CN1159205A - 能够与不混溶制冷剂共同使用的改进烃润滑剂 - Google Patents

能够与不混溶制冷剂共同使用的改进烃润滑剂 Download PDF

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CN1159205A
CN1159205A CN95194942A CN95194942A CN1159205A CN 1159205 A CN1159205 A CN 1159205A CN 95194942 A CN95194942 A CN 95194942A CN 95194942 A CN95194942 A CN 95194942A CN 1159205 A CN1159205 A CN 1159205A
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composition
hydrocarbon lubricants
oil
refrigeration
hydrocarbon
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CN1053006C (zh
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J·L·雷耶斯-加维兰
A·D·艾克德
G·T·弗兰克
T·R·特里克
L·阿考斯基
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Witco Corp
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Witco Corp
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Priority claimed from US08/301,694 external-priority patent/US5792383A/en
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Abstract

流体制冷组合物，含有烃润滑剂，不混溶制冷剂和能降低烃润滑剂与制冷剂之间界面张力的添加剂。

Description

能够与不混溶制冷剂共同使用的改进烃润滑剂
该申请为于1995年4月20日提交的系列号08/426500与于1994年9月7日提交的系列号08/301694的部分继续申请。
本发明涉及含有烃润滑剂如矿物油、不与烃润滑剂混溶的制冷剂以及能够降低烃润滑剂与不混溶制冷剂之间界面张力的添加剂的流体制冷组合物。更具体地，本发明涉及含有烃润滑剂如矿物油、不与烃润滑剂混溶的氟代烃制冷剂以及能够降低烃润滑剂与氟代烃制冷剂之间界面张力的表面活性剂的流体制冷组合物。
在过去约60年中，含氯氟烃(CFC)已经以工业规模在被设计进行制冷和空调应用的系统中被用作换热流体。这类化合物还可被用作推进剂，发泡剂和电子与航空航天工业的清洁剂。这类化合物的实例为CFC-12(二氯二氟甲烷)、CFC-115(1-氯-1，1，2，2，2-五氟乙烷)和CFC-113(1，1，2-三氯-1，2，2-三氟乙烷)。
Rowland与Molina在70年代初期提出假想：CFC固有的高稳定性使其分子在低大气层中具有非常长的寿命。其结果是它们缓慢地进入同温层，在那里由于太阳的紫外辐射效果使氯自由基脱离CFC分子。这些自由基随后进攻该大气层中的臭氧进而使其浓度下降。这就促使气溶胶工业在70年代中期逐渐用满足产品规格的对环境更安全的替代物取代这些化学品。
