JP2013151683A - 熱伝達組成物 - Google Patents
熱伝達組成物 Download PDFInfo
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- JP2013151683A JP2013151683A JP2013029366A JP2013029366A JP2013151683A JP 2013151683 A JP2013151683 A JP 2013151683A JP 2013029366 A JP2013029366 A JP 2013029366A JP 2013029366 A JP2013029366 A JP 2013029366A JP 2013151683 A JP2013151683 A JP 2013151683A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D7/50—Solvents
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
- F03C—POSITIVE-DISPLACEMENT ENGINES DRIVEN BY LIQUIDS
- F03C99/00—Subject matter not provided for in other groups of this subclass
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- G—PHYSICS
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- G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
- G06Q30/00—Commerce
- G06Q30/018—Certifying business or products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
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Abstract
【解決手段】(i)トランス‐1,3,3,3‐テトラフルオロプロペン(R‐1234ze(E));(ii)ジフルオロメタン(R‐32)、プロペン(R‐1270)、プロパン(R290)およびそれらの混合物から選択される第二成分;(iii)ペンタフルオロエタン(R‐125)、1,1,1,2‐テトラフルオロエタン(R‐134a)およびそれらの混合物から選択される第三成分;および所望により、(iv)フルオロエタン(R‐161)、1,1‐ジフルオロエタン(R‐152a)およびそれらの混合物から選択される第四成分;を含んでなる熱伝達組成物である。
【選択図】なし
Description
フルオロカーボン燃焼化学は複雑かつ予測不能である。不燃性フルオロカーボンと可燃性フルオロカーボンとの混合が流体の燃焼性を減らす、または空気中における可燃性組成物の範囲を減らすとは、必ずしも限らない。例えば、不燃性R‐134aが可燃性R‐152aと混合されると、該混合物の可燃下限が予測不能なように変化することを、本発明者らは発見した。三元または四元組成物が考えられると、状況はより一層複雑で予測しづらくなる。
(i)トランス‐1,3,3,3‐テトラフルオロプロペン(R‐1234ze(E))、
(ii)ジフルオロメタン(R‐32)、プロペン(R‐1270)、プロパン(R290)およびそれらの混合物から選択される第二成分、
(iii)ペンタフルオロエタン(R‐125)、1,1,1,2‐テトラフルオロエタン(R‐134a)およびそれらの混合物から選択される第三成分、および所望により、
(iv)フルオロエタン(R‐161)、1,1‐ジフルオロエタン(R‐152a)およびそれらの混合物から選択される第四成分
を含んでなる熱伝達組成物を提供することにより、上記欠点に対処したものである。
(i)2,3,3,3‐テトラフルオロプロペン(R‐1234yf)、
(ii)シス‐1,3,3,3‐テトラフルオロプロペン(R‐1234ze(Z))、および/または
(iii)3,3,3‐トリフルオロプロペン(R‐1243zf)
を含有しなくてもよい。
R‐407A 1990
R‐407B 2695
R‐407C 1653
R‐404A 3784
R507 3850
既存の化合物または組成物はフルオロカーボン化合物、例えばペルフルオロ‐、ヒドロフルオロ‐、クロロフルオロ‐またはヒドロクロロフルオロ‐カーボン化合物を含んでなるか、またはそれはフッ素化オレフィンを含んでなる。
