CN106560506B - 用于配制润滑油组合物的添加剂浓缩物 - Google Patents

用于配制润滑油组合物的添加剂浓缩物 Download PDF

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CN106560506B
CN106560506B CN201610866198.0A CN201610866198A CN106560506B CN 106560506 B CN106560506 B CN 106560506B CN 201610866198 A CN201610866198 A CN 201610866198A CN 106560506 B CN106560506 B CN 106560506B
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concentrate
lubricant additive
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derived
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CN106560506A (zh
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D·B·克拉克
S·奥伯罗伊
J·埃默特
A·W·杨
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Infineum International Ltd
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Abstract

润滑剂添加剂浓缩物,包含(i)分散剂,其是多胺和聚丁烯基琥珀酸酐的聚丁烯基琥珀酰亚胺反应产物,聚丁烯基琥珀酸酐经由烯马来化方法衍生自具有约1300至约2500道尔顿的数均分子量和至少约50%的末端乙烯叉基含量的聚丁烯和和马来酸酐;(ii)具有约300至约900mg KOH/g的总碱值的过碱性镁胶态清净剂;(iii)有机摩擦改进剂,选自C14‑C24烃的羟烷基烷基胺,C13‑C24烃的羟烷基烷基醚胺,衍生自具有C13‑C24烃基取代基的三乙醇胺的烷基酯胺,非碱性脂肪酰胺或它们的混合物;浓缩物中的(i)和(ii)的总质量%为约15至约50质量%;(i):(ii)的质量比为约1:1至约6:1;浓缩物含有约2质量%至约10质量%的(iii);所述浓缩物的其余部分由基础油和除(i)、(ii)和(iii)以外的添加剂组成。

Description

用于配制润滑油组合物的添加剂浓缩物
技术领域
本发明涉及存储稳定的用于配制润滑油组合物的添加剂浓缩物,该添加剂浓缩物含有热衍生自高度反应性聚丁烯的分散剂,以及含有过碱性镁胶态清净剂和有机摩擦改进剂。
发明背景
小客车和重载柴油发动机的曲轴箱润滑剂含有许多添加剂,从而为所述润滑剂提供相应发动机的最佳功能和保护所要求的一系列性能特征。每种独立的添加剂需要提供它所设计的性能益处,而不妨碍润滑剂中其它添加剂的功能。在每种添加剂类别(例如分散剂或清净剂)内,可获得在结构,例如分子量,金属类型,疏水性/亲水性平衡等方面不同的许多选项。任何给定配制剂的添加剂的选择必须考虑各独自添加剂的相对性能特征,以及与该油中存在的其它添加剂的协同作用或对抗作用。
含多重添加剂的添加剂包通常呈浓缩物形式销售给润滑剂配制者,以能够引入一定范围的基础油料来达到不同的目标粘度级别、性能水平和成本。这导致进一步复杂化,因为所选的添加剂必须在浓缩物中彼此相容以避免添加剂包不稳定性和相分离。这种问题由于提高发动机润滑剂的燃料经济性的驱动力而加重,这已经导致使用更高浓度的有机摩擦改进剂以降低发动机内的内摩擦。有机摩擦改进剂通常是高度表面活性的并与浓缩物中的其它极性添加剂强烈地相互作用。具体来说,某些聚合物分散剂,和/或特定过碱性胶态清净剂与大量有机摩擦改进剂的组合可能在长期储存后导致添加剂浓缩物中的相分离,尤其是在高温下。虽然需要所有这些添加剂来控制淤渣和沉积物,维持润滑剂的碱度和降低摩擦,但是在浓缩物中组合地使用这些添加剂提升困难挑战,这归因于各添加剂之间高水平的相互作用。
