CN102575183A - 含有抗磨剂的润滑组合物 - Google Patents
含有抗磨剂的润滑组合物 Download PDFInfo
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- CN102575183A CN102575183A CN201080046467XA CN201080046467A CN102575183A CN 102575183 A CN102575183 A CN 102575183A CN 201080046467X A CN201080046467X A CN 201080046467XA CN 201080046467 A CN201080046467 A CN 201080046467A CN 102575183 A CN102575183 A CN 102575183A
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Abstract
本发明提供一种润滑内燃机的铝合金表面的方法，其包括向铝合金表面提供包含具有润滑粘度的油和碱金属或碱土金属酚盐清净剂的润滑组合物。本发明公开的酚盐可在铝合金表面上进一步提供抗磨性能。
Description
发明领域
本发明提供一种润滑内燃机的铝合金表面的方法，其包括向铝合金表面提供包含具有润滑粘度的油和碱金属或碱土金属酚盐清净剂的润滑组合物。本文公开的酚盐可在铝合金表面上进一步提供抗磨性能。
发明背景
熟知润滑油含有用于保护内燃机以防腐蚀、磨损、烟灰沉积和酸建立的大量表面活性添加剂(包括抗磨剂、分散剂或清净剂)。通常，这类表面活性剂可能对发动机组件磨损(铁和铝基组件中)、轴承腐蚀或燃料经济性具有有害影响。用于发动机润滑油的常用抗磨添加剂为二烷基二硫代磷酸锌(ZDDP)。认为ZDDP抗磨添加剂通过在金属表面上形成保护膜而保护发动机。ZDDP还可对燃料经济性和效率和铜腐蚀具有有害影响。因此，发动机润滑剂还可含有摩擦改进剂以避免ZDDP对燃料经济性的有害影响以及腐蚀抑制剂以避免ZDDP对铜腐蚀的有害影响。其它添加剂也可提高铅腐蚀。
发动机设计的发展导致使用含亚铁和/或非铁组件的发动机。通常其非铁发动机组件基于铝合金、硅酸盐、氧化物或其它陶瓷材料。认为抗磨添加剂如ZDDP在铝合金基发动机中产生与铁基发动机相比更差的发动机磨损性能。
另外，含有磷化合物和硫的发动机润滑剂已显示出部分贡献于颗粒物排放和其它污染物排放。另外，硫和磷倾向于毒害催化转化器中所用的催化剂，导致所述催化剂的性能降低。
润滑具有铝表面的发动机组件的尝试已描述于EP1624044A1(2006年2月8日由Oldfield提交)和国际公开WO2008/144701(2008年5月15日由Davies等人提交)中。
EP624044A1公开了用含有有效减摩量的油溶性三核有机钼化合物的润滑组合物润滑铝合金表面的方法。
WO2008/144701公开了通过向铝合金表面提供包含具有润滑粘度的油和无灰抗磨剂的润滑组合物而润滑铝合金表面。此处公开的实例还需要1.5重量％的清净剂。然而，没有关于所用清净剂类型的具体公开内容。
发明概述
在一个实施方案中，本发明提供润滑内燃机的铝合金表面的方法，其包括向铝合金表面提供包含具有润滑粘度的油和碱金属或碱土金属(包括锂、钠、钙、镁或钡)酚盐清净剂的润滑组合物。在一个实施方案中，酚盐清净剂可以为硫化苯酚钙，特别是过碱性硫化苯酚钙。
