WO2024002858A1 - Hydrofluoroether composition and method for its preparation - Google Patents
Hydrofluoroether composition and method for its preparation Download PDFInfo
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- WO2024002858A1 WO2024002858A1 PCT/EP2023/066979 EP2023066979W WO2024002858A1 WO 2024002858 A1 WO2024002858 A1 WO 2024002858A1 EP 2023066979 W EP2023066979 W EP 2023066979W WO 2024002858 A1 WO2024002858 A1 WO 2024002858A1
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- general formula
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- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims description 42
- 238000002360 preparation method Methods 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- -1 R is selected from H Chemical group 0.000 claims abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000003880 polar aprotic solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003809 water extraction Methods 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229960000834 vinyl ether Drugs 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 1
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
Definitions
- the invention relates to a hydrofluoroether composition which can find application as solvent.
- the invention also relates to a method of preparation of said composition.
- Solvents based on hydrofluoroethers are very advantageous if compared to alternative materials which are available in the market because they have low GWP (Global warming potential) low flammability and are thus safe and easy to handle.
- GWP Global warming potential
- the present invention relates to A liquid composition comprising one or more compounds according to general formula (I): and one or more compound according to general formula (II): wherein:
- a and B are independently selected from F, Cl, H, C1-C3 fluorinated alkyl, C1- C3 fluorinated alkoxy, R is selected from H, C1-C4 alkyl, C1-C4 alkoxy or halogen, and wherein A, B and R in formulas (I) and (II) can be the same or different and are preferably the same; and wherein the amount of the one or more compounds of formula (II) is from 0.002 to 5% by weight of the one or more compounds of formula (I).
- a and B are independently selected from F, Cl, H, C1-C3 fluorinated alkyl, CI- 03 fluorinated alkoxy, R is selected from H or C1-C4 alkyl, C1-C4 alkoxy or halogen and wherein A, B and R in formulas (I) and (II) can be the same or different and are preferably the same.
- R- is H-, CH3-, CH3O-, F- or CI-, and more preferably is H.
- a and B are preferably F or Cl, and more preferably F.
- the total amount of said one or more compounds of formula (II) is from 0.002 to 5%, preferably from 0.005 to 3%, more preferably, from 0.01 to 2%, most preferably from 0.05 to 1 % by weight of the total amount of said one or more compounds of formula (I).
- the total amount of compounds according to formulas (I) and (II) is at least 50%, more preferably at least 70%, even more preferably at least 85%, most preferably at least 90% by weight, based on the total weight of the composition.
- the composition of the invention consists essentially of compounds according to formulas (I) and (II).
- “consists essentially” it is intended that the total amount of compounds according to formulas (I) and (II) represents at least 95%, preferably at least 97%, most preferably at least 99% by weight based on the total weight of the composition.
- a composition according to the invention can be prepared with any method known to the skilled person e.g. mixing the one or more compound according to formula (I) with the one or more compound according to formula (II).
- a preferred method for making the composition of the invention is a the reaction between a phenol and a fluorinated olefin in a selected polar aprotic solvent and in the presence of a basic catalyst.
- a phenol it is meant a chemical compound selected from phenol itself (CeHsOH) and similar compounds wherein one of the hydrogen atoms on the aromatic ring is replaced by a C1-C4 alkyl (such as e.g. cresol), C1-C4 alkoxy (such as e.g. methoxyphenol) or by a halogen (such as fluorophenol or chlorophenol).
- This method provides high yields and can be performed easily in mild conditions and without requiring ingredients which are harmful for the environment. It allows to obtain directly a composition according to the invention already possessing the desired balance among the compounds according to formulas (I) and (II) without the need to mix the different components.
- a hydrofluoroether is defined as a chemical compound having the general formula R’-O-R” wherein at least one of R’ and R” comprises at least one C-F bond and at least one C-H bond.
- CFA CFB (IV) wherein A and B can be selected as defined above for formulas (I) and (II) so that the fluorinated olefin can be partially or fully fluorinated.
- a mixture comprising one or more polar aprotic organic solvents and one or more phenol.
