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CN111073729A - 自动变速器油组合物 - Google Patents

自动变速器油组合物 Download PDF

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Publication number
CN111073729A
CN111073729A CN201910091449.6A CN201910091449A CN111073729A CN 111073729 A CN111073729 A CN 111073729A CN 201910091449 A CN201910091449 A CN 201910091449A CN 111073729 A CN111073729 A CN 111073729A
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China
Prior art keywords
automatic transmission
bis
oil composition
transmission oil
zirconium dichloride
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CN201910091449.6A
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CN111073729B (zh
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吴廷濬
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Hyundai Motor Co
Kia Corp
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Hyundai Motor Co
Kia Motors Corp
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Abstract

一种自动变速器油组合物，其包含80至85wt％的基础油、1至5wt％的茂金属聚α烯烃、1至5wt％的清净分散剂、0.01至0.03wt％的三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂、3至10wt％的粘度改进剂，和3至5wt％的抗磨添加剂。通过将基础油与茂金属聚α烯烃和三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂以特定的混合比例混合以制备该自动变速器油组合物，由此可以将动摩擦系数保持在同等的水平并且可以降低金属摩擦系数，从而提高传动金属之间的动力传递效率以及燃料经济性(提高1.5％或更高)、增加耐久性，并使能量损失最小化。

Description

自动变速器油组合物
技术领域
本公开涉及一种用于车辆中的润滑油组合物。
背景技术
近年来，为了鼓励有效利用能源和防止全球变暖，对车辆排放的废气(诸如二氧化碳等)的监管变得更加严格。由于这样的环境法规，已经积极地开发了改进燃料经济性的发动机和可以降低发动机能量损失的变速器油。
特别是在变速器油中，在换档时改进摩擦特性可以提高动力传递效率，从而使能量损失最小化。然而，为了改进摩擦特性，当金属摩擦系数降低时，动摩擦系数也降低，并且因此由于离合器摩擦引起的换挡滑动现象导致齿轮的耐久性恶化。此外，退化的换档质量导致燃料经济性的恶化。
发明内容
本发明的一个方面提供了一种变速器油组合物，其能够在应用于发动机和变速器时将金属摩擦系数和动摩擦系数降低到适当的范围，从而改进摩擦特性，由此提高齿轮耐久性和燃料经济性。
本发明的另一方面提供一种自动变速器油组合物，其能够将动摩擦系数保持在同等的水平并使金属摩擦系数的降低最大化，从而提高变速器的动力传递效率和燃料经济性。
