CN1484688A - 润滑油组合物 - Google Patents
润滑油组合物 Download PDFInfo
- Publication number
- CN1484688A CN1484688A CNA028034783A CN02803478A CN1484688A CN 1484688 A CN1484688 A CN 1484688A CN A028034783 A CNA028034783 A CN A028034783A CN 02803478 A CN02803478 A CN 02803478A CN 1484688 A CN1484688 A CN 1484688A
- Authority
- CN
- China
- Prior art keywords
- oil composition
- lubricating oil
- dithio
- propionic acid
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
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Abstract
一种含有β-二硫代磷酰化丙酸(A)、三芳基磷酸酯(B)和基础油的润滑油组合物,所述基础油包括矿物油和/或合成油。
Description
本发明涉及一种润滑油组合物,所述润滑油组合物即使在苛刻的高压/高负荷工作条件下也具有良好的润滑性能。
在较高压力条件下以较高速度应用工业机器以及其小型化已经造成机器元件如液压机、压缩机、透平机、齿轮元件和轴承在更苛刻的条件下操作。
因此所应用的润滑油必须具有良好的润滑性能,从而充分保证这些机器即使在高压、高速、高负荷和高温下应用时的长期寿命。
针对这些要求,已经将二烷基二硫代磷酸锌用于工业机器润滑油的耐磨润滑油组合物中。但是这些化合物的缺点是当被水污染时的水解不稳定性、在高温和高压下的热氧化不稳定性、以及当润滑油变质时产生难闻的气味。
除上述问题外,由于近来有关环境保护和毒性的问题,对于锌化合物如二烷基二硫代磷酸锌的应用越来越受关注。
含有硫化物、磷化物及其磷-硫基组合物的耐磨润滑油组合物是已知的不含锌的耐磨润滑油,这种润滑油不含二烷基二硫代磷酸锌。
具体地,硫化烃和酸性磷酸酯的组合物以及三芳基硫代磷酸酯、三芳基磷酸酯和酸性磷酸酯胺盐的组合物是已知的,如GB 1415964中所公开的,但硫化烃的腐蚀特性和气味会引起问题,并且高活性的酸性磷酸酯是不利的,这是因为它们造成水解变质并且降低热氧化稳定性。
因此本发明的目的是提供一种润滑油组合物,所述润滑油组合物含有尽可能少的灰分(如锌),并且即使在苛刻的高压、高速以及高负荷条件下应用时仍具有良好的耐磨性能,并且其在热氧化稳定性、耐水性和气味以及环境、安全和实际润滑油性能方面都是良好的。
本发明提供一种润滑油组合物,所述润滑油组合物含有β-二硫代磷酰化丙酸(A)、三芳基磷酸酯(B)和基础油,所述基础油包括矿物油和/或合成油。
在一种优选实施方案中,β-二硫代磷酰化丙酸(A)由如下通式(1)表示:
S=P(-OR1)2SCH2CH(R2)COOH (1)
其中R1可以相同或不同,代表具有3-8个碳原子的支链烷基,优选具有3-4个碳原子,并且R2代表氢原子或具有1-4个碳原子的烷基。
R1可以选自下列支链烷基:异丙基、支链丁基、支链戊基、支链己基、支链庚基以及支链辛基。
R2的例子包括氢、甲基、乙基、丙基和丁基。R2优选为甲基、乙基或氢。特别优选的是R2为甲基。
这种化合物的具体例子包括3-(O,O-二异丙基二硫代磷酰基)丙酸、3-(O,O-二异丙基二硫代磷酰基)-2-甲基-丙酸、3-(O,O-二异丁基二硫代磷酰基)-丙酸以及3-(O,O-二异丁基二硫代磷酰基)-2-甲基-丙酸。
相对于润滑油组合物的总量来说,在本发明中所加入的β-二硫代磷酰化丙酸(A)的量优选为0.001-1.0wt%,更优选为0.001-0.5wt%,甚至更优选为0.001-0.1wt%,并且最优选为0.005-0.05wt%。
如果加入的(A)量低于0.001wt%,则不能达到足够的增强效果,而如果加入的(A)量超过0.5wt%,则润滑性能达到饱和,并且可能在热氧化稳定性、水解稳定性以及腐蚀性能方面劣化,这是不希望的。
在一种优选实施方案中,三芳基磷酸酯(B)由如下通式(2)表示:
O=P(-O-R3)3 (2)
其中各R3独立地为苯基或带有1-9个碳原子烷基的苯基。
合适的三芳基磷酸酯(B)的具体例子包括三苯基磷酸酯、三羟甲苯基磷酸酯、三乙基苯基磷酸酯、三丙基苯基磷酸酯、三丁基苯基磷酸酯、三戊基苯基磷酸酯、三己基苯基磷酸酯、三庚基苯基磷酸酯、三辛基苯基磷酸酯和三壬基苯基磷酸酯。
相对于润滑油基础油的总量来说,在本发明中三芳基磷酸酯(B)的用量优选为0.05-10wt%,更优选为0.05-5wt%,并且最优选为0.1-2wt%。
如果加入的(B)量低于0.05wt%,则不可能达到足够的润滑性能,而如果加入的(B)量超过10wt%,则润滑性能达到饱和,并且可能在热氧化稳定性和水解稳定性方面劣化,这是不希望的。
在本发明的一种优选实施方案中,所述润滑油组合物具有相当于不超过150mg的磨损量,这符合“Vickers V104 C”叶轮泵试验(按照IP 281)中的DIN 51524(第2部分)标准。
在本发明的另一种优选实施方案中,所述润滑油组合物具有相当于不超过15mg的叶轮磨损量及相当于不超过75mg的环磨损量,这符合“Vickers 35VQ25A”叶轮泵试验(按照“Vickers”M-2950-S)中的“Vickers”标准M-2950-S。
在本发明的另一种优选实施方案中,所述润滑油组合物具有相当于不超过10mg的叶轮磨损量及相当于不超过50mg的环磨损量,这符合“Vickers 35VQ25A”叶轮泵试验(按照“Vickers”M-2950-S)中的“General Motors”标准LS-2LH.03.04.06。
本发明的润滑油组合物可以用作液压油组合物、压缩机油组合物、透平机油组合物、轴承油组合物和/或齿轮油组合物。
对本发明的润滑油组合物中的基础油没有特别的限制。所述基础油优选为基于石油的、基于合成烃的和/或基于酯的。
所述基础油的优选物理特性如下:
运动粘度为2-680mm2/s(40℃),优选为5-320mm2/s(40℃),以及更优选为8-220mm2/s(40℃);
总硫含量(wt%)为0-1%,并且优选为0-0.3%;
总氮含量(重量ppm)为0-100ppm,并且优选为0-30ppm;和/或
苯胺点为80-130℃,并且优选为100-125℃。
可以用于本发明的基于石油的润滑油基础油包括溶剂纯化的基础油、加氢纯化的基础油以及深度加氢裂化的基础油。这些基础油可以单独或以混合物的形式应用。
深度加氢裂化的基础油是粘度指数至少为130(通常为145-155)的基础油。所述基础油可以通过如下方法得到:取得已经通过溶剂脱蜡分离的原料蜡(疏松石蜡),在催化剂存在时使所述蜡加氢(催化降解)从而使直链链烷烃转化为支链链烷烃。另外,所述基础油可以通过如下方法得到:将由天然气(甲烷等)经气体形成过程(部分氧化)得到的氢和一氧化碳作为原料,使所述原料进行Fischer-Tropsch聚合反应以得到重的直链链烷烃,然后通过上述催化降解对所述重的直链链烷烃进行改性。
用于本发明的基于合成烃的基础油可以是烯烃低聚物,所述烯烃低聚物是由选自具有3-15个碳原子,优选为4-12个碳原子的直链或支链烯烃单体均聚或共聚得到的。
在本发明中,基于石油的基础油或基于合成烃的基础油可以单独或以混合物的形式应用。
三芳基磷酸酯是早就已知的在相对温和的条件下应用的耐磨剂,正如在US 5922657(对应于日本待审专利申请H10-67993)中所公开的,已知β-二硫代磷酰化丙酸能改进特压性能,并防止齿轮咬死。
但在本发明中,通过组合应用上述耐磨组分三芳基磷酸酯,在苛刻的高压/高负荷条件下的耐磨性能可以得到改进,与β-二硫代磷酰化丙酸单独应用时所达到的耐磨性能等同或更好。
除了上述必要组分外,如果需要的话,在本发明中也可以加入各种其它常用的添加剂,从而进一步改进其性能。
因此,可以加入公知的润滑油添加剂如抗氧化剂、防锈剂、金属去活化剂、清洁剂分散剂、耐磨剂、特压添加剂、磨擦调节剂、流点抑制剂、粘度指数改进剂、抗乳化剂和消泡剂。
例如,胺基抗氧化剂的例子包括二烷基二苯基胺如p,p′-二辛基二苯基胺(由Seiko Kagaku以商品名“Nonflex OD-3”生产)、p,p′-二-α-甲基苄基二苯基胺和N-p-丁基苯基-N-p′-辛基苯基胺;单烷基二苯基胺如单-t-丁基二苯基胺和单辛基二苯基胺;双(二烷基苯基)胺如双(2,4-二乙基苯基)胺和双(2-乙基-4-壬基苯基)胺;烷基苯基-1-萘基胺如辛基苯基-1-萘基胺和N-t-十二烷基苯基-1-萘基胺;芳基萘基胺如1-萘基胺、苯基-1-萘基胺、苯基-2-萘基胺、N-己基苯基-2-萘基胺和N-辛基苯基-2-萘基胺;亚苯基二胺如N,N′-二异丙基-p-亚苯基二胺和N,N′-二苯基-p-亚苯基二胺;以及吩噻嗪类如吩噻嗪(由HodogayaKagaku生产的吩噻嗪)和3,7-二辛基吩噻嗪。
