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Synthesis and Structural Characterization of Syndiotactic trans-1,2 and cis-1,2 Polyhexadienes (Articolo in rivista)

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Synthesis and Structural Characterization of Syndiotactic trans-1,2 and cis-1,2 Polyhexadienes (Articolo in rivista) (literal)

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Ricci, G.; Boglia, A.; Motta, T.; Bertini, F.; Boccia, A.C.; Zetta, L.; Alberti, E.; Famulari, A.; Arosio, P.; Meille, S.V. (2007)
Synthesis and Structural Characterization of Syndiotactic trans-1,2 and cis-1,2 Polyhexadienes
in Journal of polymer science. Part A, Polymer chemistry; WILEY-LISS, DIV JOHN WILEY & SONS INC, 111 RIVER ST, HOBOKEN, NJ 07030 (Stati Uniti d'America)
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Ricci, G.; Boglia, A.; Motta, T.; Bertini, F.; Boccia, A.C.; Zetta, L.; Alberti, E.; Famulari, A.; Arosio, P.; Meille, S.V. (literal)

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CNR-ISMAC Istituto per lo Studio delle Macromolecole; Politecnico di Milano. (literal)

Titolo

Synthesis and Structural Characterization of Syndiotactic trans-1,2 and cis-1,2 Polyhexadienes (literal)

Abstract

The (E) isomer in mixtures of (E) and (Z) 1,3-hexadiene was polymerized with the system CoCl2(PiPrPh2)2-MAO, a highly active and stereospecific catalyst for the preparation of 1,2 syndiotactic polybutadiene. A new crystalline polymer with a melting point of 109 °C was obtained. The polymer was characterized by IR, NMR (13C, 1H in solution and 13C in the solid-state), X-ray diffraction, DSC, GPC and it was found to have a trans-1,2 syndiotactic structure with a 5.18 ± 0.04 Å fiber periodicity. Since only the (E) isomer was polymerized, at the end of the reaction we were able to separate the (Z) isomer, which was ultimately polymerized with CpTiCl3-MAO at low temperature, obtaining a low molecular weight, stereoregular polymer that, characterized by IR and NMR methods, was found to exhibit a cis-1,2 syndiotactic structure, never reported before. Molecular mechanics calculations were carried out on the trans-1,2 syndiotactic polymer and structural models consistent with the X-ray diffraction data are proposed. (literal)

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