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Catalysts for the Controlled Polymerization of Conjugated Dienes
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Catalysts for the Controlled Polymerization of Conjugated Dienes

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

Deadline for manuscript submissions: closed (31 December 2018) | Viewed by 31156

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editor

Prof. Dr. Marc Visseaux

E-Mail Website
Guest Editor
Unité de Catalyse et Chimie du Solide—UMR CNRS 8181 ENSCL, Bâtiment C7, B.P. 90108, Université des Sciences et Technologies de Lille, 59652 Villeneuve d’Ascq CEDEX, France
Interests: coordination chemistry; rare earths; organometallic catalysis; controlled polymerization; olefins/conjugated dienes/styrene; ROP

Special Issue Information

Dear Colleagues,

The polymerization of conjugated dienes is a domain of interest for both academic and industrial research. In a context where the control of the process is always to be improved—in terms of (but not limited to) efficiency, micro-structure, etc.—and whereas environmental concerns have, nowadays, to be taken into consideration, the development of new catalysts is still a necessary and modern challenge. This includes molecular catalysts comprising less toxic metals, as single component or as dual catalytic combinations. The implementation of the recent concepts of the field, such as coordinative chain transfer polymerization or chain shuttling polymerization, and the application to the (co-)polymerization of recently introduced bio-sourced conjugated dienes as monomers are also of high interest.

The aim of this Special Issue is, thus, to cover promising recent research and novel trends in the field of the development and application of new catalysts for conjugated dienes polymerization and copolymerization. Contributions from all areas of homogeneous/supported catalysis, based on experimental results and/or mechanistic approaches, would be of great interest.

Prof. Dr. Marc Visseaux
Guest Editor

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

  • Coordination catalysis
  • Stereo-selective polymerization
  • Conjugated dienes
  • Chain transfer
  • Rare earths
  • Main-group metals
  • Allyl
  • Organometallics
  • Reaction mechanisms
  • Computational calculations

Published Papers (7 papers)

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Editorial

Jump to: Research, Review

4 pages, 161 KiB  
Editorial
Catalysts for the Controlled Polymerization of Conjugated Dienes
by Marc Visseaux
Catalysts 2018, 8(10), 442; https://doi.org/10.3390/catal8100442 - 09 Oct 2018
Cited by 6 | Viewed by 2059
Abstract
Since its first discovery at the beginning of the 1960s […]  Full article
(This article belongs to the Special Issue Catalysts for the Controlled Polymerization of Conjugated Dienes)

