CN1097086C - 操作性能增强了的自动变速器流体 - Google Patents
操作性能增强了的自动变速器流体 Download PDFInfo
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- CN1097086C CN1097086C CN98122816A CN98122816A CN1097086C CN 1097086 C CN1097086 C CN 1097086C CN 98122816 A CN98122816 A CN 98122816A CN 98122816 A CN98122816 A CN 98122816A CN 1097086 C CN1097086 C CN 1097086C
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- automatic transmission
- dispersion agent
- transmission fluids
- aliphatic
- carbon atoms
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Abstract
描述了一种自动变速器流体,包含氮与磷含量质量比为约3∶1~10∶1的分散剂以及至少一种摩擦改进剂。采用氮与磷含量质量比为约3∶1~约10∶1的分散剂,所配制的自动变速器流体在换档离合器使用中表现出优良抗颤动性能,以及与包含氮与磷含量质量比小于3∶1的分散剂的类似自动变速器流体相比,更高的中点力矩、更高的静力矩乃至更好的摩擦耐久性。
Description
技术领域
本发明涉及操作性能提高的,特别是具有抗颤动性能的基于油的自动变速器流体组合物。
发明背景
目前,汽车制造业正在世界范围内开展着研制汽车变速器的活动,包括各种电子控制转换离合器(ECCC)的设计。这方面的研制工作正受到预计美国的“协会平均燃料经济指标(Corporate AverageFuel Economy(CAFE))”要求将要提高的推动。ECCC设计使得只需对变速器做极少的改动就可提高燃料经济指标成为可能。
ECCC变速器以及装备了可连续变速变速器(CVT)的车辆的出现,由于制造具有在更高能量密度和更高工作温度下操作的更小变速器的客车而导致空气动力车身设计的进步,这一切都要求润滑剂供应者配制出新型的和具有独特性能特点,包括力矩更高的汽车变速器流体。
阻碍ECCC设计在汽车变速器中顺利推广的障碍之一是变速器颤抖。导致变速器颤抖的一个重要因素源于自动变速器流体(ATF)的摩擦特性。颤抖乃设备的耐久及可操作性所不希望的,而且会造成用户投诉和增加保证书的花费。结果,许多自主设计的设备制造者(OEM)正在寻求摩擦特性能满足ECCC设计要求的自动变速器流体。
变矩器位于引擎与汽车变速器中的变速箱之间。它的功能是作为引擎力矩放大器和通过液力耦合传递引擎动力的机构。多数新近的变速器变矩器备有锁止离合器(或离心旁通离合器)。锁止离合器在公路速度下处于接合,以便减少因泵/透平的效率低下而引起的能量损失。如果锁止离合器在行驶速度较低时也处于接合,则燃料的经济性可进一步改进。但是,低速行驶时如果锁止离合器完全接合,则无法阻抑来自引擎的动力波动。在ECCC中,锁止离合器在低速行驶时虽处于接合状态,但可连续打滑,而在以公路速度行驶时则可锁止(不打滑)。这种ECCC设计不仅可减少由于完全靠液力耦合所引起的能量损失,而且可使动力波动平稳下来。与传统的锁止变矩器式变速器相比,装有ECCC的车辆预期有较好的燃料效率(提高约2~10%)。
装有ECCC变速器的车辆经常受到讨厌的颤抖或自激振荡现象的困扰。这种振动,据信由于所谓“粘着-打滑”现象所引起,即此间交替出现两个表面彼此粘在一起,继而又打滑:当侧向力不足以大到克服摩擦力时两个表面粘在一起,而当侧向力累积达到足以克服摩擦力时它们便突然脱开。这种振荡的运动造成以发出尖锐声或发抖,或卡搭声为特征的振动。粘着-打滑最常见于低速滑动,特别是当摩擦系数随滑动速度的降低而增加时。
从用户满意的角度考虑,机动车在其使用寿命期间任何时刻均无颤动发生是至关重要的。OEM的数据表明,颤动在新材料互相摩擦时要比材料磨合之后更为严重。这就是说,工厂在填写使用情况报告数据表时,ATF必须显示,除了磨合后,更重要是磨合前要有良好的初期颤动表现。自动变速器流体可采用DEXRONIII ECCC机动车操作试验来测试颤动性能。ECCC机动车操作试验要求机动车在一系列预先规定的速度和荷载条件下行驶并根据测力计予以考核。实际道路行驶试验还可被用来检查变速器内是否有颤抖发生。
需要一种方法来有效地克服因自动变速器中所用连续打滑变矩器离合器引起的颤动问题,尤其是磨合前新材料摩擦时出现的颤动。在满足这一需要的过程中,同样重要的一点是,要保证自动变速器流体所需要的摩擦特性不随时间的推移而发生显著变化。
本发明通过提供一种不但在磨合后而且在磨合前的初期都表现出优良抗颤动性能的自动变速器流体,从而克服了颤动问题。而且,在获得这种操作优点的同时,摩擦性能不随时间推移发生显著改变。因此,本发明现已使OEM有可能在自动变速器中有效地利用ECCC设计,以获得此种设计可能带来的利益。
