CN113683578B - Preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine - Google Patents
Preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims abstract description 40
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006467 substitution reaction Methods 0.000 claims abstract description 28
- 229960001413 acetanilide Drugs 0.000 claims abstract description 26
- CHMBIJAOCISYEW-UHFFFAOYSA-N n-(4-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(N)C=C1 CHMBIJAOCISYEW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- 239000000463 material Substances 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 38
- 238000005303 weighing Methods 0.000 claims description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- 239000007983 Tris buffer Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- XJLDOQZMHZFDPZ-UHFFFAOYSA-N 4-(2-methylhexan-2-yl)cyclohexa-1,5-diene-1,4-diamine Chemical compound CC(CCCC)(C1(CC=C(C=C1)N)N)C XJLDOQZMHZFDPZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000011949 solid catalyst Substances 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 230000000850 deacetylating effect Effects 0.000 abstract description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- -1 4-dimethylpentylphenylaniline Chemical compound 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- QRKJNCRCYBKANP-UHFFFAOYSA-N 2-amino-n-phenylacetamide Chemical compound NCC(=O)NC1=CC=CC=C1 QRKJNCRCYBKANP-UHFFFAOYSA-N 0.000 description 1
- CLFLIWXLUUCHDM-UHFFFAOYSA-N 4-N-(2-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(CCCC)(C)NC1=CC=C(C=C1)N CLFLIWXLUUCHDM-UHFFFAOYSA-N 0.000 description 1
- YICAMJWHIUMFDI-UHFFFAOYSA-N 4-acetamidotoluene Chemical compound CC(=O)NC1=CC=C(C)C=C1 YICAMJWHIUMFDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FMJYAEKFCVLAKT-UHFFFAOYSA-N [C].[Rh] Chemical class [C].[Rh] FMJYAEKFCVLAKT-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- KVEDKKLZCJBVNP-UHFFFAOYSA-N n-(4-acetamidophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(NC(C)=O)C=C1 KVEDKKLZCJBVNP-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine, which comprises the following steps: carrying out catalytic hydrogenation reaction on p-aminoacetanilide and methyl isoamyl ketone to obtain N-1, 4-dimethyl amyl p-acetanilide; deacetylating N-1, 4-dimethylpentyl-p-acetanilide in an alkali solution to obtain N-1, 4-dimethylpentyl-p-acetanilide; cyanuric chloride and N-1, 4-dimethyl amyl p-phenylenediamine are subjected to substitution reaction and post treatment to obtain 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine. The invention has the advantages of high reaction selectivity and yield, less by-products, low cost and good quality.
Description
Technical Field
The invention relates to a preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine, belonging to the technical field of fine chemical engineering.
Background
The alkylaryl anti-aging agents are mainly used for preventing rubber from aging due to heat, ozone, oxygen, mechanical fatigue and the like, but the alkylaryl anti-aging agents are easy to migrate out of vulcanized rubber, react with ozone in the atmospheric environment on the surface of a tire or a rubber product to form a color-changing substance, and seriously affect the appearance of the tire or the rubber, particularly light-colored rubber products. Subsequently, the antioxidant TAPDT, which is commercially available under the name Durazone37 and is chemically named 2,4, 6-tris (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine, has been introduced by Koppon corporation, U.S. Patch, and it has a relatively large molecular mass, a slow migration rate, and the like, and is suitable for use as an antiozonant for heavy duty tires and agricultural tires.
Experiments prove that the intermediate N-1, 4-dimethyl amyl p-phenylenediamine of the anti-aging agent is prepared by reacting p-phenylenediamine and 5-methyl-2-hexanone, the one-step reaction needs to accurately control the ratio of ketone to amine, the excess proportion of amine is large, the p-phenylenediamine needs to be recovered from a mixture after the reaction is finished, N' -di (dimethyl amyl) p-phenylenediamine (namely the anti-aging agent 4030) is easy to generate, and the selectivity is not high.
Chinese patent CN108203414A uses p-nitroaniline and cyanuric chloride as raw materials, firstly prepares intermediate 2,4, 6-tri- (4-nitroaniline) -1,3, 5-triazine, and then reacts with 5-methyl-2-hexanone through reversion hydrogenation to synthesize the product, the toxicity of p-nitroaniline in the process is high, the danger of nitro hydrogenation reduction process is large, and the process safety is poor.
