Phenolic resin/polyhedral oligomeric silsesquioxane (POSS) composites: Mechanical,ablative, thermal,and flame retardant properties

Three different polyhedral oligomeric silsesquioxanes (POSS), trisilanolphenyl polyhedral oligomeric silsesquioxane (T‐POSS), octaaminophenyl polyhedral oligomeric silsesquioxanes (OAPS), and octaphenyl polyhedral oligomeric silsesquioxanes (OPS) were incorporated into phenolic resin (PR), respectively; PR/POSS composites were successfully prepared, and the properties of PR/POSS composites were studied. The limiting oxygen index (LOI), cone calorimeter, and thermal gravimetric analysis (TGA) were used for the estimation of flame retardancy and thermal stability. Oxyacetylene flame test and flexural strength test were used to study the ablative and mechanical properties of the PR/POSS composites. The results indicated that T‐POSS was more effective in improving the flame retardancy of PR than OAPS or OPS. Meanwhile, compared with pure PR, the second line ablation rates of PR/4% T‐POSS, PR/4% OAPS, and PR/4% OPS were significantly reduced by 53.3%, 61.9%, and 40.0%, respectively. In addition, the thermal stability and flexural strength of PR/4% T‐POSS were significantly higher than that of all other PR composites.     

Flame retardant epoxy composites with epoxy‐containing polyhedral oligomeric silsesquioxanes

A kind of polyhedral oligomeric silsesquioxanes (POSS) containing the propoxyl‐epoxy and phenyl groups (pr‐ep‐Ph‐POSS) was synthesized via hydrolytic condensation reaction. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry identified the structure of the pr‐ep‐Ph‐POSS, including major caged Si₆O₉ (T6), Si₁₀O₁₅ (T10), Si₁₂O₁₈ (T12), etc. The pr‐ep‐Ph‐POSS was applied into the epoxy resin to achieve EP/pr‐ep‐Ph‐POSS composites. Thermogravimetric analysis indicated that EP/pr‐ep‐Ph‐POSS showed excellent thermal properties than pure EP. The fire behaviors of EP/pr‐ep‐Ph‐POSS composites were evaluated based on the cone calorimetry, limiting oxygen index (LOI), UL‐94 vertical burning test, and smoke density test. The smoke density decreased by ~30%, the LOI value reached to 26.4%, dripping was inhibited, and the peak of heat release rate decreased by ~62%. X‐ray photoelectron spectroscopy analysis and FTIR indicated that protective‐barrier effect is the main flame‐retardant mode of action for pr‐ep‐Ph‐POSS, due to the formation of the Si‐O‐Si, Si‐O‐C, and Si‐C condensed phase, which improve the thermal stability, strength, and integrity of the char layer.     

倍半硅氧烷改性环氧树脂的研究进展

倍半硅氧烷是近年发展起来的一种分子水平的有机无机杂化材料。文章介绍了倍半硅氧烷的结构、合成以及笼型倍半硅氧烷（POSS）基高分子复合材料的结构及合成方法。倍半硅氧烷改性聚合物可以提高聚合物的热性能、阻燃性能和物理机械性能等。文章综述了倍半硅氧烷改性环氧树脂的研究进展。     

Thermo-oxygen degradation mechanisms of POSS/epoxy nanocomposites

A series of polyhedral oligomeric silsesquioxane/epoxy nanocomposites (POSS/EP) containing 0 wt%, 5 wt%, 10 wt% and 15 wt% content of POSS were prepared. Mechanical properties were used as the index to show the effect of POSS on the thermo-oxygen degradation resistance of epoxy resin. And the thermo-oxygen degradation mechanism was investigated by scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Results showed that the incorporation of POSS into epoxy networks enhanced the thermo-oxygen resistance of epoxy. POSS led to the formation of inert layer on the surface of materials which could protect the internal structure from decomposition. As a result, the retention of mechanical properties of EP/POSS hybrids increased with the POSS content increasing.     