在一个实施方案中，本发明提供润滑内燃机的铝合金表面的方法，其包括向铝合金表面提供包含(a)具有润滑粘度的油、(b)TBN为200-400(或200-350)的过碱性碱金属或碱土金属(包括锂、钠、钙、镁或钡，通常为钙)酚盐(通常为硫化酚盐)清净剂和(c)TBN为20-170(例如155)的中性酚盐(通常为不含硫的苯酚钙)的润滑组合物。不含硫的苯酚钙可包括欧洲专利申请EP1680491A或EP1778824A所述的清净剂。
在一个实施方案中，本发明提供润滑内燃机的铝合金表面的方法，其包括向铝合金表面提供包含具有润滑粘度的油和碱金属或碱土金属酚盐清净剂(通常为硫化苯酚钙)的润滑组合物。
在一个实施方案中，本发明提供控制内燃机中铝合金表面的磨损的方法，其包括向铝合金表面提供包含具有润滑粘度的油和碱金属或碱土金属酚盐清净剂(通常为硫化苯酚钙)的润滑组合物。
在一个实施方案中，本发明提供本文公开的润滑组合物减轻内燃机的铝合金表面上的磨损的用途。在一个实施方案中，本发明提供碱金属或碱土金属酚盐清净剂(通常为硫化苯酚钙)作为抗磨剂用于内燃机的铝合金表面的用途。
在一个实施方案中，本发明提供如本文所公开的润滑内燃机的方法，其中铝合金为共晶或过共晶铝合金(例如衍生自硅酸铝、氧化铝或其它陶瓷材料的那些)。
在一个实施方案中，本发明提供如本文所公开的润滑内燃机的方法，其中内燃机具有部分或所有由铝合金或铝复合物组成的气缸腔、气缸柱或活塞环。
发明详述
本发明提供如上所述润滑组合物和润滑发动机的方法。
酚盐清净剂
碱金属或碱土金属酚盐清净剂可描述为过碱性材料。过碱性材料也称为过碱性或超碱性盐，一般为单相、均匀牛顿体系，其特征为超过根据金属和与金属反应的具体酸性有机化合物的化学计量中和所需的过量金属的量。过量金属的量通常根据基质与金属比表述。术语“基质与金属比”，或者表述为金属与基质比，或简单地“金属比”为金属总当量与基质当量之比。术语金属比的更详细描述在“Chemistry and Technology ofLubricants”，第2版，由R.M.Mortier和S.T.Orszulik编辑，第85和86页，1997中提供。
过碱性碱金属或碱土金属酚盐清净剂可具有0.8-10，或1-10，或3-9，或4-8，或5-7的金属比。
在不同的实施方案中，碱金属或碱土金属酚盐清净剂可具有50-400，或200-350，或220-300的总碱值(TBN)。在一个实施方案中，碱金属或碱土金属酚盐清净剂可具有约255的TBN。碱金属或碱土金属酚盐清净剂的更详细描述例如描述于美国专利6,551,965或欧洲专利申请EP1903093A和EP0601721A中。
碱金属或碱土金属酚盐清净剂添加剂可衍生自烃基取代的苯酚，其中烃基取代的苯酚可以以酚盐清净剂的10-70重量％，或25-65重量％，或30-60重量％存在。当将添加剂加入润滑剂中，总百分数由于所有基油的稀释效果和总润滑组合物中其它添加剂的存在而降低。
碱金属或碱土金属酚盐清净剂可衍生自烃基取代的苯酚，其中碱土金属酚盐清净剂将0.75-2重量％，或0.9-1.75重量％，或1-1.5重量％的烃基取代的苯酚输送至润滑组合物中。通过碱金属或碱土金属酚盐清净剂输送的烃基取代的苯酚含量(这包括苯酚及其阴离子)可以为润滑组合物的0.75-2重量％，或0.9-1.75重量％，或1-1.5重量％。
碱金属或碱土金属酚盐清净剂烃基取代的苯酚含量和硫酸盐灰可变化。在一个实施方案中，通过酚盐输送的烃基取代的苯酚含量可以为润滑组合物的0.9-1.75重量％；且硫酸盐灰含量可以为至少0.4-1.3重量％。在一个实施方案中，通过酚盐输送的烃基取代的苯酚含量可以为润滑组合物的0.9-1.75重量％；且硫酸盐灰含量可以为至少0.4-1.2重量％。在一个实施方案中，通过酚盐输送的烃基取代的苯酚含量可以为1重量％或更高至1.5重量％；且硫酸盐灰含量可以为润滑组合物的至少0.6-1.1重量％。