Disclosure of Invention
Aiming at the defects of poor selectivity, low yield, high cost, poor process safety and the like existing in the prior art, the invention provides a preparation method of an anti-aging agent 2,4, 6-tris (N-1, 4-dimethylpentyl p-phenylenediamine) -1,3, 5-triazine, the method takes p-aminoacetanilide as a raw material, and the p-aminoacetanilide reacts with methyl isoamyl ketone to form the N-1, 4-dimethylpentyl p-acetanilide, the method has good selectivity, high yield and low cost, and provides a new thought for the preparation of the 2,4, 6-tris (N-1, 4-dimethylpentyl p-phenylenediamine) -1,3, 5-triazine.
The specific technical scheme of the invention is as follows:
a method for preparing 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine, comprising the following steps:
(1) Carrying out catalytic hydrogenation reaction on p-aminoacetanilide and methyl isoamyl ketone to obtain N-1, 4-dimethyl amyl p-acetanilide;
(2) Deacetylating N-1, 4-dimethyl amyl p-acetanilide in an alkali solution to obtain N-1, 4-dimethyl amyl p-acetanilide;
(3) Cyanuric chloride and N-1, 4-dimethyl amyl p-phenylenediamine are subjected to substitution reaction and post treatment to obtain 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine.
In step (1), the molar ratio of the aminoacetanilide to the methyl isoamyl ketone is 1 to 1.5, preferably 1.
Further, in the step (1), the catalyst is a palladium carbon catalyst, a platinum carbon catalyst, a rhodium carbon catalyst or a nickel carbon catalyst. The dosage of the catalyst is 2-4% of the mass of the p-aminoacetanilide.
Further, in the step (1), the reaction is carried out in a solvent, and the solvent is methanol.
Further, in the step (1), the reaction temperature is 60 to 120 ℃, preferably 80 to 90 ℃.
Further, in the step (1), during the reaction, the pressure of hydrogen is kept between 0.3 and 0.4Mpa, and when the pressure is lower than 0.1Mpa, hydrogen is supplemented to between 0.3 and 0.4Mpa until the reaction is finished when the pressure of hydrogen is unchanged or basically unchanged.
Further, in the step (2), the N-1, 4-dimethyl amyl acetanilide is heated in an ethanol solution of sodium hydroxide or potassium hydroxide for reflux reaction, and acetyl is removed. Wherein, the molar ratio of the N-1, 4-dimethyl amyl acetanilide to the sodium hydroxide or the potassium hydroxide is 1 to 1.3. The concentration of the ethanol solution of sodium hydroxide or potassium hydroxide may be adjusted according to actual needs, for example, 5 to 10wt%.
Further, in the step (3), the substitution reaction is carried out in three steps, and the substitution reaction comprises the following steps: mixing cyanuric chloride with a solvent to prepare a solution or slurry; mixing N-1, 4-dimethyl amyl p-aniline with a solvent to obtain a solution; the temperature of the cyanuric chloride solution or the pulp is maintained at the primary substitution reaction temperature, then the N-1, 4-dimethyl amyl p-aniline solution is dripped, the temperature is maintained after the dripping is finished to carry out the primary substitution reaction, then the temperature is raised to the secondary substitution reaction temperature to carry out the secondary substitution reaction, and then the temperature is raised to the boiling reflux state to carry out the tertiary substitution reaction.
Furthermore, in the step (3), the dripping time of the N-1, 4-dimethyl amyl p-aniline solution is about 0.5 h.
Further, in the step (3), the temperature of the primary substitution reaction is-10 to 0 ℃, and the reaction time is 1 to 2 hours; the temperature of the secondary substitution reaction is 25 to 45 ℃, and the reaction time is 3 to 4 hours; the temperature of the trisubstitution reaction is determined according to the boiling point of the solvent, and the reaction is kept to be in a boiling reflux state for 3-4h.
In step (3), the molar ratio of N-1, 4-dimethylpentyl-p-aniline to cyanuric chloride is 3 to 3.5, preferably 3.1.
Further, in the step (3), the solvent is methanol, ethanol, isopropanol, toluene, xylene, benzene or dioxane. The reaction temperature of the trisubstitution reaction differs depending on the solvent. The purpose of the solvent is to provide a reaction environment, and the amount thereof can be selected and adjusted as necessary.
Further, in the step (3), after the substitution reaction is completed, the post-treatment mode is as follows: after the substitution reaction is finished, the temperature of the materials is reduced to 50 to 60 ℃, sodium hydroxide solution with the molar quantity equal to that of hydrogen chloride generated in the reaction is dripped into the materials for neutralization reaction, water is added into the materials after the reaction to separate out solid, and then the solid is filtered, washed and dried to obtain the 2,4, 6-tris (N-1, 4-dimethylpentyl p-phenylenediamine) -1,3, 5-triazine.
