CN1103807C - 用于润滑组合物的抗磨剂 - Google Patents

用于润滑组合物的抗磨剂 Download PDF

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CN1103807C
CN1103807C CN98803628A CN98803628A CN1103807C CN 1103807 C CN1103807 C CN 1103807C CN 98803628 A CN98803628 A CN 98803628A CN 98803628 A CN98803628 A CN 98803628A CN 1103807 C CN1103807 C CN 1103807C
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J·S·普卡斯
R·F·瓦茨
R·K·尼伯特
R·A·布劳赫
J·莱尔
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Abstract

用作油质组合物的抗磨剂的含硫硼酸酯化合物，包括具有通式(I)的无环硼酸硫酯，其中R1表示具有4-12个碳原子的烃基，R2和R3独立地表示-(OR4)nSR1和-(OR4)nSR1OH；R4表示具有1-6个碳原子的烃基；n为约1-4的整数；且1和m独立地为0、1或2；或具有通式(II)的硫烷基取代环状偏硼酸酯，其中n、R1和R4定义如结构式(I)；或结构式(I)无环化合物与结构式(II)环状化合物的混合物。

Description

用于润滑组合物的抗磨剂
本发明一般涉及用作油质组合物的抗磨剂的化合物。尤其是，本发明涉及作为抗磨剂而适用于润滑和动力传递油或液体的无环硼酸硫酯和无环偏硼酸硫烷基酯化合物。
已知含硼化合物，尤其是硼酸酯在加入润滑油时可用作抗磨剂。EP-A-0216909公开了偏硼酸酯抗磨剂，它具有以下结构式：
其中每个R独立地为氢原子或包含1-18个碳原子的烃基，且每个R’独立地为包含2-4个碳原子的亚烷基。
此外熟知，含硫化合物可在润滑组合物中用作抗磨剂，并能进一步提高硼基抗磨剂的效果。上述欧洲专利说明书公开，将所定义的偏硼酸酯与油溶性硫化有机化合物结合使用，两者的相对量足以产生0.5∶1-20∶1的硫/硼重量比。
同时具有硼和硫的抗磨剂公开于，例如美国专利3303130，它描述了一种具有以下通式的有机硫烷基硼酸酯抗磨剂：
Figure C9880362800062
其中R选自氢原子、包含1-16个碳原子的烷基、芳基、烷芳基、芳烷基和环烷基，且n为2-16的整数(包含2和16)。这些化合物通过硫醇与硼酸以至少3∶1的摩尔比反应形成，这样可得到硫与硼的重量比为3.33∶1的抗磨剂。美国专利4492640公开了通过醇、羟基硫和硼化合物反应形成的类似化合物、及其作为减磨剂在润滑油组合物中的应用。
由于对润滑油添加剂的不断要求以及制造商之间的激烈竞争，一直需要对抗磨剂进行改性。本发明提供了一种用于润滑油的改进抗磨剂，它包含能够提供较高硼/硫重量比，同时又能产生抗氧化性能和摩擦调节剂性能的单个化合物。
第一方面，本发明提供了一种含硫的硼酸酯化合物，它包含：
具有通式(I)的无环硫烷基硼酸酯：
Figure C9880362800071
其中R1表示具有4-12个碳原子的烃基，R2和R3独立地表示-(OR4)nSR1或-(OR4)nSR1OH；R4表示具有1-6个碳原子的烃基；n为约1-4的整数；且l和m独立地为0、1或2；或
具有通式(II)的硫烷基取代环状偏硼酸酯：
其中n、R1和R4定义如结构式(I)；或
