CN1611486A - Fine chemical intermediate P-hydroxy diphenylamine and its preparing process - Google Patents
Fine chemical intermediate P-hydroxy diphenylamine and its preparing process Download PDFInfo
- Publication number
- CN1611486A CN1611486A CN 200310105377 CN200310105377A CN1611486A CN 1611486 A CN1611486 A CN 1611486A CN 200310105377 CN200310105377 CN 200310105377 CN 200310105377 A CN200310105377 A CN 200310105377A CN 1611486 A CN1611486 A CN 1611486A
- Authority
- CN
- China
- Prior art keywords
- fine
- chemical intermediate
- preparation technology
- resorcinol
- aniline
- 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.)
- Pending
Links
Abstract
The invention relates to a kind of fine chemistry industry midbody, P-hydroxy diphenylamine and its manufacturing method. The raw materials of P-hydroxy diphenylamine in the invention is composed with hydroquinone and aniline, according to stuff casting molar ratio with 1:1.25-1.40; after heating with high temperature and condensation reaction by catalyst, decline the temperature, and then get the products by alkali cleaning, water washing and distillation. The invention offers an ideal tere hydroxy diphenylamine product, which has high purity, fine trinct, and low pollution. The purity of products acquired by the method all exceed 95% product purity in the best foreign company, it can achieve more than 99%, and also it has safe production technology and environmental protection.
Description
One, technical field:
The present invention relates to fine-chemical intermediate p-hydroxydiphenylamine and preparation technology thereof, belong to the fine chemical technology field
Two, background technology:
P-hydroxydiphenylamine is an amine product in the organic compound, because preparation is difficult, consumption is few, value is high, so be listed in the category of fine chemical product.
P-hydroxydiphenylamine was mainly used in the manufacturing (Colour index number: [C.I sul phur Red 10 (53228)] of dyestuff sulphur red brown R in the past abroad, this dyestuff eighties of last century is domestic to be subjected to the restriction of raw material p-hydroxydiphenylamine to fail to develop always, substitutes by import or with other dyestuff.P-hydroxydiphenylamine has only several companies of the U.S., Japan, German a few countries to produce at present, so the price comparison height, and in this case, we have invented this product and have put into production, to satisfy the demand of outlet.Used this product development success sulphur red brown R dyestuff.Along with development of technology, this product has been processed into plastics, rubber one package stabilizer and rubber antioxidant abroad in recent years.Recently China and foreign countries scientific research institution is with this product development oil product antioxidant additive, so the invention of this product filled up domestic blank, also market outlook preferably will be arranged.
According to data at home and abroad, the main method of p-hydroxydiphenylamine production is to adopt para-chlorophenol and aniline to carry out condensation and get.The resulting product content of this method is low, its purity generally only has 90-92%, the best product purity of offshore company does not surpass 95% yet, and the color and luster extreme difference is chocolate, contains chlorion, influenced the quality of derived product, in addition, the raw materials used toxicity of this method is big, seriously polluted, and production process is serious to equipment and pipeline corrosion.Therefore be badly in need of a kind of product purity height of invention, color and luster good, pollute low product and replace.
Three, summary of the invention
The object of the present invention is to provide a kind of product purity height, color and luster good, pollute low p-hydroxydiphenylamine and preparation technology thereof.
The raw material of p-hydroxydiphenylamine of the present invention consists of Resorcinol and aniline, and molar ratio is 1: 1.25-1.40, preferred 1: 1.3-1.35.
P-hydroxydiphenylamine preparation technology of the present invention is to be raw material with Resorcinol and aniline, under catalyst action through heat, condensation reaction, cooling and then obtain product through alkali cleaning, washing, distillation.
The preparation technology of p-hydroxydiphenylamine is that the multicomponent mixture of major ingredient is special-purpose condensation catalyst for adopting with sulfonic acid; Distillation is made with extra care for vacuum distillation method, distills refining under-0.1Mpa; The water that condensation reaction produces shifts out with condensation phase-splitting reflow method; The condensation reaction terminal point is determined with the 102-108% of theoretical aquifer yield; It is the aqueous sodium carbonate of 4-7% that alkaline wash adopts concentration, and temperature is 80-90 ℃, and the yellow soda ash usage quantity is the 6-8% of Resorcinol input amount; Preferred concentration is that the aqueous sodium carbonate of 6-7% carries out alkali cleaning for 84 ℃-87 ℃, and the yellow soda ash usage quantity is preferably the 6.7-7.3% of Resorcinol charging capacity.
