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

Abstract

To provide a separation method capable of efficiently separating perfluorotripropylamine from a mixture that comprises the perfluorotripropylamine and at least one member selected from the group consisting of a hexafluoropropene trimer represented by C9F18, a perfluoroalkenyl ether, and a perfluoropolyether.SOLUTION: The present disclosure provides a method for separating perfluorotripropylamine from a mixture B that comprises the perfluorotripropylamine and a mixture A comprising at least one member selected from the group consisting of a hexafluoropropene trimer represented by C9F18, a perfluoroalkenyl ether, and a perfluoropolyether. The freezing point of the mixture A is at a temperature equal to or lower than the freezing point of perfluorotripropylamine, and the step of separating perfluorotripropylamine from the mixture A is performed at a temperature equal to or lower than the freezing point of perfluorotripropylamine.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] As a heat transfer fluid, it is conceivable to use hexafluoropropene (HFP) trimer, perfluoroalkene ether, or perfluoropolyether instead of perfluorotripropylamine.

[0005] In an apparatus using perfluorotripropylamine as a heat transfer fluid, when replacing perfluorotripropylamine with another heat transfer fluid (for example, hexafluoropropene trimer), it is conceivable to circulate and replace the apparatus with the other heat transfer fluid. At this time, a mixture of perfluorotripropylamine and another heat transfer fluid is obtained. If perfluorotripropylamine can be separated from the obtained mixture, the heat transfer fluid used for replacement can be reused.

[0006] The object of the present invention is C9F 18To provide a separation method capable of efficiently separating perfluorotripropylamine from a mixture containing at least one selected from the group consisting of a hexafluoropropene trimer represented by, a perfluoroalkene ether, and a perfluoropolyether, and perfluorotripropylamine.

Means for Solving the Problems

[0007] This disclosure includes the following aspects. [1] C9F 18 A method for separating perfluorotripropylamine from a mixture B containing a mixture A containing at least one selected from the group consisting of a hexafluoropropene trimer represented by, a perfluoroalkene ether, and a perfluoropolyether, and perfluorotripropylamine, wherein the freezing point of the mixture A is a temperature equal to or lower than the freezing point of perfluorotripropylamine, The step of separating perfluorotripropylamine from the mixture B is carried out at a temperature equal to or lower than the freezing point of perfluorotripropylamine. [2] The method for separating perfluorotripropylamine according to [1] above, 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 [1] or [2] above, wherein the content of perfluorotripropylamine contained in the mixture C after separation of perfluorotripropylamine is 1000 mass ppm or less. [4] The C9F 18 The hexafluoropropene trimer represented by is at least one of the following formulas (I) to (III):

Chemical formula

[10] The perfluoroalkene ether is represented by the following formula: CF3(CF2) x CF=CFCF(OR 1 )(CF2) y CF3, CF3(CF2) x C(OR 1 )=CFCF2(CF2) y CF3, CF3CF=CFCF(OR 1 )(CF2) x (CF2) y CF3, and CF3(CF2) x CF=C(OR 1 )CF2(CF2) y CF3, [wherein; R 1 is, independently of each other, a methyl group or an ethyl group, x and y are, independently of each other, 0, 1, 2 or 3, x + y is 1, 2 or 3.] A heat transfer fluid according to any one of [7] to [9] above, comprising at least one of the compounds represented by

[11] The perfluoropolyether is represented by the following formula: R 2 O-Rf-R 2’ [wherein: R and R’ are, independently of each other, -C m F 2m+1 and m is an integer from 1 to 8, Rf is a fluoropolyoxyalkylene chain containing repeating units, The repeating units are (i) -CFXO- (wherein X is F or CF3) (ii) -CF2CFXO- (wherein X is F or CF3) (iii) -CFXCF2O- (wherein X is F or CF3) (iv) -CF2CF2CF2O- (v) -CF2CF2CF2CF2O- (vi) -(CF2) k -CFZ-O- (wherein k is an integer from 0 to 3, Z is -ORFT3, where RF is a fluoropolyoxyalkylene chain containing 0 to 10 constant number of repeating units selected from the group consisting of -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, and -CF2CF2CF2CF2O-, where X is, independently of each other, F or CF3, and T3 is C1-5 It is a perfluoroalkyl group.) represented by.] The heat transfer fluid according to any one of the above items [7] to

[10] , comprising at least one of the compounds represented by.