In one embodiment of the present invention, a process for preparing 2,4, 6-tris (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine is disclosed, comprising the steps of:
first, preparation of the intermediate N-1, 4-dimethylpentyl-p-acetanilide
Dissolving p-aminoacetanilide in methanol and transferring the methanol into a high-pressure kettle, activating a catalyst by using the methanol, adding the activated catalyst into the high-pressure kettle, adding methyl isoamyl ketone into the high-pressure kettle, covering the high-pressure kettle, replacing the activated catalyst by using nitrogen for three times, replacing the activated catalyst by using hydrogen for three times, raising the reaction temperature, introducing the hydrogen for reaction, reducing the temperature and releasing the pressure after the hydrogenation reaction is finished, discharging the material, filtering out the solid catalyst, rotatably evaporating a filtrate to remove the solvent methanol and byproduct alcohol, pouring out the residual material, and cooling to obtain the N-1, 4-dimethyl amyl p-acetanilide for later use. The reaction formula is as follows:
second step, preparation of intermediate N-1, 4-dimethylpentylphenylaniline
Putting the N-1, 4-dimethylpentyl p-acetanilide and the ethanol solution of potassium hydroxide or sodium hydroxide into a reaction kettle, heating to boil, performing reflux reaction, pouring the solution into ice water after the reaction is finished to obtain the N-1, 4-dimethylpentyl p-acetanilide, filtering, washing to be alkalescent or neutral, and drying for later use. Taking sodium hydroxide as an example, the reaction formula is as follows:
third step, preparation of 2,4, 6-tris (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine
Dissolving cyanuric chloride with a solvent or preparing into slurry, transferring the obtained solution or slurry into a reaction kettle, dissolving N-1, 4-dimethyl amyl p-aniline with the solvent and transferring into a constant-pressure dropping funnel, firstly, reducing cyanuric chloride materials to a primary substitution reaction temperature, beginning to drop N-1, 4-dimethyl amyl p-aniline solution, reacting for a certain time after dropping, then, raising the materials in the reaction kettle to a secondary substitution reaction temperature, raising the materials in the kettle to a boiling reflux state after reacting for a period of time, and carrying out a tertiary substitution reaction.
After the trisubstitution reaction is finished, the temperature of the materials is reduced to 50-60 ℃, sodium hydroxide solution with the same mole number as that of chlorine elements in cyanuric chloride is dripped in the materials, the materials are stirred and reacted for a certain time, then the temperature is reduced, water is added in the materials to separate out products, and the products are washed and dried to obtain 2,4, 6-tris (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine. The reaction formula is as follows:
the invention has the following beneficial effects:
1. according to the invention, p-aminoacetanilide is selected as a raw material, the p-aminoacetanilide reacts with methyl isoamyl ketone to form N-1, 4-dimethyl amyl p-acetanilide, and then the N-1, 4-dimethyl amyl p-acetanilide is deacetylated to obtain the N-1, 4-dimethyl amyl p-acetanilide. The process route has the advantages of high reaction selectivity, less side reactions, simple product post-treatment, simple process, high yield and high purity of the obtained intermediate, and avoids the problem of difficult rectification, recovery and separation when p-phenylenediamine is used as a raw material.
2. Compared with p-nitroaniline which is used as a raw material, the p-nitroaniline-containing p-nitroaniline composite material has higher safety, low cost and good industrial application prospect.
Detailed Description
The present invention is illustrated by the following specific examples, which are intended to be merely exemplary and not limiting.
In the following examples, yield = product quality/theoretical quality of product.
Example 1
First, preparation of intermediate N-1, 4-dimethylpentyl-p-acetanilide
Weighing 15.02 g (0.1 mol) of p-aminoacetanilide, dissolving in 100ml of methanol and transferring into an autoclave; weighing 0.3 g of palladium-carbon catalyst, washing and activating with methanol, and then adding into an autoclave; weighing 12.56 g (0.11 mol) of methyl isoamyl ketone, adding the methyl isoamyl ketone into a high-pressure kettle, covering a cover, replacing the mixture with nitrogen for three times, replacing the mixture with hydrogen for three times, raising the reaction temperature to 85 ℃, introducing hydrogen for reaction, stopping introducing the hydrogen when the pressure in the kettle is 0.4MPa each time, introducing the hydrogen again until the pressure in the kettle is reduced to 0.1MPa, introducing the hydrogen again into the kettle to stop introducing the hydrogen until the pressure in the kettle is reduced to 0.4MPa, introducing the hydrogen again when the pressure in the reaction kettle is reduced to 0.1MPa, repeating the steps until the pressure in the kettle is reduced to less than or equal to 0.02MPa within half an hour, finishing the hydrogenation reaction, wherein the time is about 32 hours, then reducing the temperature and releasing the pressure to discharge the materials, filtering and filtering out a solid catalyst, removing a solvent methanol and a byproduct alcohol by rotary evaporation from a filtrate, pouring out and cooling the rest materials to obtain 26.07 g (0.099 mol) of N-1, 4-dimethyl amyl p-acetanilide, the liquid phase purity is detected to be 99.5%, the selectivity is 99.1%, and the yield is 98.6% based on the p-aminoacetanilide.
