JP7674686B2 - Composition for heat transfer fluid, device with heat transfer mechanism, and heat transfer method - Google Patents

Description

The present disclosure relates to a heat transfer fluid composition, a device equipped with a heat transfer mechanism, and a heat transfer method.

Heat management is required in electrical and electronic equipment. For example, in semiconductor wafer manufacturing, process temperatures need to be controlled. Also, excess heat generated in microprocessors, data centers, power electronics, or aircraft needs to be removed. To solve these problems, heat transfer fluids are used. In general, it is desirable for such heat transfer fluids to have low kinetic viscosity and good dielectric properties.

Heat transfer fluids are also used in applications such as two-phase immersion cooling fluids, chiller fluids, or Rankine cycle working fluids.

Currently, the following are used for these purposes:
Perfluorotripropylamine (or tris(heptafluoropropyl)amine, or N,N-bis(heptafluoropropyl)(heptafluoropropyl)amine) [N(CF ₂ CF 2 CF 3 ) n (CF(CF ₃ )CF ₃ ) 3 _-n (n is an integer from 0 to ₃ )], represented by _the product name "Fluorinert (registered trademark)" ₍ manufactured by 3M) (FC-3283) (Patent Document 1);
- Perfluoropolyethers (PFPEs), such as those with the product names GALDEN® "HT135" and GALDEN® "HT110" (manufactured by Solvay), or more specifically, tetrafluoroethylene oxide polymers (Patent Document 2); and - Methoxytridecafluoroheptene isomer mixtures, such as those with the product name "Opteon SF10" (manufactured by Chemours), or more specifically, methyl-perfluoroheptene ether (MPHE) (C ₇ F ₁₃ OCH ₃ ) (Non-Patent Document 1).

Special table 2016-505882 publication International Publication No. WO 2010/034698

Aaron M. Jubb et al., and 4 others “Methyl-Perfluoroheptene-Ethers (CH3OC7F13): MeasuredOH Radical Reaction Rate Coefficients for Several Isomers and Enantiomers andTheir Atmosphere Lifetimes and Global Warming Potentials”, 2014, Environ. Sci. Technol. , 48, 4954-4962

The objective of the present disclosure is to provide a heat transfer fluid that can replace the existing heat transfer fluids described above.

As a result of intensive research aimed at solving the above problems, the inventors have found that a compound represented by C ₉ F ₁₈ can replace the above-mentioned existing heat transfer fluids. Based on this finding, the inventors have further researched and completed the present disclosure.

項３．前記Ｃ_９Ｆ_１８で表されるヘキサフルオロプロペン三量体が、前記ヘキサフルオロプロペン三量体全体に対して８５質量％未満の式（Ｉ）で表される化合物を含む、項２に記載の組成物。
項４．下記条件（ｉ）～（ｖｉ）を満たす、項１～３のいずれか１項に記載の組成物。
（ｉ）沸点が、前記熱伝達流体の沸点の８０％以上である。
（ｉｉ）流動点が、前記熱伝達流体の流動点以下である。
（ｉｉｉ）動粘度が、前記熱伝達流体の動粘度の２００％以下である。
（ｉｖ）前記熱伝達流体と任意の割合で相溶する。
項５．Ｃ_９Ｆ_１８で表されるヘキサフルオロプロペン三量体と、パーフルオロトリプロピルアミン、パーフルオロポリエーテル、及びメトキシトリデカフルオロヘプテン異性体混合物からなる群より選択される少なくとも一種とを含む、熱伝達流体用組成物。
項６．前記Ｃ_９Ｆ_１８で表されるヘキサフルオロプロペン三量体は、下記式（Ｉ）～（ＩＩＩ）で表される化合物からなる群より選択される少なくとも一種の化合物を含む、項５に記載の熱伝達流体用組成物。

項７．前記Ｃ_９Ｆ_１８で表されるヘキサフルオロプロペン三量体が、前記Ｃ_９Ｆ_１８で表されるヘキサフルオロプロペン三量体の全体に対して８５質量％未満の式（Ｉ）で表される化合物を含む、項６に記載の熱伝達流体用組成物。
項８．前記化合物が、前記Ｃ_９Ｆ_１８で表されるヘキサフルオロプロペン三量体の全体に対して８５質量％以上の式（Ｉ）で表される化合物を含む、項６に記載の熱伝達流体用組成物。
項９．デバイスと、前記デバイスへ又は前記デバイスから、項１～４のいずれか一項に記載の組成物、又は項５～８のいずれか一項に記載の熱伝達流体用組成物を熱伝達流体として用いて熱を伝達する熱伝達機構とを備え、前記熱伝達機構が、パーフルオロトリプロピルアミン、パーフルオロポリエーテル、及びメトキシトリデカフルオロヘプテン異性体混合物からなる群より選択される少なくとも一種を含む熱伝達流体を用いて熱を伝達するよう設計されている、熱伝達機構を含むデバイス。
項１０．Ｃ_９Ｆ_１８で表されるヘキサフルオロプロペン三量体の、パーフルオロトリプロピルアミン、パーフルオロポリエーテル、及びメトキシトリデカフルオロヘプテン異性体混合物からなる群より選択される少なくとも一種を含む熱伝達流体への代替のための使用。
項１１．パーフルオロトリプロピルアミン、パーフルオロポリエーテル、及びメトキシトリデカフルオロヘプテン異性体混合物からなる群より選択される少なくとも一種を含む熱伝達流体を用いて熱を伝達するよう設計されている熱伝達機構を含むデバイスにおいて、項１～４のいずれか一項に記載の組成物、又は項５～８のいずれか一項に記載の熱伝達流体用組成物を前記熱伝達流体に代替して用いて熱伝達機構を作動させることにより、前記デバイスへ又は前記デバイスから熱を伝達する工程を含む、熱伝達方法。 That is, the present disclosure includes the following aspects.
Item 1. A composition containing a hexafluoropropene trimer represented by C ₉ F ₁₈ for use as a replacement for a heat transfer fluid containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a mixture of methoxytridecafluoroheptene isomers.
Item 2. The composition according to item 1, wherein the hexafluoropropene trimer represented by C ₉ F ₁₈ contains at least one compound selected from the group consisting of compounds represented by the following formulas (I) to (III):

