Rational design of polyhedral oligomeric silsesquioxane fillers for simultaneous improvements of thermomechanical properties and lowering refractive indices of polymer films

We describe here the design and synthesis of the polyhedral oligomeric silsesquioxane (POSS)‐based dual‐functional molecular fillers for simultaneously lowering refractive indices and improving thermomechanical properties of conventional polymers. We prepared the composite films with poly(methyl methacrylate) and polystyrene containing the series of the POSS derivatives with the single functional unit for interacting with polymer chains and heptacyclopentyl substituents for creating exclusive volumes around the POSS core. From the measurements of refractive indices of polymer composites, it was revealed that all POSS fillers can lower the refractive index of the films. In addition, thermal stabilities and mechanical properties were enhanced by adding POSS fillers. The filler effect on the thermal properties can be explained by the structural features of POSS: The highly symmetrical structure of the silica cube should suppress thermal motions, resulting in the large enhancement of thermomechanical properties of polymer matrices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3583–3589     

Side‐chain effect of octa‐substituted POSS fillers on refraction in polymer composites

To investigate the relationship between the chemical structures of the side chains of polyoctahedral oligomeric silsesquioxanes (POSS) fillers and the ability to decrease the refractive indices of the polymer composites, we examined the influence on the degree of polymer chain packing by the existence of the octa‐substituted POSS derivatives. The polymer composites containing methyl‐, ethyl‐, vinyl‐, isobutyl‐, octyl‐, octadecyl‐, cyclopentyl‐, and phenyl‐substituted POSS in poly(methyl methacrylate) (PMMA) were prepared. The packing coefficients of the PMMA composites containing POSS derivatives were evaluated from molar refractions and refractive indices of the films with the Lorentz–Lorenz equation. We found that the ethyl group shows the lowest values of the packing coefficients and a significant effect in reducing the refractive indices of the polymer composites. Finally, in summary, it was shown that POSS molecules can intrinsically offer to reduce a packing. In addition, less entanglement and smaller interactions between polymer chains and the substitution groups are favorable to release a packing, resulting in decreases in refractive indices. Our findings described here are the first efforts to quantitatively evaluate the ability of POSS fillers to lower refractive indices at the molecular level. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of novel PDMS nanocomposites using POSS derivatives as cross‐linking filler

We report the synthesis and characterization of novel elastomeric nanocomposites containing polyhedral oligomeric silsesquioxanes (POSS) as both the cross‐linker and filler within a polydimethylsiloxane (PDMS) polymer matrix. These polymer composites were prepared through the reaction of octasilane‐POSS (OS‐POSS) with vinyl‐terminated PDMS chains using hydrosilylation chemistry. In addition, larger super‐POSS cross‐linkers, consisting of two pendant hepta(isobutyl)POSS molecules attached to a central octasilane‐POSS core, were also used in the fabrication of the PDMS composites. The chemical incorporation of these POSS cross‐linkers into the PDMS network was verified by solid‐state ¹H magic angle spinning NMR. Based on dynamic mechanical analysis, the PDMS nanocomposites prepared with the octafunctional OS‐POSS cross‐linker exhibited enhanced mechanical properties relative to polymer systems prepared with the tetrafunctional TDSS cross‐linker at equivalent loading levels. The observed improvements in mechanical properties can be attributed to the increased dimensionality of the POSS cross‐linker. The PDMS elastomers synthesized from the larger super‐POSS molecule showed improved mechanical properties relative to both the TDSS and OS‐POSS composites due to the increased volume‐fraction of POSS filler in the polymer matrix. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2589–2596, 2009     

Physically cross‐linked networks of POSS‐capped poly(acrylate amide)s: Synthesis,morphologies, and shape memory behavior

In this work, we synthesized a novel organic–inorganic semitelechelic polymer from polyhedral oligomeric silsesquioxane (POSS) and poly(acrylate amide) (PAA) via reversible addition‐fragmentation chain transfer (RAFT) polymerization. The organic–inorganic semitelechelic polymers have been characterized by means of nuclear magnetic resonance spectroscopy, thermal gravimetric analysis, and dynamic mechanical thermal analysis. It was found that capping POSS groups to the single ends of PAA chains caused a series of significant changes in the morphologies and thermomechanical properties of the polymer. The organic–inorganic semitelechelics were microphase‐separated; the POSS microdomains were formed via the POSS–POSS interactions. In a selective solvent (e.g., methanol), the organic–inorganic semitelechelics can be self‐assembled into the micelle‐like nanoobjects. Compared to plain PAA, the POSS‐capped PAAs significantly displayed improved surface hydrophobicity as evidenced by the measurements of static contact angles and surface atomic force microscopy. More importantly, the organic–inorganic semitelechelics displayed typical shape memory properties, which was in marked contrast to plain PAA. The shape memory behavior is attributable to the formation of the physically cross‐linked networks from the combination of the POSS–POSS interactions with the intermolecular hydrogen‐bonding interactions in the organic–inorganic semitelechelics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 587–600     

