UV curable soybean‐oil hybrid systems based on thiol‐acrylate and thiol‐ene‐acrylate chemistry

In this study, epoxidized soybean oil was modified to prepare acrylated epoxidized soybean oil (AESO) and vinyl/acrylate ended soybean oil (VASO), which were blended with mercaptopropyl polyhedral oligomericsilsequioxane (POSS‐SH) to prepare UV curable thiol‐acrylate and thiol‐ene‐acrylate hybrid coatings. Photopolymerization processes of the coatings were measured and the results showed that addition of POSS‐SH obviously increased the conversion of double bond. The physical and mechanical properties of all cured samples were investigated, which indicated that the pencil hardness, tensile strength, and fracture toughness were significantly improved by POSS‐SH. Moreover, with increasing POSS‐SH content, the water contact angles of cured samples were increased, and the water resistance was greatly improved. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42095.     

Epoxidized pine oil‐siloxane: Crosslinking kinetic study and thermomechanical properties

In this study, a novel approach to toughen biobased epoxy polymer with different types of siloxanes was explored. Three different modified siloxanes, e.g., amine‐terminated polydimethyl siloxane (PDMS‐amine), glycidyl‐terminated polydimethyl siloxane (PDMS‐glycidyl), and glycidyl‐terminated polyhedral oligomeric silsesquioxane (POSS‐glycidyl) were used as toughening agents. The curing and kinetics of bioepoxy was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy. The mechanical, thermal, and morphological properties of the cured materials were investigated. Rheological characterization revealed that the inclusion of POSS‐glycidyl slightly increased the complex viscosity compared to the neat resin. The morphology of the cured bioresin was characterized by transmission electron microscopy and scanning electron microscopy. The inclusion of POSS‐glycidyl to bioepoxy resin resulted in a good homogeneity within the blends. The inclusion of PDMS‐amine or PDMS‐glycidyl was shown to have no effect on tensile and flexural properties of the bioresins, but led to a deterioration in the impact strength. However, the inclusion of POSS‐glycidyl enhanced the impact strength and elongation at break of the bioresins. Dynamic mechanical analysis showed that the siloxane modified epoxy decreased the storage modulus of the bioresins. The thermal properties, such as decomposition temperature, coefficient of linear thermal expansion, and heat deflection temperature were improved by inclusion of POSS‐glycidyl. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42451.     

Synthesis and effects of MDT silicone resin on PMPS‐based ablative composites

A novel methylphenyl silicone resin, with M, D, and T units, was synthesized by cohydrolysis and cocondensation method from dimethyldimethoxysilane (Me₂Si(OMe)₂), phenyltrimethoxysilane (PhSi(OMe)₃), hexamethyldisiloxane, and 1,3‐divinyl‐1,1,3,3‐tetramethyldisiloxane in toluene/water mixture catalyzed by hydrochloric acid and trifluoromethanesulfonic acid. The vinyl end‐capped MDT silicone resins were chosen for reinforcement filler to enhance the mechanical properties of silicone‐based ablative composites. The effects of resins with various R/Si ratios, vinyl content, and loadings on mechanical properties of PMPS rubbers were investigated. It was revealed that on the premise of good fluidity and processing performance, MDT resin showed excellent reinforcing effect and thermal stability compared with silica. MDT reinforced ablative composite showed satisfactory mechanical and antiablative properties. The linear ablation rate was 0.01 mm/s, which maybe associated with high yield of charred residue in thermogravimetric analysis results. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41571.     

Low dielectric and high thermal conductivity epoxy nanocomposites filled with NH2‐POSS/n‐BN hybrid fillers

Hybrid fillers of mono‐amine polyhedral oligomeric silsesquioxane/nanosized boron nitride (NH₂‐POSS/n‐BN) were performed to fabricate NH₂‐POSS/n‐BN/epoxy nanocomposites. Results revealed that the dielectric constant and dielectric loss values were decreased with the increasing addition of NH₂‐POSS obviously, but increased with the increasing addition of BN fillers. For a given loading of NH₂‐POSS (5 wt %), the thermal conductivities of NH₂‐POSS/n‐BN/epoxy nanocomposites were improved with the increasing addition of n‐BN fillers, and the thermal conductivity of the nanocomposites was 1.28 W/mK with 20 wt % n‐BN fillers. Meantime, the thermal stability of the NH₂‐POSS/n‐BN/epoxy nanocomposites was also increased with the increasing addition of n‐BN fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41951.     

