CN112574053B - Synthesis process of antioxidant 1098 - Google Patents
Synthesis process of antioxidant 1098 Download PDFInfo
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- CN112574053B CN112574053B CN202011439988.3A CN202011439988A CN112574053B CN 112574053 B CN112574053 B CN 112574053B CN 202011439988 A CN202011439988 A CN 202011439988A CN 112574053 B CN112574053 B CN 112574053B
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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Abstract
The invention provides a synthesis process of an antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, which is characterized in that beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate synthesized by adding 2, 6-di-tert-butylphenol and methyl acrylate and 1, 6-hexamethylenediamine are subjected to ammonolysis reaction to obtain the antioxidant 1098.
Description
Technical Field
The invention belongs to a preparation method of aromatic carboxylic acid amide containing hydroxyl, and particularly relates to a preparation process of (N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine used as an antioxidant 1098.
Background
During the storage and use of the polyolefin material, the polyolefin material is inevitably interfered by external factors such as illumination, heating, catalytic action of metal ions and the like, so that the surface of the polyolefin material gradually becomes hard and brittle, discolors, cracks, stickiness and the like, the air permeability of the material is increased, the mechanical property is reduced, the elongation and the like are greatly reduced, and finally the use value, namely the aging of the material is lost. Therefore, an antioxidant, which is a substance capable of retarding the aging of polyolefin materials, is added in the preparation process of the polyolefin materials. The antioxidant can prolong the service life of the polyolefin material and improve the use value of the polyolefin material. (N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine is an antioxidant Irganox 1098, is a high molecular weight hindered phenol antioxidant developed by Ciba-Geigy of original Switzerland, has dual functions of hindered phenol and hindered amine antioxidants, has good thermal stability and precipitation resistance, is an excellent antioxidant and heat stabilizer for high molecular materials, is mainly used for polyamide and polyacetal, and can also be used for polyolefin, poly-vinegar, natural or synthetic rubber and other high molecular compounds sensitive to thermal oxidation, the appearance of the antioxidant Irganox 1098 is white crystal, the melting point is 157-.
The chemical structural formula of (N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098) is as follows:
in the prior art, antioxidant 1098 is prepared by amidation condensation in condensation reaction, methyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (3, 5-methyl) is synthesized by adding 2, 6-di-tert-butylphenol and methyl acrylate, and antioxidant 1098 is obtained by ammonolysis reaction of methyl 3, 5-propionate and 1, 6-hexamethylenediamine. On the basis of the prior art, the invention deeply explores the process modes of scale production and industrialization of the antioxidant 1098, realizes cost saving by effectively recycling and circulating the solvent, and realizes green and environment-friendly integral reaction process by centralized treatment of waste gas and the like.
Disclosure of Invention
The invention provides a preparation process of an antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, which has the advantages of mild reaction conditions, excellent product purity and yield, low cost and environmental protection.
The invention provides a preparation process of an antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, which comprises the following specific reaction steps:
(1) ammonolysis reaction: beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate (3, 5-methyl ester for short) and 1, 6-hexamethylene diamine are taken as reaction raw materials, organic tin or tetraisopropyl titanate is taken as a catalyst, inert gas is introduced, the reaction is carried out for a certain time in a solvent I under the condition of 100 ℃ and 150 ℃, and methanol generated is separated from the system in the reaction process to obtain an antioxidant 1098 mother liquor;
(2) mother liquor treatment: distilling and separating the antioxidant 1098 mother liquor under reduced pressure and recovering a solvent I to obtain a solid substance A, dissolving the solid substance A with a solvent II, filtering under pressure to obtain an antioxidant 1098 filtrate, and separating and recovering a catalyst from the filter residue;
(3) a crystallization process: cooling the filtrate to 0-5 ℃, separating out crystals in the system, performing centrifugal separation and drying to obtain an antioxidant 1098, and packaging to obtain an antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine finished product;
(4) recycling and waste gas treatment: crystallizing the antioxidant 1098 filtrate, centrifuging to obtain a crystallization mother liquor, sending the crystallization mother liquor into a distillation tower for continuous rectification to recover a crystallization solvent, recycling the recovered crystallization solvent, mixing the mother liquor rectification concentrate which is an antioxidant 1098 crude product after recrystallization with the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine finished product obtained in the step (3), collecting waste gas generated in the distillation and condensation processes, condensing again to remove the solvent mixed in the waste gas, and spraying water to obtain a gas which can be recycled.
