CN111039778A - Preparation method of HFPO tetramer - Google Patents
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- CN111039778A CN111039778A CN201911399684.6A CN201911399684A CN111039778A CN 111039778 A CN111039778 A CN 111039778A CN 201911399684 A CN201911399684 A CN 201911399684A CN 111039778 A CN111039778 A CN 111039778A
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- C07—ORGANIC CHEMISTRY
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention belongs to the field of fluorine-containing fine chemicals, and discloses a preparation method of an HFPO tetramer, which comprises the following steps: (1) under the atmosphere of protective gas, adding an aprotic solvent and a catalyst into a reaction kettle, and uniformly stirring and dispersing, wherein the catalyst is a mixture of silver nitrate and alkali metal fluoride; (2) introducing HFPO gas into the reaction kettle, and controlling the temperature of the reaction kettle at 0-10 ℃ to carry out polymerization reaction; and (3) after the reaction is finished, adjusting the temperature of the reaction kettle to room temperature, standing and layering the reaction liquid, and recovering lower-layer substances to obtain the HFPO tetramer. The preparation method has the advantages of good selectivity to HFPO tetramer, high product yield, low reaction energy consumption and environmental protection.
Description
Technical Field
The invention belongs to the field of fluorine-containing fine chemicals application, and particularly relates to a preparation method of an HFPO tetramer.
Background
Hexafluoropropylene oxide tetramer (HFPO tetramer) is an important fluorine-containing active intermediate and has important industrial applications, for example, HFPO tetramer can be used for synthesizing perfluoropolyether, and can be used as a high-temperature inert medium due to the excellent thermal stability and chemical stability; the tetramer has good biodegradability, and is expected to become a new environment-friendly fluorine-containing surfactant variety.
At present, the prior art reports a lot of methods for preparing hexafluoropropylene oxide oligomers, but most of the methods have low selectivity to hexafluoropropylene oxide tetramer and have large limitation. For example, in US20060199942, a method for preparing hexafluoropropylene oxide oligomer with an average molecular weight of 2000-3000 by using potassium fluoride/tetraglyme as a catalytic system is reported, and although expensive, difficult-to-dry and toxic cesium fluoride is eliminated, the molecular weight of the product is not high enough, and the method has no great commercial value. Patent CN103788363 discloses a method for preparing perfluoropolyether with high molecular weight by HFPO ring-opening addition reaction, which requires harsh reaction conditions, uses cesium fluoride as a catalyst which is expensive and toxic and does not have large-scale production conditions. Therefore, a preparation method capable of improving the selectivity of HFPO tetramer is continuously researched for solving the problems that the existing preparation method of HFPO oligomer has poor selectivity of HFPO tetramer, so that the yield of HFPO tetramer is low and the requirement of industrial production cannot be met.
Disclosure of Invention
In view of the problems and disadvantages of the prior art, it is an object of the present invention to provide a method for preparing HFPO tetramers.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for preparing HFPO tetramers comprising the steps of:
(1) under the atmosphere of protective gas, adding an aprotic solvent and a catalyst into a reaction kettle, and uniformly stirring and dispersing, wherein the catalyst is a mixture of silver nitrate and alkali metal fluoride;
(2) introducing HFPO gas into the reaction kettle, and controlling the temperature of the reaction kettle at 0-10 ℃ to carry out polymerization reaction; and (3) after the reaction is finished, adjusting the temperature of the reaction kettle to room temperature, standing and layering the reaction liquid, and recovering lower-layer substances to obtain the HFPO tetramer.
According to the preparation method, the mass ratio of silver nitrate to alkali metal fluoride in the catalyst is preferably 1 (1.25-2.5). More preferably, the mass ratio of silver nitrate to alkali metal fluoride in the catalyst is 1: 1.5.
According to the above production method, preferably, the alkali metal fluoride is at least one of potassium fluoride, cesium fluoride, sodium fluoride, and lithium fluoride. More preferably, the alkali metal fluoride is potassium fluoride.
According to the above production method, preferably, the water contents of the aprotic solvent, the catalyst and the HFPO gas are not more than 100 ppm. More preferably, the water content of the aprotic solvent, the catalyst and the HFPO gas are not more than 50 ppm.
According to the above preparation method, preferably, the amount of the catalyst is 0.1% to 1.5% by mass of HFPO gas. More preferably, the catalyst is used in an amount of 0.5% by mass of HFPO gas.
According to the above preparation method, preferably, the aprotic solvent is used in an amount of 1% to 15% by mass of HFPO gas. More preferably, the dosage of the aprotic solvent is 5 to 15 percent of the mass of HFPO gas
According to the above production method, preferably, the aprotic solvent is at least one of acetonitrile, adiponitrile, diglyme, triglyme, and tetraglyme. Further preferably, the inert solvent is acetonitrile; more preferably, the amount of acetonitrile is 11.85% by mass of HFPO gas.
According to the above production method, preferably, the HFPO gas is introduced at a rate of 40g/h to 100g/h in the step (2), and the HFPO gas is introduced while stirring. More preferably, the HFPO gas is introduced at a rate of 50 g/h.
According to the above production method, preferably, the protective gas in the step (1) is nitrogen.
According to the above production method, preferably, the reaction vessel temperature in the step (2) is 10 ℃.
According to the above-mentioned production method, the lower layer material in the step (2) is preferably distilled under atmospheric pressure to obtain highly pure HFPO tetramer.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) the invention adopts silver nitrate and anhydrous alkali metal fluoride to carry out compounding as a catalyst, and the mass ratio of the silver nitrate to the anhydrous alkali metal fluoride is regulated to be 1: (1.25-2.5), the polymerization temperature is controlled to be 0-10 ℃, the polymerization reaction can be controlled to proceed towards the direction of generating HFPO tetramer, and the content of the HFPO tetramer in the finally prepared reaction product is up to 92% at most and is far higher than that of the existing preparation method; solves the technical problems of poor HFPO tetramer selectivity and low yield caused by the incapability of controlling the polymerization reaction selectivity in the prior art.
(2) The existing method for preparing the HFPO tetramer is generally carried out at the low temperature of-20 to-30 ℃, so that the energy consumption is high, the production cost is high, and the reaction time is long; according to the preparation method of the HFPO tetramer, the HFPO tetramer can be better synthesized at 0-10 ℃ by regulating the mass ratio of silver nitrate to anhydrous alkali metal fluoride, and the content of the HFPO tetramer in the prepared reaction product is far higher than that of the existing preparation method, so that compared with the prior art, the preparation method of the HFPO tetramer has the advantages of good selectivity to the HFPO tetramer, high product yield, low reaction energy consumption and environmental friendliness.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
Catalyst composition discussion experiment
To investigate the effect of catalyst composition on HFPO tetramer synthesis, the present invention performed the following experiments, see specifically examples 1-5; the experimental results are shown in Table 1.
Example 1:
a method for preparing HFPO tetramers comprising the steps of:
(1) adding 5g of catalyst and 150ml of aprotic solvent into a reaction kettle under the nitrogen protection atmosphere, purging the reaction kettle and a pipeline for 30min by using nitrogen, and then uniformly stirring and dispersing the catalyst and the aprotic solvent, wherein the water contents of the aprotic solvent and the catalyst are not more than 50 ppm; wherein the aprotic solvent is acetonitrile; the catalyst is a mixture of silver nitrate and potassium fluoride, and the mass ratio of the silver nitrate to the potassium fluoride in the catalyst is 1: 1.5;
(2) introducing 1kg of HFPO gas into the reaction kettle, wherein the water content of the HFPO gas does not exceed 50ppm, the aeration rate of the HFPO is 50g/h, the HFPO gas is continuously stirred in the introduction process, the temperature in the reaction kettle is controlled at 5 ℃ by cooling circulation, and the reaction is continuously stirred for 1h after the introduction of the HFPO gas is finished; after the reaction is finished, the temperature of the reaction kettle is adjusted to room temperature, the reaction liquid is kept stand for layering, and lower-layer substances are recovered.
The conversion of the reaction (conversion: mass of lower layer/mass of HFPO × 100%) was measured, and the lower layer was analyzed by gas chromatography to determine the content of HFPO tetramer in the lower layer. The detection conditions of the gas chromatography are as follows: the detection was carried out by GC-2030 (Shimadzu, Japan) gas chromatography using a hydrogen Flame Ionization Detector (FID) as a DB-1 capillary column having a length of 30m and an inner diameter of 0.25 mm. The sample amount was 1. mu.l, and the data was processed by area normalization. The analysis conditions were programmed to 50 ℃ for 2min, then increased to 250 ℃ at a rate of 25 ℃/min and held for 5 min.
Example 2:
the content of example 2 is substantially the same as that of example 1, except that: the catalyst is silver nitrate.
Example 3:
the content of example 3 is substantially the same as that of example 1, except that: the catalyst is silver nitrate, and the using amount of the silver nitrate is 2 g.
Example 4:
example 4 is substantially the same as example 1 except that: the catalyst is potassium fluoride.
Example 5:
the content of example 5 is substantially the same as that of example 1, except that: the catalyst is potassium fluoride, and the dosage of the potassium fluoride is 3 g.
TABLE 1 Effect of the catalyst on HFPO tetramer Synthesis
As can be seen from table 1, when silver nitrate (in an amount of 5g) was used alone as a catalyst, the HFPO tetramer content in the reaction product was very small, only 0.8%, and when potassium fluoride (in an amount of 5g) was used alone as a catalyst, the HFPO tetramer content in the reaction product was also only 41.8%; when silver nitrate and potassium fluoride are compounded as a catalyst, the content of HFPO tetramer in the reaction product reaches 92%, and compared with the method of singly adopting potassium fluoride (the dosage is 5g), the content of HFPO tetramer in the product is increased by about 1.2 times. Therefore, silver nitrate and potassium fluoride combinations were chosen as the preferred catalyst for the synthesis of HFPO tetramers.
Investigation experiment of silver nitrate and potassium fluoride ratio in catalyst
In order to discuss the influence of the ratio of silver nitrate to potassium fluoride in the catalyst on the synthesis of the HFPO tetramer, the invention carries out the following experiments, specifically referring to the examples 6 to 10; the experimental results are shown in Table 2.
Example 6:
a method for preparing HFPO tetramers comprising the steps of:
(1) adding 5g of catalyst and 150ml of aprotic solvent into a reaction kettle under the nitrogen protection atmosphere, purging the reaction kettle and a pipeline for 30min by using nitrogen, and then uniformly stirring and dispersing the catalyst and the aprotic solvent, wherein the water contents of the aprotic solvent and the catalyst are not more than 50 ppm; wherein the aprotic solvent is acetonitrile; the catalyst is a mixture of silver nitrate and potassium fluoride, and the mass ratio of the silver nitrate to the potassium fluoride in the catalyst is 1: 1;
(2) introducing 1kg of HFPO gas into the reaction kettle, wherein the water content of the HFPO gas does not exceed 50ppm, the aeration rate of the HFPO is 50g/h, the HFPO gas is continuously stirred in the introduction process, the temperature in the reaction kettle is controlled at 5 ℃ by cooling circulation, and the reaction is continuously stirred for 1h after the introduction of the HFPO gas is finished; after the reaction is finished, the temperature of the reaction kettle is adjusted to room temperature, the reaction liquid is kept stand for layering, and lower-layer substances are recovered.
The conversion of the reaction (conversion: mass of lower layer/mass of HFPO × 100%) was measured, and the lower layer was analyzed by gas chromatography to determine the content of HFPO tetramer in the lower layer. The detection conditions of the gas chromatography are as follows: the detection was carried out by GC-2030 (Shimadzu, Japan) gas chromatography using a hydrogen Flame Ionization Detector (FID) as a DB-1 capillary column having a length of 30m and an inner diameter of 0.25 mm. The sample amount was 1. mu.l, and the data was processed by area normalization. The analysis conditions were programmed to 50 ℃ for 2min, then increased to 250 ℃ at a rate of 25 ℃/min and held for 5 min.
Example 7:
example 7 is substantially the same as example 6 except that: the mass ratio of silver nitrate to potassium fluoride in the catalyst is 1: 1.25.
Example 8:
example 8 is substantially the same as example 6 except that: the mass ratio of silver nitrate to potassium fluoride in the catalyst is 1: 1.75.
Example 9:
example 9 is substantially the same as example 6 except that: the mass ratio of silver nitrate to potassium fluoride in the catalyst is 1:2.
Example 10:
the contents of example 10 are substantially the same as those of example 6, except that: the mass ratio of silver nitrate to potassium fluoride in the catalyst is 1: 2.5.
TABLE 2 influence of silver nitrate to potassium fluoride ratio in the catalyst on the synthesis of HFPO tetramer
As can be seen from Table 2, the mass ratio of silver nitrate to potassium fluoride in the catalyst is in the range of 1 (1.25-2.5), the content of HFPO trimer in the reaction product can reach more than 70%, and when the mass ratio of silver nitrate to potassium fluoride in the catalyst is 1:1.5, the conversion rate of the reaction is the highest, and the content of HFPO trimer in the reaction product is also the highest, and is 92%. Therefore, the mass ratio of the silver nitrate to the potassium fluoride in the catalyst is preferably 1 (1.25-2.5); more preferably 1: 1.5.
(III) investigation experiment of reaction temperature
To investigate the effect of reaction temperature on HFPO tetramer synthesis, the present inventors performed the following experiments, specifically referring to examples 11-15; the experimental results are shown in Table 3.
Example 11:
a method for preparing HFPO tetramers comprising the steps of:
(1) adding 5g of catalyst and 150ml of aprotic solvent into a reaction kettle under the nitrogen protection atmosphere, purging the reaction kettle and a pipeline for 30min by using nitrogen, and then uniformly stirring and dispersing the catalyst and the aprotic solvent, wherein the water contents of the aprotic solvent and the catalyst are not more than 50 ppm; wherein the aprotic solvent is acetonitrile; the catalyst is a mixture of silver nitrate and potassium fluoride, and the mass ratio of the silver nitrate to the potassium fluoride in the catalyst is 1: 1.5;
(2) introducing 1kg of HFPO gas into the reaction kettle, wherein the water content of the HFPO gas does not exceed 50ppm, the aeration rate of the HFPO is 50g/h, the HFPO gas is continuously stirred in the introduction process, the temperature in the reaction kettle is controlled to be-20 ℃ by cooling circulation, and the reaction is continuously stirred for 1h after the HFPO gas is completely introduced; after the reaction is finished, the temperature of the reaction kettle is adjusted to room temperature, the reaction liquid is kept stand for layering, and lower-layer substances are recovered.
The conversion of the reaction (conversion: mass of lower layer/mass of HFPO × 100%) was measured, and the lower layer was analyzed by gas chromatography to determine the content of HFPO tetramer in the lower layer. The detection conditions of the gas chromatography are as follows: the detection was carried out by GC-2030 (Shimadzu, Japan) gas chromatography using a hydrogen Flame Ionization Detector (FID) as a DB-1 capillary column having a length of 30m and an inner diameter of 0.25 mm. The sample amount was 1. mu.l, and the data was processed by area normalization. The analysis conditions were programmed to 50 ℃ for 2min, then increased to 250 ℃ at a rate of 25 ℃/min and held for 5 min.
Example 12:
the contents of example 12 are substantially the same as those of example 11, except that: in the step (2), the temperature in the reaction kettle is controlled to be-10 ℃.
Example 13:
example 13 is substantially the same as example 11 except that: and (3) controlling the temperature in the reaction kettle to be 0 ℃ in the step (2).
Example 14:
example 14 is substantially the same as example 11 except that: and (3) controlling the temperature in the reaction kettle to be 10 ℃ in the step (2).
Example 15:
example 15 is substantially the same as example 11 except that: and (3) controlling the temperature in the reaction kettle to be 20 ℃ in the step (2).
TABLE 3 influence of silver nitrate to potassium fluoride ratio in the catalyst on the synthesis of HFPO tetramer
As can be seen from Table 3, the reaction temperature is between 0 ℃ and 10 ℃, which is favorable for the synthesis of HFPO trimer, the HFPO tetramer content in the reaction product is high, and the HFPO tetramer content in the reaction product reaches up to 92% when the reaction temperature is controlled at 5 ℃. Therefore, the reaction temperature is preferably 0 to 10 ℃. Since the HFPO tetramer content in the reaction product is not significantly different at the reaction temperature of 5 ℃ and 10 ℃, the reaction temperature is more preferably 10 ℃ in consideration of energy consumption for the reaction.
Example 16:
example 16 is substantially the same as example 1 except that: the catalyst in the step (1) is a mixture of silver nitrate and sodium fluoride, and the mass ratio of the silver nitrate to the sodium fluoride in the catalyst is 1: 1.5; the aprotic solvent is diethylene glycol dimethyl ether.
