CN1494583A - 致冷机润滑剂组合物 - Google Patents
致冷机润滑剂组合物 Download PDFInfo
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- CN1494583A CN1494583A CNA028057775A CN02805777A CN1494583A CN 1494583 A CN1494583 A CN 1494583A CN A028057775 A CNA028057775 A CN A028057775A CN 02805777 A CN02805777 A CN 02805777A CN 1494583 A CN1494583 A CN 1494583A
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- lubricant compositions
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- C10M105/06—Well-defined hydrocarbons aromatic
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Abstract
用于旋转叶片压缩机的润滑剂组合物有这样一种基础油组分，所述的基础油组分含有烷基苯作为主要组分和多元醇酯作为次要组分。特别是，基础油组分含有至少55重量％烷基苯和至多45重量％多元醇酯，更优选55－75重量％烷基苯和45－25重量％多元醇酯，特别是60－75重量％烷基苯和45－25重量％多元醇酯。
Description
本发明涉及致冷剂应用的润滑剂组合物，特别是用于致冷设备的旋转叶片压缩机的润滑剂组合物；以及涉及使用这样的组合物润滑的压缩机，特别是旋转叶片压缩机。
致冷系统由用于压缩致冷剂气体的压缩机、用于冷凝压缩的气体的冷凝器、膨胀设备和蒸发器部分组成，经冷凝的气体在蒸发器中汽化，以提供冷却作用，蒸发器通过返回管线与压缩机相连。有运动部件的压缩机需要润滑，以便减少摩擦和磨损，以及在某些设计中还提供密封作用。
历史上，用于致冷系统的润滑剂组合物含有矿物油、烷基苯、石蜡基油、环烷基油和聚α烯烃(PAOs)作为基础油，致冷剂通常为含氟氯烃(CFCs)和含氢氟氯烃(HCFCs)。但是，根据1987年蒙特利尔协定，由于这样的致冷剂的消耗臭氧性质，CFCs随后是HCFCs要逐步停止使用。
采用的替代致冷剂包括含氟烃(FCs)和含氢氟烃(HFCs)。但是，传统致冷剂的润滑剂组合物例如矿物油和烷基苯由于与新型致冷剂的不混溶性，人们认为它们不适合这些应用。例如，这样的传统润滑剂存在回油问题，在起动时由于低温下其高粘度，在发动机中产生高转矩。认为适合用于新型致冷剂的润滑剂组合物包括多元醇酯(POEs)、聚乙烯醚(PVEs)和聚亚烷基二醇(PAGs)，因为它们有较高极性，因此与新型致冷剂有更大的混溶性。
但是，在致冷应用中使用的旋转叶片压缩机的压缩部件上的叶片产生的高负荷给装有这样的润滑剂组合物的压缩机的操作产生一种困难的环境。通常，某些润滑剂组合物不能充分地起作用，使压缩机中的叶片和压缩部件产生明显的磨损。例如，POEs由于其在致冷剂中的溶解性和低的粘度压力系数，它不能在操作条件下维持足够的粘度，以便防止金属与金属接触和磨损。此外，由于在叶片端部产生的热量，某些润滑剂组合物可分解成不希望的分解产物，例如POEs可降解成酸，后者可产生腐蚀作用和其它有害的作用。
人们企图克服这些问题。
例如在EP 0533957中，在装有1，1，1，2-四氟乙烷(R134a)、HFC和含有POE的润滑剂组合物的致冷系统中使用的固定叶片的旋转压缩机用硬度和熔点比制作压缩机部件的材料要高的材料制成。
类似的压缩机在US 5966949中公开。但是，在这一情况下，POE润滑剂组合物还含有极压添加剂，例如磷酸三酯。
已发现PVEs特别适用于旋转叶片压缩机，但它相对于其它润滑剂组合物来说是较昂贵的。
更一般地说，人们企图将含有矿物油、烷基苯等的传统润滑剂组合物与新型致冷剂气体一起使用。
例如在EP 0622445中，提出使用这样一种含氟的致冷剂气体的混合物，其中至少一种致冷剂气体为不可燃的，所述的混合物是不可燃的；在致冷系统的工作条件下，润滑剂组合物在致冷剂气体混合物中的溶解度为0.5-7重量％。致冷剂气体混合物选自HFCs、氟代胺、氟代醚、氟丙烷、氟乙烷和氟硅烷。润滑剂组合物可选自含氟氯烃聚合物、全氟烃聚合物、全氟烷基聚醚、改性的硅酮或氯化的芳烃或选自烷基苯、聚α烯烃、石蜡基油、萘油、聚苯醚、聚苯硫醚和氯化石蜡。
在EP 1018538中，提出使用烃油作为润滑剂组合物的基础油，致冷剂含有烃类。可能的致冷剂特别是包括甲烷、乙烯、乙烷、丙烯、丙烷、丁烷或它们的混合物或与HFC的混合物。可能的润滑剂组合物含有萘属矿物油、石蜡基矿物油、烯烃聚合物、萘化合物、烷基苯及其混合物的基础油。
但是，由于这些传统润滑剂组合物在HFCs中的低溶解度，仍然存在从致冷系统回油的问题以及由于这些组合物在相对低温下的高粘度产生的起动问题。
本发明的一个目的是要提供这样一种润滑剂组合物，它能减少或消除上述的一个或多个缺点。
根据本发明，用于旋转叶片压缩机的润滑剂组合物有这样的基础油组分，它含有烷基苯作为其主要组分以及多元醇酯作为其次要组分。
