CN110184033A - E-HFO-1438ez和E-1-氯-三氟丙烯的类共沸组合物及其用途 - Google Patents
E-HFO-1438ez和E-1-氯-三氟丙烯的类共沸组合物及其用途 Download PDFInfo
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Abstract
本发明公开了类共沸组合物。所述类共沸组合物为HFO‑E‑1,3,4,4,4‑五氟‑3‑三氟甲基‑1‑丁烯和E‑1‑氯‑3,3,3‑三氟丙烯的混合物。本发明还公开了通过使用此类类共沸组合物作为发泡剂来制备热塑性或热固性泡沫的方法。本发明还公开了通过使用此类类共沸组合物来制冷的方法。本发明还公开了使用此类类共沸组合物作为溶剂的方法。本发明还公开了通过使用此类类共沸组合物制备气溶胶产品的方法。本发明还公开了使用此类类共沸组合物作为传热介质的方法。本发明还公开了通过使用此类类共沸组合物来灭火或抑燃的方法。本发明还公开了使用此类类共沸组合物作为电介质的方法。
Description
本申请是申请号为“201480055261.1”,发明名称为“FO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯的类共沸组合物及其用途”的发明申请的分案申请。
背景技术
发明领域
本公开涉及HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯的类共沸组合物。
相关领域说明
在过去的几十年中,许多行业一直致力于寻找替代物以替换会损耗臭氧的氯氟烃(CFC)和氢氯氟烃(HCFC)。氯氟烃和氢氯氟烃已被用于各式各样的应用中,包括将它们用作气溶胶抛射剂、制冷剂、清洁剂、热塑性和热固性泡沫的膨胀剂、传热介质、气体电介质、灭火剂和抑燃剂、动力循环工作流体、聚合反应介质、去除颗粒物的流体、载液、抛光研磨剂和置换干燥剂。在寻求这些多功能化合物的替代物的过程中,许多行业转向使用氢氟烃(HFC)。
氢氟烃对平流层的臭氧不具破坏性,但令人担忧的是这种物质会促进“温室效应”(即它们会促进全球变暖)。由于氢氟烃会促进全球变暖,因此已受到严格审查,其广泛应用在将来也会受到限制。
发明内容
因此,需要对平流层臭氧不具有破坏性并且还具有低全球变暖潜势(GWP)的组合物。某些氢氟烯烃诸如HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1丁烯((CF3)2CFCH=CHF,反式-HFO-1438ez,
E-HFO-1438ez,E-1438ez)据信可满足这两个目标。本公开提供基本上由(a)HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和(b)E-1-氯-3,3,3-三氟丙烯组成的组合物;其中所述E-1-氯-3,3,3-三氟丙烯以与HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯形成类共沸混合物的有效量存在。
附图说明
图1-图1为在约27.8℃的温度下HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯与E-1-氯-3,3,3-三氟丙烯的类共沸组合物的图示。
具体实施方式
在许多应用中,期望使用单一的纯组分或共沸或类共沸混合物。例如,当发泡剂组合物(还被称为泡沫膨胀剂或泡沫膨胀组合物)不是单一的纯组分或共沸或类共沸混合物时,所述组合物在其应用于泡沫形成过程期间会发生变化。这种组成变化会不利地影响处理,或导致应用中性能变差。同样,在制冷应用中,制冷剂通常在操作期间经由轴密封件、软管连接、焊接接头和接折线中的裂缝而流失。此外,所述制冷剂可在制冷设备的维护过程期间被释放到大气中。如果所述制冷剂不是单一的纯组分或共沸或类共沸组合物,则当从制冷设备渗漏或排放到大气中时,所述制冷剂组成会变化。制冷剂组成的变化可导致制冷剂变得易燃,或导致具有较差的制冷性能。因此,需要在这些应用以及其它应用中使用共沸或类共沸混合物,例如包含HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯的共沸或类共沸混合物。
在陈述下文实施例的详情之前,首先定义或阐明一些术语。
如本文所用,术语“包含”、“包括”、“具有”或它们的任何其他变型均旨在涵盖非排他性的包括。例如,包括要素列表的工艺、方法、制品或设备不必仅限于那些要素,而是可以包括未明确列出的或此类工艺、方法、制品或设备所固有的其他要素。此外,除非明确规定相反的意思,否则“或”是指包含性的而非排他性的“或”。例如,下列任一种情况都表示条件A或B得到满足:A为真(或存在A)且B为假(或不存在B),A为假(或不存在A)且B为真(或存在B),A和B都为真(或既存在A,又存在B)。
而且,采用“一个”或“一种”来描述本文所述的元素和组分。这样做只是为了方便,并给出本发明范围的一般意义。除非意思明显相反,否则该描述应当理解为包括一个/种或至少一个/种,并且单数也包括复数的意思。
除非另外规定,否则本文所用的全部科技术语的含义都与本发明所属领域的普通技术人员通常理解的一致。尽管与本文描述的方法和材料类似或等同的方法和材料也可用于实践或测试本发明的实施例,但下文描述了适宜的方法和材料。除非引用具体段落,否则本文提及的全部出版物、专利申请、专利以及其他参考文献均以全文引用方式并入本文。如发生矛盾,以本说明书及其包括的定义为准。此外,描述的材料、方法和实例只是示例性的,而非限制性的。
