A kind of sulfide bisphenol acrylate multi-effect antioxidant and preparation method thereof

Abstract

The invention discloses a thioether-based bisphenol acrylate multi-effect antioxidant, which has a molecular structure shown in the following formula: the molecule of the thioether-based bisphenol acrylate multi-effect antioxidant contains both the main antioxidant The hindered phenol functional group of the agent and the thioether bond of the auxiliary antioxidant also contain the acrylate phenol ester structure with the function of capturing carbon free radicals, which can play a three-in-one antioxidant effect in the process of processing and using polymer materials , can better protect polymer materials, avoid product degradation and aging, solve the problem of poor anti-oxidation effect of single-functional antioxidants on polymer materials, and the corresponding preparation process has low reaction temperature, low energy consumption, and side effects The product can be removed by filtration, no waste water is generated, the solvent can be recycled, and it is environmentally friendly.

Description

technical field

[0001] The invention relates to plastic additives, in particular to a sulfide bisphenol acrylate multi-effect antioxidant and a preparation method thereof. Background technique

[0002] Antioxidants are a kind of polymer additives. When only a small amount exists in the polymer system, it can delay or inhibit the oxidation process of the polymer, thereby preventing the aging of the polymer and prolonging its service life. called anti-aging agent. The thermal oxidation process of organic compounds is a series of free radical chain reactions. Under the action of heat or light, the chemical bonds of molecules are broken to generate active free radicals. These free radicals can trigger a series of free radical chain reactions. It causes fundamental changes in the structure and properties of organic compounds. The mechanism of action of antioxidants is to eliminate the newly generated free radicals and prevent the chain reaction from proceeding, thereby preventin...

Examples

Embodiment 1

[0016] The synthesis of embodiment 1 compound a

[0017] Add 358.5g (1mol) of 2,2'-thiobis(4-methyl-6-tert-butylphenol) into a 3L three-necked flask, then add 1000ml of n-heptane, 404g (4mol) of triethylamine, acrylic acid 86.5g (1.2mol), stir and raise the temperature to 60°C, start to add 199g (1.3mol) of phosphorus oxychloride dropwise, control the temperature at 60-80°C during the dropwise addition, add the time for 1h, raise the temperature to 85°C and keep it for 1.5 h. After the reaction, wait for the reaction solution to cool slightly and suction filter, the filter cake is triethylamine salt, rinse with 500ml of n-heptane, combine the organic phases, distill out 1200ml of n-heptane under reduced pressure, and stir the remaining liquid to cool down and crystallize , crystallized at 0 to 5° C., and filtered with suction to obtain 338.3 g of the product with a yield of 82%.

Embodiment 2

[0018] The synthesis of embodiment 2 compound b

[0019] Add 386.5g (1mol) of 2,2'-thiobis(4-ethyl-6-tert-butylphenol) into a 3L three-necked flask, then add 1100ml of n-heptane, 505g (5mol) of triethylamine, acrylic acid 93.7g (1.3mol), stir and heat up to 65°C, start dropwise adding 199g (1.3mol) of phosphorus oxychloride, control the temperature at 65-80°C during the dropwise addition, add dropwise for 1h, raise the temperature to 85°C and keep for 1.5 h. After the reaction is finished, wait for the reaction solution to cool slightly and filter with suction. The filter cake is triethylamine salt, rinse with 500ml of n-heptane, combine the organic phases, distill out 1300ml of n-heptane under reduced pressure, and stir the remaining liquid to cool down and crystallize. , crystallized at 2 to 5° C. to obtain 373 g of the product with a yield of 84.6%.

