Antioxidant 1098 as well as synthesis method and application thereof

Abstract

The invention relates to the field of antioxidants, and particularly discloses an antioxidant 1098 as well as a synthesis method and application thereof. According to the synthesis method of the antioxidant 1098, used catalysts comprise a sodium tetrahydroborate modified titanium dioxide catalyst and a metal composite solid acid catalyst, and effective metal elements in the metal composite solid acid catalyst comprise zinc, titanium and aluminum. The product provided by the invention can be compounded with an antioxidant 1076, an antioxidant 168 and a light stabilizer to be used as an antioxidant composition; the synthesis method has the advantages that the yield of the obtained product is high, the catalyst is easy to remove and recycle, and the yield can reach 99.13% or above; besides, the anti-radiation capability of the polymer can be remarkably optimized by the anti-oxidation composition, and by taking ABS resin as an example, the anti-oxidation composition can maintain the chromatic aberration of a product to be 4.5 or below, the tensile strength is improved to be 60% or above of the original tensile strength, and the impact strength is improved to be 33% or above of the original impact strength.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of antioxidants, and particularly relates to an antioxidant 1098 and a synthesis method and application thereof. BACKGROUND

[0002] Antioxidants are widely used in the field of industrial products to prevent the degradation of polymer materials such as rubber, plastic and adhesive due to oxidation, so as to lose strength and toughness. The molecular main chain of many polymers will be oxidized under the condition of light, heat and the like, so that the molecular main chain is broken, and at this time, the exposed surface of the polymer material begins to crack, which is mainly because the ultraviolet radiation or the excessively high temperature will cause the chemical bond to be broken to generate free radicals, and the generated free radicals will react with oxygen to generate peroxide radicals, which will cause further damage in a chain reaction manner. Other polymers including polypropylene and polyethylene are also susceptible to oxidation, so it is necessary to add antioxidants to industrial products.

[0003] The antioxidant 1098, full name N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, is a high-performance general antioxidant which does not discolor, does not pollute, is resistant to thermal oxidation and is resistant to extraction. The synthesis reaction of the antioxidant 1098 is an aminolysis reaction of 3,5-di-tert-butyl-4-hydroxybenzene propionic acid methyl ester and hexanediamine in a toluene solution, and during the reaction, organic tin supported molecular sieve, tetraisopropyl titanate, triethylamine and piperidine and the like are added as catalysts. The above catalysts can stabilize the yield of the antioxidant 1098 at a high level. The yield of the antioxidant 1098 under the catalysis of the organic tin supported molecular sieve is generally 95-96%, and the yield of the antioxidant 1098 under the catalysis of tetraisopropyl titanate, triethylamine and piperidine is 94-99%. It can be seen from this that although the solid catalyst has the advantage of being easy to separate, the yield still has room for improvement, and the yield of the liquid catalyst is relatively high, but the separation step is relatively complicated. SUMMARY

[0004] In order to improve the yield of the antioxidant 1098 and simplify the removal step of the catalyst, the present application provides an antioxidant 1098 and a synthesis method and application thereof.

[0005] In a first aspect, the present application provides a synthesis method of an antioxidant 1098, which comprises the following steps: dispersing 3,5-di-tert-butyl-4-hydroxybenzene propionic acid methyl ester, hexanediamine and a catalyst in an organic solvent and reacting, performing vacuum distillation, filtering to obtain a solid, dissolving the solid and filtering to obtain a mother liquor, and performing post-treatment on the mother liquor to obtain the antioxidant 1098. The catalyst comprises a sodium tetrahydroborate modified titanium dioxide catalyst and a metal composite solid acid catalyst. The effective metal elements in the metal composite solid acid catalyst include zinc, titanium and aluminum.

[0006] Specifically, the synthesis method of the antioxidant 1098 is as follows: 3,5-di-tert-butyl-4-hydroxybenzene propionic acid methyl ester and a catalyst are placed in a reaction device, after being protected by inert gas, hexanediamine and an organic solvent are added, and stirring is carried out under the conditions of a temperature of 130-140℃ and a pressure of 8-10mmHg, the reaction is completed after 5-5.3h, the obtained mixture is subjected to reduced pressure distillation to recover the organic solvent, the solid is obtained by filtration, the solid is dissolved and filtered again to remove the catalyst, a mother liquor is obtained, the mother liquor is heated and dissolved, and then crystallization is carried out at a temperature of 5-10℃ until no crystals are precipitated in the system, a crude product is obtained, the crude product is subjected to pressurized filtration, centrifugation, drying and grinding to obtain the antioxidant 1098, wherein the inert gas can be one or more of nitrogen, helium, argon and neon, the organic solvent can be benzene, toluene, xylene and cyclohexane, the solvent used for heating and dissolving the mother liquor can be any one of methanol or ethanol, and there is no significant difference between the above-mentioned substances, therefore, nitrogen, toluene and ethanol are used for illustration in the specific embodiments of the present application, which only represent one implementation scheme, and a person skilled in the art can adjust and replace according to the actual situation.

[0007] By adopting the above technical solution, the catalyst of the present application includes a sodium tetrahydroborate modified titanium dioxide catalyst and a metal composite solid acid catalyst, both of which are solid substances and can be removed by filtration in the synthesis process, easy to separate, and effectively optimize the operation simplicity of the synthesis method of the antioxidant 1098. Meanwhile, the sodium tetrahydroborate modified titanium dioxide catalyst has a large number of active sites, high catalytic activity, and higher stability and catalytic capacity than the unmodified titanium dioxide catalyst, the zinc element in the metal composite solid acid catalyst can improve the specific surface area of the metal composite solid acid catalyst, increase the contact area with the reactants in the system, and also improve the dispersion uniformity of titanium element, and there is a good coordination effect among zinc, titanium and aluminum, so that the metal composite solid acid catalyst as a whole has high catalytic activity, catalytic selectivity and larger effective contact area. In summary, the catalyst of the present application is not only easy to remove, but also has excellent catalytic capacity, which can significantly improve the product yield, and experimental data shows that the yield of the antioxidant 1098 can reach more than 99%.

