CN105503536A - Industrial preparation method of biphenol compounds with high purity - Google Patents
Industrial preparation method of biphenol compounds with high purity Download PDFInfo
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- 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
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
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Abstract
The invention discloses an industrial preparation method of biphenol compounds with high purity. The preparation method comprises the following steps: (1) a phenolic compound A containing a tert-butyl group whose ortho-position or para-position is a hydrogen atom is used as a raw material, an oxidative coupling reaction and a disproportionation reaction are carried out, and a tert-butyl-containing 4,4'-biphenol or 2,2'-biphenol compound is obtained; (2) a de-tert-butylation reaction is carried out for the tert-butyl-containing 4,4'-biphenol or 2,2'-biphenol compound at 100-220 DEG C with a strongly acidic catalyst in phenols or aliphatic solvents with high-boiling point, and a 4,4'-biphenol compound B or a 2,2'-biphenol compound C with high-purity is obtained. The preparation method of the 4,4'-biphenol or 2,2'-biphenol compound has the advantages of simple steps, mild reaction condition, low cost, cyclic utilization of reaction raw materials, excellent color of the product and high yield; the purity of the product reaches 99.9%, and the method is suitable for industrial production.
Description
Technical field
The invention belongs to Chemicals preparation field, be specifically related to a kind of preparation method of Chemicals, be specifically related to a kind of industrialized process for preparing of high purity Biphenol compound.
Background technology
4,4'-'-biphenyl diphenol and 2,2'-Biphenol compound are all important organic chemical industry's intermediate feed.Mainly can be used as the raw material of epoxy resin, vibrin, polycarbonate resin etc., also can be used as the stablizer of petroleum products, fluidizer, oxidation inhibitor and catalyst ligand etc.In recent years, Biphenol compound gets most of the attention as the starting raw material of heat-resistant engineering plastic, but is doing, in the use of regarding polymerization raw material, have very high requirement to raw materials quality.
In industrial production, the preparation method of Biphenol compound mainly contains four kinds: 1, melted through sulfonation, alkali by connection benzene and its derivative, hydrolysis prepared, as US Patent No. 6410238; 2, in organic low boiling point solvent or the aqueous solution, do oxygenant single stage method with superoxide to obtain, as Chinese patent CN201010164715.2; 3, carry out oxidative coupling and disproportionation reaction by phenol compound, then carry out de-t-butylation in aromatic hydrocarbon solvent, as Chinese patent CN201410203108.0, Japanese Patent JPH04338347A; 4, by the Biphenol compound replaced containing the tertiary butyl in an inert atmosphere, high-temperature fusion takes off tertiary butyl preparation, as US Patent No. 4205187.
Wherein first method, although can obtain high yield product, need in reaction process to consume a large amount of concentrated acid, highly basic, production cost is expensive, easily to environment.Second method, reaction process employs superoxide and makees oxygenant, carry out oxidizing reaction and easily blast, and in actual production process, by product is more, need purify through special process, be only suitable for laboratory small serial production under high temperature at low boiling point solvent.The Biphenol compound containing tertiary butyl replacement that the third method is produced has a large amount of tawny benzoquinones class by product to generate, aromatic hydrocarbon solvent is used to do de-t-butylation solvent toxicity large, product purity is not high, need in aftertreatment to use a large amount of low boiling point solvent crystallization and purification, or adopting expensive device to carry out sublimation purification, production cost is higher.The 4th kind of solvent-free de-tertiary butyl of method high temperature, the large stirring difficulty of system viscosity, generates the easy coking of product.
But, present inventor has carried out long-term further investigation to this type of reaction, after abundant grasp reaction mechanism, solve emphatically the problem of target product selectivity generation and the sustainable cyclic production of environmental protection, provide a kind of novel method preparing high purity Biphenol compound.This preparation method's technique is simple, and target product purity is high and reaction yield is high, is very suitable for suitability for industrialized production.
Summary of the invention
The object of the invention is to the defect overcoming above-mentioned prior art, provide one can prepare high purity, high yield, low cost, the simple Biphenol compound Industrialized synthesis method of processing method.
