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CN102666817A - 润滑组合物 - Google Patents

润滑组合物 Download PDF

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CN102666817A
CN102666817A CN2010800483238A CN201080048323A CN102666817A CN 102666817 A CN102666817 A CN 102666817A CN 2010800483238 A CN2010800483238 A CN 2010800483238A CN 201080048323 A CN201080048323 A CN 201080048323A CN 102666817 A CN102666817 A CN 102666817A
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lubricating composition
detergent
koh
purification agent
base oil
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J·L·加西亚奥赫达
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Shell Internationale Research Maatschappij BV
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Abstract

本发明提供一种润滑组合物，所述润滑组合物至少包含基油和清净剂；其中所述清净剂以清净剂总量计包含至少30mol％BN(碱数)为0.1-80mg KOH/g的磺酸盐清净剂；其中所述清净剂以清净剂总量计包含30-70mol％的酚盐清净剂；其中所述润滑组合物以润滑组合物总重量计包含至少4wt％的清净剂；其中所述润滑组合物的TBN(总碱数)为至少10mg KOH/g(按ASTM D 2896)。

Description

润滑组合物
技术领域
本发明涉及一种润滑组合物，特别涉及在持续高负荷条件下操作的内燃机中应用的润滑组合物，例如在船用柴油机和发电用途中应用的润滑组合物。更特别地，本发明涉及一种船用润滑剂。
技术背景
船用润滑剂在本领域中是已知的。例如，EP1086195公开了一种含润滑基油和过碱性清净剂组分的船用汽缸油组合物，所述组合物的TBN为50-90，和所述清净剂组分包含在100℃下粘度为至少180cSt及TBN为约400或更大的过碱性磺酸钙。
在内燃机中应用的润滑组合物将承受高应力。重要的是所述润滑组合物能在各种条件下提供好的润滑性能，以有助于保持发动机清洁、热和氧化稳定，提供好的耐磨、防腐保护并从发动机带走热量。
由于船用发动机经常在偏远地区通常在接近满载状态下长期连续运行，因此船用柴油机中应用的润滑组合物将承受特别高的应力。另外，由于经常很少或几乎没有机会更换船用发动机中的润滑组合物，因此希望润滑组合物具有长的寿命。
现有技术中将理解的是术语″船用″并不局限于在水载容器中应用的那些发动机。也就是说，所述术语还包括用于发电用途的发动机。这些高级的、燃料有效的、慢和中速船用发动机和固定式柴油机在高压、高温和长冲程下操作。
发明内容
本发明的一个目的是提高特别是在内燃机如船用柴油机中应用的润滑组合物的沉积物形成性能。
本发明的另一个目的是提供在内燃机中使用的替代润滑组合物。
本发明通过提供一种润滑组合物可以达到一个或多个上述或其它目的，所述润滑组合物至少包含基油和清净剂；其中所述清净剂以清净剂总量计包含至少30mol％BN(碱数)为0.1-80mg KOH/g的磺酸盐清净剂；其中所述清净剂以清净剂总量计包含30-70mol％的酚盐清净剂；其中所述润滑组合物以润滑组合物总重量计包含至少4wt％的清净剂；和其中所述润滑组合物的TBN(总碱数)为至少10mg KOH/g(按ASTM D 2896)。
按照本发明现在已经令人惊奇地发现，本发明的润滑组合物表现出按DIN51392和Komatsu Hot Tube Test(Komatsu热管法)确定的改进的沉积物形成控制性能。
对在本发明的润滑组合物中应用的基油没有特别限制，和可以方便地使用各种常规的矿物油、合成油和天然衍生的酯如植物油。
在本发明中应用的基油可以方便地包括一种或多种矿物油和/或一种或多种合成油的混合物；因此，按照本发明，术语″基油″可以指含多种基油的混合物。矿物油包括液态石油和链烷、环烷或混合链烷/环烷类型的溶剂处理或酸处理的矿物润滑油，其可以通过加氢精制过程和/或脱蜡进一步精制。
在本发明的润滑组合物中应用的合适基油为第I-III类矿物基油、第IV类聚α-烯烃(PAO)、第I-III类费-托衍生基油和它们的混合物。
在本发明中，″第I类″、″第II类″、″第III类″和″第IV类″基油指按照美国石油组织(API)的第I-IV类定义的润滑油基油。这些API分类在API出版物1509，第15版，附录E，2002年4月中进行了定义。
费-托衍生基油在现有技术中是已知的。术语″费-托衍生″指基油是或衍生自费-托法的合成产品。费-托衍生基油也可以称为GTL(气至液)基油。可以方便地用作本发明润滑组合物的基油的合适费-托衍生基油为例如在EP0776959、EP0668342、WO97/21788、WO00/15736、WO00/14188、WO00/14187、WO00/14183、WO00/14179、WO00/08115、WO99/41332、EP1029029、WO01/18156和WO01/57166中公开的那些。