- Suitable polar aprotic organic solvents for use in the process of the present invention are polar aprotic organic solvents having a boiling point measured at atmospheric pressure (1 atm) of from of 60 to 170°C, preferably of from 70°C to 90°C.
- Particularly suitable polar aprotic solvents for use herein are those carrying a nitrile group, a particularly preferred solvent is acetonitrile.
- the other essential component of the mixture to be provided in step A of the process of the present invention is a phenol.
- solvents may be present in the mixture, but preferably the total amount of the one or more phenol and of the one or more selected polar aprotic solvents represents at least 70%, more preferably at least 80%, even more preferably at least 90%, most preferably at least 95% by weight of the mixture.
- the fluorinated olefin is selected among the fully halogenated olefins and more preferably from the group consisting of perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP) and more preferably is TFE.
- the fluorinated olefin can be initially loaded in the reaction vessel or can be advantageously continuously fed in the required amount during the reaction.
- step B of the process of the present invention the mixture provided in step A is reacted with a fluorinated olefin in the presence of a basic catalyst.
- the reaction can be typically performed in a stirred reactor which is preferably sealed.
- the molar ratio between the -OH groups and the fluorinated olefins is in principle stoichiometric i.e. in order to have complete reaction and not have residual reagents the same molar amount of double bonds from the olefins should be present as the molar amount of -OH groups in the phenol. While a stoichiometric ratio between double bonds and OH groups is ideal, the present invention can be effectively carried out also when one of the components is in a molar excess up to 50%, preferably up to 30%, more preferably up to 20% most preferably up to 10%. In case one component is in excess said component in excess is preferably the fluorinated olefin.
- the basic catalyst can be any chemical compound capable of creating a basic environment i.e. to subtract protons from the reagents thus promoting the ionic reaction.
- Preferred basic catalyst are selected from inorganic hydroxides (such as NaOH, KOH, LiOH, Ca(OH)2, Mg(OH)2), inorganic salts of weak acids (such as alkali metal phosphates or carbonates), organic basic compounds (such as alcolates). Most preferred basic catalysts are NaOH and KOH.
- the amount of catalyst to be used is typically from 5% to 100%, preferably 10%-70%, more preferably 15%-50% by moles with respect to the total moles of -OH groups.
- the basic catalyst is added to the reactor adding it to the mixture provided in step A under agitation.
- the reactor is then typically sealed and the fluorinated olefin is pumped in gas form up to a pressure of from 1 to 50 bar, preferably 2-30 bar, more preferably 3-20bar, most preferably between 4 and 14 bar.
- the fluorinated olefin is in liquid form the olefin can be introduced as a liquid and if it remains in liquid status at the temperature of reaction, the reaction can be carried out at a lower pressure or even at atmospheric pressure.
- the reactor is typically vented to remove the excess of fluorinated olefin.
- the reactor contains a liquid reacted mixture comprising one or more compounds of formula (I) and one or more compounds of formula (II), in combination with the polar aprotic solvent and with residues of the basic catalyst.
- step D of the present invention the liquid reacted mixture directly resulting from the reaction of step B is completely evaporated and recondensed in liquid form thereby obtaining a purified reacted mixture.
- Any available technique can be used to evaporate the liquid reacted mixture, for example heating and a vacuum can be used individually or in combination to evaporate the mixture.
- a conventional evaporation equipment e.g. a rotary evaporation equipment
- a solid residue is formed comprising the residual basic catalyst and salts obtained as by-products of the reaction which can be discarded or recycled.
- Agitation can be performed with any suitable technique used for extractions as known to the skilled person and a separatory funnel or similar equipment can be used separate the water phase from the phase containing the aprotic polar solvent and the one or more compounds of formula (I) and one or more compounds of formula (II).
- a separatory funnel or similar equipment can be used separate the water phase from the phase containing the aprotic polar solvent and the one or more compounds of formula (I) and one or more compounds of formula (II).
- distillation allows to separate the one or more compounds of formula (I) and one or more compounds of formula (II) from the solvent. Distillation can be performed using conventional techniques and if necessary can be repeated to further purify the composition. In general the solvent will be recovered with known methods in order to be reused.
