CN1175973A - 内燃机用润滑油 - Google Patents
内燃机用润滑油 Download PDFInfo
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- CN1175973A CN1175973A CN96192083A CN96192083A CN1175973A CN 1175973 A CN1175973 A CN 1175973A CN 96192083 A CN96192083 A CN 96192083A CN 96192083 A CN96192083 A CN 96192083A CN 1175973 A CN1175973 A CN 1175973A
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Abstract
一种内燃机用润滑油,其中含有一种矿物油和/或一种合成润滑油作为基础油,和以下化学式(1)表示的硫化二硫代氨基甲酸氧钼,式中,R1或R1与R3代表含不少于14个碳原子的支链脂族烃基,R2~R4或R2与R4代表含不少于4个碳原子的脂族烃基,按钼(Mo)计算时,其数量为0.005~0.2%(重量)。
Description
本发明涉及一种内燃机用润滑油组合物,如汽油汽车用发动机油。更具体地说,本发明涉及一种可长时间保持节省燃料效果的内燃机用润滑油。
从减少大气中被认为是使地球变暖的原因之一的CO2含量,以及资源保护的观点出发,除了如抗磨性、氧化稳定性、清洗性和分散性等性能外,还强烈要求汽油汽车用发动机油(下文简称为发动机油)具有低的燃料消耗量。
通常,发动机油由石油得到的精制矿物油或由合成润滑油,如α-烯烃低聚物和酯组成,其中加有各种添加剂,如清洗剂、分散剂、抗氧化剂、抗磨剂和粘度指数改进剂。为了提高燃料效率,降低发动机油的粘度是有效的。但是,粘度越低越会增加边界润滑区,在某些情况下它会使摩擦增加。由于这一原因,最近开始将摩擦改进剂(FM)加到发动机油中,以便减少边界润滑区的摩擦。在摩擦改进剂中,有机金属添加剂比无灰添加剂如酯、胺和酰胺添加剂更有效。已知在这些有机金属添加剂中,有机钼化合物如二硫代氨基甲酸钼(MoDTC)和有机硫化二硫代磷酸氧钼(MoDTP)(译注:氧硫化钼复合盐)是十分有效的,如在日本专利未决公开No.3-23595中公开的。另据报导,MoDTC与二硫代磷酸锌(InDTP)一起使用可得到更高的减摩效果。
但是,发动机油使用一段时间后会伴有MoDTC的品质下降和消耗。所以,存在这样一个问题,虽然新鲜的发动机油有低的燃料消耗量,但是经过一段时间,发动机油的低燃料经济性会变差。为了解决上述问题,可以考虑在新鲜的油中增加MoDTC的加入量。此外,由于其中烷基较短的MoDTC的溶解性通常较低,所以增大加入量会降低贮存稳定性。另外,由于其中烷基较长的MoDTC的溶解性较高,但热阻较低,所以很难被长期使用。
因此,本发明的目的是提供这样一种内燃机用润滑油,甚至在长期使用后,它仍使摩擦损失保持在较低的水平,并且不会导致由新方法制备的MoTDC在使用前产生沉淀,这样便抑制了MoDTC的沉淀与少量淤渣的出现,即使经过长期贮存之后其质量也不会变差。
经过为实现上述目的而全力地进行研究,本发明人发现,使用预定数量的有特定结构的硫化二硫代氨基甲酸氧钼可明显延长低燃料消耗量的时间,同时甚至在长期使用和贮存后仍可稳定地被使用,从而完成了本发明。
也就是说,一种内燃机用润滑油,其中含有
(a)一种矿物油和/或一种合成润滑油作为基础油,
(b)以下化学式(1)表示的硫化二硫代氨基甲酸氧钼,按钼(Mo)计算时,其数量为0.005~0.2%(重量);式中,R1代表含不少于14个碳原子的支链脂族烃基,R2~R4代表含不少于4个碳原子的脂族烃基。
在上述式(I)中,X1~X4代表氧原子或硫原子,并且可以相同或不同。
一种内燃机用润滑油,其中含有硫化二硫代氨基甲酸氧钼,其中R1与R3为不少于14个碳原子的支链脂族烃基,R2与R4代表上述化学式(1)的脂族烃基,当按照钼(Mo)计算时,其数量为0.005~0.2%(重)。