于80年代中期，人们检测到南极州上空臭氧浓度下降，这一效应目前已传播到世界的其它地方，这促使许多国家严格限制并且最终在本世纪末禁止生产与使用CFC。因此，已经提议采用多种化合物作为替代制冷剂，这些化合物属于氯氟烃(HCFC)和氟代烃(HFC)化学家族。HCFC的实例为R-22(氯二氟甲烷)、R-123(1，1-二氯-2，2，2-三氟乙烷)和R-124(1-氯-1，2，2，2-四氟乙烷)。尽管HCFC中存在氯，但是其消耗臭氧的能力远远低于CFC，其中所含的氢原子导致其在大气层的较低高度上分解。然而，由于臭氧层目前在继续被消耗而这现象在向世界的其它地区扩散，因而存在很大的立法压力以便限制与禁止使用这些化合物。因此，这些被视作短期制冷剂替代物。目前被使用的环烷基矿物油、烷基苯与环烷矿物油/烷基苯混合物从传统的观点出发已经满足了被充有HCFC的制冷系统的润滑与操作要求。
HFC的实例为R-134a(1，1，1，2-四氟乙烷)、R-152a(1，1-二氟乙烷)、R-32(二氟甲烷)、R-143a(1，1，1-三氟乙烷)、R-125(1，1，1，2，2-五氟乙烷)和含有其中任意一种的共沸与非共沸混合物或其它HFC组分。这些分子并非消耗臭氧的物质，因而目前被视作长期的替代制冷剂。在HFC制冷剂可以具有能够使其成为适宜的长期制冷剂替代物的所需物理特性的同时，却缺乏与传统地用作制冷压缩机润滑剂的环烷矿物油相互混溶的能力。矿物油的化学稳定性和与CFC及HCFC制冷剂的混溶性、与所有体系组分的化学相溶性、低絮凝点与低倾点、高介电强度和适宜的粘度提供了在其被导入系统之时能够使其总体性能得到提高的特性。
由于彼此不能混溶，所以某些人认为将环烷制冷油用于HFC被用作制冷剂的制冷或空调应用场合是不适宜的。人们认为在单元操作温度下制冷剂与润滑剂之间的不混溶性或低分散性会使油不适宜地回流至压缩机中。这样，由于油在换热盘管的内表面上形成涂层而导致传热不充分，在极端情况下，会使压缩机中润滑剂不足。前者导致能量利用效率下降，后者致使装置被烧毁。
Jolly等在US4941986中指出由制冷剂与润滑剂形成的混合物必须在宽温度范围内是可以混溶/可溶性的并且是化学和热稳定的，该温度覆盖了制冷和空调系统的操作温度范围。通常期望在-40-80℃的温度范围内在约5-15％的浓度下润滑剂可以混溶/可溶于制冷剂中。该温度范围包括了许多目前市场上制冷与空调系统设计的操作温度。
这些专利权人随后指出用不同种类比烃油昂贵得多的合成材料替代烃类润滑油。显然，尽管烃油/替代制冷剂流体不混溶，但是从经济与环境保护的角度出发仍然期望将其用于这些系统。
在美国加热、制冷与空调工程师协会杂志中，Sanvordenker(1989)与Reyes-Gavilan(1993)分别指出在用HFC-134a与直链烃油填充的家庭制冷系统中存在适当的油回流。Sanvordenker进一步解释道，这一状况取决于装置构造；带有水平蒸发器的叠放式装置操作良好，而具有直立蒸发器的并排式装置也能发挥作用，但是不如前者运行良好。Reyes-Gavilan表明通过在与由Sanvordenker测试的种类相同的装置中采用低粘度环烷矿物油(70sus，于37.8℃)可以根除油回流对装置构造的依赖性。对家庭制冷系统中发生油回流负责的试剂，除了在该系统中具有良好流动性和在压缩机中具有适宜的润滑性能的低粘度矿物油以外，还属于制冷速度快和在蒸发器与压缩机之间回流线路短的物质。可以设想，那些制冷速度低和/或在蒸发器与压缩机之间具有长回流管线的制冷或空调系统的油回流性能差，从而产生上述任意一种系统性能问题。
先有技术指出在使用HFC制冷剂的制冷或空调系统中烃油的使用受到限制。U.S.5096606(Kao公司)描述并且要求保护含有可以与其它润滑剂混合的HFC与多醇酯的组合物。
授予Mitsui Petrochemical的US5114605介绍了一种含有氟代烃、多醚碳酸酯与矿物油或α-烯烃低聚物的组合物。
日本专利NO.4018491的摘要指出由酯油与烃油如矿物油形成的混合物可以与其中酯油与烃油的比值至少为1的氟代烃制冷剂相容。
日本专利NO.1115998的摘要披露了由烷基苯、矿物油和氟代烃制冷剂组成的混合物。
Lubrizol PCT WO/12849指出可以采用诸如环烷矿物油之类的粘度调节剂。然而，并未提及在HFC制冷剂存在下对烃润滑剂的分散性或混溶性/溶解性进行改进。