- the Evaporation/recondensation method described above is in general preferred to the water extraction method because the water extraction method generates a large amount of waste water which is contaminated with the impurities of the system and therefore needs to be treated before being discarded or reused.
- compositions according to the invention consist essentially of one or more compounds according to general formulas (I) and one or more compound according to general formula
- the process of the invention can be carried out under mild conditions, additionally and a very high yield is obtained.
- the reacted mixture was then washed with 3 times its volume of a water phase containing demineralized water and 4% by weight of sodium chloride.
- the organic layer was then separated as a purified reacted mixture.
- the purified reacted mixture was then distilled in a 70cm rashig i.d. column 30mm with reflux head condenser.
- the overall yield was 96.4% based on the phenol.
Abstract
A liquid composition comprising one or more compounds according to general formula (I): and one or more compound according to general formula (II): wherein: A and B, are independently selected from F, Cl, H, C1-C3 fluorinated alkyl, C1- C3 fluorinated alkoxy, R is selected from H, C1-C4 alkyl, C1-C4 alkoxy or halogen, and wherein A, B and R in formulas (I) and (II) can be the same or different and are preferably the same; and wherein the amount of the one or more compounds of formula (II) is from 0.002 to 5% by weight of the one or more compounds of formula (I).
Description
HYDROFLUOROETHER COMPOSITION AND METHOD FOR ITS PREPARATION
Technical Field
[0001] This application claims priority from the European patent application filed on 29 June 2022 in EUROPE with Nr. 22181826.3, the whole content of this application being incorporated herein by reference for all purposes.
[0002] The invention relates to a hydrofluoroether composition which can find application as solvent. The invention also relates to a method of preparation of said composition.
Background Art
[0003] Various methods for producing hydrofluoroethers are known in the art. US4208081 (Du Pont) describes the preparation of hydrofluoroethers using ethylene glycol in a diethyl ether solution and tetrafluoroethylene (TFE). However the reaction is not complete as two reaction products are formed in almost equal amounts, one where both -OH groups of the ethylene glycol are converted to ether groups, and another where only one of the -OH groups of the ethylene glycol has been converted to ether, while the other remains as a free hydroxyl group.
[0004] RU1810324 to Natalya Guseva reports the preparation of hydrofluoroethers from a reaction between ethylene glycol and TFE in diglyme solvent in a anhydrous process with a 78% yield.
[0005] Solvents based on hydrofluoroethers are very advantageous if compared to alternative materials which are available in the market because they have low GWP (Global warming potential) low flammability and are thus safe and easy to handle.
[0006] The composition of the present invention is a stabilized aromatic hydrofluoroether composition which has an extended shelf life so that it can maintain its effectiveness and appearance for a longer time. Also the composition of the invention can be easily prepared using a processes which is simple and has a high yield. The present invention also relates to such a process.
[0007] Summary of the Invention
The present invention relates to A liquid composition comprising one or more compounds according to general formula (I):
and one or more compound according to general formula (II):
wherein:
A and B, are independently selected from F, Cl, H, C1-C3 fluorinated alkyl, C1- C3 fluorinated alkoxy, R is selected from H, C1-C4 alkyl, C1-C4 alkoxy or halogen, and wherein A, B and R in formulas (I) and (II) can be the same or different and are preferably the same; and wherein the amount of the one or more compounds of formula (II) is from 0.002 to 5% by weight of the one or more compounds of formula (I).
Detailed description of the Invention
[0008] It is thus an object of the present invention to provide a liquid composition comprising one or more compounds of formula (I):
(I), and one or more compound of formula (II):
wherein:
A and B, are independently selected from F, Cl, H, C1-C3 fluorinated alkyl, CI- 03 fluorinated alkoxy, R is selected from H or C1-C4 alkyl, C1-C4 alkoxy or halogen and wherein A, B and R in formulas (I) and (II) can be the same or different and are preferably the same.
Preferably R- is H-, CH3-, CH3O-, F- or CI-, and more preferably is H. A and B are preferably F or Cl, and more preferably F.
[0009] In the composition of the invention the total amount of said one or more compounds of formula (II) is from 0.002 to 5%, preferably from 0.005 to 3%, more preferably, from 0.01 to 2%, most preferably from 0.05 to 1 % by weight of the total amount of said one or more compounds of formula (I).
