CN1082088A - 氟代醚和氟代烃组合物 - Google Patents
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Abstract
本发明涉及包括至少一种氟代醚和至少一个氟
代烃的组合物。本发明包括式CaFbH2a+2-bOc的环
或无环氟代烃的组合物,式中a=2或3并且3≤b≤
8和c=1或2以及1≤n≤4和1≤m≤8。这样的组
合物可以用作制冷剂、清洁剂、聚烯烃和聚氨基甲酸
乙酯的膨胀剂、气雾剂推进剂、热交换介质、气体电介
质、灭火剂、动力循环工作流体、聚合介质、颗粒除去
流体,载流体、磨光磨蚀剂和置换干燥剂。
Description
本发明涉及包括至少一种氟代醚和至少一种氟代烃(hydrofluorocarbon)的组合物。这样的组合物可以用作制冷剂、清洁剂、聚烯烃和聚氨基甲酸乙酯的膨胀剂气雾剂推进剂、热交换介质、气体电介质、灭火剂、动力循环工作流体、聚合介质、颗粒除去流体、载流体、磨光磨蚀剂、置换干燥剂以及止繁殖剂气体的载体。
本发明包括组合物,该组合物包括氟代醚和氟代烃,其中氟代烃的囟化碳全球变暖能力(halocarbon global warmming potential(HGWP)]由将氟代醚加到氟代烃中所降低。本发明也包括共沸或类共沸物的氟代醚和氟代烃的组合物。
氟化烃有许多用途,其一是作为制冷剂。这样的制冷剂包括二氯二氟甲烷(CFC-12)和氯二氟甲烷(HCFC-22)。
近年来人们认为某些含氯氟烃(CFC)和氯氟代烃(hydrochlorofluorocarbon)(HCFC)制冷剂释放到大气中会对臭氧层产生不利的影响。尽管这个提议尚未得到完全证实,但在国际协定下正朝着控制使用和生产某些CFC和HCFC的方向发展。
为解决潜在的臭氧耗褐问题,有人提议用氟代烃制冷剂代替含氯氟烃制冷剂和氯氟代烃制冷剂。由于氟代烃(HFC)制冷剂不含氯,因此它们不消耗臭氧。
另一个环境关心的问题是CFC在“温室效应”中的作用。温室效应是指当大气相对地可为可见光所透射并可使阳光直达地球时,大气通过吸收地球释放的红外辐射而捕集到热量使地球的气候变暖。
目前尚未有可以将所有相关的因素都结合到单一的关于诸如CFC气体的发射物的全球变暖能力的普遍可接受的方法。一个方法是相对于已知的标准根据增强全球变暖的能力来定义化合物的温室效应。一个这样的定义被认为是囟化碳全球变暖能力(HGWP),这是一个比率,其为气体的发射物在该气体在大气中的生存期间所产生的增长的辐射变暖与由相同质量的对照气体CFC-11释放的计算出来的变暖之比。
尽管HFC的臭氧消耗能力为零,但某些HFC有可能是具不合需要的HGWP,并受到政府的控制。因此有必要开发出具低的臭氧消耗能力而同时有低HGWP的制冷剂。
优选的包括一种以上成分的制冷剂为共沸或类共沸物,这使得制冷剂从制冷设备中泄漏或排放到大气中时其组成不会发生改变。制冷剂组成的改变会影响它的性质,例如性能或可燃性。
使用组合物也是合乎需要的,所述组合物具低的臭氧消耗能力和/或低HGWP和/或为共沸或类共沸物;可用作清洁剂,生产闭孔聚氨基甲酸乙酯、酚醛泡沫体和热塑泡沫体中的发泡剂,气雾剂中的推进剂,热交换介质,气体电介质,灭火剂,如用于加热泵的动力循环工作流体,聚合反应的惰性介质,用于从金属表面除去颗粒的流体,例如可被用来在金属部件上形成细的润滑剂膜的载流体,或从诸如金属表面去除磨光磨蚀化合物的磨光磨蚀剂,例如用来从宝石或金属部件中除去水的置换干燥剂,在常规循环制造技术中的抗显影剂包括氯型显影剂以及当与例如氯代烃像1,1,1-三氯乙烷或三氯乙烯一同使用时可用作抗光蚀剂的剥离剂。
本发明涉及包括氟代醚和氟代烃的组合物。本发明包括式CaFbH a+2-bOc的环或无环氟代醚以及式CnFmH2n+2-m的环或无环氟代烃的组合物;式中a=2或3并且3≤b≤8和c=1或2以及1≤n≤4和1≤m≤8。这样的组合物可以用作制冷剂、清洁剂、聚烯烃和聚氨基甲酸乙酯的膨胀剂、气雾剂推进剂、热交换介质、气体电介质、灭火剂、动力循环工作流体、聚合介质、颗粒除去流体、载流体、磨光磨蚀剂和置换干燥剂。
本发明的另一方面涉及将HGWP低于氟代烃的氟代醚加到氟代烃中可降低氟代烃的HGWP这一发现。因此,本发明涉及第一成分和第二成分的组合物;所述第一成分包括氟代烃;所述第二成分包括氟代醚,其HGWP小于第一成分的HGWP;这样组合物的HGWP小于第一成分的HGWP。
本发明也包括共沸或类共沸物的包括氟代醚和氟代烃的组合物。
本发明涉及包括氟代醚和氟代烃的组合物。本发明包括式CaFbH a+2-bOc的环或无环氟代醚以及式CnFmH2n+2-m的环或无环氟代烃的组合物;式中a=2或3并且3≤b≤8和c=1或2以及1≤n≤4和1≤m≤8。这样的组合物可以用作制冷剂、清洁剂、聚烯烃和聚氨基甲酸乙酯的膨胀剂、气雾剂推进剂、热交换介质、气体电介质、灭火剂、动力循环工作流体、聚合介质、颗粒除去流体、载流体、磨光磨蚀剂和置换干燥剂。
包括在本发明中的氟代醚有2或3个碳原子。这样的氟代醚的例子包括下面的化合物:
1.六氟二甲基醚(116E,或CF3OCF3,沸点=-59.0℃),
2.五氟二甲基醚(125E,或CHF2OCF3,沸点=-36.2℃),
3.二(二氟甲基)醚(134E,或CHF2OCHF2,沸点=5℃),
4.氟甲基三氟甲基醚(134aE,或CH2FOCF3,沸点=-20.0℃),
5.三氟甲基甲基醚(143aE,或CH3OCF3,沸点=-24.2℃),
6.全氟氧杂环丁烷(C-216E,或
沸点=-29.2℃),
7.2,2,4,4,5,5-六氟-1,3-二氧戊环(C-216E2,或C3F6O2,结构为:
沸点=-22.1℃)
8.全氟甲基乙基醚(218E,或CF3OCF2CF3,沸点=-23.3℃),
9.全氟二甲氧基甲烷(218E2,或CF3OCF2OCF3,沸点=-10.2℃),
10.2,2,3,4,4-五氟氧杂环丁烷(C-225eEαβ,或C3HF5O,结构为:
沸点=3.4℃),
11.1-三氟甲氧基-1,1,2,2-四氟乙烷(227caEαβ,或CF3OCF2CHF2,沸点=约-3℃),
12.二氟甲氧基五氟乙烷(227caEβγ,或CHF2OCF2CF3,沸点=-8.0℃),
13.1-三氟甲氧基-1,2,2,2-四氟乙烷(227eaE,或CF3OCHFCF3,沸点=-9.4℃),
14.2,2,4,4-四氟氧杂环丁烷(C-234f Eαβ,或C3H2F4O,结构为:
沸点=21.2℃),
15.2,2,3,3-四氟氧杂环丁烷(C-234fEβγ,或C3H2F4O,结构为:
沸点=28℃),
16.1-二氟甲氧基-1,1,2,2-四氟乙烷(236caE,或CHF2OCF2CHF2,沸点=28.5℃),
17.1-二氟甲氧基-1,2,2,2-四氟乙烷(236eaEβγ,或CHF2OCHFCF3,沸点=23.2℃),
18.1-三氟甲氧基-2,2,2-三氟乙烷(236faE,或CF3OCH2CF3,沸点=5.6℃),
19.1-二氟甲氧基-2,2,2-三氟乙烷(245faEβγ,或CHF2OCH2CF3,沸点=29℃)。
116E(CAS登记号1479-49-8)已按Simons在美国专利2519983中公开的方法由二甲醚的电化氟化来制备。
125E(CAS登记号3822-68-2)已按Fox等人在美国专利3511760和Hutchinson在美国专利3887439中公开的方法由二甲醚(CH3OCH3)的电化氟化制得。
134E(CAS登记号1691-17-4)可按O′Neill在英车专利2248617中公开的方法通过三氟化锑与CHF2OCHCl2反应来制备。
134aE(CAS登记号2261-01-0)已按Berenblit等人在Zh.Org.Khim.12卷,676-770页(1976)中报道的方法由2-甲氧基丙酸甲酯的电化氟化制得。
143aE(CAS登记号421-14-7)已按Aldrick和Sheppard在J.Am.Chem.Soc.,29卷,11-15页(1964)中报道的方法通过氟甲酸甲酯与四氟化硫反应制得。
C-216E(CAS登记号425-82-1)可按Kauck和Simons在美国专利2594272中公开的方法由氧杂环丁烷在无水氟化氢中的电化氟化制得。
C-216E2(CAS登记号21297-65-4)已按Throckmorton在J.Org.Chem.,第34卷,3838-3440页(1969)中报道的方法通过在汽相或液相中用UV照射全氟-b-氧杂-戊内酯制得。该内酯由KF与全氟氧联二乙酰氯(Perfluorooxydiacetyl chloride)反应制得。
218E(CAS登记号665-16-7)已按Sekiya和Ueda在Chemistry Letters,第609-612页(1990)中报道的方法由CF OCH CF(由CF OF与1,1-二氟乙烯反应制得)的直接氟化制得。
218E2(CAS登记号53772-78-4)已按Berenblit等人在Zh.Org.Klim.,12卷,767-770页(1976)中报道的方法由2-甲氧基丙酸甲酯的电化氟化制得。
C-225eEαβ(CAS登记号144109-03-5)可用Lagow和Margrave在Progress in Inorganic Chemistry,26卷,161-210页(1979)或Adcock和cherry在Ind.Eng.Chem.Res.,26卷,208-215页(1987)中所述技术由氧杂环丁烷(环-CH2CH2CH2O-)的直接氟化制得。该直接氟化进行到氟结合进原料达到所需的程度,产物通过分馏回收。
227caEαβ(CAS登记号2356-61-8)已按Eisemann在美国专利3362190中公开的方法通过二氟乙酰氟与氟化铯和碳酰氟反应并随后用四氟化硫处理制得。
227caEβγ(CAS登记号53997-64-1)已按Okazaki等人在J.Fluorine Chem.,4卷,387-397页(1974)中报道的方法由CHCl2OCF2CHClF的电化氟化制得。
227eaE(CAS登记号2356-62-9)已按Eisemann在美国专利3362190中公开的方法由2-三氟甲氧基-四氟丙酰氟(CF3CF(OCF3)COF)与含水氢氧化钾于230℃反应制得。
C-234fEαβ可以按Lagow和Margrave在Progress in Inorganic Chemistry,26卷,161-210页(1979)或Adcock和Cherry在Ind.Eng.Chem.Res.,26卷,208-215页(1987)中所述技术由氧杂环丁烷(环-CH2CH2CH2O-)的直接氟化制得。该直接氟化进行到氟结合进原料达到所需的程度,产物通过分馏回收。
C-234fEβγ(CAS登记号765-63-9)已由Weinmayr(J.Org.Chem.,28卷,492-494页(1963))作为TFE与甲醛在HF中反应的付产物被制得。
236caE(CAS登记号32778-11-3)已按Terrell等人在J.Medicnal Chem.,15卷,604-606页(1972)中报道的方法通过用无水氟化氢与五氯化锑催化剂氟化CHCl2OCF2CHF2(由CH3OCF2CHF2的再氯化制得)制得。
236eaEβγ(CAS登记号57041-67-5)已按Halpern和Robin在美国专利4888139中公开的方法制得,该方法为:氯化甲氧基乙酰氯得到中间产物-CHCl2OCHCl.COCl,将其分离并与四氟化硫于150℃反应得到产物。
236faE(CAS登记号20193-67-3)已按Eisemann在美国专利3394878中公开的方法制得,所述方法为:2,2,2-三氟乙醇与碳酰氟反应得到中间体CF3CH2OCOF,该中间体再与四氟化硫于150-200℃反应制得产物。
245faEβγ(CAS登记号1885-48-9)已按Croix在美国专利第3637477中公开的方法通过氯二氟甲烷与三氟乙醇在氢氧化钾存在下反应制得。
可与氟代醚混合的HFC包括一种或多种下列HFC:二氟甲烷(HFC-32),氟甲烷(HFC-41),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),1,1,2-三氟乙烷(HFC-143),1,1,1-三氟乙烷(HFC-143a),1,1-二氟乙烷(HFC-152a),氟乙烷(HFC-161),1,1,1,2,2,3,3-七氟丙烷(HFC-227ca),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),1,1,2,2,3,3-六氟丙烷(HFC-236ca),1,1,1,2,2,3-六氟丙烷(HFC-236cb),1,1,2,2,3-五氟丙烷(HFC-245ca),1,1,1,2,2-五氟丙烷(HFC-245cb),1,1,2,3,3-五氟丙烷(HFC-245ea),1,1,1,3,3-五氟丙烷(HFC-245fa),1,2,2,3-四氟丙烷(HFC-254ca),1,1,2,2-四氟丙烷(HFC-254cb),1,1,1,2-四氟丙烷(HFC-254cb),1,2,2-三氟丙烷(HFC-263ca),1,1,1-三氟丙烷(HFC-263fb),2,2-二氟丙烷(HFC-272ca),1,2-二氟丙烷(HFC-272ea),1,1-二氟丙烷(HFC-272fb),2-氟丙烷(HFC-281ea),1-氟丙烷(HFC-281fa),1,1,1,3,3,4,4,4-八氟丁烷(HFC-338mf),1,1,1,4,4,4-六氟丁烷(HFC-356mff),或(CF3)2CHCH3,(HFC-356mmz)。
下面的化合物可以用作制冷剂:式CaFbH2a+2-bOc的环或无环氟代醚和式CnFmH2n+2-m的氟代烃的组合物;式中a=2或3并且3≤b≤8和c=1或2,1≤n≤4并且1≤m≤8。这样的组合物的例子包括以下组合物:
1-99重量百分数mt116E和1-99重量百分数ntHFC-32,HFC-41,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236ea,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数125E和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea或HFC-281fa.
