CN1065267C - 用于润滑基油的改进的抗氧化剂体系 - Google Patents
用于润滑基油的改进的抗氧化剂体系 Download PDFInfo
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- CN1065267C CN1065267C CN98115983A CN98115983A CN1065267C CN 1065267 C CN1065267 C CN 1065267C CN 98115983 A CN98115983 A CN 98115983A CN 98115983 A CN98115983 A CN 98115983A CN 1065267 C CN1065267 C CN 1065267C
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- oil
- weight
- molybdenum
- antioxidant
- sulphur
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- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
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- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- IBYFOBGPNPINBU-UHFFFAOYSA-N tetradecenoic acid Natural products CCCCCCCCCCCC=CC(O)=O IBYFOBGPNPINBU-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical compound ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 description 1
- IBYFOBGPNPINBU-OUKQBFOZSA-N trans-2-tetradecenoic acid Chemical compound CCCCCCCCCCC\C=C\C(O)=O IBYFOBGPNPINBU-OUKQBFOZSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
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- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
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Classifications
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Abstract
本发明涉及抗氧化剂体系,它包含(A)至少为一种的二芳基仲胺,(B)至少为一种的硫化烯烃和/或硫化受阻酚,和(C)至少为一种的油溶性的钼化合物。这些抗氧化剂组合物可高效地为润滑剂组合物,特别是为高饱和的、低硫润滑基油提供氧化稳定性。
Description
本发明涉及一种具有优异的腈弹性体密封兼容性的抗氧化剂体系及其在完全配制润滑剂中的应用。更具体地说,本发明涉及一种包含(A)至少为一种的二芳基仲胺,(B)至少为一种的硫化烯烃和/或硫化受阻酚,和(C)至少为一种的油溶性的钼化合物的抗氧化剂组合物。
用于汽车和货车内燃机的润滑油在使用过程中要经受环境的考验。环境可导致油发生氧化,这种氧化作用可因油中杂质的存在而被催化并且可通过在使用过程中油温的升高而加速。通常,通过使用可延长油的使用寿命的抗氧添加剂,特别是通过降低或防止不受欢迎的粘度升高能够在某种程度上控制润滑油在使用过程中的氧化。
现已发现:通过(A)至少为一种的二芳基仲胺,(B)至少为一种的硫化烯烃和/或硫化受阻酚,和(C)至少为一种的油溶性钼化合物的结合能够产生一种高效的抗氧化剂体系。
美国专利5605880披露了在润滑剂组合物中与二硫代氨基甲酸硫化氧钼和有机磷二硫代羧酸硫化氧钼结合使用的烷基化的二苯胺和苯基-α-萘胺。然而,这些参考内容并没有教导使用硫化烯烃或硫化受阻酚。
WO95/07963披露了包含含硫的钼化合物和烷基化二苯胺的混合物。该参考文献提及可以存在其他抗氧化剂如硫化烯烃或硫化受阻酚,但是该参考文献并未特别指出使用三组分抗氧化剂体系,或认为三组分抗氧化剂体系具有比该参考文献中的二组分组合物更加明显有效的抗氧作用。
本发明的一个目的是通过向所述的润滑剂组合物中加入包含(A)至少为一种的二芳基仲胺,(B)至少为一种的硫化烯烃和/或硫化受阻酚,和(C)至少为一种的油溶性钼化合物的抗氧化剂组合物,为使用加氢裂解和/或加氢异构的矿物基油的、包含低含量(通常磷含量小于850ppm)的ZDDP衍生磷的完全配制润滑剂组合物提供一种甚高水平的防氧化作用和粘度控制能力,而不会使腈弹性体密封装置发生硬化。该三组分抗氧化剂体系为以上提及的基油所提供的防氧化作用要优于这些组分中任意两种的结合所取得的防护作用。
一方面,本发明涉及包含基油和抗氧化剂组合物的润滑油组合物,其中抗氧化剂组合物包含(A)至少为一种的二芳基仲胺,(B)至少为一种的硫化烯烃和/或硫化受阻酚,和(C)至少为一种的油溶性的钼化合物。
另一方面,本发明涉及一种通过向润滑剂中加入抗氧化剂组合物用于改进润滑剂的抗氧化性和腈弹性体密封兼容性的方法,其中抗氧化剂组合物包含(A)至少为一种的二芳基仲胺,(B)至少为一种的硫化烯烃和/或硫化受阻酚,和(C)至少为一种的油溶性钼化合物。
另外还有一方面,本发明涉及一种包含溶剂;和由(A)至少为一种的二芳基仲胺,(B)至少为一种的硫化烯烃和/或硫化受阻酚,和(C)至少为一种的油溶性钼化合物组成的混合物的润滑剂浓缩物。
组分(A)-二芳基仲胺
