CN1807564A - 含钼和聚合物分散剂的润滑剂 - Google Patents

含钼和聚合物分散剂的润滑剂 Download PDF

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CN1807564A
CN1807564A CNA200510108419XA CN200510108419A CN1807564A CN 1807564 A CN1807564 A CN 1807564A CN A200510108419X A CNA200510108419X A CN A200510108419XA CN 200510108419 A CN200510108419 A CN 200510108419A CN 1807564 A CN1807564 A CN 1807564A
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molybdenum
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ethylene
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CN100357414C (zh
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C·A·麦克
小C·K·埃舍
M·T·德夫林
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Afton Chemical Intangibles LLC
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Abstract

通过在一种具有润滑粘度的润滑油中包括至少一种从乙烯-α-烯烃共聚物衍生的聚合物分散剂和一种含钼化合物,而提高润滑油的边界摩擦性能。还公开了一种加入到具有润滑粘度的油中的浓缩物。

Description

含钼和聚合物分散剂的润滑剂
本发明是中国专利申请01142421.4的分案申请。
技术领域
本发明涉及具有增强的摩擦性能和改进的燃油效率的发动机油润滑剂和发动机油润滑剂浓缩物、其制备方法及其用途。本发明的润滑油组合物特别适用于曲轴箱润滑剂。
背景技术
众所周知,汽车曲轴箱内极高的热量和摩擦会使发动机油破坏,同时促使包括脏物,积炭,水和其他微粒物质等在内的污染物的出现。
这种环境使得油受到氧化,该氧化通过油中存在的杂质如铁化合物而得到催化,而且由于发动机使用过程中温度升高使氧化加强。
用于改进发动机内部操作条件的各种发动机油添加剂是已知的,包括抗摩擦剂,抗氧化剂,摩擦改性剂,清净剂和分散剂。每一种添加剂均可以通过控制油在使用过程中受到的各种降解的任何一种而改善其性能。
添加剂可以适当地加入到燃油组合物,发动机油或其他润滑剂和润滑脂中,其可以是合成的,也可以是天然的。
各种形式的分散剂是已知的。这些主要是用于润滑油的添加剂,在低温时用于阻止或减缓淤渣的生成,也用于溶解已经生成的淤渣。在结构上,大多数分散剂含有极性和非极性部分。非极性部分经常是聚丁烯,而极性部分含有氨基。
工业上趋向于提供无灰分散剂,即不包含金属。
丁二酰亚胺分散剂是公知的,他们通常以与各种多胺,如四亚乙基五胺或三亚乙基四胺反应的马来酸酐的聚丁烯(Mn为900-3000)加合物为基础。双丁二酰亚胺一般比单丁二酰亚胺更优选,即使其产品粘度较高。用多元醇,如季戊四醇酯化的聚丁烯加合物为基础的丁二酸酯也是已知的。
由聚丁烯烷基酚,甲醛和多胺缩合产物组成的曼尼希碱产品也是已知的。
