A diester ring hydrogenated bisphenol antioxidant and its preparation method and application

Abstract

The present invention discloses a diester ring hydrogenated bisphenol antioxidant, its preparation method, and application. The structural formula of the diester ring hydrogenated bisphenol antioxidant is shown in Formula I: wherein R1 and R2 are independently selected from one of hydrogen, an alkyl group, an amine group, a halogen group, a sulfonic acid group, a hydroxyl group, and an ester group. The modifiability and interchangeability of the side groups in the diester ring hydrogenated bisphenol antioxidant provided by the present invention greatly enrich the variety of phenolic antioxidants and provide new ideas for the design and preparation of high-performance phenolic antioxidants. Furthermore, the diester ring hydrogenated bisphenol antioxidant of the present invention not only has long-lasting antioxidant capacity but also exhibits anti-aging properties.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis and polymer materials, and in particular to a diester ring hydrogenated bisphenol antioxidant and a preparation method and application thereof. Background Art

[0002] Polymer materials have become indispensable in production and daily life due to their high performance, ease of modification, and lightweight properties. However, polymer materials can oxidize and age during processing, storage, and use. There are many methods to slow the oxidation of polymer materials, and adding antioxidants is a simple and effective method.

[0003] Amine antioxidants are the earliest and fastest-growing class of antioxidants used in polymer materials. However, their application has been limited by concerns about product color and the high toxicity of some varieties. Consequently, they have been gradually replaced by lighter-colored, less toxic phenolic antioxidants. However, compared to amine antioxidants, phenolic antioxidants have inferior antioxidant properties, necessitating further improvements in their performance. Summary of the Invention

[0004] In view of the above-mentioned deficiencies in the prior art, the present invention provides a diester ring hydrogenated bisphenol antioxidant and a preparation method and application thereof, so as to solve the problem that the antioxidant performance of existing phenolic antioxidants cannot meet the demand.

[0005] The technical solutions adopted by the present invention to solve the above technical problems are as follows:

[0006] In a first aspect of the present invention, a diester ring hydrogenated bisphenol antioxidant is provided, wherein the structural formula of the diester ring hydrogenated bisphenol antioxidant is shown in Formula I:

[0007]

[0008] Wherein, R1 and R2 are independently selected from one of hydrogen, alkyl, amino, halogen, sulfonic acid, hydroxyl and ester groups.

[0009] The second aspect of the present invention provides a method for preparing the above-mentioned diester ring hydrogenated bisphenol antioxidant, the preparation method comprising the following steps:

[0010] A hydrogenated bisphenol A as shown in Formula II and a 4-(2-bromoethyl)-2,3-disubstituted phenol as shown in Formula III are subjected to a nucleophilic addition reaction, and after purification, a diester ring hydrogenated bisphenol antioxidant as shown in Formula I is obtained; wherein R1 and R2 in Formula III are independently selected from one of hydrogen, alkyl, amino, halogen, sulfonic acid, hydroxyl, and ester groups;

[0011] The above reaction scheme is as follows:

[0012]

[0013] Preferably, the step of subjecting hydrogenated bisphenol A as shown in Formula II and 4-(2-bromoethyl)-2,3-disubstituted phenol as shown in Formula III to a nucleophilic addition reaction and obtaining the diester ring hydrogenated bisphenol antioxidant as shown in Formula I after purification specifically comprises:

[0014] Mixing hydrogenated bisphenol A as shown in formula II, 4-(2-bromoethyl)-2,3-disubstituted phenol as shown in formula III, a first solvent and a catalyst, and reacting at 60-120° C. for 2-12 hours;

[0015] After the reaction is completed, a second solvent is added for crystallization, and the filter cake obtained after filtration is washed with the second solvent. Finally, the washed filter cake is vacuum-dried at a temperature of 60-100° C. to obtain a diester ring hydrogenated bisphenol antioxidant as shown in Formula I.

[0016] Preferably, the equivalent ratio of the hydrogenated bisphenol A to the 4-(2-bromoethyl)-2,3-disubstituted phenol is 1:(2-4).

[0017] Preferably, the ratio of the volume of the first solvent to the sum of the masses of the hydrogenated bisphenol A and 4-(2-bromoethyl)-2,3-disubstituted phenol is (2-10) mL:1 g.

[0018] Preferably, the molar ratio of the catalyst to the hydrogenated bisphenol A is (1.3-5):1.

