CN1201066A - 协合有机钼组合物和含有它的润滑组合物 - Google Patents

协合有机钼组合物和含有它的润滑组合物 Download PDF

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CN1201066A
CN1201066A CN98101624A CN98101624A CN1201066A CN 1201066 A CN1201066 A CN 1201066A CN 98101624 A CN98101624 A CN 98101624A CN 98101624 A CN98101624 A CN 98101624A CN 1201066 A CN1201066 A CN 1201066A
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molybdenum
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CN1098348C (zh
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托马斯·J·卡罗尔
史蒂文·G·唐纳利
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Vanderbilt Minerals Ltd
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Abstract

本发明涉及包括有机钼化合物和选自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,二硫代磷酸金属盐和二硫代磷酸酯的有机硫化合物的一种协合抗磨损组合物。含有协合组合物的润滑组合物具有良好的抗磨损性能和改进的氧化稳定性。

Description

协合有机钼组合物和含有它的润滑组合物
本发明涉及具有改进性能的润滑组合物。本发明的另一方面涉及一种赋予用于内燃机如汽油机和柴油机的润滑组合物以抗磨和抗擦性能的添加剂组合物。
已知为抗磨剂的添加剂被用来提高润滑剂的承载能力。抗磨剂促进表面膜的形成从而防止接触表面的磨损。通过降低摩擦损失增强的机械效率进一步促使低燃料消耗和能量节约。
已知的是某些有机钼配合物具有抗磨性以及其它所需润滑特性，如US4,889,647中所述。令人惊奇的是，现已发现所述钼配合物与某些有机硫化合物结合产生了协合的抗磨效果。
根据本发明，提供了一种协合抗磨组合物，包括：
(1)有机钼配合物，通过约1摩尔脂肪油，约1.0-2.5摩尔二乙醇胺和足以得到以配合物重量为基础计约0.1-12.0％的钼的钼源进行反应而制备，和
(2)有机硫化合物，选自：
(i)具有下式的1，3，4-噻二唑类：
Figure A9810162400061
其中R和R1独立地选自C1-22烷基，萜烯残基和下式的马来酸残基
Figure A9810162400062
和R2和R3表示C1-22烷基和C5-7环烷基，R2或R3可以是氢和当R2或R3是C9-22烷基时R或R1可以是氢；
(ii)具有下式的二硫代氨基甲酸酯化合物
Figure A9810162400071
其中R4，R5，R6和R7是具有1-13个碳原子的烃基和R8是具有1-8个碳原子的亚烷基；
(iii)具有下式的二硫代氨基甲酸盐其中R4和R5表示具有1-8个碳原子的烷基，M表示周期表IIA，IIIA，VA，VIA，IB，VIB，VIII族的金属和从结构式
Figure A9810162400073
的胺形成的盐结构部分，R11，R12和R13独立地选自氢和具有1-18个碳原子的脂族基团和n是M的价态；
(iv)具有下式的二硫代磷酸盐
其中X和X1独立地选自S和O，R9和R10表示氢和具有1-22个碳原子的烷基，M表示周期表IIA，IIIA，VA，VIA，IB，VIB，VIII族的金属和从结构式 的胺形成的盐结构部分，R11，R12和R13独立地选自氢和具有1-18个碳原子的脂族基团和n是M的价态；和
(v)具有下式的二硫代磷酸酯
其中R4和R5可以相同或不同并选自具有1-8个碳原子的烷基；和钼配合物与硫化合物的比例是约1∶5-约5∶1。
本发明的另一方面涉及具有改进润滑性能和包括主要部分的具有润滑粘度的油和约0.1-10.0wt％的组合物的润滑组合物，前一组合物包括(1)通过约1摩尔脂肪油、约1.0-2.5摩尔二乙醇胺和足以得到以配合物重量为基础计约0.1-12.0％的钼的钼源进行反应而制备的有机钼配合物，和(2)通式I，II，III，IV或V的硫化合物。
                    本发明的详细叙述
本发明的有机钼组分是由US4,889,647(被引入本文供参考)中描述的缩合方法将脂肪油、二乙醇胺和钼源顺序进行反应来制备。反应得到反应产物混合物。据信主组分具有以下结构式
