CN102173981A - Method for synthesizing 2-tertiary butyl hydroquinone (TBHQ) - Google Patents
Method for synthesizing 2-tertiary butyl hydroquinone (TBHQ) Download PDFInfo
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- CN102173981A CN102173981A CN2011100554371A CN201110055437A CN102173981A CN 102173981 A CN102173981 A CN 102173981A CN 2011100554371 A CN2011100554371 A CN 2011100554371A CN 201110055437 A CN201110055437 A CN 201110055437A CN 102173981 A CN102173981 A CN 102173981A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for synthesizing 2-tertiary butyl hydroquinone (TBHQ). The method comprises the following steps of: heating hydroquinone serving as a raw material to 105 to 115 DEG C in a binary mixed solvent system consisting of a hydrocarbon solvent and a ketone solvent under the action of an acidic catalyst; starting to add a mixed solvent consisting of an aromatic solvent and tertiary butanol dropwise for 4 to 5 hours; continuously heating the materials to 125 to 135 DEG C; performing a heat-preserving reaction for 1 to 2 hours to generate the 2-TBHQ. The method has the advantages of simple process, mild reaction condition, recoverable catalyst, good product quality, low production cost and the like.
Description
Technical field
The present invention relates to chemosynthesis technical field, be specifically related to a kind of synthetic method of 2-Tert. Butyl Hydroquinone.
Background technology
2-Tert. Butyl Hydroquinone (TBHQ) is a kind of low toxicity, novel food product antioxidant efficiently, applied range.In industries such as rubber, plastics makeup application is arranged all.The important use of TBHQ is the oxidation inhibitor as food oils, and TBHQ is as the oxidation inhibitor of food oils, has efficient, low toxicity, thermally-stabilised good advantage.
The method of at present synthetic TBHQ mainly contains two kinds: (1) is catalyzer with the liquid inorganic acid, and Resorcinol (HQ) carries out alkylated reaction with the trimethyl carbinol, iso-butylene or methyl tertiary butyl ether (MTBE) in the mixed solvent of water and organic solvent composition; (2) be catalyzer with the solid acid, Resorcinol and isobutyl carry out alkylated reaction in organic solvent.
The advantage of first method is that the TBHQ selectivity reaches 77%, but the aftertreatment trouble, acid catalyst pollutes big; The advantage of second method is that catalyst separating is convenient, can be recycled, and pollutes little, but strict to the moisture controlled in the reaction system.
The tertiary butyl one substitution reaction takes place on the phenyl ring of TBHQ Resorcinol to be generated.2,5 di tert butyl hydroquinone (DTBQ) is to produce the by product that TBHQ is easy to generate most.The generation of two substitution reaction by product ditert-butylhydro quinones (DTBHQ) has reduced the utilization ratio of Resorcinol, and the DTBHQ anorexia is used, as aldehydes matter, if it is discarded with contaminate environment, in the technology of the production TBHQ that is reported at present, the ratio that generates TBHQ is generally 68～75%, and the ratio that generates DTBHQ is generally 18～25%, and this shows that nearly 15～20% Resorcinol is converted into DTBHQ and loses.
The principal reaction formula:
Summary of the invention
The object of the present invention is to provide a kind of technology simple, the reaction conditions gentleness, catalyzer is recyclable, good product quality, the synthetic method of the 2-Tert. Butyl Hydroquinone that production cost is low.
Purpose of the present invention is achieved by taking following technical scheme:
A kind of synthetic method of 2-Tert. Butyl Hydroquinone, it is characterized in that, be raw material with the Resorcinol, in the binary mixed solvent system of varsol and ketones solvent composition, under the effect of an acidic catalyst, be warming up to 105～115 ℃, begin to drip the mixed solvent of aromatic hydrocarbon solvent and trimethyl carbinol composition, the dropping time is 4～5 hours, after dripping, continue to be warming up to 125～135 ℃, insulation reaction 1～2 hour generates the 2-Tert. Butyl Hydroquinone.
