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, an apparatus for heat transfer, and a method for heat transfer. [Background technology]

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

[0003] [Patent Document 1] Special Publication No. 2016-505882 Summary of the Invention [Problem to be solved by the invention]

[0004] Instead of perfluorotripropylamine, it is contemplated to use hexafluoropropene (HFP) trimer, perfluoroalkene ethers, or perfluoropolyethers 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 replace the perfluorotripropylamine by passing the other heat transfer fluid through the device. At this time, a mixture of perfluorotripropylamine and the other heat transfer fluid is obtained. If perfluorotripropylamine can be separated from this mixture, it becomes possible to reuse the heat transfer fluid used for the replacement.

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

[0007] The present disclosure includes the following aspects. [1] C9F 18 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: The freezing point of the mixture A is a temperature equal to or lower than the freezing point of perfluorotripropylamine, The method for separating perfluorotripropylamine, wherein 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 the above [1], wherein the difference in freezing point between mixture A and perfluorotripropylamine is 20°C or more. [3] The method for separating perfluorotripropylamine according to the above [1] or [2], wherein the content of perfluorotripropylamine contained in the mixture C after separation of perfluorotripropylamine is 1000 mass ppm or less. [4] C9F 18 The hexafluoropropene trimer represented by the following formulas (I) to (III): [ka] The method for separating perfluorotripropylamine according to any one of the above [1] to [3], which contains at least one kind of hexafluoropropene trimer represented by the following formula: [5] The perfluoroalkene ether has 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, [In formula; R 1 are 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. The method for separating perfluorotripropylamine according to any one of the above [1] to [4], wherein the compound contains at least one kind of compound represented by the following formula: [6] The perfluoropolyether has the following formula: R 2 O-Rf-R 2’ [In formula: 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- or Rf is (vi) -(CF2) k -CFZ-O- (wherein k is an integer of 0 to 3, Z is -ORFT3, where RF is a fluoropolyoxyalkylene group containing a certain number of repeating units of 0 to 20 selected from the group consisting of -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, and -CF2CF2CF2CF2O-, where each X is independently F or CF3, and T3 is C 1-5 It is a divalent group represented by the formula: The method for separating perfluorotripropylamine according to any one of the above [1] to [5], wherein the compound contains at least one kind of compound represented by the following formula: [7] C9F 18 and perfluorotripropylamine, wherein the content of perfluorotripropylamine is 1000 ppm by mass or less. [8] C9F 18 The hexafluoropropene trimer represented by the following formulas (I) to (III): [ka] The heat transfer fluid according to [7] above, comprising at least one hexafluoropropene trimer represented by the formula: [9] The heat transfer fluid according to the above [8], wherein the compound represented by formula (I) is present in an amount of 85 mass% or more based on the total amount of the hexafluoropropene trimer.

[10] The perfluoroalkene ether has 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, [In formula; R 1 are 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. The heat transfer fluid according to any one of the above [7] to [9], comprising at least one compound represented by the following formula:

[11] The perfluoropolyether has the following formula: R 2 O-Rf-R 2’ [In formula: R and R' are each independently -C m F 2m+1 and 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 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 of 0 to 3, Z is -ORFT3, where RF is a fluoropolyoxyalkylene chain containing a certain number of repeating units of 0 to 10 selected from the group consisting of -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, and -CF2CF2CF2CF2O-, where each X is independently F or CF3, and T3 is C1-5 is a perfluoroalkyl group. The heat transfer fluid according to any one of the above [7] to

[10] , comprising at least one compound represented by the following formula:

[12] A heat transfer fluid as defined in any one of [7] to

[11] above, further comprising a stabilizer.

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

[12] , for use 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 device, 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] . An apparatus for heat transfer comprising:

[16] The heat transfer apparatus according to

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

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

[15] or

[16] above.

[18] Providing a device; transferring heat to or from the device using the heat transfer fluid according to any one of the above [7] to

[13] ; A method of heat transfer comprising:

[19] The heat transfer method according to

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

[0008] According to the present disclosure, C9F 18 The present invention provides a method for efficiently separating perfluorotripropylamine from a mixture containing perfluorotripropylamine and at least one member selected from the group consisting of a hexafluoropropene trimer represented by the formula: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In this specification, regardless of whether "independently" or a similar expression is explicitly stated, unless otherwise stated, when a term (symbol) that may occur 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. That is, 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 disclosed herein is 18 A method for separating perfluorotripropylamine from a mixture A containing at least one selected from the group consisting of hexafluoropropene trimer represented by the formula (I), perfluoroalkene ether, and perfluoropolyether, and a mixture B containing perfluorotripropylamine, wherein the freezing point of the mixture A is a temperature below the freezing point of perfluorotripropylamine, and the step of separating perfluorotripropylamine from the mixture B is carried out at a temperature below the freezing point of perfluorotripropylamine. The mixture obtained as a result of the treatment by the method for separating perfluorotripropylamine of the present disclosure is also referred to as mixture C.

