CN1084551A - 功能液 - Google Patents
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- Publication number
- CN1084551A CN1084551A CN93108716A CN93108716A CN1084551A CN 1084551 A CN1084551 A CN 1084551A CN 93108716 A CN93108716 A CN 93108716A CN 93108716 A CN93108716 A CN 93108716A CN 1084551 A CN1084551 A CN 1084551A
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- China
- Prior art keywords
- composition
- heavy
- phosphoric acid
- alkyl
- acid ester
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/14—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring containing at least 2 hydroxy groups
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- C10M129/66—Epoxidised acids or esters
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Abstract
一种功能液,含有新的基础油组合物,其含有约
50%—70%(重)其中烷基取代基都是C3-C8并通过
伯碳原子键合到磷酸酯部分的磷酸三烷基酯、约
18%—35%(重)其中烷基取代基都是C-C并通过
伯碳原子键合到磷酸酯部分的二烷基芳基磷酸酯和
0—约5%(重)烷基二芳基磷酸酯。还含有酸清除
剂、防腐添加剂、粘度指数增进剂和抗氧化剂。优选
的是该组合物还含有4,5-二氢咪唑衍生物,以提高
该功能液的稳定性。
Description
本发明涉及磷酸酯功能液,更具体地说,本发明涉及改善热、水解和氧化稳定性的用作航空液压液的磷酸酯功能液。
功能液已经被用作电子冷却剂、扩散泵液、润滑剂、减震液、脂的基础油、电力输送液的基础油、液压液、传热液、热泵液、冷冻设备液及作为空调系统的过滤介质。要用于操作各种机构和航空控制系统的航空液压系统的液压液必须精确满足功能和使用的需要。对航空液压液的最重要的要求是其在提高的温度下有稳定的抗氧化性和水解降级。
使用时,航空液压液常常被湿气污染。水和废气从发动机压缩机段进入液压系统。在操作中,在Ⅳ型航空液压液中水分的量一般为约0.2-0.35%(重)。水导致磷酸酯的水解分解,产生磷酸的偏酯。如果水含量超过约0.5%(重),就加速酯的水解破坏。通常,配制的磷酸酯航空液压液含有酸清除剂,酸清除剂中和由三酯水解破坏所释放的磷酸偏酯。但是,超过时间,酸清除剂就变坏,并且,由于包括磷酸三酯、磷酸偏酯及通常含有液压液的金属环境的表面的复合反应形成有机金属化合物。这些有机金属化合物(其中磷酸铁通常是最突出的付产物)都不溶于液压液。
操作较高性能的飞机是在把液压液暴露于增加的温度的条件下进行的。目前A级液操作的最高温度是225-240°F。但是,设计的飞机应用要暴露航空液压液到275°F或更高范围的散装液温度中,在这样的温度下,磷酸酯的氧化和水解破坏的可能性明显增加。
当该液压液暴露到压缩空气中时,也加速磷酸酯液压液的降级。这种液体的空气氧化速度也随温度的增加而增加。因此,在275°F或更高的温度应用时,对该液体就需要有提高的热氧化稳定性和提高的热水解稳定性。
也可以预料腐蚀问题随散装液温度增加,腐蚀是电化学腐蚀的一种形式,更精确地是指Z腐蚀,其速度也随温度增加。气穴的影响,其是一种腐蚀问题的机械来源,大概也随温度而增加。随着腐蚀的进行,金属或其他不溶组分的存在可能引起过滤器阻塞及替换,并且可能引起该液体的物理及化学性质的变化,因此,需要过早的从系统排出液体。金属污染物也降低该液体的氧化稳定性,加速腐蚀。除了由金属(或其他污染物的污染所产生的影响外,该液体可能在许多其他方面受到损害,包括:a)粘度改变;b)酸值增加;c)增加化学活性;及d)脱色。
用于航空的液压液可以以商标Skydrol
LD-4从申请人的受让人买到。这种组合物含有30-35%(重)的磷酸二丁基苯基酯、50-60%(重)磷酸三丁基酯、5-10%(重)粘度指数增进剂、0.13-1%二苯基二硫代乙烷铜缓蚀剂、0.005%-约1%(重),但优选0.0075%-0.075%的全氟烷基磺酸盐缓蚀剂、4-8%(重)的在U.S.P.3,723,320所述类型的酸清除剂和约1%(重)的作为抗氧化剂的2,6-二叔丁基对甲酚。这种组合物在高性能的航空器的应用中是很满意的,但是,其不能被指定在275°F的温度范围连续操作。
因此,可以注意到,在本发明的几个目的中,提供一种用作航空应用中的液压液的改进的功能液;提供这样一种特别是在提高的温度下呈现出改善的水解稳定性的液体;提供这样一种在提高的温度F呈现出改善的氧化稳定性的液体;提供这样一种在剪切条件下呈现也优越的粘度特性和特殊的粘度稳定性的液体;提供这样一种相对低密度的液体;提供这样一种不仅有高的耐氧化性而且毒性低的液体;提供这样一种具有改善的耐腐性能的组合物;并且提供这样一种呈现出耐航空器式其他液压液系统的金属组分的腐蚀的液体组合物。
因此,简单的说,本发明涉及一种适用作航空液压液的液体组合物。该组合物包括一种耐火磷酸酯基础油,该基础油包括约50%-约72%(重)的磷酸三烷基酯、约18%-约35%(重)磷酸二烷基芳基酯和0-约5%(重)的烷基的烷基二芳基磷酸酯。磷酸三烷基酯和磷酸二烷基芳基酯的烷基取代基含有3-8个碳原子并且都通过伯碳原子键合到磷酸酯部分。该组合物进一步含有一种酸清除剂,其量有效的中和由该基础油的任何磷酸酯的水解就地形成的磷酸偏酯;一种有效量的防腐添加剂,以抑制在液压系统液压伺服阀的测流边缘的流动引起的电化学或Z腐蚀;一种有效量的粘度指数增进剂,使得该液体组合物呈现出的粘度指数在约210°F时至少约3.0厘沲;在约100°F时至少约9.0厘沲,在-65°F时小于约4200厘沲;和一种有效量的抗氧化剂,以抑制在氧的存在下液体组合物组分的氧化。
优选的是,三烷基磷酸酯和二烷基芳基磷酸酯的烷基取代基大体上都是C4或C5,最优选异丁基或异戊基。
本发明还涉及一种适用作航空液压液并含有新的添加剂混合物的液体组合物。该组合物含有耐火磷酸酯基础油,该基础油含有约10%-约90%(重)的磷酸三烷基酯、约0-约70%(重)的二烷基芳基磷酸酯和约0%-25%(重)的烷基二芳基磷酸酯。该磷酸三烷基酯和二烷基芳基磷酸酯的烷基取代基含有3-8个碳原子并都通过伯碳原子键合到磷酸酯部分。该组合物还含有一种粘度指数增进剂,其量为组合物的约3%-约10%(重)。该粘度指数增进剂含有甲基丙烯酸酯聚合物,该聚合物的重复单元主要包括丁基和己基甲基丙烯酸酯,该聚合物的至少95%(重)具有约50000-约1500000的分子量。该组合物还含有一种防腐剂,其量为组合物的约0.02%-约0.08%(重),该防腐剂含有一种全氟烷基磺酸的碱金属盐,其烷基取代基是己基、庚基、辛基、壬基或癸基。该组合物含有一种酸清除剂,其量为组合物的约1.5-10%(重),该酸清除剂含有一种在U.S.P.4,206,067中公开的3,4-环氧环己烷羧酸酯或双环氧化合物的衍生物。该组合物还含有2,4,6-三烷基苯酚,其量为约0.1%-约1%(重);二(烷基苯基)胺,其量为约0.3%-约1%(重),和一种受阻多酚组合物,该多酚组合物选自双(3,5-二烷基-4-羟基芳基)甲烷、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基芳基)苯和它们的混合物,其量为组合物的约0.3%-约1%(重)。磷酸三烷基酯和二烷基芳基磷酸酯的烷基取代基最好是丁基或戊基。