Example 17:
example 17 is substantially the same as example 1 except that: the catalyst in the step (1) is a mixture of silver nitrate and lithium fluoride, and the mass ratio of the silver nitrate to the lithium fluoride in the catalyst is 1: 1.75; the aprotic solvent is triethylene glycol dimethyl ether.
Example 18:
example 18 is substantially the same as example 1 except that: in the step (1), the aprotic solvent is tetraethylene glycol dimethyl ether.
Example 19:
example 19 is substantially the same as example 1 except that: the catalyst in the step (1) is a mixture of silver nitrate and cesium fluoride, and the mass ratio of the silver nitrate to the cesium fluoride in the catalyst is 1: 1.5; the aprotic solvent is adiponitrile.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, but rather as the following description is intended to cover all modifications, equivalents and improvements falling within the spirit and scope of the present invention.
Claims (8)
1. A method for preparing HFPO tetramer, which is characterized by comprising the following steps:
(1) under the atmosphere of protective gas, adding an aprotic solvent and a catalyst into a reaction kettle, and uniformly stirring and dispersing, wherein the catalyst is a mixture of silver nitrate and alkali metal fluoride;
(2) introducing HFPO gas into the reaction kettle, and controlling the temperature of the reaction kettle at 0-10 ℃ to carry out polymerization reaction; and (3) after the reaction is finished, adjusting the temperature of the reaction kettle to room temperature, standing and layering the reaction liquid, and recovering lower-layer substances to obtain the HFPO tetramer.
2. The method according to claim 1, wherein the mass ratio of silver nitrate to anhydrous alkali metal fluoride in the catalyst is 1 (1.25 to 2.5).
3. The method according to claim 2, wherein the alkali metal fluoride is at least one of potassium fluoride, cesium fluoride, sodium fluoride, and lithium fluoride.
4. The production method according to claim 1, wherein the water contents of the aprotic solvent, the catalyst and the HFPO gas are not more than 100 ppm.
5. The method according to any one of claims 1 to 4, wherein the catalyst is used in an amount of 0.1 to 1.5% by mass of HFPO gas, and the aprotic solvent is used in an amount of 1 to 15% by mass of HFPO gas.
6. The method according to claim 5, wherein the aprotic solvent is at least one of acetonitrile, adiponitrile, diglyme, triglyme, and tetraglyme.
7. The method according to claim 6, wherein the HFPO gas is introduced at a rate of 40g/h to 100g/h in the step (2), and the HFPO gas is introduced while stirring.
8. The method according to claim 7, wherein the protective gas in the step (1) is nitrogen.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112034682A (en) * | 2020-08-04 | 2020-12-04 | 甘肃华隆芯材料科技有限公司 | Fluoropolymer for photoresist, top anti-reflection film composition comprising same and application of fluoropolymer to photoresist |
| CN114057553A (en) * | 2021-11-23 | 2022-02-18 | 四川弘聚氟新材料科技有限公司 | Method for preparing hexafluoropropylene oxide tetramer |
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| CN1034199A (en) * | 1987-11-07 | 1989-07-26 | 赫彻斯特股份公司 | The production method of perfluoro-carbonyl fluoride |
| JPH11116529A (en) * | 1997-10-16 | 1999-04-27 | Asahi Glass Co Ltd | Production of perfluoro(2-methyl-3-oxa-hexanoyl fluoride) |
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Patent Citations (2)
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| CN1034199A (en) * | 1987-11-07 | 1989-07-26 | 赫彻斯特股份公司 | The production method of perfluoro-carbonyl fluoride |
| JPH11116529A (en) * | 1997-10-16 | 1999-04-27 | Asahi Glass Co Ltd | Production of perfluoro(2-methyl-3-oxa-hexanoyl fluoride) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112034682A (en) * | 2020-08-04 | 2020-12-04 | 甘肃华隆芯材料科技有限公司 | Fluoropolymer for photoresist, top anti-reflection film composition comprising same and application of fluoropolymer to photoresist |
| CN114057553A (en) * | 2021-11-23 | 2022-02-18 | 四川弘聚氟新材料科技有限公司 | Method for preparing hexafluoropropylene oxide tetramer |
| CN114057553B (en) * | 2021-11-23 | 2024-03-19 | 四川弘氟新材料有限公司 | Method for preparing hexafluoropropylene oxide tetramer |
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