CN113200942A - Antioxidant and method for preparing antioxidant - Google Patents

Antioxidant and method for preparing antioxidant Download PDF

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CN113200942A
CN113200942A CN202110515513.6A CN202110515513A CN113200942A CN 113200942 A CN113200942 A CN 113200942A CN 202110515513 A CN202110515513 A CN 202110515513A CN 113200942 A CN113200942 A CN 113200942A
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reaction kettle
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rotation speed
antioxidant
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Shangshao Tongenda Shaoxing New Material Technology Co ltd
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    • C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
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    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/65719—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonous acid derivative

Abstract

The invention discloses an antioxidant and a method for preparing the antioxidant, wherein the antioxidant is prepared by reacting an intermediate 2 with an intermediate 5 to prepare an intermediate 14, oxidizing the intermediate 14 by potassium permanganate, then carrying out esterification with an intermediate 13 to prepare an intermediate 15, reducing the intermediate 15 by tin powder to prepare an intermediate 16, and carrying out dehydration condensation on the intermediate 16 and an intermediate 8.

Description

Antioxidant and method for preparing antioxidant
Technical Field
The invention relates to the technical field of antioxidant preparation, and particularly relates to an antioxidant and a method for preparing the antioxidant.
Background
An antioxidant is an organic composition that inhibits or delays the thermal oxidation of polymers and other organic compounds in air, and is generally very effective when added at a minute concentration of 1%. For example, foods are susceptible to oxidative deterioration and small amounts of antioxidants may be added to prolong their shelf life. High polymer materials such as plastics, synthetic fibers, rubber and the like are easy to generate thermal oxidative degradation reaction, and the antioxidant is added to keep the excellent performance of the high polymer materials and prolong the service life.
The performance of the existing antioxidant is generally greatly reduced under the influence of the environment on a polymer, the antioxidant is easily separated out from the polymer material, and after the antioxidant is used for a long time, an antioxidant substance is separated out from the surface of the polymer, so that the antioxidant effect is influenced.
Disclosure of Invention
The invention aims to provide an antioxidant and a method for preparing the antioxidant.
The technical problems to be solved by the invention are as follows:
the performance of the existing antioxidant is generally greatly reduced under the influence of the environment on a polymer, the antioxidant is easily separated out from the polymer material, and after the antioxidant is used for a long time, an antioxidant substance is separated out from the surface of the polymer, so that the antioxidant effect is influenced.
The purpose of the invention can be realized by the following technical scheme:
an antioxidant is prepared by the following steps:
step S1: adding m-chloro diphenylamine, sulfur and iodine into a reaction kettle, reacting at the rotation speed of 200-180 ℃ at 300r/min and at the temperature of 170-180 ℃ until no hydrogen sulfide gas is generated to prepare an intermediate 1, containing cyanuric chloride into acetone, adding the intermediate 1, and reacting at the rotation speed of 150-200r/min and at the temperature of 80-90 ℃ for 5-8h to prepare an intermediate 2;
the reaction process is as follows:
Figure BDA0003061816140000021
step S2: adding o-toluidine, glacial acetic acid and zinc powder into a reaction kettle, stirring for 20-30min under the conditions of a rotation speed of 150-, stirring for 20-30min, filtering, and adjusting the filtrate with ammonia water to pH 8-9 to obtain intermediate 5;
the reaction process is as follows:
Figure BDA0003061816140000031
step S3: adding 2-methyl-1, 3-propanediol and toluene into a reaction kettle, stirring and dropwise adding phosphorus trichloride under the conditions of a rotation speed of 150-;
the reaction process is as follows:
Figure BDA0003061816140000032
Figure BDA0003061816140000041
step S4: adding p-chloronitrobenzene, p-methylaniline, potassium carbonate, a phase transfer agent PEG-600, copper oxide and toluene into a reaction kettle, introducing nitrogen for protection, reacting for 6-8h at the temperature of 185-190 ℃ to obtain an intermediate 9, adding the intermediate 9, ethanol and palladium carbon into the reaction kettle, introducing nitrogen for protection, introducing hydrogen until the pressure is 1.5-2.0MPa, reacting at the rotation speed of 800-1000r/min and the temperature of 80-100 ℃ until the pressure is stable to obtain an intermediate 10, adding the intermediate 10, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 11;
the reaction process is as follows:
Figure BDA0003061816140000042
Figure BDA0003061816140000051
step S5: adding the intermediate 11, methyl isobutyl ketone and palladium carbon into a reaction kettle, replacing air with nitrogen, then introducing hydrogen until the pressure is 0.2-0.3MPa, keeping the temperature at 40-50 ℃, reacting for 2-3h under the conditions of the pressure of 1.3-1.6MPa, the rotating speed of 600-800r/min and the temperature of 110-120 ℃ to obtain an intermediate 12, adding the intermediate 12, a potassium carbonate solution and tetraethylammonium bromide into the reaction kettle, and refluxing for 1-1.5h under the condition of the temperature of 100-110 ℃ to obtain an intermediate 13;
the reaction process is as follows:
Figure BDA0003061816140000052
step S6: adding the intermediate 2, the intermediate 5, potassium tert-butoxide and 1, 2-dioxane into a reaction kettle, introducing nitrogen for protection, reacting for 3-5h at the temperature of 110-115 ℃ to obtain an intermediate 14, adding the intermediate 14 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at the temperature of 100-110 ℃, reacting for 3-5h, adding the intermediate 13 and concentrated sulfuric acid, reacting for 2-3h at the temperature of 50-60 ℃ to obtain an intermediate 15, adding the intermediate 15, tin powder and concentrated hydrochloric acid into the reaction kettle, reacting for 30-40min at the rotation speed of 150-200r/min in a boiling water bath to obtain an intermediate 16, and adding the intermediate 16, the intermediate 8, 1-hydroxybenzotriazole, 1-hydroxy benzotriazole, Adding dimethyl sulfoxide into a reaction kettle, reacting for 3-5h at the rotation speed of 200-300r/min, and removing the dimethyl sulfoxide to obtain the antioxidant.