[0013] Mixture A is C9F 18 The compound contains at least one selected from the group consisting of hexafluoropropene trimers represented by the formula:

[0014] Mixture B is a mixture containing mixture A and perfluorotripropylamine, and typically consists of mixture A and perfluorotripropylamine. In other words, mixture A is 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 in which part or all of perfluorotripropylamine has been removed from mixture B.

[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 content of compounds other than perfluorotripropylamine is different. For example, the content (mass basis) 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 with respect to the entire mixture.

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

[0018] C9F 18 The hexafluoropropene trimer represented by the formula (I) is not particularly limited, and may be, for example, C9F 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): [ka] The compound contains at least one hexafluoropropene trimer represented by the formula:

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

[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 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) 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, 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 is reduced.

[0024] The compound represented by formula (I) is, 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) and 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: 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, [In formula; R 1 are 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. The compound includes at least one of the compounds represented by the formula:

[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 Examples include:

[0028] The perfluoroalkene ether is preferably methylperfluoroheptene ether. The methylperfluoroheptene ether may comprise a mixture of two or more structures and / or stereoisomers. For example, the methylperfluoroheptene ether is 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 The mixture may include:

[0029] The perfluoroalkene ether is specifically methyl-perfluoroheptene ether (MPHE) (CF 13 OCH3) is included. A specific example is the product name "Opteon SF10" (manufactured by Chemours).

[0030] The perfluoropolyether has the following formula: R 2 O-Rf-R 2’ [In formula: 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- or Rf is (vi) -(CF2) k -CFZ-O- (wherein k is an integer of 0 to 3, Z is -ORFT3, where RF is a fluoropolyoxyalkylene group containing a certain number of repeating units of 0 to 20 selected from the group consisting of -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, and -CF2CF2CF2CF2O-, where each X is independently F or CF3, and T3 is C 1-5 It is a divalent group represented by the formula: The compound includes at least one of the compounds 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)-(CF2O) a -(CF2CF2O) b -(CF2-(CF2) z’ -CF2O) c [In the formula, 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 comprised between 0.1 and 10. (2)-(C3F6O) c’ -(C2F4O) b -(CFXO) t - [In the formula, Each X is independently -F or -CF; 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 between 0.2 and 5.0, and (c'+b) / t is between 5 and 50.] (3)-(C3F6O) c’ -(CFXO) t - [In the formula, Each X is independently -F or -CF; c' and t are each independently an integer of 100 or less, c'>0, t≧0, Preferably, t>0 and c' / t is between 5 and 50.

[0033] Perfluoropolyethers include, but are not limited to, those available from Solvay Solexis SpA under the trade names GALDEN® HT110 and GALDEN® 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 in the above range, that is, a lower kinematic viscosity, mixture A has improved filterability. Therefore, when performing precision filtration using a filter with a fine pore size, it is possible to shorten the process time and reduce energy loss. In addition, filtration with higher accuracy 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 not less than 90° C., more preferably not less than 95° C., and even more preferably not less than 100° C. 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 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 approximately -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 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 freezing point difference between mixture A and perfluorotripropylamine in 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 lower than the freezing point of perfluorotripropylamine and higher 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 process of separating perfluorotripropylamine from mixture B is not particularly limited, but may be extraction, concentration, freeze-drying, precipitation, adsorption, distillation, rectification, or chromatography. The process 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 adsorption, the adsorbent may be a molecular sieve, activated carbon, silica gel, zeolite, coordination polymer, porous polymer, metal organic framework, porous silica, etc., and preferably a molecular sieve. A specific example of the molecular sieve is molecular sieve 13X.

[0051] The content of perfluorotripropylamine in the mixture C may be preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, even 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. The mixture C may be substantially free of perfluorotripropylamine. "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] Mixture C is preferably C9F 18 The hexafluoropropene trimer is represented by the formula:

[0054] Mixture C is preferably a heat transfer fluid. 18 and perfluorotripropylamine, and at least one member selected from the group consisting of a hexafluoropropene trimer represented by the formula (I) and a perfluoroalkene ether and a perfluoropolyether, wherein the content of the perfluorotripropylamine is 1000 ppm by mass or less.

[0055] The heat transfer fluid 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 includes, in addition to hexafluoropropene trimer, m F 2m and / or C. n F (2n-2) [In the formula, 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 more, preferably an integer of 5 or more, and more preferably an integer of 6 or more. 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 more, preferably an integer of 5 or more, and more preferably an integer of 6 or more. Also, 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 a straight chain or a branched chain.

[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 a straight chain or a branched chain.

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

[0064] C m F 2m and / or C. n F (2n-2) The content of may be preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less in the heat transfer fluid of the present disclosure. 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 further comprise other components.

