Flame retardancy and thermal stability of polyhedral oligomeric silsesquioxane nanocomposites

The flame retardancy and thermal stability of polyhedral oligomeric silsesquioxane (POSS) nanocomposites are reviewed. Results are summarized and compared on the basis of structure–property relationships. Because of the variability of groups attached on POSS, they exhibit different performance in polymer nanocomposites: metal‐containing POSS show good catalytic charring ability; vinyl‐containing and phenyl‐containing POSS promote the strength of char. Improvements in the cone calorimeter (such as reduced peak heat release rate) are advantages of POSS as preceramics for fire retardancy compared with traditional flame retardants, and it will pave the way to the design of inorganic–organic hybrid polymer nanocomposites with enhanced flame retardancy and thermal stability. Copyright © 2011 John Wiley & Sons, Ltd.     

Montmorillonite intercalated by ammonium of octaaminopropyl polyhedral oligomeric silsesquioxane and its nanocomposites with epoxy resin

The octaammonium chloride salt of octaaminopropyl polyhedral oligomeric silsesquioxane (OapPOSS) was synthesized via the hydrolytic condensation of γ-aminopropyltrimethoxysilane in the methanol solution catalyzed by concentrated hydrochloric acid and was further used as the intercalating agent to modify sodium montmorillonite (MMT). X-ray diffraction (XRD) data indicate that the MMT was successfully intercalated by the ammonium of OapPOSS, as evidenced by the fact that the basal spacing of MMT galleries was expanded from 1.3 to 1.7 nm. The intercalation method used here introduced only the octaammonium POSS salt in contrast to the introduction of all hydrolyzed products from γ-aminopropyltriethoxysilane (APTEOS). The POSS-modified MMT was exploited to prepare the epoxy-MMT nanocomposites. Using a two-step technique, the disorderly exfoliated epoxy-MMT nanocomposites were obtained. XRD studies showed that the formation of the nanocomposites in all the cases with the disappearance of the peaks corresponding to the basal spacing of MMT. Transmission electronic microscopy (TEM) was used to investigate the morphology of the nanocomposites and indicates that the nanocomposites are comprised of a random dispersion of intercalated/exfoliated aggregates throughout the matrix. Differential scanning calorimetry (DSC) indicates that the glass transition temperatures of the as-prepared epoxy-MMT nanocomposites remained invariant in comparison with that of the control epoxy when the POSS-MMT content is less than 10 wt%. However, the nanocomposite containing 15 wt% of POSS-MMT displayed a decreased T_g, which could be attributed to the incomplete curing reaction resulting from the POSS-MMT loading. Thermogravimetric analysis (TGA) shows that the incorporation of POSS-MMT into epoxy networks displayed an apparent improvement in the thermal stability, and the char residue increased with increasing the concentration of POSS-MMT.     

Synthesis and characterization of polybenzoxazine networks nanocomposites containing multifunctional polyhedral oligomeric silsesquioxane (POSS)

A new class of polybenzoxazine/POSS nanocomposites with network structure is prepared by reacting multifunctional benzoxazine POSS (MBZ-POSS) with benzoxazine monomers (Pa and Ba) at various compositional ratios. Octafunctional cubic silsesquioxane (MBZ-POSS) is used as a curing agent, which is synthesized from eight organic benzoxazine tethers through hydrosilylation of vinyl-terminated benzoxazine monomer (VP-a) with octakis(dimethylsiloxy)silsesquioxane () using a platinum complex catalyst (Pt-dvs). Incorporation of the silsesquioxane core into polybenzoxazine matrix could significantly hinder the mobility of polymer chains and enhance the thermal stability of these hybrid materials. For these nanocomposites, increasing the POSS content in the hybrids is expected to improve its thermal properties with respect to the neat polybenzoxazine. The morphology feature is useful to explain the thermal property changes (T_g and T_d) and AFM images show that the presence of POSS aggregation in larger scales occurs at higher POSS contents. The reason of the heterogeneous phase separation may be from the less compatibility of the inorganic silsesquioxane core with organic benzoxazine species and the homopolymerization of MBZ-POSS. In the course of the formation of the polybenzoxazine/POSS hybrids, POSS particles were separated from the polybenzoxazine rich region, leading to POSS rich domains in the range of 50-1000 nm.     

