CN105712885B - A kind of process for refining of bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2- - Google Patents
A kind of process for refining of bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2- Download PDFInfo
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- CN105712885B CN105712885B CN201410790967.4A CN201410790967A CN105712885B CN 105712885 B CN105712885 B CN 105712885B CN 201410790967 A CN201410790967 A CN 201410790967A CN 105712885 B CN105712885 B CN 105712885B
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Abstract
The present invention relates to a kind of more particularly to a kind of process for refining of 2,2 bis- (3 nitro, 4 hydroxy phenyl) hexafluoropropane, it is characterized in that including step：(1), by 2,2 bis- (3 nitro, 4 hydroxy phenyl) hexafluoropropane crude products, potassium carbonate is added or sodium hydroxide solution is stirred to product and all dissolved；(2) dissolved solution is filtered, filter impurity；(3) hydrochloric acid solution modulation 17 solids of pH are added dropwise into the solution of step (2) to be precipitated；(4) after solid addition dichloromethane dissolving will be precipitated, washed, be layered with sodium carbonate liquid, oil reservoir concentration, crystallisation by cooling filters, washs, vacuum drying, obtaining 2,2 bis- (3 nitro, 4 hydroxy phenyl) hexafluoropropane.The product purity refined with organic solvent dichloromethane extraction method is high, and environmental benefit is good, and pollution is less, can thorough elimination reaction by-product, the product being easy to get to ideal yield and purity.
Description
Technical field
The present invention relates to the preparation process of bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2- of one kind, more particularly to one
The process for refining of kind bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2-.
Background technology
In recent years, since problem of environmental pollution is increasingly that various countries are paid close attention to, organism unit reaction is industrially widely used at present
Nitrating agent have nitric-sulfuric acid, nitrate, metal nitrate etc., the side reactions such as polynitration, oxidation for occurring in reaction can also produce
The quality of raw serious security risk and next step reactor product.Since bisphenol AF contains active phenolic hydroxyl group, it is affected by it benzene
Be easy on ring occur nitration reaction, in this reaction process often because be added dropwise nitric acid, heat release, cause internal temperature significantly on
It rises, by-product and oxide is caused to increase.Bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2- are the bis- (3- of synthesis 2,2-
Amino-4-hydroxylphenyl) hexafluoropropane raw material.Due to its unique design feature, make its electronics industry, light wave communication,
Aerospace and gas separation field have wide development prospect.
Trifluoroacetic acid is used to dissolve raw materials bisphenol AF [bis- (4- hydroxy phenyls) hexafluoros third of 2,2- for solvent in the prior art
Alkane)], potassium nitrate is added portionwise in controlling reaction temperature, and insulation reaction terminates, and is added in ice water and is precipitated, and filters, after washing and drying
It is impregnated with methanol, is dried in vacuo after elution and obtains yellow solid.Since trifluoroacetic acid is expensive in the above method, corrosivity is strong
And it is not suitable for industrialized production；Nitric acid in the reaction be easy to generate by-product, to operation require it is relatively high, and obtain product
Often do not reach requirement.
It also uses and is reported using acetic acid as solvent in the prior art, by the way that nitric acid is added dropwise, nitrifies bisphenol AF at normal temperatures and obtain
To bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2-.It is added in ice water and is precipitated, filter, impregnated with ethyl alcohol after washing and drying,
Vacuum drying obtains yellow solid after elution, but the synthesis yield that the above method generates is high, simple for process, but acetic acid is not easy back
It receives, it is of high cost；Nitric acid is easy to generate oxidized byproduct in the reaction.
In addition, in the prior art using chloroform as solvent, nitric acid nitrating bisphenol AF is added dropwise at normal temperatures and prepares bis- (the 3- nitre of 2,2-
Base -4- hydroxy phenyls) hexafluoropropane, additional acid catalyst is not needed, solvent can have with recovery and prepare simple side
Just feature.But due to the toxicity of chloroform, and it is the easy industrial chemicals that controls of system poison, since boiling point low-loss is big when recycling,
Using above receiving limitation.
Traditional handicraft is refined with methanol, ethyl alcohol, and product purity improves unobvious, and reaction impurities are difficult to remove.With organic
The refined product purity of solvent dichloroethanes, n-hexane extraction method is high, and environmental benefit is good, and pollution is less, can thoroughly eliminate anti-
By-product is answered, the product being easy to get to ideal yield and purity.The present invention find in a kind of processing adjacent nitro bisphenol AF oxidation peak and
The method of its by-product can overcome the influence brought by nitric acid.
