Method for separating perfluorotripropylamine, heat transfer fluid, heat transfer device, and heat transfer method

Abstract

The present disclosure provides a method for separating perfluorotripropylamine from a mixture B comprising: a mixture A containing at least one substance selected from the group consisting of hexafluoropropene trimers represented by C9F18, perfluoroalkene ethers, and perfluoropolyethers; and perfluorotripropylamine. The solidification point of the mixture A is at or below the solidification point of perfluorotripropylamine, and the step for separating perfluorotripropylamine from the mixture A is performed at a temperature equal to or lower than the solidification point of perfluorotripropylamine.

Description

Method for separating perfluorotripropylamine, heat transfer fluid, heat transfer device, and heat transfer method

[0001] The present disclosure relates to a method for separating perfluorotripropylamine, a heat transfer fluid, an apparatus for heat transfer, and a method for heat transfer.

[0002] It is known to use perfluorotripropylamine as a heat transfer fluid (Patent Document 1).

[0003] Special table 2016-505882 publication

[0004] Instead of perfluorotripropylamine, hexafluoropropene (HFP) trimer, perfluoroalkene ether, or perfluoropolyether may be used as the heat transfer fluid.

[0005] In a device using perfluorotripropylamine as a heat transfer fluid, when replacing perfluorotripropylamine with another heat transfer fluid (e.g., hexafluoropropene trimer), it is possible to consider passing the other heat transfer fluid through the device. In this case, a mixture of perfluorotripropylamine and the other heat transfer fluid is obtained. If perfluorotripropylamine can be separated from this mixture, the heat transfer fluid used for the replacement can be reused.

[0006] The object of the present invention is to ９ F １８ The object of the present invention is to provide a separation method capable of efficiently separating perfluorotripropylamine from a mixture containing perfluorotripropylamine and at least one selected from the group consisting of hexafluoropropene trimer represented by the formula (I), perfluoroalkene ether, and perfluoropolyether.

[0007] The present disclosure includes the following aspects: [1] C ９ F １８

[0013] A method for separating perfluorotripropylamine from a mixture A containing at least one selected from the group consisting of a hexafluoropropene trimer represented by the formula (I), a perfluoroalkene ether, and a perfluoropolyether, and a mixture B containing perfluorotripropylamine, wherein the freezing point of the mixture A is a temperature not higher than the freezing point of perfluorotripropylamine, and the step of separating perfluorotripropylamine from the mixture B is carried out at a temperature not higher than the freezing point of perfluorotripropylamine. [2] The method for separating perfluorotripropylamine according to the above item [1], wherein the difference in freezing point between the mixture A and perfluorotripropylamine is 20°C or more. [3] The method for separating perfluorotripropylamine according to the above item [1] or [2], wherein the content of perfluorotripropylamine contained in the mixture C after separation of perfluorotripropylamine is 1000 mass ppm or less. [4] ９ F １８ The hexafluoropropene trimer represented by the following formulas (I) to (III): [5] The method for separating perfluorotripropylamine according to any one of the above [1] to [3], wherein the perfluoroalkene ether contains at least one hexafluoropropene trimer represented by the following formula: CF ３ (CF ２ ) ｘ CF=CFCF(OR １ ) (CF ２ ) ｙ CF ３ , C.F. ３ (CF ２ ) ｘ C (OR １ ) = CFCF ２ (CF ２ ) ｙ CF ３ , C.F. ３ CF=CFCF(OR １ ) (CF ２ ) ｘ (CF ２ ) ｙ CF ３ , and CF ３ (CF２ ) ｘ CF = C(OR １ )CF ２ (CF ２ ) ｙ CF ３ , [wherein; R １ are each independently a methyl group or an ethyl group, x and y are each independently 0, 1, 2, or 3, and x + y is 1, 2, or 3.]. [6] The perfluoropolyether is a compound represented by the following formula: R ２ O-Rf-R ２’ wherein R and R′ are each independently —C ｍ F ２ｍ＋１ m is an integer from 1 to 8, and Rf is a divalent fluoropolyoxyalkylene group containing 2 to 20 repeating units, said repeating units being: (i) -CFXO-, where X is F or CF ３ (ii) -CF ２ CFXO- (wherein X is F or CF ３ (iii) -CFXCF ２ O— (wherein X is F or CF ３ (iv) -CF ２ CF ２ CF ２ O-, and (v) -CF ２ CF ２ CF ２ CF ２ O-, or Rf is represented by (vi) -(CF ２ ) ｋ -CFZ-O- (wherein k is an integer of 0 to 3, and Z is -ORFT) ３ where RF is -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O- and -CF ２ CF ２ CF ２ CF ２and a fluoropolyoxyalkylene group containing 0 to 20 repeating units selected from the group consisting of: O—, where each X is independently F or CF ３ and T ３ is C １－５ The method for separating perfluorotripropylamine according to any one of the above items [1] to [5], comprising at least one compound represented by the formula: [7] C ９ F １８ [8] A heat transfer fluid comprising perfluorotripropylamine and at least one selected from the group consisting of a hexafluoropropene trimer represented by the formula (I), a perfluoroalkene ether, and a perfluoropolyether, wherein the content of perfluorotripropylamine is 1000 mass ppm or less. ９ F １８ The hexafluoropropene trimer represented by the following formulas (I) to (III): [9] The heat transfer fluid according to the above [7], which contains at least one hexafluoropropene trimer represented by the following formula:

[10] The heat transfer fluid according to the above [8], wherein the compound represented by formula (I) is 85 mass % or more based on the total amount of the hexafluoropropene trimer.

