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Molecular weight distribution formed through chain‐length‐dependent crosslinking reactions
Author(s) -
Tobita Hidetaka
Publication year - 1998
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/(sici)1521-3919(19980301)7:2<225::aid-mats225>3.0.co;2-r
Subject(s) - polymer , copolymer , molar mass distribution , molecule , polymer chemistry , double bond , monte carlo method , chemistry , materials science , organic chemistry , mathematics , statistics
The molecular weight distribution formed through chain‐length‐dependent crosslinking reactions in free‐radical vinyl/divinyl copolymerization is investigated by using Monte Carlo simulations. When the crosslinking reaction rates for larger polymer molecules are reduced, the high molecular weight tails cannot extend smoothly, resulting in distorted, sometimes bimodal distribution profiles, which exhibit qualitative similarity with those reported experimentally. Although the reduced crosslinking reaction rates between larger polymer molecules may not affect the average crosslinking density levels significantly, they can delay the developments of the weight‐average molecular weight significantly. Because the wastage of pendant double bonds through cyclization would result in a similar tendency, one cannot distinguish these two types of nonidealities through the measurements of the pendant double bond consumption and the average molecular weight development.