Second step, preparation of intermediate N-1, 4-dimethylpentylphenylaniline
Weighing 21.15 g (0.08 mol) of the intermediate, putting the intermediate into a reaction kettle with a reflux device, weighing 5.6 g of potassium hydroxide, dissolving the potassium hydroxide in 100ml of ethanol to prepare a potassium hydroxide ethanol solution, adding the solution into the reaction kettle, heating to boil, carrying out reflux reaction for about 3 hours, neutralizing the pH value of the material with dilute hydrochloric acid to be alkalescent or neutral, then pouring the solution into ice water to obtain crystals, filtering, washing the crystals, and drying to obtain 17.62 g (0.08 mol) of N-1, 4-dimethyl amyl p-aniline, wherein the liquid phase purity is 99.7 percent, and the yield is 99.5 percent based on the N-1, 4-dimethyl amyl p-acetanilide.
The third step is 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine group) -1,3, 5-triazine
Weighing 2.98 g (0.0162 mol) of cyanuric chloride, dissolving the cyanuric chloride with 50 ml of isopropanol, transferring the cyanuric chloride into a reaction kettle, weighing 11.07 g (0.05 mol) of N-1, 4-dimethyl amyl p-aniline, dissolving the N-1, 4-dimethyl amyl p-aniline with isopropanol, transferring the solution into a constant-pressure dropping funnel, firstly reducing the cyanuric chloride isopropanol solution to the primary substitution reaction temperature of-5 ℃, beginning to dropwise add the N-1, 4-dimethyl amyl p-aniline isopropanol solution, reacting for 1 hour after the dropwise addition is finished, then increasing the material in the reaction kettle to the secondary substitution reaction temperature of 35 ℃, reacting for 3 hours, then increasing the material in the kettle to a boiling reflux state, and carrying out a tertiary substitution reaction at the temperature of 85 ℃ for 3 hours. After the reaction is finished, the temperature of the materials is reduced to 50-60 ℃, aqueous solution of sodium hydroxide is dripped to carry out neutralization reaction, the materials are stirred to react for 1 hour, then the materials are cooled to room temperature and poured into a beaker, 50 ml of deionized water is added to separate out the product, and 10.99 g (0.016 mol) of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine is obtained after washing and drying, the liquid phase purity is 99.1 percent, and the yield is 98.3 percent based on cyanuric chloride.
Example 2
First, preparation of intermediate N-1, 4-dimethylpentyl-p-acetanilide
Weighing 30.04 (0.2 mol) g of p-aminoacetanilide, dissolving the p-aminoacetanilide in 220 ml of methanol, transferring the p-aminoacetanilide into an autoclave, weighing 0.9 g of rhodium-carbon catalyst, washing and activating the rhodium-carbon catalyst by methanol, adding the activated rhodium-carbon catalyst into the autoclave, weighing 27.41 (0.24 mol) of methyl isoamyl ketone, adding the methyl isoamyl ketone into the autoclave, covering the autoclave, replacing the rhodium-carbon catalyst with nitrogen for three times, replacing the rhodium-carbon catalyst with hydrogen for three times, increasing the temperature to 90 ℃, introducing hydrogen for reaction, stopping introducing the hydrogen each time until the pressure in the autoclave reaches 0.4MPa, when the pressure in the autoclave is reduced to 0.1MPa, introducing the hydrogen again to 0.4MPa, stopping introducing the hydrogen when the pressure in the autoclave is reduced to 0.1MPa, repeating the steps until the pressure in the autoclave is reduced to 0.02MPa or less for a last time, the hydrogenation reaction is about 30 hours, then decompressing and reducing the temperature, discharging the material, filtering the solid catalyst, rotationally steaming the solvent methanol and the byproduct alcohol are removed, the remaining material is poured out and cooled to obtain 51.56 g (0.195 mol) of N-1, the p-dimethylacetanilide, the selectivity of the p-acetylaniline is 97%, the p-amino yield is 97.8%, the yield is 99.5%, and the purity of the p-methylacetanilide is 99.5%.
