New types of hyperbranched 1,2,3-triazole-alkoxysiloxane functional polymers for metal embedded nanocomposite surface coatings.

In this study, using the "click-chemistry" azide-alkyne cycloaddition reaction, two new types of polymers, namely, water-soluble amine-functional and water-insoluble pyridine-functional hyperbranched 1,2,3-triazoleorganoethoxysiloxane polymers, capable of stabilizing ultra-small silver nanoparticles and efficient for chemical surface modification were synthesized and characterized by 1H-NMR, 13C-NMR, 29Si-NMR and FT-IR spectroscopy, MALDI and GPC. Coordinatively active hetero-organic polymers with a flexible branched polyethoxysiloxane backbone bearing chelating 1,2,3-triazolyl-dimethylamine and -pyridine conjugated functional groups were exploited towards coordination with Ag+ metal ions, and formation and stabilization of narrowly dispersed silver nanoparticles (Ag-NPs) obtained in the process of radiation induced metal ion reduction. The influence of the chemically assisted radiation process on the Ag-NP size and size distribution was investigated. Hyperbranched polyorganoethoxysiloxanes loaded with Ag-NPs were covalently cross-linked on a Stöber silica surface, demonstrating the efficiency of the developed hetero-organic functional polymers in the preparation of functional nanocomposite coatings for various applications (heterogeneous catalytic systems, antibacterial materials, nanoparticle-based optical sensing devices, etc.). The nanocomposites were investigated and characterized by TEM-EDS, DLS, UV-Vis spectroscopy and 29Si MAS NMR spectroscopy.

Synthesis of Vinyl-Containing Polydimethylsiloxane in An Active Medium.

This research deals with the synthesis of copoly(methylvinyl)(dimethyl)siloxanes by the copolycondensation of dimethyldiethoxy- and methylvinyldimethoxysilane in an active medium, followed by thermal condensation in a vacuum. We achieved a range of copolymers exhibiting finely tuned molecular weights spanning between 1500 and 20,000 with regulated functional methylvinylsiloxane units. Analysis of the microstructure showed that the copolymerization predominantly formed products demonstrating a random distribution of units (R~1). However, an increase in the content of vinyl-containing monomers increases the R parameter, indicating an enhanced tendency towards alternating linkages within the copolymer matrix.

Thioether-Containing Zirconium(Alkoxy)Siloxanes: Synthesis and Study of Dielectric and Mechanical Properties of Silica-Filled Polydimethylsiloxane Compositions Cured by Them.

A number of thioether-containing zirconium siloxanes, differing in their composition and metal atom shielding degree with a siloxy substituent, were synthesized and characterized. Synthesis of such compounds made it possible to evaluate the effect of sulfur atoms' presence in the cured compositions on their dielectric properties, as well as to evaluate their curing ability and influence on mechanical characteristics compared to the sulfur-free analogs obtained earlier. Studying a wide range of compositions differing in their content and ratio of metallosiloxane and silica components revealed that such systems are still typical dielectrics. At the same time, the introduction of thioether groups can provide increased dielectric constant and conductivity in comparison with previously obtained sulfur-free similar compositions in the <102 Hz frequency range (dielectric constant up to ~10-30 at frequency range 1-10 Hz). As before, the dielectric parameters increase is directly determined by the silica component proportion in the cured material. It is also shown that varying sulfur-containing zirconium siloxanes structure and functionality and its combination with previously obtained sulfur-free analogs, along with varying the functionality and rubber chain length, can be an effective tool for changing the dielectric and mechanical material parameters in a wide range (tensile strength 0.5-7 Mpa, elastic deformation 2-300%), which determine the prospects for the use of such cured systems as dielectric elastomers for various purposes.

True Molecular Composites: Unusual Structure and Properties of PDMS-MQ Resin Blends.

Poly(dimethyl siloxane)-MQ rubber molecular composites are easy to prepare, as it does not require a heterophase mixing of ingredients. They are characterized by perfect homogeneity, so they are very promising as rubber materials with controllable functional characteristics. The manuscript reveals that MQ resin particles can significantly, more than by two orders of magnitude, enhance the mechanical properties of poly(dimethyl siloxane), and, as fillers, they are not inferior to aerosils. In the produced materials, MQ particles play a role of the molecular entanglements, so rubber molecular weight and MQ filler concentration are the parameters determining the structure and properties of such composites. Moreover, a need for a saturation of the reactive groups and minimization of the surface energy of MQ particles also determine the size and distribution of the filler at different filler rates. An unusual correlation of the concentration of MQ component and the interparticle spacing was revealed. Based on the extraordinary mechanical properties and structure features, a model of the structure poly(dimethyl siloxane)-rubber molecular composites and of its evolution in the process of stretching, was proposed.

New Principles of Polymer Composite Preparation. MQ Copolymers as an Active Molecular Filler for Polydimethylsiloxane Rubbers.

Colorless transparent vulcanizates of silicone elastomers were prepared by mixing the components in a common solvent followed by solvent removal. We studied the correlation between the mechanical behavior of polydimethylsiloxane (PDMS)-rubber compositions prepared using MQ (mono-(M) and tetra-(Q) functional siloxane) copolymers with different ratios of M and Q parts as a molecular filler. The composition and molecular structure of the original rubber, MQ copolymers, and carboxyl-containing PDMS oligomers were also investigated. The simplicity of the preparation of the compositions, high strength and elongation at break, and their variability within a wide range allows us to consider silicone elastomers as a promising alternative to silicone materials prepared by traditional methods.