Item 3. The composition according to item 2, wherein the hexafluoropropene trimer represented by C ₉ F ₁₈ contains less than 85% by mass of the compound represented by formula (I) based on the entire hexafluoropropene trimer.
Item 4. The composition according to any one of items 1 to 3, which satisfies the following conditions (i) to (vi):
(i) The boiling point is 80% or more of the boiling point of the heat transfer fluid.
(ii) the pour point is equal to or less than the pour point of said heat transfer fluid;
(iii) the kinetic viscosity is 200% or less of the kinetic viscosity of the heat transfer fluid;
(iv) be miscible in any proportion with said heat transfer fluid;
Item 5. A heat transfer fluid composition comprising a hexafluoropropene trimer represented by C ₉ F ₁₈ and at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a mixture of methoxytridecafluoroheptene isomers.
Item 6. The heat transfer fluid composition according to Item 5, wherein the hexafluoropropene trimer represented by C ₉ F ₁₈ contains at least one compound selected from the group consisting of compounds represented by the following formulas (I) to (III):

Item 7. The heat transfer fluid composition according to item ₆ , wherein the hexafluoropropene trimer represented by _C9F18 contains less than 85% by mass of the compound represented by formula (I) based on the total amount of the hexafluoropropene trimer represented _{by C9F18} .
Item 8. The heat transfer fluid composition according to Item 6, wherein the compound contains 85 mass % or more of the compound represented by formula (I) based on the total amount of the hexafluoropropene trimer represented by C ₉ F ₁₈ .
Item 9. A device including a heat transfer mechanism, comprising: a device; and a heat transfer mechanism that transfers heat to or from the device using the composition according to any one of Items 1 to 4 or the composition for a heat transfer fluid according to any one of Items 5 to 8 as a heat transfer fluid, wherein the heat transfer mechanism is designed to transfer heat using a heat transfer fluid containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a methoxytridecafluoroheptene isomer mixture.
Item 10. Use of hexafluoropropene trimer represented by _{C 9} F ₁₈ to replace a heat transfer fluid containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and methoxytridecafluoroheptene isomer mixture.
Item 11. A method for transferring heat to or from a device including a heat transfer mechanism designed to transfer heat using a heat transfer fluid containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a methoxytridecafluoroheptene isomer mixture, comprising a step of operating the heat transfer mechanism by using the composition according to any one of Items 1 to 4 or the composition for heat transfer fluid according to any one of Items 5 to 8 in place of the heat transfer fluid.

The present disclosure provides a heat transfer fluid that can replace heat transfer fluids containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a mixture of methoxytridecafluoroheptene isomers.

In this specification, "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist of." In addition, in this specification, when a numerical range is indicated as "A to B," it means A or more and B or less.

1. Composition containing a compound represented by C ₉ F ₁₈
(1) Heat Transfer Fluid The compositions of the present disclosure include a heat transfer fluid compound, which includes a compound represented by C ₉ F ₁₈ .

The compound represented by C ₉ F ₁₈ is preferably a hexafluoropropene (HFP) trimer.

As the hexafluoropropene trimer, any known hexafluoropropene represented by C ₉ F ₁₈ can be widely used, and there is no particular limitation.

Specific examples of such hexafluoropropene trimers include compounds represented by the following formulas (I) to (III).

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

The hexafluoropropene trimer contained in the compound represented by C ₉ F ₁₈ of the present disclosure may be only one of the compounds represented by the above formulas (I) to (III), or may be a mixture containing two or three of these compounds.

