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Free radical addition of hydrogen sulfide and thiols to linseed oil and methyl oleate
Author(s) -
Schwab A. W.,
Gast L. E.,
Cowan J. C.
Publication year - 1968
Publication title -
journal of the american oil chemists' society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.512
H-Index - 117
eISSN - 1558-9331
pISSN - 0003-021X
DOI - 10.1007/bf02655509
Subject(s) - linseed oil , sulfur , chemistry , hydrogen sulfide , dithiol , sulfide , free radical addition , hydrogen , organic chemistry
Free radical additions of hydrogen sulfide, ethanedithiol, and 1,6‐hexanedithiol have been made to methyl oleate and linseed oil with ultraviolet radiation. Reactions were carried out in dichloromethane at −70C and in benzene at 25C. With the dithiols, a new dibasic ester has been prepared from methyl oleate in which bridging is accomplished through a dithiol moiety. Hydrogen sulfide has been added to linseed oil in suitable solvents at both −70C and 25C. It appears that zero‐order kinetics control the additions at both temperatures. Infrared data show a linear relationship between mercapto absorption and the amount of sulfur incorporated. Nuclear magnetic resonance (NMR) spectra demonstrate a decrease in olefinic protons with an increase in sulfur content. Fair agreement on the extent of reaction exists between data from NMR, sulfur content, and infrared analyses. Hydrogen sulfide‐treated linseed oil films air‐dry slowly at room temperature; at 250C for 1 hr under a CO 2 atmosphere these oils cure to brown films with Sward Rocker values of 24 to 32 and pencil hardness values of five to greater than six. Pencil hardness and alkali resistance increased with sulfur content. The film from the 4.2% sulfur sample resisted alkali at room temperature for 24 hr.