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TW200418970A - Pentafluoropropene-based compositions - Google Patents

Pentafluoropropene-based compositions Download PDF

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Publication number
TW200418970A
TW200418970A TW092129751A TW92129751A TW200418970A TW 200418970 A TW200418970 A TW 200418970A TW 092129751 A TW092129751 A TW 092129751A TW 92129751 A TW92129751 A TW 92129751A TW 200418970 A TW200418970 A TW 200418970A
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TW
Taiwan
Prior art keywords
composition
weight
azeotrope
hfo
hfc
Prior art date
Application number
TW092129751A
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English (en)
Inventor
Rajiv R Singh
Hang T Pham
David P Wilson
Original Assignee
Honeywell Int Inc
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=32179849&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=TW200418970(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Honeywell Int Inc filed Critical Honeywell Int Inc
Publication of TW200418970A publication Critical patent/TW200418970A/zh

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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02803—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing fluorine
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    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N29/00—Biocides, pest repellants or attractants, or plant growth regulators containing halogenated hydrocarbons
    • A01N29/02—Acyclic compounds or compounds containing halogen attached to an aliphatic side-chain of a cycloaliphatic ring system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • 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
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Description

200418970 玖、發明說明： 此申請案係關於及申請優先權於美國臨時申請按序號 60/421，435 號及 60/421，263 號，其各申請於 2⑻2，μ 美國專利商標局，並以引用方式併入本文供參考。本案 亦關於以引用方式併入下列各目前申請中美國專利申請 案：代理人檔案號Η00044 ^(26,269)標題為，，氟化鏈烯^ 凍劑組合物’’，Raymond Thomas及：代理人檔案號 H0003789(26,267)標題為，，製造氟丙烯之方法”，Hsueh Sung Tung等人。 【發明所屬之技術領域】 本發明通常關於五氟丙烯之組合物。明確而言，本發 明提供一種包含五氟丙烯之似共沸組合物及其用途。 【先前技術】 氟碳為主流體在工業界具有廣泛用途，包括作為冷凍 劑、氣溶膠推進劑、吹製劑、熱轉移媒介及氣態介電質。 由於使用此等流體相關的環保問題，最好使用低或零臭 氧消耗潛力的流體如氫氟碳（“HFC，S”）。因此使用不含氯 氟碳（“CFCs”）或氫氯氟碳（“HCFCs”）之流體較佳。此外最 好使用在沸騰及蒸發時不會分餾的單一成分流體或共沸 混合物。然而’經證實新穎、環境上安全、非分餾性混 a物很複雜，因為共沸物之形成不易預期。 工業界持續尋求新穎氟碳為主混合物，其提供替代 性，且在環境上被視為對〇〇及HCFC0^安全取代物。 特別是含有低臭氧消耗潛力的氫氟碳之混合物。該混合
