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

• Published in: European polymer journal 2000-12, Vol.36 (12), p.2655-2663
• Main Authors: Warwel, S, Wiege, B, Fehling, E, Kunz, M
• Format: Article
• Language: English
• Subjects: Aluminoxane; Applied sciences; Comb structure; Epoxide; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polyether; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Ring-opening polymerization
• ISSN: 0014-3057; 1873-1945
• DOI: 10.1016/S0014-3057(00)00046-X

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.