Search Results (45)

The interest in macromolecular alkoxysilyl-functionalized hybrids (self-assembling or nanostructured), which could be used as precursors in biomimetic silica precipitation and for the synthesis of hollow spherical silica particles, is growing. Nevertheless, reports on all-organosilicon systems for bioinspired silica precipitation are scarce. Therefore, a new kind of polyalkoxysilane macromonomer–linear polysilsesquioxane (LPSQ) of ladder-like backbone, functionalized in side chains with trimethoxysilyl groups (LPSQ-R-Si(OMe)₃), was designed following this approach. It was obtained by photoinitiated thiol-ene addition of 3-mercaptopropyltrimethoxysilane to the vinyl-functionalized polysilsesquioxane precursor, carried out in situ in tetraethoxysilane (TEOS). The mixture of LPSQ-R-Si(OMe)₃ and TEOS (co-monomers) was used in a sol–gel process conducted under acidic conditions (0.5 M HCl/NaCl) in the presence of Pluronic^® F-127 triblock copolymer as a template. LPSQ-R-Si(OMe)₃ played a key role for the formation of microparticles of a spherical shape that were formed under the applied conditions, while their size (as low as 3–4 µm) was controlled by the stirring rate. The hybrid materials were hydrophobic and showed good thermal and oxidative stability. Introduction of zinc acetate (Zn(OAc)₂) as an additive in the sol–gel process influenced the pH of the reaction medium, which resulted in structural reinforcement of the hybrid microparticles owing to more effective condensation of silanol groups and a relative increase of the content of SiO₂. The proposed method shows directions in designing the properties of hybrid materials and can be translated to other silicon–organic polymers and oligomers that could be used to produce hollow silica particles. The established role of various factors (macromonomer structure, pH, and stirring rate) allows for the modulation of particle morphology. Full article

Nanocomposite materials composed of an organic matrix and an inorganic nanofiller have been the subject of intense research in recent years. Indeed, the synergy between these two phases confers improved properties thanks to an increased surface–volume ratio, which reinforces the interactions between the particles and the polymer matrix. These interactions depend on many factors such as the shape, size and dispersion of the nanoobjects. Polysilsesquioxanes (PSQs) are a silicon polymer family that offers different sizes, shapes and structures and possesses ceramics properties (i.e., high thermal and/or oxidative resistance and high chain rigidity), thanks to the siloxane backbone. In this article, we propose to incorporate polymer-grafted ladder polysilsesquioxanes (LPSQs) as nanofillers in thermoplastic matrices. Chloride-functionalized LPSQs were synthesized from two different precursors and thoroughly characterized by ¹H, ¹³C and ²⁹Si NMR, as well as by SEC and WAXS. The well-defined LPSQ was then converted into an azide analog. The resulting hybrid material was functionalized with poly(ethylene glycol) (PEG) chains and incorporated into poly(ethylene oxide) or poly(methyl methacrylate) matrices. We found that the viscoelastic properties of the nanocomposite materials were impacted by plasticizing or the reinforcement effect depending on the grafted PEG chain length. Full article

The requirement for the development of advanced technologies is the need to create new functional thermostable soluble polysilsesquioxanes. Combining the potential of organosilicon chemistry and the chemistry of heterocyclic compounds is a promising direction for the formation of novel organosilicon polymer systems with new properties and new possibilities for their practical application. Using the classical method of hydrolysis and polycondensation of previously unknown trifunctional (trimethoxysilylpropyl)glutarimide in the presence or absence of an acid or base catalyst, a universal approach to the formation of new thermostable soluble polysilsesquioxanes with glutarimide side-chain groups is proposed, which forms the basis for the synthesis of polysilsesquioxane polymers with different functionality. The weight average molecular weight of silsesquioxanes, determined by gel permeation chromatography, is practically independent of the reaction conditions and is 10–12 kDa; at the same time, the molecular weight distribution remains low and amounts to 1.38–1.47. According to thermogravimetric analysis, the resulting polysiloxanes have high thermal stability up to 335 °C. By the dynamic light scattering method, it was established that in an aqueous solution, silsesquioxane macromolecules are in an associated state, forming supramolecular structures due to the intermolecular interaction of individual macromolecules. The average hydrodynamic diameter of the particles was 46 nm. X-ray diffraction analysis showed the amorphous nature of the polymer. Polymer film coatings based on synthesized silsesquioxanes are characterized by 98% transmission in the visible spectrum and resistance to ultraviolet radiation, which is promising for the creation of functional transparent film coatings. Full article

