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     

Preparation of fluorinated methacrylate/clay nanocomposite via in‐situ polymerization: Characterization,structure, and properties

Novel fluorinated coating containing well‐dispersed silicate nanolayers is successfully produced via in‐situ free radical polymerization of 2,2,2‐trifluoroethyl methacrylate in the presence of vinylbenzyl‐functionalized montmorillonite with different loading. The organic modification of sodium montmorillonite is achieved through an ion exchange reaction with triphenylvinylbenzylphosphonium chloride as surfactant prepared before use by reaction with vinylbenyl chloride and phosphine. The following in‐situ polymerization in the presence of organomodified clay leads to fluorinated nanocomposites with of partially exfoliated and intercalated morphologies, as determined via XRD and TEM analysis. The nanoscale dispersion of clay layers is also evidenced by thermal analysis; a moderate decrease of the glass transition temperature about 2–8 °C compared to their virgin PMATRIF and an improvement of their thermal stability as evidenced by TGA. The wettability of the nanocomposite films is also studied by contact angle measurements with water. The incorporation of organomodified clays not only increases the hydrophobicity of the fluorinated polymers but also improves the surface properties of obtained nanocomposites. Compared the virgin homopolymer, the mechanical properties of the nanocomposites are reduced by addition of organomodifed clay at temperature from 30 to 60 °C, whereas this trend is gradually decreased at higher temperature. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 411–418     

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     

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     

Designed organo‐layered silicates as nanoreactors for 1,3‐butadiene stereospecific polymerization toward rubber nanocomposites synthesis

Organo‐modified layered silicates were synthesized and used as inorganic carriers for CoCl₂(P^tBu₂Me)₂‐MAO catalyst in the polymerization of 1,3‐butadiene, yielding cis‐1,4‐enriched polybutadiene. The organoclays were prepared by: (i) intercalation of (ar‐vinyl‐benzyl)trimethyl ammonium chloride salt through an ion exchange reaction, and (ii) the edge‐surface grafting by trimethylchlorosilane. The ammonium modifier acts as “spacer” increasing the layer d‐spacing and as “filler” favoring the silylation of the edge‐surface clay hydroxyls. The grafted silane prevents the MAO cocatalyst from reacting with the edge‐OHs, by forcing it to react within the interlayer clay region. MAO lead to methylation of the cobalt complex and carbanion abstraction to give a cobalt‐methyl cation that is stabilized by the MAO anion. The nanoconfined cationic alkylated species insert the butadiene on the Co‐Me bond affording the growth of the polymer chains within the clay layers. The growing of the macromolecular chains fills the interlayer silicate region giving an intercalated polybutadiene rubber nanocomposite. The role of the silicate organo modification on the heterogeneous catalyst structural features, the polymerization behavior and the nanocomposite structures are discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

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     

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     

Morphology and elastic modulus of novel poly[oligo(ethylene glycol) diacrylate]‐montmorillonite nanocomposites

Novel thermosetting poly[oligo(ethylene glycol) diacrylate]‐sodium montmorillonite nanocomposites containing a range of clay volume fractions were prepared by an in situ polymerization method. X‐ray diffraction showed that the basal plane spacing of the clay was increased to approximately 1.7 nm regardless of clay volume fraction. Transmission electron microscopy confirmed the basal spacing and intercalated structure. The elastic moduli of the composites were measured using ultrasonic pulse‐echo equipment. The results show that the Young's modulus and shear modulus increase with nominal clay volume fraction up to 0.22, and are in good agreement with the well‐established Christensen method and derived Hashin–Shtrikman bounds for conventional composites provided that the true volume fraction of clay reinforcement filler is calculated. At low clay volume fractions, the composites were transparent. When the nominal clay volume fraction was further increased, cracks and porous surfaces appeared, as observed by scanning electron microscopy. These defects decreased the elastic modulus, indicating an upper limit for clay additions in this preparation route. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1785–1793, 2005     

Efficient photoinduced In situ preparation of clay/poly(glycidyl methacrylate) nanocomposites using hydrogen‐donor silane

Clay/poly(glycidyl methacrylate) nanocomposites (clay/PGMA) were prepared by in situ radical photopolymerization using N,N‐dimethylaminopropyltrimethoxysilane(DMA)‐modified bentonite clay acting as hydrogen donor for benzophenone in solution. This initiating system permits to photopolymerize glycidyl methacrylate between the lamellae of the DMA‐modified clay. The approach provides exfoliated nanocomposites as judged by the measurements of X‐ray diffraction. However, a low fraction of persistent intercalated clay regions was visible by transmission electron microscopy. X‐ray photoelectron spectra analyses indicate that the nanocomposites have PGMA‐rich surface. The clay/PGMA nanocomposites can be readily dispersed in ethanol. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 800–808     

