新型无硫无磷醚-酯化合物的合成及其作为无灰摩擦改进剂的性能研究

doi:10.6023/A23030101

化学学报 ›› 2023, Vol. 81 ›› Issue (5): 461-468.DOI: 10.6023/A23030101 上一篇下一篇

研究论文

新型无硫无磷醚-酯化合物的合成及其作为无灰摩擦改进剂的性能研究

王俊^a^,^b, 许晓梅^b^,^c, 周姣龙^b, 赵雅男^b, 孙秀丽^b, 唐勇^b, 何素芳^*^,^a(), 杨红梅^b^,^*()

a 昆明理工大学材料科学与工程学院云南昆明 650093
b 中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032
c 上海理工大学材料与化学学院上海 200093

投稿日期:2023-03-30 发布日期:2023-05-08
基金资助:
受云南“万人计划”青年拔尖人才专项(YNWR-QNBJ-2018-067); 受云南“万人计划”青年拔尖人才专项(YNWR-QNBJ-2020-002); 中核集团领创科研项目和中国科学院战略性先导科技专项(A类)“变革性洁净能源关键技术与示范”(XDA21021203)

Synthesis of New Sulfur-free and Phosphorus-free Ether-ester and Study on Its Properties As Ashless Friction Modifier

Wang Jun^a^,^b, Xu Xiaomei^b^,^c, Zhou Jiaolong^b, Zhao Yanan^b, Sun Xiuli^b, Tang Yong^b, He Sufang^a(), Yang Hongmei^b()

a Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
c School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China

Received:2023-03-30 Published:2023-05-08
Contact: E-mail: shucai1983@163.com; yanghm@sioc.ac.cn
Supported by:
Yunnan Ten Thousand Talents Plan Young & Elite Talents Project(YNWR-QNBJ-2018-067); Yunnan Ten Thousand Talents Plan Young & Elite Talents Project(YNWR-QNBJ-2020-002); LingChuang Research Project of China National Nuclear Corporation and Strategic Pilot Science and Technology Special Project of the Chinese Academy of Sciences (Class A) “Key Technologies and Demonstration of Transformative Clean Energy”(XDA21021203)

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摘要/Abstract

伴随机械设备的升级换代和“双碳”政策的推行实施, 长换油周期、清洁环保的高品质润滑油需求与日俱增, 而新型添加剂和基础油以及二者之间配伍规律的研究始终贯穿于高性能润滑油的研发. 摩擦改进剂作为提升低粘化油品耐久性润滑保护及燃油经济性至关重要的一类添加剂, 其结构的设计与开发是润滑技术发展的前沿问题. 为此, 本工作设计并合成了新型无硫无磷醚-酯化合物DOA-mPEG350, 通过核磁(NMR)、高分辨质谱(HR-MS)、红外(FT-IR)和凝胶色谱(GPC)表征了其结构, 同时采用热重(TGA)和紫外分光光度法(UV-Vis)分析了DOA-mPEG350的热稳定性、以及其与合成烃基础油的相容性, 利用四球摩擦磨损试验机系统研究了DOA-mPEG350作为无灰摩擦改进剂在合成烃基础油中的摩擦学行为. 结果表明, DOA-mPEG350具有良好的热稳定性以及与合成烃基础油的相容性, 其作为摩擦改进剂应用时能有效缩短跑合期, 1.0% (w)加剂量即可使合成烃CTL6基础油和PAO6基础油的平均摩擦系数、磨斑直径分别下降20.6%、20.1%和28.9%、34.8%, 综合性能优于所选市售添加剂. 通过摩擦表面分析及密度泛函理论(DFT)计算, 揭示了醚-酯化合物的微观润滑机理, 即通过醚链的“线接触”和酯基的“点接触”协同在金属表面形成有厚度且致密的保护膜, 故表现出比仅含醚链或酯基结构化合物更优的摩擦学性能.

