Ring-opening polymerization of oleochemical epoxides catalyzed by aluminoxane/acetyl acetone

Abstract

Terminal epoxides based on oleochemicals were homopolymerized and copolymerized to high molecular weight polyethers ( M w=2.3 × 10 5–29.0 × 10 5 g/mol, GPC based on polystyrene calibration standards) with a comb structure using aluminoxanes/acetyl acetone catalysts. Poly(methyl ω-epoxy alkanoates) were achieved in yields of 56–92% after reaction times of 72 h at 100°C. ω-Epoxy undecenyl silyl ethers were polymerized in yields of 40–94% after 24 h. Copolymerization of 1,2-decene oxide with C 10, C 11 and C 14 ω-epoxy alkanoates was performed under identical conditions in almost quantitative yields in 24–48 h ( M w=1.5 × 10 5–8.3 × 10 5 g/mol). The copolymers exhibited compositions similar to the comonomer feed ratio. Sodium salts and polyacids from poly(methyl ω-epoxy alkanoates) were obtained by alkaline hydrolysis and neutralization with acetic acid. A poly(epoxy alcohol) was synthesized by cleaving the corresponding trimethylsilyl ether.