CN102140329B - 含有氟取代烯烃的组合物 - Google Patents
含有氟取代烯烃的组合物 Download PDFInfo
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- CN102140329B CN102140329B CN201110006890.3A CN201110006890A CN102140329B CN 102140329 B CN102140329 B CN 102140329B CN 201110006890 A CN201110006890 A CN 201110006890A CN 102140329 B CN102140329 B CN 102140329B
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- heat transfer
- hfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
- C23G5/02803—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing fluorine
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
本发明揭示五氟丙烯(HFO‑1225)和四氟丙烯(HFO‑1234)在制冷设备中的用途。这些材料通常用作加热及冷却用的制冷剂、用作发泡剂、用作气溶胶推进剂、用作溶剂组合物、及用作灭火与抑燃剂。
Description
本案是分案申请,其母案是申请日为2003年10月27日、申请号为200380107462.3、发明名称为“含有氟取代烯烃的组合物”的申请。
相关申请案参照
本申请案与美国临时申请案第60/421,263号和第60/421,435号有关并主张优先于该等申请案,这两个申请案皆于2002年10月25日提出申请,且其皆以引用方式并入本文中。本申请案还与下述同时提交的美国专利申请案有关:Raymond Thomas提交的题为“Fluorina ted Alkene Refrigerant Composition(氟代烯烃制冷剂组合物)”的美国专利申请案(代理档案号为H0004412(26269);及Hsueh Sung Tung等人提交的题为“ProcessFor Producing Fluoropropenes(制备氟丙稀的方法)”的美国专利申请案(代理档案号为H0003789(26267)。
技术领域
本发明涉及在多种应用场合具有实用性的组合物,尤其包括制冷系统,且本发明亦涉及使用这些组合物的方法和系统。在一些较佳方面中,本发明涉及包括至少一种本发明多氟代烯烃的制冷剂组合物。
背景技术
以氟碳化合物为主的流体已广泛使用于许多商业和工业应用中。例如,以氟碳化合物为主的流体常常在诸如空调、热泵和制冷系统等应用中用作工作流体。蒸气压缩循环是一种在制冷系统中完成冷却或加热的最常用类型的方法。蒸气压缩循环通常包括制冷剂在较低压力下通过吸热由液相到气相的相变和随后制冷剂在较高压力和温度下通过热量移除由气相到液相的相变,将蒸气压缩到相对较高的压力,在此相对较高的压力和温度下通过热量移除将所述蒸气冷凝为液相,并随后减小压力重新开始循环。
制冷的主要目的是在一较低温度下从一物体或其它流体移除热量,而热泵的主要目的是在相对于环境更高的温度下增加热量。
多年以来,某些氟碳化合物在许多应用中一直是多种热交换流体(例如制冷剂)中的较佳组分。例如,由于氟代烷(例如,氯氟甲烷和氯氟乙烷衍生物)具有独特的化学和物理性质组合,因此其作为制冷剂已在包括空调和热泵等应用中获得了广泛使用。许多普遍应用于蒸气压缩系统的制冷剂可为单一组分的流体或者为共沸混合物。
近年来,人们对地球大气和气候潜在破坏的关注逐渐增加,因此,某些氯基化合物被视为可引起显著问题。由于许多含氯组合物(例如,氟氯碳化合物(CFC)、氢氯氟碳化合物(HCF)等等)具有臭氧消耗性质,因此,此类化合物作为制冷剂在空调和制冷系统中的使用已变得不受欢迎。因此,越来越需要可为制冷和热泵应用提供替代物的新颖氟碳和氢氟碳化合物及组合物。例如,人们期望通过用不会消耗臭氧层的不含氯制冷化合物(例如,氢氟碳化合物(HFC))替代含氯制冷剂来改进含氯制冷系统。
然而,通常认为重要的是,任何潜在的制冷剂替代物必须亦具备存在于最广泛使用的流体中的性质,其中包括例如极好的传热性质、化学稳定性、低毒性或无毒性、不可燃性和润滑剂相容性。
申请者逐渐认识到润滑剂相容性在许多应用中特别重要。更具体而言,人们非常期望制冷流体能够与用于大多数制冷系统压缩机装置中的润滑剂相容。遗憾的是,包括HFC在内的许多不含氯制冷流体在通常与CFC及HFC一起使用的各类型润滑剂中相对不溶及/或难于混溶,所述润滑剂包括矿物油、烷基苯或聚(α-烯烃)。为使一制冷流体-润滑剂组合在在压缩制冷、空调及/或热泵系统中以预期效率工作,润滑剂应能在宽广的操作温度范围中充分溶解于制冷流体。这样的溶解性可降低润滑剂的黏度并允许润滑剂更易于流过整个系统。若缺少这样的溶解性,润滑剂则会易于滞留在该制冷、空调或热泵系统的蒸发器螺旋管以及此系统的其它部分中,从而降低系统效率。
