CN103221523A - 用于冲击设备的润滑剂 - Google Patents

用于冲击设备的润滑剂 Download PDF

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CN103221523A
CN103221523A CN2011800553729A CN201180055372A CN103221523A CN 103221523 A CN103221523 A CN 103221523A CN 2011800553729 A CN2011800553729 A CN 2011800553729A CN 201180055372 A CN201180055372 A CN 201180055372A CN 103221523 A CN103221523 A CN 103221523A
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N·诺茨
A·G·希
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Abstract

本发明公开了适用于冲击设备的润滑剂。该润滑剂包含以协同量与齿轮油添加剂包和摩擦改进剂调合的选自I类或II类的基础油。该润滑剂由于齿轮油添加剂包和摩擦改进剂的协同效应而表现出优越的磨损性能和优越的极压性能。在优选实施方案中,该齿轮油添加剂包包含聚甲基丙烯酸烷基酯聚合物和含有合成酯的摩擦改进剂。

Description

用于冲击设备的润滑剂
发明领域
本申请涉及适用于冲击设备(percussion equipment)的包含I类或II类油、齿轮油添加剂包和合成酯的润滑剂,以及制备这样的润滑剂的方法。
背景技术
冲击式气动设备例如凿岩机、手提钻和架式凿岩机(drifter)的主要OEM商已公开了在他们的设备中应适用的流体的规格要求。润滑剂要满足的规格的一个性能是能够在极压下或“EP”条件下产生润滑。润滑剂的EP性能由Timken(ASTM D2782)和Falex EP(ASTMD2670)试验标准所定义。EP性能通常通过提高配方中硫(无活性和活性)以及磷化合物的量得到提高。可能还使用摩擦改进剂来改变边界润滑性能。
冲击装置润滑剂必须显示出的特性是长的设备寿命、在潮湿条件下的可靠性、在潮湿环境中的防护性和低的存货成本。极压性能经受住凿岩机使用中典型的重的冲击载荷,从而保护设备不受快速磨损。凿岩机活塞、来复杆和螺母因此受到保护。润滑剂附着到被润滑的部件并且耐受被压缩空气中的痕量水洗去。防锈性能保护关键部件免受潮湿环境的腐蚀作用。润滑剂应当是多用途的,用于手工油润和链传动,从而使存藏的润滑剂数目最小。该润滑剂在闭式齿轮、工业平轴承和抗摩擦轴承的润滑中是有效的。其显示出低的气味和低毒性。
作为一般规则,摩擦改进剂损害抗磨损添加剂和/或极压添加剂的性能。通常,润滑剂中的抗磨损添加剂或极压添加剂通过在设备的运动部件之间维持润滑剂层来减少损伤。提供抗磨损或极压的润滑剂添加剂有助于减少金属与金属的有害接触。需要提供摩擦性能和抗磨损/极压性能之间的平衡的凿岩机润滑剂。本申请的润滑剂具有这样的协同平衡。
发明概述
本发明公开了适用于冲击设备的润滑剂。该润滑剂包含以协同量与齿轮油添加剂包(gear oil package)和摩擦改进剂调合的选自I类或II类的基础油。该润滑剂由于齿轮油添加剂包和摩擦改进剂的协同效应而表现出优越的磨损性能和优越的极压性能。
发明详述
润滑剂基础油通常划分为I类、II类、III类、IV类和V类润滑剂基础油及其混合物。润滑剂基础油包括合成润滑剂基础油,例如费-托衍生的润滑剂基础油,以及非合成润滑剂基础油和合成润滑剂基础油的混合物。下表I中显示了在API Interchange Guidelines(APIPublication1509)中使用硫含量、饱和化合物含量和粘度指数定义的润滑剂基础油的规格:在本发明中,I类和II类润滑剂是优选的。
表I
Figure BDA00003203821500021
