CN1057557C - 与氢氯氟烃和氢氟烃制冷剂一起使用的制冷机油组合物 - Google Patents
与氢氯氟烃和氢氟烃制冷剂一起使用的制冷机油组合物 Download PDFInfo
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- CN1057557C CN1057557C CN96100875A CN96100875A CN1057557C CN 1057557 C CN1057557 C CN 1057557C CN 96100875 A CN96100875 A CN 96100875A CN 96100875 A CN96100875 A CN 96100875A CN 1057557 C CN1057557 C CN 1057557C
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- ester
- acid
- refrigeration agent
- oil
- machine oil
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Abstract
本发明公开了供蒸汽压缩或制冷机使用的制冷机油组合物,该组合物可以与HCFC制冷剂和HFC制冷剂中的任一种一同使用。本发明的机油组合物包括多元醇酯(酯化合物)作为基油。此外,此基油含有按重量计为1.0至少于5.0%的磷酸酯,按重量计0.1至2.0%的硫代磷酸烷基酯和/或硫代磷酸芳基酯,以及按重量计为0.05至2.0%的环氧化合物。由于这些添加剂的协同效应,本发明组合物无多元醇酯所具有的有淤渣形成和润滑能力不足的缺点。另一方面,本发明组合物提供了所希望的多元醇酯基油所具有的性能,即与制冷剂有良好的相容性,高电绝缘性质和低吸湿性。
Description
发明领域
本发明涉及制冷机油组合物,该组合物可与氢氯氟烃(HCFC)制冷剂和氢氟烃(HFC)制冷剂中的任何一种一起使用。
更准确地说,本发明涉及可供采用氢氯氟烃或氢氟烃作为制冷剂的蒸汽压缩式制冷机使用的制冷机油组合物。本发明制冷机油组合物显示出优越的耐磨性,载荷能力,热和化学稳定性,低温流动性及优越的制冷剂混溶性。
发明背景
1.制冷机油的一般性能要求
重要的制冷机油的一般性能要求是指其耐磨性,载荷能力,热和化学稳定性,低温流动性,以及制冷剂混溶性。
制冷机油被用于润滑和冷却压缩机的滑动部分,发散制冷压缩热,在制冷压缩步骤中密封压缩机,以及除去耐磨颗粒以及磨损组件的外来杂质,等等。
鉴于上述要求,制冷机油不但必须能提供包括耐磨性和载荷能力在内的优良润滑性能,而且也必须在制冷剂和压缩机材料如电子绝缘体和金属组件两者都存在下具有热和化学稳定性,以便机油不会对这些材料有不利作用。
制冷机中,部分制冷机油进入压缩致冷气体端并通过制冷***循环流入到包括蒸发器,毛细管和膨胀阀在内的低温端。
因此制冷机油必须具有低温流动性并且也必须与制冷剂相混溶,以便提高蒸发器的冷却能力,改进油从低温端返回到压缩机中的能力,并且当在低温下重新启动压缩机时能使压缩器的滑动部分达到充分的润滑。
2.制冷剂与制冷机油间的关系
氯氟烃(CFC)和氢氯氟烃(HCFC)制冷剂通常单独或相互结合在蒸汽压缩式制冷剂中使用。
由于其低极性,CFC和HCFC制冷剂一般与非极性烃油是可混溶的。CFC和HCFC制冷剂分子含有一个或多个氯原子,它们在压缩机的滑动表面上反应产生氯化物,氯化物用作润滑剂。此外,烃油显示出令人满意的润滑能力。
在使用如CFC和HCFC制冷剂的制冷机中使用的制冷机油一般包括基油(烃油),它包括适当精炼的环烷基矿物油,链烷族矿物油,烷基苯,聚-α-烯烃,或类似物或它们的两种或多种混合物,以及添加剂如抗氧剂,抗磨添加剂和缓蚀剂。
在烃油中具有低溶解度并在低浓度下显示出耐磨性效力的磷酸酯通常以多至1%重量比的量加入到烃类基油中。
在CFC和HCFC制冷剂破坏同温层中的臭氧层的假设发表之后,制定了国际章程用于管理这些制冷剂,保护全球环境。同样,业已进行了开发制冷剂替代物(新型制冷剂)的尝试。国际协议禁止1996年后继续生产CFC制冷剂,并且在2020年后完全禁止HCFC制冷剂的生产。
代表性的HCFC制冷剂是HCFC-22(R-22)。HCFC-22制冷剂的可能替代物是氢氟烃(HCF),如HFC-134a,HFC-143a,HFC-125,HFC-32等以及它们的混合物。
这些HFC制冷剂的每一种都具有强极性,因此它们与烃油具有较差的混溶性。因而研究人员正在寻求开发适合与HFC致冷剂一同使用的制冷机油。
