Preparation method of alkylated diphenylamine antioxidant with high color stability

Abstract

The invention relates to a preparation method of an alkylated diphenylamine antioxidant with high color stability, belonging to the technical field of chemical engineering of production of synthetic material antioxidants. In the process of preparing and storing the alkylated diphenylamine antioxidant product, a small amount of functional antioxidant with high color stability is added to improve the color stability. The method is implemented in a way that: an atlapulgite catalyst, diphenylamine, styrene, dimerized isobutylene, nonylene and alpha-methylstyrene alkylating reagent are subjected to catalytic alkylation reaction to prepare the alkylated diphenylamine antioxidant product; and in the preparation process, a heat stabilizer and a color protection-color reduction agent method is utilized to obtain the alkylated diphenylamine antioxidant product with high color stability. The product is still light yellow after being stored in a closed white glass bottle at the indoor temperature of 10-35 DEG C for 6 months.

Description

technical field

[0001] The invention belongs to the chemical technology field of synthetic material antioxidant production, and in particular relates to a preparation method of an alkylated diphenylamine antioxidant product with stable color and luster. Background technique

[0002] As an antioxidant, diphenylamine has the disadvantages of being easy to volatilize and having poor resistance to oxygen, which is generally improved by adding a group with a large relative molecular mass. It has been found that the alkylation reaction between diphenylamine and the corresponding active olefin can obtain a product with good antioxidant properties. For example, diphenylamine undergoes alkylation reaction with styrene, nonene, dimer isobutylene, α-methylstyrene, etc. to generate corresponding alkylated diphenylamine products, which are widely used in rubber tires, various rubber products, lubricants, etc. In oil, it is used to replace other amine antioxidants with strong pollution a...

Examples

Embodiment 1

[0042] Add 300 grams of diphenylamine, 45 grams of catalyst FS, 1.5 grams of 2,6-di-tert-butyl-4 - methylphenol, cyclohexane 400 g. Raise the temperature to 80~82°C for reflux dehydration for 1 hour, then distill off the cyclohexane in the reaction solution, lower it to normal temperature under nitrogen protection, add 230 grams of dimeric isobutylene, fully replace the air in the reactor with nitrogen, and start Stir and heat, so that the temperature in the kettle rises to 160~170°C, the pressure inside the kettle is 0.2~0.25 MPa, heat preservation reaction for 10 hours, add 80 grams of dimerized isobutylene, heat preservation reaction at 160~170°C for 15 hours, add dimerized isobutylene 40 grams, 160 ~ 170 ℃ heat preservation reaction for 20 hours, the reaction is over. Cool down, add 500 grams of cyclohexane, filter at 60~70°C, remove the solid catalyst, collect the filtrate in a distillation pot, distill off the cyclohexane, under the protection of nitrogen, vacuum -0.095...

Embodiment 2

[0046] In a 500mL reaction flask equipped with a stirrer, thermometer, water separator, reflux condenser, dropping funnel, and nitrogen conduit, add 60 grams of diphenylamine, 8 grams of catalyst FS, tetrakis [β-(3,5-ditertiary 0.3 g of butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, and 80 g of cyclohexane. Replace with nitrogen, stir and heat up under the protection of nitrogen, and carry out reflux dehydration at 80~82°C for 1 hour, then distill off the cyclohexane in the reaction liquid, then raise the temperature to 135~138°C, and start to add 81 grams of styrene dropwise , 3 hours to complete the addition, 138 ° C heat preservation reaction for 2 hours, the reaction ended. Cool down, add 100 grams of cyclohexane, filter at 60~70°C, remove the solid catalyst, distill the filtrate, distill off the cyclohexane, under the protection of nitrogen, vacuum -0.095MPa, 140~150°C to remove some unreacted raw materials, cool down, To obtain a light yellow viscous liquid, ...