用于本发明的二芳基仲胺在包装配制油或包装浓缩液中应该是水溶性的。二芳基仲胺最好具有通式:R1-NH-R2,其中R1和R2分别独立地表示具有6-30个碳原子的取代或未取代芳基。可列举的芳基取代基包括具有1-20个碳原子的烷基、烷芳基、羟基、羧基和硝基。芳基最好是取代或未取代的苯基或萘基,特别是其中的一个或两个芳基是被烷基取代的。最好是两个芳基都被烷基取代。
可用于本发明的二芳基仲胺的例子包括二苯胺、烷基化二苯胺、3-羟基二苯胺、N-苯基-1,2-苯二胺、N-苯基-1,4-苯二胺、丁基二苯胺、二丁基二苯胺、辛基二苯胺、二辛基二苯胺、壬基二苯胺、二壬基二苯胺、苯基-α-萘胺、苯基-β-萘胺、庚基二苯胺、二庚基二苯胺、甲基苯乙烯基二苯胺、丁基/辛基混合烷基化二苯胺、丁基/苯乙烯基混合烷基化二苯胺、乙基/壬基混合烷基化二苯胺、辛基/苯乙烯基混合烷基化二苯胺、乙基/甲基苯乙烯基混合烷基化二苯胺、辛基烷基化的苯基-α-萘胺以及通常用于石油工业的不同纯度的这些物质的混合物。
商业上二芳基仲胺的例子包括来自Ciba-Geigy公司的Irganox_L06和Irganox_L57;来自Uniroyle化学公司的Naugalube_AMS、Naugalube_438、Naugalube_438R、Naugalube_438L、Naugalube_500、Naugalube_640、Naugalube_680和Naugard_PANA;来自BF Goodrich Speciality Chemicals的Goodrite_3123、Goodrite_3190X36、Goodrite_3127、Goodrite_3128、Goodrite_3185X1、Goodrite_3190X29、Goodrite_3190X40和Goodrite_3191;来自R.T.Vanderbilt有限公司的Vanlube_DND、Vanlube_NA、Vanlube_PNA、Vanlube_SL、Vanlube_SLHP、Vanlube_SS、Vanlube_81、Vanlube_848、Vanlube_和Vanlube_849。
二芳基仲胺中的氮含量最好在净添加剂浓缩物的约2重量%和12重量%之间。二芳基仲胺在配制润滑油中的浓度可随着用户的需要和应用,以及特定配制油所需的理想水平的抗氧化保护作用而作相应的变化。通常二芳基仲胺存在于配制油中的数量为约0.05重量%~0.5重量%,优选为约0.1重量%~0.4重量%。
组分(B)-硫化烯烃和/或硫化受阻酚
在本发明中有用的硫化烯烃可通过许多已知方法来制备。它们是由在其生产中所用的烯烃种类及其最终的硫含量来表征的。高分子量烯烃,即,那些平均分子量为168~351g/mole的烯烃被优选。可使用的烯烃的例子包括α-烯烃、异构化的α-烯烃、支链烯烃、环烯烃以及它们的混合物。
适有的α-烯烃包括任何C4~C25的α-烯烃。α-烯烃可在硫化反应之前或在硫化反应过程中被异构化。也可以使用包含内部双键和/或支化结构的α-烯烃的结构上的和/或构象上的同分异构体。例如,异丁烯是α-烯烃1-丁烯的支链烯烃对应物。
可被用于硫化反应的硫源包括:元素硫、一氯化硫、二氯化硫、硫化钠、多硫化钠以及在硫化工艺的不同阶段被同时加入或被分别加入的这些物质的混合物。
由于其不饱和性,不饱和脂肪酸和油也可被硫化并用于本发明。可被使用的脂肪酸的例子包括十二烯酸、十四烯酸、十六烯酸、油酸、反油酸、异油酸、亚油酸、亚麻酸、二十碳烯酸、花生四烯酸、芥酸以及这些的混合物。可被使用的油或脂的例子包括玉米油、棉子油、柚子油、橄榄油、棕榈油、花生油、菜子油、红花子油、芝麻子油、豆油、向日葵子油以及这些的混合物。
硫化烯烃在配制润滑油中的浓度可随着用户的需要和应用,以及特定配制油所需的理想水平的抗氧化保护作用而作相应的变化。选择用于配制油的硫化烯烃浓度的一个重要准则是硫化烯烃本身的硫含量。硫化烯烃应将0.05重量%~0.30重量%的硫供给成品的润滑剂配方。例如,硫含量为20重量%的硫化烯烃应以0.25重量%~1. 5重量%的浓度被使用以便将0.05重量%~0.30重量%的硫供给成品油。硫含量为10重量%的硫化烯烃应以0.5重量%~3.0重量%的浓度被使用以便将0.05重量%~0.30重量%的硫供给成品油。
可被用于本发明的商业上硫化烯烃的例子,包括均来自Ethyl公司的硫含量约为20重量%的HiTEC_7084、硫含量约为12重量%的HiTEC_7188、硫含量约为47.5重量%的HiTEC_312和硫含量约为47.5重量%的HiTEC_313,以及来自Rhein Chemie公司的硫含量约为38重量%的Additin_RC2540-A。可用于本发明的商业上可得到的硫化脂肪油、或硫化脂肪油与烯烃的混合物,包括均来自Rhein Chemie公司的硫含量约为9.5重量%的Additin_RC4410、硫含量约为12.5重量%的Additin_R4412-F、硫含量约为17.5重量%的Additin_R4417、硫含量约为15重量%的Additin_RC2515、硫含量约为26重量%的Additin_RC2526、硫含量约为10重量%的Additin_RC2810-A、硫含量约为14重量%的Additin_RC2814-A和硫含量约为16重量%的Additin_RC2818-A。硫化烯烃和/或脂肪油最好是一种低腐蚀性的且活性硫含量低(按ASTM-D 1662测定)的液体。
适用于本发明的硫化受阻酚可通过许多已知方法来制备。它们是由在其生产中所用的受阻酚种类及其最终的硫含量来表征的。受阻叔丁酚被优选。硫化受阻酚可以是无氯的,由无氯硫源如元素硫、硫化钠或多硫化钠制备;或者它们可以是含氯的,由氯化的硫源如一氯化硫和二氯化硫来制备。优选的硫化受阻酚包括那些具有以下通式结构的硫化受阻酚。
其中R为烷基,R1选自烷基或氢,Z或Z1之一为OH而另一个为氢,Z2或Z3之一为OH而另一个为氢,x在1~6的范围内,而且y在0~2的范围内。