本发明还涉及一种适用作航空液压液的液体组合物,其含有耐火有机磷酸酯基础油。该基础油含有10%-约90%(重)的磷酸三烷基酯,其中烷基取代基基本上是异丁基或异戊基;0-70%(重)的二烷基芳基磷酸酯,其中烷基取代基基本上是异丁基或异戊基;和约0-25%(重)的烷基二芳基磷酸酯。该组合物还有有效量的酸清除剂,以中和由基础油的任何磷酸酯的水解就地形成的磷酸偏酯;一种有效量的防腐剂,以抑制液压系统中液压伺服阀的测流边缘的流动引起的电化学腐蚀;一种有效量的粘度指数增进剂,以使该液体组合物呈现的粘度指数在约210°F时为至少约3.0厘沲,在约100°F时至少约9.0厘沲,在约-65°F时小于约4200厘沲;和一种有效量的抗氧化剂,以抑制在氧的存在下液体组合物组分的氧化。
本发明还涉及一种适用作航空液压液的含有磷酸酯基础油的液体组合物。该基础油含有约10%-90%(重)的磷酸三烷基酯,其中烷基取代基基本上是丁基或戊基;约0-70%(重)的二烷基芳基磷酸酯,其中烷基取代基基本上是丁基或戊基;和约0%-25%(重)的烷基二芳基磷酸酯。该组合物还含有一种有效量的酸清除剂,以中和由基础油的任何磷酸酯水解就地形成的磷酸偏酯;一种有效量的防腐剂,以抑制液压系统中的液压伺服阀的测流边缘的流动引起的电化学腐蚀或Z腐蚀;一种有效量的粘度指数的改进剂,以使该组合物呈出的粘度指数在约210°F时至少约3.0厘沲,在约100°F时至少约9.0厘沲,在-65°F时小于4200厘沲;一种有效量的抗氧化剂,以抑制在氧存在下液体组合物组分的氧化;和一种有效量的4,5-二氢咪唑化合物,以使在300°F时组合物中的磷酸三酯破坏或磷酸偏酯速度减少至少25%其是通过环氧化物消耗测定的。4,5-二氢咪唑化合物相当于式
其中R1是氢、烷基、链烯基、羟烷基、羟烯基、烷氧基烷基或烷氧基烯基,R2是烷基、链烯基或脂族羧酸酯。
图1-12是在温度、水分含量和其他参数变化的条件下试验的液压液制剂的环氧化物消耗与时间的曲线图;和
图13是说明本发明的功能液的优异防腐性能的条形图。
按照本发明,已经发现,通过使用含有高浓度的烷基酯部分并含有比较少量的苯基或其他芳基酯的磷酸酯基础油就可以提供改善热稳定性、水解稳定性和氧化稳定性的液压液。该基础油含有磷酸三烷基酯和二烷基芳基磷酸酯的混合物,在其每一种磷酸酯中,烷基取代基是C3-C8,优选C4或C5。该烷基取代基通过伯碳原子键合到磷酸酯部分。任意地,该基础油还含有少量的烷基二芳基磷酸酯。如果磷酸三烷基酯和二烷基芳基磷酸酯的烷基取代基主要是由异丁基或异戊基,优选是其正构异构体时就会有其他优点。在这个优选的例子中,烷基取代是与磷酸的连接应该是通过伯碳原子。
除了改进的基础油外,本发明的组合物最好含有与用于本领域航空液压系统的当前可以买到的液压液比较能够进一步提高该液压液的性能的添加剂的混合物。而且,已发现本发明的添加剂的混合物在提高本领域已公知的基础油组合物的性能方面是有效的,否则就不同于本发明的功能液的优选的基础油。但是。已认识到使用本发明的添加剂混合物及基础油,特别是磷酸三烷基酯和二烷基芳基磷酸酯的烷基取代基是异丁基或异戊基的基础油具有最优越的性能。
该优选的基础油特征在于很低的烷基二芳基磷酸酯含量,优选不大于5%(重),最优选不大于2%(重)。另外优选的是含有芳基取代基即二烷基芳基、烷基二芳基的酯和磷酸三烷基酯的总量不大于基础油的约25%(重)。
更具体地说,优选的是基础油组合物含有约50-72%(重)的其中烷基取代基基本上是C4或C5的磷酸三烷基酯;约18%-35%(重)的其中烷基取代基基本上是C4或C5的二烷基芳基磷酸酯和约0-5%(重)的烷基二芳基磷酸酯。优选的是,该芳基取代基是苯基或烷基取代的苯基例如甲苯基、乙苯基或异丙苯基。与例如Skydrol
LD-4液压液大不相同,该LD-4液压液有明显高的二苯基酯含量,本发明的液压液的基础油在基本上高于225°F的温度下用与加入到LD-4相同的酸清除剂体系明显的呈现出改善的水解稳定性。用与LD-4相同的抗氧化剂时,含有本发明的基础油的组合物明显的呈现出提高的热氧化安定性。由于该基础油的相对低二苯基酯含量的结果,本发明的液压液是相对低密度的,其在航空液压液中应用是很有利的。
在本发明的优选的基础油中,特别优选的是烷基取代基是异丁基或异戊基。最优选异丁基。已经发现,含有三异丁基或三异戊基磷酸酯及二异丁基或二异戊基苯基磷酸酯的基础油组合物与其中烷基取代基是正丁基或正戊基的相同组合物比较能提供多种优越性。毒性研究表明,异丁基和异戊基酯比它们的正丁基和正戊基类似物质有平稳的低的毒性。尤其是,异丁基和异戊基酯使得比正构烷基酯有低的皮肤敏化作用。对全身性毒性也比较低。表A比较了丁基与异丁基磷酸酯的毒性性能。
表A
TBP TIBP
口服LD501200mg/Kg >5000mg/Kg
皮肤LD50>10000mg/Kg >5000mg/Kg
眼刺激 中等刺激 实际上无刺激
皮肤刺激 严重刺激 温和刺激
TBP TIBP
亚慢性的囊细
胞增生 用♂鼠>1000ppm 未观察到
用♀鼠>5000ppm
NOEL200ppm NOEL5000ppm
母鸡毒害神经 没有毒害神经 没有毒害神经
在LD50=1500mg/Kg 在LD50>5000mg/Kg
试验 试验
遗传毒性 Ames CHO/HGPRT 迄今未试验
体外细胞遗传
体内细胞遗传
显然,在本发明这方面,进一步已发现,在暴露于高性能航空液压系统的高温下,该异丁基和异戊基酯比相应的正烷基酯呈现出优异的水解稳定性。异丁基和异戊基酯也明显地具有密封完整性,通常所制造的液压系统密封的物质当与异烷基接触,比与相应的正烷基酯接触时膨胀的更少。另外,发现异丁酯和异戊酯比正烷基酯的密度低,这就意味着在给定的航空液压系统中液压液的重量少,从而改善航空燃料的效率。
除了改善的基础油外,本发明的组合物最好含有与用于本领域航空液压系统当前可以买到的液压液比较可进一步提高该液压液性能的添加剂的混合物。
更具体地说,该组合物中加入一种酸清除剂,其量要足以中和在使用液压液组合物的条件下由磷酸酯基础油组分的水解就地形成的磷酸偏酯。优选的是该酸清除剂是在U.S.P.3,723,320中介绍的3,4,-环氧环己烷羧酸酯组合物类型。也用如在U.S.P.4,206,067中公开的那些二环氧化物,其含有两个键合的环己基,其二者各稠合一个环氧化物基。这样的二环氧化物相应于下式:
其中R3是含有1-10个碳原子、0-6个氧原子和0-6个氮原子的有机基团,R4-R9分别选自氢和含有1-5个碳原子的脂族基。举例性的二环氧化物包括3,4-环氧环己基甲基-3,4-环氧环己烷、双(3,4-环氧-6-甲基环己基甲基己二酸酯)、2-(3,4-环氧环己基)-5,5-螺(3,4-环氧)环己烷-间二氧杂环己烷。在液体组合物中该酸清除剂的浓度优选为约1.5%-10%,更优选约2%-8%(重),其一般地足以维持液压液在可工作的条件下直至大约航空操作3000小时。
为了限制温度对粘度的影响,该组合物还包括聚合物粘度指数增进剂。优选的是,该粘度指数增进剂含有在U.S.P.3,718,596中公开的聚(烷基甲基丙烯酸酯)酯。一般地,粘度指数增进剂有高的分子量,数均分子量为约50000-100000,重均分子量为约200000-300000。优选的是,本发明的粘度指数增进剂有比较窄的分子量范围,大约95%(重)的粘度指数增进剂组分的分子量为约50000-1500000。通过使用主要为丁基和己基甲基丙烯酸酯就可部分达到这一结果。粘度指数增进剂存在的量足以使达到运动粘度:在210°F至少约3.0,优选约3-5厘沲;在100°F至少约9,优选约9-15厘沲;和在-65°F不大于约4200厘沲。通过将该粘度指数增进剂用于该组合物也可以提供优异的剪切稳定性能。优选的是该液体组合物含有约3%-10%(重)的粘度指数增进剂。特别优选的粘度指数增进剂是由Rohm & Hass销售的商标号PA6703和/或PA6477的粘度指数增进剂。通常以在磷酸酯溶剂,优选磷酸三烷基酯如磷酸三丁酯或磷酸三异丁酯,或烷基和苯基衍生物的混合物中的溶液的形式提供粘度指数增进剂。上述粘度指数增进剂的比例是以固体(甲基丙烯酸酯聚合物)为基准。磷酸酯溶剂变成基础油的有效部分,磷酸酯的比例范围(如上所述)影响作为粘度指数增进剂溶剂加入的磷酸酯。