[0010] In the composition of the invention it is preferred that the total amount of compounds according to formulas (I) and (II) is at least 50%, more preferably at least 70%, even more preferably at least 85%, most preferably at least 90% by weight, based on the total weight of the composition.
[0011] In one embodiment the composition of the invention consists essentially of compounds according to formulas (I) and (II). For “consists essentially” it is intended that the total amount of compounds according to formulas (I) and (II) represents at least 95%, preferably at least 97%, most preferably at least 99% by weight based on the total weight of the composition.
[0012] A composition according to the invention can be prepared with any method known to the skilled person e.g. mixing the one or more compound according to formula (I) with the one or more compound according to formula (II).
[0013] A preferred method for making the composition of the invention is a the reaction between a phenol and a fluorinated olefin in a selected polar aprotic solvent and in the presence of a basic catalyst. By “a phenol” it is meant a chemical compound selected from phenol itself (CeHsOH) and similar compounds wherein one of the hydrogen atoms on the aromatic ring is replaced by a C1-C4
alkyl (such as e.g. cresol), C1-C4 alkoxy (such as e.g. methoxyphenol) or by a halogen (such as fluorophenol or chlorophenol). This method provides high yields and can be performed easily in mild conditions and without requiring ingredients which are harmful for the environment. It allows to obtain directly a composition according to the invention already possessing the desired balance among the compounds according to formulas (I) and (II) without the need to mix the different components.
[0014] As apparent to the skilled person the one or more compounds according to formula (I) are hydrofluoroethers. A hydrofluoroether is defined as a chemical compound having the general formula R’-O-R” wherein at least one of R’ and R” comprises at least one C-F bond and at least one C-H bond.
[0015] One way of forming hydrofluoroethers for the composition of the present invention is to react a phenol with a fluorinated olefin having general formula:
CFA=CFB (IV) wherein A and B can be selected as defined above for formulas (I) and (II) so that the fluorinated olefin can be partially or fully fluorinated. The reaction between the -OH group and the C=C double bond of the olefin can be described as an addition to the C=C double bond where one of its carbon atoms forms a C-0 bond and the other a C-H bond.
[0016] In a first step (A) of the process of the present invention a mixture is provided comprising one or more polar aprotic organic solvents and one or more phenol.
[0017] Suitable polar aprotic organic solvents for use in the process of the present invention are polar aprotic organic solvents having a boiling point measured at atmospheric pressure (1 atm) of from of 60 to 170°C, preferably of from 70°C to 90°C.
Particularly suitable polar aprotic solvents for use herein are those carrying a nitrile group, a particularly preferred solvent is acetonitrile.
[0018] The other essential component of the mixture to be provided in step A of the process of the present invention is a phenol.
[0019] Phenols for use in the present invention correspond to the general formula (III):
wherein R is defined as above for the formulas (I) and (II).
[0020] Examples of suitable phenols suitable in the present invention are phenol, o- cresol, m-cresol, p-cresol, methoxyphenol, chlorophenol, fluorophenol, preferably phenol CeHsOH is used.
[0021] In the process of the present invention one or more phenol as defined above is provided in a mixture with one or more polar aprotic solvents selected as defined above. Such solvents are generally good solvents for the phenol so that preferably the mixture provided is homogeneous. The relative amount of the selected one or more polar aprotic organic solvents and of the one or more phenol is preferably at least 1 :1 by weight, preferably at least 2:1 more preferably at least 3:1 , most preferably at least 4:1 . Other solvents may be present in the mixture, but preferably the total amount of the one or more phenol and of the one or more selected polar aprotic solvents represents at least 70%, more preferably at least 80%, even more preferably at least 90%, most preferably at least 95% by weight of the mixture.
[0022] The mixture provided in step A is reacted in step B of the process of the invention with one or more fluorinated olefin having general formula CFA=CFB, wherein A and B are defined as above for formulas (I) and (II).
[0023] Preferably the fluorinated olefin is selected among the fully halogenated olefins and more preferably from the group consisting of perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP) and more preferably is TFE.