Bridged polysilsesquioxanes (BPSs) are emerging biomaterials composed of synergistic inorganic and organic components. These materials have been investigated as ideal carriers for therapeutic and diagnostic systems for their favorable properties, including excellent biocompatibility, physiological inertia, tunable size and morphology, and their extensive design flexibility of functional organic groups to satisfy diverse application requirements. Stimuli-responsive BPSs can be activated by both endogenous and exogenous stimuli, offering a precise, safe, and effective platform for the controlled release of various targeted therapeutics. This review aims to provide a comprehensive overview of stimuli-responsive BPSs, focusing on their synthetic strategies, biocompatibility, and biodegradability, while critically assessing their capabilities for controlled release in response to specific stimuli. Furthermore, practical suggestions and future perspectives for the design and development of BPSs are presented. This review highlights the significant role of stimuli-responsive BPSs in advancing biomedical research. Full article

The miniaturization and high-power density of modern electronic devices pose significant thermal management issues, particularly affecting their performance and lifetime. Ladder-like polysilsesquioxanes (LPSQs) offer a promising solution due to their remarkable thermal, mechanical, and chemical properties. By incorporating thermally conductive fillers, LPSQ composites can achieve high thermal conductivity (TC), making them ideal for thermal management in advanced electronic applications. In this study, LPSQ-based nanocomposites containing functionalized alumina nanoparticles were prepared by solution casting and UV curing, and the effects of varying amounts of Irgacure-184 photoinitiator on their structural and thermal properties were investigated. Three sets of samples were prepared with a fixed amount of LPSQs, 80 wt.% of nanoparticles, and 1, 5, or 10 wt.% of photoinitiator with respect to the matrix. TC was evaluated from the measured values of heat capacity, density, and thermal diffusivity. TC values increased by 60%, 71.2%, and 93.1% for the three samples, respectively, compared to the neat matrix. Results indicate that an intermediate amount of photoinitiator (5%) preserved LPSQs’ structural integrity, namely the presence of long linear silsesquioxane chains, and provided good filler dispersion and distribution, high polymerization degree, thermal stability, and high TC. Full article

Control of the porous structure and particle size is essential for improving the properties of polysilsesquioxane (PSQ) microspheres. Herein, using the strategy combining inverse suspension polymerization, two-step sol–gel- and polymerization-induced phase separation processes, micron-sized thiol-containing macroporous PSQ (TMPSQ) microspheres with controllable morphologies, adjustable particle diameters (4.9–17.3 μm), and pore sizes (40–3774 nm) were prepared. The morphology and size of the TMPSQ microspheres were characterized by SEM. The mercury intrusion method was employed to analyze the porous structure of the microspheres. The effects of the composition of the sol–gel disperse phase, the mass ratio of the sol–gel disperse phase to the oil continuous phase (WR_W/O), and the Span 80 mass content in the oil continuous phase on the morphology, particle diameter and pore size of the TMPSQ microspheres were investigated. Results indicated that the composition of the sol–gel disperse phase determines the morphology and porous structure of the microspheres, and WR_W/O and Span 80 content have remarkable impacts on the morphology and particle size of the microspheres. This study is beneficial to the design and fabrication of functional PSQ microspheres with desired properties and promising application prospects. Full article

This study delineates a methodology for the preparation of new composites based on a photocurable urethane-acrylate resin, which has been modified with (3-thiopropyl)polysilsesquioxane (SSQ-SH). The organosilicon compound combines fully enclosed cage structures and incompletely condensed silanols (a mixture of random structures) obtained through the hydrolytic condensation of (3-mercaptopropyl)trimethoxysilane. This process involves a thiol-ene “click” reaction between SSQ-SH and a commercially available resin (Ebecryl 1271^®) in the presence of the photoinitiator DMPA, resulting in composites with significantly changed thermal properties. Various tests were conducted, including thermogravimetric analysis (TGA), Fourier transmittance infrared spectroscopy (FT-IR), differential scanning calorimetry (Photo-DSC), and photoreological measurement mechanical property, and water contact angle (WCA) tests. The modification of resin with SSQ-SH increased the temperature of 1% and 5% mass loss compared to the reference (for 50 wt% SSQ-SH, T_5% was 310.8 °C, an increase of 20.4 °C). A composition containing 50 wt% of SSQ-SH crosslinked faster than the reference resin, a phenomenon confirmed by photorheological tests. This research highlights the potential of new composite materials in coating applications across diverse industries. The modification of resin with SSQ-SH not only enhances thermal properties but also introduces a host of functional improvements, thereby elevating the performance of the resulting coatings. Full article