[0019] Preferably, the volume ratio of the second solvent to the first solvent is 20% to 150%.

[0020] Preferably, the first solvent is selected from one or more of toluene, xylene, solvent oil, chlorobenzene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and 1,2-dichloroethane, and the second solvent is selected from one or more of isopropanol, tert-butyl alcohol, isobutanol, acetonitrile, dioxane, ethylene glycol dimethyl ether, and methyl tert-butyl ether.

[0021] Preferably, the catalyst is selected from one or more of potassium carbonate, cesium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate.

[0022] Preferably, the diester ring hydrogenated bisphenol antioxidant or the diester ring hydrogenated bisphenol antioxidant prepared by the above preparation method is used in polymer materials.

[0023] Beneficial effects:

[0024] The present invention discloses a diester ring hydrogenated bisphenol antioxidant, its preparation method, and application. The modifiability and interchangeability of the side groups in the diester ring hydrogenated bisphenol antioxidant provided by the present invention significantly enrich the variety of phenolic antioxidants and provide new ideas for the design and preparation of high-performance phenolic antioxidants. Furthermore, the diester ring hydrogenated bisphenol antioxidant of the present invention not only exhibits long-lasting antioxidant capacity but also exhibits anti-aging properties. Furthermore, the preparation method provided by the present invention is simple, utilizes a wide range of inexpensive raw materials, and produces a high product yield. DETAILED DESCRIPTION

[0025] The present invention provides a diester ring hydrogenated bisphenol antioxidant, its preparation method, and application. To clarify the objectives, technical solutions, and effects of the present invention, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.

[0026] An embodiment of the present invention provides a diester ring hydrogenated bisphenol antioxidant, the structural formula of the diester ring hydrogenated bisphenol antioxidant is shown in Formula I:

[0027]

[0028] Wherein, R1 and R2 are independently selected from one of hydrogen, alkyl, amino, halogen, sulfonic acid, hydroxyl and ester groups.

[0029] In the present invention, different types of bisphenolic hindered phenol antioxidants are obtained by introducing different functional groups into the R1 and R2 substituents of the compound represented by Formula I and reacting them with the intermediate hydrogenated bisphenol A. Phenolic antioxidants are characterized by a benzene ring structure, in which the aromatic ring is rich in π electrons. These electrons can participate in the antioxidant process and neutralize active oxygen free radicals. Furthermore, phenolic antioxidants are generally stable to ultraviolet radiation and water vapor, thus exhibiting good weather resistance.

[0030] Moreover, compared with monophenolic hindered phenol antioxidants, the bisphenolic hindered phenol antioxidants provided in the embodiments of the present invention have a larger relative molecular mass, lower mobility in polymers, and higher thermal stability, and therefore have better anti-aging properties.

[0031] In some embodiments, the diester ring hydrogenated bisphenol antioxidant may be one of the following structural formulas, but is not limited thereto:

[0032]

[0033]

[0034] The present invention provides a method for preparing the above-mentioned diester ring hydrogenated bisphenol antioxidant, which comprises the following steps:

[0035] A hydrogenated bisphenol A as shown in Formula II and a 4-(2-bromoethyl)-2,3-disubstituted phenol as shown in Formula III are subjected to a nucleophilic addition reaction, and after purification, a diester ring hydrogenated bisphenol antioxidant as shown in Formula I is obtained; wherein R1 and R2 in Formula III are independently selected from one of hydrogen, alkyl, amino, halogen, sulfonic acid, hydroxyl, and ester groups;

[0036] The above reaction scheme is as follows:

[0037]

[0038] In some embodiments, when R1 and R2 in Formula III are both hydrogen, the structural formula of Formula III is The structure of the diester ring hydrogenated bisphenol antioxidant is

[0039] In some embodiments, when R1 and R2 in Formula III are both hydrogen, the structural formula of Formula III is The reaction formula for preparing the diester ring hydrogenated bisphenol antioxidant is:

[0040]

[0041] In some embodiments, when R1 in Formula III is amino and R2 is hydrogen, the structural formula of Formula III is The structure of the diester ring hydrogenated bisphenol antioxidant is

[0042] In some embodiments, when R1 in Formula III is amino and R2 is hydrogen, the structural formula of Formula III is The reaction formula for preparing the diester ring hydrogenated bisphenol antioxidant is:

[0043] In some embodiments, the steps of subjecting hydrogenated bisphenol A as shown in Formula II and 4-(2-bromoethyl)-2,3-disubstituted phenol as shown in Formula III to a nucleophilic addition reaction and purifying to obtain a diester ring hydrogenated bisphenol antioxidant as shown in Formula I specifically include:

[0044] Mixing hydrogenated bisphenol A as shown in formula II, 4-(2-bromoethyl)-2,3-disubstituted phenol as shown in formula III, a first solvent and a catalyst, and reacting at 60-120° C. for 2-12 hours;

[0045] After the reaction is completed, a second solvent is added for crystallization, and the filter cake obtained after filtration is washed with the second solvent. Finally, the washed filter cake is vacuum-dried at a temperature of 60-100° C. to obtain a diester ring hydrogenated bisphenol antioxidant as shown in Formula I.

[0046] In some embodiments, the equivalent ratio of the hydrogenated bisphenol A to the 4-(2-bromoethyl)-2,3-disubstituted phenol is 1:(2-4).

[0047] Among them, 4-(2-bromoethyl)-2,3-disubstituted phenol should participate in the reaction in a ratio of not less than 2 equivalents, because the diester ring hydrogenated bisphenol antioxidant of the embodiment of the present invention is a disubstituted structure; in addition, appropriately increasing the ratio of 4-(2-bromoethyl)-2,3-disubstituted phenol can accelerate the reaction rate and shorten the reaction time; however, a feed ratio greater than 4 equivalents leads to an excessively high concentration of 4-(2-bromoethyl)-2,3-disubstituted phenol, which will reduce the reaction rate and cause waste of raw materials.

[0048] In some preferred embodiments, the equivalent ratio of the hydrogenated bisphenol A to the 4-(2-bromoethyl)-2,3-disubstituted phenol is 1:(2.2-4).

[0049] In some embodiments, the ratio of the volume of the first solvent to the sum of the masses of the hydrogenated bisphenol A and 4-(2-bromoethyl)-2,3-disubstituted phenol is (2-10) mL:1 g.

[0050] When the ratio of the first solvent is less than 2, the solubility of the reaction raw materials decreases, the probability of collision between the raw materials decreases, and the reaction rate decreases; when the ratio of the first solvent is greater than 10, the concentration of the reaction raw materials is too low, which also leads to a decrease in reaction rate and waste of solvent. Therefore, in the embodiment of the present invention, the ratio of the volume of the first solvent to the sum of the masses of the hydrogenated bisphenol A and 4-(2-bromoethyl)-2,3-disubstituted phenol is set at (2-10) mL:1 g.

[0051] In some preferred embodiments, the ratio of the volume of the first solvent to the sum of the masses of the hydrogenated bisphenol A and 4-(2-bromoethyl)-2,3-disubstituted phenol is (2-8) mL:1 g.

[0052] In some embodiments, the molar ratio of the catalyst to the hydrogenated bisphenol A is (1.3-5):1.

[0053] In the preparation process of the present invention, the primary function of the catalyst is to remove hydrogen atoms from hydrogenated bisphenol A, facilitating the attack of the nucleophilic reagent. When the catalyst ratio is less than 1.3, the hydrogen removal efficiency is low. When the catalyst ratio is greater than 5, the solution becomes too alkaline, interfering with the nucleophilic substitution reaction and wasting the catalyst.

[0054] In some preferred embodiments, the molar ratio of the catalyst to the hydrogenated bisphenol A is (2-4):1.

[0055] In some embodiments, the volume ratio of the second solvent to the first solvent is 20% to 150%.

[0056] The main function of the second solvent is to wash away unreacted raw materials or impurities. If the amount is too small, it cannot be thoroughly washed away; if the amount is too large, it will cause partial product loss and waste solvent.

[0057] In some preferred embodiments, the volume ratio of the second solvent to the first solvent is 80% to 120%.

[0058] In some embodiments, the first solvent is selected from one or more of toluene, xylene, solvent oil, chlorobenzene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and 1,2-dichloroethane, and the second solvent is selected from one or more of isopropanol, tert-butanol, isobutanol, acetonitrile, dioxane, ethylene glycol dimethyl ether, and methyl tert-butyl ether.

[0059] In some preferred embodiments, the first solvent is selected from xylene or solvent oil, and the second solvent is selected from isopropyl alcohol or ethylene glycol dimethyl ether.

