CN113004150A - Synthesis method of diphenylamine L57 and L67 - Google Patents
Synthesis method of diphenylamine L57 and L67 Download PDFInfo
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- CN113004150A CN113004150A CN202110252410.5A CN202110252410A CN113004150A CN 113004150 A CN113004150 A CN 113004150A CN 202110252410 A CN202110252410 A CN 202110252410A CN 113004150 A CN113004150 A CN 113004150A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/90—Stabilisation; Use of additives
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- 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
Abstract
The invention provides a method for synthesizing liquid alkyl diphenylamine antioxidant, in particular to nonyl diphenylamine (antioxidant L67) and octyl/butyl diphenylamine (antioxidant L57). The method uses AlCl3‑SnCl2The bi-component supported catalyst has high catalytic efficiency, good selectivity, easy separation from a reaction system, cyclic utilization and outstanding economical efficiency and environmental protection; the obtained liquid alkyl diphenylamine antioxidant has high quality, good durability and high oxidation resistance. Therefore, the synthesis method is suitable for being applied to industrial production.
Description
Technical Field
The invention relates to the field of medicinal chemistry, in particular to a preparation method of cimetidine.
Background
Alkyl diphenylamine antioxidants have been in the history for over half a century and have received much attention as being excellent in oxidation resistance and good in compatibility with oils and rubbers. The common alkyl diphenylamine antioxidants are classified according to physical forms, one is solid alkyl diphenylamine, and the other is light brown or off-white powder, and comprises octyl diphenylamine (antioxidant OD) and cumyl diphenylamine (antioxidant KY-405), and is mainly used as an antioxidant for light-colored or bright-colored rubber; the other is liquid alkyl diphenylamine, which comprises octyl/butyl diphenylamine (antioxidant L57), nonyl diphenylamine (antioxidant L67), styryl diphenylamine (antioxidant DFC-34) and the like, and is mainly used as a lubricating oil antioxidant, a soft foam polyurethane additive and a rubber antioxidant. Compared with solid alkyl diphenylamine, the liquid alkyl diphenylamine can be directly added into lubricating oil or rubber for blending, so that the process of dissolving by using a diluent before use is omitted, the use is more convenient, and the market prospect is wider.
The liquid alkyl diphenylamine antioxidant is prepared by carrying out Friedel-Crafts alkylation reaction on diphenylamine and olefins such as diisobutylene, nonene, styrene and the like, usually using anhydrous AlCl3 or acid catalysts such as activated clay and the like, and filtering and distilling the product under reduced pressure to obtain a finished product of the liquid alkyl diphenylamine. However, the quality of the liquid alkyl diphenylamine product is greatly changed under the influence of conditions such as raw material purity, catalysts, process parameters and the like, and particularly, the color of the liquid alkyl diphenylamine is deepened due to the oxidation of diphenylamine in the reaction process and the residual discoloration in the product, and meanwhile, the quality of the liquid alkyl diphenylamine is reduced, the irritation and the carcinogenicity of the liquid alkyl diphenylamine to the skin are increased, and the storage stability is also influenced. Therefore, the synthesis of liquid alkyldiphenylamines has been of great interest for a long time.
