CN101747156A - New method for preparing 2,4-ditert-pentyl-phenol - Google Patents
New method for preparing 2,4-ditert-pentyl-phenol Download PDFInfo
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- CN101747156A CN101747156A CN200910245132A CN200910245132A CN101747156A CN 101747156 A CN101747156 A CN 101747156A CN 200910245132 A CN200910245132 A CN 200910245132A CN 200910245132 A CN200910245132 A CN 200910245132A CN 101747156 A CN101747156 A CN 101747156A
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Abstract
The invention relates to a new method for preparing 2,4-ditert-pentyl-phenol by two steps of alkylating and by using different catalysts. The method comprises the steps of: firstly, in the presence of catalyst aluminum phenoxide, singly alkylating phenol and phenol to obtain a reaction solution, the main content of which is o-tert-pentyl-phenol; and secondly, alkylating the reaction solution and isoamylene under the action of catalyst atlapulgite to obtain a dialkyl reaction solution, and rectifying the dialkyl reaction solution to obtain the 2,4-ditert-pentyl-phenol. The new method is characterized in that the high-yield high-quality product can be obtained by controlling the selection of catalysts in all reaction steps and main reaction conditions. The invention adopts a two-step method to prepare the 2,4-ditert-pentyl-phenol and has the advantages of high yield, low cost, simple and reliable operation process and stable and easily controlled reaction process; in addition, the method is a green and environment-friendly process and is beneficial to large-scale industrial implementation.
Description
Technical field
The present invention relates to 2, a kind of new preparation process of 4-two tert-amyl phenols belongs to 2, the technology of preparing of 4-two tert-amyl phenols.
Background technology
2,4-two tert-amyl phenols are a kind of Organic Chemicals, are widely used in fields such as dyestuff intermediate, photosensitive material additive, bisphenolmonoacryates oxidation inhibitor GS, benzotriazole UV light absorber UV-328, synthetic resins.
2, the preparation method that 4-two tert-amyl phenol main preparation methods are reported is as follows:
1) U.S. Pat 4260833 has reported that with phenol and isopentene be raw material, in the presence of activated bauxite catalyst through the catalytic alkylation Synthetic 2,4-two tert-amyl phenol technology, this method is a single stage method.
2) Fusun PetroleumCollege's journal the 21st the 3rd phase of volume of calendar year 2001 has been reported following method, is raw material with phenol and isopentene promptly, and the employing solid super-strong acid is a catalyzer, through the catalytic alkylation Synthetic 2, and 4-two tert-amyl phenols.
3) " meticulous Organic Chemicals and intermediate handbook, Chemical Industry Press, in June, 1998 first version " reported to be that the alkylated reaction of catalyst phenol and isopentene obtains 2, the method for 4-two tert-amyl phenols with the boron trifluoride ethyl ether complex.
4) Chinese patent CN101239889A discloses with phenol and isomerizing olefins and made 2 through alkylated reaction, the method for 4-two tert-amyl phenols in the presence of self-control atlapulgite class catalyzer.This method is that a step alkylation process makes the purpose product, and 2, the yield of 4-two tert-amyl phenols is on the low side.
The above-mentioned preparation method who reports adopts different types of catalyzer to exist down and obtains 2 through a step alkylated reaction, 4-two tert-amyl phenols, but all there is raw material isopentene large usage quantity, the recovery that needs complex engineering to carry out iso-butylene just can reduce cost, gained purpose product 2,4-two tert-amyl phenol yields are low, and once through yield is～60%, thereby cause product cost higher, be uneconomic preparation method.
Summary of the invention
In order to overcome the existing weak point of aforesaid method, the invention provides a kind of 2, the new preparation process of 4-two tert-amyl phenols.This method operating process adopts two step alkylations to realize 2, the preparation of 4-two tert-amyl phenols, its process operation is simple and easy to do, processing condition are easy to control, and suitable suitability for industrialized production, the raw materials cost of whole process of production greatly reduces, and products obtained therefrom purity high quality is good, solved problem of environmental pollution simultaneously, be convenient to industrially scalable and implement.Like this, of the present invention 2, the new preparation process of 4-two tert-amyl phenols has overcome the deficiency of former method fully, has realized economy, environmental protection, high-quality 2, the preparation of 4-two tert-amyl phenols.
