CN1332004C - 用于传动流体的润滑剂组合物 - Google Patents

用于传动流体的润滑剂组合物 Download PDF

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CN1332004C
CN1332004C CNB2004100923997A CN200410092399A CN1332004C CN 1332004 C CN1332004 C CN 1332004C CN B2004100923997 A CNB2004100923997 A CN B2004100923997A CN 200410092399 A CN200410092399 A CN 200410092399A CN 1332004 C CN1332004 C CN 1332004C
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CN1626634A (zh
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R·N·耶尔
S·H·特尔西尼
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Afton Chemical Corp
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Abstract

一种添加剂组合物，可以包含至少一种含磷和含硼分散剂，至少一种含硼分散剂和至少一种清洁剂。这种组合物可以用于传动以提供抗震颤性能和/或提高耐磨寿命。

Description

用于传动流体的润滑剂组合物
技术领域
本发明所述的组合物可以用于多种润滑和传动应用，例如，用于自动传动，如连续变速传动和/或自动化手动传动，传动可以有或没有如变矩器的启动装置。
背景技术
使用或计划使用连续可变传动(CVTs)来代替传统自动传动的汽车制造厂逐年稳定增加。已经表明，连续可变传动与传统自动传动相比，提高了燃料效率和驱动性能，同时减少了排放。
连续可变传动可以包括钢推动带和滑轮装置、链条和滑轮装置、或轮盘装置(在为环形连续可变传动的情况时)，与变矩器或其它形式的启动装置相结合。扭矩通过在滑轮装置和带或链或盘之间的金属-金属接触而传送。扭矩的有效传送要求滑轮装置与带或盘之间相对高的钢-钢摩擦，并且磨损最小。低摩擦将导致所述带打滑或严重的磨损。因此，钢-钢摩擦是扭矩传送的关键要求。用以提高钢-钢之间摩擦的添加剂技术将导致更高的钢-纸(steel-on-paper)摩擦。在装配有作为启动装置的变矩器的连续可变传动中，变矩离合器的存在要求连续可变传动流体具有适当程度的钢-纸摩擦力，以避免困扰高摩擦传动流体的问题。这样的问题的一个例子是震颤。连续可变传动启动离合器除了要满足连续可变传动的要求之外，还必须提供如在传统自动传动中的同样功能。这样，开发连续可变传动流体的配方设计师所面临主要问题之一是平衡钢-钢摩擦和钢-纸摩擦的要求。
发明内容
本发明描述了满足钢-钢摩擦和钢-纸摩擦的性能要求的流体。
在本发明的一个实施方式中，添加剂组合物可以含有(a)至少一种第一含磷和硼的分散剂，(b)至少一种第二含硼不含磷的分散剂，和(c)至少一种清洁剂。在添加组合物中大约含20重量％的第一种分散剂。
另一个实施方式中，传动流体组合物可以包含占主要含量的基油和添加组合物，包含(a)至少第一种含有磷和硼的分散剂，(b)至少第二种含硼分散剂，没有磷，和(c)至少一种清洁剂。在流体中含有约2.0重量％或更多的第一种分散剂。
另一个实施方式中，增加钢-钢摩擦和/或稳定钢-纸摩擦的方法包括用润滑组合物来对传动进行润滑，这种组合物包括占主要含量的基油和一种添加剂组合物，包含(a)至少一种第一含磷和硼的分散剂，在流体中含有2.0重量％或更多；(b)至少一种第二含硼不含磷的分散剂；和(c)至少一种清洁剂。
具体实施方式
本发明的实施方式可以包含含有高水平分散剂的组合物，所述分散剂含有硼和磷。本发明的实施方式给出了改进的钢-钢摩擦和钢-纸摩擦性能效力。与传统的传动流体相比，使用高磷和硼水平的传动流体为其摩擦性能带来好处，如，对于自动传动、连续可变传动和/或与连续可变传动联合操作的启动装置，如变矩器。