Improving Thermal and Flame Retardant Properties of Epoxy Resin with Organic NiFe‐Layered Double Hydroxide‐Carbon Nanotubes Hybrids

To improve the dispersion of carbon nanotubes (CNTs) and flame retardancy of layered double hydroxide (LDH) in epoxy resin (EP), organic nickel‐iron layered double hydroxide (ONiFe‐LDH‐CNTs) hybrids were assembled through co‐precipitation. These hybrids were further used as reinforcing filler in EP. EP/ONiFe‐LDH‐CNTs nanocomposites containing 4 wt% of ONiFe‐LDH‐CNTs with different ratios of ONiFe‐LDH and CNTs were prepared by ultrasonic dispersion and program temperature curing. The structure and morphology of the obtained hybrids were characterized by different techniques. The dispersion of nanofillers in the EP matrix was observed by transmission electron microscopy (TEM). The results revealed a coexistence of exfoliated and intercalated ONiFe‐LDH‐ CNTs in polymer matrix. Strong combination of the above nanofillers with the EP matrix provided an efficient thermal and flame retardant improvement for the nanocomposites. It showed that EP/ONiFe‐LDH‐CNTs nanocomposites exhibited superior flame retardant and thermal properties compared with EP. Such improved thermal properties could be attributed to the better homogeneous dispersion, stronger interfacial interaction, excellent charring performance of ONiFe‐LDH and synergistic effect between ONiFe‐LDH and CNTs.     

POSS nanocrosslinked poly (ethylene glycol) hydrogel as hybrid material support for silver nanocatalyst

Silver nanoparticles supported on polyhedral oligomeric silsesquioxane (OA‐POSS) nanocrosslinked poly (ethylene glycol)‐based hydrogels (PEG₆₀₀‐POSS/Ag NPs) as novel nanohybrid catalysts were synthesized for the first time. The as‐prepared nanohybrid hydrogels were fully characterized by FT‐IR, SEM, EDX, XRD, TEM and TGA. PEG₆₀₀‐POSS/Ag NPs exhibited excellent catalytic performance for the reduction of 4‐nitrophenol (4‐NP) to 4‐aminophenol (4‐AP) in water at room temperature in the presence of borohydride.     

Flame retardancy mechanisms of phosphorus‐containing polyhedral oligomeric silsesquioxane (DOPO‐POSS) in polycarbonate/acrylonitrile‐butadiene‐styrene blends

The flame retardancy mechanisms of a novel polyhedral oligomeric silsesquioxane containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO‐POSS) in polycarbonate/acrylonitrile‐butadiene‐styrene (PC/ABS) blends are discussed. The thermal stability of PC/ABS composites with different DOPO‐POSS loadings are investigated by TGA and the enhancement of the thermal stability could be found at high temperature range. Their fire behavior is tested by the LOI, UL‐94, and cone calorimeter. Excellent flame retardancy of PC/ABS composites have been discovered with 10 wt% DOPO‐POSS loading. TGA‐FTIR, FTIR, XPS, and SEM, respectively, are used to characterize the gaseous products and the condensed residue in thermal decomposition, and the micro‐structure of the chars from cone calorimeter tests. The decomposition of PC/ABS with 10 wt% DOPO‐POSS shows significant changes compared with PC/ABS by TGA, FTIR, TGA‐FTIR, and XPS analysis. The enhancement of the thermal‐oxidative stability of PC/ABS with DOPO‐POSS is attributed to the interaction between DOPO‐POSS and PC/ABS at high temperature, which might be the key for improvement of the flame retardancy. Copyright © 2011 John Wiley & Sons, Ltd.     