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

[11] , further comprising a stabilizer.

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

[12] , used in a semiconductor manufacturing process.

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

[13] .

[15] A device, A mechanism for transferring heat to or from the device, comprising the heat transfer fluid according to any one of the above items [7] to

[13] , and A heat transfer device comprising.

[16] The heat transfer device according to the above

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

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

[15] or

[16] .

[18] A step of preparing a device, A step of transferring heat to or from the device using the heat transfer fluid according to any one of the above items [7] to

[13] , and A heat transfer method comprising.

[19] The heat transfer method according to the above

[18] , wherein the device is a wafer used for manufacturing a semiconductor. [Effect of the Invention]

[0008] According to the present disclosure, a separation method capable of efficiently separating perfluorotripropylamine from a mixture containing at least one selected from the group consisting of hexafluoropropene trimer, perfluoroalkene ether, and perfluoropolyether represented by C9F 18 and perfluorotripropylamine is provided. [Embodiments for Carrying Out the Invention]

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

[0010] In this specification, the numerical range "A to B" is intended to include the numerical values of the lower and upper limits themselves. That is, the numerical range "A to B" means A or more and B or less.

[0011] Hereinafter, the heat transfer fluid of the present disclosure will be described.

[0012] (Method for Separating Perfluorotripropylamine) The method for separating perfluorotripropylamine of the present disclosure is a method for separating perfluorotripropylamine from a mixture B containing a mixture A containing at least one selected from the group consisting of a hexafluoropropene trimer represented by C9F 18 and perfluorotripropylamine, wherein the freezing point of the mixture A is a temperature equal to or lower than the freezing point of perfluorotripropylamine, and the step of separating perfluorotripropylamine from the mixture B is carried out at a temperature equal to or lower than the freezing point of perfluorotripropylamine. The mixture obtained as a result of treating by the method for separating perfluorotripropylamine of the present disclosure is also referred to as mixture C.

[0013] The mixture A contains at least one selected from the group consisting of a hexafluoropropene trimer represented by C9F 18 and perfluoroalkene ether and perfluoropolyether.

[0014] The mixture B is a mixture containing the mixture A and perfluorotripropylamine, and typically consists of the mixture A and perfluorotripropylamine. In other words, it can be said that the mixture A is the one obtained by removing perfluorotripropylamine from the mixture B.

[0015] Mixture C is a mixture obtained as a result of being treated by the method for separating perfluorotripropylamine of the present disclosure, and is a mixture in which part or all of perfluorotripropylamine has been removed from mixture B.

[0016] Mixture A, mixture B, and mixture C may typically have a similar composition except for the content of perfluorotripropylamine. It is not excluded that the contents of compounds other than perfluorotripropylamine are different. For example, the content (by mass) of each compound other than perfluorotripropylamine may differ within the range of 10% or less, 5% or less, 3% or less, or 1% or less with respect to the whole mixture.

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

[0018] C9F 18 The hexafluoropropene trimer represented by is not particularly limited, and may be any compound having any structure represented by C9F 18 The hexafluoropropene trimer preferably contains at least one of the hexafluoropropene trimers represented by the following formulas (I) to (III):

[0019] In the present specification, unless otherwise specified, the compound represented by the above formula (I) includes both the E-form and the Z-form of the diastereomer.

Chemical formula

[0020] In the present specification, unless otherwise specified, the compound represented by the above formula (I) includes both the E-form and the Z-form of the diastereomer.

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

[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, still 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 the above 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) is preferably contained in an amount of 1% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, even 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 the above formulas (I) to (III). By increasing the content of the compound represented by formula (I), the viscosity decreases.