When the HFP trimer is a mixture, the blending ratio of the compound represented by the above formula (I) in the whole (i.e., the total of the compounds represented by formulas (I), (II) and (III) contained in the mixture) is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, particularly preferably 45% by mass or more, and even particularly preferably 50% by mass or more, based on the whole HFP trimer. The compound represented by formula (I) is preferably 99% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less (or less), even more preferably 80% by mass or less, particularly preferably 70% by mass or less, and most preferably 60% by mass or less, based on the whole HFP trimer. The blending ratio of the compound represented by the above formula (I) is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, particularly preferably 45% by mass or more, and even more preferably ₅₀ % by mass or more. Relative to the total amount of the compound represented by ₁₈ , for example, 10% by mass or more and 90% by mass or less, 30% by mass or more and 90% by mass or less, 10% by mass or more and 85% by mass or less, 35% by mass or more and 85% by mass or less, 10% by mass or more and less than 85% by mass, 20% by mass or more and less than 85% by mass, 30% by mass or more and less than 85% by mass, 40% by mass or more and less than 85% by mass, 50% by mass or more and less than 85% by mass, 40% by mass or more and less than 85% by mass, 55% by mass or more and 80% by mass or less, 60% by mass or more and 75% by mass or less, or 65% by mass or more and 70% by mass or less, 35% by mass or more and 60% by mass or less, 50% by mass or more and 60% by mass or less, and 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.

Similarly, the compound represented by formula (II) is preferably present in an amount of 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, based on the total amount of the HFP trimer. The compound represented by formula (II) is preferably present in an amount of 70% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total amount of the HFP trimer.

Similarly, the compound represented by formula (III) is preferably present in an amount of 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, based on the total amount of the HFP trimer. The compound represented by formula (III) is preferably present in an amount of 70% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total amount of the HFP trimer.

The mass ratio of the compound represented by formula (II) and the compound represented by formula (III) in the HFP trimer is not particularly limited, but 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.

The content of the compound represented by C ₉ F ₁₈ in the HFP trimer is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, based on the entire heat transfer fluid composition. The content of the compound represented by C ₉ F ₁₈ contained in the heat transfer fluid composition is preferably 99.9999% by mass or less based on the entire heat transfer fluid composition.

The mass ratio of the compound represented by formula (II) and the compound represented by formula (III) in the entire HFP trimer is not particularly limited, but 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.

The HFP trimer may include a hexafluoropropene trimer represented by C ₉ F ₁₈ other than the compounds represented by formulas (I) to (III).

The HFP trimer may also contain hexafluoropropene dimer.

The hexafluoropropene dimer may 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.

The HFP trimer may include a hexafluoropropene tetramer.

Hexafluoropropene tetramer may include 1,1,1,2,5,6,6,6-octafluoro-2,3,5-tris(trifluoromethyl)-4-(perfluoropropyl-2-yl)-3-hexene.

The compounds represented by the above formulas (I) to (III) can be produced by conventional methods, for example, the method described in WO 2018/172919, but are not limited thereto and can be obtained by adopting a wide range of known methods. They may also be obtained by trimerization using HFP as a raw material.

The composition of the present disclosure may include an additional heat transfer fluid compound other than the compound represented by C ₉ F _18. The additional heat transfer fluid compound may be one or more. Examples of the additional heat transfer fluid include perfluorotripropylamine, perfluoropolyether, and methoxy tridecafluoroheptene isomer mixture, perfluorotributylamine, etc.

Perfluorotripropylamine is also called tris(heptafluoropropyl)amine or N,N-bis(heptafluoropropyl)(heptafluoropropyl)amine, and is represented by the general formula: N(CF ₂ CF ₂ CF ₃ ) _n (CF(CF ₃ )CF ₃ ) _3-n (n is an integer of 0 to 3). Perfluorotripropylamine may contain only one type of compound represented by the above general formula, or may contain multiple types. N(CF ₂ CF ₂ CF ₃ ) ₃ is preferred, but N(CF ₂ CF ₂ CF ₃ ) _n (CF(CF ₃ )CF ₃ ) _3-n (n is an integer of 0 to 2) may be contained as an impurity. Specifically, the product name "Fluorinert (registered trademark)" (manufactured by 3M) (FC-3283) and the like can be mentioned.

The perfluoropolyether preferably has the general formula:
RO-Rf ¹ -R'
It is expressed as
In the formula,
R and R' are the same or different and are a monovalent group represented by _{-CmF2m +1} , where m is an integer from 1 to 8, and ^Rf1 is a divalent fluoropolyoxyalkylene group containing 2 to 20 repeating units, the repeating units being:
(i) -CFXO-, where X is F or _CF3 ;
(ii) _-CF2CFXO- (wherein X is F or _CF3 );
(iii) _-CFXCF2O- (wherein X is F or _CF3 );
(iv) -CF ₂ CF ₂ CF ₂ O-; or (v) -CF ₂ CF ₂ CF ₂ CF ₂ O-; or Rf ¹ is
(vi) A divalent group represented by -(CF ₂ ) _n -CFY-O- (wherein n is an integer from 0 to 3, Y is a monovalent group represented by the general formula -ORf ² Z, where Rf ² is a divalent fluoropolyoxyalkylene group containing 2 to ₂₀ repeating units represented by -CFXO-, -CF ₂ CFXO-, -CF ₂ CF ₂ CF ₂ O-, or -CF ₂ CF 2 CF ₂ CF ₂ O-, where each X is the same or different and is F or _CF3 , and Z is a monovalent C _1-5 perfluoroalkyl group).

