CN101372644A - 用于具有催化转化器的发动机的、具有降低的磷含量的润滑剂组合物 - Google Patents

用于具有催化转化器的发动机的、具有降低的磷含量的润滑剂组合物 Download PDF

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CN101372644A
CN101372644A CNA2008101449050A CN200810144905A CN101372644A CN 101372644 A CN101372644 A CN 101372644A CN A2008101449050 A CNA2008101449050 A CN A2008101449050A CN 200810144905 A CN200810144905 A CN 200810144905A CN 101372644 A CN101372644 A CN 101372644A
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lubricant compositions
oil
weight
compound
rust
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M·沃杜普斯
G·C·莱霍乌雷乌克斯
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Infineum International Ltd
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Abstract

本发明涉及用于具有催化转化器的发动机的、具有降低的磷含量的润滑剂组合物。该润滑剂组合物含有(a)无灰分散剂，(b)含金属的清净剂，(c)含磷的化合物，(d)防锈剂和(e)基础油料，其中该润滑剂组合物具有小于或等于0.08重量％的磷浓度。

Description

用于具有催化转化器的发动机的、具有降低的磷含量的润滑剂组合物
技术领域
本发明涉及能够提供提高的防锈保护并具有降低的磷浓度的润滑剂组合物，特别是用于需要使用催化转化器的4冲程循环船用发动机用途的润滑剂组合物。
背景技术
润滑剂组合物由用在曲轴箱液、汽车传动液、游船发动机润滑液等中的复合添加剂配制。游船发动机用途传统上包括舷外发动机、尾机驱动发动机和舷内发动机。任何润滑剂组合物的具体化学组成取决于其性能要求。由于性能要求不断改变，因此需要新的最终润滑剂组合物。
例如，游船发动机的排放要求越来越严格。因此，预期这些发动机将开始包含催化转化器以减少排放物。本领域中公知的是，具有较低磷含量的润滑剂组合物延长了催化转化器的有效寿命。本领域中同样公知的是，在游船发动机的润滑剂组合物中包括一种或多种防锈剂，以保护发动机免受其运行中的恶劣环境的影响。
本发明提供了船用润滑剂组合物，其包含(a)无灰分散剂，(b)含金属的清净剂，(c)含磷的化合物，(d)防锈剂和(e)基础油料。本发明的润滑剂组合物具有低的磷含量，并为具有催化转化器的游船发动机中所用的润滑剂组合物提供显著的防锈保护。本发明的润滑剂组合物可以配制成符合美国船舶制造商协会(NMMA)FC-W规格的要求。
发明概要
在一个非限制性实施方案中，本发明是船用润滑剂组合物，其包含:(a)无灰分散剂，(b)含金属的清净剂，(c)含磷的化合物，(d)防锈剂和(e)基础油料，其中该润滑剂组合物中的磷浓度等于或小于0.08质量％。