[0066] The heat transfer fluid of the present disclosure may contain any other components that do not impair the effects and objects of the present disclosure. Examples of such other components include water and stabilizers.

[0067] The stabilizer exerts a stabilizing effect, thereby exerting a function as a so-called acid acceptor or antioxidant. The main stabilizing effects include 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. Among them, it is preferable to use one or more stabilizers selected from the group consisting of unsaturated alcohol stabilizers, nitro stabilizers, amine stabilizers, phenol stabilizers, and epoxy stabilizers, because they can effectively suppress the occurrence of metal corrosion caused by the composition.

[0069] As the unsaturated alcohol-based stabilizer, a wide variety of known ones can be used. 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-hexadiene-1-ol and oleyl alcohol can be used.

[0070] As the nitro stabilizer, a wide variety of known stabilizers can be used. As the aliphatic nitro compound, for example, nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, etc. can be mentioned. As the aromatic nitro compound, for example, 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 can be used.

[0071] As the amine-based stabilizer, it is possible to widely adopt known ones. For example, it is possible to use 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.

[0072] As the phenol-based stabilizer, a wide variety of known stabilizers can be used, 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 can be used.

[0073] As the epoxy stabilizer, a wide variety of known ones can be used, 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] The combination of stabilizers having different stabilizing effects more effectively prevents decomposition of the hexafluoropropene trimer, which may occur due to various causes. 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 caused by the liquid composition, the content of the stabilizer in the entire heat transfer fluid is preferably 0.0001 mass% or more, more preferably 0.01 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 mass% or less, more preferably 5 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 objects to which heat is transferred. The objects to which heat is transferred in the present disclosure are articles, devices, and atmospheres that are cooled, heated, or maintained at a temperature to be controlled. Such objects to which heat is transferred include electrical components, mechanical components, and optical components, as well as processed products and assemblies thereof. Specific examples of objects to which heat is transferred in the present disclosure include, but are not limited to, wafers used to manufacture semiconductor devices, microprocessors, power control semiconductors, electric branch switches, power transformers, circuit boards, multi-chip modules, mounted and unmounted semiconductor devices, chemical reactors, nuclear reactors, fuel cells, lasers, missile parts, and the like.

[0077] The heat transfer fluid of the present disclosure has a small pressure loss during circulation during use, and is therefore suitable for use in applications requiring a large amount 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 which heat is transferred in the semiconductor manufacturing process is a wafer used to manufacture a semiconductor device.

[0078] (Heat transfer device) 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] Devices include, for example, 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, and examples of such elements include a CPU, a GPU, and an SSD. The semiconductor element is composed of, for example, single elements such as silicon and germanium, and compound semiconductors such as gallium arsenide (GaAs), gallium phosphide (GaP), indium phosphide (InP), gallium nitride (GaN), and silicon carbide (SiC).

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

[0082] The heat transfer device is a heat transfer device for transferring heat between an object to which heat is transferred using the above-mentioned heat transfer fluid, and transfers heat by thermal contact with the object to which heat is transferred. For example, cooling is used when removing heat from the object to which heat is transferred, and heating is used when supplying heat. 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 fluid 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 method) The present disclosure discloses a method of heat transfer comprising the steps of providing a device and transferring heat to or from the device using a heat transfer fluid as described above, where heat may 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 or 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. EXAMPLES

[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 a peak due to endothermic heat was observed when the temperature was increased from 25°C at 5°C / min. The freezing point was the temperature at which a peak due to endothermic heat was observed when the composition was cooled to -150°C or lower (the temperature at which it was confirmed that the composition became solid) with liquid nitrogen and then heated at 5°C / min.

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

[0093] <Production Example 1> 990 g of the 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> Raw material composition 3 (mixture B) was obtained by mixing 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.

[0096] <Production Example 4> Raw material composition 4 (mixture B) was obtained by mixing 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.