O:\88\88927 DOC 200418970 物為本發明之主題。 【發明内容】 本發明人等發展可滿足對CFCs及HCFCs取代物持續 需要之組合物。在某些具體例中，本發明提供一種似共 沸組合物，包含五氟丙烯（HFO-1225)與一種選自由3,3,3-三氟丙烯（”HF〇-1243zf”）、1，1-二氟乙烷（"HFC-152a”）、 反式]，3,3,3-四氟丙烯（”HF〇-1234ze”）及其二種或多種 之組合所組成之群之流體所組成。因此，本發明可藉提 供貫質上不具CFCs及HCFCs且顯示相當固定沸點及蒸氣 壓力特性之似共沸組合物。 【實施方式】 本文所用對五氟丙烯之術語”（hf〇-1225)"意指涵蓋所 包括，例如， 1，1，1，2,3-五氟丙稀
溫度下相等。實務上， 定歷:力與 此意指共沸混合物之成分為恆沸 有五氣丙細之異構物， (nHFO-1225yen)，以及 1 與1，1，2,3,3-五氟丙稀（” 且無法在相改變期間分離。 似共沸組合物為恆沸或大體 共彿組合物， 上恆沸。 在沸騰或蒸發期間形成 。換言之，關於似 之洛氣之组合物相
O:\88\88927 DOC 200418970 同或貫質上相同於最初液態組合物。因此，隨著沸騰或 蒸發’液態組合物改變僅最小或可忽視的程度。此對照 於非似共沸組合物，其中，在沸騰或蒸發期間，液態組 合物改變相當程度。所有本發明似共沸組合物在指定範 圍内以及某種組合物在此範圍外皆為似共沸。 本發明之似共沸組合物可包括附加成分，其無法形成 新穎似共沸系統，或附加成分，其不在第一餾份内。第 一餾份為在全部回流條件下蒸餾柱顯示穩定狀態操作後 所取的第一餾份。測定是否加入成分之一方式為形成新 穎似共沸系統，俾可在此發明外側可在預期分離非共沸 混合物成為其分離成分之條件下蒸餾具有成分之組合物 樣品。若含有附加成分之混合物為非似共沸時，附加成 分可自似共沸成分分餾。若混合物為似共沸時，可得某 種限量第一餾份，其含有所有恆沸或作為單一物質之混 合物成分。 隨後 似共沸組合物之另 特性為，有組合物之範圍 希望所有該 已知在不同 以不同比例含有相同似共沸或恆沸之成分 組合物涵蓋術語’’似共沸”及”怪沸”。例如 壓力下，指定共沸物之組合物至少略為改變，如&合@ 之沸點般。因此，AD之共沸物表示㈣關係類型:但 是具有可變組合物，端視溫度及/或壓力而定。隨後，關 於似共沸組合物 同似共沸之成分 5吾似共〉弗。 有組合物之範圍，以 M不同比例含有相 希望所有該組合物、、7金丄 物涵盍本文所用之術
〇 \88\88927 DOC 200418970 根據某種較佳具體例，本發明提供似共沸組合物，包 含較佳主要由HFO-1225與選自由HF〇]243zf、 HFCM52a、HF〇-1234ze及其二種或多種組合所組成之群 之流體。較佳的是，該似共沸組合物包含，較佳主要由 大於〇至約99重量％ HFCM225與約！重量％至低於1〇〇重 量％選自由 HFO-1243zf、HFC-152a、HF〇-1234Ze及其二 種或夕種組合所組成之群之流體所組成。更佳的是，本 發明似共沸組合物包含，及較佳主要由約5重量％至約％ 重量％ HFCM225與約1〇重量％至約9〇重量％選自由 HFO 1243zf、HFC-152a、HFO-1234ze及其二種或多種組 合所組成之群之流體所組成。其他較佳組合物包含，或 主要由大於〇至約75重量％ HF〇_1225與約25重量％至低 於 100 重量 ％選自由 HF〇-1243zf、HFCM52a、ίίΡΟ-1234κ 及其二種或多種組合所組成之群之流體所組成。本發明 之某種其他較佳組合物包含大於0至約20重量％ HFO-1225與約8〇重量％至低於1〇〇重量％選自由 UFO 124〇zf、、HF〇 及其二種或多種組 口所、、且成之群之流體所組成。本發明之其他較佳組合物 已含、勺40重嚴〇/〇至約90重量％ HFO-1225與約1〇重量％至 約 6〇 重軍 °/〇選自由 HFO-1243zf、HFC-152a、HF〇-1234ze 及其一種或多種組合所組成之群之流體所組成。除非另 予才曰明’本文所述之所有重量°/。乃基於HFO-1225與一種 自由 3 3 3 、 ’ 5、三氟丙烯（"HF〇-1243zf”）、1，1-二氟乙烷 (，，HFC-1 52a，，、 J、反式-1，3,3,3-四氟丙烯（，，HFO-1234ze")及
