CN101104827A - 润滑剂组合物 - Google Patents
润滑剂组合物 Download PDFInfo
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Abstract
公开包含含磷化合物和基础油的润滑剂组合物,所述基础油包含小于约3重量%四环烷。还公开制造和应用该润滑剂组合物的方法。
Description
技术领域
[0001]本公开涉及包含含磷化合物和基础油的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
背景技术
[0002]近些年来已越来越关心生产高能效润滑部件。而且,现代发动机油的规格需要润滑剂来验证标准化发动机试验中的燃油效率。已知润滑剂薄膜的厚度和摩擦特性会影响油的燃油经济性。
[0003]薄膜摩擦是在2个表面之间推动的流体,如润滑剂,所产生的摩擦,其中2个表面之间的距离非常窄。已经知道,常存在于润滑剂组合物中的不同添加剂形成不同厚度的薄膜,这会影响薄膜摩擦。而且,有些添加剂只有很窄的条件范围能使润滑剂组合物具有减小的摩擦性能。更进一步,已知有些添加剂,如二烷基二硫代磷酸锌(ZDDP)会增加薄膜摩擦。
[0004]但是,也已经知道,有些添加剂很贵。而且,对于制造方来说,为减小薄膜摩擦而使用额外用量的添加剂,成本相当高。
[0005]润滑剂组合物中的主要组分可以是基础油,较便宜。基础油是已知的并已分类为I-IV组。基础油纳入给定组的根据是它们的%饱和物、%硫含量和粘度指数。例如,所有组II的基础油都含有90%以上的饱和物、小于0.03%的硫以及粘度指数为≥80~≤120。但是,在组II基础油中,芳族化合物、链烷和环烷的比例能变化很大。已知这些比例的差别会影响润滑剂组合物的性能,如氧化稳定性。
[0006]目前所需要的是便宜且能提供至少下列性能之一的润滑剂组合物:减小的薄膜摩擦和提高的燃油经济。
发明内容
[0007]按照本公开,公开了包含含磷化合物和基础油的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
[0008]而且,公开了包含基础油、不含金属的含磷化合物、分散剂和摩擦改性剂的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
[0009]公开了包含基础油、不含金属的含磷化合物、乙烯-丙烯共聚物和摩擦改性剂的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
[0010]在另一个方面中,公开了减小表面间流体薄膜摩擦的方法,包含向流体供给包含含磷化合物和基础油的组合物,所述基础油包含小于约3重量%四环烷。
[0011]在一个方面中,公开了提高车辆燃油效率的方法,包含向车辆供给包含含磷化合物和基础油的组合物,所述基础油包含小于约3重量%四环烷。
[0012]进一步,公开了制造润滑剂组合物的方法,包含组合含磷化合物和基础油,所述基础油包含小于约3重量%四环烷。
[0013]本公开的其它目的和优点将在以下说明书中部分提出,并可通过实践本公开而得以体会。本公开的目的和优点将通过所附权利要求中特别指出的要素及其组合而得以实现和获得。
[0014]应该理解,前面的概述和下面的详述只是本公开的举例和解释,而非限制,如前所述。
具体说,本发明包含如下内容:
1.包含含磷化合物和基础油的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
2.上述1的组合物,其中含磷化合物是不含金属的含磷化合物。
3.上述2的组合物,其中不含金属的含磷化合物选自酸式磷酸戊酯、亚磷酸新戊二醇酯、亚磷酸新戊二醇酯的盐和膦酸酯。
4.上述1的组合物,其中含磷化合物是含硫含磷化合物。
5.上述4的组合物,其中含硫含磷化合物选自硫代磷酸酯、二硫代磷酸酯、含硫亚磷酸新戊二醇酯和含硫亚磷酸新戊二醇酯的盐。
6.上述1的组合物,还包含分散剂。
7.上述6的组合物,其中分散剂是下列物质中至少一种:琥珀酰亚胺、含硼琥珀酰亚胺、曼尼希分散剂、官能化烯烃共聚物和聚(甲基)丙烯酸酯共聚物。
8.上述7的组合物,其中分散剂是琥珀酰亚胺。
9.上述6的组合物,其中分散剂是高度接枝的胺衍生官能化乙烯-丙烯共聚物。
10.上述1的组合物,还包含摩擦改性剂。
11.上述10的组合物,其中摩擦改性剂是下列物质中至少一种:非-含氮化合物、含氮化合物和含灰化合物。
12.上述11的组合物,其中含氮化合物是长链亚烷基胺。
13.上述12的组合物,其中长链亚烷基胺选自下列一组:N-油基-三亚甲基二胺、N-牛脂-三亚甲基二胺、椰油-三亚甲基二胺和它们的混合物。
14.上述11的组合物,其中含氮化合物是二乙醇胺。
15.上述11的组合物,其中含灰化合物选自下列一组:含钼化合物、含钛化合物和含钨化合物。
16.上述15的组合物,其中含钼化合物包含硫。
17.上述15的组合物,其中含钼化合物选自下列一组:羧酸钼、氨基钼、硫代磷酸钼、硫代氨基甲酸钼和它们的混合物。
18.上述11的组合物,其中非-含氮化合物是多元醇酯。
19.上述18的组合物,其中多元醇酯选自单油酸甘油酯和单月桂酸甘油酯。
20.包含基础油、不含金属的含磷化合物、分散剂和摩擦改性剂的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
21.上述20的组合物,其中分散剂是琥珀酰亚胺。
22.上述20的组合物,其中摩擦改性剂是非-含氮化合物和含钼化合物中至少一种。
23.包含基础油、不含金属的含磷化合物、乙烯-丙烯共聚物和摩擦改性剂的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
24.减小表面间流体薄膜摩擦的方法,包含向流体供给包含含磷化合物和基础油的组合物,所述基础油包含小于约3重量%四环烷。
25.提高车辆燃油效率的方法,包含向车辆供给包含含磷化合物和基础油的组合物,所述基础油包含小于约3重量%四环烷。
26.用按照上述1的润滑剂组合物润滑的发动机、变速器和齿轮组。
27.制造润滑剂组合物的方法,包含组合含磷化合物和基础油,所述基础油包含小于约3重量%四环烷。
28.润滑机器的方法,包含向机器供给上述1的润滑剂组合物。
29.上述28的方法,其中所述机器是齿轮。
30.上述28的方法,其中所述机器是发动机。
具体实施方式
[0015]本公开涉及包含含磷化合物和基础油的润滑剂组合物,所述基础油包含小于约3重量%四环烷。在一个方面中,润滑剂组合物还能包含摩擦改性化合物。在又一个方面中,润滑剂组合物还能包含分散剂。
