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Organosilicon Polymers: From New Structures towards New Properties

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

Deadline for manuscript submissions: closed (20 March 2022) | Viewed by 17030

Special Issue Editor


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Guest Editor
A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 28 Vavilova St., GSP-1, V-334, 119991 Moscow, Russia
Interests: new polymeric forms; structure–properties relationship; supramolecular organization; organosilicon compounds; hybrid organic-inorganic structures; active media concept; organoalkoxysilanes; chlorine-free technology; functional metallosiloxanes; dendrimers; hyperbranched polymers; highly crosslinked nanogels; multiarm stars; macromolecular brushes
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Special Issue Information

Dear Colleague,

Organosilicon polymers, confidently standing on the basis of the endless supply of silica and renewable organics, maintain sustainable growth over a long time. This is primarily due to the complexity of the unique properties inherent in polydimethylsiloxane and the huge variety of its forms. In recent decades, considerable progress has been achieved in the creation of organosilicon polymers of a well-defined structure thanks to the development of new synthetic methods based on the unique properties of organosilicon reagents, catalytic systems, and amazing reactions.

A separate area in the structural diversity of organosilicon polymers belongs to polyorganosilsesquioxanes. Numerous hyperbranched structures and nanogels have made it possible to open up the walls of the sol-gel synthesis “black box” and to obtain a whole series of new molecular nanofluids and nanoscale fillers with the properties controlled in the coordinates of a macromolecule-particle, i.e., slow and gradual transformation of the hyperbranched macromolecule into a colloidal particle. Another variation of a similar process has obtained light and transparent aerogels, demonstrating substantial flexibility. The ongoing development of the chemistry of ladder polyphenylsilsesquioxanes is also worth mentioning.

The potential of silicone polymers to produce hybrid organoelement structures has also increased. Entire sets of linear, branched, polycyclic, and dendritic carborane-containing polysiloxanes are nothing more than prefabricated building blocks for new hybrid molecular composites. In addition to the unique stereoregular metallosiloxane scaffolds, numerous types of branched functional metallosiloxane oligomers were synthesized that demonstrate remarkable progress in regulating properties of their interpenetrating networks with liquid silicone resins.

Despite the fact that organosilicon polymers later moved to the sufficient level of controlling properties by controlling the structure, the unique possibilities of combining silicone and organofunctional reagents have not only allowed organosilicon polymers to catch up, but also to take a leading position in a number of development areas.

In this Special Issue, we will present a snapshot of this rapidly developing field to inspire scientists working in this and related areas and to draw attention to new unique opportunities for cooperation in this fascinating field.

Dr. Aziz Mansurovich Muzafarov
Guest Editor

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Keywords

  • Organosilicon polymers
  • Structure–properties relationship
  • Carbosilane dendrimers
  • Organosilicon dendrimers
  • Hyperbranched polymers
  • Dense molecular brushes 
  • Multiarm stars
  • Nanogels
  • Polyorganosilsesquioxanes
  • Ladder polyphenylsilsesquioxanes
  • Carborane-containing polysiloxanes
  • Functional metallosiloxane oligomers
  • Stereoregular metallosiloxanes

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Published Papers (5 papers)

