CN101415793B - 包含氟烯烃的组合物 - Google Patents

包含氟烯烃的组合物 Download PDF

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Publication number
CN101415793B
CN101415793B CN200680054110XA CN200680054110A CN101415793B CN 101415793 B CN101415793 B CN 101415793B CN 200680054110X A CN200680054110X A CN 200680054110XA CN 200680054110 A CN200680054110 A CN 200680054110A CN 101415793 B CN101415793 B CN 101415793B
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hfc
weight
composition
trans
refrigeration
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CN101415793A (zh
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B·H·米诺尔
V·N·M·劳
D·B·比文斯
D·珀蒂
M·S·邦查尔克
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority claimed from US11/393,109 external-priority patent/US20060243945A1/en
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Abstract

本发明涉及用在制冷、空调和热泵系统中的组合物,其中该组合物包含氟烯烃和至少一种其它组分。本发明的组合物可用在制冷或制热方法中、用作传热流体、发泡剂、气溶胶推进剂和抑火和灭火剂。

Description

包含氟烯烃的组合物
发明背景
1.发明领域
本发明涉及用在制冷、空调和热泵系统中的组合物,其中该组合物包含氟烯烃和至少一种其它组分。本发明的组合物可用在制冷或制热方法中、用作传热流体、发泡剂、气溶胶推进剂和抑火和灭火剂。
2.相关技术描述
制冷工业过去几十年一直在寻找因蒙特利尔协定而逐步淘汰的消耗臭氧的氯氟烃(CFC)和氢氯氟烃(HCFC)的替代制冷剂。多数制冷剂制造商的解决方案是氟代烃(HFC)制冷剂的商业化。新型HFC制冷剂,此时最广泛使用的HFC-134a,具有0臭氧损耗潜势(ozone depletionpotential)并因此不受蒙特利尔协定引发的当前规章规定的逐步淘汰的影响。
进一步的环境规章可能最终造成某些HFC制冷剂的全球逐步淘汰。目前,汽车工业面临与汽车空调中所用的制冷剂的全球变暖潜势相关的规章。因此,汽车空调市场当前非常需要找出具有降低的全球变暖潜势的新型制冷剂。如果这些规章在将来更广泛地应用,则制冷和空调工业的所有领域中可用的制冷剂会面临更大的要求。
目前提出的对HFC-134a的替代制冷剂包括HFC-152a、纯烃,如丁烷或丙烷,或“天然”制冷剂,如CO2。许多这些被推荐的替代物是有毒的、易燃的,和/或具有低能量效率。因此,需要新型的替代制冷剂。
本发明的目的是提供新型制冷剂组合物和传热流体组合物,它们提供独特的特性以符合低或0臭氧损耗潜势和与现有制冷剂相比更低的全球变暖潜势的要求。
发明简述
本发明涉及包含HFC-1225ye和NH3的组合物。
本发明进一步涉及包含HFC-1234ze和NH3的组合物。
发明详述
本发明涉及包含至少一种氟烯烃的组合物。本发明的组合物进一步包含至少一种附加组分,其可以是第二氟烯烃、氟代烃(HFC)、烃、二甲醚、双(三氟甲基)硫化物、CF3I或CO2。本发明组合物的氟烯烃化合物和其它组分列在表1中。
表1
 
化合物 化学名称 化学式
HFC-1225ye 1,2,3,3,3-五氟丙烯 CF3CF=CHF
HFC-1234ze 1,3,3,3-四氟丙烯 CF3CH=CHF
HFC-1234yf 2,3,3,3-四氟丙烯 CF3CF=CH2
HFC-1234ye 1,2,3,3-四氟丙烯 CHF2CF=CHF
HFC-1243zf 3,3,3-三氟丙烯 CF3CH=CH2
HFC-32 二氟甲烷 CH2F2
HFC-125 五氟乙烷 CF3CHF2
HFC-134 1,1,2,2-四氟乙烷 CHF2CHF2
HFC-134a 1,1,1,2-四氟乙烷 CH2FCF3
HFC-143a 1,1,1-三氟乙烷 CH3CF3
HFC-152a 1,1-二氟乙烷 CHF2CH3
HFC-161 氟乙烷 CH3CH2F
HFC-227ea 1,1,1,2,3,3,3-七氟丙烷 CF3CHFCF3
HFC-236ea 1,1,1,2,3,3-六氟丙烷 CF3CHFCHF2
HFC-236fa 1,1,1,3,3,3-六氟乙烷 CF3CH2CF3
HFC-245fa 1,1,1,3,3-五氟丙烷 CH3CH2CHF2
HFC-365mfc 1,1,1,3,3-五氟丁烷 CF3CH2CH2CHF2
丙烷 CH3CH2CH3
正丁烷 CH3CH2CH2CH3
异丁烷 异丁烷 CH3CH(CH3)CH3
2-甲基丁烷 CH3CH(CH3)CH2CH3
正戊烷 CH3CH2CH2CH2CH3
 
环戊烷 环-(CH2)5-
DME 二甲醚 CH3OCH3
CO2 二氧化碳 CO2
CF3SCF3 双(三氟甲基)硫醚 CF3SCF3
三氟碘甲烷 CF3I
R717 NH3
表1中列出的各组分可以通过本领域已知的方法制备。
本发明的组合物中所用的氟烯烃化合物HFC-1225ye、HFC-1234ze和HFC-1234ye可以作为不同的构型异构体或立体异构体存在。本发明旨在包括所有单一的构型异构体、单一的立体异构体或其任何组合或混合物。例如,1,3,3,3-四-氟丙烯(HFC-1234ze)意在代表顺式-异构体、反式-异构体或这两种异构体的任何比率的任何组合或混合物。另一实例是HFC-1225ye,其代表顺式-异构体、反式-异构体或这两种异构体的任何比率的任何组合或混合物。本发明的组合物主要含有HFC-1225ye的顺式或Z异构体。
本发明的组合物包括下列:
HFC-1225ye和至少一种选自HFC-1234ze、HFC-1234yf、HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-245fa、HFC-365mfc、丙烷、正丁烷、异丁烷、2-甲基丁烷、正戊烷、环戊烷、二甲基醚、CF3SCF3、CO2、NH3和CF3I的化合物;
HFC-1234ze和至少一种选自HFC-1234yf、HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-245fa、HFC-365mfc、丙烷、正丁烷、异丁烷、2-甲基丁烷、正戊烷、环戊烷、二甲基醚、CF3SCF3、CO2和CF3I的化合物;
HFC-1234yf和至少一种选自HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-245fa、HFC-365mfc、丙烷、正丁烷、异丁烷、2-甲基丁烷、正戊烷、环戊烷、二甲基醚、CF3SCF3、CO2、NH3和CF3I的化合物;
HFC-1243zf和至少一种选自HFC-1234ye、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-245fa、HFC-365mfc、丙烷、正丁烷、异丁烷、2-甲基丁烷、正戊烷、环戊烷、二甲基醚、CF3SCF3、CO2和CF3I的化合物;和
HFC-1234ye和至少一种选自HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-245fa、HFC-365mfc、丙烷、正丁烷、异丁烷、2-甲基丁烷、正戊烷、环戊烷、二甲基醚、CF3SCF3、CO2和CF3I的化合物。
在氟烯烃以大约1重量%至大约99重量%,优选大约20重量%至大约99重量%,更优选大约40重量%至大约99重量%且再更优选大约50重量%至大约99重量%存在时,本发明的组合物通常可用。
本发明进一步提供了如表2中所列的组合物。
表2
Figure G200680054110XD00041
Figure G200680054110XD00051
Figure G200680054110XD00061
Figure G200680054110XD00071
Figure G200680054110XD00081
Figure G200680054110XD00091
Figure G200680054110XD00111
Figure G200680054110XD00121
Figure G200680054110XD00131
表2中所列的本发明的最优选组合物通常在各组分以所列值+/-2重量%的浓度存在时预计保持所需性质和功能。含有CO2的组合物在CO2以所列浓度+/-0.2重量%存在时预计保持所需性质和功能。
本发明的组合物可以是共沸或近共沸的组合物。共沸组合物是指两种或更多种物质的表现为单一物质的恒沸混合物。共沸组合物的一种表征方式在于,通过液体的部分蒸发或蒸馏产生的蒸气具有与用于蒸发或蒸馏的液体相同的组成,即该混合物在无组成变化的情况下蒸馏/回流。恒沸组合物的特征在于共沸,因为它们与相同化合物的非共沸混合物相比表现出最大或最小沸点。共沸组合物在制冷或空调系统内在运行过程中不分馏,这可能降低该系统的效率。另外,共沸组合物在从制冷或空调系统中泄漏时不分馏。在混合物的一种组分可燃的情况下,泄漏过程中的分馏会在该系统内或该系统外产生可燃组合物。
近共沸组合物(通常也称作“类共沸物的组合物”)是两种或多种物质的基本表现为单一物质的基本恒沸的液体混合物。近共沸组合物的一种表征方式在于,通过液体的部分蒸发或蒸馏产生的蒸气具有与用于蒸发或蒸馏的液体相同的组成,即该混合物在基本无组成变化的情况下蒸馏/回流。近共沸组合物的另一表征方式在于,该组合物在特定温度下的泡点蒸气压和露点蒸气压基本相同。在此,如果在例如通过蒸发或煮沸除去50重量%的组合物后,原始组合物和除去50重量%原始组合物后留下的组合物之间的蒸气压差小于大约10%,则该组合物是近共沸的。
在指定温度下的本发明的共沸组合物显示在表3中。
表3
 
组分A 组分B Wt%A Wt%B Psia kPa T(C)
HFC-1234yf HFC-32 7.4 92.6 492 339 -25
HFC-1234yf HFC-125 10.9 89.1 40.7 281 -25
HFC-1234yf HFC-134a 70.4 29.6 18.4 127 -25
HFC-1234yf HFC-152a 91.0 9.0 17.9 123 -25
 
HFC-1234yf HFC-143a 17.3 82.7 39.5 272 -25
HFC-1234yf HFC-227ea 84.6 15.4 18.0 124 -25
HFC-1234yf 丙烷 51.5 48.5 33.5 231 -25
HFC-1234yf 正丁烷 98.1 1.9 17.9 123 -25
HFC-1234yf 异丁烷 88.1 11.9 19.0 131 -25
HFC-1234yf DME 53.5 46.5 13.1 90 -25
HFC-1225ye 反式-HFC-1234ze 63.0 37.0 11.7 81 -25
HFC-1225ye HFC-1243zf 40.0 60.0 13.6 94 -25
HFC-1225ye HFC-134 52.2 47.8 12.8 88 -25
HFC-1225ye HFC-152a 7.3 92.7 14.5 100 -25
HFC-1225ye 丙烷 29.7 70.3 30.3 209 -25
HFC-1225ye 正丁烷 89.5 10.5 12.3 85 -25
HFC-1225ye 异丁烷 79.3 20.7 13.9 96 -25
HFC-1225ye DME 82.1 17.9 10.8 74 -25
HFC-1225ye CF3SCF3 37.0 63.0 12.4 85 -25
反式-HFC-1234ze HFC-1243zf 17.0 83.0 13.0 90 -25
反式-HFC-1234ze HFC-134 45.7 54.3 12.5 86 -25
反式-HFC-1234ze HFC-134a 9.5 90.5 15.5 107 -25
反式-HFC-1234ze HFC-152a 21.6 78.4 14.6 101 -25
反式-HFC-1234ze HFC-227ea 59.2 40.8 11.7 81 -25
反式-HFC-1234ze 丙烷 28.5 71.5 30.3 209 -25
反式-HFC-1234ze 正丁烷 88.6 11.4 11.9 82 -25
反式-HFC-1234ze 异丁烷 77.9 22.1 12.9 89 -25
反式-HFC-1234ze DME 84.1 15.9 10.8 74 -25
反式-HFC-1234ze CF3SCF3 34.3 65.7 12.7 88 -25
HFC-1243zf HFC-134 63.0 37.0 13.5 93 -25
HFC-1243zf HFC-134A 25.1 74.9 15.9 110 -25
HFC-1243zf HFC-152A 40.7 59.3 15.2 104 -25
HFC-1243zf HFC-227ea 78.5 21.5 13.1 90 -25
HFC-1243zf 丙烷 32.8 67.2 31.0 213 -25
HFC-1243zf 正丁烷 90.3 9.7 13.5 93 -25
 
HFC-1243zf 异丁烷 80.7 19.3 14.3 98 -25
HFC-1243zf DME 72.7 27.3 12.0 83 -25
顺式-HFC-1234ze HFC-236ea 20.9 79.1 30.3 209 25
顺式-HFC-1234ze HFC-245fa 76.2 23.8 26.1 180 25
顺式-HFC-1234ze 正丁烷 51.4 48.6 6.08 42 -25
顺式-HFC-1234ze 异丁烷 26.2 73.8 8.74 60 -25
顺式-HFC-1234ze 2-甲基丁烷 86.6 13.4 27.2 188 25
顺式-HFC-1234ze 正戊烷 92.9 7.1 26.2 181 25
HFC-1234ye HFC-236ea 24.0 76.0 3.35 23.1 -25
HFC-1234ye HFC-245fa 42.5 57.5 22.8 157 25
HFC-1234ye 正丁烷 41.2 58.8 38.0 262 25
HFC-1234ye 异丁烷 16.4 83.6 50.9 351 25
HFC-1234ye 2-甲基丁烷 80.3 19.7 23.1 159 25
HFC-1234ye 正戊烷 877 12.3 21.8 150 25
另外,三元共沸物组合物据发现如表4中所列。
表4
 
组分A 组分B 组分C Wt%A Wt%B Wt%C 压力(psi) 压力(kPa) 温度(℃)
HFC-1234yf HFC-32 HFC-143A 3.9 74.3 21.8 50.02 345 -25
HFC-1234yf HFC-32 异丁烷 1.1 92.1 68 50.05 345 -25
HFC-1234yf HFC-125 HFC-143A 14.4 43.5 42.1 38.62 266 -25
HFC-1234yf HFC-125 异丁烷 97 89.1 1.2 40.81 281 -25
HFC-1234yf HFC-134 丙烷 4.3 39.1 567 34.30 236 -25
HFC-1234yf HFC-134 DME 15.2 67.0 17.8 10.38 71.6 -25
HFC-1234yf HFC-134a 丙烷 24.5 31.1 44.5 34.01 234 -25
HFC-1234yf HFC-134a 正丁烷 60.3 35.2 4.5 18.58 128 -25
HFC-1234yf HFC-134a 异丁烷 48.6 37.2 143 19.86 137 -25
HFC-1234yf HFC-134a DME 24.0 67.9 8.1 17.21 119 -25
HFC-1234yf HFC-143a 丙烷 177 71.0 11.3 40.42 279 -25
 
HFC-1234yf HFC-143a DME 5.7 93.0 1.3 39.08 269 -25
HFC-1234yf HFC-152a 正丁烷 86.6 10.8 2.7 17.97 124 -25
HFC-1234yf HFC-152a 异丁烷 75.3 11.8 12.9 19.12 132 -25
HFC-1234yf HFC-152a DME 24.6 43.3 32.1 11.78 81.2 -25
HFC-1234yf HFC-227ea 丙烷 35.6 17.8 46.7 33.84 233 -25
HFC-1234yf HFC-227ea 正丁烷 81.9 16.0 2.1 18.07 125 -25
HFC-1234yf HFC-227ea 异丁烷 70.2 18.2 11.6 19.27 133 -25
HFC-1234yf HFC-227ea DME 283 55.6 16.1 15.02 104 -25
HFC-1234yf 正丁烷 DME 48.9 4.6 46.4 13.15 90.7 -25
HFC-1234yf 异丁烷 DME 31.2 26.2 42.6 14.19 97.8 -25
HFC-1234yf DME CF3I 16.3 10.0 73.7 15.65 108 -25
HFC-1234yf DME CF3SCF3 34.3 10.5 55.2 14.57 100 -25
HFC-1225ye 反式-HFC-1234ze HFC-134 47.4 5.6 47.0 12.77 88.0 -25
HFC-1225ye 反式-HFC-1234ze HFC-227ea 28.4 52.6 19.0 11.63 80.2 -25
HFC-1225ye 反式-HFC-1234ze 丙烷 20.9 9.1 70.0 30.36 209 -25
HFC-1225ye 反式-HFC-1234ze 正丁烷 65.8 24.1 10.1 12.39 85.4 -25
HFC-1225ye 反式-HFC-1234ze DME 41.0 40.1 18.9 10.98 75.7 -25
HFC-1225ye 反式-HFC-1234ze CF3SCF3 1.0 33.7 65.2 12.66 87.3 -25
HFC-1225ye HFC-1243zf HFC-134 28.7 47.3 24.1 13.80 95.1 -25
HFC-1225ye HFC-1243zf 正丁烷 37.5 55.0 7.5 13.95 96.2 -25
HFC-1225ye HFC-1243zf 异丁烷 40.5 43.2 16.3 14.83 102 -25
HFC-1225ye HFC-1243zf DME 19.1 51.0 29.9 12.15 83.8 -25
HFC-1225ye HFC-1243zf CF3I 10.3 27.3 62.3 14.05 96.9 -25
HFC-1225ye HFC-134 HFC-152a 63.6 26.8 9.6 12.38 85.4 -25
HFC-1225ye HFC-134 HFC-227ea 1.3 52.3 46.4 12.32 84.9 -25
HFC-1225ye HFC-134 正丁烷 18.1 67.1 14.9 14.54 100 -25
HFC-1225ye HFC-134 异丁烷 0.7 74.0 25.3 16.68 115 -25
HFC-1225ye HFC-134 DME 29.8 52.5 17.8 9.78 67.4 -25
HFC-1225ye HFC-227ea DME 63.1 31.0 5.8 10.93 754 -25
HFC-1225ye 正丁烷 DME 66.0 13.0 21.1 11.34 78.2 -25
HFC-1225ye 正丁烷 CF3SCF3 71.3 5.6 23.0 12.25 84.5 -25
 
HFC-1225ye 异丁烷 DME 49.9 29.7 20.4 12.83 88.5 -25
HFC-1225ye 异丁烷 CF3I 27.7 2.2 70.1 13.19 90.9 -25
反式-HFC-1234ze HFC-1243zf HFC-227ea 7.1 73.7 19.2 13.11 90.4 -25
反式-HFC-1234ze HFC-1243zf 正丁烷 9.5 81.2 9.3 13.48 92.9 -25
反式-HFC-1234ze HFC-1243zf 异丁烷 3.3 77.6 19.1 14.26 98.3 -25
反式-HFC-1234ze HFC-1243zf DME 2.6 70.0 27.4 12.03 82.9 -25
反式-HFC-1234ze HFC-134 HFC-152a 52.0 42.9 5.1 12.37 85.3 -25
反式-HFC-1234ze HFC-134 HFC-227ea 30.0 43.2 26.8 12.61 86.9 -25
反式-HFC-1234ze HFC-134 DME 27.7 547 17.7 9.76 67.3 -25
反式-HFC-1234ze HFC-134a HFC-152a 14.4 34.7 51.0 14.42 99.4 -25
反式-HFC-1234ze HFC-152a 正丁烷 5.4 80.5 14.1 15.41 106 -25
反式-HFC-1234ze HFC-152a DME 59.1 16.4 24.5 10.80 74.5 -25
反式-HFC-1234ze HFC-227ea 正丁烷 40.1 48.5 11.3 12.61 86.9 -25
反式-HFC-1234ze 正丁烷 DME 68.1 13.0 18.9 11.29 77.8 -25
反式-HFC-1234ze 正丁烷 CF3I 81.2 9.7 9.1 11.87 81.8 -25
反式-HFC-1234ze 异丁烷 DME 55.5 28.7 15.8 12.38 85.4 -25
反式-HFC-1234ze 异丁烷 CF3I 34.9 6.1 59.0 12.57 86.7 -25
反式-HFC-1234ze 异丁烷 CF3SCF3 37.7 1.1 61.7 12.66 87.3 -25
HFC-1243zf HFC-134 HFC-227ea 58.6 34.1 7.3 13.54 93.4 -25
HFC-1243zf HFC-134 正丁烷 27.5 58.7 13.9 14.72 101 -25
HFC-1243zf HFC-134 DME 18.7 63.5 17.8 10.11 69.7 -25
HFC-1243zf HFC-134 CF3I 11.4 23.9 64.7 14.45 99.6 -25
HFC-1243zf HFC-134a HFC-152a 41.5 21.5 37.1 14.95 103 -25
HFC-1243zf HFC-134A 正丁烷 70 81.4 11.6 17.03 117 -25
HFC-1243zf HFC-152a 丙烷 2.9 34.0 63.0 31.73 219 -25
HFC-1243zf HFC-152a 正丁烷 28.8 60.3 11.0 15.71 108 -25
HFC-1243zf HFC-152a 异丁烷 6.2 68.5 25.3 17.05 118 -25
HFC-1243zf HFC-152a DME 33.1 36.8 30.1 11.41 78.7 -25
HFC-1243zf HFC-227ea 正丁烷 62.0 28.4 9.6 13.67 94.3 -25
HFC-1243zf HFC-227ea 异丁烷 27.9 51.0 21.1 15.00 103 -25
HFC-1243zf HFC-227ea DME 48.1 44.8 7.2 12.78 88.1 -25
 
HFC-1243zf 正丁烷 DME 60.3 10.1 29.6 12.28 84.7 -25
HFC-1243zf 异丁烷 DME 47.1 26.9 25.9 13.16 90.7 -25
HFC-1243zf 异丁烷 CF3I 32.8 1.1 66.1 13.97 96.3 -25
HFC-1243zf DME CF3SCF3 41.1 2.3 56.6 13.60 938 -25
在指定温度下的本发明的近共沸组合物列在表5中。
表5
 
组分A 组分B (wt%A/wt%B) T(C)
HFC-1234yf HFC-32 1-57/99-43 -25
HFC-1234yf HFC-125 1-51/99-49 -25
HFC-1234yf HFC-134 1-99/99-1 -25
HFC-1234yf HFC-134a 1-99/99-1 -25
HFC-1234yf HFC-152a 1-99/99-1 -25
HFC-1234yf HFC-161 1-99/99-1 -25
HFC-1234yf HFC-143a 1-60/99-40 -25
HFC-1234yf HFC-227ea 29-99/71-1 -25
HFC-1234yf HFC-236fa 66-99/34-1 -25
HFC-1234yf HFC-1225ye 1-99/99-1 -25
HFC-1234yf 反式-HFC-1234ze 1-99/99-1 -25
HFC-1234yf HFC-1243zf 1-99/99-1 -25
HFC-1234yf 丙烷 1-80/99-20 -25
HFC-1234yf 正丁烷 71-99/29-1 -25
HFC-1234yf 异丁烷 60-99/40-1 -25
HFC-1234yf DME 1-99/99-1 -25
HFC-1225ye 反式-HFC-1234ze 1-99/99-1 -25
HFC-1225ye HFC-1243zf 1-99/99-1 -25
HFC-1225ye HFC-134 1-99/99-1 -25
HFC-1225ye HFC-134a 1-99/99-1 -25
HFC-1225ye HFC-152a 1-99/99-1 -25
 
