聚苯胺类材料的合成及电流变性能研究
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摘要
电流变流体是一种流变行为可由外加电场控制的智能材料,具有非常重要的学术研究价值和广泛的工程应用前景。本论文对电流变流体的组成、历史起源、分类及电流变效应的特点和影响因素等进行了文献综述,研究了邻甲苯胺和中性红聚合物材料的合成及作为分散相材料的电流变流体在电场下的流变行为,主要内容如下：
采用溶液氧化聚合与乳液聚合的方法分别合成了六个聚苯胺类共轭聚合物：聚邻甲苯胺(POT)、聚中性红(PNR)、邻甲苯胺与中性红的共聚物(POT/NR),对甲苯磺酸掺杂的聚邻甲苯胺(TSA-POT)、对甲苯磺酸掺杂的聚中性红(TSA-PNR)及对甲苯磺酸掺杂的邻甲苯胺与中性红的共聚物(TSA-POT/NR);对聚合物粒子的化学结构、形貌、热稳定性及粒子的电性能进行了表征,研究了各聚合物在不同反掺杂条件下所得粒子的硅油悬浮体系的电流变效应。结果表明各聚合物的硅油体系均体现出正的电流变效应,体系的剪切应力随电场强度的增加而增大,表现出电致屈服应力及电致增稠；聚合物的反掺杂条件影响着聚合物流体体系的电流变效应；TSA-POT, TSA-POT/NR体系的屈服应力与电场强度的平方具有线性关系；由于共聚物中p-π共轭及极性的磺酸基团与聚合物主链的结合,使得TSA-POT/NR及TSA-POT粒子具有较好的容纳电荷的能力,表现出较大的介电常数,由此导致TSA-POT/NR及TSA-POT硅油体系良好的电流变性能。所研究的聚苯胺共轭聚合物体系的电流变效应的强弱由聚合物粒子的介电常数而非电导率决定。
Electrorheological fluid (ER fluid) whose rheological properties were controlled by the application of electric field, is a kind of intelligent materials, and has showed remarkable academic interest and extensive potential engineering application. In this paper, the nature of the electrorheological fluid, its development, its composition and the influence elements on ER effect have been reviewed. Polymers of o-toluidine and neutral red were synthesized; the electrorheological properties of the synthesized polymer-based electrorheological fluids were studied. The main contents are as follows:
Six polyaniline(PANI) derivatives, including poly(o-toluidine) (POT), poly(neutral red) (PNR), poly(o-toluidine-co-neutral red) (POT/NR), p-toluene-sulfonic acid doping poly(o-toluidine) (TSA/POT),p-toluenesulfonic acid doping poly(neutral red) (TSA-POT/NR) and p-toluenesulfonic acid doping poly (o-toluidine-co-neutral red) (TSA-POT/NR) were synthesized by oxidative polymerization and emulsion polymerization; The molecular structure, morphology, thermal properties, dielectric properties and density of these polymers were investigated, and the ER effect based on the particles of anti-doping of the resulting polymers were investigated. The results show that all the polymer-based suspensions of silicone oil exhibited positive ER effect, the suspensions showed yield stress and the increasing viscosity with shear rate under external electric field. The anti-doping condition made great differences on the ER effect of the particle-based suspensions. The yield stress of TSA/POT and TSA-POT/NR suspensions were proportion to the square of electric field strength. Among all the polymer-based suspensions, TSA-POT/NR and TSA/POT suspensions showed best ER effect, which were ascribed to the big dielectric constant of the particles. The p-πconjugated system combined with the highly polarity of sulfonic acid group suspended on the polymer main chain made the two polymers novel capacity of bearing and transferring charges, which in turn to the big dielectric constant. It is the dielectric constant but not the conductivity of the particles that cause the different ER effect for our studied PANI-based suspensions.
采用溶液氧化聚合与乳液聚合的方法分别合成了六个聚苯胺类共轭聚合物：聚邻甲苯胺(POT)、聚中性红(PNR)、邻甲苯胺与中性红的共聚物(POT/NR),对甲苯磺酸掺杂的聚邻甲苯胺(TSA-POT)、对甲苯磺酸掺杂的聚中性红(TSA-PNR)及对甲苯磺酸掺杂的邻甲苯胺与中性红的共聚物(TSA-POT/NR);对聚合物粒子的化学结构、形貌、热稳定性及粒子的电性能进行了表征,研究了各聚合物在不同反掺杂条件下所得粒子的硅油悬浮体系的电流变效应。结果表明各聚合物的硅油体系均体现出正的电流变效应,体系的剪切应力随电场强度的增加而增大,表现出电致屈服应力及电致增稠；聚合物的反掺杂条件影响着聚合物流体体系的电流变效应；TSA-POT, TSA-POT/NR体系的屈服应力与电场强度的平方具有线性关系；由于共聚物中p-π共轭及极性的磺酸基团与聚合物主链的结合,使得TSA-POT/NR及TSA-POT粒子具有较好的容纳电荷的能力,表现出较大的介电常数,由此导致TSA-POT/NR及TSA-POT硅油体系良好的电流变性能。所研究的聚苯胺共轭聚合物体系的电流变效应的强弱由聚合物粒子的介电常数而非电导率决定。
Electrorheological fluid (ER fluid) whose rheological properties were controlled by the application of electric field, is a kind of intelligent materials, and has showed remarkable academic interest and extensive potential engineering application. In this paper, the nature of the electrorheological fluid, its development, its composition and the influence elements on ER effect have been reviewed. Polymers of o-toluidine and neutral red were synthesized; the electrorheological properties of the synthesized polymer-based electrorheological fluids were studied. The main contents are as follows:
Six polyaniline(PANI) derivatives, including poly(o-toluidine) (POT), poly(neutral red) (PNR), poly(o-toluidine-co-neutral red) (POT/NR), p-toluene-sulfonic acid doping poly(o-toluidine) (TSA/POT),p-toluenesulfonic acid doping poly(neutral red) (TSA-POT/NR) and p-toluenesulfonic acid doping poly (o-toluidine-co-neutral red) (TSA-POT/NR) were synthesized by oxidative polymerization and emulsion polymerization; The molecular structure, morphology, thermal properties, dielectric properties and density of these polymers were investigated, and the ER effect based on the particles of anti-doping of the resulting polymers were investigated. The results show that all the polymer-based suspensions of silicone oil exhibited positive ER effect, the suspensions showed yield stress and the increasing viscosity with shear rate under external electric field. The anti-doping condition made great differences on the ER effect of the particle-based suspensions. The yield stress of TSA/POT and TSA-POT/NR suspensions were proportion to the square of electric field strength. Among all the polymer-based suspensions, TSA-POT/NR and TSA/POT suspensions showed best ER effect, which were ascribed to the big dielectric constant of the particles. The p-πconjugated system combined with the highly polarity of sulfonic acid group suspended on the polymer main chain made the two polymers novel capacity of bearing and transferring charges, which in turn to the big dielectric constant. It is the dielectric constant but not the conductivity of the particles that cause the different ER effect for our studied PANI-based suspensions.
引文
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