POSS‐nylon 6 nanocomposites: Influence of POSS structure on surface and bulk properties

Hybrid organic/inorganic nanocomposites based on polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals and nylon 6 were prepared via melt mixing. Two structurally and chemically different POSS molecules, a closed cage, nonpolar octaisobutyl POSS (Oib‐POSS) and an open cage, polar trisilanolphenyl POSS (Tsp‐POSS) with differing predicted solubility parameters were evaluated in the nylon matrix. Surface analysis, including quasi‐static and dynamic nanoindentation and nanotribological techniques, revealed exceptional improvements in modulus and hardness along with significant reductions in friction. Additionally, surface wetting characteristics of the nylon were reversed, with POSS incorporation yielding low surface energy, highly hydrophobic surfaces. AFM, TEM/EDAX, spectroscopic techniques and thermomechanical analysis were used to evaluate nanoscale dispersion and bulk properties of the composites. Both POSS molecules exhibit preferential surface segregation behavior in the nylon matrix. Tsp‐POSS, with its higher predicted solubility in nylon, exhibited enhanced dispersion and tribomechanical properties at both nano and bulk scale. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1088–1102, 2009     

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

3‐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 (T_g'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     

Role of adsorbed chain rigidity in reinforcement of polymer nanocomposites

The thermomechanical behavior of polymer nanocomposites is mostly governed by interfacial properties which rely on particle–polymer interactions, particle loading, and dispersion state. We recently showed that poly(methyl methacrylate) (PMMA) adsorbed nanoparticles in poly(ethylene oxide) (PEO) matrices displayed an unusual thermal stiffening response. The molecular origin of this unique stiffening behavior resulted from the enhanced PEO mobility within glassy PMMA chains adsorbed on nanoparticles. In addition, dynamic asymmetry and chemical heterogeneities existing in the interfacial layers around particles were shown to improve the reinforcement of composites as a result of good interchain mixing. Here, the role of chain rigidity in this interfacially controlled reinforcement in PEO composites is investigated. We show that particles adsorbed with less rigid polymers improve the mechanical properties of composites. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 9–14     

Graphitic nanofillers in PMMA nanocomposites—An investigation of particle size and dispersion and their influence on nanocomposite properties

Mechanical, thermal, and electrical properties of graphite/PMMA composites have been evaluated as functions of particle size and dispersion of the graphitic nanofiller components via the use of three different graphitic nanofillers: “as received graphite” (ARG), “expanded graphite,” (EG) and “graphite nanoplatelets” (GNPs) EG, a graphitic materials with much lower density than ARG, was prepared from ARG flakes via an acid intercalation and thermal expansion. Subsequent sonication of EG in a liquid yielded GNPs as thin stacks of graphitic platelets with thicknesses of ～10 nm. Solution‐based processing was used to prepare PMMA composites with these three fillers. Dynamic mechanical analysis, thermal analysis, and electrical impedance measurements were carried out on the resulting composites, demonstrating that reduced particle size, high surface area, and increased surface roughness can significantly alter the graphite/polymer interface and enhance the mechanical, thermal, and electrical properties of the polymer matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2097–2112, 2007     

Dynamic mechanical analyses of Nafion®/organically modified silicate nanocomposites

