CN102066536A - 基于天然和可再生的原料的润滑剂组合物 - Google Patents

基于天然和可再生的原料的润滑剂组合物 Download PDF

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CN102066536A
CN102066536A CN200980122020.3A CN200980122020A CN102066536A CN 102066536 A CN102066536 A CN 102066536A CN 200980122020 A CN200980122020 A CN 200980122020A CN 102066536 A CN102066536 A CN 102066536A
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oil
lubricant compositions
ester
natural
weight
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CN102066536B (zh
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T.基尔特奥
M.施密特-阿梅伦克森
S.齐克尔
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Klueber Lubrication Muenchen GmbH and Co KG
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Klueber Lubrication Muenchen GmbH and Co KG
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Abstract

本发明涉及基于改性的天然和可再生的原料的润滑剂组合物，其粘度能依应用而调节。本发明特别涉及可生物降解的润滑剂组合物。

Description

基于天然和可再生的原料的润滑剂组合物
本发明涉及一种基于改性的天然和可再生的原料的润滑剂组合物，其粘度可依应用调节。本发明特别涉及可生物降解的润滑剂组合物。
从DE 103 29 761 A1已知用电离辐射改性天然油和可再生油。其中该电离辐射的作用以多个作用时间段实现，在处理步骤之间总存在休息期。这种改性反应在加入引发剂如化学催化添加剂、络合性化合物和/或有机促进剂下进行。此外还已知，该要用电离辐射处理的油的改性程度受剂量、温度、剂量率、氧以及引发剂或抑制剂作用的影响。但这类已知的改性方法的缺点是其不可以大工业规模实施，并且通常导致不能完全重复的结果。
因此，US 4 327 030 A中描述了一种改变基于甘油三酯的天然油的方法，其中使该油在100-200℃温度与过氧化物反应。在留下的残余物中的多不饱和的聚合脂肪酸酯经分离和处置。该方法用于降低亚油酸的含量，以提高油酸含量。由此得到含更高油酸含量的油。
此外，还描述了植物油的天然氧化。原则上暗示了天然甘油三酯的优良润滑特性。但其有很大的局限性，因为该油由于其高的双键含量极易受氧化，并由此大大限制了其应用领域。此外，氧化的残余物由于磨损导致构件如滚动轴承的失效。
为改进这类油的耐氧化性，提出混入酚类和芳香类的胺-抗氧化剂或加入油溶性的铜化合物。
由于石油(其矿物油成分仍然用作制备润滑剂组合物的基料)的日益短缺，需要在将来可以用可再生原料来代替该矿物油成分。但该基于天然和可再生原料的天然油作为润滑剂的应用由于其小的粘度仅限于少数应用领域。
本发明的目的在于提供一种基于甘油三酯的天然的可再生油类的润滑剂组合物，其粘度可依所需应用而调节。本发明的另一目的在于提供一种润滑剂组合物，该润滑剂组合物含改性的天然油和在高温区域和低温区域的极端温度下具有好的摩擦特性和好的耐氧化性。
本发明的目的是通过润滑剂组合物实现的，该润滑剂组合物中的基于甘油三酯的天然油与过氧化物反应，并借助于自由基加成反应使脂肪酸的不饱和成分相互键合。通过该反应改变该改性油的粘度。该粘度可依过氧化物/油-比例调节到所需值，并由此适合于各个应用的要求。依该改性油的粘度，该润滑剂组合物可用作NLGI级000.00的润滑脂、用作集中润滑装置(Zentralschmieranlage)和传动润滑领域的润滑脂以及用作在滑动轴承、滚动轴承中和适于NLGI 1-4级水泵的所谓软脂或用作NLGI 5和6级的作为密封脂或脂块用的所谓硬脂。
本发明的润滑剂组合物的基础是改变基于甘油三脂的天然油的粘度的方法，其中该天然油与过氧化物在165℃-190℃的温度反应3-5小时，接着该不饱和的双键通过自由基加成反应而键合。然后该在聚合中所形成的副产物在高真空下经分离。如此得到的粘度改变过的油可就地经再加工以制备润滑剂。为使天然油与过氧化物化合物反应，可按待制备的油的所需粘度使用4.8%-10.3%的相应的过氧化物化合物。这可得到粘度为100-1250 mm2/sec的油。图1示出粘度与过氧化物浓度之间的关系。通过不同量的过氧化物化合物也可用简单方式可重现地制备高粘度油及低粘度油。
所用的过氧化物可以是芳族的也可以是脂族的过氧化物化合物。优选地，该过氧化物选自1,3-双(叔丁基过氧基异丙基)苯、1,4-双(叔丁基过氧基异丙基)苯、二枯基过氧化物、叔丁基枯基过氧化物、2,5-二甲基-2,5-二-(叔丁基过氧基)己烷、正丁基-4,4’-二(叔丁基过氧基)戊酸酯、1,1-二-(叔丁基过氧基)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二-(叔丁基过氧基)己烷。特别优选的是脂族过氧化物化合物如2,5-二甲基-2,5-二-(叔丁基过氧基)己烷或二-叔丁基过氧化物。
为与上述过氧化物反应并接着进行自由基加成反应，具有高含量的不饱和组分的油特别适用，该不饱和组分可以是单不饱和或多不饱和的。特别适用的是含高油酸含量的植物油。油酸含量为65%-85%的橄榄油特别适合作为天然的非转基因的油。此外，优选油酸含量至少为60%的植物油。这些油也可以是转基因的，以提高油酸含量。天然油可选自高油酸含量的红花油、高油酸含量的玉米油、高油酸含量的菜子油、高油酸含量的葵花油、高油酸含量的大豆油、高油酸含量的亚麻油、高油酸含量的花生油、高油酸含量的“雷斯克懒勒”油、高油酸含量的棕榈油、高油酸含量的篦麻油、高油酸含量的亚麻子油或高油酸含量的橄榄油以及上述油的混合物。
如此得到的具有比起始油更高粘度的改性油在其摩擦特性、耐氧化性和在 -30℃至180℃应用范围方面是低成本的且可重复地制备。与矿物油相比，其优点为可生物降解且在时间上可不受限制地提供使用。
如上所述，利用油中的不饱和组分通过与过氧化物反应经自由基加成反应使不饱和的脂肪酸完全或部分相互键合。在此方法中，该改性油的聚合度与油对过氧化物的比有关。反应温度和反应时间也对聚合程度有附加影响。如此得到的改性油在低温下具有强的改进特性，但也可在高温下使用，并具有非常高的特性粘度（VI），其大于210。此外，其具有非常好的摩擦特性和优异的耐氧化性。
本发明的基于天然改性油的润滑剂组合物具有极性特性，并可作为薄的粘附膜施加于金属表面上，由此实现优异的润滑作用。与基于矿物油或烃的润滑剂相反，该润滑膜不能容易地从金属表面剥落，这使得本发明的润滑剂的应用范围还扩展到液压应用。特别是通过该润滑剂的交联结构使其在热负荷和机械负荷方面比直链烃组合物更为稳定。
基于可再生原料的高粘性油也适合完全或部分代替在许多润滑剂中用作基础组分的所谓的“光亮油(Brightstock)”。
含基于甘油三酯的改性的天然油的润滑剂组合物概括地说其优点为，其由可再生的原材料制备，原料可生物降解和是无毒的，具有高的燃点，热稳定和具有优异的低温特性。此外，在金属表面上还有改进的粘附能力。
如下所述，相应于该润滑剂组合物的上述应用，可再生和天然油的运动粘度在40℃为100-1250 mm2/sec。
用改性的天然油制备的润滑剂组合物包含：
(a) 50-90重量%的基于甘油三酯的含高油酸成分改性的天然油，其选自葵花油、菜子油、篦麻油、亚麻子油、玉米油、红花油、大豆油、亚麻油、花生油、“雷斯克懒勒”油、棕榈油、橄榄油或上述油的混合物，该天然油与过氧化物反应，并通过自由基加成反应使不饱和双键键合，和
(b) 5-10重量%的添加剂或添加剂混合物，
其中改性天然油的粘度为100-1250 mm2/sec。
这类润滑剂组合物优选用作变速器油。
该润滑剂组合物还可含：
(c) 5-30重量%的增稠剂。
这种组合物通常用作润滑脂。
如果该润滑剂组合物除含组分(a)-(c)外，还可含
(d) 5-10重量%的固体润滑剂，
则其可优选用作传动润滑脂。
如上所述，可用改性的天然油替代一部分所谓的“光亮油”。在这类润滑剂组合物中除含组分(a)-(d)外还含组分(e) 5-45重量%的其它基油成分或多种基油成分。
该润滑剂组合物的增稠剂选自脲、铝复合皂、周期表的第1和第2主族元素的金属简单皂、周期表的第1和第2主族元素的金属复合皂、膨润土、磺酸盐、硅酸盐、聚酰亚胺或PTFE或上述增稠剂的混合物。
该固体润滑剂选自石墨、氮化硼、MoS2、WS2、SnS、SnS2、或Bi2S3或上述固体润滑剂的混合物。
该添加剂或添加剂混合物选自丁基羟基甲苯、二烷基二苯基胺、烷基化苯基-α-萘胺、聚合的三甲基二氢喹啉、硫化的脂肪酸酯、二苯基甲苯基磷酸酯、胺中和的磷酸盐/酯、烷基化和未烷基化的三芳基磷酸酯、烷基化和未烷基化的三芳基硫代磷酸酯、二烷基二硫代磷酸锌、氨基甲酸盐/酯、硫代氨基甲酸盐/酯、二硫代氨基甲酸锌、二巯基-噻二唑、琥珀酸半酯、磺酸钙、苯并三唑衍生物、五硼酸钾、硫代硫酸钠和焦磷酸钠。
该润滑剂组合物的基油成分选自基于链烷烃的和基于环烷烃的矿物油、合成烃、聚-α-烯烃(PAO)、聚内烯烃(PIO)、乙烯-丙烯-共聚物、III类油(Gruppe III-Öl)、合成酯、聚亚烷基二醇或烷基芳族化合物以及其混合物。
特别有利的是，在应用前使该油与过氧化物反应，然后将相应的添加物如增稠剂，如硅酸盐、磺酸盐、聚酰亚胺、金属皂、金属皂复合物、脲和膨润土就地加入到预先聚合的油中。该聚合的油也可与其它基油成分如基于链烷烃的和基于环烷烃的矿物油、合成烃(聚-α-烯烃、聚内烯烃、乙烯-丙烯-共聚物)、III类油、合成酯、聚亚烷基二醇(PAG)或烷基芳族化合物混入润滑剂配制剂中。其中可使用通常的防磨损添加剂和固体润滑剂添加剂如三芳基磷酸酯、三芳基硫代磷酸酯、二烷基二硫代磷酸锌、氨基甲酸盐/酯、硫代氨基甲酸盐/酯、二硫代氨基甲酸锌、MoS2、石墨、氮化硼、PTFE、硫代硫酸钠、焦磷酸钠等。酚类和胺类的抗氧化剂通常作为抗氧化剂，其中优选使用聚合的三甲基二氢喹啉或硫化的脂肪酸酯。
有利的是，本发明的润滑剂组合物可在使用前短时间内以所谓的一锅反应方式快速和可重现地混合。
下面描述本发明的润滑剂组合物作为针对蜗轮蜗杆传动装置的变速器油(Getriebeöl)的用途。与合适的基于磷和基于基的添加剂以及丁基羟基甲苯、二烷基二苯基胺、二苯基甲苯基磷酸酯、胺中和的磷酸盐/酯、琥珀酸半酯和三唑衍生物一起研制基于ISO VG 460标准的含高油酸含量的聚合葵花油。上述添加剂混合物的量约为大约6%。该润滑剂组合物在蜗轮蜗杆传动装置试验台架上试验300小时。该研究表明，该改性的葵花油的效率为70-80%，由此达到常规的基于聚-α-烯烃和聚亚烷基二醇的变速器油的效率。从降低磨损和在摩擦位置上的流体动力润滑膜的快速建立来看，本发明的润滑剂组合物远优于常规的变速器油。图2中所示的由蜗轮蜗杆传动装置试验台架所得出的结果表明了这点。
特别是经300小时运行时间的非常小的磨损和非常快建立起来的流体动力润滑表明这种天然的变速器油的优良润滑特性。
作为本发明的润滑剂组合物的另一实例研制了NLGI 1级的脲基酯。这种滚动轴承脂含52重量%的具有高油酸含量的ISO VG 460改性的聚合葵花油、38.3重量%的矿物油(光亮油)以及6.59重量%的增稠剂和3.05重量%的由二烷基二硫代磷酸锌、硫化的脂肪酸酯、苯并三唑和抗氧化剂组成的用于热稳定化的添加剂混合物。用该脂配方可在FE9试验机上于140℃达到＞100小时的L50值。图3示出FE9试验的试验条件和结果。
图4所示结果表明，从光亮油含量＜20%起就可明显延长运行时间，并且该改性的葵花油可通过合适的添加剂而热稳定化。
无色的可生物降解的传动润滑脂的实例是由改性的葵花油组成的组合物，该油中加有钙皂作为增稠剂，其40℃的粘度为700 mm2/sec。这种润滑剂组合物曾与基于矿物油和铝皂作为增稠剂的润滑剂组合物进行比较，该增稠剂还含石墨作为固体润滑剂。
表 1
。
如表1所示，本发明的基于改性的可生物降解的葵花油的润滑剂组合物与标准润滑脂相比相同的结果，如果不比其更好的话。此外，该润滑剂组合物可生物降解并是无色的，即可不使用固体润滑剂如石墨。可满足客户对尽可能不是黑的脂的需要。
基于甘油三酯的改性天然油的另一应用是在应用套件中使用，该应用套件含70-90重量%的运动粘度在40℃为100-1250 mm2/sec，特别是在40℃为350-550 mm2/sec的改性的葵花油聚合物和30-10重量%锂基皂，在使用紧前面将这些组分相互混合，由此得到NLGI级为0-2的脂，并且锂基皂可通过用LiOH x H2O以1∶1摩尔比直接皂化改性的葵花油聚合物制备。这类套件例如可用于滑动轴承中。
权利要求书(按照条约第19条的修改)
1. 润滑剂组合物，其包含：
(a) 50-90重量%的基于甘油三酯的具有至少60％的油酸含量的改性的天然油，所述天然油选自葵花油、菜子油、篦麻油、亚麻子油、玉米油、红花油、大豆油、亚麻油、花生油、“雷斯克懒勒”油、棕榈油、橄榄油或上述油的混合物，其中使该天然油与过氧化物反应，并通过自由基加成反应使不饱和双键键合，和
(b) 5-10重量%的添加剂或添加剂混合物，
(c) 5-30重量%的增稠剂，
其中该改性的天然油的运动粘度在40℃为100-1250mm2/sec。
2. 权利要求1的润滑剂组合物，其还含
(d) 5-10重量%的固体润滑剂。
3. 前述权利要求之一的润滑剂组合物，其中5-45重量%的天然改性油被其它基油成分或多种基油成分所替代。
4. 前述权利要求之一的润滑剂组合物，其中该增稠剂选自脲、铝复合皂、周期表第1和第2主族元素的金属简单皂、周期表第1和第2主族元素的金属复合皂、膨润土、磺酸盐、硅酸盐、聚酰亚胺或PTFE或上述增稠剂的混合物。
5. 前述权利要求2或3之一的润滑剂组合物，其中该固体润滑剂选自石墨、氮化硼、MoS2、WS2、SnS、SnS2或Bi2S3或上述固体润滑剂的混合物。
6. 前述权利要求之一的润滑剂组合物，其中该添加剂或添加剂混合物选自丁基羟基甲苯、二烷基二苯基胺、烷基化苯基-α-萘胺、聚合的三甲基二氢喹啉、硫化的脂肪酸酯、二苯基甲苯基磷酸酯、胺中和的磷酸盐/酯、烷基化和未烷基化的三芳基磷酸酯、烷基化和未烷基化的三芳基硫代磷酸酯、二烷基二硫代磷酸锌、氨基甲酸盐/酯、硫代氨基甲酸盐/酯、二硫代氨基甲酸锌、二巯基-噻二唑、琥珀酸半酯、磺酸钙、苯并三唑衍生物、五硼酸钾、硫代硫酸钠、焦磷酸钠。
7. 前述权利要求3-6之一的润滑剂组合物，其中基油成分选自基于链烷烃的和基于环烷烃的矿物油、合成烃、聚-α-烯烃、聚内烯烃、乙烯-丙烯-共聚物、III类油、合成酯、聚亚烷基二醇或烷基芳族化合物以及其混合物。
8. 前述权利要求之一的润滑剂组合物，其中该天然油与芳族或脂族的过氧化物反应，该过氧化物选自1,3-双(叔丁基过氧基异丙基)苯、1,4-双(叔丁基过氧基异丙基)苯、二枯基过氧化物、叔丁基枯基过氧化物、2,5-二甲基-2,5-二-(叔丁基过氧基)己烷、正丁基-4,4’-二(叔丁基过氧基)戊酸酯、1,1-二-(叔丁基过氧基)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二-(叔丁基过氧基)己烷或二-叔丁基过氧化物。
9. 前述权利要求之一的润滑剂组合物的用途，作为变速器油，用于油润滑锥齿轮传动和圆柱齿轮传动，作为滚动轴承脂来润滑连续铸锭装置中的滚轮轴承和连续式加热炉中的传送滚轮轴承，或作为传动润滑脂用于对水泥工业、石灰工业、石膏工业、矿业和化学工业中的转筒炉、管式磨、滚筒和混合器进行敞开式齿环润滑。
10. 应用套件，其包含
70-90重量%的运动粘度在40℃为100-1250 mm2/sec，特别是在40℃为350-550 mm2/sec的改性的葵花油聚合物，和
30-10重量%的锂基皂，
其中在使用紧前面将这些组分相互混合，由此得到NLGI-级为0-2的脂，并且其中锂基皂通过用LiOH x H2O以1∶1摩尔比直接皂化该改性的葵花油聚合物制备。

Claims (11)

1. 一种润滑剂组合物，其含
(a) 50-90重量%的基于甘油三酯的含高油酸成分改性的天然油，所述天然油选自葵花油、菜子油、篦麻油、亚麻子油、玉米油、红花油、大豆油、亚麻油、花生油、“雷斯克懒勒”油、棕榈油、橄榄油或上述油的混合物，其中使该天然油与过氧化物反应，并通过自由基加成反应使不饱和双键键合，和
(b) 5-10重量%的添加剂或添加剂混合物，
其中该改性天然油的运动粘度为100-1250mm2/sec。
2. 权利要求1的润滑剂组合物，其还含
(c) 5-30重量%的增稠剂。
3. 权利要求1或2的润滑剂组合物，其还含
(d) 5-10重量%的固体润滑剂。
4. 前述权利要求之一的润滑剂组合物，其中5-45重量%的天然改性油被其它基油成分或多种基油成分所替代。
5. 前述权利要求之一的润滑剂组合物，其中该增稠剂选自脲、铝复合皂、周期表第1和第2主族元素的金属-简单皂、周期表第1和第2主族元素的金属复合皂、膨润土、磺酸盐、硅酸盐、聚酰亚胺或PTFE或上述增稠剂的混合物。
6. 前述权利要求之一的润滑剂组合物，其中该固体润滑剂选自由下列组成的组：石墨、氮化硼、MoS2、WS2、SnS、SnS2、或Bi2S3，或上述固体润滑剂的混合物。
7. 前述权利要求之一的润滑剂组合物，其中该添加剂或添加剂混合物选自丁基羟基甲苯、二烷基二苯基胺、烷基化苯基-α-萘胺、聚合的三甲基二氢喹啉、硫化的脂肪酸酯、二苯基甲苯基磷酸酯、胺中和的磷酸盐/酯、烷基化和未烷基化的三芳基磷酸酯、烷基化和未烷基化的三芳基硫代磷酸酯、二烷基二硫代磷酸锌、氨基甲酸盐/酯、硫代氨基甲酸盐/酯、二硫代氨基甲酸锌、二巯基-噻二唑、琥珀酸半酯、磺酸钙、苯并三唑衍生物、五硼酸钾、硫代硫酸钠和焦磷酸钠。
8. 前述权利要求之一的润滑剂组合物，其中基油成分选自基于链烷烃的和基于环烷烃的矿物油、合成烃、聚-α-烯烃、聚内烯烃、乙烯-丙烯-共聚物、III类油、合成酯、聚亚烷基二醇或烷基芳族化合物以及其混合物。
9. 前述权利要求之一的润滑剂组合物，其中该天然油与芳族或脂族的过氧化物反应，该过氧化物选自1,3-双(叔丁基过氧基异丙基)苯、1,4-双(叔丁基过氧基异丙基)苯、二枯基过氧化物、叔丁基枯基过氧化物、2,5-二甲基-2,5-二-(叔丁基过氧基)己烷、正丁基-4,4’-二(叔丁基过氧基)戊酸酯、1,1-二-(叔丁基过氧基)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二-(叔丁基过氧基)己烷或二-叔丁基过氧化物。
10. 前述权利要求之一的润滑剂组合物的用途，作为变速器油，用于油润滑锥齿轮传动和圆柱齿轮传动，作为滚动轴承脂来润滑连续铸锭装置中的滚轮轴承和连续式加热炉中的传送滚轮轴承，或作为传动润滑脂用于对水泥工业、石灰工业、石膏工业、矿业和化学工业中的转筒炉、管式磨、滚筒和混合器进行敞开式齿环润滑。
11. 应用套件，其包含
70-90重量%的运动粘度在40℃为100-1250 mm2/sec，特别是在40℃为350-550 mm2/sec的改性的葵花油聚合物，和
30-10重量%的锂基皂，
其中在使用紧前面将这些组分相互混合，由此得到NLGI-级为0-2的脂，并且其中锂基皂通过用LiOH x H2O以1∶1摩尔比直接皂化该改性的葵花油聚合物制备。
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BRPI0913418A2 (pt) 2015-11-24
SI2300581T1 (sl) 2012-11-30
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AU2009256887A1 (en) 2009-12-17
US8455411B2 (en) 2013-06-04
US20110124537A1 (en) 2011-05-26
CA2727157C (en) 2014-03-04
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DE102009022593A1 (de) 2009-12-17
AU2009256887B2 (en) 2013-10-10
EP2300581A1 (de) 2011-03-30
HK1157811A1 (en) 2012-07-06
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BRPI0913418B1 (pt) 2017-12-12

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