CN108395363A - 2,2- of one kind is bis-（3,4- xylyls）The preparation method of hexafluoropropane - Google Patents
2,2- of one kind is bis-（3,4- xylyls）The preparation method of hexafluoropropane Download PDFInfo
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- CN108395363A CN108395363A CN201810173489.0A CN201810173489A CN108395363A CN 108395363 A CN108395363 A CN 108395363A CN 201810173489 A CN201810173489 A CN 201810173489A CN 108395363 A CN108395363 A CN 108395363A
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- hexafluoropropane
- bis
- sulfonic acid
- xylyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 title claims abstract description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 14
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000012043 crude product Substances 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 4
- -1 4- xylyl Chemical group 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 5
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 229910006069 SO3H Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 2
- 150000002596 lactones Chemical class 0.000 claims 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 125000005023 xylyl group Chemical group 0.000 abstract 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- 238000011017 operating method Methods 0.000 abstract 1
- 239000004642 Polyimide Substances 0.000 description 16
- 229920001721 polyimide Polymers 0.000 description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RLTPXEAFDJVHSN-UHFFFAOYSA-N 4-(trifluoromethyl)benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=C(C(F)(F)F)C=C1 RLTPXEAFDJVHSN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- SNZAEUWCEHDROX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-one;trihydrate Chemical compound O.O.O.FC(F)(F)C(=O)C(F)(F)F SNZAEUWCEHDROX-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- GLFKFHJEFMLTOB-UHFFFAOYSA-N 4-[2-(3,4-dimethylphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-1,2-dimethylbenzene Chemical compound C1=C(C)C(C)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C)C(C)=C1 GLFKFHJEFMLTOB-UHFFFAOYSA-N 0.000 description 1
- CMIFONGOYJFOST-UHFFFAOYSA-N O.CC(=O)C.[F] Chemical compound O.CC(=O)C.[F] CMIFONGOYJFOST-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- OBHWOLDGXCOBAK-UHFFFAOYSA-N [F].CS(O)(=O)=O Chemical compound [F].CS(O)(=O)=O OBHWOLDGXCOBAK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of doing catalyst preparation 2, the synthesis technology of 2 bis- (3,4 xylyl) hexafluoropropane, including following operating procedure with sulfonic acid：1), ortho-xylene, sulfonic acid and solvent are mixed in proportion, obtain mixture；2) Hexafluoro acetone gas, is passed into the mixture in step 1), under reaction temperature and reaction pressure, crude product is obtained by the reaction, after crude product alkali cleaning, washing, concentration, crystallized solvent crystal, vacuum drying obtain 2,2 bis- (3,4 xylyl) hexafluoropropane.Present invention process is novel, and mild condition can obtain the LITHIUM BATTERY 2 of high-purity, 2 bis- (3,4 xylyl) hexafluoropropane.
Description
Technical field
The present invention relates to the synthesis technologies of the monomeric compound of fluorinated polyimide material, and in particular to 2,2- it is bis- (3,
4- xylyls) hexafluoropropane synthesis technology.
Background technology
Polyimides (PI) is a kind of high molecular material that phthalimide repetitive unit is carried on strand, rigid acid imide knot
Structure imparts the unique performance of polyimides, such as excellent high temperature resistance, resistance to environmental stability and good mechanical performance,
These characteristics make polyimides be widely used in fields such as Aeronautics and Astronautics, machinery, electrician and electronics, still
Polyimides is maximum the disadvantage is that infusibility indissoluble, is not easy processing and forming and production cost is high, this just brings to industrial production huge
Difficulty, to limit the application of PI.Fluorinated polyimide can significantly make up this defect, and the introducing of fluoro-containing group is not only big
The big dissolubility for improving PI, and assign the functionality such as the superior physical chemistry of PI, light, electricity and gas separation, make its
The fields such as electronics industry, light wave communication, aerospace and gas separation have unique advantage and wide development prospect, therefore fluorine-containing
Polyimides has become the hot subject studied both at home and abroad.
The chemical constitution of 2,2- bis- (3,4- xylyl) hexafluoropropane (abbreviation 6FXY) is as follows：
6FXY is synthesis 4, the raw material of 4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids (6FDA), use hexafluorodianhydride (6FDA) (6FDA) as
The polyimides of monomer mainly has following advantage in performance：The dielectric constant of low-k, common polyimides exists
3.4 or so, and after 6FDA is added, dielectric constant can be reduced to 2.5.Transparent and controllable refractive index, because of polyimides
Slightly yellowish or brown, after 6FDA is added, can so that it becomes transparent, and according to 6FDA be added how much, it can be controlled
Refractive index, chemistry and thermal stability.After introducing fluorine atom, because of the strong elecrtonegativity of fluorine atom, the chemistry and heat of polyimides are steady
It is qualitative to improve so that product can special chemistry or at a temperature of working lubrication.Because of the low polarity of fluorine atom,
So that fluorine-containing quasi-polyimide has very low surface free energy, surface is smooth, and frictional force is small.