Embodiment example 3

[0020] The synthesis of embodiment case 3 compound c

[0021] Add 414.5g (1mol) of 2,2'-thiobis(4,6-di-tert-butylphenol) into a 3L three-necked flask, then add 1100ml of toluene, 535g (5.3mol) of triethylamine, and 93.7g of acrylic acid ( 1.3mol), stirred and raised the temperature to 60°C, began to dropwise add 207g (1.35mol) of phosphorus oxychloride, the temperature was controlled at 65-85°C during the dropwise addition, the dropwise time was 1h, and the temperature was raised to 90°C for 1.5h after the dropwise addition. After the reaction, wait for the reaction solution to cool slightly and filter with suction. The filter cake is triethylamine salt, rinse with 600ml of toluene, combine the organic phases, distill 1200ml of toluene under reduced pressure, and stir the remaining residual solution to cool down and crystallize. 5 to 10 Crystallized at ℃ to obtain 414.6 g of the product with a yield of 88.5%.

technical field

[0001] The invention relates to plastic additives, in particular to a sulfide bisphenol acrylate multi-effect antioxidant and a preparation method thereof. Background technique

[0002] Antioxidants are a kind of polymer additives. When only a small amount exists in the polymer system, it can delay or inhibit the oxidation process of the polymer, thereby preventing the aging of the polymer and prolonging its service life. called anti-aging agent. The thermal oxidation process of organic compounds is a series of free radical chain reactions. Under the action of heat or light, the chemical bonds of molecules are broken to generate active free radicals. These free radicals can trigger a series of free radical chain reactions. It causes fundamental changes in the structure and properties of organic compounds. The mechanism of action of antioxidants is to eliminate the newly generated free radicals and prevent the chain reaction from proceeding, thereby preventin...

Examples

Embodiment 1

[0016] The synthesis of embodiment 1 compound a

[0017] Add 358.5g (1mol) of 2,2'-thiobis(4-methyl-6-tert-butylphenol) into a 3L three-necked flask, then add 1000ml of n-heptane, 404g (4mol) of triethylamine, acrylic acid 86.5g (1.2mol), stir and raise the temperature to 60°C, start to add 199g (1.3mol) of phosphorus oxychloride dropwise, control the temperature at 60-80°C during the dropwise addition, add the time for 1h, raise the temperature to 85°C and keep it for 1.5 h. After the reaction, wait for the reaction solution to cool slightly and suction filter, the filter cake is triethylamine salt, rinse with 500ml of n-heptane, combine the organic phases, distill out 1200ml of n-heptane under reduced pressure, and stir the remaining liquid to cool down and crystallize , crystallized at 0 to 5° C., and filtered with suction to obtain 338.3 g of the product with a yield of 82%.

Embodiment 2

[0018] The synthesis of embodiment 2 compound b

[0019] Add 386.5g (1mol) of 2,2'-thiobis(4-ethyl-6-tert-butylphenol) into a 3L three-necked flask, then add 1100ml of n-heptane, 505g (5mol) of triethylamine, acrylic acid 93.7g (1.3mol), stir and heat up to 65°C, start dropwise adding 199g (1.3mol) of phosphorus oxychloride, control the temperature at 65-80°C during the dropwise addition, add dropwise for 1h, raise the temperature to 85°C and keep for 1.5 h. After the reaction is finished, wait for the reaction solution to cool slightly and filter with suction. The filter cake is triethylamine salt, rinse with 500ml of n-heptane, combine the organic phases, distill out 1300ml of n-heptane under reduced pressure, and stir the remaining liquid to cool down and crystallize. , crystallized at 2 to 5° C. to obtain 373 g of the product with a yield of 84.6%.

Embodiment example 3

[0020] The synthesis of embodiment case 3 compound c

[0021] Add 414.5g (1mol) of 2,2'-thiobis(4,6-di-tert-butylphenol) into a 3L three-necked flask, then add 1100ml of toluene, 535g (5.3mol) of triethylamine, and 93.7g of acrylic acid ( 1.3mol), stirred and raised the temperature to 60°C, began to dropwise add 207g (1.35mol) of phosphorus oxychloride, the temperature was controlled at 65-85°C during the dropwise addition, the dropwise time was 1h, and the temperature was raised to 90°C for 1.5h after the dropwise addition. After the reaction, wait for the reaction solution to cool slightly and filter with suction. The filter cake is triethylamine salt, rinse with 600ml of toluene, combine the organic phases, distill 1200ml of toluene under reduced pressure, and stir the remaining residual solution to cool down and crystallize. 5 to 10 Crystallized at ℃ to obtain 414.6 g of the product with a yield of 88.5%.

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