Olefin polymerization and copolymerization
Nona Ghasemi Hamedani; Fatemeh Poorsank; Hassan Arabi; Seyed Mehdi Ghafelehbashi
Abstract
Insights have been developed into the influence of different structures, including bismethoxymethylfluorene (B) and 2,2-diisopropyl succinate (I), on both internal donor (ID) and external donor (ED) roles on the performance of MgCl2/ID/TiCl4. Catalyst performance including activity, hydrogen response, ...
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Insights have been developed into the influence of different structures, including bismethoxymethylfluorene (B) and 2,2-diisopropyl succinate (I), on both internal donor (ID) and external donor (ED) roles on the performance of MgCl2/ID/TiCl4. Catalyst performance including activity, hydrogen response, molecular weight distribution and thermal properties is explained through the coordination nature of external donors and its correlation with the internal donor. Replacement of the typical alkoxysilane ED with B and I leads to an overall decrease in activity, which is more pronounced (average 1.4 times) in systems with similar structures as ID and ED. However, these compounds significantly enhance hydrogen response. The use of B as ED leads to an average 1.5-fold increase in MFI and usage of I as ED results in an average 1.1 times increase in MFI. Changing the ED influenced the thermal properties so that in the catalyst with the succinate structure as ID, altering the ED from alkoxysilane to I, leads to an increase in crystallinity from 43.86% to 48.12%. These findings suggest that the choice of package of internal and external donor can significantly influence the resulting polymer characteristics.
Catalysis
Gholam-Reza Nejabat; Mehdi Nekoomanesh; Hassan Arabi; Hamid Salehi-Mobarakeh; Gholam-Hossein Zohuri; Mohammad-Mahdi Mortazavi; Saeid Ahmadjo; Stephen A. Miller
Abstract
Several types of hybrid catalysts are made through mixing of 4th generation Ziegler-Natta (ZN) and (2-PhInd)2ZrCl2 metallocene catalysts using triethylaluminum (TEA) as coupling agent. Response surface methodology (RSM) is used to evaluate the interactive effects of different parameters including ...
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Several types of hybrid catalysts are made through mixing of 4th generation Ziegler-Natta (ZN) and (2-PhInd)2ZrCl2 metallocene catalysts using triethylaluminum (TEA) as coupling agent. Response surface methodology (RSM) is used to evaluate the interactive effects of different parameters including amounts of metallocene and TEA and temperature on metallocene loading. Analyzing the amounts of Al and Zr elements in the hybrid catalysts through ICP-OES and EDXA reveals that temperature plays a crucial role on anchoring of the metallocene catalyst on ZN while TEA has the least determining effect. The ICP analysis shows that as the concentration of Al goes up in the hybrid catalyst the concentration of Zr passes a maximum, while EDXA shows a direct relationship between the Al and Zr contents. Using triisobutylaluminum (TIBA) and methylaluminoxane (MAO) as the coupling agents, almost similar metallocene loadings are observed. Finally, the performance of hybrid catalysts is investigated in propylene polymerization and the obtained polymers are characterized using DSC and DMTA through which the presence of two types of polymers in the final product are confirmed.
Reaction engineering
Marzieh Nouri; Mahmoud Parvazinia; Hassan Arabi; Mohsen Najafi
Abstract
A two-dimensional (2D) single particle model for the copolymerization of propylene-ethylene with heterogeneous Ziegler-Natta catalyst is developed. The model accounts for the effects of the initial shape of the catalyst and carck/ pore patterns on the copolymer composition, polymerization rate and the ...
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A two-dimensional (2D) single particle model for the copolymerization of propylene-ethylene with heterogeneous Ziegler-Natta catalyst is developed. The model accounts for the effects of the initial shape of the catalyst and carck/ pore patterns on the copolymer composition, polymerization rate and the average molecular weight properties. The spherical and oblate ellipsoidal shapes of catalyst particle and four different pattern distributions of cracks and pores in a growing particle are studied in this simulation. It is assumed that the diffusion coefficient of monomers in the cracks/pores is 10 times higher than the compact zone of the particle.In other word, the cracks are distinguished from parts with higher monomer diffusion coefficient.The dynamic 2D monomer diffusion-reaction equation is solved together with a two-site catalyst kinetic mechanism using the finite element method. Simulation results indicate that the initial shape of catalyst changes the average copolymer composition only in the early stage of polymerization, but the crack/pore patterns in the growing particle have a strong impact on the copolymer composition in the polymer particles due to the change ofmass transfer limitations.