烯基取代的丁二酸酐衍生的分散剂是公知的。这种烯基取代的丁二酸酐通常由热法(见例如US 3361673)或热/氯化混合方法(见例如US 3172892)制备。聚异丁烯基丁二酸酐(“PIBSA”)包括单体加合物(见例如US 3219 666;3381022)和用丁二酸基加合的产物,其中对每个聚烯基衍生的取代基加合至少1.3个丁二酸基(见例如Meinhardt的US 4234435)。
PIBSA用作几种曲轴箱无灰分散剂的一种普遍存在的前体,包括丁二酰亚胺,丁二酸酯,丁二酸酯酰胺和三唑(US 3272746,4234435,3219666,4873009,4908145和5080815)。在丁二酰亚胺的制备中,PIBSA与多胺反应生成一种结构复杂的混合物,其可以包含亚胺,酰胺和咪唑啉和二酰胺基团。
上面提到的曼尼希碱分散剂代表另一种已知类型的曲轴箱分散剂(如位于Richmond,Virginia的Ethyl公司出售的HiTEC7049分散剂)。这些化合物通常通过烷基取代的酚与醛及胺反应来制备,例如在US 3539633;3697574;3704308;3736353;3736357;4334085和5433875中描述的。
官能化的烯烃共聚物以及其用作燃油和润滑油组合物的添加剂也是已知的,例如在US 6107258中描述了一种交联的低分子量乙烯-丙烯丁二酸酐分散剂。其中公开的官能化的烯烃共聚物包括一种烯烃共聚物,其上接枝了一种烯属不饱和羧酸或其衍生物以生成一种含有反应性羧基官能团的酰基化了的烯烃共聚物。然后,该酰基化了的烯烃共聚物与一种偶联化合物反应,所述偶联化合物包含一个以上的胺、硫醇和/或羟基官能团,其能够与优选一个以上的酰基化了的烯烃共聚物中的羧基官能团发生反应。
另外,酰基化了的烯烃共聚物,在与偶联化合物反应之前或之后,与提高性能的化合物,即仅含有一个能与酰基化了的烯烃共聚物的羧基官能团反应的官能团的化合物反应,以得到更进一步的优势,如改进的抗氧化性,抗磨性和另外的分散性能。
钼是一种公知的抗磨剂(摩擦改性剂),其有多种市售产品。
羰酸钼盐可提高燃油效率是已知的。用于润滑油中的各种有机钼化合物可以直接买到,包括二(十三烷基)二硫代碳酸钼等。
US 3144712公开了在润滑油中使用的油溶性钼添加剂,如有机氮碱的钼酸盐。
在US 4098705;4846 983;5916851;3356702;3509051和4098705中描述了二烷基二硫代氨基甲酸钼。
Coupland的US 4176074公开了无灰噁唑啉分散剂的钼复合物作为润滑油的减少摩擦的抗磨添加剂。
Karn的US 4266945公开了含钼组合物,其由钼的酸或盐,酚或酚与至少一种低级醛的反应产物,和胺、胺缩合物、胺或胺缩合物的盐反应制备。
Levine的US 4324672公开了高分子量烯基丁二酰亚胺的钼衍生物。
Fletcher的US 5650380公开了一种润滑组合物,其包括与二硫化钼、环烷酸锌,和一种或多种金属二硫代磷酸盐,任选地包括一种或多种金属二硫代氨基甲酸盐结合的矿物油或合成油的基础油。
Gatto等的US 5650381公开了一种润滑油组合物,其包括一种钼化合物,其基本上不包括活性硫和二芳基仲胺。该组合物被认为能为润滑油提供提高的氧化控制性能和摩擦改性性能。
Patel的US 5736491公开了通过将润滑剂与C2-C12脂肪族效酸钼盐与二烷基二硫代磷酸锌或二烷基二硫代氨基甲酸锌混合而减少摩擦从而提高润滑剂的燃油效率特性。
Inoue等人的US 5744430,在一些限定性的条件下,公开了一种基础油,其含有碱土金属水杨酸盐清洁剂、二烷基二硫代磷酸锌、包含聚丁烯基团的丁二酰亚胺无灰分散剂、酚无灰抗氧剂、二硫代氨基甲酸钼盐摩擦改性剂和粘度指数改进剂。
已知含钼添加剂能使润滑剂具有许多好的性能。由于钼的加入而受益的润滑剂的例子包括客车发动机油,天然气发动机油,重负荷柴油及铁路用油。近年来,钼在正确使用时已表现出可以提供改进的抗磨保护,改进的氧化控制,改进的沉积控制和改进的摩擦改性,从而提高了燃油效能。
