掺杂态聚苯胺的研究
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摘要
本研究以未经提纯的苯胺(Aniline，An)为单体，过硫酸铵(APS)为氧化剂，水为溶剂，以几种不同的掺杂剂，按照一定的比例配合，采用一步法直接在苯胺聚合反应中制备了掺杂态的聚苯胺，研究了反应条件对苯胺聚合的影响，得到了苯胺聚合的较佳条件，并研究了不同掺杂剂制备的聚苯胺的性能。
研究表明，以盐酸与十二烷基苯磺酸钠摩尔比1／1混和溶液(LAS-HCl)为掺杂剂制备聚苯胺的最佳条件是：LAS与An的摩尔比为1／1，APS与An的摩尔比为1／1，反应温度在20℃左右，反应时间6h最为合适。
研究发现，LAS-HCl掺杂的聚苯胺与盐酸掺杂的聚苯胺相比，其热稳定性有很大提高，热分解起始温度提高到200℃左右，在250℃的热失重是2.9％，而在281℃时，其质量损失仅为5％，在250℃，真空处理30min，其电导率仅下降了一个数量级。
本文分别制备了盐酸与聚乙烯磺酸钠混合溶液(PSVS-HCl)掺杂聚苯胺和盐酸与乙烯基磺酸钠混和溶液(SVS-HCl)掺杂聚苯胺。研究表明，与SVS-HCl掺杂聚苯胺相比，PSVS-HCl掺杂聚苯胺在导电性上变化不大，只是产率略有提高；PSVS-HCl掺杂所得的聚苯胺热稳定性没有得到改善。
同时，本文分别制备了盐酸与聚苯乙烯磺酸钠混合溶液(PSSS-HCl)掺杂聚苯胺与盐酸与苯乙烯磺酸钠混和溶液(SSS-HCl)掺杂聚苯胺。与SSS-HCl掺杂聚苯胺相比，PSSS-HCl掺杂聚苯胺的脱掺杂起始温度由222℃提高到282℃；PSSS-HCl掺杂聚苯胺的产率和导电性均有较大提高。
此外，本文用乙醇作为助溶剂，利用DBSA(十二烷基苯磺酸)一步掺杂合成聚苯胺，研究表明合成聚苯胺的最佳条件是：DBSA／An(摩尔比)为1.2，APS／An(摩尔比)为1.0，乙醇和水的体积比是1／1。
研究发现，使用乙醇作为助溶剂对合成聚苯胺的脱掺杂温度没有影响。通过使用乙醇作为助溶剂，不仅可以提高产量，而且还消除了实验中起泡，结块等不利因素。
Polyaniline were synthesized in water by oxidation, in which Aniline (An) unrefined is monomer and Ammonium persulfate is oxidant. In aniline polymerization process several kinds of different dopants were added by one-step method. The effects of different reaction conditions on polyaniline properties were studied and optimum condition was obtained. The polyanilines containing different dopants were characterized. The conclusions were gotten as follows.
The optimum conditions for aniline polymerization with the dopant of the solution blended with hydrochloric acid and LAS at the proportion of 1/1 (LAS-HCl) are that the mole ratio of LAS and An is 1/1, and that of APS and An is also 1/1, the temperature of the polymerization is about 20℃, the proper reaction time is about 6 hours.
The thermal stability of the polyaniline doped with LAS-HCl has been improved a lot in contrast with that doped with HCl, and the start thermal decomposition temperature is about 200℃, the thermal weightlessness is 2.9% at 250℃, and only 5% at 281℃, the conductivity decreases at one order of magnitude after being kept in vacuum at 250℃ for 30 minutes.
The polyaniline were synthesized respectively with the dopants of the solution blended with hydrochloric acid and PSVS (PSVS-HCl) and the solution blended with hydrochloric acid and SVS (SVS-HCl), The conductivity of the polyaniline doped with PSVS-HCl do not change much in contrast with the one doped with SVS-HCl, but the productivity increases a little. The thermal stability of the polyaniline doped with PSVS-HCl was not improved.
And the polyaniline were synthesized respectively with the dopants of the solution blended with hydrochloric acid and PSSS (PSSS-HCl) and the solution blended with hydrochloric acid and SSS (SSS-HCl), the start undoped temperature of the polyaniline doped with PSSS-HCl increases from 222℃ to 282℃ comparing to that of the one doped with SSS-HCl, while the productivity and conductivity of the polyaniline doped with PSSS-HCl increase very much too.
When the assistant solvent is ethanol and the dopant is DBSA, the optimum conditions for aniline polymerization by one-step method are that the mole ratio of
DBSA and An is 1.2, the mole ratio of APS and An is 1.0, and the volume ratio of ethanol and water is 1/1.
The thermal stability of the polyaniline is not influenced using ethanol as assistant solvent, and by this way the production increases and the bad factors such as frothiness and agglomeration in the polymerization process are removed.
研究表明，以盐酸与十二烷基苯磺酸钠摩尔比1／1混和溶液(LAS-HCl)为掺杂剂制备聚苯胺的最佳条件是：LAS与An的摩尔比为1／1，APS与An的摩尔比为1／1，反应温度在20℃左右，反应时间6h最为合适。
研究发现，LAS-HCl掺杂的聚苯胺与盐酸掺杂的聚苯胺相比，其热稳定性有很大提高，热分解起始温度提高到200℃左右，在250℃的热失重是2.9％，而在281℃时，其质量损失仅为5％，在250℃，真空处理30min，其电导率仅下降了一个数量级。
本文分别制备了盐酸与聚乙烯磺酸钠混合溶液(PSVS-HCl)掺杂聚苯胺和盐酸与乙烯基磺酸钠混和溶液(SVS-HCl)掺杂聚苯胺。研究表明，与SVS-HCl掺杂聚苯胺相比，PSVS-HCl掺杂聚苯胺在导电性上变化不大，只是产率略有提高；PSVS-HCl掺杂所得的聚苯胺热稳定性没有得到改善。
同时，本文分别制备了盐酸与聚苯乙烯磺酸钠混合溶液(PSSS-HCl)掺杂聚苯胺与盐酸与苯乙烯磺酸钠混和溶液(SSS-HCl)掺杂聚苯胺。与SSS-HCl掺杂聚苯胺相比，PSSS-HCl掺杂聚苯胺的脱掺杂起始温度由222℃提高到282℃；PSSS-HCl掺杂聚苯胺的产率和导电性均有较大提高。
此外，本文用乙醇作为助溶剂，利用DBSA(十二烷基苯磺酸)一步掺杂合成聚苯胺，研究表明合成聚苯胺的最佳条件是：DBSA／An(摩尔比)为1.2，APS／An(摩尔比)为1.0，乙醇和水的体积比是1／1。
研究发现，使用乙醇作为助溶剂对合成聚苯胺的脱掺杂温度没有影响。通过使用乙醇作为助溶剂，不仅可以提高产量，而且还消除了实验中起泡，结块等不利因素。
Polyaniline were synthesized in water by oxidation, in which Aniline (An) unrefined is monomer and Ammonium persulfate is oxidant. In aniline polymerization process several kinds of different dopants were added by one-step method. The effects of different reaction conditions on polyaniline properties were studied and optimum condition was obtained. The polyanilines containing different dopants were characterized. The conclusions were gotten as follows.
The optimum conditions for aniline polymerization with the dopant of the solution blended with hydrochloric acid and LAS at the proportion of 1/1 (LAS-HCl) are that the mole ratio of LAS and An is 1/1, and that of APS and An is also 1/1, the temperature of the polymerization is about 20℃, the proper reaction time is about 6 hours.
The thermal stability of the polyaniline doped with LAS-HCl has been improved a lot in contrast with that doped with HCl, and the start thermal decomposition temperature is about 200℃, the thermal weightlessness is 2.9% at 250℃, and only 5% at 281℃, the conductivity decreases at one order of magnitude after being kept in vacuum at 250℃ for 30 minutes.
The polyaniline were synthesized respectively with the dopants of the solution blended with hydrochloric acid and PSVS (PSVS-HCl) and the solution blended with hydrochloric acid and SVS (SVS-HCl), The conductivity of the polyaniline doped with PSVS-HCl do not change much in contrast with the one doped with SVS-HCl, but the productivity increases a little. The thermal stability of the polyaniline doped with PSVS-HCl was not improved.
And the polyaniline were synthesized respectively with the dopants of the solution blended with hydrochloric acid and PSSS (PSSS-HCl) and the solution blended with hydrochloric acid and SSS (SSS-HCl), the start undoped temperature of the polyaniline doped with PSSS-HCl increases from 222℃ to 282℃ comparing to that of the one doped with SSS-HCl, while the productivity and conductivity of the polyaniline doped with PSSS-HCl increase very much too.
When the assistant solvent is ethanol and the dopant is DBSA, the optimum conditions for aniline polymerization by one-step method are that the mole ratio of
DBSA and An is 1.2, the mole ratio of APS and An is 1.0, and the volume ratio of ethanol and water is 1/1.
The thermal stability of the polyaniline is not influenced using ethanol as assistant solvent, and by this way the production increases and the bad factors such as frothiness and agglomeration in the polymerization process are removed.
引文
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