CN115160130A - Preparation method of high-thermal-conductivity fluorinated liquid - Google Patents
Preparation method of high-thermal-conductivity fluorinated liquid Download PDFInfo
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- CN115160130A CN115160130A CN202210803692.8A CN202210803692A CN115160130A CN 115160130 A CN115160130 A CN 115160130A CN 202210803692 A CN202210803692 A CN 202210803692A CN 115160130 A CN115160130 A CN 115160130A
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- 239000007788 liquid Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 238000005406 washing Methods 0.000 claims abstract description 33
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- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 239000003377 acid catalyst Substances 0.000 claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 14
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- -1 ester compound Chemical class 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 9
- SAPOZTRFWJZUFT-OWOJBTEDSA-N (e)-1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)pent-2-ene Chemical compound FC(F)(F)C(/F)=C(\F)C(F)(C(F)(F)F)C(F)(F)F SAPOZTRFWJZUFT-OWOJBTEDSA-N 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- FYQFWFHDPNXORA-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C FYQFWFHDPNXORA-UHFFFAOYSA-N 0.000 claims description 4
- PDFSXHZXNZCKNF-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorodeca-1,9-diene Chemical compound C=CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C PDFSXHZXNZCKNF-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- FAEGGADNHFKDQX-UHFFFAOYSA-N 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)pent-2-ene Chemical compound FC(F)(F)C(C(F)(F)F)=C(F)C(F)(F)C(F)(F)F FAEGGADNHFKDQX-UHFFFAOYSA-N 0.000 claims description 2
- PBVZTJDHQVIHFR-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F PBVZTJDHQVIHFR-UHFFFAOYSA-N 0.000 claims description 2
- RMHCWMIZBMGHKV-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluorohex-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RMHCWMIZBMGHKV-UHFFFAOYSA-N 0.000 claims description 2
- DDWZJDVOCYVHKD-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6-undecafluorohex-1-ene Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)C(F)=C(F)F DDWZJDVOCYVHKD-UHFFFAOYSA-N 0.000 claims description 2
- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 claims description 2
- YBMDPYAEZDJWNY-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluorocyclopentene Chemical compound FC1=C(F)C(F)(F)C(F)(F)C1(F)F YBMDPYAEZDJWNY-UHFFFAOYSA-N 0.000 claims description 2
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 2
- CKQSBYDHYWBCJM-UHFFFAOYSA-N 2,3,3-trifluoropropanoic acid Chemical compound OC(=O)C(F)C(F)F CKQSBYDHYWBCJM-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 230000017525 heat dissipation Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 48
- 238000009833 condensation Methods 0.000 description 12
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- 125000000524 functional group Chemical group 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 239000000376 reactant Substances 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
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- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
Abstract
The invention discloses a preparation method of high-thermal-conductivity fluorinated liquid, and particularly relates to an addition esterification reaction of perfluoroolefin and organic carboxylic acid, a fluorine-containing ester compound is generated after the reaction, and the fluorine-containing ester compound has the characteristics of excellent heat conductivity, electric insulation property, chemical stability, thermal stability, low boiling point and the like, and the preparation method of the fluorinated liquid comprises the following steps: performing addition esterification reaction on a carbon-carbon double bond and a carboxyl oxygen-hydrogen bond of perfluoroolefin and organic carboxylic acid in a strong acid catalyst under a heating condition, washing the reacted mixture with a weak alkaline solution and pure water in sequence, separating liquid, drying and dehydrating to obtain the target product. And (3) performing a thermal conductivity test on the target product, wherein the thermal conductivity coefficient is more than 0.2W/m.k, and performing a water content test, wherein the water content is less than 50ppm. The heat dissipation system can be applied to a chip heat dissipation system, a large-scale server heat dissipation system, a super-computation data center heat dissipation system, a new energy vehicle heat management system and the like.
Description
Technical Field
The invention relates to the technical field of preparation of fluorinated liquid, in particular to a preparation method of high-thermal-conductivity fluorinated liquid.
Background
The fluoridized liquid is a chemical solvent, colorless, transparent, tasteless, safe and nontoxic. The perfluorinated liquid has the characteristics of excellent dielectric constant, stable chemical inertness, good heat conducting property, extremely low surface tension and kinematic viscosity, system compatibility and inertness of insulation and non-combustibility, is applied to the cooling liquid of a data center, and is the sinking cooling liquid which is most widely applied at present.
The fluorizated liquid product is applied to precise temperature control cooling of semiconductors, liquid crystals and other high value-added electronic industries. Meanwhile, the method can be applied to a data center and a refrigerant in the aspect of electric power heat dissipation. And the method is also widely applied to various fields of national defense war industry, aerospace, electronic and electric appliances, semiconductors, special automobiles, machinery, chemical engineering, textiles, buildings, medicines and the like.
The fluorizated liquid product has the following characteristics: 1. permeability: low viscosity, extremely low surface tension, capability of penetrating into tiny gaps and small viscosity change at low temperature. 2. Chemical properties: excellent thermal conductivity, thermal stability and chemical stability. 3. Drying property: moderate boiling point, small heat of vaporization during evaporation, high evaporation speed, excellent drying performance, short drying time, and no water mark left after removing water. 4. Effect on solid materials: excellent material compatibility, and no damage to the surface of plastic, resin, metal and other materials. 5. Reproducibility: can be distilled and regenerated, can be repeatedly used and reduces the cost. 6. Electrical insulation: is very stable and does not change with the temperature change.
The current commercial fluorinated liquid products are mainly FC series of 3M company, and the heat conductivity of the products is generally less than 0.1W/(m.k). Its application has its limitation in the heat dissipation in the fields such as server, semiconductor chip. The invention is especially provided for solving the problem of low heat conductivity of the current commercial product. The heat dissipation requirements of a chip heat dissipation system, a large-scale server heat dissipation system, a super-computation data center heat dissipation system and a new energy vehicle heat management system are increased day by day.
Disclosure of Invention
The invention aims to: in order to solve the problems, a preparation method of a high-thermal-conductivity fluorinated liquid is provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of high thermal conductivity fluorinated liquid comprises the addition esterification reaction of perfluoroolefin and organic carboxylic acid, and a fluorine-containing ester compound is generated after the reaction, wherein the compound is the high thermal conductivity low dielectric fluorinated liquid, and is characterized in that the preparation method comprises the following steps: under the heating condition of a strong acid catalyst, carbon-carbon double bonds in perfluoroolefin and carboxyl oxygen-hydrogen bonds in perfluoroolefin undergo an addition esterification reaction, and the mixed solution after the reaction is sequentially washed by weak alkaline solution and pure water, and then subjected to liquid separation, drying and dehydration to obtain the target product.
Preferably, the perfluoroolefin is: hexafluoropropylene dimer, perfluoro (4-methyl-2-pentene), perfluoro (2-methyl-2-pentene), perfluorocyclopentene, perfluorohex-1-ene, hexafluoropropylene trimer, perfluorobutylethylene, perfluorodecylene, hexafluoro-1, 3-butadiene, perfluorohexylethylene, dodecafluoro-1, 9-decadiene, 6H-perfluoro-1-hexene.
Preferably, the organic carboxylic acid is: formic acid, acetic acid, propionic acid, trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid, pentafluoropropionic acid, 2, 3-tetrafluoropropionic acid, 3-trifluoropropionic acid.
Preferably, the strongly acidic catalyst is: concentrated sulfuric acid, phosphotungstic acid, silicotungstic acid and phosphomolybdic acid.
Preferably, the heating conditions are: the initial temperature of the heating reaction is controlled to be 70-150 ℃ according to the type of the selected raw materials.
Preferably, the carbon-carbon double bond in the perfluoroolefin and the carboxyl oxygen hydrogen bond have addition esterification reaction: an organic carboxylic acid containing a strongly acidic catalyst is used as a reaction substrate, and a perfluoroolefin is added dropwise to the reaction substrate to perform an esterification addition reaction under a heating condition.
Preferably, the mixed solution after the reaction is washed by weak alkaline solution and pure water in sequence, and then liquid separation is carried out to obtain a target product: and adding a sodium carbonate or sodium bicarbonate solution into the mixed solution after the reaction, stirring and washing, separating, collecting a lower-layer product, adding pure water into the lower-layer product, stirring and washing, separating again, and collecting the lower-layer product to obtain the high-thermal-conductivity fluorinated liquid.
Preferably, after the lower-layer product is dried and dehydrated by calcium oxide, the water content of the product is required to be less than 50ppm, and then the high-thermal-conductivity fluorinated liquid can be obtained.
Preferably, the high-thermal conductivity fluorinated liquid meets the requirements of thermal conductivity coefficient being more than 0.2W/(m.K) and water content being less than 50ppm through tests.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the heat-conducting property of the current commercially available fluorinated liquid product is generally less than 0.1W/(m.k), and in order to improve the condition that the overall heat-conducting property of the commercially available common fluorinated liquid is low, the heat-conducting property of the target fluorinated liquid product obtained by the invention is greatly improved, the heat-conducting coefficient is more than 0.2W/(m.K), and the target fluorinated liquid product has low dielectric constant and good insulating property. The variety of the immersion type cooling liquid is expanded.
2. The invention fully considers the atom economy, the addition esterification reaction, the reaction condition is mild and controllable, the utilization rate of reactants in the raw materials is high, and the product yield is high.
3. The product post-treatment purification operation of the invention is convenient and simple, green and pollution-free, and has good economic benefit.
Drawings
FIG. 1 is a schematic diagram illustrating a preparation process of a fluorinated liquid according to an embodiment of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment shown in fig. 1 is as follows:
example 1
Perfluoro (4-methyl-2-pentene) and formic acid are used as raw materials, concentrated sulfuric acid (98.3%) is used as a catalyst, and the heating reaction starting temperature is controlled at 70 ℃. Weighing 55.2g of formic acid, putting the formic acid into a reaction kettle which is connected with a condensation reflux device and can be electrically stirred, wherein the condensation reflux device is used for reducing the volatilization loss of reaction raw materials and ensuring that the pressure in the reaction kettle is normal pressure, raising the temperature of the reaction kettle and starting the electric stirring, adding 17.8g of catalyst concentrated sulfuric acid (98.3%) at one time when the temperature of the formic acid reaches 70 ℃, dropwise adding 300g of perfluoro (4-methyl-2-pentene) into the reaction kettle by using a constant-pressure dropping funnel, controlling the dropwise adding time to be 1hr, maintaining the external heating temperature to be 70 ℃ after the dropwise adding is finished, and continuously stirring and reacting for 5hrs.
The amount of reactants is calculated by the molar ratio of the reactive functional groups, and the feeding molar ratio of the reactive functional groups is controlled as follows: carbon-carbon double bond: carboxy oxygen hydrogen bond = 1.2, formic acid in excess to suppress side reactions and hydrolysis reactions of the product. The reaction process comprises the steps of taking organic carboxylic acid containing a strong acid catalyst as a reaction substrate, wherein the amount of the strong acid catalyst is 5% of the total mass of reaction raw materials, and carrying out esterification addition reaction in a manner of dropwise adding perfluoroolefin into the reaction substrate under the heating and stirring conditions.
Washing the reacted mixed solution with alkalescent solution and pure water in sequence, separating liquid, drying and dehydrating to obtain a target product: adding sodium carbonate or sodium bicarbonate solution into the mixed solution after reaction, stirring and washing, then separating liquid, repeating the steps for 3 times, collecting the lower-layer product, adding pure water into the lower-layer product, stirring and washing, repeating the steps for 5 times, separating liquid again, collecting the lower-layer product, and drying the product through calcium oxide to obtain the high-thermal-conductivity low-dielectric-property fluorinated liquid.
Example 2
Perfluoro (4-methyl-2-pentene) and acetic acid are used as raw materials, concentrated sulfuric acid (98.3%) is used as a catalyst, and the initial temperature of the heating reaction is controlled at 90 ℃. Weighing 72g of acetic acid, putting the acetic acid into a reaction kettle which is connected with a condensation reflux device and can be electrically stirred, wherein the condensation reflux device is used for reducing the volatilization loss of reaction raw materials and ensuring that the pressure in the reaction kettle is normal pressure, raising the temperature of the reaction kettle and starting the electric stirring, adding 18.6g of catalyst concentrated sulfuric acid (98.3%) at one time when the temperature of the acetic acid reaches 90 ℃, dropwise adding 300g of perfluoro (4-methyl-2-pentene) into the reaction kettle by using a constant-pressure dropping funnel, controlling the dropwise adding time to be 1hr, maintaining the external heating temperature to be 90 ℃ after the dropwise adding is finished, and continuously stirring and reacting for 5 hr.
The amount of reactants is calculated by the molar ratio of the reactive functional groups, and the feeding molar ratio of the reactive functional groups is controlled as follows: carbon-carbon double bond: carboxy oxygen hydrogen bond = 1.2, acetic acid in excess to suppress side reactions and hydrolysis reactions of the product. The reaction process comprises the steps of taking organic carboxylic acid containing a strong acid catalyst as a reaction substrate, wherein the amount of the strong acid catalyst is 5% of the total mass of reaction raw materials, and carrying out esterification addition reaction in a heating condition in a manner of dropwise adding perfluoroolefin into the reaction substrate.
Washing the reacted mixed solution with alkalescent solution and pure water in sequence, separating liquid, drying and dehydrating to obtain a target product: adding sodium carbonate or sodium bicarbonate solution into the mixed solution after reaction, stirring and washing, then separating the solution, repeating the stirring and washing for 3 times, collecting the lower-layer product, adding pure water into the lower-layer product, stirring and washing, repeating the stirring and washing for 5 times, separating the solution again, collecting the lower-layer product, and drying the product by calcium oxide to obtain the high-thermal-conductivity low-dielectric-property fluorinated solution
Example 3
Perfluoro (4-methyl-2-pentene) and trifluoroacetic acid are used as raw materials, concentrated sulfuric acid (98.3%) is used as a catalyst, and the heating reaction initial temperature is controlled at 70 ℃. Weighing 136.8g of trifluoroacetic acid, putting the trifluoroacetic acid into a reaction kettle which is connected with a condensation reflux device and can be electrically stirred, wherein the condensation reflux device is used for reducing the volatilization loss of reaction raw materials and ensuring that the pressure in the reaction kettle is normal pressure, raising the temperature of the reaction kettle and starting the electric stirring, when the temperature of the trifluoroacetic acid reaches 70 ℃, adding 21.84g of catalyst concentrated sulfuric acid (98.3 percent) at one time, dropwise adding 300g of perfluoro (4-methyl-2-pentene) into the reaction kettle by using a constant-pressure dropping funnel, controlling the dropwise adding time to be 1hr, maintaining the external heating temperature to be 90 ℃ after the dropwise adding is finished, and continuously stirring and reacting for 5hrs.
The amount of reactants is calculated by the molar ratio of the reactive functional groups, and the feeding molar ratio of the reactive functional groups is controlled as follows: carbon-carbon double bond: carboxy oxygen hydrogen bond = 1.2, trifluoroacetic acid in excess to inhibit side reactions and hydrolysis of the product. The reaction process comprises the steps of taking organic carboxylic acid containing a strong acid catalyst as a reaction substrate, wherein the amount of the strong acid catalyst is 5 percent of the total mass of reaction raw materials, and carrying out esterification addition reaction in a heating condition in a manner of dropwise adding perfluoroolefin into the reaction substrate.
Washing the reacted mixed solution with alkalescent solution and pure water in sequence, separating liquid, drying and dehydrating to obtain a target product: adding sodium carbonate or sodium bicarbonate solution into the mixed solution after reaction, stirring and washing, then separating the solution, repeating the stirring and washing for 3 times, collecting the lower-layer product, adding pure water into the lower-layer product, stirring and washing, repeating the stirring and washing for 5 times, separating the solution again, collecting the lower-layer product, and drying the product by calcium oxide to obtain the high-thermal-conductivity low-dielectric-property fluorinated solution
Example 4
Perfluorobutyl ethylene and acetic acid are used as raw materials, phosphotungstic acid is used as a catalyst, and the heating reaction initial temperature is controlled at 100 ℃. Weighing 72g of acetic acid, putting the acetic acid into a reaction kettle which is connected with a condensation reflux device and can be electrically stirred, wherein the condensation reflux device is used for reducing the volatilization loss of reaction raw materials and ensuring that the pressure in the reaction kettle is normal pressure, raising the temperature of the reaction kettle and starting the electric stirring, adding 15.9g of catalyst phosphotungstic acid once when the temperature of the acetic acid reaches 100 ℃, dropwise adding 246g of perfluorobutyl ethylene into the reaction kettle by using a constant-pressure dropping funnel, controlling the dropwise adding time to be 1hr, maintaining the external heating temperature to be 100 ℃ after the dropwise adding is finished, and continuously stirring and reacting for 5 hr.
The amount of the reactants is measured by the molar ratio of the reactive functional groups, and the feeding molar ratio of the reactive functional groups is controlled as follows: carbon-carbon double bond: carboxy oxygen hydrogen bond = 1.2, acetic acid in excess to suppress side reactions and hydrolysis reactions of the product. The reaction process comprises the steps of taking organic carboxylic acid containing a strong acid catalyst as a reaction substrate, wherein the amount of the strong acid catalyst is 5% of the total mass of reaction raw materials, and carrying out esterification addition reaction in a heating condition in a manner of dropwise adding perfluoroolefin into the reaction substrate.
Washing the reacted mixed solution with alkalescent solution and pure water in sequence, separating liquid, drying and dehydrating to obtain a target product: adding sodium carbonate or sodium bicarbonate solution into the mixed solution after reaction, stirring and washing, then separating the solution, repeating the stirring and washing for 3 times, collecting the lower-layer product, adding pure water into the lower-layer product, stirring and washing, repeating the stirring and washing for 5 times, separating the solution again, collecting the lower-layer product, and drying the product by calcium oxide to obtain the high-thermal-conductivity low-dielectric-property fluorinated solution
Example 5
Perfluorohexylethylene and monofluoroacetic acid are used as raw materials, silicotungstic acid is used as a catalyst, and the heating reaction starting temperature is controlled at 150 ℃. Weighing 93.6g of monofluoroacetic acid, putting the monofluoroacetic acid into a reaction kettle which is connected with a condensation reflux device and can be electrically stirred, wherein the condensation reflux device is used for reducing the volatilization loss of reaction raw materials and ensuring that the pressure in the reaction kettle is normal pressure, raising the temperature of the reaction kettle and starting the electric stirring, 22.0g of catalyst silicotungstic acid is added at one time when the temperature of the monofluoroacetic acid reaches 150 ℃, 346g of perfluorohexylethylene is dropwise added into the reaction kettle by using a constant-pressure dropping funnel, the dropwise adding time is controlled to be 1hr, the external heating temperature is maintained at 150 ℃ after the dropwise adding is finished, and the reaction is continuously stirred for 5hrs.
The amount of the reactants is measured by the molar ratio of the reactive functional groups, and the feeding molar ratio of the reactive functional groups is controlled as follows: carbon-carbon double bond: carboxy oxy hydrogen bond = 1.2, with an excess of monofluoroacetic acid to inhibit side reactions and hydrolysis of the product. The reaction process comprises the steps of taking organic carboxylic acid containing a strong acid catalyst as a reaction substrate, wherein the amount of the strong acid catalyst is 5% of the total mass of reaction raw materials, and carrying out esterification addition reaction in a heating condition in a manner of dropwise adding perfluoroolefin into the reaction substrate.
Washing the reacted mixed solution with alkalescent solution and pure water in sequence, separating liquid, drying and dehydrating to obtain a target product: adding sodium carbonate or sodium bicarbonate solution into the mixed solution after reaction, stirring and washing, then separating the solution, repeating the stirring and washing for 3 times, collecting the lower-layer product, adding pure water into the lower-layer product, stirring and washing, repeating the stirring and washing for 5 times, separating the solution again, collecting the lower-layer product, and drying the product by calcium oxide to obtain the high-thermal-conductivity low-dielectric-property fluorinated solution.
Example 6
The dodecafluoro-1, 9-decadiene and propionic acid are used as raw materials, concentrated sulfuric acid is used as a catalyst, and the initial temperature of the heating reaction is 120 ℃. Weighing 88.8g of propionic acid, putting the propionic acid into a reaction kettle which is connected with a condensation reflux device and can be electrically stirred, wherein the condensation reflux device is used for reducing the volatilization loss of reaction raw materials and ensuring that the pressure in the reaction kettle is normal pressure, raising the temperature of the reaction kettle and starting the electric stirring, 22.2g of catalyst concentrated sulfuric acid (98.3%) is added at one time when the temperature of the propionic acid reaches 120 ℃, 354g of dodecafluoro-1, 9-decadiene is dropwise added into the reaction kettle by using a constant-pressure dropping funnel, the dropwise adding time is controlled to be 1hr, the external heating temperature is maintained at 120 ℃ after the dropwise adding is finished, and the propionic acid is continuously stirred and reacted for 5hrs.
The amount of reactants is calculated by the molar ratio of the reactive functional groups, and the feeding molar ratio of the reactive functional groups is controlled as follows: carbon-carbon double bond: carboxy oxygen hydrogen bond = 1.2, propionic acid in excess to suppress side reactions and hydrolysis of the product. The reaction process comprises the steps of taking organic carboxylic acid containing a strong acid catalyst as a reaction substrate, wherein the amount of the strong acid catalyst is 5 percent of the total mass of reaction raw materials, and carrying out esterification addition reaction in a heating condition in a manner of dropwise adding perfluoroolefin into the reaction substrate.
Washing the reacted mixed solution with alkalescent solution and pure water in sequence, separating liquid, drying and dehydrating to obtain a target product: adding sodium carbonate or sodium bicarbonate solution into the mixed solution after reaction, stirring and washing, then separating the solution, repeating the stirring and washing for 3 times, collecting the lower-layer product, adding pure water into the lower-layer product, stirring and washing, repeating the stirring and washing for 5 times, separating the solution again, collecting the lower-layer product, and drying the product by calcium oxide to obtain the high-thermal-conductivity low-dielectric-property fluorinated solution.
In the above embodiment, a preparation method of a high thermal conductivity low dielectric fluorinated liquid is to use a laser thermal conductivity meter to test the thermal conductivity of a post-treated product, and according to astm e1461 standard, from the thermal conductivity data obtained after the test, the product shows higher thermal conductivity (the thermal conductivity of a commercially available immersion fluorinated liquid is generally 0.04-0.07W/m · k), and the water content is tested by a water content tester and is less than 50ppm.
The thermal conductivity data are as follows:
| serial number | Thermal conductivity (W/(m.k)) | Water content (ppm) |
| Example 1 | 0.23 | 33 |
| Example 2 | 0.25 | 29 |
| Example 3 | 0.36 | 34 |
| Example 4 | 0.31 | 41 |
| Example 5 | 0.28 | 44 |
| Example 6 | 0.33 | 21 |
The previous description of the embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of high thermal conductivity fluorinated liquid comprises the addition esterification reaction of perfluoroolefin and organic carboxylic acid, and a fluorine-containing ester compound is generated after the reaction, wherein the compound is the high thermal conductivity fluorinated liquid, and is characterized in that the preparation method comprises the following steps: under the condition of a strong acid catalyst and heating conditions, carbon-carbon double bonds in perfluoroolefin and carboxyl oxygen-hydrogen bonds in perfluoroolefin undergo an addition esterification reaction, and the mixed solution after the reaction is washed by weak alkaline solution and pure water in sequence, and then is subjected to liquid separation, drying and dehydration to obtain the target product.
