Highly soluble polyamide–polyhedral oligomeric silsesquioxane hybrid nanocomposites: Synthesis and characterization

A method of preparing linear polyamide‐polyhedral oligomeric silsesquioxane (PA‐POSS) hybrid nanocomposites in a reactor using thionyl chloride/triethylamine (TEA) as the activating agent was investigated. Soluble polyamic acid (PAA) having carboxylic acid end groups were first synthesized by condensation reaction of 2,2‐ bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]‐1,1,1,3,3,3‐hexafluoropropane, (6FODA). The PAA was acylated by SOCl₂/TEA and followed by the addition of different mole percentages of aminopropyl heptacyclopentyl POSS (AP‐POSS) and 3‐(trifluoromethyl) aniline to get the PA‐POSS hybrid nanocomposites. The chemical structure of PA‐POSS hybrid nanocomposites were investigated by ATR‐FTIR and NMR spectroscopic techniques. Thermal and morphological properties of PA‐POSS were influenced by changing the percentage of POSS and investigated by thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. Wide angle X‐ray diffraction and contact angle measurements. The PA‐POSS with hexafluoroisopropylidene and POSS groups have higher bulk density resulting in higher free volume and then increasing the solubility property. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Morphology and mechanical properties of polypropylene‐POSS hybrid nanocomposites obtained by reactive blending

The polypropylene‐polyhedral oligomeric silsesquioxane (PP‐POSS) organic–inorganic hybrids were obtained and studied. The hybrids were prepared by grafting of POSS on PP chains during a reactive melt‐blending of polypropylene (iPP), maleic anhydride functionalized PP (PP‐g‐MA), and amine‐functionalized POSS (aminopropylheptaisobutyl‐POSS, ambPOSS, aminopropylheptaisooctyl‐POSS, amoPOSS, or aminoethylaminopropylheptaisobutyl‐POSS, am2bPOSS), taking advantage of the high efficiency of amino‐anhydride reaction in the molten state. The structure, morphology, and physical properties of the obtained hybrids and blends were studied by means of wide‐ and small‐angle X‐ray scattering, dynamic scanning calorimetry, scanning electron microscopy, dynamic mechanical thermal analysis, as well as tensile and impact experiments. The influence of POSS chemical structure and grafting degree on the morphological characteristics and mechanical properties was investigated. It was found that grafting of POSS cages on PP chains leads to the POSS dispersion on the molecular level. On contrary, when POSS was mixed with plain iPP any grafting of POSS on iPP chains was impossible, which resulted in phase‐separated blend with crystallites of POSS dispersed in iPP matrix. The mechanical tests revealed that modification of polypropylene by grafting with POSS molecules does not affect significantly its mechanical properties, both static and dynamic, except ultimate strain, which is markedly lower in hybrids and their blends than in plain iPP. Also the impact properties of PP were practically not improved by modification with POSS. POLYM. COMPOS., 34:929–941, 2013. © 2013 Society of Plastics Engineers     

Low‐κ nanocomposite films based on polyimides with grafted polyhedral oligomeric silsesquioxane

Nanocomposites of polyimides (PI) with covalently grafted polyhedral oligomeric silsesquioxane (R₇R′Si₈O₁₂ or POSS) units were prepared by thermally‐initiated free‐radical graft polymerization of methacrylcyclopentyl‐POSS (MA‐POSS) with the ozone‐pretreated poly[N,N′‐(1,4‐phenylene)‐3,3′,4,4′‐benzophenonetetra‐carboxylic amic acid] (PAA), followed by thermal imidization. The chemical composition and structure of the PI with grafted methacrylcyclopentyl‐POSS side chains (PI‐g‐PMA‐POSS copolymers) were characterized by nuclear magnetic resonance (NMR), X‐ray diffraction (XRD), and thermogravimetric analysis (TGA). The POSS molecules in each grafted PMA side chain of the amorphous PI films retained the nanoporous crystalline structure, and formed an aggregate of crystallites. The PI‐g‐PMA‐POSS nanocomposite films had both lower and tunable dielectric constants, in comparison with that of the pristine PI films. Dielectric constants (κ's) of about 3.0–2.2 were obtained. The present approach offers a convenient way for preparing low‐κ materials based on existing PI's. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Properties and morphology of supertoughened polyamide 6 hybrid composites

