Syntheses, thermal properties, and phase morphologies of novel benzoxazines functionalized with polyhedral oligomeric silsesquioxane (POSS) nanocomposites

We have successfully synthesized a novel benzoxazine ring-containing polyhedral oligomeric silsesquioxane (BZ-POSS) monomer by two routes: (1) hydrosilylation of a vinyl-terminated benzoxazine using the hydro-silane functional group of a polyhedral oligomeric silsesquioxane (H-POSS) and (2) reaction of a primary amine-containng POSS (Amine-POSS) with phenol and formaldehyde. The benzoxazine-containing POSS (BZ-POSS) monomer can be copolymerized with other benzoxazine monomers through ring-opening polymerization under conditions similar to that used for polymerizing pure benzoxazines. Thermal properties of these POSS-containing organic/inorganic polybenzoxazine nanocomposites have been improved over the pure polybenzoxazine analyzed by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The BZ-POSS monomer is poorly miscible with the benzoxazine monomer and tends to aggregate and forms its own domains, both before and after polymerization. At a higher BZ-POSS content, gross aggregation occurs and results in a lower than expected improvement in the thermal properties.     

Properties of POSS‐filled polypropylene: Comparison of physical blending and reactive blending

Polypropylene (PP)/octavinyl polyhedral oligomeric silsesquioxane (OvPOSS) composites were prepared by physical blending or reactive blending methods. The comparison of the PP/OvPOSS composites prepared by these two methods was investigated by mechanical tests, thermogravimetric analysis, and cone calorimeter. The graft ratio of OvPOSS to PP chain increased with increasing OvPOSS and dicumyl peroxide content for the reactive blending composites. The reactive blending composites had better mechanical properties, thermal stability than physical blending composites. The peak of the heat release rate and mass loss rate of PP/OvPOSS had also decreased, indicating better flame retardancy of PP/OvPOSS composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ultralight and Low Thermal Conductivity Polyimide–Polyhedral Oligomeric Silsesquioxanes Aerogels

The research on rapid growing, organic, and ultralight cross‐linking polyimide aerogels is receiving significant interest. In this work, poly(aminophenyl) silsesquioxanes (PAPSQ) are introduced as a cross‐linker into the polymide (PI) aerogel. A comparative aerogel is prepared, using 1,3,5‐triaminophenoxybenzene (TAB) as a cross‐linker. The aerogels are characterized in terms of their micro‐ and nanostructures, density, shrinkage, thermal conductivity and insulation, and mechanical properties. It is found that the PI‐PAPSQ aerogel have lower density, smaller shrinkage, lower thermal conductivity, higher thermal stability and insulation, and higher compression strength than the PI‐TAB aerogel. The 1.1 wt% PI‐PAPSQ shows the lowest aerogel density (0.010 g cm^?3) and the 2.2 wt% PI‐PAPSQ has a lower thermal conductivity (22.90 mW (m K)^?1 than air. A model of the PI‐TAB and PI‐PAPSQ cross‐linking networks are proposed to explain the excellent performance of the PI‐PAPSQ aerogel.     

Epoxy‐functionalized polyhedral oligomeric silsesquioxane/cyanate ester resin organic–inorganic hybrids with enhanced mechanical and thermal properties

A series of cyanate ester resin (CE) based organic–inorganic hybrids containing different contents (0, 5, 10, 15 and 20 wt%) of epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS‐Ep) were prepared by casting and curing. The hybrid resin systems were studied by the gel time test to evaluate the effect of POSS‐Ep on the curing reactivity of CE. The impact and flexural strengths of the hybrids were investigated. The micromorphological, dynamic mechanical and thermal properties of the hybrids were studied by SEM, dynamic mechanical analysis (DMA) and TGA, respectively. Results showed that POSS‐Ep prolonged the gel time of CE. CE10 containing 10 wt% POSS‐Ep displayed not only the optimum impact strength but the optimum flexural strength. SEM results revealed that the improvement of mechanical properties was attributed to the large amount of tough whirls and fiber‐like pull‐outs observed on the fracture surfaces of CE10. DMA results indicated that POSS‐CE tended to decrease E′ of the hybrids in the glassy state but to increase E′ of the hybrids in the rubbery state. TGA results showed that CE10 also possesses the best thermal stability. The initial temperature of decomposition (T_i) of CE10 is 426 °C, 44 °C higher than that of pristine CE. © 2013 Society of Chemical Industry     

Mechanical,thermal properties,and flame retardancy of PC/ultrafine octaphenyl‐POSS composites

