CN1076718A - 有银轴承部件的内燃机润滑油组合物 - Google Patents
有银轴承部件的内燃机润滑油组合物 Download PDFInfo
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- CN1076718A CN1076718A CN93103064A CN93103064A CN1076718A CN 1076718 A CN1076718 A CN 1076718A CN 93103064 A CN93103064 A CN 93103064A CN 93103064 A CN93103064 A CN 93103064A CN 1076718 A CN1076718 A CN 1076718A
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- Prior art keywords
- silver
- bearing
- lubricating composition
- heavy
- composition
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- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
基本上不含氯的总碱值为10—30的润滑组合
物用于装有银轴承零件的内燃机,它通过掺入某些不
饱和脂肪族羧酸来保护所述的轴承。也公开了该润
滑组合物的添加剂浓缩物。
Description
本发明涉及用于装有银轴承发动机的润滑油组合物,进一步说,本发明涉及内燃机中银轴承部件的保护。
众所周知,用于重负荷柴油发动机的润滑油要求其曲轴箱润滑具有氧化安定性并能限制发动机沉积物的形成,此外,这些曲轴箱润滑油还必须具有高的碱度以中和燃料燃烧过程中生成的酸。
由于装有表面是银的发动机部件,如银轴承或镀银轴承,在美国使用的许多重负荷铁路和拖船用柴油发动机提出了一个附加的润滑问题。虽然上述的氧化安定性、沉积物控制和碱度可通过使用已知技术的润滑油添加剂来获得,但许多这样配成的润滑油对发动机银表面部件却造成了不可接受的腐蚀和磨损。银或镀银轴承部件提出了一个特殊的问题,因为许多轴承保护添加剂对表面为其他材料,如黄铜、铜-铅、青铜、铝,的轴承能提供有效的保护,而对保护银轴承零件则无效,例如一些物质,诸如通常用于汽车点燃式发动机润滑剂的二硫代磷酸锌,已知对银轴承是有害的。另一问题是,铁路和内陆船用发动机许多都装有非银轴承,如铜-铅轴承,但实际上,用户情愿对所有发动机,不管是银轴承还是铜-铅轴承,都用相同的润滑油,因而润滑组合物不仅要对银轴承有效,而且还应对非银轴承有效。
目前主要通过使用含氯化石蜡或其他氯化添加剂提供银保护。美国专利4169799、4171269和4131551中介绍了用来提供银保护的卤化添加剂。但是使用卤化添加剂提出了一个新问题,即人们发现它们会带来环境保护问题,因而要求能提供银保护而又不含卤代物的添加剂。
鉴于这种需要,本领域已经开发了一些含无卤或低卤的银腐蚀抑制剂的润滑剂,例如美国专利4764269和4734211,公开了一种含有某些多羟基酯作为银磨损抑制剂的船用和铁路柴油发动机润滑油组合物,这些专利也公开了含有这些多羟基酯和氯化石蜡混合物的润滑油组合物。美国专利4820431公开了一种类似的润滑油组合物降低船用和铁路柴油发动机部件中银磨损的方法。美国专利4171270公开了含有硫含量为1-6(重)%的高碱性硫化烷基酚钙和硫化环烷基油的润滑油组合物。这些组合物亦被认为具有银保护性能。美国专利48771465公开了含有以下物质作为银保护剂的润滑油:(a)硫化烯烃、硫化脂肪酸、硫化羟基芳烃、含硫杂环化合物、有机硫化物或二硫代氨基甲酸盐;(b)饱和脂肪二羧酸与一种任选取代的氨基胍的反应产物。
其他有机化合物也被公开以提供银保护。美国专利4278533公开了一种含有0.5-2.0(重)%苯三唑化合物作为银腐蚀抑制剂的铁路柴油发动机润滑剂,美国专利4285823则公开了一种含有氮取代的5-氨基-1H-四唑银腐蚀抑制剂的柴油发动机润滑组合物。
