Temperature‐responsive characteristics of poly(N‐isopropylacrylamide) hydrogels with macroporous structure

Macroporous poly(N‐isopropylacrylamide) (PNIPA) hydrogels were synthesized by free‐radical crosslinking polymerization in aqueous solution from N‐isopropylacrylamide monomer and N,N‐methylenebis (acrylamide) crosslinker using poly(ethylene glycol) (PEG) with three different number‐average molecular weights of 300, 600 and 1000 g mol^?1 as the pore‐forming agent. The influence of the molecular weight and amount of PEG pore‐forming agent on the swelling ratio and network parameters such as polymer–solvent interaction parameter (χ) and crosslinking density (ν_E) of the hydrogels is reported and discussed. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying different molecular weights and compositions of PEG during polymerization. At a temperature below the volume phase transition temperature, the macroporous hydrogels absorbed larger amounts of water compared to that of conventional PNIPA hydrogels, and showed higher equilibrated swelling ratios in aqueous medium. Particularly, the unique macroporous structure provides numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to external temperature changes during the swelling and deswelling process. These macroporous PNIPA hydrogels may be useful for potential applications in controlled release of macromolecular active agents. Copyright © 2006 Society of Chemical Industry     

Semi‐interpenetrating networks based on poly(N‐isopropyl acrylamide) and poly(N‐vinylpyrrolidone)

Three series of novel semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropylacrylamide), PNIPA, and different amounts of the linear poly(N‐vinylpyrrolidone), PVP, were synthesized to improve the mechanical properties and thermal response of PNIPA gels. The effect of the incorporation of the linear PVP into the temperature responsive networks on the temperature‐induced transition, swelling/deswelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with varying molar ratios (25/1 to 100/1) of the monomer (N‐isopropylacrylamide) to the crosslinker (N,N′‐methylenebisacrylamide). The hydrogels were characterized by determination of the equilibrium degree of swelling, the dynamic shear modulus and the effective crosslinking density, as well as tensile strength and elongation at break. Furthermore, the deswelling kinetics of the hydrogels was studied by measuring their water retention capacity. The inclusion of the linear hydrophilic PVP in the PNIPA networks increased the equilibrium degree of swelling. The tensile strength of the semi‐interpenetrating networks (SIPNs) reinforced with linear PVP was higher than that of the PNIPA networks. The elongation at break of these SIPNs varied between 22% and 55%, which are 22 – 41% larger than those for pure PNIPA networks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly (styrene‐n‐butyl acrylate‐methyl methacrylate)/silica nanocomposites prepared by emulsion polymerization

Poly (styrene‐n‐butyl acrylate‐methyl methacrylate) (PSBM)/silica nanocomposite was prepared by emulsion polymerization in the presence of oleic acid surface modified nanosilica. The structure, morphology, size, and size distribution were characterized by Fourier transform infrared (FTIR), transmission electron microscopy (TEM), and dynamics laser scattering. The chemical bond was formed between PSBM and nanosilica revealed by FTIR and TEM studies. The composite particles with an averaged diameter ranging from 30 to 80 nm have the core‐shell structure. The effect of silica content on the glass transition temperature T_g, pyrolyze temperature, and rheological behavior of PSBM composites was systematically investigated. The results indicated that the addition of nanosilica could effectively inhibit chain movement, and improved the pyrolyze temperature of PSBM. The steady viscosity and dynamic modulus were strongly dependent on the content and distribution of nanosilica in PSBM nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,characterization and,swelling behavior of semi‐IPN nanocomposite hydrogels of alginate with poly(N‐isopropylacrylamide) crosslinked by nanoclay

pH and temperature responsive nanocomposite hydrogels were synthesized with sodium alginate (NaAlg), N‐isopropylacrylamide (NIPA), and nanoclay. The structure, morphology, thermal behavior, and swelling and deswelling behaviors of the hydrogels were studied. The NaAlgm/PNIPA/Clayn hydrogels revealed a highly porous structure in which the pore sizes decreased and the amount of pores increased with increasing the nanoclay content in the hydrogels. PNIPA retained its own characteristics regardless of the amount of NaAlg and nanoclay. The effect of pH and nanoclay content on the swelling and effect of temperature on the deswelling behavior were investigated. The equilibrium swelling ratios of the nanocomposite hydrogels increased with increasing the pH from 2 to 6. The maximum swelling was attained at pH 6. Deswelling increased with increasing the nanoclay content in the hydrogels. The hydrogels were found to be pH and temperature responsive. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43222.     

