A new triphenylamine-containing aromatic diamine, N,N-bis(4-aminophenyl)-N‘,N‘-diphenyl-1,4-phenylenediamine, was synthesized from the amination reaction between 4-aminotriphenylamine and 4-fluoronitrobenzene and subsequent reduction of the dinitro intermediate. A series of novel aromatic poly(amine-imide)s with pendent triphenylamine units were prepared from the newly synthesized diamine and various tetracarboxylic dianhydrides by either a one-step or a conventional two-step polymerization process. All the poly(amine-imide)s were amorphous and readily soluble in many organic solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide, and chloroform. These polymers could be solution cast into transparent, tough, and flexible films with good mechanical properties. They had useful levels of thermal stability associated with relatively high glass transition temperatures (264−352 °C), 10% weight-loss temperatures in excess of 568 °C, and char yields at 800 °C in nitrogen higher than 63%. These polym...

http://homepage.ntu.edu.tw/~gsliou/FPML/Paper/2005/Macro%20307,%2005.pdf

Novel Aromatic Poly(Amine-Imide)s Bearing A Pendent Triphenylamine Group: Synthesis, Thermal, Photophysical, Electrochemical, and Electrochromic Characteristics

Solution-processable triarylamine-based electroactive high performance polymers for anodically electrochromic applications

A 4-methoxy-substituted triphenylamine containing the aromatic diamine, 4,4′-diamino-4″-methoxytriphenylamine (2), was synthesized by the caesium fluoride-mediated condensation of p-anisidine with 4-fluoronitrobenzene, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediate. A series of new polyamides with pendent 4-methoxy-substituted triphenylamine (TPA) units having inherent viscosities of 0.27–1.39 dL g−1 were prepared via the direct phosphorylation polycondensation of various dicarboxylic acids and the diamine (2). All the polymers were readily soluble in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc), and could be solution-cast into tough and flexible polymer films. These aromatic polyamides had useful levels of thermal stability associated with their relatively high softening temperature (242–282 °C), 10% weight-loss temperatures in excess of 470 °C, and char yields at 800 °C in nitrogen higher than 60%. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium-tin oxide (ITO)-coated glass substrate exhibited reversible oxidation at 0.73–0.79 V versus Ag/AgCl in acetonitrile solution, and revealed excellent stability of electrochromic characteristics with a color change from colorless to green at applied potentials ranging from 0.00 to 1.05 V. These anodically polymeric electrochromic materials not only showed excellent reversible electrochromic stability with good green coloration efficiency (CE = 374 cm2 C−1) but also exhibited high contrast of optical transmittance change (ΔT %) up to 85% at 787 nm and 30% at 391 nm. After over 1000 cyclic switches, the polymer films still exhibited excellent stability of electrochromic characteristics.

http://homepage.ntu.edu.tw/~gsliou/FPML/Paper/2007/J.%20Mater.%20Chem.,%202007,%2017,%201007-1015.pdf

Highly stable anodic green electrochromic aromatic polyamides: synthesis and electrochromic properties

▪ Abstract High-temperature polymers have found widespread use in aerospace and electronics applications. This review deals with recent developments in the chemistry of these materials that have led to improvements in processability and high-temperature stability.

Recent advances in the development of processable high-temperature polymers1

A new adamantane-based dietheramine, 2,2-bis[4-(4-aminophenoxy)phenyl]adamantane, was prepared in two steps from chloro displacement or p-chloronitrobenzene with the potassium phenolate of 2,2-bis(4-hydroxyphenyl)adamantane, followed by hydrazine catalytic reduction of the intermediate dinitro compound. A series of polyimides with the adamantane-2,2-diyl unit as a cardo group was prepared from the adamantane-based dietheramine and various aromatic dianhydrides by a conventional two-stage synthesis in which the poly(amic acid)s obtained in the first stage were heated stage-by-stage at 150-270 °C to give the polyimides. The intermediate poly(amic acid)s had inherent viscosities between 0.82 and 1.66 dL/g. Except for the polyimide from pyromellitic dianhydride, all of the polyimides could be dissolved in NMP, and several polyimides also showed good solubility in other organic solvents. All of the polyimides were amorphous in nature as evidenced by X-ray diffractograms. The glass-transition temperatures (Tg) of these polyimides were recorded between 248 and 308 °C by differential scanning calorimetry (DSC), and the softening temperatures (T s ) determined by thermomechanical analysis (TMA) stayed in the range of 254-335 °C. Decomposition temperatures for 10% weight loss all occurred above 500 °C in both air and nitrogen atmospheres.

Synthesis and characterization of new adamantane-based polyimides

Having previously demonstrated the possibility of synthesizing high molecular weight poly(ether imide)s with ortho-linked main-chain units from bis(ether anhydride)s derived from catechol or its derivatives, we now provide a preliminary assessment of the properties of the polymers prepared from the catechol bis(ether anhydride) and a variety of diamines. The polymers have low color, are soluble in a variety of solvents, and are thermally stable to temperatures in excess of 470 °C. Glass transition temperatures are comparable with or higher than that of the commercial poly(ether imide) Ultem. Solvent-cast films have high modului and strengths. Extensions to break are relatively low, except for the polymer based on 4,4‘-bis(4-aminophenoxy)biphenyl, which has an extension of 170%. All the polymers can be drawn to produce materials with higher moduli and strengths and, in most cases, higher extensions to break. Thus the polymers can be processed from the melt or from solution.

R. S. Irwin

Papers

Melt-Processable Poly(ether imide)s Based on Catechol Bis(ether anhydride)

1,2-Bis(carboxyphenoxy)arylenes and aramids and polyarylates therefrom: synthesis and properties