现有技术以实际例子充分地说明了钼作为抗氧化剂,沉积控制添加剂,抗磨添加剂和摩擦改性剂的用途。这样一些例子包括US 4360438;4501678;4529526;4692256;4705641;4812246;4832867;5458807;5605880;5650381;5658862;5665684;5688748;5696065;5736491;5763369;5786307;5807813;5814587;5837657;5840672;5880073;6034038;6051537;6103673和6103674,PCT申请WO 95/07966;WO 95/07964;WO 95/07963;WO 95/27022;WO 95/07961和EP 0447916A1和EP 0768366A1。
很多油溶性钼化合物及其制备方法已经在本领域中进行了描述。例如,在US 3285942中描述了二醇钼酸盐复合物;在US 4832857中公开了高碱性的碱金属和碱土金属磺酸盐、石炭酸盐和水杨酸盐组合物;在US 4889 647中公开了由脂肪油、二乙醇胺和钼源反应制备的钼配合物;在US 5137647中提到了一种不含硫和磷的有机酰胺的有机钼配合物;在US 5143633中描述了由胺,二胺,烷氧基化的胺,二醇和多元醇制备的高碱性的钼配合物;以及在US 5412130中描述了2,4-杂原子取代的氧化钼-3,3-二噁环烷。
虽然有很多可以分类为抗磨剂、减摩剂或极压剂的润滑剂,每一种可能以完全不同的物理方式或化学方式起作用,而且经常可能互相竞争以占据移动部件的金属表面。因此,在选择能够相容且有效的添加剂时必须特别小心。
发明内容
尽管不同油添加剂可以提高润滑油的单独的性能,仍希望以最小的成本得到最大的提高。因此,本申请人开发了一种新型的润滑油组合物,其令人惊奇地提高了含钼摩擦改性剂的效果。
出乎意料地,业已发现,分散剂的选择可以提高含钼摩擦改性剂的效力。
更具体地,乙烯-α-烯烃聚合物分散剂与钼化合物协同作用可以减少润滑油系统的摩擦。
因此,一方面,本发明涉及提供一种润滑油组合物,其包括(i)主要量的润滑油,(ii)油溶性钼化合物和(iii)乙烯-α-烯烃衍生的共聚物分散剂。
另一方面,本发明涉及通过在基础油中引入钼化合物和聚合物分散剂而降低润滑剂中的摩擦。
本发明还在于提供用如下润滑油组合物润滑的机动车辆和/或发动机。机动车辆或发动机可以是汽油或柴油发动机,而且用一种组合物进行了润滑,所述组合物包括一种具有润滑粘度的润滑油,一种含钼化合物和一种乙烯-α-烯烃衍生的共聚物分散剂。
另一方面,本发明在于提供一种用于加入到基础油中以降低摩擦的浓缩物的制备,所述浓缩物包括一种乙烯-α-烯烃共聚物分散剂和一种钼源,其含量可有效地降低成品油组合物的摩擦。
由于成本和环境或两者共同的原因,人们希望能降低润滑油中不同添加剂的数量和使用量。而且,人们同样希望燃油效率提高不仅是为了降低排放的目的,而且还为了保护短缺的自然资源。
然而,这两个目标常常处于矛盾之中,因为改进更通常地是通过在润滑或燃油组合物中加入另外的组分来实现的。
需要包括在组合物中的添加剂越少,则成本越低,然后这种节省可以以较低价格的形式传递给消费者。另外,内燃机的排放越来越引起人们的关注,通过协同作用提高效能可以使得排放减少,原因是其包括更少的化合物。
申请人发现,使得内燃机中摩擦系数出乎意料地大幅度降低是由于聚合物分散剂与钼化合物之间的协同作用。
因此,在本发明的一个优选实施方案中,提供了一种润滑油组合物,其包括至少如下的组分:
a)具有润滑粘度的油;
b)衍生自乙烯-α-烯烃共聚物的聚合物分散剂;
c)钼化合物。
