Polyhedral Oligomeric Silsesquioxane Molecules Research Articles

Crystallization and morphology study of polyhedral oligomeric silsesquioxane (POSS)/polysiloxane elastomer composites prepared by melt blending

Composites of poly(methylvinylsiloxane) (“silicone”) elastomers with polyhedral oligomeric silsesquioxane (POSS) were prepared by melt blending. One goal was to establish conditions that would lead to morphologies different from that of a simple filler dispersed in a polymer matrix for the purposes of reinforcement. To this end, the study focused on the dispersion and state of POSS in silicone rubber blends as determined by X-ray diffraction (XRD), polarizing optical microscopy (POM), scanning electron microscopy (SEM), and analysis using a rubber processing analyzer (RPA). Of particular interest were the thermal stability of POSS macromers, and the effects of mixing temperature and subsequent vulcanization of the polysiloxane. The results showed that highly crystalline POSS macromers could undergo condensation reactions at 230 °C in air, leading to partially amorphous structures. Also, POSS crystals apparently dissolved in the polysiloxane at high temperatures and POSS crystals with hexahedral or flake-like structures recrystallized out upon cooling. Both crystallites and POSS molecules co-existed in these blends, with the amount of dispersed molecular POSS being increased at higher temperatures. The POSS molecules exhibited some physical interactions with the polysiloxane uncross-linked chains, but phase separation was induced by the process of cross-linking. In this curing process, POSS molecules could react with the polysiloxane, resulting in decreases in cross-link density. The original POSS crystals could also be dissolved in the polysiloxane during the initial curing stages, but recrystallization upon cooling gave regenerated crystals that were roughly spherical.

In‐situ Synthesis and Characterization of Polyamide 6/POSS Nanocomposites

AbstractThe nanocomposites of polyamide 6 (PA6) and polyhedral oligomeric silsesquioxane (POSS) containing primary and secondary amino groups were synthesized through in‐situ polymerization. The chemical structure of the PA6/POSS nanocomposites was characterized with FT‐IR and 1H‐NMR spectroscopies. The solution viscosity results showed the increase in intrinsic viscosity with increasing POSS loadings. The random positioning of the POSS molecules in PA6 chain was confirmed by x‐ray diffraction studies. The gradual decrease in the melting point and crystallization temperature with increasing POSS content was observed by the differential scanning calorimetry. The thermogravimetric analysis results showed that the POSS incorporation does not enhance the thermal resistance of PA6/POSS nanocomposites.

Molecular simulation and theoretical modeling of polyhedral oligomeric silsesquioxanes

Polyhedral oligomeric silsesquioxane (POSS) molecules are unique nanometre-size inorganic/organic hybrid structures based on a (SiO1.5)8 core. Depending on the functionalization of the POSS cages, the resulting systems can be solid or liquid, or, upon crosslinking, turned into a network. While much is known experimentally about the chemical synthesis of POSS systems, very little theoretical understanding exists at the molecular level or beyond. Of particular interest is the study of the effect of tether groups on the thermodynamic properties and phase behaviour of POSS fluids, which is addressed in this work through both molecular simulation and the statistical associating fluid theory for potentials of variable attractive range (SAFT-VR). In this application of SAFT-VR to POSS molecules the hetero-SAFT-VR approach is used. The POSS cage is represented as a single sphere and the tether groups by one or more smaller spheres, depending on chain length. Since very limited experimental data is available for the thermodynamic properties of POSS systems, molecular dynamics simulations are used to obtain pseudo-experimental data with which to validate the theoretical approach. Good agreement is obtained between the simulation data and the theoretical results and predictions are made for systems yet to be studied by simulation or experiment.