特别是，润滑剂组合物的基础油组分含有至少55重量％烷基苯和至多45重量％多元醇酯；更优选55-75重量％烷基苯和45-25重量％多元醇酯，特别是60-75重量％烷基苯和45-25重量％多元醇酯。更特别的是，润滑剂组合物的基础油组分主要由烷基苯和多元醇酯组成。
烷基苯和多元醇酯及其制备方法在《合成润滑剂和高性能功能液》(第1版由Ronald L Shubkin编辑，1993年，ISBN 0-8247-8715-3；第2版由Leslie R Rudnick和Ronald L Shubkin编辑，1999年，0-8247-0194-1)中描述。具体指第1版的第I部的第2和5部分和第II部的第19部分，以及第2版的第I部的第3和7部分和第II部的第24和25部分。
特别适用于本发明的烷基苯包括单烷基苯、二烷基苯、二苯基烷烃及其混合物。优选的是，烷基苯的烷基组分为支链的，并由丙烯低聚物制得。
用于本发明的优选烷基苯有这样的分子量分布，其中至少80％、更优选100％的分子量大于200；更特别的是，至少75％的分子量大于300；尤其是，至少40％、更特别是50％的分子量大于350。优选的是，至少70％的分子量小于500，更特别的是至少50％的分子量小于450。
在40℃下，优选烷基苯的运动粘度为至少10厘沱、更优选至少25厘沱，但不大于70厘沱；而在100℃下，其运动粘度为至少2厘沱、更优选至少3.5厘沱，但不大于10厘沱。
优选的烷基苯的倾点小于-10℃、更优选小于-20℃，特别是小于-30℃。
优选的烷基苯的酸值小于0.04毫克KOH/克。
特别适用于本发明的多元醇酯由多元醇和一元羧酸制得。特别优选的多元醇酯由选自新戊二醇(NPG)、三羟甲基丙烷(TMP)和季戊四醇(PE)的一种或多种醇及其二聚物和三聚物与选自直链的和/或支链的C5-C18酸、特别是C5-C13酸且更特别是C5-C9酸的一种或多种酸制得。
在40℃下，优选的多元醇酯的运动粘度为至少5厘沱，但不大于40厘沱、更优选小于25厘沱；而在100℃下，其运动粘度为至少1.5厘沱，但不大于5厘沱、更优选小于4厘沱。
优选的多元醇酯的倾点小于-40℃、更优选小于-50℃，特别是小于-55℃。
优选的多元醇酯的酸值小于0.04毫克KOH/克。
在40℃下，本发明优选的润滑剂组合物的运动粘度为至少5厘沱，但不大于40厘沱、更优选小于25厘沱；而在100℃下，其运动粘度为至少2厘沱，但不大于6厘沱、更优选小于5厘沱。
优选的润滑剂组合物的倾点不大于-40℃、更优选不大于-45℃，特别是不大于-50℃。
本发明的润滑剂组合物还含有一种或多种其它已知功能的润滑剂添加剂，按基础油组分的重量计，其含量为0.0001-20重量％、更优选0.01-10重量％、更特别是0.01-5重量％。适合的添加剂包括抗氧化剂、抗磨添加剂、极压添加剂、酸消除剂、起泡剂、消泡剂、稳定剂、表面活性剂、粘度指数改进剂、腐蚀抑制剂、金属减活剂或钝化剂、润滑改进剂或油性添加剂和摩擦改进剂。
根据本发明的另一方面，在旋转叶片压缩机中使用这样一种润滑剂组合物，所述的润滑剂组合物含有烷基苯作为主要组分和多元醇酯作为次要组分的基础油组分。
根据本发明的另一方面，润滑旋转叶片压缩机的方法包括使用含有烷基苯作为主要组分和多元醇酯作为次要组分的基础油组分的润滑剂组合物。
根据本发明的另一方面，旋转叶片压缩机加有这样一种润滑剂组合物，它含有烷基苯作为主要组分和多元醇酯作为次要组分的基础油组分。
根据本发明的另一方面，致冷系统包含旋转叶片压缩机，所述的系统加有这样一种致冷剂，所述的致冷剂含有无氯含氟的传热液以及烷基苯作为主要组分和多元醇酯作为次要组分的基础油组分的润滑剂组合物。
在本发明一优选的实施方案中，旋转叶片压缩机为固定叶片的压缩机。
优选的是，致冷剂为含氢氟烃，更优选选自二氟甲烷(R-32)、三氟甲烷(R-23)、1，1，2，2-四氟乙烷(R-134)、1，1，1，2-四氟乙烷(R-134a)、1，1，1-三氟乙烷(R-143a)、1，1-二氟乙烷(R-152a)、五氟乙烷(R-125)和六氟乙烷(R-116)及其两种或两种以上的混合物。特别适用的致冷剂为R-32、R-116、R-125、R-134a、R-143a及其混合物。
与迄今使用的润滑剂组合物相比，本发明的润滑剂组合物以相对低的费用下提供良好的润滑、回油和低的起始转矩条件。
现仅根据附图和以下的实施例作为例子进一步描述本发明。
在附图中：
图1表示固定叶片的压缩机的简化分解透视图；
图2为实施例7得到的结果的图示说明，以及
图3和图4为实施例11得到的结果的图示说明。
关于图1，固定叶片的压缩机10有一圆柱形外壳12，其中同心安装一轴14，它与外壳12轴同心旋转。轴14安装在密封件16和凸轮部件18之间。圆柱形压缩部件20在凸轮18周围，以致轴14穿过使它旋转的凸轮部件18。固定叶片22安装在外壳12的周边，并弹性偏压到固定叶片伸向外壳的内部。叶片22在其端部24与压缩部件20的外表面啮合。
在操作中，压缩部件20偏心地在外壳12内通过凸轮部件18的旋转使叶片22沿外壳12的径向运动。借助压缩部件20的旋转，通过入口(未示出)进入外壳12的流体在叶片22和压缩部件20之间被压缩。经压缩的流体通过外壳中靠近叶片22的阀门或节流出口(未示出)流出，相对于压缩部件20的旋转方向在叶片22的上游。
