A novel organic-inorganic hybrid containing allyl benzoxazine and polyhedral oligomeric silsesquioxane (POSS) was synthesized by the thiol-ene (click) reaction. The benzoxazine (BOZ)-containing POSS (SPOSS-BOZ) copolymerized with benzoxazine/epoxy resin was used to prepare composites of SPOSS-PBZ-E nanocomposites(NPs). The polymerization behavior was monitored by FTIR and non-isothermal differential scanning calorimetry (DSC), which showed that the composites had completely cured with multiple polymerization mechanisms according to the oxazine ring-opening and epoxy resin (EP) polymerization. The thermal properties of the organic–inorganic polybenzoxazine (PBZ) nanocomposites were analyzed by DSC and thermogravimetric analysis (TGA). Furthermore, the X-ray diffraction analysis and the scanning electron microscopy (SEM) micrographs of the SPOSS-PBZ-E nanocomposites indicated that SPOSS was chemically incorporated into the hybrid nanocomposites in the size range of 80–200 nm. The flame retardancy of the benzoxazine epoxy resin composites was investigated by limiting oxygen index (LOI), UL 94 vertical burn test, and cone calorimeter tests. When the amount of SPOSS reached 10% or more, the vertical burning rating of the curing system arrived at V-1, and when the SPOSS-BOZ content reached 20 wt %, the thermal stability and flame retardancy of the material were both improved. Moreover, in the cone calorimeter testing, the addition of SPOSS-BOZ hindered the decomposition of the composites and led to a reduction in the peak heat release rate (pHRR), the average heat release rate (aHRR), and the total heat release (THR) values by about 20%, 25%, and 25%, respectively. The morphologies of the chars were also studied by SEM and energy dispersive X-ray spectroscopy (EDX), and the flame-retardant mechanism of POSS was mainly a condensed-phase flame retardant. The ceramic layer was formed by the enrichment of silicon on the char surface. When there are enough POSS nanoparticles, it can effectively protect the combustion of internal polymers. Full article

In this work, a series of heptaphenyl siloxane trisilanol/polyhedral oligomeric silsesquioxane (T₇-POSS) modified by polyols with different molecular weights were synthesized into liquid-like nanoparticle–organic hybrid materials using the grafted-from method. All grafted POSS nanoparticles changed from solid powders to liquid at room temperature. Polyurethane (PU) nanocomposites with POSS contents ranging from 1.75 to 9.72 wt % were prepared from these liquefied polyols-terminated POSS with polyepichlorohydrin (POSS–PECH). Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to characterize the morphology of the POSS–PECH/PU nanocomposites. The results showed that the polyol-terminated POSS particles overcame the nanoagglomeration effect and evenly disperse in the polymeric matrix. The damping factor (tan δ) of resultant nanocomposites increased from 0.90 to 1.16, while the glass transition temperature decreased from 15.8 to 9.4 °C when POSS contents increased from 0 to 9.75 wt %. The gel content, tensile strength and Fourier transform infrared (FTIR) analyses demonstrated that the molecular thermal movement ability of the polyurethane (PU) matrix increased with increasing POSS hybrid content. Therefore, the improvement of the damping properties of the composites was mainly due to the friction-related losses occurring in the interface region between the nanoparticles and the matrix. Full article

Polyhedral oligomeric silsesquioxane (POSS)-derived Si@C anode material is prepared by the copolymerization of octavinyl-polyhedral oligomeric silsesquioxane (octavinyl-POSS) and styrene. Octavinyl-polyhedral oligomeric silsesquioxane has an inorganic core (-Si₈O₁₂) and an organic vinyl shell. Carbonization of the core-shell structured organic-inorganic hybrid precursor results in the formation of carbon protected Si-based anode material applicable for lithium ion battery. The initial discharge capacity of the battery based on the as-obtained Si@C material Si reaches 1500 mAh g⁻¹. After 550 charge-discharge cycles, a high capacity of 1430 mAh g⁻¹ was maintained. A combined XRD, XPS and TEM analysis was performed to investigate the variation of the discharge performance during the cycling experiments. The results show that the decrease in discharge capacity in the first few cycles is related to the formation of solid electrolyte interphase (SEI). The subsequent rise in the capacity can be ascribed to the gradual morphology evolution of the anode material and the loss of capacity after long-term cycles is due to the structural pulverization of silicon within the electrode. Our results not only show the high potential of the novel electrode material but also provide insight into the dynamic features of the material during battery cycling, which is useful for the future design of high-performance electrode material. Full article

