CN110621767A - 防降解自修复润滑油 - Google Patents
防降解自修复润滑油 Download PDFInfo
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Abstract
一种润滑油包括:基础油;以及抗降解添加剂,所述抗降解添加剂包括微胶囊、纳米胶囊,或包括前述至少一者的组合;所述微胶囊和所述纳米胶囊各自独立地具有中和材料的核和聚合物囊封剂,所述聚合物囊封剂被配置成通过使所述聚合物囊封剂中的交联键或氢键断裂而在酸性环境中释放所述中和材料。所释放的中和材料可以防止形成粘性的高分子量分子,从而延长所述润滑油的使用寿命并且提高其可靠性。
Description
相关应用的交叉引用
本申请要求2017年4月6日提交的美国申请No.15/480640的权益,所述美国申请以全文引用的方式并入本文中。
背景技术
本发明涉及润滑油,具体是具有抗降解和/或自修复特性的润滑油。
润滑油用于多种应用,包括为发动机、电动机、轴承和其它金属表面提供润滑。润滑油还可以通过带走发动机或移动部件内生成的热来减少移动部件的磨损、清除移动部件的污泥、抑制腐蚀、改善密封性并且降低操作温度。润滑油确保恰当的功能性,并且可以延长车辆和其它电动设备(例如ESP泵)的使用寿命。
然而,润滑剂在升高的温度和压力下易于热降解和氧化降解。当长时间在恶劣环境中使用时,会形成较高分子量的分子,从而降低润滑油的润滑性。因此,希望提供具有抗降解或自修复特性的润滑油。
发明内容
在一个实施方案中,一种润滑油包括:基础油;以及抗降解添加剂,所述抗降解添加剂包括微胶囊、纳米胶囊,或包括前述至少一者的组合;所述微胶囊和所述纳米胶囊各自独立地具有中和材料的核和被配置成在酸性环境中释放所述中和材料的聚合物囊封剂。
一种减少润滑油的降解的方法包括:向基础油中加入包括微胶囊、纳米胶囊或包括前述至少一者的组合的抗降解添加剂;所述微胶囊和所述纳米胶囊各自独立地具有中和材料的核和被配置成在酸性环境中释放所述中和材料的聚合物囊封剂。
在另一实施方案中,一种发动机润滑系统包括:循环系统,所述循环系统用于提供润滑油到内燃机的连续流动;以及润滑油,所述润滑油设置在所述循环系统内,所述润滑油包括基础油;以及抗降解添加剂,所述抗降解添加剂包括微胶囊、纳米胶囊,或包括前述至少一者的组合;所述微胶囊和所述纳米胶囊各自独立地具有中和材料的核和被配置成在酸性环境中释放所述中和材料的聚合物囊封剂。
在又一实施方案中,一种电动机包括:可旋转轴;定子;转子,所述转子设置在所述定子内并且与所述定子之间隔开运行间隙,所述转子被配置成用于使所述轴旋转;以及设置在所述运行间隙中的如上文公开的润滑油。
附图说明
以下描述不应被视为以任何方式进行限制。参考附图,相同的元件被相同地编号:
图1示出了根据本公开的实施方案的具有中和材料的核和聚合物囊封剂的示例性微胶囊/纳米胶囊;
图2示出了图1的中和材料从聚合物囊封剂的释放;
图3示出了含吡啶的聚氨酯囊封剂在中性或碱性条件下的示例性结构;
图4示出了含吡啶的聚氨酯囊封剂在酸性条件下的示例性结构;以及
图5是被配置成使用本文公开的润滑油组合物的井下潜水泵的示例性实施方案的横截面图。
具体实施方式
本文的发明人发现,包括微胶囊、纳米胶囊或其组合的抗降解添加剂赋予润滑油抗降解和/或自修复特性。所述微胶囊和纳米胶囊各自独立地具有中和材料的核和被配置成在酸性环境中释放中和材料的聚合物囊封剂。不希望受理论束缚,据信常规润滑油会发生氧化降解而生成副产物,例如羧酸。羧酸又会低聚或聚合并且形成粘性高分子量分子,从而降低润滑油的润滑性。通过在常规润滑油中包括本文公开的微胶囊和/或纳米胶囊,当生成羧酸副产物时,聚合物囊封剂对酸性环境作出响应并且释放中和材料。所释放的中和材料与羧酸副产物反应,并且防止它们形成粘性高分子量分子,从而延长润滑油的寿命并且提高其可靠性。
