CN101745423B - Catalyst and diphenylamine alkylation method - Google Patents
Catalyst and diphenylamine alkylation method Download PDFInfo
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- CN101745423B CN101745423B CN2008102278285A CN200810227828A CN101745423B CN 101745423 B CN101745423 B CN 101745423B CN 2008102278285 A CN2008102278285 A CN 2008102278285A CN 200810227828 A CN200810227828 A CN 200810227828A CN 101745423 B CN101745423 B CN 101745423B
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Abstract
The invention provides a method for preparing a catalyst. The method comprises the steps of allowing aqueous solution of acid in a concentration of less than 20 percent by weight to be in contact with activated clay, dehydrating and drying the obtained product. The invention also provides a diphenylamine alkylation method, which comprises the steps of subjecting diphenylamine and diisobutylene to contact reaction under alkylation conditions in the presence of the catalyst in an inert gas atmosphere, wherein the catalyst is obtained by the method provided by the invention. According to the method provided by the invention, the catalyst is low in consumption, and increases the yield of final products compared with the prior art. In addition, the catalyst is good in reusability, can be directly used after the catalyst is removed from the final products, and can be repeatedly reused.
Description
Technical field
The present invention relates to the alkylation of a kind of catalyst and diphenylamines.
Background technology
Chemical reaction in use and can take place and oxidation deterioration after airborne oxygen and metal surface contact in mineral oil and artificial oil, generates acidic materials, causes the corrosion of machinery equipment.In order to delay the oxidizing process of oil product, improve serviceability, usually effective method is in oil product, to add anti-oxidant.
Alkylating diphenylamines is a kind of octyl group and the substituted amine type of butyl mixed alkyl antioxidant; Its characteristics are that oil-soluble is good, good with the functional additive compatibility of other type, use still has good antioxidant effect under higher temperature conditions, and especially the effect with the compound use of phenolic ester type antioxidant is more outstanding.Simultaneously; The quality upgrading of lubricating oil more and more requires lubricating oil to have lower phosphorus content, means and will still less use phosphorus-containing antioxidant zinc dialkyl dithiophosphate (ZDDP); Therefore non-phosphorus antioxidant is favored gradually, and this also is the development trend of oil formula technical research.This type of alkylating diphenylamines product has obtained extensive use in high-quality internal combustion engine oil product at present, and it can be controlled oil viscosity effectively and increase and reduce sedimental generation.In addition, the application of alkylating diphenylamines in industrial lubricant also has good effect, like greases such as steam turbine oil, compressor oil, antiwear hydraulic oil, lubricating grease.The general effective dose of this antioxidant in engine oil is 0.3-1.0 weight %, and the effective dose in industrial lubricant is 0.1-0.5 weight %.
At present, had a lot of methods to be used for preparing alkylating diphenylamines both at home and abroad, normally adopted different catalyst to carry out alkylated reaction, catalyst commonly used comprises AlCl
3, heteropoly acid and atlapulgite.
AlCl
3Be the catalyst that is used for preparing alkylating diphenylamines that adopts the earliest; Adopt this catalyst can produce HCl gas usually, and generally contain two more substitution products in the resulting product, and residual the chlorine element arranged; This product that obtains is a dark brown; Especially color is darker for the substituted product of diisobutylene, and this product is solid-state or paste at normal temperatures, is unfavorable for the mediation in oil product.
Heteropoly acid is the catalyst of latest development, and consumption is few during alkylated reaction, but reaction temperature is higher, the catalyst function of not decolouring, and product colour is darker, and simultaneously, unreacted diphenylamines content is higher, generally greater than 3%.
Therefore; In alkylated reaction, using at present maximum is activated bauxite catalyst; General catalyst amount is 10-20 weight %, diisobutylene is had cracking function preferably, like this in alkylating diphenylamines product; The ratio of various products has good distribution, can make product have good mobility.