生产I类润滑剂基础油的设施典型地使用溶剂来提取较低粘度指数(VI)的组分,使原料油的VI提高到所需规格。这些溶剂典型地是苯酚或糠醛。溶剂提取得到具有小于90%饱和化合物和大于300ppm硫的产品。世界上大多数润滑剂产量为I类范畴。
生产II类润滑剂基础油的设施典型地使用加氢加工例如加氢裂化或苛刻加氢处理以使原料油的VI提高到规格值。加氢加工的使用典型地使饱和化合物含量提高到高于90,并使硫含量下降到低于300ppm。世界上约10%润滑剂基础油产量为II类范畴,而美国约30%产量为II类。
生产III类润滑剂基础油的设施典型地使用蜡异构化技术来生产非常高的VI的产品。因为起始进料为蜡质减压瓦斯油(VGO)或含所有饱和化合物和少量硫的蜡,所以III类产品具有高于90%的饱和化合物含量和低于300ppm的硫含量。对于蜡异构化法生产III类润滑剂基础油而言,费-托蜡是理想的进料。世界上润滑剂供应中仅一小部分为III类范畴。
通过正构α烯烃的低聚衍生得到IV类润滑剂基础油,并将其称为聚α烯烃(PAO)润滑剂基础油。
V类润滑剂基础油为所有其它润滑剂基础油。这类包括合成酯类、硅润滑剂、卤化的润滑剂基础油和VI值低于80的润滑剂基础油。V类润滑剂基础油典型地通过用于生产I类和II类润滑剂基础油的相同方法但在不太苛刻的条件下由石油来制备。
合成润滑剂基础油符合API Interchange Guidelines,但通过费-托合成、乙烯低聚、正构α烯烃低聚或沸点低于C10的烯烃低聚来制备。就本申请而言,合成润滑剂基础油不包括合成酯和硅润滑剂。
如本发明概述中所指出,本发明的润滑剂包含与齿轮油添加剂包或摩擦改进剂以协同量调合的选自I类或II类的基础油。
本发明中使用的优选的齿轮油添加剂包表现出许多积极特征。这些受功能特性例如倾点和粘度指数的影响。例如,所述包可溶于I类和II类基础料。所述包显示出优异的热和氧化稳定性,以及与通常所用的密封材料的优异相容性。该齿轮包显示了经证明的传动性能、在极压条件下优异的防护和耐久性、以及对防止铜被腐蚀的优越防护性。强破乳性和泡沫防止以及优越的贮存稳定性也得到证明。
在表II中提供了适用于本发明的齿轮油添加剂包的典型特性。
表II-适用于本发明的汽车齿轮油添加剂包的典型特性
外观 透明琥珀色液体
在100℃的粘度 10-15mm2/s
比重15.6/15/6℃ 1.005
闪点 >80℃(COC)
组成 硫-磷烃
硫含量 15-25wt%
磷含量 0.75-0.1.25wt%
本发明优选的添加剂包包含如上文所定义的根据本发明使用的C12-C20聚甲基丙烯酸烷基酯聚合物。将该添加剂包加到矿物油基润滑油中,使得所述聚甲基丙烯酸烷基酯聚合物以重量计占成品润滑油的0.1-0.3%。优选地,将该添加剂包加到矿物油基润滑油中,使得该添加剂包的含量以重量计占成品润滑油的至多15%。典型地,将该添加剂包加到矿物油基润滑油中,使得该添加剂包的含量以重量计占成品润滑油的4-10%。这样的添加剂包可以包括本技术领域的技术人员已知的任何油添加剂,该油添加剂在按照本发明使用时不干扰聚甲基丙烯酸烷基酯聚合物的性能。可以与本发明结合使用的其它合适添加剂对于本技术领域的技术人员来说是显而易见的,可以包括倾点下降剂、抗磨剂、抗氧化剂、防锈剂、分散剂、硼酸化分散剂、粘度指数改进剂、清净剂和摩擦改进剂。
粘度指数改进剂
表III-不同ISO等级的工业流体润滑剂的粘度范围
Figure BDA00003203821500041
粘度指数增进剂赋予润滑油高温和低温操作性,并且使其在提高的温度下仍是相对粘性的,而且在低的温度下还表现出有可接受的粘度或流动性。粘度指数改进剂一般是高分子量烃类聚合物,包括聚酯。还可以使粘度指数增进剂衍生以包括其它性能或功能,例如增加分散性能。这些油溶性粘度增进聚合物一般应有103-106,优选104-106的平均分子量,其分子量是采用凝胶渗透色谱法或渗透压力测定法测定的。
用于本文的粘度指数改进剂可以包括基于聚甲基丙烯酸酯的粘度指数改进剂、基于烯烃共聚物的粘度指数改进剂(例如基于异丁烯和基于乙烯-丙烯共聚物的粘度指数改进剂)、基于聚烷基苯乙烯的粘度指数改进剂、基于氢化苯乙烯-丁二烯共聚物的粘度指数改进剂,以及基于苯乙烯-马来酸酐酯共聚物的粘度指数改进剂。
