Preparation,characterization, and properties of poly(aryl ether sulfone) systems with double‐decker silsesquioxane in the main chains by reactive blending

A series of copoly(aryl ether sulfone)s containing double‐decker‐shaped silsesquioxane (DDSQ) in the main chain was prepared. Toward this end, a novel diphenol polyhedral oligomeric silsesquioxane macromer was synthesized by hydrosilylation between 3,13‐dihydro octaphenyl double‐decker silsesquioxane (denoted dihydro DDSQ) and eugenol. The poly(aryl ether sulfone)s were synthesized from diphenol DDSQ, bisphenol A (BPA), and 4‐fluorophenyl sulfone using a one‐step high‐temperature solution method. By adjusting the ratio of diphenol DDSQ to BPA, copolymers with variable DDSQ content in the main chains were obtained. With increased DDSQ content in the main chain, the glass transition temperature decreased based on differential scanning calorimetry, and anti‐degradation was enhanced based on thermogravimetric analysis. Moreover, the dielectric constant κ of pure polymer (3.19 at 1 MHz) initially increased to 4.04 (DDSQ molar ratio = 10%), and then decreased to 2.68 at 1 MHz (DDSQ molar ratio = 100%). Crystallization behavior, solubility, and surface hydrophobicity were also investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 780–788     

Organic–inorganic copolymers with double‐decker silsesquioxane in the main chains by polymerization via click chemistry

A series of novel organic–inorganic copolymers with polyhedral oligomeric silsesquioxane (POSS) in the main chains were synthesized via the copper‐catalyzed Huisgen 1,3‐dipolar cycloaddition polymerization approach. Toward this end, we synthesized 3,13‐azidopropyloctaphenyl double‐decked silsesquioxane (DDSQ). This difunctional POSS macromer was used to copolymerize with α,ω‐dialkynyl‐terminated oligoethylenes with variable number of ethylene units. The organic–inorganic copolymers were obtained with the mass fraction of POSS up to 79%. Gel permeation chromatography showed that the high‐molecular‐weight copolymers were successfully obtained in all the cases. Differential scanning calorimetry showed that the amplitude of glass transitions for these copolymers was very feeble, suggesting that the segmental motions responsible for the glass transitions was highly restricted with DDSQ cages in the main chains. Thermogravimetric analysis showed that the organic–inorganic hybrid copolymers displayed extremely high thermal stability. Contact angle measurements showed that these organic–inorganic copolymers are highly hydrophobic and possessed very low surface energy. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4221–4232     

Organic–inorganic poly(N‐vinylpyrrolidone) copolymers with double‐decker silsesquioxane in the main chains: Synthesis,glass transition,and self‐assembly behavior

An organic–inorganic copolymer with polyhedral oligomeric silsesquioxane (POSS) and xanthate moieties in the main chain was synthesized via the polycondensation between 3,13‐di(2‐bromopropionate)propyl double‐decker silsesquioxane (DDSQ) and 1,4‐di(xanthate potassium)butane. This hybrid copolymer was used as the macromolecular chain transfer agent to obtain the organic–inorganic poly(N‐vinylpyrrolidone) (PVPy) copolymers via a reversible addition fragmentation chain transfer/macromolecular design via the interchange of xanthates (RAFT/MADIX) polymerization approach; the polymerization behavior of N‐vinyl pyrrolidone was investigated by means of gel permeation chromatography. It was found that the polymerization was in a living and controlled manner. Transmission electron microscopy (TEM) showed that the organic–inorganic PVPy copolymers with DDSQ in the main chains were microphase‐separated in bulks. Compared to plain PVPy, the organic–inorganic PVPy copolymers displayed the decreased glass transition temperatures (T_gs); the decreased T_gs are attributable to the effect of the introduced DDSQ cages on the packing of PVPy chains as evidenced by means of Fourier transform infrared spectroscopy (FTIR). In water, the organic–inorganic PVPy copolymers can self‐assemble into the spherical nano‐objects with the size of 20–50 nm in diameter. In the self‐assembled nano‐objects, the aggregates of the hydrophobic DDSQ constituted the cores of the polymeric micelles whereas the PVPy chains between the DDSQ behaved as the coronas of the polymeric micelles. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2949–2961     

