CN1199087A - 柴油机油组合物 - Google Patents

柴油机油组合物 Download PDF

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CN1199087A
CN1199087A CN98109257A CN98109257A CN1199087A CN 1199087 A CN1199087 A CN 1199087A CN 98109257 A CN98109257 A CN 98109257A CN 98109257 A CN98109257 A CN 98109257A CN 1199087 A CN1199087 A CN 1199087A
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片渕正
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Abstract

本发明公开了一种柴油机油组合物,其含有润滑油基础油和一种或多种金属清净分散剂,该金属清净分散剂选自高碱性碱土金属磺酸盐、酚盐和水杨酸盐。该组合物的总的磷的含量抑制在100ppm(重)或更少,由此提供具有很好的氧化安定性和耐磨性能的柴油机油组合物。

Description

柴油机油组合物
本发明涉及柴油机油组合物，更具体地说，本发明涉及适用于船用和柴油发电厂的中速柴油机的柴油机油组合物。
在船用柴油机或发电厂用的柴油机，特别是中速柴油机中，机油消耗的突然增加的现象是一个问题。该突然增加的现象是由于发动机中的环和衬套之间的条件的变化，即由于环和衬套之间的机油降解的产物或很差的润滑性能引起的环的粘着造成的。换句话说，机油的降解和润滑性能的降低，特别是机油的耐磨性能的降低在油耗的突然增加方面起着重要的作用。于是，由于发生了油耗的突然增加而使机油的使用期限期满。在机油使用的过程中特殊组分的降解可能影响油耗，因为在新鲜机油使用时几乎没有观察到油耗的变化。鉴于具有长的使用期限的机油有很好的氧化安定性和耐磨性能，就需要开发氧化稳定性和耐磨性能都很好的机油。日本专利申请公开号7-197067公开了一种机油添加剂，该机油添加剂含有特殊的高碱性或中性磺酸盐与特殊的聚烯基琥珀酰亚胺和二烷基二硫代磷酸锌的混合物。但是，该添加剂的氧化安定性和耐磨性能都很差。
鉴于上述而作出了本发明，本发明的一个目的是提供一种具有很好的氧化安定性和耐磨性能的柴油机油组合物。
本发明人已经进行了认真地研究，发现通过使用含有规定的高碱性碱土金属化合物的清净分散剂和通过调节规定的元素组分的量可以有效的达到上述的目的。
因此，本发明提供一种柴油机油组合物，该柴油机油组合物含有润滑油基础油和一种或多种金属清净分散剂，该金属清净分散剂选自高碱性碱土金属磺酸盐、酚盐和水杨酸盐，其中，总的磷含量是100ppm(重)或更少，优选70ppm(重)或更少。
在本发明的一个优选的实施方案中，提供一种具有总碱值15-50mgKOH/g的柴油机油组合物。
在本发明的另一个优选的实施方案中，提供一种具有总的氮含量和总的磷含量的总数为150ppm(重)或更少的柴油机油组合物。
另外，在本发明的一个特别优选的实施方案中，提供一种具有总的氮含量为50ppm(重)或更少的柴油机油组合物。
下面将描述实施本发明的模式。
本发明的柴油机油组合物可以用在各种发动机中，例如船用发动机和柴油发电厂的发动机，特别优选的是用于速度为200-1500rpm，优选300-1300rpm的中速柴油机。这些柴油机一般地输出功率为100-30,000HP，优选500-20,000HP。在这些柴油机中，润滑油可能被未用的燃料、燃烧残渣和在燃料以及金属分散剂中所含的硫所产生的酸性物质之间的反应产生的淤泥污染。特别优选的是本发明的柴油机油组合物用在装配有除渣设备例如大型的过滤器、滤净器或离心分离器的柴油发动机中。
作为在本发明的柴油机油组合物中的润滑油基础油，可以使用在100℃的运动粘度为3-35mm2/s，优选8-25mm2/s的矿物油和/或合成油。当该基础油的运动粘度过高时，提供到润滑部件的润滑油就少，而当该基础油的运动粘度过低时，其蒸汽压就高，使得产生高比例油耗的缺点。对于倾点没有提出特别的限制，倾点是低温流动性的指数，倾点为-10℃或更低是优选的。另外，在基础油中所含的氮的总量优选40ppm重或更少，更优选30ppm重或更少。当在基础油中总氮含量过高时，形成的污泥的量就增加，就导致增加了润滑油的降解。