Second step, preparation of intermediate N-1, 4-dimethylpentylphenylaniline
Weighing 39.66 g (0.15 mol) of the intermediate, putting the intermediate into a reaction kettle with a reflux device, weighing 6.6 g of sodium hydroxide, dissolving the sodium hydroxide in 100 g of ethanol to prepare a sodium hydroxide ethanol solution, adding the sodium hydroxide ethanol solution into the reaction kettle, heating to boil, carrying out reflux reaction for about 4 hours, neutralizing the pH value of the material with dilute hydrochloric acid to be alkalescent or neutral, pouring the neutralized material into ice water to obtain crystals, filtering, washing the crystals, and drying to obtain 29.89 g (0.135 mol) of N-1, 4-dimethyl amyl p-aniline, wherein the liquid phase purity is 99.8 percent, and the yield is 99 percent based on the N-1, 4-dimethyl amyl p-acetanilide.
The third step, 2,4, 6-tris (N-1, 4-dimethylpentylP-phenylenediamine) -1,3, 5-triazine
Weighing 7.38 g (0.04 mol) of cyanuric chloride, dissolving the cyanuric chloride with 150 ml of isopropanol, transferring the cyanuric chloride into a reaction kettle, weighing 26.57 g (0.12 mol) of N-1, 4-dimethyl amyl p-aniline, dissolving the N-1, 4-dimethyl amyl p-aniline with isopropanol, transferring the solution into a constant-pressure dropping funnel, reducing the temperature of the cyanuric chloride isopropanol to-10 ℃ of the primary substitution reaction temperature, beginning to dropwise add the N-1, 4-dimethyl amyl p-aniline isopropanol solution, reacting for 1.5 hours after the dropwise addition is finished, raising the temperature of materials in the reaction kettle to 40 ℃ of the secondary substitution reaction temperature, reacting for 4 hours, and raising the materials in the kettle to a boiling reflux state to carry out the tertiary substitution reaction at the temperature of 70 ℃ for 4 hours. After the reaction is finished, the temperature of the materials is reduced to 50-60 ℃, 4.8 g of aqueous solution of sodium hydroxide is dripped, the mixture is stirred and reacted for 1.5 hours, then the mixture is cooled to room temperature and poured into a beaker, 200 ml of deionized water is added to separate out the product, and 27.08 g (0.0391 mol) of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine is obtained after washing and drying, the liquid phase purity is 99.3 percent, and the yield is 97.7 percent based on cyanuric chloride.
Example 3
First, preparation of the intermediate N-1, 4-dimethylpentyl-p-acetanilide
Weighing 22.53 (0.15 mol) g of p-aminoacetanilide, dissolving the p-aminoacetanilide in 180 ml of methanol, transferring the p-aminoacetanilide into an autoclave, weighing 0.6 g of platinum-carbon catalyst, washing and activating the platinum-carbon catalyst by using methanol, adding the platinum-carbon catalyst into the autoclave, weighing 19.7 (0.173 mol) of methyl isoamyl ketone, adding the methyl isoamyl ketone into the autoclave, covering the autoclave, replacing the platinum-carbon catalyst by nitrogen for three times, replacing the platinum-carbon catalyst by hydrogen for three times, increasing the reaction temperature to 80 ℃, introducing hydrogen for reaction, stopping introducing the hydrogen each time when the pressure in the autoclave reaches 0.4MPa, introducing the hydrogen again to 0.4MPa when the pressure in the autoclave reaches 0.1MPa, releasing the pressure and cooling until the pressure in the autoclave is reduced to 0.1MPa or less at the end of the hydrogenation reaction, stopping introducing the hydrogen for about 35 hours, then releasing the pressure and cooling the material, filtering the solid catalyst, rotatably steaming the solvent methanol and the byproduct alcohol from the filtrate, pouring out the rest of the rest material, cooling to obtain 38.35 g (0.145 mol) of N-1, 97% of the p-dimethylacetanilide, the selectivity of 96.7%, and the p-dimethylanilide is 99.7%, the yield of the p-acetaminoacetanilide, and the yield is 99.7% of the selectivity of the p-acetamino.
Second step, preparation of intermediate N-1, 4-dimethylpentylphenylaniline
Weighing 31.73 g (0.12 mol) of the intermediate, putting the intermediate into a reaction kettle with a reflux device, weighing 5.5 g of sodium hydroxide, dissolving the sodium hydroxide in 100 g of ethanol to prepare a sodium hydroxide ethanol solution, adding the sodium hydroxide ethanol solution into the reaction kettle, heating to boil, carrying out reflux reaction for about 4 hours, neutralizing the pH value of the material to be alkalescent or neutral by using dilute hydrochloric acid, pouring the neutralized material into ice water to obtain crystals, filtering, washing the crystals, and drying to obtain 26.22 g (0.118 mol) of N-1, 4-dimethyl amyl p-aniline, wherein the purity of a liquid phase is 99.8 percent, and the yield is 98.7 percent based on the N-1, 4-dimethyl amyl p-acetanilide.
The third step, 2,4, 6-tris (N-1, 4-dimethylpentylP-phenylenediamine) -1,3, 5-triazine
Weighing 5.535 g (0.03 mol) of cyanuric chloride, dissolving the cyanuric chloride with 130 ml of isopropanol, transferring the cyanuric chloride into a reaction kettle, weighing 21.04 g (0.095 mol) of N-1, 4-dimethyl amyl p-aniline, dissolving the N-1, 4-dimethyl amyl p-aniline with isopropanol, transferring the solution into a constant pressure dropping funnel, firstly reducing the cyanuric chloride isopropanol solution to a primary substitution reaction temperature of-7 ℃, beginning to dropwise add the N-1, 4-dimethyl amyl p-aniline isopropanol solution, reacting for 2 hours after the dropwise addition is finished, then increasing the material in the reaction kettle to a secondary substitution reaction temperature of 30 ℃, reacting for 3.5 hours, then increasing the material in the kettle to a boiling reflux state, and carrying out a tertiary substitution reaction at a temperature of 70 ℃ for 3.5 hours. After the reaction is finished, the temperature of the materials is reduced to 50-60 ℃, 3.72 g of aqueous solution of sodium hydroxide is dripped, the mixture is stirred and reacted for 1.5 hours, then the mixture is cooled to room temperature and poured into a beaker, 150 ml of deionized water is added to separate out the product, and 20.37 g (0.0294 mol) of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine is obtained after washing and drying, the liquid phase purity is 99.5 percent, and the yield is 98 percent based on cyanuric chloride.
Example 4
First, preparation of intermediate N-1, 4-dimethylpentyl-p-acetanilide
Weighing 22.53 g (0.15 mol) of p-aminoacetanilide, dissolving in 180 ml of methanol, transferring to an autoclave, weighing 0.6 g of platinum-carbon catalyst, washing and activating with methanol, adding to the autoclave, weighing 19.7 g (0.173 mol) of methyl isoamyl ketone, adding to the autoclave, covering, replacing with nitrogen for three times, replacing with hydrogen for three times, increasing the reaction temperature to 60 ℃, introducing hydrogen for reaction, stopping introducing hydrogen until the pressure in the autoclave reaches 0.4MPa, introducing hydrogen again into the autoclave until the pressure in the autoclave falls to 0.1MPa, stopping introducing hydrogen until the pressure in the autoclave reaches 0.4MPa, introducing hydrogen again until the pressure in the autoclave falls to 0.1MPa, repeating the steps until the pressure in the autoclave falls to 0.02MPa or less within half an hour, finishing the hydrogenation reaction, about 38 hours, reducing the pressure, discharging the material by pressure, filtering to remove the solid catalyst, evaporating the solvent methanol and the byproduct alcohol, pouring out the rest material, cooling to obtain 37.0 g of N-1, 98-dimethylacetanilide, and the selectivity of 3.9% of p-aminoacetanilide, and the yield is 93%.
The second step, the preparation of the intermediate N-1, 4-dimethyl amyl p-aniline: the same as in example 3.
Third step, 2,4, 6-tris (N-1, 4-dimethylpentylP-phenylenediamine) -1,3, 5-triazine: the same as in example 3.