Specific examples of perfluoropolyethers include products with the names GALDEN (registered trademark) "HT135" and GALDEN (registered trademark) "HT110" (manufactured by Solvay).

The methoxytridecafluoroheptene isomer mixture specifically includes methyl-perfluoroheptene ether (MPHE) (C ₇ F ₁₃ OCH ₃ ). Specific examples include the product name "Opteon SF10" (manufactured by Chemours).

The composition of the present disclosure preferably contains 20% by mass or more of the compound represented by C ₉ F ₁₈ , more preferably 40% by mass or more, even more preferably 60% by mass or more, and most preferably 80% by mass or more, based on the entire heat transfer fluid. However, when perfluorotripropylamine, perfluoropolyether, and methoxytridecafluoroheptene isomer mixture are contained, the properties as a heat transfer fluid of the entire composition are basically unchanged regardless of the content ratio of these, since these and the compound represented by C ₉ F ₁₈ have similar properties as a heat transfer fluid. Therefore, in this case, the composition of the present disclosure preferably contains 40% by mass to 99.9% by mass of the compound represented by C ₉ F ₁₈ , more preferably 60% by mass to 99.9% by mass, and even more preferably 80% by mass to 99.9% by mass, based on the entire heat transfer fluid.

(2) Other Components The compositions of the present disclosure may further comprise other components in addition to the heat transfer fluid compound.

The composition of the present disclosure may contain a stabilizer. The stabilizer exerts a stabilizing effect, thereby functioning as a so-called acid acceptor or antioxidant. The main stabilizing effects include the effect of preventing decomposition of the heat transfer fluid compound by capturing radicals generated in the system, and the acid-accepting effect of preventing further decomposition of the heat transfer fluid compound by the acid by capturing the acid generated in the system.

As such a 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, since they can effectively suppress the occurrence of metal corrosion caused by the composition.

As the unsaturated alcohol-based stabilizer, a wide variety of known stabilizers 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.

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

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

A wide variety of known phenol-based 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.

A wide variety of known epoxy stabilizers 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.

The combination of stabilizers with different stabilizing effects more effectively prevents decomposition of the heat transfer fluid compound, which may occur due to various causes. For this reason, it is preferable to use one or more stabilizers selected from the group consisting of the above-mentioned epoxy stabilizers, as well as unsaturated alcohol stabilizers, nitro stabilizers, and phenol stabilizers.

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

The composition of the present disclosure may contain a compound represented by C _m F _2m and/or C _n F _(2n-2) (wherein m is an integer of 4 or more and 12 or less except 9, and n is an integer of 4 or more and 12 or less).

In the above general formula, m 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. However, m does not include 9.

In the above general formula, 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, it is particularly preferable that n is 9.

In the composition of the present disclosure, the stability of the compound represented by C ₉ F ₁₈ is improved by containing C _m F _2m and/or C _n F _(2n-2) .

The content of C _m F _2m and/or C _n F _(2n-2) is preferably 0.0001 mass % or more based on the total mass of the composition of the present disclosure.

On the other hand, the content of C _m F _2m and/or C _n F _(2n-2) is preferably 10 mass % or less, more preferably 5 mass % or less, and further preferably 1 mass % or less, based on the entire composition of the present disclosure.

In one embodiment, the content of C _m F _2m and/or C _n F _(2n-2) in the composition of the present disclosure is preferably 0.0001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the total of the HFP trimer.

On the other hand, in the composition of the present disclosure, the content of C _m F _2m and/or C _n F _(2n-2) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the total of the HFP trimer.

When multiple types of C _m F _2m and/or C _n F _(2n-2) are contained, the above content means the total amount of these.

By setting the content of C _m F _2m and/or C _n F _(2n-2) within the above range, the decomposition of the HFP trimer represented by C ₉ F ₁₈ can be suppressed, and thus an increase in fluoride ions and an increase in acidity can be suppressed.

The composition of the present disclosure may contain fluoride ions. When fluoride ions are contained, the content is preferably 0.0000001 to 5 mass % and more preferably 0.000001 to 1 mass % based on the entire composition in terms of the thermal stability of the heat transfer fluid during long-term use.

The composition of the present disclosure may contain water. When water is contained, the content of water is preferably 1 to 1000 ppm by mass based on the entire composition in terms of the thermal stability of the heat transfer fluid during long-term use.

In one embodiment, the content of water is preferably 0.0001 parts by mass or _more , more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass in total of the compound represented _by C 9 F 18.

On the other hand, the water content is preferably 10 parts by mass or less _, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, relative to ₁₀₀ parts by mass of the total of the compound represented by C9F18.

The composition of the present disclosure may contain a conductive substance. The conductive substance may be at least one selected from the group consisting of metals, metal ions, metal oxides, metal nitrides, carbon, conductive polymers, and superconducting ceramics, as well as mixtures thereof. When a conductive substance is contained, the content is preferably 10,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, and even more preferably 1 ppm by mass or less, based on the entire composition, in order to suppress defects such as short circuits caused by the intrusion of the conductive substance through gaps in the device.

