CN111621352A - 用于液压油的润滑剂组合物 - Google Patents
用于液压油的润滑剂组合物 Download PDFInfo
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Abstract
本发明涉及润滑剂组合物,并且更具体地涉及即使在高温高压的苛刻条件下也具有优异的氧化稳定性和摩擦特性并因此适用于液压油的润滑剂组合物。本发明的润滑剂组合物包含基础油、液态烯烃共聚物、硫代磷酸酯化合物和磷酸鏻。
Description
技术领域
本发明涉及润滑剂组合物,并且更具体地涉及即使在高温高压的苛刻条件下也具有优异的氧化稳定性和摩擦特性并因此适用于液压油的润滑剂组合物。
背景技术
润滑剂是用于减少机器的摩擦表面上的摩擦力的产生或者使从摩擦表面产生的摩擦热消散的油性材料。由于需要润滑的机器各种各样以及这样的机器在其下工作的条件各种各样,因此润滑剂的类型和品质各不相同。根据其应用,必须使用不同类型的基础油。特别地,当将润滑剂用于飞机或先进液压系统时,需要具有强阻燃效果的液压油。
工业领域中使用的任何类型的液压油都是动力传递的介质,并且在液压设备的各个部分的润滑、防锈、密封和冷却中起作用。液压油是通过向基础油中添加添加剂而制造的,并且根据基础油的类型,大致分为矿物液压油(基于石油的液压油)和合成液压油,合成液压油分为基于聚α烯烃的液压油和基于酯的液压油。
同时,液压油的工作温度范围变化,并且尤其是在夏天,可能为75℃至85℃或更高。然而,在这样的温度下,矿物液压油和基于聚α烯烃的液压油产生大量的油蒸气。这样的油蒸气的出现引起增加液压油的蒸发损失的问题,并且还促进液压油的氧化。因此,必须使油蒸气的产生最小化。特别地,占液压油大部分的矿物液压油由于基础原料油的特性而需要额外的措施来提高氧化稳定性。此外,由于液压系统近来变得越来越复杂,因此要求液压油具有优异的摩擦特性。
因此,本发明人开发了用于液压油的润滑剂组合物,其具有优异的热稳定性和氧化稳定性并且能够减少液压设备的机械磨损。
[引用列表]
[专利文献]
(专利文献0001)韩国专利第10-0201759号
(专利文献0002)韩国专利申请公开第10-2008-0109015号
发明内容
技术问题
因此,牢记相关技术中遇到的问题而做出了本发明,并且本发明的一个目的是提供这样的润滑剂组合物:其中将用于减小摩擦的功能添加剂和具有高粘度指数的乙烯-α烯烃液态无规共聚物混合,从而表现出优异的摩擦特性、热稳定性和氧化稳定性。
本发明的另一个目的是提供用于液压油的润滑剂组合物,其在应用于液压设备时能够减少液压设备的机械磨损和能量消耗,并且由于液压油的物理特性的低变化而能够减少蒸发损失,因此可以长时间使用。
技术方案
为了实现上述目的,本发明提供了一种润滑剂组合物,其包含基础油、液态烯烃共聚物、硫代磷酸酯化合物和磷酸鏻。
基础油可以是选自矿物油、聚α烯烃(PAO)和酯中的至少一者。
液态烯烃共聚物可以通过使乙烯和α烯烃在单位点催化剂体系的存在下共聚合来制备,并且单位点催化剂体系优选包含茂金属催化剂、有机金属化合物和离子化合物。
液态烯烃共聚物的热膨胀系数可以为3.0至4.0。
液态烯烃共聚物可以以0.5重量%至30重量%,并且优选0.5重量%至25重量%的量包含在本发明的润滑剂组合物中。
