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Advanced Catalysts for Polyolefin Production
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Advanced Catalysts for Polyolefin Production

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Reaction Engineering".

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 12323

Special Issue Editors

Dr. Adriano G. Fisch

E-Mail Website
Guest Editor
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB T6G 1H9, Canada
Interests: polymerization; reaction engineeering; catalysis; mathematical modelling
Dr. Yue Yu

E-Mail Website
Guest Editor
National Institute of Clean-and-Low-Carbon Energy, Beijing 102211, China
Interests: Polyolefins; Ziegler-Natta Catalysis; Kinetics; Microstructures; Reaction Engineering

Special Issue Information

Dear Colleagues,

Polyolefins are undoubtedly related to modern lifestyles and the impact of any technological improvement in this area will affect people’s daily routines. Although polyolefin development has been steady, with high user satisfaction, nowadays, new drives are working on the requirements of environmentally friendly products in terms of water and energy demands, gas emissions, and after-use disposal. For polyolefins produced by coordination catalysis, the catalyst plays an important role in controlling the polymer microstructure and therefore the end-user properties and applications. In this sense, innovations in polyolefin catalysis are preponderant to address the current environmental demands of society.

This Special Issue of Catalysts focuses on research driven by the environmental benefits that polyolefin technology can achieve through catalyst innovation. We look forward to accepting manuscripts dealing with:

  • The development of new supports and immobilization strategies;
  • Catalyst design is driven by process performance and polymer property requirements;
  • Alternative methods for reaction kinetic studies and modeling;
  • Methods for catalyst performance evaluation in the laboratory;
  • Methods for catalyst characterization;
  • Environmentally friendly catalyst synthesis.

Other topics are also encouraged. When submitting your paper, please introduce the environmental benefit that your research can bring to polyolefin technology.

Dr. Adriano G. Fisch
Dr. Yue Yu
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Ziegler-Natta
  • metallocene
  • polyolefin
  • kinetic of polymerization
  • catalyst characterization
  • catalyst synthesis
  • catalyst testing
  • catalyst synthesis scale-up

Published Papers (5 papers)