1-99重量百分数134E和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236ea,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,HFC-281fa,HFC-338mf或356mff.
1-99重量百分数134aE和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数143aE和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数C216E,和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数C-216E2和1-99重量百分数HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161或HFC-245cb.
1-99重量百分数218E和1-99重量百分数HFC-32,HFC-125,
HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数218E2和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fa,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数C-225eEαβ和1-99重量百分数HFC-143,HFC-236cb,HFC-236ea,or HFC-245cb.
1-99重量百分数227caEαβ和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数227caEβγ和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数-227eaE和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数tC-234fEαβ和1-99w重量百分数HFC-245cb,HFC-245eb,HFC-356mff或HFC-356mmz.
1-99w重量百分数C-234fEβγ和1-99重量百分数ntHFC-245ca,HFC-245cb,HFC-245ea,HFC-254ca,HFC-356mff或HFC-356mmz.
1-99重量百分数236caE和1-99重量百分数tHFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数t236eaEβγ和1-99重量百分数tHFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,
HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,HFC-281fa,HFC-338mf,HFC-356mff或HFC-356mmz.
1-99重量百分数t236faE和1-99重量百分数HFC-32,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,或HFC-281fa.
1-99重量百分数245faEβγand1-99重量百分数HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a,HFC-161,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236fa,HFC-245ca,HFC-245cb,HFC-245ea,HFC-245fa,HFC-254ca,HFC-254cb,HFC-254eb,HFC-263ca,HFC-263fb,HFC-272ca,HFC-272ea,HFC-272fb,HFC-281ea,HFC-281fa,或HFC-356mff.
本发明也涉及共沸或类共沸物组合物这一发现,该组合物为在特定温度或压力下有效量的下列化合物生成的共沸或类共沸物组合物:
116E和HFC-32,HFC-41,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a或HFC-161;125E和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a或HFC-161;134E和HFC-143,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236ea,HFC-236fa,HFC-245cb,HFC-254cb,HFC-254eb,HFC-338mf,或HFC-356mff;134aE和HFC-32,HFC-134,HFC-143,HFC-152a,HFC-227ca,HFC-227ea或HFC-245cb;143aE和HFC-32,HFC-134,HFC-143a,HFC-152a,HFC-227ca,HFC-227ea或HFC-245cb;C216E和HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161或HFC-245cb;C216E2和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161或HFC-245cb;218E和HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161或HFC-263fb;218E2和HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161,HFC-236fa或HFC-263fb;
C-225eEαβ和HFC-143,HFC-236cb,HFC-236ea或HFC-245cb;227caEαβ和HFC-32,HFC-143,HFC-245cb,HFC-272ca,HFC-281ea或HFC-281fa;227caEβγ和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161,HFC-263fb,HFC-272ca,HFC-281ea或HFC-281fa;227eaE和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161,HFC-263fb,HFC-272ca,HFC-281ea或HFC-281fa;C-234fEαβ和HFC-245cb,HFC-245eb,HFC-356mff或HFC-356mmz;C-234fEβγ和HFC-245ca,HFC-245cb,HFC-245ea,HFC-254ca,HFC-356mff或HFC-356mmz;236caE和HFC-143,HFC-245ca,或HFC-254ca;236eaEβγ和HFC-143,HFC-245ca,HFC-263ca,HFC-338mf,HFC-356mff或HFC-356mmz;或236faE和HFC-32,HFC-143,HFC-272ca,HFC-272fb,HFC-281fa;245faEβγ和HFC-356mff.
“共沸”组合物指表现为单一物质的两个或两个以上物质的恒沸液体混合物。共沸组合物的特征之一是该液体的部分蒸发或蒸馏所产生的蒸气的组成与所蒸发或蒸馏的液体的组成相同,即该混合物蒸馏/回流不改变组成。恒沸组合物称为共沸是因为它们与相同成分的非共沸混合物的混点相比较或者表现出最高沸点或者表现出最低沸点。
“类共沸物”组合物指表现为单一物质的两个或两个以上物质的恒沸或基本上恒沸的液体混合物。类共沸物组合物的特征之一是该液体部分蒸发或蒸馏所产生的蒸气的组成基本上与所蒸发或蒸馏的液体的组成相同,即该混合物蒸馏/回收基本不改变组成。
在本领域人们公认:对于类共沸物组合物,若50%(重量)组合物,如径蒸发或沸腾除去,则原组合物和50%(重量)原组合物已被除去后剩余的组合物间的蒸气压差在按绝对单位测量时小于10%。绝对单位是指压力的测量,例如磅/平方英寸,大气压、巴、托、达因/平方厘米、毫米汞柱、水柱英寸数和其它本领域熟知的相当的术语。如果是共沸物,则原组合物和50%(重量)原组合物已被除去后剩余的组合物间的蒸气压差为零。
因此,本发明包括含有效量的氟代醚和HFC的组合物,以使原组合物和50%原组合物被蒸发或沸出以后产生的剩余组合物间的蒸气压差为约10%或低于10%。这样的组合物包括以下例子:
5 116E和HFC-32,HFC-41,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a或HFC-161;125E和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a或HFC-161;134E和HFC-143,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236ea,HFC-236fa,HFC-245cb,HFC-254cb,HFC-254eb,HFC-338mf或HFC-356mff;134aE和HFC-32,HFC-134,HFC-143,HFC-
10 152a,HFC-227ca,HFC-227ea或HFC-245cb;143aE和HFC-32,HFC-134,HFC-143a,HFC-152a,HFC-227ca,HFC-227ea或HFC-245cb;C216E和HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161或HFC-245cb;C-216E2和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161或HFC-245cb;218E和HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161或HFC-263fb;218E2和
15 HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161,HFC-236fa或HFC-263fb;C-225eEαβ和HFC-143,HFC-236cb,HFC-236ea或HFC-245cb;227caEαβ和HFC-32,HFC-143,HFC-245cb,HFC-272ca,HFC-281ea或HFC-281fa;227caEβγ和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161,HFC-263fb,HFC-272ca,HFC-281ea或HFC-281fa;227eaE和HFC-32,HFC-134,HFC-134a,
20 HFC-143,HFC-152a,HFC-161,HFC-263fb,HFC-272ca,HFC-281ea或HFC-281fa;C-234fEαβ和-HFC-245cb,HFC-245eb,HFC-356mff或HFC-356mmz;C-234fEβγ和HFC-245ca,HFC-245cb,HFC-245ea,HFC-254ca,HFC-356mff或HFC-356mmz;236caE和HFC-143,HFC-245ca或HFC-254ca;236eaEβγ和HFC-143,HFC-245ca,HFC-263ca,HFC-338mf,HFC-356mff或HFC-356mmz;
25 236faE和HFC-32,HFC-143,HFC-272ca,HFC-272fb或HFC-281fa;或245faEβγ和HFC-356mff.
本发明基本恒沸、共沸或类共沸物
组合物包括以下组合物(均于25℃)
表1
30
成分 重量范围 优选
116E/HFC-32 50.0-88.0/12.0-50.0 50.0-88.0/12.0-50.0
116E/HFC-41 5.0-84.0/16.0-95.0 40.0-84.0/16.0-60.0
116E/HFC-125 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
35 116E/HFC-134 52.0-99.0/1.0-48.0 70.0-99.0/1.0-30.0
116E/HFC-134a 53.0-99.0/1.0-47.0 53.0-99.0/1.0-47.0
116E/HFC-143 60.0-99.0/1.0-40.0 60.0-99.0/1.0-40.0
116E/HFC-143a 1.0-99.0/1.0-99.0 30.0-99.0/1.0-70.0
116E/HFC-152a 60.0-99.0/1.0-40.0 60.0-99.0/1.0-40.0
40 116E/HFC-161 60.0-99.0/1.0-40.0 60.0-99.0/1.0-40.0
125E/HFC-32 25.0-73.0/27.0-75.0 30.0-70.0/30.0-70.0
125E/HFC-134 37.0-99.0/1.0-63.0 70.0-99.0/1.0-30.0
125E/HFC-134a 1.0-99.0/1.0-99.0 1.0-50.0/50.0-99.0
125E/HFC-143 1.0-43.0/57.0-99.0 1.0-30.0/70.0-99.0
125E/HFC-152a 1.0-61.0/39.0-99.0 1.0-40.0/60.0-99.0
125E/HFC-161 1.0-71.0/29.0-99.0 30.0-50.0/50.0-70.0
134E/HFC-143 1.0-99.0/1.0-99.0 1.0-50.0/50.0-99.0
134E/HFC-227ca 1.0-51.0/49.0-99.0 1.0-40.0/60.0-99.0
134E/HFC-227ea 1.0-49.0/51.0-99.0 1.0-40.0/60.0-99.0
134E/HFC-236ca 1.0-99.0/1.0-99.0 30.0-99.0/1.0-70.0
134E/HFC-236cb 1.0-99.0/1.0-99.0 1.0-70.0/30.0-99.0
134E/HFC-236ea 1.0-99.0/1.0-99.0 30.0-70.0/30.0-70.0
134E/HFC-236fa 1.0-99.0/1.0-99.0 1.0-80.0/20.0-99.0
134E/HFC-245cb 1.0-62.0/38.0-99.0 1.0-50.0/50.0-99.0
134E/HFC-254cb 1.0-99.0/1.0-99.0 1.0-70.0/30.0-99.0
134E/HFC-254eb 1.0-99.0/1.0-99.0 1.0-99.0/1.0-99.0
134E/HFC-338mf 27.0-99.0/1.0-73.0 40.0-80.0/20.0-60.0
134E/HFC-356mff 40.0-99.0/1.0-60.0 40.0-99.0/1.0-60.0
134aE/HFC-32 1.0-55.0/45.0-99.0 1.0-55.0/45.0-99.0
134aE/HFC-134 1.0-99.0/1.0-99.0 20.0-60.0/40.0-80.0
134aE/HFC-143 52.0-99.0/1.0-48.0 52.0-99.0/1.0-48.0
134aE/HFC-152a 1.0-99.0/1.0-99.0 1.0-99.0/1.0-99.0
134aE/HFC-227ca 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
134aE/HFC-227ea 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
134aE/HFC-245cb 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
143aE/HFC-32 1.0-54.0/46.0-99.0 1.0-54.0/46.0-99.0
143aE/HFC-134 1.0-99.0/1.0-99.0 30.0-99.0/1.0-70.0
143aE/HFC-143a 1.0-53.0/47.0-99.0 1.0-53.0/47.0-99.0
143aE/HFC-152a 1.0-99.0/1.0-99.0 20.0-80.0/20.0-80.0
143aE/HFC-227ca 1.0-99.0/1.0-99.0 1.0-80.0/20.0-99.0
143aE/HFC-227ea 1.0-99.0/1.0-99.0 1.0-90.0/10.0-99.0
143aE/HFC-245cb 20.0-99.0/1.0-80.0 20.0-80.0/20.0-80.0
C216E/HFC-134 1.0-99.0/1.0-99.0 50.0-99.0/1.0-50.0
C216E/HFC-134a 1.0-99.0/1.0-99.0 20.0-80.0/20.0-80.0
C216E/HFC-143 61.0-99.0/1.0-39.0 61.0-99.0/1.0-39.0
C216E/HFC-152a 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
C216E/HFC-161 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
C216E/HFC-245cb 1.0-99.0/1.0-99.0 30.0-99.0/1.0-70.0
C216E2/HFC-32 1.0-70.0/30.0-99.0 30.0-70.0/30.0-70.0
C216E2/HFC-134 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
C216E2/HFC-134a 1.0-99.0/1.0-99.0 1.0-80.0/20.0-99.0
C216E2/HFC-143 58.0/99.0/1.0-42.0 58.0-99.0/1.0-42.0
C216E2/HFC-152a 1.0-99.0/1.0-99.0 40.0-99.0/1.0-60.0
C216E2/HFC-161 1.0-84.0/16.0-99.0 20.0-84.0/16.0-80.0
C216E2/HFC-245cb 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