在一些情形下,根据性能观点的最合意的添加剂结构与其它备选物相比在浓缩物中更加强烈地相互作用。例如,已经出人意料地发现,衍生自具有窄分子量分布的经由热“烯”反应官能化并用多胺衍生的聚合物的高分子量分散剂与衍生自具有更宽分子量分布的经由氯辅助方法官能化的聚合物的相应分散剂相比,对还含有胶态清净剂和高浓度的有机摩擦改进剂的浓缩物中的相分离更加敏感。然而,使用前一类分散剂在排除残余氯并提供最佳活塞沉积物控制的一些应用中是尤其有利的,例如,美国专利Nos.6,743,757和6,734,148中所述那样。相似地,尤其有利的有机摩擦改进剂,单油酸甘油酯(GMO)尤其倾于引起含高分子量分散剂和/或过碱性胶态清净剂的添加剂浓缩物中的相分离,即使当按低于提供有效的摩擦降低所要求的浓度存在时仍如此。这限制了GMO用作现代发动机的燃料经济性添加剂。
美国专利No.7,786,060示出了与形成含过碱性磺酸钙清净剂和高浓度有机摩擦改进剂例如单油酸甘油酯和/或乙氧基化牛脂胺(ETA)的稳定添加剂浓缩物相关的问题。如该专利所示,分别仅含1.1质量%和1.7质量%上述摩擦改进剂(总计2.8质量%)的浓缩物没有通过在高温下的长期稳定性试验。含3.4质量%的这些摩擦改进剂的浓缩物在整个试验持续时间的足够稳定性仅能通过添加5.6-11.1质量%的烃基酚醛浓缩物达到。美国预授权公开2014/0179570;2014/0179572和EP 2746374描述了包含添加剂的组合的发动机油组合物,所述添加剂包括具有明确结构的酰氨基-酯、酰氨基-酰胺或酰氨基羧酸酯摩擦改进剂。美国预授权公开2014/0045734描述了含弱水溶性磷基摩擦改进剂的功能流体组合物的稳定化。制备含琥珀酰亚胺分散剂和过碱性清净剂的抗混浊组合物的高温预共混方法描述在美国专利No.5451333中,该专利还允许存在其它添加剂,包括一定范围的含酯、酰胺、金属、磷或硫的摩擦改进剂。
仍需要能够递送配制现代曲轴箱润滑剂要求的所需高水平的聚合物分散剂、胶态清净剂和摩擦改进剂的添加剂浓缩物,该添加剂浓缩物甚至在高温下延长的存储时期后仍保持稳定,优选不需要添加高水平的相容性助剂,所述相容性助剂本身不为完全配制润滑油组合物提供一些增强特性的性能。
本发明涉及添加剂浓缩物,按规定的浓度范围和比例包含:(i)分散剂,其衍生自具有大于50%的末端乙烯叉基含量的高分子量聚异丁烯,用马来酸酐经由热“烯”反应官能化,并用多胺衍生的琥珀酰亚胺;(ii)过碱性镁胶态清净剂;和(iii)有机摩擦改进剂,其包含选自至少一种羟烷基烷基胺,至少一种羟烷基烷基醚胺,至少一种衍生自三乙醇胺的烷基酯胺,至少一种非碱性脂肪酰胺或它们的混合物的摩擦改进剂。令人惊奇地,已经发现这些添加剂浓缩物维持长期稳定性,即使当在高温下储存时仍如此,同时在用其配制的曲轴箱润滑剂中提供足以达到优异的淤渣和沉积控制和低摩擦性能的量的添加剂。
发明内容
根据本发明的第一个方面,提供了润滑剂添加剂浓缩物,其包含(i)分散剂,其是多胺和聚丁烯基琥珀酸酐(PIBSA)的聚丁烯基琥珀酰亚胺反应产物,所述聚丁烯基琥珀酸酐经由热或“烯”马来化方法衍生自具有大约1300至大约2500道尔顿的数均分子量(Mn)和至少大约50%的末端乙烯叉基含量的聚丁烯和马来酸酐;(ii)过碱性镁胶态清净剂,其具有大约300至大约900mg KOH/g的TBN(基于A.I.);和(iii)有机摩擦改进剂,其包含选自至少一种羟烷基烷基胺,至少一种羟烷基烷基醚胺,至少一种衍生自三乙醇胺的烷基酯胺,至少一种非碱性脂肪酰胺或它们的混合物的有机摩擦改进剂;其中所述浓缩物中的分散剂(i)和过碱性镁胶态清净剂(ii)的总质量%为大约15至大约40质量%(基于A.I.);(i):(ii)的质量比为大约1:1至大约6:1;和所述浓缩物含有大约2质量%至大约10质量%的有机摩擦改进剂(iii);所述浓缩物的其余部分包含基础油和除(i)、(ii)和(iii)以外的添加剂。
根据本发明的第二方面,提供了如第一方面中的润滑剂添加剂浓缩物,其中所述分散剂(i)具有大约1.3至大约2.2的官能度和/或衍生自具有大约1.2至大约3.0的分子量分布(MWD;Mw/Mn)的聚丁烯。
根据本发明的第三个方面,提供了如第一或第二方面中的润滑剂添加剂浓缩物,其中过碱性镁胶态清净剂(ii)是衍生自两种或更多种不同表面活性剂的混杂清净剂或者包括衍生自两种或更多种不同表面活性剂的混杂清净剂。
根据本发明的第四方面,提供了如第一、第二或第三方面中的润滑剂添加剂浓缩物,其中所述浓缩物包含镁和钙和/或钠清净剂的混合物。
根据本发明的第五方面,提供了如第一、第二、第三或第四方面中的润滑剂添加剂浓缩物,其中所述浓缩物包含有机摩擦改进剂(iii)和除(iii)以外的有机摩擦改进剂的混合物。
根据本发明的第六方面,提供了如第一、第二、第三、第四或第五方面中的润滑剂添加剂浓缩物,其中所述浓缩物中的有机摩擦的总浓度为大约4质量%至大约10质量%。