在美国专利No.5,075,383、5,102,566、5,139,688、5,238,588和6,107,257中可找到合适粘度指数改进剂的代表性实例。
倾点下降剂
使用倾点下降剂改善油基组合物的低温性能。例如参见C.V.Smalheer和R.Kennedy Smith的《润滑剂添加剂(LubricantAdditives)》第8页(Lezius Hiles Co.publishers,Cleveland,Ohio,1967)。有用的倾点下降剂的实例是聚甲基丙烯酸酯、聚丙烯酸酯、聚丙烯酰胺;卤代石蜡和芳族化合物的缩合产物;羧酸乙烯酯共聚物;以及二烷基富马酸酯、脂肪酸乙烯酯和烷基乙烯醚的三聚物。倾点下降剂描述于美国专利No.2,387,501、2,015,748、2,655,479、1,815,022、2,191,498、2,666,746、2,721,877、2,721,878和3,250,715中。
分散剂
用于本发明的分散剂可以是成灰分的或无灰分的。本文使用的合适分散剂可以典型地包括通过桥接基团与聚合物主链连接的胺、醇、酰胺或酯极性部分。分散剂可以例如选自油溶性的盐、酯、氨基-酯、酰胺、酰亚胺和长链烃取代的单和二羧酸或它们的酸酐的
Figure BDA00003203821500051
唑啉;链烃的硫代羧酸盐衍生物;长链脂族烃,具有直接与其连接的多胺;和由长链取代的苯酚与甲醛和多亚烷基多胺的缩合而生成的Mannich缩合产物;以及Koch反应产物。长链脂族烃可以是聚合物,例如聚烯烃,例如包括聚异丁烯、聚乙烯、聚丙烯及其共聚物和/或与其它α-烯烃的共聚物。用于本文的典型PIB分子量可以是约950-6000。
在美国专利No.5,075,383、5,139,688、5,238,588和6,107,257中可找到适用于本发明的分散剂的代表性实例。在美国专利申请公布No.2001/0036906A1中找到另外的代表性实例。
清净剂
清净剂是减少在发动机中生成活塞沉积物,例如高温清漆和漆沉积物的添加剂。清净剂通常具有酸中和性能,并且能使细粒固体保持为悬浮状。金属清净剂优选用于改善所得润滑油组合物的酸中和性能、高温清净性和抗磨损性能。
用于本文的清净剂可以是在润滑油配方中使用的任何洗涤剂,可以是成灰分或无灰分的品种。适用于本发明的清净剂包括在润滑油中通常使用的所有洗涤剂,其中包括金属清净剂。金属清净剂的具体实例是选自碱金属或碱土金属磺酸盐、碱金属或碱土金属酚盐、碱金属或碱土金属水杨酸盐的那些金属清净剂。在一个实施方案中,这种润滑油配方基本上不含硫化酚盐。
在美国专利No.6,008,166中可找到适用于本发明的清净剂的代表性实例。在美国专利申请No.2002/0142922A1、2002/0004069A1和2002/0147115A1中可以找到合适清净剂的其它代表性实例。通过引用将上述参考文献的内容并入本文。
抗氧化剂
有用的抗氧化剂物质包括油溶性的酚化合物、油溶性的含硫有机化合物、油溶性的胺抗氧化剂、油溶性的有机硼酸酯、油溶性的有机亚磷酸酯、油溶性的有机磷酸酯、油溶性的有机二硫代磷酸酯和它们的混合物。这样的抗氧化剂可以是不含金属的(即不含能产生含硫酸盐灰分的金属),因此非常优选地是无灰分的(硫酸盐灰分值不大于1重量%SASH,该值是采用ASTM D874测定的)。
在美国专利No.5,102,566中可找到适用于本发明的抗氧化剂的代表性实例。在美国专利申请公布No.2001/0012821A1中可找到适用于本发明的抗氧化剂的另外代表性实例。通过引用将上述参考文献的内容并入本文。
摩擦改进剂
摩擦改进剂用于赋予润滑油组合物适当的摩擦特性。
摩擦改进剂包括例如如下化合物:脂族胺或乙氧基化脂族胺,脂族脂肪酸胺,脂族羧酸,脂族羧酸多元醇酯,例如脂肪酸甘油酯,如甘油酚酯所例示,脂族羧酸酯-酰胺,脂族膦酸酯,脂族磷酸酯,脂族硫代膦酸酯,脂族硫代磷酸酯等,其中脂族基团通常含有约8个以上的碳原子以便使所述化合物具有适当的油溶性。另外合适的是通过使一种或多种脂族琥珀酸或酸酐与氨反应生成的脂族取代的琥珀酰亚胺。另外,适用于本发明的是含钼的摩擦改进剂。
