Isospecific Polymerization of Halide- and Amino-Substituted Styrenes Using a Bis(phenolate) Titanium Catalyst

Isospecific polymerization of polar styrenes is a challenge of polymer science. Particularly challenging are monomers bearing electron-withdrawing substituents or bulky substituents. Here, we report the coordination polymerization of halide- and amino-functionalized styrenes including para-fluorostyrene (pFS), para-chlorostyrene (pClS), para-bromostyrene (pBrS), and para-(N,N-diethylamino)styrene (DMAS) using 2,2′-sulfur-bridged bis(phenolate) titanium precursor (1). The combination of 1 and [Ph3C][B(C6F5)4] and AliBu3 provides crystalline poly(pFS)s with perfect isotacticity (mmmm > 95%) and high molecular weights (≤16.0 × 104 g mol−1). Upon activation with a large excess of DMAO, 1 reaches polymerization activity of 5.58 × 105 g molTi−1 h−1 producing isotactic poly(pFS)s featuring higher molecular weights (≤39.6 × 104 g mol−1). The distinguished performance of the 1/DMAO system has been extended to the polymerization of pClS and pBrS, both usually involve halogen abstraction during the polymerization, to produce isotactic and high molecular weight (Mn = 32.2 × 104 vs. 13.7 × 104 g mol−1) polymers in good activities (2.18 × 105 vs. 1.31 × 105 g molTi−1 h−1). Surprisingly, 1/DMAO is nearly inactive for DMAS polymerization, on contrary, the system 1/[Ph3C][B(C6F5)4]/AliBu3 displays isoselectivity (mmmm > 95%) albeit in a moderate activity.