In situ synthesis of A3‐type star polymer/clay nanocomposites by atom transfer radical polymerization

A series of A₃‐type star poly(methylmethacrylate)/clay nanocomposites is prepared by in situ atom transfer radical polymerization (ATRP) initiated from organomodified montmorillonite containing quaternary trifunctional ATRP initiator. The first order kinetic plot shows a linear behavior, indicating the controlled character of the polymerization. The resulting nanocomposites are characterized by spectroscopic (XRD), thermal (DSC and TGA), and microscopic (TEM) analyses. The exfoliated nanocomposite has been obtained when polymerization was conducted with 1% of organic clay loading. Thermal analyses show that all nanocomposites have higher glass transition values and thermal stabilities compared to neat polymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5257–5262     

Synthesis of polybenzoxazine/clay nanocomposites by in situ thermal ring‐opening polymerization using intercalated monomer

A new class of polybenzoxazine/montmorillonite (PBz/MMT) nanocomposites has been prepared by the in situ polymerization of the typical fluid benzoxazine monomer, 3‐pentyl‐5‐ol‐3,4‐dihydro‐1,3‐benzoxazine, with intercalated benzoxazine MMT clay. A pyridine‐substituted benzoxazine was first synthesized and quaternized by 11‐bromo‐1‐undecanol and then used for ion exchange reaction with sodium ions in MMT to obtain intercalated benzoxazine clay. Finally, this organomodified clay was dispersed in the fluid benzoxazine monomers at different loading degrees to conduct the in situ thermal ring‐opening polymerization. Polymerization through the interlayer galleries of the clay led to the PBz/MMT nanocomposite formation. The morphologies of the nanocomposites were investigated by both X‐ray diffraction and transmission electron microscopic techniques, which suggested the partially exfoliated/intercalated structures in the PBz matrix. Results of thermogravimetric analysis confirmed that the thermal stability and char yield of PBz nanocomposites increased with the increase of clay content. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of organosoluble,thermoplastic elastomer/clay nanocomposites

We synthesized organosoluble, thermoplastic elastomer/clay nanocomposites by making a jelly like solution of ethylene vinyl acetate containing 28% vinyl acetate (EVA‐28) and blending it with organomodified montmorillonite. Sodium montmorillonite (Na⁺‐MMT) was made organophilic by the intercalation of dodecyl ammonium ions. X‐ray diffraction patterns of Na⁺‐MMT and its corresponding organomodified dodecyl ammonium ion intercalated montmorillonite (12Me‐MMT) showed an increase in the interlayer spacing from 11.94 to 15.78 Å. However, X‐ray diffraction patterns of the thermoplastic elastomer and its hybrids with organomodified clay contents up to 6 wt % exhibited the disappearance of basal reflection peaks within an angle range of 3–10°, supporting the formation of a delaminated configuration. A hybrid containing 8 wt % 12Me‐MMT revealed a small hump within an angle range of 5–6° because of the aggregation of silicate layers in the EVA‐28 matrix. A transmission electron microscopy image of the same hybrid showed 3–5‐nm 12Me‐MMT particles dispersed in the thermoplastic elastomer matrix; that is, it led to the formation of nanocomposites or molecular‐level composites with a delaminated configuration. The formation of nanocomposites was reflected through the unexpected improvement of thermal and mechanical properties; for example, the tensile strength of a nanocomposite containing only 4 wt % organophilic clay was doubled in comparison with that of pure EVA‐28, and the thermal stability of the same nanocomposite was higher by about 34 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2065–2072, 2002     

Gas barrier properties of poly(ε‐caprolactone)/clay nanocomposites: Influence of the morphology and polymer/clay interactions

Poly(ε‐caprolactone)/montmorillonite nanocomposites were prepared maintaining a constant inorganic content with three means: melt blending of poly(ε‐caprolactone) with natural or organomodified clays, in situ polymerization of ε‐caprolactone in the presence of organomodified clays, and initiation of ε‐caprolactone polymerization from the silicate layer with appropriate organomodified montmorillonites and activator. In this last case, the polymer chains were grafted to the silicate layers and it was possible to tune up the grafting density. The presence of clays did not modify the polymer crystallinity. It was shown that the in situ polymerization process from the clay surface improved the clay dispersion. The gas barrier properties of the different composite systems were discussed both as a function of the clay dispersion and of the matrix/clay interactions. The highest barrier properties were obtained for an exfoliated morphology and the highest grafting density. Similar evolution of the permeability and the diffusion coefficients was observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 205–214, 2005     

