PROBING THE ROLES OF DIETHYLALUMINUM CHLORIDE IN PROPYLENE POLYMERIZATION WITH MgCl2-SUPPORTED ZIEGLER-NATTA CATALYSTS
Special Issue: Coordination Polymerization of Olefins|Updated:2023-01-03
|
PROBING THE ROLES OF DIETHYLALUMINUM CHLORIDE IN PROPYLENE POLYMERIZATION WITH MgCl2-SUPPORTED ZIEGLER-NATTA CATALYSTS
Chinese Journal of Polymer ScienceVol. 31, Issue 4, Pages: 583-590(2013)
Affiliations:
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
Jie Hu, Bin Han, Xian-rong Shen, et al. PROBING THE ROLES OF DIETHYLALUMINUM CHLORIDE IN PROPYLENE POLYMERIZATION WITH MgCl2-SUPPORTED ZIEGLER-NATTA CATALYSTS[J]. Chinese Journal of Polymer Science, 2013, 31(4): 583-590. DOI: 10.1007/s10118-013-1260-5.
DOI:
Jie Hu, Bin Han, Xian-rong Shen, et al. PROBING THE ROLES OF DIETHYLALUMINUM CHLORIDE IN PROPYLENE POLYMERIZATION WITH MgCl2-SUPPORTED ZIEGLER-NATTA CATALYSTS[J]. Chinese Journal of Polymer Science, 2013, 31(4): 583-590. DOI: 10.1007/s10118-013-1260-5.DOI:
PROBING THE ROLES OF DIETHYLALUMINUM CHLORIDE IN PROPYLENE POLYMERIZATION WITH MgCl2-SUPPORTED ZIEGLER-NATTA CATALYSTS
the effect of diethylaluminum chloride (DEAC) in propylene polymerization with MgCl
2
-supported Ziegler-Natta catalyst was studied. Addition of DEAC in the catalyst system caused evident change in catalytic activity and polymer chain structure. The activity decrease in raising DEAC/Ti molar ratio from 0 to 2 is a result of depressed production of isotactic polypropylene chains. The number of active centers in fractions of each polymer sample was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and fractionating the polymer into isotactic
mediumisotactic and atactic fractions. The number of active centers in isotactic fraction ([C
i
*
]/[Ti]
) was lowered by increasing DEAC/Ti molar ratio to 2
but further increasing the DEAC/Ti molar ratio to 20 caused marked increase of [C
i
*
]/[Ti]
. The number of active centers that produce atactic and medium-isotactic PP chains was less influenced by DEAC in the range of DEAC/Ti = 0−10
but increased when the DEAC/Ti molar ratio was further raised to 20. The propagation rate constant of C
i
*
(
k
pi
) was evidently increased when DEAC/Ti molar ratio was raised from 0 to 5
but further increase in DEAC/Ti ratio caused gradual decrease in
k
pi
. The complicated effect of DEAC on the polymerization kinetics
catalysis behaviors and polymer structure can be reasonably explained by adsorption of DEAC on the central metal of the active centers or on Mg atoms adjacent to the central metal.
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