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1.
We have prepared epoxy/polyhedral oligomeric silsesquioxane (POSS) nanocomposites by photopolymerization from octakis(glycidylsiloxy)octasilsesquioxane (OG) and diglycidyl ether of bisphenol A. We used nuclear magnetic resonance, Raman, and Fourier transform infrared spectroscopies to characterize the chemical structure of the synthetic OG. Differential scanning calorimetry and dynamic mechanical analysis (DMA) revealed that the nanocomposites possessed higher glass transition temperatures than that of the pristine epoxy resin. Furthermore, DMA indicated that all of the nanocomposites exhibited enhanced storage moduli in the rubbery state, a phenomenon that we ascribe to both the nano‐reinforcement effect of the POSS cages and the additional degree of crosslinking that resulted from the reactions between the epoxy and OG units. Thermogravimetric analysis revealed that the thermal stability of the nanocomposites was better than that of the pristine epoxy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1927–1934, 2009  相似文献   

2.
Octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) was used as a nanocrosslinking agent to prepare the crosslinked poly(N-isopropylacrylamide) (PNIPAM) networks with POSS content up to 50 wt%. The inter-component crosslinking was achieved via the reaction between NH moieties in amide group of PNIPAM and epoxide groups of OpePOSS. When the organic-inorganic nanocomposites were swollen in water the POSS-crosslinked PNIPAM exhibited the characteristics of hydrogels. With the moderate contents of POSS, the POSS-containing hybrid hydrogels displayed much faster response rates in swelling, deswelling and reswelling experiments than the PNIPAM hydrogels prepared via the free radical copolymerization of N-isopropylacrylamide (NIPAM) and N,N(')-methylenebisacrylamide (viz. the conventional crosslinker). The improved hydrogel properties have been interpreted on the basis of the formation of the nanosized hydrophobic microdomains around the POSS moieties (i.e., the nanocrosslinking sites).  相似文献   

3.
Summary: Octaaminophenyl polyhedral oligomeric silsesquioxane (OapPOSS) was used as a crosslinking agent together with 4,4‐methylenebis‐(2‐chloroaniline) to prepare polyurethane networks containing POSS. Fourier transform infrared spectroscopy (FT‐IR), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) were employed to characterize the POSS‐reinforced polyurethane. The POSS‐containing PU networks displayed enhanced glass transition temperatures (Tgs) and the storage moduli of the networks of the glassy state and rubber plateaus were also observed to be significantly higher than that of the control polyurethane although only a small amount of POSS was incorporated into the systems. The results can be ascribed to the significant nanoscale reinforcement effect of POSS cages on the polyurethane matrix. TGA results showed the thermal stability was also improved with incorporation of POSS into the system.

Dynamic mechanical spectra of PU and PU nanocomposites containing POSS.  相似文献   


4.
Epoxy/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were obtained from octakis(glycidyldimethylsiloxy)octasilsesquioxane (OG) and diglycidyl ether of bisphenol A cured with small‐molecule curing agents of diethylphosphite (DEP) and dicyandiamide (DICY). An increase in the POSS contents of the nanocomposites and an improvement in the nanocomposite homogeneity were observed with the use of the small‐molecule curing agents. Phosphorus in DEP and nitrogen in DICY also performed synergism with POSS for thermal stability enhancement and flammability improvement in the nanocomposites. The nanocomposites possessing high OG contents exhibited good thermal stability, improved flammability, and high storage moduli. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3825–3835, 2006  相似文献   

5.
Summary: Octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane (OpePOSS) was used as the crosslinking agent to prepare the nanocrosslinked poly(4‐vinylpyridine) (P4VP) with POSS content up to 55.2 wt.‐%. The formation of the crosslinked structure is ascribed to the macromolecular reaction between pyridine rings of P4VP and epoxide groups of OpePOSS. The POSS‐crosslinked P4VP displayed enhanced glass transition temperatures (Tgs) and an improved thermal stability in terms of the results of thermal analysis.