合适的无氯的硫化受阻酚可用美国专利№3929654中所教导的方法加以制备或者通过在(a)极性溶剂中制备一种由(ⅰ)至少为一种的无氯的受阻酚、(ⅱ)无氯硫源、和(ⅲ)至少为一种的碱金属氢氧化物促进剂组成的混合物,然后(b)使组分(ⅰ)、(ⅱ)、和(ⅲ)在足够的温度下反应充分长的时间,以便形成至少为一种的无氯硫化受阻酚,这正如1996年6月3日递交的待决申请08/657141和1997年2月19日递交的待决申请08/877533所教导的。
由氯化的硫源制备的合适的硫化受阻酚产品包括在美国专利No3250712和4946610中所教导的那些产品,特此编入这两项专利作为本发明的参考文献。
可被用于本发明的硫化受阻酚的例子包括4,4’-硫代双(2,6-二叔丁酚)、4,4’-二硫代双(2,6-二叔丁酚)、4,4’-硫代双(2-叔丁基-6-甲基苯酚)、4,4’-二硫代双(2-叔丁基-6-甲基苯酚)、4,4’-硫代双(2-叔丁基-5-甲基苯酚)以及这些物质的混合物。
硫化受阻酚最好是基本上为液态的产品。这里所用的“基本上为液态”是指主要为液态的组合物。因此,硫化受阻酚的陈化样品可能形成微量结晶,通常在产品与空气和玻璃容器表面接触的容器侧壁周围。更被优选的是,硫化受阻酚为无氯的、低腐蚀性的并具有高的一硫化物含量,正如1996年6月3日递交的待决的申请08/657141和1997年2月19日递交的待决的申请08/877533中所描述的那类硫化受阻酚。同样优选的是,硫化受阻酚中的含硫量为含添加剂的浓缩物的4.0重量%~12.0重量%。
硫化受阻酚在配制润滑油中的浓度可随着用户的需要和应用,以及特定配制油所需的理想水平的抗氧化保护作用而作相应的变化。在成品配制油中,优选的用量为0.3重量%~1. 5重量%。
也可以使用硫化烯烃和硫化受阻酚的混合物。
组分(c)-油溶性钼化合物
任何油溶性钼化合物都可用于本发明。严格要求的是供给成品配制油的钼的量。该量可随着用户的需要和应用,以及特定配制油所需的理想水平的抗氧化保护作用而作相应的变化。在成品配制油中,优选的钼的浓度为60ppm~1000ppm之间。例如,钼含量为8.0重量%的油溶性钼化合物应以0.08重量%~1. 25重量%的用量使用以便将64ppm~1000ppm的钼供给成品油。
可被用于本发明的一些油溶性钼化合物的例子包括二硫代氨基甲酸钼、二硫代氨基甲酸硫化氧钼、二硫代黄原酸钼、二硫代黄原酸硫化氧钼、有机磷二硫代羧酸钼、有机磷二硫代羧酸硫化氧钼、羧酸钼、钼的胺配合物、钼的醇配合物、钼的酰胺配合物、钼的胺/醇/酰胺混合配合物以及这些物质的混合物。可被用于本发明的商业上可得到的油溶性钼化合物的例子,包括由Shepherd化学公司得到的钼含量为约8.5重量%的辛酸钼;由OM Group得到的钼含量为约15.0重量%的钼HEX-CEM;均由R.T.Vanderbilt有限公司得到的钼含量为约8.0重量%的Molyvan_855,钼含量为约4.9重量%的Molyvan_807和钼含量为约4.9重量%的Molyvan_822;均由AsahiDenka Kogyo K.K.得到的钼含量为约4.1重量%的SAKURA-LUBE_100,钼含量为约4.5重量%的SAKURA-LUBE_155,钼含量为约27.5重量%的SAKURA-LUBE_600和钼含量为约4.5重量%的SAKURA-LUBE_700。
由于降低车用机油的磷含量以改善汽车催化剂的兼容性已成为一种趋势,在曲轴箱油配方中最好使用无磷的钼化合物。进而,值得注意的是,由于活性硫在这些添加剂中的存在,使得硫化烯烃和硫化受阻酚在成品油中的使用受到限制。活性硫可用一些方法加以确定。一种测定活性硫在添加剂中量的试验方法是ASTM-D 1662。活性硫的量还可以通过对活性硫敏感的润滑剂台架试验来测定。例如,ASTM-D 130对包含显著量活性硫的润滑剂显示出较高程度的铜腐蚀性。还有,Allison C-4腈密封试验对包含显著量活性硫的润滑剂显示出较高程度的腈密封硬化作用。由于这些密封兼容性和腐蚀之故,具有高活性硫量的润滑剂是不合要求的。然而,这些相同的添加剂仍是高效的高温抗氧化剂。因此需要一种能够允许使用含活性硫的抗氧化剂但不造成严重的铜腐蚀性或腈密封不兼容性的配制方法。将油溶性的无硫钼化合物,与上述的二芳基仲胺和硫化烯烃和/或受阻酚的结合使用,能够提供优异的抗氧性能以及优异的腈密封兼容性,而这是合适的润滑油配方所需的。
通常,抗氧化剂组合物是以包装浓缩物的形式被加入到油中的。浓缩物中产品的量一般在约5重量%~75重量%,优选在约5重量%~50重量%之间变化。浓缩物还可含有其他添加剂如分散剂、洗涤剂、抗磨剂、辅助抗氧化剂、粘度指数改进剂、倾点下降剂、缓蚀剂、防锈剂、抑泡剂和摩擦改进剂。
分散剂通常为包含被结合到高分子量烃链上的氮或氧的极性基团的非金属添加剂。烃链提供在烃基料中的溶解性。分散剂起将油的降解产物悬浮在油中的作用。适用的分散剂的例子包括聚甲基丙烯酸酯和苯乙烯马来酯的共聚物,取代的琥珀酰亚胺,多胺琥珀酰亚胺,多羟基琥珀酯,取代的曼尼期碱和取代的三唑。一般说,如果使用的话,分散剂在成品油中的量为约3重量%~约10重量%。
洗涤剂通常为包含金属离子和极性基团的金属添加剂,例如,具有脂族链、环脂族链或烷芳基链的磺酸盐或羧酸盐。洗涤剂通过去除发动机各表面上的沉积物而起作用。适用的洗涤剂的例子包括中性的和高碱性的碱金属或碱土金属的磺酸盐,中性的和高碱性的碱金属或碱土金属的苯酚盐,硫化苯酚盐,以及高碱性的碱土金属的水杨酸盐。一般来说,如果使用的话,洗涤剂在成品油中的量为约1重量%~约5重量%。
抗磨添加剂一般被加入到润滑剂配方中。常用的,特别是用于配制曲轴箱润滑油的抗磨剂是二烃基二硫代磷酸锌(ZDDP)。这些添加剂通过与金属表面反应形成一种新的其自身发生变形并因此保护了原发动机表面的表面活性化合物而起作用的。ZDDP能将磷供给成品配制润滑油。在曲轴箱的应用中,现今客车的SJ油的最大极限含磷量为100ppm,这是成品油所允许的。据信,磷在成品的配制曲轴箱油中的存在提高了汽车的排放并由此造成污染。因此在成品油中降低磷含量,并由此降低ZDDP的含量是受欢迎的。然而,ZDDP是很强的抗氧化剂。从成品油中去除了ZDDP则会加强对油中所存在的其他抗氧化剂的要求。本发明的三组分抗氧化剂体系在不损害抗氧化剂性能的情况下,在低含磷量例如500ppm~850ppm时仍是高效的。
