that: The supported base catalyst in step (2) is prepared by the following steps: adding metal nitrate, template F127 and deionized water into a reactor, adding mesoporous silica after dissolving, stirring at 50-100 r / min for 4-6 hours, filtering, transferring to a muffle furnace and calcining at 500-600° C. for 6-8 hours to obtain the supported base catalyst.
6. The method for preparing the hindered amine light stabilizer 119 according to claim 5, characterized in that: The metal nitrate is selected from one of sodium nitrate, calcium nitrate, copper nitrate, zinc nitrate or cerium nitrate; the mass ratio of the metal nitrate to the mesoporous silica is 1:3-5.
7. The method for preparing the hindered amine light stabilizer 119 according to claim 1, characterized in that: The aldehyde compound is selected from formaldehyde or paraformaldehyde.
8. The method for preparing the hindered amine light stabilizer 119 according to claim 1, characterized in that: In the step (3), the mass ratio of the precatalyst, the intermediate II and the aldehyde compound is (0.1-0.2):(4-6):(1-2).
9. The method for preparing the hindered amine light stabilizer 119 according to claim 1, characterized in that: The precatalyst in step (3) is selected from one of bis(2-methylallyl)palladium chloride dimer and crotonylpalladium chloride dimer.
10. The hindered amine light stabilizer 119 obtained by the preparation method of the hindered amine light stabilizer 119 according to any one of claims 1 to 9.