就使用效率而言,应重点注意的是,制冷剂热力学性能或者能量效率的损失可能会通过因电能需求增加引起的矿物燃料的用量增加而对环境造成负面影响。
而且,人们通常期望CFC制冷剂替代物是有效的,且不需对目前用于CFC制冷剂的蒸气压缩技术进行较大的设计改变。
对于许多应用而言,可燃性是另一重要性质。即,据认为在许多应用中,尤其是在传热应用中,使用不可燃组合物是十分重要的或是必需的。因此,在这些组合物中使用不可燃化合物通常较为有利。本文所用术语“不可燃”指根据2002年的ASTM标准E-681确定为不可燃的化合物或组合物,所述标准以引用方式并入本文中。遗憾的是,许多期望在制冷剂组合物中使用的HFC是可燃的。例如,氟代烷二氟乙烷(HFC-152a)和氟烯烃1,1,1-三氟丙稀(HFO-1234zf)都是可燃的,因此不适合用于许多应用场合。
有人建议使用高级氟烯烃亦即含有至少五个碳原子的氟取代烯烃来作为制冷剂。美国专利第4,788,352号-Smutny涉及至少具有一定程度不饱和度的C5-C8氟化化合物的制备。专利Smutny认为这些已知的高级烯烃可用作制冷剂、杀虫剂、电介质流体、传热流体、溶剂和各种化学反应中间体(见第1栏,11-22行)。
虽然Smutny中阐述的氟烯烃在传热应用中具有一定程度的有效性,但据信这样的化合物亦可能具有某些缺点。例如,一些所述化合物可能易于破坏基质,特别是常用的塑料制品,例如丙烯酸树脂和ABS树脂。而且,由于Smutny中阐述的高级烯烃化合物可能具有一定程度的由杀虫剂活性引起的毒性(如Smutny中所述),因此这些化合物可能亦不适合某些应用。同时,这些化合物具有过高的沸点,因而不可用作某些应用的制冷剂。
溴氟甲烷和溴氯氟甲烷衍生物,尤其是溴三氟甲烷(Halon 1301)和溴氯二氟甲烷(Halon 1211)已广泛用作诸如飞机舱和计算机房等密封区域的灭火剂。然而,由于各种哈龙(Halon)的臭氧消耗很高,因此对它们的使用正逐渐 停止。此外,由于哈龙常常用于存在人类的区域,因此合适的替代物还必须在抑燃或灭火所需的浓度下对人类安全。
因此,申请者已认识到人们对适用于包括蒸气压缩加热和冷却系统及方法等多种应用场合同时可避免一或多种上述缺点的组合物的需求,具体而言对传热组合物、灭火/阻燃组合物、发泡剂、溶剂组合物和增容剂的需求。
发明内容
申请者已发现可通过包括一或多种C3或C4氟烯烃的组合物来满足上述需求及其它需求,较佳化合物具有下述式I:
XCFzR3-z(I)
其中X为一非饱和的、经取代或未经取代的C2或C3烷基,每个R独立为Cl、F、Br、I或H,并且z为1至3。
本发明还提供使用本发明组合物的方法和系统,其包括用于传热、发泡、溶合和气溶胶产生的方法和系统。
具体实施方式
组合物
本发明涉及包括至少一种氟烯烃的组合物,所述氟烯烃含有3至4个碳原子和至少一个碳-碳双键。为方便起见,如果本发明的氟烯烃化合物含有至少一个氢,则有时将其称为氢氟烯烃或HFO。虽然本发明涵盖,上述HFO可含有两个碳-碳双键,但目前认为此类化合物并非较佳。
如上所述,本发明组合物包括一种或多种根据式I的化合物。在较佳实施例中,所述组合物包括具有下列式II的化合物:
其中,每个R独立为Cl、F、Br、I或H,
R′为(CR2)nY,
Y为CRF2,
并且,n为0或1。
在更佳实施例中,Y为CF3,n为0,且在式II中剩余的标记为“R”的取代基中至少有一个为F。
概言之,申请者认为具有上述式I和式II的化合物通常是有效的,且其可在本发明制冷剂组合物、发泡剂组合物、增容剂及溶剂组合物中使用。然而,申请者已惊奇和意外地发现,具有上式结构的某些化合物与其它此类化合物相比较可表现出更期望的低水平毒性。应了解,此发现具有潜在的巨大优势和益处,不仅对制冷剂组合物的调配如此,而且对任何及所有含有满足上式的相对有毒化合物的组合物的调配也如此。更具体而言,申请者认为相对低的毒性水平与式II所示化合物相关,较佳地,其中Y为CF3,至少有一个位于所述不饱和末端碳上的R为H,且在式II中剩余的标记为“R”的取代基中至少有一个为F。申请者还认为这些化合物的所有结构、几何构像和立体异构体皆是有效的,并且具有有益的低毒性。
在更佳实施例中,尤其是包括上述低毒性化合物的实施例中,n为0。因此,在某些较佳实施例中,本发明组合物包括一或多种选自由下列物质组成的组的化合物:四氟丙烯(HFO-1234)和五氟丙烯(HFO-1225)及这些化合物的组合。