HFC-1225ye HFC-161 1-84/99-16,90-99/10-1 -25
HFC-1225ye HFC-227ea 1-99/99-1 -25
HFC-1225ye HFC-236ea 57-99/43-1 -25
HFC-1225ye HFC-236fa 48-99/52-1 -25
HFC-1225ye HFC-245fa 70-99/30-1 -25
HFC-1225ye 丙烷 1-72/99-28 -25
HFC-1225ye 正丁烷 65-99/35-1 -25
HFC-1225ye 异丁烷 50-99/50-1 -25
HFC-1225ye DME 1-99/99-1 -25
HFC-1225ye CF3I 1-99/99-1 -25
HFC-1225ye CF3SCF3 1-99/99-1 -25
反式-HFC-1234ze 顺式-HFC-1234ze 73-99/27-1 -25
反式-HFC-1234ze HFC-1243zf 1-99/99-1 -25
反式-HFC-1234ze HFC-134 1-99/99-1 -25
反式-HFC-1234ze HFC-134a 1-99/99-1 -25
反式-HFC-1234ze HFC-152a 1-99/99-1 -25
反式-HFC-1234ze HFC-161 1-52/99-48,87-99/13-1 -25
反式-HFC-1234ze HFC-227ea 1-99/99-1 -25
反式-HFC-1234ze HFC-236ea 54-99/46-1 -25
反式-HFC-1234ze HFC-236fa 44-99/56-1 -25
反式-HFC-1234ze HFC-245fa 67-99/33-1 -25
反式-HFC-1234ze 丙烷 1-71/99-29 -25
反式-HFC-1234ze 正丁烷 62-99/38-1 -25
反式-HFC-1234ze 异丁烷 39-99/61-1 -25
反式-HFC-1234ze DME 1-99/99-1 -25
反式-HFC-1234ze CF3SCF3 1-99/99-1 -25
反式-HFC-1234ze CF3I 1-99/99-1 -25
HFC-1243zf HFC-134 1-99/99-1 -25
HFC-1243zf HFC-134a 1-99/99-1 -25
 
HFC-1243zf HFC-152a 1-99/99-1 -25
HFC-1243zf HFC-161 1-99/99-1 -25
HFC-1243zf HFC-227ea 1-99/99-1 -25
HFC-1243zf HFC-236ea 53-99/47-1 -25
HFC-1243zf HFC-236fa 49-99/51-1 -25
HFC-1243zf HFC-245fa 66-99/34-1 -25
HFC-1243zf 丙烷 1-71/99-29 -25
HFC-1243zf 正丁烷 62-99/38-1 -25
HFC-1243zf 异丁烷 45-99/55-1 -25
HFC-1243zf DME 1-99/99-1 -25
顺式-HFC-1234ze HFC-236ea 1-99/99-1 25
顺式-HFC-1234ze HFC-236fa 1-99/99-1 25
顺式-HFC-1234ze HFC-245fa 1-99/99-1 25
顺式-HFC-1234ze 正丁烷 1-80/99-20 -25
顺式-HFC-1234ze 异丁烷 1-69/99-31 -25
顺式-HFC-1234ze 2-甲基丁烷 60-99/40-1 25
顺式-HFC-1234ze 正戊烷 63-99/37-1 25
HFC-1234ye HFC-134 38-99/62-1 25
HFC-1234ye HFC-236ea 1-99/99-1 -25
HFC-1234ye HFC-236fa 1-99/99-1 25
HFC-1234ye HFC-245fa 1-99/99-1 25
HFC-1234ye 顺式-HFC-1234ze 1-99/99-1 25
HFC-1234ye 正丁烷 1-78/99-22 25
HFC-1234ye 环戊烷 70-99/30-1 25
HFC-1234ye 异丁烷 1-68/99-32 25
HFC-1234ye 2-甲基丁烷 47-99/53-1 25
HFC-1234ye 正戊烷 57-99/43-1 25
包含氟烯烃的三元和更高级近共沸物组合物也如表6中所列。
表6
 
组分 近共沸物范围(wt%) 温度(℃)
HFC-1225ye/HFC-134a/HFC-152a 1-98/1-98/1-98 25
HFC-1225ye/HFC-134a/HFC-161 1-98/1-98/1-98 25
HFC-1225ye/HFC-134a/异丁烷 1-98/1-98/1-40 25
HFC-1225ye/HFC-134a/DME 1-98/1-98/1-20 25
HFC-1225ye/HFC-152a/异丁烷 1-98/1-98/1-50 25
HFC-1225ye/HFC-152a/DME 1-98/1-98/1-98 25
HFC-1225ye/HFC-1234yf/HFC-134a 1-98/1-98/1-98 25
HFC-1225ye/HFC-1234yf/HFC-152a 1-98/1-98/1-98 25
HFC-1225ye/HFC-1234yf/HFC-125 1-98/1-98/1-20 25
HFC-1225ye/HFC-1234yf/CF3I 1-98/1-98/1-98 25
HFC-1225ye/HFC-134a/HFC-152a/HFC-32 1-97/1-97/1-97/1-10 25
HFC-125/HFC-1225ye/异丁烷 80-98/1-19/1-10 25
HFC-125/反式-HFC-1234ze/异丁烷 80-98/1-19/1-10 25
HFC-125/HFC-1234yf/异丁烷 80-98/1-19/1-10 25
HFC-32/HFC-125/HFC-1225ye 1-98/1-98/1-4 25
HFC-32/HFC-125/反式-HFC-1234ze 1-98/1-98/1-50 25
HFC-32/HFC-125/HFC-1234yf 1-98/1-98/1-55 25
HFC-125/反式-HFC-1234ze/正丁烷 80-98/1-19/1-10 25
HFC-125/HFC-1234yf/正丁烷 80-98/1-19/1-10 25
HFC-1234yf/HFC-32/HFC-143a 1-50/1-98/1-98 -25
HFC-1234yf/HFC-32/异丁烷 1-40/59-98/1-30 -25
HFC-1234yf/HFC-125/HFC-143a 1-60/1-98/1-98 -25
HFC-1234yf/HFC-125/异丁烷 1-40/59-98/1-20 -25
HFC-1234yf/HFC-134/丙烷 1-80/1-70/19-90 -25
HFC-1234yf/HFC-134/DME 1-70/1-98/29-98 -25
HFC-1234yf/HFC-134a/丙烷 1-80/1-80/19-98 -25
HFC-1234yf/HFC-134a/正丁烷 1-98/1-98/1-30 -25
 
HFC-1234yf/HFC-134a/异丁烷 1-98/1-98/1-30 -25
HFC-1234yf/HFC-134a/DME 1-98/1-98/1-40 -25
HFC-1234yf/HFC-143a/丙烷 1-80/1-98/1-98 -25
HFC-1234yf/HFC-143a/DME 1-40/59-98/1-20 -25
HFC-1234yf/HFC-152a/正丁烷 1-98/1-98/1-30 -25
HFC-1234yf/HFC-152a/异丁烷 1-98/1-90/1-40 -25
HFC-1234yf/HFC-152a/DME 1-70/1-98/1-98 -25
HFC-1234yf/HFC-227ea/丙烷 1-80/1-70/29-98 -25
HFC-1234yf/HFC-227ea/正丁烷 40-98/1-59/1-20 -25
HFC-1234yf/HFC-227ea/异丁烷 30-98/1-69/1-30 -25
HFC-1234yf/HFC-227ea/DME 1-98/1-80/1-98 -25
HFC-1234yf/正丁烷/DME 1-98/1-40/1-98 -25
HFC-1234yf/异丁烷/DME 1-98/1-50/1-98 -25
HFC-1234yf/DME/CF3I 1-98/1-98/1-98 -25
HFC-1234yf/DME/CF3SCF3 1-98/1-40/1-80 -25
HFC-1225ye/反式-HFC-1234ze/HFC-134 1-98/1-98/1-98 -25
HFC-1225ye/反式-HFC-1234ze/HFC-227ea 1-98/1-98/1-98 -25
HFC-1225ye/反式-HFC-1234ze/丙烷 1-60/1-60/1-98 -25
HFC-1225ye/反式-HFC-1234ze/正丁烷 1-98/1-98/1-30 -25
HFC-1225ye/反式-HFC-1234ze/DME 1-98/1-98/1-98 -25
HFC-1225ye/反式-HFC-1234ze/CF3SCF3 1-98/1-98/1-98 -25
HFC-1225ye/HFC-1243zf/HFC-134 1-98/1-98/1-98 -25
HFC-1225ye/HFC-1243zf/正丁烷 1-98/1-98/1-30 -25
HFC-1225ye/HFC-1243zf/异丁烷 1-98/1-98/1-40 -25
HFC-1225ye/HFC-1243zf/DME 1-98/1-98/1-98 -25
HFC-1225ye/HFC-1243zf/CF3I 1-98/1-98/1-98 -25
HFC-1225ye/HFC-134/HFC-152a 1-98/1-98/1-98 -25
HFC-1225ye/HFC-134/HFC-227ea 1-98/1-98/1-98 -25
 
HFC-1225ye/HFC-134/正丁烷 1-98/1-90/1-40 -25
HFC-1225ye/HFC-134/异丁烷 1-98/1-90/1-40 -25
HFC-1225ye/HFC-134/DME 1-98/1-98/1-40 -25
HFC-1225ye/HFC-227ea/DME 40-98/1-59/1-30 -25
HFC-1225ye/正丁烷/DME 1-98/1-30/1-98 -25
HFC-1225ye/正丁烷/CF3SCF3 1-98/1-20/1-98 -25
HFC-1225ye/异丁烷/DME 1-98/1-60/1-98 -25
HFC-1225ye/异丁烷/CF3I 1-98/1-40/1-98 -25
反式-HFC-1234ze/HFC-1243zf/HFC-227ea 1-98/1-98/1-98 -25
反式-HFC-1234ze/HFC-1243zf/正丁烷 1-98/1-98/1-30 -25
反式-HFC-1234ze/HFC-1243zf/异丁烷 1-98/1-98/1-40 -25
反式-HFC-1234ze/HFC-1243zf/DME 1-98/1-98/1-98 -25
反式-HFC-1234ze/HFC-134/HFC-152a 1-98/1-98/1-98 -25
反式-HFC-1234ze/HFC-134/HFC-227ea 1-98/1-98/1-98 -25
反式-HFC-1234ze/HFC-134/DME 1-98/1-98/1-40 -25
反式-HFC-1234ze/HFC-134a/HFC-152a 1-98/1-98/1-98 -25
反式-HFC-1234ze/HFC-152a/正丁烷 1-98/1-98/1-50 -25
反式-HFC-1234ze/HFC-152a/DME 1-98/1-98/1-98 -25
反式-HFC-1234ze/HFC-227ea/正丁烷 1-98/1-98/1-40 -25
反式-HFC-1234ze/正丁烷/DME 1-98/1-40/1-98 -25
反式-HFC-1234ze/正丁烷/CF3I 1-98/1-30/1-98 -25
反式-HFC-1234ze/异丁烷/DME 1-98/1-60/1-98 -25
反式-HFC-1234ze/异丁烷/CF3I 1-98/1-40/1-98 -25
反式-HFC-1234ze/异丁烷/CF3SCF3 1-98/1-40/1-98 -25
HFC-1243zf/HFC-134/HFC-227ea 1-98/1-98/1-98 -25
HFC-1243zf/HFC-134/正丁烷 1-98/1-98/1-40 -25
HFC-1243zf/HFC-134/DME 1-98/1-98/1-98 -25
HFC-1243zf/HFC-134/CF3I 1-98/1-98/1-98 -25
 
