Random propene/4‐methyl‐1‐pentene copolymers synthesized with C 2 symmetric highly isospecific metallocenes

Propene (P)/4‐methyl‐1‐pentene (Y) copolymers in a wide range of composition were prepared with isospecific single center catalysts, rac ‐Et(IndH 4 ) 2 ZrCl 2 ( EBTHI ), rac ‐Me 2 Si(2‐Me‐BenzInd) 2 ZrCl 2 ( MBI ), and rac ‐CH 2 (3‐ t BuInd) 2 ZrCl 2 ( TBI ). 13 C NMR analysis of copolymers and statistical elaboration of microstructural data at triad level were performed. Unprecedented and surprising results are here reported. Random P/Y copolymers were prepared with the most isospecific catalyst, TBI , that is known to prepare ethene/propene and ethene/4‐methyl‐1‐pentene copolymers with long homosequences of both comonomers, whereas longer homosequences of both comonomers were observed in copolymers from the less enantioselective metallocenes EBTHI and MBI . These findings, which are against what is acknowledged in the field, can pave the way for the preparation on a large scale of random propene‐based copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53 , 2575–2585