一直需要提供具有银保护性能而又不致引起潜在的环保问题,并且最好是容易得到,较便宜,对非银轴承,比如铜-铅轴承也无害的添加剂。如上所述,为满足这个要求一个重要的问题是添加剂对银轴承系统的影响之不可预见性,人们不能简单地根据添加剂在非银轴承发动机润滑剂中的性质或该添加剂的性质或作用的一般特征来预测它是否可提供对银轴承的保护,例如,广泛用于提供磨损和氧化保护性能的二硫代磷酸锌就是对发动机的银轴承零件有害的。
本领域基于各种理由曾建议将不饱和羧酸及其各种酯加到各种类型的润滑油中。早在1958年,美国专利2851 422就建议在传动液中加入某种硫化物(如硫化鲸鱼油),以防止腐蚀,并将油酸作为消噪音剂加入该组合物中。
美国专利2830956针对液压传动液讲到,众所周知,各种普通脂肪酸、脂肪油酸及其氯代衍生物都具有很好的油性,按照专利权人的发明,提出将具有12-24个碳原子的油溶性脂肪酸和硫化或未硫化的脂肪油组合物加入到传动液中以改过其油性,专利权人指出,使用这两种油性剂以及他提出的具体的比例都是该发明的关键所在。专利权人还指出,油酸、硬脂酸和芥酸对某些种类的金属有腐蚀性,但此缺陷可通过加入一般抗腐蚀剂来克服,并提出硫烯烃可作为满意的腐蚀抑制剂。
针对内燃机特别是动力传送装置用润滑油添加剂的美国专利3267033介绍的一种添加剂混合物由,1-3份(重量)一种油溶性脂肪酸,最好是不饱和脂肪酸,特别是油酸,和1-3份(重量)部分酯化的磷酸脂肪族叔碳基伯胺盐以提供所需的摩擦性质,专利权人也指出了一种用于齿轮装置或齿轮差速器润滑油的特别有效的添加剂组合物,它由上述的添加剂混合物和一种多硫化烃和/或一种胺和某些酸的中和产物构成。
加拿大专利1228847介绍的润滑剂组合物由一种脂肪族烯烃化合物和一种硫化烯烃加入加氢精制的润滑油组成,据称这种润滑剂组合物能提供较长的使用寿命和抗磨能力,并减少铜部件的锈蚀,专利权人指出,该脂肪族烯烃化合物最好是一种脂肪酸,尤其是一种脂肪酸酯。该专利,举出各种酸的实例,其中包括托尔油和脂肪水解得到的酸,如棕榈油酸、油酸、亚油酸、亚麻酸等。虽然该专利主要针对用于齿轮、液压传动装置及其他专门应用的多功能工业润滑油,但是该专利也泛泛地指出,它的润滑油组合物能用于各种用途,包括点燃式和压燃式内燃机曲轴箱润滑油,包括汽车和载重车发动机,二冲程发动机,航空活塞式发动机,船用和铁路柴油发动机,并能用作固定式动力发动机、汽轮机、传动装置、传动油、金属加工润滑剂及其他润滑油和润滑脂。
美国专利3112269及3112271粗略地指出,羧酸或磷酸酯类,如脂肪酸与多元醇的部份酯化产物,或亚磷酸或磷酸的烷基酯,或游离脂肪酸及其硫化衍生物,如C10-C18脂肪酸(油酸或硬脂酸)与硫化不饱和脂肪酸例如硫化油酸,都是用于烃类燃烧的抗磨和极压剂,但当用于经受高温高压的润滑油时,在极端条件下它们将破坏而不能给予其预期的性质。
美国专利2788826指出,通过用热聚合含多个羟基的多官能团有机化合物如脱水山梨糖醇油酸酯能得到改进的极压润滑剂。
美国专利4780111和4412738系指用对苯二酸提供铅轴承的腐蚀防护。
美国专利3041284建议用脂肪酸和脂肪酸酯作为含某种巯基改性酸或醇添加剂润滑油的澄清剂。
美国专利4428850提出在铁路柴油发动机润滑油加入一种羟基脂肪酸的交酯作为一种抗泡剂。
早在七十年代,油酸就被研究用作轿车发动机和重负荷柴油载重车用润骨油的摩擦改进剂以降低燃料消耗。虽然人们发现油酸能作为一种好的摩擦改进剂降低燃料消耗,但是据信对于通常用于这类发动机的铅-铜轴承,尤其是对轴承的铅组份引起严重的腐蚀,此后,研究工作就从酸本身转向腐蚀性较小的酯。美国专利4376056指出,在点燃式或压燃式发动机润滑剂中使用油酸季戊四醇酯来降低摩擦并改进其燃料经济性。英国公开的专利申请GB2038356A认为类似的效用是甘油脂肪酸酯,例如甘油油酸酯和甘油牛脂酸酯造成的,也见美国专利4304678,该专利将这种效用扩展到羟基酸的酯类,例如甘油油酸酯和脱水山梨糖醇油酸酯。欧洲专利申请0092946A指出,使用既含甘油酯又含某种油溶性有机铜化合物的润滑油能改进该润滑剂的性能和燃料经济性,公开的美国专利申请2038355指出,用含有甘油酯和0,0-二(2-乙基己基)二硫代磷酸锌的润滑剂可改进燃料经济性。