关键词: 无硫无磷, 醚-酯化合物, 合成, 无灰摩擦改进剂, 润滑机理

With the upgrading of mechanical equipment and the implementation of the “double-carbon” policy, the demand for high-quality lubricants with longer drain period, more clean and environmental friendly is increasing day by day. The study on new additives and base oils, as well as the compatibility law between the two has always run through the development of high-performance lubricants. As an important additive to improve the durability of lubricating protection and fuel economy, the design and development of friction modifier is the forefront of the development of lubrication technologies. Based on these, a new sulfur-free and phosphorus-free ether-ester DOA-mPEG350 was designed and synthesized, and characterized by nuclear magnetic resonance (NMR), high resolution mass spectrometer (HR-MS), Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). Meanwhile, the thermal stability of DOA-mPEG350 and its compatibility with synthetic hydrocarbon base oil were analyzed by thermogravimetric analysis (TGA) and ultraviolet visible spectroscopy (UV-Vis). The tribological behaviors of DOA-mPEG350 as an ashless friction modifier in synthetic hydrocarbons were studied using a four-ball friction and wear tester. The results show that DOA-mPEG350 has good thermal stability and compatibility with synthetic hydrocarbon base oil, and can effectively shorten the running-in period, and 1.0% (w) addition of DOA-mPEG350 could decrease the ave. coefficient of friction (COF) and wear scar diameter (WSD) of synthetic hydrocarbons such as CTL6 and PAO6 base oils by 20.6%, 20.1% and 28.9%, 34.8%, respectively. The comprehensive friction reduc ing and anti-wear performance of DOA-mPEG350 is better than that of the selected commercial friction modifier and extreme pressure anti-wear additives, which are usually contain sulfur, phosphorus, or metals that can not meet the increasingly stringent environmental requirements, that is, the synthesized DOA-mPEG350 has the potential to replace these additives. Through analyzing the worn friction surface and density functional theory (DFT) calculation, the micro-lubrication mechanism of ether-ester is revealed, namely, it can combine the “line contact” of ether with the “point contact” of ester to form a thick and dense protective film on metal surfaces, thus showing better tribological performance than that only contain ether chain or ester group.

Key words: sulfur-free and phosphorus-free, ether-ester, synthesis, ashless friction modifier, lubricating mechanism

引用此文

王俊, 许晓梅, 周姣龙, 赵雅男, 孙秀丽, 唐勇, 何素芳, 杨红梅. 新型无硫无磷醚-酯化合物的合成及其作为无灰摩擦改进剂的性能研究[J]. 化学学报, 2023, 81(5): 461-468.

Wang Jun, Xu Xiaomei, Zhou Jiaolong, Zhao Yanan, Sun Xiuli, Tang Yong, He Sufang, Yang Hongmei. Synthesis of New Sulfur-free and Phosphorus-free Ether-ester and Study on Its Properties As Ashless Friction Modifier[J]. Acta Chimica Sinica, 2023, 81(5): 461-468.

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图/表 11

图1. DOA-mPEG350在CTL 6中的UV-Vis分析: (a) 0.5% (w)加剂量的UV-Vis谱图; (b)不同加剂量在227 nm处的吸光度(插图为0.5%~5.0% (w)加剂量时吸光度的线性拟合)

Figure 1. UV-Vis analysis of DOA-mPEG350 in CTL 6: (a) UV-Vis spectrum of 0.5% (w) addition; (b) absorbance of different additions at 227 nm (Inset is the linear fitting of absorbance of 0.5%~5.0% (w) additions)

Residual mass/%	130 ℃	250 ℃	350 ℃	400 ℃
IPG	1.5	1.4	1.4	1.4
IPG-OTs	97.4	45.9	18.8	17.9
IPG-mPEG350	95.8	76.4	1.3	0.8
DOA-mPEG350	99.1	96.2	84.0	34.5