In order to improve the performance of traditional sodium alginate (SA) hydrogels cross-linked by Ca²⁺ ions to meet greater application demand, a strategy was designed to structure novel SA-based gels (named OP-PN gels) to achieve both stimulus responsiveness and improved mechanical strength. In this strategy, the SA chains are co-cross-linked by CaCl₂ and cationic octa-ammonium polyhedral oligomeric silsesquioxane (Oa-POSS) particles as the first network, and an organically cross-linked poly(N-isopropyl acrylamide) (PNIPA) network is introduced into the gels as the second network. Several main results are obtained from the synthesis and characterization of the gels. For OP-PN gels, their properties depend on the content of both uniformly dispersed Oa-POSS and PNIPA network directly. The increased Oa-POSS and PNIPA network content significantly improves both the strength and resilience of gels. Relatively, the increased Oa-POSS is greatly beneficial to the modulus of gels, and the increased PNIPA network is more favorable to advancing the tensile deformation of gels. The gels with hydrophilic PNIPA network exhibit better swelling ability and remarkable temperature responsiveness, and their volume phase transition temperature can be adjusted by altering the content of Oa-POSS. The deswelling rate of gels increases gradually with the increase of POSS content due to the hydrophobic Si–O skeleton of POSS. Moreover, the enhanced drug loading and sustained release ability of the target drug bovine serum albumin displays great potential for this hybrid gel in the biomedical field. Full article

The effect of the anchoring group on the detailed polymerization kinetics was investigated using monomethacryloxy-heptaisobutyl POSS (1M-POSS). This compound was copolymerized with lauryl methacrylate (LM) as the base monomer, at various molar ratios. The process was initiated photochemically. The polymerization kinetics were followed by photo-DSC and photorheology while the polymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). For comparison, a methacrylate containing the branched siloxy-silane group (TSM) was also studied. It was found that the modifiers with a bulky substituent have a dual effect on the termination process: (i) At low concentrations, they increase the molecular mobility by increasing the free volume fraction, which leads to an acceleration of the termination and slows the polymerization; while (ii) at higher concentrations, they retard molecular motions due to the “anchor effect” that suppresses the termination, leading to acceleration of the polymerization. The anchor effect can also be considered from a different point of view: The possibility of anchoring a monomer with a long substituent (LM) around the POSS cage, which can further enhance propagation. These conclusions were derived based on kinetic results, determination of polymerization rate coefficients, and copolymer analysis. Full article

A series of hybrid thermoplastic polyurethanes (PUs) were synthesized from bi-functional polyhedral oligomeric silsesquioxane (B-POSS) and polycaprolactone (PCL) using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent for the first time. The newly synthesized hybrid materials were fully characterized in terms of structure, morphology, thermal and mechanical performance, as well as their toughening effect toward polyesters. Thermal gravimeter analysis (TGA) and differential scanning calorimetry (DSC) showed enhanced thermal stability by 76 °C higher in decomposition temperature (T_d) of the POSS PUs, and 22 °C higher glass transition temperature (T_g) when compared with control PU without POSS. Static contact angle results showed a significant increment of 49.8° and 53.4° for the respective surface hydrophobicity and lipophilicity measurements. More importantly, both storage modulus (G’) and loss modulus (G’’) are improved in the hybrid POSS PUs and these parameters can be further adjusted by varying POSS content in the copolymer. As a biodegradable hybrid filler, the as-synthesized POSS PUs also demonstrated a remarkable effect in toughening commercial polyesters, indicating a simple yet useful strategy in developing high-performance polyester for advanced biomedical applications. Full article

