CN102952609A - 含有官能化分散剂的润滑剂组合物 - Google Patents
含有官能化分散剂的润滑剂组合物 Download PDFInfo
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- CN102952609A CN102952609A CN2012102838476A CN201210283847A CN102952609A CN 102952609 A CN102952609 A CN 102952609A CN 2012102838476 A CN2012102838476 A CN 2012102838476A CN 201210283847 A CN201210283847 A CN 201210283847A CN 102952609 A CN102952609 A CN 102952609A
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- Prior art keywords
- acid
- engine
- lubricant
- oil
- carboxylic acid
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 123
- 239000000314 lubricant Substances 0.000 title claims description 51
- 239000002270 dispersing agent Substances 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 35
- 239000002199 base oil Substances 0.000 claims abstract description 32
- 239000010705 motor oil Substances 0.000 claims abstract description 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 15
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- 150000008065 acid anhydrides Chemical class 0.000 claims description 46
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- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 8
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- 239000000806 elastomer Substances 0.000 claims description 3
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 8
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- 150000001875 compounds Chemical class 0.000 description 18
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 9
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- 239000011733 molybdenum Substances 0.000 description 8
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- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 6
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
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- 229910052791 calcium Inorganic materials 0.000 description 5
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 5
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
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Abstract
一种发动机润滑剂组合物、保持发动机润滑剂的烟灰或油泥处理能力而对发动机中的弹性体密封材料无不利影响的方法和操作发动机的方法。所述发动机润滑剂包括基础油和分散剂。所述分散剂是A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物。
Description
相关申请
本申请涉及2011年8月11日提交的美国临时申请号61/522,276和2011年9月8日提交的美国临时申请号61/532,129。
技术领域
本公开内容涉及润滑剂组合物，且特别是用于改进发动机润滑剂组合物的烟灰或油泥处理特征，同时使添加剂对发动机密封的有害作用最小化的添加剂。
背景与概述
可以选择发动机润滑剂组合物以在提供增加的燃料经济性和降低的排放的同时提供增加的发动机保护。然而，为实现改进燃料经济性和降低排放的益处，对于润滑剂组合物，需要发动机保护和润滑性能之间的平衡。例如摩擦调节剂的量的增加可有益于燃料经济性的目的，但可导致润滑剂组合物处理水的能力降低。同样地，增加润滑剂中抗磨剂的量可提供改进的对磨损的发动机保护，但却可有害于用于降低排放的催化剂性能。
对于润滑剂组合物的烟灰和油泥处理组分同样如此。随着分散剂在润滑剂组合物中的量增加，通常，润滑剂的烟灰和油泥处理性质改进。然而，增加分散剂的量可对弹性体密封有不利影响，因为分散剂通常为有害于密封的胺式(aminic)含氮化合物。相信通过将多芳香官能度引入到分散剂，改进分散剂对烟灰相关的粘度增加的控制能力。因此，相信使分散剂与邻苯二甲酸酐或萘二甲酸酐反应并用环状碳酸酯封端提供与常规分散剂相比更好的烟灰处理能力。然而，此类官能化分散剂经常显示不良的弹性体密封适应性，甚至在相对低的处理速率下也如此。因此，存在对可提供改进的烟灰处理以及改进的密封适应性而且适合于满足或超出当前提出的和将来的润滑剂性能标准的分散剂的需要。
关于前面所述，本公开内容的实施方案提供发动机润滑剂组合物、保持发动机润滑剂的烟灰或油泥处理能力而对发动机中的弹性体密封材料无不利影响的方法和操作发动机的方法。发动机润滑剂包括基础油和分散剂，所述分散剂为A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物。