加入有效量的防腐剂,以抑制流动产生的电化学腐蚀,更精确的是指Z腐蚀。防腐添加剂优选的碱金属盐,更优选的是全氟烷基磺酸钾盐。在U.S.P.3,679,587中较全面地介绍了这样的防腐添加剂。一般地,烷基组分包括己基、庚基、辛基、壬基、癸基或其混合物,用全氟辛基一般得到最好的性能。特别优选是的该防腐剂主要地包括全氟辛基磺酸钾盐,其量为约250-1000ppm,最优选至少约500ppm。在航空液压液系统的操作中,防腐剂的磺酸部分往往降低液压液的表面张力,因此,最好把通常与液压液接触的金属表面覆盖起来。伺服阀的测量边缘一般是需要保护的以防止电化学腐蚀的最重要的金属部件。在液压液中的正离子,包括防腐剂的碱金属离子吸附在金属的表面,并中和金属上的负电荷,该负电荷是另外由于伺服阀测量边缘附近的液压液的迅速流动产生的。本发明的组合物提供增强的抗腐蚀性,该组合物最好含有全氟烷基磺酸盐,其量约是以LD4销售的现有组合物中的两倍。
基础油的限定的二芳基酯含量有助于该液体的热稳定性、氧化安定性和水解安定性。本发明的组合物也含有抗氧化添加剂的混合物,最好包括受阻酚和受阻多酚。已经发现,通过部分地取代酚的受阻多酚可以改善水解稳定性,因此,最好该组合物所含的酚如2,4,6-三烷基酚的量不大于约1.0%,优选不大于0.7%(重)。一般地,最好该组合物含有约0.1%-0.7%的2,4,6-三烷基酚,优选2,6-二叔丁基对甲酚(“Ionol”)。该组合物还应该包括约0.3-1.0%的受阻多酚组合物像双(3,5-二烷基-4-羟基芳基)甲烷,例如由Ethyl Corp销售的商标牌号为Ethanox
702的双(3,5-二叔丁基-4-羟基苯基)甲烷,1,3,5-三烷基-2,4,6-三(3,5-二烷基-4-羟基芳基)芳族化合物,例如由Ethyl Corp销售的牌号为Ethanox
330的1,3,5-三甲基-2,4-6-三(3,5-二叔丁基-4-羟基苯基)苯,或其混合物。该组合物也可以包括胺抗氧化剂,优选二芳基胺,例如苯基-α-萘胺或烷基苯基-α萘胺,或由Ciba-Geigy销售的商标牌号Irganox
L-57的N-苯基苄胺与2,4,4-三甲基戊烯的反应产物;二苯基胺、二甲苯基胺、苯基甲苯基胺、4,4′-二氨基二苯基胺、二对甲氧基二苯基胺或4-环己基氨基二苯基胺;咔唑化合物例如N-甲基咔唑、N-乙基咔唑或3-羟基咔唑;氨基苯酚如N-丁基氨基苯酚、N-甲基-N-戊基氨基苯酚或N-异辛基-对氨基-苯酚;氨基二苯基烷烃例如氨基二苯基甲烷、4,4′-二氨基二苯基甲烷等,氨基二苯基醚;氨基二苯基硫醚;芳基取代的亚烷基二胺例如1,2-二邻甲苯氨基乙烷、1,2-二苯胺基乙烷或1,2-二苯胺基丙烷;氨基联苯如5-羟基-2-氨基联苯等;醛或酮与胺的反应产物例如丙酮与二苯基胺的反应产物;二芳胺配合物和酮或醛的反应产物;吗啉例如N-(对羟基苯基)吗啉等;脒例如N,N′-双(羟基苯基)乙脒等;二氢化吖啶例如9,9′-二甲基二氢化吖啶,吩呐噻嗪例如吩呐噻嗪,3,7-二丁基吩呐噻嗪或6,6-二辛基吩呐噻嗪;环己基胺;或它们的混合物。烷基取代的二苯基胺例如二(对辛基苯基)胺是优选的。某些胺组分也可以作为润滑添加剂。最好也存在胺抗氧化剂,其量为约0.3-1%(重)。通过维持该液体组合物的Ionol含量低于1.0%,优选低于0.7%,更优选低于0.5%(重),该组合物的毒性就比Skydrol
LD-4液压液的低。
作为铜腐蚀抑制剂,本发明的组合物优选包括苯并三唑衍生物,如以商标牌号Petrolite 57068销售的产品。该腐蚀抑制剂的存在量足以钝化与该液体组合物接触的金属表面,防止在与该液体接触的金属表面上形成金属氧化物,由此降低铜溶于液压液的速度,并且也许会降低由铜合金制造的部件的溶解。有利的是,该组合物含有约0.005%-0.09%(重)的苯并三唑衍生物,优选约0.02-0.07%(重)。
人们知道磷酸酯功能液腐蚀铁合金及铜合金。许多铁腐蚀抑制剂用于功能液中是有效的,但是人们知道,在很多情况下它们增加浸蚀速度,因此对液压液的性能有一种净的不利的影响。然而,根据本发明,已发现某些4,5-二氢基咪唑化合物是有效的铁腐蚀抑制剂,而没有对该液体的浸蚀性能的不利影响。有用的4,5-二氢基咪唑化合物包括如下结构式的相应化合物:
其中R1是氢、烷基、链烯基、羟烷基、羟基链烯基、烷氧基烷基、或烷氧基链烯基,R2是烷基、链烯基或脂族羧酸酯。这些基团的例子中,R1包括氢、甲基、乙基、丙基、丁基、戊基、辛基、乙烯基、丙烯基、辛烯基、己烯基、羟乙基、羟己基、甲氧基丙基、丙氧基乙基、丁氧基丙烯基等。这些基团的例子中,R2包括辛基、十二烷基、十六烷基、十七链烯基、或脂肪酸取代基如8-羧辛基、12-羧十二烷基、16-羧十六链烯基或18-羧十八烷基。在一个特别有效的实施方案中,R1是氢或低级烷基,R2是含有至少约9个碳原子的脂肪酸残基,即-C8-COOH至-C18-COOH,优选C18-C18-COOH。在另一个优选的实施方案中,R1是低级羟烷基,R2是C8-C18链烯基。但是,在后一个例子中,只有当4,5-二氢-咪唑与氨基酸衍生物,更具体的说是其中N-取代基含有极性和亲油部分的N-取代的氨基酸例如N-烷基-N-氧代-链烯基氨基酸一起使用时,人们认识到这是最满意的铁腐蚀抑制剂。
另外的和未预料到的发现是,如4,5-二氢 咪唑化合物的存在,一般存在量为约0.01%-0.1%(重),不仅抑制铁腐蚀,而且明显地有利于由环氧化物消耗所指明的功能液的稳定性。已经发现,如果4,5-二氢咪唑化合物与酚的抗氧化剂特别是复合受阻多酚如双(3,5-二烷基-4-羟基芳基)甲烷或1,3,5-三芳基-2,4,6-三(3,5-叔丁基-4-羟基芳基)芳香化合物混合使用,可以提高4,5-二氢咪唑化合物的有益效果。使用4,5-二氢-1H-咪唑和C16-C18脂肪酸的缩合产物(由Vanderbilt Co.销售的商标牌号Vanlube RI-G)与受阻多酚和烷基取代的二芳基胺例如二(对辛基苯基)胺的混合物观察到对稳定性有最佳效果。在这样的混合物中像4,5-二氢咪唑化合物那样的也有效的化合物是2-(8-十七 烯基)-4,5-二氢-1H-咪唑-1-乙醇(由Ciba-Geigy销售的,商标牌号为Amine-O),作为铁腐蚀抑制剂,后一化合物优选的与氨基酸衍生物例如N-甲基-N(1-氧代-9-十八 烯基)甘氨酸(由Ciba-Geigy销售,商标牌号Sarkosyl
-O)一起使用。为了起到铁腐蚀抑制剂的作用,后一种化合物应该与氨基酸衍生物例如N-甲基-N(1-氧代-9-十八 烯基)甘氨酸(由Ciba-Geigy销售,商标牌号Sarkosyl
-O)一起混合使用。
已经发现,如果4,5-二氢咪唑化合物与其中酯取代基基本上是异丁基或异戊基的基础油混合使用,仍然可以进一步提高高温稳定性。
虽然没有发现通过使用4,5-二氢咪唑化合物而产生对高温稳定性明显的有利效果,但是已发现其他铁腐蚀抑制剂在本发明的功能液中是有效的,其对腐蚀性能没有什么有害的影响。可以接受的铁腐蚀抑制剂包括例如由Petrolite销售的商标牌号Petrolite P-31001的产品。
如果需要,该液体组合物也可以含有抗泡剂。优选的这是一种硅酮液,更优选的是聚烷基硅氧烷,例如由Dow Corning销售的商标牌号DC200的聚甲基硅氧烷。优选的是该抗泡剂的含量要足以在ASTM方法892的试验条件下抑制泡沫的形成。一般地,组合物中抗泡剂的含量为至少约0.0005%(重),一般约0.0001%~0.001%(重)。