辅助抗氧化剂,即除了本发明抗氧化剂体系三组分之外的抗氧化剂,可被用于氧化稳定性较差的油或经受异常恶劣条件的油中。本发明的三组分体系所提供的抗氧化保护作用可能不需要另外的抗氧化剂。然而,由于成本因素以及发动机油的兼容性问题可能需要使用其他的抗氧化剂。合适的辅助抗氧化剂包括受阻酚、受阻双酚、硫化烷基酚、二硫代氨基甲酸二烷基酯、噻吩嗪、和油溶性铜化合物。
在本发明中可随意选用的粘度指数改进剂(Ⅶ)选自任何已知的Ⅶ。Ⅶ通过降低粘度随温度的变化率而起作用,即,它们使发动机油的粘度在低温下升高极小而在高温下显著升高。适合的Ⅶ的例子包括聚异丁烯、聚甲基丙烯酸酯、乙烯/丙烯共聚物、官能化的乙烯/丙烯共聚物、聚丙烯酸酯、苯乙烯/马来酯共聚物、和氢化的苯乙烯/丁二烯共聚物。
被用于形成本发明的润滑组合物的基油,与Ⅰ组基油相比,是以高含量的饱和物和非常低含量的硫来表征的;而且它包括在石油添加剂工业中被称为Ⅱ组和Ⅲ组基油的基油。可使用各种方法来生产这些油。所生产的油通常被称为强加氢油或强加氢裂化油。它们可由惯用的原料使用强加氢步骤以降低芳族化合物、硫和氮的含量,然后经过脱蜡、加氢精制、抽提和/或蒸馏步骤而生产出成品的基油来制备。本发明的油一般包含大于或等于90%的饱和物,小于或等于0.03重量%的硫并且粘度指数大于或等于80。
最近,在石油添加剂工业中存在一些趋势,即可能禁止和/或限制某些添加剂在配制曲轴箱油中的使用。主要趋势是降低油的含磷量、满足新的燃料经济要求、使用更加深度精制的油品以及为成品油制定更加严格的发动机和台架试验的条件。这种变化可能表示某些现在使用的抗氧化剂添加剂并不能对油的氧化产生理想的保护作用。本发明的三组分抗氧化剂体系为这种需求提供了一种解决办法。本发明还涉及一种配制方法,使得过去由于腐蚀性问题和腈密封兼容性问题而不能使用的硫化抗氧化剂有可能被使用。
实施例1
如表1中所示,掺混一系列客车用机油。通过使用高分子分散剂、磺酸盐洗涤剂、ZDDP、抑泡剂、粘度指数改进剂、倾点下降剂和稀释剂工艺用油来配制油而制得SAE级的5W-30车用机油。所用的抗氧添加剂和基油如表1所示。在按照ASTM STP 315H第一部分进行的第ⅢE号发动机试验中,对这些油进行评估。ⅢE试验是在高速(3000rpm)和149℃的很高油温下,使用231CID(3.8)升的BuickV-6发动机进行64小时。该试验是被用来评估发动机油的减少氧化、变稠、淤渣、漆膜、沉积和高温磨损的能力的。
掺混含添加剂的包装浓缩物#1以向成品油提供约900ppm的ZDDP衍生磷,然后用其量足以能有效地控制一般加氢精制油中淤渣的高分子分散剂进行配制。掺混含添加剂的包装浓缩物#2以向成品油提供约900ppm的ZDDP衍生磷,然后用其量足以能有效地控制超低硫加氢裂化油中淤渣的高分子分散剂进行配制。掺混含添加剂的包装浓缩物#3以向成品油提供约820ppm的ZDDP衍生磷,然后用其量足以能有效地控制超低硫加氢裂化油中淤渣的高分子分散剂进行配制。
100N和240N的加氢裂化基油是从Chevon化学公司得到的,并且通常含有小于50ppm的硫、小于5ppm的氮、95~99%的饱和物、以及1~4%的芳族化合物。100N和325N的加氢精制基油是从AshlandOil公司得到的,分别含有0.31重量%和0.88重量%的硫,并且相对于加氢裂化油而言,它们的特征在于具有较高的氮含量、较低浓度的饱和物、以及较高浓度的芳族化合物。
所用的硫化烯烃为包含约20重量%硫的C16-18硫化烯烃,可从Ethyl公司以商品HiTEC_7084硫化烯烃购得。所用的2-乙基己酸钼为钼HEX-CEM,一种得自OM Group的钼含量为约15.0重量%的油溶性钼化合物。有机钼的配合物为Molyvan_855,一种得自R.T.Vanderbilt有限公司的无硫和磷的钼化合物。烷基化二苯胺为Naugalube_680,一种得自Uniroyle化学有限公司的辛基/苯乙烯基混合烷基化二苯胺。
表1.在第ⅢE号试验中对抗氧化剂的评估
油#1* | 油#2* | 油#3* | 油#4* | 油#5* | 油#6 | 油#7 | |
包装类型 | |||||||
含添加剂的包装浓缩物#1 | 17.715 | 17.715 | |||||
含添加剂的包装浓缩物#2 | 16.150 | 16.015 |
含添加剂的包装浓缩物#3 | 15.500 | 15.500 | 15.500 | ||||
抗氧化剂类型 | |||||||
硫化烯烃 | 0.700 | 0.700 | 0.700 | ||||
2-乙基己酸钼 | 0.085 | 0.085 | 0.150 | 0.085 | 0.112 | ||
有机钼配合物 | 0.210 | ||||||
烷基化二苯胺 | 0.200 | 0.200 | 0.200 | 0.400 | 0.300 | 0.300 | 0.300 |
基油类型 | |||||||
100N低硫加氢裂解油 | 77.000 | 72.900 | 72.900 | 72.900 | 72.900 | 72.900 | |
240N低硫加氢裂解油 | 5.000 | 10.600 | 10.600 | 10.600 | 10.600 | 10.600 | |
100N加氢补充精制油 | 76.000 | ||||||
325N加氢精制油 | 6.000 | ||||||
分析内容 | |||||||
计算出的P(ppm) | 900 | 900 | 900 | 900 | 820 | 820 | 820 |
计算出的Mo(ppm) | 128 | 128 | 225 | 128 | 0 | 168 | 168 |
粘度升高(%变化) | |||||||
8小时 | 16 | 11 | -5 | -5 | -3 | -3 | -4 |
16小时 | 23 | 18 | -6 | -5 | -2 | -3 | -4 |
24小时 | 25 | 22 | -8 | -4 | 1 | 0 | -1 |
32小时 | 26 | 16 | 16 | -4 | 1 | 2 | 0 |
40小时 | 45 | 54 | 73 | 17 | -3 | 5 | -2 |
48小时 | 85 | 140 | 194 | 84 | 146 | 6 | -6 |
56小时 | 159 | 422 | 672 | 216 | 522 | 6 | 9 |
64小时(375最大) | 300 | 2541 | 2486 | 854 | 3576 | -1 | 40 |
IIIE结果 极限值 | |||||||
粘度升高375%的小时数最小64分钟 | 66.4 | 54.7 | 51 | 58 | 52.9 | 85.8 | 81 |
AE淤渣最小9.2分钟 | 9.56 | 9.34 | 9.25 | 9.36 | 9.25 | 9.75 | 9.62 |
仰S漆膜最小8.9分钟 | 9.38 | 9.1 | 8.78 | 8.9 | 8.6 | 9.33 | 9 |
0RL沉积 最小3.5分钟 | 4.8 | 3.59 | 2.54 | 3.54 | 2.88 | 4.46 | 3.76 |
AC磨损 最大30 | 6.5 | 7.6 | 10.4 | 10.6 | 10.5 | 11.8 | 8.8 |
MC磨损 最大64 | 11 | 11 | 14 | 20 | 13 | 15 | 13 |
油耗,L 最大5.1 | 3.55 | 3.61 | 3.73 | 3.21 | 3.89 | 2.56 | 2.78 |
*对比例
表1中的ⅢE试验结果显示出各种效果。(1)由钼和烷基化二苯胺组成的二组分抗氧化剂体系在控制粘度上是有效的并在高硫加氢精制油(油#1)项目上通过了ⅢE试验,但对超低硫加氢裂解油(油#2~4),即使调整了低硫加氢裂解油中的抗氧化剂处理浓度,效果也较差。(2)由硫化烯烃和烷基化二苯胺组成的二组分抗氧化剂(油#5)在控制粘度上没有效果并且在含磷量降低(820ppm)的低硫加氢裂解油(油#2~4)项目上未通过ⅢE试验。(3)当由硫化烯烃、烷基化二苯胺和钼组成的本发明三组分抗氧化剂体系(油#6和7)用于超低硫加氢裂解油时,可看出油的控制粘度的能力大为改善并通过了ⅢE试验。
表1的结果清楚地显示出:为了在低含磷量下配制成的超低硫加氢裂解油中有效地控制粘度,由硫化烯烃、烷基化二苯胺和油溶性钼组成的三组分抗氧化剂体系得到了比常规的二组分(即钼与二苯胺,或硫化烯烃与烷基化二苯胺)抗氧化剂体系远为优异的结果。
实施例2
如表2中所示,掺混SAE级的5W-30客车用机油。油#8和9是使用由高分子分散剂、磺酸盐洗涤剂、二烷基二硫代磷酸锌(ZDDP)、抑泡剂、粘度指数改进剂、倾点下降剂、稀释剂工艺用油和表2所列的抗氧化剂组成的含添加剂包装浓缩物来配制的。在如实施例1中所描述的ⅢE发动机试验中,通过以下所作的改进对两种油进行评估。由于本发明三组分抗氧化剂体系表现出非常高的有效性,因此有必要延长ⅢE试验。在表2的粘度结果部分指出每次ⅢE试验实际进行的时间。将这些油掺混以向成品油提供约740ppm的ZDDP衍生磷,然后用其量足以能有效地控制超低硫加氢裂化油中淤渣的高分子分散剂进行配制。所用的100N和240N的超低硫加氢裂化基油与实施例1中的相同。硫化受阻酚可用一种与1996年6月3日递交的待决申请08/657141的实施例2中所描述的相似方法加以制备,它含有10.75重量%的硫。所用的2-乙基己酸钼为辛酸钼,一种可由Shepherd化学公司买到的含有约8.5重量%钼的油溶性钼化合物。所用的烷基化二苯胺为Naugalube_680,一种得自Uniroyle化学有限公司的辛基/苯乙烯基二苯胺。
表2.在ⅢE试验中对抗氧化剂的评估结果:
油#8 | 油#9 | |
抗氧化剂类型 | ||
硫化受阻叔丁酚 | 0.600 | 1.000 |
2-乙基己酸钼 | 0.100 | 0.800 |
烷基化二苯胺 | 0.300 | 0.300 |
基油类型 | ||
100N低硫加氢裂解基油 | 74.000 | 73.186 |
240N低硫加氢裂解基油 | 8.000 | 7.912 |
分析内容 | ||
计算出的P(ppm) | 740 | 732 |
计算出的Mo(ppm) | 85 | 680 |
粘度升高的日期(%变化) | ||
8小时 | -4.2 | -6 |
16小时 | -0.9 | -5.1 |
24小时 | 4 | -1.5 |
32小时 | 7.8 | 2.2 |
40小时 | 9.7 | 5.5 |
48小时 | 6.3 | 8.5 |
56小时 | 33.2 | 10.9 |
64小时(完成一轮试验) | 143.9 | 12.9 |
72小时 | 543.9 | 16 |
80小时 | TVTM* | 17.5 |
88小时 | TVTM* | 19.2 |
96小时 | 20.1 | |
104小时 | 22.7 | |
U2小时 | 27.5 | |
120小时 | 34.8 | |
128小时(完成两轮试验) | 49.4 |
*粘度太高,无法测量
表2中的ⅢE试验结果说明本发明的三组分抗氧化剂体系的各种益处。当本发明的三组分抗氧化剂体系被用于超低硫加氢裂解油时,在ⅢE试验中可看出油的控制粘度的能力大为改善(由实施例1中的油#2~5与实施例2中的油#8和9比较可见)。即使油#8与9中的ZDDP衍生磷的浓度(约740ppm)低于实施例1中的ZDDP衍生磷的浓度(900和820ppm),由此得到一种对氧化作用与粘度升高更加敏感的油,但由于本发明三组分抗氧化剂体系的原因可看出该油是一种更加稳定的油。
此外,当三组分抗氧化剂体系的处理浓度提高时,可得到甚至更好的ⅢE粘度结果(油#8与油#9相比),即,油#9通过了两轮ⅢE试验,而粘度参数则反映出粘度升高很小。
实施例3