硫代磷酸酯化合物可以以0.1重量%至5.0重量%,并且优选0.1重量%至3.0重量%的量包含在润滑剂组合物中。
磷酸鏻可以以0.05重量%至3.0重量%,并且优选0.1重量%至1.5重量%的量包含在润滑剂组合物中。
润滑剂组合物可以具有0.1至0.35的SRV摩擦系数和0.15至0.3的牵引系数。
发明效果
根据本发明,润滑剂组合物包含硫代磷酸酯、磷酸鏻和具有高粘度指数的乙烯-α烯烃液态无规共聚物,它们被混合在一起,从而改善了摩擦特性以及热稳定性和氧化稳定性,并且在应用于液压设备时能够减少液压设备的机械磨损和能量消耗,从而使节能效果最大化。
另外,根据本发明,润滑剂组合物具有低的液压油的物理特性变化,从而减少了蒸发损失,并且在RBOT氧化稳定性试验(ASTM D2271)中,可以持续1000分钟或更长,并且优选1200分钟或更长,从而使其能够长期用作液压油。
具体实施方式
在下文中,将给出本发明的详细描述。
本发明涉及润滑剂组合物,其具有优异的氧化稳定性和摩擦特性并因此适用于液压油。因此,本发明的润滑剂组合物包含基础油、液态烯烃共聚物、硫代磷酸酯化合物和磷酸鏻。
在此,基础油根据制造方法或精炼方法而在粘度、耐热性、氧化稳定性等方面有所不同,但是通常分为矿物油和合成油。API(AmericanPetroleum Institute,美国石油学会)将基础油分为五种类型,即第I类、第II类、第III类、第IV类和第V类。基于API范围,这些类型在2002年4月的API出版物1509,第15版,附录E中定义,并示于下表1中。
[表1]
在本发明的润滑剂组合物中,基础油可以是选自矿物油、聚α烯烃(PAO)和酯中的至少一者,并且可以是基于API范围的第I至V类中的任何类型。
更具体地,基于API范围,矿物油属于第I至III类,并且矿物油可以包括:由使通过原油的常压蒸馏和/或真空蒸馏获得的润滑剂馏出物馏分经历溶剂脱沥青、溶剂萃取、氢解、溶剂脱蜡、催化脱蜡、加氢精制、硫酸清洗和白粘土处理中的至少一种精炼过程而得到的油;蜡异构化矿物油;或经由费-托法(Fischer-Tropsch process)获得的天然气制油(gas-to-liquid,GLT)。
基于API范围,合成油属于第IV类或第V类,属于第IV类的聚α烯烃可以通过使用酸催化剂的高级α烯烃的低聚反应来获得,如美国专利第3,780,128号、美国专利第4,032,591号、日本专利申请公开号平1-163136等中所公开的,但是本发明不限于此。
属于第V类的合成油的实例包括烷基苯、烷基萘、异丁烯低聚物或其氢化物、石蜡、聚氧化亚烷基二醇、二烷基二苯醚、聚苯醚、酯等。
在此,烷基苯和烷基萘通常是烷基链长度为6至14个碳原子的二烷基苯或二烷基萘,并且烷基苯或烷基萘通过苯或萘与烯烃的弗瑞德-克来福特(Friedel-Crafts)烷基化来制备。用于制备烷基苯或烷基萘的烷基化烯烃可以是线性或支化的烯烃或其组合。
另外,酯的实例包括但不限于:戊二酸双十三烷基酯、己二酸二-2-乙基己酯、己二酸二异癸酯、己二酸双十三烷基酯、癸二酸二-2-乙基己酯、壬酸十三烷基酯、己二酸二-2-乙基己酯、壬二酸二-2-乙基己酯、三羟甲基丙烷辛酸酯、三羟甲基丙烷壬酸酯、三羟甲基丙烷三庚酸酯、季戊四醇2-乙基己酸酯、季戊四醇壬酸酯、季戊四醇四庚酸酯等。
