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Molcular Weight Distribution in Di Metal Cyanide Catalyzed Polymerization 1: Fundamental Distribution for Length Dependent Propagation Constant and Segments
Author(s) -
Bachmann Rolf,
Klinger Marcel,
Jupke Andreas
Publication year - 2021
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.202100012
Subject(s) - dispersity , molar mass distribution , polymerization , inverse , constant (computer programming) , distribution (mathematics) , chemistry , cyanide , reaction rate constant , kinetics , thermodynamics , computational chemistry , polymer chemistry , materials science , mathematics , mathematical analysis , physics , polymer , classical mechanics , geometry , organic chemistry , computer science , programming language
Di metal cyanide (DMC) catalyzed living polymerization is characterized by a) the “catch‐up” kinetics with a length dependent propagation rate constantk P ≈ n − 2( n : chain length), favoring the growth of small molecules and b) segmental growth caused by the repeated attachment and detachment of a growing end to a catalyst site. Whereas the inverse square law reduces polydispersity, growth in segments increases it. Analytic expressions of “catch‐up” molecular weight distributions (MWD) are given fork P ≈ n 0 , n − 1, and n − 2 . To include segments, the theory originally developed for quasi living polymerizations is generalized to arbitrary distributions for the number of segments as well as the MWD of the segments themselves. General simple relationships allow calculating the moments of composite distributions in terms of the moments of the underlying distributions.