CN1315998C - 润滑油组合物 - Google Patents
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Abstract
一种润滑油组合物,所述的润滑油组合物含有:a)粘度指数为至少95的润滑粘度的油;b)至少一种钙去污剂;c)至少一种油溶性的含钼化合物;d)至少一种不含氮的无灰有机摩擦改进剂;以及e)至少一种二烃基二硫代磷酸金属盐化合物,所述的组合物的Noack挥发性为约15%(重)或更小,含有约0.05%~0.6%(重)来自钙去污剂的钙,至少10ppm来自含钼化合物的钼和最高约0.1%(重)来自二烃基二硫代磷酸金属盐化合物的磷。
Description
技术领域
本发明涉及润滑油组合物。更具体地说,本发明涉及这样的润滑油组合物,它们同时有改进的低温阀系磨损性能、与常用于现代内燃发动机密封件的含氟弹性体有极好的相容性以及改进的燃料经济性。
背景技术
用于润滑内燃发动机的润滑油组合物含有润滑粘度的基础油或这样的油的混合物,以及用来改进基础油性能特性的添加剂。例如,添加剂用来改进去污力、降低发动机磨损、提供热和氧化稳定性、减少油耗、抑制腐蚀、作为分散剂和减少摩擦损失。某些添加剂提供多种效益,例如分散剂-粘度指数改进剂。另一些添加剂虽然能改进润滑油的一种特性,但对其他特性有不良的影响。因此,为了提供有最佳整体性能的润滑油,必需表征和了解可得到的各种添加剂的所有影响,并仔细地均衡润滑油的添加剂含量。
在许多专利和文献(例如:U.S.专利No.4164473;4176073;4176074;4192757;4248720;4201683;4289635和4479883)中已提出,油溶性的含钼化合物适宜用作润滑油的添加剂。具体地说,含钼化合物特别是二硫代氨基甲酸钼加到油中可得到改进边界摩擦特性的油品,小型试验证明含有这样的含钼化合物的油品的摩擦系数通常低于含有机摩擦改进剂的油品。摩擦系数的这一下降可得到改进的抗磨性,并在汽油发动机或柴油发动机中得到高的燃料经济性,包括短期和长期燃料经济性(燃料经济性保留性)。为了达到抗磨效果,通常将约350~2000ppm钼的含钼化合物加到油品中。虽然含钼化合物是有效的抗磨剂并可进一步提供燃料经济效益,但这样的含钼化合物相对于更传统的不含金属(无灰)的有机摩擦改进剂是昂贵的。
U.S.专利No.6300291公开了一种含有规定粘度指数的基础油、钙基去污剂、二烃基二硫代磷酸锌(ZDDP)抗磨剂、含钼化合物和含氮摩擦改进剂的、有规定的Noack挥发性的润滑油组合物。含钼化合物的用量为使配方润滑剂中钼含量达到350ppm的量。与仅含有含钼化合物的组合物相比,该专利所公开的材料提供了更高的燃料经济效益。
现代内燃发动机包含许多由含氟弹性体例如VitonTM制得的垫片和其他密封件。人们怀疑含氮的添加剂有时会造成这样的材料损坏。所以,希望寻找这样一种能提供燃料经济效益,显示有极好的抗磨特性,相对低成本以及不含含氮摩擦改进剂的润滑油组合物。
现已发现,少量的一种或多种油溶性的含钼化合物与无灰的不含氮的有机摩擦改进剂、ZDDP和钙去污剂的组合可得到低成本的润滑油,它有可证明的燃料经济效益;极好的抗磨特性;以及对VitonTM和类似的含氟弹性体制成的发动机密封件有较小的不良影响。
本发明还提供许多另外的优点,从下面的描述中这些优点将变得很明显。
发明内容
根据第一方面,本发明提供一种有极好低温阀系磨损性能、改进的燃料经济性保留性能和与含氟弹性体为基础的发动机密封件相容性改进的润滑油组合物,所述的组合物含有粘度指数(VI)为至少95的润滑粘度基础油;其用量为可向该组合物引入0.05%~0.6%(重)钙的含钙去污剂;其用量为可向该组合物引入0.1%(重)磷(1000ppm)的二烃基二硫代磷酸金属盐;其其用量为足以向该组合物引入10ppm钼的至少一种含钼化合物;以及有效量的至少一种不含氮的无灰有机摩擦改进剂;所述组合物的Noack挥发性小于15%。
根据第二方面,本发明涉及一种改进内燃发动机的燃料经济性、密封件寿命和/或磨损特性的方法。所述的方法包括以下步骤:用第一方面的润滑油组合物润滑内燃发动机,以及操作发动机。
根据第三方面,本发明涉及第一方面的润滑油组合物在改进内燃发动机的燃料经济性、密封件寿命和/或磨损特性方面的应用。