Activity and stability spontaneously enhanced toward ethylene polymerization by employing 2‐(1‐(2,4‐dibenzhydrylnaphthylimino)ethyl)‐6‐(1‐(arylimino)ethyl) pyridyliron(II) dichlorides

A series of 2‐(1‐(2,4‐dibenzhydrylnaphthylimino)ethyl)‐6‐(1‐(arylimino)ethyl)pyridyliron(II) complexes ( Fe1 ? Fe5 ) was synthesized and characterized. The molecular structure of the representative Fe2 was determined by single‐crystal X‐ray diffraction, revealing a distorted pseudo‐square‐pyramidal geometry around the iron center. On activation with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all these iron complex precatalysts performed with high activities (up to 1.58 × 10⁷ g (PE) mol^?1 (Fe) h^?1) toward ethylene polymerization, producing highly linear polyethylenes with high molecular weight and bimodal distribution, which was in accordance with high temperature ¹³C NMR, high T _m values (T _m ～130 °C) and the GPC curves of the obtained polyethylenes. Meanwhile, DFT calculation results also showed the good correlation between net charges on iron and experimental activities. Compared with previous bis(imino)pyridyliron analogues, the current iron complexes containing the benzhydrylnaphthyl groups exhibited relatively higher activities and better thermal‐stability at elevated temperatures, especially at 80 °C as the industrial operating temperature, and still showed high activities toward ethylene polymerization up to 8.57 × 10⁶ g (PE) mol^?1 (Fe) h^?1 in the presence of co‐catalyst MMAO. In addition, these iron complex precatalysts all exhibited long lifetimes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 988–996     

Polymer–silicate nanocomposites produced by in situ atom transfer radical polymerization

Polymer–silicate nanocomposites were synthesized with atom transfer radical polymerization (ATRP). An ATRP initiator, consisting of a quaternary ammonium salt moiety and a 2‐bromo‐2‐methyl propionate moiety, was intercalated into the interlayer spacings of the layered silicate. Subsequent ATRP of styrene, methyl methacrylate, or n‐butyl acrylate with Cu(I)X/N,N‐bis(2‐pyridiylmethyl) octadecylamine, Cu(I)X/N,N,N′,N′,N″‐pentamethyldiethylenetriamine, or Cu(I)X/1,1,4,7,10,10‐hexamethyltriethylenetetramine (X = Br or Cl) catalysts with the initiator‐modified silicate afforded homopolymers with predictable molecular weights and low polydispersities, both characteristics of living radical polymerization. The polystyrene nanocomposites contained both intercalated and exfoliated silicate structures, whereas the poly(methyl methacrylate) nanocomposites were significantly exfoliated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 916–924, 2004     

In situ‐generated Ru(III)‐mediated ATRP from the polymeric Ru(III) complex in the absence of activator generation agents

Past research has examined the atom transfer radical polymerization (ATRP) with high oxidation state metal complexes and without the need for any additives such as reducing agent or free radical initiator. To extend this research, half‐metallocene ruthenium(III) (Ru(III)) catalysts were used for the polymerization of methyl methacrylate (MMA) for the first time. These catalysts were generated in situ simply by mixing phosphorus‐containing ligand and pentamethylcyclopentadienyl (Cp*) Ru(III) polymer ((Cp*RuCl₂)_n). The complexes in their higher oxidation state such as Cp*RuCl₂(PPh₃) were air‐stable, highly active, and removable catalysts for the ATRPs of MMA with both precision control of molecular weight and narrow polydispersity index. The addition of ppm amount of metal catalyst contributed to the formation of very well‐defined homopolymers and copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

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     

Synthesis and structural characterizations of [chromophore]+‐saponite/polyurethane nanocomposites

In this study, three chromophores—p‐nitroaniline, 4‐(4‐nitrophenylazo)aniline, and 4‐[(E)‐2‐{4‐[(E)‐2‐(4‐nitrophenyl)‐1‐diazenyl]phenyl}‐1‐diazenyl]aniline—were intercalated into layered aluminosilicate saponite and then dispersed into the polyurethanes matrix. The intercalated chromophore/saponite complexes were examined by inductively coupled plasma emission and element analysis technologies. The molecular orbital package computation simulation and X‐ray diffraction (XRD) analysis showed that possible configurations of chromophore ions on the gallery surfaces of saponite suggest that the chromophore molecules lie parallel to the basal planes of silicate as an inclined paraffin structure or as pseudo‐multilayers. The XRD and transmission electron microscopy analysis indicated that the delamination of organoclay in the polyurethanes matrix exhibited nanolayers, exfoliated structure, or both. In particular, even at high doping levels up to 15 wt % of organoclay, the [chromophore]⁺‐saponite/polyurethanes film did not display a macroscopic aggregation of layered silicates and showed high transparency. The thermal stability of chromophore was significantly enhanced as intercalated into the layered aluminosilicate saponite, and the glass‐transition temperature of [chromophore]⁺‐saponite/polyurethanes nanocomposites proportionally increased with increased clay content. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1690–1703, 2002     

