Kinetics of the catalytic polymerization of pyrene with AlCl3. (August 2018)

• Record Type: Journal Article
• Authors: Lamie, W. Cabell; Bruce, David A.; Hoffman, Wesley P.; Thies, Mark C.
• Is Part Of: Carbon. Volume 134(2018)
• Page Start: 1
• Page End: 8
• Publication Date: 2018-08
• Subjects: Carbon -- Periodicals; Carbone -- Périodiques; Koolstof; Toepassingen; Electronic journals; 546.681
• DOI: 10.1016/j.carbon.2018.03.073
• Languages: English
• ISSNs: 0008-6223

Abstract

Abstract: The kinetics of the catalytic polymerization of pyrene monomer to pyrene pitch in the presence of aluminum trichloride (AlCl3 ) were studied at temperatures between 330 and 370 °C in a 1-L batch reactor. Both reactants and reaction products were isolated from the bulk pitch using supercritical extraction (SCE), so that they could be quantified. Concentrations of monomer, dimer, and trimer were measured at discrete reaction times, and each was found to exhibit first-order reaction behavior. Analysis of the oligomerization reaction behavior at differing temperatures enabled the calculation of apparent activation energies and pre-exponential factors for each reaction. Relatively low activation energies that decreased with increasing oligomer size were obtained, suggesting that the reactions are mass-transfer-limited. The microkinetic model that was developed can be used to estimate the reaction time for which the formation of liquid crystalline, mesophase-forming pyrene trimer is maximized. Other groups have developed models for bulk mesophase formation, but this is the first time that reaction kinetics have been measured for individual oligomers in a carbonaceous pitch formed from pure polycyclic aromatic hydrocarbons (PAHs) or mixtures thereof. Graphical abstract: Image 1