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

Abstract

The present invention provides a method for separating perfluorotripropylamine from a mixture B, the mixture B containing a mixture A and perfluorotripropylamine, the mixture A containing at least one selected from the group consisting of hexafluoropropylene trimer represented by C9F18, perfluoroolefin ether and perfluoropolyether, and the mixture B containing at least one selected from the group consisting of hexafluoropropylene trimer represented by C9F18, perfluoroolefin ether and perfluoropolyether, and the mixture B containing at least one selected from the group consisting of hexafluoropropylene trimer represented by C9F18, perfluoroolefin ether and perfluoropolyether. The freezing point of the mixture A is equal to or lower than the freezing point of the perfluorotripropylamine, and the step of separating the perfluorotripropylamine from the mixture A is carried out at a temperature equal to or lower than the freezing point of the perfluorotripropylamine.

Description

Technical Field

[0001] This invention relates to a method for separating perfluorotripropylamine, a heat transfer fluid, a heat transfer apparatus, and a heat transfer method. Background Technology

[0002] Perfluorotripropylamine is known to be used as a heat transfer fluid (Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Publication No. 2016-505882 Summary of the Invention

[0006] The technical problem that the invention aims to solve

[0007] As a heat transfer fluid, hexafluoropropylene (HFP) trimer, perfluoroolefin ether, or perfluoropolyether should be considered as alternatives to perfluorotripropylamine.

[0008] In devices using perfluorotripropylamine as a heat transfer fluid, when replacing the perfluorotripropylamine with another heat transfer fluid (such as hexafluoropropylene trimer), the other heat transfer fluid can be allowed to circulate within the device for replacement. This results in a mixture of perfluorotripropylamine and the other heat transfer fluid. If the perfluorotripropylamine can be separated from this mixture, the heat transfer fluid used for replacement can be reused.

[0009] The purpose of this invention is to provide a separation method that can separate substances containing C9F. 18 Perfluorotripropylamine can be effectively separated from a mixture of at least one of hexafluoropropylene trimer, perfluoroolefin ether and perfluoropolyether and perfluorotripropylamine.

[0010] Technical solutions for solving technical problems

[0011] The present invention includes the following methods.

[0012] [1] A method for separating perfluorotripropylamine, comprising separating perfluorotripropylamine from a mixture B, wherein the mixture B contains a mixture A and perfluorotripropylamine, and the mixture A contains a compound selected from C9F. 18 At least one of the following: hexafluoropropylene trimer, perfluoroolefin ether, and perfluoropolyether.

[0013] The freezing point of the above mixture A is a temperature below the freezing point of perfluorotripropylamine.

[0014] The process of separating perfluorotripropylamine from the above mixture B is carried out at a temperature below the freezing point of perfluorotripropylamine.

[0015] [2] The method for separating perfluorotripropylamine as described in [1] above, wherein the freezing point difference between mixture A and perfluorotripropylamine is greater than 20°C.

[0016] [3] The method for separating perfluorotripropylamine as described in [1] or [2] above, wherein the content of perfluorotripropylamine in the mixture C after separating perfluorotripropylamine is less than 1000 ppm by mass.

[0017] [4] The method for separating perfluorotripropylamine as described in any one of [1] to [3] above, wherein the above C9F 18 The hexafluoropropylene trimer shown includes at least one of the hexafluoropropylene trimers represented by formulas (I) to (III) below.

[0018] .

[0019] [5] The method for separating perfluorotripropylamine as described in any one of [1] to [4] above, wherein the perfluoroolefin ether comprises at least one of the compounds shown in the following formula,

[0020] CF3 (CF2) x CF = CFCF (OR 1 (CF2) y CF3

[0021] CF3 (CF2) x C(OR 1 )=CFCF2(CF2) y CF3

[0022] CF3CF = CFCF (OR 1 (CF2) x (CF2) y CF3, and

[0023] CF3 (CF2) x CF = C(OR) 1 )CF2(CF2) y CF3,

[0024] [In the formula:]

[0025] R 1 Each can be independently methyl or ethyl.

[0026] x and y are independently 0, 1, 2 or 3,

[0027] x + y is 1, 2, or 3.

[0028] [6] The method for separating perfluorotripropylamine as described in any one of [1] to [5] above, wherein the perfluoropolyether comprises at least one of the compounds shown in the following formula,

[0029] R 2 O-Rf-R 2’

[0030] [In the formula:]

[0031] R and R' are independently -C m F 2m＋1 ,

[0032] m is an integer from 1 to 8.

[0033] Rf is a divalent fluorinated polyoxyalkylene group containing 2 to 20 repeating units.

[0034] The aforementioned repeating units are represented by the following equations (i) to (v).

[0035] (i) -CFXO- (where X is F or CF3),

[0036] (ii)-CF2CFXO-(where X is F or CF3)

[0037] (iii) -CFXCF2O- (where X is F or CF3).

[0038] (iv)-CF2CF2CF2O-, and

[0039] (v)-CF2CF2CF2CF2O-, or

[0040] Rf is (ⅵ)-(CF2) k -CFZ-O- (where k is an integer from 0 to 3, Z is -ORFT3, RF is a fluorinated polyoxyalkylene group containing 0 to 20 repeating units selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O- and -CF2CF2CF2CF2O-, where X is independently F or CF3, and T3 is C 1－5 Perfluoroalkyl. (The divalent group shown is ).

[0041] [7] A heat transfer fluid containing a mixture selected from C9F 18 The present invention includes at least one of hexafluoropropylene trimer, perfluoroolefin ether and perfluoropolyether, and perfluorotripropylamine, wherein the content of perfluorotripropylamine is less than 1000 ppm by mass.