本发明的更佳化合物是四氟丙烯和五氟丙烯化合物,其中末端不饱和碳上至多有一个F取代基,特别是:1,3,3,3-四氟丙烯(HFO-1234ze)、2,3,3,3-四氟丙烯(HFO-1234yf)和1,2,3,3,3-五氟丙烯(HFO-1225ye),及这些化合物中任一者的所有立体异构体。通过小鼠和大鼠的吸入暴露测量,申请者发现这些化合物具有非常低的急性毒性水平。另一方面,申请者发现相对高的毒性水平可能与可适用于本发明组合物的某些化合物相关,即那些其末端不饱和碳上有一个以上F的化合物,或者其末端不饱和碳上没有H的化合物。例如,通过小鼠和大鼠的吸入暴露测量,申请者发现1,1,3,3,3-五氟丙烯(HFO-1225zc)表现出不可接受的高度毒性。
本发明的较佳化合物(即HFO-1225和HFO-1234)是已知材料,且其列于美国化学文摘(Chemical Abstract)数据库中。HFO-1225可从(例如)Syntex Chemical公司购买。而且,在专利文献中通常会阐述用于制备氟烯烃的方法。例如,通过催化气相氟化各种饱和及不饱和的含卤素C3化合物来制备氟丙烯(例如CF3CH=CH2)的方法阐述于美国专利第2,889,379号、第4,798,818号及第4,465,786号中,上述专利皆以引用方式并入本文中。美国专利第5,532,419号揭示了使用氯-或溴-卤代氟碳化合物及HF来制备氟烯烃的气相催化方法,此专利也以引用方式并入本文中。EP 974,571还揭示了1,1,1,3-四氟丙烯的制备,它是通过使在高温下气相的1,1,1,3,3-五氟丙烷(HFC-245fa)与以铬为主的催化剂接触进行,或者通过使液相的1,1,1,3,3-五氟丙烷(HFC-245fa)与KOH、NaOH、Ca(OH)2或Mg(OH)2的醇溶液接触进行,所述EP 974,571也以引用方式并入本文中。另外,用于制备根据本发明的化合物的方法亦概述于同时提出的题为“Process for Producing Fluorpropenes(氟丙烯制备方法)”的美国专利申请案(代理档案号为H0003789(26267))中,此案亦以引用方式并入本文中。
据信,本发明组合物具有多个对于许多重要理由而言有利的性质。例如,至少部分地基于数学模拟,申请者认为与其它一些卤化物质相比,本发明的氟烯烃不会对大气化学造成实质性的负面影响,其对臭氧消耗的影响可忽略不计。因此,本发明的较佳组合物具有对臭氧消耗没有实质影响的优点。与目前所用的许多氢氟烷相比,本发明的较佳组合物对全球变暖也没有实质影响。
较佳地,本发明组合物具有一不大于150的全球变暖潜能值(GWP),更佳地其GWP不大于100且尤佳不大于75。本文所用的“GWP”是在100年时间范围内相对于二氧化碳GWP值测量的,如世界气象学联合会的全球臭氧研究和监测项目(World MeteorologicalAssociation’s Global Ozone Research and Monitoring Project)中一篇名为“TheScientific Assessment of Ozone Depletion(臭氧消耗的科学评估)”(2002)的报告中的定义,此报告以引用方式并入本文中。
同时,本发明组合物较佳具有一不大于0.05的臭氧消耗潜能值(ODP),更佳地,其ODP不大于0.02且尤佳约为0。本文所用的“ODP”如世界气象学联 合会的全球臭氧研究和监测项目(World Meteorological Association’s Global Ozone Research andMonitoring Project)中一篇名为“The Scientific Assessment of Ozone Depletion(臭氧消耗的科学评估)”(2002)的报告中的定义,此报告以引用方式并入本文中。
传热组合物
尽管本发明涵盖,本发明组合物可包括各种数量的本发明化合物,但通常较佳的是,本发明制冷剂组合物包括其量占所述组合物至少约50重量%且尤佳占至少约70重量%的式I且尤佳为式II化合物。
为了增强组合物的某项功能或为组合物提供某项功能,或者在某些情形下为了降低组合物成本,本发明组合物可包括其它组分。例如,本发明的制冷剂组合物(尤其是那些用于蒸气压缩系统的制冷剂组合物)可包括润滑剂,通常润滑剂的用量占组合物重量的约30重量%至约重量50%。而且,本发明组合物还可包括如丙烷等增容剂,以达到增加润滑剂相容性及/或可溶性的目的。这些增容剂(包括丙烷、丁烷和戊烷)的量较佳占组合物重量的自约0.5至约5重量%。如美国专利第6,516,837号(其以引用方式并入本文中)所揭示,亦可将表面活性剂和增溶剂组合添加到本发明组合物中以增加油可溶性。常用制冷润滑剂,例如在制冷机中与氢氟碳化合物(HFC)制冷剂一起使用的多元醇酯(POE)和聚烷撑二醇(PAG),可同本发明制冷剂组合物一起使用。
发泡剂、发泡体和可发泡组合物
发泡剂也可用于形成或构成一或多种本发明组合物。如上所述,本发明组合物可包括各种数量的本发明化合物。然而,通常较佳的是,对于用作本发明发泡剂的较佳组合物而言,式I且尤佳为式II化合物的用量占所述组合物的至少约5重量%且尤佳占至少约15重量%。
在其它实施例中,本发明提供由本发明组合物制备的可发泡组合物,较佳为聚氨基甲酸酯、聚异氰酸酯及挤出型热塑性发泡体组合物。在这些发泡体实施例中,可发泡组合物中可包括一或多种本发明组合物作为发泡剂或发泡剂的一部分,所述可发泡组合物较佳包括一种或多种能够在适宜条件下反应及/或发 泡以形成发泡体或者泡孔结构的额外组分,如业内所熟知。本发明还涉及发泡体,且较佳为闭孔发泡体,其由含有发泡剂(其构成本发明组合物)的聚合物发泡调配物来制备。在另一实施例中,本发明提供一用于形成热塑性发泡体的可发泡组合物,例如聚苯乙烯和聚乙烯(PE),较佳为低密度PE。
在某些较佳实施例中,分散剂、泡孔稳定剂、表面活性剂和其它添加剂也可包括在本发明发泡剂组合物中。表面活性剂可视情况添加,但最好添加其作为泡孔稳定剂。一些代表性材料以DC-193、B-8404和L-5340商品名出售,其通常为例如美国专利第2,834,748号、第2,917,480号、和第2,846,458号所揭示的那些聚硅氧烷聚氧化烯嵌段共聚物,上述专利皆以引用方式并入本文中。其它可选择用于发泡剂混合物的添加剂包括阻燃剂,例如,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、磷酸氢二铵、各种卤代芳香族化合物、氧化锑、氢氧化铝、聚氯乙烯,等等。
推进剂组合物
另一方面,本发明提供含有本发明组合物或基本由本发明组合物组成的推进剂组合物,此推进剂组合物较佳为可喷射组合物。较佳地,本发明推进剂组合物包括一拟喷射材料和一推进剂,其包括本发明组合物、基本由或由本发明组合物组成。可喷射混合物中可包含惰性成分、溶剂和其它材料。较佳地,可喷射组合物为一气溶胶。适宜喷射材料包括但不限于化妆品材料,例如芳香剂、香料、发胶、清洁剂和磨砂剂以及医药材料,例如抗哮喘和抗口臭药剂。
方法和系统
本发明组合物适用于多种方法和系统,包括作为传热方法和系统中的传热流体,例如用作制冷、空调和热泵系统中的制冷剂。本发明组合物亦可有利地用于产生气溶胶的系统和方法中,较佳包括这些系统和方法中的气溶胶推进剂或由所述气溶胶推进剂组成。形成发泡体的方法和灭火及抑燃方法也包括在本发明的某些方面中。本发明某些方面还提供去除物件残余物的方法,其中本发明组合物在这些方法和系统中用作溶剂组合物。
传热方法
较佳传热方法通常包括提供一种本发明组合物并使热量传递到所述组合物或由所述组合物传出从而改变此组合物的相态。例如,本发明方法通过吸收一流体或物件的热量提供冷却,较佳地,通过蒸发拟冷却主体或流体附近的本发明制冷剂组合物产生含有本发明制冷剂组合物的蒸气来提供冷却。较佳地,所述方法包括另一压缩制冷剂蒸气的步骤,通常在一较高压力下使用压缩机或类似设备来生成本发明组合物蒸气。一般而言,蒸气压缩步骤导致蒸气热量的增加,因而引起高压蒸气温度升高。较佳地,本发明方法包括自该高温高压蒸气移除至少一部分通过蒸发和压缩步骤增加的热量。热移除步骤较佳包括在较高压力条件下冷凝所述高温高压蒸气以产生以产生较高压力的包括一种本发明组合物的液体。然后,此较高压力液体较佳经历一额定等焓减压过程,从而生成相对低温低压的液体。在此等实施例中,该低温制冷剂液体进而吸收来自拟冷却主体和流体的热量而蒸发。
在本发明的另一方法实施例中,本发明组合物可用于产热方法中,所述方法包括冷凝一制冷剂,此制冷剂包括位于拟加热液体或主体附近的组合物。上述方法通常是上述制冷循环的反向循环。
发泡方法
本发明一实施例涉及形成发泡体的方法,较佳地,涉及形成聚氨基甲酸酯发泡体和聚异氰酸酯发泡体的方法。所述方法通常包括提供一种本发明发泡剂组合物,向可发泡组合物中直接或间接地添加所述发泡剂组合物,并在适于形成发泡体或泡孔结构的条件下使所述可发泡组合物反应,如业内所习知。任一种业内已熟知的方法,例如“PolyurethanesChemistry and Technology(聚氨基甲酸酯化学与技术)”第一、二卷(Saunders和Frisch,1962,John Wiley和Sons,New York,NY)中所介绍的那些方法(此文献以引用方式并入本文中),皆可用于或经改变用于本发明发泡体实施例中。通常,这些较佳方法包括通过组合一异氰酸酯、一多元醇或多元醇混合物、一含有一或多种本发明组合物的发泡剂或发泡剂混合物及其它材料(例如催化剂、表面活性剂、和视情况阻燃 剂、着色剂或其它添加剂)来制备聚氨基甲酸酯发泡体和聚异氰酸酯发泡体。
在许多应用中可方便地以预混调配物的形式提供用于聚氨基甲酸酯发泡体或聚异氰酸酯发泡体的组分。最常见的是将发泡体调配物预混为两种组分。异氰酸酯及视情况某些表面活性剂和发泡剂构成第一种组分,通常称为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组分构成第二种组分,通常称为B组分。因此,可通过将A和B两种组分混合在一起来很容易地制备聚氨基甲酸酯发泡体或聚异氰酸酯发泡体,当少量制备时可通过手动方式混合,或者较佳地通过机器混合技术来形成块、平板、薄片、浇注面板和其它成品、喷射用发泡体、泡沫等等。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等其它成分作为第三组分添加至混合头或反应位置。然而,最佳地,可将它们合并至上述一B组分中。