The reaction process is as follows:
Figure BDA0003061816140000061
Figure BDA0003061816140000071
Figure BDA0003061816140000081
further, the molar ratio of the m-chlorodiphenylamine, the sulfur and the iodine used in the step S1 is 25:50:0.1, and the molar ratio of the cyanuric chloride to the intermediate 1 is 1:3.
Further, in step S2, the dosage ratio of o-toluidine, glacial acetic acid, and zinc powder is 2mol:5mol:2g, the dosage ratio of intermediate 3, dichloromethane, and mixed acid is 0.1mol:30mL:5mL, the mixed acid is a mixture of concentrated nitric acid with a mass fraction of 68% and concentrated sulfuric acid with a mass fraction of 98% in a molar ratio of 5:7, the dosage ratio of intermediate 4 and concentrated hydrochloric acid is 0.1mol:30mL, and the mass fraction of concentrated hydrochloric acid is 36%.
Further, the molar ratio of the 2-methyl-1, 3-propanediol to the phosphorus trichloride in step S3 is 1:1, the molar ratio of the intermediate 6, the deionized water to the potassium permanganate is 2.5g:80mL:4.3g, and the molar ratio of the 2, 4-di-tert-butylphenol, the triethylamine and the intermediate 7 is 0.2mol:0.3g:0.2 mol.
Further, the dosage ratio of p-chloronitrobenzene, p-methylaniline, potassium carbonate, phase transfer agent PEG-600 and copper oxide in the step S4 is 0.1mol:0.15mol:7.5g:3g:0.8g, the dosage ratio of intermediate 9, ethanol and palladium carbon is 0.3mol:100mL:1.3g, and the dosage ratio of intermediate 10, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride is 0.15mol:0.15mol:0.3g:200 mL.
Further, the molar ratio of the intermediate 11 to the methyl isobutyl ketone in step S5 is 1:3.5, the amount of palladium on carbon is 3-5% of the sum of the intermediate 11 and the methyl isobutyl ketone, the ratio of the intermediate 12, the potassium carbonate solution and the tetraethylammonium bromide is 5g:100mL:4.7mL, and the mass fraction of the potassium carbonate solution is 10%.
Further, the dosage ratio of the intermediate 2, the intermediate 5, the potassium tert-butoxide and the 1, 2-dioxane described in the step S6 is 0.025mol:0.03mol:0.035mol:70mL, the dosage ratio of the intermediate 14, the deionized water, the potassium permanganate, the intermediate 13 and the concentrated sulfuric acid is 0.01mol:80mL:4.3g:0.03mol:8mL, the mass fraction of the concentrated sulfuric acid is 95%, the dosage ratio of the intermediate 15, the tin powder and the concentrated hydrochloric acid is 5g:8g:20mL, the mass fraction of the concentrated hydrochloric acid is 38%, and the dosage molar ratio of the intermediate 16, the intermediate 8 and the 1-hydroxybenzotriazole is 1:3: 0.5.
