Polyhedral Oligomeric Silsesquioxane Content Research Articles

TriSilanolPhenyl POSS–polyimide nanocomposites: Structure–properties relationship

Polyhedral Oligomeric Silsesquioxane (POSS)–polyimide (PI) thin films were synthesized from pre-mixed solution of oxydianiline–pyromellitic dianhydryde (ODA–PMDA) and TriSilanolPhenyl (TSP) POSS. POSS–PI polymerization reaction kinetics was studied using Fourier Transform Infrared (FTIR) spectroscopy. The POSS–PI films were then investigated by tensile tests, followed by surface morphology examination using Atomic Force Microscopy (AFM) and Environmental Scanning Electron Microscopy (ESEM). An interdisciplinary approach was applied for establishing a relation between POSS–PI composites chemical microstructure properties and failure mechanisms. Inter molecular POSS–POSS interaction by either phase separation, or chemical POSS–POSS condensation reaction were observed as key factors, affecting the nanocomposite mechanical properties via formation of aggregates. The amount and density of these aggregates were shown to be composition dependent. A model based on formation and coalescence of voids during tensile tests was suggested for understanding the effect of the POSS content on the POSS–PI mechanical response.

Effect of POSS on morphology and properties of poly(2,6-dimethyl-1,4-phenylene oxide)/polyamide 6 blends

Poly(2,6-dimethyl-1,4-phenylene oxide)/polyamide 6 (PPO/PA6) (50/50 w) blends filled with epoxycyclohexyl polyhedral oligomeric silsesquioxane (POSS) were prepared via melt-mixing. The reactions between POSS and PPO/PA6 blends were studied by Fourier transform infrared spectroscopy, end group and gel content tests. The morphology of PPO/PA6/POSS composites was observed by field emission scanning electron microscope and transmission electron microscope. As a chain extender and a crosslinking agent for PA6, POSS largely affected the morphology of the composites, which was mainly dependent on the melt-viscosity ratio and interfacial tension between the components. With increasing POSS content from 2 to 4 phr, the morphology of the composites transformed from droplet/matrix to co-continuous morphology. The PPO/PA6/POSS composites with co-continuous morphology had the better mechanical properties than those with droplet/matrix morphology. Dynamic mechanical thermal analysis showed that the addition of POSS increased the T g of PA6.

Preparation of polymer/POSS nanocomposites by radiation processing

Multifunctional polyhedral oligomeric silsesquioxane (POSS)-reinforced polypropylene (PP) nanocomposites were prepared by a simple and economical radiation processing, which has a great potential for the preparation of high-performance materials. The tensile strength of PP/POSS nanocomposites increased with an increasing POSS content up to 5 wt% and with an increasing absorption dose up to 50 kGy. The tensile strength of irradiated PP/POSS nanocomposites decreased at high absorption dose due to the main chain scission of PP by radiation. The PP/POSS nanocomposites showed improved thermal stability due to the formation of crosslinked network between PP and POSS by radiation.

Organic–inorganic hybrid hydrogels involving poly(N‐isopropylacrylamide) and polyhedral oligomeric silsesquioxane: Preparation and rapid thermoresponsive properties

Abstract3‐Acryloxypropylhepta(3,3,3‐trifluoropropyl) polyhedral oligomeric silsesquioxane (POSS) was synthesized and used as a modifier to improve the thermal response rates of poly(N‐isopropylacrylamide) (PNIPAM) hydrogel. The radical copolymerization among N‐isopropylacrylamide (NIPAM), the POSS macromer and N,N′‐methylenebisacrylamide was performed to prepare the POSS‐containing PNIPAM cross‐linked networks. Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) showed that the POSS‐containing PNIPAM networks displayed the enhanced glass transition temperatures (Tg's) and improved thermal stability when compared with plain PNIPAM network. The POSS‐containing PNIPAM hydrogels exhibited temperature‐responsive behavior as the plain PNIPAM hydrogels. It is noted that with the moderate contents of POSS, the POSS‐containing PNIPAM hydrogels displayed much faster response rates in terms of swelling, deswelling, and re‐swelling experiments than plain PNIPAM hydrogel. The improved thermoresponsive properties of hydrogels have been interpreted on the basis of the formation of the specific microphase‐separated morphology in the hydrogels, that is, the POSS structural units in the hybrid hydrogels were self‐assembled into the highly hydrophobic nanodomains, which behave as the microporogens and promote the contact of PNIPAM chains and water. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 504–516, 2009

Preparation and thermal properties of hybrid nanocomposites of poly(methyl methacrylate)/octavinyl polyhedral oligomeric silsesquioxane blends

