Triazine ring group hindered phenol antioxidant and preparation method thereof

Abstract

The invention relates to a triazine ring group hindered phenol antioxidant and a preparation method thereof. The method comprises the following steps: reacting a system containing long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran at 0-5 DEG C for 6-8 hours to obtain an intermediate; reacting a system containing the intermediate, 2, 6-di-tert-butyl-4-hydroxymethylphenol, potassium carbonate and xylene at 40-60 DEG C for 2-4 hours, and then reacting at 80-100 DEG C for 5-8 hours to obtain a crude product; and dissolving the crude product with a methanol aqueous solution to obtain a crude product dissolving system, crystallizing the crude product dissolving system, and carrying out suction filtration and drying to obtain the triazine ring group hindered phenol antioxidant. The method is mild in preparation condition and simple and easy to operate, the prepared triazine ring group hindered phenol antioxidant is reasonable and novel in product structure and high in yield, DPPH can be efficiently removed, and the removal rate reaches up to 88% or above when DPPH is removed in a balanced mode.

Description

Technical Field

[0001] The invention relates to the technical field of hindered phenol antioxidants, in particular to a triazine ring-based hindered phenol antioxidant and a preparation method thereof. Background Art

[0002] Polymer materials play an indispensable role in modern industry and daily life. However, during their processing, storage and use, especially under the influence of light, heating or heavy metal ions, they will react with oxygen in the air, accelerate the cross-linking and degradation of polymer chains, and significantly reduce the performance and service life of the materials. This phenomenon is usually called aging or degradation of materials.

[0003] In order to effectively delay the aging of polymer materials, the use of antioxidants is particularly critical. Antioxidants are chemical additives that can significantly inhibit the oxidation process. They can interrupt the oxidation chain reaction by capturing free radicals or decomposing peroxides, thereby delaying the aging process of polymer materials. Antioxidants can be divided into primary antioxidants and secondary antioxidants according to their mechanism of action. Primary antioxidants mainly prevent the occurrence of oxidation reactions by capturing free radicals, such as phenolic and amine antioxidants; while secondary antioxidants work by decomposing peroxides, and common ones are phosphite and sulfide antioxidants.

[0004] At present, hindered phenol antioxidants are the most widely used type of antioxidants. In recent years, due to their unique structural characteristics, no color change, no pollution and other advantages, hindered phenol antioxidants have been widely used in synthetic rubber, polyolefin plastics and textiles. However, the current hindered phenol antioxidants still have one or more problems such as unreasonable product structure, low yield, low DPPH free radical scavenging rate, and long scavenging time. However, with the continuous increase in demand for polymer materials and the rapid development of the industry, the social demand for antioxidants is also increasing, and the development of new and efficient antioxidants has become a top priority.

[0005] In summary, it is very necessary to provide a triazine ring-based hindered phenol antioxidant and a preparation method thereof. Summary of the invention

[0006] In order to solve one or more technical problems existing in the prior art, the present invention provides a triazine ring-based hindered phenol antioxidant and a preparation method thereof.

[0007] In a first aspect, the present invention provides a triazine ring-based hindered phenol antioxidant, the structural formula of the triazine ring-based hindered phenol antioxidant is shown in the following formula I:

[0008]

[0009] In Formula I, 10≤n≤16, and n is a positive integer.

[0010] In a second aspect, the present invention provides a method for preparing a triazine ring-based hindered phenol antioxidant, the method comprising the following steps:

[0011] (1) reacting a system comprising a long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran at 0 to 5° C. for 6 to 8 hours to obtain an intermediate;

[0012] (2) reacting a system comprising an intermediate, 2,6-di-tert-butyl-4-hydroxymethylphenol, potassium carbonate and xylene at 40 to 60° C. for 2 to 4 hours, and then reacting at 80 to 100° C. for 5 to 8 hours to obtain a crude product;

[0013] (3) dissolving the crude product with methanol aqueous solution to obtain a crude product solution system, then crystallizing the crude product solution system, and then filtering and drying to obtain a triazine ring-based hindered phenol antioxidant.

[0014] Preferably, the long-chain fatty amine is one or more of dodecylamine, tetradecylamine, hexadecylamine and octadecylamine.

[0015] Preferably, in step (1), the molar ratio of the long-chain fatty amine, the cyanuric chloride and the potassium carbonate is (1.8-2.2):(1.8-2.2):1, preferably 2:2:1.

[0016] Preferably, in step (2), the molar ratio of the intermediate, the 2,6-di-tert-butyl-4-hydroxymethylphenol and the potassium carbonate is 1:(1.8-2.2):1, preferably 1:2:1.

[0017] Preferably, the reaction in step (1) and / or step (2) is carried out under a nitrogen atmosphere.

[0018] Preferably, in step (1), the system comprising long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran is prepared by: uniformly mixing cyanuric chloride and long-chain fatty amine with tetrahydrofuran to obtain a cyanuric chloride solution and a long-chain fatty amine solution, respectively; and then simultaneously adding a long-chain fatty amine and a potassium carbonate solution dropwise into the cyanuric chloride solution to obtain a system comprising long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran.

[0019] Preferably, in step (2), the system comprising the intermediate, 2,6-di-tert-butyl-4-hydroxymethylphenol, potassium carbonate and xylene is prepared by uniformly mixing the intermediate and 2,6-di-tert-butyl-4-hydroxymethylphenol with xylene to obtain an intermediate solution and a 2,6-di-tert-butyl-4-hydroxymethylphenol solution, respectively, and then simultaneously adding the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the potassium carbonate solution dropwise to the intermediate solution to obtain a system comprising the intermediate, 2,6-di-tert-butyl-4-hydroxymethylphenol, potassium carbonate and xylene.

[0020] Preferably, the structural formula of the obtained triazine ring-based hindered phenol antioxidant is as shown in the following formula I:

[0021]

[0022] In Formula I, 10≤n≤16, and n is a positive integer.

[0023] The present invention provides, in a third aspect, a oxazine ring-based hindered phenol antioxidant prepared by the preparation method described in the second aspect of the present invention.