In this study, supertoughened polyamide (PA) nanocomposites were prepared by the incorporation of epoxidized polyhedral oligomeric silsesquioxane (POSS) into the polyamide 6 (PA6)/methyl methacrylate–butadiene–styrene copolymer (MBS) blend via a melt‐blending method. The effect of POSS on the rheological properties, mechanical properties, water uptake, and morphology of the hybrid PA6 nanocomposites was studied. The results show that under impact loading, the hybrid PA6 composites exhibited significant improvements in both the crack initiation energy and the crack propagation energy. This hybrid composite showed supertough behavior. Meanwhile, the tensile strength and the water absorption resistance was also improved with the addition of epoxidized POSS. The capillary and torque rheological results indicated that the epoxidized POSS, which acted as nanoscale ball bearings, significantly decreased the melt viscosity of the matrices and facilitated the melting process. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were performed to study the microstructure–property relationships of the hybrid PA6 composites. The TEM results showed that the MBS particles were dispersed homogeneously in the PA6 matrix. The mean diameter of the MBS particles decreased, and the size distribution of the MBS particles narrowed down with the introduction of the epoxidized POSS and compatiblizer. The SEM micrographs indicated that the impact fracture surfaces of the PA composites showed morphological characteristics of supertough polymers because of the synergistic effect of the functionalized POSS and compatibilized MBS particles. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of POSS on morphology and mechanical properties of polyamide 12/montmorillonite nanocomposites

Sodium-montmorillonite (MMT) was modified with two types of AP-POSS and OA-POSS and dual-surfactants (POSS with a ditallow-based second surfactant: 04AP-POSS/08DTDMA and 04OA-POSS/08DTDMA), respectively, via ion-exchange reaction. The interlayer space, interlamellar structure, thermal and surface properties of these organo-montmorillonites were investigated by X-ray diffraction, thermogravimetric analysis, and contact angle measurement. The interlayer space of POSS modified clay was strongly dependent on the arrangement of POSS surfactants, but less on the POSS concentration. The POSS modified montmorillonites have partially exchanged silicate surfaces and good thermal stabilities due to steric hindering and thermal stability of the POSS molecules. Dual-surfactant modified montmorillonites showed higher exchange ratio and possessed better compatibility with PA12 due to the lower interfacial free energy. Polyamide 12-montmorillonite nanocomposites were prepared by conventional melt compounding with the four POSS based organo-montmorillonites. The best dispersion of modified montmorillonite was observed for 3 mass% 04AP-POSS/08DTDMA/MMT filled PA12 nanocomposites, which resulted in the best mechanical performance with an increase of 60% in tensile modulus and 10% in yield strength, respectively, compared to that of pure PA12. Compatibility between montmorillonites and polymer was not the only key factor affecting dispersion, thermal stability and interlayer space were also crucial for good dispersion of montmorillonites in polymer matrix.     

Effect of drawing on the molecular orientation,polymorphism, and properties of melt‐spun nanocomposite fibers based on nylon 6 with polyhedral oligomeric silsesquioxane,montmorillonite, and their combination

In this work, binary and ternary nanocomposite systems based on nylon 6 with montmorillonite (MMT), polyhedral oligomeric silsesquioxane (POSS), and their combination were prepared using a melt‐compounding process. In the transmission electron microscope (TEM) images, the MMT was found to be generally well dispersed in all materials resulting in its good chemical compatibility with nylon 6, affording intercalated disordered microstructures. On the other hand, the TEM images showed that POSS formed micron‐size crystalline agglomerates possibly resulting from a lack in chemical compatibility with nylon 6. These nanocomposite systems were melt‐spun into fibers, and the relevant structure–property relationships that occur during the cold drawing process was established by correlating the tensile properties to the changes in crystallinity, polymorphic crystal forms, and molecular orientation. The properties of the resulting fibers were found to be rather skewed and significantly affected by the polymer/nanoparticles interface. The agglomeration of POSS and POSS–MMT particles coupled with the weak nylon 6/POSS interface, reflected on the tensile properties of the nylon 6/POSS and nylon 6/MMT‐POSS fibers which underperformed. Some nanocomposite fiber systems offered significant improvements in modulus without excessively compromising the extensibility of the fibers. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