[0042] [8] The heat transfer fluid as described in [7] above, wherein the above-mentioned C9F 18The hexafluoropropylene trimer shown includes at least one of the hexafluoropropylene trimers represented by formulas (I) to (III) below.

[0043] .

[0044] [9] The heat transfer fluid as described in [8] above, wherein the compound represented by formula (I) is 85% by mass or more relative to the total hexafluoropropylene trimer.

[0045]

[10] The heat transfer fluid as described in any one of [7] to [9] above, wherein the perfluoroolefin ether comprises at least one of the compounds shown in the following formula,

[0046] CF3 (CF2) x CF = CFCF (OR 1 (CF2) y CF3

[0047] CF3 (CF2) x C(OR 1 )=CFCF2(CF2) y CF3

[0048] CF3CF = CFCF (OR 1 (CF2) x (CF2) y CF3, and

[0049] CF3 (CF2) x CF = C(OR) 1 )CF2(CF2) y CF3,

[0050] [In the formula:]

[0051] R 1 Each can be independently methyl or ethyl.

[0052] x and y are independently 0, 1, 2 or 3,

[0053] x + y is 1, 2, or 3.

[0054]

[11] The heat transfer fluid as described in any one of [7] to

[10] above, wherein the perfluoropolyether comprises at least one of the compounds shown in the following formula,

[0055] R 2 O-Rf-R 2’

[0056] [In the formula:]

[0057] R and R' are independently -C m F2m＋1 ,

[0058] m is an integer from 1 to 8.

[0059] Rf is a fluorinated polyoxyalkylene chain containing repeating units.

[0060] The aforementioned repeating units are represented by the following equations (i) to (vi).

[0061] (i) -CFXO- (where X is F or CF3),

[0062] (ii)-CF2CFXO-(where X is F or CF3)

[0063] (iii) -CFXCF2O- (where X is F or CF3).

[0064] (iv)-CF2CF2CF2O-,

[0065] (v)-CF2CF2CF2CF2O-,

[0066] (vi) - (CF2) k -CFZ-O- (where k is an integer from 0 to 3, Z is -ORFT3, RF is a fluorinated polyoxyalkylene chain containing 0 to 10 repeating units selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O- and -CF2CF2CF2CF2O-, where X is independently F or CF3, and T3 is C 1－5 Perfluoroalkyl. ]

[0067]

[12] The heat transfer fluid as described in any one of [7] to

[11] above further contains a stabilizer.

[0068]

[13] The heat transfer fluid as described in any one of [7] to

[12] above is used in a semiconductor manufacturing process.

[0069]

[14] The use of the heat transfer fluid described in any one of [7] to

[13] above for heat transfer.

[0070]

[15] A heat transfer device, comprising:

[0071] Devices; and

[0072] An apparatus comprising the heat transfer fluid described in any one of [7] to

[13] above and used for transferring heat to or from the device described above.

[0073]

[16] The heat transfer device as described in

[15] above, wherein the device is a wafer used to manufacture semiconductors.

[0074]

[17] A semiconductor manufacturing apparatus having the heat transfer apparatus described in

[15] or

[16] above.

[0075]

[18] A heat transfer method, comprising:

[0076] The process of preparing components; and

[0077] The process of transferring heat to or from the device using the heat transfer fluid described in any one of [7] to

[13] above.

[0078]

[19] The heat transfer method as described in

[18] above, wherein the device is a wafer used to manufacture semiconductors.

[0079] Invention Effects

[0080] Using this invention, a separation method can be provided that can separate substances containing C9F. 18 Perfluorotripropylamine can be effectively separated from a mixture of at least one of hexafluoropropylene trimer, perfluoroolefin ether and perfluoropolyether and perfluorotripropylamine. Detailed Implementation

[0081] In this specification, whether or not the expression "separately and independently" or the same expression is explicitly stated, except where there is an indication of an exception, if multiple terms (symbols) are defined in the chemical structure, the definition applies independently to each occurrence.

[0082] In this specification, the numerical range "A~B" refers to the numerical value itself, including both the lower and upper limits. That is, the numerical range "A~B" means above A and below B.

[0083] The heat transfer fluid of the present invention will be described below.

[0084] (Separation method of perfluorotripropylamine)

[0085] The method for separating perfluorotripropylamine according to the present invention is a method for separating perfluorotripropylamine from mixture B, which contains mixture A and perfluorotripropylamine, wherein mixture A contains substances selected from C9F. 18 The mixture A is at least one of hexafluoropropylene trimer, perfluoroolefin ether, and perfluoropolyether, and the freezing point of mixture A is a temperature below the freezing point of perfluorotripropylamine. The process of separating perfluorotripropylamine from mixture B is carried out at a temperature below the freezing point of perfluorotripropylamine. The mixture obtained as a result of processing by the perfluorotripropylamine separation method of the present invention is also referred to as mixture C.

[0086] Mixture A contains a compound selected from C9F. 18 At least one of the following: hexafluoropropylene trimer, perfluoroolefin ether, and perfluoropolyether.

[0087] Mixture B is a mixture containing mixture A and perfluorotripropylamine, typically consisting of mixture A and perfluorotripropylamine. In other words, mixture A can be considered the substance obtained by removing perfluorotripropylamine from mixture B.

[0088] Mixture C is a mixture obtained as a result of processing by the separation method of perfluorotripropylamine of the present invention, and is a mixture after removing part or all of the perfluorotripropylamine from mixture B.

