CN102701997A - Process for purifying dialkyl diphenylamine - Google Patents
Process for purifying dialkyl diphenylamine Download PDFInfo
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- CN102701997A CN102701997A CN2012102350015A CN201210235001A CN102701997A CN 102701997 A CN102701997 A CN 102701997A CN 2012102350015 A CN2012102350015 A CN 2012102350015A CN 201210235001 A CN201210235001 A CN 201210235001A CN 102701997 A CN102701997 A CN 102701997A
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Abstract
The invention relates to a process for purifying dialkyl diphenylamine and belongs to the field of purification of material antioxidants. The process comprises: firstly heating dialkyl diphenylamine crude products to be melt, slowly cooling to the temperature of 60-75 DEG C, keeping the temperature of 60-75 DEG C for 5-10 hours, and discharging mother liquid after melt dialkyl diphenylamine crude products are crystallized to obtain a dialkyl diphenylamine crystal layer; heating the dialkyl diphenylamine crystal layer through a method of gradient increased temperature until the temperature rises to be close to a melting point of the dialkyl diphenylamine, and discharging liquid phase to obtain the purified dialkyl diphenylamine. The quality of the dialkyl diphenylamine purified through the process can meet quality requirements of high-purity-level products, and high-quality dialkyl diphenylamine can be obtained through the process while only a distillation process or a solvent crystallization process can not obtain the high-quality dialkyl diphenylamine. The process is simple in operation, free of consumption of any solvent, high in product yield, good in environmental friendliness and capable of causing no waste water or waste gas.
Description
Technical field
The present invention relates to a kind of purifying technique of dialkyl diphenylamine, particularly a kind of method for preparing the high-content dialkyl diphenylamine belongs to material oxidation inhibitor purification field.
Background technology
Along with rubber, plastics, oil product industrial expansion, the research of oxidation inhibitor and production more and more receive people's attention.At present, no matter be common rubber item, still high-grade aerospace lubricating oil, engine lubrication wet goods have all proposed requirement to high performance oxidation inhibitor, and this requirement is more and more harsher.So need high-performance, highly purified oxidation inhibitor to satisfy these requirements.
The demand can be satisfied by the oxidation inhibitor dialkyl diphenylamine.Dialkyl diphenylamine belongs to a kind of of alkylated diphenylamine oxidation inhibitor; Because its purity is high, fusing point is high, antioxidant property is remarkable; So in a lot of high-grade rubber items and high-grade oils, use more; But because its complex manufacturing, particularly purifying technique is loaded down with trivial details, does not cause output high and cost an arm and a leg.
Dialkyl diphenylamine oxidation inhibitor tends to produce normal monoalkyl pentanoic in the preparation process; Even also contain the not alkene and the pentanoic of complete reaction; And these monoalkyl pentanoic, alkene, pentanoic be we do not hope to obtain, if these impurity are not removed, the finished product might be in a liquid state; Also might cause the finished product fusing point very low, reach the not requirement of high purity antioxygen.
US2776994 discloses a kind of method for preparing solid diphenylamine oxidation inhibitor.This method is that pentanoic and excessive diisobutylene react under the effect of catalyzer and obtain the octylated diphenylamine mixture, remove impurity such as unreacted diisobutylene, pentanoic, single octyl diphenylamine through underpressure distillation then, and distillation temperature is up to 250 ℃.Still liquid cooling back after the distillation makes it the performance stirred crystallization and forms crystal through a pipeline with quick agitating function, and be cooled to room temperature then and form comparatively hard solid, final grind into powder, the fusing point of products obtained therefrom is merely about 85 ℃.This method has following shortcoming:
1, distillation temperature is too high, and up to 250 ℃, and octylated diphenylamine itself is a heat-sensitive material, has the part cracking under the high temperature, and can make the product variable color, thereby influences final quality product.
2, purification efficiency is not high, is merely 85 ℃ through the octylated diphenylamine fusing point after purifying.