根据本发明的第七方面,提供了如第一、第二、第三、第四、第五或第六方面中的润滑剂添加剂浓缩物,其中所述浓缩物进一步含有低分子量烃基或烯烃基((hydrocarbenyl))琥珀酸酐或琥珀酰亚胺相容性助剂,其衍生自具有大约150至大约1200道尔顿的数均分子量(Mn)的烃基或烯烃基,例如十八碳烯基琥珀酸酐(ODSA)或聚异丁烯基琥珀酸酐(PIBSA),优选以大约0.2至大约8质量%的量含有所述相容性助剂。
本发明的其它和另外的目的、优点和特征壳参考以下说明书理解。
具体实施方式
可用于本发明的分散剂是聚丁烯基琥珀酰亚胺分散剂,它们是多胺和聚丁烯基琥珀酸酐(PIBSA)的反应产物,该聚丁烯基琥珀酸酐衍生自具有大于大约1300,1500和优选大于1800,且小于大约2500,例如小于大约2400的数均分子量(Mn)的聚丁烯。聚丁烯基琥珀酸酐(PIBSA)经由“烯”或热马来化方法衍生自具有至少大约50%、60%、70%,优选至少大约80%的末端乙烯叉基含量的聚丁烯和琥珀酸酐和/或马来酸酐。
本发明的分散剂优选具有大约1.3至大约2.2的官能度,例如大约1.4至大约2.0,更优选大约1.5至大约1.9的官能度。官能度(F)可以根据以下式确定:
F=(SAP×Mn)/((1122×A.I.)-(SAP×MW)) (1)
其中SAP是皂化值(即,完全中和一克含琥珀酰的反应产物中的酸基所消耗的KOH的毫克数,根据ASTM D94测定);Mn是起始烯烃聚合物(聚丁烯)的数均分子量;A.I.是含琥珀酰的反应产物的活性成分百分率(其余部分是未反应的聚丁烯和稀释剂);和MW是产生二元羧酸的结构部分的分子量(对于马来酸酐,是98)。一般而言,每个产生二元羧酸的结构部分(琥珀酰基)将与亲核基团(多胺结构部分)反应并且该PIBSA中的琥珀酰基的数目将决定制成的分散剂中的亲核基团的数目。
可以通过各种已知的技术测定聚合物分子量,特别是Mn。一种方便的方法是凝胶渗透色谱(GPC),其还提供分子量分布信息(参见W.W.Yau,J.J.Kirkland and D.D.Bly,“Modern Size Exclusion Liquid Chromatography”,John Wiley and Sons,New York,1979)。测定分子量的另一种有用的方法,尤其是对于较低分子量聚合物,是蒸气压渗透压测定法(参见例如ASTM D3592)。
本发明的分散剂形成中采用的适合的烃或聚合物包括通过异丁烯的阳离子聚合制备的聚合物。这类的常用聚合物包括通过使具有大约35至大约75wt.%的丁烯含量,和大约30至大约60wt.%的异丁烯含量的C4精炼厂料流在路易斯酸催化剂,例如三氟化硼(BF3)存在下聚合获得的聚异丁烯。优选地,聚异丁烯由纯异丁烯料流或残液I(Raffinate I)料流制备以制备具有末端乙烯叉基烯烃的反应性异丁烯聚合物。优选地,这些聚合物(称为高度反应性聚异丁烯(HR-PIB))具有至少60%,例如70%,更优选至少80%,最优选至少85%的末端乙烯叉基含量。此类聚合物的制备例如在美国专利No.4,152,499中进行了描述。此类聚合物通常称为HR-PIB,HR-PIB可从Texas Petrochemical Corporation(TPC)或从BASF(以商品名GlissopalTM)商购。使HR-PIB与不饱和羧酸或酸酐热反应,并进一步使所得的酰化剂(PIBSA)与胺反应的方法是已知的并例如描述在美国专利Nos.4,152,499和EP 0 355895中。优选地,用于制备本发明的分散剂的HR-PIB具有窄分子量分布(MWD,也称为多分散度),由重均分子量(Mw)与数均分子量(Mn)之比测定。具体来说,衍生本发明的分散剂的HR-PIB具有大约1.2至大约3.0,例如大约1.5至大约2.5或大约1.6至大约2.3,更优选大约1.7至大约2.2的Mw/Mn。
为了提供所要求的官能度,单不饱和羧类反应物(马来酸酐)通常按大约5至大约300%过量,优选大约10-200%,例如20-100%过量的量使用,基于聚合物的摩尔数。可以通过例如汽提从最终分散剂产物除去未反应的过量单不饱和羧类反应物,如果需要,在真空下进行。
可用于形成本发明的分散剂的多胺包括具有或平均具有3-8个氮原子/分子,优选大约5至大约8个氮原子/分子的多胺。这些胺可以是烃基胺,或可以是主要烃基胺,在主要烃基胺中烃基包括其它基团,例如羟基、烷氧基、酰胺基、腈、咪唑啉基等。可以有利地使用胺化合物的混合物,例如通过亚烷基二卤化物与氨反应制备的那些。优选的胺是脂族饱和胺,包括,例如,多亚乙基胺如二亚乙基三胺;三亚乙基四胺;四亚乙基五胺;和多亚丙基胺例如二(1,2-亚丙基)三胺。此类多胺混合物(称为PAM)是可商购的。有用的多胺混合物还包括通过从PAM产物蒸馏轻馏分获得的混合物。所得的混合物(称为“重质”PAM,或HPAM)也是可商购的。PAM和/或HPAM两者的性能和属性例如描述在美国专利Nos.4,938,881;4,927,551;5,230,714;5,241,003;5,565,128;5,756,431;5,792,730和5,854,186中。