一种内燃机用润滑油,其中含有
(a)作为基油的矿物油和/或合成润滑油,
(b)上述化学式(1)表示的硫化二硫代氨基甲酸氧钼,其中R1代表在β-位具有支链并且不少于10个碳原子的脂族烃基,R2~R4代表具有少于4个碳原子的脂族烃基,当按钼(Mo)计算时,其数量为0.005~0.2%(重)。
一种内燃机用润滑油,其中含有硫化二硫代氨基甲酸氧钼,其中R1与R3为不少于10个碳原子并且在β-位具有支链的脂族烃基,R2~R4代表上述化学式(1)具有少于4个碳的脂族烃基,当按照钼(Mo)计算时,其数量为0.005~0.2%(重)。
本发明的内燃机用润滑油还含有以磷(P)计算的数量为0.01~0.2%(重)的二硫代磷酸锌。
本发明的内燃机用润滑油还含有以硫(S)计算的数量为0.01~0.5%(重)的硫添加剂。
此外,本发明的内燃机用润滑油还含有0.2~5%(重)具有酯基的酚类抗氧剂。
再者,本发明的内燃机用润滑油含有硫化二硫代氨基甲酸氧钼,其中R1或R1与R3上从第2至第5个碳原子之间具有一个不少于4个碳原子的侧链,而在链端它与化学式(1)中的氮结合。
本发明使用的基础油是一种矿物油润滑油馏分或一种合成油。任何润滑基础油都可用作基础油,基础油用作占大部分润滑组合物的基础组分。为了得到特别优选的减摩效果,使用粘度指数不小于135的基础油是优选的。
具体地说,作为矿物油,可以使用用以下步骤生产的润滑油基础油:在减压下蒸馏如石蜡基原油的常压蒸馏渣油得到一种馏分,用溶剂如糠醛抽提生成的馏分,然后用加氢精制和溶剂如甲乙酮/甲苯脱蜡精制;可以使用由上述减压蒸馏渣油脱沥青得到的脱沥青油和用上述适合的方法处理脱沥青油制得的润滑油基础油;可以使用通过含油蜡异构化和用溶剂甲乙酮/甲苯使异构化油的适合馏分脱蜡得到的高度精制的基础油;或者可使用它们的适合混合物。
作为合成油,可以使用α烯烃的低聚物,由二元酸如己二酸和伯醇合成的二酯;由高碳醇如新戊二醇、三羟甲基丙烷或季戊四醇和一元酸合成的多元醇酯;烷基苯或聚氧亚烷基二醇;或它们的适合混合物。此外,不用说,矿物油与合成油按适与的方式混合得到的混合油当然也可用作本发明的基础油。
用于本发明的硫化二硫代氨基甲酸氧钼(MoDTC)用下列化学式(1)表示,
式中X1~X4表示氧原子或硫原子并且可以彼此相同或不同。
其中R1或R1与R3代表不少于14个碳的支链脂族烃基或在β-位具有支链且不少于10个碳的脂族烃基。优选地,R1或R1与R3代表在β-位具有支链且不少于14个碳的脂族烃基,尤其是从热稳定性出发以伯烷基为佳。该碳数优选为10-36,尤以14-24为佳。当碳数低于上述范围时,其溶解性不充分。另外,当碳数高于上述范围时,钼含量较低。为此,脱离上述范围是不适宜的作法。
该支化脂肪烃基中支链的位置,优选地导致该基团的侧链处在由第2~第5个碳原子上,在链端部,它与氮原子连接。最优选地,该基团的侧链处在第二个碳原子(即β-位)上。这是因为当该基团的支链处于α-位(例如,仲烷基等)或该基团呈直链时,MoDTC降解和不稳定。此外,当该基团在其一端部具有短支链时,情况几乎与上述直链的情况相同,属于非优选的情况。
作为侧链,优选C1-16烷基。尤为优选的是侧链的碳数几乎等于主链中的碳数,更具体地,当R1(或R3)的碳数为n时,侧链的碳数范围为{(n-2)/2}~{(n-6)/2}。其优选实例包括其中侧链碳数为{(n-4)/2}的2-己基癸基、2-庚基十一烷基、2-辛基十二烷基与2-癸基十四烷基。
式中R2~R4或R2与R4不同于上述R1或R1与R3,代表不少于4个碳的脂肪烃基,优选C4-12支链脂肪烃基,从热稳定性出发,尤其是以在β位具有支链的C4-10烷基为佳。其优选实例包括2-乙基己基与2-甲基丁基。
本文中的脂肪烃基优选为诸如烷基、环烷基与链烯基之类视具体情况而定含有酯基、醚基、醇基或羧基的烃基。此外,在式中,X1~X4代表氧原子或硫原子。优选地,X1~X4中氧原子数与硫原子数之比为1/3~3/1。
