CN113072430A - Preparation method of 2,4, 6-tri-tert-butylphenol - Google Patents
Preparation method of 2,4, 6-tri-tert-butylphenol Download PDFInfo
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- CN113072430A CN113072430A CN202110357096.7A CN202110357096A CN113072430A CN 113072430 A CN113072430 A CN 113072430A CN 202110357096 A CN202110357096 A CN 202110357096A CN 113072430 A CN113072430 A CN 113072430A
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- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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Abstract
The invention relates to a preparation method of 2,4, 6-tri-tert-butylphenol, which comprises the steps of carrying out alkylation reaction on phenol and isobutene in the presence of an acid catalyst, weighing raw materials according to the mass ratio of the phenol to the catalyst of 100: 1-6, heating and fully mixing, adding isobutene according to the molar ratio of the phenol to the isobutene of 1: 2.5-3.1, controlling the reaction temperature to be 70-100 ℃ and the reaction time to be 4-8 hours, and obtaining 2,4, 6-tri-tert-butylphenol alkylation liquid. The alkylation solution is neutralized, crystallized, washed, filtered and dried to obtain the 2,4, 6-tri-tert-butyl phenol. Rectifying the crystallization mother liquor at normal pressure to recover ethanol, wherein the recovered ethanol can be reused in the crystallization process; the crystallization mother liquor after ethanol removal can be used independently or added with phenol for partial reuse and then subjected to alkylation reaction. The preparation method has the advantages of simple process flow, short reaction period, recyclable raw materials, less three wastes, high product purity and high yield.
Description
Technical Field
The invention relates to the field of organic synthesis, and particularly relates to a preparation method of 2,4, 6-tri-tert-butylphenol.
Background
2,4, 6-tri-tert-butylphenol, abbreviated as antioxidant 246, can effectively improve the weather resistance of the polymer, is mainly used as an antioxidant and an anti-aging agent of rubber, plastic, oil products and other products, can effectively protect the products from yellowing in the storage and use processes, and improves the stability and the weather resistance of the products. Meanwhile, the material has wide application in other fields, for example, when the material is used as a heat stabilizer of polyethylene, polypropylene and impact-resistant polystyrene, the material has the advantages of no pollution and no discoloration; when used as a stabilizer for lubricating oil, fuel oil and biodiesel, the stabilizer has the advantage of preventing the increase of the acid value and the viscosity of the stabilizer. It is also the main raw material for preparing phosphite antioxidants 633, 641, and has good synergistic effect when used together with phosphite antioxidants and ultraviolet absorbers.
No proprietary literature reports have been found regarding the synthetic technology of antioxidant 246. At present, most domestic enterprises mainly produce 2, 4-phenol and co-produce a small amount of 2,4, 6-tri-tert-butylphenol, namely the antioxidant 246 is sold as a byproduct, and the yield is low and the purity is low. With the new requirements of the application field of new materials in recent years, antioxidant BHT must not be contained in materials such as textile industry, automobile industry, furniture industry and the like, so that the antioxidant with better stability is urgently needed to be found. The antioxidant 246 has larger molecular weight than antioxidant BHT (2, 6-di-tert-butyl-4-methylphenol), has lower thermal volatility and better heat resistance, is an efficient stabilizer, can completely replace BHT and meets the new requirements of the application field of new materials.
However, the yield of the antioxidant 246 at home and abroad is small at present, and the market demand can not be met, so that the development of the preparation method of the 2,4, 6-tri-tert-butylphenol with simple process flow, high yield and high product purity has important significance.
Disclosure of Invention
The invention mainly aims to fill the blank of the domestic 2,4, 6-tri-tert-butylphenol preparation process and provide the preparation method of the 2,4, 6-tri-tert-butylphenol, which has the advantages of simple process flow, short reaction period, recyclable raw materials, less three wastes, high product purity and high yield.