Improving Damping Properties and Thermal Stability of Epoxy/Polyurethane Grafted Copolymer by Adding Glycidyl POSS

Modified castor oil-based epoxy resin (EP)/polyurethane (PU) grafted copolymer by glycidyl polyhedral oligomeric silsesquioxane (glycidyl POSS) was synthesized. The damping properties, thermal stability, mechanical properties and morphology of the grafted copolymer modified by glycidyl POSS were studied systematically. The results revealed that the incorporation of glycidyl POSS improved the damping performance evidently and broadened damping temperature range, especially when the glycidyl POSS content was0.2%–1%. At the same time, there was a slight increase in thermal stability with the increase of POSS content. The tensile properties changed with the change of the copolymer's Tg, decreased at low POSS contents and increased at high POSS contents. This modified copolymer has the potential to be used as film damping material or constrained damping layer.     

Efficient Photocatalytic Cleavage of Lignin Models by a Soluble Perylene Diimide/Carbon Nitride S-Scheme Heterojunction

3,4,9,10-Perylenetetracarboxylic dianhydride (PDI) is one of the best n-type organic semiconductors and an ideal light-driven catalyst for lignin depolymerization. However, the charge localization effect and the excessively strong intermolecular aggregation trend in PDI result in rapid electron-hole (e⁻−h⁺) recombination, which limits photocatalytic performance. Herein, polymeric carbon nitride/polyhedral oligomeric silsesquioxane PDI (p-CN/P-PDI) S-scheme heterojunction photocatalyst was prepared by the solvent evaporation-deposition method for C−C bond selective cleavage of lignin β-O-4 model. Based on the material characterization results, the synergic role of polyhedral oligomeric silsesquioxane (POSS) and S-scheme heterojunction maintains appropriate aggregation domains, achieves better solar light utilization, faster charge-transfer efficiency, and greater redox capacity. Notably, the 3 % p-CN/P-PDI heterostructure exhibits a remarkable enhancement in cleavage conversion efficiency, achieving approximately 16.42 and 2.57 times higher conversion rates compared to polyhedral oligomeric silsesquioxane modified PDI (POSS-PDI) and polymeric carbon nitride (p-CN), respectively.     

Blowing‐out effect and temperature profile in condensed phase in flame retarding epoxy resins by phosphorus‐containing oligomeric silsesquioxane

A series of flame retardant epoxy resins (EPs) containing phosphorus‐containing oligomeric silsesquioxane are prepared, and an interesting blowing‐out effect is detected in flame retardant EPs. The temperature profiles show that blowing‐out effect slows the heat transfer from the fire to the unburned matrix; furthermore, this blowing‐out effect can even take away some heat from the surface zone by the spurting gases. The thermo gravimetric analyzer and Fourier transform infrared spectrometer result shows that the spurting gases during the blowing‐out effect have a high content of CO₂, which could reduce the combustion capability of the jetting gases. The flame retardancy of these EPs is tested by limit oxygen index and UL‐94. The incorporation of 2.5 wt% phosphorus‐containing oligomeric silsesquioxane into EP gives a remarkable blowing‐out effect, which results in a significant enhancement of limit oxygen index value and UL‐94 rating. The flame retardancy mechanism of blowing‐out effect is quite different from the traditional mechanisms. The char strength and morphology of EP composites are also investigated to explain the mechanism of the blowing‐out effect. Copyright © 2013 John Wiley & Sons, Ltd.     

Co-flame retarding effect of ethanolamine modified titanium-containing polyhedral oligomeric silsesquioxanes in epoxy resin

A metal-doped organic and inorganic hybrid polyhedral oligomeric silsesquioxanes (POSS) with a titanium atom in the POSS cage and an ethanolamine substitute group in the corner, namely MEA-Ti-POSS, was synthesized through simple condensation reaction and substitute reaction. It was blended with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to form a kind of blending-type flame retardant system for the modification of epoxy resins. The thermal stability, flame retardancy and mechanical properties of cured epoxy resin composites were studied. Comparing with pure epoxy resin, the LOI value of EP/MEA-Ti-POSS/DOPO composites was raised from 25.2% to 32.7%, and the UL-94 grade reached V-0 level at a loading of the mixture of 5% MEA-Ti-POSS and 5% DOPO. In addition, the cone calorimetry results showed that the heat release rate, total heat release and total smoke production as well as smoke production rate were all reduced during the combustion of EP/MEA-Ti-POSS/DOPO composites. The residual char analysis revealed that carbon residues of EP/MEA-Ti-POSS/DOPO composite served as a physical protective layer to insulate the oxygen and combustible gases to reduce the ablation of the matrix. It was concluded that the mixture of MEA-Ti-POSS and DOPO not only effectively raised the thermal stability and flame retardancy of epoxy composited materials, but also improved their mechanical properties, which expanded a promising application of the metal-POSS derivatives as non-halogen additives in the flame retardant polymers.     

