CN100412043C - Process for preparing 4,6-di-tert-butyl resorcin with resin as catalyst - Google Patents
Process for preparing 4,6-di-tert-butyl resorcin with resin as catalyst Download PDFInfo
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- CN100412043C CN100412043C CNB2006100139876A CN200610013987A CN100412043C CN 100412043 C CN100412043 C CN 100412043C CN B2006100139876 A CNB2006100139876 A CN B2006100139876A CN 200610013987 A CN200610013987 A CN 200610013987A CN 100412043 C CN100412043 C CN 100412043C
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- resorcinol
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Abstract
The present invention provides a method for preparing 4, 6-di-tert-butyl resorcinol by resin catalysis. The present invention has the specific technical scheme that resorcinol, tert-butyl alcohol and 1, 2-dichloroethane as solvent are put in a reaction vessel and are heated into a temperature of 30 to 40 DEG C; after the whole raw materials are dissolved, acid-exchange resin as a catalyst is added and the temperature continuously rises to 60 to 65 DEG C to carry out tertiary-butyl reaction for 5 to 8 hours; after the alkylation reaction, reacted products are filtered while hot to separate out acid-exchange resin for recovery; filter liquor is added to water to separate out products; after filtration and washing, the purpose product of 4, 6-di-tert-butyl resorcinol is obtained. The present invention has the advantages of mild reaction condition, easy control, purpose product with good quality and yield because of side reaction reduction, high catalyst selectivity of acid-exchange resin, simple and convenient separation, recovery, production cost reduction and little environment pollution; the present invention avoids a large amount of liquid acid being used as catalysts to reduce the equipment corrosion, and does not generate a large amount of waste acid and waste water.
Description
Technical field
The invention belongs to the preparation method of alkyl-substituted phenols compounds, proposed a kind of resin catalysis preparation 4 especially, the method for 6-di-tert-butyl resorcin.
Background technology
4, the 6-di-tert-butyl resorcin claims 4 again, 6-di-t-butyl-1, and the 3-dihydroxy-benzene is the intermediate of important synthetic organic fine chemical, and is of many uses.
Its main preparation methods is to be raw material with the Resorcinol, under the acid catalyst effect, by the Friedel-Crafts alkylated reaction, respectively introduces a tertiary butyl 4,6 of Resorcinols, promptly can obtain 4, the 6-di-tert-butyl resorcin.The catalyzer of Cai Yonging mainly was the vitriol oil in the past, and phosphoric acid etc., tert-butylation reagent mainly are iso-butylene, the trimethyl carbinol etc.Adopt the vitriol oil to make the catalyst technology maturation, product yield is higher, but vitriol oil consumption is big, and equipment corrosion is serious, the product aftertreatment is comparatively loaded down with trivial details, reaction process produces a large amount of spent acid waste water, has increased production cost and discharge of wastewater, simultaneously, the vitriol oil is done the side reactions such as polymerization, esterification, dehydration and oxidation that catalyzer may produce aromatic hydrocarbons sulfonation, alkylating reagent, to catalyst levels, concentration has higher requirements, and has influenced quality product and yield.
Summary of the invention
Make Preparation of Catalyst 4 at the existing vitriol oil that adopts, the deficiency of 6-di-tert-butyl resorcin, it is a kind of 4 that the present invention proposes especially, the new preparation process of 6-di-tert-butyl resorcin.Use a kind of acidic ion exchange resin to make catalyzer, successfully prepared 4, the 6-di-tert-butyl resorcin, and reduce the influence of side reaction, improved quality product, reduced corrosion equipment, reduce production costs, avoid the pollution of spent acid, waste water environment.
The present invention adopts a kind of acidic ion exchange resin to replace the vitriol oil to make catalyzer, is raw material, 1 with Resorcinol, the trimethyl carbinol, and the 2-ethylene dichloride prepares 4 as reaction solvent, the 6-di-tert-butyl resorcin, and concrete steps are as follows:
With Resorcinol, the trimethyl carbinol and solvent 1, the 2-ethylene dichloride drops in the reactor, is heated to 30～40 ℃, treats that raw material all after the dissolving, adds acidity of catalyst ion exchange resin, continues to be warming up to 60～65 ℃, carries out tertiary butyl reaction, reaction times 5～8h; After alkylated reaction finished, filtered while hot was told acidic ion exchange resin recovery set usefulness, and filtrate is added in the entry, separates out product, filtered, and obtained purpose product 4 after the washing, the 6-di-tert-butyl resorcin.Solvent 1, reclaim 2-ethylene dichloride distillation back.