优选地,本发明的分散剂具有大约0.7至大约1.3,优选大约0.8至大约1.2,最优选大约0.9至大约1.1的偶联比。在本公开内容范围中,“偶联比”可以定义为PIBSA中的琥珀酰基与多胺反应物中的伯胺基团之比。
本发明润滑剂添加剂浓缩物可以含有除本发明高分子量高官能度分散剂以外的聚合物分散剂添加剂,然而,本发明的分散剂优选占浓缩物中的分散剂的总质量的至少61质量%,例如至少70质量%,更优选至少80质量%,例如至少85或90或95质量%。此类“其它聚合物分散剂添加剂”可以包括多胺和聚丁烯基琥珀酸酐(PIBSA)的聚丁烯基琥珀酰亚胺反应产物,所述聚丁烯基琥珀酸酐经由烯马来化方法衍生自具有小于1300的数均分子量(Mn)和至少50%的末端乙烯叉基含量的聚丁烯和马来酸酐,以及包括使用卤素(例如,氯)辅助烷基化方法制备的琥珀酰亚胺分散剂。所述“其它聚合物分散剂添加剂”还可以包括衍生自聚丁烯以外的聚合物,例如聚丙烯聚合物,乙烯-丙烯共聚物,乙烯-丁烯共聚物以及丁烯和马来酸酐的共聚物的分散剂。
本发明的高分子量、高官能度分散剂和所述“其它聚合物分散剂添加剂”中的任一种或每一种可以通过各种常规后处理进行后处理,例如硼化,如美国专利Nos.3,087,936和3,254,025中一般教导的那样。通过用硼化合物,例如氧化硼、硼酸和硼酸的酯处理含酰基氮的分散剂,可以容易地实现分散剂的硼化,所述硼化合物以足以为每摩尔酰化的氮组成提供大约0.1至大约20原子比例的硼的量使用。有用的分散剂含有大约0.05至大约2.5质量%,例如大约0.05至大约1.5质量%硼。认为,所述硼(作为脱水硼酸聚合物(主要是(HBO2)3)出现在产物中)与分散剂酰亚胺和二酰亚胺以胺盐连接,例如二酰亚胺的偏硼酸盐。硼化可以如下进行:将大约0.5-4质量%,例如大约1至大约3质量%(基于酰基氮化合物的质量)硼化合物,优选硼酸(通常作为浆料)添加到酰基氮化合物中并在大约135℃至大约190℃,例如140℃-170℃下,在搅拌下,加热大约1至大约5小时,接着氮气汽提。或者,硼处理可以通过将硼酸添加到二元羧酸材料和胺的热反应混合物中同时除水来进行。还可以应用本领域中通常已知的其它后反应方法。优选地,本发明的高分子量、高官能度分散剂是未硼化的。其它后处理剂包括碳酸亚乙酯,脂族芳族酸和酚类化合物。
含金属清净剂或灰分形成清净剂既用作清净剂以减少或除去沉积物又用作酸中和剂或防锈剂,从而减少磨损和腐蚀并延长发动机寿命。清净剂一般包含具有长疏水性尾的极性头。所述极性头包含酸性有机化合物的金属盐。所述盐可以含有基本上化学计量量的金属,在这种情况下,它们一般描述为正盐或中性盐,通常具有0-80mg KOH/g(基于A.I.)或0-150mg KOH/g(基于非A.I.,稀释在油中)的总碱值或TBN(如可以通过ASTM D2896测量)。通过使过量的金属化合物(如氧化物或氢氧化物)与酸性气体(如二氧化碳)反应可引入大量金属碱。所得过碱性清净剂包括中和的清净剂作为金属碱(例如氢氧化物或碳酸盐)胶束的外层。此类过碱性清净剂可以具有300mg KOH/g或更大的TBN(基于A.I.),并通常具有400-1000mg KOH/g或更大的TBN(基于A.I.)。
本发明添加剂浓缩物含有一种或多种具有大约300至大约900mg KOH/g的总碱值(TBN)(基于A.I.)的过碱性镁胶态清净剂。这些过碱性镁胶态清净剂(一种或多种)可以衍生自一种或多种选自(a)磺酸盐;(b)酚盐和(c)羟基苯甲酸盐(例如,水杨酸盐)表面活性剂的表面活性剂。
磺酸盐清净剂可以是脂族或芳族的。芳族磺酸盐清净剂可由磺酸制备,磺酸通常通过烷基取代的芳族烃的磺化而获得,所述烷基取代的芳族烃例如为由石油的分馏或通过芳族烃的烷基化获得的那些。实例包括通过使苯、甲苯、二甲苯、萘、联苯或它们的卤素衍生物如氯苯、氯甲苯和氯萘烷基化获得的那些。烷基化可在催化剂存在下进行,其中烷基化剂具有约3至大于70个碳原子。烷芳基磺酸盐通常对于每个烷基取代的芳族结构部分含有大约9至大约80或更多个碳原子,优选大约16至大约60个碳原子。
油溶性烷基磺酸盐或烷芳基磺酸可用金属的氧化物、氢氧化物、醇盐、碳酸盐、羧酸盐、硫化物、氢硫化物、硝酸盐、硼酸盐和醚来中和。金属化合物的量根据最终产物期望的TBN来选择,但是通常为化学计量所需量的大约100-220质量%(优选至少125质量%)。
