导电高分子材料的制备与性能研究
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摘要
高分子材料由于其质量轻、易加工、耐热、耐腐蚀及良好的机械性能，作为结构材料在众多领域得到广泛的应用。导电高分子材料根据其导电物质的不同，可分为结构型导电高分子材料和复合型导电高分子材料。随着90年代后大量的实验与研究，导电高分子材料已经逐步进入了实际应用阶段。
本论文从四个方面制备了不同类型导电高分子材料，研究了合成方法、制备工艺等对导电高分子材料结构与性能的影响，并用SEM、TEM、IR、DTG、电导率测试仪等仪器对其进行表征，结论如下：
1.以苯胺酚醛树脂为前驱体，掺杂ZnCl_2改性剂，制得了改性酚醛树脂导电高分子材料。分别研究了ZnCl_2加入量、原料配比、合成温度、固化温度对产物结构与导电性能的影响。研究结果表明：(1)、通过SEM观察，所制备的产物为含有ZnCl_2微球的酚醛树脂；(2)、在IR曲线中观察到酚醛树脂骨架中含有氮元素；(3)、在氯化锌与酚醛树脂质量比3:1，升温速率1℃/min、固化温度180℃时，固化产物的电导率可达7.8×10~(-5)S/cm。
2.以苯胺酚醛树脂为前驱体，氮气保护下在不同温度下加热使苯胺酚醛树脂裂解，制备了酚醛树脂热解碳材料。研究结果表明：所制备的苯胺酚醛树脂热解碳材料为三维网状碳骨架结构，以0.5℃/min的升温速率升温至800℃并维持2h，其比表面积达到70m~2/g、电导率为8.63S/cm。
3.本实验利用化学氧化法制备了质子酸掺杂的聚苯胺粉末，并研究了在不同工艺条件下的产物电导率与产率变化关系。研究结果表明：(1)、不同的工艺条件对产物的电导率有较大影响，对产率影响相对较低；(2)、以APS为氧化剂、反应温度为30℃、APS与苯胺单体摩尔比为1.0、25min滴加完APS溶液，掺杂反应时间为15h时，所制得的聚苯胺电导率最高，达5.39S/cm。
4.将所制备聚苯胺还原为本征态，在丙酮中分别与氯化镧、氯化铈混合浸泡，制得稀土掺杂聚苯胺。通过海量数据筛选出最佳工艺条件，研究结果表明：(1)、通过SEM可以观察到：稀土元素掺杂的聚苯胺由三维棒状网络结构组成，相比本征态聚苯胺具有更高的孔隙率；(2)、在IR曲线中发现：掺杂过程中稀土元素只影响醌式结构中的亚胺基，其接受一个质子后变为=NH~+结构，因此掺杂过程可以看做是赝质子化过程；(3)、在掺杂时间为24h时，两种不同掺杂聚苯胺产物电导率均达到最大，分别为4.29×10~(-3)S/cm与1.31×10~(-2)S/cm。
Polymer materials used as a structural material because of its light weight, easy processing,heat resistance, corrosion resistance and fine mechanical properties, have been extensivelyapplied in many fields. With the fast development of information technology, all kinds offunctional polymer materials emerge as the times require, and the conductive polymer materialsare one of the most outstanding one. Conductive polymer material is divided into structuralconductive material and composite material. With the large number of experiments and researchafter90’s, conductive polymer materials has been gradually used into practical application.
In this paper, four different types of conductive polymer materials were prepared accordingto four aspects. The influences of the synthesis and preparation on the structures and propertieswere studied, which were characterized through SEM, TEM, IR, DTG and conductivity meter.the conclusions are as follows:
1. conductive phenol formaldehyde resin was obtained by heat treatment of aniline-phenolformaldehyde (APF) resin doped with different contents of a modifier (ZnCl_2). The influences ofthe contents of ZnCl_2, the ratio of raw materials, synthesis temperature, and curing temperatureon product conductivity were also studied respectively. The researchresults showed that:1. Thestructure of PF-resin contained ZnCl_2microsphere;2. In IR curve, the nitrogen element wasfound in the PF-resin matrix;3. When resin-ZnCl_2mass ratio was1:3, and the speed of heattreatment,1℃/min, and the curing temperature,180℃, the conductivity of the cured materialcould increase to7.8×10~(-5)S/cm.
2. phenolic resin pyrolysis carbon materials were prepared by different heat treatments withaniline phenolic resin as precursor, under the protection of nitrogen gas. The research resultsshow that: aniline phenolic resin pyrolysis carbon materials were constructed by three-dimensio-nal network of carbon skeleton structure. With0.5℃/min heating rate up to900℃andmaintaining2h, the specific surface area was70m~2/g, and the conductivity of the anilinephenolic resin pyrolysis carbon materials was8.63S/cm.
3. The experiments used chemical oxidation method for preparing polyaniline dark greenpowder which doped protonic acid, and studied the varieties of the products conductivity and theyield under different conditions. The research results show that:1. Different process conditionson product conductivity has great effect but relatively low on the yield;2. When APS and anilinemonomer molar ratio was1:1, the reaction temperature30℃, doped APS solution in25min, andthe reaction time was15h, the conductivity of the polyaniline could increase to5.39S/cm.
4. the rare earth doped polyaniline materials were obtained by the immersion of theeigenstate polyaniline and anthanum chloride, cerium chloride mixture in acetone. Themorphology and molecular structure were characterized by SEM and infrared spectrum analysis.The best conditions of preparing the highest conductivity of the materials were also recordedthrough mass experimental statistics. The research results show that:1. The rare earth elementsdoped polyaniline were constructed by three dimensional rod-like network structure throughSEM. They had higher porosity compared to polyaniline;2. Rare earth elements affected onlythe quinoid structure of imine, which accepts a proton into=NH+structure, so the dopingprocess could be regarded as a pseudo protonation process;3. when doping time was24h, boththe conductivity of the two kinds of doped polyaniline reached their maximum of4.29×10-3S/cm
本论文从四个方面制备了不同类型导电高分子材料，研究了合成方法、制备工艺等对导电高分子材料结构与性能的影响，并用SEM、TEM、IR、DTG、电导率测试仪等仪器对其进行表征，结论如下：
1.以苯胺酚醛树脂为前驱体，掺杂ZnCl_2改性剂，制得了改性酚醛树脂导电高分子材料。分别研究了ZnCl_2加入量、原料配比、合成温度、固化温度对产物结构与导电性能的影响。研究结果表明：(1)、通过SEM观察，所制备的产物为含有ZnCl_2微球的酚醛树脂；(2)、在IR曲线中观察到酚醛树脂骨架中含有氮元素；(3)、在氯化锌与酚醛树脂质量比3:1，升温速率1℃/min、固化温度180℃时，固化产物的电导率可达7.8×10~(-5)S/cm。
2.以苯胺酚醛树脂为前驱体，氮气保护下在不同温度下加热使苯胺酚醛树脂裂解，制备了酚醛树脂热解碳材料。研究结果表明：所制备的苯胺酚醛树脂热解碳材料为三维网状碳骨架结构，以0.5℃/min的升温速率升温至800℃并维持2h，其比表面积达到70m~2/g、电导率为8.63S/cm。
3.本实验利用化学氧化法制备了质子酸掺杂的聚苯胺粉末，并研究了在不同工艺条件下的产物电导率与产率变化关系。研究结果表明：(1)、不同的工艺条件对产物的电导率有较大影响，对产率影响相对较低；(2)、以APS为氧化剂、反应温度为30℃、APS与苯胺单体摩尔比为1.0、25min滴加完APS溶液，掺杂反应时间为15h时，所制得的聚苯胺电导率最高，达5.39S/cm。
4.将所制备聚苯胺还原为本征态，在丙酮中分别与氯化镧、氯化铈混合浸泡，制得稀土掺杂聚苯胺。通过海量数据筛选出最佳工艺条件，研究结果表明：(1)、通过SEM可以观察到：稀土元素掺杂的聚苯胺由三维棒状网络结构组成，相比本征态聚苯胺具有更高的孔隙率；(2)、在IR曲线中发现：掺杂过程中稀土元素只影响醌式结构中的亚胺基，其接受一个质子后变为=NH~+结构，因此掺杂过程可以看做是赝质子化过程；(3)、在掺杂时间为24h时，两种不同掺杂聚苯胺产物电导率均达到最大，分别为4.29×10~(-3)S/cm与1.31×10~(-2)S/cm。
Polymer materials used as a structural material because of its light weight, easy processing,heat resistance, corrosion resistance and fine mechanical properties, have been extensivelyapplied in many fields. With the fast development of information technology, all kinds offunctional polymer materials emerge as the times require, and the conductive polymer materialsare one of the most outstanding one. Conductive polymer material is divided into structuralconductive material and composite material. With the large number of experiments and researchafter90’s, conductive polymer materials has been gradually used into practical application.
In this paper, four different types of conductive polymer materials were prepared accordingto four aspects. The influences of the synthesis and preparation on the structures and propertieswere studied, which were characterized through SEM, TEM, IR, DTG and conductivity meter.the conclusions are as follows:
1. conductive phenol formaldehyde resin was obtained by heat treatment of aniline-phenolformaldehyde (APF) resin doped with different contents of a modifier (ZnCl_2). The influences ofthe contents of ZnCl_2, the ratio of raw materials, synthesis temperature, and curing temperatureon product conductivity were also studied respectively. The researchresults showed that:1. Thestructure of PF-resin contained ZnCl_2microsphere;2. In IR curve, the nitrogen element wasfound in the PF-resin matrix;3. When resin-ZnCl_2mass ratio was1:3, and the speed of heattreatment,1℃/min, and the curing temperature,180℃, the conductivity of the cured materialcould increase to7.8×10~(-5)S/cm.
2. phenolic resin pyrolysis carbon materials were prepared by different heat treatments withaniline phenolic resin as precursor, under the protection of nitrogen gas. The research resultsshow that: aniline phenolic resin pyrolysis carbon materials were constructed by three-dimensio-nal network of carbon skeleton structure. With0.5℃/min heating rate up to900℃andmaintaining2h, the specific surface area was70m~2/g, and the conductivity of the anilinephenolic resin pyrolysis carbon materials was8.63S/cm.
3. The experiments used chemical oxidation method for preparing polyaniline dark greenpowder which doped protonic acid, and studied the varieties of the products conductivity and theyield under different conditions. The research results show that:1. Different process conditionson product conductivity has great effect but relatively low on the yield;2. When APS and anilinemonomer molar ratio was1:1, the reaction temperature30℃, doped APS solution in25min, andthe reaction time was15h, the conductivity of the polyaniline could increase to5.39S/cm.
4. the rare earth doped polyaniline materials were obtained by the immersion of theeigenstate polyaniline and anthanum chloride, cerium chloride mixture in acetone. Themorphology and molecular structure were characterized by SEM and infrared spectrum analysis.The best conditions of preparing the highest conductivity of the materials were also recordedthrough mass experimental statistics. The research results show that:1. The rare earth elementsdoped polyaniline were constructed by three dimensional rod-like network structure throughSEM. They had higher porosity compared to polyaniline;2. Rare earth elements affected onlythe quinoid structure of imine, which accepts a proton into=NH+structure, so the dopingprocess could be regarded as a pseudo protonation process;3. when doping time was24h, boththe conductivity of the two kinds of doped polyaniline reached their maximum of4.29×10-3S/cm
引文
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