CN101184828B - 具有改进的储存稳定性的润滑组合物 - Google Patents

具有改进的储存稳定性的润滑组合物 Download PDF

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CN101184828B
CN101184828B CN2006800186983A CN200680018698A CN101184828B CN 101184828 B CN101184828 B CN 101184828B CN 2006800186983 A CN2006800186983 A CN 2006800186983A CN 200680018698 A CN200680018698 A CN 200680018698A CN 101184828 B CN101184828 B CN 101184828B
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J·A·扎卡里安
M·J·海尔
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Abstract

公开了具有优异储存稳定性和承载效果的润滑油组合物。组合物包括四个组分：(1)碱金属硼酸盐；(2)油溶性的硫化合物；(3)亚磷酸氢三烷基酯；和(4)被中和了50％以上的酸性的磷酸酯的混合物，所述的磷酸酯基本上不含单硫代磷酸酯。

Description

具有改进的储存稳定性的润滑组合物
发明背景 
本发明涉及极压润滑油，特别是含碱金属硼酸盐的润滑剂。 
碱金属硼酸盐因其有效用作极压剂而为润滑剂工业界所熟知。参见，例如，美国专利Nos.3313727、3565802、3819521、3846313、3853772、3907691、3912639、3912643、3912644、3997454和4089790。 
美国专利№4459215公开了含碱金属硼酸盐、含硫化合物和锆盐的润滑组合物。 
美国专利№4575431公开了含磷酸酯混合物的润滑油，所述磷酸酯基本不含单硫代磷酸酯。 
美国专利No.4089790要求保护增效的润滑剂混合物，其含有：(1)水合硼酸钾；(2)抗磨剂，选自(a)二硫代磷酸锌二烃基酯、(b)二烃基二硫代磷酸的C1-C20酯、C1-C20酰胺或C1-C20铵盐、(c)烷基芳基磺酸锌和(d)它们的混合物；和(3)油溶性的抗氧剂有机硫化合物。 
美国专利№4171268要求保护含羧酸的锆盐和油溶性的含硫极压剂的润滑剂组合物。 
美国专利№4563302和4204969公开了用于润滑油的硫化烯烃。 
授权给Salentine的美国专利№4717490公开了润滑组合物，它是碱金属硼酸盐、硫化合物、亚磷酸酯和＞50％中和的酸性的磷酸酯的组合。然而，该组合物受困于其保存期比不用碱金属硼酸盐固体分散的其它市售润滑剂短。特别地，该组合物将呈现添加剂随时间而“失效”的现象。当存储温度提高时该问题变得愈加严重。工业界中标准补救方法是向该组合物中加入更多的分散剂或清净剂添加剂来改进保存期。然而，这些添加剂会对齿轮润滑剂的其它性能有负面影响。因此，本发明的目标是提供具有优异承载性能和改进的储存稳定性的含碱金属硼酸盐的润滑剂。 