R‐32 30%、R‐125 25%、R‐134a 25%およびR‐1234ze(E) 20%(重量基準)を含んでなる組成物の性能を、中温度および低温冷却用途のモデルにした(“ブレンドA”)。選択されたサイクル条件は以下であった:
(a)中温度用途
平均凝縮温度 40℃
平均蒸発温度 −10℃
吸引ラインリターン温度 15℃
過冷 5K
蒸発器過熱 5K
圧縮器(等エントロピー)効率 65%
冷却力(Cooling duty) 10kW
吸引ライン管直径 22.7mm
平均凝縮温度 40℃
平均蒸発温度 −35℃
吸引ラインリターン温度 −10℃
過冷 5K
蒸発器過熱 5K
圧縮器(等エントロピー)効率 65%
冷却力 10kW
吸引ライン管直径 22.7mm
圧縮器温度を制御するための液体注入の開始温度:130℃
表1の場合と同一の条件で、能力、エネルギー効率および吸引ライン圧力降下の比較のために参照流体としてR‐407Cを用いて、範囲20〜35%w/wでR‐32;範囲15〜30%w/wでR‐125;範囲15〜50%w/wでR‐134aおよび残部であるR‐1234zeを含んでなる本発明の別な組成物について性能をモデル化した。本発明の組成物は、R‐407A、R‐407CまたはR‐404Aより低いGWPおよび低い全体TEWIで、許容しうるまたは改善された性能を呈する。
以下でさらに詳細に説明されているように、本発明の別な組成物について性能をモデル化した。用いられたモデルの誘導法は次の通りである。
上記モデルを用いて、16〜40重量%のR‐32、10〜24重量%のR‐125、16〜28重量%のR‐134aおよび8〜56重量%のR‐1234ze(E)を含有している本発明の選択組成物の性能が下記表3〜34で示されている。
‐匹敵しうる能力で改善されたエネルギー効率
‐改善された体積効率および低い圧力比
‐システムの高圧ラインから冷媒の漏出の可能性減少
‐冷媒の直接GWP減少
という理由から、匹敵する公知のHFC冷媒(例えば、R‐407A、R‐407FおよびR‐404a)と比較した場合に、非常に予想外な有意の改善された環境性能を発揮している。
実施例3で前述されたものと同一の冷却サイクル条件を用いて、20〜46重量%のR‐32、10〜60重量%のR‐161、10〜22重量%のR‐134aおよび8〜60重量%のR‐1234ze(E)を含有する本発明の選択組成物の分析が行われた。結果が下記表35〜105で示されている(参考のため前記表X参照)。
実施例3で前述されたものと同一の冷却サイクル条件を用いて、16〜40重量%のR‐32、10〜30重量%のR‐161、10〜25重量%のR‐125および10〜64重量%のR‐1234ze(E)を含有する本発明の選択組成物の分析が行われた。結果が下記表106〜124で示されている(参考のため前記表X参照)。
Claims (63)
- (i)トランス‐1,3,3,3‐テトラフルオロプロペン(R‐1234ze(E))、
(ii)ジフルオロメタン(R‐32)、プロペン(R‐1270)、プロパン(R290)およびそれらの混合物から選択される第二成分、
(iii)ペンタフルオロエタン(R‐125)、1,1,1,2‐テトラフルオロエタン(R‐134a)およびそれらの混合物から選択される第三成分、および所望により
(iv)フルオロエタン(R‐161)、1,1‐ジフルオロエタン(R‐152a)およびそれらの混合物から選択される第四成分、
を含んでなる熱伝達組成物。 - 約5〜約50重量%のR‐1234ze(E)を含んでなる、請求項1に記載の組成物。
- 約10〜約40重量%の第二成分を含んでなる、請求項1または2に記載の組成物。
- 約10〜約80重量%の第三成分を含んでなる、請求項1〜3のいずれか一項に記載の組成物。
- 第二成分がR‐32を含んでなる、請求項1〜4のいずれか一項に記載の組成物。
- 第三成分がR‐125およびR‐134aである、請求項1〜5のいずれか一項に記載の組成物。
- R‐1234ze(E)、R‐32、R‐125およびR‐134aを含んでなる、請求項1〜6のいずれか一項に記載の組成物。
- 約5〜約40重量%のR‐1234ze(E)、約20〜約35重量%のR‐32、約15〜約30重量%のR‐125および約12〜約50重量%のR‐134aを含んでなる、請求項7に記載の組成物。
- 約10〜約50重量%のR‐1234ze(E)、約22〜約40重量%のR‐32、約10〜約30重量%のR‐125および約15〜約30重量%のR‐134aを含んでなる、請求項7に記載の組成物。
- 第四成分としてR‐161を含んでなる、請求項1〜5のいずれか一項に記載の組成物。
