CN104204163A - 冷冻机用工作流体组合物以及冷冻机油 - Google Patents

冷冻机用工作流体组合物以及冷冻机油 Download PDF

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CN104204163A
CN104204163A CN201380016642.4A CN201380016642A CN104204163A CN 104204163 A CN104204163 A CN 104204163A CN 201380016642 A CN201380016642 A CN 201380016642A CN 104204163 A CN104204163 A CN 104204163A
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alkyl
oil
phenyl
working fluid
refrigerator oil
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斋藤正典
奈良文之
松本朋也
阿出川邦子
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Eneos Corp
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JX Nippon Oil and Energy Corp
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Abstract

本发明涉及一种冷冻机用工作流体组合物,其含有,碳数2~4的烃制冷剂,和冷冻机油,所述冷冻机油含有选自矿物油以及合成油中的至少1种润滑油基础油和选自具有1个碳数3~5的烷基的单(烷基苯基)二苯基磷酸酯以及具有2个碳数3~5的烷基的二(烷基苯基)苯基磷酸酯中的至少1种磷化合物,该磷化合物的含量以冷冻机油总量为基准计为0.01~5质量%。

Description

冷冻机用工作流体组合物以及冷冻机油
技术领域
本发明涉及冷冻机用工作流体组合物以及冷冻机油,更详细而言,涉及可以维持低摩擦系数、耐磨耗性高、可以有助于可靠性提高与省电化的冷冻机用工作流体组合物以及冷冻机油。
背景技术
以往作为冰箱、汽车空调、室内空调、工业用冷冻机等的制冷剂,广泛使用作为氢氟烃(HFC)的1,1,1,2-四氟乙烷(R134a)、二氟乙烷(R32)与五氟乙烷(R125)的质量比为1/1的混合制冷剂的R410A等。
然而,这些HFC制冷剂的全球变暖潜能(GWP)高达1000以上,因此由于所谓F-气体规定导致使用受限制。作为HFC制冷剂的代替候选,需要为低GWP,作为其中之一,存在已经在冰箱用中实用化的异丁烷(R600a)那样的烃制冷剂。烃制冷剂的GWP为20以下极低、物性值是适宜的,因此进行了广泛的研究。
在烃制冷剂共存下,在烃分子内没有提高润滑性的氯、氟,因此与HFC制冷剂等不同,不能期待基于制冷剂的润滑性提高,此外,烃对冷冻机油的溶解度高、降低油的粘度,因此润滑条件严苛,冷冻机油中谋求以往以上的高耐磨耗性。进而从省电化的观点出发,也谋求可以维持低摩擦系数的性能。
