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1.
By using Heck polycondensation, we have synthesized carbazole-based alt-copolymers tethered with polyhedral oligomeric silsesquioxanes (POSS), which had well-defined architectures, similar polymerization degrees and the different contents of POSS. The effect of POSS content and the length of the side chain containing POSS on the electroluminescence properties of these polymers were investigated. POSS particles in these alt-copolymers showed excellent dispersity and prevented the interchain aggregation of polymers in film state well. Besides, POSS benefited charge balance by increasing the electron current density, which led to a higher luminance and current efficiency, as well as purer blue light-emitting.  相似文献   

2.
Frontal polymerization (FP) has been successfully applied, for the first time, to obtain polymeric nanocomposites containing polyhedral oligomeric silsesquioxanes (POSS) in an amine‐cured epoxy matrix. Variations of maximum temperature (Tmax) and front velocity (Vf) have been studied. A comparison of these products with the corresponding materials, obtained by the classical batch polymerization technique, demonstrated that FP allows a higher degree of conversion than batch polymerization. The products have been characterized in terms of their thermal behavior with DSC analysis. SEM and X‐ray analyses revealed the morphology and the structures of the nanocomposites. The nanocomposites obtained by FP have the same characteristics of those synthesized, in much longer times, by batch polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4514–4521, 2007  相似文献   

3.
Octaphenylsilsesquioxane (PH‐POSS) and octa(γ‐methacryloxypropyl)silsesquioxane (MA‐POSS) were successfully synthesized by hydrolytic condensation of phenyltrichlorosilane and γ‐methacryloxypropyltrimethoxysilane, and characterized by Fourier transform infrared (FT‐IR), 1H and 29Si nuclear magnetic resonance (NMR), and matrix‐assisted laser desorption/ionization‐time of flight (MALDI‐TOF) mass spectrum. Morphology, degradation behavior, thermal, and mechanical properties of hybrid composites were studied by transmission electron microscopy (TEM), polarized optical microscopy (POM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), surface contact angle (SCA), tensile, and impact testing. Domains of PH‐POSS and MA‐POSS dispersed in the matrix with a wide size distribution in a range of 0.1–0.5 µm, while PH‐POSS exhibited a preferential dispersion. Because of the possible homopolymerization of MA‐POSS during the melt blending, the glass transition temperature of polycarbonate (PC)/MA‐POSS composites remained nearly unchanged with respect to PC/PH‐POSS composites that showed a depression of Tg due to the plasticization effect. It is interesting to note that the incorporation of POSS retarded the degradation rates of PC composites and thus significantly improved the thermal stabilities. Si? O fractions left during POSS degradations were a key factor governing the formation of a gel network layer on the exterior surface. This layer possessed more compact structures, higher thermal stabilities, and some thermal insulation. In addition, percentage residues at 700°C (C700) significantly increased from 10.8% to 15.8–22.1% in air. Fracture stress of two composites showed a slight improvement, and the impact strength of them decreased monotonically with the increase of POSS loading. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

4.
Various cotton fiber based boronate‐affinity adsorbents are recently developed for the sample pretreatment of cis‐diol‐containing biomolecules, but most do not have efficient capacity due to limited binding sites on the surface of cotton fibers. To increase the density of boronate groups on the surface of cotton fiber, polyhedral oligomeric silsesquioxanes were used to modify cotton fiber to provide plentiful reactive sites for subsequent functionalization with 4‐formylphenylboronic acid. The new adsorbent showed special recognition ability towards cis‐diols and high adsorption capacity (175 μg/g for catechol, 250 μg/g for dopamine, 400 μg/g for adenosine). The in‐pipette‐tip solid‐phase extraction was investigated under different conditions, including pH and ionic strength of solution, adsorbent amount, pipette times, washing solvent, and elution solvent. The in‐pipette‐tip solid‐phase extraction coupled with high‐performance liquid chromatography was used to analyze four nucleosides in urine samples. Under the optimal extraction conditions, the detection limits were determined to be between 5.1 and 6.1 ng/mL (S/N  =  3), and the linearity ranged from 20 to 500 ng/mL for these analytes. The accuracy of the analytical method was examined by studying the relative recoveries of analytes in real urine samples with recoveries varying from 83 to 104% (RSD = 3.9–10.2%, n = 3).  相似文献   