合成油包括烃油如烯烃低聚物(包括聚α-基油；PAO)、二元酸酯、多元醇酯、聚亚烷基二醇(PAG)、烷基萘和脱蜡的蜡质异构体。可以方便地应用由Shell Group以名称″Shell XHVI″(商标)出售的合成烃基油。
聚α-烯烃基油(PAO)和它们的制备在本领域中是公知的。可在本发明润滑组合物中应用的优选聚α-烯烃基油可以衍生自直链C2-C32、优选C6-C16α-烯烃。对于聚α-烯烃来说特别优选的原料为1-辛烯、1-癸烯、1-十二碳烯和1-十四碳烯。
以润滑组合物的总重量计，在本发明润滑组合物中结合的基油的总量优选为60-99wt％，更优选为65-98wt％，和最优选为70-95wt％。
按照本发明的优选实施方案，所述基油以基油的总量计包含至少50wt％的第II类基油，优选为至少60wt％，更优选为至少70wt％。
对于在本发明的润滑组合物中应用的清净剂没有特别限制(只要符合权利要求1的要求即可)，和可以方便地应用各种常规清净剂。术语“清净剂”可以指单个清净剂，也可以指含两种或更多种不同清净剂的混合物。可以应用的清净剂的实例包括油溶性的中性和过碱性磺酸盐、酚盐、硫化酚盐、硫代膦酸盐、水杨酸盐和环烷酸盐以及其它油溶性的金属羧酸盐，所述金属特别是碱金属或碱土金属，如钠、钾、锂和特别是钙和镁。优选的金属清净剂是中性的和TBN(总碱数，按ASTM D 2896)为至多450mg KOH/g的过碱性清净剂。可以使用清净剂的组合物，所述清净剂可以是过碱性清净剂或中性清净剂或两者均有。
正如前面所提到的，在本发明的组合物中，所述清净剂按清净剂的总量计包含至少30mol％BN(碱数)为0.1-80mg KOH/g的磺酸盐清净剂。这种具有相对低BN的磺酸盐清净剂在本领域中是公知的。例如，WO96/26919公开了低BN磺酸钙及其制备。
按照本发明的优选实施方案，所述清净剂包含至少35mol％的磺酸盐清净剂，优选为至少40mol％，更优选为至少45mol％，甚至更优选为至少50mol％，最优选至少55mol％。另外优选的是所述磺酸盐清净剂具有至多50mg KOH/g、更优选至多40mg KOH/g的BN。
正如前面所提到的，在本发明的组合物中，所述清净剂以清净剂的总量计包含30-70mol％的酚盐清净剂。所述清净剂优选包含至少35mol％的酚盐清净剂；所述清净剂优选包含至多65mol％的酚盐清净剂，更优选为至多60mol％，甚至更优选为至多55mol％，仍更优选为至多50mol％，最优选为至多45mol％的酚盐清净剂。另外优选的是所述酚盐清净剂为过碱性清净剂，其BN为至少190mg KOH/g，优选为至少200，更优选为至少220，最优选为至少240mg KOH/g。这种清净剂在本领域中是公知的。
以润滑组合物的总重量计，在本发明的组合物中清净剂的总量通常为至多35.0wt％。以组合物的总重量计，本发明的组合物包含至少4wt％、优选至少8wt％、更优选至少12wt％的清净剂。
本发明的润滑组合物还可以包含一种或多种其它添加剂，如抗氧化剂、耐磨剂、分散剂、其它清净剂、极压添加剂、其它摩擦调节剂、粘度调节剂、降倾点剂、金属钝化剂、防腐剂、破乳剂、消泡剂、密封相容剂和添加剂稀释剂基油等。优选地，除清净剂外，在本发明的组合物中还至少存在分散剂；更优选地，至少存在分散剂和耐磨剂。
以润滑组合物的总重量计，上述添加剂的存在量通常为0.01-35.0wt％，优选为0.5-30.0wt％。更优选地，本发明的润滑组合物包含小于5.0wt％的不同于一种或多种清净剂的任意其它添加剂。优选地，所述组合物不含除一种或多种清净剂、一种或多种分散剂和一种或多种耐磨剂以外的其它添加剂。
由于本领域熟练技术人员熟悉上述和其它添加剂，因此这里不再详细讨论。这些添加剂的具体实例在例如Kirk-Othmer的Encyclopedia of Chemical Technology，第三版，第14卷，477-526页中有述。
优选地，所述组合物的总碱数(TBN)值优选为至多75mg KOH/g，优选为至多70mg KOH/g，更优选为至多65mg KOH/g，甚至更优选为至多60mg KOH/g(具体按ASTM D 2896测量)。所述组合物的总碱数(TBN)值(按ASTM D 2896)为至少10mg KOH/g。
另外，优选的是所述组合物在100℃下的运动粘度(按ASTM D 445)大于5.6mm2/s和小于21.9mm2/s，优选大于12.5mm2/s，更优选大于16.3mm2/s。
本发明的润滑组合物可以方便地通过混合一种或多种添加剂和基油来制备。
在另一个方面，本发明提供本发明润滑组合物改进沉积物形成控制性能(具体按DIN51392测量)的用途。
本发明的润滑组合物通常用于润滑设备，但特别用作用于内燃机的发动机油。这些发动机油包括客车发动机、柴油发动机、船用柴油机、燃气发动机、双循环和四循环发动机等，和特别是船用柴油机。
下面参考如下实施例描述本发明，所述实施例不以任何方式限制本发明的范围。
实施例
润滑油组合物
配制在船用柴油机中用作船用汽缸油的各种润滑组合物。
表1列出了所测试的配方的组成和性能；组分含量基于完全配制的配方总重量计以wt％表示。
所有测试的船用柴油机油配方均按SAE 50配方配制，这些配方满足所谓的SAE J 300规格(2009年1月修订，SAE代表汽车工程师协会)。所有测试的配方在100℃下的运动粘度(按ASTM D 445)均大于16.3mm2/s和小于21.9mm2/s。
所有测试的船用汽缸油配方均包含基油、清净剂组合物和分散剂的组合。
″基油1″为第I类基油与光亮油的共混物，其由Shell ChemicalsLtd.(London，UK)以商品名“Catenex”商购得到。
″基油2″为包含增稠剂和75wt％第I I类基油的基油共混物；这种共混物由例如Chevron Products Company(San Ramon，CA，USA)以商品名“Chevron 600R”商购得到。
