CN116969844A - Synthesis method of N-2-ethylhexyl-N' -phenyl p-phenylenediamine - Google Patents
Synthesis method of N-2-ethylhexyl-N' -phenyl p-phenylenediamine Download PDFInfo
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- VSRZZEOGDJPHPB-UHFFFAOYSA-N 1-N-ethyl-4-N-hexyl-4-N-phenylbenzene-1,4-diamine Chemical compound CCNC1=CC=C(C=C1)N(C1=CC=CC=C1)CCCCCC VSRZZEOGDJPHPB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 36
- PYLMCYQHBRSDND-SOFGYWHQSA-N (E)-2-ethyl-2-hexenal Chemical compound CCC\C=C(/CC)C=O PYLMCYQHBRSDND-SOFGYWHQSA-N 0.000 claims abstract description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 229940126062 Compound A Drugs 0.000 claims abstract description 17
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002798 polar solvent Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 18
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- OLFQLEJXIHEDEJ-UHFFFAOYSA-N CCCCC(CC)CO.CC(C)CCCCCO Chemical compound CCCCC(CC)CO.CC(C)CCCCCO OLFQLEJXIHEDEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NKUJQQWJJANFIN-UHFFFAOYSA-N hepta-1,4,6-trien-3-one Chemical compound C=CC=CC(=O)C=C NKUJQQWJJANFIN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application discloses a synthesis method of N-2-ethylhexyl-N' -phenyl p-phenylenediamine. The method takes a compound A and 4-aminodiphenylamine as raw materials to carry out hydrogenation reaction to obtain N-2-ethylhexyl-N' -phenyl-p-phenylenediamine; wherein compound A is 2-ethyl-2-hexenal; the synthesis method further comprises the step of adding n-butyraldehyde into a strong alkaline solvent to react to prepare the 2-ethyl-2-hexenal before the step of carrying out the hydrogenation reaction on the 2-ethyl-2-hexenal and the 4-aminodiphenylamine, wherein the reaction temperature is 70-110 ℃ and the reaction time is 0.3-8 h. In a word, the synthesis method of the N-2-ethylhexyl-N' -phenyl-p-phenylenediamine provided by the application has the advantages of simple process, low cost and environmental friendliness.
Description
Technical Field
The application relates to the field of preparation of p-phenylenediamine rubber antioxidants, in particular to a synthetic method of N-2-ethylhexyl-N' -phenyl p-phenylenediamine.
Background
The properties of rubber, plastics and articles thereof tend to gradually decrease with aging, even losing their value in use entirely. In order to extend the service life of rubber-plastic articles, it is often necessary to incorporate substances which inhibit aging, known as antioxidants, therein.
The compound N-2-ethylhexyl-N' -phenyl-p-phenylenediamine is called an anti-aging agent S789 in the chemical industry. The compound is mainly used for synthetic rubber such as isoprene rubber, butadiene rubber, acryl butadiene rubber and the like, and the ageing resistance of the compound is improved. In addition, the compounds can also be used as heat stabilizers for certain labile compounds. In summary, N-2-ethylhexyl-N' -phenyl-p-phenylenediamine is an indispensable modifier in modern synthetic rubbers and synthetic compounds.
Currently, synthesis of N-2-ethylhexyl-N' -phenyl-p-phenylenediamine is mainly based on synthesis of related fatty alcohols (mainly isooctanol (2-ethylhexanol)) with RT pessary (4-aminodiphenylamine) under strong alkali and high temperature and pressure conditions, such as russian patent RU2417981C1, RU2293077C, RU2362767, RU2406720C1, RU2010146340a, etc. There are also a few other foreign patents for similar compound studies such as WO2009038064A, EP0510493A, etc. The technical schemes described in the patents have the defects of complex process (such as high temperature, high pressure and special catalyst), high equipment requirement, high production cost and the like.
Disclosure of Invention
The application aims to provide a synthesis method of N-2-ethylhexyl-N '-phenyl-p-phenylenediamine, which aims to solve the problems of complex synthesis process, high production cost and the like of N-2-ethylhexyl-N' -phenyl-p-phenylenediamine in the prior art.