当数量、浓度或其他数值或参数以范围、优选范围或优选上限数值和/或优选下限数值的列表形式给出时,它应理解为具体地公开了由任何范围上限或优选数值和任何范围下限或优选数值的任何一对所构成的所有范围,而不管所述范围是否被单独地公开。除非另外指明,否则凡在本文中给出某一数值范围之处,该范围均旨在包括其端点,以及位于该范围内的所有整数和分数。
本申请包括基本上由(a)HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成的组合物;其中所述E-1-氯-3,3,3-三氟丙烯以与HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯形成类共沸混合物的有效量存在。
有效量是指当与HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯组合时导致形成类共沸混合物的E-1-氯-3,3,3-三氟丙烯的量。该定义包括每种组分的量,所述量可根据施加在所述组合物上的压力而变化,只要所述类共沸组合物在不同的压力下持续存在,但却具有可能不同的沸点。因此,有效量包括在不同于本文所述的温度或压力下形成类共沸组合物的本发明的组合物中每种组分的量,诸如以重量百分比或摩尔百分比表示的量。
如本领域所认识到的,共沸组合物是两种或更多种不同组分的混合物,当在给定压力下为液体形式时,所述混合物将在基本上恒定的温度下沸腾,所述温度可以高于或低于单独组分的沸腾温度,并且将提供基本上与经历沸腾的整个液体组成相同的蒸汽组成。(参见例如M.F.Doherty and M.F.Malone,Conceptual Design of DistillationSystems,McGraw-Hill(New York),2001,185-186,351-359(M.F.Doherty和M.F.Malone,《蒸馏系统的概念设计》,麦格劳希尔图书公司(纽约),2001年,第185-186卷,第351-359页))。
因此,共沸组合物的基本特征在于:在给定压力下,液体组合物的沸点是固定的,并且沸腾组合物上方的蒸气组成基本上就是整个沸腾液体组合物的组成(即,未发生液体组合物组分的分馏)。本领域还认识到,当共沸组合物在不同压力下经历沸腾时,共沸组合物中每种组分的沸点和重量百分比均可变化。因此,特征在于在特定压力下具有固定沸点的共沸组合物可从以下几方面进行定义:存在于组分之间的独特关系、或所述组分的组成范围、或所述组合物中每种组分的精确重量百分比。
对于本发明的目的而言,类共沸组合物是指行为类似共沸组合物的组合物(即在沸腾或蒸发时具有恒沸特性或无分馏趋势)。因此,在沸腾或蒸发期间,如果蒸气和液体组合物发生一些变化,则也仅发生最小程度或可忽略程度的变化。这与非类共沸组合物形成对比,在所述非类共沸组合物中,蒸气和液体组成在沸腾或蒸发期间发生显著程度的变化。
此外,类共沸组合物表现出几乎无压差的露点压力和泡点压力。也就是说,在给定温度下,露点压力和泡点压力之差是很小的值。在本发明中,露点压力和泡点压力的差值小于或等于5%(基于泡点压力)的组合物被认为是类共沸的。
本领域认识到,当体系的相对挥发度接近1.0时,所述体系被定义为形成共沸或类共沸组合物。相对挥发度是组分1的挥发度与组分2的挥发度的比率。蒸汽态的组分与液态的组分的摩尔分数的比率为所述组分的挥发度。
可使用被称为PTx方法的方法来测定任何两种化合物的相对挥发度。可等温或等压测定气-液平衡(VLE),以及因此测定相对挥发度。等温方法需要测定已知组成的混合物在恒定温度下的总压力。在该方法中,测定不同组成的两种化合物在恒定的温度下在已知体积的单元中的总绝对压力。等压方法需要测定已知组成的混合物在恒定压力下的温度。在该方法中,测定在恒定压力下含有两种化合物的不同组合物在已知体积的单元中的温度。PTx方法的使用更详细地描述于由Harold R.Null撰写的“Phase Equilibrium inProcess Design”(工艺设计中的相平衡)(威利数据库出版社(Wiley-IntersciencePublisher),1970年)第124至126页中。
通过使用活度系数方程模型诸如非随机两液体(Non-Random,Two-Liquid)(NRTL)方程来表示液相非理想因素,可将这些量度转换成PTx单元中的平衡蒸气和液体组成。活度系数方程诸如NRTL方程的应用更详细地描述于由Reid、Prausnitz和Poling撰写、由McGrawHill出版的“The Properties of Gases and Liquids”(气体和液体的性质)第4版第241至387页,以及由Stanley M.Walas撰写、由Butterworth Publishers出版的“PhaseEquilibria in Chemical Engineering”(化学工程中的相平衡)(1985年)第165至244页中。不希望受任何理论或解释的束缚,据信NRTL方程与PTx单元数据一起可足以预测本发明的HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯/E-1-氯-3,3,3-三氟丙烯组合物的相对挥发度,因而可预测这些混合物在多级分离设备诸如蒸馏塔中的行为。
通过实验发现,HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯形成类共沸组合物。
使用上述的PTx方法来测定该二元对的相对挥发度。测量各种二元组合物在恒定的温度下在已知体积的PTx单元中的压力。然后使用NRTL方程将这些量度还原成所述单元中的平衡蒸汽和液体组成。