相对于润滑油总重的MoDTC加入数量在这样的范围内,以致MoDTC溶解在基础油中;按钼(Mo)计算时,其数量为0.005~0.2、优选0.02~0.15、更优选0.03~0.10%(重量)。当加入数量小于0.005%(重)时,减摩效果差;而当加入数量超过0.2%(重)时,减摩效果不会继续增加,而费用增大。此外,还可以加入其中烃基R1、R2、R3与R4不处在上述限定范围的MoDTC,只要它们对本发明的效果不产生不利影响即可。
另外,在某些情况下,用下列结构式表示二硫代氨基甲酸氧钼(MoDTC):
无论C-S2-Mo中的键被构筑成kelule结构或双键结构均可以得到上述结构式。该结构只是理论推断,其中哪一种是实际存在的结构均不会对本发明产生不利影响。
通常已知的用于制备硫化二硫代氨基甲酸氧钼(MoDTC)的方法如JA-P-62-81396所述,其中(a)三氧化钼或碱金属或铵的钼酸盐,(b)碱金属氢硫化物或通式M2S(M表示碱金属,或铵)表示的碱金属硫化物,(c)二硫化碳和(d)仲胺反应。在此情况下,二硫代氨基甲酸钼中的4个烃基R1、R2、R3与R4依据仲胺中的烃基确定。作为制备仲胺的方法,存在已知的卤代烷与氨或伯胺之间的反应,以及醇与伯胺之间的反应。
然而,在用于本发明的MoDTC中,与一个氮原子连接的2个烃基中的一个为长链基,例如,具有不少于14个碳,而另一个烃基则为短链基,例如具有不多于10个碳(下文称其为“部分长链MoDTC”)。基于下列原因,这种部分长链MoDTC的合成方法难以进行。
为了合成部分长链MoDTC、需要采用相应的仲胺。当通过使卤代烷或醇与氨反应来合成仲胺时,除了仲胺以外还包含伯胺与叔胺在内,作为烃基的组合形式,除了长链与短链的组合体以外,还包括长链与长链和短链与短链的组合形式。此外,关于仲胺的提纯过程,在碳数较少的情况下,例如在总碳数不大于16的情况下,所需仲胺可以通过蒸馏等方式提纯。然而,碳数较大的仲胺例如总碳数不小于18、尤其是不小于22的仲胺由于沸点较高和沸点差较小而难以分离。因此,难以有效地制备所需的部分长链MoDTC。
因此,为了有效地以更高的纯度和更少的副产物即与目的产物相比其中烃基部分结构不同的MoDTC的方式获得所需的MoDTC,优选通过下列方式制备部分长链MoDTC:(a)以具有卤素、羟基、磺酸基或硝基的烃衍生物与伯胺作为原料合成仲胺,(b)使仲胺、金属源与硫和碳源反应。
按照该制备方法,具有所需结构的仲胺可以在不产生非目的产物的副产物胺的条件下通过采用具有预定结构烃部分的烃衍生物和具有预定结构的烃基的伯胺被制得。这种仲胺可被用作原料以便有效地制备部分长链MoDTC。
在此制备方法中,作为仲胺生产原料的烃衍生物,可以使用具有卤素、羟基、磺酸基或硝基取代基的衍生物。优选地,由于卤代烷易于反应而被采用。作为卤代烷,其反应活性以氟代烷、氯代烷、溴代烷和碘代烷的次序递增。从操作容易的角度考虑问题,优选氯代烷。优选化合物的实例包括氯代支链烷如2-己基癸基氯、2-庚基十一烷基氯、2-辛基癸基氯和2-癸基十四烷基氯。
作为被用于该制备方法的伯胺,优选具有支链烷基的胺如2-乙基己胺和2-甲基丁胺。优选地,烷基伯胺中烷基的碳数少于烷基衍生物的碳数,其原因在于伯胺易于提纯。该制备方法中,仲胺由上述烃衍生物与伯胺反应制成。当利用卤代烷与烷基伯胺之间的反应时,出于产率与反应效率方面的考虑,卤代烷与烷基伯胺之间的摩尔比为1∶1~1∶5,尤其是1∶1.2~1∶4,反应温度为50-250℃、尤其是150-200℃。关于反应溶剂,适宜采用诸如卤化化合物与卤代烃之类的溶剂。然而,即使是在未使用溶剂的情况下,反应仍能够进行。反应之后,通过蒸馏等方式脱除未反应原料等。然而,不一定必须完成脱除副产物胺的步骤。
在此制备方法中,通过使金属源、硫与碳源与仲胺在水溶液与有机溶剂中反应来合成MoDTC。在水溶液中进行的该反应过程中,pH值优选为1~13,尤其是1.5~3.5,必要时加入诸如硫酸与盐酸之类的酸。反应温度优选地为60-110℃,尤其是95-105℃。仲胺与金属源的摩尔比优选为1∶0.8~1∶3,尤其是1∶0.9~1∶2.5。当金属源过量时,未反应物料的脱除过程变得复杂。从脱除杂质的角度出发,作为润滑添加剂,其性能上的具体改进之处优选地在于在反应之后脱除溶剂并且借助吸附剂如硅胶提纯二硫代氨基甲酸盐。另外,该合成法还可以在有机溶剂如N,N’-二甲基甲酰胺中进行。