润滑剂组合物在压缩机10中存在，当它与压缩部件20的外表面接触时，使叶片22的端部24润滑，也使与外壳12滑动接触的叶片22侧面润滑。润滑剂组合物也使系统的其它部件例如轴承润滑，此外还在叶片22的端部24和压缩部件20的高压和低压侧之间提供良好的密封。
实施例1
用于评价的样品的组分列入表1，而用于评价的样品列入表2。
表1
| 编号 | |
| 1 | 为Chevron Company以商品名Zerol 55提供的烷基苯 |
| 2A、2B、2C和2D | 为Chevron Company以商品名Zerol 150提供的烷基苯样品 |
| 3 | 为含有磷酸盐抗磨添加剂的烷基苯，它与R-22(一种HCFC)致冷剂一起用于固定叶片的旋转压缩机。 |
| 4A | 为一种PE与直链C5一元羧酸反应制得的多元醇酯 |
| 4B | 为一种PE与直链C5一元羧酸反应制得的多元醇酯 |
| 4C | 为一种NPG与直链C7酸(NPG nC7)反应制得的多元醇酯。 |
| 4D | 为一种50∶50PE和di-PE混合物与直链C5、直链C7和支链C9(25∶25∶50)反应制得的多元醇酯。 |
| 5A | 为一种由Japan Energy Corporation提供的多元醇酯，它与HFC致冷剂一起用于固定叶片的旋转压缩机。 |
| 5B | 为一种由Japan Sunoil提供的多元醇酯，它与HFC致冷剂一起用于固定叶片的旋转压缩机。 |
| 6 | 为一种由Idemitsu Kosan提供的PVE，它与HFC致冷剂一起用于固定叶片的旋转压缩机。 |
| 7 | 为一种由Japan Sunoil以商品名SUNISO 4GS提供的矿物油。 |
在表2中：
·表示比较样品；
·BHT为3，5-二丁基-4-羟基甲苯，一种抗氧化剂；
·TCP为磷酸三甲苯酯；
·按基础油组分的重量计，基础油各组分表示为该组分的重量％，而添加剂表示为重量％。
样品的性质列入表3，其中：
*1每种样品的低温混溶性通过将准确称重的样品(约0.6克)放入与真空泵相连的观察孔以便评估样品，用丙酮/干冰混合物冷却观察孔并加入准确称重的致冷剂(约5.4克)。样品和致冷剂等于10％润滑剂组合物致冷剂。然后使观察孔和它的物料达到室温。在观察孔物料的研究时，如果有两相或两相以上存在，那么润滑剂组合物与致冷剂在室温下是不混溶的，这一事实被给出。在观察孔物料的研究时，如果有一相存在，然后以约1℃/5分的速率将观察孔和物料冷却直到混合物变混浊时，即开始相分离，混浊点温度被给出。
*2IM＝不混溶的。
表2
| No | 烷基苯 | POE | PVE | 矿物油 | 添加剂 | |
| 9 | 31.5％No1和58.5％No2A | 10％No4A | 0.05％BHT | |||
| 10 | 90％No2D | 10％No4A | 0.05％BHT | |||
| 11 | 70％No2D | 30％No4C | 0.05％BHT | |||
| 12 | 70％No2D | 30％No4C | 3％TCP | 0.05％BHT | ||
| 13A | 65％No2B | 35％No4C | 2.25％TCP | 0.05％BHT | ||
| 13B | 65％No2C | 35％No4C | 2.25％TCP | 0.05％BHT | ||
| 13C | 66％No2C | 34％No4C | ||||
| 13D | 65％No2B | 35％No4C | 3％TCP | 0.05％BHT | ||
| 14A* | 100％No4B | 6％TCP | 0.1％BHT | |||
| 14B* | 100％No4D | 6％TCP | 0.1％BHT | |||
| 15A* | 100％No2C | |||||
| 15B* | 100％No2D | |||||
| 16* | 100％No3 | |||||
| 17* | 100％No5A | |||||
| 18* | 100％No6 | |||||
| 19* | 100％No5B | |||||
| 20* | 100％No7 |
烷基苯为聚合化合物，其分子量分布可用许多不同的方法表征。其中一个这样的表征为数均分子量(Mn)。它为分子量的正常计数型。另一方法为重圴分子量(Mw)，它提高了分子量分布的更高端。
对于样品2A、2B和2C即Zerol 150来说，Mn和Mw在下表4中列出。
表4
| 样品编号 | Mw | Mn |
| 2A | 379 | 440 |
| 2B | 362 | 400 |
| 2C | 380 | 351 |
在这些样品中，Mn和Mw数值接近，表明这些样品有窄的分子量分布。
样品1、2A、2B和2C的％分子量分布列入表5。
表5
| 样品编号 | MW＜200 | MW200-300 | MW 301-350 | MW＞350 | |
| 1 | 13 | 80 | 6 | 1 | |
| 2A | ＜0.5 | 17 | 23 | 60 | |
| MW＜350 | MW 350-400 | MW 401-450 | MW 451-500 | MW＞500 | |
| 2B | 22.3 | 16.5 | 18.3 | 14.4 | 28.5 |
| 2C | 42 | 20.7 | 14.7 | 11.2 | 11.4 |
样品2D用来表示Zerol 150烷基苯的样品，表4和5中的参数未确定它们；但是，这些样品与其它样品有类似分子量和分子量分布。