ε-Caprolactam polymerization in presence of polyhedral oligomeric silsesquioxanes (POSS)

Polyhedral oligomeric silsesquioxanes (POSS) have been covalently linked to polyamide 6 (PA6) chains with the aim of synthesizing hybrid organic/inorganic polymer materials. The synthesis has been achieved by in situ polymerization of ε-caprolactam (CL) in presence of increasing amounts of POSS molecules, using two polymerization mechanisms (hydrolytic and anionic). The latter method has been carried out by three different approaches, in order to get PA6 samples characterized by various morphologies and content of structural defects: (i) quasi-adiabatic bulk polymerization; (ii) isothermal bulk polymerization; (iii) quasi-isothermal suspension polymerization. The products obtained have been characterized in term of structure, morphology, thermal properties and molecular mass.     

Investigations on the formation of composites by injection molding of PA6 and different grafted polypropylenes and their blends

Blends of different types of polypropylenes (PP) with polyamide 6 (PA6) were produced by extrusion. The PPs used were a PP homopolymer, a maleic anhydride‐grafted homopolymer, and an acrylic acid‐grafted homopolymer. The blends were characterized by DSC measurements, selective extraction, infrared spectroscopy, REM microscopy, melt rheology, and their mechanical properties. Three types of interactions in the blends as well as in two‐component composites mold by the core‐back process could be identified. Blends of PP with PA6 were not compatible, and two‐component bars could not be produced. Blends of PPgAA and PA6 were made compatible during reactive extrusion. Two‐component bars could be produced only with a blend containing 50 wt % PA6. The composite formation was based on the interdiffusion of PA6 in both components and the reactive compatibilization in the blends. Blends of PPgMAn were also compatibilized during reactive extrusion. The composite formation on two‐component injection molding was based on two mechanisms: the interdiffusion at sites, where PA6 chains of both the components came into contact, and an interfacial reaction, where PPgMAn and PA6 came into contact. The interfacial reaction was supported by the high mobility of the first component at the temperature of the melt of the second component. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2992–2999, 2006     

Morphology and mechanical properties of high density polyethylene‐POSS hybrid nanocomposites obtained by reactive blending

The high density polyethylene‐polyhedral oligomeric silsesquioxane (HDPE‐POSS) organic–inorganic hybrids were obtained and their properties studied. The hybrids were prepared by grafting of POSS on polyethylene chains during reactive melt‐blending of HDPE, maleic anhydride functionalized HDPE and amine‐functionalized POSS, taking advantage of the high efficiency of amine‐anhydride reaction in the molten state. The structure, morphology, and physical properties of the obtained hybrids and blends were studied to find the influence of POSS chemical structure and grafting degree on the morphological characteristics and mechanical properties of hybrid nanocomposites. It was found that grafting of POSS cages on HDPE chains leads to the POSS dispersion at the molecular level. On the contrary, when POSS was mixed with plain HDPE any grafting of POSS on polyethylene chains was not possible, which resulted in phase‐separated blend. The mechanical tests revealed that modification of polyethylene by grafting with POSS molecules does not affect significantly its mechanical properties, both static and dynamic, except ultimate strain, which is lower in hybrids and their blends than in plain HDPE. The impact properties (Izod impact strength) were slightly improved by grafting of HDPE with POSS. HDPE‐g‐POSS hybrids demonstrated also much enhanced thermo‐oxidative stability comparing to plain polyethylene. POLYM. ENG. SCI., 55:2058–2072, 2015. © 2014 Society of Plastics Engineers     

Allylated novolac/4,4′‐bismaleimidodiphenylmethane resin containing polyhedral oligomeric silsesquioxane: Preparation,morphology and thermal stability

