CN113620925B - Synthetic method of fluorine-containing monomer 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle - Google Patents
Synthetic method of fluorine-containing monomer 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle Download PDFInfo
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- CN113620925B CN113620925B CN202111075837.9A CN202111075837A CN113620925B CN 113620925 B CN113620925 B CN 113620925B CN 202111075837 A CN202111075837 A CN 202111075837A CN 113620925 B CN113620925 B CN 113620925B
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- 239000000178 monomer Substances 0.000 title claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 20
- 239000011737 fluorine Substances 0.000 title claims abstract description 20
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 18
- YSAVZVORKRDODB-WDSKDSINSA-N diethyl tartrate Chemical compound CCOC(=O)[C@@H](O)[C@H](O)C(=O)OCC YSAVZVORKRDODB-WDSKDSINSA-N 0.000 claims abstract description 11
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 4
- JIDAGSJRPLGWQX-UHFFFAOYSA-N 2,2-difluoro-4,5-bis(trifluoromethyl)-1,3-dioxolane Chemical compound C1(C(OC(O1)(F)F)C(F)(F)F)C(F)(F)F JIDAGSJRPLGWQX-UHFFFAOYSA-N 0.000 claims description 18
- TWJBTDKQXJODFN-UHFFFAOYSA-N OC(C(C(C(O)=O)O1)OC1(F)F)=O Chemical compound OC(C(C(C(O)=O)O1)OC1(F)F)=O TWJBTDKQXJODFN-UHFFFAOYSA-N 0.000 claims description 17
- WEHMRMJXORNKAL-UHFFFAOYSA-N FC(C(C(C(F)(F)F)(O1)Cl)(OC1(F)F)Cl)(F)F Chemical compound FC(C(C(C(F)(F)F)(O1)Cl)(OC1(F)F)Cl)(F)F WEHMRMJXORNKAL-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QOQDXCOIEQMTHN-UHFFFAOYSA-N CCOC(C(C(C(OCC)=O)O1)OC1S(O)(=O)=O)=O Chemical compound CCOC(C(C(C(OCC)=O)O1)OC1S(O)(=O)=O)=O QOQDXCOIEQMTHN-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- UAAMOJRODPRTNJ-UHFFFAOYSA-N diethyl 2,2-difluoro-1,3-dioxolane-4,5-dicarboxylate Chemical compound CCOC(C(C(C(OCC)=O)O1)OC1(F)F)=O UAAMOJRODPRTNJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- FQFKTKUFHWNTBN-UHFFFAOYSA-N trifluoro-$l^{3}-bromane Chemical compound FBr(F)F FQFKTKUFHWNTBN-UHFFFAOYSA-N 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 150000007530 organic bases Chemical class 0.000 claims description 7
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 claims description 6
- SDFBBZOTQLIIBC-UHFFFAOYSA-N FC(C(CO1)C(C(F)(F)F)OC1(F)F)(F)F Chemical compound FC(C(CO1)C(C(F)(F)F)OC1(F)F)(F)F SDFBBZOTQLIIBC-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- VLGORTLNRFBGEY-UHFFFAOYSA-N CCOC(=O)C1OC(=S)OC1C(=O)OCC Chemical compound CCOC(=O)C1OC(=S)OC1C(=O)OCC VLGORTLNRFBGEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- BWZHKRSSCFRVIE-UHFFFAOYSA-N 1-n,4-n-dimethyl-2h-pyridine-1,4-diamine Chemical compound CNN1CC=C(NC)C=C1 BWZHKRSSCFRVIE-UHFFFAOYSA-N 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 12
- 229920005548 perfluoropolymer Polymers 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229960001701 chloroform Drugs 0.000 description 5
- 229920002313 fluoropolymer Polymers 0.000 description 5
- 239000004811 fluoropolymer Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- MFILUIBHWRPXFZ-UHFFFAOYSA-N CCOC(C1OC(OS(O)(=O)=O)OC1C(OCC)=O)=O Chemical compound CCOC(C1OC(OS(O)(=O)=O)OC1C(OCC)=O)=O MFILUIBHWRPXFZ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 2
- JWKJOADJHWZCLL-UHFFFAOYSA-N 1,2,3,4,5,5,6,6,6-nonafluoro-1-(1,2,3,4,5,5,6,6,6-nonafluorohexa-1,3-dienoxy)hexa-1,3-diene Chemical compound FC(OC(F)=C(F)C(F)=C(F)C(F)(F)C(F)(F)F)=C(F)C(F)=C(F)C(F)(F)C(F)(F)F JWKJOADJHWZCLL-UHFFFAOYSA-N 0.000 description 2
- JSGITCLSCUKHFW-UHFFFAOYSA-N 2,2,4-trifluoro-5-(trifluoromethoxy)-1,3-dioxole Chemical compound FC1=C(OC(F)(F)F)OC(F)(F)O1 JSGITCLSCUKHFW-UHFFFAOYSA-N 0.000 description 2
