CN1320151A - 高性能润滑油 - Google Patents
高性能润滑油 Download PDFInfo
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- CN1320151A CN1320151A CN99811367A CN99811367A CN1320151A CN 1320151 A CN1320151 A CN 1320151A CN 99811367 A CN99811367 A CN 99811367A CN 99811367 A CN99811367 A CN 99811367A CN 1320151 A CN1320151 A CN 1320151A
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- lubricant
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- oil
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Abstract
一种可用作齿轮油、循环油、压缩机油和其它用途的润滑油,其特点是很好综合平衡抗磨性和防锈性,所述润滑油基于包括主烃基原料如PAO的主要部分和辅助原料组分的高质量的基本原料,所述辅助原料组分较好的是长链烷基化芳烃如烷基萘。包括取代的***如苯并***或取代的苯并***如甲苯基***(TTZ)与磷酸胺加合物和三烃基磷酸酯如磷酸甲苯二苯酯(CDP)的添加剂协同组合,可提供要求的抗磨性和防锈性综合平衡。另外,本发明油品通常包括抗氧化组分和防锈剂以及其它任选添加剂组分。
Description
本发明涉及润滑油,更具体的涉及合成油源或矿物油源的润滑油,可用于轴承、齿轮润滑,以及要求宽温度范围特性的其它工业应用。本发明的润滑油特点是很好综合了各种性能,包括改善了抗磨性和防锈性。本发明润滑油可用作齿轮油、循环油、压缩机油、以及其它应用例如湿离合器***、鼓风机齿轮、煤粉磨机驱动器、冷却塔轴承箱、窑驱动器、造纸设备驱动器和旋转螺杆压缩机。
要求齿轮油和工业油满足一些确切的性能指标。它们必须具备长期的稳定性,在结合其它性能包括抗磨性的宽温度范围,显示良好的抗氧化性。根据具体应用,会要求其它的性能特征。例如,对高温循环油,主要要求高温稳定性,对防锈性的要求最小,因为高温时存在的水很少。然而,在其它应用中,防锈性变得很重要,例如在使用于造纸设备的潮湿应用中。
油品性能可根据这些性能是整体性能还是与表面有关的性能来区别,整体性能是在与其它材料例如设备的部件的表面接触时对其没有明显影响的性能,与表面有关的性能是受到与油接触的表面影响的性能。例如,抗氧化性,大都归在前一类,尽管油品在使用时氧化的速度受到与油接触的金属表面特性的影响。抗特压性也可归入此类中。其它性能例如抗蚀性、防锈性、抗磨性都直接取决于表面,一般是使用时与油品接触的金属表面的性能。取决于表面的性能是成品润滑油配方中另一个需要考虑方面,因为用于改善润滑油基本原料性能以及提供要求的综合性能的添加剂会竞争在金属表面上的有用点。由于这一原因,在取决于表面的表现性能之间很难达到良好平衡。一个例子就是抗磨性与防锈性之间,很难生产一种同时具备良好的这两种性能的油品。
不同类型的原料具有不同的性能特征。酯基原料例如新戊基多醇酯如一元羧酸的季戊四醇酯,在用于燃气轮机润滑剂时,表明具有优良的性能。当存在常用的抗磨添加剂时还提供了优良的抗磨性能,并且对防锈剂性能没有任何不利作用。另一方面,酯类的水解稳定性相对较差,甚至在中等温度下,只要存在水就容易水解。因此,它们不适合在湿应用如造纸设备中使用。
通过使用烃基原料可提高水解稳定性。例如,在美国专利5,602,086(相当于EP 496486)中描述了烷基芳烃与其它烃基原料如加氢聚α-烯烃(PAO)合成烃结合使用,以及通过结合使用改善了水解稳定性。然而,含PAO的传统配方存在其它的性能问题。尽管包括PAO的烃基原料的水解稳定性优于酯类,但是很难达到取决于表面的性能如抗磨性和防锈性之间的良好平衡,因为与表面有关的性能取决于原料中添加剂的存在量,这些添加剂竞争应受到它们保护的金属表面上的点,而且高质量的烃基原料如PAO并没有与用于这种目的的添加剂顺利作用。基于烃基原料如PAO的合成油要达到很好结合与表面有关性能包括抗磨性和防锈性方面还存在问题。
本发明人研制基于合成油源或矿物油源的烃基原料的润滑油,这种润滑油很好地综合了性能特征。这些润滑油的特征是很好综合了抗磨性和防锈性。如下面所述,抗磨性由不大于0.35毫米最大划痕直径(在钢上的钢)四球磨损试验(ASTM D 4172)值与可达到的不大于0.30毫米值,以及由其它优良性能标记表示。可获得0.07毫米磨损划痕直径的ASTM四球青铜上钢的值。用通过合成海水的ASTM D 665B来表示防锈性能。优良的水解稳定性、高温性能、抗锈、抗蚀、抗氧化和油品的长寿命都是本发明油品的如下所述的特征。