现在惊奇地发现,某些含有不饱和羧酸,其中包括抗油酸,的润滑油组合物,当用于装有银表面部件的内燃机曲轴箱润骨油中时,是极有效的银腐蚀抑制剂,而且还可效地用于装有铜-铅轴承的发动机中而不致产生腐蚀问题。
本发明提供一种基本上无氯的润滑组合物,它的总碱值(TBN)约为10-30,由大量具有润滑粘度的油和一定量具有12-24个碳原子的不饱和脂肪族羧酸或其混合物所组成,该组合物有效地抑制或减少装有银轴承部件的内燃机的磨损或损坏。
术语“基本上无氯“是指不存在起银保护作用的氯化物,也不存在任何被认为对环境有害的氯化物。TBN(总碱值)是润滑油对酸中和能力的量度,用ASTM D2896-85中描述的方法测定,一般指一克润滑组合物的中和能力,用能提供等当量中和的氢氧化钾的毫克数来表示,因而TBN10是指1克该组合物具有相当于10毫克氢氧化钾的中和能力。
在一实施方案中,本发明提供了一种用该润滑组合物减少装有银轴承部件的内燃机的银轴承磨损的方法。
在一实施方案中,本发明提供了一种复合添加剂或浓缩物,它具有90-120的TBN,含有少量的通常是20(重量)%以下的稀释油,和一种具有12-24个碳原子的不饱和脂肪族羧酸,其中所述的羧酸和提供TBN的添加剂按一定的重量比组成,该复合添加剂可与具有润滑粘度的油混和以提供一种TBN为10-30,并含有一定量的所述羧酸或其混合物来提供有效的具有银轴承保护性能的润滑剂。
如上所述,本发明的组合物含有一定量的某种不饱和脂肪族羧酸以对装有银轴承的发动机提供有效的银保护,同时又可安全地用于装有其他材料制成的轴承的发动机。至于为什么一种材料能保护银,一般有两种理论:即该物质可作为一种润滑剂起作用或作为银的“稳定剂”起作用(即通过参与和银的化学反应形成一种不易磨损的轴承表面来保护银轴承)。虽然人们不能从一种添加剂对其他材料制成的轴承所表现出来的性能来预计它对银轴承的性能,但是据信,在本发明的组合物中羧酸对银轴承起着润滑作用。从理论上讲,本润滑组合物对于用非银材料制成的轴承,特别是铜-铅轴承是安全的,因为它比普通用于汽车发动机或柴油载重车发动机的润滑组合物有更高的总碱值,从理论上讲,较高的碱度起着某种形式的中和作用。出乎意料的是根据化学计量,用于汽车和卡车发动机的润滑剂的碱度,即5个TBN,已超过足以中和少量用作银保护剂的羧酸所需的值。无论如何,不管上述理论的准确性如何,本组合物可对银轴承提供有效的银保护,又能安全地用于装有其他材料制成的轴承的发动机润滑剂。
现在来详细说明本发明的润滑剂组合物。典型的本组合物含有占组合物总量约0.8-3(重量)%,最好是0.85-2(重量)%的具有12-24个碳原子,最好是14-22个碳原子的不饱和脂肪羧酸或这类酸的混合物,更好的是,该润滑剂组合物含有约0.9-1.5(重量)%的脂肪族酸。这些酸可以是单不饱和的和/或二或多不饱和的。最经济的办法常常是制得这些不饱和脂肪族酸的混合物,可含有少量通常具有大约相同的碳原子链长的饱和脂肪族羧酸,少量这种饱和酸的存在,既无害也无益于银保护。在使用饱和酸与不饱和酸的混合物时,仅把不饱和酸的量计算作为本发明的有效量。适合的不饱和脂肪族羧酸的实例包括油酸、亚油酸、棕榈酸、亚麻酸、月桂烯酸、肉豆寇脑酸等等及其混合物,不饱和羧酸最好是一种直链的(即不分支的)不饱和脂肪酸。
本润滑剂组合物的总碱值是10-30,最好是15-25,这是其碱度或中和能力的量度,一般由加入碱性清净剂或高碱性物质达到。碱性组份的作用是中和酸性氧化产物,如在用柴油作燃料时生成的硫酸。在本发明的情况下,正如以上所推想的,碱性组份也降低了不饱和脂肪酸的腐蚀性而不需使用专门的防腐剂。可用各种类型的高碱构成的可混性的复合剂,并含有按照本发明使用的不饱和脂肪族羧酸和碱性清净剂或高碱性物质。