In order to achieve the above object, according to one aspect of the present application, there is provided a method for synthesizing N-2-ethylhexyl-N '-phenyl-p-phenylenediamine, which comprises subjecting a compound a to hydrogenation with 4-aminodiphenylamine to obtain N-2-ethylhexyl-N' -phenyl-p-phenylenediamine; wherein the compound A is 2-ethyl-2-hexenal or 2-ethyl-2-hexanal.
Further, the molar ratio between the compound A and the 4-aminodiphenylamine is 0.8-1.2:1.
Further, in the reaction process of the compound A and the 4-aminodiphenylamine, the reaction temperature is 0-180 ℃, preferably 25-45 ℃; the reaction pressure is 0.1 to 5MPa, preferably 1 to 2.5MPa.
Further, the compound A and 4-aminodiphenylamine are subjected to hydrogenation reaction in the presence of a polar solvent, a catalyst and hydrogen to obtain N-2-ethylhexyl-N' -phenyl-p-phenylenediamine.
Further, the catalyst is a metal catalyst, preferably one or more selected from copper-based catalysts, palladium-carbon-based catalysts, nickel-based catalysts, platinum-carbon-based catalysts and reduced iron powder.
Further, the polar solvent is selected from one or more of methanol, toluene, ethanol, n-butanol and dichloromethane.
Further, the catalyst is used in an amount of 0.5 to 50% by weight, preferably 20 to 40% by weight, based on 4-aminodiphenylamine.
Further, in the reaction process of the compound A and the 4-aminodiphenylamine, 0.2 to 1g of 4-aminodiphenylamine is contained in each milliliter of polar solvent.
Further, the compound A is 2-ethyl-2-hexenal, and the step of adding n-butyraldehyde into a strong alkaline solvent for reaction to prepare 2-ethyl-2-hexenal is further included before the step of carrying out hydrogenation reaction on the 2-ethyl-2-hexenal and 4-aminodiphenylamine.
Further, the strong base solvent is selected from aqueous sodium hydroxide or aqueous potassium hydroxide; the mass concentration of the strong alkali solvent is 0.5-10%, preferably 0.8-2%; the amount of the strong base solvent is 50 to 200% by weight, preferably 80 to 100% by weight, based on the weight of n-butyraldehyde.
By using the method for synthesizing the N-2-ethylhexyl-N' -phenyl-p-phenylenediamine, 2-ethyl-2-hexenal or 2-ethyl-2-hexanal is used as a raw material to carry out hydrogenation reaction with 4-aminodiphenylamine. The reactivity of 2-ethyl-2-hexenal and 2-ethyl-2-hexanal is higher and the cost is lower than other raw materials, especially isooctanol. Meanwhile, when the catalyst is subjected to hydrogenation reaction with 4-aminodiphenylamine, the reaction conditions are mild, the requirements on reaction equipment are low, the yield of target products is high, the post-treatment is simple, and the pollution is small. In a word, the synthesis method of the N-2-ethylhexyl-N' -phenyl-p-phenylenediamine provided by the application has the advantages of simple process, low cost and environmental friendliness.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As described in the background art, the existing synthetic route of N-2-ethylhexyl-N' -phenyl-p-phenylenediamine has the problems of complex process, high production cost and the like. In order to solve the problem, the application provides a synthesis method of N-2-ethylhexyl-N '-phenyl-p-phenylenediamine, which takes a compound A and 4-aminodiphenylamine as raw materials to carry out hydrogenation reaction to obtain N-2-ethylhexyl-N' -phenyl-p-phenylenediamine; wherein the compound A is 2-ethyl-2-hexenal or 2-ethyl-2-hexanal.
In the synthesis method of N-2-ethylhexyl-N' -phenyl p-phenylenediamine provided by the application, 2-ethyl-2-hexenal or 2-ethyl-2-hexanal is used as a raw material to carry out hydrogenation reaction with 4-aminodiphenylamine. The reactivity of 2-ethyl-2-hexenal and 2-ethyl-2-hexanal is higher and the cost is lower than other raw materials, especially isooctanol. Meanwhile, when the two raw materials and 4-aminodiphenylamine are subjected to hydrogenation reaction, the reaction conditions are mild, the requirements on reaction equipment are low, the yield of target products is high, the post-treatment is simple, and the pollution is small. In a word, the synthesis method of the N-2-ethylhexyl-N' -phenyl-p-phenylenediamine provided by the application has the advantages of simple process, low cost and environmental friendliness.