- R‐1234ze(E)、R‐32、R‐134aおよびR‐161を含んでなる、請求項10に記載の組成物。
- 約5〜約60重量%のR‐1234ze(E)、約20〜約50重量%のR‐32、約10〜約60重量%のR‐161および約10〜約40重量%のR‐134aを含んでなる、請求項11に記載の組成物。
- 約30〜約60重量%のR‐1234ze(E)、約20〜約50重量%のR‐32、約10〜約30重量%のR‐161および約10〜約25重量%のR‐134aを含んでなる、請求項12に記載の組成物。
- R‐1234ze(E)、R‐32、R‐125およびR‐161を含んでなる、請求項10に記載の組成物。
- 約10〜約65重量%のR‐1234ze(E)、約15〜約40重量%のR‐32、約10〜約30重量%のR‐161および約10〜約25重量%のR‐125を含んでなる、請求項14に記載の組成物。
- 約25〜約60重量%のR‐1234ze(E)、約20〜約40重量%のR‐32、約10〜約20重量%のR‐161および約10〜約25重量%のR‐125を含んでなる、請求項15に記載の組成物。
- 組成物が2800未満、好ましくは1500未満のGWPを有している、請求項1〜16のいずれか一項に記載の組成物。
- 温度勾配が約15K未満、好ましくは約10K未満である、請求項1〜17のいずれか一項に記載の組成物。
- 組成物が、置き換えようと意図される既存の冷媒の約15%以内、好ましくは約10%以内の体積冷却能力を有している、請求項1〜18のいずれか一項に記載の組成物。
- 組成物がR‐32単独よりも可燃性が低い、請求項1〜19のいずれか一項に記載の組成物。
- 組成物が、R‐32単独と比べて、
(a)高い可燃限界、
(b)高い点火エネルギー、および/または
(c)低い火炎速度、
を有している、請求項20に記載の組成物。 - 不燃性である、請求項20または21に記載の組成物。
- 組成物が、置き換えようと意図される既存の冷媒の約10%以内のサイクル効率を有している、請求項1〜22のいずれか一項に記載の組成物。
- 組成物が、置き換えようと意図される既存の冷媒の約15K以内、好ましくは約10K以内の圧縮器吐出温度を有している、請求項1〜23のいずれか一項に記載の組成物。
- 潤滑剤と、請求項1〜24のいずれか一項に記載の組成物を含んでなる、組成物。
- 潤滑剤が、鉱油、シリコーン油、ポリアルキルベンゼン類(PABs)、ポリオールエステル類(POEs)、ポリアルキレングリコール類(PAGs)、ポリアルキレングリコールエステル類(PAGエステル類)、ポリビニルエーテル類(PVEs)、ポリ(アルファ‐オレフィン類)およびそれらの組合せから選択される、請求項25に記載の組成物。
- 安定剤をさらに含んでなる、請求項25または26に記載の組成物。
- 安定剤が、ジエン系化合物類、ホスフェート類、フェノール化合物類およびエポキシド類とそれらの混合物から選択される、請求項27に記載の組成物。
- 難燃剤と、請求項1〜28のいずれか一項に記載の組成物を含んでなる、組成物。
- 追加の難燃剤が、トリ(2‐クロロエチル)ホスフェート、(クロロプロピル)ホスフェート、トリ(2,3‐ジブロモプロピル)ホスフェート、トリ(1,3‐ジクロロプロピル)ホスフェート、リン酸二アンモニウム、様々なハロゲン化芳香族化合物、酸化アンチモン、アルミニウム三水和物、ポリ塩化ビニル、フッ素化ヨードカーボン、フッ素化ブロモカーボン、トリフルオロヨードメタン、ペルフルオロアルキルアミン類、ブロモ‐フルオロアルキルアミン類およびそれらの混合物からなる群より選択される、請求項29に記載の組成物。
- 冷媒組成物である、請求項1〜30のいずれか一項に記載の組成物。
- 請求項1〜31のいずれか一項に記載の組成物を含有している、熱伝達装置。
- 熱伝達装置における、請求項1〜31のいずれか一項に記載の組成物の使用。
- 冷却装置である、請求項32または33に記載の熱伝達装置。
- 自動車空調システム、住宅用空調システム、業務用空調システム、住宅用冷蔵庫システム、住宅用冷凍庫システム、業務用冷蔵庫システム、業務用冷凍庫システム、冷却機空調システム、冷却機冷却システムと、業務用または住宅用ヒートポンプシステムからなる群より選択される、請求項34に記載の熱伝達装置。
- 圧縮器を内蔵している、請求項34または35に記載の熱伝達装置。
- 請求項1〜31のいずれか一項に記載の組成物を含んでなる、発泡剤。
- 発泡体を形成可能な1種以上の成分と請求項1〜31のいずれか一項に記載の組成物とを含んでなる発泡性組成物であって、発泡体を形成可能な1種以上の成分が、ポリウレタン類、熱可塑性ポリマーおよび樹脂、例えばポリスチレン、およびエポキシ樹脂、ならびにそれらの混合物から選択される、発泡性組成物。