[0097] <Example 1> 1000g of raw material composition 1 and 50g of unused molecular sieve 13X (MS13X) were placed in a flask that had been dried in advance. The liquid temperature in the flask was controlled to be -75°C, and the mixture was treated for 20 hours while being stirred occasionally. After 20 hours, the mixture was filtered to obtain a composition of Example 1 (mixture C) after treatment. 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> 1000g of the raw material composition 1 and 100g of unused molecular sieve 13X were placed in a flask that had been dried in advance. The liquid temperature in the flask was controlled to be -75°C, and the mixture was treated for 20 hours while stirring occasionally. After 20 hours, the mixture was filtered to obtain a composition of Example 2 (mixture C) after treatment. 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> 1000g of raw material composition 1 and 400g of unused molecular sieve 13X were placed in a flask that had been dried in advance. The liquid temperature in the flask was controlled to be -75°C and treated for 20 hours with occasional stirring. After 20 hours, the mixture was filtered to obtain a composition of Example 3 (mixture C) after treatment. 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> 1000g of the raw material composition 2 and 400g of unused molecular sieve 13X were placed in a flask that had been dried in advance. The liquid temperature in the flask was controlled to be -75°C, and the mixture was treated for 20 hours while stirring occasionally. After 20 hours, the mixture was filtered to obtain a composition of Example 4 (mixture C) after treatment. 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> 1000g of the raw material composition 3 and 400g of unused molecular sieve 13X were placed in a flask that had been dried in advance. The liquid temperature in the flask was controlled to be -75°C, and the mixture was treated for 20 hours while stirring occasionally. After 20 hours, the mixture was filtered to obtain a composition of Example 5 (mixture C) after treatment. 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> 1000g of the raw material composition 4 and 400g of unused molecular sieve 13X were placed in a flask that had been dried in advance. The liquid temperature in the flask was controlled to be -75°C, and the mixture was treated for 20 hours while being stirred occasionally. After 20 hours, the mixture was filtered to obtain a composition of Example 6 (mixture C) after treatment. 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> 1000g of raw material composition 1 and 50g of unused molecular sieve 13X were placed in a flask that had been dried in advance. The liquid temperature in the flask was controlled to be 25°C, and the mixture was treated for 20 hours while stirring occasionally. After 20 hours, the mixture was filtered to obtain a 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 5723ppm.

[0104] [Table 1] [Industrial Applicability]

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

Claims

1. C ９ F １８ 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: The freezing point of the mixture A is a temperature lower than the freezing point of perfluorotripropylamine, The method for separating perfluorotripropylamine, wherein 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. 2. The method for separating perfluorotripropylamine according to claim 1, wherein the freezing point difference between mixture A and perfluorotripropylamine is 20° C. or more.

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

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

5. The perfluoroalkene ether has 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 、 [In formula; R １ are 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. The method for separating perfluorotripropylamine according to claim 1, comprising at least one compound represented by the following formula:

6. The perfluoropolyether has the following formula: R ２ O-Rf-R ２’ [In the formula: 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 CF ３ (It is) (ii) -CF ２ CFXO- (wherein X is F or CF ３ (It is) (iii) -CFXCF ２ O- (wherein X is F or CF ３ (It is) (iv) -CF ２ CF ２ CF ２ O-, and (v) -CF ２ CF ２ CF ２ CF ２ O- or Rf is (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 is a perfluoroalkyl group.) is a divalent group represented by the formula: The method for separating perfluorotripropylamine according to claim 1, comprising at least one compound represented by the following formula:

7. C ９ F １８ and perfluorotripropylamine, the content of perfluorotripropylamine being 1000 mass ppm or less; ９ F １８ The content of the hexafluoropropene trimer represented by the formula (I) is 80% by mass or more, Furthermore, C ｍ F ２ｍ and / or C ｎ F （２ｎ－２） and one or more selected from the group consisting of an epoxy-based stabilizer, an unsaturated alcohol-based stabilizer, a nitro-based stabilizer, and a phenol-based stabilizer, C ｍ F ２ｍ and / or C ｎ F （２ｎ－２） The content is 10% by mass or less, A heat transfer fluid, comprising at least one stabilizer selected from the group consisting of an epoxy-based stabilizer, an unsaturated alcohol-based stabilizer, a nitro-based stabilizer, and a phenol-based stabilizer, the content of which is 10 mass % or less.

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

9. 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 the hexafluoropropene trimer.

10. The heat transfer fluid of claim 7, further comprising at least one selected from the group consisting of perfluoroalkene ethers and perfluoropolyethers.

11. The perfluoroalkene ether has 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 、 [In formula; R １ are 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. The heat transfer fluid of claim 10, comprising at least one compound represented by the formula:

12. The perfluoropolyether has the following formula: R ２ O-Rf-R ２’ [In the formula: R and R′ are each independently —C ｍ F ２ｍ＋１ and 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 (It is) (ii) -CF ２ CFXO- (wherein X is F or CF ３ (It is) (iii) -CFXCF ２ O- (wherein X is F or CF ３ (It is) (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 is a perfluoroalkyl group. The heat transfer fluid of claim 10, comprising at least one compound represented by the formula:

13. The heat transfer fluid of claim 7 further comprising a stabilizer.

14. 8. The heat transfer fluid of claim 7 used in semiconductor manufacturing processes.

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

16. A device, A mechanism for transferring heat to or from the device, comprising the heat transfer fluid of claim 7. An apparatus for heat transfer comprising:

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

18. A semiconductor manufacturing device comprising the heat transfer device according to claim 16.

19. Providing a device; transferring heat to or from said device using the heat transfer fluid of claim 7; A method of heat transfer comprising:

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

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