HFC-1243zf/HFC-134a/HFC-152a 1-98/1-98/1-98 -25
HFC-1243zf/HFC-134a/正丁烷 1-98/1-98/1-40 -25
HFC-1243zf/HFC-152a/丙烷 1-70/1-70/29-98 -25
HFC-1243zf/HFC-152a/正丁烷 1-98/1-98/1-30 -25
HFC-1243zf/HFC-152a/异丁烷 1-98/1-98/1-40 -25
HFC-1243zf/HFC-152a/DME 1-98/1-98/1-98 -25
HFC-1243zf/HFC-227ea/正丁烷 1-98/1-98/1-40 -25
HFC-1243zf/HFC-227ea/异丁烷 1-98/1-90/1-50 -25
HFC-1243zf/HFC-227ea/DME 1-98/1-80/1-90 -25
HFC-1243zf/正丁烷/DME 1-98/1-40/1-98 -25
HFC-1243zf/异丁烷/DME 1-98/1-60/1-98 -25
HFC-1243zf/异丁烷/CF3I 1-98/1-40/1-98 -25
HFC-1243zf/DME/CF3SCF3 1-98/1-40/1-90 -25
本发明的某些组合物是非共沸组合物。在表2的优选范围内但在表5和表6的近共沸范围外的本发明的那些组合物可以被视为是非共沸的。
非共沸组合物可能具有优于共沸或近共沸混合物的某些优点。非共沸组合物是表现为混合物而非单一物质的两种或多种物质的混合物。非共沸组合物的一种表征方式在于,通过液体的部分蒸发或蒸馏产生的蒸气具有与用于蒸发或蒸馏的液体基本不同的组成,即该混合物蒸馏/回流伴随着显著的组成变化。非共沸组合物的另一表征方式在于,该组合物在特定温度下的泡点蒸气压和露点蒸气压基本不同。在此,如果在例如通过蒸发或煮沸除去50重量%的组合物后,原始组合物和除去50重量%原始组合物后留下的组合物之间的蒸气压差大于大约10%,则该组合物是非共沸的。
本发明的组合物可以通过任何方便的方法制备以合并所需量的各组分。优选方法是称出所需组分量并此后在适当的容器中合并所述组分。如果需要,可以使用搅拌。
制造本发明的组合物的另一方式可以是制造制冷剂掺合物组合物的方法,其中所述制冷剂掺合物组合物包含本文所公开的组合物,所述方法包括(i)从至少一个制冷剂容器中回收制冷剂组合物的一定量的一种或多种组分,(ii)充分除去杂质以便使所述一种或多种回收的组分能够再利用,(iii)和任选地,将所有或部分的所述回收量的组分与至少一种附加制冷剂组合物或组分合并。
制冷剂容器可以是存储在制冷装置、空调装置或热泵装置中已经使用的制冷剂掺合物组合物的任何容器。所述制冷剂容器可以是在其中使用制冷剂掺合物的制冷装置、空调装置或热泵装置。另外,制冷剂容器可以是用于收集回收的制冷剂掺合物组分的存储容器,包括但不限于加压气筒。
残留制冷剂是指可以通过已知用于转移制冷剂掺合物或制冷剂掺合物组分的任何方法从制冷剂容器中移出的任何量的制冷剂掺合物或制冷剂掺合物组分。
杂质可以是由于其在制冷装置、空调装置或热泵装置中使用而存在于制冷剂掺合物或制冷剂掺合物组分中的任何组分。这类杂质包括,但不限于,上文所述的制冷润滑剂,可能出自制冷装置、空调装置或热泵装置的颗粒,包括但不限于金属、金属盐或弹性体粒子,和可能不利地影响制冷剂掺合物组合物的性能的任何其它污染物。
可以充分除去这类杂质以便在不会不利地影响使用该制冷剂掺合物或制冷剂掺合物组分的设备性能的情况下再利用该制冷剂掺合物或制冷剂掺合物组分。
可能必须在残留的制冷剂掺合物或制冷剂掺合物组分中提供附加的制冷剂掺合物或制冷剂掺合物组分以制造符合给定产品所需的规格的组合物。例如,如果制冷剂掺合物具有在特定重量百分比范围内的3种组分,可能必须以给定量加入一种或多种组分以使该组成恢复到规格界限内。
本发明的组合物具有0或低的臭氧损耗潜势和低的全球变暖潜势(GWP)。另外,本发明的组合物具有比目前使用的许多氟代烃制冷剂小的全球变暖潜势。本发明的一个方面是提供全球变暖潜势小于1000,小于500,小于150,小于100或小于50的制冷剂。本发明的另一方面是通过在所述混合物中加入氟烯烃来降低制冷剂混合物的净GWP。
本发明的组合物可用作目前使用的制冷剂的低全球变暖潜势(GWP)替代物,目前使用的制冷剂包括但不限于,R134a(或HFC-134a,1,1,1,2-四氟乙烷)、R22(或HCFC-22,氯二氟甲烷)、R123(或HFC-123,2,2-二氯-1,1,1-三氟乙烷)、R11(CFC-11,氟三氯甲烷)、R12(CFC-12,二氯二氟甲烷)、R245fa(或HFC-245fa,1,1,1,3,3-五氟丙烷)、R114(或CFC-114,1,2-二氯-1,1,2,2-四氟乙烷)、R236fa(或HFC-236fa,1,1,1,3,3,3-六氟丙烷)、R124(或HCFC-124,2-氯-1,1,1,2-四氟乙烷)、R407C(52重量%R134a、25重量%R125(五氟乙烷)和23重量%R32(二氟甲烷)的掺合物的ASHRAE名称)、R410A(50重量%R125和50重量%R32的掺合物的ASHRAE名称)、R417A(46.6重量%R125、50.0重量%R134a和3.4重量%正丁烷的掺合物的ASHRAE名称)、R422A、R422B、R422C和R422D(85.1重量%R125、11.5重量%R134a和3.4重量%异丁烷的掺合物的ASHRAE名称)、R404A(44重量%R125、52重量%R143a(1,1,1-三氟乙烷)和4.0重量%R134a的掺合物的ASHRAE名称)和R507A(50重量%R125和50重量%R143a的掺合物的ASHRAE名称)。另外,本发明的组合物可用作R12(CFC-12,二氯二氟甲烷)或R502(51.2重量%CFC-115(氯五氟乙烷)和48.8重量%HCFC-22的掺合物的ASHRAE名称)的替代物。
通常,替代制冷剂如果能用在为不同制冷剂设计的原始制冷设备中,则是最有用的。本发明的组合物可在原始设备中用作上述制冷剂的替代物。另外,本发明的组合物可以在设计成使用上述制冷剂的设备中用作上述制冷剂的替代物。
本发明的组合物可以进一步包含润滑剂。本发明的润滑剂包含制冷润滑剂,即适合与制冷、空调或热泵装置一起使用的那些润滑剂。这些润滑剂包括传统上用在采用氯氟烃制冷剂的压缩制冷装置中的那些。在1990 ASHRAE Handbook,Refrigeration Systems and Applications,第8章,标题"Lubricants in Refrigeration Systems",第8.1至8.21页中论述了这类润滑剂和它们的性质。本发明的润滑剂可以包含在压缩制冷润滑领域中常被称作“矿物油”的那些。矿物油包含链烷烃(即直链和支链碳链,饱和烃)、环烷(即环烷烃)和芳烃(即含有一个或多个以交替双键为特征的环的不饱和环烃)。本发明的润滑剂进一步包含在压缩制冷润滑领域中常被称作“合成油”的那些。合成油包含烷基芳基(即直链和支链烷基烷基苯)、合成链烷和环烷、和聚(α烯烃)。本发明的代表性的传统润滑剂是市售BVM 100 N(BVA Oils出售的链烷矿物油)、
Figure G200680054110XD00261
3GS和 5GS(Crompton Co.出售的环烷矿物油)、
Figure G200680054110XD00263
 372LT(Pennzoil出售的环烷矿物油)、
Figure G200680054110XD00271
 RO-30(Calumet Lubricants出售的环烷矿物油)、
Figure G200680054110XD00272
 75、 150和
Figure G200680054110XD00274
 500(ShrieveChemicals出售的直链烷基苯)和HAB22(Nippon Oil出售的支链烷基苯)。
本发明的润滑剂进一步包含已经设计成与氟代烃制冷剂一起使用并且在压缩制冷、空调或热泵装置操作条件下与本发明的制冷剂混溶的那些。在"Synthetic Lubricants and High-Performance Fluids",R.L.Shubkin,editor,Marcel Dekker,1993中论述了这类润滑剂及其性质。这类润滑剂包括但不限于,多元醇酯(POE),例如
Figure G200680054110XD00275
 100(Castrol,UnitedKingdom),聚烷撑二醇(PAG),例如来自Dow(Dow Chemical,Midland,Michigan)的RL-488A,和聚乙烯醚(PVE)。这些润滑剂容易获自各种商业来源。
通过考虑给定压缩机的要求和润滑剂的暴露环境来选择本发明的润滑剂。本发明的润滑剂优选具有在40℃至少大约5cs(厘沲)的动粘度。
可以任选按需要在本发明的组合物中添加常用的制冷系统添加剂以增强润滑性和系统稳定性。这些添加剂通常是制冷压缩机润滑领域内已知的,并包括抗磨剂、极压润滑剂、腐蚀和氧化抑制剂、金属表面钝化剂、自由基清除剂、发泡和防沫控制剂、泄漏检测剂和类似物。通常,这些添加剂相对于总润滑剂组合物仅少量存在。它们通常以每种添加剂小于大约0.1%至多达大约3%的浓度使用。基于各系统要求选择这些添加剂。这类添加剂的一些典型实例可以包括,但不限于,润滑增强添加剂,例如磷酸的烷基或芳基酯和硫代磷酸的烷基或芳基酯。另外,本发明的组合物中可以使用二烷基二硫代磷酸的金属盐(例如二硫代磷酸二烷基酯锌或ZDDP,Lubrizol 1375)和该化学品族的其它成员。其它抗磨添加剂包括天然产物油和不对称聚羟基润滑添加剂,例如SynergolTMS(International Lubricants)。类似地,可以使用稳定剂,如抗氧化剂、自由基清除剂和水清除剂。这类中的化合物可以包括,但不限于,丁基化羟基甲苯(BHT)和环氧化物。
本发明的组合物可以进一步包含大约0.01重量%至大约5重量%的添加剂,例如稳定剂、自由基清除剂和/或抗氧化剂。这类添加剂包括但不限于,硝基甲烷、受阻酚、羟胺、硫醇、亚磷酸酯或内酯。可以使用单种添加剂或组合。
本发明的组合物可以进一步包含大约0.01重量%至大约5重量%的水清除剂(干燥化合物)。这类水清除剂可以包含原酸酯,例如三甲基-、三乙基-、或三丙基原甲酸酯。
本发明的组合物可以进一步包含选自氟代烃(HFC)、氘化烃、氘化氟代烃、全氟化碳、氟醚、溴化化合物、碘化化合物、醇、醛、酮、一氧化二氮(N2O)及其组合的示踪剂。示踪剂化合物以如2005年2月18日提交的美国专利申请系列号11/062044中所述预先测得的能够检测该组合物的任何稀释、污染或其它变化的量添加到组合物中。
用在本组合物中的典型的示踪剂化合物列在表7中。
表7
Figure G200680054110XD00291
Figure G200680054110XD00301
Figure G200680054110XD00311
Figure G200680054110XD00321
表7中所列的化合物可购得(购自化学供应机构)或可以通过本领域中已知的方法制备。
单种示踪剂化合物可以与制冷/加热流体结合用在本发明的组合物中,或多种示踪剂化合物可以以任何比例组合以充当示踪剂掺合物。示踪剂掺合物可以含有来自同一化合物类型的多种示踪剂化合物或来自不同化合物类型的多种示踪剂化合物。例如,示踪剂掺合物可以含有两种或更多的氘化氟代烃,或与一种或多种全氟化碳结合的一种氘化氟代烃。
另外,表7中的一些化合物作为多种结构或光学异构体存在。同一化合物的单种异构体或多种异构体可以以任何比例使用以制备示踪剂化合物。此外,给定化合物的单种或多种异构体可以与任何数量的其它化合物以任何比例结合以充当示踪剂掺合物。
示踪剂化合物或示踪剂掺合物可以在组合物中以按重量计百万分之大约50份(ppm)至大约1000ppm的总浓度存在。优选地,示踪剂化合物或示踪剂掺合物以大约50ppm至大约500ppm的总浓度存在,最优选地,示踪剂化合物或示踪剂掺合物以大约100ppm至大约300ppm的总浓度存在。
本发明的组合物可以进一步包含选自聚氧化亚烷基二醇醚、酰胺、腈、酮、氯碳化合物、酯、内酯、芳基醚、氟醚和1,1,1-三氟烷烃的增容剂。使用增容剂改进氟代烃制冷剂在传统制冷润滑剂中的溶解度。需要制冷润滑剂以润滑制冷、空调或热泵装置的压缩机。润滑剂必须与制冷剂一起移动通过整个装置,特别是其必须从非压缩机区域回到压缩机中以继续充当润滑剂并避免压缩机故障。
氟代烃制冷剂通常与传统的制冷润滑剂,例如矿物油、烷基苯、合成链烷、合成环烷和聚(α)烯烃不相容。已经提出了许多替代润滑剂,但是,被推荐与氟代烃制冷剂一起使用的聚烷撑二醇、多元醇酯和聚乙烯基醚昂贵并且容易吸收水。制冷、空调系统或热泵中的水会造成腐蚀和粒子形成,这些粒子可能堵塞该系统中的毛细管和其它小孔口,最终造成系统失效。另外,在现有设备中,需要耗时和昂贵的吹洗程序以更换成新的润滑剂。因此,如果可能,合意的是继续使用原始润滑剂。
本发明的增容剂改进了氟代烃制冷剂在传统制冷润滑剂中的溶解度并由此改进到压缩机的回油。
本发明的聚氧化亚烷基二醇醚增容剂如式R1[(OR2)xOR3]y所示,其中:x是1-3的整数;y是1-4的整数;R1选自氢和具有1至6个碳原子和y键合位点的脂族烃基;R2选自具有2至4个碳原子的脂族亚烃基;R3选自氢和具有1至6个碳原子的脂族和脂环族烃基;R1和R3至少一个是所述烃基;且其中所述聚氧化亚烷基二醇醚具有大约100至大约300原子质量单位的分子量。本文所用的键合位点是指可用于与其它基团形成共价键的基团位点。亚烃基是指二价烃基。在本发明中,优选的聚氧化亚烷基二醇醚增容剂如R1[(OR2)xOR3]y所示:x优选为1-2;y优选为1;R1和R3优选独立地选自氢和具有1至4个碳原子的脂族烃基;R2优选选自具有2或3个碳原子,最优选3个碳原子的脂族亚烃基;聚氧化亚烷基二醇醚分子量优选为大约100至大约250原子质量单位,最优选大约125至大约250原子质量单位。具有1至6个碳原子的R1和R3烃基可以是直链、支链或环状的。代表性的R1和R3烃基包括甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、新戊基、叔戊基、环戊基、和环己基。当这种聚氧化亚烷基二醇醚增容剂上的游离羟基可能与某些压缩制冷装置构造材料(例如Mylar
Figure G200680054110XD0033133506QIETU
)不相容时,R1和R3优选为具有1至4个碳原子,最优选1个碳原子的脂族烃基。具有2至4个碳原子的R2脂族亚烃基构成重复氧化烯基团-(OR2)x-,包括氧乙烯基、氧丙烯基和氧丁烯基。一个聚氧化亚烷基二醇醚增容剂分子中的包含R2的氧化烯基团可以相同,或一个分子可以含有不同的R2氧化烯基团。这种聚氧化亚烷基二醇醚增容剂优选包含至少一个氧丙烯基团。在R1是具有1至6个碳原子和y键合位点的脂族或脂环族烃基的情况下,该基团可以是直链、支链或环状的。代表性的具有两个键合位点的R1脂族烃基包括,例如,亚乙基、亚丙基、亚丁基、亚戊基、亚己基、环亚戊基和环亚己基。代表性的具有三个或四个键合位点的R1脂族烃基包括由聚醇,例如三羟甲基丙烷、丙三醇、季戊四醇、1,2,3-三羟基环己烷和1,3,5-三羟基环己烷,通过除去其羟基而产生的残基。
代表性的聚氧化亚烷基二醇醚增容剂包括但不限于:CH3OCH2CH(CH3)O(H或CH3)(丙二醇甲基(或二甲基)醚)、CH3O[CH2CH(CH3)O]2(H或CH3)(二丙二醇甲基(或二甲基)醚)、CH3O[CH2CH(CH3)O]3(H或CH3)(三丙二醇甲基(或二甲基)醚)、C2H5OCH2CH(CH3)O(H或C2H5)(丙二醇乙基醚(或二乙基)醚)、C2H5O[CH2CH(CH3)O]2(H或C2H5)(二丙二醇乙基(或二乙基)醚)、C2H5O[CH2CH(CH3)O]3(H或C2H5)(三丙二醇乙基醚(或二乙基)醚)、C3H7OCH2CH(CH3)O(H或C3H7)(丙二醇正丙基(或二正丙基)醚)、C3H7O[CH2CH(CH3)O]2(H或C3H7)(二丙二醇正丙基(或二正丙基)醚)、C3H7O[CH2CH(CH3)O]3(H或C3H7)(三丙二醇正丙基(或二正丙基)醚)、C4H9OCH2CH(CH3)OH(丙二醇正丁基醚)、C4H9O[CH2CH(CH3)O]2(H或C4H9)(二丙二醇正丁基(或二正丁基)醚)、C4H9O[CH2CH(CH3)O]3(H或C4H9)(三丙二醇正丁基(或二正丁基)醚)、(CH3)3COCH2CH(CH3)OH(丙二醇叔丁基醚)、(CH3)3CO[CH2CH(CH3)O]2(H或(CH3)3)(二丙二醇叔丁基(或二叔丁基)醚)、(CH3)3CO[CH2CH(CH3)O]3(H或(CH3)3)(三丙二醇叔丁基(或二叔丁基)醚)、C5H11OCH2CH(CH3)OH(丙二醇正戊基醚)、C4H9OCH2CH(C2H5)OH(丁二醇正丁基醚)、C4H9O[CH2CH(C2H5)O]2H(二丁二醇正丁基醚)、三羟甲基丙烷三正丁基醚(C2H5C(CH2O(CH2)3CH3)3)和三羟甲基丙烷二正丁基醚(C2H5C(CH2OC(CH2)3CH3)2CH2OH)。
本发明的酰胺增容剂包含式R1C(O)NR2R3和环-[R4C(O)N(R5)]所示的那些,其中R1、R2、R3和R5独立地选自具有1至12个碳原子的脂族和脂环族烃基;R4选自具有3至12个碳原子的脂族亚烃基;且其中所述酰胺具有大约100至大约300原子质量单位的分子量。所述酰胺的分子量优选为大约160至大约250原子质量单位。R1、R2、R3和R5可以任选包括取代烃基,即含有选自卤素(例如氟、氯)和烷氧化物(例如甲氧基)的非烃取代基的基团。R1、R2、R3和R5可以任选包括杂原子取代的烃基,即在另外由碳原子构成的基团链中含有原子氮(氮杂-)、氧(氧杂-)或硫(硫杂-)的基团。通常,对于R1-3中的每10个碳原子,存在不多于3个非烃取代基和杂原子,优选不多于1个,且在施加上述分子量限制时必须考虑任何这样的非烃取代基和杂原子的存在。优选的酰胺增容剂由碳、氢、氮和氧构成。代表性的R1、R2、R3和R5脂族和脂环族烃基包括甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、新戊基、叔戊基、环戊基、环己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基和它们的构型异构体。酰胺增容剂的优选实施方案是上述式环-[R4C(O)N(R5)-]中的R4可以表示为亚烃基(CR6R7)n的这些,换言之,式环-[(CR6R7)nC(O)N(R5)-],其中:适用针对分子量的上述值;n是3至5的整数;R5是含有1至12个碳原子的饱和烃基;R6和R7独立地通过之前提供的定义R1-3的规则选择(对于各n)。在式:环-[(CR6R7)nC(O)N(R5)-]所示的内酰胺中,所有R6和R7优选为氢,或在n个亚甲基单元中含有单个饱和烃基,且R5是含有3至12个碳原子的饱和烃基。例如,1-(饱和烃基)-5-甲基吡咯烷-2-酮。
代表性的酰胺增容剂包括但不限于:1-辛基吡咯烷-2-酮、1-癸基吡咯烷-2-酮、1-辛基-5-甲基吡咯烷-2-酮、1-丁基己内酰胺、1-环己基吡咯烷-2-酮、1-丁基-5-甲基哌啶-2-酮、1-戊基-5-甲基哌啶-2-酮、1-己基己内酰胺、1-己基-5-甲基吡咯烷-2-酮、5-甲基-1-戊基哌啶-2-酮、1,3-二甲基哌啶-2-酮、1-甲基己内酰胺、1-丁基-吡咯烷-2-酮、1,5-二甲基哌啶-2-酮、1-癸基-5-甲基吡咯烷-2-酮、1-十二烷基吡咯烷-2-酮、N,N-二丁基甲酰胺和N,N-二异丙基乙酰胺。
本发明的酮增容剂包含式R1C(O)R2所示的酮,其中R1和R2独立地选自具有1至12个碳原子的脂族、脂环族和芳基烃基,且其中所述酮具有大约70至大约300原子质量单位的分子量。所述酮中的R1和R2优选独立地选自具有1至9个碳原子的脂族和脂环族烃基。所述酮的分子量优选为大约100至200原子质量单位。R1和R2可以一起形成连接形成5、6或7元环酮,例如环戊酮、环己酮和环庚酮的亚烃基。R1和R2可以任选包括取代烃基,即含有选自卤素(例如氟、氯)和烷氧化物(例如甲氧基)的非烃取代基的基团。R1和R2可以任选包括杂原子取代的烃基,即在另外由碳原子构成的基团链中含有原子氮(氮杂-)、氧(氧代、氧杂-)或硫(硫杂-)的基团。通常,对于R1和R2中的每10个碳原子,存在不多于3个非烃取代基和杂原子,优选不多于1个,且在施加上述分子量限制时必须考虑任何这样的非烃取代基和杂原子的存在。通式R1C(O)R2中的代表性R1和R2脂族、脂环族和芳基烃基包括甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基,异戊基、新戊基、叔戊基、环戊基、环己基,庚基、辛基、壬基、癸基,十一烷基、十二烷基和它们的构型异构体,以及苯基、苄基、枯烯基、
Figure G200680054110XD0036134038QIETU
基、甲苯基、二甲苯基和苯乙基。
代表性的酮增容剂包括但不限于:2-丁酮、2-戊酮、苯乙酮、丙基苯基酮、苯己酮、环己酮、环庚酮、2-庚酮、3-庚酮、5-甲-2-己酮、2-辛酮、3-辛酮、二异丁基酮、4-乙基环己酮、2-壬酮、5-壬酮、2-癸酮、4-癸酮、2-萘烷酮(decalone)、2-十三烷酮、二己基酮和二环己基酮。
本发明的腈增容剂包含式R1CN所示的腈,其中R1选自具有5至12个碳原子的脂族、脂环族或芳基烃基且其中所述腈具有大约90至大约200原子质量单位的分子量。所述腈增容剂中的R1优选选自具有8至10个碳原子的脂族和脂环族烃基。所述腈增容剂的分子量优选为大约120至大约140原子质量单位。R1可以任选包括取代烃基,即含有选自卤素(例如氟、氯)和烷氧化物(alkoxide)(例如甲氧基)的非烃取代基的基团。R1可以任选包括杂原子取代的烃基,即在另外由碳原子构成的基团链中含有原子氮(氮杂-)、氧(氧代、氧杂-)或硫(硫杂-)的基团。通常,对于R1中的每10个碳原子,存在不多于3个非烃取代基和杂原子,优选不多于1个,且在施加上述分子量限制时必须考虑任何这样的非烃取代基和杂原子的存在。通式R1CN中的代表性R1脂族、脂环族和芳基烃基包括戊基、异戊基、新戊基、叔戊基、环戊基、环己基、庚基、辛基、壬基、癸基,十一烷基、十二烷基和它们的构型异构体,以及苯基、苄基、枯烯基、
Figure G200680054110XD0036134117QIETU
基,、甲苯基、二甲苯基和苯乙基。
代表性的腈增容剂包括但不限于:1-氰基戊烷、2,2-二甲基-4-氰基戊烷、1-氰基己烷、1-氰基庚烷、1-氰基辛烷、2-氰基辛烷、1-氰基壬烷、1-氰基癸烷、2-氰基癸烷、1-氰基十一烷和1-氰基十二烷。
本发明的含氯烃增容剂包含式RClx所示的含氯烃,其中:x选自1或2的整数;R选自具有1至12个碳原子的脂族和脂环族烃基;且其中所述含氯烃具有大约100至大约200原子质量单位的分子量。所述含氯烃增容剂的分子量优选为大约120至150原子质量单位。通式RClx中的代表性R脂族和脂环族烃基包括甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、新戊基、叔戊基、环戊基、环己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基和它们的构型异构体。
代表性的含氯烃增容剂包括但不限于:3-(氯甲基)戊烷、3-氯-3-甲基戊烷、1-氯己烷,1,6-二氯己烷、1-氯庚烷、1-氯辛烷、1-氯壬烷、1-氯癸烷、和1,1,1-三氯癸烷。
本发明的酯增容剂包含通式R1CO2R2所示的酯,其中R1和R2独立地选自直链和环状的、饱和和不饱和的烷基和芳基。优选的酯基本由元素C、H和O构成,具有大约80至大约550原子质量单位的分子量。
代表性的酯包括但不限于:
(CH3)2CHCH2OOC(CH2)2-4OCOCH2CH(CH3)2(二异丁基二价酸酯)、己酸乙酯、庚酸乙酯、丙酸正丁酯、丙酸正丙酯、苯甲酸乙酯、邻苯二甲酸二正丙酯、苯甲酸乙氧基乙酯、碳酸二丙酯、"Exxate 700"(商品乙酸C7烷基酯)、"Exxate 800"(商品乙酸C8烷基酯)、邻苯二甲酸二丁酯和乙酸叔丁酯。
本发明的内酯增容剂包含结构[A]、[B]和[C]所示的内酯:
这些内酯在六个(A)或优选五个原子(B)的环中含有官能团-CO2-,其中对于结构[A]和[B],R1至R8独立地选自氢或直链、支链、环状、双环的饱和和不饱和的烃基。各R1至R8可以与另一R1至R8连接形成环。内酯可以如结构[C]中那样具有环外烷叉基,其中R1至R6独立地选自氢或直链、支链、环状、双环的饱和和不饱和的烃基。各R1至R6可以与另一R1至R6连接形成环。内酯增容剂具有大约100至大约300原子质量单位,优选大约100至大约200原子质量单位的分子量范围。
代表性的内酯增容剂包括但不限于表8中所列的化合物。
表8
Figure G200680054110XD00381
Figure G200680054110XD00391
内酯增容剂通常具有在40℃小于大约7厘沲的动粘度。例如,γ-十一烷酸内酯具有5.4厘沲的动粘度且顺式-(3-己基-5-甲基)二氢呋喃-2-酮具有4.5厘沲的粘度,两者均在40℃。内酯增容剂可购得或通过2004年8月3日提交的美国专利申请10/910,495中所述的方法制备,其经此引用并入本文。
本发明的芳基醚增容剂进一步包含式R1OR2所示的芳基醚,其中:R1选自具有6至12个碳原子的芳基烃基;R2选自具有1至4个碳原子的脂族烃基,且其中所述芳基醚具有大约100至大约150原子质量单位的分子量。通式R1OR2中的代表性R1芳基包括苯基、联苯基、枯烯基、
Figure 200680054110X100002G200680054110XD0036134117QIETU
基、甲苯基、二甲苯基、萘基和吡啶基。通式R1OR2中的代表性R2脂族烃基包括甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基和叔丁基。代表性的芳基醚增容剂包括但不限于:甲基苯基醚(苯甲醚)、1,3-二甲氧基苯、乙基苯基醚和丁基苯基醚。
本发明的氟代醚增容剂包含通式R1OCF2CF2H所示的那些,其中R1选自具有大约5至大约15个碳原子的脂族、脂环族和芳族烃基,优选为直链的饱和伯烷基。代表性的氟代醚增容剂包括但不限于:C8H17OCF2CF2H和C6H13OCF2CF2H。应该指出的是,如果制冷剂是氟代醚,则增容剂可以不是相同的氟代醚。
氟代醚增容剂可以进一步包含由氟烯烃和多元醇生成的醚。氟烯烃可以为CF2=CXY类型的,其中X是氢、氯或氟,且Y是氯、氟、CF3或ORf,其中Rf是CF3、C2F5或C3F7。代表性的氟烯烃是四氟乙烯、氯三氟乙烯、六氟丙烯和全氟甲基乙烯基醚。多元醇可以是直链或支链的。直链多元醇可以是HOCH2(CHOH)x(CRR′)yCH2OH类型的,其中R和R′是氢或CH3或C2H5且其中x是0-4的整数,且y是0-4的整数。支链多元醇可以是C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w的类型,其中R可以是氢CH3或C2H5,m可以是0至3的整数,t和u可以是0或1,v和w是0至4的整数,且其中t+u+v+w=4。代表性的多元醇是三羟甲基丙烷、季戊四醇、丁二醇和乙二醇。
本发明的1,1,1-三氟烷烃增容剂包含通式CF3R1所示的1,1,1-三氟烷烃,其中R1选自具有大约5至大约15个碳原子的脂族和脂环族烃基,优选为直链的饱和伯烷基。代表性的1,1,1-三氟烷烃增容剂包括但不限于:1,1,1-三氟己烷和1,1,1-三氟十二烷。
有效量的增容剂是指造成润滑剂在该组合物中有效溶解并由此提供充足回油以优化制冷、空调或热泵装置的操作的量的增容剂。
本发明的组合物通常在本发明的组合物中含有大约0.1至大约40重量%,优选大约0.2至大约20重量%,最优选大约0.3至大约10重量%的增容剂。
本发明进一步涉及改进压缩制冷、空调或热泵装置中回油到压缩机的方法,所述方法包括在所述装置中使用包含增容剂的本发明的组合物。该增容剂选自烃、二甲基醚、聚氧化亚烷基二醇醚、酰胺、酮、腈、含氯烃、酯、内酯、芳基醚、氢氟代醚、烃醚和1,1,1-三氟烷烃。
本发明进一步涉及在选自矿物油、烷基苯、合成链烷、合成环烷和聚(α)烯烃的制冷润滑剂中增溶包含本发明的组合物的制冷剂或传热流体组合物的方法,其中所述方法包括使所述润滑剂与所述组合物在有效量的增容剂存在下接触,其中所述增容剂选自聚氧化亚烷基二醇醚、酰胺、腈、酮、含氯烃、酯、内酯、芳基醚、氟代醚和1,1,1-三氟烷烃。
本发明的组合物可以进一步包含紫外线(UV)染料和任选增溶剂。UV染料是通过使人能够在泄漏点或制冷、空调或热泵装置附近观察组合物中染料的荧光来检测该组合物的泄漏的可用组分。可以在紫外线下观察染料的荧光。由于这种UV染料在一些组合物中的差溶解度,可能需要增溶剂。
“紫外线”染料是指在电磁谱的紫外线或“近”紫外线区域中吸收光的UV荧光组合物。可以检出UV荧光染料在发出波长为10纳米至750纳米之间的辐射的紫外线照射下产生的荧光。因此,如果含有这些UV荧光染料的组合物从制冷、空调或热泵装置中的给定位置泄漏,可以在泄漏位置检测出荧光。这种UV荧光染料包括但不限于萘二酰亚胺、苝、香豆素、蒽、菲(phenanthracenes)、咕吨、噻吨,苯并夹氧杂蒽、荧光素及其衍生物或组合。
根据本发明,提供了在压缩制冷、空调或热泵装置中检测包含上一句中所述的染料的本发明的组合物的方法。该方法包括向该装置提供该组合物并提供适合在泄漏点或该装置附近检测该组合物的工具。
本发明的增溶剂包含至少一种选自烃、烃醚、二甲基醚、聚氧化亚烷基二醇醚、酰胺、腈、酮、含氯烃、酯、内酯、芳基醚、氟代醚和1,1,1-三氟烷烃的化合物。聚氧化亚烷基二醇醚、酰胺、腈、酮、含氯烃、酯、内酯、芳基醚、氟代醚和1,1,1-三氟烷烃增溶剂之前在本文中作为与传统制冷润滑剂一起使用的增容剂进行定义。
本发明的烃增溶剂包含烃,包括含有5个或更少碳原子和仅仅氢且不含其它官能团的直链、支链或环状烷烃或烯烃。代表性的烃增溶剂包含丙烷、丙烯、环丙烷、正丁烷、异丁烷、2-甲基丁烷和正戊烷。应该指出的是,如果该组合物含有烃,则增溶剂可以不是相同的烃。
本发明的烃醚增溶剂包含仅含碳、氢和氧的醚,例如二甲基醚(DME)。
本发明的增溶剂可以作为单一化合物存在,或可以作为一种以上增溶剂的混合物存在。增溶剂的混合物可以含有两种来自相同化合物类型的增溶剂,如两种内酯,或两种来自两种不同类型的增溶剂,例如内酯和聚氧化亚烷基二醇醚。
在包含制冷剂和UV荧光染料的或包含传热流体和UV荧光染料的本组合物中,该组合物的大约0.001重量%至大约1.0重量%是UV染料,优选大约0.005重量%至大约0.5重量%,最优选0.01重量%至大约0.25重量%。
增溶剂,例如酮可能具有讨厌的气味,其可以通过添加气味遮蔽剂或香料来遮蔽。气味遮蔽剂或香料的典型实例可以包括Evergreen(常绿植物)、Fresh Lemon(清新柠檬)、Cherry(樱桃)、Cinnamon(肉桂)、Peppermint(薄荷)、Floral(花香)或Orange Peel(橙皮),它们均可购得,以及d-苧烯和蒎烯。这种气味遮蔽剂可以以气味遮蔽剂和增溶剂总重量的大约0.001%至多达大约15重量%的浓度使用。
这些UV荧光染料在本发明的组合物中的溶解度可能差。因此,将这些染料引入制冷、空调或热泵装置的方法是难以实施的、昂贵且耗时的。美国专利no.RE36,951描述了使用可插入制冷、空调或热泵装置的部件中的染料粉末、固体丸粒或染料浆的方法。随着制冷剂和润滑剂循环通过该装置,将染料溶解或分散并运载通过整个装置。在该文献中描述了将染料引入制冷或空调装置的许多其它方法。
理想地,UV荧光染料可以溶解在制冷剂本身中,由此不需要任何引入制冷、空调装置或热泵中的专门方法。本发明涉及包括UV荧光染料的组合物,其可以作为在制冷剂中的溶液引入该系统。本发明的组合物即使在低温下也能存储和输送含染料的组合物同时使该染料保持溶解。
在包含制冷剂、UV荧光染料和增溶剂的或包含传热流体和UV荧光染料和增溶剂的本组合物中,总组合物的大约1至大约50重量%,优选大约2至大约25重量%,最优选大约5至大约15重量%是增溶剂。在本发明的组合物中,UV荧光染料以大约0.001重量%至大约1.0重量%,优选0.005重量%至大约0.5重量%,最优选0.01重量%至大约0.25重量%的浓度存在。
本发明进一步涉及在制冷、空调或热泵装置中使用进一步包含紫外线荧光染料和任选增溶剂的组合物的方法。该方法包括将该组合物引入制冷、空调或热泵装置。这可以通过在增溶剂存在下将UV荧光染料溶解在该组合物中并将该组合引入该装置来进行。或者,这可以通过将增溶剂和UV荧光染料合并并将所述组合引入含有制冷剂和/或传热流体的制冷或空调装置来进行。所得组合物可以用在制冷、空调或热泵装置中。
本发明进一步涉及使用包含紫外线荧光染料的组合物检测泄漏的方法。染料在该组合物中的存在能够检出制冷、空调或热泵装置中的制冷剂泄漏。泄漏检测有助于处理、解决或防止该装置或系统的低效运行或设备失效。泄漏检测也有助于人们收纳(contain)该装置运行中所用的化学品。
该方法包括为制冷、空调或热泵装置提供包含本文所述的制冷剂、紫外线荧光染料和任选包含本文所述的增溶剂的本发明的组合物,并使用适合在泄漏点或该装置附近检测含UV荧光染料的制冷剂的工具。适合检测染料的工具包括,但不限于,紫外线灯,常被称作“黑光”或“蓝光”。这种紫外线灯可购自专门为此用途设计的许多来源。一旦已经将含有紫外线荧光染料的组合物引入制冷、空调或热泵装置并已经使其循环通过该系统,可以通过将所述紫外线灯照在该装置上并在任何泄漏点附近观察染料荧光来发现泄漏。
本发明进一步涉及在制冷、空调或热泵装置中替代高GWP制冷剂的方法,其中所述高GWP制冷剂选自R134a、R22、R123、R11、R245fa、R114、R236fa、R124、R12、R410A、R407C、R413A、R417A、R422A、R422B、R422C和R422D、R423A、R507A、R502和R404A,所述方法包括向使用、用过或被设计成使用所述高GWP制冷剂的制冷、空调或热泵装置提供本发明的组合物。
在上一段中所述的方法的具体实施方案中,高GWP制冷剂选自上述R134a、R22、R123、R11、R245fa、R114、R236fa、R124、R12、R410A、R407C、R413A、R417A、R422A、R422B、R422C和R422D、R423A、R507A、R502和R404A。该方法进一步包括向使用、用过或被设计成使用所述高GWP制冷剂的所述制冷、空调或热泵装置提供组合物,其中该组合物选自:大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1234yf;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%反式-HFC-1234ze;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1243zf;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC~134a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-227ea;和大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%CF3I。
蒸气压缩制冷、空调或热泵系统包括蒸发器、压缩机、冷凝器和膨胀器。蒸气压缩循环在多个步骤中重复使用制冷剂,在一个步骤中产生冷却效果并在不同的步骤中产生加热效果。该循环可以简单地如下描述。液体制冷剂通过膨胀器进入蒸发器且液体制冷剂在蒸发器中在低温下沸腾以形成气体并制冷。低压气体进入压缩机,在此气体压缩以提高其压力和温度。较高压力的(压缩的)气体制冷剂随后进入冷凝器,在此制冷剂冷凝并将其热排出到环境中。制冷剂回到膨胀器,由此液体从在冷凝器中的较高压力级膨胀到在蒸发器中的低压级,由此重复该循环。
根据本发明,提供了含有本发明的组合物的制冷、空调或热泵装置。特别地,制冷或空调装置可以是移动装置。
本文所用的移动制冷装置或移动空调装置是指并入公路、铁路、海洋或空中运输装置中的任何制冷或空调装置。此外,意在为被称作“联运”系统的系统(与任何移动载体无关)提供制冷或空调的装置包括在本发明中。这种联运系统包括“集装箱”(联合海/陆运输)以及“可拆卸车体”(联合公路铁路运输)。本发明特别可用于公路运输制冷或空调装置,例如汽车空调装置或制冷的公路运输设备。
本发明的组合物也可用在固定空调和热泵,例如冷却器、高温热泵、住宅和照明商业和商业空调系统中。在固定制冷用途中,本组合物可用在如家用冰箱、制冰机、步入式(walk-in)和伸手可取式(reach-in)冷却器和冷冻机和超市系统的设备中。
本发明进一步涉及制冷方法,包括在要冷却的物体附近蒸发任何本发明的组合物并此后冷凝所述组合物。
本发明进一步涉及制热方法,包括在要加热的物体附近冷凝任何本发明的组合物并此后蒸发所述组合物。
本发明进一步涉及含有本发明的组合物的制冷、空调或热泵装置,其中所述组合物包含至少一种氟烯烃。
本发明进一步涉及含有本发明的组合物的移动空调装置,其中所述组合物包含至少一种氟烯烃。
本发明进一步涉及在制冷、空调或热泵装置中早期检测制冷剂泄漏的方法。该方法包括在所述装置中使用非共沸组合物并监测冷却性能的降低。非共沸组合物在从制冷、空调或热泵装置中泄漏时分馏且较低沸点(较高蒸气压)的组分先从该装置中漏出。发生这种情况时,如果该组合物中的较低沸点组分提供了大部分制冷能力,该装置的能力且因此性能显著降低。在汽车空调系统中,例如,汽车中的乘客会察觉该系统冷却能力的降低。冷却能力的这种降低可以被视为意味着制冷剂泄漏且该系统需要修理。
本发明进一步涉及使用本发明的组合物作为传热流体组合物的方法。该方法包括将所述组合物从热源转移到热沉。
使用传热流体通过辐射、传导或对流从一个空间、位置、物体或对象将热传递、转移或去除到不同的空间、位置、物体或对象。传热流体可以通过提供用于从远程制冷(或加热)系统进行冷却(或加热)的传递手段来充当第二冷却剂。在一些系统中,传热流体可以在整个传递过程中保持恒定状态(即不蒸发或冷凝)。或者,蒸发性冷却法也可以使用传热流体。
热源可以被定义为是理想地从中传递、转移或去除热的任何空间、位置、物体或对象。热源的实例可以是要求制冷或冷却的空间(开放或封闭的),例如超市中的制冷机或冷冻机外壳,需要空调的建筑空间、或需要空调的汽车车厢。热沉可以被定义为是能够吸热的任何空间、位置、物体或对象。蒸气压缩制冷系统是这种热沉的一个实例。
在某些实施方案中,可以以特定重量百分比使用上述组分的特定组合。下列组合物是这类实施方案的实例,而本发明的组合物的范围不限于下列。
在一个实施方案中,本发明涉及组合物,其包含:至少一种选自多元醇酯、聚烷撑二醇、聚乙烯基醚、矿物油、烷基苯、合成链烷、合成环烷和聚(α)烯烃的润滑剂;和选自下列的组合物:大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1234yf;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%反式-HFC-1234ze;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1243zf;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-134a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-227ea;和大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%CF3I。
在另一实施方案中,本发明涉及组合物,其包含选自下述的制冷剂或传热流体组合物:大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1234yf;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%反式-HFC-1234ze;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1243zf;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-134a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-227ea;和大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%CF3I。该组合物也包含增容剂,其选自:i)式R1[(OR2)xOR3]y所示的聚氧化亚烷基二醇醚,其中:x是1至3的整数;y是1至4的整数;R1选自氢和具有1至6个碳原子和y键合位点的脂族烃基;R2选自具有2至4个碳原子的脂族亚烃基;R3选自氢和具有1至6个碳原子的脂族和脂环族烃基;R1和R3的至少一个选自所述烃基;且其中所述聚氧化亚烷基二醇醚具有大约100至大约300原子质量单位的分子量;ii)式R1C(O)NR2R3和环-[R4CON(R5)-]所示的酰胺,其中R1、R2、R3和R5独立地选自具有1至12个碳原子的脂族和脂环族烃基和最多一个具有6至12个碳原子的芳族基团;R4选自具有3至12个碳原子的脂族亚烃基;且其中所述酰胺具有大约100至大约300原子质量单位的分子量;iii)式R1C(O)R2所示的酮,其中R1和R2独立地选自具有1至12个碳原子的脂族、脂环族和芳基烃基,且其中所述酮具有大约70至大约300原子质量单位的分子量;iv)式R1CN所示的腈,其中R1选自具有5至12个碳原子的脂族、脂环族或芳基烃基,且其中所述腈具有大约90至大约200原子质量单位的分子量;v)式RClx所示的含氯烃,其中:x是1或2;R选自具有1至12个碳原子的脂族和脂环族烃基;且其中所述含氯烃具有大约100至大约200原子质量单位的分子量;vi)式R1OR2所示的芳基醚,其中:R1选自具有6至12个碳原子的芳基烃基;R2选自具有1至4个碳原子的脂族烃基;且其中所述芳基醚具有大约100至大约150原子质量单位的分子量;vii)式CF3R1所示的1,1,1-三氟烷烃,其中R1选自具有大约5至大约15个碳原子的脂族和脂环族烃基;viii)式R1OCF2CF2H所示的氟代醚,其中R1选自具有大约5至大约15个碳原子的脂族、脂环族和芳族烃基;或其中所述氟代醚由氟烯烃和多元醇生成,其中所述氟烯烃是CF2=CXY类型的,其中X是氢、氯或氟,且Y是氯、氟、CF3或ORf,其中Rf是CF3、C2F5或C3F7;且所述多元醇是直链或支链的,其中所述直链多元醇是HOCH2(CHOH)x(CRR′)yCH2OH类型的,其中R和R′是氢、CH3或C2H5,x是0-4的整数,y是0-3的整数且z是0或1,且所述支链多元醇是C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w类型的,其中R可以是氢、CH3或C2H5,m是0至3的整数,t和u是0或1,v和w是0至4的整数,且其中t+u+v+w=4;和ix)结构[B]、[C]和[D]所示的内酯:
Figure G200680054110XD00481
其中,R1至R8独立地选自氢或直链、支链、环状、双环的饱和和不饱和的烃基;且分子量为大约100至大约300正确原子质量单位;和x)通式R1CO2R2所示的酯,其中R1和R2独立地选自直链和环状的饱和和不饱和的烷基和芳基;且其中所述酯具有大约80至大约550原子质量单位的分子量。
根据本发明,提供了含有上一段中所述的组合物的制冷、空调或热泵装置。特别地,制冷或空调装置可以是移动装置。
此外,根据该具体实施方案,本发明涉及改进压缩制冷、空调或热泵装置中回油到压缩机的方法。该方法包括在压缩制冷、空调或热泵装置中使用上一段中所述的组合物。
在另一具体实施方案中,本发明涉及组合物,其包含(a)至少一种选自萘二酰亚胺、苝、香豆素、蒽、菲(phenanthracenes)、呫吨、噻吨、苯并夹氧杂蒽、荧光素、所述染料的衍生物及其组合的紫外线荧光染料;和(b)选自下列的组合物:大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1234yf;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%反式-HFC-1234ze;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1243zf;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-134a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-227ea;和大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%CF3I。
根据本发明,提供了在压缩制冷、空调或热泵装置中检测如上一段中所述包含染料的组合物的方法。该方法包括向该装置提供该组合物并提供适合在泄漏点或该装置附近检测该组合物的工具。
根据本发明,提供了含有如前两段所述的组合物的制冷、空调或热泵装置。特别地,该制冷或空调装置可以是移动装置。
此外,根据该具体实施方案,如前三段所述的包括(a)和(b)的组合物进一步包括选自烃、二甲基醚、聚氧化亚烷基二醇醚、酰胺、酮、腈、含氯烃、酯、内酯、芳基醚、氢氟醚和1,1,1-三氟烷烃的增溶剂。
根据本发明,提供了在压缩制冷、空调或热泵装置中检测如上一段中所述包含染料的组合物的方法。该方法包括向该装置提供该组合物并提供适合在泄漏点或该装置附近检测该组合物的工具。
上一段中所述的组合物的增溶剂选自:i)式R1[(OR2)xOR3]y所示的聚氧化亚烷基二醇醚,其中:x是1至3的整数;y是1至4的整数;R1选自氢和具有1至6个碳原子和y键合位点的脂族烃基;R2选自具有2至4个碳原子的脂族亚烃基;R3选自氢和具有1至6个碳原子的脂族和脂环族烃基;R1和R3的至少一个选自所述烃基;且其中所述聚氧化亚烷基二醇醚具有大约100至大约300原子质量单位的分子量;ii)式R1C(O)NR2R3和环-[R4CON(R5)-]所示的酰胺,其中R1、R2、R3和R5独立地选自具有1至12个碳原子的脂族和脂环族烃基和最多一个具有6至12个碳原子的芳族基团;R4选自具有3至12个碳原子的脂族亚烃基;且其中所述酰胺具有大约100至大约300原子质量单位的分子量;iii)式R1C(O)R2所示的酮,其中R1和R2独立地选自具有1至12个碳原子的脂族、脂环族和芳基烃基,且其中所述酮具有大约70至大约300原子质量单位的分子量;iv)式R1CN所示的腈,其中R1选自具有5至12个碳原子的脂族、脂环族或芳基烃基,且其中所述腈具有大约90至大约200原子质量单位的分子量;v)RClx所示的含氯烃,其中:x是1或2;R选自具有1至12个碳原子的脂族和脂环族烃基;且其中所述含氯烃具有大约100至大约200原子质量单位的分子量;vi)式R1OR2所示的芳基醚,其中:R1选自具有6至12个碳原子的芳基烃基;R2选自具有1至4个碳原子的脂族烃基;且其中所述芳基醚具有大约100至大约150原子质量单位的分子量;vii)式CF3R1所示的1,1,1-三氟烷烃,其中R1选自具有大约5至大约15个碳原子的脂族和脂环族烃基;viii)式R1OCF2CF2H所示的氟代醚,其中R1选自具有大约5至大约15个碳原子的脂族、脂环族和芳族烃基;或其中所述氟代醚由氟烯烃和多元醇生成,其中所述氟烯烃是CF2=CXY类型的,其中X是氢、氯或氟,且Y是氯、氟、CF3或ORf,其中Rf是CF3、C2F5或C3F7;且所述多元醇是直链或支链的,其中所述直链多元醇是HOCH2(CHOH)x(CRR′)yCH2OH类型的,其中R和R′是氢、CH3或C2H5,x是0-4的整数,y是0-3的整数且z是0或1,且所述支链多元醇是C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w类型的,其中R可以是氢、CH3或C2H5,m是0至3的整数,t和u是0或1,v和w是0至4的整数,且其中t+u+v+w=4;和ix)结构[B]、[C]和[D]所示的内酯:
Figure G200680054110XD00511
其中,R1至R8独立地选自氢、直链、支链、环状、双环的饱和和不饱和的烃基;且分子量为大约100至大约300原子质量单位;和x)通式R1CO2R2所示的酯,其中R1和R2独立地选自直链和环状的饱和和不饱和的烷基和芳基;且其中所述酯具有大约80至大约550原子质量单位的分子量。
包括上述增容剂或包括上述染料或包括上述染料和增溶剂的特定组合物可用在制冷方法中。制冷方法包括在要冷却的物体附近蒸发该组合物并此后冷凝所述组合物。这些特定组合物也可以用在制热方法中。制热方法包括在要加热的物体附近冷凝该组合物并此后蒸发所述组合物。
在另一具体实施方案中,本发明进一步涉及在选自矿物油、烷基苯、合成链烷、合成环烷和聚(α)烯烃的制冷润滑剂中增溶本发明的制冷剂或传热流体组合物的方法,其中所述方法包括使所述润滑剂与所述制冷剂或传热流体组合物在有效量的增容剂存在下接触,其中所述增容剂选自:
a)式R1[(OR2)xOR3]y所示的聚氧化亚烷基二醇醚(polyoxyalkyleneglycol ether),其中:x是1至3的整数;y是1至4的整数;R1选自氢和具有1至6个碳原子和y键合位点的脂族烃基;R2选自具有2至4个碳原子的脂族亚烃基;R3选自氢和具有1至6个碳原子的脂族和脂环族烃基;R1和R3的至少一个选自所述烃基;且其中所述聚氧化亚烷基二醇醚具有大约100至大约300原子质量单位的分子量;b)式R1C(O)NR2R3和环-[R4CON(R5)-]所示的酰胺,其中R1、R2、R3和R5独立地选自具有1至12个碳原子的脂族和脂环族烃基和最多一个具有6至12个碳原子的芳族基团;R4选自具有3至12个碳原子的脂族亚烃基;且其中所述酰胺具有大约100至大约300原子质量单位的分子量;c)式R1C(O)R2所示的酮,其中R1和R2独立地选自具有1至12个碳原子的脂族、脂环族和芳基烃基,且其中所述酮具有大约70至大约300原子质量单位的分子量;d)式R1CN所示的腈,其中R1选自具有5至12个碳原子的脂族、脂环族或芳基烃基,且其中所述腈具有大约90至大约200原子质量单位的分子量;e)式RClx所示的含氯烃,其中:x是1或2;R选自具有1至12个碳原子的脂族和脂环族烃基;且其中所述含氯烃具有大约100至大约200原子质量单位的分子量;f)式R1OR2所示的芳基醚,其中:R1选自具有6至12个碳原子的芳基烃基;R2选自具有1至4个碳原子的脂族烃基;且其中所述芳基醚具有大约100至大约150原子质量单位的分子量;g)式CF3R1所示的1,1,1-三氟烷烃,其中R1选自具有大约5至大约15个碳原子的脂族和脂环族烃基;h)式R1OCF2CF2H所示的氟代醚,其中R1选自具有大约5至大约15个碳原子的脂族和脂环族烃基;或其中所述氟代醚由氟烯烃和多元醇生成,其中所述氟烯烃是CF2=CXY类型的,其中X是氢、氯或氟,且Y是氯、氟、CF3或ORf,其中Rf是CF3、C2F5或C3F7;且所述多元醇是HOCH2CRR′(CH2)z(CHOH)xCH2(CH2OH)y类型的,其中R和R′是氢、CH3或C2H5,x是0-4的整数,y是0-3的整数且z是0或1;和i)结构[B]、[C]和[D]所示的内酯:
Figure G200680054110XD00521
其中R1至R8独立地选自氢、直链、支链、环状、双环的饱和和不饱和的烃基;且分子量为大约100至大约300原子质量单位;和j)通式R1CO2R2所示的酯,其中R1和R2独立地选自直链和环状的饱和和不饱和的烷基和芳基;且其中所述酯具有大约80至大约550原子质量单位的分子量。
在具体实施方案中,上一段的制冷剂或传热流体组合物选自:其中所述制冷剂或传热流体包含选自下列的组合物:大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1234yf;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%反式-HFC-1234ze;大约1重量%至大约99重量%HFC-1225ye和大约99重量%至大约1重量%HFC-1243zf;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-134a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-152a;大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%HFC-227ea;和大约1重量%至大约99重量%反式-HFC-1234ze和大约99重量%至大约1重量%CF3I。
在另一实施方案中,本发明涉及用于制备泡沫的包含本文所述的本发明的含氟烯烃的组合物的发泡剂组合物。在另一些实施方案中,本发明提供了可发泡组合物,和优选聚氨酯和聚异氰酸酯泡沫组合物,和制备泡沫的方法。在这样的泡沫实施方案中,包含一种或多种本发明的含氟烯烃的组合物作为可发泡组合物中的发泡剂,该组合物优选包括一种或多种能够在适当条件下反应和发泡形成泡沫或多孔结构的附加组分。本领域中公知的任何方法,例如经此引用并入本文的"PolyurethanesChemistry and Technology,"卷I和II,Saunders和Frisch,1962,JohnWiley and Sons,New York,N.Y.中所述的那些可以根据本发明的泡沫实施方案使用或经调节使用。
本发明进一步涉及形成泡沫的方法,包括(a)在可发泡组合物中加入本发明的含氟烯烃的组合物;和(b)使该可发泡组合物在有效形成泡沫的条件下反应。
本发明的另一实施方案涉及本文所述的含氟烯烃的组合物用作可喷施组合物中的推进剂的用途。另外,本发明涉及包含本文所述的含氟烯烃的组合物的可喷施组合物。在可喷施组合物中也可以存在要与惰性成分、溶剂和其它材料一起喷施的活性成分。优选地,该可喷施组合物是气溶胶。要喷施的合适的活性材料包括但不限于,化妆品材料,例如除臭剂、香精、喷发剂、清洁剂、和磨光剂以及医药材料,例如抗气喘剂和抗口臭药剂。
本发明进一步涉及制造气溶胶产品的方法,包括在气溶胶容器中向活性成分中添加本文所述的含氟烯烃的组合物的步骤,其中所述组合物充当推进剂。
另一方面提供了抑制火焰的方法,所述方法包括使火焰与包含本公开的含氟烯烃的组合物的流体接触。可以使用任何合适的使火焰与本组合物接触的方法。例如,可以将本公开的含氟烯烃的组合物喷射、倾倒和以类似方式施加到火焰上,或可以将火焰的至少一部分浸在火焰抑制组合物中。考虑到本文的教导,本领域技术人员容易将各种火焰抑制传统装置和方法用在本公开中。
另一实施方案提供了在全淹没用途中熄灭或抑制火的方法,包括提供包含本公开的含氟烯烃的组合物的试剂;将该试剂装在加压排出系统中;并将该试剂排出到区域中以熄灭或抑制该区域中的火。
另一实施方案提供了使区域钝化以防止着火或爆炸的方法,包括提供包含本公开的含氟烯烃的组合物的试剂;将该试剂装在加压排出系统中;并将该试剂排出到该区域中以防止发生着火或爆炸。
术语“熄灭”通常用于表示火焰的完全消灭;而“抑制”通常用于表示火焰或爆炸的减轻,而不一定完全消灭。本文所用的术语“熄灭”和“抑制”可互换使用。有四种常见类型的卤代烃防火和防爆炸用途。(1)在全淹没火焰熄灭和/或抑制用途中,将该试剂排出到一定空间中以达到足以熄灭或抑制现有火焰的浓度。全淹没应用包括保护封闭的可能有人的空间,例如计算机房,以及专用的通常无人的空间,例如飞机发动机机舱和车辆中的发动机隔室。(2)在流动(streaming)用途中,该试剂直接施加到火焰上或施加到着火区域中。这通常使用手工操作的带轮的或便携的装置实现。作为流动用途被包含的第二方法使用“局部化”系统,其将试剂从一个或多个固定喷嘴排向火焰上。局部化系统可以手动或自动激活。(3)在爆炸抑制中,排出本公开的含氟烯烃的组合物以抑制已经引发的爆炸。在此用途中通常使用术语“抑制”,因为爆炸通常是自限的。但是,该术语的使用不一定意味着爆炸未被该试剂熄灭。在此用途中,通常使用检测器检测来自爆炸的膨胀火球,并迅速排出该试剂以抑制爆炸。在防卫用途中主要而非单独使用爆炸抑制。(4)在钝化(inertion)中,将本公开的含氟烯烃的组合物排出到空间中以防止引发爆炸或着火。通常,使用与全淹没火焰熄灭或抑制所用的类似或相同的系统。通常,检测危险条件(例如易燃或爆炸性气体的危险浓度)的存在,然后排出本公开的含氟烯烃的组合物以防止发生爆炸或着火直至该状况可以补救。
可以通过将该组合物引入火焰周围的封闭区域来进行熄灭方法。可以采用任何已知的引入方法,只要以适当时间间隔将适当量的该组合物计量加入该封闭区域。例如,可以通过流动,例如使用传统的便携(或固定)灭火设备;通过喷雾;或通过淹没,例如通过将该组合物释放(使用适当的管道、阀和控制装置)到火焰周围的封闭区域中,来引入组合物。该组合物可以任选与惰性推进剂,例如氮气、氩气、缩水甘油基叠氮聚合物的分解产物或二氧化碳结合以提高该组合物从所用的流动或淹没设备排出的速率。
优选地,熄灭方法包括将本公开的含氟烯烃的组合物以足以灭火或火焰的量引到火或火焰上。本领域技术人员会认识到,熄灭特定火焰所需的火焰抑制剂的量取决于危险的性质和程度。当火焰抑制剂通过淹没引入时,可以使用杯燃烧器试验数据测定熄灭特定类型和大小的火焰所需的火焰抑制剂的量或浓度。
例如在美国专利No.5,759,430中描述了可用于测定在全淹没用途或火焰钝化中用于熄灭或抑制火焰时含氟烯烃的组合物的有效浓度范围的实验室试验。
实施例
实施例1
蒸气泄漏的影响
在容器中装入在-25℃或如果指定的话在25℃的初始组合物,并测量该组合物的初始蒸气压。使该组合物从容器中泄漏,同时保持温度恒定,直至去除50重量%的初始组合物,此时测量容器内留下的组合物的蒸气压。结果显示在表9中。
表9
组合物     初始P     初始P      50%泄漏后   50%泄漏后    ΔP
wt%       (Psia)    (kPa)      (Psia)       (kPa)        (%)
HFC-1234yf/HFC-32
7.4/92.6   49.2      339        49.2         339          0.0%
1/99       49.2      339        49.2         339          0.0%
20/80      49.0      338        48.8         337          0.3%
40/60      47.5      327        47.0         324          1.0%
57/43      44.9      309        40.5         280          9.6%
58/42      44.6      308        40.1         276          10.2%
HFC-1234yf/HFC-125
10.9/89.1  40.8      281        40.8         281          0.0%
1/99       40.3       278        40.2        277          0.0%
20/80      40.5      279        40.3         278          0.4%
40/60      38.7      267        37.0         255          4.4%
50/50      37.4      258        34.0         235          9.0%
51/49      37.3      257        33.7         232          9.6%
52/48      37.1      256        33.3         229          10.3%
HFC-1234yf/HFC-134
1/99       11.7      81         11.6         80           0.7%
10/90      12.8      88         12.2         84           4.5%
20/80      13.7      95         13.0         89           5.6%
40/60      15.2      105        14.6         101          4.1%
60/40      16.3      113        16.0         110          2.0%
80/20      17.2      119        17.1         118          0.6%
90/10      17.6      121        17.5         121          0.2%
99/1       17.8      123        17.8         123          0.0%
HFC-1234yf/HFC-134a
70.4/29.6  18.4      127        18.4         127          0.0%
80/20       18.3       126      18.3       126        0.1%
90/10       18.2       125      18.1       125        0.1%
99/1        17.9       123      17.9       123        0.1%
40/60       17.9       123      17.8       123        0.7%
20/80       17.0       117      16.7       115        1.7%
10/90       164        113      16.1       111        1.5%
1/99        15.6       107      15.6       107        0.3%
HFC-1234yf/HFC-152a
91.0/9.0    17.9       123      17.9       123        0.0%
99/1        17.9       123      17.8       123        0.1%
60/40       17.4       120      17.2       119        0.7%
40/60       16.6       115      16.4       113        1.6%
20/80       15.7       108      15.4       106        2.0%
10/90       15.1       104      14.9       103        1.5%
1/99        14.6       100      14.5       100        0.2%
HFC-1234yf/HFC-161
1/99        25.3       174      25.3       174        0.0%
10/90       25.2       174      25.2       174        0.1%
20/80       24.9       172      24.8       171        0.8%
40/60       23.8       164      23.2       160        2.6%
60/40       22.0       152      21.3       147        3.2%
80/20       19.8       137      19.5       134        1.9%
90/10       18.8       129      18.6       128        0.9%
99/1        17.9       123      17.9       123        0.1%
HFC-1234yf/FC-143a
17.3/82.7   39.5       272      39.5       272        0.0%
10/90       39.3       271      39.3       271        0.1%
1/99        38.7       267      38.6       266        0.1%
40/60       38.5       266      37.8       260        1.9%
60/40       36.3       250       32.8       226       9.5%
61/39       36.1       249       32.4       223       10.2%
HFC-1234yf/HFC-227ea
84.6/15.4   18.0       124       18.0       124       0.0%
90/10       18.0       124       18.0       124       0.0%
99/1        17.9       123       17.9       123       0.0%
60/40       17.6       121       17.4       120       1.2%
40/60       16.7       115       15.8       109       5.4%
29/71       15.8       109       14.2       98        9.7%
28/72       15.7       108       14.1       97        10.2%
HFC-1234yf/HFC-236fa
99/1        17.8       122       17.7       122       0.2%
90/10       17.0       117       16.6       115       2.4%
80/20       16.2       112       15.4       106       5.1%
70/30       15.3       106       14.0       97        8.5%
66/34       15.0       103       13.5       93        10.0%
HFC-1234yf/HFC-1225ye
1/99        11.6       80        11.5       79        0.5%
10/90       12.6       87        12.2       84        3.2%
20/80       13.5       93        12.9       89        4.3%
40/60       15.0       103       14.4       99        3.7%
60/40       16.2       111       15.8       109       22%
80/20       17.1       118       16.9       117       0.9%
90/10       17.5       120       17.4       120       0.3%
99/1        17.8       123       17.8       123       0.0%
HFC-1234yf/反式-HFC-1234ze
1/99        11.3       78        11.3       78        0.4%
10/90       12.2       84        11.8       81        3.3%
20/80       13.1       90       12.5       86       4.6%
40/60       14.6       101      14.0       96       4.3%
60/40       15.8       109      15.4       106      2.7%
80/20       16.9       117      16.7       115      1.1%
90/10       17.4       120      17.3       119      05%
99/1        17.8       123      17.8       123      0.1%
HFC-1234yf/HFC-1243zf
1/99       13.1        90       13.0       90       0.2%
10/90      13.7        94       13.5       93       1.6%
20/80      14.3        99       14.0       97       2.4%
40/60      15.5        107      15.1       104      2.2%
60/40      16.4        113      16.2       112      1.4%
80/20      17.2        119      17.1       118      0.5%
90/10      17.5        121      17.5       121      0.2%
99/1       17.8        123      17.8       123      0.0%
HFC-1234yf/丙烷
51.5/48.5   33.5       231      33.5       231      0.0%
60/40       33.4       230      33.3       229      0.4%
80/20       31.8       220      29.0       200      8.9%
81/19       31.7       218      28.5       196      10.0%
40/60       33.3       230      33.1       228      0.6%
20/80       32.1       221      31.2       215      2.9%
10/90       31.0       214      30.2       208      2.6%
1/99        29.6       204      29.5       203      0.4%
HFC-1234yf/正丁烷
98.1/1.9    17.9       123      17.9       123      0.0%
99/1        17.9       123      17.9       123      0.0%
100/0       17.8       123      17.8       123      0.0%
80/20       16.9       116      16.1       111      4.4%
70/30       16.2       112       14.4       99       10.8%
71/29       16.3       112       14.6       101      9.9%
HFC-1234yf/异丁烷
88.1/11.9   19.0       131       19.0       131      0.0%
95/5        18.7       129       18.6       128      0.7%
99/1        18.1       125       18.0       124      0.6%
60/40       17.9       123       16.0       110      10.3%
61/39       17.9       123       16.2       112      9.4%
HFC-1234yf/DME
53.5/46.5   13.1       90        13.1       90       0.0%
40/60       13.3       92        13.2       91       0.7%
20/80       14.1       97        13.9       96       1.3%
10/90       14.3       99        14.3       98       0.5%
1/99        14.5       100       14.5       100      0.0%
80/20       14.5       100       14.0       96       3.3%
90/10       15.8       109       15.3       105      3.5%
99/1        17.6       121       17.5       121      0.6%
HFC-1234yf/CF3SCF3
1/99        12.1       83        12.0       83       0.2%
10/90       12.9       89        12.7       87       2.0%
20/80       13.8       95        13.4       92       2.8%
40/60       15.1       104       14.7       101      2.7%
60/40       16.2       112       15.9       110      1.9%
80/20       17.1       118       16.9       117      0.9%
90/10       17.5       120       17.4       120      0.5%
99/1        17.8       123       17.8       123      0.0%
HFC-1234yf/CF3I
1/99        12.0       83        12.0       83       0.2%
10/90       12.9       89       12.7       87       1.7%
20/80       13.7       94       13.3       92       2.6%
40/60       15.1       104      14.7       101      2.7%
60/40       16.2       111      15.8       109      2.0%
80/20       17.1       118      16.9       116      1.1%
90/10       17.5       120      17.4       120      0.5%
99/1        17.8       123      17.8       123      0.1%
HFC-125/HFC-1234yf/异丁烷(25℃)
85.1/11.5/3.4 201.3    1388     201.3      1388     0.0%
HFC-125/HFC-1234yf/正丁烷(25℃)
67/32/1     194.4      1340     190.2      1311     2.2%
HFC-32/HFC-125/HFC-1234yf(25℃)
40/50/10    240.6      1659     239.3      1650     0.5%
23/25/52    212.6      1466     192.9      1330     9.3%
15/45/40    213.2      1470     201.3      1388     5.6%
10/60/30    213.0      1469     206.0      1420     3.3%
HFC-1225ye/反式-HFC-1234ze
63.O/37.O   11.7       81       11.7       81       0.0%
80/20       11.6       80       11.6       80       0.0%
90/10       11.6       80       11.6       80       0.1%
99/1        11.5       79       11.5       79       0.0%
60/40       11.7       81       11.7       81       0.0%
40/60       11.6       80       11.6       80       0.1%
20/80       11.5       79       11.4       79       0.2%
10/90       11.3       78       11.3       78       0.1%
1/99        11.2       77       11.2       77       0.1%
HFC-1225ye/HFC-1243zf
40.0/60.0   13.6       94       13.6       94       0.0%
20/80       13.4       93       13.4       92       0.1%
10/90       13.2       91       13.2       91       0.2%
1/99        13.0       90       13.0       90       0.0%
60/40       13.4       92       13.4       92       0.4%
80/20       12.8       88       12.6       87       1.4%
90/10       12.3       85       12.1       83       1.5%
99/1        11.6       80       11.5       79       0.3%
HFC-1225ye/HFC-134
52.2/47.8   12.8       88       12.8       88       0.0%
80/20       12.4       85       12.3       85       0.6%
90/10       12.0       83       11.9       82       0.8%
99/1        11.5       79       11.5       79       0.2%
40/60       12.7       88       12.7       87       0.2%
20/80       12.3       85       12.2       84       0.8%
10/90       12.0       83       11.9       82       0.9%
1/99        11.6       80       11.6       80       0.2%
HFC-1225ye/HFC-134a
1/99        15.5       107      15.5       107      0.0%
10/90       15.2       105      15.2       105      0.3%
20/80       15.0       103      14.9       103      0.5%
40/60       14.4       99       14.2       98       1.0%
60/40       13.6       94       13.4       93       1.4%
80/20       12.7       88       12.5       86       1.6%
90/10       12.2       84       12.0       83       1.3%
99/1        11.5       80       11.5       79       0.2%
HFC-1225ye/HFC-152a
7.3/92.7    14.5       100      14.5       100      0.0%
1/99        14.5       100      14.5       100      0.0%
40/60       14.2       98       14.2       98       0.4%
60/40       13.7       95       13.6       93       1.1%
80/20       12.9       89       12.7       87       1.5%
90/10       12.2       84       12.1       83       1.1%
99/1        11.5       80       11.5       79       0.1%
HFC-1225ye/HFC-161
1/99        25.2       174      25.2       174      0.0%
10/90       24.9       172      24.8       171      0.6%
20/80       24.5       169      24.0       165      2.0%
40/60       22.9       158      21.4       148      6.5%
56/44       20.9       144      18.8       130      10.0%
99/1        11.7       81       11.6       80       1.0%
90/10       14.1       97       13.0       90       7.5%
84/16       15.5       107      14.0       96       9.9%
83/17       15.8       109      14.2       98       10.2%
HFC-1225ye/HFC-227ea
1/99        10.0       69       10.0       69       0.0%
10/90       10.1       70       10.1       70       0.2%
20/80       10.3       71       10.3       71       0.2%
40/60       10.6       73       10.6       73       0.4%
60/40       10.9       75       10.9       75       0.4%
80/20       11.2       77       11.2       77       03%
90/10       11.3       78       11.3       78       0.1%
99/1        11.5       79       11.5       79       0.0%
HFC-1225ye/HFC-236ea
99/1        11.4       79       11.4       79       0.0%
90/10       11.3       78       11.2       77       0.5%
80/20       11.0       75       10.7       74       2.0%
60/40       10.2       70       9.4        65       8.3%
57/43       10.1       69       9.1       63       9.9%
56/44       10.0       69       9.0       62       10.6%
HFC-1225ye/HFC-236fa
99/1        11.4       79       11.4      79       0.1%
90/10       11.1       77       11.0      76       1.1%
80/20       10.7       74       10.4      72       2.4%
60/40       9.8        68       9.2       63       6.6%
48/52       9.2        63       8.2       57       10.0%
HFC-1225ye/HFC-245fa
99/1        11.4       79       11.4      78       0.3%
90/10       10.9       75       10.6      73       2.5%
80/20       10.4       72       9.8       68       5.7%
70/30       9.9        68       8.9       61       9.9%
69/21       9.8        68       8.8       60       10.5%
HFC-1225ye/丙烷
29.7/70.3   30.4       209      30.4      209      0.0%
20/80       30.3       209      30.2      208      0.2%
10/90       30.0       207      29.9      206      0.4%
1/99        29.5       203      29.5      203      0.1%
60/40       29.5       203      28.5      197      3.3%
72/28       28.4       195      25.6      176      9.8%
73/27       28.2       195      25.2      174      10.8%
HFC-1225ye/正丁烷
89.5/10.5   12.3       85       12.3      85       0.0%
99/1        11.7       81       11.6      80       0.9%
80/20       12.2       84       12.0      83       1.5%
65/35       11.7       80       10.5      72       9.9%
64/36       11.6       80       10.4      71       10.9%
HFC-1225ye/异丁烷
79.3/20.7   13.9       96       13.9       96       0.0%
90/10       13.6       94       13.3       92       2.4%
99/1        11.9       82       11.6       80       2.8%
60/40       13.5       93       13.0       89       4.1%
50/50       13.1       91       11.9       82       9.6%
49/51       13.1       90       11.8       81       10.2%
HFC-1225ye/DME
82.1/17.9   10.8       74       10.8       74       0.0%
90/10       10.9       75       10.9       75       0.3%
99/1        11.4       78       11.4       78       0.2%
60/40       11.5       79       11.2       77       2.4%
40/60       12.8       88       12.1       84       4.8%
20/80       13.9       96       13.5       93       3.0%
10/90       14.3       98       14.1       97       1.1%
1/99        14.5       100      14.4       100      0.1%
HFC-1225ye/CF3I
1/99        11.9       82       11.9       82       0.0%
10/90       11.9       82       11.8       82       0.1%
20/80       11.8       81       11.8       81       0.0%
40/60       11.7       80       11.7       80       0.0%
60/40       11.6       80       11.6       80       0.0%
80/20       11.5       79       11.5       79       0.0%
90/10       11.5       79       11.5       79       0.0%
99/1        11.5       79       11.5       79       0.0%
HFC-1225ye/CF3SCF3
37.0/63.0   12.4       86       12.4       86       0.0%
20/80       12.3       85       12.3       85       0.1%
10/90       12.2       84       12.2        84       0.1%
1/99        12.0       83       12.0        83       0.1%
60/40       12.3       85       12.3        85       0.2%
80/20       12.0       83       11.9        82       04%
90/10       11.7       81       11.7        81       0.3%
99/1        11.5       79       11.5        79       0.1%
HFC-1225ye/HFC-134a/HFC-152a(25℃)
76/9/15     81.3       561       80.5       555      1.0%
HFC-1225ye/HFC-134a/HFC-161(25℃)
86/10/4     82.1       566       80.2       553      2.3%
HFC-1225ye/HFC-134a/异丁烷(25℃)
87/10/3     83.4       575       80.3       554      3.7%
HFC-1225ye/HFC-134a/DME(25℃)
87/10/3     77.2       532       76.0       524      1.6%
HFC-1225ye/HFC-152a/异丁烷(25℃)
85/13/2     81.2       560       79.3       547      2.3%
HFC-1225ye/HFC-152a/DME(25℃)
85/13/2     76.6       528       76.0       524      0.8%
HFC-1225ye/HFC-1234yf/HFC-134a(25℃)
70/20/10    86.0       593       84.0       579      2.3%
20/70/10    98.2       677       97.5       672      0.7%
HFC-1225ye/HFC-1234yf/HFC-152a(25℃)
70/25/5     85.1       587       83.4       575      2.0%
25/70/5     95.4       658       94.9       654      0.5%
HFC-1225ye/HFC-1234yf/HFC-125(25℃)
25/71/4       105.8       729       96.3       664       9.0%
75/21/4       89.5        617       83.0       572       7.3%
75/24/1       85.3        588       82.3       567       3.5%
25/74/1       98.0        676       95.1       656       3.0%
HFC-1225ye/HFC-1234yf/CF3I(25℃)
40/40/20      87.5        603       86.0       593       1.7%
45/45/10      89.1        614       87.7       605       1.6%
HFC-1225ye/HFC-134a/HFC-152a/HFC-32(25℃)
74/8/17/1     86.1        594       81.5       562       5.3%
HFC-125/HFC-1225ye/异丁烷(25℃)
85.1/11.5/3.4 186.2       1284      179.2      1236      3.8%
HFC-32/HFC-125/HFC-1225ye(25℃)
30/40/30      212.7       1467      194.6      1342      8.5%
反式-HFC-1234ze/顺式-HFC-1234ze
99/1          11.1         77       11.1        76       0.4%
90/10         10.5         72       10.1        70       3.4%
80/20         9.8          68       9.1         63       7.1%
73/27         9.3          64       8.4         58       99%
72/28         9.3          64       8.3         57       10.3%
反式-HFC-1234ze/HFC-1243zf
17.0/83.0     13.0         90       13.0        90       0.0%
10/90         13.0         90       13.0        90       0.0%
1/99          13.0         90       13.0        90       0.0%
40/60         12.9         89       12.9        89       0.1%
60/40       12.6        87       12.5       86       0.6%
80/20       12.1        83       12.0       82       0.8%
90/10       11.7        80       11.6       80       0.7%
99/1        11.2        77       11.2       77       0.1%
反式-HFC-1234ze/HFC-134
45.7/54.3   12.5        86       12.5       86       0.0%
60/40       12.4        85       12.4       85       0.2%
80/20       12.0        83       11.9       82       0.7%
90/10       11.7        80       11.6       80       0.7%
99/1        11.2        77       11.2       77       0.1%
20/80       12.2        84       12.2       84       0.4%
10/90       11.9        82       11.9       82       0.6%
1/99        11.6        80       11.6       80       0.1%
反式-HFC-1234ze/HFC-134a
9.5/90.5    15.5        107      15.5       107      0.0%
1/99        15.5        107      15.5       107      0.0%
10/60       15.1        104      15.0       103      0.9%
60/40       14.3        99       14.0       96       2.5%
80/20       13.1        90       12.6       87       4.0%
90/10       12.3        85       11.9       82       3.3%
99/1        11.3        78       11.3       78       0.5%
反式-HFC-1234ze/HFC-152a
21.6/78.4   14.6        101      14.6       101      0.0%
10/90       14.6        101      14.6       101      0.0%
1/99        14.5        100      14.5       100      0.0%
40/60       14.5        100      14.5       100      0.1%
60/40       14.1        97       13.9       96       1.1%
80/20       13.2        91       12.8       88       2.5%
90/10       12.4        85       12.0       83       2.6%
99/1        11.3       78       11.3       78       0.4%
反式-HFC-1234ze/HFC-161
1/99        25.2       174      25.2       174      0.0%
10/90       25.0       172      24.8       171      0.6%
20/80       24.5       169      24.0       165      2.1%
40/60       22.8       157      21.2       146      7.0%
52/48       21.3       147      19.2       132      9.9%
53/47       21.2       146      19.0       131      10.2%
99/1        11.5       79       11.3       78       1.2%
90/10       13.8       95       12.6       87       8.6%
88/12       14.3       99       12.9       89       9.5%
87/13       14.5       100      13.1       90       10.0%
反式-HFC-1234ze/HFC-227ea
59.2/40.8   11.7       81       11.7       81       0.0%
40/60       11.6       80       11.5       79       0.3%
20/80       11.1       76       10.9       75       1.3%
10/90       10.6       73       10.5       72       1.3%
1/99        10.0       69       10.0       69       0.2%
80/20       11.6       80       11.5       80       0.2%
90/10       11.4       79       11.4       78       0.3%
99/1        11.2       77       11.2       77       0.0%
反式-HFC-1234ze/HFC-236ea
99/1        11.2       77       11.2       77       0.0%
90/10       11.0       76       11.0       76       0.4%
80/20       10.8       75       10.6       73       1.6%
60/40       10.2       70       9.5        66       6.6%
54/46       9.9        69       9.0        62       9.5%
53/47       9.9        68       8.9        61       10.1%
反式-HFC-1234ze/HFC-236fa
99/1        11.2       77       11.2       77       0.1%
90/10       10.9       75       10.8       75       0.8%
80/20       10.6       73       10.4       71       2.0%
60/40       9.8        67       9.3        64       5.4%
44/56       9.0        62       8.1        56       9.7%
43/57       8.9        62       8.0        55       10.1%
反式-HFC-1234ze/HFC-245fa
99/1        11.2       77       11.1       77       0.2%
90/10       10.7       74       10.5       73       2.0%
80/20       10.3       71       9.8        68       4.7%
70/30       9.8        68       9.0        62       8.2%
67/33       9.7        67       8.7        60       9.7%
66/34       9.6        66       8.7        60       10.2%
反式-HFC-1234ze/丙烷
28.5/71.5    30.3      209      30.3       209      0.0%
10/90        30.0      206      29.9       206      0.3%
1/99         29.5      203      29.5       203      0.1%
40/60        302       208      30.1       207      0.4%
60/40        29.3      202      28.3       195      3.4%
71/29        284       196      25.7       177      9.3%
72/28        283       195      25.4       175      10.2%
反式-HFC-1234ze/正丁烷
88.6/11.4   11.9       82       11.9       82       0.0%
95/5        11.7       81       11.7       80       0.7%
99/1        11.4       78       11.3       78       0.6%
70/30       11.5       79       11.0       76       42%
62/38       11.2       77       10.2       70       9.3%
61/39       11.2       77       10.0       69       10.1%
反式-HFC-1234ze/异丁烷
77.9/22.1   12.9       89       12.9       89       0.0%
90/10       12.6       87       12.4       85       1.6%
99/1        11.4       79       11.3       78       1.1%
60/40       12.6       87       12.3       85       2.4%
39/61       11.7       81       10.6       73       9.8%
38/62       11.7       81       10.5       72       10.1%
反式-HFC-1234ze/DME
84.1/15.9   10.8       74       10.8       74       0.0%
90/10       10.8       75       10.8       75       0.0%
99/1        11.1       77       11.1       77       0.0%
60/40       11.5       79       11.3       78       2.2%
40/60       12.7       88       12.2       84       4.4%
20/80       13.9       96       13.5       93       2.9%
10/90       14.3       98       14.1       97       1.0%
1/99        14.5       100      14.5       100      0.0%
反式-HFC-1234ze/CF3SCF3
34.3/65.7   12.7       87       12.7       87       0.0%
20/80       12.6       87       12.6       87       0.2%
10/90       12.4       85       12.3       85       0.3%
1/99        12.0       83       12.0       83       0.1%
60/40       12.4       86       12.4       85       0.5%
80/20       12.0       82       11.8       81       1.1%
90/10       11.6       80       11.5       79       0.9%
99/1        11.2       77       11.2       77       0.2%
反式-HFC-1234ze/CF3I
1/99        11.9       82       11.9       82       0.0%
10/90       11.9       82       11.9       82       0.0%
20/80       11.8       81       11.8       81       0.0%
40/60       11.6       80       11.6       80       0.1%
60/40       11.4       79       11.4       79       0.1%
80/20       11.3       78       11.3       78       0.1%
90/10       11.3       78       11.2       77       0.1%
99/1        11.2       77       11.2       77       0.0%
HFC-32/HFC-125/反式-HFC-1234ze(25℃)
30/40/30    221.5      1527     209.4      1444     5.5%
30/50/20    227.5      1569     220.2      1518     3.2%
HFC-125/反式-HFC-1234ze/正丁烷(25℃)
66/32/2     180.4      1244     170.3      1174     5.6%
HFC-1243zf/HFC-134
63.0/37.0   13.5       93       13.5       93       0.0%
80/20       13.4       93       13.4       92       0.1%
90/10       13.2       91       13.2       91       0.2%
99/1        13.0       90       13.0       90       0.0%
40/60       13.3       92       13.3       91       0.5%
20/80       12.7       88       12.6       87       1.3%
10/90       12.3       84       12.1       83       1.5%
1/99        11.6       80       11.6       80       0.3%
HFC-1243zf/HFC-134a
25.1/74.9   15.9       110       15.9       110      0.0%
10/90       15.8       109       15.8       109      0.1%
1/99        15.5       107       15.5       107      0.1%
40/60       15.8       109       15.8       109      0.2%
60/40       15.3       106       15.1       104      1.2%
80/20       14.4       99        14.1       97       2.1%
90/10       13.8       95        13.5       93       1.7%
99/1        13.1       90       13.0       90       0.2%
HFC-1243zf/HFC-152a
40.7/59.3   15.2       104      15.2       104      0.0%
20/80       15.0       103      15.0       103      0.2%
10/90       14.8       102      14.7       102      0.3%
1/99        14.5       100      14.5       100      0.1%
60/40       15.0       103      14.9       103      0.3%
80/20       14.4       99       14.2       98       1.1%
90/10       13.8       95       13.6       94       1.2%
99/1        13.1       90       13.1       90       0.2%
HFC-1243zf/HFC-161
1/99        25.2       174      25.2       174      0.0%
10/90       24.9       172      24.8       171      0.3%
20/80       24.5       169      24.2       167      0.9%
40/60       23.3       160      22.6       156      2.9%
60/40       21.5       148      20.1       139      6.3%
78/22       18.8       130      16.9       117      10.0%
90/10       16.2       111      14.6       101      9.5%
99/1        13.4       92       13.1       90       1.7%
HFC-1243zf/HFC-227ea
78.5/21.5   13.1       90       13.1       90       0.0%
90/10       13.1       90       13.1       90       0.0%
99/1        13.0       90       13.0       90       0.0%
60/40       13.0       90       13.0       89       0.2%
40/60       12.6       87       12.5       86       1.1%
20/80       11.8       81       11.5       79       2.7%
10/90       11.1       76       10.7       74       2.8%
1/99        10.1       69       10.0       69       0.6%
HFC-1243zf/HFC-236ea
99/1        13.0       89       13.0       89       0.0%
90/10       12.8       88       12.7       87       0.5%
80/20       12.5       86       12.3       84       1.8%
60/40       11.7       81       11.0       76       6.6%
53/47       11.4       79       10.3       71       9.9%
52/48       11.4       78       10.2       70       10.5%
HFC-1243zf/HFC-236fa
99/1        13.0       89       12.9       89       0.1%
90/10       12.6       87       12.5       86       1.0%
80/20       12.2       84       11.9       82       2.5%
60/40       11.3       78       10.5       73       6.6%
49/51       10.6       73       9.6        66       9.9%
48/52       10.6       73       9.5        65       10.2%
HFC-1243zf/HFC-245fa
99/1        12.9       89       12.9       89       0.2%
90/10       12.5       86       12.2       84       2.1%
80/20       12.0       83       11.4       79       4.6%
70/30       11.5       79       10.6       73       7.9%
66/34       11.3       78       10.2       70       9.6%
65/35       11.2       77       10.1       69       10.2%
HFC-1243zf/丙烷
32.8/67.2   31.0       213      31.0       213      0.0%
10/90       30.3       209      30.1       207      0.7%
1/99        295        204      29.5       203      0.1%
60/40       30.1       208      29.2       201      3.2%
72/28       29.0       200      26.1       180      10.2%
71/29       29.2       201      26.5       182      9.3%
HFC-1243zf/正丁烷
90.3/9.7    13.5       93       13.5       93       0.0%
99/1        13.1       90       13.1       90       0.2%
62/38       12.6       87       11.4       79       9.4%
61/39       12.6       87       11.3       78       10.3%
HFC-1243zf/异丁烷
80.7/19.3   14.3       98       14.3       98       0.0%
90/10       14.1       97       14.0       96       0.9%
99/1        13.2       91       13.1       90       0.7%
60/40       13.8       95       13.4       92       3.2%
45/55       13.1       91       11.9       82       9.5%
44/56       13.1       90       11.8       81       10.1%
HFC-1243zf/DME
72.7/27.3   12.0       83       12.0       83       0.0%
90/10       12.4       85       12.3       85       0.5%
99/1        12.9       89       12.9       89       0.1%
60/40       12.2       84       12.1       84       0.5%
40/60       13.0       90       12.7       88       2.2%
20/80       14.0       96       13.7       95       2.0%
10/90       14.3       99       14.2       98       0.6%
1/99        14.5       100      14.5       100      0.0%
顺式-HFC-1234ze/HFC-236ea(25℃)
20.9/79.1   30.3       209      30.3       209      0.0%
10/90       30.2       208      30.2       208      0.0%
1/99        29.9       206      29.9       206      0.0%
40/60       30.0       207      30.0       207      0.2%
60/40       29.2       201      28.9       199      0.9%
80/20       27.8       191      27.4       189      1.4%
90/10       26.8       185      26.5       183      1.1%
99/1        25.9       178       25.8       178       0.2%
顺式-HFC-1234ze/HFC-236fa(25℃)
1/99        39.3       271       39.3       271       0.0%
10/90       38.6       266       38.4       265       0.3%
20/80       37.6       259       37.3       257       0.9%
40/60       35.4       244       34.5       238       2.5%
60/40       32.8       226       31.4       216       4.3%
78/22       29.6       204       28.2       195       4.8%
90/10       27.8       192       26.9       185       3.4%
99/1        26.0       179       25.8       178       0.5%
顺式-HFC-1234ze/HFC-245fa(25℃)
76.2/23.7   26.2       180       26.2       180       0.0%
90/10       26.0       179       26.0       179       0.0%
99/1        25.8       178       25.8       178       0.0%
60/40       26.0       179       25.9       179       0.2%
40/60       25.3       174       25.0       173       0.9%
20/80       23.9       164       23.5       162       1.7%
10/90       22.8       157       22.5       155       1.5%
1/99        21.6       149       21.5       149       0.2%
顺式-HFC-1234ze/正丁烷
51.4/48.6   6.1        42        6.1        42        0.0%
80/20       5.8        40        5.2        36        9.3%
81/19       5.8        40        5.2        36        10.4%
40/60       6.1        42        6.0        41        0.7%
20/80       5.8        40        5.6        39        3.3%
10/90       5.6        38        5.4        37        3.1%
1/99        5.3        36        5.2        36        0.6%
顺式-HFC-1234ze/异丁烷
26.2/73.8   8.7       60       8.7       60       0.0%
10/90       8.7       60       8.6       59       0.3%
1/99        8.5       59       8.5       59       0.0%
40/60       8.7       60       8.6       60       0.5%
60/40       8.4       58       8.0       55       4.3%
70/30       8.1       56       7.3       50       10.3%
69/31       8.2       56       7.4       51       9.4%
顺式-HFC-1234ze/2-甲基丁烷(25℃)
86.6/13.4   27.3       188     27.3      188      0.0%
90/10       27.2       187     27.2      187      0.1%
99/1        26.0       180     25.9      179      0.5%
60/40       25.8       178     24.0      166      6.9%
55/45       25.3       174     22.8      157      10.0%
顺式-HFC-1234ze/正戊烷(25℃)
92.9/9.1    26.2       181     26.2      181      0.0%
99/1        25.9       178     25.9      178      0.1%
80/20       25.6       177     25.2      174      1.8%
70/30       24.8       171     23.5      162      5.6%
64/36       24.3       167     22.0      152      9.2%
63/37       24.2       167     21.8      150      9.9%
HFC-1234ye/HFC-134(25℃)
1/99        75.9       523     75.8      523      0.1%
10/90       73.8       509     73.0      503      1.1%
20/80       71.3       491     69.0      476      3.1%
38/62       66.0       455     59.6      411      9.7%
39/61       65.7       453     58.9      406      10.2%
HFC-1234ye/HFC-236ea(-25℃)
24.0/76.0   3.423              3.4       23       0.0%
10/90       3.3       23       3.3       23       0.3%
1/99        3.3       23       3.3       23       0.0%
40/60       3.3       23       3.3       23       0.0%
60/40       3.2       22       3.2       22       0.9%
80/20       3.1       21       3.0       21       1.6%
90/10       2.9       20       2.9       20       1.4%
99/1        2.8       19       2.8       19       0.0%
HFC-1234ye/HFC-236fa(25℃)
1/99        39.2       270     39.2      270      0.1%
10/90       37.7       260     37.3      257      1.1%
20/80       36.1       249     35.2      243      2.5%
40/60       32.8       226     31.0      213      5.7%
60/40       29.3       202     26.7      184      8.8%
78/22       25.4       175     23.1      159      9.1%
90/10       23.2       160     21.7      150      6.3%
99/1        21.0       145     20.8      144      0.8%
HFC-1234ye/HFC-245fa(25℃)
42.5/57.5   22.8       157     22.8      157      0.0%
20/80       22.5       155     22.4      155      0.3%
10/90       22.1       152     22.0      152      0.3%
1/99        21.5       148     21.5      148      0.0%
60/40       22.6       156     22.6      156      0.2%
80/20       22.0       152     21.9      151      0.6%
90/10       21.5       148     21.3      147      0.6%
99/1        20.8       144     20.8      143      0.1%
HFC-1234ye/顺式-HFC-1234ze(25℃)
1/99        25.7       177     25.7      177      0.0%
10/90       25.6       176     25.6      176      0.0%
20/80       25.3       175     25.3      174      0.1%
40/60       24.7       170       24.5       169       0.5%
60/40       23.7       163       23.5       162       1.0%
78/22       22.4       155       22.2       153       1.2%
90/10       21.7       149       21.5       148       0.9%
99/1        20.9       144       20.8       144       0.1%
HFC-1234ye/正丁烷(25℃)
41.2/58.8   38.0       262       38.0       262       0.0%
20/80       37.3       257       37.0       255       0.8%
10/90       36.4       251       36.1       249       0.9%
1/99        35.4       244       35.3       243       0.2%
60/40       37.4       258       36.9       254       1.4%
70/30       36.5       252       34.9       241       4.4%
78/22       35.3       243       31.8       219       9.9%
79/21       35.1       242       31.3       216       10.9%
HFC-1234ye/环戊烷(25℃)
99/1        20.7       143       20.7       143       0.0%
90/10       20.3       140       20.0       138       1.0%
80/20       19.5       134       18.7       129       4.1%
70/30       18.6       128       16.9       116       9.5%
69/31       18.5       128       16.6       115       10.3%
HFC-1234ye/异丁烷(25℃)
16.4/83.6   50.9       351       50.9       351       0.0%
10/90       50.9       351       50.9       351       0.0%
1/99        50.5       348       50.5       348       0.0%
40/60       50.1       345       49.6       342       1.0%
60/40       47.8       330       45.4       313       5.2%
68/32       46.4       320       42.0       289       9.5%
69/31       46.2       318       41.4       286       10.3%
HFC-1234ye/2-甲基丁烷(25℃)
80.3/19.7   23.1       159       23.1       159       0.0%
90/10       22.8       157       22.6       156       1.1%
99/1        21.2       146       20.9       144       1.0%
60/40       22.5       155       21.7       149       3.6%
47/53       21.5       148       19.4       134       9.6%
46/54       21.4       148       19.2       133       10.1%
HFC-1234ye/正戊烷(25℃)
87.7/12.3   21.8       150       21.8       150       0.0%
95/5        21.5       149       21.4       148       0.5%
99/1        21.0       145       20.9       144       0.4%
60/40       20.5       141       18.9       131       7.7%
57/43       20.3       140       18.3       126       9.7%
56/44       20.2       139       18.1       125       10.4%
对本发明的组合物而言,原始组合物与除去50重量%后留下的组合物之间的蒸气压差小于大约10%。这表明本发明的组合物是会共沸或近共沸的。
实施例2
制冷性能数据
表10表明与HFC-134a相比本发明的各种制冷剂组合物的性能。在表10中,Evap Pres是蒸发器压力,Cond Pres是冷凝器压力,Comp DischT是压缩机排放温度,COP是能量效率,且CAP是容量。数据基于下列条件。
蒸发器温度      40.0℉(4.4℃)
冷凝器温度      130.0℉(54.4℃)
过冷量          10.0℉(5.5℃)
返回气体温度    60.0℉(15.6℃)
压缩机效率是    100%
要指出的是,在冷却能力中包括过热。
表10
 