Composites of ultrafine polyhedral oligomeric octaphenyl silsesquioxane (OPS) and polycarbonate (PC) were prepared by melt blending. The mechanical and thermal properties of the composites were characterized by tensile and flexural tests, impact test, differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), and thermal gravimetric analysis (TGA). Rheological properties of these melts were tested by torque rheometer. The flame retardancy of the composites was tested by limiting oxygen index (LOI), the vertical burning (UL‐94), and cone calorimeter test. The char residue was characterized by scanning electron microscope (SEM) and ATR‐FTIR spectrum. Furthermore, the dispersion of OPS particles in the PC matrix was evidenced by SEM. The results indicate that the glass transition temperatures (T_g) and torque of the composites decrease with increasing OPS loading. The onset decomposition temperatures of composites are lower than that of PC. The LOI value and UL‐94 rating of the PC/OPS composites increase with increasing loading of OPS. When OPS loading reaches 6 wt %, the LOI value is 33.8%, UL‐94 (1.6 mm) V‐0 rating is obtained, and peak heat release rate (PHRR) decreases from 570 to 292 kJ m^?2. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on thermal enhancement mechanism of POSS‐containing hybrid nanocomposites and relationship between thermal properties and their molecular structure

In this study, a series of poly(4‐acetoxystyrene) (PAS)‐octavinyl polyhedral oligomeric silsesquioxane (POSS) blends and the polystyrene (PS)‐octavinyl POSS blends were prepared by the solution‐blending method and characterized with Fourier transform infrared (FTIR), X‐ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) techniques. The results show that the glass‐transition temperature (T_g) of the PAS‐POSS blends increases at a relatively low POSS content and then decreases at a relatively high POSS content. POSS can effectively improve the thermal stability of the PAS‐POSS blends at low POSS content, and T_g of PAS‐POSS blends decreases with the increase in POSS content at relatively high POSS content. However, the T_g of the PS‐POSS blends persistently decreases even at very low POSS content. T_g change mechanism was investigated in detail by XRD, TEM, and FTIR spectra. The influence mechanism of POSS content and dispersion in composites, and parent polymer structure on thermal properties of the blends was investigated in detail. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of polyhedral oligomeric silsesquioxane nano‐crosslinked poly(ethylene glycol)‐based hybrid hydrogels for drug delivery and antibacterial activity

The synthesis is reported of novel hybrid hydrogels based on ethylenediaminetetraacetic acid dianhydride and poly(ethylene glycol) (PEG) with octa‐aminopropyl polyhedral oligomeric silsesquioxane hydrochloride salt (OA‐POSS) as a nano‐crosslinker under solvent‐free conditions. The molecular weight of PEG was varied between 600 and 1000 Da. The synthesized hydrogels were characterized using various techniques. Further, the swelling behavior and antibacterial activity of the hydrogels and release kinetics of metronidazole (MTZ) as a model drug from them were evaluated. Experimental results demonstrate that hydrogels with tunable properties can be synthesized by varying the PEG molecular weight and type of crosslinker (hybrid or organic). Among the synthesized hybrid hydrogels, that crosslinked by OA‐POSS with long PEG chains (1000 Da) showed the highest swelling degree (2000%), drug encapsulation efficiency (88%) and extent of MTZ release (96%). © 2018 Society of Chemical Industry     

Allylated novolac/4,4′‐bismaleimidodiphenylmethane resin containing polyhedral oligomeric silsesquioxane: Preparation,morphology and thermal stability

Allylated novolac/4,4′‐bismaleimidodiphenylmethane resin (AN/BDM) had been modified with well‐defined inorganic building blocks‐polyhedral oligomeric silsesquioxane (POSS). Octamaleimidophenyl polyhedral silsesquioxane (OMPS) was used as the cocuring reagent of the AN/BDM resin to prepare POSS‐modified AN/BDM resin, and POSS content was between 0 and 17.8 wt %. The curing reaction of the POSS‐modified AN/BDM resin was monitored by means of Fourier transform infrared spectroscopy (FTIR), and the results revealed that maleimide groups on OMPS molecule could undergothe curing reaction between allyl groups and maleimide groups. Therefore, the crosslinked network containing POSS was formed. Scanning electron microscopy (SEM) and X‐ray diffraction (XRD) were employed to study the morphology of the cured POSS‐modified AN/BDM resins. The homogeneous dispersion of POSS cages in AN/BDM matrices was evidenced. Thermogravimetric analysis (TGA) indicated that incorporation of POSS into AN/BDM crosslinked network led to enhanced thermal stability. The improved thermal stability could be ascribed to higher crosslink density and inorganic nature of POSS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3903–3908, 2007     

Double Dianhydride Backbone Polyimide Aerogels with Enhanced Thermal Insulation for High‐Temperature Applications

