Preparation and thermal property of hybrid nanocomposites by free radical copolymerization of styrene with octavinyl polyhedral oligomeric silsesquioxane

The poly(styrene‐co‐octavinyl‐polyhedral oligomeric silsesquioxane) (PS–POSS) organic–inorganic hybrid nanocomposites containing various percent of POSS were prepared via one‐step free radical polymerization and characterized by FTIR, high‐resolution ¹H NMR, ²⁹Si NMR, GPC, DSC, and TGA technologies. The POSS contents in these nanocomposites were determined using FTIR calibration curve. The result shows that the POSS contents in nanocomposites can be tailored by varying the POSS feed ratios. On the basis of the POSS contents in the nanocomposites and the ¹H NMR spectra, the number of reacted vinyl groups of each octavinyl‐POSS macromonomer were calculated to be 6–8. DSC and TGA measurements indicate that the incorporation of POSS into PS homopolymer can apparently improve the thermal properties of the polymeric materials. The dramatic T_g and T_dec increases are mainly due to the formation of star and low cross‐linking structure of the nanocomposites, where POSS cores behave as the joint points and hinder the motion and degradation of the polymeric chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Characterization of poly(vinyl pyrrolidone‐co‐isobutylstyryl polyhedral oligomeric silsesquioxane) nanocomposites

Poly(vinyl pyrrolidone‐co‐isobutyl styryl polyhedral oligomeric silsesquioxane)s (PVP–POSS) were synthesized by one‐step polymerization and characterized using FTIR, high‐resolution ¹H‐NMR, solid‐state ¹³C‐NMR, ²⁹Si‐NMR, GPC, and DSC. The POSS content can be controlled by varying the POSS feed ratio. The T_g of the PVP–POSS hybrid is influenced by three main factors: (1) a diluent role of the POSS in reducing the self‐association of the PVP; (2) a strong interaction between the POSS siloxane and the PVP carbonyl, and (3) physical aggregation of nanosized POSS. At a relatively low POSS content, the role as diluent dominates, resulting in a decrease in T_g. At a relatively high POSS content, the last two factors dominate and result in T_g increase of the PVP–POSS hybrid. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2208–2215, 2004     

Synthesis of phosphorus‐containing polyhedral oligomeric silsesquioxanes via hydrolytic condensation of a modified silane

A simple route to synthesize a new type of phosphorus‐containing polyhedral oligomeric silsesquioxanes (DOPO–POSS) in high yield, by the hydrolytic condensation of a modified silane, is reported. The starting material was a phosphorus‐containing triethoxy silane (DOPO–VTES), which was synthesized by addition reaction between 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and vinyl triethoxy silane (VTES). This product was subjected to hydrolytic condensation using an HCl catalyst in methanol. The new types of phosphorus‐containing POSS were obtained and characterized using ¹H, ¹³C, ²⁹Si‐NMR, MALDI‐TOF MS, XRD, DSC, and FTIR. All of these results suggested that the DOPO–POSS were amorphous mixtures of T₈, T₉(OH), and TGA curve of DOPO–POSS shows that the cage‐like compound has high thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Direct synthesis and characterization of crosslinked polysiloxanes via anionic ring‐opening copolymerization with octaisobutyl‐polyhedral oligomeric silsesquioxane and octamethylcyclotetrasiloxane

The crosslinked polysiloxanes were directly synthesized by anionic ring‐opening copolymerization of octaisobutyl‐polyhedral oligomeric silsesquioxane (POSS) as a multifunctional monomer with octamethylcyclotetrasiloxane (D₄) under base catalysts such as potassium hydroxide (KOH) or tetramethylammonium hydroxide (Me₄ NOH) siloxanolate. The mechanism of anionic ring‐opening copolymerization of octaisobutyl‐POSS and D₄ was discussed and the influences of the polar additive N,N‐dimethylacetamide on gelation time at different temperatures were investigated. The results of gel content and swelling ratio, GPC, solid‐state ²⁹Si and ¹³C NMR, FTIR, XRD show that octaisobutyl‐POSS is reacted and most of the product is crosslinked. The DSC and TG results indicate that the crosslinked polysiloxanes exhibit distinct glass transition temperatures (T_g) and excellent thermal stability. Compared to that under KOH siloxanolate, the crosslinked polysiloxane synthesized with Me₄NOH siloxanolate has better preferable thermal stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3848–3856, 2006     