[0008] Preferably, the weight ratio of the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst is 1:(0.4-0.6).

[0009] By adopting the technical scheme, the weight ratio of the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst is further controlled, so that the catalytic capacity of the catalyst as a whole is further optimized, and the number of active sites of the catalyst and the contact area with the reactants in the system are more optimally balanced. If the sodium tetrahydroborate modified titanium dioxide catalyst is used in too large an amount, the contact area of the catalyst with the reactants in the system is insufficient, and if the metal composite solid acid catalyst is used in too large an amount, the number of active sites of the catalyst is insufficient.

[0010] Preferably, the weight ratio of the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst is 1:0.52.

[0011] By adopting the technical scheme, the weight ratio of the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst is strictly controlled to be 1:0.52, at which time the number of active sites of the catalyst and the contact area with the reactants in the system are optimally balanced, so that the catalytic capacity of the catalyst is at an optimal level. Experimental data show that the yield of antioxidant 1098 is 99.24% at this time.

[0012] Specifically, the preparation of the sodium tetrahydroborate modified titanium dioxide catalyst includes the following steps: The titanium dioxide and the sodium tetrahydroborate are mixed and ground until the color changes, and then the mixture is placed in a tube furnace and heated under inert gas protection. After a period of time, it is cooled to room temperature, dispersed in water and left to stand for 12 h. Then the obtained mixed solution is centrifuged and washed to obtain solid material. The solid material is mixed with a 50wt% ethanol aqueous solution and then centrifuged and washed again. After filtration, a solid crude product is obtained. The crude product is dried to constant weight to obtain the sodium tetrahydroborate modified titanium dioxide catalyst.

[0013] Preferably, in the preparation of the sodium tetrahydroborate modified titanium dioxide catalyst, the weight ratio of the titanium dioxide and the sodium tetrahydroborate is 2:(1-3).

[0014] Preferably, the weight ratio of the titanium dioxide and the sodium tetrahydroborate is 2:2.

[0015] By adopting the technical scheme, the titanium dioxide is modified by sodium tetrahydroborate, the oxygen vacancy concentration on the surface of the titanium dioxide is increased, the catalytic activity of the titanium dioxide is significantly improved, and the chemical stability is also enhanced. Moreover, the weight ratio of the titanium dioxide and the sodium tetrahydroborate in the preparation of the sodium tetrahydroborate modified titanium dioxide catalyst is strictly controlled, the catalytic performance of the sodium tetrahydroborate modified titanium dioxide catalyst is further optimized, if the sodium tetrahydroborate is too small, the modification effect cannot be achieved, if the sodium tetrahydroborate is too large, the selectivity of the sodium tetrahydroborate modified titanium dioxide catalyst is reduced, therefore, no matter the sodium tetrahydroborate is too large or too small, the catalytic effect of the sodium tetrahydroborate modified titanium dioxide catalyst on the reactants in the system is affected, and the yield of antioxidant 1098 is reduced.

[0016] Preferably, the metal composite solid acid catalyst is prepared by the following method. The active Al2O3 is dispersed in anhydrous ethanol, stirred uniformly, and then adjusted to pH≤7 to obtain an aluminum liquid, then tetrabutyl titanate and zinc nitrate are also dispersed in anhydrous ethanol to obtain a titanium-zinc mixed liquid, anhydrous ethanol, water and glacial acetic acid are mixed to obtain a random liquid, the titanium-zinc mixed liquid and the random liquid are added to the aluminum liquid to obtain a mixed metal mother liquor, the mixed metal mother liquor is stirred uniformly, and then the system is adjusted to pH=8-8.2, then the temperature is increased and stirred, aged, filtered, washed, dried, calcined, and finally the metal composite solid acid catalyst is obtained, and the mixed metal mother liquor includes zinc, titanium and aluminum with a molar ratio of (2-6):(8-11):62.5.

[0017] Specifically, the mass ratio of anhydrous ethanol, water and glacial acetic acid in the random liquid is 1:1:1.

[0018] Preferably, the mixed metal mother liquor includes zinc, titanium and aluminum with a molar ratio of 4:10:62.5.

[0019] By adopting the technical scheme, the active Al2O3 is dispersed in anhydrous ethanol, then tetrabutyl titanate and zinc nitrate are also dispersed in anhydrous ethanol, and finally a metal composite solid acid catalyst containing zinc, titanium and aluminum is prepared through a series of reactions, which has high catalytic activity, catalytic selectivity and larger effective contact area with the reactants in the system. The molar ratio of zinc, titanium and aluminum in the mixed metal mother liquor is strictly controlled, so as to further optimize the catalytic effect of the metal composite solid acid catalyst, and experimental data proves that when the molar ratio of zinc, titanium and aluminum in the mixed metal mother liquor is 4:10:62.5, the yield of antioxidant 1098 can be increased by 0.05%.

[0020] In the second aspect, the application provides an antioxidant 1098.

[0021] In a third aspect, the present application provides an antioxidant composition, comprising antioxidant 1098, an auxiliary agent, and a light stabilizer, wherein the weight ratio of the antioxidant 1098, the auxiliary agent, and the light stabilizer is 5:1.2:(4-5), and the auxiliary agent comprises antioxidant 1076 and antioxidant 168 in a weight ratio of 1:(0.3-0.6).