Nafion®/organically modified silicate (ORMOSIL) hybrids were generated via polymer in situ sol–gel copolymerizations of tetraethylorthosilicate (TEOS) with difunctional and trifunctional organoalkoxysilane monomers, and the dynamic mechanical relaxations and thermomechanical stability of the resultant composites were investigated. All ORMOSIL fillers restrict main‐chain and side‐chain mobility. The results suggest that sulfonic acid side chains become entrapped in silicate or ORMOSIL structures that evolve during the in situ sol–gel process. Some but not all of the ORMOSIL combinations display trends in the α or β relaxation temperature with respect to the TEOS comonomer ratio. All of the hybrids have greater high‐temperature thermomechanical stability than the unfilled acid form. There are definite composition trends in the vertical displacement of the storage‐modulus–temperature curves. For some of the semiorganic comonomers, there is a monotonic increase in storage modulus with decreasing comonomer content in the high‐temperature regime, which is understood in terms of a progressive immobilization of the long side chains by progressively more rigid ORMOSIL nanostructures. For other semiorganic comonomers, the high‐temperature plateau shifts upward to a maximum and then shifts downward with decreasing comonomer fraction. In addition to the chemical nature of the imparted nanophases, these molecular motions are expected to influence the transport properties of these novel heterogeneous membranes. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1282–1295, 2001     

Volume‐exclusion effects in polyethylene blends filled with carbon black,graphite, or carbon fiber

Conductive polymer composites possessing a low percolation‐threshold concentration as a result of double percolation of a conductive filler and its host phase in an immiscible polymer blend afford a desirable alternative to conventional composites. In this work, blends of high‐density polyethylene (HDPE) and ultrahigh molecular weight polyethylene (UHMWPE) were used to produce ternary composites containing either carbon black (CB), graphite (G), or carbon fiber (CF). Blend composition had a synergistic effect on electrical conductivity, with pronounced conductivity maxima observed at about 70–80 wt % UHMWPE in the CB and G composites. A much broader maximum occurred at about 25 wt % UHMWPE in composites prepared with CF. Optical and electron microscopies were used to ascertain the extent to which the polymers, and hence filler particles, are segregated. Differential scanning calorimetry of the composites confirmed that the constituent polymers are indistinguishable in terms of their thermal signatures and virtually unaffected by the presence of any of the fillers examined here. Dynamic mechanical analysis revealed that CF imparts the greatest stiffness and thermal stability to the composites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1013–1023, 2002     

Facile and quick synthesis of poly(N‐methylolacrylamide)/polyhedral oligomeric silsesquioxane graft copolymer hybrids via frontal polymerization

We report on a new strategy for fabricating well‐defined POSS‐based polymeric materials with and without solvent by frontal polymerization (FP) at ambient pressure. First, we functionalize polyhedral oligomeric silsesquioxane (POSS) with isophorone diisocyanate (IPDI). With these functionalized POSS‐containing isocyanate groups, POSS can be easily incorporated into a poly(N‐methylolacrylamide) (PNMA) matrix via FP in situ. Constant velocity FP is observed without significant bulk polymerization. The morphology and thermal properties of POSS‐based hybrid polymers prepared via FP are comparatively investigated on the basis of scanning electronic microscopy (SEM) and thermogravimetric analysis (TGA). Results show that the as‐prepared POSS‐based polymeric materials exhibit a higher glass transition temperature than that of pure PNMA, ascribing to modified POSS well‐dispersed in these hybrid polymers. Also, the products with different microstructures display different thermal properties. The pure PNMA exhibits a featureless morphology, whereas a hierarchical morphology is obtained for the POSS‐based polymeric materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1136–1147, 2009     

Polyurethanes from polyols obtained by ADMET polymerization of a castor oil‐based diene: Characterization and shape memory properties

The acyclic diene metathesis polymerization (ADMET) of 1,3‐di‐10‐undecenoxy‐2‐propanol, a castor oil based diene, is reported. 10‐Undecenol was used as renewable comonomer to end‐cap polymer chains and limit the molecular weight. The poly ols obtained in this way were reacted with 4,4′‐methylenebis(phenylisocyanate) (MDI) to yield a series of amorphous and semicrystalline polyurethane networks. The thermal stability and the thermomechanical and mechanical properties of these thermosets have been studied and showed good shape memory properties for the semicrystalline polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Surface energetics,dispersion, and nanotribomechanical behavior of POSS/PP hybrid nanocomposites