[0060] In some embodiments, the catalyst is selected from one or more of potassium carbonate, cesium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate.

[0061] In some preferred embodiments, the catalyst is potassium carbonate.

[0062] In some embodiments, the diester ring hydrogenated bisphenol antioxidant or the diester ring hydrogenated bisphenol antioxidant prepared by the above preparation method is used in polymer materials.

[0063] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them, and are intended only to illustrate the present invention and in no way limit the present invention. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are also within the scope of protection of the present invention.

[0064] Example 1

[0065] A preparation method of a diester ring hydrogenated bisphenol antioxidant comprises the following steps:

[0066] Xylene (150 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 4-(2-bromoethyl)phenol (23.99 g, 0.12 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 80°C for 8 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (90 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times. Finally, it was dried in vacuo at 100°C to obtain Yield 99.1%.

[0067] The above reaction scheme is as follows:

[0068]

[0069] Example 2

[0070] Xylene (330 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 4-(2-bromoethyl)phenol (39.98 g, 0.2 mol) and potassium carbonate (20.73 g, 0.15 mol) were added to the reactor in sequence and reacted at 60°C for 12 h. The reaction progress was monitored by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (225 mL) was added for crystallization. The filter cake was washed with 60 mL of isopropanol three times and finally dried in vacuo at 80°C to obtain Yield 97.3%.

[0071] The above reaction scheme is as follows:

[0072]

[0073] Example 3

[0074] Toluene (150 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 4-(2-bromoethyl)-2,3-dimethylphenol (38.76 g, 0.17 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 100 ° C for 10 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (100 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times and finally dried in vacuo at 90 ° C to obtain Yield 98.4%.

[0075] The above reaction scheme is as follows:

[0076]

[0077] Example 4

[0078] Toluene (260 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 4-(2-bromoethyl)-2,3-dimethylphenol (34.2 g, 0.15 mol) and potassium carbonate (20.73 g, 0.15 mol) were added to the reactor in sequence and reacted at 100 ° C for 8 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (230 mL) was added for crystallization. The filter cake was washed with 60 mL of isopropanol three times and finally dried in vacuo at 80 ° C to obtain Yield 99.3%.

[0079] The above reaction scheme is as follows:

[0080]

[0081] Example 5

[0082] Toluene (150 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 4-(2-bromoethyl)-2,3-diethylphenol (43.52 g, 0.17 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 100 ° C for 10 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (100 mL) was added for crystallization. The filter cake was washed with 60 mL of isopropanol three times and finally dried in vacuo at 90 ° C to obtain Yield 97.5%.

[0083] The above reaction scheme is as follows:

[0084]

[0085] Example 6

[0086] Toluene (180 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 4-(2-bromoethyl)-2,3-diethylphenol (51.2 g, 0.2 mol) and potassium carbonate (20.73 g, 0.15 mol) were added to the reactor in sequence and reacted at 100°C for 11 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (150 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times and finally dried in vacuo at 80°C to obtain Yield 98.5%.

[0087] The above reaction scheme is as follows:

[0088]

[0089] Example 7

[0090] Acetonitrile (150 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 2-amino-4-(2-bromoethyl)phenol (25.79 g, 0.12 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 100°C for 10 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (100 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times and finally dried in vacuo at 80°C to obtain Yield 93.8%.

[0091] The above reaction scheme is as follows:

[0092]

[0093] Example 8

[0094] Acetonitrile (200 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 2-amino-4-(2-bromoethyl)phenol (42.98 g, 0.2 mol) and potassium carbonate (20.73 g, 0.15 mol) were added to the reactor in sequence and reacted at 70°C for 12 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (140 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times. Finally, it was dried in vacuo at 100°C to obtain Yield 97.6%.

[0095] The above reaction scheme is as follows:

[0096]

[0097] Example 9

[0098] Dichloromethane (150 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 2-amino-4-(2-bromoethyl)-3-fluorophenol (27.95 g, 0.12 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 60°C for 10 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (100 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times and finally dried in vacuo at 60°C to obtain Yield 98.8%.

[0099] The above reaction scheme is as follows:

[0100]

[0101] Example 10

[0102] Dichloromethane (230 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 2-amino-4-(2-bromoethyl)-3-fluorophenol (41.925 g, 0.18 mol) and potassium carbonate (20.73 g, 0.15 mol) were added to the reactor in sequence and reacted at 90°C for 8 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (160 mL) was added for crystallization. The filter cake was washed with 60 mL of isopropanol three times and finally dried in vacuo at 65°C to obtain Yield 98.5%.