Isothermal crystallization behavior of isotactic polypropylene blended with small loading of polyhedral oligomeric silsesquioxane

The isothermal crystallization kinetics and morphology development of isotactic polypropylene (iPP) blended with small loading of nanostructure of polyhedral oligomeric silsesquioxane (POSS) were studied with differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The crystallization behaviors of iPP/POSS composites presented an unusual crystallization behavior during isothermal and nonisothermal crystallization conditions. The exothermic morphologies of isothermal and nonisothermal crystallization of iPP/POSS composites changed remarkably with increasing POSS. Moreover, the developments of spherulitic morphology for iPP/POSS composites showed that the major dispersed POSS molecules became nanocrystals first and then aggregated together forming thread- or network-like morphologies, respectively, depending on POSS content, which was observed. It implies that these major POSS nanocrystals' morphologies appeared as an effective nucleating agent and promoted the nucleation rate of iPP, whereas the minor dispersed POSS molecules that had slight miscibility between iPP retarded the nucleation and growth rates of iPP in the remaining bulk region. Therefore, the isothermal crystallization showed a single exothermic peak at pure iPP and POSS-1.0, whereas at POSS-2.0 and POSS-3.0, displayed the multi-exothermic peaks during isothermal crystallization. These faces indicated that POSS molecules were both influence on the transport of iPP chain in the melted state and on the free-energy of formation the critical nuclei of iPP assisted by the POSS structures were observed. Therefore, we postulated that the crystallization mechanisms of multi-exothermic peaks in isothermal crystallization may proceed to combine the “ nucleating agent inducing nucleation of iPP event assisted by the POSS domains” that the nucleation of iPP does occur preferentially on the surfaces of the POSS “threads” or “networks” structures, and “ nucleation and growth of iPP in the remaining bulk melted iPP region retarded by dispersed POSS molecules”. Therefore, effects of POSS content on the isothermal and nonisothermal crystallization behaviors of iPP/POSS composites due to the POSS molecules partially miscible with iPP, at very small loading of POSS molecules, promoted or retarded the rates of nucleation and growth of iPP depending on the POSS content and crystallization temperature were discussed.

Organic-inorganic telechelic molecules: Solution properties from simulations

We report molecular dynamics simulations for telechelic molecules composed of two polyhedral oligomeric silsesquioxane (POSS) cages connected by one hydrocarbon backbone dissolved in liquid normal hexane. Silsesquioxanes are novel hybrid organic-inorganic molecules that are useful as building blocks for the synthesis of nanostructured materials. By including POSS molecules within a polymeric material it is possible to modify mechanical properties such as resistance to heat and glass transition temperatures. Unfortunately, the molecular mechanisms responsible for these enhancements are at present not completely understood. In an effort to elucidate the molecular phenomena responsible for these effects, we have studied the conformation of telechelic POSS molecules in solution, as well as their self-diffusion coefficients, as a function of the length of the hydrocarbon backbone. We focus on molecules in which the radius of gyration of the alkane backbone is comparable to the size of the silsesquioxane cages. Our results indicate that the backbone has a significant influence on both the equilibrium and the transport properties of dissolved telechelic hybrid molecules. These observations are useful for developing strategies to direct the self-assembly of nanostructured materials.

Water‐Responsive Shape Memory Polyurethane Block Copolymer Modified with Polyhedral Oligomeric Silsesquioxane

Nanostructured polyurethane block copolymers with shape memory were synthesized by using polyhedral oligomeric silsesquioxane (POSS) molecules and poly(ethylene glycol) (PEG), which acted as the hydrophobic and hydrophilic groups, respectively. The hard segment domains appeared to be dominantly governed by POSS molecules according to X‐ray diffraction and Fourier transform‐infrared (FT‐IR) measurements. As the POSS content increased, the phase separation between hard and soft segments gradually developed, followed by the crystallization of POSS molecules, and the melting temperature and heat of fusion for POSS crystals increased. The water‐responsive shape memory behavior which resulted from the dissolution of soft segments was demonstrated at 30°C. More than 70% shape recovery was achieved in the water‐responsive shape recovery test, which depended on the POSS content.

Preparation and Characterization of Polyurethane Hybrids from Reactive Polyhedral Oligomeric Silsesquioxanes

AbstractSummary: Hybrid polyester resins containing polyhedral oligomeric silsesquioxanes (POSS), and their polyurethanes were prepared using reactive POSS as a substitution for partial diol monomer. They were investigated by FT‐IR, rheometry, dynamic mechanical analysis, wide‐angle X‐ray diffraction, contact‐angle measurement, atomic force microscopy, and thermogravimetric analysis, respectively. The results showed that the hybrid polyester‐POSS resins had a shear thinning behavior, and the more the POSS was embedded, the stronger the shear thinning behavior, and the higher the viscosity. Incorporation of POSS could increase the glass transition temperature and thermal stability and decrease the surface free energy of the polyurethanes. When the POSS content was relatively high, the POSS molecules in hybrid polyurethane‐POSS had a strong self‐assembling ability to form nanocrystalline domains.Loss tangent curves of polyurethanes.magnified imageLoss tangent curves of polyurethanes.