In order to achieve the above object, the present invention has adopted two-step synthesis preparation 2,4-two tert-amyl phenols.The first step is a raw material with phenol and isopentene at first, is catalyzer with phenol aluminium, and obtaining with adjacent tert-amyl phenol is the reaction solution of main content.Second step added activated bauxite catalyst in this reaction solution, carry out the dioxane glycosylation reaction with isopentene again, obtained 2,4-two tert-amyl phenols.Its reaction principle is as follows:
The inventive method is characterised in that:
It is catalyzer that the first step alkylated reaction adopts phenol aluminium, and isopentene is an alkylating agent.Wherein phenol aluminium is by aluminium bits and phenol reactant and get.To the first step alkylated reaction, be that benchmark calculates with 1mol phenol, aluminium bits consumption is 0.1g～2.0g, isopentene 0.8～1.5mol, temperature of reaction is 70～150 ℃, holding temperature stirred 0.5～5 hour when reaction pressure is constant.It is catalyzer that the second step alkylated reaction adopts atlapulgite, and isopentene is an alkylating agent, is that benchmark calculates with 1mol phenol, and its consumption is atlapulgite 1.0～10.0g, isopentene 0.8～1.5mol, and the alkylated reaction temperature is 70～150 ℃.
The inventive method is compared with original synthetic route, has yield height, remarkable advantage that cost is low, because operating process is simple and easy to do, reaction conditions is easy to control simultaneously, and non-environmental-pollution is beneficial to industrial-scale production, and quality product also can reach excellent level.
Following example helps to understand better the present invention, but does not limit the present invention in any form.
Embodiment
Example 1
In the 1L stainless steel autoclave, add 188.0g (2.0mol) phenol, 0.3g aluminium bits vacuumize and use nitrogen replacement 3 times, stir, and are warming up to 170～190 ℃, stir 2h, are cooled to room temperature then, put pressure.Add 168.0g (2.4mol) isopentene then, stir, be warming up to 100 ℃.Along with the carrying out of reaction, reacting kettle inner pressure descends gradually, and holding temperature when pressure is constant stirs stopped reaction after 4 hours.Add less water after reaction is cooled to about 60 ℃, stir 2h, be cooled to room temperature.Reaction solution is filtered, obtain the monoalkylation reaction solution.
In the 500ml four-hole boiling flask, add above-mentioned gained monoalkylation reaction solution, add atlapulgite 10.0g again, stir then and be warming up to 100 ℃.To wherein being added dropwise to isopentene 162.0g (2.3mol), rate of addition is as the criterion with emission-free overflowing.After treating that isopentene adds, insulated and stirred is 1 hour again.Reacting liquid filtering is got 2,4-two tert-amyl phenol reaction solutions.Extract reaction solution and carry out gas chromatographic analysis, wherein 2,4-two tert-amyl phenol content are 80.5%.Obtain 2 through rectification process, 4-two tert-amyl phenols, content can reach 99.2%.
Example 2
In the 1L stainless steel autoclave, add 188.0g (2.0mol) phenol, 2.0g aluminium bits vacuumize and use nitrogen replacement 3 times.Open and stir, be warming up to 170～190 ℃, stirred 0.5 hour, be cooled to room temperature then, put pressure.In still, add 213.0g (3.0mol) isopentene, stir, be warming up to 100 ℃.Along with the carrying out of reaction, reacting kettle inner pressure descends gradually.Holding temperature when pressure is constant stirs stopped reaction after 0.5 hour.Reaction solution is cooled to about 60 ℃, adds less water, stir 2h, be cooled to room temperature.Reaction solution is filtered, obtain the monoalkylation reaction solution.
In the 500ml four-hole boiling flask, add above-mentioned gained monoalkylation reaction solution, atlapulgite 20.0g stirs then and is warming up to 100 ℃, drips isopentene 213.0g.Rate of addition is as the criterion with emission-free overflowing.After treating that isopentene adds, insulated and stirred is 1 hour again.Reacting liquid filtering is got 2,4-two tert-amyl phenol reaction solutions.Extract reaction solution and carry out gas chromatographic analysis, wherein 2,4-two tert-amyl phenol content 75.2%.