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     

Preparation and characterization of poly(methyl methacrylate) nanocomposites containing octavinyl polyhedral oligomeric silsesquioxane

A series of poly(methyl methacrylate) (PMMA) containing octavinyl-polyhedral oligomeric silsesquioxane (OV-POSS) nanocomposites were synthesized by solution polymerization. The products were characterized by FTIR, ¹H NMR, GPC, TEM, DSC and TGA. The actual contents of OV-POSS in the obtained products and the reaction degree of the vinyl groups in the POSS were calculated on the basis of FTIR, TGA and ¹H NMR data respectively. The DSC and TGA results indicate that the incorporation of POSS molecules could improve the thermal properties of PMMA nanocomposites significantly. The glass transition temperature (T_g) and thermal decomposition temperature (T_dec1) of the nanocomposite with 12.27 wt % of OV-POSS were increased by 23 °C and 93 °C correspondingly. In our experiment, the improved thermal properties were largely attributed to the nanoreinforcement effect of POSS cages and the formation of star-shaped structures with cubic silsesquioxane core.     

Synthesis,structure, and properties of high‐impact polystyrene/octavinyl polyhedral oligomeric silsesquioxane nanocomposites

The organic–inorganic hybrid nanocomposites from high‐impact polystyrene/octavinyl polyhedral oligomeric silsesquioxane (HIPS/POSS) containing various percentages of POSS were prepared by free radical polymerization and characterized by Fourier transform infrared spectroscopy (FTIR), ¹H‐NMR, thermal gravity analysis (TGA), X‐ray diffraction (XRD), and transmission electron microscopy (TEM). The octavinyl POSS has formed covalent bond connected PS‐POSS hybrid with polystyrene. POSS can well disperse in the composites at the composition of 0.5 and 1 wt%. The mechanical properties and thermostability of HIPS/POSS nanocomposites were significantly improved. The tensile strength, the izod impact strength, and the elongation at break of the nanocomposite containing 1 wt% of POSS was increased, respectively, by 15.73%, 75.62%, and 72.71% in comparison with pristine HIPS. The thermal decomposition temperature of HIPS/POSS (1 wt% of POSS) was 33°C higher than that of pristine HIPS. The HIPS/POSS nanocomposites showed great potential for applications in many fields, such as electric appliance and automotive trim. POLYM. COMPOS. 37:1049–1055, 2016. © 2014 Society of Plastics Engineers     

POSS‐based molecular hybrids with low dielectric constant: Effect of chemical structure and molecular architecture

Three kinds of hybrids with different architectures including dumbbell‐type, bead‐type, and cross‐linked structure, were prepared via the Heck reaction between octavinyl‐polyhedral oligomeric silsesquioxane (OV‐POSS) and different bromo‐substituted aromatic amide monomers. The molecular architecture can be successfully achieved by simply varying the feed ratio of OV‐POSS to monomers. Their structure and properties were characterized by FTIR, ¹H NMR, ²⁹Si NMR, provide the expansion for FTIR and NMR] All the POSS‐based hybrids exhibited good thermal stability and low dielectric constant properties. The relationship between chemical structure, molecular architecture, and the dielectric constant of these hybrids were investigated in detail. The results show that POSS content dominated the low dielectric constant of the hybrids, while the chemical structure of organic chains and molecular architecture also play an important role on the formation of low dielectric constant. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42292.     

Novel phenyl‐POSS/polyurethane aqueous dispersions and their hybrid coatings

A facile and rapid preparation of 3‐(2‐aminoethylamino)propylheptaphenylPOSS (AA‐POSS), a special phenyl‐POSS that contains two functional amino groups (Scheme 1), is demonstrated by the corner‐capping method. Then AA‐POSS forms a series of novel phenyl‐POSS/PU aqueous dispersions. The structure of AA‐POSS has been confirmed by ¹H, ¹³C, ²⁹Si NMR, and ESI‐MS. The POSS/PU hybrid films are studied by Fourier transform infrared spectrometer (FT‐IR), gel permeation chromatography (GPC), scanning electron microscope (SEM), X‐ray diffraction (XRD) spectra, differential scanning calorimetry (DSC) analysis, and thermal gravimetric analyzer (TGA). FT‐IR and GPC are conducted to validate the chemical structure of the hybrid PU. The properties of hybrid films display significant changes with notable increases in T_g, thermal properties, tensile strength, as well as surface hydrophobicity. These changes are attributed to the incorporation of novel POSS into PU. Moreover, these significant material property enhancements are achieved at low levels of POSS incorporation (only 4%). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1611–1620, 2013     