A preparation method of an antioxidant specifically comprises the following steps:
step S1: adding m-chloro diphenylamine, sulfur and iodine into a reaction kettle, reacting at the rotation speed of 200-180 ℃ at 300r/min and at the temperature of 170-180 ℃ until no hydrogen sulfide gas is generated to prepare an intermediate 1, containing cyanuric chloride into acetone, adding the intermediate 1, and reacting at the rotation speed of 150-200r/min and at the temperature of 80-90 ℃ for 5-8h to prepare an intermediate 2;
step S2: adding o-toluidine, glacial acetic acid and zinc powder into a reaction kettle, stirring for 20-30min under the conditions of a rotation speed of 150-, stirring for 20-30min, filtering, and adjusting the filtrate with ammonia water to pH 8-9 to obtain intermediate 5;
step S3: adding 2-methyl-1, 3-propanediol and toluene into a reaction kettle, stirring and dropwise adding phosphorus trichloride under the conditions of a rotation speed of 150-;
step S4: adding p-chloronitrobenzene, p-methylaniline, potassium carbonate, a phase transfer agent PEG-600, copper oxide and toluene into a reaction kettle, introducing nitrogen for protection, reacting for 6-8h at the temperature of 185-190 ℃ to obtain an intermediate 9, adding the intermediate 9, ethanol and palladium carbon into the reaction kettle, introducing nitrogen for protection, introducing hydrogen until the pressure is 1.5-2.0MPa, reacting at the rotation speed of 800-1000r/min and the temperature of 80-100 ℃ until the pressure is stable to obtain an intermediate 10, adding the intermediate 10, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 11;
step S5: adding the intermediate 11, methyl isobutyl ketone and palladium carbon into a reaction kettle, replacing air with nitrogen, then introducing hydrogen until the pressure is 0.2-0.3MPa, keeping the temperature at 40-50 ℃, reacting for 2-3h under the conditions of the pressure of 1.3-1.6MPa, the rotating speed of 600-800r/min and the temperature of 110-120 ℃ to obtain an intermediate 12, adding the intermediate 12, a potassium carbonate solution and tetraethylammonium bromide into the reaction kettle, and refluxing for 1-1.5h under the condition of the temperature of 100-110 ℃ to obtain an intermediate 13;
step S6: adding the intermediate 2, the intermediate 5, potassium tert-butoxide and 1, 2-dioxane into a reaction kettle, introducing nitrogen for protection, reacting for 3-5h at the temperature of 110-115 ℃ to obtain an intermediate 14, adding the intermediate 14 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at the temperature of 100-110 ℃, reacting for 3-5h, adding the intermediate 13 and concentrated sulfuric acid, reacting for 2-3h at the temperature of 50-60 ℃ to obtain an intermediate 15, adding the intermediate 15, tin powder and concentrated hydrochloric acid into the reaction kettle, reacting for 30-40min at the rotation speed of 150-200r/min in a boiling water bath to obtain an intermediate 16, and adding the intermediate 16, the intermediate 8, 1-hydroxybenzotriazole, 1-hydroxy benzotriazole, Adding dimethyl sulfoxide into a reaction kettle, reacting for 3-5h at the rotation speed of 200-300r/min, and removing the dimethyl sulfoxide to obtain the antioxidant.
The invention has the beneficial effects that: the invention takes m-chloro diphenylamine and sulfur as raw materials, takes iodine as a catalyst to react to prepare an intermediate 1, the intermediate 1 reacts with cyanuric chloride to prepare an intermediate 2, o-toluidine is protected by amino with glacial acetic acid to prepare an intermediate 3, the intermediate 3 reacts with mixed acid to prepare an intermediate 4, the intermediate 4 is hydrolyzed by concentrated hydrochloric acid to prepare an intermediate 5, 2-methyl-1, 3-propanediol reacts with phosphorus trichloride to prepare an intermediate 6, the intermediate 6 is oxidized to prepare an intermediate 7, 2, 4-di-tert-butylphenol reacts with the intermediate 7 to prepare an intermediate 8, p-chloronitrobenzene reacts with p-methylbenzene to prepare an intermediate 9, the intermediate 9 is reduced by palladium carbon to prepare an intermediate 10, the intermediate 10 reacts with nitrogen-bromosuccinimide to prepare an intermediate 11, the intermediate 11 reacts with methyl isobutyl ketone to prepare an intermediate 12, the intermediate 12 reacts to prepare an intermediate 13, the intermediate 2 reacts with the intermediate 5 to prepare an intermediate 14, the intermediate 14 is oxidized by potassium permanganate and then esterified with the intermediate 13 to prepare an intermediate 15, the intermediate 15 is reduced by tin powder to prepare an intermediate 16, the intermediate 16 and the intermediate 8 are subjected to dehydration condensation to prepare the antioxidant, the antioxidant contains a large amount of sulfur atoms, the sulfur atoms can be oxidized to form sulfoxide and sulfone compounds, the antioxidant has good oxidation resistance, free radicals generated by macromolecules can be captured, the free radical branching reaction is inhibited, and the oxidation resistance of the high polymer material is improved, and the molecular weight of the polymer is large, so that the polymer is difficult to separate out from the polymer material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An antioxidant is prepared by the following steps:
step S1: adding m-chlorodiphenylamine, sulfur and iodine into a reaction kettle, reacting at the rotation speed of 200r/min and the temperature of 170 ℃ until no hydrogen sulfide gas is generated to prepare an intermediate 1, containing cyanuric chloride in acetone, adding the intermediate 1, and reacting at the rotation speed of 150/min and the temperature of 80 ℃ for 5 hours to prepare an intermediate 2;
step S2: adding o-toluidine, glacial acetic acid and zinc powder into a reaction kettle, stirring for 20min at the rotation speed of 150r/min and the temperature of 100 ℃, cooling to 20 ℃ to prepare an intermediate 3, adding the intermediate 3, dichloromethane and mixed acid into a reaction kettle, reacting for 30min under the conditions of the rotating speed of 200r/min and the temperature of 10 ℃, distilling to remove dichloromethane, cooling to reaction solution temperature of 0 deg.C, filtering to remove filtrate, washing filter cake with deionized water to pH 7 to obtain intermediate 4, adding intermediate 4, concentrated hydrochloric acid and zeolite into reaction kettle, refluxing for 3h at 100 ℃, cooling to separate out a solid, stirring for 20min at the rotation speed of 200r/min, filtering, and adjusting the filtrate with ammonia water until the pH value is 8 to obtain an intermediate 5;
step S3: adding 2-methyl-1, 3-propylene glycol and toluene into a reaction kettle, stirring and dropwise adding phosphorus trichloride under the conditions of the rotation speed of 150r/min and the temperature of 30 ℃ for reacting for 3 hours to obtain an intermediate 6, adding the intermediate 6 and deionized water into the reaction kettle, refluxing and adding potassium permanganate under the condition of the temperature of 100 ℃ for reacting for 4 hours to obtain an intermediate 7, adding 2, 4-di-tert-butylphenol, toluene and triethylamine into the reaction kettle, stirring and adding the intermediate 7 under the conditions of the rotation speed of 120r/min and the temperature of 40 ℃ for reacting for 3 hours to obtain an intermediate 8;
step S4: adding p-chloronitrobenzene, p-methylaniline, potassium carbonate, a phase transfer agent PEG-600, copper oxide and toluene into a reaction kettle, introducing nitrogen for protection, reacting for 6 hours at 185 ℃ to obtain an intermediate 9, adding the intermediate 9, ethanol and palladium carbon into the reaction kettle, introducing nitrogen for protection, introducing hydrogen until the pressure is 1.5MPa, reacting at the rotation speed of 800r/min and the temperature of 80 ℃ until the pressure is stable to obtain an intermediate 10, adding the intermediate 10, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 8 hours at 80 ℃ to obtain an intermediate 11;
step S5: adding the intermediate 11, methyl isobutyl ketone and palladium carbon into a reaction kettle, replacing air with nitrogen, introducing hydrogen until the pressure is 0.2MPa, keeping the temperature at 40 ℃ for 10min, reacting for 2h under the conditions of the pressure of 1.3MPa, the rotating speed of 600r/min and the temperature of 110 ℃ to obtain an intermediate 12, adding the intermediate 12, a potassium carbonate solution and tetraethylammonium bromide into the reaction kettle, and refluxing for 1h under the condition of the temperature of 100 ℃ to obtain an intermediate 13;
step S6: adding the intermediate 2, the intermediate 5, potassium tert-butoxide and 1, 2-dioxane into a reaction kettle, introducing nitrogen for protection, reacting for 3 hours at 110 ℃ to obtain an intermediate 14, adding the intermediate 14 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at 100 ℃, reacting for 3 hours, adding the intermediate 13 and concentrated sulfuric acid, reacting for 2 hours at 50 ℃ to obtain an intermediate 15, adding the intermediate 15, tin powder and concentrated hydrochloric acid into the reaction kettle, reacting for 30 minutes in a boiling water bath at 150r/min to obtain an intermediate 16, adding the intermediate 16, the intermediate 8, 1-hydroxybenzotriazole and dimethyl sulfoxide into the reaction kettle, reacting for 3 hours at 200r/min, removing dimethyl sulfoxide to obtain antioxidant.
