Electrochemical Synthesis and Electrochromic Properties of Highly Crosslinked Polyarylamines from Bis(triphenylamine)s with Multiple Triphenylamine or N-Phenylcarbazole End-Cappers

• Main Authors: CHIU, CHIA-YU, 邱佳俞
• Other Authors: HSIAO, SHENG-HUEI
• Format: Others
• Language: en_US
• Published: 2019
• Online Access: http://ndltd.ncl.edu.tw/handle/65587x

碩士 === 國立臺北科技大學 === 化學工程與生物科技系化學工程碩士班 === 107 === Two novel aromatic tetraamines, namely N,N,N',N'-tetra(4-aminophenyl)-m-phenylenediamine (TAPMPD) and N,N,N’,N’-tetra(4-aminophenyl)-p-phenylenediamine (TAPPPD), were synthesized by aromatic substitution reactions of m-phenylenediamine and p-phenylenediamine, respectively, with four equivalent amounts of p-fluoronitrobenzene in the presence of potassium carbonate in dimethyl sulfoxide, followed by hydrazine Pd/C-catalyzed reduction. Four electro-polymerizable monomers featuring with bis(triphenylamine) as an interior core via amide groups linked to four terminal electroactive triphenylamine (TPA) or N-phenylcarbazole (NPC) units, coded as MPD-(TPA)4, MPD-(NPC)4, PPD-(TPA)4, and PPD-(NPC)4, were prepared by the condensation reaction from TAPMPD or TAPPPD with four equivalent amounts of 4-carboxytriphenylamine and N-(4-carboxyphenyl)carbazole, respectively. Since these monomers have multiple reactive sites, robust polymeric films of highly crosslinked polyarylamines could be easily deposited on the indium tin oxide (ITO)/glass surface by repetitive cyclic voltammetry scanning of the monomer solutions containing an electrolyte between 0.0 and 1.4─1.6 V. Due to the triarylamine-rich polymer matrix, the electropolymerized films (especially for the PPD series polymers) showed multi-staged redox processes and multi-colored anodic electrochromic behaviors. As compared to that of the MPD series polymers, the bis(triphenylamine) core of the PPD series counterparts provided a lower onset oxidation potential, a clearer and wider separation of the first two redox couples, and a better electrochromic performance. Single-layer electrochromic devices using the electrodeposited polymer films as active layers were fabricated and tested as the preliminary investigation for their electrochromic applications.