本发明的又一方面提供一种润滑油组合物，其中自动变速器的动摩擦系数被保持在适当水平并且其金属摩擦系数被显著减小，从而提高变速器的动力传递效率和燃料经济性，并且还增加耐磨性。
本发明的又另一方面提供一种自动变速器油组合物，其能够增加变速器的耐磨性并使能量损失最小化。
本发明的各方面不限于前述内容，并且将能够通过以下描述被清楚地理解并且通过权利要求中描述的手段及其组合来实现。
本发明的进一步方面提供一种自动变速器油组合物，其包含：80至85wt％的基础油，1至5wt％的茂金属聚α烯烃，1至5wt％的清净分散剂，0.01至0.03wt％的三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂，3至10wt％的粘度改进剂和3至5wt％的抗磨添加剂。
该基础油可以具有在100℃下的2.8至3.2cSt的运动粘度。
茂金属聚α烯烃可以被配置使得茂金属化合物与α-烯烃共聚合。
该茂金属化合物可以是选自由以下各项组成的组中的至少一种：双(环戊二烯基)二氯化锆、双(甲基环戊二烯基)二氯化锆、双(乙基环戊二烯基)二氯化锆、双(异丙基环戊二烯基)二氯化锆、双(正丙基环戊二烯基)二氯化锆、双(正丁基环戊二烯基)二氯化锆、双(叔丁基环戊二烯基)二氯化锆、双(癸基环戊二烯基)二氯化锆、双(三甲基硅基环戊二烯基)二氯化锆、双(三甲基硅基甲基环戊二烯基)二氯化锆、双(环戊二烯基)氯化羟锆(zirconium chlorohydride)、双(环戊二烯基)甲基氯化锆和双(环戊二烯基)乙基氯化锆。
α-烯烃可以是C6-C12单体。
该茂金属聚α烯烃可以具有在100℃下的150至160cSt的运动粘度，以及1000至30000g/mol的重均分子量(Mw)。
该清净分散剂可以是水杨酸钙、磺酸钙或其混合物。
三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂可以是由以下化学式2表示的化合物。
[化学式2]
Figure BDA0001963389190000031
(在化学式2中，R1至R4彼此相同或不同并且各自独立地为C1-C24烷基，并且X1至X7彼此相同或不同并且各自独立地为硫或氧。)
该粘度改进剂可以是选自由以下各项组成的组中的至少一种：聚甲基丙烯酸酯(PMA)、烯烃共聚物和聚异丁烯。
该抗磨添加剂可以是选自由以下各项组成的组中的至少一种：烷基二硫代磷酸锌、胺亚磷酸酯和异丁炔基琥珀酸酯。
该自动变速器油组合物可以具有在100℃下的5.3至5.5cSt的运动粘度，以及在速度为1m/s且温度为110℃的条件下的0.075至0.078的金属摩擦系数。
根据本发明的实施方式，通过将基础油与茂金属聚α烯烃和三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂以特定的混合比混合制备自动变速器油组合物，由此可以将动摩擦系数保持在同等的水平并且可以降低金属摩擦系数，从而使传动金属之间的动力传递效率最大化并且改进燃料经济性(1.5％或更多)。
此外，在根据本发明实施方式的自动变速器油组合物中，该茂金属聚α烯烃和三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂的各个官能团由于范德华力而通过交联吸附到变速器的金属表面，由此改进自动变速器的耐久性并且还降低金属间阻力，最终减少整体摩擦阻力并使能量损失最小化。
本发明的实施方式的效果不限于前述内容，并且应当理解为包括以下描述中的所有合理可能的效果。
具体实施方式
从下面讨论的实施方式中，将更清楚地理解本发明的上述和其它方面、特征和优点。然而，本发明不限于本文公开的实施方式，并且可以修改为不同的形式。提供这些实施方式是为了彻底说明本发明并将本发明的精神充分地传递给本领域技术人员。
可以理解的是，尽管本文可能使用诸如“第一”、“第二”等术语来描述各种要素，但是这些要素不受这些术语的限制。这些术语仅用于将一个要素与另一个要素区分开。例如，在不脱离本发明范围的条件下，以下讨论的“第一”要素可以称为“第二”要素。类似地，“第二”要素也可以称为“第一”要素。如本文所用，除非上下文另有明确说明，否则单数形式也旨在包括复数形式。