在另一非限制性实施方案中，本发明是船用润滑剂组合物，其包含:(a)无灰分散剂，(b)含金属的清净剂，(c)含磷的化合物，(d)防锈剂和(e)基础油料，其中润滑剂组合物具有等于或小于0.08质量％的磷浓度，并配制成符合美国船舶制造商协会(NMMA)FC-W规格的要求。
在另一非限制性实施方案中，本发明是润滑装配有催化剂的4冲程游船发动机的方法，包括用上述润滑剂组合物润滑发动机。
发明详述
除非另行指明，说明书和权利要求书中所用的表示成分量、反应条件、尺寸、物理特性、工艺参数等的所有数字被理解为在所有情况下用术语“大约”修饰。相应地，除非作出相反的指示，下列说明书和权利要求书中所列的数值可以随试图通过本发明获得的所需性质而变。至少且不是要限制等同原则应用于权利要求的范围，各数值应该至少根据所报道的有效数字和通过应用普通舍入技术来解释。此外，本文公开的所有范围被理解为包括开端和末端范围值和其中所含的任何和所有子范围。例如，“1至10”的所述范围应该被认为包括在最小值1和最大值10之间(包括端点)的任何和所有的子范围；也就是说，以最小值1或更大值开始并以最大值10或更小值结束的所有子范围，例如5.5至10。
在下列说明书中提到的任何美国专利或专利文献或参考文献都将经引用并入本文，且被理解为全文并入。
本发明是船用润滑剂组合物，其包含(a)无灰分散剂，(b)含金属的清净剂，(c)含磷的化合物，(d)防锈剂和(e)稀释剂，其中该润滑剂组合物中的磷浓度等于或小于0.08质量％。
根据本发明，该润滑剂组合物包含无灰分散剂。合适的无灰分散剂包括但不限于烃基琥珀酰亚胺、烃基琥珀酰胺、混合的烃基取代的琥珀酸的酯/酰胺、烃基取代的琥珀酸的羟基酯、和烃基取代酚、甲醛与多胺的曼尼希缩合产物。多胺与烃基取代的苯基酸的缩合产物也是合适的无灰分散剂。也可以使用上述无灰分散剂的混合物。
本发明中所用的无灰分散剂是公知的，并在专利文献中描述了它们的制备方法。烃基取代的琥珀酰亚胺和琥珀酰胺及其制备方法描述在美国专利第3,018,247、3,018,250、3,018,291、3,361,673和4,234,435号中。混合的烃基取代的琥珀酸的酯-酰胺及其制备方法描述在美国专利第3,576,743、4,234,435和4,873,009中。曼尼希分散剂及其制备方法描述在美国专利第3,368,972、3,413,347、3,539,633、3,697,574、3,725,277、3,725,480、3,726,882、3,798,247、3,803,039、3,985,802、4,231,759和4,142,980中。胺分散剂及其制备方法描述在美国专利第3,275,554、3,438,757和3,565,804中。
在本发明的非限制性实施方案中，无灰分散剂包含烯基琥珀酰亚胺和/或烯基琥珀酰胺。可以使用本领域中公知的方法制备烯基琥珀酰亚胺和/或烯基琥珀酰胺分散剂。
根据本发明，可以用许多试剂后处理无灰分散剂，这是本领域技术人员已知的。例如，可以用硼酸化试剂处理无灰分散剂，这是本领域中公知的。
在本发明的一个非限制性实施方案中，基于润滑剂组合物的总重量，无灰分散剂的存在量为1.1至18.5重量％，例如3.0至12.0重量％，或3.5至4.5重量％。除非另行指明，本文所含的所有重量百分比都基于活性成分。
根据本发明，润滑剂组合物包含含金属的清净剂。含金属的清净剂既充当用于减少或去除沉积物的清净剂，又充当酸中和剂或防锈剂，由此减少磨损和腐蚀并延长发动机寿命。本发明的含金属的清净剂通常包含具有极性头和长疏水尾的化合物。极性头可以包含酸有机化合物的金属盐。
在本发明的一个非限制性实施方案中，该盐含有基本化学计算量的金属，并具有根据ASTM D-2896测得的0至80的总碱值(TBN)。这类盐通常被称作“正”盐或“中性”盐。
在本发明的另一非限制性实施方案中，含金属的清净剂是高碱性清净剂，它是通过使过量的金属化合物(例如氧化物或氢氧化物)与酸气体(例如二氧化碳)反应而形成的。高碱性清净剂包含中和的清净剂作为金属碱(例如碳酸盐)胶束的外层。这类高碱性清净剂通常具有150或更高的TBN。
合适的含金属的清净剂还包括金属的油溶性中性和高碱性磺酸盐、苯酚盐、硫化苯酚盐、硫代膦酸盐、水杨酸盐、环烷酸盐及其它油溶性羧酸盐。例如，金属可以是碱金属或碱土金属，例如钠、钾、锂、钙和镁。在本发明的一个非限制性实施方案中，金属是钙、镁、或钙和/或镁与钠的混合物。
在本发明的一个非限制性实施方案中，基于润滑剂组合物的总重量，所述含金属的清净剂的存在量为0.2至3.0重量％，例如0.8至2.0重量％或1.0至1.4％。
根据本发明，润滑剂组合物包含具有抗磨性的含磷的化合物。在一个非限制性实施方案中，所述含磷的化合物是二烃基二硫代磷酸锌(ZDDP)。合适的ZDDP的实例包括(a)具有式Zn[SP(S)(OR1)(OR2)]2的那些，其中R1和R2含有1至18个碳原子，和(b)其中仲烷基比伯烷基多的ZDDP，例如基于总烷基的质量具有至少50质量％的仲烷基的ZDDP。ZDDP和制备ZDDP的方法是本领域中公知的。参见美国专利第6,642,188号，其经此引用并入本文。
在本发明一个非限制性实施方案中，所述含磷的化合物的存在量为在最终油中提供0.03至0.08重量％、例如0.05至0.08或0.07至0.08重量％的磷含量。
根据本发明，润滑剂组合物包含一种或多种防锈剂。合适的防锈剂包括但不限于下列:脂肪酸、烯基琥珀酸半酯、脂肪酸皂、脂肪酸与多元醇的酯、乙氧基化的胺、脂肪酸胺、氧化的石蜡、烷基多氧化亚乙基醚、非离子型多氧化亚烷基多元醇及其酯、其它多氧化亚烷基酚、阴离子型烷基磺酸、烷基萘磺酸的金属盐，例如可获自King Industries的“NA-SUL 129”，和亚磷酸氢二烷基酯或磷酸氢二烷基酯。也可以使用防锈剂的混合物。
在本发明的一个非限制性实施方案中，防锈剂包含乙氧基化的壬基酚或C4-C18烷基酚防锈剂(它们每摩尔含有大约2至10摩尔氧化亚乙基)与四丙基琥珀酸的混合物。
在本发明的一个非限制性实施方案中，润滑剂组合物中防锈剂的含量为能够提供与NMMA参比油5973的性能相等或更好的防锈保护。因此，在此实施方案中，当NMMA参比油5973落在20-40％锈蚀的范围内时，所述润滑剂组合物表现出比参比油5973低的NMMA FC-W锈蚀试验值。
在本发明的一个非限制性实施方案中，基于润滑剂组合物的总重量，防锈剂的存在量为0.1至2.0重量％，例如0.2至1.0或0.2至0.6重量％。
根据本发明，润滑剂组合物包含基础油料。基础油料包含第I类、第II类、第III类、第IV类和/或第V类基础油料掺合物。在美国石油学会(API)出版物“Engine Oil Licensing and Certification System(发动机润滑油注册与证明系统)”，Industry Services Department，第14版，1996年12月，Addendum，1998年12月1日中定义了各种基础油料掺合物。在本发明的一个非限制性实施方案中，基础油料的存在量为大于或等于润滑剂组合物的50重量％。
在本发明的一个非限制性实施方案中，润滑剂组合物包含含钼的化合物。合适的含钼的化合物包括各种油溶性有机钼化合物。在本发明的一个非限制性实施方案中，所述含钼的化合物包含二烷基二硫代氨基甲酸盐、二烷基二硫代磷酸盐、二烷基二硫代亚膦酸盐、黄原酸盐、噻吨盐、羧酸盐或其混合物。
在本发明的一个非限制性实施方案中，所述含钼的化合物的存在量为，基于润滑剂组合物的总重量，提供0.001至1.0重量％，例如0.002至0.5重量％或0.005至0.1重量％的钼浓度。
根据本发明，可以在润滑剂组合物中加入各种任选的化合物和材料。这些任选的化合物和材料包括但不限于摩擦改性剂、粘度改进剂、稳定剂、氧化抑制剂、破乳剂、防沫添加剂、增粘剂和倾点下降剂。
在本发明的一个非限制性实施方案中，润滑剂组合物进一步包含粘度改进剂。合适的粘度改进剂包括但不限于油溶性聚合物，例如通过凝胶渗透色谱法或光散射法测得的重均分子量为大约10,000至1,000,000、优选大约20,000至500,000的聚酯。合适的粘度改进剂的代表性实例是聚异丁烯、乙烯与丙烯和更高α烯烃的共聚物、聚甲基丙烯酸酯/盐、聚甲基丙烯酸烷基酯、甲基丙烯酸酯/盐共聚物、不饱和二羧酸与乙烯基化合物的共聚物，苯乙烯与丙烯酸酯的互聚物、和苯乙烯/异戊二烯、苯乙烯/丁二烯和异戊二烯/丁二烯的部分氢化的共聚物、以及丁二烯与异戊二烯和异戊二烯/二乙烯基苯的部分氢化的均聚物。
合适的粘度改进剂还包括乙烯基取代的芳族化合物与共轭二烯的氢化共聚物。这些氢化苯乙烯-异戊二烯嵌段共聚物产物可作为Infineum SV140和Infineum SV150获自Infineum USA L.P.(New Jersey)。
在本发明的另一非限制性实施方案中，润滑剂组合物进一步包含本领域中公知的下列一种或多种:稳定剂、氧化抑制剂、破乳剂、防沫添加剂、和倾点下降剂。
已知氧化抑制剂的实例包括受阻酚、烷基酚硫代酯(优选具有C5至C12烷基侧链)的碱土金属盐、壬基酚硫化钙、无灰油溶性苯酚盐、硫化苯酚盐、硫化烃、金属硫代氨基甲酸盐、具有至少两个直接与氮成分连接的芳基的芳族胺、和如美国专利第4,867,890号中所述的油溶性铜化合物。
合适的破乳剂的实例包括EP 330,522中所述的那些。合适的倾点下降剂的实例包括富马酸C8至C18二烷基酯/乙酸乙烯酯共聚物、聚甲基丙烯酸烷基酯，等等。合适的防沫添加剂的实例包括氟硅氧烷和聚硅氧烷化合物，例如硅油或聚二甲基硅氧烷。
本发明的润滑剂组合物可以使用本领域中公知的方法和技术由上述各组分配制。在本发明的一个非限制性实施方案中，本发明的润滑剂组合物可以配制成符合美国船舶制造商协会(NMMA)FC-W规格的要求。
本发明还包括用于配制所述润滑剂组合物的复合添加剂。
在本发明的一个非限制性实施方案中，当润滑剂组合物进行ASTMD4683试验时，其在如ASTM D6278剪切稳定性试验中所述经受30个剪切周期后，表现出在150℃等于或大于3.3cP的高温高剪切(“HTHS”)粘度。ASTM D6278模拟了油在发动机中可能承受的剪切类型。在150℃下3.3cP的最小HTHS粘度确保了足够的粘度，可对发动机轴承适当地润滑。
本发明的润滑剂组合物具有等于或小于0.08质量％的磷含量，并提供了改进的防锈保护。因此，该润滑剂组合物理想地适用在配有催化转化器的船用发动机中。具有低磷含量的润滑剂组合物在工业中已知有助于延长催化剂寿命。
本发明还包括润滑装配有催化剂的4冲程游船发动机的方法，包括用上述润滑剂组合物润滑该发动机。
实施例
通过五个非限制性实施例，实施例1-5，例证本发明。各个实施例通过将指定的组分以下表1中所示的量混合并掺合而制备。使用标准实验室掺合技术和温度制备实施例中的油。
表1.实施例1-5的组成信息
 