在本发明的润滑剂组合物中,液态烯烃共聚物通过使乙烯和α烯烃单体在单位点催化剂体系的存在下共聚合以使α烯烃单元均匀地分布在共聚物链中来制备。优选地,液态烯烃共聚物通过使乙烯和α烯烃单体在单位点催化剂体系的存在下反应来制备,所述单位点催化剂体系包含交联的茂金属化合物、有机金属化合物和用于通过与交联的茂金属化合物反应形成离子对的离子化合物。
在此,单位点催化剂体系中包含的茂金属化合物可以是选自以下化学式1至6中的至少一者。
[化学式1]
[化学式2]
[化学式3]
[化学式4]
在化学式1至4中,
M是选自钛、锆和铪的过渡金属,
B不存在或者为包括以下的连接基团:C1-C20亚烷基、C6-C20亚芳基、C1-C20二烷基硅、C1-C20二烷基锗、C1-C20烷基膦基或C1-C20烷基胺基,
X1和X2彼此相同或不同,各自独立地为卤素原子、C1-C20烷基、C2-C20烯基、C2-C20炔基、C6-C20芳基、C7-C40烷基芳基、C7-C40芳基烷基、C1-C20烷基酰胺基、C6-C20芳基酰胺基、C1-C20烷叉基或C1-C20烷氧基,以及
R1至R10彼此相同或不同,各自独立地为氢、C1-C20烷基、C2-C20烯基、C6-C20芳基、C7-C20烷基芳基、C7-C20芳基烷基、C5-C60环烷基、C4-C20杂环基、C1-C20炔基、含C6-C20芳基的杂基或甲硅烷基。
[化学式5]
[化学式6]
在化学式5和6中,
M是选自钛、锆和铪的过渡金属,
B不存在或者为包括以下的连接基团:C1-C20亚烷基、C6-C20亚芳基、C1-C20二烷基硅、C1-C20二烷基锗、C1-C20烷基膦基或C1-C20烷基胺基,
X1和X2彼此相同或不同,各自独立地为卤素原子、C1-C20烷基、C2-C20烯基、C2-C20炔基、C6-C20芳基、C7-C40烷基芳基、C7-C40芳基烷基、C1-C20烷基酰胺基、C6-C20芳基酰胺基、C1-C20烷叉基或C1-C20烷氧基,以及
R1至R10彼此相同或不同,各自独立地为氢、C1-C20烷基、C2-C20烯基、C6-C20芳基、C7-C20烷基芳基、C7-C20芳基烷基、C5-C60环烷基、C4-C20杂环基、C1-C20炔基、含C6-C20芳基的杂基或甲硅烷基。
此外,R11、R13和R14全部为氢,每个R12基团彼此相同或不同,可以独立地为氢、C1-C20烷基、C2-C20烯基、C6-C20芳基、C7-C20烷基芳基、C7-C20芳基烷基、C5-C60环烷基、C4-C20杂环基、C1-C20炔基、含C6-C20芳基的杂基或甲硅烷基。
另外,化学式2至6的茂金属化合物可以包括通过加氢反应取代的化合物,并且其优选实例包括二甲基甲硅烷基双(四氢茚基)二氯化锆。
单位点催化剂体系中包含的有机金属化合物可以是选自有机铝化合物、有机镁化合物、有机锌化合物和有机锂化合物中的至少一者,并且优选为有机铝化合物。有机铝化合物可以是选自以下中的至少一者:例如,三甲基铝、三乙基铝、三异丁基铝、三丙基铝、三丁基铝、二甲基氯铝、二甲基异丁基铝、二甲基乙基铝、二乙基氯铝、三异丙基铝、三异丁基铝、三环戊基铝、三戊基铝、三异戊基铝、乙基二甲基铝、甲基二乙基铝、三苯基铝、甲基铝氧烷、乙基铝氧烷、异丁基铝氧烷和丁基铝氧烷,并且优选为三异丁基铝。