烃基取代的苯酚的各个烃基可含有平均6个或更多，8个或更多，或10个或更多碳原子。每烃基的最大碳原子数可以为至多300，或至多100，或至多70，或至多50，或至多20。在一个实施方案中，各个烃基可含有8-20，或10-12个碳原子(通常各个烃基可以为十二烷基)。
通过过碱性碱金属或碱土金属酚盐清净剂输送的硫酸盐灰的量可以为润滑组合物的0.4-1.2重量％，或0.6-1.1重量％。
用于内燃机的润滑剂组合物可适于任何发动机润滑剂而不管硫、磷或硫酸盐灰(ASTM D-874)含量。机油润滑剂的硫含量可以为1重量％或更少，或0.8重量％或更少，或0.5重量％或更少，或0.3重量％或更少。在一个实施方案中，硫含量可以为0.001-0.5重量％，或0.01-0.3重量％。
磷含量可以为0.2重量％或更少，或0.12重量％或更少，或0.1重量％或更少，或0.085重量％或更少，或0.08重量％或更少，或甚至0.06重量％或更少，0.055重量％或更少，或0.05重量％或更少。在一个实施方案中，磷含量可以为100-1000ppm，或200-600ppm。
润滑组合物的硫酸盐灰含量可以为润滑组合物的至少0.3重量％，或至少0.4重量％，至少0.6至2重量％，或1.5重量％，或1.3重量％，或1.1重量％。在不同的实施方案中，硫酸盐灰含量可以为润滑组合物的0.3-2重量％，或0.4-1.5重量％，或0.6-1.3重量％，或0.6-1.1重量％。
在一个实施方案中，润滑组合物可表征为具有(i)0.5重量％或更少的硫含量，(ii)0.06重量％或更少的磷含量，和(iii)1.3重量％或更少的硫酸盐灰含量。
具有润滑粘度的油
润滑组合物包含具有润滑粘度的油。这类油包括天然和合成油，衍生自加氢裂化、氢化和加氢精制的油，未精炼、精炼和再精炼油或其混合物。未精炼、精炼和再精炼油的更详细描述在国际公开WO2008/147704，第[0054]-[0056]段中提供。天然和合成润滑油的更详细描述分别描述于WO2008/147704第[0058]-[0059]段中。合成油还可通过费托反应制备，通常可以为加氢异构的费托法合成的烃或蜡。在一个实施方案中，油可通过费托法气-至-液合成油合成程序制备以及其它气-至-液油。
具有润滑粘度的油也可如“Appendix E-API Base OilInterchangeability Guidelines for Passenger Car Motor Oils and DieselEngine Oils”的2008年4月版本，第1.3部分，小标题1.3.“Base StockCatagories”所述定义。在一个实施方案中，具有润滑粘度的油可以为API组I、或组II或组III或组IV油。在一个实施方案中，具有润滑粘度的油可以为API组II或组III油。
存在的具有润滑粘度的油的量通常为在从100重量％中减去本发明化合物和其它性能添加剂的量之和以后的余数。
润滑组合物可以为浓缩物和/或完全配制润滑剂的形式。如果本发明润滑组合物(包含本文所公开的添加剂)为浓缩物的形式(其可与其它油组合形成全部或部分最终润滑剂)，则这些添加剂与具有润滑粘度的油和/或与稀释油之比为1∶99-99∶1重量，或80∶20-10∶90重量。
其它性能添加剂
组合物任选包含其它性能添加剂。其它性能添加剂包括以下物质中的至少一种：金属减活剂、粘度改进剂、清净剂(除先前作为本发明的一部分描述的酚盐外)、摩擦改进剂、抗磨剂、腐蚀抑制剂、分散剂、分散剂粘度改进剂、特压剂、抗氧化剂、抑泡剂、反乳化剂、倾点下降剂、密封溶胀剂及其混合物。通常，完全配制润滑油含有这些性能添加剂中的一种或多种。