US4824601 discloses a kind of method for preparing liquid antioxidant composition of reacting through diphenylamines and diisobutylene; This method is included in activated bauxite catalyst and exists down; Reaction temperature at least 160 ℃ under; With diphenylamines and diisobutylene molar ratio reaction with 1: 1.1 to 1: 2.5, this reaction proceed to 4,4 '-two uncle's octyl diphenylamine content in the final reaction mass except that catalyst be lower than 25% and the content of diphenylamines accomplish when being lower than 10 weight %.And explain that this atlapulgite is preferably
22B that is purchased from LaporteIndustries.This method is carried out under normal pressure, requires reaction temperature higher more than at least 160 ℃, because the diisobutylene boiling point is 102 ℃; Be liquid at normal temperatures, and diphenylamines is solid-state, diisobutylene one gets into reaction system and gasifies immediately, refluxes; The reactant contact is insufficient; Cause the reaction time long, the product color is darker, is dark-brown.On the other hand, the reaction speed of this reaction is along with reaction reduces gradually, when the rate of addition of diisobutylene during greater than reaction speed capacity of returns increase, make reaction temperature be lower than the control point; And when rate of addition during less than reaction speed, temperature sharply rises again, causes temperature fluctuation excessive, and it is steady that operating process is difficult to reach.
CN1288000A discloses a kind of preparation method of liquid alkylated diphenylamines; This method comprises, in the presence of activated bauxite catalyst, under 170-230 ℃ the temperature and under the pressure of 0.2-0.5MPa; Make diisobutylene and diphenylamines haptoreaction; In product 4, the content of 4-two uncle's octyl diphenylamines stopped reaction and collected product less than 20% o'clock.This method is compared with above-mentioned patent US4824601, and the reaction time has shortened 4-5 hour, has solved the unstable problem of temperature fluctuation in the course of reaction that causes owing to the diisobutylene backflow simultaneously.And the lighter color of alkylating diphenylamines, for light yellow.But the catalyst use amount is more in this method, nearly about 20 weight % of diphenylamines consumption.Because catalyst consumption is more, when removing catalyst, can carry more product, therefore reduced the output of end product.And the repeat performance of this catalyst is relatively poor, and when reusing one time, the content of residual diphenylamines is just up to more than the 5 weight % in the product.
Summary of the invention
The objective of the invention is to overcome the catalyst amount that exists in the above-mentioned prior art more with the relatively poor defective of repeat performance catalyst, the repeat performance that the less and catalyst of a kind of catalyst amount is provided is the alkylation of Preparation of catalysts method and diphenylamines preferably.
The invention provides a kind of Preparation of catalysts method, this method comprises, is that aqueous acid below the 20 weight % contacts with atlapulgite with concentration, and dehydration, drying; The temperature of said contact is 20-80 ℃, and the time of contact is 2-7 hour.
The present invention also provides a kind of alkylation of diphenylamines; This method comprises, under alkylation conditions and in the presence of the catalyst, in inert gas atmosphere, with diphenylamines and diisobutylene haptoreaction; Wherein, said catalyst makes for adopting Preparation of catalysts method of the present invention.
According to the alkylation of Preparation of catalysts method provided by the invention and diphenylamines, catalyst consumption is less, when removing catalyst, only can carry a spot of product, therefore compared with prior art, has improved the output of end product.And; The repeat performance of this catalyst is fine; Can directly use after from end product, removing, and when reusing repeatedly, the content of residual diphenylamines still can be controlled in the 4 weight % in the product; And the catalyst of prior art is when repeating one time, and residual diphenylamines content promptly surpasses 4 weight % in the product.
The specific embodiment
The term " atlapulgite " that this paper uses is to well known to a person skilled in the art term, is to be that the clay of silica and aluminium oxide obtains after with acid treatment with main component, is also referred to as Emathlite.Be mainly used in the decolorizing and refining of lubricating oil and animal and plant fat, the decolouring of petroleum distillate or dehydration and solvent refining etc.The common employed method for preparing atlapulgite does in this area; Solvent and solute weight ratio with greater than 1.5 is immersed in clay in the concentrated acid (general acid strength is more than 30%); The temperature of soaking is 80-120 ℃, and the time of immersion is 12-24 hour, make then water repeatedly wash pH to cleaning solution near neutrality till; Oven dry is ground then, and sieving obtains finished product.
The term " equi-volume impregnating " that this paper uses is to well known to a person skilled in the art term, at first measures the saturation capacity (that is, up to carrier surface to be impregnated just till the complete wetting) of carrier adsorbed water to be impregnated, converses the volume of adsorbed water; The liquid to be impregnated of the volume equal volume of the water that obtains with converting therewith then floods this carrier to be impregnated.