在上述组合物的一个实施方案中，组分A包含聚烯基-取代琥珀酸或酸酐。
在上述组合物的一个实施方案中，约0.25-约1.5摩尔的组分D与每摩尔组分B反应。
在上述组合物的一个实施方案中，组合物还包含以下一种或多种：去污剂、分散剂、摩擦调节剂、抗氧化剂、防锈剂、粘度指数改进剂、乳化剂、反乳化剂、防腐剂、抗磨剂、金属二烃基二硫代磷酸盐、无灰胺磷酸盐、消泡剂和倾点下降剂。
在上述组合物的一个实施方案中，组合物还包含油溶性含钛添加剂。
本公开内容的另一实施方案提供保持用于发动机的发动机润滑剂的烟灰处理能力而对发动机的弹性体密封无不利影响的方法。所述方法包括用基础油和添加剂配制发动机的润滑剂组合物，所述添加剂为A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物。
在上述方法的一个实施方案中，组分C包含1,8-萘二甲酸酐。
在上述方法的一个实施方案中，组分A包含马来酸酐。
在上述方法的一个实施方案中，润滑剂组合物包含约0.5-约5重量%的分散剂。
在上述方法的一个实施方案中，酰亚胺反应产物包含聚异丁烯基琥珀酸或酸酐和含有3-5个氮原子的聚胺的反应产物。
在上述方法的一个实施方案中，稠合芳香族化合物与酰亚胺反应产物反应的摩尔比的范围为约0.25-约1.5且非芳香族二元羧酸或酸酐与双酰亚胺反应产物反应的摩尔比的范围为约0.25-约1.5。
在上述方法的一个实施方案中，润滑剂组合物还包含以下一种或多种：去污剂、分散剂、摩擦调节剂、抗氧化剂、防锈剂、粘度指数改进剂、乳化剂、反乳化剂、防腐剂、抗磨剂、金属二烃基二硫代磷酸盐、无灰胺磷酸盐、消泡剂和倾点下降剂。
在上述方法的一个实施方案中，润滑剂组合物还包含油溶性含钛添加剂。
本公开内容的再一实施方案提供操作发动机的方法，所述方法包括配制具有基础油和润滑剂添加剂包的用于发动机的发动机润滑剂，所述润滑剂添加剂包含有A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物；并用所述发动机润滑剂操作发动机。
在上述方法的一个实施方案中，与缺少组分D的情况下制造的反应产物相比，所述反应产物显示改进的氟弹性体密封适应性。
在上述方法的一个实施方案中，润滑剂组合物包含约0.5-约5重量%的分散剂。
在上述方法的一个实施方案中，所述烃基二元羧酸或酸酐包含聚异丁烯和琥珀酸或酸酐的反应产物，所述聚异丁烯具有大于60摩尔%的末端亚乙烯基含量。
使用所公开的实施方案的官能化分散剂的一个意外优势是：在官能化分散剂适合于处理烟灰的同时，官能化分散剂具有优良的弹性体密封保护性质。使用本文描述的官能化分散剂的进一步的优势是：与常规分散剂相比，可以使用更少量的官能化分散剂来实现烟灰处理能力。
提供下面的术语定义以明确本文所用某些术语的含义。
本文所用术语“油组合物”、“润滑组合物”、“润滑油组合物”、“润滑油”、“润滑剂组合物”、“润滑组合物”、“充分配制的润滑剂组合物”和“润滑剂”被视为同义的完全可互换的术语，是指包含大量基础油加少量添加剂组合物的润滑成品。
本文所用术语“添加剂包(additive package)”、“添加剂浓缩物(additive concentrate)”和“添加剂组合物”被视为同义的完全可互换的术语，是指除大量基础油原料混合物以外的润滑组合物的部分。
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普通意义使用。具体地讲，其是指具有与分子的其余部分直接连接的碳原子并主要具有烃特性的基团。烃基的实例包括：
(1) 烃取代基，即脂族(例如烷基或烯基)、脂环族(例如环烷基、环烯基)取代基和芳族取代的、脂族取代的和脂环族取代的芳族取代基以及环式取代基，其中环通过分子的另一个部分成环(例如2个取代基一起形成脂环族基团)；
(2) 取代的烃取代基，即含有非烃基的取代基，所述非烃基在本发明的情况下不改变主要的烃取代基(例如卤素(尤其是氯和氟)、羟基、烷氧基、巯基、烷基巯基、硝基、亚硝基和磺氧基(sulfoxy))；
(3) 杂取代基，即以下取代基，其在本发明的情况下，虽然具有主要的烃特性，但在本来由碳原子组成的环或链中含有非碳。杂原子包括硫、氧、氮，并包括诸如吡啶基、呋喃基、噻吩基和咪唑基等取代基。一般而言，烃基中每10个碳原子可存在不超过2个(例如不超过1个)非烃取代基；通常，在烃基没有非烃取代基。
除非另有明确说明，否则本文所用术语“重量%”意指所述组分占整个组合物的重量的百分比。
本文所用术语“油溶性的”或“可分散的”可能但不一定是指化合物或添加剂全部可溶于、溶解于、混溶于或能够悬浮于油中。然而，以上术语的确意指例如它们可溶于或稳定分散于油中至在使用油的环境中足以发挥其预期作用的程度。此外，如有需要，额外掺入其它添加剂还可允许掺入较高水平的特定添加剂。
可通过将下文详述的一种或多种添加剂加到合适的基础油制剂中来配制本公开内容的润滑油、发动机润滑油和/或曲轴箱润滑油。可将添加剂以添加剂包(或浓缩液)形式与基础油混合，或者，可单独与基础油混合。根据所加入的添加剂及其各自的比例，充分配制的润滑剂、发动机润滑剂和/或曲轴箱润滑剂可显示改进的性能特性。
本公开内容的其它详情和优势将在接下来的描述中部分给出，和/或可通过本公开内容的实践来学习。可通过随附权利要求书中具体指出的要素和组合实现和获得本公开内容的详情和优势。
要理解的是，前面的概述和下面的详细描述二者仅是示例性和说明性的，并不限制所要求保护的本公开内容。
附图简述
图1为用于确定根据本公开实施方案的组合物的烟灰分散性的粘度对剪切速率的图像表示。
示例性实施方案的描述
下面将以其实施方案更有限的方面，包括本公开内容的制剂和用途的各个实例，对本公开内容进行描述。应了解的是，这些实施方案仅为了说明本发明的目的而提供，不应视作对其范围的限制。
发动机或曲轴箱润滑剂组合物用于装有火花点火和压燃式发动机的交通工具。这类发动机可用于汽车、货车和/或火车应用，并可依靠燃料(包括但不限于汽油、柴油、醇、压缩天然气等)运作。本公开内容可描述适合用作发动机润滑剂的润滑剂，比如满足或超出ILSAC GF-5和/或API CJ-4润滑剂标准的汽车曲轴箱润滑剂。
基础油
适用于配制发动机润滑剂组合物的基础油可选自任何合适的合成油、动物油、植物油、矿物油或其混合物。可使用动物油和植物油(例如猪油、蓖麻油)以及矿物润滑油，例如液体石油和链烷烃型、环烷型或混合链烷烃-环烷型的溶剂处理的或酸处理的矿物润滑油。来源于煤或页岩的油也可能是适宜的。基础油通常在100℃下可具有约2-约15 cSt的粘度，或者再举例来说具有约2-约10 cSt的粘度。此外，来源于气液加工的油也是适宜的。
合适的合成基础油可包括二羧酸的烷基酯、聚二醇和醇、聚α-烯烃(包括聚丁烯)、烷基苯、磷酸的有机酯和聚硅酮油(polysilicone oil)。合成油包括烃油，例如聚合烯烃和共聚烯烃(例如聚丁烯、聚丙烯、丙烯异丁烯共聚物等)；聚(1-己烯)、聚-(1-辛烯)、聚(1-癸烯)等及其混合物；烷基苯(例如十二烷基苯、十四烷基苯、二-壬基苯、二-(2-乙基己基)苯等)；聚苯(例如联苯、三联苯、烷基化聚苯等)；烷基化二苯醚和烷基化二苯硫及其衍生物、类似物和同系物等。