Crystallization behavior and morphological development of isotactic polypropylene blended with nanostructured polyhedral oligomeric silsesquioxane molecules

AbstractThe thermal properties and morphological development of isothermally crystallized isotactic polypropylene (iPP) blended with nanostructured polyhedral oligomeric silsesquioxane (POSS) molecules at very small loading of POSS were studied with differential scanning calorimeter (DSC), thermal gravimetric analysis, dynamic mechanical analysis, polarized optical microscopy (POM), and wide‐angle X‐ray diffraction (WAXD). The result of DSC indicated that the crystallization rate of iPP increases with the increase in POSS contents during crystallization; moreover, the melting temperature of iPP/POSS nanocomposites slightly decreases, while the heat of fusion increases with the addition of POSS molecules at melting and remelting traces. The storage modulus and thermal stability, respectively, remarkably decrease, while the glass transition temperature of isothermally crystallized iPP/POSS nanocomposites increases slightly with the increase in POSS contents. The morphologies results of WAXD and POM show that the POSS molecules form about 35 nm sized nanocrystals and aggregate to form thread‐like and network structure morphologies, respectively, in the molten state even when the POSS content is very small. These results, therefore, suggest that the interaction force between the POSS molecules should be larger than the force between POSS molecules and iPP matrix; however, those interactions depend on the chain length of functionalized substituents on the POSS cage. Therefore, the POSS molecules aggregate forming nanocrystals and act as an effective nucleating agent for iPP and influence the thermal properties of iPP/POSS nanocomposites due to the shorter chain length of functionalized substituents, methyl, on the POSS cage. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2122–2134, 2006

Phenolic resin–trisilanolphenyl polyhedral oligomeric silsesquioxane (POSS) hybrid nanocomposites: Structure and properties

The structure and properties of organic–inorganic hybrid nanocomposites prepared from a resole phenolic resin and a POSS mixture containing >95 wt% trisilanolphenyl POSS was investigated by POM (polarized optical microscopy), SEM, TEM, WAXD, FT-IR, DSC, and TGA techniques. Composites with 1.0–10.4 wt% of POSS were prepared by dissolving the POSS and the phenolic resin into THF, followed by solvent removal and curing. Both nano- and micro-sized POSS filler aggregates and particles were shown to be heterogeneously dispersed in the cured matrix by POM, TEM, SEM, and X-EDS. POSS was found everywhere, including in both dispersed phase domains and in the matrix. The nanocomposite morphology appears to form by a multi-step POSS aggregation during the process of phase separation. Both the matrix and dispersed ‘particulate’ phase domains are mixtures of phenolic resin and POSS. POSS micro-crystals act as the core of the dispersed phase. The bigger dispersed domains consist of smaller particles or aggregates of POSS molecules that exhibit some order but regions of matrix resin are interspersed. A WAXD peak at 2 θ∼7.3° indicates crystalline order in the POSS aggregates. This characteristic peak's intensity increases with an increase in POSS loading, suggesting that more POSS molecules have aggregated or crystallized. FT-IR spectra confirm that hydrogen bonding exists between the phenolic resin and POSS Si–OH groups. This increases their mutual compatibility, but H-bonding does not prevent POSS aggregation and phase separation during curing. TGA measurements in air confirmed the temperature for 5% mass loss in increases with increase of POSS loading and at T>550° the thermal stability increases more sharply with POSS loading. The nanocomposite glass transition temperatures ( T g) are only slightly be affected by the POSS filler.

