CN102976901A - Synthetic method for hybrid tertiary butyl phenol - Google Patents
Synthetic method for hybrid tertiary butyl phenol Download PDFInfo
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- CN102976901A CN102976901A CN2012105159513A CN201210515951A CN102976901A CN 102976901 A CN102976901 A CN 102976901A CN 2012105159513 A CN2012105159513 A CN 2012105159513A CN 201210515951 A CN201210515951 A CN 201210515951A CN 102976901 A CN102976901 A CN 102976901A
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Abstract
The invention belongs to the preparation of chemical products and in particular relates to a synthetic method for hybrid tertiary butyl phenol. According to the synthetic method for the hybrid tertiary butyl phenol, phenol and isobutene are used as materials, phenol aluminum is used as catalyst, isobutene is ventilated to a reactor in a controlled manner, so that the phenol is prepared to hybrid tertiary butyl phenol which mainly contains 2,6-ditertiary butyl phenol at an alkylation temperature under the pressure, wherein the alkylation is completed under a low-pressure sealed condition; the reaction pressure is 0.05-0.5 MPa; the reaction temperature is 70 DEG C to 150 DEG C; the phenol aluminum is pre-prepared by adding aluminum to the phenol before isobutene is ventilated to the reactor; the molar ratio of the phenol aluminum to the phenol is in a range of 1:(20-800); the phenol is industrial phenol; the isobutene is more than 99.5% in percentage by weight; a diluted mineral acid aqueous solution is firstly used to hydrolyze the phenol aluminum in the hybrid tertiary butyl phenol, and then a washing method is adopted to remove the phenol aluminum salt in the crude product; filtering and distilling are used for refining the crude product, so the reaction risk is reduced, and the investment to the reaction device and production cost are reduced.
Description
Technical field
The invention belongs to the preparation of Chemicals, particularly a kind of synthetic method of mixed tertbutyl-phenol.
Background technology
1958, kalla, the people such as A.J, U.S, Pat.No.2,831,898, found the ortho position that organic aluminium salt can optionally be introduced alkyl the phenol hydroxyl.Soon, U.S. Ethyl, corp. company has released commodity " HITEC4733 " mixed tertbutyl-phenol oxidation inhibitor, and its main component is 2,6 di t butyl phenol.At present, published about selectivity in the document of synthetic 2,6 di t butyl phenol major part be to use aluminium phenolate as the ortho position catalysts selective.For example: U.S. Ethyl, the patent of corp.: U.S, Pat.No.3,185,737(1965, Jamee, Gedes etc.); U.S, Pat.No.4,870,215 and 4,870,216(1989, stelen L etc.); Japanese Patent: Mitsui Petrochemical Industries Ltd.; Clear 57-95428(1982, strong lucky in the mountain), all kind Petro Chemicals Co., Ltd.; Clear 61-50931(1986, high bridge English is second-class), large Japanese ィ ソ キ chemical industry Co., Ltd.; Flat 3-153642(1991, high bridge is risen and is controlled etc.); Etc..During with the synthetic 2,6 di t butyl phenol of the described method of above-mentioned patent, add the iso-butylene method and be: the aequum iso-butylene is pressed in the reactor with liquid form during disposable will the reaction.Be characterized in: because the speed of response of initial reaction stage phenol and iso-butylene is fast, thermal discharge is concentrated greatly, when the heat that has little time to remove from reaction system rises rapidly temperature of charge, reaction pressure is increased to about 2.5Mpa by 0.1Mpa at short notice, the result is: the temperature of reaction process system, pressure surge is large, reaction must be finished in the reactor of ability elevated pressures, make 2, the facility investment that the 6-DI-tert-butylphenol compounds is produced, production cost improve, and simultaneous reactions pressure more high risk is larger.
In 2 of formula (1) expression, in the 6-DI-tert-butylphenol compounds, the ortho position (2 of phenolic hydroxyl group,-6) occupied by the tertiary butyl of sterically hindered larger supplied for electronic after, the electron density of phenolic hydroxyl group Sauerstoffatom is strengthened, phenolic hydroxyl group is subject to the shielding of the tertiary butyl simultaneously, has improved the antioxygenic activity of 2,6 di t butyl phenol.Mixed tertbutyl-phenol is made an addition in the oil fuel such as gasoline, diesel oil, aviation kerosene and such as: turbine machine oil in the general-purpose machine wet goods Industrial Oil, demonstrates preferably low temperature resistance of oxidation.The mixed tertbutyl-phenol that is in a liquid state under the normal temperature can cooperate with the various kinds of lubricating oil additive composite additive that is formed in the lubricating oil mediation.2,6 di t butyl phenol is synthetic such as T1010, T1033, and T1076, KY-7930, the important source material of the contour performance antioxidant of KY-BHT, these high performance antioxidation agent are widely used in the macromolecular materials such as rubber, plastics.