The synthesis of 6FXY mainly has following report at present：
Japan Patent JP2006248961 reports ortho-xylene, and Hexafluoro acetone, anhydrous hydrofluoric acid is 90 DEG C in autoclave
Reaction 30 hours, equipment are complicated, it is difficult to operate, reaction pressure is higher.
Scholar Zhu is just et al. in J.F.C (2003), vol123, nb2, is also reported with adjacent diformazan in the paper of P221-225
Benzene, Hexafluoro acetone, anhydrous hydrofluoric acid in autoclave under 20atm 110 DEG C react 20 hours, yield 67%, at the same they use
Hexafluoropropylene oxide (HFPO), alchlor makees catalyst, in autoclave under 20atm 110 DEG C react 216 hours, yield
Only 25%.
Chinese patent CN101696199 is reported, with ortho-xylene, 2,2- dichlorohexafluoropr.panes, in ionic liquid (such as
1- butyl -3- methylimidazole quinolines tetrafluoroborate), the lower reaction of lewis' acid (such as alchlor) catalysis, but raw material 2,2- bis-
Chlorine hexafluoropropane, ionic liquid are difficult to obtain.
Chinese patent CN101851147 is reported, and with hexafluoropropylene oxide, ortho-xylene, anhydrous hydrofluoric acid is in autoclave
Interior reaction, is equally equipment complexity, and reaction pressure is higher, it is difficult to operate.
Chinese patent CN106699504 is reported, and becomes six with ortho-xylene and Hexafluoro acetone trihydrate reflux water-dividing
After fluorine acetone monohydrate, anhydrous hydrofluoric acid reaction is added, the hydrofluoric acid extremely strong again without corrosivity is detached from.
In conclusion being nearly all to have used Hexafluoro acetone gas, anhydrous hydrofluoric acid is as catalyst, or uses hexafluoro
Propylene oxide, lewis' acid make catalyst, are primarily present etching apparatus, complicated for operation, detach difficult problem.
Invention content
In order to solve prior art problem, the first aspect of the present invention provides bis- (3, the 4- xylyl) hexafluoros of 2,2- of one kind
The preparation method of propane, catalyst used by the preparation method includes sulfonic acid.
In some embodiments, the preparation method includes at least following steps：
1), ortho-xylene, sulfonic acid and solvent are mixed in proportion, obtain mixture；
2) Hexafluoro acetone gas, is passed into the mixture in step 1), under reaction temperature and reaction pressure, is reacted
To crude product, after crude product alkali cleaning, washing, concentration, crystallized solvent crystal, vacuum drying obtain bis- (3, the 4- diformazans of 2,2-
Phenyl) hexafluoropropane.
In some embodiments, the molar ratio of the ortho-xylene and sulfonic acid is 1.0：0.1~1.0：1.0.
In some embodiments, the sulfonic acid has following general formula CxHyFzSO3H, X are the number of 1~n, and Y is 1~n
Number, Z be 0~n number.
In some embodiments, the sulfonic acid is selected from pyrovinic acid, trifluoromethanesulfonic acid, 1- trifluoroethyls sulfonic acid, five fluorine
In ethylsulfonic acid, propyl sulfonic acid, 1- trifluoro propyls sulfonic acid, benzene sulfonic acid, 4- toluenesulfonic acids, 4- trifluoromethyl benzene sulfonic acids at least
It is a kind of.
In some embodiments, the solvent is tetrahydrofuran, ethyl acetate, methyl acetate, acetonitrile, glycol dinitrate
In ether, diethylene glycol dimethyl ether, ether, Isosorbide-5-Nitrae-dioxane, dichloromethane, dichloroethanes, gamma-butyrolacton, dimethyl carbonate
Any one is combined.
In some embodiments, the reaction temperature is 0~150 DEG C.
In some embodiments, the reaction pressure is 101kPa-150kPa.
In some embodiments, the crystallization solvent is methanol, ethyl alcohol, isopropanol, dimethyl sulfoxide, N, N- dimethyl
Formamide, n,N-dimethylacetamide, water, toluene, ethyl acetate, acetonitrile, methyl acetate, dichloromethane, dichloroethanes, second
Ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, one kind in Isosorbide-5-Nitrae-dioxane, gamma-butyrolacton or combination.