Amphiphilic membranes crosslinked and reinforced by POSS

This article concerns the synthesis and characterization of novel tricomponent amphiphilic membranes consisting of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments cocrosslinked and reinforced by octasilane polyhedral oligomeric silsesquioxane (octasilane‐POSS) cages. Rapid and efficient network synthesis was effected by cocrosslinking diallyl‐telechelic PEG (A‐PEG‐A) and divinyl‐telechelic PDMS (V‐PDMS‐V) with pentamethylpentacyclosiloxane (D₅H), using Karstedt's catalyst in conjunction with Et₃N cocatalyst and water. Films were prepared by pouring charges in molds and crosslinking by heating at 60 °C for several hours. The films were characterized by sol fractions and equilibrium swelling both in hexane and water, extent of crosslinking, contact angle hysteresis, oxygen permeability, thermogravimetric analysis, and mechanical properties. The crosslinking of octasilane‐POSS achieved by the same catalyst system was studied in separate experiments. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4337–4352, 2004     

Synthesis and characterization of poly(aryl ether sulfonate)s with fluorinated phenyl-radicals in the side chain

A series of novel poly(aryl ether sulfone)s (PAESs) were prepared from bis(4-chlorophenyl) sulfone and various bisphenol monomers via nucleophilic aromatic substitution polycondensation. The polycondensation proceeded quantitatively in N,N-dimethylacetamide and afforded PAESs with inherent viscosities of 0.62–0.81 dL/g. The obtained PAESs showed high-glass transition temperatures beyond 177°C and excellent thermal stability with 10% weight loss temperatures in the range of 541–571°C. The PAESs 2a–c could dissolve readily in common organic solvents and their solubility was improved by the introduction of bulky pendant groups. The PAESs formed transparent, strong and flexible films, with tensile strengths of 88.1–98.7 MPa, Young modulus of 3.14–3.52 GPa, and elongation at break of 18–34%. Furthermore, the resulting PAES films showed low dielectric constants (2.77–3.02 at 1 MHz) and low water absorption (0.51–0.83%).     

Novel epoxy nanocomposite of low Dk introduced fluorine‐containing POSS structure

A nanoporous additives, polyhedral oilgomeric silisesquioxane containing eight functional hexafluorine groups, octakis(dimethylsiloxyhexafluoropropyl ether)silsesquioxane (OF) has been synthesized and blended with the UV‐cured epoxy resin. The OF containing (10%) epoxy has significantly lower dielectric constant (2.65) than the plain epoxy (3.71). The incorporation of fluorine containing additives is well‐known to reduce dielectric constant due to lower its polarizability. In addition, the presence of the bulky POSS structure is able to create additional free space or pores and further reduces the dielectric constant of the epoxy matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 502–510, 2007     

Structural and dielectric properties of POSS reinforced polyimide nanocomposites

In this study, a series of [3-(2-aminoethyl)amino]propyl-heptaisobutyl substituted polyhedral oligomeric silsesquioxane (AHIP) containing polyimide (PI) nanocomposites were successfully prepared. Structural, thermal and electrical properties of the polyimide nanocomposites were studied. The properties of AHIP containing polyimides were compared with those of the neat polyimide films. The surface morphology of the prepared AHIP containing polyimides were determined by using Scanning Electron Microscopy (SEM). The hydrophilic/hydrophobic nature of AHIP/polyimide composites were analyzed by measuring their water contact angles. It was found that the addition of AHIP into the polyimide slightly increased the contact angle values. The incorporation of 5% AHIP to the PI matrix decreased the dielectric constant value of pure PI from 8.6 to 11.7, respectively. Furthermore he dielectric permittivity was changed from 8.6 (neat polyimide) to 5.5 (PI3).     