如表3中所示,将硫化受阻酚、硫化烯烃、烷基化二苯胺、和油溶性钼化合物掺混到SAE级的5W-30客车用机油中。通过使用相同的包含高分子分散剂、磺酸盐洗涤剂、二烷基二硫代磷酸锌(ZDDP)、抑泡剂、粘度指数改进剂、倾点下降剂和稀释剂工艺用油的含添加剂包装浓缩物来配制油。将这些油掺混合以向成品油提供约820ppm的ZDDP衍生磷,然后用其量足以能有效地控制超低硫加氢裂化油中淤渣的高分子分散剂进行配制。100N和240N的超低硫加氢裂化基油与实施例1中的相同。硫化受阻酚可用一种与1996年6月3日递交的待决申请08/657141的实施例2中所描述的相似方法加以制备,它含有10.22重量%的硫。所用的2-乙基己酸钼为辛酸钼,一种可从Shepherd化学公司买到的含有约8.5重量%钼的油溶性钼化合物。所用的烷基化二苯胺为Naugalube_680,一种得自Uniroyle化学有限公司的辛基/苯乙烯基二苯胺。所用的硫化烯烃为实施例1中所述的HiTEC_7084硫化烯烃。
这些油的氧化稳定性可通过J.A.Walker和W.Tsang在“用差示扫描量热法对润滑油进行的表征”,SAE技术论文系列,801383(1980年,10月20-23日)中所描述的加压差示扫描量热法(PDSC)来测量。用环烷酸铁催化剂(55ppm的Fe)处理油样品,然后在一个开口的铝制密封盘中对约2毫克的样品进行分析。用400psi的含有约55ppm的作为氧化催化剂的NO2的空气对DSC盒进行加压。随后进行以下的加热步骤:以20℃/min的速度升至120℃,以10℃/min的速度升至150℃,以2.5℃/min的速度升至250℃,等温保持1分钟。在温度上升的过程中,可观察到放热现象。这种放热现象表示氧化反应。观察到放热现象时的温度称为氧化开始温度,它是对油的氧化稳定性的一种度量(即,氧化开始温度越高,油的氧化稳定性越大)。所有的油被评估三次然后取平均值,结果被示于表3中。
表3中的开始温度值清楚地显示出,三组分抗氧化剂体系在控制完全配制客车机油的氧化方面的优点。要指出的是,对于仅包含三组分抗氧化剂体系中的一种或两种组分的抗氧化剂体系来说,有一种达到等效或更好结果的三组分抗氧化剂体系,即,相同或更高的开始温度的三组分抗氧化剂体系。例如,油#15使用0.9重量%的由仍使用两组分抗氧化剂体系(二苯胺代表一种组分,硫化烯烃和硫化受阻酚的混合物代表第二种组分)而能达到206.5℃的开始温度。在试验误差范围内,油#17和#18分别使用0.675重量%和0.75重量%的由三组分体系衍生的抗氧化剂,却得到了相同的开始温度。油#20仅使用0.575重量%的由三组分体系衍生的抗氧化剂,得到了更高的开始温度。在将仅包含一种或两种组分的油与包含所有三组分的油相比时,可看出这种特性。同样重要的是,硫化烯烃和硫化受阻酚的混合物可被用来代表三组分体系中的一种组分。当硫化烯烃和硫化受阻酚的混合物代表一种组分,而剩余两组分为钼和二苯胺时(油#22至#26),可被视为最有效的抗氧化剂混合物。
表3.通过PDSC评估抗氧化剂:
油# | 烷基化二苯胺,% | 硫化烯烃,% | 硫化烯烃的含S量,% | 硫化受阻酚,% | 油溶性钼,% | ppm Mo | 所用的总的抗氧化剂,% | 开始温度,℃ |
10* | 0.20 | 0.2 | 196.9 | |||||
11* | 0.20 | 0.40 | 0.080 | 0.6 | 200.6 | |||
12* | 0.20 | 0.80 | 0.160 | 1 | 203.5 | |||
13* | 0.20 | 0.60 | 0.8 | 205.7 | ||||
14* | 0.20 | 0.150 | 128 | 0.35 | 202.0 |
15* | 0.20 | 0.40 | 0.080 | 0.30 | 0.9 | 206.5 | ||
16* | 0.20 | 0.80 | 0.160 | 0.60 | 1.6 | 210.8 | ||
17 | 0.20 | 0.40 | 0.080 | 0.075 | 64 | 0.675 | 206.2 | |
18 | 0.20 | 0.40 | 0.080 | 0.150 | 128 | 0.75 | 206.3 | |
19 | 0.20 | 0.80 | 0.160 | 0.150 | 128 | 1.15 | 207.9 | |
20 | 0.20 | 0.30 | 0.075 | 64 | 0.575 | 207.8 | ||
21 | 0.20 | 0.60 | 0.150 | 128 | 0.95 | 210.8 | ||
22 | 0.20 | 0.40 | 0.080 | 0.30 | 0.075 | 64 | 0.995 | 210.3 |
23 | 0.20 | 0.40 | 0.080 | 0.60 | 0.075 | 64 | 1.275 | 212.3 |
24 | 0.20 | 0.40 | 0.080 | 0.30 | 0.150 | 128 | 1.05 | 211.9 |
25 | 0.20 | 0.80 | 0.160 | 0.30 | 0.075 | 64 | 1.375 | 212.1 |
26 | 0.20 | 0.80 | 0.160 | 0.60 | 0.150 | 128 | 1.75 | 215.9 |
*对比例
实施例4
以下实施例显示出在曲轴箱润滑剂中使用无硫的钼化合物比硫化的钼化合物的好处。
按表Ⅳ中的规定掺混一系列的重负荷柴油机油。通过使用高分子分散剂、磺酸盐和苯酚盐洗涤剂、ZDDP、抑泡剂、粘度指数改进剂、倾点下降剂、抗氧化剂、稀释剂工艺用油、和基油来配制油,制备出无钼的SAE级15W-40车用机油。然后用各种含硫和无硫的钼化合物对成品油进行彻底处理,为每种掺合物提供约500ppm的钼。所用钼化合物如下:Sakura-Lube_155,一种得自Asahi Denka Kogyo K.K.的含硫的二硫代氨基甲酸钼;Sakura-Lube_700,一种得自AsahiDenka Kogyo K.K.的无硫的钼的胺配合物;Molyvan_807和822,得自R.T.Vanderbilt有限公司的含硫的二硫代氨基甲酸钼;Molyvan_855,一种得自R.T.Vanderbilt有限公司的无硫的有机钼化合物;以及辛酸钼,一种得自Shepherd化学公司的无硫的羧酸钼。使用Allison C-4腈密封试验(GM 6137-M方法,J1试验,条件为:全部浸渍)对这些油的腈弹性体兼容性进行评估。评定被测的腈弹性体的硬度变化级别。该参数对成品油中的硫化添加剂特别敏感。活性硫具有硬化这些密封装置的效果,即在硬度变化率上有提高。结果示于表4中。要注意的是,尽管所有的钼化合物相对无钼的参照物来说有所改进,但是无硫的钼化合物所作的改进最大。这就是无硫的钼化合物的益处,因为它对能够与钼和二苯胺一起使用的混合的硫化抗氧化剂的含量和种类具有较大的适应性。
