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Coordination Catalysis in Additive Polymerization

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (31 August 2020) | Viewed by 16570

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Special Issue Editor

Prof. Dr. Ilya E. Nifant'ev

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Guest Editor

Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1–3, Moscow 119991, Russia
Interests: organic and inorganic synthesis; homogeneous catalysis; macromolecules; coordination catalysis and organocatalysis for ring-opening polymerization; single-site catalysis in polymerization and transformations of α-olefins and dienes; synthesis of advanced petrochemical products; biodegradable polymers; actual materials for biomedical applications
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Special Issue Information

Dear Colleagues,

Since the mid-twentieth century coordination catalysis was playing a key role in design of novel polymers, in finding innovative polymerization processes and in development of modern technologies for polymer industry. Discovery of coordination polymerization of α-olefins by Karl Ziegler and Giulio Natta in 1950s, followed by R&D in coordination polymerization of dienes, ring-opening methathesis polymerization and ring-opening coordination polymerization of cyclic esters, have led to basic understanding of the dominant role of the metal centers in formation of new bonds during the synthesis of macromolecules with given polymerization degree, microstructure and stereochemistry. Advanced polyolefins, "green" polydienes, biodegradable polyesters and special biocompatible materials for tissue engineering, drag delivery and controlled drag release – this is far not full list of the materials developed for humanity in recent decades using coordination catalysis.

This Special Issue focuses on creating a multidisciplinary forum of discussion on recent advances in the design of coordination catalysts and their applications in the broad area of additive polymerization processes, including homogeneous and heterogeneous polymerization and oligomerization of α-olefins, dienes, polar vinyl monomers, cyclic esters, epoxides, CO₂, for creating a new-age materials.

Prof. Ilya E. Nifant'ev
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. Polymers is an international peer-reviewed open access semimonthly 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 polymerization
metallocenes
methathesis polymerization
stereoregular polydienes
polyesters
polyolefins
post-metallocene catalysts
ring-opening polymerizations
single-site catalysts
Ziegler-Natta catalysts

Published Papers (5 papers)

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Research

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20 pages, 3079 KiB

Open AccessArticle

Raman Spectroscopy Study of Structurally Uniform Hydrogenated Oligomers of α-Olefins

by Sergey M. Kuznetsov, Maria S. Iablochnikova, Elena A. Sagitova, Kirill A. Prokhorov, Gulnara Yu. Nikolaeva, Leila Yu. Ustynyuk, Pavel V. Ivchenko, Alexey A. Vinogradov, Alexander A. Vinogradov and Ilya E. Nifant’ev

Polymers 2020, 12(9), 2153; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12092153 - 21 Sep 2020

Cited by 6 | Viewed by 3597

Abstract

The expansion of the range of physico-chemical methods in the study of industrially significant α-olefin oligomers and polymers is of particular interest. In our article, we present a comparative Raman study of structurally uniform hydrogenated dimers, trimers, tetramers, and pentamers of 1-hexene and 1-octene, that are attractive as bases for freeze-resistant engine oils and lubricants. We found out that the joint monitoring of the disorder longitudinal acoustic mode (D-LAM) and symmetric C–C stretching modes allows the quantitative characterization of the number and length of alkyl chains (i.e., two structural characteristics), upon which the pour point and viscosity of the hydrocarbons depend, and to distinguish these compounds from both each other and linear alkanes. We demonstrated that the ratio of the contents of CH₂ and CH₃ groups in these hydrocarbons can be determined by using the intensities of the bands in the spectra, related to the asymmetric stretching vibrations of these groups. The density functional theory (DFT) calculations were applied to reveal the relations between the wavenumber and bandshape of the symmetric C–C stretching mode and a conformation arrangement of the 1-hexene and 1-octene dimers. We found that the branched double-chain conformation results in the splitting of the C–C mode into two components with the wavenumbers, which can be used as a measure of the length of branches. This conformation is preferable to the extended-chain conformation for hydrogenated 1-hexene and 1-octene dimers. Full article

(This article belongs to the Special Issue Coordination Catalysis in Additive Polymerization)

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11 pages, 1962 KiB

Open AccessArticle

Living Chain-Walking (Co)Polymerization of Propylene and 1-Decene by Nickel α-Diimine Catalysts

by Pei Li, Xiaotian Li, Shabnam Behzadi, Mengli Xu, Fan Yu, Guoyong Xu and Fuzhou Wang

Polymers 2020, 12(9), 1988; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12091988 - 31 Aug 2020

Cited by 4 | Viewed by 2508

Abstract

Homo- and copolymers of propylene and 1-decene were synthesized by controlled chain-walking (co)polymerization using phenyl substituted α-diimine nickel complexes activated with modified methylaluminoxane (MMAO). This catalytic system was found to polymerize propylene in a living fashion to furnish high molecular weight ethylene-propylene (EP) copolymers. The copolymerizations proceeded to give high molecular weight P/1-decene copolymers with narrow molecular weight distribution (M_w/M_n ≈ 1.2), which indicated a living nature of copolymerization at room temperature. The random copolymerization results indicated the possibility of precise branched structure control, depending on the polymerization temperature and time. Full article