[0089] Mixtures A, B, and C typically have the same composition except for the content of perfluorotripropylamine. It should be noted that differences in the content of compounds other than perfluorotripropylamine are not excluded. For example, the content (by mass) of each compound other than perfluorotripropylamine relative to the whole mixture may vary in the range of less than 10%, less than 5%, less than 3%, or less than 1%.

[0090] Mixtures A, B, and C can be used as heat transfer fluids.

[0091] As C9F 18 The hexafluoropropylene trimer shown is not particularly limited and can be any compound with C9F. 18 Compounds with any of the structures shown.

[0092] The aforementioned hexafluoropropylene trimer preferably comprises at least one of the hexafluoropropylene trimers shown in formulas (I) to (III) below.

[0093] .

[0094] Unless otherwise specified in this specification, the compound represented by formula (Ⅰ) above comprises both the diastereomer E-body and the diastereomer Z-body.

[0095] As a hexafluoropropylene trimer, it may contain only one of the compounds shown in formulas (I) to (III), or it may be a mixture containing two or three of them.

[0096] Relative to the total amount of compounds shown in formulas (I) to (III) above, the mixture may contain 99% or less by mass, preferably 90% or less by mass, more preferably 85% or less by mass, further preferably less than 85% by mass, for example 80% or less by mass, 70% or less by mass, 65% or less by mass, or 60% or less by mass of the compound shown in formula (I). By reducing the content of the compound shown in formula (I), the boiling point of mixture A increases. In other words, the vapor pressure of mixture A decreases.

[0097] Relative to the total amount of compounds shown in formulas (I) to (III) above, the content may include preferably 1% or more by mass, preferably 10% or more by mass, more preferably 30% or more by mass, further preferably 40% or more by mass, further more preferably 45% or more by mass, particularly preferably 50% or more by mass, for example 60% or more by mass, 65% or more by mass, 75% or more by mass, or 85% or more by mass of the compound shown in formula (I). By increasing the content of the compound shown in formula (I), the viscosity decreases.

[0098] Relative to the total stoichiometry of the compounds shown in formulas (I) to (III) above, the compound shown in formula (I) can be, for example, 1% to 99% by mass, 10% to 90% by mass, 30% to 90% by mass, 10% to 85% by mass, 35% to 85% by mass, 10% to 85% by mass, 20% to 85% by mass, 30% to 85% by mass, 40% to 85% by mass, or 50% to 85% by mass. The percentages are: 40% to 80% by mass, 55% to 80% by mass, 60% to 75% by mass, 65% to 70% by mass, 35% to 60% by mass, or 50% to 60% by mass, preferably 30% to 90% by mass, preferably 40% by mass and less than 85% by mass, more preferably 40% to 80% by mass, even more preferably 45% to 70% by mass, and even more preferably 50% to 60% by mass.

[0099] The mass ratio of the compound shown in formula (II) to the compound shown in 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.

[0100] The aforementioned perfluoroolefin ethers preferably comprise at least one compound represented by the following formula.

[0101] CF3 (CF2) x CF = CFCF (OR 1 (CF2) y CF3

[0102] CF3 (CF2) x C(OR 1 )=CFCF2(CF2) y CF3

[0103] CF3CF = CFCF (OR 1 (CF2) x (CF2)y CF3, and

[0104] CF3 (CF2) x CF = C(OR) 1 )CF2(CF2) y CF3

[0105] [In the formula:]

[0106] R 1 Each can be independently methyl or ethyl.

[0107] x and y are independently 0, 1, 2 or 3,

[0108] x + y is 1, 2, or 3.

[0109] Examples of the aforementioned perfluoroolefin ethers include...

[0110] 5-Methoxyperfluoro-3-heptene,

[0111] 3-Methoxyperfluoro-3-heptene,

[0112] 4-Methoxyperfluoro-2-heptene,

[0113] 3-Methoxyperfluoro-2-heptene,

[0114] 4-Methoxyperfluoro-2-pentene,

[0115] 2-Methoxyperfluoro-2-pentene,

[0116] 3-Methoxyperfluoro-2-pentene,

[0117] 2-Methoxyperfluoro-3-pentene,

[0118] cis- and trans-2-methoxyperfluoro-2-octene, and

[0119] 2-Methoxyperfluoro-3-octene.

[0120] The aforementioned perfluoroolefin ether is preferably methyl perfluoroheptene ether. Methyl perfluoroheptene ether may also contain a mixture of two or more structural and / or stereoisomers. For example, methyl perfluoroheptene ether may contain a mixture of about 48 to about 52% by weight of 5-methoxyperfluoro-3-heptene, about 18 to about 22% by weight of 3-methoxyperfluoro-3-heptene, about 18 to about 22% by weight of 4-methoxyperfluoro-2-heptene, and about 6 to about 10% by weight of 4-methoxyperfluoro-3-heptene.

[0121] The aforementioned perfluoroolefin ethers specifically include methyl-perfluoroheptenyl ether (MPHE) (C7F 13OCH3). Specific examples include product names such as "Opteon SF10" (manufactured by Chemours).

[0122] The above-mentioned perfluoropolyethers include at least one of the compounds shown in the following formulas.

[0123] R 2 O-Rf-R 2’

[0124] [In the formula:]

[0125] R and R' are independently -C m F 2m＋1 ,

[0126] m is an integer from 1 to 8.

[0127] Rf is a divalent fluorinated polyoxyalkylene group containing 2 to 20 repeating units.

[0128] The aforementioned repeating units are represented by equations (i) to (v).

