CN103553880B - Synthetic method of para-tert-butylcatechol - Google Patents
Synthetic method of para-tert-butylcatechol Download PDFInfo
- Publication number
- CN103553880B CN103553880B CN201310567693.8A CN201310567693A CN103553880B CN 103553880 B CN103553880 B CN 103553880B CN 201310567693 A CN201310567693 A CN 201310567693A CN 103553880 B CN103553880 B CN 103553880B
- Authority
- CN
- China
- Prior art keywords
- butylcatechol
- tert
- para
- catalyst
- synthetic method
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- 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
- C07C37/16—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 condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
Abstract
The invention provides a synthetic method of para-tert-butylcatechol, and particularly provides a method for synthesizing the para-tert-butylcatechol by taking loading type polyoxometalates as a catalyst and heterogeneously catalyzing tert-butyl alcohol and catechol. According to the invention, the used catalyst is a loading type polyoxometalates catalyst which contains positive ions, namely Rb, Cs, Rh, and the like, has the characteristics of high activity, high selectivity and long life and can be recycled. The synthetic method provided by the invention has very small usage amount of the used catalyst, can directly obtain the crude product and directly carry out distillation and purification and has good application prospect in the industrial production of the para-tert-butylcatechol.
Description
Technical field
The present invention relates to catalytic field, relate in particular to a kind of synthetic method of p-ten.-butylcatechol.
Background technology
P-ten.-butylcatechol is called for short TBC, for white is to pale yellow crystals, mainly with being high-efficiency polymerization inhibitor when olefinic monomer distillation and accumulating, be specially adapted to vinylbenzene, divinyl, vinylchlorid, vinyl pyridine, vinylformic acid, methacrylic acid and other vinyl monomer; P-ten.-butylcatechol also can be used for polymkeric substance and the oils such as polyethylene, polyhutadiene, nylon and synthetic rubber, lubricating oil, hexanolactam, the oxidation inhibitor of the multiple compounds such as maleic anhydride and metallic soap, also can be used as the passivator of urethane catalyst, the stablizer etc. of various organic compound, soil, sterilant simultaneously.
Day JP 49-127932, day special permission discloses flat 2-152939 and individually discloses pyrocatechol and iso-butylene reacts the method preparing TBC under oleum exists, namely be catalyzer with oleum, control sulfuric acid, iso-butylene and pyrocatechol amount ratio, react at a certain temperature, react and neutralized with sodium hydroxide solution, or add the organic solvent extractions such as toluene, rectifying obtains product, above-mentioned synthetic method only makes catalyst with oleum, reaction is fierce, be difficult to control, impurity is many, need neutralization simultaneously, washing catalyzer, bring the problems such as acid-bearing wastewater process and the loss of raw material pyrocatechol.
At present, domestic synthesis TBC main technique is that the phosphoric acid method of pyrocatechol and sulfuric acid process catalyze and synthesize, pyrocatechol phosphoric acid method and sulfuric acid process catalysis synthesis process are under about 1:1 phosphoric acid or sulfuric acid and catalyzer existent condition, drip trimethyl carbinol synthesis, carry out layering, in and, washing, obtain finished product after underpressure distillation.The production cost of existing method is higher, and product yield is low, and quality index is relatively low, unless be further processed, and discharge acid, salt is more, contaminate environment is more serious.The method mentioned in Chinese patent CN1303843A, adopts single acid or resin cation (R.C.) to synthesize TBC as catalyzer, also directly rectifying can obtain product, but the method uses catalytic amount larger, poor selectivity, by product is more, affects quality product and synthesis yield.
At present, not yet have with carried heteropoly acid salt for catalyzer, the method report of synthesis TBC.
summary of the invention:
The object of the invention is to overcome above operational path Problems existing, provide that a kind of method is simple, high reactivity, the method for the synthesis of p-ten.-butylcatechol of high life.
Main technical schemes of the present invention is: a kind of synthetic method of p-ten.-butylcatechol, it is characterized in that with the trimethyl carbinol, pyrocatechol for raw material, working load type heteropolyacid salt catalyst, under nitrogen atmosphere, reacts 0.5 ~ 5 hour, temperature of reaction 80
oc ~ 120
oc, control reaction pressure is negative pressure, the trimethyl carbinol: pyrocatechol (mol ratio) is 1:1 ~ 2.5.