Specifically, US2943112 discloses the preparation of octyl/butyl diphenylamine mixtures by the catalytic reaction of diisobutylene with diphenylamine in the presence of sulfuric acid and activated clay as catalysts; US3496230 discloses the preparation of a liquid nonylated diphenylamine mixture by catalytic reaction of nonenes with diphenylamine in the presence of AlCl3 as catalyst; US3714257 discloses the preparation of liquid octyl/butyl diphenylamine or nonylated diphenylamine mixtures by catalytic reaction of diisobutylene or nonene with diphenylamine in the presence of AlCl3 as catalyst; US4163757 discloses the preparation of liquid styrenated diphenylamine mixtures by the catalytic reaction of styrene with diphenylamine using sulfuric acid impregnated natural montmorillonite as a catalyst; US4704219 discloses a process for the preparation of liquid alkylated diphenylamines substituted with butyl and octyl groups in the para-position and ethyl groups in the ortho-position, by using AlCl3 as a catalyst, first adding ethylene and HCl gas for reaction, and then adding diisobutylene for reaction; JPH2188555 discloses a liquid nonylated diphenylamine mixture obtained by reacting propylene trimer with diphenylamine in the presence of activated clay as a catalyst; EP149422 discloses a solid-liquid two-phase reaction of diphenylamine and diisobutylene with activated clay as a catalyst to obtain an octyl/butyl diphenylamine mixture; CN101353445A discloses a method for preparing a liquid styrenated diphenylamine mixture by catalytic reaction of styrene and diphenylamine in the presence of activated clay as a catalyst; CN1288000A discloses a method for preparing liquid octylated diphenylamine mixture by catalytic reaction of diisobutylene and diphenylamine as raw materials in a high-pressure kettle at 170-180 ℃ and 0.30-0.50MPa, activated clay as a catalyst and hydroquinone as a polymerization inhibitor; CN101538208A discloses that activated clay is used as a catalyst, alpha-methylstyrene and diphenylamine are used as raw materials to carry out catalytic reaction, the obtained reaction solution is distilled at high temperature of 200-250 ℃ under reduced pressure to obtain a solid particle antioxidant of a mixture of 4- (A, A-dimethylbenzyl) diphenylamine and 4,4' -bis (A, A-dimethylbenzyl) diphenylamine, and the product is gradually changed into gray after being exposed in the air; CN102320983A discloses a method for preparing a liquid octylated diphenylamine mixture by catalytic reaction of diisobutylene and diphenylamine as raw materials in a high-pressure kettle by using activated clay as a catalyst; CN102659606A discloses that an alkylated diphenylamine solid antioxidant product with stable color is obtained by taking activated clay as a catalyst, reacting diphenylamine with an alkylating agent and then adding a color retention-color reduction agent. The supported heteropolyacid is used for catalytic synthesis of alkyl diphenylamine, Zhang Long, Song Wei, Jiang Dan bud, Xuxu Xueli, etc., the petrochemical industry, No. 2 of volume 35 in 2006, page 141-144 discloses that the supported heteropolyacid is used as catalyst, and alpha-C14 olefine and diphenylamine are used as raw materials to catalytically synthesize long-chain alkyl diphenylamine. A common disadvantage of these disclosed techniques is that the quality, yield and/or production cost of the product is unsatisfactory. For example, anhydrous AlCl3, when used as a catalyst, tends to retain elemental chlorine, resulting in a dark brown color and also risks corrosion of equipment; the catalytic activity of the activated clay is not high, and the product is too average and is only suitable for low-quality alkylated diphenylamine antioxidant without requirements on the positions and the number of substituents; although the amount of heteropoly acid is small, the reaction temperature is high, the catalyst has no decolorizing function, the product color is dark, and the like.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for synthesizing a liquid alkyl diphenylamine antioxidant, in particular to nonyl diphenylamine (antioxidant L67) and octyl/butyl diphenylamine (antioxidant L57), which can efficiently synthesize the liquid alkyl diphenylamine antioxidant and is suitable for industrial production of the liquid alkyl diphenylamine antioxidant.
The invention provides a method for synthesizing a liquid alkyl diphenylamine antioxidant, which comprises the following steps:
1)AlCl3-SnCl2preparation of a bicomponent supported catalyst: soaking an activated catalyst carrier in an acid solution, then sequentially and thoroughly cleaning the catalyst carrier with water and an alcohol solvent, drying the catalyst carrier, adding the catalyst carrier into an organic solvent, then adding anhydrous aluminum trichloride and anhydrous stannous chloride, heating the mixture for a period of time, filtering the mixture, collecting solids, carrying out heat treatment at the temperature of 200-400 ℃, grinding the solids to the particle size of 40-100 meshes to obtain AlCl3-SnCl2A bicomponent supported catalyst;
2) preparing a liquid alkyl diphenylamine antioxidant: diphenylamine, olefin and AlCl3-SnCl2The bi-component supported catalyst and the polymerization inhibitor are placed in a high-pressure reaction kettle and heated to 180 ℃ for reaction under the protection of nitrogen, and the liquid alkyl diphenylamine antioxidant is obtained.