The composition of the present disclosure may contain insoluble matter. If insoluble matter is contained, the content is preferably 5000 ppm by mass or less, and more preferably 1000 ppm by mass or less, relative to the entire composition, in order to prevent blockage of piping or resistance in the circuit during repeated use.

2. Replacement use for heat transfer fluid The composition of the present disclosure can be used as a replacement composition for heat transfer fluids containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and methoxy tridecafluoroheptene isomer mixture. The composition of the present disclosure can replace the following heat transfer fluids that are currently in practical use.
- perfluorotripropylamine (or tris(heptafluoropropyl)amine, or N,N-bis(heptafluoropropyl)(heptafluoropropyl)amine) [N(CF ₂ CF 2 CF 3 ) n (CF(CF ₃ )CF ₃ ) _3-n (n is an integer from 0 to 3)], represented by _the product name "Fluorinert (registered trademark)" ₍ manufactured by 3M) (FC-3283) _;
- Perfluoropolyethers (PFPEs) such as those represented by the product names GALDEN (registered trademark) "HT135" and GALDEN (registered trademark) "HT110" (manufactured by Solvay), or more specifically, compounds represented by the above general formula: RO-Rf-R', and even more specifically, tetrafluoroethylene oxide polymers and hexafluoropropylene oxide; and - Methoxytridecafluoroheptene isomer mixtures such as those represented by the product name "OpteonSF10" (manufactured by Chemours), or more specifically, methyl-perfluoroheptene ether (MPHE) (C ₇ F ₁₃ OCH ₃ ).

Specifically, in devices designed to transfer heat using the above-mentioned heat transfer fluids, the composition of the present disclosure can be used in place of the heat transfer fluids.

The composition of the present disclosure can be a drop-in replacement, a near drop-in replacement, or a retrofit replacement for the above heat transfer fluids. Note that "drop-in replacement" means that it can be substituted without any changes to the equipment. "Near drop-in replacement" means that it can be substituted with almost no changes to the equipment. "Retrofit replacement" means that it can be substituted with minimal changes (no major changes) to the equipment. The composition of the present disclosure is preferably a drop-in replacement or a near drop-in replacement for the above heat transfer fluids.

Whether or not the composition of the present disclosure can be a drop-in replacement, a near drop-in replacement, or a retrofit replacement can be determined based on whether or not all of the following conditions are satisfied.
(i) The boiling point of the composition of the present disclosure is at least about 80% or more, and preferably at least about 85% or more, of the boiling point of the heat transfer fluid prior to exchange.
(ii) the pour point of the composition of the present disclosure is equal to or less than the pour point of the heat transfer fluid prior to exchange;
(iii) The kinematic viscosity of the composition of the present disclosure is at least about 200% or less, and preferably at least about 150% or less, of the kinematic viscosity of the heat transfer fluid prior to exchange.
(iv) the compositions of the present disclosure are compatible in all proportions with the heat transfer fluid prior to replacement.

By making the boiling point of the composition of the present disclosure at least about 80% or more, preferably at least about 85% or more, of the boiling point of the heat transfer fluid before replacement, it is possible to suppress the occurrence of cavitation and leakage from the device. The upper limit of the boiling point of the heat transfer fluid is not particularly limited, but may be, for example, at least about 130% or less of the boiling point of the heat transfer fluid before replacement.

By setting the pour point of the composition of the present disclosure to be equal to or lower than the pour point of the heat transfer fluid before replacement, it becomes possible to use the composition at temperatures lower than the conventional use temperature, and the use temperature range can be expanded. The upper limit of the pour point of the heat transfer fluid is not particularly limited, but may be, for example, a temperature 30°C higher than the pour point of the heat transfer fluid before replacement.

By setting the kinetic viscosity of the composition of the present disclosure to at least about 200% or less, and preferably at least about 150% or less, of the kinetic viscosity of the heat transfer fluid before replacement, it is possible to suppress an increase in power consumption or reduce power consumption. It is preferable to compare the kinetic viscosity at the operating temperature, but this is not limited thereto, and the kinetic viscosity can be compared at any temperature between -20°C and -40°C, specifically at -20°C, for example.

The composition of the present disclosure is compatible with the heat transfer fluid being replaced in any proportion, making replacement easy.

Furthermore, the composition of the present disclosure satisfies the following conditions, making it more suitable as a drop-in replacement, near drop-in replacement, or retrofit replacement.
(v) The composition of the present disclosure has a dielectric constant that is 120% or less than that of the heat transfer fluid prior to replacement.
(vi) The composition of the present disclosure has a dielectric strength of at least 90% of the heat transfer fluid prior to replacement.
(vii) The composition of the present disclosure has a specific heat of 90% or more of the heat transfer fluid prior to exchange.
(viii) the composition of the present disclosure has a thermal conductivity of at least 85% of the heat transfer fluid prior to replacement.