在一个实施方案中，润滑组合物进一步包含其它添加剂。在一个实施方案中，本发明提供进一步包含分散剂、抗磨剂、分散剂粘度改进剂、摩擦改进剂、粘度改进剂、抗氧化剂、清净剂(除先前作为本发明的一部分描述的酚盐外)中至少一种或其混合物的润滑组合物。
本发明分散剂可以为琥珀酰亚胺分散剂或其混合物。在一个实施方案中，分散剂可作为单一分散剂存在。在一个实施方案中，分散剂可作为两种或三种不同分散剂的混合物存在，其中至少一种可以为琥珀酰亚胺分散剂。
琥珀酰亚胺分散剂可衍生自脂族多胺或其混合物。脂族多胺可以为脂族多胺如亚乙基多胺、亚丙基多胺、亚丁基多胺或其混合物。在一个实施方案中，脂族多胺可以为亚乙基多胺。在一个实施方案中，脂族多胺可选自乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺、多胺釜残及其混合物。
分散剂可以为N-取代的长链链烯基琥珀酰亚胺。N-取代的长链链烯基琥珀酰亚胺的实例包括聚异丁烯琥珀酰亚胺。通常衍生出聚异丁烯琥珀酸酐的聚异丁烯具有350-5000，或550-3000或750-2500的数均分子量。琥珀酰亚胺分散剂和它们的制备方法例如公开于美国专利3,172,892、3,219,666、3,316,177、3,340,281、3,351,552、3,381,022、3,433,744、3,444,170、3,467,668、3,501,405、3,542,680、3,576,743、3,632,511、4,234,435、Re26,433和6,165,235、7,238,650及美国专利申请0355895A中。
也可将分散剂通过常规方法通过与任何多种试剂反应而后处理。其中，这些为硼化合物、脲、硫脲、二巯基噻二唑、二硫化碳、醛、酮、羧酸、烃取代的琥珀酸酐、马来酸酐、腈、环氧化物和磷化合物。
分散剂可以以润滑组合物的0.01-20重量％，或0.1-15重量％，或0.1-10重量％，或1-6重量％存在。
在一个实施方案中，本发明润滑组合物进一步包含分散剂粘度改进剂。分散剂粘度改进剂可以以润滑组合物的0-5重量％，或0-4重量％，或0.05-2重量％存在。
分散剂粘度改进剂可包括官能化聚烯烃，例如已用酰化剂如马来酸酐和胺官能化的乙烯-丙烯共聚物；用胺官能化的聚甲基丙烯酸酯，或与胺反应的苯乙烯-马来酸酐共聚物。分散剂粘度改进剂的更详细描述公开于国际公开WO2006/015130或美国专利4,863,623；6,107,257；6,107,258和6,117,825中。在一个实施方案中，分散剂粘度改进剂可包括美国专利4,863,623(参见第2栏第15行至第3栏第52行)或国际公开WO2006/015130(参见第2页第[0008]段)和第[0065]-[0073]段所述的制备实施例)中所述那些。
如本文所用术语“脂肪”具有至少6或至少8-30或20个碳原子。
在一个实施方案中，摩擦改进剂可选自胺的脂肪酸衍生物、脂肪酯，或脂肪环氧化物；脂肪咪唑啉；烷基磷酸的胺盐。摩擦改进剂可以以润滑组合物的0-6重量％，或0.05-4重量％，或0.1-2重量％存在。
在一个实施方案中，本发明提供进一步包含二烷基二硫代磷酸锌或其混合物的润滑组合物。二烷基二硫代磷酸锌是本领域中已知的。二烷基二硫代磷酸锌可以以润滑组合物的0-5重量％，或0.1-3重量％，或0.5-2重量％存在。
在一个实施方案中，本发明提供进一步包含钼化合物的润滑组合物。钼化合物可选自二烷基二硫代磷酸钼、二硫代氨基甲酸钼、钼化合物的胺盐及其混合物。钼化合物可提供具有0-1000ppm，或5-1000ppm，或10-750ppm、5-300ppm或20-250ppm钼的润滑组合物。
在一个实施方案中，本发明提供除先前作为本发明的一部分描述的酚盐外，进一步包含中性或过碱性清净剂的润滑组合物。中性或过碱性清净剂可选自磺酸盐、salixarate、水杨酸盐、水杨苷及其混合物。通常中性或过碱性清净剂可以为钠、钙或镁的磺酸盐、salixarate和水杨酸盐。