环氧烷聚合物和共聚物及其其中末端羟基通过酯化、醚化等修饰的衍生物，构成另一类可以使用的已知合成油。这类油的典型实例为通过环氧乙烷或环氧丙烷聚合制备的油、这些聚氧化烯聚合物的烷基醚和芳基醚(例如平均分子量约为1000的甲基-聚异丙二醇醚、分子量约为500-1000的聚乙二醇的二苯醚、分子量约为1000-1500的聚丙二醇的二乙醚等)或其单羧酸酯和聚羧酸酯，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。
另一类可以使用的合成油包括二羧酸(例如酞酸、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、亚油酸二聚体、丙二酸、烷基丙二酸、烯基丙二酸等)与各种醇(例如丁醇、己醇、十二烷醇、2-乙基己醇、乙二醇、二甘醇单醚、丙二醇等)的酯。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、富马酸二正己酯、癸二酸二辛酯、壬二酸二异辛酯、壬二酸二异癸酯、酞酸二辛酯、酞酸二癸酯、癸二酸二(二十烷基)酯、亚油酸二聚体的2-乙基己二酯、通过使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混合酯等。
可用作合成油的酯还包括由C5-C12一元羧酸与多元醇和多元醇醚(例如新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇、三季戊四醇等)制备的酯。
因此，可用于制备本文所述发动机润滑剂组合物的所用基础油可选自美国石油协会(API)基础油互换准则(American Petroleum Institute(API)Base Oil Interchangeability Guidelines)中规定的I-V类中的任何基础油。这类基础油类别如下：
表1
1 第I-III类为矿物油基本原料。
基础油可含有少量或大量聚α-烯烃(PAO)。通常，聚α-烯烃来源于具有约4个-约30个、或约4个-约20个、或约6个-约16个碳原子的单体。有用的PAO的实例包括来源于辛烯、癸烯、其混合物等的PAO。PAO在100℃下的粘度可为约2-约15、或约3-约12、或约4-约8 cSt。PAO的实例包括100℃下为4 cSt的聚α-烯烃、100℃下为6 cSt的聚α-烯烃及其混合物。可以使用矿物油与前述聚α-烯烃的混合物。
基础油可以是来源于Fischer-Tropsch合成烃的油。Fischer-Tropsch合成烃使用Fischer-Tropsch催化剂由含有H2和CO的合成气制备。这类烃通常需要进一步加工以便可用作基础油。例如，烃可采用美国专利号6,103,099或6,180,575中公开的方法加氢异构化；可采用美国专利号4,943,672或6,096,940中公开的方法加氢裂化和加氢异构化；可采用美国专利号5,882,505中公开的方法脱蜡；或可采用美国专利号6,013,171、6,080,301或6,165,949中公开的方法加氢异构化和脱蜡。
未精炼、精炼和再精炼的油(上文所公开类型的天然或合成油(以及任何这些油的两种或更多种的混合物))可用于基础油。未精炼油是从天然或合成来源直接获得的未进行进一步纯化处理的油。例如直接获自干馏操作的页岩油、直接获自初级蒸馏的石油或直接获自酯化过程的酯油，未进行进一步处理便使用，是未精炼油。精炼油类似于未精炼油，只是它们在一个或多个纯化步骤中进一步处理以改进一个或多个性质。许多这类纯化技术为本领域技术人员所知，例如溶剂萃取、二级蒸馏、酸或碱萃取、过滤、渗滤等。通过将类似于用于获得精炼油的方法应用于已投入使用的精炼油，获得再精炼油。这类再精炼油亦称为再生油或再加工油，并常常通过涉及除去废添加剂、污染物和油分解产物的技术再次加工。
基础油可与本文实施方案公开的添加剂组合物混合以提供发动机润滑剂组合物。因此，基础油可以占润滑剂组合物总重量的范围为约50重量%-约95重量%的量存在于发动机润滑剂组合物中。
官能化分散剂
在本公开实施方案的一个方面，分散剂添加剂为官能化分散剂添加剂，所述官能化分散剂添加剂为A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物。
组分A
组分A的烃基-二元羧酸或酸酐的烃基部分可来源于丁烯聚合物例如异丁烯的聚合物。本文使用的合适的聚异丁烯包括由具有至少约60%，比如约70%-约90%及以上的末端亚乙烯基含量的聚异丁烯或高活性聚异丁烯形成的那些。合适的聚异丁烯可包括那些用BF3催化剂制备的聚异丁烯。聚烯基取代基的数均分子量可大范围变化，例如约100-约5000，比如约500-约5000，用如上所述的聚苯乙烯作为校准基准通过GPC确定。
组分A的二元羧酸或酸酐可选自马来酸酐或除马来酸酐以外的含羧基的反应物，比如马来酸、富马酸、苹果酸、酒石酸、衣康酸、衣康酸酐、柠康酸、柠康酸酐、中康酸、乙基马来酸酐、二甲基马来酸酐、乙基马来酸、二甲基马来酸、己基马来酸等，包括相应的酰卤和低级脂肪族酯。合适的二羧基酸酐为马来酸酐。用于制造组分A的反应混合物中的马来酸酐同烃基部分的摩尔比可广泛变化。相应地，所述摩尔比可从约5:l至约1:5，例如从约3:l至约1:3变化，且作为另一个实例，马来酸酐可在化学当量过量下使用以促使反应完成。未反应的马来酸酐可通过真空蒸馏除去。
组分B
众多聚胺的任意种类可在制备官能化分散剂中用作组分B。非限制性的示例性聚胺可包括氨基胍碳酸氢盐(AGBC)、二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)、五亚乙基六胺(PEHA)和重聚胺。重聚胺可包含具有少量低级聚胺低聚物比如TEPA和PEHA，但主要为具有七个或更多氮原子的低聚物的聚亚烷基聚胺的混合物，所述聚亚烷基聚胺每分子有两个或更多个伯胺，并比常规聚胺混合物更广泛支化。另外的可用来制备烃基-取代琥珀酰亚胺分散剂的非限制性聚胺在美国专利号6,548,458中公开，其公开内容通过引用全文结合到本文中。在本公开内容的一个实施方案中，聚胺可选自四亚乙基五胺(TEPA)。
在一个实施方案中，官能化分散剂可来源于式(I)的化合物：
其中n表示0或1到5的整数，且R2为如以上所定义的烃基取代基。在一个实施方案中，n为3且R2为聚异丁烯基取代基，比如来源于具有至少约60%，比如约70%-约90%及以上的末端亚乙烯基含量的聚异丁烯的那些。式(I)的化合物可为烃基-取代琥珀酸酐比如聚异丁烯基琥珀酸酐(PIBSA)和聚胺例如四亚乙基五胺(TEPA)的反应产物。
上述式(I)的化合物的(A)聚异丁烯基-取代琥珀酸酐同(B)聚胺在化合物中的摩尔比在约4:3至约1:10的范围内。特别有用的分散剂含有数均分子量(Mn)在约500-5000范围内(使用聚苯乙烯作为校准基准通过GPC确定)的聚异丁烯基-取代琥珀酸酐的聚异丁烯基，和(B)通式为H2N(CH2)m-[NH(CH2)m]n-NH2的聚胺，其中m在2至4的范围内且n在1至2的范围内。
组分C
