Polyhedral Oligomeric Silsesquioxane Compounds Research Articles

Molecular simulations of the miscibility in binary mixtures of PVDF and POSS compounds

The miscibility behavior of binary mixtures of poly(vinylidene difluoride) (PVDF) and six different kinds of polyhedral oligomeric silsesquioxanes (POSS) compounds ((ethylic)8Si8O12 (E-POSS), (phenyl)8Si8O12 (P-POSS), (3, 3, 3-trifluoropropyl)8Si8O12(FP-POSS), (1H, 1H, 2H, 2H-nonafluorohexyl)8Si8O12 (FH-POSS), (1H, 1H, 2H, 2H-tridecafluorooctyl)8Si8O12 (FO-POSS) and (1H, 1H, 2H, 2H-heptadecafluorodecyl)8Si8O12 (FD-POSS)) was studied using molecular simulations and the extended Flory–Huggins model. First, the pairwise binding energies Eij and coordination numbers Zij were computed by means of a Monte Carlo approach. Then the mixing energies Emix, the Flory–Huggins interaction parameters χ and the free energies ΔGmix in the temperature range 100–600 K and phase diagrams of the six different mixtures were obtained. All these results indicate that PVDF/FP-POSS, PVDF/FH-POSS, PVDF/FO-POSS and PVDF/FD-POSS are fully miscible at any temperature. PVDF/E-POSS and PVDF/P-POSS are immiscible except at very high temperatures. The lowest energy frames and the frame energies show that the miscibility of PVDF and the four kinds of fluorinated POSS compounds is derived from the polar C–F bonds and the electrostatic interactions in their molecules.

Ab initio molecular orbital study of the insertion of H2 into POSS compounds

The insertion of one and two H2 molecules into polyhedral oligomeric silsesquioxanes (POSS) was investigated as a function of the size of the cage, using both Hartree-Fock (HF) and second order perturbation theory (MP2) methods. Also investigated was the same reaction into the heavier groups 4 and 14 metal-substituted POSS (metallasilsesquioxanes) such as Ge-POSS, Si/Ge-mixed POSS, and Ti- and Zr-POSS. The properties of these species in comparison with those of POSS are discussed.

Incorporation of metallic POSS, POSS copolymers, and new functionalized POSS compounds into commercial dental resins

AbstractAn array of polyhedral oligomeric silsesquioxane (POSS) compounds, including metal, methacrylate, and amine functional POSS, and POSS copolymers were incorporated into aromatic and aliphatic dental resins. Heptaphenyl‐propylamine POSS and methacrylate derivatives were synthesized by corner‐capping and Michael addition reactions, respectively. The POSS compounds were tested for solubility in commercial resins at concentrations of 1, 5, 10, and 15 wt %, followed by UV polymerization of all soluble combinations. The POSS compounds generally increased modulus and had an unpredictable effect on Tg. The modulus of the aliphatic resin increased 83% by incorporation of 15 wt % aluminum‐phenyl POSS, while aromatic resins saw a maximum modulus improvement of 18% at 30°C and 72% at 160°C by incorporating 1 wt % of heptaphenyl‐methacrylate POSS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2856–2862, 2006

Application of ion mobility to the gas-phase conformational analysis of polyhedral oligomeric silsesquioxanes (POSS)

Ion mobility experiments and molecular modeling calculations were used to investigate the gas-phase conformational properties of various polyhedral oligomeric silsesquioxanes (POSS) cationized by sodium. POSS, (RSiO 3/2) n , has a rigid SiO cage with organic substituents attached to each Si atom. Na +POSS ions were formed by electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) and their collision cross-sections were measured in helium using ion mobility methods. Calculated cross-sections of theoretical models of the POSS ions, generated by molecular mechanics (MM) calculations, were compared to experiment for conformational identification. The calculations predict that the Na + ion remains outside of the SiO cage and binds to one to two oxygen atoms in the cage or interacts with two neighboring organic substituents. Cross-sections of X-ray structures were also compared to the experimental and theoretical data to determine if any changes occur to POSS in the gas phase (compared to the condensed phase) and to provide a check for the geometries predicted by theory (which used untested Si parameters). Several types of POSS compounds were investigated that had different SiO cage sizes (Si 6O 9, Si 8O 12, Si 10O 15, Si 12O 18, …) and different “R” substituents such as cyclohexyl, cyclopropyl, vinyl, and phenyl groups. Experimental, theoretical, and X-ray cross-sections differed by <2% for each POSS compound.

Nanoscale reinforcement of polyhedral oligomeric silsesquioxane (POSS) in polyurethane elastomer

A unique class of polyurethane (PU) elastomer containing inorganic molecules (polyhedral oligomeric silsesquioxane, POSS) as molecular reinforcement in the hard segment was investigated by means of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. WAXD results indicate that POSS molecules form nanoscale crystals showing distinct reflection peaks. The formation of POSS crystals is probably prompted by the microphase separation between solid-like hard segments and rubbery soft segments in PU. The microphase separation of hard and soft segments was observed by SAXS, which shows a long period of 111 A for 34 wt% POSS-PU and 162 A for 21 wt% POSS-PU, and hard segment domains with sizes of about 34 A for both of them. WAXD results from a series of POSS compounds with a corner substituted by a functional group of varying length were compared with POSS-PU, which also confirms the presence of nanoscale POSS crystals in the polymer matrix. © 2000 Society of Chemical Industry

Thermoplastic Hybrid Materials: Polyhedral Oligomeric Silsesquioxane (Poss) Reagents, Linear Polymers, and Blends

Polyhedral Oligomeric SilSesquioxanes (POSS) are structurally well defined cage-like molecules represented by the generic formula (RSiO{sub 1.5}){sub n}. POSS compounds possess a unique hybrid composition with an oxygen to silicon ratio of 1.5, intermediate between that for silica and silicone. An entire monomer catalogue (chemical tree) of hybrid POSS-based reagents suitable for polymerization and grafting reactions has been developed from R{sub 7}Si{sub 7}O{sub 9}(OH){sub 3} and related precursors. POSS reagents containing no more than one or two reactive groups enable the preparation of hybrid materials with desirable physical properties such as thermoplasticity, and elasticity. An overview of the synthesis of POSS monomers and thermoplastic POSS-acrylic polymers is given. The thermal and physical properties for POSS-acrylic monomers, homopolymers, and copolymers, and blends with poly(methylmethacrylate) are described.