[0016]基础油可以是分类为I-IV组中的任何基础油。在一个方面中,基础油是II组基础油。基础油能包含相对于基础油总重量小于约3重量%,例如,小于约2重量%,又如,小于约1重量%的四环烷。
[0017]所公开的基础油,与不包含小于3重量%四环烷的基础油相比,具有更低的薄膜摩擦系数。而且,不受任何特定理论的限制,相信当基础油结构的浓度减小时,会改变各添加剂对薄膜摩擦的影响。在一个方面中,某些添加剂与本公开基础油的组合能具有协同效应。
[0018]基础油能以任何所需量或有效量存在于润滑组合物内。例如,基础油可以主要量存在。“主要量”应理解为指大于或等于组合物总重量的50重量%。又如,基础油相对于组合物总重量的存在量,可以大于或等于80重量%,又如大于或等于90%。
[0019]本公开的润滑组合物能包含含磷化合物。在一个方面中,含磷化合物可以是不含金属的含磷化合物。
[0020]此外,含磷化合物能包括磷酸酯的油溶剂胺盐,如U.S.专利号5,354,484和5,763,372所提出的那些,其公开内容引于此供参考;和二环戊二烯与硫代磷酸的反应产物。
[0021]磷酸酯的胺盐可以通过磷酸酯与氨气或碱性氮化合物,如胺,的反应而成。盐可独立地生成,然后可以把磷酸酯的盐加进润滑组合物。
[0022]适用于制备本发明胺盐的磷酸酯可以下式为特征
其中R1可以是氢或烃基,R2可以是烃基,以及2个X基可以是O或S。
[0023]制造包含(I)的组合物的典型方法包含使至少一种通式为ROH的羟基化合物与通式为P2X5的磷化合物反应,其中R可以是烃基和X可以是O或S。由这种方法获得的含磷化合物可以是磷化合物的混合物,且一般是单-和二-烃基取代磷酸和/或二硫代磷酸的混合物,取决于磷反应物(即P2O5或P2S5)的选择。
[0024]在制备本公开的磷酸酯中所用的羟基化合物能以通式ROH为特征,其中R可以是烃基。与磷化合物反应的羟基化合物能包含通式为ROH的羟基化合物的混合物,其中烃基R能含约1~约30个碳原子。但是必须满足:最终制成的取代磷酸酯的胺盐能溶于本公开的润滑组合物中。R基将一般含至少约2个碳原子,典型地,约3~约30个碳原子。
[0025]R基可以是脂族或芳族烃基,如烷基、芳基、烷芳基、芳烷基和脂环烃基。通式为ROH的适用羟基化合物的非限定性实例包括,例如,乙醇、异丙醇、正丁醇、戊醇、己醇、2-乙基-己基醇、壬醇、十一烷醇、硬脂醇、戊基苯酚、辛基苯酚、壬基苯酚、甲基环己醇和烷基化萘醇等。
[0026]在一个方面中,醇,即ROH,可以是脂族醇,例如,含至少约4个碳原子的伯脂醇。因此,能适用于本公开的单羟基醇ROH的典型实例包括戊醇、1-辛醇、1-癸醇、1-十二烷醇、1-十四烷醇、1-十六烷醇、1-十八烷醇、油醇、亚油醇、亚麻醇、植醇、蜂花醇、月桂醇、肉豆蔻醇、鲸蜡醇、硬脂醇和山萮醇。这里可考虑用商品醇(包括混合物在内),而且这类商品醇能包含少量虽然本文未提及但不会有损于本公开主要目的的醇。
[0027]羟基化合物ROH与磷反应物P2X5的摩尔比应在约1∶1~约4∶1范围内,例如3∶1。该反应可通过在约50℃以上~任何反应物或所需产物的组成温度的高温下简单混合两种反应物而进行。在一个方面中,该温度范围可以是约50℃~约150℃,且最常用约100℃以下。反应能在有利于温度控制和反应物混合的溶剂存在下进行。溶剂可以是一种或两种反应物溶于其中或产物溶于其中的任何惰性流质。这类溶剂包括苯、甲苯、二甲苯、正己烷、环己烷、石脑油、二乙基醚卡必醇、二丁基醚二烷、氯苯、硝基苯、四氯化碳或氯仿。
[0028]上述反应的产物是酸性的,但尚未精确地得知其化学组成。但证据表明,产物是主要包含磷酸(或硫代-或二硫代磷酸)的单-和二-酯的酸性磷酸酯的混合物,酯基衍生自醇ROH。
[0029]本公开的胺盐能通过由式(I)代表的上述磷酸酯和至少一种伯或仲氨基化合物的反应而制成。在一个方面中,与取代磷酸发生反应以形成胺盐的胺是通式如下的伯烃基胺:
R’NH2
其中R’可以是最多含约150个碳原子的烃基,而且将更经常是含约4~约30个碳原子的脂肪烃基。
[0030]在一个方面中,适用于制备本公开胺盐的烃基胺可以是烃基中含约4~约30个碳原子,例如,烃基中含约8~约20个碳原子的伯烃基胺。烃基可以是饱和或不饱和的。伯饱和胺的代表性实例是称做脂肪族伯脂肪胺的那些。典型的脂肪胺包括烷基胺,如正己胺、正辛胺、正癸胺、正十二烷基胺、正十四烷基胺、正十五烷基胺、正十六烷基胺、正十八烷基胺(硬脂胺)等。这些伯胺的商品有蒸馏级和技术级。虽然蒸馏级将产生更纯的产物,但所需的酰胺和酰亚胺将在反应中用技术级胺形成。混合脂肪胺也适用。
[0031]在另一个方面中,含磷化合物的胺盐可以是衍生自烷基中含至少约4个碳原子的叔脂伯胺的那些。绝大多数能衍生自烷基中含总共不到约30个碳原子的烷基胺。
叔脂伯胺通常是下式代表的单胺:
R(CH3)2CNH2
其中R可以是含1~约30个碳原子的烃基。这类胺的实例可以有叔丁基胺、叔己基伯胺、1-甲基-1-氨基-环己烷、叔辛基伯胺、叔癸基伯胺、叔十二烷基伯胺、叔十四烷基伯胺、叔十六烷基伯胺、叔十八烷基伯胺、叔二十四烷基伯胺、叔二十八烷基伯胺。
[0032]胺的混合物也适用于本公开的目的。这类混合胺的例子是C11~C14叔烷基伯胺的混合物和C18~C22叔烷基伯胺的类似混合物。叔烷基伯胺和它们的制备方法是本领域一般技术人员周知的,因此不必进一步讨论。适用于本公开目的的叔烷基伯胺及其制备方法已描述在U.S.专利号2,945,749中,该文献引于此供这方面参考。
[0033]烃链包含烯烃不饱和物的伯胺也相当有用。因此,R’和R”基能含有一个或多个烯烃不饱和键,取决于链的长度,通常是每10个碳原子不超过1个双键。代表性胺是十二碳烯胺、肉豆蔻脑基胺、棕榈油基胺、油基胺和亚油基胺。
[0034]仲胺包括含2个上述烷基的二烷基胺,包括这类工业脂肪仲胺在内,还有混合二烷基胺,其中R’是脂肪胺和R”可以是低级烷基(1~9个碳原子),如甲基、乙基、正丙基、异丙基、丁基等,或R”可以是带其它非反应性或极性取代基(CN基、烷基、烷酯基、酰胺基、醚基、硫醚基、卤基、亚砜基、砜基)的烷基,从而自由基的基本烃特性不受破坏。脂肪多胺二胺包括单或二烷基,不论对称或不对称,的乙二胺、丙二胺(1,2或1,3)和与以上类似的多胺。适用的多胺包括N-椰油-1,3-二氨基丙烷、N-大豆油烷基三亚甲基二胺、N-牛脂-1,3-二氨基丙烷或N-油基-1,3-二氨基丙烷。
[0035]油溶性胺盐可以通过在室温或更高的温度下混合上述磷酸酯和上述胺而制成。一般在室温下混合最多约1小时就够了。与磷酸酯反应以形成本公开的盐的胺用量为每当量磷酸至少约1重量当量胺(以氮为基础),以及当量比一般为约1。
