CN107922877B - 具有含硫聚亚烷基二醇的润滑剂 - Google Patents

具有含硫聚亚烷基二醇的润滑剂 Download PDF

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CN107922877B
CN107922877B CN201680048662.3A CN201680048662A CN107922877B CN 107922877 B CN107922877 B CN 107922877B CN 201680048662 A CN201680048662 A CN 201680048662A CN 107922877 B CN107922877 B CN 107922877B
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M·R·格里夫斯
R·范伍尔斯特
M·米尔特恩斯
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Abstract

一种流体含有基础油和抗氧化剂，所述基础油由含硫聚亚烷基二醇组成，其中所述流体中有大于80重量百分比是含硫聚亚烷基二醇并且所述流体中有小于1重量百分比是水，其中重量百分比基于总流体重量，其中所述含硫聚亚烷基二醇不含直接与硫结合的氧。

Description

具有含硫聚亚烷基二醇的润滑剂
技术领域
本发明涉及一种含有含硫聚亚烷基二醇基础油和抗氧化剂的流体。
背景技术
耐火工业流体，特别是那些具有热氧化稳定性的工业流体，对于高温应用，如钢铁加工和发电中的润滑剂和液压流体，是理想的。提高此类工业流体的耐火性和热氧化稳定性是一个持续的愿望和挑战。历来被用作润滑剂的烃油由于其可燃性而在此类应用中通常是不希望的。水基润滑剂(water-based lubricant)比烃油具有更好的耐火特性，但往往不适用于可能蒸发水的高温应用。高温应用通常需要无水润滑剂。
已知常规的聚亚烷基二醇(PAG)是烃和水的润滑油基础油替代品。常规PAG是使用一元醇、二元醇或三元醇引发并与环氧乙烷和/或环氧丙烷反应以形成典型地具有大于500g/mol并且高达50,000g/mol的分子量的聚合物的PAG。使用这种常规PAG作为基础油的润滑剂组合物提供作为液压流体和涡轮机油有利的性能益处。然而，除非存在抗氧化剂，否则常规PAG倾向于遭受氧化不稳定性。因此，当传统的基于PAG的润滑剂组合物耗尽抗氧化剂时，润滑剂的氧化稳定性受到不希望的影响。
理想的是鉴定出一种提供耐火特性和热氧化稳定性的工业流体，同时还提供PAG的润滑能力，尤其是如果润滑剂基础油的性能超过常规PAG的性能，因此流体的氧化稳定性较少地取决于存在的抗氧化剂的量。
发明内容
本发明提供一种具有出人意料的高耐火特性和热氧化稳定性的流体，同时还提供PAG的润滑能力。本发明润滑剂的基础油倾向于比常规PAG具有更高的耐火性能和/或热氧化稳定性。
在第一方面，本发明是一种包含基础油和抗氧化剂的流体，所述基础油由含硫聚亚烷基二醇组成，其中流体中有大于80重量百分比是含硫聚亚烷基二醇并且流体中有小于1重量百分比是水，其中重量百分比基于总流体重量，并且其中含硫聚亚烷基二醇不含直接与硫结合的氧。
在第二方面，本发明是一种使用第一方面的流体的方法，所述方法包含将任何前述权利要求的流体作为选自由液压流体和润滑流体组成的组的材料引入设备中。
本发明的流体适用作润滑剂和液压流体，特别是用于不希望含水润滑剂的高温和高压应用中。
具体实施方式
“和/或”意指“和，或或者”。除非另外说明，否则所有范围都包括端点。
测试方法参考本文件优先权日期之前的最新测试方法，除非测试方法编号中标明日期为带有连字符的两位数。参考测试方法含有参考测试协会和测试方法编号两者。通过以下缩写中的一个来参考测试方法组织：ASTM是指ASTM国际(已知原名为美国测试与材料协会(American Society for Testing and Materials))；EN是指欧洲标准(EuropeanNorm)；DIN是指德国标准化学会(Deutsches Institut für Normung)；以及ISO是指国际标准化组织(International Organization for Standards)。
根据ASTM D7042测定运动粘度。根据ASTM D2270计算润滑剂调配物的粘度指数。根据ASTM D97测定倾点。根据ASTM D4274测量羟值。根据ASTM方法D92测定燃点值。
本发明是一种包含基础油和抗氧化剂的流体。所述流体宜作为液压流体和/或润滑剂流体。由于其阻燃性，流体是特别理想的。
本发明的基础油是不含直接与硫结合的氧的含硫聚亚烷基二醇(S-PAG)。理想地，S-PAG包含共聚环氧丙烷、环氧丁烷或共聚环氧丙烷和环氧丁烷的组合。另外或替代地，S-PAG可以不含多于两种，优选不含多于一种，并且可以完全不含共聚环氧乙烷。理想地，S-PAG不含由环氧乙烷聚合得到的-C2H4O-组分。例如，来源于醇引发剂(例如丁醇或硫代二甘醇)的-C2H4O-不会将由环氧乙烷聚合得到的-C2H4O-组分提供到所得S-PAG中。例如，S-PAG可以不含不直接与硫结合的-C2H4O-基团。
S-PAG可以具有结构(I)的结构：
Figure BDA0001580595440000041
其中R1、R2、R3和R4独立地选自由以下组成的组：甲基(-CH3)和乙基(-CH2CH3)；R5选自由以下组成的组：氢、含有1-6个碳原子的脂族基团和含有6个碳原子的芳香族基团；x是选自由1和2组成的组的数字；m、m′、n和n′独立地选自0到20范围内的数字，使得m、m′、n和n′的总和至少为6，并且A选自由-C2H4-和C6H4基团组成的组。一种特别理想的S-PAG具有结构(I)的结构，其中x是1，并且A是-C2H4-。另外或作为结构(I)的这些选择的任何组合的替代，R1、R2、R3和R4全部可以是-CH3基团。当m、n、m′和n′各自为1或更大时，聚合物是无规或嵌段共聚物。当反应性氧化物同时加入到引发剂中时会产生无规共聚物。随着聚合物的生长，氧化物随机添加到聚合物主链中，形成最终的无规共聚物。当一种氧化物加入到引发剂中并且当它完全反应后再加入第二种氧化物时，产生嵌段结构。最终的结构被描述为嵌段结构，因为它包含氧化物嵌段。
流体含有相对于总流体重量大于80重量百分比(wt％)，优选85wt％或更多，更优选90wt％或更多，并且可以是95wt％或更多的S-PAG基础油。
本发明的抗氧化剂可以选自由自由基清除剂，过氧化物分解剂和酚类抗氧化剂组成的组。自由基清除剂的实例包括芳香族类胺类抗氧化剂，如烷基化二苯胺和苯基-α-萘胺以及烷基化苯基-α-萘胺。过氧化物分解剂抗氧化剂包括氨基甲酸酯型抗氧化剂，如烷基化二硫代氨基甲酸酯。自由基清除剂作为抗氧化剂是理想的，尤其是胺类。一种特别理想的抗氧化剂是辛基化/丁基化二苯胺。
希望抗氧化剂基于总流体重量以0.25wt％或更多，优选0.5wt％或更多，同时以5wt％或更少，优选2wt％或更少的浓度存在。
流体中有小于1wt％是水，其中wt％。优选地，流体含有0.5wt％或更少，更优选0.1wt％或更少，更优选0.05wt％或更少，并且可以含有0.01wt％或更少或甚至不含水。水的wt％是相对于总流体重量来说。如果流体用于可能从流体中蒸发出水的高温应用中，那么水是不合需要的。
流体可以含有或不含任何一种或多于一种添加剂的组合，包括选自由抗磨、极压、腐蚀抑制剂、黄色金属钝化剂、染料和泡沫控制添加剂组成的组的那些添加剂。
出人意料的是，本发明已发现，如根据ASTM方法D92测定，在PAG主链中包括硫可以提高PAG的燃点。本发明还出人意料地发现，相对于主链中不含硫的相似组合物，将S-PAG与抗氧化剂混合会产生出人意料的高热氧化稳定性。增强的氧化稳定性为流体提供更长的使用寿命，而不会由于氧化而降解。
使用本发明流体的方法包括将流体作为选自由液压流体和润滑流体组成的组的材料引入设备中。
实例
表1列出了实例和对比实例中所用的材料。
表1
Figure BDA0001580595440000061
Figure BDA0001580595440000071
S-PAG1的合成：2，2′-硫代二乙醇的环氧丙烷均聚物
将1190克(g)2，2′-硫代二乙醇装入配有搅拌器、环氧烷加料系统、温度控制系统和施加真空的构件的不锈钢烷氧基化反应器中。加入26.5g 45wt％的氢氧化钾水溶液作为催化剂。关闭反应器并用氮气置换反应器中的空气。将反应器加热到115摄氏度(℃)，并通过在30毫巴下施加真空120分钟来除去水，以将水的浓度降低到小于每百万份总内含物重量3000重量份(ppm)。进一步将反应器加热到130℃，并在6小时内加入4750g环氧丙烷。添加全部环氧丙烷后，停止进给环氧丙烷并将反应器维持在130℃持续6小时以使剩余的氧化物反应。用硅酸镁处理所得聚二醇，并加以过滤以除去催化剂。产物(S-PAG1)在40℃下的运动粘度为45.8厘沲(cSt)，100℃下的运动粘度为6.96cSt，粘度指数为109，并且羟值为每克188.0毫克氢氧化钾。
S-PAG1具有结构(I)的结构，其中R1、R2、R3和R4各自为甲基，R5为氢，并且平均m、m′、n和n′之和为8.4。
S-PAG2的合成：2，2′-硫代二乙醇的环氧丁烷均聚物
将582g 2，2′-硫代二乙醇装入配有搅拌器、环氧烷加料系统、温度控制系统和施加真空的构件的不锈钢烷氧基化反应器中。加入13.9g 45wt％的氢氧化钾水溶液作为催化剂。关闭反应器并用氮气置换反应器中的空气。将反应器加热到115℃，并通过在30毫巴下真空干燥120分钟来除去水，以将水浓度降低到小于3000ppm。进一步将反应器加热到130℃，并在6小时内加入2514g 1，2-环氧丁烷。添加全部1，2-环氧丁烷后，停止进给1，2-环氧丁烷并将反应器维持在130℃持续6小时以使剩余的氧化物反应。用硅酸镁处理所得聚二醇，并加以过滤以除去催化剂。产物(S-PAG2)在40℃下的运动粘度为50.7cSt，100℃下的运动粘度为6.80cSt，粘度指数为84，并且羟值为每克179.0毫克氢氧化钾。
S-PAG2具有结构(I)的结构，其中R1、R2、R3和R4各自为乙基，R5为氢，并且平均m，m′，n和n′之和为7.3。
S-PAG3的合成：2，2＇-硫代二乙醇的环氧丙烷/环氧丁烷无规共聚物
将600g 2，2′-硫代二乙醇装入配有搅拌器、环氧烷加料系统、温度控制系统和施加真空的构件的不锈钢烷氧基化反应器中。加入14.2g 45wt％的氢氧化钾水溶液作为催化剂。关闭反应器并用氮气置换反应器中的空气。将反应器加热到115℃，并通过在30毫巴下真空干燥120分钟来除去水，以将水浓度降低到小于3000ppm。进一步将反应器加热到130℃，并在6小时内加入2590g 50/50混合物(按环氧丙烷和1，2-环氧丁烷的重量计)。添加全部环氧烷后，停止进给环氧烷并将反应器维持在130℃持续6小时以使剩余的氧化物反应。用硅酸镁处理所得聚二醇，并加以过滤以除去催化剂。产物(S-PAG3)在40℃下的运动粘度为48.7cSt，100℃下的运动粘度为7.05cSt，粘度指数为101，并且羟值为每克179.0毫克氢氧化钾。
S-PAG3具有结构(I)的结构，其中R1和R2是甲基，R3和R4是乙基，平均m+m′是4.5，n+n′是3.7。
比较实例(Comp Ex)A-H：基础油的燃点表征
根据ASTM方法D92表征表2中鉴别的基础油的燃点。这些值用作流体调配物的参考值。
表2
样品 基础油 燃点(℃)
Comp Ex A 50-30B 245
Comp Ex B 100-30B 244
Comp Ex C OSP-32 240
Comp Ex D OSP-46 254
Comp Ex E OSP-68 242
Comp Ex F S-PAG1 284
Comp Ex G S-PAG2 276
Comp Ex H S-PAG3 278
比较实例I-M和实例(Ex)1-4：具有抗氧化剂的流体的燃点值
如表3所述制备由基础油和抗氧化剂组成的流体。wt％基于总流体重量。根据ASTM方法D92表征所得流体的燃点。结果在表3中。
表3
Figure BDA0001580595440000101
Figure BDA0001580595440000111
表3中的数据表明，添加抗氧化剂倾向于会增加基础油的燃点。然而，与表1中的数据相比，显然S-PAG流体较不依赖于抗氧化剂而达到高于275℃的燃点，而不是不含硫的PAG基础油。因此，即使在抗氧化剂耗尽的情况下，本发明的实例在流体的使用寿命期间也将维持较高的燃点。
比较实例N和实例5-7：流体的氧化稳定性
使用改进的ASTM D-2893B测试表征表4中所鉴别的流体的氧化稳定性。将300毫升基础油放入硼硅酸盐玻璃管中，并使用ASTM D2893中所述的装置，在干燥空气流(10升/小时流速)下加热到121℃持续28天。在加热之前和在121℃下28天之后，根据ASTM D664测量总酸值(TAN)。这两个测量值之间的TAN值的变化确定流体是否通过或不通过氧化稳定性测试。TAN值的小变化对应于比TAN值的大变化更高的氧化稳定性。显示TAN增加量小于2.0mgKOH/g的流体“通过”测试，而显示TAN增加量超过2.0mgKOH/g的流体“未通过”测试。
表4
Figure BDA0001580595440000121
Figure BDA0001580595440000131
表4中的数据表明，S-PAG材料与抗氧化剂组合的协同增强的氧化稳定性。在0.5wt％的抗氧化剂装填量下，具有S-PAG基础油的流体容易通过氧化稳定性测试，而其他基础油即使具有两倍的抗氧化剂也无疑不能通过氧化稳定性测试。

Claims (9)

1.一种包含基础油和抗氧化剂的流体，所述基础油由含硫聚亚烷基二醇组成，所述含硫聚亚烷基二醇选自由具有下式的聚亚烷基二醇组成的组：
Figure FDA0002938166830000011
其中R1、R2、R3和R4独立地选自由以下组成的组：-CH3和-CH2CH3基团；R5选自由以下组成的组：氢；x是选自由1和2组成的组的数字；m、m'、n和n'独立地选自0到20范围内的整数，使得m、m'、n和n'的总和至少为6，并且A选自由-C2H4-和C6H4基团组成的组，其中所述流体有大于80重量百分比是含硫聚亚烷基二醇并且所述流体中有小于1重量百分比是水，其中重量百分比基于总流体重量，并且其中所述含硫聚亚烷基二醇不含直接与硫结合的氧。
2.根据权利要求1所述的流体，其中x是1，并且A是-C2H4-。
3.根据权利要求1所述的流体，其中R1、R2、R3和R4全部是-CH3基团。
4.根据权利要求1所述的流体，其中所述流体包含基于总流体重量，大于90重量百分比的所述含硫聚亚烷基二醇。
5.根据权利要求1所述的流体，其中所述抗氧化剂选自烷基化二苯胺。
6.根据权利要求1所述的流体，其中所述抗氧化剂是辛基化/丁基化二苯胺。
7.根据权利要求1所述的流体，其中所述流体不含具有不直接与硫结合的-C2H4O-基团的聚亚烷基二醇。
8.一种使用根据权利要求1所述的流体的方法，所述方法包括将所述的流体作为液压流体的材料引入设备中。
9.一种使用根据权利要求1所述的流体的方法，所述方法包括将所述的流体作为润滑流体的材料引入设备中。
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