组合物(wt%) EvapPres(Psia) EvapPres(kPa) CondPres(Psia) CondPres(kPa) CompDischT(F) CompDischT(C) Cap(Btu/ min) Cap(kW) COP
HFC-134a 50.3 346 214 1476 156 68.9 213 3.73 4.41
HFC-1225ye 37.6 259 165 1138 146 63.3 162 2.84 4.41
HFC-1225ye/HFC-152a(85/15) 398 274 173 1193 151 66.1 173 3.03 4.45
HFC-1225ye/HFC-32(95/5) 46.5 321 197 1358 151 66.1 200 3.50 4.53
HFC-1225ye/HFC-32(96/4) 442 305 189 1303 150 65.6 191 335 4.51
HFC-1225ye/HFC-32(97/3) 43.1 297 184 1269 149 65.0 186 3.26 450
HFC-1225ye/HFC-32(94/6) 473 326 200 1379 153 67.2 203 3.56 4.52
HFC-1225ye/HFC-32(93/7) 48.8 336 205 1413 154 67.8 210 3.68 4.53
HFC-1225ye/HFC-32(90/10) 53.0 365 222 1531 157 69.4 227 3.98 4.52
HFC-1225ye/HFC-134a(90/10) 39.5 272 172 1186 147 63.9 169 2.96 4.40
HFC-1225ye/CO2(99/1) 43.2 298 179 1234 146 63.3 177 3.10 4.63
HFC-1225ye/HFC-134a/HFC-32(88/9/3) 44.5 307 190 1310 150 65.6 191 3.35 449
HFC-1225ye/HFC-134a/HFC-32(88/8/4) 45.5 314 194 1338 151 66.1 195 3.42 449
HFC-1225ye/HFC-134a/HFC-152a(76/9/15) 41.0 283 178 1227 153 67.2 178 3.12 4.44
HFC-1225ye/HFC-134a/HFC-161(86/10/4) 42.0 290 181 1248 150 65.6 179 3.13 442
HFC-1225ye/HFC-134a/丙烷(87/10/3) 47.0 324 195 1345 148 64.4 197 345 4.49
HFC-1225ye/HFC-134a/异丁烷(87/10/3) 41.7 288 178 1227 146 63.3 175 3.06 4.39
 