It is that aqueous acid below the 20 weight % contacts with atlapulgite that Preparation of catalysts method provided by the invention comprises concentration, and dehydration, drying; The temperature of said contact is 20-80 ℃, and the time of contact is 2-7 hour.
According to preparation method provided by the invention, under preferable case, said aqueous acid adopts equi-volume impregnating to carry out with contacting of atlapulgite.
According to preparation method provided by the invention, under preferable case, the concentration of said acid is lower than 20 weight %, is preferably 1-12 weight %, more preferably 1-10 weight %.And said acid can be for well known to a person skilled in the art various acid, for example water-soluble inorganic acid and/or p-methyl benzenesulfonic acid.Wherein water-soluble inorganic acid can be selected from one or more in sulfuric acid, phosphoric acid, hydrochloric acid, phosphotungstic acid and the phosphomolybdic acid.The acid of being selected for use is preferably one or more in sulfuric acid, phosphoric acid, hydrochloric acid and the p-methyl benzenesulfonic acid.
According to preparation method provided by the invention, under preferable case, the temperature of said dipping is 20-80 ℃, can adopt the mode of water-bath heating usually, and the time of dipping is 2-7 hour.
The alkylation of diphenylamines provided by the invention comprises; Under alkylation conditions and in the presence of the catalyst, in inert gas atmosphere; With diphenylamines and diisobutylene haptoreaction, wherein, said catalyst makes for adopting Preparation of catalysts method provided by the invention.
According to alkylation provided by the invention, inert gas can adopt the various inert gases that well known to a person skilled in the art, preferably uses in nitrogen, helium and the argon gas one or more.
According to alkylation provided by the invention, under preferable case, said catalyst consumption is the 1-10 weight % of diphenylamines weight, 2-8 weight % more preferably.
According to alkylation provided by the invention, under preferable case, this method comprises that also the content that proceeds to residual diphenylamines in the reaction gained mixture when said reaction stops this reaction and collecting reaction product when being lower than 4 weight %.
According to alkylation provided by the invention, under preferable case, said reaction condition comprises, reaction pressure is above, the preferred 0.2-0.5MPa of 0.15MPa, and reaction temperature is more than 140 ℃, preferred 150-250 ℃, more preferably 155-220 ℃.
According to alkylation provided by the invention, under preferable case, the mol ratio of diphenylamines and diisobutylene is 1: 1-2, more preferably 1: 1.1-1.9.
According to alkylation provided by the invention, under preferable case, can diisobutylene once or several times be added in the diphenylamines, preferably adopt to add the diisobutylene method in batches, reacting balance is carried out.For example can divide and add diisobutylene 2-5 time, preferably divide 2-3 time.Under the preferable case, the amount of the diisobutylene that adds for the first time is the 50-70 weight % of diisobutylene total amount.
According to alkylation provided by the invention, under normal conditions, after finishing, reaction needs unreacted diisobutylene is steamed, and the performance of the diisobutylene that steams is unaffected, can get back in the system to reuse.And the resulting product of filtering reaction is with the catalyst in the system of removing while hot, obtains the mixture of flaxen liquid alkylated diphenylamines thus.
In the process after above-mentioned reaction finishes, can take to filter the method for afterwards distilling earlier, also can take to distill earlier the method for afterwards filtering.For the color that makes resulting end product can not deepen, vapo(u)rizing temperature is usually less than 150 ℃.
Mixture according to the alkylating diphenylamines of the resulting end product of method provided by the invention has following structural formula:
R
1And R
2The tert-butyl group or iso-octyl be can be, and the ortho position or the contraposition of imino group on the phenyl ring are positioned at.
The mixture of the alkylating diphenylamines that method of the present invention makes has good oil-soluble ability and antioxygenic property.Can with the composite use of different additives, and have better effect after the composite use; Also can be widely used in I. C. engine oil and the industrial lubricant simultaneously, additive capacity is generally 0.01-1.0 weight %.
To adopt the mode of embodiment that the present invention is described in further detail below.
Embodiment 1
1, Preparation of catalysts
Adopting equi-volume impregnating that atlapulgite (Yi County, Jinzhou oil carclazyte Co., Ltd product) is immersed in temperature, to remain on 20 ℃, concentration be in the sulfuric acid of 2 weight %, flood 2 hours, and dephlegmate then 100 ℃ of dryings 2 hours down, obtains catalyst.