Long‐lived layered silicates‐immobilized 2,6‐bis(imino)pyridyl iron (II) catalysts for hybrid polyethylene nanocomposites by in situ polymerization: Effect of aryl ligand and silicate modification

Heterogeneous‐layered silicate‐immobilized 2,6‐bis(imino)pyridyl iron (II) dichloride/MMAO catalysts, in which the active polymerization species are intercalated within sodium‐ and organomodified‐layered silicate galleries, were prepared for producing hybrid exfoliated polyethylene (PE) nanocomposites by means of in situ polymerization. The inorganic filler was first treated with modified‐methylaluminoxane (MMAO) to produce a supported cocatalyst: MMAO reacts with silicates replacing most of the organic surfactant, thus modifying the original crystallographic clay order. MMAO anchored to the nanoclay was able to activate polymerization iron complexes initiating the polymer growth directly from the filler lamellae interlayer. The polymerization mechanism taking place in between the montmorillonite lamellae separates the layers, thus promoting deagglomeration and effective clay dispersion. Transmission electron microscopy revealed that in situ polymerization by catalytically active iron complexes intercalated within the lower organomodified clay led to fine dispersion and high exfoliation extent. The intercalated clay catalysts displayed a longer polymerization life‐time and brought about ethylene polymerization more efficiently than analogous homogeneous systems. PEs having higher molecular masses were obtained. These benefits resulted to be dependent more on the filler nature than on the ligand environment around the iron metal center and the experimental synthetic route. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 548–564, 2009     

Preparation and characterization of a novel biodegradable poly(p‐dioxanone)/montmorillonite nanocomposite

Poly(p‐dioxanone) (PPDO)/montmorillonite nanocomposites were prepared through the in situ ring‐opening polymerization of p‐dioxanone (PDO) and three types of montmorillonites (natural sodium montmorillonite, montmorillonite modified by octadecyltrimethyl ammonium chloride, and montmorillonite modified by hydroxyethylhexadecyldimethyl ammonium bromine) in the presence of triethylaluminum. Montmorillonite could accelerate the polymerization of PDO, and the viscosity‐average molecular weight of PPDO could reach 44,900 g/mol in 0.5 h. A nucleating effect of montmorillonite was observed, and the crystallization temperature of PPDO was increased by 18 °C. All three montmorillonites could improve the thermal stability of PPDO and increase the glass‐transition and melting temperatures of PPDO. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2298‐2303, 2005     

Poly(styrene‐b‐tetrahydrofuran)/clay nanocomposites by mechanistic transformation

Synthesis of poly(styrene‐block‐tetrahydrofuran) (PSt‐b‐PTHF) block copolymer on the surfaces of intercalated and exfoliated silicate (clay) layers by mechanistic transformation was described. First, the polystyrene/montmorillonite (PSt/MMT) nanocomposite was synthesized by in situ atom transfer radical polymerization (ATRP) from initiator moieties immobilized within the silicate galleries of the clay particles. Transmission electron microscopy (TEM) analysis showed the existence of both intercalated and exfoliated structures in the nanocomposite. Then, the PSt‐b‐PTHF/MMT nanocomposite was prepared by mechanistic transformation from ATRP to cationic ring opening polymerization (CROP). The TGA thermogram of the PSt‐b‐PTHF/MMT nanocomposite has two decomposition stages corresponding to PTHF and PSt segments. All nanocomposites exhibit enhanced thermal stabilities compared with the virgin polymer segments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2190–2197, 2009     

Synthesis,rheology, and morphology of nylon‐11/layered silicate nanocomposite

Exfoliated nylon‐11/layered silicate nanocomposites were prepared via in situ polymerization by dispersing organoclay in 11‐aminoundecanoic acid monomer. The original clay was modified by a novel method with 11‐aminoundecanoic acid. In situ Fourier transform infrared spectroscopy results show that stronger hydrogen bonds exist between nylon‐11 and organoclay than that of between nylon‐11 and original clay. The linear dynamic viscoelasticity of organoclay nanocomposites was investigated. Before taking rheological measurements, the exfoliated and intercalating structures and the thermal properties were characterized using X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The results show that the clay was uniformly distributed in nylon‐11 matrix during in situ polymerization of clay with 4 wt % or less. The presence of clay in nylon‐11 matrix increased the crystallization temperature and the thermal stability of nanocomposites prepared. Rheological properties such as storage modulus, loss modulus, and relative viscosity have close relationship with the dispersion favorably compatible with the organically modified clay. Comparing with neat nylon‐11, the nanocomposites show much higher dynamic modulus and stronger shear thinning behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2161–2172, 2006     