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- 229940029284 trichlorofluoromethane Drugs 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- YSAVZVORKRDODB-UHFFFAOYSA-N Diethyl tartrate Chemical compound CCOC(=O)C(O)C(O)C(=O)OCC YSAVZVORKRDODB-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a synthesis method of a fluorine-containing monomer 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxygen heterocycle, which adopts diethyl tartrate as a starting raw material to obtain the fluorine-containing monomer 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxygen heterocycle after a series of reactions such as cyclization, fluorination, hydrolysis, substitution, dechlorination and the like. The method disclosed by the invention is reasonable in design, short in route, cheap and easily available in raw materials, simple to operate, easy to control and beneficial to realizing industrial production.
Description
Technical Field
The invention relates to the technical field of synthesis of fluorine-containing monomers, in particular to a synthesis method of a fluorine-containing monomer 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle.
Background
All commercial fluoropolymers were semi-crystalline materials before the 80's of the 20 th century, which greatly limited their use due to poor light transmission and solubility of crystalline polymers. In 1985, DuPont firstly copolymerized 2, 2-bis (trifluoromethyl) -4, 5-difluoro-1, 3-dioxole (PDD) with tetrafluoroethylene to obtain a perfluorinated amorphous polymer Teflon AF, and opened the research field of preparation and application technology of the perfluorinated amorphous polymer. Thereafter, the Asahi nitroxide was cyclopolymerized using perfluorobutenyl vinyl ether (PBVE) to obtain an amorphous resin, i.e., Cytop; suwei incorporated 2,2, 4-trifluoro-5-trifluoromethoxy-1, 3-dioxole (TTD) into the polymer to give Hyflon AD; the molecular structural formulas of these several typical Amorphous Fluoropolymers (AF) are as follows:
as amorphous perfluoropolymers, there are certain performance advantages over crystalline perfluoropolymers. Amorphous perfluoropolymers inherit their excellent chemical, thermal and electrical properties from crystalline perfluoropolymers, while they also have high transparency, good solubility and better mechanical properties. Films made from amorphous perfluoropolymers possess excellent optical clarity, the lowest refractive index of all known organic materials, and are particularly useful for certain specialty optical applications, they exhibit extremely high UV transparency, visibility at near IR wavelengths, and the lowest dielectric constant of the perfluoropolymer in the known polymers.
Amorphous perfluoropolymers can be melt processed by all conventional processing techniques. Good solubility in certain solvents makes them flexible for a variety of specialty applications, such as ultra-thin films or integrated circuits. For example, spin coating of amorphous perfluoropolymer solutions is an excellent process for thin, regular coatings on planar substrates, and non-planar surfaces are typically sprayed or dipped. The lowest dielectric constant and extremely low water absorption are extremely useful for interlayer dielectrics. The high optical clarity and extremely low refractive index make amorphous perfluoropolymers useful as optical lenses and protective coatings. A novel application of amorphous perfluoropolymers is as the core and cladding of optical fibers, such as Lucina, Asahi glass. Other applications include electronic lithography applications, tuning of low dielectric constant insulators for computer integrated circuits and high performance electronic connection products.
