CN100575467C - 改进的抗氧化添加剂组合物和含有此添加剂组合物的润滑剂组合物 - Google Patents

改进的抗氧化添加剂组合物和含有此添加剂组合物的润滑剂组合物 Download PDF

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CN100575467C
CN100575467C CN02817700A CN02817700A CN100575467C CN 100575467 C CN100575467 C CN 100575467C CN 02817700 A CN02817700 A CN 02817700A CN 02817700 A CN02817700 A CN 02817700A CN 100575467 C CN100575467 C CN 100575467C
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托马斯
J·卡罗尔
史蒂文
G·唐纳利
罗纳德
J·赫泽
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Abstract

本发明公开一种抗氧剂组合物，其包括：(1)有机钼化合物；(2)烷基化二苯胺；及(3)含硫化合物，其选自：(a)噻二唑；(b)二硫代氨基甲酸酯；及(c)(a)和(b)的混合物。

Description

改进的抗氧化添加剂组合物和含有此添加剂组合物的润滑剂组合物
发明背景
本发明涉及添加剂组合物和含有所述添加剂组合物的润滑剂组合物，它们都具有改进的抗氧化效果。当把这些抗氧化添加剂组合物添加到基础油中以形成润滑剂组合物时，其引起的沉积程度较低，并表现出改善的铜腐蚀抑制性及减摩性。
从现有技术中已经知道一些有机钼配合物具有理想的润滑特性，包括抗磨性或抗氧化性。
专利权人为Tonen公司的美国专利第5,364,545号描述了一种具有低摩擦系数和降低的铜腐蚀性的润滑油组合物，此专利据此引为参考，该润滑油组合物是三组分体系，包括：(a)润滑油基础油；(b)按润滑油组合物计重量为0.01-10％的至少一种选自甘油单酯氧钼和二乙醇酰胺氧钼的有机钼化合物；(c)按润滑油组合物计重量为0.5-7％的至少一种选自二硫代磷酸锌(ZnDTP)和二硫代氨基甲酸锌的有机锌化合物。
从Tonen公司的发明所描述的实施例可看出其涉及含有ZnDTP的组合物。ZnDTP类组分在润滑剂中作为抗磨剂、金属钝化剂和抗氧化剂。然而，这些磷酸金属盐化合物的使用经常导致催化转化器中毒，因此仍然需要一种不采用磷酸金属盐化合物的添加剂组合物。
专利权人为Ethyl公司的美国专利第5,840,672号描述了一种用于润滑油的抗氧化体系，此专利据此引为参考，该抗氧化体系是三组分体系，包括855(有机酰胺的有机钼配合物)/ADPA(烷基化二苯胺)/硫化异丁烯和/或硫化苯酚。此发明涉及抗氧化组合物，其包括(A)至少一种二芳基仲胺；(B)至少一种硫化烯烃和/或硫化受阻酚；和(C)至少一种油溶性的钼化合物。
然而，本技术领域公知的是尽管该添加剂组合物可能是良好的抗氧化体系，但是加入该添加剂组合物后得到的润滑油组合物在高温时，例如发动机的工作温度下，其产生的沉积物或者油泥则可能到达不能接受的程度。
专利权人均是R.T.Vanderbilt公司的美国专利第6,017,858和第6,369,005号描述了基于二组分协同体系的协同有机钼化合物和润滑剂组合物，这些专利据此引为参考，该二组分体系包括：(1)
Figure C0281770000061
855润滑剂添加剂和(2)1，3，4-噻二唑化合物或者DTC(二硫代氨基甲酸酯)化合物或者DTP(二硫代磷酸酯)化合物。此发明涉及协同抗磨损组合物，其包括有机钼配合物和有机硫化合物，有机硫化合物选自2，5-二巯基-1，3，4-噻二唑衍生物、双二硫代氨基甲酸酯、二硫代氨基甲酸金属盐、二硫代磷酸金属盐及二硫代磷酸酯。有机钼配合物是通过使1摩尔的脂肪油、1.0-2.5摩尔的二乙醇胺和钼源反应而得到的反应产物。