[11] The perfluoroalkene ether is a compound represented by the following formula: CF ３ (CF ２ ) ｘ CF=CFCF(OR １ ) (CF ２ ) ｙ CF ３ , C.F. ３ (CF ２ ) ｘ C (OR １ ) = CFCF ２ (CF ２ ) ｙ CF ３ , C.F. ３ CF=CFCF(OR １ ) (CF ２ ) ｘ (CF ２ ) ｙ CF ３ , and CF ３ (CF ２ )ｘ CF = C(OR １ )CF ２ (CF ２ ) ｙ CF ３ , [wherein; R １ are each independently a methyl group or an ethyl group, x and y are each independently 0, 1, 2, or 3, and x + y is 1, 2, or 3.

[11] The perfluoropolyether is a compound represented by the following formula: R ２ O-Rf-R ２’ wherein R and R′ are each independently —C ｍ F ２ｍ＋１ m is an integer from 1 to 8, and Rf is a fluoropolyoxyalkylene chain comprising repeating units, the repeating units being: (i) -CFXO-, where X is F or CF ３ (ii) -CF ２ CFXO- (wherein X is F or CF ３ (iii) -CFXCF ２ O— (wherein X is F or CF ３ (iv) -CF ２ CF ２ CF ２ O-(v)-CF ２ CF ２ CF ２ CF ２ O- (vi) -(CF ２ ) ｋ -CFZ-O- (wherein k is an integer of 0 to 3, and Z is -ORFT) ３ where RF is -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O- and -CF ２ CF ２ CF ２ CF ２ Fluoropolyoxyalkylene chains containing a number of repeating units from 0 to 10 selected from the group consisting of: O—, where each X is independently F or CF ３and T ３ is C １－５

[12] The heat transfer fluid according to any one of the above [7] to

[11] , further comprising a stabilizer.

[13] The heat transfer fluid according to any one of the above [7] to

[12] , used in a semiconductor manufacturing process.

[14] Use of the heat transfer fluid according to any one of the above [7] to

[13] for heat transfer.

[15] A heat transfer apparatus comprising: a device; and a mechanism for transferring heat to or from the device, the mechanism comprising the heat transfer fluid according to any one of the above [7] to

[13] .

[16] The heat transfer apparatus according to the above

[15] , wherein the device is a wafer used for manufacturing semiconductors.

[17] A semiconductor manufacturing apparatus comprising the heat transfer apparatus according to the above

[15] or

[16] .

[18] A heat transfer method comprising the steps of: preparing a device; and transferring heat to or from the device using the heat transfer fluid according to any one of [7] to

[13] above.

[19] The heat transfer method according to

[18] above, wherein the device is a wafer used for manufacturing semiconductors.

[0008] According to the present disclosure, C ９ F １８ The present invention provides a separation method capable of efficiently separating perfluorotripropylamine from a mixture containing perfluorotripropylamine and at least one selected from the group consisting of hexafluoropropene trimer represented by the formula (I), perfluoroalkene ether, and perfluoropolyether.

[0009] In this specification, regardless of whether "each independently" or similar expressions are explicitly stated, unless otherwise stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently at each occurrence.

[0010] In this specification, the numerical range "A to B" is intended to include the lower and upper limit numerical values ​​themselves. In other words, the numerical range "A to B" means A or more and B or less.

[0011] The heat transfer fluid of the present disclosure will now be described.

[0012] (Method for separating perfluorotripropylamine) The method for separating perfluorotripropylamine of the present disclosure is ９ F １８ and a mixture B containing perfluorotripropylamine, wherein the freezing point of mixture A is a temperature not higher than the freezing point of perfluorotripropylamine, and the step of separating perfluorotripropylamine from mixture B is carried out at a temperature not higher than the freezing point of perfluorotripropylamine. The mixture obtained as a result of treatment by the perfluorotripropylamine separation method of the present disclosure is also referred to as mixture C.

[0013] Mixture A is C ９ F １８ The compound contains at least one selected from the group consisting of hexafluoropropene trimer represented by the formula (I), perfluoroalkene ether, and perfluoropolyether.

[0014] Mixture B is a mixture containing mixture A and perfluorotripropylamine, and typically consists of mixture A and perfluorotripropylamine. In other words, mixture A can be said to be mixture B excluding perfluorotripropylamine.

[0015] Mixture C is a mixture obtained as a result of treatment by the perfluorotripropylamine separation method of the present disclosure, and is a mixture from mixture B in which some or all of the perfluorotripropylamine has been removed.

[0016] Mixture A, Mixture B, and Mixture C may typically have the same composition except for the content of perfluorotripropylamine. However, this does not exclude that the contents of compounds other than perfluorotripropylamine may differ. For example, the contents (by mass) of each compound other than perfluorotripropylamine may differ within a range of 10% or less, 5% or less, 3% or less, or 1% or less relative to the total mixture.

[0017] Mixture A, Mixture B, and Mixture C can be used as heat transfer fluids.

[0018] C ９ F １８ The hexafluoropropene trimer represented by the formula (I) is not particularly limited, and examples thereof include C ９ F １８ The compound may have any structure represented by the following formula:

[0019] The hexafluoropropene trimer is preferably represented by the following formulas (I) to (III): The hexafluoropropene trimer contains at least one hexafluoropropene trimer represented by the formula:

[0020] In this specification, unless otherwise specified, the compound represented by the above formula (I) includes both E and Z diastereomers.

[0021] The hexafluoropropene trimer may contain only one of the compounds represented by formulas (I) to (III), or may be a mixture containing two or three of these compounds.