参考以下的描述,将理解本发明的其他目的、优点和特性。
具体实施方式
润滑粘度的油可为至少一种选自I类、II类或III类基本油料或上述基本油料的基础油调合油中的一种油,条件是基础油或基础油调合油的粘度为至少95,并使润滑油组合物的配方有小于15%的Noack挥发性,Noack挥发性即为按ASTM D5880步骤在250℃1小时后测定的油品质量损失百分数。此外,润滑粘度的油可为一种或多种IV类或V类基本油料或它们的组合物或含有一种或多种IV类或V类基本油料与一种或多种I类、II类和/或III类基本油料组合的基础油混合物。
对于燃料经济性保留性来说,最优选的油品是:
(a)III类基础油与I类或II类基本油料的基础油调合油,其中组合物的粘度指数为至少110;或
(b)III类、IV类或V类基本油料或一种以上III类、IV类或V类基本油料的基础油调合油,其中粘度指数为约120~140。
本发明中基本油料和基础油的定义与美国石油学会(API)出版物“Engine Oil Licensing and Certification System”,Industry ServicesDepartment,Fourteenth Edition,December 1996,Addendum1,December 1998中的相同。所述的出版物将基础油分类如下:
a)I类基础油含有小于90%饱和烃和/或大于0.03%硫,粘度指数大于或等于80且小于120,用表E-1规定的试验方法测定。
b)II类基础油含有大于或等于90%饱和烃和小于或等于0.03%硫,粘度指数大于或等于80且小于120,用表E-1规定的试验方法测定。
c)III类基础油含有大于或等于90%饱和烃和小于或等于0.03%硫,粘度指数大于或等于120,用表E-1规定的试验方法测定。
d)IV类基础油为聚α烯烃(PAO)。
e)V类基础油包括I类、II类III类或IV类中不包括的所有其他基础油。
表E-1基础油的分析方法
性质 | 试验方法 |
饱和烃 | ASTM D 2007 |
粘度指数 | ASTM D 2270 |
硫 | ASTM D 2622 |
ASTM D 4294 | |
ASTM D 4927 | |
ASTM D 3120 |
对于本发明的润滑油组合物来说,在润滑油组合物中,具有摩擦改进性和/或抗磨性的任何适合的油溶性的有机含钼化合物都可使用。作为这样的油溶性的有机含钼化合物的例子,可提到的是二硫代氨基甲酸盐、二硫代磷酸盐、二硫代次磷酸盐、黄原酸盐、硫代黄原酸盐、硫化物等,以及它们的混合物。特别优选的是二硫代氨基甲酸钼、二烷基二硫代磷酸钼、烷基黄原酸钼和烷基硫代黄原酸钼。
含钼化合物可为单核的、双核的、三核的或四核的。双核的和三核的含钼化合物是优选的。含钼化合物优选为有机含钼化合物。更优选的是,含钼化合物选自二硫代氨基甲酸钼(MoDTC)、二硫代磷酸钼、二硫代次磷酸钼、黄原酸钼、硫代黄原酸钼、硫化钼及其混合物。最优选的是,含钼化合物以二硫代氨基甲酸钼或三核的有机含钼化合物存在。
此外,含钼化合物可为酸性的含钼化合物。这些化合物将与碱性的含氮化合物反应,正如按ASTM试验D-664或D-2896滴定法测量的,它们通常为六价的。包括钼酸、钼酸铵、钼酸钠、钼酸钾和其他碱金属钼酸盐和其他钼盐,例如钼酸氢钠、MoOCl4、MoO2Br2、Mo2O3Cl6、三氧化钼,或类似的酸性含钼化合物。或者,本发明的组合物所含的钼可由含有碱性含氮化合物的钼/硫配合物提供,例如在U.S.专利No.4263152;4285822;4283295;4272387;4265773;4261843;4259195;4259194和WO94/06897中公开的。
在适用于本发明组合物中的含钼化合物中,包括下式的有机含钼化合物
Mo(ROCS2)4和
Mo(RSCS2)4
式中R有机基团选自烷基、芳基、芳烷基和烷氧烷基,通常有1~30个碳原子、优选2~12个碳原子,最优选2~12个碳原子的烷基。特别优选的是二烃基二硫代氨基甲酸钼。