A novel and facile method for the synthesis of octa(aminophenyl)silsesquioxane and its nanocomposites with bismaleimide‐diamine resin

Octa(aminophenyl)silsesquioxane (OAPS) was prepared from octa(nitrophenyl)silsesquioxane (ONPS) by using the stable, inexpensive, and readily available hydrazine hydrate as the reducing agent with a yield of around 86%. The product was characterized by FTIR, GPC, ¹H NMR, ²⁹Si NMR, and XRD. It was found that the time period for preparation of ONPS from octaphenylsilsesquioxane could be considerably shortened, reaching the complete nitration and avoiding double nitration of the aromatic rings. The polyimides were prepared by the reaction of N,N′‐bismaleimido‐4,4′‐diphenylmethane with OAPS and 4,4′‐diamino‐diphenyl ether. The structure of resulting organic–inorganic hybrid nanocomposites was characterized by XRD and FTIR. The decomposition temperature and char yield of resulting materials increased with increasing OAPS loading. The DSC data showed that the glass transition temperature of nanocomposite was enhanced by 36°C with the content of OAPS around 15 wt %. As the feed amount of OAPS increased further, the decrease in T_g's could be observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1004–1010, 2007     

Poly(acetoxystyrene-co-isobutylstyryl POSS) Nanocomposites: Characterization and Molecular Interaction

The poly(acetoxystyrene-co-isobutyl styryl polyhedral oligomeric silsesquioxanes)s (PAS-POSS) were synthesized by free radical polymerization and characterized by FTIR, high resolution NMR, FTIR, GPC, and DSC. The results show that the POSS content can be controlled by varying the POSS feed ratios. The interactions between organic components and inorganic POSS core, and the effects of inorganic POSS core on the properties of the resulting hybrids were investigated by high resolution solid state ¹³C NMR, ²⁹Si NMR and FTIR spectra. The results provide detailed understandings of the effects of POSS moiety on properties of hybrid polymers.     

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

A 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 (T_g) of the PMMA–POSS blends showed a tendency of first increasing and then decreasing with an increase in the POSS content. The maximum T_g 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 T_g 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 T_g 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 T_g decrease in these hybrid nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly (imide–benzimidazole) hybrid nanocomposites using nano‐cluster of octa‐amino functionalized polyhedral oligomeric silsesquioxane

Poly (imide–benzimidazole)/polyhedral oligomeric silsesquioxane (POSS), nanocomposites were prepared by the reaction of the heterocyclic diamine monomer 2,2‐(1,2‐phenylene)‐bis(5‐aminobenzimidazole), octa(aminophenyl)silsesquioxane(OAPS), and benzophenonetetra carboxylic dianhydride (BTDA). The structure of the prepared monomers was confirmed by FTIR and NMR (²⁹Si, ¹H, and ¹³C) spectral studies. The thermal stability behavior of the poly (imide–benzimidazole) and poly (imide–benzimidazole)–POSS nanocomposite films were studied by differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA). Dynamic mechanical analysis shows that the glass transition temperatures of the polyhedral oligomeric silsesquioxane (POSS) containing poly (imide–benzimidazole) nanocomposites are higher than that of the corresponding neat poly (imide–benzimidazole) systems. Decrease in the dielectric constant was observed with an increase in the determined amount of amino‐functionalized POSS in the poly (imide–benzimidazole) matrix. Further, the morphological studies were carried out by X‐ray diffraction and transmission electron microscopy. POLYM. COMPOS., 34:825–833, 2013. © 2013 Society of Plastics Engineers     

Synthesis and characterization of organic–inorganic hybrid polymers with a well‐defined structure from diamines and epoxy‐functionalized polyhedral oligomeric silsesquioxanes

A new class of organic‐inorganic hybrid polymers with well‐defined structure was prepared by reacting diepoxyhexavinyl polyhedral oligomeric silsesquioxanes (DehvPOSS) with diamines of different chain lengths. The structures and properties of these hybrid polymers were well characterized by FTIR, ²⁹Si‐NMR, GC‐MS, and TGA. A modeling characterization was employed to help identify the structures of organic tethers linked between the POSS cages. The results indicated that at the stoichiometric ratio of DehvPOSS to diamine, well‐defined organic–inorganic hybrid polymers with controlled variation of the organic tether architecture can be made, and each organic tether connected four POSS cages. Thermal stability (T_dec) increased with an increase in the tether length of the diamine molecules, and the highest T_dec was obtained with butanediamine (rather than propanediamine or ethanediamine) as the organic tether. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3730–3735, 2006     

