Synthesis and characterization of poly(styrene‐co‐butyl acrylate)/clay nanocomposite latexes in miniemulsion by AGET ATRP

Polymer/clay nanocomposite latexes in the form of positively charged nanoparticles were synthesized by a newly developed initiating system, activators generated by electron transfer (AGET), which has been employed in atom transfer radical polymerization (ATRP). These clay‐dispersed latexes were synthesized using AGET ATRP of styrene and butyl acrylate in a miniemulsion system in which, ascorbic acid as a reducing agent was added drop wise to reduce termination reactions. Particle size and particle size distribution of resulted nanocomposite latexes were characterized by dynamic light scattering (DLS). These latexes were in the range of 138 to 171 nm in size. Gel permeation chromatography (GPC) was used to characterize the molecular weight and molecular weight distribution of the resultant copolymer nanocomposites. GPC traces showed that polymers of narrow molecular weight distribution and low Polydispersity Index (PDI) have been synthesized; this clearly shows ATRP reaction is conducted successfully. By increasing nanoclay content, molecular weight of the nanocomposites decreases. The presence of the nanofiller increases the thermal stability of the nanocomposites as investigated by thermogravimetric Analysis (TGA). Glass transition temperature of nanocomposites increases compared with the neat copolymer which was studied by differential scanning calorimetry (DSC). scanning electron microscope (SEM) showed sphere morphology of polymer particles synthesized by miniemulsion polymerization. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that mixed intercalated and exfoliated morphology is obtained. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Synthesis of clay‐dispersed poly(styrene‐co‐methyl methacrylate) nanocomposite via miniemulsion atom transfer radical polymerization: A reverse approach

Poly(styrene‐co‐methyl methacrylate) nanocomposites were synthesized using reverse atom transfer radical polymerization (RATRP) in miniemulsion. Cetyltrimethylammonium bromide (CTAB) as a cationic surfactant applicable at higher temperatures was used for miniemulsion stabilization. Successful RATRP was carried out by using 4,4′‐dinonyl‐2,2′‐bipyridine (dNbPy) as ligand. Monodispersed droplets and particles with sizes in the range of 200 nm were revealed by dynamic light scattering (DLS). Conversion and molecular weight study was carried out using gravimetry and size exclusion chromatography (SEC) respectively. By adding clay content, a decrease in the conversion and molecular weight and an increase in the PDI value of the nanocomposites are observed. Thermal stability of the nanocomposites in comparison with the neat copolymer is revealed by thermogravimetric analysis (TGA). Increased T_g values by adding clay content was also obtained using differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) images of the nanoconposite with 1 wt % of nanoclay loading, display monodispersed spherical particles with sizes in the range of ～ 200 nm. SEM findings are more compiled with dynamic light scattering (DLS) results. Well‐dispersed exfoliated clay layers in the polymer matrix of the nanocomposite with 1 wt % nanoclay loading is confirmed by transmission electron microscopy (TEM) images and X‐ray diffraction (XRD) data. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nanoclay‐encapsulated polystyrene microspheres by reverse atom transfer radical polymerization

Nanoclay‐encapsulated polystyrene microspheres were synthesized using reverse atom transfer radical polymerization in miniemulsion. Conversion and molecular weight were evaluated using gravimetry and gel permeation chromatography, respectively. Accordingly, conversion and molecular weight decrease by adding clay content. However, polydispersity index of the nanocomposites with higher clay content is higher. At high temperatures, thermal stability of the nanocomposites is relatively higher than the neat polystyrene, according to the thermogravimetric analysis results. Differential scanning calorimetry results show that glass transition temperature decreases by increasing clay content. Transmission electron microscopy result is in coincidence with X‐ray diffraction data and shows that clay layers are exfoliated in the matrix of PSNM 1. Scanning electron microscopy images display a homogeneous distribution of spherical particles with sizes in the range of ∼200 nm and also confirm dynamic light scattering (DLS) results. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Encapsulation of organomodified montmorillonite with PMMA via in situ SR&;NI ATRP in miniemulsion

