CN101506327B - 高性能磷酸酯液压油 - Google Patents

高性能磷酸酯液压油 Download PDF

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CN101506327B
CN101506327B CN200680021243.7A CN200680021243A CN101506327B CN 101506327 B CN101506327 B CN 101506327B CN 200680021243 A CN200680021243 A CN 200680021243A CN 101506327 B CN101506327 B CN 101506327B
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phosphoric acid
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T·C·沃尔夫
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Abstract

本申请公开了一种适于作为飞行器液压流体使用的高性能液压流体，含有主要量的三(正丁基)磷酸酯，少量的三芳基磷酸酯以及可选的少量三(异丁基)磷酸酯。本发明的组合物提供了与闪点和燃点以及延长的有效流体使用寿命有关的优异性能。作为液压流体现代喷气飞行器这些性能是非常有价值的。

Description

高性能磷酸酯液压油
本发明涉及磷酸酯功能流体组合物，及更特别地涉及提供与闪点和燃点以及更长有效流体使用寿命有关的优异性能的组合物。 
发明背景 
大多数民用飞行器中使用的飞行器液压油(hydraulic fluid)含有包括三烷基磷酸酯、二烷基芳基磷酸酯、烷基二芳基磷酸酯、和三芳基磷酸酯的磷酸酯的某些结合。该配方在Deetman的RE37101中公开并宣称提供优异的热、氧化和水解稳定性。飞行器中使用的液压流体可从申请人的受让人处获得，商品名为Skydrol RTM LD4。该组合物通常含有以重量计18-25％的二丁基苯基磷酸酯，以重量计50-60％的三丁基磷酸酯，4-8％的丁基二苯基磷酸酯，5-10％的粘度指数改进剂，0.13-1％的二苯基二硫代乙烷铜阻蚀剂，以重量计0.005％到约1％、但优选0.0075％-0.075％的全氟烷基磺酸盐防腐蚀剂，以重量计4％-8％如专利号US3723320中所述种类的酸清除剂清除剂，以及以重量计约1％的2，6-二叔丁基对甲酚作为抗氧化剂。该组合物已被证实在高性能飞行器应用中非常令人满意。 
自Deetman专利公开以来，已经公开了多种由Deetman公开的基本原料演化得到的配方，以提供具有不同性质的液压流体。Okazaki等人的US专利6319423和6649080专利公开了这些变型。这些基本原料含有主要量的三烷基磷酸酯其中烷基部分优选异丁基或异戊基，以及少量的三芳基磷酸酯。典型的基本原料配方是含有30％-45％三异丁基磷酸酯，30％-45％三正丁基磷酸酯和10％-15％三芳基磷酸酯的那些。其它在这些专利中公开的基本原料配方包括具有35％-45％三异丁基磷酸酯，40％-50％三正丁基磷酸酯以及12％-16％三芳基磷酸酯的那些。由于液压流体降解产物对用于液压体系封口上的弹性体腐蚀引起的关注，Okazaki等人的基本原料提供了三异丁基磷酸酯和三正丁基磷酸酯与一定量的三芳基磷酸酯一起的混合物，以使得基于基本原料的总重量，该流体在标准测试程序下会产生不高于25％的弹性体封口膨胀，其中在所述标 准测试程序中三异丁基磷酸酯的量从约35％到约50％。其声明这种流体具有作为飞行器液压流体组合物的有用性能的结合，包括可接受的水解稳定性、高闪点、良好的耐磨性、可接受的耐腐蚀性、可接受的低温流动性以及弹性体相容性。 
虽然上述专利表明了向液压飞行器流体体系统提供具有最适宜性能的有用流体的高效成果，但飞行器工业对更高要求的需求在持续增长。由更高性能的飞行用飞行器引发了对全面改进的液压流体性能的需求。因此，考虑到流体的寿命(热稳定性和低温粘度，同时保持可接受的燃点/闪点，自燃温度以及与飞行器液压体系使用材料的相容性)，需要甚至更高水平的性能。 
发明概述 
本发明涉及磷酸酯基本原料组合物，和含有具有新型磷酸酯组分组合的基本原料的飞行器液压流体组合物。 
依照本发明，提供含有主要量的三(正丁基)磷酸酯和少量三芳基磷酸酯和可选的三(异丁基)磷酸酯的混合物的组合物。该组合物表现出了改进的热稳定性和低温粘度。 
说明书和权利要求中使用的术语“主要量”至少为50％，但是不高于约80％。 
说明书和权利要求中使用的术语“少量”为少于约25％，基于基本原料的总重量。 
如本领域已知的，液压流体中使用多种添加剂，特别是那些在飞行器液压体系中使用的流体中。与现有技术中可得的用于飞行器液压体系的流体相比，这些添加剂进一步增强了流体的性能。基于流体的总重量，通常含有的添加剂以重量计为大约15％。因此，本说明书和权利要求中提供的磷酸酯组分的量以基于最终组合物总重量的百分数计，包括在飞行器液压流体中经常使用的添加剂。 
简单的说，本发明涉及适于飞行器液压流体使用的流体组合物。该组合物包括阻燃磷酸酯基本原料，该基本原料含有约50％到约80％、优选55％到约65％的三(正丁基)磷酸酯，约5％到约15％、优选约8％到约12％的三(异丙基苯基)磷酸酯，以及至多约20％、优选约8％到约12％的三(异丁基)磷 酸酯，附带条件为各基本原料组分和添加剂相应量的总和必须等于100％。 
本发明的高性能流体是满足现代喷气式客机严格标准的那些。为了满足最新的高性能喷气式飞行器的需要，用于这种飞行器液压体系的流体必须具有在0.5％水和25ppm氯含量下125℃下的标准实验室测试中大于1000小时的流体寿命，并同时在60℃下大于10000小时的流体寿命。流体寿命定义为流体样本达到在ASTM D974程序下达到中和数1.5mg KOH／g样本的时间。 
发明详述 
本发明特别优选的磷酸酯基本原料含有约60％三(正丁基)磷酸酯，约10％三(异丙醇化)芳基磷酸酯和约10％三(正丁基)磷酸酯，附带条件为各基本原料和添加剂相应量的总和必须等于100％。 
或者，本发明的优选组合物含有约65％的三(正丁基)磷酸酯，约10％的三(异丙基苯基)磷酸酯和约10％的三(异丁基)磷酸酯。 
如上所述，本发明的磷酸酯基本原料含有本领域熟知的各种添加剂，以提供对流体的多种有益性能或有助于防止降解或使用中的降解影响。这些添加剂在Deetman的RE37101中有述，其公开的全部内容在此一并引入作为参考。 
为限制温度对粘度的影响，组合物进一步含有聚合的粘度指数改进剂。优选粘度指数改进剂含有专利号为US3718596所述类型的聚(烷基甲基丙烯酸)酯。通常，该粘度指数改进剂具有约30000到约150000数均分子量以及约40000到约300000重均分子量的高分子量。粘度改进剂的例子包括相应的分别以商品名为HF411和HF460销售的聚丁基甲基丙烯酸酯聚合物和聚烷基甲基丙烯酸酯聚合物。 
防腐蚀剂以抑制流动引起的电化学腐蚀的有效量引入，该腐蚀更准确地称为ζ(zeta)腐蚀。添加的防腐蚀添加剂优选是碱金属盐，更优选全氟烷基磺酸的钾盐。该防腐添加剂在专利号为US3679587中更加详细地描述，并可包括全氟乙基环己基磺酸钾。 
本发明的基本原料中使用的三芳基磷酸酯通常为苯基，但是也可以是烷基取代的苯基(烷基苯基)，其中烷基取代基为C1-C9，优选C3-C5。非限制性 芳基磷酸酯和烷基取代的芳基磷酸酯的例子有，例如，三苯基磷酸酯、取代的苯基磷酸酯如三(异丙基苯基)磷酸酯、三(异丁基苯基)磷酸酯、三(叔丁基)磷酸酯。三芳基取代的苯基取代基包括甲苯基(也称为甲基苯基)、乙苯基、异丙基苯基、异丁基苯基、叔丁基苯基等等。优选的三芳基磷酸酯为三(异丙基苯基)磷酸酯和三(叔丁基苯基)磷酸酯。也优选大部分芳基基团仅被一个烷基基团取代。 