Poly(dicyclopentadiene)‐montmorillonite nanocomposite formation via simultaneous intergallery‐surface initiation and chain crosslinking using ROMP

Exfoliated poly(dicyclopentadiene) (pDCPD)—montmorillonite (MMT) nanocomposites were synthesized via intergallery‐surface‐initiated ring opening metathesis polymerization (ROMP). This is the first example of in situ polymerization of pDCPD from clay intergallery surfaces using ROMP. Grubbs catalyst was immobilized on the surface of MMT clay modified with vinylbenzyl dimethyloctadecyl ammonium chloride (VOAC), and DCPD polymerized from the clay surface while simultaneously crosslinking to form a thermoset nanocomposite in a one‐pot reaction. X‐ray diffraction and transmission electron microscopy analysis indicated that the resultant nanocomposites exhibited exfoliated morphologies with heterogeneous clay platelet distribution. Conventional bulk‐initiated nanocomposites containing VOAC modified MMT were also synthesized as a comparison, and these resulted in nanocomposites with intercalated morphologies. The differences between the morphologies demonstrated that growing polymer chains from the initiator sites on the intergallery surface of the clay platelets pushed the platelets apart during the polymerization of the intergallery‐surface‐initiated nanocomposites, aiding in the exfoliation process. Compression testing indicated that the intergallery‐surface‐initiated nanocomposites led to improvements of up to 50% in the compressive Young's Modulus, while the bulk‐initiated nanocomposites at the same clay loadings did not exhibit improved properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

In situ intercalative polymerization of conducting polypyrrole/montmorillonite nanocomposites

Conducting polypyrrole (PPy)‐montmorillonite (MMT) clay nanocomposites have been synthesized by the in situ intercalative polymerization method. The PPy‐MMT nanocomposites are characterized by field‐emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), ultraviolet–visible (UV–vis) spectroscopy, thermogravimetric analysis (TGA), and Fourier‐transform infrared (FTIR) spectroscopy. XRD patterns show that after polymerization by the in situ intercalative method with ammonium persulfate and 1 M HCl, an increase in the basal spacing from 1.2 to 1.9 nm was observed, signifying that PPy is synthesized between the interlayer spaces of MMT. TEM and SEM micrographs suggest that the coexistence of intercalated MMT layers with the PPy macromolecules. FTIR reveals that there might be possible interfacial interactions present between the MMT clay and PPy matrix. The study also shows that the introduction of MMT clay results in thermal stability improvement of the PPy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2279–2285, 2008     

Thermal properties of polystyrene nanocomposites formed from rigid intercalation agent‐treated montmorillonite

Polystyrene (PS)/clay nanocomposites were prepared with two different new intercalation organophilic clays, the phosphonium salt (APP) and the ammonium 4‐(4‐adamantylphenoxy)‐1‐butanamine (APB) salts, by emulsion polymerization technique. X‐ray diffraction and transmission electron microscopy were performed to characterize the layered structures of APB‐ and APP‐treated polymer–clay nanocomposites, and both resulted in exfoliated structures. Molecular weights of PS obtained from these nanocomposites are slightly lower than the virgin PS formed under similar polymerization conditions. Coefficient of thermal expansion showed approximately a 44–55% decrease for APB‐ and APP‐intercalated clay nanocomposites relative to the pure PS. Both T_g and thermal decomposition temperature of the PS component in the nanocomposite are higher than the virgin PS, implying that the presence of clay is able to enhance thermal stabilities of the PS. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1781–1787, 2007     

Polymer/clay nanocomposites through multiple hydrogen‐bonding interactions

An 2‐ureido‐4[1H]pyrimidinone (UPy) motif with self‐association capability (through quadruple hydrogen bonds) was successfully anchored onto montmorillonite clay layers. Polymer/clay nanocomposites were prepared by specific hydrogen bonding interactions between surface functionalized silica nanoclays and UPy‐bonded supramolecular poly(ethylene glycol) or poly(?‐caprolactone). The mixed morphologies including intercalated layers with a non‐uniform separation and exfoliated single layers isolated from any stack were determined by combined X‐ray diffraction and transmission electron microscopic measurements. Thermal analyses showed that all nanocomposites had higher decomposition temperatures and thermal stabilities compared with neat polymer. The differential scanning calorimetric data implied that the crystallinity of polymers did not show essential changes upon introduction of organomodified UPy clays. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 650–658     

Stereoregular P(MMA)‐clay nanocomposites by metallocene catalysts: In situ synthesis and stereocomplex formation

