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第 1 期 李朝明,等: 3,6-二叔丁基咔唑在Ⅱ类基础油中的抗氧化性能 ·173·
3,6-二叔丁基咔唑的抗氧化机理:目前普遍接受
pair. Part I. Metal damage and fracture model[J]. Wear, 1996,
的润滑油氧化机理是自由基链反应,咔唑因其 N 上 194(1/2): 71-79.
[2] Dašić P, Franek F, Assenova E, et al. International standardization
的 H 比较活泼,可以作为自由基清除剂,它能和润 and organizations in the field of tribology[J]. Industrial Lubrication
滑油氧化过程中产生的自由基结合,终止自由基的 and Tribology, 2003, 55(6): 287-291.
[3] Xi Xuanjin (郗选金). Several different mechanisms of wear in mach-
增长,切断链反应的发展。其实质是氢给予体,而 inery[J]. Mechanical Building and Automation (机械制造与自动化),
2007, 36(5): 74-75.
咔唑给出 H 后形成的自由基本身在强共轭作用下非
[4] He Weilian (何维廉). Oxidation of lubricating oils[J]. Drive System
常稳定,很难继续发生反应。因此,将 3,6-二叔丁基 Technique (传动技术), 1997, (2): 29-33.
[5] Maleville X, Faure D, Legros A, et al. Oxidation of mineral base oils
咔唑作为润滑油抗氧剂可以减缓润滑油的氧化速度。 of petroleum origin: The relationship between chemical position,
2.6 抗氧剂油溶性的测试 thickening, and composition of degradation products[J]. Lubrication
Science, 1996, 9(1): 1-60.
按照 1.5 节方法,将抗氧剂加入Ⅱ类基础油中 [6] Wang Gang (王刚), Wang Jian (王鉴), Wang Lijuan (王立娟), et al.
Antioxidant mechanism and research progress[J]. Synthetic Materials
使其充分溶解,静置 30 d 后,观察抗氧剂在基础油 Aging and Application(合成材料老化与应用), 2006, 35(2): 38-42.
中的溶解情况,如图 7 所示,a 图是刚配制好的油 [7] Liu Dongning (刘冬宁). The general trend of the development of
domestic amines, phenols and other antioxidants[J]. Chemical Enter-
样,b 图是静置 30 d 后的油样。图 7 中从左至右依 prise Management (化工管理), 2013,(22): 199-201.
[8] Yang Daosheng (杨道胜), Shi Zonggang (史宗冈), Hu Hua (胡华).
次是加入咔唑、3,6-二叔丁基咔唑、MoE 以及 3,6- Challenges to base oils and additives in a new phase of automotive
二叔丁基咔唑和 MoE 复配混合物的基础油,可以看 emissions and oil upgrades[J]. Lubricating Oil (润滑油), 2006,(1): 1-8.
[9] Xue Weiguo (薛卫国), Zhou Xuguang (周旭光). A review of amine
到,在配制时就有大量咔唑未溶解在基础油中,其 antioxidants[J]. Synthetic Lubricants(合成润滑材料), 2014, 41(4):
26-30.
油溶性不好;静置 30 d 后,除了咔唑配制成的油样 [10] DeVries L, King J M. Antioxidant combinations of molybdenum
外,其他配制成的油样依然处于澄清透明状态,说 complexes and organic sulfur compounds for lubricating oils: US
4369119[P]. 1983-09-06.
明在咔唑的苯环上引入叔丁基,增加了咔唑在Ⅱ类 [11] King J M, DeVries L. Process of preparing molybdenum complexes,
the complexes so-produces and lubricants containing same 555: US
基础油中的溶解性,油品的稳定性比较好。 4263152[P]. 1981-05-05.
[12] Gatto V J, Bezjak Y L. The antioxidant properties of organomolybde-
num compounds in engine oils[J]. Tribology and Lubrication Techno-
logy, 2006, (1): 32-39.
[13] Zhou Jing (周璟). Study on improving the oxidation resistance of
phosphorus-free and sulfur-free antioxidants with molybdenum contai-
ning additives[D]. Beijing: China University Of Petroleum (Beijing)
〔中国石油大学(北京)〕, 2018.