Example 2
An antioxidant is prepared by the following steps:
step S1: adding m-chloro diphenylamine, sulfur and iodine into a reaction kettle, reacting at the rotation speed of 200r/min and the temperature of 180 ℃ until no hydrogen sulfide gas is generated to prepare an intermediate 1, containing cyanuric chloride in acetone, adding the intermediate 1, and reacting at the rotation speed of 150r/min and the temperature of 90 ℃ for 5 hours to prepare an intermediate 2;
step S2: adding o-toluidine, glacial acetic acid and zinc powder into a reaction kettle, stirring for 30min at the rotation speed of 200r/min and the temperature of 100 ℃, cooling to 20 ℃ to prepare an intermediate 3, adding the intermediate 3, dichloromethane and mixed acid into a reaction kettle, after the reaction is carried out for 40min under the conditions that the rotating speed is 300r/min and the temperature is 10 ℃, distilling to remove dichloromethane, cooling to reaction solution temperature of 0 deg.C, filtering to remove filtrate, washing filter cake with deionized water to pH 7 to obtain intermediate 4, adding intermediate 4, concentrated hydrochloric acid and zeolite into reaction kettle, refluxing for 3h at 110 ℃, cooling to separate out a solid, stirring for 20min at the rotation speed of 300r/min, filtering, and adjusting the filtrate with ammonia water until the pH value is 9 to obtain an intermediate 5;
step S3: adding 2-methyl-1, 3-propylene glycol and toluene into a reaction kettle, stirring and dropwise adding phosphorus trichloride under the conditions of the rotating speed of 150r/min and the temperature of 35 ℃ for reacting for 3 hours to obtain an intermediate 6, adding the intermediate 6 and deionized water into the reaction kettle, refluxing and adding potassium permanganate under the condition of the temperature of 110 ℃ for reacting for 4 hours to obtain an intermediate 7, adding 2, 4-di-tert-butylphenol, toluene and triethylamine into the reaction kettle, stirring and adding the intermediate 7 under the conditions of the rotating speed of 150r/min and the temperature of 40 ℃ for reacting for 5 hours to obtain an intermediate 8;
step S4: adding p-chloronitrobenzene, p-methylaniline, potassium carbonate, a phase transfer agent PEG-600, copper oxide and toluene into a reaction kettle, introducing nitrogen for protection, reacting for 8 hours at 185 ℃ to obtain an intermediate 9, adding the intermediate 9, ethanol and palladium carbon into the reaction kettle, introducing nitrogen for protection, introducing hydrogen until the pressure is 1.5MPa, reacting at the rotation speed of 1000r/min and the temperature of 80 ℃ until the pressure is stable to obtain an intermediate 10, adding the intermediate 10, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 8 hours at 90 ℃ to obtain an intermediate 11;
step S5: adding the intermediate 11, methyl isobutyl ketone and palladium carbon into a reaction kettle, replacing air with nitrogen, introducing hydrogen until the pressure is 0.3MPa, keeping the temperature at 40 ℃ for 15min, reacting for 3h under the conditions of the pressure of 1.3MPa, the rotating speed of 800r/min and the temperature of 110 ℃ to obtain an intermediate 12, adding the intermediate 12, a potassium carbonate solution and tetraethylammonium bromide into the reaction kettle, and refluxing for 1.5h under the condition of the temperature of 100 ℃ to obtain an intermediate 13;
step S6: adding the intermediate 2, the intermediate 5, potassium tert-butoxide and 1, 2-dioxane into a reaction kettle, introducing nitrogen for protection, reacting for 5 hours at 110 ℃ to obtain an intermediate 14, adding the intermediate 14 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at 100 ℃, reacting for 5 hours, adding the intermediate 13 and concentrated sulfuric acid, reacting for 3 hours at 50 ℃ to obtain an intermediate 15, adding the intermediate 15, tin powder and concentrated hydrochloric acid into the reaction kettle, reacting for 40 minutes in a boiling water bath at a rotation speed of 150r/min to obtain an intermediate 16, adding the intermediate 16, the intermediate 8, 1-hydroxybenzotriazole and dimethyl sulfoxide into the reaction kettle, reacting for 5 hours at a rotation speed of 200r/min, removing dimethyl sulfoxide to obtain antioxidant.
Example 3
An antioxidant is prepared by the following steps:
step S1: adding m-chloro diphenylamine, sulfur and iodine into a reaction kettle, reacting at the rotation speed of 300r/min and the temperature of 180 ℃ until no hydrogen sulfide gas is generated to prepare an intermediate 1, containing cyanuric chloride in acetone, adding the intermediate 1, and reacting at the rotation speed of 200r/min and the temperature of 90 ℃ for 8 hours to prepare an intermediate 2;