Evaluation of Force Fields for Molecular Simulation of Polyhedral Oligomeric Silsesquioxanes

Polyhedral oligomeric silsesquioxanes (POSS) are nanometer-size molecules suitable for the production of organic-inorganic nanocomposite materials. These organic-inorganic nano-building blocks show promise for enabling the production of polymeric materials of exceptional mechanical properties as well as novel composite materials. While the experimental studies of these materials have rapidly evolved in the past decade, their theoretical investigation is still in its infancy. Toward the validation of force fields for the molecular simulation of POSS-containing systems, we present the charge-transfer reactive (CTR) force field for the molecular simulation of polyhedral oligomeric silsesquioxane (POSS) molecules and compare the ability of this, and several force fields taken from the literature, to predict the thermophysical properties of POSS-containing systems. The literature force fields compared include the universal force field (UFF) and the COMPASS and Hybrid-COMPASS force fields. Predictions from molecular dynamics simulations of the structural parameters (unit cell vectors), melting temperature, and FT-IR spectra of crystals of POSS monomers are presented. The POSS monomers investigated are octahydride, octamethyl, and octapropyl POSS. Predicted quantities are compared to experimental results where available and provide molecular-level physical insight into several aspects of the behavior of POSS molecules. While all the force fields tested perform reasonably well, our results indicate that the Hybrid-COMPASS and CTR force fields predict structural properties that are in good agreement with experimental data.

Thermal and mechanical properties of polyhedral oligomeric silsesquioxane (POSS)/polycarbonate composites

A series of composite materials were produced incorporating polyhedral oligomeric silsesquioxane (POSS) derivatives into polycarbonate (PC), by melt blending. Significant differences in compatibility were observed depending on the nano-scale filler's specific structure: trisilanol POSS molecules generally provided better compatibility with PC than fully-saturated cage structures, and phenyl-substituted POSS grades were shown to be more compatible with PC than fillers with other functional groups. Trisilanolphenyl-POSS/PC composites possess the best overall performance among the POSS materials tested. The high compatibility between the trisilanolphenyl-POSS and polycarbonate matrix results in generation of transparent samples up to 5 wt% POSS content. Slightly enhanced mechanical properties including tensile and dynamic mechanical modulus are observed with the increase of trisilanolphenyl-POSS loading at the cost of decreasing ductility of the nanocomposites. Importantly, upon orientation of the PC/POSS nanocomposite, crystallization of POSS within the oriented material results—this observation is consistent with a growing number of observations which suggest that ‘bottom-up’ formation of structures incorporating multiple POSS cages result from orientation of these nanocomposites, and that the hybrid organic–inorganic inclusions may be at the heart of observed nano-scale reinforcement.

Sorption of Dimethyl Methylphosphonate within Langmuir−Blodgett Films of Trisilanolphenyl Polyhedral Oligomeric Silsesquioxane

Trisilanolphenyl polyhedral oligomeric silsesquioxane (POSS) molecules are used to create well-ordered Langmuir-Blodgett films containing silanol groups that interact strongly with dimethyl methylphosphonate (DMMP), a commonly used simulant for the chemical warfare agent sarin. The interaction of DMMP within multilayer POSS films is studied by uptake coefficient and temperature-programmed desorption (TPD) measurements, as well as reflection-absorption infrared spectroscopy (RAIRS). Results indicate a low uptake probability; however, in a DMMP-saturated atmosphere, the organophosphonate molecules are capable of diffusing into and adsorbing within the films. TPD and RAIRS measurements reveal no evidence of DMMP decomposition within the film. Rather, DMMP is found to desorb molecularly with a desorption energy of 122 kJ/mol. RAIRS reveals that strong hydrogen-bonding interactions between the phosphoryl groups of the organophosphonate molecules and the silanol groups of the POSS molecules are responsible for the high sorption energy of the system.

ε-Caprolactam polymerization in presence of polyhedral oligomeric silsesquioxanes (POSS)

Polyhedral oligomeric silsesquioxanes (POSS) have been covalently linked to polyamide 6 (PA6) chains with the aim of synthesizing hybrid organic/inorganic polymer materials. The synthesis has been achieved by in situ polymerization of ε-caprolactam (CL) in presence of increasing amounts of POSS molecules, using two polymerization mechanisms (hydrolytic and anionic). The latter method has been carried out by three different approaches, in order to get PA6 samples characterized by various morphologies and content of structural defects: (i) quasi-adiabatic bulk polymerization; (ii) isothermal bulk polymerization; (iii) quasi-isothermal suspension polymerization. The products obtained have been characterized in term of structure, morphology, thermal properties and molecular mass.