令人惊讶地是，发现了一种具有出乎意料的抗氧化性能的添加剂组合物，其包括(1)有机钼化合物；(2)烷基化二苯胺；及(3)含硫化合物，其选自：(a)噻二唑；(b)二硫代氨基甲酸酯；及(c)(a)和(b)的混合物。此外，当本发明的添加剂组合物加入到基础油中形成润滑剂组合物时，其引起的沉积程度较低并且具有改善的铜腐蚀抑制性和减摩性。
发明概述
由此本发明提供改进的抗氧化添加剂组合物，其包括：
(1)有机钼化合物；
(2)烷基化二苯胺；及
(3)含硫化合物，其选自：
(a)噻二唑；
(b)二硫代氨基甲酸酯；及
(c)(a)和(b)的混合物。
本发明还提供一种含有上述改进的抗氧化添加剂组合物的润滑剂组合物。
当把本发明的抗氧化添加剂组合物添加到基础油中以形成润滑剂组合物时，其引起的沉积程度较低，并表现出改善的铜腐蚀抑制性和减摩性。
发明详细说明
(1)有机钼化合物
有机钼配合物是通过在高温(即高于室温)下使约1摩尔的脂肪油、约1.0-2.5摩尔的二乙醇胺及足够产生按配合物重量计约为0.1-12.0％钼的钼源反应而制备的。约70-160℃的温度范围被认为是本发明实施方案的一个实施例。本发明的有机钼组分是通过按照美国专利第4,889,647号所述的缩合方法连续使脂肪油、二乙醇胺和钼源反应而制备的，其商品化产品为Norwalk，CT的R.T.Vanderbilt公司的
Figure C0281770000071
855润滑剂添加剂。该反应得到的反应产物为混合物。主要成分被认为具有如下的结构式：
Figure C0281770000072
其中R’表示脂肪油残基。本发明一个实施方案的脂肪油是含有至少12个碳原子、可能含有22个碳原子或更多个碳原子的高级脂肪酸的甘油酯。这些酯通常被称为植物油和动物油。有用的植物油的例子是源于椰子、玉米、棉籽、亚麻仁、花生、大豆、向日葵子的油。同样可以使用动物脂肪油如牛脂。钼源可以是含氧钼化合物，该化合物能够和脂肪油与二乙醇胺的中间反应产物反应而形成酯型钼配合物。钼源也可以包括钼酸铵、氧化钼及其混合物。
(2)烷基化二苯胺(ADPA)
烷基化二苯胺广泛用作润滑剂的抗氧化剂。本发明中烷基化二苯胺的一个可行的实施方案是烷基化的二苯基仲胺，如美国专利第5,840,672中所述的那些烷基化的二苯基仲胺，此专利据此引为参考。这些烷基化二苯基仲胺被描述为式X-NH-Y，其中X和Y分别代表取代的或未取代的苯基，其中苯基的取代基包括具有1-20个碳原子的烷基、烷基芳基、羟基、羧基及硝基，且其中至少一个苯基被具有1-20个碳原子的烷基取代。本发明中所用的另外一个可能的ADPA是N-苯基-苯胺和2，4，4-三甲基戊烯的反应产物。也可能使用从商业上可购得的ADPAs，包括由R.T.Vanderbilt公司生产的
Figure C0281770000081
SL、DND、NA、81和961烷基化二苯胺，Uniroyal Chemical生产的640、680和438L烷基化二苯胺，Ciba-Geigy生产的
Figure C0281770000083
L-57和L-67二苯胺以及Lubrizol生产的Lubrizol 5150A&C二苯胺。
(3)含硫化合物
(a)噻二唑
式I的1，3，4-噻二唑可以用美国专利第4,761,482号和美国专利第4,880,437号所公开的方法制备，这些专利在此引为参考：
Figure C0281770000084
其中R和R1分别选自氢、烷基、羟烷基、烷硫基、苯基烷基、烷基化苯基烷基、萜烯残基和下式的顺丁烯二酸残基
Figure C0281770000085
其中R2和R3分别选自氢、支链或直链的烷基和环状脂族基，
其中R和R1中的至少一个不是氢。
本发明一个实施方案中烷基具有1-50个碳原子，其可是支链或直链烷基并且可被羟基和芳基取代。本发明另一个实施方案中R和R1是含有1-22个碳原子的烷基和烷硫基，可以是支链或直链的烷基和烷硫基。本发明再一个实施方案中的化合物其中在R和R1的烷基和/或烷硫基中一共含有的碳原子总数至少为22个。
本发明萜烯残基的实施方案包括源于松烯和柠檬烯的萜烯。
本发明顺丁烯二酸残基的实施方案包括其中R2和R3分别代表具有1-22个碳原子的烷基或C5-C7-环烷基的顺丁烯二酸残基。另一个实施方案中R2和R3的碳原子总数是8-44个碳原子。