优选的是,本发明的组合物的PH至少为约7.5,最好在约7.5-9.0之间。为了达到这一范围的PH,并提高制剂的酸清除能力,该组合物可以进一步包括约0.0035-0.10%,优选约0.01-0.1%(重),最优选约0.02%-0.07%的碱金属酚盐或其他芳基化物。苯酚钾是优选的。除了中和该组合物的酸性组分外,当该组合物已加到液压系统中时,碱金属芳基化物用来安定金属表面,由此而减少腐蚀。
虽然用低烷基二芳基磷酸酯含量的组合物及特别是用上述本发明的基础油的组合物可以得到最佳的性能,但是本发明的添加剂混合物当与本领域已知的各种基础油的任何一种混合使用时也得到很有利的效果。使用烷基取代基主要是由异丁基或异戊基组成的酯的优点也使得超过上面概括的优选浓度范围。一般地说,该添加剂组合物可以与有机磷酸酯基础油一起使用,该有机磷酸酯基础油含有约10%-90%(重)的其中烷基取代基主要是丁基或戊基的磷酸三烷基酯、约0-70%(重)的其中烷基取代基主要是丁基或戊基的二烷基芳基磷酸酯和约0%-25%(重)的烷基二芳基磷酸酯。更优选的是,该添加剂组合物与基础油一起使用,该基础油含有约35%-90%(重)三丁基或三戊基磷酸酯、约0%-35%(重)二丁基芳基或二戊基芳基磷酸酯和约0%-20%(重)的三芳基磷酸酯。该添加剂组合物与下述其他范围的基础油组合物混合使用也是有效的;
表 1
重%
酯 基础油Ⅰ 基础油Ⅱ 基础油Ⅲ 基础油Ⅳ
三(C4/C5烷基) 10-72% 10-25% 50-72% 80-90%
二(C4/C5烷基) 18-70% 45-70% 18-25%
芳基
烷基二芳基 0-25% 5-25% 0-10%
三芳基 10-20%
如上所述,通过混合优选的异丁基和异戊基酯基础油与本发明的添加剂混合物可以达到最佳性能,但是,使用异烷基酯与其他添加剂组合物也可以达到低毒性、低密度、水解稳定性、热稳定性和密封完全性的优点。优选的是该异烷基酯基础油含有约50-72%(重)的其中烷基取代基基本上为异丁基或异戊基的磷酸三烷基酯,约18-35%(重)的其中烷基取代基基本上为异丁基或异戊基的二烷基芳基磷酸酯和约0-10%(重),优选约0-5%(重)的烷基二芳基磷酸酯。但是,使用异烷基取代基的优点是如此明显,以致于它们对相当宽范围的组合物都达到很显著的程度。因此,一般地,用异烷基酯的基础油可以含有约10%-90%(重)的三异丁基或三异戊基磷酸酯、约0-70%(重)的二异丁基或二异戊基芳基磷酸酯和约0-25%(重)的烷基二芳基磷酸酯。优选的是烷基二芳基磷酸酯的烷基取代基也是异丁基或异戊基,特别是当烷基二芳基磷酸酯含量超过约5%时,这些酯的芳基取代基一般是苯基,但是也可以是烷基苯基例如甲苯基、乙苯基或异丙苯基。
该异烷基基础油应该与有效量的酸清除剂混合,以中和基础油的任意磷酸酯的水解就地形成的磷酸偏酯。优选的是上述酸清除剂,但是其他的本领域已知的酸清除剂也可以用。该异烷基基的功能液也应该含有有效量的防腐添加剂,以抑制液压系统中的液压伺服阀的测流边缘的流动产生的电化学腐蚀。这些液体也应该含有有效量的粘度指数增进剂,以使得该液体组合物达到上述的粘度指数。该组合物还应该包括有效量的抗氧化剂,以抑制在氧化剂存在下液体组合物组分的氧化。优选的该防腐剂、粘度指数增进剂和抗氧化剂组合物如上所述,但是使用异烷基基础油的优点用其他本领域已知的添加剂混合物也能达到。
本领域熟练的技术人员已知的方法可以用来制备本发明的组合物。例如,含有磷酸酯的基础油可以通过在搅拌的不锈钢容器中混合来制备。然后,添加剂可以在同样的容器中调配到基础油中。如上所述,优选的是,粘度指数增进剂以在磷酸酯溶剂中的溶液形式加入。
在200°F以上的温度,本发明的较优选的功能液组合物呈现的热稳定性、氧化安定性和水解稳定性是由随作用时间而消耗的环氧化物酸清除剂所决定Skydrol
LD-4液压液的二到三倍。即使在含卤素的化合物例如三氯乙烷的存在下也呈现出优异的稳定性。当包括4,5-二氢咪唑化合物时,改善的程度甚至更大。由于相对低苯基酯含量的结果,本发明的组合物的密度低于1克/毫升,一般地为约0.98-0.99克/毫升。从在飞机上燃料燃烧(消耗)的观点看这是合乎要求的特性。
该液体组合物的剪切稳定性与市场上可买到的航空液压液比较也是有利的。因此,例如在一般的航空液压泵系统中暴露到加速降级试验500小时后,在-65°F该组合物的粘度仅从4000降到2400。这一优点部分的被认为是由于该粘度指数增进剂的窄范围分子量的结果。暴露到剪切条件下往往降解高分子量的粘度指数增进剂,所以粘度指数增进剂的分子量的分布范围较宽的组合物,在超时时由于较高分子量种类的破坏超向于遭受功效的较大损失。
部分的由于较低浓度的2,6-二叔丁基对甲酚,所以本发明的液压液组合物的毒性是很低的。使用异烷基酯基础油时毒性甚至更低。
下面的实施例说明本发明。
实施例1
具有表1所示组合物的液压液是通过在室温下,在用有锚式叶轮的25马力的搅拌器搅拌的50加仑的不锈钢罐中混合而制备的。首先将磷酸酯组分加入罐中,初步混合30分钟之后,按表2所指出的顺序加入其它的添加剂。
表 2
基准: 基准:
100克配料 80加仑配料
组分 克 克/磅
磷酸三丁酯,纯的二苯 49.0135 148,216.8/326.8
基含量低的(小于2% 26.34 79,652.2/175.6
(重))磷酸二丁基苯 DRUM2(~220#)
基酯
甲基丙烯酸酯 16.56 50,077/110.4
粘度指数增进剂 22684.9
(PA6477,在 gSLDS
54.7%磷酸三丁酯
中45.3%固体)
3,4环氧环已烷羧酸酯 6.3 19,051/42
全氟辛基磺酸钾(FC98) 0.05 151.2/
苯并三唑型
铜缓蚀剂 0.05 151.2/
(P57068,Petrolite
(50%活性的)EXI663
基准: 基准:
100克配料 80加仑配料
组分 克 克/磅
铁缓蚀剂 0.05 151.2/
(90-31001,Petrolite
(50%活性的)
染料 0.001 3.024/
苯酚钾 0.035 105.84/
双(3,5-二叔丁基-4- 0.90 2,722/6
羟基苯基)甲烷
二(对辛基苯基)胺 0.45 1,361/3
2,6-二叔丁基对甲酚 0.25 756/1.667
抗泡剂(Dow-Corning) 0.0005 1.512/
这种组合物在25℃温度下密度为0.996g/cc。磷酸二丁基苯基酯源中77.135%(重)是磷酸二丁基苯基酯或磷酸丁基二苯基酯,以致整个组合物的20.3%(重)是由含有苯基部分的磷酸酯组成。不过,磷酸丁基二苯基酯含量小于1%(重)。磷酸三苯酯含量基本为零。
实施例2
第二种航空液压液组合物通常是按实施例1所述方法制备的。这种液的组成列于表3。
表 3
组分的密度 基准: 基准:
100g配料 80加仑配料
变量 克 克/磅
磷酸三丁酯 50.5988 152,999.3/337.3
二苯基含量低的(小于 24.0947 72,862.3/106.63
2%(重))磷酸二丁基
苯基酯
甲基丙烯酸酯 22,684.9
粘度指数增进剂 gSLDS
(PA6477, 总量(Total)
43.8%固体/
56.2%磷酸三丁酯)
3,4环氧环已烷羧酸酯 6.3 19,051/42
全氟辛基磺酸钾(FC98) 0.05 151.2/
苯并三唑型
铜缓蚀剂 0.05 151.2/
(P57068,Petrolite
(50%活性的)
铁缓蚀剂 0.05 151.2/
(90-31001,Petrolite
(50%活性的)EXI663
组分的密度 基准: 基准:
100g配料 80加仑配料
变量 克 克/磅
染料 0.001 3.024/
苯酚钾 0.035 105.84/
双(3,5-二叔丁基-4- 0.90 2,722/6
羟基苯基)甲烷
(Ethanox702)
二(对辛基苯基)胺 0.45 1,361/3
Dow-Corning抗泡剂 0.0005 1.512/
2,6-二叔丁基对甲酚 0.25 756/1,667