本发明的润滑组合物也可以含有少量的,一般约小于润滑组合物总量1(重量)%的辅助防腐剂,它无害于该润滑组合物的性质,也许还有些额外的好处,如上所述,当使用粘度指数改进剂时,有可能是需要的。当然,这类防腐剂不是像二硫代磷酸锌那样本身对银轴承有腐蚀的防腐剂。若使用防腐剂时,其用量一般约为润滑组份量的0.02-1(重)%,更多量的辅助防腐剂可能不会有害,但一般不会有益。比如该组合物可含占组合物总量约0.02-0.08(重量)%的硫化烯烯烃防腐剂(例如共硫化的烯基酯/α-烯烃),和/或最大约1(重)%,最好是0.5-0.8(重)%的对苯二酸或其盐或其衍生物。各种硫化烯烃防腐剂以及其他种防腐剂在出版的文献中已有介绍,并可在市场上买到,例如共硫代的烯基酯/α-烯烃添加剂一般可用已知的工艺通过使所需的烯烃(有代表性的是C12-C20直链烯烃)不饱和酯(如油酸酯、亚油酸酯)的混合物与硫一起在适度的或高温下反应制得。各种硫化烯烃防腐剂或抗磨剂已记述在美国专利4053427,4119549和4240549。在使用对苯二酸防腐剂时,或用溶解形式的酸,或更方便地,当在复合添加剂中包括有丁二酰亚胺分散剂时,该酸通过与丁二酰亚胺分散剂反应形成油溶性的对苯二酸盐而很容易地被溶解。
本发明也提供了一种添加剂的复合剂或浓缩物,它可作为仅有的添加剂,也可与其他添加剂混合加入有润滑粘性的油中,(一般说,本复合添加剂不含粘度指数改进剂,因为即使需要,粘度指数改进剂一般也是由润滑油调配者加入基础油中的)。较好的添加剂浓缩物含有约5-14(重)%,更好者为6-10(重)%的不饱和脂肪族羧酸或其混合物,能提供给浓缩物约60-180TBN是足够的碱性物(通常是高碱性清净剂),和约1-10(重)%,最好是2-6(重)%的稀释油。该浓缩物也常常含有用于专门用途的需要的其他添加剂,通常含有30-60(重)%的无灰分散剂,在含高碱性清净剂的同时也常常含有中性或弱碱性清净剂。用于提供所需总碱值的高碱性清净剂的量当然随着该高碱性清净剂的总碱值而变化,但典型的是浓缩物的20-80(重)%。
上述各种添加剂或添加剂类别都是已知物并可由已经工艺或显而易见改进工艺来制备,它们常常是很容易在市场上买到。
从下列非限定性实施例中可获得对本发明进一步的理解。
实施一:银磨损评价
表1中的润滑油组合物用EMO2-576标准银轴承磨损试验来评价其银磨损保护性能,该试验通常也称为“双杆试验(2-Holertest),用来评价镀银活塞销在25小时的运转之后损坏状况的评分。
将所需量所示的添加剂与含4.0(重)%粘度指数改进剂及为达到表1中所列出的总碱值所需的高碱性硫化烷基酚钙的调好的性物质,例如硫化的和/或碳酸化的酸盐、水杨酸盐和磺酸盐,美国专利2680096,3036971,3336224,3437595,3801507及4251379中介绍了各种高碱性酸盐。美国专利2616904,2626207,2767209,3126340,3524814及3609076中介绍了各种高碱性磺酸盐。
一种具有润滑粘性的基础油通常由大部份本润滑油组合物构成,它除了含不饱和脂肪族羧酸或它们的混合物外,一般也含有赋于装有银轴承部件内燃机润滑油组合物以所需性质的其它添加剂,于是,该润滑剂组合物通常含有选自清净一分散剂,无灰分散剂,高碱性添加剂和抗氧化剂,最好是含这些添加剂的复合剂,亦可选择性地应用某些粘度抑制剂。
基础油可为矿物油,合成油或天燃油(植物或动物得到的油类),不过从经济观点看最好是矿物油,也可用溶剂精制和加氢精制的基础油。常把不同油的混合物用作基础油。每种润滑100℃时的粘度通常是4-40厘沱,最好是8-14厘沱。一般预先选好基础油或基础油混合物的粘度,致使含有各种添加剂的配好的润滑油的100℃粘度为4-22厘沱,最好是10-17厘沱,尤其为13-17厘沱。
清净一分散剂是用来保持油泥、碳粒和因柴油燃料或基础油的部分氧化所生成的产物悬浮在基础油中,适用的清净分散剂包括酚盐和磺酸盐金属清净剂,如酸钙及磺酸钙。各种无灰剂在美国专利3172892,3219666,3282955和3361673中均有记述,丁二酰亚胺和丁二酸酯无灰分散剂通常由聚异丁烯基丁烯基丁二酸酐分别与多烯多胺或多元醇反应制备。
