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Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure
The kinetics of ethylene and propylene polymerization catalyzed by homogeneous metallocene were investigated using 2-thiophenecarbonyl chloride followed by quenched-flow methods. The studied metallocene catalysts are: rac-Me(2)Si(2-Me-4-Ph-Ind)(2)ZrCl(2) (Mt-I), rac-Et(Ind)(2)ZrCl(2) (Mt-II) activat...
Autores principales: | , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7830494/ https://www.ncbi.nlm.nih.gov/pubmed/33467427 http://dx.doi.org/10.3390/polym13020268 |
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author | Ali, Amjad Muhammad, Nadeem Hussain, Shahid Jamil, Muhammad Imran Uddin, Azim Aziz, Tariq Tufail, Muhammad Khurram Guo, Yintian Wei, Tiantian Rasool, Ghulam Fan, Zhiqiang Guo, Li |
author_facet | Ali, Amjad Muhammad, Nadeem Hussain, Shahid Jamil, Muhammad Imran Uddin, Azim Aziz, Tariq Tufail, Muhammad Khurram Guo, Yintian Wei, Tiantian Rasool, Ghulam Fan, Zhiqiang Guo, Li |
author_sort | Ali, Amjad |
collection | PubMed |
description | The kinetics of ethylene and propylene polymerization catalyzed by homogeneous metallocene were investigated using 2-thiophenecarbonyl chloride followed by quenched-flow methods. The studied metallocene catalysts are: rac-Me(2)Si(2-Me-4-Ph-Ind)(2)ZrCl(2) (Mt-I), rac-Et(Ind)(2)ZrCl(2) (Mt-II) activated with ([Me(2)NPh][B(C(6)F(5))(4)] (Borate-I), [Ph(3)C][B(C(6)F(5))(4)] (Borate-II), and were co-catalyzed with different molar ratios of alkylaluminum such as triethylaluminium (TEA) and triisobutylaluminium (TIBA). The change in molecular weight, molecular weight distribution, microstructure and thermal properties of the synthesized polymer are discussed in detail. Interestingly, both Mt-I and Mt-II showed high activity in polyethylene with productivities between 3.17 × 10(6) g/mol(Mt)·h to 5.06 × 10(6) g/mol(Mt)·h, activities were very close to each other with 100% TIBA, but Mt-II/borate-II became more active when TEA was more than 50% in cocatalyst. Similarly, Polypropylene showed the highest activity of 11.07 10(6) g /mol(Mt)·h with Mt-I/Borate-I/TIBA. The effects of alkylaluminum on PE molecular weight were much more complicated; MWD curve changed from mono-modal in Mt-I/borate-I/TIBA to bimodal type when TIBA was replaced by different amounts of TEA. In PE, the active center fractions [C*]/[Zr] of Mt-I/borate were higher than that of Mt-II/borate and average chain propagation rate constant (k(p)) value slightly decreased with the increase of TEA/TIBA ratio, but the Mt-II/borate systems showed higher k(p) 1007 k(p) (L/mol·s). In PP, the Mt-I/borate presented much higher [C*]/[Zr] and k(p) value than the Mt-II. This work also extend to investigate the mechanistic features of zirconocenes catalyzed olefin polymerizations that addressed the largely unknown issues in zirconocenes in the distribution of the catalyst, between species involved in polymer chain growth and dormant state. In both metallocene systems, chain transfer with alkylaluminum is the dominant way of chain termination. To understand the mechanism of cocatalyst effects on PE M(w) and (MWD), the unsaturated chain ends formed via β-H transfer have been investigated by (1)H NMR analysis. |
format | Online Article Text |
id | pubmed-7830494 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-78304942021-01-26 Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure Ali, Amjad Muhammad, Nadeem Hussain, Shahid Jamil, Muhammad Imran Uddin, Azim Aziz, Tariq Tufail, Muhammad Khurram Guo, Yintian Wei, Tiantian Rasool, Ghulam Fan, Zhiqiang Guo, Li Polymers (Basel) Article The kinetics of ethylene and propylene polymerization catalyzed by homogeneous metallocene were investigated using 2-thiophenecarbonyl chloride followed by quenched-flow methods. The studied metallocene catalysts are: rac-Me(2)Si(2-Me-4-Ph-Ind)(2)ZrCl(2) (Mt-I), rac-Et(Ind)(2)ZrCl(2) (Mt-II) activated with ([Me(2)NPh][B(C(6)F(5))(4)] (Borate-I), [Ph(3)C][B(C(6)F(5))(4)] (Borate-II), and were co-catalyzed with different molar ratios of alkylaluminum such as triethylaluminium (TEA) and triisobutylaluminium (TIBA). The change in molecular weight, molecular weight distribution, microstructure and thermal properties of the synthesized polymer are discussed in detail. Interestingly, both Mt-I and Mt-II showed high activity in polyethylene with productivities between 3.17 × 10(6) g/mol(Mt)·h to 5.06 × 10(6) g/mol(Mt)·h, activities were very close to each other with 100% TIBA, but Mt-II/borate-II became more active when TEA was more than 50% in cocatalyst. Similarly, Polypropylene showed the highest activity of 11.07 10(6) g /mol(Mt)·h with Mt-I/Borate-I/TIBA. The effects of alkylaluminum on PE molecular weight were much more complicated; MWD curve changed from mono-modal in Mt-I/borate-I/TIBA to bimodal type when TIBA was replaced by different amounts of TEA. In PE, the active center fractions [C*]/[Zr] of Mt-I/borate were higher than that of Mt-II/borate and average chain propagation rate constant (k(p)) value slightly decreased with the increase of TEA/TIBA ratio, but the Mt-II/borate systems showed higher k(p) 1007 k(p) (L/mol·s). In PP, the Mt-I/borate presented much higher [C*]/[Zr] and k(p) value than the Mt-II. This work also extend to investigate the mechanistic features of zirconocenes catalyzed olefin polymerizations that addressed the largely unknown issues in zirconocenes in the distribution of the catalyst, between species involved in polymer chain growth and dormant state. In both metallocene systems, chain transfer with alkylaluminum is the dominant way of chain termination. To understand the mechanism of cocatalyst effects on PE M(w) and (MWD), the unsaturated chain ends formed via β-H transfer have been investigated by (1)H NMR analysis. MDPI 2021-01-15 /pmc/articles/PMC7830494/ /pubmed/33467427 http://dx.doi.org/10.3390/polym13020268 Text en © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Ali, Amjad Muhammad, Nadeem Hussain, Shahid Jamil, Muhammad Imran Uddin, Azim Aziz, Tariq Tufail, Muhammad Khurram Guo, Yintian Wei, Tiantian Rasool, Ghulam Fan, Zhiqiang Guo, Li Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure |
title | Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure |
title_full | Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure |
title_fullStr | Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure |
title_full_unstemmed | Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure |
title_short | Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure |
title_sort | kinetic and thermal study of ethylene and propylene homo polymerization catalyzed by ansa-zirconocene activated with alkylaluminum/borate: effects of alkylaluminum on polymerization kinetics and polymer structure |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7830494/ https://www.ncbi.nlm.nih.gov/pubmed/33467427 http://dx.doi.org/10.3390/polym13020268 |
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