[0024] The fluorinated olefin can be initially loaded in the reaction vessel or can be advantageously continuously fed in the required amount during the reaction.
[0025] In step B of the process of the present invention the mixture provided in step A is reacted with a fluorinated olefin in the presence of a basic catalyst.
[0026] The reaction of an -OH carrying compound with a fluorinated olefin can be schematized as follows:
[0027] In parallel a competing reaction leads to the formation of a vinyl ether in small amounts. The vinyl ether is an essential component (the one or more compound of formula (II)) of the composition of the invention.
[0028] The reaction can be typically performed in a stirred reactor which is preferably sealed. The molar ratio between the -OH groups and the fluorinated olefins is in principle stoichiometric i.e. in order to have complete reaction and not have residual reagents the same molar amount of double bonds from the olefins should be present as the molar amount of -OH groups in the phenol. While a stoichiometric ratio between double bonds and OH groups is ideal, the present invention can be effectively carried out also when one of the components is in a molar excess up to 50%, preferably up to 30%, more preferably up to 20% most preferably up to 10%. In case one component is in excess said component in excess is preferably the fluorinated olefin.
[0029] The basic catalyst can be any chemical compound capable of creating a basic environment i.e. to subtract protons from the reagents thus promoting the ionic reaction. Preferred basic catalyst are selected from inorganic hydroxides (such as NaOH, KOH, LiOH, Ca(OH)2, Mg(OH)2), inorganic salts of weak acids (such as alkali metal phosphates or carbonates), organic basic compounds (such as alcolates). Most preferred basic catalysts are NaOH and KOH.
[0030] The amount of catalyst to be used is typically from 5% to 100%, preferably 10%-70%, more preferably 15%-50% by moles with respect to the total moles of -OH groups.
[0031] Typically the basic catalyst is added to the reactor adding it to the mixture provided in step A under agitation. The reactor is then typically sealed and the fluorinated olefin is pumped in gas form up to a pressure of from 1 to 50 bar, preferably 2-30 bar, more preferably 3-20bar, most preferably between 4 and 14 bar. In case the fluorinated olefin is in liquid form the olefin can be introduced as a liquid and if it remains in liquid status at the temperature of reaction, the reaction can be carried out at a lower pressure or even at atmospheric pressure.
[0032] The reaction typically starts immediately. Preferably, during the reaction, the reactor is maintained at a temperature of from 20° to 90°C, preferably from 30° to 80°C, most preferably from 40° to 70°C. The reaction time can be variable depending on the temperature, pressure and reagents used. Typically the reaction will require from 1 to 20 hours to complete.
[0033] After the reaction is completed the reactor is typically vented to remove the excess of fluorinated olefin. At this stage the reactor contains a liquid reacted mixture comprising one or more compounds of formula (I) and one or more compounds of formula (II), in combination with the polar aprotic solvent and with residues of the basic catalyst.
[0034] The one or more compounds of formula (I) and one or more compounds of formula (II) can be extracted directly from the reacted mixture with known techniques such as distillation (in optional step C of the present invention). However the reacted mixture obtained in step B still contains dissolved or dispersed solids, typically inorganic solids deriving from the basic catalyst, so that the direct distillation of said reacted mixture would cause the build-up of unwanted solid deposits on the distillation equipment which, while it can be acceptable in lab scale, are more problematic at an industrial scale as it could force the equipment to have frequent stops for cleaning/restoring it. Therefore, preferably, before extracting the one or more compounds of formula (I) and one or more compounds of formula (II) via distillation the reacted mixture is purified to remove catalyst residues and solid by-products.
[0035] In one embodiment the reacted mixture is purified via an extraction with water. In another embodiment the reacted mixture is purified trough evaporation and re-condensation. These two embodiments will be described in detail below.
[0036] Evaporation/recondensation method:
In the optional step D of the present invention the liquid reacted mixture directly resulting from the reaction of step B is completely evaporated and recondensed in liquid form thereby obtaining a purified reacted mixture. Any available technique can be used to evaporate the liquid reacted mixture, for example heating and a vacuum can be used individually or in combination to evaporate the mixture. A conventional evaporation equipment (e.g. a rotary evaporation equipment) may be used. Following the evaporation of the liquid reacted mixture, a solid residue is formed comprising the residual basic catalyst and salts obtained as by-products of the reaction which can be discarded or recycled.