By setting the dielectric constant of the composition of the present disclosure to 120% or less of the dielectric constant of the heat transfer fluid before replacement, the composition can be suitably used as a replacement composition. The upper limit of the dielectric constant of the heat transfer fluid is not particularly limited, but may be, for example, 80% or more of the dielectric constant of the heat transfer fluid before replacement.

By making the dielectric strength of the composition of the present disclosure 90% or more of the dielectric strength of the heat transfer fluid before replacement, it can be suitably used as a replacement composition. The upper limit of the dielectric strength of the heat transfer fluid is not particularly limited, but may be, for example, 120% or less of the dielectric strength of the heat transfer fluid before replacement.

By making the specific heat of the composition of the present disclosure 90% or more of the specific heat of the heat transfer fluid before replacement, it can be suitably used as a replacement composition. There is no particular upper limit to the specific heat of the heat transfer fluid, but it may be, for example, 120% or less of the specific heat of the heat transfer fluid before replacement.

By making the thermal conductivity of the composition of the present disclosure 85% or more of the thermal conductivity of the heat transfer fluid before replacement, it can be suitably used as a replacement composition. The upper limit of the thermal conductivity of the heat transfer fluid is not particularly limited, but may be, for example, 120% or less of the thermal conductivity of the heat transfer fluid before replacement.

The boiling point of the composition of the present disclosure may be preferably 105°C or higher, more preferably 108°C or higher. The upper limit of the boiling point of the composition of the present disclosure is not particularly limited, but may be, for example, 150°C or lower, 130°C or lower, or 120°C or lower.

The pour point of the composition of the present disclosure may preferably be -80°C or lower, more preferably -100°C or lower, and even more preferably -110°C or lower. The lower limit of the pour point of the composition of the present disclosure is not particularly limited, but may be, for example, -180°C or higher, or -160°C or higher.

The kinematic viscosity of the composition of the present disclosure at -20°C may be preferably 6.0 cSt or less, more preferably 5.0 cSt or less, even more preferably 4.0 cSt or less, and even more preferably 3.0 cSt or less. The lower limit of the kinematic viscosity of the composition of the present disclosure is not particularly limited, but may be, for example, 1.0 cSt or more.

The dielectric constant of the composition of the present disclosure may be preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. The lower limit of the dielectric constant of the composition of the present disclosure is not particularly limited, but may be, for example, 1.1 or more.

The dielectric strength of the composition of the present disclosure may be preferably 40 kV or more, more preferably 50 kV or more, and even more preferably 50 kV or more. The upper limit of the dielectric strength of the composition of the present disclosure is not particularly limited, but may be, for example, 150 kV or less, or 100 kV or less.

The specific heat of the composition of the present disclosure may be, at 30°C, preferably 800 J/kg·K or more, more preferably 900 J/kg·K or more, and even more preferably 1000 J/kg·K or more. The upper limit of the specific heat of the composition of the present disclosure is not particularly limited, but may be, for example, 2000 J/kg·K or less, or 1500 J/kg·K or less.

The thermal conductivity of the composition of the present disclosure at 30°C may be preferably 0.055 W/mK or more, more preferably 0.060 W/mK or more, and even more preferably 0.065 W/mK or more. The upper limit of the thermal conductivity of the composition of the present disclosure is not particularly limited, but may be, for example, 0.090 W/mK or less, or 0.080 W/mK or less.

The boiling point of the composition of the present disclosure is the temperature at which a peak due to endothermic heat is observed when the temperature is increased from 25°C at 5°C/min using DSC (differential scanning calorimetry).

The pour point of the composition of the present disclosure is the temperature at which an endothermic peak is observed when the composition is cooled to below the freezing point with liquid nitrogen and then heated at a rate of 5°C/min using DSC.

The dielectric constant of the composition disclosed herein is the value observed using a capacitance method at a temperature of 25°C, a humidity of 60%, and a frequency of 1 kHz.

The kinematic viscosity and density of the compositions disclosed herein were measured using an Anton Paar SVM3001 kinematic viscometer.

The dielectric strength of the composition of the present disclosure is the dielectric breakdown voltage when a liquid sample is immersed between spherical electrodes adjusted to a predetermined distance and the voltage is increased at a constant rate. The measurement conditions are as follows:
Electrode shape: spherical (φ12.5mm)
Electrode spacing: 2.5mm
Voltage rise rate: 2 kV/sec Measurement atmosphere: in air (22°C, 57% RH)

The specific heat of the composition of the present disclosure is a value obtained using DSC under the following conditions:
Measurement device: Perkin-Elmer differential scanning calorimeter DSC8500
Heating rate: 10°C/min. Standard sample: sapphire (-Al2O3)
Atmosphere: Dry nitrogen gas flow Sample container: Aluminum airtight container

The thermal conductivity of the composition disclosed herein is a value obtained by the unsteady thin wire method.

The compatibility of the composition of the present disclosure is determined by whether or not it is compatible when mixed with the target solvent. Compatibility here means that when the two are mixed together, they become homogeneous, i.e., there is no phase separation.