″清净剂1″为TBN为417mg KOH/g(按ASTM D 2896)和皂含量为236mM Ca2+的过碱性磺酸盐清净剂，其由Chevron Oronite(Windsor，UK)以商品名“OLOA 249SX”商购得到。
″清净剂2″为TBN为375mg KOH/g和皂含量为317mM Ca2+的过碱性磺酸盐清净剂，其由JinZhou KangTai Lubricant Additives Co.Ltd.(Liaoning，China)以商品名“T106”商购得到。
″清净剂3″为TBN为246mg KOH/g和皂含量为397mM Ca2+的过碱性酚盐清净剂，其由Lubrizol(Wickliffe，Ohio，USA)以商品名“Lubrizol 6499”商购得到。
″清净剂4″为TBN为250mg KOH/g和皂含量为282mM Ca2+的过碱性酚盐清净剂，其由Chevron Oronite以商品名“OLOA 219C”商购得到。
″清净剂5″为TBN为16mg KOH/g和皂含量为410mM Ca2+的低BN磺酸盐清净剂，其由Chevron Oronite以商品名“OLOA 246S”商购得到。
″清净剂6″为TBN为34mg KOH/g和皂含量为395mM Ca2+的低BN磺酸盐清净剂，其由Chemtura Corporat ion(Middlebury，USA)以商品名“LOBASE C-4503”商购得到。
″清净剂7″为TBN为9mg KOH/g和皂含量为441mM Ca2+的过碱性磺酸盐清净剂，其由Chemtura Corporat ion以商品名“LOBASEC-4506”商购得到。
“分散剂”为高MW的聚异丁烯琥珀酰亚胺，其由Afton ChemicalCorporation(Richmond，VA，USA)以商品名“HiTEC”商购得到。
实施例1-10和对比例1-2的组合物通过应用传统润滑剂混合程序混合基油与清净剂、分散剂获得。
应用表1中所指出的如下方法：
1TBN值按ASTM D 2896确定；
2各清净剂的清净剂含量(或“皂含量”)在经历V.A.Zakupra和S.V.Timoshenko(All-Union Scientific-Research and DesignInstitute of the Petroleum Refining and PetrochemicalIndustry(VNIIPKnef tekhim)，USSR)的文章“Separation of lube oildetergent additives on silica gel”，in Khimiya i TekhnologiyaTopliv i Masel，No.2，pp.48-52，February，1980中描述的分离程序后，应用清净剂的皂分率的TAN测量(按ASTM D 664)确定。所测定的皂含量值用每kg清净剂添加剂的当量毫摩尔Ca2+表示(参见上面针对清净剂1-7确定的皂含量)。每种清净剂类型(例如低BN磺酸盐)的清净剂(摩尔)含量通过整个配方中各清净剂添加剂的贡献(wt％)乘以各清净剂含量后进行加和获得。
3清净剂的比例通过计算(每种清净剂组分除以总数)确定，并以mol％表示。在实施例中，酚盐比例与磺酸盐比例的和为100％；低BN磺酸盐(即BN为0.1-80mg KOH/g、优选为0.1-50mg KOH/g的磺酸盐)的比例为磺酸盐比例的一部分。
4标称沉积物基于按DIN 51392测试之后的总沉积物值计。以对比例3作参比时，已经表明标称沉积物(而不是总沉积物)更好地反映了相对值。
Figure BDA0000157406990000091
Wolf Strip测试
为了验证本发明的沉积物形成控制性能，按DIN 51392应用WolfStrip测试程序(测试持续时间12小时，盘温度为280℃)进行测量。在测试中，应用如下测试条件：在闭路循环中应用150ml的油流量；测试过程中将油以薄膜形式在280℃下以50(±5)ml/h的流量在可移动测试带上泵送12小时，其中所述带相对水平方向的倾角为8°。
测量得到的标称沉积物在上表1中列出，结果表示与具有最高总沉积物量的实施例(即对比例3)相比的相对量。
Komatsu热管测试
在验证本发明的沉积物形成控制性能的替代测试中，按照在Swiss Testing procedure No.STS Nr.452中解释的视觉评级应用Komatsu热管测试程序进行测量。Komatsu热管测试评价润滑剂的高温稳定性。在加热的细玻璃毛细管内部的空气向上推起油滴，和通过玻璃管上漆膜形成程度来测量润滑剂的薄膜氧化稳定性，管子的最终颜色按0-10的标尺评级。评级0指很重的沉积物形成，而评级10指在测试结束仍为干净的玻璃管。该方法在SAE论文840262中也有描述。在管中漆膜的形成水平反映了油的高温稳定性及其在使用期间在发动机的高温区域内形成沉积物的倾向。测量得到的评级(在290和320℃下)在下表2中给出。
表2
 实施例2  实施例3  实施例5  实施例6  对比例1
  290℃   9.5   9.5   9.5   9.5   8.5
  320℃   5.0   5.0   8.5   8.5   堵塞
讨论
从表1可以看出，当与对比例1-2相比时，本发明组合物的沉积物形成控制性能明显提高。
从实施例1-10的沉积物形成控制性能的比较可以看出，按照本发明，优选其中至少40mol％的清净剂为低BN磺酸盐清净剂(即BN数为0.1-80，优选低于50mg KOH/g)和同时大于35mol％的清净剂总量为酚盐清净剂(实施例1-7)的实施方案。另外，实施例5和6特别优选，因为它们具有更小的沉积物量。另外，优选的是基油包含至少50wt％的第II类基油。
本发明的理想沉积物形成控制性能在Komatsu热管测试中得到了确认(参见表2)。实施例2、3、5和6在290℃下得到了极好的评级(在总评级10中为9.5)，在320℃下仍有可接受(实施例2和3为5.0)至良好(实施例5和6为8.5)的值，而对比例1在320℃下没有通过测试(堵塞)。