美国专利5,344,579、5,372,735、5,441,656及5,578,236公开了表现出良好抗颤动性能的自动变速器流体组合物、上述专利指出,优选的分散剂是含磷或硼的分散剂,虽然也可用非磷酸化或非硼化的分散剂来代替或添加到,含磷及含硼分散剂中。但是这些参考文献未能指出或暗示本发明分散剂中所给出的具体的氮-磷比例。而且,这些文献也未能公开或依推理暗示,包含本发明分散剂的自动变速器流体所配制成的组合物在换档离合器使用中可表现出,与所含分散剂的氮-磷比例低于本发明的类似自动变速器流体相比,较高的中点力矩、较高的静力矩以及较好的摩擦耐久性。
EP 0,747,464 A1公开了一种供抗颤动摩擦耐久的自动变速器使用的组合物。该组合物要求联合使用至少3种选自一张列举了11类摩擦改进剂的清单的摩擦改进剂。该公开没有指出或暗示本发明的分散剂。况且,本发明的组合物不要求使用这至少3种摩擦改进剂,就能获得良好的抗颤性能。
发明概述
本发明,按其实施方案之一,提供一种自动变速器流体,它包含作为关键成分的一种氮与磷含量质量比为约3∶1~约10∶1的分散剂。
本发明的分散剂可按照至少两种方法制备。在一种方法中,将无灰分分散剂磷酸化,使氮与磷含量质量比达到约3∶1~约10∶1。在另一种实施方案中,将磷酸化的分散剂与未磷酸化的分散剂掺混在一起,使掺混后分散剂的总氮与磷含量质量比达到约3∶1~约10∶1。
在一种实施方案中,本发明的分散剂被用来配制自动变速器流体,该流体在按照DEXRONIII程序进行的GM带式(摩擦材料)离合器试验(GM Band Clutch Test)(GM(通用动力公司)操作规范:GM6417 M,1997年4月)中,整个试验期间均表现出至少185 Nm的中点力矩。已发现,通过采用氮与磷含量质量比约3∶1~约10∶1的分散剂并配合加入至少一种摩擦改进剂,所获得的动力传递流体可在换档离合器的应用中显示出,与氮与磷含量质量比小于3∶1的分散剂的类似自动变速器流体相比,优良的抗颤性能以及较高中点力矩及较高静力矩,乃至较好的摩擦耐久性。
在本发明另一种实施方案中,提出了一种消除自动变速器中初期颤动的方法以及一种提供良好抗颤耐久性的方法。所述方法包括向变速器中加入自动变速器流体并让该流体工作在变速器中,该流体包含(1)占多数的基础油以及(2)少量的添加剂组合物,后者包含的关键成分是:(A)具有氮与磷含量质量比约3∶1~约10∶1的分散剂以及(B)至少一种摩擦改进剂,其中自动变速器流体在按照DEXRONIII程序进行的GM带式离合器试验(GM操作规范:GM 6417 M,1997年4月)中,整个试验期间自动变速器流体均表现出至少185 Nm的中点力矩。抗颤耐久性的定义是,在机动车的使用寿命期间不发生显著颤动。
附图简述
图1~8显示出,在按照DEXRONIII程序进行的GM带式离合器试验(GM操作规范:GM 6417 M,1997年4月)中,本发明自动变速器流体(ATF A、B及D)的动(中点)力矩及最大力矩,与本发明范围以外的自动变速器流体(ATF C及E)相比的提高。
发明详述
本发明的自动变速器流体包含作为重要成分的(A)氮与磷含量质量比为约3∶1~约10∶1的分散剂以及(B)至少一种摩擦改进剂。
成分(A)
成分(A)包含至少一种油溶性含磷无灰分散剂。该含磷无灰分散剂的制备方法可为:将一种在分子中含碱性氮和/或至少一个羟基的无灰分散剂,例如琥珀 酰亚胺分散剂、琥珀酸酯分散剂、琥珀酸酯-酰胺分散剂、曼尼期碱分散剂、烃基多胺分散剂或聚合的多胺分散剂,予以磷酸化。
那些含至少30碳原子的烃基取代的琥珀酰基多胺琥珀酰亚胺,例如可参见美国专利3,172,892、3,202,678、3,216,936、3,219,666、3,254,025、3,272,746以及4,234,435。链烯基琥珀酰亚胺可用传统方法制备,例如将链烯基琥珀酸酐、酸、酸酯、酰基卤或低级烷基酯,与含至少一个伯氨基的多胺一起加热。链烯基琥珀酸酐可通过,将烯烃与马来酐混合加热到例如180~220℃来方便地制备。该烯烃优选地是诸如乙烯、丙烯、1-丁烯、异丁烯之类低级单烯或其混合物的聚合物或共聚物。更优选的链烯基来源选自一定的聚异丁烯,其凝胶渗透色谱(GPC)数均分子量最高达10,000或更高,优选在约500~约2,500,最优选在约800~约1,200。
本文所使用的术语“琥珀 酰亚胺”意在涵盖由一种或多种多胺反应物与烃基取代的琥珀酸或酸酐(或琥珀酰化试剂之类)之间的反应获得的全部反应产物,而且意在涵盖那些产物中包含由伯氨基与酸酐部分反应生成的酰胺、脒和/或盐键,乃至酰亚胺键等的化合物。
含2~20个碳原子及2~6个羟基基团的多元醇与链烯基琥珀酸的酯及二酯,也可用来配制该含磷无灰分散剂。有代表性的例子可见诸于美国专利3,331,776、3,381,022及3,522,179。这些酯的链烯基琥珀酰部分对应于上述琥珀酰亚胺的链烯基琥珀酰部分。
适合用于配制磷酸化无灰分散剂的链烯基琥珀酸酯-酰胺,例如可见诸于美国专利3,184,474、3,576,743、3,632,511、3,804,763、3,836,471、3,862,981、3,936,480、3,948,800、3,950,341、3,957,854、3,957,855、3,991,098、4,071,548以及4,173,540。