广泛的润滑油领域中,作为耐磨耗添加剂,通常已知醇、酯、长链脂肪酸等油性剂,磷酸酯、二硫代磷酸金属盐等耐磨耗剂,有机硫化合物、有机卤化合物等极压剂。另一方面,冷冻机油的情况下,若不是即便与制冷剂共存也不析出并且对稳定性没有坏影响的添加剂则不能使用。因此,以往的冷冻机油中的醇系、酯系的油性剂、磷酸酯之中,使用三苯基磷酸酯、磷酸三甲苯酯。
此外,专利文献1中公开了并用添加磷系添加剂与特定的环氧化合物的包含冷冻机用途的润滑油,专利文献2中公开了作为HFC制冷剂用途并用添加三苯基磷酸酯与三(烷基苯基)磷酸酯的压缩机用润滑油,专利文献3中公开了作为HFC制冷剂用的添加磷酸三甲苯酯、与包含缩水甘油醚的环氧或碳二亚胺的冷冻机油。
现有专利文献
专利文献
专利文献1:日本特开平5-171174号公报
专利文献2:日本特开平8-157847号公报
专利文献3:日本特开平9-189453号公报
发明内容
发明要解决的问题
然而,根据本发明人的研究,使用上述的添加剂的冷冻机油作为烃制冷剂用冷冻机油在以下方面还有改善的余地。
即,首先上述添加剂之中,油性剂通过吸附而形成润滑覆膜。因此,混合润滑区域那样的负载条件较温和的情况下可以维持低摩擦系数,但在烃制冷剂共存下负载条件变严苛时,耐磨耗的效果丧失。
另一方面,三苯基磷酸酯、磷酸三甲苯酯具有耐磨耗的效果,但在滑动部表面形成硬覆膜,因此摩擦系数变高,不适于进行省电化的冷冻机,尤其在对地球环境优异的烃制冷剂共存下如前所述润滑条件变严苛,因此谋求高耐磨耗性并且低摩擦系数的添加剂。
本发明是鉴于上述以往技术具有的问题而成的,其目的在于提供即便在烃制冷剂共存下的严苛的润滑条件下也可以得到优异的耐磨耗性并且可以维持足够低的摩擦系数、省电化以及长期可靠性优异的冷冻机用工作流体组合物以及冷冻机油。
用于解决问题的方案
本发明人等发现通过在润滑油基础油中配合特定的磷化合物,从而在烃制冷剂共存下对其它的特性没有坏影响、可以提高冷冻机用工作流体组合物以及冷冻机油的耐磨耗性、并且可以维持低摩擦系数,从而完成本发明。
即,本发明提供一种冷冻机用工作流体组合物,其含有冷冻机油与碳数2~4的烃制冷剂,所述冷冻机油含有选自矿物油以及合成油中的至少1种润滑油基础油和选自具有1个碳数3~5的烷基的单(烷基苯基)二苯基磷酸酯以及具有2个碳数3~5的烷基的二(烷基苯基)苯基磷酸酯中的至少1种磷化合物,该磷化合物的含量以冷冻机油总量为基准计为0.01~5质量%。
上述磷化合物优选选自具有1个碳数4的烷基的单(丁基苯基)二苯基磷酸酯以及具有2个碳数4的烷基的二(丁基苯基)苯基磷酸酯。
上述润滑油基础油为选自矿物油、烷基苯、聚-α-烯烃、酯以及醚中的至少1种,该润滑油基础油的40℃下的运动粘度优选为3~500mm2/s。
进而,上述润滑油基础油为选自矿物油、烷基苯、聚-α-烯烃、二酯、多元醇酯、复合酯、聚亚烷基二醇、聚亚烷基二醇化合物以及聚乙烯基醚中的至少1种以上,该润滑油基础油的40℃下的运动粘度优选为3~300mm2/s。
上述烃制冷剂优选选自丙烷(R290)、丙烯(R1270)、正丁烷(R600)以及异丁烷(R600a)中的至少1种。
此外,本发明提供一种与碳数2~4的烃制冷剂一起使用的冷冻机油,所述冷冻机油含有选自矿物油以及合成油中的至少1种润滑油基础油、和选自具有1个碳数3~5的烷基的单(烷基苯基)二苯基磷酸酯以及具有2个碳数3~5的烷基的二(烷基苯基)苯基磷酸酯中的至少1种磷化合物,该磷化合物的含量以冷冻机油总量为基准计为0.01~5质量%。
发明的效果
根据本发明提供即便在烃制冷剂共存下的严苛润滑条件下也可以维持耐磨耗的效果以及低摩擦系数,实现省电化,并且可以发挥经过长期也可以稳定地使用的特殊的效果的冷冻机用工作流体组合物以及冷冻机油。