218E/HFC-134 35.0-99.0/1.0-65.0 50.0-80.0/20.0-50.0
218E/HFC-134a 1.0-99.0/1.0-99.0 20.0-80.0/20.0-80.0
218E/HFC-143 57.0-99.0/1.0-43.0 57.0-99.0/1.0-43.0
218E/HFC-152a 41.0-99.0/1.0-59.0 41.0-99.0/1.0-59.0
218E/HFC-161 39.0-84.0/16.0-61.0 39.0-84.0/16.0-61.0
218E/HFC-263fb 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
218E2/HFC-134 1.0-79.0/21.0-99.0 20.0-70.0/30.0-80.0
218E2/HFC-134a 1.0-72.0/28.0-99.0 1.0-60.0/40.0-99.0
218E2/HFC-143 52.0-91.0/9.0-48.0 52.0-91.0/9.0-48.0
218E2/HFC-152a 1.0-81.0/19.0-99.0 20.0-70.0/30.0-80.0
218E2/HFC-161 1.0-77.0/23.0-99.0 20.0-77.0/23.0-80.0
218E2/HFC-236fa 1.0-99.0/1.0-99.0 30.0-99.0/1.0-70.0
218E2/HFC-263fb 1.0-99.0/1.0-99.0 20.0-90.0/10.0-80.0
C225eEαβ/HFC-143 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
C225eEαβ/HFC-236cb 1.0-99.0/1.0-99.0 1.0-80.0/20.0-99.0
C225eEαβ/HFC-236ea 1.0-99.0/1.0-99.0 30.0-99.0/1.0-70.0
C225eEαβ/HFC-245cb 1.0-65.0/35.0-99.0 1.0-65.0/35.0-99.0
227caEαβ/HFC-32 1.0-61.0/39.0-99.0 1.0-61.0/39.0-99.0
227caEαβ/HFC-143 42.0-99.0/1.0-58.0 42.0-95.0/5.0-58.0
227caEαβ/HFC-245cb 1.0-82.0/18.0-99.0 1.0-80.0/20.0-99.0
227caEαβ/HFC-272ca 1.0-99.0/1.0-99.0 30.0-99.0/1.0-70.0
227caEαβ/HFC-281ea 1.0-99.0/1.0-99.0 40.0-99.0/1.0-60.0
227caEαβ/HFC-281fa 1.0-99.0/1.0-99.0 40.0-99.0/1.0-60.0
227caEβγ/HFC-32 1.0-67.0/33.0-99.0 1.0-67.0/33.0-99.0
227caEβγ/HFC-134 1.0-76.0/24.0-99.0 10.0-50.0/50.0-90.0
227caEβγ/HFC-134a 1.0-67.0/33.0-99.0 1.0-67.0/33.0-99.0
227caEβγ/HFC-143 46.0-91.0/9.0-54.0 46-91.0/9.0-54.0
227caEβγ/HFC-152a 1.0-78.0/22.0-99.0 10.0-78.0/22.0-90.0
227caEβγ/HFC-161 1.0-72.0/28.0-99.0 10.0-72.0/28.0-90.0
227caEβγ/HFC-263fb 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
227caEβγ/HFC-272ca 1.0-99.0/1.0-99.0 30.0-99.0/1.0-70.0
227caEβγ/HFC-281ea 1.0-99.0/1.0-99.0 40.0-99.0/1.0-60.0
227caEβγ/HFC-281fa 1.0-99.0/1.0-99.0 40.0-99.0/1.0-60.0
227eaE/HFC-32 1.0-68.0/32.0-99.0 10.0-68.0/32.0-90.0
227eaE/HFC-134 1.0-78.0/22.0-99.0 10.0-60.0/40.0-90.0
227eaE/HFC-134a 1.0-70.0/30.0-99.0 1.0-60.0/40.0-99.0
227eaE/HFC-143 47.0-92.0/8.0-53.0 47.0-92.0/8.0-53.0
227eaE/HFC-152a 1.0-80.0/20.0-99.0 10.0-80.0/20.0-90.0
227eaE/HFC-161 1.0-73.0/27.0-99.0 20.0-73.0/27.0-80.0
227eaE/HFC-263fb 1.0-99.0/1.0-99.0 30.0-99.0/1.0-70.0
227eaE/HFC-272ca 30.0-99.0/1.0-70.0 30.0-99.0/1.0-70.0
227eaE/HFC-281ea 1.0-99.0/1.0-99.0 40.0-99.0/1.0-60.0
227eaE/HFC-281fa 1.0-99.0/1.0-99.0 40.0-99.0/1.0-60.0
C234fEαβ/HFC-245cb 1.0-58.0/42.0-99.0 1.0-58.0/42.0-99.0
C234fEαβ/HFC-245eb 1.0-99.0/1.0-99.0 20.0-99.0/1.0-80.0
就本发明的目的而言,“有效量”被定义为混合后能生成共沸或类共沸物组合物的本发明组合物中每个成分的数量。该定义包括每个成分的数量,该数量可以根据施加到组合物上的压力变动,但需保证在不同的压力下该共沸或类共沸物组合物继续存在。然而组合物可能具有不同的沸点。
因此,有效量包括例如可用重量百分数表示的在与这里所述的温度或压力下生成共沸或类共沸物组合物。
就本发明的目的而言,共沸或恒沸也意指基本上共沸或基本上恒沸。换言之,这些术语的含义不仅包括上述真正的共沸物,也包括其它按不同的比例含相同的成分并在其它温度和压力下是真正的共沸物的组合物以及那些是部分相同共沸体系并且在性质上是类共沸物的等效组合物。正如本领域所公认的那样,有一系列组合物,该组合物含与共沸物相同的成分,不仅在制冷和其它应用上表现出基本相同的性质而且也表现现与根据恒沸特征或倾向在沸腾时不分离或不分馏的真正的共沸组合物基本相同的性质。
实际上,可以根据所选择的条件用任何下述标准来表示显露出多种外观的恒混合物的特性。
*由于正是“共沸物”这个术语既确定又具限定性,组合物可以定义为A、B、C(和D…)的共沸物,并且为了这个恒温组合物物质的唯一组成需要有效量的A、B、C(和D…)。
*本领域技术人员周知:在不同的压力下,给定共沸物的组成至少会在某种程度上发生变化,改变压力至少在某种程度上也会改变沸点温度。因此A、B、C(和D…)的共沸物代表一个独特的关系型,但它的组成可随温度和/或压力而变化。因此,常用组成范围而不用固定组成定义共沸物。
*组成可以定义为特定的A、B、C(和D…)的重量下分数关系或摩尔百分数关系,尽管公认为这样的特定值指出了唯一一种特定的关系而且实际上对于给定的共沸物来说实际存在由A、B、C(和D…)所代表随压力的影响而变化的一系列这样的关系。
*A、B、C(和D…)的共沸物的特性可以通过将组合物定义为以给定压力下的沸点为特征的共沸物来表示,这样通过特定数字组成给出了鉴定特征而对本发明范围无过分限制,该组成受可用分析设备限制并且是唯一的与可用分析设备一样精确。
本发明共沸或类共沸物组合物可按任何常规方法来制备,包括将需要量的物质混合的方法。优选的方法是称出所需成分的重量,然后在适当的容器内将它们混合。
目前尚未有将所有相关的因素都结合到单一的由于温室气体发射物所致的全球变暖能力的普遍可接受的方法,定义化合物的温室效应的途径之一是相对于已知的标准化合物根据增强全球变暖的能力来定。在本发明中,一些氟代醚和HFC的囟化碳全球变暖能力(HGWP)由已知的测定技术测得。
HGWP被定义为气体的发射物在该气体在大气中的生存期间所产生的增长的辐射变暖与相同质量的对照气体CFC-11释放的计算出来的变暖之比,CFC-11的HGWP为1.0。HGWP的计算由Fisher等人在Nature,344卷,513-516页(1990),“CFC及其替代物对全球变暖的相对影响的模型计算”一文中作了论述,这里将其全文作为参考。
业已发现HFC的HGWP可以通过将HGWP低于HFC的氟代醚加到HFC中而被降低,这样,HFC和氟代醚的混合物就具低于HFC的HGWP。因此,本发明涉及第一成分和第二成分的组合物;所述第一成分包括氟代烃;所述第二成分包括氟代醚,其HGWP小于第一成分的HGWP;这样,组合物的HGWP小于第一成分的HGWP。
本发明范围包括单一的氟代醚化合物加到单一的HFC中,也包括单一的氟代醚加到两个或两个以上HFC的混合物中,此外,本发明包括一种或一种以上氟代醚混合物加到单一的HFC中,也包括一种或一种以上氟代醚混合物加到两种或两种以上HFC混合物中。
成分A和成分B的组合物的HGWP等于[A的馏分组成]×[A的HGWP]+[B的馏分组成]×[B的HGWP]。两种以上成分的组合物的HGWP按同样方法测定,即通过将成分的馏分组成与其HGWP相乘,然后再将所有成分的部分HGWP加到一起。
说明本发明的具体实施例见下述,若无另外说明,本文所有百分数为重量百分数。应该明确的是:这些实施例仅说明本发明而决不应看作是对本发明范围的限制。实施例中给出的所有数值均为+/-5%。
实施例1
相研究
对下列组合物的相研究表明下列组合物是共沸的,在该研究中于恒定温度25℃改变组成并测定蒸气压。
表2
蒸气压
氟代醚重量百分数 HFC重量百分数 磅/平方英寸(KPa)
75.2wt.%116E 24.8wt.%HFC-32 490.5(3382)
58.6wt.%116E 41.4wt.%HFC-41 575.6(3969)
86.0wt.%116E 14.0wt.%HFC-125 295.6(2038)
90.2wt.%116E 9.8wt.%HFC-134 302.7(2087)
90.0wt.%116E 10.0wt.%HFC-134a 299.5(2065)
94.9wt.%116E 5.1wt.%HFC-143 305.9(2109)
94.8wt.%116E 5.2wt.%HFC-143a 293.1(2021)
92.1wt.%116E 7.9wt.%HFC-152a 305.4(2106)
87.3wt.%116E 12.7wt.%HFC-161 344.3(2374)
86.5wt.%125E 13.5wt.%HFC-134 130.7(901)
92.0wt%125E 8.0wt%HFC-143 132.0(910)
84.4wt%125E 15.6wt%HFC-152a 134.1(925)
66.5wt%125E 33.5wt%HFC-161 171.1(1179)
37.9wt%134E 62.1wt%HFC-143 34.0(235)
13.6wt%134E 86.4wt%HFC-227ca 65.9(454)
7.3wt%134E 92.7wt.%HFC-227ea 67.2(463)
78.0wt%134E 22.0wt%HFC-236ca 63.8(440)
36.3wt%134E 63.7wt%HFC-236cb 36.3(250)
52.8wt%134E 47.2wt%HFC-236ea 33.3(229)
14.2wt.%134E 85.8wt.%HFC-236fa 39.8(274)
28.5wt%134E 71.5wt%HFC-245cb 80.0(551)
29.7wt%134E 70.3wt%HFC-254cb 34.9(241)
28.6wt.%134E 71.4wt.%HFC-254eb 35.5(245)
97.1wt.%134E 2.9wt.%HFC-356mff 30.4(210)
65.5wt%134E 34.5wt%HFC-338mf 33.2(229)
11.5wt.%134aE 88.5wt.%HFC-32 249.2(1718)
42.6wt.%134aE 57.4wt.%HFC-134 78.3(540)
98.1wt.%134aE 1.9wt.%HFC-143 73.9(510)
19.1wt.%134aE 80.9wt.%HFC-152a 86.0(593)
65.5wt%134aE 34.5wt%HFC-227ca 76.3(526)
65.4wt.%134aE 34.6wt.%HFC-227ea 75.4(520)
57.7wt.%134aE 42.3wt.%HFC-245cb 91.7(632)
6.2wt.%143aE 93.8wt.%HFC-32 247.4(1706)
92.4wt.%143aE 7.6wt.%HFC-134 127.6(880)
8.7wt.%143aE 91.3wt.%HFC-143a 182.2(1256)
48.6wt.%143aE 51.4wt.%HFC-152a 87.3(602)
71.5wt%143aE 28.5wt%HFC-227ca 85.9(592)
75.6wt.%143aE 24.4wt.%HFC-227ea 84.8(585)
59.6wt.%143aE 40.4wt.%HFC-245cb 102.8(709)
79.8wt.%C216E 20.2wt.%HFC-134 104.4(720)
61.7wt.%C216E 38.3wt.%HFC-134a 108.0(744)
91.9wt.%C216E 8.1wt.%HFC-143 103.5(714)
77.6wt.%C216E 22.4wt.%HFC-152a 109.1(752)
58.8wt.%C216E 41.2wt.%HFC-161 148.3(1022)
95.1wt.%C216E 4.9wt.%HFC-245cb 100.6(693)
36.0wt.%C216E2 64.0wt.%HFC-32 272.4(1878)
60.5wt.%C216E2 39.5wt.%HFC-134 88.6(611)
20.6wt.%C216E2 79.4wt.%HFC-134a 99.0(683)
87.1wt.%C216E2 12.9wt.%HFC-143 82.9(572)
60.5wt.%C216E2 39.5wt.%HFC-152a 95.6(659)
45.7wt.%C216E2 54.3wt.%HFC-161 138.3(954)
74.7wt.%C216E2 25.3wt.%HFC-245cb 81.3(561)
63.3wt.%218E 36.7wt.%HFC-134 116.6(804)
53.0wt.%218E 47.0wt.%HFC-134a 122.3(843)
85.3wt.%218E 14.7wt.%HFC-143 103.7(715)
68.2wt.%218E 31.8wt.%HFC-152a 124.0(855)
62.6wt.%218E 37.4wt.%HFC-161 170.9(1178)
96.3wt.%218E 3.7wt.%HFC-263fb 84.0(579)
46.1wt.%218E2 53.0wt.%HFC-134 89.6(617)
24.7wt.%218E2 75.3wt.%HFC-134a 101.1(697)
78.3wt.%218E2 21.7wt.%HFC-143 72.6(501)
51.0wt.%218E2 49.0wt.%HFC-152a 98.1(676)
46.4wt.%218E2 53.6wt.%HFC-161 145.1(1000)
89.8wt.%218E2 10.2wt.%HFC-236fa 52.6(363)
60.5wt.%218E2 39.5wt.%HFC-263fb 57.9(399)
55.9wt.%C225eEαβ 44.1wt.%HFC-143 38.0(2626)
16.7wt.%C225eEαβ 83.3wt.%HFC-236cb 33.7(232)
91.5wt.%C225eEαβ 8.5wt.%HFC-236ea 31.1(214)
22.4wt.%C225eEαβ 77.6wt.%HFC-245cb 70.1(483)
17.9wt.%227caEαβ 82.1wt.%HFC-32 253.4(1747)
70.9wt.%227caEαβ 29.1wt.%HFC-143 53.7(370)
8.1wt.%227caEαβ 91.9wt.%HFC-245cb 67.4(465)
94.3wt.%227caEαβ 5.7wt.%HFC-272ca 41.5(286)
31.5wt.%227caEαβ 68.5wt.%HFC-281ea 47.3(326)
84.3wt.%227caEαβ 15.7wt.%HFC-281fa 42.5(293)
28.4wt.%227caEβγ 71.6wt.%HFC-32 269.7(1859)
34.8wt.%227caEβγ 65.2wt.%HFC-134 82.7(570)
1.9wt.%227caEβγ 98.1wt.%HFC-134a 98.3(678)
73.8wt.%227caEβγ 26.2wt.%HFC-143 66.2(456)
38.3wt.%227caEβγ 61.7wt.%HFC-152a 91.4(630)
34.4wt.%227caEβγ 65.6wt.%HFC-161 137.5(948)
32.9wt.%227caEβγ 67.1wt.%HFC-263fb 54.6(376)
89.0wt.%227caEβγ 11.0wt.%HFC-272ca 49.6(342)
73.1wt.%227caEβγ 26.9wt.%HFC-281ea 54.0(372)
85.9wt.%227caEβγ 14.1wt.%HFC-281fa 51.1(352)
30.0wt.%227eaE 70.0wt.%HFC-32 272.2(1877)
38.2wt.%227eaE 61.8wt.%HFC-134 84.7(584)
9.3wt.%227eaE 90.7wt.%HFC-134a 98.6(680)
74.9wt.%227eaE 25.1wt.%HFC-143 68.9(475)