结构式(I)无环硫烷基硼酸酯与结构式(II)硫烷基取代环状偏硼酸酯的混合物。
第二，本发明提供了一种油质组合物，它包含或通过混合以下成分而制成：主要量的润滑粘性油或动力传递油以及少量的在本发明第一方面定义的含硫硼酸酯。
第三，本发明提供了一种制备油质组合物的方法，包括，将主要量的润滑粘性油或动力传递油与少量的在本发明第一方面定义的含硫硼酸酯进行混合。
第四，本发明提供了一种添加剂浓缩物，其中包含按照本发明第一方面定义的含硫硼酸酯化合物和用于其的油质载体。
第五，本发明提供了一种用于形成含硫化合物，例如在本发明第一方面定义的含硫硼酸酯化合物的方法，该方法包括将至少当量摩尔量的硼酸与烷氧基烷基硫进行反应。
第六，本发明提供了含硫硼酸酯化合物在提高润滑油或动力传递油或液体的抗磨性能中的应用。
现在，将本发明详细讨论如下。
在本发明的含硫硼酸酯化合物中，无论是无环的还是环状的，优选的是，R1表示具有6-9个碳原子的烃基，R4表示具有2-4个碳原子的烃基；且l、m和n都1。是更优选的是，R1表示具有6个碳原子的烃基，且R4表示具有2个碳原子的烃基。
本发明的无环硼酸硫酯和环状偏硼酸硫酯抗磨剂可以是烷氧基烷基与硼酸以至少约1∶1的摩尔比的缩合产物。合适的烷氧基烷基硫是具有结构式(III)的化合物：
R1SR4OH(III)
其中R1和R4定义如上。优选的结构式III化合物包括羟乙基十二烷基硫、1-羟基-2-甲基-3-硫代-癸烷和羟乙基辛基硫(HEOS)。烷氧基烷基硫可包含单个化合物或其混合物。
在与硼酸反应时，烷氧基烷基硫可形成能够同时包含结构式I无环化合物和结构式II环状化合物的反应产物。该反应非常有利于形成环状偏硼酸硫酯，而且该反应产物实际上可仅包含微量、或基本上没有无环硼酸硫酯。硼酸和羟基烷基硫可以约1∶1的摩尔比进行反应，或在稍微摩尔过量的烷氧基烷基硫(不超过约2∶1)的存在下进行反应。该反应可在0-150℃，优选60-120℃的温度，以及-100至0，优选-70至-30kPa的压力下进行反应。
硼酸和烷氧基烷基硫可在纯净态下或在惰性或非参与性极性溶剂中进行。拿羟乙基辛基硫(HEOS)和硼酸反应物作为例子，该反应据信进行如下：
Figure C9880362800091
本发明抗磨剂可有利加入的润滑油和动力传递油衍生自天然油、合成油或天然油与合成油的混合物。合适的油包括通过合成蜡与疏松石蜡的异构化而得到的基本原料、以及通过加氢裂化原油的芳族和极性组分而制成的基本原料。
合成油包括烃油和卤代烃油，如低聚的、聚合的和共聚的烯烃(如，聚丁烯、聚丙烯、丙烯-异丁烯共聚物、氯化聚乙烯、聚(1-己烯)、聚(1-辛烯)、聚(1-癸烯)、及其混合物)；烷基苯(如，十二烷基苯、十四烷基苯、二壬基苯、二(2-乙基己基)苯)；聚苯(如，联苯基、三苯基、烷基化聚苯)就烷基化二苯醚、烷基化二苯硫、及其衍生物、类似物和同系物。
合成油还包括烯化氧聚合物、共聚物及其衍生物，其中端羟基已通过(例如)酯化或醚化反应而改性。这种合成油的例子为，通过氧化乙烯或氧化丙烯的聚合反应而制成的聚氧化烯聚合物；以及这些聚氧化烯聚合物的烷基或芳基醚(如，数均分子量为1000的甲基聚异丙二醇醚、和数均分子量为1000-1500的聚丙二醇的二苯醚)、及其单-和多羧酸酯(如，乙酸酯、混合C3-C8脂肪酸酯、和四亚乙基二醇的C12氧代二酯)。