A kind of high purity Biphenol compound Industrialized synthesis method of the present invention, comprises following two-step reaction:
(1) with the phenolic compound A that is hydrogen atom containing the tertiary butyl, ortho position or contraposition for raw material, through oxidative coupling and disproportionation reaction, obtain 4, the 4'-'-biphenyl diphenols containing the tertiary butyl or 2,2'-Biphenol compound;
(2) in phenols or high boiling point aliphatic solvent, 4, the 4'-'-biphenyl diphenols or 2 of the tertiary butyl will be contained with strongly acidic catalyst at 100 ~ 220 DEG C, 2'-Biphenol compound carries out de-tert-butylation reaction, obtain high purity 4,4'-'-biphenyl diphenol or 2,2'-Biphenol compound B or C.Reaction result is as follows:
In the above-mentioned preparation method of the present invention, be the R of the phenolic compound A of hydrogen atom containing the tertiary butyl, ortho position or contraposition in described preparation method
1for the tertiary butyl, R2 is the perfluoroalkyl of hydrogen, the alkyl of 1 ~ 15 carbon atom, the alkoxyl group of 1 ~ 15 carbon atom or 1 ~ 5 carbon atom.
Now phenolic compound A is that 2-replaces-6-tert.-butyl phenol, the 2-tertiary butyl-4-fortified phenol, 2-replacement-4-TBP.Preferred R
2can be methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, methoxyl group, oxyethyl group or trifluoromethyl.As 2,6-DI-tert-butylphenol compounds, 2,4-DTBP, 2-methyl-6-tert-butylphenol, 2-ethyl-6-tert.-butyl phenol, 2-methoxyl group-6-tert.-butyl phenol, 2-oxyethyl group-6-tert.-butyl phenol, 2-trifluoromethyl-6-tert.-butyl phenol, 2-tert-butyl-4-methyl-Phenol, the 2-tertiary butyl-4-ethylphenol, the 2-tertiary butyl-4-methoxyphenol, 2-methyl-4-TBP, 2-ethyl-4-TBP, 2-methoxyl group-4-TBP, 2-trifluoromethy-4-TBP etc.
Oxidative coupling in described preparation method comprises the steps: the oxyhydroxide of the phenolic compound A containing the tertiary butyl, ortho position or contraposition being hydrogen atom, basic metal or alkaline-earth metal or slightly acidic an alkali metal salt, different phenol oxidation conditioning agent to add in reactor, control temperature of reaction 65 DEG C ~ 185 DEG C, constantly blasts oxygen or air carries out oxidative coupling.Described basic metal or the oxyhydroxide of alkaline-earth metal or slightly acidic an alkali metal salt comprise the mixture of one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium-acetate, its consumption be raw material contain that the tertiary butyl, ortho position or contraposition are the phenolic compound A weight of hydrogen atom 0.1 ~ 8.0%, be preferably 0.5 ~ 5.0%.
Described different phenol oxidation conditioning agent comprises 2,4,6-tri (C9 ~ C55), 2,4,6-tri-alkoxy phenol (C9 ~ C55), 2,4,6-tri-perfluoroalkyl phenol (C9 ~ C45), be the mixture of one or more in the phenolic compound A of hydrogen atom, antioxidant 1010, antioxidant 1076, oxidation inhibitor 1035, oxidation inhibitor 245 containing the tertiary butyl, ortho position or contraposition, consumption is be 0.01 ~ 5.0% of the phenolic compound A weight of hydrogen atom containing the tertiary butyl, ortho position or contraposition, is preferably 0.05 ~ 3.0%.Described oxidative coupling temperature is at 65 DEG C ~ 185 DEG C, and oxidation time is 1 ~ 8h.
After disproportionation reaction in described preparation method comprises the steps: to regulate reaction solution to neutrality with acidic substance, change into and carry out disproportionation reaction in 165 ~ 245 DEG C in inert gas environment, must containing 4,4'-'-biphenyl diphenols of the tertiary butyl or 2,2'-Biphenol compound.
Described acidic substance are one or more mixtures in hydrochloric acid, phosphoric acid, sulfuric acid, Phenylsulfonic acid, tosic acid, formic acid, acetic acid, propionic acid, oxalic acid, and its consumption is 0.8 ~ 1.5 times of basic catalyst material molar weight; Described disproportionation reaction is at 165 ~ 245 DEG C, and the disproportionation reaction time is 15min ~ 8h.
De-tert-butylation reaction in described preparation method comprises the steps: in phenols or high boiling point aliphatic solvent, 4 of the tertiary butyl will be contained at 100 ~ 220 DEG C with strongly acidic catalyst, 4'-'-biphenyl diphenol or 2,2'-Biphenol compound carries out de-tert-butylation reaction, obtain highly purified 4,4'-'-biphenyl diphenol or 2,2'-Biphenol compound B or C.
