CN107406784A - 船用柴油机润滑油组合物 - Google Patents
船用柴油机润滑油组合物 Download PDFInfo
- Publication number
- CN107406784A CN107406784A CN201680007190.7A CN201680007190A CN107406784A CN 107406784 A CN107406784 A CN 107406784A CN 201680007190 A CN201680007190 A CN 201680007190A CN 107406784 A CN107406784 A CN 107406784A
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- CN
- China
- Prior art keywords
- detersive
- parlkaline
- oil
- isomerization
- lubricant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000314 lubricant Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 47
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- 238000006317 isomerization reaction Methods 0.000 claims abstract description 34
- 239000002199 base oil Substances 0.000 claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003599 detergent Substances 0.000 claims abstract description 24
- -1 alkyl aryl sulphonic acid Chemical compound 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 49
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- 239000010687 lubricating oil Substances 0.000 claims description 15
- 150000001447 alkali salts Chemical class 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 claims description 9
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- 239000000126 substance Substances 0.000 claims description 4
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
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- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
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- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/02—Sulfurised compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/0406—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbased sulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
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Abstract
一种具有约5至约120的TBN的船用柴油机润滑油组合物，其含有润滑粘度的基础油，过碱性烷基芳基C10‑40磺酸盐清净剂和过碱性异构化C10‑40正α‑烯烃基酚盐清净剂，其中所述过碱性磺酸盐清净剂与所述过碱性异构化正α‑烯烃基酚盐清净剂的重量比范围从1：9至9：1。
Description
技术领域