[0022] Optionally, the light stabilizer is any one of light stabilizer 622, light stabilizer 944, and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.

[0023] Preferably, the light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.

[0024] In the preparation of disposable plastics, irradiation disinfection is a very common disinfection method, which has high and rapid sterilization efficacy, and has great utilization value in medical supplies made of disposable plastics. However, many polymers will have color change and mechanical property damage (especially the tensile strength and impact strength will be significantly reduced) after irradiation disinfection, which brings serious use limitations to many polymers. Therefore, in the existing polymer treatment, an antioxidant is added to improve the anti-irradiation capacity to maintain the stability of the mechanical properties.

[0025] By using the above technical solution, the antioxidant 1098, the auxiliary agent, and the light stabilizer are compounded to obtain an antioxidant composition with good anti-irradiation capacity. Experimental data show that in the irradiation disinfection of ABS resin, the addition of the antioxidant composition of the present application can maintain the color difference of the product below 4.5 at an irradiation intensity of 30 kGy, and at the same time, the tensile strength is improved to more than 60% of the original, and the impact strength is improved to more than 33% of the original, achieving good anti-irradiation effect.

[0026] The present application also uses bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate as a light stabilizer, which can further improve the anti-irradiation capacity of the antioxidant composition compared to light stabilizer 622 and light stabilizer 944. Experimental detection shows that it can further improve the tensile strength and impact strength of the ABS resin after irradiation.

[0027] In summary, the present application has the following beneficial technical effects: 1. In the synthesis method of the antioxidant 1098 of the present application, the catalysts used are sodium tetrahydroborate modified titanium dioxide catalyst and metal composite solid acid catalyst, both of which are solid substances. They are not only easy to remove, but also have high catalytic activity, catalytic selectivity, a large number of active sites, stability, and a larger effective contact area. Experimental data show that the yield of antioxidant 1098 can reach 99.13% at this time. 2. The antioxidant composition of the present application comprises antioxidant 1098, auxiliary agent and light stabilizer, has good anti-radiation ability, and can maintain the color difference of the product below 4.5 and improve the tensile strength to more than 60% of the original and the impact strength to more than 33% of the original at an irradiation intensity of 30 kGy in the irradiation sterilization of ABS resin. DETAILED DESCRIPTION

[0028] Material sources The raw materials used in the present application are commercially available products, specifically: Sodium tetrahydroborate was purchased from Merck Chemical Technology Co., Ltd., CAS No. 16940-66-2; Tetrabutyl titanate was purchased from Jinan Jiayang Chemical Co., Ltd., CAS No. 5593-70-4; 3,5-di-tert-butyl-4-hydroxybenzene propionic acid methyl ester was purchased from Zhongshan Dixin Chemical Co., Ltd., CAS No. 6386-38-5; Hexanediamine was purchased from Jinan Shidada Chemical Co., Ltd., CAS No. 65953-56-2; Titanium dioxide catalyst was purchased from Shandong Zhonghao Environmental Protection Technology Co., Ltd.; Antioxidant 1076 was purchased from Yuncheng Chemical Co., Ltd., CAS No. 2082-79-3; Antioxidant 168 was purchased from Nanjing Milan Chemical Co., Ltd., CAS No. 31570-04-4; Light stabilizer 622, light stabilizer 944 and di(2,2,6,6-tetramethyl-4-piperidine) sebacate were purchased from Changzhou Xinzhe Polymer Material Co., Ltd., CAS No. 65447-77-0, 71878-19-8 and 52829-07-9, respectively; Antioxidant 626 was purchased from Nanjing Milan Chemical Co., Ltd., CAS No. 26741-53-7; Antioxidant 1010 was purchased from Zhengzhou Yuhuo Food Additive Co., Ltd., CAS No. 6683-19-8.

[0029] The present application is further described in detail below in combination with examples, application examples and comparative examples.

[0030] Preparation Example 1.1 The preparation method of the sodium tetrahydroborate modified titanium dioxide catalyst comprises the following steps: After mixing 2 kg of titanium dioxide and 1 kg of sodium tetrahydroborate, the mixture was ground for 30 min, the mixture in the system changed color, grinding was stopped, and then the mixture was placed in a tube furnace, heated to 400°C at a heating rate of 2°C / min under N2protection, and treated at this temperature for 4 h, and then cooled to room temperature. The mixture obtained after heating was rapidly dispersed in water, left to stand for 12 h, and then the obtained mixture was centrifuged at a speed of 9000 rpm for 3 min to obtain solid material, the washing was repeated 6 times, and then the solid material was mixed with a 50 wt% ethanol aqueous solution and centrifuged again at the same speed for 3 min, filtered, and a solid crude product was obtained. The crude product was dried at a temperature of 90°C to a constant weight to obtain a sodium tetrahydroborate modified titanium dioxide catalyst.

[0031] Preparation Example 1.2 A method for preparing a sodium tetrahydroborate modified titanium dioxide catalyst includes the following steps: After mixing 2 kg of titanium dioxide and 1.7 kg of sodium tetrahydroborate, the mixture was ground for 30 min, the mixture in the system changed color, grinding was stopped, and then the mixture was placed in a tube furnace, heated to 410°C at a heating rate of 2°C / min under Ar protection, and treated at this temperature for 4 h, and then cooled to room temperature. The mixture obtained after heating was rapidly dispersed in water, left to stand for 12 h, and then the obtained mixture was centrifuged at a speed of 9200 rpm for 3 min to obtain solid material, the washing was repeated 6 times, and then the solid material was mixed with a 50 wt% ethanol aqueous solution and centrifuged again at the same speed for 3 min, filtered, and a solid crude product was obtained. The crude product was dried at a temperature of 95°C to a constant weight to obtain a sodium tetrahydroborate modified titanium dioxide catalyst.

