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Recent Advances in the Synthesis and Application of Polysiloxanes

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

Deadline for manuscript submissions: closed (31 July 2023) | Viewed by 24401

Special Issue Editors


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Guest Editor
Enikolopov Institute of Synthetic Polymeric Materials of Russian Academy of Sciences (ISPM RAS), 117393 Moscow, Russia
Interests: functional polysiloxanes; carbosilane dendrimers; Janus dendrimers; hydrophobic siloxanes; antibacterial siloxanes; renewable polymers
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Guest Editor
Enikolopov Institute of Synthetic Polymeric Materials of Russian Academy of Sciences (ISPM RAS), 117393 Moscow, Russia
Interests: polydimethylsiloxanes; siloxane polymers; polyorganosiloxanes; dendrimers; hybrid dendrimers; carbosilane dendrimers; functional polymers; hybrid copolymers
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

This Special Issue is devoted to a discussion regarding new strategies and recent advances in the synthesis of polysiloxanes, as well as their new applications, in the possession of a long history. In 2021, the term "silicone" turned exactly 120 years old, formerly proposed by F. Kipping, now, polyorganosiloxanes being the most important large-scale polymer. However, the topic of the synthesis and application of those already mentioned, as well as new, polysiloxanes is still relevant, and the search for new green methods for their fabrication has become an extremely important task, the demand for new functional siloxane polymers and copolymers with different architectures presently growing. Thanks to the synthesis of such polymers, it became possible to develop new materials with unique properties, which will undoubtedly bring polyorganosiloxanes to a new level of development.

We invite you to participate in this Special Issue, sharing your latest achievements in this field, vision of the current trend and evaluating the work of your colleagues.

Sincerely,
Dr. Fedor V. Drozdov
Dr. Sergey A. Milenin
Guest Editors 

Manuscript Submission Information

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Keywords

  • polysiloxanes
  • silicone
  • PDMS
  • organosilicon chemistry
  • organosilicon polymers

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Published Papers (6 papers)