组分 实施例1[活性成分的重量％] 实施例2[活性成分的重量％] 实施例3[活性成分的重量％] 实施例4[活性成分的重量％] 实施例5[活性成分的重量％]
烯基琥珀酰亚胺无灰分散剂 3.543 3.543 0.000 2.943 2.943
硼酸化的烯基琥珀酰亚胺无灰分散剂 0.000 0.675 4.447 0.720 0.720
高碱性磺酸钙清净剂 1.018 1.018 0.000 0.000 0.000
高碱性磺酸镁清净剂 0.000 0.000 0.726 0.719 0.719
碳酸化的低碱值硫化苯酚钙清净剂 0.230 0.230 0.487 0.483 0.483
烯基琥珀酸酐 0.360 0.360 0.000 0.144 0.144
 
含磷的化合物[二烃基二硫代磷酸锌] 0.698 0.698 0.705 0.705 0.705
抗氧化剂[壬基烷基化的二苯基胺] 0.600 0.600 0.000 0.625 0.625
抗氧化剂[C7-C9受阻酚] 0.000 0.000 0.339 0.335 0.335
破乳剂 0.000 0.000 0.003 0.000 0.000
含钼的化合物[二烷基二硫代氨基甲酸钼 0.042 0.042 0.042 0.023 0.023
60,000cSt硅酮防沫添加剂 0.000 0.000 0.000 0.002 0.002
聚二甲基-硅氧烷防沫添加剂 0.001 0.001 0.000 0.000 0.000
12,500cSt硅酮防沫添加剂 0.000 0.000 0.001 0.000 0.000
单油酸甘油酯(GMO)摩擦改性剂 0.200 0.200 0.200 0.200 0.000
乙氧基化的壬基酚防锈剂 0.360 0.360 0.120 0.150 0.200
四丙基琥珀酸防锈剂 0.252 0.252 0.084 0.105 0.200
富马二烷基酯/乙酸乙烯酯共聚物倾点下降剂 0.300 0.300 0.000 0.000 0.000
倾点下降剂[获自Lubrizol的LZ6662A] 0.000 0.000 0.200 0.200 0.000
粘度改进剂[Lubegard2004] 0.000 0.000 8.550 11.000 0.000
粘度改进剂[Infineum SV205] 0.000 0.000 0.000 0.000 6.000
V类基础油料[TMP酯] 2.000 2.000 0.000 0.000 0.000
IV类基础油料[聚α烯烃] 8.000 8.000 0.000 0.000 0.000
II类基础油料 0.000 0.000 35.900 30.000 0.000
I类基础油料 82.396 81.721 48.196 51.646 86.601
磷浓度1 0.075 0.075 0.075 0.075 0.075
1基于组合物中ZDDP的量的计算值
对实施例1-4进行修改的NMMA FC-W锈蚀试验。NMMA FC-W锈蚀试验提供了用于定性评测发动机油的防腐蚀保护性能的方法。NMMAFC-W锈蚀试验程序使用由NMMA认可的钢试块(从实际汽缸套上切下)，钢试块在湿润盐环境中悬挂24小时。在该试验的这种修改中，明确地遵循NMMA FC-W试验程序，不同之处在于为了筛选目的每种油使用两个试块而非每种油四个试块。
每种油使用四个试块根据NMMA FC-W进行实施例5。根据该程序，一个试块作为统计异常值舍去。
修改的NMMA FC-W锈蚀试验的结果见下表2。表2显示了试块的平均锈蚀试验值和试块的单独锈蚀试验值。单独锈蚀试验值在括号中。还显示了NMMA 5973参比油在试验过程中的锈蚀试验值，以支持所有试验的有效性。
表2.修改的NMMA FC-W锈蚀试验结果
 
实施例1 实施例2 实施例3 实施例4 实施例5
平均锈蚀试验值 14(15和12) 17(20和14) 35(33和37) 36(23和48) 25(30，24和22)
NMMA5973的平均锈蚀试验值 39(38和39) 21(22和20) 40(40和40) 37(38和36) 38(40，40，38和36)
结果 通过 通过 通过 通过 通过
为了通过NMMA FC-W锈蚀试验，实施例必须表现出等于或优于被标作NMMA 5973的并行参比油的锈蚀性能。另外，为了使NMMA FC-W锈蚀试验的结果有效，NMMA 5973必须落在20-40％锈蚀的范围内。如表2中所示，本发明的所有实施例都通过了该试验。