本发明的合成油包括主要部分的饱和烃的主要原料组分,可以和其它润滑剂原料组分混合。被认为适合这一目的的原料组分包括烃如主要是饱和的、粘度指数为110或更大、硫含量一般小于0.3%(重量)、芳烃和烯烃总含量分别小于10%(重量)的那些。这种类型的烃基原料包括API组Ⅲ原料(以及一些组Ⅱ中的油品)、组Ⅳ原料(PAOs)以及API组Ⅴ中的其它合成烃基原料。通过加入烃基取代的芳烃如较长链取代的芳烃,这些组分可任选与其它混合组分混合。较好的辅助原料组分是具有润滑粘性的油,它们是烃取代的芳烃化合物,如长链烷基取代的芳烃,包括烷基取代的萘、烷基取代的苯、烷基取代的联苯基化合物和烷基取代的联苯基甲烷。通常,这种辅助原料组分占总原料的50%以下,较好的不超过25%。
本发明组合物的特征是在原料中没有酯类情况下很好地结合了抗磨性和防锈性,尽管可以任选包含酯类,以改善一些性能例如雾度。如果包含酯类,酯的用量通常不超过基本原料的10%,通常要求不超过5%,以处理可能出现的任何雾度问题。可以存在最少量的其它材料作为有意的液体组分或作为添加剂的溶剂或载体液体。
添加剂的协同组合赋予本发明组合物要求的抗磨性和防锈性综合配合。这种组合物是取代的***如苯并***或取代的苯并***如甲苯基***(tolyltriazole)(TTZ)与磷酸芳胺的加合物、连同磷酸三烃酯,较好是磷酸三芳烃酯如磷酸甲苯二苯酯(CDP)的独特混合物。已发现***/磷酸胺组合物为润滑剂组合物提供了优良的氧化稳定性、抗磨性和防锈性,但是通过加入磷酸三烃酯,尤其当烃基为芳基如在CDP时这种修改达到增强。另外,本发明油品一般包括抗氧化组分以及其它任选的添加剂组分,如一种或多种抗腐蚀剂、另外的防锈剂、消泡剂、生色剂等。
本发明的油品适合用作齿轮油、循环油、压缩机油、以及其它应用例如湿离合器***、鼓风机齿轮。在齿轮应用中,这些油品可用于钢与钢(正齿轮)以及钢上青铜(涡轮)的应用。下面进一步描述工业应用。
本油品使用了一种包括润滑粘性的主要烃基原料组分的基本流体。这种组分的特点是饱和的,粘度指数为110或更大,硫含量小于0.3%(重量),总芳烃和烯烃含量各自小于10%(重量)。这种类型的烃基原料包括在API组Ⅲ的(以及一些组Ⅱ中的油品)矿物油、组Ⅳ原料(PAOs)以及API组Ⅴ中的其它合成烃基原料。较好的这种类型的烃基原料是API组Ⅳ的聚α烯烃。润滑剂总量的至少50%包括主要烃组分,这一组分量一般至少为原料总量的60%。在一个较好的实施方案中,这一组分占组合物总量的至少75%。
这种主要原料组分可以是合成来源或矿物油来源,尽管合成材料为较好的。合适矿物油原料的特点在于主要是饱和的(链烷烃)组合物、相对无硫和大于110的高粘度指数(ASTM D 2270)。饱和度(ASTM D 2007)至少为90%(重量)。受到控制的硫含量不大于0.03%(重量)(ASTM D 2622、D 4294、D 4927、D 3120)。这种矿物油来源的原料组分包括加氢处理过的原料,尤其是加氢处理和加氢脱蜡过的馏出原料、催化加氢脱蜡过的残油、加氢裂解和加氢异构化的石油蜡,包括被称作XHVI油的润滑油、以及一般分类为API组Ⅲ原料的矿物来源的其它油。通过加氢处理转化为合适的高品质原料的矿物来源的例子包括蜡馏出原料如汽油、疏松石蜡、去油蜡和微晶蜡,以及燃料氢化裂化器底部馏份。在美国专利5,885,438;5,643,440;5,358,628;5,302,279;5,288,395;2,275,719;5,264,116和5,110,445中描述了加氢异构化石油蜡和其它原料制备高品质润滑原料的方法。在美国专利5,468,368中描述了从燃料氢化裂化器底部生产高粘度指数的高品质润滑油基本原料。
合成烃基本原料包括聚α烯烃(PAOs)和来自Fischer Tropsch高沸点馏份包括蜡的加氢裂化或加氢异构化的合成油。它们都是包括与其合成来源相一致的低杂质量的饱和物。加氢异构化的Fischer Tropsch蜡是特别合适的原料,包括异链烷烃特点的饱和组分(产生于Fischer Tropsch蜡的主要正链烷烃的异构化),由这类原料能得到高粘度指数和低流点的优良混合物。在美国专利5,362,378;5,565,086;5,246,566和5,135,638、以及EP710710、EP321302和EP321304中描述了Fischer Tropsch蜡加氢异构化方法。
PAO是已知的物质,一般包括α烯烃的分子量相对较低的加氢过的聚合物或低聚物,这些α烯烃包括但不限于C2-C32α烯烃,较好的是C8-C16α烯烃,如1-辛烯、1-癸烯、1-十二碳烯等。较好的聚α烯烃是聚-1-癸烯和聚-1-十二碳烯,尽管在C14-C18范围的较高级烯烃的二聚物可提供低粘度的基本原料。