Obtain 2 through rectification process, 4-two tert-amyl phenols, content can reach 99.5%.
Example 3
In the 1L stainless steel autoclave, add 188.0g (2.0mol) phenol, 1.0g aluminium bits vacuumize and use nitrogen replacement 3 times, open and stir.Wait to be warming up to 170～190 ℃ and stir 2h down, be cooled to room temperature then, put pressure.Add 142.0g (2.0mol) isopentene, stir, be warming up to 150 ℃.Along with the carrying out of reaction, reacting kettle inner pressure descends gradually, and holding temperature when pressure is constant stirs stopped reaction after 1.5 hours.Reaction is cooled to about 60 ℃, adds less water, stirred 2 hours, be cooled to 40～50 ℃ again, reaction solution is filtered, obtain the monoalkylation reaction solution.
In the 500ml four-hole boiling flask, add above-mentioned gained monoalkylation reaction solution, atlapulgite 10.0g stirs then and is warming up to 150 ℃, is added dropwise to isopentene 142.0g (2.0mol), and rate of addition is as the criterion with emission-free overflowing.After treating that isopentene adds, insulated and stirred is 0.5 hour again.With reacting liquid filtering, get 2,4-two tert-amyl phenol reaction solutions.Extract reaction solution and carry out gas chromatographic analysis, wherein 2,4-two tert-amyl phenol content 75.6%.
Obtain 2 through rectification process, 4-two tert-amyl phenols, content can reach 99.3%.
Example 4
In the 1L stainless steel autoclave, add 188.0g (2.0mol) phenol, 4.0g aluminium bits vacuumize with nitrogen replacement 3 times, stir, and are warming up to 170～190 ℃ and stir 2h down, put pressure after being cooled to room temperature then.Add 142.0g (2.0mol) isopentene, open and stir, be warming up to 80 ℃.Along with the carrying out of reaction, reacting kettle inner pressure descends gradually, keeps when pressure is constant under this temperature and stirs 1 hour, and stopped reaction is cooled to about 60 ℃ with reaction solution, adds less water, stirs 2h, is cooled to room temperature.Reaction solution is filtered, obtain the monoalkylation reaction solution.
In the 500ml four-hole boiling flask, add above-mentioned monoalkylation reaction solution, atlapulgite 10.0g stirs then and is warming up to 90 ℃, drips isopentene 113.6g (1.6mol), and rate of addition is as the criterion with emission-free overflowing.After treating that isopentene adds, insulated and stirred is 4 hours under this temperature.Reaction solution is filtered, get 2,4-two tert-amyl phenol reaction solutions.Extract reaction solution and carry out gas chromatographic analysis, wherein 2,4-two tert-amyl phenol content 78.2%.
Obtain 2 through rectification process, 4-two tert-amyl phenols, content can reach 99.5%.
Claims (6)
1. the present invention is 2, and the novel method of 4-two tert-amyl phenols preparations is to be raw material with phenol and isopentene, in the presence of different catalysts through two going on foot alkylated reactions, carrying out rectification process again and obtain 2,4-two tert-amyl phenols.
2. according to claim 12, the novel method of 4-two tert-amyl phenols preparation, it is characterized in that: the first step is a raw material with phenol and isopentene, obtaining in the presence of the phenol Al catalysts with adjacent tert-amyl phenol is the monoalkylation reaction solution of main content.Second step was that the dioxane glycosylation reaction is finished in catalyzer and isopentene reaction with adding atlapulgite in this reaction solution, and the gained reaction solution obtains 2 through rectifying, 4-two tert-amyl phenols.
3. according to claim 12, the novel method of 4-two tert-amyl phenols preparation is characterized in that:
1) the first step monoalkylation reaction employing phenol aluminium is catalyzer, make by phenol and the reaction of aluminium bits, and with the isopentene alkylating agent.Phenol aluminium usage quantity is that benchmark calculates with 1.0mol phenol, and aluminium bits usage quantity is 0.1～2.0g.
