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Catalysts
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Innovative Catalytic Approaches in Polymerization
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Innovative Catalytic Approaches in Polymerization

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalysis in Organic and Polymer Chemistry".

Deadline for manuscript submissions: 31 October 2025 | Viewed by 1667

Special Issue Editor

Prof. Dr. Kotohiro Nomura

E-Mail Website
Guest Editor
Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University (TMU), 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, Japan
Interests: catalysis; organometallic chemistry; polymer chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

This Special Issue, Innovative Catalytic Approaches in Polymerization, will cover recent trends in metal-catalyzed polymerization, including olefin coordination–insertion polymerization, metathesis polymerization, ring-opening polymerization, and condensation polymerization. The design of molecular catalysis clearly plays a very important role in the synthesis of functional materials through precise olefin polymerization. These efforts aim to contribute toward the development of sustainable green chemistry and a circular economy.

As is well known, polyolefins, produced by metal catalyzed olefin coordination polymerization, are important commercial synthetic polymers; considerable attention has been paid to produce new polymers with specified functions, properties which cannot be prepared by conventional, ordinary catalysts and/or technology. Furthermore, recent progress in the design of efficient transition metal complex catalysts offers promising possibilities, and related research has attracted considerable attention not only in the field of catalysis and organometallic chemistry, but also in the field of polymer chemistry.

In this Special Issue, we seek manuscripts which focus not only on the design of new (homogeneous and heterogeneous) catalysts and the synthesis of (co)polymers, but also those concerning polymerization methodologies and mechanistic studies. Research ralated to chemical recycling is also highly welcome.

We hope this Special Issue is of interest to you as we are take the opportunity to look at recent developments and to explore the future scope of 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 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. Catalysts 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 2200 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

  • olefin polymerization
  • ring-opening polymerization
  • metathesis polymerization/depolymerization
  • organometallics
  • homogeneous catalysts
  • heterogeneous catalysts
  • chemical recycling
  • upcycling

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Published Papers (3 papers)

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Research

12 pages, 573 KB  
Article
Polymerization of Ethylene and 1,3-Butadiene Using Methylaluminoxane-Phosphine Catalyst Systems
by Nanako Kimura and Daisuke Takeuchi
Catalysts 2025, 15(10), 942; https://doi.org/10.3390/catal15100942 - 1 Oct 2025
Viewed by 385
Abstract
Although transition metal catalysts have been used extensively for the polymerization of hydrocarbon monomers, several cationic aluminum catalysts have been also known to promote polymerization of ethylene and 1,3-butadiene. Transition-metal catalyzed polymerization generally proceeds via coordination and insertion of the monomer on one [...] Read more.
Although transition metal catalysts have been used extensively for the polymerization of hydrocarbon monomers, several cationic aluminum catalysts have been also known to promote polymerization of ethylene and 1,3-butadiene. Transition-metal catalyzed polymerization generally proceeds via coordination and insertion of the monomer on one metal center. In contrast, in ethylene polymerization using aluminum catalysts, a bimolecular chain growth mechanism, including the reaction between neutral aluminum species and the monomer activated by cationic aluminum species, is proposed. Although previously reported aluminum catalysts are based on a monoaluminum complex, a dialuminum complex is expected to catalyze the polymerization more efficiently, considering the proposed mechanism. In this work, we found that a combination of diphosphines and MAO promotes polymerization of ethylene and 1,3-butadiene. The 1,4-bis(diphenylphosphino)butane (DPPB)/methylaluminoxane (MAO) system showed a much higher activity toward ethylene polymerization than other monophosphine or diphosphine/MAO systems. NMR analysis of a mixture of diphosphine and MAO indicates the formation of cationic dialuminum species in the presence of DPPB, whereas the formation of cationic monoaluminum species occurs in the presence of other diphosphines. The 2,2′-bis(diphenylphosphino)-1,1′-biphenyl (BIPHEP)/MAO system promoted 1,3-butadiene polymerization to give polybutadiene having a cis-1,4 selectivity of up to 93.8%. Full article
(This article belongs to the Special Issue Innovative Catalytic Approaches in Polymerization)
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13 pages, 1377 KB  
Article
2-(5-Phenylpyrazol-3-yl)-8-arylimino-5,6,7-trihydroquinolyliron Chlorides as Precatalysts for Ethylene Oligomerization
by Jiahao Gao, Yaling Fang, Yanping Ma, Liqun Jin, Yizhou Wang, Xinquan Hu, Wenjuan Zhang and Wen-Hua Sun
Catalysts 2025, 15(9), 898; https://doi.org/10.3390/catal15090898 - 17 Sep 2025
Viewed by 400
Abstract
A series of 2-(5-phenylpyrazol-3-yl)-8-arylimino-5,6,7-trihydroquinolyliron chlorides (Fe1–Fe6) have been prepared and characterized by FT-IR spectra and elemental analysis. In single-crystal X-ray crystallography, Fe4 shows a distorted trigonal–bipyramidal geometry along with a self-assembling network through intermolecular NH···HO and OH···Cl hydrogen bonding. [...] Read more.
A series of 2-(5-phenylpyrazol-3-yl)-8-arylimino-5,6,7-trihydroquinolyliron chlorides (Fe1–Fe6) have been prepared and characterized by FT-IR spectra and elemental analysis. In single-crystal X-ray crystallography, Fe4 shows a distorted trigonal–bipyramidal geometry along with a self-assembling network through intermolecular NH···HO and OH···Cl hydrogen bonding. In the presence of MAO, all iron complexes perform with good activity and high selectivity for 1-butene. In addition, mixed solvents with different ratios of methylcyclohexane and toluene have been explored with a view to optimizing the catalytic performance. Full article
(This article belongs to the Special Issue Innovative Catalytic Approaches in Polymerization)
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Figure 1