抗降解添加剂的核中的中和材料是C1-30胺、C1-30醇,或包括前述至少一者的组合。优选地,中和材料是C10-20胺、C15-20胺、C10-20醇或C15-20醇。如本文所用,胺包括伯胺、仲胺或叔胺。具体提及伯胺,例如十八烷基胺。
中和材料被聚合物囊封剂囊封,因此不会过早消耗。聚合物囊封剂对pH值敏感,并且被配置成通过破坏聚合物囊封剂的聚合物链之间的交联键和/或氢键而在酸性环境中释放中和材料。在一实施方案中,聚合物囊封剂包括具有酸不稳定交联键的壳聚糖、含吡啶的聚氨酯、含吡啶的聚脲,或包括前述至少一者的组合。
壳聚糖是由N-乙酰氨基葡萄糖和氨基葡萄糖单元组成的生物聚合物。壳聚糖可以被官能化以并有各种官能团。示例性官能团包括羧酸、烯基、烷基、羰基等。酸不稳定交联键可以在壳聚糖上的胺或羟基之间形成或经由引入到壳聚糖上的其它官能团形成。壳聚糖的示例性酸不稳定交联剂包括β硫代丙酸酯、戊二醛、表氯醇,或包括前述至少一者的组合。制备具有酸不稳定基团的壳聚糖的方法在Langmuir2014,30,4111-4119中进行了说明。
图1示出了根据本公开的实施方案的具有中和材料15的核和聚合物囊封剂的示例性微胶囊/纳米胶囊。聚合物囊封剂可以包括基于壳聚糖的聚合物链100和在基于壳聚糖的聚合物链之间的酸不稳定交联键12。如图2所示,当润滑油开始降解并且生成羧酸副产物时,酸性副产物会破坏交联键12,从而从胶囊中释放中和材料15。
含吡啶的聚氨酯和含吡啶的聚脲是指具有并入于聚合物主链中的吡啶部分的聚氨酯和聚脲。有利地,在中性或碱性条件下,如图3所示,在吡啶的氮原子与聚氨酯或聚脲的主链上的H-N-部分的H原子之间形成氢键。如图4所示,在酸性条件下,吡啶的氮原子被质子化,并且氢键断裂。不希望受理论束缚,据信当氢键断裂时,胶囊变弱,并且由于例如内摩擦的机械剪切,胶囊破裂而释放中和材料。
聚氨酯由多元醇和多异氰酸酯形成。吡啶部分可以经由多元醇或多异氰酸酯单体、低聚物或预聚物并入到聚氨酯的主链中。吡啶部分也可以经由扩链剂并入到聚氨酯的主链中。制备含吡啶的聚氨酯的方法在Polym.Chem.,2014,5,5168-5174中进行了说明。吡啶部分可以经由用于制备聚合物的单体或低聚物并入到聚脲的主链中。
微米或纳米大小的胶囊可以具有不同的大小、形状和表面形态。形状包括球形、管状等。微米或纳米大小的胶囊也可以是无定形的。颗粒可以具有约1nm至约500微米、或约5nm至约250微米、或约100nm至约100微米的平均粒径。如本文所用,“平均粒径”是指基于颗粒的最大线性尺寸(有时称为“直径”)的数均粒径。包括平均、最大和最小粒径的粒径可以通过使用激光源确定颗粒大小的适当方法(例如静态或动态光散射(SLS或DLS))来确定。对于具有核/壳结构的颗粒,壳的厚度为约至约5nm至约100nm或约10nm至约50nm或约5nm至约15nm。
在一实施方案中,抗降解添加剂包括平均粒径小于或等于约500nm、具体是约1至约500nm或约5至约400nm、更具体是约10至约300nm、甚至更具体地为约10至约250nm的纳米胶囊。具有本文公开的大小的纳米胶囊干扰润滑油的粘度的趋势可能较小。
通过各种合成方法如溶胶-凝胶、反胶束等来生产微米或纳米大小的胶囊。在示例性方法中,在超声处理下将聚合物囊封剂与中和剂混合以形成微胶囊或纳米胶囊。所形成的微胶囊或纳米胶囊可以在并入润滑油之前被隔离。