HFC-1225ye/HFC-134a/DME(87/10/3) 38.7 267 169 1165 149 65.0 168 2.94 4.44
HFC-1225ye/HFC-134a/CO2(88.5/11/.5) 42.4 292 180 1241 147 63.9 182 3.18 4.51
HFC-1225ye/HFC-134/HFC-32(88/9/3) 43.0 296 185 1276 150 65.6 187 3.27 4.51
HFC-1225ye/HFC-152a/HFC-32(85/10/5) 46.7 322 198 1365 155 68.3 203 3.55 4.53
HFC-1225ye/HFC-152a/HFC-32(81/15/4) 45.5 314 193 1331 155 68.3 198 3.47 4.52
HFC-1225ye/HFC-152a/HFC-32(82/15/3) 44.1 304 188 1296 155 68.3 192 3.36 4.50
HFC-1225ye/HFC-152a/丙烷(85/13/2) 44.4 306 185 1276 151 66.1 190 3.33 4.52
HFC-1225ye/HFC-152a/异丁烷(85/13/2) 40.9 282 176 1214 150 65.6 175 3.06 4.44
HFC-1225ye/HFC-152a/DME(85/13/2) 39.0 269 170 1172 152 66.7 171 3.00 4.46
HFC-1225ye/HFC-152a/CO2(84/15/1) 44.8 309 185 1276 151 66.1 195 3.42 4.64
HFC-1225ye/HFC-152a/CO2(84/15.5/0.5) 42.3 292 179 1234 151 66.1 184 3.22 4.55
HFC-1225ye/HFC-152a/CF3I(70/20/10) 42.0 290 180 1241 155 68.3 181 3.17 4.46
HFC-1234yf/HFC-32(95/5) 58.6 404 230 1586 149 65.0 228 4.00 4.36
HFC-1234yf/HFC-134a(90/10) 52.7 363 210 1448 145 62.8 206 3.61 4.33
HFC-1234yf/HFC-152a(80/20) 53.5 369 213 1468 150 65.6 213 3.73 4.38
反式-HFC-1234ze/HFC-32(95/5) 42.6 294 183 1262 153 67.2 186 3.26 4.51
反式-HFC-1234ze/HFC-32/CF3I(70/2/28) 43.5 300 182 1255 154 67.8 184 3.22 4.46
 