2, the preparation of alkylating diphenylamines
In the autoclave of 250ml, add 50.7 gram diphenylamines, 60.5 gram diisobutylene, the above-mentioned catalyst for preparing of 2 grams, with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed that when temperature reaches 100 ℃, begins with 200 rev/mins stirs.Pick up counting during at heat temperature raising to 170 ℃, reaction system pressure for 0.30MPa; After reaction was carried out 10 hours, along with the carrying out of reaction, pressure was reduced to 0.17MPa gradually; Record residual diphenylamines content with gas chromatography and be lower than 4 weight %, finish reaction this moment.With material cooling and be transferred in the there-necked flask of 250ml,, remove unreacted diisobutylene raw material and low amounts of water decompression distillation under 140 ℃ the temperature, under the residual voltage of 60mmHg 20 minutes.Then temperature of charge is reduced to 120 ℃, remove by filter catalyst waste slag.Obtain the faint yellow liquid thickness product of 86.9 grams.The content of residual diphenylamines is 1.029 weight % in the gas chromatographic analysis product.
Embodiment 2
1, Preparation of catalysts
Adopting equi-volume impregnating that atlapulgite (Yi County, Jinzhou oil carclazyte Co., Ltd product) is immersed in temperature, to remain on 30 ℃, concentration be in the sulfuric acid of 4 weight %, flood 3 hours, and dephlegmate then 120 ℃ of dryings 3 hours down, obtains catalyst.
2, the preparation of alkylating diphenylamines
In the autoclave of 250ml, add 50.7 gram diphenylamines, 67.2 gram diisobutylene, the above-mentioned catalyst for preparing of 3 grams, with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed that when temperature reaches 100 ℃, begins with 200 rev/mins stirs.Pick up counting during at heat temperature raising to 170 ℃, reaction system pressure for 0.38MPa; After reaction was carried out 12 hours, along with the carrying out of reaction, pressure was reduced to 0.15MPa gradually; Record residual diphenylamines content with gas chromatography and be lower than 4 weight %, finish reaction this moment.With material cooling and be transferred in the there-necked flask of 250ml,, remove unreacted diisobutylene raw material and low amounts of water decompression distillation under 140 ℃ the temperature, under the residual voltage of 60mmHg 20 minutes.Then temperature of charge is reduced to 120 ℃, remove by filter catalyst waste slag.Obtain the faint yellow liquid thickness product of 88.2 grams.The content of residual diphenylamines is 0.655 weight % in the gas chromatographic analysis product.
Embodiment 3
1, Preparation of catalysts
Adopting equi-volume impregnating that atlapulgite (Yi County, Jinzhou oil carclazyte Co., Ltd product) is immersed in temperature, to remain on 40 ℃, concentration be in the phosphoric acid of 5 weight %, flood 4 hours, and dephlegmate then 130 ℃ of dryings 4 hours down, obtains catalyst.
2, the preparation of alkylating diphenylamines
In the stainless autoclave of 250ml, add 50.7 gram diphenylamines, 39 gram diisobutylene, the above-mentioned catalyst for preparing of 1 gram, with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed that when temperature reaches 100 ℃, starts with 200 rev/mins stirs.Pick up counting during for 0.30MPa at heat temperature raising to 180 ℃, reaction system pressure, after reaction was carried out 2 hours, reaction pressure was reduced to 0.18MPa gradually; The diisobutylene that adds 12.8 grams keeps 180 ℃ temperature to continue reaction, after reaction is carried out 4 hours; Add 12 gram diisobutylene again, keep 180 ℃ temperature to continue reaction, after reaction is carried out 7 hours; Record residual diphenylamines content with gas chromatography and be lower than 4 weight %, finish reaction this moment.With material cooling and be transferred in the there-necked flask of 250ml,, remove unreacted diisobutylene raw material and low amounts of water decompression distillation under 150 ℃ the temperature, under the residual voltage of 60mmHg 20 minutes.Then temperature of charge is reduced to 120 ℃, remove by filter catalyst waste slag.Obtain the faint yellow liquid thickness product of 89.6 grams.The content of residual diphenylamines is 0.358 weight % in the gas chromatographic analysis product.