组分C为羧酸或聚羧酸或聚酸酐，其中羧酸或酸酐的官能度直接稠合到芳基上。这种含羧基的芳香族化合物可选自1,8-萘二甲酸或酸酐和1,2-萘二甲酸或酸酐、2,3-二元羧酸或酸酐、萘-1,4-二甲酸、萘-2,6-二甲酸、邻苯二甲酸酐、苯均四酸酐、1,2,4-苯三甲酸酐、联苯甲酸或酸酐、2,3-吡啶二甲酸或酸酐、3,4-吡啶二甲酸或酸酐、1,4,58-萘四甲酸或酸酐、茈-3,4,9,10-四甲酸酐、芘二甲酸或酸酐等。每摩尔组分B反应的组分C的摩尔范围可为约0.1:1至约2:1。反应混合物中的组分C同组分B的摩尔比的通常范围可为约0.2:1至约2.0:1。另一可用的组分C同组分B的摩尔比的范围可为0.25:1至约1.5:1。组分C可在约140℃-约180℃的温度范围内与其它组分反应。
组分D
组分D为非芳香族羧酸或酸酐。合适的二元羧酸或其酸酐可包括，但不局限于乙酸或乙酸酐、草酸及草酸酐、丙二酸及丙二酸酐、琥珀酸及琥珀酸酐、烯基琥珀酸或烯基琥珀酸酸酐、戊二酸及戊二酸酐、己二酸及己二酸酐、庚二酸及庚二酸酐、辛二酸及辛二酸酐、壬二酸及壬二酸酐、癸二酸及癸二酸酐、马来酸及马来酸酐、富马酸及富马酸酐、酒石酸或酒石酸酐、羟基乙酸或羟基乙酸酐、1,2,3,6-四氢萘二甲酸或1,2,3,6-四氢萘二甲酸酐等。组分D与组分B反应的摩尔比的范围为约0.1-约2.5摩尔组分D每摩尔反应的组分B。通常，使用的组分D的量与组分B中仲氨基的数目有关。因此，约0.2-约2.0摩尔组分D每组分B中的仲氨基可与其它组分反应以提供根据本公开内容的实施方案的分散剂。可使用的另一组分D同组分B的摩尔比的范围可为0.25:1至约1.5:1摩尔组分D每摩尔组分B。组分D可在约140℃-约180℃的温度范围内与其它组分反应。
润滑剂组合物可含有基于润滑剂组合物总重量的约0.5重量%-约10.0重量%的上述官能化分散剂。分散剂的通常范围可为基于润滑剂组合物总重量的约2重量%-约5重量%。除上述的官能化分散剂以外，润滑剂组合物可包括其它常规成分，所述成分包括、但不限于摩擦调节剂、另外的分散剂、金属去污剂、抗磨剂、消泡剂、抗氧化剂、粘度调节剂、倾点下降剂、防腐剂等。
含金属去污剂
可与以上所述的分散剂反应产物使用的金属去污剂一般包含极性头与长的疏水尾，其中极性头包含酸性有机化合物的金属盐。该盐可含有大致化学计算量的金属，在这种情况下，其常被描述为中式盐或中性盐，并且通常可具有约0至低于约150的总碱值或TBN(通过ASTM D2896测量)。可通过使过量的金属化合物(例如氧化物或氢氧化物)与酸性气体(例如二氧化碳)反应而包含大量的金属碱。所得高碱性去污剂包含围绕无机金属碱(例如水化碳酸盐)核的中和去污剂的胶束。这类高碱性去污剂的TBN可为约150或更大，例如约150-约450或更大。
可适用于本发明实施方案的去污剂包括金属特别是碱金属或碱土金属(例如钠、钾、锂、钙和镁)的油溶性的高碱性、低碱性和中性磺酸盐、酚盐、硫化酚盐和水杨酸盐。可存在不止一种金属，例如钙和镁两者。钙和/或镁与钠的混合物也可以是适宜的。合适的金属去污剂可以是TBN为150-450 TBN的高碱性磺酸钙或磺酸镁、TBN为150-300的高碱性钙或镁酚盐或硫化酚盐和TBN为130-350的高碱性水杨酸钙或水杨酸镁。还可使用这类盐的混合物。
含金属去污剂可以约0.5重量%-约5重量%的量存在于润滑组合物中。再举例来说，含金属去污剂可以约1.0重量%-约3.0重量%的量存在。含金属去污剂可以足以向润滑剂组合物提供基于润滑剂组合物总重量的约500-约5000 ppm碱金属和/或碱土金属的量存在于润滑组合物中。再举例来说，含金属去污剂可以足以提供约1000-约3000 ppm碱金属和/或碱土金属的量存在于润滑组合物中。
基于磷的抗磨剂
可使用基于磷的防磨剂，且其可包含金属二烃基二硫代磷酸盐化合物，例如但不限于二烃基二硫代磷酸锌化合物。合适的金属二烃基二硫代磷酸盐可包含二烃基二硫代磷酸金属盐，其中金属可以是碱金属或碱土金属或铝、铅、锡、钼、锰、镍、铜或锌。
可按照已知技术，通常通过一种或多种醇或酚与P2S5反应首先形成二烃基二硫代磷酸(DDPA)，然后用金属化合物中和所形成的DDPA，来制备二烃基二硫代磷酸金属盐。例如，二硫代磷酸可通过使伯醇和仲醇的混合物反应来制备。或者，可制备多种二硫代磷酸，其中一个二硫代磷酸上的烃基在性质上全是仲烃基而在其它二硫代磷酸上的烃基在性质上全是伯烃基。为了制备金属盐，可使用任何碱性或中性金属化合物，但最常使用氧化物、氢氧化物和碳酸盐。市售添加剂通常因在中和反应中使用过量碱性金属化合物而含有过量金属。
二烃基二硫代磷酸锌(ZDDP)是二烃基二硫代磷酸的油溶性盐，可由下式表示：
其中R和R'可为相同或不同的烃基，含有1-18个、例如2-12个碳原子并且包括例如以下基团：烷基、烯基、芳基、芳基烷基、烷芳基和脂环基。R和R'基团可为2-8个碳原子的烷基。因此，该基团可为例如乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、戊基、正己基、异己基、正辛基、癸基、十二烷基、十八烷基、2-乙基己基、苯基、丁基苯基、环己基、甲基环戊基、丙烯基、丁烯基。为了得到油可溶性，二硫代磷酸中碳原子的总数(即R和R')一般可为约5个或更多个。因此，二烃基二硫代磷酸锌可包括二烷基二硫代磷酸锌。
可用作基于磷的防磨剂的其它合适组分包括任何合适的有机磷化合物，例如但不限于磷酸酯、硫代磷酸酯、二硫代磷酸酯、亚磷酸酯及其盐和膦酸盐。合适的实例为磷酸三甲苯酯(TCP)、二烷基亚磷酸酯(例如亚磷酸氢二丁酯)和戊酸磷酸酯。
另一种合适的组分是磷酸化琥珀酰亚胺，例如来自烃基取代的琥珀酸酰化剂和与磷源(例如无机或有机磷酸或酯)混合的聚胺之间的反应的完全反应产物。此外，其可包含这样的化合物，即其中除由伯氨基和酐部分反应产生的类型的酰亚胺键以外，产物还可具有酰胺、脒和/或盐键。
基于磷的防磨剂可以足以提供约200-约2000 ppm磷的量存在于润滑组合物中。再举例来说，基于磷的防磨剂可以足以提供约500-约800 ppm磷的量存在于润滑组合物中。
基于磷的防磨剂可以这样的量存在于润滑组合物中，所述量足以提供约1.6-约3.0(ppm/ppm)的基于润滑组合物中碱金属和/或碱土金属总量的碱金属和/或碱土金属含量(ppm)与基于润滑组合物中磷的总量的磷含量(ppm)的比率。
摩擦调节剂
本公开内容的实施方案可包括一种或多种摩擦调节剂。合适的摩擦调节剂可包括含金属和不含金属的摩擦调节剂，可包括但不限于咪唑啉、酰胺、胺、琥珀酰亚胺、烷氧基化胺、烷氧基化醚胺、胺氧化物、酰氨基胺、腈、甜菜碱、季铵、亚胺、胺盐、氨基胍、烷醇酰胺、膦酸盐、含金属化合物、甘油酯等。
合适的摩擦调节剂可含有选自直链、支链或芳族烃基或其混合物的烃基，并且可以是饱和或不饱和的。烃基可由碳和氢或杂原子(例如硫或氧)组成。烃基可为约12-约25个碳原子，可以是饱和或不饱和的。
胺式摩擦调节剂可包括聚胺的酰胺。这类化合物可具有饱和或不饱和的线性烃基或其混合物，可含有约12-约25个碳原子。
合适摩擦调节剂的另外实例包括烷氧基化胺和烷氧基化醚胺。这类化合物可具有饱和的、不饱和的线性烃基或其混合物。它们可含有约12-约25个碳原子。实例包括乙氧基化胺和乙氧基化醚胺。