具体实施方式
以下,对于本发明的适宜的实施方式进行详细地说明。
[第1实施方式:冷冻机油]
本发明的第1实施方式中所述的冷冻机油含有选自矿物油以及合成油中的至少1种润滑油基础油、和选自具有1个碳数3~5的烷基的单(烷基苯基)二苯基磷酸酯以及具有2个碳数3~5的烷基的二(烷基苯基)苯基磷酸酯中的至少1种磷化合物,该磷化合物的含量以冷冻机油总量为基准计为0.01~5质量%。所述冷冻机油与碳数2~4的烃制冷剂一起使用。
对于本实施方式所述的冷冻机油,作为润滑油基础油含有选自矿物油以及合成油中的至少1种。
作为矿物油,可以为石蜡系、环烷烃系、混合基系的任一种。此外,可以适宜地使用对这些矿物油的1种或2种以上的混合物进行常压蒸馏进而减压蒸馏而得到的润滑油馏分通过适宜组合脱溶剂、溶剂萃取、加氢精制、加氢裂化、溶剂脱蜡、氢化脱蜡、白土处理等润滑油精制手段进行处理而得到的精制润滑油馏分。可以单独或组合使用2种以上根据各种的原料与各种的精制手段的组合而得到的性状不同的精制润滑油馏分。
此外,作为合成油系的润滑油基础油,可以列举出酯、醚那样的含氧化合物,或聚-α-烯烃(PAO)、乙烯-α-烯烃低聚物、烷基苯、烷基萘那样的烃油。
含氧化合物基础油之中,对于酯,各种分子结构的化合物均有销售,为具有如下特征的基础油:具有各种特有的粘度特性、低温特性,与相同粘度的烃系基础油相比时闪点高。酯可以使醇与脂肪酸脱水缩合反应而得到,本发明中,从化学稳定性方面考虑,可以列举出将二元酸与一元醇形成的二酯、多元醇(特别是新戊多元醇)与1元脂肪酸形成的多元醇酯、或者多元醇与多元酸与一元醇(或1元脂肪酸)形成的复合酯作为适宜的基础油成分。其中,优选稳定性优异的多元醇酯。
作为醚,可以列举出聚亚烷基二醇、聚乙烯基醚等。作为聚亚烷基二醇,有聚丙二醇、聚乙二醇、环氧丙烷与环氧乙烷的共聚物等。末端结构从吸湿性的观点出发优选至少一者为烷基、特别优选为甲基。此外,从制造容易性以及成本的观点出发,优选任一末端为烷基,另一端为氢原子,特别优选一者为甲基、另一者为氢原子。对于主骨架,从润滑性的观点出发优选包含氧代亚乙基(EO)与氧代亚丙基(PO)的共聚物,氧代亚乙基在氧代亚乙基与氧代亚丙基的总和中所占的比例(EO/PO+EO)优选为0.1~0.8的范围、更优选为0.3~0.6的范围。此外,在吸湿性、热/化学稳定性的观点上EO/(PO+EO)的值优选为0~0.5的范围,更优选为0~0.2的范围,最优选为0(即环氧丙烷均聚物)。
聚乙烯基醚具有由下述通式(1)表示的结构单元。本实施方式中的聚乙烯基醚可以为其结构单元相同的均聚物、也可以为由2种以上的结构单元构成的共聚物,通过制成共聚物可以平衡性良好地调整特性,因此优选。
[式(1)中、R1、R2以及R3可以相同也可以不同,分别表示氢原子或者碳数1~8的烃基,R4表示碳数1~10的二价烃基或者碳数2~20的二价的含有醚键氧的烃基,R5表示碳数1~20的烃基,m表示对于前述聚乙烯基醚的m的平均值为0~10那样的数,各结构单元的R1~R5可以相同也可以不同,一结构单元中m为2以上时,多个R4O可以相同也可以不同。]
合成系烃油之中,聚-α-烯烃(PAO)为α-烯烃的聚合物,因此根据其聚合度可以适宜选定特性。
此外,烷基苯根据烷基的结构具有直链型和支链型,由于特性不同,因此可以根据目的分别使用。
本实施方式中,上述的矿物油以及合成油之中可以单独使用1种,此外,也可以组合使用2种以上。