在一个实施方案中,润滑剂是一种II级或更高级别的油,聚合物分散剂最优选衍生自酰基化的乙烯-丙烯共聚物的丁二酰亚胺。
在另一个实施方案中,丁二酰亚胺衍生自芳族胺,如US 5135671中公开的(n-苯基对苯二胺)。
本发明的组合物降低了边界摩擦系数并提高了用所述组合物润滑的发动机的燃油效率。
从随后的说明和所附权利要求,本发明的其他实施方案将变得显而易见。
说明书和权利要求中提到的分散剂添加剂的重量百分含量以不含油为基础,除非特别提及。例如,当本发明的油组合物描述为包含至少1wt%的分散添加剂时,油包括至少1wt%的分散添加剂,以不含油为基础。因此,如果购得的分散剂添加剂为40wt%的油溶液时,油组合物将包括至少2.5wt%的这种分散剂油溶液。
基础油
本发明的润滑油组分可以选自可用作润滑剂的任何合成或天然油或其混合物,例如用于以火花点燃和压缩点燃内燃机,如汽车或卡车发动机,船用和铁路用柴油发动机的曲轴箱润滑油。合成基础油包括二羧酸烷基酯,聚二醇和醇,聚-a-烯烃,包括,尤其是聚丁烯、烷基苯、有机磷酸酯和聚硅酮油。
天然基础油包括矿物润滑油,这种矿物润滑油根据其原始来源而在较宽范围内变化,如他们或者是脂肪基的、环烷基的或者是混合的脂肪-环烷基的。
润滑油基础料在100℃的粘度通常为约2.5-约15cSt(mm2/s),优选为约2.5-约11cSt(mm2/s)。
合适的基础料油包括第I、II、III和IV级基础油,其对于本领域技术人员是已知的。在某些情况下,一般根据本发明润滑剂组合物的最终用途优选I级,而在另外一些情况下,优选II和III级。
I级基础料包括低于90%的饱和物质(通过ASTM D 2007测定)和/或大于0.03%的硫(通过ASTM D 2622,D 4294,D4927或D3120测定),其粘度指数大于或等于80并小于120(通过ASTM D 2270测定)。
用上述方法测定,II级基础料包括大于或等于90%的饱和物质和低于或等于0.03%的硫,其粘度指数大于80并小于120。也可以用II+级油。这种油在VI谱的高端的VI值为例如约120。
用上述方法测定,III级基础料包括大于或等于90%的饱和物质和低于或等于0.03%的硫,其粘度指数大于或等于120。
IV级基础料为聚α-烯烃(PAO)。
钼化合物
适合的钼化合物包括那些从羧酸、羧酸酰胺或脂肪酸酰胺衍生的钼化合物,如在US 3578690;4765918;4889647;5137647中描述的化合物。
一些市售的适用于本发明的从羧酸衍生的钼化合物包括:OM集团公司提供的15%的钼HEX-CEM,Cincinnati,Ohio的ShepherdChemical公司提供的6%的环烷酸钼,和8%的辛酸钼,一种2-乙基己酸钼。
钼HEX-CEMTM由Cleveland,Ohio的OM集团有限公司提供,是一种2-乙基己酸钼。
其他由有机胺制备的适合的市售钼化合物包括Molyvan807,一种50wt%的二(十三烷基)二硫代碳酸钼,其含有约50wt%的具有大约38.4SUS的比重的芳香油,并含有约4.6wt%的钼;Molyvan855(一种无硫无磷的可分解的有机钼摩擦改性剂,其为一种有机胺的有机钼配合物);Molyvan856B,同样为一种有机钼配合物;Molyvan822(一种含硫的钼摩擦改性剂);Molyvan-A,通常含有28.8wt%的Mo、31.6wt%的C、5.4wt%的H和25.9wt%的S;Molyvan-L,一种磺酸化氧化钼的二烷基二硫代磷酸盐(US 5,055,174),均由Norwalk,Connecticut的R.T.Vanderbilt公司提供。
同为市售产品的有SAKURA LUBE500,一种可溶性二硫代氨基甲酸钼和含胺的润滑剂,其含有20.2wt%的Mo、43.8wt%的C、7.4wt%的H和22.4wt%的S,由日本Tokyo的Asahi Denki公司提供。