In a preferred embodiment of the invention, the catalyst support is selected from at least one of montmorillonite, bentonite, sepiolite, hydroxyapatite, preferably sepiolite. The activation comprises calcining the catalyst support at 600-1000 ℃, preferably 650-850 ℃, more preferably 700-800 ℃.
In a preferred embodiment of the present invention, the acidic solution is selected from at least one of a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, a phosphoric acid solution; the mass concentration of the acid is 1 to 30%, preferably 5 to 20%, more preferably 10 to 15%. The alcohol solvent is selected from at least one of absolute methanol and absolute ethanol, and the alcohol solvent is used for washing and drying the catalyst carrier soaked in the acidic solvent, so that the removal of water in the catalyst carrier is facilitated, and the influence on the diphenylamine alkylation reaction is avoided.
The catalyst carrier is rich in hydroxyl groups by activating the catalyst carrier and impregnating the catalyst carrier with an acidic solution, and is easy to combine with aluminum trichloride and stannous chloride, so that the loading capacity and the combination strength are improved, and the catalyst can be conveniently recycled and can keep the catalytic activity under the condition of repeated use.
In a preferred embodiment of the present invention, the organic solvent is preferably selected to have a solubility for aluminum trichloride and stannous chloride, more preferably at least one selected from carbon tetrachloride, chloroform, toluene, and most preferably carbon tetrachloride. In the case of carbon tetrachloride, the AlCl of the invention3-SnCl2The bi-component supported catalyst has the best catalytic activity.
In a preferred embodiment of the present invention, the heating means heating to 60 to 120 ℃, preferably to the reflux temperature of the organic solvent.
In a preferred embodiment of the invention, the loading of aluminum trichloride and stannous chloride on the catalyst support is from 5 to 40 wt.%, preferably from 10 to 35 wt.%, more preferably from 20 to 30 wt.%. The loading amount is calculated based on the mass of the catalyst support. In a preferred embodiment of the invention, the loading mass ratio of the aluminum trichloride to the stannous chloride on the catalyst carrier is 1: 0.15-0.5, preferably 1: 0.2 to 0.4, more preferably 1: 0.3-0.35.
In a preferred embodiment of the present invention, the heat treatment is preferably carried out at 230-350 ℃, more preferably at 280-300 ℃; the milling is preferably to a particle size of 60-80 mesh.
AlCl prepared by the above method of the present invention3-SnCl2The bi-component supported catalyst has high catalyst loading and bonding strength, can be conveniently recycled, and can maintain the catalytic activity under the condition of multiple use.
In a preferred embodiment of the invention, the olefins include nonene and diisobutylene and the liquid alkyl diphenylamine antioxidants include nonyl diphenylamine (antioxidant L67) and octyl/butyl diphenylamine (antioxidant L57).
In a preferred embodiment of the invention, the polymerization inhibitor comprises a hydrogenated cardanol-based polymerization inhibitor, in particular 5-pentadecyl-2- (((4- (phenylamino) phenyl) amino) methyl) phenol. Through screening of a large amount of polymerization inhibitor, the invention finds that the polymerization inhibitor is particularly suitable for the production of the liquid alkyl diphenylamine antioxidant, and compared with hydroquinone and the like which are conventionally used, the polymerization inhibitor can effectively reduce the generation of reaction impurities and improve the quality of products.
In a preferred embodiment of the present invention, the diphenylamine and the olefin are used in a molar ratio of 1: 2-6, preferably 1: 2.5-5, more preferably 1: 3.5-4. The AlCl3-SnCl2The amount of the two-component supported catalyst is 5-20%, preferably 7-15%, more preferably 8-10% of the mass of diphenylamine. The amount of the polymerization inhibitor to be used is 10 to 200ppm, preferably 20 to 60ppm based on the mass of the starting system.
