TWI643834B - 含hfo-e-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯及e-1-氯-3,3,3-三氟丙烯的類共沸組成物及其應用 - Google Patents

含hfo-e-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯及e-1-氯-3,3,3-三氟丙烯的類共沸組成物及其應用 Download PDF

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TWI643834B
TWI643834B TW103135002A TW103135002A TWI643834B TW I643834 B TWI643834 B TW I643834B TW 103135002 A TW103135002 A TW 103135002A TW 103135002 A TW103135002 A TW 103135002A TW I643834 B TWI643834 B TW I643834B
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馬克L 羅賓
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Abstract

本發明揭示類共沸組成物。該等類共沸組成物係HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯之混合物。亦揭示一種藉由使用該等類共沸組成物作為發泡劑製備熱塑性或熱固性泡沫之方法。亦揭示一種藉由使用該等類共沸組成物產生冷凍作用之方法。亦揭示一種使用該等類共沸組成物作為溶劑之方法。亦揭示一種藉由使用該等類共沸組成物來生產氣溶膠產品之方法。亦揭示一種使用該等類共沸組成物作為熱傳介質之方法。亦揭示一種藉由使用該等類共沸組成物來滅火或阻燃之方法。亦揭示一種使用該等類共沸組成物作為介電質之方法。

Description

含HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯及E-1-氯-3,3,3-三氟丙烯的類共沸組成物及其應用
本揭露係關於HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯及E-1-氯-3,3,3-三氟丙烯的類共沸組成物。
在過去數十年來,許多產業不斷致力於尋找耗竭臭氧之氟氯碳化合物(CFC)及氫氟氯碳化合物(HCFC)的替代品。CFC及HCFC已被運用於各式廣泛應用,包括作為氣溶膠推進劑、冷媒、洗淨劑、用於熱塑性及熱固性泡沫之膨脹劑、熱傳介質、氣體介電質、滅火及阻燃劑、動力循環工作流體、聚合作用介質、微粒移除流體、載體流體、拋光研磨劑以及置換乾燥劑。在尋找這些多用途化合物之替代品的過程中,許多產業已轉向使用氫氟碳化合物(HFC)。
HFC不會對平流層臭氧造成破壞,但仍會造成「溫室效應」(亦即其促使全球暖化)而存有疑慮。由於HFC造成全球暖化,因此其使用已受到嚴格檢視,且未來亦將可能對其廣泛使用予以限制。
所以,需要一種不造成平流層臭氧破壞且同時具有低全球暖化潛勢(GWP)之組成物。咸信某些氫氟烯烴,例如HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯((CF3)2CFCH=CHF、反HFO-1438ez、E-HFO-1438ez、E-1438ez),可符合這兩項目標。本揭露提供一種主要由下列組成之組成物:(a)HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及(b)E-1-氯-3,3,3-三氟丙烯;其中該E-1-氯-3,3,3-三氟丙烯係以與HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯形成類共沸混合物的有效量存在。
圖1-圖1係HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯及E-1-氯-3,3,3-三氟丙烯的類共沸組成物在約27.8℃的溫度下之圖形表示。
在許多應用中,理想為使用一種純單一組分或一種共沸或類共沸混合物。舉例而言,當一發泡劑組成物(又名泡沫膨脹劑或泡沫膨脹組成物)並非純單一組分或共沸或類共沸物混合物時,則該組成物於應用於泡沫形成製程時可能會改變。在組成物中的此種改變會不良地影響製程,或造成應用上的效能不佳。再者,在冷凍應用中,冷煤於操作時經常從軸封、軟管連接、焊接頭及破裂管線處流失。此外,冷煤可能於冷凍設備維護程序時釋放至大氣中。若冷煤不是純單一組分或共沸或類共沸物組成物,則冷煤組成物從冷凍設備流 出或排至大氣時可能會改變。冷煤組成物的改變可能造成冷煤變得易燃或冷凍效能不佳。因此,在這些及其他應用中,有使用共沸或類共沸混合物(例如含有HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯及E-1-氯-3,3,3-三氟丙烯的共沸或類共沸混合物)之需求。
在提出下述實施例之細節前,先定義或闡明一些術語。
如本文中所用者,術語「包含」、「包括」、「具有」或其任何其它變型均旨在涵蓋非排他性的包括。舉例而言,包含一表列元件的製程、方法、物件或裝置不一定僅限於該些元件,而是可包括其他未明確列出或為該製程、方法、物件或裝置所固有的元件。此外,除非另有明確地相反陳述,否則「或」係指包含性的「或」,而不是指排他性的「或」。例如,以下任何一種情況均滿足條件A或B:A為真(或存在的)且B為假(或不存在的)、A為假(或不存在的)且B為真(或存在的),以及A和B均為真(或存在的)。
又,使用「一」或「一個」來描述本文所述的元件和組件。這樣做僅僅是為了方便,並且對本發明範疇提供一般性的意義。除非很明顯地另指他意,這種描述應被理解為包括一個或至少一個,並且該單數也同時包括複數。
除非另有定義,本文所用之所有技術與科學術語均與本發明所屬技術領域具有一般知識者所通常理解的意義相同。儘管類似或同等於本文所述內容之方法或材料可用於本發明之實施例的實施或測試,但合適的方法與材料仍如下所述。除非引用特定段落,否則本文中所提及之所有公開案、專利申請案、專利及其他參考文獻均以引 用方式全文併入本文中。在發生衝突的情況下,以本說明書(包括定義)為準。此外,該等材料、方法及實例僅係說明性質,而不意欲為限制拘束。
若量、濃度或其他數值或參數係給定為一範圍、較佳範圍或一系列較大之較佳值及/或較小之較佳值,則應將此視為特別揭示所有由任一對任何較大範圍限值或較佳值與任何較小範圍限值或較佳值所形成的所有範圍,不論是否另外揭示這些範圍。若本說明書中敘述一數值範圍,除非另有說明,否則該範圍意欲包括其端點以及該範圍內的所有整數和小數。
此應用包括主要由下列組成的組成物:(a)HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯;其中該E-1-氯-3,3,3-三氟丙烯係以與HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯形成類共沸混合物的有效量存在。
有效量意指當E-1-氯-3,3,3-三氟丙烯與HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯組合時導致形成類共沸混合物之該E-1-氯-3,3,3-三氟丙烯的量。此定義包括各組分之量,該量可能依施加於該組成物的壓力而改變,前提為該類共沸物組成物在不同壓力下係持續存在,但可能具有不同沸點。因此,有效量包括在本文所述之溫度或壓力以外形成類共沸物組成物之本發明組成物之各組分之量,例如以重量或莫耳百分比表示。
如本領域所認同的,一共沸組成物為兩個或多個不同的組分之摻和物,當其在一給定壓力下呈液態時,將會在一大致恆定的 溫度下沸騰,該溫度可高於或低於該些個別組分的沸點,且其將提供一實質上與沸騰中的該整體液體組成物相同的蒸氣組成物。(參考例如M.F.Doherty and M.F.Malone,Conceptual Design of Distillation Systems,McGraw-Hill(New York),2001,185-186,351-359)。
因此,共沸組成物之主要特徵為在一給定壓力下,該液體組成物之沸點為固定,且在該沸騰組成物上方之蒸氣組成實質上即為該整體沸騰液體組成物之組成(即不會發生液體組成物之組分分餾)。亦如本領域中所認知,當共沸組成物於不同壓力下沸騰時,該共沸組成物之各組分的沸點及重量百分比可能會改變。因此,共沸組成物可就特定壓力下具有固定沸點之組成物的組分之間的獨特關係來定義,或就組分的組成範圍來定義,或就各組分之確切重量百分比來定義。
為本發明之目的,類共沸物組成物意指表現類似共沸組成物之組成物(即具有固定沸騰特性或在沸騰或蒸發時不會分餾之傾向)。因此,在沸騰或蒸發時,其蒸氣及液體組成若有任何改變,此改變也僅是極少或屬可忽略之程度。此與非類共沸物組成物於沸騰或蒸發時其蒸氣及液體組成會大幅改變形成對比。
此外,類共沸物組成物所展現之露點壓力及泡點壓力幾乎沒有壓差。也就是說,在給定溫度下露點壓力和泡點壓力的差異係一微小數值。在本發明中,露點壓力和泡點壓力差異小於或等於百分之五(以泡點壓力為基準)的組成物係視為類共沸物。
如本領域中所認知,當系統相對揮發度接近1.0,則該系統係定義為形成共沸或類共沸組成物。相對揮發度為組分1的揮發度與組分2的揮發度之比率。一組分在蒸氣中的莫耳分率與該組分在液體中的莫耳分率之比率即為該組分的揮發度。
為測定任兩種化合物的相對揮發度,可使用一種稱為PTx法之已知方法。汽液平衡(VLE)及據此之相對揮發性可在等溫或等壓下測定。等溫法需要在恆溫下量測已知組成的混合物之總壓力。在此程序中,乃於恒溫下測量兩種化合物之各種組成在體積已知之槽中的總絕對壓力。等壓法需要在恆壓下量測已知組成的混合物之溫度。在此程序中,乃於恆壓下測量兩種化合物之各種組成在體積已知之槽中的溫度。PTx方法之使用係詳細描述於"Phase Equilibrium in Process Design",Wiley-Interscience Publisher,1970,written by Harold R.Null,on pages 124 to 126。
這些量測值可藉由使用如非隨機兩液體(NRTL)方程式之活性係數方程式模型,轉換為PTx槽中的平衡氣體和液體組成物,以代表液相非理想性。活性係數方程式(例如NRTL方程式)之使用係詳細描述於"The Properties of Gases and Liquids,"4th edition,published by McGraw Hill,written by Reid,Prausnitz and Poling,on pages 241 to 387,以及"Phase Equilibria in Chemical Engineering," published by Butterworth Publishers,1985,written by Stanley M.Walas,pages 165 to 244。儘管不欲受到任何理論或解說之限制,咸信NRTL方程式以及PTx槽數據可足以預測本發明之HFO-E-1,3,4,4,4- 五氟-3-三氟甲基-1-丁烯/E-1-氯-3,3,3-三氟丙烯組成物的相對揮發性,因此可預測此等混合物於多段分離設備例如蒸餾塔中之行為。
透過實驗,發現HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯及E-1-氯-3,3,3-三氟丙烯形成類共沸組成物。
使用上述之PTx法測定此二元對之相對揮發度。於恆溫下量測各種二元組成物在已知體積之PTx槽中的壓力。接著使用NRTL方程式將這些量測值還原為槽中的平衡氣體和液體組成物。
圖1所示為HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯混合物於PTx槽中所測得之壓力相對於組成之變化,其描繪於27.8℃及約18至21psia之範圍的壓力下形成主要由1至44莫耳%的HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及56至99莫耳%的E-1-氯-3,3,3-三氟丙烯組成的類共沸組成物,且亦描繪於27.8℃及約13至14psia之範圍的壓力下形成主要由84至99莫耳%的HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及1至16莫耳%的E-1-氯-3,3,3-三氟丙烯組成的類共沸組成物。
根據計算,主要由1至99莫耳%的HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及1至99莫耳%的E-1-氯-3,3,3-三氟丙烯組成之類共沸組成物係在約-40℃至約140℃之範圍的溫度下形成(即,在此溫度範圍內,該組成物在特定溫度下的露點壓力及泡點壓力之差係小於或等於5個百分點(以該泡點壓力為基準))。
類共沸組成物的一些實施例係列於表1。
本發明之類共沸物組成物可藉由任何簡便之方法製備,包括混合或組合所需的量。在本發明之一實施例中,類共沸物組成物可藉由秤量所欲組分之量以及之後於適當容器中將其組合而製備。
本發明之類共沸物組成物可被運用於各式廣泛應用,包括作為氣溶膠推進劑、冷媒、溶劑、洗淨劑、用於熱塑性及熱固性泡沫之發泡劑(泡沫膨脹劑)、熱傳介質、氣體介電質、滅火及阻燃劑、動力循環工作流體、聚合作用介質、微粒移除流體、載體流體、拋光研磨料以及置換乾燥劑。
本發明之一實施例提供一種用於製備熱塑性及熱固性泡沫之方法。該方法包含使用類共沸組成物作為發泡劑,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
本發明之另一實施例提供一種用於產生冷凍作用之方法。該方法包含將類共沸組成物冷凝以及之後使該類共沸組成物於接近待冷卻之主體處蒸發,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
本發明之另一實施例提供一種方法,其使用類共沸組成物作為溶劑,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
本發明之另一實施例提供一種用於生產氣溶膠產品之方法。該方法包含使用類共沸組成物作為推進劑,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
本發明之另一實施例提供一種方法,其使用類共沸組成物作為熱傳介質,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
本發明之另一實施例提供一種用於滅火或阻燃之方法。該方法包含使用類共沸組成物作為滅火劑或阻燃劑,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
本發明之另一實施例提供一種方法,其使用類共沸組成物作為介電質,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。

Claims (9)

  1. 一種類共沸組成物,其主要由下列組成:(a)HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯;以及(b)E-1-氯-3,3,3-三氟丙烯;其中該E-1-氯-3,3,3-三氟丙烯係以與該HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯形成一類共沸組合的一有效量存在。
  2. 一種用於製備一熱塑性或熱固性泡沫之方法,其包含使用一類共沸組成物作為一發泡劑,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
  3. 一種用於產生冷凍作用之方法,其包含將一類共沸組成物冷凝以及之後使該類共沸組成物於接近待冷卻之主體處蒸發,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
  4. 一種包含使用一類共沸組成物作為一溶劑之方法,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
  5. 一種用於生產一氣溶膠產品之方法,其包含使用一類共沸組成物作為一推進劑,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
  6. 一種包含使用一類共沸組成物作為一熱傳介質之方法,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
  7. 一種用於滅火或阻燃之方法,其包含使用一類共沸組成物作為一滅火劑或阻燃劑,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
  8. 一種包含使用一類共沸組成物作為介電質之方法,其中該類共沸組成物主要由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及E-1-氯-3,3,3-三氟丙烯組成。
  9. 如請求項2用於製備一熱塑性或熱固性泡沫之方法,其中該類共沸組成物主要由95至99莫耳%的HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯以及1至5莫耳%的E-1-氯-3,3,3-三氟丙烯組成。
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