CN1332784A - 高温用润滑油组合物 - Google Patents

高温用润滑油组合物 Download PDF

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CN1332784A
CN1332784A CN99815084A CN99815084A CN1332784A CN 1332784 A CN1332784 A CN 1332784A CN 99815084 A CN99815084 A CN 99815084A CN 99815084 A CN99815084 A CN 99815084A CN 1332784 A CN1332784 A CN 1332784A
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ester
high temperature
lubricant compositions
weight
antioxidant
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CN1179024C (zh
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上村秀人
永川浩
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Abstract

一种高温用润滑油组合物,其在薄膜状态时在高温下的蒸发受到抑制并保持长时间的流动性。该组合物是通过混合一种含(a)20%－100%重量的特定芳族酯化合物和(b)0－80%重量的其它基油的基油组合物与(c)按全部润滑油组合物量计,0.1－10%重量的抗氧化剂得到的。

Description

高温用润滑油组合物
技术领域
本发明涉及高温用润滑剂组合物。更具体地说，本发明涉及用于链条、滚轴链、链式输送机和轴承等的高温润滑剂组合物。
发明背景
由于在链条、滚轴链、链式输送机和轴承等中使用的润滑剂是暴露于高温的，所以润滑剂的蒸发量大大影响器械的寿命。因而，润滑剂在高温条件下丧失通常的粘度和变成薄膜，以致润滑剂的蒸发量必须在较严格的条件下加以控制。作为普通的高温用润滑剂，采用高粘度的高分子油控制蒸发量。尽管这种油的蒸发量不大，但功率损失是大的，而且从润滑剂的总性能来看是不理想的。加之，当这种油暴露于薄膜和高温时，残渣量很大，而且它们是固化的。不仅是作为液体的特征丧失，而它变成固化的淤渣，阻止了油的流动，招致润滑部分的不良润滑作用。
因此，高温用润滑剂需要控制高温下其在薄膜中的蒸发量和保持其在长时间内的流动性。
根据这一观点，作出了本发明，其目的在于提供一种高温润滑剂组合物，它在高温下薄膜内的蒸发量受到控制，和它的流动性在长时间内能够保持。
本发明的公开
本发明者经过刻苦调查研究，结果发现，本发明的目标可通过应用特定的芳族酯化合物作为基油来完成。这一发现导致了本发明的完成。
本发明的要点如下。
(1)一种通过混合含有(a)20％-100％重量的由如下通式(I)代表的芳族酯化合物
Figure A9981508400031
(其中R1代表具有6-16个碳原子的烷基，和n代1-6的整数)和(b)0-80％重量的另一种基油的基油组合物与(c)按润滑剂总量计0.1％-10％重量的抗氧化剂而得到的高温润滑剂组合物。
(2)如上面(1)中所述的高温润滑剂组合物，其中所述基油组合物含(a)30％-80％重量的芳族酯化合物和(b)20％-70％重量的另一种基油。
(3)如在上面(1)或(2)所述的高温润滑剂组合物，其中芳族酯化合物(a)是选自1，2，4-苯三酸烷基酯和均苯四酸烷基酯的一种。
(4)上面(1)-(3)所述的任一种高温润滑剂组合物，其中另一种基油(b)是选自α-烯烃低聚物、乙烯-α-烯烃低聚物、聚丁烯和它们的氢化物的一种或两种或多种。
(5)上面(1)-(4)所述任一种高温润滑剂组合物，其中抗氧化剂(c)是分子中含硫和/或磷的氧化剂。
(6)上面(1)-(5)中所述高温润滑剂组合物，其中抗氧化剂(c)选自二硫代磷酸盐和硫代磷酯中的一种。
(7)上面(1)-(5)所述高温润滑剂组合物，其中抗氧化剂(c)是2，6-二叔丁基-4-(4，6-二(辛硫基)-1，3，5-三嗪-2-基氨基)酚。
实现本发明的最佳方式
实现本发明的最佳方式如下所述。
构成本发明高温润滑剂组合物的基油组合物包含(a)20％-100％重量的由上面通式(I)所代表的芳族酯化合物和(b)0-80％重量的另一种基油。
就构成作为组分(a)的芳族酯化合物的芳族羧酸来说，键合于苯上的羧酸数目优选3或4。其中，1，2，4-苯三酸和均苯四酸是优选的。在芳族羧酸酯中采用的脂族醇，优选具有6-16个碳原子的线型或支化醇。其具体实例可包括1，2，4-苯三酸三正己基酯，1，2，4-苯三酸三-2-乙基己基酯，1，2，4-苯三酸三正辛基酯，1，2，4-苯三酸三-3，5，5-三甲基己基酯，均苯四酸四正己基酯，均苯四酸四-2-乙基己基酯，均苯四酸四正辛基酯，均苯四酸四-3，5，5-三甲基己基酯等。顺便提一句，芳族羧酸酯可以单一使用，或以两种或多种的混合物使用，和部分酯可被包含在全酯中。
作为另一种基油(b)，用作普通装备油的基油的任何矿物油类或合成油类均可使用。作为矿物油类基油，例如通过精炼润滑剂馏分所生成的精制油品，而润滑剂馏分是用普通的方法从石蜡基原油，中间基原油或环烷基原油的常压蒸馏或真空蒸馏得到的，如溶剂脱沥青，溶剂萃取，加氢裂化，溶剂脱蜡，催化脱蜡，氢化精炼，硫酸处理，粘土处理过程等。
此外，作为合成的油类基油，各种物质如α-烯烃低聚物，乙烯-0-低聚物，聚丁烯，二元酸酯，聚亚烷基二醇，受阻酯，烷基苯，烷基萘，聚醚等可以应用。在它们当中，α-烯烃低聚物，乙烯-α-低聚物，聚丁烯或这些物质的氢化物是优选的，因为它们可保持长时间的流动性。顺便说及，作为组分(b)，一种或两种或多种的混合物可以应用，以及矿物油和合成油的混合物可以应用。
芳族羧酸酯(a)和另一种基油(b)的比例是，组分(a)为20％-100％重量和组分(b)是0-80％重量，和优选组分(a)为30％-80％重量和组分(b)为20％-70％重量。当组分(a)少于20％重量时，达不到本发明的效果。
其次，对于与基油混合的作为组分(c)的抗氧化剂来说，胺类抗氧化剂和酚类抗氧化剂可以应用。从效力来看，分子中含硫和/或磷的抗氧化剂是优选的。
胺类抗氧化剂的实例包括单烷基二苯基胺，如单辛基二苯胺、单壬基二苯胺等；二烷基二苯胺，如4，4′-二丁基二苯胺、4，4′-二戊基二苯胺、4，4′-二己基二苯胺、4，4′-二庚基二苯胺、4，4′-二辛基二苯胺、4，4′-二壬基二荣胺等；多烷基二苯胺，如四丁基二苯胺、四己基二苯胺、四辛基二苯胺、四壬基二苯胺等；和萘胺，如α-萘胺、苯基-α-萘胺、丁基苯基-α-萘胺、戊基苯基-α-萘胺、己基苯基-α-萘胺、庚基苯基-α-萘胺、辛基苯基-α-萘胺、壬基苯基-α-萘胺等。
酚类抗氧化剂的实例可以包括单酚类，如2，6-二叔丁基-4-甲基酚、2，6-二叔丁基-4-乙基酚等；和联苯酚类，如4，4′-亚甲基双(2，6-二叔丁基酚)、2，2′-亚甲基双(4-乙基-6-叔丁基酚)等。
在分子中含硫和/或磷的抗氧化剂的实例可以是在分子中含硫和/或磷并具有抗氧化能力的添加剂，和它可因其它目的被加入。
首先说明分子中含硫的抗氧化剂。例如，可提及的有硫化油，硫化矿物油，硫化脂肪酸，硫化酯，硫化烯烃，二烃基多硫化物，噻二唑化合物，烷基硫化氨基甲酰化合物，三嗪化合物，硫代萜类化合物，二烷基硫代二丙酸酯化合物等。
这里，硫化油是通过硫或含硫化合物与油(猪油、鲸油、植物油、鱼油等)反应所得到的油，而其中的硫含量并不特别限定。通常，硫含量优选5％-30％重量。其特定实例包括硫化猪油，硫化菜子油，硫化海狸香油，硫化豆油，硫化米糠油等。硫化脂肪酸的实例包括硫化油酸等。硫化酯的实例包括硫化油酸甲酯，硫化米糠脂肪酸辛酯等。
作为硫化烯烃，例如，由下列通式(II)代表的化合物
R2-Sa-R3    (II)(其中R2代表具有2-15个碳原子的链烯基，R3代表具有2-15个碳原子的烷基或链烯基，和a代表1-8的整数)。
这种化合物是通过具有2-15个碳原子的烯烃或其二聚体至四聚体与硫化剂，如硫、氯化硫等反应而得到的。作为烯烃，丙烯、异丁烯、二异丁烯等是优选的。
此外二烃基多硫化物是由下列通式(III)代表的化合物
R4-Sb-R5    (III)(其中R4和R5各代表具有1-20个碳原子的烷基或环烷基，具有6-20个碳原子的芳基，具有7-20个碳原子的烷芳基或具有7-20个碳原子的芳烷基，和R4和R5可以相同或不同，而b代表2-8的整数)。
当其中R4和R5都是烷基时，该化合物称为烷基硫化物。
上面通式(III)中R4和R5的特定实例包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、各种戊基、各种己基、各种庚基、各种辛基、各种壬基、各种癸基、各种十二烷基、环己基、环辛基、苯基、萘基、甲苯基、二甲苯基、苄基、乙氧苯基等。
二烃基多硫化物的优选实例包括二苄基多硫化物，各种二壬基多硫化物，各种双十二烷基多硫化物，各种二丁基多硫化物，各种二辛基多硫化物，二苯基多硫化物，二环己基多硫化物等。
作为噻二唑化合物，例如，优选使用1，3，4-噻二唑和1，2，4-噻二唑化合物，它们由如下列通式(IV)代表
Figure A9981508400071
(其中R6和R7各代表氢原子或具有1-20个碳原子的烃基，而c和d各代表0-8的整数)。
噻二唑化合物的具体实例可包括2，5-二(己基二硫代)-1，3，4-噻二唑，2，5-二(正辛基二硫代)-1，3，4-噻二唑，2，5-二(正壬基二硫代)-1，3，4-噻二唑，2，5-二(1，1，3，3-四甲基丁基二硫代)-1，3，4-噻二唑，3，5-二(正己基二硫代)-1，2，4-噻二唑，3，5-二(正辛基二硫代)-1，2，4-噻二唑，3，5-二(正壬基二硫代)-1，2，4-噻二唑，3，5-二(1，1，3，3-四甲基丁基二硫代)-1，2，4-噻二唑等。
作为烷基硫代氨基甲酰基化合物，例如，下列通式(V)代表的化合物是可优选使用的。(其中R8-R11各代表具有1-20个碳原子的烷基，和e代表1-8的整数)。
烷基硫代氨基甲酰基化合物的具体实例包括二(二甲基硫代氨基甲酰基)一硫化物，二(二丁基硫代氨甲酰基)一硫化物，二(二甲基硫代氨甲酰基)二硫化物，二(二丁基硫代氨甲酰基)二硫化物，二(二戊基硫代氨甲酰基)二硫化物，二(二辛基硫代氨甲酰基)二硫化物等。
三嗪化合物的优选实例包括2，6-二叔丁基-4-(4，6-二(辛硫基)-1，3，5-三嗪-2-基氨基)酚等。
此外，硫代萜类化合物包括五硫化二磷和蒎烯的反应产物。二烷基硫代二丙酸酯化合物的实例包括二月桂基硫代二丙酸酯，二硬脂酰硫代二丙酸酯等。
此外，作为含硫和金属的抗氧化剂，也可以采用二烷基二硫代氨基甲酸锌(Zn-DTC)，二烷基二硫代氨基甲酸钼(Mo-DTC)，二烷基二硫代氨基甲酸铅，二烷基二硫代氨基甲酸锡，磺酸钠，磺酸钙等。
下面叙述分子中含磷的抗氧化剂。典型实例包括磷酸酯和其胺盐。
磷酸酯包括磷酸酯，酸式磷酸酯，亚磷酸酯和酸式亚磷酸酯，它们由下列通式(VI)-(X)代表。
Figure A9981508400081
在通式(VI)-(X)中，R12-R14各代表烷基，链烯基，烷芳基和芳烷基，它们具有4-30个碳原子，和R12-R14可以相同或不同。
所述磷酸酯包括磷酸三芳基酯，磷酸三烷基酯，磷酸三烷芳基酯，磷酸三芳烷基酯，三链烯基磷酸酯等。它们的特定实例包括磷酸三苯基酯，磷酸三(甲苯酯)，磷酸苄基二苯基酯，磷酸乙基二苯基酯，磷酸三丁酯，磷酸乙基二丁基酯，磷酸甲苯·联苯酯，磷酸二甲苯基苯基酯，磷酸乙基苯基联苯基酯，磷酸二乙基苯基苯基酯，磷酸丙基苯基联苯基酯，磷酸二丙基苯基苯基酯，磷酸三乙基苯基酯，磷酸三丙基苯基酯，磷酸丁基苯基联苯基酯，磷酸二丁基苯基苯基酯，磷酸三丁基苯基酯，磷酸三己基酯，磷酸三(2-乙基己基)酯，磷酸三癸基酯，磷酸三月桂基酯，磷酸三肉豆蔻基酯，磷酸三棕榈基酯，磷酸三硬脂酰酯，磷酸三油基酯等。
酸式磷酸酯的特定实例包括酸式磷酸2-乙基己基酯，酸式磷酸乙酯，酸式磷酸丁酯，酸式磷酸油基酯，酸式磷酸二十四烷基酯，酸式磷异癸酯，酸式磷酸月桂基酯，酸式磷酸十三烷基酯，酸式磷酸硬脂酰酯，酸式磷酸异硬脂酰酯等。
亚磷酸酯的特定实例包括亚磷酸三乙酯，亚磷酸三丁酯，亚磷酸三苯基酯，亚磷酸三(甲苯酯)，亚磷酸三(壬基苯基)酯，亚磷酸三(2-乙基己基)酯，亚磷酸三癸酯，亚磷酸三月桂基酯，亚磷酸三异辛酯，亚磷酸二苯基异癸酯，亚磷酸三硬脂酰酯，亚磷酸三油基酯等。
酸式亚磷酸酯的具体实例是亚磷酸二丁基氢酯，亚磷酸二月桂基氢酯，亚磷酸二油基氢酯，亚硫酸二硬脂酰氢酯，亚磷酸二苯基氢酯等。
此外，与包括一取代胺，二取代胺和三取代胺形成胺盐的胺类由通式(XI)代表
R15 mNH3-m    (XI)(其中R15代表具有3-30个碳原子的烷基或链烯基，具有6-30个碳原子的芳基或芳烷基或具有2-30个碳原子的羟基烷基，m代表1，2或3，和当R15是复数基团时，多个R15可以是相同或不同的)。
在通式(XI)的R15中，具有3-30个碳原子的烷基或链烯基可以是线型的，支化的或环状的。
这里，一取代胺的实例可包括丁胺，戊胺，己胺，环己胺，辛胺，月桂基胺，硬脂酰胺，油胺，苄胺等。二取代胺的实例可包括二丁胺，二戊胺，二己胺，二环己胺，二辛胺，二月桂基胺，二硬脂酰胺，二油胺，二苄胺，硬脂酰单乙醇胺，癸基·单乙醇胺，己基·单丙醇胺，苄基·单乙醇胺，苯基·单乙醇胺，甲苯基·单丙醇胺等。三取代胺的实例包括三丁胺，三戊胺，三己胺，三环己胺，三辛胺，三月桂基胺，三硬脂酰胺，三油胺，三苄胺，二油基·单乙醇胺，二月桂基·单丙醇胺，二辛基·单乙醇胺，二己基·单丙醇胺，二丁基·单丙醇胺，油基·二乙醇胺，硬脂酰·二丙醇胺，月桂基·二乙醇胺，辛基·二丙醇胺，丁基·二乙醇胺，苄基·二乙醇胺，苯基·二乙醇胺，甲苯基·二丙醇胺，二甲苯基·二乙醇胺，三乙醇胺，三丙醇胺等。
含磷和卤原子的抗氧化剂的实例可包括氯化磷酸酯。
分子中含硫和磷的抗氧化剂的实例可包括硫化磷油，硫化磷烯烃，硫代磷酸酯(硫代亚磷酸酯和硫代磷酸酯)等。它们当中，硫代亚磷酸酯(烷芳基型)和硫代磷酸酯(烷芳基型)是优选的。
含硫、磷和金属的抗氧化剂的实例可包括二硫代磷酸盐，如二硫代磷酸锌(Zn-DTP)，二硫代磷酸钼(Mo-DTP)，二硫代磷酸铅，二硫代磷酸锡等。
在上述抗氧化剂中，2，6-叔丁基-4-(4，6-二(辛硫基)-1，3，5-三嗪-2-基氨基)酚，Zn-DTP(烷芳基型)，硫代亚磷酸酯(烷基型)和硫代磷酸酯(烷芳基型)是优选的。
此外，上述抗氧化剂既可单独使用，也可结合使用。
上述抗氧化剂优选的混合量，按组合物总量计，在0.1％-10％重量范围内。当混合量少于0.1％重量时，本发明的目标不能充分显示。当混合量超过10％重量时，有时观察不到效力的改进，即使等于10％重量也如此，而且在基油中的溶解性有时减少。更优选的混合量是1％-7％的范围。
根据需要，本发明的高温用润滑剂组合物可以含有各种已知的添加剂，如抗锈剂，洗涤分散剂，金属钝化剂，消泡剂等，除非有损于本发明的目标。
抗锈剂的实例可包括金属磺酸盐，琥珀酸酯等。
洗涤分散剂的实例可包括金属磺酸盐，金属水杨酸盐，金属finate，琥珀酰亚胺等。
金属钝化剂的实例可包括苯并三唑，噻二唑等。
消泡剂的实例可包括甲基硅油，氟硅油，聚丙烯酸酯等。
为了达到既定目标，将本发明的高温用润滑剂组合物40℃的运动粘度调节到10-50mm2/s是可取的。更优选在50-320mm2/s范围。
顺便地说，当温度超过150℃，在多于50％使用周期的时间内，优选使用本发明的高温用润滑剂组合物。
以下，参考实例更具体地说明本发明。然而，本发明并不完全限于这些实例。
[实例1-6和对比例1和2]
如表1中所示，将基油与抗氧化剂混合，以制备润滑剂组合物。该组合物的粘度通过调节α-烯烃低聚物的粘度进行，依此，在40℃时的运动粘度全部被调节到220mm2/s。该组合物的薄膜残留试验按下面方式进行。此外，倾斜容器和目测评定此时的流动性。所得结果示于表1中。
薄膜残留试验
用一个容器和一个JISK 2540润滑剂热稳定性试验所需的恒温空气浴在200℃24小时时间内测量该残留量。该量用百分数表示，定义为残留比。顺便说，10升/小时的空气总是引起测量期间的浮动。
                        表1(1)
   Ex.1   Ex.2   Ex.3    Ex.4
混合比重量％ α-烯烃低聚物*1    平衡   平衡   平衡    平衡
聚丁烯*2     20     20     20     20
芳族酯1*3     50     50     50     50
芳族酯2*4     -     -     -     -
双酚*5     1     1     1     1
二苯胺*6     1     1     1     1
二硫代磷酸盐*7     -     2     -     -
硫代磷酸酯*8     -     -     2     -
三嗪类含硫化物     -     -     -     2
