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Silsesquioxanes—Precursors to Functional Materials: Synthesis and Applications—a Themed Issue to Honor Professor Bogdan Marciniec on the Occasion of His 80th Birthday

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A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 24894

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Prof. Dr. Beata Dudziec

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Guest Editor

Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University in Poznan, Poznan, Poland
Interests: organosilicon/germanium chemistry; homogeneous catalysis; syntheses of silsesquioxanes; silsesquioxane-based materials

Prof. Dr. Krzysztof Matyjaszewski

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Co-Guest Editor

Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA
Interests: chemistry; polymers; polymer chemistry; polymer science; materials

Special Issue Information

Dear Colleagues,

It is our pleasure to present this Special Issue of Materials dedicated to silsesquioxanes and Professor Bogdan Marciniec. Professor Marciniec is a distinguished Polish chemist who profoundly contributed to the development of the chemistry of organometalloid (Si, Ge, B) compounds and their specific architectures, also silsesquioxanes. His main research activity focuses on the TM (transition metal)-mediated catalytic modifications of the aforementioned compounds. His expertise in the field of catalysis led to the discovery of a new type of catalytic transformation and C-H activation in vinyl metalloids, i.e., metallative coupling, also known as Marciniec coupling, and broadly exploited the hydrosilylation reaction of olefins and alkynes. His contributions concern not only the elaboration of new methodologies in the catalytic transformations of organometalloids but also the search for novel catalysts of those reactions. Prof. Marciniec’s scientific experience has also resulted in many collaborations between his research group and leading silicone manufacturers, i.e., General Electric Silicones, Momentive Performance Materials, and Dow Corning, in the area of developing new catalytic systems used for silicone curing via hydrosilylation.

Professor Bogdan Marciniec was born in 1941 in Seceminie near Kielce, Poland. He received an M.Sc. (1963) and Ph.D. (1970) from the Adam Mickiewicz University, Poznan, Poland. In 1975, he finished his habilitation and received the title of professor in 1986. He was always very closely connected with the Alma Mater and held the position of Dean of Faculty of Chemistry and Rector of the Adam Mickiewicz University. Additionally, he contributed to linking chemistry with other life sciences, being a creator of the University Foundation, Poznan Science and Technology Park (https://ppnt.poznan.pl/about-us/) as well as the Centre for Advanced Technologies (http://wczt.pl/en). He was honored with numerous state and international scientific awards. Professor Bogdan Marciniec is an author or co-author of over 470 publications (cited over 6,500 times), 200 patents, and over 17 technologies implemented in the industry, as well as 23 book chapters (e. g., Handbook of Metathesis (Wiley-VCH, 2003). He is also the editor and co-author of 15 books, e.g., “Hydrosilylation – A Comprehensive Review on Recent Advances” (Springer, 2009). Finally, he coined the term “silicometallics” for compounds with M-Si bonds, which was successfully introduced to the scientific nomenclature.

His research interests also concern functionalized silsesquioxanes (SQs), i.e., the specific organosilicon structures that feature cage-like architectures with Si–O–Si linkages and tetrahedral Si vertices. Due to the presence of a well-defined inorganic core that is a scaffold for attached organic moieties, they have become representatives of building blocks for hybrid materials. Thanks to their finely tunable physical and chemical properties, SQs meet the requirements of science and also industry.

Materials is pleased to dedicate a Special Issue to Professor Bogdan Marciniec on the occasion of his 80th birthday and for his contribution to the development of organosilicon chemistry, and especially silsesquioxanes, which are compounds of his particular scientific interest.

This Special Issue contains manuscripts that explore the chemistry of organosilicon chemistry and especially functionalized silsesquioxanes that are interesting compounds on their own but also precursors to many advanced materials.

You are invited and welcome to submit a manuscript to this Special Issue in the form of a regular article, a communication, or a review.

Prof. Dr. Beata Dudziec
Prof. Dr. Krzysztof Matyjaszewski
Guest Editors

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Keywords

Silsesquioxanes (SQs)
Organic–inorganic frameworks
Hybrid materials
Nanocomposites
Silsesquioxane-based materials
Linear and 3D SQ-based systems
Polymer nanofillers and modifiers
Dendrimers
Catalyst immobilization
Drug carriers

Published Papers (10 papers)

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Research

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24 pages, 25240 KiB

Open AccessArticle

Effect of Shear Stress during Processing on Structure, Morphology, and Properties of Isotactic Polypropylene Nucleated with Silsesquioxane-Based β-Nucleating Agent

by Mateusz Barczewski, Olga Mysiukiewicz, Michał Dutkiewicz, Mariusz Szołyga, Monika Dobrzyńska-Mizera and Adam Piasecki

