Syntheses and Polymerizations of Unsaturated Dibasic Acid Derivatives

Yamada Masamori, Takase Iwao, Mishima Toshio

doi:10.1295/koron1944.26.393

The homopolymerizations of N-(4-substituted phenyl) maleimides, _??_(X: OCH₃, CH₃, H, Cl, OCOCH₃, COOC₂H₅, COCH₃) were carried out with azobisisobutyronitrile as an initiator in dimethylformamide. In the equation which expresses the initial rate of polymerization, R_p=k[AIBN]^x[M]^v the values of x and y were found to be in the range of 0.6-0.9 and 1.0-1.5, respectively, according to the monomer. Also the over-all activation energies and the frequency factors were measured to be 23.8-29.1 kcal/mole and 6.6×10¹³-6.6×10¹⁷. The relationship between logarithm of initial rate of polymerization (R_p) and σ of Hammett's equation did not give a straight line, the initial rates being greater than expected from the equation for electron releasing substituents and smaller for electron attracting substituents. The above curve was converted to a straight line by applying the Yamamoto- Otsu's equation, which contains a correcting term concerning resonance effects as compared with Hammett's equation. Thus the relationships between the reactivities of N-(4-substituted phenyl) maleimides in the copolymerization with vinyl acetate or methyl methacrylate and those in the homopolymerizations were explained. The anionic polymerizations of the above monomers were carried out with n-BuLi or C₂H₅ONa as initiator in tetrahydrofuran. With n-BuLi initiator the polymeryield was high but the reduced viscosity was found to be about 0.07 which corresponded to oligomers.

Syntheses and Polymerizations of Unsaturated Dibasic Acid Derivatives

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