可用来进行磷酸化的烃基多胺分散剂的通常制法为,让平均含至少约40个碳原子的脂族或脂环族卤化物(或其混合物)与一种或多种胺,优选聚亚烷基多胺,进行反应。此类烃基多胺的例子可见诸于美国专利3,275,554、3,394,576、3,438,757、3,454,555、3,565,804、3,671,511及3,821,302。
一般地,该烃基取代的多胺是分子中包含碱性氮原子的高分子量烃基-N-取代多胺。烃基的典型数均分子量,按GPC测定,为约750~10,000,更常见在约1,000~5,000,并且是由适当的聚烯烃转化而来的。优选的烃基取代胺或多胺可由聚异丁烯氯化物(polyisobutenyl chlorides)与含2~约12个胺氮原子及2~约40个碳原子的多胺制备。
可用来配制该磷酸化无灰分散剂的曼尼期多胺分散剂是:烷基苯酚,其典型是在环上包含长链烷基取代基的,与一种或多种含1~约7个碳原子的脂族醛(尤其是甲醛及其衍生物)及多胺(尤其是聚亚烷基多胺)之间的反应产物。曼尼期缩合产物的例子及其制法可见诸于美国专利2,459,112、2,962,442、2,984,550、3,036,003、3,166,516、3,236,770、3,368,972、3,413,347、3,442,808、3,448,047、3,454,497、3,459,661、3,493,520、3,539,633、3,558,743、3,586,629、3,591,598、3,600,372、3,634,515、3,649,229、3,697,574、3,703,536、3,704,308、3,725,277、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、3,872,019、3,904,595、3,957,746、3,980,569、3,985,802、4,006,089、4,011,380、4,025,451、4,058,468、4,083,699、4,090,854、4,354,950以及4,485,023。
用于配制曼尼期多胺分散剂的优选烃类来源是,那些由基本饱和的石油馏分及烯烃聚合物,优选含2~约6个碳原子的单烯的聚合物,经转化而来的烃类。该烃类源通常包含至少约40,优选至少约50个碳原子,以便为分散剂提供基本上为油溶的性质。GPC数均分子量为约600~5,000的烯烃聚合物之所以优选的原因在于容易起反应和成本低。然而,分子量更高的聚合物也可使用。尤其合适的烃类源是异丁烯聚合物。
用于此目的的优选曼尼期碱分散剂是,由约1摩尔比例的长链烃取代苯酚与约1~2.5摩尔甲醛,及约0.5~2摩尔聚亚烷基多胺进行缩合制备的曼尼期碱无灰分散剂。
适合用于配制磷酸化无灰分散剂的聚合多胺分散剂是,包含碱性胺基团及油溶性基团(如含至少约8个碳原子的烷基侧基)的聚合物。此种材料的范例是,由诸如甲基丙烯酸癸基酯、乙烯基癸基醚以及分子量较高的烯烃之类各种单体,与丙烯酸氨基烷基酯及氨基烷基丙烯酰胺等单体制成的共聚体。聚合多胺分散剂的例子可见诸于美国专利3,329,658、3,449,250、3,493,520、3,519,565、3,666,730、3,687,849及3,702,300。
对上述各种类型无灰分散剂进行磷酸化的操作程序可见诸于美国专利3,184,411、3,342,735、3,403,102、3,502,607、3,511,780、3,513,093、3,513,093、4,615,826、4,648,980、4,857,214以及5,198,133。
在优选的实施方案中,本发明的含磷分散剂还要进行硼化。可用于上述各种类型无灰分散剂硼化(或硼酸化)的方法可见诸于美国专利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以及4,652,387。
用于诸如以上所给出的那些优选无灰分散剂的磷酸化和硼化的优选程序可见诸于美国专利4,857,214及5,198,133。
磷酸化无灰分散剂的用量,以活性成分为基准(即除掉典型地与此相联系的杂质、稀释剂及溶剂的重量),一般在约0.5~约7.5%(重量),典型地在约0.5~5.0%(重量),优选地在约0.5~约3.0%(重量),最优选在约2.0~约3.0%(重量)范围内。
如果氮与磷含量质量比为至少3∶1的本发明分散剂是通过将磷酸化并任选地硼化的无灰分散剂,与未磷酸化无灰分散剂进行掺混,得到一种总氮与磷含量质量比介于约3∶1~约10∶1的分散剂而制成的,则合适的不含磷的分散剂包括上面所描述的无灰分散剂。然而,作为成分(B)的该无灰分散剂是不经磷酸化的。该未磷酸化的无灰分散剂的用量,以活性成分为基准(即除掉典型地与此相联系的杂质、稀释剂及溶剂的重量),一般在约0.5~约7.5%(重量),典型地在约0.5~约4.0%(重量),优选地在约1.0~约3.5%(重量)范围内。
磷酸化无灰分散剂对未磷酸化无灰分散剂的相对比例优选在1∶10~10∶1,更优选1∶5~5∶1(重量),最优选2∶1~1∶2(重量)。再有,任何比例,只要全部分散剂的氮与磷含量质量比在约3∶1~约10∶1范围,都是合适的。
在一种优选的实施方案中,分散剂(A)的氮与硼的质量比为5∶1~约15∶1。
成分(B)