3.与HFC制冷剂一同使用的制冷机油的先有技术
与HFC制冷剂相容的含氧合成烃油如酯类合成油和聚醚类合成油已被考虑用作供采用HFC制冷剂的制冷机中使用的制冷机油。酯类合成油比聚醚类合成油具有高电绝缘特性,更好的高温配伍性,以及较低的收湿性等优点。
基于酯类合成油的制冷机油已在如JP-A-56-133241(本文所用术语“JP-A是指未经审查已公开的日本专利申请”)和JP-A-59-164393中公开。JP-A-2-276894公开了上述种类制冷机油特别适合与含氯氟烃或氟代烃制冷剂一同使用。此外,在如JP-A-3-88892,JP-A-3-128991和JP-A-3-128992中也公开了上述种类制冷机油特别适合与氢氟烃制冷剂一同使用。
包含酯类合成油且其中掺有磷酸酯或亚磷酸酯的制冷机油已公开于下述专利中:JP-A-55-92799,JP-A-56-36570,JP-A-56-125494,JP-A-62-156198,JP-A-3-24197和JP-A-5-59388,并且JP-B-57-43593(本文所用术语“JP-B”是指“已审查的日本专利公开书”)中公开了上述种类制冷机油用作热泵油。
上述制冷机油中,JP-A-5-59388(相应的美国专利申请已授权,为美国专利5,342,533号)中所公开的制冷机油组合物打算供采用HFC制冷剂的制冷机中使用。这种机油主要包括作为基油的多元醇的二元酸二酯或羧酸酯,以及加在基油中的磷酸酯或亚磷酸酯,其加入量为5.0至90.0%(重量)。JP-A-5-59388(U.S.P.5342533)公开了如果磷酸酯或亚磷酸酯的加入量少于5.0%(重量),则其抑制淤渣形成及改进耐磨性的效力将不足的技术情报。
此外,JP-A-5-17792公开了一种制冷机油组合物,它包含作为基油的酯油,烷基苯或矿物油以及掺合在其中的亚烷基二元醇二环氧甘油酯或具有特殊结构的脂族环状氧化合物。
制冷机油应当具有适合同时使用的制冷剂的特殊结构。与CFC和HCFC制冷剂一同使用的制冷机油在采用HFC制冷剂的制冷机中难以使用,其中所述的HFC制冷剂为一种新型制冷剂。例如,尽管酯类合成油具有优良的与HFC制冷剂的混溶性,但当与HCFC制冷剂一同使用时会产生淤渣。
因此,所有基于酯类合成油打算供采用HFC制冷剂的制冷机中使用的现有制冷油都不适合采用HCFC制冷剂的制冷机使用。
由于HCFC制冷剂的生产被分阶段地限制并且在2020年之后被完全禁止,因此采用HCFC制冷剂的制冷机不仅需要用HFC制冷剂替代其中使用的HCFC制冷剂,而且也需要用适合HFC制冷剂的油来替代所用的制冷机油。如果当替代制冷剂时不需要替代早已在实际使用的制冷机内的制冷机油,则这类制冷机的维修就变得十分容易。
发明概述
本发明的目的是提供一种制冷机油组合物,该组合物包含多元醇酯(酯类合成油)作为基油,并且该组合物适合与HCFC制冷剂和HFC制冷剂的任何一种一同使用。
本发明的目的完全与传统方法相反。为实现该目的,希望具有下述特性:
(i)与HCFC制冷剂一同使用的适配性
由于HCFC制冷剂的分子中含有一个或多个氯原子,受氯原子的作用,多元醇酯易于热解。这种热解分解特压添加剂,由此导致淤渣形成。
为了与HCFC制冷剂一同使用多元醇酯,必须选择适当的添加剂,抑制淤渣形成。
(ii)与HFC制冷剂一同使用的适配性
由于HFC制冷剂与HCFC制冷剂不同,在其分子中不含氯原子,这些制冷剂不产生可用作润滑剂的氯化物。而且与烃油相比,多元醇酯具有较差的润滑性。
此外,由于多元醇酯比烃油具有较高的化学活性,故它们在加热压缩机内倾向于产生淤渣。
与HFC制冷剂一同使用多元醇酯时,应选择适当的添加剂来补偿不足的润滑性并在高温操作期间抑制淤渣形成。
为实现上述特性并由此达到本发明的目的,本发明的发明者研究了多种添加剂,以便选择适合多元醇酯的添加剂。结果,本发明的发明人员发现恰恰在加入到多元醇酯内的磷酸酯的量少于5.0%重量时,通过进一步以最佳比例掺入特殊添加剂可以改善润滑能力并抑制淤渣形成。基于该发现完成了本发明。
本发明提供了可供采用氢氯氟烃或氢氟烃作为制冷剂的蒸汽压缩机中使用的制冷机油组合物。
更准确地讲,本发明的上述目的已通过提供包含多元醇酯作为基油的制冷机油组合物达到,其中所述基油包含:
(a)其量为从1.0至少于5.0%重量的磷酸盐;
(b)至少一种硫代磷酸烷基酯和硫代磷酸芳基酯,其量为0.1至2.0%重量比;和
(c)按重量计为0.05至2.0%的环氧化合物,其中组分(a)、(b)及(c)的量各自基于所述基油的量。
附图简介
附图1是使用四球试验机测量摩擦转矩的装置的简图。