AbstractA series of poly(methyl methacrylate) (PMMA)/octavinyl polyhedral oligomeric silsesquioxane (POSS) blends were prepared by the solution‐blending method and characterized with Fourier transform infrared, X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis techniques. The glass‐transition temperature (Tg) of the PMMA–POSS blends showed a tendency of first increasing and then decreasing with an increase in the POSS content. The maximum Tg reached 137.2°C when 0.84 mol % POSS was blended into the hybrid system, which was 28.2°C higher than that of the mother PMMA. The X‐ray diffraction patterns, transmission electron microscopy micrographs, and Fourier transform infrared spectra were employed to investigate the structure–property relationship of these hybrid nanocomposites and the Tg enhancement mechanism. The results showed that at a relatively low POSS content, POSS as an inert diluent decreased the interaction between the dipolar carbonyl groups of the homopolymer molecular chains. However, a new stronger dipole–dipole interaction between the POSS and the carbonyl of PMMA species formed at the same time, and a hindrance effect of nanosize POSS on the motion of the PMMA molecular chain may have played the main role in the Tg increase of the hybrid nanocomposites. At relatively high POSS concentrations, the strong dipole–dipole interactions that formed between the POSS and carbonyl groups of the PMMA gradually decreased because of the strong aggregation of POSS. This may be the main reason for the resultant Tg decrease in these hybrid nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Viscoelastic properties and residual stresses in polyhedral oligomeric silsesquioxane‐reinforced epoxy matrices

AbstractFiber‐filled thermosetting polymer composites are extensively used in aerospace industries. One disadvantage of these materials is cure induced or thermally induced residual stresses in the matrix, which may result in deteriorated performance and premature failure. This article explores the use of epoxy/multifunctional polyhedral oligomeric silsesquioxane (POSS) nanocomposites as resins with reduced thermal stress coefficients that result in mitigated residual stresses. The effect of POSS loading on the thermal stress coefficient of the epoxy/POSS nanocomposite resins was investigated from below the β‐relaxation to the α‐relaxation, or glass transition temperature, (i.e., from −100 to 180 °C) by measuring the shear modulus and linear thermal expansion coefficient. The thermal stress coefficient of the epoxy/POSS nanocomposites is found to be a strong function of temperature, decreasing rapidly with decreasing temperature through the α‐relaxation region, increasing in the vicinity of the β‐relaxation, and then decreasing below the temperature associated with the peak in the β‐relaxation. With increasing POSS content, the thermal stress coefficient is reduced compared with the neat resin in the vicinity of the α‐relaxation; however, the thermal stress coefficient increases with increasing POSS content below the temperature of the β‐relaxation peak. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2719–2732, 2008

Polyhedral oligomeric silsesquioxane-reinforced polyurethane acrylate

Hybride nanocomposite films of polyhedral oligomeric silsesquioxane (POSS) and polyurethane acrylate (PUA) were prepared by introducing POSS into PUA by free-radical photopolymerization, to enhance thermo-mechanical properties of PUA. The addition of POSS to PUA resulted in increases in the following properties: elasticity, glass transition temperature, thermal stability and dimensional stability. With increasing POSS content, the elastic modulus and thermal stability of PUA films increased due to an increased crosslinking density and the reinforcing effect of POSS particles on the PUA, whereas the surface free energies of these films decreased. The water contact angle against water increased due to the enhancement of the hydrophobicity of the polymer surface, caused by the low surface energy of POSS molecular. However, at high POSS content the mechanical properties of the films were decreased, as a result of aggregation of the POSS particles.

Preparation and characterization of styrene/styryl–polyhedral oligomeric silsesquioxane hybrid copolymers

AbstractBACKGROUND: Organic–inorganic nanocomposites were prepared by copolymerization of various monomers and polyhedral oligomeric silsesquioxane (POSS) derivatives. Preliminary results showed that styrene/styryl–POSS copolymers could be obtained using CpTiCl3 catalyst. In the work reported here, the copolymerization of styrene and styryl‐substituted POSS was studied in detail for a more effective catalyst, Cp*TiCl3.RESULTS: The glass transition temperature (Tg) of the copolymers prepared increased with increasing POSS content. The degradation temperature (Td) of the copolymers was 60 °C higher than that of syndiotactic polystyrene under nitrogen. Although the thermal properties were improved by incorporation of POSS, the catalytic activity decreased with POSS content. The racemic triad and syndiotactic index of the copolymers decreased with increasing POSS content. Gel permeation chromatograms of the copolymers exhibited multimodal distribution due to the presence of multi‐active centres, which were formed by interaction of Ti with the POSS siloxane linkage.CONCLUSION: With the incorporation of POSS, the thermal properties of polystyrene were improved. The styrene/styryl–POSS copolymers are formed through the various active sites arising from the interactions of Ti with POSS. Copyright © 2008 Society of Chemical Industry