酚盐清净剂,酚和硫化酚的金属盐,通过与适当的金属化合物如氧化物或氢氧化物的反应来制备,并且中性或过碱性产物可由本领域众所周知的方法来获得。硫化酚可通过使酚与硫或含硫化合物如硫化氢、一卤化硫或二卤化硫反应来制备,形成的产物通常为其中2个或更多个酚通过含硫的桥基桥接的化合物的混合物。本文提及表面活性剂类型所使用的术语“酚盐”还旨在包括烷基-桥联的酚缩合物,例如,美国专利No.5,616,816中所述;取代有–CHO或CH2OH基的桥联或未桥联酚缩合物,有时称为“水杨醛”,例如,美国专利No.7,462,583中所述;以及通过羧酸,例如硬脂酸改性的酚盐,例如,美国专利Nos.5,714,443,5,716,914,6,090,759中所述。
羟基苯甲酸盐清净剂,例如水杨酸盐可以由烃基取代的羟基苯甲酸制备。羟基苯甲酸通常通过Kolbe-Schmitt方法将苯氧化物羧化来制备,并且在那种情况下,通常与未羧化的苯酚混合地获得(通常在稀释剂中)。羟基苯甲酸可以是未硫化或硫化的,并且可以是化学改性的和/或可含有其它取代基。将烃基取代的羟基苯甲酸硫化的方法是本领域技术人员熟知的,并例如,在US 2007/0027057中进行了描述。
在烃基取代的羟基苯甲酸中,烃基优选是烷基(包括直链或支链烷基),并且所述烷基有利地含有5-100,优选9-30,特别是14-24个碳原子。优选地,烃基取代的羟基苯甲酸盐表面活性剂是衍生自烃基取代的水杨酸的烃基取代的水杨酸盐表面活性剂。如同烃基取代的羟基苯甲酸的情况一样,一般而言,油溶性水杨酸中的优选的取代基是烷基取代基,并在烷基-取代的水杨酸中,烷基有利地含有5-100,优选9-30,特别是14-24个碳原子。当存在多于一个烷基时,在所有烷基中的碳原子的平均数优选至少大约9以确保足够的油溶性。
烃基取代的羟基苯甲酸可用金属的氧化物、氢氧化物、醇盐、碳酸盐、羧酸盐、硫化物、氢硫化物、硝酸盐、硼酸盐和醚来中和。金属化合物的量根据最终产物期望的TBN来选择,但是通常为化学计量所需量的大约100-220质量%(优选至少125质量%)。
本文提及表面活性剂类型所使用的术语“羟基苯甲酸盐”旨在包括水杨酸盐,以及所谓的“酚盐”,例如,美国专利Nos.5,808,145和6,001,785中所述,和任选取代的桥联酚/水杨酸盐缩合物,有时称为“salixarates”,它们例如,在美国专利No.6,200,936中进行了描述。
本发明的过碱性镁胶态清净剂还可以是与混合表面活性剂体系形成的“混杂”清净剂,例如酚盐/水杨酸盐、磺酸盐/酚盐、磺酸盐/水杨酸盐和磺酸盐/酚盐/水杨酸盐,例如,美国专利Nos.6,153,565,6,281,179,6,429,178和6,429,179中所述那样。
本发明的润滑剂添加剂浓缩物还可以含有中性镁清净剂以及基于除镁以外的金属,例如钙和/或钠的中性和过碱性清净剂。然而,本发明的过碱性镁胶态清净剂(一种或多种)优选占浓缩物中的清净剂的总质量的至少15质量%,例如至少20质量%,至少30质量%或至少40质量%,优选至少50质量%,例如至少60、70或80质量%。
本发明的有机摩擦改进剂包含选自如下的有机摩擦改进剂(iii):至少一种C14-C24烃的羟烷基烷基胺(例如,双(2-羟乙基)牛脂胺),至少一种C13-C24烃的羟烷基烷基醚胺(例如,双(2-羟乙基)十八烷氧基丙胺),至少一种衍生自具有C13-C24烃基取代基的三乙醇胺的烷基酯胺(例如,三乙醇胺的三、二和单牛脂基酯),至少一种非碱性脂肪酰胺(例如油酰胺),或它们的混合物。除了上述有机摩擦改进剂(iii)之外,本发明润滑剂添加剂浓缩物还可以含有其它有机摩擦改进剂或燃料节约剂。这些材料的实例包括更高级脂肪酸的甘油基单酯,例如,单油酸甘油基酯;烷基化酒石酸衍生物;长链多元羧酸与二醇的酯,例如,二聚不饱和脂肪酸的丁烷二醇酯;和噁唑啉化合物。
本发明的润滑剂添加剂浓缩物可以任选地进一步含有低分子量烃基或烯烃基琥珀酰亚胺或琥珀酸酐相容性助剂,衍生自具有大约150至大约1200道尔顿的数均分子量(Mn)的烃基或烯烃基,例如十八碳烯基琥珀酸酐(ODSA)或聚异丁烯基琥珀酸酐(PIBSA)。PIBSA相容性助剂,或衍生低分子量琥珀酰亚胺相容性助剂的PIBSA经由热“烯”反应,或使用卤素(例如氯)辅助烷基化方法形成。
可以用作本发明添加剂浓缩物中的稀释剂的润滑粘度的油可以选自天然润滑油、合成润滑油和它们的混合物。一般而言,这些油的粘度为大约2mm2/sec(厘沱)至大约40mm2/sec,特别是大约4mm2/sec至大约20mm2/sec,在100℃下测得。
天然油包括动物油和植物油(例如蓖麻油、猪油);液体石油和链烷、环烷和混合链烷-环烷烃类型的加氢精制、溶剂处理或酸处理的矿物油。源自煤炭或页岩的润滑粘度的油也用作有用的基础油。