本发明涉及船用润滑油组合物，特别是用作十字头发动机和柱塞发动机的船用柴油机润滑剂。所述润滑油组合物显示出改善的氧化稳定性、粘度增加控制、清净性和耐水性。
背景技术
柴油发动机被用作海洋船舶运行的内燃机，并且通常分类为慢速、中速或高速发动机。
慢速柴油发动机在尺寸和操作方法上是独特的。发动机转速每分钟60到约200转条件下这些发动机的输出可高达100000制动马力。它们一般为十字头设计且以二冲程循环运行。归因于这些发动机的设计和结构，其中十字头将点火气缸与曲轴箱分开，并且填料箱完成密封，气缸和曲轴箱由船用油缸油和船用系统油分别润滑。
船用气缸润滑剂的主要功能是在气缸套和活塞环之间提供强油膜。在发动机运行期间消耗船用气缸润滑剂，因此在总损失的基础上润滑气缸。虽然定期补充新鲜的润滑油以补偿消耗的部分，但是暴露于热和其他应力(例如使用残留燃料)会导致增加量的氧化硫化合物和燃烧残余物在润滑油中增加并保留。因此，在发动机长时间连续运转后，润滑油由于沉积物污染和油的氧化而遭受劣化和粘度增加。
船用系统油润滑十字头船用柴油发动机的曲轴箱，并且可以冷却发动机的零件，特别是活塞顶。在一些发动机中，系统油还具有润滑齿轮和燃料泵的功能。系统油通常重要的性能是氧化稳定性、粘度增加控制和油的清净性。
另一方面，中速发动机典型的在约250至约1100rpm的范围内运行，并且通常基于四冲程循环来运行。这些发动机通常是柱塞设计。与慢速发动机相比，连杆直接连接到活塞上。因此，在柱塞发动机中使用单个润滑剂用于曲轴箱和气缸润滑。因此，这些油需要具有在运动表面之间形成保护层、中和酸并保持污染物悬浮在油中的能力，这些特性可能会受到油氧化反应的不利影响而导致粘度增加、中和能力及清净性的损失。
在本领域中需要在各种船舶应用中表现出改进的氧化稳定性、粘度增加控制、清净性和耐水性的润滑油组合物。使用过碱性含金属的清净剂如碱土金属磺酸盐、酚盐和水杨酸盐是本领域已知的用于中和由燃料燃烧产生的氧化硫并分散燃料沉积物如污泥的添加剂。
使用中链至长链烷基芳族化合物来制备大量添加剂和表面活性剂。这类化合物的实例是用于润滑剂添加剂的烷基芳族酚盐。酚盐由于它们的清净性和抗氧化性能而得到广泛使用。
低分子量烷基酚例如四丙烯基苯酚(TPP)被生产商用作硫化的过碱性酚盐的原料。通常在制备硫化的过碱性酚盐时，最终反应产物中存在未反应的烷基苯酚。美国化学理事会石油添加剂专门研究小组资助的最近在大鼠中的生殖毒性研究表明，高浓度的未反应TPP可以在雄性和雌性生殖器官中造成不利影响。
为了降低对用户的任何潜在健康风险并且避免潜在的监管问题，需要降低过碱性且硫化的烷基化羟基芳族化合物的盐中未反应的低分子量烷基羟基芳族化合物的量。线性烯烃是避免衍生的烷基酚的生殖毒性的可能替代物；然而，所述烯烃的线性度可导致含有衍生的硫化过碱性酚盐的润滑油的差的低温性能。
本发明旨在通过使用最佳比例的特定组合的过碱性清净剂来实现船用柴油机润滑剂性能的改进。
发明概述
本发明的第一方面是一种具有约5至约120的TBN的船用柴油机润滑剂组合物，包括：
(a)主要量的润滑粘度的基础油；
(b)第一清净剂，其为过碱性C10-40烷基芳基磺酸的碱土金属盐清净剂；和
(c)第二清净剂，其为过碱性异构化C10-40正α烯烃基硫化酚的碱土金属盐清净剂；
其中所述第一清净剂与所述第二清净剂的重量比为1:9至9:1。
本发明的第二方面是一种船用柴油机润滑油添加剂浓缩物，含有相容的有机稀释剂；第一清净剂，其为过碱性C10-40烷基芳基磺酸的碱土金属盐清净剂；和第二种清净剂，其为过碱性异构化C10-40正α烯烃基硫化酚的碱土金属盐清净剂；其中所述第一清净剂与所述第二清净剂的重量比为1:9至9:1。
本发明的第三方面涉及通过将润滑油组合物的组分的混合物混合在一起来生产本发明的船用柴油机润滑油组合物的方法。所得的润滑油组合物显示出改善的氧化稳定性、粘度增加控制、清净性和耐水性。
本发明的第四方面是一种操作船用柴油发动机的方法，包括用具有约5至约120的TBN的润滑油组合物润滑所述发动机，所述润滑油组合物包括：
(a)主要量的润滑粘度的基础油；
(b)第一清净剂，其为过碱性C10-40烷基芳基磺酸的碱土金属盐清净剂；和
(c)第二清净剂，其为过碱性异构化C10-40正α烯烃基硫化酚的碱土金属盐清净剂；
其中第一清净剂与第二清净剂的重量比为1:9至9:1。
本发明的第五方面是一种润滑船用柴油发动机的气缸的方法，包括用具有约5至约120的TBN的润滑油组合物润滑所述气缸，所述润滑油组合物包括：
(a)主要量的润滑粘度的基础油；
(b)第一清净剂，其为过碱性C10-40烷基芳基磺酸的碱土金属盐清净剂；和
(c)第二清净剂，其为过碱性异构化C10-40正α烯烃基硫化酚的碱土金属盐清净剂；
其中第一清净剂与第二清净剂的重量比为1:9至9:1。