At present, the core preparation technology of amorphous fluoropolymer is not mastered at home, and the development of the amorphous fluoropolymer at home and abroad mainly focuses on deep development of downstream application of various approaches; moreover, the extremely high price of amorphous perfluoropolymers limits the use of common fields other than specialty applications. For a long time, the main factor restricting the development of amorphous fluoropolymer is that the preparation technology of corresponding special monomer for copolymerization is relatively backward, and because of the factors of more monomer synthesis steps, low yield, large process difficulty and the like, the production cost of the monomer is very high, and the industrial production is difficult to realize.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for synthesizing 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle by using a fluorine-containing monomer, so as to solve the problems of multiple steps, low yield, harsh reaction conditions and high process difficulty of the fluorine-containing monomer in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthetic method of 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle containing fluorine monomer comprises the following steps:
step 1, reacting diethyl tartrate with thiophosgene in the presence of organic base to obtain 2-sulfo-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester;
step 2, carrying out fluorination reaction on 2-sulfo-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester and bromine trifluoride to obtain 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester;
step 3, performing hydrolysis reaction on 2, 2-difluoro-1, 3-dioxolane-4, 5-diethyl phthalate in an alkaline environment to obtain 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid;
step 4, converting two carboxyl groups in the 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid into trifluoromethyl under the action of sulfur tetrafluoride and anhydrous hydrogen fluoride to generate 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane;
step 5, reacting 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane with chlorine under the illumination condition to obtain 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane;
and 6, carrying out dechlorination on 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane under the action of magnesium powder and 1, 2-dibromoethane to obtain the 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a method for synthesizing a novel special fluorine-containing monomer 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle for the first time, diethyl tartrate is used as an initial raw material, the whole synthetic route is short, other adopted raw materials are cheap and easy to obtain, the reaction conditions of each intermediate are very mild and easy to control, and the method is suitable for industrial production.
2. The fluorine-containing monomer 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxygen heterocycle prepared by the invention can be polymerized with tetrafluoroethylene, and the polymer of the monomer has excellent chemical, thermal and electrical properties, high transparency, good solubility and better mechanical properties; the film prepared by the polymer has excellent optical transparency, the refractive index is lowest in all known organic materials, and the polymer is particularly suitable for certain special optical applications, shows extremely high UV transparency and visibility of near IR wavelength, has better solubility and lower viscosity in fluorine solvent with the lowest dielectric constant in the known polymer, is suitable for solution processing technology, and can be used as a gas separation membrane; the monomer and a perfluoro vinyl ether monomer with a sulfonyl fluoride group at the tail end are subjected to free radical copolymerization to obtain a perfluoro sulfonic acid polymer with a dioxa ring structure on the main chain, and the perfluoro vinyl ether monomer is used for a solid electrode material in a polymer fuel cell, so that the perfluoro sulfonic acid polymer has good gas permeability and a better softening point, and can be better adapted to the high-temperature use environment of the solid polymer fuel cell.
Detailed Description
The present invention will be further described with reference to the following examples.
Synthetic method of fluorine-containing monomer 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle
Step 1, reacting diethyl tartrate (1) with thiophosgene in the presence of organic base to obtain 2-sulfo-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester (2); wherein, trichloromethane is used as a solvent, 4-dimethylamino pyridine is used as an organic base, the reaction is carried out at room temperature, and the molar ratio of diethyl tartrate to the organic base to thiophosgene is 1 (2-4) to 1-1.5.
Step 2, carrying out fluorination reaction on 2-sulfo-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester (2) and bromine trifluoride to obtain 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester (3); dissolving bromine trifluoride in a solvent trichloromethane, adding 2-sulfo-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester into a reaction system, and reacting at the temperature of-10-0 ℃, wherein the molar ratio of the 2-sulfo-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester to the bromine trifluoride is 1: 1-3.
Step 3, performing hydrolysis reaction on 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester (3) in an alkaline environment to obtain 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid (4); methanol is selected as a solvent, a reaction system is heated to 60-70 ℃ and forms reflux, and the molar ratio of diethyl 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylate to sodium hydroxide is 1: 2-4.