说明书和权利要求中所述的所有百分数除另有说明外均以重量计。 
举下述实施例说明本发明。 
实施例 
具有表1所示组成的液压流体通过室温下在合适容器中在提供足够共混的搅拌下混合制备。最后将磷酸酯组分引入罐中。其它添加剂按照表1所示的顺序首先加入。表1中，“TBP”和“TIBP”分别表示三正丁基磷酸酯和三异丁基磷酸酯。“IPTPP”表示异丙基三苯基磷酸酯。“Van Lube”表示商购防锈剂，可以Van Lub RIG从Vanderbilt获得。“FC-98”表示含有全氟乙基环己基磺酸钾盐的防腐蚀剂，也称作全氟乙基环己基磺酸。“IONOL”表示2，6-二叔丁基对甲酚，一种抗氧化剂，可从Shell化学品公司商购。“E-330”表示1，3，5-三甲基-2，4，6-三(3，5-二叔丁基羟苯基)苯，一种抗氧化剂，从Ethyl公司以Ethanox.RTM 330商品名下商购获得。“DODPA”表示二辛基二苯基胺，可从Vanderbilt购得，“FH-132”表示1，2-二(苯基硫代)乙烷、一种铜阻蚀剂，“MCS-1562”表示2-乙己基环氧基环己基羧酸酯，可从Dixie Chemicals购得，“HF411”表示聚(丁基甲基丙烯酸酯)以及“HF460”表示TBP中的聚烷基甲基丙烯酸酯聚合物，均为粘度指数改进剂，“消泡剂”表示可由Dow Corning Co.购得的硅树脂流体。 
表1 
  组分   样品1   样品2   样品3
  TBP   61.2885   60.3885   60.3735
  TIBP   10   10   10
  IPTPP   10   10   10
  VanLube   0.025   0.025   0.025
  FC-98   0.025   0.025   0.04
  IONOL   0.7   0.7   0.7
  E330   0.45   0.45   0.45
  DODPA   0.45   0.45   0.45
  FH-132   0.5   0.5   0.5
  染料   0.001   0.001   0.001
  MCS-1562   6.2   6.2   6.2
  消泡剂   0.0005   0.0005   0.0005
  HF411(35.5％固体)   5.76   6.26   6.26
  HF460(58％固体)   4.6   5   5
进行测试来测定表1所述流体的防火安全性、低温粘度、倾点和比重。闪点和燃点通过ASTM D-92程序的方法测定。然后在ASTM D-2155程序下检测组合物来测定其关于自燃温度(AIT)、粘度、倾点和比重的性质。表1中，所有例子均基于100g样品。测试结果在下表2中给出。 
表2 
    样品1   样品2   样品3
  AIT℃     792   807
  闪点℃     366   346
  燃点℃     383   376
  54℃下的粘度   972   1076   1052
  37.7℃下的粘度   8.89   9.28   9.52
  99℃下的粘度   3.11   3.33   3.31

Claims (3)

1.一种适于作为飞行器液压液使用的组合物，以重量百分数计，含有55％到65％的三(正丁基)磷酸酯，8％到12％的三(异丙基苯基)磷酸酯和8％到12％的三(异丁基)磷酸酯。
2.权利要求1的组合物，含有约65％的三(正丁基)磷酸酯，约10％的三(异丙基苯基)磷酸酯和约10％的三(异丁基)磷酸酯。
3.权利要求1的组合物，基于最终组合物的重量，进一步含有约15％的添加剂。
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