CN105777552B - The preparation method of solid alkylation diphenylamines - Google Patents
The preparation method of solid alkylation diphenylamines Download PDFInfo
- Publication number
- CN105777552B CN105777552B CN201410815360.7A CN201410815360A CN105777552B CN 105777552 B CN105777552 B CN 105777552B CN 201410815360 A CN201410815360 A CN 201410815360A CN 105777552 B CN105777552 B CN 105777552B
- Authority
- CN
- China
- Prior art keywords
- diphenylamines
- preparation
- solid
- alkene
- solid alkylation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of solid alkylation diphenylamines preparation methods, wherein the method includes under the action of solid Lewis acid catalysis and bleaching earth decoloration, alkene is mixed with diphenylamines, at 80 DEG C~200 DEG C and it is alkylated reaction under certain pressure, stop reaction when being less than 1% to diphenylamine content, filtering, after catalyst and alkene is distilled off, head product is recrystallized using polar organic solvent, products therefrom is white powder by this method, base number is more than 120, remaining diphenylamine content is less than 1%, no waste water and gas discharge, it is good for the environment.
Description
Technical field
The present invention relates to a kind of solid alkylation diphenylamines preparation methods.
Background technology
Alkylated diphenylamine antioxidant has excellent antioxygenic property and higher thermal stability, good oil-soluble
And the features such as ashless without phosphorus, it is widely used in I. C. engine oil, industrial gear oil, gear box oil etc., solid alkylation diphenylamines
For product compared with liquid alkyl diphenylamines product, inoxidizability is stronger, and thermal weight loss temperature higher is applied in harsh environment
More extensively.
Solid alkylation diphenylamines customary preparation methods are as follows：Using diphenylamines as raw material, urged in lewis acid or Bronsted acid
Under agent catalysis, by the way that crude product is made with the alkylated reaction of alkene, after walked by the series of process such as distilling, recrystallizing
Suddenly, product is finally obtained.
US 5672752B1 disclose a kind of preparation process preparing fluidization alkylation aniline, and this method can pass through
Clay catalyst obtains mono-substituted alkyl diphenylamine, while can also obtain the monoalkylated product much needed, and few portion
Divide unwanted product and diphenylamines.
US 5520848 is described to be alkylated by using the alumino-silicate of activation, and natural layered silicate is through peracid
After activation, carbonium ion can be promoted to react, to be alkylated, but catalytic activity will be less than traditional Louis such as aluminium chloride
Acid catalyst.
US 4824601 discloses a kind of preparation method of fluidization alkyl diphenylamine, this experiment is by diphenylamines and gathers different
Butylene is reacted in the clay catalyst of acid activation under the temperature condition not less than 160 DEG C, material molar ratio range 1:1.1~
1:2.5, when being reacted to the sum of bis-alkylated product and catalyst quality always less than total reactant quality 25%, stop reaction,
At this moment the product obtained is exactly the alkyl diphenylamine of fluidization.
CN 1882651A disclose a kind of method preparing octylated diphenylamine, which includes 65%-98
The dioctyl diphenylamine of weight %, the trioctylphosphine diphenylamines of at most 1.5% weight, the at most diphenylamines of 1% weight, can by
With diisobutylene diphenylamines is alkylated in the presence of catalyst obtained.
CN 102276480A disclose a kind of preparation method preparing high-purity solid alkylated diphenylamine, belong to fine
Chemical technology field is related to the preparation method of antioxidant for lubricant oil, under 80~230 DEG C and 0.2~0.5MPa, makes alkene and two
Aniline reaction stops reacting and collecting product when diphenylamine content is less than 0.5% in reaction, by washing, neutralizes, hot water
Washing, is recrystallized using polar solvent, is obtained the solid alkylation hexichol amine product of 97% or more purity, is urged using acidity
Agent system, product are grizzled particle.