PAO流体一般是通过在聚合反应催化剂如Friedel-Crafts催化剂包括例如三氯化铝、三氟化硼或三氟化硼与水的配合物,醇类如乙醇、丙醇或丁醇,羧酸或酯类如乙酸乙酯或丙酸乙酯存在下,聚合α烯烃来制得。例如,本文中一般采用美国专利4,149,178和3,382,291中揭示的方法。PAO合成的其它描述可见于下列美国专利:3,742,082(Brennan);3,769,363(Brennan);3,876,720(Heilman);4,239,930(Allphin);4,367,352(Watts);4,413,156(Watts);4,434,408(Larkin);4,910,355(Shubkin);4,956,122(Watts);5,068,487(Theriot)。最有用的一类PAO基本原料是通过还原过的铬催化剂与α烯烃作用制得的高粘度指数PAO(HVI-PAOs);在U.S.4,827,073(Wu);4,827,064(Wu);4,967,032(Ho等);4,926,004(Pelrine等);4,914,254(Pelrine)中描述了这种HVI-PAOs。在美国专利4,218,330中描述了C14-18烯烃的二聚物。
PAO的平均分子量一般在250-10,000范围,较好的为300-3,000,100℃粘度为3-200cS。PAO是配方中的主要组分,对最后产品的粘度和其它粘度性质会有最大影响。由于制成的产品是按照粘度等级销售。通常PAO组分包括一种或多种不同粘度的PAO,最轻的组分通常为2cS(100℃)组分,与其它存在的多种粘性PAO,以达到最后配方要求的粘度。通常,制得的PAO粘度高达1,000cS(100℃),尽管在大多数情况,并不要求粘度大于100cS,除了少量粘度指数改进剂外。
除了主要烃组分外,基本原料还可以包括具备需要的润滑性质的辅助液体组分。较好的是烃取代的芳烃化合物如长链烷基取代的芳烃。对所有这些物质较好的烃取代基是有至少8个碳原子,一般至少有10个碳原子的长链烷基,以提供主要烃混合物组分良好的溶解度。12-18个碳原子的烷基取代基为合适的,可采用使用烯烃或其它烷基化剂的常规烷基化法加上这些取代基。分子的芳烃部分可以是烃或非烃,如下面举出的例子。
包括在这类基本原料中的混合物组分例如是长链烷基苯和长链烷基萘,长链烷基萘为特别好的原料,因为它们是水解稳定的,因此可以和PAO组分组合用于湿应用。烷基萘是已知物质,在美国专利4,714,794(Yoshida等)中描述了这类物质。使用烷基化和多烷基化萘作为合成功能流体的原料可参阅美国专利4,604,491(Dressler)。较好的烷基萘是有10-40个碳原子的长链烷基的那些,尽管如果需要可使用更长的链。通过用有14-20个碳原子的烯烃来烷基化萘制得的烷基萘具有特别优良的性质,尤其当使用沸石如大孔径沸石作为烷基化催化剂时。如美国专利5,602,086(对应于EP 496486)中描述了这些物质的合成。这些烷基萘主要是单取代萘,连接有主要在烷基链的1-位或2-位的烷基。长链烷基的存在提供烷基萘良好的粘度性质,尤其当用于和本身为高粘度指数、低流点和良好流动性的PAO组分组合时。
另一种辅助混合用基本原料是烷基苯或烷基苯混合物。这些流体中的烷基取代基一般是有8-25个碳原子,较好是10-18个碳原子的烷基,最多可存在三个这样的取代基,如ACS Petroleum Chemistry Preprint 1053-1058,“Poly n-AlkylbenzeneCompounds:A Class of Thermally Stable and Wide Liquid Range Fluids”,Eapen et al,Phila.1984中所述。如美国专利5,055,626中所述,通过8-12个碳原子的1-炔的环化二聚,也可制得三烷基苯。在EP 168534和4,658,072中描述了其它的烷基苯。烷基苯可用作润滑剂基本原料,尤其对低温应用(极地用的机动车和冷冻油)和造纸用油;一般可从线型烷基苯(LABs)生产商如Vista Chem.Co,Hunstman Chemical Co.以及Chevron Chemical Co.和Nippon Oil Co.购得。线型烷基苯一般具有良好的低流点、低温粘度、大于100的VI值,以及对添加剂的良好溶解性。需要时可使用其它烷基化的芳烃,例如在“合成润滑剂和高性能的功能流体”,Dressier,H.,chap 5,(R.L.Shubkin(Ed.)),Marcel Dekker,N.Y·993中所述的。
包括在这类中并具有要求的润滑特性的还有烷基化的芳烃化合物,包括烷基化的二苯基化合物如烷基化的二苯醚、烷基化的二苯硫和烷基化的二苯甲烷和烷基化的吩噻噁以及烷基噻吩、烷基苯并呋喃和含硫芳烃的醚。例如,在美国专利5,552,071;5,171,195;5,395,538;5,344,578;5,371,248和EP 815187中描述了这种类型的润滑剂混合组分。