[0032] Preparation Example 1.3 A method for preparing a sodium tetrahydroborate modified titanium dioxide catalyst includes the following steps: After mixing 2 kg of titanium dioxide and 2.3 kg of sodium tetrahydroborate, the mixture was ground for 30 min, the mixture in the system changed color, grinding was stopped, and then the mixture was placed in a tube furnace, heated to 390°C at a heating rate of 2°C / min under He protection, and treated at this temperature for 4 h, and then cooled to room temperature. The mixture obtained after heating was rapidly dispersed in water, left to stand for 12 h, and then the obtained mixture was centrifuged at a speed of 8700 rpm for 3 min to obtain solid material, the washing was repeated 6 times, and then the solid material was mixed with a 50 wt% ethanol aqueous solution and centrifuged again at the same speed for 3 min, filtered, and a solid crude product was obtained. The crude product was dried at a temperature of 95°C to a constant weight to obtain a sodium tetrahydroborate modified titanium dioxide catalyst.

[0033] Preparation Example 1.4 A method for preparing a sodium tetrahydroborate-modified titanium dioxide catalyst includes the following steps: After mixing 2 kg of titanium dioxide and 3 kg of sodium tetrahydroborate, grinding for 30 min, the mixture in the system changes color, stop grinding, then the mixture is placed in a tube furnace, heated to 405℃ at a heating rate of 2℃ / min under Ne protection, and treated at this temperature for 4 h, then cooled to room temperature, the mixture obtained after heating is rapidly dispersed in water, left to stand for 12 h, then the obtained mixture is centrifuged at a speed of 8500 rpm for 3 min to obtain solid material, the washing is repeated for 6 times, then the solid material is mixed with 50 wt% ethanol aqueous solution and centrifuged again at the same speed for 3 min, filtered to obtain a solid crude product, and the crude product is dried at a temperature of 90℃ until the weight is constant to obtain a sodium tetrahydroborate-modified titanium dioxide catalyst.

[0034] Preparation Example 2.1 A method for preparing a sodium tetrahydroborate-modified titanium dioxide catalyst, which is different from Preparation Example 1.1 in that the amount of sodium tetrahydroborate is 1.5 kg. The rest is the same as Preparation Example 1.1.

[0035] Preparation Example 2.2 A method for preparing a sodium tetrahydroborate-modified titanium dioxide catalyst, which is different from Preparation Example 1.1 in that the amount of sodium tetrahydroborate is 2 kg. The rest is the same as Preparation Example 1.1.

[0036] Preparation Example 2.3 A method for preparing a sodium tetrahydroborate-modified titanium dioxide catalyst, which is different from Preparation Example 1.1 in that the amount of sodium tetrahydroborate is 2.5 kg. The rest is the same as Preparation Example 1.1.

[0037] Preparation Example 2.4 A method for preparing a sodium tetrahydroborate-modified titanium dioxide catalyst, which is different from Preparation Example 1.1 in that the amount of sodium tetrahydroborate is 3 kg. The rest is the same as Preparation Example 1.1.

[0038] Preparation Example 2.5 A method for preparing a sodium tetrahydroborate-modified titanium dioxide catalyst, which is different from Preparation Example 1.1 in that the amount of sodium tetrahydroborate is 0.5 kg. The rest is the same as Preparation Example 1.1.

[0039] Preparation Example 2.6 A method for preparing a sodium tetrahydroborate-modified titanium dioxide catalyst, which is different from Preparation Example 1.1 in that the amount of sodium tetrahydroborate is 3.5 kg. The rest is the same as Preparation Example 1.1.

[0040] Preparation Example 3.1 A method for preparing a metal-composite solid acid catalyst includes the following steps: The active Al2O3 is dispersed in anhydrous ethanol according to a solid-liquid ratio of 1:20, stirred uniformly, and then adjusted to pH≤7 to obtain an aluminum liquid. Then, tetrabutyl titanate and zinc nitrate are also dispersed in anhydrous ethanol according to a solid-liquid ratio of 1:20 to obtain a titanium-zinc mixed liquid. Anhydrous ethanol, water, and glacial acetic acid are mixed according to a weight ratio of 1:1:1 to obtain a random liquid. The titanium-zinc mixed liquid and the random liquid are added to the aluminum liquid together, and the addition ratio is controlled so that the molar ratio of zinc, titanium, and aluminum in the obtained mixed metal mother liquor is 2:11:62.5. Then, the mixed metal mother liquor is stirred at a rotation speed of 8000 rpm for 2.5 h, the pH of the system is adjusted to 8, and then the stirring is continued at a temperature of 80°C and a rotation speed of 8000 rpm. The aging treatment is performed at a temperature of 80°C for 20 h. Filtration is performed, the filter cake is washed with deionized water at 80°C, and the washed filter cake is placed in an oven at 80°C for drying overnight. Finally, the filter cake is calcined at a temperature of 850°C to obtain a metal composite solid acid catalyst.

