Polyhedral Oligomeric Silsesquioxane Molecules Research Articles

Properties and self-assembled packing morphology of long alkyl-chained substituted polyhedral oligomeric silsesquioxanes (POSS) cages

Polyhedral oligomeric silsesquioxane (POSS) cubic cage systems (octa-n-octadecyloctasilsesquioxane, (T8C18) and octakis(n-octadecyldimethylsiloxy)octasilsesquioxane, (Q8C18)) were synthesised with eight long n-alkyl chain (R = C18H37) substituent arms, as model nano-functionalized compounds. The crystalline packing morphology of the cages was studied using time-resolved Small- and Wide-angle X-ray scattering (SAXS/WAXS), thermal and optical techniques. From thermal analysis the melting and crystallization temperatures of the Q8 cage were significantly less than those for the T8 cage. X-ray scattering showed that both cage systems have long-range crystalline ordering where the alkyl chains align in a parallel axial disposition from the POSS core giving a 'rod-like' self-assembled packing morphology. The packing length-scale can be directly related to the overall dimensions of the POSS molecules. Compared to the T8 cages, the Q8 cages pack more efficiently allowing the interdigitation of the alkyl chain arms. Different packing modes and thermal behaviour observed for the T8 and Q8 cages is directly attributed to their structural chemistry. For the Q8 cage, the presence of the OSiMe2 spacer groups which tether the alkyl chain arms to the cage (absent in the T8 cages) allows greater flexibility of the arms letting them interdigitate with each other when packing which is not observed for the analogous T8 cages.

Surface Modification and Reinforcement of Silica Aerogels Using Polyhedral Oligomeric Silsesquioxanes

This study evaluated polyhedral oligomeric silsesquioxane (POSS) molecules as useful, multifunctional reinforcing agents of silica aerogels. Silica aerogels have low-density and high surface area, although their durability is often compromised by the inherent fragility and strong moisture absorption behavior of the silica networks. POSS molecules carrying phenyl, iso-butyl, and cyclohexyl organic side groups, and several Si-OH functionalities were incorporated into silica networks via reactions between Si-OH functionalities in POSS molecules and silanes. Solid state (13)C and (29)Si NMR spectra established that greater than 90% of POSS molecules grafted onto silica networks and led to an increase in fractal dimensions. An almost 6-fold increase in compressive modulus was achieved with less than 5 wt % trisilanol phenyl POSS, and a 50-fold decrease in polarity with negligible changes in density were seen in aerogels modified with less than 5 wt % trisilanol isobutyl POSS.

Effects of 2 nm size added heterogeneity on non-exponential dielectric response, and the dynamic heterogeneity view of molecular liquids

To investigate how non-exponential response could vary under different conditions, we studied the effects of adding 2 nm size polyhedral oligomeric silsesquioxane (POSS) to diglycidyl ether of bisphenol-A, whose molecules have the same terminal (epoxide) dipoles as the tentacle-like side chains attached to the silsesquioxane core of the POSS molecule. Dielectric relaxation spectra show that, on initial addition, the POSS nano-heterogeneity decreases the non-exponential response parameter β, which is consistent with the dynamic heterogeneity view, but it also decreases the relaxation time τ(m), which is inconsistent with that view. The variations in β and τ(m) with the composition have a thermal equivalence. Despite the lack of translational diffusion required for dynamic heterogeneity, plastic crystals show non-exponential response and non-Arrhenius dynamics. Measurements of β and τ(m) seem more appropriate than using probe molecules or modeling nonlinear response data as a sum of linear responses for testing the dynamic heterogeneity view. Data on molecular liquid mixtures is not generally consistent with this view, and adding a solute does not always decrease β. Studies of mixtures of different size rigid molecules with identical dipolar groups, including polymers, may be useful for comparing the relative effects of temperature and molecular size on β and τ(m).

UV-stabilisation of polystyrene-based nanocomposites provided by polyhedral oligomeric silsesquioxanes (POSS)

The photo-ageing behaviour of Polyhedral Oligomeric SilSequioxane (POSS)-polystyrene (PS) nanocomposites has been investigated for the first time. POSS having different inorganic framework and pendant organic groups have been used in the PS nanocomposite preparation and the formulated films were subjected to accelerated weathering. Compared to pristine PS, the POSS-containing PS developed a lower level of carbonyl and hydroxyl groups as a function of the exposure time, indicating a significantly improved resistance of the nanocomposites to photo-degradation. The results suggest that all of the investigated POSS molecules play a protective role and may extend the in-use lifetime of the polymeric matrix. The protection efficiency seems to depend on the structure of the POSS used, i.e. the type of their inorganic framework and organic pendant groups. The efficacy of the protection provided by POSS is more pronounced for the open-cage POSS-triols than for the closed-cage POSS, suggesting an active role of the POSS-triol free OH group in the PS stabilisation process. The pendant organic groups significantly influence the nanocomposite's local morphology by controlling the formation of POSS re-aggregates and/or the POSS dispersion into the matrix, and its response to photo-oxidation.