样品1和2A/B/C/D(分别为Zerol 55和Zerol 150)为支链的烷基苯，其化学结构可能由以下分子类型组成。
样品3为可能与样品1和2A/B/C/D有类似结构的支链烷基苯。
实施例2
按ASTM标准D-4172(四球法)进行了样品13D和16-18的小型磨损试验。四球法包括一个旋转的钢球压向其它三个钢球，并通过测量产生的磨痕的直径来定量。试验的条件为在空气气氛下在40公斤负荷下1小时。球上磨痕的直径为磨损数量的直接量度。在这些条件下，磨痕越小，防止磨损的润滑剂组合物越好。
试验结果列入表6。
表6
| 样品编号 | 13D | 16 | 17 | 18 |
| 磨损痕迹(毫米) | 0.642 | 1.77 | 1.047 | 0.605 |
数据表明，对于样品13D(根据本发明)和18来说，在这些试验条件下磨损性能是可比的，两者都比样品16和17的磨损好得多。
表3
| 性质 | 试验方法 | 样品编号 | ||||||||||
| 1 | 2A | 2B | 3 | 4A | 4B | 4C | 4D | 5B | 6 | 7 | ||
| 粘度(厘沱)40℃100℃ | ASTMD-445 | 5.71.7 | 33.54.4 | 31.34.5 | 48.2 | 15.23.6 | 15.53.6 | 5.61.9 | 729.8 | 65.48.2 | 67.88.4 | 54.76.1 |
| 粘度指数 | ASTMD-2270 | 25 | 8 | 121 | 115 | 167 | 120 | 91 | 91 | 25 | ||
| 倾点(℃) | ASTMD-97 | -40 | -55 | ＜-60 | -39 | -35 | -38 | |||||
| 闪点COC(℃) | ASTMD-92 | 170 | 228 | 184 | 270 | 274 | 194 | |||||
| 20℃密度(克/毫升) | ASTMD-1298 | 0.87 | 1.02 | 0.93 | 0.98 | 0.93 | ||||||
| 酸值(毫克KOH/克) | ASTMD-974 | 0.02 | 0.02 | 0.01 | 0.02 | 0.01 | 0.02 | 0.01 | 0.01 | |||
| 水含量(ppm) | ASTMD-1064 | ＜40 | ＜40 | ＜40 | ＜40 | |||||||
| 颜色(ASTM) | ASTMD-1209 | ＜0.5 | ＜0.5 | ＜0.5 | ＜0.5 | ＜0.5 | ＜0.5 | ＜0.5 | ||||
| 低温混溶性(℃)10％润滑剂在R-12中10％润滑剂在R-22中10％润滑剂在R-134a中10％润滑剂在R-404A中10％润滑剂在R-407C中 | 在外壳内*1 | ＜-73-72IM*2IM*2IM*2 | -56 | -30-50-15 | ||||||||
| 四球磨损痕迹(毫米)40公斤，1小时 | ASTMD-2783 | 1.67 | 1.02 | 0.99 | ||||||||
| 故障的Falex负荷(磅) | ASTMD-3233 | 1500 | 1800 | |||||||||
| Falex(磨损齿)5小时，400磅，钢/钢在R-134a中 | ASTMD-1209 | 127 | ||||||||||
表3(续)
| 性质 | 试验方法 | 样品编号 | |||||||
| 9 | 10 | 11 | 12 | 13A | 13B | 13C | 13D | ||
| 粘度(厘沱)40℃100℃ | ASTMD-445 | 14.52.9 | 27.44.3 | 15.43.2 | 15.53.24 | 14.2 | 14.3 | 14.63.1 | 14.13.1 |
| 粘度指数 | ASTMD-2270 | 11 | 16 | 55 | 55 | 50 | 53 | ||
| 倾点(℃) | ASTMD-97 | -42 | ＜-50 | -55 | -57 | ＜-50 | ＜-50 | ||
| 闪点COC(℃) | ASTMD-92 | 164 | 192 | 179 | 195 | 190 | |||
| 20℃密度(克/毫升) | ASTMD-1298 | 0.88 | 0.89 | 0.89 | 0.89 | 0.89 | |||
| 酸值(毫克KOH/克) | ASTMD-974 | 0.02 | 0.01 | 0.02 | 0.03 | 0.02 | |||
| 水含量(ppm) | ASTMD-1064 | ＜40 | ＜40 | ＜40 | ＜40 | ＜40 | ＜40 | ＜40 | ＜40 |
| 颜色(ASTM) | ASTMD-1209 | ＜0.5 | 1-1.5 | 1-1.5 | 1-1.5 | 1-1.5 | |||
| 低温混溶性(℃)10％润滑剂在R-12中10％润滑剂在R-22中10％润滑剂在R-134a中10％润滑剂在R-404A中10％润滑剂在R-407C中 | 在外壳内*1 | IM*2IM*2IM*2 | IM*2IM*2IM*2 | IM*2IM*2IM*2 | IM*2IM*2IM*2 | IM*2IM*2IM*2 | IM*2IM*2IM*2 | IM*2IM*2IM*2 | |