连续可变传动可以包含与滑轮装置结合布置的钢推动带或链或轮盘装置，其与变矩器或其它形式的启动装置相结合来运行。扭矩通过滑轮和带或链或轮盘装置之间的金属-金属接触而传送。扭矩的有效传送要求相对高的钢-钢摩擦，以及带或链与滑轮之间最小的磨损。低摩擦导致皮带打滑和严重的磨损。因此，钢-钢摩擦是扭矩传送的一个关键要求。用于增加钢-钢摩擦的添加剂技术会潜在地导致较高的钢-纸摩擦。在带有如变矩器的启动装置的连续可变传动装置中，启动装置的存在要求连续可变传动流体具有一个合适水平的钢-纸摩擦。如果没有合适水平的钢-纸摩擦，问题将会出现，如震颤。这样，开发连续可变传动流体的配方设计师的其中一个主要问题是平衡钢-钢摩擦与钢-纸摩擦的要求。
本发明描述了流体组合物，它能满足钢-钢摩擦和钢-纸摩擦的性能要求。
含硼分散剂
在一个实施方式中，添加剂组合物可以包括至少一种含硼分散剂，其中，含硼分散剂不含磷。形成含硼酸分散剂的方法是把分子中含有碱氮和/或至少一个羟基的无灰硼化，所述分散剂如丁二酰亚胺分散剂、丁二酰胺分散剂、丁二酸酯分散剂、丁二酸酯酰胺分散剂、Mannich碱分散剂、烃基胺或聚胺分散剂。制备前述的无灰分散剂的方法被本领域普通技术人员熟知，此方法专利文献有报道。例如，下述专利描述了前述的各种无灰分散剂的合成：专利号为2,459,112；2,962,442；2,984,550；3,036,003；3,163,603；3,166,516；3,172,892；3,184,474；3,202,678；3,215,707；3,216,936；3,219,666；3,236,770；3,254,025；3,271,310；3,272,746；3,275,554；3,281,357；3,306,908；3,311,558；3,316,177；3,331,776；3,340,281；3,341,542；3,346,493；3,351,552；3,355,270；3,368,972；3,381,022；3,399,141；3,413,347；3,415,750；3,433,744；3,438,757；3,442,808；3,444,170；3,448,047；3,448,048；3,448,049；3,451,933；3,454,497；3,454,555；3,454,607；3,459,661；3,461,172；3,467,668；3,493,520；3,501,405；3,522,179；3,539,633；3,541,012；3,542,680；3,543,678；3,558,743；3,565,804；3,567,637；3,574,101；3,576,743；3,586,629；3,591,598；3,600,372；3,630,904；3,632,510；3,632,511；3,634,515；3,649,229；3,697,428；3,697,574；3,703,536；3,704,308；3,725,277；3,725,441；3,725,480；3,726,882；3,736,357；3,751,365；3,756,953；3,973,202；3,798,165；3,798,247；3,803,039；3,804,763；3,836,471；3,862,981；3,936,480；3,948,800；3,950,341；3,957,854；3,957,855；3,980,569；3,991,098；4,071,548；4,173,540；4,234,435；5,137,980的美国专利和Re 26,433，在这里一起引作参考。可以发现其它适合的分散剂，如专利号为5,198,133；5,256,324；5,389,273和5,439,606的美国专利，在此引作参考。以下专利描述了用于把上述各种无灰分散剂硼化的方法：专利号为3,087,936；3,254,025；3,281,428；3,282,955；3,338,832；3,344,069；3,533,945；3,658,836；3,703,536；3,718,663；4,455,243；和4,652,387的美国专利。