In a preferred embodiment of the invention, it is preferred to add a portion of the olefin and then make up the remainder of the olefin as the reaction proceeds. Preferably, the olefin is initially charged in an amount of 30 to 70%, preferably 40 to 60%, more preferably 50 to 55% of the total olefin. Preferably, the make-up of olefin is carried out in two portions, each with half of the remainder of the olefin added.
In a preferred embodiment of the present invention, the reaction system is preferably heated to 60 to 90 ℃ to melt the diphenylamine, and then the stirring is started. Preferably, it is possible to heat to 65 to 85 ℃ and more preferably 70 to 80 ℃.
In a preferred embodiment of the present invention, the reaction is preferably carried out at 160-170 ℃.
In a preferred embodiment of the present invention, the reaction pressure is controlled to be initially 0.3 to 0.5 MPa. Preferably, make-up of the balance of olefin begins when the pressure drops to 40% -60% of the initial value.
In a preferred embodiment of the present invention, the supported catalyst in the reaction solution is separated after the completion of the reaction, preferably by filtration, centrifugation or the like. Preferably, the separated and collected catalyst can be recycled. After the supported catalyst is separated, unreacted olefin and a small amount of unreacted diphenylamine are removed, preferably by distillation under reduced pressure and rectification.
Has the advantages that:
the method of the invention canProduction of liquid alkyldiphenylamine antioxidants, especially nonyldiphenylamine (antioxidant L67) and octyl/butyldiphenylamine (antioxidant L57), from AlCl3-SnCl2The bi-component supported catalyst can efficiently catalyze the reaction, the diphenylamine conversion rate is high, the residual quantity is small, the selectivity of dinonyl diphenylamine is high, and the antioxidant activity of the obtained liquid alkyl diphenylamine antioxidant is superior to that of the antioxidant obtained by the method in the prior art. This indicates AlCl3-SnCl2The double-component supported catalyst has the synergistic effect. In addition, the AlCl of the invention3-SnCl2The bi-component supported catalyst is easy to separate from a reaction system and can be recycled, and the economical efficiency and the environmental protection are very outstanding. The invention also finds that the hydrogenated cardanol-based polymerization inhibitor 5-pentadecyl-2- (((4- (phenylamino) phenyl) amino) methyl) phenol is particularly suitable for the production of the liquid alkyl diphenylamine antioxidant, can effectively reduce the generation of reaction impurities, and improves the quality of products. In a word, the synthetic method of the invention can produce the high-quality liquid alkyl diphenylamine antioxidant, has high economical efficiency and environmental protection, and is suitable for being applied to industrial production.
Detailed Description
Hereinafter, preferred examples of the invention will be described in detail. The examples are given for the purpose of better understanding the inventive content and are not intended to be limiting. Insubstantial modifications and adaptations of the embodiments in accordance with the present disclosure remain within the scope of the invention.
Preparation example 1: AlCl3-SnCl2Preparation of bicomponent supported catalyst
Sepiolite was calcined in a muffle furnace at 700 ℃ for 6h for activation. And soaking the activated sepiolite in a 10% sulfuric acid solution for 24h, then centrifuging to separate solid particles, sequentially and thoroughly cleaning with water and absolute ethyl alcohol, and drying in vacuum for 4h to obtain the catalyst carrier. Taking 20g of the catalyst carrier, adding 250mL of carbon tetrachloride, then adding 6.0g of anhydrous aluminum trichloride and 2.0g of anhydrous stannous chloride, and stirring for 2h under reflux. Filtering, washing with carbon tetrachloride for 3 times, vacuum drying at 75 deg.C for 10 hr, and placing in muffle furnaceCalcining at 280 ℃ for 3h to prepare AlCl3-SnCl2A bicomponent supported catalyst. The loading was 25.6% (calculated on the basis of sepiolite) using atomic absorption spectroscopy, where the mass ratio of aluminium trichloride to stannous chloride was 1: 0.31. the obtained catalyst is ground for 15min at the speed of 500r/min until the particle size is 60-80 meshes for later use.