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

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

Simultaneous Preparation of PI/POSS Semi‐IPN Nanocomposites

Summary: This investigation presents a simultaneous and convenient approach to produce a high‐performance polyimide with a low dielectric constant by introducing the octa‐acrylated polyhedral oligomeric silsesquioxane (methacrylated‐POSS) into a polyimide matrix to form polyimide semi‐interpenetrating polymer network (semi‐IPN) nanocomposites. The differential scanning calorimetry (DSC) and Fourier‐transform infrared (FT‐IR) results indicate that the self‐curing of methacrylated‐POSS and the imidization of polyamic acid (PAA) occurs simultaneously. The morphology of a semi‐IPN structure of polyimide/POSS‐PI/POSS nanocomposites with POSS nanoparticles embedded inside the matrix is elucidated. The POSS particles are uniform and are aggregated to a size of approximately 50–60 nm inside the polyimide matrix. The interconnected POSS particles are observed at high POSS content. The structure is highly cross‐linked, so the PI/POSS nanocomposites have an enhanced glass transition temperature. The high porosity of the PI/POSS nanocomposites markedly reduces the dielectric constant of PI because of the nanometer‐scale porous structure of POSS.

FT‐IR spectra of the various compounds of A) methacrylate‐POSS before curing, B) methacrylate‐POSS after curing, C) PAA containing 15 wt.‐% POSS, and D) PI/POSS containing 15 wt.‐% POSS.     

Characterization of PBT/POSS nanocomposites prepared by in situ polymerization of cyclic poly(butylene terephthalate) initiated by functionalized POSS

Novel poly(butylene terephthalate) (PBT)/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were synthesized by ring‐opening polymerization of cyclic poly(butylene terephthalate) initiated by functionalized POSS with various feed ratios. The impact of POSS incorporation on melting and crystallization behaviors of PBT/POSS nanocomposites was investigated by means of X‐ray diffraction and differential scanning calorimetry. It was found that the novel organic–inorganic association result in the significant alterations in the melting and crystallization behavior of PBT. Thermal studies confirmed that the incorporation of POSS can enhance the thermal stability of the polymers, and the copolymer glass transition temperature increased with the increasing of POSS macromonomer content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1853–1859, 2010     

Effect of POSS on crystalline transitions and physical properties of polyamide 12

Polyamide 12/Trisilanolphenyl‐POSS (PA 12/POSS) composites were prepared via melt‐compounding. The effect of polyhedral oligomeric silsesquioxane (POSS) on crystalline structure and crystalline transition of PA 12 was investigated by wide‐angle X‐ray diffraction (WAXD) and real time fourier transform infrared spectroscopy (FTIR). WAXD results indicated that PA 12 crystallized into γ‐form as slowly cooling from melt and the presence of POSS did not influence the crystalline structure of PA 12. Both PA 12 and PA 12/POSS composites underwent Brill transitions when they were heated from room temperature to melt point. Real time FTIR patterns showed that an absorption band at 697 cm^?1 ascribed to Amide V (α) mode was emerged along with the disappearance of Amide VI (γ) band at 628 cm^?1 with the increase of the temperature for PA 12 and PA 12/POSS composites, which suggested that the γ‐form crystalline has transformed into α form. The Brill bands were identified and the transformed mechanism was discussed based on the real FTIR results. The addition of POSS enhanced the tensile strength and thermal stability of PA 12. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 121–129, 2009     

POSS Ionic Liquid

We report the synthesis of a stable room-temperature ionic liquid consisting of an octacarboxy polyhedral oligomeric silsesquioxane (POSS) anion and an imidazolium cation. The introduction of the POSS moiety enhances the thermal stability and reduces the melting temperature. From an evaluation of the thermodynamic parameters during the melting, it was found that the rigidity and cubic structure of POSS can contribute to the enhancement of these thermal properties.     

Synthesis and characterization of block and random POSS/fluorinated PAES tricopolymers

Block and random polyhedral oligomeric silsesquioxane (POSS)/fluorinated poly aryl ether sulfone tricopolymers were synthesized using different synthetic strategies to investigate the effect of sequence distribution on their thermal, dielectric, and surface properties. Analyses indicated that all block and random copolymers showed similar growth tendency of water contact angles and T_g values, downward tendency of k values with increased content of POSS. The block copolymer displayed higher T_g values up to 187°C than random copolymers (173°C) under the same POSS molar percentage, which were highly related to their different sequence distribution. The dielectric constants of the tricopolymers were drastically reduced because of the presence of POSS and fluorine, and the dielectric constant could achieve as low as 2.71 (1 MHz). Besides, sequence distribution has no obvious influence on its surface properties and properties. Meanwhile, the yields of degradation residues of the tricopolymers were significantly improved by the ceramic formation from POSS moieties during thermal decomposition. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal degradation behaviors of epoxy resin/POSS hybrids and phosphorus–silicon synergism of flame retardancy