此润滑油组合物也可任选地含有粘度指数改进剂(Ⅵ改进剂)来调节其粘度,即降低由于温度改变而引起的粘度变化例如多级油。但是在使用粘度指数改进剂时必须要很小心,因为它可能对银轴承有害,因此当使用粘度指度改进剂时,有可能需要增加不饱和指肪族羧酸的用量或加入别的防腐剂。粘度指数改进剂可以是非分散性的,也可以是分散性的,后者能起分散剂的作用,也能起粘度调节作用。非分散型粘度改进剂的例子包括各种分子量一般在20000到1000000范围内的油溶性聚合物,如甲基丙烯酸烷基酯的聚合物,乙烯丙烯共聚物,混合的甲基丙烯酸烷基酯-乙烯-丙烯聚合物,异丁烯聚合物,加氢的苯乙烯-二烯聚合物等等。分散型粘度改进剂也是典型的聚合物,但它除了粘度调节作用外,还某种程度地加过了使其分子再分散性的氮官能度,分散型粘度改进剂的例子包括含有丁二酰亚胺或取代的丁二酰亚胺[如N-(3′-吗啉-4-基丙基)丁二酰亚胺]单元的苯乙烯为基础的聚酯,混合甲基丙烯酸烷基酯-乙烯基吡咯烷酮的聚合物,胺化乙烯-丙烯聚合物等等。也可用可混性的粘度改进剂的混合物。
除了可能加入粘度指数改进剂外,通常给予装有银轴承内燃机的现代润滑油组合物以所需要最全面的性质方案是这样的润骨油组合物,它含有由有效量的一种或多种,最好是每种上述的各种添加剂20W/40润滑油掺和在一起制成试验制剂,此外,该调制好的20W/40油还含有少量标准的清净剂和分散剂,其中包括丁二酰亚胺和0.05(重)%商品共硫化的烯基酯/α-烯烃防腐剂及0.78(重)%的对苯二酸。在一个试验中也用了40W油,该40W油的基础油稍稍不同,但用了与20W/40油相同的复合添加剂,只是取消了其中的粘度指数改进剂。两种类型或两种来源的油酸,即商品和食品级的油酸,用作银保护剂。用于试验的商品油酸中含91(重)%的C14-C18不饱和脂肪酸,即含73(重)%油酸,8(重)%亚油酸,6(重)%棕榈油酸,3(重)肉豆冠脑酸及1(重)%亚麻酸,其余(重)%系C14-C17饱和脂肪酸。试验中用的食品级油酸也含91(重量)%C14-C18不饱和脂肪酸(即含75(重量)%的油酸,6(重)%的亚油酸,6(重)%的棕榈油酸,3(重)%肉豆冠脑酸,和9(重)%的饱和脂肪酸,即5(重)%棕榈酸,3(重)%肉豆冠酸及1(重量)珠光脂酸)。
在“双杆试验”中,用来经保护的银轴瓦代替普通经保护的活塞肘节销轴瓦组合中的银轴瓦,(一般用薄铅沉积镀层来保护轴瓦的银表面不腐蚀及经受磨合过程中的严重摩擦)。铅沉积镀层的除去极大地增加了试验的苛刻度。评价用试验机是按D-1型装配的(D-1构型系将三个镀铬及一个含有铁氧体的铸铁压缩环装在活塞销上部,在活塞下面装有一个鼻形刮油环和一个换气铸铁环,其额定压缩比为20∶1)。
通过定期更换缸套、活塞、环、主动机构、止推垫圈、凸轮轴承、连杆、连杆轴承、主轴承,用修磨过的缸头和新阀以及重装的喷射器来保持发动机处于新构造状态。
对于每次银磨损试验,都要用市售石油基溶剂彻底清洗发动机,用新活塞销和未保护的,即非铅处理的镀银销轴承来代替用过的。在进行银磨损试验前,先将发动机进行九小时又二十分钟的EMD-型充分磨合,磨合后,检查曲轴箱及空气箱是否有轴承损坏的迹象后才开始试验步骤。在试验中,发动机用分布式数控计算机保持在每分钟835转,燃料速度91±1.0磅/小时,空气背压6.8时汞柱。将进水及进油温度分别控制在180°±2°F及210°±2°F,曲轴箱及所有油路均用试油冲洗,将曲轴箱充油至其最大容量,45美国加仑。试验燃料为含硫0.1%,额定十六烷值为47-50的2#柴油。每一个试验都用相同的条件。试验前后将销轴承称重,试验前后还要测量活塞销直径及支架间隙。
试验结果时,要取下销轴承并按照EMD缺点评分步骤,即测量从轴承上转移到油槽中的银量并给出其缺点评分的办法,进行评价,平均30或小于30,同时两个轴承均不高于40的评分值被认定是通过值。