Hybrid organic–inorganic polymer nanocomposites incorporating polyhedral oligomeric silsesquioxane (POSS) nanoparticles are of increasing interest for high performance materials applications. Octaisobutyl POSS/polypropylene nanocomposites were prepared at varying POSS concentrations via melt blending. The interplay of POSS molecular geometry, composition, and concentration in relation to the tribological, nanomechanical, surface energy, and bulk properties of the nanocomposites were investigated. Ultra‐low friction and enhanced hardness, modulus, and hydrophobicity were observed for the nanocomposite surfaces, with minimal changes in the bulk thermomechanical properties. Parallel AFM, SEM, TEM, and spectroscopic analyses demonstrated significant differences in POSS distribution and aggregation in the surface and the bulk, with preferential segregation of POSS to the surface. Additionally, contact angle studies reveal significant reduction in surface energy and increase in hysteresis with incorporation of POSS nanoparticles. The differences in bulk and surface properties are largely explained by the gradient concentration of POSS in the polymer matrix, driven by POSS/POSS and POSS/polymer interactions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2441–2455, 2007     

Polymers and cyclic compounds based on a side‐opening type cage silsesquioxane

Polymers having polyhedral oligomeric silsesquioxane (POSS) in the main chains are an important class of organic–inorganic hybrid materials. Despite the increasing attention to the POSS polymers, variation of the monomers is still limited. Herein, we have proposed side‐opening POSS (SO‐POSS) monomers. Platinum‐catalyzed hydrosilylation polymerization proceeded to produce polysiloxanes having SO‐POSS in the main chains. The obtained polysiloxanes showed good solubility, high thermal stability, high transparency, and tunable reflective index. In addition, cyclic compounds were obtained during the investigation of the polymerization, and were synthesized with high selectivity under the slightly diluted conditions. The obtained cyclic compounds showed high thermal stability due to the silsesquioxane backbone, and the high dispersibility as a filler in poly(methyl methacrylate) was demonstrated. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2243–2250     

Thermal properties and moisture absorption of nanofillers‐filled epoxy composite thin film for electronic application

This current study aimed to enhance the thermal conductivity of thin film composites without compromising other polymer qualities. The effect of adding high thermal conductivity nanoparticles on the thermal properties and moisture absorption of thin film epoxy composites was investigated. Three types of fillers in nanosize with high thermal conductivity properties, boron nitride (BN), synthetic diamond (SD), and silicon nitride (Si₃N₄) were studied. SN was later used as an abbreviation for Si₃N₄. The contents of fillers varied between 0 and 2 vol.%. An epoxy nanocomposite solution filled with high thermal conductivity fillers was spun at 1500–2000 rpm to produce thin film 40–60 µm thick. The effects of the fillers on thermal properties and moisture absorption were studied. The addition of 2 vol.% SD produced the largest improvement with 78% increment in thermal conductivity compared with the unfilled epoxy. SD‐filled epoxy thin film also showed good thermal stability with the lowest coefficients of thermal expansion, 19 and 124 ppm, before and after T_g, respectively, which are much lower compared with SN‐filled and BN‐filled epoxy thin film composites. However the SD‐filled epoxy film has its drawback as it absorbs more moisture compared with BN‐filled and SN‐filled epoxy film. Copyright © 2012 John Wiley & Sons, Ltd.     

Preparation,Tg improvement,and thermal stability enhancement mechanism of soluble poly(methyl methacrylate) nanocomposites by incorporating octavinyl polyhedral oligomeric silsesquioxanes

The soluble poly(methyl methacrylate‐co‐octavinyl‐polyhedral oligomeric silsesquioxane) (PMMA–POSS) hybrid nanocomposites with improved T_g and high thermal stability were synthesized by common free radical polymerization and characterized using FTIR, high‐resolution ¹H NMR, ²⁹Si NMR, GPC, DSC, and TGA. The POSS contents in the nanocomposites were determined based on FTIR spectrum, revealing that it can be effectively adjusted by varying the feed ratio of POSS in the hybrid composites. On the basis of the ¹H NMR analysis, the number of the reacted vinyl groups on each POSS molecules was determined to be about 6–8. The DSC and TGA measurements indicated that the hybrid nanocomposites had higher T_g and better thermal properties than the pure PMMA homopolymer. The T_g increase mechanism was investigated using FTIR, displaying that the dipole–dipole interaction between PMMA and POSS also plays very important role to the T_g improvement besides the molecular motion hindrance from the hybrid structure. The thermal stability enhances with increase of POSS content, which is mainly attributed to the incorporation of nanoscale inorganic POSS uniformly dispersed at molecular level. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5308–5317, 2007     

Organic–inorganic copolymers with double‐decker silsesquioxane in the main chains by polymerization via click chemistry

