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1

Some aspects of propylene and ethylene copolymenzation over titanium-magnesium and metallocene catalysts

Klyamkina A. N., Aladyshev A. M., Nedorezova P. M., Tsvetkova V. I., Dubnikova I. L.

Polimery

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2001

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T. 46, nr 6

402-405

EN

Propylene/ethylene copolymers were prepared over two complex catalyst systems: (i) an AlEt3-activated MgCl2-supported titanium catalyst TiCl4/MgCl2 with dibutyl phthalate and propyltrimethoxysilane used as respectively internal and external donors and (ii) two methylaluminoxane (MAO)-activated, unsupported zirconocene catalyst systems differing in indenyl ligand structure, viz., Me2SiInd2ZrCl2 and [Me,Si(4-Ph-2-Et-Ind)2]ZrCl2 (rac:meso = 1:2). The olefins were copolymerized (Table 1) in liquid propylene at 50-60°C at constant ethylene overpressures (above C3 pressure) varying over 0.3 to 3 atm corresponding to ethylene concentrations of 0.07 to 0.69 mol/L in the liquid phase. The copolymers contained 1.6-18% of C2 mers. Catalyst activity (Fig. 1) and kinetics of copolymenzation (Fig. 1) were studied and the microstructure, molecular weight characteristics (Table 2) and mechanical properties (Tables 3, 5) of the resulting copolymers were determined. IR spectra (recorded, not included) are discussed. The comonomer reactivity coefficients were evaluated for the copolymerizations run over the three catalytic systems.

PL

Kopolimery propylen/etylen zawierające 1,6-18% merów C2 otrzymywano w obecności dwóch kompleksowych układów katalitycznych: a) nośnikowego katalizatora tytanowo-magnezowego TiO4/MgCl2 aktywowanego trietyloglinem, z udziałem ftalanu dibutylowego jako donora wewnętrznego i propylotrimetoksysilanu jako donora zewnętrznego oraz b) dwóch beznośnikowych katalizatorów cyrkonocenowych, różniących się strukturą ligandu indenylowego - Me2SiInd2ZrCl2 i [Me2Si(4-Ph-2-Et-Ind)2]ZrCl2, aktywowanych mety-loaluminoksanem (MAO). Olefiny kopolimeryzowano w ciekłym propylenie w temp. 50-60°C pod stałym nadciśnieniem etylenu (tabela 1). Określono aktywność katalizatorów (rys. 1) oraz scharakteryzowano skład, mikrostrukturę i ciężary cząsteczkowe (tabela 2), jak również właściwości mechaniczne (tabele 3 i 5) uzyskanych kopolimerów. Wyznaczono współczynniki reaktywności komonomerów w kopolimeryzacji wobec badanych katalizatorów. Wskazano na możliwość regulowania struktury i właściwości kopolimerów propylen/etylen otrzymywanych wobec katalizatorów metalocenowych.

2

Stereospecific bulk polymerization of propylene over ansa-zirconocene catalysts

Nedorezova P. M., Tsvetkova V. I., Aladyshew A. M., Savinov D. V., Dubnikova I. L., Optov V. A., Lemenovskii D. A.

Polimery

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2000

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T. 45, nr 5

333-338

EN

Bulk polymerization of propylene was studied over four ansa-zirconocene catalysts, viz., Me2SiInd2ZrCl2 (1), Me2Si(4-Ph-2-Et-Ind)2ZrCl2 (2) (rac:meso = 1:2), Ph2C(CpFlu)ZrCl2 (3), and Me2C(3-Me-CpFlu)ZrCl2 (4), which were characterized by different symmetries (C1, C2, Cs). The structure of the metallocene affected the structure of PP. Upon reactions with methylaluminoxane (MAO) or triisobutylaluminum (TIBA), compounds 1–4 pro-duced very active catalytic systems which catalyzed the polymerization to yield various structures of PP. Catalysts 1 and 2 gave isotactic PP, catalyst 3 gave syndiotactic PP and catalyst 4 gave hemiisotactic PP. Hemiiso-PP was similar in structure to amorphous PP and had no melting point. The catalytic activity of the system and molecular weight and stereospecificity of PP were studied in relation to the mode of preparation of the catalyst. Kinetic parameteres were evaluated, viz., time of insertion of the propylene molecule (0.001–0.0001 s) and the time of growth of a single PP macromo-lecule (3–6 s), and from these data the minimum degree of polymerization was determined. Activation energies were evaluated for the polymerization carried out over each catalyst system. Young's modulus, molecular weight and stereoregularity of the PP prepared were determined.

3

Polymerization of propylene over isospecific catalysts immobilazed on MAO-pretreated supports with triisobutylaluminum as activator

Khukanova O. M., Babkina O. N., Rishina L. A., Nedorezova P. M., Bravaya N. M.

Polimery

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2000

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T. 45, nr 5

328-332

EN

The effect of support type on the activity of zirconocene-triisobutylaluminum (TIBA) systems was studied in the polymerization of propylene, and on the properties of the resulting PP.

PL

Zbadano wpływ nośnika na aktywność układu katalitycznego cyrkonocen-triizobutyloglin (TIBA) w polimeryzacji propylenu i na charakterystykę otrzymywanego polimeru.