CN1445204A - Reaction method of aromatics of tertiary butyl by using methyl tert-butyl ether as alkylating agent - Google Patents
Reaction method of aromatics of tertiary butyl by using methyl tert-butyl ether as alkylating agent Download PDFInfo
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- CN1445204A CN1445204A CN 03113595 CN03113595A CN1445204A CN 1445204 A CN1445204 A CN 1445204A CN 03113595 CN03113595 CN 03113595 CN 03113595 A CN03113595 A CN 03113595A CN 1445204 A CN1445204 A CN 1445204A
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- tertiary butyl
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Abstract
A process for using methyl tert-butyl ether as hydroxylating agent in tert-butylation reaction of aryhydrocarbon compound features use of acid as catalyst. Its advantages are mild reaction, short reaction time and low cost.
Description
Technical field
The present invention relates to the chemical reaction method that a kind of fine chemical product is produced, particularly a kind of is the aromatic hydrocarbon tertiary butyl reaction method of alkylating agent with the methyl tertiary butyl ether.
Background technology
Classical Fridel-Crafts alkylated reaction (being called for short the F-C alkylated reaction), be with haloalkane, alcohol, olefines in the presence of catalyzer, the alkylated reaction of aromatic nucleus takes place, " name reaction in the organic chemistry " 125-129 page or leaf of the Yu Ling Chong that Science Press published in 1984 is on the books, on aromatic nucleus, introduce the tertiary butyl, then be F-C tertiary butyl reaction.A series of fine chemical product has been developed in this reaction, as the high-efficiency polymerization inhibitor p-ten.-butylcatechol of monomer alkene in refining and storage and transport process; Superpolymer such as polypropylene and elastomeric oxidation inhibitor or anti-aging agent, food antioxidant 2, the 6-toluene di-tert-butyl phenol; The intermediate of lubricating oil and greasy stablizer and UV light absorber etc.For a long time, introducing alkylating agent that the tertiary butyl adopted on aromatic nucleus has two kinds of the trimethyl carbinol or iso-butylenes, all need use solvent such as dimethylbenzene etc. during reaction.The trimethyl carbinol costs an arm and a leg, and causes purpose product price height; Iso-butylene needs from splitting gas C
4Separate in the fraction, and C
4The boiling point of contained butene-1, butene-2, divinyl, iso-butylene is-6.3 ℃, 3.5 ℃ ,-4.45 ℃ ,-6 ℃ respectively in the fraction, and is of slight difference each other, therefore, the rectifying device of separation and purification iso-butylene take and operational cost all higher.And when making the alkylating agent of tertiary butyl reaction with iso-butylene, the reaction times is very long; Make alkylating agent with iso-butylene, also can be with C
4Fraction directly feeds reactor and carries out tertiary butyl reaction without separation, but energy consumption is bigger like this, has increased process cost, and cost is higher.
Methyl tertiary butyl ether is in separation of C
4Add methyl alcohol in the fraction process, the iso-butylene in this fraction promptly reacts generation, its boiling point and C with methyl alcohol under the catalysis of storng-acid cation exchange resin
4All the other component boiling points in the fraction differ big (55.2 ℃), thus be easy to be separated, promptly from C
4Obtain methyl tertiary butyl ether in the fraction than from C
4It is much lower to obtain the required expense of iso-butylene in the cut.The purposes of methyl tertiary butyl ether is to be used for replacing the octane number additive of tetraethyllead as gasoline.
When making alkylating agent with iso-butylene, for example when preparing high-efficiency polymerization inhibitor to the tert-butyl o diphenol, it is raw material with the pyrocatechol, with dimethylbenzene is solvent, phosphoric acid does catalyst, obtain 105～110 ℃ of following successive reactions of temperature 67～72 hours, see Liaoning petrochemical technology information master station " Organic Chemicals and intermediate brief guide)) next part, 56～57 pages.Topic is a long reaction time between its existence, the 2nd, and solvent xylene is deleterious flammable and explosive substance, operational danger is big, and the cost height, influences economic benefit.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art and provide a kind of new be the aromatic hydrocarbon tertiary butyl reaction method of alkylating agent with the methyl tertiary butyl ether, simplify production technique, shorten the reaction times, reduce production costs, increase economic efficiency.
Purpose of the present invention can realize by following technical measures: present method is raw material with the arene compound, add methyl tertiary butyl ether as alkylating agent, acid as catalyst, its temperature of reaction is 60～160 ℃, be preferably 80～150 ℃, reaction times is 1.0～8 hours, the molar ratio of arene compound and methyl tertiary butyl ether is 1: 0.8～3, be preferably 1: 1.05～1.3, arene compound is 1: 0.05～0.3 with the weight ratio of acid, be preferably 1: 0.1～0.2, the weight of acid is the weight of pure acid.
Described arene compound can be monoalkyl substituted benzene, many alkyl substituted benzenes, phenol, alkyl substituted phenol and neighbour, to, Resorcinol;
Used acid can be the mixture that phosphoric acid, tosic acid, sulfuric acid and solid Zeo-karb or solid Zeo-karb add mineral acid, and above-mentioned solid Zeo-karb needs to handle through transition.
Aromatic hydrocarbon is introduced tertiary butyl reaction can adopt a step feed way, and arene compound, methyl tertiary butyl ether, acid are added in the reactor together, and heating is then stirred and reacted; Also can adopt the substep feed way, arene compound is added in the reactor, heating then adds methyl tertiary butyl ether, acid is stirred and to be reacted again.
