Page 187 - 《精细化工》2020年第1期
P. 187

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
   182   183   184   185   186   187   188   189   190   191   192