胺和酰胺可照原样使用或以与例如氧化硼、卤化硼、偏硼酸盐/酯、硼酸或单烷基硼酸酯、二烷基硼酸酯或三烷基硼酸酯等硼化合物的加合物或反应产物的形式使用。其它合适的摩擦调节剂描述于US 6,300,291，其通过引用结合到本文中。
其它合适的摩擦调节剂可包括有机、无灰(无金属)、无氮有机摩擦调节剂。这类摩擦调节剂可包括通过使羧酸和酐与烷醇反应形成的酯。其它有用的摩擦调节剂一般包括与亲油烃链共价结合的极性端基(例如羧基或羟基)。羧酸和酐与烷醇的酯描述于U.S. 4,702,850。有机无灰无氮摩擦调节剂的另一个实例一般称为甘油单油酸酯(GMO)，其可含有油酸的单酯和二酯。其它合适的摩擦调节剂描述于US 6,723,685，其通过引用结合到本文中。无灰摩擦调节剂可以占润滑剂组合物总重量约0.1-约0.4重量%的量存在于润滑剂组合物中。
合适的摩擦调节剂还可包括一种或多种钼化合物。钼化合物可选自二硫代氨基甲酸钼(MoDTC)、二硫代磷酸钼、二硫代亚膦酸钼、黄原酸钼、硫代黄原酸钼、硫化钼、三核有机钼化合物、钼/胺络合物及其混合物。另外，钼化合物可以是酸性钼化合物。包括钼酸、钼酸铵、钼酸钠、钼酸钾和其它碱金属钼酸盐和其它钼盐，例如钼酸氢钠、MoOCl4、MoO2Br2、Mo2O3Cl6、三氧化钼或类似的酸性钼化合物。或者，可通过以下文献描述的碱性氮化合物的钼/硫络合物向组合物提供钼：例如美国专利号4,263,152、4,285,822、4,283,295、4,272,387、4,265,773、4,261,843、4,259,195和4,259,194和WO 94/06897。
合适的二硫代氨基甲酸钼可用下式表示：
其中R1、R2、R3和R4各自独立地表示氢原子、C1-C20烷基、C6-C20环烷基、芳基、烷基芳基或芳烷基或者含有酯、醚、醇或羧基的C3-C20烃基；X1、X2、Y1和Y2各自独立地表示硫或氧原子。
R1、R2、R3和R4各自合适的基团的实例包括2-乙基己基、壬基苯基、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、正己基、正辛基、壬基、癸基、十二烷基、十三烷基、月桂基、油基、亚油基、环己基和苯基甲基。R1-R4各自可具有C6-C18烷基。X1和X2可相同，Y1和Y2可相同。X1和X2两个可包含硫原子，Y1和Y2两个可包含氧原子。
二硫代氨基甲酸钼的另外实例包括C6-C18二烷基二硫代氨基甲酸酯或二芳基二硫代氨基甲酸酯或者烷基-芳基二硫代氨基甲酸酯，例如二硫代氨基甲酸二丁酯、二硫代氨基甲酸二戊基-二-(2-乙基-己基)酯、二硫代氨基甲酸二月桂酯、二硫代氨基甲酸二油酯和二硫代氨基甲酸二环己酯。
另一类别的合适有机钼化合物是三核钼化合物，例如式Mo3SkLnQz的三核钼化合物及其混合物，其中L表示独立选择的配基，其具有有足够数目的碳原子以使化合物可溶于或可分散于油中的有机基团，n为1-4，k从4到7不等，Q选自中性供电子化合物，例如水、胺、醇、膦和醚，z的范围为0-5，并包括非化学计量值。至少共21个碳原子可存在于所有配配基的有机基团中，例如至少25个、至少30个或至少35个碳原子。其它合适的钼化合物描述于US 6,723,685，其通过引用结合到本文中。
钼化合物可以提供约5 ppm-200 ppm钼的量存在于充分配制发动机润滑剂中。再举例来说，钼化合物可以提供约50-100 ppm钼的量存在。
消泡剂
在一些实施方案中，抑泡剂可构成适用于组合物的另一种组分。抑泡剂可选自硅酮、聚丙烯酸脂等。本文所述发动机润滑剂制剂的消泡剂的量可占制剂总重的约0.001重量%-约0.1重量%。再举例来说，消泡剂可以约0.004重量%-约0.008重量%的量存在。
分散剂组分
润滑剂组合物中含有的另外的分散剂可包括，但不局限于具有能够与待分散的颗粒缔合的官能团的油溶性聚合烃骨架。通常，分散剂包含常通过桥连基与聚合物骨架连接的胺、醇、酰胺、或酯极性部分。分散剂可选自美国专利号3,697,574和3,736,357中描述的曼尼希分散剂；美国专利号4,234,435和4,636,322中描述的无灰琥珀酰亚胺分散剂；美国专利号3,219,666、3,565,804和5,633,326中描述的胺分散剂；美国专利号5,936,041、5,643,859和5,627,259中描述的Koch分散剂以及美国专利号5,851,965、5,853,434和5,792,729中描述的聚亚烷基琥珀酰亚胺分散剂。。
氧化抑制剂组分
氧化抑制剂或抗氧化剂降低使用中的基本原料变质的倾向，可通过沉积在金属表面的氧化产物(例如油泥和清漆样沉积物)及通过润滑剂成品粘度增加来证实变质。这类氧化抑制剂包括受阻酚、硫化受阻酚、具有C5-C12烷基侧链的烷基酚硫酯的碱土金属盐、硫化烷基酚、硫化或非硫化烷基酚的金属盐例如壬基酚硫化钙、无灰油溶性酚盐和硫化酚盐、硫磷化烃或硫化烃、磷酯、金属硫代氨基甲酸酯和油溶性铜化合物，参见美国专利号4,867,890。
可使用的其它抗氧化剂包括空间受阻酚及其酯、二芳基胺、烷基化吩噻嗪、硫化化合物和无灰二烷基二硫代氨基甲酸酯。空间受阻酚的非限制性实例包括但不限于2,6-二-叔丁基苯酚、2,6二-叔丁基甲基苯酚、4-乙基-2,6-二-叔丁基苯酚、4-丙基-2,6-二-叔丁基苯酚、4-丁基-2,6-二-叔丁基苯酚、4-戊基-2,6-二-叔丁基苯酚、4-己基-2,6-二-叔丁基苯酚、4-庚基-2,6-二-叔丁基苯酚、4-(2-乙基己基)-2,6-二-叔丁基苯酚、4-辛基-2,6-二-叔丁基苯酚、4-壬基-2,6-二-叔丁基苯酚、4-癸基-2,6-二-叔丁基苯酚、4-十一烷基-2,6-二-叔丁基苯酚、4-十二烷基-2,6-二-叔丁基苯酚；亚甲基桥接空间受阻酚包括但不限于4,4-亚甲基双(6-叔丁基-邻甲酚)、4,4-亚甲基双(2-叔戊基-邻甲酚)、2,2-亚甲基双(4-甲基-6叔丁基苯酚、4,4-亚甲基-双(2,6-二-叔丁基苯酚)及其混合物，参见美国公开号2004/0266630。
二芳基胺抗氧化剂包括但不限于具有下式的二芳基胺：
其中R’和R’’各自独立表示具有6-30个碳原子的取代或未取代芳基。芳基的说明性取代基包括脂族烃基团，例如具有1-30个碳原子的烷基、羟基、卤素基团、羧酸或酯基团或者硝基。
芳基优选为取代或未取代苯基或萘基，特别是其中一个或两个芳基被至少一个具有4-30个碳原子、优选4-18个碳原子、最优选4-9个碳原子的烷基取代。优选一个或两个芳基是取代的，例如单-烷基化二苯胺、二-烷基化二苯胺或单-烷基化二苯胺和二-烷基化二苯胺的混合物。
二芳基胺可具有在分子中含有不止一个氮原子的结构。因此，二芳基胺可含有至少两个氮原子，其中至少一个氮原子具有与之连接的两个芳基，例如正如在具有仲氮原子以及氮原子之一上有两个芳基的各种二胺情况。
可使用的二芳基胺的实例包括但不限于：二苯胺、各种烷基化二苯胺、3-羟基二苯胺、N-苯基-1,2-苯二胺、N-苯基-1,4-苯二胺、一丁基二苯基-胺、二丁基二苯胺、一辛基二苯胺、二辛基二苯胺、一壬基二苯胺、二壬基二苯胺、单十四烷基二苯胺、双十四烷基二苯胺，苯基-α-萘胺、一辛基苯基-α-萘胺、苯基-β-萘胺、一庚基二苯胺、二庚基-二苯胺、对位取向的苯乙烯化二苯胺(p-oriented styrenated diphenylamine)、混合的丁基辛基二-苯胺和混合的辛基苯乙烯基二苯胺。