CN 102584601A disclose a kind of preparation method 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 into synthesis reaction vessel, it is good
Good nitrogen protection, is added dropwise α-methylstyrene, insulation reaction obtains alkylated diphenylamine after reaction at the reaction temperatures
Mixed liquor；It is separated by filtration catalyst, filtrate is through recrystallization.It is filtered, washed, is dried to obtain antioxidant product of the present invention.This method
There are free H ions and chlorion in catalyst, product is caused to turn to be yellow or black, this is the color that post-processing can not remove.
This patent catalyst is after bleaching earth and Γ-aluminium oxide mixing through acid activation mixture, without free in catalyst
H ions and chlorion, be made product be pure white solid powder.
Invention content
The present invention provides a kind of solid alkylation diphenylamines preparation methods, by the way that catalyst and a certain amount of bleaching is added
Soil controls reaction condition, and it is white powder to obtain product, and base number is more than 120, and remaining diphenylamine content is less than 1%.
The invention aims to provide a kind of solid alkylation diphenylamines preparation method, this method is compared to current system
Preparation Method can be effectively improved product colour and improve alkene utilization rate, promote product by using bleaching earth and polymerization inhibitor
Can, alkene, catalyst can be recycled.
The present invention provides a kind of preparation method of solid alkylation diphenylamines, it is characterised in that includes the following steps：
A, by diphenylamines and alkene in molar ratio 1:3.5~1:8.0 mixing are added solid Lewis acid and are mixed with bleaching earth
The catalyst and polymerization inhibitor of preparation, and it is alkylated reaction under 80 DEG C~200 DEG C, normal pressure to 0.5MPa, until reactant
Middle diphenylamine content stops reaction when being less than 1%；
B, after reaction mixture being cooled to 80 DEG C -100 DEG C, filtering, vacuum distillation；
C, product in step b is recrystallized with polar organic solvent, obtains alkylated diphenylamine powder.
Wherein, it is in terms of 100% by the weight of diphenylamines, the solid Lewis acid catalyst levels are 15%-40%, institute
It is 10%~25% to state bleaching earth dosage；The polymerization inhibitor dosage is 100ppm~220ppm.
The commercially available bleaching earth of bleaching earth obtains after the heating 1~2 hour of 100 DEG C of baking oven.
The alkene is Diisobutylene, octene, tripropylene or nonene.
The solid Lewis acid catalyst be in the group being made of aluminium oxide, boron fluoride, silicate at least
It is a kind of.
It is in terms of 100% by diphenylamines mole, the alkene dosage is 350%~800%.
The temperature of the vacuum distillation is 100 DEG C~130 DEG C, and pressure is 0.06MPa~0.09MPa, and the time is 1.5~2
Hour.
The polymerization inhibitor is di-tert-butyl hydroquinone, m-dinitrobenzene, beta-naphthylamine or 8- aminoquinolines.
The polar organic solvent is mixture, ethyl alcohol, butanol, dioxane or the ether of petroleum ether and ethyl acetate.
The present invention can be with details are as follows：
Method provided by the invention includes：Carbon 8,9 alkene of carbon are mixed with diphenylamines, in the effect of catalyst and bleaching earth
Under be alkylated reaction at 80 DEG C~200 DEG C.
Diphenylamines and alkene can in molar ratio 1：3.5~1：8.0 being added.
Catalyst be with activity solid lewis acid, by the weight of diphenylamines be 100% in terms of, catalyst amount 15-
40%.
Bleaching earth is handled using physical method, commercially available bleaching earth and alumina mixture elder generation acid activation, deionization washing
To after without the H ions of dissociating, 100 DEG C of heating in an oven can be used after 1~2 hour, and bleaching earth addition is diphenylamines quality
10%~25%.
Polymerization inhibitor can prevent alkene autohemagglutination in reaction, and alkene dosage is larger in reaction, therefore polymerization inhibitor can be played and be weighed very much
The effect wanted.
Polymerization inhibitor addition is 100~220ppm.
Reaction temperature is 80 DEG C~200 DEG C, is carried out under normal pressure to 0.5MPa.
Reaction time is 0.5~20 hour.
Until diphenylamine content is less than 1% in reactant, stop reaction.