硫基抗氧化剂的例子包括二烷基硫酸酯类如双十二烷基硫酸酯和双十八烷基硫酸酯;硫代二丙酸酯如双十二烷基硫代二丙酸酯、双十八烷基硫代二丙酸酯、双肉豆蔻基硫代二丙酸酯和十二烷基十八烷基硫代二丙酸酯以及2-巯基苯并咪唑。
酚基抗氧化剂的例子包括2,6-二-t-丁基-4-烷基酚类如2-t-丁基苯酚、2-t-丁基-4-甲基苯酚、2-t-丁基-5-甲基苯酚、2,4-二-t-丁基苯酚、2,4-二甲基-6-t-丁基苯酚、2-t-丁基-4-甲氧基苯酚、3-t-丁基-4-甲氧基苯酚、2,5-二-t-丁基对苯二酚(由Kawaguchi Kagaku以商品名“AntageDBH”生产)、2,6-二-t-丁基苯酚、2,6-二-t-丁基-4-甲基苯酚和2,6-二-t-丁基-4-乙基苯酚;2,6-二-t-丁基-4-烷氧基酚类如2,6-二-t-丁基-4-甲氧基苯酚和2,6-二-t-丁基-4-乙氧基苯酚;烷基-3-(3,5-二-t-丁基-4-羟基苯基)丙酸酯类如3,5-二-t-丁基-4-羟基苄基巯基辛基乙酸酯、n-十八烷基-3-(3,5-二-t-丁基-4-羟基苯基)丙酸酯(由Yoshitomi Seiyaku以商品名“Yoshinox SS”生产)、n-十二烷基-3-(3,5-二-t-丁基-4-羟基苯基)丙酸酯和2′-乙基己基-3-(3,5-二-t-丁基-4-羟基苯基)丙酸酯;2,6-二-t-丁基-α-二甲基氨基-p-甲酚;2,2′-亚甲基二(4-烷基-6-t-丁基苯酚)类如2,2′-亚甲基二(4-甲基-6-t-丁基苯酚)(由Kawaguchi Kagaku以商品名“Antage W-400”生产)和2,2′-亚甲基二(4-乙基-6-t-丁基苯酚)(由Kawaguchi Kagaku以商品名“Antage W-500”生产);双酚类如4,4′-亚丁基二(3-甲基-6-t-丁基苯酚)(由Kawaguchi Kagaku以商品名“Antage W-300”生产)、4,4′-亚甲基二(2,6-二-t-丁基苯酚)(由LaportePerformance Chemicals以商品名“Ionox 220AH”生产)、4,4′-二(2,6-二-t-丁基苯酚)、2,2-(二-p-羟基苯基)丙烷(双酚A)、2,2-二(3,5-二-t-丁基-4-羟基苯基)丙烷、4,4′-环-亚己基双(2,6-t-丁基苯酚)、1,6己二醇双[3-(3,5-二-t-丁基-4-羟基苯基)丙酸酯](由Ciba Speciality Chemicals以商品名“Irganox L109”生产)、三甘醇双[3-(3-t-丁基-4-羟基-5-甲基苯基)丙酸酯](由Yoshitomi Seiyaku以商品名“Tominox 917”生产)、2,2′-硫-[二乙基-3-(3,5-二-t-丁基-4-羟基苯基)丙酸酯](由Ciba SpecialityChemicals以商品名“Irganox L115”生产)、3,9-二{1,1-二甲基-2-[3-(3-t-丁基-4-羟基-5-甲基苯基)丙酰基氧]乙基}-2,4,8,10-四氧螺环[5,5]十一烷(由Sumitomo Kagaku以商品名“Sumilyzer GA80”生产)、4,4′-硫双(3-甲基-6-t-丁基苯酚)(由Kawaguchi Kagaku以商品名“Antage RC”生产)、以及2,2′-硫双(4,6-二-t-丁基)间苯二酚;多酚类如四[亚甲基-3-(3,5-二-t-丁基-4-羟基苯基)丙酸酯]甲烷(由CibaSpeciality Chemicals以商品名“Irganox L101”生产)、1,1,3-三(2-甲基-4-羟基-5-t-丁基苯基)-丁烷(由Yoshitomi Seiyaku以商品名“Yoshinox930”生产)、1,3,5-三甲基-2,4,6-三(3,5-二-t-丁基-4-羟基苄基)苯(由CibaSpeciality Chemicals以商品名“Irganox 1330”生产)、双-[3,3′-二-(4′-羟基-3′-t-丁基-苯基)丁酸]乙二醇酯、2-(3′,5′-二-t-丁基-4-羟基苯基)甲基-4-(2″,4″-二-t-丁基-3″-羟基苯基)甲基-6-t-丁基苯酚和2,6-双(2′-羟基-3′-t-丁基-5′-甲基苄基)-4-甲基苯酚;以及酚醛缩合物如p-t-丁基苯酚和甲醛的缩合物以及p-t-丁基苯酚和乙醛的缩合物。
