CN101014680A - 含有经氟取代的烯烃的组合物 - Google Patents
含有经氟取代的烯烃的组合物 Download PDFInfo
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- CN101014680A CN101014680A CNA2005800135366A CN200580013536A CN101014680A CN 101014680 A CN101014680 A CN 101014680A CN A2005800135366 A CNA2005800135366 A CN A2005800135366A CN 200580013536 A CN200580013536 A CN 200580013536A CN 101014680 A CN101014680 A CN 101014680A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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Abstract
本发明揭示四氟丙烯、尤其是(HFO-1234)的e在包括致冷设备在内的多种应用中的用途。所述材料通常用作加热和冷却的致冷剂、用作发泡剂、用作气雾剂推进剂、用作溶剂组合物以及用作灭火剂和火灾抑制剂。
Description
技术领域
本发明是关于在尤其包括致冷系统的多种应用中具有效用的组合物,并且也是关于利用所述组合物的方法和系统。在优选方面,本发明是针对包含本发明的至少一种多氟代烯烃的致冷剂组合物。
背景技术
已发现碳氟化合物基流体广泛用于多种商业和工业应用中。举例而言,碳氟化合物基流体通常用作诸如空气调节、热泵和致冷应用的系统中的工作流体。蒸气压缩循环是在致冷系统中实现冷却或加热的最常用类型的方法之一。蒸气压缩循环通常涉及致冷剂在相对低的压力下通过吸热由液相变为气相且随后在相对低的压力和温度下通过热移除由气相变为液相的相变;将蒸气压缩至相对高的压力;在此相对高的压力和温度下通过热移除将气相冷凝成液相;及随后降低压力以再次起始循环。
致冷的主要目的是在相对低的温度下将热量自目标流体或其它流体中移除,而热泵的主要目的是在相对环境更高的温度下增加热量。
多年来,在许多应用中,某些碳氟化合物已成为诸如致冷剂的许多热交换流体中的优选组份。举例而言,诸如氯氟甲烷和氯氟乙烷衍生物的氟代烷已由于其独特的化学和物理特性组合而在包括空气调节和热泵应用的应用中广泛用作致冷剂。蒸气压缩系统中常用的多种致冷剂都为单一组份流体或共沸混合物。
近年来,已愈来愈关注对于地球大气和气候的潜在危害,且已将某些氯基化合物识别为在此点上尤其有问题的化合物。由于与许多此类化合物有关的臭氧损耗特性,在空气调节和致冷系统中用作致冷剂的含氯组合物(诸如氯氟碳化物(CFC)、氢氯氟碳化物(HCFC)及其类似物)已变得不受欢迎。因此,已愈来愈需要可提供致冷和热泵应用的替代选择的新碳氟化合物和氢氟碳化合物和组合物。举例而言,通过用不会损耗臭氧层的不含氯致冷剂化合物(诸如氢氟碳化物(HFC))替代含氯致冷剂来改进含氯致冷系统已变得合乎需要。
然而,通常认为重要的是任何潜在的代用致冷剂也必须具有许多最广泛使用的流体中所存在的那些特性,诸如极佳的传热特性、化学稳定性、低毒性或无毒性、不易燃性和润滑剂相容性等。
申请者已开始意识到润滑剂相容性在许多应用中尤为重要。更尤其是,非常需要致冷流体与大多数致冷系统中使用的用于压缩机组中的润滑剂相容。不幸的是,包括HFC的许多不含氯致冷流体相对不溶和/或不混溶于传统上与CFC和HFC一起使用的润滑剂类型中,所述润滑剂包括(例如)矿物油、烷基苯或聚(α-烯烃)。为使致冷流体-润滑剂组合以在压缩致冷、空气调节和/或热泵系统内有效的理想水平工作,润滑剂应在各种操作温度下充分溶于致冷液体中。所述溶解性降低润滑剂的粘性,并使其更易于在整个系统中流动。在缺少所述溶解性的情况下,润滑剂易于积存在致冷、空气调节或热泵系统的蒸发器旋管以及所述系统的其它部分中,且因此降低系统效率。
关于使用效率,重要的是应注意致冷剂热力学效能或能效的损失可通过因电能需求增加而增加的化石燃料使用对环境造成次级影响。
此外,通常认为需要对当前用于CFC致冷剂中的习知蒸气压缩技术不会造成主要工程改变的有效CFC致冷剂代用品。
对于许多应用而言,易燃性是另一重要特性。也就是说,应认为在尤其包括传热应用的许多应用中使用不易燃组合物是重要或必要的。因此,使用所述不易燃组合物化合物通常是有益的。如本文所使用的术语“不易燃”是指当根据2002年实施的ASTM标准E-681(其是以引用的方式并入本文)确定时经确定为不易燃的化合物或组合物。不幸的是,可能另外需要用于致冷剂组合物中之许多HFC也并非不易燃的。举例而言,氟代烷二氟乙烷(HFC-152a)和氟代烯1,1,1-三氟丙烯(HFO-1234zf)各为易燃的,且因此不可用于许多应用中。
已建议将较高碳数的氟代烯,亦即经氟取代的具有至少五个碳原子的烯烃用作致冷剂。Smutny的美国专利第4,788,352号是针对具有至少某一不饱和度的氟代C5至C8化合物的制备。Smutny专利识别出已知所述较高碳数的烯烃可用作致冷剂、杀虫剂、介电流体、传热流体、溶剂和多种化学反应中的中间体(参看第1列,第11-22行)。
尽管Smutny中所述的氟代烯烃可在传热应用中具有某种程度的效用,但据信所述化合物也可以具有某些缺点。举例而言,所述化合物中的一些可易于侵蚀衬底,尤其通用塑料,诸如丙烯酸树脂和ABS树脂。此外,Smutny中所述的较高碳数的烯烃化合物也可以由于所述化合物可由Smutny中所述的杀虫剂活性引起潜在程度的毒性而不适用于某些应用中。另外,所述化合物也可具有因过高而致使其不能在某些应用中用作致冷剂的沸点。
溴氟甲烷和溴氯氟甲烷衍生物,尤其溴三氟甲烷(哈龙(Halon)1301)和溴氯二氟甲烷(哈龙1211)已在封闭区域(诸如飞机舱和电脑室)中日益广泛地用作灭火剂。然而,多种哈龙因其高臭氧损耗而正逐渐退出使用。而且,由于哈龙通常用于人类出现的区域中,所以适当的代用品也必须在抑制或灭火所需的浓度下对人类安全。