附图2示出了在HFC-134a制冷剂环境下使用图1所示装置的摩擦转矩试验的结果。
附图3示出在HCFC-22制冷剂环境下使用图1所示装置进行的摩擦转矩试验的结果。
附图4示出了延长压缩机寿命试验的结果。
发明详细描述
1.基油
在本发明中多元醇酯被用作基油。
可在本发明中使用的多元醇酯是指通过至少一种多元醇与羧酸(如线性饱和脂肪酸,带有烷基支链的脂肪酸,或带有两个或多个烷基支链的脂肪酸)反应所得到的酯,这些酯的混合物,以及通过多元醇混合物与至少一种羧酸反应所得到的酯。
多元醇的实例包括新戊二醇,三羟甲基丙烷,季戊四醇和双季戊四醇(dipentaerythritol)。
线性饱和脂肪酸包括乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一酸及十二酸。
带有一个烷基支链的脂肪酸实例包括异丁酸,2-甲基丁酸,异戊酸,三甲基丙酸,2-甲基戊酸,3-甲基戊酸,4-异己酸,8-乙基己酸,4-丙基戊酸,4-乙基戊酸,2-甲基癸酸,3-甲基癸酸,4-甲基癸酸,5-甲基癸酸,6-甲基癸酸,6-乙基壬酸,5-丙基辛酸,3-甲基十一酸及6-丙基壬酸。
带有两个或多个烷基支链的脂肪酸包括2,2-二甲基丁酸;2,2-二甲基戊酸;2,2,3-三甲基丁酸;2,2-二甲基己酸;2-甲基-3-乙基戊酸;2,2,3-三甲基戊酸;2,2-二甲基庚酸;2-甲基-3-乙基己酸;2,2,4-三甲基己酸;2,2-二甲基-3-乙基戊酸;2,2,3-三甲基戊酸;2,2-二甲基辛酸;2-丁基-5-甲基戊酸;2-异丁基-5-甲基戊酸;2,3-二甲基壬酸;4,8-二甲基壬酸及2-丁基-5-甲基己酸。
多元醇酯一般具有5至150mm2/s(40℃)的粘度,并可以具有高至1mg KOH/g的酸值且以及高至500ppm的水含量。多元醇酯优选具有0.01mg KOH/g或更低的酸值以及100ppm或更低的水含量。这些特性可通过下述步骤得到:将酯蒸馏,过滤,用吸附剂和脱水剂处理除去影响热稳定性的杂质,污染物,以及水。
2.添加剂
(1)磷酸酯
可在本发明中使用的磷酸酯是指磷酸与酚或醇所形成的酯。
磷酸酯的实例包括磷酸三甲酯,磷酸三乙酯,磷酸三丁酯,磷酸三辛酯,磷酸三(丁氧基乙基酯),磷酸三苯酯,磷酸三(甲苯酯),磷酸三(二甲苯酯),磷酸甲苯,联苯酯,磷酸二苯,邻联苯酯,磷酸辛基二苯基酯,磷酸苯基异丙基苯基酯,磷酸二苯基异丙基苯酯,磷酸三(异丙苯酯),磷酸三(氯乙酯)以及磷酸三(二氯丙酯)。
这些酯中,特别优选磷酸三(甲苯酯),磷酸苯基异丙基苯基酯,磷酸二苯基异丙基苯酯及磷酸三(异丙苯酯)。
磷酸酯在本发明组合物中的比例按基于多元醇酯基油的重量计为1.0至少于5.0%。
按照上述JP-A-5-59388(U.S.P5,342,533),磷酸酯的比例少于5.0%重量比时将导致耐磨能力不足以及抑制淤渣形成的能力不足。然而,按照本发明,当磷酸酯与硫代磷酸烷基酯或芳基酯以及环氧化合物以最佳比例加入到多元醇酯基油中时,即使磷酸酯的比例小于5.0%重量比,其优点能完全实现。如果磷酸酯的比例低于1.0%重量比,则其与硫代磷酸烷基酯或芳基酯和环氧化合物结合使用不会产生所期望的效果,由此导致耐磨能力不足。
(2)硫代磷酸烷基酯和硫代磷酸芳基酯
硫代磷酸烷基酯的实例包括硫代磷酸三甲酯,硫代磷酸三乙酯,硫代磷酸三丁酯,硫代磷酸三辛酯,硫代磷酸三癸酯及硫代磷酸三月桂酯。
硫代磷酸芳基酯的实例包括硫代磷酸三苯酯。
硫代磷酸烷基酯和硫代磷酸芳基酯中的每一种可以单独使用或者以它们的混合物形式使用。
按基于多元醇酯基油的重量计,硫代磷酸烷基酯和/硫代磷酸芳基酯在本发明组合物中的比例为0.1至2.0%。如果它们的比例低于0.1%重量比,耐磨性不会被改善。当它们的比例超出2.0%重量比时,不但会导致在制冷剂及多元醇酯中的溶解作用较差,而且它们增加的加入量的作用也不明显。
(3)环氧化合物
环氧化合物的实例包括苯基缩水甘油基醚,烷基苯基缩水甘油醚,1.2-环氧烷烃和乙烯基环己烯二氧化物。它们可以单独使用或以其混合物形式使用。其中优选1,2-环氧烷烃和乙烯基环己烯二氧化物。
烷基苯基缩水甘油基醚的实例包括丁基苯基缩水甘油基醚,戊基苯基缩水甘油基醚,己基苯基缩水甘油基醚,庚基苯基缩水甘油基醚,辛基苯基缩水甘油基醚,壬基苯基缩水甘油基醚及癸基苯基缩水甘油基醚。
1,2-环氧烷烃的实例包括1,2-环氧己烷;1,2-环氧庚烷;1,2-环氧辛烷;1,2-环氧癸烷;1,2-环氧十一烷;1,2-环氧十二烷;1,2-环氧十三烷;1,2-环氧十四烷;1,2-环氧十六烷;1,2-环氧十七烷以及1,2-环氧十八烷。
乙烯基环己烯二氧化物包括各种异构体,并且它们的典型实例具有下述结构式:
按基于多元醇酯基油的重量计,环氧化合物在本发明组合物中的比例为0.05至2.0%。
如果环氧化合物的比例低于0.05%重量比,润滑能力得不到改善,并且抑制多元醇酯变质的效力也不足。其比例超过2.0%重量比时将导致在制冷剂和多元醇酯中的溶解作用较差。
(4)其它添加剂
通常用于制冷机油的添加剂如抗氧剂,金属减活剂和消泡剂可以掺合在本发明的制冷机油组合物内,只要这些添加剂不会对本发明的制冷机油的性能产生不利影响即可。
抗氧剂可以是受阻酚化合物,胺化合物,硫的化合物等。它们的实例包括2,6-二叔丁基-4-甲基苯酚;4,4′-亚甲基双(2,6-二叔丁基苯酚);2,2′-硫代双(4-甲基-6-叔丁基苯酚),三甲基二氢醌酮;p,p′-二辛基二苯胺;3,7-二辛基吩噻嗪;吩噻嗪-1-羧酸烷基酯;苯基-2-萘胺,2,6-二-叔丁基-2-二甲基-对-甲苯酚;5-乙基-10,10′-二苯基吩嗪(5-ethyl-10,10′-diphenylphenazarine)和烷基化二硫。
金属减活剂的实例包括alizanin,quilizanin,苯并***和巯基苯并***。
消泡剂的实例包括二甲基聚硅氧烷和羧酸金属盐。
本发明组合物中所使用的基油为多元醇酯,它与HCFC制冷剂和HFC制冷剂中的任一个具有良好的混溶性并具有令人满意的低温流动性和低收湿性。
与HCFC制冷剂一同使用的,环烷基矿物油,石蜡族矿物油,烷基苯,以及聚-α-烯烃不能在本发明制冷机油组合物中用作基油,这是由于它们与HFC制冷剂间具有较差的混溶性。
当多元醇酯与HCFC制冷剂一同使用时,它存在着能产生淤渣的缺点,当与HFC制冷剂一同使用时它具有润滑能力不足的缺点,并在高温时倾向于产生淤渣。
通过加入1.0至少于5.0%重量比的磷酸酯,以及最佳比例量的硫代磷酸烷基酯和/或硫代磷酸芳基酯,由此产生这些添加剂的协同效应,从而使上述多元醇酯的缺点从本发明组合物中除去。
磷酸酯,硫代磷酸烷基酯和硫代磷酸芳基酯各自均为特压添加剂,并且当与HCFC制冷剂和HFC制冷剂中的任一种一同使用时,磷酸酯和硫代磷酸酯的结合能改善润滑能力。
更具体地讲是发现了下述情况。当与HCFC制冷剂一同使用时,磷酸酯和硫代磷酸烷基酯和/或硫代磷酸芳基酯被吸收并与滑动表面反应产生磷酸铁和硫化铁。另一方面,HCFC制冷剂中所包含的氯原子在滑动表面上反应产生氯化物。因此,添加剂与反应所产生的产物产生协同效应,从而得到令人满意的耐磨性。加入环氧化合物可进一步改善耐磨性。
当与HFC制冷剂一同使用时,由于制冷剂不合有氯原子,少量磷酸酯本身独自不足以提供特压添加剂所有的有效作用。然而,当磷酸酯与硫代磷酸烷基酯和/或硫代磷酸芳基酯结合使用时,由于这些添加剂的协同效应,在滑动表面上形成磷酸铁和硫化铁,从而形成具有高润滑能力的高度耐用膜。结果可在长久操作期间维持其耐磨性和载荷能力。
环氧化合物起着氯受体,以及热和化学稳定性改进剂的作用。当与HCFC制冷剂和HFC制冷剂中的任一种一同使用时,环氧化合物能有效地防止多元醇酯的变质所造成的淤渣形成。
更具体地讲,当与HCFC制冷剂一同使用时,多元醇酯被热解并且其变坏作用被HCFC制冷剂中所包含的氯原子的作用而加快。由于环氧化合物能迅速地与所产生的氯反应,故环氧化合物能抑制多元醇酯的变坏作用。此外,由于磷酸酯和硫代磷酸烷基酯和/或硫代磷酸芳基酯相对于HCFCX制冷剂是热和化学稳定的,故这些添加剂不会施加任何不利影响。
当与HFC制冷剂一同使用时,由于环氧化合物能改善热和化学稳定性,故它能在高温范围内抑制淤查形成。
本发明将通过下述实施例和对比实施例更详尽说明。应当理解本发明并不仅局限于这些实施例。实施例和对比实施例中所用的基油,添加剂以及试验方法和试验结果见下所述。
1.基油
(1)实施例1至8和对比实施例1至12
多元醇酯被用作基油,它们各自通过使季戊四醇与具有7,8和9碳原子的支链脂肪酸(C7-脂肪酸为2-甲基己酸和2-乙基戊酸;C8-脂肪酸为2-乙基己酸;C9-脂肪酸为3,5,5-三甲基己酸)的混合物反应合成得到。多元醇酯具有0.01mgKOH/g或更低的酸价和100ppm或更低浓度的水含量。
(2)对比实施例13
烷基苯ABA-H(日本Mitsubishi Chemical Ltd.生产的硬型烷基苯)被用作基油。
这种烷基苯通常用作供采用HCFC-22制冷剂的制冷机中使用的制冷机油的基油。
2.添加剂
磷酸三(甲苯酯)用作磷酸酯。
硫代磷酸三苯酯被用作硫代磷酸芳基酯,以及硫代磷酸三辛酯被用作硫代磷酸芳基酯。
乙烯基环己烯二氧化物被用作环氧化合物。
基于基油量的这些添加剂的加入量见表1至4所示。