一类适用于本发明润滑油组合物的优选有机含钼化合物为三核的含钼化合物,特别是分子式Mo3SkLnQz的那些三核含钼化合物及其混合物,其中L独立选自有足够碳原子数的有机基团的配体,以使化合物在油中可溶或可分散,n为1~4,k为4~7,Q选自中性给电子化合物,例如水、胺类、醇类、膦类和醚类,z为0~5,并包括非化学计量数值。在所有配体的有机基团中应至少存在21个总碳原子数,例如至少25、至少30或至少35个碳原子。
配体独立选自以下基团
和它们的混合物,其中X、X1、X2和Y独立选自氧和硫,R1、R2和R独立选自氢和相同的或不同的有机基团。优选地,有机基团为烃基例如烷基(例如其中连接到配体其余部分的碳原子为伯碳原子或仲碳原子)、芳基、取代的芳基和醚基。更优选的是,每一配体有相同的烃基。
术语“烃基”表示碳原子直接连接到配体其余部分的取代基,主要为具有本发明内特性的烃基。这样的取代基包括如下取代基:
1.烃取代基,即脂肪族的(例如烷基或链烯基)、脂环族(例如环烷基或环烯基)取代基,芳族的、脂肪族的和脂环族的取代芳环等,以及环状取代基,其中通过配体的另外部分形成环(即任何两个所示的取代基可一起形成脂环基团)。
2.取代的烃取代基,即在本发明内的含有非烃基团的那些取代的烃取代基,它不改变取代基的主要烃基特性。熟悉本专业的技术人员会认识到适合的基团(例如卤素特别是氯和氟、氨基、烷氧基、巯基、烷基巯基、硝基、亚硝基、次硫基等)。
3.杂取代基,即在本发明内在链或环中有除碳原子外的其他原子的取代基,同时有主要的烃基特性。
重要的是,配体的有机基团有足够的碳原子数目,以使化合物在油中可溶或可分散。例如,在每一基团中的碳原子数通常为约1~100、优选约1~30、更优选约4~20。优选的配体包括二烷基二硫代磷酸根、烷基黄原酸根和二烷基二硫代氨基甲酸根,其中二烷基二硫代氨基甲酸根是更优选的。含有两个或两个以上上述官能团的有机配体也可作为配体并连接到一个或多个核上。熟悉本专业的技术人员会认识到本发明化合物的形成需要选择有适当电荷的配体,以平衡核电荷。
有分子式Mo3SkLnQz的化合物有被阴离子配体包围的阳离子核,并用以下结构式表示,
和
并有+4的净电荷。因此,为了使这些核增溶,所有配体的总电荷必需为-4。4个一价阴离子配体是优选的。不希望受任何理论的束缚,据认为可通过一个或多个配体连接两个或两个以上三核含钼化合物的核,配体可为多齿的。这包括对单一核有多重连接的多齿配体的情况。据认为氧和/或硒可取代核中的硫。
油可溶的或可分散的三核含钼化合物可通过钼源(例如(NH4)2Mo3S13·n(H2O)其中n为0~2,包括非化学计量数值)与适当的配体源例如二硫化四烷基秋兰姆在适当液体/溶剂中反应来制备。其他油溶的或油可分散的三核含钼化合物可由钼源(例如(NH4)2Mo3S13·n(H2O))、配体源(例如二硫化四烷基秋兰姆、二烷基二硫代氨基甲酸盐或二烷基二硫代磷酸盐)以及硫抽提剂(例如氰化物离子、硫离子或取代的膦)在适当溶剂中的反应过程中生成。或者,三核的钼-硫卤化物盐(例如[M’]2[Mo3S7A6],其中M’为反离子,A为卤素例如Cl、Br或I)可与配体源(例如二烷基二硫代氨基甲酸盐或二烷基二硫代磷酸盐)在适当液体/溶剂中反应,生成油可溶的或可分散的三核含钼化合物。适当液体/溶剂例如可为含水的或含有机物的。
化合物的油溶性或油分散性可能受配体的有机基团中的碳原子数影响。在本发明的化合物中,所有的配体的有机基团应有至少21个总碳原子。优选的是,所选的配体源的有机基团中有足够的碳原子数,以使化合物在润滑油组合物中可溶或可分散。
这里使用的术语“油可溶的”或“油可分散的”不一定表示化合物或添加剂以所有比例在油中是可溶的、可溶混的或能悬浮的。但是,它们指化合物或添加剂例如在油中按一定程度可溶或可稳定分散,足以在油使用的环境中达到所要求的效果。而且,如果需要,其他添加剂的加入还可允许更高数量的特定添加剂加入。
本发明的润滑油组合物含有含钼化合物,其用量为可向组合物提供至少10ppm钼。已发现由含钼化合物提供的至少10ppm钼与不含氮的无灰有机摩擦改进剂一起使用可有效实现燃料经济效益。优选的是,按润滑油组合物的总重计,含钼化合物提供的钼的量为约10~750ppm,例如10~350ppm、更优选为约30~200ppm、进一步优选为约50~100ppm。因为这样的含钼化合物还为润滑油组合物提供抗磨性,它的使用能减少二烃基二硫代磷酸金属盐抗磨剂(例如ZDDP)的用量。工业趋势是使加到润滑油中的ZDDP的量减少,以使油中的磷含量降到1000ppm以下,例如250~750ppm或250~500ppm。为了在这样的低磷润滑油组合物中提供足够的抗磨性,含钼化合物的用量为至少提供50ppm(质量)钼。钼和/或锌的量可用感应耦合等离子体(ICP)发射谱用ASTM D5185中描述的方法测定。