本发明组合物包含一种或多种摩擦改进剂。它们包括如下的化合物:例如脂肪胺或乙氧基化脂肪胺、脂族的脂肪酸酰胺、乙氧基化脂族醚胺、脂族羧酸、甘油酯、脂族羧酸酯-酰胺、脂族膦酸酯、脂族磷酸酯、脂族硫代膦酸酯、脂族硫代磷酸酯、脂肪咪唑啉、脂肪叔胺等,其中脂族基团一般包含约8个以上碳原子以便赋予该化合物以适当的油溶性。同样合适的是,由一种或多种脂族琥珀酸或酸酐与氨或其他伯胺反应生成的脂族取代的琥珀 酰亚胺。
一类优选的摩擦改进剂体系由N-脂族烃基取代的二乙醇胺构成,其中该N-脂族烃基取代基是至少一种不含炔键不饱和部分的、含约14~约20个碳原子的直链脂族烃基。
尤其优选的摩擦改进剂体系由至少一种N-脂族烃基取代的二乙醇胺与至少一种N-脂族烃基取代的三亚甲基二胺的组合构成,其中N-脂族烃基取代基是至少一种不含炔键不饱和部分的、含约14~约20个碳原子的直链脂族烃基。有关这类摩擦改进剂体系的进一步细节可见诸于美国专利5,372,735及5,441,656,该两篇文献一并收作本文的参考。
另一类特别优选的摩擦改进剂体系基于以下的组合:(1)至少一种二(羟烷基)脂族叔胺,其中羟烷基可以相同或不同,每一个包含2~约4个碳原子,而其中脂族基团是含约10~约25个碳原子的无环烃基,以及(2)至少一种羟烷基脂族咪唑啉,其中羟烷基包含约2~约4个碳原子,且脂族基团是包含约10~约25个碳原子的无环烃基。有关这类摩擦改进剂体系的进一步细节可见诸于美国专利5,344,579,该文收作本文的参考。
成分(1),即二(羟烷基)脂族叔胺,包含与两个羟烷基基团及一个含10~25个碳原子,优选13~19个碳原子的无环脂族烃基基团键合的氮原子。该叔胺的羟烷基可以相同或不同,但每一个包含2~4个碳原子。羟基可位于羟烷基中的任何位置,但是优选位于β-位。优选的是,成分(1)中的这两个羟烷基相同,且最优选是2-羟乙基基团。该叔胺的脂族基团可为直链或支链,且它可以是饱和的或烯键不饱和的,而若为不饱和的,就典型而言它包含1~3个烯烃双键。成分(1)可包含单一类型的脂族基团,或者它可包含具有不同脂族基团的化合物的混合物,但其中碳原子的平均数目应介于10~25个碳原子的上述范围。
从以上可清楚地看出,成分(1)可以是满足上述结构准则的单一化合物或多种化合物的混合物。
适合用于实施本发明的羟烷基脂族咪唑啉,即成分(2),特征是,在咪唑啉环的1-位上带有包含2~4个碳原子的羟烷基,而且在环的相邻的2-位上带有包含10~25个碳原子的无环羟烷基。虽然该羟烷基的羟基可位于其任何位置上,但优选位于β-碳原子上,如2-羟乙基、2-羟丙基或2-羟丁基。就典型而言,该脂族基团是饱和或烯键不饱和烃基基团,而当为烯键不饱和的时,该脂族基团可包含1、2或3个此类双键。成分(2)可以是单一、基本纯净的化合物,或者是其中脂族基团为平均含10~25个碳原子的多种化合物的混合物。优选的是,该脂族基团包含15~19个碳原子,或平均包含15~19个碳原子。最优选的是,该脂族基团包含或平均包含17个碳原子。该(一个或多个)脂族基团可以是直链的或支链的基团,而以基本直链的基团为优选。一种特别优选的化合物是1-羟乙基-2-十七碳烯基咪唑啉。
因此可清楚地看出,成分(2)可以是满足上述结构准则的单一化合物或多种化合物的混合物。
一般而言,本发明组合物将包含,按活性成分计,最多约1.25%(重量),优选,按活性成分计,约0.05~约1%(重量)一种或多种摩擦改进剂。
成分(C)
本发明组合物任选地,但优选地包含粘度指数改进剂(VII)。优选的VII,包括但不限于烯烃共聚物VII、聚甲基丙烯酸烷基酯VII以及苯乙烯-马来酸酯VII。这当中,聚甲基丙烯酸烷基酯是特别优选的。粘度指数改进剂是以在惰性溶剂中,就典型而言在矿物油溶剂中,的溶液形式供应的,它通常是严格精制的矿物油。供货形式的粘度指数改进剂溶液,其沸点应高于200℃,25℃下的比重小于1。优选的是,该粘度指数改进剂具有足够高的剪切稳定性,以便使成品组合物,在按照ASTM D-5275进行的FISST(燃油喷嘴剪切稳定性试验)中经40次循环之后,其100℃下的运动粘度至少是5,更优选至少是6.8 cSt.按活性成分计(即除掉与所提供的粘度指数改进剂相联系的惰性稀释剂或溶剂),本发明流体组合物制成品一般含有约1~约20%(重量)聚合物粘度指数改进剂。视可能的具体情况而异,必要或希望时可酌情对上述范围做少量增减。
适合用作成分(C)的材料包括苯乙烯-马来酸酯VII,如LUBRIZOL3702、LUBRIZOL3706以及LUBRIZOL3715,可由Lubrizol公司购得;聚甲基丙烯酸烷基酯VII,如可从RHM公司(RHM GMbH)(Darmstadt,德国)按商品名VISCOPLEX5543、VISCOPLEX5548、VISCOPLEX5549、VISCOPLEX5550、VISCOPLEX5551以及VISCOPLEX5151购得,从Rohm & Haas公司(费城,宾州)按商品名ACRYLOID1277、ACRYLOID1265以及ACRYLOID1269购得,及从乙基公司(Ethyl Corporation)(里士满,弗吉尼亚)按商品名HiTEC5710粘度指数改进剂购得;以及烯烃共聚物VII,诸如由乙基公司供应的商品名为HiTEC5747的VII、HiTEC5751的VII、HiTEC5770的VII以及HiTEC5772的VII,以及壳牌化学公司供应的SHELLVIS200。上述产品的混合物也可用作分散剂和分散剂/抗氧剂VII。从其他制造公司也有可能获得具有作为成分(C)使用所要求操作性能的粘度指数改进剂。有关此类产品的化学组成及其制法的细节被相应产品的制造公司视为秘密加以保守。
