双/三氮杂冠醚化合物的合成及其作为摩擦改进剂的性能研究※

doi:10.6023/A21120570

摘要/Abstract

现代汽车工业的发展以及环保法规的日益严格对车用润滑油的性能提出了更高要求, 摩擦改进剂在提高发动机油减摩性能及燃油经济性方面发挥着重要作用. 有机钼化合物作为目前使用最为广泛的摩擦改进剂, 会增加油品热氧化沉积物的生成, 且油品氧化会导致其减摩性能下降. 针对摩擦改进剂所存在的诸如有害元素、灰分及活性吸附位点有限等问题, 设计并合成了两种双/三氮杂冠醚化合物, 将活性氮原子及长链烷基引入冠醚结构中以提高吸附性能和油溶性, 并研究其作为摩擦改进剂的减摩和抗磨性能. 结果表明, 所合成双/三氮杂冠醚能有效降低油品的摩擦系数和磨损率, 其中含有吡啶结构的三氮杂冠醚表现出更优的摩擦学性能, 可使摩擦系数和磨损率相对于基础油分别降低8.8%和42%. 机理分析表明, 所合成的双/三氮杂冠醚化合物能够在钢表面发生不同程度的吸附, 并进一步发生摩擦化学反应形成润滑保护膜, 防止滑动表面微凸体的直接接触进而改善摩擦学性能.

关键词: 氮杂冠醚, 合成, 减摩, 抗磨, 润滑作用机理

The development of modern automobile industry and the increasingly strict environmental protection regulations continuously drive the development of automobile lubricating oil. Friction modifiers play an important role in improving the friction reduction and fuel economy of the engine oil. Organic molybdenum compounds are the most widely used friction modifiers, the metal elements of which will increase the thermal oxidation deposits, and further affect the ternary catalytic converter system. Additionally, the friction reduction performance will decrease with the oxidation of oil. In view of the problems existing in friction modifiers such as harmful elements, ash content and limited active adsorption sites, two bis/triaza crown ethers were designed and synthesized in this paper. Active nitrogen atoms and long-chain alkyl groups were introduced into the structure of crown ether to provide adsorption sites and oil solubility. UMT-tribolab and 3D profilometer were applied to study the friction-reducing and anti-wear properties of the synthesized azacrown ethers under boundary lubrication regime. The adsorption properties of additive molecules on metal surface were analyzed by using steel surface contact angle measurement. And the composition of lubrication film on metal friction pair surface was analyzed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, in order to clarify the lubrication mechanism of the azacrown ethers. The results show that both bis/triaza crown ethers can effectively reduce the friction coefficient and wear rate of base oil. The triaza-crown ether containing pyridine structure unit shows superior tribological properties, which can reduce the friction coefficient and wear rates by up to 8.8% and 42%, respectively. It can be indicated from the mechanism analysis that azacrown ethers can be adsorbed on the surface of steel in varying degrees. Under the shear stress of friction pairs, the compounds adsorbed on the surface further undergo tribochemical reaction to form lubricating protective film. The lubricant layer with ferric oxide and carbon film will prevent the sliding surface from direct contact to improve tribology performance.

Key words: azacrown ether, synthesis, friction reduction, wear resistance, lubrication mechanism

引用此文

胡文敬, 李久盛. 双/三氮杂冠醚化合物的合成及其作为摩擦改进剂的性能研究^※[J]. 化学学报, 2022, 80(3): 310-316.

Wenjing Hu, Jiusheng Li. Synthesis of Bis/triaza Crown Ethers and Study of Their Properties as Friction Modifiers^※[J]. Acta Chimica Sinica, 2022, 80(3): 310-316.

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图/表 12

理化性质
粗糙度	钢球(直径8 mm): 0.12 μm 钢板: 0.1 μm
压力粘度系数	2.097×10^–8 Pa^–1
杨氏模量	2.10×10¹¹ Pa
泊松比	0.3
h_min λ值	12.332 nm 0.079

表1. 摩擦测试条件

Table 1. Friction test condition

图1. 双/三氮杂冠醚化合物的热重曲线

Figure 1. Thermo-gravimetric curves of bis/triaza crown ethers

图2. 平均摩擦系数随添加剂浓度的变化

Figure 2. Variation of the average friction coefficient with the additive concentration

图3. (a)不同油品的平均摩擦系数; (b)不同油品的摩擦系数曲线

Figure 3. (a) Average friction coefficient of different oils; (b) Friction coefficient curves of different oils

图4. 摩擦实验后的钢球表面三维形貌和显微镜照片(a1/b1: 基础油; a2/b2: w=1.5% Aza-CE15-5; a3/b3: w=1.5% Py-Aza-CE15-5)

Figure 4. 3D profile and microscope photos of steel ball surfaces after friction tests (a1/b1: Base oil; a2/b2: w=1.5% Aza-CE15-5 in base oil; a3/b3: w=1.5% Py-Aza-CE15-5 in base oil)

图5. 不同油品润滑的钢球表面磨损率对比

Figure 5. Comparison of surface wear rates of steel balls lubricated by different oils

图6. 油品浸渍处理后钢表面接触角

Figure 6. Contact angle of steel surface after oil impregnation

图7. 摩擦实验后磨痕处的XPS曲线

Figure 7. XPS curves at the abrasion marks after the friction tests

图8. 摩擦实验后磨痕处的拉曼光谱

Figure 8. Raman spectra of the wear marks after the friction tests

图式1. 双氮杂冠醚化合物Aza-CE15-5的合成路线

Scheme 1. Synthetic route of bisaza-crown ether Aza-CE15-5

图式2. 三氮杂冠醚化合物Py-Aza-CE15-5的合成路线

Scheme 2. Synthetic route of triaza crown ether Py-Aza-CE15-5

理化性质
运动粘度@20 ℃ (mm²/s)	44.910
运动粘度@40 ℃ (mm²/s) 运动粘度@100 ℃ (mm²/s)	19.545 3.934
密度@20 ℃ (g/cm³)	0.922
倾点/℃	–41
闪点/℃	204

表2. 基础油OSP18的理化性质

Table 2. Physicochemical properties of the base oil OSP18

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