Materials 2023, 16(10), 3627; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16103627 - 09 May 2023

Cited by 1 | Viewed by 1377

Abstract

The study aimed to determine the influence of shear stress during real-life industrial processes such as compression molding and injection molding to different cavities on the crystallization of the isotactic polypropylene nucleated with a novel silsesquioxane-based β-nucleating agent. Octakis(N²,N⁶-dicyclohexyl-4-(3-(dimethylsiloxy)propyl)naphthalene-2,6-dicarboxamido)octasilsesquioxane (SF-B01) is a highly effective nucleating agent (NA) based on the hybrid organic-inorganic silsesquioxane cage. The samples containing various amounts of the silsesquioxane-based and commercial iPP β-nucleants (0.01–0.5 wt%) were prepared by compression molding and injection molding, including forming in the cavities with different thicknesses. The study of the thermal properties, morphology, and mechanical properties of iPP samples allows for obtaining comprehensive information about the efficiency of silsesquioxane-based NA in shearing conditions during the forming. As a reference sample, iPP nucleated by commercial β-NA (namely N²,N⁶-dicyclohexylnaphthalene-2,6-dicarboxamide, NU-100) was used. The static tensile test assessed the mechanical properties of pure and nucleated iPP samples formed in different shearing conditions. Variations of the β-nucleation efficiency of the silsesquioxane-based and commercial nucleating agents caused by shear forces accompanying the crystallization process during forming were evaluated by differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). The investigations of changes in the mechanism of interactions between silsesquioxane and commercial nucleating agents were supplemented by rheological analysis of crystallization. It was found that despite the differences in the chemical structure and solubility of the two nucleating agents, they influence the formation of the hexagonal iPP phase in a similar way, taking into consideration the shearing and cooling conditions. Full article

(This article belongs to the Special Issue Silsesquioxanes—Precursors to Functional Materials: Synthesis and Applications—a Themed Issue to Honor Professor Bogdan Marciniec on the Occasion of His 80th Birthday)

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11 pages, 3405 KiB

Open AccessArticle

Silsesquioxane-Based Triphenylamine-Linked Fluorescent Porous Polymer for Dyes Adsorption and Nitro-Aromatics Detection

by Qingzheng Wang, Masafumi Unno and Hongzhi Liu

Materials 2021, 14(14), 3851; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14143851 - 09 Jul 2021

Cited by 4 | Viewed by 2027

Abstract

In order to enrich hybrid materials, a novel fluorescent silsesquioxane-based polymer (denoted as PCS-OTS) was synthesized by Friedel-Crafts reaction starting from octavinylsilsesquioxane (OVS) with triphenylamine-functionalized silsesquioxane monomer (denoted as OTS) with AlCl₃ as catalyst. PCS-OTS possessed a high surface area of 816 m²/g and a unique bimodal pore structure. The triphenylamine unit endowed PCS-OTS with excellent luminescence, which made it act as a sensitive chemical sensor and detect p-nitrophenol with high sensitivity (K_SV = 81,230 M⁻¹). Moreover, PCS-OTS can significantly remove dyes, and the respective adsorption capacity for Rhodamine B (RB), Congo red (CR) and Methyl Orange (MO) is 1935, 1420 and 155 mg/g. Additionally, it could simultaneously remove multiple dyes from water by simple filtration and be easily regenerated. This hybrid porous polymer can be a good choice for water treatment. Full article

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13 pages, 7105 KiB

Open AccessArticle

Preparation of Soluble POSS-Linking Polyamide and Its Application in Antifogging Films

by Tomoya Kozuma, Aki Mihata and Yoshiro Kaneko

Materials 2021, 14(12), 3178; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14123178 - 09 Jun 2021

Cited by 11 | Viewed by 2950

Abstract

In this study, we prepared a polyhedral oligomeric silsesquioxane (POSS)-linking polyamide (POSS polyamide) by a polycondensation of ammonium-functionalized POSS (POSS-A) and carboxyl-functionalized POSS (POSS-C) in dehydrated dimethyl sulfoxide (DMSO) using 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) as condensing agents. The obtained POSS polyamide was soluble in various highly polar solvents, and it could form a self-standing film. FT-IR, ¹H NMR, and ²⁹Si NMR analyses showed that POSS polyamide is a polymer in which POSS-A and POSS-C are linked almost linearly by amide bonds. Furthermore, the cast film obtained by heat-treating the polymer at 150 °C for 30 min exhibited excellent transparency and hard-coating (pencil scratch test: 5H) and antifogging properties (evaluation by water vapor exposure). Full article

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10 pages, 5266 KiB

Open AccessCommunication

Vinyl-Functionalized Janus Ring Siloxane: Potential Precursors to Hybrid Functional Materials

by Thanawat Chaiprasert, Yujia Liu, Nobuhiro Takeda and Masafumi Unno

Materials 2021, 14(8), 2014; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14082014 - 16 Apr 2021

Cited by 11 | Viewed by 2280

Abstract

A vinyl-functionalized all-cis-tetrasiloxycyclotetrasiloxane [ViSi(OSiMe₂H)O]₄ (Vi = vinyl group) Janus precursor was prepared from potassium cyclotetrasiloxane silanolate. The Janus precursor was selectively modified at its dimethylhydrosilyl groups [–SiMe₂H] via the Piers–Rubinsztajn reaction to obtain a family of new tetravinyl-substituted Janus rings [ViSi(OR’)O]₄ containing various functional groups in moderate yields. Remarkably, the tetravinyl groups on the structure remained intact after modification by the Piers–Rubinsztajn reaction. Since these synthesized compounds possess multiple functional groups (up to eight per molecule), they are potential precursors for advanced hybrid organic-inorganic functional materials. Full article

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16 pages, 3307 KiB

Open AccessArticle

Polysiloxanes Grafted with Mono(alkenyl)Silsesquioxanes—Particular Concept for Their Connection

by Katarzyna Mituła, Julia Duszczak, Monika Rzonsowska, Patrycja Żak and Beata Dudziec

Materials 2020, 13(21), 4784; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13214784 - 26 Oct 2020

Cited by 10 | Viewed by 2131

Abstract

Herein, a facile and efficient synthetic route to unique hybrid materials containing polysiloxanes and mono(alkyl)silsesquioxanes as their pendant modifiers (T₈@PS) was demonstrated. The idea of this work was to apply the hydrosilylation reaction as a tool for the efficient and selective attachment of mono(alkenyl)substituted silsesquioxanes (differing in the alkenyl chain length, from -vinyl to -dec-9-enyl and types of inert groups iBu, Ph at the inorganic core) onto two polysiloxanes containing various amount of Si-H units. The synthetic protocol, determined and confirmed by FT-IR in situ and NMR analyses, was optimized to ensure complete Si-H consumption along with the avoidance of side-products. A series of 20 new compounds with high yields and complete β-addition selectivity was obtained and characterized by spectroscopic methods. Full article

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13 pages, 2258 KiB

Open AccessFeature PaperArticle

Formation of Bifunctional Octasilsesquioxanes via Silylative Coupling and Cross-Metathesis Reaction

by Małgorzata Bołt, Patrycja Żak, Beata Dudziec, Anna Schulmann and Bogdan Marciniec

Materials 2020, 13(18), 3966; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13183966 - 08 Sep 2020

Cited by 5 | Viewed by 1945

Abstract

Bifunctional silsesquioxanes create an attractive group of compounds with a wide range of potential applications, and recently they have gained much interest. They are known to be obtained mainly via hydrosilylation, but we disclose novel synthetic protocols based on different but complementary reactions, i.e., cross-metathesis (CM) and silylative coupling (SC). A series of cubic T₈ type silsesquioxane derivatives with a broad scope of styryl substituents were synthesized in a one-pot procedure and characterized by spectroscopic and spectrometric methods. All of the new compounds can be obtained in a one-pot manner, which has an attractive impact on the synthetic procedure, as it is economic in terms of the isolation of intermediate products. Additionally, the methodology disclosed here enables the (E)-stereoselective introduction of styrenes derivative to the cubic T₈ type core. The presented compounds can be interesting precursors for a further functionalization that may significantly increase the possibility of their application in the design and synthesis of new functional materials. Full article

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15 pages, 7694 KiB

Open AccessArticle

Tunable Crystalline Phases in UV-Curable PEG-Grafted Ladder-Structured Silsesquioxane/Polyimide Composites

by Ryung Il Kim, Ju Ho Shin, Jong Suk Lee, Jung-Hyun Lee, Albert S. Lee and Seung Sang Hwang

Materials 2020, 13(10), 2295; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13102295 - 15 May 2020