其中R表示脂肪油残基。优选的脂肪油是含有12个碳原子的高级脂肪酸的甘油基酯并可含有22个碳原子和更多。这一酯类通常已知为植物和动物油。特别有用的植物油是从椰子、玉米、棉籽、亚麻子、花生、大豆和葵花子得到的油类。类似地，使用动物脂肪油如牛油。
钼源是能够与脂肪油和二乙醇胺的中间反应产物进一步反应形成酯型钼配合物的一种含氧的钼化合物。钼源包括钼酸铵，氧化钼和它们的混合物。
通式I的1，3，4-噻二唑可通过US4,761,842和US4,880,437中描述的方法来制备。萜烯残基优选是从具有以下结构式的蒎烯和苎烯得到的：
由R和R1表示的烷基优选含有1-22个碳原子并可以是支链或直链。特别优选的是其中两烷基一起含有总共至少22个碳原子的化合物。在通式I中的基团R2和R3表示含有1-22个碳原子的支链或直链烷基和环脂族基团如环己基、环戊基和环庚基。
通式II的二硫代氨基甲酸酯是在US4,648,985(被引入本文供参考)中描述的已知化合物。该化合物的特征在于基团R4-R7，它们可以相同或不同并是具有1-13个碳原子的烃基。基团R8是脂族基团如含有1-8个碳原子的直链和支链亚烷基。特别优选的是以商品名VANLUBE7723购自R.T.Vanderbilt Company，Inc.的亚甲基双(二硫代氨基甲酸二丁基酯)。
通式III的二硫代氨基甲酸盐是已知的化合物。一种制备它的方法公开于US2,492,314中。在通式III中的基团R4和R5表示具有1-8个碳原子的支链或直链烷基。特别优选的是二硫代氨基甲酸锑。
通式IV的二硫代磷酸盐是已知的商品物质。一种制备它的方法见于US4,215,067。基团R9和R10表示具有1-22个碳原子的支链和直链烷基并可从脂肪酸得到。通式III和IV中的金属离子选自元素周期表IIA，IIIA，VA，VIA，IB，VIB，VIII族。化合物的铵盐也是本发明的有用协合物。举例来说，盐包括由烷基胺和混合烷基胺制备的那些盐类。特别有用的是脂肪酸胺类。
通式V的二硫代磷酸酯是已知的化合物。一种制备它的方法公开于US3,567,638。在通式V中的基团R4和R5可以相同或不同并选自支链和直链烷基。优选的是含有1-8个碳原子的基团。
硫化合物已知具有某些润滑性能，如在各种润滑介质中对氧化、磨损和腐蚀的抑制作用。然而，有时候硫化合物单独对于许多工业和汽车润滑剂的不同重型应用无法提供足够的磨损保护作用。
而且，在某些条件下，高浓度的硫化合物可对润滑剂的总性能有不利影响。
出乎意外的是，以上硫化合物在按一定比例与有机钼化合物混合时将会产生协合抗磨效果。协合作用由含有约1-5重量份的硫化合物和约5-1重量份的钼化合物的组合物显示出来。
协合组合的另一优点是组合物具有良好的抗氧化性能。甚至在硫化合物不具有抗氧化活性的情况下，与钼化合物的结合提供了具有良好总体抗氧化性能的组合物。
协合组合物可由已知方法引入任何润滑介质中。该组合物使配制为油或脂的天然和合成润滑剂具有氧化抑制作用和耐特压性能。
用作润滑剂载体的基础油典型地是在汽车和工业应用中使用的天然和合成油，如汽轮机润滑油，液压油，齿轮油，曲轴箱润滑油和柴油。天然基础油包括矿物油，石油润滑油，石蜡油和生态上有益的植物油。典型的合成油包括季戊四醇酯类，聚α-烯烃，氢化矿物油，硅氧烷和硅烷。
本发明的组合物能够以足以产生所需抗磨特性的量引入到润滑剂中。约0.1-10.0％的量对于大多数应用来说是足够的。优选的范围是约0.5-约3.0wt％的总润滑剂组合物。
润滑组合物含有其它常规的添加剂，这取决于润滑剂的预定目的。例如，配制剂可含有腐蚀抑制剂如烷基萘磺酸的金属盐，破乳剂，分散剂，洗涤剂和补充抗氧化剂，尤其烷基化二苯基胺。
润滑脂配制剂含有各种增稠剂，如硅酸盐矿物，金属皂和有机聚合物。
给出下面的实施例以说明本发明但决不限定本发明。所有的百分数和份数都是以重量计，除非另有说明。
                        实施例1
使用原形法列克司摩擦机模拟汽车发动机的气门机构磨损来进行实验室试验。用超声波洗涤机将V-汽缸体和活塞销在矿油精中洗涤，用丙酮漂洗，风干和称重。将试验样品(60g)放入油杯中。开动马达并将输油臂放入大钢轮上。在达到227kg的参比负载后，脱开大钢轮和负载保持恒定达3.5小时。之后关掉马达。V-汽缸体和活塞销被洗涤，干燥和称重。记录重量损失(磨损的测量值)并列于表I中。
用钼配合物与本发明的下面无灰分硫化合物协合剂一起进行试验：S-二羰基丁氧基乙基O，O-二丙基二硫代磷酸酯(下面称作二硫代磷酸酯)和亚甲基双(二硫代氨基甲酸二丁基酯)。钼配合物是椰子油、2，2’-亚胺基双乙醇和钼酸六铵盐的反应产物。基础油是加氢精制链烷烃油(ISO VG22，由Sun Refining and Marketing Co.销售)。
表I中列出的结果表明，钼配合物和以上硫化合物可用作抑制磨损的协合剂。