Encapsulation of organomodified montmorillonite within poly (methyl methacrylate) via in situ atom transfer radical polymerization with simultaneous reverse and normal initiation system (SR&NI ATRP) was successfully performed. Miniemulsion polymerization technique has been employed for its abundant advantages to encapsulate inorganic materials. Successful SR&NI ATRP was carried out using 4,4′-dinonyl-2,2′-bipyridine (dNbPy) as a hydrophobic ligand and cetyltrimethylammonium bromide (CTAB) as an effective cationic surfactant at high temperatures. Homogeneous distribution of droplets and particles with sizes in the range of around 170 nm was evaluated by dynamic light scattering (DLS) analysis. Final monomer conversion and molecular weight were determined by gravimetry and size exclusion chromatography (SEC) respectively. By increasing nanoclay content, conversion and molecular weight of nanocomposites decreased. Meanwhile, an increase in PDI values was also observed. X-ray diffraction (XRD) analysis results display organoclay layers disordered and delaminated in the polymer matrix. Thermal stability improvement of all the nanocomposites in comparison with the neat polymer was revealed by thermogravimetric analysis (TGA). Homogeneous distribution of spherical particles with sizes in the range of 170 nm was demonstrated by scanning electron microscopy (SEM) images. These results are complied with the DLS results. Transmission electron microscopy (TEM) image display a dispersion of partially exfoliated clay stacks in the matrix of PMNM 2.     

Use of clay-anchored reactive modifier for the synthesis of poly (styrene-co-butyl acrylate)/clay nanocomposite via in situ AGET ATRP

Atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) was employed to synthesize well-defined poly (styrene-co-butyl acrylate)/clay nanocomposites. Dodecyltrimethylammonium bromide (DDTMAB) and Vinylbenzyltrimethylammonium chloride (VBTMAC) surfactants were used as clay modifier. The classical surfactant is used to expand the interlayer gallery of montmorillonite; however, double bond of reactive modifier participates in chain propagation process and forms clay-attached polymer chains. Subsequently synthesis of attached and free poly (styrene-co-butyl acrylate) chains and their composition was confirmed by Fourier-transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance spectroscopy (¹H NMR). Narrow distribution of nanocomposites molecular weight was confirmed by gel permeation chromatography (GPC). Partially exfoliated clay layers in the copolymer matrix were revealed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal properties of the nanocomposites were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Thermal decomposition of the nanocomposites was hindered in the presence of nanoclay. Dynamic mechanical thermal analysis (DMTA) results show that addition of nanoclay was also resulted in enhanced storage modulus (E′) in comparison with the neat copolymer. Lower glass transition temperature of nanocomposites was displayed by DSC.     

Preparation of tailor‐made polystyrene nanocomposite with mixed clay‐anchored and free chains via atom transfer radical polymerization

Tailor‐made polystyrene nanocomposite with mixed free and clay‐attached polystyrene chains was synthesized using atom transfer radical polymerization. Vinylbenzyl trimethylammonium chloride having a double bond, which could be incorporated into polystyrene chains by a grafting through process, was used as a nanoclay modifier. Conversion and molecular weight evaluation was carried out using gas chromatography and gel permeation chromatography, respectively. The thermogravimetric analysis results confirmed the elevated thermal stability of the nanocomposites in comparison with the neat polystyrene sample. Additionally, the T_g increases by clay loading was confirmed by differential scanning calorimetry (DSC). The difference in the degradation temperature of C? Br bond in attached and free polystyrene chains was well revealed in DSC thermograms. Finally, a lower clay loading resulted in an exfoliated structure as proved by X‐ray diffraction and transmission electron microscopy results. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Preparation of nanoclay‐dispersed polystyrene nanofibers via atom transfer radical polymerization and electrospinning