磷基抗氧化剂的例子包括三芳基亚磷酸酯类如三苯基亚磷酸酯和三甲苯基亚磷酸酯、三烷基亚磷酸酯类如三辛基亚磷酸酯和三癸基亚磷酸酯以及三(十二烷基)三硫代亚磷酸酯。
这些抗氧化剂可以单独应用或者多种组合应用,其加入量以100重量份的基础油为基准,可以适宜地为0.01-2.0重量份。
可用于本发明的润滑油组合物中的金属去活化剂的例子包括苯并三唑和苯并三唑衍生物,例如4-烷基苯并三唑类如4-甲基苯并三唑和4-乙基苯并三唑、5-烷基苯并三唑类如5-甲基苯并三唑和5-乙基苯并三唑、1-烷基苯并三唑类如1-二辛基氨基甲基-2,3-苯并三唑和1-烷基甲苯三唑类如1-二辛基氨基甲基-2,3-甲苯三唑;苯并咪唑以及苯并咪唑衍生物,例如2-(烷基二硫代)苯并咪唑类如2-(辛基二硫代)苯并咪唑、2-(癸基二硫代)苯并咪唑和2-(十二烷基二硫代)苯并咪唑、和2-(烷基二硫代)-甲苯咪唑如2-(辛基二硫代)甲苯咪唑、2-(癸基二硫代)甲苯咪唑、2-(十二烷基二硫代)甲苯咪唑;吲唑和吲唑衍生物,例如甲苯吲唑类如4-烷基-吲唑和5-烷基吲唑;苯并噻唑及苯并噻唑衍生物,例如2-(烷基二硫代)苯并噻唑类如2-巯基苯并噻唑衍生物(由ChiyodaKagaku以商品名“Thiolite B-3100”生产)、2-(己基二硫代)苯并噻唑和2-(辛基二硫代)苯并噻唑、2-(烷基二硫代)甲苯噻唑类如2-(己基二硫代)-甲苯噻唑和2-(辛基二硫代)-甲苯噻唑、2-(N,N-二烷基二硫代氨基甲酰基)苯并噻唑如2-(N,N-二乙基二硫代氨基甲酰基)苯并噻唑、2-(N,N-二丁基二硫代氨基甲酰基)苯并噻唑和2-(N,N-二己基二硫代氨基甲酰基)苯并噻唑,以及2-(N,N-二烷基二硫代氨基甲酰基)甲苯噻唑如2-(N,N-二乙基二硫代氨基甲酰基)甲苯噻唑、2-(N,N-二丁基二硫代氨基甲酰基)甲苯噻唑和2-(N,N-二己基二硫代氨基甲酰基)甲苯噻唑;苯并噁唑衍生物,例如2-(烷基二硫代)苯并噁唑如2-(辛基二硫代)苯并噁唑、2-(癸基二硫代)苯并噁唑和2-(十二烷基二硫代)苯并噁唑和2-(烷基二硫代)甲苯噁唑如2-(辛基二硫代)甲苯噁唑、2-(癸基二硫代)甲苯噁唑和2-(十二烷基二硫代)甲苯噁唑,噻二唑衍生物,例如2,5-双(烷基二硫代)-1,3,4-噻二唑、2,5-双(庚基二硫代)-1,3,4-噻二唑、2,5-双(壬基二硫代)-1,3,4-噻二唑、2,5-双(十二烷基二硫代)-1,3,4-噻二唑和2,5-双(十八烷基二硫代)-1,3,4-噻二唑、2,5-双(N,N-二烷基二硫代氨基甲酰基)-1,3,4-噻二唑如2,5-双(N,N-二乙基二硫代氨基甲酰基)-1,3,4-噻二唑、2,5-双(N,N-二丁基二硫代氨基甲酰基)-1,3,4-噻二唑、2,5-双(N,N-二辛基二硫代氨基甲酰基)-1,3,4-噻二唑和2-N,N-二烷基二硫代氨基甲酰-5-巯基-1,3,4-噻二唑如2-N,N-二丁基二硫代氨基甲酰基-5-巯基-1,3,4-噻二唑和2-N,N-二辛基二硫代氨基甲酰基-5-巯基-1,3,4-噻二唑;以及三唑衍生物,例如1-烷基-2,4-三唑如1-二辛基氨基甲基-2,4-三唑。
这些金属去活化剂可以单独应用或者多种组合应用,其加量入以100重量份的基础油为基准,可以适宜地为0.005-0.5重量份。
可以应用的消泡剂的例子包括有机硅酸酯如二甲基聚硅氧烷、二乙基硅酸酯和氟硅氧烷,以及非硅氧烷消泡剂如聚烷基丙烯酸酯。它们可以单独或多种组合应用,其加入量以100重量份的基础油为基准,可以适宜地为0.0001-0.1重量份。
粘度指数改进剂的例子包括非分散剂型粘度指数改进剂例如聚甲基丙烯酸酯和烯烃共聚物如乙烯/丙烯共聚物及苯乙烯/二烯共聚物,以及分散剂型粘度指数改进剂如通过使上述物质与含氮单体一起共聚所得到的那些。其加入量以100重量份的基础油为基准,可以适宜地为0.05-20重量份。
流点抑制剂的例子包括基于聚甲基丙烯酸酯的聚合物。其加入量以100重量份的基础油为基准,可以适宜地为0.01-5重量份。
