摘要
聚苯胺(PAN)因其性能优良、应用广泛而一直是共轭聚合物领域中被广泛研究的课题,对聚苯胺的改性,拓宽其应用领域一直是广大科学家致力研究的对象。目前,聚苯胺的研究还主要集中于无规共聚方面,合成方法主要是电化学氧化和化学氧化法,虽然方法比较简单,但是无法控制聚合物各单元的有序链接,关于聚苯胺交替共聚物方面的研究较少。因此,本论文采用Ni(II)催化法合成了联苯二胺、对苯二胺与2,1,3-苯并硒二唑、2,1,3-苯并噻二唑、噻吩以及烷基取代噻吩的交替共轭共聚物,通过碘对所得到的共聚物进行了掺杂,并对其掺杂之后的电学性能作了初步探讨。具体的研究成果如下:
1.苯胺类与噻吩单元共聚后的产率相对较高。
2.由此种方法合成所得到的联苯二胺、对苯二胺与二唑类的交替共聚物,其数均分子量数量级均在10000以上,在CF3COOH中共聚物能够发生质子酸掺杂,所得本征态的共聚物均不导电。通过比较我们还得出,含有2,1,3-苯并硒二唑单元的共聚物较含有2,1,3-苯并噻二唑单元共聚物的共轭程度大,电化学性能和规整性要好。
3.由此种方法合成所得到的联苯二胺、对苯二胺与噻吩类的交替共聚物,在CF3COOH中共聚物能够发生质子酸掺杂,随着噻吩环上烷基链的增加,共聚物的溶解性增加,但共轭程度却在降低,所得本征态的共聚物均不导电,规整度较差。
4.碘掺杂之后的共聚物,其导电率的数量级最高达到了10-6 S/cm,充放电最高达到了116 F/g。通过比较我们还得出了含有噻吩单元的共聚物经过碘掺杂之后较含有二唑单元共聚物的导电率要高,但比电容相对来讲要低。
Polyaniline (PAN) has been extensively studied because of its better properties and wide application. Many scientists devote themselves to its transformation of properties and the extension of application. Recently, many papers reported the irregular PAN. PAN are usually prepared by electrochemical polymerization and chemical oxidative polymerization. Although these two methods are simple, we can′t obtain regular linked PAN. Only limited attention has been paid to alternated copolymers of aniline. In this paper, the alternated copolymers of benzidine,p-phenylenediamine and 2,1,3-benzoselenadiazole,2,1,3-benzothiadiazole, thiophene or substituted thiophene were prepared by Ni(Ⅱ) catalyzed. The obtained copolymers were also doped with iodine. The main results are summarized as follows:
1. The copolymers of benzidine and thiophene show high yield.
2. The alternated copolymers of aniline and 2,1,3-benzoselenadiazole ,2,1,3-benzothiadiazole were characterized by FT-IR spectroscopy. Their order of magnitude of molecular weight are 104. The copolymers can be doped in CF3COOH. The neutral copolymers have no conductivity. In addition, the copolymers of aniline and 2,1,3-benzoselenadiazole have better electrochemical activity and crystal by comparison.
3. The alternated copolymers of aniline and thiophene or alkyl-substituted thiophene were characterized by FT-IR spectroscopy. The neutral copolymers have no conductivity. And they have poor crystal. Along with the substituted alkyl chain rising, the ability of solution is more increasent, but the conjugation is lower.
4. The obtained copolymers of aniline and 2,1,3-benzoselenadiazole ,2,1,3-benzothiadiazole thiophene or alkyl-substituted thiophene were doped with iodine. Their maximal conductivity order of magnitude come up to 10-6 S/cm. The maximal specific capacitance are 116 F/g. The copolymers of aniline and electron donor unit have high conductivity, but low specific capacitance.
引文
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