[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, 50% by mass or more and less than 85% by mass, 40% by mass or more and 80% 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, based on the total amount of the compounds represented by the above formulas (I) to (III), and may preferably be 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, still 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 the formula (II) and the compound represented by the formula (III) is not particularly limited, and can 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 above perfluoroalkene ether is preferably the following formula: CF3(CF2) x CF=CFCF(OR 1 )(CF2) y CF3, CF3(CF2) x C(OR 1 )=CFCF2(CF2) y CF3, CF3CF=CFCF(OR 1 )(CF2) x (CF2) y CF3, and CF3(CF2) x CF=C(OR 1 )CF2(CF2) y CF3, [wherein; R 1 is each independently a methyl group or an ethyl group, x and y are each independently 0, 1, 2 or 3, x + y is 1, 2 or 3.] and contains at least one of the compounds represented by .

[0027] Examples of the above 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 may be mentioned.

[0028] The perfluoroalkene ether is preferably methyl perfluoroheptene ether. Methyl perfluoroheptene ether may contain a mixture of two or more structures and / or stereoisomers. For example, methyl perfluoroheptene ether may be about 48 to about 52 weight percent of 5-methoxyperfluoro-3-heptene, about 18 to about 22 weight percent of 3-methoxyperfluoro-3-heptene, about 18 to about 22 weight percent of 4-methoxyperfluoro-2-heptene, and about 6 to about 10 weight percent of 4-methoxyperfluoro-3-heptene and may contain a mixture of.

[0029] The perfluoroalkene ether specifically contains methyl-perfluoroheptene ether (MPHE) (C7F 13 OCH3). Specifically, product names such as "Opteon SF10" (manufactured by Chemours) may be mentioned.

[0030] The perfluoropolyether has the following formula: R 2 O-Rf-R 2’ [wherein: R and R' are each independently -C m F 2m+1 and m is an integer from 1 to 8, Rf is a divalent fluoropolyoxyalkylene group containing 2 to 20 repeating units, the repeating unit is (i) -CFXO- (wherein X is F or CF3) (ii) -CF2CFXO- (wherein X is F or CF3) (iii) -CFXCF2O- (wherein X is F or CF3) (iv) -CF2CF2CF2O-, and (v) -CF2CF2CF2CF2O- represented by, or Rf is (vi) -(CF2) k -CFZ-O- (wherein k is an integer from 0 to 3, Z is -ORFT3, here, RF is a fluoropolyoxyalkylene group containing 0 to 20 constant number of repeating units selected from the group consisting of -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, and -CF2CF2CF2CF2O-, here, X is independently F or CF3 each, and T3 is C 1-5 perfluoroalkyl group.) is a divalent group represented by.] containing at least one of the compounds represented by.

[0031] m is an integer from 1 to 8, preferably an integer from 1 to 5, an integer from 1 to 3.

[0032] Rf may preferably be one of the following groups (1) to (3): (1)-(CF2O) a -(CF2CF2O) b -(CF2-(CF2) z’ -CF2O) 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 is>0, and b / a is included between 0.1 and 10.]; (2)-(C3F6O) c’ -(C2F4O) b -(CFXO) t - [wherein X is independently -F or -CF3 each, b, c’, and t are each independently an integer of 100 or less, c’ > 0, b ≥ 0, t ≥ 0, preferably b and t > 0, c’ / b is included between 0.2 and 5.0, and (c’ + b) / t is included between 5 and 50.] (3)-(C3F6O) c’ -(CFXO) t - [wherein, X is each independently -F or -CF3, c’ and t are each independently an integer of 100 or less, c’ > 0, t ≥ 0, preferably t > 0, and c’ / t is included between 5 and 50.]

[0033] The perfluoropolyether is not particularly limited, and for example, it is 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 can preferably be 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, that is, a lower kinematic viscosity, the filterability of mixture A is improved. Therefore, when performing precise filtration with a fine pore size filter, it is possible to shorten the process time and reduce energy loss. Also, more precise filtration becomes possible.

[0035] The kinematic viscosity and density of the composition for a heat transfer fluid or the 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 can preferably be 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, losses due to evaporation can be reduced.