Synthesis and characterization of temperature‐sensitive block copolymers from poly(N‐isopropylacrylamide) and 4‐methyl‐ε‐caprolactone or 4‐phenyl‐ε‐caprolactone

This study synthesizes thermally sensitive block copolymers poly(N‐isopropylacrylamide)‐b‐poly(4‐methyl‐ε‐caprolactone) (PNIPA‐b‐PMCL) and poly(N‐isopropylacrylamide)‐b‐poly(4‐phenyl‐ε‐caprolactone) (PNIPA‐b‐PBCL) by ring‐opening polymerization of 4‐methyl‐ε‐caprolactone (MCL) or 4‐phenyl‐ε‐caprolactone (BCL) initiated from hydroxy‐terminated poly(N‐isopropylacrylamide) (PNIPA) as the macroinitiator in the presence of SnOct₂ as the catalyst. This research prepares a PNIPA bearing a single terminal hydroxyl group by telomerization using 2‐hydroxyethanethiol (ME) as a chain‐transfer agent. These copolymers are characterized by differential scanning calorimetry (DSC), ¹H‐NMR, FTIR, and gel permeation chromatography (GPC). The thermal properties (T_g) of diblock copolymers depend on polymer compositions. Incorporating larger amount of MCL or BCL into the macromolecular backbone decreases T_g. Their solutions show transparent below a lower critical solution temperature (LCST) and opaque above the LCST. LCST values for the PNIPA‐b‐PMCL aqueous solution were observed to shift to lower temperature than that for PNIPA homopolymers. This work investigates their micellar characteristics in the aqueous phase by fluorescence spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS). The block copolymers formed micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range of 0.29–2.74 mg L^?1, depending on polymer compositions, which dramatically affect micelle shape. Drug entrapment efficiency and drug loading content of micelles depend on block polymer compositions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyethylene nanocomposites by gas‐phase polymerization of ethylene in the presence of a nanosilica‐supported zirconocene catalyst system

BACKGROUND: Much of the current research related to the development of in situ nanocomposites of olefins by polymerizing them with metallocenes in the presence of surface‐treated fillers is carried out in the slurry phase. In slurry‐phase methods a large amount of solvent is required and there is always a need of purification of the final product due to the possibility of traces of solvents present in the product. To overcome these drawbacks, to perform solvent‐free metallocene‐catalysed polymerizations with in situ incorporation of inorganic nanoparticles, we have used a gas‐phase polymerization technique as this does not require solvents and also utilizes monomer feed stocks efficiently. RESULTS: The catalyst used for the synthesis of in situ polyethylene nanocomposites by gas‐phase polymerization was nanosilica‐supported zirconocene. The fillers used were Cloisite‐20A, kaolin and nanosilica. Three different in situ polyethylene nanocomposites, i.e. Cloisite‐20A‐filled polyethylene (CFPE), kaolin‐filled polyethylene (KFPE) and nanosilica‐filled polyethylene (SFPE), were prepared by gas‐phase polymerization. The nanocomposites were obtained in the form of fine powder. The polyethylene content in the developed nanocomposites is in the orthorhombic crystalline phase. Using our approach, it is observed that the nanofillers are completely encapsulated by a thin layer of polyethylene. Significantly higher molecular weight polyethylene was formed in the case of KFPE in comparison to CFPE and SFPE. The thermal decomposition temperature, melting temperature and enthalpy are also observed to be higher for KFPE. CONCLUSIONS: The gas‐phase polymerization technique has been successfully carried out for the synthesis of in situ polyethylene nanocomposites. Copyright © 2007 Society of Chemical Industry     

Network parameters and volume phase transition behavior of poly(N‐isopropylacrylamide) hydrogels

Thermosensitive hydrogels were prepared by free radical polymerization in aqueous solution from N‐isopropylacrylamide (NIPA) monomer and N,N‐methylenebis(acrylamide) (MBAAm) crosslinker. The swelling equilibrium of the hydrogels in deionized water was investigated as a function of temperature and MBAAm content. The results indicated that the swelling behavior and temperature sensitivity of the hydrogels were affected by the amount of MBAAm content. The average molecular mass between crosslinks and polymer–solvent interaction parameter (χ) of the hydrogels were determined from equilibrium swelling values. The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. The swelling equilibrium of the hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In deionized water, the hydrogels showed a discontinuous volume phase transition at 32°C. In SDS and DTAB solutions, the equilibrium swelling ratio and the volume phase transition temperature (lower critical solution temperature) of the hydrogels increased, which is ascribed to the conversion of nonionic PNIPA hydrogel into polyelectrolyte hydrogels because of binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method; it was found that the electric conductivity of the PNIPA–surfactant systems depended strongly on both the type and concentration of surfactant solutions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1756–1762, 2006     

PMMA‐grafted‐silica/PVC nanocomposites: Mechanical performance and barrier properties

Poly(vinyl chloride) (PVC)/SiO₂ nanocomposites were prepared via melt mixture using a twin‐screw mixing method. To improve the dispersion degree of the nanoparticles and endow the compatibility between polymeric matrix and nanosilica, SiO₂ surface was grafted with polymethyl methacrylate (PMMA). The interfacial adhesion was enhanced with filling the resulting PMMA‐grafted‐SiO₂ hybrid nanoparticles characterized by scanning electron microscopy. Both storage modulus and glass transition temperature of prepared nanocomposites measured by dynamic mechanical thermal analysis were increased compared with untreated nanosilica‐treated PVC composite. A much more efficient transfer of stresses was permitted from the polymer matrix to the hybrid silica nanoparticles. The filling of the hybrid nanoparticles caused the improved mechanical properties (tensile strength, notched impact strength, and rigidity) when the filler content was not more than 3 wt %. Permeability rates of O₂ and H₂O through films of PMMA‐grafted‐SiO₂/PVC were also measured. Lower rates were observed when compared with that of neat PVC. This was attributed to the more tortuous path which must be covered by the gas molecules, since SiO₂ nanoparticles are considered impenetrable by gas molecules. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of porous poly(N‐isopropylacrylamide) gel beads by sedimentation polymerization and their morphology

Sedimentation polymerization of aqueous solutions of N‐isopropylacrylamide (NIPA) was carried out to prepare porous poly(N‐isopropylacrylamide) (PNIPA) beads. When small amounts of DMF and a radical accelerator were added to the monomer solution, the polymerization proceeded smoothly to give polymer beads with a very narrow size distribution. The rate of swelling of the resulting bead increased with increasing crosslinker content and was also affected by the type of crosslinker used. When amounts higher than 1 mol % N,N′‐methylenebisacrylamide or 3 mol % diethylene glycol diacrylate (DEGDA) were used as a crosslinker, the resulting beads underwent rapid swelling in water at 20°C, reaching the equilibrium within 5 min. A cross‐sectional photograph of a typical dried bead showed that it had a very complex morphology consisting of a large and irregular void, highly porous region, and nonporous region. The swelling rate was directly dependent on the morphology of the beads. PNIPA beads with well‐developed porous areas show a high swelling rate. Although PNIPA beads produced from DEGDA had well‐developed porous structures, they were able to effectively concentrate blue dextran from the dilute aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 842–850, 2007     

Synthesis and characterization of nylon‐6/mesoporous silica nanocomposites via in situ synchronous hydrolytic polymerization of tetraethylorthosilicate and ε‐caprolactam

Nylon 6 (N6)/mesoporous silica (MS) nanocomposites (NMSNs) were synthesized via in situ synchronous hydrolytic polymerization of tetraethylorthosilicate (TEOS) and ε‐caprolactam. The novelty of this technique lies in that the nanosilica generated in situ has unique mesoporous structure and ultrahigh‐specific surface area (SSA). Mechanical test showed that, compared to conventional precipitated silica (PS) nanofillers, the MS generated in situ shows better reinforcing efficiency on N6. At a loading of only 3.0 wt % MS, the tensile modulus, flexural modulus, and the heat distortion temperature of NMSNs exhibit increase of 54.8%, 77.9%, and 55.9°C, respectively. The effects of MS on the crystallization behaviors of N6 have been studied by differential scanning calorimetry (DSC), which shows that the incorporation of MS influences the crystallization behaviors of N6 obviously: (1) increases crystallization temperature (T_c) by serving as heterogonous nucleating agent; (2) favors the formation of γ‐phase by hindering the mobility of N6 chains. Dynamic mechanical analysis confirmed that, compared ti that of neat N6, the temperature of the main α‐relaxation (T_α) and the secondary β‐relaxation (T_β) of NMSNs is shifted 6.1°C and 5.3°C toward higher temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Property modulation of poly(N‐isopropylacrylamide) hydrogels by incorporation of modified silica