42.1wt.%227eaE 57.9wt.%HFC-152a 93.3(643)
37.5wt.%227eaE 62.5wt.%HFC-161 139.5(962)
49.3wt.%227eaE 50.7wt.%HFC-263fb 55.7(384)
90.7wt.%227eaE 9.3wt.%HFC-272ca 52.1(359)
76.8wt.%227eaE 23.2wt.%HFC-281ea 56.0(386)
87.6wt.%227eaE 12.4wt.%HFC-281fa 53.4(368)
13.5wt.%C-234fEαβ 86.5wt.%HFC-245cb 69.9(482)
49.1wt.%C-234fEαβ 50.9wt.%HFC-245eb 17.6(121)
59.0wt.%C-234fEαβ 41.0wt.%HFC-356mff 18.8(130)
50.1wt.%C-234fEαβ 49.9wt.%HFC-356mmz 20.1(139)
33.6wt.%C-234fEβγ 66.4wt.%HFC-245ca 14.5(100)
10.2wt.%C-234fEβγ 89.8wt.%HFC-245cb 69.1(476)
36.0wt.%C-234fEβγ 64.0wt.%HFC-245ea 14.5(100)
36.0wt.%C-234fEβγ 64.0wt.%HFC-254ca 13.8(95)
43.1wt.%C-234fEβγ 56.9wt.%HFC-356mff 17.1(118)
35.8wt.%C-234fEβγ 64.2wt.%HFC-356mmz 18.6(128)
12.0wt.%236caE 88.0wt.%HFC-143 33.4(230)
17.6wt.%236caE 82.4wt.%HFC-254ca 13.8(95)
25.9wt.%236eaEβγ 74.1wt.%HFC-143 34.7(239)
69.1wt.%236eaEβγ 30.9wt.%HFC-245ca 16.1(111)
4.1wt.%236eaEβγ 95.9wt.%HFC-263ca 18.3(126)
92.6wt.%236eaEβγ 7.49wt.%HFC-338mf 18.9(130)
96.9wt.%236eaEβγ 3.1wt.%HFC-356mff 15.7(108)
15.1wt.%236eaEβγ 84.9wt.%HFC-356mmz 16.7(115)
8.5wt.%236faE 91.5wt.%HFC-32 248.6(1714)
56.9wt.%236faE 43.1wt.%HFC-143 45.1(311)
27.8wt.%236faE 72.2wt.%HFC-272ca 34.8(240)
82.3wt.%236faE 17.7wt.%HFC-272fb 30.2(208)
9.3wt.%236faE 90.7wt.%HFC-281fa 37.7(260)
4.4wt.%245faEβγ 95.6wt.%HFC-356mff 14.9(103)
实施例2
25℃时蒸气泄漏对蒸气压的影响
将起始组合物于25℃装入容器中并测量该组合物的蒸气压。将温度维持恒定在25℃时使组合物从容器中泄漏出直至50%(重量)起始组合物被除去,这时测量残留在容器中的组合物的蒸气压,结果总结如下。
表3
0%(重量)蒸发磅 50%(重量)蒸发磅
制冷剂组成 /平方英寸(KPa) /平方英寸(KPa) 蒸气压变化百分数
116E/HFC-32
75.2/24.8 490.6(3385) 490.6(3385) 0.0
89/11 484.3(3341) 434.4(2297) 10.3
88/12 485.8(3352) 451.4(3114) 7.1
70/30 490.4(3383) 490.0(3381) 0.6
60/40 489.6(3378) 488.0(3367) 0.3
50/50 488.8(3372) 486.1(3354) 0.6
80/20 490.2(3382) 489.1(3374) 0.2
116E/HFC-41
58.6/41.4 575.6(3971) 575.6(3971) 0.0
70/30 572.4(3949) 566.7(3910) 1.0
85/15 540.4(3728) 483.1(3333) 10.6
84/16 544.9(3759) 493.7(3406) 9.3
40/60 571.3(3942) 558.5(3853) 2.2
30/70 565.7(3903) 515.9(3559) 8.8
28/72 564.1(3892) 505.8(3490) 10.3
29/71 564.9(3897) 510.7(3523) 9.6
5/95 512.9(3539) 477.9(3297) 6.6
116E/HFC-125
86.0/14.0 295.6(2039) 295.6(2039) 0.0
99/1 292.7(2019) 292.6(2018) 0.0
70/30 292.2(2016) 291.1(2008) 0.4
60/40 297.3(2051) 284.0(1959) 4.5
50/50 280.6(1936) 273.9(1889) 2.4
40/60 272.0(1876) 260.5(1797) 4.4
30/70 261.0(1800) 244.0(1683) 6.5
5 10/90 227.3(1568) 209.5(1445) 7.2
1/99 202.5(1397) 199.8(1378) 1.3
116E/HFC-134
99.0/1.0 294.8(2033) 294.0(2027) 0.3
10 90.2/9.8 302.7(2087) 302.7(2087) 0.0
70.0/30.0 293.5(2024) 285.2(1967) 2.8
52.0/48.0 283.9(1957) 258.0(1779) 9.1
116E/HFC-134a
15 90.0/10.0 299.5(2066) 299.5(2066) 0.0
99/1 293.8(2027) 293.5(2025) 0.0
52/48 276.8(1909) 248.6(1715) 10.2
53/47 277.5(1914) 251.8(1737) 9.3
60/40 282.6(1949) 267.0(1842) 5.5
20 70/30 289.7(1998) 281.6(1943) 2.8
80/20 296.2(2043) 293.7(2026) 0.8
116E/HFC-143
94.9/5.1 305.9(2110) 305.9(2110) 0.0
25 99/1 300.2(2071) 295.6(2039) 1.5
80/20 299.2(2064) 295.9(2041) 1.1
70/30 293.5(2025) 285.2(1967) 2.8
65/35 290.6(2005) 280.2(1933) 3.5
61/39 300.6(2074) 298.3(2058) 0.8
30 60/40 300.6(2074) 283.6(1956) 5.6
116E/HFC-143a
94.8/5.2 293.1(2022) 293.1(2022) 0.0
70/30 281.6(1943) 277.4(1914) 1.5
35 60/40 273.6(1887) 265.0(1828) 3.1
50/50 264.3(1823) 250.0(1725) 5.4
40/60 253.7(1750) 232.3(1602) 8.4
10/90 206.8(1426) 186.0(1283) 10.1
1/99 183.6(1266) 180.9(1248) 1.5
40 99/1 292.5(2018) 292.5(2018) 0.0
116E/HFC-152a
92.1/7.9 305.5(2108) 305.5(2108) 0.0
99/1 296.4(2045) 295.1(2036) 0.4
45 70/30 292.3(2016) 280.4(1934) 4.1
60/40 286.6(1977) 259.3(1789) 9.5
116E/HFC-161
87.3/12.7 344.4(2376) 244.4(2376) 0.0
50 99/1 307.4(2121) 297.5(2052) 3.2
70/30 337.9(2331) 330.2(2278) 2.3
5 60/40 334.1(2305) 308.4(2128) 7.7
95/5 335.6(2315) 324.8(2241) 3.2
125E/HFC-32
1.0/99.0 246.2(1697) 245.9(1695) 0.1
10 10.0/90.0 241.2(1663) 238.8(1646) 1.0
20.0/80.0 235.0(1620) 230.0(1586) 2.1
30.0/70.0 227.8(1571) 220.1(1518) 3.4
40.0/60.0 219.4(1513) 209.3(1443) 4.6
50.0/50.0 209.5(1444) 197.4(1361) 5.8
15 60.0/40.0 197.9(1364) 184.7(1273) 6.7
70.0/30.0 184.4(1271) 171.2(1180) 7.2
80.0/20.0 168.5(1162) 157.2(1084) 6.7
90.0/10.0 149.9(1034) 142.8(985) 4.7
99.0/1.0 130.8(902) 129.9(896) 0.7
20
125E/HFC-134
37.0/63.0 116.3(802) 105.1(725) 9.6
25 70.0/30.0 128.6(887) 127.6(880) 0.8
86.5/13.5 130.7(901) 130.7(901) 0.0
99.0/1.0 128.9(889) 128.8(888) 0.1
125E/HFC-134a
30 1.0/99.0 98.5(679) 98.5(679) 0.0
10.0/90.0 100.9(696) 100.4(692) 0.5
20.0/80.0 103.5(714) 102.6(707) 0.9
30.0/70.0 106.2(732) 105.0(724) 1.1
40.0/60.0 108.9(751) 107.6(742) 1.2
35 50.0/50.0 111.8(771) 110.4(761) 1.3
60.0/40.0 114.8(792) 113.4(782) 1.2
70.0/30.0 117.9(813) 116.7(805) 1.0
80.0/20.0 121.3(836) 120.3(829) 0.8
90.0/10.0 124.8(860) 124.2(856) 0.5
40 99.0/1.0 128.1(883) 128.1(883) 0.0
125E/HFC-143
57.0/43.0 123.5(852) 112.1(773) 9.2
60.0/40.0 124.2(856) 115.9(799) 6.7
45 70.0/30.0 126.9(875) 122.4(844) 3.6
92.0/8.0 132.0(910) 132.0(190) 0.0
99.0/1.0 129.5(893) 129.3(892) 0.2
5 125E/HFC-152a
39.0/61.0 120.3(829) 108.6(747) 9.7
50.0/50.0 125.3(864) 118.5(817) 5.4
60.0/40.0 129.0(889) 125.6(866) 2.7
84.4/15.6 134.1(925) 134.1(925) 0.0
10 99.0/1.0 129.4(892) 129.2(891) 0.2
125E/HFC-161
29.0/71.0 161.6(1114) 145.8(1006) 9.8
50.0/50.0 169.0(1165) 166.3(1146) 1.6
15 66.5/33.5 171.1(1179) 171.1(1179) 0.0
70.0/30.0 170.9(1179) 170.8(1177) 0.1
99.0/1.0 133.2(919) 130.5(900) 2.1
134E/HFC-143
20 1.0/99.0 33.1(228) 33.1(228) 0.0
37.9/62.1 34.0(235) 34.0(235) 0.0
50.0/50.0 33.9(234) 33.9(234) 0.0
70.0/30.0 33.2(229) 33.1(228) 0.4
99.0/1.0 30.6(211) 30.5(210) 0.1
25
134E/HFC-227ca
1.0/99.0 64.2(443) 64.1(442) 0.1
13.6/86.4 65.9(454) 65.9(454) 0.0
30.0/70.0 64.6(445) 63.5(438) 1.6
30 40.0/60.0 63.0(434) 60.4(416) 4.1
51.0/49.0 60.9(420) 55.0(379) 9.6
134E/HFC-227ea
7.3/92.7 67.2(463) 67.2(463) 0.0
35 1.0/99.0 66.8(461) 66.8(461) 0.0
40.0/60.0 62.6(432) 59.3(409) 5.3
50.0/50.0 60.3(416) 54.0(372) 10.4
49.0/51.0 60.6(418) 54.6(376) 9.9
40 134E/HFC-236ca
78.0/22.0 29.5(203) 29.5(203) 0.0
90/10 29.4(202) 29.4(202) 0.0
99/1 29.2(201) 29.2(201) 0.0
70/30 29.4(202) 29.4(202) 0.0
45 60/40 29.3(202) 29.2(201) 0.3
50/50 29.0(200) 29.0(200) 0.0
30/70 28.0(193) 27.7(191) 1.1
10/90 26.2(180) 26.0(179) 0.8
1/99 25.1(173) 25.0(172) 0.4
50
5 134E/HFC-236cb
1.0/99.0 33.8(233) 33.8(233) 0.0
36.3/63.7 36.3(250) 36.3(250) 0.0
40.0/60.0 36.3(250) 36.3(250) 0.0
70.0/30.0 34.8(240) 34.3(236) 1.6
10 99.0/1.0 30.6(211) 30.5(210) 0.3
134E/HFC-236ea
1.0/99.0 28.9(199) 28.9(199) 0.0
30.0/70.0 32.6(225) 32.4(223) 0.7
15 52.8/47.2 33.3(229) 33.3(229) 0.0
70.0/30.0 32.9(227) 32.8(226) 0.3
99.0/1.0 30.6(211) 30.5(210) 0.3
134E/HFC-236fa
20 14.2/85.8 39.8(274) 39.8(274) 0.0
1.0/99.0 39.4(272) 39.4(272) 0.0
40.0/60.0 38.8(268) 38.6(266) 0.5
60.0/40.0 37.1(256) 36.3(250) 2.2
80.0/20.0 34.4(237) 33.3(230) 3.2
25 99.0/1.0 30.7(212) 30.5(210) 0.7
134E/HFC-245cb
1.0/99.0 69.0(476) 67.8(467) 1.7
28.5/71.5 80.0(551) 80.0(551) 0.0
30 40.0/60.0 79.6(549) 79.0(545) 0.7
50.0/50.0 78.9(544) 77.4(534) 1.9
62.0/38.0 77.9(537) 71.4(492) 8.4
134E/HFC-254cb
35 1.0/99.0 34.2(236) 34.2(236) 0.0
29.7/70.3 34.9(241) 34.9(241) 0.0
40.0/60.0 34.8(240) 34.8(240) 0.0
70.0/30.0 33.6(232) 33.4(230) 0.7
99.0/1.0 30.6(211) 30.5(210) 0.1
40
134E/HFC-254eb
28.6/71.4 35.5(245) 35.5(245) 0.0
15.0/85.0 35.3(243) 35.3(243) 0.0
1.0/99.0 34.8(240) 34.8(240) 0.0
45 60.0/40.0 34.7(239) 34.5(238) 0.6
80.0/20.0 33.1(228) 32.7(225) 1.2
99.0/1.0 30.6(211) 30.5(210) 0.3
134E/HFC-338mf
50 27.0/73.0 30.5(210) 27.6(190) 9.4
40.0/60.0 32.2(222) 31.1(214) 3.4
5 65.5/34.5 33.2(229) 33.2(229) 0.0
80.0/20.0 32.9(227) 32.6(225) 0.8
99.0/1.0 30.6(211) 30.5(210) 0.4
134E/HFC-356mff
10 97.1/2.9 30.4(210) 30.4(210) 0.0
99.0/1.0 30.4(210) 30.4(210) 0.0
60.0/40.0 28.7(198) 27.8(192) 3.1
40.0/60.0 26.4(182) 23.9(165) 9.5
39.0/61.0 26.3(181) 23.6(163) 10.3
15
134aE/HFC-32
11.5/88.5 249.1(1718) 249.1(1718) 0.0
1/99 247.2(1705) 247.1(1705) 0.0
20/80 248.3(1713) 247.7(1709) 0.2
20 30/70 245.8(1695) 243.0(1676) 1.1
56/44 231.1(1594) 207.6(1432) 10.2
55/45 232.0(1600) 210.0(1449) 9.5
40/60 241.9(1669) 234.5(1618) 3.0
25 134aE/HFC-134
99.0/1.0 74.0(510) 74.0(510) 0
