Compositional Distribution of Binary Living Copolymers and Their End Sequences. Issue 4 (25th April 2021)

• Record Type: Journal Article
• Authors: Trhlíková, Olga; Walterová, Zuzana; Janata, Miroslav; Kanizsová, Lívia; Horský, Jiří
• Is Part Of: Macromolecular theory and simulations. Volume 30:Issue 4(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-04-25
• Subjects: bivariate compositional distribution -- combinatorial analysis -- end sequences of copolymers -- terminal model of living copolymerization; Macromolecules -- Periodicals; Polymers -- Periodicals; Polymerization -- Periodicals; Macromolécules -- Périodiques; 547.705
• DOI: 10.1002/mats.202100002
• Languages: English
• ISSNs: 1022-1344

Abstract

Abstract: Statistical analysis is carried out for the compositional distribution (CD) of binary copolymers prepared by living copolymerization. The CDs of both block and random (Bernoullian) binary copolymers are found to be the product of two Poisson distributions. The analysis is further developed for instantaneous first‐order Markovian copolymers (the terminal model). The relations are derived for the CD of i) copolymers with fixed polymerization degree and ii) of copolymers with variable polymerization degree. The relations ad (i) describe also CD of copolymer end sequences; however, they cannot be used for interpretation of tandem mass spectrometry where end‐sequence CD for isobaric copolymers is required. Such relations are also derived. Stepwise application of the equations affords approximation of high‐conversion living copolymerization. Fair agreement of the derived relations with kinetic Monte–Carlo simulation and qualitative agreement with the experimental data on n‐butyl acrylate/methyl methacrylate copolymers prepared by quasi‐living radical polymerization is found. Abstract : Combinatorial analysis leads to explicit relations for binary living copolymerization. The abundance of individual copolymers can be calculated independently. Bivariate distributions of diblock and random instantaneous copolymers are found to be identical. The derived relations apply also to distributions of copolymer end sequences. Special relations are given for end‐sequence distributions of isobaric copolymers useful for MS‐MS analysis. ​