中性清净剂可具有小于200，或通常小于170的TBN。例如，“中性”或“轻微过碱性”磺酸盐清净剂可具有0-100或20-100(例如80或85)的TBN。润滑组合物可含有0-5重量％或0.5-3重量％的TBN为80或85的中性磺酸盐清净剂(通常为磺酸钙)。润滑组合物可含有0-3重量％，或0.5-2重量％的TBN为155的苯酚钙清净剂。(中性酚盐清净剂，即非过碱性，通常仍显示出可测量的TBN。)
过碱性酚盐和水杨酸盐通常具有200-450TBN的总碱值。过碱性磺酸盐通常具有250-600，或300-500(通常为300或400)的总碱值。过碱性清净剂是本领域中已知的。在一个实施方案中，磺酸盐清净剂可以为TBN为400的具有至少8至40的金属比的主要线性烷基苯磺酸盐清净剂，如美国专利申请2005065045(以及授予US7,407,919)的第[0026]-[0037]段所述。主要线性烷基苯磺酸盐清净剂可特别用于帮助改进燃料经济性。除所要求保护的酚盐外，可以存在的中性和过碱性清净剂的总量为润滑组合物的0-15重量％，或0.1-10重量％，或0.2-8重量％(包括已知通常与清净剂联合的稀释油的量。这可例如为提出的范围的30-50重量％)。
在一个实施方案中，润滑组合物包含抗氧化剂或其混合物。抗氧化剂可以以润滑组合物的0-15重量％，或0.1-10重量％，或0.5-5重量％存在。
抗氧化剂包括硫化烯烃、烷基化二苯胺(通常为二壬基二苯胺、辛基二苯胺、二辛基二苯胺)、受阻酚、钼化合物(例如二硫代氨基甲酸钼)，或其混合物。
受阻酚抗氧化剂通常含有仲丁基和/或叔丁基作为位阻基团。酚基可以进一步被烃基(通常为线性或支化烷基)和/或连接在第二个芳基上的桥联基团取代。合适的受阻酚抗氧化剂的实例包括2，6-二叔丁基苯酚、4-甲基-2，6-二叔丁基苯酚、4-乙基-2，6-二叔丁基苯酚、4-丙基-2，6-二叔丁基苯酚或4-丁基-2，6-二叔丁基苯酚或4-十二烷基-2，6-二叔丁基苯酚。在一个实施方案中，受阻酚抗氧化剂可以为酯，可包括例如来自Ciba的IrganoxTM L-135。合适的含酯受阻酚抗氧化剂化学的更详细描述在美国专利6,559,105中找到。
合适摩擦改进剂的实例包括胺的脂肪酸衍生物、脂肪酯或脂肪环氧化物；脂肪咪唑啉，例如羧酸与聚亚烷基-多胺的缩合产物；烷基磷酸的胺盐；酒石酸脂肪烷基酯；脂肪烷基酒石酰亚胺；或脂肪二烷基酒石酰胺。
摩擦改进剂还可包括材料如硫化脂肪化合物和烯烃、二烷基二硫代磷酸钼、二硫代氨基甲酸钼、向日葵油或多元醇与脂族羧酸的单酯。
在一个实施方案中，摩擦改进剂可选自胺的脂肪酸衍生物、脂肪酯或脂肪环氧化物；酒石酸脂肪烷基酯；脂肪烷基酒石酰亚胺；和脂肪烷基酒石酰胺。酒石酸脂肪烷基酯；脂肪烷基酒石酰亚胺；脂肪烷基酒石酰胺可以与上述羟基-羧酸的酰胺、酯或酰亚胺衍生物相同或不同。
在一个实施方案中，摩擦改进剂可以为脂肪酸酯。在另一实施方案中，脂肪酸酯可以为单酯，在另一实施方案中，脂肪酸酯可以为(三)甘油酯。
其它性能添加剂如腐蚀抑制剂包括作为WO2006/047486出版的美国申请US05/038319第5-8段中所述那些、辛胺辛酸盐，或十二碳烯基琥珀酸或酐和脂肪酸如油酸与多胺的缩合产物。在一个实施方案中，腐蚀抑制剂包括腐蚀抑制剂。
腐蚀抑制剂可以为氧化丙烯的均聚物或共聚物。
腐蚀抑制剂更详细地描述于Dow ChemicalCompany出版的产品手册Form No.118-01453-0702AMS中。该产品手册标题为“SYNALOX Lubricants，High-Performance Polyglycols forDemanding Applications”。
