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Special Issue "Organometallic Catalysis for Olefin Polymerization/Oligomerization"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: 10 August 2017

Special Issue Editor

Guest Editor
Prof. Dr. Kotohiro Nomura

Department of Chemistry, Faculty of Science and Engineering, Tokyo Metropolitan University, 1-1 minami Osawa, Hachioji, Tokyo 192-0397, Japan
Website | E-Mail
Interests: organometallics, catalysis, synthetic chemistry, polymer chemistry

Special Issue Information

Dear Colleagues,

We are calling for great contributions for the Special Issue, “Organometallic Catalysis for Olefin Polymerization/Oligomerization. The issue will cover the following topics: (i) synthesis of metal complex catalysts for olefin polymerization/oligomerization; (ii) metal catalyzed polymerizations; (iii) organometallic reactions related to efficient carbon–carbon bond formation; and (iv) synthesis of functional materials (polymers) by olefin polymerization and efficient carbon–carbon bond formation. It is clear that the design of molecular catalysis plays a very important role for synthesis of functional materials by precise olefin polymerization and efficient C–C bond formation. For example, metal catalyzed olefin coordination/insertion polymerization is a core technology in chemical industry, and olefin metathesis is an important reaction for synthesis of fine chemicals and advanced materials (polymers).

I hope this topic is of interest to you as we are taking the opportunity to look at recent developments as well as exploring the future scope in this field.

Prof. Dr. Kotohiro Nomura
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 papers will be 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. Molecules 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 1800 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

  • Synthesis of metal complex catalysts for olefin polymerization/oligomerization
  • Metal catalyzed polymerizations
  • Organometallic reactions
  • Synthesis of functional materials (polymers) by efficient C–C bond formation

Published Papers (7 papers)