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     

The synthesis and characterization of polystyrene/magnetic polyhedral oligomeric silsesquioxane (POSS) nanocomposites

Fc-CHCH-C₆H₆-(C₅H₉)₇Si₈O₁₂ (POSS1, Fc: ferrocene) which contain both metal and CC double bond was firstly synthesized by Wittig reaction. The chemical structure of POSS1 was characterized by FTIR, ¹H, ¹³C and ²⁹Si NMR, mass spectrometry and elemental analysis, and the magnetic property of POSS1 have also been studied. Polystyrene composites containing inorganic-organic hybrid polyhedral oligomeric silsesquioxane (POSS1) were prepared by bulk free radical polymerization. XRD and TEM studies indicate that POSS1 is completely dispersed at molecular level in PS matrix when 1 wt% POSS1 is introduced, while some POSS1-rich nanoparticals are present when content of POSS1 is beyond 3 wt%. GPC results show that molecular weight of the PS/POSS1 nanocomposites are increased with addition of POSS1. TGA and TMA data show the thermal stabilities of PS/POSS1 nanocomposites have been improved compared to neat PS. The PS/POSS1 nanocomposites also display higher glass transition temperatures (T_g) in comparison with neat PS. Viscoelastic properties of PS/POSS1 nanocomposites were investigated by DMTA. The results show the storage modulus (E′) values (temperature>T_g) and the loss factor peak values of the PS/POSS1 nanocomposites are higher than that of neat PS. Mechanical properties of the PS/POSS1 nanocomposites are improved compared to the neat PS.     

Phenolic resin-trisilanolphenyl polyhedral oligomeric silsesquioxane (POSS) hybrid nanocomposites: Structure and properties

The structure and properties of organic-inorganic hybrid nanocomposites prepared from a resole phenolic resin and a POSS mixture containing >95 wt% trisilanolphenyl POSS was investigated by POM (polarized optical microscopy), SEM, TEM, WAXD, FT-IR, DSC, and TGA techniques. Composites with 1.0-10.4 wt% of POSS were prepared by dissolving the POSS and the phenolic resin into THF, followed by solvent removal and curing. Both nano- and micro-sized POSS filler aggregates and particles were shown to be heterogeneously dispersed in the cured matrix by POM, TEM, SEM, and X-EDS. POSS was found everywhere, including in both dispersed phase domains and in the matrix. The nanocomposite morphology appears to form by a multi-step POSS aggregation during the process of phase separation. Both the matrix and dispersed ‘particulate’ phase domains are mixtures of phenolic resin and POSS. POSS micro-crystals act as the core of the dispersed phase. The bigger dispersed domains consist of smaller particles or aggregates of POSS molecules that exhibit some order but regions of matrix resin are interspersed. A WAXD peak at 2θ∼7.3° indicates crystalline order in the POSS aggregates. This characteristic peak's intensity increases with an increase in POSS loading, suggesting that more POSS molecules have aggregated or crystallized. FT-IR spectra confirm that hydrogen bonding exists between the phenolic resin and POSS Si-OH groups. This increases their mutual compatibility, but H-bonding does not prevent POSS aggregation and phase separation during curing. TGA measurements in air confirmed the temperature for 5% mass loss in increases with increase of POSS loading and at T>550° the thermal stability increases more sharply with POSS loading. The nanocomposite glass transition temperatures (T_g) are only slightly be affected by the POSS filler.     