不受缚于任何特定理论，我们已发现添加剂失效的主要原因是使用了亚磷酸氢二烷基酯，其在Salentine的专利中作为组合物的必要组分而公开。此材料是酸性的和不稳定的，且似乎与硼酸盐颗粒或与用来稳定硼酸盐颗粒的碱性分散剂和/或清净剂添加剂发生反应而产生沉降到润滑剂容器或包装底部的沉淀物。酸性来自于直接与磷连接或与杂原子连接而该杂原子再与磷连接的氢。本发明涉及用亚磷酸三烷基酯替代Salentine专利的亚磷酸氢二烷基酯。亚磷酸三烷基酯为非反应性的，且所得组合物的储存稳定性得到出乎意料的和引人注目的改进。 
Salentine专利声称具有由四种组分组合所获得的增效的承载效果。当按照本发明用亚磷酸三烷基酯替换亚磷酸氢二烷基酯时，甚至仍维持了此改进的承载效果。 
本发明的组合物的另一好处在于它比Salentine专利所公开的组合物更易生产。亚磷酸氢二烷基酯是固体材料，在工厂处进行调合过程中很难处置。因其对水的反应性和敏感性，必须一次性使用整个容器内的该化学品。另一方面，亚磷酸三烷基酯在室温下是液体，这样就非常容易调合。它对水的反应性也低得多。 
发明概述 
本发明涉及润滑组合物，包括其中已分散少量如下混合物的润滑粘度油： 
(a)水合的碱金属硼酸盐组分； 
(b)油溶性的含硫化合物组分； 
(c)亚磷酸氢三烷基酯组分，至少90wt％的该组分具有式(RO)3P，其中R为4-24个碳原子的烷基；和 
(d)被中和了50％以上的酸性的磷酸酯混合物组分，所述磷酸酯基本不含单硫代磷酸酯。 
优选的实施方案的描述 
本发明的润滑油组合物包括四个组分：(1)碱金属硼酸盐；(2)油溶性的硫化合物；(3)亚磷酸氢三烷基酯；和(4)被中和了50％以上的酸性的磷酸酯的混合物，所述磷酸酯基本上不含单硫代磷酸酯。 
碱金属硼酸盐 
本发明的润滑油组合物的第一组分是水合的颗粒状碱金属硼酸盐。水合的颗粒状碱金属硼酸盐是本领域众所周知的且可商购得到。公开了适宜的硼酸盐和制备方法的代表性专利包括美国专利3313727、3819521、3853772、3907601、3997454和4089790，将这些专利的全文引入本文作为参考。 
水合的碱金属硼酸盐可由下式表示： 
M2O.mB2O3·nH2O 
其中M是原子序数为11-19的金属，即钠和钾；m是2.5-4.5的数(整数和分数兼有)；且n是1.0-4.8的数。优选的是水合硼酸钾，特别是硼/钾比为约2.5-4.5的水合三硼酸钾微粒。水合硼酸盐颗粒的平均颗粒尺寸一般小于1微米。 
油溶性的硫化合物 
本发明的润滑油组合物的第二组分是至少一种油溶性的含硫化合物。任何已知类型的迄今已被提议可用作极压剂的有机硫化合物都可用作本发明的含硫试剂。它们包括有机硫化物和多硫化物、硫化的油和酯或脂肪酸，以及它们的混合物。这些硫化合物可含有其它有益的基团，这些基团包括卤基。 
用作EP剂的有机硫化合物和多硫化物的实例包括脂族和芳族硫化物和多硫化物，例如二己硫醚、双十八烷基硫醚、二硫化二丁基、二硫化二戊基、二硫化二己基、二硫化双十八烷基、二苯硫、二苄基硫、二甲苄基硫、二苯基二硫化物、二萘基二硫化物、二苯酚二硫化物、二苄基二硫化物、二(氯苄基)二硫化物、二苄基三硫化物、二丁基四硫化物、硫化双戊烯和硫化萜烯。 
含硫添加剂的优选的类型是通过硫和/或一氯化硫与烯烃如异丁烯反应制得的那些。特别优选的是公开于美国专利№4563302和4204969的硫化烯烃，本文引入其公开内容作为参考。 