表4.钼化合物的腈密封性能评估
油# | SAE15W-40油(重量%) | 钼化合物 | 钼化合物的重量% | 稀释油(重量%) | 提供给油的ppm Mo | 硬度变化(+5至-5) |
27 | 98.2 | 无 | 0 | 1.8 | 0 | +5 |
28 | 98.2 | Molyvan_855 | 0.63 | 1.18 | 500 | 0 |
29 | 98.2 | Sakura-Lube_700 | 1.11 | 0.69 | 500 | +1 |
30 | 98.2 | 辛酸钼 | 0.59 | 1.21 | 500 | +1 |
31 | 98.2 | Molyvan_807 | 1.02 | 0.78 | 500 | +2 |
32 | 98.2 | Molyvan_822 | 1.02 | 0.78 | 500 | +2 |
33 | 98.2 | Sakura-Lube_155 | 1.11 | 0.69 | 500 | +2 |
实施例5
以下的实施例显示出,无硫的钼化合物是如何能被用于本发明而生产出与腈密封装置相容性的润滑剂的。
如表Ⅴ中所示,将硫化受阻酚、硫化烯烃、烷基化二苯胺和油溶性钼化合物掺混到SAE级的5W-30客车用机油中。通过使用高分子分散剂、磺酸盐洗涤剂、ZDDP、抑泡剂、粘度指数改进剂、倾点下降剂、抗氧化剂和稀释剂工艺用油来配制油。掺混这些油以向成品油提供820ppm的ZDDP衍生磷,然后用其量足以能有效地控制超低含硫量的加氢裂化油中淤渣的高分子分散剂进行配制。所用的100N和240N的超低含硫量的加氢裂化油均与实施例1中的相同。硫化受阻酚可用一种与1997年2月19日递交的待决申请08/877533中所描述的相似方法制备,它含有约6.6重量%的硫。所用的钼化合物为Molyvan_855,一种得自R.T.Vanderbilt有限公司的有机酰胺的油溶性有机钼配合物,它含有约8.0重量%的钼。所用的烷基化二苯胺为一种得自BF Goodrich有限公司的辛基/苯乙烯基烷基化二苯胺。所用的硫化烯烃为HiTEC_7084硫化烯烃,它是一种得自Ethyl公司的包含约20重量%硫的C16-18硫化烯烃。使用实施例4所规定的Allison C-4腈密封试验对这些油的腈弹性体密封兼容性进行评估。结果被示于表5中。要指出的是,无钼的试样未能通过评定硬度等级的腈密封试验,而含钼的试样通过该试验。这种效果是重要的,因为它允许人们能够使用较高含量的硫化烯烃和硫化受阻酚而不会导致腈密封的不兼容性。
表5.腈密封性能评估
油# | 二苯胺(重量%) | 硫化受阻酚(重量%) | 硫化烯烃(重量%) | 钼化合物(重量%,ppmMo) | 稀释油(重量%) | SAE 5W-30油(重量%) | 硬度变化(+5至-5) |
34 | 0.3 | 0,0 | 1.7 | 98 | +6 | ||
35 | 0.3 | 0.7 | 0,0 | 1 | 98 | +6 | |
36 | 0.3 | 0.7 | 1.0,800 | 98 | +1 | ||
37 | 0.3 | 0.7 | 0, 0 | 1 | 98 | +7 | |
38 | 0.3 | 0.7 | 1.0,800 | 98 | +1 |
实施例6
按表6中所示,将硫化受阻酚、烷基化二苯胺和油溶性钼化合物掺混到SAE级5W-30客车用机油中。使用高分子分散剂、磺酸盐洗涤剂、ZDDP、抑泡剂、粘度指数改进剂、倾点下降剂、和稀释剂工艺用油来配制油。掺合这些油以向成品油提供700ppm的ZDDP衍生磷,然后用其量足以能有效地控制超低硫加氢裂化油中的淤渣的高分子分散剂进行配制。所用的100N的超低硫加氢裂化油如实施例1中的规定。所用的硫化受阻酚是通过一种与1997年2月19日递交的待决申请08/877533的实施例1中所述的相似方法制备的,它包含约6.6重量%的硫。所用的钼化合物如下:辛酸钼,一种得自Shepherd化学公司的包含约8.5重量%钼的无硫的钼化合物;Sakura-Lube_700,一种得自Asahi Denka Kogyo K.K.的无硫的钼的胺配合物;Molyvan_822,一种得自R.T.Vanderbilt有限公司的含硫的二硫代氨基甲酸钼;和Molyvan_855,一种得自R.T.Vanderbilt有限公司的无硫的有机钼化合物。所用的烷基化二苯胺为一种得自BFGoodrich化学有限公司的辛基/苯乙烯基烷基化二苯胺。这些油的氧化稳定性可通过实施例3中所规定的加压差示扫描量热法(PDSC)来测量。结果被示于表6中。所有的样品(油#39~53)包含97.3重量%的5W-30基油掺合物以及足够数量的工艺用稀释油以构成100重量%的包括基油掺合物、抗氧化剂和稀释油在内的总的组合物。要指出的是,如果没有本发明的一种或两种组分(油掺合物40-49),油的氧化稳定性就不好。该实施例说明,使用所有的三种组分,即二芳胺、硫化受阻酚、和油溶性钼化合物对于生产具有高度氧化稳定性(如所想望的较高的开始温度所示)的油(油掺合物50-53)是重要的。
表6.通过PDSC对抗氧化剂的评估
油# | 烷基化二苯胺(%) | 硫化受阻酚(重量%) | 钼化合物 | 油溶性钼(重量%,ppmMo) | 开始温度℃ |
39* | 177.7 | ||||
40* | 0.70 | 195.3 | |||
41* | Molyvan_855 | 0.63,500 | 180.2 | ||
42* | Molyvan_822 | 1.02,500 | 186.4 | ||
43* | 0.70 | 辛酸钼 | 0.59,500 | 196.7 | |
