CN102741203A - 顺式-1,1,1,4,4,4-六氟-2-丁烯的类共沸物组合物 - Google Patents
顺式-1,1,1,4,4,4-六氟-2-丁烯的类共沸物组合物 Download PDFInfo
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- CN102741203A CN102741203A CN201080063807XA CN201080063807A CN102741203A CN 102741203 A CN102741203 A CN 102741203A CN 201080063807X A CN201080063807X A CN 201080063807XA CN 201080063807 A CN201080063807 A CN 201080063807A CN 102741203 A CN102741203 A CN 102741203A
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Abstract
Description
对相关申请的交叉引用
本申请要求2009年12月16日提交的美国临时专利申请序号No. 61/287,041的权益,其公开内容经此引用并入本文。
发明领域
本发明涉及可用于许多用途的类共沸物组合物、方法和系统,特别是包含或基本由有效量的具有下列结构的化合物顺式-1,1,1,4,4,4-六氟-2-丁烯(Z-HFO-1336mzzm)和选自水、氟酮、醇、氢氯氟烯烃及其两种或更多种的组合的另外的材料构成的类共沸物组合物的用途:
发明背景
本发明的类共沸物组合物是对下一代低全球变暖潜势材料的持续研究的一部分。这种材料必须具有通过超低全球变暖潜势和接近零的臭氧消耗潜势测得的低环境影响。
本发明的类共沸物组合物可用于多种用途,如发泡剂、制冷剂、加热剂、动力循环剂(power cycle agents)、清洁剂、气溶胶推进剂、灭菌剂、润滑剂、香精和香料萃取剂、可燃性降低剂和火焰抑制剂,列举几个优选用途。
发明概述
申请人已经开发出几种包括Z-HFO-1336mzzm作为基本组分的类共沸物组合物。在某些实施方案中,该类共沸物组合物的另一部分是至少一种C1至C12醇化合物。在另一些实施方案中,该类共沸物组合物的所述另一部分是水。在另一些实施方案中,该类共沸物组合物的所述另一部分是氟酮化合物。在另一些实施方案中,该类共沸物组合物的所述另一部分是氢氯氟烯烃化合物。
根据某些实施方案,本发明提供包含或优选基本由大于0至大约99重量%的化合物Z-HFO-1336mzzm和大约1重量%至小于100重量%的醇及其两种或更多种的组合构成的类共沸物组合物。优选的醇是C1至C12醇。尤其优选的是甲醇和乙醇。
应该指出,被称作Z-HFO-1336mzzm的产物通常和预计包括较小百分比,例如大约0.5重量%至大约5重量%的其它组分,特别包括E-HFO-1336mzzm。本文中所用的术语“基本由Z-HFO-1336mzzm构成”意在大致包括这样的组合物。本文所用的术语“由...构成”不包括这样的其它组分。如果需要,本文所述的本发明的所有实施方案可以以基本纯化形式获得,以使这些实施方案优选除微量(例如ppm)杂质外仅由指定的实际组分构成。
本发明优选提供包含或优选基本由Z-HFO-1336mzzm/乙醇或Z-HFO-1336mzzm/甲醇构成的共沸物和类共沸物组合物。优选地,本发明的类共沸物组合物包含或更优选基本由有效量的Z-HFO-1336mzzm和乙醇或Z-HFO-1336mzzm和甲醇构成。本文所用的术语“有效量”是指在与其它组分合并时导致形成本类共沸物组合物的各组分的量。
在某些实施方案中该类共沸物组合物包含或优选基本由大约75重量%至小于100重量%的Z-HFO-1336mzzm和从大于0至大约25重量%的醇及其两种或更多种的组合构成。
在另一些实施方案中,该类共沸物组合物包含或优选基本由大约85重量%至小于100重量%的Z-HFO-1336mzzm和从大于0至大约15重量%的醇及其两种或更多种的组合构成。
本发明的另一实施方案涉及包含从大于0至大约99重量%的复合水(compound water )和大约1重量%至小于100重量%的Z-HFO-1336mzzm的类共沸物组合物。
在某些实施方案中该类共沸物组合物包含或优选基本由大于0至大约50重量%的水和大约50重量%至小于100重量%的Z-HFO-1336mzzm构成。
在另一些实施方案中,该类共沸物组合物包含或优选基本由大于0至大约10重量%的水和大约90重量%至小于100重量%的Z-HFO-1336mzzm构成。
本发明的一个实施方案是包含或基本由一种或多种本发明的类共沸物组合物构成的发泡剂。
本发明的另一实施方案是形成泡沫的方法,包括向可发泡组合物中加入包含或基本由一种或多种本发明的类共沸物组合物构成的发泡剂。该发泡剂可进一步包含多元醇和发泡剂的预混物,其中该发泡剂包含本发明的类共沸物组合物。
本发明的再一实施方案是通过使可发泡组合物在包含或基本由一种或多种本发明的类共沸物组合物构成的发泡剂存在下发泡而制成的闭孔泡沫。该闭孔泡沫优选由进一步包含聚氨酯、聚异氰脲酸酯、聚苯乙烯、聚乙烯及其混合物的可发泡组合物形成。
本发明的一个实施方案是包含或基本由一种或多种本发明的类共沸物组合物构成的制冷剂组合物。本发明的另一实施方案是包含本发明的制冷剂组合物的制冷系统。本发明的再一实施方案是冷却制品的方法,其包括在要冷却的制品附近蒸发本发明的制冷剂组合物。
本发明的另一实施方案是加热制品的方法,其包括在要加热的制品附近冷凝包含或基本由一种或多种本发明的类共沸物组合物构成的制冷剂组合物。
本发明的一个实施方案是包含要喷施的材料和包含或基本由一种或多种本发明的类共沸物组合物构成的推进剂的可喷组合物。
本发明的再一实施方案是降低流体的可燃性的方法,包括将一种或多种本发明的类共沸物组合物添加到所述流体中。
本发明的另一实施方案是抑制火焰的方法,包括使所述火焰与包含一种或多种本发明的类共沸物组合物的流体接触。任选地,这种流体可进一步包括一种或多种氟酮化合物。一种优选的氟酮化合物是十二氟-2-甲基戊-3-酮。这种化合物的一种来源是以商标名Novec 1230获自3M Company。