Claims (10)

1.一种润滑组合物，所述润滑组合物包含：
基油；和
清净剂；
其中所述清净剂以清净剂总量计包含至少30mol％BN(碱数)为0.1-80mg KOH/g的磺酸盐清净剂；
其中所述清净剂以清净剂总量计包含30-70mol％的酚盐清净剂；
其中所述润滑组合物以润滑组合物总重量计包含至少4wt％的清净剂；和
其中所述润滑组合物的TBN(总碱数)为至少10mg KOH/g(按ASTMD 2896)。
2.权利要求1的润滑组合物，其中所述清净剂包含至少35mol％的磺酸盐清净剂，优选为至少40mol％，更优选为至少45mol％，最优选为至少50mol％。
3.权利要求1或2的润滑组合物，其中所述磺酸盐清净剂具有至多50mg KOH/g的BN。
4.权利要求1-3任一项的润滑组合物，其中所述清净剂包含至少35mol％的酚盐清净剂。
5.权利要求1-4任一项的润滑组合物，其中所述酚盐清净剂为BN为至少190mg KOH/g、优选至少200、更优选至少220、最优选至少240mg KOH/g的过碱性清净剂。
6.权利要求1-5任一项的润滑组合物，其中所述组合物以组合物的总重量计包含至少8wt％、优选为至少12wt％的清净剂。
7.权利要求1-6任一项的润滑组合物，其中所述组合物的TBN(总碱数)值为至多75mg KOH/g，优选为至多70mg KOH/g，更优选为至多60mg KOH/g。
8.权利要求1-7任一项的润滑组合物，其中所述基油以基油总量计包含至少50wt％的第II类基油，优选为至少60wt％，更优选为至少70wt％。
9.权利要求1-8任一项的润滑组合物，其中所述组合物为船用柴油机油。
10.权利要求1-9任一项的润滑组合物改进沉积物形成控制性能的用途。
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