It being filtered after mixture suitably cooling, decompression boils off alkene, and polar organic solvent is added and is recrystallized,
Dialkyl diphenylamine product is finally obtained, product appearance is white powder, and base number is more than 120, and diphenylamine content is small
In 1%.
The present invention relates to preparing solid alkylation diphenylamines with the method for additional addition bleaching earth, compared to prior art,
It the techniques such as need not wash, neutralize, product is fine white powder, and product base number increases, and remaining diphenylamine content reduces, and without three
Useless emission problem, is good for the environment.
Product can carry out structure elucidation after separating-purifying, and data are shown in attached drawing 1, attached drawing 2.
With reference to embodiments, the present invention is described in detail.
Description of the drawings
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.
Specific implementation mode
Embodiment 1
The commercially available bleaching earth of bleaching earth obtains after the heating 1 hour of 100 DEG C of baking oven, equipped with blender, thermometer plus
Hot jacket, reflux condensing tube, water knockout drum, nitrogen pipeline 1000ml glass containers in be added diphenylamines 101.4g and 67.2g C8 alkene
Hydrocarbon and 10.0g bleaching earths and 20.4 silicate catalysts, are passed through nitrogen protection, are stirred with magnetic stirring apparatus, complete in 80 DEG C
After portion's melting, temperature is gradually risen to 165 DEG C, 201.6g C8 alkene was added at 5~10 hours, controls back-flow velocity and heating
Temperature makes temperature of charge be not less than 140 DEG C, and the reaction time is 20 hours.It is reacted to DPA according to TLC tracking to disappear substantially, fit
Alkene is removed when being cooled in 80 DEG C of filterings, being evaporated under reduced pressure, after ethyl alcohol recrystallization, final products is obtained, recycles alkene and catalyst,
Product is white powder, and data from gas chromatography shows diphenylamine content 0.5%, base number 124.
Embodiment 2
The commercially available bleaching earth of bleaching earth obtains after the heating 2 hours of 100 DEG C of baking oven, equipped with blender, thermometer plus
Hot jacket, reflux condensing tube, water knockout drum, nitrogen pipeline 1000ml glass containers in be added diphenylamines 101.4g and 75.6g C9 alkene
Hydrocarbon and 10.0g bleaching earths and 15.8g activated alumina catalysts, are passed through nitrogen protection, are stirred with magnetic stirring apparatus, in 80
DEG C all after melting, gradually rise temperature to 165 DEG C, be added 378.2g C9 alkene at 8~12 hours, control back-flow velocity and
Heating temperature makes temperature of charge be not less than 140 DEG C, and the reaction time is 20 hours.DPA is reacted to according to TLC tracking substantially to disappear
Lose, be suitably cooled in 80 DEG C of filterings, vacuum distillation removing alkene obtain final products with petroleum ether, re-crystallizing in ethyl acetate,
Alkene and catalyst are recycled, product is white powder, and data from gas chromatography shows diphenylamine content 0.8%, base number 122.
Claims (7)
1. a kind of preparation method of solid alkylation diphenylamines, it is characterised in that include the following steps：
A, by diphenylamines and alkene in molar ratio 1:3.5~1:8.0 mixing are added solid Lewis acid and are mixed with bleaching earth
Catalyst and polymerization inhibitor, and reaction is alkylated under 80 DEG C~200 DEG C, normal pressure to 0.5MPa, until in reactant two
Aniline content stops reaction when being less than 1%；
B, after reaction mixture being cooled to 80 DEG C -100 DEG C, filtering, vacuum distillation；
C, product in step b is recrystallized with polar organic solvent, obtains alkylated diphenylamine powder；
The solid Lewis acid is selected from least one of the group being made of aluminium oxide, boron fluoride, silicate；
The commercially available bleaching earth of bleaching earth obtains after the heating 1~2 hour of 100 DEG C of baking oven.
2. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that：With the weight of diphenylamines
For 100% meter, the solid Lewis acid catalyst levels are 15%-40%, and the bleaching earth dosage is 10%~25%；Institute
It is 100ppm~220ppm to state polymerization inhibitor dosage.
3. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that：The alkene is dimerization
Isobutene, octene, tripropylene or nonene.