在一个实施方案中，所述过碱性碱土金属烷基芳基磺酸盐清净剂和所述过碱性碱土金属异构化正α-烯烃基硫化酚盐清净剂中的碱土金属是钙。
在一个实施方案中，通过使C14-C24正α-烯烃的混合物异构化来制备过碱性异构化正α烯烃基酚盐清净剂的烷基取代基。
在一个实施方案中，过碱性碱土金属烷基芳基磺酸盐清净剂与过碱性碱土金属异构化正α-烯烃基硫化酚盐清净剂的重量比范围从1:9至9:1。
具体实施方式
在其最广泛的方面，本发明涉及用于船舶的润滑油组合物。
定义：
为了便于对本文公开的主题的理解，下面定义了本文所使用的多个术语，缩写或其它简写。任何未定义的术语，缩写或简写应被理解为具有与本申请的提交时具有的本领域技术人员使用的普通含义。
本文所用的术语“主要量”是指润滑油组合物中的浓度为至少约40重量％。在一个实施方案中，术语“主要量”是指润滑油组合物中的浓度为至少约50重量％。在另一个实施方案中，术语“主要量”是指润滑油组合物中的浓度为至少约60重量％。在另一个实施方案中，术语“主要量”是指润滑油组合物中的浓度为至少约70重量％。在另一个实施方案中，术语“主要量”是指润滑油组合物中的浓度为至少约80重量％。在另一个实施方案中，术语“主要量”是指润滑油组合物中的浓度或至少约90重量％。
术语“碱土金属”是指钙、钡、镁和锶。
术语“碱金属”是指锂、钠、钾、铷和铯。
术语“烯烃”是指具有一个或多个碳-碳双键的一类不饱和脂族烃。含有一个双键的那些称为单烯烃，具有两个双键的那些称为二烯、烷基二烯或二烯烃。α-烯烃特别活泼，因为双键位于烃链的第一和第二碳原子之间。α-烯烃的实例包括1-辛烯和1-十八碳烯，其用作中等可生物降解的表面活性剂的起点。线性和支链烯烃也包括在烯烃的定义中。
术语“正烯烃”，包括“正α烯烃”，是指在链中存在至少一个碳-碳双键的直链、非支链烃的烯烃。
术语“异构化烯烃”是指通过使烯烃异构化获得的烯烃。通常异构化的烯烃在与它们衍生的起始烯烃在不同的位置具有双键，并且也可以具有不同的特性。
术语“石灰”是指氢氧化钙，也称为熟石灰或消石灰。
术语“酚盐”是指苯酚的盐。
术语“过碱性”用于描述金属清净剂，其中金属部分的当量数与酸部分的当量数之比大于1。短语“高过碱性”是指约250或更大的TBN。
术语“清净剂的过碱性钙盐”是指金属盐的金属阳离子基本上是钙阳离子的过碱性清净剂。少量的其它阳离子可以存在于金属盐中，但金属盐中的阳离子通常为钙离子，通常至少为80，更典型地至少为90，例如至少为95摩尔％。
术语“总碱值”或“TBN”或“BN”是指中和1克产物所需的KOH的当量数毫克。因此，高TBN反映了强过碱性产品，因此，中和酸的碱储备更高。产品的TBN可以通过ASTM标准D2896或等效程序确定。
术语“物料摩尔比”或“CMR”，在涉及酚盐清净剂时，是在过碱化过程中使用的烷基酚清净剂的摩尔数/石灰摩尔数之比。
除非另有说明，本申请中公开的所有物质浓度和比例，均基于“活性物质”基准；即添加剂物质而非稀释剂或溶剂。
润滑粘度的基础油：
用于本发明润滑油组合物的润滑粘度的基础油(也称为基础油)通常以主要量存在，例如大于50重量％，优选大于约70重量％，更优选约80-约99.5重量％，最优选约80-约98重量％，基于组合物的总重量。本文所用的“基础油”一词应被理解为基础料或基础料混合物，其由单一制造商按照相同规格生产(不依赖于进料来源或制造商的地点)；满足相同制造商的规格；并且由唯一配方、产品识别码或这两者加以识别。用于本文的基础油可以是任何目前已知的或后来发现的用于配制用于船用柴油发动机的润滑油组合物的润滑粘度的油。
在一个实施方案中，润滑基础油的运动粘度在40℃下为22至300mm2/s，优选在40℃下为22至140mm2/s，运动粘度在100℃下为2至40mm2/s，优选在100℃下为3至15mm2/s。
基础料可以使用包括但不限于蒸馏、溶剂精制、氢处理、低聚、酯化和再精制的各种不同方法进行制造。精制料应该基本上不含通过制造、污染或先前使用引入的物质。本发明润滑油组合物的基础油可以是任何天然或合成的润滑基础油。
基础油可以衍生自天然润滑油、合成润滑油或它们的混合物。合适的基础油包括通过合成蜡和散蜡(slack wax)异构化获得的基础料，以及通过使粗产物的芳族和极性组分加氢裂化(而不是溶剂抽提)产生的加氢裂化基础料。合适的基础油包括如在API出版物1509,第14版,Addendum I,December 1998所定义的所有API类别即I、II、III、IV和V中的那些基础油。IV类基础油是聚α-烯烃(PAO)。V类基础油包括在I、II、III或IV类以外的所有其它基础油。在一个实施方案中，润滑粘度的基础油是I类和/或II类基础油。
有用的天然油包括矿物润滑油，例如，液体石油；溶剂处理的或酸处理的链烷属、环烷属或混合链烷属-环烷属型的矿物润滑油；衍生自煤或页岩的油；动物油；和植物油(例如油菜籽油、蓖麻油和猪油)。