羧酸钼盐与二烷基二硫代磷酸锌的结合在US 5,736,491中进行了描述,其他钼化合物在US 4,824,611;4,633,001;3,595,891中进行了描述。
二烷基二硫代氨基甲酸钼在US 4,098,705;4,846,983;5,916,851;3,356,702;3,509,051;和4,098,705中进行了描述。
可供使用的市售二烷基二硫代氨基甲酸钼包括Molyvan807和Molyvan822,由Norwalk,Connecticut的R.T.Vanderbilt公司提供,和Sakura Lube100,Sakura Lube155,Sakura Lube165,和Sakura Lube600,由日本Tokyo的Asahi Denkakk公司提供。
加入最终成品油中的钼的量取决于客户需求及具体用途。处理量可以变化,作为例子而非限制,变化范围为约50-约1500ppm,优选为100-450ppm,更优选为约100-250,尤其是约125-250ppm,其值通常取决于最终成品油的使用需求。但是,足以得到出乎意料但所需的协同作用的本发明组分的任何量均在本发明范围之内。
钼的实际加入量是基于润滑组合物中所需要的钼含量。因此,添加剂的量将以形成具有有利性能的最终成品油所需的钼的活性量为基础。如果钼以浓缩的形式加入到成品油中,浓缩物中钼的活性量就应该进行调节以为最终成品油中提供正确的活性钼量,这种调节是基于调节在成品油中的浓缩物的加入量。
“活性”钼意为可从含钼组合物中释放出来的元素钼。
钼的加入量应该能使其与乙烯-α-烯烃聚合物分散剂一起以协同方式有效地降低摩擦系数。一般来说,该加入量至少为约50ppm,优选为至少约100ppm,更优选为至少200ppm,最高为约1600ppm,优选最高为约800ppm,更优选最高为约500ppm。钼也能有利地提供抗氧化效能。
对于完全调配的油组合物,本发明对于配制能满足ILSAC GF-3客车发动机油标准的油尤其有效,所述标准由国际润滑剂标准化和审定委员会于2000年10月12日公布,其在此引入作为参考。
聚合物分散剂
市售的分散剂适用于本发明。例如,由Richmond,Virginia的Ethyl公司制造的HiTEC1910分散剂,一种乙烯-丙烯分散剂,尤其优选用于本发明。HiTEC1910分散剂是一种用马来酸酐接枝的乙烯-丙烯共聚物,且与n-苯基苯二胺进行了反应。
在US 5075383和6117825中描述的低分子量乙烯-a-烯烃丁二酸酐分散剂也适用于本发明。市售的低分子量乙烯-丙烯丁二酸酐分散剂(LEPSAD)的例子为Richmond,Virginia的Ethyl公司制造的HiTEC1910分散剂。
在US 5266 223;5350532;5435926中描述的乙烯-α-烯烃聚合物同样适用于本发明。乙烯-丙烯二烯聚合物,如在US 4952637;5356999;5374364和5424366中描述的那些也是适用的。
交联的低分子量乙烯-丙烯丁二酸酐分散剂也适用于本发明。这些交联的分散剂类似于上述低分子量乙烯-α-烯烃丁二酸酐分散剂,但另外包含一种多官能团的多胺以达到优良的交联,如在US 6107258中所描述的。
适合的分散剂衍生自分子量为约300-约25000,优选为约1000-约15000,更优选为约5000-约15000的乙烯-α-烯烃聚合物。
本发明的分散剂可以引入到成品油的基料或浓缩物中。
考虑到钼化合物与聚合物分散剂之间的协同作用,成品油中分散剂的有效量可以有一个很宽的范围,其量为基于组合物总重量的约0.001-约5.0wt%,优选为约0.005-约3.5wt%,更优选为约0.1-约1.0wt%。
在意欲稀释入成品油产品的浓缩物中,分散剂的量应成比例地提高。
钼/分散剂组合