In particular, compared with 2-ethyl-2-hexenal, the hydrogenation reaction of 2-ethyl-2-hexanal and 4-aminodiphenylamine is more beneficial to reducing the reaction difficulty, and the reaction impurities are less.
In the above synthesis method provided by the application, the person skilled in the art can adjust the relation of the amount of the reaction raw materials according to the reaction principle. In a preferred embodiment, the molar ratio between compound A and 4-aminodiphenylamine is in the range from 0.8 to 1.2:1. The molar ratio between the 2-ethyl-2-hexenal and the 4-aminodiphenylamine is controlled within the above range, which is beneficial to further improving the yield of the target product. Meanwhile, the molar ratio can also reduce the generation of side reactions and improve the purity of the product. More preferably the molar ratio of the two is 1:1.
In the synthetic method provided by the application, the hydrogenation reaction can be carried out under milder process conditions. In a preferred embodiment, the reaction temperature during the reaction of compound a with 4-aminodiphenylamine is in the range of 0 to 180 ℃, preferably 25 to 45 ℃; the reaction pressure is 0.1 to 5MPa, preferably 1 to 2.5MPa. Under the conditions of the temperature and the pressure, the reaction rate of the compound A and the 4-aminodiphenylamine is higher, and the yield of the target product is higher. Meanwhile, the method is also beneficial to reducing the reaction energy consumption, so that the method is more suitable for industrialized mass production.
In a preferred embodiment, the above synthesis method comprises the steps of: the compound A and 4-aminodiphenylamine are subjected to hydrogenation reaction in the presence of a polar solvent, a catalyst and hydrogen to obtain N-2-ethylhexyl-N' -phenyl-p-phenylenediamine. The compound A and the 4-aminodiphenylamine are subjected to hydrogenation reaction in the presence of a polar solvent, a catalyst and hydrogen, and the reaction stability and the reaction rate are improved, so that the effectiveness and the safety of industrial application are further ensured.
In the synthesis method provided by the application, 2-ethyl-2-hexenal or 2-ethyl-2-hexanal is used as a reaction raw material, the requirement on a catalyst is low, and the adopted catalyst can be a catalyst commonly used in the field. In a preferred embodiment, the catalyst includes, but is not limited to, a metal catalyst, preferably one or more selected from the group consisting of copper-based catalyst, palladium-carbon-based catalyst, nickel-based catalyst, platinum-carbon-based catalyst, and reduced iron powder. The hydrogenation reaction of the application is catalyzed by the above catalysts, the catalytic activity is higher, and the reaction rate can be further improved. Meanwhile, the catalyst has lower requirements on equipment, and is more beneficial to simplifying the production process. More preferably, a palladium-carbon type catalyst, a nickel type catalyst or a platinum-carbon type catalyst is used.
The polar solvents used in the hydrogenation process may be selected by those skilled in the art in light of the above teachings of the present application. In a preferred embodiment, the polar solvent includes, but is not limited to, one or more of methanol, toluene, ethanol, n-butanol, and methylene chloride. The polar solvents and the reaction raw materials have better compatibility, and can provide a more stable synthesis environment for hydrogenation reaction. More preferably, the polar solvent is methanol.
In a preferred embodiment, the catalyst is used in an amount of 0.5 to 50% by weight of 4-aminodiphenylamine. This is advantageous in improving the reaction rate of the hydrogenation reaction and, at the same time, in reducing the production cost. More preferably, the catalyst is used in an amount of 20 to 40% by weight of 4-aminodiphenylamine.
In the synthesis method provided by the application, the stability of the reaction can be improved by only carrying out hydrogenation reaction on 2-ethyl-2-hexenal or 2-ethyl-2-hexanal and 4-aminodiphenylamine in a polar solvent. In a preferred embodiment, the compound A and 4-aminodiphenylamine are reacted in the hydrogenation reaction, and each milliliter of polar solvent contains 0.2 to 1g of 4-aminodiphenylamine. The dosage relation between the main reaction raw materials and the polar solvent reaction medium is set in the range, so that the stability and the safety of hydrogenation reaction can be improved, and the problems of resource waste, energy consumption and time consumption of post-treatment and the like caused by excessive solvents can be avoided.