有用的合成润滑油包括但不限于烃油和卤素取代的烃油，例如聚合和共聚的烯烃如聚丁烯、聚丙烯、丙烯-异丁烯共聚物、氯化聚丁烯、聚(1-己烯)、聚(1-辛烯)、聚(1-癸烯)以及它们的混合物；烷基苯如十二烷基苯、十四烷基苯、二壬基苯、二(2-乙基己基)-苯等，聚苯如联苯、三联苯、和烷基化的聚苯、烷基化的二苯醚和烷基化的二苯硫醚以及它们的衍生物、类似物和同系物等。这些有用的合成润滑油包括但不限于通过使小于5个碳原子的烯烃例如乙烯、丙烯、丁烯、异丁烯、戊烯以及它们的混合物进行聚合制备的油。制备这类聚合物油的方法对于本领域技术人员而言是公知的。
合适的烃合成油包括但不限于由乙烯聚合或由1-烯烃聚合以提供例如聚α烯烃或PAO油的聚合物制备的油，或者由使用一氧化碳和氢气的烃合成方法例如按费-托方法所制备的油。
另外的有用合成烃油包括具有适当粘度的α烯烃液体聚合物。特别有用的合成烃油是C6-C12α烯烃的氢化液体低聚物，例如1-癸烯三聚体。
另一类有用的合成润滑油包括但不限于其中末端羟基通过例如酯化或醚化加以改性的环氧烷聚合物，即其均聚物、共聚物和衍生物。这些油例示为通过环氧乙烷或环氧丙烷的聚合制备的油，聚氧亚烷基聚合物的烷基和苯基醚(例如具有1,000平均分子量的甲基聚丙二醇醚，具有500-1000分子量的聚乙二醇的二苯基醚，和具有1,000-1,500分子量的聚丙二醇的二乙基醚)或者它们的单-和多羧酸酯例如乙酸酯、混合的C3-C8脂肪酸酯、或四甘醇的C13含氧酸二酯。
又一类有用的合成润滑油包括但不限于二羧酸与各种醇的酯，所述二羧酸例如邻苯二甲酸、琥珀酸、烷基琥珀酸、烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、富马酸、己二酸、亚油酸二聚物、丙二酸、烷基丙二酸、烯基丙二酸，所述醇例如丁醇、己醇、十二烷基醇、2-乙基己醇、乙二醇、二乙二醇单醚、丙二醇。这些酯的具体实例包括己二酸二丁酯、癸二酸二(2-乙基己基)酯、富马酸二正己基酯、癸二酸二辛基酯、壬二酸二异辛基酯、壬二酸二异癸基酯、邻苯二甲酸二辛基酯、邻苯二甲酸二癸基酯、癸二酸双二十烷基酯、亚油酸二聚物的2-乙基己基二酯、由使1摩尔癸二酸与2摩尔四甘醇和2摩尔2-乙基己酸反应形成的复合酯。
用作合成油的酯还包括但不限于由具有约5至约12个碳原子的羧酸与醇例如甲醇和乙醇、多元醇和多元醇醚例如新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇、三季戊四醇制备的那些酯。
硅基油例如聚烷基-、聚芳基-、聚烷氧基-或聚芳氧基-硅氧烷油和硅酸酯油，构成另一类有用的合成润滑油。这些的具体实例包括但不限于硅酸四乙酯、硅酸四异丙酯、硅酸四(2-乙基己基)酯、硅酸四-(4-甲基-己基)酯、硅酸四(对叔丁基苯基)酯、己基-(4-甲基-2-戊氧基)二硅氧烷、聚(甲基)硅氧烷和聚(甲基苯基)硅氧烷。还有其它有用的合成润滑油包括但不限于含磷的酸的液体酯，例如磷酸三甲苯酯，磷酸三辛酯和癸烷膦酸的二乙酯和聚合的四氢呋喃。
润滑油可以衍生自未精制油、精制油和再精制油，可以是天然、合成或上文公开的这些类型中任意两种或更多种的混合物。未精制油是直接由天然或合成来源(例如煤、页岩或焦油砂沥青)而不进一步纯化或处理获得的那些。未精制油的实例包括但不限于直接由干馏操作获得的页岩油，直接由蒸馏获得的石油或直接由酯化工艺获得的酯油，然后它们中每一种在不进一步处理的情况下使用。精制油除了它们在一个或多个纯化步骤中进一步处理以改善一种或多种性能外与未精制油类似。这些纯化技术对于本领域技术人员是已知的，包括例如溶剂提取、二次蒸馏、酸或碱提取、过滤、渗滤、加氢处理、脱蜡等。再精制油通过将使用过的油按类似于用于获得精制油的那些方法进行处理来获得。这类再精制油还称作再生油或再加工油并且经常通过涉及除去废添加剂和油分解产物的技术进行另外处理。
衍生自蜡加氢异构化的润滑油基础料还可以单独使用或与上述天然和/或合成的基础料组合使用。这种蜡异构油通过将天然或合成的蜡它们的混合物在加氢异构化催化剂上加氢异构化产生。
天然蜡典型地是通过矿物油的溶剂脱蜡回收的散蜡；合成蜡典型地是通过费-托方法产生的蜡。
过碱性烷基芳基磺酸盐清净剂：
过碱性烷基芳基磺酸盐清净剂是具有至少250的BN的碱土金属烷基芳基磺酸盐，其中芳基不是苯酚，并且烷基是含有14至40个碳原子的直链。过碱性烷基芳基磺酸盐清净剂可以以0.2-20.0重量％的量掺入润滑油组合物中，优选2.5-10.0重量％，基于润滑油组合物的总量。
过碱性烷基芳基磺酸盐清净剂优选为高过碱性清净剂，并且具有至少250，优选大于350，更优选大于450的总碱值(TBN，以mg KOH/g计，按ASTM 2896定义)。