Described phenols or high boiling point aliphatic solvent comprise phenol, adjacent phenyl methylcarbamate, to phenyl methylcarbamate, containing the tertiary butyl, ortho position or contraposition are the phenolic compound A of hydrogen atom, 2, 4, 6-tri (C9 ~ C55), 2, 4, 6-tri-alkoxy phenol (C9 ~ C55), 2, 4, 6-tri-perfluoroalkyl phenol (C9 ~ C45), undecane, dodecane, tridecane, the tetradecane, white oil, whiteruss, DMF, DMAC, NMP, tetramethylene sulfone, sulfobenzide, ethylene glycol, glycerol, dimethyl silicone oil, polyoxyethylene glycol, poly glycol monomethyl ether, one or more mixtures in Polyethylene glycol dimethyl ether.Described phenols or high boiling point aliphatic solvent consumption are containing 4,4'-'-biphenyl diphenols of the tertiary butyl or 0.1 ~ 10 times of 2,2'-Biphenol compound mole number.
Described strongly acidic catalyst comprises one or more mixtures in tosic acid, benzene methanesulfonic acid, sulfuric acid, aluminum chloride, iron trichloride.Described strongly acidic catalyst consumption is containing 4,4'-'-biphenyl diphenols of the tertiary butyl or 0.1 ~ 10% of 2,2'-Biphenol compound weight.Described de-tert-butylation reaction temperature is 100 ~ 220 DEG C.
Described de-tert-butylation reaction gained 4,4'-'-biphenyl diphenol or 2,2'-Biphenol compound B or C purity reach more than 99.9%.
Beneficial effect of the present invention:
Preparation method's step of 4,4'-'-biphenyl diphenols of the present invention or 2,2'-Biphenol compound is simple, reaction conditions is gentle and cost is low, reaction raw materials reusable edible, and product colour is excellent, productive rate is high, and product purity, up to 99.9%, is very suitable for suitability for industrialized production.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are by the restriction of following embodiment.
Embodiment 1
Add 140Kg2 in 200L stainless steel still, 6-DI-tert-butylphenol compounds and 0.6Kg2,4,6-trimethoxy phenol, after nitrogen replacement, be heated to 150 DEG C, add the granular NaOH of 1.8kg fast.Subsequently, with after pure oxygen replaced in system, constantly import oxygen and react at 145 DEG C, react and stop oxygen importing after 5 hours.Add 1.4Kg phosphoric acid and system regulated PH to 5.8, be warming up to 218 DEG C reaction 4h after stopped reaction.Reaction intermediate is added 100kg2, in 4,6-pseudocuminol solvent, adds after 2.1kg tosic acid is warming up to 200 DEG C of reaction 8h and obtain high purity 4,4'-'-biphenyl diphenol.Product fusing point 283-286 DEG C, can reach more than 99.9% through HPLC evaluating objects product purity.
Embodiment 2
Add 140Kg2 in 200L stainless steel still, 4-DI-tert-butylphenol compounds and 0.8Kg antioxidant 1010, after nitrogen replacement, be heated to 150 DEG C, add the granular NaHCO of 1.6kg fast
3.Subsequently, with after pure oxygen replaced in system, constantly import oxygen and react at 105 DEG C, react and stop oxygen importing after 8 hours.Add 1.8Kg acetic acid and system regulated PH to 6.8, be warming up to 230 DEG C reaction 4h after stopped reaction.Reaction intermediate is added in 120kg polyoxyethylene glycol solvent, add after 2.2kg sulfuric acid is warming up to 180 DEG C of reaction 8h and obtain high purity 2,2'-'-biphenyl diphenol.Product fusing point 108-110 DEG C, can reach more than 99.9% through HPLC evaluating objects product purity.
Embodiment 3
Add 140Kg2-methyl-6-tert-butylphenol and 0.6Kg antioxidant 1076 in 200L stainless steel still, after nitrogen replacement, be heated to 140 DEG C, add the granular KOH of 1.7kg fast.Subsequently, with after pure oxygen replaced in system, constantly import oxygen and react at 135 DEG C, react and stop oxygen importing after 4 hours.Add 1.9Kg acetic acid and system regulated PH to 6.8, be warming up to 215 DEG C reaction 3h after stopped reaction.Reaction intermediate is added in 100kg2-methyl-6-tert-butylphenol, add after 2.1kg tosic acid is warming up to 150 DEG C of reaction 5h and obtain high purity 3,3'-dimethyl-4,4'-'-biphenyl diphenol.Product fusing point 153-155 DEG C, can reach more than 99.9% through HPLC evaluating objects product purity.