[0024] Compared with the prior art, the present invention has at least the following beneficial effects:

[0025] The invention uses cyanuric chloride as a core, firstly mono-substituted with a long-chain fatty amine to synthesize an intermediate, and then uses the intermediate as a bridging group to di-substituted with 2,6-di-tert-butyl-4-hydroxymethylphenol to synthesize a novel high-efficiency hindered phenol antioxidant. The method of the invention has mild preparation conditions, is simple and easy to operate, and the triazine ring-based hindered phenol antioxidant prepared by the invention has a reasonable and novel product structure, high yield, can efficiently remove DPPH, and the removal rate when removing DPPH in equilibrium is as high as more than 88%, the time to reach the equilibrium removal rate is short, and the removal efficiency is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is the infrared spectra of the intermediates prepared in Examples 1 to 4 of the present invention;

[0027] Figure 2 is the infrared spectrum of the triazine ring hindered phenol antioxidant prepared in Examples 1 to 4 of the present invention;

[0028] Figure 3 is a curve diagram showing the relationship between the scavenging efficiency and scavenging time of the triazine ring hindered phenol antioxidants prepared in Examples 1 to 4 of the present invention on DPPH free radicals;

[0029] Figure 4 This is a graph showing the scavenging rate of the triazine ring hindered phenol antioxidants prepared in Examples 1 to 4 of the present invention when scavenging DPPH equilibrium. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0031] In a first aspect, the present invention provides a triazine ring-based hindered phenol antioxidant, the structural formula of the triazine ring-based hindered phenol antioxidant is shown in the following formula I:

[0032]

[0033] In Formula I, 10≤n≤16, and n is a positive integer.

[0034] The triazine ring hindered phenol antioxidant provided by the invention has a reasonable and novel product structure, high yield, can efficiently remove DPPH, and the removal rate when removing DPPH in equilibrium is as high as more than 88%, the time to reach the equilibrium removal rate is short, and the removal efficiency is high.

[0035] In a second aspect, the present invention provides a method for preparing a triazine ring-based hindered phenol antioxidant, the method comprising the following steps:

[0036] (1) A system comprising a long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran is reacted at 0 to 5°C (e.g., 0°C, 1°C, 2°C, 3°C, 4°C or 5°C) for 6 to 8 hours (e.g., 6, 7 or 8 hours) to obtain an intermediate; in the present invention, for example, dodecylamine, tetradecylamine, hexadecylamine and octadecylamine are used to replace cyanuric chloride to synthesize C12-CNCl, C14-CNCl, C16-CNCl and C18-CNCl, respectively, and the reaction principle is, for example, as shown in the following formula (1):

[0037]

[0038] In formula (1), 10≤n≤16, and n is a positive integer; in the reaction of step (1) of the present invention, it is necessary to control the low temperature reaction environment (0-5°C), which helps to improve the selectivity of the reaction, can effectively control the specific single substitution reaction between cyanuric chloride and long-chain fatty amine, helps to preferentially generate the target intermediate instead of generating too many by-products, and is beneficial to improving the yield and purity of the target intermediate. In addition, slow reaction at a low temperature of 0-5°C is beneficial to the full contact and uniform reaction of the reactants in step (1), ensuring the uniformity of the reaction and the uniformity of the product, which is very critical for the smooth progress of subsequent reactions and ensuring the quality control of the synthesis of the triazine ring-based hindered phenol antioxidant with a specific structure, and is beneficial to ensuring that a triazine ring-based hindered phenol antioxidant with high yield and high scavenging rate for DPPH free radicals is obtained. The present invention finds that if the reaction temperature of step (1) is too high, undesirable intermediates will be generated, which will change the specific molecular structure of the target product triazine ring-based hindered phenol antioxidant and significantly reduce its antioxidant activity.

[0039] (2) reacting a system comprising an intermediate, 2,6-di-tert-butyl-4-hydroxymethylphenol, potassium carbonate and xylene at 40 to 60° C. (e.g., 40° C., 45° C., 50° C., 55° C. or 60° C.) for 2 to 4 h (e.g., 2, 3 or 4 h), and then reacting at 80 to 100° C. (e.g., 80° C., 85° C., 90° C., 95° C. or 100° C.) for 5 to 8 h (e.g., 5, 6, 7 or 8 h) to obtain a crude product; the substitution process of chlorine atoms in cyanuric chloride molecules can be achieved by controlling the temperature. The present invention finds that the substitution reaction of the second chlorine atom is preferably carried out at 40 to 60° C., and the substitution reaction of the third chlorine atom is preferably carried out at 80 to 100° C. In step (2) of the present invention, The step-by-step temperature increase reaction strategy effectively combines the selectivity and completeness of the reaction, avoids the situation where the reaction is not completely carried out in a single temperature range, and makes full use of the reaction characteristics at different temperatures in the reaction process, thereby maximizing the yield and purity of the target product, the triazine ring-based hindered phenol antioxidant, while ensuring the high antioxidant performance of the final product; the step-by-step temperature increase strategy adopted in the present invention not only optimizes the reaction conditions and reduces the generation of by-products, but also ensures the high quality and high efficiency of the final product, which is of great significance for realizing the industrial production of high-performance triazine ring-based hindered phenol antioxidants with cyanuric chloride as the core, monosubstituted with long-chain fatty amines and disubstituted with 2,6-di-tert-butyl-4-hydroxymethylphenol;

[0040] (3) dissolving the crude product with methanol aqueous solution to obtain a crude product solution system, and then crystallizing the crude product solution system, and then filtering and drying to obtain a triazine ring hindered phenol antioxidant; in the present invention, for example, C12-CNCl, C14-CNCl, C16-CNCl and C18-CNCl are used as bridging groups to respectively di-substituted with 2,6-di-tert-butyl-4-hydroxymethylphenol to synthesize triazine ring hindered phenol antioxidant series products C12-hindered phenol, C14-hindered phenol, C16-hindered phenol and C18-hindered phenol, and the reaction principle is shown in the following formula (2):

[0041]

[0042] In formula (2), 10≤n≤16, and n is a positive integer.

[0043] The invention uses cyanuric chloride as a core, firstly mono-substituted with a long-chain fatty amine to synthesize an intermediate, and then uses the intermediate as a bridging group to di-substituted with 2,6-di-tert-butyl-4-hydroxymethylphenol to synthesize a novel high-efficiency hindered phenol antioxidant. The method of the invention has mild preparation conditions, is simple and easy to operate, and the triazine ring-based hindered phenol antioxidant prepared by the invention has a reasonable and novel product structure, high yield, can efficiently remove DPPH, and the removal rate when removing DPPH in equilibrium is as high as more than 88%, the time to reach the equilibrium removal rate is short, and the removal efficiency is high.

[0044] According to some preferred embodiments, the long-chain fatty amine is one or more of dodecylamine, tetradecylamine, hexadecylamine and octadecylamine.

[0045] According to some preferred embodiments, in step (1), the molar ratio of the long-chain fatty amine, the cyanuric chloride and the potassium carbonate (K2CO3) is (1.8-2.2): (1.8-2.2): 1, preferably 2:2:1.