In the synthesis method provided by the application, the sources of the reaction raw materials are wide, the cost is low, and the synthesis method can be commercially available. In a preferred embodiment, compound a is 2-ethyl-2-hexenal, further comprising the step of adding n-butyraldehyde to a strongly basic solvent for reaction to produce 2-ethyl-2-hexenal, prior to the step of hydrogenating 2-ethyl-2-hexenal with 4-aminodiphenylamine. The method takes the n-butyraldehyde as the raw material, and utilizes the strong alkali solvent to prepare the 2-ethyl-2-hexenal, and the reaction process is simple and easy to operate, and has higher conversion rate. This is advantageous for further reducing the production cost of N-2-ethylhexyl-N' -phenyl-p-phenylenediamine.
In the above synthetic method provided by the application, the strong alkaline solvent used in the preparation of 2-ethyl-2-hexenal by using n-butyraldehyde as a raw material can be any strong alkaline solvent. In a preferred embodiment, the strong base solvent includes, but is not limited to, aqueous sodium hydroxide or aqueous potassium hydroxide; the mass concentration of the strong alkali solvent is 0.5-10%, preferably 0.8-2%; the amount of the strong base solvent is 50 to 200% by weight, preferably 80 to 100% by weight, based on the weight of n-butyraldehyde. The adoption of the strong alkaline solvent can accelerate the reaction rate and conversion rate of the n-butyraldehyde, and the prepared 2-ethyl-2-hexenal has higher purity and lower impurity content. Thereby providing high-quality raw materials for the later hydrogenation reaction.
In the synthesis method provided by the application, in the process of adding n-butyraldehyde into a strong alkaline solvent for reaction, the reaction temperature is 70-110 ℃, and the reaction time is 0.3-8 h. Under the reaction condition, the 2-ethyl-2-hexenal with higher purity and higher yield can be produced with less energy consumption. More preferably, n-butyraldehyde is added into the strong alkaline solvent in a dropwise manner, wherein the dropwise addition temperature is 70-110 ℃; after the dripping is finished, the temperature of the reaction system is controlled to be 80-110 ℃, and the reaction is carried out for 0.5-3 hours at constant temperature. The n-butyraldehyde is added dropwise at the temperature, which is favorable for preventing the risk of too slow reaction and heating reflux caused by too low temperature. Meanwhile, the method is also beneficial to preventing the problems of excessive energy consumption and unnecessary waste caused by excessive temperature. Secondly, after the completion of the dropwise addition of n-butyraldehyde, setting the constant temperature within the above-mentioned range is advantageous in preventing the problem of a large residual amount of n-butyraldehyde caused by too low a temperature. Meanwhile, the energy consumption waste caused by the overhigh temperature is prevented. In addition, the reaction time is controlled within the range, which is favorable for improving the conversion rate of the n-butyraldehyde in a shorter time, and the reaction has higher conversion rate and production efficiency.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Example 1
Into a four-necked flask, 50g of a sodium hydroxide solution having a mass concentration of 1% was charged, and the flask was heated to about 90 ℃. 50g of n-butyraldehyde is added dropwise into the system, the reaction temperature is kept at 90 ℃ after the dropwise addition, and the mixture is separated after the reaction is carried out for 1 hour, so that an oil layer is obtained, namely a 2-ethyl-2-hexenal product (hereinafter referred to as 2-enal).
33.5g of the oil layer was taken and put into a 500mL autoclave, then 46.2g of 4-aminodiphenylamine (RT), 200mL of methanol and 15g of Raney nickel catalyst were added into the autoclave, and hydrogenation reaction was carried out after hydrogen substitution. Keeping the reaction temperature at 40 ℃ until the complete reaction is finished, filtering, and rectifying to obtain a viscous liquid product N-2 ethylhexyl-N' -phenyl-p-phenylenediamine, wherein the content is up to more than 95%, and the yield is 96-100%.
