Special Issue "Catalysts for the Controlled Polymerization of Conjugated Dienes"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: closed (15 November 2017)

Special Issue Editor

Guest Editor
Prof. Dr. Marc Visseaux

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
Website | E-Mail
Phone: (+33)-03-20-33-64-83
Fax: (+33)-03-20-43-65-85
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

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Keywords

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

Published Papers (5 papers)

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Research

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Open AccessArticle Novel Allyl Cobalt Phosphine Complexes: Synthesis, Characterization and Behavior in the Polymerization of Allene and 1,3-Dienes
Catalysts 2017, 7(12), 381; doi:10.3390/catal7120381
Received: 16 November 2017 / Revised: 1 December 2017 / Accepted: 1 December 2017 / Published: 7 December 2017
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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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Open AccessFeature PaperArticle Synthesis, Structure and 1,3-Butadiene Polymerization Behavior of Vanadium(III) Phosphine Complexes
Catalysts 2017, 7(12), 369; doi:10.3390/catal7120369
Received: 9 November 2017 / Revised: 24 November 2017 / Accepted: 25 November 2017 / Published: 28 November 2017
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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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Figure 1

Open AccessFeature PaperArticle Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials
Catalysts 2017, 7(12), 361; doi:10.3390/catal7120361
Received: 3 November 2017 / Revised: 24 November 2017 / Accepted: 25 November 2017 / Published: 27 November 2017
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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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Figure 1

Open AccessFeature PaperArticle Synthesis of Stereodiblock Polybutadiene Using Cp*Nd(BH4)2(thf)2 as a Catalyst
Catalysts 2017, 7(10), 284; doi:10.3390/catal7100284
Received: 7 September 2017 / Revised: 18 September 2017 / Accepted: 19 September 2017 / Published: 25 September 2017
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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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Open AccessFeature PaperReview Recent Advances in Rare Earth Complexes Bearing Allyl Ligands and Their Reactivity towards Conjugated Dienes and Styrene Polymerization
Catalysts 2017, 7(12), 378; doi:10.3390/catal7120378
Received: 15 November 2017 / Revised: 29 November 2017 / Accepted: 30 November 2017 / Published: 5 December 2017
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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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