Premium
Productive Synthesis and Properties of Polydiaminoanthraquinone and Its Pure Self‐Stabilized Nanoparticles with Widely Adjustable Electroconductivity
Author(s) -
Li XinGui,
Li Hu,
Huang MeiRong
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700541
Subject(s) - polymerization , materials science , chemical engineering , thermal stability , differential scanning calorimetry , photoluminescence , nanomaterials , nanoparticle , polymer chemistry , polymer , nanotechnology , physics , optoelectronics , engineering , composite material , thermodynamics
Wholly aromatic poly(1,5‐diaminoanthraquinone) (PDAA) particles were productively synthesized for the first time by chemically oxidative polymerization of 1,5‐diaminoanthraquinone (DAA) by using CrO 3 , K 2 Cr 2 O 7 , K 2 CrO 4 , or KMnO 4 as oxidants in acidic DMF. The effects of the oxidant species, oxidant/DAA ratio, polymerization temperature, and medium on the polymerization yield, macromolecular structure, size, electroconductivity, solubility, solvatochromism, thermostability, photoluminescence, and silver‐ion sorption of the PDAA particles were systematically studied by IR, UV/Vis, fluorescence, and solid‐state 13 C NMR spectroscopies, wide‐angle X‐ray diffraction, scanning and transmission electron microscopies, and laser particle‐size, differential scanning calorimetry (DSC), and thermal gravimetric (TG) analyses. It seems that the DAA is oxidatively polymerized at the 1,4‐ and 5,8‐positions. Surprisingly, the chemical oxidative polymerization of DAA with CrO 3 at 0 °C in H 2 SO 4 /DMF in the absence of external stabilizer simply affords novel PDAA nanoparticles of around 30 nm in diameter with high purity, clean surfaces, inherent semiconductivity, and self‐stability that can be ascribed to the presence of a large number of 1,4‐benzoquinone units that are negatively charged on their macromolecular chains. The polymers exhibit a high thermal stability at temperatures below 400 °C. Two unique nanoeffects were found, namely the strongest silver‐ion adsorbability and photoluminescence of the PDAA nanoparticles. This gives a facile and general route for the application of the versatilities of PDAA nanomaterials. The PDAA particles are good semiconductors with a widely adjustable conductivity that moves across seven orders of magnitude through simple HClO 4 redoping or Ag + sorption, as expected.