在一些实施方式中，无灰分散剂可以包含含有至少一种可以形成酰亚胺基的伯氨基的胺的一种或更多的烯基丁二酰亚胺。烯基丁二酰亚胺可以通过传统的方法形成，如加热烯基丁二酸酐、酸、酸酯、卤代酸或低烷基酯和含有至少一个伯氨基的胺。烯基丁二酸酐可以通过加热聚烯烃和顺丁烯二酐混合物到大约180℃-220℃而制成。聚烯烃可以是如乙烯、丙稀、异丁烯等的低单烯烃的聚合物或共聚物，具有由凝胶渗透色谱法(GPC)确定的大约900到3000的数均分子量。
用于合成无灰分散剂的胺包括包含至少一个可以反应生成酰亚胺基的伯氨基和至少一个附加的伯和仲氨基和/或至少一个羟基的任何物质。几个代表性的例子如下：N-甲基-丙二胺，N-十二烷丙二胺，N-氨丙基-哌嗪，乙醇胺，N-乙醇-乙二胺等。
适合的胺可以包括亚烷基多胺，如丙二胺，二丙烯三胺，二-(1，2-丁稀)三胺和四-(1，2-丙稀)-五胺。更多的例子包括亚乙基多胺，用化学式H2N(CH2CH2NH)nH表达，其中，n可以是约1到10的一个整数。包括：乙二胺，二亚乙基三胺，三亚乙基四胺，四亚乙基五胺，五亚乙基六胺等，还包括他们的混合物，此时的n是混合物的平均值。上述的这些亚乙基多胺每端包含一个伯氨基，这样可以形成单烯基丁二酰亚胺和双烯基丁二酰亚胺。商业供应的乙烯多胺混合物可能包含少量的支链种类和环类，如N-氨乙基哌嗪，N，N’-二(氨乙基)哌嗪，N，N’-二(哌嗪基)乙烷等组合物。商业混合物可能含有总成分大约落入相应于二乙基三胺到四乙基五胺的范围。聚烯基丁二酐与聚亚烃基多胺的摩尔比例大约为从1∶1到2.4∶1。用于此用途的Mannich碱无灰分散剂合成方法为：冷凝大约1摩尔比例的长链烃代苯酚和大约1到2.5摩尔甲醛和大约0.5到2摩尔的聚亚烃基多胺。
在一些实施方式中，无灰分散剂可能包含如三亚乙基四胺或四亚乙基五胺的聚亚烃基多胺与烃代羧基酸或酐与不饱和聚羧基酸或酐反应的产物，烃代羧基酸或酐由具有合适分子量的如聚异丁烯的聚烯烃反应制的，不饱和聚羧基酸或酐的例子有，顺丁烯二酸酐，顺丁烯二酸，反丁烯二酸等，也包括两种或多种这些物质的混合物。
在一些实施方式中，含硼分散剂可能包含，如含硼酸的聚异丁烯丁二酰亚胺或双丁二酰亚胺或二者的混合物。聚异丁烯分子量大约为210到1300amu，另一个例子大约为900到1300amu，甚至还有一个例子为大约1200到1300amu。
含硼和含磷分散剂
在一个实施方式中，添加剂的组合物可以含有至少一种含磷和硼的分散剂(或，换句话说为磷酸化或硼化的分散剂)。如上述方法磷酸化和硼化分散剂来制备含磷和硼的分散剂。这样，含磷和硼的分散剂可以包含磷酸化和硼化的聚异丁烯丁二酰亚胺或双丁二酰亚胺或它们的混合物。含磷和硼的分散剂可以包含分子量大约为900amu的聚异丁烯。含磷和硼的分散剂可以包含聚异丁烯丁二酰亚胺与硼酸反应的产物，如B(OH)3和磷酸H3PO3。
含硼和磷的分散剂的量大约占润滑组合物(或成品流体)的2.0重量％。含硼和磷分散剂的量大约占添加剂组合物的20重量％。
清洁剂
在一些实施方式中，添加剂的组合物也可以含有清洁剂。清洁剂可以包含高碱性的清洁剂。清洁剂可以含有磺酸盐或苯酚盐。此外，清洁剂可以含有含钙、含镁或含钠的组合物。清洁剂可以含有，如，磺酸钙、磺酸镁、磺酸钠、苯酚钙、和/或苯酚锌。例如，磺酸钙清洁剂可以含有大约1.5重量％到20重量％钙，进一步地，含有大约12重量％到15重量％的钙。此外，磺酸钙清洁剂可以含有大约3mgKOH/g到450mgKOH/g的总碱值(TBN)，另一个例子是大约250mgKOH/g到400mgKOH/g，更优化的一个例子是从大约250mgKOH/g到350mgKOH/g。苯酚钙清洁剂可以包含大约2.5重量％到大约8.5重量％的钙，如大约5重量％的钙。此外，苯酚钙清洁剂可以包含大约50mgKOH/g到300mgKOH/g的总碱值，如大约150mgKOH/g。
除上述的清洁剂外，实施方式还包括碱金属清洁剂和/或碱土金属清洁剂，也可替代上述的清洁剂。碱金属和碱土金属清洁剂的用途由以下例子说明：碱金属和碱土金属和以下酸物质(或酸物质混合物)的油溶中性或高碱性的盐：磺酸、羧酸、水杨酸、烷基酚和硫化烷基酚。