2) the second step dioxane glycosylation reaction is a raw material with above-mentioned monoalkylation reaction solution, and the employing atlapulgite is a catalyzer, is alkylating agent with the isopentene.With 1.0mol phenol is that benchmark calculates, and the atlapulgite usage quantity is 1.0～10.0g.
4. according to claim 12, the novel method of 4-two tert-amyl phenols preparation is characterized in that: during the reaction of the first step monoalkylation, be that benchmark calculates with 1.0mol phenol, the consumption of isopentene is 0.8～1.5mol; Second step was that benchmark calculates with 1.0mol phenol during the dioxane glycosylation reaction, and the consumption of isopentene is 0.8～1.5mol.
5. according to claim 12, the novel method of 4-two tert-amyl phenols preparation, it is characterized in that: the first step monoalkylation temperature of reaction is 70～150 ℃, the second step dialkyl group temperature of reaction is 70～150 ℃.
6. according to claim 12, the novel method of 4-two tert-amyl phenols preparation, it is characterized in that: the first step monoalkylation reaction times is controlled at and adds after isopentene is warming up to temperature of reaction, and reacting kettle inner pressure no longer reduced stable back clock reaction 0.5～4 hour.The dialkyl group reaction times is for reacting 0.5～4.0 hour after dripping isopentene again.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274905A (en) * | 2013-06-13 | 2013-09-04 | 杨锌荣 | Ortho-position monoalkyl phenol and preparation method thereof |
| CN104529713A (en) * | 2014-12-31 | 2015-04-22 | 蓬莱红卫化工有限公司 | Method for removing phenol-aluminum catalyst from alkylphenol product |
| CN105061157A (en) * | 2015-08-03 | 2015-11-18 | 哈尔滨理工大学 | Method for preparing 4-tert-octyl-2,6-dicumyl phenol |
| CN106699677A (en) * | 2016-12-28 | 2017-05-24 | 利安隆（中卫）新材料有限公司 | Preparation method of ultraviolet absorber UV-571 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4628127A (en) * | 1985-06-25 | 1986-12-09 | Ethyl Corporation | Heterogeneous catalytic alkylation |
| CN1199040A (en) * | 1998-05-09 | 1998-11-18 | 临湘市氨基化学品厂 | Process for preparation of o-secondary butyl phenol |
| CN101239889A (en) * | 2008-02-26 | 2008-08-13 | 江苏工业学院 | Method for preparing reaction liquid containing alkylphenol product |
-
2009
- 2009-12-29 CN CN200910245132A patent/CN101747156A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4628127A (en) * | 1985-06-25 | 1986-12-09 | Ethyl Corporation | Heterogeneous catalytic alkylation |
| CN1199040A (en) * | 1998-05-09 | 1998-11-18 | 临湘市氨基化学品厂 | Process for preparation of o-secondary butyl phenol |
| CN101239889A (en) * | 2008-02-26 | 2008-08-13 | 江苏工业学院 | Method for preparing reaction liquid containing alkylphenol product |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274905A (en) * | 2013-06-13 | 2013-09-04 | 杨锌荣 | Ortho-position monoalkyl phenol and preparation method thereof |
| CN104529713A (en) * | 2014-12-31 | 2015-04-22 | 蓬莱红卫化工有限公司 | Method for removing phenol-aluminum catalyst from alkylphenol product |
| CN104529713B (en) * | 2014-12-31 | 2016-04-13 | 蓬莱红卫化工有限公司 | A kind of method of the phenol Al catalysts removed in alkylphenol product |
| CN105061157A (en) * | 2015-08-03 | 2015-11-18 | 哈尔滨理工大学 | Method for preparing 4-tert-octyl-2,6-dicumyl phenol |
| CN105061157B (en) * | 2015-08-03 | 2017-01-18 | 哈尔滨理工大学 | Method for preparing 4-tert-octyl-2,6-dicumyl phenol |
| CN106699677A (en) * | 2016-12-28 | 2017-05-24 | 利安隆（中卫）新材料有限公司 | Preparation method of ultraviolet absorber UV-571 |
| CN106699677B (en) * | 2016-12-28 | 2019-07-09 | 利安隆（中卫）新材料有限公司 | The preparation method of ultraviolet absorbing agent UV-571 |
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Application publication date: 20100623 |