单位点催化剂体系中包含的离子化合物可以是选自有机硼化合物例如二甲基苯胺四(全氟苯基)硼酸盐/酯、三苯基碳鎓四(全氟苯基)硼酸盐/酯等中的至少一者。
可以考虑到催化活性来确定单位点催化剂体系的组分比,并且茂金属催化剂:离子化合物:有机金属化合物的摩尔比优选在1:1:5至1:10:1000的范围内调整以确保期望的催化活性。
此外,单位点催化剂体系的组分可以同时或以任何顺序添加到合适的溶剂中并且因此可以起活性催化剂体系的作用。在此,溶剂可以包括但不限于烃溶剂例如戊烷、己烷、庚烷等,或芳族溶剂例如苯、甲苯、二甲苯等,并且可以使用可用于制备的任何溶剂。
另外,用于制备液态烯烃共聚物的α烯烃单体包括C2-C20脂族烯烃,并且具体地可以是选自以下中的至少一者:乙烯、丙烯、1-丁烯、1-戊烯、3-甲基-1-丁烯、1-己烯、4-甲基-1-戊烯、3-甲基-1-戊烯、1-庚烯、1-辛烯、1-癸烯、1-十二碳烯和1-十四碳烯,并且可以包括异构形式,但是本发明不限于此。在共聚合中,单体含量为1mol%至95mol%,优选5mol%至90mol%。
本发明中需要的液态烯烃共聚物具有3.0至4.0的热膨胀系数和0.1或更小的溴值。
基于100重量%的润滑剂组合物,液态烯烃共聚物可以以0.5重量%至30重量%,并且优选0.5重量%至25重量%的量包含在内。如果基于100重量%的润滑剂组合物,液态烯烃共聚物的量小于0.5重量%,则稳定性可能劣化。另一方面,如果其量超过30重量%,则将所得组合物应用于液压油变得困难,这是不期望的。
用作减摩剂的硫代磷酸酯化合物可以是选自单硫代磷酸酯、二硫代磷酸酯、三硫代磷酸酯、甲基硫代磷酸酯、乙基硫代磷酸酯和磺酰基硫代磷酸酯中的至少一者。当润滑剂组合物中包含硫代磷酸酯化合物时,其可以表现出与现有的耐磨剂的协同效应和减小摩擦的效果,此外,可以通过减小摩擦来实现节能效果。
基于100重量%的润滑剂组合物,硫代磷酸酯化合物可以以0.1重量%至5.0重量%,并且优选0.1重量%至3.0重量%的量包含在内。如果基于100重量%的润滑剂组合物,硫代磷酸酯化合物的量小于0.1重量%,则减小摩擦的效果不明显。另一方面,如果其量超过5.0重量%,则尽管其过量添加,但是附加的减小效果不明显,这是不期望的。
磷酸鏻是具有以下化学式7的结构的物质,并且用作减摩剂/减磨损剂。特别地,当其与硫代磷酸酯化合物一起使用时,其效果可以最大化。
[化学式7]
磷酸鏻以具有鏻阴离子和磷酸根阳离子二者的离子液体的形式存在,并且在各种鏻化合物中,表现出特征性的减小摩擦/磨损的效果。
另外,基于100重量%的润滑剂组合物,磷酸鏻可以以0.05重量%至3.0重量%,并且优选0.1重量%至1.5重量%的量包含在内。如果基于100重量%的润滑剂组合物,磷酸鏻的量小于0.05重量%,则减小摩擦/磨损的效果可能不明显。另一方面,如果其量超过3.0重量%,则其与硫代磷酸酯化合物没有协同效应,并且磨损可能增加,这是不期望的。
本发明的润滑剂组合物还可以包含选自抗氧化剂、金属清洗剂、防腐剂、泡沫抑制剂、倾点下降剂、粘度改进剂、耐磨剂、及其组合的添加剂。