Embodiment 4
Add 140Kg2 in 200L stainless steel still, 6-DI-tert-butylphenol compounds and 0.6Kg antioxidant 1076, after nitrogen replacement, be heated to 135 DEG C, add the granular K of 1.9kg fast
2cO
3.Subsequently, with after pure oxygen replaced in system, constantly import oxygen and react at 140 DEG C, react and stop oxygen importing after 5.5 hours.Add 1.8Kg hydrochloric acid and system regulated PH to 7.8, be warming up to 225 DEG C reaction 4h after stopped reaction.Reaction intermediate is added in 50kgNMP solvent, add after 2.3kg iron trichloride is warming up to 170 DEG C of reaction 6h and obtain high purity 4,4'-'-biphenyl diphenol.Product fusing point 283-286 DEG C, can reach more than 99.9% through HPLC evaluating objects product purity.
Embodiment 5
Add 140Kg2 in 200L stainless steel still, 4-DI-tert-butylphenol compounds and 1.2Kg2,4,6-pseudocuminol, after nitrogen replacement, be heated to 120 DEG C, add the granular KHCO of 1.6kg fast
3.Subsequently, with after pure oxygen replaced in system, constantly import oxygen and react at 125 DEG C, react and stop oxygen importing after 8 hours.Add 1.8Kg acetic acid and system regulated PH to 6.8, be warming up to 190 DEG C reaction 4h after stopped reaction.Reaction intermediate is added in 110kg ethylene glycol solvent, add after 2.2kg benzene methanesulfonic acid is warming up to 190 DEG C of reaction 6h and obtain high purity 2,2'-'-biphenyl diphenol.Product fusing point 108-110 DEG C, can reach more than 99.9% through HPLC evaluating objects product purity.
Claims (10)
1. an industrialized process for preparing for high purity Biphenol compound, is characterized in that, comprises the following steps:
(1) with the phenolic compound A that is hydrogen atom containing the tertiary butyl, ortho position or contraposition for raw material, through oxidative coupling and disproportionation reaction, obtain 4, the 4'-'-biphenyl diphenols containing the tertiary butyl or 2,2'-Biphenol compound;
(2) in phenols or high boiling point aliphatic solvent, 4, the 4'-'-biphenyl diphenols or 2 of the tertiary butyl will be contained with strongly acidic catalyst at 100 ~ 220 DEG C, 2'-Biphenol compound carries out de-tert-butylation reaction, obtain high purity 4,4'-'-biphenyl diphenol or 2,2'-Biphenol compound B or C; Reaction result is as follows:
2. the industrialized process for preparing of a kind of high purity Biphenol compound according to claim 1, is characterized in that, is the R of the phenolic compound A of hydrogen atom in described preparation method containing the tertiary butyl, ortho position or contraposition
1for the tertiary butyl, R2 is the perfluoroalkyl of hydrogen, the alkyl of 1 ~ 15 carbon atom, the alkoxyl group of 1 ~ 15 carbon atom or 1 ~ 5 carbon atom.
3. the industrialized process for preparing of a kind of high purity Biphenol compound according to claim 1, it is characterized in that, described oxidative coupling comprises the steps: that by the oxyhydroxide of the phenolic compound A containing the tertiary butyl, ortho position or contraposition being hydrogen atom, basic metal or alkaline-earth metal or slightly acidic an alkali metal salt be basic catalyst, different phenol oxidation conditioning agent adds in reactor, control temperature of reaction 65 DEG C ~ 185 DEG C, constantly blast oxygen or air carries out oxidative coupling, oxidation time is 1 ~ 8h.
4. the industrialized process for preparing of a kind of high purity Biphenol compound according to claim 3, it is characterized in that, described basic metal or the oxyhydroxide of alkaline-earth metal or slightly acidic an alkali metal salt comprise the mixture of one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium-acetate, and its consumption is be 0.1 ~ 8.0% of the phenolic compound A weight of hydrogen atom containing the tertiary butyl, ortho position or contraposition.
5. the industrialized process for preparing of a kind of high purity Biphenol compound according to claim 3, it is characterized in that, described different phenol oxidation conditioning agent comprises 2, 4, 6-tri (C9 ~ C55), 2, 4, 6-tri-alkoxy phenol (C9 ~ C55), 2, 4, 6-tri-perfluoroalkyl phenol (C9 ~ C45), containing the tertiary butyl, ortho position or contraposition are the phenolic compound A of hydrogen atom, antioxidant 1010, antioxidant 1076, oxidation inhibitor 1035, the mixture of one or more in oxidation inhibitor 245, consumption is for containing the tertiary butyl, ortho position or contraposition are 0.01 ~ 5.0% of the phenolic compound A weight of hydrogen atom.
