铜表面聚合物刷的制备及其电化学性能
Preparation and Electrochemical Performance of Polymer Brush on Copper Substrate
摘 要
采用N-[亚苄基-1, 2-乙二氨基乙基]-2-溴异丁酰胺为引发剂, 联吡啶为配体, 溴化亚铜为催化剂, 实现了铜表面引发甲基丙烯酸甲酯原子转移自由基聚合, 在铜表面形成一层聚甲基丙烯酸甲酯(PMMA)聚合物刷, 在0.5 mol/L NaCl介质中, 采用极化曲线和电化学阻抗法, 考察了聚合物刷的电化学性能。结果表明, 铜表面接枝的PMMA分子量达到1.27×105时, 腐蚀电位提高到22 mV, 腐蚀电流密度降低到0.88 μA/cm2, 缓蚀效率达到96.61%, 膜的电容值为0.398×10-7 F/cm2, 在0.5 mol/L NaCl溶液中浸泡24 h后, NaCl水溶液渗透进入PMMA薄膜的百分比为77.06%。
表面引发原子转移自由基聚合
聚合物刷
电化学性能
copper
surface-initiated atom transfer radical polymerization
polymer brush
electrochemical performance
Abstract
Poly(methylmethacrylate) (PMMA) brushes were grafted from copper substrate by surface-initiated atom transfer radical polymerization from a surface-bound N-[salicylidene-1, 2-ethanediaminoethyl]-2-Bromoisobutyramide (SEB) initiator, with CuBr as catalyst and 2, 2′-bipyridine as ligand. The electrochemical performance of PMMA brush was evaluated by electrochemical impedance spectroscopy (EIS)and polarization curves in 0.5 mol/L NaCl solution. The results showed that when molecular weight of PMMA brush on copper surface reached 1.27×105, the corrosion potential was 22 mV, and the corrosion current density was 0.88 μA/cm2, the capacitance was 0.398×10-7 F/cm2 and the inhibition efficiency was 96.61%, after soaked in 0.5 mol/L NaCl solution for 24 h, 77.06% NaCl solution permeated into the film of PMMA brush.
中图分类号 TG174.42
所属栏目 试验研究
基金项目
收稿日期 2010/4/16
修改稿日期 2010/5/13
网络出版日期
作者单位点击查看
引用该论文: LU Gang,LU Chun-hua,XU Zhong-zi,LI Yi-min. Preparation and Electrochemical Performance of Polymer Brush on Copper Substrate[J]. Corrosion & Protection, 2011, 32(4): 285
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参考文献
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【2】王春涛, 陈慎豪. 分子结构对硫脲类化合物在铜表面自组装能力的影响[J]. 化学学报, 2007, 65 (5): 390-394.
【3】何建波, 周虎林. 铜表面聚苯酚耐蚀膜的电化学制备及表征[J]. 腐蚀与防护, 2008, 29(9): 540-543.
【4】Schweinsberg D P, Hope G A, Trueman A, et al. An electrochemical and SERS study of the action of polyvinylpyrrolidone and polyethylenimine as inhibitors for copper in aerated H2SO4[J]. Corros.Sci., 1995, 38(4):587-599.
【5】Zhao B, Brittain W J. Synthesis of tethered polystyrene-block-poly(methyl methacrylate) monolayer on a silicate substrate by sequential carbocationic polymerization and atom transfer radical polymerization[J]. J.Am.Chem.Soc., 1999, 121:3557-3558.
【6】Jordan R, Ulman A, Kang J F, et al. Surface-initiated anionic polymerization of styrene by means of self-assembled monolayers[J]. J, Am, Chem, Soc, , 1999, 121:1016.
【7】Baum M, Brittain W J. Synthesis of Polymer Brushes on Silicate Substrates via Reversible Addition Fragmentation Chain Transfer Technique[J]. Macromolecules, 2002, 35:610-615.
【8】Nanda A K, Matyjaszewski K. Effect of [bpy]/[Cu(I)] ratio, solvent, counterion, and alkyl bromides on the activation rate constants in atom transfer radical polymerization[J]. Macromolecules, 2003, 36:599-604.
【9】Wang J S, Matyjaszewski K. ′Living′/controlled radical polymerization. Transition-metal-catalyzed atom transfer radical polymerization in the presence of a conventional radical initiator[J]. Macromolecules, 1995, 28:7572-7573.
【10】Zhao B, Brittain W J. Polymer brushes:surface-immobilized, macromolecules[J]. Prog.Polym.Sci., 2000, 25:677-710.
【11】Kim J B, Bruening M L, Baker G L. Surface-initiated atom transfer radical polymerization on gold at ambient temperature[J]. J.Am.Chem.Soc., 2000, 122:7616-7617.
【12】Jones D M, Brown A A, Huck W T S. Surface-initiated polymerizations in aqueous media:Effect of initiator density[J]. Langmuir, 2002, 18:1265-1269.
【13】周峰, 牟宗刚, 于波, 等. 金表面聚合物刷及图案化微结构的制备[J]. 化学学报, 2004, 62(15): 1437-1442.
【14】Chen R X, Zhu S P, Maclaughlin S. Grafting acrylic polymers from flat nickel and copper surfaces by surface-initiated atom transfer radical polymerization[J]. Langmuir, 2008, 24:6889-6896.
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