[0103] The above reaction scheme is as follows:

[0104]

[0105] Example 11

[0106] Benzene (150 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), methyl 6-(2-bromoethyl)-3-hydroxy-2-methylbenzoate (32.64 g, 0.12 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 90°C for 10 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (100 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times and finally dried in vacuo at 90°C to obtain Yield 97.5%.

[0107] The above reaction scheme is as follows:

[0108]

[0109] Example 12

[0110] Benzene (300 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), methyl 6-(2-bromoethyl)-3-hydroxy-2-methylbenzoate (48.96 g, 0.18 mol) and potassium carbonate (20.73 g, 0.15 mol) were added to the reactor in sequence and reacted at 110°C for 9 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (210 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times and finally dried in vacuo at 70°C to obtain Yield: 88.6%.

[0111] The above reaction scheme is as follows:

[0112]

[0113] Example 13

[0114] Benzene (150 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 5-(2-bromoethyl)-2-hydroxybenzenesulfonic acid (33.59 g, 0.12 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 90°C for 10 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (100 mL) was added for crystallization. The filter cake was washed with 60 mL of isopropanol three times and finally dried in vacuo at 80°C to obtain Yield 96.2%.

[0115] The above reaction scheme is as follows:

[0116]

[0117] Example 14

[0118] Benzene (260 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 5-(2-bromoethyl)-2-hydroxybenzenesulfonic acid (53.18 g, 0.19 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 100°C for 8 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (150 mL) was added for crystallization. The filter cake was washed with 60 mL of isopropanol three times and finally dried in vacuo at 90°C to obtain Yield 98.9%.

[0119] The above reaction scheme is as follows:

[0120]

[0121] Example 15

[0122] Solvent oil (150 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 6-(2-bromoethyl)-3-hydroxy-2-methylbenzenesulfonic acid (35.27 g, 0.12 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 80°C for 10 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (100 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times and finally dried in vacuo at 60°C to obtain Yield 98.3%.

[0123] The above reaction scheme is as follows:

[0124]

[0125] Example 16

[0126] Solvent oil (180 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), 6-(2-bromoethyl)-3-hydroxy-2-methylbenzenesulfonic acid (58.78 g, 0.2 mol) and potassium carbonate (20.73 g, 0.15 mol) were added to the reactor in sequence and reacted at 100 ° C for 8 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (90 mL) was added for crystallization. The filter cake was washed with 60 mL of isopropanol three times and finally dried in vacuo at 65 ° C to obtain Yield 99.2%.

[0127] The above reaction scheme is as follows:

[0128]

[0129] Example 17

[0130] Solvent oil (150 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), methyl 3-(2-bromoethyl)-2,6-dihydroxybenzoate (32.87 g, 0.12 mol) and potassium carbonate (13.82 g, 0.10 mol) were added to the reactor in sequence and reacted at 90°C for 10 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (100 mL) was added for crystallization. The filter cake was filtered and washed with 60 mL of isopropanol three times and finally dried in vacuo at 60°C to obtain Yield 95.2%.

[0131] The above reaction scheme is as follows:

[0132]

[0133] Example 18

[0134] Solvent oil (320 mL), hydrogenated bisphenol A (12.01 g, 0.05 mol), methyl 3-(2-bromoethyl)-2,6-dihydroxybenzoate (54.78 g, 0.2 mol) and potassium carbonate (27.64 g, 0.2 mol) were added to the reactor in sequence and reacted at 115°C for 8 h. The reaction progress was tracked by TLC. When the reaction point of hydrogenated bisphenol A disappeared, isopropanol (250 mL) was added for crystallization. The filter cake was washed with 60 mL of isopropanol three times and finally dried in vacuo at 90°C to obtain Yield 97.7%.

[0135] The above reaction scheme is as follows:

[0136]

[0137] Performance testing experiment

[0138] 1. Antioxidant effect test

[0139] The samples of the antioxidants prepared in Examples 1-18 blended with polypropylene and the commercial 1076 antioxidant blended with polypropylene were subjected to thermal decomposition tests under air conditions. The test results are shown in Table 1:

[0140] Table 1

[0141]

[0142]

[0143] As can be seen from Table 1, compared with the commercial 1076 antioxidant, the onset thermal degradation temperature of the composite material is significantly increased after adding the antioxidant of the present invention, indicating that the antioxidant prepared by the present invention has a better antioxidant effect than the widely used commercial antioxidant.