[0036]制备这类胺盐的方法是周知的且已报告在文献中。见,例如,U.S.专利号2,063,629;2,224,695;2,447,288;2,616,905;3,984,448;4,431,552;5,354,484;Pesin等,Zhurnal Obshchei Khimii,Vol.31,No.8,pp.2508~2515(1961);和PCT国际申请出版号WO 87/07638,所有这些文献的公开内容均引于此供参考。
[0037]或者,当把酸性磷酸酯与上述胺共混时,也能原位形成盐,这时形成齿轮油浓缩物或配方齿轮油本身。
[0038]用于本文润滑组合物中的另一种含磷化合物包含二环戊二烯和硫代磷酸的反应产物,本文也称之为二环戊二烯二硫代酸酯(dithioates)。硫代磷酸的通式为:
其中R可以是含约2~约30个碳原子,例如,含约3~约18个碳原子的烃基。在一个方面中,R包含约3~约18个碳原子的烃基的混合物。
[0039]在一个方面中,含磷化合物是至少一种下列化合物:亚磷酸新戊二醇酯、含硫的亚磷酸新戊二醇酯和含硫亚磷酸新戊二醇酯的盐。
[0040]二环戊二烯二硫代酸酯可以通过在足以使硫羰酸与二环戊二烯发生反应的温度下混合二环戊二烯和二硫代磷酸一段时间而制成。典型的反应时间可以是30min~6h,但适用的反应条件很易由本领域的技术人员确定。反应产物可经受传统的后反应处理,包括真空汽提和过滤在内。
[0041]本公开的添加剂组合物还可包含摩擦改性化合物。适用于本公开润滑组合物的摩擦改性剂可选自适用于使润滑剂组合物具有该功能的很多适用化合物和材料。摩擦改性剂能以单一类化合物或不同类化合物的混合物使用。摩擦改性剂的非限定性实例包括含氮化合物、含灰化合物和非-含氮化合物。在一个方面中,本公开的润滑组合物可包含非-含氮化合物和含钼化合物。
[0042]含氮化合物可以是包含碱性氮的任何化合物。在一个方面中,含氮化合物可以是长链亚烷基胺。长链亚烷基胺摩擦改性化合物包括,例如,N-脂族烃基取代的三亚甲基二胺,在其中N-脂族烃基取代基是至少一种无炔属不饱和键并含约14~约20个碳原子的直链脂族烃基。这类摩擦改性剂化合物的非限定性实例是N-油基-三亚甲基二胺。其它适用化合物包括N-牛脂-三亚甲基二胺和N-椰油-三亚甲基二胺。
[0043]一组摩擦改性剂包括N-脂族烃基取代的二乙醇胺,在其中N-脂族烃基取代基是至少一种无炔属不饱和键并含有约14~约20个碳原子的直链脂族烃基。
[0044]如本文所用,术语“烃基取代基”或“烃基”按其原意使用,这是本领域技术人员所熟知的。具体地说,它是指含有直接连接在分子其余部分的碳原子上并主要具有烃特性的基团。烃基的实例包括:
[0045](1)烃取代基,即脂族(例如,烷基或链烯基)、脂环族(例如,环烷基、环链烯基)取代基和芳族-、脂族-和脂环族-取代的芳族取代基以及其中的环是通过分子的另一部分完成(例如,2个取代基一起形成脂环自由基)的环取代基。
[0046](2)取代烃取代基,即含有在本发明内容中不改变多数烃取代基(如,卤基(尤其氯和氟)、羟基、烷氧基、巯基、烷巯基、硝基、亚硝基和亚砜基)的非烃取代基;
[0047](3)杂原子取代基,即虽然具有明显的烃特性,但在本发明内容中,在原本由碳原子组成的环或链内含有非碳原子。杂原子包括硫、氧、氮,并包括吡啶基、呋喃基、噻吩基和咪唑基之类的取代基。一般在烃基内每10个碳原子存在不超过2个,例如,不超过1个,非烃取代基;一般在烃基内将无非烃取代基。
[0048]如上所述,摩擦改性剂能包含不同化合物的混合物,如至少一种N-脂族烃基取代的二乙醇胺和至少一种N-脂族烃基取代的三亚甲基二胺的组合,在其中N-脂族烃基取代基是至少一种无炔属不饱和键并含约14~约20个碳原子的直链脂族烃基。关于摩擦改性剂组合更详细的情况已在U.S.专利号5,372,735和5,441,656中提出,其公开内容引于此供参考。
[0049]摩擦改性剂可以是含灰化合物。在一个方面中,含灰化合物可以是含钼化合物。适用于本文公开的润滑组合物的含钼化合物可以是无硫和/或无磷的。无硫和无磷的含钼化合物可以由无硫和无磷钼源与含氨基和/或醇基的有机化合物反应而制成。无硫和无磷钼源的实例包括三氧化钼、钼酸铝、钼酸钠和钼酸钾。氨基可以是单胺、二胺或多胺。醇基可以是单取代醇、二醇或双醇,或多元醇。例如,二胺与脂肪油的反应生成同时含有能与无硫和无磷钼源反应的氨基和醇基的产物。
[0050]全都引于此供参考的专利和专利申请中出现的无硫和无磷含钼化合物的实例包括如下:由某些碱性氮化合物与钼源反应所制成的化合物,如U.S.专利号4,259,195和4,261,843中所定义。由烃取代羟基烷基化胺与钼源反应所制成的化合物,如U.S.专利号4,164,473中所定义。由酚醛缩合产物、单烷基化亚烷基二胺和钼源反应所制成的化合物,如U.S.专利号4,266,945中所定义。由脂肪油、二乙醇胺和钼源反应所制成的化合物,如U.S.专利号4,889,647中所定义。由脂肪油或酸与2-(2-氨基乙基)氨基乙醇和钼源反应所制成的化合物,如U.S.专利号5,137,647中所定义。由仲胺与钼源反应所制成的化合物,如U.S.专利号4,692,256中所定义。由二醇、二氨基或氨基-醇化合物与钼源反应所制成的化合物,如U.S.专利号5,412,130中所定义。由脂肪油、单烷基化亚烷基二胺和钼源反应所制成的化合物,如欧洲专利申请EP1136 496 A1中所定义。由脂肪酸、单烷基化亚烷基二胺、甘油酯和钼源反应所制成的化合物,如欧洲专利申请EP 1 136 497 A1中所定义。由脂肪油、二乙醇胺和钼源反应所制成的化合物,如U.S.专利号4,889,647中所定义。
[0051]在一个方面中,含硫含钼化合物也可用于本文公开的润滑组合物。含硫含钼化合物可以用多种方法制备。一种方法涉及使无硫和/或无磷钼源与氨基和一种或多种硫源反应。硫源可包括,例如,但不限于,二硫化碳、硫化氢、硫化钠和元素硫。或者,含硫含钼化合物也可以由含硫钼源与氨基或秋兰姆基和,任选地,第二硫源反应而制成。例如,三氧化钼与仲胺和二硫化碳的反应生成二硫代氨基甲酸钼。或者,(NH4)2Mo3S13 *n(H2O),其中n为约0~2,与二硫化四烷基秋兰姆的反应生成三核含硫二硫代氨基甲酸钼。