还可以理解的是，当在本说明书中使用时，术语“包含(comprise)”、“包括(include)”、“具有(have)”等详细指明所叙述的特征、整数、步骤、操作、元素、组分或其组合的存在，但不排除存在或添加一个或多个其它特征、整数、步骤、操作、元素、组件或其组合。另外，可以理解的是，当诸如层、膜、区域或片材等要素被称为在另一要素“上”时，其可经直接在所述另一要素上，或者在它们之间可以存在中间要素。类似地，当诸如层、膜、区域或片材等要素被称为在另一要素“之下”时，其可以直接在该其它要素之下，或者它们之间可以存在中间要素。
除非另有说明，表达本文所用的组分、反应条件、聚合物组成和混合物的含量的所有数字、数值和/或表示均应视为近似值，包括影响在获得这些值时基本上发生的测量的各种不确定性等，因此应该理解为在所有情况下都用术语“约”来修饰。另外，当在本说明书中公开数值范围时，该范围是连续的，并且包括从所述范围的最小值到其最大值的所有值，除非另有说明。此外，当这样的范围涉及整数值时，除非另有说明，包括最小值到最大值的所有整数均包括在内。
在本公开中，当为变量描述范围时，应该理解该变量包括所有值，包括在所述范围内描述的端点。例如，“5至10”的范围将被理解为包括任何子范围，例如6至10、7至10、6至9、7至9等以及5、6、7、8、9和10的单个值，并且还将被理解为包括在所述范围内的有效整数之间的任何值，诸如5.5、6.5、7.5、5.5至8.5、6.5至9等。另外，例如，范围“10％至30％”应理解为包括任何子范围，诸如10％至15％、12％至18％、20％至30％等以及所有整数，包括值10％、11％、12％、13％等至高达30％，并且还应理解为所述范围内的有效整数之间的任何值，诸如10.5％、15.5％、25.5％等。
如本文使用的，术语“金属摩擦系数”是指通过金属和金属表面之间的直接接触产生的摩擦系数。另外，术语“动摩擦系数”是指抵抗与另一个物体表面接触的物体运动的力(动摩擦力)与垂直于接触表面的反向力的比值。另外，“流体摩擦阻力”是指施加到流动的流体(润滑剂等)的阻力。
本发明的实施方式涉及一种自动变速器油组合物或自动变速器流体组合物，其是将基础油与茂金属聚α烯烃和三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂以特定的混合比混合制备的，由此可以将动摩擦系数维持在同等的水平并且可以降低金属摩擦系数，从而使传动金属之间的动力传递效率最大化并改进燃料经济性(1.5％或更高)。
此外，在根据本发明的实施方式的自动变速器油组合物中，该茂金属聚α烯烃和三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂的各官能团由于范德华力而通过交联吸附到变速器的金属表面，由此改进自动变速器的耐久性并且还降低金属间阻力，最终减少整体摩擦阻力并使能量损失最小化。
更具体地，根据本发明的实施方式的自动变速器油组合物可以包含80至85wt％的基础油、1至5wt％的茂金属聚α烯烃(mPAO)、1至5wt％的清净分散剂、0.01至0.03wt％的三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂、3至10wt％的粘度改进剂和3至5wt％的抗磨添加剂。
在实施方式中，在该自动变速器油组合物中，该基础油存在的量为79、79.5、80、80.5、81、81.5、82、82.5、83、83.5、84、84.5、85、85.5或86wt％。在实施方式中，该基础油的存在量为由从前一句子中所列数字中选择的任何两个数字形成的范围内的重量％(wt％)。
在实施方式中，在该自动变速器油组合物，茂金属聚α烯烃(mPAO)的存在量为0.5、1、1.5、2、2.5、3、3.5、4、4.5、5或5.5wt％。在实施方式中，茂金属聚α烯烃(mPAO)的存在量为由从前一句子中所列数字中选择的任何两个数字形成的范围内的重量％(wt％)。