Wherein material proportion is:
Resorcinol and 1, the mass ratio of 2-ethylene dichloride are 1: 4～8
The mass ratio of Resorcinol and acidic ion exchange resin is 1: 0.9～1.8
The mass ratio of the Resorcinol and the trimethyl carbinol is 1: 1.6～1.9.
The trade names of acidic ion exchange resin are NKC-9,001 * 1,001 * 7, but better with NKC-9.Its chemical structure is strongly acidic styrene type cation exchange resin.
It is a kind of 4 that the present invention proposes, and the new preparation process of 6-di-tert-butyl resorcin adopts acidic ion exchange resin to make catalyzer, has compared following advantage with existing concentrated sulfuric acid catalyst technology; The reaction conditions gentleness is easy to control, owing to reduced side reaction, has obtained quality, the better purpose product of yield; Acidic ion exchange resin catalyst selectivity height, use to separate easy, can recovery set usefulness, reduce production costs; Avoid using a large amount of liquid acid as catalyst, reduce corrosion equipment; Do not produce a large amount of spent acid waste water, environmental pollution is little.
Embodiment
Embodiment 1
With 100mL 1,2-ethylene dichloride, the 41g trimethyl carbinol and 22g Resorcinol input are equipped with in the 250mL four-hole bottle of reflux exchanger, stir down heat temperature raising to 30 ℃, after treating that material fully dissolves, adding the 35g trade names is the strongly acidic styrene type cation exchange resin of NKC-9, continues to be warming up to 65 ℃ of reaction 6h, and solution colour is deepened gradually, reaction finishes, and obtains the scarlet clear solution.The material filtered while hot is divided disacidify ion exchange resin, and filtrate is poured in the 100mL cold water, stir, separate out white products immediately, solution is red, leave standstill, treat that product is fully separated out after, filter, filter cake washs with the making beating of 100mL hot water, refilter, oven dry obtains 4,6-di-tert-butyl resorcin 38.1g, yield 85.8%.
Embodiment 2
With 100mL 1,2-ethylene dichloride, the 41g trimethyl carbinol and 22g Resorcinol input are equipped with in the 250mL four-hole bottle of reflux exchanger, stir down heat temperature raising to 30 ℃, after treating that material fully dissolves, add 30g acidic ion exchange resin NKC-9, continue to be warming up to 60 ℃ of reaction 6h, solution colour is deepened gradually, reaction finishes, and obtains the scarlet clear solution.The material filtered while hot is divided disacidify ion exchange resin, and filtrate is poured in the 100mL cold water, stir, separate out white products immediately, solution is red, leave standstill, treat that product is fully separated out after, filter, filter cake washs with the making beating of 100mL hot water, refilter, oven dry obtains 4,6-di-tert-butyl resorcin 36.2g, yield 81.5%.
Embodiment 3
With 100mL 1,2-ethylene dichloride, the 37g trimethyl carbinol and 22g Resorcinol input are equipped with in the 250mL four-hole bottle of reflux exchanger, stir down heat temperature raising to 40 ℃, treat that material fully dissolves, add 35g acidic ion exchange resin NKC-9, continue to be warming up to 65 ℃ of reaction 6h, solution colour is deepened gradually, reaction finishes, and obtains the scarlet clear solution.The material heat filtering divides disacidify ion exchange resin, and filtrate is poured in the 100mL cold water, stir, separate out white products immediately, solution is red, leave standstill, treat that product is fully separated out after, filter, filter cake washs with the making beating of 100mL hot water, refilter, oven dry obtains 4,6-di-tert-butyl resorcin 35.5g, yield 80.0%.
Embodiment 4
With 140mL 1,2-ethylene dichloride, the 41g trimethyl carbinol and 22g Resorcinol input are equipped with in the 250mL four-hole bottle of reflux exchanger, stir down heat temperature raising to 30 ℃, treat that material fully dissolves, add 39g acidic ion exchange resin NKC-9, continue to be warming up to 65 ℃ of reaction 8h, solution colour is deepened gradually, reaction finishes, and obtains the scarlet clear solution.The material heat filtering divides disacidify ion exchange resin, and filtrate is poured in the 100mL cold water, stir, separate out white products immediately, solution is red, leave standstill, treat that product is fully separated out after, filter, filter cake washs with the making beating of 100mL hot water, refilter, oven dry obtains 4,6-di-tert-butyl resorcin 36.8g, yield 83.0%.