清洁剂分散剂的例子包括金属基清洁剂,例如中性或碱性的碱土金属磺酸盐、碱土金属酚盐和碱土金属水杨酸盐,以及无灰的分散剂,例如由烷烯基琥珀酸酰亚胺、烷烯基琥珀酸酯或其硼化合物、硫化合物等得到的改性产品。它们可以单独应用或多种组合应用,其加入量以100重量份的基础油为基准,可以适宜地为0.01-1重量份。
特压添加剂和磨擦调节剂的例子包括硫基特压添加剂如二烷基硫化物、二苄基硫化物、二烷基多硫化物、二苄基二硫化物、烷基硫醇、二苯并噻吩和2,2′-二硫代二(苯并噻唑);磷基特压添加剂如三烷基磷酸酯、三烷基膦酸酯、三烷基亚磷酸酯、三芳基亚磷酸酯、二烷基氢亚磷酸酯、三烷基三硫代亚磷酸酯及三芳基硫代磷酸酯;脂族磨擦调节剂如脂肪酸酰胺和脂肪酸酯;胺基磨擦调节剂如伯至叔烷基胺以及烷基胺的烯化氧加合物;以及特压添加剂如烷基二硫代磷酸锌。这些特压添加剂和磨擦调节剂可以单独应用或多种组合应用,其加入量以100重量份的基础油为基准,可以适宜地为0.05-5.0重量份。
可以应用的防锈剂的例子包括N-烷基肌氨酸(sarcosinic acids)、烷基化的苯氧基乙酸酯、咪唑啉、由King Industry生产的“KX1031”及其碱土金属盐及其胺盐、日本待审专利申请H6-200268所公开的N-酰基-N-烷氧基烷基天冬酰胺酯、EP-A-0801116所公开的磷酸酯的碱土金属盐和基于烷烯基琥珀酸酯的防锈剂。这些防锈剂可以单独应用或多种组合应用,其加入量以100重量份的基础油为基准,可以适宜地为0.005-1.0重量份。
抗乳化剂(用于打破乳液从而使其分离为两个液体层)的例子包括通常用作润滑油添加剂的公知物质,例如基于聚亚烷基二醇的非离子性表面活性剂如聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚和聚氧乙烯烷基萘基醚。其加入量以100重量份的基础油为基准,可以适宜地为0.0005-0.5重量份。
使用本发明的润滑油组合物作为上述液压油组合物是特别合适的。但所述润滑油组合物也可以按其它方式应用,例如用作压缩机油组合物、透平机油组合物、轴承油组合物和齿轮油组合物。
下面将参照如下实施例描述本发明,这些实施例不以任何方式限制本发明的范围。
实施例:
下面通过液压油工作实例具体描述本发明。
将40℃下运动粘度为31mm2/s的加氢纯化基础油用作基础油,并且加入下示组分以得到基础润滑油组合物。
向这种基础润滑油组合物A(表1)中加入表2、3和4所示的耐磨剂,从而产生在40℃下运动粘度为32mm2/s的试验油。
在工作例1和2以及比较例1-10的实验油中,各种添加剂组分的量以相对于试验油的重量份给出。
表1
基础润滑油组合物A | |
加氢纯化的基础油:40℃时运动粘度为31mm2/s | 99.15重量份 |
抗氧化剂:(由Echiru以商品名Hitec 4733”生产) | 0.5重量份 |
金属去活化剂:(由Ciba Speciality Chemicals以商品名Irgamet 39”生产) | 0.05重量份 |
流点抑制剂:(由Toho Kagaku Kogyo以商品名“Lubran141”生产) | 0.3重量份 |
通过比较,按表2和3所示的比例制备本发明的润滑油组合物(工作例1和2)及不包含本发明组合物的常规耐磨组合物(比较例1-6)。
对工作例和比较例的组合物按下文所描述进行叶轮泵实验,结果示于表5中。
另外,为了进行比较,针对应用表4所示的无锌无灰耐磨液压油(比较例7和8)得到的工业产品也进行相同的性能评价实验,这些结果也示于表5中。应该注意的是针对工作例和比较例进行的性能实验的方法如下。
IP 281“Vickers V104C”叶轮泵试验
为了评价在叶轮泵中试验油的耐磨性能,应用“Vickers V104C”泵在压力为140kgf/cm2、1500rpm、油温为65℃下进行泵试验250h,并在试验后测量叶轮和环的磨损量。用于耐磨液压油的DIN 51524(第二部分)标准为叶轮和环上的总磨损量相当于不超过150mg。
“Vickers 35VQ-25A”叶轮泵试验
为了评价在高压、高速和高温下在叶轮泵中试验油的耐磨性能,应用“Vickers 35VQ-25A”泵在压力为210kgf/cm2、2400rpm、油温为93℃下进行泵试验50h,并在试验后测量叶轮和环的磨损量。“Vickers”M-2950-S标准为叶轮磨损量相当于不超过15mg,环磨损量相当于不超过75mg。