Synthesis and Luminescent Property of Polycarbazole/Polyhedral Oligomeric Silsesquioxane Nanocomposites

Polyvinylcarbazole(PVK) composites containing organic-inorganic hybrid polyhedral oligomeric silsesquioxane(POSS) PVK-POSS were prepared by free radical polymerization. POSS monomers reacted with vinylcarbazole and were completely dispersed at molecular level in PVK matrix and PVK-POSS nanocomposites display higher glass transition temperature(Tg) in comparison with neat PVK. Optical properties of PVK/POSS nanocomposites were investigated by UV-spectrum and PL-spectrum and the results show that the PVK-POSS nanoparticles have a good interface effect and improve color purity effectively. The maximum absorption wavelength bathochromically shifts gradually with the increasing of the content of POSS. The luminescent intensity becomes higher and higher with the increase of POSS content, and reaches its maximum luminescent intensity when the POSS content is 3% (mass fraction), while some POSS-rich nanoparticles are present in matrix when contents of POSS are beyond 5%.

Preparation and properties of POSS grafted polypropylene by reactive blending

The octavinyl polyhedral oligomeric silsesquioxane (POSS) grafted polypropylene (PP) was first prepared by reactive blending. The structure and properties of physical blending and reactive blending composites of PP/POSS were investigated by wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA). WAXD analysis shows that the POSS in the reactive blending composites has better compatibility with PP than in the physical blending composites. The β-form crystalline hence disappears even the non-reactive POSS can act as an effective β-nucleating agents. DSC analysis shows the reactive blending composites have higher crystalline temperature while POSS in the physical blending composites have little effect on the crystalline temperature. The modulus of reactive blending composites increases in the presence of POSS, while that of the physical blending composites decreases with increasing POSS content.

Mechanism of Thermal Degradation of an Inorganic‐Organic Hybrid Based on an Epoxy‐POSS

AbstractA novel inorganic‐organic hybrid material, belonging to the family of polyhedral oligomeric silsesquioxanes (POSS), was used to reduce the trend of a conventional epoxy‐amine system to undergo combustion. The mixtures with different percentages in weight of POSS, and equal number of equivalents between of epoxy and amino groups were tested by thermogravimetic analysis (TGA) in both, argon and oxygen atmospheres. The results indicated that the char/ceramic yield values increase with the content of POSS and therefore, fire resistance is enhanced. Activation energies of degradation processes were obtained by Kissinger‐Akahira‐Sunose method. An empirical kinetic model satisfactorily explained the degradation mechanism of different blends.

Characterization of negative-type photoresists containing polyhedral oligomeric silsesquioxane methacrylate

A series of negative-type photoresists made by blending with various contents of polyhedral oligomeric silsesquioxane (POSS) methacrylate were prepared and characterized. These POSS macromers tend to crystallize or aggregate to form their own domains within the photoresist matrix. Sensitivity of the POSS modified photoresist is significantly improved with the increase of the POSS content. Results from photo-DSC analyses indicate that both induction time and peak maximum of heat flux are reduced by blending with POSS macromer. Addition of the proper amount (<13 wt%) of POSS can effectively increase photo-polymerization rate and exothermic heat. Hydrogen bonding interaction between the hydroxyl of photoresist and the siloxane of POSS tends to attract methacrylate double bonds surrounding POSS particles locally and thus enhances the rate of photo-polymerization and sensitivity.

Epoxy nanocomposites containing mercaptopropyl polyhedral oligomeric silsesquioxane: Morphology, thermal properties, and toughening mechanism