Preparation and characterization of novel polydimethylsiloxane composites used POSS as cross‐linker and fumed silica as reinforcing filler

A series of novel polydimethylsiloxane (PDMS) composites were prepared using octa[(trimethoxysilyl)ethyl]‐POSS (OPS) as cross‐linker and fumed silica as reinforcing filler. The cross‐linked networks, morphologies, thermal and mechanical properties of these novel PDMS composites were examined by attenuated total reflection infrared spectroscopy and the extraction/swelling experiment, scanning electron microscope, thermogravimetric analysis, and universal tensile testing machine, respectively. It was found that both the resistance to thermal degradation and mechanical properties of the novel PDMS composites were improved greatly by adding fumed silica. The prominent improvements in resistance to thermal degradation and mechanical properties of novel PDMS composites were likely attributed to the enhanced interaction of PDMS chains and aggregated particles resulted from synergistic effect between POSS and fumed silica. Meanwhile, we also found that the resistance to thermal degradation of the PDMS composites was lowered slightly with the further increment in loading fumed silica, but their mechanical properties were enhanced. The slight decrease in trend of the resistance to thermal degradation of the novel PDMS composites was likely ascribed to the increasing amount of hydroxyl groups resulting from fumed silica. And the improving mechanical properties were mainly attributed to the increasing interaction of PDMS chains and aggregated particles originated from synergistic effect between POSS and fumed silica. POLYM. COMPOS., 34:1041–1050, 2013. © 2013 Society of Plastics Engineers     

Mechanical properties,flame retardancy,hot‐air ageing,and hot‐oil ageing resistance of ethylene‐vinyl acetate rubber/hydrogenated nitrile‐butadiene rubber/magnesium hydroxide composites

The mechanical properties, flame retardancy, hot‐air ageing, and hot‐oil ageing resistance of ethylene‐vinyl acetate rubber (EVM)/hydrogenated nitrile‐butadiene rubber (HNBR)/magnesium hydroxide (MH) composites were studied. With increasing HNBR fraction, elongation at break and tear strength of the EVM/HNBR/MH composites increased, whereas the limited oxygen index and Shore A hardness decreased slightly. Hot‐air ageing resistance and hot‐oil ageing resistance of the composites became better with increasing HNBR fraction. Thermal gravimetric analysis results demonstrated that the presence of MH and low HNBR fraction could improve the thermal stability of the composites. Differential scanning calorimeter revealed that the glass transition temperature (T_g) of the composites shifted toward low temperatures with increasing HNBR fraction, which was also confirmed by dynamic mechanical thermal analysis. Atomic force microscope images showed MH has a small particle size and good dispersion in the composites with high HNBR fraction. The flame retardancy, extremely good hot‐oil ageing, and hot‐air ageing resistance combined with good mechanical properties performance in a wide temperature range (?30°C to 150°C) make the EVM/HNBR/MH composites ideal for cables application. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of maleated rosin‐modified fluorosilicone resin and its fluorosilicone rubber

Imide‐containing vinyl fluorosilicone resin (MR‐VFS) was synthesized from maleated rosin (MR). And then, with MR‐VFS as a new polar cross‐linking agent in a heat curable fluorosilicone rubber composition, a series of maleated rosin‐modified fluorosilicone rubbers (MR‐FSR) were obtained. The effects of MR‐VFS on the mechanical properties, oil resistance, thermal stability, and low‐temperature performance were studied in detail. It was found that MR‐VFS could increase the tearing strength and high‐temperature thermal stability of fluorosilicone rubber. When the MR‐VFS weight content reached to 2 wt %, the tearing strength of MR‐FSR increased by 20.1% compared with that of common fluorosilicone rubber. However, MR‐FSR showed a similar low‐temperature resistance and a little worse oil resistance. The morphological study showed that incorporation of maleated rosin could intensify the microphase separation of fluorosilicone rubber. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41888.     