In order to achieve the above object, the present invention provides a method for preparing 2,4, 6-tri-tert-butylphenol, comprising the steps of:
s1: preparing raw materials: sequentially adding phenol and an acid catalyst into a reaction kettle according to a proportion, introducing nitrogen for three times for replacement, starting a heating and stirring switch of the reaction kettle, and controlling the temperature and the stirring speed of the reaction kettle to set values to fully mix the phenol and the acid catalyst;
s2: alkylation reaction: adding isobutene into the reaction kettle in which the phenol and the acidic catalyst are fully mixed in the step S1, keeping the temperature of the reaction kettle, carrying out heat preservation reaction, and obtaining 2,4, 6-tri-tert-butylphenol alkylation liquid after the reaction is finished;
s3: and (3) post-treatment: the alkylation solution of 2,4, 6-tri-tert-butylphenol in the step S2 is sequentially subjected to the working procedures of neutralization, crystallization, washing, filtration, drying and the like to obtain a 2,4, 6-tri-tert-butylphenol product;
s4: the solvent is used mechanically: rectifying the crystallization mother liquor remaining from the crystallization step in the step S3 at normal pressure to recover a crystallization solvent ethanol, and using the recovered ethanol in the crystallization step in the step S3; the mother liquid after ethanol removal can be used alone or added with phenol to be used in the alkylation reaction process in the step S2.
Further, the acidic catalyst in step S1 is one or more of sulfuric acid, p-toluenesulfonic acid, heteropolyacid, and strongly acidic cation exchange resin.
Further, the mass ratio of the acidic catalyst to the phenol is 1-6: 100.
Further, the temperature of the reaction kettle in the step S1 is 70-100 ℃.
Further, the molar ratio of the phenol to the isobutene in the step S2 is 1: 2.5-3.1.
Further, the time for the heat preservation reaction in the step S2 is 4-8 h.
Further, the neutralizing agent in step S3 is one or more of sodium hydroxide, potassium hydroxide, or sodium carbonate.
Further, the pH value of the reaction solution after neutralization is 6.8-7.2.
Further, in the step S3, the mass ratio of ethanol to the reaction product during the crystallization process is 1: 2-2: 1.
compared with the prior art, the invention has the beneficial effects that:
the invention fills the blank of the domestic 2,4, 6-tri-tert-butylphenol preparation process, and provides the preparation method of the 2,4, 6-tri-tert-butylphenol, which has the advantages of simple process, short reaction period, easily available raw materials, less three wastes and high product purity.
The attached drawings of the specification:
FIG. 1 is a process flow diagram of a method for preparing 2,4, 6-tri-tert-butylphenol according to the present invention.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of 2,4, 6-tri-tert-butylphenol comprises the following operation steps in sequence:
adding 600g of phenol and 18g of acid catalyst into a 5L reaction kettle, heating after nitrogen replacement, controlling the reaction temperature to be 70-80 ℃, introducing isobutene for reaction for 7-8 hours, completely converting the phenol, and adding a sodium carbonate aqueous solution for neutralization until the mixture is neutral, standing, layering oil and water, removing a water washing layer, adding 1000g of alcohol for crystallization, and filtering. Washing and drying to obtain the 2,4, 6-tri-tert-butylphenol, wherein the purity of the product is 99.34%.
Example 2:
a preparation method of 2,4, 6-tri-tert-butylphenol comprises the following operation steps in sequence:
adding 600g of phenol and 18g of acid catalyst into a 5L reaction kettle, heating after nitrogen replacement, controlling the reaction temperature to be 80-90 ℃, introducing isobutene for reaction for 5-6 hours, completely converting the phenol, and adding sodium carbonate aqueous solution for neutralization until the mixture is neutral, standing, layering oil and water, removing a water washing layer, adding 1500g of alcohol for crystallization, and filtering. Washing and drying to obtain the 2,4, 6-tri-tert-butylphenol, wherein the purity of the product is 99.86%.
Example 3:
a preparation method of 2,4, 6-tri-tert-butylphenol comprises the following operation steps in sequence:
adding 600g of phenol and 18g of acid catalyst into a 5L reaction kettle, heating after nitrogen replacement, controlling the reaction temperature to 90-100 ℃, introducing isobutene for reaction for 4-5 hours, completely converting the phenol, and adding a sodium carbonate aqueous solution for neutralization until the mixture is neutral, standing, layering oil and water, removing a water washing layer, adding 2000g of alcohol for crystallization, and filtering. Washing and drying to obtain the 2,4, 6-tri-tert-butylphenol, wherein the purity of the product is 99.97%.