The reaction mechanism of the present invention and the employing trimethyl carbinol or iso-butylene are made alkylating agent, and the mechanism of carrying out tertiary butyl reaction with arene compound is identical.Ether bond rupture takes place in acid as under the catalyzer in methyl tertiary butyl ether, produces tertiary butyl carbonium ion, and the big л key on aromatic nucleus starts close electric attack and makes the aromatic nucleus tert-butylation.
Technology of the present invention is simple, the reaction conditions gentleness is feasible, the alkylating agent source is easy, and reaction does not need solvent, and energy consumption is little, reaction times is short, process cost is low, can effectively reduce the cost of purpose product, increases economic efficiency, for the intermediate of various high-efficiency polymerization inhibitors, oxidation inhibitor, anti-aging agent and lubricating oil and greasy stablizer, UV light absorber has been opened up a kind of new synthetic method, and provide a kind of new purposes for methyl tertiary butyl ether.
Embodiment
The temperature of reaction that aromatic hydrocarbon is introduced the tertiary butyl is preferably 80～150 ℃, reaction times is preferably 2.5～5 hours, the molar ratio of arene compound and methyl tertiary butyl ether is preferably 1: 1.05～and 1.3, arene compound is preferably 1: 0.1 with the weight ratio of acid～and 0.2.
Embodiment one:
In the reactor that has thermometer, agitator and reflux exchanger, add pyrocatechol 28g, methyl tertiary butyl ether 22g, concentration is 98% sulfuric acid 1.4g, stirs and is warming up to 100 ℃, hold-time 1.5h, the product of acquisition is 55.66% to tert-butyl o diphenol content.
Embodiment two:
In the reactor that has thermometer, agitator and reflux exchanger, add pyrocatechol 28g, methyl tertiary butyl ether 22g, 701 type Zeo-karb 2.75g were warming up to 120 ℃ of stirring reactions 2.5 hours, and the acquisition product is 25.36% to the content of tert-butyl o diphenol.
Embodiment three:
In the reactor that has thermometer, agitator and reflux exchanger, add phenol 23.5g, be heated to 130 ℃ after, add methyl tertiary butyl ether 23.7g, concentration is 98% sulfuric acid 2.57g, stirring reaction 3 hours obtains the p-tert-butylphenol 23g of product.
Embodiment four:
In the reactor that has thermometer, agitator and reflux exchanger, add phenol 28.2g, methyl tertiary butyl ether 22g, concentration is 86% phosphoric acid 2.64g, stirs and is warming up to 130 ℃, add the back and keep reaction 2.5 hours, the content that obtains the product p-tert-butylphenol is 24.7%.
Embodiment five:
In the reactor that has thermometer, agitator and reflux exchanger, add toluene 23g, methyl tertiary butyl ether 23g, concentration is 98% sulfuric acid 2.6g, stirs and is warming up to 110 ℃, add the back and keep reaction 2 hours, the content that obtains the product p-tert-butyltoluene is 15.7%.
Claims (7)
1. one kind is the aromatic hydrocarbon tertiary butyl reaction method of alkylating agent with the methyl tertiary butyl ether, is raw material with the arene compound, it is characterized in that adding methyl tertiary butyl ether as alkylating agent, acid as catalyst.
2. reaction method according to claim 1, the molar ratio that it is characterized in that arene compound and methyl tertiary butyl ether is 1: 0.8～3, and arene compound is 1: 0.05～0.3 with the weight ratio of acid, and temperature of reaction is 60～160 ℃.
3. reaction method according to claim 1, it is characterized in that arene compound be monoalkyl substituted benzene, many alkyl substituted benzenes, phenol, alkyl substituted phenol and neighbour, to, Resorcinol.
4. reaction method according to claim 1, the acid that it is characterized in that catalyzer are the mixture that phosphoric acid, tosic acid, sulfuric acid and solid Zeo-karb or solid Zeo-karb add mineral acid.
5. reaction method according to claim 1, the molar ratio that it is characterized in that arene compound and methyl tertiary butyl ether is 1: 1.05～1.3.
6. reaction method according to claim 1 is characterized in that the arene compound and the weight ratio of acid are 1: 0.1～0.2.
7. reaction method according to claim 1 is characterized in that temperature of reaction is 80～150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03113595 CN1445204A (en) | 2003-01-15 | 2003-01-15 | Reaction method of aromatics of tertiary butyl by using methyl tert-butyl ether as alkylating agent |
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| CN 03113595 CN1445204A (en) | 2003-01-15 | 2003-01-15 | Reaction method of aromatics of tertiary butyl by using methyl tert-butyl ether as alkylating agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352795C (en) * | 2005-09-28 | 2007-12-05 | 茂名学院 | 2-tertiary-butyl hydroquinone preparation method |
| CN103319315A (en) * | 2013-06-17 | 2013-09-25 | 湖北工业大学 | Method for producing aggregate-type hindered phenol antioxidant |
| CN103420807A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
| CN109081771A (en) * | 2018-03-20 | 2018-12-25 | 江苏极易新材料有限公司 | A kind of preparation method of 2,4- DI-tert-butylphenol compounds |
-
2003
- 2003-01-15 CN CN 03113595 patent/CN1445204A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352795C (en) * | 2005-09-28 | 2007-12-05 | 茂名学院 | 2-tertiary-butyl hydroquinone preparation method |
| CN103420807A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
| CN103319315A (en) * | 2013-06-17 | 2013-09-25 | 湖北工业大学 | Method for producing aggregate-type hindered phenol antioxidant |
| CN109081771A (en) * | 2018-03-20 | 2018-12-25 | 江苏极易新材料有限公司 | A kind of preparation method of 2,4- DI-tert-butylphenol compounds |
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