US3714257 discloses a kind of method for preparing dialkyl diphenylamine.This method is that 1 part of pentanoic reacts under 0.1 part of catalyzer with at least 4 parts of diisobutylene; The intermediate liquid that obtains carries out air distillation earlier and removes unreacted diisobutylene; And then some heavy-gravity low-boiling point liquids are removed in underpressure distillation; The fusing point that final cooling obtains the octylated diphenylamine finished product is 75-85 ℃, and the content of dioctyl diphenylamine is merely about 85%.This method also is typically to distill method of purification, but efficient is lower, and the content of dialkyl diphenylamine is merely about 85% in the gained finished product, and fusing point is also only between 75-85 ℃, and this separating effect can't reach the requirement of high-purity oxidation inhibitor.
US7928265 discloses a kind of preparation method of octylated diphenylamine antioxidant composition.The obtained intermediates of this method comprise 65-70 weight % dioctyl diphenylamine; The single octyl diphenylamine of 29 weight % at the most; 5 weight % octyl group butyl pentanoic, 1.5 weight % trioctylphosphine pentanoic, 1 weight % pentanoic at the most at the most at the most; Intermediates are through methyl alcohol, ethanol, Virahol, hexalin, hexanaphthene and/or diisobutylene crystallization and purification finished product, and the weight content of dioctyl diphenylamine is about 95% in the gained finished product.This method is through solvent crystallization purification dialkyl diphenylamine; Shortcomings such as and solvent crystallization exists yield low, and solvent consumption is big, using has certain limitation; And the content of dioctyl diphenylamine is about 95% in the product of being purified in the method, and purity is still waiting to improve.
CN102276480 discloses a kind of preparation method of high-purity solid-state alkylated diphenylamine.This method is to react under catalyst action through pentanoic and excessive olefin; When the content of reaction species pentanoic less than 0.5% the time; Stopped reaction is also collected product, adopts polar solvent crystallization process purified reaction thing then, and obtaining purity is solid-state alkylated diphenylamine product more than 97%.This method is to adopt solvent crystallization to purify to obtain solid-state alkylated diphenylamine, has shortcomings such as solvent loss, product content are not high, product yield is low equally.
It is thus clear that the method for general purification dialkyl diphenylamine mainly is divided into two kinds, a kind of is the distillation method of purification, and another kind is a solvent crystallization.The distillation method of purification is applicable to that generally boiling point is lower, the material of non-thermo-sensitivity, but a kind of as oxidation inhibitor of alkylated diphenylamine; At high temperature easy to change, decomposition influence product quality, and the dialkyl diphenylamine product content that uses the distillation method of purification to obtain thus is low; Color is dark, and quality is low.And solvent crystallization need be used solvent; In the solvent crystallization process; Except that the crystallization operating unit; Also need unit such as centrifugal, oven dry and solvent recuperation, so long flow path, main equipment are many, have shortcomings such as investment is high, the treating process energy consumption is high, solvent loss is many, the discharging of waste liquid amount is big, product yield is low.
Summary of the invention
In order to solve above-mentioned technical barrier, the invention provides a kind of employing pentanoic and alkene is raw material, and alkylated reaction takes place under the effect of atlapulgite catalytic alkylation, and the purity that obtains is the method for purification of 50～80% dialkyl diphenylamine bullion.
The present invention includes following steps:
1) the dialkyl diphenylamine bullion is heated to fusion after, slowly cooling is cooled to 60～75 ℃ and keeps 5～10h, discharges mother liquor after the crystallization, obtains the dialkyl diphenylamine crystal layer;
2) the dialkyl diphenylamine crystal layer is adopted gradient heating, rise to fusing point, after the discharge liquid phase, obtain the dialkyl diphenylamine of purification near dialkyl diphenylamine up to temperature.
Because dialkyl diphenylamine is in process of cooling, the molecule activity ability is hindered, and is difficult to oneself and forms nucleus; Unavoidably low can the generation of crystal contained phenomenon; The mother liquor that contains impurity is contained, and is clipped in the crystal or is wrapped in plane of crystal, and crystal purity is descended; So the present invention is the induced crystallization solvent with remaining excessive alkene in the reaction intermediate liquid, the fractional crystallization through primary crystallization and sweating obtains high purity product at least.The purity of the dialkyl diphenylamine after the present invention purifies can reach more than 99.0%.After this technology, but reheat makes the whole fusions of dialkyl diphenylamine after the purification, the finished product after the fusion is transferred to carried out follow-up granulation, pulverizing in the finished product jar, finally obtains high-purity dialkyl diphenylamine commodity.