可使用金属减活剂，包括苯并三唑(通常为甲苯基三唑)的衍生物、二巯基噻二唑衍生物、1，2，4-三唑、苯并咪唑、2-烷基二硫代苯并咪唑或2-烷基二硫代苯并噻唑；抑泡剂，包括丙烯酸乙酯和丙烯酸2-乙基己酯和任选乙酸乙烯酯的共聚物；反乳化剂，包括磷酸三烷基酯、聚乙二醇、聚氧化乙烯、聚氧化丙烯和(氧化乙烯-氧化丙烯)聚合物；倾点下降剂，包括马来酸酐-苯乙烯的酯、聚甲基丙烯酸酯、聚丙烯酸酯或聚丙烯酰胺。可用于本发明组合物中的抑泡剂包括丙烯酸乙酯和丙烯酸2-乙基己酯和任选乙酸乙烯酯的共聚物；反乳化剂，包括磷酸三烷基酯、聚乙二醇、聚氧化乙烯、聚氧化丙烯和(氧化乙烯-氧化丙烯)聚合物。
可用于本发明组合物中的倾点下降剂包括聚α烯烃、马来酸酐-苯乙烯的酯、聚(甲基)丙烯酸酯、聚丙烯酸酯或聚丙烯酰胺。
在不同的实施方案中，润滑组合物可具有除本发明清净剂外，进一步含有如下表所述范围的添加剂的组成：
脚注：
以上所述范围以无油计算，即稀释油除外的活性物质的量。
工业应用
润滑组合物可用于内燃机中。内燃机可具有或可不具有废气再循环系统。内燃机可安装有排放净化系统或涡轮增压器。排放净化系统包括柴油机排气烟尘过滤器(DPF)，或使用选择性催化还原(SCR)的系统。
在一个实施方案中，内燃机可以为柴油机(通常为重型柴油机)、汽油机、天然气发动机或混合汽油/醇发动机。在一个实施方案中，内燃机可以为柴油机，在另一实施方案中为汽油机。
内燃机可以为2冲程或4冲程发动机。合适的内燃机包括船用柴油机、航空用活塞式发动机、低负荷柴油机及汽车和卡车发动机。
以下实施例提供对于本发明的阐述。这些实施例不是穷举的，且不意欲限制本发明的范围。
实施例
对比润滑剂实施例1-5(CE1-CE5)通过将琥珀酰亚胺分散剂(8.3重量％的琥珀酰亚胺分散剂总量，包括40重量％稀释油)混合物、3重量％的以
5777市售的分散剂粘度改进剂(包括稀释油)、4重量％的抗氧化剂混合物(包括胺和酚类抗氧化剂)和1.2重量％的甘油单油酸酯摩擦改进剂混合而制备。另外，CE1-CE5含有如下表所述的过碱性清净剂。还包括表示硫酸盐灰含量和总碱值(TBN mg KOH/g)的各润滑剂的表征数据。
脚注：
所述各清净剂的量包括稀释油的常规量(通常为30-50重量％)。
然后在使用钢球(即球组成包含铁)的四球磨损试验中评估各润滑剂。程序与Institute of Petroleum Method IP239所述的相同。所得结果如下：
| 润滑剂 | 清净剂类型 | 四球磨痕(μm)(钢) |
| CE1 | 钙salixarate | 433 |
| CE2 | 水杨酸钙 | 483 |
| CE3 | 水杨苷镁 | 482 |
| CE4 | 磺酸钙 | 511 |
| CE5 | 硫化苯酚钙 | 603 |
结果表明在钢上，硫化苯酚钙在控制磨损方面最小有效。关于硫化苯酚钙所得的磨痕比关于磺酸钙所得的高18％。
对比润滑剂实施例6-7(CE6-CE7)通过将琥珀酰亚胺分散剂(7.9重量％的琥珀酰亚胺分散剂总量，包括40重量％稀释油)混合物、抗氧化剂混合物(包括胺和酚类抗氧化剂)和0.57重量％二烷基二硫代磷酸锌混合而制备。CE6和CE7分别含有2重量％(包括稀释油)和2.7重量％(包括稀释油)的过碱性磺酸钙。
本发明润滑剂实施例1和2(EX1和EX2)类似于CE6和CE7，不同之处在于代替过碱性磺酸钙，EX1分别含有1.9重量％(包括39重量％稀释油)和2.75重量％(包括39重量％稀释油)的过碱性硫化苯酚钙。
CE6、CE7、EX1和EX2表征如下：
试验：HFRR磨损