辅助组分的用量一般不超过总组成的40%(重量),大多数情况下不超过25%(重量)。烷基萘用量宜为5-25%(重量),一般为10-25%(重量)。烷基苯和其它烷基芳烃用量可以相同,尽管已发现在有些润滑剂配方中烷基萘在一些应用中氧化性能优良。
尽管现有的润滑剂一般是以烃为基的组合物,在有些应用中这些润滑剂可以利用少量其它原料,例如用于改善雾度、溶解性或大多数情况的密封溶胀,烷基萘组分提供了良好的这些性能。可存在的另外的原料包括聚(亚烷基)二醇(PAGs)和酯油类,两者都是常用型。这样的添加组分的量一般不应超过总组成的5%(重量)。如果雾度值需要改善,存在多达5%(重量)的酯一般可纠正这一问题。
可用于这一目的的酯类包括二元酸与单烷基醇的酯和单羧酸的多元醇酯。前一种酯类包括例如二元羧酸如苯二甲酸、琥珀酸、烷基琥珀酸、烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、富马酸、己二酸、亚油酸二聚体、丙二酸、烷基丙二酸、烯基丙二酸等与各种醇类如丁醇、己醇、十二烷醇、2-乙基己醇等的酯。这些类型的酯的例子包括己二酸二丁酯、癸二酸二(2-乙基己基)酯、富马酸二正丁酯、癸二酸二辛酯、壬二酸二异辛酯、壬二酸二异癸酯、苯二甲酸二辛酯、苯二甲酸二癸酯、癸二酸二(二十烷基)酯等。
特别有用的合成酯类是通过一种或多种多元醇,较好的是有位阻的多元醇,例如新戊基多元醇如新戊二醇、三羟甲基乙烷、2-甲基-2-丙基-1,3-丙二醇、三羟甲基丙烷、季戊四醇和双季戊四醇与含至少4个碳原子的链烷酸,通常是C5-C30酸,如饱和直链脂肪酸包括辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸和山萮酸,或相应的带支链的脂肪酸或不饱和脂肪酸如油酸反应制得的那些酯。
最合适的合成酯油是三羟甲基丙烷、三羟甲基丁烷、三羟甲基乙烷、季戊四醇和/或双季戊四醇与一种或多种含5-10个碳原子的单羧酸(均为市场可购得的,例如Mobil P-41和P-51酯(Mobil Chemical Company))的酯。
通过适当混合不同粘度的基本原料组分,如果需要可使用增稠剂,来调节最终产品的粘度等级。不同粘度的各种基本原料组分(主要是烃基本原料、辅助基本原料和任何添加的基本原料组分)以不同量适当混合,制得的基本原料混合物具有适合与最终润滑剂的其它组分混合的粘度。最终产品的粘度等级在ISO 20-ISO 1000范围,甚至更高,可用于齿轮润滑剂应用,例如高达ISO 46,000。对低粘度等级,一般为ISO20-ISO 100,混合后原料的粘度略高于最终产品的粘度,通常为ISO 22-ISO 120,但是更粘的等级可高达ISO 46000,添加剂常常会略降低原料混合物的粘度值。例如对ISO 680等级的润滑剂,根据添加剂的性能和含量,原料混合物粘度为780-800cS(40℃)。
尤其在制备高粘度等级产品,如ISO 680-ISO 46000,通过使用聚合物增稠剂,使最终产品粘度达到要求等级。可使用的增稠剂包括聚异丁烯、以及乙烯-丙烯聚合物、聚甲基丙烯酸酯和各种二烯嵌段聚合物和共聚物、聚烯烃和聚烷基苯乙烯。这些增稠剂一般用作粘度指数改进剂(Ⅶs)或粘度指数改性剂(ⅥMs),一般能对温度-粘度关系提供有用的效果。可以根据市场需要、制造要求粘度等级的最终产品的设备制造商的说明书,来混合这些组分。市场上可购得的典型的浓度指数改进剂是聚异丁烯、聚合的和共聚的甲基丙烯酸烷酯、苯乙烯马来酸酐共聚体与含氮化合物反应的混合酯。
通常分子量为10,000-15,000的聚异丁烯是可购得的重要的一类Ⅵ改进剂,由于其分子结构,能明显提高粘度。二烯聚合物,通常是1,3-二烯如丁二烯或异戊二烯单独或与苯乙烯的共聚物,也是重要的一类,其中有以ShellvisTM名销售的。由丁二烯和苯乙烯一般可制备统计聚合物,而由丁二烯/异戊二烯和异戊二烯/苯乙烯则可制得嵌段共聚物。这些聚合物一般可经加氢除去残余的二烯不饱和性,提高稳定性。分子量在15,000-25,000的聚甲基丙烯酸酯是另一类重要的增稠剂商品,例如可以AcryloidTM商标购得。
有一类聚合增稠剂是通过不饱和单体包括苯乙烯、丁二烯和异戊二烯的阴离子聚合制备的嵌段共聚物。在美国专利5,187,236;5,268,427;5,276,100;5,292,820;5,352,743;5,359,009;5,376,722和5,399,629中描述这种类型的共聚物。嵌段共聚物可以是线型或星形共聚物,对本发明目的,优选线型共聚物。较好的聚合物是异戊二烯-丁二烯和异戊二烯-苯乙烯阴离子二嵌段和三嵌段共聚物。特别好的高分子量聚合物组分是由Shell Chemical Company销售的牌号为ShellvisTM 40、ShellvisTM 50和ShellvisTM 90的那些,都是线型阴离子共聚物,其中ShellvisTM 50是阴离子二嵌段共聚物,ShellvisTM 200、ShellvisTM 260和ShellvisTM 300是星形共聚物。