本发明的再一实施方案是清洁和/或消毒制品的方法,所述方法包括使要清洁或消毒的所述制品与包含或基本由一种或多种本发明的类共沸物组合物构成的组合物接触。该组合物任选进一步包括环氧乙烷。
类共沸物
术语类共沸物是指表现得像共沸混合物的组合物,即在沸腾或蒸发过程中形成的蒸气的组成与原始液体组成相同或基本相同。因此,在沸腾或蒸发时,该液体组合物仅以微小或可忽略的程度(如果有的话)改变。这不同于非类共沸物组合物,其中在沸腾或蒸发过程中,该液体组合物显著改变。
术语“类共沸物”因此在其广义内意在包括严格共沸的组合物或表现得像共沸混合物的组合物。根据基本原理,流体的热力学状态取决于压力、温度、液体组成和蒸气组成。共沸混合物是两种或更多种组分的体系,其中液体组成和蒸气组成在指定压力和温度下相等。实践中,这意味着共沸混合物的组分是恒沸的并在相变过程中不会分离。
术语“类共沸物”尤其是指化合物Z-HFO-1336mzzm与基本表现得像单一化合物的一种或多种化合物的组合,只要与液体基本平衡的蒸气具有该液体中存在的组分的基本相同浓度。
本发明的类共沸物组合物包括绝对共沸物(其中在特定压力下在所有温度值(直至临界阶段)都满足共沸条件的组合物)或有限共沸物(其中在特定条件下仅在一定温度范围内满足共沸条件的组合物)。本发明的类共沸物组合物还包括均相共沸物——其中在给定压力下该组合物以单相存在,或多相共沸物——其中在给定压力下该组合物以两个或更多个液相存在。此外,根据该组合物分别由2、3、4还是5种(或更多)化合物构成,本发明的类共沸物组合物可以是二元、三元、四元或五元共沸物。
本发明的类共沸物组合物可包括不形成新的类共沸物体系的附加组分或不在第一馏分中的附加组分。第一馏分是在蒸馏塔在全回流条件下表现出稳态运行后获取的第一馏分。确定组分的添加是否形成新的类共沸物体系以致超出本发明的一种方式是在预计将非共沸混合物分离成其独立组分的条件下蒸馏含该组分的组合物的样品。如果含有附加组分的混合物不是类共沸物的,附加组分会与类共沸物的组分分馏。如果该混合物是类共沸物的,将获得恒沸或表现得像单物质的含有所有混合物组分的一定有限量的第一馏分。
由此确定类共沸物组合物的另一特征在于,存在以不同比例含有相同组分的一系列组合物,它们是类共沸物的或恒沸的。本文所用的“恒沸”是指在类共沸物组合物改变时该组合物的沸点改变不大于大约± 2℃,优选不大于大约± 1℃,更优选不大于大约± 0.5℃,最优选不大于大约± 0.2℃。术语“类共沸物”和“恒沸”意在涵盖所有这样的组合物。例如,公知的是,在不同压力下,给定共沸物的组成至少轻微改变,该组合物的沸点也如此。
如上所述,本发明的类共沸物组合物是恒沸或基本恒沸的。换言之,对这些类共沸物组合物而言,在沸腾或蒸发过程中形成的蒸气的组成与原始液体组成相同或基本相同。因此,在沸腾或蒸发时,该液体组合物仅以微小或可忽略的程度(如果有的话)改变。这不同于非类共沸物组合物,其中在沸腾或蒸发过程中,该液体组合物显著改变。
因此,组分A和组分B的类共沸物组合物代表独特类型的关系,但根据温度和/或压力具有可变组成。因此,对类共沸物组合物而言,存在以不同比例含有相同组分的一系列组合物,它们是类共沸物的。本文所用的术语“类共沸物”意在涵盖所有这样的组合物。
本发明的优选类共沸物组合物是环保的并且不造成地球平流臭氧层的消耗。本发明的化合物和组合物基本无臭氧消耗潜势(ODP),具有优选不大于大约0.5的ODP,再更优选不大于大约0.25的ODP,最优选不大于大约0.1的ODP;和/或不大于大约150的全球变暖潜势(GWP),再更优选不大于大约50的GWP。该组合物优选同时符合这两个标准。
本文所用的ODP如经此引用并入本文的“Scientific Assessment of Ozone Depletion, 2002”——World Meteorological association的报告中所规定。
本文所用的GWP相对于二氧化碳并经100年期规定,并在与上文提到的ODP相同的参考资料中规定。
在一个优选实施方案中,本发明提供包含或优选基本由Z-HFO-1336mzzm和乙醇构成的类共沸物组合物。本发明的另一优选实施方案提供包含或优选基本由Z-HFO-1336mzzm和甲醇构成的类共沸物组合物。同样可以使用其它醇,如丙醇、丁醇、戊醇、己醇、辛醇、壬醇、癸醇等。
附图简述
图1图解聚氨酯泡沫的k系数。
优选实施方案详述
在本发明的类共沸物组合物,Z-HFO-1336mzzm的量可广泛变化,在所有情况下包括构成计算组合物中的所有其它组分后该组合物的余量。
如上所述,甲醇和乙醇是本发明的优选类共沸物组合物中所用的优选醇。这些实施方案优选提供包含并优选由大于0至大约50重量份乙醇和大约50至小于100重量份Z-HFO-1336mzzm,更优选大于0至大约20重量份乙醇和大约80至小于100重量份Z-HFO-1336mzzm,再更优选大于0至大约10重量份乙醇和大约90至小于100重量份Z-HFO-1336mzzm构成的类共沸物组合物。本发明的优选的乙醇基类共沸物组合物以在14.3 psia下大约31.3℃,优选± 2℃,更优选± 1℃的沸点为特征。
这些实施方案优选提供包含并优选由大约1至大约50重量份甲醇和大约50至大约99重量份Z-HFO-1336mzzm,更优选大约1至大约70重量份甲醇和大约30至大约99重量份Z-HFO-1336mzzm,再更优选大约1至大约85重量份甲醇和大约15至大约99重量份Z-HFO-1336mzzm构成的类共沸物组合物。本发明的优选组合物以在14.3 psia下大约29.7℃,优选± 2℃,更优选± 1℃的沸点为特征。
可以按需要添加附加组分以调节本发明的类共沸物组合物的性质。例如,在本发明的类共沸物组合物用作制冷剂的情况下可添加助油溶剂。也可以添加稳定剂和其它材料以增强本发明的类共沸物组合物的性质。
可以使用萃取剂,如水从该共沸物中除去乙醇或甲醇。由于各醇在水中的高溶解度,醇被移除到水相中,Z-HFO-1336mzzm与水相相分离,留下纯化Z-HFO-1336mzzm。可随后使用普通干燥技术如分子筛从水中萃取醇。
