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Possible mechanisms in thermal polymerization of vegetable oils. II. Polymer formation
Author(s) -
Sims R. P. A.
Publication year - 1957
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/bf02638007
Subject(s) - polymerization , monomer , viscosity , chemistry , polymer , double bond , conjugated system , distillation , polymer chemistry , order of reaction , reaction rate constant , linseed oil , organic chemistry , kinetics , materials science , composite material , physics , quantum mechanics
Summary From molecular distillation data, and information obtained by hydrogenation in dilute solution, extents of reaction have been calculated for the polymerization of linseed, safflower, tung, and oiticica oils. The hydrogenation data indicate that more than one double bond per molecule can be consumed during polymerization. The kinetic order of the polymerization of nonconjugated oils increases from an initial value of unity to approach a value of two. With conjugated oils, second‐order characteristics were maintained during the course of the bodying. An explanation of this difference in reaction order based on monomer disappearance is presented. Rate constants and overall energies of activation were calculated and compared with those obtained from viscosity measurements. Agreement between the two sets of values was obtained. Oiticica oil, which gives curved viscosity plots that cannot be resolved, has been treated successfully in this manner. Intraglyceride reactions have been studied, and differences in behavior between nonconjugated and conjugated oils at high and low polymerization temperatures have been observed.