对比实施例13的制冷机油中烷基苯被用作基油,不含添加剂。
3.试验方法
(1)磨损试验
利用法列克司试验机(ASTM D2714),采用钢环和钢滑块作为试验材料,在HFC-134a制冷剂和HCFC-22制冷剂的环境中进行磨损试验。试验后测量钢滑块表面的磨损体积。试验条件包括100℃温度,试验期为1小时,以及气压为600kPa。
所得到的结果以相对比率表示,其中以实施例13(制冷剂,HCFC-22;基油,烷基苯)中的磨损体积作为参比,看作1.0。
(2)热及化学稳定性试验
在HFC-134a制冷剂和HCFC-22制冷剂的环境中进行密闭管试验。
密闭管试验通常用于检测制冷机油的热及化学稳定的。在此试验中,在玻璃管内放置1ml制冷剂,1ml油样,以及各自具有1.6mm直径且长度为30mm的铁丝,铜丝及铝丝,将管密闭并加热观察油样的颜色变化,即淤渣形成,该试验条件包括温度为175℃且试验期为14天。
试验结束之后,基于所产生的颜色变化评估油样。颜色不发生变化的样品用○表示,颜色发生明显变化的样品用×表示,且颜色发生轻微变化的样品用△表示。
4.试验结果
均在HFC-134a制冷剂环境中进行的磨损试验和热及化学稳定性试验的结果见表1和2内所示。
表1
在HFC-134a制冷剂环境中的试验结果
实施例 对比实施例
1 2 3 4 5 6 7 8 1 2 3 4
组合物
基油 多元醇酯 多元醇酯
添加剂(wt%)
磷酸酯 1.0 1.0 4.9 1.0 1.0 1.0 1.0 4.9 - 1.0 - -硫代磷酸芳基酯 0.5 - 0.5 0.1 2.0 0.5 0.5 2.0 - - 0.5 -硫代磷酸烷基酯 - 0.5 - - - - - - - - - -
环氧化合物 0.5 0.5 0.5 0.5 0.5 0.05 2.0 0.5 - - - 0.5
试验结果磨损试验(磨损体积比)0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.6 4.0 2.5 3.5 4.0热和化学稳定性试验
Fe ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ○
Cu ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Al ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
表2
在HFC-134a制冷剂环境中的试验结果
对比实施例
5 6 7 8 9 10 11 12 13
组合物
基油 多元醇酯 烷基苯
添加剂(wt%)
磷酸酯 - 1.0 1.0 1.0 4.9 0.5 1.0 1.0 -硫代磷酸芳基酯 0.5 - 0.5 2.0 2.0 0.5 0.05 3.0 -
环氧化合物 0.5 0.5 - - - 0.5 0.5 0.5 -
试验结果磨损试验(磨损体积比) 4.0 4.0 0.9 0.9 0.6 2.0 2.0 0.9 1.0热和化学稳定性试验
Fe ○ ○ △ △ △ ○ ○ △ ○
Cu ○ ○ ○ ○ ○ ○ ○ ○ ○
Al ○ ○ ○ ○ ○ ○ ○ ○ ○
注:对比实施例13中的制冷剂为HCFC-22。
均在HCFC-22制冷剂的环境中进行的磨损试验和热及化学稳定性试验的结果见表3和表4内所示。
表3
在HCFC-22制冷剂环境中的试验结果
实施例 对比实施例
1 2 3 4 5 6 7 8 1 2 3 4
组合物
基油 多元醇酯 多元醇酯
添加剂(wt%)
磷酸酯 1.0 1.0 4.9 1.0 1.0 1.0 1.0 4.9 - 1.0 - -硫代磷酸芳基酯 0.5 - 0.5 0.1 2.0 0.5 0.5 2.0 - - 0.5 -硫代磷酸烷基酯 - 0.5 - - - - - - - - - -
环氧化合物 0.5 0.5 0.5 0.5 0.5 0.05 2.0 0.5 - - - 0.5
试验结果磨损试验(磨损体积比)0.6 0.6 0.6 0.9 0.5 0.5 0.5 0.4 1.5 1.5 1.5 1.5热和化学稳定性试验
Fe ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ○
Cu ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Al ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
表4
在HCFC-22制冷剂环境中的试验结果
对比实施例
5 6 7 8 9 10 11 12 13