作为用于上述合成法的金属源,可以使用在反应时能溶于溶剂中的各种金属化合物。在MoDTC的情况下,可以采用三氧化钼、碱金属钼酸盐或钼酸铵盐作为金属源。作为有待与金属源和仲胺反应的硫与碳源,优选采用硫化物如碱金属硫化物例如硫化钠、硫化铵,碱金属氢硫化物如NaSH以及二硫化碳。
上述部分长链MoDTC的制备方法同样适用于非二硫代氨基甲酸钼的二硫代氨基甲酸盐。一般地,二硫代氨基甲酸盐可用化学式(2)表示:
式中M代表金属元素如钼、钨、钛、铅、锌与铜,R与R’代表具有不同结构的烃基如烷基与芳基。金属元素与硫之间的结合方式可以依据金属元素而有所不同。一般情况下,烃基R与R’中碳数优选为4~28。二硫代氨基甲酸盐优选地被用作润滑油添加剂或胶乳与橡胶的硫化促进剂。该制备方法优选地在烃基R与R’中总碳数不少于18,尤其是不少于22或者在烃基R与R’为烷基、尤其是支链烷基的情况下被采用。
优选地,进一步加入下列通式(3)表示的二硫代磷酸锌(ZnDTP)。式中,R11~R14为烃基,如平均碳原子数不小于3的直链或支链烷基与芳基。作为R11~R14,有3~18个碳原子的烷基是优选的。具体地说,可提及的是丙基、丁基、戊基、己基、辛基和月桂基。R11~R14彼此相同或不同。
当按磷(P)计算时,ZnDTP相对于润滑油总重的加入数量为0.01~0.2、优选0.04~0.2%(重量)。在这一范围内,可以由借助MoDTC产生的协同效应获得更好的耐磨性能。当该数量大于0.2%(重)时,磷组分对废气处理催化活性产生更大的影响。
优选地,添加硫添加剂。作为硫添加剂,可以使用特压添加剂如硫化油或脂肪、硫化物、硫代碳酸盐与金属硫代氨基甲酸盐。具体地,可以使用硫化鲸蜡油、硫化蒎烯油、硫化豆油、硫化聚烯烃、二烷基二硫醚、二烷基多硫醚、二苄基二硫醚、二叔丁基二硫醚、聚烯烃多硫醚、双烷基聚磺氨基(sulfanyl)噻二唑、硫化酚与金属如锌、铅与锑的二硫代氨基甲酸盐。
具体地,优选采用下列化学式(4)所示的二硫代氨基甲酸锌(ZnDTC)与化学式(5)表示的噻二唑型聚硫醚化合物
式中R21~R24代表烃基如平均碳数不少于6的烷基、环烷基、芳基、烷基芳基、芳基烷基与链烯基,其中视具体情况而定含酯基、醚基、醇基或羧基。优选地,采用平均碳数为8-18的烷基。具体地,可被提及的有2-乙基己基、异十三烷基和十八烷基(硬脂基)。通常情况下,采用具有相同结构的R21~R24当R21~R24具有预定平均碳数时,可以混合具有不同结构的ZnDTC。由于当采用非锌金属如铅的DTC时,一部分机油燃烧并且被含在废气之中,从环境保护的观点出发,这不是优选情况。
式中R31和R32代表烃基如平均碳数不少于3的烷基、环烷基、芳基、烷基芳基、芳基烷基与链烯基,其中视具体情况而定含酯基、醚基、醇基或羧基。优选地,采用平均碳数为3-18的烷基。具体地,可被提及的有辛基、壬基和十二烷基。通常采用具有相同结构的R31与R32。当R31与R32具有预定平均碳数时,可以混合具有不同结构的聚醚化合物。“X”与“Y”代表整数2-5,通常为2-3。
硫添加剂的添加量相对于润滑油总重按照硫(S)计算为0.01-0.5%(重)、优选为0.05~0.4%(重)、更优选为0.07-0.3%(重)。当添加量少于0.01%(重)时,其使用寿命延长效果很差。另外,即使是当该数量大于0.5%(重)时,预期效果也不会继续得到改善。此外,当其中R21~R24的平均碳数小于6的MoDTC与ZnDTC同时存在于润滑油中时,润滑油变得混浊且其贮存稳定性变差,这样该润滑剂在某些情况下不适用作内燃机润滑油。
式中m代表整数1-3。
在该式中,R41与R42代表C1-12烷基,优选C3-8支链烷基。R43代表烃基如C4-50烷基、环烷基、芳基、烷基芳基、芳基烷基与链烯基,其中视具体情况而定含酯基、醚基、醇基或羧基。优选地,采用C6-16烷基。R41与R42可以彼此相同或不同。作为可供选择替代的方式,可以采用由具有不同R41~R43的2种或多种抗氧剂组成的混合物。