[0022] The compound represented by formula (I) may be contained in an amount of 99% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably less than 85% by mass, for example, 80% by mass or less, 70% by mass or less, 65% by mass or less, or 60% by mass or less, based on the total amount of the compounds represented by formulas (I) to (III). By reducing the content of the compound represented by formula (I), the boiling point of mixture A increases. In other words, the vapor pressure of mixture A decreases.

[0023] The compound represented by formula (I) may be contained in an amount of preferably 1% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, still more preferably 45% by mass or more, particularly preferably 50% by mass or more, for example 60% by mass or more, 65% by mass or more, 75% by mass or more, or 85% by mass or more, based on the total amount of the compounds represented by formulas (I) to (III). Increasing the content of the compound represented by formula (I) reduces the viscosity.

[0024] The compound represented by formula (I) may be, for example, 1% by mass or more and 99% by mass or less, 10% by mass or more and 90% by mass or less, 30% by mass or more and 90% by mass or less, 10% by mass or more and 85% by mass or less, 35% by mass or more and 85% by mass or less, 10% by mass or more and less than 85% by mass, 20% by mass or more and less than 85% by mass, 30% by mass or more and less than 85% by mass, 40% by mass or more and less than 85% by mass, 5 ... It may be 0% by mass or less, 55% by mass or more and 80% by mass or less, 60% by mass or more and 75% by mass or less, 65% by mass or more and 70% by mass or less, 35% by mass or more and 60% by mass or less, or 50% by mass or more and 60% by mass or less, preferably 30% by mass or more and 90% by mass or less, preferably 40% by mass or more and less than 85% by mass, more preferably 40% by mass or more and 80% by mass or less, even more preferably 45% by mass or more and 70% by mass or less, and even more preferably 50% by mass or more and 60% by mass or less.

[0025] The mass ratio of the compound represented by formula (II) to the compound represented by formula (III) is not particularly limited, and may be, for example, 1:9 to 9:1, 2:8 to 8:2, 3:7 to 7:3, 4:6 to 6:4, or 4.5:5.5 to 5.5:4.5.

[0026] The perfluoroalkene ether preferably has the following formula: CF ３ (CF ２ ) ｘ CF=CFCF(OR １ ) (CF ２ ) ｙ CF ３ , C.F. ３ (CF ２ ) ｘ C (OR１ ) = CFCF ２ (CF ２ ) ｙ CF ３ , C.F. ３ CF=CFCF(OR １ ) (CF ２ ) ｘ (CF ２ ) ｙ CF ３ , and CF ３ (CF ２ ) ｘ CF = C(OR １ )CF ２ (CF ２ ) ｙ CF ３ , [wherein; R １ are each independently a methyl group or an ethyl group, x and y are each independently 0, 1, 2, or 3, and x+y is 1, 2, or 3.

[0027] Examples of the perfluoroalkene ether include 5-methoxyperfluoro-3-heptene, 3-methoxyperfluoro-3-heptene, 4-methoxyperfluoro-2-heptene, 3-methoxyperfluoro-2-heptene, 4-methoxyperfluoro-2-pentene, 2-methoxyperfluoro-2-pentene, 3-methoxyperfluoro-2-pentene, 2-methoxyperfluoro-3-pentene, cis- and trans-2-methoxyperfluoro-2-octene, and 2-methoxyperfluoro-3-octene.

[0028] The perfluoroalkene ether is preferably methylperfluoroheptene ether. The methylperfluoroheptene ether may comprise a mixture of two or more structural and / or stereoisomers. For example, the methylperfluoroheptene ether may comprise a mixture of about 48 to about 52 weight percent 5-methoxyperfluoro-3-heptene, about 18 to about 22 weight percent 3-methoxyperfluoro-3-heptene, about 18 to about 22 weight percent 4-methoxyperfluoro-2-heptene, and about 6 to about 10 weight percent 4-methoxyperfluoro-3-heptene.

[0029] The perfluoroalkene ether is specifically methyl-perfluoroheptene ether (MPHE) (C ７ F １３ OCH ３ ) Specifically, a product name "Opteon SF10" (manufactured by Chemours) can be mentioned.

[0030] The perfluoropolyether has the following formula: ２ O-Rf-R ２’ wherein R and R′ are each independently —C ｍ F ２ｍ＋１ m is an integer from 1 to 8, and Rf is a divalent fluoropolyoxyalkylene group containing 2 to 20 repeating units, said repeating units being: (i) -CFXO-, where X is F or CF ３ (ii) -CF ２ CFXO- (wherein X is F or CF ３ (iii) -CFXCF ２ O— (wherein X is F or CF ３ (iv) -CF ２ CF ２ CF ２ O-, and (v) -CF ２ CF ２ CF ２ CF ２ O-, or Rf is represented by (vi) -(CF ２ ) ｋ-CFZ-O- (wherein k is an integer of 0 to 3, and Z is -ORFT) ３ where RF is -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O- and -CF ２ CF ２ CF ２ CF ２ and a fluoropolyoxyalkylene group containing 0 to 20 repeating units selected from the group consisting of: O—, where each X is independently F or CF ３ and T ３ is C １－５ is a divalent group represented by the formula:

[0031] m is an integer of 1 to 8, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

[0032] Rf may preferably be any of the following groups (1) to (3): (1) -(CF ２ O) ａ -(CF ２ CF ２ O) ｂ -(CF ２ -(CF ２ ) ｚ’ -CF ２ O) ｃ [wherein a, b, and c are each independently an integer of 100 or less, preferably 50 or less, z' is 1 or 2, a≧0, b≧0, c≧0, a+b>0, preferably each of a and b>0, and b / a is in the range of 0.1 to 10.]; (2)-(C ３ F ６ O) ｃ’ -(C ２ F ４ O) ｂ -(CFXO) ｔ wherein each X is independently —F or —CF ３and b, c', and t are each independently an integer of 100 or less, and c'>0, b≧0, and t≧0, preferably b and t>0, c' / b being in the range of 0.2 to 5.0, and (c'+b) / t being in the range of 5 to 50.] (3)-(C ３ F ６ O) ｃ’ -(CFXO) ｔ wherein each X is independently —F or —CF ３ wherein c' and t are each independently an integer of 100 or less, c'>0, t≧0, preferably t>0, and c' / t is in the range of 5 to 50.