Crosslinking of poly(4‐vinylpyridine) with octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane.  相似文献   


6.
Poly[isobutyl methacrylate‐co‐butanediol dimethacrylate‐co‐3‐methacrylylpropylheptaisobutyl‐T8‐polyhedral oligomeric silsesquioxane] [P(iBMA‐co‐BDMA‐co‐MA‐POSS)] nanocomposites with different crosslink densities and different polyhedral oligomeric silsesquioxane (MA‐POSS) percentages (5, 10, 15, 20, and 30 wt %) were synthesized by radical‐initiated terpolymerization. Linear [P(iBMA‐co‐MA‐POSS)] copolymers were also prepared. The viscoelastic properties and morphologies were studied by dynamic mechanical thermal analysis, confocal microscopy, and transmission electron microscopy (TEM). The viscoelastic properties depended on the crosslink density. The dependence of viscoelastic properties on MA‐POSS content at a low BDMA loading (1 wt %) was similar to that of linear P(iBMA‐co‐MA‐POSS) copolymers. P(iBMA‐co‐1 wt % BDMA‐co‐10 wt % MA‐POSS) exhibited the highest dynamic storage modulus (E′) values in the rubbery region of this series. The 30 wt % MA‐POSS nanocomposites with 1 wt % BDMA exhibited the lowest E′. However, the E′ values in the rubbery region for P(iBMA‐co‐3 wt % BDMA‐co‐MA‐POSS) nanocomposites with 15 and 30 wt % MA‐POSS were higher than those of the parent P(iBMA‐co‐3 wt % BDMA) resin. MA‐POSS raised the E′ values of all P(iBMA‐co‐ 5 wt % BDMA‐co‐MA‐POSS) nanocomposites in the rubbery region above those of P(iBMA‐co‐5 wt % BDMA), but MA‐POSS loadings < 15 wt % had little influence on glass‐transition temperatures (Tg's) and slightly reduced Tg values with 20 or 30 wt % POSS. Heating history had little influence on viscoelastic properties. No POSS aggregates were observed for the P(iBMA‐co‐1 wt % BDMA‐co‐MA‐POSS) nanocomposites by TEM. POSS‐rich particles with diameters of several micrometers were present in the nanocomposites with 3 or 5 wt % BDMA. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 355–372, 2005  相似文献   

7.
Nanocomposites composed of a poly(vinylidene fluoride) (PVDF) matrix and 0, 3, 5, and 8 wt % fluoropropyl polyhedral oligomeric silsesquioxane (FP‐POSS) were prepared by using the solvent evaporation method. The morphology and the crystalline phase of the nanocomposites were investigated by digital microscopy, scanning probe microscopy, X‐ray diffractometer, and Fourier transform infrared spectroscopy. FP‐POSS acted as nucleating agent in PVDF matrix. A small content of FP‐POSS resulted in an incomplete nucleation of PVDF and generated bigger spherical particles, whereas higher contents led to a complete nucleation and formed more separate and less‐crosslinked particles. Nanoindentation, nanoscratch, and nanotensile tests were carried out to study the influence of different contents of FP‐POSS on the key static and dynamic mechanical properties of different systems. The nanocomposite with 3 wt % FP‐POSS was found to possess enhanced elastic properties and hardness. However, with the increase of the FP‐POSS content, the elastic modulus and hardness were found to decrease, and the improvement on stiffness was negative at contents of 5 and 8 wt %. Compared with neat PVDF, the scratch resistance of the PVDF/FP‐POSS nanocomposites was decreased due to a rougher surface derived from the bigger spherulites. Nanotensile testing results showed both the stiffness and toughness of PVDF‐FP3% were enhanced and further additions of FP‐POSS brought dramatic enhancements in toughness while associated with a decline in stiffness. Dynamical mechanical properties indicated the viscosity of the nanocomposites increased with the increasing FP‐POSS contents. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   