The quality product that the present invention obtains can satisfy high-purity grade of quality product requirement, has obtained the high-quality dialkyl diphenylamine that only perhaps only can't realize with solvent crystallization technology with rectification process.The present invention is simple to operate in addition, does not consume any solvent, and product yield is high, does not have waste water and gas to produce, and the feature of environmental protection is good.
It is the speed cooling with 1.0～4.0 ℃/h that the present invention slowly lowers the temperature in said step 1).The too fast meeting of cooling rate cause nucleus to produce between the fast and nucleus of speed fast autohemagglutination produces bulky crystal, will containing mother liquor in the bulky crystal, to cause separating refining effect poor; Cooling rate is crossed and then can be caused crystallizing cycle long slowly, influences purification efficiency.Through test of many times, confirm that the speed cooling with 1.0～4.0 ℃/h is the best.
The present invention is in said step 2) in earlier the dialkyl diphenylamine crystal layer is warming up to 90～99 ℃ with the speed of 1.0～4.0 ℃/h, classification section again adopts and heats up, the homothermic circulation means, and the dialkyl diphenylamine crystal layer is warming up to the dialkyl diphenylamine fusing point.
The dialkyl diphenylamine crystal layer is warming up to 90～99 ℃ with 1.0～4.0 ℃/h speed makes partial melting (this step is called " sweating process ", and the liquid that fusion obtains is called " sweat "); Can adopt the classification sweating, keep lesser temps when sweating is initial, after a period of stabilisation temperature raise; Keep for some time in this temperature, so near temperature rises to the fusing point of pure article, discharge sweat gradually; Sampling; When the purity of dialkyl diphenylamine in the sweat >=99.0%, stop sweating, promptly obtain the dialkyl diphenylamine of purifying.
It is raw material that the present invention provides a kind of employing pentanoic and alkene; Alkylated reaction takes place under the effect of atlapulgite catalytic alkylation; Gained dialkyl diphenylamine bullion (mass percent of dialkyl diphenylamine is 50～80%), the method for purification through fusion-crystallization obtains high-purity dialkyl diphenylamine then.
Embodiment
One, preparation dioctyl diphenylamine bullion
100kg pentanoic and 20kg catalyst activity carclazyte input are had in whisking appliance and the Dropping feeder reactor drum, drip the 268kg diisobutylene then and carry out alkylated reaction, filtration promptly gets the dioctyl diphenylamine bullion after removing catalyzer.
Above diisobutylene can alpha-methyl styrene or tetrapropylene substitute.
Through analyzing, the mass percent of dioctyl diphenylamine is 61% in the dioctyl diphenylamine bullion, and all the other are diisobutylene, single octyl diphenylamine etc.
Two, purify
Bullion is joined in the mold, heat whole fusions after, (preferred 4.0 ℃/h) speed is slowly lowered the temperature, and is cooled to 60～75 ℃ and keeps 5～10h (preferred 7h), discharges mother liquor after the crystallization, obtains the dioctyl diphenylamine crystal layer with 1.0～4.0 ℃/h.
Earlier (preferred 4.0 ℃/h) speed is warming up to 90～99 ℃ (preferred 90 ℃) with the dialkyl diphenylamine crystal layer, makes the fusion of part dioctyl diphenylamine crystal layer, discharges sweat with 1.0～4.0 ℃/h with the dioctyl diphenylamine crystal layer; And then be warming up to 98 ℃ with 2.0 ℃/h speed, discharge sweat gradually, sampling; When the purity of dioctyl diphenylamine in the sweat >=99.0%; Stop to heat up, then in mold, obtain the dioctyl diphenylamine of purifying, purity can reach 99.0%.