[0033] The perfluoropolyether is not particularly limited, but examples thereof include those available from Solvay Solexis S.p.A. under the trade names GALDEN (registered trademark) HT110 and GALDEN (registered trademark) HT135.

[0034] The kinematic viscosity of mixture A at −75° C. may be preferably 100 cSt or less, more preferably 80 cSt or less, and even more preferably 60 cSt or less. By having a kinematic viscosity within the above range, i.e., a lower kinematic viscosity, mixture A has improved filterability. Therefore, when performing microfiltration using a filter with a small pore size, it is possible to shorten the process time and reduce energy loss. Furthermore, higher precision filtration is possible.

[0035] The kinematic viscosity and density of the heat transfer fluid composition or heat transfer fluid of the present disclosure are values ​​measured using a kinematic viscometer SVM3001 manufactured by Anton Paar.

[0036] The boiling point of mixture A may be preferably 90° C. or higher, more preferably 95° C. or higher, and even more preferably 100° C. or higher. When the boiling point of mixture A is high, loss due to evaporation can be reduced.

[0037] The boiling point of mixture A is the temperature at which a peak resulting from endothermic heat is observed when the temperature is increased from 25° C. at a rate of 5° C. / min using a differential scanning calorimeter (DSC).

[0038] The freezing point of mixture A may be preferably −70° C. or lower, more preferably −75° C. or lower, even more preferably −80° C. or lower, and even more preferably −85° C. or lower. The lower the freezing point of mixture A, the greater the difference in the freezing points of perfluorotripropylamine, making separation easier.

[0039] The freezing point of Mixture A can be determined by differential scanning calorimetry (DSC).

[0040] The freezing point of perfluorotripropylamine is about -65°C.

[0041] The freezing point difference between mixture A and perfluorotripropylamine may be preferably 5° C. or more, more preferably 10° C. or more, even more preferably 15° C. or more, and still more preferably 20° C. or more, for example, 30° C. or more, 35° C. or more, or 40° C. or more. By setting the freezing point difference between mixture A and perfluorotripropylamine within the above range, separation of perfluorotripropylamine becomes easy.

[0042] The upper limit of the freezing point difference between mixture A and perfluorotripropylamine is not particularly limited, but may be, for example, 100°C or less, 80°C or less, 60°C or less, 50°C or less, 40°C or less, or 30°C or less.

[0043] The step of separating perfluorotripropylamine from mixture B is carried out at a temperature below the freezing point of perfluorotripropylamine.

[0044] The step of separating perfluorotripropylamine from mixture B is carried out at a temperature that is preferably 5°C or more lower, more preferably 10°C or more lower, and even more preferably 15°C or more lower, for example, 20°C or more lower, or 30°C or more lower than the freezing point of perfluorotripropylamine.

[0045] The step of separating perfluorotripropylamine from mixture B is preferably carried out at a temperature not higher than the freezing point of perfluorotripropylamine and not lower than the freezing point of mixture A.

[0046] The step of separating perfluorotripropylamine from mixture B is carried out at a temperature that is preferably at least 1°C higher, more preferably at least 5°C higher, for example at least 10°C higher, or at least 15°C higher than the freezing point of mixture A.

[0047] The step of separating perfluorotripropylamine from mixture B is preferably carried out at a temperature closer to the freezing point of mixture A than to the freezing point of perfluorotripropylamine.

[0048] The step of separating perfluorotripropylamine from mixture B is not particularly limited, and may be extraction, concentration, freeze-drying, precipitation, adsorption, distillation, rectification, or chromatography. The step of separating perfluorotripropylamine from mixture A is preferably freeze-drying, recrystallization, adsorption, distillation, rectification, or chromatography, and particularly preferably adsorption.

[0049] The above methods may be used alone or in combination of two or more. For example, separation may be performed as a pretreatment by a certain method, and then separation may be performed as a main treatment.

[0050] When the step of separating perfluorotripropylamine from mixture B is performed by adsorption, the adsorbent may be a molecular sieve, activated carbon, silica gel, zeolite, coordination polymer, porous polymer, metal organic framework, porous silica, or the like, with a molecular sieve being preferred. A specific example of the molecular sieve is molecular sieve 13X.

[0051] The content of perfluorotripropylamine in mixture C is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, even more preferably 200 mass ppm or less, still more preferably 100 mass ppm or less, particularly preferably 50 mass ppm or less, 10 mass ppm or less, 5 mass ppm or less, or 1 mass ppm or less. Mixture C may be substantially free of perfluorotripropylamine. "May be substantially free of perfluorotripropylamine" means that the content of perfluorotripropylamine is below the detection limit.

[0052] The content of perfluorotripropylamine in the mixture can be analyzed by gas chromatography.