有些增稠剂由于其双重作用被分类为分散剂-粘度指数改进剂,如美国专利4,594,378中所述。该专利中揭示的分散剂-粘度指数改进剂是含羧酸的共聚体的含氮酯和丙烯酸酯的油溶的丙烯酸酯聚合产物,单独一种或它们的组合。可购得的分散剂-粘度指数改进剂有Rohm and Hass以AcryloidTM 1263和1265商品名销售的产品,由Rohm GMBHOTM Registered TM销售的ViscoplexTM 5151和5089,以及LubrizolTM 3702和3715。
Klamann在Lubricants and Related Products,Verlag Chemie,Weinheim 1984,ISBN3-527-26022-6一书中详细讨论了可用作增稠剂或Ⅵ改进剂的高分子量聚合物,Deerfied Beach,FL 0-89573-177-0(英译本)也详细讨论其它润滑剂添加剂,如下面所述。可参考“Lubricant Additives”,M.W Ranney,由Noyes Data Corporation ofParkridge,N.J.(1993)出版。
使用抗氧化剂提供氧化稳定性,有许多市售产品适合此目的。可用于本组合物的最普通的抗氧化剂是酚类抗氧化剂、胺类抗氧化剂、烷基芳族硫化物、磷化合物如亚磷酸和膦酸酯、以及硫-磷化合物如二硫代磷酸酯和其它类型如双二硫代氨基甲酸烷基酯类如亚甲基双(二硫代氨基甲酸正丁基酯)。它们可以单独使用或与另一种组合使用。较好的是不同类型的酚或胺的混合物。
具备抗氧化性能的硫化合物包括二烷基硫醚如二苄基硫醚、聚硫化物、二芳基硫醚、改性硫醇、巯基苯并咪唑、噻吩衍生物、黄原酸酯和硫代二醇。在前面引用的Lubricant and Related Products,Klamann著的一书中描述了这种类型的物质和可使用的其它抗氧化剂。
可用于本发明润滑剂的酚类抗氧化剂中合适的是无灰(没有金属)的酚化合物或一些酚化合物的中性或碱金属盐。润滑剂流体中酚化合物加入量可根据加入的酚化合物的具体用途,可以在宽的范围内变动。在功能流体中一般包含0.1-10%(重量)的酚化合物。更常用量为0.1-5%(重量),如2%(重量)。
较好的酚化合物是含有一个空间位阻羟基的位阻酚,包括二羟基芳基化合物的衍生物,两个羟基彼此为邻位或对位。典型的酚抗氧化剂包括有C6+烷基取代的位阻酚,以及中心位阻酚的亚烷基偶联衍生物。这种类型酚的例子包括2-叔丁基-4-庚基苯酚;2-叔丁基-4-辛基苯酚;2-叔丁基-4-十二烷基苯酚;2,6-二叔丁基-4-庚基苯酚;2,6-二叔丁基-4-十二烷基苯酚;2-甲基-6-二叔丁基-4-庚基苯酚和2-甲基-6-二叔丁基-4-十二烷基苯酚。邻位偶联的酚的例子包括:2,2′-双(6-叔丁基-4-庚基苯酚);2,2′-双(6-叔丁基-4-辛基苯酚)和2,2′-双(6-叔丁基-4-十二烷基苯酚)。使用含硫酚也有很大好处。硫可以芳族硫或脂族硫存在于酚抗氧化剂分子中。
还可以使用非酚类氧化抑制剂,尤其是芳胺类抗氧化剂,或与酚组合使用。非酚类抗氧化剂的典型例子包括:烷基化和非烷基化芳胺如通式R3R4R5N的芳烃单胺,其中R3是一个脂族、芳族、或取代的芳族基团,R4是一个芳族或取代的芳族基团,R5是H、烷基、芳基或R6S(O)xR7,其中R6是亚烷基、亚烯基(alkenylene)或芳亚烷基(aralkylene),R7是高级烷基或烯基、芳基或烷基芳基,x是0、1或2。脂族基团R3可含有1-20个碳原子,较好的含有6-12个碳原子。脂族基团是饱和脂族基团。较好的R3和R4都是芳族或取代芳族基团,芳族基团可以是稠环芳族基团如萘。芳族基团R3和R4可以和另一个基团如S结合在一起。
典型的芳胺抗氧化剂具有至少6个碳原子的烷基或芳基取代基。脂族基团的例子包括己基、庚基、辛基、壬基和癸基。芳基的例子包括苯乙烯化或取代的苯乙烯化的基团。一般,脂族基团的碳原子数不超过14。可用于本发明组合物的常用的胺类抗氧化剂包括二苯胺、苯基萘胺、吩噻嗪、亚氨二苄基和二苯基苯二胺。也可以使用两种或多种芳胺的混合物。还可以使用聚合胺抗氧化剂。用于本发明的芳胺抗氧化剂的具体例子包括:p,p′-二辛基二苯胺;辛基苯基-β-萘胺;叔辛基苯基-α-萘胺;苯基-α-萘胺;苯基-β-萘胺;p-辛基苯基-α-萘胺;4-辛基苯基-辛基-β-萘胺。
可使用的典型的二烷基二硫代磷酸酯盐是二硫代磷酸二烷酯锌,特别是二硫代磷酸二辛酯锌和二硫代磷酸二苄酯锌。这些盐常用作抗磨剂,但它们也具有抗氧化功能,尤其当与油溶性铜盐组合用作共抗氧化剂时。与磷和锌的化合物如二硫代磷酸烷基酯盐组合用作抗氧化剂的铜盐包括羧酸如硬脂酸、棕榈酸和油酸的铜盐、酚铜、磺酸铜、乙酰丙酮铜、由分子量一般为200-500的环烷酸得到的环烷酸铜、以及铜取代锌的二硫代氨基甲酸铜和二硫代磷酸二烷基酯铜。在美国专利4,867,890中描述了这种类型的铜盐和将它们用作抗氧化剂。