Ab initio study of the binding strength of POSS-cation complexes

Polyhedral oligomeric silsesquioxane (POSS) is a cage-shaped molecule comprised of alternating silicon and oxygen atoms that have found increasing use as filler in polymer nanocomposites. The presence of four oxygen atoms on each face of the POSS cage suggests that the molecule forms a stable complex with a cationic atom or molecule. Although experimental evidence exists for gas-phase binding, the lack of an estimate of this binding strength makes it difficult to predict if complex formation is feasible in condensed systems. This paper presents an ab initio DFT study of the binding strength of POSS-cation complexes based on cation type, POSS cage functionalization, and the presence of a counterion. The binding strength of an unfunctionalized (i.e. with H-terminated corners) POSS molecule with a Li + ion is found to be ∼80 kT at room temperature in vacuo. In a poly(styrene) solvent, the polarity of the medium is estimated to affect little this binding energy. Cyclohexyl ligand substitution is found to increase the binding strength by an additional 30 kT. In the presence of a tightly bound counterion (Cl −), the binding energy drops to the still substantial value of ∼20 kT. POSS is found also to bind cationic surfactants (through study of the model +NH 3CH 3) at ∼25 kT, suggesting a possible new route to POSS modification to hinder agglomeration. This study supports the conclusion that POSS-cation complex formation is feasible in the presence of polymer.

Epoxy Networks Reinforced with Polyhedral Oligomeric Silsesquioxanes (POSS). Structure and Morphology

Epoxy−amine networks were modified with well-defined inorganic building blockspolyhedral oligomeric silsesquioxanes (POSS). POSS molecules were incorporated in the organic−inorganic networks as dangling units of a network chain or as network junctions. Mono- or polyepoxide POSS monomers were used to prepare the two types of networks. The structure of the POSS-containing networks, including the structure evolution during network formation, was determined by SAXS, WAXS, and TEM. The POSS pendant on a network chain shows a strong tendency toward aggregation and crystallization, depending on the POSS organic ligands. During network formation, ordering of the crystal domains takes place. The POSS−POSS interaction is the main factor controlling the network structure. Also, the polyepoxy POSSs monomers aggregate in the organic matrix; however, during network formation the system becomes more homogeneous and POSSs as network cross-links become better dispersed. Still, in the cured organic−inorganic networks the P...

Styrene−Butadiene−Styrene Triblock Copolymers Modified with Polyhedral Oligomeric Silsesquioxanes

A novel hybrid organic/inorganic triblock copolymer of polystyrene−butadiene−polystyrene (SBS) containing grafted polyhedral oligomeric silsesquioxane (POSS) molecules was synthesized by a hydrosilation method. The POSS molecules were designed to contain a single silane functional group, which was used to graft onto the dangling 1,2-butadienes in the polybutadiene soft block. Unlike typical free radical copolymerizations commonly used for many other POSS incorporations investigated, this synthesis method allows us to make a series of polymers with varying amounts of POSS without any change to the overall degree of polymerization or structure of the main SBS backbone. This gives us a unique opportunity to study the POSS behavior in the matrix and know that all differences are solely due to the POSS grafted to the soft continuous butadiene phase. X-ray diffraction revealed that the grafted POSS are very well dispersed in the matrix of the hybrid polymer, which is compared to the strong phase segregation obs...

Unique Rodlike Surface Morphologies in Trisilanolcyclohexyl Polyhedral Oligomeric Silsesquioxane Films

A trisilanol derivative of polyhedral oligomeric silsesquioxane (POSS), trisilanolisobutyl-POSS, has recently been reported to form stable monolayers at the air/water interface. This paper explores the mono- and multilayer properties of another POSS derivative, trisilanolcyclohexyl-POSS, with pi-A isotherm and Brewster angle microscopy measurements. Results show that with continuously increasing surface concentration via symmetrical compression, trisilanolcyclohexyl-POSS amphiphiles at the air/water interface undergo a series of phase transitions from traditional Langmuir monolayers (one-POSS-molecule thick) to unique rodlike hydrophobic aggregates in multilayer films (approximately eight-POSS-molecules thick) that are dramatically different from "collapsed" morphologies seen in other systems. Stable and hydrophobic rodlike structure formation on water is presumably due to trisilanolcyclohexyl-POSS' unique molecular structure and strong tendency to form intermolecular hydrogen bonds in the solid state. This result is consistent with existing POSS/polymer composite research, which shows that POSS molecules tend to aggregate and crystallize into lamellar nanocrystals.

