Towards the design of a mixture of diether and succinate as an internal donor in a MgCl<sub>2</sub>-supported Ziegler–Natta catalyst

Hamedani, Nona Ghasemi; Hassan, Abbas; Poorsank, Fatemeh

doi:10.1039/d0nj02676j

Cited by 15 publications

(5 citation statements)

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“…This approach has been used to understand the distribution of active site types in Ziegler-Natta catalysts for propylene polymerization as a function of polymerization temperature and time, type of cocatalyst and electron donor, copolymerizations with other α-olefins, and catalyst synthesis conditions. [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.…”

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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“…Hypothesis IV Another hypothesis on the role of IDs for catalyst stereospecificity is their efficiency in transforming low isospecific sites into highly isospecific sites. This could be achieved by introducing sterically hindered groups on ID moiety [100,101]. Steric hindrance of the coordinated donor in the nearby active Ti center is responsible for the formation of isospecific MgCl 2 sites.…”

Section: Coordination Mode Of Internal Donors On Mgcl 2 Supportmentioning

confidence: 99%

Internal donors on supported Ziegler Natta catalysts for isotactic polypropylene: a brief tutorial review

Paghadar¹,

Sainani²,

Samith³

et al. 2021

J Polym Res

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The scientific and technical advances in the field of polymer science has been abundant in recent years. Amongst the various polymeric materials available in market, synthesis of polyolefins has been in the forefront since decades. A major challenge in this domain remains in attaining stereoregular polyolefins especially polypropylene (PP) and significant efforts were carried out by synthesizing various internal donors (ID) aiding the catalysts involved in producing them. This short review gives an overview of i) various generations of Ziegler–Natta (ZN) catalyst systems ii) general classes of ID that has been demonstrated by the researchers over the past decades iii) their influence on PP isotacticity and polymer properties. The coordination modes of different donor classes on supported ZN system and comparative study especially between phthalate and diether ID classes were also addressed here. This review also presents the studies carried out on phthalate catalyst structure analysis, detailed comparison study on phthalate and diether IDs in terms of PP isotacticity, regioselectivity, hydrogen response, and also their cross combination study and competitive behavior. Further a brief description on other structurally varied IDs like malonates, maleates, silyl diol esters, bifunctional donors, multi ether donors demonstrated for isotactic PP were also presented. Studies conducted on compatibility of incorporation of two different classes of IDs on a single supported ZN system for the fundamental understanding of the catalyst behavior; and also on how mixed donor approach enables in tuning the catalyst for polymer properties were also presented. This review also provides an opportunity to the young minds and the basic researchers from academic point of view by and large to create new polymeric materials with useful properties or modify the existing materials for new applications by incorporating new IDs for further improvisation of the stereo regularity in obtaining the polymers. Graphic Abstract

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“…It is resulted in the development of different generations of Z–N catalyst technology based on various internal donor systems 4–7 . These internal donors have different functional groups such as monoester, diester, succinate, malonate, diether, carbonate, and others 8–13 …”

Section: Introductionmentioning

confidence: 99%

Insight of polypropylene synthesis with high performance multidentate internal donor catalyst system

Trivedi

Gocher

Balachandran

et al. 2023

J of Applied Polymer Sci

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Propylene polymerization using magnesium dichloride (MgCl 2 ) supported Ziegler-Natta (Z-N) system is a robust and preferred catalytic process for producing polypropylene (PP) grades. Herein, synthesis of polypropylene products is reported using MgCl 2 supported multidentate (3,3,3 0 ,3 0 -tetramethyl-2,2 0 ,3,3 0tetrahydro-1,1 0 -spirobiindane-5,5 0 ,6,6 0 -tetracarbonate) Z-N pre-catalyst. The catalyst performance evaluation over propylene polymerization found that multidentate Z-N pre-catalyst has better hydrogen response with controlled isotacticity of PP products as compared to conventional bidentate Z-N pre-catalysts. Melt rheology analysis showed higher loss modulus and storage modulus for ultra-high molecular weight isotactic polypropylene (UHMWiPP) as compared to PP resins with medium molecular weight. Further, GPC analysis reveal medium to broad unimodal molecular weight distribution (MWD) of PP products produced with multidentate Z-N pre-catalyst system.

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Towards the design of a mixture of diether and succinate as an internal donor in a MgCl₂-supported Ziegler–Natta catalyst

Abstract: An insight into the impact of mixed-internal donors, comprised of bis-methoxymethyl-fluorene (BMF) and 2,2-diisopropyl succinate (DIS), on the crystalline structure of MgCl2 supported Ziegler-Natta catalyst are developed. The propylene polymerization...

Cited by 15 publications

References 60 publications

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

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

Internal donors on supported Ziegler Natta catalysts for isotactic polypropylene: a brief tutorial review

Insight of polypropylene synthesis with high performance multidentate internal donor catalyst system

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Towards the design of a mixture of diether and succinate as an internal donor in a MgCl2-supported Ziegler–Natta catalyst

Abstract: An insight into the impact of mixed-internal donors, comprised of bis-methoxymethyl-fluorene (BMF) and 2,2-diisopropyl succinate (DIS), on the crystalline structure of MgCl2 supported Ziegler-Natta catalyst are developed. The propylene polymerization...

Cited by 15 publications

References 60 publications

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

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

Internal donors on supported Ziegler Natta catalysts for isotactic polypropylene: a brief tutorial review

Insight of polypropylene synthesis with high performance multidentate internal donor catalyst system

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Product

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About

Towards the design of a mixture of diether and succinate as an internal donor in a MgCl₂-supported Ziegler–Natta catalyst