5.
A metal-doped organic and inorganic hybrid polyhedral oligomeric silsesquioxanes (POSS) with a titanium atom in the POSS cage and an ethanolamine substitute group in the corner, namely MEA-Ti-POSS, was synthesized through simple condensation reaction and substitute reaction. It was blended with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to form a kind of blending-type flame retardant system for the modification of epoxy resins. The thermal stability, flame retardancy and mechanical properties of cured epoxy resin composites were studied. Comparing with pure epoxy resin, the LOI value of EP/MEA-Ti-POSS/DOPO composites was raised from 25.2% to 32.7%, and the UL-94 grade reached V-0 level at a loading of the mixture of 5% MEA-Ti-POSS and 5% DOPO. In addition, the cone calorimetry results showed that the heat release rate, total heat release and total smoke production as well as smoke production rate were all reduced during the combustion of EP/MEA-Ti-POSS/DOPO composites. The residual char analysis revealed that carbon residues of EP/MEA-Ti-POSS/DOPO composite served as a physical protective layer to insulate the oxygen and combustible gases to reduce the ablation of the matrix. It was concluded that the mixture of MEA-Ti-POSS and DOPO not only effectively raised the thermal stability and flame retardancy of epoxy composited materials, but also improved their mechanical properties, which expanded a promising application of the metal-POSS derivatives as non-halogen additives in the flame retardant polymers.  相似文献   

6.
Inorganic polyhedral oligomeric silsesquioxane (POSS) was used as the core for the synthesis of poly(Llysine) peptide dendrimer via copper-catalyzed azide-alkyne click chemistry. The inorganic/organic composite dendrimer was characterized by MS, 1H NMR, FTIR, GPC and DLS.  相似文献   

7.
Molecular dynamics simulations were carried out on copolymers of both styrene and methyl methacrylate with polyhedral oligomeric silsesquioxane (POSS) derivatives to identify the origin of the property changes imparted upon the chemical incorporation of POSS. Simulations were carried out on these hybrid copolymers and the parent homopolymers to elucidate the effect of the T8, T10, and T12 POSS cages. These POSS comonomers were derivatized with a single polymerizable function and 7, 9, and 11 nonpolymerizable hydrocarbon moieties, respectively. Glass transition temperatures (Tg) were computed from specific volume versus temperature plots. The packing of POSS units around the polymer backbone was analyzed via their radial distribution functions. The effect of POSS on polymer motion was analyzed through the mean square displacement function. The improvements in the elastic moduli upon incorporation of POSS were computed by employing the static deformation method. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 234–248, 2006  相似文献   

8.
Polyhedral Oligomeric Silsesquioxanes (POSS) are cage‐structured inorganic–organic hybrid materials which can be used in various industrial applications. It is recently discovered that POSS structures with certain functional groups can be solubilized in supercritical CO2 allowing their applications in environmentally benign supercritical processing of materials. In this theoretical study, nature and energetics of the interactions of octatrifluoropropyl POSS, octatrifluoromethyl POSS, and octamethyl POSS with CO2 are investigated according to the principles of density functional theory (DFT) by use of Gaussian 09 software. Simulations show that CO2‐octamethyl POSS pair has hydrogen bonding between the O atom of CO2 and the H atom of the methyl group, and CO2‐octatrifluoromethyl POSS pair has interactions between the C atom of CO2 and the F atom of the trifluoromethyl group. CO2‐octatrifluoropropyl POSS pair is found to have both interaction types. The octamethyl, the octatrifluoromethyl and the octatrifluoropropyl POSS structures have interaction energies of ?2.18 kcal/mol, ?3.10 kcal/mol, and ?3.77 kcal/mol, respectively. This shows that the presence of Lewis acid–Lewis base interaction between C and F instead of hydrogen bonding between O and H atoms enhances the interaction of the molecule with CO2, while the presence of both interactions between the octatrifluoropropyl POSS‐CO2 pair makes the intermolecular interaction even stronger.  相似文献   

9.
We report here the fabrication of periodic sub-25 nm diameter size cylinder structures using block copolymer (BCP) directed self-assembly on nanoimprinted topographically patterned substrates. Tailored polyhedral oligomeric silsesquioxanes (POSSs) films were spin coated onto silicon substrates and were patterned by nanoimprint lithography to produce topographies commensurable with the BCP domain spacing. The chemistry of the POSS was tuned to control the alignment and orientation of the BCP films. The substrates were used to direct the microphase separation (following toluene solvent annealing) of a hexagonal structure forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS) having a domain spacing of 42.6 nm and PDMS cylinder widths of 23.7 nm. On more hydrophilic POSS substrates the cylinders were obtained parallel to the substrate plane and aligned with the topography. In contrast, in more hydrophobic POSS patterns, the cylinders align perpendicular to the substrate plane. The use of these methods for the nanofabrication of vias, nanofluidic devices or interconnect structures of sub-25 nm feature size is discussed.  相似文献   