根据成品油产品的最终用途,钼与分散剂的比例可以在很宽范围内变化。然而,目前钼与乙烯-α-烯烃分散剂的比例优选为每份分散剂约0.01-约0.4份(重量)钼,以活性钼的量为基础。优选地,(活性)钼与分散剂的比例为约0.02-约0.2。
以另一种方式进行叙述,对于钼的处理量为约250ppm-约800ppm,本发明优选分散剂处理量为约0.06wt%-约8wt%(优选为约0.13wt%-约4.0wt%)。
适合的共分散剂
适合用作共分散剂的其他分散剂包括非金属添加剂,其包含有连接到高分了量烃链上的氮或氧极性基团。烃链提供其在烃基础油中的溶解度。分散剂用于将油降解产物悬浮于油中。通常使用的分散剂的例子包括共聚物如聚甲基丙烯酸酯和苯乙烯-马来酸酯共聚物,丁二酰亚胺,取代的丁二酰胺,多胺丁二酰胺,多羟基丁二酸酯,取代的曼尼希碱和取代的三唑。一般情况下,另外的分散剂在成品油中的量为约0.1-5.0wt%,基于分散剂的活性量。
清洁剂
清洁剂为金属添加剂,其包含带电荷的极性基团,如磺酸盐或羧酸盐,其具有脂肪族、环脂族或烷基芳香链和几个金属离子。清洁剂的作用是从发动机的各种表面去除沉积物。通常用作清洁剂的例子包括中性的和高碱性的碱金属和碱土金属磺酸盐,中性的和高碱性的碱金属和碱土金属石炭酸盐,硫化的石炭酸盐,高碱性的碱土金属水杨酸盐,膦酸盐,硫代焦膦酸盐和硫代膦酸盐。一般情况下,成品油中存在的清洁剂的量为约1.0-2.5wt%,以活性清洁剂量为基础。
ZDDP’S
ZDDP’S(二烃基二硫代磷酸锌)适合作为抗磨添加剂用于本发明。这些添加剂的功能在于与发动机金属表面反应形成一层新的表面活性化合物,后者自身被磨损,从而保护了发动机原来的表面。其他适用的抗磨添加剂的例于包括三甲酚磷酸酯,二(十二烷基)磷酸酯,硫化萜烯和硫化脂肪。ZDDP’S也可作为抗氧剂使用。通常,ZDDP在成品油中的含量应为基于活性化合物的约0.25-1.5wt%,或基于活性化合物的约1.0-1.5%。使用时,从环保角度考虑应使用较低的ZDDP含量。
抗氧剂
对于本发明的油,除二烃基二硫代磷酸锌之外的其他抗氧剂也可用于保护油品使之免于被氧化降解。辅助抗氧剂的量取决于基础油的氧化稳定性。本发明的最终成品中典型的添加量可在约0.25-约2.5wt%之间变化。通常使用的辅助抗氧剂包括受阻酚,受阻双酚,硫化酚,烷基化二苯胺,硫化烯烃,烷基硫化物和二硫化物,二烷基二硫代氨基甲酸盐,和吩噻嗪。
钼的加入可以降低对此类抗氧剂的需求。但是,对于氧化稳定性不好的油或将被用于异常苛刻条件下的油,可以使用辅助抗氧剂。
粘度指数改进剂
聚合物粘度指数改进剂(VII)成份可用于本发明,且此组分可选自任何已知的粘度指数改进剂。VII的功能是降低粘度随温度的变化率,即它们使发动机油的粘度在低温下增加值最小但在高温下显著提高。粘度指数改进剂的例子包括聚异丁烯,聚甲基丙烯酸酯,乙/丙共聚物,聚丙烯酸酯,苯乙烯/马来酸酯共聚物,和氢化苯乙烯/丁二烯共聚物。
其他组分
除上文提及的润滑剂添加剂外,有时需要其他补充添加剂以实现主组分未能提供的特殊功能。这些补充添加剂包括,倾点抑制剂,缓蚀剂,防锈剂,防泡剂和补充摩擦改进剂。
浓缩物
本发明组合物可以是润滑油浓缩物的形式。润滑油浓缩物在混合时加入基础油中,并制造出最终油品共混物。加入量可在大范围内变化,但优选的是使加入量更低。
润滑油浓缩物含有溶剂和约2.5-90重量百分比(wt%),优选的5-75wt%的本发明的钼添加剂和乙/丙共聚物分散剂的结合物。溶剂可以是烃油,例如,矿物润滑油或合成油。浓缩组合物中钼与分散剂的比例为每份分散剂约0.02-0.6份钼,优选为每份分散剂约0.04-0.4份钼(重量比)。
除本发明的钼和聚合物分散剂添加剂外,浓缩物还可含有其他本领域惯用的添加剂,例如,分散剂,清洁剂,抗氧剂和二烃基二硫代磷酸锌。
