Functional polymers. XLVIII. Polymerization of ω-alkenoate derivatives

Esters of ω-alkenoic acids have been homopolymerized with transition metal initiating systems. The key to the successful polymerization was the complexation of the monomer prior to its addition to the initiating system. Titanium trichloride, aluminum activated, was found to be best as the transition metal part of the initiator systems, with diethyl-, or better, diisobutylaluminum chloride as the reducing agents and n-hexane or toluene as the solvents. Best results for polymerizations were obtained with 2,6-dimethylphenyl esters of the functional α-olefin monomers; however, other phenyl esters also polymerized well. Attempts to polymerize methyl 10-undecenoate gave the corresponding polymer in only low yields. Polymers of the 2,6-dimethylphenyl esters, obtained in high molecular weight, were characterized. Polymers were also obtained from 2,6-dimethylphenyl 7-octenoate, but not from ω-alkenoates with less than three methylene units between the ester group and the terminal olefin group. Poly(2,6-dimethylphenyl 10-undecenoate) was hydrolyzed in an aqueous sodium hydroxide/1,4-dioxane solution to poly(sodium 10-undecenoate) that in turn was neutralized with acetic acid to poly(10-undecenoic acid).