润滑油基础油的40℃下的运动粘度优选为3~500mm2/s、更优选为3~300mm2/s、进一步优选为5~150mm2/s。此外,润滑油基础油的粘度指数优选为10以上。需要说明的是,本发明中所谓40℃下的运动粘度以及粘度指数分别是指基于JIS K2283而测定的值。
此外,润滑油基础油的倾点优选为-10℃以下、更优选为-20℃以下。需要说明的是,本发明中所谓倾点是指基于JIS K2269而测定的值。
此外,润滑油基础油的闪点优选为120℃以上、更优选为200℃以上。需要说明的是,本发明中所谓闪点是指基于JIS K2265而测定的值。
此外,本实施方式中所述冷冻机油含有选自具有1个碳数3~5的烷基的单(烷基苯基)二苯基磷酸酯以及具有2个碳数3~5的烷基的二(烷基苯基)苯基磷酸酯中的至少1种的磷化合物。
本实施方式中的上述的磷化合物可以由下述通式(2)表示。
(R6-Ph)n-P(=O)-(Ph)3-n  (2)
[式(2)中,R6表示碳数3~5的烷基、Ph表示苯基、n表示1或2的整数。]
n为1时,由上述通式(2)表示的磷化合物为具有1个碳数3~5的烷基的单(烷基苯基)二苯基磷酸酯。为该单(烷基苯基)二苯基磷酸酯,具体而言,可以列举出异丙基苯基二苯基磷酸酯、叔丁基苯基二苯基磷酸酯、正丁基苯基二苯基磷酸酯等。
n为2时,由上述通式(2)表示的磷化合物为具有2个碳数3~5的烷基的二(烷基苯基)苯基磷酸酯。作为该二(烷基苯基)二苯基磷酸酯,可以列举出二(异丙基苯基)苯基磷酸酯、二(叔丁基苯基)苯基磷酸酯、二(正丁基苯基)苯基磷酸酯等。
通式(2)中的R6从冷冻机油的润滑性的观点出发优选丁基。作为丁基,可以列举出为直链烷基的正丁基、为支链烷基的叔丁基等。需要说明的是,R6的碳数为2以下时,摩擦系数变高、难以达成省电化。本发明人推测其原因在于,形成于滑动部的磷化合物的覆膜变硬。另一方面,R6的碳数超过5时,耐磨耗的效果变小。本发明人推测其原因在于,磷化合物对润滑油基础油的亲和力变大,在滑动部的磷化合物的浓度急剧减少。
上述磷化合物的含量以冷冻机油总量为基准计为0.01~5质量%、优选为0.1~3质量%。含量不足前述下限值时,不能发挥润滑性提高的效果。此外,含量超过前述上限值时,对于冷冻机油的稳定性、体系内的有机材料的溶胀等的影响变大。
本实施方式中所述的冷冻机油可以仅包含上述的润滑油基础油以及磷化合物,在不损害本发明的目的的范围内,为了进一步提高性能还可以含有抗氧化剂、摩擦调整剂、防锈剂、金属减活剂、消泡剂等添加剂。
作为抗氧化剂,可以列举出二叔丁基对甲酚那样的酚系化合物、烷基二苯胺那样的胺系化合物等,作为摩擦调整剂,可以列举出脂肪族胺、脂肪族酰胺、脂肪族酰亚胺、醇、酯、酸性磷酸酯胺盐,亚磷酸酯胺盐等,作为防锈剂,可以列举出链烯基琥珀酸酯或者部分酯等,作为金属减活剂,可以列举出苯并三唑等,作为消泡剂,可以列举出硅化合物、酯系消泡剂等。
本实施方式中所述冷冻机油可以优选用作使用碳数2~4的烃制冷剂的冷冻机用的润滑油。在此,将本实施方式中所述冷冻机油应用于使用异丁烷作为制冷剂的冰箱的情况下,需要具有适于电动机内藏型(密闭型)的压缩机的冷冻机油的特性、即高电绝缘性。因此,本实施方式中所述的冷冻机油在添加剂配合之后,体积电阻率优选为109Ω·m以上。需要说明的是,本发明中的体积电阻率意味着基于JIS C2101而测定的值。此外,该体积电阻率意味着使用添加剂时配合添加剂之后的冷冻机油的体积电阻率。
