Synthesis of Bis/triaza Crown Ethers and Study of Their Properties as Friction Modifiers※

doi:10.6023/A21120570

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (3): 310-316.DOI: 10.6023/A21120570 Previous Articles Next Articles

Special Issue: 中国科学院青年创新促进会合辑

Article

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^※

胡文敬, 李久盛^*()

中国科学院上海高等研究院先进润滑材料实验室上海 201210

投稿日期:2021-12-17 发布日期:2022-02-15
通讯作者: 李久盛
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
中科院青年创新促进会(2019288); 上海市浦东新区科技发展基金(PKJ2019-C01); 中国科学院任务/战略性先导科技专项(A类)(XDA21021202)

Synthesis of Bis/triaza Crown Ethers and Study of Their Properties as Friction Modifiers^※

Wenjing Hu, Jiusheng Li()

Laboratory for Advanced Lubricating Materials, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210

Received:2021-12-17 Published:2022-02-15
Contact: Jiusheng Li
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
Youth Innovation Promotion Association, CAS(2019288); Shanghai Pudong New Area Science and Technology Development Fund(PKJ2019-C01); Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21021202)

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Abstract

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

Cite this article

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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Fig. & Tab. 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

Table 1. Friction test condition

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

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

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

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)

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

Figure 6. Contact angle of steel surface after oil impregnation

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

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

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

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

Table 2. Physicochemical properties of the base oil OSP18

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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^※

Synthesis of Bis/triaza Crown Ethers and Study of Their Properties as Friction Modifiers^※

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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※

Synthesis of Bis/triaza Crown Ethers and Study of Their Properties as Friction Modifiers※

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Supporting Info.

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Abstract

Cite this article

share this article

Fig. & Tab. 12

References 35

Related Articles 15

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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^※

Synthesis of Bis/triaza Crown Ethers and Study of Their Properties as Friction Modifiers^※