这些文献向本领域专业人员揭示了在HFC制冷与空调应用场合采用含有烃润滑剂的组合物的可能性。然而，该工业领域已经注意到许多被翻新改进采用HFC/多元醇酯流体的烃润滑剂CFC体系在多元醇酯中残余矿物油含量超出该体系中润滑剂总量1％时已经表现出性能变坏的现象，这说明油返回压缩机的性能不好。
在本发明中，“不混溶”一词意味着在制冷剂与润滑剂之间至少在制冷或空调系统的典型操作范围-40～80℃中任一温度下形成二相体系。
本发明的一般目的是提供含有烃润滑剂，优选矿物油润滑剂和与烃润滑剂不混溶的含有至少一个碳和一个氟原子的制冷剂的制冷流体组合物。本发明的一个更具体的目的是提供含有矿物油润滑剂和与矿物油不混溶的氟代烃制冷剂的制冷流体组合物。
业已发现，本发明的这些目的可以借助下列制冷流体组合物实现：其中含有烃润滑剂、与烃润滑剂不混溶的含有至少一个碳原子和一个氟原子的制冷剂以及有效量能够降低烃润滑剂与不混溶制冷剂之间表面张力的添加剂。
本发明的组合物可被用于在被充入直链烃油与HFC制冷剂的情况下具有潜在的油返回困难的制冷与空调系统。其目的是通过使制冷剂与烃润滑剂更易于彼此分散、使制冷剂将润滑剂自换热器内表面上洗下来而促进油返回到压缩机中。本发明在保持该系统具有充分的化学与热稳定性的条件下向装置提供适宜的润滑与能量效率。
简言之，本发明的制冷流体组合物含有烃润滑油、含有至少一个碳和一个氟原子的制冷剂以及能够降低烃润滑剂与制冷剂之间界面张力的添加剂。
适用于本发明的烃润滑剂包括环烷矿物油、烷基苯油、聚α-烯烃及其低聚物、链烷矿物油，及其混合物。少量(1-20％(重))烷基苯与多数(99-80％(重))环烷矿物油特别适用于改进烃油中某些添加剂(即表面活性剂如2，4，7，9-四甲基-5-癸炔-4，7-二醇)的溶解性或分散性。
适用于本发明的制冷剂包括含有至少一个碳原子和一个氟原子的种类。适宜的制冷剂的实例包括R-22(氯二氟甲烷)、R-124(1-氯-1，2，2，2-四氟乙烷)、R-134a(1，1，1，2-四氟乙烷)、R-143a(1，1，1-三氟乙烷)、R-152a(1，1-二氟乙烷)、R-32(二氟甲烷)、R-125(1，1，1，2，2-五氟乙烷)及其混合物如R-404a[R-125(44％(重))、R-143a(52％(重))、R-134a(4.0％(重))]。这些混合物还可以含有作为下列应用场合的混合物中组分之一的丙烷，在这些应用场合换热流体将被用作现有制冷与空调设备的临时翻新改进流体。必要的话，尤其是在被改进翻新的系统中存在残余量这些制冷剂的情况下，这些适宜的制冷剂可以与CFC制冷剂共同被使用。
本发明中用于降低润滑剂与制冷剂之间界面张力的添加剂具有促进制冷剂将油排挤出金属表面的特性。该特性可以通过将在室温下不与烃润滑剂混溶的制冷剂如R134a、烃润滑剂与添加剂密封在装有钢或铁屑的玻璃管中来确定。这样便形成一个二相体系，其中润滑油构成顶层，制冷剂构成底层。随后借助磁铁使金属屑升至管中油层，通过在油中迅速上下移动金属屑使油完全润湿金属表面。如果当金属屑缓慢地降至液体制冷剂层之中之时制冷剂能够置换出油，则该添加剂便适用于本发明。
适宜的添加剂包括表面活性剂如2，4，7，9-四甲基-5-癸炔-4，7-二醇(商品名为Srufynol SE)、含氟烃酯(商品名为FC-430)、阴离子含氟烃亚磷酸盐、磷酸盐、羧酸盐(盐与酸)、磺酸盐等如F(CF2CF2)3-8-CH2CH2SCH2CH2CO2Li(商品名ZonylFSA)、 与[F(商品名为Zonyl FSP、Zonyl FSJ等)的混合物。
在某些情况下，有必要借助共溶剂或由2种以上组分组成的烃润滑剂提高表面活性剂在烃润滑剂中的溶解性。举例来说，如上所述，少量烷基苯烃类可以改善某些添加剂在矿物油中的溶解性或分散性。
尽管申请人不希望受到任何理论的束缚，但是申请人认为制冷剂(液体)/1GS界面处的界面张力被降至钢材上制冷剂液体的铺展系数(S)略大于或非常接近于零的程度，这可以使制冷剂通过微小的扰动或由于比重之差来替代油。
铺展系数被定义为Y＝γ
