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Generalized statistical gelation theory
Author(s) -
Rolfes Heidi,
Stepto Robert F. T.
Publication year - 1992
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.1992.040010405
Subject(s) - polymerization , monomer , chemistry , polymer chemistry , group (periodic table) , type (biology) , gel point , kinetics , thermodynamics , polymer , physics , organic chemistry , quantum mechanics , ecology , biology
Abstract Gel points in random polymerizations of the general type Σ i RA f a i+ Σ j RB f b jin which A‐groups react with A‐ and B‐groups, and B‐groups react only with A‐groups are considered. (The symbols Σ i and Σ i signify that the A‐ and B‐bearing reactants RA f a iand RB f b jcan be mixtures of monomers of different functionalities, denoted generally as f a i and f b j .) The usual case of A‐groups reacting only with B‐groups is a special case of the present theory. The effects of chemical kinetics, the competitive reaction of A‐ and B‐groups, are separated from the generalized statistical condition for gelation. The former are used to define reaction curves and the latter, gelation curves. Both types of curve are represented as p a as a function of p b . For a given polymerization, gelation occurs when the reaction curve and the gelation curve intersect. When A‐groups react only with B‐groups, the gel points are those for the usual type of Σ i RA f a i+ Σ j RB f b jpolymerization, and, in the limit of A‐groups only reacting with A‐groups, the gel points are those for Σ i RA f iself polymerizations.