44* | 0.70 | Molyvan_855 | 0.63,500 | 197.1 | |
45* | 0.70 | Molyvan_822 | 1.02,500 | 201.2 | |
46* | 0.70 | Sakura-Lube_700 | 1.11,500 | 198.2 | |
47* | 0.20 | Molyvan_855 | 0.63,500 | 198.5 | |
48* | 0.20 | Molyvan_822 | 1.02,500 | 201.2 | |
49* | 0.20 | 0.70 | 202.4 | ||
50 | 0.20 | 0.70 | 辛酸钼 | 0.59,500 | 209.5 |
51 | 0.20 | 0.70 | Molyvan_855 | 0.63,500 | 209.1 |
52 | 0.20 | 0.70 | Molyvan_822 | 1.02,500 | 212.6 |
53 | 0.20 | 0.70 | Sakura-Lube_700 | 1.11,500 | 210.0 |
*对比例
本发明在其实际应用中容易出现大的变化。因此,本发明不局限于以上所提出的特定实施例。相反,本发明是处在所附的包括其在法律上适用的等同物的权利要求书的主旨和范围内的。
本专利权人不想因为公开某些已披露的具体例,以致于造成某些已披露的改进或变化不可能完全落入权利要求书的范围,根据等同原则它们应被认为是本发明的一部分。
Claims (14)
1.一种抗氧化剂体系,包含:
(A)二芳基仲胺,
(B)至少为一种的硫化烯烃和/或受阻酚,和
(C)油溶性钼化合物。
2.根据权利要求1的抗氧化剂体系,其中(B)为具有以下结构式的硫化受阻酚:
其中R为烷基,R1选自烷基或氢,Z或Z1之一为OH而另一个为氢,Z2或Z3之一为OH而另一个为氢,x为1~6,而y为0~2。
3.根据权利要求1的抗氧化剂体系,其中(B)是由至少为一种的硫化烯烃与至少为一种的硫化受阻酚组成的混合物。
4.根据权利要求1的抗氧化剂体系,其中(C)为油溶性的、无硫的钼化合物。
5.一种润滑剂组合物,包含一种具有润滑粘度的油以及权利要求1的抗氧化剂组合物。
6.根据权利要求5的润滑剂组合物,其中具有润滑粘度的油包含大于或等于90重量%的饱和物,以及小于或等于500ppm的硫。
7.根据权利要求5的润滑剂组合物,它还包含选自分散剂、洗涤剂、抗磨剂、辅助抗氧化剂、粘度指数改进剂、倾点下降剂、缓蚀剂、防锈剂、抑泡剂和摩擦改进剂中的至少为一种的。
8.根据权利要求7的润滑剂组合物,其中润滑剂组合物的总的含磷量小于850ppm。
9.根据权利要求5的润滑剂组合物,其中组分(A)存在于总的润滑剂组合物中的量为约0.05重量%~约0.5重量%。
10.根据权利要求5的润滑剂组合物,其中组分(C)是以这样的量存在的以致使得总的钼含量占总的润滑剂组合物重量的约60~约1000ppm。
11.根据权利要求5的润滑剂组合物,其中组分(B)选自硫化烯烃,其量能够使硫化烯烃向成品润滑剂组合物提供约0.05~约0.30重量%的硫;和硫化受阻酚,其量为总的润滑剂组合物的约0.3~约1. 5重量%。
12.一种含添加剂的浓缩物,包含权利要求1的抗氧化剂体系和稀释剂工艺用油。
13.根据权利要求12的含添加剂的浓缩物,它还包含至少一种的选自分散剂、洗涤剂、抗磨剂、辅助抗氧化剂、粘度指数改进剂、倾点下降剂、缓蚀剂、防锈剂、抑泡剂和摩擦改进剂中的物质。
14.一种用于减少润滑油组合物中的氧化因素的方法,该方法包括向所述的润滑油加入有效量的权利要求1的抗氧化剂体系。
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- 1998-06-18 CA CA002240973A patent/CA2240973C/en not_active Expired - Fee Related
- 1998-07-07 DE DE0892037T patent/DE892037T1/de active Pending
- 1998-07-07 DE DE69802148T patent/DE69802148T2/de not_active Expired - Lifetime
- 1998-07-07 EP EP98305406A patent/EP0892037B1/en not_active Expired - Lifetime
- 1998-07-15 CN CN98115983A patent/CN1065267C/zh not_active Expired - Fee Related
- 1998-07-16 JP JP10216542A patent/JP3135229B2/ja not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
EP0892037B1 (en) | 2001-10-24 |
CN1206041A (zh) | 1999-01-27 |
JP2001089782A (ja) | 2001-04-03 |
CA2240973A1 (en) | 1999-01-17 |
DE892037T1 (de) | 1999-08-19 |
JP3135229B2 (ja) | 2001-02-13 |
DE69802148T2 (de) | 2002-06-20 |
JPH11228981A (ja) | 1999-08-24 |
CA2240973C (en) | 1999-08-03 |
EP0892037A1 (en) | 1999-01-20 |
US5840672A (en) | 1998-11-24 |
JP3812637B2 (ja) | 2006-08-23 |
DE69802148D1 (de) | 2001-11-29 |
SG64492A1 (en) | 1999-04-27 |
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