S＝Y23-Y12-Y13其中S为在作为第3相的一种固体(3)表面上流体(1)相对于流体(2)的铺展系数。Y分别为界面张力。如果S＞0，会发生同时铺展。其它影响因素如比重差异或机械剪切能量上的差异也会起作用，但是S将表示在添加剂或表面活性剂影响下界面张力的贡献。1＝制冷剂，2＝1GS，3＝钢表面。在无添加剂存在下，0＞Y23-Y12-Y13由两相间的主液面可以看出Y12是有效正数。此外，由于即使在某种程度搅拌下油也会优选地润湿与继续润滑钢；
Y13＞Y23这导致结论Y12+Y13＞Y23成立。
加入一定表面活性剂之后，通过观察发现Y12→0(平液面)Y23≥Y13(制冷剂排代处在钢表面上的油)不同的行为结果被表述为：
0≤Y23-Y12-Y13
因而，得出结论：钢上制冷剂的铺展系数在能够使Y12+Y13降低速度大于Y23减少速度的特定添加剂存在下接近0或略微大于0。
添加剂或表面活性剂的用量范围相对于每100重量份润滑油为0.001-5重量份。可以制备相对于每100重量份润滑油含多达100重量份表面活性剂的浓缩物；以便将其加入不含表面活性剂或其含量不足以适用于预期目的的含烃润滑油的制冷体系中。
润滑油与不混溶制冷剂的重量比取值范围正如本领域常见值那样相对于每100重量份制冷剂为0.10-15重量份。
如上所述，本工业领域已经注意到许多经过翻新改样的烃润滑油/CFC体系采用HFC/多醇酯流体，其性能变差，这表明当多醇酯中残余矿物油含量超过体系中润滑剂总量的1％时，油返回压缩机的性能不良。申请人出人意料地发现向本发明组合物中加入少量多醇酯润滑剂可以改善某些添加剂(即表面活性剂如2，4，7，9-四甲基-5-癸炔-4，7-二醇)于烃油中的溶解性或分散性。在此情况下，多醇酯与烃润滑剂的重量比约为1∶99-1∶3、优选1∶19-1∶4。
因此，申请人相信有利的是改样翻新烃润滑剂CFC体系以便通过将含多醇酯与表面活性剂如2，4，7，9-四甲基-5-癸炔-4，7-二醇或氟化酯的浓缩组合物直接加入带有或不带有其它烃润滑剂的压缩机系统来采用HFC，条件是压缩机系统中的表面活性剂至少占压缩机中润滑流体的0.001％(重)。
多醇酯/表面活性剂浓缩物可以含有每100重量份多醇酯约0.1-100重量份表面活性剂。
适宜的多醇酯含有C4-25脂族单羧酸自身或与二或三元羧酸一起形成的多元醇酯。适宜的多元醇可以含2-6个羟基如新戊醇、1，1，1-三羟甲基乙烷、1，1，1-三羟甲基丙烷、季戊四醇等。适宜的脂族羧酸包括支链与非支链酸如丁酸、异丁酸、2-乙基己酸、正辛酸、戊酸、异戊酸、己酸、庚酸、壬酸、硬脂酸等。二元羧酸如马来酸、琥珀酸、己二酸等以及三元羧酸如1，2，4-苯三酸可以少量被用于调节多醇酯的粘度。
表1给出了适宜的能够提高稳定性与耐磨性的添加剂，它们可以与烃润滑剂一起被使用，这些润滑剂在其中润滑剂不与制冷剂混溶的制冷与空调应用场合使用表面活性剂。
                                表1
               适宜添加剂的实例(稳定剂与抗磨添加剂)
商品名 添加剂的化学与官能特征 ％(重)
2，6-二叔丁基对甲酚 酚类抗氧剂 0.5
烷基化二苯胺 胺抗氧剂 0.5
Reomet  39 三唑衍生物防铜腐蚀剂 0.5
ERL 4221 环氧化物 0.5
Syn-o-Ad  8478 三芳基磷酸酯抗磨添加剂 5.0
Durad  620B 磷酸酯抗磨添加剂 5.0
添加剂 RC8210 硫化特压添加剂 2.5
实施例I
向一个9ml玻璃管中加入0.050ml含有0.5％(重)待选表面活性剂的70SUS环烷基矿物油(Suniso 1GS)、6mm钢屑和0.70ml1，1，1，2-四氟乙烷(R-134a)并且将其密封。形成一个2相体系，环烷基矿物油构成上层，氟代烃构成下层。通过采用磁铁将金属屑在油相中迅速上下移动使油将金属屑全部润湿。随后缓慢地将金属屑降至四氟乙烷层中。结果如表II所示。
                     表II
表面活性剂 掺混行为
琥珀酸二异戊酯(PIB) 油粘附于金属屑和玻璃上
EXP5159-197(由Organics制造的氟化酯) 分散性有所改善，但是油粘附于金属屑与玻璃上
四(2-乙基己醇)季戊四醇 油粘附于金属屑和玻璃上
Surfynol SE 油被制冷剂从金属屑和玻璃上脱除，两层分散性非常好