O:\88\88927 DOC 200418970 其一種或多種之組合所組成之群之流體於似共沸組合物 内之全部重量。 根據某種較佳具體例，本發似共沸組合物 在約14 psia下具有沸點為約_18它至約-28t：，較佳為約 -22C至約-28°C，更佳為約_23°C至約-27°C。在某種其他 較佳具體例中，本發明組合物具有沸點為約-2(rc ±2它， 較佳為約-20°C±1°C。此外，在某種較佳具體例中，本發 明之HFO-1225組合物實質上為均相似共沸組合物。 HFO-1225/HFO_1243zf 本發明之某種較佳具體例提供包含HF〇-1225與 HFO-1243zf之似共沸組合物。較佳的是，本發明之新穎 似共沸組合物包含有效量之册〇-1225與HF〇_1243zf。本 文所用之術語”有效量”意指各成分之量，當與其他成分 或諸成分組合時，其導致本發明似共沸組合物之形成。 此等具體例較佳提供似共沸組合物，包含及較佳主要由 0至約50重量％ HFO-1225與約50重量％至低於1〇〇重量％ HFO-1243zf，較佳為大於〇至約25重量％ HF〇-1225與約 75重里/ί>至低於重量％ HF〇_1243zf，更佳為約1至約 2〇重量％ HFO-1225與約80重量％至約99重量％ HF〇-1243zf 〇 較佳的是，本發明之HFO-1225/HF〇-1243zf之組合物 在約14 psia下具有沸點為約-25它±yc。在某種具體例 中’組合物在約14psia下具有沸點較佳為約_25°C ±2°C。 本發明之某種較佳1^〇-1225/；«?〇-12432!\组合物包含
0:\88\88〇27 DOC -10- 200418970 似共沸組合物，包含或主要由有效量之HF〇-1225ye(E-異構物 ffE-HFO-1225yen，Z-異構物 f’Z-HFO-1225ye” 與 HF〇-1243zf，或其組合，fE/Z-HFO-1225ye")與 HFO-1243zf 所組成。該具體例較佳提供似共沸組合物，包含及較佳 主要由大於0至約50重量％ HFO-1225ye與約50重量％至 低於100重量°/〇 HFO-1243zf，較佳為大於0至約25重量％ HFO-1225ye與約75重量％至低於100重量％ HF〇-1243zf，更佳為約1至約20重量％ HFO-1225ye與約 80重量％至約99重量％ HFO-1243zf，仍更佳為約1至約15 重量％ HFO-1225ye與約85重量％至約99重量％ HFO-1243zf。 在某種較佳具體例中，本發明之HF0_1225ye/HFO1243zf 組合物包含似共沸組合物，包含或主要由HFO-1225ye與 HF〇-1243zf 或 E/Z-HFO-1225ye 與 HF〇-1243zf 組成。在某 種更佳具體例中，本發明之1^〇-122576/^^0-12432：[\组合 物包含或主要由Z-HFO-122 5ye與HFO-1243zf組成。 較佳的是，本發明之HFO-1225ye/HFO-1243zf組合物 在約14.4 psia下具有沸點為約-24°C至約-28°C，較佳為約 -25°C至約-28°C，更佳為約-26°C至約-28°C。 本發明之某種其他較佳1^〇-1225/1^〇-12432!\组合物 包含似共沸組合物，包含或主要由有效量之HF〇-1225zc 與HFO-1243zf組成。該具體例較佳提供似共沸組合物， 包含及較佳主要由大於0至約50重量％ HF〇-1225zc與約 50重量％至低於100重量％ HFO-1243zf，較佳為大於0至 O:\88\88927.DOC -11 - 200418970 約40重量％ HF〇-122 5zc與約60重量％至低於1〇〇重量％ HFO-1243zf，更佳為約}至約2〇重量％ hf〇M225zc與約 δ〇重量％至約99重量％HFO-1243zf，仍更佳為約3至約2〇 重i /〇 HF〇-1225zc與約80重量％至約97重量〇/0 HF〇-1243zf。 較佳的是，本發明之册〇-12252(：/1^〇-12432：^组合物在 約14 psia下具有沸點為約至約，較佳為約_23t 至約-26°C，更佳為約-24°C至約-26°C。 HFO-1225/HFC_152a 在某種其他較佳具體例中，本發明提供包含hf〇-1225 與HFC-152a之似共沸組合物。較佳的是，本發明之該新 穎似共沸組合物包含或主要由有效量之HFCm225與 HFC-152a組成。此等具體例較佳提供似共沸組合物，包 含及較佳主要由大於〇至約99重量％ HFO-1225與約1重 量％至低於100重量％ HFC-152a，較佳為大於〇至約75重 量％ HFO-1225與約25重量％至低於1〇〇重量％ HFC-15 2a，更佳為約2至約60重量。/。HFO-1225與約40重 量％至約98重量％ HFC-1 52a所組成。其他較佳組合物包 含或主要由約5重量％ HFO-1225與約10重量％至約95重 量％1^€-15 23所組成。 較佳的是，本發明之HFO-1225/HFC-152a之組合物在 約14psia下具有沸點為約-2TC至約-26°C。 本發明之某種較佳HFO-1225/HFC-152a組合物包含似 共沸組合物，包含或主要由有效量之HF〇-1225ye(E，Z， O:\88\88927 DOC -12- 200418970 或E/Z)與HFC-152a所組成。該具體例較佳提供似共沸組 合物，包含及較佳主要由大於〇至約75重量％ HF〇-1225ye與約25重量％至低於1〇〇重量％ HFC-152a， 較佳為大於0至約60重量％ HF〇-1225ye與約40重量％至 低於100重量％ HFC-15 2a，更佳為約1至約40重量％ HFO-1225ye與約60重量％至低於1〇〇重量％ HFC-152a， 仍更佳為約1至約25重量％ HF〇-1225ye與約75重量°/〇至 約 99 重量 ％ HFC-152a。 在某種較佳具體例中，本發明之HFO-1225ye/HFC-152a 組合物包含或主要由HFO-1225ye與HFC-152a或 E/Z-HFO-1225ye與HFC-152a組成。