油溶中性碱金属和碱土金属清洁剂是含有按化学计量与清洁剂中的酸一半的量相对应的等量碱金属和碱土金属的量的清洁剂。这样，通常，中性的碱金属和碱土金属清洁剂与它们高碱性对应物相比，具有相对低的碱度。制备高碱性碱金属和碱土金属清洁剂的方法在本领域是众所周知的，市场上提供很多高碱性的清洁剂。
碱金属和碱土金属清洁剂包括中性和高碱性磺酸钠、羧酸钠、水杨酸钠、苯酚钠、硫化苯酚钠、磺酸钙、羧酸钙、水杨酸钙、苯酚钙、硫化苯酚钙、磺酸锂、羧酸锂、水杨酸锂、苯酚锂、硫化苯酚锂、磺酸镁、羧酸镁、水杨酸镁、苯酚镁、硫化苯酚镁、磺酸钾、羧酸钾、水杨酸钾、苯酚钾、硫化苯酚钾。适用于本发明实施方式的其它分散剂，如专利号为6,482,778的美国专利，在此一并引作参考。
在一些实施方式中，添加剂的组合物可以与基油结合来提供动力传动流体。这样的动力传动流体可以包含成品流体。
硼和磷以总硼和磷在润滑组合物(或成品流体)中占大约200ppm或更多的的含量存在。作为另一个例子，硼和磷以总硼和磷在润滑组合物(或成品流体)中占大约400ppm或更多的含量存在。
在另一个实施方式中，自动传动流体，连续可变传动流体，双向离合器流体，或启动装置流体，如变矩器流体，可能包含在这里公开的添加剂的合物。流体适合于传统的自动传动，如包括变矩器的步进式自动传动。
在另一个实施方式中，增加钢-钢摩擦和/或稳定钢-纸摩擦的方法为：采用润滑传动组合物来润滑传动，润滑传动组合物包括主要的基油和这里所述的添加剂组合物。
润滑流体可以包括其它添加剂，如，一种或多种极压添加剂、抗磨剂、如胺抗氧化剂或酚类抗氧化剂的抗氧化剂或抗氧化系统、腐蚀抑制剂或腐蚀抑制系统、金属钝化剂、防锈剂、摩擦调节剂、分散剂、清洁剂、燃料、密封膨胀剂、防沫剂、表面活性剂、粘度指数改进剂、香气剂或掩臭剂、和任何这些物质的合适组合。例如，当摩擦调节剂按常规加入到润滑流体中，摩擦调节剂的类型和剂量对于每一种特殊的使用是唯一的和特定的。
进一步，基油可以含有适合特殊用途的任何基油或基油的混合物。在一些实施方式中，添加剂可以由添加剂包的浓缩物提供。进一步，一些实施方式可以含有稀释液，如稀释油。稀释可能包含在混合、溶解和传送添加包的程序中。稀释剂与基油和/或添加包兼容。稀释剂在浓缩物中可以以任何合适的量存在，合适的稀释剂可以含有润滑剂粘度的操作油。
基油可以含有矿物油，矿物油的混合物、合成油，合成油的混合物，或它们的混合物。合适的基油可以包括组I、组II、组III、组IV、或组V的基本组份。合适的基油可以由气态-液态的工艺制造。
实施例
用于试验的流体以合适的基本组份准备。准备完全配制的流体，混合组分的比例如下面表1所示。表1说明了调配的成分和剂量的实施例。
表1试验流体的成分
  成分   实施例1，重量％     实施例2，重量％
  胺抗氧化剂   0-0.6     0.2-0.6
  防锈剂   0.02-0.15     0.02-0.15
  极压剂/抗磨剂   0.04-1.0     0.04-1.0
  防沫剂   0.01-0.2     0.01-0.2
  摩擦调节剂   0-2.0     0.005-0.25
  分散剂A   1-5     1-5
  分散剂B   0-5     0-5
  清洁剂C   0-5     0-5
  密封膨胀剂   0-10     0-10
  聚甲基丙烯酸酯VII   1-30     3-30
  基本组分   60-90     60-90
   稀释油   1-30     2-5
表1中，“EP/AW”表示极压剂/抗磨剂，“聚甲基丙烯酸酯VII”表示聚甲基丙烯酸酯粘度指数改进剂。此外，分散剂A包含磷酸化和硼化分散剂，包括大约0.76重量％的磷(P)和大约0.37重量％的硼(B)；分散剂B包括含有约1.3％的B的硼化分散剂；清洁剂C包含磺酸钙，总碱值(TBN)为大约300mgKOH/g。
采用Falex block-on-ring摩擦测试仪测量钢-钢摩擦，在Falex测试仪中，摩擦系数在给定温度，并且在特定负荷条件下，在旋转S10环和静止H60块之间测量。测量的钢-钢摩擦(μ)是增加速度(v)到大约0.53m/s的最大值的函数。采用的条件是在大约110℃，滑动速度在大约0到0.60m/s之间，大约1000N负荷。大约0.130或更高的钢-钢摩擦系数(表2中的μ)表示好的性能。