Claims (17)

1.润滑剂组合物，包含:
a.无灰分散剂；
b.含金属的清净剂；
c.含磷的化合物；
d.防锈剂；和
e.基础油料，
其中所述润滑剂组合物具有等于或小于0.08质量％的磷浓度。
2.根据权利要求1的润滑剂组合物，其中所述防锈剂的存在量为，在NMMA FC-W锈蚀试验中，当NMMA参比油5973落在20-40％锈蚀的范围内时，能够提供与参比油5973的性能相等或更好的防锈保护。
3.根据权利要求2的润滑剂组合物，其中基于润滑剂组合物的总重量，所述防锈剂的存在量为0.1至2.0重量％。
4.根据权利要求1的润滑剂组合物，其中所述无灰分散剂选自由烃基琥珀酰亚胺、烃基琥珀酰胺、混合的烃基取代的琥珀酸的酯/酰胺、烃基取代的琥珀酸的羟基酯、和烃基取代酚、甲醛与多胺的曼尼希缩合产物及其混合物组成的组。
5.根据权利要求1的润滑剂组合物，其中基于润滑剂组合物的总重量，所述无灰分散剂的存在量为1.1至18.5重量％。
6.根据权利要求1的润滑剂组合物，其中所述含金属的清净剂选自由金属的油溶性中性和高碱性磺酸盐、苯酚盐、硫化苯酚盐、硫代膦酸盐、水杨酸盐、和环烷酸盐、其它油溶性羧酸盐及其混合物组成的组。
7.根据权利要求1的润滑剂组合物，其中基于润滑剂组合物的总重量，所述含金属的清净剂的存在量为0.2至3.0重量％。
8.根据权利要求1的润滑剂组合物，其中所述基础油料选自由第I类掺合油、第II类掺合油、第III类掺合油、第IV类掺合油、第V类掺合油及其混合物组成的组。
9.根据权利要求1的润滑剂组合物，进一步包含含钼的化合物。
10.根据权利要求9的润滑剂组合物，其中所述含钼的化合物的存在量为，基于润滑剂组合物的总重量，提供0.001至1.0重量％的钼浓度。
11.根据权利要求1的润滑剂组合物，其中所述含磷的化合物是ZDDP。
12.根据权利要求1的润滑剂组合物，进一步包含下列物质的一种或多种:摩擦改性剂、粘度改进剂、稳定剂、氧化抑制剂、破乳剂、防沫添加剂、增粘剂和倾点下降剂。
13.船用润滑剂组合物，其包含:
a.无灰分散剂；
b.含金属的清净剂；
c.含磷的化合物；
d.防锈剂；和
e.基础油料，
其中该润滑剂组合物具有等于或小于0.08质量％的磷浓度，并配制成符合美国船舶制造商协会(NMMA)FC-W规格的要求。
14.根据权利要求13的船用润滑剂组合物，进一步包含含钼的化合物。
15.根据权利要求14的船用润滑剂组合物，其中所述含钼的化合物的存在量为，基于润滑剂组合物的总重量，提供0.001至1.0重量％的钼浓度。
16.根据权利要求13的船用润滑剂组合物，其中当该润滑剂组合物进行ASTM D4683试验时，其在按照ASTM D6278剪切稳定性试验中所述经受30个剪切周期之后，在150℃具有等于或大于3.3cP的HTHS粘度。
17.润滑装配有催化剂的4冲程船用发动机的方法，包括:
用包含无灰分散剂、含金属的清净剂、含磷的化合物、防锈剂和基础油料的润滑剂组合物润滑发动机，其中该润滑剂组合物具有小于或等于0.08质量％的磷浓度。
CNA2008101449050A 2007-08-09 2008-08-07 用于具有催化转化器的发动机的、具有降低的磷含量的润滑剂组合物 Pending CN101372644A (zh)

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