[0053] The mixture C is preferably C ９ F １８ The hexafluoropropene trimer is represented by the formula:

[0054] Mixture C is preferably a heat transfer fluid. ９ F １８ and perfluorotripropylamine, and at least one selected from the group consisting of hexafluoropropene trimer represented by the formula (I), perfluoroalkene ether, and perfluoropolyether, wherein the content of perfluorotripropylamine is 1,000 ppm by mass or less.

[0055] The heat transfer fluids of the present disclosure may include hexafluoropropene dimer and / or hexafluoropropene tetramer.

[0056] Hexafluoropropene dimers include (E)-1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene, (Z)-1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene, or 1,1,3,4,4,5,5-nonafluoro-2-(trifluoromethyl)-2-pentene.

[0057] Hexafluoropropene tetramers include 1,1,1,2,5,6,6,6-octafluoro-2,3,5-tris(trifluoromethyl)-4-(perfluoropropyl-2-yl)-3-hexene.

[0058] The heat transfer fluid of the present disclosure comprises, in addition to hexafluoropropene trimer, C ｍ F ２ｍ and / or C ｎ F （２ｎ－２） [wherein m is an integer of 4 or more and 12 or less except 9, and n is an integer of 4 or more and 12 or less].

[0059] m is an integer of 4 or greater, preferably an integer of 5 or greater, and more preferably an integer of 6 or greater. Furthermore, n is an integer of 12 or less, preferably an integer of 11 or less, and more preferably an integer of 10 or less, provided that m does not include 9.

[0060] n is an integer of 4 or greater, preferably an integer of 5 or greater, and more preferably an integer of 6 or greater. Furthermore, n is an integer of 12 or less, preferably an integer of 11 or less, and more preferably an integer of 10 or less. Furthermore, n is particularly preferably 9.

[0061] C ｍ F ２ｍ may be a chain compound or a cyclic compound which may have a substituted structure. The chain compound may be a so-called alkene, and may be linear or branched.

[0062] C ｎ F （２ｎ－２） may be a chain compound or a cyclic compound which may have a substituted structure. The chain compound may be a diene or an alkyne, and may be linear or branched.

[0063] In the heat transfer fluid of the present disclosure, C ｍ F ２ｍ and / or C ｎ F （２ｎ－２） The coexistence of C with hexafluoropropene trimer improves the function as a heat transfer fluid. ｍ F ２ｍ and / or C ｎ F （２ｎ－２） By including the compound (I), the stability of the hexafluoropropene trimer is improved.

[0064] C ｍ F ２ｍ and / or C ｎ F （２ｎ－２） The content of C in the heat transfer fluid of the present disclosure may be preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. ｍ F ２ｍ and / or C ｎ F（２ｎ－２） The content of C in the heat transfer fluid of the present disclosure may be preferably 0.0001% by mass or more, more preferably 0.001% by mass or more. ｍ F ２ｍ and / or C ｎ F （２ｎ－２） is not an essential component in the heat transfer fluid of the present disclosure and may not be included.

[0065] The heat transfer fluids of the present disclosure may also contain other components.

[0066] The heat transfer fluid of the present disclosure may contain any other components that do not impair the effects and purposes of the present disclosure, such as water or a stabilizer.

[0067] The stabilizer functions as a so-called acid acceptor or antioxidant by exhibiting a stabilizing effect, which mainly includes an effect of preventing decomposition of the hexafluoropropene trimer by capturing radicals generated in the system, and an acid-accepting effect of preventing further decomposition of the hexafluoropropene trimer by the acid by capturing the acid generated in the system.

[0068] As the stabilizer, a wide variety of known stabilizers can be used, but among them, it is preferable to use one or more stabilizers selected from the group consisting of unsaturated alcohol-based stabilizers, nitro-based stabilizers, amine-based stabilizers, phenol-based stabilizers, and epoxy-based stabilizers, because they can effectively suppress the occurrence of metal corrosion due to the composition.

[0069] A wide variety of known unsaturated alcohol stabilizers can be used, including, for example, one or more selected from the group consisting of 3-buten-2-ol, 2-buten-1-ol, 4-propen-1-ol, 1-propen-3-ol, 2-methyl-3-buten-2-ol, 3-methyl-3-buten-2-ol, 3-methyl-2-buten-1-ol, 2-hexen-1-ol, 2,4-hexadien-1-ol, and oleyl alcohol.

[0070] A wide variety of known nitro stabilizers can be used. Examples of aliphatic nitro compounds include nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. Examples of aromatic nitro compounds that can be used include one or more selected from the group consisting of nitrobenzene, o-, m-, or p-dinitrobenzene, o-, m-, or p-nitrotoluene, dimethylnitrobenzene, m-nitroacetophenone, o-, m-, or p-nitrophenol, o-nitroanisole, m-nitroanisole, and p-nitroanisole.

[0071] A wide variety of known amine stabilizers can be used as the amine stabilizer. For example, one or more selected from the group consisting of pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, α-methylbenzylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, tripropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, dipentylamine, tribenzylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, and diethylhydroxylamine can be used.

[0072] A wide variety of known phenolic stabilizers can be used, including, for example, one or more selected from the group consisting of 2,6-ditertiarybutyl-4-methylphenol, 3-cresol, phenol, 1,2-benzenediol, 2-isopropyl-5-methylphenol, and 2-methoxyphenol.

[0073] A wide variety of known epoxy stabilizers can be used, including, for example, one or more selected from the group consisting of butylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, butyl glycidyl ether, diethylene glycol diglycidyl ether, and 1,2-epoxy-3-phenoxypropane.