POSS Core star‐shape molecular hybrid materials: Effect of the chain length and POSS content on dielectric properties

A series of inorganic–organic molecular hybrids, poly(styrene‐co‐octavinyl‐polyhedral oligomeric silsesquioxane)s (PS‐POSSs), were synthesized, and their structures and properties were characterized by FTIR, ¹H‐NMR, ²⁹Si‐NMR, XRD, optical microscopy (OM), and atomic force microscopy (AFM). The chemical incorporation of POSS into polymer matrixes achieves uniform dispersion and makes the resultant hybrids display good film formability. The relationship between molecular structure of these hybrids and their dielectric constants and formation mechanism of low dielectric constant were investigated. The low dielectric constant of the hybrids mainly originates from the increase of free volume, involving the free volume of intrinsic porosity from POSS and an increase in the free volume owing to steric hindrance of bulky POSS. The latter plays a dominant role to increase the free volume and formation of low dielectric constant. Simultaneously, the polymer arm‐length has an important influence on the dielectric constant of the star‐type hybrids. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of poly(HEMA‐co‐MMA)‐g‐POSS nanocomposites by combination of reversible addition fragmentation chain transfer polymerization and click chemistry

New hybrid poly(hydroxyethyl methacrylate‐co‐methyl methacrylate)‐g‐polyhedral oligosilsesquioxane [poly(HEMA‐co‐MMA)‐g‐POSS] nanocomposites were synthesized by the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and click chemistry using a grafting to protocol. Initially, the random copolymer poly(HEMA‐co‐MMA) was prepared by RAFT polymerization of HEMA and MMA. Alkynyl side groups were introduced onto the polymeric backbones by esterification reaction between 4‐pentynoic acid and the hydroxyl groups on poly(HEMA‐co‐MMA). Azide‐substituted POSS (POSS? N₃) was prepared by the reaction of chloropropyl‐heptaisobutyl‐substituted POSS with NaN₃. The click reaction of poly(HEMA‐co‐MMA)‐alkyne and POSS? N₃ using CuBr/PMDEATA as a catalyst afforded poly(HEMA‐co‐MMA)‐g‐POSS. The structure of the organic/inorganic hybrid material was investigated by Fourier transformed infrared, ¹H‐NMR, and ²⁹Si‐NMR. The elemental mapping analysis of the hybrid using X‐ray photoelectron spectroscopy and EDX also suggest the formation of poly(HEMA‐co‐MMA)‐anchored POSS nanocomposites. The XRD spectrum of the nanocomposites gives evidence that the incorporation of POSS moiety leads to a hybrid physical structure. The morphological feature of the hybrid nanocomposites as captured by field emission scanning electron microscopy and transmission electron microscopic analyses indicate that a thick layer of polymer brushes was immobilized on the POSS cubic nanostructures. The gel permeation chromatography analysis of poly(HEMA‐co‐MMA) and poly(HEMA‐co‐MMA)‐g‐POSS further suggests the preparation of nanocomposites by the combination of RAFT and click chemistry. The thermogravimetric analysis revealed that the thermal property of the poly(HEMA‐co‐MMA) copolymer was significantly improved by the inclusion of POSS in the copolymer matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characteristics of photoactive‐hydrogenated rosin epoxy methacrylate for pressure sensitive adhesives

Hydrogenated rosin epoxy methacrylate (HREM), based on hydrogenated rosin and glycidyl methacrylate (GMA), was synthesized for use as an advanced tackifier in the UV‐crosslinking pressure sensitive adhesives (PSAs) system. The HREM, as a tackifier, contained UV‐curing sites; thus, allowed photopolymerization to occur by UV irradiation. This UV‐curable tackifier, HREM, can improve the curing rate and adhesion performance of UV‐crosslinking PSAs. The characteristics of HREM were analyzed by GPC and DSC and its synthetic mechanism studied using FTIR and ¹H NMR; the characteristic peaks of hydrogenated rosin and GMA vanished, but new peaks for HREM appeared. The PDI and the T_g by DSC were 1 and ?25.6°C, respectively. The photopolymerization of HREM was studied using photo‐DSC. Heat flow was observed during UV irradiation, and the curing rate and conversion both increased with rising photoinitiator content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nanocomposites based on copolymers of fluorinated imide and polyhedral oligomeric silsesquioxane macromonomer: microstructure and morphology studies