[0052]在专利和专利申请中出现的含硫含钼化合物的非限定性实例包括如下:由三氧化钼与仲胺和二硫化碳反应所制成的化合物,如U.S.专利号3,509,051和3,356,702中所定义。由无硫钼源与仲胺、二硫化碳和外加硫源反应所制成的化合物,如U.S.专利号4,098,705中所定义。由卤化钼与仲胺和二硫化碳反应所制成的化合物,如U.S.专利号4,178,258中所定义。由钼源与碱性氮化合物和硫源反应所制成的化合物,如U.S.专利号4,263,152、4,265,773、4,272,387、4,285,822、4,369,119、4,395,343中所定义。由四硫代钼酸铵与碱性氮化合物反应所制成的化合物,如U.S.专利号4,283,295中所定义。由烯烃、硫、胺和钼源反应所制成的化合物,如U.S.专利号4,362,633中所定义。由四硫代钼酸铵与碱性氮化合物和有机硫源反应所制成的化合物,如U.S.专利号4,402,840中所定义。由酚醛化合物、胺和钼源与硫源反应所制成的化合物,如U.S.专利号4,466,901中所定义。由三甘油酯、碱性氮化合物、钼源和硫源反应所制成的化合物,如U.S.专利号4,765,918中所定义。由碱金属烷基硫代黄原酸酯盐与卤化钼反应所制成的化合物,如U.S.专利号4,966,719中所定义。由二硫化四烷基秋兰姆与六羰基钼反应所制成的化合物,如U.S.专利号4,978,464中所定义。由烷基二黄原酸基与六羰基钼反应所制成的化合物,如U.S.专利号4,990,271中所定义。由碱金属烷基黄原酸酯盐与四乙酸二钼反应所制成的化合物,如U.S.专利号4,995,996中所定义。由(NH4)2Mo3S13 *2H2O与二烷基二硫代氨基甲酸碱金属盐或二硫化四烷基秋兰姆反应所制成的化合物,如U.S.专利号6,232,276中所定义。由酯或酸与二胺、钼源和二硫化碳反应所制成的化合物,如U.S.专利号6,103,674中所定义。由二烷基二硫代氨基甲酸酯的碱金属盐与3-氯丙酸,然后与三氧化钼反应所制成的化合物,如U.S.专利号6,117,826中所定义。
[0053]含钼化合物的非限定性实例包括羧酸钼、氨基钼、硫代磷酸钼、硫代氨基甲酸钼、二硫代氨基甲酸钼等等。
[0054]含灰化合物的其它实例包括,但不限于,含钛化合物和含钨化合物。
[0055]另一组适用的摩擦改性剂包括非-含氮化合物,如多元醇酯,例如,单油酸甘油酯(GMO)、单月桂酸甘油酯(GML)等等。
[0056]摩擦改性剂化合物能以任何所需量或有效量存在于润滑组合物内。在一个方面中,润滑剂组合物能占润滑组合物总重量的约0.05~约3重量%,例如,约0.2~约1.5重量%,又如,约0.3~约1重量%。但本领域的一般技术人员能会理解可以用任意量。
[0057]用于本公开润滑组合物的分散剂可选自本领域技术人员已知的任何无灰分散剂。适用的无灰分散剂可包括琥珀酰亚胺分散剂、曼尼希碱分散剂和聚合物多胺分散剂之类的无灰分散剂。烃基取代的琥珀酰化剂能用来制造烃基取代的琥珀酰亚胺。烃基取代的琥珀酰化剂包括,但不限于,烃基取代的琥珀酸、烃基取代的琥珀酸酐、烃基取代的琥珀酸卤化物(例如,酸氟化物和酸氯化物)及烃基取代琥珀酸和低级醇(例如,含最多7个碳原子)的酯,即能起羧酸酰化剂作用的烃基取代化合物。
[0058]烃基取代的酰化剂能由分子量合适的聚烯烃或氯化聚烯烃与马来酸酐反应而制成。类似的羧酸反应物能用来制造酰化剂。这类反应物能包括,但不限于,马来酸、富马酸、苹果酸、酒石酸、衣康酸、衣康酸酐、柠康酸、柠康酸酐、中康酸、乙基马来酸酐、二甲基马来酸酐、乙基马来酸、二甲基马来酸、己基马来酸等等,包括相应的酸卤化物和较低级脂族酯在内。
[0059]烯烃的分子量可以随拟用的取代琥珀酸酐而变。取代琥珀酸酐一般能含有约8~500个碳原子的烃基。但是,用来制造润滑油分散剂的取代琥珀酸酐一般带有约40~500个碳原子的烃基。对于高分子量取代琥珀酸酐,用数均分子量(Mn)更精确,因为用来制造这些取代琥珀酸酐的烯烃能包括乙烯、丙烯和异丁烯之类低分子量烯烃单体的聚合所产生的不同分子量级分的混合物。
[0060]马来酸酐与烯烃的摩尔比可以变化很大。例如,可以从约5∶1~约1∶5变化,或例如,从约1∶1~约3∶1。对于数均分子量约500~约7000,或者,又如,约800~约3000或更高的聚异丁烯之类的烯烃和乙烯-α-烯烃共聚物,马来酸酐的用量可以超过化学计量,例如,每mol烯烃1.1~3摩尔马来酸酐。未反应马来酸酐可以从所得反应混合物中挥发出去。
[0061]聚链烯基琥珀酸酐能用传统的还原条件,如催化氢化法,转化为聚烷基琥珀酸酐。对于催化氢化,合适的催化剂是在炭上的钯。同样,聚链烯基琥珀酰亚胺可以用类似的还原条件转化成聚烷基琥珀酰亚胺。
[0062]这里所用的琥珀酸酐上的聚烷基或聚链烯基取代基一般能衍生自单烯烃,尤其1-单烯烃,如乙烯、丙烯和丁烯的聚合物或共聚物的聚烯烃。所用的单烯烃能含有约2~约24个碳原子,或,又如,约3~约12个碳原子。适用的其它单烯烃包括丙烯、丁烯,尤其异丁烯、1-辛烯和1-癸烯。由这类单烯烃制成的聚烯烃包括聚丙烯、聚丁烯、聚异丁烯和从1-辛烯和1-癸烯生成的聚α-烯烃。
[0063]在有些方面中,无灰分散剂能包括一种或多种含有至少一个能形成酰亚胺基的伯氨基的胺的链烯基琥珀酰亚胺。链烯基琥珀酰亚胺能用传统法,如加热链烯基琥珀酸酐、酸、酸酯、酸卤化物或较低级烷基酯与含至少一个伯氨基的胺来形成。链烯基琥珀酸酐很容易通过把聚烯烃和马来酸酐加热到约180~220℃而制成。聚烯烃可以是较低级的单烯烃,如乙烯、丙烯、异丁烯等数均分子量在约300~约3000的聚合物或共聚物,分子量用凝胶渗透色谱法(GPC)测定。
[0064]能用来形成无灰分散剂的胺包括含有至少一个能反应成酰亚胺基的伯氨基和至少一个其它伯或仲氨基和/或至少一个羟基的任何胺。几个代表性实例是:N-甲基-丙二胺、N-十二烷基丙二胺、N-氨基丙基-哌嗪、乙醇胺、N-乙醇-乙二胺等等。
[0065]适用的胺能包括亚烷基多胺,如丙二胺、二亚丙基三胺、二-(1,2-亚丁基)三胺和四-(1,2-亚丙基)五胺。另一个实例包括能由式H2N(CH2CH2-NH)nH代表的亚乙基多胺,其中n可以是约1~约10的整数。这些胺包括:乙二胺、二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)、五亚乙基六胺(PEHA)等等,包括它们的混合物在内,在这种情况下,n是混合物的平均值。这类亚乙基多胺每端有一个伯胺基,所以它们能形成单链烯基琥珀酰亚胺和双-链烯基琥珀酰亚胺。商品亚乙基多胺混合物能含少量支化和环化多胺,如N-氨基乙基哌嗪、N,N’-双(氨基乙基)哌嗪、N,N’-双(哌嗪基)乙烷及类似化合物。商品混合物能含有落在对应于二亚乙基三胺至四亚乙基五胺范围内的几乎所有组成。聚链烯基琥珀酸酐与聚亚烷基多胺的摩尔比可以为约1∶1~约3.0∶1。