                     表I
           改性法列克司磨损试验
               组分，质量％样品                 1      2      3    4    5    6钼配合物             1.0    1.5    --   0.5  --   0.5二硫代磷酸酯         --     --     1.0  0.5  --   --亚甲基双(二硫代氨    --     --     --   --   1.5  1.0基甲酸二丁基酯)试验参数试验时间(分钟)       40*   75*   20* 210  210  210总重量损失(mg)       433    542.8  --   14.6 86.4 3.4
*因过多的磨损而中止试验。实施例2
用同样的钼配合物与下面的硫化合物协合剂的金属盐结合来进行实施例1中所描述的改性法列克司磨损试验：二月桂基二硫代氨基甲酸镍、二-2-乙基己基二硫代磷酸钙、二-2-乙基己基二硫代磷酸铝、二-2-乙基己基二硫代磷酸碲、和叔辛基磷酸的C12-14烷基铵盐(下面称作二硫代磷酸铵盐)。基础油是加氢精制链烷烃油(ISO VG22)。
列于表II中的结果表明，钼配合物和以上硫化合物的盐可用作抑制磨损的协合剂。
                        表II
              改性法列克司磨损试验
                   组分，质量％样品              7       8       9      10      11     12     13     14     15     16     17钼配合物          1.5     --      0.5    --      0.5    --     0.5    --     0.5    --     0.5二硫代氨基甲酸镍  --      1.5     1.0    --      --     --     --     --     --     --     --二硫代磷酸钙      --      --      --     1.5     1.0    --     --     --     --     --     --二硫代磷酸铝      --      --      --     --      --     1.5    1.0    --     --     --     --二硫代磷酸碲      --      --      --     --      --     --     --     1.5    1.0    --     --二硫代磷酸铵盐    --      --      --     --      --     --     --     --     --     1.5    1.0试验参数试验时间(分钟)    75*    5*     210    5*     210    210    210    120*  210    2*    210总重量损失(mg)    542.8   366.8   14.9   366.6   90.1   33.5   18.4   84.8   17.7   5.6** 41.9
*因过多的磨损而中止试验。
**高磨损破坏实施例3
基本上根据Chia-Soon Ju等人(J.Am.Soc.Lubricating Eng.，40，2，75-83，1984年)描述的方法进行薄膜吸氧试验。借助于改进旋转弹内氧化试验方法ASTM D-2272在汽车发动机中模拟高温氧化过程的条件下测量润滑剂的氧化诱导时间。用1.5g加氢精制链烷烃油(ISOVG22)样品进行该试验。在实施例1中描述的本发明组合物和供对比用的各组分以表III中列出的量加入到油中。在160℃和初始氧气压力620.6kPa(90psi)下进行测试。“通过”油具有高诱导时间，而“未通过”油具有低诱导时间。本发明的组合物显示出良好的抗氧化效果，如表III中数据所说明。
                表III
             薄膜吸氧试验
             组分，质量％样品                18     19     20    21钼配合物            1.0    1.5    --    0.5亚甲基双(二硫代            --     1.5   1.0氨基甲酸二丁基酯)试验参数平均诱导时间(分钟)  10     10     75    93
上述实施方案揭示了本发明的各个方面。对于本技术领域中普通专业人员来说各种变化是显然的，而且这些改进被包括在所附权利要求限定的本发明的范围内。