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Research

16 pages, 5166 KiB  
Article
A Versatile Equilibrium Method for the Synthesis of High-Strength, Ladder-like Polyphenylsilsesquioxanes with Finely Tunable Molecular Parameters
by Tatyana O. Ershova, Anton A. Anisimov, Maxim N. Temnikov, Maxim A. Novikov, Mikhail I. Buzin, Galina G. Nikiforova, Yulia S. Dyuzhikova, Ivan E. Ushakov, Olga I. Shchegolikhina and Aziz M. Muzafarov
Polymers 2021, 13(24), 4452; https://doi.org/10.3390/polym13244452 - 18 Dec 2021
Cited by 12 | Viewed by 3260
Abstract
A versatile equilibrium method for synthesizing ladder-like polyphenylsilsesquioxanes (L-PPSQs) with various molecular weights (from 4 to 500 kDa) in liquid ammonia was developed. The effect of diverse parameters, such as temperature, monomer concentration, reaction time, addition or removal of water from the reaction [...] Read more.
A versatile equilibrium method for synthesizing ladder-like polyphenylsilsesquioxanes (L-PPSQs) with various molecular weights (from 4 to 500 kDa) in liquid ammonia was developed. The effect of diverse parameters, such as temperature, monomer concentration, reaction time, addition or removal of water from the reaction medium, on the polycondensation process was determined. The molecular weight characteristics and structure of the L-PPSQ elements obtained were determined by GPC, 1H, 29Si NMR, IR spectroscopy, viscometry, and PXRD methods. The physicochemical properties of L-PPSQs were determined by TGA and mechanical analyses. Full article
(This article belongs to the Special Issue Organosilicon Polymers: From New Structures towards New Properties)
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19 pages, 8799 KiB  
Article
Phase Structure and Properties of Ternary Polylactide/Poly(methyl methacrylate)/Polysilsesquioxane Blends
by Anna Kowalewska, Agata S. Herc, Joanna Bojda, Maria Nowacka, Mariia Svyntkivska, Ewa Piorkowska, Witold Kaczorowski and Witold Szymański
Polymers 2021, 13(7), 1033; https://doi.org/10.3390/polym13071033 - 26 Mar 2021
Cited by 2 | Viewed by 3095
Abstract
Ternary blends of polylactide (PLA, 90 wt.%) and poly(methyl methacrylate) (PMMA, 10 wt.%) with functionalized polysilsesquioxanes (LPSQ-R) were obtained by solution blending. R groups in LPSQ containing hydroxyethyl (LPSQ-OH), methylglycolic (LPSQ-COOMe) and pentafluorophenyl (LPSQ-F5) moieties of different chemical properties were designed to modify [...] Read more.
Ternary blends of polylactide (PLA, 90 wt.%) and poly(methyl methacrylate) (PMMA, 10 wt.%) with functionalized polysilsesquioxanes (LPSQ-R) were obtained by solution blending. R groups in LPSQ containing hydroxyethyl (LPSQ-OH), methylglycolic (LPSQ-COOMe) and pentafluorophenyl (LPSQ-F5) moieties of different chemical properties were designed to modify PLA blends with PMMA. The effect of the type of LPSQ-R and their content, 1–3 wt.%, on the structure of the blends was studied with scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (SEM-EDS), dynamic mechanical thermal analysis (DMTA) and Raman spectroscopy. Differential scanning calorimetry (DSC) and tensile tests also showed various effects of LPSQ-R on the thermal and mechanical properties of the blends. Depth-sensing indentation was used to resolve spatially the micro- and nano-scale mechanical properties (hardness and elastic behaviour) of the blends. The results showed clearly that LPSQ-R modulate the structure and properties of the blends. Full article
(This article belongs to the Special Issue Organosilicon Polymers: From New Structures towards New Properties)
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16 pages, 3457 KiB  
Article
Spatially Controlled Highly Branched Vinylsilicones
by Mengchen Liao, Yang Chen and Michael A. Brook
Polymers 2021, 13(6), 859; https://doi.org/10.3390/polym13060859 - 11 Mar 2021
Cited by 4 | Viewed by 2525
Abstract
Branched silicones possess interesting properties as oils, including their viscoelastic behavior, or as precursors to controlled networks. However, highly branched silicone polymers are difficult to form reliably using a “grafting to” strategy because functional groups may be bunched together preventing complete conversion for [...] Read more.