The catalyzer used in the present invention is carried heteropoly acid salt catalyst, heteropolyacid anions is the heteropolymolybdate of structure with Keggin, heteroatoms is P or As, and counter cation is H or Cs, and the carrier of load can be dealuminzation USY molecular sieve, MCM-41 molecular sieve or ion exchange resin etc.
In the present invention, use catalyst levels less, the consumption of catalyzer is 0.03% ~ 1%(mass percent of trimethyl carbinol intake), and catalyzer can be recycled.
In the present invention, can directly obtain thick product, impurity is few, and directly rectifying can obtain product, productive rate is greater than 90%.
Method advantage used in the present invention is: both do not had the neutralization needed for traditional method, water washing process, additionally reduces the problem of environmental pollution brought containing alcohol, acid-bearing wastewater; And the method for the invention, the carried heteropoly acid salt catalyst of use is heterogeneous catalyst, is easily separated, high-activity high-selectivity, and product can directly rectifying, and impurity is few, and product yield is high; And this carried heteropoly acid salt catalyst, capable of circulationly repeatedly uses, by simple process and renewable after activity decrease, and keep and fresh same activity.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
Containing carried heteropoly acid salt catalyst (Cs
3pMo
12o
40, load on MCM-41, charge capacity 5%) fixed bed reactor in, pass into N
2ten minutes, be heated to 100
oc, add 200g pyrocatechol to dissolving, lower bubbling passes into trimethyl carbinol 60g, and keep system pressure negative pressure, react 3 hours, transformation efficiency 82%, the direct rectifying of material, obtains p-ten.-butylcatechol product purity>=99%, yield 90%.
Reaction mixture gas chromatographic analysis result following (%):
Pyrocatechol 16.6; TBC 82.9; 3,5-DTBC 0.5.
Embodiment 2
Containing carried heteropoly acid salt catalyst (H
3asMo
12o
40, load in dealuminzation USY molecular sieve, charge capacity 3%) fixed bed reactor in, pass into N
2ten minutes, be heated to 120
oc, add 200g pyrocatechol to dissolving, lower bubbling passes into trimethyl carbinol 80g, and keep system pressure negative pressure, react 2 hours, transformation efficiency 92%, the direct rectifying of material, obtains p-ten.-butylcatechol product purity>=99%, yield 95%.
Reaction mixture gas chromatographic analysis result following (%):
Pyrocatechol 7.6; TBC 92.0; 3,5-DTBC 0.4.
Embodiment 3
Containing carried heteropoly acid salt catalyst (H
3asMo
12o
40, load in dealuminzation USY molecular sieve, charge capacity 5%) fixed bed reactor in, pass into N
2ten minutes, be heated to 80
oc, add 180g pyrocatechol to dissolving, lower bubbling passes into trimethyl carbinol 60g, and keep system pressure negative pressure, react 4 hours, transformation efficiency 85%, the direct rectifying of material, obtains p-ten.-butylcatechol product purity>=99%, yield 88%.
Reaction mixture gas chromatographic analysis result following (%):
Pyrocatechol 13.2; TBC 80.7; 3,5-DTBC 6.1.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (1)
1. a synthetic method for p-ten.-butylcatechol, is characterized in that, with the trimethyl carbinol, pyrocatechol for raw material, working load type heteropolyacid salt catalyst, under nitrogen atmosphere, reacts 0.5 ~ 5 hour, temperature of reaction 80
oc ~ 120
oc, reaction pressure is negative pressure; Described catalyzer is carried heteropoly acid salt catalyst, and heteropolyacid anions is the heteropolymolybdate of structure with Keggin, and heteroatoms is P or As, and counter cation is H or Cs, and the carrier of load is dealuminzation USY molecular sieve, MCM-41 molecular sieve or ion exchange resin;
The mol ratio of the described raw material trimethyl carbinol and pyrocatechol is 1:1 ~ 2.5;
The consumption of described catalyzer is 0.03% ~ 1% of trimethyl carbinol consumption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310567693.8A CN103553880B (en) | 2013-11-15 | 2013-11-15 | Synthetic method of para-tert-butylcatechol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310567693.8A CN103553880B (en) | 2013-11-15 | 2013-11-15 | Synthetic method of para-tert-butylcatechol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103553880A CN103553880A (en) | 2014-02-05 |