Novel polyhedral oligomeric silsesquioxane‐substituted dendritic polyester tougheners for linear thermoplastic polyurethane

AbstractBoltorn hyperbranched aliphatic polyesters were functionalized with polyhedral oligomeric silsesquioxane (POSS) and incorporated into linear thermoplastic polyurethane (TPU). Increasing POSS‐functionalized Boltorn concentration led to an increase in agglomerate size and frequency, due to interactions between POSS molecules. The Boltorn dendrimer primarily influenced the morphology of the blends. Blends displayed enhanced thermal stability, due to restrictions on chain segmental motions imparted by the Boltorn and thermal shielding by POSS. Increasing the blend concentration resulted in higher tensile modulus and strength, while ductility decreased due to increased rigidity. Creep deformation decreased and permanent deformation increased with increased Boltorn content, while E′, E″, and Tg values all increased. TPU blended with higher generation functionalized‐Boltorn displayed superior thermal and mechanical properties than those containing lower generation dendrimer, due to enhanced interaction and restrictions on TPU chain segments. Both the Boltorn and POSS contributed to material properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Properties of POSS/HNBR Elastomer Nanocomposites

A series of composite materials containing polyhedral oligomeric silsesquioxanes (POSS) and hydrogenated butadiene-acrylonitrile rubber (HNBR) were prepared. The goal of the work was to evaluate the effect of the type and reactivity of functional groups in the POSS cage on properties of the resulting elastomeric nanocomposites. The paper presents some of the preliminary results obtained from the studies. The results indicate that incorporation of POSS into silica-filled HNBR elastomer network increases interfacial interactions of the systems and the POSS molecules can be successfully used as coagents of crosslinking towards the elastomer matrix and efficient additives improving the mechanical properties of elastomeric nanocomposites. Furthermore, evaluation of changes in mechanical properties, induced in a result of POSS/HNBR composites ageing, show that the inclusion of POSS in the HNBR network is directly influencing the stabilizing effect and improves the ageing resistance of elastomer composites.

Silsesquioxanes as Modifying Agents of Methylvinylsilicone Rubber

The idea and methods of methylvinylsilicone rubber modification are present. Polyhedral oligomeric silsesquioxanes (POSS) functionalized by vinyl-, carboxyl or amino-organic groups were used with the goal of modifying the rubber matrix. Additionally, oxazoline derivative and itaconic acid were used as the coupling agents. Generally, the process of modification contributed to increasing of rubber-filler interactions, however the useful properties of composites depended on a kind of active groups and way of modifications. It has been shown how grafting of POSS molecules to silicone backbone affects the cross-link density, rheometrical and mechanical properties, hysteresis and relaxation rates of the methylvinylsilicone rubber vulcanizates. Moreover, both the presence of silsesquioxanes and the way of composites preparing affect the improvement of filler dispersion degree in the rubber matrix, as indicated by SEM images. The most significant effect was observed for vinylisobutyl-POSS grafting to the silicone backbone which resulted in the considerably improved mechanical properties of the resulting network.

Self-assembled structure formation from interactions between polyhedral oligomeric silsesquioxane and sorbitol in preparation of polymer compounds

This study investigated the factors responsible for molecular interactions leading to self-assembly between the molecules of sorbitol and polyhedral oligomeric silsesquioxane (POSS) carrying organic and inorganic side groups. The study also assessed the utility of such molecular adducts as processing aids which will aid preparation of polymer compounds, films, and spun fibers. Several POSS molecules containing silanol functionalities and alkyl and phenyl substituents were used to separately evaluate the effects of hydrogen bonding and π−π interactions on formation of molecular adducts. The molecular adducts were studied using differential scanning calorimetry, wide angle X-ray diffraction, scanning electron microscopy, mass spectrometry, oscillatory shear rheology, and molecular dynamics simulation. The study revealed that POSS-sorbitol self-assembled structures were formed only when hydrogen bonding and π−π interactions worked cooperatively. In addition, self-assembled molecules were of amorphous nature although POSS and sorbitol were crystalline.