12 pages, 1210 KB  
Communication
Synthesis of New Phenoxide-Modified Half-Titanocene Catalysts for Ethylene Polymerization
by Jiahao Gao, Wen-Hua Sun and Kotohiro Nomura
Catalysts 2025, 15(9), 840; https://doi.org/10.3390/catal15090840 - 2 Sep 2025
Viewed by 629
Abstract
A series of half-titanocenes containing different trialkylsilyl para-phenoxy substituents, Cp*TiCl2(O-2,6-iPr2-4-R-C6H2) [Cp* = C5Me5; R = Si(n-Bu)3 (5), SiMe2(n-C8 [...] Read more.
A series of half-titanocenes containing different trialkylsilyl para-phenoxy substituents, Cp*TiCl2(O-2,6-iPr2-4-R-C6H2) [Cp* = C5Me5; R = Si(n-Bu)3 (5), SiMe2(n-C8H17) (6), SiMe2(t-Bu) (7)], were prepared and identified. Catalytic activity in ethylene polymerization by Cp*TiCl2(O-2,6-iPr2-4-R-C6H2) [R = H (1), SiMe3 (2), SiEt3 (3), Si(i-Pr)3 (4), 5–7]–MAO (methylaluminoxane) catalysts increased in the following order (in toluene at 25 °C, ethylene 4 atm): R = H (1) < SiMe3 (2), SiEt3 (3), Si(i-Pr)3 (4) < SiMe2(t-Bu) (7) < SiMe2(n-C8H17) (6) < Si(n-Bu)3 (5, activity = 6.56 × 104 kg-PE/mol-Ti·h). The results thus suggest that the introduction of an alkyl group into a silyl substituent led to an increase in activity. The activities of 5 were affected by the Al/Ti molar ratio (amount of MAO charged), and the highest activity (7.00 × 105 kg-PE/mol-Ti·h) was observed under optimized conditions at 50 °C, whereas the activity decreased at 80 °C. In ethylene copolymerization with 1-dodecene, the Si(n-Bu)3 analog (5) exhibited remarkable catalytic activity (4.32 × 106 kg-polymer/mol-Ti·h at 25 °C), which was higher than those of the reported catalysts (1–3), affording poly(ethylene-co-1-dodecene)s with efficient comonomer incorporation as observed in 3 [rE = 3.77 (5) vs. 3.58 (3)]. Full article
(This article belongs to the Special Issue Innovative Catalytic Approaches in Polymerization)
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