在某種更佳具體例 中，本發明之HF〇-1225ye/HFC-152a組合物包含或主要 由 Z-HFO-1225ye 與 HFC-152a 組成。 較佳的是，本發明之册〇-1225乂6/1^(：-1523組合物在約 14 psia下具有沸點為約-23t：±2°C，較佳為約-23°C±1°C。 本發明提供之某種其他較佳包含HFO-1225/ HFC-152a 之似共彿組合物。該組合物較佳包含或主要由大於〇至約 99重量。/〇 HF〇-1225zc與約1重量％至低於1〇〇重量〇/〇 HFC-152a ’較佳為約1〇重量。至約99重量％ hf〇_1225zc 與約1重.量％至約9〇重量％ HFC-152a，更佳為約1〇重量〇/〇 至約60重量％ HF〇-1225ZC與約90重量％至約40重量％ HFC-152a，仍更佳為約1〇重量％至約5〇重量0/〇 册〇-122 52(：與約90重量％至約50重量。/()1^(^152&。 較佳的是，本發明之HFCM225zc/HFCM52a組合物在約
O:\88\88927 DOC -13 - 200418970 14psia下具有沸點為約_24t：±2t，較佳為約_24^±ι^。 HF〇-1225/HFO-1234zc 在某種其他較佳具體例中，本發明提供包含hf〇_1225 與HFCM234ze之似共沸組合物。較佳的是，本發明之該 新穎似共沸組合物包含或主要由有效量之HFO-1225與 HFO-USdze組成。此等具體例較佳提供似共沸組合物， 包含及較佳主要由1重量％至99重量％ HFO-1225與約1重 量％至99重量％ HFO-1234ze，較佳為25重量％至約99重 1 /〇 HFO-1225與約 1 重量。/〇至約 75 重量 ％ HFO-1234ze， 更佳為約30重量％至約9〇重量％ HFO-1225與約10重量％ 至約70重量％ HFO-1234ze，仍更佳為約50重量％至約9〇 重量％ HFO-1225與約1〇重量％至約5〇重量0/〇 HFO-1234ze 所組成。 較佳的是，本發明之HFO-1225/HFO-1234ze之組合物在約 14.40 psia下具有沸點為約^代土沈，較佳為約^代土丨艺。 本电明之某種較佳HFO-1225/HFO-1234ze組合物包含 似共沸組合物，包含或主要由有效量之HF〇-1225ye(E，z， 或E/Z異構物）與HFO-1234ze所組成。該具體例較佳提供 似共沸組合物，包含及較佳主要由約1重量％至99重量％ HFO-122 5ye與約1重量％至99重量％ HFO-1234ze，較佳 為約25重量％至約99重量❶/。HFO-1225ye與1重量％至約 75重量％ HF〇-1234ze ,更佳為約30至約90重量〇/〇 HFO-1225ye與約 1〇 重量。/。至約 7〇 重量 ％ HFO-1234ze，仍 更佳為約50重量％至約9〇重量％ HFO-1225ye與約10重量 O:\88\88927 DOC -14- 200418970 %至約50重量％ HF〇-1234ze。 在某種較佳具體例中，本發明之HF〇-1225ye/HFO-1234ze 組合物包含或主要由Z-HFO-1225ye與HF〇-1234ze或 E/Z-HF〇-1225ye與HFO-1234ze組成。在某種更佳具體例 中，本發明之HFCM225ye/HFO-1234ze組合物包含或主 要由Z」HF〇-1225ye與HFO-1234ze組成。 較佳的是，本發明之HF〇-1225ye/HFO-1234ze組合物 在約14.40 psia下具有沸點為約-2〇°C ±2t：，較佳為約-2(TC ±1°C。 組合物之用途 本發明組合物具有廣泛範圍之實用性。例如，本發明 之一具體例係關於包含本發明似共沸組合物之冷凍劑組 合物。 本發明之冷凍劑組合物可用於各種冷凍系統，包括空 氣調節、冷凍、熱泵、HVAC系統等。本發明之較佳組合 物可顯示許多HFC冷凍劑之所欲特性，包括gWP ,其較 傳統HFC冷凍劑者低得多，及壓縮機排放溫度，其較該 冷凍劑更低。此外，本發明組合物之相當恆沸本質使之 較用作冷凍劑於各種應用之某種傳統HFCs更適合。 根據某種其他具體例，本發明提供包含本發明冷凍劑 之冷凍系統及藉冷凝及/或蒸發本發明組合物產生加熱 或~部之方法。在某種較佳具體例中，根據本發明冷卻 物品之方法包括冷凝包含本發明似共沸組合物之冷凍劑 組合物，然後在欲冷卻之物品附近蒸發該冷凍劑組合
O:\88\88927 DOC -15 - 200418970 物。加熱物品之某種較佳方法包括在欲加熱之物品附近 冷凝包含本發明似共沸組合物之冷凍劑組合物，然後蒸 發該冷凍劑組合物。雲於本文之揭示物，熟習此技藝者 當可容易加熱及冷卻根據本發明之物品而無不當實驗。 在另一具體例中，本發明似共沸組合物可單獨或與已 知推進劑組合。推進劑組合物包含，較佳主要由，更佳 由本發明似共沸組合物所組成。欲喷霧之活性成分與惰 性成分、溶劑及其他物質一起可呈現於可噴霧混合物 内。可喷霧組合物最好是氣溶膠。欲喷霧之適當活性成 分包括，但不受限制，化妝品材料如芳香劑、香料、髮 膠、清潔劑及拋光劑以及藥材如抗氣喘及抗口臭藥物。 本發明之另一具體例係關於包含一種或多種本發明似 共沸組合物之吹製劑。在其他具體例中，本發明提供可 發泡組合物，較佳為聚脲烷及聚異氰酸酯發泡體組合 物，及製備發泡體之方法。