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

[0038] The freezing point of mixture A can preferably be -70°C or lower, more preferably -75°C or lower, still 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 point of perfluorotripropylamine, and the easier the separation becomes.

[0039] The freezing point of mixture A can be determined by a differential scanning calorimeter (DSC).

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

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

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

[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 preferably 5°C or more lower, more preferably 10°C or more lower, still 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 below the freezing point of perfluorotripropylamine and above the freezing point of mixture A.

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

[0048] The step of separating perfluorotripropylamine from mixture B is not particularly limited, but can 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 only one, or two or more may be combined. For example, separation as a pretreatment may be carried out by a certain method, and then separation as the main treatment may be carried out.

[0050] When the step of separating perfluorotripropylamine from mixture B is adsorption, as the adsorbent, molecular sieve, activated carbon, silica gel, zeolite, coordination polymer, porous polymer, metal organic framework, porous silica, etc. can be used, and molecular sieve is preferred. Specific molecular sieve includes 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, still more preferably 200 mass ppm or less, even 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 substantially not contain perfluorotripropylamine. "May substantially not contain 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] Mixture C preferably contains a hexafluoropropene trimer represented by C9F 18 and including.

[0054] Mixture C is preferably a heat transfer fluid. That is, the present disclosure provides a heat transfer fluid containing at least one selected from the group consisting of a hexafluoropropene trimer represented by C9F 18 and including, a perfluoroalkene ether, and a perfluoropolyether, and perfluorotripropylamine, and the content of perfluorotripropylamine is 1000 mass ppm or less.

[0055] The heat transfer fluid of the present disclosure may contain a hexafluoropropene dimer and / or a hexafluoropropene tetramer.

[0056] The hexafluoropropene dimer includes (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] The hexafluoropropene tetramer includes 1,1,1,2,5,6,6,6 - octafluoro - 2,3,5 - tris(trifluoromethyl) - 4 - (perfluoropropyl - 2 - yl) - 3 - hexene.

[0058] In addition to the hexafluoropropene trimer, the heat transfer fluid of the present disclosure contains C m F 2m and / or C n F (2n-2) [wherein, m is an integer of 4 or more and 12 or less and not 9, and n is an integer of 4 or more and 12 or less.]

[0059] m is an integer of 4 or more, preferably an integer of 5 or more, more preferably an integer of 6 or more. Also, n is an integer of 12 or less, preferably an integer of 11 or less, more preferably an integer of 10 or less. However, m does not include 9.

[0060] n is an integer of 4 or more, preferably an integer of 5 or more, more preferably an integer of 6 or more. Also, n is an integer of 12 or less, preferably an integer of 11 or less, more preferably an integer of 10 or less. Further, 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 so - called diene or 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)By coexisting with hexafluoropropene trimer, its function as a heat transfer fluid is improved. Further, the heat transfer fluid of the present disclosure contains C m F 2m and / or C n F (2n-2) to improve the stability of the hexafluoropropene trimer.

[0064] C m F 2m and / or C n F (2n-2) The content may preferably be 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less in the heat transfer fluid of the present disclosure. Also, C m F 2m and / or C n F (2n-2) The content may preferably be 0.0001% by mass or more, more preferably 0.001% by mass or more in the heat transfer fluid of the present disclosure. Note that C 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 contained.

[0065] The heat transfer fluid of the present disclosure may further contain other components.

[0066] The other components contained in the heat transfer fluid of the present disclosure may be any components that do not inhibit the effects and purposes of the present disclosure. Examples of such other components include water or stabilizers.

[0067] The stabilizer exerts a stabilizing effect and functions as a so-called acid acceptor or antioxidant. As the stabilizing effect, the main ones include the effect of preventing the decomposition of the hexafluoropropene trimer by scavenging radicals generated in the system, and the acid-accepting effect of preventing further decomposition of the hexafluoropropene trimer by acid by capturing the acid generated in the system.

[0068] As such stabilizers, it is possible to widely adopt known stabilizers. Among them, since it is possible to effectively suppress the occurrence of metal corrosion due to the composition, 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.