10.
Ramírez  C.  Abad  M. J.  Barral  L.  Cano  J.  Díez  F. J.  López  J.  Montes  R.  Polo  J. 《Journal of Thermal Analysis and Calorimetry》2003,72(2):421-429
A new material belongs to the family of polyhedral oligomeric silsesquioxanes, the 1-(3-glycidyl) propoxy-3,5,7,9,11,13,15-isobutylpentacyclo-[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane (glycidylisobutyl-POSS) is characterized by differential scanning calorimetry, thermogravimetric analysis and atomic force microscopy. Epoxy systems based on diglycidyl ether of bisphenol A (DGEBA) cured with the diamines, 4,4'-diamine-diphenylmethane (DDM) and 1,4-phenylenediamine (pPDA), were kinetically studied by differential scanning calorimetry in isothermal and dynamic modes. The thermal behaviour of these systems as the glycidylisobutyl-POSS was added, is discussed later. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

11.
Three new octyloxy substituted spirobifluorenes, 2,7-diphenyl-3′,6′-bis(octyloxy)-9,9′-spirobifluorene (DPBSBF, 1a), 2,7-dibiphenyl-3′,6′-bis(octyloxy)-9,9′-spirobifluorene (DBBSBF, 1b) and 2,7-diterphenyl-3′,6′-bis(octyloxy)-9,9′-spirobifluorene (DTBSBF, 1c) were prepared. All the compounds had been fully characterized by 1H and 13C NMR, UV-Vis, DSC, mass spectrometry and gave satisfactory elemental analyses. They possessed good solubility in common organic solvents and good homogeneous film formation. The optical energy band gap of DBBSBF was 3.27 eV between the HOMO energy level, 5.85 eV, measured by UPS and the LUMO, 2.58 eV, calculated from absorption spectrum. A blue organic light emitting diode (OLED) based on the structure of ITO/TPD (60 nm)/DBBSBF (40 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (100 nm) showed good performance. The luminance of 3125 cd/m2 was observed at a drive voltage of 12.8 V and the colour coordinate in CIE chromaticity was (0.14, 0.12). The external quantum efficiency was obtained to be 2.8% at 100 cd/m2.  相似文献   

12.
In this study, porous sandwich structure Fe3O4 nanoparticles coated by polyhedral oligomeric silsesquioxanes and β‐cyclodextrin were prepared by surface polymerization and were used as the magnetic solid phase extraction adsorbent for the extraction and determination of carbaryl and carbofuran. The Fe3O4 nanoparticles coated with polyhedral oligomeric silsesquioxanes and β‐cyclodextrin were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, vibrating sample magnetometry, and scanning electron microscopy. After optimizing the extraction conditions, a method that combined magnetic solid phase extraction with high‐performance liquid chromatography was developed for the determination of carbaryl and carbofuran in apple. The method exhibited a good linearity in the range of 2–400 μg/kg for carbaryl and carbofuran (R= 0.9995), respectively. The limits of detection were 0.5 μg/kg of carbaryl and 0.7 μg/kg for carbofuran in apple, respectively. Extraction recoveries ranged from 94.2 to 103.1% with the preconcentration factor of 300 and the relative standard deviations were less than 5.9%. These results indicated that the method combined magnetic solid phase extraction with high‐performance liquid chromatography and was promising for the determination of carbaryl and carbofuran at trace amounts.  相似文献   

13.
A series of white polymer light emitting displays (PLEDs) based on a polymer blend of polyalkylfluorenes and poly(2‐methoxy‐5,2′‐ethyl‐hexyloxy‐1,4‐phenylene vinylene) (MEH‐PPV) was developed. MEH‐PPV or red light emitting alkyfluorene copolymer (PFR) was blended with blue light emitting alkyfluorene copolymer (PFB), and MEH‐PPV was blended with both green light emitting alkyfluorene copolymer (PFG) and PFB to generate white light emission PLEDs. Low turn on voltage (2.7 V), high brightness (12,149 nits), high efficiency (4.0 cd/A, 4.0 lm/W), and good color purity (Commission Internationale de L'Eclairage (CIEx,y) co‐ordinates (0.32, 0.34)) were obtained for the white PLEDs based on the PFB and MEH‐PPV polymer blend. Exciplex formation in the interface between PFR and PFB induced a new green emission peak for these two components based white PLEDs. As a result, strong white emission (4078 nits) was obtained by mixing the red, green, and blue (RGB) three primary colors. High color purity of blue (CIE, x = 0.14, y = 0.08), green (CIE, x = 0.32, y = 0.64) and red (CIE, x = 0.67, y = 0.33) emissions was achieved for white PLEDs combining with dielectric interference color‐filters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 330–341, 2007  相似文献   

