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Polymers
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Catalytic Olefin Polymerization and Polyolefin Materials
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Catalytic Olefin Polymerization and Polyolefin Materials

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

Deadline for manuscript submissions: 10 June 2024 | Viewed by 7041

Special Issue Editors

Dr. Incoronata Tritto

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Guest Editor
Istituto di Scienze e Tecnologie Chimiche (CNR), SCITEC "G. Natta", Via Corti 12, Milan, Italy
Interests: olefin polymerization; homogeneous and heterogeneous catalytic systems; α-olefin and cyclic olefin homo- and copolymers; ROMP; stereochemistry; NMR analysis; block copolymers; nanostructured hybrid polymers; polymers from renewable sources
Special Issues, Collections and Topics in MDPI journals
Dr. Laura Boggioni

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Istituto di Scienze e Tecnologie Chimiche (CNR), SCITEC "G. Natta", via Corti 12, Milan, Italy
Interests: olefin polymerization; homogeneous catalytic systems; α-olefin and cyclic olefin homo- and copolymers; microstructure analysis; polymers from renewable sources
Special Issues, Collections and Topics in MDPI journals
Dr. Simona Losio

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Guest Editor
Istituto di Scienze e Tecnologie Chimiche (CNR), SCITEC "G. Natta", via Corti 12, Milan, Italy
Interests: olefin polymerization; homogeneous catalytic systems; α-olefin homo- and copolymers; microstructural analysis; polymers from renewable sources
Special Issues, Collections and Topics in MDPI journals
Dr. Selena Silvano

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Guest Editor
Istituto di Scienze e Tecnologie Chimiche (CNR), SCITEC "G. Natta", via Corti 12, Milan, Italy
Interests: olefin polymerization; anionic polymerization; ROMP; polymers and materials from renewable sources and waste

Special Issue Information

Dear Colleagues,

Sixty years ago, Ziegler and Natta were awarded the Chemistry Nobel Prize for their discovery of olefin polymerization catalysts. The major advantage of coordination catalysis is the outstanding control over the polymer microstructure, which determines polymer characteristics, such as mechanical, thermal, and optical properties, and thus their final commercial values.

Since then, the striking developments in catalytic olefin polymerizations at the academic and industrial levels have led to a family of materials that comprise thermoplastics, thermoplastic elastomers, and rubbers. Their low cost, processing versatility, and range of mechanical properties have made them essential in our everyday lives and modern infrastructure. Nowadays, polyolefins account for the largest segment of commercial polymeric materials.

Advancements in the performance of organometallic catalysts in olefin (co)polymerization are a key driving force in this field. Tailoring polyolefins via advanced polymerization catalysis is crucial for moving beyond the frontiers of commodity polyolefins and developing a sustainable and circular plastics economy.

Despite environmental concerns, polyolefins have the highest hydrogen and oil-like energy content among any plastic and can be converted back into oil and gas via thermal and catalytic cracking or recycled due to their durability. They could be perfect for enabling a circular plastic economy.

The scope of this Special Issue is to focus on recent progress and current trends in the field of catalytic polymerization, including the development of new metal catalysts, as well as advances in polymerization catalysis and the synthesis and properties of novel polymeric materials. Both original articles and reviews are welcome.

Dr. Incoronata Tritto
Dr. Laura Boggioni
Dr. Simona Losio
Dr. Selena Silvano
Guest Editors

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

  • homo- and copolymerization
  • metal catalysts
  • microstructure
  • characterization
  • material properties
  • olefins, polar monomers and non-olefinic monomers
  • material applications

Published Papers (7 papers)