6. the industrialized process for preparing of a kind of high purity Biphenol compound according to claim 1, it is characterized in that, after described disproportionation reaction comprises the steps: to regulate reaction solution to neutrality with acidic substance, change into and carry out disproportionation reaction in 165 ~ 245 DEG C in inert gas environment, reaction times is 15min ~ 8h, must containing 4,4'-'-biphenyl diphenols of the tertiary butyl or 2,2'-Biphenol compound.
7. the industrialized process for preparing of a kind of high purity Biphenol compound according to claim 6, it is characterized in that, described acidic substance are one or more mixtures in hydrochloric acid, phosphoric acid, sulfuric acid, Phenylsulfonic acid, tosic acid, formic acid, acetic acid, propionic acid, oxalic acid, and its consumption is 0.8 ~ 1.5 times of basic catalyst material molar weight.
8. the industrialized process for preparing of a kind of high purity Biphenol compound according to claim 1, it is characterized in that, described phenols or high boiling point aliphatic solvent comprise phenol, adjacent phenyl methylcarbamate, to phenyl methylcarbamate, containing the tertiary butyl, ortho position or contraposition are the phenolic compound A of hydrogen atom, 2, 4, 6-tri (C9 ~ C55), 2, 4, 6-tri-alkoxy phenol (C9 ~ C55), 2, 4, 6-tri-perfluoroalkyl phenol (C9 ~ C45), undecane, dodecane, tridecane, the tetradecane, white oil, whiteruss, DMF, DMAC, NMP, tetramethylene sulfone, sulfobenzide, ethylene glycol, glycerol, dimethyl silicone oil, polyoxyethylene glycol, poly glycol monomethyl ether, one or more mixtures in Polyethylene glycol dimethyl ether, described phenols or high boiling point aliphatic solvent consumption are containing 4,4'-'-biphenyl diphenols of the tertiary butyl or 0.1 ~ 10 times of 2,2'-Biphenol compound mole number.
9. the industrialized process for preparing of a kind of high purity Biphenol compound according to claim 1, it is characterized in that, described strongly acidic catalyst comprises one or more mixtures in tosic acid, benzene methanesulfonic acid, sulfuric acid, aluminum chloride, iron trichloride; Described strongly acidic catalyst consumption is containing 4,4'-'-biphenyl diphenols of the tertiary butyl or 0.1 ~ 10% of 2,2'-Biphenol compound weight.
10. the industrialized process for preparing of a kind of high purity Biphenol compound according to claim 1, is characterized in that, described de-tert-butylation reaction gained 4,4'-'-biphenyl diphenol or 2,2'-Biphenol compound B or C purity reach more than 99.9%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956135A (en) * | 2021-11-15 | 2022-01-21 | 宁夏清研高分子新材料有限公司 | Preparation method of high-yield 4, 4' -biphenol |
| CN115626866A (en) * | 2022-09-25 | 2023-01-20 | 宿迁思睿屹新材料有限公司 | Industrial synthesis method of high-purity 4,4' -biphenol compound |
| CN115872841A (en) * | 2022-12-12 | 2023-03-31 | 江苏极易新材料有限公司 | Method for synthesizing 4,4' -dihydroxybiphenyl by disproportionation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956135A (en) * | 2021-11-15 | 2022-01-21 | 宁夏清研高分子新材料有限公司 | Preparation method of high-yield 4, 4' -biphenol |
| CN113956135B (en) * | 2021-11-15 | 2024-02-13 | 宁夏清研高分子新材料有限公司 | Preparation method of high-yield 4,4' -biphenol |
| CN115626866A (en) * | 2022-09-25 | 2023-01-20 | 宿迁思睿屹新材料有限公司 | Industrial synthesis method of high-purity 4,4' -biphenol compound |
| CN115872841A (en) * | 2022-12-12 | 2023-03-31 | 江苏极易新材料有限公司 | Method for synthesizing 4,4' -dihydroxybiphenyl by disproportionation method |
| CN115872841B (en) * | 2022-12-12 | 2024-04-09 | 江苏极易新材料有限公司 | Method for synthesizing 4,4' -dihydroxybiphenyl by disproportionation method |
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Application publication date: 20160420 |
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