Embodiment 4
1, Preparation of catalysts
Adopting equi-volume impregnating that atlapulgite (Yi County, Jinzhou oil carclazyte Co., Ltd product) is immersed in temperature, to remain on 50 ℃, concentration be in the hydrochloric acid of 6 weight %, flood 5 hours, and dephlegmate then 150 ℃ of dryings 5 hours down, obtains catalyst.
2, the preparation of alkylating diphenylamines
In the stainless autoclave of 250ml, add 50.7 gram diphenylamines, 39 gram diisobutylene, the above-mentioned catalyst for preparing of 2 grams, with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed with 200 rev/mins when temperature reaches 100 ℃ stirs.Pick up counting during for 0.30MPa at heat temperature raising to 180 ℃, reaction system pressure, after reaction was carried out 2 hours, reaction pressure was reduced to 0.18MPa gradually; The diisobutylene that adds 12.8 grams keeps 180 ℃ temperature to continue reaction, after reaction is carried out 4 hours; Add 12 gram diisobutylene again, keep 180 ℃ temperature to continue reaction, after reaction is carried out 7 hours; Record residual diphenylamines content with gas chromatography and be lower than 4 weight %, finish reaction this moment.With material cooling and be transferred in the there-necked flask of 250ml,, remove unreacted diisobutylene raw material and low amounts of water decompression distillation under 150 ℃ the temperature, under the residual voltage of 60mmHg 20 minutes.Then temperature of charge is reduced to 100 ℃, remove by filter catalyst waste slag.Obtain the faint yellow liquid thickness product of 87.6 grams.The content of residual diphenylamines is 0.635 weight % in the gas chromatographic analysis product.
Embodiment 5
1, Preparation of catalysts
Adopting equi-volume impregnating that atlapulgite (Yi County, Jinzhou oil carclazyte Co., Ltd product) is immersed in temperature, to remain on 60 ℃, concentration be in the p-methyl benzenesulfonic acid of 8 weight %; Flooded 6 hours; Dephlegmate descended dry 6 hours at 160 ℃ then, obtained catalyst.
2, the preparation of alkylating diphenylamines
In the 250ml stainless steel autoclave, add 50.7 gram diphenylamines, 44 gram diisobutylene, the above-mentioned catalyst for preparing of 4 grams, with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed with 150 rev/mins when temperature reaches 100 ℃ stirs.Pick up counting during at heat temperature raising to 180 ℃, reaction system pressure for 0.40MPa; React after 6 hours, reaction pressure is reduced to 0.20MPa gradually, adds the diisobutylene of 23 grams again; Keep 180 ℃ temperature to continue reaction; After reaction is carried out 5 hours, record residual diphenylamines content with gas chromatography and be lower than 4 weight %, finish reaction this moment.With material cooling and filter, with under residual voltage, carrying out decompression distillation in filtrate filtered transferred product to the there-necked flask, remove unreacted diisobutylene and low amounts of water under 150 ℃ the temperature, at 60mmHg, obtain the faint yellow liquid thickness product of 88.5 grams.The content of residual diphenylamines is 0.292 weight % in the gas chromatographic analysis product.
Embodiment 6
1, Preparation of catalysts
Adopting equi-volume impregnating that atlapulgite (Yi County, Jinzhou oil carclazyte Co., Ltd product) is immersed in temperature, to remain on 80 ℃, concentration be in the phosphotungstic acid of 10 weight %; Flooded 7 hours; Dephlegmate descended dry 8 hours at 190 ℃ then, obtained catalyst.
2, the preparation of alkylating diphenylamines
In the stainless autoclave of 250ml, add 50.7 gram diphenylamines, 39 gram diisobutylene, the above-mentioned catalyst for preparing of 2 grams, with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed with 200 rev/mins when temperature reaches 100 ℃ stirs.Pick up counting during at heat temperature raising to 180 ℃, reaction system pressure, after reaction is carried out 2 hours, when reaction pressure is reduced to 0.18MPa gradually for 0.30MPa; The diisobutylene that adds 12.8 grams keeps 180 ℃ temperature to continue reaction, after reaction is carried out 4 hours; Add 12 gram diisobutylene again, keep 180 ℃ temperature to continue reaction, react after 7 hours; Record residual diphenylamines content with gas chromatography and be lower than 4 weight %, finish reaction this moment.With material cooling and be transferred in the there-necked flask of 250ml,, remove unreacted diisobutylene raw material and low amounts of water decompression distillation under 150 ℃ the temperature, under the residual voltage of 60mmHg 20 minutes.Temperature of charge is reduced to 140 ℃, remove by filter catalyst waste slag.Obtain the faint yellow liquid thickness product of 87.8 grams.The content of residual diphenylamines is 0.929 weight % in the gas chromatographic analysis product.