抗氧化剂总量一般不超过总组成的10%(重量),一般更低,小于5%(重量)。一般抗氧化剂的合适用量为0.5-2%(重量),尽管如果需要,有些应用中可使用更多的抗氧化剂。
使用抑制剂组合剂,可提供要求的抗磨和防锈/防腐蚀性能的综合平衡。这种组合剂中的一个组分是取代的苯并***/磷酸胺加合物,其余是三取代磷酸酯,特别是三芳基磷酸酯如磷酸甲苯基二苯基酯盐,一种可购得的已知材料。这种组分存在量最多为组合物的5%(重量)。一般小于总组成的3%,如0.5-2%(重量),就足以提供要求的抗磨性。
抗磨/防锈组合物的辅助组分是苯并***或取代的苯并***与磷酸胺的加合物,这种加合物还提供抗磨性和抗氧化性能。在美国专利4,511,481中描述了这类多功能加合物及其制备方法。简单说来,这些加合物包括下式的取代苯并***
即烷基取代的苯并***,其中取代基R是氢或C1-C6低级烷基,较好是甲基。较好的***是甲苯基***(TTZ)。为方便起见,这种组分在此称作TTZ,尽管也可以使用其它的苯并***,如美国专利4,511,481中所述。
加合物的胺组分可以是美国专利4,511,481中列出式的芳族磷酸胺盐,(HO)x-P(O)(O-NH3 +-Ar)y,其中(x+y)=3,Ar是芳基。或者,主要组分是脂族胺盐,例如有机酸磷酸盐和烷基胺如二烷基胺。磷酸烷基胺加合物可按照与芳胺加合物同样方式制备。这种类型的较好的盐是长链(C11-C14)烷基胺的单/二己酸磷酸盐,可与TTZ制成加合物用于本发明。该加合物的TTZ和长链烷基/有机酸磷酸盐的比值在1∶3至3∶1(摩尔)范围,较好的加合物的比值为75:25(重量)。TTZ磷酸胺盐加合物的用量相对较少,一般小于5%(重量),通常为0.1-1%(重量)范围,如在与磷酸三烃基酯如磷酸甲苯基二苯基酯组合使用时,为达到抗磨性和防锈性良好的综合平衡,0.25%(重量)就足够。通常,使用CDP和TTZ加合物的重量比为2∶1至5∶1。
还可以使用另外的防锈添加剂。可用于这一目的的市售金属减活化剂例如包括N,N-二取代氨基甲基-1,2,4-***和N,N-二取代氨基甲基-苯并***。N,N-二取代氨基甲基-1,2,4-***可通过已知方法制备,即使1,2,4-***与甲醛和一种胺反应(如美国专利4,734,209中所述)。N,N-二取代氨基甲基-苯并***同样可通过使苯并***与甲醛和一种胺反应来制备,正如美国专利4,701,273中所述。较好的金属减活化剂是1-[双(2-乙基己基)氨基甲基]-1,2,4-***或1-[双(2-乙基己基)氨基甲基]-4甲基苯并***(甲苯基***∶甲醛∶二-2-乙基己基胺(1∶1∶1)的加合物),市场可购得。其它用于提供额外防锈作用的防锈剂包括琥珀酰胺的衍生物如高级烷基取代的亚十二烷基琥珀酸酰胺(也可购得)、亚十二烷基琥珀酸高级烷基取代酰胺如四丙烯基琥珀酸单酯(可购得)和咪唑啉琥珀酸酐衍生物,如四丙烯基琥珀酸酐的咪唑啉衍生物。即,这些另外的防锈剂的用量相对较小,小于2%(重量),尽管对有些应用如造纸设备的机油,如果需要可高达5%(重量)。
根据具体用途的需要,油品还可以包括其它的常规添加剂,例如分散剂、洗涤剂、摩擦改进剂、引力改进添加剂(traction improving additive)、破乳剂、消泡剂、生色团(染料)、雾度抑制剂,根据用途,采用常规混合法,混合上述市售材料添加剂。
如上所述,本发明润滑油具有优良的性能,包括特别是综合了良好的防锈性和抗磨性。这种性能的综合平衡非常显著,对于以烃为基的原料的油品尤其好。
抗磨性在FZG Scuffing试验(DIN 51534)中性能表示良好,失败阶段值至少为8,常用值在9-13或更高范围。FZG试验是在正齿轮上进行的钢与钢接触的性能标志;该试验中性能优良表示可预期良好的正齿轮性能。通常高粘度等级的油品如ISO 100可达到较高的FZG试验值,与粘度等级低于ISO 100,FZG值为9-12的油品相比,更高等级粘度油品的FZG值可达12或更高,甚至13或更高。对ISO 300和更高,可达到13或更高(A/16.6/90)或12和更高(A/8.3/140)。
抗磨性还可以用不大于0.35毫米最大划痕直径(钢在钢上,1小时,180rpm,54℃,20kg/cm2)的4-球(ASTM D 4172)磨耗试验值,易达到不大于0.30毫米值表示。可达到120或更大,通常为150或更大的4-球EP值。ASTM4-球钢在青铜上值通常为0.07毫米(磨耗划痕直径)。
防锈性用合成海水的ASTM D 665B中的Pass表示。在121℃,铜条24小时腐蚀(ASTM D130)通常最大为2A,一般为1B或2A。
多个性能标准包括Mobil催化氧化试验1表明具有优良的高温氧化性能。本发明组合物的特点是不大于5毫克KOH(ΔTAN,163℃,120小时)的试验值,可达到小于3毫克KOH,甚至更小,小于0毫克KOH。在催化氧化试验中粘度提高通常不超过15%,可低到8-10%。
