CN1427070A - 压缩制冷机润滑油及其用于制冷/空调机的用途 - Google Patents

压缩制冷机润滑油及其用于制冷/空调机的用途 Download PDF

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CN1427070A
CN1427070A CN02140314A CN02140314A CN1427070A CN 1427070 A CN1427070 A CN 1427070A CN 02140314 A CN02140314 A CN 02140314A CN 02140314 A CN02140314 A CN 02140314A CN 1427070 A CN1427070 A CN 1427070A
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lubricating oil
weight
addition
oil
refrigeration agent
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CN1228425C (zh
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松浦秀树
野村雅树
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Daikin Industries Ltd
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Daikin Industries Ltd
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Abstract

将粘度不大于70cSt(40℃)的PAG按0.1至20％(重)(优选2至10％(重))的数量加至一种合成润滑油如PVE或酯油中，制备一种与HFC制冷剂及污物二者均配伍性良好的润滑剂。因此，一种装有同时利用HFC制冷剂及润滑剂作为工作液的压缩机的制冷及/或空调机装置，不致引起在该装置中混合物的比例失调，也不致降低清洁毛细管的作用。在这种情况下，也不需对冷冻及/或空调装置进行改造，而且可以低成本得到高可靠性的制冷/空调装置。

Description

压缩制冷机润滑油及其用于制冷/空调机的用途
本申请是1998年10月15日提交的题为“压缩制冷机润滑油及使用它的制冷/空调装置”的PCT/JP98/04654号发明专利申请的分案申请，原申请于1999年6月17日进入中国国家阶段，并获得中国专利申请号98801541.2。
技术领域
本发明涉及一种与氟代烃(hydrofluocarbon)制冷剂一起使用的压缩制冷机润滑油，和应用这种润滑油的制冷/空调机。
技术背景
至今，为防止在将制冷剂系统由氯氟代烃转换为氟代烃时产生污物引起毛细管及膨胀阀阻塞的现象，已进行过许多研究尝试。例如，在日本专利JP-A 103616/1995披露的“制冷机及制冷剂压缩机”中，采用一种由薄膜材料如氟树脂及纤维素混合酯组成的过滤器，安装在制冷通路上。此外，在日本专利JP-A 235569/1994披露的“制冷机及制冷剂压缩机”中，将一种由孔径不超过80微米的烧结孔隙金属组成的过滤器插入制冷机的干燥器中。还有，日本专利JP-A105673/1996披露的“制冷机”中，采用在操作时用高压气体吹扫毛细管的方法清除淤泥。
此外，在日本专利JP-A 247582/1996披露的“制冷循环”中，为防止由于制冷循环中产生的污物积累引起的各种弊端：
(1)、采用由用以分隔制冷剂通路内装过滤器或分支阀的管子所构成的许多机构，作为一种节流机构；和
(2)、提供一种与调节通路无关的、经直接控制阀的净化管，或
