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Syndiotactic and isotactic polypropylene were produced using the metallocene compounds Ph 2 C(Flu)(Cp)ZrCl 2 and SiMe 2 (2-Me,4-Ph-Ind) 2 ZrCl 2 in homogeneous system and supported on silica/MAO. These catalysts were evaluated either isolated or as a binary system. In the latter case, the iso-and syndiospecific metallocene complexes were immobilized together during the preparation of the supported catalyst. In a further experimental set, the syndio-and isospecific isolated heterogeneous catalysts were mixed at the moment of propylene polymerization. The polypropylenes obtained were evaluated using differential scanning calorimetry. The catalytic activities were also investigated. At all the studied polymerization temperatures, the results showed that the binary catalyst produced polypropylenes with lower melting temperatures in comparison with those obtained when the mixture of isolated supported syndio-and isospecific catalysts was employed. Moreover, the activation energies for the polymerization of all catalysts systems were calculated, resulting in a lower value for the binary system when compared to that employing the catalyst mixture and to both the isolated supported metallocene catalysts.

ABSTRACT:In this work, ethylene was polymerized by using Cp 2 ZrCl 2 supported on silica pretreated with methylaluminoxane (MAO) as the catalyst system. The influence of the conditions for the preparation of the heterogeneous catalyst, such as temperature, washing method of the catalytic solid, MAO and metallocene concentration in the support treatment, time of MAO, and metallocene immobilization on the support, type of alkylaluminum used in the support pretreatment, and calcination temperature of the support were investigated. Aluminum and zirconium content fixed on the silica surface were determined by inductively coupled plasma emission spectroscopy. Polymer characteristics were determined by gel permeation chromatography and differential scanning calorimetry. According to the results, the activity of some supported catalysts were far higher than with the homogeneous system. Moreover, polyethylene with very high molecular weights were also obtained and with molecular weight distribution larger than those produced with the homogeneous precursor.

In this work, propylene was polymerized with isospecific and syndiospecific catalysts in homogeneous and heterogeneous systems. The binary metallocene system of both isospecific and syndiospecific catalysts in the heterogeneous system was also used. Besides the type of catalyst, parameters such as polymerization temperature and pressure were varied to achieve the better conditions for the polymerization. The objective of this work is to investigate the influence of these parameters on the characteristics of the produced polymer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2979–2986, 2002