该抗氧剂相对于润滑油总重的添加量为0.2~5%(重)、优选0.5-2%(重)。当添加量少于0.2%(重)时,防止氧化效果较差。另外,即使是当抗氧剂加入量大于5%(重)时,防止氧化效果也不会继续得到改善而成本却增加。
为了确保适合预定用途的性能,可将除上述添加剂外的其他润滑油添加剂适当加到本发明内燃机用润滑油中,以便提高总的性能。作为这样的发动机油添加剂,可提到的是所谓的金属清洗剂,如碱土金属如Ca、Mg和Ba和碱金属如Na的磺酸盐、酚盐和水杨酸盐;不具有酯基的酚类抗氧化剂,胺类抗氧化剂,如二苯胺;无灰分散剂如链烯基琥珀酰亚胺、琥珀酸酯、琥珀酰胺与苄胺以及粘度指数改进剂,如烯烃共聚物或聚甲基丙烯酸酯。此外,也可适当加入其他一些添加剂,如倾点下降剂、防腐蚀剂和防泡剂。
实施例
参考实施例和对比实施例更详细地说明本发明。首先制备有待被用于本发明的部分长链MoDTC。
合成2-己基癸基氯
将240g(0.99摩尔)2-己基癸醇与900ml氯仿放入3升配有回流冷凝器与加料漏斗的三颈烧瓶中。在70分钟内滴加120ml(1.6mol)亚硫酰氯,室温下搅拌1小时,加入130ml(0.16摩尔)吡啶,在室温下搅拌1小时并且在75℃下继续搅拌5小时。反应完成后,用2升水洗涤该混合物,用无水硫酸钠干燥有机层。蒸除所得褐色液体中所含的溶剂,随后在减压下进行蒸馏以便得到150g(0.58摩尔)浅黄色液体。产率为59%。
合成仲胺
将5.0g(0.019摩尔)2-己基癸基氯与5.0g(0.039摩尔)2-乙基己胺放入配有回流冷凝器的100ml单颈烧瓶中,随后在180℃下搅拌11小时。由于反应生成了盐酸仲胺,所以经过碱洗,减压蒸馏得到5.9克浅黄色液体。(2-己基癸基)(2-乙基己基)胺的产率为85%。
MoDTC的合成法1
将5.1g(0.021摩尔)Na2MoO4·2H2O、5.1g(0.021摩尔)Na2S·9H2O和7ml水放入100ml单颈烧瓶中,借助20%硫酸水溶液将混合物的pH值调至2.5。于室温下搅拌30分钟后,向其中加入5.0g(0.014摩尔)(2-己基癸基)(2-乙基己基)胺和1.1g(0.14摩尔)二硫化碳,将烧瓶密封,随后在室温下搅拌1小时。此后,在单颈烧瓶上配备回流冷凝器,随后在105℃搅拌5小时。反应完毕,将反应混合物溶于100ml甲苯,用300ml水洗涤该溶液,用无水硫酸钠干燥有机层,蒸除溶剂,随后用硅胶柱进行提纯,以便得到6.6g黄绿色粘液(合成1)。
MoDTC的合成法2
将24g(0.17摩尔)MoO3、63g15~18%NaSH水溶液和200ml水放入500ml烧瓶中。用20%硫酸水溶液将混合物的pH值调至3.0。于室温下被搅拌30分钟后,加入60g(0.17摩尔)(2-己基癸基)(2-乙基己基)胺与14g(0.181摩尔)二硫化碳。反应完毕,加入500ml甲苯,将烧瓶密封,并且用1000ml水洗涤有机层。萃取有机相,用无水硫酸钠干燥,蒸除溶剂,采用硅胶提纯残余物,用丁醇洗涤,减压干燥得到60g棕黄色粘液(合成2)。
分析MoDTC
由合成1得到的MoDTC的元素分析结果如下所示:Mo.16.8%(重);S,16.7%(重);N,2.35%(重)。C50H100N2S4Mo2O4的理论值如下所示:Mo,16.8%(重);S,16.8%(重);N,2.45%(重)。此外,由13C-NMR分析结果可以证实,存在由二硫代氨基甲酸酯结构衍生的单峰(208.7ppm)。
对由合成2得到的MoDTC进行元素分析的结果如下所示:Mo,17.4%(重);S,19.4%(重);N,2.35%(重)。此外,13C-NMR分析结果可以证实,存在由二硫代氨基甲酸酯结构衍生的单峰(208.7ppm)。