(3)、按规定的比例采用一种合成酯油和选自环烷基矿物油、石蜡基矿物油及烷基苯矿物油中的任何一种矿物油，作为压缩机的润滑油。此外，在日本专利JP-A 143486/1997披露的“制冷机组合及制冷循环”中，为防止由酯基制冷机油所引起的阻塞现象，采用了一种制冷机油，内含由5-30份重的选自环烷基矿物油、石蜡基矿物油、聚α-烯烃矿物油和烷基苯的矿物油中的任何一种矿物油与70-95份重的多醇所组成的基础油。
但是，对于日本专利JP-A 103616/1995所披露的“制冷机及制冷剂的压缩机”和JP-A 235569/1996披露的“制冷机及制冷剂压缩机”及JP-A 247582披露的“制冷循环”的情况，均有一个问题，即由于以前的制冷机及空调机均不能按他们要求那样地使用，而均需另外有过滤器、高压气鼓风机、装有过滤器的节流机构及污物净化管，导致了成本增加。此外，在使用前述过滤器时，还进一步引起了过滤器本身阻塞的问题。
另外，对于在日本专利JP-A 247582/1996披露的“制冷循环”及JP-A 143486/1997“制冷机组合及制冷循环”的情况，上述制冷机油与HFC制冷剂已是可混溶的，尤其是对于R410A的情况，问题在于，其混合的数量要受到严格限制。此外，还有一个问题，与操作条件有关，在制冷机内出现混合油比例偏差会降低洗涤毛细管的效率。
发明内容
为克服上述缺点进行了本发明工作。本发明目的在于，提供一种在使用HFC制冷剂时可防止由于污物引起毛细管和膨胀阀阻塞的润滑油，而无需对压缩制冷机进行机器改造，以及一种使用这种润滑油的制冷/空调机。
为达到上述目的，本发明以一种与HFC制冷剂一起使用的压缩制冷机润滑油为特征，它包括一种具有下述通式的化合物：
                         R1(R2O)n(R3O)mR4式中R1：烷基团、烷氧基团及芳基团中的任何一种基团；
R2：碳数2-4的亚烷基团；
R3：碳数2-4的亚烷基团；
R4：氢或烷基团。
按这样的基本特征，将一种与HFC制冷剂可混溶性的和与使用HFC制冷剂中产生的污物可互溶的化合物，添加至本压缩制冷机的润滑油中。为此，不会因本润滑油与HFC制冷剂一起使用作为工作液而引起上述制冷/空调机内本润滑油与HFC制冷剂间出现比例偏差。因此，可防止对毛细管及膨胀阀洗涤效率的下降。这就是说，按照本发明可以增强使用HFC制冷剂的制冷/空调机的可靠性，无需为此对机器作任何改造。
此外，本发明以一种与HFC制冷剂一起使用的压缩制冷机聚乙烯醚润滑油为特征，它包括一种其添加数量不低于5％(重)和不超过10％(重)的化合物，所述化合物具有如下通式：
                 R1(C4H8O)n(R5O)mR4其中R1：烷基团、烷氧基团及芳基团中的任何一种；
R4：氢或烷基团；
R5：碳数2-3的亚烷基团；
n/m：1/9-10/0。
按照这样的基本特征，由于上述化合物含有碳数为4的环氧丁烷(C4H8O)，其与HFC制冷剂及污物的可互溶性非常好。而且将该化合物添加至压缩制冷机的本聚乙烯醚润滑油中，其数量不低于5％(重)。因而，可使由于采用本润滑油及HFC制冷剂作为工作液时制冷/空调机毛细管及膨胀阀阻塞所引起的流量下降率充分降低，至0-10％，因此可有效地防止由污物引起的毛细管和膨胀阀的阻塞。另外，由于添加至本润滑油中的上述化合物数量不超过10％(重)，可以减少本润滑油作为整体的容积绝缘强度的下降。这样，密封型电机泄漏电流不可能增大。这就是说，按照本发明，可以提高采用HFC制冷剂的制冷/空调机的可靠性，而无需对机器的任何改造。
此外，本发明以装有采用HFC制冷剂及润滑油作为工作液的压缩机的制冷/空调机为特征，该工作液包括一种通式一般为下述的化合物：
                    R1(R2O)n(R3O)mR4式中R1：烷基团、烷氧基团及芳基团中的任何一种基团；
R2：碳数2-4的亚烷基团；
R3：碳数2-4的亚烷基团；
R4：氢或烷基团。
按照这样的基本特征，这里采用了与添加化合物及HFC制冷剂一起使用的一种润滑油，作为制冷/空调机的压缩机的工作液，所述化合物与该HFC制冷剂可混溶，而与使用HFC制冷剂中所产生的污物可互溶。为此，不会引起上述润滑油与HFC制冷剂之间比例的偏差，因而也可以防止毛细管及膨胀阀的洗涤效率下降。也就是说，按照本发明，可以以低价格得到高可靠性的使用HFC制冷剂的制冷/空调机，而无需对其进行改造。