这种组合物在25℃温度下密度也为0.996g/cc。磷酸二丁基苯基酯源中84.751%(重)是由不含苯基部分的酯组成。整个组合物含有20.3%(重)具有一个苯基部分的磷酸酯,而磷酸丁基二苯基酯小于1%(重)。磷酸三苯酯基本上没有。
实施例1和实施例2的组合物的部分元素分析和所测的物理性质列于表4。这些数据表明实施例1和实施例2的液体组合物对于使用作航空液压液的产品合格所需的性质而言,其满足或超过飞机制造商的规格。
表 4
配料1 配料2
颜色 通过 通过
氯,ppm 20 21
K+106 99
S 57 83
Ca <1 <1
Na 1.4 1.5
比重(sp.G) 0.9972 0.9975
粘度(VISC)210F CST 4.75 4.81
100 13.65 13.91
-65 1635 1628
水分 0.10 0.12
中和值(NEUT NO) 0.01 0.02
倾点(POUR PT)°F ?-; ?-;
自燃点(AIT)F 850 920
闪点(FLASH PT) 350 360
燃点(FIRE PT) 360 390
导电率 0.65 0.55
环氧乙烷值 0.39 0.40
配料1 配料2
泡沫 SEQ 1 170/65 180/20
2 30/10 40/44
3 80/35 140/56
粒子计数 5-15 7247 3116
15-25 1444 513
25-50 460 180
50-100 75 53
>100 14 10
污淤指数 1.18 1.05
实施例3
试验比较实施例1和实施例2的液压液组合物与市场上可买到的液压液组合物的热安定性、氧化安定性和水解安定性。在每一个这些试验中,向301不锈钢管中装入要试验的液体至钢管容积的80%。在每个试验中保持温度不变。比较试验在250°F和275°F下进行,本发明的组合物进一步在300°F下进行试验。在所有试验中,五个腐蚀试件浸在液压液中。
在一些试验中,钢管的顶部空间充满空气,在另一些试验中,顶部空间充满氮气。在每根管装了合适的试验组合物之后,将钢管盖好并加热到预定的试验温度维持在这个温度下从而可测定在这个温度下的水解安定性。整个期间监测每根钢管,根据在液压液的化学组合物中的趋势取出试样,特别是根据在试样中存在的酸性清除剂(环氧化物)的浓度取出试样。当环氧化物100%消耗掉时,该液体一般降级至基本上不能用做航空液压液的程度。当环氧化物消耗量达100%时,滴定试验样品的酸度。当液体的中和值达到1.5或大于1.5时,停止试验。
本发明的组合物与以前可买到的航空液压液比较环氧化物消耗曲线示于图1-3。在这些曲线中,以及有关下面列出的进一步的实施例的曲线中,符号“W17”和“W17R”表示上面表1或表2的组合物“2495B1”指表1的组合物,“2495B2”系指2的组合物。“H4A”系指Chevron以商标牌号“Hyjet IVA
”销售的商品液压液。“Epox A”指的是不锈钢管顶部空间采用空气进行试验,这样试样受到热作用、水解作用和氧化作用。“Epox T”指的是顶部空间装有氮,这样试验主要只是测定热水解作用。
实施例4
进行实施例1和实施例2的组合物的进一步热安定性、水解安定性和氧化安定性试验。除了在试样中引入0.5%的水分以确定水分对热安定性的影响外,这些试验一般是按实施例3所述方法进行。试验温度为250°F和275°F。这些试验的结果绘于图4和图5中。
实施例5
比较本发明的组合物和本领域以前可得的组合物的另外的热安定性、氧化安定性和水解安定性试验是在密封的派累克斯管中进行。在某些试验中,腐蚀试件浸在派累克斯管里所含液体中。除了使用派累克斯管而不使用不锈钢管外,试验基本上是按实施例3所述方法进行。用五个腐蚀试件浸在试样中,在300°F下在有0.1-0.5%水分的条件下试验本发明的组合物和比较液的组合物。这些试验的结果示于图6-8。另外的有关本发明的组合物的试验是在375°F下没有水分加入的条件下进行。这些试验结果示于图9。
实施例6
除了加入不同量的三氯乙烷到试样中以确定对安定性的影响外,进一步的热安定性试验、氧化安定性和水解安定性试验一般是按实施例3所述的方法进行。试验温度是275°F和300°F。这个实施例的试验结果示于图10和图11。
实施例7
通过根据联邦试验方法FTM5308.7的试验,将实施例1和2的液体组合物的抗氧化性和抗腐蚀性与以前可得的航空液压液的抗氧化性和抗腐蚀性进行比较。这些试验严格地着重于液体的氧化安定性。
在每个试验中,液体加到玻璃管中,按照FTM5308.7进行试验。液体加热到一定的温度即350°F,此后以每小时51的速率通过试验液体吹干燥的空气。每24小时取样,或者更频繁地取样,当液体的中和值达到1.5或>1.5时,停止试验。这个实施例的试验结果示于图12。
实施例8
因为冲蚀是电化学腐蚀的一种形式,因此凭借液体通过类似于试验伺服阀的孔的模似小孔流动时得到的壁电流,可以测定液压液组合物的冲蚀特性。使用标准的冲蚀试验装置进行试验,比较实施例1和实施例2的组合物与本领域以前可得的航空液压液组合物的冲蚀性能。在这个试验系统中,壁电流低表示冲蚀性能好,负的壁电流表示冲蚀性能特别好。试验本发明的组合物和以前市场上可买到的组合物所得的数据汇总列于表5。
进一步的冲蚀试验是试验在玻璃容器中于225°F下空气接触储存后的各种功能液组合物。储存了指定的小时数的样品的这些试验结果列于表6。
在这些表中,试样的导电率列出了两个测定值,一个是申请受让人得到的,另一个是局外人的试验室试验得到的。Iw表示壁电流,it表示阈电流,Rv是冲蚀速度。Rv是通过函数Rv=150Iw-18il与Iw和it关联的。在表5和表6中,术语“LD4”系指Monsanto以商标“Skydrol
LD-4”销售的产品;“SKY500B”和“B4”系指以商标牌号“Skydrol
500B4”从Monsanto买到的另一种功能液产品。“LD5”系指本发明的组合物;“FC96”系指含有全氟己基磺酸的钾盐的一种抗蚀剂;“Ca+2”系指在试验液中存在二全氟甲基磺酸Ca+2;“AO”意指存在抗氧化剂,其一般为亚诺(Ionol)和受阻多酚如象双(3,5-二叔丁基羟基苯基)甲烷的结合;关于在LD-4中的耐磨剂“X1”指的是耐磨剂FC98以标准的工业浓度存在;“X2”和“X3”指的是FC98的浓度增加一倍或两倍;“TBP”系指磷酸三丁酯;“DBPP”系指磷酸二丁基苯基酯;“TEHP”系指磷酸三乙基己基酯;“Si-HC”系指四烷基硅烷组分;“HT”代表Skydrol
HT(由申请受让人销售的一种功能液制剂);“TiBP”系指磷酸三异丁酯;“FC98”系指含有全氟辛基磺酸钾盐的一种耐磨剂;“EXI663”系指苯并三唑型铜缓蚀剂;31001系指petrolite的铁缓蚀剂;HALS系指受阻胺光稳定剂;“H4A”系指由Chevron以商标牌号Hyjet IVA在市场销售的功能液的各种样品;“W6”、“W7”、“W8”等系指本发明的组合物;“ERT”指的是用在耐磨试验中的试样;“ECT”指的是用在冲蚀对照试验中的试样。
实施例9
在铁存在下于375°F下的储存试验中将实施例1和实施例2的组合物与可得的商品液压液比较,在这样的条件下储存21小时后,分析在液体中生成的固体。较详细地,测定值包括金属固体生成量、其它固体生成量和总的固体生成量。这些试验的结果示于图13。
实施例10
基本上按实施例1所述方法配制本发明的航空液压液,并且该液经受耐火液压液波音材料规格的耐磨试验BMS3-11G(参看7/17/86)。试验过的液体组合物列于表7、表7A和表7B。冲蚀试验的结果列于表8。经受冲蚀试验前后液体性质的比较列于表9和表9A。在这些表中。“HF400,”“HF-411,”和“HF-460”系指聚(丁基/己基甲基丙烯酸酯)粘度指数增进剂。在每个项目中,该表代表丁基甲基丙烯酸酯聚合物固体含量,平衡量是磷酸三烷基酯溶剂。“AEA”系指一种耐磨剂;“PANA”代表苯基-α-萘胺;“APANA”代表烷基苯基-α-萘胺;“DODPA”系指二(对辛基苯基)胺;“P58526Petrolite”是一种铁缓蚀剂;“DC200,100CST”是道康宁(Dow-Corning)抗泡剂;“SARK O”系指由Ciba-Geigy以商标牌号“Sarkosyl-O”销售的(N-甲基-N-1-氧代-9-十八碳烯基(octadeny)甘氨酸),“AMINE O”系指由Ciba-Geigy以商标牌号“Amino-O”销售的2-(8-十七碳烯基)-4,5-二氢-1H-咪唑-1-乙醇;“90-31001”系指Petrolite 31001;“FH-132”系指二苯基二硫代乙烷。
实施例11
制备基本上符合实施例1组合物的制剂,只是三烷基磷酸酯和二烷基芳基磷酸酯组分分别为三异丁基磷酸酯和二异丁基苯基磷酸酯,并且组合物根据所含的铁缓蚀剂化合物而变化。按实施例9所过的方法进行这些组合物的冲蚀阀泄漏试验,一般按实施例1所述的方法进行这些组合物的环氧化物消耗试验。这些试验的结果列于表10。
该表表明组合物M-1使用抗氧化剂“组合物”。起初,M-1含有Ionol、Ethanox 702和二(对辛基苯基)胺(DODPA)。在冲蚀试验进行25小时之后,在组合物中再加一些Ethanox 702和DODPA。在153小时时加入苯酚型抗氧剂;在267小时时加入胺抗氧剂;在503小时时加入Ethanox 703和Ethanox 330的混合物。Ethanox 703是2,6-二叔丁基-α-二甲基胺基邻甲酚。在153小时时加的酚型抗氧剂是Ciba-Geigy以商标牌号IganoxL-130销售的叔丁基苯酚衍生物的混合物。在267小时时加入的胺抗氧剂是由Ciba-Geigy以商标牌号L-57销售的、N-苯基苄基胺和2,4,4-三甲基戊烯的反应产物。
这些数据和实施例9的数据表明铁防腐剂Petrolite 31001和Vanlube RI-G对冲蚀的作用都是令人满意的。两者似乎都不明显地加速冲蚀,并且含有这些添加剂的组合物显示出满意的耐磨性能。
磷酸三异丁基酯/磷酸二异丁基苯基酯基础油与Vanlube RI-G4,5-二氢咪唑衍生物的组合物对高温时组合物的安定性提供了显著的出乎意料的有利作用。使用除上述类型的4,5-二氢咪唑之外的其它铁缓蚀剂观察不到这种作用。
Claims (45)
1、一种适用作航空液压液的液体组合物,其包括:
耐火的磷酸酯基础油,所说的基础油包括约50%-72%(重)的其中烷基取代基含有3-8个碳原子并通过一个伯碳原子键合到磷酸酯部分的磷酸三烷基酯、约18%-35%(重)的其中烷基取代基含有3-8个碳原子并通过一个伯碳原子键合到磷酸酯部分的二烷基芳基磷酸酯和约0-5%(重)的烷基二芳基磷酸酯;
有效量的酸清除剂以中和由所述基础油的任意磷酸酯的水解就地形成的磷酸偏酯;
有效量的防腐蚀添加剂以抑制在液压系统中液压伺服阀的测量流量的边缘流动产生的电化学腐蚀或Z腐蚀;
有效量的粘度指数增进剂以使该液体组合物呈现的粘度指数在约210°F至少约3.0厘沲,在约100°F至少约9.0厘沲,在-65°F低于约4200厘沲;和有效量的抗氧化剂以抑制在氧化剂存在下液体组合物组分的氧化。
2、一种适用作航空液压液的液体组合物,其包括:
一种耐火的磷酸酯基础油,所说的基础油包括约50%-72%(重)的其中烷基取代基基本上是C4或C5的磷酸三烷基酯、约18%-35%(重)的其中烷基取代基基本上是C4或C5的二烷基芳基磷酸酯和0-约5%(重)的烷基二芳基磷酸酯;
有效量的酸清除剂以中和由所述基础油的任意的磷酸酯的水解就地形成的磷酸偏酯;
有效量的防腐蚀添加剂以抑制在液压系统中的液压伺服阀的测量流量的边缘流动产生的电化学腐蚀或Z腐蚀;
有效量的粘度指数增进剂以使该液体组合物呈现的粘度指数在约210°F为约3.0厘沲,在约100°F为约9.0厘沲和在-65°F小于约4200厘沲;和
有效量的抗氧化剂以抑制在氧化剂存在下液体组合物组分的氧化。
3、按照权利要求2的液体组合物,其中所说的二烷基芳基磷酸酯是二烷基苯基磷酸酯。
4、按照权利要求2的组合物,其中所说的粘度指数增进剂以有效量存在以使得该液体组合物呈现的粘度指数在约210°F为约3-5厘沲在100°F约9-15厘沲。
5、按照权利要求2的组合物,其中所含的粘度指数增进剂的量为所述组合物的约3%-10%(重),所述的粘度指数增进剂含有甲基丙烯酸酯聚合物,其重复单元基本上包括丁基和己基甲基丙烯酸酯,所述聚合物的至少95%(重)的分子量为约50000-1500000。
6、按照权利要求2的组合物,含有所述组合物的约0.1%-1.0%(重)的2,4,6-三烷基苯酚、所述组合物的约0.3%-1%(重)的二(烷基苯基)胺和一种受阻多酚组合物,该受阻多酚组合物选自双(3,5-二烷基-4-羟基芳基)甲烷和1,3,5-三烷基-2,4,6-三(3,5-二叔丁基-4-羟基芳基)苯及其混合物,其量为所述组合物的约0.3%-1%(重)。
7、按照权利要求2的组合物,其中含有一个芳基取代基的酯不大于所述基础油的约25%(重)
8、按照权利要求1的组合物,其中所述烷基基本上都是异丁基或异戊基。
9、一种适用作航空液压液的液体组合物,其含有:
一种耐火磷酸酯基础油,该基础油含有约10%-90%(重)的其中烷基取代基含有3-8个碳原子并通过一个伯碳原子键合到磷酸酯部分的磷酸三烷基酯、约0-70%(重)的其中烷基取代基含有3-8个碳原子并通过一个伯碳原子键合到磷酸酯部分的二烷基芳基磷酸酯和约0%-25%(重)的烷基二芳基磷酸酯;
一种粘度指数增进剂,其量为所述组合物的约3%-10%(重),所述粘度指数增进剂含有甲基丙烯酸酯聚合物,所述聚合物的重复单元基本上包含丁基和己基甲基丙烯酸酯,所述聚合物的至少95%(重)的分子量为约50000-1500000;
一种防腐剂,其量为所述组合物的约0.02%-0.08%(重),所述防腐剂含有全氟烷基磺酸的碱金属盐,其烷基取代基是己基、庚基、辛基、壬或癸基或其混合物;
一种酸清除剂,其量为所述组合物的约1.5%-10%(重),所述酸清除剂含有环氧化合物;
2,4,6-三烷基苯酚,其量为所述组合物的约0.1%-1.0%(重);
二(烷基苯基)胺,其量为所述组合物的约0.3%-1%;和
一种受阻多酚组合物,其选自双(3,5-二烷基-4-羟基芳基)甲烷、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基芳基)苯及其混合物,其量为所述组合物的约0.3%-1%(重)。
10、一种适用作航空液压液的液体组合物,其含有:
一种耐火磷酸酯基础油,该基础油含有约10%-90%(重)的其中烷基基本上都是丁基或戊基的磷酸三烷基酯约0-70%(重)的其中烷基取代基基本上都是丁基或戊基的二烷基芳基磷酸酯和约0%-25%(重)的烷基二芳基磷酸酯;
一种粘度指数增进剂,其量为所述组合物的约3%-10%(重),所述粘度指数增进剂含有甲基丙烯酸酯聚合物,该聚合物的重复单元主要含有丁基和己基甲基丙烯酸酯,所述聚合物的至少95%(重)的分子量为约50000-1500000;
一种防腐剂,其量为所述组合物的约0.02%-0.08%(重),所述防腐剂含有全氟烷基磺酸的碱金属盐,它的烷基取代基是己基、庚基、辛基、壬基或癸基或其混合物;
一种酸清除剂,其量为所述组合物的约1.5%-10%(重),所述酸清除剂选自3,4-环氧环己烷羧酸酯的衍生物和相当于下式的二环氧化合物:
其中R3是含有1-10个碳原子、0-6个氧原子和0-6个氮原子的有机基,R4-R9分别选自氢、含有1-5个碳原子的脂族基和所述3,4-环氧环己烷羧酸酯与所述二环氧化合物的混合物;
2,4,6-三烷基苯酚,其量为所述组合物的约0.1-1.0%(重);
二(烷基苯基)胺,其量为所述组合物的约0.3%-1%(重);和
一种受阻多酚组合物,其选自双(3,5-二烷基-4-羟基芳基)甲烷、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基芳基)苯及其混合物;其量为所述组合物的约0.3%-1%(重)。
11、按照权利要求10的组合物,还含有苯并三唑或苯并三唑衍生物,其量为约0.005%-0.09%作为铜腐蚀抑制剂。
12、按照权利要求10的组合物,还含有约0.0035%-0.10%(重)的碱金属芳基化物。
13、按照权利要求10的液体组合物,其中所说的基础油含有约35%-90%(重)的其中烷基取代基基本上都是丁基或戊基的磷酸三烷基酯和约0-35%(重)的其中烷基取代基基本上都是丁基或戊基的二烷基芳基磷酸酯及约0-20%(重)的三芳基磷酸酯。
14、按照权利要求13的液体组合物,其中所说的基础油含有约80%-90%(重)的其中烷基取代基基本上都是丁基或戊基的磷酸三烷基酯和约10%-20%(重)的三(烷芳基)磷酸酯。
15、按照权利要求14的液体组合物,其中所说的三(烷芳基)磷酸酯包括三(异丙基苯基)磷酸酯。
16、按照权利要求10的液体组合物,其中所说的基础油含有约10%-72%(重)的其中烷基取代基基本上都是丁基或戊基的磷酸三烷基酯、约18%-70%(重)的其中烷基取代基基本上都是丁基或戊基的二烷基芳基磷酸酯和约0%-25%(重)的烷基二芳基磷酸酯。
17、按照权利要求16的液体组合物,其中所说的基础油含有约10%-25%(重)的其中烷基取代基基本上都是丁基或戊基的磷酸三烷基酯、约45%-70%(重)的其中烷基基本上都是丁基或戊基的二烷基芳基磷酸酯及约5%-25%(重)的其中烷基取代基基本上都是丁基或戊基的烷基二芳基磷酸酯。
18、按照权利要求16的液体组合物,其中所说的基础油含有约50%-72%(重)的其中烷基取代基基本上都是丁基或戊基的磷酸三烷基酯、约18%-35%(重)的其中烷基取代基基本上都是丁基或戊基的二烷基芳基磷酸酯和约0-10%(重)的烷基二芳基磷酸酯。
19、按照权利要求10的液体组合物,其中所说的基础油含有约0-5%(重)的烷基二芳基磷酸酯。
20、按照权利要求10的组合物,其中所说的烷基取代基基本上都是异丁基或异戊基。
21、一种适用作航空液压液的液体组合物,其包括:
一种耐火磷酸酯基础油,所述基础油含有约10%-90%(重)的其中烷基取代基基本上都是异丁基或异戊基的磷酸三烷基酯、约0-70%(重)的其中烷基取代基基本上都是异丁基或异戊基的二烷基芳基磷酸酯和约0%-25%(重)的烷基二芳基磷酸酯;
一种有效量的酸清除剂,以中和所述基础油的任何磷酸酯的水解就地形成的磷酸偏酯;
一种有效量的防腐添加剂以抑制在液压系统中液压伺服阀的测流边缘的流动产生的电化学腐蚀;
一种有效量的粘度指数增进剂,以使该液体组合物呈现的粘度指数在约210°F至少约3.0厘沲,在约100°F至少约9.0厘沲,在-65°F小于约4200厘沲;和
一种有效量的抗氧化剂以抑制在氧化剂存在下液体组合物组分的氧化。
22、按照权利要求21的组合物,其中所述磷酸三烷基酯是三异丁基磷酸酯,所述二烷基芳基磷酸酯是二异丁基苯基磷酸酯。
23、按照权利要求21的组合物还含有苯并三唑或苯并三唑衍生物,其量为约0.005%-0.09%(重)作为铜腐蚀抑制剂。
25、按照权利要求24的组合物,其中所说的4,5-二氢咪唑选自2-(8-十七烯基)-4,5-二氢-1H-咪唑-1-乙醇和C14-C18脂肪酸与4,5-二氢-1H-咪唑的缩合产物。
26、按照权利要求25的组合物,其中所说的4,5-二氢咪唑化合物是C16-C18脂肪酸与4,5-二氢-1H-咪唑的缩合产物。
27、按照权利要求24的组合物,其中所说的抗氧化剂包括受阻酚。
28、按照权利要求27的组合物,其中所说的受阻酚包括选自双(3,5-二烷基-4-羟基芳基)甲烷、1,3,5-三烷基-2,4,6-三(3,5-二叔丁基-4-羟基芳基)苯及其混合物的受阻多酚化合物。
29、按照权利要求27的组合物,其中所说的抗氧化剂还含有一种胺化合物。
30、按照权利要求29的组合物还含有二芳基胺抗氧化剂。
31、按照权利要求30的组合物,其中所说的二芳基胺包括二(对辛基苯基)胺。
32、按照权利要求30的组合物还含有直至约0.7%(重)的2,6-二叔丁基对甲酚。
33、一种适用作航空液压液的液体组合物,其包括:
一种耐火磷酸酯基础油,其含有约10%-90%(重)的其中烷基取代基基本上都是丁基或戊基的磷酸三烷基酯、约0-70%(重)的其中烷基取代基基本上都是丁基或戊基的二烷基芳基磷酸酯和约0%-25%(重)的烷基二芳基磷酸酯;
一种有效量的酸清除剂,以中和所述基础油的任何磷酸酯的水解就地形成的磷酸偏酯;
一种有效量的防腐添加剂以抑制在液压系统中液压伺服阀的测流边缘的流动产生的化学腐蚀或Z腐蚀:
一种有效量的粘度指数增进剂,以使该液体组合物呈现的粘度指数为在约210°F约3.0厘沲,在约100°F约9.0厘沲,在-65°F小于约4200厘沲;
一种有效量的抗氧化剂以抑制在氧化剂存在下液体组合物组分的氧化;和
有效量的4,5-二氢咪唑化合物以使在300°F由环氧化物消耗测定的该组合物的安定性增加至少25%,所说的4,5-二氢咪唑化合物相应于下式
其中R1选自氢、烷基、链烯基、羟烷基、羟基链烯基、烷氧基烷基和烷氧基链烯基,R2选自烷基、链烯基和脂族羧酸酯。
34、按照权利要求33的组合物,其中R1是氢或低级烷基,R2是脂肪酸残基。
35、按照权利要求33的组合物,其中R1是羟烷基,R2是链烯基。
36、按照权利要求33的组合物,其中所说的4,5-二氢咪唑选自2-(8-十七 烯基)-4,5-二氢-1H-咪唑-1-乙醇和C14-C18脂肪酸与4,5-二氢-1H-咪唑的缩合产物。
37、按照权利要求36的组合物,其中所说的4,5-二氢咪唑化合物是C16-C18脂肪酸与4,5-二氢-1H-咪唑的缩合产物。
38、按照权利要求37的组合物,其中所说的磷酸三烷基酯和所述二烷基芳基磷酸酯的所说烷基取代基基本上都是异丁基或异戊基。
39、按照权利要求33的组合物,其中所说的抗氧化剂包括受阻酚。
40、按照权利要求39的组合物,其中所说的受阻酚包括选自双(3,5-二烷基-4-羟基芳基)甲烷、1,3,5-三烷基-2,4,6-三(3,5-二叔丁基-4-羟基芳基)苯及其混合物的受阻多酚化合物。
41、按照权利要求39的组合物,其中所说的抗氧化剂还含有一种胺化合物。
42、按照权利要求41的组合物还含有二芳基胺抗氧化剂。
43、按照权利要求42的组合物,其中所说的二芳基胺包括二(对辛基苯基)胺。
44、按照权利要求42的组合物还含有直到约1.0%(重)的2,6-二叔丁基对甲酚。
45、按照权利要求33的组合物,其中所说的磷酸三烷基酯和所说的二烷基芳基磷酸酯的所说的烷基取代基基本上都是异丁基或异戊基。
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US89718992A | 1992-06-11 | 1992-06-11 | |
US897,189 | 1992-06-11 |
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EP (1) | EP0644922B2 (zh) |
JP (1) | JP3420235B2 (zh) |
KR (1) | KR0161554B1 (zh) |
CN (1) | CN1040018C (zh) |
AT (1) | ATE166102T1 (zh) |
AU (1) | AU669184B2 (zh) |
BR (1) | BR9306530A (zh) |
CA (1) | CA2136739C (zh) |
CZ (1) | CZ308794A3 (zh) |
DE (1) | DE69318555T3 (zh) |
ES (1) | ES2072239T1 (zh) |
FI (1) | FI945809A (zh) |
HU (1) | HUT69300A (zh) |
IL (1) | IL105981A (zh) |
MX (1) | MX9303478A (zh) |
NO (1) | NO944776L (zh) |
NZ (1) | NZ253574A (zh) |
RU (1) | RU2167921C2 (zh) |
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- 1993-06-01 JP JP50154794A patent/JP3420235B2/ja not_active Expired - Fee Related
- 1993-06-01 WO PCT/US1993/005201 patent/WO1993025641A1/en not_active Application Discontinuation
- 1993-06-01 AT AT93914295T patent/ATE166102T1/de not_active IP Right Cessation
- 1993-06-01 EP EP93914295A patent/EP0644922B2/en not_active Expired - Lifetime
- 1993-06-01 ES ES93914295T patent/ES2072239T1/es active Pending
- 1993-06-01 HU HU9403526A patent/HUT69300A/hu unknown
- 1993-06-01 CZ CZ943087A patent/CZ308794A3/cs unknown
- 1993-06-01 KR KR1019940704510A patent/KR0161554B1/ko not_active IP Right Cessation
- 1993-06-01 AU AU44006/93A patent/AU669184B2/en not_active Expired
- 1993-06-01 NZ NZ253574A patent/NZ253574A/en unknown
- 1993-06-01 DE DE69318555T patent/DE69318555T3/de not_active Expired - Lifetime
- 1993-06-01 CA CA002136739A patent/CA2136739C/en not_active Expired - Lifetime
- 1993-06-01 BR BR9306530A patent/BR9306530A/pt not_active IP Right Cessation
- 1993-06-01 RU RU94046225/04A patent/RU2167921C2/ru active
- 1993-06-10 IL IL10598193A patent/IL105981A/en not_active IP Right Cessation
- 1993-06-10 MX MX9303478A patent/MX9303478A/es unknown
- 1993-06-10 CN CN93108716A patent/CN1040018C/zh not_active Expired - Lifetime
- 1993-06-10 ZA ZA934121A patent/ZA934121B/xx unknown
- 1993-07-28 US US08/099,267 patent/US5464551A/en not_active Ceased
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1994
- 1994-12-09 FI FI945809A patent/FI945809A/fi not_active Application Discontinuation
- 1994-12-09 NO NO944776A patent/NO944776L/no unknown
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CN102041142A (zh) * | 2010-12-25 | 2011-05-04 | 锦州惠发天合化学有限公司 | 一种含氟润滑油 |
CN103666650A (zh) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | 磷酸酯液压油组合物 |
CN103666650B (zh) * | 2012-09-25 | 2015-03-18 | 中国石油化工股份有限公司 | 磷酸酯液压油组合物 |
CN108138069A (zh) * | 2015-10-30 | 2018-06-08 | 雪佛龙奥伦耐有限责任公司 | 含有脒抗氧化剂的润滑油组合物 |
CN108138069B (zh) * | 2015-10-30 | 2021-09-24 | 雪佛龙奥伦耐有限责任公司 | 含有脒抗氧化剂的润滑油组合物 |
CN110088256A (zh) * | 2016-12-14 | 2019-08-02 | 赢创油品添加剂有限公司 | 聚酯作为飞机液压流体的粘度指数改进剂的用途 |
CN111057606A (zh) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | 一种黏度指数改进剂及其制备方法、用途 |
CN112226265A (zh) * | 2020-10-23 | 2021-01-15 | 中国石油化工股份有限公司 | 一种磷酸酯液压液组合物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
FI945809A (fi) | 1995-02-02 |
CN1040018C (zh) | 1998-09-30 |
IL105981A (en) | 1996-06-18 |
KR0161554B1 (ko) | 1999-01-15 |
WO1993025641A1 (en) | 1993-12-23 |
JP3420235B2 (ja) | 2003-06-23 |
KR950701967A (ko) | 1995-05-17 |
DE69318555T3 (de) | 2008-02-21 |
FI945809A0 (fi) | 1994-12-09 |
CA2136739A1 (en) | 1993-12-23 |
ES2072239T1 (es) | 1995-07-16 |
ZA934121B (en) | 1994-01-17 |
AU4400693A (en) | 1994-01-04 |
BR9306530A (pt) | 1998-09-15 |
MX9303478A (es) | 1994-02-28 |
RU94046225A (ru) | 1996-09-27 |
EP0644922B2 (en) | 2007-06-13 |
RU2167921C2 (ru) | 2001-05-27 |
HUT69300A (en) | 1995-09-28 |
NZ253574A (en) | 1996-01-26 |
JPH07507830A (ja) | 1995-08-31 |
DE69318555D1 (de) | 1998-06-18 |
CZ308794A3 (en) | 1996-01-17 |
EP0644922A1 (en) | 1995-03-29 |
AU669184B2 (en) | 1996-05-30 |
NO944776L (no) | 1995-01-25 |
ATE166102T1 (de) | 1998-05-15 |
EP0644922B1 (en) | 1998-05-13 |
CA2136739C (en) | 1999-10-05 |
NO944776D0 (no) | 1994-12-09 |
DE69318555T2 (de) | 1998-12-03 |
IL105981A0 (en) | 1993-10-20 |
US5464551A (en) | 1995-11-07 |
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