另一些实施方案优选提供包含并优选由大约1至大约50重量份水和大约50至大约99重量份Z-HFO-1336mzzm,更优选大约10至大约40重量份水和大约60至大约90重量份Z-HFO-1336mzzm,再更优选大约15至大约35重量份水和大约65至大约85重量份Z-HFO-1336mzzm构成的类共沸物组合物。本发明的优选组合物以在14.5 psia下大约31.4℃,优选± 2℃,更优选± 1℃的沸点为特征。
另一些实施方案优选提供包含并优选由大约1至大约50重量份氟酮十二氟-2-甲基戊-3-酮和大约50至大约99重量份Z-HFO-1336mzzm,更优选大约5至大约45重量份Novec 1230和大约55至大约95重量份Z-HFO-1336mzzm,再更优选大约10至大约30重量份氟酮和大约70至大约90重量份Z-HFO-1336mzzm构成的类共沸物组合物。本发明的优选组合物以在14.5 psia下大约32.0℃,优选± 2℃,更优选± 1℃的沸点为特征。
本发明的组合物,包括优选类共沸物组合物,可包括一种或多种不形成新的类共沸物组合物的组分,如添加剂。在本组合物中可以使用已知添加剂以针对特定用途调节该组合物。也可以向本组合物中加入抑制剂以抑制分解,与不合意的分解产物反应,和/或防止金属表面腐蚀。通常,可以使用占类共沸物组合物总重量的最多大约2%的抑制剂。
共沸物添加剂
本发明的类共沸物组合物可进一步包括各种任选添加剂,包括稳定剂、金属钝化剂、缓蚀剂等。
根据某些实施方案,本发明的类共沸物组合物进一步包含稳定剂。可以使用适用于稳定本发明的类共沸物组合物的各种化合物。某些优选稳定剂的实例包括包含至少一种酚组合物和至少一种选自芳族环氧化物、烷基环氧化物、烯基环氧化物及其两种或更多种的组合的环氧化物的稳定剂组合物。该稳定剂混合物可进一步包含硝基甲烷、1,2-环氧丁烷和1,3-二氧戊环或1,4-二氧杂环己烷。还已经发现,各种萜烯烃和萜烯醇以及矿油精(mineral spirits)、二醇醚、醇和酮可以与上述稳定剂混合物联合使用。
各种酚化合物适用于本组合物。尽管申请人不希望受制于任何操作理论,但据信,酚充当该类共沸物组合物中的自由基清除剂并由此倾向于提高此类组合物的稳定性。本文所用的术语酚化合物通常是指任何取代或未取代的酚。合适的酚化合物的实例包括包含一个或多个取代或未取代的环状、直链或支化脂族取代基的酚,如烷基化单酚,包括:2,6-二-叔丁基-4-甲基苯酚;2,6-二-叔丁基-4-乙基苯酚;2,4-二甲基-6-叔丁基苯酚;生育酚;等等,氢醌和烷基化氢醌,包括:叔丁基氢醌;氢醌的其它衍生物;等等,羟基化硫代二苯基醚,包括:4,4'-硫代双(2-甲基-6-叔丁基苯酚);4,4'-硫代双(3-甲基-6-叔丁基苯酚);2,2'-硫代双(4-甲基-6-叔丁基苯酚);等等,亚烷基-双酚,包括:4,4'-亚甲基双(2,6-二-叔丁基苯酚);4,4'-双(2,6-二-叔丁基苯酚;2,2-或4,4-联苯二醇的衍生物;2,2'-亚甲基双(4-乙基-6-叔丁基苯酚);2,2'-亚甲基双(4-甲基-6-叔丁基苯酚);4,4,-亚丁基双(3-甲基-6-叔丁基苯酚);4,4,-异亚丙基双(2,6-二-叔丁基苯酚);2,2'-亚甲基双(4-甲基-6-壬基苯酚);2,2'-异亚丁基双(4,6-二甲基苯酚);2,2'-亚甲基双(4-甲基-6-环己基苯酚), 2,2-或4,4-联苯二醇,包括2,2'-亚甲基双(4-乙基-6-叔丁基苯酚)、丁基化羟基甲苯(BHT)、包含杂原子的双酚,包括:2,6-二-叔-.α.-二甲基氨基-对甲酚;4,4-硫代双(6-叔丁基-间甲酚);等等;酰基氨基酚;2,6-二-叔丁基-4(N,N'-二甲基氨基甲基苯酚);硫化物,包括:双(3-甲基-4-羟基-5-叔丁基苄基)硫化物;双(3,5-二-叔丁基-4-羟基苄基)硫化物;等等;以及酚式UV吸收剂和光稳定剂。
某些优选的酚包括烷基化单酚,如生育酚、BHT、氢醌等。某些特别优选的酚包括生育酚等。大多数酚可购得。在本组合物中可以使用单一酚化合物和/或两种或更多种酚的混合物。各种环氧化物适用于本发明的类共沸物组合物。尽管申请人不希望受制于任何操作理论,但据信,本发明的环氧化物充当该类共沸物组合物中的酸清除剂并由此倾向于提高此类组合物的稳定性。在本组合物中可以使用单一芳族环氧化物和/或两种或更多种芳族环氧化物的混合物。
在某些其它优选实施方案中,用作本组合物中的酸清除剂的烷基环氧化物包含聚丙二醇二缩水甘油醚。适用于本发明的聚丙二醇二缩水甘油醚的实例包括可购自SACHEM, Europe的醚。
此外,在某些实施方案中,用于本发明的环氧化物包含两个或更多个芳族、烷基和/或烯基取代基的组合。此类环氧化物通常被称作“多取代环氧化物”。根据某些优选实施方案,用于本发明的稳定剂包含至少一种酚化合物和至少一种芳族环氧化物、烷基环氧化物或烯基环氧化物的组合。合适的组合的实例包括包含:生育酚和烯丙基缩水甘油醚、BHT和缩水甘油基丁基醚等的稳定剂。某些特别优选的组合包括包含生育酚和烯丙基缩水甘油醚等的稳定剂。
在优选稳定剂中可以使用任何合适的相对量的所述至少一种酚化合物和所述至少一种芳族环氧化物、烷基环氧化物或烯基环氧化物。例如,酚化合物与芳族环氧化物或氟化烷基环氧化物的重量比可以为大约1:99至大约99:1不等。在某些优选实施方案中,酚化合物与芳族环氧化物、烷基环氧化物、烯基环氧化物、多取代或氟化烷基环氧化物的重量比为大约30至大约1,更优选大约7至大约1,更优选大约2至大约1,再更优选大约1:1。
共沸物实施例
实施例1
将69.4重量% Z-HFO-1336mzzm、3.1重量%乙醇、7.6重量%轻质物和余量重质物的样品装入Monel蒸馏塔中。该蒸馏塔是在大气压下运行的旋带精馏塔。使用恒温丙二醇水溶液冷却该冷凝器。
该蒸馏塔最初在全回流下运行并使其在各所需条件下达到温度和压力平衡。一旦该塔达到平衡,从蒸馏塔的塔顶提取蒸气样品。在收集馏出物时定期从该塔的塔顶取样。在从蒸馏塔中除去轻质物后取样。该样品表明Z-HFO-1336mzzm中2.0重量%乙醇。乙醇持续存在(persisted)于Z-HFO-1336mzzm馏分中,表明已形成共沸物。
实施例2
使用沸点计测量Z-HFO-1336mzzm和乙醇的共沸物。沸点计由在底部密封并在顶部朝大气敞开的真空隔绝玻璃容器构成。该沸点计的顶部或冷凝器部分被干冰包围以确保所有蒸气冷凝并流回到沸点计中。先将Z-HFO-1336mzzm装入沸点计中并计量加入乙醇。
表1显示表明已形成的共沸物的最低温度。该混合物的始沸点温度保持恒定,表明这种混合物在大的组成范围内是类共沸物的。