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Research

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10 pages, 1510 KiB  
Article
Fragmentation-Oriented Design of Olefin Polymerization Catalysts: Support Porosity
by Adriano G. Fisch
Catalysts 2023, 13(1), 160; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13010160 - 10 Jan 2023
Viewed by 1114
Abstract
The development of catalysts for the production of polyethylene and polypropylene is ordinarily accomplished on a trial-and-error experimentation program. From the point-of-view of the fragmentation performance, support porosity is the key property affecting the mechanical support resistance, and, therefore, it determines the fragmentation [...] Read more.
The development of catalysts for the production of polyethylene and polypropylene is ordinarily accomplished on a trial-and-error experimentation program. From the point-of-view of the fragmentation performance, support porosity is the key property affecting the mechanical support resistance, and, therefore, it determines the fragmentation process during the early moments of polymerization. The design of the support porosity can be more accurately determined by applying the theoretical knowledge acquired from previous research, but this is not consolidated for catalyst design. This article reports a methodology to optimize the support porosity using a simple fundamental model of the fragmentation process. Using this approach, the design of fragmentation-oriented supports can be achieved for polymerization reactors. Full article
(This article belongs to the Special Issue Advanced Catalysts for Polyolefin Production)
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15 pages, 2586 KiB  
Article
PNP-Ligated Rare-Earth Metal Catalysts for Efficient Polymerization of Isoprene
by Rongqing Ma, Hongfan Hu, Xinle Li, Yi Zhou, Huashu Li, Xin Sun, Xueqin Zhang, Guoliang Mao and Shixuan Xin
Catalysts 2022, 12(10), 1131; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12101131 - 28 Sep 2022
Cited by 1 | Viewed by 1547
Abstract
The tridentate PNP ligand-supported rare-earth metal complexes, i.e., bis[o-diphenylphosphinophenyl]amido-Re-bis[o-dimethylaminobenzyl], [(Ph2P-o-C6H4)2N]Re[(CH2-o-Me2N(C6H4))2]: (Re = Y, 1; Nd, 2 [...] Read more.
The tridentate PNP ligand-supported rare-earth metal complexes, i.e., bis[o-diphenylphosphinophenyl]amido-Re-bis[o-dimethylaminobenzyl], [(Ph2P-o-C6H4)2N]Re[(CH2-o-Me2N(C6H4))2]: (Re = Y, 1; Nd, 2; Gd, 3) were applied to isoprene polymerization. When activated with borate activator ([PhMe2NH][B(C6F5)4] (NH-BARF), catalysts 1 and 3 exhibited excellent catalytic efficiency in aromatic media, produced very-high to ultrahigh molecular weight (Mw over 130 × 104 g/moL) polyisoprene rubber (PIR), and the obtained PIR contained over 98% cis-1,4 head-to-tail repeating unites. In most cases, the borate-activated polymerization reaction proceeded in a quasi-living pattern (PDI = 1.2–1.5) under controlled monomer conversion; whereas, activated with the commercially available modified methylaluminoxane (MMAO3A) in aliphatic hydrocarbon media, complexes 1, 2 and 3 all showed high catalytic efficiency, produced high molecular weight PIR with narrow molecular weight distribution (PDI ≤ 2.0) and high cis-1,4 head-to tail repeating unites in the range of 91–95%. Thus, the catalyst systems that consisted of 1, 2 and 3/MMAO3A, are closely relevant to the current industrial polybutadiene rubber (PBR) and PIR production processes. Full article
(This article belongs to the Special Issue Advanced Catalysts for Polyolefin Production)
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10 pages, 1088 KiB  
Article
Propylene Polymerization Performance with Ziegler-Natta Catalysts Combined with U-Donor and T01 Donor as External Donor
by Padavattan Govindaswamy, Emiko Wada, Hiroyuki Kono, Toshiya Uozumi and Hideo Funabashi
Catalysts 2022, 12(8), 864; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12080864 - 05 Aug 2022
Viewed by 4142
Abstract
In propylene (C3) polymerization with Ziegler-Natta catalyst, not only internal donor but also external donor is very important to make isotactic polypropylene (PP) with higher yield. Most propylene-based polymers have been commercially produced with Ziegler-Natta catalysts combined with dialkyl-dialkoxy silane compounds (R2 [...] Read more.
In propylene (C3) polymerization with Ziegler-Natta catalyst, not only internal donor but also external donor is very important to make isotactic polypropylene (PP) with higher yield. Most propylene-based polymers have been commercially produced with Ziegler-Natta catalysts combined with dialkyl-dialkoxy silane compounds (R2Si(OR)2) such as C-donor, P-donor, and D-donor as external donors. In this paper, we will introduce the propylene polymerization performance with aminosilane compounds, i.e., diethylamino triethoxy silane (U-donor) and bis(ethylamino) di-cyclopentyl silane (T01 donor), as external donor in Ziegler–Natta catalyst. The polymerization screening experiments were conducted using some triethoxyalkylsilanes compounds (1–7) and performances were compared with U-donor. The polymerization results of the binary donor system show improvement in stereoregularity. These aminosilane compounds exhibit high hydrogen response in propylene polymerization and high copolymerization performance of propylene (C3) and ethylene (C2) in ICP production compared with dialkyl-dialkoxy silane compounds. While using methanol as an additive along with external electron donor, as a serendipitous, the copolymerization activity, block ratio, EPR (ethylene-propylene rubber) content improve significantly for U-donor as compared with T01 donor and C-donor. Full article
(This article belongs to the Special Issue Advanced Catalysts for Polyolefin Production)
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9 pages, 1167 KiB  
Communication
Isospecific Polymerization of Halide- and Amino-Substituted Styrenes Using a Bis(phenolate) Titanium Catalyst
by Qiyuan Wang, Zhen Zhang, Yang Jiang, Yanfeng Zhang, Shihui Li and Dongmei Cui
Catalysts 2022, 12(4), 439; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12040439 - 13 Apr 2022
Viewed by 2007
Abstract
Isospecific polymerization of polar styrenes is a challenge of polymer science. Particularly challenging are monomers bearing electron-withdrawing substituents or bulky substituents. Here, we report the coordination polymerization of halide- and amino-functionalized styrenes including para-fluorostyrene (pFS), para-chlorostyrene (pClS), [...] Read more.
Isospecific polymerization of polar styrenes is a challenge of polymer science. Particularly challenging are monomers bearing electron-withdrawing substituents or bulky substituents. Here, we report the coordination polymerization of halide- and amino-functionalized styrenes including para-fluorostyrene (pFS), para-chlorostyrene (pClS), para-bromostyrene (pBrS), and para-(N,N-diethylamino)styrene (DMAS) using 2,2′-sulfur-bridged bis(phenolate) titanium precursor (1). The combination of 1 and [Ph3C][B(C6F5)4] and AliBu3 provides crystalline poly(pFS)s with perfect isotacticity (mmmm > 95%) and high molecular weights (≤16.0 × 104 g mol−1). Upon activation with a large excess of DMAO, 1 reaches polymerization activity of 5.58 × 105 g molTi−1 h−1 producing isotactic poly(pFS)s featuring higher molecular weights (≤39.6 × 104 g mol−1). The distinguished performance of the 1/DMAO system has been extended to the polymerization of pClS and pBrS, both usually involve halogen abstraction during the polymerization, to produce isotactic and high molecular weight (Mn = 32.2 × 104 vs. 13.7 × 104 g mol−1) polymers in good activities (2.18 × 105 vs. 1.31 × 105 g molTi−1 h−1). Surprisingly, 1/DMAO is nearly inactive for DMAS polymerization, on contrary, the system 1/[Ph3C][B(C6F5)4]/AliBu3 displays isoselectivity (mmmm > 95%) albeit in a moderate activity. Full article
(This article belongs to the Special Issue Advanced Catalysts for Polyolefin Production)
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Review