Step 4, converting two carboxyl groups in the 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid (4) into trifluoromethyl under the action of sulfur tetrafluoride and anhydrous hydrogen fluoride to generate 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane (5); the reaction is carried out in a high-pressure reaction kettle by vacuumizing, and the reaction temperature is 15-25 ℃; the molar ratio of the 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid to the sulfur tetrafluoride is 1: 2-5, a reaction system is neutralized after the reaction is finished, and the lower-layer liquid is taken out in a layered mode and washed to obtain colorless liquid.
Step 5, under the condition of illumination, 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane (5) reacts with chlorine to obtain 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane (6); the reaction is carried out at 120-130 ℃, and the reaction system after the reaction is washed by alkaline aqueous solution.
Step 6, carrying out dechlorination on 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane (6) under the action of magnesium powder and 1, 2-dibromoethane to obtain 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane (7); tetrahydrofuran is used as a solvent, the reaction temperature is 60-65 ℃, and the molar ratio of 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane to magnesium powder to 1, 2-dibromoethane is 1 (2-4) to 0.1-0.3.
The whole reaction route is as follows:
the invention carries out intensive research on the synthesis process of the fluorine-containing monomer, and finds that a short synthetic route of the perfluorinated monomer can be formed by adopting cheap and easily-obtained diethyl tartrate as an initial raw material, carrying out cyclization reaction with thiophosgene in the presence of organic alkali, carrying out fluorination reaction with bromine trifluoride to graft fluorine element on a ring, and carrying out combined action of hydrolysis, fluoride and substitution reaction; the synthesis conditions of each intermediate are very mild, harsh reaction conditions are not needed, the reaction process is easy to control, the yield is high, and the method is very favorable for realizing industrial production.
Second, preparation of examples
Example 1:
(1) synthesis of diethyl 2-sulfoxy-1, 3-dioxolane-4, 5-dicarboxylate (2)
Diethyl tartrate (10.3g, 50.0mmol) and 4-dimethylaminopyridine (14.7g, 120.0mmol) were dissolved in 100mL of chloroform at room temperature, a 75mL trichloromethane solution of thiophosgene (3.8mL, 50.0mmol) was added dropwise, and after the addition, the reaction was stirred at room temperature for 4 hours, thereby completing the reaction.
13g of crude 2-sulfoxy-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester with the content of 99 percent, tartaric acid diethyl ester with the content of 0.3 percent, 4-dimethylaminopyridine with the content of 0.3 percent and other contents with the content of 0.4 percent are collected, and the yield reaches 96 percent.
(2) Synthesis of diethyl 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylate (3)
A solution of bromine trifluoride (45.0mmol) in 5mL of trichlorofluoromethane at 0 ℃ was added dropwise to 100mL of trichloromethane of diethyl 2-thioxo-1, 3-dioxolane-4, 5-dicarboxylate (11.2g, 45.0mmol) through a constant pressure funnel. Then, an aqueous solution of sodium sulfite was added dropwise to the reaction system until colorless, and the reaction was completed.
13g of crude 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester with a content of 97%, bromine trifluoride with a content of 1%, trichlorofluoromethane with a content of 1%, 2-sulfoxy-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester with a content of 0.5%, and the other contents with a content of 0.5% were collected, and the yield reached 94%.
(3) Synthesis of 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid (4)
Diethyl 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylate (9.7g, 38.2mmol) was dissolved in 100mL of methanol, 20mL of an aqueous solution of sodium hydroxide (3.4g, 84.0mmol) was added, and then the reaction system was heated to 65 ℃ for reaction for 30 minutes. And cooling to room temperature, evaporating methanol under reduced pressure, adjusting the pH value of the system to 2-3 by using 1M hydrochloric acid, and finishing the reaction.
8.5g of crude 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid with a content of 98%, 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid with a content of 1%, the other contents being 1%, was collected, and the yield was 98%.
(4) Synthesis of 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane (5)
2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid (7.4g, 37.4mmol) was placed in a 100mL stainless steel autoclave, evacuated, cooled to-60 ℃ and then added with 5mL anhydrous hydrogen fluoride and sulfur tetrafluoride (8.9g, 82.3mmol) in that order. The obtained reaction system is heated to 20 ℃ and stirred for 20 hours, and the reaction is finished.
9.2g of crude 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane was collected, the content of 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid was 98%, the content of the other 1%, and the yield was 95%.
(5) Synthesis of 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane (6)
Under the irradiation of a fluorescent lamp, chlorine gas is introduced into 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane (6.9g, 28.0mmol), and the reaction is carried out at 120-130 ℃. The progress of the reaction was monitored by gas chromatography until the substrate was completely chlorinated. The reaction system was washed with 2M aqueous sodium hydroxide and the product was dried and used directly in the next step.
(6) Synthesis of 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxan (7)
Magnesium powder (2.0g, 84.0mmol) is dissolved in 30mL of dry tetrahydrofuran, 1, 2-dibromoethane (0.24mL, 2.8mmol) is added under the protection of nitrogen, then 10mL of tetrahydrofuran solution of the obtained 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane (28.0mmol) is added dropwise through a constant pressure funnel, the temperature of the system rises to 60-65 ℃ for reaction after the dropwise addition is finished, and the reaction progress is monitored by gas chromatography.
The collected product contains 98% of 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle, 0.5% of 1, 2-dibromoethane, 0.5% of 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane and 1% of other components, and the yield in two steps reaches 92%.
The same preparation method as in example 1 was used to prepare the raw materials shown in table 1, thereby obtaining examples 2 to 6.
TABLE 1
The purity of the product obtained by the preparation method of the embodiment 1-6 is over 98 percent, the product purity is high, and the method can be directly used for synthesizing the fluorine-containing polymer. In the preparation process, the yield of each intermediate is high, the obtained intermediate has high purity, almost no by-product is generated, the reaction process in each step is easy to control, and the method is very suitable for industrial production.
Third, product verification
Taking example 1 as an example, ESI-MS and GC/MS were used to examine the intermediate compounds during the reaction, and the results are shown in the following table.
TABLE 2
| Item | Compound 2 | Compound 3 | Compound 4 | Compound 5 | Compound 6 | Compound 7 |
| ESI-MS(g/mol) | 248.25 | 254.18 | 198.08 | 246.06 | 314.95 | 244.04 |
| GC/MS(％) | 98 | 99 | 96 | 99 | 99 | 98 |
As can be seen from Table 2, the desired intermediate compound can be prepared during the preparation process, and the purity of the intermediate compound is high, which is beneficial for the next reaction and can ensure that the fluorine-containing monomer is finally obtained.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (7)
1. A synthetic method of 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle containing fluorine monomer is characterized by comprising the following steps:
step 1, reacting diethyl tartrate with thiophosgene in the presence of organic base to obtain 2-sulfo-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester;
step 2, carrying out fluorination reaction on 2-sulfo-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester and bromine trifluoride to obtain 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid diethyl ester;
step 3, performing hydrolysis reaction on 2, 2-difluoro-1, 3-dioxolane-4, 5-diethyl phthalate in an alkaline environment to obtain 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid;
step 4, converting two carboxyl groups in the 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid into trifluoromethyl under the action of sulfur tetrafluoride and anhydrous hydrogen fluoride to generate 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane;
step 5, reacting 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane with chlorine under the illumination condition to obtain 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane;
and 6, carrying out dechlorination on 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane under the action of magnesium powder and 1, 2-dibromoethane to obtain the 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane.
2. The method for synthesizing 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle as a fluorine-containing monomer according to claim 1, wherein chloroform is used as a solvent in the step 1, 4-dimethylaminopyridine is used as an organic base, and the reaction is carried out at room temperature, wherein the molar ratio of diethyl tartrate to the organic base to thiophosgene is 1 (2-4) to 1-1.5.
3. The method for synthesizing 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxan as a fluoromonomer according to claim 1, wherein bromine trifluoride is dissolved in chloroform as a solvent in the step 2, and the reaction is carried out at-10 ℃ to 0 ℃ and the molar ratio of diethyl 2-thioxo-1, 3-dioxolane-4, 5-dicarboxylate to bromine trifluoride is 1:1 to 3.
4. The method for synthesizing 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle containing fluoromonomer according to claim 1, wherein methanol is used as a solvent in step 3, the reaction system is heated to 60-70 ℃ to form reflux, and the molar ratio of diethyl 2, 2-difluoro-1, 3-dioxypentane-4, 5-dicarboxylate to sodium hydroxide is 1: 2-4.
5. The method for synthesizing 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxyheterocycle containing fluoromonomer according to claim 1, wherein the reaction in step 4 is carried out in a high-pressure reaction kettle by vacuumizing, and the reaction temperature is 15-25 ℃; the molar ratio of the 2, 2-difluoro-1, 3-dioxolane-4, 5-dicarboxylic acid to the sulfur tetrafluoride is 1: 2-5, a reaction system is neutralized after the reaction is finished, and the lower-layer liquid is taken out in a layered mode and washed to obtain colorless liquid.
6. The method for synthesizing 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxan as a fluoromonomer according to claim 1, wherein the reaction in the step 5 is carried out at 120 to 130 ℃ and the reaction system after the reaction is washed with an aqueous alkaline solution.
7. The method for synthesizing 2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxan as a fluorine-containing monomer according to claim 1, wherein tetrahydrofuran is used as a solvent in the step 6, and the reaction temperature is 60-65 ℃ and the molar ratio of 4, 5-dichloro-2, 2-difluoro-4, 5-bis (trifluoromethyl) -1, 3-dioxolane to magnesium powder to 1, 2-dibromoethane is 1 (2-4) to (0.1-0.3).
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|---|---|---|---|---|
| US4393227A (en) * | 1981-08-12 | 1983-07-12 | E. I. Du Pont De Nemours And Company | Process for dechlorinating organic compounds |
| US4399264A (en) * | 1981-11-19 | 1983-08-16 | E. I. Du Pont De Nemours & Co. | Perfluorodioxole and its polymers |
| CA1198119A (en) * | 1981-11-19 | 1985-12-17 | Edward N. Squire | 4,5-dichloro-2,2,4,5 tetrafluoro-1,3-dioxolane |
| US4908410A (en) * | 1989-01-27 | 1990-03-13 | E. I. Du Pont De Nemours And Company | Modified polytetrafluoroethylene fine powder and preparation thereof |
| US4908461A (en) * | 1987-12-21 | 1990-03-13 | E. I. Du Pont De Nemours And Company | Process for dechlorinating 4,5-dichlorofluorodioxolanes to obtain fluorodioxoles |
| US5177224A (en) * | 1989-08-28 | 1993-01-05 | E. I. Du Pont De Nemours And Company | Process for the preparation of halogenated 2,2-bis(trifluoromethyl)-1,3-dioxolanes |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4393227A (en) * | 1981-08-12 | 1983-07-12 | E. I. Du Pont De Nemours And Company | Process for dechlorinating organic compounds |
| US4399264A (en) * | 1981-11-19 | 1983-08-16 | E. I. Du Pont De Nemours & Co. | Perfluorodioxole and its polymers |
| CA1198119A (en) * | 1981-11-19 | 1985-12-17 | Edward N. Squire | 4,5-dichloro-2,2,4,5 tetrafluoro-1,3-dioxolane |
| US4908461A (en) * | 1987-12-21 | 1990-03-13 | E. I. Du Pont De Nemours And Company | Process for dechlorinating 4,5-dichlorofluorodioxolanes to obtain fluorodioxoles |
| US4908410A (en) * | 1989-01-27 | 1990-03-13 | E. I. Du Pont De Nemours And Company | Modified polytetrafluoroethylene fine powder and preparation thereof |
| US5177224A (en) * | 1989-08-28 | 1993-01-05 | E. I. Du Pont De Nemours And Company | Process for the preparation of halogenated 2,2-bis(trifluoromethyl)-1,3-dioxolanes |
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