3. Devices Comprising Heat Transfer Fluids The devices of the present disclosure comprise the compositions of the present disclosure.

The apparatus of the present disclosure includes a device having a heat transfer mechanism for transferring heat to or from the device.

Specifically, the device of the present disclosure that includes a heat transfer mechanism includes a device and a heat transfer mechanism that transfers heat to or from the device using the composition of the present disclosure as a heat transfer fluid, and the heat transfer mechanism is designed to transfer heat using a heat transfer fluid that includes at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a methoxytridecafluoroheptene isomer mixture.

Devices include, for example, computers, servers including server computers and 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.

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

When the device is a server computer, one or more 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, for example, a chipset; memory, graphics chips, network chips, RAM, power supplies, daughter cards; storage drives, such as solid state drives, mechanical hard disks, etc.

The heat transfer mechanism is a heat transfer mechanism for transferring heat between an object to which heat is transferred using the composition of the present disclosure, and transfers heat by thermal contact with the object to which heat is transferred. For example, cooling is used when heat is removed from the object to which heat is transferred, and heating is used when heat is supplied. Different mechanisms may be used depending on the case, but one heat transfer mechanism may be used to cover both cooling and heating.

Heat transfer mechanisms 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.

More specifically, these include temperature controlled wafer chucks in plasma enhanced chemical vapor deposition (PECVD) tools, temperature controlled test heads for die performance testing, temperature controlled work areas in semiconductor processing equipment, thermal shock test bath fluid reservoirs, thermostatic chambers, etc.

The object to which heat is transferred, which is brought into thermal contact with the heat transfer mechanism, is an article, device, or atmosphere that is to be 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 this disclosure include, but are not limited to, microprocessors, wafers used to manufacture semiconductor devices, power control semiconductors, electrical branch switches, power transformers, circuit boards, multi-chip modules, mounted and unmounted semiconductor devices, chemical reactors, nuclear reactors, fuel cells, heat exchangers, electrochemical cells, lasers, and missile parts.

When using the device of the present disclosure, the temperature conditions for the composition of the present disclosure are preferably -100 to 100°C, more preferably -90 to 90°C, and even more preferably -70 to 90°C. The composition of the present disclosure has the advantage of exhibiting low kinetic viscosity even at low temperatures below -20°C, and especially at -70 to -60°C, so that the device can be suitably used even in the above temperature range.

The equipment of the present disclosure further includes two-phase immersion cooling fluids, chiller fluids, and Rankine cycle working fluids, etc.

4. Heat Transfer Method The heat transfer method of the present disclosure is a heat transfer method comprising a step of transferring heat in a device designed to transfer heat using a heat transfer fluid containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a methoxytridecafluoroheptene isomer mixture, by replacing the heat transfer fluid with the composition of the present disclosure.

The equipment includes devices having a device and a heat transfer mechanism for transferring heat to or from the device, two-phase immersion cooling fluids, chiller fluids, and Rankine cycle working fluids.

In the above, the device includes the device described in "3. Equipment containing a heat transfer fluid". When the above device is used, the heat transfer method of the present disclosure is a heat transfer method that includes a step of transferring heat to or from a device that includes a heat transfer mechanism designed to transfer heat using a heat transfer fluid containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a methoxytridecafluoroheptene isomer mixture, by operating the heat transfer mechanism using the composition of the present disclosure instead of the heat transfer fluid.

In the heat transfer methods of the present disclosure above, heat may be transferred by placing a heat transfer mechanism in thermal contact with a device. When the heat transfer mechanism is placed in thermal contact with the device, it removes heat from the device, 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 mechanism.

Although the embodiments of the present invention have been described above, the present invention is not limited to these examples, and can of course be embodied in various forms without departing from the spirit of the present invention.

The following provides a more detailed explanation of the present invention based on examples, but the present invention is not limited to these.

Example 1
The heat transfer fluid composition of Example 1 was obtained based on the method described in Chem Ber 1973, 106, 2950-2959. The obtained HFP trimer was purified by distillation to remove impurities such as hexafluoropropene dimers and tetramers. The purified HFP trimer was further separated into compounds represented by formulas (I), (II) and (III) by distillation. Each of the separated HFP trimers was dehydrated using silica gel.

The compounds represented by formulas (I), (II), and (III) obtained above were mixed so that the ratios of the compounds represented by formulas (I), (II), and (III) were as shown in the table below, to obtain the trimer mixtures of Examples 1 to 4.

量％含まれていることが確認された。

It was confirmed that it contained % by volume.

<Comparative Example 1>
As Comparative Example 1, FC-3283 manufactured by 3M was prepared, which did not contain the compounds represented by (I), (II) and (III).

<Comparative Example 2>
As Comparative Example 2, HFE7100 manufactured by 3M was prepared, which did not contain the compounds represented by (I), (II) and (III).

The compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated for boiling point, pour point, dielectric constant, kinetic viscosity, dielectric strength, specific heat, thermal conductivity, and compatibility.