The chemical equation of said process is:
The following Technology of concrete employing realizes: with Resorcinol and aniline is raw material, adding is that the multicomponent mixture of major ingredient is special-purpose condensation catalyst with sulfonic acid, through being heated to 110 ℃, Resorcinol is dissolved in the aniline, continue heating and stirring, when being heated to 170 ℃, the beginning condensation reaction, along with reaction generate product p-hydroxydiphenylamine and water, water is vaporized through condenser condenses with aniline and separates water outlet, aniline under the condensation is back to reactor, along with reaction is constantly carried out, product is on the increase, and temperature also progressively rises, the water that reaction generates constantly is moved out of, and reaction is carried out to positive dirction.When temperature rises to 220 ℃, when the water yield that shifts out has reached theoretical amount, react and finish.Be cooled to 100 ℃ then through using 80-90 ℃ of 5% aqueous sodium carbonate alkali cleaning, again through 80-90 ℃ of washing, remove the Resorcinol and the catalyzer of traces of unreacted, dewater then and deviate from excessive aniline, obtain the liquid p-hydroxydiphenylamine through underpressure distillation again, be condensed into canescence or faint yellow xln p-hydroxydiphenylamine after the packing.
The characteristics of above Technology are:
1, adopt special catalyzer, carry out condensation reaction, otherwise condensation reaction is very faint, does not go down through catalyst;
2, the mol ratio of raw material Resorcinol and raw material aniline is 1: 1.25-1.40;
3, condensation reaction adopts the method for condenser phase-splitting backflow to shift out the water of generation;
4, alkaline wash employing aqueous sodium carbonate concentration is 4-7%, and temperature is 80-90 ℃, and sodium carbonate amount is the 6-8% of Resorcinol amount;
5, adopt underpressure distillation.
The invention provides a kind of p-hydroxydiphenylamine product, the purity height, color and luster is good, pollution is low, is a kind of ideal p-hydroxydiphenylamine product, its preparation technology's safety, environmental protection.
Four, embodiment
Embodiment 1: having on the electric mantle of regulator, and dress 500ml four-hole bottle, four-hole bottle has the speed governing whipping appts, and thermometer, prolong and reflux water-dividing device are housed.With 166g (1.5mol) 99.5% Resorcinol and 182g (1.95mol) the 99.5% aniline four-hole bottle of packing into, adding is the multicomponent mixture 6.7g (Resorcinol 4%) of major ingredient with sulfonic acid, will saturated aqueous common salt be housed to the scale of regulation and weigh in the water trap.Send electrically heated, when rising to 110 ℃, temperature opens stirring, when temperature rises to 170 ℃, the aniline vaporization, cooling down by condenser flows into the reflux water-dividing device, and along with the rising gradually of temperature, condensation reaction is constantly carried out, the p-hydroxydiphenylamine that produces is stayed in the four-hole bottle, aniline in company with being vaporized enters water trap through condenser condenses, and aniline is back to four-hole bottle on the upper strata, water is stayed in the salt solution, when reflux water-dividing device water level rises to certain altitude, emit some water metered volume, when temperature rises to 220 ℃, the water of telling reaches 28ml, and condensation reaction finishes.Stop to send, cooling when temperature is reduced to 110 ℃, is pulled down condenser, the reflux water-dividing device, saturated brine that adds and the 28ml water of telling mixing are weighed, cut and add former saturated aqueous common salt, can accurately measure reaction and shift out the water yield and be about 26.5-27.5g, pour reactant into the 2000ml wide-necked bottle, the sodium carbonate solution 200ml that adds 5%85 ℃, shook 5 minutes, and moved into separating funnel then, left standstill 10 minutes, after isolating wash water, with 85 ℃ of hot water 200ml washings 2 times, the material after the washing is put back to former four-hole bottle again, connect water distilling apparatus and vacuum pump, under-0.1Mpa vacuum, send electrically heated, do not separate clean water when at first washing and taken off, water is purified when temperature rises to 110 ℃, has aniline to be deviate from, aniline has been taken off when temperature reaches 170 ℃, the front-end volatiles thing that has side reaction to produce is then steamed, and when temperature rises to 180 ℃, begins to receive the product p-hydroxydiphenylamine, when reaching 240 ℃ of distillations, the still temperature finishes, get product 208g, purity 99%, yield 74.2%.