[0074] The combination of stabilizers having different stabilizing effects more effectively prevents decomposition of the hexafluoropropene trimer, which may occur for various reasons. For this reason, the stabilizer is preferably one or more selected from the group consisting of the above-mentioned epoxy-based stabilizer, as well as unsaturated alcohol-based stabilizers, nitro-based stabilizers, and phenol-based stabilizers.

[0075] From the viewpoint of effectively suppressing acid liberation from the hexafluoropropene trimer and suppressing metal corrosion by the liquid composition, the content of the stabilizer in the entire heat transfer fluid is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more. On the other hand, in consideration of avoiding undesirable changes in the physical properties of the heat transfer fluid due to excessive addition of the stabilizer, the content of the stabilizer in the entire heat transfer fluid is preferably 10% by mass or less, more preferably 5% by mass or less.

[0076] (Use of Heat Transfer Fluid) The heat transfer fluid of the present disclosure is used to remove heat from or supply heat to various heat transfer targets. Heat transfer targets in the present disclosure include articles, devices, and atmospheres that are cooled, heated, or maintained at a controlled temperature. Examples of such heat transfer targets include electrical components, mechanical components, and optical components, as well as processed products and assemblies thereof. Specific examples of heat transfer targets in the present disclosure include, but are not limited to, wafers used in manufacturing semiconductor devices, microprocessors, power control semiconductors, electrical branch switches, power transformers, circuit boards, multi-chip modules, mounted and unmounted semiconductor devices, chemical reactors, nuclear reactors, fuel cells, lasers, and missile components.

[0077] The heat transfer fluid of the present disclosure has low pressure loss during circulation during use, making it suitable for use in applications requiring large amounts of heat transfer. In a preferred embodiment, the heat transfer fluid of the present disclosure is used in a semiconductor manufacturing process. The object to be heat transferred in the semiconductor manufacturing process is a wafer used to manufacture a semiconductor device.

[0078] Apparatus for Heat Transfer The present disclosure further provides an apparatus for heat transfer comprising a device and a mechanism for transferring heat to or from the device, the mechanism comprising a heat transfer fluid as described above.

[0079] Examples of devices include wafers used to manufacture semiconductors, semiconductor elements, computers, server computers, servers including blade servers; disk arrays / storage systems; storage area networks; network-attached storage; storage communication systems; workstations; routers; telecommunications infrastructure / switches; wired, optical, and wireless communication devices; cell processing devices; printers; power supplies; displays; optical devices; measurement systems including handheld systems; military electronics; and the like, preferably wafers used to manufacture semiconductors.

[0080] A semiconductor element is a heat-generating element mounted on a device, such as a CPU, a GPU, or an SSD. The semiconductor element is made of, for example, a single element such as silicon or germanium, or a compound semiconductor such as gallium arsenide (GaAs), gallium phosphide (GaP), indium phosphide (InP), gallium nitride (GaN), or silicon carbide (SiC).

[0081] When the device is a server computer, one or more logic boards are disposed within the interior space. The logic boards include a number of heat-generating electronic components, including at least one processor, such as a CPU, a GPU, etc. In addition, other heat-generating computer components may be used, such as a chipset; memory, graphics chips, network chips, RAM, power supplies, daughter cards; and storage drives, such as solid-state drives and mechanical hard disks.

[0082] The heat transfer device is a heat transfer device for transferring heat between the heat transfer object and the heat transfer target object using the heat transfer fluid, and transfers heat by thermal contact with the heat transfer target object. For example, when removing heat from the heat transfer target object, it is called cooling, and when supplying heat, it is called heating. Different mechanisms may be used depending on the case, but one heat transfer device may perform both cooling and heating.

[0083] Examples of heat transfer devices include, but are not limited to, pumps, valves, fluid containment systems, pressure control systems, coolers, heat exchangers, heat sources, heat sinks, refrigeration systems, active temperature control systems, and passive temperature control systems.

[0084] More specifically, the heat transfer apparatus includes a temperature-controlled wafer chuck in a plasma-enhanced chemical vapor deposition (PECVD) tool, a temperature-controlled test head for die performance testing, a temperature-controlled work area in semiconductor processing equipment, a thermal shock test bath liquid reservoir, a thermostatic chamber, and the like, preferably a temperature-controlled work area in semiconductor processing equipment.

[0085] The object to which heat is transferred, which is brought into thermal contact with the heat transfer device, is the same as described above.

[0086] The present disclosure also provides a semiconductor manufacturing apparatus including the heat transfer apparatus of the present disclosure.

[0087] Heat Transfer Methods The present disclosure discloses heat transfer methods that include providing a device and transferring heat to or from the device using a heat transfer fluid as described above. Here, heat can be transferred by placing a heat transfer apparatus in thermal contact with the device. When placed in thermal contact with the device, the heat transfer apparatus removes heat from the device, supplies heat to the device, or maintains the device at a selected temperature or temperature range. The direction of heat flow (from or to the device) is determined by the relative temperature difference between the device and the heat transfer apparatus.

[0088] Although the present invention has been described above, the present invention is not limited to the above and can be embodied in various forms without departing from the gist of the present invention.

[0089] The present disclosure will be described below with reference to examples, but the present disclosure is not limited to the following examples.

[0090] The content of perfluorotripropylamine in the composition was measured by gas chromatography analysis.