[第2实施方式:冷冻机用工作流体组合物]
本发明的第2实施方式中所述的冷冻机用工作流体组合物含有冷冻机油和碳数2~4的烃制冷剂,所述冷冻机油含有选自矿物油以及合成油中的至少1种的润滑油基础油、和选自具有1个碳数3~5的烷基的单(烷基苯基)二苯基磷酸酯以及具有2个碳数3~5的烷基的二(烷基苯基)苯基磷酸酯中的至少1种的磷化合物,该磷化合物的含量以冷冻机油总量为基准计为0.01~5质量%。需要说明的是,本实施方式中所述冷冻机用工作流体组合物中含有的冷冻机油与上述的第1实施方式中所述的冷冻机油同样,因此在此省略重复的说明。
作为本实施方式中的碳数2~4的烃制冷剂,具体而言,可以列举出乙烷、丙烷、正丁烷、异丁烷等。其中,异丁烷(R600a)用作冰箱用途,丙烷(R290)作为室内空气调节装置用途进行实用化研究,本实施方式中,可以适宜使用这些烃制冷剂。尤其,本实施方式所述的冷冻机用工作流体组合物由于冷冻机油的低粘度化可以达成省电力,因此适宜作为主要使用省电力效果大的往复型压缩机的冰箱用途,特别是优选作为异丁烷制冷剂用途。
本实施方式中所述冷冻机用工作流体组合物中,制冷剂与冷冻机油的含有比例没有特别限制,制冷剂/冷冻机油优选为10/90~90/10、更优选为30/70~70/30。
实施例
以下,基于实施例以及比较例更详细地说明本发明,本发明并不限定于以下的实施例。
[实施例1~8、比较例1~6]
实施例1~8以及比较例1~6中,分别使用以下所示的润滑油基础油以及添加剂,制备具有表1~4所示的组成的冷冻机油。
(A)润滑油基础油
A1:季戊四醇与2-乙基己酸以及3,5,5-三甲基己酸的混合酸(质量比1:1)形成的酯(40℃下的运动粘度68.0mm2/s、粘度指数90、倾点-40℃、闪点260℃)
A2:癸二酸二辛酯(40℃下的运动粘度11.6mm2/s、粘度指数150、倾点-50℃、闪点220℃)
A3:两末端由甲基进行醚封端的聚氧丙烯(平均分子量1000、40℃下的运动粘度46.0mm2/s、粘度指数190、倾点-45℃、闪点218℃)
A4:石蜡系精制矿物油(40℃下的运动粘度22.0mm2/s、粘度指数95、倾点-15℃、闪点210℃)
A5:直链型烷基苯(40℃下的运动粘度8.1mm2/s、粘度指数45、倾点-50℃、闪点154℃)
(B)由通式(2)表示的磷化合物
B1:单(正丁基苯基)二苯基磷酸酯
B2:二(异丙基苯基)苯基磷酸酯
B3:单(叔丁基苯基)二苯基磷酸酯/二(叔丁基苯基)苯基磷酸酯=65/35(质量比)的混合物
(C)其它的添加剂
C1:油性剂:单油酸甘油酯(GMO)
C2:耐磨耗剂;三苯基磷酸酯(TPP)
C3:耐磨耗剂:磷酸三甲苯酯(TCP)
接着,使用实施例1~8以及比较例1~6的冷冻机油,进行以下的润滑性试验以及热稳定性试验。
(润滑性试验)
使用ASTM D-2714-88的Falex块对环(block on ring)摩擦磨耗试验机,对于试验片,块:合金工具钢SKS3(JIS G4404)、环:镍铬钼钢(Nickelchromium molybdenum steel)SNCM220(JIS G4103),将试验条件设为载荷:300N圆周速度:0.1m/s温度:50℃试验时间:30分钟,进行摩擦磨耗试验。需要说明的是,试样油量为100ml,模拟用烃制冷剂进行稀释,加入20ml作为未气化的烃的正癸烷进行稀释,将总的样品量设为120ml。