本发明中的钼化合物,在某些场合下,优选地基本不含磷且基本不含活性硫,而且在低硫应用中,使钼化合物基本不含硫(无论是否是活性的)是有用的。
不需要更详尽的细节,使用上述描述,相信本领域技术人员可以在最全面的范围内应用本发明。以下优选的具体实验方案仅仅在于说明而不在任何意义上限制其他的公开。
以上或以下提到的所有申请,专利,和公布的全部公开在此引入作为参考。
具体实施方式
实施例
测定了本发明的和用于比较的油品组合物的摩擦特性以进一步说明本发明的出乎意料的协同性能。
用高频往复装置测定油的摩擦性能。在该仪器中,将1-2ml(毫升)样品油放置于一个温度可以控制的钢盘上。连接到一个可运动的臂上的钢球下降至盘中。在钢球/臂组件上施加400g的负荷,钢球/臂组件在20hz频率下被振荡移动1mm(毫米)长度的距离。臂在振荡的过程中,每5秒测定一次摩擦系数。
测定持续3分钟,得到大约30个数据点,计算其平均值得到油在一个给定测试中的摩擦系数。摩擦系数的降低相当于油摩擦性能的提高。对每一种油在130℃下重复进行测试,每一种油的平均摩擦系数列在实施例中。
在实施例1-3中,基础流体是API II级基料。II级基料的特性在于其粘度指数为80-120,低于90wt%的饱和物质和/或低于0.03wt%的硫。在实施例4和5中,基础流体是完全调配的SAE 5W-30发动机油,其中共混了API II级基料和市售的添加剂,包括清洁剂,ZDDP,抗氧剂,消泡剂,倾点抑制剂,粘度指数改进剂,摩擦改性剂和稀释工艺油。
用本发明的油进行测试的结果见于表I和II,而且可以清楚地看出其效果。
  表I:用高频往复装置测定的API II级基料中共混物的摩擦性能
  实施例   WT%活性A   WT%活性B WT%活性C   PPMD   130℃的摩擦系数   相对于实施例1A的降低,%
  1A*   3.66   0 0   0   0.141   0
  1B*   3.66   0 0   200   0.146   增加
  1C*   3.66   0 0   500   0.097   31
  1D*   1.22   0 0   200   0.139   1
  2A*   0   1.98 0   0   0.127   0
  2B   0   1.98 0   200   0.119   6
  2C   0   1.98 0   500   0.056   56
  2D   0   0.66 0   200   0.119   6
  3A*   0   0 1.2   0   0.128   0
  3B   0   0 1.2   200   0.113   12
3C 0 0 1.2 500 0.062 52
  3D   0   0 0.4   200   0.069   46
*表示对比例
A为从分子量大约为1350的聚异丁烯衍生的聚异丁烯丁二酰亚胺
B为从Mn大约为10000的乙烯-丙烯共聚物衍生的乙烯-丙烯丁二酰亚胺
C为从Mn大约为10000的乙烯-丙烯共聚物衍生的交联的乙烯-丙烯丁二酰亚胺
D为R.T.Vanderbilt公司出售的Molyvan822产品。
  表II:用高频往复装置测定的完全调配的SAE 5W-30发动机油的摩擦性能
  实施例 WT%活性E   WT%活性F   PPMG   PPMH   130℃的摩擦系数   相对于4A(4B,4C)或5A(5B,5C)的降低,%
  4A* 1.92   0   0   0   0.112   0
  4B* 1.92   0   500   0   0.099   13
  4C* 1.92   0   0   800   0.064   43
  5A* 0   0.96   0   0   0.098   0
  5B 0   0.96   500   0   0.074   24