合成润滑油包括烃油和卤取代的烃油,例如聚合和互聚合烯烃(例如,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));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);聚苯(例如,联苯、三联苯、烷基化的聚酚);和烷基化的二苯醚和烷基化的二苯硫醚及其衍生物、类似物和同系物。
其中末端羟基已经通过酯化、醚化等改性的氧化烯聚合物和互聚物和它们的衍生物构成另一类已知的合成润滑油。它们的实例包括由氧化乙烯或氧化丙烯的聚合而制备的聚氧化烯聚合物,和聚氧化烯聚合物的烷基和芳基醚(例如,分子量为1000的甲基-聚异丙二醇醚或分子量为1000-1500的聚乙二醇的二苯基醚);和它们的单和多元羧酸酯(例如乙酸酯、混合的C3-C8脂肪酸酯和四乙二醇的C13含氧酸二酯)。
另一类适合的合成润滑油包括二羧酸(例如邻苯二甲酸、琥珀酸、烷基琥珀酸和链烯基琥珀酸、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、十二醇、2-乙基己醇、乙二醇、二乙二醇单醚、丙二醇等)的酯。这类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、邻苯二甲酸二辛酯、邻苯二甲酸二癸酯、癸二酸二(二十烷基)酯、亚油酸二聚体的2-乙基己基二酯,和由1摩尔的癸二酸与2摩尔的四乙二醇和2摩尔的2-乙基己酸反应而形成的复合酯。
可用作合成油的酯还包括由C5-C12单羧酸和多元醇以及多元醇酯如新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇、三季戊四醇制成的那些。
基于硅的油如多烷基、多芳基、多烷氧基或多芳氧基硅酮油和硅酸酯油构成另一类有用的合成润滑剂;这种油包括硅酸四乙酯、硅酸四异丙酯、硅酸四(2-乙基己基)酯、硅酸四(4-甲基-2-乙基己基)酯、硅酸四(对叔丁基苯基)酯、六(4-甲基-2-乙基己基)二硅氧烷、聚(甲基)硅氧烷和聚(甲基苯基)硅氧烷。其它合成润滑油包括含磷的酸的液态酯(例如磷酸三甲苯酯、磷酸三辛酯、癸基膦酸的二乙基酯)和聚合四氢呋喃。
稀释油可以包括第I组、第II组、第III组、第IV组或第V组基础油料或上述基础油料的共混物。本发明中对基础油料和基础油的定义与美国石油协会(API)出版物“EngineOil Licensing and Certification System”,Industry Service Department,第十四版,1996年12月,附录1,1998年12月中的那些定义相同。
本发明润滑剂添加剂浓缩物包含如下所述量的:(i)分散剂,其是多胺和聚丁烯基琥珀酸酐(PIBSA)的聚丁烯基琥珀酰亚胺反应产物,所述聚丁烯基琥珀酸酐经由热或“烯”马来化方法衍生自具有大约1300至大约2500道尔顿的数均分子量(Mn)和至少大约50%的末端乙烯叉基含量的聚丁烯和马来酸酐;(ii)过碱性镁胶态清净剂,其具有大约300至大约900mg KOH/g的总碱值(TBN)(基于A.I.);和(iii)有机摩擦改进剂,选自至少一种C14-C24烃的羟烷基烷基胺(例如,双(2-羟乙基)牛脂胺),至少一种C13-C24烃的羟烷基烷基醚胺(例如,双(2-羟乙基)十八烷氧基丙胺),至少一种衍生自具有C13-C24烃基取代基的三乙醇胺的烷基酯胺(例如,三乙醇胺的三、二和单牛脂基酯),至少一种非碱性脂肪酰胺(例如油酰胺),或它们的混合物,它们的用量使得所述浓缩物中的分散剂(i)和过碱性镁胶态清净剂(ii)的总质量%为大约15至大约50质量%(基于A.I.);(i):(ii)的质量比为大约1:1至大约6:1,例如大约1.4:1至大约5.0:1,优选大约1.5:1至大约4.0:1;并且所述浓缩物含有大约2至大约10质量%有机摩擦改进剂(iii);所述浓缩物的其余部分包含基础油和除(i)、(ii)和(iii)以外的添加剂。优选地,本发明润滑剂添加剂浓缩物中的有机摩擦改进剂(包括有机摩擦改进剂(iii)和任何其它有机摩擦改进剂)的总浓度为大约4质量%至大约10质量%。
如果要求润滑剂添加剂浓缩物的额外稳定化,则可以用大约0.25质量%至大约8质量%,例如大约0.5质量%至大约7质量%,大约0.75质量%至大约7质量%或大约1.0至大约6质量%(基于浓缩物的总质量)的一种或多种上述相容性助剂中代替等量的基础油。应该指出,如果要将相容性助剂添加到本发明润滑剂添加剂浓缩物中,则不应该将它引入不存在清净剂的浓缩物中。如果在没有清净剂的情况下将相容性助剂与分散剂一起引入,则相容性助剂的功效可能降低。