Effect of side chain architecture on dielectric relaxation in polyhedral oligomeric silsesquioxane/polypropylene oxide nanocomposites

Segmental and normal mode dynamics in polyhedral oligomeric silsesquioxane (POSS)/poly(propylene oxide) (PPO) non-reactive and reactive nanocomposites were investigated using a broadband dielectric relaxation spectroscopy (DRS) over wide ranges of frequency and temperature. Three POSS reagents with varying side chain architecture were selected for the study: OctaGlycidyldimethylsilyl (OG), TrisGlycidylEthyl (TG) and MonoGlycidylEthyl (MG). Spectra of OG and TG show a segmental (α) process at lower frequency and a local (β) relaxation at higher frequency, while MG displays only a local relaxation. Neat PPO has both segmental and normal mode (α_N) process. In POSS/PPO non-reactive nanocomposites, the presence of OG and TG causes a decrease in the time scale of α_N and α relaxation, while MG has no impact on the dynamics of PPO. Chemical reactions in POSS/PPO reactive nanocomposites lead to the formation of nanonetworks. Prior to the onset of reaction, POSS nanoparticles promote the motions of PPO chains, decrease the time scale of relaxation and give rise to thermodielectrically simple spectra. During the reaction, however, the network formation leads to spectral broadening and a gradual increase in the time scale of both segmental (α) and normal mode (α_N) relaxation. A detailed account of the effects of structure, concentration and dispersion of POSS in the matrix, molecular weight of PPO, extent of reaction and temperature on the molecular origin, temperature dependence and spectral characteristics of relaxation processes in POSS/PPO nanocomposites is provided.     

Molecular dynamics simulation of mixed matrix nanocomposites containing polyimide and polyhedral oligomeric silsesquioxane (POSS)

Mixed matrix blends containing polyimide (PI) and polyhedral oligomeric silsesquioxanes (POSS) are studied with atomistic molecular dynamics simulation. To examine the effect of functional group, two types of POSS are considered, either octahydrido silsesquioxane (OHS) or octaaminophenyl silsesquioxane (OAPS). The glass transition temperature of the model PI-OAPS blends increases with the incorporation of OAPS, an observation consistent with recent experiments on these systems. A decrease in glass transition temperature is shown for the model PI-OHS blends. Radial distribution functions for both blends are presented to show how packing between the inorganic (POSS) and organic (PI) species in the mixed matrix varies as a function of POSS loading and POSS functionalization. In addition, we report the mobility of the PI chains and POSS molecules in the material by calculating the mean square displacement. These results provide molecular insight about thermal property enhancements afforded by POSS-based additives.     

Polyimide/POSS nanocomposites: interfacial interaction, thermal properties and mechanical properties

A series of functional polyhedral oligomer silsesquioxnae (POSS)/polyimide (PI) nanocomposites were prepared using a two-step approach, first, the octa(aminophenyl)silsesquioxane (OAPS)/NMP solution was mixed with polyamic acid (PAA) solution prepared by reacting 4,4′-diaminodiphenylmethane and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride in NMP, and second, the polycondensation solution was treated by thermal imidization. The well-defined ‘hard particles’ (POSS) and the strong covalent bonds between the PI and the ‘hard particles’ lead to a significant improvement in the thermal mechanical properties of the resulting nanocomposites. The glass transition temperature dramatically increases while the coefficient of thermal expansion (CTE) decreases, owing to the significant increase of the cross-linking density in the PI-POSS nanocomposites. The thermal stability and mechanical property of the nanocomposites were also improved.     

Organic–inorganic polyimide nanocomposites containing a tetrafunctional polyhedral oligomeric silsesquioxane amine: synthesis,morphology and thermomechanical properties

5,11,14,17‐Tetraanilinooctaphenyl double decker silsesquioxane, a well‐defined tetraamino polyhedral oligomeric silsesquioxane (POSS), was synthesized in this work. This novel tetrafunctional POSS amine was employed to prepare polyimide nanocomposites. It was found that the hybrid polyimide nanocomposites displayed nanostructures in which the POSS component was aggregated into spherical microdomains with a diameter of 40 ? 80 nm. Compared to unmodified polyimide, the POSS‐containing polyimide nanocomposites displayed improved thermal stability and surface hydrophobicity. Owing to the introduction of the POSS microdomains, the dielectric constants of the polyimide nanocomposites were significantly decreased in comparison with plain polyimide. © 2017 Society of Chemical Industry     