在該發泡體具體例中，包括 一種或多種本發明似共沸組合物於可發泡組合物内作為 吹製劑，該組合物較佳包括一種或多種附加成分，可在 適當條件下反應並發泡以形成發泡體或多孔結構，如此 技藝已知。任何此技藝已知方法，如”聚脲烷化學與技術，,， Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons，紐約市，紐約州，其併入本文供參考，可根據 本發明之發泡體具體例使用或採用。 此外，根據某種具體例，本發明之吹製劑用以吹製熱 塑性發泡體如聚苯乙烯及聚乙烯發泡體，包括低密度聚 0\88\88927.DOC -16- 200418970 乙烯發泡體。任何吹製該熱塑性發泡體之傳統方法本文 皆可採用。 根據某種其他較佳具體例，本發明提供減少流體燃燒 性之方法’該方法包括將本發明似共沸組合物加入該流 體内。與任何可燃性流體相關之燃燒性可根據本發明減 少。例如，與流體相關之燃燒性如氧化乙烯、可燃性氮 氟石反及fe，包括：HFC- 152a、1，1，1-三氟乙烧（HFC-1 43 a)、 二氟甲烷（HFC-32)、丙烷、己烷、辛烷等可根據本發明 減少。為了本發明之目的起見，可燃性流體可為任何在 空氣中顯示燃燒性範圍之流體，如藉由任何標準傳統試 驗方法如ASTME-681等測定。 可加入任何適量之本發明似共沸組合物以減少根據本 發明之流體的燃燒性。如此技藝者所認同，加入之量至 少部分端視對象流體之可燃程度及希望減少其燃燒性之 程度而定。在某種較佳具體例中，加入可燃性流體之似 共沸組合物之量可有效提供所得流體非可燃性。 本發明進一步提供抑制火焰之方法，該方法包括將火 焰接觸包含本發明似共沸組合物之流體。可使用任何將 火焰接觸本發明組合物之適當方法。例如，本發明似共 '/弗組合物可喷霧、洗在火焰上，或者至少一部分火焰可 浸泡於似共沸組合物内。鑒於本文之教示，熟習此技藝 者當可谷易採用各種用於本發明之傳統火焰抑制之裝置 及方法。 此外，許多物品、裝置及材料，尤其是用於醫藥領域 0 \88\88927 DOC -17- 200418970 者，必須在用於健康及安全理由如病人及醫院員工之健 康與安全性以前消#。本發明提供消毒方法，包括將欲 消毒之物品、裝置及材料與本發明之化合物或組合物接 觸。該方法可為高溫或低溫消毒法。在某些具體例中， 尚溫消毒法包括在約250至約270卞下暴露欲消毒之物 品、裝置及材料至包含本發明之化合物或組合物之熱流 體，較佳於貫質上密閉的室内。該方法通常在約2小時内 完成。然而，有些物品如塑膠物品及電器零件卻無法抗 拒該高溫而需要低溫消毒。 本發明之低溫消毒法涉及在溫度約1〇〇至約2〇〇卞下使 用本發明之化合物或組合物。本發明之化合物可與其他 通用化學消毒劑，包括例如，氧化乙烯（E〇）、甲醛水、 過氧化氫、二氧化氣及臭氧結合以形成本發明之消毒劑 組合物。 本發明之低溫消毒法最好為進行於實質上密閉，較佳 為氣在式至内之至少一步驟之方法。在第一步驟中（消毒 步驟），清潔並包裝於透氣袋内之物品放入室内。然後， 藉拉真空或許用蒸氣取代空氣自室内抽空空氣。在某種 具體例中’最好將蒸氣射入室内以達成範圍最好是約 3 0%至約70%之相對溼度。該溼度可使在達成所欲相對溼 度後‘入至内之’肖毋劑之消毒效果最適化。在消毒劑足 以滲透包裝物並到達物品之空隙之一段時間後，自室抽 空消毒劑與蒸氣。 在該法之較佳第二步驟（充氣步驟）中，充氣物品以除 O:\88\88927.DOC -18- 去消毒劑殘餘物。在有毒性 铨铷M wI β毋d之凊况下，除去該殘 之怦、、Fπ日,、 乃之男貝上無毒性化合物 之清况下則視需要而定。业 ^ ^ /、土充虱法包括空氣洗滌、持 、只丨生充氣及二種之組合。 冼淼為分批法，通常包括 在相當短時間如12分鐘抽 # 至然後在大氣壓力或以上 、工氣V入室内。重複此循環 人直到達到清潔劑 除為止。持續性充氣通常涉及透過在室之一側 之入口導入空氣’然後藉施加輕微真空至出口透過在室 之另一側之出σ將空氣引出。時常結合二種方式。例如， 共用方式涉及進行空氣洗滌，然後充氣循環。 本發明似共沸組合物之其他用途包括用作溶劑、清潔 劑等。熟習此技藝者當可容易㈣本發明組合物供該等 應用而無不當實驗。 實例 本發明以任何方式例示下列希望為例示性而非限制性 之實例。 關於貝例1-15使用沸點計，如swiet〇isi〇wski於其奎 ”沸點測定法"（Reinhold，1945)所述。 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步没有石英溫度計。約26克HF〇-1243zf裝入彿點 計，然後以小增量測定加入Z_HF〇_1225ye。當 Z-HFO-122 5ye加入HF〇-1243zf内時，可見溫度下降，顯 示形成最低沸點共沸物。如表1所示，自大於約〇至約25 重量％ Z-HFO-122 5ye，組合物之沸點改變約1。〇或以下。 O:\88\88927 DOC -19- 200418970 表1 重量％ Z-HF〇-1225ye/HF〇-1243zf組合物在 14.40psia 下 HF〇-1243zf Z-HFO-1225ye 溫度(°C) 100.00 0.00 -27.151 99.36 0.64 -27.201 99.04 0.96 -27.251 94.16 5.84 -27.281 89.49 10.51 -27.400 82.05 17.95 -26.254 78.14 21.86 -26.005 75.65 24.35 ^ -25.855 實例2 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約26克HFO-1243zf裝入沸點 計，然後以小增量測定加入E-HFO-1225ye。