60.0/40.0 77.9(537) 77.9(537) 0
42.6/57.4 78.3(540) 78.3(540) 0
20.0/80.0 77.7(536) 77.7(536) 0
30 1.0/99.0 76.2(525) 76.2(525) 0
134aE/HFC-143
99.0/1.0 73.8(509) 73.8(509) 0
98.1/1.9 73.9(510) 73.9(510) 0
35 52.0/48.0 65.0(448) 58.7(405) 9.7
134aE/HFC-152a
19.1/80.9 86.1(594) 86.1(594) 0.0
10/90 86.0(593) 86.0(593) 0.0
40 1/99 85.8(592) 85.8(592) 0.0
30/70 86.0(593) 86.0(593) 0.0
50/50 85.0(586) 84.9(585) 0.1
70/30 82.7(570) 82.2(567) 0.6
80/20 80.7(556) 80.0(552) 0.9
45 99/1 74.3(512) 74.2(512) 0.1
134aE/HFC-227ca
65.5/34.5 76.2(525) 76.2(525) 0.0
80/20 75.8(523) 75.8(523) 0.0
50 90/10 75.0(517) 74.9(516) 0.1
99/1 74.0(510) 73.9(510) 0.1
5 50/50 75.7(522) 75.6(521) 0.1
40/60 74.8(516) 74.4(513) 0.5
30/70 73.4(506) 72.7(501) 1.0
20/90 71.2(491) 70.2(484) 1.4
1/99 64.2(443) 64.1(442) 0.3
10
134aE/HFC-227ea
65.4/34.6 75.5(521) 75.5(521) 0.0
80/20 75.2(518) 75.1(518) 0.1
90/10 74.6(514) 74.6(514) 0.0
15 99/1 73.9(509) 73.9(509) 0.0
50/50 75.1(518) 75.0(517) 0.1
30/70 73.4(506) 73.0(503) 0.5
10/90 69.6(480) 69.2(477) 0.6
1/99 67.0(462) 67.0(462) 0.0
20
134aE/HFC-245cb
57.7/42.3 91.6(632) 91.6(632) 0.0
70/30 90.9(627) 90.1(621) 0.9
80/20 89.0(614) 85.9(592) 3.5
25 92/8 83.3(574) 77.4(534) 7.1
99/1 75.5(521) 74.1(511) 1.8
30/70 87.6(604) 84.3(581) 3.8
20/80 83.4(575) 78.4(541) 6
10.90 76.9(530) 72.3(498) 6
30 1/99 67.7(467) 67.8(467) 0.1
143aE/HFC-32
6.2/98.8 247.4(1707) 247.4(1707) 0.0
1/99 246.9(1703) 246.9(1703) 0.0
35 20/80 245.1(1691) 243.9(1682) 0.5
30/70 241.4(1665) 237.3(1637) 1.7
40/60 236.1(1629) 226.9(1565) 3.9
50/50 228.8(1578) 210.9(1455) 7.8
55/45 224(1545) 200.1(1380) 10.6
40 54/46 225(1552) 202(1393) 10.0
143aE/HFC-134
99.0/1.0 127.5(879) 127.5(879) 0
92.4/7.6 127.6(880) 127.6(880) 0
45 30.0/70.0 123.4(851) 123.1(849) 0.2
1.0/99.0 118.3(815) 118.2(815) 0
143aE/HFC-143a
8.7/91.3 182.1(1256) 182.1(1256) 0.0
50 1/99 181.0(1248) 181.0(1248) 0.0
20/80 180.5(1245) 179.7(1239) 0.4
5 40/50 172.4(1189) 165.0(1138) 4.3
55/45 161.8(1116) 144.7(998) 10.6
54/46 162.7(1122) 146.3(1009) 10.1
53/47 163.5(1128) 147.9(1020) 9.5
10 143aE/HFC-152a
48.6/51.4 87.4(603) 87.4(603) 0.0
40/60 87.3(602) 87.3(602) 0.0
30/70 87.2(601) 87.1(601) 0.1
10/90 86.3(595) 86.3(595) 0.0
15 1/99 85.8(592) 85.8(592) 0.0
60/40 87.2(601) 87.2(601) 0.0
70/30 86.9(599) 86.8(598) 0.1
90/10 85.2(587) 85.2(587) 0.0
99/1 84.0(579) 84.0(579) 0.0
20
143aE/HFC-227ca
71.5/28.5 85.9(592) 85.9(592) 0.0
80/20 85.7(591) 85.7(591) 0.0
99/1 84.0(579) 84.0(579) 0.0
25 60/40 85.6(590) 85.4(589) 0.2
40/60 83.2(574) 82.1(566) 1.3
30/70 80.8(557) 78.9(544) 2.3
20/80 77.2(532) 74.5(514) 3.5
1/99 64.7(446) 64.3(443) 0.6
30
143aE/HFC-227ea
75.6/24.4 84.9(585) 84.9(585) 0.0
90/10 84.5(583) 84.5(583) 0.0
99/1 83.9(578) 83.9(578) 0.0
35 70/30 84.8(585) 84.8(585) 0.0
60/40 84.4(582) 84.3(581) 0.1
50/50 83.6(576) 83.2(574) 0.5
30/70 80.1(552) 78.9(544) 1.5
10/90 72.8(502) 71.3(492) 2.1
40 1/99 67.3(464) 67.1(463) 0.3
143aE/HFC-245cb
59.6/40.4 102.8(709) 102.8(709) 0.0
70/30 102.2(705) 101.5(700) 0.7
45 80/20 100.5(693) 96.9(668) 3.6
99/1 85.8(592) 84.0(579) 2.1
40/60 100.7(694) 98.2(677) 2.5
30/70 97.4(672) 91.6(632) 6.0
20/80 91.8(633) 82.7(570) 9.9
50 19/81 91.0(627) 81.7(563) 10.2
5 C-216E/HFC-134
1.0/99.0 76.9(530) 76.3(526) 0.8
50.0/50.0 100.1(690) 98.0(676) 2.1
79.8/20.2 104.4(720) 104.4(720) 0
99.0/1.0 100.8(695) 100.7(694) 0.1
10
C216E/HFC-134a
61.7/38.3 108.0(745) 108.0(745) 0.0
80/20 106.6(735) 106.4(734) 0.2
90/10 104.4(720) 105.0(724) 0.6
15 99/1 100.8(695) 100.7(694) 0.1
50/50 107.6(742) 107.4(741) 0.1
30/70 105.2(725) 104.6(721) 0.2
10/90 101.0(696) 100.4(692) 0.5
1/99 98.6(680) 98.5(679) 0.1
20
C216E/HFC-143
99.0/1.0 101.2(698) 101.0(696) 0.2
91.9/8.1 103.5(714) 103.5(714) 0
61.0/39.0 96.6(666) 87.3(602) 9.6
25
C216E/HFC-152a
77.6/22.4 109.1(752) 109.1(752) 0.0
90/10 107.2(739) 106.7(736) 0.5
99/1 101.4(699) 101.1(697) 0.3
30 70/30 108.7(759) 108.5(748) 0.2
60/40 107.2(739) 106.2(732) 0.9
30/70 99.2(684) 94.8(654) 4.4
20/80 95.4(658) 91.0(627) 4.6
10/90 91.0(627) 87.9(606) 3.4
35 1/99 86.3(595) 86.0(593) 0.3
C216E/HFC-161
58.8/41.2 148.3(1023) 148.3(1023) 0.0
70/30 147.2(1015) 146.3(1009) 0.6
40 80/20 143.3(988) 139.1(959) 2.9
99/1 105.4(727) 102.2(705) 3.0
50/50 147.8(1019) 147.4(1017) 0.3
40/60 146.4(1010) 144.7(998) 1.2
30/70 144.1(994) 140.6(970) 2.4
45 20/80 140.8(971) 136.3(940) 3.2
1/99 130.9(903) 130.4(899) 0.4
C216E/HFC-245cb
95.1/4.9 100.6(694) 100.6(694) 0.0
50 99/1 100.4(692) 100.4(692) 0.0
70/30 96.9(668) 95.6(659) 1.3
5 60/40 94.1(694) 91.8(633) 2.4
50/50 90.8(626) 87.4(603) 3.7
40/60 87.0(600) 87.9(606) 1.0
30/70 82.8(571) 78.3(540) 5.4
20/80 78.0(538) 74.1(511) 5.0
10 1/99 68.0(469) 68.0(469) 0.0
C-216E2/HFC-32
36.0/64.0 272.4(1878) 272.4(1878) 0.0
15.0/85.0 269.3(1857) 256.1(1766) 4.9
15 1.0/99.0 250.4(1726) 246.8(1702) 1.4
60.0/40.0 269.3(1857) 261.3(1802) 3.0
80.0/20.0 250.6(1728) 179.7(1239) 28.3
70.0/30.0 263.9(1820) 238.7(1646) 9.5
71.0/29.0 263.0(1813) 235.0(1620) 10.6
20
C-216E2/HFC-134
60.5/39.5 88.6(611) 88.6(611) 0.0
80.0/20.0 86.7(598) 85.9(592) 0.9
99.0/1.0 77.6(535) 77.3(533) 0.4
25 40.0/60.0 87.2(601) 86.4(596) 0.9
20.0/80.0 83.2(574) 81.4(561) 2.2
1.0/99.0 76.5(527) 76.3(526) 0.3
C-216E2/HFC-134a
30 20.6/79.4 99.0(683) 99.0(683) 0.0
1.0/99.0 98.3(678) 98.3(678) 0.0
50.0/50.0 97.2(670) 96.8(667) 0.4
80.0/20.0 89.6(618) 87.6(604) 2.2
99.0/1.0 77.6(535) 77.3(533) 0.4
35
C-216E2/HFC-143
87.1/12.9 82.9(572) 82.9(572) 0.0
99.0/1.0 78.1(538) 77.5(534) 0.8
50.0/50.0 77.2(532) 55.6(383) 28.0
40 70.0/30.0 80.8(557) 78.5(541) 2.8
60.0/40.0 79.0(545) 73.1(504) 7.5
58.0/42.0 78.7(543) 71.2(491) 9.5
57.0/43.0 78.5(541) 70.1(483) 10.7
45 C-216E2/HFC-152a
60.5/39.5 95.6(659) 95.6(659) 0.0
80.0/20.0 93.2(643) 92.1(635) 1.2
99.0/1.0 78.4(541) 77.7(536) 0.9
40.0/60.0 94.2(649) 93.5(645) 0.7
50 20.0/80.0 90.9(627) 89.5(617) 1.5
1.0/99.0 86.1(594) 85.9(592) 0.2
5
C-216E2/HFC-161
45.7/54.3 138.3(954) 138.3(954) 0.0
20.0/80.0 135.8(936) 134.6(928) 0.9
1.0/99.0 130.6(900) 130.4(899) 0.2
10 60.0/40.0 137.3(947) 136.4(940) 0.7
80.0/20.0 129.0(889) 120.3(829) 6.7
85.0/15.0 123.7(853) 111.0(765) 10.3
84.0/16.0 124.9(861) 113.1(780) 9.4
15 C-216E2/HFC-245cb
74.7/25.3 81.3(561) 81.3(561) 0.0
99.0/1.0 77.2(532) 77.1(532) 0.1
50.0/50.0 79.3(547) 78.6(542) 0.9
20.0/80.0 73.1(504) 71.8(495) 1.8
20 1.0/99.0 67.7(467) 67.6(466) 0.1
218E/HFC-134
99.0/1.0 87.3(602) 84.7(584) 3.0
80.0/20.0 113.8(785) 109.9(758) 3.4
25 63.3/36.7 116.6(804) 116.6(804) 0
50.0/50.0 115.8(798) 114.5(789) 1.1
35.0/65.0 113.5(783) 102.7(708) 9.5
218E/HFC-134a
30 53.0/47.0 122.3(843) 122.3(843) 0.0
70/30 120.2(829) 117.8(812) 2.0
80/20 115.6(797) 109.1(752) 5.6
99/1 86.8(598) 84.7(584) 2.4
40/60 121.5(838) 120.3(830) 1.0
35 30/70 119.6(825) 115.6(797) 3.3
20/80 116.3(802) 108.0(745) 7.1
1/99 99.9(689) 98.4(679) 1.5
218E/HFC-143
40 99.0/1.0 90.6(625) 84.5(583) 6.7
85.3/14.7 103.7(715) 103.7(715) 0
57.0/43.0 102.4(706) 99.0(683) 3.3
218E/HFC-152a
45 68.2/31.8 124.0(855) 124.0(855) 0.0
80/20 112.4(775) 120.0(828) 6.8
99/1 89.5(617) 85.1(587) 4.9
60/40 123.6(852) 123.0(848) 0.5
50/50 122.6(845) 119.5(824) 2.5
50 40/60 121.0(834) 108.5(748) 10.3
41/59 121.2(836) 110.3(761) 9.0
5
218E/HFC-161
62.6/37.4 170.9(1179) 170.9(1179) 0.0
80/20 167.8(1157) 160.2(1105) 4.5
85/15 163.8(1130) 146.4(1010) 10.6
10 84/16 164.9(1137) 149.9(1034) 9.1
60/40 170.9(1179) 170.8(1178) 0.5
38/62 169.4(1168) 152.3(1050) 10.1
39/61 169.5(1169) 156.5(1079) 7.7
15 218E/HFC-263fb
96.3/3.7 84.0(579) 84.0(579) 0.0
99/1 83.9(578) 83.9(578) 0.0
70/30 80.0(552) 78.5(541) 1.9
40/60 71.6(494) 66.1(456) 7.7
20 23/77 65.4(451) 59.1(407) 9.6
24/76 65.8(454) 59.4(409) 9.7
25/75 66.2(456) 60.2(415) 9.6
10/90 59.5(410) 55.5(383) 6.7
1/99 54.6(376) 54.1(373) 0.9
25
218E2/HFC-134
1.0/99.0 77.1(532) 76.2(525) 1.2
20.0/80.0 86.9(599) 83.1(573) 4.4
36.1/53.9 89.6(618) 89.6(618) 0
30 70.0/30.0 86.8(598) 83.0(572) 4.4
79.0/21.0 83.0(572) 74.8(516) 9.9
218E2/HFC-134a
24.7/75.3 101.1(697) 101.1(697) 0.0
35 10/90 100.2(691) 99.9(689) 0.3
1/99 98.5(679) 98.4(679) 0.1
40/60 100.2(691) 99.6(687) 0.6