Star-shaped poly(?-caprolactone) with polyhedral oligomeric silsesquioxane core

A readily available octa(3-chloropropyl) polyhedral oligomeric silsesquioxane (POSS) [(ClCH₂CH₂CH₂)₈Si₈O₁₂] framework was used to prepare octa(3-hydroxypropyl) POSS [(HOCH₂CH₂CH₂)₈Si₈O₁₂], which was further used as an initiator to synthesize star poly(?-caprolactone) with POSS core via ring-opening polymerization catalyzed by Stannous (II) octanoate [Sn(Oct)₂]. The organic-inorganic star PCLs were characterized by means of gel permeation chromatograph (GPC), Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). The wide-angle X-ray diffraction (WAXRD) experiments indicate that the presence of POSS cores did not alter the crystal structure of PCL. The star PCLs exhibited enhanced melting temperatures in comparison with the linear counterpart. The isothermal crystallization kinetics shows that both the overall crystallization rate and the spherulitic growth rate of the star PCLs increased with increasing the concentration of POSS (or with decreasing the arm lengths of the stars). The fold surface free energy of the star PCLs decreased with increasing the concentration of POSS. These results could be interpreted based on the effect of the heterogeneous nucleation of POSS cores, which accelerates the process of crystallization.     

Formation of nanostructured epoxy networks containing polyhedral oligomeric silsesquioxane (POSS) blocks

Nanostructured epoxy networks, based on DGEBA and poly(oxypropylene)diamine (Jeffamine D), containing nano-sized inorganic blocks, polyhedral oligomeric silsesquioxanes (POSS), were investigated. The POSS were incorporated in the network as crosslinks or as pendant units by using octa- or monoepoxy-POSS monomers, respectively, as well as diepoxides with pendant POSS. The authors focused on investigating the relationship between the network formation process and the final product properties. The reactivity of the epoxy-functional POSS monomers, the hybrid systems' time of gelation, the gel fractions and the phase structure of the networks were determined using ¹H or ¹³C NMR spectroscopy, chemorheology experiments, sol-gel analysis and transmission electron microscopy (TEM).All the POSS epoxides tested show a reduced reactivity if compared to their respective model compounds due to sterical crowding in the neighborhood of their functional groups and due to reduced epoxy group mobility. The incorporation of pendant POSS into networks of the type DGEBA-Jeffamine D-monoepoxy-POSS hence took place only in the late reaction stage. Together with the high tendency of these POSS to aggregation, the kinetics favors the formation of small nano-phase-separated POSS domains, which act as physical crosslinks due to their covalent bonds to the organic matrix. At POSS loadings higher than 70%, topological constraint by POSS leads to a strongly reduced elastic chain mobility, thus additionally strongly reinforcing the networks. The network build-up and gelation of the octaepoxy-POSS-Jeffamine D system were slow compared to the reference DGEBA-Jeffamine D network due to a low octaepoxy-POSS reactivity and due to its strong tendency to cyclization reactions with primary amines. The topology of the amino groups is shown to be very important. In contrast to monoepoxy-POSS, the octaepoxy-POSS becomes dispersed as oligomeric junctions (purely chemical crosslinks) of the network in the cured product. The octaepoxide's reinforcing effect is small and is given only by its high functionality and not by its inorganic nature. The functionality effect is reduced by the mentioned cyclizations.     

Low-dielectric, nanoporous polyimide films prepared from PEO-POSS nanoparticles

Dielectric insulator materials that have low dielectric constants (k<2.5) are required as inter-level dielectrics to replace silicon dioxide (SiO₂) in future semiconductor devices. In this paper, we describe a novel method for preparing nanoporous polyimide films through the use of a hybrid PEO-POSS template. We generated these nanoporous foams are generated by blending polyimide as the major phase with a minor phase consisting of the thermally labile PEO-POSS nanoparticles. The labile PEO-POSS nanoparticles would undergoes oxidative thermolysis to releases small molecules as byproducts that diffuse out of the matrix to leave voids into the polymer matrix. We achieved significant reductions in dielectric constant (from k=3.25 to 2.25) for the porous PI hybrid films, which had pore sizes in the range of 10-40 nm.     

