MgCl<sub>2</sub>‐supported TiCl<sub>4</sub>catalysts containing diethyl norbornene‐2,3‐dicarboxylate internal electron donor for 1‐butene polymerization: Effects of internal electron donor configuration

Dong, Xiaofang; Zhang, Li; Liu, Zhibo; Yang, Min; Duan, Zhongyu; Hou, Kun; Liu, Binyuan; Kim, Il

doi:10.1002/app.40758

Cited by 4 publications

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“…[51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66] Similar deconvolution studies were used to understand the effect of polymerization conditions and catalyst formulations for the polymerization of ethylene and α-olefins with Ziegler-Natta [67][68][69][70][71][72][73][74][75][76][77][78][79][80][81] and Phillips/chromium catalysts. [82][83][84] Other studies used MWD deconvolution to identify active site populations for the polymerization of 1-octene, [85] 1-hexene, [86][87][88][89] and 1-butene [90,91] with Ziegler-Natta catalysts. An alternative MWD deconvolution algorithm, using the cumulative version of Flory distribution, has also been proposed but has not been widely adopted.…”

Section: Looking Back At the Literaturementioning

confidence: 99%

Polyolefin microstructural deconvolution methods: The good, the bad, and the ugly

Soares

2023

Can J Chem Eng

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The deconvolution of the molecular weight distribution (MWD) of polyolefins into Schultz–Flory most probable distributions has become the standard method to identify the number of site types on multiple‐site‐type olefin polymerization catalysts such as Ziegler–Natta, Phillips, and some supported metallocenes. This method has been used to quantify the effect of polymerization conditions and catalyst formulations on polyolefin MWD and olefin polymerization kinetics. Related methods have also been developed to deconvolute other polyolefin microstructure features, such as the chemical composition and comonomer sequence length distributions. In this paper, I explain the premises behind these deconvolution models and review the publications in this area, highlighting the advantages, disadvantages, and misuses of these methods. I also propose a revised formulation on how to model the MWD of polyolefins made with multiple‐site‐type catalysts using ratio distributions for propagation and chain transfer frequencies. The main objective of this overview article is to highlight the strengths, but also show the pitfalls, of polyolefin microstructure deconvolution methods.

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Section: Looking Back At the Literaturementioning

confidence: 99%

Polyolefin microstructural deconvolution methods: The good, the bad, and the ugly

Soares

2023

Can J Chem Eng

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Mechanism of internal and external electron donor effects on propylene polymerization with MgCl₂‐supported Ziegler–Natta catalyst: New evidences based on active center counting

Weng

Jiang

et al. 2018

J of Applied Polymer Sci

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Two TiCl 4 /Di/MgCl 2 type supported Ziegler-Natta catalysts were prepared by loading dibutylphthalate or dicyclopentyldimethoxysilane (DCPDMS) (internal donor, Di) and TiCl 4 on activated d-MgCl 2 in sequence, and a blank catalyst was prepared by loading TiCl 4 on the same d-MgCl 2 without adding Di. These catalysts have similar specific surface area and pore size distribution, thus form a suitable base for comparative studies. Propylene polymerization with the catalysts was conducted in n-heptane slurry using triethylaluminum (TEA) as cocatalyst, and the effects of Di as well as De (external donor, in this work it was DCPDMS) on the number of active centers, the distribution of active centers among three polypropylene (PP) fractions (isotactic, medium isotactic, and atactic PP chains), and chain propagation rate constants of the PP fractions were studied by counting the number of active centers in the PP fractions using a method based on selective quench-labeling of the propagation chains by 2-thiophenecarbonyl chloride. When De was not added in the polymerization, introducing a phthalate type Di in the catalyst evidently changed the active center distribution by enhancing the proportion of active centers producing isotactic PP (iPP) (C Ã i ), but scarcely changed reactivities of the three groups of active centers forming the three fractions. When the De was added in the polymerization system with TiCl 4 / phthalate/MgCl 2 catalyst, further shifting of active center distribution in favor of C Ã i took place, meanwhile reactivities of the three groups of active centers also remarkably changed in favor of C Ã i . Mutual effects of these changes led to overwhelming dominance of iPP production in the TiCl 4 /Di/MgCl 2 -TEA/De system (Di 5 phthalate, De 5 alkoxysilane). In contrast, though using alkoxysilane as Di also caused shifting of active center distribution in favor of C Ã i when De was not added, addition of alkoxysilane De caused reverse shifting of active center distribution in favor of those producing PP of lower stereoregularity. This unfavorable change largely counteracted the reactivity changes in favor of C Ã i caused by the De, rendering the catalytic system rather poor isospecificity. V C 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46605.

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Effect of Aminosilane Compounds as External Donors on Isospecific Polymerizations of 1-Butene with MgCl2/TiCl4/DIBP Catalyst

Ren

2016

Catal Lett

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MgCl₂‐supported TiCl₄catalysts containing diethyl norbornene‐2,3‐dicarboxylate internal electron donor for 1‐butene polymerization: Effects of internal electron donor configuration

Cited by 4 publications

References 46 publications

Polyolefin microstructural deconvolution methods: The good, the bad, and the ugly

Polyolefin microstructural deconvolution methods: The good, the bad, and the ugly

Mechanism of internal and external electron donor effects on propylene polymerization with MgCl₂‐supported Ziegler–Natta catalyst: New evidences based on active center counting

Effect of Aminosilane Compounds as External Donors on Isospecific Polymerizations of 1-Butene with MgCl2/TiCl4/DIBP Catalyst

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MgCl2‐supported TiCl4catalysts containing diethyl norbornene‐2,3‐dicarboxylate internal electron donor for 1‐butene polymerization: Effects of internal electron donor configuration

Cited by 4 publications

References 46 publications

Polyolefin microstructural deconvolution methods: The good, the bad, and the ugly

Polyolefin microstructural deconvolution methods: The good, the bad, and the ugly

Mechanism of internal and external electron donor effects on propylene polymerization with MgCl2‐supported Ziegler–Natta catalyst: New evidences based on active center counting

Effect of Aminosilane Compounds as External Donors on Isospecific Polymerizations of 1-Butene with MgCl2/TiCl4/DIBP Catalyst

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MgCl₂‐supported TiCl₄catalysts containing diethyl norbornene‐2,3‐dicarboxylate internal electron donor for 1‐butene polymerization: Effects of internal electron donor configuration

Mechanism of internal and external electron donor effects on propylene polymerization with MgCl₂‐supported Ziegler–Natta catalyst: New evidences based on active center counting