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Research

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13 pages, 4672 KiB  
Article
Synthesis of Multifunctional Oligomethylsilsesquioxanes by Catalyst-Free Hydrolytic Polycondensation of Methyltrimethoxysilane under Microwave Radiation
by Alexandra A. Kalinina, Olga B. Gorbatsevich, Nikita G. Yakhontov, Nina V. Demchenko, Nataliya G. Vasilenko, Valentina V. Kazakova and Aziz M. Muzafarov
Polymers 2023, 15(2), 291; https://doi.org/10.3390/polym15020291 - 6 Jan 2023
Cited by 2 | Viewed by 1442
Abstract
The catalyst-free hydrolytic polycondensation of methyltrimethoxysilane under microwave radiation has been studied. The effect of molar ratios of the reagents (MTMS/H2O = 1/0.5–1/9), radiation power (20–300 W), temperature (30–50 °C) and duration of exposure (2.5–90 min) on the course of the [...] Read more.
The catalyst-free hydrolytic polycondensation of methyltrimethoxysilane under microwave radiation has been studied. The effect of molar ratios of the reagents (MTMS/H2O = 1/0.5–1/9), radiation power (20–300 W), temperature (30–50 °C) and duration of exposure (2.5–90 min) on the course of the process is considered. It has been shown that the use of microwave radiation promotes the activation of the process, and almost complete conversion of the monomer can be achieved in 5 min at 30 °C, 20 W and an MTMS/H2O ratio of 1/3. The optimal radiation power for the maximum conversion of the monomer and MeO-groups is in the range from 20 to 100 W. An increase in the water amount, the duration and temperature of the process contribute to an increase in the monomer conversion, a decrease in the content of residual MeO-groups and the yield of non-volatile oligomethylsilsesquioxanes. The limits of this approach using to the synthesis of multifunctional branched polyorganosilsesquioxanes are determined. Depending on the process conditions, homogeneous water–alcohol solutions of oligomethylsilsesquioxane with a concentration of 20 to 50 wt.% can be obtained. The OH-group content and the molecular weight of the obtained oligomers vary from 10 to 30 wt.% and from 1000 to 600 Da, respectively. Full article
(This article belongs to the Special Issue Recent Advances in the Synthesis and Application of Polysiloxanes)
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16 pages, 1662 KiB  
Article
A Polysiloxane Delivery Vehicle of Cyclic N-Halamine for Biocidal Coating of Cellulose in Supercritical CO2
by Leixuan Li, Yan Xin, Fengze Wu, Xiangrong Lyu, Qiyuan Yao, Xiaoting Yin, Qiang Zhang, Wenjuan Shan, Yong Chen and Qiuxia Han
Polymers 2022, 14(23), 5080; https://doi.org/10.3390/polym14235080 - 23 Nov 2022
Cited by 1 | Viewed by 1302
Abstract
Cyclic N-halamines are highly antimicrobial, very stable, and not susceptible to bacterial resistance. A polysiloxane delivery vehicle was synthesized to deliver cyclic imide N-halamine onto cellulose via a benign and universal procedure that does not require a harmful solvent or chemical [...] Read more.
Cyclic N-halamines are highly antimicrobial, very stable, and not susceptible to bacterial resistance. A polysiloxane delivery vehicle was synthesized to deliver cyclic imide N-halamine onto cellulose via a benign and universal procedure that does not require a harmful solvent or chemical bonding. In brief, Knoevenagel condensation between barbituric acid and 4-hydroxybenzaldehyde furnished 5-(4-hydroxybenzylidene)pyrimidine-2,4,6-trione, whose phenolic O−H was subsequently reacted with the Si−H of poly(methylhydrosiloxane) (PMHS) via silane alcoholysis. The product of silane alcoholysis was interpenetrated into cellulose in supercritical CO2 (scCO2) at 50 °C, to form a continuous modification layer. The thickness of the modification layer positively correlated with interpenetration pressure in the experimental range of 10 to 28 MPa and reached a maximum value of 76.5 nm, which demonstrates the ability for tunable delivery, to control the loading of the imide N−H bond originating from barbituric acid unit. The imide N−H bonds on cellulose with the thickest modifier were then chlorinated into N−Cl counterparts using tert-butyl hypochlorite, to exert a powerful biocidability, providing ~7 log reductions of both S. aureus and E. coli in 20 min. The stability and rechargeability of the biocidability were both very promising, suggesting that the polysiloxane modifier has a satisfactory chemical structure and interlocks firmly with cellulose via scCO2 interpenetration. Full article
(This article belongs to the Special Issue Recent Advances in the Synthesis and Application of Polysiloxanes)
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25 pages, 6558 KiB  
Article
Cross-Linked Luminescent Polymers Based on β-Diketone-Modified Polysiloxanes and Organoeuropiumsiloxanes
by Eleonora E. Kim, Yuriy N. Kononevich, Yulia S. Dyuzhikova, Dmitry S. Ionov, Dmitry A. Khanin, Galina G. Nikiforova, Olga I. Shchegolikhina, Viktor G. Vasil’ev and Aziz M. Muzafarov
Polymers 2022, 14(13), 2554; https://doi.org/10.3390/polym14132554 - 23 Jun 2022
Cited by 8 | Viewed by 2168
Abstract
Nowadays, luminescent materials attract wide attention due to their valuable characteristics and broad area of potential application. Luminescent silicone-based polymers possess unique properties, such as flexibility, hydrophobicity, thermal and chemical stabilities, etc., which allow them to be utilized in various fields, such as [...] Read more.
Nowadays, luminescent materials attract wide attention due to their valuable characteristics and broad area of potential application. Luminescent silicone-based polymers possess unique properties, such as flexibility, hydrophobicity, thermal and chemical stabilities, etc., which allow them to be utilized in various fields, such as optoelectronics, solid-state lasers, luminescent solar concentrators, sensors, and others. In the present work, a metal-ligand interaction approach was applied to obtain new cross-linked luminescent polymers based on multiligand polysiloxanes with grafted β-diketone fragments and organoeuropiumsiloxanes containing various organic substituents. Organoeuropiumsiloxanes were utilized as a source of Eu3+ ions due to their compatibility with the silicon matrix. All synthesized polymers were fully characterized and their physicochemical, mechanical, self-healing, optical, and thermal properties were studied. Full article
(This article belongs to the Special Issue Recent Advances in the Synthesis and Application of Polysiloxanes)
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Review