[0129] (i) -CFXO- (where X is F or CF3),

[0130] (ii)-CF2CFXO- (where X is F or CF3),

[0131] (iii) -CFXCF2O- (where X is F or CF3),

[0132] (iv)-CF2CF2CF2O-, and

[0133] (v)-CF2CF2CF2CF2O-, or

[0134] Rf is (ⅵ)-(CF2) k -CFZ-O- (where k is an integer from 0 to 3, Z is -ORFT3, RF is a fluorinated polyoxyalkylene group containing 0 to 20 repeating units selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O- and -CF2CF2CF2CF2O-, where X is independently F or CF3, and T3 is C 1－5 Perfluoroalkyl. (The divalent group shown is ).

[0135] m is an integer from 1 to 8, preferably an integer from 1 to 5 or an integer from 1 to 3.

[0136] Rf is preferably one of the following groups (1) to (3).

[0137] (1)-(CF2O) a -(CF2CF2O) b-(CF2-(CF2) z’ -CF2O) c

[0138] [In the formula:]

[0139] a, b, and c are each an integer less than 100, preferably less than 50.

[0140] z' is 1 or 2.

[0141] a≥0, b≥0, c≥0,

[0142] a + b > 0,

[0143] Preferably, a and b are both greater than 0, and b / a is between 0.1 and 10.

[0144] (2) - (C3F6O) c’ -(C2F4O) b —(CFXO) t -

[0145] [In the formula:]

[0146] X can be independently -F or -CF3.

[0147] b, c', and t are each an independent integer less than 100.

[0148] c'>0, b≥0, t≥0,

[0149] Preferably, b and t > 0, c' / b is between 0.2 and 5.0, and (c'+b) / t is between 5 and 50.

[0150] (3)-(C3F6O) c’ —(CFXO) t -

[0151] [In the formula,]

[0152] X can be independently -F or -CF3.

[0153] c' and t are independent integers less than 100.

[0154] c'>0, t≥0,

[0155] Preferably, t > 0, and c' / t is between 5 and 50.

[0156] There are no particular limitations on perfluoropolyethers; for example, they can be obtained from Solvay Solexis SpA under trademarks such as GALDEN (registered trademark) HT110 and GALDEN (registered trademark) HT135.

[0157] The kinematic viscosity of mixture A at -75°C is preferably 100 cSt or less, more preferably 80 cSt or less, and even more preferably 60 cSt or less. Mixture A, by having a kinematic viscosity within the above range, i.e., a lower kinematic viscosity, exhibits improved filterability. Therefore, in the case of precision filtration with fine filter pores, process time can be shortened and energy loss reduced. Furthermore, higher precision filtration is possible.

[0158] The kinematic viscosity and density of the heat transfer fluid composition or heat transfer fluid of the present invention are values ​​measured using an Anton Paar SVM3001 kinematic viscometer.

[0159] The boiling point of mixture A is preferably 90°C or higher, more preferably 95°C or higher, and even more preferably 100°C or higher. A higher boiling point of mixture A reduces losses due to evaporation.

[0160] The boiling point of mixture A is the temperature obtained by observing the endothermic peak when the temperature is increased from 25°C to 5°C / min using a differential scanning calorimeter (DSC).

[0161] The freezing point of mixture A is preferably below -70°C, more preferably below -75°C, even more preferably below -80°C, and even more preferably below -85°C. The lower the freezing point of mixture A, the greater the difference between its freezing point and that of perfluorotripropylamine, making separation easier.

[0162] The freezing point of mixture A can be determined using differential scanning calorimetry (DSC).

[0163] The freezing point of perfluorotripropylamine is approximately -65°C.

[0164] The freezing point difference between mixture A and perfluorotripropylamine is 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 keeping the freezing point difference between mixture A and perfluorotripropylamine within the above range, the separation of perfluorotripropylamine becomes easier.

[0165] There is no particular upper limit to the difference in freezing point between mixture A and perfluorotripropylamine; for example, it can be below 100°C, below 80°C, below 60°C, below 50°C, below 40°C, or below 30°C.

[0166] The process of separating perfluorotripropylamine from mixture B is carried out at a temperature below the freezing point of perfluorotripropylamine.

[0167] The process of separating perfluorotripropylamine from mixture B is carried out at a temperature preferably 5°C or more lower than the freezing point of perfluorotripropylamine, more preferably 10°C or more lower, even more preferably 15°C or more lower, for example, 20°C or more lower or 30°C or more lower.

[0168] The process 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.

[0169] The process of separating perfluorotripropylamine from mixture B is carried out at a temperature preferably 1°C or higher, more preferably 5°C or higher, for example 10°C or higher, or 15°C or higher than the freezing point of mixture A.

[0170] The process of separating perfluorotripropylamine from mixture B is preferably carried out at a temperature that is closer to the freezing point of mixture A than the freezing point of perfluorotripropylamine.

[0171] The procedure for separating perfluorotripropylamine from mixture B is not particularly limited and may include extraction, concentration, freeze-drying, precipitation, adsorption, distillation, rectification, or chromatography. Preferred procedures for separating perfluorotripropylamine from mixture A include freeze-drying, recrystallization, adsorption, distillation, rectification, or chromatography, with adsorption being particularly preferred.

[0172] The above methods can be used individually or in combination of two or more. For example, a method can be used for preprocessing separation, followed by separation for main processing.

[0173] When the process of separating perfluorotripropylamine from mixture B is adsorption, molecular sieves, activated carbon, silica gel, zeolites, coordination polymers, porous polymers, organometallic structures, porous silica, etc., can be used as adsorbent materials, with molecular sieves being preferred. A specific example of a molecular sieve is molecular sieve 13X.