Preparation example 2: AlCl3-SnCl2Preparation of bicomponent supported catalyst
Sepiolite was calcined in a muffle furnace at 700 ℃ for 6h for activation. And soaking the activated sepiolite in a 15% sulfuric acid solution for 24h, then centrifuging to separate solid particles, sequentially and thoroughly cleaning the solid particles by using water and absolute ethyl alcohol, and drying the solid particles for 4h in vacuum to obtain the catalyst carrier. Taking 20g of the catalyst carrier, adding 250mL of carbon tetrachloride, then adding 7.5g of anhydrous aluminum trichloride and 2.5g of anhydrous stannous chloride, and stirring for 2h under reflux. Filtering, washing with carbon tetrachloride for 3 times, vacuum drying at 75 deg.C for 10 hr, and calcining at 280 deg.C in muffle furnace for 3 hr to obtain AlCl3-SnCl2A bicomponent supported catalyst. The loading was 29.4% (calculated on the basis of sepiolite) using atomic absorption spectroscopy, where the mass ratio of aluminium trichloride to stannous chloride was 1: 0.32. the obtained catalyst is ground for 15min at the speed of 500r/min until the particle size is 60-80 meshes for later use.
Comparative preparation example 1: AlCl3Preparation of single-component supported catalyst
Sepiolite was calcined in a muffle furnace at 700 ℃ for 6h for activation. And soaking the activated sepiolite in a 10% sulfuric acid solution for 24h, then centrifuging to separate solid particles, sequentially and thoroughly cleaning with water and absolute ethyl alcohol, and drying in vacuum for 4h to obtain the catalyst carrier. 20g of the catalyst carrier is taken, 250mL of carbon tetrachloride is added, 7.5g of anhydrous aluminum trichloride is added, and stirring is carried out for 2 hours under reflux. Filtering, washing with carbon tetrachloride for 3 times, vacuum drying at 75 deg.C for 10 hr, and calcining at 280 deg.C in muffle furnace for 3 hr to obtain AlCl3Single component supported catalysts. The loading was found to be 26.3% (calculated on the basis of sepiolite) using atomic absorption spectroscopy. Will obtainThe catalyst is ground for 15min at the speed of 500r/min until the particle size is 60-80 meshes for later use.
Comparative preparation example 2: SnCl2Preparation of single-component supported catalyst
Sepiolite was calcined in a muffle furnace at 700 ℃ for 6h for activation. And soaking the activated sepiolite in a 10% sulfuric acid solution for 24h, then centrifuging to separate solid particles, sequentially and thoroughly cleaning with water and absolute ethyl alcohol, and drying in vacuum for 4h to obtain the catalyst carrier. Taking 20g of the catalyst carrier, adding 250mL of carbon tetrachloride, then adding 8.0g of anhydrous stannous chloride, and stirring for 2h under reflux. Filtering, washing with carbon tetrachloride for 3 times, vacuum drying at 75 deg.C for 10 hr, and calcining at 280 deg.C for 3 hr in muffle furnace to obtain SnCl2Single component supported catalysts. The loading was determined to be 22.6% using atomic absorption spectroscopy (calculated on the basis of sepiolite). The obtained catalyst is ground for 15min at the speed of 500r/min until the particle size is 60-80 meshes for later use.