1在催化氧化反应中,将50毫升油品、与铁、铜和铝催化剂以及称重的铅腐蚀油品一起放入一个玻璃瓶中。该瓶和其内物料置于保持在163℃的浴,以10升/小时流量,干空气鼓泡通过样品40分钟。从该浴中取出瓶,从瓶中除去聚集的催化剂。检测油品中浆料的存在和中和值变化(ASTM D 664)和100℃时运动粘度(ASTM D 445)。清洁铅油品并称重,决定其重量损失。
用不大于0.020%(重量),通常不大于0.015%(重量)的TOST糊料(1,000小时)获得至少8,000小时的TOST值(ASTM D943),通常至少10,000小时,也表明良好的抗氧化性。
本发明的润滑油可用于润滑承载体、齿轮和其它要求宽温度范围的工业应用。本发明油品特点是很好综合平衡各种性能包括改进的抗磨性和防锈性。本发明油品用作齿轮油、循环油、压缩机油以及在其它应用如湿离合器***、鼓风机齿轮、煤粉磨机驱动器、冷却塔轴承箱、窑驱动器、造纸设备驱动器和旋转螺杆压缩机中的使用。由下面的应用来说明这些应用对润滑剂性能的具体要求:
煤粉磨机驱动器 沉降控制
冷却塔轴承箱 抗腐蚀性
窑驱动器 高温稳定性
造纸设备驱动器 高温、水解稳定性
旋转螺杆压缩机 延长油寿命、沉降控制
实施例1-2
下面两种油品为本发明配方的例子:
表1合成油配方
组分 | 实施例1 | 实施例2 |
PAO,5-6cS | 23.07 | 16.07 |
PAO,100cS | 53.00 | 61.01 |
C14烷基萘 | 20.00 | 20.00 |
酚/非酚,抗氧化剂 | 1.50 | 1.50 |
CDP | 0.95 | 0.75 |
TTZ/磷酸胺 | 0.25 | 0.25 |
亚铁/亚非铁抗腐蚀剂组合物1 | 0.23 | 0.23 |
消泡剂 | 1.00 |
注:
1.含胺和烷基酯的混合抗腐蚀剂
实施例3
按照下面(重量百分数)配制ISO等级32的油品
表2
ISO VG32
组分 | |
C14烷基萘 | 20.00 |
40cS PAO | 8.50 |
6cS PAO | 68.28 |
胺抗氧化剂 | 0.75 |
CDP | 0.95 |
亚铁/非亚铁抗腐蚀剂1 | 0.26 |
TTZ/磷酸胺 | 0.25 |
消泡剂组合物 | 1.00 |
染料 | 0.01 |
注:
1.含胺和烷基酯的混合抗腐蚀剂。对实施例3的油品进行各种标准试验,试验结果列于表3。
表3
试验 | 试验方法 | 结果(典型) |
TAN | D664 | 0.42 |
ASTMRustB | D665B | 通过 |
铜条,24小时,121℃ | D130 | 1B |
TOST糊料,1000小时 | D943 | 0.015 |
TOST寿命 | D943 | 10,000 |
催化氧化,120小时,163℃,Vis.Inc. | 10.0 | |
催化氧化,120小时,163℃,在TAN中变化. | -0.3 | |
催化氧化,120小时,163℃,糊料 | 轻 | |
RBOT,150℃ | D2272 | 1,750 |
FZG,失败阶段 | DIN51534 | 10 |
Claims (20)
1.一种改进了抗磨性和防锈性的润滑油组合物,所述组合物包括一种包含至少50%重量的烃基流体和包含(1)取代***和烃胺磷酸盐的加合物和(2)磷酸三烃基酯的组合添加剂。
2.如权利要求1所述的润滑剂,其特征在于所述烃基流体包含一种润滑粘性的烃,这种烃为饱和的,其粘度指数为110或更大,硫含量小于0.3%重量,芳烃总含量和烯烃总含量各自小于10%重量。
3.如权利要求2所述的润滑剂,其特征在于所述烃基流体包括矿物来源的加氢异构化蜡或加氢异构化Fischer Tropsch蜡。
4.如权利要求1所述的润滑剂,其特征在于所述烃基流体包括至少50%重量的聚α-烯烃合成烃。
5.如权利要求1所述的润滑剂,其特征在于所述烃胺磷酸盐包括甲苯基***和烷基胺烷基酸磷酸盐的加合物。
6.如权利要求1所述的润滑剂,其特征在于所述润滑剂包括多达25%重量的油组合物,所述油组合物包括润滑粘性的长链烷基芳族化合物。
7.如权利要求6所述的润滑剂,其特征在于所述润滑剂包括多达该组合物25%重量的长链烷基化萘作为烷基芳族化合物。
8.如权利要求7所述的润滑剂,其特征在于所述润滑剂包括多达该组合物25%重量的有C10-C14烷基取代基的长链的主要为单烷基化的萘。
9.如权利要求1所述的润滑剂,其特征在于所述润滑剂具有不大于0.35毫米最大划痕直径(钢在钢上)的4-球(ASTM D 4172)磨耗试验值和符合ASTM D 665B的防锈性能。
10.如权利要求1所述的润滑剂,其特征在于所述润滑剂具有不大于0.30毫米最大划痕直径(钢在钢上)的4-球(ASTM D 4172)磨耗试验值和符合ASTM D 665B的防锈性能。