Comparative Examples 1
Method according to embodiment 1 prepares alkylating diphenylamines, and different is that the Preparation of catalysts method is following:
Adopting equi-volume impregnating that atlapulgite (Yi County, Jinzhou oil carclazyte Co., Ltd product) is immersed in temperature, to remain on 20 ℃, concentration be in the sulfuric acid of 25 weight %, flood 2 hours, and dephlegmate then 100 ℃ of dryings 2 hours down, obtains catalyst.
The amount of the alkylating diphenylamines that finally obtains is 82.1 grams.The content of residual diphenylamines is 13.237 weight % in the gas chromatographic analysis product.
In this Comparative Examples, the concentration of the acid of dipping atlapulgite surpasses 20 weight %, and the content of residual diphenylamines is very high in the product at this moment.
Comparative Examples 2
In the stainless autoclave of 250ml, add 50.7 gram diphenylamines, 39 gram diisobutylene, 2 gram atlapulgite (Yi County, Jinzhou oil carclazyte Co., Ltd products?) catalyst, with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed with 200 rev/mins when temperature reaches 100 ℃ stirs.Pick up counting during at heat temperature raising to 180 ℃, reacting system pressure, after reaction is carried out 2 hours, when reaction pressure is reduced to 0.18MPa gradually for 0.30MPa; The diisobutylene that adds 12.8 grams keeps 180 ℃ temperature to continue reaction, after reaction is carried out 4 hours; Add 12 gram diisobutylene again; Keep 180 ℃ temperature to continue reaction, reacted 7 hours, finish reaction.With cooled materials and be transferred in the there-necked flask of 250ml,, remove unreacted diisobutylene raw material and low amounts of water decompression distillation under 150 ℃ the temperature, under the residual voltage of 60mmHg 20 minutes.Then temperature of charge is reduced to 120 ℃, remove by filter catalyst waste slag.Obtain the faint yellow liquid thickness product of 84 grams.The content that uses gas chromatography to record residual diphenylamines is 6.569 weight %.
The amount of the existing catalyst that in this Comparative Examples, uses is identical with embodiment's 6, and the content of residual diphenylamines is very high in the product.
Comparative Examples 3
In the stainless autoclave of 250ml, add 50.7 gram diphenylamines, 39 gram diisobutylene, 10 gram atlapulgite (Yi County, Jinzhou oil carclazyte Co., Ltd product) catalyst, with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed with 200 rev/mins when temperature reaches 100 ℃ stirs.Pick up counting during at heat temperature raising to 180 ℃, reacting system pressure, after reaction is carried out 2 hours, when reaction pressure is reduced to 0.18MPa gradually for 0.30MPa; The diisobutylene that adds 12.8 grams keeps 180 ℃ temperature to continue reaction, after reaction is carried out 4 hours; Add 12 gram diisobutylene again; Keep 180 ℃ temperature to continue reaction, reacted 7 hours, finish reaction.With cooled materials and be transferred in the there-necked flask of 250ml,, remove unreacted diisobutylene raw material and low amounts of water decompression distillation under 150 ℃ the temperature, under the residual voltage of 60mmHg 20 minutes.Then temperature of charge is reduced to 120 ℃, remove by filter catalyst waste slag.Obtain the faint yellow liquid thickness product of 86.6 grams.The content that uses gas chromatography to record residual diphenylamines is 2.213 weight %.
The amount of employed existing catalyst is 20 weight % of diphenylamines in this Comparative Examples, and the content of residual diphenylamines is below the 4 weight % in the product at this moment, but still than the height among each embodiment.