优选的是,粘度指数改进剂以聚合物含量为约25~约80%(重量)范围、氮含量为约0~约0.5%(重量)范围的烃类溶液形式供应。此类产品优选具有的永久剪切稳定性指数(PSSI值),采用ASTM试验,方法D-3945A,不大于约75。优选小于或等于50,最优选小于或等于35。
本发明自动变速器流体还包含密封润胀剂(seal swellagents)、抗氧剂、缓蚀剂、消泡剂、铜缓蚀剂、抗磨/抗极压添加剂、润滑剂及染料。
在选择上述任选添加剂中任何一种时,重要的是应确认,所选择的这种(或几种)成分可溶于或可稳定地分散在整个添加剂包中和成品ATF组合物中,而且应与组合物的其他成分相容,不会显著干扰组合物的操作性能,如整个成品组合物的摩擦、粘度和/或剪切稳定性等这样一些整个组合物必备或至少希望具有的性能。
一般地,这些辅助添加剂在油中的用量应为足以改进该基础流体性能特征及性质的较少数量。故而,该数量将随诸如所使用的基础流体的粘度特性、所要求的成品流体粘度特性、预期成品流体的工作条件,以及希望成品流体所达到的操作性能等因素的不同,而有所变化。然而,一般而言,下面给出的添加剂成分活性成分在基础流体中的含量(质量百分率)具有示范意义:
典型范围 | 优选范围 | |
总分散剂 | 1-15 | 1-8 |
摩擦改进剂 | 0.05-1.25 | 0.05-1 |
粘度指数改进剂 | 0-20 | 0-10 |
密封润胀剂 | 0-30 | 0-20 |
抗氧剂 | 0-1 | 0.25-1 |
缓蚀剂 | 0-0.5 | 0.01-0.1 |
抑泡剂 | 0-0.01 | 0.0001-0.005 |
铜缓蚀剂 | 0-0.5 | 0.01-0.05 |
抗磨/抗极压剂 | 0-1 | 0.25-1 |
润滑剂 | 0-1.5 | 0.5-1 |
染料 | 0-0.05 | 0.015-0.035 |
应注意,所采用的个别成分可分开掺混到基础流体中去,亦或按各种不同亚组合(subcombination)掺混到其中,可酌定。通常,对此类掺混步骤的特定顺序并无严格要求。而且,此类成分还可以各自的稀释剂溶液形式进行掺混。然而优选的是,将所有要使用的添加剂成分以一种浓缩液的形式一起掺入,因为这样能简化掺混操作,减少掺混误操作的可能,并利用该全体浓缩液所提供的相容性和溶解性方面的优点。
因此,可配制一种包含全部添加剂成分的添加剂浓缩液,而且希望的话,还可加入一定量的基础油成分,各种成分的数量应按比例配制,配成与上面所述浓度相一致的调制流体掺混液。在多数情况下,该添加剂浓缩液将包含一种或多种稀释剂,如轻质矿物油,以利于对浓缩液的操作及成分之间的掺混。于是,就可使用包含最高约50%(重量)一种或多种稀释剂或溶剂的浓缩液,条件是溶剂的含量不影响成品动力传递流体组合物的高、低温及闪点特性及操作性能。就这一点而论,应选择按本发明使用的添加剂成分及其比例,使由这些成分配制的添加剂浓缩液或添加剂包的闪点,按ASTM D-92试验程序测定,为170℃或更高,优选闪点为至少180℃。
还可使用极少量的某些含金属的洗涤剂,如钙的硫化酚盐。然而,若使用此种油溶性酚盐,则应按比例配制,以便使成品流体包含不大于约250ppm的金属,优选不大于约100ppm的金属,最优选不大于约50ppm的金属。优选这些硫化酚盐为含化学计算量钙的中性盐,在任何情况下总碱值(TBN)不得超过约200mg KOH/g。
在成品流体的含磷不完全是由加入含磷无灰分散剂(或含硼-及磷的无灰分散剂)提供的情况下,所含磷的其余部分优选通过在组合物中加入一种或多种含磷酯或酸酯来提供,如油溶性有机亚磷酸酯、油溶性有机酸亚磷酸酯、油溶性有机磷酸酯、油溶性有机酸磷酸酯、油溶性氨基磷酸酯。例子包括三烃基磷酸酯、三烃基亚磷酸酯、二烃基磷酸酯、二烃基膦酸酯或二烃基亚磷酸酯及其混合物、单烃基磷酸酯、单烃基亚磷酸酯,以及以上任何两种或多种的混合物。有机酸磷酸酯的油溶性铵盐是用于本发明流体优选的一类辅助含磷添加剂。任何上述化合物的含硫类似物也可使用,然而不那么优选。作为有商品供应的辅助磷添加剂,最优选的是Ciba-Geigy公司的商品Irgalube349,这是一种磷酸酯胺(amine phosphate)抗磨/抗极压添加剂。
根据以上所述,在其实施方案之一中,本发明提供一种组合物,它包含诸如琥珀 酰亚胺之类的含磷及硼的无灰分散剂,并配合至少一种选自下列成分的含磷物质:(1)一种或多种磷的无机酸,或(2)一种或多种磷的无机硫代酸,或(3)一种或多种磷的无机酸的单烃基酯,或(4)一种或多种磷的无机硫代酸的单烃基酯,或者(5)上述成分的任意组合;或者选自(1)、(2)、(3)、(4)及(5)中至少一种的油溶性铵盐或配合物或者加成产物,任选地,所述胺整个或部分地是诸如琥珀酰亚胺之类的含磷、硼及碱性氮原子的无灰分散剂中的胺部分。
本发明组合物所含的硼优选地完全通过加入含硼及磷的无灰分散剂来提供。当成品流体所含硼不完全是采用这样的方式提供的时候,所含硼的不足部分可通过在组合物中加入一种或多种油溶性硼酯来提供,如加入乙二醇硼酸酯或乙二醇二硼酸酯。