基于100重量%的润滑剂组合物,抗氧化剂可以以0.01重量%至5.0重量%的量包含在内,并且优选以酚类抗氧化剂和胺类抗氧化剂的混合物,更优选0.01重量%至3.0重量%的酚类抗氧化剂和0.01重量%至3.0重量%的胺类抗氧化剂的混合物的形式使用。
酚类抗氧化剂可以是选自2,6-二丁基苯酚、受阻双酚、高分子量受阻酚和受阻酚与硫醚中的任一者。
胺类抗氧化剂可以是选自二苯胺、烷基化二苯胺和萘胺中的任一者,并且优选地,烷基化二苯胺是二辛基二苯胺、辛基化二苯胺或丁基化二苯胺。
金属清洗剂可以是选自金属酚盐、金属磺酸盐和金属水杨酸盐中的至少一者,并且优选地,基于100重量%的润滑剂组合物,金属清洗剂以0.1重量%至10.0重量%的量包含在内。
防腐剂可以是苯并三唑衍生物,并且优选是选自苯并三唑、2-甲基苯并三唑、2-苯基苯并三唑、2-乙基苯并三唑和2-丙基苯并三唑中的任一者。基于100重量%的润滑剂组合物,防腐剂可以以0重量%至4.0重量%的量包含在内。
泡沫抑制剂可以是聚氧化烯多元醇,并且优选地,基于100重量%的润滑剂组合物,泡沫抑制剂以0重量%至4.0重量%的量包含在内。
倾点下降剂可以是聚(甲基丙烯酸酯),并且优选地,基于100重量%的润滑剂组合物,倾点下降剂以0.01重量%至5.0重量%的量包含在内。
粘度改进剂可以是聚异丁烯或聚甲基丙烯酸酯,并且优选地,基于100重量%的润滑剂组合物,粘度改进剂以0重量%至15重量%的量包含在内。
耐磨剂可以是选自有机硼酸盐/酯、有机亚磷酸盐/酯、有机含硫化合物、二烷基二硫代磷酸锌、二芳基二硫代磷酸锌和磷硫化烃中的至少一者,并且优选地,耐磨剂以0.01重量%至3.0重量%的量包含在内。
本发明的润滑剂组合物的SRV摩擦系数为0.1至0.35。此外,润滑剂组合物的牵引系数为0.15至0.3。
发明实施方式
通过以下实施例更好地理解本发明。然而,本发明不限于这些实施例,而是可以以其他形式来实施。提供这些实施例以彻底解释本发明并将本发明的精神充分地传达给本领域技术人员。
1.添加剂组合物的制备
如下表2所示制备用于本发明的润滑剂组合物的添加剂组合物。
[表2]
2.液态烯烃共聚物的制备
使用低聚方法通过催化反应过程制备液态烯烃共聚物。根据随后的反应时间和条件,制备具有不同分子量的液态烯烃共聚物,并且其特性示于下表3中。
反应时间和条件从20小时开始各自增加4小时。在此,向其中添加的氢和共聚单体C3的量各自增加10%,并在单独的条件下进行聚合,并且根据其分子量对所得聚合物进行分类。
[表3]
3.用于液压油的润滑剂组合物的制备
如下表4和5所示,通过将基础油、液态烯烃共聚物、硫代磷酸酯化合物、磷酸鏻和以上制备的添加剂混合来制备润滑剂组合物。在此,基础油是在100℃下运动粘度为4cSt的聚α烯烃(PAO 4cSt,可获自ChevronPhilips),硫代磷酸酯化合物为单硫代磷酸酯。
制备例1至67和比较例1至14.包含添加剂A的用于液压油的润滑剂组合物
[表4]
制备例68至116和比较例15至53.包含添加剂B的用于液压油的润滑剂组合物
[表5]
4.特性的评估
如下测量制备例和比较例中制备的润滑剂组合物的特性。结果示于下表6和7中。
摩擦系数
在盘上球(ball-on-disc)模式下,通过在50Hz下依次将温度以10℃的增量从40℃升高至120℃并比较在各个温度下的平均摩擦系数来评估摩擦性能。在此,摩擦系数值随着有效性的增加而减小。