[0046] According to some preferred embodiments, in step (2), the molar ratio of the intermediate, the 2,6-di-tert-butyl-4-hydroxymethylphenol and the potassium carbonate is 1:(1.8-2.2):1, preferably 1:2:1; in the present invention, preferably, the molar ratio of the long-chain fatty amine, the cyanuric chloride and the potassium carbonate is (1.8-2.2):(1.8-2.2):1, and the molar ratio of the intermediate, the 2,6-di-tert-butyl-4-hydroxymethylphenol and the potassium carbonate is 1:(1.8-2.2):1. The appropriate molar ratio can ensure the full progress of the reaction and the minimization of side reactions, and is the key to obtaining triazine ring hindered phenol antioxidants with high yield, high purity and high antioxidant performance; this precise ratio design not only optimizes the reaction conditions, but also ensures the quality and stable performance of the final product.

[0047] According to some preferred embodiments, the reaction in step (1) and / or step (2) is carried out under a nitrogen atmosphere.

[0048] According to some preferred embodiments, in step (1), the system comprising long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran is prepared as follows: cyanuric chloride and long-chain fatty amine are uniformly mixed with tetrahydrofuran to obtain a cyanuric chloride solution and a long-chain fatty amine solution, respectively; then, the long-chain fatty amine and the potassium carbonate solution are simultaneously added dropwise to the cyanuric chloride solution to obtain a system comprising long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran; the present invention does not specifically limit the amount of tetrahydrofuran used, and those skilled in the art can conventionally select, for example, the mass of tetrahydrofuran used for mixing cyanuric chloride is 5 to 20 times the mass of cyanuric chloride, and the mass of tetrahydrofuran used for mixing long-chain fatty amine is 5 to 20 times the mass of long-chain fatty amine; in the present invention, the potassium carbonate solution is, for example, an aqueous potassium carbonate solution (K2CO3 aqueous solution) with a concentration of 3 to 5 mol / L.

[0049] According to some specific implementation methods, step (1) is: accurately weigh the required raw materials according to the molar ratio of n (dodecylamine): n (cyanuric chloride): n (potassium carbonate) = 2:2:1; dissolve the weighed cyanuric chloride in an appropriate amount of tetrahydrofuran to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 0-5°C and N2 environment; dissolve the weighed dodecylamine in an appropriate amount of tetrahydrofuran to obtain a dodecylamine solution (long-chain fatty amine solution), and slowly add the dodecylamine solution to the cyanuric chloride solution using a constant pressure dropping funnel, and at the same time, A 5 mol / L K2CO3 aqueous solution is added dropwise in proportion; after all the dodecylamine solution and the K2CO3 aqueous solution are added dropwise, the temperature is maintained at 0-5°C and the reaction is continued for 7 hours under a nitrogen atmosphere; during the reaction, thin layer chromatography is used to track the progress of the reaction and to detect the product; after the reaction is completed, the solid inorganic salt KCl is removed by negative pressure filtration; the organic solvent tetrahydrofuran is removed by rotary evaporation, and the obtained substance is vacuum dried in a vacuum drying oven at 45°C for 12 hours to obtain a dodecylamine intermediate (denoted as C12-CNCl).

[0050] According to some preferred embodiments, in step (2), the system comprising the intermediate, 2,6-di-tert-butyl-4-hydroxymethylphenol, potassium carbonate and xylene is prepared by: mixing the intermediate and 2,6-di-tert-butyl-4-hydroxymethylphenol with xylene to obtain an intermediate solution and a 2,6-di-tert-butyl-4-hydroxymethylphenol solution, respectively, and then simultaneously adding the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the potassium carbonate solution to the intermediate solution to obtain a system comprising the intermediate, 2,6-di-tert-butyl-4 -hydroxymethylphenol, potassium carbonate and xylene system; the present invention does not specifically limit the amount of xylene used, and those skilled in the art can make a conventional selection, for example, the mass of xylene used for the mixed intermediate is 40 to 80 times the mass of the intermediate, and the mass of xylene used for 2,6-di-tert-butyl-4-hydroxymethylphenol is 20 to 40 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol; in the present invention, the potassium carbonate solution is, for example, an aqueous potassium carbonate solution (K2CO3 aqueous solution) with a concentration of 3 to 5 mol / L.

[0051] According to some specific implementation methods, step (2) is: accurately weigh the required raw materials according to the molar ratio of n(C12-CNCl):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:2:1; dissolve the weighed intermediate C12-CNCl in an appropriate amount of xylene under ultrasonic conditions to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C and N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene to obtain a 2,6-di-tert-butyl-4-hydroxymethylphenol solution, and slowly add the 2,6-di-tert-butyl-4-hydroxymethylphenol solution using a constant pressure dropping funnel. Slowly add the 2,6-di-tert-butyl-4-hydroxymethylphenol solution to the intermediate solution, and at the same time, add a 3 mol / L K2CO3 aqueous solution in proportion; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution have been added, maintain the temperature at 50°C and continue to react for 3 hours under a nitrogen atmosphere, then increase the temperature to 90°C and continue to react for 6 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; use reduced pressure distillation to remove the organic solvent xylene, and the resulting substance is vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product.

[0052] According to some specific embodiments, step (3) is: in order to purify the product, the crude product is added to a three-necked flask, and methanol aqueous solution is added thereto (the methanol aqueous solution is composed of methanol and water, and the volume ratio of methanol to water is (6-8): (2-4), and the mass of the methanol aqueous solution is 5-10 times the mass of the crude product; while slowly stirring, the system is heated to 85°C and condensed and refluxed until the crude product is completely dissolved and the system is clarified (continue to condense and reflux at 85°C for 10-15 minutes); then, the system temperature is lowered to allow the system to slowly crystallize (gradually lower from 85°C to room temperature). The present invention does not make any specific restrictions on the operation of lowering the system temperature, for example, the system temperature can be lowered by natural cooling; after the system is cooled to room temperature (or placed in a refrigerator for continued crystallization), the final refined product of triazine ring hindered phenol antioxidant is obtained by reduced pressure filtration and vacuum drying; in the present invention, room temperature refers to, for example, room temperature of 20-30°C; the present invention does not make any specific restrictions on the slow stirring rate, for example, it can be 200-800r / min.

[0053] According to some preferred embodiments, the structural formula of the obtained triazine ring-based hindered phenol antioxidant is shown in the following formula I:

[0054]

[0055] In Formula I, 10≤n≤16, and n is a positive integer.

[0056] The present invention provides, in a third aspect, a oxazine ring-based hindered phenol antioxidant prepared by the preparation method described in the second aspect of the present invention.