50/50 98.7(681) 96.8(667) 1.9
70/30 92.0(634) 84.1(580) 8.6
40 73/27 90.2(622) 81.1(559) 10.1
72/28 90.8(626) 82.1(566) 9.6
218E2/HFC-143
91.0/9.0 70.7(487) 65.0(448) 8.1
45 78.3/21.7 72.6(501) 72.6(501) 0
52.0/48.0 71.8(495) 67.5(465) 6.0
218E2/HFC-152a
51.0/49.0 98.1(676) 98.1(676) 0.0
50 70/30 96.4(665) 93.9(647) 2.6
82/18 91.3(630) 82.0(565) 10.2
5 81/19 92.0(634) 83.5(576) 9.2
40/60 97.7(674) 97.1(670) 0.6
30/70 96.7(667) 94.5(652) 2.3
20/80 94.8(654) 90.5(624) 4.5
10/90 91.5(631) 87.3(602) 4.6
10 1/99 86.5(596) 85.9(592) 0.7
218E2/HFC-161
46.4/53.6 145.1(1001) 145.1(1001) 0.0
60/40 144.4(996) 143.2(988) 0.8
15 77/23 139.4(961) 126.7(874) 9.1
78/22 138.8(957) 124.5(859) 10.3
40/60 145.0(1000) 144.7(998) 0.2
30/70 144.3(995) 142.0(979) 1.6
20/80 142.7(984) 135.6(935) 5.0
20 10/90 139.1(959) 131.3(906) 5.6
1/99 131.5(907) 130.2(898) 1.0
218E2/HFC-236fa
89.8/10.2 52.6(362) 52.6(362) 0.0
25 99/1 52.3(360) 52.4(361) 0.2
70/30 51.8(357) 51.6(356) 0.4
60/40 50.8(350) 50.3(347) 1.0
50/50 49.7(342) 48.8(336) 1.8
30/70 46.6(321) 44.9(309) 3.6
30 20/80 44.6(307) 42.9(296) 3.8
10/90 42.2(291) 41.0(282) 2.8
1/99 39.7(273) 39.5(272) 0.5
218E2/HFC-263fb
35 60.5/39.5 57.9(399) 57.9(399) 0.0
70/30 57.7(398) 57.7(398) 0.0
90/10 55.4(382) 55.1(380) 0.5
99/1 52.7(363) 52.6(362) 0.2
50/50 57.7(398) 57.7(398) 0.0
40 30/70 56.7(391) 56.5(389) 0.4
20/80 56.0(386) 56.0(386) 0.0
10/90 55.0(379) 54.8(378) 0.4
1/99 54.1(373) 54.1(373) 0.0
45 C-225eEαβ/HFC-143
55.9/44.1 38.0(262) 38.0(262) 0.0
80.0/20.0 36.7(253) 36.1(249) 1.6
99.0/1.0 31.6(218) 31.4(216) 0.6
20.0/80.0 36.1(249) 35.4(244) 1.9
50 1.0/99.0 33.3(230) 33.2(229( 0.3
5 C-225eEαβ/HFC-236cb
16.7/83.3 33.7(232) 33.7(232) 0.0
1.0/99.0 33.6(232) 33.6(232) 0.0
50.0/50.0 33.3(230) 33.3(230) 0.0
80.0/20.0 32.3(223) 32.2(222) 0.3
10 99.0/1.0 31.2(215) 31.2(215) 0.0
C-225eEαβ/HFC-236ea
91.5/8.5 31.1(214) 31.1(214) 0.0
99.0/1.0 31.1(214) 31.1(214) 0.0
15 60.0/40.0 30.8(212) 30.8(212) 0.0
40.0/60.0 30.4(210) 30.3(209) 0.3
20.0/80.0 29.7(205) 29.6(204) 0.3
1.0/99.0 28.8(199) 28.8(199) 0.0
20 C-225eEαβ/HFC-245cb
22.4/77.6 70.1(483) 70.1(483) 0.0
1.0/99.0 67.7(467) 67.6(466) 0.1
50.0/50.0 67.7(467) 65.7(453) 3.0
60.0/40.0 66.0(455) 61.7(425) 6.5
25 65.0/35.0 65.0(448) 58.5(403) 10.0
227caEαβ/HFC-32
17.9/82.1 253.4(1748) 253.4(1748) 0.0
10/90 252.8(1744) 251.8(1737) 0.4
30 1/99 247.9(1710) 247.1(1705) 0.3
40/60 251.3(1734) 248.0(1711) 1.3
60/40 244.7(1688) 223.4(1541) 8.7
61/39 244.0(1683) 221.0(1524) 9.4
62/38 243.4(1679) 218.2(1505) 10.4
35
227caEαβ/HFC-143
99.0/1.0 43.0(296) 41.8(288) 2.8
95.0/5.0 47.6(328) 44.4(306) 6.7
70.9/29.1 53.7(370) 53.7(370) 0
40 42.0/58.0 52.0(359) 46.9(323) 9.8
227caEαβ/HFC-245cb
8.1/91.9 67.5(465) 67.5(465) 0.0
1/99 67.4(465) 67.4(465) 0.0
45 30/70 66.7(460) 66.5(458) 0.3
50/50 64.5(445) 63.4(437) 1.7
70/30 60.2(415) 56.8(391) 5.6
77/23 57.9(399) 53.2(367) 8.1
80/20 56.6(390) 51.5(355) 9.0
50 82/18 55.8(385) 50.3(347) 9.8
83/17 55.3(381) 49.7(342) 10.1
5
227caEαβ/HFC-272ca
94.3/5.7 41.4(285) 41.4(285) 0.0
99/1 41.4(285) 41.4(285) 0.0
80/20 41.0(282) 41.0(282) 0.0
10 60/40 39.7(273) 39.4(271) 0.8
40/60 38.1(262) 37.6(259) 1.3
20/80 36.4(251) 35.9(247) 1.4
10/90 35.5(245) 35.2(242) 0.8
1/99 34.6(238) 34.6(238) 0.0
15
227caEαβ/HFC-281ea
31.5/68.5 47.4(327) 47.4(327) 0.0
20/80 47.3(326) 47.3(326) 0.0
10/90 47.2(325) 47.2(325) 0.0
20 1/99 47.1(325) 47.1(325) 0.0
50/50 47.2(325) 47.2(325) 0.0
70/30 46.5(320) 46.4(320) 0.2
90/10 44.2(305) 43.9(302) 0.7
99/1 41.7(287) 41.6(287) 0.2
25
227caEαβ/HFC-281fa
84.3/15.7 42.4(292) 42.4(292) 0.0
90/10 42.3(291) 42.3(291) 0.0
99/1 41.5(286) 41.5(286) 0.0
30 60/40 41.6(287) 41.4(285) 0.5
40/60 40.3(278) 40.0(276) 0.7
20/80 39.0(269) 38.7(267) 0.8
10/90 38.4(265) 38.2(263) 0.5
1/99 37.8(260) 37.8(260) 0.0
35
227caEβγ/HFC-32
28.4/71.6 269.7(1860) 269.7(1860) 0.0
10/90 268.6(1853) 247.0(1704) 8.0
1/99 255.3(1761) 246.7(1702) 3.4
40 40/60 269.4(1858) 268.8(1854) 0.2
60/40 266.6(1839) 255.3(1761) 4.2
67/33 263.7(1819) 238.6(1646) 9.5
68/32 263.1(1815) 235.0(1621) 10.6
45 227caEβγ/HFC-134
34.8/65.2 82.7(571) 82.7(571) 0.0
10/90 80.0(552) 78.7(543) 1.6
5/95 78.4(541) 77.3(533) 1.4
1/99 76.6(529) 76.3(527) 0.0
50 50/50 81.9(565) 81.1(560) 1.0
60/40 80.3(554) 77.8(537) 3.1
5 70/30 77.3(533) 72.2(498) 6.6
77/23 74.1(511) 66.7(460) 10.0
76/24 74.6(515) 67.6(466) 9.4
227caEβγ/HFC-134a
10 1.9/98.1 98.3(678) 98.3(678) 0.0
1/99 98.3(678) 98.3(678) 0.0
20/80 97.2(670) 96.9(668) 0.3
30/70 95.8(661) 94.8(654) 1.0
50/50 91.0(627) 87.1(601) 4.3
15 68/32 83.3(574) 74.8(516) 10.2
67/33 83.8(578) 75.6(521) 9.8
227caEβγ/HFC-143
91.0/9.0 63.1(435) 57.4(396) 9.0
20 73.8/26.2 66.2(456) 66.2(456) 0
46.0/54.0 65.1(449) 59.1(407) 9.2
227caEβγ/HFC-152a
38.3/61.7 91.4(630) 91.4(630) 0.0
25 20/80 90.4(623) 89.6(618) 0.9
10/90 88.7(612) 87.6(604) 1.2
1/99 86.1(594) 85.9(592) 0.2
60/40 89.8(619) 88.0(607) 2.0
70/30 87.2(601) 82.7(570) 5.2
30 80/20 82.1(566) 73.1(504) 11
78/22 83.4(575) 75.4(520) 9.6
79/21 82.8(571) 74.3(512) 10.2
227caEβγ/HFC-161
35 34.4/65.6 137.5(948) 137.5(948) 0.0
20/80 136.7(943) 135.6(935) 0.8
10/90 134.7(929) 132.6(914) 1.6
1/99 130.8(902) 130.4(899) 0.3
40/60 134.4(927) 137.3(947) 2.2
40 60/40 135.0(931) 131.0(903) 3.0
72/28 130.2(898) 117.8(812) 9.5
73/27 129.6(894) 116.0(800) 10.4
227caEβγ/HFC-263fb
45 32.9/67.1 54.6(376) 54.6(376) 0.0
20/80 54.5(376) 54.5(376) 0.0
10/90 54.3(374) 54.3(374) 0.0
1/99 54.0(372) 54.0(372) 0.0
50/50 54.4(375) 54.4(375) 0.0
50 70/30 53.4(368) 53.2(367) 0.4
90/10 50.9(351) 50.7(349) 0.4
5 99/1 49.0(338) 48.9(337) 0.2
227caEβγ/HFC-272ca
89.0/11.0 49.6(342) 49.6(342) 0.0
99/1 48.9(337) 48.9(337) 0.0
10 60/40 47.1(325) 46.0(317) 2.3
40/60 44.1(304) 41.3(285) 6.3
30/70 42.2(291) 38.9(268) 7.8
20/80 40.1(276) 36.9(254) 8.0
10/90 37.6(259) 35.4(244) 5.9
15 1/99 34.8(240) 34.6(238) 0.6
80/20 49.3(340) 49.2(339) 0.2
227caEβγ/HFC-281ea
73.1/26.9 54.0(372) 54.0(372) 0.0
20 80/20 53.8(371) 53.8(371) 0.0
90/10 52.6(362) 52.3(360) 0.0
99/1 49.3(340) 49.2(339) 0.6
60/40 53.4(368) 53.4(368) 0.2
40/60 52.0(358) 51.4(354) 0.0
25 30/70 51.0(351) 50.1(345) 1.8
10/90 48.6(335) 48.0(331) 1.2
1/99 47.3(326) 47.2(325) 0.2
227caEβγ/HFC-281fa
30 85.9/14.1 51.0(351) 51.0(351) 0.0
90/10 50.9(351) 50.9(351) 0.0
99/1 49.1(338) 49.1(338) 0.0
70/30 50.0(345) 49.5(341) 1.0
40/60 45.9(316) 43.3(298) 5.7
35 30/70 44.2(305) 41.2(284) 6.8
20/80 42.3(291) 39.6(273) 6.4
10/90 40.1(276) 38.5(265) 4.0
1/99 38.0(262) 37.8(260) 0.5
40 227eaE/HFC-32
30.0/70.0 272.3(1878) 272.3(1878) 0.0
20/80 272.1(1877) 270.9(1869) 0.4
10/90 271.2(1871) 246.7(1702) 9.0
1/99 257.1(1774) 246.7(1702) 4.0
45 50/50 271.4(1872) 268.6(1853) 1.0
60/40 269.6(1860) 259.6(1791) 3.7
68/32 266.4(1838) 240.8(1661) 9.6
69/31 265.8(1834) 237.1(1636) 10.8
50 227eaE/HFC-134
1.0/99.0 76.7(529) 76.3(526) 0.5
5 10.0/90.0 80.9(558) 78.9(544) 2.5
38.2/61.8 84.7(584) 84.7(584) 0
60.0/40.0 82.7(570) 80.7(556) 2.4
78.0/22.0 76.4(527) 69.1(476) 9.6
10 227eaE/HFC-134a
9.3/90.7 98.6(680) 98.6(680) 0.0
1/99 98.3(678) 98.3(678) 0.0
30/70 97.2(670) 96.5(665) 0.7
40/60 95.5(659) 93.8(647) 1.8
15 60/40 89.6(618) 83.9(578) 6.4
70/30 84.6(583) 76.2(525) 9.0
71/29 84.0(579) 75.3(519) 10.4
227eaE/HFC-143
20 92.0/8.0 65.4(451) 59.1(408) 9.6
74.9/25.1 68.9(475) 68.9(475) 0.0
47.0/53.0 67.7(469) 61.7(426) 8.9
80.0/20.0 68.8(475) 68.4(472) 0.6
93.0/7.0 64.6(451) 57.7(398) 10.7
25 60.0/40.0 68.4(446) 67.6(466) 1.2
50.0/50.0 67.9(472) 65.2(450) 4.0
46.0/54.0 67.7(474) 59.0(407) 12.8
227eaE/HFC-152a
30 42.1/57.9 93.2(643) 93.2(643) 0.0
20/80 91.6(632) 90.3(623) 1.4
10/90 89.4(616) 87.8(605) 1.8
1/99 86.2(594) 85.9(592) 0.3
60/40 92.0(634) 90.7(625) 1.4
35 70/30 89.7(618) 85.8(592) 4.3
80/20 84.9(585) 76.5(527) 9.9
81/19 84.2(581) 75.2(518) 10.7
30/70 92.8(640) 92.3(636) 0.5
40 227eaE/HFC-161
37.5/62.5 139.5(962) 139.5(962) 0.0
20/80 138.3(954) 136.4(941) 1.4
10/90 135.8(937) 132.6(914) 2.4
1/99 131.0(903) 130.3(899) 0.5
45 60/40 137.5(948) 134.2(926) 2.4
70/30 134.2(926) 124.8(866) 7.0
73/27 132.6(914) 120.1(828) 9.4
74/26 131.9(910) 118.3(816) 10.3
30/70 139.3(961) 139.0(959) 0.2
50
227eaE/HFC-263fb