作为试验结果,对于摩擦系数测量试验后半部分(大约25分钟)稳定时的值来表示,对于磨耗用带刻度的显微镜测量试验终止后的块上的磨耗宽(mm)来表示。在表1~4中示出所得到的结果。
(热稳定性试验)
称量90g含有水分量调整为100ppm以下的试样油到高压釜中,封入催化剂(铁、铜、铝的线、外径均为1.6mm×50mm)与10g异丁烷制冷剂之后,加热至175℃,测定100小时后的试样油的外观与酸值(JIS C2101)。在表1~4中示出所得到的结果。需要说明的是,热稳定性试验前的试样油(新油)的酸值均为0.01mgKOH/g。
表1
表2
表3
表4
如表1、2所示,实施例1~8的冷冻机油与比较例1的冷冻机油相比,显示出摩擦系数低、磨耗宽小的结果。
接着,实施例1~8与比较例2、4比较,作为磨耗的指标的磨耗宽在比较例2、4的情况下显示出远大于实施例1~8的值。该结果支持如下观点:吸附型的油性剂的摩擦系数为一定水平,但耐磨耗性差。
此外,实施例1~8与比较例3、5、6比较,比较例3、5、6的摩擦系数显示出比实施例1~8高约20%的值。从冷冻机压缩机的省电化的观点出发其是很大的差。
从这些结果出发,可知实施例1~8的冷冻机油为稳定性良好,对于润滑性即便用烃稀释的情况下耐磨耗也高、也可以将摩擦系数维持在较低的冷冻机油。
产业上的可利用性
在冷冻机用制冷剂根据现行HFC制冷剂的规定替换为全球变暖潜能、即GWP更低的物质的行动中,本发明的冷冻机油即便使用作为冷冻机用制冷剂的代替候选之一的烃制冷剂,也可以维持其高耐磨耗性与摩擦系数的特性,从而省电化、并且作为长期可靠性高的油可以适宜地用于已经部分实用化的冰箱、室内空调、一般工业用冷冻机等。

Claims (6)

1.一种冷冻机用工作流体组合物,其含有冷冻机油、和碳数2~4的烃制冷剂,
所述冷冻机油含有选自矿物油以及合成油中的至少1种润滑油基础油、和选自具有1个碳数3~5的烷基的单(烷基苯基)二苯基磷酸酯以及具有2个碳数3~5的烷基的二(烷基苯基)苯基磷酸酯中的至少1种磷化合物,该磷化合物的含量以冷冻机油总量为基准计为0.01~5质量%。
2.根据权利要求1所述的冷冻机用工作流体组合物,其中,所述磷化合物为选自具有1个碳数4的烷基的单(丁基苯基)二苯基磷酸酯以及具有2个碳数4的烷基的二(丁基苯基)苯基磷酸酯中的至少1种。
3.根据权利要求1或2所述的冷冻机用工作流体组合物,其中,所述润滑油基础油为选自矿物油、烷基苯、聚-α-烯烃、酯以及醚中的至少1种,该润滑油基础油的40℃下的运动粘度为3~500mm2/s。
4.根据权利要求1~3中任一项所述的冷冻机用工作流体组合物,其中,所述润滑油基础油为选自矿物油、烷基苯、聚-α-烯烃、二酯、多元醇酯、复合酯、聚亚烷基二醇、聚亚烷基二醇化合物以及聚乙烯基醚中的至少1种以上,该润滑油基础油的40℃下的运动粘度为3~300mm2/s。
5.根据权利要求1~4中任一项所述的冷冻机用工作流体组合物,其中,所述烃制冷剂为选自丙烷、丙烯、正丁烷以及异丁烷中的至少1种。
6.一种冷冻机油,其与碳数2~4的烃制冷剂一起使用,
所述冷冻机油含有选自矿物油以及合成油中的至少1种润滑油基础油、和选自具有1个碳数3~5的烷基的单(烷基苯基)二苯基磷酸酯以及具有2个碳数3~5的烷基的二(烷基苯基)苯基磷酸酯中的至少1种磷化合物,
该磷化合物的含量以冷冻机油总量为基准计为0.01~5质量%。
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