“General Motors”LS-2 LH.03.04.06标准更为严格:叶轮磨损量相当于不超过10mg,环磨损量相当于不超过50mg。
表2
实施例 | 比较例1 | 比较例2 | 比较例3 | 比较例4 |
基础润滑油组合物A(wt%) | 100 | 99.5 | 99.0 | 99.0 |
组分1:β-二硫代磷酰化丙酸 | - | - | - | - |
组分2:三烷基苯基磷酸酯 | - | 0.5 | 1.0 | - |
三苯基硫代磷酸酯 | - | - | - | 1.0 |
表3
实施例 | 工作例1 | 工作例2 | 比较例5 | 比较例6 |
基础润滑油组合物A(wt%) | 99.18 | 99.18 | 99.975 | 99.48 |
组分1:β-二硫代磷酰化丙酸 | 0.02 | - | 0.025 | 0.2 |
组分2:三烷基苯基磷酸酯 | 0.8 | 0.8 | - | - |
组分3:β-二硫代磷酰化丙酸 | - | 0.02 | - | - |
三苯基硫代磷酸酯 | - | - | - | 0.5 |
在上表2和3中,组分1为β-二硫代磷酰化丙酸,其由通式(1)表示,其中R1为异丁基,R2为甲基。
在表2和3中的组分2为以商品名“Reofos 65”ex.Ajinomoto出售的三芳基磷酸酯。
组分3为β-二硫代磷酰化丙酸,其由通式(1)表示,其中R1为异丁基,R2为氢。
在表3中的三苯基硫代磷酸酯为以商品名“Irgalube TPPT”ex.Ciba.出售的物质。
表4
工业耐磨液压油 | 比较例7 | 比较例8 |
磷含量(wt%) | 0.163 | 0.092 |
硫含量(wt%) | - | 0.020 |
40℃下运动粘度cSt100℃下运动粘度cSt | 30.65.46 | 30.45.29 |
注:所应用的所有工业耐磨液压油都不含锌。
表5
实施例 | 比较例1 | 比较例2 | 比较例3 | 比较例4 | 比较例5 | 比较例6 | 比较例7 | 比较例8 | 工作例1 | 工作例2 |
IP 281“Vickers V104C”叶轮泵实验叶轮磨损量(mg)环磨损量(mg)总磨损量(mg) | 49415464 | 37213250 | 86573 | 63440 | 336 | 8159167 | 454085 | 93645 | 235 | 314 |
“Vickers 35VQ25A”叶轮泵实验叶轮磨损量(mg)环磨损量(mg)总磨损量(mg) | --- | --- | 38606644 | 8108116 | 3710 | --- | 22351373 | 39755794 | 235 | 224 |
比较例1和2在“Vickers V104C”叶轮泵试验中不具有足够的耐磨性能,并且不具有通过德国标准German Standard DIN 51524(第二部分)所要求的耐磨性能。比较例3和4在“Vickers V104C”叶轮泵试验中确实通过了德国标准German Standard DIN 51524(第二部分),但在“Vickers 35VQ25A”叶轮泵试验中不具有足够的耐磨性能,并且没有通过“Vickers”M-2950-S标准或“General Motors”LS-2 LH.03.04.06标准。比较例7和8在V104C叶轮泵试验中表现出足够的耐磨性能,通过了德国标准German Standard DIN 51524(第二部分),但它们的耐磨性能不足以通过“Vickers”M-2950-S标准或“General Motors”LS-2LH.03.04.06标准。
从表3所示的组合物以及表5所示的结果可以很清楚地看出,本发明的润滑油组合物(工作例1和2)具有很好的耐磨性能,在“Vickers”V104C和35VQ25A叶轮泵试验中足以通过德国标准German StandardDIN 51524(第二部分)、“Vickers”M-2950-S标准和“General Motors”LS-2 LH.03.04.06标准,并且它们的润滑油性能足以在高压应用中用作液压油。与工作例1和2相比,比较例5在两个试验中均显示出更高的总磨损量。
但当不应用本发明的添加剂组合物(比较例)并且为工业上不含锌的液压油以及锌基液压油的情况下,其耐磨性能和特压性能都很差,并且对于趋向于小型化并且在高速、高压和高精度下工作的现代机器,将这些油用作润滑油时会有问题。