Epoxy resin (EP)/polyhedral oligomeric silsesquioxane (POSS) hybrids were prepared based on octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) and phosphorus‐containing epoxy resin (PCEP). The PCEP was synthesized via the reaction between bisphenol A epoxy resin (DGEBA) and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO). The structure and morphology of PCEP/OVPOSS hybrids were characterized by Fourier transform infrared spectroscopy and transmission electron microscopy. Differential scanning calorimetry revealed that the PCEP/OVPOSS hybrids possessed higher glass transition temperatures than that of PCEP. The thermal stability of the PCEP/OVPOSS hybrids was studied using thermogravimetric analysis (TGA). The TGA results illustrated the synergistic effect of phosphorus–silicon of flame retardancy: phosphorus promotes the char formation, and silicon protects the char from thermal degradation. The thermal degradation mechanism of the PCEP/OVPOSS hybrids was investigated by real time Fourier transform infrared spectra and pyrolysis/gas chromatogram/mass spectrometry (Py‐GC/MS) analysis. It was found that OVPOSS migrated to the surface of the matrix and then sublimed from the surface in nitrogen; whereas, the vinyl groups of OVPOSS were oxidated to form a radical trap which could react with pyrolysis radicals derived from PCEP to form the branched and crosslinked structure in air. The combustion behaviors of the hybrids were evaluated by micro combustion calorimetry. The addition of OVPOSS obviously decreased the value of peak heat release rate and total heat release of the hybrids. Moreover, scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy were used to explore the char residues of the PCEP and the hybrids. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 693–705, 2010     

Synthesis and properties of low‐dielectric‐constant polyimides with introduced reactive fluorine polyhedral oligomeric silsesquioxanes

A high‐performance, low‐dielectric‐constant polyimide (PI) nanocomposite from poly(amic acid) (PAA) cured with a reactive fluorine polyhedral oligomeric silsesquioxane (POSS) isomer was successfully synthesized. The features of this reactive fluorine POSS isomer [octakis(dimethylsiloxyhexafluoropropylglycidyl ether)silsesquioxane (OFG)] provided two important approaches (containing fluorine or being porous in the polymer matrix) of reducing the dielectric constant of PI. This reactive POSS isomer had an average of four epoxy groups and four fluorine groups on the POSS cage, and the epoxy groups could be cured with PAA to form a network framework of a PI/POSS nanocomposite. The PI/OFG nanocomposite had a high crosslinking density, high porosity (24.3%), high hydrophobicity, and low polarizability. These properties enhanced the thermal (glass‐transition temperature ～ 362 °C) and dielectric (dielectric constant ～2.30) properties of PI more than other POSS derivatives introduced into the PI backbone. A large number of small POSS particles (<10 nm) were embedded inside the PI matrix when the OFG content was low, whereas interconnected POSS aggregation domains were observed when the OFG content was high. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5391–5402, 2006     

A design of shape memory networks of poly(ε‐caprolactone)s via POSS‐POSS interactions

In this contribution, we reported a design of shape memory networks of poly(ε‐caprolactone)s (PCLs) via POSS‐POSS interactions. First, a series of novel organic‐inorganic PCL stars with polyhedral oligomeric silsesquioxane (POSS) termini were synthesized via the combination of ring‐opening polymerization of ε‐caprolactone and the copper (I)‐catalyzed cycloaddition of alkynyl with azido groups. It was found that the organic‐inorganic PCL stars significantly displayed shape memory properties with about 100% of recovery. The morphological observation showed that in the organic‐inorganic PCL stars, the POSS cages at the ends of PCL chains were self‐organized into the spherical POSS microdomains with the size of 10 to 20 nm in diameter. The POSS microdomains behaved as the netpoints, resulting in the formation of physically crosslinked networks. The novel physically crosslinked networks endowed the organic‐inorganic nanocomposites with shape memory properties.     