[0174] The content of perfluorotripropylamine in mixture C is preferably less than 1000 ppm by mass, more preferably less than 500 ppm by mass, even more preferably less than 200 ppm by mass, even more preferably less than 100 ppm by mass, and particularly preferably less than 50 ppm by mass, less than 10 ppm by mass, less than 5 ppm by mass, or less than 1 ppm by mass. Mixture C may also be substantially free of perfluorotripropylamine. "May also be substantially free of perfluorotripropylamine" means that the content of perfluorotripropylamine is below the detection limit.

[0175] The content of perfluorotripropylamine in the mixture can be analyzed by gas chromatography.

[0176] Mixture C preferably contains C9F 18 The hexafluoropropylene trimer shown.

[0177] The mixture C is preferably a heat transfer fluid. That is, the present invention provides a heat transfer fluid containing a mixture selected from C9F. 18 The present invention includes at least one of hexafluoropropylene trimer, perfluoroolefin ether and perfluoropolyether, and perfluorotripropylamine, wherein the content of perfluorotripropylamine is less than 1000 ppm by mass.

[0178] The heat transfer fluid of the present invention may also contain hexafluoropropylene dimer and / or hexafluoropropylene tetramer.

[0179] Hexafluoropropylene dimers comprise (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.

[0180] Hexafluoropropylene tetramer contains 1,1,1,2,5,6,6,6-octafluoro-2,3,5-tris(trifluoromethyl)-4-(perfluoropropyl-2-yl)-3-hexene.

[0181] In addition to hexafluoropropylene trimer, the heat transfer fluid of this invention also contains C m F 2m and / or C n F (2n－2) [In the formula, m is an integer greater than 4 and less than 12, and excluding 9; n is an integer greater than 4 and less than 12.]

[0182] m is an integer of 4 or higher, preferably an integer of 5 or higher, and more preferably an integer of 6 or higher. Additionally, n is an integer of 12 or lower, preferably an integer of 11 or lower, and more preferably an integer of 10 or lower. However, m does not include 9.

[0183] n is an integer of 4 or more, preferably an integer of 5 or more, and more preferably an integer of 6 or more. Additionally, 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.

[0184] C m F 2m It can be a chain compound or a cyclic compound that can have substituted structures. Chain compounds can be so-called alkenes, and can be straight-chain or branched.

[0185] C n F (2n－2) It can be a chain compound or a cyclic compound with substituted structures. Chain compounds can be dienes or alkynes, and can be straight-chain or branched.

[0186] In the heat transfer fluid of the present invention, by making C m F 2m and / or C n F (2n－2) The coexistence with hexafluoropropylene trimer enhances its performance as a heat transfer fluid. Furthermore, the heat transfer fluid of this invention, by containing C... m F 2m and / or C n F (2n－2) The stability of hexafluoropropylene trimer is improved.

[0187] C m F 2m and / or C n F (2n－2) The content of [C] in the heat transfer fluid of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. Additionally, C m F 2m and / or C n F (2n－2) The content of [C] in the heat transfer fluid of the present invention is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more. It should be noted that C m F 2m and / or C n F (2n－2) This is not an essential component in the heat transfer fluid of this invention and may be omitted.

[0188] The heat transfer fluid of the present invention may also contain other components.

[0189] The other components contained in the heat transfer fluid of the present invention can be any type of component that does not impair the effects and objectives of the present invention. Examples of such other components include water or stabilizers.

[0190] Stabilizers function as acid absorbers or antioxidants by exerting a stabilizing effect. Their stabilizing effects can be categorized as follows: preventing the decomposition of hexafluoropropylene trimer by capturing free radicals generated within the system; and preventing further decomposition of hexafluoropropylene trimer by capturing acids generated within the system.

[0191] Well-known stabilizers can be widely used as such stabilizers. Among them, from the viewpoint of effectively suppressing metal corrosion caused by the composition, it is preferable to use one or more stabilizers selected from unsaturated alcohol stabilizers, nitro stabilizers, amine stabilizers, phenol stabilizers, and epoxy stabilizers.

[0192] As an unsaturated alcohol stabilizer, a wide range of well-known substances can be used. For example, one or more of the following can be used: 3-butene-2-ol, 2-butene-1-ol, 4-propylene-1-ol, 1-propylene-3-ol, 2-methyl-3-butene-2-ol, 3-methyl-3-butene-2-ol, 3-methyl-2-butene-1-ol, 2-hexene-1-ol, 2,4-hexadien-1-ol, and oleyl alcohol.

[0193] As nitro stabilizers, widely known substances can be used. Examples of aliphatic nitro compounds include nitromethane, nitrobenzene, 1-nitropropane, and 2-nitropropane. Examples of aromatic nitro compounds include one or more selected from nitrobenzene, o-dinitrobenzene, m-dinitrobenzene or p-dinitrobenzene, o-nitrotoluene, m-nitrotoluene or p-nitrotoluene, dimethylnitrobenzene, m-nitroacetophenone, o-nitrophenol, m-nitrophenol or p-nitrophenol, o-nitroanisole, m-nitroanisole, and p-nitroanisole.

[0194] As an amine stabilizer, a wide range of well-known substances can be used. For example, one or more of the following can be used: pentylemine, 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, tripentylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, and diethylhydroxylamine.

