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Polymers
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Catalytic Applications in Polymerization
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Catalytic Applications in Polymerization

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

Deadline for manuscript submissions: closed (30 November 2023) | Viewed by 6341

Special Issue Editor

Dr. Pavel Ivchenko

E-Mail Website
Guest Editor
Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia
Interests: single-site catalysis in polymerization and transformations of α-olefins; coordination catalysis and organocatalysis for ring-opening polymerization; synthesis of high-margin petrochemical products; biodegradable polymers; DFT modeling of the mechanisms of organic reactions and catalytic processes
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The global strategy of resource efficiency implies the use of mankind's limited resources in a sustainable manner, while minimising the impact on the environment. Its specific embodiment allows us to create larger amounts of higher-quality materials at lower cost, to develop and use waste-free technologies, and to enhance our share of renewable raw materials. The very idea of catalysis inherently fits within this strategy. It is through the development of the science of catalysis that we are capable of coordinating the polymerization of α-olefins, dienes and cyclic esters, all types of metathesis polymerization, a variety of polycondensation processes, etc. Catalytic methods are invaluable in the design of new monomers and polymer microstructures and architectures. It is no exaggeration to say that polymer chemistry is inseparable from catalysis, at least in the fields of polymer design, synthesis and technology.

This Special Issue focuses on creating a multidisciplinary forum of discussion on recent advances in the use of catalysis in polymer chemistry.

Dr. Pavel Ivchenko
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

  • catalysis
  • coordination polymerization
  • metathesis polymerization
  • organocatalysts
  • polycondensation
  • regioselectivity
  • ring-opening polymerization
  • single-site catalysts
  • stereoselectivity

Published Papers (4 papers)

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Research

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15 pages, 4289 KiB  
Article
Dimethylformamide Impurities as Propylene Polymerization Inhibitor
by Joaquín Hernández-Fernández, Rafael González-Cuello and Rodrigo Ortega-Toro
Polymers 2023, 15(18), 3806; https://doi.org/10.3390/polym15183806 - 18 Sep 2023
Viewed by 981
Abstract
This research study examined how the use of dimethylformamide (DMF) as an inhibitor affects the propylene polymerization process when using a Ziegler–Natta catalyst. Several experiments were carried out using TiCl4/MgCl2 as a catalyst, aluminum trialkyl as a cocatalyst, and different [...] Read more.
This research study examined how the use of dimethylformamide (DMF) as an inhibitor affects the propylene polymerization process when using a Ziegler–Natta catalyst. Several experiments were carried out using TiCl4/MgCl2 as a catalyst, aluminum trialkyl as a cocatalyst, and different amounts of DMF. Then, we analyzed how DMF influences other aspects of the process, such as catalyst activity, molecular weight, and the number of branches in the polymer chains obtained, using experimental and computational methods. The results revealed that as the DMF/Ti ratio increases, the catalyst activity decreases. From a concentration of 5.11 ppm of DMF, a decrease in catalyst activity was observed, ranging from 45 TM/Kg to 44 TM/Kg. When the DMF concentration was increased to 40.23 ppm, the catalyst activity decreased to 43 TM/Kg, and with 75.32 ppm, it dropped even further to 39 TM/Kg. The highest concentration of DMF evaluated, 89.92 ppm, resulted in a catalyst productivity of 36.5 TM/Kg and lost productivity of 22%. In addition, significant changes in the polymer’s melt flow index (MFI) were noted as the DMF concentration increased. When 89.92 ppm of DMF was added, the MFI loss was 75%, indicating a higher flowability of the polymer. In this study, it was found that dimethylformamide (DMF) exhibits a strong affinity for the titanium center of a Ziegler–Natta (ZN) catalyst, with an adsorption energy (Ead) of approximately −46.157 kcal/mol, indicating a robust interaction. This affinity is significantly higher compared to propylene, which has an Ead of approximately −5.2 kcal/mol. The study also revealed that the energy gap between the highest occupied molecular orbital (HOMO) of DMF and the lowest unoccupied molecular orbital (SOMO) of the Ziegler–Natta (ZN) catalyst is energetically favorable, with a value of approximately 0.311 eV. Full article
(This article belongs to the Special Issue Catalytic Applications in Polymerization)
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13 pages, 8083 KiB  
Article
Research of Potential Catalysts for Two-Component Silyl-Terminated Prepolymer/Epoxy Resin Adhesives
by Ritvars Berzins, Remo Merijs-Meri and Janis Zicans
Polymers 2023, 15(10), 2269; https://doi.org/10.3390/polym15102269 - 11 May 2023
Cited by 2 | Viewed by 1250
Abstract
The current research is devoted to the research of potential catalysts for the two-component silyl-terminated prepolymer/epoxy resin system. The catalyst system must catalyze the prepolymer of the opposite component while not curing the prepolymer in the component in which the catalyst is located. [...] Read more.
The current research is devoted to the research of potential catalysts for the two-component silyl-terminated prepolymer/epoxy resin system. The catalyst system must catalyze the prepolymer of the opposite component while not curing the prepolymer in the component in which the catalyst is located. Mechanical and rheological characterization of the adhesive was performed. The results of the investigation showed that certain alternative catalyst systems, which are less toxic, may be used instead of traditional catalysts for individual systems. Two-component systems, obtained by using these catalysts systems, cure in an acceptable time scale and demonstrate relatively high tensile strength and deformation values. Full article
(This article belongs to the Special Issue Catalytic Applications in Polymerization)
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Review

