Catenation Equilibria Between Ring Oligomers and Their Relation to Effective Molarities: Models From Theories and Simulations. Issue 1 (7th October 2015)

• Record Type: Journal Article
• Authors: Di Stefano, Stefano; Ercolani, Gianfranco
• Is Part Of: Macromolecular theory and simulations. Volume 25:Issue 1(2016)
• Page Start: 63
• Page End: 73
• Publication Date: 2015-10-07
• Subjects: catenane -- catenation constant -- effective molarity -- Jacobson–Stockmayer theory -- macrocyclization equilibria; Macromolecules -- Periodicals; Polymers -- Periodicals; Polymerization -- Periodicals; Macromolécules -- Périodiques; 547.705
• DOI: 10.1002/mats.201500050
• Languages: English
• ISSNs: 1022-1344

Abstract

Abstract : Five models are discussed giving the equilibrium constant for the catenation of two ring oligomers as a function of their Effective Molarity (EM), the physico‐chemical parameter expressing the ease of cyclization of a chain. The first three models (A–C) are derived from the revision of previous theories of catenation, that neglect excluded volume effects. A fourth model (D) is obtained from the results of Monte Carlo simulations by Deguchi and co, that can also account for excluded volume effects. Finally, a fifth model (E) is introduced which has the same functional form of models A, B, D, but is parameterized using the available experimental catenation constant. Abstract : On the basis of theories and simulations, the authors propose five models giving the equilibrium constant Kij for the catenation of two ring oligomers, C i and C j, as a function of the Effective Molarity EM1, that is the physico‐chemical parameter expressing the ease of cyclization of the strainless ring monomer C1 .