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Findings pertaining to polyethylene photooxidation
Author(s) -
Gugumus F.
Publication year - 1989
Publication title -
makromolekulare chemie. macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 0258-0322
DOI - 10.1002/masy.19890250103
Subject(s) - homolysis , photodissociation , polyethylene , photochemistry , intramolecular force , kinetics , bond cleavage , chemistry , intermolecular force , decomposition , reaction mechanism , polymer , thermal decomposition , radical , organic chemistry , catalysis , molecule , physics , quantum mechanics
The kinetics and mechanisms of photolysis of the hydroperoxides formed on thermal oxidation of polyethylene have been investigated. The difficulties to explain the results by the generally accepted decomposition mechanism based on homolytic splitting of the hydroperoxy bond are discussed. New mechanisms of hydroperoxide photolysis are proposed. The intermolecular reactions considered account for the main products found experimentally, ketones and trans‐vinylene groups. They are also in agreement with the kinetics of product formation. The intramolecular photolysis reactions envisaged seem to involve a small amount only of the hydroperoxides present in polyethylene after thermal oxidation. However, they affect directly the mechanical properties of the polymer because they involve main‐chain scission.