可以将额外的添加剂结合到本发明组合物中以便能够满足特定的性能要求。可以包括在本发明润滑油组合物中的添加剂的实例是金属防锈剂、腐蚀抑制剂、氧化抑制剂、非有机摩擦改进剂、消泡剂、抗磨剂和倾点下降剂。下文将更详细地讨论一些添加剂。
二烃基二硫代磷酸金属盐常用作抗磨剂和抗氧化剂。所述金属可以是碱金属或碱土金属,或铝、铅、锡、钼、锰、锌、镍或铜。锌盐最常按大约0.1质量%至大约10质量%,优选大约0.2质量%至大约2质量%的量用于润滑油,基于所述润滑油组合物的总重量,并因此,通常按大约2质量%至大约20质量%的量存在于添加剂浓缩物中。它们可以按照已知的技术如下制备:首先通常通过一种或多种醇或酚与P2S5的反应形成二烃基二硫代磷酸(DDPA),然后用锌化合物中和所形成的DDPA。例如,可以通过伯醇和仲醇混合物的反应来制造二硫代磷酸。或者,可以制备多种二硫代磷酸,其中一种二硫代磷酸上的烃基在性质上完全是仲烃基,其它二硫代磷酸上的烃基在性质上完全是伯烃基。为了制造锌盐,可以使用任何碱性或中性锌化合物,但是最常使用氧化物、氢氧化物和碳酸盐。市售添加剂通常包含过量的锌,这归因于在中和反应中使用过量的碱性锌化合物。
氧化抑制剂或抗氧化剂降低矿物油在使用中变质的倾向。氧化变质可通过润滑剂中的淤渣、金属表面的清漆状沉积物以及通过粘度增加得以证实。这类氧化抑制剂包括受阻酚,具有至少两个与氮直接连接的芳族基的芳族胺(例如,二-苯胺),优选含有C5-C12烷基侧链的烷基酚硫酯的碱土金属盐,壬基酚硫化钙,油溶性酚盐和硫化酚盐,磷硫化或硫化的烃或酯、磷酯、金属硫代氨基甲酸盐,如美国专利No.4,867,890中所述的油溶性铜化合物,和含钼化合物。
非有机摩擦改进剂包括油溶性氧化钼复合物和有机钼化合物。该类有机钼摩擦改进剂还为润滑油组合物提供抗氧化剂和抗磨剂的作用。油溶性有机钼化合物包括二硫代氨基甲酸盐、二硫代磷酸盐、二硫代次膦酸盐、黄原酸盐、硫代黄原酸盐、硫化物等,以及它们的混合物。尤其优选的是钼的二硫代氨基甲酸盐、二烷基二硫代磷酸盐、烷基黄原酸盐和烷基硫代黄原酸盐。此外,所述钼化合物可以是酸性钼化合物。这些化合物如由ASTM试验D-664或D-2896滴定程序所测得的那样与碱性氮化合物反应并且通常是六价的。包括的是钼酸,钼酸铵,钼酸钠,钼酸钾和其它的碱金属钼酸盐和其它的钼盐,例如钼酸氢钠、MoOCl4、MoO2Br2、Mo2O3Cl6、三氧化钼或类似的酸性钼化合物。
倾点下降剂,也称作润滑油流动改进剂(LOFI),降低流体将流动或可以被倾倒时的最低温度。此类添加剂是众所周知的。改进流体低温流动性的那些典型添加剂是富马酸C8-C18二烷基酯/乙酸乙烯酯共聚物,和聚甲基丙烯酸酯。可以通过聚硅氧烷型消泡剂,例如硅酮油或聚二甲基硅氧烷来提供泡沫控制。
本发明的润滑剂添加剂浓缩物的总添加剂含量可以为大约20质量%至大约70质量%,例如大约35质量%至大约50质量%,基于浓缩物的总质量。为了确保可接受的处理能力,本发明的润滑剂添加剂浓缩物优选具有小于大约300cSt,例如小于大约250cSt或小于大约200cSt的100℃运动粘度(kv100)。
本发明可参照下列实施例进一步理解,其中所有的份数都是重量份数,除非另作说明,并且这些实施例包括本发明的优选实施方案。
实施例
如上述美国专利7,786,060中所描述的,评价浓缩物的长期储存稳定性。具体来说,将浓缩物在60℃的温度下储存数周(至多12周),其中周期性测量所形成的沉积物的量。在测量的沉积物的量基于浓缩物的总质量超过0.05质量%时,添加剂浓缩物在稳定性试验中不合格。稳定性试验的结果示于以下表1-3中。
表1
Figure BDA0001123830710000151
痕量
表1示出了,相对于由常规聚丁烯制备经由氯-辅助方法官能化的类似分散剂,与包含本发明的分散剂(i)的稳定添加剂浓缩物的制备相关的增加的挑战。在上述浓缩物中,本发明的分散剂(i)和由常规聚丁烯制备经由氯-辅助方法官能化的类似分散剂都衍生自具有2200的Mn的聚丁烯(PIB)。衍生本发明的分散剂(i)的PIB是高度反应性PIB(HR-PIB),具有大约80%的末端乙烯叉基含量和大约2.0的分子量分布(MWD)。衍生非本发明的分散剂的PIB是具有大约2.3的MWD的常规PIB。用于浓缩物中的每一种的清净剂是具有600mg KOH/g的TBN(基于AI)的过碱性烷基磺酸钙清净剂。使用三乙醇胺酯摩擦改进剂(TEEMA),测试两种分散剂官能度值(FV),和分散剂:清净剂比例的范围。
表2
Figure BDA0001123830710000161
痕量