- 請求項38に記載の発泡性組成物から得られる、発泡体。
- 請求項1〜31のいずれか一項に記載の組成物を含んでなる、請求項39に記載の発泡体。
- スプレーされるべき物質と、請求項1〜31のいずれか一項に記載の組成物を含んでなる噴射剤とを含んでなる、スプレー用組成物。
- 請求項1〜31のいずれか一項に記載の組成物を凝縮させ、その後、冷却されるべき物品の近くで該組成物を蒸発させることを含んでなる、物品を冷却する方法。
- 加熱されるべき物品の近くで請求項1〜31のいずれか一項に記載の組成物を凝縮させ、その後、該組成物を蒸発させることを含んでなる、物品を加熱する方法。
- 請求項1〜31のいずれか一項に記載の組成物を含んでなる溶媒とバイオマスを接触させ、該溶媒から物質を分離することを含んでなる、バイオマスから物質を抽出する方法。
- 請求項1〜31のいずれか一項に記載の組成物を含んでなる溶媒と物品を接触させることを含んでなる、物品を清浄化する方法。
- 請求項1〜31のいずれか一項に記載の組成物を含んでなる溶媒と水溶液を接触させ、該溶媒から物質を分離することを含んでなる、水溶液から物質を抽出する方法。
- 請求項1〜31のいずれか一項に記載の組成物を含んでなる溶媒と粒状固体マトリックスを接触させ、該溶媒から物質を分離することを含んでなる、粒状固体マトリックスから物質を抽出する方法。
- 請求項1〜31のいずれか一項に記載の組成物を含有している、機械的動力発生装置。
- ランキンサイクルまたはその変法を用いて熱から動力を発生するように構成されている、請求項48に記載の機械的動力発生装置。
- 既存の熱伝達流体を除去して、請求項1〜31のいずれか一項に記載の組成物を導入する工程を含んでなる、熱伝達装置を改修する方法。
- 熱伝達装置が冷却装置である、請求項50に記載の方法。
- 熱伝達装置が空調システムである、請求項51に記載の方法。
- 既存の化合物または組成物を含んでなる製品の取扱いから生じる環境影響を減らす方法であって、少なくとも部分的に既存の化合物または組成物を請求項1〜31のいずれか一項に記載の組成物で置き換えることを含んでなる、方法。
- 組成物または熱伝達装置がR‐134aを含有する、請求項1〜31のいずれか一項に記載の組成物、および/または請求項32または34〜36のいずれか一項に記載の熱伝達装置を製造する方法であって、R‐1243ze(E)、第二成分、所望によりR‐125、所望により第四成分、および所望により潤滑剤、安定剤および/または追加の難燃剤を、R‐134aである既存の熱伝達流体を含有した熱伝達装置へ導入することを含んでなる、方法。
- R‐1243ze(E)、第二成分、所望によりR‐125、所望により第四成分、および所望により潤滑剤、安定剤および/または追加の難燃剤を導入する前に、既存のR‐134aの少なくとも一部を熱伝達装置から除去する工程を含んでなる、請求項54に記載の方法。
- (i)既存の化合物または組成物を請求項1〜31のいずれか一項に記載の組成物で置き換え、このとき請求項1〜31のいずれか一項に記載の組成物は既存の化合物または組成物より低いGWPを有しているものとし、(ii)該置き換え工程で温室効果ガス排出権を得ることを含んでなる、温室効果ガス排出権を生み出す方法。
- 本発明の組成物の使用が、既存の化合物または組成物の使用により達成される場合と比べて、より低い総等価温暖化影響および/またはより低いライフサイクル炭素排出量をもたらす、請求項56に記載の方法。
- 空調、冷却、熱伝達、発泡剤、エアロゾルまたはスプレー用噴射剤、気体誘電体、凍結手術、獣医処置、歯科処置、消火、火炎抑制、溶媒、クリーナー、エアホーン、ペレットガン、局所麻酔剤および膨張用途の分野からの製品で行われる、請求項56または57の方法。
- 製品が熱伝達装置、発泡剤、発泡性組成物、スプレー用組成物、溶媒または機械的動力発生装置から選択される、請求項53または58に記載の方法。
- 製品が熱伝達装置である、請求項59に記載の方法。
- 既存の化合物または組成物が熱伝達組成物である、請求項53および56〜60のいずれか一項に記載の方法。
- 熱伝達組成物が、R‐22、R‐410A、R‐407A、R‐407B、R‐407C、R507およびR‐404aから選択される冷媒である、請求項61に記載の方法。
- 所望により実施例を参照しつつ、実質的にここまでに記載されるような、あらゆる新規の熱伝達組成物。
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