Modification of liquid silicone rubber by octavinyl‐polyhedral oligosilsesquioxanes

To develop an efficient, simple, and biocompatible method for improving the thermal and mechanical properties of an addition‐type liquid silicone rubber (LSR), octavinyl‐polyhedral oligosilsesquioxane (OPOSS) modified LSR samples were prepared through the addition of 0.5–4.0 wt % OPOSS as a modifier to a platinum‐based silicone curing system before vulcanization. The characterization and measurement of the OPOSS and LSR samples were carried out by Fourier transform infrared spectroscopy, X‐ray diffraction, NMR, gas chromatography/mass spectrometry (electron impact ionization), scanning electron microscopy, thermogravimetric analysis/differential scanning calorimetry, and universal testing. The experimental results show that the crosslinking of the OPOSS and LSR polymer had a significantly positive effect on the thermal and mechanical properties. Compared with the unmodified sample, its tensile strength was enhanced by 423–508%, its tear resistance was increased from 22 to 44%, the residue at 600 °C was increased by 36–75% in an N₂ atmosphere and 8–65% in an air atmosphere, respectively. These results were obviously superior to those from other similar reported methods that used larger molecular or nonreactive polyhedral oligosilsesquioxane (POSS) derivatives as modifiers at similar POSS loadings. Furthermore, a significant correlation was found between the loading rate of OPOSS and the thermal properties. However, the mechanical properties seemed negatively correlated with the OPOSS content within the experimental range; this may have been due to a material defect caused by the uneven distribution and agglomeration. The results of this study proved that the incorporation of OPOSS into an LSR polymer matrix by a hydrosilylation reaction could be an efficient way to improve the mechanical properties, thermal stability, and biocompatibility of LSR in the future. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43906.     

Light‐diffusing materials for LED illumination applications: Comparing the effectiveness of two typical light‐diffusing agents

Light‐diffusing materials (LDMs) are the primary lampshade materials used for indoor light‐emitting diode (LED) illumination. In this work, two varieties of typical LDMs filled with acrylic or silicone diffusing agents were fabricated via a twin‐screw extruder, and the influences of the particle size, refractive index and light‐diffusing surface area of the light‐diffusing agents on the properties of the LDMs, including their light‐diffusing properties, thermal stability and mechanical properties, were explored in depth. The results indicated that both acrylic and silicone light‐diffusing agents can be dispersed evenly in a polycarbonate (PC) matrix. The light‐diffusing surface area and refractive index are the main factors that influence the diffusing properties of LDMs. Compared with the silicone LDM, the acrylic LDM exhibited higher transmittance but poorer thermal stability and impact strength, making this material suitable for a rapid injection molding process to form half‐sphere covers that combine high haze and transmittance for LED light bulbs. Silicone LDMs exhibit good stability and impact strength, favoring a slow single‐screw extrusion molding process to prepare tubular or panel covers for tubular LED lamps and panel lamps. In this study, a method for producing LDMs with both high transmittance and high haze is reported. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42923.     

Polyhedral oligomeric silsesquioxane/silica/polydimethylsiloxane rubber composites with enhanced mechanical and thermal properties

Composites of polydimethylsiloxane (PDMS) rubber modified by three kinds of polyhedral oligomeric silsesquioxanes (POSSs) as well as fumed silica were prepared through solution blending and then open two‐roll mill blending with curing agent. Subsequently, the influences of POSS on mechanical and thermal properties of the resulting composites were investigated in detail. The addition of POSS significantly enhanced the tensile strength and elongation at break of the composite but lowered the tensile modulus, which could be ascribed to the interruption of silica–silica and silica–PDMS interactions. Octamethylsilsesquioxane (OMS)/silica/PDMS and octaphenylsilsesquioxane (OPS)/silica/PDMS composites did not show desirable mechanical and thermal properties. Nevertheless, heptaphenylvinylsilsesquioxane (VPS)/silica/PDMS composite with 5 wt % VPS exhibited enhanced glass transition temperature (T_g), mechanical properties, and thermal stability. Further studies revealed that more VPS unfavorably affected properties of the composite. Scanning electron microscope and X‐ray diffraction demonstrated that owing to the grafting reaction, 5 wt % VPS in the rubber matrix could form microcrystal domains the most effectively. Thus, the improved mechanical properties and thermal stability just resulted from the the formation of microcrystal domains and the increase in stiffness of PDMS chains because of the graft of VPS onto PDMS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42173.     