5 49.3/50.7 55.7(384) 55.7(384) 0.0
30/70 55.4(382) 55.3(381) 0.2
20/80 55.0(379) 55.0(379) 0.0
10/90 54.6(376) 54.5(376) 0.2
1/99 54.1(373) 54.0(372) 0.2
10 70/30 55.2(380) 55.1(380) 0.2
80/20 54.4(375) 54.3(374) 0.2
90/10 53.2(367) 53.0(365) 0.4
99/1 51.5(355) 51.5(355) 0.0
15 227eaE/HFC-272ca
90.7/9.3 52.0(358) 52.0(358) 0.0
99/1 51.4(354) 51.4(354) 0.0
70/30 50.3(347) 49.6(342) 1.4
50/50 47.3(326) 44.7(308) 5.5
20 35/65 44.5(307) 40.4(278) 9.2
30/70 43.4(299) 39.1(269) 9.9
29/71 43.2(298) 38.8(267) 10.2
80/20 51.4(354) 51.2(353) 0.4
25 227eaE/HFC-281ea
76.8/23.2 55.9(385) 55.9(385) 0.0
90/10 54.9(378) 54.7(377) 0.4
99/1 51.8(357) 51.7(356) 0.2
60/40 55.2(380) 54.8(378) 0.7
30 40/60 53.2(367) 52.1(359) 2.1
30/70 51.9(358) 50.6(349) 2.5
20/80 50.4(347) 49.2(339) 2.4
10/90 48.9(337) 48.1(331) 1.6
1/99 47.3(326) 47.2(325) 0.2
35
227eaE/HFC-281fa
87.6/12.4 53.3(367) 53.3(367) 0.0
99/1 51.7(356) 51.6(356) 0.2
60/40 50.5(348) 48.9(337) 3.2
40 40/60 47.2(325) 43.7(301) 7.4
30/70 45.2(311) 41.4(285) 8.4
20/80 43.0(296) 39.6(273) 7.9
10/90 40.5(279) 38.4(265) 5.2
1/99 38.0(262) 37.8(260) 0.5
45 70/30 51.9(358) 51.2(353) 1.3
C-234fEαβ/HFC-245cb
13.5/86.5 69.9(482) 69.9(482) 0.0
1.0/99.0 67.9(468) 67.7(467) 0.3
50 40.0/60.0 67.6(466) 65.6(452) 3.0
50.0/50.0 66.4(458) 63.6(439) 4.2
5 55.0/45.0 65.9(454) 62.0(427) 5.9
57.0/43.0 65.7(453) 60.7(419) 7.6
58.0/42.0 65.6(452) 59.5(410) 9.3
59.0/41.0 65.5(452) 57.5(396) 12.2
10 C-234fEαβ/HFC-245eb
49.1/50.9 17.6(121) 17.6(121) 0.0
20.0/80.0 17.3(119) 17.3(119) 0.0
1.0/99.0 16.9(117) 16.9(117) 0.0
80.0/20.0 17.3(119) 17.3(119) 0.0
15 99.0/1.0 16.8(116) 16.8(116) 0.0
C-234fEαβ/HFC-356mff
59.0/41.0 18.8(130) 18.8(130) 0.0
80.0/20.0 18.4(127) 18.2(125) 1.1
20 99.0/1.0 16.9(117) 16.8(116) 0.6
40.0/60.0 18.5(128) 18.3(126) 1.1
20.0/80.0 17.3(119) 16.8(116) 2.9
10.0/90.0 16.2(112) 15.7(108) 3.1
1.0/99.0 14.8(102) 14.8(102) 0.0
25
C-234fEαβ/HFC-356mmz
50.1/49.9 20.1(139) 20.1(139) 0.0
20.0/80.0 19.1(132) 18.7(129) 2.1
1.0/99.0 16.8(116) 16.7(115) 0.6
30 80.0/20.0 19.2(132) 18.7(129) 2.6
99.0/1.0 16.9(117) 16.8(116) 0.6
C-234fEβγ/HFC-245cb
10.2/89.8 69.1(476) 69.1(476) 0.0
35 1.0/99.0 67.8(467) 67.7(467) 0.1
40.0/60.0 66.4(458) 64.4(444) 3.0
50.0/50.0 65.4(451) 62.7(432) 4.1
55.0/45.0 65.0(448) 61.0(421) 6.2
58.0/42.0 64.7(446) 52.6(363) 18.7
40 57.0/43.0 64.8(447) 57.9(399) 10.6
56.0/44.0 64.9(447) 60.0(414) 7.6
C-234fEβγ/HFC-245ca
33.6/66.4 14.5(100) 14.5(100) 0.0
45 15.0/85.0 14.4(99) 14.4(99) 0.0
1.0/99.0 14.2(98) 14.2(98) 0.0
60.0/40.0 14.3(99) 14.3(99) 0.0
80.0/20.0 13.9(96) 13.9(96) 0.0
99.0/1.0 13.3(92) 13.3(92) 0.0
50
C-234fEβγ/HFC-245ea
5 36.0/64.0 14.5(100) 14.5(100) 0.0
15.0/85.0 14.4(99) 14.4(99) 0.0
1.0/99.0 14.2(98) 14.2(98) 0.0
60.0/40.0 14.4(99) 14.3(99) 0.7
80.0/20.0 14.0(97) 13.9(96) 0.7
10 99.0/1.0 13.3(92) 13.3(92) 0.0
C-234fEβγ/HFC-254ca
36.0/64.0 13.8(95) 13.8(95) 0.0
15.0/85.0 13.8(95) 13.8(95) 0.0
15 1.0/99.0 13.7(94) 13.7(94) 0.0
60.0/40.0 13.8(95) 13.8(95) 0.0
80.0/20.0 13.6(94) 13.6(94) 0.0
99.0/1.0 13.3(92) 13.3(92) 0.0
20 C-234fEβγ/HFC-356mff
43.1/56.9 17.1(118) 17.1(118) 0.0
20.0/80.0 16.5(114) 16.3(112) 1.2
1.0/99.0 14.8(102) 14.8(102) 0.0
70.0/30.0 16.5(114) 16.0(110) 3.0
25 90.0/10.0 15.0(103) 14.0(97) 6.7
99.0/1.0 13.5(93) 13.3(92) 1.5
C-234fEβγ/HFC-356mmz
35.8/64.2 18.6(128) 18.6(128) 0.0
30 15.0/85.0 18.0(124) 17.8(123) 1.1
1.0/99.0 16.7(115) 16.7(115) 0.0
60.0/40.0 18.1(125) 17.6(121) 2.8
80.0/20.0 16.8(116) 15.3(105) 8.9
85.0/15.0 16.2(112) 14.5(100) 10.5
35 83.0/17.0 16.5(114) 14.8(102) 10.3
82.0/18.0 16.6(114) 15.0(103) 9.6
236caE/HFC-143
60.0/40.0 30.4(210) 27.4(189) 9.9
12.0/88.0 33.4(230) 33.4(231) 0.0
40 10.0/90.0 33.4(230) 33.4(230) 0.0
1.0/99.0 33.1(228) 33.1(228) 0.0
5.0/95.0 33.3(230) 33.3(230) 0.0
30.0/70.0 33.0(228) 33.0(228) 0.0
40.0/60.0 32.4(224) 31.7(219) 2.2
45 61.0/39.0 30.3(209) 27.1(187)10.6
236caE/HFC-245ca
1.0/99.0 14.2(98) 14.2(98) 0.0
10.0/90.0 14.1(97) 14.1(97) 0.0
50 20.0/80.0 14.0(97) 14.0(97) 0.0
30.0/70.0 13.9(96) 13.9(96) 0.0
5 40.0/60.0 13.8(95) 13.7(94) 0.7
50.0/50.0 13.6(94) 13.6(94) 0.0
60.0/40.0 13.5(93) 13.4(92) 0.7
70.0/30.0 13.3(92) 13.3(92) 0.0
80.0/20.0 13.2(91) 13.2(91) 0.0
10 90.0/10.0 13.1(90) 13.0(90) 0.8
99.0/1.0 12.9(89) 12.9(89) 0.0
236caE/HFC-254ca
15 17.6/82.4 13.7(94) 13.7(94) 0.0
10/90 13.7(94) 13.7(94) 0.0
1/99 13.7(94) 13.7(94) 0.0
30/70 13.7(94) 13.7(94) 0.0
50/50 13.6(93) 13.6(93) 0.0
20 70/30 13.4(92) 13.4(92) 0.0
90/10 13.1(90) 13.1(90) 0.0
99/1 13.0(89) 13.0(89) 0.0
40/60 13.7(94) 13.7(94) 0.0
25 236eaEβγ/HFC-143
66.0/34.0 32.1(221) 29.1(201) 9.3
25.9/74.1 34.6(239) 34.6(239) 0
10.0/90.0 34.1(235) 33.9(234) 0.6
1.0/99.0 33.2(229) 33.2(229) 0
30
236eaEβγ/HFC-245ca
1.0/99.0 14.7(101) 14.7(101) 0.0
10.0/90.0 15.0(103) 15.0(103) 0.0
20.0/80.0 15.4(106) 15.3(105) 0.6
35 30.0/70.0 15.6(108) 15.6(108) 0.0
40.0/60.0 15.8(109) 15.8(109) 0.0
50.0/50.0 16.0(110) 16.0(110) 0.0
60.0/40.0 16.1(111) 16.1(111) 0.0
69.1/30.9 16.1(111) 16.1(111) 0.0
40 80.0/20.0 16.1(111) 16.1(111) 0.0
90.0/10.0 15.9(110) 15.9(110) 0.0
99.0/1.0 15.7(108) 15.7(108) 0.0
236eaEβγ/HFC-263ca
45 4.1/95.9 18.2(125) 18.2(125) 0.0
1/99 18.2(125) 18.2(125) 0.0
30/70 18.1(124) 18.1(124) 0.0
50/50 17.9(123) 17.8(122) 0.6
70/30 17.3(119) 17.2(118) 0.6
50 90/10 16.4(113) 16.3(112) 0.6
99/1 15.8(109) 15.8(109) 0.0
5
236eaEβγ/HFC-338mf
92.6/7.4 16.2(111) 16.1(111) 0.6
99/1 15.8(109) 15.7(108) 0.6
70/30 17.4(120) 17.2(118) 1.1
10 50/50 18.1(124) 18.0(124) 0.6
40/60 18.4(127) 18.4(127) 0.0
30/70 18.6(128) 18.6(128) 0.0
10/90 18.8(129) 18.8(129) 0.0
1/99 18.8(129) 18.8(129) 0.0
15
236eaEβγ/HFC-356mff
1.0/99.0 14.9(103) 14.9(103) 0.0
10.0/90.0 15.1(104) 15.1(104) 0.0
20.0/80.0 15.2(105) 15.2(105) 0.0
20 30.0/70.0 15.3(106) 15.3(106) 0.0
40.0/60.0 15.4(106) 15.4(106) 0.0
50.0/50.0 15.5(107) 15.5(107) 0.0
60.0/40.0 15.6(108) 15.6(108) 0.0
70.0/30.0 15.6(108) 15.6(108) 0.0
25 80.0/20.0 15.7(108) 15.7(108) 0.0
90.0/10.0 15.7(108) 15.7(108) 0.0
96.9/3.1 15.7(108) 15.7(108) 0.0
99.0/1.0 15.7(108) 15.7(108) 0.0
30 236eaEβγ/HFC-356mmz
15.1/84.9 16.6(114) 16.6(114) 0.0
1/99 16.6(114) 16.6(114) 0.0
30/70 16.6(114) 16.6(114) 0.0
50/50 16.5(113) 16.5(113) 0.0
35 70/30 16.2(111) 16.2(111) 0.0
90/10 15.9(109) 15.9(109) 0.0
99/1 15.7(108) 15.7(108) 0.0
236faE/HFC-32
40 8.5/91.5 248.6(1715) 248.6(1715) 0.0
1/99 247.2(1705) 247.0(1704) 0.1
20/80 247.5(1707) 246.5(1700) 0.4
40/60 243.5(1680) 236.4(1631) 2.9
50/50 240.0(1656) 224.0(1545) 6.7
45 55/45 237.3(1637) 213.8(1475) 9.9
56/44 236.7(1633) 211.3(1458) 10.7
5 236faE/HFC-143
84.0/16.0 42.2(291) 38.2(264) 9.5
56.9/43.1 45.1(311) 45.1(311) 0.0
30.0/70.0 43.8(302) 40.4(279) 7.8
28.0/72.0 43.6(301) 39.5(272) 9.4
10 40.0/60.0 44.6(308) 43.6(301) 2.2
27.0/73.0 43.5(300) 39.0(269) 10.3
70.0/30.0 44.6(308) 43.9(303) 1.6
80.0/20.0 43.2(298) 40.5(280) 6.3
86.0/14.0 41.4(286) 37.0(255) 10.6
15 85.0/15.0 41.8(288) 37.6(259) 10.0
236faE/HFC-272ca
27.8/72.2 34.8(240) 34.8(240) 0.0
10/90 34.7(239) 34.7(239) 0.0
20 1/99 34.5(238) 34.5(238) 0.0
40/60 34.7(239) 34.7(239) 0.0
60/40 34.2(236) 34.1(235) 0.3
70/30 33.7(232) 33.5(231) 0.6
90/10 31.6(218) 31.3(216) 0.9
25 99/1 29.8(205) 29.8(205) 0.0
236faE/HFC-272fb
82.3/17.7 30.2(208) 30.2(208) 0.0
99/1 29.7(204) 29.7(204) 0.0
30 70/30 30.0(207) 30.0(207) 0.0
50/50 29.3(202) 29.2(201) 0.3
40/60 28.9(199) 28.6(197) 1.0
30/70 28.3(195) 28.0(193) 1.1
20/80 27.7(191) 27.5(189) 0.7
35 10/90 27.1(187) 26.9(185) 0.7
1/99 26.5(182) 26.5(182) 0.0
236faE/HFC-281fa
9.3/90.7 37.7(260) 37.7(260) 0.0
40 1/99 37.7(260) 37.7(260) 0.0
20/80 37.7(260) 37.7(260) 0.0
40/60 37.4(258) 37.4(258) 0.0
60/40 36.6(252) 36.4(251) 0.5
70/30 35.9(247) 35.6(245) 0.8
45 80/20 34.8(240) 34.2(236) 1.7
90/10 32.9(227) 32.3(222) 1.8
99/1 30.0(207) 29.9(206) 0.3
245faEβγ/HFC-356mff
50 1.0/99.0 14.9(103) 14.9(103) 0.0
4.4/95.6 14.9(103) 14.9(103) 0.0
10.0/90.0 14.9(103) 14.9(103) 0.0
20.0/80.0 14.8(102) 14.8(102) 0.0
30.0/70.0 14.7(101) 14.7(101) 0.0
40.0/60.0 14.6(100) 14.6(100) 0.0
50.0/50.0 14.4(99) 14.3(99) 0.7
60.0/40.0 14.2(98) 14.1(97) 0.7
70.0/30.0 13.9(96) 13.8(95) 0.7