Summary of the invention
The invention provides a kind of preparation method who mixes tert.-butyl phenol, the technological process that comprises is: take phenol, iso-butylene as raw material, use phenol aluminium to be catalyzer, under alkylation temperature, continuously the iso-butylene low-pressure gas is joined in the reaction mixture, the method of synthetic mixed tertbutyl-phenol take 2,6 di t butyl phenol as main content.In the method for the invention, the alkylated reaction of phenol and iso-butylene is to finish in the airtight reactor of low pressure, and better reaction pressure is 0.05-0.5MPa, and better temperature of reaction is 70-150 ℃.
Being used for catalyzer of the present invention is the compound aluminium phenolate of phenol or phenol and fortified phenol.The catalyzer that is used for alkylated reaction namely can prefabricatedly add afterwards reactor again, also can be by adding the material preparation that can generate with phenol reactant phenol aluminium in the alkylated reaction still, after for example the phenol of reacting weight being joined alkylation reactor, add such as aluminum alkylss such as metallic aluminium, aluminum hydride and triethyl aluminum, triisobutyl aluminiums, heating is fully reacted it and is formed desired phenol Al catalysts again.The mole of aluminium phenolate and phenol is take 1:20-800 as good.
Being used for phenol of the present invention is commercial-grade phenol, and the phenol water content should be lower than 0.03%.When phenol water content a little higher than 0.03%, should suitably strengthen the consumption of phenol aluminium, perhaps required phenol is dewatered.
Be used for its weight percentage of iso-butylene of the present invention greater than 99.5%.
In the present invention, the mol ratio of phenol and iso-butylene is advisable with 1:1.75-2.5.If be lower than 1.75, single isobutyl-product increases in the mixed tertbutyl-phenol, is higher than at 2.5 o'clock and will produces more tri-butyl-phenol, and the two all will cause the mixed tertbutyl-phenol availability performance to descend.
Before alkylated reaction begins, the iso-butylene of reaction consumption is pressed in the iso-butylene vaporizer, be preheating to iso-butylene vapor pressure: 0.6-1.0Mpa, under default temperature of reaction, iso-butylene added in the reactor continuously, until the iso-butylene that is filled with reaches the quantity of expection.
Processing about the phenol Al catalysts in the mixed tertbutyl-phenol crude product: make it generate aluminium hydroxide or aluminium salt with the diluted mineral acid aqueous solution in 60-70 ℃ of method that is hydrolyzed in the present invention, by washing, the methods such as filtration are separated with reaction product thereafter.Applicable acid has: hydrochloric acid, sulfuric acid, phosphoric acid etc.Acid concentration is with 2-10%, consumption should a little more than in and the theoretical consumption of phenol aluminium.
According to the mixed tertbutyl-phenol of method preparation of the present invention, the weight percentage of 2,6 di t butyl phenol 〉=80%, one, two (not comprising the 2.6-substituent) of phenol and phenol, the total content of tri-butyl-phenol≤20%.
The invention has the beneficial effects as follows: in the method for preparing mixed tertbutyl-phenol of the present invention, owing to take in reaction process, to be filled with continuously the method for iso-butylene, effectively solved the concentrated release of reaction heat, temperature of reaction and the large shortcoming of reaction pressure fluctuation, can be prepared reaction with withstand voltage lower reactor, the result has reduced the danger of reaction, has reduced conversion unit investment and production cost.
Embodiment
The invention will be further described by the following examples.
Embodiment 1:
(1) 400 gram phenol, 80 are restrained the matrass that toluene are put into two mouths of 1000ml successively, a mouth of matrass connects water trap successively, and reflux exchanger connects calcium chloride tube in the exit of reflux exchanger.Dewater with the azeotropic dehydration Pyrogentisinic Acid, in 80-100 ℃ 1.6-2.0 being restrained aluminium wire puts in the matrass, back flow reaction to aluminium wire all dissolves, intensification also steams toluene, kept 45 minutes in 160 ℃, be cooled to 100 ℃, the phenol solution that will contain phenol aluminium moves in the withstand voltage still of stainless steel of 2000ml drying.