Invention content
The process for refining of bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2- of the present invention discloses new scheme, and 1.2,
The process for refining of bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2-, it is characterized in that including step：
(1), by bis- (3- nitro -4- hydroxy phenyls) the hexafluoropropane crude products of 2,2-, potassium carbonate is added or sodium hydroxide solution stirs
It mixes to product and all dissolves；
(2) dissolved solution is filtered, filter impurity；
(3) hydrochloric acid is added dropwise into the solution of step (2), solution is adjusted to pH value 1-7, solid is precipitated；
(4) after solid addition dichloromethane dissolving will be precipitated, washed, be layered with sodium carbonate liquid, oil reservoir concentration is cooling
Crystallization filters, washing, is dried in vacuo, obtains bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2-.Wherein carbon in step (1)
The content of sour potassium is 9-11%, and it is 2-20 times that wherein dichloromethane solution amount, which inserts,.Hydrochloric acid is wherein added dropwise in step (3) by solution
It is adjusted to pH value 1-2, solid is precipitated., the content of sodium carbonate is 10% wherein in step (4).Wherein step (3) dropwise addition hydrochloric acid will be molten
Liquid is adjusted to pH value 5-7.
In addition the process for refining of bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2- of the present invention discloses new scheme,：
The process for refining of 2,2- bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane, it is characterized in that including step：
(1), by bis- (3- nitro -4- hydroxy phenyls) the hexafluoropropane crude products of 2,2-, addition solution of potassium carbonate stirs complete to product
It dissolves in portion；
(2) dissolved solution is filtered, filter impurity；
(3) hydrochloric acid solution modulation PH 1-2 solids are added dropwise into the solution of step (2) to be precipitated；
(4) after solid addition normal hexane dissolving will be precipitated, washed, be layered with sodium carbonate liquid, oil reservoir concentration is cooling to tie
Crystalline substance filters, washing, is dried in vacuo, obtains bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2-.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Fig. 2 be bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of the 2,2- of preparation process embodiment one of the present invention through extraction,
HPLC spectrogram spectrograms after washing, crystallization.
Fig. 3 is the HPLC spectrograms after ethyl alcohol recrystallization of preparation process embodiment two of the present invention.
Specific implementation mode
Below in conjunction with process flow chart and experimental data, the invention will be further described.
As shown in Figure 1, bis- (3- nitro -4- hydroxy phenyls) the hexafluoropropane process flow charts of 2,2- of the present invention.Bis- (the 3- of 2,2-
Nitro -4- hydroxy phenyls) the refined preparation process of hexafluoropropane includes the following steps.
Embodiment 1：In three-necked flasks of the 500ml equipped with electric mixer, the bis- (3- nitros -4- of 33.6 grams of 2,2- are added
Hydroxy phenyl) hexafluoropropane crude product (purity 92.61%), 10% solution of potassium carbonate is added and stirs to product and all dissolves, it will be molten
Solution after solution filters, and filters impurity.1MOL/L hydrochloric acid is added dropwise into solution, solution is adjusted to pH value 1-2, solid is precipitated.It is precipitated
Solid adds 2-20 times of dichloromethane dissolving, is washed, is layered with 10% sodium carbonate liquid of 30ml, oil reservoir concentration, crystallisation by cooling,
It filters, washing, be dried in vacuo, obtain bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 29.5 grams of 2,2-.It is measured through HPLC, it is pure
Degree is 99.77%, and main impurity contains 0.05%.Attached drawing one is HPLC spectrograms.
Embodiment 2
Test method finally uses 1MOL/L with experimental example one the difference is that Extraction solvent replaces dichloromethane with normal hexane
Solution PH is adjusted to 5-7 by hydrochloric acid, and solid occurs, crystallisation by cooling, is filtered, washing, is dried in vacuo, obtains 28.9 grams of bis- (3- of 2,2-
Nitro -4- hydroxy phenyls) hexafluoropropane.It is measured through HPLC, purity 99.72%.
Embodiment 3
Test method, the difference is that replacing 10% solution of potassium carbonate with 10% caustic lye of soda, is finally used with experimental example one
Solution PH is adjusted to 5-7 by hydrochloric acid, and solid occurs, crystallisation by cooling, is filtered, washing, is dried in vacuo, obtains 28.0 grams of bis- (3- of 2,2-
Nitro -4- hydroxy phenyls) hexafluoropropane.It is measured through HPLC, purity 99.70%.