由上述步骤制得化学式(1)代表的其中R1与R3代表2-己基癸基、R2与R4表示2-乙基己基的MoDTC(下文称其为“MoDCT-1”)。类似地,化学式(1)表示的MoDTC(下文称其为“MoDTC-2”)按照上述相同的方式进行制备,不同的是采用通过将等量(2-己基癸基)(2-乙基己基)胺与二(2-乙基己基)胺混合得到的仲胺替代(2-己基癸基)(2-乙基己基)胺,这些MoDTC中X1~X4中氧原子与硫原子的比值约为1。
采用这些MoDTS,制备作为实施例与对比实施例的机油的试验油品1~8。作为基础油,采用其特性如表1所示的矿物油1-2。
表 1
矿物油1 | 矿物油2 | |
密度(15℃)[g/cm3] | 0.862 | 0.821 |
动态粘度(40℃)[mm2/s] | 17.7 | 19.7 |
动态粘度(100℃)[mm2/s] | 3.78 | 4.51 |
粘度指数[-] | 99 | 147 |
倾点[℃] | -15.0 | -15.0 |
饱和组分含量[%] | 76.5 | 98.8 |
采用下列物质作为添加剂
MoDTC-A:市售MoDTC,其中R1~R4代表化学式(1)中的2-乙基己基。
MoDTC-B:市售MoDTC,其中R1~R4代表化学式(1)中的C13烷基。
ZnDTP:化学式(3)表示的ZnDTP,其中R11~R14代表2-乙基己基。
ZnDTC:化学式(4)表示的Zn DTC,其中R21~R24代表2-乙基己基。
将上述基础油和添加剂按表2和3所示的比例混合,制得实施例和对比实施例中的试验用油。混合比以相对于润滑油重量的%(重量)表示。此外,作为共同的添加剂组分,可将金属清洗剂、无灰分散剂、酚类抗氧化剂、胺类抗氧化剂、粘度指数改进剂、防腐蚀剂和防泡剂加到这些试验用油中。
表2
试验用油1 | 试验用油2 | 试验用油3 | 试验用油4 | |
配方矿物油1[%重]矿物油2[%重]MoDTC-1[%重]MoDTC-2[%重]MoDTC-A[%重]MoDTC-B[%重]ZnDTP[%重]ZnDTC[%重]动态粘度40℃[ mm2/s]100℃[mm2/s]油中元素Mo[Mo%重]磷[P%重]摩擦系数新鲜油用过油热管试验[ mg]贮存稳定性(沉淀/无沉淀) | -84.90.45--1.2-42.58.370.080.0950.0460.07460无沉淀 | 84.5-0.45-1.2-47.58.250.080.0950.0470.08075无沉淀 | -84.9-0.43--1.2-42.28.310.080.0950.0450.07154无沉淀 | -84.40.45--1.20.5542.18.290.080.0950.0460.05725无沉淀 |
表3
试验用油5 | 试验用油6 | 试验用油7 | 试验用油8 | |
配方矿物油1[%重]矿物油2[%重]MoDTC-1[%重]MoDTC-2[%重]MoDTC-A[%重]MoDTC-B[%重]ZnDTP[%重]ZnDTC[%重]动态粘度40℃[mm2/s]100℃[mm2/s]油中元素Mo[Mo%重]磷[P%重]摩擦系数新鲜油用过油热管试验[mg]贮存稳定性(沉淀/无沉淀) | -85.0--0.38-1.2-42.58.350.080.0950.0460.07565沉淀 | 84.6---0.38-1.2-47.78.210.080.0950.0600.08279沉淀 | -83.6---1.741.2-42.48.300.080.0950.0450.140120不沉淀 | -85.2--0.14-1.2-42.18.290.030.0950.0460.14058不沉淀 |
对如此制得的试验用油1~8在耐磨性、热管试验与在新鲜油和用过的油中贮存稳定性等方面进行评估。其结果如表2与3所示。
与耐磨性相同,摩擦系数也是针对新鲜油与用过的油进行测定的。采用SRV试验仪按照下列条件进行测定的。
试件:用SUJ-2制成的直径为10mm的球与盘
试验条件:
负荷 100N
振幅 1.5mm
频率 50Hz
温度 80℃
时间 20分钟
新鲜油为刚刚配制的润滑油,而用过的油则为按照JISK2514对内燃机用润滑油进行氧化稳定性试验后得到的润滑油。氧化稳定性试验在150℃下进行168小时。