Poly(N‐isopropylacrylamide) (PNIPA)/silica composite hydrogels were prepared and the effects of the silica incorporation on the swelling and breaking characteristics of the hydrogels were investigated. To improve the dispersive property of silica in the PNIPA matrix via the formation of covalent bonds between the polymer and silica, vinyl groups were introduced in the silica by reacting it with a coupling agent, 3‐methacryloxypropyltrimethoxysilane. When unmodified silica was used as filler in the PNIPA‐composite hydrogel, the swelling ratio of the composite hydrogel below the critical gel transition temperature (CGTT) increased with increasing silica content. However, when the modified silica was used as the filler, the swelling ratio below CGTT decreased with increasing silica content because of the enhanced distribution and additional crosslinking. Above CGTT, the swelling ratios of the PNIPA/silica hydrogels were similar regardless of the silica modification. The gel breaking stress of the hydrogels increased with increasing silica content, and this enhancement was larger for the modified silica hydrogel. Scanning electron microscopy images showed that the modified silica particles were distributed more evenly in the PNIPA matrix than the unmodified ones were and that the size of cell‐like structure of the hydrogel decreased with increasing modified silica content. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Macroporous poly(N-isopropylacrylamide) networks

Summary Effects of the gel preparation temperature T _prep and the initial monomer concentration c on the swelling and the porosity properties of poly(N-isopropylacrylamide) (PNIPA) networks are described. PNIPA networks were prepared by free-radical crosslinking copolymerization of N-isopropylacrylamide and N,N'-methylene(bis)acrylamide (BAAm) in aqueous solutions. The crosslinker (BAAm) concentration in the initial monomer mixture was kept constant at 30 wt %. It was shown that macroporous PNIPA networks with a stable porous structure can be prepared at T _prep = 22.5°C and at an initial monomer concentration c > 5 w/v %. The PNIPA networks contain pores of about 0.1 μm in radius, corresponding to the interstices between the microspheres. The experimental data also show collapse of the porous structure in PNIPA networks formed at higher temperatures. Received: 30 January 2002 / Revised version: 16 May 2002 / Accepted: 1 June 2002     

Thermomechanical properties of styrene‐butyl acrylate/organo‐silica nanocomposite films prepared by seed emulsion polymerization

Organo‐silica nanoparticles were prepared by sol–gel technique of triethoxyvinylsilane (VTES) in aqueous solution. The vinyl groups located on the surface of organo‐silica were used to induce the polymerization process and the encapsulation into styrene‐butyl acrylate copolymer emulsion. The prepared latex samples were characterized using FTIR, ¹HNMR, UV–visible, thermal analysis, field emission‐SEM and TEM. Results of TGA revealed that nanosilica has retarded the decomposition of nanocomposite polymers with at least 10°C higher than that of pure emulsions. DSC has shown an increase in the nanosilica ratio up to 5% which leads to a dramatic decrease in the glass transition (T _g) of nanocomposite polymer due to the formation of silica nanoparticles homopolymer. DMTA results indicated that the storage modulus of pure polymer is less than nanocomposite, which proves the reinforcing role of nanosilica in the matrix of polymer. Water resistance and UV‐blocking ability have improved by introducing the nanosilica into the matrix of prepared polymer. POLYM. COMPOS., 38:61–67, 2017. © 2015 Society of Plastics Engineers     

Swelling characteristics of thermo‐ sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] porous hydrogels