含钼摩擦改进剂的代表性实例包括可在下述文献中找到的那些摩擦改进剂:美国专利No.5,650,381;RE37,363E;美国专利No.5,628,802;4,889,647;5,412,130;4,786,423;4,812,246;5,137,647;5,364,545;5,840,672;5,925,600;5,962,377;5,994,277;6,017,858;6,150,309;6,174,842;6,187,723;6,268,316;欧洲专利No.EP222 143B1;EP281992B1;EP719314B1;EP719315B1;EP874040A1;EP892037A1;EP931 827A1;EP1 041 134A1;EP1 041 135A1;EP1 087 008A1;EP1 088 882A1;EP;日本专利No.JP11035961;和国际公布No.WO95/07965;WO00/08120;WO00/71649。
在下述文献中找到合适摩擦改进剂的代表性实例:美国专利No.3,933,659;4,105,571;3,779,928;3,778,375;3,852,205;3,879,306;3,932,290;3,932,290;4,028,258;4,344,853;5,102,566;6,103,674;6,174,842;6,500,786;6,500,786;和6,509,303。在美国专利申请公布No.2002/0137636A1中找到合适摩擦改进剂的另外代表性实例。
在本申请的一个实施方案中特别理想地用作摩擦改进剂的是合成酯。这些包括Lubrizol Syn-estherTM GY-25,即一种设计用来完全替代或很大地减少工业油和冷却剂中极压添加剂例如氯或硫的量的高分子量聚酯。在直链油中,当这样的酯与含磷添加剂或者油溶性的活性或无活性硫化合物一起配制时获得最大的有效性。当使用这些酯时,活性硫的量通常可减少约50-75%。在可溶性油和半合成液(semi-synthetics)中,除这些酯外不需要极压添加剂。
也适宜的其它合成酯包括ADDCOTM EP-50,SynEsterTM SE-110,Syn-EsterTM SE-115,Syn-EsterTM GY-HTO,Syn-EsterTM GY-56,Syn-EsterTM GY-500,Syn-EsterTM GY-10和Syn-EsterTM GY-15。
这些聚酯是无灰的和烧除干净的。由于它们的低不饱和度,这些合成酯不导致染色并且具有优异的热、氧化和水解稳定性。它们理想地适用于直链油,其中在高温下的性能是所需的。合成酯倾向于可溶于环烷属油,在链烷属油中的溶解度取决于具体所选择的油、酯浓度、油粘度和加氢处理程度。其是猪油和相关润滑性添加剂的优异替代品。合成酯例如Syn-Ester TM GY-25是饱和的支链聚合物。预期它们与常规脂肪添加剂相比对生物侵蚀较不敏感。Syn-ester TMGY-25不含氯、硫或磷。
表IV-合成酯的典型性能-
1模糊是酸碱滴定的结果,不表示不溶解性或颗粒物质。SYN-ESTERTMGY-25在加热到32℃时变得透明。在室温下在一般处理水平下产物在油中是透明的。
除摩擦改进剂外,还可以加入少量增粘剂以提高润滑剂的粘着性。
Falex Pin and Vee Block method(ASTM D2670-95)是测量流体润滑剂的磨损性能的标准试验方法。其概述如下:
使旋转钢轴颈顶紧两个浸没在润滑剂样品中的固定的钢制V形块运转。向V形块施加负荷并通过棘轮机构进行维持。测定磨损并将其作为在规定的测试时间期间为维持负荷不变而行进的棘轮机构的齿数加以记录。可以使用该试验方法来确定在规定的试验条件用流体润滑剂获得的磨损。