表1列出了实验结果,从表1可见,含有1(重)%的食品级或市售油酸的润滑油,即含有0.91(重)%C14-C18不饱和羧酸者,均通过了试验,而含有0.75或0.85(重)%食品级油酸(其不饱和脂肪族羧酸含量,分别为0.68(重)%及0.77(重量)%)或0.3(重量)%市售油酸的润滑油则未能通过该试验,虽然含0.85(重)%食品级油酸的润滑油已接近通过。
实施例二:L-38发动机试验
在此实施例中,表2列出的制剂用莱别克L-38试验,ASTMD5119-90,来评价其在含铜-铅轴承发动机中的性能。将所需量的试验添加剂与含有足以达到表2指出的总碱值的高碱性硫化烷基酚钙配好的20W/40油掺合来制备本试验制剂,除表2列出者外,其余均与实施例一中的20W/40油相同。
ASTM D5119-90莱别克L-38试验方法是设计用来评价润滑油高温操作条件下氧化安定性及腐蚀、游泥和漆膜性质的,当试验油作为多级油时,它也能评价其剪切安定性,其操作步骤包括:在四个半小时的磨合周期后,使单缸CLR评油发动机在恒速、恒燃气比和恒定燃料消耗条件下运转,并将其标准周期延长,一般为80小时。每次试验前将发动机彻底清洗,如实地测量发动机动部,装配好新的活塞、活塞环和铜-铅连杆轴承轴衬。在40小时及延长试验周期后的终结点则量轴承失重数据。
此评价试验的关键发动机操作条件为:
试验周期 40,80小时(可延长)
速度 3150±转/分
负荷 在特定燃、气比下调到适当供油速度
燃料流速 4.75±0.25磅/小时
空气/燃料比 14.0±0.5
夹套外温度 200±2°F
夹套内外温差 10±2°F
主油路温度 对于SAE20、30、50及多级油:
290±2°F
对于SAE级油:275±2°F
试验结束,将发动机拆卸,按照以下几条来判断试油的性能:
1)目测发动机沉积物;
2)测定铜-铅轴承失重;
3)将试验中定期抽样分析结果与新油分折对比。
试验结果列于表2。正如从表2结果提到的,总碱值17的润滑油都通过了本试验,既便延长到200小时也能通过;而总碱值为5,其余均与总碱值17者相同的润滑油则仅仅40小时就明显地失败了,尽管它也含有0.05(重)%共硫化的烯基酯/α-烯烃抗腐剂和0.78(重)%对苯二酸。
显然,可将此发明进行许多改进而不背离本发明的精神和其范围。
Claims (22)
1、一种基本上不含氯的、总碱值(TBN)为10-30的,适用于装有银轴承或铜-铅轴承之内燃机的润滑组合物,它包括大量的油或有润滑性粘度的油的混合物和一定量能有效地抑制或减少银轴承磨损或损伤而又不损害铜-铅轴承的银保护剂,该银保护剂选自具有12到24个碳原子的不饱和脂肪族羧酸或其混合物。
2、权利要求1的润滑组合物,其中所述的银保护剂选自14到22个碳原子的不饱和脂肪族羧酸。
3、权利要求1的润滑组合物,其中所述的银保护剂的主要成份是油酸。
4、权利要求1的润滑组合物,其中所述的银保护剂是该组合物中唯一的银保护添加剂或腐蚀抑制添加剂。
5、权利要求1的润滑组合物,其中该组合物的总碱值约为15-25。
6、权利要求1的润滑组合物,其中所述的银保护剂选自不饱和直链脂肪酸及其混合物。
7、权利要求1的润滑组合物,其中所述润滑组合物有约0.8(重)%至3(重)%的所述银保护剂。
8、权利要求6的润滑组合物,其中该润滑组合物含有约0.85(重)%至2(重)%的所述银保护剂。
9、权利要求1的润滑组合物,其中所述组合物含有大约0.02(重)%至1(重)%的对银无害的辅助腐蚀抑制剂或其混合物。
10、权利要求1的润滑组合物,其中所述的组合物含有大约0.02-0.08(重)%的硫化烯烃腐蚀抑制剂。
11、权利要求10的润滑组合物,其中所述的腐蚀抑制剂是一种共硫化的烯基-酯/α-烯烃。
12、权利要求1的润滑组合物,其中所述的组合物含有大约0.5-1(重)的油溶性对苯二酸腐蚀抑制剂。
13、一种基本上不含氯的用于装有银轴承的内燃机的润滑组合物。该组合物含有大量的矿物油或有润滑性粘度的合成油,约1-5(重)%的碱性清净剂、约1-7(重)%的丁二酰亚胺无灰分散剂、约0.5-0.8(重)%对苯二酸、约0.02-0.08(重)%的硫化烯烃腐蚀抑制剂、足够量的高碱性清净剂(以使该润滑组份的总碱值为约10-30)以及一定量的选自具有12-24个碳原子的不饱和脂肪族羧酸及这类酸的混合物的银保护剂以有效地抑制或减少所述的银轴承的磨损磨耗。