反式-HFC-1234ze/HFC-134a(90/10) 38.1 263 166 1145 149 65.0 165 2.89 4.44
反式-HFC-1234ze/HFC-152a(80/20) 41.0 284 176 1214 154 67.8 177 3.10 4.48
反式-HFC-1234ze/HFC-125(96/4) 38.6 266 167 1151 148 64.4 167 2.92 4.45
HFC-1225ye/HFC-1234yf(51/49) 46.0 317 190 1310 145 62.8 186 3.26 4.35
HFC-1225ye/HFC-1234yf(60/40) 44.0 303 187 1289 146 63.3 179 3.13 4.30
HFC-1225ye/HFC-1234yf/HFC-134a(70/20/10) 43.0 296 183 1261 147 63.9 179 3.13 4.38
HFC-1225ye/HFC-1234yf/HFC-134a(20/70/10) 50.7 350 205 1412 145 62.8 200 3.50 4.34
HFC-1225ye/HFC-1234yf/HFC-32(25/73/2) 53.0 365 212 1464 146 63.3 210 3.68 4.37
HFC-1225ye/HFC-1234yf/HFC-32(75/23/2) 453 312 190 1312 148 64.4 189 3.31 443
HFC-1225ye/HFC-1234yf/HFC-32(85/10/5) 47.6 328 200 1379 151 66.1 203 3.56 4.50
HFC-1225ye/HFC-1234yf/HFC-32(90/5/5) 46.7 322 197 1358 151 66.1 200 3.50 4.51
HFC-1225ye/HFC-1234yf/HFC-152a(70/25/5) 42.8 295 181 1250 147 63.9 179 3.13 4.40
HFC-1225ye/HFC-1234yf/HFC-152a(25/70/5) 49.9 344 202 1392 146 63.3 199 3.49 4.35
HFC-1225ye/HFC-1234yf/HFC-125(25/71/4) 51.6 356 207 1429 145 62.8 202 3.54 4.33
HFC-1225ye/HFC-1234yf/HFC-125(75/21/4) 43.4 299 184 1268 146 63.3 180 3.15 4.38
HFC-1225ye/HFC-1234yf/HFC-125(75/24/1) 42.4 292 180 1241 145 62.8 176 3.08 4.39
HFC-1225ye/HFC-1234yf/HFC-125(25/74/1) 50.2 346 202 1395 144 62.2 198 3.47 4.33
HFC-1225ye/HFC-1234yf(25/75) 49.8 343 201 1383 144 62.2 196 3.43 4.34
 
HFC-1225ye/HFC-1234yf/CF3I(40/40/20) 47.9 330 195.0 1344 147.5 64.2 192 3.36 4.34
HFC-1225ye/HFC-1234yf/CF3I(45/45/10) 47.0 324 192.9 1330 146 63.3 189 3.31 4.35
HFC-1225ye/HFC-1234yf/HFC-32(49/49/2) 49.5 341 202.5 1396 146.9 63.8 201 3.52 4.4
HFC-1225ye/HFC-134a/HFC-152a/HFC-32(74/8/17/1) 42.5 293 183 1260 154 67.8 184.3 3.23 447
HFC-1225ye/HFC-134a/HFC-32(87/8/5) 47.5 328 201 1386 152 66.7 204 3.57 4.49
HFC-1225ye/HFC-1234yf/HFC-125(48/48/4) 48.1 332 198 1365 145 62.8 193 3.38 4.35
HFC-1225ye/HFC-1234yf/HFC-32/CF3I(45/44/2/9) 50.5 348 205 1413 148 64.4 204 3.57 4.39
HFC-1225ye/HFC-1234yf/HFC-32/CF3I(47/46/2/5) 50.1 345 204 1407 148 64.4 202 3.54 4.39
HFC-1225ye/HFC-32/HFC-125(94/2/4) 43.2 298 192 1324 151 66.1 181 3.17 4.28
HFC-1234yf/HFC-32/CF3I(60/2/38) 58.2 401 224 1544 152 66.7 225 3.94 4.37
HFC-1234yf/HFC-32/CF3I(60/1/39)) 56.2 387 217 1496 151 66.1 217 3.80 4.35
HFC-1234yf/CF3I(60/40)对比? 54.1 373 210 1448 149 65.0 209 3.66 4.34
HFC-1234yf/HFC-125/CF3I(70/4/26) 56.8 392 220 1517 147 63.9 217 3.80 4.31
HFC-1234yf/HFC-125/CF3I(80/4/16) 56.4 389 219 1510 146 63.3 215 3.77 4.32
HFC-1234yf/HFC-125(96/4) 55.1 380 217 1496 144 62.2 212 3.71 4.31
HFC-1234yf/HFC-134a/CF3I(70/10/20) 54.7 377 215 1482 148 64.4 211 3.70 4.32
HFC-1234yf/HFC-152a/CF3I(50/10/40) 55.1 380 214 1475 154 67.8 216 3.78 4.36
数种组合物具有比HFC-134a更高的能量效率(COP),同时保持较低的排放压力和温度。表10中列出的组合物的容量也类似于R134a,表明这些组合物可以是制冷和空调中,特别是移动空调用途中R134a的替代制冷剂。结果也表明可以添加其它化合物,例如HFC-32、HFC-134a、CO2或HFC-1234yf以改进HFC-1225ye的冷却能力。那些含烃的组合物也可以改进与传统矿物油和烷基苯润滑剂的油溶性。
实施例3
制冷性能数据
表11给出与R404A和R422A相比本发明的各种制冷剂组合物的性能。在表11中,Evap Pres是蒸发器压力,Cond Pres是冷凝器压力,CompDisch T是压缩机排放温度,EER是能量效率,且CAP是容量。数据基于下列条件。
蒸发器温度      -17.8℃
冷凝器温度      46.1℃
过冷量          5.5℃
返回气体温度    15.6℃
压缩机效率是70%
要指出的是,在冷却能力中包括过热。
表11
 