Nanostructured hyperbranched polyurethane elastomer hybrids that incorporate polyhedral oligosilsesquioxane

Novel thermoplastic hyperbranched polyurethane (HBP) elastomer hybrids containing polyhedral oligomeric silsesquioxane (POSS) have been synthesized using an A2+B3 approach. Different compositions of these hybrid nanomaterials were obtained from reactions of POSS-diol, triethanolamine, poly(ε-caprolactone)diol, and 4,4′-methylenebis(phenyl isocyanate) with a chain extender. The covalent attachment of POSS molecules to the backbone of the polyurethane chain was characterized with FT-IR and NMR spectroscopies. The non-agglomerated homogeneous dispersion obtained through the covalent attachment of POSS molecules and the HBP matrix was observed by SEM imaging. The mechanical properties, including the tensile and yield strengths, Young’s modulus, and toughness, significantly increased after the introduction of POSS molecules into the hybrids; this increase can be ascribed to the nano-reinforcement effect of the POSS cages and the long-range branched structure of the polymer. Thermogravimetric analyses indicated that the thermal stability of the polymer matrix was improved by the introduction of a small amount of POSS.

Influence of minor POSS molecules additions on the microstructure and hardness of Sn3Ag0.5Cu–xPOSS composite solders

The influence of minor POSS (polyhedral oligomeric silsesquioxanes) molecules additions on the microstructure and hardness of SnAgCu–xPOSS (x = 1, 3 and 5) was investigated. A mechanical mixture method was adopted by adding POSS molecules as dispersoids into SnAgCu solder to fabricate SnAgCu–xPOSS composite solders. The microstructural evolution and the hardness of the solders were investigated in details by microstructural observations, Vickers hardness tester and nanoindentation tests. The results showed that the effects of the dispersed POSS molecules in eutectic SnAgCu structure and the refined Ag3Sn IMC particles increased the hardness of eutectic SnAgCu phase and then increased the hardness of composite solder. In addition, because of the agglomeration of POSS molecule, a coarse lath-shaped structure (composed of POSS molecules, Ag3Sn phase and minor Cu6Sn5 phase) formed in SnAgCu–5POSS solder matrix, which reduced the hardness of SnAgCu–5POSS solder.

Novel elastomer dye-functionalised POSS nanocomposites: Enhanced colourimetric, thermomechanical and thermal properties

Nanocomposites consisting of poly(styrene-b-butadiene-b-styrene) (SBS) and polyhedral oligomeric silsesquiox- anes (POSS) were prepared using a solvent dispersion method. POSS molecules were functionalised with two dichlorotri- azine reactive dyes (CI Reactive Blue 4, CI Reactive Red 2) prior to compounding. Infrared spectroscopy confirmed func- tionalisation. Scanning electron microscopy revealed an increase in filler aggregation with concentration, with preferential phase selectivity. Ultraviolet spectroscopy and colourimetry confirmed colour uniformity and suggested that colour inten- sity could be controlled. Functionalised POSS improved thermal stability by imparting restrictions on SBS chain motions. Tensile stress-strain analysis revealed an increase in modulus with filler concentration, while creep deformation decreased and permanent strain increased with POSS content. Storage modulus, loss modulus and glass transition temperature increased with filler content due to effective SBS-POSS interaction. Nanocomposite properties were influenced by the phase the filler was dispersed throughout and the structure of the dye chromophore.

Structure-properties relationships of polyhedral oligomeric silsesquioxane (POSS) filled PS nanocomposites

The polyhedral oligomeric silsesquioxane (POSS) additivated polystyrene (PS) based nanocomposites were pre- pared by melt processing and the structure-properties relationships of the POSS-PS systems were compared to those of the neat PS. In order to investigate the effect of these structural parameters on the final properties of the polymer nanocompos- ites, five different kinds of POSS samples were used, in particular, POSS with different inorganic cage and with different organic pendent groups. The rheological investigation suggests clearly that the POSS acts as a plasticizer and that the processability of the PS was positively modified. The affinity between the POSS samples and the PS matrix was estimated by the calculated theoretical solubility parameters, considering the Hoy's method and by morphology analysis. Minor dif- ference between the solubility parameter of POSS and the matrix means better compatibility and no aggregation tendency. Furthermore, the POSS loading leads to a decrease of the rigidity, of the glass transition temperature and of the damping factor of the nanocomposite systems. The loading of different POSS molecules with open cage leads to a more pronounced effect on all the investigated properties that the loading of the POSS molecules with closed cage. Moreover, the melt prop- erties are significantly influenced by the type of inorganic framework, by the type of the pendent organic groups and by the interaction between the POSS organic groups and the host matrix, while, the solid state properties appears to be influenced more by the kind of cage.