表1
Z-HFO-1336mzzm和乙醇在14.3 psia下的沸点计测量值
Z-HFO-1336mzzm, 重量% | 乙醇, 重量% | Temp, ℃ |
100.00 | 0.00 | 31.6 |
99.59 | 0.41 | 31.3 |
97.97 | 2.03 | 31.2 |
95.65 | 4.35 | 31.1 |
93.43 | 6.57 | 31.1 |
89.95 | 10.05 | 31.1 |
84.30 | 15.70 | 31.2 |
79.32 | 20.68 | 31.3 |
74.90 | 25.10 | 31.3 |
70.53 | 29.47 | 31.3 |
66.64 | 33.36 | 31.4 |
63.15 | 36.85 | 31.4 |
实施例2
使用如实施例2中的沸点计测量Z-HFO-1336mzzm和甲醇的共沸物。先将Z-HFO-1336mzzm装入沸点计中并计量加入甲醇。
表2显示表明已形成共沸物的最低温度。该混合物的始沸点温度保持恒定,表明这种混合物在大的组成范围内是类共沸物的。
表2
Z-HFO-1336mzzm和甲醇在14.3 psia下的沸点计测量值
Z-HFO-1336mzzm, 重量% | 甲醇, 重量% | Temp, ℃ |
100.00 | 0.00 | 32.02 |
99.59 | 0.41 | 30.81 |
98.78 | 1.22 | 29.92 |
97.20 | 2.80 | 29.68 |
94.19 | 5.81 | 29.66 |
91.35 | 8.65 | 29.66 |
86.17 | 13.83 | 29.78 |
81.55 | 18.45 | 29.80 |
77.39 | 22.61 | 29.90 |
73.19 | 26.81 | 29.94 |
69.43 | 30.57 | 29.99 |
66.03 | 33.97 | 30.14 |
62.96 | 37.04 | 30.24 |
60.15 | 39.85 | 30.44 |
实施例3
使用如实施例2中的沸点计测量Z-HFO-1336mzzm和十二氟-2-甲基戊-3-酮(Novec 1230)的共沸物。先将Z-HFO-1336mzzm装入沸点计中并计量加入氟酮Novec 1230 (3M Company)。
表3显示表明已形成共沸物的最低温度。该混合物的始沸点温度保持恒定,表明这种混合物在大的组成范围内是类共沸物的。
表3
Z-HFO-1336mzzm和Novec 1230在14.5 psia下的沸点计测量值
Z-HFO-1336mzzm,重量% | NOVEC 1230,重量% | Temp, ℃ |
100.00 | 0.00 | 32.7 |
99.25 | 0.75 | 32.6 |
97.77 | 2.23 | 32.4 |
94.95 | 5.05 | 32.2 |
89.78 | 10.22 | 32.0 |
82.99 | 17.01 | 32.0 |
75.39 | 24.61 | 32.1 |
69.06 | 30.94 | 32.1 |
63.72 | 36.28 | 32.2 |
58.61 | 41.39 | 32.4 |
54.27 | 45.73 | 32.5 |
50.52 | 49.48 | 32.7 |
47.26 | 52.74 | 32.8 |
44.39 | 55.61 | 33.0 |
实施例4
也已发现化合物E-HCFO-1233zd(反式-1,1,1-三氟-3-氯丙烯)与Z-HFO-1336mzzm形成类共沸物组合物。如下表4中所示,已经发现,这种组合物的类共沸物性质持续至大约10重量% Z-HFO-1336mzzm。这些组合物尤其可用于喷涂泡沫用途。
表4
Z-HFO-1336mzzm和E-HCFO-1233zd在14.5 psia下的沸点计测量值
实施例5
使用如实施例2中的沸点计测量Z-HFO-1336mzzm和水的共沸物。先将Z-HFO-1336mzzm装入沸点计中并计量加入水。表5显示表明已形成共沸物的最低温度。该混合物的始沸点温度保持恒定,表明这种混合物在大的组成范围内是类共沸物的。
表5
Z-HFO-1336mzzm和水在14.5 psia下的沸点计测量值
Z-HFO-1336mzzm,重量% | 水,重量% | Temp, ℃ |
100.0 | 0.0 | 32.4 |
99.4 | 0.6 | 32.3 |
98.2 | 1.8 | 32.0 |
97.1 | 2.9 | 31.8 |
96.0 | 4.0 | 31.7 |
93.9 | 6.1 | 31.5 |
89.8 | 10.2 | 31.4 |
82.8 | 17.2 | 31.4 |
76.7 | 23.3 | 31.4 |
71.5 | 28.5 | 31.4 |
66.9 | 33.1 | 31.4 |
62.9 | 37.1 | 31.4 |
59.4 | 40.6 | 31.4 |
类共沸物组合物的用途
如上所述,任何本发明的类共沸物组合物可作为CFC和含有较不合意的HCFC的组合物的替代品用于多种用途。
具体而言,包含或基本由有效量的Z-HFO-1336mzzm和选自水、氟酮、醇、氢氯氟烯烃及其两种或更多种的组合的另外的材料构成的类共沸物组合物可用作发泡剂、制冷剂、加热剂、动力循环剂(power cycle agents)、清洁剂、气溶胶推进剂、灭菌剂、润滑剂、香精和香料萃取剂、可燃性降低剂和火焰抑制剂,列出几个优选用途。下面更详细论述这些各用途。
发泡剂
本发明的一个实施方案涉及包含一种或多种本发明的类共沸物组合物的发泡剂。在另一些实施方案中,本发明提供可发泡组合物,优选聚氨酯和聚异氰脲酸酯泡沫组合物和制备泡沫的方法。在这样的泡沫实施方案中,一种或多种类共沸物组合物作为发泡剂包含在可发泡组合物中,所述组合物优选包括一种或多种如本领域中公知的能在适当条件下反应和发泡形成泡沫或多孔结构的附加组分。
本方法优选包括提供这种可发泡组合物并使其在有效获得泡沫,优选闭孔泡沫的条件下反应。本发明还涉及由含有包含本发明的类共沸物组合物的发泡剂的聚合物泡沫制剂制成的泡沫,优选闭孔泡沫。
在某些实施方案中, 一种或多种下列HFC异构体优选用作本发明的类共沸物组合物中的助发泡剂:
1,1,1,2,2-五氟乙烷 (HFC-125)
1,1,2,2-四氟乙烷 (HFC-134)
1,1,1,2-四氟乙烷 (HFC-134a)
1,1-二氟乙烷 (HFC-152a)
1,1,1,2,3,3,3-七氟丙烷 (HFC-227ea)
1,1,1,3,3,3-六氟丙烷 (HFC-236fa)
1,1,1,3,3-五氟丙烷 (HFC-245fa)和
1,1,1,3,3-五氟丁烷 (HFC-365mfc)。
任何上述附加助发泡剂以及可包括在本发明的类共沸物组合物中的任何附加组分的相对量可根据该组合物的特定用途在本发明的大致宽范围内广泛变动,所有这样的相对量都被认为在其范围内。
泡沫
本发明还涉及由含有包含类共沸物组合物的发泡剂的聚合物泡沫制剂制成的所有泡沫,包括但不限于闭孔泡沫、开孔泡沫、硬质泡沫、软质泡沫(flexible foam)、整皮泡沫(integral skin)等,所述类共沸物组合物包含或基本由Z-HFO-1336mzzm和一种或多种醇,优选甲醇或乙醇构成。申请人已经发现,本发明的泡沫,特别是热固性泡沫,如聚氨酯泡沫的一个优点是能够实现(优选与热固性泡沫实施方案结合)如图1中所示的优异热性能,如可通过K-系数或λ测得,特别和优选在低温条件下。
尽管本泡沫,特别是本发明的热固性泡沫预计可用于多种用途,但在某些优选实施方案中,本发明包括根据本发明的器械用泡沫(appliance foam),包括冷藏机泡沫、冷冻机泡沫、冷藏机/冷冻机泡沫、板材泡沫和其它冷或低温制造用途。
根据本发明制成的泡沫在某些优选实施方案中除与本发明的许多优选发泡剂相关的低臭氧消耗潜势和低全球变暖潜势外还提供一种或多种优异的特征、特性和/或性质,包括:隔热效率(特别是对热固性泡沫而言)、尺寸稳定性、压缩强度、隔热性质的老化。
在某些非常优选的实施方案中,本发明提供热固性泡沫,包括成形成泡沫制品的这种泡沫,其与使用相同量的相同发泡剂(或常用发泡剂HFC-245fa)但不用本发明的类共沸物组合物制成的泡沫相比表现出改进的热导率。
本领域中公知的任何方法,如经此引用并入本文的Polyurethanes Chemistry and technology, 第I和II卷, Saunders和Frisch, 1962, John Wiley and Sons, New York, N.Y.中描述的那些可以根据本发明的泡沫实施方案使用或改编使用。通常,这种优选方法包括通过合并异氰酸酯、多元醇或多元醇混合物、包含一种或多种本组合物的发泡剂或发泡剂混合物和其它材料,如催化剂以及表面活性剂和任选阻燃剂、着色剂或其它添加剂来制备聚氨酯或聚异氰脲酸酯泡沫。
在许多用途中便利的是在预掺合制剂中提供聚氨酯或聚异氰脲酸酯泡沫的组分。最通常将该泡沫制剂预掺合成两种组分。异氰酸酯和任选某些表面活性剂和发泡剂构成第一组分,常称作“A”组分。多元醇或多元醇混合物、表面活性剂、催化剂、发泡剂、阻燃剂和其它异氰酸酯反应性组分构成第二组分,常称作“B”组分。相应地,通过用于小型制品的手动混合或优选机械混合技术将A和B组分合并在一起,容易制备聚氨酯或聚异氰脲酸酯泡沫,以形成块、厚板、层合材料、现场浇注板和其它制品、喷施泡沫、泡沫(froths)等。任选地,其它成分,如阻燃剂、着色剂、辅助发泡剂和甚至其它多元醇可作为第三料流添加至混合头或反应位点。但是,最优选地,它们都并入如上所述的一个B组分中。
也可以使用本发明的类共沸物组合物制造热塑性泡沫。例如,常规泡沫聚氨酯和异氰脲酸酯制剂可以以常规方式与该类共沸物组合物合并以制造硬质泡沫。
也可以将分散剂、泡孔稳定剂和表面活性剂并入该发泡剂混合物中。添加表面活性剂,最尤其是硅油以充当泡孔稳定剂。一些代表性材料以DC-193、B-8404和L-5340为名出售,它们通常是聚硅氧烷聚氧化烯嵌段共聚物,如美国专利Nos. 2,834,748、2,917,480和2,846,458中公开的那些。用于发泡剂混合物的其它任选添加剂包括阻燃剂,如三(2-氯乙基)磷酸盐、三(2-氯丙基)磷酸盐、三(2,3-二溴丙基)-磷酸盐、三(1,3-二氯丙基)磷酸盐、磷酸二铵、各种卤化芳族化合物、氧化锑、三水合铝、聚氯乙烯等。
通常,用于形成本发明的可发泡组合物的共混混合物中存在的发泡剂的量取决于最终聚氨酯或聚异氰脲酸酯泡沫产品的所需泡沫密度。制成的聚氨酯泡沫的密度为对硬质聚氨酯泡沫而言大约0.5磅/立方英尺至大约40磅/立方英尺,优选大约1.0至大约20.0磅/立方英尺,最优选大约1.5至大约6.0磅/立方英尺,和对软质泡沫而言大约1.0至大约4.0磅/立方英尺不等。所得密度取决于若干因素,包括多少发泡剂或发泡剂混合物存在于A和/或B组分中或在制备泡沫时添加。
发泡剂 & 泡沫实施例
此实施例验证用于聚氨酯泡沫制备的包含Z-HFO-1336mzzm和醇的发泡剂的性能。三种单独发泡剂准备用于此实施例。第一发泡剂是HFC-245fa。第二发泡剂是Z-HFO-1336mzzm。第三发泡剂包含含有总发泡剂的大约98重量%浓度的Z-HFO-1336mzzm和总发泡剂的大约2重量%浓度的乙醇的类共沸物组合物。
在各体系中,发泡剂以基本相同的摩尔浓度添加到多元醇共混物中。然后使用各发泡剂形成泡沫并测量泡沫的k-系数。所用配方包含在下表6中。用3秒浇注时间和8秒混合时间制备泡沫。原材料温度为50℉多元醇/ 70℉ MDI。
表6 - 多元醇母料组合物
组分 | php |
Manich聚醚多元醇, OH 470 | 80.00 |
芳族聚酯多元醇 | 70.00 |
二乙二醇 | 10.00 |
有机硅表面活性剂 | 2.00 |
二甲基乙醇胺 | 3.20 |
中性氯化磷酸酯 | 20.00 |
水 | 2.00 |
总计 | 187.20 |
发泡剂摩尔数 | 0.698 |
指数 | 110 |
下表7和图1显示这三种发泡剂的k-系数性能
表7 - 聚氨酯泡沫的k系数
此实施例表现出的一个出乎意料的结果是98重量% Z-HFO-1336mzzm和2重量%乙醇共混物与纯Z-HFO-1336mzzm发泡剂相比改进的低温k系数。
喷涂泡沫
在喷涂泡沫实施例中,令人惊讶地发现,使用基本由4重量% Z-HFO-1336mzzm和96重量% 1233zd(E)构成的类共沸物组合物对泡沫的热导率具有显著和出乎意料的积极作用。用这种发泡剂组合物制成的泡沫与用仅含1233zd(E)的发泡剂制成的泡沫相比在所有温度范围内都更慢老化并具有更好的热导率性质。