In this study, clay‐dispersed polystyrene (PS) nanocomposites were prepared with the in situ atom transfer radical polymerization method and were subsequently electrospun to form nanofibers 450–650 nm in diameter. The polymer chains extracted from the clay‐dispersed nanofibers exhibited a narrow range of molecular weight distribution. Thermogravimetric analysis (TGA) confirmed a higher thermal stability of the resulting nanocomposites compared to PS. The effect of the weight ratio of montmorillonite on the thermal properties of the nanocomposites was also studied by TGA. Differential scanning calorimetry revealed that the addition of the nanoclay increased the glass‐transition temperature. Moreover, degradation of the bromide chain‐end functionality took place at low temperatures. Scanning electron microscopy showed that the average diameter of the fibers was around 500 nm. The dispersion of clay layers was also evaluated by Al atoms in the PS matrix with the energy‐dispersive X‐ray detection technique. Transmission electron microscopy confirmed the exfoliation of the nanoclay within the matrix. However, the clay layers were oriented along the nanofiber axis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of clay dispersed polystyrene nanocomposite via atom transfer radical polymerization

Finely well‐defined polystyrene nanocomposites were prepared by ATRP method in bulk at 110°C using organically modified montemorillonite, cloisite 30B. The living nature of ATRP reaction was employed to in situ synthesize tailor‐made polystyrene nanocomposite with narrow molecular weight distribution and controlled molecular weight polystyrene chains. The amount of clay loading and time of swelling of clay in the monomer before polymerization were proved to have a positive effect on polymerization rate and also broadened the molecular weight destribution. The gas chromatography (GC) results showed the linear increase of Ln(M₀/M) versus time, which indicates the controlled/living polymerization in the presence of nanoclay. Another confirmation of the living nature of the polymerization was linear elevation of molecular weight against monomer conversion concluded from gel permeation chromatography (GPC) data. X‐ray diffraction analysis showed the interlayer spacing of nanoclay platelets as well as the exfoliated clay morphology in the nanocomposite samples. Transfer electron microscopy (TEM) revealed the exfoliated morphology of the in situ prepared nanocomposite as opposed to conventional solution‐blending technique which resulted in an intercalated structure. The effect of nanoclay on acceleration of polymerization was proved by GC and GPC; similarly, Fourier transform infrared spectroscopy (FTIR) was used to discuss the reasons of such a rate acceleration. A shifting in the wave number of characteristic bonds of nanoclay after polymerization mostly in the case of O H and Si O bonds, revealed the interaction between polymer chains and clay layers which resulted in an accelerated polymerization process. The living nature of polymeric chains was more elucidated by FTIR data. Atomic force microscopy (AFM) images also confirmed the proper dispersion of nanoparticles in the polymer medium. POLYM. COMPOS., 31:1829–1837, 2010. © 2010 Society of Plastics Engineers     

Evaluation of the confinement effect of nanoclay on the kinetics of styrene atom transfer radical polymerization

The grafting through method was employed to study the effect of nanoclay confinement on the atom transfer radical polymerization (ATRP) of styrene. An ammonium salt containing a double bond on its structure was used as a clay modifier. Employing ATRP to polymerize styrene in the presence of modified montmorillonite resulted in a finely well‐defined polystyrene nanocomposite. The gas chromatography (GC) results showed the linear increase of ln(M₀/M) versus time, which indicated the controlled behavior of the polymerization. Another confirmation of the living nature of the polymerization was the linear increase of molecular weight against monomer conversion concluded from the gel permeation chromatography (GPC) data. Nanoclay exerted acceleration on the polymerization of free polystyrene chains. The polydispersity indexes of polymer chains increased by the addition of nanoclay. In the case of clay‐attached polystyrene chains, number and weight‐average molecular weights were lower than that of freely dispersed polystyrene chains. The polydispersity index of the clay‐attached chains was higher in respect to the freely dispersed polystyrene chains. The living nature of polymer chains was more elucidated by Fourier transform infrared spectroscopy (FTIR). Exfoliation of the clay layers in the polymer matrix of polystyrene nanocomposite containing the lowest amount of nanoclay has proven by Transmission Electron Microscopy (TEM). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterizations of poly(α‐naphthylamine)—Nanocomposites