[0057] The technical scheme in the embodiment of the present invention will be clearly and completely described below. Obviously, the described embodiment is only a part of the embodiment of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. Unless otherwise specified, each reaction raw material used in the embodiment of the present invention and the comparative example can be obtained by commercial purchase or synthesized by existing methods.

[0058] Example 1

[0059] This embodiment provides a method for preparing a triazine ring-based hindered phenol antioxidant, and the specific steps are as follows:

[0060] ①Accurately weigh the required raw materials according to the molar ratio of n(dodecylamine):n(cyanuric chloride):n(potassium carbonate)=2:2:1; dissolve the weighed cyanuric chloride in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 5 times the mass of cyanuric chloride) to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 3°C ​​and N2 environment; dissolve the weighed dodecylamine in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 12.5 times the mass of dodecylamine) to obtain a dodecylamine solution (long-chain fatty amine solution), A constant pressure dropping funnel is used to slowly drop the dodecylamine solution into the cyanuric chloride solution, and a 5 mol / L K2CO3 aqueous solution is dropped in proportion at the same time; after all the dodecylamine solution and the K2CO3 aqueous solution are dropped, the temperature is maintained at 3°C ​​and the reaction is continued for 7 hours under a nitrogen atmosphere; after the reaction is completed, the solid inorganic salt KCl is removed by negative pressure filtration; the organic solvent tetrahydrofuran is removed by rotary evaporation, and the obtained substance is vacuum dried in a vacuum drying oven at 45°C for 12 hours to obtain a dodecylamine intermediate (denoted as C12-CNCl).

[0061] ②Accurately weigh the required raw materials according to the molar ratio of n(C12-CNCl):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:2:1; dissolve the weighed intermediate C12-CNCl in an appropriate amount of xylene (the mass of xylene is 60 times the mass of the intermediate C12-CNCl) to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C under N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol) to obtain 2,6-di-tert-butyl-4 -hydroxymethylphenol solution, slowly add the 2,6-di-tert-butyl-4-hydroxymethylphenol solution to the intermediate solution using a constant pressure dropping funnel, and at the same time, add a 3 mol / L K2CO3 aqueous solution in proportion; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution have been added, maintain the temperature at 50°C, continue to react for 3 hours under a nitrogen atmosphere, then increase the temperature to 90°C, and continue to react for 6 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; use reduced pressure distillation to remove the organic solvent xylene, and the resulting substance is vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product.

[0062] ③ The crude product was added to a three-necked flask, and methanol aqueous solution was added thereto (the methanol aqueous solution consisted of methanol and water, and the volume ratio of methanol to water was 8:2), the mass of the methanol aqueous solution was 8 times the mass of the crude product; while slowly stirring, the system was heated to 85°C and condensed and refluxed until the final crude product was completely dissolved and the system was clarified and continued to condense and reflux at 85°C for 15 minutes; then, the system temperature was lowered to allow the system to slowly crystallize, and after the system was cooled to room temperature 25°C, it was filtered off under reduced pressure and vacuum dried at 55°C for 12 hours to obtain the final refined product, triazine ring hindered phenol antioxidant (denoted as C12-hinderedphenol).

[0063] Example 2

[0064] This embodiment provides a method for preparing a triazine ring-based hindered phenol antioxidant, and the specific steps are as follows:

[0065] ①Accurately weigh the required raw materials according to the molar ratio of n (tetradecylamine): n (cyanuric chloride): n (potassium carbonate) = 2:2:1; dissolve the weighed cyanuric chloride in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 5 times the mass of cyanuric chloride) to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 3°C ​​and N2 environment; dissolve the weighed tetradecylamine in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 12 times the mass of tetradecylamine) to obtain a tetradecylamine solution (long-chain fatty amine solution), and take Use a constant pressure dropping funnel to slowly add the tetradecamine solution to the cyanuric chloride solution, and at the same time, add a 5 mol / L K2CO3 aqueous solution in proportion; after all the tetradecamine solution and the K2CO3 aqueous solution have been added, maintain the temperature at 3°C ​​and continue the reaction for 7 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; use rotary evaporation to remove the organic solvent tetrahydrofuran, and the resulting substance is vacuum dried in a vacuum drying oven at 45°C for 12 hours to obtain the tetradecamine intermediate (referred to as C14-CNCl).

[0066] ②Accurately weigh the required raw materials according to the molar ratio of n(C14-CNCl):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:2:1; dissolve the weighed intermediate C14-CNCl in an appropriate amount of xylene (the mass of xylene is 65 times the mass of the intermediate C14-CNCl) to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C under N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol) to obtain 2,6-di-tert-butyl-4 -hydroxymethylphenol solution, slowly add the 2,6-di-tert-butyl-4-hydroxymethylphenol solution to the intermediate solution using a constant pressure dropping funnel, and at the same time, add a 3 mol / L K2CO3 aqueous solution in proportion; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution have been added, maintain the temperature at 50°C, continue to react for 3 hours under a nitrogen atmosphere, then increase the temperature to 90°C, and continue to react for 6 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; use reduced pressure distillation to remove the organic solvent xylene, and the resulting substance is vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product.

[0067] ③ The crude product was added to a three-necked flask, and methanol aqueous solution was added thereto (the methanol aqueous solution consisted of methanol and water, and the volume ratio of methanol to water was 8:2), the mass of the methanol aqueous solution was 8 times the mass of the crude product; while slowly stirring, the system was heated to 85°C and condensed and refluxed until the final crude product was completely dissolved and the system was clarified and continued to condense and reflux at 85°C for 15 minutes; then, the system temperature was lowered to allow the system to slowly crystallize, and after the system was cooled to room temperature 25°C, it was filtered off under reduced pressure and vacuum dried at 55°C for 12 hours to obtain the final refined product, triazine ring hindered phenol antioxidant (denoted as C14-hinderedphenol).

[0068] Example 3

[0069] This embodiment provides a method for preparing a triazine ring-based hindered phenol antioxidant, and the specific steps are as follows:

[0070] ①Accurately weigh the required raw materials according to the molar ratio of n (hexadecylamine): n (cyanuric chloride): n (potassium carbonate) = 2:2:1; dissolve the weighed cyanuric chloride in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 5 times the mass of cyanuric chloride) to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 3°C ​​and N2 environment; dissolve the weighed hexadecylamine in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 9.2 times the mass of hexadecylamine) to obtain a hexadecylamine solution (long-chain fatty amine solution), and take Slowly add the hexadecylamine solution to the cyanuric chloride solution using a constant pressure dropping funnel, and at the same time, add a 5 mol / L K2CO3 aqueous solution in proportion; after all the hexadecylamine solution and the K2CO3 aqueous solution have been added, maintain the temperature at 3°C ​​and continue the reaction for 7 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; use rotary evaporation to remove the organic solvent tetrahydrofuran, and the resulting substance is vacuum dried in a vacuum drying oven at 45°C for 12 hours to obtain the hexadecylamine intermediate (denoted as C16-CNCl).