Surfynol TG 油粘附于金属屑与玻璃上
EX1038(羧酸二聚体酯) 油粘附于金属屑与玻璃上
氟化烷基酯FC-430 油被R-134a从金属屑与玻璃上脱除，两层分散性非常好
FC-431 油粘附于金属屑与玻璃上
氟化烷基酯FC-740 油粘附于金属屑与玻璃上，过度起沫
上述数据清楚地表明含有2，4，7，9-四甲基-5-癸炔-4，7-二醇的Srufynol SE与含有氟化酯的FC-430适用于本发明。
实施例II
向一个9ml玻璃管中加入0.050ml含有0.05％(重)待选表面活性剂(Surfynol SE或FC-430)的70SUS环烷基矿物油(Suniso 1GS)、6mm钢屑和0.70ml1，1，1，2-四氟乙烷(R-134a)并且将其密封。形成一个2相体系，环烷基矿物油构成上层，氟代烃构成下层。通过采用磁铁将金属屑在油相中迅速上下移动使油将金属屑全部润湿。随后缓慢地将金属屑降至四氟乙烷层中。对这两种待选表面活性剂来说，均通过R-134a脱除金属屑与玻璃上的油。这两个润滑剂与制冷剂层彼此非常易分散，致使油在R-134a的作用下脱离金属屑与玻璃表面。
实施例III
对一个配有二个5门冷冻箱(每个105.6ft3)、一个距地面约6-7英尺的压缩机(Copelametic型R-76WMT3T)和每个冷冻箱上的蒸发器的多区域泵下螺旋管中等温度超市冷冻机(新英格兰)进行改型。制冷剂气体与油通过约20英尺直径为7/8英寸的直立与水平的抽吸回流管线，随后通过一个 英寸管到达压缩机。该系统被充入R-402A(装填30磅)，其中含有38％(重)R125(五氟乙烷)、60％(重)R22(氯二氟甲烷)，以及2％(重)R290(丙烷)和200SUS含有抗磨添加剂与发泡剂的烷基苯润滑油。在该装置于-5°F进行操作时，压缩机中润滑剂数量减少进而油压降低，装置停止工作。随后，该系统在约0°F操作以便保持适当的油压与润滑作用。
由该系统流出的油留下一些残余烷基苯；充入主要含有环烷基矿物油、10％(重)烷基苯和0.05％(重)Surfynol SE的150SUS油；排放0.5小时并且使其流动1小时以便冲洗来自该系统的残余烷基苯油。在此期间，油压开关未关闭，每一冷冻箱均达到-17～-10°F。1小时后，油再次从系统中流出，用主要含有环烷基矿物油、10％(重)烷基苯和0.05％(重)Surfynol SE的新鲜150SUS油替代。这两个冷冻机均在-10～-15°F下在不存在油回流困难的条件下操作2个月。
实施例IV
表III所示组合物与R-134a和2，4，7，9-四甲基-5-癸炔-4，7-二醇表面活性剂一道经过试验，结果使人满意。表中H-1代表40℃的12cst环烷基矿物油，H-2代表40℃的38cst白色环烷基矿物油，H-3代表40℃的29-30cst环烷基矿物油，H-4代表40℃的18cst环烷基矿物油，H-5代表40℃的29-30cst烷基苯，P1代表三羟甲基丙烷、70％戊酸与30％异戊酸的聚酯，P2代表季戊四醇与2-乙基己酸的聚酯，P3代表季戊四醇、戊酸、异戊酸和己二酸的聚酯。
                   表III
润滑剂(重量份) 表面活性剂(重量份)
99.95 H-191.90 H-1和8.0 P-187.80 H-1和12.0 P-1 .05.10.20
99.95 H-284.90 H-2和15.0 P-284.80 H-2和15.0 P-2 .05.10.20
89.95 H-3和10.0 H-589.90 H-3和10.0 P-384.80 H-3和15.0 P-3 .05.10.20
94.45 H-4和5.0 H-594.40 H-4和5.0 P-392.80 H-4和7.0 P-3 .05.10.20
实施例V
该实施例表明阴离子含氟烃表面活性剂可被用于本发明。采用下表所示的ISO10环烷基矿物油与待选阴离子和非离子含氟烃表面活性剂重复实施例II。Zonyl FSN与Zonyl FSO为具有不同氧化亚乙基链节含量的F(CF2CF2)3-8-CH2CH2O(CH2CH2O)xH。表中AN代表阴离子，NON代表非离子。