Embodiment 5
With 70mL 1,2-ethylene dichloride, the 35.5g trimethyl carbinol and 22g Resorcinol input are equipped with in the 250mL four-hole bottle of reflux exchanger, stir down heat temperature raising to 35 ℃, treat that material fully dissolves, add 20g acidic ion exchange resin NKC-9, continue to be warming up to 60 ℃ of reaction 5h, solution colour is deepened gradually, reaction finishes, and obtains the scarlet clear solution.The material heat filtering divides disacidify ion exchange resin, and filtrate is poured in the 100mL cold water, stir, separate out white products immediately, solution is red, leave standstill, treat that product is fully separated out after, filter, filter cake washs with the making beating of 100mL hot water, refilter, oven dry obtains 4,6-di-tert-butyl resorcin 35.1g, yield 79.0%.
Embodiment 6
Except acidic ion exchange resin NKC-9 being changed into trade names is that other operation and processing condition are with embodiment 1 001 * 1 the strongly acidic styrene type cation exchange resin, and the result obtains 4,6-di-tert-butyl resorcin 34.5g, yield 77.7%.
Embodiment 7
Except acidic ion exchange resin NKC-9 being changed into trade names is that other operation and processing condition are with embodiment 1 001 * 7 the strongly acidic styrene type cation exchange resin, and the result obtains 4,6-di-tert-butyl resorcin 35.5g, yield 80%.
Embodiment 6
Except the ethylene dichloride of the NKC-9 that use to reclaim and recovery, other operation and processing condition are with embodiment 1, and the result obtains 4,6-di-tert-butyl resorcin 37.5g, yield 84.5%.
The present invention is not limited to the technology described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on present technique field personnel according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (3)
1. resin catalysis preparation 4, the method of 6-di-tert-butyl resorcin, it is characterized in that: with Resorcinol, the trimethyl carbinol and solvent 1, the 2-ethylene dichloride drops in the reactor, be heated to 30～40 ℃, treat that raw material all after the dissolving, adds the strongly acidic styrene type cation exchange resin catalyzer, continue to be warming up to 60～65 ℃, reaction times 5～8h; Filtered while hot adds filtrate in the entry, separates out product;
Wherein material proportion is:
Resorcinol and 1, the mass ratio of 2-ethylene dichloride are 1: 4～8
The mass ratio of Resorcinol and acidic ion exchange resin is 1: 0.9～1.8
The mass ratio of the Resorcinol and the trimethyl carbinol is 1: 1.6～1.9.
2. resin catalysis preparation 4 as claimed in claim 1, the method for 6-di-tert-butyl resorcin is characterized in that described strongly acidic styrene type cation exchange resin is NKC-9,001 * 1 or 001 * 7.
3. resin catalysis preparation 4 as claimed in claim 1, the method for 6-di-tert-butyl resorcin, the strongly acidic styrene type cation exchange resin recovery set usefulness of telling after it is characterized in that filtering, 1, reclaim 2-ethylene dichloride distillation back.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100139876A CN100412043C (en) | 2006-05-31 | 2006-05-31 | Process for preparing 4,6-di-tert-butyl resorcin with resin as catalyst |
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| CNB2006100139876A CN100412043C (en) | 2006-05-31 | 2006-05-31 | Process for preparing 4,6-di-tert-butyl resorcin with resin as catalyst |
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| CN1884244A CN1884244A (en) | 2006-12-27 |
| CN100412043C true CN100412043C (en) | 2008-08-20 |
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| CN110803980B (en) * | 2019-11-25 | 2022-05-06 | 重庆东寰科技开发有限公司 | Method for preparing 4-n-butylresorcinol by one-pot method |
| CN111909209A (en) * | 2020-08-10 | 2020-11-10 | 惠州凯特立斯科技有限公司 | Preparation method of biphenyl tetradentate phosphonite ligand |
| CN112341494A (en) * | 2020-10-14 | 2021-02-09 | 惠州凯特立斯科技有限公司 | Novel large steric hindrance biphenyl triphenol skeleton and synthetic method of tridentate phosphonite ligand thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030125586A1 (en) * | 2001-03-30 | 2003-07-03 | Narayanan Sankarasubbier | Process for preparing alkylated dihydroxybenzene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030125586A1 (en) * | 2001-03-30 | 2003-07-03 | Narayanan Sankarasubbier | Process for preparing alkylated dihydroxybenzene |
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