Poly(ethylene imine) hybrids containing polyhedral oligomeric silsesquioxanes: Preparation, structure and properties

Both octaglycidyletherpropyl polyhedral oligomeric silsesquioxane and hepta(3,3,3-trifluoropropyl)glycidyletherpropyl polyhedral oligomeric silsesquioxane were synthesized via the hydrosilylation reactions between octahydrosilsesquioxane [and/or hepta(3,3,3-trifluoropropyl)hydrosilsesquioxane] and allyl glycidyl ether. The polyhedral oligomeric silsesquioxane (POSS) macromers were characterized by means of Fourier transform infrared and nuclear magnetic resonance spectroscopy. The inter-component macromolecular reactions between the POSS macromers and poly(ethylene imine) (PEI) were employed to prepare the POSS-containing organic-inorganic PEI hybrids. The inclusion of octaglycidyletherpropyl POSS into PEI results in the formation of the organic-inorganic hybrid networks whereas the introducing hepta(3,3,3-trifluoropropyl)glycidyletherpropyl POSS to PEI affords the linear POSS-grafted PEI copolymers. Differential scanning calorimetry and thermogravimetric analysis show that the POSS-containing PEI hybrids displayed increased glass transition temperatures (T_g’s) and enhanced thermal stability compared to the plain PEI. These PEI hybrid composites can be significantly swollen with water without dissolving, suggesting the formation of hydrogels. The PEI hydrogels containing octaglycidyletherpropyl POSS is in reality the chemically-crosslinked hydrogels whereas the those containing hepta(3,3,3-trifluoropropyl)glycidyletherpropyl POSS displayed the behavior of physical hydrogels. The formation of physical hydrogels is ascribed to the microphase-separated morphology in the hybrids. In addition, the hybrids containing hepta(3,3,3-trifluoropropyl)glycidyletherpropyl POSS exhibited the typical amphiphilicity as evidenced by the increase in surface hydrophobilicity.     

Thermal and dynamic mechanical properties of epoxy resin/poly(urethane‐imide)/polyhedral oligomeric silsesquioxane nanocomposites

Linear isocyanate‐terminated poly(urethane‐imide) (PUI) with combination of the advantages of polyurethane and polyimide was directly synthesized by the reaction between polyurethane prepolymer and pyromellitic dianhydride (PMDA). Then octaaminophenyl polyhedral oligomeric silsesquioxane (OapPOSS) and PUI were incorporated into the epoxy resin (EP) to prepare a series of EP/PUI/POSS organic–inorganic nanocomposites for the purpose of simultaneously improving the heat resistance and toughness of the epoxy resin. Their thermal degradation behavior, dynamic mechanical properties, and morphology were studied with thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and transmission electron microscope (TEM). The results showed that the thermal stability and mechanical modulus was greatly improved with the addition of PUI and POSS. Moreover, the EP/PUI/POSS nanocomposites had lower glass transition temperatures. The TEM results revealed that POSS molecules could self assemble into strip domain which could switch to uniform dispersion with increasing the content of POSS. All the results could be ascribed to synergistic effect of PUI and POSS on the epoxy resin matrix. Copyright © 2010 John Wiley & Sons, Ltd.     