This contribution reports the synthesis and characterization of stereochemically controlled, as well as crystalline stereocomplex, P(MMA)‐clay nanocomposites using metallocene complexes and alane‐intercalated clay activators. The ligand elimination and exchange reactions involving Lewis acids E(C₆F₅)₃ (E = Al, B) and an organically modified montmorillonite clay were employed to synthesize the alane‐intercalated clay activators. When combined with dimethyl metallocenes of various symmetries, these clay activators brought about efficient MMA polymerizations leading to in situ polymerized, stereochemically controlled P(MMA)‐intercalated clay nanocomposites. The most noticeable thermal property enhancement observed for the clay nanocomposite P(MMA), when compared with the pristine P(MMA) having similar molecular weight and stereomicrostructure, has a considerable increase in T_g (≥10 °C). Mixing of dilute THF solutions of two diastereomeric nanocomposites in a 1:2 isotactic to syndiotactic ratio, followed by reprecipitation or crystallization procedures, yielded unique double‐stranded helical stereocomplex P(MMA)‐clay nanocomposites with a predominantly exfoliated clay morphology. Remarkably, the resulting crystalline stereocomplex P(MMA) matrix is resistant to the boiling‐THF extraction and its clay nanocomposites exhibit high T_m of 201 to 210 °C. Furthermore, the stereocomplex P(MMA)‐clay nanocomposite shows a one‐step, narrow decomposition temperature window and a single, high maximum rate decomposition temperature of 377 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2581–2592, 2007     

In situ polymerization of ethylene with bis(imino)pyridine iron(II) catalysts supported on clay: The synthesis and characterization of polyethylene–clay nanocomposites

Polyethylene–clay nanocomposites were synthesized by in situ polymerization with 2,6‐bis[1‐(2,6‐diisopropylphenylimino)ethyl] pyridine iron(II) dichloride supported on a modified montmorillonite clay pretreated with methylaluminoxane (MAO). The catalysts and the obtained nanocomposites were examined with wide‐angle X‐ray scattering. The exfoliation of the clay was further established by transmission electron microscopy. Upon the treatment of the clay with MAO, there was an increase in the d‐spacing of the clay galleries. No further increase in the d‐spacing of the galleries was observed with the iron catalyst supported on the MAO‐treated clay. The catalyst activity for ethylene polymerization was independent of the Al/Fe ratio. The exfoliation of the clay inside the polymer matrix depended on various parameters, such as the clay content, catalyst content, and Al/Fe ratio. The crystallinity percentage and crystallite size of the nanocomposites were affected by the degree of exfoliation of the clay. Moreover, when ethylene was polymerized with a mixture of the homogeneous iron(II) catalyst and clay, the degree of exfoliation was significantly lower than when the polymerization was performed with a preformed clay‐supported catalyst. This observation suggested that in the supported catalyst, at least some of the active centers resided within the galleries of the clay. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 304–318, 2005     

Effect of the premelting temperature and sample thickness on the polymorphic behavior of syndiotactic polystyrene/clay nanocomposites

X‐ray diffraction methods and differential scanning calorimetry thermal analysis have been used to investigate the structural changes of syndiotactic polystyrene (sPS)/clay nanocomposites. sPS/clay nanocomposites have been prepared by the mixing of sPS polymer solutions with organically modified montmorillonite. X‐ray diffraction data and differential scanning calorimetry results indicate that the dominating crystal forms and their relative fractions in sPS and sPS/clay nanocomposites are different for various premelting temperatures (T_max's). Higher T_max's favor the formation of the thermodynamically more stable β‐crystalline form, and its relative fraction has been obtained from the X‐ray diffraction data in the range of 11.5–13°. The intensity of the X‐ray diffraction data in the range of 11.5–13° decreases as the thickness of sPS/clay nanocomposites decreases from 150 to 20 μm. At the same time, the intensity of the X‐ray data in the range of 6–7° becomes sharper as the thickness of sPS/clay nanocomposites decreases. The calculation ratio based on the peak intensities at 6.2 and 6.8° for sPS/clay nanocomposites of equal thickness and crystallinity in the pure β and α forms has also been determined in this study. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1730–1738, 2003     

Effects of melt‐processing conditions on the quality of poly(ethylene terephthalate) montmorillonite clay nanocomposites