In some embodiments, the vacuum drying time is 0~72 hour；Temperature is 30~230 DEG C；Vacuum degree
For -0.1~0.1MPa.
The second aspect of the present invention provides bis- (3, the 4- xylyl) hexafluoropropane of 2,2- of one kind, by making as described above
Preparation Method is prepared.
In some embodiments, the GC purity of bis- (3, the 4- xylyl) hexafluoropropane of 2, the 2- is greater than or equal to
99.5%.
The positive effect of the present invention is that overcoming the existing side for preparing bis- (3, the 4- xylyl) hexafluoropropane of 2,2-
Generation in method, complicated for operation, to equipment requirement height, safety is insufficient, and quantity of three wastes is big etc. is unfavorable for the defect of industrialized production,
One kind is provided and has excellent performance synthesis technology.Its preparation condition is mild, and danger coefficient is low, and the three wastes are less, is suitble to industrialization extensive
Production, can obtain bis- (3, the 4- xylyl) hexafluoropropane of 2,2- of high-purity, and there is larger implementary value and society to pass through
Ji benefit.
Specific implementation mode
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim be closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to the element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " arbitrary
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
The first aspect of the present invention provides the preparation method of bis- (3, the 4- xylyl) hexafluoropropane of 2,2- of one kind, the system
Catalyst used by Preparation Method includes sulfonic acid.
In some embodiments, the preparation method includes at least following steps：
1), ortho-xylene, sulfonic acid and solvent are mixed in proportion, obtain mixture；
2) Hexafluoro acetone gas, is passed into the mixture in step 1), under reaction temperature and reaction pressure, is reacted
To crude product, after crude product alkali cleaning, washing, concentration, crystallized solvent crystal, vacuum drying obtain bis- (3, the 4- diformazans of 2,2-
Phenyl) hexafluoropropane.
In some embodiments, the molar ratio of the ortho-xylene and sulfonic acid is 1.0：0.1~1.0：1.0.、
In some embodiments, the sulfonic acid has following general formula CxHyFzSO3H, X are the number of 1~n, and Y is 1~n
Number, Z be 0~n number.
In some embodiments, the sulfonic acid is selected from pyrovinic acid, trifluoromethanesulfonic acid, 1- trifluoroethyls sulfonic acid, five fluorine
In ethylsulfonic acid, propyl sulfonic acid, 1- trifluoro propyls sulfonic acid, benzene sulfonic acid, 4- toluenesulfonic acids, 4- trifluoromethyl benzene sulfonic acids at least
It is a kind of.
Its specific example of sulfonic acid of the present invention includes but not limited to：Pyrovinic acid, trifluoromethanesulfonic acid, 1- trifluoroethyls
Sulfonic acid, pentafluoroethyl group sulfonic acid, propyl sulfonic acid, 1- trifluoro propyls sulfonic acid, benzene sulfonic acid, 4- toluenesulfonic acids, 4- trifluoromethylbenzene sulphurs
Acid.Has general formula CxHyFzSO3H, X are the number of 1~n, and Y is the number of 1~n, and Z is the number of 0~n.
In some embodiments, the solvent is tetrahydrofuran, ethyl acetate, methyl acetate, acetonitrile, glycol dinitrate
In ether, diethylene glycol dimethyl ether, ether, Isosorbide-5-Nitrae-dioxane, dichloromethane, dichloroethanes, gamma-butyrolacton, dimethyl carbonate
Any one is combined.
In some embodiments, the reaction temperature is 0~150 DEG C.
In some embodiments, the reaction pressure is 101kPa-150kPa.
In some embodiments, the crystallization solvent is methanol, ethyl alcohol, isopropanol, dimethyl sulfoxide, N, N- dimethyl
Formamide, n,N-dimethylacetamide, water, toluene, ethyl acetate, acetonitrile, methyl acetate, dichloromethane, dichloroethanes, second
Ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, one kind in Isosorbide-5-Nitrae-dioxane, gamma-butyrolacton or combination.
In some embodiments, the vacuum drying time is 0~72 hour；Temperature is 30~230 DEG C；Vacuum degree
For -0.1~0.1MPa.
The second aspect of the present invention provides bis- (3, the 4- xylyl) hexafluoropropane of 2,2- of one kind, by making as described above
Preparation Method is prepared.
In some embodiments, the GC purity of bis- (3, the 4- xylyl) hexafluoropropane of 2, the 2- is greater than or equal to
99.5%.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available.