采用Modified Low Speed SAE No.2试验设备测量钢-纸摩擦，检测流体在高负荷、低滑动速度条件下的钢-纸摩擦特性。在滑动速度的摩擦比(表3中的μ20/μ100和μ40/μ300)为大约1或更少表示好的抗震颤性能。
表2表示在大约0.25m/s时，Falex测试仪测试的1-9的实施例的钢-钢摩擦。直接比较了流体1-8和9-10，其中，只有变量被表示在表2中。流体1-8和9-10和11是可比的，只有流体中一些其它成分的微小变化。
表2：钢-钢摩擦
实施例   1  2  3  4  5  6  7  8  9  10   11
分散剂A，ppm   2.00  4.00  4.00  2.00  2.00  4.00  2.00  4.00  2.00  4.00   4.50
分散剂B，ppm   2.00  2.00  2.00  2.00  0.00  0.00  0.00  0.00  4.00  0.00   2.00
清洁剂C，ppm   0.45  0.45  0.00  0.00  0.00  0.45  0.45  0.00  0.00  0.00   0.15
硼的量(B)，ppm   334  408  408  334  74  148  74  148  594  148   427
磷的量(P)，ppm   150  300  300  150  150  300  150  300  150  300   338
(B+P)，ppm   484  708  708  484  224  448   224  448  744  448   764
Ca，ppm   549  549  0  0  0  549  549  0  0  0   183
μ(中点)   0.112  0.139  0.133  0.127  0.097  0.128  0.113  0.137  0.130  0.135   0.135
表2中的测量值表明增加分散剂A的量，钢-钢摩擦增加(如，比较例5和例8、10)。在没有清洁剂C时，高含量的分散剂A能充分提高钢-钢摩擦(如，例3、8和10)。此外，添加分散剂B到含有清洁剂C的配方中，有助于保持或提高钢-钢摩擦(如，比较例2和例6)。这样，清洁剂高含量的硼和磷可以有效地提高钢-钢摩擦。
摩擦与速度比(μ/s)的正斜率表示好的抗震颤耐久性。采用LowSpeed SAE No.2试验设备测量钢-纸摩擦。表3表示在大约20、40、100和300rpm的摩擦值(分别为μ20、μ40、μ100、μ300)。
表3钢-纸摩擦
    实施例     2   3   4   6   7   8
    分散剂A，ppm     4.00   4.00   2.00   4.00   2.00   4.00
    分散剂B，ppm     2.00   2.00   2.00   0.00   0.00   0.00
    清洁剂C，ppm     0.45   0.00   0.00   0.45   0.45   0.00
    μ20     0.132   0.148   0.137   0.128   0.105   0.140
    μ40     0.135   0.148   0.139   0.131   0.110   0.141
    μ100     0.138   0.146   0.140   0.134   0.114   0.138
    μ300     0.138   0.140   0.139   0.129   0.112   0.135
    μ20/μ100     0.96   1.01   0.98   0.96   0.921   1.01
    μ40/μ300     0.98   1.06   1.00   1.02   0.982   1.04