[0144] 2. Test of long-term antioxidant effect of antioxidants

[0145] The samples of the antioxidants prepared in Examples 1-18 blended with polypropylene and the commercial 1076 antioxidant blended with polypropylene were subjected to long-term heat aging tests at 200°C. The test results are shown in Table 2:

[0146] Table 2

[0147]

[0148]

[0149] As can be seen from Table 2, compared with the commercial 1076 antioxidant, the onset thermal degradation time of the composite material is significantly increased after adding the antioxidant of the present invention, indicating that the antioxidant prepared by the present invention has better long-term effectiveness than the widely used commercial antioxidant.

[0150] It should be understood that the application of the present invention is not limited to the above examples. For those skilled in the art, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A diester ring hydrogenated bisphenol antioxidant, characterized in that: The structural formula of the diester ring hydrogenated bisphenol antioxidant is shown in Formula I: Wherein, R1 and R2 are independently selected from one of hydrogen, alkyl, amino, halogen, sulfonic acid, hydroxyl and ester groups.

2. A method for preparing the diester ring hydrogenated bisphenol antioxidant according to claim 1, characterized in that: The preparation method comprises the following steps: A hydrogenated bisphenol A as shown in Formula II and a 4-(2-bromoethyl)-2,3-disubstituted phenol as shown in Formula III are subjected to a nucleophilic addition reaction, and after purification, a diester ring hydrogenated bisphenol antioxidant as shown in Formula I is obtained; wherein R1 and R2 in Formula III are independently selected from one of hydrogen, alkyl, amino, halogen, sulfonic acid, hydroxyl, and ester groups; The above reaction scheme is as follows:

3. The method for preparing the diester ring hydrogenated bisphenol antioxidant according to claim 2, wherein: The steps of subjecting hydrogenated bisphenol A as shown in Formula II and 4-(2-bromoethyl)-2,3-disubstituted phenol as shown in Formula III to a nucleophilic addition reaction and obtaining a diester ring hydrogenated bisphenol antioxidant as shown in Formula I after purification specifically include: Mixing hydrogenated bisphenol A as shown in formula II, 4-(2-bromoethyl)-2,3-disubstituted phenol as shown in formula III, a first solvent and a catalyst, and reacting at 60-120° C. for 2-12 hours; After the reaction is completed, a second solvent is added for crystallization, and the filter cake obtained after filtration is washed with the second solvent. Finally, the washed filter cake is vacuum-dried at a temperature of 60 to 100° C. to obtain a diester ring hydrogenated bisphenol antioxidant as shown in Formula I; The catalyst is selected from one or more of potassium carbonate, cesium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate.

4. The method for preparing a diester ring hydrogenated bisphenol antioxidant according to claim 2, wherein: The equivalent ratio of the hydrogenated bisphenol A to the 4-(2-bromoethyl)-2,3-disubstituted phenol is 1:(2-4).

5. The method for preparing the diester ring hydrogenated bisphenol antioxidant according to claim 3, characterized in that: The ratio of the volume of the first solvent to the sum of the masses of the hydrogenated bisphenol A and 4-(2-bromoethyl)-2,3-disubstituted phenol is (2-10) mL:1 g.

6. The method for preparing the diester ring hydrogenated bisphenol antioxidant according to claim 3, characterized in that: The molar ratio of the catalyst to the hydrogenated bisphenol A is (1.3-5):

1.

7. The method for preparing the diester ring hydrogenated bisphenol antioxidant according to claim 3, characterized in that: The volume ratio of the second solvent to the first solvent is 20% to 150%.

8. The method for preparing the diester ring hydrogenated bisphenol antioxidant according to claim 3, characterized in that: The first solvent is selected from one or more of toluene, xylene, solvent oil, chlorobenzene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and 1,2-dichloroethane, and the second solvent is selected from one or more of isopropyl alcohol, tert-butyl alcohol, isobutanol, acetonitrile, dioxane, ethylene glycol dimethyl ether, and methyl tert-butyl ether.

9. Use of the diester ring hydrogenated bisphenol antioxidant according to claim 1 or the diester ring hydrogenated bisphenol antioxidant prepared by the preparation method according to claims 2 to 8 in polymer materials.

Images