因此,申请者已开始意识到需要潜在可用于多种应用(包括蒸气压缩加热和冷却系统及方法)中并避免上述缺点中的一个或一个以上缺点的组合物,且尤其需要传热组合物、灭火/抑制火灾组合物、发泡剂、溶剂组合物和相容剂。
发明内容
申请者已发现上述需求和其它需求可通过一些组合物来满足,所述组合物包含一种或一种以上的C3或C4氟代烯,优选具有下式I的化合物:
XCFzR3-z (I),
其中X为C2或C3不饱和、经取代或未经取代的烷基,各R独立为Cl、F、Br、I或H,且z为1至3。在式I化合物中,尤其优选1,3,3,3-四氟丙烯的顺和反异构体(HFO-1234ze)。
本发明也提供利用本发明组合物的方法和系统,其包括用于传热、发泡、溶剂化、调味剂和芳香剂提取和/或传递及气雾剂产生的方法和系统。
附图说明
无
具体实施方式
组合物
本发明是针对包含至少一种含有3至4个碳原子(优选3个碳原子)和至少一个碳碳双键的氟代烯的组合物。如果本发明的氟代烯化合物含有至少一个氢,则在本文中有时出于便利的目的将其称为氢氟-烯烃或“HFO”。尽管预期本发明的HFO可含有两个碳碳双键,但目前认为所述化合物并非优选的。
如上文所提及,本发明组合物包含一种或一种以上根据式I的化合物。在优选实施例中,所述组合物包括下式II的化合物:
其中各R独立为Cl、F、Br、I或H,
R′为(CR2)nY,
Y为CRF2,
且n为0或1。
在尤其优选的实施例中,Y为CF3,n为0且剩余R中的至少一者为F。
申请者认为,一般而言,上文所识别的式I和II化合物通常有效且在本发明的致冷剂组合物、发泡剂组合物、相容剂、气雾剂、推进剂、芳香剂、调味剂调配物和溶剂组合物中显示出效用。然而,申请者已惊奇且出人意料地发现某些具有根据上述各式的结构的化合物显示出相比其它此类化合物更合乎人意的低毒性含量。应易于了解,所述发现不仅对于致冷剂组合物,而且对于将另外含有满足上述各式的相对有毒化合物的任何和所有组合物的调配物都具有潜在地巨大优势和益处。更特定言之,申请者认为相对低的毒性含量与式II的化合物有关,优选其中Y为CF3,其中不饱和末端碳上至少一个R为H且剩余R中的至少一者为F。申请者也认为所述化合物的所有结构、几何和立体异构体都有效且有利地具有低毒性。
在特别优选的实施例中,尤其在包含上文所述的低毒性化合物的实施例中,n为零。在某些特别优选的实施例中,本发明的组合物包含一种或一种以上四氟丙烯。本文中使用的术语“HFO-1234”是指所有四氟丙烯。在所述四氟丙烯中,尤其优选顺-与反-1,3,3,3-四氟丙烯(HFO-1234ze)。本文中使用的术语HFO-1234ze一般是指1,3,3,3-四氟丙烯,而与其为顺式或反式无关。本文中使用的术语“顺HFO-1234ze”和“反HFO-1234ze”分别描述顺式-和反式-的1,3,3,3-四氟丙烯。因此,术语“HFO-1234ze”在其范畴内包括顺HFO-1234ze、反HFO-1234ze及所述物质的所有组合和混合物。
尽管在至少某些方面顺HFO-1234ze和反HFO-1234ze的特性不同,但预期所述化合物的每一者都适于单独或与包括其立体异构体的其它化合物一起与本文所述的每一应用、方法和系统结合使用。举例而言,当反HFO-1234ze由于其相对低的沸点(-19℃)而可优选用于某些致冷系统中时,仍预期沸点为+9℃的顺HFO-1234ze也在本发明的某些致冷系统中具有效用。因此,应了解术语“HFO-1234ze”和1,3,3,3-四氟丙烯指两种立体异构体,而且使用这一术语意欲表明除非另作指示,否则顺式-和反式的每一者都应用于和/或可用于指定目的。
HFO-1234化合物是已知材料且列于化学文摘(Chemical Abstract)数据库中。通过多种饱和与不饱和含卤素C3化合物的催化气相氟化来制备诸如CF3CH=CH2的氟代丙烯已在美国专利第2,889,379号、第4,798,818号和第4,465,786号中得以描述,所述专利的每一者都以引用的方式并入本文。EP974,571(也以引用的方式并入本文中)揭示通过在高温下使气相1,1,1,3,3-五氟丙烷(HFC-245fa)与铬基催化剂接触,或使液相1,1,1,3,3-五氟丙烷(HFC-245fa)与KOH、NaOH、Ca(OH)2或Mg(OH)2的醇溶液接触来制备1,1,1,3-四氟丙烯。此外,用于制备根据本发明的化合物的方法通常结合申请中的标题为“Process for Producing Fluoropropenes”、代理人案号(attorney docket number)为(H0003789(26267))的美国专利申请案加以描述,所述专利申请案也以引用的方式并入本文中。
据信,本发明组合物、尤其是那些包含HFO-1234ze的组合物具有因许多重要原因而有益的特性。例如,申请者至少部分基于数学建模认为本发明的氟代烯烃将对大气化学大体无实质性负面影响,即与某些其它卤化物相比,其对臭氧损耗的作用可忽略。因此,本发明的优选组合物具有大体上不促进臭氧损耗的益处。相比目前使用的许多氢氟烷,优选组合物也大体上不会促进全球变暖。
在某些优选形式中,本发明的组合物具有不大于约1000、更优选不大于约500且甚至更优选不大于约150的全球变暖潜能(GWP)。在某些实施例中,本发明组合物的GWP不大于约100且甚至更优选不大于约75。如“The Scientific Assessment of Ozone Depletion,2002,a report of the World Meteorological Association′s Global Ozone Research andMonitoring Project”(其以引用的方式并入本文)中所定义,如本文所使用的“GWP”是相对于二氧化碳的GWP且历时100年时程测量。
在某些优选形式中,本发明组合物也优选具有不大于0.05、更优选不大于0.02且甚至更优选约为零的臭氧损耗潜势(ODP)。如本文所使用的“ODP”是如“The ScientificAssessment of Ozone Depletion,2002,A report of the World Meteorological Association′sGlobal Ozone Research and Monitoring Project”(其以引用的方式并入本文)中所定义。