(This article belongs to the Special Issue Coordination Catalysis in Additive Polymerization)

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8 pages, 2781 KiB

Open AccessArticle

Copolymerization of Ethylene and Vinyl Fluoride by Self-Assembled Multinuclear Palladium Catalysts

by Qian Liu and Richard F. Jordan

Polymers 2020, 12(7), 1609; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12071609 - 19 Jul 2020

Viewed by 2724

Abstract

The self-assembled multinuclear Pd^II complexes {(Li-OPO^OMe2)PdMe(4-5-nonyl-pyridine)}₄Li₂Cl₂ (C, Li-OPO^OMe2 = PPh(2-SO₃Li-4,5-(OMe)₂-Ph)(2-SO₃⁻-4,5-(OMe)₂-Me-Ph)), {(Zn-OP-P-SO)PdMe(L)}₄ (D, L = pyridine or 4-^tBu-pyridine, [OP-P-SO]³⁻ = P(4-^tBu-Ph)(2-PO₃²⁻-5-Me-Ph)(2-SO₃⁻-5-Me-Ph)), and {(Zn-OP-P-SO)PdMe(pyridine)}₃ (E) copolymerize ethylene and vinyl fluoride (VF) to linear copolymers. VF is incorporated at levels of 0.1–2.5 mol% primarily as in-chain -CH₂CHFCH₂- units. The molecular weight distributions of the copolymers produced by D and E are generally narrower than for catalyst C, which suggests that the Zn-phosphonate cores of D and E are more stable than the Li-sulfonate-chloride core of C under copolymerization conditions. The ethylene/VF copolymerization activities of C–E are over 100 times lower and the copolymer molecular weights (MWs) are reduced compared to the results for ethylene homopolymerization by these catalysts. Full article

(This article belongs to the Special Issue Coordination Catalysis in Additive Polymerization)

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21 pages, 5549 KiB

Open AccessArticle

Experimental and Theoretical Study of Zirconocene-Catalyzed Oligomerization of 1-Octene

by Ilya Nifant’ev, Alexander Vinogradov, Alexey Vinogradov, Stanislav Karchevsky and Pavel Ivchenko

Polymers 2020, 12(7), 1590; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12071590 - 17 Jul 2020

Cited by 11 | Viewed by 2725

Abstract

Zirconocene-catalyzed coordination oligomerization of higher α-olefins is of theoretical and practical interest. In this paper, we present the results of experimental and theoretical study of α-olefin oligomerization, catalyzed by (η⁵-C₅H₅)]₂ZrX₂ 1/1′ and O[SiMe₂(η⁵-C₅H₄)]₂ZrX₂ 2/2′ (X = Cl, Me) with the activation by modified methylalymoxane MMAO-12 or by perfluoroalkyl borate [PhNMe₂H][B(C₆F₅)₄] (NB^F) in the presence and in the absence of organoaluminium compounds, Al(CH₂CHMe₂)₃ (TIBA) and/or Et₂AlCl. Under the conditions providing a conventional mononuclear reaction mechanism, 1′ catalyzed dimerization with low selectivity, while 2′ initiated the formation of oligomers in equal mass ratio. The presence of TIBA and especially Et₂AlCl resulted in an increase of the selectivity of dimerization. Quantum chemical simulations of the main and side processes performed at the M-06x/ DGDZVP level of the density functional theory (DFT) allowed to explain experimental results involving traditional mononuclear and novel Zr-Al₁ and Zr-Al₂ mechanistic concepts. Full article

(This article belongs to the Special Issue Coordination Catalysis in Additive Polymerization)

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Review

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31 pages, 6697 KiB

Open AccessFeature PaperReview

Fair Look at Coordination Oligomerization of Higher α-Olefins

by Ilya Nifant’ev and Pavel Ivchenko

Polymers 2020, 12(5), 1082; https://0-doi-org.brum.beds.ac.uk/10.3390/polym12051082 - 09 May 2020

Cited by 24 | Viewed by 4389

Abstract

Coordination catalysis is a highly efficient alternative to more traditional acid catalysis in the oligomerization of α-olefins. The distinct advantage of transition metal-based catalysts is the structural homogeneity of the oligomers. Given the great diversity of the catalysts and option of varying the reaction conditions, a wide spectrum of processes can be implemented. In recent years, both methylenealkanes (vinylidene dimers of α-olefins) and structurally uniform oligomers with the desired degrees of polymerization have become available for later use in the synthesis of amphiphilic organic compounds and polymers, high-quality oils or lubricants, and other prospective materials. In the present review, we discussed the selective dimerization and oligomerization of α-olefins, catalyzed by metallocene and post-metallocene complexes, and explored the prospects for the further applications of the coordination α-olefin dimers and oligomers. Full article

(This article belongs to the Special Issue Coordination Catalysis in Additive Polymerization)

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