Modeling of Superacid Catalyzed Step‐Growth Polymerization of Isatin and Biphenyl or Terphenyl Monomers. Issue 5 (4th July 2017)

• Record Type: Journal Article
• Authors: Romero‐Hernández, Juan Enrique; Cruz‐Rosado, Alfredo; Zolotukhin, Mikhail G.; Vivaldo‐Lima, Eduardo
• Is Part Of: Macromolecular theory and simulations. Volume 26:Issue 5(2017)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2017-07-04
• Subjects: A2 + B2 step‐growth polymerization -- bi‐ and terphenyl -- isatin -- mathematical modeling -- nonstoichiometric step‐growth polymerization -- polymerization kinetics -- superacid catalyzed polyhydroxyalkyations; Macromolecules -- Periodicals; Polymers -- Periodicals; Polymerization -- Periodicals; Macromolécules -- Périodiques; 547.705
• DOI: 10.1002/mats.201700031
• Languages: English
• ISSNs: 1022-1344

Abstract

Abstract : By using different kinetic rate constants for the four reactions involved in an otherwise conventional model for A2 + B2 step‐growth polymerization, the attainment of ultrahigh molecular weights at stoichiometric imbalance ratios smaller than one, observed in superacid catalyzed polyhydroxyalkylations of isatin and modified isatin with biphenyl and terphenyl, is adequately explained. Good agreement between model predictions and experimental data is obtained. Abstract : A mathematical model for the kinetics and molecular weight development of superacid catalyzed step‐growth polymerization of isatin and biphenyl or terphenyl monomers is developed. By considering different reactivities among the several types of polymer molecules present in an otherwise conventional A2 + B2 step‐growth polymerization system, ultrahigh molecular weights are predicted by the model for superacid catalyzed polyhydroxyalkylation reactions, a result that remains unclear in the literature since it seems to be in disagreement with the classical A2 + B2 theory. Three polymerization systems are addressed in this study: (a) polymerization of isatin and biphenyl, (b) modified isatin and biphenyl, and (c) modified isatin and terphenyl. Overall good agreement between calculated and experimental results of polymerization rate, and evolution of number‐ and weight‐average molecular weights ( M n and M w, respectively) is observed. However, some discrepancies for molar mass dispersity ( Ð ) are observed.