當 E-HFO-1225ye加入HFO-1243zf内時，可見溫度下降，顯 示形成最低沸點共沸物。 實例3 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約26克HF〇-1243zf裝入沸點 計，然後以小增量測定加入E/Z-HFO-1225ye。當 E/Z-HFO-1225ye加入HFO-1243zf内時，可見溫度下降， 顯示形成最低沸點共沸物。 實例4 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約18克HF〇-1243zf裝入沸點 計，然後以小增量測定加入HFO-1225zc。當HFO-1225zc 加入HFO-1243zf内時，可見溫度下降，顯示形成最低沸 0 \88\88927 DOC -20- 200418970 點共沸物。如表2所示，自大於約0至約40重量％ HF〇- 1225zc，組合物之沸點改變約1°C或以下。 表2 重量％ HF〇-1225zc/HFO-1243zf組合物在 14.34psia 下 HFO-1243zf HFO-1225zc 溫度fc) 100.00 0.00 -24.95 96.40 3.60 -25.03 90.66 9.34 -25.10 86.43 13.57 -25.12 81.39 18.61 -25.14 77.53 22.47 -25.03 71.01 28.99 -24.97 65.99 34.01 -24.91 60.89 39.11 -24.67
實例5 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約26克HFO-1243zf裝入沸點 計，然後以小增量測定加入HFO-1225yc。當HF〇-1225yc 加入HF〇-1243zf内時，可見溫度下降，顯示形成最低沸 點共沸物。 實例6 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約15克HFC-152a裝入沸點 計，然後以小增量測定加入Z-HFO-1225ye。當 Z-HF0-1225ye加入HFC-152a内時，可見溫度下降，顯示 形成最低沸點共沸物。如表3所示，自大於約0至約53重 量％ Z-HF〇-122 5ye，組合物之沸點改變約1°C或以下。 表3 重量％ Z-HF〇-1225ye/HFC-152a組合物在 14.44 psia下 O:\88\88927.DOC -21 - HFC-152a Z-HFO-1225ye 溫度(°C) 100.00 0.00 -23.441 98.02 1.98 -23.470 92.88 7.12 -23.745 82.29 17.71 -23.745 76.96 23.04 -23.666 69.61 30.39 -23.637 62.33 37.67 -23.558 55.57 44.43 -23.509 46.96 53.04 -23.313 200418970 實例7 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約15克HFC-152a裝入沸點 計，然後以小增量測定加入E-HFO-1225ye。當 E-HF〇-1225ye加入HFCM52a内時，可見溫度下降，顯示 形成最低沸點共沸物。 實例8 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約15克HFC-152a裝入沸點 計，然後以小增量測定加入E/Z-HFO-1225ye。當 E/Z-HFO-1225ye加入HFC-15 2a内時，可見溫度下降，顯 示形成最低沸點共沸物。 實例9 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約15克HFC-152a裝入沸點 計，然後以小增量測定加入HFO-1225zc。當HFO-1225zc 加入HFC-152a内時，可見溫度下降，顯示形成最低沸點 共沸物。如表4所示，自大於約0至約60重量°/〇 O:\88\88927 DOC -22- 200418970 HF〇-1225zc，組合物之沸點改變低於2°C。 表4 重量％ HF〇-1225zc/HFC-152a組合物在 14.40 psia下 HFC-152a HFO-1225zc 溫度(°C) 100.00 0.00 -22.68 97.41 2.59 -22.92 91.70 8.30 -23.36 85.16 14.84 -23.96 72.61 27.39 -24.28 64.34 35.66 -24.38 59.48 40.52 -24.40 53.81 46.19 -24.38 47.82 52.18 -24.31 44.63 55.37 -24.28 43.46 56.64 -24.20 實例10 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約15克HFC-152a裝入沸點 計，然後以小增量測定加入HF〇-1225ye。