14、权利要求13中的润滑组合物,其中该润滑组合物含有约0.9-1.5(重)%所述银保护剂。
15、一种基本上不含氯的用于装有银轴承的柴油机的润滑添加剂浓缩物,该浓缩物是由约1-10(重)%的稀释油、约20-80(重)%的高碱性清净剂足以使此浓缩物总碱值达90-120、以及约5-14(重)%的选自含12至24个碳原子的不饱和脂肪族羧酸及其混合物的银保护剂。
16、权利要求15中的浓缩物,其中该浓缩物含有6-10(重)%的所述不饱和脂肪族羧酸或其混合物。
17、权利要求16中的浓缩物,其中该不饱和脂肪族羧酸有14到22个碳原子。
18、一种减少装有银轴承内燃机的银轴承之磨损或磨耗的方法,该方法包括用权利要求1的润滑组合物润滑所述的轴承。
19、一种减少装有银轴承内燃机的银轴承之磨损或磨耗的方法,该方法包括用权利要求3中的润滑组合物润滑所述的轴承。
20、一种减少装有银轴承内燃机的银轴承之磨损或磨耗的方法,该方法包括用权利要求5中的润滑组合物润滑所述的轴承。
21、一种减少装有银轴承内燃机的银轴承之磨损或磨耗的方法,该方法包括用权利要求9中的润滑组合物润滑所述的轴承。
22、权利要求1中的润滑组合物,其中所述的银保护剂选自具有14至18个碳原子的不饱和脂肪族羧酸及其混合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/855,955 US5244591A (en) | 1992-03-23 | 1992-03-23 | Lubricating oil compositions for internal combustion engines having silver bearing parts |
US855,955 | 1992-03-23 |
Publications (1)
Publication Number | Publication Date |
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CN1076718A true CN1076718A (zh) | 1993-09-29 |
Family
ID=25322523
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Application Number | Title | Priority Date | Filing Date |
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CN93103064A Pending CN1076718A (zh) | 1992-03-23 | 1993-03-22 | 有银轴承部件的内燃机润滑油组合物 |
Country Status (4)
Country | Link |
---|---|
US (1) | US5244591A (zh) |
CN (1) | CN1076718A (zh) |
CA (1) | CA2090647A1 (zh) |
ZA (1) | ZA931636B (zh) |
Cited By (2)
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CN100381545C (zh) * | 2001-12-27 | 2008-04-16 | 新日铁化学株式会社 | 流体轴承装置及轴承用润滑油组成物 |
CN101180386B (zh) * | 2005-04-29 | 2012-08-29 | 切夫里昂美国公司 | 中速柴油发动机油 |
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DE4310593C2 (de) * | 1993-03-31 | 1996-11-28 | Wacker Chemie Gmbh | Stabilisierte Organopolysiloxanöle und deren Verwendung |