适用于本发明润滑油组合物的不合氮的无灰有机摩擦改进剂通常是已知的,包括通过羧酸和酸酐与链烷醇反应制得的酯。其他适用的摩擦改进剂通常包括通过共价键连到亲油烃链的极性端基(例如羧基或羟基)。羧酸和酸酐与链烷醇反应所得的酯在US4702850中公开。其他传统的有机摩擦改进剂的例子由M.Belzer在“Journal of Tribology”(1992),Vol.114,pp.675-682和M.Belzer and S.Jahanmir在“Lubrication Science”(1988),Vol.1,pp.3-26中描述。
有机摩擦改进剂包合在本发明的润滑油组合物中,其用量为能与含钼化合物一起有效地使组合物可靠地通过层序(Sequence)VIB燃料经济性试验。例如,不含氮的无灰有机摩擦改进剂可加到含钼的润滑油组合物中,其用量为在ASTM程序VIB燃料经济性试验中96小时(II阶段性能)下测量,SAE 5W-20润滑油足以得到至少1.7%;5W-30润滑油得到1.1%;10W-30润滑油得到0.6%的保留的燃料经济性改进。通常,为了提供所需的效果,按润滑油组合物的总重计,加入约0.25%~2.0%(重量)(AI)不含氮的无灰有机摩擦改进剂。优选的不含氮的无灰有机摩擦改进剂为酯类;特别优选的不含氮的无灰有机摩擦改进剂为单油酸甘油酯(GMO)。
从本发明组合物中排除的无灰胺类摩擦改进剂包括油溶性的烷氧基化的单胺和二胺,它们能改进边界层润滑性,但有时可能损害含氟弹性体密封材料。一类常用的这类不含金属的含氮摩擦改进剂为乙氧基化的胺类。当以硼化合物例如氧化硼、卤化硼、偏硼酸盐、硼酸或硼酸单烷基酯、硼酸二烷基酯或硼酸三烷基酯的加成物或反应产物形式存在时,这些胺也被排除。
含金属的或生成灰分的去污剂既作为减少或除去沉积物的去污剂又用作酸中和剂或防锈剂,从而降低了磨损和腐蚀并延长了发动机寿命。去污剂通常含有带长憎水尾的极性头,极性头含有酸性有机化合物的金属盐。所述的盐可含有实际化学计量数量的金属,通常称为正盐或中性盐,通常总碱值(TBN)为0~80,用ASTM D-2896测量。可能包含大量过量金属化合物例如氧化物或氢氧化物与酸性气体例如二氧化碳反应得到的金属碱。生成的高碱性去污剂含有已中和的去污剂作为金属碱(例如碳酸盐)胶束的外层。这样的高碱性去污剂的TBN可为150或更大,通常为250~450或更大。
已知的去污剂包括油溶性的中性和高碱性的磺酸盐、酚盐、硫化的酚盐、硫代磷酸盐、水杨酸盐和环烷酸盐以及其他油溶性的羧酸金属盐,特别是碱金属或碱土金属,例如钠、钾、锂、钙和镁的盐。最常用的金属为钙和镁(它们可存在于润滑剂使用的去污剂中)和钙和/或镁与钠的混合物。特别方便的金属去污剂为中性的或高碱性的磺酸钙,其TBN为20~450,以及中性的和高碱性的酚钙和硫化的酚钙,其TBN为50~450。
在本发明中,使用一种或多种钙基去污剂,其用量为可向该组合物引入0.05%~0.6%(重)的钙。钙的量可用ASTM D5185中描述的方法用感应耦合等离子体(ICP)发射谱来测定。优选地,钙基去污剂为高碱性的,其总碱值为约150~450。更优选地,钙基去污剂为高碱性的磺酸钙去污剂。本发明的组合物还可包含中性的或高碱性的镁基去污剂,但优选地,本发明的润滑油组合物不含镁。
可加到本发明润滑油组合物中的二烃基二硫代磷酸金属盐抗磨剂为这样的二烃基二硫代磷酸金属盐,其中金属可为碱金属或碱土金属或铝、铅、锡、钼、锰、镍、铜或优选锌。锌盐最常用于润滑油。
二烃基二硫代磷酸金属盐可按已知的技术制备,通常首先通过一种或多种醇或酚与P2S5反应制得二烃基二硫代磷酸(DDPA),然后用金属化合物中和生成的DDPA。例如,可通过伯醇和仲醇的混合物反应来制备二烃基二硫代磷酸。或者,可制备多重二烃基二硫代磷酸,其中一个上的烃基完全是仲基特性,而在另一个上的烃基完全是伯基特性。为了制备金属盐,任何碱性的或中性的金属化合物都可使用,但通常最常用的是氧化物、氢氧化物和碳酸盐。由于在中和反应中使用过量碱性金属化合物,商业添加剂常常含有过量的金属。