Poly(α‐naphthylamine) (PNA)—natural clay nanocomposites were prepared by in situ polymerization method through oxidative initiation method. Effect of nanoclay on the rate of polymerization (R_p) of Naphthylamine (NA), thermal stability of PNA, and conductivity of PNA were tested. Effect of nanoclay on the morphology of PNA was also tested. The TGA results inferred that the % weight residue remain above 700°C was increased with the increase of amount of clay. XRD results confirmed the intercalation of PNA into the basal spacing of natural clay. TEM showed the presence of nanosized particle in the PNA‐natural clay nanocomposites. The conductivity value of polymer‐nanocomposite has increased with the increase of amount of natural clay. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of PLLA‐PEOMA comb‐block‐comb type molecular brushes based on AGET ATRP and ring‐opening polymerization

BACKGROUND: Molecular brushes are types of macromolecules with densely grafted side chains on a linear backbone. The synthesis of macromolecular brushes has stimulated much interest due to their great potential in applications in various fields. Poly(L ‐lactide)–poly(ethylene glycol) methyl ether methacrylate (PLLA‐PEOMA) comb‐block‐comb molecular brushes with controlled molecular weights and narrow molecular weight distributions were successfully synthesized based on a combination of activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP) and ring‐opening polymerization. The synthetic route is a combination of the ‘grafting through’ method for AGET ATRP of the PEOMA comb block and the ‘grafting from’ method for the synthesis of the PLLA comb block. Poly(2‐hydroxyethyl methacrylate) (PHEMA) was synthesized by ATRP, and PLLA side chains and PEOMA side chains were grown from the backbones and the terminal sites of PHEMA, respectively. RESULTS: The number‐average degrees of polymerization of PLLA chains and poly[poly(ethylene glycol) methyl ether methacrylate] (PPEOMA) comb blocks were determined using ¹H NMR spectroscopy, and the apparent molecular weights and molecular weight distributions of the brush molecules were measured using gel permeation chromatography. The crystallization of the components in the comb‐block‐comb copolymers was also investigated. The crystallization of PLLA side chains is influenced by PLLA chain length and the content of PPEOMA in the molecular brushes. The comb‐block‐comb copolymer composed of hydrophobic PLLA and hydrophilic PEOMA can self‐assemble into a micellar structure in aqueous solution. CONCLUSION: A combination of AGET ATRP and ring‐opening polymerization is an efficient method to prepare well‐defined comb‐block‐comb molecular brushes. The physical properties of the molecular brushes are closely related to their structures. Copyright © 2009 Society of Chemical Industry     

Preparation of polyacrylate‐clay nanocomposites by in‐situ polymerization and heterocoagulation

Polyacrylate‐clay nanocomposites were prepared by an in situ polymerization method followed by heterocoagulation. In the heterocoagulation method, a cationic polyacrylate emulsion was prepared by emulsion polymerization using a cationic initiator in the presence/absence of free surfactant, cetyl trimethylammonium bromide (CTABr), followed by mixing with an aqueous clay slurry. WAXD results and TEM images suggest that morphologies of these nanocomposites depend on preparation method, mixing method, and the amount of free surfactant. TG‐DTG analyses demonstrate the improvement in thermal stability of these nanocomposites, while DSC results indicate no significant changes in glass transition temperature of these nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3850–3855, 2006     

Preparation of thermoplastic elastomer nanocomposites based on polyamide‐6/polyepichlorohydrin‐co‐ethylene oxide

This work is aimed at determining the effect of nanoclay and polyepichlorohydrin‐co‐ethylene oxide (ECO) content on the microstructure and mechanical properties of PA6/ECO thermoplastic elastomers (TPEs). TPE nanocomposites were prepared in a laboratory mixer using polyamide 6 (PA6), ECO, and an organoclay by a two‐step melt mixing process. First, the PA6 was melt blended with Cloisite 30B and then mixed by ECO rubber. X‐ray diffraction results and transmission electron microscopy image showed that the nanoclay platelets were nearly exfoliated in both the phases. The SEM photomicrograph of PA6 with ECO showed that the elastomer particles are dispersed throughout the polyamide matrix and the size of rubber particles is less than 3 μm. Introduction of organoclay in the PA6 matrix increased the size of dispersed rubber particles in comparison with the unfilled but otherwise similar blends. The nanoscale dimension of the dispersed clay results in an improvement of the tensile modulus of the nanocomposites. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Synthesis and characterization of chlorine‐containing flame‐retardant polyurethane nanocomposites via in situ polymerization