含硫抗氧化剂包括但不限于硫化烯烃，其特征在于用于其产生的烯烃的类型和抗氧化剂的最终硫含量。优选高分子量烯烃，即平均分子量为168-351 g/摩尔的烯烃。可使用的烯烃的实例包括α-烯烃、异构化α-烯烃、支链烯烃、环状烯烃和这些烯烃的组合。
α-烯烃包括但不限于任何C4-C25 α-烯烃。α-烯烃可在硫化反应前或在硫化反应期间异构化。也可使用含有内部双键和/或支链的α烯烃的结构和/或构象异构体。例如，异丁烯是α-烯烃1-丁烯的支链烯烃对应物。
可用于烯烃硫化反应中的硫源包括：元素硫、一氯化硫、二氯化硫、硫化钠、多硫化钠和一起加入或在硫化过程不同阶段加入的这些硫源的混合物。
不饱和油因其未饱和，也可硫化并用作抗氧化剂。可以使用的油或脂肪的实例包括玉米油、低芥酸菜子油、棉籽油、葡萄籽油、橄榄油、棕榈油、花生油、椰子油、油菜籽油、红花籽油、芝麻籽油、豆油、葵花籽油、动物脂和这些油的组合。
供给润滑剂成品中的硫化烯烃或硫化脂肪油的量以硫化烯烃或脂肪油的硫含量和待供给润滑剂成品中的所需硫水平为基础。例如，含有20重量%硫的硫化脂肪油或烯烃，当以1.0重量%处理水平加到润滑剂成品中时，将向润滑剂成品提供2000 ppm硫。含有10重量%硫的硫化脂肪油或烯烃，当以1.0重量%处理水平加入润滑剂成品中时，将向润滑剂成品提供1000 ppm硫。期望硫化烯烃或硫化脂肪油向润滑剂成品提供介于200 ppm和2000 ppm之间的硫。
概括地讲，合适的发动机润滑剂可包含下表所列范围的添加剂组分。
表2。
| 组分 | 重量%(宽泛的) | 重量%(典型的) |
| 分散剂(组分A、B、C和D的反应产物) | 0.5 - 10.0 | 1.0 - 5.0 |
| 另外的分散剂 | 0 - 10% | 1.0 - 6.0% |
| 抗氧化剂 | 0 - 5.0 | 0.01 - 3.0 |
| 缓蚀剂 | 0 - 5.0 | 0 - 2.0 |
| 金属二烃基二硫代磷酸盐 | 0.1 - 6.0 | 0.5 - 4.0 |
| 无灰胺磷酸盐 | 0 - 6.0 | 0.0 - 4.0 |
| 消沫剂 | 0 - 5.0 | 0.001 - 0.15 |
| 抗磨剂 | 0 - 1.0 | 0 - 0.8 |
| 倾点下降剂 | 0.01 - 5.0 | 0.01 - 1.5 |
| 粘度调节剂 | 0.01 - 20.00 | 0.25 - 10.0 |
| 摩擦调节剂 | 0 - 2.0 | 0.1 - 1.0 |
| 基础油 | 余量 | 余量 |
| 总计 | 100 | 100 |
另外任选的可包括在本文描述的润滑剂组合物中的添加剂包括，但不局限于防锈剂、乳化剂、反乳化剂和油溶性含钛添加剂。
可将用于配制本文所述组合物的添加剂单独或以各种子组合形式混入基础油中。然而，使用添加剂浓缩物(即添加剂加稀释剂，例如烃溶剂)将所有组分同时混合可为合适的。当呈添加剂浓缩物的形式时，使用添加剂浓缩物可利用由各成分组合所提供的相互相容性。另外，使用浓缩液可减少混合时间，并可降低混合错误的可能性。
本公开内容提供特别配制用作机动车发动机润滑剂的新的润滑油混合物。本公开内容的实施方案可提供适于发动机应用的润滑油，它在一个或多个以下特征提供改进：抗氧化性、抗磨损性、防锈作用、燃料经济性、耐水性、加气处理、密封保护和泡沫减少性质。
为了证实本公开内容的润滑剂组合物的益处和优势，提供下面的非限制性实施例。
实施例1
该装置需要1 L的4-颈烧瓶，带有搅拌器、加料漏斗、温度传感器、温度控制器、加热罩、迪安-斯达克榻分水器(Dean-Stark trap)和冷凝器。烧瓶装入2100 Mn聚异丁烯琥珀酸酐(PIBSA)(195.0 g；0.135摩尔)并在氮气覆盖层下加热到160℃。逐滴添加聚亚乙基胺混合物(21.17 g；0.112摩尔)经30分钟。将反应混合物搅拌4小时，然后在mm Hg下真空汽提1小时。添加工艺用油(172.0 g)并将混合物搅拌15分钟。在160℃下整体(in one portion)添加1，8-萘二甲酸酐(13.39 g；0.068摩尔)。将反应混合物加热到165℃。并搅拌4小时。施加真空(771 mm Hg)1小时以除去任何残留水。将反应产物经Hiflow Super Cel Celite加压过滤以产生364 g暗褐色粘性液体(% N，1.75；TBN，36.0)。
实施例2
500 mL烧瓶装入来自实施例1的材料(200.0 g；0.102摩尔)并在氮气覆盖层下加热到160℃。整体添加碳酸乙二酯(4.0 g；0.045摩尔)。将反应混合物搅拌4小时，然后在711 mm Hg下真空汽提1小时。添加工艺用油(4.0 g)并将混合物搅拌15分钟。将反应产物经Hiflow Super Cel Celite加压过滤以产生171 g暗褐色粘性液体(% N，1.69；TBN，34.3)。
实施例3
500 mL烧瓶装入来自实施例1的材料(200.0 g；0.102摩尔)并在氮气覆盖层下加热到160℃。整体添加硼酸(2.81 g；0.045摩尔)。将反应混合物搅拌4小时，然后在711 mm Hg下真空汽提1小时。添加工艺用油(2.81 g)并将混合物搅拌15分钟。将反应产物经Hiflow Super Cel Celite加压过滤以产生162 g暗褐色粘性液体(% N，1.75；TBN，36.7)。
实施例4
500 mL烧瓶装入来自实施例1的材料(200.0 g；0.102摩尔)并在氮气覆盖层下加热到160℃。整体添加马来酸酐(4.48 g；0.045摩尔)。将反应混合物搅拌4小时，然后在711 mm Hg下真空汽提1小时。添加工艺用油(4.48 g)并将混合物搅拌15分钟。将反应产物经Hiflow Super Cel Celite加压过滤以产生165 g暗褐色粘性液体(% N，1.67；TBN，24.1)。
实施例5
500 mL烧瓶装入来自实施例1的材料(200.0 g；0.102摩尔)并在氮气覆盖层下加热到160℃。整体添加1,8-萘二甲酸酐(9.02 g；0.045摩尔)。将反应混合物搅拌4小时，然后在711 mm Hg下真空汽提1小时。添加工艺用油(9.02 g)并将混合物搅拌15分钟。将反应产物经Hiflow Super Cel Celite加压过滤以产生159 g暗褐色粘性液体(% N，1.62；TBN，25.1)。
实施例6
组装4 L的四颈烧瓶，其带有搅拌器、加料漏斗、温度传感器、温度控制器、加热罩、迪安-斯达克榻分水器和冷凝器。将烧瓶装入2100 Mn PIBSA(975 g；0.677摩尔)并在氮气覆盖层下加热到160℃。向反应混合物逐滴添加聚亚乙基胺混合物(85.81 g；0.454摩尔)经30分钟。将反应混合物搅拌4小时，然后在771 mm Hg下真空汽提1小时。 添加工艺用油(850 g)并将混合物搅拌15分钟。将反应产物经Hiflow Super Cel Celite加压过滤以产生1700 g暗褐色粘性液体。
实施例7