Claims (10)

1.协合抗磨损组合物，由以下组分组成：
(a)有机钼配合物，通过约1摩尔脂肪油，约1.0-2.5摩尔二乙醇胺和足以得到以配合物重量为基础计约0.1-12.0％的钼的钼源进行反应而制备，和
(b)有机硫化合物，选自具有下式的1，3，4-噻二唑类：
Figure A9810162400021
其中R和R′独立地选自C1-22烷基，萜烯残基和下式的马来酸残基
和R2和R3表示C1-22烷基和C5-7环烷基，R2或R3可以是氢和当R2或R3是C9-22烷基时R和R1可以是氢；和钼配合物与硫化合物的比例是约1∶5-约5∶1。
2.根据权利要求1的组合物，其中1，3，4-噻二唑化合物是2，5-双蒎烷基-1，3，4-噻二唑。
3.由以下组分组成的协合抗磨损组合物：
(a)有机钼配合物，通过约1摩尔脂肪油，约1.0-2.5摩尔二乙醇胺和足以得到以配合物重量为基础计约0.1-12.0％的钼的钼源进行反应而制备，和
(b)具有下式的
其中R4，R5，R6和R7是具有1-13个碳原子的烃基和R8是具有1-8个碳原子的亚烷基；和钼配合物与硫化合物的比例是约1∶5-约5∶1。
4.根据权利要求3的组合物，其中二硫代氨基甲酸酯化合物是亚甲基双(二硫代氨基甲酸二丁基酯)。
5.由以下组分组成的协合抗磨损组合物：
(a)有机钼配合物，通过约1摩尔脂肪油，约1.0-2.5摩尔二乙醇胺和足以得到以配合物重量为基础计约0.1-12.0％的钼的钼源进行反应而制备，和
(b)具有下式的二硫代氨基甲酸盐
Figure A9810162400031
其中R4和R5表示具有1-8个碳原子的烷基，M表示周期表IIA，IIIA，VA，VIA，IB，VIB，VIII族的金属和从结构式
Figure A9810162400032
的胺形成的盐结构部分，R11，R12和R13独立地选自氢和具有1-18个碳原子的脂族基团和n是M的价态；和钼配合物与硫化合物的比例是约1∶5-约5∶1。
6.根据权利要求5的协合组合物，其中二硫代氨基甲酸盐是锑盐。
7.由以下组分组成的协合抗磨损组合物：
(a)有机钼配合物，通过约1摩尔脂肪油，约1.0-2.5摩尔二乙醇胺和足以得到以配合物重量为基础计约0.1-12.0％的钼的钼源进行反应而制备，和
(b)具有下式的二硫代磷酸盐
其中X和X1独立地选自S和O，R9和R10表示氢和具有1-22个碳原子的烷基，M表示周期表IIA，IIIA，VA，VIA，IB，VIB，VIII族的金属和从结构式
Figure A9810162400034
的胺形成的盐结构部分，R11，R12和R13独立地选自氢和具有1-18个碳原子的脂族基团和n是M的价态；和钼配合物与硫化合物的比例是约1∶5-约5∶1。
8.由以下组分组成的协合抗磨损组合物：
(a)有机钼配合物，通过约1摩尔脂肪油，约1.0-2.5摩尔二乙醇胺和足以得到以配合物重量为基础计约0.1-12.0％的钼的钼源进行反应而制备，和
(b)具有下式的二硫代磷酸酯
Figure A9810162400041
其中R4和R5可以相同或不同并选自具有1-8个碳原子的烷基；和钼配合物与硫化合物的比例是约1∶5-约5∶1。
9.根据权利要求8的组合物，其中酯是S-二羰基丁氧基乙基O，O-二丙基二硫代磷酸酯。
10.润滑组合物，它包括主要部分的具有润滑粘度的油和约0.1-10.0wt％的协合抗磨损组合物，该抗磨损组合物由以下组分组成：
(a)有机钼配合物，通过约1摩尔脂肪油，约1.0-2.5摩尔二乙醇胺和足以得到以配合物重量为基础计约0.1-12.0％的钼的钼源进行反应而制备，和
(b)有机硫化合物，选自：
(i)具有下式的1，3，4-噻二唑类：其中R和R1独立地选自C1-22烷基，萜烯残基和下式的马来酸残基
Figure A9810162400043
和R2和R3表示C1-22烷基和C5-7环烷基，R2或R3可以是氢和当R2或R3是C9-22烷基时R和R1可以是氢；
(ii)具有下式的二硫代氨基甲酸酯化合物
其中R4，R5，R6和R7是具有1-13个碳原子的烃基和R8是具有1-8个碳原子的亚烷基；
(iii)具有下式的二硫代氨基甲酸盐其中R4和R5表示具有1-8个碳原子的烷基，M表示周期表IIA，IIIA，VA，VIA，IB，VIB，VIII族的金属和从结构式
Figure A9810162400053
的胺形成的盐结构部分，R11，R12和R13独立地选自氢和具有1-18个碳原子的脂族基团和n是M的价态；
(iv)具有下式的二硫代磷酸盐
其中X和X1独立地选自S和O，R9和R10表示氢和具有1-22个碳原子的烷基，M表示金属和如上定义的盐部分，以及n是M的价态；和
(v)具有下式的二硫代磷酸酯
其中R4和R5可以相同或不同并选自具有1-8个碳原子的烷基；和钼配合物与硫化合物的比例是约1∶5-约5∶1。
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EP0874040A1 (en) 1998-10-28
CA2235182C (en) 2004-08-10
JP3090904B2 (ja) 2000-09-25
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DE69714213D1 (de) 2002-08-29
CN1098348C (zh) 2003-01-08

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