P-hydroxydiphenylamine product purity height, the color and luster that present embodiment provides is good, pollution is low, is a kind of ideal p-hydroxydiphenylamine product, its production technique safety, environmental protection.
Embodiment 2: add Resorcinol 440Kg (4Kmol) in 1500 liters of glassed steel reaction vessels, 99% aniline 490Kg (5.21Kmol), with sulfonic acid is the multicomponent mixture 18Kg of major ingredient, add 120 liters of saturated aqueous common salts in the phase splitter, surveying its proportion is 1.18, send heating agent to reacting kettle jacketing, heating is opened stirring when temperature in the kettle rises to 110 ℃.When temperature in the kettle rises to 170 ℃, the aniline vaporization produces aniline steam, condensation reaction simultaneously begins to carry out, there are p-hydroxydiphenylamine and water to generate, water is vaporized simultaneously together with aniline steam and enters condenser, condensation enters phase splitter, and aniline flows into reactor on the upper strata, water is sneaked into saturated brine, raise with temperature, reaction is constantly carried out, and the water level in the phase splitter rises, when being raised to certain scale, emit portion water and measure, when temperature in the kettle rises to 220 ℃, emit the about 87Kg of water (containing salt solution) condensation reaction and finish.Reacting kettle jacketing changes refrigerant, and cooling is when temperature is reduced to 110 ℃, 600 liters of aqueous sodium carbonates that in still, add 5%85 ℃, stirred 10 minutes, and stopped then to stir, left standstill 1 hour, with special-purpose drinking-water pipe the upper strata wash water is extracted out then, the hot water that adds 600 liters 85 ℃ again stirred 10 minutes, stopped then to stir to leave standstill to extract wash water in 1 hour again out, and the reaction mixture of washing is moved in the precipitation still kettle, thermal dehydration under vacuum, when vacuum is-0.1Mpa, during 110 ℃ of temperature, dehydration finishes, continue to deviate from excessive aniline, when temperature reaches 170 ℃, deviate from aniline and finish the reconfiguration front-end volatiles, when temperature reaches 180 ℃, the positive cut of reconfiguration product, when temperature reaches 240 ℃, the distillation finish product 550Kg, purity 99%, yield 73.6%.
The p-hydroxydiphenylamine product that present embodiment provides can reach the purity height equally, color and luster is good, pollution is low, is a kind of ideal p-hydroxydiphenylamine product, its production technique safety, environmental protection.
The statistic data that draws by a series of experiment shows: the invention provides a kind of ideal p-hydroxydiphenylamine product, the purity height, color and luster is good, pollution is low, resulting product purity all surpasses 95% best product purity of offshore company, can reach more than 99% its production technique safety, environmental protection.
Claims (9)
1. a fine-chemical intermediate p-hydroxydiphenylamine is characterized in that its raw material consists of Resorcinol and aniline, and molar ratio is 1: 1.25-1.40.
2. according to claims 1 described a kind of fine-chemical intermediate p-hydroxydiphenylamine, it is characterized in that raw material Resorcinol and aniline batching mol ratio preferred 1: 1.3-1.35.
3. the preparation technology of a fine-chemical intermediate p-hydroxydiphenylamine, it is characterized in that with Resorcinol and aniline being that raw material is under catalyst action, through heat, condensation reaction, cooling and then obtain product through alkali cleaning, washing, distillation, its chemical process reaction formula is:
4. according to the preparation technology of claims 3 described a kind of fine-chemical intermediate p-hydroxydiphenylamines, it is characterized in that adopting with sulfonic acid is that the multicomponent mixture of major ingredient is special-purpose condensation catalyst.
5. according to the preparation technology of claims 3 described a kind of fine-chemical intermediate p-hydroxydiphenylamines, it is characterized in that distillation makes with extra care for vacuum distillation method, under-0.1Mpa, distill refining.
6. according to the preparation technology of claims 3 described a kind of fine-chemical intermediate p-hydroxydiphenylamines, it is characterized in that the water that condensation reaction produces shifts out with condenser phase-splitting reflow method.
7. according to the preparation technology of claims 3 described a kind of fine-chemical intermediate p-hydroxydiphenylamines, it is characterized in that the condensation reaction terminal point determines with the 102-108% of theoretical aquifer yield.