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Research

14 pages, 2264 KiB  
Article
Experimental and Theoretical Insights into the Effect of Dioldibenzoate Isomers on the Performance of Polypropylene Catalysts
by Huasheng Feng, Changxiu Li, Junling Zhou, Xiaofan Zhang, Shuxuan Tang, Xiangya Xu and Zhihui Song
Polymers 2024, 16(4), 559; https://doi.org/10.3390/polym16040559 - 19 Feb 2024
Viewed by 542
Abstract
Experimental investigations and density functional theory (DFT) calculations were carried out to study the comprehensive effect of different 3,5-heptanedioldibenzoate (HDDB) optical isomers as the internal electron donor on the catalytic performance of Ziegler−Natta catalysts. The experimental catalytic activity of HDDB has a positive [...] Read more.
Experimental investigations and density functional theory (DFT) calculations were carried out to study the comprehensive effect of different 3,5-heptanedioldibenzoate (HDDB) optical isomers as the internal electron donor on the catalytic performance of Ziegler−Natta catalysts. The experimental catalytic activity of HDDB has a positive correlation with the relative content of the mesomer incorporated during catalyst preparation, while the hydrogen response of HDDB displayed a negative correlation with the relative content of the mesomer. In order to apply the DFT calculation results to the macroscopic activity of the catalyst, the content of the active centers of the catalyst was analyzed. Assuming that the content of the active centers is proportional to the internal electron donor content of the catalyst, binary linear regression was carried out, which showed a good linear correlation between experimental activity data and internal electron donor content. Furthermore, the fitted activity of the single active centers aligned well with the calculated activation energies. These results revealed that the catalytic activity of polypropylene (PP) catalysts is dependent on both the active center content and the catalytic activity of an individual active center. Additionally, the lower hydrogen response of HDDB leads to a higher molecular weight of polypropylene obtained from the RS-containing catalyst compared to the SS-containing catalyst. Further study reveals that the hydrogen transfer reactions of 2,4-pentanediol dibenzoate (PDDB)/HDDB are influenced by the orientation of the methyl/ethyl groups in different isomers, which affect the activation energy differences between the hydrogen transfer reaction and the propylene insertion reaction, and finally influence the molecular weight of PP. Full article
(This article belongs to the Special Issue Catalytic Olefin Polymerization and Polyolefin Materials)
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11 pages, 2384 KiB  
Article
Amorphous Elastomeric Ultra-High Molar Mass Polypropylene in High Yield by Half-Titanocene Catalysts
by Simona Losio, Fabio Bertini, Adriano Vignali, Taiga Fujioka, Kotohiro Nomura and Incoronata Tritto
Polymers 2024, 16(4), 512; https://doi.org/10.3390/polym16040512 - 14 Feb 2024
Viewed by 555
Abstract
Propylene polymerizations with different ketimide-modified half-titanocene catalysts, Cp’TiCl2(N=CtBu2) [Cp’ = C5H5 (1), C5Me5 (2), Me3SiC5H4 (3)], with MAO as a [...] Read more.
Propylene polymerizations with different ketimide-modified half-titanocene catalysts, Cp’TiCl2(N=CtBu2) [Cp’ = C5H5 (1), C5Me5 (2), Me3SiC5H4 (3)], with MAO as a cocatalyst, were investigated. The obtained polymers were studied in detail by determining their microstructure, molar masses, thermal, and mechanical properties. The Cp*-ketimide, (C5Me5)TiCl2(N=CtBu2) (2), exhibited higher catalytic activities than Cp’TiCl2(N=CtBu2) (1,3), yielding higher molar mass polymers, Mw up to 1400 Kg/mol. All the synthesized polypropylenes (PP) are atactic and highly regioregular, with predominant rrrr pentads, especially PP prepared with catalyst 1. Differential scanning calorimetry (DSC) established that the polymers are fully amorphous aPP, and no melting endotherm events are detected. Glass transition temperatures were detected between −2 and 2 °C. These polypropylenes have been established to be high-performance thermoplastic elastomers endowed with remarkably high ductility, and a tensile strain at break higher than 2000%. Full article
(This article belongs to the Special Issue Catalytic Olefin Polymerization and Polyolefin Materials)
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12 pages, 2347 KiB  
Article
Synthesis of Network Biobased Aliphatic Polyesters Exhibiting Better Tensile Properties than the Linear Polymers by ADMET Polymerization in the Presence of Glycerol Tris(undec-10-enoate)
by Lance O’Hari P. Go, Mohamed Mehawed Abdellatif, Ryoji Makino, Daisuke Shimoyama, Seiji Higashi, Hiroshi Hirano and Kotohiro Nomura
