水溶性聚合物溶液中聚苯胺的合成与表征
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摘要
聚苯胺(PANI)由于稳定性好、合成方便、电导率可调等优点,在电子元件、二次电池、防腐等领域有着广阔的应用前景。微/纳米结构的PANI材料在科学和技术上引起了人们广泛的关注。本文使用原位聚合的方法,选取合适的高分子作为合成PANI的模板,一方面对了解PANI的合成与组装具有重要意义;另一方面,也为聚苯胺及其他新型聚合物纳米材料的的应用开发提供了理论和实验依据。
利用聚乙烯醇(PVA)作为软模板,首次在PVA水溶液体系中合成了由纳米片堆积而成的纳米线。实验结果表明,盐酸和苯胺单体的浓度对PANI产物的形貌有显著的影响;其他实验参数如反应温度、PVA浓度等对PANI产物形貌有一定的影响。提出了PANI在PVA水溶液中的生成与组装机理,认为,PVA分子间通过氢键形成的平行结构及其苯胺聚集体对聚苯胺纳米结构的形成起关键作用。
首次使用可溶性淀粉作为软模板,在控制条件下合成了PANI纳米球、纳米线、微米毯等多种结构。考查了实验条件如反应温度、苯胺浓度、掺杂酸浓度、反应温度等因素对PANI形貌的影响。结果表明,苯胺/掺杂酸摩尔比对PANI形貌影响显著。提出了PANI在淀粉水溶液中的生成机理,认为在淀粉水溶液中,PANI纳米线的团聚和交联是影响最终产物形貌的重要因素:如果PANI纳米线发生团聚,则最终产物是纳米球;如果PANI纳米线发生交联,则得到微米毯。
One of the most studied inherent conducting polymers, polyaniline (PANI) has advantages over some other conducting polymers in cost-effective, good environmental stability, and the controllable conductivity adjusted by the doping/dedoping process. PANI also has promising applications in electronic devices, polymer rechargeable batteries, anticorrosion and so on. PANI with nano/micro-structure has attracted widespread interests in science and technology. Using in-situ polymerization methods, choosing appropriate polymers as soft-template to synthesize aimed polyaniline nanostructures is not only helpful to understand the mechanism of the polymerization and assembly of PANI, but also provides theoretical and experimental basises for developing PANI and other new polymeric composite materials.
Using polyvinyl alcohol (PVA) as soft template, PANI nanofibers accumulated by nanoflakes were obtained for the first time. The influence of reaction parameters, such as reaction time, concentration of reactants, and the content of PVA on the morphology of PANI were investigated. The results indicate that the concentration of HCl and Aniline have significant effect on the morphology of PANI, while other parameters such as reaction time and content of PVA are less significant. The formation mechanism of the PANI nanofibers was proposed. The hydroxyl groups on the parallel-oriented PVA chains play a‘template’role in the assembly process.
Soluble starch was also usd as soft template for polymerization of PANI for the first time, PANI nanostructures such as nanoparticles, nanofibers and micromats assembled by PANI nanofibers were successfully synthesized. The influences of reaction parameters on the morphology of PANI were investigated. The results indicate that the HCl/Aniline molar ratio has significant effect on the morphology of the PANI. The formation mechanism of PANI nanostructures was proposed. Crosslinking and aggregation of PANI have great influence on the morphology of PANI products. If the crosslinking predominates, the products will be micromats, while when aggregation predominates, the products will be nanoparticles.
利用聚乙烯醇(PVA)作为软模板,首次在PVA水溶液体系中合成了由纳米片堆积而成的纳米线。实验结果表明,盐酸和苯胺单体的浓度对PANI产物的形貌有显著的影响;其他实验参数如反应温度、PVA浓度等对PANI产物形貌有一定的影响。提出了PANI在PVA水溶液中的生成与组装机理,认为,PVA分子间通过氢键形成的平行结构及其苯胺聚集体对聚苯胺纳米结构的形成起关键作用。
首次使用可溶性淀粉作为软模板,在控制条件下合成了PANI纳米球、纳米线、微米毯等多种结构。考查了实验条件如反应温度、苯胺浓度、掺杂酸浓度、反应温度等因素对PANI形貌的影响。结果表明,苯胺/掺杂酸摩尔比对PANI形貌影响显著。提出了PANI在淀粉水溶液中的生成机理,认为在淀粉水溶液中,PANI纳米线的团聚和交联是影响最终产物形貌的重要因素:如果PANI纳米线发生团聚,则最终产物是纳米球;如果PANI纳米线发生交联,则得到微米毯。
One of the most studied inherent conducting polymers, polyaniline (PANI) has advantages over some other conducting polymers in cost-effective, good environmental stability, and the controllable conductivity adjusted by the doping/dedoping process. PANI also has promising applications in electronic devices, polymer rechargeable batteries, anticorrosion and so on. PANI with nano/micro-structure has attracted widespread interests in science and technology. Using in-situ polymerization methods, choosing appropriate polymers as soft-template to synthesize aimed polyaniline nanostructures is not only helpful to understand the mechanism of the polymerization and assembly of PANI, but also provides theoretical and experimental basises for developing PANI and other new polymeric composite materials.
Using polyvinyl alcohol (PVA) as soft template, PANI nanofibers accumulated by nanoflakes were obtained for the first time. The influence of reaction parameters, such as reaction time, concentration of reactants, and the content of PVA on the morphology of PANI were investigated. The results indicate that the concentration of HCl and Aniline have significant effect on the morphology of PANI, while other parameters such as reaction time and content of PVA are less significant. The formation mechanism of the PANI nanofibers was proposed. The hydroxyl groups on the parallel-oriented PVA chains play a‘template’role in the assembly process.
Soluble starch was also usd as soft template for polymerization of PANI for the first time, PANI nanostructures such as nanoparticles, nanofibers and micromats assembled by PANI nanofibers were successfully synthesized. The influences of reaction parameters on the morphology of PANI were investigated. The results indicate that the HCl/Aniline molar ratio has significant effect on the morphology of the PANI. The formation mechanism of PANI nanostructures was proposed. Crosslinking and aggregation of PANI have great influence on the morphology of PANI products. If the crosslinking predominates, the products will be micromats, while when aggregation predominates, the products will be nanoparticles.
引文
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