抗降解添加剂的存在量可以至多为润滑油的约30体积%。或者,抗降解添加剂的存在量可以至多为约20体积%。在其它实施方案中,抗降解添加剂的存在量可以至多为约10体积%。在某些实施方案中,抗降解添加剂的存在量可以在约0.001体积%与约30体积%之间、优选地在约0.01体积%与约20体积%之间或在约0.01体积%至约15体积%之间,其各自是基于润滑油的总体积。
适用于润滑剂的基础油是烃基油,并且可以是天然油或合成油。如本文所用,天然油是指含有具有各种分子量的烃的混合物的天然存在的液体,其已经从地下岩层中回收,并且可能已经进行了精制过程。如本文所用,合成油是指由最初不存在于原油中,而是从其它化合物人工合成的化合物组成的烃液体。
基础油可以是任何天然油,包括各种石油馏出物,或任何流变形式的合成油,包括液态油、油脂、凝胶、油溶性聚合物组合物等,特别是用于润滑行业的矿物基础油或合成基础油,例如第I组(溶剂精制矿物油)、第II组(加氢裂化矿物油)、第III组(重度加氢裂化油,有时被描述为合成或半合成油)、第IV组(聚α烯烃(PAO)),和第V组(酯、环烷及其它)。示例包括聚α烯烃、合成酯和聚烷基二醇。
合成润滑油包括烃油和卤代烃油,例如聚合和共聚的烯烃(例如聚丁烯、聚丙烯、丙烯异丁烯共聚物、氯化聚丁烯、聚(1-辛烯)、聚(1-癸烯)等,以及其混合物);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);聚苯基(例如,联苯、三联苯、烷基化聚苯基等)、烷基化二苯基、醚和烷基化二苯基硫化物及其衍生物、类似物和同系物等。其中封端羟基已通过酯化、醚化等改性的环氧烷聚合物及其互聚物及衍生物构成另一类已知的合成油。
另一类合适的合成油包括二羧酸(例如邻苯二甲酸、琥珀酸、烷基琥珀酸和烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、反丁烯二酸、己二酸、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。这些酯的具体示例包括己二酸二丁酯、癸二酸二(2-乙基己基)酯、反丁烯二酸二己酯、癸二酸二辛酯、癸二酸二异辛基壬二酸酯、邻苯二甲酸二辛基酯、邻苯二甲酸二癸基酯、癸二酸癸二酸酯、亚油酸酯二聚物的2-乙基己基二酯、通过使一摩尔癸二酸与两摩尔四甘醇和两摩尔2-乙基己酸反应而形成的复合酯,等等。
可用作合成油的酯还包括由C5至C12一元羧酸和多元醇以及多元醇醚(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)制成的那些酯。其它合成油包括含磷酸(phosphorus-containing acid)的液态酯(例如,磷酸三甲苯酯、磷酸三辛酯、癸基膦酸的二乙酯等)、聚合四氢呋喃等。
基于润滑油的总体积,基础油在润滑油中的存在量可以大于约60体积%、大于约70体积%或大于约80体积%。
润滑油可以任选地包括额外化合物,包括但不限于抗氧化剂、清洁剂、摩擦改进剂、粘度改进剂、缓蚀添加剂、抗磨添加剂、消泡剂、表面活性剂、调理剂和分散剂。
本文公开的润滑油具有改进的抗降解和自修复性质。润滑油的动态粘度在23℃为约1cP至约2000cP。在一实施方案中,与除了不含抗降解添加剂之外在其它方面相同的润滑油相比,所述润滑油具有较小的粘度增加。在另一实施方案中,与除了不含抗降解添加剂之外在其它方面相同的润滑油相比,所述润滑油具有更长的寿命。所述润滑油可用于各种应用中。在一些实施方案中,本发明的润滑油可用于汽车、船舶、航空以及工业发动机和机器部件中。如本文所用,润滑油包括机油。