如表3所示，摩擦增加常会导致在大约20到100rpm和大约40到300rpm之间的负斜率。例如，例3和8有大于1.00的一个μ20/μ100值和一个μ40/μ300值，表示是负斜率。例如，如实施例2、4和7所示，小于1.00的μ20/μ100值和μ40/μ300值表示正斜率。这样，含有清洁剂C(如磺化清洁剂)的实施例具有低钢-纸摩擦，完全的正斜率(例如，实施例2、6和7).正斜率表示没有震颤问题的传动，是理想的特征。
因此，把清洁剂与高含量(这里限定的)的硼化/磷酸化分散剂和硼化分散剂结合使用使可变传动流体尽管具有较高的钢-钢摩擦特性，也能改进连续可变传动流体的钢-纸摩擦特性。
本发明提供了增加钢-钢摩擦的组合物，把高含量的硼化和磷酸化分散剂和硼化分散剂与清洁剂结合使用。(例如，比较表2中的例2和6，表3中的例2)。此外，本发明提供了一种组合物，可以保持高的钢-钢摩擦，同时最小化钢-纸摩擦，以提高浸油离合器的性能。
这里描述的组合物可以适用于以下传动流体配方：应用于连续可变传动、传统自动传动和具有不同启动离合器的传动流体配方。
如说明书和权利要求中所用的，“a”和/或“an”可以涉及一或多于一。除非有特殊说明，所有说明书和权利要求中使用的表示成分、性能量的数字，如分子量、百分比、反应条件等应该这样理解：“大约”一词在所有实施例中表示可以更改。据此，除非有相反的说明，说明书和权利要求中陈述的数字参数是近似值，可以依据的本发明所期望获得的性能变化。至少，不限定仅与权利要求范围表面相同的应用，每一个数字参数应当至少依照所述的有效数字构造，并使用通常的舍入算法。虽然本发明数字范围和参数设定的较宽范围是近似值，但实施方式中报道的数值是尽可能精确的。然而，在它们各自的试验测量值中发现，任何数值含有与标准偏离而必然造成固有的某些错误。
通过图表和例证详细描述了本发明，应当理解实施方式允许有各种变化和替代形式，而不仅限于所列出的特定实施方式。还应当理解这些特定的实施方式不限定本发明，而是，力图覆盖落入本发明实质保护范围的所有的变化、等同和代替形式。

Claims (6)

1.一种添加剂组合物，包含：
(a)  至少一种在添加剂组合物中占20重量％或更多的第一含磷和硼分散剂；
(b)至少一种第二含硼不含磷的分散剂，和
(c)至少一种清洁剂。
2.一种传动流体，包括：
(a)主要量的基油；和
(b)添加剂组合物，包括
(i)至少一种在流体中占2.0重量％或更多量的第一含磷和硼分散剂；
(ii)至少一种第二含硼不含磷的分散剂；和
(iii)至少一种清洁剂。
3.一种连续可变传动流体，包括：
(a)主要量的基油；和
(b)添加剂组合物，包括
(i)至少一种在流体中占2.0重量％或更多量的第一含磷和硼的分散剂；
(ii)至少一种第二含硼不含磷的分散剂；和
(iii)至少一种清洁剂。
4.一种增加钢-钢摩擦的方法，包括：
采用润滑组合物润滑具有钢-钢摩擦的传动，所述润滑组合物包含占主要量的基油和添加剂组合物，所述添加剂组合物包括：
(a)至少一种在流体中占2.0重量％或更多量的第一含磷和硼的分散剂；
(b)至少一种第二含硼不含磷的分散剂，和
(c)至少一种清洁剂。
5.一种增加抗震颤的方法，包括：
采用润滑组合物润滑带震颤的传动，所述润滑组合物包含占主要量的基油和添加剂组合物，所述添加剂组合物包括：
(a)至少一种在流体中占2.0重量％或更多量的第一含磷和硼的分散剂；
(b)至少一种第二含硼不含磷的分散剂，和
(c)至少一种清洁剂。
6.一种稳定钢-纸摩擦的方法，包括：
采用润滑组合物润滑具有钢-纸摩擦的传动，所述润滑组合物包含占主要量的基油和添加剂组合物，所述添加剂组合物包括：
(a)至少一种在流体中占2.0重量％或更多量的第一含磷和硼的分散剂；
(b)至少一种第二含硼不含磷的分散剂，和
(c)至少一种清洁剂。
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KR100639086B1 (ko) 2006-10-30
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US20080009426A1 (en) 2008-01-10
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