用于配制本发明自动变速器流体的基础油可以是具有此类用途所必备粘度性能的任何适当天然或合成油。天然油包括动物油及植物油(如蓖麻油、猪油等)、液态石油油品,以及石蜡、环烷及混合石蜡-环烷型加氢精制的、严格加氢处理的、异构-脱蜡的、溶剂处理的或酸处理的矿物润滑油。由煤或页岩提炼、具有润滑用粘度的油也是有用的基础油。适用于本发明的合成润滑油包括众多普遍使用的合成烃类油当中的任何一种,包括但不限于:聚α-烯烃、合成酯、烷基化芳烃、氧化烯聚合物,共聚体,共聚物及羟端基已被酯化、醚化等改性的衍生物、二羧酸酯以及硅基油类。因此,基础油可完全由诸如矿物油的粘度适当的天然油构成,或者完全由诸如聚α-烯烃低聚物之类粘度适当的合成油构成。同样,基础油还可以是天然与合成基础油的掺混物,条件是该掺混油具备用于配制自动变速器流体所要求的性质。一般地,基础油在100℃下的运动粘度应为3~8 cSt。用于实施本发明的优选自动变速器流体,可不需要添加粘度指数改进剂便配制成具有在100℃下运动粘度至少是4.0 cSt,且-40℃下Brookfield粘度不大于20,000厘泊的配制油,或者可添加粘度指数改进剂来配制,以便获得100℃下运动粘度至少是5.0,优选至少6.8 cSt且-40℃下Brookfield粘度不大于20,000厘泊的配制油。
实施例
ATF摩擦性能的评价可在SAE 2号摩擦机上按照DEXRONIII及MERCON摩擦试验程序进行。低速(最大)及动(中点)力矩以及时间曲线,可在包括24,000次循环的100小时试验期间取得。要通过该测试,ATF的中点动力矩必须介于150~180 Nm,而接合时间必须介于0.45~0.60秒。DEXRONIII带式离合器试验(GM操作规范:GM6417 M,1997年4月)涉及在135℃及每分钟4次循环的速率下进行100小时(即24,000次)的接合离合器试验。DEXRONIII带式离合器试验对中点力矩的极限值是185~220 Nm。
在下面的实例1~3中给出了适合用于实施本发明的范例组合物,其中所有的份数和百分数均指重量而言。成分(A’)是聚异丁烯基(PIB)琥珀酰亚胺分散剂,其中PIB的数均分子量为约900,该分散剂包含磷和硼这两种元素,其制备方法基本上如美国专利4,857,214的实例1A中所述。成分(A)是未磷酸化、未硼化的聚异丁烯基琥珀酰亚胺分散剂,其中PIB数均分子量为约900。摩擦改进剂(1)是羟烷基脂族咪唑啉,摩擦改进剂(2)是二(羟烷基)脂族叔胺。对比例2(ATF E)包含与美国专利5,344,579中所载的相同分散剂/摩擦改进剂组合物。所有的配制物均包含市售辅助添加剂,如粘度指数改进剂、密封润胀剂、抗氧剂、缓蚀剂、抑泡剂、抗磨/抗极压剂以及润滑剂,各自的用量按均按常规。用作ATF A、B、D及E的基础油是100 N矿物油。用于ATF C的基础油是70 N与100 N矿物油的掺混物。全部含量均按活性成分含量计算。
实施例1(ATF A)
组分 | Wt.% in ATF |
组分(A’) | 1.51 |
组分(A”) | 2.92 |
磨擦改进剂(i) | 0.05 |
摩擦改进剂(ii) | 0.10 |
分散剂的N∶P比 | 6∶1 |
实施例2(ATF B)
组分 | Wt.% in ATF |
组分(A’) | 1.51 |
组分(A”) | 2.92 |
磨擦改进剂(i) | 0.05 |
摩擦改进剂(ii) | 0.10 |
分散剂的N∶P比 | 6∶1 |
实施例3(ATF D)
组分 | Wt.% in ATF |
组分(A’) | 1.51 |
组分(A”) | 1.10 |
磨擦改进剂(i) | 0.02 |
摩擦改进剂(ii) | 0.12 |
分散剂的N∶P比 | 3.6∶1 |
对比例1(ATF C)
组分 | Wt.% in ATF |
组分(A’) | 2.07 |
组分(A”) | 0.00 |
摩擦改进剂(ii) | 0.15 |
分散剂的N∶P比 | 2.15∶1 |
对比例2(ATF E)
组分 | Wt.% in ATF |
组分(A’) | 2.07 |
组分(A”) | 0.00 |
磨擦改进剂(i) | 0.05 |
摩擦改进剂(ii) | 0.10 |
分散剂的N∶P比 | 2.15∶1 |
以上ATF组合物,包括实例1~3以及对比例1和2中的A~E,全都显示出良好的抗颤动性能,正如从没有初期颤动和良好的抗颤耐久性所反映出来的。然而,本发明的ATF组合物A、B及D(实例1~3)在换档离合器使用中显示出,比那些所含分散剂的氮与磷含量质量比小于3∶1的ATF C及ATF E(分别为对比例1及2)更高的中点力矩和更高的静力矩,以及更好的摩擦耐久性。
图1及图2举例说明的试验中所使用的带式摩擦材料与图3~8中所使用的带状摩擦材料不同,因此当把图1与图3或图5,以及把图2与图4或图6做一比较时,ATF C的中点力矩及最大力矩看上去有所不同。所有GM带式离合器试验均按照DexronIII规程进行。
