Ethen/1-Hexen- und 1-Octadecen-Copolymerisation mit dem stereorigiden Zirkon-Katalysatorsystem iPr(CpFlu)ZrCl2/MAO: Einfluß der Temperatur / Copolym erization of Ethene/1-Hexene and 1-Oetadecen with the Stereorigid Zirconium Catalyst System iPr(CpFlu)ZrCl2/MAO : Influence of the Temperature

Abstract

Ethene was copolymerized with 1-hexene and 1-octadecene at different temperatures to study the influence of the temperature. The stereorigid catalyst [2,4-cyclopentadien-1-yliden- (iso-propyliden)fluoren-9-yliden]zirconium dichloride iPr(CpFlu )ZrCl2 1 in combination with methylalumoxane MAO was used. The polymerization rate of ethene depends in a wide range on the temperature and the com onom er content in solution. In each case a large rate enhancem ent at low ratios [com onom er]/[ethene] was observed. A t 25 °C the polymerization rate of ethene increases continuously with increasing [1-hexene]/[ethene]-ratio. At 40 °C the consumption of ethene is nearly independent of the 1-hexene content in solution. Finally, at 60 °C, similar to the ethene/1-octadecene-copolymerisation at different temperatures, the polymerization rate of ethene decreases with increasing [1-hexene]/[ethene]-ratio. It is suggested that this behavior is caused by the mobility of the side chains in the copolym er near the active center, probably for sterical reasons. W ith increasing temperatures, the side chain becomes more and more flexible and thus the sterical hindrance is increased. This effect is even stronger with long chain α-olefins. The microstructure of the copolymer was investigated with respect to Marcovian statistic 1. and 2. order. The experimental triad distribution is described satisfactorily only with the second order statistic. Independent of the temperature the r22 parameter is considerably greater than the r12 parameter, the insertion of an α-olefin thus being more favored for he sequence {R -(α-olefine)-(α-olefine)-Kat.} than for {R -(ethene)-(α-olefine)-Kat.}. It therefore appears that both last inserted monomers influence the insertion of the subsequent monomer, especially at high comonomer contents. Furthermore, the parameters for the α-olefin insertions r22 and r12 are nearly independent of the temperature of polymerization, whereas the r11 and r21 parameters increase with increasing temperature.