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Molecular Weight Development during Simultaneous Chain Scission, Long‐Chain Branching and Crosslinking, 1
Author(s) -
Tobita Hidetaka
Publication year - 2003
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.200390005
Subject(s) - branching (polymer chemistry) , chain (unit) , connection (principal bundle) , markov chain , eigenvalues and eigenvectors , representation (politics) , polymer , polymerization , materials science , polymer chemistry , mathematics , chemistry , polymer science , physics , composite material , geometry , quantum mechanics , statistics , politics , political science , law
A general matrix formula is proposed for the weight‐average molecular weights of the polymer systems formed through simultaneous scission, branching and crosslinking of N types of chains, assuming the chain connection statistics are Markovian. For the polymerization systems in which chains are generated consecutively, such as for free‐radical polymerization, the present theory can be applied by increasing the number of chain types N to infinity, by considering the chains formed at different times as different types of chains. The gel point determination reduces to the eigenvalue problem and the present theory extends the classical gelation theory to non‐random, history‐dependent reaction systems. From the mathematical point of view, this theory is capable of describing complex molecular build‐up processes through end‐linking, T‐ and H‐shaped chain connections, irrespective of reaction/reactor types used.Schematic representation of the 0 th generation segment and the connection to the 1 st generation segments.