We have developed flame‐retardant polyurethanes (FRPUs) and polyurethane (PU) nanocomposites via in situ polymerization. Three series of thermoplastic elastomeric PUs were synthesized to investigate the effect of incorporating 3‐chloro‐1,2‐propanediol (CPD) and nanoclay on mechanical, thermal properties, and also resistance to burning. PU soft segments were based on poly(propylene glycol). Hard segments were based on either CPD or 1,4‐buthane diol (BDO) in combination with methyl phenyl di‐isocyanate named PU or FRPU, respectively. In the third series, CPD was used as chain extender also nanoclay (1% wt) and incorporated and named as flame‐retardant polyurethane nanocomposites (FRPUN). Mechanical properties and LOI of PUs and nanocomposites have been evaluated. Results showed that increasing the hard segment (chlorine content) leads to the increase in flame retardancy and burning time. Addition of nanoclay to CPD‐containing PUs leads to obtain self‐extinguish PUs using lower CPD contents, higher Young's modulus, and strength without any noticeable decrease in elongation at break. Investigation of the TGA results showed that copresence of nanoclay and chlorine structure in the PU backbone can change thermal degradation pattern and improve nanocomposite thermal stability. X‐ray diffraction and transmission electron microscopy studies confirmed that exfoliation and intercalation have been well done. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical,thermal and dynamic‐mechanical behavior of banana fiber reinforced polypropylene nanocomposites

Natural fiber‐reinforced nanocomposites based on polypropylene/nanoclay/banana fibers were fabricated by melt mixing in a twin‐screw extruder followed by compression molding in this current study. Maleic anhydride polypropylene copolymer (MA‐g‐PP) was used as a compatibilizer to increase the compatibility between the PP matrix, clay, and banana fiber to enhance exfoliation of organoclay and dispersion of fibers into the polymer matrix. Variation in mechanical, thermal, and physico‐mechanical properties with the addition of banana fiber into the PP nanocomposites was investigated. It was observed that 3 wt% of nanoclay and 5 wt% of MA‐g‐PP within PP matrix resulted in an increase in tensile and flexural strength by 41.3% and 45.6% as compared with virgin PP. Further, incorporation of 30 wt% banana fiber in PP nanocomposites system increases the tensile and flexural strength to the tune of 27.1% and 15.8%, respectively. The morphology of fiber reinforced PP nanocomposites has been examined by using scanning electron microscopy and transmission electron microscopy. Significant enhancement in the thermal stability of nanocomposites was also observed due to the presence of nanoclay under thermogravimetric analysis. Dynamic mechanical analysis tests revealed an increase in storage modulus (E′) and damping factor (tan δ), conforming the strong interaction between nanoclay/banana fiberand MA‐g‐PP in the fiber‐reinforced nanocomposites systems. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Rheological properties of poly(acrylonitrile‐co‐methyl acrylate)/clay nanocomposites prepared via emulsion polymerization

Poly(acrylonitrile‐co‐methyl acrylate)/clay nanocomposites were prepared by free radical polymerization in emulsion using 2‐acrylamido‐2‐methyl‐1‐propanesulphonic acid (AMPS) as a compatibilizer. The resultant nanocomposites were of partially exfoliated morphology despite the variations in clay content among the nanocomposites, as confirmed by transmission electron microscopy and small‐angle X‐ray scattering analysis. Rheological studies of these materials were carried out using parallel plate geometry. The storage modulus increased monotonically with increasing clay content throughout the frequency range studied. However, the neat copolymer, poly(acrylonitrile‐co‐methyl acrylate) and its nanocomposites, exhibited long relaxation behavior as the storage modulus (G′) was greater than the loss modulus (G″) throughout the angular frequency range studied. The complex viscosity of the nanocomposites increased with increasing clay content and they exhibited shear‐thinning behavior. Despite the enhanced rheological properties observed, the copolymer and its nanocomposites underwent structural changes during oscillatory measurements due to cyclization reactions. POLYM. COMPOS., 32:59–66, 2011. © 2010 Society of Plastics Engineers     