上述硫化物和多硫化物的卤代衍生物是有用的，实例包括二乙基硫和二乙基二硫化物、二辛基硫、二戊基硫和二戊基二硫化物、二苯 硫和二苯基二硫化物以及二苄基硫和二苄基二硫化物的卤代的和氟代的衍生物。可用的硫和卤素EP试剂的更详尽列表见美国专利№2208163。硫化的油的实例包括硫化的鲸油、硫化的油酸甲酯、硫化的鲸油替代品。硫化的油的其它实例包括硫化的亚油酸甲酯、硫化的动物和植物油、硫化的猪油和硫化的棉籽油。 
亚磷酸酯 
本发明的润滑油的第三组分是亚磷酸三烷基酯。适用于本发明的亚磷酸三烷基酯包括(RO)3P，其中R是约4-24个碳原子、更优选约8-18个碳原子、最优选约10-14个碳原子的烃基。烃基可以是饱和或不饱和的。优选地，亚磷酸三烷基酯含有至少90wt％的(RO)3P结构，其中R的定义同上。代表性的亚磷酸三烷基酯包括但不限于亚磷酸三丁酯、亚磷酸三己酯、亚磷酸三辛酯、亚磷酸三癸酯、亚磷酸三月桂酯和亚磷酸三油烯基酯。特别优选的亚磷酸三烷基酯是亚磷酸三月桂酯，例如Rhodia Incorporated Phosphorus and Performance Derivative市售的Duraphos TLP或Dover Chemical Corporation市售的Doverphos 53(TLP)。这些磷酸三烷基酯可含少量的亚磷酸二烷基酯作为杂质，在某些情况下可多达5wt％。优选的是含约10-20个碳原子烃基的亚磷酸酯的混合物。这些混合物通常衍生自动物或天然植物源。椰子、牛脂、妥尔油和大豆作为代表性的烃基混合物通常是已知的。 
中和的磷酸酯 
本发明的润滑油的第四组分是中和的磷酸酯混合物。此混合物公开于美国专利№4575431中，将其引入本文作为参考。该组分包括磷酸酯混合物，所述磷酸酯基本不含单硫代磷酸酯，且包括：(a)二硫代磷酸氢二烃基酯；和(b)磷酸二氢烃基酯和磷酸氢二烃基酯的不含硫的混合物，所述组合物至少50％被所述烃基具有10-26个碳原子的烃基胺所中和。 
本申请中所用术语“基本不含单硫代磷酸酯”的意思是润滑剂或润滑剂添加剂不含任何对润滑剂的极压性能有实质性损害的单硫代磷酸酯。优选地，本发明的润滑剂或润滑剂添加剂不含任何单硫代磷酸酯。 
用来制备中和的磷酸酯混合物的磷酸酯各个组分是本领域众所周知的。 
二硫代磷酸酯 
典型的二硫代磷酸酯是含两个烃基和一个氢官能团的那些，因而是酸性的。这里有用的烃基优选是3-8个碳原子的脂族烷基。 
代表性的二硫代磷酸二烃基酯包括：二硫代磷酸氢二-2-乙基-1-己酯、二硫代磷酸氢二异辛酯、二硫代磷酸氢二丙酯和二硫代磷酸氢二-4-甲基-2-戊酯。 
优选的二硫代磷酸酯是二硫代磷酸氢二己酯、二硫代磷酸氢二丁酯和二硫代磷酸氢二正己酯。 
不含硫的磷酸酯 
典型的不含硫的磷酸酯包括磷酸氢二烃基酯和磷酸二氢单烃基酯，其中烃基含1-10个碳原子，且优选含3-5个碳原子，且最优选含4个碳原子。该烃基是脂族烷基。 
代表性的磷酸酯包括：磷酸二氢甲酯、磷酸二氢丙酯、磷酸二氢丁酯、磷酸氢二丁酯、磷酸氢二戊酯、磷酸二氢戊酯、磷酸二氢己酯、磷酸二氢癸酯等。 
磷酸氢二丁酯和磷酸二氢丁酯的混合物是优选的。 
用胺中和该磷酸酯 
酸性的磷酸酯的混合物通过与烷基胺反应被部分或完全中和。得到的组合物是复杂混合物，其中含有不含硫的磷酸单烃基酯或磷酸二烃基酯的烷基铵盐、混和酸-烷基铵盐和酸，以及二硫代磷酸二烃基酯的烷基铵盐和游离酸。中和必须完成至少50％、优选至少80％。为了得到最佳结果，中和率应为85％-95％，其中100％中和是指一个烷基胺与每个酸氢原子进行反应。 
胺烷基的长度为10-30个碳原子、优选12-18个碳原子。典型的胺包括十五烷基胺、十八烷基胺、十六烷基胺等。最优选的是油胺。二硫代磷酸酯与不含硫的磷酸酯的摩尔比应为70∶30至30∶70、优选55∶45至45∶55且最优选为1∶1。一取代磷酸二氢酯与二取代磷酸氢酯 的摩尔比应为30∶70至55∶45、优选35∶65至50∶50且最优选为45∶55。 
润滑油和添加剂的浓度 
要向其中加入硼酸盐、硫化合物、亚磷酸酯和磷酸酯的润滑油可以是任何烃基润滑油或合成基的油原料。烃润滑油可衍生自合成的或天然的来源且可以是链烷基、环烷基或沥青基的或它们的混合物。此润滑油用于所述润滑剂组合物且浓度补足到100wt％。 
碱金属硼酸盐通常占润滑剂组合物的0.1-20wt％、优选0.5-15.0wt％，且更优选2.0-9.0wt％。油溶性的硫化合物占润滑剂组合物的0.1-10.0wt％、优选0.5-4.0wt％，且更优选1.0-3.0wt％。亚磷酸酯占润滑剂组合物的0.01-10.0wt％、优选0.05-5.0wt％，且更优选0.10-1.0wt％。磷酸酯占润滑剂组合物的0.03-3.0wt％、优选0.07-1.5wt％，且更优选0.15-0.9wt％。 
可通过将浓缩物加入润滑基础油中来制备上述润滑组合物。通常润滑剂含1.0-10.0wt％的该浓缩物且优选含5.0-8.0wt％的该浓缩物。 
其它添加剂 
本发明的润滑油中可存在各种其它添加剂。这些添加剂包括抗氧剂、粘度指数改进剂、分散剂、防锈剂、消泡剂、抗蚀剂、其它抗磨剂、破乳剂、摩擦改进剂、降倾点剂以及各种熟知的其它添加剂。优选的分散剂包括熟知的琥珀酰亚胺和乙氧基化的烷基苯酚和醇。特别优选的额外的添加剂是油溶性的琥珀酰亚胺和油溶性的碱金属或碱土金属磺酸盐。 
实施例
下列实施例对本发明例示说明，但并不是想要以除下文权利要求中所含内容以外的任何方式限定本发明。 
实施例1-2
表1示出两种不同的制备用于生产极压润滑油的添加剂混合物的方法。实施例1是按美国专利№4717490的教导所制备的添加剂包。实施例2是按本发明的教导所制备的添加剂包。两种制备方法之间唯一的不同是实施例1使用亚磷酸氢二烷基酯而实施例2则使用亚磷酸 三烷基酯，具体为亚磷酸三月桂酯。每个实施例中亚磷酸酯的配制重量百分数已调整到使磷对成品润滑油调合物的贡献相等。 
表1还示出了添加剂包储存稳定性试验的结果。通过将添加剂样品放入4盎司洁净玻璃瓶中，然后让瓶子静置放在实验室搁架上(20℃下的数据)或在实验室烘箱中(66℃下的数据)来实施存储稳定性试验。定期用亮光检查样品外观。记录样品中絮状物或雾状物的量和瓶底处沉淀物的量。若在样品瓶的底部未发现沉淀物，则认为储存稳定性极好。本发明惊奇的发现是实施例2的储存稳定性比实施例1好的多。实施例2的记录值“＞19周”的意思是储存试验在19周末终止。因此，室温下储存时，实施例2远优于实施例1，后者仅1星期后就形成大量的沉淀物。实施例2的优异储存性结果还沿伸到66℃的加速储存条件下。 
Figure 2006800186983A00800071
实施例3-6
表2示出了使用实施例1或实施例2的添加剂的极压润滑油的配方。实施例3和4是在100℃下具有相同粘度的润滑油，且它们原本预计呈现出相同的极压性能和储存稳定性。然而，表2的数据显示用 含亚磷酸三月桂酯的添加剂制备的实施例4的油在储存稳定性方面有出乎意料的极大改进。在由ASTM方法D2783所测的极压性能方面实施例3和实施例4的油之间没有差异。 