POSS基聚合物的热性能和阻燃性

本文介绍了POSS单体和POSS基聚合物的结构、性能和制备方法。重点阐述了各类POSS基聚合物以及它们的热性能。同时简单介绍了POSS对聚合物阻燃性的影响,分析了POSS提高聚合物热性能和阻燃性的原因,并展望了POSS基聚合物的发展方向。     

ABA triblock copolymers containing polyhedral oligomeric silsesquioxane pendant groups: synthesis and unique properties

The synthesis and characterization of POSS containing ABA triblock copolymers is reported. The use of atom transfer radical polymerization (ATRP) enabled the preparation of well-defined model copolymers possessing a rubbery poly(n-butyl acrylate)(pBA) middle segment and glassy poly(3-(3,5,7,9,11,13,15-heptaisobutyl-pentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]-octasiloxane-1-yl)propyl methacrylate(p(MA-POSS)) outer segments. By tuning the relative composition and degree of polymerization (DP) of the two segments, phase separated microstructures were formed in thin films of the copolymer. Specifically, dynamic mechanical analysis and transmission electron microscopy (TEM) observations reveal that for a small molar ratio of p(MA-POSS)/pBA (DP=6/481/6) no evidence of microphase separation is evident while a large ratio (10/201/10) reveals strong microphase separation. Surprisingly, the microphase-separated material exhibits a tensile modulus larger than expected (ca. 2×10⁸ Pa) for a continuous rubber phase for temperatures between a pBA-related T_g and a softening point for the p(MA-POSS)-rich phase. Transmission electron microscopy (TEM) images with selective staining for POSS revealed the formation of a morphology consisting of pBA cylinders in a continuous p(MA-POSS) phase. Thermal studies have revealed the existence of two clear glass transitions in the microphase-separated system with strong physical aging evident for annealing temperatures near the T_g of the higher T_g phase (p(MA-POSS). The observed aging is reflected in wide-angle X-ray scattering as the strengthening of a low-angle POSS-dominated scattering peak, suggesting some level of ordering during physical aging. The T_g of the POSS-rich phase observed in the microphase separated triblock copolymer was nearly 25 °C higher than that of a POSS-homopolymer of the same molecular weight, suggesting a strong confinement-based enhancement of T_g in this system.     

Polysiloxanes containing polyhedral oligomeric silsesquioxane groups in the side chains; synthesis and properties

Linear polysiloxanes having different amounts of polyhedral oligomeric silsequioxane (POSS) side groups were prepared from the hydrosilylation reaction of poly(ethylhydrosiloxane) with different amount of POSS and 1-octene using platinum(0)-divinyl tetramethyldisiloxane as a catayst. 1-Octene and platinum(0)-divinyl tetramethyldisiloxane were found to be very important for the preparation of the linear polymer without any cross-linked structures. The linear polysiloxanes with POSS side groups are soluble in various organic solvents. When the content of POSS-containing monomeric unit is larger than 10 mol%, free standing films can be prepared from a routine solution casting method, although this polysiloxane is not cross-linked.     

Investigation of the thermal,mechanical and morphological properties of poly(vinyl chloride)/polyhedral oligomeric silsesquioxane nanocomposites

Research into organic–inorganic nanocomposites has recently become popular, particularly the development of new polymer nanocomposites. Compared to pristine polymers or conventional composites, these nanocomposites exhibit improved properties. The storage modulus of a poly(vinyl chloride) (PVC)/polyhedral oligomeric silsesquioxane (POSS) nanocomposite slightly decreased with POSS content, but had a higher modulus from 50 to 100 °C. Some of the material appeared to be aggregated with 1 wt% POSS in the polymeric matrix. Conversely, with a POSS content of 5 wt%, a better dispersion of the nanoparticles was observed. The presence of POSS in the plasticised PVC compound had little influence on the final properties of the nanocomposites, showing weaker interactions between the POSS and the plasticised PVC compound. Copyright © 2010 Society of Chemical Industry     