方法和系统
本发明的类共沸物组合物也可用于许多方法和系统,包括作为传热方法和系统中的传热流体,如制冷、空调和热泵系统中所用的制冷剂。本发明的类共沸物组合物也有利地用在生成气溶胶的系统和方法中,在这种系统和方法中优选包括或由气溶胶推进剂构成。在本发明的某些方面中还包括形成泡沫的方法以及灭火和抑制火焰的方法。本发明在某些方面中还提供从制品上除去残留物的方法,其中在这样的方法和系统中使用本发明的类共沸物组合物作为溶剂组合物。
传热方法
优选传热方法通常包括提供本发明的类共沸物组合物和通过改变该组合物的相以使热向或从该组合物传递。例如,本方法通过从流体或制品吸收热,优选通过在要冷却的物体或流体附近蒸发本制冷剂组合物以产生包含本组合物的蒸气来提供冷却。
该方法优选包括通常用压缩机或类似设备压缩制冷剂蒸气以产生在相对升高压力下的本组合物的蒸气的进一步步骤。通常,压缩蒸气的步骤导致向该蒸气增加热,由此使该相对高压蒸气的温度提高。优选地,本方法包括从这种相对高温高压蒸气中除去至少一部分由蒸发和压缩步骤增加的热。除热步骤优选包括在高温高压蒸气处于相对高压条件下的同时冷凝该蒸气以产生包含本发明的组合物的相对高压液体。这种相对高压液体优选随后发生名义上等焓的减压以产生相对低温低压液体。在这样的实施方案中,这种温度降低的制冷剂液体随后被来自要冷却的物体或流体的热汽化。
在本发明的另一工艺实施方案中,本发明的类共沸物组合物可用在加热方法中,其包括在要加热的液体或物体附近冷凝包含或基本由本发明的类共沸物组合物构成的制冷剂组合物。如上所述的这种方法通常是上述制冷周期的逆向周期(reverse cycle)。
制冷剂组合物
本发明的类共沸物组合物适用于汽车空调系统和装置、商业制冷系统和装置、制冷机、住宅冰箱和冷冻机、通用空调系统、热泵等。
许多现有制冷系统目前适合与现有制冷剂结合使用,本发明的类共沸物组合物据信适用于许多这样的系统,进行或不进行系统修改。在许多用途中,本发明的类共沸物组合物可以在目前基于具有相对较高能力的制冷剂的系统中提供作为替代品的优点。此外,在出于例如效率原因而希望使用较低能力的本发明的制冷剂组合物替代较高能力的制冷剂的实施方案中,本组合物的这些实施方案提供潜在优点。
因此,在某些实施方案中优选使用包含或基本由Z-HFO-1336mzzm和一种或多种醇构成的类共沸物组合物替代现有制冷剂,如HCFC-123或HFC-134a。在某些用途中,本发明的制冷剂可能允许有利地使用更大排量的压缩机,由此带来比其它制冷剂,如HCFC-123或HFC-134a更好的能量效率。因此,本发明的制冷剂组合物为制冷剂替代用途提供在能量基础上实现竞争优势的可能性。
尽管本发明的类共沸物组合物预计可包括宽范围的量的组分,但本发明的制冷剂组合物通常优选以该组合物的至少大约50重量%,再更优选至少大约70重量%的量包含或基本由Z-HFO-1336mzzm构成。
动力循环用途
朗肯循环系统已知是将热能转化成机械轴功率的简单可靠的方式。在遇到低等级热能时,有机工作流体可用于替代水/蒸汽。在低等级热能(通常400℉和更低)下运行的水/蒸汽系统具有相关的高体积和低压力。为了保持小系统尺寸和高效率,使用沸点接近室温的有机工作流体。与在低运行温度下的水相比,这种流体具有更高气体密度,以带来更高能力和有利的输送和传热性质,以实现更高效率。在工业设置中更有机会使用可燃工作流体,如甲苯和戊烷,特别是在工业设置具有在工艺或储存中已在现场的大量易燃物时。对与可燃工作流体的使用相关的危险不可接受的情况,如在人口稠密区或建筑物附近的发电而言,使用其它流体如CFC-113和CFC-11。尽管这些材料不可燃,但由于它们的臭氧消耗潜势,它们对环境有危险。理想地,有机工作流体应环保、不可燃、具有低毒性级别并在正压力下工作。
本文所用的术语“不可燃”是指没有表现出通过标准闪点法之一,例如ASTM-1310-86 “Flash point of liquids by tag Open-cup apparatus”测得的闪点的本发明的化合物和组合物。
有机朗肯循环系统常用于从工业工艺中回收废热。在热电联产(废热发电)用途中,回收来自用于驱动发电机组的原动机的燃料燃烧的废热并用于例如制造热水以积蓄热,或用于供应热以运行吸收式制冷机从而提供冷却。在一些情况下,对热水的需求小或不存在。最难的情况是在热需求可变且负载匹配变难时,这扰乱热电联产系统的有效运行。在这种情况下,使用有机朗肯循环系统将废热转化成轴功率更有用。轴功率可用于运行例如泵,或其可用于发电。通过使用这种方法,总系统效率较高且燃料利用率较大。可以降低燃料燃烧的空气排放,因为可以在相同的燃料输入量下生成更多电力。
产生废热的工艺是选自燃料电池、内燃机、内压缩机、外压缩机和涡轮机的至少一种。可以与在炼油厂、石油化工厂、油气管道、化学工业、商业建筑物、旅馆、购物中心、超级市场、面包房、食品加工工业、餐馆、漆固化炉、家具制作、塑料成型机、水泥窑、木材干燥窑(干燥)、煅烧操作、钢工业、玻璃工业、铸造厂、熔炼、空调、制冷和集中供暖的作业相关地发现其它废热源。参见美国专利No. 7,428,816,其公开内容经此引用并入本文。
这种化合物的动力循环用途的一个具体实施方案是在有机朗肯循环系统中回收废热的方法,其中工作流体是包含或基本由Z-HFO-1336mzzm和一种或多种醇,优选甲醇或乙醇构成的类共沸物组合物。
动力循环实施例
此实施例示范本发明的类共沸物组合物用作朗肯动力循环组合物的用途。
根据Smith, J. M.等人, Introduction to Chemical Engineering Thermodynamics;McGraw-Hill (1996)中概述的程序,可以比较各种工作流体在有机朗肯循环中的效率。此实施例中的有机朗肯循环计算中所用的条件是75%的泵效率、80%的膨胀机效率、190℃的锅炉温度、45℃的冷凝器温度和向锅炉供应1000 W的热。将Z-HFO-1336mzzm:甲醇的95:5重量% 混合物的性能与市售流体HFC-245fa(可获自Honeywell)进行比较。HFC-245fa和Z-HFO-1336mzzm:甲醇的95:5重量%混合物在规定条件下的热效率分别为0.142和0.158。这表明Z-HFO-1336mzzm:甲醇的95:5重量%混合物在动力循环中表现得好于HFC-245fa。