Claims (9)
1. A preparation method of 2,4, 6-tri-tert-butylphenol is characterized in that: the operation steps are as follows in sequence:
s1: preparing raw materials: sequentially adding phenol and an acid catalyst into a reaction kettle according to a proportion, introducing nitrogen for three times for replacement, starting a heating and stirring switch of the reaction kettle, and controlling the temperature and the stirring speed of the reaction kettle to set values to fully mix the phenol and the acid catalyst;
s2: alkylation reaction: adding isobutene into the reaction kettle in which the phenol and the acidic catalyst are fully mixed in the step S1, keeping the temperature of the reaction kettle, carrying out heat preservation reaction, and obtaining 2,4, 6-tri-tert-butylphenol alkylation liquid after the reaction is finished;
s3: and (3) post-treatment: the alkylation solution of 2,4, 6-tri-tert-butylphenol in the step S2 is sequentially subjected to the working procedures of neutralization, crystallization, washing, filtration, drying and the like to obtain a 2,4, 6-tri-tert-butylphenol product;
s4: the solvent is used mechanically: rectifying the crystallization mother liquor remaining from the crystallization step in the step S3 at normal pressure to recover a crystallization solvent ethanol, and using the recovered ethanol in the crystallization step in the step S3; the mother liquid after ethanol removal can be used alone or added with phenol to be used in the alkylation reaction process in the step S2.
2. The method of claim 1, wherein the acidic catalyst in step S1 is one or more of sulfuric acid, p-toluenesulfonic acid, heteropoly acid, and strongly acidic cation exchange resin.
3. The method for preparing 2,4, 6-tri-tert-butylphenol according to claim 2, wherein the mass ratio of the acidic catalyst to phenol is 1-6: 100.
4. The method for preparing 2,4, 6-tri-tert-butylphenol according to claim 1, wherein the temperature of the reaction vessel in step S1 is 70-100 ℃.
5. The method for preparing 2,4, 6-tri-tert-butylphenol according to claim 1, wherein the molar ratio of phenol to isobutylene in step S2 is 1: 2.5 to 3.1.
6. The method according to claim 1, wherein the time for the heat-preservation reaction in step S2 is 4-8 h.
7. The method of claim 1, wherein the neutralizing agent in step S3 is one or more of sodium hydroxide, potassium hydroxide, and sodium carbonate.
8. The method of claim 7, wherein the pH of the neutralized reaction solution is 6.8 to 7.2.
9. The method for preparing 2,4, 6-tri-tert-butylphenol according to claim 1, wherein in step S3, the mass ratio of ethanol to reaction product during the crystallization is 1: 2-2: 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113636916A (en) * | 2021-09-17 | 2021-11-12 | 陕西万汇能聚科技有限公司 | Method for synthesizing 2,4, 6-tri-tert-butylphenol |
| CN117801197A (en) * | 2024-02-27 | 2024-04-02 | 安徽觅拓材料科技有限公司 | Preparation method and application of phenol anti-crystallization agent |
| CN117801197B (en) * | 2024-02-27 | 2024-05-17 | 安徽觅拓材料科技有限公司 | Preparation method and application of phenol anti-crystallization agent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092331A (en) * | 2007-07-06 | 2007-12-26 | 宁波金海雅宝化工有限公司 | Method for synthesizing alkyl phenol by fixed bed |
-
2021
- 2021-04-01 CN CN202110357096.7A patent/CN113072430A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092331A (en) * | 2007-07-06 | 2007-12-26 | 宁波金海雅宝化工有限公司 | Method for synthesizing alkyl phenol by fixed bed |
Non-Patent Citations (1)
| Title |
|---|
| 李杰等: "苯酚烷基化催化剂研究进展", 《应用化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113636916A (en) * | 2021-09-17 | 2021-11-12 | 陕西万汇能聚科技有限公司 | Method for synthesizing 2,4, 6-tri-tert-butylphenol |
| CN113636916B (en) * | 2021-09-17 | 2023-08-29 | 陕西万汇能聚科技有限公司 | Method for synthesizing 2,4, 6-tri-tert-butylphenol |
| CN117801197A (en) * | 2024-02-27 | 2024-04-02 | 安徽觅拓材料科技有限公司 | Preparation method and application of phenol anti-crystallization agent |
| CN117801197B (en) * | 2024-02-27 | 2024-05-17 | 安徽觅拓材料科技有限公司 | Preparation method and application of phenol anti-crystallization agent |
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Inventor after: Yang Xianglian Inventor after: Chen Fuxin Inventor after: Dai Jie Inventor after: He Jinyi Inventor after: Xin Xuan Inventor before: He Jinyi Inventor before: Chen Fuxin Inventor before: Yang Xianglian Inventor before: Dai Jie Inventor before: Xin Xuan |
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Application publication date: 20210706 |
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