Comparative Examples 4
Active soil (employed
22B from Laporte Industries among the US4824601 embodiment) catalyst that in the stainless autoclave of 250ml, adds 50.7 gram diphenylamines, 39 gram diisobutylene, 2 gram acid activations is with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed with 200 rev/mins when temperature reaches 100 ℃ stirs.Pick up counting during at heat temperature raising to 180 ℃, reacting system pressure, after reaction is carried out 2 hours, when reaction pressure is reduced to 0.18MPa gradually for 0.30MPa; The diisobutylene that adds 12.8 grams keeps 180 ℃ temperature to continue reaction, after reaction is carried out 4 hours; Add 12 gram diisobutylene again; Keep 180 ℃ temperature to continue reaction, reacted 7 hours, finish reaction.With cooled materials and be transferred in the there-necked flask of 250ml,, remove unreacted diisobutylene raw material and low amounts of water decompression distillation under 150 ℃ the temperature, under the residual voltage of 60mmHg 20 minutes.Then temperature of charge is reduced to 120 ℃, remove by filter catalyst waste slag.Obtain the faint yellow liquid thickness product of 87.3 grams.The content that uses gas chromatography to record residual diphenylamines is 4.869 weight %.
The amount of the existing catalyst that uses in this Comparative Examples is identical with embodiment's 6, and the content of residual diphenylamines is higher in the product at this moment.
Comparative Examples 5
Active soil (employed
22B from Laporte Industries among the US4824601 embodiment) catalyst that in the stainless autoclave of 250ml, adds 50.7 gram diphenylamines, 39 gram diisobutylene, 10 gram acid activations is with nitrogen replacement reaction system three times.Begin to heat up, the rotating speed with 200 rev/mins when temperature reaches 100 ℃ stirs.Pick up counting during at heat temperature raising to 180 ℃, reacting system pressure, after reaction is carried out 2 hours, when reaction pressure is reduced to 0.18MPa gradually for 0.30MPa; The diisobutylene that adds 12.8 grams keeps 180 ℃ temperature to continue reaction, after reaction is carried out 4 hours; Add 12 gram diisobutylene again; Keep 180 ℃ temperature to continue reaction, reacted 7 hours, finish reaction.With cooled materials and be transferred in the there-necked flask of 250ml,, remove unreacted diisobutylene raw material and low amounts of water decompression distillation under 150 ℃ the temperature, under the residual voltage of 60mmHg 20 minutes.Then temperature of charge is reduced to 120 ℃, remove by filter catalyst waste slag.Obtain the faint yellow liquid thickness product of 83.6 grams.The content that uses gas chromatography to record residual diphenylamines is 0.832 weight %.
The amount of employed existing catalyst is 20 weight % of diphenylamines in this Comparative Examples,, close in this moment product among content and the embodiment 6 of residual diphenylamines.
Performance test
1, the repeat performance of catalyst
Respectively the catalyst among the foregoing description 1-6 and the Comparative Examples 1-5 is repeated the process 5 times of the alkylating diphenylamines of above-mentioned preparation, and measure the content that each course of reaction finishes the residual diphenylamines in back through gas chromatography.Gained is the result be shown in Table 1.
Table 1
The result shows, adopts method catalyst of the present invention to be repeatedly used, and catalyst consumption seldom catalytic effect is also fine.
2, the antioxygenic property of alkylating diphenylamines
Adopt rotary oxygen bomb method (ASTM D-2272) that the instance product is carried out oxidation test, measure oil oxidation induction period, induction period is long more, and antioxygenic property is good more.Base oil is selected the 150SN neutral oil of Dalian Petrochemical Industry Company for use, the alkylating diphenylamines for preparing among each embodiment of adding 0.5%.Result of the test is seen table 2.
Table 2
| Additive | Dosage/% | Oxidation induction period/min |
| Embodiment 1 | 0.5 | 107 |
| Embodiment 2 | 0.5 | 103 |
| Embodiment 3 | 0.5 | 102 |
| Embodiment 4 | 0.5 | 102 |
| Embodiment 5 | 0.5 | 104 |
| Embodiment 6 | 0.5 | 103 |
| Comparative Examples 1 | 0.5 | 105 |
| Comparative Examples 2 | 0.5 | 109 |
| Comparative Examples 3 | 0.5 | 104 |
| Comparative Examples 4 | 0.5 | 106 |
| Comparative Examples 5 | 0.5 | 101 |
The result shows, the antioxygenic property of the prepared alkylating diphenylamines of method provided by the invention and of the prior art suitable.