Embodiment 1：In 1000 milliliters of vial, 600 grams of 1,2- dichloroethanes of addition, 212 grams of ortho-xylenes, 15 gram three
Fluorine methanesulfonic acid, 30 DEG C of temperature control are slowly introducing 250 grams of Hexafluoro acetone gases, after having led to, are warming up to reflux 6 hours, cool down, use
NaHCO3Saturated aqueous solution is washed to pH=7~8, and organic phase is washed once with pure water again, and concentration, obtained solid uses isopropanol
600 grammes per square metres crystallize, and 40 DEG C of wet product is dried in vacuo 12 hours, obtain 330 grams of product, yield 91.7%, and GC purity is 99.5%,
Single impurity is less than 0.1%, and all metal ions are less than 1ppm.
Embodiment 2：In 2000 milliliters of vial, 1000 grams of tetrahydrofurans are added, 424 grams of ortho-xylenes, 60 grams to first
Base benzene sulfonic acid, 40 DEG C of temperature control is hereinafter, be slowly introducing 400 grams of Hexafluoro acetone gases, after having led to, is warming up to reflux 12 hours, cooling,
Use NaHCO3500 grams of toluene is added in saturated aqueous solution, washing to pH=7~8, and layering, organic phase is washed once with pure water again, dense
Contracting, obtained solid are crystallized with 1200 grammes per square metre of ethyl alcohol, and 40 DEG C of wet product is dried in vacuo 12 hours, obtains 670 grams of product, yield is
93.1%, GC purity are 99.6%, and single impurity is less than 0.1%, and all metal ions are less than 1ppm.
Embodiment 3：In 2000 milliliters of vial, 1000 grams of glycol dimethyl ethers of addition, 424 grams of ortho-xylenes, 100 grams
Ethylsulfonic acid, 40 DEG C of temperature control is hereinafter, be slowly introducing 350 grams of Hexafluoro acetone gases, after having led to, is warming up to reflux 12 hours, cooling,
Use NaHCO31000 grams of dichloromethane, layering are added in saturated aqueous solution, washing to pH=7~8, and organic phase washes one with pure water again
Secondary, concentration, obtained solid is crystallized with 1400 grammes per square metre of isopropanol, and 40 DEG C of wet product is dried in vacuo 12 hours, obtains 648 grams of product,
Yield is that 90.1%, GC purity is 99.7%, and single impurity is less than 0.1%, and all metal ions are less than 1ppm.
Example above-mentioned is merely illustrative, some features for explaining the disclosure.The attached claims are intended to
The range as wide as possible being contemplated that is sought, and embodiments as presented herein is only the combination according to all possible embodiment
Selection embodiment explanation.Therefore, the purpose of applicant is the feature that the attached claims are not illustrated the present invention
Exemplary selectional restriction.And the progress in science and technology will be formed language express inaccuracy due to and it is not current
The possible equivalent or son considered is replaced, and these variations should also be interpreted to be wanted by appended right in the conceived case
Ask covering.
Claims (11)
1. one kind 2, the preparation method of bis- (3, the 4- xylyl) hexafluoropropane of 2-, which is characterized in that the preparation method is adopted
Catalyst includes sulfonic acid.
2. preparation method as described in claim 1, which is characterized in that the preparation method includes at least following steps：
1), ortho-xylene, sulfonic acid and solvent are mixed in proportion, obtain mixture；
2) Hexafluoro acetone gas, is passed into the mixture in step 1), under reaction temperature and reaction pressure, is obtained by the reaction thick
Product, after crude product alkali cleaning, washing, concentration, crystallized solvent crystal, vacuum drying obtain 2,2- bis- (3,4- xylyls)
Hexafluoropropane.
3. preparation method as claimed in claim 2, which is characterized in that the molar ratio of the ortho-xylene and sulfonic acid is 1.0：
0.1~1.0：1.0.
4. preparation method as claimed in claim 2, which is characterized in that the sulfonic acid has following general formula CxHyFzSO3H, X 1
The number of~n, Y are the number of 1~n, and Z is the number of 0~n.
5. preparation method as claimed in claim 2, which is characterized in that the solvent is tetrahydrofuran, ethyl acetate, acetic acid first
Ester, acetonitrile, glycol dimethyl ether, diethylene glycol dimethyl ether, ether, Isosorbide-5-Nitrae-dioxane, dichloromethane, dichloroethanes, γ-fourth
Any one in lactone, dimethyl carbonate or combination.
6. preparation method as claimed in claim 2, which is characterized in that the reaction temperature is 0~150 DEG C.
7. preparation method as claimed in claim 2, which is characterized in that the reaction pressure is 101kPa-150kPa.