Kinetic studies of the preparation of nanocomposites based on encapsulated Cloisite 30B in poly[styrene‐co‐(butyl acrylate)] via mini‐emulsion polymerization

Mini‐emulsion polymerization of poly[styrene‐co‐(butyl acrylate)] encapsulating various contents of Cloisite 30B was performed. The kinetic behaviours of mini‐emulsions were investigated using the gravimetric method and the effect of nanoclay content on the polymerization rate was investigated. The average number of radicals per particle was estimated by calculating the number of particles. The results showed that by increasing the nanoclay content, the average diameter of polymer particles increased. Studies of the polymerization rate indicated that the increase in particle size provided a greater average number of reactive radicals per polymer particle, which increased from 0.0520 for the neat copolymer to 0.2462 for the nanocomposite containing 5.3 wt% encapsulated nanoclay. This study also confirmed our previous claim about the role of sodium dodecylsulfate (SDS) molecules in the exfoliation of nanoclay platelets. On increasing the clay content, fewer SDS molecules will be available on particle surfaces resulting in larger particles at the end of the reaction. Copyright © 2011 Society of Chemical Industry     

Functionalization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) films via surface‐initiated atom transfer radical polymerization: Comparison with the conventional free‐radical grafting procedure

We modified hydrophobic poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBHV) films with hydrophilic chains to control their surface properties. We designed and investigated surface‐initiated atom transfer radical polymerization (SI‐ATRP) to modify the PHBHV films by grafting poly(2‐hydroxyethyl methacrylate) (PHEMA) from the surface. This method consisted of two steps. In the first step, amino functions were formed on the surface by aminolysis; this was followed by the immobilization of an atom transfer radical polymerization initiator, 2‐bromoisobutyryl bromide. In the second step, the PHEMA chains were grafted to the substrate by a polymerization process initiated by the surface‐bound initiator. The SI‐ATRP technique was expected to favor a polymerization process with a controlled manner. The experimental results demonstrate that the grafting density was controlled by the reaction conditions in the first step. The grafted films were analyzed by Fourier transform infrared spectroscopy, contact angle testing, scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy. The results show that grafted chains under the SI‐ATRP method were preferentially located on the surface for surface grafting and in the bulk for conventional free‐radical polymerization initiated by benzoyl peroxide. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of poly(ε‐caprolactone)/clay nanocomposites using polyhedral oligomeric silsesquioxane surfactants as organic modifier and initiator

Poly(ε‐caprolactone)/clay nanocomposites were synthesized by in situ ring‐opening polymerization of ε‐caprolactone in the presence of montmorillonite modified by hydroxyl functionalized, quaternized polyhedral oligomeric silsesquioxane (POSS) surfactants. The octa(3‐chloropropyl) polyhedral oligomeric silsesquioxane was prepared by hydrolytic condensation of 3‐chloropropyltrimethoxysilane, which was subsequently quaternized with 2‐dimethylaminoethanol. Montmorillonite was modified with the quaternized surfactants by cation exchange reaction. Bulk polymerization of ε‐caprolactone was conducted at 110°C using stannous octoate as an initiator/catalyst. Nanocomposites were analyzed by X‐ray diffraction, transmission electron microscopy, thermo gravimetric analysis, and differential scanning calorimetry. Hydroxyl functionalized POSS was employed as a surface modifier for clay which gives stable clay separation for its 3‐D structure and also facilitates the miscibility of polymer with clay in the nanocomposites due to the star architecture. An improvement in the thermal stability of PCL was observed even at 1 wt % of clay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011