Anionic synthesis of [1,4-poly(diene)-b-syndiotactic poly(methyl methacrylate)] diblock copolymers: 7Li NMR study of the intermediate reaction of lithium poly(diene) anion with 1,1-diphenylethylene

The end-capping with 1,1-diphenylethylene (DPE) of living 1,4-poly(diene) lithiated anions prepared in cyclohexane (Chx) and toluene is a major but poorly controlled step in the synthesis of syndiotactic poly(methyl methacrylate) (sPMMA) containing block copolymers. The kinetics of the reaction have been studied by means of 7Li NMR not only in Chx and toluene but also in their mixtures with polar solvents, since the solvent polarity must be increased for MMA to be predominantly converted into sPMMA. Although the addition of a polar solvent (tetrahydrofuran (THF), diethyl ether) to Chx and toluene is known to increase the reactivity of living polymeric anions, contaminating lithium salts, such as lithium hydroxide, slow down the end-capping reaction even when 10 vol.-% polar solvent is added. Moreover, the polymeric diphenylalkyllithium anions are unstable in 1/9 (v/v) THF/Chx mixture, as a result of the nucleophilic attack of THF. On the basis of all these observations, new experimental conditions are proposed for improving the control of the anionic block copolymerization of 1,3-dienes and MMA to yield 1,4-poly(diene) and sPMMA containing block copolymers.