表2示出了在甚至较小浓度的有机摩擦改进剂例如单油酸甘油酯(GMO)和TEEMA存在下,与具有表1的热分散剂和清净剂的稳定浓缩物的制备相关的进一步增加的挑战。一般要求更高浓度的有机摩擦改进剂以获得现代发动机的期望的低摩擦(高燃料经济性)性能。GMO尤其显示在远低于达到燃料经济性能目标所需要的浓度的水平下引起相分离。
表3
Figure BDA0001123830710000162
痕量
**50%GMO和50%TEEMA
表3比较了按3.0-5.3质量%的有机摩擦改进剂浓度包含本发明元素使用摩擦改进剂GMO和TEEMA的浓缩物与包含过碱性镁清净剂而不是过碱性钙清净剂的相应浓缩物的稳定性。所述镁清净剂是具有700mg KOH/g的TBN(基于AI)的过碱性烷基苯磺酸盐清净剂。所述钙清净剂与表1和2中相同。在表2和表3中的每一个中,具有1050道尔顿的Mn的聚异丁烯琥珀酸酐(PIBSA)用作相容性助剂。
应该指出的是,本发明的润滑剂添加剂浓缩物和润滑油组合物包含所限定的个体的(即独立的)的组分,它们在混合之前和之后可以保持或可以未保持化学不变。因此,应当理解,组合物的各种组分(必要的以及任选的和常用的组分)可以在配制、存储或使用条件下反应,并且本发明还涉及和涵盖由于任何这样的反应可获得的或获得的产物。
本文描述的所有专利、文章及其它材料的公开内容在此通过引用全文并入本说明书。本发明的原理,优选的实施方案和操作模式已经在前面说明中进行了描述。然而,申请人认为它们的发明不应理解为限于所公开的具体实施方案,因为所公开的实施方案认为是说明性的而不是限制性的。本领域技术人员在不脱离本发明精神的情况下可以作出改变。

Claims (15)

1.润滑剂添加剂浓缩物,包含(i)分散剂,其是多胺和聚丁烯基琥珀酸酐的聚丁烯基琥珀酰亚胺反应产物,所述聚丁烯基琥珀酸酐经由烯马来化方法衍生自具有1300至2500道尔顿的数均分子量和至少50%的末端乙烯叉基含量的聚丁烯和马来酸酐;(ii)过碱性镁胶态清净剂,其具有300至900mg KOH/g的总碱值(TBN);和(iii)有机摩擦改进剂,其包含选自如下的有机摩擦改进剂:至少一种C14-C24烃的羟烷基烷基胺,至少一种C13-C24烃的羟烷基烷基醚胺,至少一种衍生自具有C13-C24烃基取代基的三乙醇胺的烷基酯胺,至少一种非碱性脂肪酰胺,或它们的混合物;其中所述浓缩物中的分散剂(i)和过碱性镁胶态清净剂(ii)的总质量%为15至50质量%;(i):(ii)的质量比为1:1至6:1;和所述浓缩物含有2质量%至10质量%的有机摩擦改进剂(iii);所述浓缩物的其余部分包含基础油和除分散剂(i)、过碱性镁胶态清净剂(ii)和有机摩擦改进剂(iii)以外的添加剂。
2.权利要求1的润滑剂添加剂浓缩物,其中分散剂(i)具有1.3至2.2的官能度。
3.权利要求1的润滑剂添加剂浓缩物,其中分散剂(i)衍生自具有1.2至3.0的分子量分布(MWD)的聚丁烯。
4.权利要求2的润滑剂添加剂浓缩物,其中分散剂(i)衍生自具有1.2至3.0的分子量分布(MWD)的聚丁烯。
5.权利要求1的润滑剂添加剂浓缩物,其中所述过碱性镁胶态清净剂(ii)衍生自选自(a)磺酸盐;(b)酚盐;和(c)羟基苯甲酸盐表面活性剂中的一种或多种的表面活性剂。
6.权利要求5的润滑剂添加剂浓缩物,其中所述过碱性镁胶态清净剂(ii)衍生自两种或更多种不同的表面活性剂。
7.权利要求1的润滑剂添加剂浓缩物,包含镁和钙清净剂的混合物。
8.权利要求1的润滑剂添加剂浓缩物,包含有机摩擦改进剂(iii)和除(iii)以外的有机摩擦改进剂的混合物。
9.权利要求1的润滑剂添加剂浓缩物,其中所述浓缩物中的有机摩擦改进剂的总浓度为4质量%至10质量%。
10.权利要求8的润滑剂添加剂浓缩物,其中所述浓缩物中的有机摩擦改进剂的总浓度为4质量%至10质量%。
11.权利要求1的润滑剂添加剂浓缩物,还包含低分子量烃基取代的琥珀酰亚胺或琥珀酸酐相容性助剂,其衍生自具有150至1200道尔顿的数均分子量的烃基。
12.权利要求1的润滑剂添加剂浓缩物,还包含低分子量烯烃基取代的琥珀酰亚胺或琥珀酸酐相容性助剂,其衍生自具有150至1200道尔顿的数均分子量的烯烃基。
13.权利要求11或12的润滑剂添加剂浓缩物,包含0.25质量%至8质量%的所述相容性助剂。
14.权利要求13的润滑剂添加剂浓缩物,其中所述相容性助剂是十八碳烯基琥珀酸酐,或聚异丁烯基琥珀酸酐或它们的混合物。
15.权利要求1的润滑剂添加剂浓缩物,还包含至少一种选自锌-磷抗磨剂、含钼抗磨剂和/或含钼摩擦改进剂、抗氧化剂、粘度改进剂和倾点下降剂的其它添加剂。
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