The purified reacted mixture obtained in step D, differently from the reacted mixture obtained in step B, is pure enough to be distilled in a conventional distillation equipment. This is performed in step E of the process of the present invention.
[0037] Water extraction method:
In the optional step F of the process of the present invention the liquid reacted mixture directly resulting from the reaction of step B is mixed with water and subject to agitation and or stirring so to extract in the water phase the water soluble impurities such as residues of the basic catalyst and other impurities and by-products. The relative amounts of water and reacted mixture to use in this step are from 1 : 15 to 15: 1 by weight, preferably from 1 :5 to 5: 1 , more preferably from 2:1 to 1 :2. Agitation can be performed with any suitable technique used for extractions as known to the skilled person and a separatory funnel or similar equipment can be used separate the water phase from the phase containing the aprotic polar solvent and the one or more compounds of formula (I) and one or more compounds of formula (II). The resulting phase
containing the aprotic polar solvent and the one or more compounds of formula
(I) and one or more compounds of formula (II) once separated from the water phase constitutes the purified reacted mixture which is pure enough to be subject to distillation in a conventional distillation equipment in step G of the process of the present invention.
[0038] In all embodiments distillation allows to separate the one or more compounds of formula (I) and one or more compounds of formula (II) from the solvent. Distillation can be performed using conventional techniques and if necessary can be repeated to further purify the composition. In general the solvent will be recovered with known methods in order to be reused.
[0039] The Evaporation/recondensation method described above is in general preferred to the water extraction method because the water extraction method generates a large amount of waste water which is contaminated with the impurities of the system and therefore needs to be treated before being discarded or reused.
[0040] Both methods lead to a composition according to the invention wherein the composition consists essentially of one or more compounds according to general formulas (I) and one or more compound according to general formula
(II)in the weight ratio which is required by the invention.
[0041] The process of the invention can be carried out under mild conditions, additionally and a very high yield is obtained.
[0042] The invention will be now described in more detail with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention. Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
[0043] EXAMPLES
[0044] Product identification were performed by NMR (F-NMR and H-NMR) and GC and GC-MS analysis (GC using CP-WAX52CB column and CP-SH8CB column for GC-MS peaks attribution).
[0045] EXAMPLE1 - phenol + TFE + water extraction
3000g of phenol, 3956g of acetonitrile and 420g of sodium hydroxide were loaded into a 22L stirred Hastelloy reactor. After purging 4 times with nitrogen and vacuum at 0.3bar, the reactor was heated at 60°C and, under stirring, pressurized up to 3.8 bar with TFE (tetrafluoroethylene) and TFE was continuously fed to maintain the initial pressure. When the reaction started the temperature increased due to hexothermic reaction, the temperature of the reactor was controlled at 70°C for 8.5 hours (total TFE fed was 3536g). After cooling the reactor was purged with nitrogen, a reacted mixture was recovered and discharged. The reacted mixture was then washed with 3 times its volume of a water phase containing demineralized water and 4% by weight of sodium chloride. The organic layer was then separated as a purified reacted mixture. The purified reacted mixture was then distilled in a 70cm rashig i.d. column 30mm with reflux head condenser. The distillation product was a composition comprising the hydrofluoroether (5999g) and the vinylether C6H5-O-CF=CF2 (3,7g, 0.06% by weight of the hydrofluoroether.
The overall yield was 96.4% based on the phenol.
[0046] When comparing the purity and the yield of the process of the present invention with that of the prior art it is clear that the process of the present invention provides for higher yields, higher purity of the hydrofluoroethers obtained.
[0047] Possible modifications and/or additions may be made by those skilled in the art to the hereinabove disclosed and illustrated embodiment while remaining within the scope of the following claims.