在实施方式中，在该自动变速器油组合物中，该清净分散剂的存在量为0.5、1、1.5、2、2.5、3、3.5、4、4.5、5或5.5wt％。在实施方式中，该清净分散剂的存在量为由从前一句子中所列数字中选择的任何两个数字形成的范围内的重量％(wt％)。
在实施方式中，在该自动变速器油组合物中，该三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂存在的量为0.01、0.015、0.02、0.025、0.03或0.035wt％。在实施方式中，该三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂存在的量为由从前一句子中所列数字中选择的任何两个数字形成的范围内的重量％(wt％)。
在实施方式中，在该自动变速器油组合物中，该粘度改进剂存在的量为2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5、10或10.5wt％。在实施方式中，该粘度改进剂存在的量为由从前一句子中所列数字中选择的任何两个数字形成的范围内的重量％(wt％)。
在实施方式中，在该自动变速器油组合物中，该抗磨添加剂存在的量为2.5、3、3.5、4、4.5、5或5.5wt％。在实施方式中，该抗磨添加剂存在的量为由从前一句子中所列数字中选择的任何两个数字形成的范围内的重量％(wt％)。
在实施方式中，该基础油可以是对应于按照美国石油协会(API)指定的矿物基础油标准分类的第3组的基础油。该基础油可以具有在100℃下的2.8至3.2cSt的运动粘度。
该茂金属聚α烯烃是降低流体摩擦阻力的合成基础油，并且可以经配置使得茂金属化合物通过交联与α-烯烃共聚合。
该茂金属化合物可以是选自由以下各项组成的组中的至少一种：双(环戊二烯基)二氯化锆、双(甲基环戊二烯基)二氯化锆、双(乙基环戊二烯基)二氯化锆、双(异丙基环戊二烯基)二氯化锆、双(正丙基环戊二烯基)二氯化锆、双(正丁基环戊二烯基)二氯化锆、双(叔丁基环戊二烯基)二氯化锆、双(癸基环戊二烯基)二氯化锆、双(三甲基硅基环戊二烯基)二氯化锆、双(三甲基硅基甲基环戊二烯基)二氯化锆、双(环戊二烯基)氯化羟锆、双(环戊二烯基)甲基氯化锆和双(环戊二烯基)乙基氯化锆。
α-烯烃可以是C6-C12单体。α-烯烃能够与摩擦改进剂的官能团一起降低变速器的金属表面的摩擦阻力。
在实施方式中，该茂金属聚α烯烃是由以下化学式1表示的化合物。该茂金属聚α烯烃通过将作为化学式1的官能团的烃分子吸附到变速器的金属表面上而发挥平滑流体流动的功能，由此降低流体阻力。
[化学式1]
Figure BDA0001963389190000081
该茂金属聚α烯烃可以具有在100℃下的150至160cSt的运动粘度，以及1000至30000g/mol的重均分子量(Mw)。当茂金属聚α烯烃的运动粘度等于或大于150cSt时，其在降低金属摩擦阻力方面发挥了足够的作用。当其运动粘度等于或小于160cSt时，可以避免或最小化油粘度的增加并且进一步避免或最小化不希望的燃料经济性降低。在一个实施方式中，该茂金属聚α烯烃具有在100℃下的154至158cSt的运动粘度，以及15000至20000g/mol的重均分子量(Mw)。
基于该自动变速器油组合物的总量，该茂金属聚α烯烃的含有量可以为1至5wt％。此处，当其量等于或大于1wt％，可以使降低金属摩擦系数的效果最大化。当其量等于或小于5wt％，可以避免或最小化流体摩擦阻力的增加，并且可以最大化燃料经济性的改进。在一个实施方式中，为了有效地降低流体摩擦阻力，茂金属聚α烯烃的量在2至4wt％的范围内。
该清净分散剂能够使由自动变速器油组合物在发动机和变速器中氧化形成的氧化物或污泥等沉积物以细颗粒的形式分散为浮游物，由此可以保持离合器清洁。该清净分散剂可以是水杨酸钙、磺酸钙或其混合物。
基于该自动变速器油组合物的总量，该清净分散剂的含有量可以为1至5wt％。当其量等于或大于1wt％时，可以使分散效果最大化，因此可以保持离合器清洁。当其量等于或小于5wt％时，可以避免或最小化分子间阻力的增加并且进一步避免或最小化离合器摩擦性能的劣化。在一个实施方式中，该清净分散剂的量在3至5wt％的范围内。
摩擦改进剂的作用是赋予自动变速器油组合物以降低金属摩擦系数的特性，同时保持离合器动摩擦系数在同等的水平，从而提高变速器的动力传递效率。摩擦改进剂可以是三核钼基二烷基二硫代氨基甲酸酯，如由以下化学式2表示。特别地，作为化学式2中官能团的硫化合物可以通过范德华力而吸附到变速器的金属表面，由此与茂金属聚α烯烃一起，降低金属材料之间的摩擦阻力并且提高耐磨性。
[化学式2]
Figure BDA0001963389190000091
(在化学式2中，R1至R4彼此相同或不同并且各自独立地为C1-C24烷基，并且X1至X7彼此相同或不同并且各自独立地为硫或氧。)
基于该自动变速器油组合物的总量，该摩擦改进剂的含有量可以为0.01至0.03wt％。当其量等于或大于0.01wt％时，可以使降低金属摩擦系数的效果最大化。当其量等于或小于0.03wt％时，可以避免或最小化动摩擦系数的减小并且使耐久性的劣化最小化。在一个实施方式中，该摩擦改进剂的量设定为0.02wt％。
该粘度改进剂用于在自动变速器油组合物处于低温时降低该组合物的高粘度，使得离合器可以平稳地操作，并且还用于当自动变速器油组合物处于高温时提高该组合物的低粘度，由此防止金属间摩擦和磨损的发生。该粘度改进剂可以是选自由以下各项组成的组中的至少一种：聚甲基丙烯酸酯(PMA)、烯烃共聚物和聚异丁烯。
基于该自动变速器油组合物的总量，该粘度改进剂的含有量可以为3至10wt％。当其量等于或大于3wt％时，可以使增加粘度的效果最大化，并且使耐久性的劣化最小化。当其量等于或小于10wt％时，可以抑制低温粘度过高并且使低温可操作性的劣化最小化。在一个实施方式中，该粘度改进剂的量在8至10wt％的范围内。
该抗磨添加剂通过在摩擦材料、金属板等的摩擦金属表面上形成保护膜来起到防止磨损的作用。该抗磨添加剂可以是选自由以下各项组成的组中的至少一种：烷基二硫代磷酸锌、胺亚磷酸酯和异丁炔基琥珀酸酯。
如上所述，本发明的实施方式的自动变速器油组合物可以具有在100℃下5.3至5.5cSt的运动粘度，以及在速度为1m/s和温度为110℃的条件下的0.075至0.078的金属摩擦系数。此外，该自动变速器油组合物可以具有在3600rpm、230kPa和120℃条件下的0.122至0.125的动摩擦系数。当满足与金属摩擦系数和动摩擦系数有关的所有条件时，变速器的动力传递效率和燃料经济性可以最大化。
通过以下实施例将更好地理解本发明的实施方式，这些实施例仅用于说明而不应解释为限制本发明的范围。
实施例1至7以及比较例1至7
使用下表1和表2所示量的组分，通过经典工艺制备相应的自动变速器油组合物。[表1]
Figure BDA0001963389190000111
[表2]
Figure BDA0001963389190000112
Figure BDA0001963389190000121
测试例
通过以下方法测量实施例1至7和比较例1至7的自动变速器组合物的性质。结果示于下表3和4中。
(1)金属摩擦系数：使用块-环试验机，在1m/s x 110℃下测量金属摩擦材料和用于钢板的金属材料之间的金属摩擦。
(2)动摩擦系数：在3600rpm x 230kPa x 120℃下测量纸摩擦材料和钢板之间的动摩擦。
(3)燃料经济性改善(％)：使用底盘测功机以车辆燃料经济性的FTP 75模式测量燃料经济性。上述燃料经济性测量方法与CVS 75相同，CVS 75是韩国的燃料经济性测试模式。
(4)耐久性试验后的Fe磨损含量(ppm)：在从发动机转速为260到1600rpm的从1档到6档切换所有档位的同时，对发动机300至2000N扭矩评价700小时。
[表3]
Figure BDA0001963389190000122
Figure BDA0001963389190000131
[表4]
Figure BDA0001963389190000132
从表3和4的结果可以明显看出，与比较例1至7相比，实施例1至7中的动摩擦系统保持在同等的水平并且金属摩擦系数显著降低。另外，由于金属摩擦系数的减小，燃料经济性得到改进且耐磨性提高。在实施例2至4和7中，与当前说明书的比较例1相比，燃料经济性改进并且耐久性试验后的磨损减少显著增加。特别是，实施例3表现出优异的值。
相比之下，在比较例1、2和5中，其中没有加入茂金属聚α烯烃和摩擦改进剂中的一种或两种，降低金属摩擦系数的效果不明显，或者燃料经济性和耐磨性显著恶化。
在比较例3中，其中茂金属聚α烯烃的量较低，由于低摩擦减小效应导致燃料经济性改进较差。在另一方面，在比较例4中，其中茂金属聚α烯烃的量过高，由于分子间相互作用导致流体摩擦增加，因此燃料经济性和耐磨性恶化。
在比较例6中，其中含有极少量的摩擦改进剂，降低金属摩擦系数的效果不显著，如比较例5，并因此燃料经济性和耐磨性恶化。
在比较例7中，其中摩擦改进剂的量较高，金属摩擦系数与实施例1至7一样低，但动摩擦系数减小，因而燃料经济性改进和耐磨性均显著恶化。
尽管已经描述了本发明的实施方式，但是本领域技术人员可以理解的是，在不改变其技术精神或基本特征的条件下，本发明可以以其它具体形式实施。因此，上述实施方式应理解为是非限制性的且完全是示例性的。

Claims (11)

1.一种自动变速器油组合物，其包含：
80至85wt％的基础油；
1至5wt％的茂金属聚α烯烃；
1至5wt％的清净分散剂；
0.01至0.03wt％的三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂；
3至10wt％的粘度改进剂；和
3至5wt％的抗磨添加剂。
2.根据权利要求1所述的自动变速器油组合物，其中所述基础油具有在100℃下的2.8至3.2cSt的运动粘度。
3.根据权利要求1所述的自动变速器油组合物，其中所述茂金属聚α烯烃经配置使得茂金属化合物与α-烯烃共聚合。
4.根据权利要求3所述的自动变速器油组合物，其中所述茂金属化合物包含选自由以下各项组成的组中的至少一种：双(环戊二烯基)二氯化锆、双(甲基环戊二烯基)二氯化锆、双(乙基环戊二烯基)二氯化锆、双(异丙基环戊二烯基)二氯化锆、双(正丙基环戊二烯基)二氯化锆、双(正丁基环戊二烯基)二氯化锆、双(叔丁基环戊二烯基)二氯化锆、双(癸基环戊二烯基)二氯化锆、双(三甲基硅基环戊二烯基)二氯化锆、双(三甲基硅基甲基环戊二烯基)二氯化锆、双(环戊二烯基)氯化羟锆、双(环戊二烯基)甲基氯化锆和双(环戊二烯基)乙基氯化锆。
5.根据权利要求3所述的自动变速器油组合物，其中所述α-烯烃包含C6-C12单体。
6.根据权利要求1所述的自动变速器油组合物，其中所述茂金属聚α烯烃具有在100℃下的150至160cSt的运动粘度，以及具有1000至30000g/mol的重均分子量。
7.根据权利要求1所述的自动变速器油组合物，其中所述清净分散剂包含水杨酸钙、磺酸钙或其混合物。
8.根据权利要求1所述的自动变速器油组合物，其中所述三核钼基二烷基二硫代氨基甲酸酯摩擦改进剂包含由以下化学式表示的化合物，
Figure FDA0001963389180000021
其中R1至R4彼此相同或不同并且各自独立地为C1-C24烷基基团，并且X1至X7彼此相同或不同并且各自独立地为硫或氧。
9.根据权利要求1所述的自动变速器油组合物，其中所述粘度改进剂包含选自由以下各项组成的组中的至少一种：聚甲基丙烯酸酯、烯烃共聚物和聚异丁烯。
10.根据权利要求1所述的自动变速器油组合物，其中所述抗磨添加剂包含选自由以下各项组成的组中的至少一种：烷基二硫代磷酸锌、胺亚磷酸酯和异丁炔基琥珀酸酯。
11.根据权利要求1所述的自动变速器油组合物，其中所述自动变速器油组合物具有在100℃下的5.3至5.5cSt的运动粘度，以及具有在速度为1m/s且温度为110℃条件下的0.075至0.078的金属摩擦系数。
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