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Inter‐ and Intramolecular Crosslinking Kinetics: Partitioning According to Number of Crosslinks
Author(s) -
Li Rujun,
McCoy Benjamin J.
Publication year - 2004
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.200400058
Subject(s) - intramolecular force , kinetics , intermolecular force , polymer , materials science , polymer chemistry , chemistry , thermodynamics , molecule , stereochemistry , organic chemistry , physics , composite material , quantum mechanics
Summary: Intramolecular crosslinking is important in many processes, including nanoparticle fabrication, but quantitative models of the kinetics have not been extensively investigated. We propose a distribution kinetics analysis for simultaneous intramolecular and intermolecular crosslinking. For realistic cases, moment equations can be solved and crosslink density computed according to the number of crosslinks. An analytical solution for the ratio of intramolecular to intermolecular crosslinking rates varies inversely with the initial polymer concentration and initial molecular weight, in agreement with published experimental data.Time dependence of crosslink density p cd in a batch reactor for ω 1 = ω 2 = 1 with κ 2 = 1 and κ 1 = 0, 0.2, 0.5, and 1 (lines 1, 2, 3, and 4), and κ 2 = 0 and κ 1 = 1 (line 5). p cd increases linearly with time for all cases.