[0091] The boiling point and freezing point of the composition were measured using a differential scanning calorimeter (DSC). Specifically, the boiling point was the temperature at which an endothermic peak was observed when the composition was heated from 25°C at 5°C / min. The freezing point was the temperature at which an endothermic peak was observed when the composition was cooled with liquid nitrogen to -150°C or below (the temperature at which the composition was confirmed to become solid) and then heated at 5°C / min.

[0092] Synthesis Example of Heat Transfer Fluid a (Mixture A) 750 g of DMF and 7.2 g of cesium fluoride were placed in an SUS autoclave and sealed. After evacuating the autoclave, 2268 g of hexafluoropropylene was added over 4.5 hours while maintaining the temperature inside the autoclave at 70 to 110°C. The lower layer was separated from the resulting reaction solution and washed with ultrapure water to obtain 2219 g of heat transfer fluid composition a (Mixture A) containing HFP trimer. GC-FID and GC-MS analyses were performed, and it was confirmed by area percentage analysis that the HFP trimer was contained in 87% by mass of the total composition (100% by mass), and that the compounds represented by formulas (I), (II), and (III) described herein were contained in 78%, 9%, and 13% by mass, respectively, of the total HFP trimer (100% by mass).

[0093] Production Example 1 990 g of heat transfer fluid a (mixture A) and 10 g of FC-3283 (perfluorotripropylamine) manufactured by 3M Company were mixed to obtain raw material composition 1 (mixture B).

[0094] Production Example 2 990 g of Opteon SF10 (methyl perfluoroheptene ether) (mixture A) manufactured by Chemours and 10 g of FC-3283 (perfluorotripropylamine) manufactured by 3M were mixed to obtain raw material composition 2 (mixture B).

[0095] Production Example 3 990 g of Galden HT110 (perfluoropolyether, boiling point 110°C, freezing point -100°C) (mixture A) manufactured by Solvay and 10 g of FC-3283 (perfluorotripropylamine) manufactured by 3M were mixed to obtain raw material composition 3 (mixture B).

[0096] Production Example 4 990 g of Galden HT135 (perfluoropolyether, boiling point 110°C, freezing point -100°C) (mixture A) manufactured by Solvay and 10 g of FC-3283 (perfluorotripropylamine) manufactured by 3M were mixed to obtain raw material composition 4 (mixture B).

[0097] Example 1 1000 g of raw material composition 1 and 50 g of unused molecular sieve 13X (MS13X) were placed in a pre-dried flask. The mixture was treated for 20 hours with occasional stirring while controlling the liquid temperature in the flask to -75°C. After 20 hours, the mixture was filtered to obtain the treated composition of Example 1 (mixture C). A portion of the obtained composition of Example 1 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 1 was calculated to be 483 ppm.

[0098] Example 2: 1,000 g of raw material composition 1 and 100 g of unused molecular sieve 13X were placed in a pre-dried flask. The mixture was treated for 20 hours with occasional stirring while controlling the liquid temperature in the flask to -75°C. After 20 hours, the mixture was filtered to obtain a treated composition of Example 2 (mixture C). A portion of the obtained composition of Example 2 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 2 was calculated to be 234 ppm.

[0099] Example 3: 1,000 g of raw material composition 1 and 400 g of unused molecular sieve 13X were placed in a pre-dried flask. The mixture was treated for 20 hours with occasional stirring while controlling the liquid temperature in the flask to -75°C. After 20 hours, the mixture was filtered to obtain a post-treatment composition of Example 3 (mixture C). A portion of the obtained composition of Example 3 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 3 was calculated to be 1 ppm.

[0100] Example 4 1,000 g of raw material composition 2 and 400 g of unused molecular sieve 13X were placed in a pre-dried flask. The mixture was treated for 20 hours with occasional stirring while controlling the liquid temperature in the flask to -75°C. After 20 hours, the mixture was filtered to obtain a post-treatment composition of Example 4 (mixture C). A portion of the obtained composition of Example 4 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 4 was calculated to be 6 ppm.

[0101] Example 5: 1000 g of raw material composition 3 and 400 g of unused molecular sieve 13X were placed in a pre-dried flask. The mixture was treated for 20 hours with occasional stirring while controlling the liquid temperature in the flask to -75°C. After 20 hours, the mixture was filtered to obtain the treated composition of Example 5 (mixture C). A portion of the obtained composition of Example 5 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 5 was calculated to be 8 ppm.

[0102] Example 6 1000 g of raw material composition 4 and 400 g of unused molecular sieve 13X were placed in a pre-dried flask. The mixture was treated for 20 hours with occasional stirring while controlling the liquid temperature in the flask to -75°C. After 20 hours, the mixture was filtered to obtain the treated composition of Example 6 (mixture C). A portion of the obtained composition of Example 6 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 6 was calculated to be 3 ppm.

[0103] <Comparative Example 1> 1000 g of raw material composition 1 and 50 g of unused molecular sieve 13X were placed in a pre-dried flask. The liquid temperature in the flask was controlled to 25 ° C. and treated for 20 hours with occasional stirring. After 20 hours, the mixture was filtered to obtain a treated composition. A portion of the obtained composition was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition was calculated to be 5723 ppm.

[0104]

[0105] The method for separating perfluorotripropylamine of the present disclosure can be suitably used for purifying heat transfer fluids.

Claims

1. C ９ F １８ and a mixture B containing perfluorotripropylamine, the mixture A containing at least one selected from the group consisting of a hexafluoropropene trimer represented by the formula (I) and a perfluoroalkene ether and a perfluoropolyether, the mixture A having a freezing point at a temperature equal to or lower than the freezing point of perfluorotripropylamine, and a step of separating perfluorotripropylamine from the mixture B being carried out at a temperature equal to or lower than the freezing point of perfluorotripropylamine.