step S2: adding o-toluidine, glacial acetic acid and zinc powder into a reaction kettle, stirring for 30min at the rotation speed of 200r/min and the temperature of 110 ℃, cooling to 25 deg.C to obtain intermediate 3, adding intermediate 3, dichloromethane and mixed acid into reaction kettle, after the reaction is carried out for 40min under the conditions that the rotating speed is 300r/min and the temperature is 15 ℃, distilling to remove dichloromethane, cooling to reaction solution temperature of 3 deg.C, filtering to remove filtrate, washing filter cake with deionized water to pH 7 to obtain intermediate 4, adding intermediate 4, concentrated hydrochloric acid and zeolite into reaction kettle, refluxing for 4h at 110 ℃, cooling to separate out a solid, stirring for 30min at the rotation speed of 300r/min, filtering, and adjusting the filtrate with ammonia water until the pH value is 9 to obtain an intermediate 5;
step S3: adding 2-methyl-1, 3-propylene glycol and toluene into a reaction kettle, stirring and dropwise adding phosphorus trichloride under the conditions of a rotation speed of 200r/min and a temperature of 35 ℃ for reacting for 5 hours to obtain an intermediate 6, adding the intermediate 6 and deionized water into the reaction kettle, refluxing and adding potassium permanganate under the condition of a temperature of 110 ℃ for reacting for 6 hours to obtain an intermediate 7, adding 2, 4-di-tert-butylphenol, toluene and triethylamine into the reaction kettle, stirring and adding the intermediate 7 under the conditions of a rotation speed of 150r/min and a temperature of 50 ℃ for reacting for 5 hours to obtain an intermediate 8;
step S4: adding p-chloronitrobenzene, p-methylaniline, potassium carbonate, a phase transfer agent PEG-600, copper oxide and toluene into a reaction kettle, introducing nitrogen for protection, reacting for 8 hours at the temperature of 190 ℃ to prepare an intermediate 9, adding the intermediate 9, ethanol and palladium carbon into the reaction kettle, introducing nitrogen for protection, introducing hydrogen until the pressure is 1.5-2.0MPa, reacting at the rotation speed of 1000r/min and the temperature of 100 ℃ until the pressure is stable to finish the reaction to prepare an intermediate 10, adding the intermediate 10, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 10 hours at the temperature of 90 ℃ to prepare an intermediate 11;
step S5: adding the intermediate 11, methyl isobutyl ketone and palladium carbon into a reaction kettle, replacing air with nitrogen, introducing hydrogen until the pressure is 0.3MPa, keeping the temperature at 50 ℃, keeping the temperature for 15min, reacting for 3h under the conditions of the pressure of 1.6MPa, the rotating speed of 800r/min and the temperature of 120 ℃ to obtain an intermediate 12, adding the intermediate 12, a potassium carbonate solution and tetraethylammonium bromide into the reaction kettle, and refluxing for 1.5h under the condition of the temperature of 110 ℃ to obtain an intermediate 13;
step S6: adding the intermediate 2, the intermediate 5, potassium tert-butoxide and 1, 2-dioxane into a reaction kettle, introducing nitrogen for protection, reacting for 5 hours at 115 ℃ to obtain an intermediate 14, adding the intermediate 14 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at 110 ℃, reacting for 5 hours, adding the intermediate 13 and concentrated sulfuric acid, reacting for 3 hours at 60 ℃ to obtain an intermediate 15, adding the intermediate 15, tin powder and concentrated hydrochloric acid into the reaction kettle, reacting for 40 minutes in a boiling water bath at 200r/min to obtain an intermediate 16, adding the intermediate 16, the intermediate 8, 1-hydroxybenzotriazole and dimethyl sulfoxide into the reaction kettle, reacting for 5 hours at 300r/min, removing dimethyl sulfoxide to obtain antioxidant.
Comparative example
The comparative example is a common antioxidant on the market.
The antioxidants prepared in examples 1 to 3 and comparative example were subjected to performance tests, the test results of which are shown in table 1 below;
the antioxidants prepared in examples 1 to 3 and comparative example were added to the plastic preparation process to prepare plastic sheets, the tensile strength and impact strength of the plastic sheets were measured, and the plastic sheets were irradiated with light having a wavelength of 340nm and a pre-irradiation degree of 0.68W/m2The temperature of the blackboard is 60 ℃, and the condensation temperature is 60 ℃; a single cycle process; illuminating for 3h, and blowing for 10 min; the circulation process is repeated continuously, and the total experiment time is 168 h; after aging, testing whether the tensile strength and the impact strength are reduced;
TABLE 1
Example 1 Example 2 Example 3 Comparative example
Tensile strength Is not lowered Is not lowered Is not lowered Descend
Impact strength Is not lowered Is not lowered Is not lowered Descend
From the above table 1, it can be seen that the antioxidant prepared by the present invention has a very good antioxidant effect. The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (8)

1. An antioxidant, characterized by: the method comprises the following steps:
step S1: adding m-chloro diphenylamine, sulfur and iodine into a reaction kettle, reacting at the rotation speed of 200-180 ℃ at 300r/min and at the temperature of 170-180 ℃ until no hydrogen sulfide gas is generated to prepare an intermediate 1, containing cyanuric chloride into acetone, adding the intermediate 1, and reacting at the rotation speed of 150-200r/min and at the temperature of 80-90 ℃ for 5-8h to prepare an intermediate 2;
step S2: adding o-toluidine, glacial acetic acid and zinc powder into a reaction kettle, stirring for 20-30min under the conditions of a rotation speed of 150-, stirring for 20-30min, filtering, and adjusting the filtrate with ammonia water to pH 8-9 to obtain intermediate 5;
step S3: adding 2-methyl-1, 3-propanediol and toluene into a reaction kettle, stirring and dropwise adding phosphorus trichloride under the conditions of a rotation speed of 150-;
step S4: adding p-chloronitrobenzene, p-methylaniline, potassium carbonate, a phase transfer agent PEG-600, copper oxide and toluene into a reaction kettle, introducing nitrogen for protection, reacting for 6-8h at the temperature of 185-190 ℃ to obtain an intermediate 9, adding the intermediate 9, ethanol and palladium carbon into the reaction kettle, introducing nitrogen for protection, introducing hydrogen until the pressure is 1.5-2.0MPa, reacting at the rotation speed of 800-1000r/min and the temperature of 80-100 ℃ until the pressure is stable to obtain an intermediate 10, adding the intermediate 10, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 11;
step S5: adding the intermediate 11, methyl isobutyl ketone and palladium carbon into a reaction kettle, replacing air with nitrogen, then introducing hydrogen until the pressure is 0.2-0.3MPa, keeping the temperature at 40-50 ℃, reacting for 2-3h under the conditions of the pressure of 1.3-1.6MPa, the rotating speed of 600-800r/min and the temperature of 110-120 ℃ to obtain an intermediate 12, adding the intermediate 12, a potassium carbonate solution and tetraethylammonium bromide into the reaction kettle, and refluxing for 1-1.5h under the condition of the temperature of 100-110 ℃ to obtain an intermediate 13;
step S6: adding the intermediate 2, the intermediate 5, potassium tert-butoxide and 1, 2-dioxane into a reaction kettle, introducing nitrogen for protection, reacting for 3-5h at the temperature of 110-115 ℃ to obtain an intermediate 14, adding the intermediate 14 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at the temperature of 100-110 ℃, reacting for 3-5h, adding the intermediate 13 and concentrated sulfuric acid, reacting for 2-3h at the temperature of 50-60 ℃ to obtain an intermediate 15, adding the intermediate 15, tin powder and concentrated hydrochloric acid into the reaction kettle, reacting for 30-40min at the rotation speed of 150-200r/min in a boiling water bath to obtain an intermediate 16, and adding the intermediate 16, the intermediate 8, 1-hydroxybenzotriazole, 1-hydroxy benzotriazole, Adding dimethyl sulfoxide into a reaction kettle, reacting for 3-5h at the rotation speed of 200-300r/min, and removing the dimethyl sulfoxide to obtain the antioxidant.
2. An antioxidant according to claim 1, wherein: the molar ratio of the m-chlorodiphenylamine, the sulfur and the iodine used in the step S1 is 25:50:0.1, and the molar ratio of the cyanuric chloride to the intermediate 1 is 1:3.
3. An antioxidant according to claim 1, wherein: the dosage ratio of the o-toluidine, the glacial acetic acid and the zinc powder in the step S2 is 2mol:5mol:2g, the dosage ratio of the intermediate 3, the dichloromethane and the mixed acid is 0.1mol:30mL:5mL, the mixed acid is formed by mixing concentrated nitric acid with mass fraction of 68% and concentrated sulfuric acid with mass fraction of 98% in a molar ratio of 5:7, the dosage ratio of the intermediate 4 and the concentrated hydrochloric acid is 0.1mol:30mL, and the mass fraction of the concentrated hydrochloric acid is 36%.
4. An antioxidant according to claim 1, wherein: the molar ratio of the 2-methyl-1, 3-propanediol to the phosphorus trichloride in the step S3 is 1:1, the molar ratio of the intermediate 6, the deionized water and the potassium permanganate is 2.5g:80mL:4.3g, and the molar ratio of the 2, 4-di-tert-butylphenol, the triethylamine and the intermediate 7 is 0.2mol:0.3g:0.2 mol.
5. An antioxidant according to claim 1, wherein: the dosage ratio of p-chloronitrobenzene, p-methylaniline, potassium carbonate, phase transfer agent PEG-600 and copper oxide in the step S4 is 0.1mol:0.15mol:7.5g:3g:0.8g, the dosage ratio of intermediate 9, ethanol and palladium carbon is 0.3mol:100mL:1.3g, and the dosage ratio of intermediate 10, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride is 0.15mol:0.15mol:0.3g:200 mL.
6. An antioxidant according to claim 1, wherein: the molar ratio of the intermediate 11 to the methyl isobutyl ketone in the step S5 is 1:3.5, the amount of palladium-carbon is 3-5% of the mass sum of the intermediate 11 and the methyl isobutyl ketone, the amount ratio of the intermediate 12, the potassium carbonate solution and the tetraethylammonium bromide is 5g:100mL:4.7mL, and the mass fraction of the potassium carbonate solution is 10%.