The inert gas is nitrogen or argon.
The solvent I is selected from any one or combination of benzene, toluene, ethylbenzene and xylene.
The reaction process of the ammonolysis reaction is as follows:
the solvent II is selected from any one or combination of ethanol, methanol, propanol and butanol.
The mol ratio of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate (3, 5-methyl ester for short) to the 1, 6-hexanediamine is 1: 0.5-0.6, and the ammonolysis reaction time is 2-6 h, preferably 3-5 h.
The organotin catalyst preferably has the following structure: R1R2Sn ═ O, where R1 and R2 are the same or different C1 to C30 hydrocarbon groups, alkoxy groups, alkylthio groups, halogen atoms, hydroxyl groups, mercapto groups, or acyloxy groups. The organotin catalyst is preferably triphenyltin chloride, dioctyltin oxide, dihexyltin oxide, di-n-butyltin dilaurate, dihexylundecyltin chloride, di-n-octyltin bis (monobutyl maleate), trioctyltin hydroxide, triethylbenzoyloxytin, dibenzyltin dichloride, triethylacetoxytin, bis (methyl propionate) tin dichloride, dibutyltin laurate maleate, di-n-butyltin dodecanethiolate, di-n-octyltin β -mercaptopropionate or bis (methoxycarbonylethyl) tin S, S' -bis (isooctyl thioglycolate).
The dosage of the catalyst is 0.1-0.5 percent of the weight of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, and preferably 0.2-2.5 percent.
The technical scheme of the application has the following advantages: in the technical scheme, reaction raw material selection, catalyst selection, extractant selection, reagent dosage, reaction time and reaction temperature are obtained through long-term complex experiments, and the beneficial effects of the invention are supported by the synergistic effect of the factors, namely the invention shortens the reaction time, improves the product yield to be more than 95% and has high product purity. The invention researches the process modes of scale production and industrialization of the antioxidant 1098, and achieves the aim of recycling by effectively recycling the solvent and the gas, thereby saving resources and realizing the unification of environmental benefits and economic benefits.
Detailed Description
The invention is further described below by way of examples, which are not intended to limit the present invention further. It will be understood by those skilled in the art that equivalent substitutions and corresponding modifications of the technical features of the present invention can be made and still fall within the scope of the present invention.
Example 1
30Kg of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, 5.96Kg of hexamethylenediamine, 60g of dioctyltin oxide and 50L of toluene are added into a reaction kettle, nitrogen is introduced into the system, the mixture is stirred and fully mixed, the temperature is slowly raised to 110 ℃, the reaction is carried out for 3 hours, and the methanol generated in the reaction is removed by condensation in the reaction process. And after the reaction is finished, stopping heating, distilling and separating and recovering the solvent toluene, wherein the recovered solvent can be used as a reaction solvent for recycling. Adding ethanol, heating, stirring, dissolving the solid obtained by distillation, and filtering while the solution is hot to obtain an antioxidant 1098 filtrate; slowly cooling the filtrate to 0-5 ℃, separating out crystals in a system, performing centrifugal separation and drying to obtain an antioxidant 1098, packaging the antioxidant 1098 to obtain a finished antioxidant 1098(N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product, crystallizing the antioxidant 1098 filtrate, performing centrifugal separation to obtain a crystallization mother liquor, sending the crystallization mother liquor to a distillation tower for continuous rectification and recovery of a crystallization solvent, recycling the recovered crystallization solvent, recycling the mother liquor rectification concentrate to obtain an antioxidant 1098 crude product, performing recrystallization, combining the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product obtained in the step (3), collecting waste gas generated in the distillation and condensation processes, and after the solvent included in the waste gas is removed by secondary condensation treatment, obtaining gas which can be recycled after water spraying treatment. The operation described above gave 63.4Kg of antioxidant 1098 in 98% yield, which was 98% pure by gas chromatography. The product has a melting point of 157-.