商业上可购得的噻二唑衍生物是由R.T.Vanderbilt公司生产的
Figure C0281770000091
871(烷基聚羧酸酯2，5-二巯基-1，3，4-噻二唑)、
Figure C0281770000092
826(2，5-二巯基-1，3，4-噻二唑)和
Figure C0281770000093
484(烷基噻二唑)。
(b)二硫代氨基甲酸酯
(i)双二硫代氨基甲酸酯
式II的双二硫代氨基甲酸酯是由美国专利第4,648,985号所揭示的已知化合物，此专利在此引为参考：
Figure C0281770000094
该化合物的特征在于R4、R5、R6和R7可相同或可不相同，并且是具有1-13个碳原子的烃基。
本发明的实施方案包括双二硫代氨基甲酸酯，其中R4、R5、R6和R7可相同或可不相同，并且是具有1-8个碳原子的支链或直链烷基。
R8是脂族基团，如含有1-8个碳的直链和支链亚烷基。对于R8而言的一个实施方案是亚甲基双(二硫代氨基甲酸二丁酯)，其可从R.T.Vanderbilt公司以7723的商品名购得。
(ii)无灰的二硫代氨基甲酸酯
Figure C0281770000096
式III化合物的特征在于基团R9、R10、R11和R12可相同或可不相同，并且是具有1-13个碳原子数的烃基。商业上可从R.T.Vanderbilt公司购得
Figure C0281770000101
732(二硫代氨基甲酸酯衍生物)和
Figure C0281770000102
981(二硫代氨基甲酸酯衍生物)。
(iii)二硫代氨基甲酸金属盐
Figure C0281770000103
式IV的二硫代氨基甲酸盐是已知的化合物。美国专利第2,492,314号揭示了一种制备方法，此专利在此引为参考。式IV中的R13和R14代表具有1-8个碳原子的支链和直链烷基，M是金属阳离子，n是以金属阳离子化合价为基础的整数(例如，对于钠(Na+)，n＝1；对于锌(Zn2+)，n＝2等)。美国专利第3,356,702号、第4,098,705号和第5,627,146号揭示了二硫代氨基甲酸钼的制备方法，每一个专利在此引为参考。每个烷基取代基是碳原子数为8-13的支链或直链烷基。
本发明的实施方案包括二硫代氨基甲酸金属盐，其是二硫代氨基甲酸锑盐、锌盐和钼盐。
下面描述本发明组合物中上述组分不同含量的各种实施方案，数值是总润滑剂组合物的重量百分比：
 组分   实施方案1(％)   实施方案2(％)   实施方案3(％)
 总组合物：(1)+(2)+(3)   0.15-12.0   0.40-8.5   0.75-3.5
 (1)有机钼化合物   0.05-3.0   0.10-2.0   0.15-1.0
 (2)ADPA   0.05-5.0   0.1-2.0   0.20-1.5
 (3)含硫化合物<sup>*</sup>   0.05-4.0   0.20-2.5   0.40-1.0
 (a)噻二唑   0-4.0   0-2.5   0-1.0
 (b)二硫代氨基甲酸酯   0-4.0   0-2.5   0-1.0
*噻二唑、二硫代氨基甲酸酯或其混合物
本发明的添加剂组合物在与含有磷的二硫代磷酸盐或酯配合使用时是有效的。
本发明二硫代磷酸酯的实施方案包括：
(1)二硫代磷酸金属盐
Figure C0281770000111
式V的二硫代磷酸金属盐是已知的商业上可购得的原料。美国专利第4,215,067号教导了一种制备方法，此专利在此引为参考。(M和n的定义与上面二硫代氨基甲酸金属盐的相同)R15和R16代表碳原子数为1-22的支链和直链烷基，并可源于脂肪酸。一个实施方案是二硫代磷酸锌。式V中的金属离子可从元素周期表中的IIA、IIIA、VA、VIA、IB、IIB、VIB和VIII族选取。此化合物的胺盐也是本发明有用的增效剂。这种胺盐的实施方案包括从烷基胺和混合烷基胺制得的胺盐。另一实施方案包括基于脂肪酸胺的胺盐。
(2)二硫代磷酸酯
Figure C0281770000112
式VI的二硫代磷酸酯为已知的化合物。美国专利第3,567,638号揭示了一种制备方法，此专利在此引为参考。R17、R18、R19和R20可相同或可不相同，并且是支链和直链烷基。本发明的实施方案包括含有1-8个碳原子的支链或直链烷基。
实施方案中二硫代磷酸酯(phosphorodithioate)(也称为二硫代磷酸酯(dithiophosphate))化合物或其混合物的加入量为0.05-2.00％、0.5-1.50％、和0.5-0.8％(每个百分比是基于润滑剂组合物的总重量计的重量百分比)。
可选择地，本发明的抗氧化润滑剂组合物还可包括摩擦改性剂、抗氧化剂和/或铜腐蚀抑制剂。
例如在美国专利第4,792,410号和第5,110,488号中可找到可选择性添加的摩擦改性剂的实施方案，这些专利在此引为参考，这些改性剂包括脂肪亚磷酸酯、脂肪酸酰胺、脂肪环氧化物、硼化脂肪环氧化物、脂肪胺、甘油酯、硼化甘油酯、烷氧基化脂肪胺、硼化烷氧基化脂肪胺、脂肪酸金属盐、硫化烯烃、脂肪咪唑啉及其混合物。
可选择性添加的抗氧化剂实施方案包括受阻酚抗氧化剂、芳香仲胺抗氧化剂、硫化酚抗氧化剂、油溶性铜化合物、含磷抗氧化剂、有机硫化物、二硫化物和多硫化物。
可选择性添加的铜腐蚀抑制剂包括噻唑、三唑和噻二唑。这些化合物的示例性实施方案包括苯并三唑、甲苯基三唑、辛基三唑，癸基三唑、十二烷基三唑、2-巯基苯并噻唑、2，5-二巯基-1，3，4-噻二唑，2-巯基-5-烃基硫代-1，3，4-噻二唑、2-巯基-5-烃基二硫代-1，3，4-噻二唑、2，5-双(烃基硫代)-1，3，4-噻二唑及2，5-双(烃基二硫代)-1，3，4-噻二唑。
有机钼化合物、烷基化二苯胺和含硫化合物可以分别添加到基础油中形成本发明的润滑剂组合物，或者可以先将它们预混合形成组合物然后再添加到基础油中。所制得的润滑剂组合物应该含有大量(即按重量计至少为90％)的基础油和少量(即按重量计少于10％)的添加剂组合物。
实施例
在表1和表2中，将本发明与美国专利第5,840,672(对比实施例1和对比实施例4)所教导的组合物相比较。表1和表2将含有不同硫化合物的本发明组合物与现有化合物相比较。实施例2和实施例5是本发明的组合物，其中保留了与对比实施例1和对比实施例4中相应的三种组分相同的重量百分比。也就是说除了或者是硫化异丁烯或者是噻二唑的硫组分外，组合物(比较实施例2和对比实施例1以及实施例5和对比实施例4)是相同的。除了所示的不同硫化合物外，实施例3和实施例6分别与对比实施例1和对比实施例4相同。在这些实施例中，在每个组合物中的硫化合物和其含量不同，但是每个实施例中硫含量是相同的。因此，第二组实施例表明采用不同硫化合物的效果，并与硫的含量无关。
表1--润滑剂组合物中添加剂组合物的试验
(有机钼化合物、烷基化二苯胺和噻二唑)
下表比较了本发明的添加剂组合物的实施例(实施例2、实施例3、实施例5和实施例6)和美国专利5,840,672中应用硫化异丁烯作为硫化合物的实施例(对比实施例1和对比实施例4)。
所有试验基本按照下面括号中指定的ASTM试验方法进行。
Figure C0281770000131
实施例2和实施例3相对于对比实施例1而言显示出沉积减少和抗氧化性能提高。实施例5和实施例6相对于对比实施例4而言显示出摩擦系数减小。
表2--润滑剂组合物中添加剂组合物的试验
(有机钼化合物、烷基化二苯胺和二硫代氨基甲酸酯)
下表比较了本发明的添加剂组合物的实施例(实施例8、实施例10和实施例11)和美国专利5,840,672中应用硫化异丁烯作为硫化合物的实施例(对比实施例7和对比实施例9)。
所有试验基本按照下面括号中指定的ASTM试验方法进行。
Figure C0281770000141
实施例8相对于对比实施例7而言显示出改善的铜腐蚀性。实施例10和实施例11相对于对比实施例9而言显示出改善的减摩性。
表3--润滑剂组合物中添加剂组合物的试验
(有机钼化合物、烷基化二苯胺和二硫代氨基甲酸酯)
本发明的添加剂组合物被添加到标准的基础油(5W-20)中形成本发明润滑剂组合物的实施例(实施例20-23)，并与不含本发明添加剂组合物的三种组分的润滑剂组合物比较。(除非另有所指下面的数字是重量百分比)
Figure C0281770000142
855(有机酰胺的有机钼配合物)
Figure C0281770000151
AZ(二戊基二硫代氨基甲酸锌)
Figure C0281770000152
SL(烷基化二苯胺)
TEOST MHT-4--发动机油热氧化模拟实验-适度高温(ASTM批准的方法)
实施例23与实施例22类似，但是各组分在加到基础油中之前预先混合在一起。
以上的每一个润滑剂组合物经历TEOST MHT-4条件下的测试，即在285℃下持续24小时。从以上数据可以看出，与单一组分或二组分组合物的结果相比，有机钼化合物、烷基化二苯胺和硫化合物的三组分混合物使得总沉积物出乎意外地降低。

Claims (11)

1.一种润滑剂组合物，包括主要量的基础油和少量的抗氧剂组合物，所述抗氧剂组合物包括：
(1)有机钼化合物，其通过使
(a)1摩尔的具有12个或更多个碳原子的脂肪油；
(b)1.0-2.5摩尔的二乙醇胺；及
(c)足够产生按配合物重量计为0.1-12.0％钼的钼源
起反应而制备，所述反应在70℃～160℃下进行；
(2)烷基化二苯胺，其为
(a)式X-NH-Y的烷基化二苯基仲胺，其中X和Y分别代表取代的或未取代的苯基，其中苯基的取代基选自具有1-20个碳原子的烷基、烷基芳基、羟基、羧基及硝基，且至少一个苯基被具有1-20个碳原子的烷基取代；或
(b)N-苯基-苯胺和2，4，4-三甲基戊烯反应的反应产物；及
(3)含硫化合物，其选自一种或多种以下物质：
(a)式(I)的噻二唑，
Figure C028177000002C1
其中R和R1分别选自氢、烷基、羟烷基、烷硫基、苯基烷基、烷基化苯基烷基、萜烯残基和下式的顺丁烯二酸残基
Figure C028177000002C2
其中R2和R3分别选自氢、支链或直链的烷基和环状脂族基，其中R和R1中的至少一个不是氢；
(b)式(II)的二硫代氨基甲酸酯，
其中
R4、R5、R6和R7相同或不相同，并且是具有1-13个碳原子的烃基；及
R8是脂族基团，选自具有1-8个碳原子的直链和支链亚烷基；及
(c)式(IV)的二硫代氨基甲酸金属盐，
Figure C028177000003C2
其中R13和R14代表含有1-8个碳的支链或直链烷基；M是金属阳离子；及n是一个基于金属阳离子化合价的整数；
其中基于所述组合物的总重量计(1)的重量为0.05-3.0％、(2)的重量为0.05-5.0％及(3)的重量为0.05-4.0％。
2.如权利要求1所述的润滑剂组合物，其中R和R1分别选自氢、烷基、萜烯残基和顺丁烯二酸残基。
3.如权利要求1所述的润滑剂组合物，其中：
所述的烷基化二苯胺包括N-苯基-苯胺和2，4，4-三甲基戊烯的反应产物；及
所述硫化合物选自以下一种或几种：烷基聚羧酸酯2，5-二巯基-1，3，4-噻二唑，亚甲基双二硫代氨基甲酸二丁酯，及二硫代氨基甲酸锌。
4.如权利要求1所述的润滑剂组合物，其还包括摩擦改性剂、抗氧化剂和/或铜腐蚀抑制剂。
5.如权利要求1所述的润滑剂组合物，其中所述的含硫化合物包括式(I)的噻二唑。
6.如权利要求5所述的润滑剂组合物，其中所述的噻二唑包括烷基聚羧酸酯2，5-二巯基-1，3，4-噻二唑。
7.如权利要求1所述的润滑剂组合物，其中所述的含硫化合物包括式(II)的二硫代氨基甲酸酯。
8.如权利要求7所述的润滑剂组合物，其中所述的二硫代氨基甲酸酯包括亚甲基双二硫代氨基甲酸二丁酯。
9.如权利要求1所述的润滑剂组合物，其中所述的含硫化合物包括式(IV)的二硫代氨基甲酸金属盐。
10.如权利要求9所述的润滑剂组合物，其中所述的二硫代氨基甲酸金属盐包括二硫代氨基甲酸锌。
11.如权利要求1所述的润滑剂组合物，其中所述的烷基化二苯胺包括N-苯基-苯胺和2，4，4-三甲基戊烯反应的反应产物。
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WO2003027215A2 (en) 2003-04-03
EP1468063A4 (en) 2010-07-21
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