CN1087669A - 耐腐蚀的润滑剂组合物 - Google Patents

耐腐蚀的润滑剂组合物 Download PDF

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CN1087669A
CN1087669A CN93119560A CN93119560A CN1087669A CN 1087669 A CN1087669 A CN 1087669A CN 93119560 A CN93119560 A CN 93119560A CN 93119560 A CN93119560 A CN 93119560A CN 1087669 A CN1087669 A CN 1087669A
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alkyl
composition
acid
triazole
formula
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CN1042643C (zh
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J·W·A·普拉格内尔
A·J·马克森
M·A·爱德华
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Castrol Ltd
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Castrol Ltd
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Abstract

本发明提供的耐腐蚀润滑剂组合物，包括：(a)一 种合成酯基本原料；(b)至少一种芳族的胺抗氧化剂； (c)一种分子式为(R1O)3PO的中性有机磷酸酯，式中 R1是甲苯基、苯基、二甲苯基、烷基或环烷基的基团， 该烷基或环烷基基团具有多达10个碳原子；(d)一种 饱和或不饱和的二羧酸，其通式和各基团如说明书中 所示；(e)一种直链或支链、饱和或不饱和的一元羧 酸，该一元羧酸可以是硫化的；或该种酸的酯；和(f)一 种如说明书中所示结构的三唑。

Description

本发明涉及耐腐蚀的润滑剂组合物。
在运行和贮存飞机的燃气轮机时，腐蚀可以成为严重的问题，在靠海环境中运行的燃气轮机腐蚀问题尤为严重。这类燃气轮机或其它类型的发动机因遭受腐蚀而投入维修、更换零件、发动机检修时间以及男/女工时的费用非常昂贵。因此，需要有一种能显著降低燃气轮机的腐蚀和避免随之而产生上述严重后果的润滑剂。
为了达到较高的抗腐蚀性能标准（鉴于上述严重问题已将其视为重要的目标），美国海军最近已修订了其MIL-L-23699D军事规程，该军事规程的修订本标志为XAS-L-5724，其中规定了用于燃气轮机的润滑油必须符合的要求。
本发明的目的在于提供一种耐腐蚀的润滑剂，该润滑剂符合标志为ARP  4249的防腐试验（XAS-L-5724中规定）和DERD方法18（DERD2458中规定）的要求。
本发明的组合物已能达到上述目的。
根据本发明所提供的耐腐蚀润滑剂组合物包括：
（a）一种合成酯基本原料;
（b）至少一种芳族的胺抗氧化剂;
（c）一种分子式为（R1O）3PO的中性有机磷酸酯，式中R1是甲苯基、苯基、二甲苯基、烷基或环烷基的基团，该烷基或环烷基基团具有至多10个碳原子;
（d）一种饱和或不饱和的二羧酸，其通式如下：
Figure 931195608_IMG7
式中，x+y+z是包括2至22在内的整数，而且R1至R5基团中至少一种是羧酸基团，其余的R1至R5的基团选自烷基、羟基、羰基、硝基、氨基、羧基、氢或烷基的衍生物，所述烷基是短链的，其碳原子数至多为5;或下列三种结构式之一的二羧酸：
Figure 931195608_IMG8
式中，R′ 1是-COOH、烷基、羟基、羰基、硝基、氨基、氢或烷基的衍生物;R′2是-COOH;n是包括1至4在内的整数;
（e）一种直链或支链、饱和或不饱和的一元羧酸，该一元羧酸可任意地被硫化，硫化量至多可达35%（重量）;或该种酸的酯;和
（f）一种下列结构式的三唑：
Figure 931195608_IMG9
式中，R″ 1是-COOH或其烷基衍生物或至多5个碳原子的短链烷基;n是零或包括1至3在内的整数;R″ 2是氢、吗啉代、烷基、酰胺基、氨基或羟基，或其烷基或芳基被取代的衍生物;或选自以下的一种三唑：1，2，4-三唑、1，2，3-三唑、5-苯胺基-1，2，3，4-噻三唑、3-氨基-1，2，4-三唑、1-H-苯并三唑-1-基-甲胩、亚甲基-双-苯并三唑和萘并三唑。
在上述组分（d）中，该二环结构式旨在表明R2基团可连接到一个或两个芳环上。
中性液体多元醇酯是组成本发明的润滑剂组合物的基本原料，它可以通过被多元醇或多元醇醚类（例如新戊二醇、二甲醇丙烷、三甲醇丙烷、季戊四醇或二季戊四醇）酯化的C5至C12的一元羧酸制成。上述物质都是常规的合成酯类的基本原料。优选的是USA-A-4826 633中介绍的酯类。
组成本发明组合物组分（b）的芳族胺抗氧化剂，其含量范围可以为0.5%-5%（以该组合物的重量计）。优选含有至多3种芳族胺抗氧化剂，更优选两种，且更优选包括含量范围在1%-3%（以该组合物的重量计）的抗氧化剂。本发明组合物中使用的是常规的包含在润滑剂组合物中的芳族胺抗氧化剂。适合的实例是单一辛基苯基α-萘胺和p，p-二辛基二苯胺，优选同时使用。
上述组合物中，组成组分（c）的中性有机磷酸酯，其含量范围可以为0.5%-5%（以该组合物的重量计）。该中性有机磷酸酯也是常规的润滑剂组合物中的成分，任一种符合上述分子式限定的中性有机磷酸酯均可使用。磷酸三甲苯脂是本发明优选使用的磷酸酯。
所述的三组分体系（包括指定的二羧酸、指定的一元羧酸和指定的三唑）构成具有创造性的组合，按照上述美国海军规程中规定的滚珠轴承腐蚀试验法测定，该组合使本发明的组合物在耐腐蚀性能上特别有效。此外可以认为，在下文中举例说明的这种特定的组合物，是迄今唯一完全符合上述两个美国海军规程（MIL-L-23699D和XAS-L-5724）并据以获得批准的组合物。本发明的申请人认为上述三种中的每一种成分在实现综合的润滑剂耐腐蚀性能上都是必不可少的。
组成第一种耐腐蚀组合的组分可以是符合上述规定的任一种二羧酸。所述二羧酸的含量可以按比例多至0.15%（以该组合物的重量计）。然而应该注意的是，即使在另一种符合上述规定的二羧酸存在的情况下，仍要求该组合物中始终含有癸二酸或其同等物，因为除了滚珠轴承腐蚀试验之外还需满足规程的其它规定，例如满意的抗铅腐蚀的性能。
可以用于本发明的二元酸（癸二酸除外）的实例是己二酸、壬二酸、十二烷二羧酸、3-甲基己二酸、3-硝基苯二酸、1，10-癸烷二羧酸和富马酸。
第二种抗腐蚀组合的组分是直链或支链的、饱和或不饱和的一元羧酸或其酯，其可任意地被硫化且硫化量至多可达35%（重量）。优选的这种酸是C4至C22的直链不饱和一元羧酸。优选该添加剂的浓度为0.001%-0.35%（以润滑剂组合物的总重计）。优选的一元羧酸是硫化的油酸。然而，其它适合的原料是油酸本身;戊酸和芥酸。
第三种抗腐蚀组合的组分是如上所述的三唑。所述三唑必须在0.005%-0.25%（以组合物的总重计）的浓度下使用。优选的三唑是苯并三唑。
优选符合本发明的一种组合物的实例如下：
单一辛基苯基α-萘胺  1%
p，p-二辛基二苯胺  0.75%
苯并三唑  0.1%
硫化的油酸  0.05%
癸二酸  0.01%
磷酸三甲苯脂  1.5%
硅防沫剂  2ppm
合成酯基本原液  96.59%
优选的合成酯基本原液由季戊四醇和/或三甲醇丙烷和包括C5至C10的直链和支链酸的酸混合物的反应产物组成。这种基本原料的粘度在100℃下至少应为4.9厘斯。
应该了解，在组成本发明基本组合的这三种组分中，每一种组分早已用于一些润滑剂组合物。然而，就申请人所知，根据上述规程的规定，这三种组分的组合就其应用到耐腐蚀方面而言迄今是新颖的。本申请人认为，正是这种组合能使本发明包括的组合物达到符合上述美国海军规程XAS-L-5724规定的全部要求（包括腐蚀试验要求）的独特技术效果。

Claims (14)