New polysilsesquioxane (PSQ)-based CO₂ separation membranes with succinic anhydride and monoalkylurea units as thermally degradable CO₂-philic units were prepared by the copolymerization of a 1:1 mixture of [3-(triethoxysilyl)propyl]succinic anhydride (TESPS) or [3-(triethoxysilyl)propyl]urea (TESPU) and bis(triethoxysilyl)ethane (BTESE). The succinic anhydride and monoalkylurea units underwent thermal degradation to form ester and dialkylurea units, respectively, with the liberation of small molecules (e.g., CO₂ and NH₃) under N₂ atmosphere. The effects of thermal degradation on the performance of the obtained membranes were investigated. The TESPS-BTESE- and TESPU-BTESE-based membranes calcined at 250 °C and 200 °C exhibited good CO₂/N₂ permselectivities of 20.2 and 14.4, respectively, with CO₂ permeances of 7.7 × 10⁻⁸ and 7.9 × 10⁻⁸ mol m⁻²·s⁻¹·Pa⁻¹, respectively. When the membranes were further calcined at elevated temperatures of 350 °C and 300 °C, respectively, to promote the thermal degradation of the organic units, the CO₂ permeances increased to 1.3 × 10⁻⁷ and 1.2 × 10⁻⁶ mol m⁻²·s⁻¹·Pa⁻¹ (3.9 × 10² and 3.6 × 10³ GPU), although the CO₂/N₂ permselectivities decreased to 19.5 and 8.4, respectively. These data indicate that the controlled thermal degradation of the organic units provides a new methodology for possible tuning of the CO₂ separation performance of PSQ membranes. Full article

In this study, thiol-functionalized ladder-like polysesquioxanes end-capped with methyl and phenyl groups were synthesized via a simple sol-gel method and characterized through gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and thermogravimetric analysis (TGA). Additionally, epoxy blends of different formulations were prepared. Their structural, flame-retardant, thermal, and mechanical properties, as well as volatile organic compound (VOC) emissions, were determined using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), TGA, scanning electron microscopy (SEM), limiting oxygen index (LOI), cone calorimetry, and a VOC analyzer. Compared to epoxy blends with flame retardants containing elemental phosphorus alone, those with flame retardants containing elemental phosphorus combined with silicon and sulfur exhibited superior thermal, flame-retardant, and mechanical properties with low VOC emissions. SEM of the residual char revealed a dense and continuous morphology without holes or cracks. In particular, LOI values for the combustion of methyl and phenyl end-capped polysilsesquioxane mixtures were 32.3 and 33.7, respectively, compared to 28.4% of the LOI value for the blends containing only phosphorus compounds. The silicon–sulfur–phosphorus-containing blends displayed reduced flammability concerning the blends using a flame retardant containing only phosphorus. This reflects the cooperative effects of various flame-retardant moieties. Full article

Polysilsesquioxane (PSQ) microspheres have shown promise in many fields, but previous studies about porous PSQ microspheres are scarce. Herein, we fabricated novel micron-sized thiol-functional polysilsesquioxane (TMPSQ) microspheres with open and interconnected macropores by combining inverse suspension polymerization with two-step sol–gel and polymerization-induced phase separation processes, without using phase-separation-promoting additives or sacrificial templates. The chemical composition of the TMPSQ microspheres was confirmed using FTIR and Raman spectroscopy. The morphology of the TMPSQ microspheres was characterized using SEM and TEM. TGA was employed to test the thermal stability of the TMPSQ microspheres. Mercury intrusion porosimetry and nitrogen adsorption–desorption tests were performed to investigate the pore structure of the TMPSQ microspheres. The results showed that the TMPSQ microspheres had open and interconnected macropores with a pore size of 839 nm, and the total porosity and intraparticle porosity reached 70.54% and 43.21%, respectively. The mechanism of porous generation was proposed based on the morphological evolution observed using optical microscopy. The macropores were formed through the following four steps: phase separation (spinodal decomposition), coarsening, gelation, and evaporation of the solvent. The macropores can facilitate the rapid mass transfer between the outer and inner spaces of the TMPSQ microspheres. The TMPSQ microspheres are promising in various fields, such as catalyst supports and adsorbents. Full article

Soluble polysilsesquioxane containing side-chain phthalimide groups (PSQ-PhI) was synthesized via a solvent- and catalyst-free hydrolytic polycondensation reaction using 2-[3-(triethoxysilyl)propyl]-1H-isoindole-1,3(2H)-dione. The composition and structure of polysilsesquioxane was confirmed via ¹H, ¹³C, and ²⁹Si NMR spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, dynamic light scattering, X-ray diffraction analysis, and elemental analysis. The synthesized silsesquioxane showed a monomodal molecular weight distribution. The average molecular weight of polysilsesquioxane is 11,200 Da, and the polydispersity index is 1.10. ²⁹Si NMR analysis showed a half-peak width w_1/2 3.1 ppm at δ −68.3, which corresponds to the PhI(CH₂)₃SiO_3/2 unit and indicates an ordered structure in the polymer, with some defects caused by the presence of uncondensed silanol groups. PSQ-PhI showed good thermal stability (T_d5% decomposition at 345 °C). The polysilsesquioxane-based coating was transparent in the visible region. Full article