另外，一组实施方案特征在于，上述添加至该润滑油中的化合物的数量不低于0.1％(重)和不高于20％(重)。
按照这样的基本特征，由于上述化合物添加量为0.1％(重)或以上，可使制冷/空调机的流量下降率减少到低于用以前的HFC制冷剂/聚乙烯醚(或聚醇醚)时的下降率。此外，由于上述容积绝缘强度低的化合物的数量在20％(重)或以下，整个润滑油的容积绝缘强度就不可能变得太小乃至使封闭型电机的电流泄漏增大到不适用的程度。
此外，一组实施方案特征在于，上述添加至润滑油中的化合物的数量不低于2％(重)和不高于10％(重)。
按照这样的基本特征，制冷/空调机的流量下降率可以降低至0％-17％。因此，可有效地防止由于污物引起的毛细管及膨胀阀中的阻塞。
另外，一组实施方案特征在于，上述化合物40℃时的粘度为70cSt(厘沲)或以下。
按照这样的基本特征，由于上述化合物的40℃粘度为70cSt或更低，上述化合物的分子量就应当在数千以下。因此可以防止由于在低温区时粘度增加至数万所引起的上述化合物本身的阻塞，诸如毛细管的阻塞。
此外，一组实施方案特征在于，在上述化合物中的亚烷基团R2及R3二者碳数均为4。
按照这样的基本特征，由于亚烷基团碳数大，增大了其与HFC制冷剂的互溶性，而因此流量下降率可以有效地降低至0％-10％，因而，可以更为有效地防止由于污物引起的毛细管及膨胀阀的阻塞。
另外，本发明是以装有使用HFC制冷剂及聚乙烯醚润滑油作为工作液的压缩机的制冷/空调机为特征，在该工作液中添加了其量不低于5％(重)和不超过10％(重)的具有下述通式的化合物：
                      R1(C4H8O)n(R5O)mR4其中R1：烷基团、烷氧基团及芳基基团中的任何一种基团；
R4：氢或烷基团；
R5：碳数2-3的亚烷基团；
n/m：1/9-10/0。
按照这样的基本特征，由于上述化合物含有碳数为4的环氧丁烷(C4H8O)，其与HFC制冷剂及污物的互溶性非常好。而且由于该化合物是添加至聚乙烯醚润滑油中，数量不低于5％(重)，因而可充分降低制冷/空调机内流量下降率至0-10％，从而能有效地防止污物所引起的毛细管和膨胀阀阻塞。另外，由于添加至本润滑油中的上述化合物数量为10％(重)或更低，可以减少整个润滑油的容积绝缘强度的下降。因此，密封型电机泄漏电流不可能增加。这就是说，按照本发明，可以得到高可靠性的采用HFC制冷剂的制冷/空调机，而无需其任何改造。
此外，一组实施方案特征在于，在上述通式中对于n及m的比例n/m为7/3或更高。
按照这样的基本特征，由于在上述通式中n对m的比例n/m为7/3或更高，环氧丁烷的比例高，因而制冷/空调机中的流量下降率可进一步降低至0-5％。因此可以更为有效地防止由于污物所引起的毛细管及膨胀阀的阻塞。
另外，一组实施方案特征在于，上述化合物在40℃的粘度在32cSt以上，而不高于70cSt。
按照这样的基本特征，由于上述化合物40℃的粘度在32cSt以上，可以减少整个润滑油的容积绝缘强度的下降。再则，由于上述化合物的粘度在70cSt或以下，上述化合物的分子量应当在数千以下，因此，可以防止由于在低温区时粘度增加至几万所引起的上述化合物自身的阻塞，如毛细管的阻塞。
附图简述
图1为说明将PAG添加至用于本发明制冷/空调机所用的制冷机油中的条件与其性能间的关系图。
图2为说明将PAG添加至制冷机油中的条件与其性能间的关系图，为图1的续图。
图3为说明图1及图2结果的数据比较图。
图4为说明当R1(EO)n(PO)mR4加至PVE中时添加量与流量下降率间的关系图。
图5为说明R1(BO)n(EO)mR4加至PVE中时添加量与流量下降率间的关系图。
图6为说明R1(BO)n(EO)mR4加至PVE中时添加量与粘度及容积绝缘强度间的关系图。
实施本发明的最佳方式
