CN101910385A - 制备润滑组合物的方法 - Google Patents

制备润滑组合物的方法 Download PDF

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CN101910385A
CN101910385A CN2009801023633A CN200980102363A CN101910385A CN 101910385 A CN101910385 A CN 101910385A CN 2009801023633 A CN2009801023633 A CN 2009801023633A CN 200980102363 A CN200980102363 A CN 200980102363A CN 101910385 A CN101910385 A CN 101910385A
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lubricating grease
dihydroquinoline
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艾兰·理查德·惠特里
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Shell Internationale Research Maatschappij BV
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Abstract

本发明提供制备润滑组合物、特别是润滑脂的方法，该方法至少包括下述步骤：a)提供任选含有一种或多种添加剂的基油组合物；b)提供一种或多种烷基取代的喹啉或其低聚衍生物在溶剂内的溶液；和c)在低于150℃的温度下，添加步骤b)的溶液到步骤a)的基油组合物中。

Description

制备润滑组合物的方法
本发明涉及制备润滑组合物、特别是润滑脂的方法。
已知烷基取代的喹啉及其聚合衍生物是数种用途(其中包括在润滑组合物中使用)的非常有效的低成本的抗氧化剂。
作为实例，WO94/24235公开了烷基取代的1，2-二氢喹啉(包括单体、二聚物、三聚物及四聚物)在发动机油、传动油、齿轮油、金属加工液、液压流体、润滑脂等中的用途。这些烷基取代的1，2-二氢喹啉的例举实例是2，2，4-三甲基-1，2-二氢喹啉、2-甲基-2，4-二乙基-1，2-二氢喹啉、2，2，4，6-四甲基-1，2-二氢喹啉、2，2，4，7-四甲基-1，2-二氢喹啉、6，6′-双(2，2，4-三甲基-1，2-二氢喹啉)和类似物。
此外，US5246606公开了二聚、三聚和四聚的四氢喹啉衍生物适合于稳定有机材料防止光诱导、热和/或氧化降解。US 5246606建议在功能性流体如润滑剂和液压流体中使用这些化合物。
尽管烷基取代的喹啉例如2，2，4-三甲基-1，2-二氢喹啉(也称为“TMQ”、“TMDQ”和“TMHQ”)及其低聚(即二聚、三聚和四聚)衍生物广泛用作抗氧化剂，但它们具有许多缺点。
作为实例，TMQ在室温下为易碎固体形式，且通常为单体和低聚物的混合物形式，它没有确定的熔点。尽管它随温度升高而软化，但在约80-100℃的典型添加剂添加温度下，它仍然是非常粘稠和可拉丝的材料。
若在80-100℃的这一典型温度范围内将TMQ加入到润滑组合物例如润滑脂中，则它不会合适地分散到润滑脂中并会导致例如润滑脂传输系统内过滤器堵塞。即使这些润滑脂传输系统的过滤器负载不足以立即堵塞过滤器，但一些抗氧化剂被带出润滑脂，结果这会缩短寿命。
鉴于上述问题，在基油内建立增稠剂体系之后，在润滑脂完成其临界冷却阶段之后，常常在高于150℃的温度，通常在150-160℃之间，将烷基取代的喹啉加入到润滑脂中。
但与该已知方法有关的问题是，如果在润滑脂内合适地分散，则添加烷基取代喹啉的机会窗口通常是窄的。若例如在10分钟之后添加烷基取代的喹啉，则由于润滑脂可能冷却太多而可能太迟。
