Catalysis in α-Olefin Polymerization/Oligomerization

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

Deadline for manuscript submissions: closed (30 April 2019) | Viewed by 7196

Special Issue Editor

Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama, Japan
Interests: organometallic chemistry; main group chemistry; coordination chemistry; early transition metal; controlled polymerization; post metallocene

Special Issue Information

Dear Colleagues,

Fifty-five years after the Nobel Prize was awarded to Ziegler and Natta in 1963,  polymerization/oligomerization of α-olefins by transition-metal catalysts has grown to one of the most enchanting areas in academic and industrial research. The transition-metal catalysts have enabled precise synthesis of polyolefins and oligomers with the suitable choice of an ancillary ligand for the transition-metal complex. In recent decades, extensive research efforts have been devoted to developing new early- and late transition metal catalysts that can achieve higher activities and stereospecificities, and controlled polymer properties in various α-olefin polymerization. Progress in research on coordination polymerization catalyzed by transition-metal complexes continues to produce new α-olefin-based materials that are economically and environmentally favorable.

This Special Issue aims to cover promising progress and novel trends in the broad field of polymerization/oligomerization of α-olefins and co-polymerization of ethylene with α-olefins, employing new transition-metal catalysts systems. The catalytic species include homogeneous catalysts, such as metallocene and half-metallocene complexes, post-metallocene complexes possessing ancillary donor ligands, as well as late transition-metal complexes based on nickel and palladium atoms. Studies on mechanistic insights and polymer characterization would also be of great interest.

Prof. Dr. Norio Nakata
Guest Editor

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Keywords

  • α-Olefin
  • Polyolefin
  • Homogeneous catalyst
  • Polymerization
  • Oligomerization
  • Copolymerization
  • Mechanism
  • Characterization
  • Early transition-metal catalysts
  • Late transition-metal catalysts

Published Papers (2 papers)

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Research

11 pages, 1323 KiB  
Communication
Synthesis of Brominated Polyethylene by Copolymerization of Ethylene with ω–bromoalkene Catalyzed by a Metallocene and Methylaluminoxane System
by Tomoyuki Toda, Itaru Miura, Masamitsu Miya and Katsuhiko Takenaka
Catalysts 2019, 9(8), 660; https://doi.org/10.3390/catal9080660 - 31 Jul 2019
Cited by 4 | Viewed by 3601
Abstract
The metallocene-catalyzed copolymerization of ethylene and 11–bromo–1–undecene was carried out to synthesize brominated polyethylene (PE). A modified methylaluminoxane (MMAO) solution was used as a cocatalyst and rac–Et(H4Ind)2ZrCl2 as a catalyst. The copolymerization showed a high activity and [...] Read more.
The metallocene-catalyzed copolymerization of ethylene and 11–bromo–1–undecene was carried out to synthesize brominated polyethylene (PE). A modified methylaluminoxane (MMAO) solution was used as a cocatalyst and rac–Et(H4Ind)2ZrCl2 as a catalyst. The copolymerization showed a high activity and afforded the copolymer with a 11-bromo-1-undecene incorporation ranging from 1.0 to 4.3 mol%. When using a dried methylaluminoxane (dMAO) as a cocatalyst, the incorporation ratio of 11-bromo-1-undecene increased remarkably to 25.2 mol%. It was demonstrated that the type of MAO used as a cocatalyst affects the composition of the ethylene/11-bromo-1-undecene copolymer without changing the structure of the catalytic complex. Full article
(This article belongs to the Special Issue Catalysis in α-Olefin Polymerization/Oligomerization)
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9 pages, 1004 KiB  
Article
Carbazolyl-Substituted [OSSO]-Type Zirconium(IV) Complex as a Precatalyst for the Oligomerization and Polymerization of α-Olefins
by Norio Nakata, Kazuaki Nakamura, Shotaro Nagaoka and Akihiko Ishii
Catalysts 2019, 9(6), 528; https://doi.org/10.3390/catal9060528 - 13 Jun 2019
Cited by 6 | Viewed by 3184
Abstract
The dibenzyl zirconium(IV) complex (4) incorporating with a carbazolyl(Cbz)-substituted [OSSO]-type bis(phenolate) ligand was synthesized. Upon activation with dried modified methylaluminoxane (dMMAO), precatalyst 4 at relatively low catalyst loadings was found to promote the 1,2-regioselective oligomerization of 1-hexene to produce the corresponding [...] Read more.
The dibenzyl zirconium(IV) complex (4) incorporating with a carbazolyl(Cbz)-substituted [OSSO]-type bis(phenolate) ligand was synthesized. Upon activation with dried modified methylaluminoxane (dMMAO), precatalyst 4 at relatively low catalyst loadings was found to promote the 1,2-regioselective oligomerization of 1-hexene to produce the corresponding vinylidene-ended oligomers with moderate turnover frequencies (TOFs) up to 2080 h−1. The 13C NMR analysis of the resulting oligomers revealed the formation of dimer-enriched oligo(1-hexene)s in 39–62% distributions. The precatalyst 4 with dried methylaluminoxane (dMAO) also exhibited good performance in the polymerization of styrene yielding isotactic polystyrenes ([mm] > 99%) with quite large molecular weights (Mw < 508,100 g mol−1) and relatively high catalytic activity (up to 2810 g mmol(4)−1 h−1). Full article
(This article belongs to the Special Issue Catalysis in α-Olefin Polymerization/Oligomerization)
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