图1及图2为说明将聚亚烷基二醇添加至用于本发明这种模式的制冷/空调机的制冷机油中各种条件与其性能间的关系图。另外，本发明这种模式的制冷/空调机装有应用HFC制冷剂及润滑油作为工作液的压缩机。此外，上述聚亚烷基二醇(PAG)以下述通式为代表：
                         R1(R2O)n(R3O)mR4式中R1：烷基团、烷氧基团及芳基团中的任一种基团；
R2：碳数2-4的亚烷基团；
R3：碳数2-4的亚烷基团；
R4：氢或烷基团。
图中符号a-n表示聚乙烯醚(PVE)用作制冷机油的情况，只要R1-R4的基本特征是在a-d范围内变化的。此外，如果在d-g、k、l、m及n之内，添加至PVE中的数量则随R1-R4所固定的基本特征变化。另外，在h及i内，R1的碳数是变化的。图中符号o表示使用酯油作为制冷机油的情况。另外，在图1及图2中的流量下降率是在当上述PVE/PAG或酯油/PAG的润滑油与HFC制冷剂一起使用时，毛细管、膨胀阀或其它部件阻塞所引起的流量速率下降。此外，在图1中，“PO”指的是环氧丙烷，“EO”指的是环氧乙烷，“BO”指的是环氧丁烷。
图3说明与图1及图2中结果的对比数据。图中符号p-r代表未加添加剂的情况，其中，p代表制冷剂为HCFC R22和制冷机油为Suniso油的情况。此外，q代表制冷剂为HFC和制冷机油为PVE的情况。而r代表制冷剂为HFC制冷剂和制冷机油为多元醇酯(POE)的情况。图中符号s及t代表加有添加剂的情况，而其中s代表制冷剂为PVE和添加剂为聚丁烯的情况。此外，t代表制冷机油为PVE及添加剂为烷基萘的情况。另外，在s及t的情况下，流量下降率是当PVE/聚丁烯或PVE/烷基萘的润滑油与HFC制冷剂一起使用时由于毛细管、膨胀阀或其它部件的阻塞而引起的流量下降率。
图1至3表明，对PAG的添加数量，要求在0.1％(重)或以上，以使流重下降率降低到低于HFC/PVE/-(图3中q)情况的下降率。此外，如众所周知，PAG的容积绝缘强度较低(约109-1010 Ωcm(欧姆厘米))，而当添加量过大时，整个制冷机油的容积绝缘强度会变得太低，从而使经常用于制冷/空调机的封闭型电机电流泄漏增加到电机不适用的程度。从这种观点来看，要求添加PAG的数量应在20％(重)或以下。也就是说，按照本发明的模式，PAG的添加量是不低于0.1％(重)和不高于20％(重)。另外，在希望有明显的效应时，最好添加量不低于2％(重)和不多于10％(重)。
此外，当PAG 40℃的粘度在70cSt以上时，由于其分子量应当在几千以上，在低温区，如在毛细管内，其粘度会增加至几万cSt，这就会导致由于PAG自身的阻塞。而另一方面，甚至在粘度非常低的时候，在添加量又在约0.1％(重)时，整个制冷机油的粘度不致降低至有害的程度。从上述点来看，按照本发明的这种模式，PAG 40℃的粘度要设定在70cSt或以下。
从图1及2中的a-n可以看出，在采用HFC制冷剂及PVE时，流量下降率数值较低，为0-17％，表明将PAG添加至PVE中对防止毛细管、膨胀阀及其它部件的阻塞是有效的。此外，当上述PAG的亚烷基团R2的碳数为4时(相当于图1及图2中的d-n)，流量下降率比采用R22(HCFC制冷剂)/Suniso油在添加至PVE中的数量为2.5％(重)-10％(重)时的小了很多。因此，可以看出将R2及R3的二者的亚烷基碳数设定在4而不是3时，可以抑制流量下降率。
此外，当用上述HFC制冷剂及POE(酯油)时，如图3的r所示，其流量下降率大(25％-33％)。但是，如图2中o所示，将PAG添加至酯油中时，使流量下降率充分降低至5％-10％，说明上述PAG的添加对酯油是有效的。
如上所述，按照本发明的这种模式，将40℃粘度不超过70cSt的PAG添加至合成润滑油中，如PVE及酯油，其数量不低于0.1％(重)和不多于20％(重)(最好，不低于2％(重)和不多于10％(重))，可以得到与HFC制冷剂及污物二者互溶性均良好的润滑油。因此，在装配有同时使用HFC制冷剂和上述润滑油作为工作液的压缩机的制冷/空调机中，不会引起机内本润滑油及HFC制冷剂之间比例的偏差，因而可以防止毛细管及膨胀阀洗涤效率的下降。在这样的情况下，就可以以低成本获得高可靠性的制冷/空调机，而无需对机器进行改造。