8. preparation method as claimed in claim 2, which is characterized in that the crystallization solvent be methanol, ethyl alcohol, isopropanol, two
Methyl Asia phenol, n,N-Dimethylformamide, n,N-dimethylacetamide, water, toluene, ethyl acetate, acetonitrile, methyl acetate, two
Chloromethanes, dichloroethanes, ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, γ-fourth
One kind in lactone or combination.
9. preparation method as claimed in claim 2, which is characterized in that the vacuum drying time is 0~72 hour；Temperature
It is 30~230 DEG C；Vacuum degree is -0.1~0.1MPa.
10. one kind 2, bis- (3, the 4- xylyl) hexafluoropropane of 2-, by claim 1-9 any one of them preparation method systems
It is standby to obtain.
11. bis- (3, the 4- xylyl) hexafluoropropane of 2,2- as claimed in claim 9, which is characterized in that 2, the 2- it is bis- (3,
4- xylyls) hexafluoropropane GC purity be greater than or equal to 99.5%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678826A (en) * | 2019-02-21 | 2019-04-26 | 浙江诺诚技术发展有限公司 | A kind of method that temperate condition prepares hexafluorodianhydride (6FDA) |
| CN111302944A (en) * | 2020-03-31 | 2020-06-19 | 上海如鲲新材料有限公司 | Preparation method of bis (3-amino-4-hydroxyphenyl) hexafluoropropane |
| CN111470936A (en) * | 2020-06-08 | 2020-07-31 | 福建省漳平市九鼎氟化工有限公司 | Equipment and process for directly producing di-o-xylyl hexafluoroacetone from HFPO |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4307024A (en) * | 1978-03-30 | 1981-12-22 | Nasa | 1,1,1-Triaryl-2,2,2-trifluoroethanes and process for their synthesis |
| US4758380A (en) * | 1986-10-29 | 1988-07-19 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis |
| JPH0686393B2 (en) * | 1990-06-22 | 1994-11-02 | セントラル硝子株式会社 | Method for purifying aromatic compound containing hexafluoropropylidene group |
| CN1106372A (en) * | 1993-10-29 | 1995-08-09 | 日本梅克特隆株式会社 | Process for preparing 2,2-diphenylhexafluoropropanes |
| CN101696199A (en) * | 2009-11-06 | 2010-04-21 | 武邑新邑兴精细化工有限公司 | Preparation method of 4,4'-(Hexafluoroisopropylidene) diphthalic anhydride |
| CN106699504A (en) * | 2015-11-18 | 2017-05-24 | 浙江蓝天环保高科技股份有限公司 | Preparation method of 2,2-bis(3,4-dimethylphenyl)hexafluoropropane |
-
2018
- 2018-03-02 CN CN201810173489.0A patent/CN108395363B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4307024A (en) * | 1978-03-30 | 1981-12-22 | Nasa | 1,1,1-Triaryl-2,2,2-trifluoroethanes and process for their synthesis |
| US4758380A (en) * | 1986-10-29 | 1988-07-19 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis |
| JPH0686393B2 (en) * | 1990-06-22 | 1994-11-02 | セントラル硝子株式会社 | Method for purifying aromatic compound containing hexafluoropropylidene group |
| CN1106372A (en) * | 1993-10-29 | 1995-08-09 | 日本梅克特隆株式会社 | Process for preparing 2,2-diphenylhexafluoropropanes |
| CN101696199A (en) * | 2009-11-06 | 2010-04-21 | 武邑新邑兴精细化工有限公司 | Preparation method of 4,4'-(Hexafluoroisopropylidene) diphthalic anhydride |
| CN106699504A (en) * | 2015-11-18 | 2017-05-24 | 浙江蓝天环保高科技股份有限公司 | Preparation method of 2,2-bis(3,4-dimethylphenyl)hexafluoropropane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678826A (en) * | 2019-02-21 | 2019-04-26 | 浙江诺诚技术发展有限公司 | A kind of method that temperate condition prepares hexafluorodianhydride (6FDA) |
| CN109678826B (en) * | 2019-02-21 | 2023-03-14 | 浙江诺诚技术发展有限公司 | Method for preparing hexafluoro dianhydride under mild condition |
| CN111302944A (en) * | 2020-03-31 | 2020-06-19 | 上海如鲲新材料有限公司 | Preparation method of bis (3-amino-4-hydroxyphenyl) hexafluoropropane |
| CN111470936A (en) * | 2020-06-08 | 2020-07-31 | 福建省漳平市九鼎氟化工有限公司 | Equipment and process for directly producing di-o-xylyl hexafluoroacetone from HFPO |
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