CN115959975B - Novel perfluoro ether electronic fluorinated liquid production process and device - Google Patents
Novel perfluoro ether electronic fluorinated liquid production process and device Download PDFInfo
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- 229920001774 Perfluoroether Polymers 0.000 title claims abstract description 44
- 239000007788 liquid Substances 0.000 title claims abstract description 44
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 239000002994 raw material Substances 0.000 claims abstract description 71
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 39
- 239000011737 fluorine Substances 0.000 claims abstract description 39
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 26
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001265 acyl fluorides Chemical class 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 78
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000003860 storage Methods 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- 239000011949 solid catalyst Substances 0.000 claims description 9
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 6
- 239000012263 liquid product Substances 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000000110 cooling liquid Substances 0.000 abstract description 5
- 238000010292 electrical insulation Methods 0.000 abstract description 5
- 238000004334 fluoridation Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- POYLATBDQFPQSM-UHFFFAOYSA-N F.FOF Chemical compound F.FOF POYLATBDQFPQSM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 37
- 238000001514 detection method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
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- 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
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a novel perfluoro ether electronic fluorinated liquid production process and a matched production device, which firstly use hexafluoropropylene oxide tetramer acyl fluoride with a single structure as a raw material, adopt a reaction rectifying device, greatly improve the fluorination efficiency in a gas-gas contact mode, timely separate out products in the fluorination process, realize continuous operation and be beneficial to large-scale production. The perfluoro ether fluoride liquid obtained by fluorination has high electrical insulation, and is ideal single-phase immersed electronic cooling liquid. According to the novel perfluoro ether electronic fluorinated liquid production process, the conversion rate of raw materials is improved to the greatest extent by adjusting the key factors such as the flow rate ratio of the raw materials to fluorine gas, the temperature, the catalyst, the length-diameter ratio of a rectifying column and the like; the fluorine gas in the product is removed to the maximum extent by adjusting key factors such as the reflux ratio of the flow divider, the product preheating tank and the like, so that the purity of the product fluoridation liquid is improved.
Description
Technical Field
The invention belongs to the technical field of chemical preparation, and particularly relates to a novel perfluoro ether electronic fluorinated liquid production process and a novel perfluoro ether electronic fluorinated liquid production device.
Background
The electronic fluoridation liquid is colorless, transparent, low-viscosity, nonflammable, high in electrical insulation, safe and environment-friendly, and is often used as an electronic test liquid, a cleaning agent, a coolant and the like in the fields of semiconductors, precise electronic devices, aerospace, medical treatment and the like. In recent years, the internet, artificial intelligence, cloud computing and High Performance Computing (HPC) have been rapidly developed, and internet data centers as carriers thereof have also been developed in a blowout manner. As is well known, the energy consumption in the data is very high, and an immersed liquid cooling method using an electronic fluoridation liquid as a cooling liquid is generated. At present, the existing electronic fluorinated liquid in the liquid cooling market mainly comprises hydrofluoroether type electronic fluorinated liquid, such as 3M Novec series electronic fluorinated liquid, but the hydrofluoroether type electronic fluorinated liquid has unsatisfactory dielectric electric property due to the fact that the molecular structure of the electronic fluorinated liquid contains hydrogen. The GOLDEN series developed by the company suwei is a perfluoroether type electronic fluorinated solution, but the perfluoroether is a series of perfluoroether mixtures with similar boiling ranges, so that the development of a perfluoroether type electronic fluorinated solution with a definite single molecular structure is a problem to be solved.
Hexafluoropropylene oxide is copolymerized to obtain a series of K-type perfluoropolyethers, and the reaction can be stopped in the oligomerization stage by controlling the process conditions, for example, chinese patent CN108264458A discloses a method for preparing hexafluoropropylene oxide dimer. Chinese patent CN110041192a mentions a process for preparing hexafluoropropylene oxide trimer. Chinese patent CN114057553a mentions a method for preparing hexafluoropropylene oxide tetramer. The perfluoro ether intermediate with a definite single molecular structure can be obtained by separating the single polymerization degree.
