Li Xin-Gui, Kang Yan, Huang Mei-Rong
Institute of Materials Chemistry, Key Laboratory of Advanced Civil Engineering Materials, College of Materials Science and Engineering, Tongji University, Shanghai 200092, China.
J Comb Chem. 2006 Sep-Oct;8(5):670-8. doi: 10.1021/cc060014m.
A high-throughput multiparameter optimization of chemical oxidative polymerization conditions has been developed for a facile synthesis of furan homopolymers and furan/aniline copolymers using a combinatorial method. The polymerization yield, molecular structure, and properties of the polymers would be optimized against typical polymerization parameters, including oxidant species, medium species, temperature, oxidant/monomer ratio, monomer concentration, dopant concentration, and furan/aniline comonomer ratio. The electrical conductivity, lead ion adsorptivity, chemical resistance, and thermal behavior of the polymers were also elaborated. It is found that only a combination of FeCl(3) and nitromethane as oxidant and medium, respectively, is appropriate for the furan homopolymerization. The homopolymerization yield increases consistently with an increase in the monomer concentration from 0.05 to 0.2 M and the FeCl(3)/furan molar ratio from 0.25 to 1.25. Although the as-prepared polyfuran exhibits very low conductivity, down to 10(-11) S cm(-1), the HCl- and HClO(4)-doped polyfurans possess much higher conductivities of 9.2 x 10(-8) and 2.38 x 10(-5) S cm(-1), respectively. In addition, the conductivity of the furan/aniline copolymer rises steadily with increasing aniline content, although the copolymerization yield shows a minimum at the furan/aniline molar ratio of 60/40, which is evidence of the occurrence of a real copolymerization between the furan and aniline monomers. The difficulty of synthesizing conducting polyfuran could be overcome to some extent by the polymerization in an appropriate condition optimized in this study. Particularly, the difficulty of synthesizing poly(furan-co-aniline) having much higher conductivity than the polyfuran would be largely conquered by chemical oxidative copolymerization of furan with aniline.
已开发出一种用于化学氧化聚合条件的高通量多参数优化方法,采用组合方法简便合成呋喃均聚物和呋喃/苯胺共聚物。将针对典型的聚合参数优化聚合物的聚合产率、分子结构和性能,这些参数包括氧化剂种类、介质种类、温度、氧化剂/单体比例、单体浓度、掺杂剂浓度以及呋喃/苯胺共聚单体比例。还阐述了聚合物的电导率、铅离子吸附性、耐化学性和热行为。发现仅分别将FeCl₃和硝基甲烷作为氧化剂和介质的组合适用于呋喃均聚反应。均聚产率随着单体浓度从0.05 M增加到0.2 M以及FeCl₃/呋喃摩尔比从0.25增加到1.25而持续增加。尽管所制备的聚呋喃表现出非常低的电导率,低至10⁻¹¹ S cm⁻¹,但HCl掺杂和HClO₄掺杂的聚呋喃分别具有9.2×10⁻⁸和2.38×10⁻⁵ S cm⁻¹的高得多的电导率。此外,呋喃/苯胺共聚物的电导率随着苯胺含量的增加而稳步上升,尽管共聚产率在呋喃/苯胺摩尔比为60/40时显示出最小值,这证明了呋喃和苯胺单体之间发生了真正的共聚反应。通过本研究中优化的适当条件下的聚合,可以在一定程度上克服合成导电聚呋喃的困难。特别是,通过呋喃与苯胺的化学氧化共聚,将在很大程度上克服合成具有比聚呋喃高得多的电导率的聚(呋喃 - 共 - 苯胺)的困难。