[14] Neugebauer F A, Fischer H. tert-Butyl-substituierte carbazole[J].
Chemische Berichte, 1972, 105(8): 2686-2693.
[15] Mcclenaghan N D, Passalacqua R, Frédérique L, et al. Ruthenium(Ⅱ)
dendrimers containing carbazole-based chromophores as branches[J].
图 7 抗氧剂在Ⅱ类基础油中的溶解情况 Journal of the American Chemical Society, 2003, 125(18): 5356-5365.
[16] Ding J, Lv J H, Cheng Y, et al. Solution-processible red iridium
Fig. 7 Solubility of antioxidants in group Ⅱ base oil dendrimers based on oligocarbazole host dendrons: Synthesis,
properties, and their applications in organic light-emitting diodes[J].
Advanced Functional Materials, 2008, 18(18): 2754-2762.
3 结论 [17] Li J, Li Q, Liu D. Novel thieno-[3,4-b]-pyrazines cored dendrimers
with carbazole dendrons: Design, synthesis, and application in solution-
processed red organic light-emitting diodes[J]. ACS Applied Materials
在 AlCl 3 的催化下,通过氯代叔丁烷和咔唑的 and Interfaces, 2011, 3(6): 2099-2107.
Friede-Crafts 反应合成了 3,6-二叔丁基咔唑,将 3,6- [18] Chen Libo (陈立波), Song Lanqi (宋兰琪). Application of high
pressure differential scanning analysis technology in thermal oxidation
二叔丁基咔唑作为Ⅱ类基础油的抗氧剂,并与 MoE of lubricating oils[J]. Lubrication Engineering (润滑与密封), 2003, (1):
51-52.
复配,提高了Ⅱ类基础油的抗氧化性能。通过 DSC [19] Xu Jinlong (徐金龙), Li Bin (栗斌), Chen Deyou (陈德友), et al.
动态法和 RPVOT 法对其在Ⅱ类基础油中的抗氧化 Study on diesel oil oil change period by PDSC method[J]. Lubricating
Oil (润滑油), 2004, 19(5): 48-50.
性能进行了测试。DSC 和 RPVOT 结果表明,3,6- [20] Jie Minjie (颉敏杰), Xue Weiguo (薛卫国), Lei Ailian (雷爱莲), et
二叔丁基咔唑可以有效提高Ⅱ类基础油的氧化安定 al. Application of pressure differential scanning calorimetry in
thermal oxidation of lubricating oil[J]. Synthetic Lubricants (合成润
性,延长其使用时间,和 MoE 复配后效果更好。在 滑材料), 2009, 36(1): 17-20.
[21] Yu Xianmin (余先民), Tan Gejiang (檀革江), Wang Yijiong (王轶炯).
咔唑苯环上引入叔丁基后,改善了咔唑在Ⅱ类基础 Study on oxidation stability of lubricating oils and base oils by pdsc
油中的溶解性。因此,3,6-二叔丁基咔唑具有用作润 thermal analysis [J]. Lubricating Oil (润滑油), 1999, 14(1): 11-14.
[22] Bonesi S M, Erra-Balsells R. On the synthesis and isolation of chlo-
滑油添加剂的可能。后续研究建议提高有机钼助剂 rocarbazoles obtained by chlorination of carbazoles[J]. Journal of
Heterocyclic Chemistry, 1997, 34(3): 877-889.
中的钼含量及合成长链咔唑衍生物,以期进一步提 [23] Rowan E V, Karol T J, Farmer H H. Organic molybdenum
高其抗氧化效率。 complexes: US 4889647[P]. 1989-09-26.
[24] National Development and Reform Commission (中华人民共和国国
家发展和改革委员会). Lubricating oils-determination of oxidation
参考文献: stability-rotating pressure vessel method: SH/T 0193-2008[S]. Beijing:
China Petrochemical Press (中国石化出版社), 2008.
[1] Kolmogorov V. Friction and wear model for a heavily loaded sliding