清洁和除污
本发明还提供通过在制品上施加本发明的类共沸物组合物来从产品、部件、组件、基底或任何其它制品或其部分上除污的方法。为方便起见,术语“制品”在本文中用于表示所有这样的产品、部件、组件、基底等并进一步意在表示其任何表面或部分。此外,术语“污染物”意在表示该制品上存在的任何不想要的材料或物质,即使这种物质是有意置于制品上的。例如,在半导体器件的制造中,通常将光致抗蚀剂材料沉积到基底上以形成用于蚀刻操作的掩模和随后从该基底上除去光致抗蚀剂材料。本文所用的术语“污染物”意在涵盖和包括这种光致抗蚀剂材料。
本发明的优选方法包括将本组合物施加到制品上。尽管许多不同的清洁技术预计可有利地使用本发明的类共沸物组合物,但与超临界清洁技术结合使用本组合物被认为特别有利。在转让给本发明的受让人并经此引用并入本文的美国专利No.6,589,355中公开了超临界清洁。
对超临界清洁用途而言,在某些实施方案中优选在本清洁组合物中除本发明的类共沸物组合物外还包括另一组分,如CO2和已知用于超临界清洁用途的其它附加组分。
在某些实施方案中也可以和合意地,与特定的亚临界蒸气除油和溶剂清洁方法结合使用本清洁组合物。
本发明的另一清洁实施方案包括在制造和检修这些系统时从蒸气压缩系统和它们的附属组件中除去污染物。本文所用的术语“污染物”是指在这些系统的制造中使用或在它们的使用过程中生成的加工流体、润滑剂、微粒、淤渣和/或其它材料。通常,这些污染物包含如烷基苯、矿物油、酯、聚亚烷基二醇、聚乙烯醚和主要由碳、氢和氧制成的其它化合物之类的化合物。本发明的类共沸物组合物可用于此用途。
清洁组合物实施例
此实施例示范本发明的类共沸物组合物用作清洁组合物的用途。
制备含有95重量% Z-HFO-1336mzzm与大约5重量%乙醇的类共沸物组合物。用矿物油、松香焊剂或其它污染物弄脏几个不锈钢试块。然后将这些试块浸在溶剂共混物中。该共混物可以在短时间内除去油。目测试块的清洁度。其它混合物预计有类似结果。硅油也预计有类似结果。
用于可喷组合物的推进剂
在另一实施方案中,本发明的类共沸物组合物可以单独或与已知推进剂结合用作可喷组合物中的推进剂。该推进剂组合物包含,更优选基本由,再更优选由本发明的类共沸物组合物构成。在该可喷混合物中还可存在要与惰性成分、溶剂和其它材料一起喷施的活性成分。该可喷组合物优选是气溶胶。要喷施的合适活性材料包括,但不限于,润滑剂、杀虫剂、清洁剂、化妆品材料,如除臭剂、芳香剂和喷发剂,摩擦剂(polishing agents)以及医用材料,如皮肤冷却剂(晒伤处理)、局部麻醉剂和止喘药物。
该可喷组合物包括要喷施的材料和包含本发明的类共沸物组合物的推进剂。在该可喷混合物中还可存在惰性成分、溶剂和其它材料。该可喷组合物优选是气溶胶。要喷施的合适材料包括,但不限于,化妆品材料,如除臭剂、芳香剂、喷发剂、清洁剂和摩擦剂,以及医用材料,如止喘药和防口臭药。
消毒
出于健康和安全原因,如患者和医院工作人员的健康和安全,特别用于医疗领域的许多制品、装置和材料在使用前必须消毒。本发明提供消毒方法,包括使要消毒的制品、装置或材料与本发明的类共沸物组合物(并任选与一种或多种附加灭菌剂结合)接触。
尽管许多灭菌剂是本领域中已知的并且被认为适用于本发明,但在某些优选实施方案中,灭菌剂包含环氧乙烷、甲醛、过氧化氢、二氧化氯、臭氧和这些的组合。在某些实施方案中,环氧乙烷是优选灭菌剂。本领域技术人员根据本文所含的教导容易确定要与本消毒组合物和方法结合使用的灭菌剂和本化合物的相对比例,所有这样的范围都在其宽范围内。
如本领域技术人员已知的那样,某些灭菌剂,如环氧乙烷是极易燃的组分,本发明的化合物以与该组合物中存在的其它组分一起有效地将该消毒组合物的可燃性降至可接受水平的量包含在本组合物中。本发明的消毒方法可以是高温或低温消毒,本发明涉及在大约250℉至大约270℉的温度下,优选在基本密封室中使用本发明的化合物或组合物。该方法通常在少于大约2小时内完成。但是,一些制品,如塑料制品和电气部件不能承受这样的高温并且需要低温消毒。
消毒实施例
在低温消毒方法中,使要消毒的制品在大约室温至大约200℉的温度下,更优选在大约室温至大约100℉的温度下暴露在包含本发明的组合物的流体中。
本发明的低温消毒优选至少是在基本密封,优选气密的室中进行的两步法。在第一步骤(消毒步骤)中,将已经清洁和包裹在可透气袋中的制品置于该室中。
随后通过抽真空和可能通过用蒸汽置换空气从该室中抽空空气。在某些实施方案中,优选将蒸汽注入该室中以实现优选大约30%至大约70%的相对湿度。这种湿度可以使在实现所需相对湿度后引入该室中的消毒剂的消毒效力最大化。在足以使消毒剂渗透包装并到达制品空隙的时间后,从该室中排空消毒剂和蒸汽。
在该方法的优选第二步骤(通气步骤)中,将该制品通气以除去消毒剂残留物。除去这种残留物在有毒消毒剂的情况下特别重要,尽管在使用本发明的基本无毒化合物的情况下这是任选的。典型通气法包括空气洗涤、连续通气和两者的组合。空气洗涤是分批法并通常包括排空该室相对较短时间,例如12分钟,然后在大气压或更高压力下将空气引入该室中。
本文所用的术语“无毒”是指具有如通过经此引用并入本文的Anesthesiology, 第14卷, 第466-472页, 1953中公开的方法测得的明显低于HFO-1223xd的毒性水平(优选低至少大约30相对百分比)的急性毒性水平的本发明的化合物和组合物。
这种周期重复任何次数直至实现消毒剂的所需清除。连续通气通常涉及经由该室一侧上的入口引入空气,随后通过对室另一侧上的出口施加轻微真空而经由该出口抽出空气。通常,合并这两种方法。例如,常用方法涉及进行空气洗涤和随后通气周期。
润滑剂
在某些优选实施方案中,本发明的类共沸物组合物可进一步包含润滑剂。在本发明的类共沸物组合物中可以使用各种各样的常规润滑剂。对润滑剂的一个重要要求在于,当用在制冷剂系统中时,必须有足够的润滑剂返回该系统的压缩机中以润滑压缩机。因此,润滑剂对任何给定系统的适用性部分取决于制冷剂/润滑剂特性并且部分取决于要使用其的系统的特性。