[0066]在有些方面中,分散剂能包括聚亚乙基多胺,例如,三亚乙基四胺或四亚乙基五胺,与烃取代羧酸或酸酐的反应产物,所述烃取代羧酸或酸酐由合适分子量的聚烯烃,如聚异丁烯,与马来酸酐、马来酸、富马酸等,包括2种或多种这类物质的混合物在内,的不饱和多羧酸或酸酐反应而成。
[0067]也适合于制备本文所述分散剂的聚酰胺包括N-芳基苯二胺,如N-苯基苯二胺,例如,N-苯基-1,4-苯二胺、N-苯基-1,3-苯二胺和N-苯基-1,2-苯二胺;氨基噻唑,如氨基噻唑、氨基苯并噻唑、氨基苯并噻二唑和氨基烷基噻唑;氨基咔唑;氨基吲哚;氨基吡咯;氨基吲哚满酮;氨基巯基三唑;氨基啶;氨基烷基咪唑,如1-(2-氨基乙基)咪唑-e,1-(3-氨基丙基)咪唑;和氨基烷基吗啉,如4-(3-氨基丙基)吗啉。这些多胺已更详细地描述在U.S.专利号4,863,623和5,075,383中,其公开内容引于此供参考。
[0068]适用于形成烃基取代琥珀酰亚胺的其它多胺包括分子内含至少一个伯或仲氨基和至少一个叔氨基的多胺,如U.S.专利号5,634,951和5,725,612所述,其公开内容引于此供参考。适用多胺的非限定性实例包括N,N,N”,N”-四烷基二亚烷基三胺(2个端叔氨基和1个中心仲氨基)、N,N,N’,N”-四烷基三亚烷基四胺(1个端叔氨基、2个内叔氨基和1个端伯氨基)、N,N,N’,N”,N-五烷基三亚烷基四胺(1个端叔氨基、2个内叔氨基和1个端仲氨基)、三(二烷基氨基烷基)氨基烷基甲烷(3个端叔氨基和1个端伯氨基)和类似化合物,其中烷基是相同或不同的,且一般每个含不超过12个碳原子,而且每个能含约1~约4个碳原子。又例如,这些烷基可以是甲基和/或乙基。这类多胺反应物能包括二甲基氨基丙胺(DMAPA)和N-甲基哌嗪。
[0069]适用于此羟基胺包括含至少一种能与烃基取代琥珀酸或酸酐反应的伯或仲胺的化合物、齐聚体或聚合物。适用于此的羟基胺的实例包括氨基乙基乙醇胺(AEEA)、氨基丙基二乙醇胺(APDEA)、乙醇胺、二乙醇胺(DEA)、部分丙氧基化的六亚甲基二胺(例如,HMDA-2PO或HMDA-3PO)、3-氨基-1,2-丙二醇、三(羟基甲基)氨基甲烷和2-氨基-1,3-丙二醇。
[0070]胺与烃基取代的琥珀酸或酸酐的摩尔比可以是约1∶1~约3.0∶1。又如,胺与羟基取代的琥珀酸或酸酐的摩尔比的可以是约1.5∶1~约2.0∶1。
[0071]前述分散剂也可以是,例如,通过如U.S.专利号5,789,353所述,用马来酸酐和硼酸处理分散剂,或通过如U.S.专利号5,137,980所述,用壬基苯酚、甲醛和乙酸处理分散剂,所制成的已后处理分散剂,这些文献的公开内容全都引于此供参考。
[0072]曼尼希碱分散剂可以是环上一般带有长链烷基取代基的烷基苯酚与一种或多种含约1~约7个碳原子的脂族醛(如甲醛及其衍生物)和多胺(尤其多亚烷基多胺)的反应产物。例如,曼尼希碱无灰分散剂可以形成如下:缩合约1mol比例的长链烃取代苯酚及约1~约2.5mol甲醛和约0.5~约2mol聚亚烷基多胺。
[0073]制造曼尼希多胺分散剂的烃源可以是衍生自基本饱和石油馏分和烯烃聚合物,如含2~约6个碳原子的单烯烃的聚合物,的那些。烃源一般含有,例如,至少约40个碳原子,又如,至少约50个碳原子,以使分散剂具有良好的油溶性。GPC数均分子量为约600~5,000的烯烃聚合物能适用。但也能用更高分子量的聚合物。适用烃源可以是异丁烯聚合物和从异丁烯和提余液流的混合物制成的聚合物。
[0074]适用的曼尼希碱分散剂可以是通过缩合约1mol比例长链烃基取代苯酚及约1~约2.5mol甲醛和约0.5~约2mol聚亚烷基多胺所形成的曼尼希碱无灰分散体。
[0075]适合作无灰分散剂的聚合物多胺分散剂是含碱性胺基和油溶性基(如含至少约8个碳原子的侧烷基)的聚合物。这类材料的实例有从多种单体,如甲基丙烯酸癸酯、乙烯基癸基醚或较高分子量的烯烃与丙烯酸氨烷酯和氨烷基丙烯酰胺所形成的共聚体。聚合物多胺分散体的实例已在U.S.专利号3,329,658;3,449,250;3,493,520;3,519,565;3,666,730;3,687,849;和3,702,300中提出。聚合物多胺可包括烃基多胺,其中烃基由异丁烯和提余液流的聚合产物组成,如上所述。也可以用PIB-胺和PIB多胺。
[0076]生成上述无灰分散体的方法是本领域技术人员已知的并已报告在专利文献中。例如,前述多种无灰分散剂的合成已描述在下列U.S.专利号中2,459,112;2,962,442,2,984,550;3,036,003;3,163,603;3,166,516;3,172,892;3,184,474;3,202,678;3,215,707;3,216,936;3,219,666;3,236,770;3,254,025;3,271,310;3,272,746;3,275,554;3,281,357;3,306,908;3,311,558;3,316,177;3,331,776;3,340,281;3,341,542;3,346,493;3,351,552;3,355,270;3,368,972;3,381,022;3,399,141;3,413,347;3,415,750;3,433,744;3,438,757;3,442,808;3,444,170;3,448,047;3,448,048;3,448,049;3,451,933;3,454,497;3,454,555;3,454,607;3,459,661;3,461,172;3,467,668;3,493,520;3,501,405;3,522,179;3,539,633;3,541,012;3,542,680;3,543,678;3,558,743;3,565,804;3,567,637;3,574,101;3,576,743;3,586,629;3,591,598;3,600,372;3,630,904;3,632,510;3,632,511;3,634,515;3,649,229;3,697,428;3,697,574;3,703,536;3,704,308;3,725,277;3,725,441;3,725,480;3,726,882;3,736,357;3,751,365;3,756,953;3,793,202;3,798,165;3,798,247;3,803,039;3,804,763;3,836,471;3,862,981;3,872,019;3,904,595;3,936,480;3,948,800;3,950,341;3,957,746;3,957,854;3,957,855;3,980,569;3,985,802;3,991,098;4,006,089;4,011,380;4,025,451;4,058,468;4,071,548;4,083,699;4,090,854;4,173,540;4,234,435;4,354,950;4,485,023;5,137,980,和Re 26,433,引于此供参考。
