原位核磁共振技术考察L-缬氨酸导引下合成花状纳米结构聚苯胺形成机理的研究

袁丽; 刘空; 卑凤利; 武晓东

doi:10.11777/j.issn1000-3304.2017.16206

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原位核磁共振技术考察L-缬氨酸导引下合成花状纳米结构聚苯胺形成机理的研究

研究论文 | 更新时间：2021-05-18

- 原位核磁共振技术考察L-缬氨酸导引下合成花状纳米结构聚苯胺形成机理的研究
- Formation Mechanism of Flower-like Nanostructured Polyaniline Prepared under Guidance of L-valine
- 高分子学报 2017年第4期页码：605-615
- 作者机构：
  
  南京理工大学化工学院软化学与功能材料教育部重点实验室南京 210094
- 作者简介：
  
  武晓东, E-mail:wuxd@mail.njust.edu.cn Xiao-dong Wu, E-mail:wuxd@mail.njust.edu.cn
- 基金信息：
  
  国家自然科学基金(21474053);国家自然科学基金(21370053)
- DOI：10.11777/j.issn1000-3304.2017.16206
  中图分类号：
- 纸质出版日期：2017-4，
  
  收稿日期：2016-6-22，
  
  修回日期：2016-8-15，
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袁丽, 刘空, 卑凤利, 武晓东. 原位核磁共振技术考察L-缬氨酸导引下合成花状纳米结构聚苯胺形成机理的研究[J]. 高分子学报, 2017,(4):605-615.

Li Yuan, Kong Liu, Feng-li Bei, Xiao-dong Wu. Formation Mechanism of Flower-like Nanostructured Polyaniline Prepared under Guidance of L-valine[J]. Acta Polymerica Sinica, 2017,(4):605-615.
袁丽, 刘空, 卑凤利, 武晓东. 原位核磁共振技术考察L-缬氨酸导引下合成花状纳米结构聚苯胺形成机理的研究[J]. 高分子学报, 2017,(4):605-615. DOI： 10.11777/j.issn1000-3304.2017.16206.

Li Yuan, Kong Liu, Feng-li Bei, Xiao-dong Wu. Formation Mechanism of Flower-like Nanostructured Polyaniline Prepared under Guidance of L-valine[J]. Acta Polymerica Sinica, 2017,(4):605-615. DOI： 10.11777/j.issn1000-3304.2017.16206.

摘要

利用

H-NMR原位追踪在L-缬氨酸存在下合成花状纳米聚苯胺的形成过程中发现此结构的形成经历3个阶段：首先在苯胺与缬氨酸构成的类胶束结构内聚合成吩嗪类寡聚物；其次通过

重叠作用及胶束融合过程成为片状聚集体；最终通过与缬氨酸形成氢键组装成花瓣状纳米聚苯胺.通过改变反应条件，对比形成过程中核磁共振图谱及产物形貌的变化发现花状纳米聚苯胺的形成有如下特征：反应初期L-缬氨酸作为缓冲试剂可以避免苯胺的骤然质子化，有利于生成具有吩嗪结构的寡聚物；反应前苯胺单体与缬氨酸形成稳定的反应环境保证寡聚物始终在其内聚集生长，有效避免了外部环境的影响.

Abstract

The formation mechanism of flower-like nanostructured polyaniline prepared in the presence of L-valine was explored by a series of

in situ

H-NMR experiments. Depending on the signal evolution of the major species

the flower-like nanostructured polyaniline was observed to be formed through three continuous stages. At first

aniline and L-valine were packed loosely into micelle-like aggregates before the polymerization

and the phenazine-like oligomers were abundantly formed within this kind of micelles; subsequent steady aggregation through

stacking interactions rendered the oligomers to arrange into structurally regular polyaniline nanosheets due to their highly conjugated fused rings; further intermolecular packing of these nanosheets under guidance of L-valine through hydrogen bonds generated the desired flower-like architectures. Moreover

a careful comparison between the samples prepared under varied concentration of L-valine and aniline revealed that the formation of the flower-like nanostructure was closely related to the following characters from L-valine: (1) being amphoteric

which could have served as the buffering agent to prevent abrupt protonation of aniline and to induce several aniline molecules to share the charges together so that the electron density at each reactive site on aniline was nearly identical before the polymerization

the formation of phenazine-like oligomers was therefore favored with a steady proton induced aggregation of these oligomers; (2) locating at the outer-most layer of the aggregates upon the formation of L-valine stabilized monomer micelle due to its amphiphilic feature

which could not only stabilize the monomers and the nascent produced oligomers but also would allow the aggregation of the oligomers to form nanosheets and the subsequent formation of the nanoflowers in the micelle or through fusion of the micelles respectively. This way

any irregular structural arrangement induced by the disturbance from the reaction system or the surroundings might be eliminated

leading to the highly thermodynamic stable product to be produced eventually.

关键词

吩嗪结构寡聚物纳米片氢键π-π重叠作用

Keywords

Phenazine-like oligomersNanosheetsπ-π Stacking interactionsHydrogen-bonds

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