8. according to the preparation technology of claims 3 described a kind of fine-chemical intermediate p-hydroxydiphenylamines, it is characterized in that it is the aqueous sodium carbonate of 4-7% that alkaline wash adopts concentration, temperature is 80-90 ℃, and the yellow soda ash usage quantity is the 6-8% of Resorcinol input amount.
9. according to the preparation technology of claims 8 described a kind of fine-chemical intermediate p-hydroxydiphenylamines, it is characterized in that preferred concentration is that the aqueous sodium carbonate of 6-7% carries out alkali cleaning for 84 ℃-87 ℃, the yellow soda ash usage quantity is preferably the 6.7-7.3% of Resorcinol charging capacity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310105377 CN1611486A (en) | 2003-10-29 | 2003-10-29 | Fine chemical intermediate P-hydroxy diphenylamine and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310105377 CN1611486A (en) | 2003-10-29 | 2003-10-29 | Fine chemical intermediate P-hydroxy diphenylamine and its preparing process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1611486A true CN1611486A (en) | 2005-05-04 |
Family
ID=34757279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310105377 Pending CN1611486A (en) | 2003-10-29 | 2003-10-29 | Fine chemical intermediate P-hydroxy diphenylamine and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1611486A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177266A (en) * | 2013-05-24 | 2014-12-03 | 中国石油化工股份有限公司 | Parahydroxydiphenylamine synthesis method |
| WO2022048565A1 (en) * | 2020-09-01 | 2022-03-10 | 圣奥化学科技有限公司 | Preparation method for asymmetric diaryl substituted p-phenylenediamine compound |
-
2003
- 2003-10-29 CN CN 200310105377 patent/CN1611486A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177266A (en) * | 2013-05-24 | 2014-12-03 | 中国石油化工股份有限公司 | Parahydroxydiphenylamine synthesis method |
| WO2022048565A1 (en) * | 2020-09-01 | 2022-03-10 | 圣奥化学科技有限公司 | Preparation method for asymmetric diaryl substituted p-phenylenediamine compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101439849B (en) | Comprehensive utilization process for waste aluminum etching solution | |
| CN1911890B (en) | Method of producing high-purity hydroxypivalaldehyde and/or dimer thereof | |
| CN100393677C (en) | Process for extracting 1-methylnaphthalene and 2-methylnaphthalene from tar | |
| US2877274A (en) | Production of sodium methoxide | |
| CN106699808A (en) | Acidolysis and solvent recycling process and device for producing glyphosate by using glycine method | |
| CN108404637A (en) | A kind of alkyl esterification method glyphosate hydrolyzing tail gas reclaimer and technique | |
| CN1280122A (en) | Method for producing acetylacetic ester | |
| CN102796035A (en) | Condensation method of m-,p-mixed di-(tert-butyl isopropyl peroxide)benzene | |
| CN1611486A (en) | Fine chemical intermediate P-hydroxy diphenylamine and its preparing process | |
| JPS62238224A (en) | Separation of phenol and base from coal tar oil by extraction | |
| CN109134215B (en) | Production method for preparing trimethyl orthoformate by liquid metal sodium slag method | |
| CN1031706C (en) | Process for producing antioxidant | |
| CN101821222A (en) | Process for production of ditrimethylolpropane | |
| CN105085165B (en) | The separation method of ethylene glycol and diethylene glycol | |
| CN1070877C (en) | Method to manufacture liquid epoxy resins | |
| CN102432510B (en) | Synthetic method of dimethyl cysteamine hydrochloride | |
| CN102701922B (en) | Method for synthesizing methylal | |
| EP0031695B1 (en) | Production of mixture of branched and linear carboxylic acid salts | |
| CN1132825C (en) | Process for preparing N-formyl morpholine | |
| GB1587958A (en) | Production of tertiary butyl amine sodium and methyl or sodium formate | |
| CN115215894B (en) | Preparation method of low-acid-value tetramethyl dihydro disiloxane | |
| CN110003266A (en) | A kind of environment-protection production method of the 3- Octanoylthio -1- propyl-triethoxysilicane of high-quality | |
| CN115181019B (en) | Process for preparing electronic grade glycollic acid solution by methyl glycolate hydrolysis | |
| CN109651088A (en) | The method for extracting neopentyl glycol in neopentyl glycol purifying waste liquid | |
| CN1114956A (en) | Extraction of natural guaiacol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |