201139639 六、發明說明： 【發明所屬之技術領域】 本申請案主張2010年4月26曰申請之美國專利申請案第 61/327746號及2011年1月25日申請之美國專利申請案第 61/435875號之優先權。 本文所揭示者係關於E-l，l，l，4,4,4-六氟-2-丁烯之共沸或 類共沸物組成物。 【先前技術】 在過去數十年來’許多產業不斷致力於尋找破壞臭氧之 氟氣碳化合物（CFC)及氫氟氣碳化合物（HCFC)的替代品。 CFC及HCFC已廣泛應用於包括作為氣膠推喷劑、冷媒、 洗淨劑、用於熱塑性及熱固性發泡體之膨脹劑、熱傳介 質、氣相介電質、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。在尋找這些多種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HFC有促成「溫室 效應」的疑慮，亦即其促使全球暖化。由於HFC會促成全 球暖化，其使用已受到審慎注意，且於未來亦將大幅限制 其使用範圍。所以，業界對於發展不引起平流層臭氧損害 以及具有低全球暖化潛在值（Gwp)之組成物有其需求。特 定之氫氟烯烴，例如mu4·六氟_2_ 丁烯（CF3cH= CHCF3、FC-1336mzz、FO-1336mzz)，據信可滿足上述需 求。 155860.doc 201139639 【發明内容】 本申請案包括兩種不同類型的共沸或類共沸物混合物。 本揭露提供一種組成物，其係主要由以下物質所組成： (a) E-F〇-1336mzz以及（b) E-HCFO-1233zd(E-l-氣-3,3,3-三 氟丙烯，E-CF3CH=CHC1);其中 E-HCFO-1233zd係以一有 效量存在以與E-FO-1336mzz形成類共沸物混合物。 本揭露亦提供一種組成物，其係主要由以下物質所組 成：（a) E-FO-1336mzz 以及（b) HCFO-1233xf (2-氯-3,3,3-二 II 丙烯 ’ CF3CC1=CH2);其中 HCFO-1233xf係以一有效 罝存在以與E-FO-1336mzz形成共沸或類共沸物混合物。 【實施方式】 在許多應用中，理想為使用一種純單 或類共沸混合物。舉例而言，當一發泡劑組成物（亦名發 泡體膨脹劑或發泡體膨脹組成物）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發泡體形成製 矛夺可月b會改變。在組成物中的此種改變會對處理有不利 影響，或造成應用上的效能不佳。再者，在冷珠應用中， 冷煤於操作時常常從軸封、軟f連接、焊接頭及斷裂管線 處流失。此外，冷煤可能於冷;東設備維護程序時釋放至大 乳中。若冷煤不是純單—組分或共沸或類共沸物組成物， 則冷煤組成從冷康設備流出或排至大氣時可能會改變。冷 、…成的改良可此造成冷煤變得易燃或冷床效能不佳。據 :’有需要在此等及其他應用中使用共彿或類共沸混合 物’例如包括E-1 1 ] 4 4 z。 ，，，，，_/、氟-2-丁稀（E-CFsCtKiiCF^， 155860.doc 201139639 E-FC-1336mzz，E-FO-1336mzz)之共沸或類共沸物混合 物。 在提出下述實施例之細節前，先定義或闡明一些術語。 FO-1336mzz可能以E或Z兩種組態異構物中之一種存 在。本說明書中所用之FO-1336mzz係指異構物，即Z-FO· 1336mzz或E-FO-1336mzz ’以及此種異構物之任何組合或 混合物。 HCFO-1233zd(l-氣-3,3,3-三氟丙烯，CF3CH=CHC1)可以 兩種組態異構物之形式存在，E或Z。於本文中，HCFO-1233zd 係指異構物 Z-HCFO-1233zd 或 E-HCFO-1233zd，以 及任何前述異構物之組合或混合物。 如本文中所用者，術語「包含」、「包括」、「具有」或其 任何其匕變型均旨在涵蓋非排他性的包括。舉例而言，包 括一系列要素的製程、方法、製品或裝置不一定僅限於該 些要素，而是可包括未明確列出或該製程、方法、製品或 裝置所固有的其他要素。此外’除非有相反的明確說明， 或」疋指包含性的「或」，而不是指排他性的「或」。例 ，、、下4何種情況均滿足條件A或B : A為真（或存在） 且8為偽（或不存在）、A為偽（或不存在）且B為真（或存在）以 及A與B皆為真（或存在）。 又，使用 「一 -V? 「 」或一個」來描述本文所述的元件和組 刀此舉僅僅是為了方便，以及對本發明的範圍提供一般 性的意義。除非报明顯地另指他意，這種描述應被理解為 個或至j一個，並且該單數也同時包括複數。 155860.doc 201139639 除非另行定義，否則本文所使用的所有技術和科學術語 之含義，具有與本發明所屬領域中具有通常知識者通常理 解的含義相g。在發生衝突的情;兄下，應以本說明書及其 包含之定義為準。儘管類似或同等於本文所述内容之方法 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。此外，該等材料、方法及實例僅係 說明性質，而沒有意欲做限制拘束。 若數量、濃度或其他數值或參數係作為一範圍、較佳範 圍或系列較大之較佳值及/或較小之較佳值，則應將此 視為特定揭露所有由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之配對所形成的所有範圍，不論是否 有另外揭露這些範圍。若本文中敘述一數值範圍，除非另 有說明，該範圍意欲包括該範圍之端點與其内之所有整數 與分數。 E-FO-1336mzz為一已知化合物，且其可藉由u二氯 -1，1’4,4,4-五氟丁烷與乾燥kf於經蒸餾之四亞甲砜 (tetramethylene sulph〇ne)中進行反應而製得，此係揭露於 美國專利第5,463，150號。 E-HCFO-1233zd為一已知化合物，且其可藉由 CChCHzCHCl2與HF在SnCU存在下進行氟化而製得，例如 Van Der Puy等人於美國專利第5,777，184號中所揭露者。 HCFO-1233xf為一已知化合物，且其可藉由在氣相反應 中將HF添加至CH2C1CCI=CC12，並使用二異丙胺作為安定 劑及〇2〇3作為催化劑而製得，例如Merkel等人於美國專 155860.doc 201139639 利申請案公開第2011/0004035號中所揭露者β 本申清案含有包括E-FO-13 3 6mzz之共彿或類共沸物組成 物。 在本發明之某些貫施例中’該組成物係主要由（a) E-FO· 1336mzz 以及（b) E-HCFO-1233zd所組成；其中 E_HCF〇_ 1233zd係以一有效量存在以與E-FO-1336mzz形成類共彿物 混合物。 在本發明之某些實施例中’該組成物係主要由（a) E-FO- 1336mzz 以及（b) HCFO-1233xf所組成；其中HCFO-1233xf 係以一有效量存在以與E-FO-1336mzz形成共彿或類共沸物 混合物。 所謂有效量是指一數量，當其與E-FO-1336mzz結合時， 可導致共沸或類共沸混合物之形成。此定義包括各組分之 量可能依作用於該組成物的壓力而改變之情形，只要在不 同壓力下共沸或類共沸物組成物係持續存在，但可能具有 不同沸點。因此，有效量包括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’其可在不同於此處所 描述之溫度或壓力下形成共沸或類共沸物組成物。 如本領域中所認知，共沸組成物為二或多種不同組成之 摻和物，當於一特定壓力下呈液態時，會在大致恆溫下彿 騰，該溫度可高於或低於各別組分之沸點溫度，且提供實 質上與發生沸騰之整體液體組成物相同的蒸氣組成物（參 見如 M. F. Doherty and M.F. Malone, Conceptual Design of Distillation Systems, McGraw-Hill (New York), 2001, 185- 153860.doc 201139639 186,351-359)。 因此，共沸組成物之主要特徵為在一特定壓力下，液體 組成物之沸點為固定，且沸騰組成物上方之蒸氣組成物實 質上係為整體沸騰液體組成物（即不會發生液體組成物組 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，各組分之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 各組分之確切重量百分比來定義，或就組分的組成範圍來 疋義，或就存在於組份間的獨特關係來定義。 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 會分館之傾向）。因此，在彿騰或蒸發時，蒸氣及液體組 成物若有任何改變’此改變也僅是極少或屬可忽、略之程 度。此與非類共㈣組成物於沸騰或蒸發時該蒸氣及液體 組成物會大幅改變可形成對比。 、，此外’類共〉弗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’在特定溫度下露點壓力和泡點壓 力的差異係-微小數值。在本發明中，露點壓力和泡點麼 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，領域中所認知，當系統相對揮發度接近1〇,則該 系統定義為係形成共沸或類共彿物組成物。相對揮發度為 組分1揮發度與組分2揮發度之比率。蒸氣中組分莫耳分率 ”液體中組分莫耳分率之比率為該組分之揮發度。 155860.doc 201139639 為測定任兩種化合物的相對揮發度，可使用一種稱為 ΡΤχ法之已知方法。氣_液平衡（vle)以及相對揮發性可等 溫或等壓測定。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，乃於恆溫下測量兩種化合物各 種組成關係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 怪壓下測量兩種化合物各種組成關係在體積已知之槽中的 溫度。ΡΤχ法的使用乃於197〇年由wiley_interscience。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Priority 435875. The azeotrope or azeotrope-like composition of E-l,l,l,4,4,4-hexafluoro-2-butene is disclosed herein. [Prior Art] In the past few decades, many industries have been continually working to find alternatives to ozone-depleting fluorine-carbon compounds (CFCs) and hydrogen-fluorine-carbon compounds (HCFCs). CFC and HCFC have been widely used as a gas gel push spray, refrigerant, detergent, expansion agent for thermoplastic and thermosetting foams, heat transfer medium, gas phase dielectric, fire extinguishing and flame retardant, power Recirculating working fluid, polymerization medium, particulate removal fluid, carrier fluid, polishing abrasive, and displacement desiccant. In the search for alternatives to these multi-purpose compounds, many industries have turned to the use of hydrofluorocarbons (HFCs). HFC does not cause damage to stratospheric ozone, but HFC has the doubt that it contributes to the "greenhouse effect," that is, it contributes to global warming. Since HFC contributes to global warming, its use has been carefully observed and will greatly limit its use in the future. Therefore, the industry has a need to develop components that do not cause stratospheric ozone damage and have a low global warming potential (Gwp). Specific hydrofluoroolefins, such as mu4·hexafluoro-2-butene (CF3cH=CHCF3, FC-1336mzz, FO-1336mzz), are believed to meet the above needs. 155860.doc 201139639 SUMMARY OF THE INVENTION This application includes two different types of azeotrope or azeotrope-like mixtures. The present disclosure provides a composition consisting essentially of: (a) EF〇-1336mzz and (b) E-HCFO-1233zd (El-gas-3,3,3-trifluoropropene, E-CF3CH =CHC1); wherein E-HCFO-1233zd is present in an effective amount to form an azeotrope-like mixture with E-FO-1336mzz. The present disclosure also provides a composition consisting essentially of (a) E-FO-1336mzz and (b) HCFO-1233xf (2-chloro-3,3,3-di II propylene' CF3CC1=CH2 Wherein HCFO-1233xf is present as an effective hydrazine to form an azeotrope or azeotrope-like mixture with E-FO-1336mzz. [Embodiment] In many applications, it is desirable to use a pure mono- or azeotrope-like mixture. For example, when a blowing agent composition (also known as a foam expansion agent or a foam expansion composition) is not a pure single component or an azeotrope or azeotrope-like mixture, the composition is applied The foam forms a spear and the b will change. Such changes in the composition can adversely affect handling or cause poor performance in the application. Furthermore, in cold bead applications, cold coal is often lost from shaft seals, soft f joints, weld joints, and fracture lines during operation. In addition, cold coal may be released into the milk during cold maintenance; If the cold coal is not a pure mono-component or azeotrope or azeotrope-like composition, the composition of the cold coal may change from the outflow or discharge to the atmosphere. Cold, improved, can cause cold coal to become flammable or poorly cooled. According to : 'There is a need to use a total or azeotrope-like mixture in such and other applications' including, for example, E-1 1 ] 4 4 z. , azeotrope or azeotrope-like mixture of fluoropropene (E-CFsCtKiiCF^, 155860.doc 201139639 E-FC-1336mzz, E-FO-1336mzz). Some terms are defined or clarified before the details of the following embodiments are presented. The FO-1336mzz may be present in one of the E or Z configuration isomers. As used herein, FO-1336mzz refers to isomers, i.e., Z-FO·1336mzz or E-FO-1336mzz' and any combination or mixture of such isomers. HCFO-1233zd (l-gas-3,3,3-trifluoropropene, CF3CH=CHC1) can exist in the form of two configurational isomers, E or Z. As used herein, HCFO-1233zd refers to the isomers Z-HCFO-1233zd or E-HCFO-1233zd, and combinations or mixtures of any of the foregoing isomers. The term "comprising", "including", "having", or any of its variants, as used herein, is intended to cover a non-exclusive inclusion. For example, a process, method, article, or device that comprises a series of elements is not necessarily limited to the elements, but may include other elements not specifically listed or inherent to the process, method, article, or device. In addition, 'unless there is a clear statement to the contrary, or '' refers to an inclusive "or" rather than an exclusive "or". Example, , and 4 situations satisfy the condition A or B: A is true (or exists) and 8 is pseudo (or non-existent), A is pseudo (or non-existent) and B is true (or exists) and Both A and B are true (or exist). Also, the use of "a-V?" or "an" to describe the elements and the knives described herein is for convenience only and provides a general sense of the scope of the invention. Unless expressly stated otherwise, this description should be understood to mean one or to one, and the singular also includes the plural. 155860.doc 201139639 Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event of a conflict; the definition of this manual and its inclusion shall prevail. Although methods or materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are still described below. Moreover, the materials, methods, and examples are illustrative only and are not intended to be limiting. If the quantity, concentration or other value or parameter is a preferred value of a range, a preferred range or a series and/or a smaller preferred value, then this should be considered as a specific disclosure. All ranges formed by the pairing of values or preferred values with any smaller range of limits or preferred values, whether or not otherwise disclosed. If a range of values is recited herein, the range is intended to include the endpoints of the range and all integers and fractions thereof. E-FO-1336mzz is a known compound, and it can be dried by distillation of u-dichloro-1,1'4,4,4-pentafluorobutane and dried kf in tetramethylene sulph〇ne It is prepared by carrying out a reaction, which is disclosed in U.S. Patent No. 5,463,150. E-HCFO-1233zd is a known compound, and it can be obtained by fluorination of CChCHzCHCl2 and HF in the presence of SnCU, as disclosed in U.S. Patent No. 5,777,184. HCFO-1233xf is a known compound, and it can be prepared by adding HF to CH2C1CCI=CC12 in a gas phase reaction, using diisopropylamine as a stabilizer and 〇2〇3 as a catalyst, for example, Merkel et al. The method disclosed in U.S. Patent Application Serial No. PCT Application No. 2011/0004035, the entire disclosure of which is incorporated herein by reference. In certain embodiments of the invention, the composition is composed primarily of (a) E-FO·1336mzz and (b) E-HCFO-1233zd; wherein E_HCF〇_1233zd is present in an effective amount to E-FO-1336mzz forms a mixture of common objects. In certain embodiments of the invention 'the composition is comprised primarily of (a) E-FO-1336mzz and (b) HCFO-1233xf; wherein HCFO-1233xf is present in an effective amount to interact with E-FO- 1336mzz forms a mixture of a total or an azeotrope. By effective amount is meant an amount which, when combined with E-FO-1336mzz, results in the formation of an azeotrope or azeotrope-like mixture. This definition includes the fact that the amount of each component may vary depending on the pressure acting on the composition, as long as the azeotrope or azeotrope-like composition system persists under different pressures, but may have different boiling points. Thus, an effective amount includes the amount of each component of the compositions of the present invention', e.g., expressed as weight or mole percent, which can form an azeotrope or azeotrope-like composition at temperatures or pressures other than those described herein. As is recognized in the art, the azeotrope composition is a blend of two or more different compositions which, when in a liquid state at a particular pressure, will be at a substantially constant temperature, which may be higher or lower than the individual. The boiling temperature of the component and provides a vapor composition substantially the same as the bulk liquid composition in which the boiling occurs (see, e.g., MF Doherty and MF Malone, Conceptual Design of Distillation Systems, McGraw-Hill (New York), 2001, 185- 153860.doc 201139639 186,351-359). Therefore, the main feature of the azeotropic composition is that the boiling point of the liquid composition is fixed at a specific pressure, and the vapor composition above the boiling composition is substantially an integral boiling liquid composition (ie, no liquid composition occurs) Fractionation of components). As is also recognized in the art, when the azeotrope is boiled under different pressures, the boiling point and weight percentage of each component may vary. Thus, the azeotrope composition can be defined as the exact weight percent of the components of the composition having a fixed boiling point at a particular pressure, or in terms of the compositional range of the components, or in the unique relationship between the components. definition. For the purposes of the present invention, an azeotrope-like composition means a composition that exhibits a similar azeotrope composition (i.e., has a tendency to have a fixed boiling characteristic or not separate when boiling or evaporating). Therefore, if there is any change in the vapor and liquid composition during the turpent or evaporation, the change is only minimal or negligible. This vaporization of the vapor and liquid compositions during boiling or evaporation of the composition with the non-classical (four) composition can be contrasted. In addition, there is almost no pressure difference between the dew point pressure and the bubble point pressure exhibited by the 'class of common' objects. That is to say, the difference between the dew point pressure and the bubble point pressure at a specific temperature is a small value. In the present invention, a composition having a difference in dew point pressure and bubble point force of less than or equal to five percent (based on the bubble point pressure) is regarded as an azeotrope-like substance. As is recognized in the art, when the relative volatility of the system is close to 1 Torr, the system is defined as forming an azeotrope or a common composition. The relative volatility is the ratio of the volatility of component 1 to the volatility of component 2. The ratio of the molar fraction of the component in the vapor "the molar fraction of the component in the liquid is the volatility of the component. 155860.doc 201139639 To determine the relative volatility of any two compounds, a method known as the hydrazine method can be used. Known methods. Gas-liquid equilibrium (vle) and relative volatility can be measured isothermally or isostatically. The isothermal method requires measuring the total pressure of a mixture of known composition at a constant temperature "in this procedure, at a constant temperature The total absolute pressure of the various compositional relationships of the two compounds in a tank of known volume is measured. The isostatic method requires measuring the temperature of the mixture of known composition at a constant pressure. In this procedure, the two compounds are measured under various pressures. The composition of the relationship in the volume of the known volume of the tank. The use of the method is in 197 years by wiley_interscience
Publisher出版、Harold R. Null所著的「Phase Equilibrium in Process Design」第 124至 126頁。 這些量測值可藉由使用如非隨機兩液體（NRTL)方程式之 活性係數方程式模式轉換為ΡΤχ槽中平衡氣體和液體組成 物，以代表液相非理想性。如NRTL方程式之活性係數方 程式的使用’於McGraw Hill出版，Reid、Prausnitz和 Poling所著的「The Properties of Gases and Liquids」一書 第四版中第 241 至 387頁以及 1985 年 Butter worth Publishers 出版 ’ Stanley M. Walas所著「Phase Equilibria in ChemicalPublisher Publishing, "Phase Equilibrium in Process Design" by Harold R. Null, pp. 124-126. These measurements can be converted to equilibrium gas and liquid compositions in the gutter by using a coefficient of coefficient equation such as the non-random two-liquid (NRTL) equation to represent liquid phase non-idealities. For example, the use of the coefficient of activity equation for the NRTL equation is published in McGraw Hill, "The Properties of Gases and Liquids" by Reid, Prausnitz and Poling, pp. 241-387, and 1985, Butter worth Publishers. "Phase Equilibria in Chemical" by Stanley M. Walas
Engineering」第165至244頁》儘管不欲受到任何理論或解 說之限制，咸信NRTL方裎式以及ΡΤχ槽數據以足以預測本 發明含有E-l，l，l，4,4,4 -六敗-2-丁稀之組成物的相對揮發 性’且因此可預測此等混合物於多段式分離設備中之性 質，例如蒸顧塔。 經實驗發現，E-FO-1336mzz及E-HCFO_1233zd形成類共 沸物組成物。 155860.doc •10· 201139639 使用上述之ΡΤχ法測定此二元對之相對揮發度。對各種 二元組成物於恆溫下量測已知體積之ΡΤχ槽中的壓力。接 者使用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。 所ϊ測得之蒸氣壓與E-FO-1336mzz/E-HCFO-1233zd混 合物於ΡΤχ槽中之組成關係乃如圖1所示’其以圖形繪示主 要由£-1，1，1，4,4,4-六氟-2-丁烯及^1^卩0-12332(1在24.7。〇 下所組成之類共彿物組成物的形成，此可見於約1至約19 莫耳％2Ε-1，1，1，4,4,4-六氟-2-丁烯及約99至約81莫耳◦/〇之 E-HCFO-1233zd之混合物，且可見於約38至約99莫耳％之 E-l，l，l，4,4,4-六氟-2-丁 烯及約 62至約 1莫耳。/。之 e-HCFO- 12 3 3 z d之混合物。 根據計算，主要由約i至約99莫耳百分比EF〇1336mzz 與約99至約1莫耳百分比E_HCF〇_1233zd所組成之類共沸 物組成物，是在約-4(TC至約14(rc之溫度範圍内形成（亦即 在此溫度範圍内’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百分之5(基於泡點壓力))。 部分類共 >弗物址成物會始^〗丨 取物貫％例列於表i中。其他類共沸物 組成物實施例列於表2中。 155860.doc 201139639 表1 ·類共沸物組成物 組分 T(°C) 莫耳％範圍 E-FO-133 6mzz/E-HCFO-1233zd -40 1-5/99-95 以及 67-99/33-1 E-FO-1336mzz/E-HCFO-1233zd -20 1-8/99-92 以及 56-99/44-1 E-FO-1336mzz/E-HCFO-1233zd 0 1-12/99-88 以及 47-99/53-1 E-FO-1336mzz/E-HCFO-1233zd 20 1-17/99-83 以及 40-99/60-1 E-FO-1336mzz/E-HCFO-1233zd 40 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 50 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 60 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 80 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 100 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 120 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 140 1-99/99-1 155S60.doc -12- 201139639 表2.類共沸物組成物 組分 T(°C) 莫耳％範圍 E-FO-1336mzz/E-HCFO-1233zd -40 67-95/33-5 E-FO-1336mzz/E-HCFO- 1233zd -20 5-8/95-92 以及 56-95/44-5 E-FO-13 3 6mzz/E-HCFO-1233zd 0 5-12/95-88 以及 47-95/53-5 E-FO-1336mzz/E-HCFO-1233zd 20 5-17/95-83 以及 40-95/60-5 E-FO-1336mzz/E-HCFO-1233zd 40 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 50 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 60 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 80 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 100 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 120 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 140 5-95/95-5 經實驗發現，E-FO-1336mzz與HCFO-1233xf形成共沸或 類共沸物組成物。使用上述之PTx法測定此二元對之相對 揮發度。對各種二元組成物於恆溫下量測已知體積之ΡΤχ 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。 所量測得之蒸氣壓與E-FO-1336mzz/HCFO-1233xf混合 物於PTx槽中之組成關係乃如圖2所示，其以圖形繪示主要 由E-FO-1336mzz及HCFO-1233xf所組成之共沸組成物的形 155860.doc •13- 201139639 成’此可見於約81.6莫耳％之丑40-133611^2及18.4莫耳〇/0 之HCFO-1233xf之混合物，其於約25.7°C下在整個組成範 圍内具有最高的壓力。 基於這些發現’藉由計算可知，在約60.2莫耳百分比至 約98.8莫耳百分比E-FO-1336mzz以及約39.8莫耳百分比至 約1.2莫耳百分比HCFO-1233xf之範圍下，E-FO-1336mzz與 HCFO-1233xf形成共沸組成物（其形成之共沸組成物在約_ 40°C至約120°C之溫度下及在約1.5 psia (10 kPa)至約328 psia (2261 kPa)之壓力下沸騰）。舉例而言，在約25.7°C及 約29.4 psia (203 kPa)下，共沸組成物係主要由約81.6莫耳 0/〇 之 E-FO-1336mzz 與約 18.4 莫耳 ％ 之 HCFO-1233xf 所組 成。再舉例而言，在約7.0°C與約大氣壓力（14.7 psia，101 kPa)下，共沸組成物係主要由約76.3莫耳％的E-FO-1336mzz與約23.7莫耳％的HCFO-1233xf所組成。部分共沸 組成物實施例列於表3中。 Ι 55860.doc Μ 201139639 表3.共沸組成物 共沸溫度(°c) 共沸壓力(psia) E-FO-1336mzz (莫耳％) HCFO-1233xf (莫耳％) -40.0 1.46 60.2 39.8 -30.0 2.60 64.1 35.9 -20.0 4.40 67.7 32.3 -10.0 7.11 71.1 28.9 0.0 11.0 74.2 25.8 10.0 16.5 77.2 22.8 20.0 24.0 80.0 20.0 25.7 29.4 81.6 18.4 30.0 33.9 82.7 17.3 40.0 46.7 85.2 14.8 50.0 63.0 87.7 12.3 60.0 83.3 90.1 9.9 70.0 108 92.3 7.7 80.0 138 94.5 5.5 90.0 175 96.4 3.6 100.0 218 97.9 2.1 110.0 268 98.8 1.2 120.0 328 98.2 1.8 此外，也可形成包含E-FO-1336mzz及HCFO-1233xf之類 共沸物組成物。根據計算，主要由約1至約99莫耳百分比 E-F〇-1336mzz與約99至約1莫耳百分比HCFO-1233xf所組 成之類共沸物組成物，是在約_4〇。(：至約120°C之溫度範圍 内开> 成（亦即在此溫度範圍内，組成物在特定溫度下的露 155860.doc •15- 201139639 點壓力及泡點壓力之差係小於或等於百分之5(基於泡點壓 力））。 此種類共沸物組成物於共沸組成物附近形成。類共沸物 組成物的一些實施例乃如表4所列。類共沸物組成物的一 些更多實施例乃如表5所列。 表4.類共沸物組成物 組分 T(°C) 莫耳百分比範圍 E-FO-1336mzz/HCFO-1233xf -40 1-99/99-1 E-FO-1336mzz/HCFO-1233xf -20 1-99/99-1 E-FO-1336mzz/HCFO-1233xf 0 1-99/99-1 E-FO-1336mzz/HCFO-1233xf 40 1-99/99-1 E-FO-1336mzz/HCFO-1233xf 80 1-99/99-1 E-FO-133 6mzz/HCF0-1233xf 120 1-99/99-1 表5.類共沸物組成物 組分 T(°C) 莫耳百分比範圍 E-FO-1336mzz/HCFO-1233xf -40 5-95/95-5 E-FO-1336mzz/HCFO-1233xf -20 5-95/95-5 E-FO-13 3 6mzz/HCFO-123 3xf 0 5-95/95-5 E-FO-1336mzz/HCFO-1233xf 40 5-95/95-5 E-FO-1336mzz/HCFO-1233xf 80 5-95/95-5 E-FO-1336mzz/HCFO-1233xf 120 5-95/95-5 155860.doc -16- 201139639 本發明之共彿或類丘难你 乂頰/、，弗物組成物可藉由任何簡便之方法 製備’包括混合或紐所帝· μ 义、、且口所站的量。在本發明之一實施例 中，共》弗或類共彿物组成物1& 卿上成物可藉由稱量所需組分之量以及 之後於適當容器中將其組合而製備。 本發明之共/弗或類共彿物組成物可作廣泛應用，包括用 於作為氣膠推喷劑、冷媒、溶劑、洗淨劑、用於熱塑性及 熱固性發泡體之發泡劑（發泡體膨脹劑）、熱傳介質、氣體 介電質、滅火及阻燃齊丨、動力循環工作流體、聚合介質、 顆粒移除流體、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製備熱塑性及熱固性發泡體 之方法。此方法包括將共沸或類共沸物組成物作為發泡 劑，其中該共沸或類共沸物組成物係主要由E_丨，丨，丨，4,4,4_ 六氟-2- 丁烯與一選自於由E-HCFO-1233zd以及HCFO-1233xf所組成之群組之組分所組成。 本發明另一實施例提供一種產生冷凍作用之方法。此方 法包括冷凝共沸或類共 >弗物組成物，並於之後於欲冷卻體 附近蒸發該共沸或類共彿物組成物，其中該共彿或類共沸 物組成物係主要由E-l，l，l，4,4,4-六氟-2-丁烯與一選自於由 E-HCF〇-l233zd以及HCFO-1233xf所組成之群組之組分所 組成。 本發明另一實施例提供一種將共沸或類共沸物組成物作 為溶劑之方法，其中該共沸或類共沸物組成物係主要由 六氟-2-丁蝉與一選自於由E-HCFO-123 3zd以 及HCF〇-i23 3xf所組成之群組之組分所組成。 155860.doc •17· 201139639 本發明另一實施例提供一種生產氣膠產品之方法。此方 法包括將共沸或類共沸物組成物作為推進劑，其中該共沸 或類共沸物組成物係主要由£_1，1，1，4,4,4_六氟_2_丁烯與一 選自於由E-HCFO-1233zd以及HCFO-1233xf所組成之群組 之組分所組成。 本發明另一實施例提供一種將共沸或類共沸物組成物作 為熱傳介質之方法，其中該共沸或類共沸物組成物係主要 由 £-1，1，1，4,4,4-六氟-2_丁烯與一選自於由£_1^1?0_12332(1 以及HCF〇-1233xf所組成之群組之組分所組成。 本發明另一實施例提供一種滅火或阻燃之方法❶此方法 包括將共沸或類共沸物組成物作為滅火或阻燃劑，其中該 共沸或類共沸物組成物係主要由E-l，l，l，4,4,4-六氟-2-丁烯 與一選自於由E-HCFO-1233zd以及HCFO-1233xf所組成之 群組之組分所組成。 本發明另一實施例提供一種將共沸或類共沸物組成物作 為介電質之方法，其中該共沸或類共沸物組成物係主要由 E-l，l，l，4,4,4-六氟-2-丁稀與一選自於由 E-HCFO-1233zd 以 及HCFO-1233xf所組成之群組之組分所組成。 【圖式簡單說明】 圖 1 為主要由 E-FO-1336mzz 及 E-HCFO-1233zd 於約 24.7°C之溫度下所組成之類共沸物組成物的示意圖。Engineering, pp. 165-244, although not wishing to be bound by any theory or explanation, the NRTL formula and the gutter data are sufficient to predict that the invention contains El, l, l, 4, 4, 4 - six defeats - The relative volatility of the 2-butadiene composition's and thus the properties of such mixtures in multi-stage separation equipment, such as steaming towers, can be predicted. It was found by experiments that E-FO-1336mzz and E-HCFO_1233zd form an azeotrope-like composition. 155860.doc •10· 201139639 The relative volatility of this binary pair was determined using the above method. The pressure in the known volume of the gutter is measured at various temperatures for the various binary compositions. The receiver uses the NRTL equation to reduce these measurements to the equilibrium gas and liquid composition in the tank. The compositional relationship between the measured vapor pressure and the E-FO-1336mzz/E-HCFO-1233zd mixture in the gutter is shown in Figure 1 'It is graphically represented mainly by £-1,1,1,4 , 4,4-hexafluoro-2-butene and ^1^卩0-12332 (1 at 24.7. The formation of a common composition of the composition of the scorpion, which can be seen from about 1 to about 19 mol% a mixture of 2Ε-1,1,1,4,4,4-hexafluoro-2-butene and from about 99 to about 81 moles per ounce of E-HCFO-1233zd, and may be found from about 38 to about 99 moles a mixture of El,l,l,4,4,4-hexafluoro-2-butene and about 62 to about 1 mole of e-HCFO-12 3 3 zd. An azeotrope composition of from about i to about 99 mole percent EF 〇 1336mzz and from about 99 to about 1 mole percent E_HCF 〇_1233zd, is in the range of about -4 (TC to about 14 (rc) Forming (ie, within this temperature range) the difference between the dew point pressure and the bubble point pressure of the composition at a particular temperature is less than or equal to 5 percent (based on the bubble point pressure). Partially common > The contents of the material will be listed in Table i. Examples of other azeotrope-like compositions are listed in Table 2. 155860.doc 201139639 Table 1 · Azeotrope-like composition component T (°C) Mohr % range E-FO-133 6mzz/E-HCFO-1233zd -40 1-5/99-95 and 67-99 /33-1 E-FO-1336mzz/E-HCFO-1233zd -20 1-8/99-92 and 56-99/44-1 E-FO-1336mzz/E-HCFO-1233zd 0 1-12/99- 88 and 47-99/53-1 E-FO-1336mzz/E-HCFO-1233zd 20 1-17/99-83 and 40-99/60-1 E-FO-1336mzz/E-HCFO-1233zd 40 1- 99/99-1 E-FO-1336mzz/E-HCFO-1233zd 50 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 60 1-99/99-1 E-FO-1336mzz/E -HCFO-1233zd 80 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 100 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 120 1-99/99-1 E-FO-1336mzz/E-HCFO-1233zd 140 1-99/99-1 155S60.doc -12- 201139639 Table 2. Azeotrope-like composition component T (°C) Mohr % range E-FO- 1336mzz/E-HCFO-1233zd -40 67-95/33-5 E-FO-1336mzz/E-HCFO- 1233zd -20 5-8/95-92 and 56-95/44-5 E-FO-13 3 6mzz/E-HCFO-1233zd 0 5-12/95-88 and 47-95/53-5 E-FO-1336mzz/E-HCFO-1233zd 20 5-17/95-83 and 40-95/60-5 E-FO-1336mzz/E-HCFO-1233zd 40 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 50 5- 95/95-5 E-FO-1336mzz/E-HCFO-1233zd 60 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 80 5-95/95-5 E-FO-1336mzz/E -HCFO-1233zd 100 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 120 5-95/95-5 E-FO-1336mzz/E-HCFO-1233zd 140 5-95/95-5 It was found by experiments that E-FO-1336mzz forms an azeotrope or azeotrope-like composition with HCFO-1233xf. The relative volatility of this binary pair was determined using the PTx method described above. The pressure in the tank of known volume is measured at various temperatures for various binary compositions. These measurements are then reduced to the equilibrium gas and liquid composition in the tank using the NRTL equation. The compositional relationship between the measured vapor pressure and the E-FO-1336mzz/HCFO-1233xf mixture in the PTx tank is shown in Figure 2. It is graphically represented by E-FO-1336mzz and HCFO-1233xf. The shape of the azeotrope composition 155860.doc •13- 201139639 into a mixture of about 81.6 mol% ugly 40-133611^2 and 18.4 mol/0 of HCFO-1233xf, which is about 25.7° C has the highest pressure throughout the composition range. Based on these findings, by calculation, E-FO-1336mzz is in the range of about 60.2 mole percent to about 98.8 mole percent E-FO-1336mzz and about 39.8 mole percent to about 1.2 mole percent HCFO-1233xf. Forming an azeotrope composition with HCFO-1233xf (which forms an azeotrope composition at a temperature of from about _40 ° C to about 120 ° C and a pressure of from about 1.5 psia (10 kPa) to about 328 psia (2261 kPa)) Boil under). For example, at about 25.7 ° C and about 29.4 psia (203 kPa), the azeotrope composition is mainly composed of about 81.6 moles of O/FO-1336mzz and about 18.4 moles of HCFO-1233xf. composition. By way of further example, at about 7.0 ° C and about atmospheric pressure (14.7 psia, 101 kPa), the azeotrope composition is predominantly from about 76.3 mole % E-FO-1336mzz and about 23.7 mole % HCFO- The 1233xf is composed of. Partial azeotrope composition examples are listed in Table 3. Ι 55860.doc Μ 201139639 Table 3. Azeotropic composition azeotropic temperature (°c) Azeotropic pressure (psia) E-FO-1336mzz (mole%) HCFO-1233xf (mole%) -40.0 1.46 60.2 39.8 - 30.0 2.60 64.1 35.9 -20.0 4.40 67.7 32.3 -10.0 7.11 71.1 28.9 0.0 11.0 74.2 25.8 10.0 16.5 77.2 22.8 20.0 24.0 80.0 20.0 25.7 29.4 81.6 18.4 30.0 33.9 82.7 17.3 40.0 46.7 85.2 14.8 50.0 63.0 87.7 12.3 60.0 83.3 90.1 9.9 70.0 108 92.3 7.7 80.0 138 94.5 5.5 90.0 175 96.4 3.6 100.0 218 97.9 2.1 110.0 268 98.8 1.2 120.0 328 98.2 1.8 In addition, an azeotrope composition containing E-FO-1336mzz and HCFO-1233xf may also be formed. According to calculations, the azeotrope composition consisting essentially of from about 1 to about 99 mole percent E-F〇-1336mzz and from about 99 to about 1 mole percent HCFO-1233xf is about _4 Torr. (: open to a temperature range of about 120 ° C) (that is, in this temperature range, the composition of the exposed temperature at a specific temperature 155860.doc •15-201139639 point pressure and bubble point pressure is less than or Equivalent to 5 percent (based on bubble point pressure). This type of azeotrope composition is formed near the azeotrope composition. Some examples of azeotrope-like compositions are listed in Table 4. Azeotrope-like compositions Some more examples of the materials are listed in Table 5. Table 4. Azeotrope-like composition components T (°C) Mohr percentage range E-FO-1336mzz/HCFO-1233xf -40 1-99/99 -1 E-FO-1336mzz/HCFO-1233xf -20 1-99/99-1 E-FO-1336mzz/HCFO-1233xf 0 1-99/99-1 E-FO-1336mzz/HCFO-1233xf 40 1-99 /99-1 E-FO-1336mzz/HCFO-1233xf 80 1-99/99-1 E-FO-133 6mzz/HCF0-1233xf 120 1-99/99-1 Table 5. Azeotrope-like composition components T(°C) Mohr percentage range E-FO-1336mzz/HCFO-1233xf -40 5-95/95-5 E-FO-1336mzz/HCFO-1233xf -20 5-95/95-5 E-FO-13 3 6mzz/HCFO-123 3xf 0 5-95/95-5 