过碱性烷基芳基磺酸盐清净剂中的芳基可以是一种芳族化合物或芳族化合物的混合物。合适的芳族化合物或芳族化合物混合物包含单环芳族化合物，例如苯、甲苯、二甲苯、异丙基苯或其混合物中的至少一种。在一个优选的实施方案中，所述烷基芳族磺酸或者盐的至少一个芳族部分不含羟基。在一个优选的实施方案中，所述烷基芳族磺酸或盐化合物的至少一个芳族部分不是苯酚。在一个实施方案中，所述至少一种芳族化合物或芳族化合物混合物是甲苯。
过碱性烷基芳基磺酸盐清净剂中的直链烷基链含有14至40个碳原子，优选14至24个碳原子，优选20至24个碳原子。优选地，碱土烷基芳基磺酸盐衍生自C14-C40正α-烯烃，更优选衍生自C20-C24正α-烯烃。
过碱性烷基芳基磺酸盐清净剂可以使用本领域已知的任何方法制备。通常，烷基芳基磺酸盐清净剂可以通过采用以下步骤来制备：
a.用碱中和烷基芳基磺酸；
b.用碱和CO2对中和的烷基芳基磺酸进行碳酸化以产生过碱性烷基芳基磺酸盐；
c.除去任何沉淀物和溶剂。
在一个实施方案中，过碱性烷基芳基磺酸盐清净剂可以通过美国专利号6,479,440实施例1中描述的方法制备，其内容通过引用并入本文。
碱的来源可以是碱土金属碱。可用于进行该步骤的合适的碱土金属碱包括钙、镁、钡或锶的氧化物或氢氧化物，特别是氧化钙、氢氧化钙、氧化镁及其混合物。在一个实施方案中，碱土金属碱是熟石灰(氢氧化钙)。
过碱性异构化正α烯烃基酚盐清净剂：
过碱性异构化正α烯烃基酚盐清净剂是烷基化羟基化合物，其中羟基化合物的烷基取代基是至少一种具有约15至约99重量％支化的烯烃的残基。异构化烯烃可以是C10-C40烯烃。在一个实施方案中，异构化的烯烃是C14-C24烯烃。在另一个实施方案中，异构化的烯烃是C20-C24烯烃。
可以通过美国专利号8,580,717(实施例1-13)中描述的方法制备过碱性异构化正α烯烃基酚盐清净剂，其内容通过引用并入本文。过碱性异构化正α烯烃基酚盐清净剂可以通过以下方法制备：
a)将至少一种羟基芳族化合物用至少一种具有约15至约99重量％支化的异构烯烃烷基化以提供至少一种烷基化羟基芳族化合物，所述异构烯烃通过异构化至少一种具有约10至约40个碳原子的正α-烯烃获得；
(b)以任意顺序中和并硫化烷基化羟基芳族化合物以提供至少一种中和的、硫化的烷基化羟基芳族化合物；和
(c)使所述至少一种中和的、硫化的烷基化羟基芳族化合物过碱化；其中所述羟基芳族化合物是苯酚、甲酚、二甲苯酚或其混合物。
可用于进行过碱性处理的碱土金属碱包括钙、镁、钡或锶的氧化物或氢氧化物，特别是氧化钙、氢氧化钙、氧化镁及其混合物。在一个实施方案中，碱土金属碱是熟石灰(氢氧化钙)。
所述过碱性异构化正α烯烃基酚盐清净剂具有大于200、优选大于250的总碱值(TBN，以mg KOH/g表示，按ASTM 2896定义)。
所述过碱性异构化正α烯烃基酚盐清净剂在润滑油组合物中的量为0.1重量％至约20重量％，基于润滑油组合物的总重量。在一个实施方案中，所述润滑油组合物中过碱性异构化正α烯烃基酚盐清净剂的量为约0.1重量％至约5重量％，基于润滑油组合物的总重量。
过碱性烷基芳基磺酸盐清净剂与过碱性异构化正α烯烃基酚盐清净剂的重量比范围从1:9至9:1，优选1:1.5至9:1，优选1:5至8:1，更优选1：2到6：1。
其他添加剂
本发明的润滑油组合物还可以含有可以赋予或改善这些添加剂分散或溶解于其中的润滑油组合物的任何所需性质的其它常规添加剂。本领域普通技术人员已知的任何添加剂可用于本文中公开的润滑油组合物。例如，润滑油组合物可以与抗氧化剂、抗磨剂、清净剂如金属清净剂、防锈剂、去雾剂、破乳剂、金属钝化剂、摩擦改性剂、倾点降低剂、消泡剂、助溶剂、包装相容剂、腐蚀抑制剂、无灰分散剂、染料、极压剂以及其混合物共混。多种添加剂是已知和市售的。这些添加剂，或它们的类似化合物，可通过常见共混程序用于制备本发明的润滑油组合物。
抗氧化剂的实例包括但不限于胺类，例如二苯胺、苯基-α-萘胺、N，N-二(烷基苯基)胺和烷基化亚苯基二胺；酚类如BHT、空间位阻烷基酚，如2,6-二叔丁基苯酚、2,6-二叔丁基对甲酚和2,6-二叔丁基-4-(2-辛基-3-丙酸)苯酚；抗氧化剂的量可以为约0.01重量％至约5重量％。
抗磨剂的实例包括但不限于二烷基二硫代磷酸锌和二芳基二硫代磷酸锌，例如在发表于Lubrication Science4-2，1992年1月的Born等人的题为“Relationship betweenChemical Structure and Effectiveness of some Metallic Dialkyl-and Diaryl-dithiophosphates in Different Lubricated Mechanisms”的论文中所描述的那些，参见例如第97-100页；芳基磷酸酯和亚磷酸酯；含硫酯；磷硫化合物；金属或无灰二硫代氨基甲酸盐，黄原酸盐，烷基硫化物及其混合物。抗磨剂的量可以为约0.01至约5重量％。