[0069] As unsaturated alcohol-based stabilizers, it is possible to widely adopt known ones. 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 can be used.

[0070] As nitro-based stabilizers, it is possible to widely adopt known ones. Examples of aliphatic nitro compounds include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, etc. Examples of aromatic nitro compounds include 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, and one or more selected from the group consisting of them can be used.

[0071] As amine stabilizers, known ones can be widely adopted. 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, dibenzylamine, tribenzylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine and diethylhydroxylamine can be used.

[0072] As phenolic stabilizers, known ones can be widely adopted. For example, one or more selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, 3-cresol, phenol, 1,2-benzenediol, 2-isopropyl-5-methylphenol, and 2-methoxyphenol can be used.

[0073] As epoxy stabilizers, known ones can be widely adopted. 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 can be used.

[0074] By using a combination of stabilizers having different stabilizing effects, the decomposition of hexafluoropropene trimer that may occur due to various causes can be more effectively prevented. For this reason, it is preferably composed of the above-described epoxy-based stabilizer and one or more selected from the group consisting of unsaturated alcohol-based stabilizers, nitro-based stabilizers, and phenol-based stabilizers.

[0075] From the viewpoint of effectively suppressing the acid liberation from the hexafluoropropene trimer and suppressing the corrosion of metals by the liquid composition, the content of the stabilizer in the entire heat transfer fluid is preferably 0.0001% by mass or more, and more preferably 0.01% by mass or more. On the other hand, considering the point of avoiding unfavorable physical property changes 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, and more preferably 5% by mass or less.

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

[0077] Since the heat transfer fluid of the present disclosure has a small pressure loss during circulation in use, it is suitably used for applications with a large heat transfer amount. 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 for manufacturing semiconductor devices.

[0078] (Device for heat transfer) The present disclosure further provides a device for heat transfer, including a device and a mechanism for transferring heat to or from the device, which contains the above-mentioned heat transfer fluid.

[0079] Examples of the device include a wafer used for manufacturing a semiconductor, a semiconductor element, a computer, a server computer, a server including a blade server; a disk array / storage system; a storage area network; storage connected to a network; a storage communication system; a workstation; a router; a telecommunication infrastructure / switch; wired, optical and wireless communication devices; a cell processor; a printer; a power supply device; a display; an optical device; a measurement system including a handheld system; military electronic equipment, etc., and preferably a wafer used for manufacturing a semiconductor.

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

[0081] When the device is a server computer, one logic board or a plurality of logic boards are arranged in the internal space. The logic board includes a number of heat-generating electronic components including at least one processor such as a CPU and a GPU. In addition, for example, other heat-generating components of a computer such as a chipset; a memory, a graphics chip, a network chip, a RAM, a power supply device, a daughter card; a storage drive such as a solid-state drive and a mechanical hard disk can also be used.

[0082] The heat transfer device is a heat transfer device for transferring heat to and from an object to be heat transferred using the heat transfer fluid, and heat transfer (transmission) occurs through heat contact with the object to be heat transferred. For example, when removing heat from the object to be heat transferred, it is cooling, and when supplying heat, it is heating. Although it may be a different mechanism depending on each case, cooling and heating may be performed with a single heat transfer device.

[0083] The heat transfer device is not particularly limited, and examples include a pump, a valve, a fluid confinement system, a pressure control system, a cooler, a heat exchanger, a heat source, a heat sink, a refrigeration system, an active temperature control system, a passive temperature control system, and the like.

[0084] More specifically, examples of the heat transfer device include 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 working area in semiconductor process equipment, a heat shock test bath solution reservoir, a constant temperature bath, and the like, and preferably a temperature-controlled working area in semiconductor process equipment.

[0085] The object to be heat transferred that is in 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 device of the present disclosure.

[0087] (Heat Transfer Method) The present disclosure discloses a heat transfer method including a step of preparing a device and a step of transferring heat to or from the device using the heat transfer fluid described above. Here, heat can be transferred by arranging the heat transfer device so as to be in thermal contact with the device. When the heat transfer device is arranged so as to be in thermal contact with the device, it 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 device.