优选的二烃基二硫代磷酸锌(ZDDP)为二烃基二硫代磷酸的油溶性的盐,可用下式表示:
式中R和R’可为含有1~18、优选2~12个碳原子的相同的或不同的烃基,包括烷基、链烯基、芳基、芳烷基、烷芳基和环脂族基团。特别优选的R和R’为2~8个碳原子的烷基。例如,所述的基团可为乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、戊基、正己基、异己基、正辛基、癸基、十八烷基、2-乙基己基、苯基、丁苯基、环己基、甲基环戊基、丙烯基、丁烯基。为了得到油溶性,在二烃基二硫代磷酸中的碳原子总数(即R和R’)通常为约5或更大。所以,二烃基二硫代磷酸锌可为二烷基二硫代磷酸锌。
为了将通过ZDDP加到润滑油组合物中的磷的量限制在不大于0.1%(重)(1000ppm),按润滑油组合物的总重计,加到润滑油组合物中的ZDDP数量优选不大于约1.1~1.3%(重量)。
例如如下的其他添加剂也可在本发明的润滑油组合物中存在。
无灰分散剂有油溶性的聚合烃主链,带有能与分散的颗粒缔和的官能基团。一般,分散剂含有通常通过桥基连接到聚合物主链上的胺、醇、酰胺或酯极性部分。例如,无灰分散剂可选自油溶性的长链烃取代的一元和二元羧酸或酸酐的盐、酯、氨基-酯、酰胺、亚酰胺和噁唑啉;长链烃的硫代羧酸盐衍生物;有多胺直接连接的长链脂族烃;以及长链取代酚与甲醛和聚亚烷基多胺缩合生成的曼尼期缩合产物。
粘度改进剂(VM)使润滑油具有高温和低温操作性。所用的VM可有单功能或多功能。
还作为分散剂的多功能粘度改进剂也是已知的。适合的粘度改进剂为聚异丁烯、乙烯和丙烯和高级α烯烃的共聚物、聚甲基丙烯酸酯、聚甲基丙烯酸烷基酯、甲基丙烯酸酯共聚物、不饱和二元羧酸和乙烯基化合物的共聚物、苯乙烯和丙烯酸酯的共聚物以及部分氢化的苯乙烯/异戊二烯、苯乙烯/丁二烯和异戊二烯/丁二烯的共聚物,以及部分氢化的丁二烯和异戊二烯和异戊二烯/二乙烯基苯的均聚物。
氧化抑制剂或抗氧化剂使基础油在使用中变质的倾向减缓,所述的变质可用氧化产物例如淤渣和在金属表面上的漆膜沉积物以及粘度增加来证实。这样的氧化抑制剂包括受阻酚类;烷基酚硫代酯的碱土金属盐,优选有C5~C12烷基侧链;硫化壬基酚钙;无灰油溶性的酚盐和硫化的酚盐;硫磷化的或硫化的烃类;磷酯;硫代氨基甲酸金属盐和油溶性的铜化合物,正如U.S.4867890中所公开的。
可使用选自非离子型聚氧亚烷基酚及其酯、聚氧亚烷基酚和阴离子型烷基磺酸的防锈剂。
可使用含铜和铅的腐蚀抑制剂,但通常本发明的配方不需要。通常,这样的化合物为含有5~50个碳原子的硫杂二唑多硫化物、它们的衍生物和聚合物。如U.S.专利Nos 2719125;2719126和3087932中公开的1,3,4硫杂二唑的衍生物是常用的。其他类似的材料在U.S.专利Nos 3821236;3904537;4097387;4107059;4136043;4188299和4193882中公开。其他添加剂为硫杂二唑的硫代的和多硫代的亚磺酰胺,如在英国专利申请书1560830中公开的。苯并三唑衍生物也在这类添加剂范围内。当这些化合物包含在润滑油组合物中时,它们优选的用量为不超过0.2%(量)活性成分。
可使用少量破乳组分。优选的破乳组分在EP330522中公开。它通过环氧烷与双环氧化物与多元醇反应得到的加成物的反应制得。应加入不超过0.1%(质量)活性成分的破乳剂。0.001%~0.05%(质量)活性成分的处理率是合适的。
流点降凝剂也称为润滑油流动改进剂使流体可流动或倾例的最低温度下降。这样的添加剂是大家熟悉的。改进流体低温流动性的这些添加剂的代表是C8~C18二烷基富马酸酯/乙酸乙烯酯共聚物、聚甲基丙烯酸烷基酯等。
可用包括聚硅氧烷型消泡剂在内的许多化合物来控制起泡,例如硅酮或聚二甲基硅氧烷。
上述添加剂中有些可提供多种效果;例如单一添加剂可作分散剂-氧化抑制剂。这一途径是大家熟悉的,不需进一步说明。
可用任何便利的方法将单个添加剂加到基础油中。例如,可直接将每一组分以所需的浓度水平分散或溶解在基础油或基础油调合油中来加入。这样的调合可在常温或升温下进行。