Preparation and characterization of transparent and foldable polysiloxane‐poly(methyl methacrylate) membrane with a high refractive index

In this article, carbazole‐grafted methacrylic polysiloxane (MA‐CZ‐PDMS) macromonomer was synthesized and its structure was confirmed by proton nuclear magnetic resonance (¹H NMR). The polysiloxane macromonomer can homogeneously copolymerize with methyl methacrylate (MMA) to prepare transparent and foldable carbazole‐grafted polysiloxane‐poly(methyl methacrylate) (PDMS‐PMMA) membranes with a high refractive index (RI). The membranes were characterized by light transmittance, RI value, and dynamic mechanical thermal analysis (DMTA). The results indicated that the carbazole‐grafted PDMS‐PMMA membranes had excellent light transmittance that decreased slightly with increasing carbazole‐grafted polysiloxane content. Incorporation of carbazole‐grafted polysiloxane in the materials improved its RI value; however decreased the glass transmission temperature (T_g) that can be adjusted to less than 30°C, enable the membrane foldable at room temperature. The data demonstrate that the carbazole‐grafted PDMS‐PMMA membranes have a potential application as high RI intraocular lens (IOL) suitable for implantation by minimally invasive surgery. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42491.     

Preparation and characterization of novel addition cured polydimethylsiloxane nanocomposites using nano‐silica sol as reinforcing filler

A series of novel addition cured polydimethylsiloxane (PDMS) nanocomposites with various amounts of nano‐silica sol were prepared via hydrosilylation for the first time. The influence of various amounts of nano‐silica sol on the morphology, thermal behavior, mechanical and optical properties of these PDMS nanocomposites was studied in detail. It was found that with an increment in the amount of nano‐silica sol the reinforcing effect of the nano‐silica sol on the thermal and mechanical properties of the PDMS nanocomposites was very noticeable compared with the reference material. The prominent improvements in resistance to thermal degradation and mechanical properties can probably be attributed to the strong interaction of PDMS chains and uniformly dispersed particles resulting from the nano‐silica sol. However, the transparency of the PDMS nanocomposites slightly decreased with an increment in weight fraction of nano‐silica, compared with that of PDMS composite without nano‐silica (Sol‐0), which can probably be ascribed to an increasing size of the aggregated particles in the PDMS nanocomposites. The optimum amount of nano‐silica sol for preparing novel addition curing PDMS nanocomposites was about 15 wt%. © 2015 Society of Chemical Industry     

Improving properties of ceramic silicone rubber composites using high vinyl silicone oil

Reactive high vinyl silicone oil (HVSO) was selected to prepare the ceramic silicone rubber composites. The effects of HVSO on the mechanical properties and thermal stabilities of ceramic silicone rubber composites were investigated. The structures of the cross‐linked network of silicone rubber with or without HVSO were studied. The intermolecular space of silicone rubber was enlarged, and the cross‐linked point was concentrated by addition of HVSO, which was demonstrated by cross‐linking densities, scanning electron microscope (SEM) images, and dynamic mechanical analysis (DMA). The cross‐linked network model was formed with the slipping of the cross‐linked points along with the silicone rubber chain. Mechanical properties of composites were enhanced by the formation of this cross‐linked network. The tear strength, tensile strength, and elongation at break of the composites were increased by 18.5%, 13.2%, and 37.4% by the adding of 2 phr HVSO, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41864.     