[0071] ②Accurately weigh the required raw materials according to the molar ratio of n(C16-CNCl):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:2:1; dissolve the weighed intermediate C16-CNCl in an appropriate amount of xylene (the mass of xylene is 45 times the mass of the intermediate C16-CNCl) to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C under N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol) to obtain 2,6-di-tert-butyl-4 -hydroxymethylphenol solution, slowly add the 2,6-di-tert-butyl-4-hydroxymethylphenol solution to the intermediate solution using a constant pressure dropping funnel, and at the same time, add a 3 mol / L K2CO3 aqueous solution in proportion; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution have been added, maintain the temperature at 50°C, continue to react for 3 hours under a nitrogen atmosphere, then increase the temperature to 90°C, and continue to react for 6 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; use reduced pressure distillation to remove the organic solvent xylene, and the resulting substance is vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product.

[0072] ③ The crude product was added to a three-necked flask, and methanol aqueous solution was added thereto (the methanol aqueous solution was composed of methanol and water, and the volume ratio of methanol to water was 8:2), the mass of the methanol aqueous solution was 8 times the mass of the crude product; while slowly stirring, the system was heated to 85°C and condensed and refluxed until the final crude product was completely dissolved and the system was clarified and continued to condense and reflux at 85°C for 15 minutes; then, the system temperature was lowered to allow the system to slowly crystallize, and after the system was cooled to room temperature 25°C, it was filtered off under reduced pressure and vacuum dried at 55°C for 12 hours to obtain the final refined product, triazine ring hindered phenol antioxidant (denoted as C16-hinderedphenol).

[0073] Example 4

[0074] This embodiment provides a method for preparing a triazine ring-based hindered phenol antioxidant, and the specific steps are as follows:

[0075] ①Accurately weigh the required raw materials according to the molar ratio of n(octadecylamine):n(cyanuric chloride):n(potassium carbonate)=2:2:1; dissolve the weighed cyanuric chloride in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 5 times the mass of cyanuric chloride) to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 3°C ​​and N2 environment; dissolve the weighed octadecylamine in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 12 times the mass of octadecylamine) to obtain an octadecylamine solution (long-chain fatty amine solution), and take Use a constant pressure dropping funnel to slowly add the octadecylamine solution to the cyanuric chloride solution, and at the same time, add a 5 mol / L K2CO3 aqueous solution in proportion; after all the octadecylamine solution and the K2CO3 aqueous solution have been added, maintain the temperature at 3°C ​​and continue the reaction for 7 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; use rotary evaporation to remove the organic solvent tetrahydrofuran, and the resulting substance is vacuum dried in a vacuum drying oven at 45°C for 12 hours to obtain an octadecylamine intermediate (denoted as C18-CNCl).

[0076] ②Accurately weigh the required raw materials according to the molar ratio of n(C18-CNCl):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:2:1; dissolve the weighed intermediate C18-CNCl in an appropriate amount of xylene (the mass of xylene is 56.5 times the mass of the intermediate C18-CNCl) to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C and N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol) to obtain 2,6-di-tert-butyl- 4-hydroxymethylphenol solution, use a constant pressure dropping funnel to slowly add the 2,6-di-tert-butyl-4-hydroxymethylphenol solution to the intermediate solution, and at the same time, add a 3 mol / L K2CO3 aqueous solution in proportion; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution have been added, maintain the temperature at 50°C and continue to react for 3 hours under a nitrogen atmosphere, then increase the temperature to 90°C and continue to react for 6 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; use reduced pressure distillation to remove the organic solvent xylene, and the resulting substance is vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product.

[0077] ③ The crude product was added to a three-necked flask, and methanol aqueous solution was added thereto (the methanol aqueous solution was composed of methanol and water, and the volume ratio of methanol to water was 8:2), the mass of the methanol aqueous solution was 8 times the mass of the crude product; while slowly stirring, the system was heated to 85°C and condensed and refluxed until the final crude product was completely dissolved and the system was clarified and continued to condense and reflux at 85°C for 15 minutes; then, the system temperature was lowered to allow the system to slowly crystallize, and after the system was cooled to room temperature 25°C, it was filtered off under reduced pressure and vacuum dried at 55°C for 12 hours to obtain the final refined product, triazine ring hindered phenol antioxidant (denoted as C18-hinderedphenol).

[0078] The infrared spectra of the intermediates obtained in Examples 1 to 4 of the present invention are as follows: Figure 1 shown; from Figure 1 It can be seen that the infrared spectra of these four long-chain fatty amine intermediates show a high degree of consistency. The absorption peak positions of the characteristic functional groups are roughly the same, and there are slight differences in the peak intensities. Taking the intermediate C18-CNCl as an example, at 796 cm -1 The peak at 1559 cm corresponds to the stretching vibration of the C-Cl bond, and -1 and 1438cm -1 The absorption peak at 2924cm -1 and 2848cm -1The absorption peaks at 725 cm-1 and 735 cm-2 correspond to the stretching vibrations of -CH3 and -CH2, respectively. -1 The peak at 3324 cm is related to the in-plane swinging motion of the CH2 group; -1 The -NH- stretching vibration absorption peak appears on the left and right, and the peak is single, proving that cyanuric chloride and octadecylamine have reacted. The infrared spectra of the triazine ring-based hindered phenol antioxidants prepared in Examples 1 to 4 of the present invention are as follows: Figure 2 shown; from Figure 2 It can be seen that the infrared spectra of these triazine ring hindered phenol antioxidants show high consistency. The absorption peak positions of the characteristic functional groups are roughly the same, but there are slight differences in the peak intensities. Taking C18-hindered phenol as an example, at 1155cm -1 The -COC- stretching vibration peak appeared at 796 cm -1 The C-Cl bond stretching vibration peak of the octadecylamine intermediate disappeared, and the peak at 3600 cm -1 There is a stretching vibration peak of -OH at , which indicates that the octadecylamine intermediate reacts with 2,6-di-tert-butyl-4-hydroxymethylphenol.