8.
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  相似文献   

9.
The thermal properties and morphological development of isothermally crystallized isotactic polypropylene (iPP) blended with nanostructured polyhedral oligomeric silsesquioxane (POSS) molecules at very small loading of POSS were studied with differential scanning calorimeter (DSC), thermal gravimetric analysis, dynamic mechanical analysis, polarized optical microscopy (POM), and wide‐angle X‐ray diffraction (WAXD). The result of DSC indicated that the crystallization rate of iPP increases with the increase in POSS contents during crystallization; moreover, the melting temperature of iPP/POSS nanocomposites slightly decreases, while the heat of fusion increases with the addition of POSS molecules at melting and remelting traces. The storage modulus and thermal stability, respectively, remarkably decrease, while the glass transition temperature of isothermally crystallized iPP/POSS nanocomposites increases slightly with the increase in POSS contents. The morphologies results of WAXD and POM show that the POSS molecules form about 35 nm sized nanocrystals and aggregate to form thread‐like and network structure morphologies, respectively, in the molten state even when the POSS content is very small. These results, therefore, suggest that the interaction force between the POSS molecules should be larger than the force between POSS molecules and iPP matrix; however, those interactions depend on the chain length of functionalized substituents on the POSS cage. Therefore, the POSS molecules aggregate forming nanocrystals and act as an effective nucleating agent for iPP and influence the thermal properties of iPP/POSS nanocomposites due to the shorter chain length of functionalized substituents, methyl, on the POSS cage. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2122–2134, 2006  相似文献   

10.
A series of polyhedral oligomeric silsesquioxane (POSS) based hybrid copolymers poly(POSS‐co‐methyl methacrylate ?co‐ 4‐vinylbenzyl fluoroether carboxylate) ( P(POSS‐MMA‐VBFC) ) were prepared via radical polymerization and characterized by nuclear magnetic resonance, fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, X‐ray powder diffraction, scanning electron microscopy and transmission electron microscopy. The thermal properties of these polymers (Td > 250 °C) were improved by the introduction of POSS cage. The cotton fabrics coated with the polymers possessed excellent water and oil repellency. The water and salad oil contact angle could be achieved from 133° to 159° and from 127° to 141° respectively as the content of POSS in the polymer increased from 0 to 7.1 wt %. Moreover, the cotton fabric coated with the terpolymer was less flammable than the uncoated one. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

11.
A new approach to achieve polymer‐mediated gold ferromagnetic nanocomposites in a polyhedral oligomeric silsesquioxane (POSS)‐containing random copolymer matrix has been developed. Stable and narrow distributed gold nanoparticles modified by 3‐mercaptopropylisobutyl POSS to form Au‐POSS nanoparticles are prepared by two‐phase liquid‐liquid method. These Au‐POSS nanoparticles form partial particle aggregation by blending with poly(n‐butyl methacrylate) (PnBMA) homopolymer because of poor miscibility between Au‐POSS and PnBMA polymer matrix. The incorporation the POSS moiety into the PnBMA main chain as a random copolymer matrix displays well‐dispersed gold nanoparticles because the POSS‐POSS interaction enhances miscibility between gold nanoparticles and the PnBMA‐POSS copolymer matrix. This gold‐containing nanocomposite exhibits ferromagnetic phenomenon at room temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 811–819, 2009  相似文献   

12.
The miscibility of a phenolic resin with polyhedral oligomeric silsesquioxane (POSS) hybrids and the specific interactions between them were investigated with Fourier transform infrared (FTIR) spectroscopy and wide‐angle X‐ray diffraction (WAXD). An analysis of the morphology and microstructure was performed with polarized optical microscopy and atomic force microscopy (AFM). The interassociation equilibrium constant between the phenolic resin and POSS (38.7) was lower than the self‐association equilibrium constant of pure phenolic (52.3) according to the Painter–Coleman association model. This result indicated that POSS was partially miscible with the phenolic resin. A polarized optical microscopy image of a phenolic/POSS hybrid material (20 wt % POSS) indicated that the crystals of POSS were arranged evenly in the phenolic matrix; the self‐assembled array of POSS crystals was also confirmed by AFM. This phenomenon was consistent with the FTIR spectroscopy and WAXD analyses. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1127–1136, 2004  相似文献   