Aerogels owe their high thermal insulation and other unique properties to their nanostructure configuration. However, controlling the aerogels' morphology is always a scientific challenge. In this study, double dianhydride backbone (double backbone) polyimide aerogels with tailored nanostructure assembly are created for the first time. This is achieved by controlled polymerization reaction of oligomers with distinct dianhydride monomers. Combining the two oligomers through a controlled polymerization reaction is a successful strategy for tailoring the aerogels nanostructure assembly as well as other properties. The fabricated double backbone aerogel presents 40% reduced thermal conductivity of 19.7 mW mK^?1 over previously studied polyimide aerogels along with the compression modulus of 1.64 MPa at a relatively low density of 0.068 g cm^?3. Such low thermal conductivity is comparable with the inorganic counterparts. Light in weight and high thermally insulated polyimide aerogels with suitable mechanical properties and high service temperature are an appropriate replacement for current fireproof insulation materials.     

Synthesis and characterization of polyimide/polyhedral oligomeric silsesquioxane nanocomposites containing quinolyl moiety

A series of functional polyhedral oligomeric silsesquioxane (POSS)/polyimide (PI) nanocomposites were prepared using a two‐step approach. First, octa(aminophenyl)silsesquioxane (OAPS) was mixed with poly(amic acid) (PAA) prepared by reacting bis(4‐amino‐3,5‐dimethylphenyl)‐3‐quinolylmethane and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride. Second, the resulting solution was subjected to thermal imidization. The well‐defined ‘hard particles’ (POSS) and the strong covalent bonds in the amide linkage between the carbon atom of the carboxyl side group in PAA and the nitrogen atom of the amino group in POSS lead to a significant improvement in the thermal and mechanical properties. Homogeneous dispersion of POSS cages in the PI is evident from scanning electron microscopy, which further confirms that the POSS molecule becomes an integral part of the organic‐inorganic inter‐crosslinked network system. Differential scanning calorimetry and dynamic mechanical analysis show that the glass transition temperatures of the POSS‐containing nanocomposites are higher than that of the corresponding neat PI system, owing to the significant increase of the crosslinking density in the PI/POSS nanocomposites. Increasing the concentration of OAPS in the PI networks decreases the dielectric constant. Pure PI and PI/POSS systems have good antimicrobial activity. Copyright © 2011 Society of Chemical Industry     

Properties of poly(butylene terephthalate) chain‐extended by epoxycyclohexyl polyhedral oligomeric silsesquioxane

Epoxycyclohexyl polyhedral oligomeric silsesquioxane (epoxy–POSS) was used to prepare a chain‐extended poly(butylene terephthalate) (PBT) with a twin‐screw extruder. The effect of epoxy–POSS on the melt flow index, mechanical properties, rheological behavior, and thermal properties of chain‐extended PBT was investigated. PBT had an intrinsic viscosity of 1.1 dL/g and a carboxy1 content of 21.6 equiv/10⁶ g, but the PBT chain‐extended with 2 wt % epoxy–POSS had an intrinsic viscosity of 1.7 dL/g and a carboxy1 content lower than 7 equiv/10⁶ g. After the addition of epoxy–POSS, the melt flow index of PBT dramatically decreased, the elongation at break increased greatly, the tensile strength increased slightly, and the thermal stability was also improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(vinyl pyrrolidone‐co‐octavinyl polyhedral oligomeric silsesquioxane) hybrid nanocomposites: Preparation,thermal properties,and Tg improvement mechanism

A series of poly(vinyl pyrrolidone‐co‐octavinyl polyhedral oligomeric silsesquioxanes) (PVP‐POSS) organic–inorganic hybrid nanocomposites containing different percentages of POSS were prepared via free radical polymerization and characterized by FTIR, high‐resolution ¹H‐NMR, solid‐state ²⁹Si‐NMR, GPC, DSC, and TGA. POSS contents in these nanocomposites can be effectively controlled by varying the POSS feed ratios which can be accurately quantified by FTIR curve calibration. On the basis of ²⁹Si‐NMR spectra, average numbers of reacted vinyl groups of each octavinyl‐POSS macromer are calculated to be 5–7, which depends on POSS feed ratios. Both GPC and DSC results indicate that these nanocomposites display network structure and the degree of crosslinking increases with the increase of the POSS content. The incorporation of POSS into PVP significantly improves their thermal properties (T_g and T_dec) primarily due to crosslinking structure and dipole–dipole interaction between POSS cores and PVP carbonyl groups. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of poly(ε‐caprolactone)/clay nanocomposites using polyhedral oligomeric silsesquioxane surfactants as organic modifier and initiator