在图1中,ATF组合物A、B及C,采用一种不符合DexronIII规范的带式摩擦材料(BW 1301)进行了GM带式离合器试验。测定出各个组合物的中点力矩,并将结果作为时间的函数作图。研究了这些数据之后可清楚地看出,包含氮与磷含量质量比至少是3∶1的分散剂的ATF组合物(ATF A及B)在整个测试期间表现出,比包含氮与磷含量质量比小于3∶1的分散剂的类似ATF组合物(ATF C)更为合意、更高的中点力矩。
在图2中,ATF组合物A、B和C接受了采用与图1中相同带式摩擦材料的GM带式离合器试验。测定出各个组合物的最大力矩并作为时间的函数作图。研究了这些数据之后可清楚地看出,与包含氮与磷含量质量比小于3∶1的分散剂的类似ATF组合物(ATF C)相比,包含氮与磷含量质量比至少是3∶1的分散剂的本发明组合物(ATF A及B)在整个测试期间表现出出乎意料更高的最大(低速)力矩。
在图3中,组合物A及C按照DEXRONIII程序采用BW 1473-2带式材料进行了GM带式离合器试验。测定了组合物的中点力矩并作为时间的函数作图。研究了这些数据之后可清楚地看出,与包含氮与磷含量质量比小于3∶1的分散剂的类似ATF组合物(ATF C)相比,包含氮与磷含量质量比至少是3∶1的分散剂的ATF组合物(ATF A)在整个测试期间表现出出乎意料高的中点力矩。
在图4中,ATF组合物A及C按照DEXRONIII程序采用BW 1473-2带式材料进行了GM带式离合器试验。测定了组合物的最大力矩并作为时间的函数作图。研究了这些数据之后可清楚地看出,与包含氮与磷含量质量比小于3∶1的分散剂的类似ATF组合物(ATF C)相比,包含氮与磷含量质量比介于约3∶1~约10∶1的分散剂的本发明的ATF组合物(ATF A)在整个测试期间表现出更高的最大(低速)力矩。
在图5中,组合物C及D按照DEXRONIII程序采用BW 1473-2带式材料进行了GM带式离合器试验。测定了组合物的中点力矩并作为时间的函数作图。研究了这些数据之后可清楚地看出,与包含氮与磷含量质量比小于3∶1的分散剂的类似ATF组合物(ATF C)相比,包含氮与磷含量质量比介于约3∶1~约10∶1的分散剂的ATF组合物(ATF D)在整个测试期间表现出更高的中点力矩。
在图6中,ATF组合物C及D按照DEXRONIII程序采用BW 1473-2带式材料进行了GM带式离合器试验。测定了组合物的最大力矩并作为时间的函数作图。研究了这些数据之后可清楚地看出,与包含氮与磷含量质量比小于3∶1的分散剂的类似ATF组合物(ATF C)相比,包含氮与磷含量质量比介于约3∶1~约10∶1的分散剂的本发明的ATF组合物(ATF D)在整个测试期间表现出更高的最大(低速)力矩。
在图7中,组合物A及E按照DEXRONIII程序采用BW 1473-2带式材料进行了GM带式离合器试验。测定了组合物的中点力矩并作为时间的函数作图。研究了这些数据之后可清楚地看出,与包含氮与磷含量质量比小于3∶1的分散剂的类似ATF组合物(ATF E)相比,包含氮与磷含量质量比介于约3∶1~约10∶1的分散剂的ATF组合物(ATF A)在整个测试期间表现出更高的中点力矩。
在图8中,组合物A及E按照DEXRONIII程序采用BW 1473-2带式材料进行了GM带式离合器试验。测定了组合物的最大力矩并作为时间的函数作图。研究了这些数据之后可清楚地看出,与包含氮与磷含量质量比小于3∶1的分散剂的类似ATF组合物(ATF E)相比,包含氮与磷含量质量比介于约3∶1~约10∶1的分散剂的本发明的ATF组合物(ATF A)在整个测试期间表现出更高的最大(低速)力矩。
从以上给出的数据可清楚看出,与本发明范围以外的组合物相比(即所含分散剂的氮与磷质量比小于3∶1的流体),本发明组合物表现出出乎意料的、更高的中点力矩和最大力矩值。因此,正如由给出的数据所证实的,现已有可能配制一种满足最近出现的功率较小、要求性能更高的变速器对高力矩需求的动力传递流体,同时它又保留了较低力矩的动力传递流体所具有的优良抗颤动特性。
本发明在实施中仍可具有相当多的变化。因此,本发明不局限于上面所给出的特定实施例。相反,就法律角度而言,本发明的精神和范围由所附权利要求及其合适的同等物规定。
本专利权所有人无意将所公开的任何实施方案奉献给公众,而当出现任何公开的变换从字面上看不属于权利要求范围内的情况时,根据等价的原则,它们均应视为本发明的一部分。
Claims (24)
1.一种表现出优良抗颤动性能的自动变速器流体组合物,包含(1)91.25-99.45重量%的基础油以及(2)0.55-8.75重量%的添加剂组合物,后者包含:
(A)总氮与磷含量质量比为3∶1~10∶1的分散剂;以及
(B)一种摩擦改进剂。
2.权利要求1的自动变速器流体,其中分散剂(A)通过将一种无灰分散剂磷酸化制成,磷酸化的程度应足以使得所获得的分散剂具有3∶1~10∶1的氮与磷含量质量比。
3.权利要求1的自动变速器流体,其中分散剂(A)的制法为:将(A’)磷酸化的分散剂与(A”)未磷酸化的分散剂掺混,以便达到掺混后分散剂的总氮与磷含量质量比为3∶1~10∶1。
4.权利要求3的自动变速器流体,其中分散剂中的一种,即(A’)或(A”),是琥珀酰亚胺分散剂。
5.权利要求2的自动变速器流体,其中分散剂(A)经过了硼化。
6.权利要求3的自动变速器流体,其中分散剂中的一种,即(A’)或(A”),经过了硼化。
7.权利要求1的自动变速器流体,还包含(C)粘度指数改进剂。