现有制冷剂产品 EvapPress(kPa)) Cond PPress(kPa) ComprDisch T(C) CAP(kJ/m3) EER
R22 267 1774 144 1697 4.99
R404A 330 2103 101.1 1769 4.64
R507A 342 2151 100.3 1801 4.61
R422A 324 2124 95.0 1699 4.54
备选替代物 wt% 4
HFC-125/HFC-1225ye/异丁烷 85.1/11.5/3.4 330 2137 93.3 1699 4.50
HFC-125/反式-HFC-1234ze/异丁烷 86.1/11.5/2.4 319 2096 94.4 1669 4.52
HFC-125/HFC-1234yf/异丁烷 87.1/11.5/1.4 343 2186 93.3 1758 4.52
 
HFC-125/HFC-1225ye/正丁烷 85.1/11.5/3.4 322 2106 93.5 1674 4.52
HFC-125/反式-HFC-1234ze/正丁烷 86.1/11.5/2.4 314 2083 94.8 1653 4.53
HFC-125/HFC-1234yf/正丁烷 87.1/11.5/1.4 340 2173 93.4 1748 4.53
HFC-32/HFC-125/HFC-1225ye 10/10/′80 173 1435 107 1159 4.97
HFC-32/HFC-125/HFC-1225ye 25/25/50 276 2041 120 1689 4.73
HFC-32/HFC-125/HFC-1225ye 25/40/35 314 2217 119 1840 4.66
HFC-32/HFC-125/HFC-1225ye 30/10/60 265 1990 125 1664 4.78
HFC-32/HFC-125/HFC-1225ye 30/15/55 276 2046 125 1710 4.76
HFC-32/HFC-125/HFC-1225ye 30/20/50 287 2102 124 1757 4.73
HFC-32/HFC-125/HFC-1225ye 30/30/40 311 2218 124 1855 4.68
HFC-32/HFC-125/HFC-1225ye 30/35/35 324 2271 123 1906 4.66
HFC-32/HFC-125/HFC-1225ye 35/15/50 296 2157 129 1820 4.72
HFC-32/HFC-125/HFC-1225ye 35/20/45 308 2212 129 1868 4.70
HFC-32/HFC-125/HFC-1225ye 35/30/35 332 2321 127 1968 4.66
HFC-32/HFC-125/HFC-1225ye 35/40/25 357 2424 126 2068 4.64
HFC-32/HFC-125/HFC-1225ye 50/30/20 390 2584 138 2277 4.54
HFC-32/HFC-125/HFC-1225ye 40/30/30 353 2418 131 2077 4.66
HFC-32/HFC-125/HFC-1225ye 40/35/25 364 2465 131 2124 4.64
HFC-32/HFC-125/HFC-1225ye 45/30/25 372 2505 135 2180 4.66
HFC-32/HFC-125/HFC-1225ye 15/5.5/79.5 184 1509 112 1235 4.97
HFC-32/HFC-125/HFC-1225ye 24/13.7/62.3 242 1851 120 1544 4.85
HFC-32/HFC-125/HFC-1225ye 27.5/17.5/55 264 1980 123 1653 4.78
HFC-32/HFC-125/HFC-1225ye 31/20/49 285 2090 126 1756 4.74
HFC-32/HFC-125/HFC-1225ye 33/22/45 298 2157 127 1820 4.72
HFC-32/HFC-125/HFC-1225ye 30/19/51 278 2056 125 1724 4.75
HFC-32/HFC-125/HFC-152a/HFC-1225ye 10/20/10/60 190 1517 110 1255 4.97
HFC-32/HFC-125/HFC-152a/HFC-1225ye 15/25/10/50 221 1709 115 1422 4.90
HFC-32/HFC-125/HFC-152a/HFC-1225ye 20/20/15/45 229 1755 121 1485 4.90
 
HFC-32/CF3I/HFC-1225ye 30/20/50 272 1984 130 1706 4.80
HFC-32/CF3I/HFC-1225ye 40/10/50 299 2159 137 1860 4.73
HFC-32/CF3I/HFC-1225ye 30/30/40 286 2030 133 1774 4.80
HFC-32/CF3I/HFC-1225ye 30/60/10 314 2120 144 1911 4.75
HFC-32/CF3I/HFC-1225ye 40/20/40 315 2214 139 1936 4.73
HFC-32/CF3I//HFC-1225ye 30/50/20 309 2101 139 1885 4.78
HFC-32/CF3I/HFC-1225ye 40/40/20 346 2309 145 2079 4.71
HFC-32/CF3I/HFC-1225ye 45/45/10 373 2432 152 2217 4.67
HFC-32/CF3I/HFC-1225ye 45/10/45 319 2260 141 1964 4.71
HFC-32/CF3I/HFC-1225ye 50/10/40 338 2353 145 2065 4.68
HFC-32/CF3I/HFC-1225ye 50/20/30 356 2410 147 2150 4.68
HFC-32/CF3I/HFC-1225ye 25/5/70 230 1781 122 1495 4.90
HFC-32/CF3I/HFC-1225ye 60/30/10 409 2626 158 2434 4.66
HFC-32/CF3I/HFC-1225ye 50/25/25 364 2437 149 2192 4.68
HFC-32/CF3I/HFC-1225ye 50/20/30 356 2410 147 2156 4.68
HFC-32/CF3I/HFC-1225ye 25/50/25 284 1964 134 1754 4.85
HFC-32/CF3I/HFC-1225ye 45/30/25 353 2368 146 2124 4.71
HFC-32/CF3I/HFC-1234yf 5/50/45 199 1377 107 1254 5.11
HFC-32/CF3I/HFC-1234yf 5/30/65 197 1382 103 1241 5.11
HFC-32/CF3I/HFC-1234yf 10/25/65 220 1542 107 1374 5.04
HFC-32/CF3I/HFC-1234yf 20/10/70 255 1786 114 1577 4.95
HFC-32/CF3I/HFC-1234yf 30/10/60 295 2020 123 1795 4.88
HFC-32/CF3I/HFC-1234yf 30/20/50 305 2057 125 1843 4.85
HFC-32/CF3I/HFC-1234yf 30/30/40 314 2091 128 1887 4.85
HFC-32/CF3I/HFC-1234yf 20/40/40 275 1861 121 1679 4.92
HFC-32/CF3I/HFC-1234yf 10/40/50 225 1558 111 1404 5.04
HFC-32/CF3I/HFC-1234yf 50/20/30 378 2447 143 2238 4.73
HFC-32/CF3I/HFC-1234yf 40/30/30 354 2305 137 2099 4.76
HFC-32/CF3I/HFC-1234yf 40/40/20 360 2336 142 2136 4.74
HFC-32/CF3I/HFC-1234yf 35/35/30 338 2217 135 2015 4.78
HFC-32/CF3I/HFC-1234yf 35/30/35 334 2202 133 1996 4.80
 
HFC-32/CF3I/HFC-1234yf 50/25/25 384 2468 145 2267 4.72
HFC-32/CF3I/HFC-1225ye/HFC-1234yf 40/20/20/20 331 2246 136 1999 4.76
HFC-32/CF3I/HFC-1225ye/HFC-1234yf 30/20/25/25 290 2029 127 1782 4.83
HFC-32/CF3I/HFC-1225ye/HFC-1234yf 30/10/30/30 279 1987 125 1728 4.83
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 25/25/25/25 297 2089 118 1772 4.76
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 20/30/25/25 286 2025 113 1702 4.64
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 20/30/30/20 290 2033 113 1717 4.76
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 20/30/40/10 297 2048 112 1746 4.78
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 30/30/20/20 328 2251 122 1925 4.71
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 30/30/1/39 312 2217 123 1858 4.68
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 30/30/39/1 342 2275 120 1979 4.73
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 30/30/10/30 320 2235 123 1891 4.68
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 35/30/5/30 337 2330 127 1986 4.66
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 20/15/10/55 240 1818 115 1513 4.85
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 30/15/10/45 284 2066 124 1743 4.76
HFC-32/HFC-125/HFC-1234yf/HFC-1225ye 40/30/15/15 341 2364 132 2022 4.66
HFC-32/HFC-125/CF3I/HFC-1234yf/HFC-1225ye 30/25/5/35/5 335 2240 121 1954 4.76
HFC-32/HFC-125/CF3I/HFC-1234yf 30/25/5/40 338 2245 121 1966 4.76
 
HFC-32/HFC-125/HFC-1225ye/异丁烷 25/35/35/5 323 2195 115 1837 4.64
HFC-32/HFC-125/HFC-1225ye/异丁烷 25/38/35/2 318 2214 117 1837 4.64
HFC-32/HFC-125/HFC-1225ye/丙烷 25/38/35/2 330 2297 118 1892 4.59
HFC-32/CF3I/HFC-1225ye/DME 50/20/25/5 321 2252 150 2010 4.76
HFC-32/HFC-125/HFC-1225ye/DME 35/30/30/5 293 2135 131 1823 4.76
HFC-32/HFC-125/HFC-1225ye/DME 35/33/30/2 320 2268 129 1925 4.68
HFC-32/HFC-125/HFC-1225ye/DME 35/35/28/2 324 2288 129 1943 4.68
HFC-32/HFC-125/HFC-1234yf 25/50/25 365 2376 115 2040 4.66
HFC-32/HFC-125/HFC-1234yf 30/30/40 343 2276 120 1982 4.73
HFC-32/HFC-125/HFC-1234yf 20/30/50 303 2059 112 1770 4.78
HFC-32/HFC-125/CF3I/HFC-1234yf 25/25/10/40 323 2154 118 1884 4.78
HFC-32/HFC-125/CF3I/HFC-1225ye 25/25/10/40 291 2088 121 1757 4.73
HFC-32/HFC-125/CF3I/HFC-1225ye 20/30/10/40 279 2017 117 1680 4.73
HFC-32/HFC-125/CF3I/HFC-1225ye 20/35/5/40 285 2056 116 1699 4.71
HFC-32/HFC-1225ye 20/80 200 1620 117 1331 4.91
HFC-32/HFC-1225ye 30/70 246 1879 126 1587 4.85
HFC-32/HFC-1225ye 40/60 284 2101 134 1788 4.74
HFC-32/HFC-1225ye/CF3I 40/50/10 299 2159 137 1860 4.74
HFC-32/HFC-1225ye/CF3I 50/40/10 337 2353 145 2065 4.69
HFC-32/HFC-134a/HFC-1225ye 30/20/50 242 1854 128 1578 4.88
FC-32/HFC-134a/HFC-1225ye 40/10/50 281 2078 135 1783 4.78
FC-32/HFC-134a/HFC-1225ye 40/20/40 277 2053 136 1775 4.81
FC-32/HFC-134a/HFC-1225ye 40/30/30 274 2029 137 1762 4.85
FC-32/HFC-134a/HFC-1225ye 40/40/20 269 2004 138 1747 4.86
FC-32/HFC-134a/HFC-1225ye 50/30/20 302 2189 145 1929 4.79
HFC-32/HFC-134a/HFC-1225ye/CF3I 40/30/20/10 287 2081 139 1828 4.88
HFC-32/HFC-134a/HFC-1225ye/CF3I 40/30/15/15 294 2106 140 1862 4.81
HFC-32/HFC-134a/HFC-1225ye/CF3I 30/30/30/10 254 1891 130 1637 4.88
HFC-32/HFC-125/HFC-134a/HFC-1225ye/CF3I 30/10/30/15/15 280 2016 131 1756 4.83
 
HFC-32/HFC-125/HFC-134a/HFC-1225ye/CF3I 30/10/20/20/20 291 2064 131 1802 4.81
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf 30/30/20/20 253 1877 127 1628 4.91
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf 30/30/10/30 259 1892 126 1651 4.90
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf 35/25/5/35 280 2003 129 1762 4.87
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf/CF3I 35/20/10/30/5 286 2032 130 1790 4.85
HFC-32/HFC-134a/HFC-1234yf/CF3I 35/20/35/10 296 2063 130 1834 4.85
HFC-32/HFC-134a/HFC-1234yf/CF3I 35/10/45/10 306 2095 128 1868 4.84
HFC-32/HFC-134a/HFC-1234yf/CF3I 25/15/50/10 267 1878 121 1660 4.91
HFC-32/HFC-134a/HFC-1234yf/CF3I 30/30/30/10 272 1939 128 1712 4.88
HFC-32/HFC-134a/HFC-1234yf/CF3I 30/20/40/10 280 1968 126 1744 4.88
HFC-32/HFC-134a/HFC-1234yf/CF3I 30/20/30/20 289 2003 129 1787 4.87
HFC-32/HFC-134a/HFC-1234yf/CF3I 30/20/20/30 297 2035 132 1831 4.87
HFC-32/HFC-134a/HFC-1234yf/CF3I 25/20/25/30 279 1928 127 1729 4.89
HFC-32/HFC-134a/HFC-1234yf/CF3I 40/20/20/20 320 2188 138 1967 4.81
HFC-32/HFC-134a/HFC-1234yf/CF3I 50/10/20/20 362 2396 145 2183 4.74
HFC-32/HFC-134a/HFC-1234yf/CF3I 50/10/30/10 351 2354 141 2127 4.76
HFC-32/NH3/HFC-1225ye 15/15/70 266 2004 152 1831 5.01
HFC-32/NH3/HFC-1225ye 20/20/60 289 2141 165 2008 5.00
HFC-32/NH3/HFC-1225ye 20/10/70 265 2002 144 1789 4.96
HFC-32/NH3/HFC-1225ye 25/25/50 302 2229 178 2118 5.00
HFC-32/NH3/HFC-1225ye 25/15/60 295 2171 158 2001 4.95
HFC-32/NH3/HFC-1225ye 30/10/60 297 2182 151 1968 4.89
HFC-32/NH3/HFC-1225ye/CF3I 25/25/40/10 305 2246 182 2138 5.00
HFC-32/NH3/HFC-1225ye/CF3I 20/20/50/10 296 2162 168 2048 5.00
HFC-32/NH3/HFC-1225ye/CF3I 15/15/55/15 278 2041 156 1899 5.00
HFC-32/NH3/HFC-1225ye/CF3I 20/10/55/15 280 2052 148 1868 4.95
 
HFC-32/NH3/HFC-1234yf/CF3I 20/10/50/20 311 2125 143 2005 4.99
HFC-32/NH3/HFC-1234yf/CF3I 10/10/20/60 280 1928 152 1857 5.05
HFC-1225ye/R717 95/5 159 1317 113 1121 5.16
HFC-1225ye/R717 90/10 194 1550 128 1368 5.14
HFC-1225ye/R717 85/15 217 1698 141 1535 5.11
HFC-1225ye/R717 80/20 243 1725 146 1750 5.43
HFC-125/HFC-1225ye/R717 5/85/10 205 1613 127 1423 5.11
HFC-125/HFC-1225ye/R717 10/80/10 212 1651 127 1455 5.09
HFC-125/HFC-1225ye/R717 15/75/10 220 1687 127 1486 5.04
HFC-125/HFC-1225ye/R717 20/70/10 227 1723 126 1516 5.02
HFC-125/HFC-1225ye/R717 25/65/10 235 1757 126 1547 5.00
HFC-125/HFC-1225ye/R717 20/65/15 248 1845 138 1674 5.04
HFC-125/HFC-1225ye/R717 20/75/5 195 1525 112 1291 5.02
R32/HFC-125/HFC-1225ye/R717 25/10/60/5 273 2029 135 1766 4.88
R32/HFC-125/HFC-1225ye/R717 20/20/55/5 273 2011 130 1740 4.85
R32/HFC-125/HFC-1225ye/R717 10/20/65/5 235 1787 121 1526 4.92
R32/HFC-125/HFC-1225ye/R717 25/10/55/10 295 2148 146 1936 4.90
R32/HFC-125/HFC-1225ye/R717 20/20/50/10 295 2125 142 1911 4.90
R32/HFC-125/HFC-1225ye/R717 10/20/60/10 262 1938 134 1722 4.95
R32/HFC-125/HFC-1225ye/R717 10/10/65/15 265 1974 147 1804 5.02
R32/HFC-125/HFC-1225ye/R717 10/20/55/15 278 2028 146 1859 5.00
R32/HFC-125/HFC-1225ye/R717 5/25/55/15 270 1967 141 1798 5.00
R32/HFC-125/HFC-1234yf/R717 10/20/60/10 295 2025 129 1865 5.00
R32/HFC-125/HFC-1234yf/R717 5/25/60/10 285 1958 125 1797 5.00
数种组合物具有与顶级R404A和R422A相当的能量效率(EER)。排放温度也低于R404A和R507A。表11中列出的组合物的容量也类似于R404A、R507A和R422A,表明这些组合物可以是制冷和空调中R404A、R507A或R422A的替代制冷剂。那些含烃的组合物也可以改进与传统矿物油和烷基苯润滑剂的油溶性。
实施例4
制冷性能数据
表12给出与HCFC-22、R410A、R407C和R417A相比本发明的各种制冷剂组合物的性能。在表12中,Evap Pres是蒸发器压力,Cond Pres是冷凝器压力,Comp Disch T是压缩机排放温度,EER是能量效率,且CAP是容量。数据基于下列条件。
蒸发器温度     4.4℃
冷凝器温度     54.4℃
过冷量         5.5℃
返回气体温度   15.6℃
压缩机效率是100%
要指出的是,在冷却能力中包括过热。
表12
 
现有制冷剂产品 EvapPress(kPa)) CondPress(kPa) ComprDisch T(C) CAP(kJ/m 3 ) EER
R22 573 2149 88.6 3494 14.73
R410A 911 3343 89.1 4787 13.07
R407C 567 2309 80.0 3397 14.06
R417A 494 1979 67.8 2768 13.78
备选替代物 wt%
HFC-32/HFC-125/HFC-1225ye 30/40/30 732 2823 81.1 3937 13.20
HFC-32/HFC-125/HFC-1225ye 23/25/52 598 2429 78.0 3409 13.54
HFC-32/HFC-125/反式-HFC-1234ze 30/50/20 749 2865 81.7 3975 13.10
HFC-32/HFC-125/反式-HFC-1234ze 23/25/52 546 2252 78.9 3222 13.80
HFC-32/HFC-125/HFC-1234yf 40/50/10 868 3185 84.4 4496 13.06
HFC-32/HFC-125/HFC-1234yf 23/25/52 656 2517 76.7 3587 13.62
HFC-32/HFC-125/HFC-1234yf 15/45/40 669 2537 73.3 3494 13.28
 
HFC-32/HFC-125/HFC-1234yf 10/60/30 689 2586 71.3 3447 12.96
HFC-125/HFC-1225ye/正丁烷 65/32/3 563 2213 66.1 2701 12.87
HFC-125/反式-HFC-1234ze/正丁烷 66/32/2 532 2130 67.2 2794 13.08
HFC-125/HFC-1234yf/正丁烷 67/32/1 623 2344 66.1 3043 12.85
HFC-125/HFC-1225ye/异丁烷 65/32/3 574 2244 66.2 2874 12.79
HFC-125/反式-HFC-1234ze/异丁烷 66/32/2 538 2146 67.4 2808 13.04
HFC-125/HFC-1234yf/异丁烷 67/32/1 626 2352 66.3 3051 12.83
组合物具有与R22、R407C、R417A和R410A相当的能量效率(EER),同时保持低排放温度。表12中列出的组合物的容量也类似于R22、R407C和R417A,表明这些组合物可以是制冷和空调中R22、R407C或R417A的替代制冷剂。那些含烃的组合物也可以改进与传统矿物油和烷基苯润滑剂的油溶性。
实施例5
制冷性能数据
表13给出与HCFC-22和R410A相比本发明的各种制冷剂组合物的性能。在表13中,Evap Pres是蒸发器压力,Cond Pres是冷凝器压力,Comp Disch T是压缩机排放温度,EER是能量效率,且CAP是容量。数据基于下列条件。
蒸发器温度      4℃
冷凝器温度      43℃
过冷量          6℃
返回气体温度    18℃
压缩机效率是70%
要指出的是,在冷却能力中包括过热。
表13
 
现有制冷剂制品 EvapPress(kPa) CondPress(kPa) ComprDischTemp(C) CAP(kJ/m3) EER
R22 565 1648 90.9 3808 9.97
R410A 900 2571 88.1 5488 9.27
备选替换产品(组合物wt%)
HFC-32/HFC-1225ye(40/60) 630 1948 86.7 4242 9.56
HFC-32/HFC-1225ye(45/55) 666 2041 88.9 4445 9.49
HFC-32/HFC-1225ye(50/50) 701 2127 91.0 4640 9.45
HFC-32/HFC-1225ye/CF3I(40/30/20) 711 2104 90.6 4605 9.56
HFC-32/HFC-1225ye/CF3I(45/30/25) 737 2176 92.2 4765 9.45
HFC-32/HFC-1225ye/CF3I(45/35/20) 724 2151 91.4 4702 9.45
HFC-32/HFC-134a/HFC-1225ye(40/30/30) 607 1880 87.8 4171 9.69
HFC-32/HFC-134a/HFC-1225ye(45/30/25) 637 1958 89.9 4347 9.66
HFC-32/HFC-134a/HFC-1225ye(45/35/20) 631 1944 90.2 4326 9.69
HFC-32/HFC-134a/HFC-1234yf/CF3I(30/20/5/45) 611 1845 89.6 4107 9.66
HFC-32/HFC-134a/HFC-1234yf/CF3I(25/20/10/45) 575 1745 86.5 3891 9.76
HFC-32/HFC-134a/HFC-1234yf/CF3I(35/10/5/40) 646 1939 91.2 4308 9.62
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf(34/12/47/7) 587 1822 84 4001 9.69
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf(30/8/52/10) 561 1752 81.9 3841 9.73
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf(35/6/52/7) 597 1852 84.3 4051 9.66
 