Examples 2 to 9
The procedure of N-2 ethylhexyl-N' -phenyl-p-phenylenediamine in example 1 was used to change the type and amount of catalyst used in the hydrogenation step, and the specific procedures and experimental results obtained for each example were as follows:
| examples | Yield of S789 (%) | S789 purity (%) | RT content (%) | Content of main impurity (%) |
| 2 | 89.54 | 85.24 | 1.61 | 8.67 |
| 3 | 96.79 | 94.27 | 0.52 | 1.42 |
| 4 | 97.02 | 94.51 | 0.28 | 1.21 |
| 5 | 99.10 | 96.81 | 0.59 | 1.09 |
| 6 | 35.11 | 25.14 | 29.02 | 11.31 |
| 7 | 99.83 | 98.28 | 0.09 | 0.67 |
| 8 | 99.50 | 96.85 | 0.06 | 0.87 |
| 9 | 95.74 | 92.3 | 0.27 | 3.75 |
Examples 10 to 18
The reaction temperature in the hydrogenation reaction step was changed by using the process step of N-2 ethylhexyl-N' -phenyl-p-phenylenediamine in example 1, and the specific process and experimental results obtained for each example were as follows:
| examples | Yield of S789 (%) | S789 purity (%) | RT content (%) | Content of main impurity (%) |
| 10 | 94.23 | 91.78 | 1.46 | 1 |
| 11 | 94.35 | 91.87 | 3.66 | 3.76 |
| 12 | 94.20 | 91.67 | 3.75 | 3.77 |
| 13 | 99.57 | 97.07 | 0.1 | 0.42 |
| 14 | 99.91 | 98.28 | 0.09 | 0.67 |
| 15 | 99.10 | 96.84 | 0.06 | 0.48 |
| 16 | 99.66 | 97.29 | 0.09 | 0.47 |
| 17 | 97.9 | 96.4 | 1.03 | 0.14 |
| 18 | 88.14 | 83.41 | 2.53 | 9.29 |
Examples 19 to 25
The reaction pressure in the hydrogenation reaction step was changed by using the process step of N-2 ethylhexyl-N' -phenyl-p-phenylenediamine in example 1, and the specific process and experimental results obtained for each example were as follows:
| examples | Yield of S789 (%) | S789 purity (%) | RT content (%) | Content of main impurity (%) |
| 19 | 99.31 | 96.81 | 0.09 | 0.87 |
| 20 | 99.28 | 96.85 | 0.06 | 0.56 |
| 21 | 98.93 | 96.01 | 0.07 | 0.99 |
| 22 | 99.48 | 96.90 | 0.05 | 0.72 |
| 23 | 92.85 | 89.74 | 2.33 | 6.88 |
| 24 | 94.33 | 90.52 | 2.46 | 5.91 |
| 25 | 88.90 | 86.76 | 2.51 | 7.4 |
Examples 26 to 33
The type and amount of polar solvents used in the hydrogenation step were varied by using the process steps of N-2 ethylhexyl-N' -phenyl-p-phenylenediamine in example 1, and the specific processes and experimental results obtained for each example were as follows:
examples 34 to 37
The molar ratio between RT substrate and 2-enal in the hydrogenation reaction step was varied by using the process steps of N-2 ethylhexyl-N' -phenyl-p-phenylenediamine in example 1, the specific process and experimental results obtained for each example were as follows:
| examples | Yield of S789 (%) | S789 purity (%) | RT content (%) | Content of main impurity (%) |
| 34 | 99.52 | 96.85 | 0.06 | 0.56 |
| 35 | 99.10 | 96.38 | 0.02 | 0.8 |
| 36 | 88.20 | 86.22 | 0.02 | 9.24 |
| 37 | 61.25 | 58.74 | 0.00 | 41.23 |
Examples 38 to 45
The mass concentration of the strong alkaline solvent was changed by adopting the preparation process of 2-ethyl-2 hexenal in example 1, and the specific process and the obtained experimental result data of each example are as follows:
examples 46 to 50
The preparation process of the 2-ethyl-2 hexenal in the example 1 is adopted, the dosage of the strong alkaline solvent is changed, and the specific process and the obtained experimental result data of each example are as follows:
examples 51 to 58
By adopting the preparation process of the 2-ethyl-2 hexenal in the example 1, the dropping temperature and the reaction temperature of the n-butyraldehyde in the hydrogenation reaction step are changed, and the specific process and the obtained experimental result data of each example are as follows:
examples 59 to 64
The preparation process of the 2-ethyl-2 hexenal in the example 1 is adopted to change the reaction time of the n-butyraldehyde in a strong alkaline solvent, and the specific process and the obtained experimental result data of each example are as follows:
example 65
33g of 2-ethyl-2 hexanal was charged into a 500mL autoclave, 46.2g of 4-aminodiphenylamine (RT), 200mL of methanol and 15g of Raney nickel catalyst were then added into the autoclave, and hydrogenation reaction was carried out after hydrogen substitution. Keeping the reaction temperature at 40 ℃ until the complete reaction is finished, filtering, and rectifying to obtain a viscous liquid product N-2 ethylhexyl-N' -phenyl-p-phenylenediamine, wherein the content is up to more than 96%, and the yield is 95-99%.
