磁场环境中聚苯胺的掺杂行为及其性能的研究与表征
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摘要
聚苯胺(PAn)具有单体价格低廉、合成简便、稳定性良好、较高电导率等优异的特性,引起了人们的广泛关注。用小分子无机酸掺杂的聚苯胺虽然具有较高的电导率,但其溶解性和稳定性较差,极大的限制了它的实用化进程。大分子磺酸具有沸点高,既含有极性基团又含有非极性基团,其稳定性也优于小分子无机酸,因此探讨采用大分子磺酸作为掺杂剂,以提高掺杂态聚苯胺的电导率及应用性具有一定的现实意义。
由于磁场能改变分子取向,控制化学反应速度,改变产物结构并提高其性能,因此研究磁场作用对苯胺聚合行为及其性能的影响已经成为人们感兴趣的热点领域之一,并取得了一定成果。但到目前为止,关于在磁场中用大分子酸掺杂聚苯胺的研究尚鲜见报道。
本文探讨了在磁场作用下采用微乳液法制备高性能聚苯胺的工艺。研究了以下工艺条件:掺杂酸的种类及用量、乳化剂的种类及用量、氧化剂的种类及用量和掺杂时间,并通过正交实验确定了最佳工艺条件。采用数字式四探针电导率仪、电化学工作站、红外光谱仪、X-射线衍射仪、热重分析仪、紫外-可见光谱仪、激光粒度分析仪等现代化分析测试手段,对产品的电导率、腐蚀电位、微观结构、结晶性、热稳定性、粒径分布等性能进行了分析和表征。研究了磁场对聚苯胺性能的影响。
实验结果表明,同等条件下与无磁场作用相比,其红外光谱各个特征峰值变化很小,X射线衍射的衍射峰增强,表明磁场对聚苯胺分子链的单元结构影响不大,但对PAn分子的取向性和规整性有明显的影响。
本文在外加磁场作用下,通过一系列条件实验的结果显示:磁场能缩短反应时间、减少掺杂剂的用量、提高产物的电导率。反应时间从3 h减少到2 h;掺杂酸浓度(CSSA)从0.4 mol·L~(-1)减小到0.3 mol·L~(-1);乳化剂与苯胺单体的摩尔比(nSDBS/nAn)从0.6减少到0.45;氧化剂与苯胺单体的摩尔比(nAPS/nAn)从0.8减少到0.6;电导率从1.65×10~(-1)S·cm~(-1)提高到为10.54×10~(-1)S·cm~(-1)。另外,聚苯胺的腐蚀电位提高了31%,热分解温度提高了6%。在磁场环境中采用本文工艺合成的聚苯胺在导电性、粒径、热稳定性、防腐性、规整性、成本等各方面与无磁场作用的产品相比都有明显的优势,具有广阔的市场开发与应用前景。
Polyaniline (PAn) is one of the most important conducting polymers because of its simple synthesis methods, particular doping mechanism, excellent environmental stability, as well as wide application. At present polyaniline has become one of the hottest focuses in conductive polymer area. With small molecular inorganic acid doping polyaniline has a higher conductivity, but its solubility and the stability are worse, limit its practical advancement. The macromolecular sulfonic acid has higher boiling point, both including the polar groups and the non-polar groups, its stability also surpasses the small molecular inorganic acid, therefore, using the macromolecular sulfonic acid to dope polyaniline can enhance the conductivity and the application, which has the certain practical significance.
As a result of magnetic field can change molecular orientation and control rate of chemical reaction and change product structure and enhance its performance, therefore, study on the synthesis and properties of doped polyaniline in magnetic field has become one of the hottest focuses. But, to our knowledge, no systematic study with respect to the properties of doped polyaniline by sulfonic acid in magnetic field has yet been published.
In this article the technology of high performance polyaniline under the circumstances of microemulsion in magnetic field were synthesized. Some technologic conditions were researched: such as the category and dosage of doped acid the category and dosage of emulsifier agent, the category and dosage of oxidant and reaction time; then, the best technologic conditions were confirmed through the orthogonal experiment. The polyaniline’s conductivity, microstructure, anticorrosion, crystallization, thermal stability, particle size and others properties were analyzed and characterized by modern testing methods, such as IR, XRD, TGA, UV, and so on. Finally, through the comparison of synthesized products without magnetic field, the optimal or the improved collocations were worked out. According to such collocations that the effect of doped polyaniline in magnetic field.
In comparison with out magnetic field, the results indicated that the change of characteristic peak values of polyaniline at their infrared spectrum is not obvious, the X-ray diffraction peaks of polyaniline becomes very intense, which showed the microstructure of polyaniline was not influenced in magnetic field, but the orientation and regularity of polyaniline is obviously improved in magnetic field.
Under magnetic field, based on the data from the experiment in lab condition, the results indicate that the time of the polymerization and the dosage of doped agent were reduced and the conductivity of polyaniline is enhanced in the presence of magnetic filed. The polymerization time decreased from 3 h to 1 h; the concentration of doped acid(CSSA)decreased from 0.4 mol·L~(-1) to 0.3 mol·L~(-1); the mole ratio of emulsifier and aniline monomer (nSDBS/nAn) decreased from 0.6 to 0.45; the mole ratio of oxidant and aniline monomer (nAPS/nAn) decreased from 0.8 to 0.6; the conductivity of polyaniline increased from 1.65×10~(-1)S·cm~(-1) to 10.54×10~(-1)S·cm~(-1) in magnetic field. The corrosition potential of polyaniline has increased by 31%, the thermal decomposition temperature has increased by 6%. Compared with the present polyaniline without magnetic field, the polyaniline synthesized by this improved technology has evident advantages in certain properties, such as conductivity, particle size, thermal stability, anticorrosion, uniform arrangenent, synthetical cost and son on, therefore, possessing bright prospects in marketing development and application.
由于磁场能改变分子取向,控制化学反应速度,改变产物结构并提高其性能,因此研究磁场作用对苯胺聚合行为及其性能的影响已经成为人们感兴趣的热点领域之一,并取得了一定成果。但到目前为止,关于在磁场中用大分子酸掺杂聚苯胺的研究尚鲜见报道。
本文探讨了在磁场作用下采用微乳液法制备高性能聚苯胺的工艺。研究了以下工艺条件:掺杂酸的种类及用量、乳化剂的种类及用量、氧化剂的种类及用量和掺杂时间,并通过正交实验确定了最佳工艺条件。采用数字式四探针电导率仪、电化学工作站、红外光谱仪、X-射线衍射仪、热重分析仪、紫外-可见光谱仪、激光粒度分析仪等现代化分析测试手段,对产品的电导率、腐蚀电位、微观结构、结晶性、热稳定性、粒径分布等性能进行了分析和表征。研究了磁场对聚苯胺性能的影响。
实验结果表明,同等条件下与无磁场作用相比,其红外光谱各个特征峰值变化很小,X射线衍射的衍射峰增强,表明磁场对聚苯胺分子链的单元结构影响不大,但对PAn分子的取向性和规整性有明显的影响。
本文在外加磁场作用下,通过一系列条件实验的结果显示:磁场能缩短反应时间、减少掺杂剂的用量、提高产物的电导率。反应时间从3 h减少到2 h;掺杂酸浓度(CSSA)从0.4 mol·L~(-1)减小到0.3 mol·L~(-1);乳化剂与苯胺单体的摩尔比(nSDBS/nAn)从0.6减少到0.45;氧化剂与苯胺单体的摩尔比(nAPS/nAn)从0.8减少到0.6;电导率从1.65×10~(-1)S·cm~(-1)提高到为10.54×10~(-1)S·cm~(-1)。另外,聚苯胺的腐蚀电位提高了31%,热分解温度提高了6%。在磁场环境中采用本文工艺合成的聚苯胺在导电性、粒径、热稳定性、防腐性、规整性、成本等各方面与无磁场作用的产品相比都有明显的优势,具有广阔的市场开发与应用前景。
Polyaniline (PAn) is one of the most important conducting polymers because of its simple synthesis methods, particular doping mechanism, excellent environmental stability, as well as wide application. At present polyaniline has become one of the hottest focuses in conductive polymer area. With small molecular inorganic acid doping polyaniline has a higher conductivity, but its solubility and the stability are worse, limit its practical advancement. The macromolecular sulfonic acid has higher boiling point, both including the polar groups and the non-polar groups, its stability also surpasses the small molecular inorganic acid, therefore, using the macromolecular sulfonic acid to dope polyaniline can enhance the conductivity and the application, which has the certain practical significance.
As a result of magnetic field can change molecular orientation and control rate of chemical reaction and change product structure and enhance its performance, therefore, study on the synthesis and properties of doped polyaniline in magnetic field has become one of the hottest focuses. But, to our knowledge, no systematic study with respect to the properties of doped polyaniline by sulfonic acid in magnetic field has yet been published.
In this article the technology of high performance polyaniline under the circumstances of microemulsion in magnetic field were synthesized. Some technologic conditions were researched: such as the category and dosage of doped acid the category and dosage of emulsifier agent, the category and dosage of oxidant and reaction time; then, the best technologic conditions were confirmed through the orthogonal experiment. The polyaniline’s conductivity, microstructure, anticorrosion, crystallization, thermal stability, particle size and others properties were analyzed and characterized by modern testing methods, such as IR, XRD, TGA, UV, and so on. Finally, through the comparison of synthesized products without magnetic field, the optimal or the improved collocations were worked out. According to such collocations that the effect of doped polyaniline in magnetic field.
In comparison with out magnetic field, the results indicated that the change of characteristic peak values of polyaniline at their infrared spectrum is not obvious, the X-ray diffraction peaks of polyaniline becomes very intense, which showed the microstructure of polyaniline was not influenced in magnetic field, but the orientation and regularity of polyaniline is obviously improved in magnetic field.
Under magnetic field, based on the data from the experiment in lab condition, the results indicate that the time of the polymerization and the dosage of doped agent were reduced and the conductivity of polyaniline is enhanced in the presence of magnetic filed. The polymerization time decreased from 3 h to 1 h; the concentration of doped acid(CSSA)decreased from 0.4 mol·L~(-1) to 0.3 mol·L~(-1); the mole ratio of emulsifier and aniline monomer (nSDBS/nAn) decreased from 0.6 to 0.45; the mole ratio of oxidant and aniline monomer (nAPS/nAn) decreased from 0.8 to 0.6; the conductivity of polyaniline increased from 1.65×10~(-1)S·cm~(-1) to 10.54×10~(-1)S·cm~(-1) in magnetic field. The corrosition potential of polyaniline has increased by 31%, the thermal decomposition temperature has increased by 6%. Compared with the present polyaniline without magnetic field, the polyaniline synthesized by this improved technology has evident advantages in certain properties, such as conductivity, particle size, thermal stability, anticorrosion, uniform arrangenent, synthetical cost and son on, therefore, possessing bright prospects in marketing development and application.
引文
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