CN105777552A - Preparation method of solid alkylated diphenylamine - Google Patents
Preparation method of solid alkylated diphenylamine Download PDFInfo
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- CN105777552A CN105777552A CN201410815360.7A CN201410815360A CN105777552A CN 105777552 A CN105777552 A CN 105777552A CN 201410815360 A CN201410815360 A CN 201410815360A CN 105777552 A CN105777552 A CN 105777552A
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Abstract
The present invention discloses a preparation method of solid alkylated diphenylamine. The method comprises the steps of: under the action of solid Lewis acid catalysis and bleaching earth discoloration, mixing olefin with diphenylamine, carrying out an alkylation reaction at 80-200 DEG C and under certain pressure until the content of diphenylamine is less than 1%; filtering, and distilling to remove a catalyst and the olefin; recrystallizing the product by using a polar organic solvent. The product obtained by the method is a white powder, has base number greater than 120, and the remaining diphenylamine content less than 1%. The method has no wastewater emissions, and is environmentally friendly.
Description
Technical field
The present invention relates to a kind of solid alkylation diphenylamines preparation method.
Background technology
Alkylated diphenylamine antioxidant has excellent antioxygenic property and higher heat stability, good oil-soluble and the ashless feature such as without phosphorus, it is widely used in I. C. engine oil, industrial gear oil, change speed gear box wet goods, solid alkylation diphenylamines product is compared with liquid alkyl diphenylamines product, non-oxidizability is higher, thermal weight loss temperature is higher, is more widely applied in harsh environment.
Solid alkylation diphenylamines customary preparation methods is as follows: with diphenylamines for raw material, under lewis acid or bronsted acid catalyst catalysis, by preparing crude product with the alkylated reaction of alkene, after through series of process steps such as distillation, recrystallization, finally obtain product.
US5672752B1 discloses a kind of preparation technology preparing fluidization alkylation aniline, this method can obtain mono-substituted alkyl diphenylamine by clay catalyst, can also obtain the monoalkylated product of a lot of needs simultaneously, and the unwanted product of small part and diphenylamines.
US5520848 describes by using the aluminosilicate of activation to be alkylated, and natural layered silicate is after acid activation, it is possible to promote carbonium ion reaction, thus being alkylated, but catalysis activity will lower than tradition lewis acid catalysts such as aluminum chloride.
The preparation method that US4824601 discloses a kind of fluidization alkyl diphenylamine, this experiment is by clay catalyst in acid activation of diphenylamines and polyisobutylene, react under being not less than the temperature conditions of 160 DEG C, material molar ratio scope 1:1.1～1:2.5, when being reacted to bis-alkylated product and catalyst quality sum less than total reactant quality 25% always, stopped reaction, the product at this moment obtained is exactly the alkyl diphenylamine of fluidization.
CN1882651A discloses a kind of method preparing octylated diphenylamine, this antioxidant composition comprises the dioctyl diphenylamine of 65%-98 weight %, the at most trioctylphosphine diphenylamines of 1.5% weight, the at most diphenylamines of 1% weight, can by being alkylated prepared with diisobutylene in the presence of a catalyst to diphenylamines.
CN102276480A discloses a kind of preparation method preparing high-purity solid alkylated diphenylamine, belong to technical field of fine, the preparation method relating to antioxidant for lubricant oil, under 80～230 DEG C and 0.2～0.5MPa, make alkene and diphenlyamine reaction, when in reaction, diphenylamine content is less than 0.5%, stopped reaction also collects product, through washing, neutralize, hot wash, polar solvent is adopted to carry out recrystallization, obtaining the solid alkylation diphenylamines product of purity more than 97%, adopt acidic resin catalyst systems, product is grizzled particle.
The preparation method that CN102584601A discloses a kind of alkylated diphenylamine antioxidant product; belong to synthetic material and technical field of lubricating oil; FS-2 catalyst, diphenylamines, polymerization inhibitor, organic solvent are proportionally added in synthesis reaction vessel; good nitrogen protection; drip α-methyl styrene at the reaction temperatures; insulation reaction, reaction obtains alkylated diphenylamine mixed liquor after terminating；Isolated by filtration catalyst, filtrate is through recrystallization.Filter, washing, dry obtain antioxidant product of the present invention.Having free H ion and chloride ion in the method catalyst, cause product jaundice or blackout, this is the color that post processing cannot be removed.
This patent catalyst is through acid activation mixture after bleaching earth and Γ-aluminium oxide mixing, does not have free H ion and chloride ion in catalyst, and prepared product is pure white solid powder.
Summary of the invention
The invention provides a kind of solid alkylation diphenylamines preparation method, by adding catalyst and a certain amount of bleaching earth, control reaction condition, obtaining product is white powder, and base number is more than 120, and residue diphenylamine content is less than 1%.
The invention aims to provide a kind of solid alkylation diphenylamines preparation method, the method is compared to current preparation method, by using bleaching earth and polymerization inhibitor, it is possible to be effectively improved product colour and improve alkene utilization rate, improving product performance, alkene, catalyst can be recycled.
The preparation method that the present invention provides a kind of solid alkylation diphenylamines, it is characterised in that comprise the following steps:
A, diphenylamines is mixed with alkene 1:3.5～1:8.0 in molar ratio, add catalyst and polymerization inhibitor that solid Lewis acid is mixed with bleaching earth, and in 80 DEG C～200 DEG C, normal pressure to 0.5MPa, be alkylated reaction, until reactant in diphenylamine content less than 1% time stopped reaction；
B, reactant mixture is cooled to 80 DEG C-100 DEG C after, filter, decompression distillation；
C, product polar organic solvent in step b is carried out recrystallization, obtain alkylated diphenylamine powder.
Wherein, with the weight of diphenylamines for 100%, described solid Lewis acid catalyst levels is 15%-40%, and described bleaching earth consumption is 10%～25%；Described polymerization inhibitor consumption is 100ppm～220ppm.
Described bleaching earth is that commercially available bleaching earth obtains after 100 DEG C of baking oven heats 1～2 hour.
Described alkene is Diisobutylene, octene, tripropylene or nonene.
Described solid Lewis acid catalyst is at least one in the group selecting free aluminium oxide, boron fluoride, silicate to form.
With diphenylamines mole for 100%, described alkene consumption is 350%～800%.
The temperature of described decompression distillation is 100 DEG C～130 DEG C, and pressure is 0.06MPa～0.09MPa, and the time is 1.5～2 hours.
Described polymerization inhibitor is di-tert-butyl hydroquinone, meta-dinitro-benzent, beta-naphthylamine or 8-quinolin-2-ylamine.
Described polar organic solvent is petroleum ether and the mixture of ethyl acetate, ethanol, butanol, dioxane or ether.
The present invention can also details are as follows:
The method include that a carbon 8, carbon 9 alkene mix with diphenylamines, under the effect of catalyst and bleaching earth, at 80 DEG C～200 DEG C, be alkylated reaction.
Diphenylamines and alkene can add by 1:3.5～1:8.0 in molar ratio.
Catalyst is and activity solid lewis acid, and with the weight of diphenylamines for 100%, catalyst amount is 15-40%.
Bleaching earth adopts physical method to process, commercially available bleaching earth and alumina mixture elder generation acid activation, and deionization is washed without after free H ion, and 100 DEG C of heating can use after 1～2 hour in an oven, and bleaching earth addition is the 10%～25% of diphenylamines quality.
In reaction, polymerization inhibitor can stop alkene autohemagglutination, alkene large usage quantity in reaction, and therefore polymerization inhibitor can play very important effect.
Polymerization inhibitor addition is 100～220ppm.
Reaction temperature is 80 DEG C～200 DEG C, and normal pressure carries out to 0.5MPa.
Response time is 0.5～20 hour.
When in reactant diphenylamine content less than 1% till, stopped reaction.
Mixture is filtered after suitably cooling down, and decompression boils off alkene, adds polar organic solvent and carries out recrystallization,
Finally giving dialkyl diphenylamine product, product appearance is white powder, and base number is more than 120, and diphenylamine content is less than 1%.
The present invention relates to and prepare solid alkylation diphenylamines by the extra method adding bleaching earth, compared to existing technique, it is not necessary to techniques such as washing, neutralizations, product is fine white powder, and product base number increases, and residue diphenylamine content reduces, and three-waste free discharge problem, be conducive to environmental protection.
Can carrying out structure elucidation after the separated purification of product, data are shown in accompanying drawing 1, accompanying drawing 2.
Below in conjunction with embodiment, the present invention is described in detail.
Accompanying drawing explanation
Fig. 1 is the nmr spectrum of the product prepared by the present invention.
Fig. 2 is the gas chromatogram of the product prepared by the present invention.
Detailed description of the invention
Embodiment 1
Bleaching earth is that commercially available bleaching earth obtains after 100 DEG C of baking oven heats 1 hour, it is being furnished with agitator, thermometer, add hot jacket, reflux condensing tube, water knockout drum, the 1000ml glass container of nitrogen pipeline adds diphenylamines 101.4g and 67.2gC8 alkene and 10.0g bleaching earth and 20.4 silicate catalysts, pass into nitrogen protection, it is stirred with magnetic stirring apparatus, after all melting in 80 DEG C, gradually rise temperature to 165 DEG C, 201.6gC8 alkene is added at 5～10 hours, control back-flow velocity and heating-up temperature, temperature of charge is made to be not less than 140 DEG C, response time is 20 hours.It is reacted to DPA according to TLC tracking substantially to disappear, suitably cools down and alkene is distilled off in 80 DEG C of filtrations, decompression, after ethyl alcohol recrystallization, obtaining final products, reclaim alkene and catalyst, product is white powder, data from gas chromatography display diphenylamine content 0.5%, base number 124.