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

Example

[0089] Hereinafter, the present disclosure will be described in 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 defined as the temperature at which a peak derived from endotherm was observed when the temperature was raised from 25 °C at a rate of 5 °C / min. The freezing point was defined as the temperature at which a peak derived from endotherm was observed when the temperature was raised at a rate of 5 °C / min after cooling to -150 °C or lower (a temperature at which solidification was confirmed) with liquid nitrogen.

[0092] <Synthesis Example of Heat Transfer Fluid a (Mixture A)> 750 g of DMF and 7.2 g of cesium fluoride were placed in a SUS autoclave and sealed. After degassing the inside of the autoclave under vacuum, 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 obtained reaction solution, washed with ultrapure water, and 2219 g of a heat transfer fluid composition a (mixture A) containing HFP trimer was obtained. GC-FID and GC-MS analyses were performed, and it was confirmed that the HFP trimer was contained in 87% by mass in the total amount of the composition of 100% by mass, and the compounds represented by the formulas (I), (II), and (III) described in this specification were contained in 78% by mass, 9% by mass, and 13% by mass, respectively, in the total amount of the HFP trimer of 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 were mixed to obtain a 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. While controlling the liquid temperature in the flask to be -75 °C and stirring occasionally, the mixture was treated for 20 hours. After 20 hours, filtration was performed to obtain the composition of Example 1 after treatment (mixture C). A part 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> 1000 g of raw material composition 1 and 100 g of unused molecular sieve 13X were placed into a pre-dried flask. While controlling the liquid temperature in the flask to be -75°C and stirring occasionally, the mixture was treated for 20 hours. After 20 hours, filtration was performed to obtain the composition (mixture C) of Example 2 after treatment. A part 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> 1000 g of raw material composition 1 and 400 g of unused molecular sieve 13X were placed into a pre-dried flask. While controlling the liquid temperature in the flask to be -75°C and stirring occasionally, the mixture was treated for 20 hours. After 20 hours, filtration was performed to obtain the composition (mixture C) of Example 3 after treatment. A part 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> 1000 g of raw material composition 2 and 400 g of unused molecular sieve 13X were placed into a pre-dried flask. While controlling the liquid temperature in the flask to be -75°C and stirring occasionally, the mixture was treated for 20 hours. After 20 hours, filtration was performed to obtain the composition (mixture C) of Example 4 after treatment. A part 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 into a pre-dried flask. While controlling the liquid temperature in the flask to be -75°C and stirring occasionally, the mixture was treated for 20 hours. After 20 hours, filtration was performed to obtain the composition (mixture C) of Example 5 after treatment. A part 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. While controlling the liquid temperature in the flask to be -75°C and stirring intermittently, the treatment was carried out for 20 hours. After 20 hours, filtration was performed to obtain the composition (mixture C) of Example 6 after treatment. A part 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. While controlling the liquid temperature in the flask to be 25°C and stirring intermittently, the treatment was carried out for 20 hours. After 20 hours, filtration was performed to obtain the composition after treatment. A part of the obtained composition was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition was calculated to be 5723 ppm.

[0104]

Table 1

Industrial Applicability

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

Claims

1. C ９ F １８ A method for separating perfluorotripropylamine from a mixture B containing a mixture A containing at least one selected from the group consisting of a hexafluoropropene trimer represented by, a perfluoroalkene ether, and a perfluoropolyether, and perfluorotripropylamine, comprising: The freezing point of the mixture A is a temperature equal to or lower than the freezing point of perfluorotripropylamine, and the step of separating perfluorotripropylamine from the mixture B is carried out at a temperature equal to or lower than the freezing point of perfluorotripropylamine, a method for separating perfluorotripropylamine.

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

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

4. Said C ９ F １８ The hexafluoropropene trimer represented by the following formula (I) to (III): 【Chemical 1】 The method for separating perfluorotripropylamine according to Claim 1, comprising at least one of the hexafluoropropene trimers represented by.

