In‐chain functionalization by alternating anionic copolymerization of styrene and 1‐(4‐dimethylaminophenyl)‐1‐phenylethylene

Anionic copolymerizations of styrene (M 1 ) with excess 1‐(4‐dimethyl‐aminophenyl)‐1‐phenylethylene (M 2 ) were conducted in benzene at 25°C for 24h, using sec ‐butyllithium as initiator. Narrow molecular weight distribution copolymers with M̄; n = 16.1 × 10 3 g/mol (M̄ w /M̄ n = 1.04) and 38.2 × 10 3 g/mol (M̄ w /M̄ n = 1.05), and 24 and 38 moles of M 2 per macromolecule, respectively, were characterized by size exclusion chromatography, 1 H NMR spectroscopy and DSC. The monomer reactivity ratio, r 1 = 5.6, was obtained from the copolymer composition at complete consumption of M 1 , assuming that the rate constant k 22 =0,i.e. r 2 =0. The polymers exhibited T g values of 128 and 119°C, respectively, which correspond to an estimated T g = 217°C for the hypothetical homopolymer of M 2 .