14.
《先进技术聚合物》2018,29(8):2373-2380
Grafting nanoscale reinforcement onto macrolevel carbon fiber (CF) surface is an efficient approach to improve interfacial strength and properties of composites. In the research, 2 different polyhedral oligomeric silsesquioxanes (POSS)/CF hybrids have been prepared by a facile 2‐step method. Carbon fiber was grafted with aniline groups by aryl diazonium reaction using water as the reaction medium, and then separately functionalized with glycidyllsobutyl POSS (EP0418) or glycidyl POSS (EP0409) by the chemical bonding. Characterization of fiber surface structures before and after modification confirmed the covalent bonding nature between both kinds of POSS and CF. Atomic force microscopy images showed the uniform distributions of EP0418 or EP0409 modified on the fiber surface and the similar enhanced degree of surface roughness (89.3 and 88.7 nm). Dynamic contact angle tests showed that EP0409‐grafted CF (CF‐g‐EP0409) had lower contact angles and higher surface free energy than those of EP0418‐grafted CF (CF‐g‐EP0418). Interfacial strength and hydrothermal aging resistance of composites enhanced significantly after POSS modification, especially for CF‐g‐EP0409 composites. Interfacial reinforcing mechanisms of composites reinforced with 2 different POSS/CF hybrids have also been analyzed and compared.  相似文献   

15.
A novel solid-phase microextraction (SPME) fiber was prepared by polymerization of an organic–inorganic hybrid polymeric coating on an anodized and derived Ti wire, and applied for the analysis of polycyclic aromatic hydrocarbons from environmental samples followed by high performance liquid chromatography (HPLC) analysis. A polyhedral oligomeric silsesquioxane (POSS) reagent containing methacryl substituent groups was used as an organic–inorganic hybrid cross-linker, and copolymerized with methyl methacrylate (MMA) to fabricate the hybrid coating via thermally initiated free radical polymerization in a glass capillary mold. The prepared fiber can be easily withdrawn from the glass capillary mold by controlling the polymerization conditions, especially polymerization solvent. A homogeneous and porous coating with thickness of about 100 μm was achieved using ethanol as polymerization solvent at the mass ratio of MMA to POSS as 1:0.5. High chemical and mechanical stability, as well as excellent durability for more than 100 times extractions with almost undiminished extraction efficiency were achieved due to the chemical immobilization and crosslinked hybrid coating. The proposed fiber showed much better extraction performance than the 100 μm commercial polydimethylsiloxane fiber for extracting PAHs from aqueous sample. The developed SPME-HPLC method for the determination of PAHs using the MMA–POSS hybrid coating achieved good linearity with good correlation coefficients (R = 0.991–0.999) and low detection limits in the range of 0.006 to 0.05 ng mL−1 (S/N = 3). The proposed fiber was successfully applied to the extraction of PAHs from environmental water samples with recoveries of 82–104% for river water, 83–103% for pool water, and 79–98% for wastewater, respectively.  相似文献   

16.
Biodegradable aliphatic–aromatic copolyester nanohybrids, with polyhedral oligomeric silsesquioxane (POSS) moieties tethered between poly(lactic acid) (PLA) and poly(butylene terephthalate) segments, is designed and prepared. First, (bis(2‐hydroxyethyl) dipropionate POSS, BH‐POSS) is synthesized under mild conditions, then in situ polycondensation is carried out in the presence of terephthalic acid, PLA oligomer, 1,4‐butanediol, and BH‐POSS. 1 H‐NMR and Fourier transfer infrared spectroscopy confirm that Michael addition reaction of amino‐POSS and hydroxyethyl acrylate takes place efficiently and forms BH‐POSS in high yield at room temperature. Owing to similar functional groups, BH‐POSS could be easily incorporated into the macromolecular chains and obtain final copolyester nanohybrids. Moreover, X‐ray diffractometry and transmission electron microscopy observations demonstrate that POSS moieties occur self‐assembly behaviors and form nanoaggregates with the diameter of 50–100 nm. The thermal stability and mechanical properties of the copolyester nanohybrids containing BH‐POSS are substantially improved. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   