| 四球磨损痕迹(毫米)40公斤，1小时 | ASTMD-2783 | 0.64 | 0.72 | 0.65 | |||||
| 故障的Falex负荷(磅) | ASTMD-3233 | 1900 | |||||||
| Falex(磨损齿)5小时，400磅，钢/钢在R-134a中 | ASTMD-1209 | 17 | |||||||
实施例3
可观测到三类混溶性性能，即：
a) 在最低的温度下在系统中是可混溶的；
b) 在某些点在系统中是不可混溶的，但在所有点在系统中仍是可溶的(部分可混溶的)；
c) 在所有点是不混溶的和不可溶的。
已测量样品13D在低于室温(21℃)的所有温度下，在HFC致冷剂内的浓度至少为5％下是不可混溶的。这一点对性能没有明显影响，条件是润滑剂组合物在约2％的浓度(在致冷系统中循环的润滑剂组合物的浓度的代表)下是可混溶的或有足够的溶解度使油回到压缩机。
实施例4
按ASHRAE 97密封管法测量了材料的相容性数据。将试验的润滑剂组合物与聚对苯二甲酸乙二醇酯(PET-通常在电机中用作绝缘材料)、聚对苯二甲酸丁二醇酯(PBT-通常在压缩机中发现)、钢、铝和铜的样品一起放在高压釜中。然后将高压釜密封并抽空，使R-134a致冷剂加入。致冷剂与润滑剂组合物的比例为50∶50。试验条件为在130℃和400psig下14天。
在试验前后润滑剂组合物的分析结果列入表7。
可观测到，在这些条件下，除了样品17的粘度有明显下降外，润滑剂组合物的条件有很小的变化。在这一试验过程中，试验材料的条件没有明显变化。
表7
| 样品编号 | 粘度(厘沱) | 酸值(毫克KOH/克) | 颜色(ASTM) | |||
| 前 | 后 | 前 | 后 | 前 | 后 | |
| 13D | 12.4 | 12.6 | 0.02 | 0.01 | 1-1.5 | 1-1.5 |
| 16 | 50.9 | 51.9 | 0.01 | 0.01 | ＜0.5 | ＜0.5 |
| 17 | 65.2 | 56.2 | 0.01 | 0.01 | ＜0.5 | ＜0.5 |
| 18 | 65.2 | 62.4 | 0.01 | 0.01 | ＜0.5 | ＜0.5 |
实施例5
按ASHRAE 97密封管法测量了热稳定性数据。将试验润滑剂组合物放在高压釜中，将它密封并抽空，使R-134a致冷剂加入。致冷剂与润滑剂组合物的比例为50∶50。试验条件为在175℃和600psig下14天。
在试验前后润滑剂组合物的分析结果列入表8。
表8
| 样品编号 | 粘度(厘沱) | 酸值(毫克KOH/克) | 颜色(ASTM) | |||
| 前 | 后 | 前 | 后 | 前 | 后 | |
| 13D | 12.4 | 13.0 | 0.02 | 0.02 | 1-1.5 | 1-1.5 |
| 16 | 50.9 | 48.1 | 0.01 | 0.01 | ＜0.5 | ＜0.5 |
| 17 | 65.2 | 65.0 | 0.01 | 0.01 | ＜0.5 | ＜0.5 |
| 18 | 65.2 | 58.7 | 0.01 | 0.01 | ＜0.5 | ＜0.5 |
同样可观测到，在这些条件下，除了样品18的粘度有明显下降外，润滑剂组合物的条件有很小的变化。这可能是由于与实施例4中的材料相容性试验相比，在这一试验的更高的温度条件下润滑剂样品18组合物的变质。
实施例6
在一替代试验中，将润滑剂组合物样品在干燥氮气流下在玻璃容器中在120℃下加热7天。在试验前后测量润滑剂组合物的条件。结果列入表9。
由这一试验得到的唯一重要结果是样品17和18的酸值增加。样品13和16的物理性质实际上与原润滑剂组合物没有变化。
表9
| 试验前分析 | ||||
| 样品编号 | 水分(ppm) | 40℃粘度(厘沱) | 酸值(毫克KOH/克) | 颜色(Hazen) |
| 13D | 17 | 14.0 | 0.017 | 346 |
| 16 | 0 | 55.1 | 0.006 | 86 |
| 17 | 3 | 66.5 | 0.003 | 44 |
| 18 | 24 | 69.3 | 0.011 | 13 |
| 试验后分析 | ||||
| 13D | 38 | 14.0 | 0.009 | 394 |
| 16 | 20 | 55.1 | 0.006 | 127 |
| 17 | 20 | 66.3 | 0.008 | 57 |
| 18 | 61 | 69.6 | 0.025 | 73 |
实施例7
吸湿性(从大气中吸收水分)是重要的，因为润滑剂组合物要在空气中短期处理，所以能使水含量增加到超过通常提供的水平。由于费用考虑，许多空调系统制造商喜欢省去在线干燥器，后者作为对防止水分进入提供的保险。据认为在致冷或空调系统中超过100ppm的水含量的存在对可靠性是有害的，因为可能与PET马达金属线绕绝缘相互作用，导致降解和马达故障。所以，润滑剂组合物从大气中吸收水分越少，系统中就越不可能达到产生这些潜在故障的含水量。
为了测量润滑剂组合物的吸湿性，使用了以下的技术。用干燥氮气鼓泡来干燥样品，并纪录最初的水含量。将干燥的润滑剂组合物装入100毫升大口烧瓶中，将后者放入装有饱和食盐溶液的干燥器中。将干燥器密封，并在室温(21℃)下放置。在前3小时每30分钟然后每小时(一直到6小时)取得润滑剂组合物的水分读数。