The perfluoro ether intermediate obtained by polymerization needs to be further fluorinated to obtain stable perfluoro ether electronic fluorinated liquid, most of the existing fluorinated patent technologies are gas-liquid contact reactions, the timely transfer of fluorinated products in the fluorination process cannot be realized, continuous fluorination cannot be realized, and the defects of low fluorination efficiency, low fluorine gas utilization rate, long fluorination time and the like are caused. For example, in chinese patent CN110092901a, although gas bubbling method is adopted for fluorination and gas-liquid contact can be increased, the above-mentioned drawbacks cannot be fundamentally solved, and the problem of low fluorination efficiency is always present. In chinese patent CN103111253a, the unreacted fluorine gas is recycled, so that the problem of continuous fluorination and the problem of changing the fluorination efficiency in the later reaction period cannot be realized although the utilization rate of the fluorine gas is improved. Chinese patent CN106311097A adopts a spraying mode, is beneficial to increasing the gas-liquid contact area, but still can not realize the problem of timely separation of products. In chinese patent CN 107383355A, although gas-liquid contact can be improved by adopting a micro-reactor for fluorination, continuous operation can be realized, but the product cannot be separated in time in the fluorination process, and the defect of low fluorination efficiency is not effectively improved.
Disclosure of Invention
The invention aims to: the invention aims to overcome the defects of the prior art and provide a novel perfluorinated ether electronic fluorinated liquid production process and device which can be produced in a large scale and have high fluorination efficiency.
The technical scheme is as follows: the first aim of the invention is to provide a novel perfluoro ether electronic fluorinated liquid production process, which is obtained by taking hexafluoropropylene oxide tetrapoly fluoride as a raw material and performing fluorinated end capping, wherein the specific reaction equation is shown as a formula (I):
further, as a preferred embodiment, the method specifically comprises the following steps:
(1) Heating hexafluoropropylene oxide tetra-polyamide fluoride raw material to gasify the raw material, enabling the raw material to enter a reaction rectifying column at a certain speed through a mass flow controller, enabling fluorine gas to enter the bottom of the reaction rectifying column at a certain speed, heating the bottom of the reaction rectifying column to a required temperature, keeping the outside of the reaction rectifying column warm, and filling a filler and a catalyst in the reaction rectifying column;
(2) Fully contacting hexafluoropropylene oxide tetrapoly fluoride raw material with fluorine gas in a reaction rectifying column, and carrying out fluorination reaction in a gas-gas contact mode to obtain a perfluoro ether electronic fluorinated liquid product; because the boiling point of the perfluoro ether electronic fluorinated liquid product is low, the product is discharged from the top and enters a condenser, and after the raw material of hexafluoropropylene oxide tetrameric acyl fluoride is rectified and refluxed by reaction, the raw material is repeatedly contacted with fluorine gas until the reaction is complete;
(3) The boiling point of the product which is completely reacted becomes low, the product is distilled from the top of a rectifying column, the rectifying column sets a condensation reflux ratio, the product is collected and enters a product preheating tank, the preheating tank sets a certain temperature, so that fluorine gas carried in the product is separated, the product enters an alkali liquor absorption tank, and the product with the separated fluorine climate enters a product storage tank; the product yield is calculated for a certain period of time by sampling from a product storage tank, detecting the infrared of the product, determining the degree of completion of the fluorination of the product, and recording the consumption of the fluorine gas.
Further, as a preferred embodiment, the heating temperature of the raw materials in the step (1) is set to 160-220 ℃, and the heated raw materials enter the reactive distillation column at a rate of 6-60 g/min; the flow rate of the fluorine gas is controlled to be 0.5-5L/min through a gas mass flowmeter;
further, as a preferred embodiment, the aspect ratio of the reactive rectifier is 10:1-20:1, the length of the rectifying column is 2-5 m, the periphery of the rectifying column is covered with a heat insulation material, the column filler is titanium alloy filler, the solid catalyst is one or more of sodium fluoride, potassium fluoride and cesium fluoride, and the solid catalyst accounts for 0.5-1% by mass.
Further, in order to realize gas-gas contact reaction and improve reaction efficiency and conversion rate, a heating device is arranged at the bottom of the reaction rectifier in the step (1), and the heating temperature of the heating device for the bottom of the reaction rectifier is controlled to be 170-250 ℃.
Further, as a preferred embodiment, a flow divider is arranged at the downstream of the condenser, and the reflux ratio is designed to be 9:1-19:1; the preheating temperature of the product preheating tank is set to be 40-60 ℃.
The second aim of the invention is to provide a novel perfluoro ether electronic fluorinated liquid, the specific structure of which is shown as the formula (II):
the third object of the invention is to provide a novel perfluoroether electronic fluorinated liquid production device, which comprises a raw material heating tank, a reaction rectifying column, a condenser, a flow divider, a product preheating tank, a product storage tank and an alkali liquor absorption tank, wherein a raw material outlet and a raw material inlet are arranged on the raw material heating tank, and the raw material inlet is connected with a raw material bin; the raw material outlet is connected with the bottom of the reaction rectifying column, and the heated raw material enters the reaction rectifying column from the bottom; a fluorine gas inlet is formed in the side part of the bottom end of the reaction rectifying column; the top outlet of the reaction rectifying column is connected with the inlet of the condenser, the condenser is divided into two outlets, and one outlet is connected with the alkali liquor absorption tank; the other outlet is connected with a flow divider, the outlet of the flow divider is connected with a product preheating tank, and the bottom outlet of the product preheating tank is connected with the product storage tank; and an outlet at the top of the product preheating tank is connected into an alkali liquor absorption tank.
Further, as a preferred embodiment, a control valve is provided on a pipe connecting the product preheating tank and the product storage tank.
Further, as a preferred embodiment, a heating device is provided at the bottom of the reaction and rectification column to heat the fluorine gas fed into the reaction and rectification column.
The beneficial effects are that: (1) According to the scheme, hexafluoropropylene oxide tetramer acyl fluoride with a single structure is used as a raw material for the first time, a reactive rectifying device is adopted, the fluorination efficiency is greatly improved in a gas-gas contact mode, and products are timely separated in the fluorination process, so that continuous operation is realized, and large-scale production is facilitated; the perfluoro ether fluoride liquid obtained by fluorination has high electrical insulation, and is ideal single-phase immersed electronic cooling liquid; (2) According to the novel perfluoro ether electronic fluorinated liquid production process, the conversion rate of raw materials is improved to the greatest extent by adjusting the key factors such as the flow rate ratio of the raw materials to fluorine gas, the temperature, the catalyst, the length-diameter ratio of a rectifying column and the like; the fluorine gas in the product is removed to the maximum extent by adjusting key factors such as the reflux ratio of the flow divider, the product preheating tank and the like, so that the purity of the product fluoridation liquid is improved.
Drawings
FIG. 1 is an infrared spectrum of a product perfluoroether electronic fluorinated solution of the present invention;
FIG. 2 is a schematic view showing the overall structure of the reaction apparatus of the present invention;
wherein: 1. the device comprises a raw material heating tank 2, a reaction rectifying column 3, a condenser 4, a flow divider 5, a product preheating tank 6, a product storage tank 7 and an alkali liquor absorbing tank.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: as shown in fig. 2, the embodiment provides a novel perfluoroether electronic fluorinated liquid production device, which comprises a raw material heating tank 1, a reaction rectifying column 2, a condenser 3, a flow divider 4, a product preheating tank 5, a product storage tank 6 and an alkali liquor absorption tank 7, wherein a raw material outlet and a raw material inlet are arranged on the raw material heating tank 1, and the raw material inlet is connected with a raw material bin; the raw material outlet is connected with the bottom of the reaction rectifying column 2, and the heated raw material enters the reaction rectifying column 2 from the bottom; a fluorine gas inlet is formed in the side part of the bottom end of the reaction rectifying column 2; the top outlet of the reaction rectifying column 2 is connected with the inlet of the condenser 3, the condenser 3 is divided into two outlets, and one outlet is connected with the alkali liquor absorption tank 7; the other outlet is connected with a flow divider 4, the outlet of the flow divider 4 is connected with a product preheating tank 5, and the bottom outlet of the product preheating tank 5 is connected with a product storage tank 6; the top outlet of the product preheating tank 6 is connected with an alkali liquor absorption tank 7; a control valve is arranged on a pipeline connected with the product preheating tank 7 and the product storage tank 6; the bottom of the reaction rectifying column 2 is provided with a heating device for heating the fluorine gas input into the reaction rectifying column 2.
Example 2: preparing perfluoro ether electronic fluorinated liquid by adopting the device of the embodiment 1, wherein the length of a reaction rectifying column is 5m, the length-diameter ratio of the reaction rectifying column is 10:1, the filler is titanium alloy filler, and the solid catalyst is sodium fluoride with the mass ratio of 0.8%;
the temperature of the raw material heating tank is set to be 180 ℃, raw material hexafluoropropylene oxide tetramer acyl fluoride is added into the raw material heating tank at the rate of 30g/min, a gas mass flowmeter is controlled to enable the hexafluoropropylene oxide tetramer acyl fluoride to enter the bottom of the reaction rectifying device at the rate of 30g/min, fluorine gas enters the bottom of the reaction rectifying device at the rate of 1.5L/min, and the temperature of the reaction rectifying column is set to be 200 ℃; the reflux ratio was set at 14:1 and the preheating tank was set at 50 ℃.
Sampling from a product storage tank, and obtaining 40.9kg of product after 24 hours with a yield of 98.8%, wherein the molar ratio of fluorine gas to raw material is calculated to be 1.48:1, as shown in FIG. 1, which is an infrared spectrogram of the perfluoroether electronic fluorinated solution obtained in the embodiment, at 1885cm -1 The nearby acyl fluoride carbonyl peak disappeared, confirming complete fluorination.
Wherein, the peak position of the characteristic functional group fully proves that the scheme successfully prepares the perfluoroether electronic fluorinated solution.
Example 3: preparing perfluoro ether electronic fluorinated liquid by adopting the device of the embodiment 1, wherein the length of a reaction rectifying column is 5m, the length-diameter ratio of the reaction rectifying column is 10:1, the filler is titanium alloy filler, and the solid catalyst is sodium fluoride with the mass ratio of 0.8%;
the temperature of the raw material heating tank is set to be 200 ℃, raw material hexafluoropropylene oxide tetramer acyl fluoride is added into the raw material heating tank at the rate of 60g/min, meanwhile, a gas mass flowmeter is controlled to enable the hexafluoropropylene oxide tetramer acyl fluoride to enter the bottom of the reaction rectifying device at the rate of 60g/min, meanwhile, 3.25L/min of fluorine gas enters the bottom of the reaction rectifying device, and the temperature of the reaction rectifying column is set to be 225 ℃. The reflux ratio was set at 14:1 and the preheating tank was set at 50 ℃.
Sampling from a product storage tank, and obtaining 81.5kg of product after 24 hours with a yield of 98.5%, wherein the molar ratio of fluorine gas to raw material is calculated to be 1.6:1.
Example 4: preparing perfluoro ether electronic fluorinated liquid by adopting the device of the embodiment 1, wherein the length of a reaction rectifying column is 5m, the length-diameter ratio of the reaction rectifying column is 10:1, the filler is titanium alloy filler, and the solid catalyst is sodium fluoride with the mass ratio of 0.8%; the temperature of the raw material heating tank is set to 170 ℃, raw material hexafluoropropylene oxide tetramer acyl fluoride is added into the raw material heating tank at the rate of 10g/min, meanwhile, a gas mass flowmeter is controlled to enable hexafluoropropylene oxide tetramer acyl fluoride to enter the bottom of the reaction rectifying device at the rate of 10g/min, meanwhile, fluorine gas enters the bottom of the reaction rectifying device at the rate of 0.4L/min, and the temperature of the reaction rectifying column is set to 190 ℃. The reflux ratio was set at 19:1 and the preheating tank was set at 50 ℃.
Sampling from a product storage tank, and obtaining 13.7kg of a product after 24 hours, wherein the yield is 99.3%, and the molar ratio of fluorine gas to raw materials is 1.19:1.
Example 5: the apparatus of example 1 was used to prepare perfluoroether electronic fluorination solution using a reaction rectification column of length 6m and aspect ratio 15:1 with titanium alloy filler and potassium fluoride as the solid catalyst at a ratio of 0.5%.
The temperature of the raw material heating tank is set to be 180 ℃, raw material hexafluoropropylene oxide tetramer acyl fluoride is added into the raw material heating tank at the rate of 30g/min, a gas mass flowmeter is controlled to enable the hexafluoropropylene oxide tetramer acyl fluoride to enter the bottom of the reaction rectifying device at the rate of 30g/min, meanwhile fluorine gas enters the bottom of the reaction rectifying device at the rate of 1.6L/min, and the temperature of the reaction rectifying column is set to be 200 ℃. The reflux ratio was set at 14:1 and the preheating tank was set at 50 ℃.
Sampling from a product storage tank, and obtaining 40.6kg of product after 24 hours with a yield of 98.1% by infrared detection results, wherein the molar ratio of fluorine gas to raw materials is 1.62:1.
Example 6: the apparatus of example 1 was used to prepare perfluoroether electronic fluorination solution using a reaction rectification column of length 6m and aspect ratio 15:1 with titanium alloy filler and cesium fluoride as the solid catalyst at a ratio of 0.5%.
The temperature of the raw material heating tank is set to be 180 ℃, raw material hexafluoropropylene oxide tetramer acyl fluoride is added into the raw material heating tank at the rate of 30g/min, a gas mass flowmeter is controlled to enable hexafluoropropylene oxide tetramer to enter the bottom of the reaction rectifying device at the rate of 30g/min, fluorine gas enters the bottom of the reaction rectifying device at the rate of 1.4L/min, and the temperature of the reaction rectifying column is set to be 200 ℃. The reflux ratio was set at 14:1 and the preheating tank was set at 50 ℃.
Sampling from a product storage tank, and obtaining 41.0kg of a product after 24 hours, wherein the yield is 99.1%, and the molar ratio of fluorine gas to raw materials is 1.38:1.
Example 7: this example is a comparative example, namely, in the case of preparing perfluoroether electronic fluorinated solution by adopting the prior art, 40.0kg of hexafluoropropylene oxide tetramer acyl fluoride raw material is added into a 50L reaction kettle, the reaction kettle is heated to 160 ℃ and vacuumized, a condensation reflux device is arranged in the reaction kettle, F2 is bubbled in from the bottom of the reaction kettle at a rate of 1.5L/min, the flow rate is adjusted to N2 20ml/min, the material is taken from a discharge valve at the bottom of the reaction kettle in the reaction process, the reaction progress is monitored by infrared spectrum, and the fluorine gas is continuously introduced for 110h. The infrared detection result shows that the end is completely blocked, 34.7kg of product is obtained, the yield is 86.8%, and the molar ratio of fluorine gas to raw materials is calculated to be 7.34:1.
As can be seen from the comparison of the results of the above examples, the yields of the perfluoro ether electronic fluorinated liquid prepared by the scheme of the invention in examples 2-6 can reach more than 98.5%, and the yield is greatly improved compared with the yield of 86.8% in the comparative example, thereby fully proving the practicability of the scheme of the invention.
The data for the detection of the dielectric constant, saturated water content, and fluoride ion content of the perfluoroether electronic fluorinated solution in examples 2 to 7 are shown in Table 1:
TABLE 1 summary of the data for the detection of perfluoroether electronic fluorinated liquids in examples 2-7
| Examples numbering | Dielectric constant | Saturated water content (ppm) | Fluoride ion content (ppm) |
| Example 2 | 1.2 | 18 | 35 |
| Example 3 | 1.3 | 21 | 48 |
| Example 4 | 1.1 | 15 | 30 |
| Example 5 | 1.3 | 25 | 45 |
| Example 6 | 1.2 | 20 | 37 |
| Example 7 | 1.9 | 51 | 171 |
For the perfluoroether electronic fluorinated liquid product, the lower the dielectric constant is, the better the electrical insulation performance is, the safer the electronic product is when being used for immersed cooling liquid of the electronic product, and the lower the acid value, the saturated water content and the fluoride ion content are, the less the corrosiveness to the electronic product is. By combining the data, the perfluoro ether electronic fluorinated liquid product obtained by adopting the scheme of the invention and the prior art has obviously good electrical insulation property, lower corrosion performance on electronic products and good effect on immersed cooling liquid of the electronic products.
As described above, although the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limiting the invention itself. Various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A novel perfluoro ether electronic fluorinated liquid production process uses hexafluoropropylene oxide tetrapoly fluoride as a raw material, and is obtained through fluorination end capping, and a specific reaction equation is shown as a formula (I):
the method is characterized by comprising the following steps of:
(1) Heating hexafluoropropylene oxide tetra-polyamide fluoride raw material to gasify the raw material, enabling the raw material to enter a reaction rectifying column at a certain speed through a mass flow controller, enabling fluorine gas to enter the bottom of the reaction rectifying column at a certain speed, heating the bottom of the reaction rectifying column to a required temperature, keeping the outside of the reaction rectifying column warm, and filling a filler and a catalyst in the reaction rectifying column;
(2) Fully contacting hexafluoropropylene oxide tetrapoly fluoride raw material with fluorine gas in a reaction rectifying column, and carrying out fluorination reaction in a gas-gas contact mode to obtain a perfluoro ether electronic fluorinated liquid product; because the boiling point of the perfluoro ether electronic fluorinated liquid product is low, the product is discharged from the top and enters a condenser, and after the raw material of hexafluoropropylene oxide tetrameric acyl fluoride is rectified and refluxed by reaction, the raw material is repeatedly contacted with fluorine gas until the reaction is complete;
(3) The boiling point of the product which is completely reacted becomes low, the product is distilled from the top of a rectifying column, the rectifying column sets a condensation reflux ratio, the product is collected and enters a product preheating tank, the preheating tank sets a certain temperature, so that fluorine gas carried in the product is separated, the product enters an alkali liquor absorption tank, and the product with the separated fluorine climate enters a product storage tank; the product yield is calculated for a certain period of time by sampling from a product storage tank, detecting the infrared of the product, determining the degree of completion of the fluorination of the product, and recording the consumption of the fluorine gas.
2. The novel perfluoroether electronic fluorinated liquid production process according to claim 1, characterized in that: the heating temperature of the raw materials in the step (1) is set to 160-220 ℃, and the heated raw materials enter a reaction rectifying column at the rate of 6-60 g/min; the flow rate of the fluorine gas is controlled to be 0.5-5L/min through a gas mass flowmeter.