Allylated novolac/4,4′‐bismaleimidodiphenylmethane resin (AN/BDM) had been modified with well‐defined inorganic building blocks‐polyhedral oligomeric silsesquioxane (POSS). Octamaleimidophenyl polyhedral silsesquioxane (OMPS) was used as the cocuring reagent of the AN/BDM resin to prepare POSS‐modified AN/BDM resin, and POSS content was between 0 and 17.8 wt %. The curing reaction of the POSS‐modified AN/BDM resin was monitored by means of Fourier transform infrared spectroscopy (FTIR), and the results revealed that maleimide groups on OMPS molecule could undergothe curing reaction between allyl groups and maleimide groups. Therefore, the crosslinked network containing POSS was formed. Scanning electron microscopy (SEM) and X‐ray diffraction (XRD) were employed to study the morphology of the cured POSS‐modified AN/BDM resins. The homogeneous dispersion of POSS cages in AN/BDM matrices was evidenced. Thermogravimetric analysis (TGA) indicated that incorporation of POSS into AN/BDM crosslinked network led to enhanced thermal stability. The improved thermal stability could be ascribed to higher crosslink density and inorganic nature of POSS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3903–3908, 2007     

Nanocomposites of poly(m‐xylene diamide) with polyhedral oligomeric silsesquioxane,montmorillonite, and their combination: Structure and properties

In this work, nanocomposites of poly (m‐xylene diamide) (MXD6) with dodecaphenyl polyhedral oligomeric silsesquioxane (POSS), montmorillonite (MMT) and their combination (MMT‐POSS) were produced by melt‐compounding and their structure–property relationships were established. The montmorillonite was found to be homogeneously dispersed affording intercalated disordered structures whilst the distribution and dispersion of the POSS was rather skewed with the presence of phase separated crystalline aggregates of up to several hundred nanometers. Significant differences in properties were observed depending on the type of nanoscale filler present in the nanocomposites. The montmorillonite provided some improvements in stiffness and dynamic response of MXD6. POSS on the other hand improved the ductility of MXD6 and had a plasticizing effect. It has been suggested that there might be a lubricating action at the interface inducing better molecular motion between polymer chains of MXD6. By combining MMT and POSS, the properties of the corresponding nanocomposites were found to be intermediate. The thermal stability of MXD6 was enhanced in the nanocomposites although a negative deviation from the theoretical model was observed when POSS was present in the nanocomposites. This observation underlies some antagonistic effects which have been attributed to the presence of catalytic benzene radicals during thermal degradation. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Ultrasonic treatment of polypropylene,polyamide 6, and their blends

The mechanical and rheological properties of polypropylene (PP), polyamide 6 (PA6), and their blends treated by high‐intensity ultrasound during extrusion were investigated. A lower head pressure was achieved in the extrusion of these thermoplastics. The mechanochemical and sonochemical effects of ultrasound led to simultaneous ionic condensation reactions and degradation in a homogeneous melt of PA6, with a prevailing effect of enhanced polycondensation reactions. The observed improvements in the mechanical properties of ultrasonically treated PA6 were attributed to condensation reactions, which yield a higher molecular weight, a higher crystallinity, and a more uniform crystal size distribution. At high ultrasound amplitudes, for PP, the degradation of polymer chains was observed with little deterioration of the mechanical properties. For ultrasonically treated PP/PA6 blends, a competition between the degradation and partial in situ compatibilization effect was found. At certain blend ratios, the tensile toughness and impact strength of the treated blends were almost double those of the untreated blends. However, full compatibilization was not achieved, possibly because of the low coupling selectivity of highly reactive radicals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2643–2653, 2006     

Preparation of VB‐a/POSS hybrid monomer and its polymerization of polybenzoxazine/POSS hybrid nanocomposites

A benzoxazine monomer (VB‐a) containing an allyl groups was synthesized through the Mannich condensation of bisphenol A, formaldehyde, and allylamine (bisphenol‐A and allylamine as VB‐a). This monomer was then reacted with polyhedral oligomeric silsesquioxane (POSS) through hydrosilylation, followed by thermal curing to form poly(VB‐a)/POSS hybrid nanocomposites. The curing behavior of the nanocomposites was monitored using Fourier transform infrared spectroscopy (FTIR), and their thermal and morphological properties were investigated through thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and scanning electron microscopy. DMA revealed that the glass transition temperatures of the poly(VB‐a)/POSS nanocomposites were higher than that of the pristine poly(VB‐a), presumably because the POSS cages effectively hindered the motion of the polymer chains. TGA confirmed that the thermal degradation temperatures and char yields of the polybenzoxazines increased after incorporation of the POSS moieties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Free‐volume hole properties of two kinds thermoplastic nanocomposites based on polymer blends probed by positron annihilation lifetime spectroscopy