1 L四颈烧瓶装入来自实施例6的材料(565.0 g；0.200摩尔)并在氮气覆盖层下加热到160℃。向烧瓶整体添加邻苯二甲酸酐(14.82 g；0.100摩尔)。将反应混合物搅拌2小时，然后在660 mm Hg下真空汽提1小时。随后逐滴添加乙酸酐(10.20 g；0.100摩尔)并在160℃下将混合物搅拌2小时。将反应产物经Hiflow Super Cel Celite加压热过滤以产生500 g暗褐色粘性液体(% N，1.46；TBN，18.2)。
实施例8
1 L四颈烧瓶装入来自实施例6的材料(293.8 g；0.104摩尔)并在氮气覆盖层下加热到160℃。向烧瓶整体添加1,2,4-苯三甲酸酐(10.01 g；0.052摩尔)。将反应混合物搅拌2小时，然后在660 mm Hg下真空汽提1小时。随后逐滴添加乙酸酐(5.30 g；0.052摩尔)并在160℃下将混合物搅拌2小时。将反应产物经Hiflow Super Cel Celite加压热过滤以产生300 g暗褐色粘性液体(% N，1.49；TBN，26.6)。
实施例9
1 L四颈烧瓶装入来自实施例6的材料(565.0 g；0.200摩尔)并在氮气覆盖层下加热到160℃。整体添加1,8-萘二甲酸酐(19.8 g；0.100摩尔)。将反应混合物搅拌2小时，然后在660 mm Hg下真空汽提1小时。随后逐滴添加乙酸酐(10.20 g；01.00摩尔)并在160℃下将混合物搅拌2小时。将反应产物经Hiflow Super Cel Celite加压热过滤以产生500 g暗褐色粘性液体(% N，1.63；TBN，19.5)。
实施例10
125 mL 3-颈烧瓶装入来自实施例6的材料(50.6 g；0.018摩尔)并在氮气覆盖层下加热到160℃。整体添加1,4,5,8-萘四甲酸二酐(2.40 g；0.009摩尔)。将反应混合物搅拌4小时，然后在711 mm Hg下真空汽提1小时。 随后整体添加顺式1,2,3,6-四氢邻苯二甲酸酐(1.40 g；0.009摩尔)并将混合物搅拌4小时。将反应产物经Hiflow Super Cel Celite真空热过滤以产生17.8 g暗褐色粘性液体(% N，1.65；TBN，21.5)。
实施例11
125 mL 3-颈烧瓶装入来自实施例6的材料(49.3 g；0.018摩尔)并在氮气覆盖层下加热到160℃。整体添加1,4,5,8-萘四甲酸二酐(2.33 g；0.009摩尔)。将反应混合物搅拌3小时，然后在711 mm Hg下真空汽提1小时。随后整体添加乙酸酐(0.889 g；0.009摩尔)并将混合物搅拌3小时。将反应产物经Hiflow Super Cel Celite真空热过滤以产生21.7 g暗褐色粘性液体(% N，1.39；TBN，14.5)。
实施例12
125 mL 3-颈烧瓶装入来自实施例6的材料(55.6 g；0.020摩尔)并在氮气覆盖层下加热到160℃。整体添加邻苯二甲酸酐(1.46 g；0.010摩尔)。将反应混合物搅拌3小时，然后在711 mm Hg下真空汽提1小时。随后整体添加(2-十二烯-1-基)琥珀酸酐(2.61 g；0.010摩尔)并将混合物搅拌3小时。将反应产物经Hiflow Super Cel Celite真空热过滤以产生20.4 g暗褐色粘性液体(% N，1.65；TBN，21.5)。
实施例13
125 mL 3-颈烧瓶装入来自实施例6的材料(50.6 g；0.018摩尔)并在氮气覆盖层下加热到160℃。整体添加1,8-萘二甲酸酐(1.81 g；0.009摩尔)。将反应混合物搅拌3小时，然后在711 mm Hg下真空汽提1小时。随后整体添加(2-十二烯-1-基)琥珀酸酐(2.40 g；0.009摩尔)并将混合物搅拌3小时。将反应产物经Hiflow Super Cel Celite真空热过滤以产生26.9 g暗褐色粘性液体(% N，1.46；TBN，16.3)。
评价烟灰分散性的试验
为评估根据本公开内容的润滑剂制剂，对多个分散剂试验其分散烟灰的能力。由点火的柴油机用不包含分散剂的流体产生具有4.3重量%烟灰的烟灰油。随后用3.5重量%的来自实施例1-5的分散剂对烟灰油顶端处理，然后在板上带有锥体的流变仪中通过剪切速率扫描进行试验以找出牛顿/非牛顿行为。结果可参见图1。
未处理的烟灰油(不包含分散剂的曲线A)显示粘度作为剪切速率函数的曲线，这意味着其为非牛顿流体且烟灰正在聚结。较低剪切下的较高粘度为烟灰聚结的标志。另一方面，实施例1-5的所有分散剂(曲线B-F)显示不随剪切增加而改变的粘度对剪切速率曲线。此外，低剪切下的粘度低于曲线A的粘度。这些结果显示实施例1-5在3.5重量%的处理率下有效地分散了烟灰。
密封适应性试验
在3.5和4.0重量%下试验实施例1-5的分散剂在表3列出的参考流体中的AK-6密封适应性。将氟弹性体橡胶用L型模头切成骨形块。随后将橡胶块浸入30 mL含有约22克待试验的油组合物的闪烁管中。将管用箔覆盖并在150℃炉中放置七天。在七天后，将管排干并将橡胶块吸干以除去多余的油。对每个橡胶块进行伸长率断裂试验并将结果记录于表4中。
表3。
| 组分 | 重量% |
| 实施例1-5的分散剂 | 3.5或4.0 |
| 烷基化二苯胺抗氧化剂 | 1.0 |
| 酚类抗氧化剂 | 1.5 |
| 金属去污剂 | 2.5 |
| 二烃基二硫代磷酸锌 | 1.2 |
| 倾点下降剂 | 0.1 |
| 粘度调节剂 | 9.5 |
| 消泡剂 | 0.01 |
| 基础油 | 余量 |
| 合计 | 100 |
表4。
| 试验号 | 分散剂 | 处理率(重量%) | 伸长率断裂(%) |
| 1 | 实施例1的基础分散剂(组分A、B和C的反应产物) | 3.5 | -52.77 |
| 2 | 实施例2的分散剂(实施例1的分散剂与碳酸乙二酯反应) | 3.5 | -59.08 |
| 3 | 实施例3的分散剂(实施例1的分散剂与硼酸反应) | 3.5 | -60.40 |
| 4 | 实施例5的分散剂(实施例1的分散剂与萘二甲酸酐反应) | 3.5 | -57.09 |
| 5 | 实施例4的分散剂(实施例1的分散剂与马来酸酐反应) | 3.5 | -27.15 |
| 6 | 实施例1的基础分散剂(实施例1的分散剂与组分A、B和C的反应产物反应) | 4.0 | -56.44 |
| 7 | 实施例2的分散剂(实施例1的分散剂与碳酸乙二酯反应) | 4.0 | -55.76 |
| 8 | 实施例3的分散剂(实施例1的分散剂与硼酸反应) | 4.0 | -64.74 |
| 9 | 实施例5的分散剂(实施例1的分散剂与萘二甲酸酐反应) | 4.0 | -56.76 |
| 10 | 实施例4的分散剂(实施例1的分散剂与马来酸酐反应) | 4.0 | -37.80 |
如上述结果所示，与实施例1的基础分散剂、以及与碳酸乙二酯(实施例2)、硼酸(实施例3)和芳香族萘二甲酸酐(实施例5)反应的那些相比，实施例4的分散剂(基础分散剂与马来酸酐反应)显示优良的伸长率断裂结果。例如，在参考油中3.5重量%的处理率下，分散剂4比基础分散剂(分散剂1)好约49%，以及比经硼酸处理的分散剂(分散剂3)或经碳酸乙二酯处理的分散剂(分散剂2)好差不多54-55%。在参考油中4重量%的处理率下，分散剂4比分散剂1、2、3和5好约32%-约41%。因此，与其它官能化分散剂相比，根据本公开内容的官能化分散剂在密封适应性方面优越。