[0195] As a phenolic stabilizer, a wide range of well-known substances can be used. For example, one or more of the following can be used: 2,6-di-tert-butyl-4-methylphenol, 3-cresol, phenol, 1,2-benzene glycol, 2-isopropyl-5-methylphenol, and 2-methoxyphenol.

[0196] As an epoxy stabilizer, a wide range of well-known substances can be used. For example, one or more of the following can be used: epoxide butane, 1,2-epoxide propylene, 1,2-epoxide butane, butyl glycidyl ether, diethylene glycol diglycidyl ether, and 1,2-epoxide-3-phenoxypropane.

[0197] Considering the need to more effectively prevent the decomposition of hexafluoropropylene trimer caused by various factors by using a combination of stabilizers with different stabilizing effects, it is preferable to use an epoxy stabilizer as described above, and one or more stabilizers selected from unsaturated alcohol stabilizers, nitro stabilizers, and phenol stabilizers.

[0198] From the viewpoint of effectively suppressing free acid from hexafluoropropylene trimer and inhibiting metal corrosion caused by the liquid composition, the content of stabilizer in the entire heat transfer fluid is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more. On the other hand, considering the avoidance of adverse changes in the physical properties of the heat transfer fluid due to excessive addition of stabilizer, the content of stabilizer in the entire heat transfer fluid is preferably 10% by mass or less, more preferably 5% by mass or less.

[0199] (Applications of heat transfer fluids)

[0200] The heat transfer fluid of the present invention is used to absorb heat from or supply heat to various objects to which heat is transferred. The objects to which heat is transferred according to the present invention are articles, apparatuses, or atmospheres that are cooled, heated, or maintained at a controlled temperature. Examples of such objects include electrical components, mechanical components, and optical components, as well as their processed and assembled products. Specific examples of the objects to which heat is transferred according to the present invention are not particularly limited, but include wafers used in the manufacture of semiconductor devices, microprocessors, power control semiconductors, electrical switchgear, power transformers, circuit boards, multi-chip modules, assembled and unassembled semiconductor devices, chemical reactors, nuclear reactors, fuel cells, lasers, missile components, etc.

[0201] The heat transfer fluid of the present invention is suitable for applications requiring large heat transfer due to its low pressure loss during circulation. In a preferred embodiment, the heat transfer fluid of the present invention is used in a semiconductor manufacturing process. The object to be heated in the semiconductor manufacturing process is a wafer used to manufacture semiconductor devices.

[0202] (Heat transfer device)

[0203] The present invention also provides a heat transfer apparatus having a device and a mechanism comprising the aforementioned heat transfer fluid for transferring heat to or from the device.

[0204] Examples of devices include: wafers for manufacturing semiconductors, semiconductor components, computers, server computers, servers including blade servers; disk arrays / storage systems; storage area networks; network-connected storage; storage communication systems; workstations; routers; electrical communication infrastructure / switches; wired, optical and wireless communication devices; cell processing devices; printers; power supply devices; displays; optical devices; measurement systems including handheld systems; military electronic equipment, etc., preferably wafers for manufacturing semiconductors.

[0205] Semiconductor components are heat-generating components mounted on devices, such as CPUs, GPUs, and SSDs. These semiconductor components are composed of single-element silicon, germanium, and compound semiconductors such as gallium arsenide (GaAs), gallium phosphide (GaP), indium phosphide (InP), gallium nitride (GaN), and silicon carbide (SiC).

[0206] In the case of a server computer, one or more logic boards are configured within the internal space. Each logic board contains multiple heat-generating electronic components, including at least one processor such as a CPU and GPU. In addition, other heat-generating computer components may be used, such as chipsets; memory, graphics card chips, network chips, RAM, power supplies, daughter cards; and storage drives such as solid-state drives and hard disk drives.

[0207] A heat transfer device is used to move heat between itself and the object being transferred using the aforementioned heat transfer fluid. Heat is transferred through thermal contact with the object. For example, absorbing heat from the object is called cooling, and supplying heat is called heating. Different mechanisms can be used depending on the specific circumstances, but a single heat transfer device can also perform both cooling and heating.

[0208] As a heat transfer device, there are no particular limitations; examples include pumps, valves, fluid closed systems, pressure control systems, coolers, heat exchangers, heat sources, radiators, refrigeration systems, active temperature control systems, passive temperature control systems, etc.

[0209] More specifically, as a heat transfer device, examples include temperature-controlled wafer chucks in plasma-enhanced chemical vapor deposition (PECVD) tools, temperature-controlled test heads for mold performance testing, temperature-controlled working areas in semiconductor process equipment, thermal shock test baths, and constant temperature baths, with the temperature-controlled working areas in semiconductor process equipment being the preferred option.

[0210] The object that is in thermal contact with the heat transfer device is the same as described above.

[0211] In addition, the present invention also provides a semiconductor manufacturing apparatus having the heat transfer device of the present invention.

[0212] (Heat transfer method)

[0213] This invention discloses a heat transfer method, comprising: a step of preparing a device; and a step of transferring heat to or from the device using the aforementioned heat transfer fluid. Heat can be transferred by configuring the heat transfer device in a manner that allows it to make thermal contact with the device. When the heat transfer device is configured to make thermal contact with the device, heat is removed from the device, heat is supplied to the device, or the device is maintained 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.

[0214] The present invention has been described above, but the present invention is not limited to the above description and can be implemented in various ways without departing from the spirit of the present invention.

[0215] Example

[0216] The present invention will be described below in the embodiments, but the present invention is not limited to the following embodiments.

[0217] The content of perfluorotripropylamine in the composition was determined by gas chromatography.