在一个实施方案中,如本文所述的润滑油用于设置在井筒中的井下潜水电泵系统(ESP)中,其中井筒可以与地下地层相交。如图5所示,ESP在下端包括电动机10、密封件(未示出),并且在上端包括泵(未示出)。电动机10与泵通过密封件分开。电动机包括转子20或多个转子20,以及安装在电动机轴40上的轴承30,其中所述轴联接到并且驱动泵。电动机轴经由密封区段联接到泵,并且电动机轴40联接到密封区段中的轴,密封区段中的轴又联接到泵中的轴。转子20可以是由叠片、铜条和端环的叠层制成的空心圆柱体,其在每个端部上由轴承30支撑。电动机10填充有具有本文所述成分的润滑油50,并且包括位于定子70的内径与转子20的外径之间的运行间隙60,其中油50为轴承30提供润滑,并且带走由摩擦和转子20以及风阻损失生成的热,并且用作定子70与转子20之间的电绝缘体。在运行间隙60内的油可以通过轴40上的孔80在电动机10内循环。电动机中的油50也用在密封件中,并且在密封件与电动机10之间连通和循环。
在本公开的替代实施方案中,提供了一种润滑可在井筒内一次性使用的潜水电泵组件的方法。所述组件包括电动机,其中电动机包括安装在轴上的多个转子和轴承、在多个转子外部的定子以及在定子的内径与转子的外径之间的运行间隙。电动机经由密封区段联接到泵,并且电动机轴联接到密封区段中的轴,密封区段中的轴又联接到泵中的轴。所述方法包括以下步骤:将例如本文所述的抗降解添加剂混合到基础油中,接着将润滑油施配到电动机和密封区段中。
还提供了一种用于内燃机的发动机润滑系统。所述发动机润滑系统包括:循环系统,所述循环系统用于提供润滑油到内燃机和发动机部件的连续流动;以及润滑油,所述润滑油设置在所述循环系统内。所述润滑油包括基础油和如本文公开的抗降解添加剂。
阐述了本公开的各种实施方案。
实施方案1.一种润滑油,所述润滑油包括:基础油;以及抗降解添加剂,所述抗降解添加剂包括微胶囊、纳米胶囊,或包括前述至少一者的组合;所述微胶囊和所述纳米胶囊各自独立地具有中和材料的核和被配置成在酸性环境中释放所述中和材料的聚合物囊封剂。
实施方案2.实施方案1的润滑油,其中所述中和材料包括C1-30胺、C1-30醇,或包括前述至少一者的组合。
实施方案3.实施方案1或实施方案2的润滑油,其中所述中和材料包括C10-20胺、C10-20醇,或包括前述至少一者的组合。
实施方案4.实施方案1至4中任一项的润滑油,其中所述聚合物囊封剂包括具有酸不稳定交联键的壳聚糖、含吡啶的聚氨酯、含吡啶的聚脲,或包括前述至少一者的组合。
实施方案5.实施方案4的润滑油,其中所述酸不稳定交联键包括β硫代丙酸酯、戊二醛、表氯醇,或包括前述至少一者的组合。
实施方案6.实施方案1至5中任一项的润滑油,所述润滑油包括至多约30体积%的所述抗降解添加剂。
实施方案7.根据实施方案1至6中任一项的润滑油,其中所述抗降解添加剂包括平均粒径为约1nm至约500nm的纳米胶囊。
实施方案8.根据实施方案1至7中任一项的润滑油,其中所述润滑油在23℃下具有约1cP至约2,000cP的动态粘度。
实施方案9.一种减少润滑油的降解的方法,所述方法包括:向基础油中加入包括微胶囊、纳米胶囊或包括前述至少一者的组合的抗降解添加剂;所述微胶囊和所述纳米胶囊各自独立地具有中和材料的核和被配置成在酸性环境中释放所述中和材料的聚合物囊封剂。
实施方案10.实施方案9的方法,其中所述聚合物囊封剂包括具有酸不稳定交联键的壳聚糖、含吡啶的聚氨酯、含吡啶的聚脲,或包括前述至少一者的组合。