Polyhedral Oligomeric Silsesquioxane Amphiphiles: Isotherm and Brewster Angle Microscopy Studies of Trisilanolisobutyl-POSS at the Air/Water Interface

A trisilanol derivative of polyhedral oligomeric silsesquioxanes (POSS), trisilanolisobutyl-POSS, has recently been reported to form stable monolayers at the air/water interface. Moreover, the trisilanolisobutyl-POSS monolayer undergoes a nonequilibrium structural transition (collapse) around a surface pressure of Rho approximately 18 mN.m(-1). This paper explores the mono- and multilayer properties of POSS molecules at the air/water interface by the Wilhelmy plate technique and Brewster angle microscopy. Surface concentrations are controlled by four mechanisms: (1) compression at a constant rate, (2) stepwise compression followed by surface pressure relaxation to an "equilibrium" value, (3) successive additions of spreading solution followed by relaxation to a stable surface pressure value, and (4) hysteresis loops to test the reversibility of the structural transitions. Results show that both an increasing compression rate and a decreasing temperature lead to an increase in the surface pressure of the structural transition, which is consistent with the formation of solidlike multilayer domains during the collapse process. For the case of compression at a constant rate, small domains initially form and later aggregate to form large solid masses. Cessation of compression allows these large solid masses to relax into equilibrium ringlike structures with a lower surface pressure, Rho approximately 13 mN.m(-1). In contrast, if the film is expanded rapidly, these large solidlike domains relax into "spaghetti" like networks with a residual surface pressure that depends on the initial amount of the solidlike collapsed phase. Finally, successive addition and stepwise compression isotherm experiments lead to different and time-dependent morphologies. Understanding these surface properties of POSS molecules affords an excellent opportunity to design and study POSS/polymer blends for coating applications where POSS molecules with rigid inorganic cores, soft organic coronae, and dimensions comparable to polymeric monolayers can serve as perfectly monodisperse nanofillers.

Synthesis and characterization of hyperbranched aromatic poly(ether imide)s with terminal amino groups

AbstractWe synthesized an AB2‐type monomer, 4‐{4‐[di(4‐aminophenyl)methyl]phenoxy}phthalic acid, which contained one phthalic acid group and two aminophenyl functionalities. The direct self‐polycondensation of the AB2‐type monomer in the presence of triphenylphosphite as an activator afforded a hyperbranched poly(ether imide) with a large number of terminal amino groups. This polymer was characterized with 1H NMR and IR spectroscopy. The degree of branching of the hyperbranched poly(ether imide) was approximately 56%, as determined by a combination of model compound studies and an analysis of 1H NMR spectroscopy integration data. The terminal amino groups underwent functionalization readily. The solubility and thermal properties of the resulting polymers depended on the nature of the chain end groups. In addition, the hyperbranched poly(ether imide) was grafted with polyhedral oligomeric silsesquioxane (POSS). Transmission electron microscopy analysis revealed that the grafted POSS molecules aggregated to form a nanocomposite material. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3726–3735, 2003

Polyimide-Side-Chain Tethered Polyhedral Oligomeric Silsesquioxane Nanocomposites for Low-Dielectric Film Applications

Low-dielectric-constant nanoporous films (dielectric constant, k = 2.4) with thermal integrity and controllable mechanical strength have been prepared by covalently tethering nanoporous polyhedral oligomeric silsesquioxane (POSS) molecules, 1-nm size, to the side chains of polyimide. The tethered POSS molecules in the amorphous polyimide retain a nanoporous crystal structure, but form an additional ordered architecture due to microphase separation. With this approach, the dielectric constant of the film can be tuned by the amount of POSS molecules introduced in the nanocomposite film; the polyimide molecules offer additional advantages of maintaining certain thermal and mechanical strengths.