Polyhedral oligomeric silsesquioxane bound fulleropyrrolidines

The first reported examples of polyhedral oligomeric silsesquioxane (POSS) cages containing a fulleropyrrolidine species are reported herein. Monosubstituted POSS‐dioxalane species were synthesized through the hydrosilylation of a silyl‐dioxalane with mono‐vinyl substituted POSS. Subsequent deprotection yielded the desired aldehyde functionality. An alternative synthetic pathway, involving the nucleophilic substitution of mono‐benzyl chloride POSS with 4‐hydroxybenzaldehyde yielded the desired aldehyde functionality. Each mono‐aldehyde POSS was then reacted with N‐methylglycine and C₆₀ to yield the desired POSS fulleropyrrolidines. The prepared compounds were characterized by multinuclear NMR, electrospray mass spectrometry, elemental analysis, UV–vis, fluorescence and optical power limiting measurements. Copyright © 2008 John Wiley & Sons, Ltd.     

Mechanical and flame‐retardant properties and thermal decomposition of vinyl ester resin modified by different phenyl silsesquioxanes

The mechanical properties and fire resistance of vinyl ester resin (VER) composites containing cage‐shaped octaphenyl silsesquioxane (OPS), incompletely cage‐shaped phenyl silsesquioxane (PhT₇POSS), and ladder‐shaped phenyl silsesquioxane (PPSQ) were investigated. The POSS structure and dispersion have a great influence on the mechanical properties, thermal stability, and decomposition process of VER composites. The bending strength at break and modulus of the VER‐POSS composites were enhanced obviously, especially for VER‐PPSQ composite and VER‐OPS composite, respectively. In addition, PhT₇POSS‐based VER composites revealed the lower values of the peak heat release rate, total heat release, and total smoke release in cone calorimetry tests due to the formation of dense carbon/silica protective layers that acted as a barrier to heat and mass transfer. Moreover, the flame‐retardant mechanisms of condensed phase and gas phase were also investigated in detail. These results illustrate VERs modified by OPS, PhT₇POSS, and PPSQ are providing an applicable method to fabricate the composites with excellent flame‐retardant and mechanical properties.     

Poly(4‐vinylpyridine) Nanocrosslinked by Polyhedral Oligomeric Silsesquioxane

Summary: Octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) was used as the crosslinking agent to prepare the nanocrosslinked poly(4‐vinylpyridine) (P4VP) with POSS content up to 55.2 wt.‐%. The formation of the crosslinked structure is ascribed to the macromolecular reaction between pyridine rings of P4VP and epoxide groups of OpePOSS. The POSS‐crosslinked P4VP displayed enhanced glass transition temperatures (T_gs) and an improved thermal stability in terms of the results of thermal analysis.

Crosslinking of poly(4‐vinylpyridine) with octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane.     

The Enhanced Encapsulation Capacity of Polyhedral Oligomeric Silsesquioxane‐based Copolymers for the Fabrication of Electrospun Core/Shell Fibers

This paper reports the use of polyhedral oligomeric silsesquioxane (POSS)‐based copolymers to stabilize the core/shell interface for the facile fabrication of electrospun core/shell fibers. For the poly[(propylmethacryl‐heptaisobutyl‐polyhedral oligomeric silsesquioxane)‐co‐(methyl methacrylate)] (POSS‐MMA)/poly(ε‐caprolactone) (PCL) system, the bicontinuity of hybrid core/shell fibers can be tuned by controlling the phase separation of POSS‐MMA/PCL in electrospinning solutions and therefore the size of PCL‐in‐POSS‐MMA emulsion droplets. Our results demonstrate the enhanced encapsulation capacity of POSS‐MMA copolymers as shell materials. Taking advantage of the rapid advancement of POSS‐based copolymer synthesis, this study can potentially be generalized to guide the fabrication of various other POSS‐based core/shell nano‐/microstructures by using single‐nozzle electrospinning or coaxial electrospinning.