Timken方法(ASTM D2782-02)是测量润滑流体的极压性能的标准试验方法。试验仪用顶紧钢制试验块旋转的钢制杯(cup)进行操作。旋转速度为123.71±0.77m/min(405.88±2.54ft/min),其等于800±5rpm的主轴速度。在开始试验前将流体样品预加热到37.8±2.8C(100±5F)。
进行两种测定:可以使旋转杯和固定块之间所测试的润滑剂膜破裂并且导致刮伤或卡咬的最小负荷(刮伤值);和旋转杯将不使润滑剂膜破裂和导致旋转杯和固定块之间的刮伤或卡咬所处的最大负荷(OK值)。
表V论述了不同ISO等级的工业流体润滑剂的标准特性。这样的润滑剂包括凿岩机油。
表V-不同ISO等级的工业流体润滑剂的标准特性
Figure BDA00003203821500101
实施例
表VI-实验结果
Figure BDA00003203821500102
表VI中给出的实验结果的讨论
虽然在新型凿岩机润滑剂的开发期间设法满足EP试验的要求,但本申请人发现了新的结果。其涉及加入少量合成酯(添加剂级-摩擦改进剂)。合成酯或摩擦改进剂的加入促进了凿岩机的EP性能。即使将在其它商业配方中使用摩擦改进剂来提高EP性能,使用具有表II的典型特性的汽车齿轮添加剂包与具有表IV中所公开的特性的合成酯(例如Lubrizol Syn-Ester GY-25,一种摩擦改进剂)以0.1wt%的处理率(参见表VI)开发凿岩机油期间似乎找到了协同点(synergistic point)。在表VI中,用于Falex EP试验的配方结果显示出对摩擦改进剂的加入的最大响应。表II的变化量的齿轮油添加剂包(例如Hitec388)在1.3wt%下给出了混合结果,其中销没有扭断但是产生扭矩峰值充分低于作为试验规格的最小值的2000lbs。该结果是由引起的试验设备中的V形块熔接(weld)到所述销上并然后摆脱(break free)而不导致销扭断。随着处理率提高到1.6wt%,结果得到改善但是仍低于规格,当测试1.9wt%时其开始降低,因此达到得自基础添加剂包的益处。还研究了加入不同的摩擦改进剂,以0.1wt范围内的处理率的加入显示出改善的FalexEP结果。随着Syn-esterGF-25的处理率为0.1wt%,出现最大的改善。

Claims (15)

1.适用于冲击设备的润滑剂,所述润滑剂包含与协同量的齿轮油添加剂包和摩擦改进剂调合的选自I类或II类的基础油。
2.权利要求1的润滑剂,其中所述润滑剂由于多种功能性能和抗磨损性能的协同效应而表现出优越的磨损和极压性能。
3.权利要求2的润滑剂,其中所述多种功能性能由齿轮油添加剂包提供,所述抗磨损性能由摩擦改进剂提供。
4.权利要求3的润滑剂,其中所述齿轮油添加剂包包含聚烷基甲基丙烯酸酯聚合物。
5.权利要求4的润滑剂,其中聚烷基为C12-C20
6.权利要求1的润滑剂,其中所述摩擦改进剂包含合成酯。
7.权利要求6的润滑剂,其中所述合成酯是饱和的支链聚合物。
8.权利要求7的润滑剂,其中所述合成酯不含氯、硫和磷。
9.权利要求2的润滑剂,其中所述抗磨损性能通过Falex试验进行测量,所述极压性能通过Timken试验进行测量。
10.权利要求9的润滑剂,其中在Falex试验下的最低可接受负荷为2000lb。
11.权利要求的润滑剂10,其中在Timken试验下的最低可接受负荷为30lb。
12.权利要求1的润滑剂,其中所述齿轮油添加剂包以1.3wt%-1.9wt%的量存在,所述摩擦改进剂以0.05wt%-2.5wt%的量存在。
13.权利要求7的润滑剂,其中所述合成酯可溶于环烷属油,所述合成酯可溶于链烷属油。
14.权利要求11的润滑剂,其中Falex负荷大于3000lbs,TimkenOK负荷大于60。
15.制备适用于冲击设备的润滑剂的方法,所述方法包括将齿轮油添加剂包和摩擦改进剂以协同量加入到II类油中。
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US8822393B2 (en) 2014-09-02
CN103221523B (zh) 2016-06-22
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