Three, finished product processing
Heat extremely all fusions of dioctyl diphenylamine of purifying, the finished product after the fusion is transferred to carried out follow-up granulation, pulverizing in the finished product jar, finally obtain high-purity dioctyl diphenylamine commodity.
The mother liquor of above production process can turn back to and proceed alkylated reaction in the reactor drum.Sweat can mix the raw material as the next batch fusion-crystallization with the dioctyl diphenylamine bullion.
Through detecting, the content of dioctyl diphenylamine is up to 99.30% in the final finished, and the fusing point of finished product is 100.5 ℃.Repeat above-mentioned steps, carry out primary crystallization, sweating purification again, can obtain the product of dioctyl diphenylamine content >=99.80%.
Claims (3)
1. the purifying technique of a dialkyl diphenylamine is characterized in that may further comprise the steps:
1) the dialkyl diphenylamine bullion is heated to fusion after, slowly cooling is cooled to 60～75 ℃ and keeps 5～10h, discharges mother liquor after the crystallization, obtains the dialkyl diphenylamine crystal layer;
2) the dialkyl diphenylamine crystal layer is adopted gradient heating, after temperature rises to the fusing point of dialkyl diphenylamine, discharges liquid phase, obtain the dialkyl diphenylamine of purification.
2. according to the purifying technique of the said dialkyl diphenylamine of claim 1, it is characterized in that: slowly lowering the temperature in the said step 1) is the speed cooling with 1.0～4.0 ℃/h.
3. according to the purifying technique of the said dialkyl diphenylamine of claim 1; It is characterized in that: elder generation is warming up to 90～99 ℃ with the speed of 1.0～4.0 ℃/h with the dialkyl diphenylamine crystal layer said step 2); Classification section again adopts and heats up, the homothermic circulation means, and the dialkyl diphenylamine crystal layer is warming up to the dialkyl diphenylamine fusing point.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012102350015A CN102701997A (en) | 2012-07-09 | 2012-07-09 | Process for purifying dialkyl diphenylamine |
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| CN2012102350015A CN102701997A (en) | 2012-07-09 | 2012-07-09 | Process for purifying dialkyl diphenylamine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601462A (en) * | 2016-02-19 | 2016-05-25 | 国药集团化学试剂有限公司 | High-purity benzene purification method |
| CN113666831A (en) * | 2021-08-05 | 2021-11-19 | 天津科技大学 | Method for preparing high-purity o-nitroaniline by layer-type melt crystallization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5750787A (en) * | 1995-09-13 | 1998-05-12 | B. F. Goodrich Company | Liquid alkylated diphenylamine antioxidant |
| WO2005052050A1 (en) * | 2003-11-25 | 2005-06-09 | Duslo A.S. | Antioxidant compositions of octylated diphenylamines and method of their preparation |
| CN101250113A (en) * | 2008-03-28 | 2008-08-27 | 上海安诺芳胺化学品有限公司 | Method for refining p-phenylene diamine |
| 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 |
-
2012
- 2012-07-09 CN CN2012102350015A patent/CN102701997A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5750787A (en) * | 1995-09-13 | 1998-05-12 | B. F. Goodrich Company | Liquid alkylated diphenylamine antioxidant |
| WO2005052050A1 (en) * | 2003-11-25 | 2005-06-09 | Duslo A.S. | Antioxidant compositions of octylated diphenylamines and method of their preparation |
| CN101250113A (en) * | 2008-03-28 | 2008-08-27 | 上海安诺芳胺化学品有限公司 | Method for refining p-phenylene diamine |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601462A (en) * | 2016-02-19 | 2016-05-25 | 国药集团化学试剂有限公司 | High-purity benzene purification method |
| CN113666831A (en) * | 2021-08-05 | 2021-11-19 | 天津科技大学 | Method for preparing high-purity o-nitroaniline by layer-type melt crystallization |
| CN113666831B (en) * | 2021-08-05 | 2024-02-06 | 天津科技大学 | Method for preparing high-purity o-nitroaniline by layered melt crystallization |
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Application publication date: 20121003 |