This contribution reports the synthesis of polyhydroxyurethane (PHU)-poly(ethylene oxide) (PEO) multiblock copolymer networks crosslinked with polysilsesquioxane (PSSQ). First, the linear PHU-PEO multiblock copolymers were synthesized via the step-growth polymerization of bis(6-membered cyclic carbonate) (B6CC) with α,ω-diamino-terminated PEOs with variable molecular weights. Thereafter, the PHU-PEO copolymers were allowed to react with 3-isocyanatopropyltriethoxysilane (IPTS) to afford the derivatives bearing triethoxysilane moieties, the hydrolysis and condensation of which afforded the PHU-PEO networks crosslinked with PSSQ. It was found that the PHU-PEO networks displayed excellent reprocessing properties in the presence of trifluoromethanesulfonate [Zn(OTf)₂]. Compared to the PHU networks crosslinked via the reaction of difunctional cyclic carbonate with multifunctional amines, the organic–inorganic PHU networks displayed the decreased reprocessing temperature. The metathesis of silyl ether bonds is responsible for the improved reprocessing behavior. By adding lithium trifluoromethanesulfonate (LiOTf), the PHU-PEO networks were further transformed into the solid polymer electrolytes. It was found that the crystallization of PEO chains in the crosslinked networks was significantly suppressed. The solid polymer electrolytes had the ionic conductivity as high as 7.64 × 10⁻⁵ S × cm⁻¹ at 300 K. More importantly, the solid polymer electrolytes were recyclable; the reprocessing did not affect the ionic conductivity. Full article

The utilization of preceramic polymers (PCPs) to produce both oxide and non-oxide ceramics has caught significant interest, owing to their exceptional characteristics. Diverse types of polymer-derived ceramics (PDCs) synthesized by using various PCPs have demonstrated remarkable characteristics such as exceptional thermal stability, resistance to corrosion and oxidation at elevated temperatures, biocompatibility, and notable dielectric properties, among others. The application of additive manufacturing techniques to produce PDCs opens up new opportunities for manufacturing complex and unconventional ceramic structures with complex designs that might be challenging or impossible to achieve using traditional manufacturing methods. This is particularly advantageous in industries like aerospace, automotive, and electronics. In this review, various categories of preceramic polymers employed in the synthesis of polymer-derived ceramics are discussed, with a particular focus on the utilization of polysiloxane and polysilsesquioxanes to generate silicate ceramics. Further, diverse additive manufacturing techniques adopted for the fabrication of polymer-derived silicate ceramics are described. Full article

The ladder phenyl/vinyl polysilsesquioxane (PhVPOSS) was used to improve the flame-retardancy performances of ethylene-vinyl acetate copolymer (EVA)/aluminum hydroxide (ATH) composites due to the reactivity of its vinyl groups. FTIR, XPS, ¹H NMR, and SEM-EDS data demonstrated the PhVPOSS grafting onto EVA molecular chains. The PhVPOSS improved the thermal stability of EVA/ATH composites, as shown by the thermogravimetric analysis (TGA). Furthermore, with the cone calorimeter (CONE) experiments, EVA/ATH/PhVPOSS showed better fire safety than the EVA/ATH composites, with the PHRR, PSPR, and PCOP reduced by 7.89%, 57.4%, and 90.9%, respectively. The mechanism investigations of flame retardancy revealed that the charring behaviors of the EVA/ATH/PhVPOSS composites were improved by the formation of Si-C bonds and Si-O bonds, and a more compact and denser char layer can contribute more to the barrier effect. Full article

A novel thiol-functionalized polysilsesqioxane containing hydroxyl and methyl groups was synthesized using a simple acid-catalyzed sol–gel method to develop an epoxy hardener with low odor, low volatile organic compound (VOC) emissions, and fast curing at low temperatures. The synthesized thiol-based hardeners were characterized using Fourier transform infrared spectroscopy, nuclear magnetic resonance, thermogravimetric analysis (TGA), and gel permeation chromatography and compared with commercially available hardeners in terms of odor intensity and VOC emissions using the air dilution olfaction method and VOC analysis. The curing behavior and thermal and mechanical properties of the epoxy compounds prepared with the synthesized thiol-based hardeners were also evaluated. The results showed that synthetic thiol-based hardeners containing methyl and hydroxyl groups initiated the curing reaction of epoxy compounds at 53 °C and 45 °C, respectively. In contrast, commercial thiol-based hardeners initiated the curing reaction at 67 °C. Additionally, epoxy compounds with methyl-containing synthetic thiol-based hardeners exhibited higher TGA at a 5% weight loss temperature (>50 °C) and lap shear strength (20%) than those of the epoxy compounds with commercial thiol-based hardeners. Full article