Temperature‐sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] [P(DEAEMA‐co‐DMAAm)] hydrogels with five different DMAAm contents were synthesized with and without the addition of sodium carbonate as porosity generator. The synthesized hydrogels were characterized with dry gel density measurements, scanning electron microscopy observation and the determination of swelling ratio. The influence of the pore‐forming agent and content of DMAAm on swelling ratio and network parameters such as polymer–solvent interaction parameter (χ), average molecular mass between crosslinks (M?_c) and mesh size (ζ) of the cryogels are reported and discussed. The swelling and deswelling rates of the porous hydrogels are much faster than for the same type of hydrogels prepared via conventional methods. At a temperature below the volume phase transition temperature, the macroporous hydrogels also absorbed larger amounts water compared to that of conventional hydrogels and showed obviously higher equilibrated swelling ratios in aqueous medium. In particular, the unique macroporous structure provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to the external temperature changes during the deswelling and swelling processes. These properties are attributed to the macroporous and regularly arranged network of the porous hydrogels. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying porosity generation methods during the polymerization reaction. Copyright © 2007 Society of Chemical Industry     

Radiation polymerization and concentration separation of P(NIPA‐co‐AMPS) hydrogels

Extraction or concentration with temperature‐sensitive hydrogels is a novel separation technology. In this study, N‐isopropylacrylamide (NIPA) was synthesized by acrylonitrile and isopropanol. Poly(N‐isopropylacrylamide) (PNIPA) and copolymer of NIPA and 2‐acrylamide‐2‐methylpropane sulfonate [P(NIPA‐co‐AMPS)] hydrogels were prepared by radiation polymerization. Dependence of their swelling behavior on temperature was studied. Effects of radiation dose on polymerization, feed composition on thermoresponse, electrolyte on relative swelling ratio, and swelling and deswelling kinetics were investigated. The experimental results showed that P(NIPA‐co‐AMPS) hydrogels with low content of AMPS/NIPA (1–5 %), prepared at a radiation dose‐rate of 1 kGy/h and total dose of 30–40 kGy, could enhance the swelling ratio of PNIPA hydrogels significantly and raise the phase‐transition temperatures. P(NIPA‐co‐AMPS) hydrogels produced under optimum conditions were used to concentrate aqueous bovine serum albumin (BSA, M = 69 000 g mol^?1) solution. When aqueous BSA concentration was below 5 %, the separation efficiency was more than 80 % with low cost and low energy consumption. Copyright © 2005 Society of Chemical Industry     

Synthesis,characterization, mechanical properties and biocompatibility of interpenetrating polymer network–super‐porous hydrogel containing sodium alginate

In this investigation an interpenetrating polymer network–superporous hydrogel containing sodium alginate (IPN‐SPH_Alg) was synthesized. The morphology of the polymer was characterized using scanning electron microscopy, light images and porosity, and the polymer was further examined by swelling ratio, mechanical strength and biocompatibility. The results indicated that the IPN‐SPH_Alg possessed both large numbers of interconnected pores and an interpenetrating network. The swelling ratio of IPN‐SPH_Alg was lower than that of the superporous hydrogel (SPH) and it decreased as the sodium alginate/monomer ratio increased. The IPN‐SPH_Alg exhibited pH responsiveness and salt‐sensitive properties. Compared to SPH and SPH composites, the mechanical strength of IPN‐SPH_Alg was significantly enhanced. Thiazolyl blue assay on AD293 cells, in situ lactate dehydrogenase assay and morphological study of rat intestine showed that the polymer induced no significant cell or mucosal damage. The fast swelling, good mechanical properties, pH sensitivity and biocompatibility of the IPN‐SPH_Alg suggested it as a potential candidate in the field of drug‐delivery systems. Copyright © 2007 Society of Chemical Industry     

High strength thermoresponsive semi‐IPN hydrogels reinforced with nanoclays

Two series of nanoclay reinforced, thermoresponsive hydrogels were prepared, one based on poly(N‐isopropylacrylamide) (PNIPA) and the other on semi‐interpenetrating networks containing PNIPA and poly(N‐vinyl pyrrolidone) (PVP), designated as SIPNs. The gels were crosslinked with 1, 3, and 5 wt % inorganic clay (hectorite) and SIPN gels additionally contained 1 wt % of PVP. The hydrogels were tested in the “as‐prepared state,” i.e., at 10 wt % PNIPA concentration in water and at equilibrium (maximum) swelling. Increasing the concentration of nanoclays increases crosslink density, modulus, tensile strength, elongation (except in equilibrium swollen gels), hysteresis and with decreases in the degree of swelling, broadening of the phase transition region, and a decrease in elastic recovery at high deformations. The presence of linear PVP in the networks increases porosity and the pore size, increases swelling, deswelling rates, and hysteresis, but decreases slightly lower critical solution temperature (LCST), tensile strength, elongation, and elastic recovery. The strongest hydrogels were ones with 10 wt % PNIPA and 5 wt % of nanoclays, displaying tensile strengths of 85 kPa and elongation of 955%. All properties of hydrogels at the equilibrium swollen state are lower than in the as‐prepared state, due to the lower concentration of chains per unit volume, but the trends are preserved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Frontal polymerization preparation of poly(acrylamide‐co‐acrylic acid)/activated carbon composite hydrogels for dye removal