5. The perfluoroalkene ether is represented by the following formula: CF ３ (CF ２ ) ｘ CF = CFCF(OR １ ) (CF ２ ) ｙ CF ３ , CF ３ (CF ２ ) ｘ C(OR １ )=CFCF ２ (CF ２ ) ｙ CF ３ , CF 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 is, independently of each other, a methyl group or an ethyl group, x and y are each independently 0, 1, 2 or 3, x + y is 1, 2 or 3. ] The method for separating perfluorotripropylamine according to Claim 1, comprising at least one of the compounds represented by.

6. The perfluoropolyether is represented by the following formula: R ２ O-Rf-R ２’ [Wherein: R and R' are each independently, -C ｍ F ２ｍ＋１ and are m is an integer from 1 to 8, Rf is a divalent fluoropolyoxyalkylene group containing 2 to 20 repeating units, The repeating unit is (i) -CFXO- (wherein X is F or CF ３ is) (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- represented by, or Rf is (vi) - (CF ２ ) ｋ -CFZ-O- (wherein k is an integer of 0 to 3, and Z is -ORFT ３ and here, RF is -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, and -CF ２ CF ２ CF ２ CF ２ O- and is a fluoropolyoxyalkylene group containing 0 to 20 constant number of repeating units selected from the group consisting of, where X is each independently F or CF ３ and T ３ is a C １－５ perfluoroalkyl group.) is a divalent group represented by.] The method for separating perfluorotripropylamine according to Claim 1, comprising at least one of the compounds represented by.

7. C ９ F １８ A heat transfer fluid comprising at least one selected from the group consisting of hexafluoropropene trimers, perfluoroalkene ethers, and perfluoropolyethers represented by the formula, and perfluorotripropylamine, wherein the content of perfluorotripropylamine is 1000 mass ppm or less.

8. Said C ９ F １８ The hexafluoropropene trimer represented by the following formula (I) to (III): 【Chemical 2】 The heat transfer fluid according to Claim 7, comprising at least one of the hexafluoropropene trimers represented by.

9. The compound represented by formula (I) is 85 mass% or more based on the total amount of the hexafluoropropene trimers, the heat transfer fluid according to Claim 8.

10. The perfluoroalkene ether is represented by the following formula: CF ３ (CF ２ ) ｘ CF = CFCF(OR １ ) (CF ２ ) ｙ CF ３ , CF ３ (CF ２ ) ｘ C(OR １ )=CFCF ２ (CF ２ ) ｙ CF ３ , CF 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 is, independently of each other, a methyl group or an ethyl group, x and y are each independently 0, 1, 2 or 3, x + y is 1, 2 or 3. ] The heat transfer fluid according to Claim 7, comprising at least one of the compounds represented by.

11. The perfluoropolyether is represented by the following formula: R ２ O-Rf-R ２’ [Wherein: R and R' are each independently, -C ｍ F ２ｍ＋１ and are m is an integer from 1 to 8, Rf is a fluoropolyoxyalkylene chain containing repeating units, The repeating unit is (i) -CFXO- (wherein 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 and here, RF is -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, and -CF ２ CF ２ CF ２ CF ２ O-; and is a fluoropolyoxyalkylene chain containing 0 to 10 constant number of repeating units selected from the group consisting of, where X is, independently of each other, F or CF ３ and T ３ is a C １－５ perfluoroalkyl group.).] represented by, the heat transfer fluid according to Claim 7, comprising at least one of the compounds represented by.

12. A heat transfer fluid according to claim 7, further comprising a stabilizer.

13. The heat transfer fluid according to claim 7, which is used in a semiconductor manufacturing process.

14. Use of the heat transfer fluid according to claim 7 for heat transfer.

15. A device, a mechanism for transferring heat to or from the device, comprising the heat transfer fluid according to claim 7 and a heat transfer device.

16. The heat transfer device according to claim 15, wherein the device is a wafer used for manufacturing a semiconductor.

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

18. A step of preparing a device, a step of transferring heat to or from the device using the heat transfer fluid according to claim 7 and a heat transfer method.

19. The heat transfer method according to claim 18, wherein the device is a wafer used for manufacturing a semiconductor.

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