Example 5
First, preparation of the intermediate N-1, 4-dimethylpentyl-p-acetanilide
Weighing 22.53 g (0.15 mol) of p-aminoacetanilide, dissolving in 180 ml of methanol, transferring to an autoclave, weighing 0.6 g of platinum-carbon catalyst, washing and activating with methanol, adding to the autoclave, weighing 19.7 g (0.173 mol) of methyl isoamyl ketone, adding to the autoclave, covering, replacing with nitrogen for three times, replacing with hydrogen for three times, increasing the reaction temperature to 120 ℃, introducing hydrogen for reaction, stopping introducing hydrogen until the pressure in the autoclave reaches 0.4MPa, introducing hydrogen again into the autoclave until the pressure in the autoclave falls to 0.1MPa, stopping introducing hydrogen until the pressure in the autoclave reaches 0.1MPa, introducing hydrogen again until the pressure in the autoclave falls to 0.1MPa, repeating the steps until the pressure in the autoclave falls to 0.02MPa or less, finishing the hydrogenation reaction, about 32 hours, reducing the pressure, discharging the material by pressure, filtering to remove the solid catalyst, evaporating the solvent methanol and the by-product alcohol, pouring out the rest material, cooling to obtain 36.64 g of N-1, 97% of p-aminoacetanilide, and the selectivity of p-aminoacetanilide is 92.8.8%, wherein the yield is calculated by the selectivity of p-aminoacetanilide.
The second step, the preparation of the intermediate N-1, 4-dimethyl amyl p-aniline: the same as in example 3.
Third step, 2,4, 6-tris (N-1, 4-dimethylpentylP-phenylenediamine) -1,3, 5-triazine: the same as in example 3.
Comparative example 1
Weighing 54.07 g (0.5 mol) of p-phenylenediamine, dissolving and transferring the p-phenylenediamine in methanol into an autoclave, sequentially weighing 1.4 g of palladium-carbon catalyst washed and activated by methanol and 40 g (0.35 mol) of methyl isoamyl ketone, adding the palladium-carbon catalyst and the methyl isoamyl ketone into the autoclave, closing a feeding valve, replacing air in the autoclave by nitrogen for 3 times, then replacing gas in the autoclave by hydrogen, heating the autoclave to 85 ℃, then introducing hydrogen into the autoclave to 0.4MPa, introducing hydrogen into the autoclave to 0.4MPa when the pressure in the autoclave is reduced to 0.1MPa, repeating the steps for several times until the pressure in the autoclave is reduced to be less than or equal to 0.02MPa in half an hour, wherein the reaction is ended, the reaction time is about 38 hours, then cooling, releasing the material, filtering and filtering out the solid catalyst, carrying out rotary evaporation on filtrate to remove the solvent methanol and the byproduct alcohol, then transferring the material into a rectifying tower to carry out rectification separation, and obtaining 90.77 g (0.41 mol) of N-1, 4-dimethylpentyl p-aniline, the purity of a liquid phase, the purity is 99.5%, the selectivity of the p-phenylenediamine is 81.6%, and the yield is 82%.
Weighing 34.32 g (0.155 mol) of the intermediate, dissolving the intermediate in isopropanol, transferring the solution into a constant-pressure dropping funnel, weighing 9.23 g (0.05 mol) of cyanuric chloride, dissolving the cyanuric chloride in isopropanol, transferring the solution into a reaction kettle, cooling macro materials of the reaction kettle to-10 ℃, starting to dropwise add the intermediate solution, reacting for 1 hour at the temperature after dropwise adding, heating the reaction materials to 35 ℃, reacting for 3 hours at the temperature, heating the reaction materials to about 85 ℃, refluxing and reacting for 3 hours, cooling the materials to 50 ℃ after the reaction is finished, dropwise adding a solution of 6.3 g of sodium hydroxide, stirring and reacting for 1 hour, cooling to room temperature, pouring the reaction materials into a beaker, adding 150 ml of deionized water to separate out a product, washing and drying to obtain 33.96 g (0.049 mol) of 2,4, 6-tris (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine with the purity of 99.2%, the yield of cyanuric chloride of 98%, and the total yield of 80.4%.
