CN114907192B - Preparation method of hydrofluoroether compound - Google Patents
Preparation method of hydrofluoroether compound Download PDFInfo
- Publication number
- CN114907192B CN114907192B CN202210421021.5A CN202210421021A CN114907192B CN 114907192 B CN114907192 B CN 114907192B CN 202210421021 A CN202210421021 A CN 202210421021A CN 114907192 B CN114907192 B CN 114907192B
- Authority
- CN
- China
- Prior art keywords
- formula
- reaction
- iii
- alcohol
- potassium fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000007259 addition reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 18
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000008346 aqueous phase Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 17
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 3
- -1 alcohol compound Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000410737 Verasper moseri Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007068 beta-elimination reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a preparation method of a hydrofluoroether compound, which comprises the following steps: in an aqueous phase system, in the presence of potassium fluoride and an additive, alcohol shown as a formula (III) and perfluoroolefin shown as a formula (II) are subjected to addition reaction to obtain a hydrofluoroether compound shown as a formula (I); wherein R is C 1 ‑C 6 An alkyl group. The method successfully realizes the addition reaction of the perfluoroolefin and the alcohol under the neutral condition by using potassium fluoride and a water system. Because the reaction is carried out under neutral condition, the generation of eliminating the product-olefin is avoided, the product is easy to purify, the reaction condition is mild, the operation is easy, the equipment is simple, and the industrialization is easy.
Description
Technical Field
The invention relates to a preparation method of a hydrofluoroether compound.
Background
The hydrofluoroether compounds, which are excellent properties such as no ozone depletion, low greenhouse effect, etc., are widely used in the fields of cleaning agents, high-performance solvents, foaming agents, etc., as third-generation freon substitutes. The usual methods for preparing hydrofluoroethers are: under alkaline conditions, the reaction proceeds by nucleophilic addition reaction of an alcohol compound and a perfluoroolefin compound. Such as: reaction of alcohols and perfluoroolefins in potassium carbonate/acetonitrile system at 35 ℃ (WO 2007/30314); alcohol and perfluoroolefins in potassium hydroxide/water systems at a temperature of 50 ℃ (j. Fluoroine chem.,1999, 95 (1-2), 5-14; wo 2006/123563); and addition reactions with perfluoroolefins in sodium alkoxide/alcohol systems (chem. Lett.,1981,107-110;J.Fluorine Chem.,1984,25,203), and the like. However, in these methods, since the reaction system is basic, the formation of by-products of fluoroolefins is unavoidable. This is mainly due to the presence of two possible pathways, namely, the production of corresponding addition products by hydrogen purup and the production of olefins by beta-elimination reaction, which are intermediates of nucleophilic addition of alkoxide anions and olefins, namely, fluorine-containing carbanion, under alkaline conditions, as shown in the following formula:
under the production conditions, the production cost of the product is increased and the difficulty for separating and purifying the subsequent final product is increased due to the generation of the byproduct fluorine-containing olefin. In order to improve the selectivity of the addition reaction and avoid the occurrence of the elimination reaction, yasuhisa et al reported a method for producing a hydrofluoroether compound by reacting an alcohol with a perfluoroolefin under neutral conditions using tetrakis (triphenylphosphine) palladium as a catalyst. The method effectively avoids the production of fluoroolefin byproducts, thereby simplifying the conditions for separating and purifying the products (Matsukawa, yasuhisa et al, angew.Chem., int.Ed.,2005,44 (7), 1128-1130). However, the method uses expensive palladium as the catalyst, and the catalyst cannot be recycled, so that the production cost of the product is greatly increased, and the method is not suitable for being applied to industrial mass production.
Disclosure of Invention
The invention aims to overcome the defects of more byproducts and high production cost in the prior art, and provides a preparation method of a hydrofluoroether compound, which uses potassium fluoride as a catalyst for reaction, and alcohol and perfluoroolefin are subjected to addition reaction in a water phase system, so that the proportion of byproducts in the reaction of perfluoroolefin and alcohol is reduced, and the production cost of the hydrofluoroether product is reduced as much as possible.
The invention solves the technical problems by the following technical proposal:
the invention provides a preparation method of a hydrofluoroether compound, which comprises the following steps: in an aqueous phase system, in the presence of potassium fluoride and an additive, alcohol shown as a formula (III) and perfluoroolefin shown as a formula (II) are subjected to addition reaction to obtain a hydrofluoroether compound shown as a formula (I);
wherein R is C 1 -C 6 An alkyl group.
In the addition reaction, the aqueous phase system is a conventional aqueous solution. The amount of the aqueous phase system is not limited so as not to affect the reaction, and the volume ratio of the alcohol to the water shown in the formula (III) is (1-4): 1, a step of; for example 1.52:1, 2:1 or 3.15:1.
In the addition reaction, R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, for example ethyl.
In the addition reaction, the alcohol represented by formula (III) may be one or more of ethanol, isopropanol and hexanol, preferably ethanol.
In the addition reaction, the amount of the alcohol represented by the formula (III) may be a conventional amount of the reaction, and the molar ratio of the alcohol represented by the formula (III) to the perfluoroolefin represented by the formula (II) is (1.0-1.5): 1.0, preferably 1.1:1.0.
In the addition reaction, the mass to volume ratio of the potassium fluoride to the alcohol represented by the formula (III) may be 0.07g/mL to 0.15g/mL, preferably 0.07g/mL to 0.1g/mL, for example: 0.075g/mL, 0.079g/mL, or 0.092g/mL.
In the addition reaction, the temperature of the reaction may be 20 to 100 ℃, such as 25 to 75 ℃, and further such as 25 ℃, 50 ℃ or 75 ℃; preferably 45-60 ℃.
In the addition reaction, the additive may be one or more of tetrabutylammonium chloride, tetrabutylammonium hydroxide, polyethylene glycol 2000, tween-20 and span-80, preferably tetrabutylammonium hydroxide.
In the addition reaction, the amount of the additive may be a conventional amount for the reaction, and the mass ratio of the additive to the potassium fluoride is (0.9 to 1.5): 1, e.g., 1:1.
In the addition reaction, the reaction can be carried out under 0.1MPa-2 MPa; for example, at 0.1MPa or 0.5MPa to 2 MPa.
In the addition reaction, stirring reaction is preferable.
In the addition reaction, hexafluoropropylene gas is introduced into a reaction flask. Preferably, hexafluoropropylene gas is introduced into the reaction flask through a bubbler via a gas conduit.
In the addition reaction, the reaction time may be 6 to 10 hours.
The progress of the addition reaction may be determined by methods conventional in the art, e.g., by 19 F-NMR is generally carried out with the elimination of the perfluoroolefin of the formula (II) as the reaction end point.
In the addition reaction, the method can further comprise the following post-treatment steps: separating phases, washing with water, and drying.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: the potassium fluoride and the water system are utilized to successfully realize the addition reaction of the perfluoroolefin and the alcohol under the neutral condition. Because the reaction is carried out under neutral condition, the generation of eliminating the product-olefin is avoided, the product is easy to purify, the reaction condition is mild, the operation is easy, the equipment is simple, and the industrialization is easy.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
Into a 1000 ml three-necked flask were added 50 ml of water, 100 ml of ethanol, 7.5 g of potassium fluoride and 7.5 g of polyethylene glycol 2000. After stirring evenly, the air duct, thermometer and reflux condenser are inserted into the bottle respectively, the upper end of the condenser is sealed by rubber plug, and then balloon is connected in parallel to display the pressure condition in the system. The three-necked flask was placed in an oil bath and heated according to the reaction conditions shown in Table 1. Hexafluoropropylene gas in the steel bottle is introduced into the reaction bottle through the gas conduit by the bubbler, and the gas introduction speed is regulated by observing the bubbling speed of the bubbler and the size of a balloon at the upper end of the condenser. After the system does not absorb hexafluoropropylene (about 6 hours, about 250-280 g of common hexafluoropropylene) any more, stopping ventilation, after the reaction is completed, standing the reaction solution for 1 hour, separating out a lower product, washing twice, drying, and sending the GC test reaction result. The results are shown in table 1 below:
table 1: reaction results at different temperatures
Sequence number | Reaction temperature (. Degree. C.) | Olefin content (%) | Yield (%) |
1 | 25 | 0 | 56 |
2 | 50 | 0 | 78 |
3 | 75 | 0 | 67 |
Example 2
Into a 1000 ml three-necked flask were charged 50 ml of water, 100 ml of ethanol, 7.5 g of potassium fluoride and 7.5 g of the additives shown in Table 2. After stirring evenly, the air duct, thermometer and reflux condenser are inserted into the bottle respectively, the upper end of the condenser is sealed by rubber plug, and then balloon is connected in parallel to display the pressure condition in the system. The three-necked flask was placed in an oil bath and heated to 50 degrees celsius to effect a reaction. Hexafluoropropylene gas in the steel bottle is introduced into the reaction bottle through the gas conduit by the bubbler, and the gas introduction speed is regulated by observing the bubbling number of the bubbler and the size of the balloon at the upper end of the condenser. After the system does not absorb hexafluoropropylene (the hexafluoropropylene is introduced into the system for 250-280 g for 6-8 hours), stopping ventilation, standing the reaction solution for 1 hour after the reaction is completed, separating out a lower product, washing twice, drying, and sending the GC test reaction result. The results are shown in the following table (table 2):
table 2: effect of additives on the reaction
Sequence number | Additive agent | Olefin content (%) | Yield (%) |
1 | Tetrabutylammonium chloride | 0 | 68 |
2 | Tetrabutylammonium hydroxide | 0 | 81 |
3 | Polyethylene glycol 2000 | 0 | 78 |
4 | Tween-20 | 0 | 44 |
5 | Span-80 | 0 | 69 |
Example 3
To a 500 ml autoclave, 50 ml of water, 100 ml of ethanol, 7.5 g of potassium fluoride and 2g of tetrabutylammonium hydroxide were added in this order. After tightening the lid, the hatchet body was cooled with a dry ice/acetone system and then about 300 grams of hexafluoropropylene was added. After the autoclave had returned to room temperature, stirring reaction was carried out at 50℃and the stirring speed was controlled at about 180 rpm, and changes in the internal pressure of the autoclave (the internal pressure of the autoclave was decreased from about 2MPa to about 0.5 MPa) were observed. After the pressure of the autoclave is kept unchanged for half an hour, stopping the reaction, and performing post-treatment to obtain the product with the yield of 67%.
Example 4:
into a 1000 ml three-necked flask were charged 50 ml of water, 76 ml of isopropyl alcohol, 7g of potassium fluoride and 7g of tetrabutylammonium chloride. After stirring evenly, the air duct, thermometer and reflux condenser are inserted into the bottle respectively, the upper end of the condenser is sealed by rubber plug, and then balloon is connected in parallel to display the pressure condition in the system. The three-necked flask was placed in an oil bath and heated to 50 degrees celsius to effect a reaction. Hexafluoropropylene gas in the steel bottle is introduced into the reaction bottle through the gas conduit by the bubbler, and the gas introduction speed is regulated by observing the bubbling number of the bubbler and the size of the balloon at the upper end of the condenser. After the system does not absorb hexafluoropropylene (6 hours, the hexafluoropropylene is introduced into the system with the amount of about 135 g), stopping ventilation, after the reaction is completed, standing the reaction solution for 1 hour, separating out a lower product, washing twice, drying, and sending the GC test reaction result. Obtaining the olefin content: 0% of the total weight of the composition; yield: 63%.
Example 5:
into a 500 ml three-necked flask were charged 20 ml of water, 63 ml of hexanol, 5g of potassium fluoride, and 5g of span-80. After stirring evenly, the air duct, thermometer and reflux condenser are inserted into the bottle respectively, the upper end of the condenser is sealed by rubber plug, and then balloon is connected in parallel to display the pressure condition in the system. The three-necked flask was placed in an oil bath and heated to 50 degrees celsius to effect a reaction. Hexafluoropropylene gas in the steel bottle is introduced into the reaction bottle through the gas conduit by the bubbler, and the gas introduction speed is regulated by observing the bubbling number of the bubbler and the size of the balloon at the upper end of the condenser. After the system does not absorb hexafluoropropylene (about 60 g of hexafluoropropylene is introduced in 10 hours), stopping ventilation, after the reaction is completed, standing the reaction solution for 1 hour, separating out a lower product, washing twice, drying, and sending a GC test reaction result. Obtaining the olefin content: 0% of the total weight of the composition; yield: 21%.
Claims (10)
1. The preparation method of the hydrofluoroether compound is characterized by comprising the following steps: in an aqueous phase system, under the existence of potassium fluoride and an additive, alcohol shown as a formula (III) and perfluoroolefin shown as a formula (II) are subjected to an addition reaction under 0.1Mpa to obtain a hydrofluoroether compound shown as a formula (I); the additive is one or two of tetrabutylammonium hydroxide and polyethylene glycol 2000; the mass ratio of the additive to the potassium fluoride is (0.9-1.5): 1, a step of; the reaction temperature is 45-60 ℃; the reaction time is 6-10 hours;
wherein R is C 1 -C 6 An alkyl group.
2. The method of claim 1, wherein the method of preparation satisfies one or both of the following conditions:
(1) In the addition reaction, the additive is tetrabutylammonium hydroxide; and
(2) The mass ratio of the additive to the potassium fluoride is 1:1.
3. The process according to claim 2, wherein the temperature of the reaction in the addition reaction is 50 ℃.
4. The method of claim 1, wherein the method of preparation satisfies one or more of the following conditions:
(1) The volume ratio of the alcohol to the water shown in the formula (III) is (1-4): 1, a step of;
(2) The molar ratio of the alcohol shown in the formula (III) to the perfluoroolefin shown in the formula (II) is (1.0-1.5) 1.0; and
(3) The mass volume ratio of the potassium fluoride to the alcohol shown in the formula (III) is 0.07g/mL-0.15g/mL.
5. The process according to claim 4, wherein the mass to volume ratio of potassium fluoride to the alcohol represented by the formula (III) is 0.07 to 0.1g/mL.
6. The method of claim 4, wherein the method of preparation satisfies one or more of the following conditions:
(1) The volume ratio of the alcohol shown in the formula (III) to the water is 1.52:1, 2:1 or 3.15:1;
(2) The molar ratio of the alcohol shown in the formula (III) to the perfluoroolefin shown in the formula (II) is 1.1:1.0; and
(3) The mass volume ratio of the potassium fluoride to the alcohol shown in the formula (III) is 0.075g/mL, 0.079g/mL or 0.092g/mL.
7. The method of claim 1, wherein the method of preparation satisfies one or more of the following conditions:
(1) R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and
(2) The alcohol shown in the formula (III) is one or more of ethanol, isopropanol and hexanol.
8. The method of claim 7, wherein the method of preparation satisfies one or more of the following conditions:
(1) R is ethyl; and
(2) The alcohol shown in the formula (III) is ethanol.
9. The method of claim 1, wherein the method of preparation satisfies one or more of the following conditions:
(1) The addition reaction is a stirring reaction;
(2) In the addition reaction, hexafluoropropylene gas is introduced into a reaction bottle; and
(3) The addition reaction comprises the following post-treatment steps: separating phases, washing with water, and drying.
10. The process according to claim 9, wherein hexafluoropropylene gas is introduced into the reaction flask through the gas conduit via the bubbler.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210421021.5A CN114907192B (en) | 2022-04-20 | 2022-04-20 | Preparation method of hydrofluoroether compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210421021.5A CN114907192B (en) | 2022-04-20 | 2022-04-20 | Preparation method of hydrofluoroether compound |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114907192A CN114907192A (en) | 2022-08-16 |
CN114907192B true CN114907192B (en) | 2023-11-14 |
Family
ID=82764846
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210421021.5A Active CN114907192B (en) | 2022-04-20 | 2022-04-20 | Preparation method of hydrofluoroether compound |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114907192B (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102066299A (en) * | 2008-06-20 | 2011-05-18 | 大金工业株式会社 | Method for producing fluorine-containing ether |
CN103360222A (en) * | 2013-07-29 | 2013-10-23 | 中国科学院上海有机化学研究所 | Preparation of 2,2,2- trifluoroethyl-1,1,2,3,3,3-hexafluoroisopropyl ether |
CN103739450A (en) * | 2013-12-30 | 2014-04-23 | 山东华夏神舟新材料有限公司 | Preparation method of hydrofluoroether |
CN106748676A (en) * | 2015-11-23 | 2017-05-31 | 浙江蓝天环保高科技股份有限公司 | A kind of method of unsaturated impurity in removal 1,1,2,3,3,3- hexafluoro propyl group hydrofluoroether crude products |
RU2641110C1 (en) * | 2017-05-31 | 2018-01-16 | Закрытое акционерное общество научно-производственное Объединение "ПиМ-Инвест" (ЗАО НПО "Пим-Инвест") | 1,1,1,2,3,3-hexafluoro-2-iodine-3-methoxypropane as semi-products for production of fluoride 2,3,3,3-tetrafluoro-2-iodpropionyl and method of producing latter |
CN111116325A (en) * | 2019-12-30 | 2020-05-08 | 天津市长芦化工新材料有限公司 | Fluoropolymer additive and method of making same |
-
2022
- 2022-04-20 CN CN202210421021.5A patent/CN114907192B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102066299A (en) * | 2008-06-20 | 2011-05-18 | 大金工业株式会社 | Method for producing fluorine-containing ether |
CN103360222A (en) * | 2013-07-29 | 2013-10-23 | 中国科学院上海有机化学研究所 | Preparation of 2,2,2- trifluoroethyl-1,1,2,3,3,3-hexafluoroisopropyl ether |
CN103739450A (en) * | 2013-12-30 | 2014-04-23 | 山东华夏神舟新材料有限公司 | Preparation method of hydrofluoroether |
CN106748676A (en) * | 2015-11-23 | 2017-05-31 | 浙江蓝天环保高科技股份有限公司 | A kind of method of unsaturated impurity in removal 1,1,2,3,3,3- hexafluoro propyl group hydrofluoroether crude products |
RU2641110C1 (en) * | 2017-05-31 | 2018-01-16 | Закрытое акционерное общество научно-производственное Объединение "ПиМ-Инвест" (ЗАО НПО "Пим-Инвест") | 1,1,1,2,3,3-hexafluoro-2-iodine-3-methoxypropane as semi-products for production of fluoride 2,3,3,3-tetrafluoro-2-iodpropionyl and method of producing latter |
CN111116325A (en) * | 2019-12-30 | 2020-05-08 | 天津市长芦化工新材料有限公司 | Fluoropolymer additive and method of making same |
Non-Patent Citations (6)
Title |
---|
1,1,2,3,3,3-Hexafluoropropene;Justyna Walkowiak;《Encyclopedia of Reagents for Organic Synthesis》;20091231;1-5 * |
Fluoride-catalyzed hydroalkoxylation of hexafluoropropene with 2,2,2-trifluoroethanol;Debby Natalia;《Journal of Fluorine Chemistry》;20080630;第129卷(第6期);474-477 * |