In the above-mentioned synthetic method:
Described varsol is toluene, dimethylbenzene or hexanaphthene, preferred dimethylbenzene.
Described ketones solvent is acetone, butanone or methyl iso-butyl ketone (MIBK), preferred butanone.
The volume ratio of described varsol and ketones solvent is 1: 0.2～0.01.
Described an acidic catalyst is the vitriol oil, phosphoric acid, p-methyl benzenesulfonic acid or macropore sulfonic acid ion exchange resin, preferred macropore sulfonic acid ion exchange resin.
Described aromatic hydrocarbon solvent is toluene, dimethylbenzene or m-xylene, preferred dimethylbenzene.
The volume percent content of the described aromatic hydrocarbon solvent and the trimethyl carbinol is 5～60%.
The consumption of the described trimethyl carbinol is 50～150% of a Resorcinol weight.
The consumption of the binary mixed solvent that described varsol and ketones solvent are formed is 2～10 times of Resorcinol weight.
The consumption of described an acidic catalyst is 3～12% of a Resorcinol weight.
Compared with prior art, technical process of the present invention is simple, and catalyzer is recyclable to be recycled, and the DTBHQ that the present invention generated is 13～15%, and generating TBHQ is 83～86%, has improved the yield of TBHQ greatly, production cost is obviously descended, be fit to very much suitability for industrialized production.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment
Embodiment 1
Adding Resorcinol 110 grams (1 mole), dimethylbenzene/butanone restrain according to binary mixed solvent 330 grams and the macropore sulfonic acid cation resin 5.5 of 1: 0.1 volume ratio composition in the there-necked flask of 1L.Stirring is warming up to 110 ℃, beginning slowly drips dimethylbenzene/trimethyl carbinol 120 grams of 10%, the dropping time is 4 hours, after dripping, continues to be warming up to 130 ℃, insulation reaction 1 hour, after reaction finished, reacting liquid filtering was removed resin catalyst, and filtrate steaming removal solvent obtains the TBHQ crude product, with its composition of gas chromatographic analysis, wherein contain TBHQ85.2%, unreacted HQ0.6%, DTBHQ13.8% (not comprising residual solvent and a small amount of other impurity).
Embodiment 2
Adding Resorcinol 110 grams (1 mole), dimethylbenzene/butanone restrain according to binary mixed solvent 550 grams and the macropore sulfonic acid cation resin 5.5 of 1: 0.1 volume ratio composition in the there-necked flask of 1L.Stirring is warming up to 115 ℃, beginning slowly drips dimethylbenzene/trimethyl carbinol 200 grams of 15%, the dropping time is 4 hours, after dripping, continues to be warming up to 130 ℃, insulation reaction 2 hours, after reaction finished, reacting liquid filtering was removed resin catalyst, and filtrate steaming removal solvent obtains the TBHQ crude product, with its composition of gas chromatographic analysis, wherein contain TBHQ84.3%, unreacted HQ0.8%, DTBHQ14.6% (not comprising residual solvent and a small amount of other impurity).
Embodiment 3
Adding Resorcinol 110 grams (1 mole), dimethylbenzene/butanone restrain according to binary mixed solvent 330 grams and the macropore sulfonic acid cation resin 8 of 1: 0.1 volume ratio composition in the there-necked flask of 1L.Stirring is warming up to 110 ℃, beginning slowly drips dimethylbenzene/trimethyl carbinol 270 grams of 20%, the dropping time is 5 hours, after dripping, continues to be warming up to 130 ℃, insulation reaction 2 hours, after reaction finished, reacting liquid filtering was removed resin catalyst, and filtrate steaming removal solvent obtains the TBHQ crude product, with its composition of gas chromatographic analysis, wherein contain TBHQ83.5%, unreacted HQ0.84%, DTBHQ14.8% (not comprising residual solvent and a small amount of other impurity).