2. The method for separating perfluorotripropylamine according to claim 1, wherein the difference in freezing point between mixture A and perfluorotripropylamine is 20°C or more.

3. A method for separating perfluorotripropylamine according to claim 1 or 2, wherein the content of perfluorotripropylamine contained in mixture C after separation of perfluorotripropylamine is 1000 mass ppm or less.

4. Above C ９ F １８ The hexafluoropropene trimer represented by the following formulas (I) to (III): The method for separating perfluorotripropylamine according to any one of claims 1 to 3, comprising at least one hexafluoropropene trimer represented by the formula:

5. The perfluoroalkene ether is represented by the following formula: CF ３ (CF ２ ) ｘ CF=CFCF(OR １ ) (CF ２ ) ｙ CF ３ , C.F. ３ (CF ２ ) ｘ C (OR １ ) = CFCF ２ (CF ２ ) ｙ CF ３ , C.F. ３ CF=CFCF(OR １ ) (CF ２ ) ｘ (CF ２ ) ｙ CF ３ , and C.F. ３ (CF ２ ) ｘ CF=C(OR １ ) CF ２ (CF ２ ) ｙ CF ３ , [wherein; R １ are each independently a methyl group or an ethyl group, x and y are each independently 0, 1, 2, or 3, and x + y is 1, 2, or 3.].

6. The perfluoropolyether is represented by the following formula: ２ O-Rf-R ２’ [In the formula: R and R′ are each independently —C ｍ F ２ｍ＋１ m is an integer from 1 to 8, Rf is a divalent fluoropolyoxyalkylene group containing 2 to 20 repeating units, said repeating units being: (i) -CFXO-, where X is F or CF ３ (ii) -CF ２ CFXO- (wherein X is F or CF ３ (iii) -CFXCF ２ O- (wherein X is F or CF ３ (iv) -CF ２ CF ２ CF ２ (v) -O-, and (v) -CF ２ CF ２ CF ２ CF ２ O-, or Rf is represented by (vi) -(CF ２ ) ｋ -CFZ-O- (wherein k is an integer from 0 to 3 and Z is -ORFT ３ Wherein, RF is -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O- and -CF ２ CF ２ CF ２ CF ２ O-, where each X is independently F or CF. ３ And T ３ is C １－５ The method for separating perfluorotripropylamine according to any one of claims 1 to 5, comprising at least one compound represented by the formula:

7. C ９ F １８ and perfluorotripropylamine, wherein the content of perfluorotripropylamine is 1000 ppm by mass or less.

8. Above C ９ F １８ The hexafluoropropene trimer represented by the following formulas (I) to (III):

8. The heat transfer fluid of claim 7, comprising at least one hexafluoropropene trimer represented by the formula:

9. The heat transfer fluid according to claim 8, wherein the compound represented by formula (I) is present in an amount of 85 mass% or more based on the total amount of hexafluoropropene trimer.

10. The perfluoroalkene ether is represented by the following formula: CF ３ (CF ２ ) ｘ CF=CFCF(OR １ ) (CF ２ ) ｙ CF ３ , C.F. ３ (CF ２ ) ｘ C (OR １ ) = CFCF ２ (CF ２ ) ｙ CF ３ , C.F. ３ CF=CFCF(OR １ ) (CF ２ ) ｘ (CF ２ ) ｙ CF ３ , and C.F. ３ (CF ２ ) ｘ CF=C(OR １ ) CF ２ (CF ２ ) ｙ CF ３ , [wherein; R １ are each independently a methyl group or an ethyl group, x and y are each independently 0, 1, 2, or 3, and x+y is 1, 2, or 3.

11. The perfluoropolyether is represented by the following formula: ２ O-Rf-R ２’ [In the formula: R and R′ are each independently —C ｍ F ２ｍ＋１ m is an integer from 1 to 8, Rf is a fluoropolyoxyalkylene chain comprising repeating units, the repeating units being: (i) -CFXO-, where X is F or CF ３ (ii) -CF ２ CFXO- (wherein X is F or CF ３ (iii) -CFXCF ２ O- (wherein X is F or CF ３ (iv) -CF ２ CF ２ CF ２ O-(v)-CF ２ CF ２ CF ２ CF ２ O- (vi) -(CF ２ ) ｋ -CFZ-O- (wherein k is an integer from 0 to 3 and Z is -ORFT ３ Wherein, RF is -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O- and -CF ２ CF ２ CF ２ CF ２ O-, where each X is independently F or CF. ３ And T ３ is C １－５ The heat transfer fluid according to any one of claims 7 to 10, comprising at least one compound represented by the formula:

12. The heat transfer fluid of any one of claims 7 to 11, further comprising a stabilizer.

13. The heat transfer fluid according to any one of claims 7 to 12, used in a semiconductor manufacturing process.

14. Use of a heat transfer fluid according to any one of claims 7 to 13 for heat transfer.

15. An apparatus for heat transfer comprising: a device; and a mechanism for transferring heat to or from said device, said mechanism comprising a heat transfer fluid according to any one of claims 7 to 13.

16. The heat transfer apparatus of claim 15, wherein the device is a wafer used to manufacture semiconductors.

17. A semiconductor manufacturing device comprising the heat transfer device according to claim 15 or 16.

18. A method of heat transfer comprising the steps of: providing a device; and transferring heat to or from said device using a heat transfer fluid according to any one of claims 7 to 13.

19. The heat transfer method of claim 18, wherein the device is a wafer used to manufacture semiconductors.

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