In sum, the preparation method of alkylating diphenylamines of the present invention compared with prior art, on the basis that obtains suitable antioxygenic property; Reduced catalyst consumption; Reduced pollution, and catalyst can be repeatedly used, improve the economy of preparation environment.
Claims (12)
1. a Preparation of catalysts method is characterized in that, it is that aqueous acid below the 20 weight % contacts with atlapulgite that this method comprises concentration, and dehydration, drying; The temperature of said contact is 20-80 ℃, and the time of contact is 2-7 hour.
2. preparation method according to claim 1, wherein, said aqueous acid adopts equi-volume impregnating to carry out with contacting of atlapulgite.
3. preparation method according to claim 1 and 2, wherein, the concentration of said acid is 1-12 weight %, and said acid is selected from water-soluble inorganic acid and/or p-methyl benzenesulfonic acid.
4. the alkylation of a diphenylamines; This alkylation comprises; Under alkylation conditions and in the presence of the catalyst, in inert gas atmosphere; With diphenylamines and diisobutylene haptoreaction, it is characterized in that said catalyst is for adopting any catalyst that described preparation method makes among the claim 1-3.
5. alkylation according to claim 4, wherein, said catalyst consumption is the 1-10 weight % of diphenylamines weight.
6. alkylation according to claim 5, wherein, said catalyst consumption is the 2-8 weight % of diphenylamines weight.
7. alkylation according to claim 4, wherein, this method comprises that also the content that proceeds to diphenylamines in the reaction gained mixture when said reaction stops this reaction and collecting reaction product when being lower than 4 weight %.
8. alkylation according to claim 4, wherein, said reaction condition comprises that reaction pressure is more than the 0.15MPa, reaction temperature is more than 140 ℃.
9. alkylation according to claim 8, wherein, said reaction pressure is 0.2-0.5MPa, said reaction temperature is 150-250 ℃.
10. alkylation according to claim 4, wherein, the mol ratio of diphenylamines and diisobutylene is 1: 1-2.
11. alkylation according to claim 4, wherein, join diisobutylene in the diphenylamines said diphenylamines and the catalytic mode of diisobutylene are comprised in batches.
12. alkylation according to claim 11, wherein, the amount of the diisobutylene that adds for the first time is the 50-70 weight % of diisobutylene total amount.
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| CN102371174B (en) * | 2010-08-12 | 2014-05-28 | 中国石油化工股份有限公司 | Diphenylamine alkylation catalyst and preparation method thereof |
| CN102531920A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Method for preparing dinonyl diphenylamine |
| CN102321498B (en) * | 2011-06-24 | 2013-06-05 | 锦州惠发天合化学有限公司 | Preparation method for high-base-number calcium alkylsalicylate detergent |
| CN106944142B (en) * | 2017-03-22 | 2019-08-16 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of composite catalyst and nonyl diphenylamine |
| CN113045429A (en) * | 2019-12-27 | 2021-06-29 | 中国石油天然气股份有限公司 | Method for simultaneously preparing antioxidant of butyl octyl diphenylamine and dioctyl diphenylamine and obtained product |
| CN112718006B (en) * | 2021-02-19 | 2022-06-10 | 宜昌兴春化工有限公司 | Catalyst for producing diisooctyl diphenylamine antioxidant and preparation method thereof |
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| US4824601A (en) * | 1983-12-08 | 1989-04-25 | Ciba-Geigy-Corporation | Liquid antioxidant produced by alkylating diphenylamine with a molar excess of diisobutylene |
| CN1288000A (en) * | 1999-09-10 | 2001-03-21 | 中国石油化工集团公司 | Method for preparing liquid alkyl diphenylamine |
| CN1504445A (en) * | 2002-11-29 | 2004-06-16 | 中国石油天然气股份有限公司 | Novel process for preparing alkyl phenol |
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| US4824601A (en) * | 1983-12-08 | 1989-04-25 | Ciba-Geigy-Corporation | Liquid antioxidant produced by alkylating diphenylamine with a molar excess of diisobutylene |
| CN1288000A (en) * | 1999-09-10 | 2001-03-21 | 中国石油化工集团公司 | Method for preparing liquid alkyl diphenylamine |
| CN1504445A (en) * | 2002-11-29 | 2004-06-16 | 中国石油天然气股份有限公司 | Novel process for preparing alkyl phenol |
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