组合物
基油 多元醇酯 烷基苯
添加剂(wt%)
磷酸酯 - 1.0 1.0 1.0 4.9 0.5 1.0 1.0 -硫代磷酸芳基酯 0.5 - 0.5 2.0 2.0 0.5 0.05 3.0 -
环氧化合物 0.5 0.5 - - - 0.5 0.5 0.5 -
试验结果磨损试验(磨损体积比)1.5 1.3 1.0 1.0 0.6 1.5 1.5 0.6 1.0热和化学稳定性试验
Fe ○ ○ △ × × ○ ○ △ ○
Cu ○ ○ ○ △ △ ○ ○ ○ ○
Al ○ ○ ○ ○ ○ ○ ○ ○ ○
(1)实施例1至8和对比实施例13。
当使用HCFC-22制冷剂时,与对比实施例13的油(先有技术组合物)相比,本发明实施例的机油组合物各自显示出更好的耐磨性。本发明实施例也显示出令人满意的热及化学稳定性且无淤渣形成。
上述结果表明本发明实施例的机油组合物适合与HFC-134a制冷剂和HCFC-22制冷剂中的任一种一同使用。该结果进一步表明即使当磷酸酯的加入量少于5.0%重量比时,当按照本发明此外还加入硫代磷酸烷基酯或硫代磷酸芳基酯和环氧化合物时能得到令人满意的耐磨性及高的热及化学稳定性。
(2)对比实施例2至9
对比实施例2至4的机油组合物,每一种是由多元醇酯和唯一的一种添加剂组成,与实施例1至8的组合物以及对比实施例13的油相比,它们的耐磨性均较差。
与实施例1至8的组合物以及对比实施例13的油相比,对比实施例5的机油组合物(含有硫代磷酸芳基酯和环氧化合物的混合物)和对比实施例6的机油组合物(含有磷酸酯和环氧化合物的混合的)均具有较差的耐磨性。
对比实施例7至9的机油组合物(含有磷酸酯和硫代磷酸芳基酯混合物)各自显示出较差的热及化学稳定性并产生淤渣。
上述结果表明结合使用磷酸酯,硫代磷酸芳基酯或硫代磷酸烷基酯以及环氧化合物对实现本发明的目的是必需的并且对达到上述工作特性也是必不可少的。
表1中实施例3和实施例8之间的比较结果,表3中实施例1,2和5与实施例4之间的比较结果,表3中实施例3与实施例8之间的比较结果以及表1至4中对比实施例2与对比实施例7和8之间的比较结果表明,当与磷酸酯结合使用时,硫代磷酸芳基酯或硫代磷酸烷基酯能有效改善耐磨性。
此外,表3和4中的实施例1和2与对比结果实施例7之间的比较以及表3和4中的实施例5与对比实施例8之间的比较结果表明,加入环氧化合物能有效地进一步改善耐磨性。
(3)对比实施例10
与实施例1至3的组合物以及对比实施例13的油相比,对比实施例10的机油组合物(含0.5wt%磷酸酯)的耐磨性较差。
上述结果表明本发明组合物中磷酸酯加入量的下限基于多元醇酯基油的量计为1.0%重量比。
(4)对比实施例11和12
与实施例4和5的组合物以及对比实施例13的油相比,对比实施例11的机油组合物(含0.05wt%硫代磷酸芳基酯)具有较差的耐磨性。与实施例4和5的组合物以及对比实施例13的油相比,对比实施例12的机油组合物(含3.0wt%硫代磷酸芳基酯)具有较差的热及化学稳定性。
上述结果表明:基于多元醇酯基油的量,硫代磷酸芳基酯在本发明组合物中的比例应在0.1至2.0%重量范围内。
(5)对比实施例7至9
与实施例6和7的组合物以及对比实施例13的油相比,对比实施例7至9的机油组合物(不含环氧化合物)具有较差的热及化学稳定性。
进行试验,该试验表明当环氧化合物的加入量超过2.0%重量比时,环氧化合物在制冷剂和在多元醇酯中的溶解作用较差。
按照上述结果,环氧化合物在本发明组合物中的比例按多元醇酯基油的量计在0.05至2.0%重量范围内。
在分离试验中,制备分别与实施例1和3至8的组合物相同的机油组合物,只是用硫代磷酸三苯酯和硫代磷酸三辛酯的混合物替代硫代磷酸三苯酯。将这些组合物按上所述的方法进行磨损试验和热及化学稳定性试验。结果,得到与实施例1和3至8相同的效应。
就此而论应注意下述情况。有时二硫化二苄和硫化脂或硫化油用作硫的化合物添加剂,它们属于硫代磷酸烷基酯或硫代磷酸芳基酯类。然而,使用二硫化二苄对改善耐磨性是无效的并且会产生大量淤渣。使用硫化脂或硫化油导致有大量淤渣产生。因此,二硫化二苄和硫化脂或硫化油比硫化磷酸烷基酯和硫化磷酸芳基酯具有更高的活性,故它们不能用于替代这些硫代磷酸酯。
5其它试验的方法及结果
(1)摩擦转矩试验
采用附图1所述的装置,循环各样油(实施例1和对比实施例1和2),在HFC-134a制冷剂的环境中,每隔一定时间周期利用四球试验机测量它们的摩擦转矩。附图1中,1表示四球试验机,2表示制冷容器(refrigerant bomb),3为样油罐,4为样油循环泵,且5为流量计。
所得结果见附图2所示。