相对于PTx单元中HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯混合物的组成所测量的压力示于图1中,该图以图形方式示出了在27.8℃和从约18到21psia范围内的压力下形成基本上由1-44摩尔%HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和56-99摩尔%E-1-氯-3,3,3-三氟丙烯组成的类共沸组合物,并且还示出了在27.8℃和从约13到14psia范围内的压力下形成基本上由84-99摩尔%HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和1-16摩尔%E-1-氯-3,3,3-三氟丙烯组成的类共沸组合物。
根据计算,在约-40℃至约140℃范围内的温度下形成基本上由1-99摩尔%HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和1-99摩尔%E-1-氯-3,3,3-三氟丙烯组成的类共沸组合物(即,在该温度范围内,所述组合物在特定温度下的露点压力与泡点压力之差小于或等于5%(基于泡点压力))。
类共沸组合物的一些实施例列于表1中
表1类共沸组合物
本发明的类共沸组合物可由任何便利的方法来制成,包括混合或组合所需的量。在本发明的一个实施例中,通过称量所需的组分量,然后将它们合并在适当的容器中来制备类共沸组合物。
本发明的类共沸组合物可用于范围广泛的应用中,包括将它们用作气溶胶抛射剂、制冷剂、溶剂、清洁剂、热塑性和热固性泡沫的发泡剂(泡沫膨胀剂)、传热介质、气体电介质、灭火剂和抑燃剂、动力循环工作流体、聚合介质、颗粒移除流体、载液、抛光研磨剂、以及置换干燥剂。
本发明的一个实施例提供了用于制备热塑性泡沫或热固性泡沫的方法。所述方法包括使用类共沸组合物作为发泡剂,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
本发明的另一个实施例提供了用于制冷的方法。所述方法包括冷凝类共沸组合物,然后在邻近待冷却主体的位置处蒸发所述类共沸组合物,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
本发明的另一个实施例提供了使用类共沸组合物作为溶剂的方法,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
本发明的另一个实施例提供了用于制备气溶胶产品的方法。所述方法包括使用类共沸组合物作为抛射剂,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
本发明的另一个实施例提供了使用类共沸组合物作为传热介质的方法,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
本发明的另一个实施例提供了用于灭火或抑燃的方法。所述方法包括使用类共沸组合物作为灭火剂或抑燃剂,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
本发明的另一个实施例提供了使用类共沸组合物作为电介质的方法,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
Claims (9)
1.一种组合物,所述组合物基本上由下列组成:
(a)HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯;和
(b)E-1-氯-3,3,3-三氟丙烯;其中所述E-1-氯-3,3,3-三氟丙烯以与所述HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯形成类共沸组合的有效量存在。
2.一种用于制备热塑性或热固性泡沫的方法,所述方法包括使用类共沸组合物作为发泡剂,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
3.一种用于制冷的方法,所述方法包括冷凝类共沸组合物,然后在邻近待冷却主体的位置处蒸发所述类共沸组合物,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
4.一种方法,所述方法包括使用类共沸组合物作为溶剂,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
5.一种用于制备气溶胶产品的方法,所述方法包括使用类共沸组合物作为抛射剂,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
6.一种方法,所述方法包括使用类共沸组合物作为传热介质,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
7.一种用于灭火或抑燃的方法,所述方法包括使用类共沸组合物作为灭火剂或抑燃剂,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
8.一种方法,所述方法包括使用类共沸组合物作为电介质,其中所述类共沸组合物基本上由HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和E-1-氯-3,3,3-三氟丙烯组成。
9.根据权利要求2所述的方法,其中所述类共沸组合物基本上由95-99摩尔%HFO-E-1,3,4,4,4-五氟-3-三氟甲基-1-丁烯和1-5摩尔%E-1-氯-3,3,3-三氟丙烯组成。
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