11.如权利要求1所述的润滑剂,其特征在于所述润滑剂的FZG失败阶段值(DIN51354)至少为10。
12.如权利要求1所述的润滑剂,其特征在于所述润滑剂的TOST(ASTM D943)至少为8,000小时。
13.如权利要求1所述的润滑剂,具有按重量百分数计的下列组成:
聚α-烯烃基原料
65-80
长链(C10-C16)单烷基萘
15-25
抗氧化剂
0.5-5
磷酸甲苯二苯酯
0.5-5
TTZ/烷基胺磷酸盐加合物
0.1-1
亚铁/非亚铁抗腐蚀剂
0.1-1
14.如权利要求13所述的润滑剂,其特征在于所述抗氧化剂包括各为0.1-1%的酚类抗氧化剂和芳胺抗氧化剂。
15.如权利要求13所述的润滑剂,其特征在于所述磷酸甲苯二苯酯的含量为0.5-1.0%。
16.如权利要求13所述的润滑剂,其特征在于所述TTZ/烷基胺磷酸盐加合物的含量为0.1-0.5%。
17.如权利要求13所述的润滑剂,其特征在于所述亚铁/非亚铁抗腐蚀剂的含量为0.1-0.5%。
18.如权利要求1所述的润滑剂,具有按重量百分数计的下列组成:
聚α-烯烃基原料
65-80
长链(C10-C16)单烷基萘
15-25
抗氧化剂
0.5-5
磷酸甲苯二苯酯
0.5-5
TTZ/烷基胺磷酸盐加合物
0.1-1
亚铁/非亚铁抗腐蚀剂
0.1-1
19.如权利要求18所述的润滑剂,其特征在于所述磷酸甲苯二苯酯的含量为0.5-1.0%。
20.如权利要求15所述的润滑剂,其特征在于所述TTZ/烷基胺磷酸盐加合物的含量为0.1-0.5%。
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- 1999-07-29 CA CA002339279A patent/CA2339279C/en not_active Expired - Lifetime
- 1999-07-29 KR KR1020017001459A patent/KR100630350B1/ko not_active IP Right Cessation
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CN101070506B (zh) * | 2006-03-22 | 2011-04-20 | 雅富顿公司 | 齿轮流体 |
CN101977879A (zh) * | 2008-03-18 | 2011-02-16 | 埃克森美孚化学专利公司 | 合成润滑剂制备方法 |
CN102808856A (zh) * | 2011-09-15 | 2012-12-05 | 王福贵 | 一种新型牙箱式轴承盒及其制作方法 |
CN102808856B (zh) * | 2011-09-15 | 2015-12-16 | 王福贵 | 一种牙箱式轴承盒 |
CN105238507A (zh) * | 2015-09-07 | 2016-01-13 | 上海纳克润滑技术有限公司 | 柴机油及其制备方法和其在柴油发动机中的应用 |
CN109477020A (zh) * | 2016-07-07 | 2019-03-15 | 道达尔销售服务公司 | 用于燃气引擎的润滑剂组合物 |
Also Published As
Publication number | Publication date |
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AU744605B2 (en) | 2002-02-28 |
KR100630350B1 (ko) | 2006-10-02 |
NO20010583L (no) | 2001-03-29 |
KR20010099607A (ko) | 2001-11-09 |
EP1121404B1 (en) | 2016-02-03 |
EP1121404A1 (en) | 2001-08-08 |
CN1231564C (zh) | 2005-12-14 |
AU5241399A (en) | 2000-02-28 |
JP2002522590A (ja) | 2002-07-23 |
JP4478332B2 (ja) | 2010-06-09 |
EP1121404A4 (en) | 2003-01-22 |
US6180575B1 (en) | 2001-01-30 |
BR9912704A (pt) | 2002-04-30 |
CA2339279C (en) | 2008-10-07 |
CA2339279A1 (en) | 2000-02-17 |
NO20010583D0 (no) | 2001-02-02 |
ZA200100871B (en) | 2002-01-31 |
WO2000008119A1 (en) | 2000-02-17 |
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