US5397486A (en) * | 1993-07-30 | 1995-03-14 | Chevron Chemical Company | Lubricating oil compositions for railroad diesel engines |
SG97808A1 (en) * | 1999-08-18 | 2003-08-20 | Oronite Japan Ltd | Lubricating oil additive composition having a high friction coefficient at elevated temperatures |
US20060264341A1 (en) * | 2005-05-20 | 2006-11-23 | Culley Scott A | Transmission composition |
US8084404B2 (en) | 2005-07-20 | 2011-12-27 | Chevron Oronite Company Llc | Crankcase lubricating oil composition for protection of silver bearings in locomotive diesel engines |
JP5249683B2 (ja) * | 2008-08-29 | 2013-07-31 | Jx日鉱日石エネルギー株式会社 | 銀含有材料と接触する潤滑油組成物 |
US9909079B2 (en) | 2013-10-18 | 2018-03-06 | Chevron Oronite Company Llc | Lubricating oil composition for protection of silver bearings in medium speed diesel engines |
WO2016065175A1 (en) * | 2014-10-23 | 2016-04-28 | Northwestern University | Lubricant additives, lubricant compositions, and applications of same |
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-
1992
- 1992-03-23 US US07/855,955 patent/US5244591A/en not_active Expired - Fee Related
-
1993
- 1993-03-01 CA CA002090647A patent/CA2090647A1/en not_active Abandoned
- 1993-03-08 ZA ZA931636A patent/ZA931636B/xx unknown
- 1993-03-22 CN CN93103064A patent/CN1076718A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100381545C (zh) * | 2001-12-27 | 2008-04-16 | 新日铁化学株式会社 | 流体轴承装置及轴承用润滑油组成物 |
CN101180386B (zh) * | 2005-04-29 | 2012-08-29 | 切夫里昂美国公司 | 中速柴油发动机油 |
Also Published As
Publication number | Publication date |
---|---|
ZA931636B (en) | 1993-10-04 |
US5244591A (en) | 1993-09-14 |
CA2090647A1 (en) | 1993-09-24 |
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