通过热管试验评估热阻。采用Komatsu工程公司(kk)制造的热管试验仪在310℃测定沉积量。通过在试验用油于玻璃沉降管中于0℃贮存1个月之后确定试验用油中是否有沉淀发生来评估贮存稳定性。
贮存之后,实施例的试验用油1~4并未产生沉淀,因此具备优良的贮存稳定性,而对比实施例的试验用油5与6则产生沉淀。此外,即使是在油质变坏之后,试验油品1~4也不会在摩尔系数方面发生有害的变化, 因此,可以在长期使用时保持较低的摩擦系数,而对比实施例的试验油品7~8的情况却相反,此外,试验用油1-4在热管试验中产生少量沉积物,这些油品具有良好的热阻。可以看出含有硫添加剂的试验油品4产生更少量沉淀物。
此外,上述基油与添加剂以表4给定的比值混合以便制备实施例和对比实施例中的试验油品9与10。作为添加剂,除了用于试验油品1~8的种类以外,还可使用下列物质:
MoDTC-C:市售MoDTC,其中R1-R4代表化学式(1)中的C8或C13烷基。
噻二唑化合物:化学式(5)所示噻二唑型聚硫醚化合物,其中R31与R32代表C9烷基,x与y代表整数2~5。,添加剂中硫含量为36%(重)。
丙酸酯抗氧剂:具有酯基的由化学式(6)表示的酚类抗氧剂,其中m代表2,R41与R42代表叔丁基,所述抗氧剂由Ciba Geigy公司以商品名Irganox L135提供。
其余组分为普通添加剂,其中包括金属除垢剂、无灰分散剂、酚类抗氧剂、胺抗氧剂、粘度指数改进剂、缓蚀剂与消泡剂。
表4
试验油品9 | 试验油品10 | |
配方 | ||
矿物油2[%重量] | 84.9 | 84.9 |
MoDTC-1[%重量][Mo%重量] | 0.550.081 | -- |
ModTC-C[%重量][Mo%重量] | -- | 2.040.081 |
ZnDTP[%重量][P%重量] | 1.20.095 | 1.20.095 |
噻二唑化合物[%重量][S%重量] | 0.20.072 | 0.20.072 |
丙酸酯抗氧剂[%重量] | 1.0 | 1.0 |
动态粘度 | ||
4[℃[mm2/s] | 42.2 | 43.2 |
100℃[mm2/s ] | 8.41 | 8.48 |
摩尔系数 | ||
新鲜油 | 0.045 | 0.047 |
用过的机油 | ||
96小时之后 | 0.037 | 0.037 |
168小时之后 | 0.062 | 0.091 |
热管试验[mg] | 27 | 85 |
贮存稳定性(沉淀/未沉淀) | 未沉淀 | 未沉淀 |
按照与试验油品1~8相同的方式评估如此制得的试验用油9~10的摩擦特性、热管试验与在新鲜油和用过的油中的贮存稳定性。其结果同样被示于表4。作为被用过的油,使用通过利用2L系列6缸汽油机、将油盘量降至2L并且使试验油品在油温为100℃和水温为100℃下以AMA操作方式进行耐久性台架试验从而使其品质变坏而得到的油。实施例的试验油品9与试验油品10相比即使是在品质变坏后其摩擦系数也只发生很小的有害变化,因此,应该理解,试验油品9可以在更长时间使用后保持较低摩尔系数。
本发明涉及内燃机润滑油,其中添加有预定量具有特定结构的硫化二硫代氨基甲酸氧钼,该润滑油在被使用较长时间后仍能够保持较低的摩擦系数并且具有良好的热阻、贮存特性与稳定性。因此,本发明润滑油可以被稳定地长期用于内燃机并且产生显著的节省燃料效果。
Claims (8)
1.一种内燃机用润滑油,其中含有
(a)一种矿物油和/或一种合成润滑油作为基础油,
(b)以下化学式(1)表示的硫化二硫代氨基甲酸氧钼式(I)中,X1-X4代表氧原子或硫原子,并且可以相同或不同,R1代表含不少于14个碳原子的支链脂族烃基,R2~R4代表含不少于4个碳原子的脂族烃基,按钼(Mo)计算时,其数量为0.005~0.2%(重量)。
2.按照权利要求1的内燃机用润滑油,其中化学式(1)中的R1与R3代表具有不少于14个碳的支链脂族烃基,R2与R4代表具有不少于4个碳的脂族烃基。
3.一种内燃机用润滑油,其中含有
作为基油的矿物物和/或合成润滑油,
上述化学式(1)表示的硫化二硫代氨基甲酸氧钼,