发现实施例1的机油组合物在长期运转过程中显示出很小的摩擦转矩变化,并且与对比实施例1的油(由作为基油的多元醇酯组成,且不含任何添加剂)以及对比实施例2的组合物(包含作为基油的多元醇酯且磷酸酯作为唯一的添加剂)相比,实施例1的机油组合物具有较长的寿命。
关于实施例1的组合物,其摩擦转矩的测量还在HCFC-22制冷剂的环境下进行。
所得结果见附图3所示。
象在HFC-134a制冷剂的环境下一样,实施例1的机油组合物在HCFC-22制冷剂环境下也具有较长的寿命。
(2)加速压缩机寿命试验
采用实际使用的压缩机,将实施例1的组合物和对比实施例13的油(由作为基油的烷基苯组成且不含添加剂)进行加速压缩机寿命试验。
所得结果见附图4所示。
已发现当与HCFC-22和HFC-134a制冷剂中的任一种一同使用时,与作为性能评估标准的对比实施例的油相比,实施例1的机油组合物具有优越的耐久性和抗变质能力。
对比实施例13的油的加速耐久性时间在确定正常使用条件下相对于压缩机寿命的指数的性能评估中用作标准。
适合蒸汽压缩机的本发明制冷机油组合物适宜与目前使用的HCFC制冷剂和HFC制冷剂中的任一种一同使用,这两种制冷剂被认为是新型制冷剂。
本发明组合物的特有性能为尽管加入到多元醇酯基油的比例少于5.0%重量比(基于基油量),但由于通过以最佳比例进一步加入除磷酸酯之外的硫代磷酸烷基酯和/或硫代磷酸芳基酯以及环氧化合物所产生的协同效应,淤渣的形成被抑制并且润滑能力被进一步改进。
本发明制冷机油组合物与制冷剂间具有优良的相容性并具本发明制冷机油组合物具有优越的电绝缘性质,并且由于使用多元醇酯(酯类合成油)作为基油,故还具有低吸湿性。
而且,本发明的制冷机油组合物基本上是由作为基油的多元醇酯和以最佳比例存在的作为特压添加剂的磷酸酯和硫化磷酸烷基酯和/或硫代磷酸芳基酯以及既作为氯受体又作为热及化学稳定性增强剂的环氧化合物所组成。
因此,本发明的制冷机油组合无淤渣形成以及润滑能力不足的缺点,而这些缺点恰恰是多元醇酯所具有的缺点。这是由于所述三种添加剂的协同效应的缘故。另一方面,本发明组合物提供了所希望的多元醇酯基油所具有的特性,即,与制冷剂之间良好的相容性,高电绝缘性质和低吸湿性。
尽管本发明借助具体实施例进行了更详尽的描述,但应当指出,只要不违背本发明的精神和范围,本专业技术人员可以进行各种变化和变更。
Claims (8)
1.供采用氢氯氟烃或氢氟烃作为制冷剂的蒸汽压缩机中使用的制冷机油组合物,该组合物包括多元醇酯作为基油,所述基油含有:
(a)按重量计1.0至少于5.0%的磷酸酯;
(b)至少一种硫代磷酸烷基酯和硫代磷酸芳基酯,其量按重量计为0.1至2.0%;和
(c)按重量计0.05至2.0%的环氧化合物,其中组合(a),(b)及(c)的量各自基于上述基油的量。
2.权利要求1的制冷机油组合物,其中所述多元醇酯基油具有5至150mm2/s(40℃)的粘度,高达1mgKOH/g的酸值以及高达500ppm的水含量。
3.权利要求1的制冷机油组合物,其中所述多元醇酯具有0.01mgKOH/g或更低的酸值以及100ppm或更低的水含量。
4.权利要求1的制冷机油组合物,其中所述磷酸酯选自磷酸三(甲苯酯),磷酯苯基异丙基苯基酯,磷酸二苯基异丙基苯基酯和磷酸三(异丙基苯酯)。
5.权利要求1的制冷机油组合物,其中所述环氧化合物选自1,2-环氧烷烃和乙烯基环己烯二氧化物。
6.权利要求1的制冷机油组合物,其中所述多元醇酯是通过选自新戊二醇,三羟甲基丙烷、季戊四醇和双季戊四醇中的至少一种多元醇而得到的多元醇酯。
7.根据权利要求1的制冷机油组合物,其中所述硫代磷酸烷基酯为硫代磷酸三甲酯,硫代磷酸三乙酯,硫代磷酸三丁酯,硫代磷酸三辛酯,硫代磷酸三癸酯和硫代磷酸三月桂酯。
8.根据权利要求1的制冷机油组合物,其中硫代磷酸芳基酯为硫代磷酸三苯酯。
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JP31663/1995 | 1995-01-27 | ||
JP03166395A JP3422869B2 (ja) | 1995-01-27 | 1995-01-27 | Hcfc冷媒及びhfc冷媒に共用可能な冷凍機油組成物 |
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CN1136586A CN1136586A (zh) | 1996-11-27 |
CN1057557C true CN1057557C (zh) | 2000-10-18 |