A series of novel organic–inorganic copolymers with polyhedral oligomeric silsesquioxane (POSS) in the main chains were synthesized via the copper‐catalyzed Huisgen 1,3‐dipolar cycloaddition polymerization approach. Toward this end, we synthesized 3,13‐azidopropyloctaphenyl double‐decked silsesquioxane (DDSQ). This difunctional POSS macromer was used to copolymerize with α,ω‐dialkynyl‐terminated oligoethylenes with variable number of ethylene units. The organic–inorganic copolymers were obtained with the mass fraction of POSS up to 79%. Gel permeation chromatography showed that the high‐molecular‐weight copolymers were successfully obtained in all the cases. Differential scanning calorimetry showed that the amplitude of glass transitions for these copolymers was very feeble, suggesting that the segmental motions responsible for the glass transitions was highly restricted with DDSQ cages in the main chains. Thermogravimetric analysis showed that the organic–inorganic hybrid copolymers displayed extremely high thermal stability. Contact angle measurements showed that these organic–inorganic copolymers are highly hydrophobic and possessed very low surface energy. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4221–4232     

Nanocomposites through copolymerization of a polyhedral oligomeric silsesquioxane and methyl methacrylate

The mechanical properties and thermal stability of polymers can be enhanced through the formation of nanocomposites. Nanocomposites consisting of hybrid copolymers of methacrylcyclohexyl polyhedral oligomeric silsesquioxane (POSS‐1) and methyl methacrylate (MMA) with up to 92 wt % (51 mol %) POSS‐1 and with superior thermal properties were synthesized using solution polymerization. The POSS‐1 contents of the copolymers were similar to or slightly higher than those in the feeds, the polydispersity indices were relatively low, and the degree of polymerization decreased with increasing POSS‐1 content. POSS‐1 enhanced the thermal stability, increasing the degradation temperature, reducing the mass loss, and preventing PMMA‐like degradation from propagating along the chain. The mass loss was reduced in a high POSS‐1 content copolymer since the polymerization of POSS‐1 with itself reduced sublimation. Exposure to 450 °C produced cyclohexyl‐POSS‐like remnants in the POSS‐1 monomer and in all the copolymers. The degradation of these remnants, for the copolymers and for the POSS‐1 monomer, yielded 75% SiO₂ and an oxidized carbonaceous residue. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4264–4275, 2007     

Dendronized polymers via Diels–Alder “click” reaction

A modular approach toward the synthesis of polymers containing dendron groups as side chains is developed using the Diels–Alder “click” reaction. For this purpose, a styrene‐based polymer appended with anthracene groups as reactive side chains was synthesized. First through third‐generation polyester dendrons containing furan‐protected maleimide groups at their focal point were synthesized. Facile, reagent‐free, thermal Diels–Alder cycloaddition between the anthracene‐containing polymer and latent‐reactive dendrons leads to quantitative functionalization of the polymer chains to afford dendronized polymers. The efficiency of this functionalization step was monitored using ¹H and ¹³C NMR spectroscopy and FTIR and UV–vis spectrometry. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 410–416, 2010     

Preparation,characterization, and properties of novel biodegradable aliphatic–aromatic copolyester nanohybrids with polyhedral oligomeric silsesquioxanes moieties

Biodegradable aliphatic–aromatic copolyester nanohybrids, with polyhedral oligomeric silsesquioxane (POSS) moieties tethered between poly(lactic acid) (PLA) and poly(butylene terephthalate) segments, is designed and prepared. First, (bis(2‐hydroxyethyl) dipropionate POSS, BH‐POSS) is synthesized under mild conditions, then in situ polycondensation is carried out in the presence of terephthalic acid, PLA oligomer, 1,4‐butanediol, and BH‐POSS. 1 H‐NMR and Fourier transfer infrared spectroscopy confirm that Michael addition reaction of amino‐POSS and hydroxyethyl acrylate takes place efficiently and forms BH‐POSS in high yield at room temperature. Owing to similar functional groups, BH‐POSS could be easily incorporated into the macromolecular chains and obtain final copolyester nanohybrids. Moreover, X‐ray diffractometry and transmission electron microscopy observations demonstrate that POSS moieties occur self‐assembly behaviors and form nanoaggregates with the diameter of 50–100 nm. The thermal stability and mechanical properties of the copolyester nanohybrids containing BH‐POSS are substantially improved. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012