防锈剂的实例包括但不限于非离子型聚氧化烯试剂，例如聚氧乙烯月桂基醚、聚氧乙烯高级醇醚、聚氧乙烯壬基苯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯辛基硬脂基醚、聚氧乙烯油醚、聚氧乙烯山梨糖醇单硬脂酸酯、聚氧乙烯山梨醇单油酸酯和聚乙二醇单油酸酯；硬脂酸和其它脂肪酸；二羧酸；金属皂类；脂肪酸胺盐；重质磺酸的金属盐；多元醇的羧酸偏酯；磷酸酯；(短链)烯基琥珀酸，其偏酯及其含氮衍生物；合成的烷芳基磺酸盐，例如金属二壬基萘磺酸盐；以及其混合物。防锈剂的量可以为约0.01重量％至约10重量％。
摩擦改性剂的实例包括但不限于烷氧基化脂肪胺；硼酸化脂肪环氧化物；脂肪亚磷酸酯；脂肪环氧化物；脂肪胺；硼酸化烷氧基化脂肪胺；脂肪酸的金属盐；脂肪酸酰胺；以及如美国专利号6,372,696中公开的脂肪咪唑啉，其内容经此引用并入本文；获自C4至C75、优选C6至C24和最优选C6至C20脂肪酸酯和选自氨和烷醇胺以及其混合物的含氮化合物的反应产物的摩擦改性剂。摩擦改进剂的量可以为约0.01重量％至约10重量％。
消泡剂的实例包括但不限于甲基丙烯酸烷基酯的聚合物；二甲基硅氧烷的聚合物，及其混合物。消泡剂的量可以为约0.01至约1重量％。
倾点降低剂的实例包括但不限于聚甲基丙烯酸酯/盐、丙烯酸烷基酯聚合物、甲基丙烯酸烷基酯聚合物、二(四-链烷烃酚)邻苯二甲酸酯/盐、四-链烷烃酚的缩合物、氯化链烷烃与萘的缩合物，以及其组合。在一个实施方案中，倾点降低剂包括乙烯-乙酸乙烯酯共聚物、氯化链烷烃与苯酚的缩合物、聚烷基苯乙烯，以及其组合。倾点降低剂的量可以为大约0.01重量％至大约10重量％。
破乳剂的实例包括但不限于阴离子表面活性剂(例如，烷基萘磺酸盐和烷基苯磺酸盐)、非离子烷氧基化烷基酚树脂、氧化烯的聚合物(例如聚环氧乙烷、聚环氧丙烷、环氧乙烷环氧丙烷的嵌段共聚物)、油溶性酸的酯、聚氧乙烯失水山梨糖醇酯，以及其组合。破乳剂的量可以为大约0.01重量％至大约10重量％。
腐蚀抑制剂的实例包括但不限于十二烷基琥珀酸的半酯或酰胺、磷酸酯、硫代磷酸盐、烷基咪唑啉、肌氨酸，以及其组合。腐蚀抑制剂的量可以为大约0.01重量％至大约5重量％。
极压剂的实例包括但不限于，硫化的动物或植物的脂肪或油、硫化的动物或植物的脂肪酸酯、磷的三价或五价酸的完全或部分酯化的酯、硫化烯烃、二烃基多硫化物、硫化的狄尔斯-阿德耳加成物、硫化的二环戊二烯、脂肪酸酯和单不饱和烯烃的硫化或共硫化的混合物、脂肪酸、脂肪酸酯和α-烯烃的共硫化共混物、官能取代的二烃基多硫化物、硫杂醛、硫杂酮、环硫化合物、含硫的乙缩醛衍生物、萜烯和非环式烯烃的共硫化共混物、多硫化物烯烃产物、磷酸酯或硫代磷酸酯的胺盐、以及其组合。极压剂的量可以为大约0.01重量％至大约5重量％。
本发明的润滑油组合物可以通过常规技术将适量的第一清净剂和第二清净剂与任何任选的添加剂与润滑粘度的基础油混合来制备。
本发明的润滑油组合物的TBN为5至120，优选5-100，优选10-100，优选15-100，优选20-100，优选5至70，更优选15至40，更优选5至40，更优选20至70，更优选20至50，更优选为15至70mgKOH/g。
本发明的润滑油组合物的粘度等级为SAE 20-50。在一个实施方案中，润滑油具有SAE 20的粘度等级。在一个实施方案中，润滑油具有SAE 30的粘度等级。在一个实施方案中，润滑油具有SAE 40的粘度等级。在一个实施方案中，润滑油具有SAE 50的粘度等级。
润滑油基础油在100℃下的运动粘度为5.6至21.9mm2/s，优选为9.3至21.9mm2/s，优选为9.3至16.3mm2/s，优选为9.3至12.5mm2/s，优选为12.5至16.3mm2/s，优选16.3至21.9mm2/s。
实施例
以下非限制性实施例是本发明的说明。
通过混合表1-3所示的组分来配制润滑油组合物。
使用以下测试方法测试所得组合物：
小松热管(KHT)试验:使润滑油组合物通过一个采用适当空气流控温的玻璃管一定的时间。然后将玻璃管冷却并洗涤，用色度仪测定留在玻璃管内表面的任何漆状沉淀物的颜色，等级范围从0到10(0＝黑，10＝清洁)。在玻璃管完全被沉积物堵塞的情况下，测试结果记录为“堵塞”。通过在较高温度范围内维持较高的KHT值来表示优良的清净性。
差示扫描量热法：该试验用于根据ASTM D-6186来评价受试油的薄膜氧化稳定性。在试验过程中，将进入或来自样品杯中受试油的热流与参比杯进行比较。氧化开始温度是受试油氧化开始时的温度。氧化诱导时间是受试油的氧化开始时的时间。氧化反应导致放热反应，其由热流显示。计算氧化诱导时间以评价受试油的薄膜氧化稳定性。该测试方法的副本可以从ASTM International at 100Barr Harbor Drive,PO Box0700,WestConshohocken,Pa.19428-2959获得，并且通过引用并入本文用于所有目的。总体上氧化诱导时间越高，薄膜氧化稳定性越好。