1、一种耐腐蚀润滑剂组合物，包括：
(a)一种合成酯基本原料；
(b)至少一种芳族的胺抗氧化剂；
(c)一种分子式为(R1O)3PO的中性有机磷酸酯，式中R1是甲苯基、苯基、二甲苯基、烷基或环烷基的基团，该烷基或环烷基基团具有至多10个碳原子；
(d)一种饱和或不饱和的二羧酸，其通式如下：
式中，x+y+z是包括2至22在内的整数，而且R1至R5基团中至少一种是羧酸基团，其余的R1至R5的基团选自烷基、羟基、羰基、硝基、氨基、羧基、氢或烷基的衍生物，所述烷基是短链的，其碳原子数至多为5；或以下三种结构式之一的二羧酸：
式中，R′ 1是-COOH、烷基、羟基、羰基、硝基、氨基、氢或烷基的衍生物；R′ 2是-COOH；n是包括1至4在内的整数；
(e)一种直链或支链、饱和或不饱和的一元羧酸，该一元羧酸可以是硫化的；或是该种酸的酯；和
(f)一种下列结构式的三唑：
Figure 931195608_IMG3
式中，R″ 1是-COOH或其烷基衍生物或至多5个碳原子的短链烷基；n是零或包括1至3在内的整数；R″ 2是氢、吗啉代、烷基、酰胺基、氨基或羟基，或其烷基或芳基被取代的衍生物；或选自以下的一种三唑：1，2，4-三唑、1，2，3-三唑、5-苯胺基-1，2，3，4-噻三唑、3-氨基-1，2，4-三唑、1-H-苯并三唑-1-基-甲胩、亚甲基-双-苯并三唑和萘并三唑。
2、根据权利要求1的组合物，其中，所述饱和或不饱和的二羧酸在组合物中的存在量至多0.15%。
3、根据权利要求1或2的组合物，其中，所述饱和或不饱和的二羧酸是癸二酸。
4、根据前述的权利要求中任一项的组合物，其中，所述一元羧酸的存在量为从0.001%至0.35%，以该组合物的重量计。
5、根据前述的权利要求中任一项的组合物，其中，一元羧酸是硫化的油酸。
6、根据前述的权利要求中任一项的组合物，其中，所述三唑的存在量为从0.005%至0.25%，以该组合物的重量计。
7、根据前述的权利要求中任一项的组合物，其中，所述三唑是苯并三唑。
8、根据前述的权利要求中任一项的组合物，其中，所述抗氧化剂包括两种芳族胺。
9、根据前述的权利要求中任一项的组合物，其中，所述抗氧化剂胺或胺类的含量包括从1%至3%，以该组合物的重量计。
10、根据前述的权利要求中任一项的组合物，其中，所述中性有机磷酸脂的含量包括从0.5%至5%，以该组合物的重量计。
11、根据前述的权利要求中任一项的组合物，其中，所述合成酯基本原料包括由一种或多种碳原子数为5至12的一元羧酸和一种或多种多元醇或多元醇醚衍生的一种或多种酯类。
12、一种实质上如上述权利要求1中的组合物。
13、下述组合用于使润滑剂组合物完全符合本文中关于美国海军规程规定的滚珠轴承腐蚀试验对耐腐蚀性能的要求：
（ⅰ）一种饱和或不饱和的二羧酸，其通式如下：
Figure 931195608_IMG4
式中，x+y+z是包括2至22在内的整数，而且R1至R5基团中至少一种是羧酸基团，其余的R1至R5的基团选自烷基、羟基、羰基、硝基、氨基、羧基、氢、或其烷基的衍生物，所述烷基是短链的，其碳原子数至多为5;或以下三种结构式之一的二羧酸：
式中，R′ 1是-COOH、烷基、羟基、羰基、硝基、氨基、氢、或其烷基的衍生物;R′ 2是-COOH;n是包括1至4在内的整数;
（ⅱ）一种直链或支链、饱和或不饱和的一元羧酸，该一元羧酸可以是硫化的;或是该种酸的酯;和
（ⅲ）一种如下列结构式的三唑：
Figure 931195608_IMG6
式中，R″ 1是-COOH或烷基的衍生物或至多5个碳原子的短链烷基;n是零或包括1至3在内的整数;R″ 2是氢、吗啉代、烷基、酰胺基、氨基、羟基、或其烷基或芳基被取代的衍生物;或选自以下的一种三唑：1，2，4-三唑、1，2，3-三唑、5-苯胺基-1，2，3，4-噻三唑、3-氨基-1，2，4-三唑、1-H-苯并三唑-1-基-甲胩、亚甲基-双-苯并三唑和萘并三唑。
14、根据权利要求1-12中任一项的一种完全符合美国海军XAS-L-5724规程要求的组合物。
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