                   表IV
表面活性剂 类型 wt％ 活性
Zonyl FSP AN .05.50 部分脱除金属屑上的油全部脱除金属屑上的油
Zonyl FSA AN .05.50 无部分脱除金属屑上的油
Zonyl FSJ AN .05.50 全部脱除金属屑上的油全部脱除金属屑上的油
Zonyl FSN NON .05.50 无无
Zonyl FSO NON .05.50 无无
上述数据清楚地表明阴离子含氟烃表面活性剂适用于本发明。
对比实施例
为了在不采用本发明添加剂的条件下将润滑剂排挤出金属屑，以实施例II所述方式测试含有由90％(重)矿物油与10％(重)聚酯组成的混合物或由70％(重)矿物油与30％(重)聚酯组成的混合物的润滑剂组合物，其中采用ISO10环烷基矿物油和代表由三羟甲基丙烷与30％戊酸形成的聚酯P-1或代表由2-乙基己酸与79％新戊二醇和21％季戊四醇形成的多醇酯的P-2。结果如表V所示。
               表V
聚酯 ％(重) 结果
P-1 10％30％ 油粘附于金属屑与玻璃上油粘附于金属屑与玻璃上
P-2 10％30％ 油粘附于金属屑与玻璃上油粘附于金属屑与玻璃上

Claims (24)

1.一种流体制冷组合物，其中含有烃润滑剂、与烃润滑剂不混溶的含有至少一个碳原子和一个氟原子的制冷剂以及能够将烃润滑剂与液体制冷剂之间界面上的界面张力降低至使钢上制冷剂液体的铺展系数略大于零或非常接近零从而使制冷剂排挤烃润滑剂离开钢的程度的添加剂，所述添加剂在钢上的浓度为每100重量份烃润滑剂0.001-5重量份。
2.按照权利要求1的组合物，其中烃润滑剂含有链烷矿物油。
3.按照权利要求1的组合物，其中烃润滑剂含有环烷油。
4.按照权利要求1的组合物，其中烃润滑剂含有烷基苯油。
5.按照权利要求1的组合物，其中烃润滑剂含有聚α-烯烃及其低聚物。
6.按照权利要求1的组合物，其中烃润滑剂含有大量环烷矿物油与少量烷基苯油。
7.按照权利要求6的组合物，其中烃润滑剂为链烷矿物油。
8.按照权利要求1的组合物，其中制冷剂含有氟代烃。
9.按照权利要求8的组合物，其中氟代烃中所有卤素基团均为氟。
10.按照权利要求9的组合物，其中氟代烃含有1，1，1，2-四氟乙烷。
11.按照权利要求9的组合物，其中氟代烃含有五氟乙烷。
12.按照权利要求9的组合物，其中所述组合物还含有二氟一氯甲烷。
13.按照权利要求1的组合物，其中添加剂含有表面活性剂。
14.按照权利要求13的组合物，其中表面活性剂含有2，4，7，9-四甲基-5-癸炔-4，7-二醇。
15.按照权利要求14的组合物，其中所述组合物含有多醇酯润滑剂，多醇酯与烃润滑剂的重量比为约1∶99-1∶3。
16.按照权利要求13的组合物，其中表面活性剂含有含氟酯。
17.按照权利要求13的组合物，其中表面活性剂含有阴离子含氟烃。
18.按照权利要求1的组合物，其中制冷剂在-40～80℃的温度范围内与润滑剂不混溶。
19.一种流体制冷组合物，其中含有烃润滑剂，该润滑剂含有至少一种选自下列种类的物质：链烷矿物油、环烷矿物油、烷基苯油、以及聚α-烯烃及其低聚物，该组合物还含有与烃润滑剂不混溶的含有至少一个碳原子和一个氟原子的制冷剂以及有效量能够降低烃润滑剂与液体制体冷剂之间界面张力从而使制冷剂能够将润滑剂从换热器与管线内表面上脱除的添加剂。
20.一种组合物，其中含有多醇酯润滑剂与2，4，7，9-四甲基-5-癸炔-4，7-二醇。
21.按照权利要求19的组合物，其中所述2，4，7，9-四甲基-5-癸炔-4，7-二醇的浓度相对于每100重量份多醇酯约为0.1-100重量份。
22.一种组合物，其中含有多醇酯润滑剂和氟化酯。
23.一种组合物，其中含有多醇酯润滑剂与阴离子氟代烃。
24.一种改进压缩机系统的方法，其中包括将含有多醇酯润滑剂与2，4，7，9-四甲基-5-癸炔-4，7-二醇的浓缩物加至压缩机系统的步骤。
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