80.0/20.0 13.6(93) 13.4(93) 1.5
90.0/10.0 13.2(91) 13.1(90) 0.8
99.0/1.0 12.8(88) 12.7(88) 0.8
实施例3
制冷性能
下表显示出各种组合物的制冷性能。除所指出的地方外,所有数据均基于以下条件:
蒸发器温度 45.0°F(72℃)
冷凝器温度 130.0°F(54.4℃)
低温冷却温度 15°F
回气温度 65.0°F(18.3℃)
压缩机效率为75%。
表4
Evap. Cond. Capacity
Refrig. Press. Press. Comp.Dis. BTU/min
Comp. Psia(kPa) Psia(kPa) Temp.°F(℃) COP (kw)
HCFC-22 90.6(625) 312.6(2155) 212.8(100.4) 3.41 351.3(6.2)
125E/HFC-32
实施例4
下表显示出各种组合物的制冷性能。数据基于以下条件:
蒸发器温度 40.0°F(4.4℃)
冷凝器温度 100.0°F(37.8℃)
压缩机效率为75%
回气温度 60.0°F
5.0/95.0 16.4(113) 49.4(341) 113.0(45.0) 5.31 85.7(1.5)
95.0/5.0 6.0(41) 22.0(152) 107.9(42.2) 5.53 38.5(0.7)
245faEβγ/HFC-272ea
5.0/95.0 9.4(65) 30.9(213) 118.9(48.3) 5.55 56.0(1.0)
95.0/5.0 5.6(39) 21.2(146) 107.5(41.9) 5.40 35.7(0.6)
245faEβγ/HFC-272fb
5.0/95.0 12.2(84) 38.9(268) 117.8(47.7) 5.46 69.4(1.2)
95.0/5.0 5.8(40) 21.5(148) 107.3(41.8) 5.50 37.2(0.7)
245faEβγ/HFC-281ea
5.0/95.0 23.1(159) 65.9(454) 118.1(47.8) 5.45 117.8(2.1)
95.0/5.0 6.5(45) 23.6(163) 110.5(43.6) 5.60 42.0(0.7)
245faEβγ/HFC-281fa
5.0/95.0 18.1(125) 53.9(372) 117.9(47.7) 5.48 97.0(1.7)
95.0/5.0 6.3(43) 22.9(158) 109.3(42.9) 5.55 40.2(0.7)
实施例5
下表显示出各种组合物的制冷性能。数据基于以下条件:
蒸发器温度 10.0°F(-12.2℃)
冷凝器温度 90.0°F(32.2℃)
回气温度 30.0°F(-1.1℃)
压缩机效率为75%。
表6
Evap. Cond. 能力
Refrig. Press. Press. Comp.Dis. BTU/min
Comp. Psia(kPa) Psia(kPa) Temp.°F(℃) COP (kw)
HCFC-22 47.9(330) 183.6(1266) 179.1(81.7) 3.62 217.7(3.8)
116E/HFC-32
5.0/95.0 16.7(115) 68.0(469) 132.1(55.6) 4.17 88.8(1.6)
95.0/5.0 89.7(618) 287.7(1983) 103.1(39.5) 3.08 266.6(4.7)
116E/HFC-281fa
5.0/95.0 14.0(96) 57.7(398) 129.9(54.4) 4.39 78.9(1.4)
95.0/5.0 85.8(591) 273.8(1887) 110.5(43.6) 2.99 249.5(4.4)
实施例6
下表显示出各种组合物的制冷性能。数据基于以下条件:
蒸发器温度 40.0°F(4.4℃)
冷凝器温度 100.0°F(37.8℃)
低温冷却温度 0°F(-17.8℃)
回气温度 40.0°F(4.4℃)
压缩机效率为75%。
表7
Evap. Cond. 能力
Refrig. Press. Press. Comp.Dis. BTU/min
Comp. Psia(kPa) Psia(kPa) Temp.°F(℃) COP (kw)
236eaEβγ/HFC-245ca
69.1/30.9 6.8(47) 25.2(174) 101.5(38.6) 5.32 42.1(0.7)
236caE/HFC-245ca
16.1/83.9 6.1(42) 23.3(161) 108.3(42.3) 5.41 39.6(0.7)
236eaEβγ/HFC-356mff*
96.9/3.1 6.8(47) 25.2(174) 113.4(45.2) 5.11 40.4(0.7)
*回气温度=55.0°F(12.8℃)
245faEβγ/HFC-356mff*
4.4/95.6 6.5(45) 23.2(160) 108.5(42.5) 5.04 36.8(0.6)
*回气温度=55.0°F(12.8℃)
下列化合物有指示HGWP(所有HGWP值均相对于CFC-11=1.0)。HGWP相对于CFC-11的HGWP被测定如下:
HGWP=(IR吸收(A)/IR吸收(CFC-11))×
(t(A)/t(CFC-11))×
(质量(CFC-11)/质量(A))
这里A是被分析气体;
IR吸收为在研究区域中截面的总红外吸收,即这里水和CO2不吸收;
t=大气的生存时间;以及
质量=原子质子
化合物 HGWP
HFC-125 0.84
HFC-134 ≈0.28
HFC-134a 0.28
HFC-143a 1.1
FC-218 >10
134E ≈0.1
143aE ≈0.2
制备氟代醚和HFC的组合物并且组合物具指示HGWP。
组合物 HGWP
(wt.%/wt/%)
134E/HFC-125 0.25
(80.0/20.0)
134E/HFC-125 0.5
(46.0/54.0)
134E/HFC-134 0.14
(80.0/20.0)
134E/HFC-134a 0.14
(80.0/20.0)
134E/HFC-143a 0.3
(80.0/20.0)
143aE/HFC-125 0.33
(80.0/20.0)
143aE/HFC-143a 0.38
(80.0/20.0)
143aE/HFC-125 0.5
(53.0/47.0)
143aE/HFC-134 0.22
(80.0/20.0)
143aE/HFC-134a 0.22
(80.0/20.0)
本发明包括共沸或类共沸物组合物的新组合物可以通过在待冷却物体附近冷凝该组合物然后再蒸发冷凝液来产生制冷作用。新组合物也可以用来产生热,这是通过在待加热的物体附近冷凝制冷剂然后再将制冷剂蒸发来完成的。
除制冷应用外,本发明新的恒沸或基本上恒沸的组合物也可以用作气雾剂推进剂、热交换介质、气体电介质、灭火剂、聚乙烯和聚氨基甲酸乙酯的膨胀剂和动力循环工作流体。
也可以将添加剂如润滑剂,腐蚀抑制剂、稳定剂、染料和其它适当的东西加到本发明新的组合物中以用于多种用途,但条件是:它们对组合物的预期的应用没有不利的影响。优选的润滑剂包括分子量在250以上的酯类。
Claims (4)
1、制冷剂组合物,包括:
(a)式CaFbH2a+2-bO它的环或无环氟代醚或CF3OCF2CF3,式中a=2或3并且b=3、4、6、7或8以及当a=3时b=5;和
(b)式CnFmH2n+2-m的氟代烃,式中1≤n≤4和1≤m≤8。
2、由重量百分数为1-49的CHF2OCF3和重量百分数为51-99的式CnFmH2n+2-m氟代烃组成的制冷剂组合物,式中1≤n≤4并且1≤m≤8。
3、含有效量以下化合物生成的共沸或类共沸物组合物。
amounts of:| 116E和
HFC-32,HFC-41,HFC-125,HFC-134,HFC-134a,HFC-143,HFC-143a,HFC-152a或HFC-161;125E和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a或HFC-161;134E和HFC-143,HFC-227ca,HFC-227ea,HFC-236ca,HFC-236cb,HFC-236ea,HFC-236fa,HFC-245cb,HFC-254cb,HFC-254eb,HFC-338mf或HFC-356mff;134aE和HFC-143,HFC-227ca,HFC-227ea或HFC-245cb;143aE和HFC-32,HFC-134,HFC-143a,HFC-152a,HFC-227ca,HFC-227ea或HFC-245cb;C216E和
HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161或HFC-245cb;C-216E2和
HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161,和
HFC-245cb;218E和
HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161或HFC-263fb;218E2和
HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161,HFC-236fa或HFC-263fb;C-225eEαβ和HFC-143,HFC-236cb,HFC-236ea,和HFC-245cb;227caEαβ和HFC-32,HFC-143,HFC-245cb,HFC-272ca,HFC-281ea或HFC-281fa;227caEβγ和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161,HFC-263fb,HFC-272ca,HFC-281ea或HFC-281fa;227eaE和HFC-32,HFC-134,HFC-134a,HFC-143,HFC-152a,HFC-161,HFC-263fb,HFC-272ca,HFC-281ea或HFC-281fa;236caE和HFC-143,HFC-245ca或HFC-254ca;C-234fEαβ和HFC-245cb,HFC-245eb,HFC-356mff和HFC-356mmz;C-234fEβγ和HFC-245ca,HFC-245cb,HFC-245ea,HFC-254ca或HFC-356mmz;236eaEβγ和HFC-143,HFC-245ca,HFC-263ca,HFC-338mf,HFC-356mff或HFC-356mmz;236faE和HFC-32,HFC-143,HFC-272ca,HFC-272fb or HFC-281fa;或245faEβγ和HFC-356mff或HFC-356mmz
azeotropic or azeotrope-like composition.
4、含有效量的第一成分和第二成分的组合物,其中第一成分包括氟代烃,并且第二成分包括氟代醚并且其卤化碳全球变暖能力小于第一成分的卤化碳全球变暖能力,这样就使组合物的卤化碳全球变暖能力低于第一成分的卤化碳全球变暖能力。
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US89050892A | 1992-05-28 | 1992-05-28 | |
US890,508 | 1992-05-28 | ||
US95499992A | 1992-10-01 | 1992-10-01 | |
US954,999 | 1992-10-01 | ||
US026,714 | 1993-03-05 | ||
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CN1082088A true CN1082088A (zh) | 1994-02-16 |
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CN93106759A Pending CN1082088A (zh) | 1992-05-28 | 1993-05-28 | 氟代醚和氟代烃组合物 |
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EP (1) | EP0642560B1 (zh) |
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1993
- 1993-03-05 US US08/026,714 patent/US5605882A/en not_active Expired - Fee Related
- 1993-05-14 TW TW082103785A patent/TW263527B/zh active
- 1993-05-20 BR BR9306614A patent/BR9306614A/pt not_active Application Discontinuation
- 1993-05-20 AU AU42500/93A patent/AU4250093A/en not_active Abandoned
- 1993-05-20 CA CA002136180A patent/CA2136180A1/en not_active Abandoned
- 1993-05-20 WO PCT/US1993/004614 patent/WO1993024586A1/en active IP Right Grant
- 1993-05-20 AT AT93911325T patent/ATE177137T1/de not_active IP Right Cessation
- 1993-05-20 EP EP93911325A patent/EP0642560B1/en not_active Expired - Lifetime
- 1993-05-20 DE DE69323743T patent/DE69323743T2/de not_active Expired - Fee Related
- 1993-05-20 JP JP6500589A patent/JPH07507342A/ja not_active Ceased
- 1993-05-20 ES ES93911325T patent/ES2130267T3/es not_active Expired - Lifetime
- 1993-05-27 MX MX9303120A patent/MX9303120A/es not_active Application Discontinuation
- 1993-05-28 CN CN93106759A patent/CN1082088A/zh active Pending
-
1995
- 1995-06-07 US US08/476,821 patent/US5648016A/en not_active Expired - Fee Related
-
1997
- 1997-06-09 US US08/871,312 patent/US5779931A/en not_active Expired - Fee Related
-
1998
- 1998-04-16 US US09/533,557 patent/US6416683B1/en not_active Expired - Fee Related
-
2002
- 2002-04-19 US US10/126,033 patent/US6632376B2/en not_active Expired - Fee Related
-
2003
- 2003-06-05 US US10/455,065 patent/US6835321B2/en not_active Expired - Fee Related
- 2003-06-05 US US10/455,040 patent/US6830703B2/en not_active Expired - Fee Related
-
2004
- 2004-06-18 US US10/871,174 patent/US6905630B2/en not_active Expired - Fee Related
-
2005
- 2005-03-07 JP JP2005062904A patent/JP2005226075A/ja not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US20030052301A1 (en) | 2003-03-20 |
US5779931A (en) | 1998-07-14 |
US6830703B2 (en) | 2004-12-14 |
US20030211956A1 (en) | 2003-11-13 |
ATE177137T1 (de) | 1999-03-15 |
WO1993024586A1 (en) | 1993-12-09 |
DE69323743D1 (de) | 1999-04-08 |
US6835321B2 (en) | 2004-12-28 |
DE69323743T2 (de) | 1999-09-09 |
CA2136180A1 (en) | 1993-12-09 |
JPH07507342A (ja) | 1995-08-10 |
TW263527B (zh) | 1995-11-21 |
US20030224957A1 (en) | 2003-12-04 |
JP2005226075A (ja) | 2005-08-25 |
EP0642560B1 (en) | 1999-03-03 |
MX9303120A (es) | 1994-06-30 |
US20040235701A1 (en) | 2004-11-25 |
EP0642560A1 (en) | 1995-03-15 |
US6632376B2 (en) | 2003-10-14 |
US5605882A (en) | 1997-02-25 |
US6416683B1 (en) | 2002-07-09 |
AU4250093A (en) | 1993-12-30 |
BR9306614A (pt) | 1998-12-08 |
US5648016A (en) | 1997-07-15 |
ES2130267T3 (es) | 1999-07-01 |
US6905630B2 (en) | 2005-06-14 |
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