表1. DOA-mPEG350的热稳定性分析

Table 1. Thermo-stability analysis of DOA-mPEG350

图2. (a) 摩擦曲线和(b) 减摩、抗磨性能随DOA-mPEG350加剂量增加的变化

Figure 2. (a) Friction profiles and (b) friction reducing and anti-wear properties with an increasing additions of DOA-mPEG350

图3. 醚-酯化合物与醚类及酯类添加剂的性能对比: (a) 摩擦曲线; (b) 减摩、抗磨性能

Figure 3. The performance comparison of ether-ester with the ether and ester additives: (a) friction profiles; (b) friction reducing and anti-wear properties

图4. 1.0% (w)不同添加剂在合成烃基础油中的(a)平均摩擦系数和(b)平均磨斑直径

Figure 4. (a) Ave. COF and (b) ave. WSD of 1.0% (w) of different additives in the synthetic hydrocarbon base oils

图5. 1.0% (w) DOA-mPEG350油样摩擦测试后的Micro-IR分析

Figure 5. Micro-IR analysis of the oil with 1.0% (w) DOA-mPEG350 after tribological test

图6. CTL6基础油及添加1.0% (w) DOA-mPEG350油样摩擦测试后的EDS分析

Figure 6. EDS analysis of CTL6 base oil and the oil with 1.0% (w) DOA-mPEG350 after tribological test

图 7. 分峰拟合后的XPS谱图: (a) C1s; (b) O1s

Figure 7. XPS spectra after peak fitting: (a) C1s; (b) O1s

图8. 静电势(ESP)理论计算: (a) IPG-mPEG350; (b) DOA-mPEG350; (c) Triolein

Figure 8. Theoretical calculation of the electrostatic potential (ESP) of (a) IPG-mPEG350, (b) DOA-mPEG350 and (c) Triolein

图9. 不同结构化合物在金属表面可能的排列方式

Figure 9. Possible arrangement of different structures on metal surfaces

图式1. 1,2-二油酸-3-mPEG350甘油酯的合成路线

Scheme 1. The synthetic route of 1,2-dioleate-3-mPEG350 glycerides

参考文献 29

[1]	Ewen, J. P.; Gattinoni, C.; Morgan, N.; Spikes, H.; Dini, D. Langmuir 2016, 32, 4450. doi: 10.1021/acs.langmuir.6b00586
	Cyriac, F.; Yi, T. X.; Poornachary, S. K.; Chow, P. S. Tribol. Int. 2022, 165.
[2]	Tang, Z. L.; Li, S. H. Curr. Opin. Solid. State Mater. Sci. 2014, 18, 119. doi: 10.1016/j.cossms.2014.02.002
[3]	Zhao, X.; Zhang, G.; Wang, L.; Xue, Q. Tribol. Lett. 2017, 65, 64. doi: 10.1007/s11249-017-0847-3
[4]	De Barros Bouchet, M. I.; Thiebaut, B.; Martin, J. M. RSC Adv. 2015, 5, 93786. doi: 10.1039/C5RA15250J
[5]	Xu, D.; Wang, C.; Espejo, C.; Wang, J.; Neville, A.; Morina, A. Langmuir 2018, 34, 13523. doi: 10.1021/acs.langmuir.8b02329
[6]	De Barros Bouchet, M. I.; Martin, J. M.; Oumahi, C.; Gorbatchev, O.; Afanasiev, P.; Geantet, C.; Iovine, R.; Thiebaut, B.; Heau, C. Tribol. Int. 2018, 119, 600. doi: 10.1016/j.triboint.2017.11.039
[7]	Gao, H.; Mcquen, J. S.; Black, E. D. Tribol. T. 2004, 47, 200. doi: 10.1080/05698190490431885
[8]	Hu, W. J.; Li, J. S. Acta Chim. Sinica 2022, 80, 310. (in Chinese) doi: 10.6023/A21120570
	(胡文敬, 李久盛, 化学学报, 2022, 80, 310.) doi: 10.6023/A21120570
[9]	Zhou, C.; Tan, L.; Hu, W.; Li, J. J. Appl. Polym. Sci. 2020, 138.
[10]	Hu, W. J.; Zhang, Z. J.; Zeng, X. Q.; Li, J. S. Ind. Eng. Chem. Res. 2019, 59, 215. doi: 10.1021/acs.iecr.9b05333
[11]	Zheng, D.; Wang, X.; Zhang, M.; Liu, Z.; Ju, C. Tribol. Int. 2019, 130, 324. doi: 10.1016/j.triboint.2018.08.014
[12]	Cyriac, F.; Tee, X. Y.; Poornachary, S. K.; Chow, P. S. Friction 2020, 9, 380. doi: 10.1007/s40544-020-0385-0
[13]	Desanker, M.; He, X. L.; Lu, J.; Johnson, B. A.; Liu, Z.; Delferro, M.; Ren, N.; Lockwood, F. E.; Greco, A.; Erdemir, A.; Marks, T. J.; Wang, Q. J.; Chung, Y. W. Tribol. Lett. 2018, 66, 50. doi: 10.1007/s11249-018-0996-z
[14]	Spikes, H. Tribol. Lett. 2015, 60, 5. doi: 10.1007/s11249-015-0589-z
[15]	Jahanmir, S. Wear 1985, 102, 331. doi: 10.1016/0043-1648(85)90176-0
[16]	Jahanmir, S.; Beltzer, M. J. Tribol. 1986, 108, 109. doi: 10.1115/1.3261129
[17]	Beltzer, M.; Jahanmir, S. Lubr. Sci. 1988, 1, 3. doi: 10.1002/(ISSN)1557-6833
[18]	Fry, B. M.; Moody, G.; Spikes, H. A.; Wong, J. S. S. Langmuir 2020, 36, 1147. doi: 10.1021/acs.langmuir.9b03668
[19]	Nalam, P. C.; Pham, A.; Castillo, R. V.; Espinosa-Marzal, R. M. J. Phys. Chem. C 2019, 123, 13672. doi: 10.1021/acs.jpcc.9b02097
[20]	Askwith, T. C.; Cameron, A.; Crouch, R. F. Proc. R Soc. A Math. Phys. Eng. Sci. 1966, 291, 500.
[21]	Davidson, J. E.; Hinchley, S. L.; Harris, S. G.; Parkin, A.; Parsons, S.; Tasker, P. A. J. Mol. Graph. Model. 2006, 25, 495. pmid: 16707267
[22]	Simic, R.; Kalin, M. Stroj. Vestn-J. Mech. Eng. 2013, 59, 707.
[23]	Luo, Y.; Zhang, S. L.; Xu, R. F.; An, W. J.; Xue, W. G.; Zheng, L. C.; Wang, L. P. Lubricating Oil 2022, 37, 35. (in Chinese)
	(罗意, 张少龙, 徐瑞峰, 安文杰, 薛卫国, 郑来昌, 汪利平, 润滑油, 2022, 37, 35.)
[24]	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, Jr., J., A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16 Rev. A.03, Wallingford, CT, 2016.
[25]	Becke, A. D. J. Chem. Phys. 1993, 98, 1372. doi: 10.1063/1.464304
[26]	Becke, A. D. Phys. Rev. A 1988, 38, 3098. doi: 10.1103/PhysRevA.38.3098
[27]	Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/physrevb.37.785 pmid: 9944570
[28]	Lu, T.; Chen, F. W. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.v33.5
[29]	Zhang, J.; Lu, T. Phys. Chem. Chem. Phys. 2021, 23, 20323. doi: 10.1039/d1cp02805g pmid: 34486612

新型无硫无磷醚-酯化合物的合成及其作为无灰摩擦改进剂的性能研究

Synthesis of New Sulfur-free and Phosphorus-free Ether-ester and Study on Its Properties As Ashless Friction Modifier

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