Example 1: synthesis of nonyl diphenylamine (antioxidant L67)
169.0 g of diphenylamine and 252.5 g of nonene were charged into a high-pressure reactor, 15g of the catalyst of preparation example 1, 50ppm of 5-pentadecyl-2- (((4- (phenylamino) phenyl) amino) methyl) phenol as a hydrogenated cardanol-based polymerization inhibitor, the gas in the system was replaced with nitrogen several times, the reactor was closed, heated to 80 ℃ to melt diphenylamine, stirred, and further heated to 170 ℃ to effect a reaction under a reaction pressure of 0.4 MPa. The pressure in the reaction kettle gradually decreases along with the reaction, 126.2g of nonene is supplemented for continuous reaction for 2 hours when the reaction pressure decreases to 0.2MPa, and then 126.2g of nonene is supplemented again for continuous reaction for 4 hours. Then stopping the reaction, and filtering and recovering the AlCl by using a fiber filter membrane3-SnCl2The two-component supported catalyst was subjected to liquid phase sampling analysis of the components, and subjected to reduced pressure distillation at 170 ℃ under a residual pressure of 10mmHg to distill off unreacted nonene and a small amount of diphenylamine, to obtain 410.2g of a translucent pale yellow liquid nonyldiphenylamine mixed product, which was sampled to analyze the composition. The gas chromatographic analysis shows that the obtained nonylated diphenylamine product contains: dinonyl diphenylamine 93.1% by weight5.2 percent by weight of mono-nonyl diphenylamine, 0.9 percent by weight of tri-nonyl diphenylamine, 0.15 percent by weight of diphenylamine; wherein, the content of 4,4' -dinonyl diphenylamine is 89.3 percent by weight. It was calculated that the conversion of diphenylamine (ratio of sum of moles of mono-, di-, and trisnonyldiphenylamines to the initial diphenylamine) was 98.5%, the selectivity of dinonyldiphenylamine (ratio of sum of moles of dinonyldiphenylamine to sum of moles of mono-, di-, and trisnonyldiphenylamines) was 91.9%, and the selectivity of 4,4 '-dinonyldiphenylamine (ratio of sum of moles of 4,4' -dinonyldiphenylamine to sum of moles of mono-, di-, and trisnonyldiphenylamines) was 90.7%.
Example 2 and comparative examples 1 to 5 were carried out according to the procedure of example 1.
Example 2: the catalyst of example 1 was replaced by the same mass of the catalyst of preparation 2.
Comparative example 1: the catalyst of example 1 was replaced by the same mass of the catalyst of comparative preparation 1.
Comparative example 2: the catalyst of example 1 was replaced by the same mass of the catalyst of comparative preparation 2.
Comparative example 3: 4g of anhydrous aluminum trichloride were used instead of the catalyst in example 1.
Comparative example 4: the catalyst in example 1 was replaced with 3g of anhydrous aluminum trichloride and 1g of anhydrous stannous chloride.
Comparative example 5: the hydrogenated cardanol-based polymerization inhibitor in example 1 was replaced with hydroquinone at the same concentration.
The products of each example and comparative example were analyzed and the results are shown in table 1 below.
TABLE 1
From the above results, it can be seen that the use of AlCl according to the present invention3-SnCl2The preparation method of the bi-component supported catalyst can realize high diphenylamine conversion rate and has high selectivity of dinonyl diphenylamine, particularly 4,4' -dinonyl diphenylamine. Since dinonyl diphenylamine is particularlyIs a better antioxidant property of 4,4' -dinonyldiphenylamine, so that the nonyl diphenylamine obtained apparently has better properties. Furthermore, the use of AlCl according to the invention3-SnCl2The preparation method of the dual-component supported catalyst not only has low diphenylamine residue, but also can obtain the product with light color, high transparency and uniform viscosity>6 months) was not discolored even when stored, and the durability was good.
In contrast to the preparation process according to the invention, if AlCl is not used3-SnCl2Bi-component supported catalysts, but using AlCl3One-component supported catalyst (comparative example 2) it can be seen that the diphenylamine conversion and dinonyldiphenylamine selectivity of the reaction are reduced to varying degrees at substantially the same loading. Moreover, the resulting nonyl diphenylamine mixture was light brown and slightly cloudy in terms of product quality. And if SnCl is used2The one-component supported catalyst (comparative example 2) has low diphenylamine conversion rate due to the low catalytic activity of stannous chloride itself, and even though the converted diphenylamine, which is a major monononylated product, is poor in dinonyldiphenylamine selectivity, the reaction is not industrially and commercially valuable. From the results, it can be seen that AlCl is used in the present invention3-SnCl2The technical effect of improving diphenylamine conversion rate and dinonyl diphenylamine selectivity brought by the dual-component supported catalyst is not only that AlCl is improved3Single-component supported catalyst and SnCl2The simple superposition of the respective effects of the single-component supported catalyst is a synergistic result.