[0218] The boiling point and freezing point of the composition were determined using a differential scanning calorimeter (DSC). Specifically, the boiling point was the temperature obtained by observing the endothermic peak when the temperature was increased from 25°C at a rate of 5°C / min. The freezing point was the temperature obtained by observing the endothermic peak when the composition was cooled to below -150°C (the temperature at which solidification can be confirmed) with liquid nitrogen and then heated at a rate of 5°C / min.

[0219] <Example of synthesis of heat transfer fluid a (mixture A)>

[0220] 750 g of DMF and 7.2 g of cesium fluoride were placed in an SUS-made autoclave and sealed. After vacuum degassing of the autoclave, 2268 g of hexafluoropropylene was added over 4.5 hours while maintaining the temperature inside the autoclave at 70–110 °C. The lower layer was separated from the resulting reaction solution and washed with ultrapure water to obtain 2219 g of a heat transfer fluid composition a (mixture A) containing HFP trimer. GC-FID and GC-MS analyses were performed, and the area percentage method confirmed that the composition contained 87% by mass of HFP trimer in 100% by mass, and 78%, 9%, and 13% by mass of the compounds represented by formulas (I), (II), and (III) as described in this specification in 100% by mass of the total HFP trimer, respectively.

[0221] <Manufacturing Example 1>

[0222] 990g of heat transfer fluid a (mixture A) and 10g of FC-3283 (perfluorotripropylamine) manufactured by 3M were mixed to obtain raw material composition 1 (mixture B).

[0223] <Manufacturing Example 2>

[0224] 990g of Opteon SF10 ((methyl perfluorohepten ether) (mixture A) manufactured by Chemours Company and 10g of FC-3283 (perfluorotripropylamine) manufactured by 3M Company were mixed to obtain raw material composition 2 (mixture B).

[0225] <Manufacturing Example 3>

[0226] Mixing 990g of Galden HT110 (perfluoropolyether, boiling point 110°C, freezing point -100°C) (mixture A) manufactured by Solvay and 10g of FC-3283 (perfluorotripropylamine) manufactured by 3M yields raw material composition 3 (mixture B).

[0227] <Manufacturing Example 4>

[0228] Mixing 990g of Galden HT135 (perfluoropolyether, boiling point 110°C, freezing point -100°C) (mixture A) manufactured by Solvay and 10g of FC-3283 (perfluorotripropylamine) manufactured by 3M yields raw material composition 4 (mixture B).

[0229] <Example 1>

[0230] 1000g of raw material composition 1 and 50g of unused molecular sieve 13X (MS13X) were added to a pre-dried flask. The mixture was intermittently stirred while maintaining the liquid temperature in the flask at -75°C for 20 hours. After 20 hours, the mixture was filtered to obtain the treated composition of Example 1 (mixture C). A portion of the obtained composition of Example 1 was analyzed by gas chromatography, and the perfluorotripropylamine content in the composition of Example 1 was calculated to be 483 ppm.

[0231] <Example 2>

[0232] 1000g of raw material composition 1 and 100g of unused molecular sieve 13X were added to a pre-dried flask. The liquid temperature in the flask was maintained at -75°C while intermittent stirring was performed for 20 hours. After 20 hours, the mixture was filtered to obtain the treated composition of Example 2 (mixture C). A portion of the obtained composition of Example 2 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 2 was calculated to be 234 ppm.

[0233] <Example 3>

[0234] 1000g of raw material composition 1 and 400g of unused molecular sieve 13X were added to a pre-dried flask. The liquid temperature in the flask was maintained at -75°C while intermittent stirring was performed for 20 hours. After 20 hours, the mixture was filtered to obtain the treated composition of Example 3 (mixture C). A portion of the obtained composition of Example 3 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 3 was calculated to be 1 ppm.

[0235] <Example 4>

[0236] 1000g of raw material composition 2 and 400g of unused molecular sieve 13X were added to a pre-dried flask. The liquid temperature in the flask was maintained at -75°C while intermittent stirring was performed for 20 hours. After 20 hours, the mixture was filtered to obtain the treated composition of Example 4 (mixture C). A portion of the obtained composition of Example 4 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 4 was calculated to be 6 ppm.

[0237] <Example 5>

[0238] 1000g of raw material composition 3 and 400g of unused molecular sieve 13X were added to a pre-dried flask. The liquid temperature in the flask was maintained at -75°C while intermittent stirring was performed for 20 hours. After 20 hours, the mixture was filtered to obtain the treated composition of Example 5 (mixture C). A portion of the obtained composition of Example 5 was analyzed by gas chromatography, and the content of perfluorotripropylamine in the composition of Example 5 was calculated to be 8 ppm.

[0239] <Example 6>

[0240] 1000g of raw material composition 4 and 400g of unused molecular sieve 13X were added to a pre-dried flask. The mixture was intermittently stirred while maintaining the liquid temperature in the flask at -75°C for 20 hours. After 20 hours, the mixture was filtered to obtain the treated composition of Example 6 (mixture C). A portion of the obtained composition of Example 6 was analyzed by gas chromatography, and the perfluorotripropylamine content in the composition of Example 6 was calculated to be 3 ppm.

[0241] <Comparative Example 1>

[0242] 1000g of raw material composition 1 and 50g of unused molecular sieve 13X were added to a pre-dried flask. The liquid temperature in the flask was maintained at 25°C while intermittent stirring was performed for 20 hours. After 20 hours, the mixture was filtered to obtain the treated composition. A portion of the obtained composition was analyzed by gas chromatography, and the perfluorotripropylamine content in the composition was calculated to be 5723 ppm.