本发明组合物中所含有的式I化合物、尤其HFO-1234的量可视特殊应用而广泛变化,并且含有大于痕量且小于100%化合物的组合物处于本发明的广泛范畴内。而且,本发明的组合物可共沸、共沸物类或不共沸。在优选实施例中,本发明组合物包含约5重量%至约99重量%且甚至更优选约5%至约95%的量的HFO-1234,优选HFO-1234ze。本发明组合物中可包括许多额外化合物,且所有所述化合物的存在都处于本发明的广泛范畴内。在某些优选实施例中,除HFO-1234ze外,本发明组合物还包括下列化合物中的一种或一种以上:
二氟甲烷(HFC-32);
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);
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);
1,1,1,3,3-五氟丁烷(HFC-365mfc);
水;
CO2。
任何上述组份以及本发明组合物中可包括的任何额外组份的相对量可根据所述组合物的特殊应用而在本发明的通用广泛范畴内广泛变化,而且可认为所有所述相对量都处于此范畴内。
传热组合物
尽管预期本发明的组合物可包括各种量的本发明化合物,但通常优选本发明的致冷剂组合物包含占所述组合物至少约50重量%且甚至更优选至少约70重量%的量的根据式I的化合物,更优选根据式II的化合物,且甚至更优选HFO-1234ze。在许多实施例中,优选本发明的传热组合物包含反HFO-1234ze。在某些优选实施例中,本发明的传热组合物包含顺∶反重量比例为约1∶99至约10∶99、更优选约1∶99至约5∶95且甚至更优选约1∶99至约3∶97的顺HFO-1234ze与反HFO-1234ze的组合。
出于增强或向所述组合物提供某些功能性的目的,或在某些降低所述组合物成本的情况下,本发明的组合物可包括其它组份。举例而言,根据本发明的致冷剂组合物、尤其用于蒸气压缩系统中的那些组合物包括通常占所述组合物约30至约50重量百分比的量的润滑剂。此外,出于辅助润滑剂相容性和/或溶解性的目的,本发明组合物也可以包括相容剂,诸如丙烷。所述包括丙烷、丁烷和戊烷的相容剂优选以占组合物约0.5至约5重量百分比的量存在。如美国专利第6,516,837号中所揭示,也可以将表面活性剂和增溶剂的组合添加至本发明组合物中以辅助油溶性,所述专利的揭示内容是以引用的方式并入本文。与氢氟碳化物(HFC)致冷剂一起用于致冷机械中的常用致冷润滑剂可用于本发明的致冷剂组合物中,所述常用致冷润滑剂诸如多元醇酯(POE)和聚烷二醇(PAG)、硅油、矿物油、烷基苯(AB)和聚(α-烯烃)(PAO)。
许多现存的致冷系统当前适于与现存致冷剂结合使用,并且据信本发明的组合物可适用于许多需要或无需系统改进的此类系统中。在许多应用中,本发明的组合物可提供作为当前基于具有相对高容量的致冷剂的系统的替代品的优势。此外,在需要使用更低容量的本发明致冷剂组合物的实施例中,出于(例如)替换更高容量致冷剂的成本原因,本发明组合物的所述实施例提供一潜在优势。因此,优选在某些实施例中使用本发明的组合物、尤其包含大比例反HFO-1234ze且在某些实施例中基本由反HFO-1234ze组成的组合物来作为诸如HFC-134a的现存致冷剂的替代品。在某些应用中,本发明的致冷剂潜在地允许有利的使用更大的容积式压缩机,藉此产生比诸如HFC-134a的其它致冷剂更高的能效。因此,本发明的致冷剂组合物、尤其包含反HFP-1234ze的组合物提供在能量方面达成致冷剂替换应用的竞争性优势的可能性。
预期尤其包括所述包含HFO-1234ze的组合物的本发明组合物对于通常与商用空气调节系统结合使用的冷却器也具有益处(在原系统中或当用作诸如R-12和R-500的致冷剂的替代品时)。在某些所述实施例中,优选在本发明HFO-1234ze组合物中包括约0.5至约5%诸如CF3I的易燃抑制剂。
因此,本发明方法、系统和组合物都适用于汽车空气调节系统和装置、商用致冷系统和装置、冷却器、家用电冰箱和冷冻器、通用空气调节系统、热泵和类似装置中。
发泡剂、发泡体和发泡组合物
发泡剂也可以包含本发明组合物中的一种或一种以上或由其构成。如上文所提及,本发明的组合物可包括各种量的本发明的组合物。然而,对于用作根据本发明的发泡剂的优选组合物而言,通常优选根据式I的化合物且甚至更优选根据式II的化合物是以占所述组合物至少约5重量%且甚至更优选至少约15重量%的量存在。在某些优选实施例中,本发明的发泡剂组合物除包括HFO-1234(优选HFO-1234ze)外还包括下列组份中的一者或一者以上来作为共发泡剂、填充剂、蒸气压力改质剂或出于任何其它目的者:
二氟甲烷(HFC-32);
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);
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);
1,1,1,3,3-五氟丁烷(HFC-365mfc);
水;
CO2。
预期本发明的发泡剂组合物可包含顺HFO-1234ze、反HFO1234ze或其组合。在某些优选实施例中,本发明的发泡剂组合物包含顺∶反重量比例为约1∶99至约10∶99且甚至更优选约1∶99至约5∶95的顺HFO-1234ze与反HFO-1234ze的组合。
在其它实施例中,本发明提供发泡组合物,且优选使用本发明的组合物制备的聚氨基甲酸酯、聚异三聚氰酸酯和挤压热塑性发泡组合物。在所述发泡体实施例中,发泡组合物中包括本发明组合物中的一种或一种以上作为发泡剂或其部分,如此项技术中已熟知,所述组合物优选包括一种或一种以上能够在形成发泡体或细胞结构的适当条件下反应和/或发泡的额外组份。本发明也是关于发泡体且优选封闭细胞发泡体,其皆是由含有包含本发明组合物的发泡剂的聚合物发泡体调配物所制备。在其它实施例中,本发明提供的发泡组合物包含热塑性或聚烯烃发泡体,诸如聚苯乙烯(PS)、聚乙烯(PE)、聚丙烯(PP)和聚对苯二甲酸乙二酯(PET)发泡体,优选低密度发泡体。
在某些优选实施例中,分散剂、细胞稳定剂、表面活性剂和其它添加剂也可以并入本发明的发泡剂组合物中。视情况但优选添加表面活性剂以将其用作细胞稳定剂。某些代表性材料是以DC-193、B-8404和L-5340的名称销售,所述材料通常为聚硅氧烷聚环氧烷嵌段共聚物,诸如美国专利第2,834,748号、第2,917,480号和第2,846,458号中所揭示的那些物质,所述专利的每一者都是以引用的方式并入本文中。发泡剂混合物中其它可选择的添加剂可包括阻燃剂,诸如磷酸三(2-氯乙基)酯、磷酸三(2-氯丙基)酯、磷酸三(2,3-二溴丙基)酯、磷酸三(1,3-二氯丙基)酯、磷酸二铵、多种经卤化芳族化合物、氧化锑、三水合铝、聚氯乙烯及其类似物。
推进剂和气雾剂组合物
另一方面,本发明提供包含本发明组合物或基本上由其组成的推进剂组合物,所述推进剂组合物优选可喷射组合物。本发明的推进剂组合物优选包含待喷射的材料,和包含根据本发明的组合物、基本上由其组成或由其组成的推进剂。可喷射混合物中也可以存在惰性成份、溶剂和其它材料。可喷射组合物优选气雾剂。待喷射的适当材料包括(不限于):化妆用材料,诸如除臭剂、香水、喷发剂、洗面乳和抛光剂;以及医药材料,诸如抗哮喘组份、防口臭组份和任何其它的药物或类似物,优选包括意欲吸入的任何其它药物或药剂。药物或其它治疗剂优选以治疗量存在于组合物中,且所述组合物的剩余部分中的相当大部分包含本发明的式I化合物,优选HFO-1234且甚至更优选HFO-1234ze。
工业、消费型或药用气雾剂产品通常含有一种或一种以上的推进剂连同一种或一种以上的活性成份、惰性成份或溶剂。推进剂提供使产品以雾化形式射出的力。尽管某些气雾剂产品是以类似二氧化碳、氮气、氧化氮及甚至空气的压缩气体推进,但大多数商业气雾剂使用液化气体推进剂。最常用的液化气体推进剂为烃,诸如丁烷、异丁烷和丙烷。也使用单独或与烃推进剂掺合的二甲醚和HFC-152a(1,1-二氟乙烷)。不幸的是,所有所述液化气体推进剂都高度易燃,且将其并入气雾剂的调配物中通常将产生易燃的气雾剂产物。
申请者已开始意识到持续需要用于调配气雾剂产物的不易燃、液化气体推进剂。本发明提供本发明的组合物,尤其且优选包含HFO-1234的组合物,且甚至更优选HFO-1234ze,其用于包括(例如)喷雾清洁剂、润滑剂及其类似物的某些工业气雾剂产品和包括(例如)将药物传递至肺部或粘膜的药用气雾剂中。此类实例包括定剂量吸入剂(MDI),其用于治疗哮喘和其它慢性阻塞性肺病并用于将药物传递至可达到的粘膜或鼻内。因此,本发明包括用于治疗有机体(诸如人类或动物)的小病、疾病和类似的健康相关问题的方法,所述方法包含将含有药物或其它治疗组份的本发明组合物应用于需要治疗的有机体。在某些优选实施例中,应用本发明组合物的步骤包含提供含有本发明的组合物的MDI(例如将所述组合物引入MDI中),及随后自所述MDI排出本发明组合物。
本发明的组合物、尤其包含HFO-1234ze或基本上由其组成的组合物能够提供大体上不会促进全球变暖的不易燃、液化气体推进剂和气雾剂。本发明组合物可用于调配多种工业气雾剂或其它可喷射组合物,诸如接点清洁剂、除尘剂、润滑剂喷雾和类似物;和消费型气雾剂,诸如个人护理产品、家用产品和汽车产品。尤其优选将HFO-1234ze用作用于诸如定剂量吸入剂的药用气雾剂中的推进剂组合物的重要组份。在许多应用中,除式(I)或(II)的化合物(优选HFO-1234ze)外,本发明的药用气雾剂和/或推进剂和/或可喷射组合物也包括一种药物,诸如β-促效剂、皮质类固醇或其它药物;和视情况存在的其它成份,诸如表面活性剂、溶剂、其它推进剂、调味剂和其它赋形剂。与先前用于所述应用中的许多组合物不同,本发明的组合物具有良好的环境特性,且不应被视为引起全球变暖的潜在促进者。因此,在某些优选实施例中,本发明组合物提供具有极低全球变暖潜能的大体上不易燃、液化气体推进剂。
调味剂和芳香剂
当本发明的组合物用作调味剂调配物和芳香剂调配物载体的部分且尤其用作其载体时,其也提供优势。出于此目的,通过一测试程序证实本发明组合物的适用性,在所述测试程序中,将0.39克茉莉酮(Jasmone)放于厚壁玻璃管中。将1.73克R-1234ze添加至所述玻璃管中。随后冷冻并密封所述管。解冻所述管后,发现混合物具有一液相。溶液中含有20重量%茉莉酮和80重量%R-1234ze,因此确定其有利于用作气雾剂和其它调配物中的调味剂调配物传递系统的载体或所述传递系统的部分。也确定其作为芳香剂(包括来自植物的芳香剂)的提取剂的潜能。
方法和系统
本发明的组合物可与多种方法和系统结合使用,包括作为传热方法和系统中的传热流体,诸如致冷、空气调节和热泵系统中所使用的致冷剂。本发明组合物也有利于用于产生气雾剂的系统和方法中,在所述系统和方法中优选包含气雾剂推进剂或由气雾剂推进剂组成。在本发明的某些方面中也包括形成发泡体的方法和灭火与扑灭火灾的方法。在某些方面中,本发明也提供将残余物自物件中移除的方法,在所述物件中本发明组合物用作所述方法和系统中的溶剂组合物。
传热方法
优选的传热方法通常包含提供本发明的组合物,和将热传送至所述组合物或自所述组合物传送热以改变所述组合物的相。举例而言,本发明方法通过自流体或物件吸收热,优选通过蒸发待冷却物体或流体邻近处的本发明致冷剂组合物以产生包含本发明组合物的蒸气来提供冷却。所述方法优选包括另一步骤,亦即通常用压缩机或类似设备来压缩致冷剂蒸气以在相对高的压力下产生本发明组合物的蒸气。一般而言,压缩蒸气的步骤致使蒸气热量增加,由此使相对高压的蒸气的温度增加。本发明方法优选包括自此相对高温、高压的蒸气中移除至少一部分通过蒸发和压缩步骤所添加的热。热移除步骤优选包括在冷凝高温、高压蒸气的同时,使所述蒸气在相对高压的条件下以产生包含本发明组合物的相对高压的液体。接着,使此相对高压的液体在产生相对低温、低压液体的压力下经历标称等焓降低。在所述实施例中,此降低温度的致冷剂液体接着通过自待冷却的物体或流体传送热而汽化。
在本发明的另一方法实施例中,本发明的组合物可用于一种用于产生加热的方法中,所述方法包含冷凝包含待加热液体或物体邻近处的组合物的致冷剂。如上文所提及的所述方法通常为上述致冷循环的逆循环。
发泡方法