Stepwise cure and properties of silicone resin for high‐ultraviolet‐transmission optical elements

A new high‐ultraviolet (UV)‐transmission silicone‐resin polymeric material was prepared via curing during hydrosilylation of tetramethyltetravinylcyclotetrasiloxane with tetramethylcyclotetrasiloxane by a liquid‐surface supernatant method, using a stepwise heating program to avoid spontaneous combustion of the reaction mixture. The relationships were investigated in detail between reactive groups, cross‐linking density, mechanical and UV‐transmission properties. For this purpose, UV transmittance and dynamic mechanical properties, respectively, of the silicone resin were measured with UV–visible spectrophotometry and dynamic mechanical thermal analysis. In addition, surface roughness was evaluated with an atomic force microscope as well as an interferometer. The curing process was monitored by Fourier transform infrared spectroscopy and rotational rheometry. The cyclic silicone oils were compared with linear ones in structure and product properties. The results indicated that stepwise temperature control during curing process was particularly indispensible due to the presence of active Si? H bonds, and that the silicone resin of high modulus, high UV transmittance (92.7%) and low surface‐roughness was largely homogeneous in cross‐linking points distribution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43308.     

Use of allyl‐functional benzoxazine monomers as replacement for styrene in vinyl ester resins

New vinyl ester systems are prepared using allyl‐functional benzoxazine monomers, 3‐allyl‐6‐methyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazine (pC‐ala) or bis(3‐allyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazin‐6‐yl)methane (BF‐ala), as reactive diluents for vinyl ester resins derived from an epoxy resin, diglycidyl ether of bisphenol A, instead of using styrene. Different initiators are used to investigate the copolymerization of allyl function from pC‐ala with vinyl function from vinyl ester resin prepolymer. The temperature dependence of viscosity is studied to demonstrate the retention of processability of the new vinyl ester resins. Dynamic mechanical and thermogravimetric analyses are used to investigate the dynamic mechanical properties and thermal stability of the new resins. Copyright © 2012 Society of Chemical Industry     

Property reinforcement of silicone dielectric elastomers filled with self‐prepared calcium copper titanate particles

In this article, submicron and micron calcium copper titanate (CCTO) crystallites with different morphologies were successfully designed and prepared by directly thermal treatment method and molten salt method, respectively. Then, the silicone elastomer filled with self‐prepared CCTO particles had high dieletric constant, low dielectric loss, and actuated strain which was greatly improved at low electric field. The dieletric constant at 50 Hz obviously increased from 2.15 for pure silicone elastomer to 4.37 and 4.18 for the submicron and micron CCTO/poly (dimethyl siloxane) (PDMS) composites. The dielectric loss of the composites retained at a low value (less than 0.06). Meanwhile, the elastic modulus of CCTO/PDMS composites was increased slightly only with a good flexibility. Compared to pure silicone elastomer (2.25%), the submicron and micron CCTO/PDMS composites with 2 wt % content exhibited a greater strain of 7.69% and 9.83% at a low electric field of 5 V/μm. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42613.     

Thermal and mechanical properties of acrylated expoxidized‐soybean oil‐based thermosets

A series of epoxidized‐soybean oil (ESO) with different epoxyl content were synthesized by in situ epoxidation of soybean oil (SBO). The acrylated epoxidized‐soybean oil (AESO) was obtained by the reaction of ring opening of ESO using acrylic acid as ring opener. The acrylated expoxidized‐soybean oil‐based thermosets have been synthesized by bulk radical polymerization of these AESOs and styrene. The thermal properties of the resins were characterized by differential scanning calorimetry (DSC) and thermo‐gravimetric analysis (TG). The results showed that these resins possess high thermal stability. There were two glass transition temperature of each resin due to the triglycerides structure of the resins. The tensile strength and impact strength of the resins were also recorded, and the tensile strength and impact strength increased as the iodine value of ESO decreased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Vi‐PDMS incorporated with protein‐based coatings designed for permeability‐enhanced applications