     

Crystallization and flame‐retardant properties of polylactic acid composites with polyhedral octaphenyl silsesquioxane

To develop environmental‐friendly and flame‐retarded polymer composites, bio‐based polylactic acid (PLA) was loaded with thermally stable polyhedral octaphenyl silsesquioxane (OPS). Pure PLA and PLA/OPS composites with the OPS of 1, 3, 5, and 10 wt% were prepared by extrusion and injection molding, respectively. The scanning electron microscopy (SEM), polarized optical microscope (POM), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and thermal gravimetric analysis (TGA) were used to analyze the dispersion of the OPS in the PLA matrix and the effects of OPS on the crystallization and thermal stability properties of PLA/OPS composites, respectively. Limited oxygen index (LOI) and cone calorimeter (CONE) measurements were used to study flame retardancy of PLA and PLA/OPS composites. In order to study the flame‐retardant mechanism, the char residues were investigated by SEM, Fourier transform infrared spectra (FTIR), and X‐ray photoelectron spectroscopy (XPS). TGA‐FTIR was used to analyze the gaseous products of their thermal decomposition. The results show that the OPS particles were submicron in the PLA and could increase the crystallization rate of PLA and form small‐sized secondary α‐form crystalline compared with the pure PLA spherulite. The PLA and OPS decomposed individually in the PLA/OPS composites by TGA. According to the LOI tests, the PLA with the OPS loading exhibited very small reduction of LOI. However, the CONE tests indicated that the OPS could improve the flame retardancy of the PLA by means of low peak heat release rate and average heat release rate. It was obtained that the degree and type of the PLA crystalline for the pure PLA and PLA/OPS affect their flame retardancy. In the max thermal decomposition stage of PLA and PLA/OPS, their gaseous products were similar; at high temperatures, the PLA/OPS produced simple and clear gaseous products of PLA with solid SiO₂ in the gas phase.     

Polyhedral oligomeric silsesquioxane‐based fluoroether‐containing terpolymers: Synthesis,characterization and their water and oil repellency evaluation for cotton fabric

A series of polyhedral oligomeric silsesquioxane (POSS) based hybrid copolymers poly(POSS‐co‐methyl methacrylate ?co‐ 4‐vinylbenzyl fluoroether carboxylate) ( P(POSS‐MMA‐VBFC) ) were prepared via radical polymerization and characterized by nuclear magnetic resonance, fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, X‐ray powder diffraction, scanning electron microscopy and transmission electron microscopy. The thermal properties of these polymers (T_d > 250 °C) were improved by the introduction of POSS cage. The cotton fabrics coated with the polymers possessed excellent water and oil repellency. The water and salad oil contact angle could be achieved from 133° to 159° and from 127° to 141° respectively as the content of POSS in the polymer increased from 0 to 7.1 wt %. Moreover, the cotton fabric coated with the terpolymer was less flammable than the uncoated one. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Interfacial strength and mechanisms of silicone resin composites reinforced with 2 different polyhedral oligomeric silsesquioxanes/carbon fiber hybrids

Grafting nanoscale reinforcement onto macrolevel carbon fiber (CF) surface is an efficient approach to improve interfacial strength and properties of composites. In the research, 2 different polyhedral oligomeric silsesquioxanes (POSS)/CF hybrids have been prepared by a facile 2‐step method. Carbon fiber was grafted with aniline groups by aryl diazonium reaction using water as the reaction medium, and then separately functionalized with glycidyllsobutyl POSS (EP0418) or glycidyl POSS (EP0409) by the chemical bonding. Characterization of fiber surface structures before and after modification confirmed the covalent bonding nature between both kinds of POSS and CF. Atomic force microscopy images showed the uniform distributions of EP0418 or EP0409 modified on the fiber surface and the similar enhanced degree of surface roughness (89.3 and 88.7 nm). Dynamic contact angle tests showed that EP0409‐grafted CF (CF‐g‐EP0409) had lower contact angles and higher surface free energy than those of EP0418‐grafted CF (CF‐g‐EP0418). Interfacial strength and hydrothermal aging resistance of composites enhanced significantly after POSS modification, especially for CF‐g‐EP0409 composites. Interfacial reinforcing mechanisms of composites reinforced with 2 different POSS/CF hybrids have also been analyzed and compared.