[0041] Preparation Example 3.2 The preparation method of the metal composite solid acid catalyst comprises the following steps: The active Al2O3 is dispersed in anhydrous ethanol according to a solid-liquid ratio of 1:20, stirred uniformly, and then adjusted to pH≤7 to obtain an aluminum liquid. Then, tetrabutyl titanate and zinc nitrate are also dispersed in anhydrous ethanol according to a solid-liquid ratio of 1:20 to obtain a titanium-zinc mixed liquid. Anhydrous ethanol, water, and glacial acetic acid are mixed according to a weight ratio of 1:1:1 to obtain a random liquid. The titanium-zinc mixed liquid and the random liquid are added to the aluminum liquid together, and the addition ratio is controlled so that the molar ratio of zinc, titanium, and aluminum in the obtained mixed metal mother liquor is 2:11:62.5. Then, the mixed metal mother liquor is stirred at a rotation speed of 8000 rpm for 2.5 h, the pH of the system is adjusted to 8, and then the stirring is continued at a temperature of 80°C and a rotation speed of 8000 rpm. The aging treatment is performed at a temperature of 80°C for 20 h. Filtration is performed, the filter cake is washed with deionized water at 80°C, and the washed filter cake is placed in an oven at 80°C for drying overnight. Finally, the filter cake is calcined at a temperature of 850°C to obtain a metal composite solid acid catalyst.

[0042] Preparation Example 3.3 The preparation method of the metal composite solid acid catalyst comprises the following steps: The active Al2O3 is dispersed in anhydrous ethanol according to a solid-liquid ratio of 1:20, stirred uniformly, and then adjusted to pH≤7 to obtain an aluminum liquid. Then, tetrabutyl titanate and zinc nitrate are also dispersed in anhydrous ethanol according to a solid-liquid ratio of 1:20 to obtain a titanium-zinc mixed liquid. Anhydrous ethanol, water and glacial acetic acid are mixed according to a weight ratio of 1:1:1 to obtain a random liquid. The titanium-zinc mixed liquid and the random liquid are added to the aluminum liquid together, and the addition ratio is controlled so that the molar ratio of zinc, titanium and aluminum in the obtained mixed metal mother liquor is 5:9:62.5. Then, the mixed metal mother liquor is stirred at a speed of 8000 rpm for 2.5 h, the pH of the system is adjusted to 8.2, and then stirring is continued at a temperature of 80℃ and a speed of 8000 rpm. The aging treatment is performed at a temperature of 80℃ for 20 h. Filtration is performed, the filter cake is washed with deionized water at 80℃, and the washed filter cake is placed in an oven at 80℃ for drying overnight. Finally, the filter cake is calcined at a temperature of 850℃ to obtain a metal composite solid acid catalyst.

[0043] Preparation Example 3.4 The preparation method of the metal composite solid acid catalyst comprises the following steps: The active Al2O3 is dispersed in anhydrous ethanol according to a solid-liquid ratio of 1:20, stirred uniformly, and then adjusted to pH≤7 to obtain an aluminum liquid. Then, tetrabutyl titanate and zinc nitrate are also dispersed in anhydrous ethanol according to a solid-liquid ratio of 1:20 to obtain a titanium-zinc mixed liquid. Anhydrous ethanol, water and glacial acetic acid are mixed according to a weight ratio of 1:1:1 to obtain a random liquid. The titanium-zinc mixed liquid and the random liquid are added to the aluminum liquid together, and the addition ratio is controlled so that the molar ratio of zinc, titanium and aluminum in the obtained mixed metal mother liquor is 5:9:62.5. Then, the mixed metal mother liquor is stirred at a speed of 8000 rpm for 2.5 h, the pH of the system is adjusted to 8.2, and then stirring is continued at a temperature of 80℃ and a speed of 8000 rpm. The aging treatment is performed at a temperature of 80℃ for 20 h. Filtration is performed, the filter cake is washed with deionized water at 80℃, and the washed filter cake is placed in an oven at 80℃ for drying overnight. Finally, the filter cake is calcined at a temperature of 850℃ to obtain a metal composite solid acid catalyst.

[0044] Preparation Example 4.1 The preparation method of the metal composite solid acid catalyst is different from that of Preparation Example 3.2 in that the molar ratio of zinc, titanium and aluminum in the obtained mixed metal mother liquor is controlled to be 5:9:62.5, and the rest is the same as that of Preparation Example 3.2.

[0045] Preparation Example 4.2 The preparation method of the metal composite solid acid catalyst is different from that of Preparation Example 3.2 in that the molar ratio of zinc, titanium and aluminum in the obtained mixed metal mother liquor is controlled to be 2:11:62.5, and the rest is the same as that of Preparation Example 3.2.

[0046] Preparation Example 4.3 The preparation method of the metal composite solid acid catalyst is different from that of Preparation Example 3.2 in that the addition ratio is controlled so that the molar ratio of zinc, titanium and aluminum in the obtained mixed metal mother liquor is 4:10:62.5, and the rest is the same as that of Preparation Example 3.2.

[0047] Preparation Example 4.4 The preparation method of the metal composite solid acid catalyst is different from that of Preparation Example 3.2 in that the addition ratio is controlled so that the molar ratio of zinc, titanium and aluminum in the obtained mixed metal mother liquor is 7:7:62.5, and the rest is the same as that of Preparation Example 3.2.

[0048] Preparation Example 4.5 The preparation method of the metal composite solid acid catalyst is different from that of Preparation Example 3.2 in that the addition ratio is controlled so that the molar ratio of zinc, titanium and aluminum in the obtained mixed metal mother liquor is 1:15:62.5, and the rest is the same as that of Preparation Example 3.2.