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CN100499431C (zh) * | 1996-03-15 | 2009-06-10 | 摩托罗拉公司 | 通信***中的功率控制方法 |
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US6998065B1 (en) * | 1989-12-28 | 2006-02-14 | Nippon Mitsubishi Oil Corporation | Fluid compositions containing refrigerator oils and chlorine-free fluorocarbon refrigerants |
US7052626B1 (en) * | 1989-12-28 | 2006-05-30 | Nippon Mitsubishi Oil Corporation | Fluid compositions containing refrigeration oils and chlorine-free fluorocarbon refrigerants |
KR100288029B1 (ko) * | 1998-01-21 | 2001-04-16 | 다니구찌 이찌로오, 기타오카 다카시 | HFC-32, HFC-125 또는 HFC-134a를 사용하는 냉동기용 윤활유 조성물 |
JP3592514B2 (ja) * | 1998-03-02 | 2004-11-24 | 松下電器産業株式会社 | 冷凍装置 |
JP4005711B2 (ja) | 1998-09-29 | 2007-11-14 | 新日本石油株式会社 | 冷凍機油 |
US6330811B1 (en) | 2000-06-29 | 2001-12-18 | Praxair Technology, Inc. | Compression system for cryogenic refrigeration with multicomponent refrigerant |
JP4537560B2 (ja) * | 2000-09-26 | 2010-09-01 | 新日本石油株式会社 | 冷凍機油組成物 |
DE10164056B4 (de) * | 2001-12-29 | 2006-02-23 | Fuchs Petrolub Ag | Betriebsmittel für Kohlendioxid-Kälte- und Klimaanlagen |
WO2004096959A1 (en) * | 2003-04-28 | 2004-11-11 | Great Lakes Chemical (Europe) Gmbh | Lubricant compositions |
MY146640A (en) * | 2003-08-01 | 2012-09-14 | Nippon Oil Corp | Refrigerating machine oil composition |
JP4772504B2 (ja) | 2003-08-01 | 2011-09-14 | Jx日鉱日石エネルギー株式会社 | 冷凍機油組成物 |
JP4493373B2 (ja) * | 2004-03-04 | 2010-06-30 | 新日本石油株式会社 | 冷凍機油組成物 |
JP4560311B2 (ja) * | 2004-03-04 | 2010-10-13 | Jx日鉱日石エネルギー株式会社 | 冷凍機油組成物 |
KR101187593B1 (ko) | 2004-03-04 | 2012-10-11 | 제이엑스 닛코닛세키에너지주식회사 | 냉동기유 |
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JP6195429B2 (ja) * | 2012-03-29 | 2017-09-13 | Jxtgエネルギー株式会社 | 冷凍機用作動流体組成物及び冷凍機油 |
CN103996886A (zh) * | 2013-02-19 | 2014-08-20 | 微宏动力***(湖州)有限公司 | 具备散热能力的电池模块 |
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JPH08209182A (ja) | 1996-08-13 |
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