表2还示出了实施例5和6，它们也是在100℃下具有相同粘度的油，但其粘度值大大高于实施例3和4。实施例5和6的油按SAE粘度等级略低于85W-140来调合，实施例3和4按SAE粘度等级略低于80W-90来调合。用亚磷酸三烷基酯制备的实施例(实施例6)再次显示出在储存稳定性方面比用亚磷酸二烷基酯制备的实施例(实施例5)有出乎意料的极大改进。储存稳定性的改进并未造成极压性能的损失。 
Figure 2006800186983A00800081
按照本文所述的教导性的和支持性的实施例，本发明可有多个变通方案。因此应理解到，在如下权利要求范围内，本发明可按不同于本文具体描述或例举的其它方式实施。 

Claims (14)

1.润滑组合物，包括其中已分散少量如下组分的混合物的润滑粘度油：
(a)水合的碱金属硼酸盐组分；
(b)油溶性的含硫化合物组分；
(c)亚磷酸三烷基酯组分，至少90wt％的该组分具有式(RO)3P，其中R为4-24个碳原子的烷基；和
(d)中和的磷酸酯的混合物组分，所述磷酸酯基本上不含单硫代磷酸酯。
2.权利要求1的组合物，其中所述润滑组合物包括：
(a)0.1-20wt％的碱金属硼酸盐；
(b)0.1-10.0wt％的含硫化合物组分；
(c)0.01-10.0wt％的亚磷酸三烷基酯组分；和
(d)0.03-3.0wt％的中和的磷酸酯的混合物组分，所述磷酸酯基本不含单硫代磷酸酯。
3.权利要求2的润滑剂组合物，其中所述硼酸盐是三硼酸钾。
4.权利要求2的润滑剂组合物，其中所述含硫化合物是硫化异丁烯。
5.权利要求2的润滑剂组合物，其中所述亚磷酸酯是C10-C20亚磷酸三烷基酯的混合物。
6.权利要求2的润滑剂组合物，其中所述磷酸酯包括：
(a)二硫代磷酸氢二烃基酯；和
(b)磷酸二氢烃基酯和磷酸氢二烃基酯的不含硫的混合物，所述组合物至少50％被在烃基中有10-30个碳原子的烃基胺所中和。
7.权利要求6的组合物，其中所述二硫代磷酸氢二烃基酯、磷酸二氢烃基酯和磷酸氢二烃基酯中的烃基是1-10个碳原子的烷基。
8.包括如下组分的混合物的润滑油浓缩物：
(a)水合的碱金属硼酸盐组分；
(b)油溶性的含硫化合物组分；
(c)亚磷酸三烷基酯组分，至少90wt％的该组分具有式(RO)3P，其中R为4-24个碳原子的烷基；和
(d)中和的磷酸酯的混合物组分，所述磷酸酯基本上不含单硫代磷酸酯。
9.润滑组合物，包括主要量的润滑油和少而有效量的权利要求8的浓缩物，以改进所述润滑组合物的承载性能。
10.权利要求9的组合物，其中所述组合物含1.0-10.0wt％的所述浓缩物。
11.权利要求8的润滑油浓缩物，其中所述硼酸盐是三硼酸钾。
12.权利要求8的润滑油浓缩物，其中所述含硫化合物是硫化异丁烯。
13.权利要求8的润滑油浓缩物，其中所述亚磷酸酯是C10-C20亚磷酸三烷基酯的混合物。
14.权利要求8的润滑油浓缩物，其中所述磷酸酯包括：
(a)二硫代磷酸氢二烃基酯；和
(b)磷酸二氢烃基酯和磷酸氢二烃基酯的不含硫的混合物，所述组合物至少50％被在烃基中有10-30个碳原子的烃基胺所中和。
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