[0049] Comparative Preparation Example 1 The preparation method of the metal composite solid acid catalyst comprises the following steps: The active Al2O3 is dispersed in anhydrous ethanol at a solid-liquid ratio of 1:20, stirred uniformly, and then adjusted to pH≤7 to obtain an aluminum liquid. Tetra-n-butyl titanate is also dispersed in anhydrous ethanol at a solid-liquid ratio of 1:20 to obtain a titanium-zinc mixed liquid. Anhydrous ethanol, water and glacial acetic acid are mixed at a weight ratio of 1:1:1 to obtain a random liquid. The titanium-zinc mixed liquid and the random liquid are added to the aluminum liquid, the addition ratio is controlled so that the molar ratio of zinc, titanium and aluminum in the obtained mixed metal mother liquor is 11:62.5, then the mixed metal mother liquor is stirred at a speed of 8000 rpm for 2.5 h, the pH of the system is adjusted to 8.1, then the stirring is continued at a temperature of 80°C and a speed of 8000 rpm, the aging treatment is carried out at a temperature of 80°C for 20 h, the filtration is performed, the filter cake is washed with deionized water at 80°C, and the washed filter cake is placed in a drying oven at 80°C overnight. Finally, the filter cake is calcined at a temperature of 850°C to obtain the metal composite solid acid catalyst.

[0050] Comparative Preparation Example 2 The preparation method of the metal composite solid acid catalyst comprises the following steps: The tetrabutyl titanate and zinc nitrate are dispersed in anhydrous ethanol according to a solid-liquid ratio of 1:20 to obtain a titanium-zinc mixed solution, anhydrous ethanol, water and glacial acetic acid are mixed according to a weight ratio of 1:1:1 to obtain a dropwise addition solution, the dropwise addition solution is added to the titanium-zinc mixed solution, the addition ratio is controlled, the molar ratio of zinc to aluminum in the obtained mixed metal mother liquor is 2:6 2.5, then the mixed metal mother liquor is stirred at a rotation speed of 8000 rpm for 2.5 h, the pH of the system is adjusted to 8.1, then the stirring is continued at a temperature of 80°C and a rotation speed of 8000 rpm, the aging treatment is carried out at a temperature of 80°C for 20 h, the filter cake is washed with deionized water at 80°C, the washed filter cake is placed in a drying oven at 80°C overnight, and finally the filter cake is calcined at a temperature of 850°C to obtain a metal composite solid acid catalyst.

[0051] Examples 1-21 A synthesis method of an antioxidant 1098, comprising the following steps: 30 kg of 3,5-di-tert-butyl-4-hydroxybenzene propionic acid methyl ester and 60 g of a catalyst (detailed in Table 1) are placed in a reaction device, after N2 protection, 5.96 kg of hexanediamine and 50 L of toluene are added, and stirring is carried out at a temperature of 140°C and a pressure of 8 mm Hg, the reaction is completed after 5.3 h, the obtained mixed solution is subjected to vacuum distillation to recover toluene, the solid is filtered to completely dissolve the solid in anhydrous ethanol, and the catalyst is removed by filtration to obtain a mother liquor, the mother liquor is heated and dissolved, and then cooled and crystallized at a temperature of 5-10°C until no crystals are precipitated in the system to obtain a crude product, the crude product is subjected to pressurized filtration, centrifugation, drying, and grinding to obtain the antioxidant 1098, the yield is detected and recorded (detailed in Table 1).

[0052] Table 1 Catalyst addition and product yield of examples 1-21 Comparative example 1 Different from example 1 in that: the amount of the metal composite solid acid catalyst prepared in preparation example 3.2 is 60 g, the rest is the same as example 1, and the yield of antioxidant 1098 is 92.7%.

[0053] Comparative example 2 Different from example 1 in that: the metal composite solid acid catalyst prepared in preparation example 3.2 is removed, the amount of the sodium tetrahydroborate modified titanium dioxide catalyst prepared in preparation example 1.1 is 60 g, the rest is the same as example 1, and the yield of antioxidant 1098 is 94.1%.

[0054] Comparative Example 3 The difference from Example 1 is that the sodium tetrahydroborate-modified titanium dioxide catalyst prepared in Preparation Example 1.1 is replaced by a titanium dioxide catalyst, and the rest is the same as Example 1, and the yield of antioxidant 1098 is 90.6%.

[0055] Comparative Examples 4-5 The difference from Example 1 is that the metal composite solid acid catalyst prepared in Preparation Example 3.2 is replaced by the metal composite solid acid catalyst prepared in Comparative Preparation Examples 1-2, respectively, and the rest is the same as Example 1, and the yield of antioxidant 1098 is 95.2%, 95.6%, respectively.

[0056] Application Example 1 An antioxidant composition is prepared as follows: 5 kg of antioxidant 1098 prepared in Example 1, 0.92 kg of antioxidant 1076, 0.28 kg of antioxidant 168, and 4 kg of light stabilizer 622 are mixed to obtain an antioxidant composition.

[0057] Application Example 2 An antioxidant composition is prepared as follows: 5 kg of antioxidant 1098 prepared in Example 1, 0.86 kg of antioxidant 1076, 0.34 kg of antioxidant 168, and 4.5 kg of light stabilizer 622 are mixed to obtain an antioxidant composition.

[0058] Application Example 3 An antioxidant composition is prepared as follows: 5 kg of antioxidant 1098 prepared in Example 1, 0.75 kg of antioxidant 1076, 0.45 kg of antioxidant 168, and 5 kg of light stabilizer 622 are mixed to obtain an antioxidant composition.

[0059] Application Examples 4-5 An antioxidant composition is prepared as follows, which is different from Application Example 1 in that the light stabilizer 622 is replaced by light stabilizer 944 and di(2,2,6,6-tetramethyl-4-piperidyl) sebacate, respectively, and the rest is the same as Application Example 1.

[0060] Comparative Application Example 1 The difference from Application Example 1 is that all of the antioxidant 1076 is replaced by antioxidant 1010, and the rest is the same as Application Example 1.