8.权利要求7的自动变速器流体,其中粘度指数改进剂(VII)选自烯烃共聚物VII、聚甲基丙烯酸烷基酯VII以及苯乙烯-马来酸酯异聚物(styrene-maleic ester isopolymer)VII。
9.权利要求1的自动变速器流体,其中摩擦改进剂(B)包含由下列成分构成的组合:(1)一种二(羟烷基)脂族叔胺,其中羟烷基可相同或不同,每一个包含2~4个碳原子,而其中脂族基团是包含10~25个碳原子的无环烃基,以及(2)一种羟烷基脂族咪唑啉,其中羟烷基包含2~4个碳原子,而其中脂族基团是包含10~25个碳原子的无环烃基。
10.权利要求1的自动变速器流体,其中摩擦改进剂(B)包含由一种N-脂族烃基取代的二乙醇胺及一种N-脂族烃基取代的三亚甲基二胺组成的组合,其中N-脂族烃基取代基是一种不含炔键不饱和部分且包含14~20个碳原子的直链脂族烃基。
11.权利要求1的自动变速器流体,还包含一种添加剂,选自密封润胀剂、抗氧剂、缓蚀剂、抑泡剂、铜缓蚀剂、抗磨/抗极压添加剂、润滑剂以及染料。
12.一种消除自动变速器中初期颤动的方法,所述方法包括向所述自动变速器中加入如权利要求1中规定的自动变速器流体并运转于其中。
13.一种使自动变速器获得抗颤耐久性的方法,所述方法包括向所述自动变速器中加入如权利要求1中规定的自动变速器流体并运转于其中。
14.一种表现出优良抗颤动性能的自动变速器流体组合物的制备方法,包括将(1)91.25-99.45重量%的基础油与(2)0.55-8.75重量%的添加剂组合物掺混,其中该添加剂组合物包含:
(A)总氮与磷含量质量比为3∶1~10∶1的分散剂;以及
(B)一种摩擦改进剂。
15.权利要求14的自动变速器流体的制备方法,其中分散剂(A)系通过将一种无灰分散剂磷酸化制成,磷酸化的程度应足以使得所获得的分散剂具有3∶1~10∶1的氮与磷含量质量比。
16.权利要求14的自动变速器流体的制备方法,其中分散剂(A)的制法为:将(A’)磷酸化的分散剂与(A”)未磷酸化的分散剂掺混,使掺混后分散剂达到总氮与磷含量质量比为3∶1~10∶1。
17.权利要求16的自动变速器流体的制备方法,其中分散剂中一种,即(A’)或(A”),是琥珀酰亚胺分散剂。
18.权利要求15的自动变速器流体的制备方法,其中分散剂(A)经过了硼化。
19.权利要求16的自动变速器流体的制备方法,其中分散剂中一种,即(A’)或(A”),经过了硼化。
20.权利要求14的自动变速器流体的制备方法,还包含(C)粘度指数改进剂。
21.权利要求20的自动变速器流体的制备方法,其中粘度指数改进剂选自烯烃共聚物VII、聚甲基丙烯酸烷基酯VII以及苯乙烯-马来酸酯异聚物VII。
22.权利要求14的自动变速器流体的制备方法,其中摩擦改进剂(B)包含由下列成分构成的组合:(1)一种二(羟烷基)脂族叔胺,其中羟烷基可相同或不同,每一个包含2~4个碳原子,而其中脂族基团是包含10~25个碳原子的无环烃基,以及(2)一种羟烷基脂族咪唑啉,其中羟烷基包含2~4个碳原子,而其中脂族基团是包含10~25个碳原子的无环烃基。
23.权利要求14的自动变速器流体的制备方法,其中摩擦改进剂(B)包含由一种N-脂族烃基取代的二乙醇胺与一种N-脂族烃基取代的三亚甲基二胺组成的组合,其中N-脂族烃基取代基是一种不含炔键不饱和部分且包含14~20个碳原子的直链脂族烃基。
24.权利要求14的自动变速器流体的制备方法,还包含一种添加剂,选自密封润胀剂、抗氧剂、缓蚀剂、抑泡剂、铜缓蚀剂、抗磨/抗极压添加剂、润滑剂以及染料。
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- 1998-11-06 SG SG1998004570A patent/SG72885A1/en unknown
- 1998-11-11 EP EP98309231A patent/EP0919605A1/en not_active Withdrawn
- 1998-11-17 CA CA002254208A patent/CA2254208A1/en not_active Abandoned
- 1998-11-20 JP JP10331299A patent/JP3111057B2/ja not_active Expired - Fee Related
- 1998-11-26 CN CN98122816A patent/CN1097086C/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
JP3111057B2 (ja) | 2000-11-20 |
SG72885A1 (en) | 2000-05-23 |
CA2254208A1 (en) | 1999-05-26 |
AU9048998A (en) | 1999-06-17 |
JPH11217580A (ja) | 1999-08-10 |
US5972851A (en) | 1999-10-26 |
CN1218101A (zh) | 1999-06-02 |
EP0919605A1 (en) | 1999-06-02 |
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