Metallocene based catalysts are excellent tools in the production of poly-α-olefins. The product properties of these catalysts can be tailor-made by controlling the microstructure as well as the molar mass and the thermal properties. Rac-[Me2Si(2-Me-4-(1-Naphtyl)Ind2]ZrCl2/MAO is a system that exhibits exceptional capabilities in respect to activity and isospecificity while producing polypropenes with high molar masses in the solution process.

Propene was polymerized using rac-dimethylsilylbis(2-methyl-4-(1-naphtyl)indenyl)zirconium dichloride (rac-[Me2Si(2-Me-4-(1-Naphtyl)Ind)2]ZrCl2) under six sets of conditions: in toluene solution, bulk, toluene slurry, bulk with the supported metallocene, a stirred bed with polyethene and a stirred bed with NaCl. The first two procedures were carried out with methylaluminoxane (MAO) as cocatalyst, the latter four were performed with methylaluminoxane supported on silicagel (MAO/SiO2) as activator. The differences between the procedures employed were examined by comparison of the polymer properties of the resulting products and of the activities at different temperatures. The polymerization procedure has a significant influence on the products. The polypropenes obtained with the homogeneous catalyst systems have generally high melting points and molar masses and exhibit very high activities. The heterogeneous analogues, on the other hand, gain enhanced stability by supporting, even at higher temperatures.

Chemie Ingenieur TechnikVolume 73, Issue 7 p. 857-861 Wissenschaftliche Kurzmitteilung Einfluss der Polymerisationsverfahren auf die Produkteigenschaften von Metallocen-Polypropen W. Kaminsky Prof. Dr., W. Kaminsky Prof. Dr.Search for more papers by this authorD. Arrowsmith, D. Arrowsmith Institut für Technische und Makromolekulare Chemie, Universität Hamburg, Bundesstraße 45, D-20146 HamburgSearch for more papers by this authorA. Laban, A. Laban Institut für Technische und Makromolekulare Chemie, Universität Hamburg, Bundesstraße 45, D-20146 HamburgSearch for more papers by this authorP. J. Lemstra, P. J. Lemstra Dutch Polymer Institute, Department of Chemical Engineering, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, NiederlandeSearch for more papers by this authorJ. Loos, J. Loos Dutch Polymer Institute, Department of Chemical Engineering, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, NiederlandeSearch for more papers by this authorU. Weingarten, U. Weingarten Institut für Technische und Makromolekulare Chemie, Universität Hamburg, Bundesstraße 45, D-20146 HamburgSearch for more papers by this author W. Kaminsky Prof. Dr., W. Kaminsky Prof. Dr.Search for more papers by this authorD. Arrowsmith, D. Arrowsmith Institut für Technische und Makromolekulare Chemie, Universität Hamburg, Bundesstraße 45, D-20146 HamburgSearch for more papers by this authorA. Laban, A. Laban Institut für Technische und Makromolekulare Chemie, Universität Hamburg, Bundesstraße 45, D-20146 HamburgSearch for more papers by this authorP. J. Lemstra, P. J. Lemstra Dutch Polymer Institute, Department of Chemical Engineering, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, NiederlandeSearch for more papers by this authorJ. Loos, J. Loos Dutch Polymer Institute, Department of Chemical Engineering, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, NiederlandeSearch for more papers by this authorU. Weingarten, U. Weingarten Institut für Technische und Makromolekulare Chemie, Universität Hamburg, Bundesstraße 45, D-20146 HamburgSearch for more papers by this author First published: 16 July 2001 https://doi.org/10.1002/1522-2640(200107)73:7<857::AID-CITE857>3.0.CO;2-8AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Volume73, Issue7July, 2001Pages 857-861 RelatedInformation

Copolymerizations of ethene and propene were carried out either with the soluble catalyst systems dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdichloride/methylaluminoxane (MAO) (1), isopropylidenecyclopentadienylfluorenylzirconiumdichloride/MAO (2) and isopropylidene(3-methylcyclopentadienyl)fluorenylzirconiumdichloride/MAO (3) in toluene or with the supported metallocenes (1)/SiO2, (2)/SiO2 and (3)/SiO2 in the gas phase. Furthermore, terpolymerizations of ethene, propene and 5-ethylidene-2-norbornene (ENB) were performed with the homogeneous system (3) and with the heterogeneous system (3)/SiO2 in the gas phase. The physical and chemical properties of the resulting polymers were compared in order to examine the behavior of the metallocenes when supported. In general, they work in much the same way as their soluble counterparts and the synthesis of EP(D)M co(ter)polymers with the above mentioned metallocenes can easily be transfered to gas phase processes.

Polymerizations of styrene were carried out with half-sandwich complexes supported on silica, CpTiX3/MAO/SiO2 (X = Cl, F). The optimum values for the polymerization time, the amount of cocatalyst and the Alsupport/Ti ratio were found for the trichlorinated system. The highest activity obtained was 3,100 g sPS/(mol Ti × h × mol/L styrene). The trihalogenated complexes were compared to one another with respect to their polymerization rate. CpTiCl3/MAO/SiO2 and CpTiF3/MAO/SiO2 behave in a similar manner, suggesting that the active species of both half-sandwich complexes on the support are the same. Furthermore, aging experiments were carried out with CpTiCl3/MAO/SiO2 and, surprisingly, deactivation was observed, as opposed to supported zirconocenes which gain stability against deactivation reactions when anchored to a carrier. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2959–2968, 1999

New functional copolymers consisting of ethene and 4-vinylcyclohexene (4-VCH) were synthesized by a stereorigid metallocene/methylalumoxane catalyst. The content of 4-VCH depends on the polymerization temperature, thus influencing the polymeric properties. Investigations of the microstructure were made using 13C NMR spectroscopy, thus revealing that 4-VCH is inserted regioselectively into the growing polymer chain. Hydroboration of selected copolymers followed by an oxidative workup yielded polyacohols which display different polymeric properties than the precursor