[0061] Comparative Application Example 2 The difference from Application Example 1 is that all of the antioxidant 168 is replaced by antioxidant 626, and the rest is the same as Application Example 1.

[0062] Comparative Application Example 3 The difference from Application Example 1 is that the amount of antioxidant 1098 prepared in Example 1 is 4 kg, the amount of antioxidant 1076 is 1.69 kg, and the amount of antioxidant 168 is 0.51 kg, and the rest is the same as Application Example 1.

[0063] Comparative Application Example 4 The difference from Application Example 1 is that the amount of antioxidant 1098 prepared in Example 1 is 6 kg, the amount of antioxidant 1076 is 0.15 kg, and the amount of antioxidant 168 is 0.05 kg, and the rest is the same as Application Example 1.

[0064] Comparative Application Example 5 The difference from Application Example 1 is that the amount of antioxidant 1076 is 1 kg, and the amount of antioxidant 168 is 0.2 kg, and the rest is the same as Application Example 1.

[0065] Comparative Application Example 6 The difference from Application Example 1 is that the amount of antioxidant 1076 is 0.6 kg, and the amount of antioxidant 168 is 0.6 kg, and the rest is the same as Application Example 1.

[0066] Performance detection The ABS resin is blended with the antioxidant composition obtained in the application examples and comparative application examples, and is melt blended and modified by a double screw extruder, is cut into particles, is dried, and is injection molded to obtain an experimental group. The pure ABS resin is not added with any antioxidant substance, and is cut into particles, dried, and injection molded according to the steps to obtain a blank group. The experimental group and the blank group are placed in a Co-γ source, a basket structure source frame, and an environment with a radioactivity of 4.44×10 15 Bq for irradiation treatment, an isochronous rotation double-sided irradiation method is used to ensure the uniformity of the irradiation sterilization dose, the irradiation sterilization dose is set to 30 kGy, the dose rate is 6 Gy / s, and after 2 days of treatment, the performance is detected according to the following method: 1. The color difference of the experimental group and the blank group after irradiation is determined according to GB / T 251-2008, and is recorded in Table 2; 2. According to GB / T 1040.1-2018, the experimental group and the blank group are made into dumbbell-shaped sample bars, and the tensile strength is tested on a UTM universal material testing machine, the tensile strength change rate of each group of the experimental group is calculated according to the tensile strength of the blank group, and the results are recorded in Table 2. The tensile strength change rate = (experimental group tensile strength after irradiation-blank group tensile strength after irradiation) / blank group tensile strength after irradiation × 100%; 3. According to the description of GB / T 1043.1-2008, the experimental group and the blank group were made into dumbbell-shaped samples, and the simply supported beam impact test was carried out on the impact testing machine, and the impact strength was obtained, the impact strength change rate of each group of the experimental group was calculated according to the impact strength of the blank group, and the results were recorded in Table 2, the impact strength change rate = (the impact strength of the experimental group after irradiation-the impact strength of the blank group after irradiation) / the impact strength of the blank group after irradiation x 100%.

[0067] Table 2 Performance of ABS resin after irradiation with the addition of antioxidant composition Group Color difference value Tensile strength change rate % Impact strength change rate % Blank group 10.3 / / Example 1 4.4 61.2 34.0 Example 2 4.5 60.5 34.1 Example 3 4.4 61.4 33.1 Example 4 4.3 60.1 33.3 Example 5 4.7 63.8 34.9 Comparative Example 1 7.3 44.9 22.4 Comparative Example 2 5.9 46.1 23.8 Comparative Example 3 5.2 51.9 27.1 Comparative Example 4 5.3 52.8 26.8 Comparative Example 5 4.8 55.1 29.7 Comparative Example 6 4.7 54.8 28.3 Data analysis: As can be seen from Tables 1-2, the yield of antioxidant 1098 of Examples 1-4 can reach 99.13-99.15%, which proves that the catalyst used in the present application, the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst, not only is easy to remove, but also has high catalytic activity, catalytic selectivity, a large number of active sites, stability and a larger effective contact area, which can significantly improve the yield of the product; Examples 5-8 differ in that the weight ratio of the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst is different, and the yield of antioxidant 1098 of Example 6 is the highest, which proves that by strictly controlling the weight ratio of the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst, the number of active sites of the catalyst and the contact area with the reactants in the system are optimally balanced, so that the catalytic ability of the catalyst reaches the optimal level; The yield of antioxidant 1098 of Examples 9-10 is significantly lower than that of Example 1, which proves that if the amount of sodium tetrahydroborate modified titanium dioxide catalyst is too large, the contact area of the catalyst with the reactants in the system is insufficient, and if the amount of metal composite solid acid catalyst is too large, the number of active sites of the catalyst is insufficient, which will affect the overall catalytic effect of the catalyst and reduce the yield of the product; Examples 11-16 differ in that the amount of sodium tetrahydroborate in the sodium tetrahydroborate modified titanium dioxide catalyst is different, and the yield of antioxidant 1098 of Example 12 is the highest, which proves that by strictly controlling the amount of sodium tetrahydroborate, the catalytic performance of the sodium tetrahydroborate modified titanium dioxide catalyst is further optimized, if the amount of sodium tetrahydroborate is too small, it cannot effectively modify, and if the amount is too large, the selectivity of the sodium tetrahydroborate modified titanium dioxide catalyst will decrease, therefore, whether the amount is too large or too small will affect the catalytic effect of the sodium tetrahydroborate modified titanium dioxide catalyst on the reactants in the system, and reduce the yield of antioxidant 1098; The difference between Examples 17-21 is that the molar ratio in the metal composite solid acid catalyst is different, wherein the antioxidant 1098 yield of Example 19 is the highest, which proves that the application further optimizes the catalytic effect of the metal composite solid acid catalyst by strictly controlling the molar ratio of zinc, titanium and aluminum in the mixed metal mother liquor; The antioxidant 1098 yield of Comparative Example 1-2 is far lower than that of Example 1, which proves that the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst of the application not only have good catalytic ability, but also have a synergistic effect with each other, and the combination of the two in the system can achieve a more excellent catalytic effect; The antioxidant 1098 yield of Comparative Example 3 is far lower than that of Example 1, which proves that the catalytic ability and stability of the sodium tetrahydroborate modified titanium dioxide catalyst of the application are far higher than those of the ordinary unmodified titanium dioxide catalyst; The antioxidant 1098 yield of Comparative Examples 4-5 is far lower than that of Example 1, which proves that there is a good synergistic effect between zinc, titanium and aluminum in the metal composite solid acid catalyst of the application, so that the metal composite solid acid catalyst as a whole has high catalytic activity, catalytic selectivity and larger effective contact area; The antioxidant composition of Application Examples 1-3 can maintain the color difference at 4.4-4.5, the tensile strength change rate can reach 60.5-61.4%, and the impact strength change rate can reach 33.1-34.1% after irradiation for 2 days at an irradiation intensity of 30 kGy, which proves that the antioxidant 1098, the auxiliary agent and the light stabilizer in the antioxidant composition of the application can fully play a synergistic effect and improve the anti-irradiation ability of the polymer; The difference between Application Examples 1, 4 and 5 is that the types of light stabilizers are different, wherein the color difference of Application Example 5 is significantly lower than that of Application Examples 1 and 4, and the tensile strength change rate and the impact strength change rate are also larger, which proves that by selecting di(2,2,6,6-tetramethyl-4-piperidyl) sebacate as the light stabilizer, compared with light stabilizer 622 and light stabilizer 944, it can further improve the anti-irradiation ability of the antioxidant composition; The color difference of Comparative Application Examples 1-6 is significantly higher than that of Application Example 1, and the tensile strength change rate and the impact strength change rate are lower than those of Application Example 1, which proves that the fixed ratio and the fixed combination of the types of the antioxidant composition of the application can significantly improve the overall anti-irradiation ability, and there is a synergistic effect between multiple substances.