优选地,除了粘度改进剂和流点降凝剂外其他所有添加剂都调合到这里所述的浓缩物或添加剂配方中,称之为添加剂配方,随后调合到基础油中,制成成品润滑油。通常将浓缩物配制成含有适当量的添加剂,以便当浓缩物与预定量的基础润滑油混合时,在最后的配方中得到所需的浓度。
浓缩物优选按US4938880中公开的方法制备。所述的专利公开在至少约100℃下预调合制备无灰分散剂和金属去污剂的预混合物。此后,再将预混合物冷却到至少85℃,然后加入另外的组分。
最后的曲轴箱用润滑油配方可使用2%~20%(质量)、优选4%~18%(质量)、最优选约5%~17%(质量)浓缩物或添加剂配方,其余为基础油。
实施例
实施例1(密封性能)
用基本上等量的Ⅱ类基础油(粘度指数为118)、粘度改进剂、流点降凝剂、分散剂、抗氧剂、乳化剂和消泡剂配制5W-30级润滑油组合物,ZDDP、含钼化合物(二硫代氨基甲酸钼)、高碱性磺酸钙去污剂(300TBN)和含氮的有机摩擦改进剂(乙氧基化的牛脂胺或ETA)和不含氮的无灰有机摩擦改进剂(单油酸甘油酯或GMO)的用量如表1中所示。
表1
油1 | 油2 | 油3(本发明) | 油4 | |
磺酸钙去污剂 | 1.6 | 1.6 | 1.6 | 1.6 |
含钼化合物 | 0.3 | 0.3 | 0.3 | |
ZDDP | 1.2 | 1.2 | 1.2 | 1.2 |
GMO | 1 | |||
ETA | 1 | |||
磷,%(质量) | 0.09 | 0.09 | 0.09 | 0.09 |
钙,%(质量) | 0.19 | 0.19 | 0.19 | 0.19 |
钼,ppm | 0 | 160 | 160 | 160 |
KV100 | 10.3 | 10.3 | 10.3 | 10.3 |
CCS-30 | 3150 | 3140 | 3250 | 3270 |
CCS-35 | 6280 | 6510 | 6560 | 6565 |
Noack | 14 | 13.5 | 13.8 | 13.9 |
用VW PV 3344法在Volkswagen Viton密封试验中评价了上述配方的性能。在拉伸强度、断裂伸长率和是否存在龟裂方面,合格/不合格判断标准下降。评价的结果列入表2。
表2
VW密封件(AK-6) | 油1 | 油2 | 油3(本发明) | 油4 |
拉伸强度,Mpa | 10.7 | 9.6 | 9.1 | 4.2(F)* |
断裂伸长率,% | 248 | 219 | 208 | 108(F)* |
龟裂评估 | 无龟裂 | 无龟裂 | 无龟裂 | 龟裂(F)* |
新密封 | ||||
拉伸强度,Mpa | 15.4 | |||
断裂伸长率,% | 322 | |||
龟裂评估 | 无龟裂 |
*(F)表示“不合格”
表2的结果表明,很显然对于所有规定的标准来说,含氮的摩擦改进剂(ETA)对密封性能有不好的影响。GMO对密封性能无影响。
实施例2(燃料经济性)
用基本上等量的II类基础油(粘度指数为118)、粘度改进剂、降凝剂、分散剂、抗氧化剂、乳化剂和消泡剂配制OW-20级润滑油组合物,ZDDP、含钼化合物(二硫代氨基甲酸钼)、高碱性磺酸钙去污剂(300TBN)和不含氮的无灰有机摩擦改进剂(单油酸甘油酯或GMA)的用量如表3中所示。为了与基准比较,油10含有不含添加剂的对比基础油。
表3
油5 | 油6 | 油7(本发明) | 油8 | 油9 | 油10 | |
磺酸钙去污剂 | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 | |
含钼化合物 | 0.3 | 0.3 | 1.5 | 0.3 | ||
ZDDP | 1.2 | 1.2 | 1.2 | 1.2 | 0.6 | |
GMO | 1 | 1 | ||||
Noack | 12.6 | 12.4 | 13.1 | 13.3 | 12.8 | 13.7 |
KV100 | 8.9 | 8.9 | 8.8 | 8.9 | 8.7 | 4.7 |
CCS-30 | 2750 | 2760 | 2790 | 2790 | 2710 | N/A |