Two type of nanocomposites—an immiscible blend, high density polyethylene/polyamide 6 (HDPE/PA‐6) with organomodified clay, and a compatibilized blend, high density polyethylene grafted with acrylic acid/PA‐6 (PEAA/PA‐6) with organomodified clay—were prepared via melt compounding. X‐ray diffraction and transmission electron microscopy results revealed that the clay was intercalated and partially exfoliated. Positron annihilation lifetime spectroscopy has been utilized to investigate the free‐volume hole properties of two type of nanocomposites. The results show a negative deviation of free‐volume size in PEAA/PA‐6 blend, and a positive deviation in HDPE/PA‐6 blend, and I₃ has a greater negative deviation in compatibilized blend than in immiscible blend due to interaction between dissimilar chains. For nanocomposites based on polymer blends, in immiscible HDPE/PA‐6/organomodified clay system, the variation of free‐volume size with clay content is not obvious and the free‐volume concentration and fraction decreased. While in the case of compatibilized PEAA/PA‐6/organomodified clay nanocomposites, complicated variation of free‐volume properties due to interactions between two phases and organomodified clay was observed. And the interaction parameter β shows the interactions between polymers and organomodified clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2463–2469, 2006     

Crystal structures and their effects on the properties of polyamide 12/clay and polyamide 6–polyamide 66/clay nanocomposites

Both polyamide 12 (PA 12)/clay and polyamide 6–polyamide 66 copolymer (PA 6/6,6)/clay nanocomposites were prepared by melt intercalation. The incorporation of 4–5 wt % modified clay largely increased the strength, modulus, heat distortion temperature (HDT), and permeation resistance to methanol of the polyamides but decreased the notched impact strength. Incorporation of the clay decreased the melt viscosities of both the PA 12 and PA 6/6,6 nanocomposites. Incorporation of the clay increased the crystallinity of PA 6/6,6 but had little effect on that of PA 12, which explained why the clay obviously increased the glass‐transition temperature of PA 6/6,6 but hardly had any effect on that of PA 12. The dispersion and orientation of both the clay and the polyamide crystals were studied with transmission electron microscopy, scanning electronic microscopy, and X‐ray diffraction. The clay was exfoliated into single layers in the nanocomposites, and the exfoliated clay layers had a preferred orientation parallel to the melt flow direction. Lamellar crystals but not spherulites were initiated on the exfoliated clay surfaces, which were much more compact and orderly than spherulites, and had the same orientation with that of the clay layers. The increase in the mechanical properties, HDT, and permeation resistance was attributed to the orientated exfoliated clay layers and the lamellar crystals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4782–4794, 2006     

Effect of clay modification on the morphological,mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 Society of Plastics Engineers     

Effects of polyhedral oligomeric silsesquioxane coatings on the interface and impact properties of carbon‐fiber/polyarylacetylene composites

Two kinds of polyhedral oligomeric silsesquioxane (POSS) coatings were used for the modification of the interface in carbon fiber (CF) reinforced polyarylacetylene (PAA) matrix composites. The effects of the organic–inorganic hybrid POSS coatings on the properties of the composites were studied with short‐beam‐bending, microdebonding, and impact tests. The interlaminar shear strength and interfacial shear strength showed that the POSS coatings resulted in an interfacial property improvement for the CF/PAA composites in comparison with the untreated ones. The impact‐test results implied that the impact properties of the POSS‐coating‐treated composites were improved. The stiffness of the interface created by the POSS coatings was larger than that of the fiber and matrix in the CF/PAA composites according to the force‐modulation‐mode atomic force microscopy test results. The rigid POSS interlayer in the composites enhanced the interfacial mechanical properties with a simultaneous improvement of the impact properties; this was an interesting phenomenon in the composite‐interface modification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5202–5211, 2006     