[0068] The examples of the specific embodiment are the preferred examples of the application, but do not limit the protection scope of the application, so that: any equivalent changes made according to the structure, shape, principle of the application should be covered within the protection scope of the application.

Claims

1. A method of synthesis of antioxidant 1098 comprising the steps of: Methyl 3,5-di-tert-butyl-4-hydroxybenzene propionate, hexanediamine and a catalyst are dispersed in an organic solvent and reacted, vacuum distillation is carried out, a solid is obtained by filtration, the solid is dissolved and filtered to obtain a mother liquor, the mother liquor is treated to obtain antioxidant 1098, characterized in that the catalyst comprises a sodium tetrahydroborate modified titanium dioxide catalyst and a metal composite solid acid catalyst, and effective metal elements in the metal composite solid acid catalyst comprise zinc, titanium and aluminum.

2. The method for synthesizing antioxidant 1098 according to claim 1, characterized in that: The weight ratio of the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst is 1: (0.4-0.6).

3. The method for synthesizing antioxidant 1098 according to claim 2, characterized in that: The weight ratio of the sodium tetrahydroborate modified titanium dioxide catalyst and the metal composite solid acid catalyst is 1:0.

52.

4. The method for synthesizing antioxidant 1098 according to claim 1, characterized in that: In the preparation of the sodium tetrahydroborate modified titanium dioxide catalyst, the weight ratio of titanium dioxide and sodium tetrahydroborate is 2: (1-3).

5. The method of claim 4, wherein: ###0002### 1098 is synthesized by the following steps: ###0003### 1098 The weight ratio of the titanium dioxide and sodium tetrahydroborate is 2:

2.

6. The method for synthesizing antioxidant 1098 according to claim 1, characterized in that: The metal composite solid acid catalyst is prepared by the following method: Active Al2O3 is dispersed in anhydrous ethanol, stirred uniformly, and then adjusted to pH≤7 to obtain an aluminum liquid, then tetrabutyl titanate and zinc nitrate are also dispersed in anhydrous ethanol to obtain a titanium-zinc mixed liquid, anhydrous ethanol, water and glacial acetic acid are mixed to obtain a random liquid, the titanium-zinc mixed liquid and the random liquid are added to the aluminum liquid to obtain a mixed metal mother liquor, the mixed metal mother liquor is stirred uniformly, then the system pH is adjusted to 8-8.2, then the temperature is raised and stirred, aged, filtered, washed, dried, calcined, and finally the metal composite solid acid catalyst is obtained, and the mixed metal mother liquor comprises zinc, titanium and aluminum in a molar ratio of (2-6): (8-11): 62.

5.

7. The method for synthesizing antioxidant 1098 according to claim 6, characterized in that: The mixed metal mother liquor comprises zinc, titanium and aluminum in a molar ratio of 4:10:62.

5.

8. The antioxidant 1098 obtained by the synthesis method of any one of claims 1-7.

9. An antioxidant composition characterized in that: It comprises the antioxidant 1098 of claim 8, an auxiliary agent and a light stabilizer in a weight ratio of 5:1.2: (4-5), the auxiliary agent comprises antioxidant 1076 and antioxidant 168 in a weight ratio of 1: (0.3-0.6).

10. The antioxidant composition of claim 9, wherein: The light stabilizer is di(2,2,6,6-tetramethyl-4-piperidyl) sebacate.

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