[0079] The relationship between the scavenging efficiency and scavenging time of the triazine ring hindered phenol antioxidants prepared in Examples 1 to 4 of the present invention on DPPH free radicals is shown in FIG. Figure 3 As shown; the result diagram of the scavenging rate of the triazine ring hindered phenol antioxidants prepared in Examples 1 to 4 of the present invention when scavenging DPPH equilibrium, as shown Figure 4 shown; according to Figure 3 and Figure 4 The results of the scavenging rate of the triazine ring hindered phenol antioxidants when scavenging DPPH (scavenging DPPH free radical) equilibrium and the time to reach the scavenging equilibrium are shown in Table 1; the results show that the scavenging rate of the triazine ring hindered phenol antioxidants in Examples 1 to 4 shows a downward trend with the increase of the bridging group carbon chain length, which may be due to the fact that these four hindered phenol antioxidants not only terminate the free radicals by providing hydrogen protons, but also terminate the free radicals by generating phenoloxy free radicals; however, with the increase of the bridging group carbon chain length, the steric hindrance also increases, the reaction probability of the phenoloxy free radical decreases, and the overall scavenging rate decreases.

[0080] Comparative Example 1

[0081] Comparative Example 1 is substantially the same as Example 1, except that:

[0082] ①Accurately weigh the required raw materials according to the molar ratio of n (dodecylamine): n (cyanuric chloride): n (potassium carbonate) = 2:2:1; dissolve the weighed cyanuric chloride in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 5 times the mass of cyanuric chloride) to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 10°C and N2 environment; dissolve the weighed dodecylamine in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 12.5 times the mass of dodecylamine) to obtain a dodecylamine solution (long-chain fatty amine solution), and slowly add the dodecylamine solution dropwise using a constant pressure dropping funnel to A 5 mol / L K2CO3 aqueous solution was added dropwise to the cyanuric chloride solution at the same time; after all the dodecylamine solution and the K2CO3 aqueous solution were added dropwise, the temperature was maintained at 10°C and the reaction was continued for 7 hours under a nitrogen atmosphere; after the reaction was completed, the solid inorganic salt KCl was removed by negative pressure filtration; the organic solvent tetrahydrofuran was removed by rotary evaporation, and the obtained substance was vacuum dried in a vacuum drying oven at 45°C for 12 hours to obtain an intermediate; in this comparative example, the intermediate obtained in step ① was used to replace the C12-CNCl obtained in step ① of Example 1 to carry out subsequent steps ② and ③.

[0083] Comparative Example 2

[0084] Comparative Example 2 is substantially the same as Example 1, except that:

[0085] ②According to the molar ratio of n(C12-CNCl):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:2:1, accurately weigh the required raw materials; dissolve the weighed intermediate C12-CNCl in an appropriate amount of xylene (the mass of xylene is 60 times the mass of the intermediate C12-CNCl) to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C and N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol) to obtain a 2,6-di-tert-butyl-4-hydroxymethylphenol solution. liquid, slowly add the 2,6-di-tert-butyl-4-hydroxymethylphenol solution to the intermediate solution using a constant pressure dropping funnel, and at the same time, add a 3 mol / L K2CO3 aqueous solution in proportion; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution have been added, maintain the temperature at 50°C and continue the reaction under a nitrogen atmosphere for 9 hours; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; remove the organic solvent xylene by reduced pressure distillation, and vacuum dry the obtained substance in a vacuum drying oven at 65°C for 12 hours to obtain a crude product; in this comparative example, the crude product obtained in step ② is used to replace the crude product obtained in step ② of Example 1 to carry out the subsequent step ③.

[0086] Comparative Example 3

[0087] Comparative Example 3 is substantially the same as Example 1, except that:

[0088] ②According to the molar ratio of n(C12-CNCl):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:2:1, accurately weigh the required raw materials; dissolve the weighed intermediate C12-CNCl in an appropriate amount of xylene (the mass of xylene is 60 times the mass of the intermediate C12-CNCl) to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C and N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol) to obtain a 2,6-di-tert-butyl-4-hydroxymethylphenol solution. liquid, slowly add the 2,6-di-tert-butyl-4-hydroxymethylphenol solution to the intermediate solution using a constant pressure dropping funnel, and at the same time, add a 3 mol / L K2CO3 aqueous solution in proportion; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution have been added, the temperature is raised to 90°C, and the reaction is continued for 9 hours under a nitrogen atmosphere; after the reaction is completed, the solid inorganic salt KCl is removed by negative pressure filtration; the organic solvent xylene is removed by reduced pressure distillation, and the obtained substance is vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product; in this comparative example, the crude product obtained in step ② is used to replace the crude product obtained in step ② of Example 1 to carry out the subsequent step ③.

[0089] Comparative Example 4

[0090] Comparative Example 4 is substantially the same as Example 1, except that:

[0091] ①Accurately weigh the required raw materials according to the molar ratio of n (dodecylamine): n (cyanuric chloride): n (potassium carbonate) = 2:1.5:1; dissolve the weighed cyanuric chloride in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 5 times the mass of cyanuric chloride) to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 3°C ​​and N2 environment; dissolve the weighed dodecylamine in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 12.5 times the mass of dodecylamine) to obtain a dodecylamine solution (long chain fatty amine solution), slowly add dodecylamine solution to cyanuric chloride solution using a constant pressure dropping funnel, and at the same time, add K2CO3 aqueous solution with a concentration of 5 mol / L in proportion; after all the dodecylamine solution and K2CO3 aqueous solution have been added, maintain the temperature at 3°C ​​and continue the reaction for 7 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; remove the organic solvent tetrahydrofuran by rotary evaporation, and the obtained substance is vacuum dried in a vacuum drying oven at 45°C for 12 hours to obtain the intermediate.

[0092] ②Accurately weigh the required raw materials according to the molar ratio of n(intermediate):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:3:1; dissolve the weighed intermediate in an appropriate amount of xylene (the mass of xylene is 60 times the mass of the intermediate) to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C and N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol) to obtain a 2,6-di-tert-butyl-4-hydroxymethylphenol solution, and slowly add 2,6-di-tert-butyl-4-hydroxymethylphenol using a constant pressure dropping funnel. The hydroxymethylphenol solution is added dropwise to the intermediate solution, and a 3 mol / L K2CO3 aqueous solution is added dropwise in proportion; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution are added dropwise, the temperature is maintained at 50°C, and the reaction is continued for 3 hours under a nitrogen atmosphere, and then the temperature is increased to 90°C, and the reaction is continued for 6 hours under a nitrogen atmosphere; after the reaction is completed, the solid inorganic salt KCl is removed by negative pressure filtration; the organic solvent xylene is removed by reduced pressure distillation, and the obtained substance is vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product; in this comparative example, the crude product obtained in step ② is used to replace the crude product obtained in step ② of Example 1 to carry out the subsequent step ③.

