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Keywords:

  • crystal structure;
  • molecular mechanics;
  • NMR;
  • polymerization;
  • 1,2 syndiotactic polyhexadiene;
  • X-ray diffraction

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. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5339–5353, 2007