Example 2
30Kg of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, 6.0Kg of hexamethylenediamine, 60g of tetraisopropyl titanate and 50L of toluene are added into a reaction kettle, nitrogen is introduced into the system, the mixture is stirred and fully mixed, the temperature is slowly raised to 110 ℃, the reaction is carried out for 3 hours, and the methanol generated in the reaction is removed by condensation in the reaction process. And after the reaction is finished, stopping heating, distilling and separating and recovering the solvent toluene, wherein the recovered solvent can be used as a reaction solvent for recycling. Adding ethanol, heating, stirring, dissolving the solid obtained by distillation, and filtering while the solution is hot to obtain an antioxidant 1098 filtrate; slowly cooling the filtrate to 0-5 ℃, separating out crystals in a system, performing centrifugal separation and drying to obtain an antioxidant 1098, packaging the antioxidant 1098 to obtain a finished antioxidant 1098(N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product, crystallizing the antioxidant 1098 filtrate, performing centrifugal separation to obtain a crystallization mother liquor, sending the crystallization mother liquor to a distillation tower for continuous rectification and recovery of a crystallization solvent, recycling the recovered crystallization solvent, recycling the mother liquor rectification concentrate to obtain an antioxidant 1098 crude product, performing recrystallization, combining the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product obtained in the step (3), collecting waste gas generated in the distillation and condensation processes, and after the solvent included in the waste gas is removed by secondary condensation treatment, obtaining gas which can be recycled after water spraying treatment. The operation described above gave 64.7Kg of antioxidant 1098 in 99% yield, which was 99% pure by gas chromatography. The product has a melting point of 157-.
Example 3
30Kg of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, 5.7Kg of hexamethylenediamine, 75g of triphenyltin chloride and 50L of dimethylbenzene are added into a reaction kettle, nitrogen is introduced into the system, the mixture is stirred and fully mixed, the temperature is slowly raised to 135 ℃, the reaction is carried out for 4 hours, and methanol generated in the reaction is removed by condensation in the reaction process. And after the reaction is finished, stopping heating, distilling and separating and recovering the solvent toluene, wherein the recovered solvent can be used as a reaction solvent for recycling. Adding ethanol, heating, stirring, dissolving the solid obtained by distillation, and filtering while the solution is hot to obtain an antioxidant 1098 filtrate; slowly cooling the filtrate to 0-5 ℃, separating out crystals in a system, performing centrifugal separation and drying to obtain an antioxidant 1098, packaging the antioxidant 1098 to obtain a finished antioxidant 1098(N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product, crystallizing the antioxidant 1098 filtrate, performing centrifugal separation to obtain a crystallization mother liquor, sending the crystallization mother liquor to a distillation tower for continuous rectification and recovery of a crystallization solvent, recycling the recovered crystallization solvent, recycling the mother liquor rectification concentrate to obtain an antioxidant 1098 crude product, performing recrystallization, combining the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product obtained in the step (3), collecting waste gas generated in the distillation and condensation processes, and after the solvent included in the waste gas is removed by secondary condensation treatment, obtaining gas which can be recycled after water spraying treatment. The operation described above gave 62.0Kg of antioxidant 1098 in 95% yield, which was 98% pure by gas chromatography. The product has a melting point of 157-.
Example 4
30Kg of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, 6.01Kg of hexamethylenediamine, 60g of di-n-butyltin dodecanethiolate and 50L of ethylbenzene were added to a reaction vessel, nitrogen gas was introduced into the system, the mixture was stirred and mixed thoroughly, the temperature was slowly raised to 136 ℃ for reaction for 5 hours, and methanol produced in the reaction was removed by condensation during the reaction. And after the reaction is finished, stopping heating, distilling and separating and recovering the solvent toluene, wherein the recovered solvent can be used as a reaction solvent for recycling. Adding methanol, heating, stirring, dissolving the solid obtained by distillation, and filtering while the solution is hot to obtain an antioxidant 1098 filtrate; slowly cooling the filtrate to 0-5 ℃, separating out crystals in a system, performing centrifugal separation and drying to obtain an antioxidant 1098, packaging the antioxidant 1098 to obtain a finished antioxidant 1098(N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product, crystallizing the antioxidant 1098 filtrate, performing centrifugal separation to obtain a crystallization mother liquor, sending the crystallization mother liquor to a distillation tower for continuous rectification and recovery of a crystallization solvent, recycling the recovered crystallization solvent, recycling the mother liquor rectification concentrate to obtain an antioxidant 1098 crude product, performing recrystallization, combining the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product obtained in the step (3), collecting waste gas generated in the distillation and condensation processes, and after the solvent included in the waste gas is removed by secondary condensation treatment, obtaining gas which can be recycled after water spraying treatment. The operation described above gave 61.4Kg of antioxidant 1098 in 94% yield, which was 98% pure by gas chromatography. The product has a melting point of 157-.