合适的润滑剂的实例包括矿物油、烷基苯、多元醇酯,包括聚亚烷基二醇,PAG油等。包含石蜡油或环烷油的矿物油可购得。市售矿物油包括来自Witco的Witco LP 250(注册商标)、来自Shrieve Chemical的Zerol 300(注册商标)、来自Witco的Sunisco 3GS和来自Calumet的Calumet R015。市售烷基苯润滑剂包括Zerol 150(注册商标)。市售酯包括可作为Emery 2917(注册商标)和Hatcol 2370(注册商标)供应的新戊二醇二壬酸酯。其它可用的酯包括磷酸酯、二元酸酯和氟代酯。优选润滑剂包括聚亚烷基二醇和酯。某些更优选的润滑剂包括聚亚烷基二醇。
香精和香料的萃取
本发明的类共沸物组合物在用于负载、萃取或分离来自生物质的合意材料时也提供优点。这些材料包括,但不限于,香精油如香精和香料、可用作燃料、药物、保健营养品等的油。
萃取实施例
通过下述试验程序证实本发明的类共沸物组合物用于此用途的适用性:将茉莉酮样品放入厚壁玻璃管中。将合适量的本发明的类共沸物组合物添加到该玻璃管中。然后冷冻和密封该管。在将该管解冻后,这时该混合物具有一个含有茉莉酮和类共沸物组合物的液相;此试验确定该组合物有利地用作香精和香料制剂的萃取剂、载体或输递体系的一部分、用于气溶胶和其它制剂。也确定其作为香精和香料的萃取剂的潜力,包括从植物物质中萃取。
可燃性降低方法
根据某些其它优选实施方案,本发明提供降低流体的可燃性的方法,所述方法包括将本发明的类共沸物组合物添加到所述流体中。根据本发明可降低与多种本来可燃的流体相关的可燃性。例如,根据本发明可以降低与流体,如环氧乙烷、可燃氢氟烃和烃,包括:HFC-152a、1,1,1-三氟乙烷(HFC-143a)、二氟甲烷(HFC-32)、丙烷、己烷、辛烷等相关的可燃性。对本发明而言,可燃流体可以是如通过任何标准的常规试验方法,如ASTM E-681等测得的那样表现出在空气中的可燃范围的任何流体。
可以添加任何合适量的本化合物或组合物以降低本发明的流体的可燃性。本领域技术人员会认识到,添加量至少部分取决于该流体的可燃程度和希望将其可燃性降至什么程度。在某些优选实施方案中,添加到可燃流体中的化合物或组合物的量有效地使所得流体基本不可燃。
可燃性降低实施例
此实施例示范本发明的类共沸物组合物用于降低另一组合物的可燃性的的用途。
在环境条件下的ASTM E681装置中,将异戊烷蒸气与97:2重量% Z-HFO-1336mzzm:乙醇的类共沸物混合物混合以发现随着加入更多97:2 wt Z-HFO-1336mzzm:乙醇的类共沸物混合物,可燃性下限(LFL)提高。这表明该共混物的可燃性低于异戊烷本身——更容易安全使用的较不可燃的材料。这种较高LFL允许在空气中的较高浓度而不用担心着火源和可能的火灾或爆炸。
两个气溶胶罐充满甲醇/水,一个用HFC-152a加压,而另一个用HFC-152a和97:2 wt% Z-HFO-1336mzzm:乙醇的类共沸物混合物加压。在如气溶胶火焰扩展试验程序中那样将来自该罐的气溶胶喷在蜡烛火焰上和蜡烛火焰中时,观察到来自用97:2重量% Z-HFO-1336mzzm:乙醇的类共沸物混合物加压的罐的较小火焰扩展。
火焰抑制方法
本发明进一步提供抑制火焰的方法,所述方法包括使火焰与本发明的类共沸物组合物接触。如果需要,也可以与本发明的组合物一起使用附加火焰抑制剂(混合或作为第二火焰抑制剂)。用于此用途的一类化合物是氟酮。一种尤其优选的氟酮是十二氟-2-甲基戊-3-酮。这种优选化合物的一个商业来源是以商品名Novec 1230获自3M Company。
可以使用任何合适的使火焰与本组合物接触的方法。例如,本发明的组合物可以喷施、倾倒到火焰上,或可以将至少一部分火焰浸在该组合物中。
尽管已参照优选实施方案特别显示和描述了本发明,但本领域普通技术人员容易认识到,可以在不背离本发明范围的情况下作出各种变动和修改。权利要求书旨在被解释为涵盖所公开的实施方案、上文已论述的那些备选方案及其所有同等物。
Claims (15)
1.类共沸物组合物,其包含有效量的从大于0至大约99重量%的化合物顺式-1,1,1,4,4,4-六氟-2-丁烯(Z-HFO-1336mzzm)和大约1重量%至小于100重量%的另外的材料,所述另外的材料选自水、氟酮、醇、氢氯氟烯烃及其两种或更多种的组合。
2.权利要求1的类共沸物组合物,其中至少一种醇是甲醇。
3.权利要求1的类共沸物组合物,其中至少一种醇是乙醇。
4.权利要求1的类共沸物组合物,其包含有效量的大约75重量%至小于100重量%的Z-HFO-1336mzzm和从大于0至大约25重量%的醇及其两种或更多种的组合。
5.权利要求1的类共沸物组合物,其包含有效量的大约85重量%至小于100重量%的Z-HFO-1336mzzm和从大于0至大约15重量%的醇及其两种或更多种的组合。
6.权利要求1的类共沸物组合物,其包含有效量的从大于0至大约50重量%的水和大约50重量%至小于100重量%的Z-HFO-1336mzzm。
7.权利要求1的类共沸物组合物,其包含有效量的从大于0至大约10重量%的水和大约90重量%至小于100重量%的Z-HFO-1336mzzm。
8.权利要求1的类共沸物组合物,其包含有效量的50重量%至大约99重量%的Z-HFO-1336mzzm和大约1重量%至小于50重量%的氟酮。
9.权利要求1的类共沸物组合物,其包含有效量的60重量%至大约95重量%的Z-HFO-1336mzzm和大约5重量%至小于40重量%的氟酮。
10.权利要求1的类共沸物组合物,其包含有效量的大约1重量%至大约99重量%的Z-HFO-1336mzzm和大约1重量%至大约99重量%的反式-1,1,1-三氟-3-氯丙烯。
11.权利要求1的类共沸物组合物,其包含大约90重量%至大约99重量%的Z-HFO-1336mzzm和大约1重量%至大约10重量%的反式-1,1,1-三氟-3-氯丙烯。
12.权利要求1的类共沸物组合物,其包含大约4重量%的Z-HFO-1336mzzm和大约96重量%的反式-1,1,1-三氟-3-氯丙烯。
13.权利要求1的类共沸物组合物,其包含HFO-1233zd和最多大约10重量% Z-HFO-1336mzzm。
14.用于喷涂泡沫的发泡剂,其包含权利要求1的类共沸物组合物。
15.包含权利要求1的类共沸物组合物的制冷剂组合物。
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