  5C 0   0.96   0   800   0.040   59
*表示对比例
E为市售的曼尼希分散剂
F为从Mn大约为10000的乙烯-丙烯共聚物衍生的交联的乙烯-丙烯丁二酰亚胺
G为Molyvan822
H为Molyvan855
实施例1-A,1-B,1-C和1-D中的分散剂为HiTEC646分散剂,由Richmond,Virginia的Ethyl公司生产并出售,标称值为61wt%的聚丁二酰亚胺分散剂油溶液。实施例1B-1D中使用了不同量的Mo-822,Molyvan822,在油中的二烷基二硫代氨基甲酸钼,包含4.5-5.3%的钼,5.0-7.0%的硫。
实施例2A,2B,2C和2D中的分散剂为HiTEC1910分散剂,由Richmond,Virginia的Ethyl公司生产并出售,标称值为33wt%的乙烯-丙烯聚合物分散剂的油溶液。
实施例3A,3B,3C和3D中的分散剂为交联的低分子量乙烯-丙烯丁二酸酐分散剂(XLEPSAD),标称值为20%的活性组分。与实施例2中使用的分散剂相似,当聚合物被胺化时,它被改性,即,一些n-苯基苯二胺被多官能团的多胺所取代。
实施例4A,4B和4C中所用的分散剂为HiTEC7049分散剂,由Richmond,Virginia的Ethyl公司出售,标称值为40wt%的曼尼希分散剂的油溶液。
从表I和II可以看出,当乙烯-丙烯聚合物分散剂与钼基摩擦改性剂结合时,摩擦性能得到改善(摩擦系数更低)。在表I和II中,H-646是一种聚合的丁二酰亚胺分散剂,H-7049是一种曼尼希分散剂,H-1910是一种EP聚合物分散剂,XLEPSAD是一种交联EP聚合物分散剂,Mo822是一种市售的二硫代氨基甲酸钼摩擦改性剂,Mo855是一种不含硫和磷的钼摩擦改性剂。据称Mo822和Mo855中均含有7-8%的钼。
对前述实施例中使用的那些本发明的一般或特别提到的组分和/或操作条件进行替代而重复前述实施例可以得到相似的成功结果。
从前述描述中,本领域技术人员可以很容易地确定本发明基本的特性,而且在不偏离本发明的精神和范围的情况下,本领域技术人员可以对本发明进行各种变化和改性以使其适于各种应用和条件。

Claims (4)

1.一种润滑油浓缩物,其包括:
a)含钼化合物,和
b)至少一种由乙烯-α-烯烃聚合物衍生的分散剂。
2.权利要求1的浓缩物,其进一步包括至少一种抑制剂,其选自氧化抑制剂,锈抑制剂,腐蚀抑制剂,泡沫抑制剂和铜蚀抑制剂。
3.一种包括汽油或柴油发动机的机动车辆,所述发动机用润滑组合物润滑,所述润滑油组合物包括:
a)具有润滑粘度的油;
b)油溶性的含钼化合物;和
c)至少一种乙烯-α-烯烃聚合物衍生的分散剂。
4.一种润滑以油润滑的汽车发动机的方法,其包括将润滑油组合物加入到供给所述发动机的润滑油中,所述润滑油组合物包括:
a)具有润滑粘度的油;
b)油溶性的含钼化合物;和
c)至少一种乙烯-α-烯烃聚合物衍生的分散剂。
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ATE317418T1 (de) 2006-02-15
EP1681340A1 (en) 2006-07-19
JP2002167592A (ja) 2002-06-11
CN1229476C (zh) 2005-11-30
DE60117095T2 (de) 2006-11-02
DE60117095D1 (de) 2006-04-20
CN1356385A (zh) 2002-07-03
EP1209220B1 (en) 2006-02-08
EP1209220A1 (en) 2002-05-29

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