Embodiment 4
Adding Resorcinol 110 grams (1 mole), dimethylbenzene/acetone restrain according to binary mixed solvent 380 grams and the macropore sulfonic acid cation resin 4 of 1: 0.08 volume ratio composition in the there-necked flask of 1L.Stirring is warming up to 110 ℃, beginning slowly drips dimethylbenzene/trimethyl carbinol 300 grams of 40%, the dropping time is 4 hours, after dripping, continues to be warming up to 135 ℃, insulation reaction 1 hour, after reaction finished, reacting liquid filtering was removed resin catalyst, and filtrate steaming removal solvent obtains the TBHQ crude product, with its composition of gas chromatographic analysis, wherein contain TBHQ75.3%, unreacted HQ2.63%, DTBHQ21.6% (not comprising residual solvent and a small amount of other impurity).
Embodiment 5
Adding Resorcinol 110 grams (1 mole), dimethylbenzene/butanone restrain according to binary mixed solvent 300 grams and the tosic acid 6 of 1: 0.15 volume ratio composition in the there-necked flask of 1L.Stirring is warming up to 110 ℃, beginning slowly drips toluene/trimethyl carbinol 250 grams of 20%, the dropping time is 5 hours, after dripping, continues to be warming up to 130 ℃, insulation reaction 2 hours, after reaction finished, reacting liquid filtering was removed resin catalyst, and filtrate steaming removal solvent obtains the TBHQ crude product, with its composition of gas chromatographic analysis, wherein contain TBHQ71.5%, unreacted HQ3.80%, DTBHQ24.2% (not comprising residual solvent and a small amount of other impurity).
Embodiment 6
Adding Resorcinol 110 grams (1 mole), hexanaphthene/methyl iso-butyl ketone (MIBK) restrain according to binary mixed solvent 400 grams and the macropore sulfonic acid cation resin 10 of 1: 0.1 volume ratio composition in the there-necked flask of 1L.Stirring is warming up to 110 ℃, beginning slowly drips dimethylbenzene/trimethyl carbinol 230 grams of 20%, the dropping time is 4 hours, after dripping, continues to be warming up to 135 ℃, insulation reaction 2 hours, after reaction finished, reacting liquid filtering was removed resin catalyst, and filtrate steaming removal solvent obtains the TBHQ crude product, with its composition of gas chromatographic analysis, wherein contain TBHQ10.7%, unreacted HQ86.4%, DTBHQ2.11% (not comprising residual solvent and a small amount of other impurity).
Embodiment 7
Adding Resorcinol 110 grams (1 mole), dimethylbenzene/methyl iso-butyl ketone (MIBK) restrain according to binary mixed solvent 330 grams and the macropore sulfonic acid cation resin 8 of 1: 0.2 volume ratio composition in the there-necked flask of 1L.Stirring is warming up to 110 ℃, beginning slowly drips m-xylene/trimethyl carbinol 400 grams of 30%, the dropping time is 5 hours, after dripping, continues to be warming up to 130 ℃, insulation reaction 1 hour, after reaction finished, reacting liquid filtering was removed resin catalyst, and filtrate steaming removal solvent obtains the TBHQ crude product, with its composition of gas chromatographic analysis, wherein contain TBHQ74.1%, unreacted HQ2.46%, DTBHQ23.0% (not comprising residual solvent and a small amount of other impurity).
In a word, the present invention has exemplified above-mentioned preferred implementation, but should illustrate that those skilled in the art can carry out various variations and remodeling.Therefore, unless such variation and remodeling have departed from scope of the present invention, otherwise all should be included in protection scope of the present invention.
Claims (10)
1. the synthetic method of a 2-Tert. Butyl Hydroquinone, it is characterized in that, be raw material with the Resorcinol, in the binary mixed solvent system of varsol and ketones solvent composition, under the effect of an acidic catalyst, be warming up to 105～115 ℃, begin to drip the mixed solvent of aromatic hydrocarbon solvent and trimethyl carbinol composition, the dropping time is 4～5 hours, after dripping, continue to be warming up to 125～135 ℃, insulation reaction 1～2 hour generates the 2-Tert. Butyl Hydroquinone.