Functional polydimethylsiloxanes containing vinyl groups (Vi‐PDMS) were used for silicone‐based organic polymers in composites and adhesive formulations. Poly(butyl acrylate/methyl methacrylate/vinyl silicone oil)/casein–caprolactam [P(BA‐MMA‐Vi‐PDMS)/CA‐CPL] nanoparticles were prepared via emulsifier‐free polymerization. The well‐defined core–shell structure of P(BA‐MMA‐Vi‐PDMS)/CA‐CPL nanoparticles was verified by transmission electron microscopy. The results of scanning electron microscopy and contact angle measurements proved that the as‐obtained coatings exhibited porous and hydrophobic properties, which were helpful for superior water vapor permeability. By comparing the appearance of the coatings before and after adhesion analysis, the excellent adhesion strength was proved to be dominated by Vi‐PDMS. The relationship between interface morphology and properties of the resultant coatings was investigated in detail. The nucleation mechanism for this soap‐free emulsion synthesis was also proposed accordingly. These results could help in designing coatings with better surface properties and wider application. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46501.     

Synthesis and characterization of hydroxy‐terminated polyether‐polydimethylsiloxane‐polyether (PE‐PDMS‐PE) triblock oligomers and their use in the preparation of thermoplastic polyurethanes

A series of hydroxy‐terminated polyether‐polydimethylsiloxane‐polyether (α,ω‐dihydroxy‐(PE‐PDMS‐PE)) ABA triblock oligomers were synthesized from silanic fluids and methyl polyallyloxide polyethers. The reaction was a one‐step solventless hydrosilylation reaction with chloroplatinic acid (CPA) catalyst in the presence of heat. These ABA oligomers were characterized via ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, FT‐IR, and GPC to demonstrate that they exhibit a 100% linear ABA structure with a siloxane Si? O chain in the center and polyether ethylene oxide (EO)/propylene oxide (PO) chains on the two sides terminated by hydroxy groups. The triblock oligomers were used to form thermoplastic polyurethanes (TPUs) using two‐step solventless bulk polymerization. The investigation of triblock oligomers impact on TPUs mechanical properties, thermal performance, surface water repellency, and morphology performance were analyzed by Instron material tester, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), water contact angles (WCA), scanning electron microscope (SEM), and transmission electron microscope (TEM). DSC and TGA indicated that PE‐PDMS‐PE modified TPUs had a clear lower T_g under ?120°C and the temperature of 50% weight loss was improved from 280 to 340°C. PE‐PDMS‐PE–modified TPU did not have the marked reduction on mechanical properties than pure polyether produced TPU. Tensile strength was maintained at 13 MPa and elongation was maintained at 300%. SEM and TEM were used to investigate the copolymers’ morphology performance and found that all PO PE‐PDMS‐PE had a pseudo‐three phase separation. WCA analysis confirmed that PE‐PDMS‐PE–modified TPU had significantly improved hydrophobic performance because the silicone structure linked into TPU copolymers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42521.     

Polybenzoxazine nanocomposites containing 3,13‐Diglycidyl double‐decker silsesquioxane

3,13‐Diglycidyloxypropyloctaphenyl double‐decker silsesquioxane (3,13‐diglydidyl DDSQ) was synthesized via hydrosilylation between 3,13‐dihydrooctaphenyl double‐decker silsesquioxane (3,13‐dihydro DDSQ) and allyl glycidyl ether. This novel difunctional polyhedral oligomeric silsesquioxanes (POSS) macromer was incorporated into polybenzoxazine (PBZ) thermosets to obtain the organic–inorganic nanocomposites. Compared to control PBZ, the organic–inorganic nanocomposites displayed the enhanced glass transition temperatures (T _g's). Under the identical condition, the organic–inorganic nanocomposites exhibited the stable rubbery plateaus in the measurements by dynamic mechanical thermal analysis, which was in marked contrast to control PBZ thermoset. The enhanced T _g's and improved dynamic mechanical properties are attributable to the formation of the additional crosslinking between PBZ and the difunctional POSS macromer and the nanoreinforcement of POSS cages on PBZ networks. Thermogravimetric analysis indicates that the organic–inorganic nanocomposites displayed improved thermal stability. POLYM. COMPOS., 38:827–836, 2017. © 2015 Society of Plastics Engineers