在可由PCS Instruments得到的程序升温高频往复试验机(HFRR)中评估润滑剂的磨损性能。用于评估的HFRR条件为500g载荷、75分钟持续时间、1000微米冲程、20赫兹频率和在40℃下15分钟，其后以2℃/分钟的速率升温至160℃的温度曲线。上部试样为来自市售发动机的6mm直径硅酸铝切片。上部和下部试样一起可由PCS Instruments(零件号HFRSSP)得到。测量对于铝基发动机组件得到的磨痕数据并显示于下表中：
| EX1 | CE6 | EX2 | CE7 | |
| 磨痕(μm) | 218 | 303 | 212 | 267 |
总之，所示数据表明含有过碱性硫化苯酚钙的润滑组合物具有与含有过碱性磺酸钙的类似润滑剂相比在铝组件上降低的磨损。数据表明含有过碱性硫化苯酚钙的润滑组合物具有比含有过碱性磺酸钙的润滑组合物小至少20％的磨损。
已知一些上述材料在最终配制剂中可能相互作用，使得最终配制剂的组分可能与起初加入的那些不同。由此形成的产品，包括经以其意欲用途使用本发明润滑剂组合物而形成的产品可能不容易描述。然而，所有这类改进和反应产物均包括在本发明的范围内；本发明包括通过将上述组分混合而制备的润滑剂组合物。
将以上涉及的各文件通过引用并入本文中。除实施例中，或另外明确说明外，在本说明书中描述材料的量、反应条件、分子量、碳原子数等的所有数量应当理解被措辞“约”修饰。除非另有说明，本文提及的各个化学品或组合物应当理解为可含有异构体、副产物、衍生物和通常应当理解存在于商品级中的其它这类材料的商品级材料。然而，除非另有说明，各个化学组分的量表示为排除了通常可存在于商业材料中的任何溶剂或稀释油。应当理解本文所述量、范围和比的上限和下限可独立地组合。类似地，本发明各个元素的范围和量可以与任何其它元素的范围或量一起使用。
如本文所用，术语“烃基取代基”或“烃基”以其本领域技术人员熟知的常用意义使用。具体而言，它指具有直接连接在分子其余部分上的碳原子且主要具有烃性质的基团。烃基的实例包括：烃取代。基，包括脂族、脂环族和芳族取代基；取代的烃取代基，即含有在本发明上下文中不改变取代基的主要烃性质的非烃基团的取代基；和杂取代基，即类似地具有主要烃性质，但在环或链中含有不同于碳的取代基。术语“烃基取代基”或“烃基”的更详细定义描述于国际公开WO2008147704的第[0118]-[0119]段中。
尽管已关于优选实施方案解释了本发明，应当理解经阅读本说明书，其各个改进会为本领域技术人员所了解。因此，应当理解此处公开的发明意欲涵盖属于所附权利要求范围的这类改进。
Claims (21)
1.一种润滑内燃机的铝合金表面的方法，其包括向铝合金表面提供包含具有润滑粘度的油和碱金属或碱土金属酚盐清净剂的润滑组合物。
2.根据权利要求1的方法，其中酚盐清净剂为锂、钠、钙、镁或钡的酚盐。
3.根据权利要求1或2的方法，其中酚盐清净剂为硫化苯酚钙。
4.根据前述权利要求1-3中任一项的方法，其中酚盐清净剂为过碱性硫化苯酚钙。
5.根据前述权利要求1-4中任一项的方法，其中润滑组合物包含(a)具有润滑粘度的油、(b)TBN为200-400的过碱性碱金属或碱土金属酚盐清净剂，且进一步包含(c)TBN为20-170(例如155)的中性酚盐(通常为不合硫的苯酚钙)。
6.根据前述权利要求1-5中任一项的方法，其中碱金属或碱土金属酚盐清净剂具有0.8-10或3-9，或4-8，或5-7的金属比。
7.根据前述权利要求1-6中任一项的方法，其中碱金属或碱土金属酚盐清净剂将0.75-2重量％，或0.9-1.75重量％，或1-1.5重量％的烃基取代的苯酚输送至润滑组合物中。
8.根据前述权利要求1-6中任一项的方法，其中碱金属或碱土金属酚盐清净剂将0.9-1.75重量％的烃基取代的苯酚及其阴离子输送至润滑组合物；且硫酸盐灰含量为润滑组合物的至少0.4至1.3重量％。