A series of poly(acrylic acid‐co‐acrylamide) (PAA)/activated carbon (AC) composite hydrogels were rapidly prepared via frontal polymerization (FP). It was found that an increase in the concentration of AC caused an increase in the front velocity (V_f) and the highest front temperature (T_max). It may be attributed to that AC particles could increase the liquid viscosity of reaction mixture and remain the reaction heat during FP. The Fourier transform infrared and scanning electron microscopy (SEM) confirmed that AC particles had entered the hydrogel network, and many spherical AC particles with an average diameter of 0.5–1 μm had been dispersed homogeneously in the PAA hydrogel matrix. The swelling behavior showed that the equilibrium swelling values of hydrogels increased when the concentration of AC particles increased. Adsorption studies showed that incorporation of AC particles into PAA hydrogel matrix could increase the sites of interaction between the hydrogels and crystal violet molecules and result in an increase of adsorption capacities of hydrogels toward dyes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of high nano‐SiO2 contents on properties of epoxy‐modified polybenzoxazine

High‐performance nanosilica composites based on epoxy‐modified polybenzoxazine matrices are developed. Chemorheological study of benzoxazine–epoxy resin mixtures reveals that processing window of the benzoxazine resin (BA‐a) is substantially broadened with an addition of the liquid epoxy. Glass transition temperature (T _g) of the BA‐a copolymerized with epoxy resin shows a synergistic behavior with a maximum T _g value (174°C) at the benzoxazine–epoxy mass ratio of 80:20. The copolymer at this composition is also used as a matrix for nano‐SiO₂ composites. A very low melt viscosity of the benzoxazine–epoxy mixtures promotes good processability with the maximum attainable nano‐SiO₂ loading up to 35 wt%. From scanning electron microscopy investigation, fracture surface of the 35 wt% nano‐SiO₂‐filled benzoxazine–epoxy composite reveals relatively homogeneous distribution of the nano‐SiO₂ in the copolymer with good particle wet‐out. In addition, very high reinforcing effect was also observed in such high content of the nano‐SiO₂, i.e., about 2.5 times in modulus improvement. This improvement is attributed to the strong bonding between the copolymer matrix and the nano‐SiO₂ through ether linkage as confirmed by Fourier‐transform infrared investigation. POLYM. COMPOS., 38:2261–2271, 2017. © 2015 Society of Plastics Engineers     

Synthesis and properties of polystyrene‐g‐mSiO2 filled polypropylene nanocomposites

Hydrophobically modified nanosilica was prepared from tetraethoxysilane (TEOS) and γ‐methacryloxypropyltrimethoxysilane (MPS) by a two step sol‐gel process. The polystyrene‐grafted‐modified nanosilica (PS‐g‐mSiO₂) hybrid particles were prepared by grafting polystyrene onto the resulting hydrophobically modified nanosilica by dispersion polymerization. The hybrid nanoparticles were subsequently used as the filler to fabricate polypropyrene (PP) nanocomposites. The crystallization kinetics, crystal morphology and crystallization phase component of PS‐g‐mSiO₂/PP nanocomposite were studied using a differential scanning calorimeter (DSC), polarizing optical microscopy (POM) and X‐ray diffraction (XRD). Crystallization half life (t_1/2) decreased, while the Arami exponent (n) of PS‐g‐mSiO₂/PP nanocomposite increased compared with that of virgin PP. A rheological study allowed the unambiguous characterization of the dispersibility of nanosilicas in PS‐g‐mSiO₂/PP nanocomposite. The storage modulus, melt viscosity and the elongation to break of the PS‐g‐mSiO₂/PP nanocomposite were found to be strongly dependent on the grafting of PS on nanosilicas. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers