Synthesis and properties of novel triptycene‐based polyimides

Abstract

Two new triptycene‐containing bis(ether amine)s, 1,4‐bis(4‐aminophenoxy)triptycene (4) and 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)triptycene (6), were synthesized, respectively, from the nucleophilic chloro‐displacement reactions of p‐chloronitrobenzene and 2‐chloro‐5‐nitrobenzotrifluoride with 1,4‐dihydroxytriptycene in the presence of potassium carbonate, followed by palladium‐catalyzed hydrazine reduction of the dinitro intermediates. The bis(ether amine)s were polymerized with six commercially available aromatic tetracarboxylic dianhydrides to obtain two series of novel triptycene‐based polyimides 8a–f and 9a–f by using a conventional two‐step synthetic method via thermal and chemical imidizations. All the resulting polyimides exhibited high enough molecular weights to permit the casting of flexible and strong films with good mechanical properties. Incorporation of trifluoromethyl groups in the polyimide backbones improves their solubility and decreases their dielectric constants. The fluorinated polyimides 9d and 9f derived from diamine 6 with 4,4′‐oxydiphthalic anhydride and 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), respectively, could afford almost colorless thin films. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Synthesis and characterization of novel organosoluble and thermally stable polyamides bearing triptycene in their backbones

“…Assignments of each carbon and proton are also indicated in these spectra, and they are in good agreement with the proposed structures of these two compounds. The IR and NMR data of dinitro compound 4 and diamine monomer 5 are essentially identical with those reported in a previous publication [33].…”

“…As described previously [33], 1,4-bis(4-aminophenoxy) triptycene (5) (mp0186-187°C) was prepared by the aromatic nucleophilic substitution reaction of p-chloronitrobenzene with 1,4-dihydroxytriptycene in the presence of potassium carbonate, followed by hydrogen Pd/C-catalyzed reduction of the intermediate bis(p-nitrophenoxy) compound. p-Fluorobenzonitrile (TCI), potassium carbonate (K 2 CO 3, Showa), potassium hydroxide (KOH, Showa), N,N-dimethylformamide (DMF, Tedia), and triphenyl phosphite (TPP) were used without further purification.…”

“…However, the synthesis and properties of triptycene-containing polymers have only begun to attract attention since 1998 [25][26][27][28][29][30][31]. The use of triptycene moiety as a rigid and shape-persistent component is a method to introduce molecular-scale free volume into a polymer film [32,33].…”

Triptycene poly(ether-imide)s with high solubility and optical transparency

“…2-Trifluoromethyl-4,4′-diaminodiphenyl ether (5d; mp: 112-113°C) [55] and 1,4-bis(4-amino-2-trifluoromethylphenoxy) benzene (5g; mp: 132-133°C) [24] were synthesized by the nucleophilic chloro-displacement reaction of 2-chloro-5-nitrobenzotrifluoride with 4-nitrophenol and hydroquinone, respectively, in the presence of potassium carbonate, followed by the hydrazine Pd/C-catalyzed reduction of the intermediate dinitro compounds. By a similar synthetic procedure, bis [4-(4-aminophenoxy)phenyl] ether (5h; mp: 128-129°C) [56] and 1,4-bis(4-aminophenoxy)triptycene (5i; mp: 254-255°C) [57] were prepared starting from the aromatic nucleophilic substitution reaction of p-chloronitrobenzene with 4,4′-dihydroxydiphenyl ether (TCI) and 1,4-dihydroxytriptycene, respectively, in the presence of potassium carbonate, followed by the hydrazine Pd/C-catalyzed reduction of the intermediate dinitro compounds.…”

Erratum to “Novel Facial Conducting Polyamide-Based Dithiophenylidene Cyclyhexanone Moiety Utilized for Selective Cu2+ Sensing”

“…[12][13][14][15][16][17] Several attempts have been done to overcome such deficiency and producing processable materials while safeguarding their favorable properties, which mainly depending on the structural design in the polymer main chains. [18][19][20][21][22][23] So that, the authors hope that the target polymers which carry sulfur-containing heterocyclic moieties in the form of thiophene and thiazole moieties will enhance their processability due to its amazing optical and electrochemical properties which are used in photovoltaic and other semiconductors devices in addition to other expected characterizations. [24,25] Heavy metal contamination is a major concern in environmental pollution due to their serious toxic effects on plants, animals, and human being.…”