AbstractA novel polyhedral oligomeric silsesquioxane (POSS) containing a mercaptopropyl group [mercaptopropyl polyhedral oligomeric silsesquioxane (MPOSS)] was synthesized via the hydrolytic condensation of γ‐mercaptopropyl triethoxysilane in an ethanol solution catalyzed by concentrated hydrochloric acid and was used to modify epoxy–amine networks by a cocuring reaction with diglycidyl ether of bisphenol A (DGEBA). The structure, morphology, and thermal and mechanical properties of these MPOSS/DGEBA epoxy nanocomposites were studied and investigated with thermogravimetric analysis/differential thermal analysis (TGA–DTA), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). From SEM analysis, we observed that the miscibility between epoxy and POSS occurred at a relatively high POSS content, which characterized this mixture as a polymer nanocomposite system. The impact test showed that MPOSS reinforced the epoxy effectively, and the SEM study of the impact fracture surface showed that the fibrous yielding phenomenon observed was an indication of the transition of the brittle stage to a ductile stage and correlated well with the large increases in the impact strength; this was in agreement with the in situ reinforcing and toughening mechanism. The TGA–DTA analysis indicated that the MPOSS/DGEBA epoxy hybrids exhibited lower thermostability at a lower temperature but higher thermostability and higher efficiency in char formation at an elevated temperature. Differential scanning calorimetry showed that the glass transition temperature (Tg) of the MPOSS/epoxy hybrids were lower than that of the neat epoxy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Synthesis and characterization of poly(trimethylene terephthalate)/polyhedral oligomeric silsesquixanes nanocomposites

AbstractThis article reports the preparation of poly(trimethylene terephthalate) (PTT)– polyhedral oligomeric silsesquioxanes (POSS) nanocomposites through in situ polymerization. The chemical structure of the PTT–POSS nanocomposites was characterized with Fourier‐transform infrared and nuclear magnetic resonance spectroscopies and the presence of POSS was further confirmed by the elemental analysis. The crystal structures as well as the position of POSS in the nanocomposites were ascertained by the X‐ray diffraction (XRD) studies. Thermal characterization studies showed the gradual decrease in the glass transition and melt crystallization temperatures. Though the thermal stability of the PTT was not affected by the incorporation of POSS, the amount of residues obtained from thermal degradation process was increased with an increase in the content of POSS. The tensile studies showed that the values of initial modulus and breaking strength were dramatically decreased with an increase in the content of POSS. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers

Rheological behavior of polypropylene/octavinyl polyhedral oligomeric silsesquioxane composites

AbstractThe reactive blending composites of isotactic polypropylene (PP)/octavinyl polyhedral oligomeric silsesquioxane (POSS) were prepared in the presence of dicumyl peroxide. Comparison of the rheological behavior of physical and reactive blending composites was made by oscillatory rheological measurements. It was found that the viscosity of physical blending composites drops at lower POSS content (0.5–1 wt %) and thereafter increases with increasing POSS content; that of reactive blending composites increases with increasing POSS content and displays a solid‐like rheological behavior at low frequency region when POSS content is higher than 1 wt %. The deviation of reactive blending composites from the scaling log G′–log G″ of linear polymer in Han plot, upturning at high viscosity in Cole–Cole plot, and from van Gurp–Palmen plot are related to the gelation behavior reactively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 526–533, 2008

Effect of polyhedral-oligomeric-sil-sesquioxanes on thermal and mechanical behavior of SC-15 epoxy

In this study, thermal and mechanical properties of nanocomposites containing SC-15 epoxy resin and polyhe- dral-oligomeric-sil-sesquioxanes (POSS) have been studied. Dynamic Mechanical Analysis (DMA) results show that the addition of 5 wt% of POSS yielded a 13% increase in the storage modulus and a 16°C enhancement in Tg. Thermo gravi- metric Analysis (TGA) results show that the thermal stability of epoxy increased with higher POSS content. Tension tests were used to evaluate the mechanical properties of materials. Both modulus and tensile strength are linear functions of POSS content. Scanning Electric Microscopy (SEM) pictures of fracture surfaces show that the roughness of the fracture surfaces of epoxy increased after adding POSS. Based on experiment results, a three-parameter nonlinear constitutive equa- tion was developed to describe the strain-softening stress-strain relationship behavior of materials. The parameters in this model are the elastic modulus, a strain exponent, m, and a compliance factor, β. Their relationships to the POSS weight fraction were obtained from the experiment results. The simulated stress-strain curves from the model agree with the test data. Analysis of the model shows that both the strain exponent, m, which controls the strain softening and hardening effect of the material, and the compliance parameter, β, which controls the flow stress level of the material, increase with higher POSS content.

Synthesis of semitelechelic POSS‐polymethacrylate hybrids by thiol‐mediated controlled radical polymerization with unusual thermal behaviors

AbstractWe have developed an efficient and versatile method for the synthesis of polyhedral oligomeric silsesquioxanes (POSS)‐polymethacrylate hybrids, such as POSS‐poly(methyl methacrylate) (POSS‐PMMA), POSS‐poly(ethyl methacrylate) (POSS‐PEMA), and POSS‐poly(benzyl methacrylate) (POSS‐PBzMA) of controllable molecular weights and low polydispersities by thiol‐mediated radical polymerization at elevated temperature (100 °C). By tuning the reactant concentrations and degree of polymerization of the grafted polymethacrylate chains, POSS content in these hybrid materials could be varied. MALDI‐TOF‐MS analysis of the hybrid molecule shows that the nanoscale POSS moiety is connected to the end of polymethacrylate chain through the sulfur atom bridge. These hybrid materials were further characterized using various techniques such as FTIR, XRD, NMR, TGA, and DSC. In all synthesized hybrids, the incorporation of POSS moiety at the end of polymethacrylate chain resulted in the decrease of glass transition temperature (Tg) compared to that of neat polymethacrylates of comparable molecular weights. Surprisingly, POSS‐PMMA hybrids only with relatively high POSS content (∼ 10 and 16 wt %) showed physical aging behavior as reveled by DSC study. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1111–1123, 2008

Self-Assembly of Methacrylic Nanostructured Copolymers Containing Polyhedral Oligomeric Silsesquioxanes

AbstractTwo hybrid copolymer series obtained by free-radical copolymerization of methacrylcyclohexyl Polyhedral oligomeric silsesquioxane (POSS) with butyl methacrylate or 2-ethylhexylmethacrylate were characterized by 1H-NMR spectroscopy, gel permeation chromatography (GPC), X-rays Diffraction (XRD), differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA). Reactivity ratios were calculated by low yield composition data suggesting the formation of random copolymers with low probability of poly-POSS sequences. XRD studies showed the crystallization behaviour of the inorganic phase independently on the POSS content; however sample processing by solvent casting effectively hindered the copolymer self-assembling ability. DSC suggests the formation of polyphasic structures with Tg increasing with POSS content, and with endothermal peaks occurring at higher temperature. Finally TGA shows an improved thermal stability of hybrid copolymers with char yield correlated to the level of inorganic phase.

Synthesis and Characterization of a POSS-Maleimide Precursor for Hybrid Nanocomposites

Epoxy polyhedral oligomeric silsesquioxane (POSS)-based hybrid nanocomposites were prepared by in situ polymerization of a homogeneous blend of the diglycidylether of bisphenol-A and 4,4'diaminodiphenylmethane (DDM) in the presence of octa(maleimidophenyl)silsesquioxane. The reaction of a maleimido-functionalized POSS cube with the epoxy resin was studied by Fourier transform infrared analysis and the formation of nanocomposites was confirmed by wide-angle X-ray diffraction and scanning electron microscopy. Dynamic mechanical analysis studies indicated that the crosslinking structures of the nanocomposite networks were predominantly formed between the terminal maleimide double bonds and the amino groups of DDM through a Michael addition reaction to form an aspartimide. The values of the glass transition temperatures ( Tg) decreased with increasing POSS-maleimide content and this was likely to be due to the inclusion of POSS cages into the system and the consequent increase in free volume. The dynamic thermal stability of the cured polymers was increased by increasing the POSS content in the hybrid epoxy matrices as evidenced from thermogravimetric analysis data.

Use of a Polyhedral Oligomeric Silsesquioxane (POSS)-Imidazolium Cation as an Organic Modifier for Montmorillonite

Recent studies on organically modified clays (OMCs) have reported enhanced thermal stabilities when using imidazolium-based surfactants over the typical ammonium-based surfactants. Other studies have shown that polyhedral oligomeric silsesquioxanes (POSS) also improve the thermal properties of composites containing these macromers. In an attempt to utilize the beneficial properties of both imidazolium surfactants and POSS macromers, a dual nanocomposite approach to prepare OMCs was used. In this study, the preparation of a new POSS-imidazolium surfactant and its use as an organic modifier for montmorillonite are reported. The purity, solubility, and thermal characteristics of the POSS-imidazolium chloride were evaluated. In addition, several OMCs were prepared by exchanging the Na+ with POSS imidazolium cations equivalent to 100%, 95%, 40%, 20%, and 5% of the cation exchange capacity of the clay. The subsequent OMCs were characterized using thermal analysis techniques (DSC, SDT, and TGA) as well as 29Si NMR to determine the POSS content in the clay interlayer both before and after thermal oxidation degradation. Results indicate the following: (1) the solvent choice changes the efficiency of the ion-exchange reaction of the clay; (2) self-assembled crystalline POSS domains are present in the clay interlayer; (3) the d-spacing of the exchanged clay is large (3.6 nm), accommodating a bilayer structure of the POSS-imidazolium; and (4) the prepared POSS-imidazolium exchanged clays exhibit higher thermal stabilities than any previously prepared imidazolium or ammonium exchanged montmorillonite.