Claims (1)
1. A preparation method of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine is characterized by comprising the following steps:
in the first step, the preparation of the intermediate N-1, 4-dimethylpentyl-p-acetanilide:
weighing 15.02 g of p-aminoacetanilide, dissolving in 100ml of methanol and transferring into an autoclave; weighing 0.3 g of palladium-carbon catalyst, washing and activating with methanol, and then adding into an autoclave; weighing 12.56 g of methyl isoamyl ketone, adding the methyl isoamyl ketone into an autoclave, covering the autoclave, replacing the mixture with nitrogen for three times, then replacing the mixture with hydrogen for three times, raising the reaction temperature to 85 ℃, introducing hydrogen for reaction, stopping introducing the hydrogen when the pressure in the autoclave is 0.4MPa each time, introducing the hydrogen into the autoclave again until the pressure in the autoclave is reduced to 0.1MPa, stopping introducing the hydrogen into the autoclave again until the pressure in the autoclave is reduced to 0.4MPa, introducing the hydrogen again when the pressure in the autoclave is reduced to 0.1MPa, repeating the steps until the pressure in the autoclave is reduced to be less than or equal to 0.02MPa within half an hour, regarding the hydrogenation reaction as the completion, taking the reaction time for 32 hours, then reducing the temperature and releasing the pressure to discharge the materials, filtering out a solid catalyst, carrying out rotary evaporation on filtrate to remove a solvent methanol and a byproduct alcohol, pouring out and cooling the residual materials to obtain 26.07 g of N-1, 4-dimethyl amyl p-acetanilide, wherein the liquid phase purity is 99.5%, the selectivity is 99.1%, and the yield is 98.6% based on the p-aminoacetanilide;
the second step, the preparation of the intermediate N-1, 4-dimethyl amyl p-aniline:
weighing 21.15 g of the intermediate, putting the intermediate into a reaction kettle with a reflux device, weighing 5.6 g of potassium hydroxide, dissolving the potassium hydroxide in 100ml of ethanol to prepare a potassium hydroxide ethanol solution, adding the solution into the reaction kettle, heating to boil for reflux reaction for 3 hours, neutralizing the pH value of the material with dilute hydrochloric acid to be alkalescent or neutral, pouring the solution into ice water to obtain crystals, filtering and washing the crystals, and drying to obtain 17.62 g of N-1, 4-dimethyl amyl p-aniline with the liquid phase purity of 99.7 percent and the yield of 99.5 percent based on the N-1, 4-dimethyl amyl p-acetanilide;
third step, preparation of 2,4, 6-tris (N-1, 4-dimethylpentyl-p-phenylenediamine) -1,3, 5-triazine:
weighing 2.98 g of cyanuric chloride, dissolving with 50 ml of isopropanol, transferring into a reaction kettle, weighing 11.07 g of N-1, 4-dimethyl amyl p-aniline, dissolving with isopropanol, transferring into a constant-pressure dropping funnel, firstly reducing the cyanuric chloride isopropanol solution to a primary substitution reaction temperature of-5 ℃, beginning to drop the N-1, 4-dimethyl amyl p-aniline isopropanol solution, reacting for 1 hour after dropping, then raising the material in the reaction kettle to a secondary substitution reaction temperature of 35 ℃, reacting for 3 hours, and then raising the material in the kettle to a boiling reflux state for carrying out a tertiary substitution reaction at a temperature of 85 ℃ for 3 hours; after the reaction is finished, the temperature of the materials is reduced to 50-60 ℃, aqueous solution of sodium hydroxide is dripped to carry out neutralization reaction, the materials are stirred to react for 1 hour, then the materials are cooled to room temperature and poured into a beaker, 50 ml of deionized water is added to separate out the product, and the product is washed and dried to obtain 10.99 g of 2,4, 6-tri (N-1, 4-dimethyl amyl p-phenylenediamine) -1,3, 5-triazine, wherein the liquid phase purity is 99.1 percent, and the yield is 98.3 percent based on cyanuric chloride.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050871A (en) * | 1987-08-28 | 1991-04-24 | 尤尼罗亚尔化学公司 | The triazine that the arylidene diamino replaces |
| US5861535A (en) * | 1997-09-23 | 1999-01-19 | Eastman Kodak Company | Reductive alkylation process to prepare tertiary aminoaryl compounds |
| JP2007223964A (en) * | 2006-02-24 | 2007-09-06 | Koei Chem Co Ltd | Method for refining 4-(n-ethyl-n-isopropylamino)aniline |
| CN105478139A (en) * | 2014-09-17 | 2016-04-13 | 江苏圣奥化学科技有限公司 | Catalyst used for preparing N-(1,4-dimethylpentyl)-p-phenylenediamine, preparation method thereof, and preparation method of N-(1,4-dimethylpentyl)-p-phenylenediamine |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050871A (en) * | 1987-08-28 | 1991-04-24 | 尤尼罗亚尔化学公司 | The triazine that the arylidene diamino replaces |
| US5861535A (en) * | 1997-09-23 | 1999-01-19 | Eastman Kodak Company | Reductive alkylation process to prepare tertiary aminoaryl compounds |
| JP2007223964A (en) * | 2006-02-24 | 2007-09-06 | Koei Chem Co Ltd | Method for refining 4-(n-ethyl-n-isopropylamino)aniline |
| CN105478139A (en) * | 2014-09-17 | 2016-04-13 | 江苏圣奥化学科技有限公司 | Catalyst used for preparing N-(1,4-dimethylpentyl)-p-phenylenediamine, preparation method thereof, and preparation method of N-(1,4-dimethylpentyl)-p-phenylenediamine |
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