Towards the development of copolymeric nanocomposites, N‐3(trifluoromethyl)phenyl‐7‐oxanorbornene‐5,6‐dicarboximide (TFI) monomer and a macromonomer of polyhedral oligomeric silsesquioxane (POSS) were synthesized. Ring‐opening metathesis polymerization to copolymerization of specified proportions of the two co‐monomers was carried out. All the monomers and polymers were characterized using Fourier transform IR analysis and ¹H and ²⁹Si NMR. Gel permeation chromatography shows that copolymeric nanocomposites have a lower average molar mass than a homopolymer of TFI (HTFI). TGA shows that the thermal stability of the copolymer is inversely proportional to the proportion of POSS units. DSC studies have demonstrated that the glass transition temperature (T_g) of a nanocomposite possessing 25 wt% POSS is at a higher temperature (180 °C) than that of HTFI (175 °C). Transmission electron microscopy and AFM images of copolymers are consistent with the self‐assembled spherical aggregation of POSS units, while X‐ray diffraction studies have confirmed the homogeneous dispersion of the same units within the nanocomposites. © 2012 Society of Chemical Industry     

Structure–property relationship of blocked diisocyanates: synthesis of polyimides using imidazole‐blocked isocyanates

Imidazole, 2‐methylimidazole and benzimidazole‐blocked aromatic and aliphatic diisocyanates have been prepared and polymerized with pyromellitic dianhydride in the presence of a basic catalyst. The polymers are characterized with FTIR, ¹H NMR and ¹³C NMR spectroscopy and GPC, DSC and TGA. The structure–property relationship of blocked diisocyanates are discussed in terms of molecular weight of the polyimides obtained. Considering the blocking agent, GPC results show that the benzimidazole blocked adduct yields higher molecular weight polymer than the 2‐methylimidazole‐blocked adduct which, in turn, yields higher molecular weight polymer than the imidazole‐blocked adduct. Considering the structure of the isocyanate, the molecular weight of polymer increases from isophorone diisocyanate to hexamethylene diisocyanate and to toluene diisocyanate (TDI). DSC traces of the polymers derived from TDI show glass transitions (T_g) in the temperature range 152–180 °C and the values increase from the polymer based on imidazole‐blocked TDI to 2‐methylimidazole‐blocked TDI and to benzimidazole‐blocked TDI. © 2000 Society of Chemical Industry     

Synthesis,characterization, and thermo mechanical properties of siloxane‐modified epoxy‐based nano composite

In this study, polymer hybrid composites were synthesized by sol‐gel process. 3‐Amino‐propyltrimethoxysilane [APTMS)/γ‐Glycidoxypropyl trimethoxy‐silane (GPTMS); (4, 4′‐Methylene‐dianiline (DDM)] and 1,4‐Bis(trimethoxysilylethyl) benzene (BTB) were added to DGEBA type epoxy resin for anticipated to exhibit excellent thermal stability. Boron trifluoride monoethylamine (BF₃MEA) was used as catalyst. The structure of nanocomposites was characterized by attenuated total reflectance (ATR) and solid‐state ²⁹Si NMR which suggest EP‐APTMS‐BTB/EP‐GPTMS‐BTB possesses T³; T¹–T⁰, and T¹ structures when the BTB content was lower than 10 wt % and higher 20 wt %, respectively. BF₃MEA was proved to be an effective catalyst for the sol‐gel reaction of APTMS, but it could not promote for GPTMS. From TEM microphotographs, EP‐APTMS‐BTB (10 wt %) possesses a dense inorganic structure (particle size around 5–15 nm) compare with the loose inorganic structure of EP‐GPTM‐/BTB (10 wt %). DSC, TGA were use to analyze the thermal properties of the nanocomposites and DMA was used to analyze the dynamic mechanical properties of hybrid composites. The T_gs of all nanocomposites decreased with the increasing BTB content. A system with BTB content lower than 10 wt % showed good dynamic mechanical property and thermal stability (Td₅ increased from 336°C to 371°C, char yield increased from 27.4 to 30.2%). The structure of inorganic network affects the Td₅ and dynamic mechanical properties of composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40984.