Example 5
30Kg of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, 7.13Kg of hexamethylenediamine, 60g of trioctyltin hydroxide and 50L of toluene are added into a reaction kettle, nitrogen is introduced into the system, the mixture is stirred and fully mixed, the temperature is slowly raised to 110 ℃, the reaction is carried out for 3 hours, and the methanol generated in the reaction is removed by condensation in the reaction process. And after the reaction is finished, stopping heating, distilling and separating and recovering the solvent toluene, wherein the recovered solvent can be used as a reaction solvent for recycling. Adding ethanol, heating, stirring, dissolving the solid obtained by distillation, and filtering while the solution is hot to obtain an antioxidant 1098 filtrate; slowly cooling the filtrate to 0-5 ℃, separating out crystals in a system, performing centrifugal separation and drying to obtain an antioxidant 1098, packaging the antioxidant 1098 to obtain a finished antioxidant 1098(N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product, crystallizing the antioxidant 1098 filtrate, performing centrifugal separation to obtain a crystallization mother liquor, sending the crystallization mother liquor to a distillation tower for continuous rectification and recovery of a crystallization solvent, recycling the recovered crystallization solvent, recycling the mother liquor rectification concentrate to obtain an antioxidant 1098 crude product, performing recrystallization, combining the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine product obtained in the step (3), collecting waste gas generated in the distillation and condensation processes, and after the solvent included in the waste gas is removed by secondary condensation treatment, obtaining gas which can be recycled after water spraying treatment. The operation described above yielded 62.7Kg of antioxidant 1098, with a yield of 96%, and a purity of 98% as determined by gas chromatography. The product has a melting point of 157-.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (4)
1. A synthesis process of an antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine) is characterized by comprising the following reaction steps:
(1) ammonolysis reaction: beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate (3, 5-methyl ester) and 1, 6-hexamethylene diamine are used as reaction raw materials, tetraisopropyl titanate is used as a catalyst, inert gas is introduced, the reaction is carried out for a certain time in a solvent I under the condition of 110 ℃, and methanol generated is separated from a system in the reaction process to obtain an antioxidant 1098 mother liquor;
(2) mother liquor treatment: distilling and separating the antioxidant 1098 mother liquor under reduced pressure, recovering the solvent I to obtain a solid substance A, dissolving the solid substance A with a solvent II, filtering under pressure to obtain an antioxidant 1098 filtrate, and separating and recovering the catalyst from the filter residue;
(3) a crystallization process: cooling the filtrate to 0-5 ℃, separating out crystals in the system, performing centrifugal separation and drying to obtain an antioxidant 1098, and packaging to obtain an antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine) finished product;
(4) recycling and waste gas treatment: crystallizing the antioxidant 1098 filtrate, performing centrifugal separation to obtain a crystallization mother liquor, sending the crystallization mother liquor into a distillation tower for continuous rectification to recover a crystallization solvent, recycling the recovered crystallization solvent, mixing the mother liquor rectification concentrate with the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine) finished product obtained in the step (3) after recrystallization, collecting waste gas generated in the distillation and condensation processes, performing condensation treatment again to remove the solvent mixed in the waste gas, and performing water spraying treatment to obtain a gas capable of being recycled;
wherein the solvent I is selected from toluene, and the solvent II is selected from ethanol; the dosage of the catalyst is 0.1-0.5% of the weight of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate.
2. The process for synthesizing the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine) according to claim 1, wherein the inert gas in the step (1) is nitrogen or argon.
3. The process for synthesizing the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine) according to claim 1, wherein the molar ratio of the methyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (3, 5-methyl ester) to the 1, 6-hexamethylenediamine is 1: 0.5-0.6, and the ammonolysis reaction time is 2-6 h.
4. The process for synthesizing the antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine) according to claim 3, wherein the ammonolysis reaction time is 3-5 h.
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