CCS-35 | 5560 | 5560 | 5650 | 5640 | 5580 | N/A |
KV-40 | 25.13 | |||||
粘度指数 | 102 | |||||
磷,%(质量) | 0.09 | 0.09 | 0.09 | 0.09 | 0.045 | |
钙,%(质量) | 0.19 | 0.19 | 0.19 | 0.19 | 0.19 | |
钼,ppm | 0 | 170 | 170 | 820 | 170 |
在层序VIB筛网试验中测试了油5~9,测量在燃料经济性方面的差别。层序VIB筛网试验用来预计在整个ASTM层序VIB试验中燃料经济性。
在层序VIB筛网试验中,测定了使用基线校正油的发动机燃料消耗。进行待测油的快速(flying)冲洗,在用待测油测量发动机的燃料消耗以前将油老化16小时。直到这时,步骤与ASTM层序VIB试验相同。在筛网中,对阶段1、2和4测量燃料经济性改进,而阶段1~5在整个试验中测量。在第一待测油以后,进行双重去污剂冲洗,并对下一待测油进行快速冲洗。按描述继续此过程直到最后的待测油被评价,然后第二次进行基线校正油的性能评价。结果作为相对于基线校正油(油10)的燃料经济性改进列出。
在层序VIB筛网试验中的阶段1测量边界摩擦的改进。在这一试验阶段中,预计较低摩擦的化合物给出强的响应。已知二硫代氨基甲酸钼使边界摩擦下降,小型摩擦设备(高频往复设备,即HFRR)表明,通常含二硫代氨基甲酸钼的油的摩擦系数大大低于含有机摩擦改进剂的油。所以,预计与二硫代氨基甲酸钼高含量的相同油相比,在边界条件下,低含量二硫代氨基甲酸钼与有机摩擦改进剂的组合将得到较差的燃料经济性能。
表4(层序VIB筛网结果)
权重响应-相对基线校正油的燃料经济性保留性% | ||||||
油5 | 油6 | 油7(本发明) | 油8 | 油9(本发明) | 油10 | |
阶段1改进 | -0.596 | -0.048 | 0.113 | 0.096 | 0.262 | N/A |
油5中既没有含钼摩擦改进剂也不含有机摩擦改进剂。油6与油5相同,不同的是它含有170ppm来自二硫代氨基甲酸钼的钼。由于不含摩擦改进剂(油5),阶段1对基线校正油是负值(比较差)。加入钼(油6)改进了阶段1的性能,但燃料经济性改进对基线校正油仍为负值。
因为在HFRR中二硫代氨基甲酸钼比有机摩擦改进剂更有效(见表5),可预计最高钼含量的油有最好的性能。但是,有170ppm钼和1.0%(质量)有机摩擦改进剂组合的油7表明比油8在燃料经济性方面有所改进,后者含有820ppm钼。含170ppm钼、1%(质量)单油酸甘油酯和500ppm来自二烷基二硫代磷酸锌的磷的油(油9)达到最佳燃料经济性。
表5(HFRR数据)
温度,℃ | 油5 | 油6 | 油7(本发明) | 油8 | 油9(本发明) |
摩擦系数 | |||||
40 | 0.166 | 0.163 | 0.154 | 0.163 | 0.15 |
60 | 0.168 | 0.165 | 0.143 | 0.151 | 0.141 |
80 | 0.18 | 0.164 | 0.134 | 0.113 | 0.133 |
100 | 0.18 | 0.124 | 0.128 | 0.086 | 0.125 |
120 | 0.174 | 0.097 | 0.123 | 0.081 | 0.121 |
140 | 0.17 | 0.089 | 0.119 | 0.075 | 0.118 |
表5提供油5~9的HFRR结果。如上讨论的,HFRR结果表明,含钼的润滑油使摩擦系数下降,特别是80和100℃下。钼和有机摩擦改进剂组合比只含170ppm钼或820ppm钼的含钼摩擦改进剂差。含有ZDDP提供500~1000ppm磷的有机摩擦改进剂,其钼含量高低之间没有差别。这一数据表明,在表4中所列的层序VIB筛网试验结果的预计不会出现。
上述所有专利、文献、试验技术规格和其他参考文献的主题内容因此全部并入本说明书。虽然根据本发明已说明和描述了几个特定的实施方案,但是对于熟悉本专业的技术人员来说,显然可容许有许多变化。所以,不能将本发明限制到所示的和所述的详细内容中,而是包括在附后的权利要求书的范围内的所有变化和改进。
Claims (21)