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Research

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Open AccessArticle Synthesis and Characterization of Constrained Geometry Oxygen and Sulphur Functionalized Cyclopentadienylchromium Complexes and Their Use in Catalysis for Olefin Polymerization
Molecules 2017, 22(5), 856; doi:10.3390/molecules22050856
Received: 11 April 2017 / Revised: 8 May 2017 / Accepted: 15 May 2017 / Published: 22 May 2017
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Abstract
A series of constrained geometry O-functionalized cyclopentadienylchromium complexes (16) and a S-functionalized cyclopentadienylchromium complex (7) were first synthesized, characterized, and tested as catalyst precursors for the olefin polymerization. In the presence of MAO, the complexes exhibited high
[...] Read more.
A series of constrained geometry O-functionalized cyclopentadienylchromium complexes (16) and a S-functionalized cyclopentadienylchromium complex (7) were first synthesized, characterized, and tested as catalyst precursors for the olefin polymerization. In the presence of MAO, the complexes exhibited high catalytic activity for the polymerization of ethylene. It is shown that ligand variations can have a substantial effect on catalyst activity and stability. The effect of Al/Cr ratio on catalytic activity was also studied. Full article
(This article belongs to the Special Issue Organometallic Catalysis for Olefin Polymerization/Oligomerization)
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Open AccessArticle Isotactic and Syndiotactic Alternating Ethylene/Propylene Copolymers Obtained Through Non-Catalytic Hydrogenation of Highly Stereoregular cis-1,4 Poly(1,3-diene)s
Molecules 2017, 22(5), 755; doi:10.3390/molecules22050755
Received: 12 April 2017 / Revised: 2 May 2017 / Accepted: 3 May 2017 / Published: 6 May 2017
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Abstract
The homogeneous non-catalytic hydrogenation of cis-1,4 poly(isoprene), isotactic cis-1,4 poly(1,3-pentadiene) and syndiotactic cis-1,4 poly(1,3-pentadiene) with diimide, formed by thermal decomposition of para-toluenesulfonylhydrazide, is examined. Perfectly alternating ethylene/propylene copolymers having different tacticity (i.e., isotactic and syndiotactic), which are difficult to
[...] Read more.
The homogeneous non-catalytic hydrogenation of cis-1,4 poly(isoprene), isotactic cis-1,4 poly(1,3-pentadiene) and syndiotactic cis-1,4 poly(1,3-pentadiene) with diimide, formed by thermal decomposition of para-toluenesulfonylhydrazide, is examined. Perfectly alternating ethylene/propylene copolymers having different tacticity (i.e., isotactic and syndiotactic), which are difficult to synthesize by stereospecific copolymerization of the corresponding monomers, are obtained. Both isotactic and syndiotactic alternating ethylene/propylene copolymers are amorphous, with very low glass transition temperatures. Full article
(This article belongs to the Special Issue Organometallic Catalysis for Olefin Polymerization/Oligomerization)
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Open AccessArticle Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization
Molecules 2017, 22(5), 751; doi:10.3390/molecules22050751
Received: 24 April 2017 / Accepted: 3 May 2017 / Published: 5 May 2017
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Abstract
Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong
[...] Read more.
Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C5Me4)SiMe2(NtBu)]Cl2, a “constrained-geometry” titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80–120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C5Me4)SiMe2(NtBu)]Me2 catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst. Full article
(This article belongs to the Special Issue Organometallic Catalysis for Olefin Polymerization/Oligomerization)
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Open AccessArticle Quasi-Living Polymerization of Propene with an Isotactic-Specific Zirconocene Catalyst
Molecules 2017, 22(5), 725; doi:10.3390/molecules22050725
Received: 6 April 2017 / Revised: 24 April 2017 / Accepted: 27 April 2017 / Published: 2 May 2017
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Abstract
Propene polymerization with isotactic (iso)-specific C2-symmetric rac-Me2Si(2-Me-Benz(e)-Ind)2ZrCl2 (1) and rac-Me2Si(2-Me-4-Ph-1-Ind)2ZrCl2 (2) were conducted under various conditions for achieving iso-specific living polymerization of
[...] Read more.
Propene polymerization with isotactic (iso)-specific C2-symmetric rac-Me2Si(2-Me-Benz(e)-Ind)2ZrCl2 (1) and rac-Me2Si(2-Me-4-Ph-1-Ind)2ZrCl2 (2) were conducted under various conditions for achieving iso-specific living polymerization of propene. When Complex 1 was activated with trialkylaluminum-free modified methylaluminoxane (dMMAO) at −40 °C, the number-average molecular weight (Mn) linearly increased against the polymerization time to reach Mn = 704,000 within 15 min of polymerization, although the molecular weight distributions was broad (Mw/Mn < 3). Thus, it was found that quasi-living polymerization of propene proceeded in the 1-dMMAO system. The living nature of iso-polypropene was confirmed by the block copolymerization, where the Mn value increased from 221,000 to 382,000 after the addition of 1-octene to yield the block copolymer with a melting point of 150 °C. Full article
(This article belongs to the Special Issue Organometallic Catalysis for Olefin Polymerization/Oligomerization)
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Open AccessArticle N-(2,2-Dimethyl-1-(quinolin-2-yl)propylidene) arylaminonickel Complexes and Their Ethylene Oligomerization
Molecules 2017, 22(4), 630; doi:10.3390/molecules22040630
Received: 30 March 2017 / Revised: 10 April 2017 / Accepted: 11 April 2017 / Published: 13 April 2017
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Abstract
A series of N-(2,2-dimethyl-1-(quinolin-2-yl)propylidene) arylamines was sophisticatedly synthesized and reacted with nickel(II) bromine for the formation of the corresponding nickel complexes. All the organic compounds were characterized by IR, NMR spectra and elemental analysis, while all the nickel complexes were characterized by
[...] Read more.
A series of N-(2,2-dimethyl-1-(quinolin-2-yl)propylidene) arylamines was sophisticatedly synthesized and reacted with nickel(II) bromine for the formation of the corresponding nickel complexes. All the organic compounds were characterized by IR, NMR spectra and elemental analysis, while all the nickel complexes were characterized by IR spectra and elemental analysis. On activation with ethylaluminium sesquichloride (EASC) and modified methylaluminoxane (MMAO), all nickel precatalysts exhibited good activities toward ethylene oligomerization, indicating the positive efficiency of gem-dimethyl substitutents; in which major hexenes were obtained with MMAO. The catalytic parameters were verified, and the steric and electronic influences of substituents with ligands were observed, with a slight change of activities under different ethylene pressures. Full article
(This article belongs to the Special Issue Organometallic Catalysis for Olefin Polymerization/Oligomerization)
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Open AccessArticle Preparation of “Constrained Geometry” Titanium Complexes of [1,2]Azasilinane Framework for Ethylene/1-Octene Copolymerization
Molecules 2017, 22(2), 258; doi:10.3390/molecules22020258
Received: 27 December 2016 / Revised: 1 February 2017 / Accepted: 7 February 2017 / Published: 9 February 2017
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Abstract
The Me2Si-bridged ansa-Cp/amido half-metallocene, [Me2Si(η5-Me4C5)(NtBu)]TiCl2, termed a “constrained-geometry catalyst (CGC)”, is a representative homogeneous Ziegler catalyst. CGC derivatives with the [1,2]azasilinane framework, in which the amide alkyl substituent
[...] Read more.
The Me2Si-bridged ansa-Cp/amido half-metallocene, [Me2Si(η5-Me4C5)(NtBu)]TiCl2, termed a “constrained-geometry catalyst (CGC)”, is a representative homogeneous Ziegler catalyst. CGC derivatives with the [1,2]azasilinane framework, in which the amide alkyl substituent is joined by the Si-bridge, were prepared, and the catalytic performances of these species was studied. Me4C5HSi(Me)(CH2CH=CH2)-NH(C(R)(R’)CH=CH2) (R, R’ = H or methyl; Me4C5H = tetramethylcyclopentadienyl) was susceptible to ring closure metathesis (RCM) when treated with Schrock’s Mo-catalyst to afford -Si(Me4C5H)(Me)CH2CH=CHC(R)(R’)NH- containing a six-membered ring framework. Using the precursors and the products of RCM, various CGC derivatives, i.e., [-Si(η5-Me4C5)(Me)CH2CH=CHC(R)(H)N-]TiMe2 (13, R = H; 15, R = Me), [-Si(η5-Me4C5)(Me)CH2CH2CH2CH2N]TiMe2 (14), [(η5-Me4C5)Si(Me)(CH2CH=CH2)NCH2CH=CH2]TiMe2 (16), [(η5-Me4C5)Si (Me)(CH=CH2)NCH2CH=CH2]TiMe2 (17), and [(η5-Me4C5)Si(Me)(CH2CH3)NCH2CH2CH3]TiMe2 (18), were prepared. The catalytic activity of the newly prepared complexes was lower than that of CGC when activated with [Ph3C][B(C6F5)4]/iBu3Al. However, the catalytic activity of these species was improved by using tetrabutylaluminoxane ([iBu2Al]2O) instead of iBu3Al and the activity of 14/[Ph3C][B(C6F5)4]/[iBu2Al]2O was comparable to that of CGC/[Ph3C][B(C6F5)4]/iBu3Al (4.7 and 5.0 × 106 g/mol-Ti, respectively). Advantageously, the newly prepared complexes produced higher molecular weight poly(ethylene-co-1-octene)s than CGC. Full article
(This article belongs to the Special Issue Organometallic Catalysis for Olefin Polymerization/Oligomerization)
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Review