[0243] [Table 1]

[0244]

[0245] Industrial availability

[0246] The method for separating perfluorotripropylamine of the present invention can be applied to the purification of heat transfer fluids.

Claims

1. A method for separating perfluorotripropylamine, characterized in that: This separation method is a method for separating perfluorotripropylamine from mixture B, which contains mixture A and perfluorotripropylamine, wherein mixture A contains substances selected from C9F. 18 At least one of the following: hexafluoropropylene trimer, perfluoroolefin ether, and perfluoropolyether. The freezing point of mixture A is a temperature below the freezing point of perfluorotripropylamine. The process of separating perfluorotripropylamine from the mixture B is carried out at a temperature below the freezing point of perfluorotripropylamine.

2. The method for separating perfluorotripropylamine as described in claim 1, characterized in that: The freezing point difference between mixture A and perfluorotripropylamine is greater than 20°C.

3. The method for separating perfluorotripropylamine as described in claim 1 or 2, characterized in that: The content of perfluorotripropylamine in mixture C after separation is less than 1000 ppm by mass.

4. The method for separating perfluorotripropylamine according to any one of claims 1 to 3, characterized in that: The C9F 18 The hexafluoropropylene trimer shown includes at least one of the hexafluoropropylene trimers represented by formulas (I) to (III) below. 。 5. The method for separating perfluorotripropylamine according to any one of claims 1 to 4, characterized in that: The perfluoroolefin ether comprises at least one of the compounds shown in 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 the formula: R 1 Each can be independently methyl or ethyl. x and y are independently 0, 1, 2 or 3, x + y is 1, 2, or 3.

6. The method for separating perfluorotripropylamine according to any one of claims 1 to 5, characterized in that: The perfluoropolyether comprises at least one of the compounds shown in the following formula. R 2 O-Rf-R 2’ In the formula: R and R' are independently -C m F 2m＋1 , m is an integer from 1 to 8. Rf is a divalent fluorinated polyoxyalkylene group containing 2 to 20 repeating units. The repeating unit is represented by the following equations (i) to (v). (i) -CFXO-, where X is F or CF3, (ii)-CF2CFXO-, where X is F or CF3, (iii) -CFXCF2O-, where X is F or CF3. (iv)-CF2CF2CF2O-, and (v)-CF2CF2CF2CF2O-, or Rf is (ⅵ)-(CF2) k The divalent group shown in the formula -CFZ-O-, where k is an integer from 0 to 3, Z is -ORFT3, RF is a fluorinated polyoxyalkylene group containing 0 to 20 repeating units selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O- and -CF2CF2CF2CF2O-, where X is independently F or CF3, and T3 is C 1－5 Perfluoroalkyl.

7. A heat transfer fluid, characterized in that: Contains C9F 18 The present invention includes at least one of hexafluoropropylene trimer, perfluoroolefin ether and perfluoropolyether, and perfluorotripropylamine, wherein the content of perfluorotripropylamine is less than 1000 ppm by mass.

8. The heat transfer fluid as described in claim 7, characterized in that: The C9F 18 The hexafluoropropylene trimer shown includes at least one of the hexafluoropropylene trimers represented by formulas (I) to (III) below. 。 9. The heat transfer fluid as described in claim 8, characterized in that: The compound shown in formula (I) accounts for more than 85% by mass relative to all hexafluoropropylene trimers.

10. The heat transfer fluid according to any one of claims 7 to 9, characterized in that: The perfluoroolefin ether comprises at least one of the compounds shown in 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 the formula: R 1 Each can be independently methyl or ethyl. x and y are independently 0, 1, 2 or 3, x + y is 1, 2, or 3.

11. The heat transfer fluid according to any one of claims 7 to 10, characterized in that: The perfluoropolyether comprises at least one of the compounds shown in the following formula. R 2 O-Rf-R 2’ In the formula: R and R' are independently -C m F 2m＋1 , m is an integer from 1 to 8. Rf is a fluorinated polyoxyalkylene chain containing repeating units. The repeating unit is represented by the following equations (i) to (vi), (i) -CFXO-, where X is F or CF3, (ii)-CF2CFXO-, where X is F or CF3, (iii) -CFXCF2O-, where X is F or CF3. (iv)-CF2CF2CF2O-, (v)-CF2CF2CF2CF2O-, (vi) - (CF2) k -CFZ-O-, where k is an integer from 0 to 3, Z is -ORFT3, RF is a fluorinated polyoxyalkylene chain containing 0 to 10 repeating units selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, and -CF2CF2CF2CF2O-, where X is independently F or CF3, and T3 is C 1－5 Perfluoroalkyl.

12. The heat transfer fluid according to any one of claims 7 to 11, characterized in that: It also contains stabilizers.

13. The heat transfer fluid according to any one of claims 7 to 12, characterized in that: Used in semiconductor manufacturing processes.

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

15. A heat transfer device, characterized in that, include: Devices; and A mechanism comprising the heat transfer fluid of any one of claims 7 to 13 and used for transferring heat to or from the device.

16. The heat transfer apparatus as described in claim 15, characterized in that: The device is a wafer used to manufacture semiconductors.

17. A semiconductor manufacturing apparatus, characterized in that: The heat transfer apparatus having the features of claim 15 or 16.

18. A heat transfer method, characterized in that, include: The process of preparing components; and The process of transferring heat to or from the device using the heat transfer fluid according to any one of claims 7 to 13.

19. The heat transfer method as described in claim 18, characterized in that: The device is a wafer used to manufacture semiconductors.

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