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22 pages, 10408 KiB  
Review
Late Transition Metal Catalysts with Chelating Amines for Olefin Polymerization
by Huiyun Deng, Handou Zheng, Heng Gao, Lixia Pei and Haiyang Gao
Catalysts 2022, 12(9), 936; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12090936 - 24 Aug 2022
Cited by 11 | Viewed by 2432
Abstract
Polyolefins are the most consumed polymeric materials extensively used in our daily life and are usually generated by coordination polymerization in the polyolefin industry. Olefin polymerization catalysts containing transition metal–organic compound combinations are undoubtedly crucial for the development of the polyolefin industry. The [...] Read more.
Polyolefins are the most consumed polymeric materials extensively used in our daily life and are usually generated by coordination polymerization in the polyolefin industry. Olefin polymerization catalysts containing transition metal–organic compound combinations are undoubtedly crucial for the development of the polyolefin industry. The nitrogen donor atom has attracted considerable interest and is widely used in combination with the transition metal for the fine-tuning of the chemical environment around the metal center. In addition to widely reported olefin polymerization catalysts with imine and amide donors (sp2 hybrid N), late transition metal catalysts with chelating amine donors (sp3 hybrid N) for olefin polymerization have never been reviewed. In this review paper, we focus on late transition metal (Ni, Pd, Fe, and Co) catalysts with chelating amines for olefin polymerization. A variety of late transition metal catalysts bearing different neutral amine donors are surveyed for olefin polymerization, including amine–imine, amine–pyridine, α-diamine, and [N, N, N] tridentate ligands with amine donors. The relationship between catalyst structure and catalytic performance is also encompassed. This review aims to promote the design of late transition metal catalysts with unique chelating amine donors for the development of high-performance polyolefin materials. Full article
(This article belongs to the Special Issue Advanced Catalysts for Polyolefin Production)
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