4. the preparation method of solid alkylation diphenylamines according to claim 1 or 3, it is characterised in that：It is rubbed with diphenylamines
Your amount is 100% meter, and the alkene dosage is 350%~800%.
5. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that：The vacuum distillation
Temperature is 100 DEG C~130 DEG C, and pressure is 0.06MPa~0.09MPa, and the time is 1.5~2 hours.
6. the preparation method of solid alkylation diphenylamines according to claim 1 or 2, it is characterised in that：The polymerization inhibitor
For di-tert-butyl hydroquinone, m-dinitrobenzene, beta-naphthylamine or 8- aminoquinolines.
7. the preparation method of solid alkylation diphenylamines according to claim 1, it is characterised in that：The polarity is organic molten
Agent is mixture, ethyl alcohol, butanol, dioxane or the ether of petroleum ether and ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410815360.7A CN105777552B (en) | 2014-12-23 | 2014-12-23 | The preparation method of solid alkylation diphenylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410815360.7A CN105777552B (en) | 2014-12-23 | 2014-12-23 | The preparation method of solid alkylation diphenylamines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105777552A CN105777552A (en) | 2016-07-20 |
| CN105777552B true CN105777552B (en) | 2018-10-16 |
Family
ID=56378283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410815360.7A Active CN105777552B (en) | 2014-12-23 | 2014-12-23 | The preparation method of solid alkylation diphenylamines |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105777552B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107522623B (en) * | 2017-08-31 | 2020-04-14 | 广东中嘉节能科技有限公司 | Preparation method of diphenylamine-based rubber antioxidant |
| 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 |
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 |
-
2014
- 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105777552A (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MX2007009457A (en) | Method for producing substituted biphenyls. | |
| AU2007267055A1 (en) | Process for preparing substituted biphenyls | |
| CN105777552B (en) | The preparation method of solid alkylation diphenylamines | |
| KR20180113970A (en) | Process for producing aryl-substituted para-phenylenediamine-based material | |
| EP1939169B1 (en) | Method to prepare nonylated diphenylamine using recycle and sequential temperatures | |
| CN105732400A (en) | Preparation method for (para, para)-diisopropylphenyl diphenylamine product | |
| CN1911939B (en) | Preparation method of phosphite ester kind antioxidant | |
| CN103694136B (en) | The method of divinyl one-step synthesis method adiponitrile | |
| JP2010195690A (en) | High-purity trialkyl gallium, and method of producing the same | |
| WO2017011159A1 (en) | Diaryl amine antioxidants prepared from branched olefins | |
| CA2863057C (en) | Process for preparing choline hydroxide from trimethylamine and ethylene oxide | |
| CN105777557A (en) | Alkylation method for mixed aromatic amine, alkylated aromatic amine and use thereof | |
| KR102658500B1 (en) | Method for producing butene polymer | |
| CN102320983A (en) | A kind of preparation method of liquid octylated diphenylamine oxidation inhibitor | |
| CN104628580B (en) | The preparation method of the nonyl diphenylamine that a kind of mixed olefins participates in | |
| CN105777537B (en) | A kind of alkylation of salicylic acid method | |
| Heydari et al. | An efficient method for synthesis of stable phosphorus ylides and 1, 4-diionic organophosphorus compounds in the presence of sodium dodecyl sulfate in aqueous media | |
| CN103804109A (en) | Vulcanizing agent synthesis method | |
| KR20080011685A (en) | Improved process for synthesizing alkylated arylamines | |
| DE10300126A1 (en) | Process for the preparation of aminodiphenylamines | |
| EP3357914B1 (en) | Aromatic compound production method | |
| US2521416A (en) | N-hydroxyphenyl-isoindolines | |
| CN102863471A (en) | Process for catalyzing preparation of tricresyl phosphite-(2-chloroethyl) ester | |
| CN109574854A (en) | A kind of alkylation N- phenyl-a- naphthylamines antioxidant and preparation method thereof | |
| Azizian et al. | Highly functionalized dihydrofuran derivatives: Synthesis by diastereoselective intramolecular Wittig reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |