CN1052031C - 含碘氟烃组合物及其应用 - Google Patents

含碘氟烃组合物及其应用 Download PDF

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CN1052031C
CN1052031C CN94191986A CN94191986A CN1052031C CN 1052031 C CN1052031 C CN 1052031C CN 94191986 A CN94191986 A CN 94191986A CN 94191986 A CN94191986 A CN 94191986A CN 1052031 C CN1052031 C CN 1052031C
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fluoroiodocarbon
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iodine
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J·S·尼米兹
L·H·兰克福德
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Abstract

本发明揭示了具有效、环境安全、不燃、低毒等特性的一组新的冷冻剂、溶剂、发泡剂、推进剂,及灭火剂等。这些作用剂是清洁的且是不导电性的,它们具有短的大气层寿命与可忽视的臭氧耗竭位能,以及低的全球温室效应位能。这些作用剂包括至少一种含碘氟烃的作用剂,可以是纯的,亦可与添加物混合,添加物选自:醇类、酯类、醚类、氟代醚类、烃类、含氢氟烃类,及全氟化碳等。

Description

含碘氟烃组合物及其应用
发明范围
本文中所揭示的发明一般是关于含有含碘氟烃的组合物,与如何制造及使用此组合物的方法。发明背景
含氯氟烃(简称CFC),诸如CFC-11,CFC-12,CFC-113,CFC-114,CFC-115,以及含有这些CFC的掺合物,诸如,R-500及R-502,它们目前是充当作冷冻剂、溶剂、发泡剂以及推进剂使用。CFC只含有氯、氟及碳其通式为CXClYFZ,其中,X=1或2,且Y+Z=2X+2。一相关的化学品,即是我们熟知的ha1on(亦称作含溴氟烃,简称BFC),它的一般式为CwBrxClYFZ,(其中,w=1或2,y=0或1,且X+Y+Z=2W+2),现今,它是充当作灭火剂使用。
因为CFC及halon具有非常好的化学稳定性,所以,当它们释放在大气中时,只有小部份于对流层经由自然方式予以破坏,因此,CFC及Halon具有长的大气层寿命,且当它们移动到同温层时,便进行光解作用而形成氯基及溴基等,这些基团严重地消耗地球的保护臭氧层。每一个化学品被指定一个臭氧耗竭位能(简称ODP),以定量地反映它破坏同温层臭氧的能力。各化学品的ODP是以CFC-11(CFCl3,三氯氟甲烷)为基准来计算,而CFC-11的ODP值是指定为1.0。现在所使用的CFC,其ODP值接近1,Halon的ODP值则介于2至14间。常用的CFC及halon,其名称,化学式及ODP值列于表1。
表1:充当作冷冻剂、溶剂、发泡剂及推进剂的CFC,其名称,化学式及ODP值
  CFC或Halon         名称     化学式   ODP值
    CFC-11CFC-12CFC-113CFC-114CFC-115R-500R-502Halon 1211Halon 1301Halon 2402     三氯氟甲烷二氯二氟甲烷1,1,2-三氯-1,2,2-三氟乙烷1,2,-二氯-1,12,2-四氟乙烷氯五氟乙烷--a--b溴氯二氟甲烷溴三氟甲烷1,2-二溴四氟乙烷   CCl3FCCl2F2CCl2FCClF2CClF2CClF2CClF2CCF3----CBrClF2CBrF3CBrF2CBrF2    1.01.01.10.80.50.30.74.112.53.9
a.CCl2F2(CFC-12,73.8重量%)与CHF2CF3(HFC-125,26.2
  重量%)的共沸掺合物(azeotropic blends)
b.CClF2CF3(CFC-115,51.2重量%)与CHClF2(HCFC-22,
  48.8重量%)的共沸掺合物。
例如,CFC-12,它大致上占有全球CFC年产量约150百万磅的26重量%。绝大部分的CFC-12最后都释放到大气中,且当它升至同温层时,被紫外线所撞击,因而分解出氯基,氯基催化地破坏保护地球的臭氧层。同温层臭氧的枯竭会使更多的紫外光进入地球的表面,导致人类皮肤癌及白内障的增加,以及造成农作物、自然生态及材料的损害,及其它不利的影响。本发明将提供环保安全的代用剂以取代CFC与halon,而可大大地减低这些不利的影响。
现在,CFC,另外还有氢氯氟烃及含氢氟烃是充当作冷冻剂、溶剂、发泡剂及推进剂。并且CFC已经广泛地运用于这些应用上,因为它们具有有效性、低毒性、不易燃性、不导电性、气化时清洁性、可与碳氢化合物及矿物油润滑剂的相混性,与铜、铝、铁类等金属较不具反应性。然而,按照蒙特利尔草约(Montreal Protocol)的规定,CFC面临停产的命运。虽然,HCFC(其ODP值介于0.02至0.11间)消耗臭氧远少于CFC,但HCFC确实也引起臭氧的枯竭,因此,最终也在蒙特利尔草约下,面临限期停产的命运。
卤化碳(halocarbons)这一大类物质是由含有碳的或可含氢,及含有下列卤素原子中至少一种:氟、氯、溴或碘等的所有分子所组成。碘化碳是卤化碳中含碘;而碘氟化碳则含氟及碘两者。卤代烷(haloalkanes)是卤化碳的一分支,其包括的化合物是由碳、卤素或氢等所组成,但不含氧、氮、或多重键。卤代烷主要是从碳氢化合物所衍生出来的,其中,是以卤素原子(F、Cl、Br或I)取代氢原子。碳氢化合物本身就已经是充当作有效的冷冻剂、溶剂、发泡剂及推进剂,但它的主要缺点是具有非常高的可燃性(尤其是指挥发性较高的碳氢化合物)。替代以高比例的卤原子将可导致不易燃性。CFC及其它高度卤化的卤化碳因而具有碳氢化合物所希望的特性,而且,可兼具不易燃性的实质优点。
毒性是在挑选冷冻剂、溶剂、发泡剂、推进剂、液压流体及灭火剂等时所主要考虑的项目。例如,卤代烷的毒性影响包括刺激或抑制中枢神经系统,引发心律不齐(cardiac arrthymias),使心脏对肾上腺素过敏。吸入卤代烷类则可引起支气管收缩,降低肺弹性,压抑呼吸量,降低平均动脉血压,及产生心跳加快。长期的影响包括肝中毒、突变的发展,畸胎形成及产生致癌物质。
卤化碳所造成的环境影响须予以考虑,其环境影响包括臭氧耗竭位能(ODP),全球温室效应位能(GWP),及对地球上所造成的影响。人们已知含氯及溴的卤代烷都消耗同温层臭氧,其中,溴较氯造成更大的问题(于每一原子而论)。在同温层里,臭氧的枯竭导致地表上紫外线辐射强度的增加,而造成皮肤癌、白内障、抑制人类免疫系统、农作物损害,及水生物损害等发生机率的增加。由于这些问题影响范围是如此严重,因此,蒙特利尔草约(Montreal Protocol)与其它立法已经限制挥发性卤化烷类的生产与使用。
抑制燃烧可由两种机制产生:物理上与化学上的。物理机制牵涉到由分子来吸热,其程度足以降低可燃性材料的温度低于点火温度及/或氧的置换,因而达到终止燃烧的目的。当灭火剂(extinguishant)分子越大(含有更多的原子及键),则具有更多的振动自由度,更高的蒸汽热容量,以及更大的除热量。化学机制牵涉到干扰包括氢、氧、及羟等自由基的燃烧传导(flame-propagation)连锁反应。在理论上而言(但尚未证实),溴原子使得连锁反应得以瓦解。
以前的灭火剂,或是利用化学作用或是利用物理作用,或两者兼用,以达到熄灭燃烧的目的。如二氧化碳取代氧并吸收热能,而像水则完全是热能吸收的功能。以前的卤化作用剂,诸如四氯化碳、溴三氟甲烷等等则是同时利两种功能方式。美国陆军于四十年代研究卤化作用剂,而导致采用闻名的Halon族作用剂。而新墨西哥工程研究学院(New Mexico Engineering Research Institute)的其它研究已经证明纯净的全氟化碳及某些纯净的碘化作用剂,未来充当作灭火剂是相当有潜力的(Nimitz等人,“具低臭氧耗竭位能与低全球温室效应位能的纯净且可降解转化的(tropodegradable)灭火剂”,美国专利申请号07/800,532,正在审查中,Nimitz等人申请,1991年11月27日)。在此研究里,证明了有几种纯净的含碘化学品表现出相近于含溴化学品的灭火特性。
对于溴化、全氟化、及纯的碘化作用剂有许多值得关心的事。溴化作用剂由于对破坏同温臭氧层具有极大的威胁,因此蒙特利尔草约通过以后,现在已不再生产。全氟化作用剂具有高的全球温室效应位能及可达数千年之久的大气层寿命,它们的生产量及使用已由立法及现今制造商应负的责任使命而予以限制。全氟化碳的成本高且它们的灭火效力较逊于溴化作用剂。对于重量及体积要求较严格的场合,诸如飞机、油槽、轮船,为了灭火而额外增加的重量和体积是无法忍受的。一种纯的碘化作用剂(三氟碘甲烷,CF3I)已经为人熟知已久,具有灭火功能的潜力(有机化合物辞典,Chapman and Hall出版,纽约,1982年,5477页)。有关CF3I的考虑始终围绕毒性及分散能力。溴三氟甲烷(CF3Br)曾是被挑中的对象以用于这些气体流溢的场合,即使到现在仍是如此。
冷冻剂、溶剂、发泡剂、推进剂、液压流体及灭火剂必须在储存及使用一段长时期内是化学安定的,也必须与它们的存放系统不起反应。冷冻剂正常的操作温度是介于-98℃至8℃两极限间。在住宅、商店、公共机构的多数应用中,温度范围为-23℃~8℃。在特别的情况下(例如,马达烧坏掉),可能会经历更高的温度,但在这些场合下,形成了其它的污染物,无论如何,将需要更换液体。虽然,溶剂,发泡剂及推进剂正常情况下是储存及使用于室温下,它们可能在不寻常的状况下,在储存期间,经历暂时性的高温,其温度可高达150℃。灭火剂储放在-20℃至50℃的温度下必须是安定的,且必须在燃烧温度能够分解以产生捕捉化学基(radical-trapping)的物种。
冷冻剂的运作是在装置的某一地方气化而吸热,然后,再与装置的另一部分凝结而放热。其所需的有效特性包括适当的蒸汽压曲线、蒸发焓、溶解度(包含与油的可混性)、毒性,与可燃性。CFC-12、114、500、502充当作冷冻剂已经行之已久,因为它们具备了所需的物理特性,储如适当的沸点及工作压,蒸发焓、与矿物油为主的润滑剂的可混性、低毒性、及不可燃性。此外,CFC对金属与封装材料是比较不具腐蚀性的。通常所使用的冷冻剂,其特性(包括典型的蒸发器及凝结器温度以及其用途)列于表2。
表2.CFC冷冻剂的典型蒸发器与凝结器的温度
CFC   蒸发器温度(°F)  凝结器温度(°F) 典型的用途
   111213113114115500502503    35至40-10至35-50至-7535至40-24至35-50-30至-80-40--100-100--200   95至105105至125100至12595至105100至125100至125100至125100至125100至125        离心式冷却机,溶剂,发泡剂自动式空气调节机,冷冻机,窗型空气调节机极低温冷冻机离心式冷却机,溶剂,清洁剂渔事用冷却机,低温冷冻机低温冷冻机超级市场冷冻柜,贩卖机,民用运输低温冷藏冷冻机
碳氢化合物,包括环丙烷、丙烷、丁烷及异丁烷亦已使用作高效率的冷冻剂。然而,碳氢化合物由于具有高可燃性,因此并没有民生用途。它们拥有其它的特性并且是不贵的。然而,就是由于其可燃性,使得有关规定限制碳氢化合物冷冻剂的使用,只能用于远离住宅的极小(总装剂量少于3磅)的组件或设备。这些禁令严格限制现有含碳氢化合物的冷冻剂的使用。
冷藏设备需要润滑剂不断地在冷冻剂液体内循环,以防止摩擦,过热,及烧坏压缩机或轴承。所以,冷冻剂与润滑剂之间的可混性是基本的要求。例如,多数润滑剂不是非常溶于含氢氟烃(HFC),这已成为使用HFC-134a作为替代冷冻剂时的主要问题。
现在,值几十亿的使用中的冷藏及空调设备存在于地球上,如果CFC无法供应,又无其它的替代品,则这些设备多半将变成无法操作,甚至可能填尸于野。有用寿命将急速减短,且绝大部分用以制造及安装设备的能量及资源将形同浪费。
溶剂应可溶解诸如油类、油脂类及蜡类等的拒水性污物(soils),应该是不燃的及较不具毒性的,且蒸发时应该是干净的。对于溶剂而言,其沸点介于35℃至120℃是较佳的,因为在此沸点范围内会使溶剂在一合理的时间内蒸发(在1分钟至2小时)。传统上,CFC-113及1,1,1,1-三氯乙烷是优选的溶剂。近来,由于对卤化溶剂的环保顾虑,人们再度对于烃类溶剂引起兴趣,即使这些溶剂具有可燃性,例如,干洗溶剂汽油(具有8至11个碳的烃类石油馏分)。这里所指的烃类石油馏分(hydrocarbon Retroleum fractions),通常是指石油英(ligroin)、矿油精(mineral spirits)、石脑油、石油醚、及石油精等,认为它们代表组成相近的馏分,且这些名称有时可互相交换使用。
发泡剂必须能够在聚合物基体内产生具有一致性且可控制的泡孔大小(cell size),而且最好应具有高绝缘值和不可燃性。有相当多不同种类的发泡剂已经在使用,包括CFC-11、HCFC-22、HCFC-123、HFC-134a、HCFC-141b,及戊烷。在发泡剂内通常都添加水(最高达约25%摩尔),以与成形用聚合物起反应,而释放二氧化碳,以帮助泡孔的形成。最近,一些制造商已转而使用水作为唯一的发泡剂,即使绝缘效果、尺寸稳定性及抗老化性会有稍微损失。
气溶胶型推进剂(aerosol propellant)须具备有高蒸气压,低蒸发热,以及储存时的安定性。在美国,例如CFC曾被充当作推进剂,直到1978年才结束,但在许多国家,CFC仍旧以此用途在使用中。继续使用CFC气溶胶型推进剂会显著地造成同温层臭氧的耗竭。美国已在1978之后,将CFC更换为丁烷及异丁烷等碳氢化合物,以用于推进剂的应用上。这些气体是极度易燃的,曾经有人陷于这些推进剂的火海中。
用以替代Halon的灭火剂必须是能有效熄灭火源的,较不具毒性的,不导电性的,且必须是蒸发时干净的,以及,对环境影响小的。Halon(含溴氟烃)虽然能够符合前四项规范,但由于它们具有长的大气层寿命及高臭氧耗竭位能,因此,按照蒙特利尔草约及其它规定,将面临停产的命运。
虽然,去辨识具有一、二或三种选定特性的化学品是较容易的,但去辨识能同时具备下列特性的化学品则是相当困难的,其特性包括:有效性能、不可燃性、低毒性、干净性、不导电性,与一般润滑剂的可混性,短的大气及环境寿命,可忽略的ODP值,及非常低的GWP。再者,对于含碘氟烃这类人们不大清楚的物质,其选定的组成份子的不寻常及希望的特性绝不是明显的。有关含碘氟烃的研究甚少,且有关该特性在文献上很少有记载。传统的化学知识指示含碘的有机化合物是非常毒且不稳定的,以至于无法用在这些目的上,因此,碘化碳被大多数熟悉此技艺者予以拒绝。部分是由于这种成见之故,对于含碘氟烃类的特性只有少许研究,且它仍旧是属于甚少人知的化学品类。
本发明的重要部分在于确认氟的独特的特性(氟是电负性最强的元素),它强化且稳定了碳—碘键,足以使所选择的含碘氟烃较不具毒性且足够安定以用于溶剂清洁、制冷、发泡及气溶胶推进等作用。为了要辨识它们是否能适用于这些新用途,曾经花费心血去收集与评估其特性,并对其是否具备希望的效力、低毒性及低环境影响进行筛选。因此,本文揭露了新的用途及新的化学品组合两者,并得到了意想不到的结果。
在此所描述的含碘氟烃,有纯的及掺合的两种,它们提供了新的环境安全的、且不易燃的冷冻剂、溶剂、发泡剂、气溶胶型推进剂及灭火剂。这些化合物具有极佳的效能、干净、不导电性、低毒性、不易燃性(自行熄灭)、短大气寿命、可忽略的ODP值、低GWP以及微小的对地球环境的影响。
虽然,某些含碘氟烃在熟知的化学文献中作过简单的描述,但它们于此所描述的用途的潜力以前却未曾予以确认过。含碘氟烃,不论是纯的形态或掺合形态的含碘氟烃未曾充当过溶剂清洁、冷冻、发泡或气溶胶型推进等作用。一种纯的含碘氟烃(CF3I)充当作灭火剂已经简单描述于公开的文献里(有机化合物辞典,Chapman and Hall出版社,纽约,1982年,第5477页)。另外少数的纯含碘氟烃已经由现今发明者之一提出充当灭火之用(Nimitz等人,“具低臭氧耗竭位能与低全球温室效应位能的干净且可降解转化的灭火剂”,正在审理中,美国专利申请号07/800,532,1991年11月27日申请)。然而,没有任何在此所描述的含有含碘氟烃的掺合物,亦没有任何新的纯含碘氟烃的作用剂曾被提出用于灭火或在此所描述的其它用途。这些掺合物与新的纯作用剂提供了实质上的好处,换言之,即低成本,低毒性,改良的物理特性,较高效力,及低的环境影响。发明概述(发明的公开)
本发明的主要目的在于提供较不具毒性的作用剂以用于冷冻、溶剂清洁、发泡、气溶胶推进以及灭火等用途。本发明的另一个目的是提供不易燃并对环境安全的物质组合物。本发明的另一个目的在于提供干净且不导电的含碘氟烃。本发明还有一个目的在于提供纯的以及掺合的含碘氟烃,它们具有可忽略的臭氧耗竭位能,低的全球温室效应位能,以及极小的对大气及地球环境的影响。
本发明的优点是以较低的成本同样获得现存的冷冻剂、溶剂、发泡剂、气溶胶型推进剂、液压流体以及灭火剂等的功能特性。本发明的另一个优点是借由选定的添加物与含碘氟烃混合以完善其特性。本发明还有一个优点是提供有效且在某些场合是上好组合物的含碘氟烃,以替代现存的化合物。较佳实施例说明(实现本发明的最佳模式)
所希望的作用剂必须具备下列所有的特性:有效性、低毒性、不易燃性、以及环境安全等。虽然,去找到能够符合这些规范中的二或三项的化学品是较容易些,但要去识别能够符合所有想要的规范的化学品则是相当困难的。本发明的新颖性即在于找到符合所有规范的化合物及掺合物(与使用它们的方法)。在此所描述的化合物及掺合物是有效的、较不具毒性、不易燃、且对环境影响是温和的。它们具有为得到最佳性能所要求的沸点、蒸气压和蒸发热。以另一化学品与含碘氟烃相混,可以得到一些主要的好处。第一,且或许是最重要的一项,那就是使得混合物完全不燃;第二,经由适当掺合的化学品,其物理特性(包括沸腾范围、密度、粘度、及润滑剂溶解度)可优化以获得最大的效能;第三,已经不高的毒性可以进一步降低;第四,作用剂的成本可以降低。
一般来说,碘化碳与相关的氯或溴化碳相比是较具反应性,较不安定,且较具毒性,因此,它们不适合用于在此所描述的应用上,所以,通常是不予考虑的。然而,本发明的一个重要部分就是确认一个事实,那就是氟所具有的独特的特性可使多氟化碘碳化合物(polyfluorinated ioducarbons)拥有异常低的反应性、高稳定性与低毒性等。由于氟是电负性最强的元素,当键合于碘原子的碳原子上有二个或三个氟原子附着于其上,将会使电子密度后移,并提供空间位阻(steric hindrance),造成在含碘氟烃内的碳—碘键异常坚固且可抗化学反应。所有的三种常见化学反应机制于含碘氟烃里都被抑制,即单分子亲核取代(unimolecular nucleophilic substitution,简称SN1),双分子亲核取代(bimolecular nucleophilic substitution简称SN2),与键均裂取代(homolytic bond cleavage)。因为这样的低反应性,所以含碘氟烃表现出异常的高稳定性及低毒性。此外,碘化碳从未牵连到同温层臭氧耗竭,全球变暖,或长期性的地球环境污染。
在应用本发明有关毒性的规范时,每一种较佳的化合物的特征是其急性毒性(或是实测的或是预测的)不大于现今使用的CFC。在此方面,毒性是按老鼠暴露于该环境下4小时后的LC50(半数致命浓度)计量。含碘氟烃的毒性的资料目前数量有限,但却是相当令人鼓舞的。所有下列的含碘氟烃根据记录均能使老鼠的一小时LC50大于10,000ppm:1-碘全氟乙烷,1-碘全氟丁烷以及1-碘全氟己烷。
若要使一化学品能够具有可忽略的ODP值,则它必须或是(1)不含氯,也不含溴;或者(2)在对流层借助自然的方法进行快速且完全的破坏(因此,永远不会到达同温层)。在对流层里,有三种机制可对卤碳化合物予以破坏,分别是光解作用,与羟基(OH)发生反应,以及与氧原子(O)发生反应。在对流层里,由于有同温层臭氧与其它大气中的成分的遮蔽效应,太阳光线的波长较长于同温层光线的波长(因而具有较低的能量)。如果分子能够在对流层予以光解,则它们必须含有吸光的基团(发色基团)与弱的键。此具有弱键的吸光基团包括碳与碘之间的σ键。碳与碘键对光解作用极度敏感,甚至在地面上也可在阳光下轻易地解理(cleave)。所以,含碘氟烃在对流层将被光解作用予以迅速催毁,而不致造成臭氧的枯竭或是实质上全球的温室效应。
本发明的化合物亦是在它们的全球温室效应位能的基础考虑下做选择的,现在已越来越多地将这问题与臭氧耗竭因素一起考虑。全球温室效应是引起大气层中的分子吸收从地球表面辐射出来的红外线。分子具有愈长的大气层寿命与具有愈大的红外线吸收量,其GWP也将愈大。可以确认的一点是一些含氯氟烃所具有的GWP几千倍于二氧化碳。含碘氟烃由于能够迅速地光解而产生短暂的大气层寿命,因此,它们的GWP相较于CFC,halon,HCFC,HFC,及全氟代烃等已经大大的降低。
含碘氟烃所具有的短暂大气层寿命是由于碳—碘键偏向于吸收紫外线能量,因而当它进入大气层后便能于短期内,在自然的日光下分解。分解后的副产物是无害的盐类,且它们在自然的沉淀下,经由环境而予以清理。含碘氟烃甚至可含有氯或溴原子而不会造成可看得见的同温层臭氧耗竭,因为分子在对流层时,其C-I键将被光解作用破坏,而无法到达同温层。
除了进行快速的光解作用外,碘代烷类进行水解的速度更快于其相关的氯代烷或溴代烷类。因此,它们迅速降解于天然水流中,以形成无害的产物,例如,碘化钾(一种普通的食用盐添加物)。就是因为能够快速的降解,含碘氟烃(对比于CFC)从来未曾牵连到长期的土壤或地表水的污染。
含碘氟烃是高度有效的燃烧抑制剂,在某些场合中,以每摩尔为基准,较halon(氟溴碳化合物)更有效。含碘氟烃不仅提供了化学性灭火作用,且借助于分子振动将热移除,也有显著的物理性灭火作用。添加足够浓度的含碘氟烃到一易燃的液体或气体中(例如是碳氢化合物)可使得材料自行熄灭。在此所描述且申请专利的本发明是特别关于液态或气态化学作用剂,其用于熄灭正在燃烧或快要燃烧的物质,包括可燃性的(combustible)、易燃性的(flammable)、及由电供能的(electrically energized)材料。
在此所描述的作用剂,在一般状况储放时具有可接受的安定性。为防止含碘氟烃光解,它们应该存放于不透光的容器内以防止遭受太阳光照射,其容器可诸如是金属圆筒或棕色玻璃瓶。如果想要长期的储存,少量的铜可以添加其中,以增加碘化物的安定性。
符合选定规范的较佳含碘氟烃列于表3。所有的含碘氟烃作用剂都具有介于-25℃至250℃的沸点,且适用于一般化学式:CaHbBrcCldFeIfNgOh,其中,a是介于并包括1和8;b是介于且包括0与2;c,d,g,及h各是介于且包括0与1;e是介于并包括1和17;f是介于且包括1与2。
用以与含碘氟烃掺合的较佳添加物列于表4。表4包含了所选择的醇类、酯类、醚类、碳氢化合物,含氢氟烃,氟代醚(fluoroethers),酮类,及全氟化碳,其沸点介于-150℃至+200℃之间。共沸掺合物是最佳的,因为它们在蒸发时不会改变组成,因此,若混合物其中有部分蒸发掉,也不会改变其特性。
        表3.较佳的含碘氟烃作用剂
        名称                                                    化学式1,1,2,2,3,3,4,4,5,5-十氟-1,5-二碘戊烷,               CF2I(CF2)3CF2I1 ,5-二碘全氟戊烷二氟二碘甲烷
                                                            CF2I21,1,2,2,3,3,4,4,5,5,6,6-十二氟-1,6-二碘己           CF2I(CF2)4CF2I烷,1,6-二碘全氟己烷1,1,1,2,3,3,3-七氟-2-碘丙烷,全氟异丙基                   CF2CFICF3碘化物1,1,2,2,3,3,3,-七氟-1-碘丙烷,          CF3CF2CF2I全氟丙基碘化物1,1,2,2,3,3,-六氟-1,3-二碘丙烷,        CF2ICF2CF2I1,3-全氟二碘丙烷1,1,2,2,3,3,4,4,4,-九氟-1-碘丁        CF3CF2CF2CF2I烷,1-碘全氟丁烷,全氟丁基碘化物1,1,2,2,3,3,4,4,-八氟-1,4-二碘丁      CF2I(CF2)2CF2I烷,1,4-二碘全氟丁烷1,1,2,2,-四氟-1,2-二碘乙烷,              CF2ICF2I1,2-二碘全氟乙烷1,1,2,2,-四氟-1-碘乙烷                     CF2ICHF21,1,2-三氟-1-碘乙烷                          CF2ICH2F十七氟-1-碘辛烷,1-碘全氟辛烷,                CF3(CF2)7I全氟辛基碘化物十五氟-1-碘庚烷,1-碘全氟庚烷,                CF3(CF2)6I全氟庚基碘化物十三氟-1-碘己烷,1-碘全氟己烷,                CF3(CF2)5I全氟己基碘化物十一氟-1-碘戊烷,1-碘全氟戊烷,                CF3(CF2)4I全氟戊基碘化物溴二氟碘甲烷                                   CBrF2I氯二氟碘甲烷                                   CClF2I碘氟氯甲烷                                     CHClFI二氟碘甲烷                                     CHF2I氟碘甲烷                                       CH2FI七氟碘环丁烷,碘全氟环丁烷                       cyclo-(CF2)3CFI五氟碘苯                                         C6F5I五氟碘环丙烷,碘全氟环丙烷,                     CF2CF2CFI全氟环丙基碘化物N-碘双-(三氟甲基)胺                              (CF3)2NI五氟碘乙烷,全氟乙基碘化物                       CF3CF2I碘三氟甲烷,三氟甲基碘化物                       CF3I(三氟甲基)·(1,1,2,2-四氟-2-碘乙              CF3OCF2CF2I基)醚
   表4.与含碘氟烃掺合的较佳添加物类别               名称                          化学式醇                 1-丁醇                        HO(CH2)3CH3
               2-丁醇                        CH3CH(OH)CH2CH3
               乙醇                          CH3CH2OH
               甲醇                          CH3OH
               2-甲基-1-丙醇                 HOCH2CH(CH3)CH3
               2-甲基-2-丙醇                 (CH3)3COH
               1-戊醇                        CH3(CH2)4OH
               2-戊醇                        CH3CHOHCH2CH2CH3
               1-丙醇                        HO(CH2)2CH3
               2-丙醇                        (CH3)2CHOH酯                 醋酸乙酯                      CH3COOCH2CH3
    丁酸乙酯                              CH3(CH2)2COOCH2CH3
    丙酸乙酯                              CH3CH2COOCH2CH3
    醋酸异丁酯                            (CH3)2CHCH2OCOCH3
    醋酸异己酯                            (CH3)2CH(CH2)3OCOCH3
    醋酸异丙酯                            CH3COOCH(CH3)2
    醋酸甲酯                              CH3COOCH3
    丁酸甲酯                              CH3(CH2)3COOCH3
    丙酸甲酯                              CH3(CH2)2COOCH3
    醋酸正丁酯                            CH3(CH2)3OCOCH3
    醋酸己酯                              CH3(CH2)5OCOCH3
    醋酸正戊酯,醋酸戊酯                  CH3(CH2)4OCOCH3
    醋酸正丙酯                            CH3(CH2)2OCOCH3
    醋酸仲丁酯                            CH3CH2CH(CH3)OCOCH3
    (二)乙醚                              (CH3CH2)2O
    (二)异丙醚                            ((CH3)2CH)2O
    (二)甲醚                              CH3OCH3
    (二)正丁醚                            (CH3(CH2)3)2O
    (二)正丙醚                            (CH3(CH2CH2))2O
    1,4-二氧杂环己烷                     环-(CH2CH2O))2
    (1,2-)环氧乙烷                       CH2OCH2
    (1,2-)环氧丙烷                       CH2OCHCH3
    四氢呋喃                              环-(CH2)4O氟代醚
    双-二氟甲基醚                         (CHF2)2O
    六氟二甲醚,全氟二甲基醚              (CF3)2O
    六氟氧环丁烷                          (CF2)3O
    甲基·三氟甲基醚                      CH3OCF3
    八氟二甲氧基甲烷                      CF3OCF2OCF3
    八氟-1,3-二氧戊环,                  CF2(OCF2CF2)2
    全氟-1,3-二氧戊环
    五氟二甲基醚                          CHF2OCF3
    1,1,2′,2′,2′-五氟甲基·乙基醚  CHF2OCH2CF3
    1-三氟甲氧基-1,1,2,2-四氟乙烷      CF3OCF2CHF2烃类
    丁烷                                  CH3(CH2)2CH3
    环丙烷                                (CH2)3
    癸烷                                  CH3(CH2)8CH3
    2,3-二甲基戊烷                       (CH3)2CHCH(CH3)CH2CH3
    2,4-二甲基戊烷                       ((CH3)2CH)2CH2
    2,2-二甲基丙烷                       (CH3)4C
    庚烷                                  CH3(CH2)5CH3
    己烷                                  CH3(CH2)4CH3
    异丁烷                                CH3CH(CH3)2
    石油英(Ligroin)                       烃类掺合物
    苎烯                                  C10H16
    2-甲基丁烷                            (CH3)2CH2CH2CH3
    3-甲基己烷                            CH3CH2CH(CH3)CH2CH2CH3
    3-甲基戊烷                            CH3CH2CH(CH3)CH2CH3
    壬烷                                  CH3(CH2)7CH3
辛烷                              CH3(CH2)6CH3
戊烷                              CH3(CH2)3CH3
石油醚                            烃类掺合物
石油精                            烃类掺合物
蒎烯                              C10H16
丙烷                              CH3CH2CH3
干洗溶剂汽油                      C8至C11碳氢化合物的掺合物
甲苯                              C6H5CH3
松节油                            烃类掺合物
十一烷                            CH3(CH2)9CH3
二甲苯                            邻,间,对-C6H4(CH3)2含氢氟烃
二氟甲烷                          CH2F2
1,1-二氟乙烷                     CHF2CH3
1,1,1,2,3,3,3,-七氟丙烷    CF3CHFCF3
五氟乙烷                          CF3CHF2
1,1,2,2,3-五氟丙烷            CHF2CF2CH2F
1,1,1,2-四氟乙烷               CF3CH2F
1,1,1,-三氟乙烷                CH3CF3
三氟甲烷                          CHF3
2-丙酮                            CH3COCH3
2-丁酮,甲基·乙基甲酮            CH3COCH2CH3
二氧化碳                          CO2
2-己酮,甲基·丁基甲酮            CH3COCH2CH2CH2CH3
3-甲基-2-丁酮                     CH3COCH(CH3)2
     2-戊酮,甲基·丙基甲酮                 CH3COCH2CH3全氟化碳
     十氟丁烷,全氟丁烷                     CF3(CF2)2CF3
     十二氟戊烷,全氟戊烷                   CF3(CF2)3CF3
     六氟环丙烷,全氟环丙烷                 (CF2)3
     六氟乙烷,全氟乙烷                     CF3CF3
     八氟环丁烷,全氟环丁烷                 (CF2)4
     八氟丙烷,全氟丙烷                     CF3CF2CF3
     十四氟己烷,全氟己烷                   CF3(CF2)4CF3
     四氟甲烷,全氟甲烷                     CF4冷冻剂
本发明揭露出一种碳氢化合物可借由添加一适当的含碘氟烃而成为更有效力的热传导液体,且达到自行熄灭的效果。此混合物是唯一的不易燃碳氢类掺合物,它们在工业及社会上有极大的用处。
在此所描述的,包括掺合物在内的所有新的冷冻剂期望能够与四种主要类别的润滑剂混溶(miscible):矿物油、烷基苯、多元醇酯(polyol esters,简称POEs)与聚亚烷基二醇(polyalkylene glycols,简称PAGs)。在作用剂里,掺合了具有较高原子量的卤原子(氯、溴或碘),由于这些原子的极化度之故,就使作用剂可与这些润滑剂混溶。含碳氢化合物的冷冻剂的另一个好处是渗漏侦测比CFC或HFC更加简化。
如表5所示,经由适当地选择纯作用剂或掺合物,可以配制出取代现存设备中CFC的投入的取代物。在此所描述的作用剂允许取代在现存设备中数以千吨计的CFC,代之而起的是环境安全,不易燃,有能源效率的冷冻剂。在新系统里,可对含有含碘氟烃的作用剂重新进行优化设计,从而获得绝佳的性能。溶剂
含碘氟烃作用剂具有希望范围内的沸点而可用作溶剂,包括,例如,1,1,2,3,3,3-七氟-1-碘丙烷,1,1,1,2,3,3,3-七氟-2-碘丙烷,氟碘甲烷,1,1,2,2-四氟-1-碘乙烷,1,1,2,2,3,3,4,4,4-九氟-1-碘丁烷,二氟二碘甲烷,十一氟-1-碘戊烷,与十三氟-1-碘己烷。添加含碘氟烃于诸如碳氢化合物,醇,酯,或酮等易燃溶剂中,可使溶剂成为不易燃的。在掺合物的情况下,为了避免含碘氟烃作用剂经由蒸发而从掺合物中损失掉,含碘氟烃成分理想上应该或是形成共沸物,或是使其沸点等于或稍大于其它的成分。发泡剂
添加适量的含碘氟烃至发泡剂里,可使所产生的泡沫变得不易燃性,且可改良其绝缘能力。气溶胶型推进剂
添加充分量的挥发性含碘氟烃后,诸如丙烷,丁烷,或异丁烷的推进剂就会变成是不易燃的。灭火剂
以含氢氟烃,全氟化碳,与氟代醚等掺合所选择的含碘氟烃,所获得的作用剂具有高效力,不耗竭臭氧,以及低毒性与低成本。在某些场合中,这些掺合的作用剂提供协同作用(Synergism,较线性预测更佳的灭火效应),这是因为含碘氟烃的化学性灭火作用与添加物的物理性灭火作用之故。蒸气压,有效性,与储存容器和运送系统的反应性,重量,成本,与毒性等皆可借由创造的掺合物而予以优化。掺合的共沸及近似共沸的含碘氟烃灭火剂可降低作用剂的成本,这是借助于它们优越的灭火能力以及较含碘氟烃成本低的含氢氟烃,全氟化碳,及氟代醚等成分。此外,它们形成固定及近似固定组成的作用剂,较非共沸掺合物具有更简便的操作方式与更可预测的效能。此掺合物始终保持它们的组合物,不会分馏成单独的成分,可保持稳定,并提供了卓越的性能。所选择的掺合物在现存的设备及运送系统中扮演着功能性的代用品,将设备所需要作的改变降至最低。工业上的适用性
本发明借助下列实施例来作进一步的说明且所举的实施例并不因此而限制申请专利范围。冷冻剂
表5显示了投入现存设备中,用以替代的冷冻作用剂(包括掺合物)的较佳实施例。
   表5:较佳的取代用冷冻剂的实施例冷冻剂       沸点       化学品               大致的比例
         (℃)                            (以摩尔计)11           23.8     C2F5I/正-C3F7I    50∶50
                  正-C3F7I/丁烷/戊烷    5∶40∶55(三元共沸
                                          物)
                  C2F5I/戊烷            50∶50
                  C2F5I/二乙醚         50∶50
                  正-C2F7I/丁烷        60∶4012           -29.8    CF3I                   纯
                  CF3I/丙烷              60∶40
                  CF3I/CF3CF2CF3     50∶50
                  CF3I/CF3CF2CF3     10∶90(二元共沸物)
                  CF3I/CHF2CH3        8∶92(二元共沸物)
                  CF3I/环丁烷            10∶90(二元共沸物)
              CF3I/CF3CF2CF3/       32∶22∶46(三元共沸
              CHF2CF3                  物)
              CF3I/氟乙烷               55∶45
              CF3I/环丙烷               30∶7022    -40.8       CF3I/丙烷                 5∶95或10∶90
              CF3I/(CF3)2O           50∶50
              CF3I/CHF2OCF3          5∶95
              CF3I/二氟甲烷             40∶60
              CF3I/五氟乙烷             30∶70
              CF3I/1,1,1-三氟乙       30∶70
              烷
              CF3I/全氟丙烷             30∶70500   -33.5       CF3I/丙烷                 45∶55
              CF3I/(CF3)2O           75∶25
              CF3I/五氟乙烷             60∶40
              CF3I/全氟乙烷             60∶40
              CF3I/1,1,1-三氟乙       60∶40
              烷
              CF3I/二氟甲烷             70∶30
              CF3I/氟乙烷               30∶70
              CF3I/全氟丙烷             20∶80502   -45.4       CF3I/二氟甲烷             20∶80
              CF3I/(CF3)2O           40∶60
              CF3I/三氟甲烷             60∶40
              CF3I/五氟乙烷             10∶90
        CF3I/1,1,1-三氟乙                   10∶90
        烷
        CF3I/全氟乙烷                         10∶90溶剂
下列所示的较佳纯作用剂或掺合物符合溶剂所应具备的要求和不易燃性,低毒性及环境冲击性,它们包括:纯的1,1,2,2,3,3,4,4,4-九氟-1-碘丁烷;纯的十一氟-1-碘戊烷;纯的十三氟-1-碘己烷;2至15%(以摩尔计)的1,1,2,2-四氟-1-碘乙烷,掺合98至85%的己烷;2至15%(以摩尔计)的1,1,2,2,3,3,3-七氟-1-碘丙烷,掺合98至85%的戊烷;2至15%(以摩尔计)的1,1,2,2,3,3,4,4,4-九氟-1-碘丁烷,掺合98至85%的己烷;2至15%(以摩尔计)的十三氟-1-碘己烷,加上98至85%的辛烷、壬烷、与/或癸烷;2至15%(以摩尔计)的1,1,2,2,3,3,4,4,4-九氟-1-碘丁烷,掺合98至85%的下列其中的一种或多种化学品;甲醇、乙醇、2-丁酮、2-丙醇、丙酮、醋酸甲酯、醋酸乙酯、四氢呋喃以及己烷,与2至15%(以摩尔计)的十一氟-1-碘戊烷掺合98至85%的下列其中至少一种化学品:庚烷、乙醇、2-丙醇及2-丁酮。发泡剂
下列所示的较佳纯作用剂及掺合物符合发泡剂所应具备的要求,它们包括:纯的二氟碘甲烷;纯的碘全氟乙烷;纯的1,1,2,3,3,3-七氟-1-碘丙烷;2至15%(以摩尔计)的五氟碘乙烷,掺合98至85%的丁烷;2至15%(以摩尔计)的二氟碘甲烷,掺合98至85%的丁烷;2至15%(以摩尔计)的1,1,2,3,3,3-七氟-1-碘丙烷,掺合98至85%的戊烷;2至15%(以摩尔计)的五氟碘乙烷,掺合98至85%的戊烷;2至15%(以摩尔计)的三氟碘甲烷,掺合98至85%的1,1-二氟乙烷;2至15%(以摩尔计)的三氟碘甲烷,掺合98至85%的丁烷;以及上列中任何一种作用剂加入上至40重量%的水。气溶胶型推进剂
下列具有不易燃性的较佳掺合物符合气溶胶型推进剂的要求,包括:2至15%(以摩尔计)的三氟碘甲烷,掺合98至85%的下列其中一种或多种化学品:丙烷、丁烷、异丁烷、二氧化碳。减火剂
下列较佳的掺合物及纯的含碘氟烃作用剂符合有效的,干净的灭火剂的要求,它们包括:CF3I与下列其中至少一种化学品组成的掺合物:三氟甲烷、二氟甲烷、五氟乙烷,与1,1,1,2-四氟乙烷;CF3CF2CF2I与下列其中至少一种化学品组成的掺合物:
CF3CF2I,CH2FI,全氟戊烷,及全氟己烷;
CF3CF2CF2CF2I与全氟己烷的掺合物;以及,纯的氯氟碘甲烷。
下列实施例显示所列的作用剂的有效性,它们是对环境安全且不易燃的冷冻剂、溶剂、发泡剂、推进剂、及灭火剂。实施例1
从一家用冰箱内移除所填充的CFC-12(大约6至8盎司),且收集起来予以回收,再制,或破坏,以不至于影响环境为原则。然后,冰箱在一封闭系统内自一压力瓶填充等量的共沸掺合物,它含有10%(以摩尔计)的CF3I,与90%的环丁烷。利用此方法,同温臭氧层可以获得确保,且符合国际间及各国家内的环境法规,而不影响冰箱原有的性能,无需新设备,抑或使服务技师或屋主承受易燃性或毒性的危险。额外的好处是如果填充物不慎溢出,它不会造成易燃,毒性,或臭氧枯竭的危险。它安定性,低反应性,及高材料相容性使得它能够储存及使用许多年。若有CFC-12残留在系统内,填充新的化学品并不会产生不利的反应。实施例2
将一商用的大冰箱内的CFC-12排出,并予以收集,回收,再制,或破坏,以不影响环境为原则。然后,再填充一种掺合物,它包含10%(以摩尔计)三氟碘甲烷,20%的全氟二甲基醚和70%的丁烷,它的性能几乎相同于CFC-12,同样的矿物油润滑剂亦可使用,不需要因材料的不相容性而更换任何材料(例如,垫圈,O型环,配管等)。实施例3
将一200吨重的离心式冷却机(centrifugal chiller)内的CFC-11(大约700磅)排出,并填充等量的一种掺合物,此掺合物是正-C3F7I/丁烷/戊烷(5∶40∶55,以摩尔计)。冷却机重新启动后保持原操作性能,而不会造成冷冻容量的损失或耗电量的增加,且不需要将马达及密封装置改型。实施例4
将一蒸汽去油机内的CFC-113,或1,1,1-三氯乙烷排出,并将此化学品予以回收、再制、或破坏。然后,再填充1,1,2,2,3,3,4,4,4-九氟-1-碘丁烷,且保持在回流状态。取一具有通孔(through-hole)及表面安装零件的印刷电路板,此印刷电路板在制作过程中受到助焊剂残余物及其它油类及蜡的污染,将此板通过蒸汽去油机之后,是完全干净的,没有造成同温层臭氧破坏,也没有易燃性及毒性的危险。实施例5
类似于实施例4,只是将置于蒸汽去油机内的取代用作用剂变成95%(以摩尔计)辛烷,掺合5%的十三氟-1-碘己烷。实施例6
在制造设备中用以将金属部份去油的溶剂(CFC-113,1,1,1-三氯乙烷,与干洗溶剂汽油)予以移除,并回收,再制,或破坏之,以不影响环境为原则。在制造过程中,一金属零件,其表面污染于350厘沲(centistoke)的切削油,以及250,000厘沲的硅润滑脂。在一通风橱内,利用注射瓶(squirt bottle),将此零件浸用1,1,2,2,3,3,4,4,4-九氟-1-碘丁烷液冲洗。之后,以干净的布擦拭,并于空气中干燥。在15分钟内,它是干的,且其表面是干净的,可以用于下一步制作。此清洁方法不会耗竭同温层臭氧或造成技术人员处于易燃或毒性的危险环境中,亦不需花费大笔投资于工程管制。实施例7
将一受到MIL-H-5606液压流体污染的陀螺仪,置于装满十三氟-1-碘己烷的超声波洗净机内。一平吸式局部排气装置(crossdraftlocal exhaust)移除任何逸出的蒸气,且洗净槽处于2瓦特/cm2的超声波能量下5分钟。取出陀螺仪,将液体排出后以热风干燥。所产生的非常干净的陀螺仪经小心的包装后,送至下一步的制造或安装。实施例8
将一干式清净机内所使用的全氯乙烯予以清除,且在不影响环境的原则下予以回收或破坏。这些溶剂以一种掺合物取代之,此掺合物含有5%(以摩尔计)的CF3(CF2)5I,与95%的石油馏出物(主要为庚烷及辛烷所组成)。新的溶剂比被取代的溶剂较有较及不易燃,且更不具毒性。再者,它较不会造成环境危险,因为地下水将不会被长寿命的全氟乙烯所污染。实施例9
调配一醇酸树脂瓷漆(alkyd enamel paint),其组成(取代纯的矿油精)为一95%的矿油精及5%的1-全氟碘己烷的掺合物。添加含碘氟烃可使得其配方在使用时不具易燃性且较安全。实施例10
调配一粘结剂,其组成(取代1,1,1-三氯乙烷)为-95%(以摩尔计)的甲苯与5%的1-碘全氟己烷的掺合物。经由此配方的改变,粘结剂可以较不具易燃性,且对环境伤害较轻微。实施例11
一聚氨基甲酸乙酯泡沫塑料,所使用的发泡剂为一5摩尔%的五氟碘乙烷,掺合95%的戊烷的混合物。相反于使用CFC-11作发泡剂,使用此种发泡剂的发泡体在制造过程中,没有释放出任何蒸气而造成臭氧的消耗。此外,因为氟碘代烷的添加,使得发泡体较不易燃。最后,在发泡体使用期限届满而须抛弃时,不会对同温层臭氧造成危险。实施例12
将一发胶喷雾罐予以加压灌入一4%(以摩尔计)的CF3I及96%的丁烷与/或异丁烷的混合物。没有易燃性的危险存在,即使喷务罐不慎溢出于一开放的火焰中,也不会点火燃烧。且溢出的成份不会对同温层臭氧造成危险。实施例13
一家用杀虫剂喷雾罐用4%CF3I和96%二氧化碳加压充灌。由于使用了含碘氟烃掺合物,消除了易燃的危险。实施例14
一由5%(以摩尔计)的CF3I,12%的环氧乙烯,及83%的氮气所组成的气体混合物使用于消毒绷带,纱布,及医疗设备。因为添加了CF3I当作补充的推进剂,在制备中,可能产生的燃烧或爆炸的危险可予以根绝。实施例15
将电脑房防火系统内的Halon 1301清除,并予以回收或破坏。在原处填充一由60%(以摩尔计)的CF3I及40%的CF3CH2F所组成的气体混合物,且只须将系统做稍微的修改(例如更改垫圈、O型环、及喷嘴)。当火灾事故发生时,此种新的作用剂迅速分散,且熄灭火焰,而不会对人体或机器设备造成伤害。灭火剂的溢出不会造成臭氧的耗竭。实施例16
将一机场使用的150磅重的轮式保养工作区灭火器内所填充的Halon 1211予以清除,并予以回收或破坏。在原处置入一由70%(以摩尔计)的1,1,2,2,3,3,3-七氟-1-碘丙烷及30%的全氟己烷所组成的混合物,且只须将灭火器稍作修改(例如更改垫圈、O型环、及喷嘴等部份)。当火灾事故发生时,将液态的作用剂的液流以人工对准火焰的基部,即可迅速灭火,而不伤人体或设备。灭火剂的溢出不会造成臭氧的耗竭。实施例17
一装置于车辆发动机罩下的罐子,内含有大致1磅重的CF3I,并配置一铅制的塞子。当遇到燃烧时,铅塞熔化后灭火器被启动,灭火剂即可自动喷出以熄灭火焰,而得以保护车辆本身,及其零组件,以及驾驶员。
上述各实施例可经由替代以本发明一般或具体描述过的反应物,与/或操作条件,而重复得到相似的成功结果。
虽然本发明已经参照这些较佳具体实施例作了详细的解说,但其它的具体实施例可以得到相同的结果。对于熟知此技艺者而言,有关本发明的任何变化及改良将是非常明显的;在后附的权利要求内尽可能覆盖所有有关于此的改良方法与其等价的方法。所有上述引用的参考文献,应用的用途,专利文献,及出版物等,其所揭露的全部内容一并纳入参考。

Claims (37)

1.一种组合物,包括以下物质的掺合物:
2至75摩尔%至少一种含碘氟烃,所述含碘氟烃是选自下列族群,其中包括有:溴二氟碘甲烷,氯二氟碘甲烷,1,1,2,2,3,3,4,4,5,5-十氟-1,5-二碘戊烷、二氟二碘甲烷、二氟碘甲烷、1,1,2,2,3,3,4,4,5,5,6,6-十二氟-1,6-二碘己烷、氟碘甲烷、1,1,1,2,3,3,3-七氟-2-碘丙烷、1,1,2,2,3,3,3-七氟-1-碘丙烷、1,1,2,2,3,3-六氟-1,3-二碘丙烷、1-碘十七氟辛烷、七氟碘环丁烷、1-碘十五氟庚烷、五氟碘环丙烷、1-碘十三氟己烷、1-碘十一氟戊烷、N-碘双-(三氟甲基)胺、1,1,2,2,3,3,4,4,4-九氟-1-碘丁烷、1,1,2,2,3,3,4,4-八氟-1,4-二碘丁烷、碘五氟乙烷、1,1,2,2-四氟-1,2-二碘乙烷、1,1,2,2-四氟-1-碘乙烷、1,1,2-三氟-1-碘乙烷和三氟碘甲烷,
25至98摩尔%至少一种选自下列物质的添加物:(1)醇类,选自1-丁醇、2-丁醇、乙醇、甲醇、2-甲基-1-丙醇、2-甲基-2-丙醇、1-戊醇、2-戊醇、1-丙醇以及2-丙醇,(2)酯类,(3)醚类,(4)碳氢化合物类,选自丁烷、环丙烷、癸烷、2,3-二甲基戊烷、2,4-二甲基戊烷、2,2-二甲基丙烷、庚烷、异丁烷、苎烯、2-甲基丁烷、3-甲基己烷、3-甲基戊烷、矿油精、壬烷、辛烷、戊烷、蒎烯、丙烷、干洗溶剂汽油、松节油以及十一烷,(5)含氢氟烃类,选自二氟甲烷、1,1-二氟乙烷、1,1,1,2,3,3,3-七氟丙烷、五氟乙烷、1,1,2,2,3-五氟丙烷、1,1,1,2-四氟乙烷和1,1,1-三氟乙烷,(6)酮类,以及(7)全氟化碳类,选自十氟丁烷、十二氟戊烷、六氟环丙烷、六氟乙烷、八氟环丁烷、八氟丙烷和十四氟己烷。
2.如权利要求1所述的组合物,其中所述添加物包括酯类,选自下列族群,其中包括有:醋酸乙酯、丁酸乙酯、丙酸乙酯、醋酸正丁酯、醋酸正戊酯、醋酸己酯、醋酸异丁酯、醋酸异丙酯、醋酸甲酯、丁酸甲酯、丙酸甲酯、醋酸正丙酯、以及醋酸仲丁酯。
3.如权利要求1所述的组合物,其中所述添加物包括醚类,选自下列族群,其中包括:(二)乙醚、(二)异丙醚、(二)甲醚、(二)正丁醚、(二)正丙醚、1,4-二氧杂环己烷、环氧乙烷、环氧丙烷以及四氢呋喃。
4.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3I,且添加物包括下列族群的至少其中一种成份,其中包括有:二氟甲烷、五氟乙烷、1,1,1-三氟乙烷、丙烷、1,1-二氟乙烷、1,1,1,2-四氟乙烷、丁烷以及五氟碘乙烷。
5.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3I,且添加物包括下列族群中至少一种成分,其中包括有:丁烷与异丁烷。
6.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3CF2CF2I,且添加物包括下列族群的至少其中一种成分,其包括:丁烷、乙醚以及戊烷。
7.如权利要求1所述的组合物,其中含碘氟烃包括CF3CF2CF2CF2I,且添加物包括下列族群的至少其中一种成份,其中包括有:丙酮、醋酸甲酯和四氢呋喃。
8.如权利要求1所述的组合物,其中含碘氟烃包括CF3CF2CF2CF2I,且添加物包括下列族群的至少其中一种成分,其中包括有:乙醇、丁酮、2-丙醇和醋酸乙酯。
9.如权利要求1所述的组合物,其中含碘氟烃包括CF3CF2CF2CF2CF2CF2I,且添加物包括下列族群的至少其中一种成分,其中包括有:庚烷和矿油精。
10.如权利要求1所述的组合物,其中含碘氟烃包括CF3CF2CF2CF2CF2CF2CF2I,且添加物包括下列族群的至少其中一种成分,其中包括有:壬烷、辛烷以及干洗溶剂汽油。
11.如权利要求1所述的组合物,其中含碘氟烃包括:CF3CF2CF2CF2CF2CF2CF2CF2I,且添加物包括下列族群的至少其中一种成分,其中包括有:癸烷、醋酸己酯、苎烯、矿油精、蒎烯、干洗溶剂汽油、松节油以及十一烷。
12.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3CF2I,且添加物包括丁烷或异丁烷。
13.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3CF2CF2I,且添加物包括丁烷。
14.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3CF2CF2I,且添加物包括乙醚。
15.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3CF2CF2I,且添加物包括戊烷。
16.如权利要求1所述的组合物,其中所述含碘氟烃的含量为20至60摩尔%。
17.如权利要求1所述的组合物,其中所述含碘氟烃的含量为30至75摩尔%。
18.如权利要求1所述的组合物,其中所述含碘氟烃的用量至少为30摩尔%。
19.如权利要求1所述的组合物,其中所述含碘氟烃为CF3I。
20.如权利要求1所述的组合物,其中所述含碘氟烃为CF3(CF2)2I、CF3(CF2)3I、CF3(CF2)4I或CF3(CF2)5I。
21.如权利要求1所述的组合物,其中所述添加物包括选自丙酮、2-丁酮和3-甲基-2-丁酮的酮类。
22.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3(CF2)3I,且添加物包括甲醇。
23.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3(CF2)3I,且添加物包括己烷。
24.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3(CF2)4I,且添加物包括乙醇。
25.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3(CF2)4I,且添加物包括丁酮。
26.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3(CF2)4I,且添加物包括2-丙醇。
27.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3(CF2)4I,且添加物包括醋酸乙酯。
28.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3(CF2)4I,且添加物包括醋酸异丙酯。
29.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3(CF2)4I,且添加物包括庚烷。
30.如权利要求1所述的组合物,其中所述添加物包括戊烷,所述含碘氟烃包括CF3I、CF3CF2I或CF3CF2CF2I。
31.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3I,且添加物包括全氟丁烷。
32.如权利要求1所述的组合物,其中所述含碘氟烃包括CF3CF2CF2I,且添加物包括全氟己烷。
33.含有如权利要求1至32中任何一项所述的组合物的冷冻剂,其中所述添加物选自醇类、醚类、碳氢化合物类、含氢氟烃类和全氟化碳类。
34.含有如权利要求1至32中任何一项所述的组合物的溶剂,
         所述含碘氟烃选自氟碘甲烷、二氟碘甲烷、二氟二碘甲烷、溴二氟碘甲烷和氯二氟碘甲烷。
35.含有如权利要求1至32中任何一项所述的组合物的发泡剂,其中所述添加物选自醚类、碳氢化合物类、含氢氟烃类、酮类和全氟化碳类。
36.含有如权利要求1至32中任何一项所述的组合物的气溶胶推进剂,其中所述添加物选自醚类、碳氢化合物类、含氢氟烃类和全氟化碳类。
37.含有如权利要求1至32中任何一项所述的组合物的灭火剂,其中所述添加物选自二氟甲烷、1,1-二氟乙烷、1,1,1,2,3,3,3-七氟丙烷、五氟乙烷、1,1,2,2,3-五氟丙烷、1,1,1,2-四氟乙烷、1,1,2,2-四氟乙烷、1,1,1-三氟乙烷、1,1,2-三氟乙烷、十氟丁烷、十二氟戊烷、六氟环丙烷、六氟乙烷、八氟环丁烷、八氟丙烷和十四氟己烷。
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US5444102A (en) 1995-08-22
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US5685915A (en) 1997-11-11
US5611210A (en) 1997-03-18
US7083742B1 (en) 2006-08-01
US5605647A (en) 1997-02-25
ATE193903T1 (de) 2000-06-15
US5562861A (en) 1996-10-08
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US5695688A (en) 1997-12-09
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