每一水分的结果为三个读数的平均值。结果列入表10。
将这一试验的结果作图，并示于图2。
实施例8
通过装入Tecumseh Europe RK5515固定叶片旋转压缩机来评价润滑剂组合物，相关样品和适合致冷剂气体与致冷系统的其它组分在线连接。
试验条件列入表11。
压缩机在这些条件下操作2000小时，然后拆卸分析金属组件的磨损。
表10
| 时间(分) | 含水量(ppm) | |||
| 样品13D | 样品16 | 样品17 | 样品18 | |
| 0 | 0 | 0 | 0 | 0 |
| 30 | 6 | 0 | 0 | 21 |
| 60 | 32 | 0 | 8 | 105 |
| 90 | 36 | 0 | 6 | 55 |
| 120 | 45 | 0 | 24 | 89 |
| 150 | 47 | 0 | 22 | 148 |
| 180 | 38 | 0 | 33 | 173 |
| 240 | 57 | 0 | 70 | 252 |
| 300 | 53 | 0 | 52 | 291 |
| 360 | 54 | 0 | 79 | 349 |
表11
| 致冷剂 | 吸入压力(psig) | 排出压力(psig) | 马达绕组温度(℃) |
| R-22 | 93 | 415 | 130 |
| R-407C | 86 | 470 | 130 |
试验以后并拆卸压缩机检查，用以下的压缩机组件划痕标准来确定压缩机试验磨损等级评价。
等级 说明
0 没有变化，没有明显的或可见的磨损迹象
1 低磨损，在小范围上有轻微磨光迹象
2 中度磨损，轻微擦伤或磨光。在局部区域表面处理可磨掉。
3 明显磨损，在某一区域内表面被磨掉。磨损可为轻度擦伤。如果划过整个表面，那么感觉稍微粗糙。
4 高度磨损，在磨损区域内表面有清楚的擦伤。磨损是明显的以及有粗糙感，可能有台阶。
5 很高度的磨损，在局部区域内有广泛的磨损。在表面和原金属之间有磨损台阶。包括裂缝和胶住。
压缩机试验结果
通过分析15个单独点的磨损得到总的磨损形状。但是，在图1所示的压缩部件20和叶片端部24的外表面的磨损形状为圆形，以确定在压缩机中发生的磨损是否可接受。根据压缩机试验磨损等级评价，在这些两个位置上的三个数据的平均值是在可接受的范围。
结果列入表12品编号
表12
| 样品编号 | 致冷剂 | 磨损痕迹 | ||
| 叶片端部24 | 压缩部件20 | 全部 | ||
| 9 | R-407C | 3 | 3 | 17.5 |
| 10 | R-407C | 2.5 | 4.5 | 31 |
| 11 | R-407C | 2.5 | 2.5 | 24 |
| 12 | R-407C | 1 | 2 | 14 |
| 14B | R-407C | 5 | 5 | 37 |
| 15B | R-407C | 2 | 3 | 28 |
| 16 | R-22 | 3.5 | 4.5 | 40 |
正如从这些结果可看出的，本发明的润滑剂组合物对压缩机的组件有很少的磨损。
实施例9
通过装入Tecumseh Europe RK5515固定叶片旋转压缩机来评价润滑剂组合物13D和18，相关样品和适合致冷剂气体R407C与致冷系统的其它组分在线连接。
试验条件列入表13。对于在线/离线试验来说，使用自动切换使压缩机在线15秒，然后离线15秒。
压缩机在所示的周期/时间的这些条件下操作，然后停机分析金属组件上的磨损。分析结果列入表14。
表13
| 试验 | 试验类型 | 吸入压力(psig) | 排出压力(psig) | 马达绕组温度(℃) |
| 1 | 在线/离线125000周期 | 96 | 556 | 100±5 |
| 2 | 500小时 | 96 | 556 | 88±3 |
| 3 | 500小时 | 13 | 320 | 88±3 |
表14
| 试验编号 | 样品编号 | 磨损痕迹 | |
| 叶片端部24 | 压缩部件20 | ||
| 1 | 13D | 0.5 | 0.5 |
| 2 | 13D | 0.5 | 0.5 |
| 3 | 13D | 0.5 | 0.5 |
| 1 | 18 | 1 | 1 |
| 2 | 18 | 1 | 1 |
| 3 | 18 | 1.5 | 2 |
试验模拟了操作条件的变化，即在线和离线周期(试验1)和不同的致冷剂致冷回路操作温度(试验2-高温；试验3-低温)。正如从表14可看出的，本发明的润滑剂组合物13D明显优于对比组合物18。
实施例10
用Guangdong Meizhi Compressor Co的PRC PH225X2C压缩机和样品13A和19在表15所列的操作条件下重复实施例9。结果列入表16，从表16可看出，本发明的润滑剂组合物13A明显优于对比组合物19。
表15
| 试验类型 | 吸入压力(psig) | 排出压力(psig) | 马达绕组温度(℃) |
| 500小时 | 96 | 556 | 85 |
表16
| 样品编号 | 磨损痕迹 | |
| 叶片端部24 | 压缩部件20 | |
| 13A | 0.5 | 0.5 |
| 19 | 1 | 1 |
实施例11
在正常情况的温度操作范围(通常为40-60℃)，起动马达驱动的压缩机所需的起动电压优选尽量小，以便使能耗最小以及减少对马达的电应力，从而提高可靠性。通过提高供给马达的电压一直到马达起动为止来确定在不同温度下，使用各种润滑剂组合物样品和不同致冷剂气体时的起动电压。对每一组合，起动电压测量两次。结果列入表17和示于图3和4。