Polymers 2024, 16(4), 468; https://doi.org/10.3390/polym16040468 - 7 Feb 2024
Viewed by 884
Abstract
Development of biobased aliphatic polyesters with better mechanical (tensile) properties in film has attracted considerable attention. This report presents the synthesis of soluble network biobased aliphatic polyesters by acyclic diene metathesis (ADMET) polymerization of bis(undec-10-enyl)isosorbide diester [M1, dianhydro-D-glucityl bis(undec-10-enoate)] [...] Read more.
Development of biobased aliphatic polyesters with better mechanical (tensile) properties in film has attracted considerable attention. This report presents the synthesis of soluble network biobased aliphatic polyesters by acyclic diene metathesis (ADMET) polymerization of bis(undec-10-enyl)isosorbide diester [M1, dianhydro-D-glucityl bis(undec-10-enoate)] in the presence of a tri-arm crosslinker [CL, glycerol tris(undec-10-enoate)] using a ruthenium–carbene catalyst, and subsequent olefin hydrogenation using RhCl(PPh3)3. The resultant polymers, after hydrogenation (expressed as HCP1) and prepared in the presence of 1.0 mol% CL, showed better tensile properties than the linear polymer (HP1) with similar molecular weight [tensile strength (elongation at break): 20.8 MPa (282%) in HP1 vs. 35.4 MPa (572%) in HCP1]. It turned out that the polymer films prepared by the addition of CL during the polymerization (expressed as a 2-step approach) showed better tensile properties. The resultant polymer film also shows better tensile properties than the conventional polyolefins such as linear high density polyethylene, polypropylene, and low density polyethylene. Full article
(This article belongs to the Special Issue Catalytic Olefin Polymerization and Polyolefin Materials)
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11 pages, 3624 KiB  
Article
Copolymerization of Ethylene with Functionalized 1,1-Disubstituted Olefins Using a Fluorenylamido-Ligated Titanium Catalyst
by Oluwaseyi Aderemi Ajala, Moeko Ono, Yuushou Nakayama, Ryo Tanaka and Takeshi Shiono
Polymers 2024, 16(2), 236; https://doi.org/10.3390/polym16020236 - 15 Jan 2024
Viewed by 1298
Abstract
Considering the sustainability of material development, coordination polymerization catalysts effective for 1,1-disubstituted olefins are receiving a great deal of attention because they can introduce a variety of plant-derived comonomers, such as β-pinene and limonene, into polyolefins. However, due to their sterically encumbered property, [...] Read more.
Considering the sustainability of material development, coordination polymerization catalysts effective for 1,1-disubstituted olefins are receiving a great deal of attention because they can introduce a variety of plant-derived comonomers, such as β-pinene and limonene, into polyolefins. However, due to their sterically encumbered property, incorporating these monomers is difficult. Herein, we succeeded in the copolymerization of ethylene with various hydroxy- or siloxy-substituted vinylidenes using a fluorenylamido-ligated titanium catalyst–MMAO system. This is the first example of ethylene/polar 1,1-disubstituted olefins’ copolymerization using an early transition metal catalyst system. The polymerization proceeded at room temperature without pressurizing ethylene, and high-molecular-weight, functionalized polyethylene was obtained. The obtained copolymer showed a reduced water contact angle compared with that of the ethylene/isobutene copolymer, demonstrating the increment in hydrophilicity by hydroxy groups. Full article
(This article belongs to the Special Issue Catalytic Olefin Polymerization and Polyolefin Materials)
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15 pages, 5037 KiB  
Article
Parallel Catalyst Synthesis Protocol for Accelerating Heterogeneous Olefin Polymerization Research
by Patchanee Chammingkwan, Mostafa Khoshsefat, Minoru Terano and Toshiaki Taniike
Polymers 2023, 15(24), 4729; https://doi.org/10.3390/polym15244729 - 17 Dec 2023
Cited by 1 | Viewed by 803
Abstract
The data scientific approach has become an indispensable tool for capturing structure–performance relationships in complex systems, where the quantity and quality of data play a crucial role. In heterogeneous olefin polymerization research, the exhaustive and multi-step nature of Ziegler-Natta catalyst synthesis has long [...] Read more.
