III International Conference

PP-II-77IMMOBILIZATION OF ORGANOMETALLIC CATALYSTS ON ZEOLITES FORDEVOLOPMENT OF FUNCTIONAL POLYMERIZATION-FILLED POLYOLEFINSMeshkova I.N., Ushakova T.A., Grinev V.G., Nikashina V.A. 1 , Kudinova O.I.,Ladygina T.A., Kiseleva E.V., Kovaleva N.Yu., Novokshonova L.A.N.N. Semenov Institute of Chemical Physics RAS, Moscow, Russia1 V.I. Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Moscow, RussiaE-mail: lnov@chph.ras.ruAn immobilization of organometallic catalysts on the surface allows one to intensify theprocess of olefin polymerization, regulate directly the molecular weight characteristics,structure and stereoregular composition of products, and to develop the polymer compositesby the monomer polymerization upon the catalytically activated supports. With the use ofsynthetic (type of ZSM-5) and natural zeolites, the zeolite (H 2 O)/AlMe 3 /Zr-сene and zeolite(H 2 O)/AlEt 2 Cl/VOCl 3 catalysts were developed. With application of these catalysts the newpolymerization-filled composite materials with functional properties were developed.An immobilization of organometallic catalysts on the surface allows one to intensify theprocess of olefin polymerization, regulate directly the molecular weight characteristics,structure and stereoregular composition of products, and to develop the polymer compositeswith functional properties by the monomer polymerization at the catalytically activatedsupports. For the preparation of immobilized zirconocene and vanadium catalysts the zeolites– synthetic (type of ZSM-5) and natural, were used as the supports. For fixation of the precatalysts(Cp 2 ZrCl 2 , Et[Ind] 2 ZrCl 2 and VOCl 3 ) the alkylaluminoxanes synthesized on thesupport surface were used. Such alkylaluminoxanes were obtained by an earlier elaboratedmethod [1] in the reaction of the partial hydrolysis of AlMe 3 and AlEt 2 Cl with the internalwater of zeolites: Na-form of ZSM-5 (Si/Al=42), NH 4 ZSM-5 (Si/Al=34), HZSM-5 (Si/Al=17and 34), NaY (Si/Al=5) and natural zeolites. They form the heterogenized complexes with Zrceneswhich are active in ethylene and propylene polymerization in the absence of otherorganoaluminium cocatalysts.The peculiarities of olefins polymerization on zeolite(H 2 O) /aluminiumalkyl/pre-catalyst[2,3]:• The nature of the zeolite support influences the activity of the heterogenized Zr-cenecatalysts. The most active catalysts were obtained on NaY and HZSM-5 (Si/Al=17) supports.• Ethylene and propylene polymerization on the zeolite supported catalysts proceeds with apositive temperature coefficient. The apparent activation energies of ethylene and304