From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects:
by adopting the synthesis process in the embodiment, the N-butyraldehyde is used for preparing 2-ethyl-2-hexenal, and then the 2-ethyl-2-hexenal reacts with RT pessary under the action of a catalyst to prepare the compound N-2-ethylhexyl-N' -phenyl-p-phenylenediamine. Meanwhile, the synthesis process is simple, the condition is mild, the post-treatment is simple, and the yield and purity of the target product are high.
More particularly, the existing process for preparing the anti-aging agent S789 can be further improved by controlling the types and the amounts of the catalysts, the proportion of materials, the reaction temperature and the like in specific ranges, so that the method has the advantages of reducing the production cost, simplifying the post-treatment operation and the like.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The synthesis method of the N-2-ethylhexyl-N '-phenyl-p-phenylenediamine is characterized in that a compound A and 4-aminodiphenylamine are used as raw materials for hydrogenation reaction to obtain the N-2-ethylhexyl-N' -phenyl-p-phenylenediamine; wherein the compound A is 2-ethyl-2-hexenal, and the synthetic method further comprises the step of adding n-butyraldehyde into a strong alkaline solvent to react to prepare the 2-ethyl-2-hexenal before the step of carrying out the hydrogenation reaction on the 2-ethyl-2-hexenal and the 4-aminodiphenylamine, wherein the reaction temperature is 70-110 ℃ and the reaction time is 0.3-8 h.
2. The synthetic method according to claim 1, wherein the molar ratio between the compound a and the 4-aminodiphenylamine is 0.8-1.2:1.
3. The synthesis according to claim 1 or 2, wherein during the reaction of compound a and 4-aminodiphenylamine, the reaction temperature is between 0 and 180 ℃, preferably between 25 and 45 ℃; the reaction pressure is 0.1 to 5MPa, preferably 1 to 2.5MPa.
4. The method according to claim 3, wherein the compound a and the 4-aminodiphenylamine are subjected to the hydrogenation reaction in the presence of a polar solvent, a catalyst and hydrogen to obtain the N-2-ethylhexyl-N' -phenyl-p-phenylenediamine.
5. The method according to claim 4, wherein the catalyst is a metal catalyst, preferably one or more selected from the group consisting of copper-based catalyst, palladium-carbon-based catalyst, nickel-based catalyst, platinum-carbon-based catalyst and reduced iron powder.
6. The method of synthesis according to claim 5, wherein the polar solvent is selected from one or more of methanol, toluene, ethanol, n-butanol and methylene chloride.
7. The method according to claim 5 or 6, wherein the catalyst is used in an amount of 0.5 to 50%, preferably 20 to 40% by weight of the 4-aminodiphenylamine.
8. The synthetic method according to any one of claims 4 to 7, wherein 0.2 to 1g of 4-aminodiphenylamine is contained per ml of the polar solvent during the reaction of the compound a and the 4-aminodiphenylamine.
9. The synthetic method according to claim 1, wherein the strong base solvent is selected from the group consisting of aqueous sodium hydroxide solution and aqueous potassium hydroxide solution; the mass concentration of the strong alkali solvent is 0.5-10%, preferably 0.8-2%; the amount of the strong base solvent is 50 to 200% by weight, preferably 80 to 100% by weight, based on the weight of the n-butyraldehyde.
10. The synthesis method according to claim 1, wherein the n-butyraldehyde is added to the strongly basic solvent in a dropwise manner at a temperature of 70 to 110 ℃; after the dripping is finished, the temperature of the reaction system is controlled to be 80-110 ℃, and the reaction is carried out for 0.5-3 hours at constant temperature.
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