<Boiling point, pour point and dielectric constant measurement>
The boiling point of the trimer mixture was measured by differential scanning calorimetry (DSC) at the temperature at which a peak due to endothermic heat was observed when the mixture was heated from 25° C. at 5° C./min. The pour point was measured by DSC at the temperature at which a peak due to endothermic heat was observed when the mixture was cooled to below the freezing point with liquid nitrogen and then heated at 5° C./min. The dielectric constant was measured at a frequency of 1 kHz by a capacitance method in an environment of 25° C. and 60% humidity.

<Kinematic Viscosity and Density Measurement>
The kinematic viscosity and density of the trimer mixture were measured using an Anton Paar SVM3001 kinematic viscometer.

<Dielectric strength measurement>
The liquid sample was immersed between spherical electrodes adjusted to a predetermined distance, and the dielectric strength of the trimer mixture was measured as the dielectric breakdown voltage when the voltage was increased at a constant rate. The detailed measurement conditions were as follows:
Electrode shape: spherical (φ12.5mm)
Electrode spacing: 2.5mm
Voltage rise rate: 2 kV/sec Measurement atmosphere: in air (22°C, 57% RH)

<Specific heat measurement>
The specific heat of the trimer mixture was measured using DSC under the following conditions:
Measurement device: Perkin-Elmer differential scanning calorimeter DSC8500
Heating rate: 10°C/min. Standard sample: sapphire (-Al2O3)
Atmosphere: Dry nitrogen gas flow Sample container: Aluminum airtight container

<Thermal conductivity measurement>
The thermal conductivity of the trimer mixture was measured by the transient hot-wire method.

<Compatibility>
The compatibility of the trimer mixtures was evaluated by mixing equal amounts of each of the trimer mixtures with the following three solvents:
Galden HT135 (Solvay)
SF-10 (manufactured by Chemours)
FC3283 (manufactured by 3M)

Claims (9)

A composition comprising a hexafluoropropene trimer represented by C ₉ F ₁₈ for use as a replacement for a heat transfer fluid comprising at least one member selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a mixture of methoxytridecafluoroheptene isomers,
The content of the hexafluoropropene trimer represented by C ₉ F ₁₈ is 80 mass% or more based on the total mass of the composition,
The hexafluoropropene trimer represented by C ₉ F ₁₈ is represented by the following formulas (I) to (III):

The compound includes at least one compound selected from the group consisting of compounds represented by
A composition, wherein the content of the compound represented by the formula (I) is 30% by mass or more and less than 85% by mass based on the total amount of the hexafluoropropene trimer represented by C ₉ F _18. The composition according to claim 1 , which satisfies the following conditions (i) to (iv) :
(i) The boiling point is 80% or more of the boiling point of the heat transfer fluid.
(ii) the pour point is equal to or less than the pour point of said heat transfer fluid;
(iii) the kinetic viscosity is 200% or less of the kinetic viscosity of the heat transfer fluid;
(iv) be miscible in any proportion with said heat transfer fluid; The present invention relates to a hexafluoropropene trimer represented by C ₉ F ₁₈ , and at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a mixture of methoxytridecafluoroheptene isomers;
A heat transfer fluid composition, wherein the content of the hexafluoropropene trimer represented by C ₉ F ₁₈ is 80 mass % or more. The heat transfer fluid composition according to claim 3, wherein the hexafluoropropene trimer represented by C ₉ F ₁₈ comprises at least one compound selected from the group consisting of compounds represented by the following formulas (I) to (III):

The heat transfer fluid composition according to claim 4, wherein the compound contains less than 85 mass% of the compound represented by formula (I) based on the total amount of the hexafluoropropene trimer represented by _{C9F18 .} The heat transfer fluid composition according to claim 4, wherein the compound contains 85 mass% or more of the compound represented by formula (I) based on the total amount of the hexafluoropropene trimer represented by _{C9F18 .} A device including a heat transfer mechanism, comprising: a device; and a heat transfer mechanism that transfers heat to or from the device using the composition according to claim 1 or the composition for heat transfer fluid according to claim 3 or 4 as a heat transfer fluid, the heat transfer mechanism being designed to transfer heat using a heat transfer fluid containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a mixture of methoxytridecafluoroheptene isomers. Use of a hexafluoropropene trimer represented by C ₉ F ₁₈ to replace a heat transfer fluid containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a mixture of methoxytridecafluoroheptene isomers,
The hexafluoropropene trimer represented by C ₉ F ₁₈ is represented by the following formulas (I) to (III):

The compound includes at least one compound selected from the group consisting of compounds represented by
The content of the compound represented by the formula (I) is 30 mass % or more and less than 85 mass % based on the total hexafluoropropene trimer represented by C ₉ F _18. A method of heat transfer comprising the step of transferring heat to or from a device including a heat transfer mechanism designed to transfer heat using a heat transfer fluid containing at least one selected from the group consisting of perfluorotripropylamine, perfluoropolyether, and a mixture of methoxytridecafluoroheptene isomers, by operating the heat transfer mechanism using the composition according to claim 1 or the composition for heat transfer fluid according to claim 3 or 4 in place of the heat transfer fluid.