烯（炔）基型双子座季铵盐的合成及其在酸性电镀镍上的应用
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摘要
光亮镀镍作为一种表面处理技术广泛地应用于五金电镀、电铸以及PCB线路板等领域。为获得光亮、整平的镍镀层,通常需要在瓦特液中加入光亮剂。光亮剂可以分为初级光亮剂、次级光亮剂和辅助光亮剂。
本文首先合成了(E)-1,4-二(溴化-2,4-二甲基吡啶)-2-丁烯(1b)和(E)-1,4-二(溴化三乙基铵)-2-丁烯(1e)等13个可用作次级光亮剂的烯(炔)型双子座季铵盐,通过氢谱和碳谱表征了其结构。
通过赫尔槽、扫描电镜、测厚仪、轮廓仪、螺旋应力仪、电化学工作站等测试手段研究了1b和1e等8种双子座季铵盐对镀层亮度、微观形貌、电沉积过程、镀液分散能力、覆盖能力及整平能力等的影响。其中,1b的综合性能是较好的。
赫尔槽实验结果表明,镀液中添加微量的1b等整平剂,即可得到晶面平整的镀层,而极化曲线和循环伏安曲线的结果也从电化学角度支持了这一结论。亮度和内应力结果说明初级光亮剂糖精和1b等吡啶类双子座季铵盐的协同作用；分散能力的结果则表明了走位剂烯丙基磺酸钠和1e等烷基类双子座季铵盐的协同作用。
极化曲线不但可以研究光亮剂的阴极行为,还能用来筛选最佳浓度范围,并且它筛选出的结果与正交试验的结果是吻合的。
此外,还分别以1b等8种双子座季铵盐为基础,辅之以其它5种商品添加剂,运用正交分析方法筛选出了8例达到商品添加剂水平的光亮剂配方,经过对比后发现1b配方的综合性能最佳。
As a surface treatment, bright nickel-plating has widely been used in metal plating, electroforming, PCB circuit boards and other fields. Brightener is usually added into Watts bath for the acquisition of bright, leveling nickel coating. Brightener can be divided into three categories, including primary, secondary and auxiliary brightener.
To begin with,14 quaternary ammonium Geminis with double (triple) bond were synthesized and characterized their structures by H1NMR and C13NMR in this thesis. These Geminis can be used as the secondary brightener. lb (E)-1,1'-(but-2-ene-1,4-diyl) bis(2,4-dimethylpyridinium) and le (E)-1,1'-(but-2-ene-l,4-diyl) bis (triethylammonium) are the representatives of these Geminis.
Then, the effects of these Geminis above on the coatings'brightness, morphology, electrodeposition, and the bath's throwing, coverage, leveling power were studied by the Hull cell experiments, color separations, scanning electron microscopy, thickness gauge, profilometer, strain gauge, electrochemical workstation and other methods.lb has better overall performance than the other 7 brighteners.
Furthermore, Hull cell test results showed that a flat crystal-surface could be obtained in the solutions with small amount of leveling additives like lb. Results of the polarization curves and cyclic voltammetry curves also supported this conclusion in the electrochemical view. In addition, the brightness and internal stress results gave evidence to the synergies of primary brightener such as saccharin and pyridine Geminis like 1b. Meanwhile, the throwing power results indicated the synergies between sodium allyl(a example of Walking Agent) and alkyl Geminis like le.
Moreover, Brighteners'polarization on the cathode not only can be used to research the agents'cathode behaviors, but also can help to select the suitable agent concentrations. There is a coincidence between these concentrations with the orthogonal result.
Finally,8 brightener formulas were optimized by orthogonal analysis. Every formula contained one Gemini and 5 other commercial additives. The formula containing lb was the best according to their overall performances.
本文首先合成了(E)-1,4-二(溴化-2,4-二甲基吡啶)-2-丁烯(1b)和(E)-1,4-二(溴化三乙基铵)-2-丁烯(1e)等13个可用作次级光亮剂的烯(炔)型双子座季铵盐,通过氢谱和碳谱表征了其结构。
通过赫尔槽、扫描电镜、测厚仪、轮廓仪、螺旋应力仪、电化学工作站等测试手段研究了1b和1e等8种双子座季铵盐对镀层亮度、微观形貌、电沉积过程、镀液分散能力、覆盖能力及整平能力等的影响。其中,1b的综合性能是较好的。
赫尔槽实验结果表明,镀液中添加微量的1b等整平剂,即可得到晶面平整的镀层,而极化曲线和循环伏安曲线的结果也从电化学角度支持了这一结论。亮度和内应力结果说明初级光亮剂糖精和1b等吡啶类双子座季铵盐的协同作用；分散能力的结果则表明了走位剂烯丙基磺酸钠和1e等烷基类双子座季铵盐的协同作用。
极化曲线不但可以研究光亮剂的阴极行为,还能用来筛选最佳浓度范围,并且它筛选出的结果与正交试验的结果是吻合的。
此外,还分别以1b等8种双子座季铵盐为基础,辅之以其它5种商品添加剂,运用正交分析方法筛选出了8例达到商品添加剂水平的光亮剂配方,经过对比后发现1b配方的综合性能最佳。
As a surface treatment, bright nickel-plating has widely been used in metal plating, electroforming, PCB circuit boards and other fields. Brightener is usually added into Watts bath for the acquisition of bright, leveling nickel coating. Brightener can be divided into three categories, including primary, secondary and auxiliary brightener.
To begin with,14 quaternary ammonium Geminis with double (triple) bond were synthesized and characterized their structures by H1NMR and C13NMR in this thesis. These Geminis can be used as the secondary brightener. lb (E)-1,1'-(but-2-ene-1,4-diyl) bis(2,4-dimethylpyridinium) and le (E)-1,1'-(but-2-ene-l,4-diyl) bis (triethylammonium) are the representatives of these Geminis.
Then, the effects of these Geminis above on the coatings'brightness, morphology, electrodeposition, and the bath's throwing, coverage, leveling power were studied by the Hull cell experiments, color separations, scanning electron microscopy, thickness gauge, profilometer, strain gauge, electrochemical workstation and other methods.lb has better overall performance than the other 7 brighteners.
Furthermore, Hull cell test results showed that a flat crystal-surface could be obtained in the solutions with small amount of leveling additives like lb. Results of the polarization curves and cyclic voltammetry curves also supported this conclusion in the electrochemical view. In addition, the brightness and internal stress results gave evidence to the synergies of primary brightener such as saccharin and pyridine Geminis like 1b. Meanwhile, the throwing power results indicated the synergies between sodium allyl(a example of Walking Agent) and alkyl Geminis like le.
Moreover, Brighteners'polarization on the cathode not only can be used to research the agents'cathode behaviors, but also can help to select the suitable agent concentrations. There is a coincidence between these concentrations with the orthogonal result.
Finally,8 brightener formulas were optimized by orthogonal analysis. Every formula contained one Gemini and 5 other commercial additives. The formula containing lb was the best according to their overall performances.
引文
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[9]高灿柱,鹿玉理.缓冲剂在电镀镍中的作用机理研究[A].中国电子学会电镀专业委员会第七届电镀年会[C].合肥：1998.
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[11]陈正法.现代镀镍光亮剂与中间体浅谈[J].材料保护,2007,40(3)：78-79,82.
[12]王赫莹,李德高.镁及镁合金表面电镀镍工艺的研究[J].表面技术,2004,33(5)：48-49,54.
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[14]李新梅,冯拉俊,李志勇.不同发展阶段的镍、铬电镀光亮剂的特性[J].材料保护,2001,34(12)：5-7.
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[16]袁诗璞.谈谈第四代镀镍光亮剂[J].电镀与涂饰,2001,20(4)：44-50.
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[19]陈桧华.光亮镀镍中间体DEP的电化学行为研究[硕士].广州：华南理工大学,2001.
[20]沈品华.第四代镀镍光亮剂研制[J].腐蚀与防护,1999,20(12)：539-542.
[21]方景礼.电镀添加剂理论及应用[M].北京：国防工业出版社,2006.
[22]M. Adamczyk, S. Rege. Microwave assisted sulfopropylation of N-heterocycles using 1,3-propane sultone[J]. Tetrahedron Letters,1998,39(52):9587-9588.
[23]钟振声,冯振宁.吡啶烷氧基磺酸盐的简便合成及助镀性能[J].电镀与涂饰,2004,23(4)：15-17.
[24]J. C. Cameron. Acetylenic compositions and nickel plating baths containing same[P]. US4421611.
[25]易祥榕.镁合金表面电沉积镍的研究[硕十].长沙：湖南大学,2007.
[26]贺同强.电镀珍珠镍及其添加剂的研究[硕士].天津：天津大学,2006.
[27]R. Ludwig, N. C. Lee, C. L. Fan, et al. Evaluation of two novel lead-free surface finishes[J]. Soldering & surface mount technology,2002,14(3):19-24.
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