可以根据其用途从各种矿物油和合成油中选择矿物油和合成油。矿物油的例子包括石蜡基矿物油、环烷基矿物油和中间基原油。具体的例子包括轻中性油、中间中性油、重中性油和光亮油料。
合成油的例子包括聚-α-烯烃、α-烯烃共聚物、聚丁烯、烷基苯、多元醇酯、二元酸酯、聚氧亚烷基二醇、聚氧亚烷基二醇酯、聚氧亚烷基二醇醚和位阻酯。
作为基础油的这些油可以单独使用或其两种或多种混合使用，并且矿物油和合成油可以混合使用。
在润滑油基础油中加入的金属清净分散剂选自高碱性碱土金属磺酸盐、酚盐和水杨酸盐。它们当中，高碱性碱土金属水杨酸盐是优选的。
该清净分散剂优选地具有总碱值100-600mgKOH/g(JIS K-2501：高氯酸盐法)，特别是120-500mgKOH/g。当该碱值过低时，就需要大量的分散剂来得到好的结果，其是不经济的；而该碱值过高时，润滑油的灰含量增加，就招致形成大量的沉淀的危险。
高碱性碱土金属磺酸盐，其是各种磺酸的碱土金属盐，其一般的是通过各种碱土金属磺酸盐的碳化得到的。磺酸的例子包括芳族石油磺酸、烷基磺酸、芳基磺酸和烷基芳基磺酸。具体例子包括十二烷基苯磺酸、二月桂基十六烷基苯磺酸、石蜡取代的苯磺酸、聚烯烃取代的苯磺酸、聚异丁烯取代的苯磺酸和萘磺酸。
高碱性碱土金属酚盐，其是烷基酚或硫化的烷基酚的碱土金属盐，一般的是通过烷基酚或硫化的烷基酚的碱土金属盐的碳化得到的。
高碱性碱土金属水杨酸盐，其是烷基水杨酸的碱土金属盐，一般的是通过下面的步骤得到的：用C8-C18α-烯烃烷基化酚，通过科尔柏-施密特反应引入羧基，双分解和碳化得到的。烷基水杨酸的例子包括十二烷基水杨酸、十二烷基甲基水杨酸、十四烷基水杨酸、十六烷基水杨酸、十八烷基甲基水杨酸和二辛基水杨酸。
上述的碱土金属磺酸盐、碱土金属酚盐和碱土金属水杨酸盐的碱土金属的例子包括钙、钡和镁，鉴于其效果钙是优选的。
在本发明中，上述的金属清净分散剂可以单独使用或其两种或多种混合使用。基于组合物的总量，优选的是其加入量为5-40％(重)，更优选10-30％(重)。当金属清净分散剂的量为5％(重)或更少时，其结果是耐磨性能和氧化安定性差，而当金属清净分散剂的量超过40％(重)时，就不能得到同等量的加入的清净分散剂的效果。
在本发明的柴油机油组合物中总的磷的含量是100ppm(重)或更少，优选70ppm(重)或更少，特别优选30ppm(重)或更少。当总的磷的含量过高时，在润滑油中的酸性物质的含量就增加，很容易导致在氧化诱导降解步骤中形成淤泥。
本发明的柴油机油组合物中的总碱值必须调整到15-50mgKOH/g(JISK-2501：高氯酸盐法)，优选20-40mgKOH/g，当该碱值过低时，对酸的中和能力就差，而该碱值过高时，就招致形成大量的沉淀。
在本发明的柴油机油组合物中的总的氮含量和总的磷含量的总数优选地调整到150ppm(重)或更少，更优选90ppm(重)或更少，特别优选70ppm(重)或更少。该总数太大可能很容易导致在氧化诱导降解步骤中形成淤泥。
另外，本发明的柴油机油组合物中的总的氮含量优选调节到50ppm(重)或更少，更优选30ppm(重)或更少。该总的氮含量太高可能很容易导致在氧化诱导降解步骤中形成淤泥。
通过在润滑油基础油中加入上述的金属清净分散剂得到本发明的组合物。一般的，该组合物还可以含有添加剂，例如抗氧化剂、粘度指数改进剂、金属钝化剂、降凝剂、抗磨剂、抑泡剂或极压添加剂，以便保持润滑油的基本的特征。对添加剂没有提出特别的限制，各种各样的常规的已知添加剂都可以使用。基于组合物的总量，用量可以为0.05-2％(重)的抗氧化剂的例子包括胺例如烷基化的二苯胺或苯基-α-萘胺，和苯酚化合物例如2，6二叔丁基酚或4，4’-亚甲基双(2，6-二叔丁基酚)。基于组合物的总量，用量可以为0.5-30％(重)的粘度指数改进剂的例子包括聚(甲基丙烯酸甲酯)、聚异丁烯、乙烯-丙烯共聚物、苯乙烯-异戊二烯共聚物和加氢的苯乙烯-丁二烯共聚物。基于组合物的总量，用量可以为0.005-1％(重)的金属钝化剂的例子包括苯并三唑、噻二唑和烯基琥珀酸酯。基于组合物的总量，用量可以为0.01-1％(重)的降凝剂的例子包括聚(甲基丙烯酸烷基酯)和聚烷基苯乙烯。基于组合物的总量，用量可以为0.1-3％(重)的抗磨剂的例子包括有机钼化合物例如MoDTP和MoDTC；有机锌化合物例如ZnDTP；有机硼化合物例如硼酸烷基硫醇酯；石墨；二硫化钼；硫化锑；硼化合物；和聚四氟乙烯。基于组合物的总量，用量可以为0.0005-1％(重)的消泡剂的例子包括二甲基聚硅氧烷和聚丙烯酸酯。基于组合物的总量，用量可以为0.1-15％(重)的极压添加剂的例子包括硫化脂肪和二烯丙基二硫化物。当上述的添加剂是含有氮和磷的化合物时，由于这些组分在添加剂中，所以在上述的润滑油组合物中氮和/或磷的总量应该调节。