HFC-32/HFC-1225ye(40/60) 630 1948 86.7 4242 9.56
HFC-32/HFC-1225ye(45/55) 666 2041 88.9 4445 9.49
HFC-32/HFC-1225ye(50/50) 701 2127 91.0 4640 9.45
HFC-32/HFC-1225ye(55/45) 734 2206 93.0 4825 9.45
HFC-32/HFC-1225ye(60/40) 764 2280 94.9 5001 9.42
HFC-32/HFC-1225ye(70/30) 801 2373 99.1 5252 942
HFC-32/HFC-1225ye/CF3I(65/30/5) 808 2376 97.5 5237 9.42
HFC-32/HFC-1225ye/CF3I(65/17.5/17.5) 845 2445 99.4 5408 9.39
HFC-32/HFC-1225ye/CF3I(65/5/30) 879 2508 101.7 5565 9.49
HFC-32/HFC-1225ye/CF3I(60/30/10) 795 2337 96.3 5140 9.42
HFC-32/HFC-1225ye/CF3I(60/20/20) 857 2319 92.5 5565 10.27
HFC-32/HFC-1225ye/CF3I(60/10/30) 852 2442 995 5404 9.39
HFC-32/HFC-1225ye/CF3I(55/40/5) 749 2235 93.6 4894 9.42
HFC-32/HFC-1225ye/CF3I(55/25/20) 793 2319 95.7 5098 9.42
HFC-32/HFC-1225ye/CF3I(55/20/25) 808 2345 96.5 5163 9.42
HFC-32/HFC-1225ye/CF3I(55/5/40) 844 2413 99.4 5332 9.39
HFC-32/HFC-1225ye/CF3I(50/45/5) 819 2350 98.3 5176 939
HFC-32/HFC-1225ye/CF3I(50/25/25) 774 2264 94.4 4970 9.42
HFC-32/HFC-1225ye/CF3I(50/5/45) 716 2156 91.6 4706 9.45
HFC-32/HFC-1225ye/CF3I(45/50/5) 680 2069 89.5 4509 9.49
HFC-32/HFC-1225ye/CF3I(45/30/25) 737 2176 922 4765 9.45
HFC-32/HFC-1225ye/CF3I(45/35/20) 724 2151 91.4 4702 9.45
HFC-32/HFC-1225ye/CF3I(45/25/30) 750 2200 93.0 4825 9.45
HFC-32/HFC-1225ye/CF3I(45/5/50) 789 2276 97.3 4996 9.39
HFC-32/HFC-1225ye/CF3I(40/50/10) 657 2003 87.9 4365 9.52
HFC-32/HFC-1225ye/CF3I(40/30/30) 711 2104 90.6 4605 9.56
HFC-32/HFC-1225ye/CF3I(40/10/50) 749 2178 94.7 4775 9.42
HFC-32/HFC-1234yf/CF3I(60/30/10) 823 2372 939 5228 9.45
HFC-32/HFC-1234yf/CF3I(60/20/20) 844 2415 96.0 5335 9.45
HFC-32/HFC-1234yf/CF3I(60/10/30) 862 2459 98.5 5433 9.49
HFC-32/HFC-1234yf/CF3I(55/35/10) 798 2305 91.7 5069 9.49
 
HFC-32/HFC-1234yf/CF3I(55/5/40) 850 2419 98.9 5347 9.39
HFC-32/HFC-1234yf/CF3I(50/40/10) 769 2232 89.4 4899 9.52
HFC-32/HFC-1234yf/CF3I(50/30/20) 790 2275 91.3 5002 9.49
HFC-32/HFC-1234yf/CF3I(50/20/30) 808 2313 93.4 5095 9.45
HFC-32/HFC-1234yf/CF3I(50/10/40) 821 2345 96.2 5168 9.42
HFC-32/HFC-1234yf/CF3I(50/5/45) 825 2357 97.8 5192 9.39
HFC-32/HFC-1234yf/CF3I(45/10/45) 792 2274 95.0 4999 9.42
HFC-32/HFC-1234yf/CF3I(45/5/50) 794 2283 96.8 5011 9.39
HFC-32/HFC-1234yf/CF3I(40/50/10) 705 2067 85.0 4523 9.59
HFC-32/HFC-1234yf/CF3I(40/40/20) 725 2108 86.5 4622 9.56
HFC-32/HFC-1234yf/CF3I(40/10/50) 759 2192 93.8 4806 9.42
HFC-32/HFC-1234yf/CF3I(40/5/55) 759 2197 95.7 4808 9.39
HFC-32/HFC-134a/HFC-1225ye(60/30/10) 713 2156 96.2 4807 9.56
HFC-32/HFC-134a/HFC-1225ye(60/20/20) 730 2196 95.8 4875 9.52
HFC-32/HFC-134a/HFC-1225ye(60/10/30) 747 2237 95.3 4941 9.49
HFC-32/HFC-134a/HFC-1225ye(55/5/40) 727 2187 93.1 4802 9.49
HFC-32/HFC-134a/HFC-1225ye(55/20/25) 704 2131 93.7 4723 9.56
HFC-32/HFC-134a/HFC-1225ye(55/40/5) 674 2060 94.7 4605 9.62
HFC-32/HFC-134a/HFC-1225ye(50/5/45) 695 2110 91.1 4623 9.49
HFC-32/HFC-134a/HFC-1225ye(50/25/25) 671 2045 91.9 4536 9.62
HFC-32/HFC-134a/HFC-1225ye(50/45/5) 645 1982 92.8 4433 9.69
HFC-32/HFC-134a/HFC-1225ye(45/5/50) 662 2027 89.0 4433 9.52
HFC-32/HFC-134a/HFC-1225ye(45/25/30) 642 1971 89.7 4367 9.66
HFC-32/HFC-134a/HFC-1225ye(45/30/25) 637 1958 89.9 4347 9.66
HFC-32/HFC-134a/HFC-1225ye(45/35/20) 631 1944 90.2 4326 9.69
HFC-32/HFC-134a/HFC-1225ye(45/50/5) 615 1903 90.9 4259 9.73
HFC-32/HFC-134a/HFC-1225ye(40/10/50) 623 1926 87.0 4224 9.62
HFC-32/HFC-134a/HFC-1225ye(40/30/30) 607 1880 87.8 4171 9.69
HFC-32/HFC-134a/HFC-1225ye(40/50/10) 589 1833 88.7 4101 9.76
HFC-32/HFC-125/HFC-1225ye(60/5/35) 784 2323 94.6 5087 9.42
HFC-32/HFC-125/HFC-1225ye(60/10/30) 803 2365 94.2 5173 9.42
 
HFC-32/HFC-125/HFC-1225ye(60/15/25) 822 2407 93.9 5256 9.39
HFC-32/HFC-125/HFC-1225ye(50/10/40) 742 2220 90.3 4820 9.42
HFC-32/HFC-125/HFC-1225ye(50/5/45) 721 2173 90.7 4730 9.45
HFC-32/HFC-125/HFC-1225ye(50/15/35) 762 2266 90.0 4911 9.42
HFC-32/HFC-125/HFC-1225ye(40/15/45) 692 2097 85.9 4518 9.45
HFC-32/HFC-125/HFC-1225ye(40/10/50) 671 2047 86.2 4425 9.49
HFC-32/HFC-125/HFC-1225ye(35/15/50) 654 2001 838 4304 9.49
HFC-32/HFC-125/HFC-1225ye(37.5/11.5/51) 643 1976 85.2 4287 9.54
HFC-32/HFC-125/HFC-1225ye(34/6/60) 593 1848 83.8 4028 9.62
HFC-32/HFC-125/HFC-1225ye(30/3/67) 548 1732 82.0 3788 9.70
HFC-32/HFC-125/HFC-1225ye(30/12.7/57.3) 590 1837 81.7 3980 9.60
HFC-32/HFC-125/HFC-1225ye(24/13.7/62.3) 544 1715 78.7 3713 9.66
HFC-32/HFC-125/HFC-1225ye(20/5/75) 471 1522 76.9 3329 982
HFC-32/HFC-125/HFC-1225ye(15/5.5/79.5) 427 1398 74.1 3061 9.89
HFC-32/HFC-134a/HFC-1234yf/CF3I(30/20/5/45) 611 1845 89.6 4107 9.66
HFC-32/HFC-134a/HFC-1234yf/CF3I(25/20/10/45) 575 1745 86.5 3891 9.76
HFC-32/HFC-134a/HFC-1234yf/CF3I(35/10/5/40) 646 1939 91.2 4308 9.62
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf(34/12/47/7) 587 1822 84.0 4001 9.69
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf(30/8/52/10) 561 1752 81.9 3841 9.73
HFC-32/HFC-134a/HFC-1225ye/HFC-1234yf(35/6/52/7) 597 1852 84.3 4051 9.66
 
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(65/5/10/20) 862 2470 98.9 5470 9.42
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(65/20/10/5) 818 2389 96.7 5270 9.42
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(65/10/5/20) 857 2465 99.3 5456 9.39
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(65/10/20/5) 828 2401 95.9 5298 9.45
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(60/30/5/5) 785 2316 95.2 5090 9.42
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(60/5/30/5) 809 2345 93.3 5163 9.45
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(60/5/5/30) 860 2448 99.0 5419 9.39
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(60/10/10/20) 835 2405 96.8 5309 9.42
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(55/10/10/25) 818 2358 95.6 5197 9.42
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(55/5/5/35) 839 2399 97.8 5298 9.42
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(55/20/20/5) 770 2263 92.1 4966 9.45
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(55/5/35/5) 783 2278 91.1 5005 9.49
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(55/35/5/5) 755 2243 93.2 4912 9.45
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(50/5/5/40) 816 2339 96.7 5153 9.42
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(50/10/10/20) 798 2303 94.3 5067 9.45
 
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(50/20/20/10) 752 2213 90.7 4848 9.49
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(40/10/10/40) 744 2161 91.6 4743 9.45
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(40/15/15/30) 728 2127 89.4 4663 9.52
HFC-32/HFC-1225ye/HFC-1234yf/CF3I(40/20/20/20) 707 2087 87.7 4566 9.52
HFC-32/HFC-125/HFC-1225ye/CF3I(60/10/10/20) 865 2481 97.0 5453 9.35
HFC-32/HFC-125/HFC-1225ye/CF3I(60/5/5/30) 873 2488 99.1 5494 9.39
HFC-32/HFC-125/HFC-1225ye/CF3I(60/5/30/5) 799 2352 95.2 5159 9.42
HFC-32/HFC-125/HFC-1225ye/CF3I(60/5/15/20) 845 2437 97.4 5367 9.39
HFC-32/HFC-125/HFC-1225ye/CF3I(50/10/5/35) 847 2414 95.2 5288 9.39
HFC-32/HFC-125/HFC-1225ye/CF3I(50/10/35/5) 758 2250 90.9 4891 9.42
HFC-32/HFC-125/HFC-1225ye/CF3I(50/5/5/40) 834 2384 96.7 5238 9.39
HFC-32/HFC-125/HFC-1225ye/CF3I(50/5/20/25) 797 2315 93.9 5070 9.42
HFC-32/HFC-125/HFC-1225ye/CF3I(50/15/5/30) 857 2440 93.9 5327 9.39
HFC-32/HFC-125/HFC-1225ye/CF3I(50/15/30/5) 779 2297 90.5 4983 9.39
HFC-32/HFC-125/HFC-1234yf/CF3I(60/10/10/20) 875 2494 96.1 5481 9.39
 
HFC-32/HFC-125/HFC-1234yf/CF3I(60/5/5/30) 879 2494 98.6 5508 9.39
HFC-32/HFC-125/HFC-1234yf/CF3I(60/5/15/20) 860 2455 96.0 5410 9.42
HFC-32/HFC-125/HFC-1234yf/CF3I(50/10/5/35) 852 2421 94.7 5304 9.39
HFC-32/HFC-125/HFC-1234yf/CF3I(50/5/5/40) 840 2391 96.2 5254 9.39
HFC-32/HFC-125/HFC-1234yf/CF3I(50/5/20/25) 818 2340 92.3 5134 9.45
HFC-32/HFC-125/HFC-1234yf/CF3I(50/15/5/30) 862 2447 93.4 5343 9.39
HFC-32/HFC-125/HFC-1225/HFC-1234yf/CF3I(50/5/20/20/5) 759 2232 89.8 4873 9.49
HFC-32/HFC-125/HFC-1225/HFC-1234yf/CF3I(50/5/5/5/35) 829 2370 95.2 5206 9.42
HFC-32/HFC-125/HFC-1225/HFC-1234yf/CF3I(50/10/20/15/5) 775 2272 89.8 4948 9.45
HFC-32/HFC-125/HFC-1225/HFC-1234yf/CF3I(50/10/5/5/30) 839 2397 93.8 5248 939
HFC1225ye/R717(90/10) 445 1433 82.2 3306 10.17
HFC1225ye/R717(85/15) 493 1569 890 3666 10.17
HFC1225ye/R717(80/20) 525 1660 95.0 3921 10.17
HFC1225ye/R717(95/5) 370 1217 74.1 2767 10.20
HFC-32/HFC-1225ye/R717(15/70/15) 594 1855 95.0 4312 10.00
HFC-32/HFC-1225ye/R717(20/70/10) 594 1855 91.2 4232 9.90
HFC-32/HFC-1225ye/R717(20/75/5) 542 1718 84.7 3846 9.86
HFC-32/HFC-1225ye/R717(10/85/5) 462 1494 79.9 3361 10.00
HFC-125/HFC-1225ye/R717(5/80/15) 513 1622 88.7 3778 10.14
HFC-125/HFC-1225ye/R717(10/75/15) 526 1652 88.4 3834 10.10
HFC-125/HFC-1225ye/R717(12.5/72.5/15) 533 1666 88.3 3861 10.07
 
HFC-125/HFC-1225ye/R717(15/70/15) 539 1680 88.1 3888 10.07
HFC-125/HFC-1225ye/R717(20/75/5) 444 1411 77.8 3142 10.00
HFC-125/HFC-1225ye/R717(10/85/5) 410 1327 74.0 2984 10.10
HFC-32/R125/HFC-1225ye/R717(5/15/65/15) 573 1776 90.1 4104 10.03
HFC-32/R125/HFC-1225ye/R717(5/17.5/60/17.5) 591 1822 92.9 4242 10.03
HFC-32/R125/HFC-1225ye/R717(10/15/60/15) 604 1861 92.1 4299 9.97
HFC-32/R125/HFC-1225ye/R717(20/10/60/10) 625 1926 90.5 4370 9.83
HFC-32/R125/HFC-1225ye/R717(25/10/60/5) 616 1905 86.3 4224 9.73
HFC-32/R125/HFC-1225ye/R717(20/10/65/5) 579 1806 84.1 4009 9.76
HFC-32/R125/HFC-1225ye/R717(20/15/60/5) 596 1845 83.9 4079 9.73
组合物具有与R22和R410A相当的能量效率(EER),同时保持合理的排放温度。表13中列出的某些组合物的容量也类似于R22,表明这些组合物可以是制冷和空调中R22的替代制冷剂。另外,表13中列出的一些组合物具有与R410A接近或相等的容量,表明那些组合物可以是制冷和空调中R410A的替代制冷剂。
实施例6
可燃性
可以通过根据ASTM(American Society of Testing and Materials)E681-01用电子点火源测试来识别可燃化合物。在HFC-1234yf、HFC-1225ye和本公开的混合物上在101kPa(14.7psia)、100℃(212℉)和50%相对湿度下,在空气中的各种浓度下进行可燃性的这种试验以测定可燃下限(LFL)和可燃上限(UFL)。结果列在表13中。
表14
 
组合物 LFL(在空气中的体积%) UFL(在空气中的体积%)
HFC-1225ye(100重量%) 不可燃 不可燃
HFC-1234yf(100重量%) 5.0 14.5
HFC-1234yf/1225ye(50/50重量%) 8.5 12.0
HFC-1234yf/1225ye(40/60重量%) 不可燃 不可燃
HFC-1225ye/HFC-32(60/40重量%) 13.0 17.0
HFC-1225ye/HFC-32(65/35重量%) 不可燃 不可燃
结果表明,尽管HFC-1234yf是可燃的,但添加HFC-1225ye降低了可燃性。因此,包含大约1重量%至大约49重量%HFC-1234yf和大约99重量%至大约51重量%HFC-1225ye的组合物是优选的。结果也表明HFC-1225ye降低了HFC-32的可燃性并在65/35wt%HFC-1225ye/HFC-32下产生不可燃的组合物。

Claims (14)

1.包含20重量%至99重量%HFC-1234yf和氨的组合物;其中所述组合物选自:
20重量%HFC-32,10重量%氨,50重量%HFC-1234yf,和20重量%CF3I;
10重量%HFC-32,10重量%氨,20重量%HFC-1234yf,和60重量%CF3I;
10重量%HFC-32,20重量%HFC-125,60重量%HFC-1234yf,和10重量%氨;和
5重量%HFC-32,25重量%HFC-125,60重量%HFC-1234yf,和10重量%氨。
2.如权利要求1中所述的组合物,进一步包含选自多元醇酯、聚烷撑二醇、聚乙烯基醚、矿物油、烷基苯、合成链烷、合成环烷和聚(α)烯烃的润滑剂。
3.如权利要求1中所述的组合物,进一步包含选自氟代烃、氘化烃、氘化氟代烃、全氟化碳、氟醚、溴化化合物、碘化化合物、醇、醛、酮、一氧化二氮(N2O)及其组合的示踪剂。
4.权利要求3的组合物,进一步包含选自CD3CD3、CD3CD2CD3、CD2F2、CF3CD2CF3、CD2FCF3、CD3CF3、CDF2CF3、CF3CDFCF3、CF3CF2CDF2、CDF2CDF2、CF3CF2CD3、CF3CD2CH3、CF2CH2CD3、CF3CF3、环-CF2CF2CF2-、CF3CF2CF3、环-CF2CF2CF2CF2-、CF3CF2CF2CF3、CF3CF(CF3)2、环-CF(CF3)CF2CF(CF3)CF2-、反式-环-CF2CF(CF3)CF(CF3)CF2-、顺式-环-CF2CF(CF3)CF(CF3)CF2-、CF3OCHF2、CF3OCH2F、CF3OCH3、CF3OCHFCF3、CF3OCH2CF3、CF3OCH2CHF2、CF3CH2OCHF2、CH3OCF2CF3、CH3CF2OCF3、CF3CF2CF2OCHFCF3、CF3CF2CF2OCF(CF3)CF2OCHFCF3、CHF3、CH2FCH3、CHF2CH3、CHF2CHF2、CF3CHFCF3、CF3CF2CHF2、CF3CF2CH2F、CHF2CHFCF3、CF3CH2CF3、CF3CF2CH3、CF3CH2CHF2、CHF2CF2CH3、CF3CHFCH3、CF3CH2CH3、CH3CF2CH3、CH3CHFCH3、CH2FCH2CH3、CHF2CF2CF2CF3、(CF3)2CHCF3、CF3CH2CF2CF3、CHF2CF2CF2CHF2、CH3CF2CF2CF3、CF3CHFCHFCF2CF3、全氟甲基环戊烷、全氟甲基环己烷、全氟-邻、间或对-二甲基环己烷、全氟乙基环己烷、全氟茚满、全氟三甲基环己烷及其异构体、全氟异丙基环己烷、顺式-全氟萘烷、反式-全氟萘烷、顺式-或反式-全氟甲基萘烷及其异构体、CH3Br、CH2FBr、CHF2Br、CHFBr2、CHBr3、CH2BrCH3、CHBr=CH2、CH2BrCH2Br、CFBr=CHF、CF3I、CHF2I、CH2FI、CF2ICH2F、CF2ICHF2、CF2ICF2I、C6F5I、乙醇、正丙醇、异丙醇、丙酮、正丙醛、正丁醛、甲乙酮、一氧化二氮及其组合的示踪剂。
5.如权利要求1中所述的组合物,进一步包含增容剂,其选自:
a)式R1[(OR2)xOR3]y所示的聚氧化亚烷基二醇醚,其中:x是1至3的整数;y是1至4的整数;R1选自氢和具有1至6个碳原子和y键合位点的脂族烃基;R2选自具有2至4个碳原子的脂族亚烃基;R3选自氢和具有1至6个碳原子的脂族和脂环族烃基;R1和R3的至少一个选自所述烃基;且其中所述聚氧化亚烷基二醇醚具有100至300原子质量单位的分子量;
b)式R1C(O)NR2R3和环-[R4CON(R5)-]所示的酰胺,其中R1、R2、R3和R5独立地选自具有1至12个碳原子的脂族和脂环族烃基和最多一个具有6至12个碳原子的芳族基团;R4选自具有3至12个碳原子的脂族亚烃基;且其中所述酰胺具有100至300原子质量单位的分子量;
c)式R1C(O)R2所示的酮,其中R1和R2独立地选自具有1至12个碳原子的脂族、脂环族和芳基烃基,且其中所述酮具有70至300原子质量单位的分子量;
d)式R1CN所示的腈,其中R1选自具有5至12个碳原子的脂族、脂环族或芳基烃基,且其中所述腈具有90至200原子质量单位的分子量;
e)式RClx所示的含氯烃,其中:x是1或2;R选自具有1至12个碳原子的脂族和脂环族烃基;且其中所述含氯烃具有100至200原子质量单位的分子量;
f)式R1OR2所示的芳基醚,其中:R1选自具有6至12个碳原子的芳基烃基;R2选自具有1至4个碳原子的脂族烃基;且其中所述芳基醚具有100至150原子质量单位的分子量;
g)式CF3R1所示的1,1,1-三氟烷烃,其中R1选自具有5至15个碳原子的脂族和脂环族烃基;
h)式R1OCF2CF2H所示的氟代醚,其中R1选自具有5至15个碳原子的脂族、脂环族和芳族烃基;或其中所述氟代醚由氟烯烃和多元醇生成,其中所述氟烯烃是CF2=CXY类型的,其中X是氢、氯或氟,且Y是氯、氟、CF3或ORf,其中Rf是CF3、C2F5或C3F7;且所述多元醇是直链或支链的,其中所述直链多元醇是HOCH2(CHOH)x(CRR′)yCH2OH类型的,其中R和R′是氢、CH3或C2H5,x是0-4的整数,y是0-3的整数且z是0或1,且所述支链多元醇是C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w类型的,其中R可以是氢、CH3或C2H5,m是0至3的整数,t和u是0或1,v和w是0至4的整数,且其中t+u+v+w=4;和
i)结构[B]、[C]和[D]所示的内酯:
Figure FSB00000995010400031
其中,R1至R8独立地选自氢、直链、支链、环状、双环的饱和和不饱和的烃基;且分子量为100至300原子质量单位;和
j)通式R1CO2R2所示的酯,其中R1和R2独立地选自直链和环状的饱和和不饱和的烷基和芳基;且其中所述酯具有80至550原子质量单位的分子量。
6.权利要求1的组合物,进一步包含至少一种选自萘二酰亚胺、苝、香豆素、蒽、菲、呫吨、噻吨、苯并夹氧杂蒽、荧光素、其衍生物及其组合的紫外线荧光染料。
7.权利要求6的组合物,进一步包含至少一种选自烃、二甲基醚、聚氧化亚烷基二醇醚、酰胺、酮、腈、含氯烃、酯、内酯、芳基醚、氢氟醚和1,1,1-三氟烷烃的增溶剂。
8.权利要求1的组合物,进一步包含稳定剂、水清除剂或气味遮蔽剂。
9.权利要求8的组合物,其中所述稳定剂选自硝基甲烷、受阻酚、羟胺、硫醇、亚磷酸酯和内酯。
10.制冷方法,所述方法包括:在要冷却的物体附近蒸发权利要求1的所述组合物并此后冷凝所述组合物。
11.制热方法,所述方法包括:在要加热的物体附近冷凝权利要求1的所述组合物并此后蒸发所述组合物。
12.在制冷、空调或热泵装置中替代高GWP制冷剂的方法,其中所述高GWP制冷剂选自R134a、R22、R123、R11、R245fa、R114、R236fa、R124、R12、R410A、R407C、R413A、R417A、R422A、R422B、R422C和R422D、R423A、R507A、R502和R404A,所述方法包括向使用、用过或被设计成使用所述高GWP制冷剂的所述制冷、空调或热泵装置提供权利要求1的组合物。
13.使用权利要求1的组合物作为传热流体组合物的方法,所述方法包括将所述组合物从热源转移到热沉。
14.含有如权利要求1中所述的组合物的制冷、空调或热泵装置。
CN200680054110XA 2006-03-30 2006-08-29 包含氟烯烃的组合物 Expired - Fee Related CN101415793B (zh)

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