改进的石油学会48(MIP-48)试验，粘度增加：将两个润滑油组合物样品加热一段时间。当空气通过另一个样品时，氮气通过一个测试样品。然后将两个样品冷却，确定每个样品的粘度。通过将鼓空气样品的100℃下运动粘度减去鼓氮气样品的100℃下运动粘度并将相减结果除以鼓氮气样品的100℃下运动粘度，来计算每个船用系统油组合物基于氧化的粘度增加率。通过较低的粘度增加可以证明更好的抗基于氧化的粘度增加的稳定性。
改进的石油学会48(MIP-48)试验，BN损耗：将两个润滑油组合物样品加热一段时间。当空气通过另一个样品时，氮气通过一个测试样品。然后将两个样品冷却，确定每个样品的TBN。通过将鼓空气样品的TBN减去鼓氮气样品的TBN并将相减结果除以鼓氮气样品的TBN，并将结果乘以100得到所述MIP-48TBN损耗％，来计算所述MIP-48TBN损耗。较低的BN损耗百分率是期望的。
离心机耐水性：含有5100g油的离心机在80℃下不断地以50L/h再循环。在离心的3小时期间，以1L/h的速度连续供给新鲜水。测定离心机盘、分配器和转筒上沉积物的最终重量。测定测试之前和之后油中的钙、磷、锌和水含量。通过在润滑油中更高的钙、磷、或锌的保留表明更好的耐水性能。
以下使用下列组分来配制实施例的船用柴油机润滑剂组合物。
清净剂A：过碱性烷基甲苯磺酸钙清净剂的油浓缩物；其中烷基衍生自C20至C24直链α-烯烃。该添加剂浓缩物含有16.1重量％Ca，约38.7重量％的稀释油，TBN为420。基于活性物质，该添加剂的TBN(不含稀释油)为685。
清净剂B：衍生自丙烯四聚体的过碱性硫化酚钙的油浓缩物。该添加剂含有9.6重量％Ca，约31.4重量％稀释油，TBN为260。
清净剂C：衍生自异构化度不低于85％且CMR为0.44的C14正α-烯烃的过碱性硫化酚钙的油浓缩物。该添加剂含有9.8重量％Ca，约31.4重量％稀释油，TBN约为260。
清净剂D：衍生自异构化度不低于85％且CMR为0.57的C14正α-烯烃的过碱性硫化酚钙的油浓缩物。该添加剂含有约10.2重量％Ca，约31.4重量％稀释油，TBN约为260。
清净剂E：衍生自异构化度为65％且CMR为0.32的C20-24正α-烯烃的过碱性硫化酚钙的油浓缩物。该添加剂含有约9.45重量％Ca，约31.4重量％稀释油，TBN约为260。
清净剂F：衍生自异构化度为65％且CMR为0.46的C20-24正α-烯烃的过碱性硫化酚钙的油浓缩物。该添加剂含有9.9重量％Ca，约31.4重量％稀释油，TBN约为260。
磨损抑制剂：从Chevron Oronite Company(San Ramon，CA)获得的C4和C6醇混合物的仲二硫代磷酸锌(ZnDTP)。
I类基础油是从ExxonMobil(Irving,TX.)获得的ExxonMobil600N基础料。
Chevron RLOP 600N:II类基础油是从Chevron Products Company(San Ramon,CA.)获得的Chevron RLOP 600N基础料。
例1：通过混合表1所示的组分配制例1的润滑油组合物。
例2：通过混合表2所示的组分配制例2的润滑油组合物。
例3：通过混合表3所示的组分配制例3的润滑油组合物。
例4：通过混合表4所示的组分配制例4的润滑油组合物。
表1-4显示涉及来自异构化烯烃的酚盐的实施例在小松热管和MIP试验表现出与比较例中相当的性能。与比较例相比，测试实施例还显示可比的或改善的耐水性。
例5：通过混合表5所示的组分配制例5的润滑油组合物。
表5表明，在高BN下，涉及衍生自异构化烯烃的酚盐的实施例在小松热管和MIP试验中显示出与比较例相当的性能。
应当明白，可以对本文公开的实施例进行各种修改。因此，上述描述不应被解释为限制性的，而仅仅是优选实施例的示例。例如，上述实现的作为操作本发明的最佳模式的功能仅用于说明的目的。在不脱离本发明的范围和精神的情况下，本领域技术人员可以实现其他布置和方法。此外，本领域技术人员可以想到在所附权利要求的范围和精神内的其它修改。
Claims (10)
1.一种具有约5至约120的TBN的船用柴油机润滑剂组合物，包括：
(a)主要量的润滑粘度的基础油；
(b)第一清净剂，其为过碱性C10-40烷基芳基磺酸的碱土金属盐清净剂；和
(c)第二清净剂，其为过碱性异构化C10-40正α烯烃基硫化酚的碱土金属盐清净剂
其中所述第一清净剂与所述第二清净剂的重量比范围从1:9至9:1。