Synthesis of EP‐POSS mixture and the properties of EP‐POSS/epoxy,SiO2/epoxy,and SiO2/EP‐POSS/epoxy nanocomposite

The hybrid material of EP‐POSS mixture was synthesized by the hydrolysis and condensation of (γ‐glycidoxypropyl) trimethoxysilane. A series of binary systems of EP‐POSS/epoxy blends, epoxy resin modified by silica nanoparticles (SiO₂/epoxy), and ternary system of SiO₂/EP‐POSS/epoxy nanocomposite were prepared. The dispersion of SiO₂ in the matrices was evidenced by transmission electron micrograph, and the mechanical properties, that is, flexural strength, flexural modulus, and impact strength were examined for EP‐POSS/epoxy blends, SiO₂/epoxy, and SiO₂/EP‐POSS/epoxy, respectively. The fractured surface of the impact samples was observed by scanning electron micrograph. Thermogravimetry analysis were applied to investigate the different thermal stabilities of the binary system and ternary system by introducing EP‐POSS and SiO₂ to epoxy resin. The results showed that the impact strength, flexural strength, and modulus of the SiO₂/EP‐POSS/epoxy system increased around by 57.9, 14.1, and 44.0% compared with the pure epoxy resin, T_i, T_max and the residues of the ternary system were 387°C, 426°C, and 25.2%, increased remarkably by 20°C, 11°C and 101.6% in contrast to the pure epoxy resin, which was also higher than the binary systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 810‐819, 2013     

Optimization of melt blending process of nylon 6‐POSS: Improving mechanical properties of spun fibers

Blends of nylon 6 and a silsesquioxane additive, aminopropyl isobutyl POSS containing 2.5% POSS by weight, were melt‐compounded with different process conditions in order to test a previously proposed mechanism for reinforcement of PA6 by POSS. In this work, we proposed that above the POSS melting temperature of 267°C POSS becomes partially soluble in the nylon 6 matrix, leading to smaller domains upon cooling, and the remaining nondiffused POSS agglomerates need to have an acceptable size distribution, typically 16 µm² or less in area. In this work, we test this hypothesis by producing blends with POSS existing as phase‐separated aggregates of even smaller size than before and processing them under various thermomechanical conditions. Although there were no significant differences in the morphology and mechanical properties between the different extruded samples, the results from the spun fibers present significant improvements in tensile properties relative to previous reports. Our results suggest that in order to maximize the tensile strength of melt spun fibers, the extruded blends should be processed at temperatures above the POSS melting temperature and at intermediate shear rates, since these conditions lead to lower debonding between POSS particles and the matrix, and smaller average particle size. POLYM. ENG. SCI., 55:1580–1588, 2015. © 2015 Society of Plastics Engineers     

Modification of cellulose fabrics with reactive polyhedral oligomeric silsesquioxanes to improve their shape‐memory performance

Reactive polyhedral oligomeric silsesquioxane (R‐POSS) containing multi‐N‐methylol is a functional and attractive staring monomer for new reinforcement materials. R‐POSS has excellent potential as a nanosized core for starburst dendrimers and highly reactive multi‐N‐methylol. R‐POSS can be used for cellulose fabric finishing to improve its shape‐memory performance. Factors affecting the crosslinking reaction of the cellulose with R‐POSS were investigated. The physical properties and morphological structure of the cellulose fabrics modified with R‐POSS are discussed with respect to the crease recovery angle, the whiteness index, micro‐Fourier transform infrared spectroscopy, and scanning electron microscopy. The results show that the crease recovery angle of the fabric modified with R‐POSS obviously increased. With increasing R‐POSS concentration, the crease recovery angle of the modified fabric sharply increased. R‐POSS readily crosslinked to cellulose and improved the elastic recovery of the cellulose fabrics. The surfaces of the cellulose fibers modified with R‐POSS were smooth and full. The inclusion of R‐POSS with dimethylol dihydroxyl ethylene urea to modify the cellulose showed very interesting results. It showed a good combination of an increase of crease recovery angle and a decrease in tensile strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010