Poly(ε‐caprolactone)/clay nanocomposites were synthesized by in situ ring‐opening polymerization of ε‐caprolactone in the presence of montmorillonite modified by hydroxyl functionalized, quaternized polyhedral oligomeric silsesquioxane (POSS) surfactants. The octa(3‐chloropropyl) polyhedral oligomeric silsesquioxane was prepared by hydrolytic condensation of 3‐chloropropyltrimethoxysilane, which was subsequently quaternized with 2‐dimethylaminoethanol. Montmorillonite was modified with the quaternized surfactants by cation exchange reaction. Bulk polymerization of ε‐caprolactone was conducted at 110°C using stannous octoate as an initiator/catalyst. Nanocomposites were analyzed by X‐ray diffraction, transmission electron microscopy, thermo gravimetric analysis, and differential scanning calorimetry. Hydroxyl functionalized POSS was employed as a surface modifier for clay which gives stable clay separation for its 3‐D structure and also facilitates the miscibility of polymer with clay in the nanocomposites due to the star architecture. An improvement in the thermal stability of PCL was observed even at 1 wt % of clay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of additive structure and size on SiO2 formation in polymer‐derived SiOC ceramics

Silicon oxycarbide (SiOC) ceramics with highly adjustable properties and microstructures have many promising applications in batteries, catalysis, gas separation, and supercapacitors. In this study, additive structures on the nucleation and growth of SiO₂ within SiOC ceramics are investigated by adding cyclic tetramethyl‐tetravinylcyclotetrasiloxane (TMTVS) or caged octavinyl‐polyhedral oligomeric silsesquioxane (POSS) to a base polysiloxane (PSO) precursor. The effects of the 2 additives on the polymer‐to‐ceramic transformation and the phase formation within the SiOC are discussed. POSS encourages SiO₂ nucleation and leads to more SiO₂ formation with significantly increased ceramic yield, which subsequently leads to higher specific surface of 1557 m²/g with a larger pore size of ～1.8 nm for the porous SiOC. High TMTVS content decreases both the specific surface area and pore volume of the resulting porous SiOCs. This study demonstrates a new approach of using Si‐rich additive POSS to increase the SiOC yield while maintaining or even increasing the specific surface area.     

含活性氢基的八聚笼型倍半硅氧烷的合成与表征

笼形倍半硅氧烷具有较低的介电常数。采用正硅酸乙酯和季铵碱为原材料,合成了八聚四甲基铵基笼型倍半硅氧烷,并采用二甲基氯硅烷对其进行烷基取代,得到了含活性氢基的八聚笼型倍半硅氧烷。采用核磁共振29Si、13C、1H谱和凝胶渗透色谱GPC对其结构进行了表征和确认。     

Synthesis and characterization of novel reactive ladder‐like polysilsesquioxanes with side‐chain ester groups (Ester‐Ts)

Two kinds of structure‐ordered reactive ladder‐like polysilsesquioxanes with different side‐chain ester groups (Ester‐Ts) have been synthesized successfully by a new route – stepwise coupling polymerization – with three steps including preaminolysis, hydrolysis and polycondensation. Two monomers, 2‐trichlorosilylethyl acetate (M₁) and 3‐trichlorosilylpropyl propionate (M₂), were first synthesized by hydrosilylation with dicyclopentadienylplatinum (II) chloride (Cp₂PtCl₂) as a catalyst. Monomer and polymer structures were characterized by FTIR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, X‐ray diffraction (XRD), differential scanning calorimetry (DSC) and vapour pressure osmometry (VPO). Characterization data indicate that these two polymers have ordered ladder‐like structures. © 2000 Society of Chemical Industry     

Synthesis and gas permeability of ABA‐type triblock copolymers derived from fluorine‐containing polyimide with polyhedral oligomeric silsesquioxane

ABA‐type triblock copolymers derived from 4,4'‐(hexafluoroisopropylidene)diphthalicanhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and methacryl phenyl polyhedral oligomeric silsesquioxane (MPPOSS) were synthesized by atom transfer radical polymerization. The chemical structure of the synthesized ABA‐type triblock copolymer was confirmed by ¹H NMR, ¹³C NMR, ²⁹Si NMR and Fourier transform infrared analyses. The ratios of 6FDA‐TeMPD and MPPOSS determined by TGA were 94/6, 85/15, 77/23, 68/32, 57/43 and 31/69. The film density of the ABA‐type triblock copolymer films did not conform to the mixing rule because of polyimide (PI) chain aggregation. Based on contact angle and water uptake analyses, the hydrophobicity of the ABA‐type triblock copolymer film was determined to be higher than the theoretical value because of POSS cage effects and PI chain aggregation. The gas permeability coefficient of the ABA‐type triblock copolymer decreased compared with that of PI because of aggregation of PI chains and inhibition of solubility decreases by substitutes with high affinity. ABA‐type triblock copolymer CO₂/H₂ separation performance increased compared with that of PI. The ABA‐type triblock copolymer derived from PI and MPPOSS can be described as a polymer material with higher hydrophobicity and higher CO₂/H₂ selectivity than PI. © 2015 Society of Chemical Industry     