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35 pages, 17554 KiB  
Review
The Use of the Thiol-Ene Addition Click Reaction in the Chemistry of Organosilicon Compounds: An Alternative or a Supplement to the Classical Hydrosilylation?
by Ilya Krizhanovskiy, Maxim Temnikov, Yuriy Kononevich, Anton Anisimov, Fedor Drozdov and Aziz Muzafarov
Polymers 2022, 14(15), 3079; https://doi.org/10.3390/polym14153079 - 29 Jul 2022
Cited by 16 | Viewed by 8116
Abstract
This review presents the main achievements in the use of the thiol-ene reaction in the chemistry of silicones. Works are considered, starting from monomers and ending with materials.The main advantages and disadvantages of this reaction are demonstrated using various examples. A critical analysis [...] Read more.
This review presents the main achievements in the use of the thiol-ene reaction in the chemistry of silicones. Works are considered, starting from monomers and ending with materials.The main advantages and disadvantages of this reaction are demonstrated using various examples. A critical analysis of the use of this reaction is made in comparison with the hydrosilylation reaction. Full article
(This article belongs to the Special Issue Recent Advances in the Synthesis and Application of Polysiloxanes)
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34 pages, 13992 KiB  
Review
Ring-Opening Polymerization (ROP) and Catalytic Rearrangement as a Way to Obtain Siloxane Mono- and Telechelics, as Well as Well-Organized Branching Centers: History and Prospects
by Kseniya A. Bezlepkina, Sergey A. Milenin, Natalia G. Vasilenko and Aziz M. Muzafarov
Polymers 2022, 14(12), 2408; https://doi.org/10.3390/polym14122408 - 14 Jun 2022
Cited by 12 | Viewed by 7519
Abstract
PDMS telechelics are important both in industry and in academic research. They are used both in the free state and as part of copolymers and cross-linked materials. At present, the most important, practically used, and well-studied method for the preparation of such PDMS [...] Read more.
PDMS telechelics are important both in industry and in academic research. They are used both in the free state and as part of copolymers and cross-linked materials. At present, the most important, practically used, and well-studied method for the preparation of such PDMS is diorganosiloxane ring-opening polymerization (ROP) in the presence of nucleophilic or electrophilic initiators. In our brief review, we reviewed the current advances in the field of obtaining polydiorganosiloxane telechelics and monofunctional PDMS, as well as well-organized branching centers by the ROP mechanism and catalytic rearrangement, one of the first and most important reactions in the polymer chemistry of silicones, which remains so at the present time. Full article
(This article belongs to the Special Issue Recent Advances in the Synthesis and Application of Polysiloxanes)
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18 pages, 2839 KiB  
Review
Organosilicone Compounds in Supercritical Carbon Dioxide
by Victor E. Sizov, Vadim V. Zefirov, Marat O. Gallyamov and Aziz M. Muzafarov
Polymers 2022, 14(12), 2367; https://doi.org/10.3390/polym14122367 - 11 Jun 2022
Cited by 6 | Viewed by 2676
Abstract
This review considers the key advantages of using supercritical carbon dioxide as a solvent for systems with organosilicon compounds. Organosilicon polymeric materials synthesis as well as the creation and modification of composites based on them are discussed. Polydimethylsiloxane and analogues used as polymerization [...] Read more.
This review considers the key advantages of using supercritical carbon dioxide as a solvent for systems with organosilicon compounds. Organosilicon polymeric materials synthesis as well as the creation and modification of composites based on them are discussed. Polydimethylsiloxane and analogues used as polymerization stabilizers and nucleation promoters in pore formation processes are analyzed as well. Full article
(This article belongs to the Special Issue Recent Advances in the Synthesis and Application of Polysiloxanes)
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