當HFO-1225ye 加入HFC-152a内時，可見溫度下降，顯示形成最低沸點 共沸物。 實例11 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約21克Z-HFO-1225ye裝入沸 點計，然後以小增量測定加入HF〇-1234ze。當 HF〇-1234ze加入Z-HF〇-1225ye内時，可見溫度下降，顯 示形成最低沸點共沸物。如表5所示，自大於約50至約100 重量％Z-HF〇-1225zc，組合物之沸點改變約1°C或以下。 0 \88\88927 DOC -23 - 200418970 表5 重量％ Z-HF〇-1225ye/HF〇-1234ze 組合物在 14.40psia 下 Z-HFO-1225ye HFO-1234ze 溫度(°C) 100.00 0.00 -20.002 99.68 0.32 -20.012 95.88 4.12 -20.349 89.64 10.36 -20.389 80.58 19.42 -20.399 71.45 28.55 -20.399 63.66 36.34 -20.399 60.56 39.44 -20.399 55.22 44.78 -20.349 49.91 50.09 -20.300 實例12 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約21克E-HFO-1225ye裝入沸 點計，然後以小增量測定加入HFO-1234ze。當 HF〇-123 4ze加入E-HFO-1225ye内時，可見溫度下降，顯 示形成最低沸點共沸物。 實例13 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約21克E/Z-HFO-1225ye裝入 沸點計，然後以小增量測定加入HF〇-1234ze。當 HF〇-1234ze加入E/Z-HF〇-1225ye内時，可見溫度下降， 顯示形成最低沸點共沸物。 實例14 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約21克HF〇-1225zc裝入沸點 計，然後以小增量測定加入HFO-1234ze。當HF〇-1234ze O:\88\88927 DOC -24- 200418970 加入HF〇- 1225zc内時，可見溫度下降，顯示形成最低沸 點共彿物。 實例15 使用上述沸點計，由真空套管，其頂部設有冷凝器， 其進一步設有石英溫度計。約21克1^〇-12257(：裝入沸點 °十’然後以小增量測定加入HF〇-i234ze。當HF〇_1234ze 加入HFCM225yc内時，可見溫度下降，顯示形成最低沸 點共〉弗物。 實例16-33 此等實例顯示本發明之恆沸摻合物比較於目前用於某 種冷;東循環之其他冷凍劑具有特定優點。 冷凍劑在特定操作條件之理論性能可使用標準冷凍循 %分析技術自冷凍劑之熱動力特性評估；參照，例如， R-C· Downing,氟碳冷凍劑手冊，Chapter 3, prentice_Haii， 1988。性能之係數（C0P)為普遍接受的測定，特別適用於 表示冷凍劑於涉及冷凍劑之蒸發或冷凝之特定加熱或冷 卻循環内之相對熱動力效率。在冷;東卫程中，此術語表 縮空氣中之比。冷 。對於壓縮機工程 供冷凍劑之指定容 具有較高容量之冷 示可用冷束對壓縮機施加之能量於壓 /東劑之容量表示冷凍劑之容積效率 師’此值表示壓縮機對泵熱量之能力 積流速。換言之，對於特定壓縮機， /東劑將輸送更多冷卻或加熱能力。 ，類型之計算對冷束/空氣調節循環進行，《中冷凝器 溫度通常為15(TF而蒸發器溫度通常為_35卞。另假設下
〇 \B8\889：7 DOC -25 - 200418970 列實施：等位溫線壓縮與壓縮機入口溫度為45°F。該計算 對HFO-122 5及HFC-15 2a或HF〇-1243zf之各種組合進 行。下表6及7顯示COP及各種摻合物之容量超過有關 1，1，1，2-四氟乙烷（HFC-134a)，通用傳統冷凍劑之冷凝器 與蒸發器範圍。 表6 實例 HFO-1225/HFC-152a (重量計） COP 容量 排放溫度 (°F) 16 90/10 0.98 0.70 252 17 80/20 0.98 0.83 255 18 70/30 0.99 0.88 258 19 60/40 1.00 0.99 262 20 50/40 1.02 0.98 266 21 40/50 Γ.03 0.97 270 22 30/70 1.02 0.96 275 23 20/80 1.01 0.95 280 24 10/90 1.01 0.94 285 表7 實例 組合物 HFO-1225/HFC-152a (重量計） COP 容量 排放溫度 (°F) 25 90/10 0.98 0.72 251 26 80/20 0.98 0.84 252 27 70/30 0.99 0.88 253 28 60/40 1.00 0.99 264 29 50/40 1.02 1.02 265 30 40/50 1.03 0.99 267 31 30/70 1.02 0.97 268 32 20/80 1.01 0.95 269 33 10/90 1.01 0.94 272 O:\88\88927 D0C -26-