7. An antioxidant according to claim 1, wherein: the dosage ratio of the intermediate 2, the intermediate 5, the potassium tert-butoxide and the 1, 2-dioxane described in the step S6 is 0.025mol:0.03mol:0.035mol:70mL, the dosage ratio of the intermediate 14, the deionized water, the potassium permanganate, the intermediate 13 and the concentrated sulfuric acid is 0.01mol:80mL:4.3g:0.03mol:8mL, the mass fraction of the concentrated sulfuric acid is 95%, the dosage ratio of the intermediate 15, the tin powder and the concentrated hydrochloric acid is 5g:8g:20mL, the mass fraction of the concentrated hydrochloric acid is 38%, and the dosage molar ratio of the intermediate 16, the intermediate 8 and the 1-hydroxybenzotriazole is 1:3: 0.5.
8. The method for preparing an antioxidant according to claim 1, wherein: step S1: adding m-chloro diphenylamine, sulfur and iodine into a reaction kettle, reacting at the rotation speed of 200-180 ℃ at 300r/min and at the temperature of 170-180 ℃ until no hydrogen sulfide gas is generated to prepare an intermediate 1, containing cyanuric chloride into acetone, adding the intermediate 1, and reacting at the rotation speed of 150-200r/min and at the temperature of 80-90 ℃ for 5-8h to prepare an intermediate 2;
step S2: adding o-toluidine, glacial acetic acid and zinc powder into a reaction kettle, stirring for 20-30min under the conditions of a rotation speed of 150-, stirring for 20-30min, filtering, and adjusting the filtrate with ammonia water to pH 8-9 to obtain intermediate 5;
step S3: adding 2-methyl-1, 3-propanediol and toluene into a reaction kettle, stirring and dropwise adding phosphorus trichloride under the conditions of a rotation speed of 150-;
step S4: adding p-chloronitrobenzene, p-methylaniline, potassium carbonate, a phase transfer agent PEG-600, copper oxide and toluene into a reaction kettle, introducing nitrogen for protection, reacting for 6-8h at the temperature of 185-190 ℃ to obtain an intermediate 9, adding the intermediate 9, ethanol and palladium carbon into the reaction kettle, introducing nitrogen for protection, introducing hydrogen until the pressure is 1.5-2.0MPa, reacting at the rotation speed of 800-1000r/min and the temperature of 80-100 ℃ until the pressure is stable to obtain an intermediate 10, adding the intermediate 10, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 11;
step S5: adding the intermediate 11, methyl isobutyl ketone and palladium carbon into a reaction kettle, replacing air with nitrogen, then introducing hydrogen until the pressure is 0.2-0.3MPa, keeping the temperature at 40-50 ℃, reacting for 2-3h under the conditions of the pressure of 1.3-1.6MPa, the rotating speed of 600-800r/min and the temperature of 110-120 ℃ to obtain an intermediate 12, adding the intermediate 12, a potassium carbonate solution and tetraethylammonium bromide into the reaction kettle, and refluxing for 1-1.5h under the condition of the temperature of 100-110 ℃ to obtain an intermediate 13;
step S6: adding the intermediate 2, the intermediate 5, potassium tert-butoxide and 1, 2-dioxane into a reaction kettle, introducing nitrogen for protection, reacting for 3-5h at the temperature of 110-115 ℃ to obtain an intermediate 14, adding the intermediate 14 and deionized water into the reaction kettle, refluxing and adding potassium permanganate at the temperature of 100-110 ℃, reacting for 3-5h, adding the intermediate 13 and concentrated sulfuric acid, reacting for 2-3h at the temperature of 50-60 ℃ to obtain an intermediate 15, adding the intermediate 15, tin powder and concentrated hydrochloric acid into the reaction kettle, reacting for 30-40min at the rotation speed of 150-200r/min in a boiling water bath to obtain an intermediate 16, and adding the intermediate 16, the intermediate 8, 1-hydroxybenzotriazole, 1-hydroxy benzotriazole, Adding dimethyl sulfoxide into a reaction kettle, reacting for 3-5h at the rotation speed of 200-300r/min, and removing the dimethyl sulfoxide to obtain the antioxidant.
CN202110515513.6A 2021-05-12 2021-05-12 Antioxidant and method for preparing antioxidant Pending CN113200942A (en)

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CN112662135A (en) * 2020-12-11 2021-04-16 安徽扬子地板股份有限公司 Epoxy resin insulating board and preparation method thereof
CN112920628A (en) * 2021-01-27 2021-06-08 叶玉婷 Vehicle paint maintenance coating agent and preparation method thereof
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CN112281492A (en) * 2020-11-05 2021-01-29 玉环德谷新材料科技有限公司 Anti-aging textile fabric and preparation method thereof
CN112321969A (en) * 2020-11-23 2021-02-05 安徽嘉美包装有限公司 Anti-aging plastic packaging film and preparation method thereof
CN112481734A (en) * 2020-12-03 2021-03-12 安徽嘉明新材料科技有限公司 Preparation method and application of electrostatic spinning TPU (thermoplastic polyurethane) fiber
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