Morphological, viscoelastic and thermal properties of poly(vinylidene Fluoride)/POSS nanocomposites

Nanocomposites of poly(vinylidene fluoride) and polyhedral oligomeric silsesquioxane were prepared through melt blending. Morphology, viscoelastic and thermal properties were investigated. Up to 1 wt.% the processing conditions were efficient to prevent formation of large POSS agglomerates. In the nanocomposites with higher POSS contents these conditions could not avoid it, because of the strong interaction among POSS molecules. The presence of two different crystalline phases in nanocomposite was evidenced by X-ray diffraction and Fourier Transformed Infra-Red Spectroscopy. The nanocomposite with 5 wt.% content had the highest values for degree of cristallinity. The polyhedral oligomeric silsesquioxane molecules are acting as lubricant in the system, once lower values for storage modulus as well as for viscosity were observed.

Synthesis and characterization of polyimide/polyhedral oligomeric silsesquioxane nanocomposites containing quinolyl moiety

AbstractA series of functional polyhedral oligomeric silsesquioxane (POSS)/polyimide (PI) nanocomposites were prepared using a two‐step approach. First, octa(aminophenyl)silsesquioxane (OAPS) was mixed with poly(amic acid) (PAA) prepared by reacting bis(4‐amino‐3,5‐dimethylphenyl)‐3‐quinolylmethane and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride. Second, the resulting solution was subjected to thermal imidization. The well‐defined ‘hard particles’ (POSS) and the strong covalent bonds in the amide linkage between the carbon atom of the carboxyl side group in PAA and the nitrogen atom of the amino group in POSS lead to a significant improvement in the thermal and mechanical properties. Homogeneous dispersion of POSS cages in the PI is evident from scanning electron microscopy, which further confirms that the POSS molecule becomes an integral part of the organic‐inorganic inter‐crosslinked network system. Differential scanning calorimetry and dynamic mechanical analysis show that the glass transition temperatures of the POSS‐containing nanocomposites are higher than that of the corresponding neat PI system, owing to the significant increase of the crosslinking density in the PI/POSS nanocomposites. Increasing the concentration of OAPS in the PI networks decreases the dielectric constant. Pure PI and PI/POSS systems have good antimicrobial activity. Copyright © 2011 Society of Chemical Industry

Sorbitol–POSS Interactions on Development of Isotactic Polypropylene Composites

This study investigates the nature of interactions between the molecules of polyhedral oligomeric silsesquioxane (POSS) containing silanol functionalities (silanol–POSS) and di(benzylidene)sorbitol (DBS) encountered in the development of nanocomposite fibers from the compounds of POSS, DBS, and isotactic polypropylene (iPP). The interactions were investigated using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, and oscillatory shear rheology. Mass and NMR spectrometry revealed that the molecules of silanol–POSS and DBS formed several amorphous noncovalent molecular complexes promoted by hydrogen bonding. More abundant complex formation was observed with silanol–POSS molecules carrying four silanol groups and phenyl substitutions. Such complex formation deterred fibrillation of DBS when the compounds of iPP, DBS, and silanol–POSS were cooled from homogeneous melt ...

Dielectric properties of polyhedral oligomeric silsesquioxane (POSS)-based nanocomposites at 77k

The goal of this study is to develop dielectric nanocomposites for high energy density applications at liquid nitrogen temperature by utilizing a unique nano-material polyhedral oligomeric silsesquioxanes (POSS). A POSS molecule is consisted of a silica cage core with 8 silicon and 12 oxygen atoms and organic functional groups attached to the corners of the cage. In this study, we utilize POSS for the fabrication of nanocomposites both as a silica nanoparticle filler to enhance the breakdown strength and as a surfactant for effective dispersion of high permittivity ceramic nanoparticles in a polymer matrix. The matrix materials selected for the study are polyvinylidene fluoride (PVDF) and poly(methyl methacrylate) (PMMA). The ceramic nanoparticles are barium strontium titanate (BST 50/50) and strontium titanate. The dielectric properties of the solution-cast nanocomposites films were correlated to the composition and processing conditions. We determined that the addition of POSS did not provide enhanced dielectric performance in PVDF- and PMMA-based materials at either room temperature or 77K. In addition, we found that the dielectric breakdown strength of PMMA is lower at 77K than at room temperature, contradicting literature data.