[0077]适用无灰分散剂的实例是含硼分散剂。含硼分散剂可形成如下:硼化分子内含碱性氮和/或至少一个羟基的无灰分散剂,如琥珀酰亚胺分散剂、琥珀酰胺分散剂、琥珀酯分散剂、琥珀酯-酰胺分散剂、曼尼希碱分散剂或烃基胺或多胺分散剂。能用来硼化上述各类无灰分散剂的方法已描述在U.S.专利号3,087,936;3,254,025;3,281,428;3,282,955;2,284,409;2,284,410;3,338,832;3,344,069;3,533,945;3,658,836;3,703,536;3,718,663;4,455,243;和4,652,387中,其公开内容全引于此供参考。
[0078]含硼分散剂可包括用硼处理过的高分子量分散剂,要使含硼分散剂包括最多约2重量%硼,例如,约0.8重量%或更少的硼,又如,约0.1~0.7重量%硼,再又如,约0.25~0.7重量%,又再如,约0.35~0.7重量%硼。分散剂可溶解在适当粘度的油内以便于处理。应理解,这里给出的重量百分数是对未加入任何稀释剂的净分散剂而言的。
[0079]分散剂还能进一步与有机酸、酸酐和/或醛/酚混合物进行反应。这种方法能提高与,例如,弹性体密封之类的相容性。含硼分散剂还可包括含硼分散剂的混合物。又如,含硼分散剂可包括含氮分散剂和/或可以是无磷的。
[0080]分散剂在润滑组合物中的存在量可以是润滑组合物的约0.1重量%~约10重量%,例如,约1重量%~7重量%,又如,约2重量%~5重量%。
[0081]在一个方面中,用于本公开润滑剂组合物中的分散剂可以是乙烯-丙烯分散剂。该分散剂尤其可以是接枝了马来酸酐并与N-苯基苯二胺反应的乙烯-丙烯共聚物。
[0082]如U.S.专利号5,075,383和6,117,825所述的低分子量乙烯-α-烯烃琥珀酸酐分散剂也适用于此,其公开内容引于此供参考。如U.S.专利号5,266,223;5,350,532;和5,435,926所述的乙烯-α-烯烃聚合物也适用于本公开,其公开内容引于此供参考。如U.S.专利号4,952,637;5,356,999;5,374,364;和5,424,366所述的乙烯-丙烯-二烯聚合物也适用,其公开内容引于此供参考。
[0083]交联低分子量乙烯-丙烯琥珀酸酐分散体也适用于本发明。这些交联分散剂类似于以上讨论的低分子量乙烯-α-烯烃琥珀酸酐分散剂,但还含有多官能度多胺,目的是实现优选的交联,如.U.S.专利号6,107,258所述,其公开内容引于此供参考。
[0084]适用的分散剂将衍生自分子量为约300~约25,000,例如,约1000~约15,000;又如约5,000~约15,000的乙烯-α-烯烃聚合物。
[0085]在另一个方面中,分散剂可以是高度接枝的胺衍生官能化乙烯-丙烯共聚物,如U.S.专利号5,139,688和6,107,257详述,其公开内容引于此供参考。
[0086]在一个方面中,分散剂可以是官能化烯烃共聚物。聚合物或共聚物基体可以从乙烯和丙烯制成,或者也可以从乙烯和至少一种C3~C23α-烯烃中的较高级烯烃制成。
[0087]适用于此的聚合物的非限定性实例包括乙烯和至少一种C3~C23α-烯烃的共聚物。在一个方面中,能用乙烯和丙烯的共聚物。适合于代替丙烯来形成共聚物或用来与乙烯和丙烯组合起来形成三元共聚物的其它α-烯烃包括1-丁烯、2-丁烯、异丁烯、1-戊烯、1-己烯、1-辛烯和苯乙烯;α,ω-二烯烃,如1,5-己二烯、1,6-庚二烯、1,7-辛二烯;支链α-烯烃,如4-甲基丁烯、1,5-甲基戊烯-1和6-甲基庚烯-1;以及它们的混合物。
[0088]更复杂的聚合物基体,常称之为共聚体,能用第三组分制备。一般用来制备共聚体基体的第三组分可以是选自非共轭二烯和三烯的多烯单体。非共轭二烯组分可以是链内含5~14个碳原子的一种。例如二烯单体能以其结构中存在乙烯基为特征且能包括环和二环化合物在内。代表性二烯包括1,4-己二烯、1,4-环己二烯、二环戊二烯、5-亚乙基-2-降冰片烯、5-亚甲基-2-降冰片烯、1,5-庚二烯和1,6-辛二烯。在制备共聚体时可用不止一种二烯的混合物。在一个实施方案中,用来制备三元共聚物或共聚体基材的非共轭二烯可以是1,4-己二烯。
[0089]三烯组分能含有至少2个非共轭双键以及链上最多含约30个碳原子。适用于制备本发明的共聚体的典型三烯可以是1-异亚丙基-3α,4,7,7α-四氢茚、1-异亚丙基环戊二烯、二氢-异二环戊二烯和2-(2-亚甲基-4-甲基-3-戊烯基)(2.2.1)二环-5-庚烯。
[0090]乙烯-丙烯或更高级α-烯烃的共聚物可包含约15~80mol%乙烯和约85~20mol%C3~C23α-烯烃,例如,摩尔比为约35~75mol%乙烯和约65~25mol%C3~C23α-烯烃,又例如,比例为50~70mol%乙烯和50~30mol%C3~C23α-烯烃,再例如,比例为55~65mol%乙烯和45~35mol%C3~C23α-烯烃。
[0091]前述聚合物中三元共聚物的变体能包含约0.1~10mol%非共轭二烯或三烯。
[0092]术语聚合物和共聚物能用来统括乙烯共聚物、三元共聚物或共聚体。这些材料能包含少量其它烯烃单体,只要乙烯共聚物的基本特性不发生本质变化即可。本领域的普通技术人员会理解怎样制造这些官能化的烯烃共聚物。例如,U.S.专利号6,107,257公开了制造官能化烯烃共聚物的方法,其公开内容引于此供参考。
[0093]分散剂也可以是包含衍生自下列单体的单元的聚(甲基)丙烯酸烷基酯共聚物:(A)约12~约18重量%甲基丙烯酸甲酯;(B)约75~约85重量%(甲基)丙烯酸C10~C15烷基酯;和(C)约2~约5重量%含氮分散剂单体。聚(甲基)丙烯酸烷基酯共聚物能包含下列单体的反应产物:(A)约12~约18重量%甲基丙烯酸甲酯;(B)约75~约85重量%(甲基)丙烯酸C10~C15烷基酯;和(C)约2~约5重量%含氮分散剂单体。
[0094]如本文所用,(甲基)丙烯酸C10~C15烷基酯是指含直链或支化烷基,每个基团含10~15个碳原子的丙烯酸或甲基丙烯酸烷基酯,包括,但不限于,(甲基)丙烯酸癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸十一烷酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸十二烷基十五烷基酯,以及它们的混合物。
