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Polymers
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Coordination Catalysis in Additive Polymerization
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Coordination Catalysis in Additive Polymerization

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 19585

Special Issue Editor

Prof. Dr. Ilya E. Nifant'ev

E-Mail Website
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
Special Issues, Collections and Topics in MDPI journals

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

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Keywords

  • coordination polymerization
  • metallocenes
  • methathesis polymerization
  • stereoregular polydienes
  • polyesters
  • polyolefins
  • post-metallocene catalysts
  • ring-opening polymerizations
  • single-site catalysts
  • Ziegler-Natta catalysts

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Published Papers (5 papers)

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Research

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20 pages, 3079 KiB  
Article
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://doi.org/10.3390/polym12092153 - 21 Sep 2020
Cited by 7 | Viewed by 4093
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 [...] Read more.
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  
Article
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://doi.org/10.3390/polym12091988 - 31 Aug 2020
Cited by 6 | Viewed by 2943
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) [...] Read more.
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 (Mw/Mn ≈ 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  
Article
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://doi.org/10.3390/polym12071609 - 19 Jul 2020
Cited by 1 | Viewed by 3247
Abstract
The self-assembled multinuclear PdII complexes {(Li-OPOOMe2)PdMe(4-5-nonyl-pyridine)}4Li2Cl2 (C, Li-OPOOMe2 = 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] [...] Read more.
The self-assembled multinuclear PdII complexes {(Li-OPOOMe2)PdMe(4-5-nonyl-pyridine)}4Li2Cl2 (C, Li-OPOOMe2 = 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  
Article
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://doi.org/10.3390/polym12071590 - 17 Jul 2020
Cited by 12 | Viewed by 3305
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 [...] Read more.
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] (NBF) 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  
Review
Fair Look at Coordination Oligomerization of Higher α-Olefins
by Ilya Nifant’ev and Pavel Ivchenko
Polymers 2020, 12(5), 1082; https://doi.org/10.3390/polym12051082 - 9 May 2020
Cited by 26 | Viewed by 5164
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 [...] Read more.
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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