Effect of polyhedral oligomeric silsesquioxane on water sorption and surface property of Bis‐GMA/TEGDMa composites

2,2‐Bis[4‐(2‐hydroxy‐3‐methacryloxypropoxy)phenyl]propane (Bis‐GMA), one of the most important light‐curable dimethacrylate resins, is widely used as dental restorative material. However, one problem of Bis‐GMA is the high water sorption due to the hydrophilic hydroxyl (–OH) group, resulting in a short life in actual application. In this study, to overcome the drawback stated above, novel organic–inorganic dimethacrylate monomer containing polyhedral oligomeric silsesquioxanes (POSS), Bis‐GMA‐graft‐POSS, is synthesized via the nucleophilic addition reaction of isocyanate functionalized POSS (IPOSS) and pendent hydroxyl group of Bis‐GMA. Then the as‐synthesized Bis‐GMA‐graft‐POSS, of which hydroxyl group was substituted by hydrophobic POSS, is also introduced into the Bis‐GMA/TEGDMA matrix to prepare a series of methacrylate‐based hybrids for dental materials under visible light with camphorquinone and ethyl‐4N,N‐dimethy‐laminobenzoae (EDMAB) as initiator and coinitiator, respectively. Compared to Bis‐GMA/TEGDMA composites, water sorption of modified composites can be significantly reduced with the addition of Bis‐GMA‐graft‐POSS. Moreover, the Bis‐GMA/TEGDMA/POSS hybrids show hydrophobic surfaces, leading to much higher water contact angles than that of Bis‐GMA/TEGDMA composites. The morphology of hybrids containing POSS was furthermore studied by X‐ray diffraction (XRD) analysis and X‐ray photoelectron spectroscopy (XPS). The results show that POSS disperses in the matrix in noncrystalline form and tend to migrate to the surface of the modified composites that lead to the lower water sorption and higher water contact angles. These results are very useful for design of novel methacrylate monomers and clinical application. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hydrophobic,Pore‐Tunable Polyimide/Polyvinylidene Fluoride Composite Aerogels for Effective Airborne Particle Filtration

Polyimide (PI) aerogels have great potential as filter materials, owing to their unique porous structure and excellent thermodynamic properties. In this work, polyvinylidene fluoride (PVDF) is introduced into the 3D network structure of crosslinked PI by phase separation to prepare PI/PVDF hybrid aerogels. By adding different amounts of PVDF, effective control of the aerogel porous structure is achieved, as a result, the air permeability of the hybrid aerogel is significantly improved while still achieving a filtration efficiency of airborne particulates of more than 99.8%. PVDF is aggregated and dispersed on the surface or inside of the aerogel in the form of nanoparticles, which effectively increases the hydrophobicity of the material. The contact angle of the prepared PI hybrid aerogel is ≈150°, and the water absorption is as low as 2.2%, which enables the aerogel to maintain structural stability in humid environments. In addition, the aerogel exhibits good adsorption effects on organic solvents.     

Synthesis,characterization and surface properties of star‐shaped polymeric surfactants with polyhedral oligomeric silsesquioxane core

Star‐shaped amphiphilic polymeric surfactants comprising a hydrophobic polyhedral oligomeric silsesquioxane (POSS) core and hydrophilic poly(ethylene glycol) (PEG) arms with various chain lengths are successfully synthesized using copper(I)‐catalysed azide–alkyne cycloaddition (CuAAC) click reaction. Their chemical structures and molecular characteristics are clearly confirmed using Fourier transform infrared and ¹H NMR spectroscopies and gel permeation chromatography, and no homopolymer is found after CuAAC click reaction. Aqueous solutions of these star‐shaped polymers have been investigated using atomic force and transmission electron microscopies and dynamic light scattering studies and it is found that they can self‐assemble into micelles. The sizes of the micelles can be adjusted by the length of the PEG arms, where longer chains not only lead to increased micelle sizes, but also reduce the contact angle values. Moreover, the melting points and root mean square roughness of the obtained star‐shaped polymers are slightly increased on increasing the chain length of the PEG arms. © 2017 Society of Chemical Industry