实施方案11.实施方案10的方法,所述方法进一步包括:使所述壳聚糖的所述酸不稳定交联键断裂;以及从包括具有所述酸不稳定交联键的所述壳聚糖的所述聚合物囊封剂释放所述中和材料。
实施方案12.实施方案11的方法,其中所述酸不稳定交联键包括β硫代丙酸酯、戊二醛、表氯醇,或包括前述至少一者的组合。
实施方案13.实施方案10的方法,所述方法进一步包括:使吡啶的氮原子与所述聚氨酯上的H-N-部分的H原子之间的氢键断裂;以及从包括所述含吡啶的聚氨酯的所述聚合物囊封剂释放所述中和材料。
实施方案14.实施方案9至13中任一项的方法,所述方法进一步包括在使用期间,用从所述聚合物囊封剂释放的所述中和材料中和由所述润滑油生成的酸性副产物。
实施方案15.实施方案9至14中任一项的方法,其中所述中和材料包括C1-30胺、C1-30醇,或包括前述至少一者的组合。
实施方案16.实施方案9至15中任一项的方法,其中所述中和材料包括C10-20胺、C10-20醇,或包括前述至少一者的组合。
实施方案17.实施方案9至16中任一项的方法,其中所述润滑油包括至多约30体积%的所述抗降解添加剂。
实施方案18.一种发动机润滑系统,所述发动机润滑系统包括:循环系统,所述循环系统用于提供润滑油到内燃机的连续流动;以及润滑油,所述润滑油设置在所述循环系统内,所述润滑油包括基础油;以及抗降解添加剂,所述抗降解添加剂包括微胶囊、纳米胶囊,或包括前述至少一者的组合;所述微胶囊和所述纳米胶囊各自独立地具有中和材料的核和被配置成在酸性环境中释放所述中和材料的聚合物囊封剂。
实施方案19.根据实施方案18的发动机润滑系统,其中所述润滑油是根据实施方案1至8中的任一项。
实施方案20.一种电动机,所述发动机包括:可旋转轴;定子;转子,所述转子设置在所述定子内并且与所述定子之间隔开运行间隙,所述转子被配置成用于使所述轴旋转;以及设置在所述运行间隙中的润滑油,所述润滑油包括基础油和抗降解添加剂,所述抗降解添加剂包括微胶囊、纳米胶囊,或包括前述至少一者的组合;所述微胶囊和所述纳米胶囊各自独立地具有中和材料的核和被配置成在酸性环境中释放所述中和材料的聚合物囊封剂。
实施方案21.根据实施方案20的电动机,其中所述润滑油是根据实施方案1至8中的任一项。
本文公开的所有范围包括端点,并且端点可以彼此独立地组合。如本文所用,“组合”包括共混物、混合物、合金、反应产物等。所有参考文献均以全文引用的方式并入本文中。井筒可以是竖直的、偏斜的或水平的。
在描述本发明的上下文中(尤其是在所附权利要求的上下文中)使用术语“一”和“所述”以及类似参考词应解释为涵盖单数和复数两者,除非在本文中另有指示或与上下文明显矛盾。“或”意指“和/或”。与量结合使用的修饰词“约”包括所述值,并且具有上下文指示的含义(例如,其包括与特定量的测量相关联的误差程度)。
Claims (15)
1.一种润滑油(50),其特征在于:
基础油;以及
抗降解添加剂,所述抗降解添加剂包括平均粒径为约1nm至约500nm的纳米胶囊;
所述纳米胶囊具有中和材料(15)的核和被配置成在酸性环境中释放所述中和材料(15)的聚合物囊封剂。
2.如权利要求1所述的润滑油(50),其中所述中和材料(15)包括C10-20胺、C10-20醇,或包括前述至少一者的组合。
3.如权利要求1所述的润滑油(50),其中所述聚合物囊封剂包括具有酸不稳定交联键(12)的壳聚糖、含吡啶的聚氨酯、含吡啶的聚脲,或包括前述至少一者的组合。
4.如权利要求3所述的润滑油(50),其中所述酸不稳定交联键(12)包括β硫代丙酸酯、戊二醛、表氯醇,或包括前述至少一者的组合。
