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13 C NMR Study of Copolymers of Propene with Higher 1‐Olefins with New Microstructures by ansa ‐Zirconocene Catalysts
Author(s) -
Wahner Udo M.,
Tincul Ioan,
Joubert Dawid J.,
Sadiku Emmanuel R.,
Forlini Fabrizio,
Losio Simona,
Tritto Incoronata,
Sacchi Maria Carmela
Publication year - 2003
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200350031
Subject(s) - comonomer , tacticity , propene , copolymer , polymer chemistry , pentene , nmr spectra database , metallocene , chemistry , materials science , catalysis , polymerization , organic chemistry , spectral line , polymer , physics , astronomy
Copolymers of propene and higher 1‐olefins (1‐butene, 1‐pentene, 1‐hexene, 1‐heptene, 1‐octene, and 4‐methyl‐1‐pentene (4M1P)), prepared with rac ‐Et(Ind) 2 ZrCl 2 ( EI ) and rac ‐Me 2 Si(2‐MeBenz‐[ e ]Ind) 2 ZrCl 2 (MBI), were comprehensively analyzed by 13 C NMR spectroscopy. These catalysts known to produce isotactic polypropene lead to two vastly different families of copolymers under the chosen experimental conditions. All copolymers produced with EI possessed comparable isotacticities as well as similar stereosequences. Furthermore, these copolymers did not significantly differ from those of the reference propene homopolymer. However, the copolymers produced with MBI significantly differed both from the reference propene homopolymer and among themselves. In fact, in contrast to the corresponding highly isotactic homopolymer, the whole series of copolymers was characterized by rather low isotacticities. The degree of tacticity was strongly influenced by the comonomer type. A detailed 13 C NMR analysis revealed that these copolymers are constituted by highly isotactic sequences and by atactic sequences of various lengths. It is proposed that the formation of atactic sequences is triggered by the insertion of a comonomer. It seems likely that MBI can shift from a stereoselective to a non‐stereoselective state due to an interaction with higher linear or branched comonomer.13 C NMR spectra of propene/1‐pentene (a) and propene/4‐methyl‐1‐pentene (b) prepared with MBI .