2. synthetic method according to claim 1 is characterized in that, described varsol is toluene, dimethylbenzene or hexanaphthene.
3. synthetic method according to claim 1 is characterized in that, described ketones solvent is acetone, butanone or methyl iso-butyl ketone (MIBK).
4. synthetic method according to claim 1 is characterized in that, the volume ratio of described varsol and ketones solvent is 1: 0.2～0.01.
5. synthetic method according to claim 1 is characterized in that, described an acidic catalyst is the vitriol oil, phosphoric acid, p-methyl benzenesulfonic acid or macropore sulfonic acid ion exchange resin.
6. synthetic method according to claim 1 is characterized in that, described aromatic hydrocarbon solvent is toluene, dimethylbenzene or m-xylene.
7. synthetic method according to claim 1 is characterized in that, the volume percent content of the described aromatic hydrocarbon solvent and the trimethyl carbinol is 5～60%.
8. synthetic method according to claim 1 is characterized in that, the consumption of the described trimethyl carbinol is 50～150% of a Resorcinol weight.
9. synthetic method according to claim 1 is characterized in that, the consumption of the binary mixed solvent that described varsol and ketones solvent are formed is 2～10 times of Resorcinol weight.
10. synthetic method according to claim 1 is characterized in that, the consumption of described an acidic catalyst is 3～12% of a Resorcinol weight.
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| CN2011100554371A CN102173981A (en) | 2011-03-09 | 2011-03-09 | Method for synthesizing 2-tertiary butyl hydroquinone (TBHQ) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110878008A (en) * | 2018-09-06 | 2020-03-13 | 天津科伦药物研究有限公司 | Preparation method of high-purity 2-tert-butylhydroquinone and purification method of 2-tert-butylhydroquinone |
| CN112479828A (en) * | 2020-12-17 | 2021-03-12 | 厦门大学 | Synthetic method of tert-butyl hydroquinone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4323713A (en) * | 1980-11-20 | 1982-04-06 | Uop Inc. | Preparation of mono-tertiary butylhydroquinone |
| CN1583698A (en) * | 2004-06-11 | 2005-02-23 | 广州优宝工业有限公司 | Preparing method for tert-butyl group hydroquinol |
| CN1962590A (en) * | 2006-11-23 | 2007-05-16 | 复旦大学 | Environment-friendly preparation method for 2-tertiary butyl hydroquinone |
-
2011
- 2011-03-09 CN CN2011100554371A patent/CN102173981A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4323713A (en) * | 1980-11-20 | 1982-04-06 | Uop Inc. | Preparation of mono-tertiary butylhydroquinone |
| CN1583698A (en) * | 2004-06-11 | 2005-02-23 | 广州优宝工业有限公司 | Preparing method for tert-butyl group hydroquinol |
| CN1962590A (en) * | 2006-11-23 | 2007-05-16 | 复旦大学 | Environment-friendly preparation method for 2-tertiary butyl hydroquinone |
Non-Patent Citations (1)
| Title |
|---|
| 张旭光等: "叔丁醇法合成邻叔丁基对苯二酚的实验研究", 《黑龙江科技学院学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110878008A (en) * | 2018-09-06 | 2020-03-13 | 天津科伦药物研究有限公司 | Preparation method of high-purity 2-tert-butylhydroquinone and purification method of 2-tert-butylhydroquinone |
| CN110878008B (en) * | 2018-09-06 | 2023-10-13 | 四川科伦药物研究院有限公司 | Preparation method of high-purity 2-tertiary butyl hydroquinone and purification method of 2-tertiary butyl hydroquinone |
| CN112479828A (en) * | 2020-12-17 | 2021-03-12 | 厦门大学 | Synthetic method of tert-butyl hydroquinone |
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Application publication date: 20110907 |