The data scientific approach has become an indispensable tool for capturing structure–performance relationships in complex systems, where the quantity and quality of data play a crucial role. In heterogeneous olefin polymerization research, the exhaustive and multi-step nature of Ziegler-Natta catalyst synthesis has long posed a bottleneck in synthetic throughput and data generation. In this contribution, a custom-designed 12-parallel reactor system and a catalyst synthesis protocol were developed to achieve the parallel synthesis of a magnesium ethoxide-based Ziegler-Natta catalyst. The established system, featuring a miniature reaction vessel with magnetically suspended stirring, allows for over a tenfold reduction in synthetic scale while ensuring the consistency and reliability of the synthesis. We demonstrate that the established protocol is highly efficient for the generation of a catalyst library with diverse compositions and physical features, holding promise as a foundation for the data-driven establishment of the structure–performance relationship in heterogeneous olefin polymerization catalysis. Full article
(This article belongs to the Special Issue Catalytic Olefin Polymerization and Polyolefin Materials)
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11 pages, 1214 KiB  
Article
Catalytic Behavior of Cobalt Complexes Bearing Pyridine–Oxime Ligands in Isoprene Polymerization
by Yuanxu Du, Shuo Gao, Hui Ma, Siqi Lu, Zhenhua Zhang and Mengmeng Zhao
Polymers 2023, 15(24), 4660; https://doi.org/10.3390/polym15244660 - 10 Dec 2023
Cited by 1 | Viewed by 885
Abstract
Several cobalt(II) complexes Co1–Co3 bearing pyridine–oxime ligands (L1 = pyridine-2-aldoxime for Co1; L2 = 6-methylpyridine-2-aldoxime for Co2; L3 = phenyl-2-pyridylketoxime for Co3) and picolinaldehyde O-methyl oxime (L4)-supported Co4 were synthesized and well characterized by FT-IR, [...] Read more.
Several cobalt(II) complexes Co1–Co3 bearing pyridine–oxime ligands (L1 = pyridine-2-aldoxime for Co1; L2 = 6-methylpyridine-2-aldoxime for Co2; L3 = phenyl-2-pyridylketoxime for Co3) and picolinaldehyde O-methyl oxime (L4)-supported Co4 were synthesized and well characterized by FT-IR, mass spectrum and elemental analysis. The single-crystal X-ray diffraction of complex Co2 reveals that the cobalt center of CoCl2 is coordinated with two 6-methylpyridine-2-aldoxime ligands binding with Npyridine and Noxime atoms, which feature a distorted octahedral structure. These Co complexes Co1–Co4 displayed extremely high activity toward isoprene polymerization upon activation with small amount of AlClEt2 in toluene, giving polyisoprene with high activity up to 16.3 × 105 (mol of Co)−1(h)−1. And, the generated polyisoprene displayed high molecular weights and narrow molecular distribution with a cis-1,4-enriched selectivity. The type of cobalt complexes, cocatalyst and reaction temperature all have effects on the polymerization activity but not on the microstructure of polymer. Full article
(This article belongs to the Special Issue Catalytic Olefin Polymerization and Polyolefin Materials)
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11 pages, 2124 KiB  
Article
Synthesis of Degradable Polyolefins Bearing Disulfide Units via Metathesis Copolymerization
by Yu Xia, Fulin Zhou, Wenyan Hao and Shan Tang
Polymers 2023, 15(14), 3101; https://doi.org/10.3390/polym15143101 - 20 Jul 2023
Cited by 2 | Viewed by 1598
Abstract
Disulfide bonds are dynamic covalent bonds, which are easy to cleave and reform upon chemical stimulus. Various methods including the oxidative coupling of thiols and polymerization of disulfide-containing monomers have been developed for the synthesis of poly(disulfide)s. However, installing small amounts of disulfide [...] Read more.
Disulfide bonds are dynamic covalent bonds, which are easy to cleave and reform upon chemical stimulus. Various methods including the oxidative coupling of thiols and polymerization of disulfide-containing monomers have been developed for the synthesis of poly(disulfide)s. However, installing small amounts of disulfide units in the main chain of polyolefins has received much less attention. Herein, we report a novel strategy for incorporating cleavable disulfide units into the backbone of polyolefins using commercially available diallyl disulfide (DADS) as a comonomer via metathesis copolymerization. The copolymerization of diallyl disulfide with cyclooctene occurred using the second-generation Grubbs catalyst under mild conditions, allowing for the synthesis of copolymers with adjustable disulfide content ranging from 0.7 to 8.5 mol%, and the molecular weight of the obtained copolymers ranged from 5.8 kg·mol−1 to 42.8 kg·mol−1. The resulting polyolefins with disulfide insertion retained excellent thermal processability and exhibited degradability. Treatment of the copolymer (8.5 mol% disulfide content) with tri-n-butylphosphine resulted in a significant reduction in molecular weight from 5.8 kg·mol−1 to 1.6 kg·mol−1. Successful copolymerization with diallyl disulfide provides a convenient and effective method for obtaining degradable polyolefins. Full article
(This article belongs to the Special Issue Catalytic Olefin Polymerization and Polyolefin Materials)
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