17.
A polyhedral oligomeric silsesquioxane-[60]fullerene (POSS-C60) dyad was designed and used as a novel electron acceptor for bulk heterojunction (BHJ) polymer solar cells (PSCs) with an inverted device configuration. The studies of time-resolved photoinduced absorption of the pristine thin film of poly[(4,4’-bis(2-ethylhexyl)dithieno[3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis (2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl] (SiPCPDTBT) and the composite thin film of SiPCPDTBT:POSS-C60 indicated efficient electron transfer from SiPCPDTBT to POSS-C60 with inhibited back-transfer. BHJ PSCs made by SiPCPDTBT mixed with POSS-C60 yielded the power conversion efficiencies (PCEs) of 1.50%. Under the same operational conditions, PCEs observed from BHJ PSCs made by SiPCPDTBT mixed with [6,6]-phenyl-C61-butyric acid methyl ester were 0.92%. These results demonstrated that POSS-C60 is a potentially good electron acceptor for inverted BHJ PSCs.  相似文献   

18.
聚苯撑乙烯(PPV)类聚合物是优异的发光材料, 有望作为全色显示中三基色的材料之一得到应用. 我们采用2-溴-1,4-亚二甲苯二乙酯为原料, 合成了商品名为Supper Yellow PPV (SY PPV)的苯基取代PPV. 中间体、单体和聚合物的结构都通过核磁共振、元素分析进行了表征. SY PPV的吸收峰在434 nm, 吸收边在510 nm, 带隙2.44 eV. 光致发光峰值和电致发光峰值分别在516和552 nm. SY PPV的器件性能为: 启动电压为2.4 V, 最大亮度大于49000 cd·m-2, 最大流明效率为21 cd·A-1, 显著优于采用老方法合成SY PPV的最大流明效率(16-18 cd·A-1).  相似文献   

19.
A polyhedral oligomeric silsesquioxane (POSS), consisting mainly of a mixture of octahedra, nonahedra, and decahedra with bulky and flexible organic substituents, with three secondary hydroxyls per organic group, was used to modify epoxy networks produced by the homopolymerization of diglycidyl ether of bisphenol A in the presence of benzyldimethylamine. Several physical, thermal, and mechanical properties of the cured materials containing 0, 10, 30, and 50 wt % POSS were determined. The addition of POSS increased the elastic modulus and the yield stress measured in uniaxial compression tests, mainly because of the increase in the cohesive energy density produced by hydrogen bonding through the hydroxyl groups. A constant yield stress/elastic modulus ratio equal to 0.03 was observed for different POSS concentrations and test temperatures. The glass‐transition temperature decreased with POSS addition because of the flexibility of organic branches present in the POSS structure and the decrease in the crosslink density (determined from the rubbery modulus). Although a combination of a reduction in the glass‐transition temperature (plasticization) with an increase in the glassy modulus (antiplasticization) is a well‐known phenomenon, what is original is that in this case it was not the result of the suppression (or reduction in intensity) of subglass relaxations but was produced by an increase in the cohesive energy density. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1451–1461, 2003  相似文献   

20.
Two novel organic–inorganic hybrid polyfluorene derivatives, poly{(9,9′‐dioctyl‐2,7‐fluorene)‐co‐(9,9′‐di‐POSS‐2,7‐fluorene)‐co‐[2,5‐bis(octyloxy)‐1,4‐phenylene]} (PFDOPPOSS) and poly{(9,9′‐dioctyl‐2,7‐fluorene)‐co‐(9,9′‐di‐POSS‐2,7‐fluorene)‐co‐bithiophene} (PFT2POSS), were synthesized by the Pd‐catalyzed Suzuki reaction of polyhedral oligomeric silsesquioxane (POSS) appended fluorene, dioctyl phenylene, and bithiophene moieties. The synthesized polymers were characterized with 1H NMR spectroscopy and elemental analysis. Photoluminescence (PL) studies showed that the incorporation of the POSS pendant into the polyfluorene derivatives significantly enhanced the fluorescence quantum yields of the polymer films, likely via a reduction in the degree of interchain interaction as well as keto formation. Additionally, the blue‐light‐emitting polyfluorene derivative PFDOPPOSS showed high thermal color stability in PL. Moreover, single‐layer light‐emitting diode devices of an indium tin oxide/poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate)/polymer/Ca/Al configuration fabricated with PFDOPPOSS and PFT2POSS showed much improved brightness, maximum luminescence intensity, and quantum efficiency in comparison with devices fabricated with the corresponding pristine polymers PFDOP and PFT2. In particular, the maximum external quantum efficiency of PFT2POSS was 0.13%, which was twice that of PFT2 (0.06%), and the maximum current efficiency of PFT2POSS was 0.38 cd/A, which again was twice that of PFT2 (0.19 cd/A). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2943–2954, 2006  相似文献   

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