比较例9和10
在β-二硫代磷酰化丙酸酸中的R2为氢或甲基时,为了考察其热氧化性稳定性是否更好,进行比较例9和10的实验。比较例9和10的组合物及结果示于表6中。
热氧化稳定性实验按下述过程进行:分别向250ml烧杯中加入200ml比较例9和10的试验油,所述油通过组合β-二硫代磷酰化丙酸和抗氧化剂及防锈剂得到,将已经用#240氧化铝抛光纸抛光、洗涤并干燥了的直径为0.6mm、长度为7.6mm的钢样品和铜样品切断,并且将试验油涂到上面,将试验油在140℃的烘箱中进行热氧化性劣化处理336h,并在试验后将试验油用0.8μm孔径的过滤器进行吸滤,测量所得到的渣油量、铜样品和钢样品的外观以及试验油的颜色(ASTM D1500)。
表6
比较例9 | 比较例10 | |
加氢纯化的基础油B*1 | 99.74 | 99.74 |
抗氧化剂*2 | 0.10 | 0.10 |
防锈剂*3 | 0.01 | 0.01 |
β-二硫代磷酰化丙酸R1:异丁基R2:氢 | 0.15 | - |
β-二硫代磷酰化丙酸R1:异丁基R2:甲基 | - | 0.15 |
试验油的颜色热氧化稳定性试验油的颜色铜的外观钢的外观渣油量(mg) | L 0.5L 5.0无锈不变10.3 | L 0.5L 4.5无锈不变0.0 |
*1加氢纯化的基础油B:运动粘度为32 Cst(40℃),硫含量不超过5ppm,粘度指数为110
*2抗氧化剂:商品名为“Irganox L135”,由Ciba SpecialityChemicals生产
*3防锈剂:商品名为“IRGAMET 39”,由Ciba Specialitv Chemicals生产
从表6所示的热氧化稳定性实验的结果可以清楚地看出,与比较例9中的化合物相比,比较例10的化合物颜色变化更少且产生更少的渣油,也就是说更为稳定,其中比较例10的化合物β-二硫代磷酰化丙酸的α-碳上的一个氢原子已经被烷基所取代,而比较例9的化合物中没有烷基取代α-碳上的氢原子。如果在α-碳上的烷基取代基有太多的碳原子,则耐磨性能会劣化,因此为了同时达到热氧化稳定性和耐磨性能,烷基取代基最优选为甲基。
本发明的优点
从环境和安全角度考虑,本发明的润滑油组合物不含或者几乎不含成灰物质如二烷基二硫代磷酸锌;对各种机器元件来说,所形成的耐磨润滑油组合物即使当这些机器元件在苛刻的高压、高速和高负荷条件下应用时仍具有非常好的耐磨性能。因此针对最近开发的高速、高压和高精度的工业机器来说,本发明的润滑油组合物为保证设备的长期可靠性而提供润滑油是极为有效的。
Claims (10)
1.一种润滑油组合物,含有β-二硫代磷酰化丙酸(A)、三芳基磷酸酯(B)及包括矿物油和/或合成油的基础油。
2.权利要求1的润滑油组合物,其中β-二硫代磷酰化丙酸(A)由如下通式(1)表示:
S=P(-OR1)2SCH2CH(R2)COOH (1)
其中R1可以相同或不同,代表具有3-8个碳原子的支链烷基,并且R2代表氢原子或具有1-4个碳原子的烷基。
3.权利要求2的润滑油组合物,其中R2为甲基、乙基或氢。
4.权利要求1-3任一项的润滑油组合物,其中β-二硫代磷酰化丙酸(A)选自3-(O,O-二异丙基二硫代磷酰基)丙酸、3-(O,O-二异丙基二硫代磷酰基)-2-甲基-丙酸、3-(O,O-二异丁基二硫代磷酰基)丙酸和3-(O,O-二异丁基二硫代磷酰基)-2-甲基-丙酸。
5.权利要求1-4任一项的润滑油组合物,其中相对于润滑油组合物的总量来说,结合了0.001-1.0wt%的β-二硫代磷酰化丙酸(A)。
6.权利要求1-5任一项的润滑油组合物,其中相对于润滑油组合物的总量来说,结合了0.001-0.5wt%的β-二硫代磷酰化丙酸(A)。
7.权利要求1-6任一项的润滑油组合物,其中三芳基磷酸酯(B)由如下通式(2)表示:
O=P(-O-R3)3 (2)
其中各R3独立地为苯基或带有1-9个碳原子烷基的苯基。
8.权利要求1-7任一项的润滑油组合物,其中相对于润滑油组合物的总量来说,结合了0.05-10wt%的三芳基磷酸酯(B)。
9.权利要求1-8任一项的润滑油组合物,其中相对于润滑油组合物的总量来说,结合了0.05-5wt%的三芳基磷酸酯(B)。
10.权利要求1-9任一项的润滑油组合物,其用作液压油组合物、压缩机油组合物、透平机油组合物、轴承油组合物和/或齿轮油组合物。
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JP2001000093 | 2001-01-04 | ||
JP93/2001 | 2001-01-04 | ||
JP57423/2001 | 2001-03-01 | ||
JP2001057423A JP4789335B2 (ja) | 2001-01-04 | 2001-03-01 | 耐摩耗性潤滑油組成物 |
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CN 200610108765 Division CN1955271A (zh) | 2001-01-04 | 2002-01-02 | 润滑油组合物 |
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US (1) | US20040053794A1 (zh) |
EP (1) | EP1354023A2 (zh) |
JP (1) | JP4789335B2 (zh) |
KR (1) | KR100850654B1 (zh) |
CN (1) | CN1484688A (zh) |
AU (1) | AU2002224973B2 (zh) |
BR (1) | BR0206298A (zh) |
CA (1) | CA2433447A1 (zh) |
WO (1) | WO2002053687A2 (zh) |
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-
2001
- 2001-03-01 JP JP2001057423A patent/JP4789335B2/ja not_active Expired - Lifetime
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2002
- 2002-01-02 KR KR1020037009000A patent/KR100850654B1/ko not_active IP Right Cessation
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- 2002-01-02 BR BR0206298-4A patent/BR0206298A/pt not_active Application Discontinuation
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- 2002-01-02 CN CNA028034783A patent/CN1484688A/zh active Pending
- 2002-01-02 US US10/250,427 patent/US20040053794A1/en not_active Abandoned
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CN112646631A (zh) * | 2020-12-22 | 2021-04-13 | 北京元泰达环保科技有限公司 | 具有高抗氧化性的润滑油制备方法 |
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JP2002265971A (ja) | 2002-09-18 |
WO2002053687A3 (en) | 2002-09-19 |
AU2002224973B2 (en) | 2006-08-31 |
KR100850654B1 (ko) | 2008-08-07 |
EP1354023A2 (en) | 2003-10-22 |
JP4789335B2 (ja) | 2011-10-12 |
WO2002053687A2 (en) | 2002-07-11 |
BR0206298A (pt) | 2004-01-13 |
CA2433447A1 (en) | 2002-07-11 |
US20040053794A1 (en) | 2004-03-18 |
KR20030065589A (ko) | 2003-08-06 |
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