| CN103553880B true CN103553880B (en) | 2015-07-22 |
Family
ID=50008298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310567693.8A Expired - Fee Related CN103553880B (en) | 2013-11-15 | 2013-11-15 | Synthetic method of para-tert-butylcatechol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103553880B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053396B (en) * | 2018-09-20 | 2021-09-24 | 上海应用技术大学 | Method for directly producing o-ethoxyphenol by using ethylene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB761613A (en) * | 1954-07-19 | 1956-11-14 | Eastman Kodak Co | Preparation of tertiary-butyl-hydroquinone |
| CN87104109A (en) * | 1986-06-10 | 1988-01-20 | 住友化学工业株式会社 | Process for producing hydroxy group-containing alkyl aromatic compound |
| CN101412663A (en) * | 2008-11-28 | 2009-04-22 | 江苏工业学院 | Preparation technique for polymerization inhibitor products |
| CN102464574A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of p-alkyl catechol |
-
2013
- 2013-11-15 CN CN201310567693.8A patent/CN103553880B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB761613A (en) * | 1954-07-19 | 1956-11-14 | Eastman Kodak Co | Preparation of tertiary-butyl-hydroquinone |
| CN87104109A (en) * | 1986-06-10 | 1988-01-20 | 住友化学工业株式会社 | Process for producing hydroxy group-containing alkyl aromatic compound |
| CN101412663A (en) * | 2008-11-28 | 2009-04-22 | 江苏工业学院 | Preparation technique for polymerization inhibitor products |
| CN102464574A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of p-alkyl catechol |
Non-Patent Citations (1)
| Title |
|---|
| 磷钼酸盐催化剂的制备及其在邻苯二酚烷基化反应中的应用;张敬畅等;《石油化工》;20010720;第30卷(第07期);第513-516页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103553880A (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2266939B1 (en) | Processes for production of tertiary butanol | |
| CN102909077B (en) | Metal-modified cation exchange resin catalyst, preparation method and application thereof | |
| CN101143819B (en) | Method for preparing sec-butyl acetate | |
| CN103980080A (en) | Preparation method of xylene by alkylation of mixed crude benzene and methanol | |
| CN109796303B (en) | Preparation method of isoprene glycol | |
| CN103553880B (en) | Synthetic method of para-tert-butylcatechol | |
| KR101134659B1 (en) | Preparation method of Propylene glycol monomethyl ether acetate | |
| CN101234948A (en) | Method for hydrolyze annular carbonic ester by using ionic liquid as catalyst | |
| CN102211971A (en) | Process for preparing propylene from methanol | |
| CN102827006A (en) | Method for preparing catalytically nitrified aromatic compound with fixed bed reactor | |
| CN102992984A (en) | Methyl ethyl ketone preparation method | |
| US6072090A (en) | Olefin hydration process | |
| CN103813855A (en) | Catalytic dehydration of alcohols and ethers over a ternary mixed oxide | |
| CN102276475A (en) | Method for synthesizing 1,5-dinitronaphthalene and 1,8-dinitronaphthalene | |
| CN103769215A (en) | Modified cation exchange resin catalyst and its preparation method and application | |
| CN102757341A (en) | Preparation method of ethyl acetate and/or isopropyl acetate | |
| CN100503537C (en) | Method for preparing cyclopentanol by hydration of cyclopentene | |
| JP5336239B2 (en) | Process for producing olefin dimer, olefin dimer | |
| CN100432039C (en) | Method for protective preparation of acidic ion exchange resin catalyst for lower fatty acid ester | |
| CN102603490B (en) | Synthesis method of high-purity p-tert-butylcatechol | |
| CN102010364B (en) | Preparation method for terpene maleimide | |
| CN104788311A (en) | Method for preparing n-propyl propionate | |
| CN103506151B (en) | C 4 olefin prepares 2-butyl acetate catalyst | |
| CN102432589B (en) | Method for azeotropic distillation and purification of thiophene | |
| CN112439405B (en) | Catalyst for preparing dimethyl carbonate from methanol, carbon dioxide and 2-cyanopyridine and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200122 Address after: 116000 Pine Island chemical industry park, Pu Wan new area, Liaoning, Dalian Patentee after: Dalian timelyrain Haiming Chemical Group Co. Ltd. Address before: 300455 No. 108, Tonghua Road, Tanggu Binhai New Area, Tianjin Patentee before: Tianjin Rutai Precision Chemicals Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150722 Termination date: 20201115 |