Research

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21 pages, 4778 KiB  
Article
1,3-Diene Polymerization Mediated by Homoleptic Tetramethylaluminates of the Rare-Earth Metals
by Christoph O. Hollfelder, Lars N. Jende, Dominic Diether, Theresa Zelger, Rita Stauder, Cäcilia Maichle-Mössmer and Reiner Anwander
Catalysts 2018, 8(2), 61; https://doi.org/10.3390/catal8020061 - 03 Feb 2018
Cited by 22 | Viewed by 5258
Abstract
During the past two decades homoleptic tetramethylaluminates of the trivalent rare-earth metals, Ln(AlMe4)3, have emerged as useful components for efficient catalyst design in the field of 1,3-diene polymerization. Previous work had focused on isoprene polymerization applying Ln(AlMe4) [...] Read more.
During the past two decades homoleptic tetramethylaluminates of the trivalent rare-earth metals, Ln(AlMe4)3, have emerged as useful components for efficient catalyst design in the field of 1,3-diene polymerization. Previous work had focused on isoprene polymerization applying Ln(AlMe4)3 precatalysts with Ln = La, Ce, Pr, Nd, Gd and Y, in the presence of Et2AlCl as an activator. Polymerizations employing Ln(AlMe4)3 with Ln = La, Y and Nd along with borate/borane co-catalysts [Ph3C][B(C6F5)4], [PhNMe2H][B(C6F5)4] and [B(C6F5)3] were mainly investigated for reasons of comparison with ancillary ligand-supported systems (cf. half-sandwich complexes). The present study investigates into a total of eleven rare-earth elements, namely Ln = La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Er and Lu. A full overview on the polymerization behavior of Ln(AlMe4)3 in the presence of perfluorinated borate/borane cocatalysts and R2AlCl-type activators (R = Me, Et) is provided, probing the monomers isoprene and 1,3-butadiene (and preliminary ethylene). Virtually complete cis-1,4-selectivities are obtained for several catalyst/cocatalyst combinations (e.g., Gd(AlMe4)3/Me2AlCl, >99.9%). Insights into the ‘black box’ of active species are obtained by indirect observations via screening of pre-reaction time and cocatalyst concentration. The microstructure of the polydienes is investigated by combined 1H/13C NMR and ATR-IR spectroscopies. Furthermore, the reaction of [LuMe6(Li(thf)x)3] with AlMe3 has been applied as a new strategy for the efficient synthesis of Lu(AlMe4)3. The solid-state structures of Gd(AlMe4)3 and Tb(AlMe4)3 are reported. Full article
(This article belongs to the Special Issue Catalysts for the Controlled Polymerization of Conjugated Dienes)
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2885 KiB  
Article
Novel Allyl Cobalt Phosphine Complexes: Synthesis, Characterization and Behavior in the Polymerization of Allene and 1,3-Dienes
by Giovanni Ricci, Antonella Caterina Boccia, Giuseppe Leone and Alessandra Forni
Catalysts 2017, 7(12), 381; https://doi.org/10.3390/catal7120381 - 07 Dec 2017
Cited by 18 | Viewed by 4091
Abstract
Novel allyl cobalt complexes, i.e., (η3-C4H7)(η4-C4H6)Co(PCyPh2) (1), (η3-C4H7)(η4-C4H6)Co(PMePh2) (2) and (η [...] Read more.
Novel allyl cobalt complexes, i.e., (η3-C4H7)(η4-C4H6)Co(PCyPh2) (1), (η3-C4H7)(η4-C4H6)Co(PMePh2) (2) and (η3-C5H9)(η4-C5H8)Co(PMePh2) (3), were synthesized by reacting CoCl2(PRPh2)2 (R = methyl, cyclohexyl) with 1,3-butadiene or isoprene in presence of metallic zinc. The complexes were fully characterized by Nuclear Magnetic Resonance (NMR) spectroscopy (1H and 2D experiments); in case of 1, single crystals, suitable for X-ray analysis, were obtained and the molecular structure was determined. The allyl cobalt phosphine complexes alone gave highly crystalline 1,2 polymers from 1,2-propadiene, but they did not polymerize 1,3-dienes. Nevertheless, in the presence of a stoichiometric amount of methylaluminoxane (MAO), they were able to polymerize 1,3-butadiene and substituted 1,3-butadienes such as isoprene, (E)-1,3-pentadiene, (E)-1,3-hexadiene, and (E)-3-methyl-1,3-pentadiene. Specifically, 1/MAO gave predominantly syndiotactic 1,2 polymers from 1,3-butadiene and terminally substituted 1,3-butadienes (e.g., 1,3-pentadiene and 1,3-hexadiene), but it was practically not active in the polymerization of internally substituted 1,3-butadienes (e.g., isoprene and 3-methyl-1,3-pentadiene); 2/MAO and 3/MAO exhibited instead an opposite behavior, giving predominantly isotactic 1,2 polymers from 3-methyl-1,3-pentadiene, and showing very low activity in the polymerization of 1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene. The results obtained are interesting from the mechanistic point of view, and some hypotheses to explain this particular behavior were formulated. Full article
(This article belongs to the Special Issue Catalysts for the Controlled Polymerization of Conjugated Dienes)
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761 KiB  
Article
Synthesis, Structure and 1,3-Butadiene Polymerization Behavior of Vanadium(III) Phosphine Complexes
by Giuseppe Leone, Giorgia Zanchin, Ivana Pierro, Anna Sommazzi, Alessandra Forni and Giovanni Ricci
Catalysts 2017, 7(12), 369; https://doi.org/10.3390/catal7120369 - 28 Nov 2017
Cited by 10 | Viewed by 3890
Abstract
A series of vanadium(III) complexes bearing monodentate tertiary phosphine ligands of the type VCl3(PRnPh3-n)2 (n = 0 (1a); n = 1 and R = Me (1b), Et (1c), [...] Read more.
A series of vanadium(III) complexes bearing monodentate tertiary phosphine ligands of the type VCl3(PRnPh3-n)2 (n = 0 (1a); n = 1 and R = Me (1b), Et (1c), iPr (1d), Cy (1e); n = 2 and R = Me (1f), Et (1g), Cy (1h)), and VCl3(PR3)2 (R = Cyp (2a), Cy (2b), nPr (2c), tBu (2d)) were synthesized and characterized. In the case of 1c, 1g and 2a single crystals were also obtained and their molecular structures were determined. All the complexes were used, in combination with methylaluminoxane (sMAO) or AlMe3–free MAO (dMAO), for the polymerization of 1,3-butadiene, exhibiting rather good activity and giving polymers with different microstructure depending on the nature of the phosphine ligand and the type of co-catalyst employed. Full article
(This article belongs to the Special Issue Catalysts for the Controlled Polymerization of Conjugated Dienes)
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2818 KiB  
Article
Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials
by Eva Laur, Alexandre Welle, Aurélien Vantomme, Jean-Michel Brusson, Jean-François Carpentier and Evgueni Kirillov
Catalysts 2017, 7(12), 361; https://doi.org/10.3390/catal7120361 - 27 Nov 2017
Cited by 22 | Viewed by 4889
Abstract
The copolymerization of bio-renewable β-myrcene or β-farnesene with styrene was examined using an ansa-neodymocene catalyst, affording two series of copolymers with high styrene content and unprecedented syndioregularity of the polystyrene sequences. The incorporation of terpene in the copolymers ranged from [...] Read more.
The copolymerization of bio-renewable β-myrcene or β-farnesene with styrene was examined using an ansa-neodymocene catalyst, affording two series of copolymers with high styrene content and unprecedented syndioregularity of the polystyrene sequences. The incorporation of terpene in the copolymers ranged from 5.6 to 30.8 mol % (β-myrcene) and from 2.5 to 9.8 mol % (β-farnesene), respectively. NMR spectroscopy and DSC analyses suggested that the microstructure of the copolymers consists of 1,4- and 3,4-poly(terpene) units randomly distributed along syndiotactic polystyrene chains. The thermal properties of the copolymers are strongly dependent on the terpene content, which is easily controlled by the initial feed. The terpolymerization of styrene with β-myrcene in the presence of ethylene was also examined. Full article
(This article belongs to the Special Issue Catalysts for the Controlled Polymerization of Conjugated Dienes)
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2347 KiB  
Article
Synthesis of Stereodiblock Polybutadiene Using Cp*Nd(BH4)2(thf)2 as a Catalyst
by Ryo Tanaka, Yuto Shinto, Yuushou Nakayama and Takeshi Shiono
Catalysts 2017, 7(10), 284; https://doi.org/10.3390/catal7100284 - 25 Sep 2017
Cited by 11 | Viewed by 5259
Abstract
Butadiene polymerization, in both a highly cis- and trans-specific manner, was achieved by using a Cp*Nd(BH4)2(thf)2–Bu2Mg system as an initiator. The cis-/trans- ratio can be tuned by the amount of [...] Read more.
Butadiene polymerization, in both a highly cis- and trans-specific manner, was achieved by using a Cp*Nd(BH4)2(thf)2–Bu2Mg system as an initiator. The cis-/trans- ratio can be tuned by the amount of trialkylaluminum-depleted modified methylaluminoxane (dMMAO). The cis-regularity of the polymer was much higher than those obtained by Nd(BH4)3(thf)3. The molecular weight of cis-regular polymer was increased according to polymer yield, showing that there was no termination or chain transfer reaction during the polymerization. Synthesis of stereodiblock polybutadiene, which showed a high melting temperature (Tm) compared with stereodiblock polyisoprene, was also performed by the addition dMMAO during the polymerization. Full article
(This article belongs to the Special Issue Catalysts for the Controlled Polymerization of Conjugated Dienes)
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Review

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1325 KiB  
Review
Recent Advances in Rare Earth Complexes Bearing Allyl Ligands and Their Reactivity towards Conjugated Dienes and Styrene Polymerization
by Jashvini Jothieswaran, Sami Fadlallah, Fanny Bonnet and Marc Visseaux
Catalysts 2017, 7(12), 378; https://doi.org/10.3390/catal7120378 - 05 Dec 2017
Cited by 26 | Viewed by 5058
Abstract
This mini-review focuses on recent advances on the synthesis, structure, and characterization of allyl-based rare earth organometallic complexes, with emphasis on their ability to catalyze the polymerization of non-polar monomers such as conjugated dienes, styrene, and their related copolymerization. Full article
(This article belongs to the Special Issue Catalysts for the Controlled Polymerization of Conjugated Dienes)
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