[0093] Comparative Example 5

[0094] Comparative Example 5 is substantially the same as Example 1, except that:

[0095] ①Accurately weigh the required raw materials according to the molar ratio of n (dodecylamine): n (cyanuric chloride): n (potassium carbonate) = 2:2.5:1; dissolve the weighed cyanuric chloride in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 5 times the mass of cyanuric chloride) to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 3°C ​​and N2 environment; dissolve the weighed dodecylamine in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 12.5 times the mass of dodecylamine) to obtain a dodecylamine solution (long chain fatty amine solution), slowly add dodecylamine solution to cyanuric chloride solution using a constant pressure dropping funnel, and at the same time, add K2CO3 aqueous solution with a concentration of 5 mol / L in proportion; after all the dodecylamine solution and K2CO3 aqueous solution have been added, maintain the temperature at 3°C ​​and continue the reaction for 7 hours under a nitrogen atmosphere; after the reaction is completed, remove the solid inorganic salt KCl by negative pressure filtration; remove the organic solvent tetrahydrofuran by rotary evaporation, and the obtained substance is vacuum dried in a vacuum drying oven at 45°C for 12 hours to obtain the intermediate.

[0096] ②According to the molar ratio of n(intermediate):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:1.5:1, accurately weigh the required raw materials; dissolve the weighed intermediate in an appropriate amount of xylene (the mass of xylene is 60 times the mass of the intermediate) to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C and N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol) to obtain a 2,6-di-tert-butyl-4-hydroxymethylphenol solution, and slowly add 2,6-di-tert-butyl-4 -Hydroxymethylphenol solution is added dropwise to the intermediate solution, and a 3 mol / L K2CO3 aqueous solution is added dropwise in proportion; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution are added dropwise, the temperature is maintained at 50°C, and the reaction is continued for 3 hours under a nitrogen atmosphere, and then the temperature is increased to 90°C, and the reaction is continued for 6 hours under a nitrogen atmosphere; after the reaction is completed, the solid inorganic salt KCl is removed by negative pressure filtration; the organic solvent xylene is removed by reduced pressure distillation, and the obtained substance is vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product; this comparative example uses the crude product obtained in step ② to replace the crude product obtained in step ② of Example 1 to carry out the subsequent step ③.

[0097] Comparative Example 6

[0098] ①Accurately weigh the required raw materials according to the molar ratio of n(cyanuric chloride):n(2,6-di-tert-butyl-4-hydroxymethylphenol):n(potassium carbonate)=1:3:1; dissolve the weighed cyanuric chloride in an appropriate amount of xylene (the mass of xylene is 5 times the mass of cyanuric chloride) to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 50°C and N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-hydroxymethylphenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-hydroxymethylphenol) to obtain a 2,6-di-tert-butyl-4-hydroxymethylphenol solution, The 2,6-di-tert-butyl-4-hydroxymethylphenol solution was slowly added to the cyanuric chloride solution using a constant pressure dropping funnel, and a 3 mol / L K2CO3 aqueous solution was added proportionally at the same time; after all the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the K2CO3 aqueous solution were added, the temperature was maintained at 50°C, and the reaction was continued for 3 hours under a nitrogen atmosphere, and then the temperature was increased to 90°C, and the reaction was continued for 6 hours under a nitrogen atmosphere; after the reaction was completed, the solid inorganic salt KCl was removed by negative pressure filtration; the organic solvent xylene was removed by reduced pressure distillation, and the obtained substance was vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product.

[0099] ② The crude product is added into a three-necked flask, and methanol aqueous solution is added thereto (methanol aqueous solution is composed of methanol and water, and the volume ratio of methanol to water is 8:2), the mass of methanol aqueous solution is 8 times the mass of the crude product; while slowly stirring, the system is heated to 85°C and condensed and refluxed until the crude product is completely dissolved and the system is clarified and continued to condense and reflux at 85°C for 15 minutes; then, the system temperature is lowered to allow the system to slowly crystallize, and after the system is cooled to room temperature 25°C, it is filtered off under reduced pressure and vacuum dried at 55°C for 12 hours to obtain a triazine ring hindered phenol antioxidant.

[0100] Comparative Example 7

[0101] Comparative Example 7 is substantially the same as Example 1, except that:

[0102] ①Accurately weigh the required raw materials according to the molar ratio of n (n-octyl mercaptan): n (cyanuric chloride): n (potassium carbonate) = 2:2:1; dissolve the weighed cyanuric chloride in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 5 times the mass of cyanuric chloride) to obtain a cyanuric chloride solution, and transfer the cyanuric chloride solution to a three-necked flask, and stir for 30 minutes at 3°C ​​and N2 environment; dissolve the weighed n-octyl mercaptan in an appropriate amount of tetrahydrofuran (the mass of tetrahydrofuran is 20 times the mass of n-octyl mercaptan) to obtain an n-octyl mercaptan solution, and slowly add the n-octyl mercaptan solution to the cyanuric chloride using a constant pressure dropping funnel. The solution was simultaneously dropwise added with a 5 mol / L K2CO3 aqueous solution in proportion; after all the n-octyl mercaptan solution and the K2CO3 aqueous solution were added, the temperature was maintained at 3°C ​​and the reaction was continued for 7 hours under a nitrogen atmosphere; after the reaction was completed, the solid inorganic salt KCl was removed by negative pressure filtration; the organic solvent tetrahydrofuran was removed by rotary evaporation, and the obtained substance was vacuum dried in a vacuum drying oven at 45°C for 12 hours to obtain an intermediate; in this comparative example, the intermediate obtained in step ① was used to replace the C12-CNCl obtained in step ① of Example 1 to carry out subsequent steps ② and ③.

[0103] Comparative Example 8

[0104] Comparative Example 8 is substantially the same as Example 1, except that:

[0105] ②Accurately weigh the required raw materials according to the molar ratio of n(C14-CNCl):n(2,6-di-tert-butyl-4-aminophenol):n(potassium carbonate)=1:2:1; dissolve the weighed intermediate C14-CNCl in an appropriate amount of xylene (the mass of xylene is 65 times the mass of the intermediate C14-CNCl) to obtain an intermediate solution, and transfer the intermediate solution to a three-necked flask, and stir for 30 minutes at 50°C and N2 environment; dissolve the weighed 2,6-di-tert-butyl-4-aminophenol in an appropriate amount of xylene (the mass of xylene is 25 times the mass of 2,6-di-tert-butyl-4-aminophenol) to obtain a 2,6-di-tert-butyl-4-aminophenol solution, and slowly add 2 ,6-di-tert-butyl-4-aminophenol solution is added dropwise to the intermediate solution, and a 3 mol / L K2CO3 aqueous solution is added dropwise in proportion; after all the 2,6-di-tert-butyl-4-aminophenol solution and the K2CO3 aqueous solution are added dropwise, the temperature is maintained at 50°C, and the reaction is continued for 3 hours under a nitrogen atmosphere, and then the temperature is increased to 90°C, and the reaction is continued for 6 hours under a nitrogen atmosphere; after the reaction is completed, the solid inorganic salt KCl is removed by negative pressure filtration; the organic solvent xylene is removed by reduced pressure distillation, and the resulting substance is vacuum dried in a vacuum drying oven at 65°C for 12 hours to obtain a crude product; in this comparative example, the crude product obtained in step ② is used to replace the crude product obtained in step ② of Example 1 to carry out the subsequent step ③.