Embodiment 4
In three-necked flasks of the 500ml equipped with electric mixer, it is bis- (3- nitro -4- hydroxy phenyls) that 33.6 grams of 2,2- are added
Ethyl alcohol 100ml is added in hexafluoropropane crude product (purity 92.61%), and heating stirring to product all dissolves, by dissolved solution
It filters, filters impurity, crystallisation by cooling filters, washing, is dried in vacuo, obtains 28.5 grams of 2,2- bis- (3- nitro -4- hydroxy phenyls)
Hexafluoropropane.It is measured through HPLC, purity 97.91%, main impurity contains 1.89%.Attached drawing 3 is HPLC spectrograms.
Based on These characteristics, bis- (3- nitro -4- hydroxy phenyls) the hexafluoropropane preparation processes of 2,2- of this programme are compared to existing
Some preparation processes have substantive distinguishing features outstanding and significant progress.
The present invention finds oxidation peak and its method of by-product in a kind of processing adjacent nitro bisphenol AF by experiment, can be with
Overcome the influence brought by nitric acid.Traditional handicraft is refined with methanol, ethyl alcohol, and product purity improves unobvious, and reaction impurities are difficult
With removal.High with the refined product purity of organic solvent dichloroethanes, n-hexane extraction method, environmental benefit is good, and pollution is less, can
With thorough elimination reaction by-product, the product that is easy to get to ideal yield and purity.
Claims (7)
- The process for refining of 1.2,2- bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane, it is characterized in that including step：(1) by bis- (3- nitro -4- hydroxy phenyls) the hexafluoropropane crude products of 2,2-, be added potassium carbonate or sodium hydroxide solution stir to Product all dissolves；(2) dissolved solution is filtered, filter impurity；(3) hydrochloric acid is added dropwise into the solution of step (2), solution is adjusted to pH value 1-7, solid is precipitated；(4) after solid addition dichloromethane dissolving will be precipitated, washed, be layered with sodium carbonate liquid, oil reservoir concentration, crystallisation by cooling, It filters, washing, be dried in vacuo, obtain bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2-.
- 2. process for refining according to claim 1, which is characterized in that the content of potassium carbonate is 9- wherein in step (1) 11%, it is 2-20 times that wherein dichloromethane solution amount, which inserts,.
- 3. process for refining according to claim 1, which is characterized in that hydrochloric acid is wherein added dropwise in step (3) and is adjusted to solution PH value 1-2, solid are precipitated.
- 4. process for refining according to claim 1, which is characterized in that the content of sodium carbonate is 10% wherein in step (4).
- 5. process for refining according to claim 1, which is characterized in that hydrochloric acid is wherein added dropwise in step (3) by solution pH value It is transferred to 5-7.
- The process for refining of 6.2,2- bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane, it is characterized in that including step：(1), by bis- (3- nitro -4- hydroxy phenyls) the hexafluoropropane crude products of 2,2-, addition solution of potassium carbonate stirs all molten to product Solution；(2) dissolved solution is filtered, filter impurity；(3) hydrochloric acid is added dropwise into the solution of step (2), solution is adjusted to pH values to 1-2, solid is precipitated；(4) after solid addition normal hexane dissolving will be precipitated, washed, be layered with sodium carbonate liquid, oil reservoir concentration, crystallisation by cooling is taken out Filter, washing, vacuum drying, obtain bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2-.
- 7. process for refining according to claim 6, which is characterized in that the content of sodium carbonate is 10% wherein in step (4).
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| CN201410790967.4A CN105712885B (en) | 2014-12-18 | 2014-12-18 | A kind of process for refining of bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2- |
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| CN201410790967.4A CN105712885B (en) | 2014-12-18 | 2014-12-18 | A kind of process for refining of bis- (3- nitro -4- hydroxy phenyls) hexafluoropropane of 2,2- |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028728A (en) * | 1987-02-10 | 1991-07-02 | Hoechst Aktiengesellschaft | Process for the preparation of reaction products of 2,2-bis-(4-hydroxphenyl)-hexafluoropropane and new derivatives of this type |
| CN1919812A (en) * | 2006-09-12 | 2007-02-28 | 上海三爱富新材料股份有限公司 | Refining method for hexafluoromethylene aromatic compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3901302B2 (en) * | 1997-10-02 | 2007-04-04 | 日本化薬株式会社 | Process for producing bis (3-nitro-4-hydroxyphenyl) s |
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- 2014-12-18 CN CN201410790967.4A patent/CN105712885B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028728A (en) * | 1987-02-10 | 1991-07-02 | Hoechst Aktiengesellschaft | Process for the preparation of reaction products of 2,2-bis-(4-hydroxphenyl)-hexafluoropropane and new derivatives of this type |
| CN1919812A (en) * | 2006-09-12 | 2007-02-28 | 上海三爱富新材料股份有限公司 | Refining method for hexafluoromethylene aromatic compound |
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