(2) with behind nitrogen replacement still Air 2-3 time, with heating material to 105 in the still ℃, 580 gram iso-butylenes are pressed in the iso-butylene evaporating pot, be warming up to that the iso-butylene vapor pressure reaches 0.5Mpa in the vaporizer, iso-butylene is passed in the withstand voltage still, regulates the adding speed of iso-butylene according to reaction severity.
(3) with 150ml, 5% aqueous sulfuric acid joins in the crude reaction product, decompose phenol aluminium, organic phase after minute anhydrating mutually is with 80 ℃ of hot washes 2 times, and water 200-300ml removes by filter the suspended substance in the organic phase at every turn, the low-boiling point material (isobutene polymer etc.) in the crude product is removed in underpressure distillation, obtain the little yellow liquid of 960 grams, gas chromatographic analysis wherein contains: 82.1% 2,6 di t butyl phenol; 5.1% 2,4-DTBP; 10.9% 2,4, the 6-tri-butyl-phenol; 2,5-DI-tert-butylphenol compounds and phenol etc. account for 2.6%.
Claims (6)
1. the synthetic method of a mixed tertbutyl-phenol, it is characterized in that take phenol, iso-butylene as raw material, use phenol aluminium to be catalyzer, in reactor, controlledly pass into iso-butylene, make phenol at alkylation temperature, the method of the mixed tertbutyl-phenol of preparation take 2,6 di t butyl phenol as main content under the pressure.
2. the method for preparing mixed tertbutyl-phenol according to claim 1 is characterized in that alkylation finishes reaction pressure 0.05-0.5MPa, temperature of reaction 70-150 ℃ under the low pressure air tight condition.
3. the method for preparing mixed tertbutyl-phenol according to claim 1, it is characterized in that phenol aluminium is phenol aluminium, this phenol aluminium is before passing into iso-butylene to reactor, and it is prefabricated to add pure aluminum in the phenol, and the mol ratio of phenol aluminium and phenol is in the scope of 1:20-800.
4. according to the claim 1 described method for preparing mixed tertbutyl-phenol, it is characterized in that phenol is commercial-grade phenol, the weight percentage of iso-butylene 〉=99.5%.
5. the method for preparing mixed tertbutyl-phenol according to claim 1 is characterized in that using first the phenol aluminium in the diluted mineral acid aqueous hydrolysis mixed tertbutyl-phenol, and the method for washing is removed aluminium phenolate in the thick product again.
6. the method for preparing mixed tertbutyl-phenol according to claim 1, base are characterised in that the method for taking to filter and distilling is with thick product purification.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012105159513A CN102976901A (en) | 2012-12-06 | 2012-12-06 | Synthetic method for hybrid tertiary butyl phenol |
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| CN2012105159513A CN102976901A (en) | 2012-12-06 | 2012-12-06 | Synthetic method for hybrid tertiary butyl phenol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104678012A (en) * | 2015-02-04 | 2015-06-03 | 新疆独山子天利实业总公司 | Method for determining content of 2,6-di-tert-butyl phenol |
| CN108026010A (en) * | 2015-09-11 | 2018-05-11 | 巴斯夫欧洲公司 | Alkylated method for phenol |
| CN108503513A (en) * | 2018-03-29 | 2018-09-07 | 江苏极易新材料有限公司 | A kind of preparation method of 2,6 di t butyl phenol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193007A (en) * | 1998-01-22 | 1998-09-16 | 义县精细化工总厂 | Process for synthesizing mixed tertbutyl-phenol |
-
2012
- 2012-12-06 CN CN2012105159513A patent/CN102976901A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193007A (en) * | 1998-01-22 | 1998-09-16 | 义县精细化工总厂 | Process for synthesizing mixed tertbutyl-phenol |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104678012A (en) * | 2015-02-04 | 2015-06-03 | 新疆独山子天利实业总公司 | Method for determining content of 2,6-di-tert-butyl phenol |
| CN108026010A (en) * | 2015-09-11 | 2018-05-11 | 巴斯夫欧洲公司 | Alkylated method for phenol |
| CN108503513A (en) * | 2018-03-29 | 2018-09-07 | 江苏极易新材料有限公司 | A kind of preparation method of 2,6 di t butyl phenol |
| CN108503513B (en) * | 2018-03-29 | 2019-02-19 | 江苏极易新材料有限公司 | A kind of preparation method of 2,6 di t butyl phenol |
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Application publication date: 20130320 |