Rigid polyurethane foams (RPUFs) were successfully modified with different weight ratios (0.5 wt%, 1.5 wt% and 5 wt%) of APIB-POSS and AEAPIB-POSS. The resulting foams were evaluated by their processing parameters, morphology (Scanning Electron Microscopy analysis, SEM), mechanical properties (compressive test, three-point bending test and impact strength), viscoelastic behavior (Dynamic Mechanical Analysis, DMA), thermal properties (Thermogravimetric Analysis, TGA, and thermal conductivity) and application properties (contact angle, water absorption and dimensional analysis). The results showed that the morphology of modified foams is significantly affected by the type of the filler and filler content, which resulted in inhomogeneous, irregular, large cell shapes and further affected the physical and mechanical properties of resulting materials. RPUFs modified with APIB-POSS represent better mechanical and thermal properties compared to the RPUFs modified with AEAPIB-POSS. The results showed that the best results were obtained for RPUFs modified with 0.5 wt% of APIB-POSS. For example, in comparison with unfilled foam, compositions modified with 0.5 wt% of APIB-POSS provide greater compression strength, better flexural strength and lower water absorption. Full article

Giant surfactants refer to a new kind of amphiphile by incorporating functional molecular nanoparticles with polymer tails. As a size-amplified counterpart of small-molecule surfactants, they serve to bridge the gap between small-molecule surfactants and amphiphilic block copolymers. This work reports the design and synthesis of single-tailed giant surfactants carrying a hydrophobic poly(ε-caprolactone) (PCL) as the tail and a hydrophilic cage-like polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the head. The modular synthetic strategy features an efficient “growing-from” and “click-modification” approach. Starting from a monohydroxyl and heptavinyl substituted POSS (VPOSS-OH), a PCL chain with controlled molecular weight and narrow polydispersity was first grown by the ring-opening polymerization (ROP) of ε-CL under the catalysis of stannous octoate, leading to a PCL chain end-capped with heptavinyl substituted POSS (VPOSS-PCL). To endow the POSS head with adjustable polarity and functionality, three kinds of hydrophilic groups, including hydroxyl groups, carboxylic acids, and amine groups, were installed to the periphery of POSS molecule by a high-efficiency thiol-ene “click” reaction. The compounds were fully characterized by NMR, gel permeation chromatography (GPC), MALDI-TOF mass spectrometry, and TGA analysis. In addition, the preliminary self-assembly study of these giant surfactants was also investigated by TEM and dynamic laser light scattering (DLS), which indicated that they can form spherical nanoparticles with different diameters in aqueous solution. This work affords a straightforward and versatile way for synthesizing single-tailed giant surfactants with diverse head surface functionalities. Full article

In this study, a novel copolymer, PbisDOPOMA-POSSMA-GMA (PDPG), containing methacryloisobutyl polyhedral oligomeric silsesquioxane (POSSMA), reactive glycidyl methacrylate (GMA), and bis-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide methacrylate (bisDOPOMA) and derivative functionalized graphene oxide (GO) were synthesized by a one-step grafting reaction to create a hybrid flame retardant (GO-MD-MP). GO-MD-MP was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). Flame-retardant epoxy resin (EP) composites were prepared by adding various amounts of GO-MD-MP to the thermal-curing epoxy resin of diglycidyl ether of bisphenol A (DGEBA, trade name E-51). The thermal properties of the EP composites were remarkably enhanced by adding the GO-MD-MP, and the residue char of the epoxy resin also increased greatly. With the incorporation of 4 wt % GO-MD-MP, the limiting oxygen index (LOI) value was enhanced to 31.1% and the UL-94 V-0 rating was easily achieved. In addition, the mechanical strength of the epoxy resin was also improved. Full article

Blends of cyanate ester and phthalonitrile–polyhedral oligomeric silsesquioxane copolymers were prepared, and their cure behavior and properties were compared via differential scanning calorimetry (DSC) analysis, thermogravimetric (TG) analysis, dynamic mechanical analysis, Fourier-transform far-infrared (FTIR) spectroscopy, and rheometric studies. The copolymer blends showed high chemical reactivity, low viscosity, and good thermal stability (TG temperatures were above 400 °C). The glass-transition temperature of the blends increased by at least 140 °C compared to cyanate ester resin. The blends are suitable for preparing carbon-fiber-reinforced composite materials via a winding process and a prepreg lay-up process with a molding technique. The FTIR data showed that the polymerization products contained triazine-ring structures that were responsible for the superior thermal properties. Full article

The incorporation of polyhedral oligomeric silsesquioxanes (POSS) molecules as nanoparticles into polymers can provide improved physico-chemical properties. The enhancement depends on the extent of dispersion of the nanofiller, which is determined by the compatibility with the polymer that is by the POSS type, and the processing method. In this study, poly(ε-caprolactone)/POSS derivatives nanocomposites (PCL/POSS) were obtained via solution-casting and melt compounding. Two amino-derivatives containing different alkyl substituents, and ditelechelic POSS-containing hybrid PCL masterbatch were used as nanofillers. The effect of preparation method, POSS content and type on the morphology, thermal, mechanical, and surface properties of nanocomposites were studied. Morphological analysis evidenced the formation of POSS crystalline aggregates, self-assembled POSS molecules of submicrometer size dispersed in the polymer matrix. The best dispersion was achieved using the ditelechelic POSS-containing hybrid PCL masterbatch, and comparing the two amino-POSS derivatives, the one with longer alkyl chain of substituents exhibited better degree of dispersion independent of preparation method. DSC analysis showed the role of POSS derivatives as nucleating agents for PCL. The incorporation of POSS derivatives into the PCL matrix improved thermal stability. The preparation method, POSS type and content had influence on mechanical properties of nanocomposites. POSS nanoparticles enhanced the surface hydrophobicity of PCL. Full article

The dual-functionalized polyhedral oligomeric silsesquioxane (POSS) derivatives, which have the seven fluorinated alkanes and the single acrylate ester on the silica cube, were designed as a filler for lowering the refractive index (RI) and improving thermomechanical properties in poly(methyl methacrylate) (PMMA). The desired dual-functionalized POSS fillers were prepared, and because of its high miscibility, homogeneous films were readily obtained, by the casting method, with the mixture solutions containing the modified POSS and the polymers. From optical measurements, it was found that the larger effects of lowering the RIs of the PMMA matrices were observed from the modified POSS than those of the octa-substituted POSS derivatives with the homogeneous substituents. It should be mentioned that the degradation temperatures and the storage moduli were able to be greatly elevated by loading the present POSS fillers. Finally, it was demonstrated that the methacrylate ester-tethered POSS should be the most effective filler for modulating PMMA (Δn = −0.020, ΔTd20 = +53 °C, ΔE’/E’ = +72%). Full article

A novel group of silsesquioxane derivatives, which are siloxane-silsesquioxane resins (S4SQ), was for the first time examined as possible flame retardants in polypropylene (PP) materials. Thermal stability of the PP/S4SQ composites compared to the S4SQ resins and neat PP was estimated using thermogravimetric (TG) analysis under nitrogen and in air atmosphere. The effects of the non-functionalized and n-alkyl-functionalized siloxane-silsesquioxane resins on thermostability and flame retardancy of PP materials were also evaluated by thermogravimetry-Fourier transform infrared spectrometry (TG-FTIR) and by cone calorimeter tests. The results revealed that the functionalized S4SQ resins may form a continuous ceramic layer on the material surface during its combustion, which improves both thermal stability and flame retardancy of the PP materials. This beneficial effect was observed especially when small amounts of the S4SQ fillers were applied. The performed analyses allowed us to propose a possible mechanism for the degradation of the siloxane-silsesquioxane resins, as well as to explain their possible role during the combustion of the PP/S4SQ composites. Full article