1.一种润滑油组合物,所述的润滑油组合物含有:
a)粘度指数为至少95的润滑粘度的油;
b)至少一种钙清净剂;
c)至少一种油溶性的含钼化合物;
d)至少一种不含氮的无灰有机摩擦改进剂;以及
e)至少一种二烃基二硫代磷酸金属盐化合物,其中所述的组合物的Noack挥发性为15重量%或更小,有0.05重量%~0.6重量%来自钙清净剂的钙,10ppm~750ppm的来自含钼化合物的钼和最高0.1重量%来自二烃基二硫代磷酸金属盐化合物的磷,所述润滑油组合物不包括含氮有机摩擦改进剂。
2.根据权利要求1的组合物,其中所述的钙清净剂选自酚钙、水杨酸钙、磺酸钙及其混合物。
3.根据权利要求1的组合物,其中所述的钙清净剂为高碱性的磺酸钙。
4.根据权利要求3的组合物,其中所述的高碱性的磺酸钙的总碱值为150~450。
5.根据权利要求1的组合物,其中由含钼化合物得到的所述的钼的量为10ppm~350ppm。
6.根据权利要求1的组合物,其中由含钼化合物得到的所述的钼的量为30ppm~200ppm。
7.根据权利要求1的组合物,其中所述的含钼化合物为有机含钼化合物。
8.根据权利要求7的组合物,其中所述的含钼化合物选自:二烷基二硫代氨基甲酸钼、二烷基二硫代磷酸钼、二烷基二硫代次磷酸钼、黄原酸钼、硫代黄原酸钼及其混合物。
9.根据权利要求8的组合物,其中所述的含钼化合物为二烷基二硫代氨基甲酸钼。
10.根据权利要求9的组合物,其中所述的含钼化合物为三核的含钼化合物。
11.根据权利要求1的组合物,其中所述的含钼化合物为碱性含氮化合物的钼/硫配合物。
12.根据权利要求1的组合物,其中所述的至少一种二烃基二硫代磷酸金属盐化合物为至少一种二烃基二硫代磷酸锌化合物。
13.根据权利要求1的组合物,其中按组合物的总重计,所述的不含氮的无灰有机摩擦改进剂的量为约0.25重量%~2.0重量%。
14.根据权利要求1的组合物,其中所述的至少一种不含氮的无灰有机摩擦改进剂为酯。
15.根据权利要求14的组合物,其中所述的酯为单油酸甘油酯。
16.根据权利要求1的组合物,其中所述的组合物含有约0.025重量%~0.1重量%由二烃基二硫代磷酸金属盐化合物提供的磷。
17.根据权利要求16的组合物,其中所述的组合物含有0.025重量%~0.075重量%由二烃基二硫代磷酸金属盐化合物提供的磷。
18.根据权利要求17的组合物,其中所述的组合物含有0.025重量%~0.05重量%由二烃基二硫代磷酸金属盐化合物提供的磷。
19.一种改进内燃发动机的燃料经济性和燃料经济性保留性的方法,所述的方法包括:(1)将权利要求1的润滑油组合物加到所述的发动机中;以及(2)操作所述的发动机。
20.一种改进内燃发动机抗磨性的方法,所述的方法包括以下步骤:(1)加入权利要求1的润滑油组合物;以及(2)操作发动机。
21.一种改进润滑油组合物与内燃发动机的密封件之间的相容性的方法,所述的方法包括以下步骤:(1)将权利要求1的润滑油组合物加到所述的发动机中;以及(2)操作发动机。
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Also Published As
Publication number | Publication date |
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SG105002A1 (en) | 2004-07-30 |
ATE550412T1 (de) | 2012-04-15 |
CN1450152A (zh) | 2003-10-22 |
CA2424510C (en) | 2009-01-06 |
EP1354933A1 (en) | 2003-10-22 |
US6723685B2 (en) | 2004-04-20 |
JP2003301192A (ja) | 2003-10-21 |
CA2424510A1 (en) | 2003-10-05 |
EP1354933B1 (en) | 2012-03-21 |
US20030199399A1 (en) | 2003-10-23 |
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