本发明的一实施例是关于形成发泡体且优选聚氨基甲酸酯和聚异三聚氰酸酯发泡体的方法。如此项技术中所熟知,所述方法通常包含提供本发明的发泡剂组合物,将所述发泡剂组合物(直接或间接)添加至发泡组合物中,及在有效形成发泡体或细胞结构的条件下使所述发泡组合物反应。此项技术中熟知的任何方法都可根据本发明的发泡体实施例使用或适用于根据所述实施例使用,诸如“Polyurethanes Chemistry andTechnology”,第I和II卷,Saunders和Frisch,1962,John Wiley and Sons,New York,NY中所述的那些方法,所述文献以引用的方式并入本文中。总的说来,所述优选方法包含通过组合异氰酸酯、多元醇或多元醇混合物、包含本发明组合物中的一种或一种以上的发泡剂或发泡剂混合物和诸如催化剂、表面活性剂的其它材料及视情况存在的阻燃剂、着色剂或其它添加剂来制备聚氨基甲酸酯或聚异三聚氰酸酯发泡体。
在许多应用中,便于将聚氨基甲酸酯或聚异三聚氰酸酯的组份提供于经预掺合的调配物中。最一般地,将所述发泡体调配物预掺合于两种组份中。异氰酸酯和视情况某些表面活性剂和发泡剂包含第一组份,其通常称为“A”组份。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份包含第二组份,通常称为“B”组份。因此,通过手工混合(用于少量制备)且优选机械混合技术使A和B副组份集合在一起以形成块状体、扁块、层状物、灌注面板和其它物件、喷射涂覆发泡体、泡沫和类似物,从而易于制备聚氨基甲酸酯或聚异三聚氰酸酯发泡体。视情况,可将诸如阻燃剂、着色剂、辅助发泡剂和甚至其它多元醇的其它成份作为第三物流添加至混合头或反应位点。然而,最优选将其都并入如上所述的一种B组份中。
也可能使用本发明的组合物制造热塑性发泡体。举例而言,可以用制造刚性发泡体的习知方式使习知聚苯乙烯和聚乙烯调配物与所述组合物组合。
清洗方法
本发明也提供通过将本发明的组合物涂覆于物件上而将污染物自产物、零件、组件、衬底或任何其它物件或其部分上移除的方法。出于便利的目的,本文使用的术语“物件”指所有所述产物、零件、组件、衬底及其类似物,且其意欲另外指任何表面或其部分。此外,术语“污染物”意欲指所述物件上所存在的任何不必要的材料或物质,即使所述物质是有意放置于所述物件上。例如,在半导体装置的制造中,通常将光阻材料沉积于一衬底上以形成一用于蚀刻操作的掩模,且随后将所述光阻材料自所述衬底上移除。如本文所使用的术语“污染物”意欲包括且涵盖此类光阻材料。
本发明的优选方法包含将本发明组合物涂覆于所述物件上。尽管预期多种且不同的清洗技术可使用本发明的组合物实现良好的益处,但结合超临界清洗技术使用本发明组合物据认为尤其有益。超临界清洗已在美国专利第6,589,355号中得以揭示,所述专利已让渡于本发明的受让人且以引用的方式并入本文。对于超临界清洗应用而言,在某些实施例中,本发明清洗组合物中除HFO-1234(优选HFO-1234ze)外优选还包括一种或一种以上额外组份,诸如CO2和已知与超临界清洗应用结合使用的其它额外组份。在某些实施例中也可能且需要结合特殊的蒸气去油和溶剂清洗方法使用本发明清洗组合物。
降低易燃性的方法
根据某些其它优选实施例,本发明提供用于降低流体易燃性的方法,所述方法包含将本发明的化合物或组合物添加至所述流体中。可根据本发明降低与各种其它易燃流体中的任一种有关的易燃性。举例而言,可根据本发明降低与流体有关的易燃性,所述流体诸如环氧乙烷、易燃氢氟碳化物和烃,其包括:HFC-152a、1,1,1-三氟乙烷(HFC-143a)、二氟甲烷(HFC-32)、丙烷、己烷、辛烷和类似物。出于本发明的目的,易燃流体可为当通过诸如ASTM E-681和类似方法的任何标准习知测试方法测量时在空气中显示出易燃范围的任何流体。
可添加任何适当量的本发明化合物或组合物以降低根据本发明的流体的易燃性。所属领域技术人员将认识到,所添加的量将至少部分视所述流体易燃的程度和需要降低其易燃性的程度而定。在某些优选实施例中,易燃流体中所添加的化合物或组合物的量对于使所得流体大体上不易燃有效。
抑制火焰的方法
本发明另外提供抑制火焰的方法,所述方法包含使火焰与包含本发明的化合物或组合物的流体接触。使火焰与本发明组合物接触的任何适当的方法都可以使用。例如,可将本发明的组合物喷射、倾倒和使用类似方法置于火焰上,或可将至少一部分火焰浸入所述组合物中。根据本文的教示,所属领域技术人员将能够易于调适本发明中使用的多种抑制火焰的习知仪器和方法。
灭菌方法
出于健康和安全(诸如患者和医护人员的健康和安全)原因考虑,许多物件、装置和材料(尤其用于医药领域)在使用之前都必须灭菌。本发明提供灭菌的方法,所述方法包含使待灭菌的物件、装置或材料和与一种或一种以上灭菌剂组合的本发明化合物或组合物接触,所述化合物或组合物包含式I的化合物、优选HFO-1234且甚至更优选HFO-1234ze。尽管此项技术中已知许多灭菌剂且认为其都适于与本发明结合使用,但在某些优选实施例中,灭菌剂包含环氧乙烷、甲醛、过氧化氢、二氧化氯、臭氧和所述物质的组合。在某些实施例中,环氧乙烷是优选的灭菌剂。鉴于本文所含有的教示,所属领域技术人员将能够易于确定待与本发明灭菌组合物和方法结合使用的灭菌剂与本发明化合物的相对比例,且所有所述范围都在其广泛范畴内。如所属领域技术人员已知,诸如环氧乙烷的某些灭菌剂是相对易燃的组份,而且本发明组合物中包括有效量的根据本发明的化合物以及所述组合物中所存在的其它组份,以使所述灭菌组合物的易燃性降低至可接受的程度。
本发明的灭菌方法可为高温或低温灭菌。本发明的灭菌方法涉及在约250至约270的温度下优选在大体上密封的室内使用本发明的化合物或组合物。所述方法通常可在不足约2小时内完成。然而,诸如塑料物件和电子组件的某些物件无法经受所述高温,且需要低温灭菌。在低温灭菌方法中,在约室温至约200的温度下,更优选在约室温至约100的温度下,使待灭菌的物件暴露于包含本发明组合物的流体中。
本发明的低温灭菌优选是在大体上密封、优选具有气密性的室中进行的至少两步骤的方法。在第一步骤(灭菌步骤)中,将已经清洗且包装于透气袋中的物件放置于所述室中。接着,通过抽真空且可能通过用蒸汽置换空气而将空气自所述室中排空。在某些实施例中,优选将蒸汽注入所述室中以达成优选处于约30%至约70%范围内的相对湿度。所述湿度可使灭菌剂的灭菌效能最大化,所述灭菌剂是在达成所需相对湿度后引入所述室中。在一段足以使灭菌剂渗透包装并达到物件空隙的时间后,将灭菌剂和蒸汽自所述室中排出。
在所述方法的优选第二步骤(通风步骤)中,使所述物件通风以移除灭菌剂残余物。移除所述残余物在有毒灭菌剂的情况下尤其重要,尽管在使用本发明的大体上无毒化合物的那些情况下其具有可选性。典型的通风方法包括空气洗涤、持续通风和两种方法的组合。空气洗涤是一种分批方法且通常包含在相对短时间内(例如12分钟)排空所述室,以及接着在大气压或更高压力下将空气引入所述室中。重复此循环多次,直至达成所需移除灭菌剂。连续通风通常涉及通过所述室一侧的入口引入空气,以及随后通过在所述室的另一侧的出口处施加少量真空将其由出口处抽出。通常,组合两种方法。举例而言,常用方法涉及进行空气洗涤且随后进行通风循环。
实例
出于描述本发明但非限制其范畴的目的,提供下列实例。
实例1
效能系数(COP)是普遍接受的致冷剂效能度量,其尤其可用于表示在涉及蒸发或冷凝致冷剂的特定加热或冷却循环中致冷剂的相对热力学效率。在致冷工程设计中,此术语表示有用致冷与通过压缩机压缩蒸气所施加的能量的比率。致冷剂的容量表示其所提供的冷却或加热的量,并且提供压缩机在致冷剂的定体积流率下抽吸热量的能力的某种度量。换言之,给定一特殊压缩机,具有更高容量的致冷剂将传递更多的冷却或加热能量。一种在特定操作条件下评估致冷剂COP的方式是使用标准致冷循环分析技术根据致冷剂热力学特性进行评估(参看例如R.C.Downing,FLUOROCARBONREFRIGERANTS HANDBOOK,第3章,Prentice-Hall,1988)。
提供一种致冷/空气调节循环系统,其中在标称等熵压缩下,冷凝器温度为约150且蒸发器温度为约-35,且压缩机入口温度为约50。基于COP值为1.00、容量值为1.00且排出温度为175的HFC-134a,确定在冷凝器和蒸发器的温度范围内本发明的若干组合物的COP值,并将其报导于下表I中。
表I
致冷剂组合物 | 相对COP | 相对容量 | 排出温度() |
HFO 1225ye | 1.02 | 0.76 | 158 |
HFO反-1234ze | 1.04 | 0.70 | 165 |
HFO顺-1234ze | 1.13 | 0.36 | 155 |
HFO 1234yf | 0.98 | 1.10 | 168 |
此实例表明某些与本发明组合物合用的优选化合物各自具有比HFC-134a更高的能效(与1.00比较为1.02、1.04和1.13),且使用本发明致冷剂组合物的压缩机将产生排出温度(与175比较为158、165和155),其由于此结果通常将可能导致维护问题减少而有益。
实例2
测试HFO-1225ye和HFO-1234ze及多种致冷润滑剂的可混溶性。所测试的润滑剂为矿物油(C3)、烷基苯(Zerol 150)、酯油(Mobil EAL 22cc和Solest 120)、聚烷二醇(PAG)油(用于134a系统的Goodwrench Refrigeration Oil)和聚(α-烯烃)油(CP-6005-100)。对于每一致冷剂/油组合而言,测试三种组合物,即5、20和50重量百分比的润滑剂,且各自的剩余部分为待测试的本发明化合物。
将润滑剂组合物放置于厚壁玻璃管中。排空所述管,添加根据本发明的致冷剂化合物,且随后将所述管密封。接着,将所述管放于空气浴环境室中,所述环境室中的温度在约-50℃至70℃之间变化。大致以10℃为间隔,目测观察管内容物以观察一种或一种以上液相的存在。在观察到一种以上液相的情况下,报导所述混合物不可混溶。在仅观察到一种液相的情况下,报导所述混合物可混溶。在观察到两种液相但所述液相之一仅占据极小体积的情况下,报导所述混合物可部分混溶。
判定聚烷二醇和酯油润滑剂在整个温度范围内以所有测试比例都可混溶,但HFO-1225ye与聚烷二醇的混合物例外,发现所述致冷剂混合物在-50℃至-30℃的温度范围内不可混溶且在-20℃至50℃的温度范围内可部分混溶。在致冷剂中PAG浓度为50重量百分比时且在60℃下,致冷剂/PAG混合物可混溶。在70℃下,致冷剂中润滑剂占5重量百分比至致冷剂中润滑剂占50重量百分比时,其可混溶。
实例3
在350℃下,测试当与致冷系统和空气调节系统中所使用的金属接触时,本发明的致冷剂化合物和组合物与PAG润滑油的相容性,表示条件比在许多致冷和空气调节应用中所发现的条件更苛刻。
将铝、铜和钢制挂片添加至厚壁玻璃管中。将两克油添加至所述管中。随后,排空所述管并添加一克致冷剂。将所述管放于烘箱中在350下历时一周,并进行目测观察。在暴露期后期,移除所述管。
对油与本发明化合物的下述组合执行此程序。
a)HFO-1234ze和GM Goodwrench PAG油
b)HF01243 zf和GM Goodwrench油PAG油
c)HFO-1234ze和MOPAR-56 PAG油
d)HFO-1243 zf和MOPAR-56 PAG油
e)HFO-1225 ye和MOPAR-56 PAG油。
在所有情况下,管中内容物的外观都存在极小改变。此表明当与致冷和空气调节系统中所发现的铝、钢和铜及可能包括于所述组合物中或与所述类型系统中的所述组合物合用的所述类型的润滑油接触时,本发明的致冷剂化合物和组合物都稳定。
比较实例
如实例3中所述,将铝、铜和钢制挂片与矿物油和CFC-12一起添加至厚壁玻璃管中,并在350℃下加热一周。在暴露期后期,移除所述管并进行目测观察。观察到液体内容物变黑,表明管中内容剧烈分解。
CFC-12和矿物油至今已在许多致冷剂系统和方法中成为所选组合。因此,本发明的致冷剂化合物和组合物及许多常用的润滑油比广泛用于先前技术中的致冷剂-润滑油组合具有显著更高的稳定性。
实例4-多元醇发泡体
此实例描述根据本发明的一个优选实施例的发泡剂的用途,即HFO-1234ze的用途,以及根据本发明的多元醇发泡体的制造。多元醇发泡体调配物的组份是根据下表制备:
多元醇组份* | PBW |
Voranol490 | 50 |
Voranol391 | 50 |
水 | 0.5 |
B-8462(表面活性剂) | 2.0 |
Polycat8 | 0.3 |
Polycat41 | 3.0 |
HFO-1234ze | 35 |
总计 | 140.8 |
异氰酸酯
M-20S 123.8,指数1.10
*Voranol 490是一种基于蔗糖的多元醇且Voranol 391是一种基于甲苯二胺的多元醇,且其各自来自Dow Chemical.B-8462是一种购自Degussa-Goldsehmidt的表面活性剂。Polycat催化剂是基于叔胺且购自Air Products。异氰酸酯M-20S是Bayer LLC的产品。
发泡体是通过首先混合其成份但不添加发泡剂来制备。将两个费歇尔-波特(Fisher-Porter)管中各填充约52.6克多元醇混合物(无发泡剂)并密封,且将其放置于冰箱中冷却并形成微真空。使用气体量管,将约17.4克HFO-1234ze添加至每一管中,且随后将所述管放置于超声波浴中的温水中,并使其静置30分钟。所产生的溶液浑浊,室温下蒸气压测量指示蒸气压为约70psig,表明溶液中并无发泡剂。接着,将所述管放置于冷冻器中,在27下历时2小时。再次测量蒸气压,并发现其为14-psig。将约87.9克的异氰酸酯混合物放置于金属容器中,并放置于冰箱中,且使其冷却至约50。接着,打开多元醇管并将其称至金属混合容器中(使用约100克多元醇掺合物)。然后,将来自经冷却的金属容器的异氰酸酯迅速倾入多元醇中,并用具有双重推进器的空气混合器以3000RPM混合10秒。通过搅动使掺合物迅速产生泡沫,且随后将其倾入8×8×4英寸的盒子中,并使其发泡。由于泡沫,无法测量乳化时间。发泡体具有4分钟凝胶时间及5分钟消粘时间。接着,使发泡体在室温下固化两天。然后,将发泡体切割成适于测量物理特性的样品,并发现其具有2.14pcf的密度。测量K-因子,并发现如下:
温度 K,BTU In/Ft2h
40 .1464
75 .1640
11O° .1808
实例5-聚苯乙烯发泡体
此实例描述根据本发明的两个优选实施例的发泡剂的用途,即HFO-1234ze和HFO-1234-yf的用途,以及聚苯乙烯发泡体的制造。已确立测试仪器和方案来作为对确定特定发泡剂和聚合物是否能够制造发泡体和发泡体品质的辅助。在一容器中组合经研磨的聚合物(Dow聚苯乙烯685D)和基本上由HFO-1234ze组成的发泡剂。所述容器的草图描述于下。容器体积为200cm3且其是由两个管凸缘以及一个4英寸长的2英寸直径标准40号(schedule40)不锈钢管的截面制成(参看图1)。将容器放置于烘箱中,并将温度设定为约190至约285,对于聚苯乙烯而言优选265,且保持在此温度下直至达到温度平衡为止。
接着,释放所述容器中的压力,快速制造发泡体聚合物。当发泡剂溶解于聚合物中时,发泡剂使所述聚合物增塑。表1中提供使用此方法由此制造的两种发泡体的所得密度且在图1中图解为使用反-HFO-1234ze和HFO-1234yf所制造的发泡体的密度。数据表明可根据本发明获得发泡体聚苯乙烯。R1234ze与聚苯乙烯的模温为约250。
表1
Dow聚苯乙烯685D发泡体密度(lb/ft^3) | ||
T, | 反HFO-1234ze | HFO-1234yf |
275 | 55.15 | |
260 | 22.14 | 14.27 |
250 | 7.28 | 24.17 |
240 | 16.93 |
Claims (64)
1.一种传热组合物,其包含:
(a)至少一种式I的氟代烯:
XCFzR3-z (I)
其中X为C2或C3不饱和、经取代或未经取代烷基;R独立地为Cl、F、Br、I或H;且z为1至3,
所述组合物具有不高于约1000的全球变暖潜能(GWP)。
3.根据权利要求1所述的传热组合物,其中所述至少一种氟代烯包含至少一种四氟丙烯(HFO-1234)。
4.根据权利要求3所述的传热组合物,其中所述至少一种HFO-1234包含HFO-1234yf。
5.根据权利要求3所述的传热组合物,其中所述至少一种HFO-1234包含HFO-1234ze。
6.根据权利要求2所述的传热组合物,其包含至少约50重量%的所述式II的组合物。
7.根据权利要求2所述的传热组合物,其中所述至少一种氟代烯包含至少一种四氟丙烯(HFO-1234)。
8.根据权利要求7所述的传热组合物,其中所述至少一种HFO-1234包含HFO-1234yf。
9.根据权利要求7所述的传热组合物,其中所述至少一种HFO-1234基本上由HFO-1234yf组成。
10.根据权利要求7所述的传热组合物,其中所述至少一种HFO-1234包含HFO-1234ze。
11.根据权利要求7所述的传热组合物,其包含约5重量%至约99重量%的HFO-1234。
12.根据权利要求7所述的传热组合物,其包含约5重量%至约95重量%的HFO-1234。
13.根据权利要求12所述的传热组合物,其中所述HFO-1234是选自由HFO-1234yf、HFO-1234ze和所述物质的组合组成的群组。
14.根据权利要求13所述的传热组合物,其中所述HFO-1234包含顺∶反重量比为约1∶99至约10∶99的反HFO-1234和顺HFO-1234ze。
15.根据权利要求1所述的传热组合物,其包含大于约痕量至小于约100重量%的所述式I的组合物。
16.根据权利要求15所述的传热组合物,其包含约5重量%至约95重量%的HFO-1234yf。
17.根据权利要求15所述的传热组合物,其包含约5重量%至约95重量%的HFO-1234ze。
18.根据权利要求17所述的传热组合物,其中所述HFO-1234ze包含至少约90重量%的反-1,3,3,3-四氟丙烯(反HFO-1234ze)。
19.根据权利要求1所述的传热组合物,其另外包含一种或一种以上选自由下列各物组成的群组的化合物:二氟甲烷(HFC-32)、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)、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)、1,1,1,3,3-五氟丁烷(HFC-365mfc)、水、CO2和所述物质中的两者或两者以上的组合。
20.根据权利要求1所述的传热组合物,其另外包含一种或一种以上润滑剂。
21.根据权利要求1所述的传热组合物,其另外包含其量占所述传热组合物的约30重量百分比至约50重量百分比的一种或一种以上润滑剂。
22.根据权利要求1所述的传热组合物,其另外包含一种或一种以上火焰抑制剂。
23.根据权利要求1所述的传热组合物,其另外包含其量占所述传热组合物的约0.5重量%至约5重量%的一种或一种以上火焰抑制剂。
24.根据权利要求1所述的传热组合物,其中所述火焰抑制剂包含CF3I。
25.一种替换致冷剂系统中所含有的现存致冷剂的方法,其包含自所述系统中替换所述现存致冷剂中的至少一部分,以及通过将包含至少一种式I的氟代烯的致冷剂组合物引入所述系统中来替换所述现存致冷剂中的至少一部分:
XCFzR3-z (I)
其中X为C2或C3不饱和、经取代或未经取代烷基;R独立地为Cl、F、Br、I或H;且z为1至3。
26.根据权利要求25所述的方法,其中所述现存致冷剂包含HFC-134a。
27.根据权利要求25所述的方法,其中所述现存致冷剂包含R-12。
28.根据权利要求25所述的方法,其中所述现存致冷剂包含R-500。
29.根据权利要求25所述的方法,其中所述现存致冷剂系统包含至少一相对大的容积式压缩机。
30.根据权利要求25所述的方法,其中所述现存致冷剂系统是用于商用空气调节系统中的冷却器系统。
31.根据权利要求25所述的方法,其中所述现存致冷剂系统是用于家用空气调节系统中的冷却器系统。
32.根据权利要求25所述的方法,其中所述致冷剂具有不大于约1000的全球变暖潜能(GWP)。
33.根据权利要求25所述的方法,其中所述致冷剂包含约5重量%至约95重量%的HFO-1234ze。
34.根据权利要求25所述的方法,其中所述致冷剂包含约5重量%至约95重量%的HFO-1234yf。
35.根据权利要求34所述的方法,其中所述现存致冷剂系统是用于商用空气调节系统中的冷却器系统。
36.一种将热传送至流体或物体或自流体或物体传送热的方法,其包含使所述流体或物体与包含式I的氟代烯的组合物接触:
XCFzR3-z (I)
其中X为C2或C3不饱和、经取代或未经取代烷基;各R独立为Cl、F、Br、I或H;且z为1至3,所述组合物具有不大于1000的全球变暖潜能(GWP)。
37.根据权利要求36所述的方法,其中所述组合物具有不大于约500的GWP。
38.根据权利要求36所述的方法,其中所述式I的氟代烯包含HFO-1234yf。
39.根据权利要求36所述的方法,其中所述式I的氟代烯包含HFO-1234ze。
40.根据权利要求36所述的方法,其中所述接触步骤包含使所述组合物在汽车空气调节系统中循环。
41.根据权利要求36所述的方法,其中所述接触步骤包含使所述组合物在商用致冷系统中循环。
42.根据权利要求36所述的方法,其中所述接触步骤包含使所述组合物在冷却器中循环。
43.根据权利要求36所述的方法,其中所述接触步骤包含使所述组合物在家用冰箱和冷冻器中循环。
44.根据权利要求36所述的方法,其中所述接触步骤包含使所述组合物在热泵中循环。
45.一种发泡组合物,其包含发泡聚合物或预聚物和包含至少一种式I的氟代烯的发泡剂:
XCFzR3-z (I)
其中X为C2或C3不饱和、经取代或未经取代烷基;R独立地为Cl、F、Br、I或H;且z为1至3,所述发泡剂具有不大于约1000的全球变暖潜能(GWP)。
46.一种发泡体,其由根据权利要求45所述的发泡组合物制成。
47.一种发泡体预混组合物,其包含聚合物或预聚物和包含至少一种式I的氟代烯的发泡剂:
XCFzR3-z (I)
其中X为C2或C3不饱和、经取代或未经取代烷基;各R独立为Cl、F、Br、I或H;且z为1至3。
48.根据权利要求47所述的发泡体预混组合物,其具有不大于约1000的全球变暖潜能(GWP)。
49.根据权利要求48所述的发泡体预混物,其另外包含火焰抑制剂。
50.一种组合物,其包含:
(a)至少一种式I的氟代烯:
XCFzR3-z (I)
其中X为C2或C3不饱和、经取代或未经取代烷基;各R独立为Cl、F、Br、I或H;且z为1至3;及
(b)至少一种佐剂,其是选自由多元醇预混物组份、调味剂、芳香剂和所述物质中的两种或两种以上的组合组成的群组。
51.根据权利要求50所述的组合物,其具有不大于约1000的全球变暖潜能(GWP)。
52.一种推进剂组合物,其包含至少一种式I的氟代烯:
XCFzR3-z (I)
其中X为C2或C3不饱和、经取代或未经取代烷基;R独立地为Cl、F、Br、I或H;且z为1至3,所述组合物具有不大于约1000的全球变暖潜能(GWP)。
53.一种发泡剂,其包含至少一种式I的氟代烯:
XCFzR3-z (I)
其中X为C2或C3不饱和、经取代或未经取代烷基;R独立地为Cl、F、Br、I或H;且z为1至3,且所述发泡剂具有不大于约1000的全球变暖潜能(GWP)。
54.根据权利要求53所述的发泡剂,其另外包含火焰抑制剂。
55.一种自植物中提取调味剂或芳香剂化合物的方法,其包含使所述植物与包含至少一种式I的氟代烯的提取剂接触:
XCFzR3-z (I)
其中X为C2或C3不饱和、经取代或未经取代烷基;R独立地为Cl、F、Br、I或H;且z为1至3。
56.根据权利要求55所述的方法,其中所述提取剂包含HFO-1234。
57.根据权利要求55所述的方法,其中所述提取剂包含HFO-1234ze。
58.根据权利要求1所述的传热组合物,其具有不大于约0.05的臭氧损耗潜势(ODP)。
59.根据权利要求1所述的传热组合物,其具有不大于约0.02的臭氧损耗潜势(ODP)。
60.根据权利要求1所述的传热组合物,其具有约为零的臭氧损耗潜势(ODP)。
61.根据权利要求1所述的组合物,其另外包含相容剂。
62.根据权利要求62所述的组合物,其中所述相容剂是以占所述组合物的约0.5重量百分比至约5重量百分比的量存在。
63.一种超临界清洗方法,其包含使待清洗的物件与根据权利要求1所述的组合物接触。
64.根据权利要求64所述的超临界清洗方法,其中根据权利要求1所述的组合物另外包含CO2。
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