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Open AccessReview Engineering of Syndiotactic and Isotactic Polystyrene-Based Copolymers via Stereoselective Catalytic Polymerization
Molecules 2017, 22(4), 594; doi:10.3390/molecules22040594
Received: 18 March 2017 / Revised: 4 April 2017 / Accepted: 5 April 2017 / Published: 7 April 2017
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Abstract
This contribution presents an updated overview of the different copolymers containing stereoregular polystyrene blocks. Special emphasis is placed on syndiospecific and isospecific copolymerization of styrene with co-monomers (ethylene and α-olefins, conjugated and non-conjugated dienes, styrene derivatives, etc.). The catalytic systems involved are described
[...] Read more.
This contribution presents an updated overview of the different copolymers containing stereoregular polystyrene blocks. Special emphasis is placed on syndiospecific and isospecific copolymerization of styrene with co-monomers (ethylene and α-olefins, conjugated and non-conjugated dienes, styrene derivatives, etc.). The catalytic systems involved are described and the polymerization mechanisms are discussed. Alternative approaches (simultaneous, living, chain-transfer and graft copolymerization) and the resulting detailed structures and characteristics of the copolymers are also reported. Full article
(This article belongs to the Special Issue Organometallic Catalysis for Olefin Polymerization/Oligomerization)
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