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Computational study of metathesis degradation of rubber, 1. Distribution of cyclic oligomers via intramolecular metathesis degradation of cis ‐polybutadiene
Author(s) -
Tlenkopatchev Mikhail A.,
Barcenas Adriana,
Fomine Serguei
Publication year - 1999
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(19991101)8:6<581::aid-mats581>3.0.co;2-0
Subject(s) - intramolecular force , metathesis , polybutadiene , chemistry , degradation (telecommunications) , salt metathesis reaction , ring (chemistry) , polymer chemistry , natural rubber , computational chemistry , polymerization , stereochemistry , organic chemistry , polymer , copolymer , telecommunications , computer science
The results of the molecular modelling of the intramolecular metathesis degradation of cis‐ polybutadiene ( cis‐ PB) into cyclic oligomers at PM3 level of theory showed that the chain‐ring equilibrium is completely shifted towards the all‐ trans cyclic isomers. The formation of cyclic products, containing from three to six butadiene units, from larger rings is thermodynamically favoured with cyclic butadiene tetramers and pentamers being the main products. These results are in reasonable agreement with most of the available experimental data. The discrepancy observed in some cases between found and calculated ring distributions for the intramolecular metathesis degradation of cis ‐PB suggests that the reaction is kinetically controlled under certain conditions.