牵引系数
使用PCS Instruments制造的MTM仪器测量牵引系数。在此,将测量条件固定为50N和SRR 50%,并且根据温度变化观察摩擦力和牵引力。温度从40℃变化至120℃,并比较平均值。
耐磨性
在20kg负载、1200rpm和54℃的条件下,使四个钢球在有润滑剂组合物的情况下经历摩擦60分钟,比较磨痕的尺寸,并根据ASTM D4172进行评估。在此,磨痕(平均磨痕直径,μm)值随着有效性的增加而减小。
氧化稳定性
根据ASTM D2271,使用RBOT(Rotational Bomb Oxidation Test,旋转氧弹试验)仪测量氧化稳定性。
[表6]
[表7]
从表6和7可以明显看出,与比较例的润滑剂组合物相比,包含本发明的量范围内的液态乙烯α烯烃共聚物、硫代磷酸酯化合物和磷酸鏻的润滑剂组合物在磨痕和摩擦系数方面显著降低,并且还表现出优异的氧化稳定性。因此,结论是,本发明的润滑剂组合物在摩擦特性和稳定性方面得到改善,并因此适用于液压油。
尽管已经出于说明目的公开了本发明的实施方案,但是本领域技术人员将理解,在不脱离如所附权利要求中公开的本发明的范围和精神的情况下,可以进行各种修改、添加和替换。
Claims (15)
1.一种润滑剂组合物,包含:
基础油、液态烯烃共聚物、硫代磷酸酯化合物和磷酸鏻。
2.根据权利要求1所述的润滑剂组合物,其中所述液态烯烃共聚物通过使用单位点催化剂体系使乙烯和α烯烃共聚合来制备。
3.根据权利要求1所述的润滑剂组合物,其中所述硫代磷酸酯化合物是选自单硫代磷酸酯、二硫代磷酸酯、三硫代磷酸酯、甲基硫代磷酸酯、乙基硫代磷酸酯和磺酰基硫代磷酸酯中的至少一者。
5.根据权利要求2所述的润滑剂组合物,其中所述单位点催化剂体系包含茂金属催化剂、有机金属化合物和离子化合物。
6.根据权利要求1所述的润滑剂组合物,其中所述液态烯烃共聚物的热膨胀系数为3.0至4.0。
7.根据权利要求1所述的润滑剂组合物,其中所述液态烯烃共聚物的溴值为0.1或更小。
8.根据权利要求1所述的润滑剂组合物,其中所述硫代磷酸酯化合物以0.1重量%至5.0重量%的量包含在所述润滑剂组合物中。
9.根据权利要求1所述的润滑剂组合物,其中所述液态烯烃共聚物以0.5重量%至30重量%的量包含在所述润滑剂组合物中。
10.根据权利要求1所述的润滑剂组合物,其中所述基础油是选自矿物油、聚α烯烃(PAO)和酯中的至少一者。
11.根据权利要求1所述的润滑剂组合物,还包含选自以下的添加剂:抗氧化剂、金属清洗剂、防腐剂、泡沫抑制剂、倾点下降剂、粘度改进剂、耐磨剂、及其组合。
12.根据权利要求1所述的润滑剂组合物,其中所述润滑剂组合物的SRV摩擦系数为0.1至0.35。
13.根据权利要求1所述的润滑剂组合物,其中所述润滑剂组合物的牵引系数为0.15至0.3。
14.根据权利要求1所述的润滑剂组合物,其中所述润滑剂组合物在氧化稳定性评估(RBOT,ASTM D2271)中持续1000分钟或更长。
15.根据权利要求1所述的润滑剂组合物,其中所述润滑剂组合物用作液压油。
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