残留比(％)     62.5    70.2    67.3    76.6
流动性(目视观测)     +     +     +     +
                                表1(2)
  Ex.5   Ex.6  CEx.1  CEx.2
混合比重量％ α-烯烃低聚物*1   平衡   平衡   平衡   平衡
聚丁烯*2     20     20     20     20
芳族酯1*3     -     -     -     -
芳族酯2*4     50     50     -     -
双酚*5     1     1     1     1
二苯胺*6     1     1     1     1
二硫代磷酸盐*7     -     2     -     2
硫代磷酸酯*8     -     2     -     2
三嗪类含硫化物     2     -     -     -
残留比(％)     78.1     84.1     50.6     55.2
流动性(目视观测)     +     +     -     -
Ex.-实例，CEx.-对比例
(注释)
*1低聚物的氢化物质，1-癸烯
(在40℃的运动粘度为20-63mm2/s)
*2数均分子量：2,300
*3三正辛基苯三酸酯
*4三正基-1，2，4，5-苯四酸酯
*5 4，4′-亚甲基双(2，6-二叔丁基苯酚)
*6 4，4′-二丁基二苯胺
*7烷芳基型Zn-DTP
*8三异壬基酚硫代磷酸酯
*9 2，6-二叔丁基-4-(4，6-二(辛硫基)-1，3，5-三嗪-2-基氨基)酚
工业实用性
按照本发明，可提供一种高温用润滑剂组合物，该组合物在薄膜内在高温下的蒸发量被控制，而且其流动性可以保持很长的时间。

Claims (7)

1.一种高温用润滑剂组合物，它是通过混合一种含(a)20％-100％重量的由下列通式(I)代表的芳族酯化合物(式中R1代表具有6-16个碳原子的烷基，和n代表1-6的整数)和(b)0-80％重量的另一种基油的基油组合物与(c)按润滑剂组合物的总量计，0.1％-10％重量的抗氧化剂得到的。
2.如权利要求1所要求的高温用润滑剂组合物，其中所述基油组合物含(a)30％-80％重量的芳族酯化合物和(b)20％-70％重量的另一种基油。
3.如权利要求1或2所要求的高温用润滑剂组合物，其中芳族酯化合物(a)是选自1，2，4-苯三酸烷基酯和均苯四酸烷基酯的一种。
4.权利要求1-3的任一项所要求的高温用润滑剂组合物，其中另一种基油(b)是选自α-烯烃低聚物，乙烯-α-烯烃低聚物、聚丁烯和它们的氢化物的一种或两种或多种。
5.权利要求1-4任一项所要求的高温用润滑剂组合物，其中抗氧化剂(c)是分子中含硫和/或磷的抗氧化剂。
6.权利要求1-5任一项所要求的高温用润滑剂组合物，其中抗氧化剂(c)是选自二硫代磷酸盐和硫代磷酸酯的一种。
7.权利要求1-5任一项所要求的高温用润滑剂组合物，其中抗氧化剂(c)是2，6-二叔丁基-4-(4，6-二(辛硫基)-1，3，5-三嗪-2-基氨基)酚。
CNB998150843A 1998-12-25 1999-12-22 高温用润滑油组合物 Expired - Fee Related CN1179024C (zh)

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