Synthesis of a “Butterfly Cage” Based on a Double‐Decker Silsesquioxane

Novel polyhedral structures were prepared with a butterfly‐shape composed of oligosiloxane wings and a double‐decker silsesquioxane (DDSQ) body. The compounds were synthesized in two steps from commercially available alkoxysilanes, and their structures were confirmed using spectroscopic methods and X‐ray crystallography. Not like other phenyl‐substituted cage silsesquioxanes, these butterfly cages show very good solubility in common organic solvents. The crystal structures clearly showed their unique features: a larger space with longer siloxane chains and a very flexible framework. Moreover, these compounds are thermally stable with a Td₅ (5 % weight loss temperature) over 320 °C.     

Preparation and characterization of Fe3O4@SiO2/APTPOSS core–shell composite nanomagnetics as a novel family of reusable catalysts and their application in the one‐pot synthesis of 1,3‐thiazolidin‐4‐one derivatives

Octakis[3‐(3‐aminopropyltriethoxysilane)propyl]octasilsesquioxane (APTPOSS) as a polyhedral oligomeric silsesquioxane derivative was prepared and used as a pioneer reagent to obtain a novel core–shell composite using magnetic iron oxide nanoparticles as the core and the inorganic–organic hybrid polyhedral oligomeric silsesquioxane as the shell. Fe₃O₄@SiO₂/APTPOSS were confirmed using Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, dynamic light scattering, thermogravimetric analysis, X‐ray diffraction and vibrating sample magnetometry. The inorganic–organic hybrid polyhedral oligomeric silsesquioxane magnetic nanoparticles were used as an efficient new heterogeneous catalyst for the one‐pot three‐component synthesis of 1,3‐thiazolidin‐4‐ones under solvent‐free conditions. Moreover, these nanoparticles could be easily separated using an external magnet and then reused several times without significant loss of catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

A novel use of Ti‐POSS as initiator of L‐lactide ring‐opening polymerization

The efficacy of a metal‐silsesquioxane, namely, heptaisobutyl (isopropoxyde)titanium‐polyhedral oligomeric silsesquioxanes (Ti‐POSS), as initiator of the ring‐opening polymerization of L ‐lactide (LLA) has been assessed. Indeed, as demonstrated by proton nuclear magnetic resonance (¹H NMR) spectroscopy and gel permeation chromatography (GPC) measurements, a well‐controlled polymerization occurs via a coordination‐insertion mechanism. Moreover, the above reaction leads to the direct insertion of the silsesquioxane molecule into the polymer backbone, thus producing a hybrid system. Differential scanning calorimetry measurements demonstrated that in comparison with a commercial poly‐L ‐lactide (PLLA), the polymers prepared with Ti‐POSS exhibit a higher crystallinity. Indeed, the presence of silsesquioxane molecules, attached to one end of the polymer chains, has been found to appreciably affect the crystal nucleation density. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Rigid polyurethane foams reinforced with disilanolisobutyl POSS: Synthesis and properties

This work reports the synthesis of rigid polyurethane (PU) foams modified by disilanolisobutyl polyhedral oligomeric silsesquioxane (DSIPOSS). This open‐cage nanostructure silsesquioxane has 2 hydroxyl groups and therefore can be chemically built directly in the PU backbone to form hybrid polyurethane‐POSS foam. Synthesis procedure using polymeric 4,4′‐diphenylmethane diisocyanate, polyetherol, and DSIPOSS has been elaborated, and the influence of POSS on the cell structure, closed cell content, apparent density, thermal conductivity, and compression strength of the rigid polyurethane composites has been evaluated. The hybrid composite foams containing 1.5 and 2.0 wt% DSIPOSS showed a reduced number of cells and an increased average area of foam cells in comparison with the unmodified PU, while the addition of 0.5wt% of DSIPOSS causes an increase in the number of cells of the foam as compared with the reference and thus a reduction in the average area of cells. X‐ray microtomography provided data on the porous structure of polyurethane hybrid materials, including reduction of the pore surface area. Scanning electron microscopy and energy‐dispersive X‐ray spectroscopy analysis revealed a good homogenization of DSIPOSS in polyurethane matrix. Thermogravimetric analysis results have shown that incorporation of POSS nanoparticles into PU foam does not significantly change the degradation process. The compressive strength of PUF‐POSS hybrids in the direction parallel and perpendicular to the direction of foam rise is greater than the strength of the reference foam already for the lowest DSIPOSS content.