Lewis Acids Activated Spontaneous Alternating Copolymerization of Maleic Anhydride and Styrene Derivatives

Synthesis of maleic anhydride (MA) and styrene (St) copolymers possessing ultra-high molecular weight, strictly alternating regularity and high glass transition temperature simultaneously is still an issure with great challenge. Herein, the spontaneous alternating copolymerization of MA and St derivatives were investigated by using various Lewis acids. In the presence of alkyl aluminum or butyl magnesium, the MA-St alternating copolymers with ultra-high molecular weight (M_n ≤166.5×10⁴ ) and high glass transition temperature (211 °C≤T_g ≤216 °C) were produced and the microstructure of MA-St copolymers were analyzed by ¹ H and ¹³ C NMR spectra. The copolymerizations of MA with St derivatives, including divinylbenzene, p-butenyl styrene, p-methoxystyrene, trans-anethole, p-fluorostyrene and p-chlorostyrene, also were explored by using AlOctyl₃ as an activator in toluene at 50 °C.