While the anhydrous aluminum trichloride conventionally used in the prior art (comparative example 3) has high diphenylamine conversion and high dinonyl diphenylamine selectivity by using the catalyst, the selectivity of dinonyl diphenylamine is different from that of the invention. In addition, due to the inherent defects of easy dechlorination and the like of the anhydrous aluminum trichloride, the chlorine content in the product is higher, the impurities are more, the color and luster of the product are poor, and the quality of the product is lower. And also has a problem of corrosion of the reaction vessel in the case of long-term use.In addition, if only the anhydrous aluminum trichloride powder and the anhydrous tin dichloride powder were used together (comparative example 4), no synergistic effect as in the present invention was observed, and it is presumed that AlCl is used3-SnCl2The combination and interrelation of aluminum trichloride and tin dichloride in the two-component supported catalyst is different from that in the powder state, resulting in distinct results in the two cases.
In the case of using hydroquinone as a polymerization inhibitor (comparative example 5), although the diphenylamine conversion and dinonyldiphenylamine selectivity of the reaction were acceptable, since the polymerization inhibitor was not sufficiently suitable, impurities in the product were large, the product was darker in color, insufficient in transparency, and turned into dark brown after 6 months of storage, as compared with example 1. This indicates that the product is of poor quality and durability.
Effect example 1: evaluation of antioxidant Properties of alkylated diphenylamines.
The 100SN neutral oil is used as base oil, and 0.5 mass percent of the nonyl diphenylamine antioxidant synthesized in each example/comparative example is added to be prepared into oil products. The oxidation induction period of the formulated oil was measured by the rotary oxygen bomb method (ASTM D-2272), and the results are shown in Table 2.
TABLE 2
| Sources of nonyl diphenylamines | Oxidation induction period (min) |
| Example 1 | 120 |
| Example 2 | 118 |
| Comparative example 1 | 105 |
| Comparative example 3 | 101 |
| Comparative example 4 | 98 |
| Comparative example 5 | 115 |
The above results indicate that the nonyl diphenylamine antioxidant prepared according to the method of the present invention has very excellent antioxidant properties, while nonyl diphenylamine antioxidants prepared by other methods have poor antioxidant properties.
Example 3: catalyst cycle test
The catalyst obtained by filtration in example 1 was recycled 6 times without additional activation, and the results are shown in table 3 below.
TABLE 3
The above results show that after repeated use, the AlCl of the present invention3-SnCl2The bi-component supported catalyst still has better catalytic activity, and the conversion rate of diphenylamine and the selectivity of dinonyl diphenylamine in the reaction are reduced to a certain extent, but the reduction degree is not obvious.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. A method for synthesizing a liquid alkyl diphenylamine antioxidant, comprising:
1) preparation of AlCl3-SnCl2 bi-component supported catalyst: soaking an activated catalyst carrier in an acid solution, then sequentially and thoroughly cleaning the activated catalyst carrier by using water and an alcohol solvent, drying the activated catalyst carrier, adding the activated catalyst carrier into an organic solvent, then adding anhydrous aluminum trichloride and anhydrous stannous chloride, heating the mixture for a period of time, filtering the mixture, collecting solids, carrying out heat treatment at the temperature of 200-400 ℃, and grinding the solids to the particle size of 40-100 meshes to obtain an AlCl3-SnCl2 bi-component supported catalyst;
2) preparing a liquid alkyl diphenylamine antioxidant: diphenylamine, olefin, AlCl3-SnCl2 bi-component supported catalyst and polymerization inhibitor are placed in a high-pressure reaction kettle, and are heated to 150-180 ℃ for reaction under the protection of nitrogen, so that the liquid alkyl diphenylamine antioxidant is obtained.
2. The synthesis method according to claim 1, wherein the catalyst carrier is selected from at least one of montmorillonite, bentonite, sepiolite and hydroxyapatite; the activation comprises calcining the catalyst support at 600-1000 ℃, preferably 650-850 ℃, more preferably 700-800 ℃; the acid solution is at least one selected from hydrochloric acid solution, sulfuric acid solution, nitric acid solution and phosphoric acid solution; the mass concentration of the acid is 1-30%, preferably 5-20%, more preferably 10-15%; the organic solvent is at least one of carbon tetrachloride, chloroform and toluene.
