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Synthesis and Characterization of Phosphonates from Methyl Linoleate and Vegetable Oils
Author(s) -
Bantchev Grigor B.,
Moser Bryan R.,
Murray Rex E.,
Biresaw Girma,
Hughes Stephen R.
Publication year - 2016
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/s11746-016-2909-3
Subject(s) - chemistry , double bond , transesterification , soybean oil , radical initiator , benzoyl peroxide , sunflower oil , linolenate , organic chemistry , gel permeation chromatography , vegetable oil , peroxide , fatty acid , catalysis , food science , polymer , polymerization
Phosphonates were synthesized on a medium scale (~200 g) from three lipids—methyl linoleate (MeLin), high‐oleic sunflower oil (HOSO) and soybean oil (SBO), and three dialkyl phosphites—methyl, ethyl and n ‐butyl, using a radical initiator. A staged addition of the lipid and the initiator was used to achieve good yields. Good results were observed with MeLin (94–99% conversions of the double bonds, as determined by NMR, and 83–99% isolated yields) and HOSO (99–100% NMR conversions, 87–96% isolated yields) using tert ‐butyl perbenzoate as the initiator. With SBO, benzoyl peroxide was used as the initiator, due to its capability to generate radicals at a higher rate at slightly lower temperatures, and thus to shorten the reaction time. Conversions of 91–93% (by NMR) and isolated yields of 80–94% were achieved. The progress of the reaction was monitored with GC–MS. The products were characterized using 1 H, 13 C and 31 P NMR, IR and gel permeation chromatography. A prolonged reaction led to some transesterification between the carboxylic and phosphite ester groups. Conditions favoring higher reaction rates led to the formation of more oligomers and benzoate fatty ester byproducts. The benzoate fatty ester byproducts were formed by the attack of a benzoate radical on a double bond. The more double bonds that were present per lipid molecule, the more oligomers were formed: MeLin 2–8%, HOSO 3–9% and SBO 8–29%.