另一种合适的合成润滑油包括二羧酸(如，邻苯二甲酸、琥珀酸、烷基琥珀酸和链烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、富马酸、己二酸、亚油酸二聚体、丙二酸、烷基丙二酸和链烯基丙二酸)与醇(如，丁醇、己醇、十二烷醇、2-乙基己醇、乙二醇、二甘醇单醚和丙二醇)的酯。这些酯的具体例子包括己二酸二丁酯、癸二酸二(2-乙基己基)酯、富马酸二正己酯、癸二酸二辛酯、壬二酸二异辛酯、壬二酸二异癸酯、间苯二甲酸二辛酯、邻苯二甲酸二癸酯、癸二酸二(二十烷基)酯、亚油酸二聚体的2-乙基己酯、以及1摩尔癸二酸与2摩尔四亚乙基二醇和2摩尔2-乙基己酸反应形成的混合酯。
可用作合成油的酯还包括，由C5-C12单羧酸和多元醇和多元醇醚，如新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇和三季戊四醇得到的那些。
硅基油(如，聚烷基-、聚芳基-、聚烷氧基-或聚芳氧基-硅氧烷油和硅酸酯油)是另一种有用的合成油。这些油包括硅酸四乙酯、硅酸四异丙基酯、硅酸四-(2-乙基己基)酯、硅酸四-(4-甲基-2-乙基己基)酯、硅酸四-(叔丁基苯基)酯、六-(4-甲基-2-戊氧基)-二硅氧烷、聚(甲基)硅氧烷和聚(甲基苯基)硅氧烷。其它的合成润滑油包括含磷酸的液体酯(如，磷酸三甲苯基酯、磷酸三辛酯、和癸基磷酸的二乙酯)、聚四氢呋喃和聚α-烯烃。
天然油包括动物油、植物油(如，蓖麻油和猪油)、石油、矿物油和衍生自煤或页岩的油。本发明抗磨剂可加入的矿物油包括所有的常用矿物油基本原料。其中包括化学结构为环烷基或链烷基类型的油。这些油可使用酸、碱、和粘土或其它试剂，如氯化铝，采用常规方法进行精炼，或可以是萃取油，例如使用苯酚、二氧化硫、糠醛或二氯二乙醚之类的溶剂进行溶剂萃取而得到。它们还可进行氢化处理或加氢精制、通过冷冻或通过催化处理而脱蜡、或加氢裂解。矿物油还可由天然粗品制成，或由异构化蜡或其它精炼工艺的残余物组成。
润滑油或动力传递油可衍生自未精炼油、高精炼油、再生润滑油或其混合物。未精炼油直接得自天然或合成原料(如，页岩或焦油砂沥青)，而无需进一步纯化或处理。未精炼油的例子包括直接得自蒸馏操作的页岩油、直接得自蒸馏的石油、或直接得自酯化工艺的酯油，它们分别都可无需进一步处理而使用。精炼油类似于未精炼油，只是精炼油已经过一个或多个纯化步骤处理以提高一种或多种性能。合适的纯化方法包括蒸馏、加氢处理、脱蜡、溶剂萃取、酸或碱萃取、过滤和渗滤，这些都是本领域普通技术人员所已知的。再生润滑油在类似于得到精炼油的工艺中，通过处理废油而得到。这些再生润滑油也称作再生或再处理油，通常另外通过各种方法进行处理以去除废添加剂和油破坏产物。
本发明的化合物可作为抗磨剂加入润滑油和动力传递油中，其用量为0.001-5，优选0.001-1.5，最优选0.2-1.0％质量。通过配制，油质物质可包含其它添加剂，如粘度调节剂、辅助抗氧化剂、摩擦调节剂、分散剂、消泡剂、辅助抗磨剂、倾点抑制剂、洗涤剂、和防锈剂。
可以理解，该组合物的各种组分，无论是基本的还是最佳的和常规的，都可在配制、储存或使用条件下进行反应，因此本发明还提供了通过任何这类反应而得到的产物。
包含以上添加剂的各种组合物通常混入原油中的量要足以产生其常规的辅助作用。这些添加剂常规混入润滑油中的量的对比例如下：添加剂        ％重量(宽)*    ％重量(优选)粘度添加剂    .01-12         .01-4阻蚀剂        .01-5          .01-1.5氧化抑制剂    .01-5          .01-1.5分散剂        .1-20          .1-8倾点抑制剂    .01-5          .01-1.5消泡剂        .001-3         .001-0.15扩链剂        .001-5         .001-1.5摩擦添加剂    .01-5          .01-3洗涤剂/防锈剂 .01-10         .01-3原油          余量           余量*活性成分
这些添加剂可以常规方式加入润滑油中。因此，它们可通过分散或溶解在油中而直接加入油。这种混合可在室温下或高温下进行。此外，可首先将添加剂形成其油质载体中包含有所述添加剂的浓缩物，然后将其与油混合。最终配方通常可包含2-20％质量的添加剂。
合适的分散剂包括烃基琥珀酰亚胺、烃基琥珀酰胺、烃基取代琥珀酸的混合酯/酰胺、烃基取代琥珀酸的羟基酯、芳族酸的酰胺、以及烃基取代苯酚、甲醛和聚胺的Mannich缩合产物。也可使用这些分散剂的混合物。分散剂可选采用本领域已知的常规试剂进行处理(参见，美国专利3254025、3505677、和4857214)。
优选与本发明硫硼抗磨剂结合使用的分散剂为链烯基琥珀酰亚胺。这些烃基取代琥珀酰亚胺是使用各种胺、聚胺和胺衍生物制成的，这是本领域普通技术人员所熟知的。特别合适的分散剂的例子为聚异丁烯琥珀酸酐的聚异丁烯基琥珀酰亚胺反应产物，其中聚异丁烯部分的数均分子量为500-5000，优选800-2500，且亚烷基聚胺，如三亚乙基四胺或四亚乙基五胺、或每个分子包含3-12个氮原子的聚胺的混合物在本领域中称作PAM。已用磷的无机酸(或其酸酐)和硼化试剂处理的链烯基琥珀酰亚胺也适于与本发明化合物结合使用，而且与由含氟弹性体和含硅弹性体之类物质制成的弹性密封更加相容。
适于与本发明添加剂结合使用的抗氧化剂包括胺类和酚类抗氧化剂。胺类抗氧化剂的例子包括苯基α-萘胺、苯基β-萘胺、和双-烷基化二苯胺(如，p，p’-双(烷基苯基)-胺，其中烷基分别包含8-12个碳原子)。酚类抗氧化剂的例子包括位阻酚(如，2，6-二叔丁基苯酚、4-甲基-2，6-二叔丁基苯酚)和双酚(如，4，4”-亚甲基双(2，6-二叔丁基苯酚)。磷化合物，如ZDDP、或磷酸酯也常作为抗氧化剂加入芳族传输液体(ATF)或客车机油(PCMO)中。除了产生抗磨性能，本发明化合物还可赋予润滑组合物以抗氧化剂作用，因此可降低专加入润滑组合物配方中的抗氧化剂添加剂的量或没有。
合适的摩擦调节剂是具有一个极性头基团和亲油尾基团的分子。极性头基团可使该分子吸附到摩擦表面上。这些基团可以是，但不限于，胺、单-和二乙氧基化胺、羧酸、酰胺、酰亚胺、醇、酚、硫醇、磺酸、磷酸盐、磷酸酯、酯及其混合物。亲油基团通常为烷基，一般为直链烷基。这些烷基的碳原子数为C8-C30，优选C12-C20。它们可以是饱和的或不饱和的，且可包含杂原子，如氮或硫，只要这些杂原子不会对该分子发挥其摩擦调节剂作用的能力产生不利影响。
适于与本发明抗磨剂结合使用的摩擦调节剂的例子包括油酰胺、牛油胺、二乙氧基化牛油胺、N，N-双(2-羟乙基)-十八烷基胺、N，N-双(2-羟乙基)-硬脂酰氧基丙胺、油酸、N，N-羟乙基，N-(N’，N’-双(2-羟乙基)乙胺)-硬脂胺、以及得自异硬脂酸与四亚乙基五胺的二酰胺。
适用作粘度调节剂的化合物一般为高分子量烃类聚合物，其中包括聚酯。油溶性粘度调节剂聚合物的重均分子量一般为10000-1000000，优选20000-500000，这是通过凝胶渗透色谱或光散射法测得的。
合适的粘度调节剂的对比例为聚异丁烯、乙烯与丙烯和高级α-烯烃的共聚物、聚甲基丙烯酸酯、聚甲基丙烯酸烷基酯、甲基丙烯酸酯共聚物、不饱和二羧酸与乙烯基化合物的共聚物、苯乙烯与丙烯酸酯的共聚物、和苯乙烯/异戊二烯、苯乙烯/异戊二烯和异戊二烯/丁二烯的部分氢化共聚物、以及丁二烯和异戊二烯和异戊二烯/二乙烯基苯的部分氢化均聚物。
加入本发明抗磨剂的润滑油和动力传递油还可包含防锈剂，如非离子聚氧化亚烷基多元醇及其酯、聚氧化亚烷基苯酚和阴离子烷基磺酸、以及缓蚀剂，如噻二唑聚硫醚(含5-50个碳原子)、其衍生物及其聚合物；1，3，4-噻三唑的衍生物；以及硫代和多硫代亚磺酰胺噻二唑。这些油还可包含消泡剂，其中包括聚丙烯酸酯型消泡剂、聚硅氧烷型消泡剂、和氟硅氧烷型消泡剂；以及洗涤剂，如过碱性和这些磺酸钙、苯酚钙、磺酸镁和苯酚镁。
现通过以下实施例来说明本发明。
实施例1(合成)
在5升三颈烧瓶中，将2280克羟乙基辛基硫(12摩尔)和744克硼酸粉末(12摩尔)混合。该烧瓶配有搅拌器、温度计和连接到真空的冷凝器。将烧瓶加热至110℃，并将烧瓶内的压力降至-70kPa。几分钟之后，水开始释放出来。将烧瓶内的温度降至100℃，这时停止反应，然后在无助条件下进行放热反应，直到放出2摩尔当量的水并收集。然后加热，直到另外放出1摩尔当量的水并收集。
该产物通过多种分析技术进行定性。HPLC分离分析表明，形成了一种主要物质。13C NMR光谱表明，该物质在62.8(1C)ppm上相对TMS具有一个与硼酸化烷氧基亚甲基碳有关的特征尖单共振。11B NMR表明，相对H2BO3只在-3ppm处有一个硼-氧酯信号。碳的简单性和硼NMR光谱结果表明一种非常对称的偏硼酸酯结构。在33(1C)、31.8(1C)、31.2(1C)、29.6(1C)、28.8(1C)、28.6(1C)、22.4(1C)和13.6(1C)处发现与羟乙基辛基硫有关的特征碳信号。
实施例2
为了说明本发明化合物在润滑油中产生抗磨和抗氧化作用的能力，如下配制添加剂包装(Adpacks)A-G，然后以7％质量的处理比率加入粘度调节剂原油以形成调配油。将该调配油进行LMOT测试(以下描述)以确定抗氧化性能的提高，并进行FZG测试(Four Squre GearTest，ASTM D-5182)以确定抗磨性能。
每个Adpack(A-G)包含：
0.45％二苯胺(抗氧化剂)；
0.15％摩擦调节剂；
0.001％氟化硅氧烷表面活性剂；
3.5％硼酸化PIBSA-PAM(分散剂)；和
基本原油。
它们的差别在于，分散剂中PIB的分子量、实施例1的HEOS-偏硼酸酯是否存在和含量、是否存在0.50％甲苯基三唑(阻蚀剂)、以及基本原油的量，如下表所示。
ADPACK  PIB的分子量 HEOS-偏硼酸酯(量) 阻蚀剂 基本原料(量)
    A     950     0.46    -    2.439
    B     950     0.46    √    1.939
    C     2200     0.46    -    2.439
    D     2200     0.46    √    1.939
    E     950     -    -    2.899
    F     950     0.92    -    2.899
    G     2200     0.92    √    1.479
√表示存在，-表示不存在
所有的百分数和量都是％质量。
在Adpack中，所有的百分数和量都是％质量。
实验室多氧化试验(LMOT)用于测定润滑剂组合物耐热和空气氧化的能力。在LMOT中，将50毫升的测试润滑剂、2.2克铁锉屑、和0.5克的1％铜溶液(NuodexCopper 82环烷酸铜在溶剂油的1％溶液，通过将Nuodex 8％铜溶解在100NLP油(Exxon Chemical)中而制成)。在150±2℃的温度下，将空气通过样品(25±2毫升/分钟)。每天将1滴样品润滑剂放在吸墨纸上，直到出现污泥。LMOT的结果以观察到污泥时的天数计(没有污泥的天数)。
下表1汇总了这些结果。
表1
                   A      B    C    D    E    F    G100℃下的粘度          8.2    8.2  8.8  8.9  8.0  8.6  10(mm2S-1)320°F(160℃)下的LMOT  8.5    9    11   10   7    11   11(没有污泥的天数)FZG(失败的阶段)        ---    ---  ---  10   8    11   12
如表1数据所示，相对没有硼酸酯(Adpack E)的调配油来说，将包含0.46％质量HEOS偏硼酸酯的adpack D加入基本原油中可提高FZG两个负载阶段。使用附加HEOS偏硼酸酯(Adpack F和G)可进一步提高抗磨性能。LMOT试验的结果表明，HEOS偏硼酸酯能够同时用作抗氧化剂。具体地说，Adpack A至D(包含0.46％质量的HEOS偏硼酸酯)的数据表明，相对没有本发明添加剂(Adpack E)的调配油来说，LMOT提高1.5-3天。与用Adpack E调配的油相比，加入Adpack F或G(包含0.92％质量的HEOS偏硼酸酯)可提高LMOT结果4天。
实施例3
为了说明将本发明添加剂与常用磷基添加剂进行共同调配时的结果，配制出3种油组合物，分别包含0.31％质量的HEOS偏硼酸酯以及0.30％质量的磷酸三苯酯(TPP)(Adpack H)、0.16％质量的混合亚磷酸酯(Adpack I)或0.19％质量的亚磷酸二丁酯(DBP)(Adpack J)。将这三种调配油进行FZG和LMOT测试。结果如下。
表2
                     H       I       J100℃下的粘度(mm2S-1)  8.03    7.99    7.99320°F(160℃)下的LMOT    10.5    9       10.5(没有污泥的天数)FZG(失败的阶段)          9       10      12
表2数据表明，包含HEOS偏硼酸酯(0.31％质量)的adpack在与磷基摩擦调节剂共调配时可在调配油中同时产生抗磨和抗氧化性能。
实施例4
在工业标准Ford MERCON Vickers Pump Test(Ford MotorCompany，MERCON Automatic Transmission F1uid Specification ForService，1987年3月5日)中，将HEOS偏硼酸酯(0.31％质量)-分散剂混合物(PIBSA PAM(950Mw聚异丁烯))(3.5％重量)与完全调配参考ATF(L)(不含任何磷基的、或其它的抗磨剂)进行比较，其中所述HEOS-偏硼酸酯存在于汽车传输液体(K)中。如下表3所示，硼酸酯-分散剂混合物具有强抗磨性能，这在不含任何其它抗磨剂的AFT看来是惊人的。表4的数据是将添加处理油的Vi ckers Pump测量值与工业标准进行比较。
表3添加剂混合物         FAZG失败负载阶段K                    13L                    8
表4ATF液体抗磨结果      GM Dextron 111*通过/失败限度12毫克总磨损         15毫克最大总磨损
*Hydra-matic Division，General motors Corp.。
实施例5
为了说明HEOS偏硼酸酯和分散剂混合物在客车机油(PCMO)中的抗磨性能，将包含3.5％重量的标准PIBSA-PAM分散剂(M)的PCMO与包含同一分散剂和0.28％重量HEOS-偏硼酸酯(N)的PCMO进行比较。使用工业标准L38磨损试验(ASTM D-5119)比较两种样品的腐蚀损耗，结果在下表5中给出。如表5数据所示，仅加入0.28％重量的本发明抗磨剂就可提高抗磨结果约50％。
表5添加剂              L38磨损结果(毫克)M                   56.7N                   25.8
实施例6
润滑油通常需要满足有关氧化性能的工业标准。通常将抗氧化剂加入这些油中以防一般发生在使用时的氧化降解。在PCMO和ATF润滑剂中，通常为此使用磷化合物，如ZDDP或磷酸酯。以下试验表明，本发明HEOS偏硼酸酯抗磨剂的抗氧化效果非常高，因此油配方中无需另外使用ZDDP或亚磷酸酯抗氧化剂。
将包含Adpack N的ATF(实施例5所述)进行Ford MERCON A1uminumBeaker Oxidation Test(ABOT)(Ford MERCON方法BJ110-4)。在表6中，将所得结果与工业标准限度进行比较。
表6ABOT                     含有Adpack N的结果  工业限度△总酸值(TAN)            1.28                ＜4.0粘度增加百分数(250小时)  8.89                ＜40％IR差异(250小时)          22.2％              ＜40％戊烷不溶百分数(250小时)  0.53                ＜1.0Cu剥脱(300小时)          3b                  3bmax
实施例7
润滑油的摩擦性能在提高汽车的燃油消耗方面作用显著。配制者可根据这些要求，通过使用减磨剂来调节摩擦系数。据发现，HEOS偏硼酸酯与分散剂的混合物可产生优异的减磨特性。为了说明这些减磨效果，采用High Frequency Reciprocal Rig(HFRR)试验，将使用分散剂(5.5％重量)、消泡剂、洗涤剂、磷基抗磨剂/抗氧化剂和破乳剂完全调配的参考油(但不含任何减磨剂)与进一步用2.11％重量的HEOS偏硼酸酯和7.69％重量的分散剂(Adpack O)调配的同一油进行比较。
在HFRR试验中，将金属盘固定在一浴中的工作台上。连接400克物体的振动臂位于工作台对面。将金属球固定到振动臂的端部。将润滑油样品吸量到浴中，浸渍该盘，然后放低振动臂，使球与盘接触。然后将振动臂以20Hz的频率进行振动，冲程为1000微米。在每5分钟之后，将油样品的温度升高20℃(6个步骤，从40至140℃)。
将盘从工作台中取出，然后使用具有校准格子线的光学显微镜来测定因接触球而产生的磨损伤痕(直径X和Y)。
结果如下。
表7温度(℃)    参考油   参考油+Adpack O40          0.12     0.09960          0.126    0.11180          0.133    0.115100         0.133    0.115120         0.134    0.116140         0.135    0.119

Claims (12)

1.一种含硫的硼酸酯化合物，它包含：
具有通式(I)的无环硫烷基硼酸酯：
其中R1表示具有4-12个碳原子的烃基，R2和R3独立地表示-(OR4)nSR1或-(OR4)nSR1OH；R4表示具有1-6个碳原子的烃基；n为1-4的整数；且1和m独立地为0、1或2；或
具有通式(II)的硫烷基取代环状偏硼酸酯：
其中n、R1和R4定义如结构式(I)；或
结构式(I)无环硫烷基硼酸酯与结构式(II)硫烷基取代环状偏硼酸酯的混合物。
2.根据权利要求1所要求的含硫硼酸酯化合物，其中R1表示具有6-9个碳原子的烃基，R4表示具有2-4个碳原子的烃基；且1、m和n都是1。
3.根据前述权利要求中任何一项所要求的含硫硼酸酯化合物，其中R1表示具有6个碳原子的烃基，且R4表示具有2个碳原子的烃基。
4.一种油质组合物，它包含主要量的润滑粘性油或动力传递油、以及少量的含硫硼酸酯化合物，或通过混合而制成，所述含硫硼酸酯化合物包含：
具有通式(I)的无环硫烷基硼酸酯：
Figure C9880362800031
其中R1表示具有4-12个碳原子的烃基，R2和R3独立地表示-(OR4)nSR1或-(OR4)nSR1OH；R4表示具有1-6个碳原子的烃基；n为1-4的整数；且1和m独立地为0、1或2；或
具有通式(II)的硫烷基取代环状偏硼酸酯：
其中n、R1和R4定义如结构式(I)；或
结构式(I)无环硫烷基硼酸酯与结构式(II)硫烷基取代环状偏硼酸酯的混合物。
5.根据权利要求4所要求的油质组合物，其中所述含硫硼酸酯化合物占所述组合物的0.001-5重量％。
6.根据权利要求4或5所要求的油质组合物，其中R1表示具有6-9个碳原子的烃基；R4表示具有2-4个碳原子的烃基；且1、m和n都是1。
7.根据权利要求6所要求的油质组合物，其中R1表示具有6个碳原子的烃基，且R4表示具有2个碳原子的烃基。
8.根据权利要求4所要求的油质组合物，其中所述油为合成油或天然油。
9.根据权利要求4所要求的油质组合物，它还包含一种或多种分散剂、粘度调节剂、阻蚀剂、倾点抑制剂、消泡剂、抗磨剂、摩擦调节剂、洗涤剂、和防锈剂。
10.根据权利要求9所要求的油质组合物，其中所述分散剂为聚异丁烯琥珀酸酐与烃基聚胺的一种反应产物。
11.一种添加剂浓缩物，其中包含一种油质载体和含硫硼酸酯化合物，后者包含：
具有通式(I)的无环硫烷基硼酸酯：
其中R1表示具有4-12个碳原子的烃基，R2和R3独立地表示-(OR4)nSR1或-(OR4)nSR1OH；R4表示具有1-6个碳原子的烃基；n为1-4的整数；且1和m独立地为0、1或2；或
具有通式(II)的硫烷基取代环状偏硼酸酯：
Figure C9880362800042
其中n、R1和R4定义如结构式(I)；或
结构式(I)无环硫烷基硼酸酯与结构式(II)硫烷基取代环状偏硼酸酯的混合物。
12.一种用于制备含硫硼酸酯化合物的方法，其中包括，将主要量的润滑粘性油与少量的含硫硼酸酯化合物混合，所述含硫硼酸酯包含：具有通式(I)的无环硫烷基硼酸酯：
其中R1表示具有4-12个碳原子的烃基，R2和R3独立地表示-(OR4)nSR1或-(OR4)nSR1OH；R4表示具有1-6个碳原子的烃基；n为1-4的整数；且1和m独立地为0、1或2；或
具有通式(II)的硫烷基取代环状偏硼酸酯：
其中n、R1和R4定义如结构式(I)；或
结构式(I)无环硫烷基硼酸酯与结构式(II)硫烷基取代环状偏硼酸酯的混合物。
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US6028210A (en) 2000-02-22
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WO1999032588A1 (en) 1999-07-01
CN1251125A (zh) 2000-04-19

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