[0095]在烷基中含10个或更多个碳原子的(甲基)丙烯酸烷基酯共聚单体一般可以用技术级长链脂肪醇的标准酯化法制备,这类商品醇是烷基中链长不同的醇的混合物。因此,为本公开的目的,(甲基)丙烯酸烷基酯意在不仅包括所命名的各种(甲基)丙烯酸烷基酯,而且还包括主要含量为所命名(甲基)丙烯酸烷基酯的(甲基)丙烯酸烷基酯。
[0096]适用于此的含氮分散剂单体包括二烷基氨基烷基(甲基)丙烯酰胺,如N,N-二甲基氨基丙基甲基丙烯酰胺;N,N-二乙基氨基丙基甲基丙烯酰胺;N,N-二甲基氨基乙基丙烯酰胺和N,N-二乙基氨基乙基丙烯酰胺;和(甲基)丙烯酸二烷基氨基烷基酯,如甲基丙烯酸N,N-二甲基氨基乙酯;丙烯酸N,N-二乙基氨基乙酯;硫代甲基丙烯酸N,N-二甲基氨基乙酯。
[0097]在一个方面中,聚(甲基)丙烯酸烷基酯共聚物基本上由(A)、(B)和(C)的反应产物组成。但是,本领域的技术人员将理解,可以存在少量能与本文公开的单体(A)、(B)和/或(C)聚合的其它单体,只要它们对完全配方流体的低温性能无不利影响即可。外加单体的典型存在量少于约5重量%,例如,少于3重量%,又如,少于1重量%。例如,加入少量(甲基)丙烯酸C2~C9烷基酯单体、含羟基或含烷氧基的聚(甲基)丙烯酸烷基酯、乙烯、丙烯、苯乙烯、乙酸乙烯酯等也认为在本公开范围内。在一个方面中,(A)、(B)和(C)的重量%之和为100%。
[0098]共聚物可以用多种聚合技术制备,包括自由基和阴离子聚合在内。
[0099]传统的自由基聚合法可用来制备共聚物。丙烯酸和/或甲基丙烯酸单体的聚合可以在多种条件下进行,包括本体聚合;通常在有机溶剂中,优选在矿物油中的溶液聚合;乳液聚合;悬浮聚合和非水分散技术。
[00100]任选地,在本公开的润滑剂和/或添加剂组合物中可存在其它组分。其它组分的非限定性实例包括抗磨剂、洗涤剂、稀释剂、脱泡剂、破乳剂、抑泡剂、缓蚀剂、极压剂、密封改良剂、抗氧剂、倾点下降剂、防锈剂和摩擦改性剂。
[00101]本文公开的润滑组合物能用来润滑任何东西。在一个方面中,润滑组合物可以是用来润滑发动机的发动机组合物。但是,本领域的普通技术人员理解,本公开的润滑剂组合物能用来润滑任何东西,例如,任何表面,如能存在薄膜摩擦的表面。此外,还公开了减小表面间流体薄膜摩擦的方法,包含向流体供给本公开的组合物。
[00102]还要展望可以把润滑组合物供给燃料经济成问题的任何机器。尤其公开了提高车辆燃油效率的方法,包含向车辆供给本公开的组合物。
[00103]本文还公开用所公开的润滑组合物润滑机器,如发动机、变速器、汽车齿轮、齿轮组和/或轴的方法。在又一个方面中,公开了提高发动机、变速器、汽车齿轮、齿轮组和/或轴之类机器的燃油效率的方法,包含把公开的润滑组合物放在发动机、变速器、汽车齿轮、齿轮组和/或轴之类的机器内。
实施例
[00104]实施例1-基础油
[00105]在工业上已知II组基础油包含90%以上的不饱和物、小于0.03%硫,以及粘度指数为约80~约120。但并非所有的II组基础油都具有相同的薄膜摩擦性。按照分析化学64:2227(1992)分析表1中的基础油,以确定油内的链烷、环烷和芳族化合物类型。
[00106]各已知油(3种II组基础油和PAO)的薄膜摩擦系数在100℃/20N载荷和20%滑动与滚动比下,以1.5m/s测定。
表1
基础油 | 薄膜摩擦系数 | 100℃的运动粘度 | 基础油中的四环烷含量,% |
A | 0.066 | 4.05cSt | 3.33 |
B | 0.044 | 4.60cSt | 1.48 |
C | 0.030 | 4.09cSt | 1.57 |
PAO | 0.027 | 4.00cSt | 0.00 |
[00107]如表1所示,基础油A和基础油C具有类似的动力学粘度,但基础油A的薄膜摩擦系数较大。此外,基础油B比基础油A具有更大的运动粘度,但其薄膜摩擦系数较低。PAO的结果表明,在没有四环烷的油中,薄膜摩擦是低的。
[00108]此外,如表1所示,四环烷含量小于约3%的基础油具有较低的薄膜摩擦。本领域的普通技术人员会理解,薄膜摩擦越低,则燃油经济越好。
[00109]实施例2-基础油和含磷化合物
[00110]SAE 2000-01-2030表明,含磷化合物在表面上形成薄膜,造成薄膜摩擦增加。例如,二烷基二硫代磷酸锌(ZDDP)能使薄膜摩擦增加。ZDDP是发动机油中最常见的含磷化合物。
[00111]把各种含磷化合物分别与基础油A(四环烷含量为3.33%的基础油)和基础油C(四环烷含量小于约3%的基础油)组合/混合/共混并如实施例1测量它们的薄膜摩擦系数。
表2
基础油A | 基础油C | |
+1%ZDDP | 0.097 | 0.074 |
+0.4%AAP | 0.040 | 0.034 |
+1%S-NPGP | 0.069 | 0.066 |
+0.4%膦酸酯 | 0.055 | 0.035 |
[00112]结果表明,包含含磷化合物和四环烷含量小于约4%的基础油的组合物具有较低的薄膜摩擦系数。本领域的普通技术人员都会理解,薄膜摩擦越低则燃油经济越好。
[00113]实施例3-基础油中的添加剂组合
[00114]已经报告:当在油内加入所有添加剂,如分散剂、洗涤剂、抗磨剂和/或抗氧剂时,薄膜摩擦增加。见M.T.Devlin,T.Hammock和T-C.Jao,“Effect of Mechanical Shear on the Thin Film Properites ofBase Oil/Polymer Mixtures(机械剪切对基础油/聚合物混合物的薄膜摩擦性能的影响)”,Lubrication Science Vol.14(2),2002,其公开内容引于此供参考。把添加剂的各种组合分别与基础油A和基础油C组合/混合/共混,以确定它们的薄膜系数。在组合物中,加入0.6重量%AAP,含钼摩擦改性剂含约480ppm钼。此外,当在添加剂包中存在单油酸甘油酯时,其加入量为0.6重量%。类似地,当添加剂包中存在分散剂时,其加入量为3.0重量%。薄膜摩擦系数如实施例1所述测量。
表3
基础油A | 基础油C | |
+1%ZDDP | 0.097 | 0.074 |
AAP/琥珀酰亚胺/单油酸甘油酯 | 0.050 | 0.041 |
AAP/琥珀酰亚胺/含钼摩擦改性剂化合物 | 0.039 | 0.036 |