其中R1代表在β位具有支链并且不少于10个碳原子的脂族烃基,R2~R4代表具有不少于4个碳原于的脂族烃基,当按钼(Mo)计算时,其数量为0.05~0.2%(重)。
4.按照权利要求3的内燃机用润滑油,其中R1与R3代表β位具有支链的含有不少于10个碳的脂族烃基,R2与R4为具有不少于4个碳的脂族烃基。
5.按照权利要求1~4中任一项的内燃机用润滑油,其中含有以磷(P)计算数量为0.01-0.2%,(重)的二硫代磷酸锌。
6.按照权利要求1~5中任一项的内燃机用润滑油,其中含有以硫(S)计算数量为0.01-0.5%(重)的硫添加剂。
7.按照权利要求1~6中任一项的内燃机用润滑油,其中含有0.2~5%(重)具有酯基的酚类抗氧剂。
8.按照权利要求1或2的内燃机用润滑油,其中R1或R1与R3在从第2至第5个碳原子之间具有一个不少于4个碳原子的侧链,而在链端它与化学式(1)中的氮结合。
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1996
- 1996-12-24 US US08/894,712 patent/US5916851A/en not_active Expired - Lifetime
- 1996-12-24 CN CN96192083A patent/CN1175973A/zh active Pending
- 1996-12-24 EP EP96942626A patent/EP0811674B1/en not_active Expired - Lifetime
- 1996-12-24 WO PCT/JP1996/003760 patent/WO1997023587A1/ja active IP Right Grant
- 1996-12-24 CA CA002213075A patent/CA2213075C/en not_active Expired - Fee Related
- 1996-12-24 DE DE69621324T patent/DE69621324T2/de not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1076393C (zh) * | 1998-10-30 | 2001-12-19 | 中国石化兰州炼油化工总厂 | 汽车自动传动液组合物 |
CN104449963A (zh) * | 2014-10-27 | 2015-03-25 | 西北有色金属研究院 | 一种高钼含量钼硫配合物润滑油添加剂的制备方法 |
CN109415650A (zh) * | 2016-06-24 | 2019-03-01 | 陶氏环球技术有限责任公司 | 润滑剂组合物 |
CN109415650B (zh) * | 2016-06-24 | 2021-11-16 | 陶氏环球技术有限责任公司 | 润滑剂组合物 |
CN110168060A (zh) * | 2017-01-24 | 2019-08-23 | 株式会社Adeka | 发动机油组合物 |
Also Published As
Publication number | Publication date |
---|---|
EP0811674B1 (en) | 2002-05-22 |
DE69621324D1 (de) | 2002-06-27 |
WO1997023587A1 (fr) | 1997-07-03 |
CA2213075A1 (en) | 1997-07-03 |
EP0811674A4 (en) | 1999-12-01 |
EP0811674A1 (en) | 1997-12-10 |
DE69621324T2 (de) | 2003-01-02 |
CA2213075C (en) | 2001-10-09 |
US5916851A (en) | 1999-06-29 |
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