13.
We report on a new strategy for fabricating well‐defined POSS‐based polymeric materials with and without solvent by frontal polymerization (FP) at ambient pressure. First, we functionalize polyhedral oligomeric silsesquioxane (POSS) with isophorone diisocyanate (IPDI). With these functionalized POSS‐containing isocyanate groups, POSS can be easily incorporated into a poly(N‐methylolacrylamide) (PNMA) matrix via FP in situ. Constant velocity FP is observed without significant bulk polymerization. The morphology and thermal properties of POSS‐based hybrid polymers prepared via FP are comparatively investigated on the basis of scanning electronic microscopy (SEM) and thermogravimetric analysis (TGA). Results show that the as‐prepared POSS‐based polymeric materials exhibit a higher glass transition temperature than that of pure PNMA, ascribing to modified POSS well‐dispersed in these hybrid polymers. Also, the products with different microstructures display different thermal properties. The pure PNMA exhibits a featureless morphology, whereas a hierarchical morphology is obtained for the POSS‐based polymeric materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1136–1147, 2009  相似文献   

14.
3‐Acryloxypropylhepta(3,3,3‐trifluoropropyl) polyhedral oligomeric silsesquioxane (POSS) was synthesized and used as a modifier to improve the thermal response rates of poly(N‐isopropylacrylamide) (PNIPAM) hydrogel. The radical copolymerization among N‐isopropylacrylamide (NIPAM), the POSS macromer and N,N′‐methylenebisacrylamide was performed to prepare the POSS‐containing PNIPAM cross‐linked networks. Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) showed that the POSS‐containing PNIPAM networks displayed the enhanced glass transition temperatures (Tg's) and improved thermal stability when compared with plain PNIPAM network. The POSS‐containing PNIPAM hydrogels exhibited temperature‐responsive behavior as the plain PNIPAM hydrogels. It is noted that with the moderate contents of POSS, the POSS‐containing PNIPAM hydrogels displayed much faster response rates in terms of swelling, deswelling, and re‐swelling experiments than plain PNIPAM hydrogel. The improved thermoresponsive properties of hydrogels have been interpreted on the basis of the formation of the specific microphase‐separated morphology in the hydrogels, that is, the POSS structural units in the hybrid hydrogels were self‐assembled into the highly hydrophobic nanodomains, which behave as the microporogens and promote the contact of PNIPAM chains and water. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 504–516, 2009  相似文献   

15.
The mechanical properties and thermal stability of polymers can be enhanced through the formation of nanocomposites. Nanocomposites consisting of hybrid copolymers of methacrylcyclohexyl polyhedral oligomeric silsesquioxane (POSS‐1) and methyl methacrylate (MMA) with up to 92 wt % (51 mol %) POSS‐1 and with superior thermal properties were synthesized using solution polymerization. The POSS‐1 contents of the copolymers were similar to or slightly higher than those in the feeds, the polydispersity indices were relatively low, and the degree of polymerization decreased with increasing POSS‐1 content. POSS‐1 enhanced the thermal stability, increasing the degradation temperature, reducing the mass loss, and preventing PMMA‐like degradation from propagating along the chain. The mass loss was reduced in a high POSS‐1 content copolymer since the polymerization of POSS‐1 with itself reduced sublimation. Exposure to 450 °C produced cyclohexyl‐POSS‐like remnants in the POSS‐1 monomer and in all the copolymers. The degradation of these remnants, for the copolymers and for the POSS‐1 monomer, yielded 75% SiO2 and an oxidized carbonaceous residue. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4264–4275, 2007  相似文献   