Branched silicones possess interesting properties as oils, including their viscoelastic behavior, or as precursors to controlled networks. However, highly branched silicone polymers are difficult to form reliably using a “grafting to” strategy because functional groups may be bunched together preventing complete conversion for steric reasons. We report the synthesis of vinyl-functional highly branched silicone polymers based, at their core, on the ability to spatially locate functional vinyl groups along a silicone backbone at the desired frequency. Macromonomers were created and then polymerized using the Piers–Rubinsztajn reaction with dialkoxyvinylsilanes and telechelic HSi-silicones; molecular weights of the polymerized macromonomers were controlled by the ratio of the two reagents. The vinyl groups were subjected to iterative (two steps, one pot) hydrosilylation with alkoxysilane and Piers–Rubinsztajn reactions, leading to high molecular weight, highly branched silicones after one or two iterations. The vinyl-functional products can optionally be converted to phenyl/methyl-modified branched oils or elastomers. Full article
(This article belongs to the Special Issue Organosilicon Polymers: From New Structures towards New Properties)
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15 pages, 2908 KiB  
Article
Hybrid Polycarbosilane-Siloxane Dendrimers: Synthesis and Properties
by Sergey A. Milenin, Elizaveta V. Selezneva, Pavel A. Tikhonov, Viktor G. Vasil’ev, Alexander I. Buzin, Nikolay K. Balabaev, Andrey O. Kurbatov, Maxim V. Petoukhov, Eleonora V. Shtykova, Lev A. Feigin, Elena A. Tatarinova, Elena Yu. Kramarenko, Sergey N. Chvalun and Aziz M. Muzafarov
Polymers 2021, 13(4), 606; https://doi.org/10.3390/polym13040606 - 17 Feb 2021
Cited by 19 | Viewed by 4627
Abstract
A series of carbosilane dendrimers of the 4th, 6th, and 7th generations with a terminal trimethylsilylsiloxane layer was synthesized. Theoretical models of these dendrimers were developed, and equilibrium dendrimer conformations obtained via molecular dynamics simulations were in a good agreement with experimental small-angle [...] Read more.
A series of carbosilane dendrimers of the 4th, 6th, and 7th generations with a terminal trimethylsilylsiloxane layer was synthesized. Theoretical models of these dendrimers were developed, and equilibrium dendrimer conformations obtained via molecular dynamics simulations were in a good agreement with experimental small-angle X-ray scattering (SAXS) data demonstrating molecule monodispersity and an almost spherical shape. It was confirmed that the glass transition temperature is independent of the dendrimer generation, but is greatly affected by the chemical nature of the dendrimer terminal groups. A sharp increase in the zero-shear viscosity of dendrimer melts was found between the 5th and the 7th dendrimer generations, which was qualitatively identical to that previously reported for polycarbosilane dendrimers with butyl terminal groups. The viscoelastic properties of high-generation dendrimers seem to follow some general trends with an increase in the generation number, which are determined by the regular branching structure of dendrimers. Full article
(This article belongs to the Special Issue Organosilicon Polymers: From New Structures towards New Properties)
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18 pages, 2606 KiB  
Article
Adsorption of Silicon-Containing Dendrimers: Effects of Chemical Composition, Structure, and Generation Number
by Andrey O. Kurbatov, Nikolay K. Balabaev, Mikhail A. Mazo and Elena Yu. Kramarenko
Polymers 2021, 13(4), 552; https://doi.org/10.3390/polym13040552 - 13 Feb 2021
Cited by 3 | Viewed by 1894
Abstract
We studied the conformational behavior of silicon-containing dendrimers during their adsorption onto a flat impenetrable surface by molecular dynamics (MD) simulations. Four homologous series of dendrimers from the 4th up to the 7th generations were modeled, namely, two types of carbosilane dendrimers differing [...] Read more.
We studied the conformational behavior of silicon-containing dendrimers during their adsorption onto a flat impenetrable surface by molecular dynamics (MD) simulations. Four homologous series of dendrimers from the 4th up to the 7th generations were modeled, namely, two types of carbosilane dendrimers differing by the functionality of the core Si atom and two types of siloxane dendrimers with different lengths of the spacers. Comparative analysis of the fractions of adsorbed atoms belonging to various structural layers within dendrimers as well as density profiles allowed us to elucidate not only some general trends but also the effects determined by dendrimer specificity. In particular, it was found that in contrast to the carbosilane dendrimers interacting with the adsorbing surface mainly by their peripheral layers, the siloxane dendrimers with the longer –O–Si(CH3)2–O spacers expose atoms from their interior to the surface spreading out on it. These findings are important for the design of functional materials on the basis of silicon-containing dendrimers. Full article
(This article belongs to the Special Issue Organosilicon Polymers: From New Structures towards New Properties)
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