表17
| 致冷剂 | 马达绕组温度(℃) | 样品/起动电压(伏) | |||
| 13B | 18 | 19 | 15A | ||
| R-407C | 30 | 128 | 125 | 130 | 133 |
| R-407C | 40 | 133 | 140 | 140 | 136 |
| R-407C | 50 | 137 | 157 | 150 | 142 |
| R-407C | 60 | 143 | 163 | 160 | 151 |
| R-404 | 30 | 133 | 132 | 134 | |
| R-404 | 40 | 134 | 134 | 136 | |
| R-404 | 50 | 135 | 136 | 138 | |
| R-404 | 60 | 136 | 138 | 140 | |
正如从表17和图3(它对R-407C致冷剂结果作图)和图4(它对R-404致冷剂结果作图)可看出的，在整个正常情况温度操作范围，本发明的样品13B的压缩机马达所需的起动电压比对比样品要低。
实施例12
在致冷系统中，不可能排除润滑剂组合物从压缩机带到回路的其它部件。因此，将润滑剂组合物有效地通过回路返回压缩机是重要的。为了测试润滑剂组合物的可输送性，准确称重约10克润滑剂组合物，然后倒入水平放置的铜盘管的一端(管内径为6.3毫米，盘管内径为93毫米，管长为2.5米)。将致冷剂气体R-134a通过管的一端吹入，润滑剂组合物以18升/分的速率送入15分钟。借助致冷剂气体流通过管子输送的润滑剂组合物在管子的出口处收集。缓慢地将收集的润滑剂组合物加热，以便除去溶解的任何致冷剂气体，并在收集的润滑剂组合物数量准确称重以前冷却到室温。每一润滑剂组合物运转许多次，结果列入表18。
表18
| 样品编号 | 输送的润滑剂％ |
| 15A | 47/38/46 |
| 14A | 75/70 |
| 13C | 68/70 |
| 20 | 45/46/46 |
正如从表18可看出的，这一试验合理地与现实性相关连，当致冷剂为HFC时，矿物油(样品20)和烷基苯(样品15)难通过致冷系统输送，而当致冷剂为HFC时，多元醇酯(样品4)能很好通过致冷系统输送。本发明的润滑剂组合物(样品13C)比多元醇酯(样品14A)更有利。
Claims (24)
1.一种用于旋转叶片压缩机的润滑剂组合物，含有烷基苯作为主要组分和多元醇酯作为次要组分的基础油组分。
2.根据权利要求1的润滑剂组合物，其中基础油组分含有至少55重量％烷基苯和至多45重量％多元醇酯；更优选55-75重量％烷基苯和45-25重量％多元醇酯；特别是60-75重量％烷基苯和45-25重量％多元醇酯。
3.根据权利要求1或2的润滑剂组合物，其中基础油组分基本上由烷基苯和多元醇酯组成。
4.根据上述权利要求中任一项的润滑剂组合物，其中烷基苯组分选自单烷基苯、二烷基苯、二苯基烷烃及其混合物。
5.根据上述权利要求任一项的润滑剂组合物，其中烷基苯组分有这样的分子量分布，其中至少80％，更特别是100％的分子量大于200；更特别的是，至少75％的分子量大于300；特别是至少40％，更特别是50％分子量大于350。
6.根据上述权利要求任一项的润滑剂组合物，其中烷基苯组分有这样的分子量分布，其中至少70％的分子量小于500；更特别的是，至少50％的分子量小于450。
7.根据上述权利要求任一项的润滑剂组合物，其中在40℃下，烷基苯组分的运动粘度为至少10厘沱、更优选至少25厘沱，但不大于70厘沱，而在100℃下，其运动粘度为至少2厘沱、更优选至少3.5厘沱，但不大于10厘沱。
8.根据上述权利要求任一项的润滑剂组合物，其中烷基苯组分的倾点小于-10℃、更优选小于-20℃、特别是小于-30℃。
9.根据上述权利要求任一项的润滑剂组合物，其中烷基苯组分的酸值小于0.04毫克KOH/克。
10.根据上述权利要求任一项的润滑剂组合物，其中多元醇酯组分含有至少一种为多元醇和一元羧酸反应产物的多元醇酯。
11.根据上述权利要求任一项的润滑剂组合物，其中多元醇酯组分含有至少一种为一种或多种选自新戊醇(NPG)、三羟甲基丙烷(TMP)和季戊四醇(PE)及其二聚物和三聚物的醇和一种或多种选自直链的和/或支链的C5-C18酸、特别是C5-C13酸、更特别是C5-C9的酸反应产物的多元醇酯。
12.根据上述权利要求任一项的润滑剂组合物，其中在40℃下，多元醇酯组分的运动粘度为至少5厘沱，但不大于40厘沱、更优选小于25厘沱，而在100℃下，其运动粘度为至少1.5厘沱，但不大于5厘沱、更优选小于4厘沱。
13.根据上述权利要求任一项的润滑剂组合物，其中多元醇酯组分的倾点小于-40℃、更优选小于-50℃、特别是小于-55℃。
14.根据上述权利要求任一项的润滑剂组合物，其中多元醇酯组分的酸值小于0.04毫克KOH/克。
15.根据上述权利要求任一项的润滑剂组合物，在40℃下，它的运动粘度为至少5厘沱，但不大于40厘沱、更优选小于25厘沱，而在100℃下，其运动粘度为至少2厘沱，但不大于6厘沱、更优选小于5厘沱。
16.根据上述权利要求任一项的润滑剂组合物，它的倾点小于-40℃、优选不大于-45℃、特别是不大于-50℃。