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49 pages, 10820 KiB  
Review
Polyisobutylenes with Controlled Molecular Weight and Chain-End Structure: Synthesis and Actual Applications
by Ilya E. Nifant’ev, Sofia A. Korchagina, Maria S. Chinova and Alexander N. Tavtorkin
Polymers 2023, 15(16), 3415; https://doi.org/10.3390/polym15163415 - 15 Aug 2023
Cited by 1 | Viewed by 1673
Abstract
The polymerization of isobutylene allows us to obtain a wide spectrum of polyisobutylenes (PIBs) which differ in their molecular weight characteristics and the chemical structure of chain-end groups. The bulk of the PIBs manufactured worldwide are highly reactive polyisobutylenes (HRPIBs) with –C(Me)=CH2 [...] Read more.
The polymerization of isobutylene allows us to obtain a wide spectrum of polyisobutylenes (PIBs) which differ in their molecular weight characteristics and the chemical structure of chain-end groups. The bulk of the PIBs manufactured worldwide are highly reactive polyisobutylenes (HRPIBs) with –C(Me)=CH2 end-groups and low-molecular weights (Mn < 5 kDa). HRPIBs are feedstocks that are in high demand in the manufacturing of additives for fuels and oils, adhesives, detergents, and other fine chemicals. In addition, HRPIBs and CMe2Cl-terminated PIBs are intensively studied with the aim of finding biomedical applications and for the purpose of developing new materials. Both chain control (molecular weight and dispersity) and chemoselectivity (formation of exo-olefinic or –CMe2Cl groups) should be achieved during polymerization. This review highlights the fundamental issues in the mechanisms of isobutylene polymerization and PIB analysis, examines actual catalytic approaches to PIBs, and describes recent studies on the functionalization and applications of HRPIBs and halogen-terminated PIBs. Full article
(This article belongs to the Special Issue Catalytic Applications in Polymerization)
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63 pages, 19681 KiB  
Review
MAO- and Borate-Free Activating Supports for Group 4 Metallocene and Post-Metallocene Catalysts of α-Olefin Polymerization and Oligomerization
by Ilya E. Nifant’ev, Pavel D. Komarov, Oksana D. Kostomarova, Nikolay A. Kolosov and Pavel V. Ivchenko
Polymers 2023, 15(14), 3095; https://doi.org/10.3390/polym15143095 - 19 Jul 2023
Cited by 2 | Viewed by 2018
Abstract
Modern industry of advanced polyolefins extensively uses Group 4 metallocene and post-metallocene catalysts. High-throughput polyolefin technologies demand the use of heterogeneous catalysts with a given particle size and morphology, high thermal stability, and controlled productivity. Conventional Group 4 metal single-site heterogeneous catalysts require [...] Read more.
Modern industry of advanced polyolefins extensively uses Group 4 metallocene and post-metallocene catalysts. High-throughput polyolefin technologies demand the use of heterogeneous catalysts with a given particle size and morphology, high thermal stability, and controlled productivity. Conventional Group 4 metal single-site heterogeneous catalysts require the use of high-cost methylalumoxane (MAO) or perfluoroaryl borate activators. However, a number of inorganic phases, containing highly acidic Lewis and Brønsted sites, are able to activate Group 4 metal pre-catalysts using low-cost and affordable alkylaluminums. In the present review, we gathered comprehensive information on MAO- and borate-free activating supports of different types and discussed the surface nature and chemistry of these phases, examples of their use in the polymerization of ethylene and α-olefins, and prospects of the further development for applications in the polyolefin industry. Full article
(This article belongs to the Special Issue Catalytic Applications in Polymerization)
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