也可使用本发明组合物制备热塑性发泡体。例如,可以常用方式将习用聚苯乙烯和聚乙烯调配物与此类组合物组合,从而生成硬质发泡体。
清洁方法
本发明还提供通过向一物件施于本发明组合物来去除一产品、零件、元件、基材、或者任何其它物件及其一部分上的污物方法。为方便起见,本文所用术语“物件”指代所有这些产品、零件、元件、基材等等,并进一步拟指代其任何表面或部分。而且,术语“污物”指代出现在所述物件上的任何不希望出现的材料或物质,即使这种物质是有意放在所述物件上。例如,在半导体装置制造中,常常会在基材上沉积一光阻材料以形成蚀刻作业遮罩,并随后将此光阻材料从所述基材上移除。本文所用术语“污物”拟包括及涵盖此一光阻材料。
本发明较佳方法包括,蒸气向物件施加本发明组合物,其中在某些应用中以蒸气除脂和溶剂清洁方法为佳,尤其对于那些复杂部件和难以去除污物的场合。较佳的蒸气脱脂和溶剂清洁方法由将一物件暴露于沸腾溶剂蒸气的步骤组成,此步骤较佳在室温下进行。冷凝在物体上的蒸气有利于提供一相对洁净的蒸馏溶剂,以洗去油脂或者其它污物。因此,这些方法所具有的一额外优势在 于,与在液体溶剂中简单地清洁物体相比较,本发明溶剂组合物最后自物体上的蒸发仅可能造成极少残留。
对于其中物件上具有难以去除污物的应用场合,本发明方法较佳包括将本发明溶剂组合物温度升高至周围温度以上,或升高到任何其它在此应用中可有效实质提高溶剂清洁作用的温度。这些方法对于其中必须快速有效清洁物件(尤其是金属零件和组件)的大规模装配线作业而言通常亦较佳。
在较佳实施例中,本发明清洁方法包括在一较高温度下且更佳系在溶剂沸点左右将拟清洁物件浸没在液体溶剂中。在这些作业中,这一步骤较佳可去除物件上的大量且尤佳为大部分目标污物。较佳地,在此步骤之后跟随一将所述物件浸没在溶剂(较佳为新蒸馏溶剂)中的步骤,其中所述溶剂的温度低于前一浸没步骤中溶剂的温度,较佳为周围温度或室温。该等较佳方法还包括随后使此物件与本发明溶剂组合物的较热蒸气接触的步骤,此步骤较佳通过将此物件暴露于溶剂蒸气(来自上述第一浸没步骤中提及的热/沸腾溶剂)中实施。这较佳会导致溶剂蒸气在此物件上的冷凝。在某些较佳实施例中,所述物件可在最后漂洗前用蒸馏溶剂喷洒。
本发明涵盖,许多种类和类型的蒸气脱脂设备皆可适用于本发明方法中。Sherliker等人在美国专利第3,085,918号(其以引用方式并入本文中)中揭示了此类设备的一个实例及其作业。Sherliker等人所揭示的设备包括一用于容纳溶剂组合物的沸腾槽、一用于容纳蒸馏溶剂的清洁槽、一水分离器和其它辅助设备。
本发明清洁方法还可包括冷清洗,其中,受到污染的物件可在周围温度或室温条件下浸没在本发明流体组合物中,或者在所述条件下用浸透溶剂的抹布及类似物擦拭所述物件。
可燃性减低方法
根据某些其它较佳实施例,本发明提供减低流体可燃性的方法,所述方法包括向所述流体中添加一本发明化合物或组合物。根据本发明,可减低与任一 广泛可燃流体相关联的可燃性。例如,根据本发明,可减低与诸如环氧乙烷、可燃氢氟碳化合物和碳氢化合物(包括HFC-152a、1,1,1-四氟乙烷(HFC-143a)、二氟甲烷(HFC-32)、丙烷、己烷、辛烷及诸如此类)等流体相关联的可燃性。为本发明的目的,可燃流体可以是通过标准常规测试方法(如ASTM E-681等)测量的在空气中表现出可燃性的任何流体。
根据本发明,可添加任何适宜量的本发明化合物或组合物以降低一流体的可燃性。如所属领域的技术人员所熟知,添加量应取决于,至少部分取决于所述流体的可燃性程度和期望其可燃性降低的程度。在某些较佳实施例中,添加至可燃流体中的化合物或组合物量能够有效地使所得流体实质上不可燃。
抑燃方法
本发明进一步提供抑燃方法,所述方法包括使火焰与含有本发明化合物或组合物的流体接触。可使用任何适宜方法使火焰与本发明组合物接触。例如,一本发明组合物可被喷洒、倾倒到火焰上或者至少一部分火焰可浸没在所述组合物中,等等。依据本文的教示,所属领域的技术人员可容易地使多种习用抑燃设备和方法适用于本发明。
消毒方法
出于健康和安全等原因,例如为了病人和医护人员的健康和安全,许多物件、装置和材料,尤其是用于医学领域的物件、装置和材料,必须在使用前消毒。本发明提供了消毒方法,所述方法包括使将要消毒的物件、装置和材料与本发明的化合物或组合物接触。这些方法可以是高温消毒方法,也可以是低温消毒方法。在某些实施例中,高温消毒法包括把将要消毒的物件、装置或材料暴露在约250℉至约270的温度下的包括本发明的化合物或组合物的热流体中,此较佳是在大体密封的容器内进行。所述方法通常可在短于约2小时内完成。然而,某些物件,如塑料物件和电元件等,不能经受如此高温,因而需低温消毒。
本发明的低温消毒法涉及在约100℉至约200℉的温度下使用本发明的化合物或组合物。本发明的化合物可与其它常用化学消毒剂组合在一起以便形成本 发明的消毒组合物,例如,所述常用化学消毒剂包括环氧乙烷(EO)、甲醛、过氧化氢、二氧化氯和臭氧。
本发明的低温消毒法最好至少是一种在一大体密封(较佳具有气密性)的容器内进行的两步骤方法。在第一步骤(消毒步骤)中,将已清洁并包装在透气袋中的物件放到容器中。然后,通过抽真空、或许通过用水蒸汽替换空气从该容器中抽出空气。在某些实施例中,最好将水蒸汽注入该容器内,从而获得在约30%至约70%范围内的相对湿度。这样的湿度可使在获得所需相对湿度后引入容器内的消毒剂的消毒效力最大化。在一段足以使消毒剂渗入包装袋并到达物件空隙的时间之后,将消毒剂和水蒸汽从容器中抽出。
在所述方法的较佳第二步骤(通气步骤)中,物件经通气以除去消毒剂残留物。去除此等残留物在使用有毒消毒剂的情况下特别重要,但在其中使用实质无毒的本发明化合物的情况下此一去除步骤为一可选步骤。典型通气过程包括空气洗涤、持续通气及二者的组合。空气洗涤是一分批过程,通常包括将容器抽真空一较短时间(例如12分钟),然后,向此容器中导入大气压力或更高压力的空气。该循环可重复任意数量的次数,直到将消毒剂去除到满意程度为止。持续通气通常包括通过自所述容器一侧的进口导入空气,然后通过在出口处施加一较小真空通过所述容器另一侧的出口抽出空气。这两种方法常常组合使用。例如,一常用方法包括实施空气洗涤并随后实施通气循环。
实例
下述实例仅用于阐释本发明目的而非意欲限制本发明的范围。
实例1
性能系数(COP)是一普遍接受的制冷剂性能指标,尤其适用于表示一制冷剂在一包括制冷剂蒸发或冷凝的加热或冷却循环中的相对热力学效率。在制冷工程中,该术语表示有效制冷量与压缩机在压缩气体时所施加能量的比值。制冷剂容量表示制冷剂所提供的冷却或加热量,并提供了在一给定制冷剂体积流率下压缩机泵送热量的能力指标。换句话说,对于一具体压缩机而言,一具有高容量的制冷剂将传送更多的冷却力或热力。一种用于在特定作业条件下评估 一制冷剂COP的方法是根据制冷剂热力学性质并使用标准制冷循环分析技术进行的(参见例如,R.C.Downing,FLUOROCARBON REFRIGERANTS HANDBOOK,第三章,Prentice-Hall,1988)。
本例提供一制冷/空调循环系统,其中在压缩机入口温度约为50℉的额定等熵压缩条件下冷凝温度约为150℉,蒸发温度约为-35℉。表1中列出了若干种本发明组合物在一冷凝温度及蒸发温度范围的COP,所述COP基于其COP值为1.00、容量值为1.00且出口温度为175的HFC-134a测定。
表1
制冷剂组合物 | 相对COP | 相对容量 | 出口温度( ) |
HFO 1225ye | 1.02 | 0.76 | 158 |
HFO trans-1234ze | 1.04 | 0.70 | 165 |
HFO cis-1234ze | 1.13 | 0.36 | 155 |
HFO 1234yf | 0.98 | 1.10 | 168 |
所述实例表明,用于本发明组合物的某些较佳化合物与HFC-134a比较皆具有更佳的能量效率(1.02、1.04及1.03与1.00比较),且使用本发明制冷剂组合物的压缩机可产生更低的出口温度(158、165和155与175比较),此种情况较为有利,因为此可减少维修问题。
实例2
本实例测试HFO-1225ye和HFO-1234ze与各种制冷润滑剂的混溶性。所测试润滑剂为矿物油(C3)、烷基苯(Zerol 150)、酯油(Mobil EAL 22cc和Solest 120)、聚烷撑二醇(PAG)油(用于134a系统的Goodwrench制冷油)和聚(α-烯烃)油(CP-6005-100)。对于每种制冷剂/油组合皆测试三种组合物,即其中润滑剂的重量百分比分别为5%、20%和50%且其余部分为待测试本发明化合物的组合物。
将润滑剂组合物放在厚壁玻璃试管中。将试管抽真空,添加本发明制冷剂化合物,并封好试管。然后将试管置于一气浴环境容器中,其温度在约-50℃至 约70℃范围内变化。大约每隔10℃目测试管内容物以观察是否存在一或多个液相。在观察到一个以上液相的情况下,则报告所述混合物不可混溶。在仅观察到一个液相的情况下,则报告所述混合物可混溶。在观察到两个液相但其中一个液相仅占很小体积的情况下,则报告所述混合物可部分混溶。
经判断,聚烷撑二醇和酯油润滑剂在整个温度范围内可以各种测试比例混溶,但HFO-1225ye和聚烷撑二醇的混合物除外,人们发现此制冷剂混合物在-50℃至-30℃的温度范围内不可混溶,在-20℃至50℃的温度范围内可部分混溶。当制冷剂中聚烷撑二醇的重量百分比浓度为50重量%且在60℃时,制冷剂/PAG混合物可混溶。在70℃且制冷剂中润滑剂的重量百分比在5重量%至50重量%范围内时,所述混合物可混溶。
实例3
当与制冷和空调系统中使用的金属相接触时,于350℃下测试本发明制冷剂化合物和组合物与PAG润滑油的相容性,所示条件比许多制冷和空调应用中采用的条件更加严格。
将铝、铜和钢试样添加至厚壁玻璃试管中。向试管中添加2克油。然后将试管抽真空,并添加1克制冷剂。将试管置于350℉烤箱中一周后进行目测观察。在暴露期结束时取出试管。
本程序针对下述油和本发明化合物的组合进行:
a)HFC-1234ze和GM Goodwrench PAG油
b)HFC1243zf和GM Goodwrench PAG油
c)HFC-1234ze和MOPAR-56 PAG油
d)HFC-1243zf和MOPAR-56 PAG油
e)HFC-1225ye和MOPAR-56 PAG油。
在所有情形下,试管内容物的外观变化皆很小。这表明,当本发明的制冷剂化合物和组合物与存在于制冷和空调系统中的铝、钢和铜接触时、以及与可能包含于这些组合物内或者和这些组合物同时用于这些类型的系统中的多种类型润滑油接触时,本发明的制冷剂化合物和组合物均可保持稳定。
比较实例
如实例3所述,将铝、铜、钢试样和矿物油及CFC-12添加至厚壁玻璃试管中,并在350℃下加热一周。当暴露期结束时,取出试管并进行目测观察。如果观察到液体内容物变黑,则说明试管内容物严重分解。
迄今,在许多制冷系统和方法中人们一直选用CFC-12和矿物油的组合。因此,与广泛使用的先前技术制冷剂-润滑油组合相比,本发明制冷剂化合物和组合物与许多常用润滑油组合具有显著较佳的稳定性。
本发明涉及以下实施方案:
1.一种传热组合物,其包括:
(a)至少一种润滑剂,其包括聚亚烷基二醇和/或多元醇酯;和
(b)至少50重量%的HFO-1234ze,所述传热组合物具有一不大于75的全球变暖潜能值(GWP)。
2.实施方案1的传热组合物,其包含5重量%的聚亚烷基二醇和95重量%的HFO-1234ze,所述聚亚烷基二醇和HFO-1234ze在约-50℃至+70℃的至少一个温度下有一个液相。
3.实施方案1的传热组合物,其包含20重量%的聚亚烷基二醇和80重量%的HFO-1234ze,所述聚亚烷基二醇和HFO-1234ze在约-50℃至+70℃的至少一个温度下有一个液相。
4.实施方案1的传热组合物,其包含50重量%的聚亚烷基二醇和50重量%的HFO-1234ze,所述聚亚烷基二醇和HFO-1234ze在约-50℃至+70℃的至少一个温度下有一个液相。
5.一种将热量传导到一流体或主体或者从一流体或主体传导热量的方法,其包括:
(a)提供一种传热组合物,其包括(i)至少一种润滑剂;和(ii)至少50重量%的HFO-1234ze;和
(b)将所要传导的热量传递到所述组合物或由所述组合物传出,从而改 变该组合物的相态;
其中所述润滑剂选自聚亚烷基二醇和多元醇酯润滑剂。
6.一种用于提供传热的蒸汽压缩系统,包括制冷剂系统,在所述制冷剂系统中包括压缩机、冷凝器和传热组合物,所述传热组合物包含(i)至少一种润滑剂,其包括聚亚烷基二醇和/或多元醇酯;和(ii)至少50重量%的HFO-1234ze,其中所述系统在压缩机入口温度约为50°F的额定等熵压缩条件下、150°F的冷凝温度、蒸发温度约为-35°F下可操作。
7.如实施方案1、5、6任一项所述的传热组合物、方法或系统,其中所述HFO-1234ze包含反式HFO-1234ze。
8.如实施方案7所述的传热组合物、方法或系统,其中所述组合物具有1.04的相对于HFC-134a的COP,所述HFC-134a的COP值为1.00、容量值为1.00且出口温度为175°F。
9.如实施方案1、5、6任一项所述的传热组合物、方法或系统,其中所述HFO-1234ze包含顺式HFO-1234ze,其具有1.13的相对于HFC-134a的COP,所述HFC-134a的COP值为1.00、容量值为1.00且出口温度为175°F。
10.如实施方案1、5、6任一项所述的传热组合物或方法,其中所述润滑剂存在的量是传热组合物的约30-约50%重量。
11.如实施方案1、5、6任一项所述的传热组合物或方法,其中所述润滑剂包括聚亚烷基二醇
12.如实施方案1、5、6任一项所述的传热组合物或方法,其中所述润滑剂包括多元醇酯。
13.如实施方案1、5、6任一项所述的传热组合物或方法,其中所述传热组合物还包含至少一种相容剂。
14.如实施方案13所述的传热组合物或方法,其中所述相容剂选自丙烷、丁烷、戊烷及它们的组合。
15.如实施方案1、5、6任一项所述的传热组合物、方法或系统,其中所述传热组合物具有不大于约150的全球变暖潜能值(GWP)。
16.如实施方案7所述的传热组合物、方法或系统,其中所述传热组合物具有不大于约75的GWP。
Claims (34)
1.一种传热组合物,其包括:
(a) 至少一种润滑剂,其包括聚亚烷基二醇和/或多元醇酯;和
(b) 至少50重量%的HFO-1234ze,其中所述传热组合物具有一不大于75的全球变暖潜能值。
2.权利要求1的传热组合物,其包含5重量%的聚亚烷基二醇和95重量%的HFO-1234ze,所述聚亚烷基二醇和HFO-1234ze在-50℃至+70℃的至少一个温度下有一个液相。
3.权利要求1的传热组合物,其包含20重量%的聚亚烷基二醇和80重量%的HFO-1234ze,所述聚亚烷基二醇和HFO-1234ze在-50℃至+70℃的至少一个温度下有一个液相。
4.权利要求1的传热组合物,其包含50重量%的聚亚烷基二醇和50重量%的HFO-1234ze,所述聚亚烷基二醇和HFO-1234ze在-50℃至+70℃的至少一个温度下有一个液相。
5.权利要求1-4中任一项的传热组合物, 其中所述HFO-1234ze是反式HFO-1234ze。
6.权利要求5的传热组合物,其中所述组合物具有1.04的相对于HFC-134a的性能系数,所述HFC-134a的性能系数值为1.00、容量值为1.00且出口温度为175℉。
7.权利要求1-4中任一项的传热组合物,其中所述HFO-1234ze是顺式HFO-1234ze,其具有1.13的相对于HFC-134a的性能系数,所述HFC-134a的性能系数值为1.00、容量值为1.00且出口温度为175℉。
8.权利要求1的传热组合物, 其中所述润滑剂存在的量为传热组合物的30-50重量%。
9.权利要求1的传热组合物, 其中所述润滑剂是聚亚烷基二醇。
10.权利要求1的传热组合物, 其中所述润滑剂是多元醇酯。
11.权利要求1的传热组合物, 其中所述传热组合物还包括至少一种相容剂。
12.权利要求11的传热组合物,其中所述相容剂选自丙烷、丁烷、戊烷及它们的组合。
13.一种将热量传导到流体或主体或者从流体或主体传导热量的方法,其包括:
(a)提供传热组合物,其包括 (i) 至少一种润滑剂;和(ii) 至少50重量%的HFO-1234ze;和
(b)将所要传导的热量传递到所述组合物和/或由所述组合物传出,从而改变该组合物的相态;
其中所述润滑剂选自聚亚烷基二醇和多元醇酯润滑剂。
14.权利要求13的方法, 其中所述HFO-1234ze是反式HFO-1234ze。
15.权利要求14的方法,其中所述组合物具有1.04的相对于HFC-134a的性能系数,所述HFC-134a的性能系数值为1.00、容量值为1.00且出口温度为175℉。
16.权利要求13的方法,其中所述HFO-1234ze是顺式HFO-1234ze,其具有1.13的相对于HFC-134a的性能系数,所述HFC-134a的性能系数值为1.00、容量值为1.00且出口温度为175℉。
17.权利要求13-16中任一项的方法,其中所述润滑剂存在的量为传热组合物的30-50重量%。
18.权利要求13-16中任一项的方法,其中所述润滑剂是聚亚烷基二醇。
19.权利要求13-16中任一项的方法,其中所述润滑剂是多元醇酯。
20.权利要求13-16中任一项的方法,其中所述传热组合物还包括至少一种相容剂。
21.权利要求20的方法,其中所述相容剂选自丙烷、丁烷、戊烷及它们的组合。
22.权利要求13-16中任一项的方法,其中所述传热组合物具有不大于150的全球变暖潜能值。
23.权利要求22的方法,其中所述传热组合物具有不大于75的全球变暖潜能值。
24.一种用于提供传热的蒸汽压缩系统,包括制冷系统,在所述制冷系统中包括压缩机、冷凝器和传热组合物,所述传热组合物包含 (a) 至少一种润滑剂,其包括聚亚烷基二醇和/或多元醇酯;和(b) 至少50重量%的HFO-1234ze,其中所述系统在压缩机入口温度为50℉的额定等熵压缩条件下、150℉的冷凝温度、蒸发温度为-35℉下可操作。
25.权利要求24的蒸汽压缩系统,其中所述HFO-1234ze是反式HFO-1234ze。
26.权利要求25的蒸汽压缩系统,其中所述组合物具有1.04的相对于HFC-134a的性能系数,所述HFC-134a的性能系数值为1.00、容量值为1.00且出口温度为175℉。
27.权利要求24的蒸汽压缩系统,其中所述HFO-1234ze是顺式HFO-1234ze,其具有1.13的相对于HFC-134a的性能系数,所述HFC-134a的性能系数值为1.00、容量值为1.00且出口温度为175℉。
28.权利要求24-27中任一项的蒸汽压缩系统,其中所述润滑剂存在的量是传热组合物的30-50重量%。
29.权利要求24-27中任一项的蒸汽压缩系统,其中所述润滑剂是聚亚烷基二醇。
30.权利要求24-27中任一项的蒸汽压缩系统,其中所述润滑剂是多元醇酯。
31.权利要求24-27中任一项的蒸汽压缩系统,其中所述传热组合物还包含至少一种相容剂。
32.权利要求31所述的蒸汽压缩系统,其中所述相容剂选自丙烷、丁烷、戊烷及它们的组合。
33.权利要求24-27中任一项所述的蒸汽压缩系统,其中所述传热组合物具有不大于150的全球变暖潜能值。
34.权利要求33所述的蒸汽压缩系统,其中所述传热组合物具有不大于75的全球变暖潜能值。
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