2.权利要求1的组合物，其中所述过碱性烷基磺酸盐清净剂和所述过碱性异构化正α-烯烃基酚盐清净剂都是过碱性钙盐。
3.权利要求1的组合物，其中所述过碱性异构化正α-烯烃基酚盐清净剂的烷基取代基通过使C14-C24正α-烯烃异构化来制备。
4.权利要求1的组合物，其中所述润滑粘度的基础油是I类基础油。
5.权利要求1的组合物，其中所述润滑粘度的基础油是I I类基础油。
6.权利要求1的组合物，其中所述组合物不含甘油酯或硼酸化甘油酯。
7.权利要求1的组合物，其中过碱性异构化正α-烯烃基酚盐清净剂是烷基化羟基化合物，其中所述羟基化合物的烷基取代基是至少一种具有约15至约99重量％支化的烯烃的残基。
8.权利要求1的组合物，其中所述过碱性异构化正α-烯烃基酚盐清净剂是烷基化羟基化合物，其中所述羟基化合物的烷基取代基是至少一种具有约15至约99重量％支化的烯烃的残基。
9.一种操作船用柴油发动机的方法，包括用具有约5至约120的TBN的润滑油组合物润滑所述发动机，所述润滑油组合物包括：
(a)主要量的润滑粘度的基础油；
(b)第一清净剂，其为过碱性C10-40烷基芳基磺酸的碱土金属盐清净剂；和
(c)第二清净剂，其为过碱性异构化C10-40正α烯烃基硫化酚的碱土金属盐清净剂；
其中第一清净剂与第二清净剂的重量比范围从1:9至9:1。
10.一种润滑船用柴油发动机的气缸的方法，包括用具有约5至约120的TBN的润滑油组合物润滑所述气缸，所述润滑油组合物包括：
(a)主要量的润滑粘度的基础油；
(b)第一清净剂，其为过碱性C10-40烷基芳基磺酸的碱土金属盐清净剂；和
(c)第二清净剂，其为过碱性异构化C10-40正α烯烃基硫化酚的碱土金属盐清净剂；
其中第一清净剂与第二清净剂的重量比为1:9至9:1。
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| US62/108,701 | 2015-01-28 | ||
| PCT/US2016/014926 WO2016123106A2 (en) | 2015-01-26 | 2016-01-26 | Marine diesel engine lubricating oil composition |
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| CN110577854A (zh) * | 2018-06-11 | 2019-12-17 | Jxtg能源株式会社 | 双循环十字头型柴油发动机用汽缸润滑油组合物和其用途 |
| CN112292441A (zh) * | 2018-06-22 | 2021-01-29 | 雪佛龙奥伦耐有限责任公司 | 润滑油组合物 |
| CN112313316A (zh) * | 2018-06-22 | 2021-02-02 | 雪佛龙奥伦耐有限责任公司 | 润滑油组合物 |
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| CN110770331B (zh) * | 2017-06-30 | 2023-01-24 | 雪佛龙奥伦耐有限责任公司 | 含有异构化酚基清净剂的低粘度发动机油 |
| US20190002783A1 (en) * | 2017-06-30 | 2019-01-03 | Chevron Oronite Company Llc | Marine diesel lubricant oil compositions having improved low temperature performance |
| EP3645684B1 (en) * | 2017-06-30 | 2022-10-19 | Chevron Oronite Company LLC | Marine diesel lubricant oil compositions |
| WO2019003173A1 (en) * | 2017-06-30 | 2019-01-03 | Chevron Oronite Company Llc | LUBRICATING OIL COMPOSITIONS FOR MARINE DIESEL ENGINE |
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| EP3250663A4 (en) | 2018-06-27 |
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| JP2018504498A (ja) | 2018-02-15 |
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