Claims (1)

  1. 200418970 拾、申請專利範圍： 1. 一種似共7弗組合物包含大於0至約9 9重量％之HF〇-12 2 5 與約1重量°/〇至低於1〇〇重量％之選自由HF〇_i243zf、 HFC-152a、HFCM23 4ze及其二種或多種組合所組成之群 之流體。 2. 如申請專利範圍第1項之似共沸組合物，包含大於〇至約 75重量％之1^0-1225與約25重量％至低於1〇〇重量％之選 自由 HFO-1243zf、HFC-152a、HFO-1234ze及其二種或多 種組合所組成之群之流體。 3 ·如申請專利範圍第1項之似共沸組合物，包含約5重量％至 約90重量％之册0-1225與約1〇重量。/❹至約9〇重量％之選 自由 HFO-1243zf、HFC-152a、HFO-1234ze及其二種或多 種組合所組成之群之流體。 4·如申請專利範圍第1項之似共沸組合物，其中該似共沸組 合物在約14 psia下具有沸點為約·丨8。〇至約_28°C。 5·如申請專利範圍第1項之似共沸組合物，其中該似共沸組 合物在約14 psia下具有沸點為約_22。(：至約-28°C。 6·如申請專利範圍第1項之似共沸組合物，其中該似共沸組 合物在約14 psia下具有沸點為約-2i°c至約_26°C。 7·如申請專利範圍第4項之似共沸組合物，其中該似共沸組 合物在約14psia下具有沸點為。 8.如申請專利範圍第5項之似共沸組合物，包含大於〇至約 50重量％之HF〇-1225與約5〇重量。/。至低於1〇〇重量。/〇之 HFO一 1 243zf 〇 O:\88\88927 DOC 200418970 9.如申請專利範圍第8項之似共沸組合物，包含大於〇至約 50重量％之HFO-1225ye與約50重量％至低於1〇〇重量％之 HFO-1243zf。 10 ·如申請專利範圍第9項之似共沸組合物，其中該 HFO-1225ye 包括 Z-HF〇-1225ye。 11 ·如申請專利範圍第9項之似共沸組合物，其中該 HF〇-1225ye 包括 E/Z-HFO-1225ye。 12·如申請專利範圍第8項之似共沸組合物，包含大於0至約 50重量。/〇之HFO-1225zc與約50重量％至低於100重量％之 HFO-1243zf 〇 1 3 ·如申請專利範圍第6項之似共沸組合物，包含大於〇至約 99重量％之HFO-1225與約1重量％至低於1〇〇重量％ HFC-152a 〇 14.如申請專利範圍第13項之似共沸組合物，包含大於〇至約 75重量％2HFO_1225ye與約25重量％至低於1〇〇重量％之 HFC-152a。 15·如申請專利範圍第14項之似共沸組合物，其中該 HFO-1225ye 包括 Z-HFO-1225ye。 16. 如申請專利範圍第14項之似共沸組合物，其中該 HFO-122.5ye 包括 E/Z-HF〇-1225ye。 17. 如申請專利範圍第13項之似共沸組合物，包含約1〇重量〇/〇 至約99重量％之HF〇-1225zc與約1重量％至約9〇重量％之 HFC-152a。 1 8.如申凊專利範圍第7項之似共沸組合物，包含約1重量。/〇至 0 \88\88927 DOC 200418970 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 約99重里/〇之HF〇-1 2 2 5與約1重量％至約99重量％之 HF〇-1234ze。 如申請專利範圍第18項之似共沸組合物，其中該 HFO-1225為 HFO-1225ye 〇 如申請專利範圍第19項之似共沸組合物，其中該 HFO-1225ye 包括 Z-HFO-1225ye。 如申請專利範圍第1項之似共沸組合物，其中該1_^〇-1225 為 HFO-1225ye 〇 一種冷凍劑組合物，包含如申請專利範圍第丨項之似共沸 組合物。 一種冷部物品之方法，其包括冷凝如申請專利範圍第22 項之冷凍劑組合物，然後在欲冷卻之物品附近蒸發該冷 凍劑組合物。 一種可喷霧組合物，包含欲喷霧之材料與包含如申請專 利範圍第1項之似共沸組合物之推進劑。 一種吹製劑，包含如申請專利範圍第丨項之似共沸組合 物。 一種在包含如申請專利範圍第丨項之似共沸組合物之吹 製劑存在下藉發泡聚異氰酸酯、聚異氰脲酸酯、聚苯乙 稀或聚乙烯製得之密閉孔發泡體組合物。 一種減少流體之燃燒性之方法，包括將如申請專利範圍 第1項之似共彿組合物加入該流體内。 種抑制火焰之方法，包括將該火焰接觸包含如申請專 利範圍第1項之似共沸組合物之流體。 O:\88\88927 DOC 200418970 29. 種消毒物品之方法，該方法包括將該欲消毒之物品接 如申請專利範圍第1項之似共沸組合物。 O:\88\S8927 DOC 200418970 柒、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件代表符號簡單說明： (無元件代表符號） 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 0\88\88927.DOC
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