3. The synthesis process according to claim 1, wherein the loading of aluminum trichloride and stannous chloride on the catalyst support is 5-40 wt%, preferably 10-35 wt%, more preferably 20-30 wt%; the loading mass ratio of the aluminum trichloride to the stannous chloride on the catalyst carrier is 1: 0.15-0.5, preferably 1: 0.2 to 0.4, more preferably 1: 0.3-0.35.
4. The method of synthesis of claim 1, wherein the olefins comprise nonene and diisobutylene and the liquid alkyl diphenylamine antioxidants comprise nonyldiphenylamine (antioxidant L67) and octyl/butyl diphenylamine (antioxidant L57).
5. A synthesis process according to claim 1, characterized in that the polymerization inhibitor comprises a hydrogenated cardanol-based polymerization inhibitor, in particular 5-pentadecyl-2- (((4- (phenylamino) phenyl) amino) methyl) phenol.
6. The synthesis method according to claim 1, wherein the molar ratio of the diphenylamine and the olefin is 1: 2-6, preferably 1: 2.5-5, more preferably 1: 3.5-4; the using amount of the AlCl3-SnCl2 bi-component supported catalyst is 5-20%, preferably 7-15%, and more preferably 8-10% of the mass of diphenylamine; the amount of the polymerization inhibitor to be used is 10 to 200ppm, preferably 20 to 60ppm based on the starting system.
7. The synthesis method according to claim 1, characterized in that a part of the olefin is added first, and then the rest of the olefin is added as the reaction proceeds; the olefin is added first in an amount of 30 to 70%, preferably 40 to 60%, more preferably 50 to 55% based on the total olefin amount.
8. The synthesis method according to claim 7, characterized in that the reaction pressure is controlled at initial 0.3-0.5 MPa; make up balance olefin is started when the pressure drops to 40% -60% of the initial value.
9. The synthesis method according to claim 1, wherein the supported catalyst in the reaction solution is separated after the reaction is completed, and the separated and collected catalyst can be recycled.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320914A (en) * | 2011-06-08 | 2012-01-18 | 南京工业大学 | Environmentally-friendly method for producing adamantine |
| CN102584601A (en) * | 2012-01-05 | 2012-07-18 | 常州大学 | Preparation method of alkylated diphenylamine antioxidant product |
| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of HAP (hydroxyapatite)-supported aluminum trichloride catalyst |
| CN103739422A (en) * | 2014-01-27 | 2014-04-23 | 锦州康泰润滑油添加剂股份有限公司 | Preparation method of dialkyl benzene |
| CN105732400A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method for (para, para)-diisopropylphenyl diphenylamine product |
-
2021
- 2021-03-08 CN CN202110252410.5A patent/CN113004150B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320914A (en) * | 2011-06-08 | 2012-01-18 | 南京工业大学 | Environmentally-friendly method for producing adamantine |
| CN102584601A (en) * | 2012-01-05 | 2012-07-18 | 常州大学 | Preparation method of alkylated diphenylamine antioxidant product |
| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of HAP (hydroxyapatite)-supported aluminum trichloride catalyst |
| CN103739422A (en) * | 2014-01-27 | 2014-04-23 | 锦州康泰润滑油添加剂股份有限公司 | Preparation method of dialkyl benzene |
| CN105732400A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method for (para, para)-diisopropylphenyl diphenylamine product |
Non-Patent Citations (3)
| Title |
|---|
| MICHAL SKLENA´R等: "Discontinuous alkylation of diphenylamine with nonene for maximum catalyst utilization", 《CHEM.PAP.》 * |
| 李博仑 等: "抗氧剂壬基二苯胺的合成及其热稳定性", 《合成化学》 * |
| 郭伟杰: "液体烷基化二苯胺抗氧剂的合成", 《江苏科技大学学报》 * |
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