AAP/琥珀酰亚胺/单油酸甘油酯和含钼摩擦改性剂化合物 | 0.061 | 0.046 |
AAP/官能化烯烃共聚物/单油酸甘油酯 | 0.010 | 0.012 |
AAP/官能化烯烃共聚物/含钼摩擦改性剂化合物 | 0.041 | 0.047 |
AAP/官能化烯烃共聚物/单油酸甘油酯和含钼摩擦改性剂化合物 | 0.050 | 0.051 |
[00115]结果表明,所有含琥珀酰亚胺分散剂的添加剂组合物,与含官能化烯烃共聚物分散剂的组合物相比,具有低的薄膜摩擦系数。结果表明,在基础油中,含AAP及各种分散剂和摩擦改性剂的组合物,与含ZDDP的组合物相比,都具有低的薄膜摩擦。
[00116]在贯穿本说明书的许多地方,已参考了很多U.S.专利、出版的国外专利申请和出版的技术论文。所有这些引用的文献都明确地引于本公开,恰如本文所述。
[00117]为本说明书和所附权利要求的目的,除非另有说明,本说明书和权利要求中用来表示量、百分数或比例的所有数值和其它数值应理解为在所有情况下都经“约”修饰过。因此,除非相反说明,在下面说明和所附权利要求中所用的数字参数都是近似值,它们能随本公开追求获得的期望性能而变。最起码,而且无意把等代原则的应用限于权利要求范围内,各数值参数应至少被看作是基于报告的有效数字并已运用一般四舍五入法处理过。
[00118]值得指出的是,如本说明书和所附权利要求中所用,单数“一”和“该”包括复数事物在内,除非明确和毫不含糊地限于一件事物。因此,例如,“一种抗氧剂”包括一种或多种不同的抗氧剂。如本文所用,术语“包括”及其语法变化意在非限定性的,因此在表内引用的事物不排除能取代或加进所列事物的其它类似事物。
[00119]虽然已描述了具体实施方案,但对于申请人和本领域的其它技术人员而言,可以出现目前尚未预见的更动、修改、变化、改进和等代体。因此,已提交和能修改的所附权利要求意在包括所有这类更动、修改、变化、改进和基本等代体。
Claims (10)
1.包含含磷化合物和基础油的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
2.权利要求1的组合物,其中含磷化合物是不含金属的含磷化合物,所述不含金属的含磷化合物选自酸式磷酸戊酯、亚磷酸新戊二醇酯、亚磷酸新戊二醇酯的盐和膦酸酯。
3.权利要求1的组合物,其中含磷化合物是含硫含磷化合物,所述含硫含磷化合物选自硫代磷酸酯、二硫代磷酸酯、含硫亚磷酸新戊二醇酯和含硫亚磷酸新戊二醇酯的盐。
4.权利要求1的组合物,还包含分散剂。
5.权利要求1的组合物,还包含摩擦改性剂,所述摩擦改性剂是下列物质中至少一种:非-含氮化合物、含氮化合物和含灰化合物。
6.包含基础油、不含金属的含磷化合物、分散剂和摩擦改性剂的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
7.包含基础油、不含金属的含磷化合物、乙烯-丙烯共聚物和摩擦改性剂的润滑剂组合物,所述基础油包含小于约3重量%四环烷。
8.减小表面间流体薄膜摩擦的方法,包含向流体供给包含含磷化合物和基础油的组合物,所述基础油包含小于约3重量%四环烷。
9.提高车辆燃油效率的方法,包含向车辆供给包含含磷化合物和基础油的组合物,所述基础油包含小于约3重量%四环烷。
10.用按照权利要求1的润滑剂组合物润滑的发动机、变速器和齿轮组。
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-
2006
- 2006-07-14 US US11/457,613 patent/US7879775B2/en not_active Expired - Fee Related
-
2007
- 2007-06-14 GB GB0711554A patent/GB2440217B8/en not_active Expired - Fee Related
- 2007-06-14 DE DE102007027343A patent/DE102007027343A1/de not_active Ceased
- 2007-07-03 JP JP2007175235A patent/JP2008019437A/ja active Pending
- 2007-07-13 FR FR0756498A patent/FR2904326B1/fr not_active Expired - Fee Related
- 2007-07-16 CN CN2007101364626A patent/CN101177644B/zh not_active Expired - Fee Related
- 2007-07-16 CN CN2007101364683A patent/CN101104827B/zh not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104830292A (zh) * | 2015-05-06 | 2015-08-12 | 天津中油渤星工程科技有限公司 | 一种钻井液用低毒低荧光润滑剂及其制备方法 |
CN104830292B (zh) * | 2015-05-06 | 2017-12-05 | 天津中油渤星工程科技有限公司 | 一种钻井液用低毒低荧光润滑剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
GB2440217A8 (en) | 2009-10-14 |
FR2904326B1 (fr) | 2011-09-16 |
FR2904326A1 (fr) | 2008-02-01 |
US20080015125A1 (en) | 2008-01-17 |
GB2440217A (en) | 2008-01-23 |
CN101177644A (zh) | 2008-05-14 |
GB0711554D0 (en) | 2007-07-25 |
CN101104827B (zh) | 2010-12-01 |
US7879775B2 (en) | 2011-02-01 |
GB2440217B8 (en) | 2009-10-14 |
CN101177644B (zh) | 2013-05-08 |
GB2440217B (en) | 2009-04-08 |
DE102007027343A1 (de) | 2008-01-17 |
JP2008019437A (ja) | 2008-01-31 |
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