5.如权利要求1所述的润滑油(50),所述润滑油包括至多约30体积%的所述抗降解添加剂。
6.如权利要求1至5中任一项所述的润滑油(50),其中所述纳米胶囊具有核/壳结构,并且所述壳的厚度为约10nm至约50nm。
7.一种减少井下使用的润滑油(50)的降解的方法,所述方法特征在于:
向基础油中加入包括平均粒径为约1nm至约500nm的纳米胶囊的抗降解添加剂,以提供润滑油(50);
所述纳米胶囊具有中和材料(15)的核和被配置成在酸性环境中释放所述中和材料(15)的聚合物囊封剂;以及
使所述润滑油(50)在设置在井筒中的潜水电泵系统中循环。
8.如权利要求7所述的方法,其中所述聚合物囊封剂包括具有酸不稳定交联键(12)的壳聚糖、含吡啶的聚氨酯、含吡啶的聚脲,或包括前述至少一者的组合。
9.如权利要求8所述的方法,所述方法特征还在于:
使所述壳聚糖的所述酸不稳定交联键(12)断裂;以及
从包括具有所述酸不稳定交联键(12)的所述壳聚糖的所述聚合物囊封剂释放所述中和材料(15)。
10.如权利要求9所述的方法,其中所述酸不稳定交联键(12)包括β硫代丙酸酯、戊二醛、表氯醇,或包括前述至少一者的组合。
11.如权利要求8所述的方法,所述方法特征还在于:
使吡啶的氮原子与所述聚氨酯上的H-N-部分的H原子之间的氢键断裂;以及
从包括所述含吡啶的聚氨酯的所述聚合物囊封剂释放所述中和材料(15)。
12.如权利要求8所述的方法,所述方法特征还在于,在使用期间,用从所述聚合物囊封剂释放的所述中和材料(15)中和由所述润滑油(50)生成的酸性副产物。
13.如权利要求7至12中任一项所述的方法,其中所述纳米胶囊具有核/壳结构,并且所述壳的厚度为约10nm至约50nm。
14.一种在井下使用的发动机润滑系统,所述发动机润滑系统特征在于:
循环系统,所述循环系统用于提供润滑油(50)到内燃机的连续流动;以及
润滑油(50),所述润滑油设置在所述循环系统内,
所述润滑油(50)包括基础油;以及
抗降解添加剂,所述抗降解添加剂包括平均粒径为约1nm至约500nm的纳米胶囊;
所述纳米胶囊具有中和材料(15)的核和被配置成在酸性环境中释放所述中和材料(15)的聚合物囊封剂。
15.一种用于井下潜水电泵系统的电动机(10),所述电动机特征在于:
可旋转轴(40);
定子(70);
转子(20),所述转子设置在所述定子(70)内并且与所述定子(70)之间隔开运行间隙(60),所述转子(20)被配置成用于使所述轴(40)旋转;以及
设置在所述运行间隙(60)中的润滑油(50),所述润滑油(50)包括基础油和抗降解添加剂,所述抗降解添加剂包括平均粒径为约1nm至约500nm的纳米胶囊;
所述纳米胶囊具有中和材料(15)的核和被配置成在酸性环境中释放所述中和材料(15)的聚合物囊封剂。
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US15/480,640 US10214704B2 (en) | 2017-04-06 | 2017-04-06 | Anti-degradation and self-healing lubricating oil |
PCT/US2018/026240 WO2018187558A1 (en) | 2017-04-06 | 2018-04-05 | Anti-degradation and self-healing lubricating oil |
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