E-FO-1336mzz/HCFO-1233xf 40 5-95/95-5 E-FO-1336mzz/HCFO-1233xf 80 5-95/95-5 E -FO-1336mzz/HCFO-1233x f 120 5-95/95-5 155860.doc -16- 201139639 The invention of the buddha or genus is difficult for you to cheek /,, the composition of the object can be prepared by any convenient method 'including mixing or New Zealand The amount of μ, and the amount of the mouth standing. In one embodiment of the invention, the total composition of the compound or the composition of the object can be weighed by the amount of the desired component and thereafter Prepared by combining them in a suitable container. The co-/fu or common-like composition of the present invention can be widely used, including as a gas-gel push spray, a refrigerant, a solvent, a detergent, for thermoplastics and Foaming agent (foaming expander), heat transfer medium, gas dielectric, fire extinguishing and flame retardant, power cycle working fluid, polymerization medium, particle removal fluid, carrier fluid, polishing and polishing of thermosetting foam Materials and Displacement Desiccants. One embodiment of the present invention provides a method of making thermoplastic and thermoset foams. The method comprises using an azeotrope or azeotrope-like composition as a blowing agent, wherein the azeotrope or azeotrope-like composition is mainly composed of E_丨, 丨, 丨, 4, 4, 4 hexafluoro-2- Butene is composed of a component selected from the group consisting of E-HCFO-1233zd and HCFO-1233xf. Another embodiment of the present invention provides a method of producing a freezing action. The method includes condensing an azeotrope or a mixture of agglomerates, and then evaporating the azeotrope or aroma-like composition near the body to be cooled, wherein the co-fossil or azeotrope-like composition is mainly composed of El,l,l,4,4,4-hexafluoro-2-butene is composed of a component selected from the group consisting of E-HCF〇-l233zd and HCFO-1233xf. Another embodiment of the present invention provides a method of using an azeotrope or azeotrope-like composition as a solvent, wherein the azeotrope or azeotrope-like composition is mainly composed of hexafluoro-2-butane and one selected from the group consisting of E-HCFO-123 3zd and HCF〇-i23 3xf consist of a group of components. 155860.doc • 17· 201139639 Another embodiment of the present invention provides a method of producing a gas gel product. The method comprises using an azeotrope or azeotrope-like composition as a propellant, wherein the azeotrope or azeotrope-like composition is mainly composed of £_1,1,1,4,4,4_hexafluoro_2_ The alkene is composed of a component selected from the group consisting of E-HCFO-1233zd and HCFO-1233xf. Another embodiment of the present invention provides a method of using an azeotrope or azeotrope-like composition as a heat transfer medium, wherein the azeotrope or azeotrope-like composition is mainly composed of £-1,1,1,4,4 , 4-hexafluoro-2-butene and a component selected from the group consisting of £_1^1?0_12332 (1 and HCF〇-1233xf. Another embodiment of the present invention provides a fire extinguishing or A method of flame retarding. The method comprises using an azeotrope or azeotrope-like composition as a fire extinguishing or flame retardant, wherein the azeotrope or azeotrope-like composition is mainly composed of El, 1, 14, 4, 4, 4 - hexafluoro-2-butene and a component selected from the group consisting of E-HCFO-1233zd and HCFO-1233xf. Another embodiment of the invention provides an azeotrope or azeotrope-like A method of using a composition as a dielectric, wherein the azeotrope or azeotrope-like composition is mainly composed of El, 1,1,4,4,4-hexafluoro-2-butene and one selected from E- The composition of the group consisting of HCFO-1233zd and HCFO-1233xf. [Simple diagram of the diagram] Figure 1 is composed mainly of E-FO-1336mzz and E-HCFO-1233zd at a temperature of about 24.7 °C. Azeotrope A schematic view thereof into.
圖 2 為主要由 E-FO-1336mzz及 HCFO-1233xf於約 25.7°C 之溫度下所組成之共沸組成物的示意圖。 I55860.doc -18 -Fig. 2 is a schematic view showing an azeotropic composition mainly composed of E-FO-1336mzz and HCFO-1233xf at a temperature of about 25.7 °C. I55860.doc -18 -