                  实施例
下面将用实施例详细地描述本发明，但是这些实施例不是要限制本发明。实施例1-3和比较例1和2
按表1所规定的比例混合组合物的组分，由此得到实施例和比较例的柴油机油组合物。把实施例和比较例的柴油机油组合物的总碱值调节到30mgKOH/g (JSK-2501；高氯酸盐法)。把这些实施例和比较例的柴油机油组合物按照下述的方法进行氧化安定性试验和耐磨试验，结果列于表1。(1)氧化安定性试验
按照“内燃机油的氧化安定性试验”(JIS K—2514)进行ISOT试验。简单地说，通过下面的步骤进行该试验：把铁-钢片放在机油中，在165℃搅拌该油，按照JIS K—2501(盐酸法)，在96小时之后测定总碱值。(2)耐磨试验(四球机负载能力试验)
为了评价该机油的耐磨性能、摩擦界面之间油-膜形成、耐磨性能的重要因素，在下面的条件下进行评价：
试验装置：Soda的四球试验装置，
旋转球的转速：500rpm，
油温：80℃，
评价方法：当液压负载以每3分钟增加0.5kg/cm2从0.5kg/cm2逐渐增加时，测定油压，观察在该油压下旋转球和固定球之间的电导性。
                                表1
  组分％(重)   实施例1   实施例2   实施例3   比较例1  比较例2
基础油(1)*1     84.1     -     83.2     83.7     82.8
基础油(2)*2     -     88.5     -     -     -
酚酸钙*3     3.8     5.8     3.8     3.8     3.8
水杨酸钙*4     12.1     -     12.1     12.1     12.1
磺酸钙*5     -     5.7     -     -     -
Zn-DTP     -     -     -     0.4     0.4
双烯基琥珀酰亚胺*6     -     -     0.9     -     0.9
    总氮(wt、ppm)     ≤5     32     100     -     100
    总磷(wt、ppm)     ≤10     ≤10     ≤10     300     300
 ISOT试验后的总碱值*7     8.0     6.0     4.5     4.0     3.5
 四球机试验(kg/cm2)     4.0     4.0     3.5     3.0     2.5
*1：高纯化石蜡基矿物油，运动粘度10mm2/s(100℃)*2：溶剂提纯的石蜡基矿物油，运动粘度10mm2/s(100℃)*3：总碱值：250mgKOH/g(JIS K-2501：高氯酸盐法)*4：总碱值：170mgKOH/g(JIS K-2501：高氯酸盐法)*5：总碱值：270mgKOH/g(JIS K-2501：高氯酸盐法)*6：聚异丁烯基的数均分子量1000；氮含量1.1％(重)*7：mgKOH/g(JIS K-2501：盐酸法)
如上所述，本发明的柴油机油组合物有很好的氧化安定性和耐磨性能，其特别适合作为船用或发电用的中速柴油机油。

Claims (8)

1.一种柴油机油组合物，其含有润滑油基础油和一种或多种金属清净分散剂，该金属清净分散剂选自高碱性碱土金属磺酸盐、酚盐和水杨酸盐，其中，组合物的总的磷的含量是100ppm(重)或更少。
2.根据权利要求1的柴油机油组合物，其中该组合物的总碱值是15-50mgKOH/g。
3.根据权利要求1的柴油机油组合物，其中该组合物的总的氮含量和总的磷含量的总数是150ppm(重)或更少。
4.根据权利要求1的柴油机油组合物，其中该组合物的总的氮含量为50ppm(重)或更少。
5.根据权利要求1的柴油机油组合物，其中该组合物的总的磷含量为70ppm(重)或更少。
6.根据权利要求5的柴油机油组合物，其中该组合物的总碱值是15-50mgKOH/g。
7.根据权利要求5的柴油机油组合物，其中该组合物的总的氮含量和总的磷含量的总数是90ppm(重)或更少。
8.根据权利要求5的柴油机油组合物，其中该组合物的总的氮含量为30ppm(重)或更少。
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