2. The method for preparing a highly thermally conductive fluorinated liquid according to claim 1, wherein said perfluoroolefin is: hexafluoropropylene dimer, perfluoro (4-methyl-2-pentene), perfluoro (2-methyl-2-pentene), perfluorocyclopentene, perfluorohex-1-ene, hexafluoropropylene trimer, perfluorobutyl ethylene, perfluorodecyl ethylene, hexafluoro-1, 3-butadiene, perfluorohexyl ethylene, dodecafluoro-1, 9-decadiene, 6H-perfluoro-1-hexene.
3. The method for preparing a highly thermal conductive fluorinated liquid according to claim 1, wherein the organic carboxylic acid is: formic acid, acetic acid, propionic acid, trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid, pentafluoropropionic acid, 2, 3-tetrafluoropropionic acid, 3-trifluoropropionic acid.
4. The method for preparing high thermal conductivity fluorinated liquid according to claim 1, wherein the strong acidic catalyst is: concentrated sulfuric acid, phosphotungstic acid, silicotungstic acid and phosphomolybdic acid.
5. The method for preparing high thermal conductivity fluorinated liquid according to claim 1, wherein the heating conditions are as follows: the initial temperature of the heating reaction is controlled between 70 ℃ and 150 ℃ according to the types of the selected raw materials.
6. The method for preparing high thermal conductivity fluorinated liquid according to claim 1, wherein the carbon-carbon double bond in perfluoroolefin and carboxyl oxygen-hydrogen bond undergo addition esterification: an organic carboxylic acid containing a strongly acidic catalyst is used as a reaction substrate, and a perfluoroolefin is added dropwise to the reaction substrate to carry out an esterification addition reaction under a heating condition.
7. The method for preparing the high thermal conductivity fluorinated solution according to claim 6, wherein the mixed solution after the reaction is washed by weak alkaline solution and pure water in sequence, and then subjected to liquid separation, drying and dehydration to obtain a target product: adding sodium carbonate or sodium bicarbonate solution into the mixed solution after reaction, stirring and washing, separating liquid, collecting the lower-layer product, adding pure water into the lower-layer product, stirring and washing, separating liquid again, and collecting the lower-layer product to obtain the high-thermal-conductivity low-dielectric-property fluorinated liquid.
8. The method for preparing the high-thermal-conductivity fluorinated liquid according to claim 7, wherein after the lower-layer product is dried and dehydrated by calcium oxide, the water content of the product is required to be less than 50ppm, and the high-thermal-conductivity fluorinated liquid can be obtained.
9. The method for preparing a highly thermal conductive fluorinated liquid according to any one of claims 1 to 8, wherein said highly thermal conductive fluorinated liquid is tested to satisfy thermal conductivity > 0.2W/(m.K) and water content < 50ppm.
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| US4478760A (en) * | 1980-04-18 | 1984-10-23 | Produits Chimiques Ugine Kuhlmann | Process for the preparation of fluorinated products |
| CN109535001A (en) * | 2018-11-20 | 2019-03-29 | 黎明化工研究设计院有限责任公司 | A method of preparing alpha-fluorocarboxylate ester |
| CN114671735A (en) * | 2022-03-17 | 2022-06-28 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of tetrafluorocyclobutane |
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| US4478760A (en) * | 1980-04-18 | 1984-10-23 | Produits Chimiques Ugine Kuhlmann | Process for the preparation of fluorinated products |
| CN109535001A (en) * | 2018-11-20 | 2019-03-29 | 黎明化工研究设计院有限责任公司 | A method of preparing alpha-fluorocarboxylate ester |
| CN114671735A (en) * | 2022-03-17 | 2022-06-28 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of tetrafluorocyclobutane |
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| SHOZO YANAGIDA等: "reactions of perfluoro-2-methyl-2-pentene with carboxylic acids, alcohols, and some cyclic amides. A new fluorinating reagent", 《BULL. CHEM. SOC. JPN.》, vol. 54, pages 1151 - 1158, XP055716064 * |
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