Cited by 4 | Viewed by 2779

Abstract

A series of UV-curable hybrid composite blends containing a carboxylic acid functionalized polyimidewith varying amounts of high molecular weight (~1 K) PEG-grafted ladder-structured polysilsesquioxanes copolymerized with methacryl groups were fabricated and their structural, thermal, mechanical, and surface properties characterized. At a composite weight ratio of polyimide above 50 wt.%, a stark shift from amorphous to crystalline polyethylene glycol (PEG) phases were observed, accompanied by a drastic increase in both surface moduli and brittleness index. Moreover, fabricated composites were shown to have a wide range water contact angle, 9.8°–73.8°, attesting to the tunable surface properties of these amphiphilic hybrid polymer composites. The enhanced mechanical properties, combined with the utility of tunable surface hydrophilicity allows for the possible use of these hybrid polymer composites to be utilized as photosensitive polyimide negative photoresists for a myriad of semiconductor patterning processes. Full article

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13 pages, 3570 KiB

Open AccessArticle

R-Silsesquioxane-Based Network Polymers by Fluoride Catalyzed Synthesis: An Investigation of Cross-Linker Structure and Its Influence on Porosity

by Nai-hsuan Hu and Joseph C. Furgal

Materials 2020, 13(8), 1849; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13081849 - 15 Apr 2020

Cited by 4 | Viewed by 2240

Abstract

Silsesquioxane-based networks are an important class of materials that have many applications where high thermal/oxidative stability and porosity are needed simultaneously. However, there is a great desire to be able to design these materials for specialized applications in environmental remediation and medicine. To do so requires a simple synthesis method to make materials with expanded functionalities. In this article, we explore the synthesis of R-silsesquioxane-based porous networks by fluoride catalysis containing methyl, phenyl and vinyl corners (R-Si(OEt)₃) combined with four different bis-triethoxysilyl cross-linkers (ethyl, ethylene, acetylene and hexyl). Synthesized materials were then analyzed for their porosity, surface area, thermal stability and general structure. We found that when a specified cage corner (i.e., methyl) is compared across all cross-linkers in two different solvent systems (dichloromethane and acetonitrile), pore size distributions are consistent with cross-linker length, pore sizes tended to be larger and π-bond-containing cross-linkers reduced overall microporosity. Changing to larger cage corners for each of the cross-linkers tended to show decreases in overall surface area, except when both corners and cross-linkers contained π-bonds. These studies will enable further understanding of post-synthesis modifiable silsesquioxane networks. Full article

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Review

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25 pages, 2403 KiB

Open AccessReview

Application of Silsesquioxanes in the Preparation of Polyolefin-Based Materials

by Marzena Białek and Krystyna Czaja

Materials 2023, 16(5), 1876; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16051876 - 24 Feb 2023

Cited by 1 | Viewed by 1368

Abstract

This paper is a review of studies on the use of the polyhedral oligomeric silsesquioxanes (POSS) of various structures in the synthesis of polyolefins and the modification of their properties, namely: (1) components of organometallic catalytic systems for the polymerization of olefins, (2) comonomers in the copolymerization with ethylene, and (3) fillers in composites based on polyolefins. In addition, studies on the use of new silicon compounds, i.e., siloxane–silsesquioxane resins, as fillers for composites based on polyolefins are presented. The authors dedicate this paper to Professor Bogdan Marciniec on the occasion of his jubilee. Full article

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18 pages, 1678 KiB

Open AccessReview

Silsesquioxanes in the Cosmetics Industry—Applications and Perspectives

by Anna Olejnik, Bogna Sztorch, Dariusz Brząkalski and Robert E. Przekop

Materials 2022, 15(3), 1126; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15031126 - 31 Jan 2022

Cited by 8 | Viewed by 4496

Abstract

The rising demand for innovative and sophisticated personal care products is a driving factor for manufacturers to obtain new formulations that will fulfill the customers’ preferences. In recent years, silsesquioxanes have attracted the attention of the cosmetics industry. These compounds have been proposed to be used in novel cosmetic formulations as emollient, dispersant, and viscosity modifiers. Therefore, this publication aims to review the main important aspects of polyhedral oligosilsesquioxanes as ingredients of personal care formulations, taking into consideration different types of products. The methods of obtaining these compounds were also presented. Additionally, the detailed analysis of patents dedicated to the application of silsesquioxanes in cosmetic formulations was also performed. Full article

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Silsesquioxanes—Precursors to Functional Materials: Synthesis and Applications—a Themed Issue to Honor Professor Bogdan Marciniec on the Occasion of His 80th Birthday

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