17.根据上述权利要求任一项的润滑剂组合物，它含有一种或多种选自抗氧化剂、抗磨添加剂、极压添加剂、酸消除剂、起泡剂、消泡剂、稳定剂、表面活性剂、粘度指数改进剂、腐蚀抑制剂、金属减活剂或钝化剂、润滑改进剂或油性添加剂和摩擦改进剂的添加剂，按基础油组分的重量计，其含量为0.0001-20重量％、更优选0.01-10重量％、更特别是0.01-5重量％。
18.上述权利要求任一项定义的润滑剂组合物在旋转叶片压缩机中的用途。
19.一种润滑旋转叶片压缩机的方法，包括利用上述权利要求中任一项定义的润滑剂组合物。
20.一种装有上述权利要求中任一项定义的润滑剂组合物的旋转叶片压缩机。
21.一种包含旋转叶片压缩机的致冷系统，所述的系统装有无氯含氟传热流体的致冷剂和上述权利要求中任一项定义的润滑剂组合物。
22.根据权利要求21的致冷系统，其中致冷剂为含氢氟烃，更优选选自二氟甲烷(R-32)、三氟甲烷(R-23)、1，1，2，2-四氟乙烷(R-134)、1，1，1，2-四氟乙烷(R-134a)、1，1，1-三氟乙烷(R-143a)、I，1-二氟乙烷(R-152a)、五氟乙烷(R-125)和六氟乙烷(R-116)及其两种或两种以上的混合物。
23.根据权利要求22的致冷系统，其中致冷剂选自R-32、R-116、R-125、R-134a、R-143a及其混合物。
24.在权利要求18-23的任一项中，旋转叶片压缩机为固定叶片的压缩机。
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| EP (1) | EP1366139B1 (zh) |
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| US10836973B2 (en) | 2015-10-07 | 2020-11-17 | Idemitsu Kosan Co., Ltd. | Freezer oil, composition for freezers, freezer, and method for selecting freezer oil |
| CN105505540A (zh) * | 2016-01-04 | 2016-04-20 | 武汉杰生润滑科技有限公司 | 一种冷冻机油组合物及其应用 |
| CN110036099A (zh) * | 2016-12-05 | 2019-07-19 | 日油株式会社 | 冷冻机油组合物以及含有该冷冻机油组合物的冷冻机用工作流体组合物 |
| CN110036099B (zh) * | 2016-12-05 | 2021-12-10 | 日油株式会社 | 冷冻机油组合物以及含有该冷冻机油组合物的冷冻机用工作流体组合物 |
| CN108676547A (zh) * | 2018-05-30 | 2018-10-19 | 浙江巨化新材料研究院有限公司 | 一种中高温热泵混合工质 |
| CN109337578A (zh) * | 2018-10-27 | 2019-02-15 | 广州领扬科技有限公司 | 一种家装专用压缩机极化冷冻镀膜剂 |
| CN110699158A (zh) * | 2019-10-21 | 2020-01-17 | 中国石油化工股份有限公司 | 一种冷冻机油、其制备方法及应用 |
| CN114901788A (zh) * | 2020-01-15 | 2022-08-12 | 出光兴产株式会社 | 润滑油组合物 |
| CN114901788B (zh) * | 2020-01-15 | 2024-03-19 | 出光兴产株式会社 | 润滑油组合物 |
| CN112011382A (zh) * | 2020-08-25 | 2020-12-01 | 抚顺欧力石化有限公司 | 一种合成冷冻机油的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100859616B1 (ko) | 2008-09-23 |
| KR20030080048A (ko) | 2003-10-10 |
| EP1366139A1 (en) | 2003-12-03 |
| JP2010189652A (ja) | 2010-09-02 |
| CN100366713C (zh) | 2008-02-06 |
| EP1366139B1 (en) | 2014-11-12 |
| BR0207575B8 (pt) | 2013-02-19 |
| WO2002070637A1 (en) | 2002-09-12 |
| JP2004526832A (ja) | 2004-09-02 |
| US7176169B2 (en) | 2007-02-13 |
| ES2529540T3 (es) | 2015-02-23 |
| US20040063590A1 (en) | 2004-04-01 |
| BR0207575A (pt) | 2004-04-27 |
| GB0105065D0 (en) | 2001-04-18 |
| BR0207575B1 (pt) | 2013-01-08 |
| DK1366139T3 (en) | 2015-02-16 |
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