Synthesis and physicochemical studies of ferrocene-containing materials

• Published in: Applied organometallic chemistry Vol. 21; no. 10; pp. 862 - 869
• Main Authors: Iqbal, Naseer, Khan, Muhammad Saif ullah, Adnan Saeed, M., Akhter, Zareen
• Format: Journal Article
• Language: English
• Published: Chichester, UK John Wiley & Sons, Ltd 01.10.2007
• Subjects: ferrocene; organometallic aramids; polyamides
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.1266

Low‐temperature solution‐phase polycondensation of 1,1′‐ferrocenedicarboxylic acid chloride with newly synthesized aromatic diamines was carried out in tetrahydrofuran in the presence of triethylamine to form several new organometallic aromatic polyamides containing ferrocene units. The organometallic aromatic polyamides derived were in good yields ranging from 75 to 80%, amorphous with melting temperatures of > 350 °C. The monomers and the resulting polymers were characterized by their physical properties, elemental analysis,1H NMR and FTIR spectroscopy. The differential scanning calorimetry and thermogravimetric studies of the resulting aramids were also carried out. All the polymers were insoluble in common organic solvents. However, all dissolved in concentrated H2SO4 forming reddish brown solutions. Their glass transition temperatures were quite high, which is characteristic of aramids. They were also stable up to 450 °C with 10% mass losses (14–23%) recorded in the range 400–470 °C. The activation energies for decomposition of each aramid were also calculated using the Horowitz and Metzger method. All polymers showed reduced solution viscosities in concentrated sulphuric acid, which may be attributed to non‐Newtonian behavior. Copyright © 2007 John Wiley & Sons, Ltd. Three aromatic diamines, 2,6‐di‐(4‐ aminophenyloxy) toluene (A), 2,2′‐di‐[4‐(4‐aminophenyloxy) phenyl] propane (B) and 4,4′ ‐di (4‐aminophenyloxy) biphenyl (C), were obtained by reacting 2,6‐dihydroxytoluene, bisphenol‐A and 4,4′‐dihydroxybiphenyl with p‐nitrochlorobenzene. The synthesized diamines were then polymerized with 1,1′‐ferrocenedicarboxylic acid chloride with low‐temperature polycondensation to produce organometallic aromatic polyamides (aramids). The synthesized monomers and polymers were characterized by their solubilities, elemental analysis, FTIR spectroscopy and 1H‐NMR spectroscopy. The inherent viscosities, differential scanning calorimetry and thermogravimetry were also used for polymer characterization.