In this paper, two different models of hybrid ionic liquids (ILs) based on polyhedral oligomeric silsesquioxanes (POSSs) have been prepared. Additionally, these ILs based on POSSs (ILs-POSSs) exhibited excellent thermal stabilities and low glass transition temperatures. ¹H, ¹³C, and ²⁹Si nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) were used to confirm the structures of the IL-POSSs. Furthermore, the spherical vesicle structures of two IL-POSSs were observed and were caused by self-assembly behaviors. In addition, we found it very meaningful that these two ILs showed lower detection limits of 2.57 × 10⁻⁶ and 3.98 × 10⁻⁶ mol/L for detecting picric acid (PA). Moreover, the experimental data revealed that the products have high sensitivity for detecting a series of nitroaromatic compounds—including 4-nitrophenol, 2,4-dinitrophenol, and PA—and relatively comprehensive explosive detection in all of the tests of IL-POSSs with nitroaromatic compounds thus far. Additionally, the data indicate that these two new ILs have great potential for the detection of explosives. Therefore, our work may provide new materials including ILs as fluorescent sensors in detecting nitroaromatic explosives. Full article

The use of polyhedral oligomeric silsesquioxanes (POSSs) for making polymer composites has grown exponentially since the last few years of the 20th century. In comparison with the other most commonly used fillers, POSSs possess the advantage of being molecules. Thus, this allows us to combine their nano-sized cage structures, which have dimensions that are similar to those of most polymer segments and produce a particular and exclusive chemical composition. These characteristics linked with their hybrid (inorganic–organic) nature allow researchers to modify POSS according to particular needs or original ideas, before incorporating them into polymers. In this present study, we first start with a brief introduction about the reasons for the rediscovery of these nanoparticles over the last 25 years. Starting from the form of POSS that is most widely used in literature (octaisobutyl POSS), this present study aims to evaluate how the reduction of symmetry through the introduction of organic groups favors their dispersion in polystyrene matrix without compromising their solubility. Full article

In acidic conditions, mesoporous molecular sieves SBA-15 and SBA-15-SH were synthesized. Structural characterization was carried out by powder X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ¹³C CP MAS-NMR, ²⁹Si CP MAS-NMR and nitrogen adsorption–desorption (BET). The results showed that in SBA-15-SH, the direct synthesis method made the absorption peak intensity weaker than that of SBA-15, while the post-grafted peak intensity did not change. Their spectra were different due to the C-H stretching bands of Si-O-Si and propyl groups. But their structure was still evenly distributed and was still hexangular mesoporous structure. Their pore size increased, and the H-SBA-15-SH had larger pore size. The adsorption of ammonia-nitrogen by molecular sieve was affected by the relative pressure and the concentration of ammonia-nitrogen, in which the adsorption capacity of G-SBA-15-SH was the largest and the adsorption capacity of SBA-15 was the smallest. Full article

Over the past two decades, organic optoelectronic materials have been considered very promising. The attractiveness of this group of compounds, regardless of their undisputable application potential, lies in the possibility of their use in the construction of organic–inorganic hybrid materials. This class of frameworks also considers nanostructural polyhedral oligomeric silsesquioxanes (POSSs) with “organic coronae” and precisely defined organic architectures between dispersed rigid silica cores. A significant number of papers on the design and development of POSS-based organic optoelectronic as well as photoluminescent (PL) materials have been published recently. In view of the scientific literature abounding with numerous examples of their application (i.e., as OLEDs), the aim of this review is to present efficient synthetic pathways leading to the formation of nanocomposite materials based on silsesquioxane systems that contain organic chromophores of complex nature. A summary of stoichiometric and predominantly catalytic methods for these silsesquioxane-based systems to be applied in the construction of photoactive materials or their precursors is given. Full article

The preparation of hybrid nanocomposite materials derived from polyhedral oligomeric silsesquioxane (POSS) nanoparticles and polyimide (PI) has recently attracted much attention from both academia and industry, because such materials can display low water absorption, high thermal stability, good mechanical characteristics, low dielectric constant, flame retardance, chemical resistance, thermo-redox stability, surface hydrophobicity, and excellent electrical properties. Herein, we discussed the various methods that have been used to insert POSS nanoparticles into PI matrices, through covalent chemical bonding and physical blending, as well as the influence of the POSS units on the physical properties of the PIs. Full article