9.根据前述权利要求1-6中任一项的方法，其中碱金属或碱土金属酚盐清净剂将0.9-1.75重量％的烃基取代的苯酚输送至润滑组合物中；且硫酸盐灰含量为润滑组合物的至少0.4至1.2重量％。
10.根据前述权利要求1-6中任一项的方法，其中碱金属或碱土金属酚盐清净剂将1重量％或更高至1.5重量％的烃基取代的苯酚输送至润滑组合物中；且硫酸盐灰为润滑组合物的至少0.6至1.1重量％。
11.根据前述权利要求1-6中任一项的方法，其中润滑组合物的硫酸盐灰含量为润滑组合物的至少0.3重量％，或至少0.4重量％，至少0.6至2重量％，或1.5重量％，或1.3重量％，或1.1重量％。
12.根据前述权利要求1-6中任一项的方法，其中润滑组合物的特征是具有(i)0.5重量％或更少的硫含量，(ii)0.06重量％或更少的磷含量，和(iii)1.3重量％或更少的硫酸盐灰含量。
13.根据前述权利要求1-12中任一项的方法，其进一步包含二烷基二硫代磷酸锌或其混合物。
14.根据权利要求13的方法，其中二烷基二硫代磷酸锌以润滑组合物的0-5重量％，或0.1-3重量％，或0.5-2重量％存在。
15.根据前述权利要求1-14中任一项的方法，其进一步包含抗磨剂、分散剂粘度改进剂、摩擦改进剂、粘度改进剂、抗氧化剂、过碱性清净剂中的至少一种或其混合物。
16.根据权利要求15的方法，其中摩擦改进剂选自胺的脂肪酸衍生物、脂肪酯、脂肪环氧化物、脂肪咪唑啉和烷基磷酸的胺盐。
17.根据前述权利要求1-16中任一项的方法，其进一步包含分散剂粘度改进剂。
18.根据前述权利要求1-17中任一项的方法，其进一步包含过碱性清净剂，其中过碱性清净剂通常选自磺酸盐、salixarate、水杨酸盐及其混合物。
19.根据前述权利要求1-18中任一项的方法，其中铝合金为共晶或过共晶铝合金(例如衍生自硅酸铝、氧化铝或其它陶瓷材料的那些)。
20.根据前述权利要求1-19中任一项的方法，其中内燃机具有部分或所有由铝合金、铝复合物组成的气缸腔、气缸柱或活塞环。
21.碱金属或碱土金属酚盐清净剂(通常为硫化苯酚钙)作为用于内燃机的铝合金表面的抗磨剂的用途。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104099158A (zh) * | 2013-04-15 | 2014-10-15 | 巫远程 | 网状晶格纳米球润滑油改善剂 |
| CN104099158B (zh) * | 2013-04-15 | 2017-10-27 | 广州泛海节能科技有限公司 | 网状晶格纳米球润滑油改善剂 |
| CN106062157A (zh) * | 2013-09-19 | 2016-10-26 | 路博润公司 | 用于直喷式发动机的润滑剂组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20120245065A1 (en) | 2012-09-27 |
| IN2012DN01625A (zh) | 2015-06-05 |
| WO2011022245A1 (en) | 2011-02-24 |
| EP2467456A1 (en) | 2012-06-27 |
| EP2467456B2 (en) | 2023-08-09 |
| EP2467456B1 (en) | 2014-10-22 |
| BR112012003694A2 (pt) | 2016-03-29 |
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