16.
Both octaglycidyletherpropyl polyhedral oligomeric silsesquioxane and hepta(3,3,3-trifluoropropyl)glycidyletherpropyl polyhedral oligomeric silsesquioxane were synthesized via the hydrosilylation reactions between octahydrosilsesquioxane [and/or hepta(3,3,3-trifluoropropyl)hydrosilsesquioxane] and allyl glycidyl ether. The polyhedral oligomeric silsesquioxane (POSS) macromers were characterized by means of Fourier transform infrared and nuclear magnetic resonance spectroscopy. The inter-component macromolecular reactions between the POSS macromers and poly(ethylene imine) (PEI) were employed to prepare the POSS-containing organic-inorganic PEI hybrids. The inclusion of octaglycidyletherpropyl POSS into PEI results in the formation of the organic-inorganic hybrid networks whereas the introducing hepta(3,3,3-trifluoropropyl)glycidyletherpropyl POSS to PEI affords the linear POSS-grafted PEI copolymers. Differential scanning calorimetry and thermogravimetric analysis show that the POSS-containing PEI hybrids displayed increased glass transition temperatures (Tg’s) and enhanced thermal stability compared to the plain PEI. These PEI hybrid composites can be significantly swollen with water without dissolving, suggesting the formation of hydrogels. The PEI hydrogels containing octaglycidyletherpropyl POSS is in reality the chemically-crosslinked hydrogels whereas the those containing hepta(3,3,3-trifluoropropyl)glycidyletherpropyl POSS displayed the behavior of physical hydrogels. The formation of physical hydrogels is ascribed to the microphase-separated morphology in the hybrids. In addition, the hybrids containing hepta(3,3,3-trifluoropropyl)glycidyletherpropyl POSS exhibited the typical amphiphilicity as evidenced by the increase in surface hydrophobilicity.  相似文献   

17.
A wrapped nanoflame retardant, designated as polyhedral oligomeric silsesquioxane (POSS)‐poly(4‐bromostyrene) (PBS)‐carbon nanotubes (CNTs), was synthesized via π‐π stacking interactions between the walls of multiwalled carbon nanotubes and the silicon‐bromine containing hybrid copolymer (designated as POSS‐PBS) that was copolymerized by 4‐bromostyrene and acryloyloxyisobutyl polyhedral oligomeric silsesquioxane. The POSS‐PBS‐CNTs exhibited good dispersibility in epoxy resin (EP) without obvious aggregation. Furthermore, the fire behaviors of this flame‐retardant EP (FR‐EP) nanocomposites were examined via limited oxygen index (LOI) and cone calorimeter (CONE) tests. The FR‐EP had an ideal LOI value of 35.3% and its residual char yield obtained from CONE test was significantly enhanced from 5.9% to 15.3% with the incorporation of 4 wt% POSS‐PBS‐CNTs and 1.33 wt% Sb2O3 into EP matrix. Additionally, the addition of 4 wt% POSS‐PBS‐CNTs or POSS‐PBS can efficiently decrease the peak heat release rate (PHRR) of EP matrix by 41.0% or 45.6%, respectively.  相似文献   

18.
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  相似文献   

19.
A top‐down approach is applied for the production of polyurethane (PU)–polyhedral oligomeric silsesquioxane (POSS) nanocomposites, namely melt blending. As opposed to the typical chemical incorporation during synthesis, a POSS moiety with two hydroxyl groups is melt blended into a commercial thermoplastic polyurethane with mass fraction up to 2 wt %. POSS disperses in the matrix in submicrometer‐sized crystals, as well as in length scale of few tens of nanometers, in the bulk. Phase separation of the produced composites was studied by both standard dynamic and isothermal annealing experiments. In an approach rare in the literature, the dynamics of phase separation is discussed based on isothermal differential scanning calorimetry curves recorded during annealing. The blended‐in nanoparticles affect the micromorphology in a complicated manner, dependent on the intrinsically complex phase separation mechanism of PU. At higher temperatures, POSS slows down the phase separation, whereas at lower ones, it enhances and accelerates it. POSS decreases the mechanical modulus of the final material, presumably as a result of changes in the microphase separation. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1133–1142  相似文献   

20.
New polymeric nanocomposites were prepared by covalent bonding of nanosized octahedral silsesquioxane particles containing reactive glycidyl group to polyamidoimides containing a carboxy group in the pendant chain. The influence of temperature, molecular weight of the polymer, and reaction time on the covalent bonding of polyhedral oligomeric silsesquioxane (POSS) nanoparticles was revealed. The effect of the POSS nanoparticle incorporation on the structure, dielectric and deformation-strength properties, and heat resistance of the new polymeric nanocomposites was examined.  相似文献   

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