CN1325620C - 含羧酸和胺的添加剂混合物作为防锈剂的润滑油组合物 - Google Patents

含羧酸和胺的添加剂混合物作为防锈剂的润滑油组合物 Download PDF

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CN1325620C
CN1325620C CNB028097017A CN02809701A CN1325620C CN 1325620 C CN1325620 C CN 1325620C CN B028097017 A CNB028097017 A CN B028097017A CN 02809701 A CN02809701 A CN 02809701A CN 1325620 C CN1325620 C CN 1325620C
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expression
oil composition
carboxylic acid
lubricating oil
alkyl
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CN1522295A (zh
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马场善治
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Shell Internationale Research Maatschappij BV
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Abstract

一种润滑油组合物，它包括少量添加剂混合物和大量的润滑油基础油，所述添加剂混合物包括：(i)羧酸基或羧酸酯基防锈剂；(ii)至少一类胺，所述胺选自：(A)可用通式(1)(R1)nNH3-n表示的烷基胺，其中R1表示具有12-30个碳原子的饱和或不饱和烷基，和n是1或2的整数值；和(B)可用通式(2)R2NH(CH2)mNH2表示的N-烷基多亚烷基二胺，其中R2表示具有12-30个碳原子的饱和或不饱和烷基，和m是2-5的整数值。

Description

含羧酸和胺的添加剂混合物 作为防锈剂的润滑油组合物
本发明涉及润滑油组合物，它在其中混合水或海水的恶劣操作环境下具有优良的防锈性能，和在各类机器中，在润滑性能和防腐蚀性能二者方面，它也显示出优良的性能。
当混合水或海水时，将防锈剂加入到润滑油中以保护机械部件防止生锈。一般地，防锈剂被强烈地吸附到金属表面上，结果在金属表面上形成防锈膜，从而防止金属与水发生直接的接触，进而抑制生锈。
另一方面，由于近年来出现的增加的运行速度、增加的负载和增加的效率，结果设备的磨损表面经受更恶劣的条件，和由于润滑油膜的破坏，结果有可能出现磨损表面的焦化。
因此，将合适用量的特压添加剂加入到在这种恶劣条件下使用的润滑油中以防止磨损表面的粘连，其中特压添加剂与金属表面反应，且在磨损表面处维持润滑性能。
EP-A-0744456描述了一种润滑剂，包括至少一种润滑粘度的油和至少(a)至少一种油溶性不含金属的含硫抗磨和/或特压剂，其具有不超过65的铜腐蚀试验活度；(b)至少一种油溶性不含金属的含磷和氮的抗磨和/或特压剂；(c)至少一种油溶性有机羧酸；和(d)至少一种油溶性有机胺。
US-A-5152908公开了一种润滑剂，包括大量的润滑粘度的油和少量添加剂包，所述添加剂包由(a)经处理的二硫代磷酸锌，(b)高碱性的羧酸盐，优选硼酸盐，(c)烷基胺和(d)硫化的烯烃组成。
WO-A-00/11122公开了一种润滑油组合物，包括(I)100重量份润滑油基础油；(II)作为抗磨剂的(i)(a)0.05-10重量份本文中描述的硫代磷酸盐，和(b)0.01-1.0重量份本文中描述的磷化合物的胺盐，和/或(ii)0.05-10重量份本文中描述的二硫代磷酸酯；(III)作为防锈剂的0.01-1.0重量份的聚亚烷基聚酰胺，其通过使(a)本文中描述的聚亚烷基多胺和(b)具有4-30个碳原子的羧酸反应而获得。
EP-A-0434464描述了一种润滑剂组合物，包括(a)无金属的抗磨或载荷能力添加剂，其含有硫和/或磷，和(b)通式R1OOC(CR3R4)CR5(NR6R7)COOR2的氨基琥珀酸酯形式的防腐剂，其中R1和R2分别为1-30个碳原子的烷基，R3、R4和R5分别为氢或1-4个碳原子的烷基，R6和R7分别为氢、1-30个碳原子的烷基、或衍生自饱和或不饱和至多为30个碳原子的羧酸的酰基，R6和R7中至少之一是酰基。
然而，已知防锈剂的配混会阻碍在磨损表面处金属表面与特压添加剂之间的反应，和结果在很大程度上损害了特压添加剂的效果。
因此希望提供无灰的润滑油组合物，它不含金属，和从润滑油的润滑性能以及防锈性能的角度考虑，甚至在恶劣的润滑条件下，它也能维持优良的特压性能，和同时具有优良的防锈性能。
现已令人惊奇地发现，通过结合特定的烷基胺和防锈剂，可大大地降低所添加的防锈剂的用量，结果可将因防锈剂而引起的特压性能的下降抑制到最小程度。
本发明提供一种润滑油组合物，它包括少量的添加剂混合物和大量的润滑油基础油，所述添加剂混合物包括：
(i)羧酸基或羧酸酯基防锈剂；
(ii)至少一类胺，所述胺选自：(A)可用通式(1)表示的烷基胺，
(R1)nNH3-n    (1)
其中R1表示具有12-30个碳原子的饱和或不饱和烷基，和n是1或2的整数值；和(B)可用通式(2)表示的N-烷基多亚烷基二胺，
R2NH(CH2)mNH2    (2)
其中R2表示具有12-30个碳原子的饱和或不饱和烷基，和m是2-5的整数值。
本发明中的“大量”是指相对于润滑油组合物的总重量至少50wt％。
所述组合物通常包括0.001-0.5重量份羧酸基或羧酸酯基防锈剂；和0.001-0.2重量份至少一类胺，以每100重量份润滑油基础油计。
所述组合物优选包括0.001-0.05重量份羧酸基或羧酸酯基防锈剂，以每100重量份润滑油基础油计。所述组合物更优选包括0.005-0.05重量份所述防锈剂，以每100重量份润滑油基础油计。
所述组合物优选包括0.001-0.05重量份至少一类胺，以每100重量份润滑油基础油计。
在本发明进一步的实施方案中，润滑油组合物包括可用通式(3)表示的β-二硫代磷酰基丙酸作为特压添加剂，
S＝P(O-R3)2SCH2CH(R4)COOH    (3)
其中R3表示具有3-8个碳原子的支链烷基，和R4是氢原子或选自具有1-4个碳原子的直链或支链烷基中的基团。
所述式(3)的特压添加剂的存在量优选为0.001-0.5重量份，更优选0.001-0.02重量份，以每100重量份润滑油基础油计。
在本发明仍进一步的实施方案中，润滑油组合物包括可用通式(4)表示的硫代磷酸三芳酯(triaryl phosphorothioate)作为特压添加剂，
S＝P(O-Ph-R5)3    (4)
其中Ph表示苯基，和R5表示氢原子或具有1-9个碳原子的直链或支链烷基。
所述式(4)的特压添加剂的存在量优选为0.05-5重量份，更优选0.05-0.5重量份，以每100重量份润滑油基础油计。
在本发明的另一实施方案中，润滑油组合物包括可用通式(5)表示的酸性磷酸酯作为特压添加剂，
O＝P(OR6)3-r(OH)r    (5)
其中R6表示具有3-13个碳原子的直链或支链烷基，和r是1或2的整数值。
所述式(5)的特压添加剂的存在量优选为0.01-0.5重量份，更优选0.01-0.1重量份，以每100重量份润滑油基础油计。
本发明的润滑油组合物可非必需地包括一种或多种式(3)-(5)的化合物作为特压添加剂。
构成本发明的润滑油组合物的润滑油基础油没有任何特别限制，只要它包括石油基油和/或合成烃基油。
运动粘度为2-680mm2/s(40℃)，优选5-320mm2/s(40℃)，和最优选8-220mm2/s(40℃)；总硫含量(wt％)为0-1wt％，和优选0-0.3wt％；总氮含量(wt.ppm)为0-100ppm，和优选0-30ppm；和苯胺点为80-130℃，和优选100-125℃的润滑油基础油是优选的。
可在本发明中使用的石油基润滑油基础油可以是例如单独的溶剂精制基础油、氢化精制基础油或高度氢化与裂解基础油或这些油的混合物。高度氢化的裂解基础油是粘度指数为至少130(典型地145-155)的润滑油基础油，它是采用已经裂解和溶剂脱蜡的疏松石蜡作为原材料，通过在催化剂存在下氢化裂解(接触裂解)，将直链烷属烃异构化为支链烷属烃而获得的；或粘度指数为至少130(典型地145-155)的润滑基油，它是使用重的直链烷属烃，并与以上所述相同的方式，对它进行催化裂解和并构化获得的，而所述重的直链烷属烃是使用一氧化碳和氢气通过Fischer-Trosch聚合获得的，而一氧化碳和氢气是通过天然气(如甲烷)的气化工艺(部分氧化)获得的。
此外，可在本发明中使用的合成烃基基础油包括通过均聚或共聚选自具有3-15个碳原子和优选4-12个碳原子的直链和支链烯烃中的单体而获得的烯烃低聚物。
在本发明中，石油基润滑油基础油和合成烃基基础油可单独或以混合物的形式使用。
可在本发明中使用的羧酸基或羧酸酯基防锈剂在防锈剂分子内具有羧酸或羧酸酯基团，和它们通常广泛用于润滑油中。
所述防锈剂包括例如具有8-30个碳原子的单羧酸、琥珀酸烷基酯或琥珀酸链烯基酯或其部分酯、具有12-30个碳原子的羟基脂肪酸及其衍生物、具有8-24个碳原子的肌氨酸及其衍生物、氨基酸及其衍生物、环烷酸及其衍生物、羊毛脂脂肪酸、巯基脂肪酸和氧化石蜡。
以下示出了特别优选的防锈剂。
单羧酸的实例(C8-C30)
辛酸、壬酸、癸酸、十一酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、二十二烷酸、蜡酸、褐煤酸、蜂花酸、油酸、二十二烷二酸(docosanic acid)、芥酸、二十烷酸、牛油脂肪酸、大豆脂肪酸、椰子油脂肪酸、亚油酸、松浆油脂肪酸、12-羟基硬脂酸、月桂基肌氨酸、肉豆蔻基肌氨酸、棕榈基肌氨酸、硬脂基肌氨酸、油基肌氨酸、烷化(C8-C20)苯氧基乙酸、羊毛脂脂肪酸和C8-C24巯基脂肪酸。
多元羧酸的实例
在CAS No.27859-58-1中所述的链烯基(C20-C100)琥珀酸及其酯衍生物、二聚酸、具有下式所示结构式的N-酰基-N-烷氧基烷基天冬氨酸酯(US-A-5275749)和CAS No.68906-34-3的化合物：
Figure C0280970100091
其中R7和R8各自独立地表示氢或选自C1-C30烷基、C1-C30酰基和烷基醚基中的基团，和R9-R13各自独立地表示氢或选自C1-C30烷基中的基团。
由通式(1)表示的前述烷基胺的实例包括伯胺如月桂胺、椰子胺、正十三烷胺、肉豆蔻胺、正十五烷胺、棕榈基胺、正十七烷胺、硬脂胺、正十九烷胺、正二十烷胺、正二十一烷胺、正二十二烷胺、正二十三烷胺、正二十五烷胺、油胺、牛油胺、氢化牛油胺和大豆胺。仲胺的实例包括二月桂胺、二椰子胺、双-正十三烷胺、二肉豆蔻胺、双-正十五烷胺、二棕榈基胺、双-正十七烷胺、二硬脂胺、双-正十九烷胺、双-正二十烷胺、双-正二十一烷胺、双-正二十二烷胺、双-正二十三烷胺、双-正二十五烷胺、二油胺、二牛油胺、二氢化牛油胺和二大豆胺。
可用通式(2)表示的前述N-烷基多亚烷基二胺的实例包括乙二胺类如月桂基乙二胺、椰子乙二胺、正十三烷基乙二胺、肉豆蔻基乙二胺、正十五烷基乙二胺、棕榈基乙二胺、正十七烷基乙二胺、硬脂基乙二胺、正十九烷基乙二胺、正二十烷基乙二胺、正二十一烷基乙二胺、正二十二烷基乙二胺、正二十三烷基乙二胺、正二十五烷基乙二胺、油基乙二胺、牛油乙二胺、氢化牛油乙二胺和大豆乙二胺；丙二胺类如月桂基丙二胺、椰子丙二胺、正十三烷基丙二胺、肉豆蔻基丙二胺、正十五烷基丙二胺、棕榈基丙二胺、正十七烷基丙二胺、硬脂基丙二胺、正十九烷基丙二胺、正二十烷基丙二胺、正二十一烷基丙二胺、正二十二烷基丙二胺、正二十三烷基丙二胺、正二十五烷基丙二胺、油基丙二胺、牛油丙二胺、氢化牛油丙二胺和大豆丙二胺；丁二胺类如月桂基丁二胺、椰子丁二胺、正十三烷基丁二胺、肉豆蔻基丁二胺、正十五烷基丁二胺、硬脂基丁二胺、正二十烷基丁二胺、正二十一烷基丁二胺、正二十二烷基丁二胺、正二十三烷基丁二胺、正二十五烷基丁二胺、油基丁二胺、牛油丁二胺、氢化牛油丁二胺和大豆丁二胺；和戊二胺如月桂基戊二胺、椰子戊二胺、肉豆蔻基戊二胺、棕榈基戊二胺、硬脂基戊二胺、油基戊二胺、牛油戊二胺、氢化牛油戊二胺和大豆戊二胺。
除了前述组分之外，可视需要将常用的适量各类辅助添加剂加入到本发明的润滑油组合物中，以便选一步改进其性能。可加入到本发明的润滑油组合物中的辅助添加剂包括已知的润滑油添加剂如抗氧剂、金属失活剂、特压添加剂、消泡剂、粘度指数增加剂、流点下降剂、清洁和分散剂、防锈剂和抗乳化剂。
胺基抗氧剂的实例包括二烷基二苯胺类如p，p`-二辛基二苯胺(由Seiko Kagaku Co.以商业牌号“N onflex OD-3”制造)、p，p`-二-α-甲基苄基二苯胺和N-p-丁基苯基-N-p`-辛基苯胺；单烷基二苯胺类如单叔丁基二苯胺和单辛基二苯胺；二(二烷基苯基)胺类如二(2，4-二乙基苯基)胺和二(2-乙基-4-壬基苯基)胺；烷基苯基-1-萘胺类如辛基苯基-1-萘胺和N-叔十二烷基苯基-1-萘胺；芳基萘胺类如1-萘胺、苯基-1-萘胺、苯基-2-萘胺、N-己基苯基-2-萘胺和N-辛基苯基-2-萘胺；苯二胺类如N，N`-二异丙基-p-苯二胺和N，N`-二苯基-p-苯二胺；和苯并噻嗪类如苯并噻嗪(由Hodogaya Kagaku Co.，制造：苯并噻嗪)和3，7-二辛基苯并噻嗪。
硫基抗氧剂的实例包括二烷基硫醚如二十二烷基硫醚和二十八烷基硫醚；硫代二丙酸酯类如硫代二丙酸二十二烷基酯、硫代二丙酸二十八烷基酯、硫代二丙酸二肉豆蔻基酯和硫代二丙酸十二烷基十八烷基酯和2-巯基苯并咪唑。
苯酚基抗氧剂的实例包括2-叔丁基苯酚、2-叔丁基-4-甲基苯酚、2-叔丁基-5-甲基苯酚、2，4-二叔丁基苯酚、2，4-二甲基-6-叔丁基苯酚、2-叔丁基-4-甲氧基苯酚、3-叔丁基-4-甲氧基苯酚、2，5-二叔丁基氢醌(由Kawaguchi Kagaku Co.以商业牌号“Antage DBH”制造)、2，6-二叔丁基苯酚和2，6-二叔丁基-4-烷基苯酚如2，6-二叔丁基-4-甲基苯酚和2，6-二叔丁基-4-乙基苯酚；2，6-二叔丁基-4-烷氧基苯酚如2，6-二叔丁基-4-甲氧基苯酚和2，6-二叔丁基-4-乙氧基苯酚、3，5-二叔丁基-4-羟苄基巯基辛基乙酸酯、烷基-3-(3，5-二叔丁基-4-羟苯基)丙酸酯如正辛基-3-(3，5-二叔丁基-4-羟苯基)丙酸酯(由Yoshitomi Seiyaku Co.以商业牌号“Yonox SS”制造)、正十二烷基-3-(3，5-二叔丁基-4-羟苯基)丙酸酯和2`-乙基己基-3-(3，5-二叔丁基-4-羟苯基)丙酸酯；2，6-二叔丁基-α-二甲基氨基-对甲酚、2，2`-亚甲基双(4-烷基-6-叔丁基苯酚)化合物如2，2`-亚甲基双(4-甲基-6-叔丁基苯酚)(由Kawaguchi Kagaku Co.以商业牌号“AntageW-400”制造)和2，2`-亚甲基双(4-乙基-6-叔丁基苯酚)(由KawaguchiKagaku Co.以商业牌号“Antage W-500”制造)；双酚类如4，4`-亚丁基双(3-甲基-6-叔丁基苯酚)(由Kawaguchi Kagaku Co.以商业牌号“Antage W-300”制造)、4，4`-亚甲基双(2，6-二叔丁基苯酚)(由Laporte Performance Chemicals以商业牌号“Ionox 220AH”制造)、4，4`-双(2，6-二叔丁基苯酚)、2，2-(二对羟苯基)丙烷(双酚A)、2，2-双(3，5-二叔丁基-4-羟苯基)丙烷、4，4`-亚环己基双(2，6-二叔丁基苯酚)、己二醇双[3-(3，5-二叔丁基-4-羟苯基)丙酸酯](由CibaSpecialty Chemicals Co.以商业牌号“Irganox L109”制造)、三甘醇双[3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯](由YoshitomiSeiyaku Co.以商业牌号“Tominox 917”制造)、2，2`-硫代[二乙基-3-(3，5-二叔丁基-4-羟苯基)丙酸酯](由Ciba Specialty ChemicalsCo.以商业牌号“Irganox L115”制造)、3，9-双{1，1-二甲基-2-[3-(3-叔丁基-4-羟基-5-甲苯基)-丙酰氧基]乙基}2，4，8，10-四氧杂螺[5，5]十一烷(由Sumitomo Kagaku Co.以商业牌号“Sumilizer GA80”制造)和4，4`-硫代双(3-甲基-6-叔丁基苯酚)(由Kawaguchi Kagaku Co.以商业牌号“Antage RC”制造)、2，2`-硫代双(4，6-二叔丁基间苯二酚)；多元酚如四[亚甲基-3-(3，5-二叔丁基-4-羟苯基)丙酸基(propionato)]甲烷(由Ciba Specialty Chemicals Co.以商业牌号“Irganox L101”制造)、1，1，3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷(由Yoshitomi Seiyaku Co.以商业牌号“Yoshinox 930”制造)、1，3，5-三甲基-2，4，6-三(3，5-二叔丁基-4-羟苄基)苯(由CibaSpecialty Chemicals Co.以商业牌号“Irganox 1330”制造)、双[3，3`-双(4`-羟基-3`-叔丁基苯基)丁酸]二元醇酯、2-(3`，5`-二叔丁基-4-羟苯基)-甲基-4-(2``，4``-二叔丁基-3``-羟苯基)甲基-6-叔丁基苯酚和2，6-双(2`-羟基-3`-叔丁基-5`-甲基苄基)-4-甲基苯酚；和酚/醛的缩合物如对叔丁基苯酚与甲醛的缩合物和对叔丁基苯酚与乙醛的缩合物。
磷基抗氧剂的实例包括亚磷酸三芳酯如亚磷酸三苯酯和亚磷酸三甲苯酯、亚磷酸三烷酯如亚磷酸三(十八烷)酯和亚磷酸十三烷酯和三硫代亚磷酸三(十二烷)酯。
这些抗氧剂可单独或以混合物的形式使用，方便地其用量范围为0.01-2.0重量份，以每100重量份基础油计。
可在本发明的润滑油组合物中使用的金属失活剂包括苯并***和4-烷基苯并***如4-甲基苯并***和4-乙基苯并***；5-烷基苯并***如5-甲基苯并***和5-乙基苯并***；1-烷基苯并***如1-二辛基氨基甲基-2，3-苯并***；苯并***衍生物如1-烷基甲基苯并***，例如1-二辛基氨基甲基-2，3-甲基苯并***(tolutriazole)；苯并咪唑和苯并咪唑衍生物如2-(烷基二硫代)苯并咪唑类，例如2-(辛基二硫代)苯并咪唑、2-(癸基二硫代)苯并咪唑和2-(十二烷基二硫代)苯并咪唑；2-(烷基二硫代)甲基苯并咪唑(toluimidazole)如2-(辛基二硫代)甲基苯并咪唑2-(癸基二硫代)甲基苯并咪唑和2-(十二烷基二硫代)甲基苯并咪唑；吲唑和甲基苯并咪唑的吲唑衍生物如4-烷基吲唑、5-烷基吲唑；苯并噻唑、2-巯基苯并噻唑衍生物(由Chiyoda KagakuCo.，以商业牌号“Thiolite B-3100”制造)和2-(烷基二硫代)苯并噻唑如2-(己基二硫代)苯并噻唑和2-(辛基二硫代)苯并噻唑；2-(烷基二硫代)甲基苯并噻唑(toluthiazole)如2-(苄基二硫代)甲基苯并噻唑和2-(辛基二硫代)甲基苯并噻唑、2-(N，N-二烷基二硫代氨基甲酰基)苯并噻唑如2-(N，N-二乙基二硫代氨基甲酰基)苯并噻唑、2-(N，N-二丁基二硫代氨基甲酰基)苯并***和2-(N，N-二己基-二硫代氨基甲酰基)苯并***；2-(N，N-二烷基二硫代氨基甲酰基)甲基苯并噻唑的苯并噻唑衍生物如2-(N，N-二乙基二硫代氨基甲酰基)甲基苯并噻唑、2-(N，N-二丁基二硫代氨基甲酰基)甲基苯并噻唑、2-(N，N-二己基-二硫代氨基甲酰基)甲基苯并噻唑；2-(烷基二硫代)苯并唑类如2-(辛基二硫代)苯并唑、2-(癸基二硫代)苯并唑和2-(十二烷基二硫代)苯并唑；2-(烷基二硫代)甲基苯并唑的苯并唑(toluoxazole)衍生物如2-(辛基二硫代)甲基苯并唑、2-(癸基二硫代)甲基苯并唑和2-(十二烷基二硫代)甲基苯并唑；2，5-双(烷基二硫代)-1，3，4-噻二唑如2，5-双(庚基二硫代)-1，3，4-噻二唑、2，5-双(壬基二硫代)-1，3，4-噻二唑、2，5-双(十二烷基二硫代)-1，3，4-噻二唑和2，5-双(十八烷基二硫代)-1，3，4-噻二唑；2，5-双(N，N-二烷基二硫代氨基甲酰基)-1，3，4-噻二唑如2，5-双(N，N-二乙基二硫代氨基甲酰基)-1，3，4-噻二唑、2，5-双(N，N-二丁基二硫代氨基甲酰基)-1，3，4-噻二唑和2，5-双(N，N-二辛基二硫代氨基甲酰基)-1，3，4-噻二唑；2-N，N-二烷基二硫代氨基甲酰基-5-巯基-1，3，4-噻二唑的噻二唑衍生物如2-N，N-二丁基二硫代氨基甲酰基-5-巯基-1，3，4-噻二唑和2-N，N-二辛基二硫代氨基甲酰基-5-巯基-1，3，4-噻二唑，和1-烷基-2，4-***的***衍生物如1-二辛基氨基甲基-2，4-***。
这些金属失活剂可单独或以混合物的形式使用，方便地其用量范围为0.01-0.5重量份，以每100重量份基础油计。
可用作消泡剂的物质包括例如二甲基聚硅氧烷、有机硅酸盐如二乙基硅酸盐、氟硅氧烷和无硅基消泡剂如聚丙烯酸亚烷酯。这些消泡剂可单独或以混合物的形式加入和使用，方便地其用量范围为0.0001-0.1重量份，以每100重量份基础油计。
可使用的粘度指数增加剂包括例如聚甲基丙烯酸酯和乙烯/丙烯共聚物、其它非分散型粘度指数增加剂如烯烃共聚物如苯乙烯/二烯共聚物，和可分散型粘度指数增加剂(其中在这种物质内含氮单体已经共聚)。这些物质可单独或以混合物的形式加入和使用，方便地其用量范围为0.05-20重量份，以每100重量份基础油计。
流点下降剂的实例包括聚甲基丙烯酸酯基聚合物。可以0.01-5重量份(以每100重量份基础油计)加入这些物质和方便地使用。
可使用的清洁和分散剂的实例包括金属基洗涤剂如中性和碱性碱土金属磺酸盐、碱土金属酚盐和碱土金属水杨酸链烯基琥珀酰亚胺和链烯基琥珀酰亚胺酯和它们的硼氢化物，和已用硫化合物改性的无灰分散剂。
这些试剂可单独或以混合物的形式加入和使用，方便地其用量为0.01-1重量份，以每100重量份基础油计。
特压添加剂的实例包括硫基特压添加剂如二烷基硫醚、二苄基硫醚、二烷基多硫醚、二苄基二硫醚、烷基硫醇、二苯并噻吩和2，2`-二硫代双(苯并噻唑)；磷基特压添加剂如磷酸三烷酯、磷酸三芳酯、膦酸三烷酯、亚磷酸三烷酯、亚磷酸三芳酯和二烷基肼(hydrozine)亚磷酸酯；和磷与硫基特压添加剂如二烷基二硫代磷酸锌、二烷基硫代磷酸、硫代磷酸三烷酯、酸性硫代磷酸酯和三硫代磷酸三烷酯。可单独或以混合物的形式使用这些特压添加剂，方便地其用量为0.1-2重量份，以每100重量份基础油计。
也可使用常用作润滑油添加剂的已知抗乳化剂。可方便地添加这些试剂，和其用量范围为0.0005-0.5重量份，以每100重量份基础油计。
抗乳化剂的实例包括聚亚烷基二醇基非离子表面活性剂，例如聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚和聚氧乙烯烷基萘基醚。
本发明的润滑油组合物可用作液压油组合物、压缩机油组合物、汽轮油组合物、轴承油组合物和/或齿轮油组合物。
现参考下述实施例描述本发明，但无论如何不打算用实施例限制本发明的范围。
例举性实施例
在作为基础油的40℃下运动粘度为31mm2/s、粘度指数为107、硫含量小于5ppm、氮含量小于1ppm和苯胺点为112℃的氢化精制基础油中，通过配混在表1所示的各种浓度下的特压添加剂和羧酸基和羧酸酯基防锈剂和胺，制备样品油。
就防锈性能和特压性能方面，研究本发明的效果。
在实施例和对比例中的性能评价所使用的试验方法如下所示。
防锈试验
为了评价样品油的防锈性能，根据ASTM D665，在人工海水存在下在60℃下进行防锈试验24小时。在试验之后，研究在钢试样上是否形成锈斑。
FZG齿轮试验
为了评价在齿轮设备中样品油的润滑性能，根据ISO/WD14635-1使用A测试齿轮，并在90℃的起始油温和1450rpm的发动机速度下，在各负载阶段(loading stage)下运行齿轮15分钟。观察当在各段中增加负载时在测试齿轮的齿轮牙表面上出现焦化的负载阶段。
实施例1-9和对比例1-9
表1-3示出了组合物和试验结果。
表1
  实施例/对比例  对比例1  对比例2  对比例3  对比例4  对比例5  对比例6  对比例7
  基础油，wt％  99.98  99.93  99.93   99.94   99.94   99.94   99.78
  特压添加剂，wt％3(O，O-二异丁基二硫代磷酰基)-2-甲基丙酸硫代磷酸三苯酯异丁基酸性磷酸酯 0.02-- 0.02-- 0.02-- 0.02-- 0.02-- 0.02-- 0.02--
  羧酸-、羧酸酯-基防锈剂组分，wt％聚亚烷基琥珀酸半酯(1)N-油基肌氨酸(2)壬基苯氧基乙酸酯(3)N-酰基-N-烷氧基烷基天冬氨酸酯A(4)N-酰基-N-烷氧基烷基天冬氨酸酯B(5) ----- ----- 0.05---- -0.04--- --0.04-- ---0.04- ----0.20
  胺组分，wt％椰子胺油胺二椰子胺牛油丙二胺 ---- 0.05--- ---- ---- ---- ---- ----
  防锈试验结果   形成锈斑   形成锈斑   无锈斑   无锈斑   无锈斑   无锈斑   无锈斑
  FZG齿轮试验结果最小失败负载阶段   ＞12   ＞12   8   8   8   9   9
表2
  实施例/对比例   对比例8   对比例9   实施例1   实施例2   实施例3  实施例4  实施例5
  基础油，wt％   99.53   99.35   99.95   99.955   99.95   99.955   99.88
  特压添加剂，wt％3(O，O-二异丁基二硫代磷酰基)-2-甲基丙酸硫代磷酸三苯酯异丁基酸性磷酸酯 -0.500.10 -0.500.10 0.02-- 0.02-- 0.02-- 0.02-- 0.02--
  羧酸-、羧酸酯-基防锈剂组分，wt％聚亚烷基琥珀酸半酯(1)N-油基肌氨酸(2)壬基苯氧基乙酸酯(3)N-酰基-N-烷氧基烷基天冬氨酸酯A(4)N-酰基-N-烷氧基烷基天冬氨酸酯B(5) ---0.05- ----- 0.01---- -0.005--- --0.01-- ---0.005- ----0.05
  胺组分，wt％椰子胺油胺二椰子胺牛油丙二胺 ---- 0.05--- 0.02--- 0.02--- 0.02--- 0.02--- 0.05---
  防锈试验结果   无锈斑   形成锈斑   无锈斑   无锈斑   无锈斑   无锈斑   无锈斑
  FZG齿轮试验结果最小失败负载阶段   9   ＞12   11   11   10   ＞12   11
表3
实施例/对比例 实施例6  实施例7  实施例8  实施例9
基础油，wt％ 99.955  99.945  99.955   99.37
特压添加剂，wt％3(O，O-二异丁基二硫代磷酰基)-2-甲基丙酸硫代磷酸三苯酯异丁基酸性磷酸酯 0.02-- 0.02-- 0.02-- -0.500.10
羧酸-、羧酸酯-基防锈剂组分，wt％聚亚烷基琥珀酸半酯(1)N-油基肌氨酸(2)壬基苯氧基乙酸酯(3)N-酰基-N-烷氧基烷基天冬氨酸酯A(4)N-酰基-N-烷氧基烷基天冬氨酸酯B(5) ---0.005- ---0.005- ---0.005- ---0.01-
胺组分，wt％椰子胺油胺二椰子胺牛油丙二胺 -0.02-- --0.03- ---0.02 0.02---
防锈试验结果 无锈斑   无锈斑  无锈斑   无锈斑
FZG齿轮试验结果最小失败负载阶段 ＞12   ＞12  ＞12   ＞12
备注：
1.由Lubrizol Co以商业牌号“Lubrizol 859”制造
2.由Ciba Specialty Chemicals Co.以商业牌号“Sarcosil O”
制造
3.由Ciba Specialty Chemicals Co.以商业牌号“Irgacore NPA”
制造
4.由Colonial Chemicals Co.以商业牌号“Korakoa 93”制造
5.CAS No.68906-34-3，27136-73-8
6.由King Industries Co.以商业牌号“K-CORR 100”制造。在US-A-5275749中披露的防锈剂。
对比例1仅具有在其中配混的特压添加剂。尽管所述实施例在齿轮试验中显示出良好的特压性能，但当没有向其中加入防锈剂和胺时，在防锈试验中形成锈斑。
相反，在对比例3-8中，已向其中加入了最小量的羧酸基或羧酸酯基防锈剂，因此在防锈试验中没有形成锈斑。然而，在FZG齿轮试验中，由于加入防锈剂导致耐久负载显著下降。
此外，在对比例2和9中仅加入胺，也没有加入羧酸基或羧酸酯基防锈剂。没有获得充足的防锈效果。
在本发明实施例1-9的情况下，由于在本发明的主要组分胺与羧酸基或羧酸酯基防锈剂之间的协同效果导致大大地降低了所要求的羧酸基或羧酸酯基防锈剂的用量，大大地改进了因防锈剂引起的特压性能下降。
本发明的润滑油组合物基本上不含或完全不含对环境和安全这两方面均有害的金属，和它们具有良好的防锈性能的同时也具有良好的特压性能，以匹配增加的速度、较高的压力、更紧密的结构和现代工业机器在耐用性要求方面的改进。
此外，可通过本发明可降低所添加的防锈剂的用量，和可更便宜地提供具有优良性能的润滑油组合物。
本发明的润滑油组合物用作要求防锈性能和特压性能这两方面的润滑油组合物，和它们可用作液压工作油、齿轮油、压缩机油、汽轮机油和轴承油。

Claims (9)

1.润滑油组合物，包括少量的添加剂混合物和大量的润滑油基础油，所述添加剂混合物包括：
(i)羧酸基或羧酸酯基防锈剂；
(ii)至少一类胺，所述胺选自：(A)通式(1)表示的烷基胺，
(R1)nNH3-n    (1)
其中R1表示具有12-30个碳原子的饱和或不饱和烷基，和n是1或2的整数值；和(B)通式(2)表示的N-烷基多亚烷基二胺，
R2NH(CH2)mNH2    (2)
其中R2表示具有12-30个碳原子的饱和或不饱和烷基，和m是2-5的整数值；
其中所述组合物包括0.001-0.5重量份羧酸基或羧酸酯基防锈剂，和0.001-0.05重量份至少一类胺，以每100重量份润滑油基础油计。
2.权利要求1的润滑油组合物，其中所述组合物包括0.001-0.05重量份羧酸基或羧酸酯基防锈剂，以每100重量份润滑油基础油计。
3.权利要求1或2的润滑油组合物，它进一步包括选自以下的一种或多种化合物作为特压添加剂：通式(3)表示的β-二硫代磷酰基丙酸
S＝P(-O-R3)2SCH2CH(R4)COOH    (3)
其中R3表示具有3-8个碳原子的支链烷基，和R4是氢原子或选自具有1-4个碳原子的直链或支链烷基中的基团；
通式(4)表示的硫代磷酸三芳酯
S＝P(O-Ph-R5)3    (4)
其中Ph表示苯基，和R5表示氢原子或具有1-9个碳原子的直链或支链烷基；
通式(5)表示的酸性磷酸酯
O＝P(OR6)3-r(OH)r    (5)
其中R6表示具有3-13个碳原子的直链或支链烷基，和r是1或2的整数值。
4.权利要求1或2的润滑油组合物，其中润滑油基础油是石油基油和/或合成烃基油。
5.权利要求3的润滑油组合物，其中润滑油基础油是石油基油和/或合成烃基油。
6.权利要求1-5任何一项的润滑油组合物作为液压油组合物、压缩机油组合物、汽轮机油组合物、轴承油组合物和/或齿轮油组合物的用途。
7.少量(i)羧酸基或羧酸酯基防锈剂和(ii)至少一类胺作为防锈添加剂混合物在包括大量润滑油基础油的润滑油组合物中的用途，其中所述胺选自：(A)通式(1)表示的烷基胺，
(R1)nNH3-n    (1)
其中R1表示具有12-30个碳原子的饱和或不饱和烷基，和n是1或2的整数值；和(B)通式(2)表示的N-烷基多亚烷基二胺，
R2NH(CH2)mNH2    (2)
其中R2表示具有12-30个碳原子的饱和或不饱和烷基，和m是2-5的整数值，
其中所述润滑油组合物包括0.001-0.5重量份羧酸基或羧酸酯基防锈剂、0.001-0.05重量份至少一类胺，以每100重量份润滑油基础油组合物计。
8.权利要求7的用途，其中所述润滑油组合物进一步包括选自以下的一种或多种化合物作为特压添加剂：通式(3)表示的β-二硫代磷酰基丙酸
S＝P(-O-R3)2SCH2CH(R4)COOH    (3)
其中R3表示具有3-8个碳原子的支链烷基，和R4是氢原子或选自具有1-4个碳原子的直链或支链烷基中的基团；
通式(4)表示的硫代磷酸三芳酯
S＝P(O-Ph-R5)3    (4)
其中Ph表示苯基，和R5表示氢原子或具有1-9个碳原子的直链或支链烷基；
通式(5)表示的酸性磷酸酯
O＝P(OR6)3-r(OH)r    (5)
其中R6表示具有3-13个碳原子的直链或支链烷基，和r是1或2的整数值。
9.权利要求7或8的用途，其中所述润滑油组合物是液压油组合物、压缩机油组合物、汽轮机油组合物、轴承油组合物和/或齿轮油组合物。
CNB028097017A 2001-05-11 2002-05-07 含羧酸和胺的添加剂混合物作为防锈剂的润滑油组合物 Expired - Lifetime CN1325620C (zh)

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ATE318881T1 (de) 2006-03-15
DK1385926T3 (da) 2006-07-10
JP4608129B2 (ja) 2011-01-05
EP1385926B1 (en) 2006-03-01
JP2002338983A (ja) 2002-11-27
DE60209497D1 (de) 2006-04-27
KR20030096370A (ko) 2003-12-24
CA2447044A1 (en) 2002-11-21
WO2002092735A1 (en) 2002-11-21
CN1522295A (zh) 2004-08-18
EP1385926A1 (en) 2004-02-04
ES2259375T3 (es) 2006-10-01
US20040214733A1 (en) 2004-10-28
KR100866811B1 (ko) 2008-11-04
DE60209497T2 (de) 2006-11-16

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