同时，如上所述，尤其是当上述PAG的亚烷基R2的碳数为“4”时，流量下降率变小。然后，再详细描述按照下述本发明的模式有关使用：
                    R1(BO)n(R5O)mR4其中R1：烷基团、烷氧基团及芳基团中的任何一种；
R4：氢或烷基团；
R5：碳数2-3的亚烷基团；
n/m：1/9-10/0的方法，其中以通式R1(R2O)n(R3O)mR4所表示的PAG的(R2O)用“BO(环氧丁烷)”取代。
图4说明，在添加R1(EO)n(PO)mR4至制冷机油PVE中时添加量与流量下降率的关系，其中亚烷基R2的碳数为2和上述PAG中亚烷基R3的碳数为3。图4中的数字为n/m。此图表明，当亚烷基R2及R3二者均为3或以下而不论n/m多少，流量下降率变为5％或以上，而在R2及R3亚烷基的碳数为3或以下的情况下，未能降低流量下降率。因此，将亚烷基R2的碳数设定在4或以上，对降低流量下降率有效。
图5表明，在将R1(BO)n(EO)mR4添加至上述制冷机油PVE中时添加量与流量下降率间的关系。此外，图6表明在将R1(BO)n(EO)mR4添加至上述制冷机油PVE中时，添加量与添加了R1(BO)n(EO)mR4的整个润滑油的容积绝缘强度之间的关系。在此二图中的数字表示n/m。图5表明，在n/m＝1/9，当添加量为10％(重)时，可以得到10％的流量下降率。另外，增加n/m比，甚至当添加量从10％(重)往下减少时，流量下降率为10％或以下，因此，可以认为在n/m＝1/9-10/0的范围内，降低流量下降率有效。此外，可以看出，当n/m的数值为7/3或以上时，流量下降率明显的低(0％-5％)，而当n/m＝5/5时，流量下降率高。另外，图5还表明，当添加量为5％(重)或以上时，流量下降率迅速下降至2.5％以下。但是，如图6所示，当添加量增至10％(重)以上，整个润滑油的容积绝缘强度明显下降。
这就是说，从上述几点来看，按照本发明模式在将R1(BO)n(EO)mR4加至制冷机油PVE中时，上述n/m设定在9/1-10/0，而添加量设定在不低于5％(重)和不高于10％(重)。另外，在希望有明显的效应时，最好将n/m值设定在7/3或以上(7/3-10/0)。
此外，图6还说明40℃下R1(BO)n(EO)mR4(n/m＝7/3)的粘度与整个润滑油的容积绝缘强度的关系。图6表明，在粘度变成为32cSt以下时，整个润滑油的容积绝缘强度明显降低。但如上所述，当粘度超过70cSt(40℃)时，其分子量应当在几千以上，而在低温区，诸如毛细管内，其粘度将会增加至几万cSt，这就导致了R1(BO)n(R3O)mR4本身的阻塞。因此，按照本发明的模式，R1(BO)n(R3O)mR4的40℃粘度设定在32cSt以上，而不超过70cSt。
工业实用性
按照本发明将压缩制冷机的润滑油与HFC制冷剂同时使用，以防止由于污物所引起的毛细管及膨胀阀阻塞，无需对制冷机进行任何改造。

Claims (6)

1、一种与氟代烃制冷剂同时使用的压缩制冷机润滑油，包含通式如下的添加化合物：
                       R1(R2O)n(R3O)mR4式中R1：烷基团、烷氧基团及芳基团中的任何一种基团；
R2：碳数2-4的亚烷基；
R3：碳数2-4的亚烷基；
R4：氢或烷基团。
2、按照权利要求1的润滑油，其中所述添加化合物的量不低于0.1％重量和不多于20％重量。
3、按照权利要求2的润滑油，其中所述添加化合物的量不低于2％重量和不多于10％重量。
4、按照权利要求1的润滑油，其中所述添加化合物40℃的粘度为70cSt或以下。
5、按照权利要求1的润滑油，其中所述添加化合物中的亚烷基R2和R3二者的碳数均为4。
6.权利要求1-5任一项的润滑油与氟代烃制冷剂一起用于制冷/空调机的用途。
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