Embodiment 3

[0050] In a 500mL reaction flask equipped with a stirrer, a thermometer, a water separator, a reflux condenser, a dropping funnel, and a nitrogen conduit, add 60 grams of diphenylamine, 10 grams of catalyst FS, and a polymerization inhibitor tetrakis [β-(3,5 - 0.3 g of di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, 85 g of cyclohexane. Replace with nitrogen, stir and heat up under the protection of nitrogen, and carry out reflux dehydration at 80~82°C for 1 hour, then distill off the cyclohexane in the reaction solution, then raise the temperature to 135~138°C, and start to add α-methyl Add 100 grams of styrene in 4 hours, keep the temperature at 135-138°C for 4 hours, and the reaction is over. Add 100 grams of cyclohexane, filter at 60~70°C, remove the solid catalyst, collect the filtrate in a distillation kettle, add 3 grams of heat stabilizer, distill the cyclohexane, under the protection of nitrogen, vacuum -0.095MPa, 200~230 Remove the light components...

technical field

[0001] The invention belongs to the chemical technology field of synthetic material antioxidant production, and in particular relates to a preparation method of an alkylated diphenylamine antioxidant product with stable color and luster. Background technique

[0002] As an antioxidant, diphenylamine has the disadvantages of being easy to volatilize and having poor resistance to oxygen, which is generally improved by adding a group with a large relative molecular mass. It has been found that the alkylation reaction between diphenylamine and the corresponding active olefin can obtain a product with good antioxidant properties. For example, diphenylamine undergoes alkylation reaction with styrene, nonene, dimer isobutylene, α-methylstyrene, etc. to generate corresponding alkylated diphenylamine products, which are widely used in rubber tires, various rubber products, lubricants, etc. In oil, it is used to replace other amine antioxidants with strong pollution a...

Examples

Embodiment 1

[0042] Add 300 grams of diphenylamine, 45 grams of catalyst FS, 1.5 grams of 2,6-di-tert-butyl-4 - methylphenol, cyclohexane 400 g. Raise the temperature to 80~82°C for reflux dehydration for 1 hour, then distill off the cyclohexane in the reaction solution, lower it to normal temperature under nitrogen protection, add 230 grams of dimeric isobutylene, fully replace the air in the reactor with nitrogen, and start Stir and heat, so that the temperature in the kettle rises to 160~170°C, the pressure inside the kettle is 0.2~0.25 MPa, heat preservation reaction for 10 hours, add 80 grams of dimerized isobutylene, heat preservation reaction at 160~170°C for 15 hours, add dimerized isobutylene 40 grams, 160 ~ 170 ℃ heat preservation reaction for 20 hours, the reaction is over. Cool down, add 500 grams of cyclohexane, filter at 60~70°C, remove the solid catalyst, collect the filtrate in a distillation pot, distill off the cyclohexane, under the protection of nitrogen, vacuum -0.095...

Embodiment 2

[0046] In a 500mL reaction flask equipped with a stirrer, thermometer, water separator, reflux condenser, dropping funnel, and nitrogen conduit, add 60 grams of diphenylamine, 8 grams of catalyst FS, tetrakis [β-(3,5-ditertiary 0.3 g of butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, and 80 g of cyclohexane. Replace with nitrogen, stir and heat up under the protection of nitrogen, and carry out reflux dehydration at 80~82°C for 1 hour, then distill off the cyclohexane in the reaction liquid, then raise the temperature to 135~138°C, and start to add 81 grams of styrene dropwise , 3 hours to complete the addition, 138 ° C heat preservation reaction for 2 hours, the reaction ended. Cool down, add 100 grams of cyclohexane, filter at 60~70°C, remove the solid catalyst, distill the filtrate, distill off the cyclohexane, under the protection of nitrogen, vacuum -0.095MPa, 140~150°C to remove some unreacted raw materials, cool down, To obtain a light yellow viscous liquid, ...

Embodiment 3

[0050] In a 500mL reaction flask equipped with a stirrer, a thermometer, a water separator, a reflux condenser, a dropping funnel, and a nitrogen conduit, add 60 grams of diphenylamine, 10 grams of catalyst FS, and a polymerization inhibitor tetrakis [β-(3,5 - 0.3 g of di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, 85 g of cyclohexane. Replace with nitrogen, stir and heat up under the protection of nitrogen, and carry out reflux dehydration at 80~82°C for 1 hour, then distill off the cyclohexane in the reaction solution, then raise the temperature to 135~138°C, and start to add α-methyl Add 100 grams of styrene in 4 hours, keep the temperature at 135-138°C for 4 hours, and the reaction is over. Add 100 grams of cyclohexane, filter at 60~70°C, remove the solid catalyst, collect the filtrate in a distillation kettle, add 3 grams of heat stabilizer, distill the cyclohexane, under the protection of nitrogen, vacuum -0.095MPa, 200~230 Remove the light components...