Functional copolymer/organo‐MMT nanoarchitectures. XIX. Nanofabrication and characterization of poly(MA‐alt‐1‐octadecene)‐g‐PLA layered silicate nanocomposites with nanoporous core–shell morphology

Novel bioengineering functional copolymer‐g‐biopolymer‐based layered silicate nanocomposites were fabricated by catalytic interlamellar bulk graft copolymerization of L‐lactic acid (LA) monomer onto alternating copolymer of maleic anhydride (MA) with 1‐octadecene as a reactive matrix polymer in the presence of preintercalated LA…organo‐MMT clay (reactive ODA‐MMT and non‐reactive DMDA‐MMT) complexes as nanofillers and tin(oct)₂ as a catalyst under vacuum at 80°C. To characterize the functional copolymer layered silicate nanocomposites and understand the mechanism of in situ processing, interfacial interactions and nanostructure formation in these nanosystems, we have utilized a combination of variuous methods such as FT‐IR spectroscopy, X‐ray diffraction (XRD), dynamic mechanical (DMA), thermal (DSC and TGA‐DTG), SEM and TEM morphology. It was found that in situ graft copolymerization occurred through the following steps: (i) esterification of anhydride units of copolymer with LA; (ii) intercalation of LA between silicate galleries; (iii) intercalation of matrix copolymer into silicate layers through in situ amidization of anhydride units with octadecyl amine intercalant; and (iv) interlamellar graft copolymerization via in situ intercalating/exfoliating processing. The main properties and observed micro‐ and nanoporous surface and internal core–shell morphology of the nanocomposites significantly depend on the origin of MMT clays and type of in situ processing (ion exchanging, amidization reaction, strong H‐bonding and self‐organized hydrophobic/hydrophilic interfacial interactions). This developed approach can be applied to a wide range of anhydride‐containing copolymers such as random, alternating and graft copolymers of MA to synthesize new generation of polymer‐g‐biopolymer silicate layered nanocomposites and nanofibers for nanoengineering and nanomedicine applications. Copyright © 2014 John Wiley & Sons, Ltd.     

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     

Phase behavior of modified montmorillonite– poly(ϵ‐caprolactone) nanocomposites

The thermal behavior and overall isothermal crystallization kinetics of a series of organophilic modified montmorillonite–poly(?‐caprolactone) nanocomposites were investigated. In general, the thermal behavior was influenced more by the type of dispersion than by the clay content. For nanocomposites in which silicate platelets were predominantly dispersed in the polymer matrix to give exfoliated structures, the thermal properties were improved with respect to those of neat poly(?‐caprolactone), whereas in those cases in which simply intercalated structures were attained, the thermal properties regularly decayed as the clay content increased. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1321–1332, 2004     

Facile green strategy for micro/nano structured conducting polyaniline‐clay nanocomposite via template polymerization using amphiphilic dopant, 3‐pentadecyl phenol 4‐sulphonic acid

Novel self‐assembled nano/microstructured conducting PANICN was prepared by in situ intercalative emulsion polymerization of aniline in aqueous dispersion of clay using bifunctional amphiphilic dopant, 3‐pentadecyl phenol‐4‐sulphonic acid (PDPSA) derivable from renewable resource. X‐ray diffraction and scanning electron microscopy (SEM) studies revealed the formation of monolayer of protonated PANI intercalated nanoclays with template polymerized self‐assembled micro/nanostructured protonated PANI. Nano/micro structured PANIs were formed by the supra molecular self‐assembling of the inter‐chain hydrogen bonding, inter‐plane phenyl stacking and electrostatic layer by layer self‐assembling (ELBS) between polarized alkyl chains present dopant anions and were manifested using fourier transform infra red spectroscopy and differential scanning calorimetry. On the basis of the results, structure‐directing effect of ‘anilinium salt micelle’ was schematically illustrated in this article. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2664–2673, 2007     

Pendant cyclic carbonate‐polymer/Na‐smectite nanocomposites via in situ intercalative polymerization and solution intercalation

Nanocomposites of sodium smectite with polyether‐ and polystyrene‐containing pendant cyclic carbonates offer a novel approach to improving hydraulic barrier properties of Na‐smectite liners to saline leachates. The cyclic carbonate polyethers were prepared by cationic ring opening polymerization of a cyclic carbonate‐containing epoxide, whilst polystyrene polymers having pendant cyclic carbonate groups were obtained from radical photopolymerization of styrene. Na‐smectite nanocomposites of these polymers were formed via clay in situ polymerization and solution intercalation methods. X‐ray diffraction (XRD) and FT‐IR analysis confirmed that the polyether can be intercalated within the layers of smectite via in situ as well as solution intercalation of the pre‐formed polymer. The cyclic carbonate polyether nanocomposite was more resistant to leaching in 3M aqueous sodium chloride than its respective cyclic carbonate. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2421–2429