Claims
Claims
Claim 1
A liquid composition comprising one or more compounds according to general formula (I):
and one or more compound according to general formula (II):
wherein:
A and B, are independently selected from F, Cl, H, C1-C3 fluorinated alkyl, C1- C3 fluorinated alkoxy, R is selected from H, C1-C4 alkyl, C1-C4 alkoxy or halogen, and wherein A, B and R in formulas (I) and (II) can be the same or different and are preferably the same; and wherein the amount of the one or more compounds of formula (II) is from 0.002 to 5% by weight of the one or more compounds of formula (I).
Claim 2
A composition according to claim 1 wherein A and B are selected from F and Cl and wherein preferably are both F.
Claim 3
A composition according to claim 1 or 2 wherein R is H.
Claim 4
A composition according to any preceding claim wherein the amount of the one or more compounds of formula (II) is from 0.005 to 3%, preferably, from 0.01 to 2%, more preferably from 0.05 to 1 % by weight of the total amount of said one or more compounds of formula (I).
Claim 5
A composition according to any preceding claim wherein the the total amount of said compounds according to formulas (I) and (II) is at least 50%, more preferably at least 70%, even more preferably at least 85%, most preferably at least 90% by weight, based on the total weight of the composition.
Claim 6
A process for making the composition of claims 1-5, the process comprising:
A) providing a mixture comprising one more polar aprotic organic solvents having a boiling point measured at atmospheric pressure of from of 60 to 170°C, preferably of from 70°C to 90°C, and one or more phenol having general formula
Wherein R is selected from H, C1-C4 alkyl or halogen,
B): reacting said and one or more phenol with one or more fluorinated olefin having general formula
CFA=CFB (IV) in the presence of a basic catalyst wherein
A and B, are independently selected from F, Cl, H, C1-C3 fluorinated alkyl, C1- C3 fluorinated alkoxy,
thus providing a reacted mixture comprising one or more compounds according to general formula (I) and one or more compounds according to general formula (II).
Claim 7
A process according to claim 6 wherein said fluorinated olefin is TFE.
Claim 8
A process according to claim 6 or 7 wherein said one or more phenol is phenol (CeHsOH).
Claim 9
A process according to claims 7-9 said one or more polar aprotic organic solvent is acetonitrile.
Claim 10
A process according to claims 6-9 comprising an additional step G wherein said one or more compounds according to general formula (I) and one or more compounds according to general formula (II) are directly separated from said reacted mixture, preferably via distillation.
Claim 11
A process according to claims 6-9 wherein said process further comprises the steps of
C) evaporating completely said reacted mixture and re-condense it in liquid form as a purified reacted mixture
D) separate said one or more compounds according to general formula (I) and one or more compounds according to general formula (II) in purified form from said purified reacted mixture via distillation.
Claim 12
A process according to claims 6-9 wherein said process further comprises the steps of
E) mix said reacted mixture with water, agitate the mixture thereby extracting water soluble impurities from said reacted mixture, and separate the purified reacted mixture as a water immiscible phase.
F) separate the one or more compounds according to general formula (I) and one or more compounds according to general formula (ll)in purified form from said purified reacted mixture via distillation.
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|---|---|---|---|---|
| US3277068A (en) * | 1962-07-31 | 1966-10-04 | Leo A Wall | Perfluorovinylphenylethers and their polymers |
| GB1320648A (en) * | 1970-06-16 | 1973-06-20 | Hoechst Ag | Process for the preparation of aryl-1,1,2,2,-tetrafluoroethyl ethers |
| US4208081A (en) | 1979-01-03 | 1980-06-17 | International Business Machines Corporation | Easily reconfigurable data entry terminal |
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| CN113929562A (en) * | 2021-10-28 | 2022-01-14 | 衢州氟硅技术研究院 | Preparation method of fluoroether |
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| US3277068A (en) * | 1962-07-31 | 1966-10-04 | Leo A Wall | Perfluorovinylphenylethers and their polymers |
| GB1320648A (en) * | 1970-06-16 | 1973-06-20 | Hoechst Ag | Process for the preparation of aryl-1,1,2,2,-tetrafluoroethyl ethers |
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| RU1810324C (en) | 1990-11-15 | 1993-04-23 | Военная Краснознаменная академия химической защиты им.Маршала Советского Союза С.К.Тимошенко | Method of synthesis of ethylene glycol polyfluoroalkyl esters |
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