Promising prospects for using partially fluorinated alcohols as O-nucleophilic reagents in organofluoric synthesis;A. A. Il"in;《RUSSIAN JOURNAL OF APPLIED CHEMISTRY》;20071231;第80卷(第3期);405-420 * |
Selective synthesis of fluorinated ethers by addition reaction of alcohols to fluorinated olefins in water;Junji Murata;《Green Chemistry》;20020201;第4卷(第1期);60-63 * |
傅献彩主编.实用化学便览.南京:南京大学出版社,1989,553-555. * |
廖铁星主编,广西医药企业管理协会仓储管理养护技术研究会编.化学试剂危险物品安全储存养护手册.桂林:广西师范大学出版社,1992,101-103. * |
Also Published As
Publication number | Publication date |
---|---|
CN114907192A (en) | 2022-08-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5188492B2 (en) | Process for producing β-alkoxypropionamides | |
Hudrlik et al. | Stereospecific synthesis of heteroatom-substituted olefins from. alpha.,. beta.-epoxysilanes. Preparation of vinyl bromides, enol acetates, enol ethers, and enamides | |
JP4976131B2 (en) | Polyglycerin monoether and method for producing the same | |
US9688621B2 (en) | Process for preparing an internal olefin sulfonate | |
CN103242139B (en) | Method for preparing 2-methyl allyl alcohol by esterification and hydrolysis | |
JP6106104B2 (en) | Method for producing narrowly dispersed polyalkylene glycol derivative having amino group at terminal | |
CN114907192B (en) | Preparation method of hydrofluoroether compound | |
CN103274959A (en) | Synthetic method of cooling agent N-, 2, 3-trimethyl-2-isopropyl butyrylamide | |
KR970008589B1 (en) | Preparation of glycolether | |
CN102173985B (en) | Method for preparing alkyl ether carboxylate | |
WO2011153656A1 (en) | Process for preparing ethylene glycol catalyzed by ion liquid | |
CN108893204B (en) | Method for synthesizing refined lanolin by inert gas with water method | |
JP6050380B2 (en) | Improved manufacturing process for ethoxylated amine compounds | |
CN109438506B (en) | Method for preparing tris (1, 3-dichloropropyl) phosphate | |
WO2014077465A1 (en) | Method for preparing glycidol | |
CN109776281B (en) | Synthesis method of ethyl isoeugenol | |
KR20150101768A (en) | Method for preparing glycidol through successive catalytic reaction | |
JP2009280543A5 (en) | ||
CN105037192B (en) | One-step method octane rating promoter is to formamido alkyl ether benzene synthetic method | |
JP6368717B2 (en) | Trifluoropyruvate derivative mixture and process for producing the same | |
CN114805427B (en) | Solvent-free synthesis method of vinyl trimethoxy silane | |
JP6278846B2 (en) | Method for producing 7-octene-1,2,3-triol | |
JP5302809B2 (en) | Process for producing aliphatic amine alkylene oxide adduct | |
KR100744834B1 (en) | Method for preparing of fluorinated alkoxysilane derivatives | |
WO2013146390A1 (en) | Method for producing 3-alkoxy-3-methyl-1-butanol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20230609 Address after: Room 402, No. 1, Donghai 8th Avenue, Taizhou Bay Economic and Technological Development Zone, Linhai City, Taizhou City, Zhejiang Province 317016 Applicant after: Zhejiang Yongtai Fule Technology Co.,Ltd. Address before: 200032 No. 345, Lingling Road, Shanghai, Xuhui District Applicant before: SHANGHAI INSTITUTE OF ORGANIC CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
|
TA01 | Transfer of patent application right | ||
GR01 | Patent grant | ||
GR01 | Patent grant |