在整个本说明书的多个地方，提及到多个美国专利。所有这类引用的文献以全文明确结合到本公开内容中，就像完整陈列在本文中。
鉴于本说明书和本文公开的实施方案的实践，本公开内容的其它实施方案对本领域技术人员而言将是显而易见的。贯穿本说明书和权利要求书使用的不定冠词“一个”和/或“一种”可指一个或不止一个。除非另有说明，否则用于本说明书和权利要求书的表示成分的量、性质例如分子量、百分比、比率、反应条件等的所有数值在所有情况下都要理解为被术语“约”修饰。因此，除非相反地说明，否则本说明书和权利要求书中给出的数值参数是近似值，其可随寻求通过本发明获得的所需性质而改变。丝毫无企图限制权利要求书范围的等同内容的原则的应用，至少应根据所报告的有效数字的数值并通过应用常用的舍入技术解释各数值参数。尽管陈述本发明宽范围的数值范围和参数是近似值，但尽可能精确报告具体实施例中给出的数值。然而，任何数值固有地包括因存在于其各自试验计量的标准差而必然产生的某些误差。旨在仅将本说明书和实施例视为示例性的，本发明的真实范围和精神由随附权利要求书规定。
前述实施方案在实践中易受到相当的改变。因此，不希望将实施方案局限于上文给出的具体实例。相反，前述实施方案落入随附权利要求书的精神和范围内，所述权利要求书包括根据法律可适用的其等同内容。
本专利权所有人无意将任何公开的实施方案奉献给公众，并且就任何公开的修改或改动可不按字面落入权利要求书的范围来说，它们被视为在等同内容原则下的本文的一部分。
Claims (10)
1. 一种发动机润滑剂组合物，所述组合物包含基础油和分散剂，所述分散剂包含A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物。
2. 权利要求1的发动机润滑剂组合物，其中组分C包含1,8-萘二甲酸酐。
3. 权利要求1的发动机润滑剂组合物，其中约0.25-约1.5摩尔的稠合芳香族化合物与每摩尔组分B反应。
4. 权利要求1的发动机润滑剂组合物，其中润滑剂组合物包含约0.5-约5重量%的分散剂。
5. 权利要求1的发动机润滑剂组合物，其中组分A包含聚异丁烯基琥珀酸或酸酐，组分C包含1,8-萘二甲酸酐，且组分D包含马来酸酐。
6. 保持发动机润滑剂的烟灰或油泥处理能力而对发动机中的弹性体密封材料无不利影响的方法，所述方法包含用润滑剂组合物润滑发动机，所述组合物包含基础油和添加剂，所述添加剂包含A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物。
7. 保持发动机润滑剂的烟灰或油泥处理能力的方法，所述方法包含用润滑剂组合物润滑发动机，所述组合物包含基础油和添加剂，所述添加剂包含A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物。
8. 保护发动机中的弹性体密封材料的方法，所述方法包含用润滑剂组合物润滑发动机，所述组合物包含基础油和添加剂，所述添加剂包含A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物。
9. 操作发动机的方法，其包含：
用发动机润滑剂润滑发动机，所述润滑剂包含基础油和润滑剂添加剂包，所述润滑剂添加剂包包含A)烃基-二元羧酸或酸酐，B)聚胺，C)含二羧基的稠合芳香族化合物和D)非芳香族二元羧酸或酸酐的反应产物；和
操作发动机。
10. 权利要求9的方法，其中约0.25-约1.5摩尔的非芳香族二元羧酸或酸酐与每摩尔组分B反应。
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| CN105316082A (zh) * | 2014-05-30 | 2016-02-10 | 雅富顿化学公司 | 具有改进的磨损特性的润滑油组合物及其添加剂 |
| CN107400547B (zh) * | 2016-05-17 | 2020-03-03 | 雅富顿化学公司 | 协同分散剂 |
| CN107400547A (zh) * | 2016-05-17 | 2017-11-28 | 雅富顿化学公司 | 协同分散剂 |
| CN109642176A (zh) * | 2016-09-20 | 2019-04-16 | 朗盛解决方案美国公司 | 烷基化烷氧基二芳基胺抗氧化剂 |
| CN111133084A (zh) * | 2017-09-18 | 2020-05-08 | 雪佛龙奥伦耐有限责任公司 | 聚酰亚胺分散剂及其制备和使用方法 |
| CN110028998A (zh) * | 2018-01-12 | 2019-07-19 | 雅富顿化学公司 | 用于润滑油中的乳化剂 |
| CN110028998B (zh) * | 2018-01-12 | 2022-11-18 | 雅富顿化学公司 | 用于润滑油中的乳化剂 |
| CN110194984A (zh) * | 2018-02-27 | 2019-09-03 | 雅富顿化学公司 | 具有烟尘处理特性的接枝聚合物 |
| CN110194984B (zh) * | 2018-02-27 | 2022-09-23 | 雅富顿化学公司 | 具有烟尘处理特性的接枝聚合物 |
| CN113423806A (zh) * | 2019-01-18 | 2021-09-21 | 雅富顿化学公司 | 用于烟灰处置和减少摩擦的发动机油 |
| CN113423806B (zh) * | 2019-01-18 | 2023-07-14 | 雅富顿化学公司 | 用于烟灰处置和减少摩擦的发动机油 |
| CN111430718A (zh) * | 2020-04-08 | 2020-07-17 | 西北工业大学 | 一种锂基电池电极浆料、制备方法及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5530486B2 (ja) | 2014-06-25 |
| SG188051A1 (en) | 2013-03-28 |
| EP2557144B1 (en) | 2018-06-06 |
| SG10201605219RA (en) | 2016-08-30 |
| CA2783526A1 (en) | 2013-02-11 |
| CA2783526C (en) | 2016-04-19 |
| EP2557144A1 (en) | 2013-02-13 |
| CN102952609B (zh) | 2016-07-06 |
| US20130040866A1 (en) | 2013-02-14 |
| JP2013040332A (ja) | 2013-02-28 |
| US8927469B2 (en) | 2015-01-06 |
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