Organically modified montmorillonite was synthesized with a novel 1,2‐dimethyl‐3‐N‐alkyl imidazolium salt or a typical quaternary ammonium salt as a control. Poly(ethylene terephthalate) montmorillonite clay nanocomposites were compounded via melt‐blending in a corotating mini twin‐screw extruder operating at 285 °C. The nanocomposites were characterized with thermal analysis, X‐ray diffraction, and transmission electron microscopy to determine the extent of intercalation and/or exfoliation present in the system. Nanocomposites produced with N,N‐dimethyl‐N,N‐dioctadecylammonium treated montmorillonite (DMDODA‐MMT), which has a decomposition temperature of 250 °C, were black, brittle, and tarlike resulting from DMDODA degradation under the processing conditions. Nanocomposites compounded with 1,2‐dimethyl‐3‐N‐hexadecyl imidazolium treated MMT, which has a decomposition temperature of 350 °C, showed high levels of dispersion and delamination. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2661–2666, 2002     

Dispersibility of clay and crystallization kinetics for in situ polymerized PET/pristine and modified montmorillonite nanocomposites

Nanocomposite materials composed of poly (ethylene terephthalate) (PET) and montmorillonite (MMT) clays were prepared by in situ polymerization. Samples consisted of PET blended with various quantities of either pristine (Na⁺‐MMT) or organically modified MMT (A10‐MMT). The morphology and thermal and mechanical properties were evaluated for each sample. TEM micrographs, acquired at a 20 nm resolution, provide direct evidence of exfoliation of the clay particles into the PET matrix and show the effect of the alkyl‐modifier on clay dispersibility. The dispersion of PET/A10‐MMT was greater than that observed for the PET/Na⁺‐MMT nanocomposites. The greatest degree of exfoliation occurred for PET/A10‐MMT 0.5 wt %. However, PET/Na⁺‐MMT exhibited higher crystallization temperatures and rates suggesting that Na⁺‐MMT is a more efficient nucleating agent. Both mechanically and thermally, PET/A10‐MMT nanocomposites exhibited superior properties over pure PET. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1022–1035, 2008     

Poly(cyclohexene oxide)/clay nanocomposites by photoinitiated cationic polymerization via activated monomer mechanism

Poly(cyclohexene oxide) (PCHO)/clay nanocomposites were prepared by in situ photoinitiated activated monomer cationic polymerization. The polymerization of cyclohexene oxide through the interlayer galleries of the clay can provide distribution of the clay layers in the polymer matrix homogenously and results in the formation of PCHO/clay nanocomposites. The exfoliated structures were characterized by X‐ray diffraction spectroscopy, thermogravimetric analysis, transmission electron microscopy, and atomic force microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5328–5335, 2009     

Synthesis of poly(2‐ethylhexyl acrylate)/clay nanocomposite by in situ living radical polymerization

This investigation reports the preparation of tailor‐made poly(2‐ethylhexyl acrylate) (PEHA) prepared via in situ living radical polymerization in the presence of layered silicates and characterization of this polymer/clay nanocomposite. Being a low T_g (?65 °C) material, PEHA has very good film formation property for which it is used in paints, adhesives, and coating applications. 2‐Ethylhexyl acrylate was polymerized at 90 °C using CuBr and Cu(0) as catalyst in combination with N,N,N′,N″,N″‐pentamethyl diethylenetriamine (PMDETA) as ligand. A tremendous enhancement in reaction rate and polymerization data was achieved when acetone was added as additive to increase the efficiency of the catalyst system. PEHA/clay nanocomposite was prepared at 90 °C using CuBr as catalyst in combination with PMDETA as ligand. Different types of clay with same loading were also used to study the effect on reaction rate. The molecular weight (M_n) and polydispersity index of the prepared nanocomposites were characterized by size exclusion chromatography. The active end group of the polymer chain was analyzed by ¹H NMR analysis and by chain extension experiment. Polymer/clay interaction was studied by Fourier Transform Infrared spectrometry and wide‐angle X‐ray diffraction analyses. Distribution of clay in the polymer matrix was studied by the transmission electron microscopy. Thermogravimetric analysis showed that thermal stability of PEHA/clay nanocomposite increases on addition of nanoclay. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Phase transition in polyamide‐66/montmorillonite nanocomposites on annealing

The crystalline‐phase transition in polyamide‐66/montmorillonite nanocomposites before melting was investigated by in situ X‐ray diffraction and is reported for the first time in this work. The phase‐transition temperature in the nanocomposites was 170 °C, 20 °C lower than that in polyamide‐66. The lower phase‐transition temperature of the nanocomposites could be attributed to the γ‐phase‐favorable environment caused by silicate layers. Meanwhile, the addition of silicate layers changed the crystal structure of the polyamide‐66 matrix and influenced the phase‐transition behavior. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 63–67, 2003