Embodiment 2
Bleaching earth is that commercially available bleaching earth obtains after 100 DEG C of baking oven heats 2 hours, it is being furnished with agitator, thermometer, add hot jacket, reflux condensing tube, water knockout drum, the 1000ml glass container of nitrogen pipeline adds diphenylamines 101.4g and 75.6gC9 alkene and 10.0g bleaching earth and 15.8g activated alumina catalyst, pass into nitrogen protection, it is stirred with magnetic stirring apparatus, after all melting in 80 DEG C, gradually rise temperature to 165 DEG C, 378.2gC9 alkene is added at 8～12 hours, control back-flow velocity and heating-up temperature, temperature of charge is made to be not less than 140 DEG C, response time is 20 hours.It is reacted to DPA according to TLC tracking substantially to disappear, suitably cools down and alkene is distilled off in 80 DEG C of filtrations, decompression, by petroleum ether, re-crystallizing in ethyl acetate, obtaining final products, reclaim alkene and catalyst, product is white powder, data from gas chromatography display diphenylamine content 0.8%, base number 122.
Claims (9)
1. the preparation method of a solid alkylation diphenylamines, it is characterised in that comprise the following steps:
A, diphenylamines is mixed with alkene 1:3.5～1:8.0 in molar ratio, add catalyst and polymerization inhibitor that solid Lewis acid is mixed with bleaching earth, and in 80 DEG C～200 DEG C, normal pressure to 0.5MPa, be alkylated reaction, until reactant in diphenylamine content less than 1% time stopped reaction；
B, reactant mixture is cooled to 80 DEG C-100 DEG C after, filter, decompression distillation；
C, product polar organic solvent in step b is carried out recrystallization, obtain alkylated diphenylamine powder.
2. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that: with the weight of diphenylamines for 100%, described solid Lewis acid catalyst levels is 15%-40%, and described bleaching earth consumption is 10%～25%；Described polymerization inhibitor consumption is 100ppm～220ppm.
3. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that: described bleaching earth is that commercially available bleaching earth obtains after 100 DEG C of baking oven heats 1～2 hour.
4. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that: described alkene is Diisobutylene, octene, tripropylene or nonene.
5. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that: described solid Lewis acid catalyst is at least one in the group selecting free aluminium oxide, boron fluoride, silicate to form.
6. the preparation method of the solid alkylation diphenylamines according to claim 1 or 4, it is characterised in that: with diphenylamines mole for 100%, described alkene consumption is 350%～800%.
7. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that: the temperature of described decompression distillation is 100 DEG C～130 DEG C, and pressure is 0.06MPa～0.09MPa, and the time is 1.5～2 hours.
8. the preparation method of solid alkylation diphenylamines according to claim 1 and 2, it is characterised in that: described polymerization inhibitor is di-tert-butyl hydroquinone, meta-dinitro-benzent, beta-naphthylamine or 8-quinolin-2-ylamine.
9. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that: described polar organic solvent is petroleum ether and the mixture of ethyl acetate, ethanol, butanol, dioxane or ether.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107522623A (en) * | 2017-08-31 | 2017-12-29 | 苏振东 | A kind of preparation method of diphenylamine rubber age inhibitor |
| CN115254088A (en) * | 2022-08-30 | 2022-11-01 | 华东理工大学 | Catalyst for producing alkyl diphenylamine and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276480A (en) * | 2010-06-08 | 2011-12-14 | 中国石油化工集团公司 | Preparation method of high-purity solid alkylated diphenylamine |
| CN102584601B (en) * | 2012-01-05 | 2014-02-05 | 常州大学 | Preparation method of alkylated diphenylamine antioxidant product |
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- 2014-12-23 CN CN201410815360.7A patent/CN105777552B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276480A (en) * | 2010-06-08 | 2011-12-14 | 中国石油化工集团公司 | Preparation method of high-purity solid alkylated diphenylamine |
| CN102584601B (en) * | 2012-01-05 | 2014-02-05 | 常州大学 | Preparation method of alkylated diphenylamine antioxidant product |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107522623A (en) * | 2017-08-31 | 2017-12-29 | 苏振东 | A kind of preparation method of diphenylamine rubber age inhibitor |
| CN115254088A (en) * | 2022-08-30 | 2022-11-01 | 华东理工大学 | Catalyst for producing alkyl diphenylamine and preparation method and application thereof |
| CN115254088B (en) * | 2022-08-30 | 2023-11-21 | 华东理工大学 | Catalyst for producing alkyl diphenylamine and preparation method and application thereof |
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| CN105777552B (en) | 2018-10-16 |
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