Nanotailoring of polyurethane adhesive by polyhedral oligomeric silsesquioxane (POSS)

The development and commercialization of nanoparticles such as nanoclays (NCs), carbon nanotubes (CNTs) and polyhedral oligomeric silsesquioxanes (POSS) offers new possibilities to tailor adhesives at the nanoscale. Four types of POSS, with reactive mono-functional groups of isocyanatopropyl, glycidoxypropyl, aminoethyl and non-reactive octaphenyl, were incorporated in concentrations of 1, 3 and 5 wt% into a polyurethane (PU)-based adhesive. Thermo-mechanical bulk properties were studied using dynamic mechanical analysis (DMA). Adhesive properties were characterized in shear and peel modes. Atomic force microscopy (AFM) was used to study the nanoscale morphology. DMA measurements indicated that the neat PU possessed a glass transition temperature (T _g) of ≈ 30°C. The T _g of PU/POSS-glycidoxypropyl nanocomposite adhesive increased gradually with POSS concentration to 50°C for 5 wt%. PU/POSS-octaphenyl nanocomposite adhesive exhibited an increased T _g by 10°C for 5 wt%. The incorporation of POSS-isocyanatopropyl in the PU had no effect on the T _g. With respect to shear properties of POSS-octaphenyl-, POSS-isocyanatopropyl- and POSS-glycidoxypropyl-based PU nanocomposite adhesives, shear strength improved by 230, 178 and 137%, respectively, compared to neat PU. POSS-aminoethyl exhibited lower shear and peel strengths, while POSS-isocyanatopropyl provided the best balance of both higher shear and peel strengths compared to neat PU. It was concluded that the grafted functional group on the POSS and its reactivity with the PU network components were the decisive factors with respect to the thermo-mechanical, morphological and adhesive properties of the resulting nanocomposite adhesives. Consequently, the POSS/polyurethane based nanocomposite adhesives could be tailored for a large range of applications.     

Preparation and characterization of styrene/styryl–polyhedral oligomeric silsesquioxane hybrid copolymers

BACKGROUND: Organic–inorganic nanocomposites were prepared by copolymerization of various monomers and polyhedral oligomeric silsesquioxane (POSS) derivatives. Preliminary results showed that styrene/styryl–POSS copolymers could be obtained using CpTiCl₃ catalyst. In the work reported here, the copolymerization of styrene and styryl‐substituted POSS was studied in detail for a more effective catalyst, Cp*TiCl₃. RESULTS: The glass transition temperature (T_g) of the copolymers prepared increased with increasing POSS content. The degradation temperature (T_d) of the copolymers was 60 °C higher than that of syndiotactic polystyrene under nitrogen. Although the thermal properties were improved by incorporation of POSS, the catalytic activity decreased with POSS content. The racemic triad and syndiotactic index of the copolymers decreased with increasing POSS content. Gel permeation chromatograms of the copolymers exhibited multimodal distribution due to the presence of multi‐active centres, which were formed by interaction of Ti with the POSS siloxane linkage. CONCLUSION: With the incorporation of POSS, the thermal properties of polystyrene were improved. The styrene/styryl–POSS copolymers are formed through the various active sites arising from the interactions of Ti with POSS. Copyright © 2008 Society of Chemical Industry     

多面体低聚倍半硅氧烷及多面体低聚倍半硅氧烷-聚合物的研究进展

综述了多面体低聚倍半硅氧烷(POSS)的结构、性质与合成方法,重点介绍了单官能团、双官能团、多官能团3类POSS可以通过共聚、缩聚、接枝、共混等多种方式引进聚合物中,形成真正的有机/无机纳米杂化材料,最后指出了POSS的发展方向.