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In-Reactor Polypropylene Functionalization─The Influence of Catalyst Structures and Reaction Conditions on the Catalytic Performance
Abstract
To unravel the relationship between silylene-bridged metallocene catalyst structures and polymerization conditions and their effect on the performance in in-reactor functionalization of polypropylene, the behaviors of rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MMAO, rac-Me2Si(Ind)2ZrCl2, rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2, and rac-Me2Si(Ind)2HfCl2 in propylene/aluminum alkyl-passivated 10-undecen-1-ol copolymerization were compared. Kinetic analysis revealed higher catalytic activities for zirconocenes compared to analogous hafnocenes. Both the zirconocene and hafnocene with substituted indenyl ligands afforded a higher molecular weight capability, improved stereo-selectivity, and enhanced ability to incorporate functionalized comonomers compared to their non-substituted congeners. An in-depth study of polypropylene functionalization using the best performing catalyst system, rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MMAO, at temperatures ranging from 40 to 100 °C, revealed a linear inversely proportional correlation of polymerization temperature with functionalized comonomer reactivity (↑Tp → ↓ r1), copolymer molecular weight (↑Tp → ↓Mn), and melting temperature (↑Tp → ↓Tm). While performing well under standard laboratory polymerization conditions, rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MMAO showed limited molecular weight and stereo-selectivity capabilities under high-temperature (130–150 °C) solution process conditions. Although immobilization of rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 onto silica, allowing it to be used under industrially relevant slurry and gas-phase conditions, led to an active catalyst, it failed to incorporate any functionalized comonomer.
Citations
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Authors (7)
-
Miloud Bouyahyi
-
Rob Duchateau
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Muhammad Naseem Akhtar
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E. A. Jaseer
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Rajesh Theravalappil
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Nestor Garcia
Cite as
Full text
- Publication version
- Accepted or Published Version
- DOI:
- Digital Object Identifier (open in new tab) 10.1021/acs.macromol.1c02220
- License
- Copyright (2022 American Chemical Society)
Keywords
Details
- Category:
- Articles
- Type:
- artykuły w czasopismach
- Published in:
-
MACROMOLECULES
no. 55,
pages 776 - 787,
ISSN: 0024-9297 - Language:
- English
- Publication year:
- 2022
- Bibliographic description:
- Bouyahyi M., Jasińska-Walc L., Duchateau R., Akhtar M. N., Jaseer E. A., Theravalappil R., Garcia N.: In-Reactor Polypropylene Functionalization─The Influence of Catalyst Structures and Reaction Conditions on the Catalytic Performance// MACROMOLECULES -Vol. 55,iss. 3 (2022), s.776-787
- DOI:
- Digital Object Identifier (open in new tab) 10.1021/acs.macromol.1c02220
- Sources of funding:
-
- COST_FREE
- Verified by:
- Gdańsk University of Technology
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