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Computation of the gel effect in multifunctional self‐polymerization in the presence of intramolecular reactions
Author(s) -
Kumar A,,
Khandelwal P. K.
Publication year - 1988
Publication title -
polymer engineering and science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.503
H-Index - 111
eISSN - 1548-2634
pISSN - 0032-3888
DOI - 10.1002/pen.760280108
Subject(s) - intramolecular force , polymerization , gel point , monomer , materials science , molecule , polymer chemistry , molar mass distribution , reaction rate constant , work (physics) , computational chemistry , chemistry , thermodynamics , polymer , organic chemistry , kinetics , physics , quantum mechanics , composite material
Intramolecular reactions in the step‐growth polymerization of multifunctional monomer, RA f , were modeled. The rate constant for this step was taken from the Monte Carlo studies of Plate and Noah. Species P vn , with v Intramolecular bonds and chain length n , was defined, and differential equations governing their molecular weight distribution (MWD) in hatch reactors were written. An algorithm of computation valid up to the gel point was developed, and the process of gelation was studied under the variation of the rate constant parameters of the intramolecular reaction step. It was found that the larger the molecule, the greater is its tendency to form intramolecular bonds. We devised a mathematical method to find the conversion of A groups on P on species. Whenever this reaches a critical value {= l/(f−1)}, conditions for gelation are generated and molecules of infinite structure begin to form. In the presence of intramolecular reactions, the tendency to form a network is reduced because larger molecules undergo cyclization and there is consequently a shift in the gel point, which has been computed in this work.