已经在相对高温下添加烷基取代的喹啉到润滑脂中的方法的进一步问题是，需要考虑更加严重的健康和安全问题，涉及例如在高温下润滑脂的危险性和当必须打开制备容器时烟雾的危险性。
本发明的目的是避免上述问题。
本发明另一目的是提供制备润滑组合物、特别是润滑脂的替代方法。
通过本发明，通过提供制备润滑组合物、特别是润滑脂的方法，实现一个或多个上述或其它目的，该方法至少包括下述步骤：
a)提供任选含有一种或多种添加剂的基油组合物；
b)提供一种或多种烷基取代的喹啉或其低聚衍生物在溶剂内的溶液；和
c)在低于150℃的温度下，添加步骤b)的溶液到步骤a)的基油组合物中。
令人惊奇地，按照本发明已发现，若烷基取代的喹啉(或其低聚衍生物)在溶剂内加入到基油组合物中，则它们可在较低温度下添加，同时仍然使它们适当分散在基油组合物内。
本发明的一个重要优点是，可在较低温度下添加烷基取代的喹啉(或其低聚衍生物)，导致不那么苛刻的安全要求。此外，添加烷基取代的喹啉(或其低聚衍生物)的时刻更灵活，因为其添加的具体温度不如其中不使用溶剂的情况那么关键。
优选地，在步骤c)中，在低于120℃的温度下，优选在10-110℃的范围内，更优选15-100℃下，添加步骤b)的溶液。
按照本发明特别优选的实施方案，一种或多种烷基取代的喹啉是烷基取代的1，2-二氢喹啉(或其低聚衍生物)。优选地，一种或多种烷基取代的1，2-二氢喹啉具有通式(I)：
Figure BPA00001184107600031
其中R1-R8独立地选自氢或具有1-8个碳原子的烷基；和n为0、1、2或3。
优选地，R1-R8独立地选自氢或具有1-4个碳原子、优选具有1-2个碳原子的烷基。优选地，R4是H。甚至更优选R4-R8全部是H。此外，优选R1-R3全部是甲基。
此外，一种或多种烷基取代的1，2-二氢喹啉优选n的平均值为1.0-2.0，优选1.3-1.6。
此外，优选在溶液内提供的一种或多种烷基取代的喹啉的溶解度低于0.1％，使用ASTM D893来测定。
本发明中所使用的烷基取代的喹啉化合物(或其低聚衍生物)可商购或者可通过本领域已知的多种反应来制备。在以上提及的WO94/24235和US5246606以及其中引述的参考文献中公开了制备方法的实例，其中的教导在此通过参考引入。在US4692258和US3910918以及其中引述的参考文献中给出了其它实例，其教导同样在此通过参考引入。
在W.R.Vaughan，“Organic synthesis”，Collective Vol.III，pp.329-30(1955)中给出了制备TMQ(2，2，4-三甲基-1，2-二氢喹啉)的一个具体实例。
对本发明的方法中所使用的溶剂没有特别限制，和可方便地使用各种常规溶剂。
优选地，溶剂包括聚二醇，更优选聚亚烷基二醇。聚二醇是本领域公知的和在此不进一步详细讨论。
作为实例，聚亚烷基二醇(PAG)可具有带1-6个碳原子的环氧烷单元(-R-O-)作为单体单元。
聚亚烷基二醇可具有氢端基、烷基、芳基、烷芳基、芳氧基、烷氧基、烷基芳氧基和/或羟基端基。烷基芳氧基还应当理解为是指芳烷基(亚基)氧基和烷芳基是指烷芳基(亚基)(如芳基CH2CH2-)。烷基类(包括烷氧基)或芳基类(包括烷芳基类、芳氧基类和烷基芳氧基类)的端基优选基于芳基类具有6-24个碳原子，特别优选6-18个碳原子，和基于烷基类优选1-12个碳原子。
本发明的聚亚烷基二醇可以是或者均聚物即聚丙二醇(和/或聚环氧丙烷)或共聚物、三元共聚物等。对于后面的情况来说，单体单元可显示出无规分布或嵌段结构。若聚亚烷基二醇不是均聚物，优选至少20％、优选至少40％的单体单元可由聚环氧丙烷(PO)产生，还优选至少20％这些聚亚烷基二醇中的全部单体单元可通过使用环氧乙烷(EO)(PO/EO共聚物)产生。按照进一步的实施方案，优选至少20％、优选至少40％的全部单体单元可由环氧丁烷(BO)获得，而且优选至少20％这些聚亚烷基二醇中的全部单体单元可通过使用环氧乙烷(BO/EO共聚物)获得。
当使用(聚)醇时，将起始化合物掺入到聚合物内，和按照本发明的含义，也称为聚合物链的端基。合适的起始基团由含活性氢的化合物组成，所述化合物例如正丁醇、丙二醇、乙二醇、辛戊二醇类如季戊四醇、亚乙基二胺、苯酚、甲酚或其它(C1-C16(单、二或三)烷基)芳烃、(羟烷基)芳烃、氢醌、氨基乙醇胺、三亚乙基四胺、多胺、山梨醇或其它糖类。其它C-H酸性化合物例如羧酸或羧酸酐也可用作起始化合物。
优选地，聚亚烷基二醇包括芳基或相应的杂芳基，例如作为侧基或端基插入到聚合物链内；该基团视需要可被直链或支链的烷基或亚烷基取代，该烷基或亚烷基总体优选具有1-18个碳原子。
环醚醇例如羟基糠基或羟基四氢呋喃、氮杂环或硫杂环也可用作起始基团。这些聚亚烷基二醇公开于WO01/57164中，其中的教导在此通过参考引入。
优选地，本发明的聚亚烷基二醇的平均分子量(数均分子量)为200-3000g/mol，更优选400-2000g/mol。聚亚烷基二醇的运动粘度优选为10-400mm2/s(cSt)，按照DIN 51562在40℃下测量。
可通过使醇类(其中包括多元醇)作为起始化合物与环氧烷例如环氧乙烷、环氧丙烷和/或环氧丁烷反应，生产本发明中所使用的聚亚烷基二醇。该反应之后，这些化合物只具有一个自由羟基作为端基。相对于具有两个自由羟基的那些，只具有一个羟基的聚亚烷基二醇是优选的。例如在进一步醚化步骤之后不再包括自由羟基的聚亚烷基二醇就稳定性、吸湿性和相容性来说，它们是特别优选的。端羟基的烷基化导致热稳定性增加。因此，在本发明特别优选的实施方案中，PAG基油包括封端PAG，即其中不存在自由羟基。
还可使用新戊基多元醇酯代替以上所述的聚亚烷基二醇。
新戊二醇类例如辛戊二醇、季戊四醇和三羟甲基丙烷与直链或支链C4-C12单羧酸例如通过加成相应的二羧酸的酯是合适的新戊基多元醇酯。通常季戊四醇以工业级季戊四醇获得，它是单季戊四醇、二季戊四醇和三季戊四醇的混合物。但它们的缩合产物例如二季戊四醇和/或三季戊四醇作为醇组分也是合适的。
季戊四醇或与二季戊四醇和/或三季戊四醇的混合物、优选主要含二季戊四醇的混合物是特别合适的。
可通过用单价和二价酸例如C4-C12二羧酸按比例酯化多元醇生产复合酯。按照这一方式，形成二聚物和低聚物。当使用新戊基二醇和/或三羟甲基丙烷作为醇基时，优选复合酯。
对在本发明方法中所使用的基油组合物没有特别限制，和可方便地使用各种常规的矿物油和合成油。对于本说明书的目的来说，术语“基油”还包括润滑脂基础原料。
本发明中所使用的基油组合物可方便地包括一种或多种矿物油和/或一种或多种合成油的混合物。
矿物油包括液体石油，和溶剂处理或酸处理过的链烷烃、脂环烃或混合链烷烃/脂环烃类的矿物润滑油，它们可通过加氢精制工艺和/或脱蜡进一步精制。
适用于本发明的润滑油组合物的基油是第I类、第II类或第III类基油、聚α-烯烃、费-托衍生的基油及它们的混合物。
在本发明中“第I类”基油、“第II类”基油和“第III类”基油是指按照American Petroleum Institute(API)分类I、II和III定义的润滑油基油。在API出版物1509，第15版，Appendix E，2002年4月中定义了这种API分类。
可方便地用作本发明润滑油组合物内的基油的合适的费-托衍生基油是例如在EP 0776959、EP 0668342、WO 97/21788、WO 00/15736、WO 00/14188、WO 00/14187、WO 00/14183、WO 00/14179、WO 00/08115、WO 99/41332、EP 1029029、WO 01/18156和WO 01/57166中公开的那些。
合成油包括烃油，例如烯烃低聚物(PAO)、二元酸酯、多元醇酯和脱蜡的蜡质残液。可方便地使用由Shell Group以名称“XHVI”(商品名)销售的合成烃基油。
在本发明的润滑组合物中掺入的基油总量相对于润滑组合物的总重量优选以范围为60-92wt％的含量存在，更优选含量范围为75-90wt％，和最优选含量范围为75-88wt％。
视需要，最终的润滑组合物可进一步包含一种或多种添加剂，例如抗氧化剂、耐磨剂、分散剂、清净剂、摩擦调节剂、粘度指数改进剂、倾点抑制剂、增粘剂、腐蚀抑制剂、破乳剂、消泡剂和密封固定或密封相容剂等。
由于本领域的技术人员熟悉上述和其它添加剂，因此在此不进一步讨论。可在步骤c)中添加一种或多种烷基取代的喹啉之前或之后，将添加剂加入到基油组合物中。此外，视需要，所述添加剂也可与一种或多种烷基取代的喹啉同时添加。
所述添加剂的存在量基于润滑组合物的总重量通常为0.01-12.5wt％，优选为0.05-10.0wt％，更优选1.0-9.0wt％，和最优选基于润滑组合物的总重量为2.0-5.0wt％。
由于润滑组合物也可以是(且优选是)润滑脂形式，因此在润滑组合物内包含的基油可含有一种或多种增稠剂如金属皂、有机物质或无机物质，例如锂皂、锂络合物皂、对苯二甲酸钠、脲/氨基甲酸酯化合物和粘土，或者与这些增稠剂配混。
优选地，润滑组合物在100℃下的运动粘度为2-80mm2/s，更优选为3-70mm2/s，最优选为4-50mm2/s。
可方便地通过混合一种或多种基油和任选地一种或多种通常存在于润滑组合物内的添加剂(例如前面所述的那些)与矿物和/或合成基油，制备本发明的润滑组合物。优选地，且如本领域惯例的是，一种或多种烷基取代的喹啉化合物(或其低聚衍生物)具有足够小的粒度(例如低于50微米，优选低于20微米)，以使其在润滑组合物内容易分散。
另一方面，本发明提供通过本发明方法获得的润滑组合物，特别是润滑脂。
下面参考下述实施例描述本发明，这些实施例不打算以任何方式限制本发明的范围。
实施例
烷基取代的喹啉的溶液
-溶液A
通过加热聚亚烷基二醇到100℃之后添加低聚2，2，4-三甲基-1，2-二氢喹啉，制备500ml低聚2，2，4-三甲基-1，2-二氢喹啉(固体，以商品名“Additin RC7010”获自Rhein Chemie Rheinau GmbH)在聚亚烷基二醇(以商品名“Oxilube 504”获自Dow Chemical Company，USA)内的50％m/m溶液。在约2分钟内缓慢添加低聚2，2，4-三甲基-1，2-二氢喹啉，从而使它在整个流体当中分散，之后再添加更多。如此获得的混合物在100℃下进一步搅拌30分钟。形成稳定的均匀溶液。
-溶液B
类似于溶液A，制备500ml低聚2，2，4-三甲基-1，2-二氢喹啉在聚二醇(以商品名“Synalox 50-50B”获自Dow Chemical Company，USA)内的50％m/m溶液。形成稳定的均匀溶液。
实施例1
使用以上提及的溶液A(50ml)和常规的润滑脂基础原料(4950g)，制备润滑脂。
常规的润滑脂基础原料含有约10％m/m锂复合增稠剂和约90％m/m由SN500和重质高粘度润滑油料共混的链烷烃矿物基油(按照ASTMD445，在40℃下的粘度为180mm2/s)。常规的润滑脂基础原料还含有耐磨添加剂(二烷基二硫代磷酸锌)、极压添加剂(硫化酯)和防锈剂(环烷酸锌)。
在润滑脂基础原料和溶液A混合之前，将二者预先加热到80℃，使用实验室桨叶式混合器，在30分钟期间内，简单地混合润滑脂基础原料和溶液A。
在肉眼观察之后，发现所得润滑脂没有明显缺陷。没有形成团块。此外，在储存12月之后，没有出现低聚2，2，4-三甲基-1，2-二氢喹啉从润滑脂中析出。
下表I中列出了所得润滑脂的其它性能。
表I
  测试   方法/条件   数值
  针入度(操作)   ASTM D217  25℃   260
  针入度(长期操作)   ASTM D217，100,000冲程   280
  油分离   IP 121，在40℃下7天   3.5％
  氧化稳定性   ASTM D942，在99℃下100h   30kPa
  铜腐蚀   ASTM D 4048，在100℃下24h   1b
  水洗出   ASTM D1264，在79℃下1h   0.5％
表I的结果表明润滑脂的所需性能例如机械稳定性、油保持性和另外令人惊奇的耐水性仍然存在于实施例1的润滑脂内，且没有受到用于溶解低聚2，2，4-三甲基-1，2-二氢喹啉所使用的溶剂(聚亚烷基二醇)的影响。
实施例2
类似于实施例1，使用溶液B制备润滑脂。
在肉眼观察之后，没有发现所得润滑脂有明显缺陷。没有形成团块。
此外，在储存12月之后，没有出现低聚2，2，4-三甲基-1，2-二氢喹啉从润滑脂中析出。类似于实施例1，实施例2的润滑脂表明所需的性能：机械稳定性、油保持性和耐水性。
对比例1
使用与实施例1和2相同量的低聚2，2，4-三甲基-1，2-二氢喹啉(没有溶剂)和相同的润滑脂基础原料，制备润滑脂。
加热该润滑脂基础原料到约160℃。然后，将一部分固体低聚2，2，4-三甲基-1，2-二氢喹啉加入到加热的润滑脂基础原料中并在这一温度下静置约10分钟。使用实验室桨叶式混合器进行混合，直到混合物达到约60℃的温度。
然后，再次加热该混合物到约160℃，并在这一温度下静置约30分钟。随后，重复添加和混合步骤，直到添加并混合所有低聚2，2，4-三甲基-1，2-二氢喹啉。
在肉眼观察之后，没有发现所得润滑脂有明显缺陷。没有形成团块。
对比例2
类似于对比例1制备润滑脂，但加热到约60℃(而不是约160℃)。
不可能将固体低聚2，2，4-三甲基-1，2-二氢喹啉分散到润滑脂基础原料内，因此在对比例2的润滑脂用于例如润滑脂传输系统中时，将导致严重的过滤器堵塞。
讨论
正如由实施例可以看出的，本发明允许在明显较低的温度下添加烷基取代的喹啉或其低聚衍生物，同时仍然获得具有所需性能的稳定润滑脂。不用说，从健康和安全角度以及从实际制备的角度考虑，这是极为理想的。
关于这一点，注意若在添加烷基取代的喹啉或其低聚衍生物时没有使用溶剂(参见对比例2)，则得不到稳定的润滑脂。

Claims (10)

1.制备润滑组合物、特别是润滑脂的方法，该方法至少包括下述步骤：
a)提供任选含有一种或多种添加剂的基油组合物；
b)提供一种或多种烷基取代的喹啉或其低聚衍生物在溶剂内的溶液；和
c)在低于150℃的温度下，添加步骤b)的溶液到步骤a)的基油组合物中。
2.权利要求1的方法，其中在步骤c)中，在低于120℃的温度下，优选在10-110℃的范围内，更优选15-100℃下，添加步骤b)的溶液。
3.权利要求1或2的方法，其中一种或多种烷基取代的喹啉是烷基取代的1，2-二氢喹啉。
4.权利要求3的方法，其中烷基取代的1，2-二氢喹啉具有通式(I)：
Figure FPA00001184107500011
其中R1-R8独立地选自氢或具有1-8个碳原子的烷基；和n为0、1、2或3。
5.权利要求4的方法，其中R1-R8独立地选自氢或具有1-4个碳原子、优选具有1-2个碳原子的烷基。
6.权利要求4或5的方法，其中R4-R8是H。
7.权利要求4-6任一项的方法，其中一种或多种烷基取代的1，2-二氢喹啉的n的平均值为1.0-2.0，优选为1.3-1.6。
8.权利要求1-7任一项的方法，其中在溶液内提供的一种或多种烷基取代的喹啉的溶解度低于0.1％，使用ASTM D893来测定。
9.权利要求1-8任一项的方法，其中所述溶剂包括聚二醇，优选聚亚烷基二醇。
10.通过权利要求1-9任一项的方法获得的润滑组合物，特别是润滑脂。
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US20110021392A1 (en) 2011-01-27
RU2492217C2 (ru) 2013-09-10
WO2009090238A1 (en) 2009-07-23
EP2242823A1 (en) 2010-10-27
CN101910385B (zh) 2014-03-05
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EP2242823B1 (en) 2013-03-13
AR070686A1 (es) 2010-04-28

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