3. The novel perfluoroether electronic fluorinated liquid production process according to claim 2, characterized in that: the length-diameter ratio of the reactive rectifier is 10:1-20:1, the length of the rectifying column is 2-5 m, the periphery of the rectifying column is covered with a heat insulation material, the column filler is titanium alloy filler, the solid catalyst is one or more of sodium fluoride, potassium fluoride and cesium fluoride, and the solid catalyst accounts for 0.5-1% by mass.
4. The novel perfluoroether electronic fluorinated liquid production process according to claim 3, wherein the production process is characterized in that: in the step (1), a heating device is arranged at the bottom of the reactive rectifier, and the heating temperature of the heating device for the bottom of the reactive rectifier is controlled to be 170-250 ℃.
5. The novel perfluoroether electronic fluorinated liquid production process according to claim 4, wherein a flow divider is arranged at the downstream of the condenser, and the design reflux ratio is 9:1-19:1; the preheating temperature of the product preheating tank is set to be 40-60 ℃.
6. The novel perfluoro ether electronic fluorinated liquid production device is characterized in that: the device comprises a raw material heating tank, a reaction rectifying column, a condenser, a flow divider, a product preheating tank, a product storage tank and an alkali liquor absorption tank, wherein a raw material outlet and a raw material inlet are arranged on the raw material heating tank, and the raw material inlet is connected with a raw material bin; the raw material outlet is connected with the bottom of the reaction rectifying column, and the heated raw material enters the reaction rectifying column from the bottom; a fluorine gas inlet is formed in the side part of the bottom end of the reaction rectifying column; the top outlet of the reaction rectifying column is connected with the inlet of the condenser, the condenser is divided into two outlets, and one outlet is connected with the alkali liquor absorption tank; the other outlet is connected with a flow divider, the outlet of the flow divider is connected with a product preheating tank, and the bottom outlet of the product preheating tank is connected with the product storage tank; and an outlet at the top of the product preheating tank is connected into an alkali liquor absorption tank.
7. The novel perfluoroether electronic fluorinated liquid production device according to claim 6, wherein: and a control valve is arranged on a pipeline connected with the product preheating tank and the product storage tank.
8. The novel perfluoroether electronic fluorinated liquid production device according to claim 6, wherein: and a heating device is arranged at the bottom of the reaction rectifying column to heat the fluorine gas input into the reaction rectifying column.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3985810A (en) * | 1974-10-30 | 1976-10-12 | Hoechst Aktiengesellschaft | Process for preparing perfluorinated ethers |
| US4523039A (en) * | 1980-04-11 | 1985-06-11 | The University Of Texas | Method for forming perfluorocarbon ethers |
| US5185473A (en) * | 1991-06-21 | 1993-02-09 | Hoechst Aktiengesellschaft | Process for the preparation of perfluorinated ethers |
| WO1996040606A1 (en) * | 1995-06-07 | 1996-12-19 | E.I. Du Pont De Nemours And Company | Manufacture of 1,1-difluoroethane by reactive distillation |
| CN110092901A (en) * | 2019-05-30 | 2019-08-06 | 上海欧勒奋生物科技有限公司 | A kind of flaorination process of perfluoropolyether unstable end-group |
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2022
- 2022-10-10 CN CN202211236536.4A patent/CN115959975B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3985810A (en) * | 1974-10-30 | 1976-10-12 | Hoechst Aktiengesellschaft | Process for preparing perfluorinated ethers |
| US4523039A (en) * | 1980-04-11 | 1985-06-11 | The University Of Texas | Method for forming perfluorocarbon ethers |
| US5185473A (en) * | 1991-06-21 | 1993-02-09 | Hoechst Aktiengesellschaft | Process for the preparation of perfluorinated ethers |
| WO1996040606A1 (en) * | 1995-06-07 | 1996-12-19 | E.I. Du Pont De Nemours And Company | Manufacture of 1,1-difluoroethane by reactive distillation |
| CN110092901A (en) * | 2019-05-30 | 2019-08-06 | 上海欧勒奋生物科技有限公司 | A kind of flaorination process of perfluoropolyether unstable end-group |
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