[0106] Comparative Example 9

[0107] Comparative Example 9: An antioxidant 565, namely 4-[(4,6-dioctylthio-1,3,5-triazine-2-yl)amino]-2,6-di-tert-butylphenol, was synthesized with reference to Example 2 in CN109651280A.

[0108] Comparative Example 10

[0109] Comparative Example 10: A hindered phenol antioxidant was synthesized with reference to Example 1 in CN115894391A.

[0110] Comparative Example 11

[0111] Comparative Example 11: A polysubstituted hindered phenol antioxidant was synthesized with reference to Example 1 in CN101805245A.

[0112] Comparative Example 12

[0113] Comparative Example 12 provides the commercially available antioxidant 3114.

[0114] The present invention tests the yield of the hindered phenolic antioxidants finally obtained in Examples 1 to 4 and Comparative Examples 1 to 8, and the results are shown in Table 1; the present invention also tests the scavenging rate of the hindered phenolic antioxidants finally obtained in each Example and each Comparative Example when scavenging DPPH equilibrium and the time to reach scavenging equilibrium, and the results are shown in Table 1. In the present invention, the scavenging DPPH (scavenging DPPH free radical) experiment is as follows: using anhydrous ethanol as a solvent, preparing a DPPH solution with a concentration of 1.0 mmol / L and a hindered phenolic antioxidant solution to be measured; taking 2 mL of the DPPH solution, using an ultraviolet-visible spectrophotometer to measure its absorbance at a wavelength of 517 nm, recorded as A0; then, fully mixing 2 mL of the DPPH solution with 2 mL of the hindered phenolic antioxidant solution to be measured to avoid errors, allowing the mixed solution to react for a period of time t under light-proof conditions, and then, using an ultraviolet-visible spectrophotometer again to measure the absorbance of the mixed solution at 517 nm, recorded as A t Finally, the scavenging rate E% of the hindered phenolic antioxidant to be measured on DPPH is calculated according to the following formula 1-1.

[0115]

[0116] Table 1

[0117]

[0118]

[0119] In Table 1, the symbol “ / ” indicates that the performance index has not been measured or is not given.

[0120] Parts of the present invention that are not described in detail are well known to those skilled in the art.

[0121] Finally, it should be noted that: the above disclosed high-efficiency triazine ring-based hindered phenol antioxidant and its preparation method are introduced in detail, and the specific examples are used in this article to illustrate the implementation mode of the present invention, etc. The description of the above embodiments is only used to help understand the method of the present invention and its core idea; at the same time, for ordinary technicians in this field, according to the idea of ​​the present invention, there will be changes in the specific implementation mode and application scope. In summary, the content of this specification should not be understood as limiting the present invention; although the present invention is described in detail with reference to the above embodiments, ordinary technicians in this field should understand that: it is still possible to modify the technical solutions recorded in the above embodiments, or to replace some of the technical features therein by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A triazine ring hindered phenol antioxidant, It is characterized in that The structural formula of the triazine ring-based hindered phenol antioxidant is shown in the following formula I: In Formula I, 10≤n≤16, and n is a positive integer.

2. A method for preparing a triazine ring-based hindered phenol antioxidant, It is characterized in that The method comprises the following steps: (1) reacting a system comprising a long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran at 0 to 5° C. for 6 to 8 hours to obtain an intermediate; (2) reacting a system comprising an intermediate, 2,6-di-tert-butyl-4-hydroxymethylphenol, potassium carbonate and xylene at 40 to 60° C. for 2 to 4 hours, and then reacting at 80 to 100° C. for 5 to 8 hours to obtain a crude product; (3) dissolving the crude product with methanol aqueous solution to obtain a crude product solution system, then crystallizing the crude product solution system, and then filtering and drying to obtain a triazine ring-based hindered phenol antioxidant.

3. The preparation method according to claim 2, Features: The long-chain fatty amine is one or more of dodecylamine, tetradecylamine, hexadecylamine and octadecylamine.

4. The preparation method according to claim 2, Features: In step (1), the molar ratio of the long-chain fatty amine, the cyanuric chloride and the potassium carbonate is (1.8-2.2):(1.8-2.2):1, preferably 2:2:

1.

5. The preparation method according to claim 2, Features: In step (2), the molar ratio of the intermediate, the 2,6-di-tert-butyl-4-hydroxymethylphenol and the potassium carbonate is 1:(1.8-2.2):1, preferably 1:2:

1.

6. The preparation method according to claim 2, Features: The reaction in step (1) and / or step (2) is carried out under a nitrogen atmosphere.

7. The preparation method according to claim 2, Features: In step (1), the system comprising long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran is prepared by: uniformly mixing cyanuric chloride and long-chain fatty amine with tetrahydrofuran to obtain cyanuric chloride solution and long-chain fatty amine solution respectively; then, simultaneously adding long-chain fatty amine and potassium carbonate solution dropwise into the cyanuric chloride solution to obtain the system comprising long-chain fatty amine, cyanuric chloride, potassium carbonate and tetrahydrofuran.

8. The preparation method according to claim 2, Features: In step (2), the system comprising the intermediate, 2,6-di-tert-butyl-4-hydroxymethylphenol, potassium carbonate and xylene is prepared by mixing the intermediate and 2,6-di-tert-butyl-4-hydroxymethylphenol with xylene to obtain an intermediate solution and a 2,6-di-tert-butyl-4-hydroxymethylphenol solution, respectively; and then simultaneously adding the 2,6-di-tert-butyl-4-hydroxymethylphenol solution and the potassium carbonate solution to the intermediate solution to obtain a system comprising the intermediate, 2,6-di-tert-butyl-4-hydroxymethylphenol, potassium carbonate and xylene.

9. The preparation method according to claim 2, It is characterized in that The structural formula of the obtained triazine ring hindered phenol antioxidant is shown in the following formula I: In Formula I, 10≤n≤16, and n is a positive integer.

10. A triazine ring-based hindered phenol antioxidant prepared by the preparation method according to any one of claims 2 to 9.

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