Hierarchical Self-Assembly of Polyhedral Oligomeric Silsesquioxane End-Capped Stimuli-Responsive Polymer: From Single Micelle to Complex Micelle

Responsive polymeric micelles have been widely studied because of their potential use in nanocontainers and nanocarriers. In this study, polyhedral oligomeric silsesquioxane (POSS) end-capped poly[2-(dimethylamino)ethyl methacrylate] (POSS-PDMAEMA), a stimuli-responsive organic-inorganic hybrid polymer, was synthesized via atom transfer radical polymerization (ATRP) using POSS-Br as a macroinitiator. The self-assembly behaviors of POSS-PDMAEMA in aqueous solution were studied by fluorescence probe, transmission electron microscopy (TEM), dynamic light scattering (DLS), high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD). The results revealed two self-assembly processes of POSS-PDMAEMA. First they self-assembled into a single micelle with the POSS molecules forming a crystal core and the PDMAEMA chains stretching as a corona. Then the single micelles, as building blocks, were able to reversibly form a hierarchical micelle-on-micelle structure (complex micelle) under external stimuli.

Novel elastomer‐dumbbell functionalized POSS composites: Thermomechanical and Morphological Properties

AbstractNanocomposites consisting of poly(styrene‐b‐butadiene‐b‐styrene) (SBS) and polyhedral oligomeric silsesquioxanes (POSS) were prepared using a solvent dispersion method. Dumbbell‐shaped POSS fillers were prepared using diacyl chlorides to bridge the POSS molecules. Infrared spectroscopy confirmed functionalization. Scanning electron microscopy revealed an increase in filler aggregation with concentration, with preferential phase selectivity. Polydispersity increased with filler concentration while d spacing was influenced by phase selectivity and domain‐filler compatibility. Functionalized POSS improved thermal stability by imparting restrictions of SBS chain motions. Tensile stress–strain analysis revealed an increase in modulus, yield strength, and strain hardening with filler concentration, while creep deformation decreased and permanent strain increased with POSS content. Storage modulus, loss modulus, and glass transition temperature increased with filler content due to effective SBS–POSS interaction. Nanocomposite properties were influenced by filler concentration, the phase of the filler was dispersed throughout and the length of the alkyl “barbell” on the dumbbell‐shaped POSS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Langmuir–Blodgett films composed of amphiphilic double-decker shaped polyhedral oligomeric silsesquioxanes

New amphiphilic polyhedral oligomeric silsesquioxanes (POSSs) were synthesized, and their monolayer behavior on a water surface and Langmuir–Blodgett (LB) film formation were studied. Two kinds of amphiphilic POSS molecules, which have two or four di(ethylene glycol) units (2OH-DDSQ and 4OH-DDSQ, respectively), were synthesized by direct hydrosilylation of di(ethylene glycol) vinyl ether with double-decker shaped polyhedral oligomeric silsesquioxanes (DDSQs). Surface pressure ( π)–area ( A) isotherms and Brewster angle microscope (BAM) measurements indicated that both amphiphilic DDSQs form a stable monolayer at the air–water interface. In addition, 4OH-DDSQ can be deposited on a solid substrate by the LB technique. Atomic force microscope (AFM) images of a one-layer 4OH-DDSQ film showed a homogenous uniform surface on a hydrophilic silicon substrate, whereas nanometer scale dots were formed on a hydrophobic silicon substrate. Multilayer deposition on a hydrophobic substrate resulted in an increase of dot size with increasing deposition number of layers. Moreover, homogenous multilayer films with a few voids were obtained on a hydrophilic substrate. The results indicate that 4OH-DDSQ is a good candidate for preparing hybrid nanoassemblies.

Role of interface in dispersion and surface energetics of polymer nanocomposites containing hydrophilic POSS and layered silicates

Three different hydrophilic nanofillers – natural and synthetic layered silicate as well as octaammonium polyhedral oligomeric silsesquioxane (POSS) – were incorporated into polyamide-6 by a solution-mixing method. The surfaces of the resulting polymer nanocomposites were characterized by X-ray diffraction, polarized optical microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and contact angle measurements. All polymer nanocomposites displayed enhancement in surface hydrophilicity as well as increase in surface free energy due to surface enrichment of the nanofillers. The degree of enhancement was found to depend on both nanofiller type and dispersion state. Interfacial interactions in the form of hydrogen bonding played an important role in affecting the dispersion state of the layered silicates. Exfoliated layered silicates caused a larger increase in hydrophilicity than aggregated layered silicate. On the other hand, aggregated POSS molecules were able to induce a large increase in hydrophilicity. Significant spreading of water was also observed on surfaces containing POSS molecules. Surface models have been proposed to explain these phenomena.