Novel polyacrylonitrile nanocomposites containing Na-montmorillonite and nano SiO2 particle

Polyacrylonitrile (PAN)/Na-montmorillonite (Na-MMT)/SiO₂ nanocomposites were prepared via in situ emulsion polymerization. X-ray diffraction (XRD) results suggest that the Na-MMT layers are exfoliated during the polymerization process. As evidenced by the transmission electron microscope (TEM), the Na-MMT and nano SiO₂ particles exhibit good dispersion in the polymer matrix. It was found that the PAN/Na-MMT/SiO₂ nanocomposites exhibit considerably enhanced mechanical properties compared with the PAN/Na-MMT and PAN/SiO₂ nanocomposites.     

Polymer/silicate nanocomposites synthesized with potassium persulfate at room temperature: polymerization mechanism, characterization, and mechanical properties of the nanocomposites

Polymer/silicate nanocomposites were synthesized using potassium persulfate (KPS) in the presence of silicate and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) without exterior redox co-catalysts at a room temperature. A mechanism for the room temperature polymerization in the presence of silicate was suggested: AMPS attached on the surface of silicate layers would oxidize Fe⁺² in silicate lattice to become Fe⁺³ and the Fe⁺³ would decompose KPS to form radicals like redox co-catalysts. Poly (acrylonitrile) (PAN)/silicate nanocomposite showed an exfoliated structure, but poly (methyl methacrylate) (PMMA)/silicate nanocomposite showed an intercalated structure. Polymers recovered from the nanocomposites synthesized at a room temperature had high isotactic configurations compared to bulk polymers. The dipole–dipole interaction between monomers and silicate surface might make the lamella of monomers to form on the silicate layer surface and produced polymers with more isotactic configurations. PAN/silicate nanocomposite showed two glass transition temperatures at 113 and 151 °C. The lower temperature might be related to the molecules with low molecular weight. PMMA/silicate nanocomposite had a storage modulus of 4.47×10⁹ Pa at 40 °C.     

Effect of chemical components of emulsion polymerization in aqueous media on Na-MMT nanostructure by XRD analysis

The effects of chemical ingredients of emulsion polymerization reaction consisting deionized water as media of polymerization, styrene and methylmethacrylate (MMA) as nonpolar and polar monomers respectively, potassium persulfate (KPS) as initiator, Dodecylbenzenesulfonic acid sodium salt (DBS-Na) and 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) as conventional and reactive surfactants respectively, on nanostructural changes of pristine sodium Montmorillonite (Na-MMT) in aqueous media at ambient temperature and moderate stirring rate (150 rpm) was studied by X-ray diffraction (XRD) analysis. According to results, water can completely destroy the structural alignment of Na-MMT (in first stage with deflocculation and in second stage with defoliation), but it needs enough time (4 days). Addition of other chemical components in 48 h had different changes on water effect on nanostructure of Na-MMT. The interaction between AMPS and Na-MMT in aqueous media also was studied by thermal analysis (thermal gravimetery analysis and differential scanning calorimetery). It is illustrated that there are some strong interactions between AMPS and Na-MMT in water media which can lead to preparation of an end-tethered polymeric nanocomposite on Na-MMT layers through emulsion polymerization with this reactive surfactant.     

Synthesize of polymer–silicate nanocomposites by in situ metal‐catalyzed living radical polymerization

Polymer–silicate nanocomposites were synthesized with atom transfer radical polymerization (ATRP). An ATRP initiator, consisting of a quaternary ammonium salt moiety and an α‐phenyl chloroacetyl chloride moiety, were intercalated into the interlayer spacings of the layered silicate. Subsequent ATRP of styrene with CuCl/2,2′‐bipyridine (bipy) as the catalyst 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. The prepared materials were characterized by XRD, SEM, TEM, FTIR, and ¹H NMR techniques. Effect of silicate on thermal properties and glass transition temperature of polystyrene was investigated using thermogravimetric analysis and differential scanning calorimetric techniques. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Synthesis of exfoliated poly(styrene-co-acrylonitrile) copolymer/silicate nanocomposite by emulsion polymerization; monomer composition effect on morphology

Two types of SAN/silicate nanocomposites were prepared to set up the relationship between the composition of monomers and the resultant morphology of the composites using a pristine sodium montmorillonite (Na-MMT). SAN I series were synthesized with acrylonitrile in initial stage and a mixture of styrene and acrylonitrile in increment stage. SAN II series were prepared with the mixture of styrene and acrylonitrile throughout polymerization. SAN I series showed exfoliated states but SAN II series exhibited intercalated states because SAN I series consisted of hydrophilic AN initially. The chemical affinity between monomer and silicate had a strong influence on the morphology of SAN/silicate nanocomposites. The exfoliated SAN I series had enhanced moduli and glass transition temperatures, T_g, compared to the intercalated SAN II series and pure SAN.     

Exfoliation of layered silicate facilitated by ring-opening reaction of cyclic oligomers in PET-clay nanocomposites

Ethylene terephthalate cyclic oligomers (ETCs) have been successfully polymerized to a high molecular weight poly(ethylene terephthalate) (PET) employing the advantages of the low viscosity of cyclic oligomers and lack of chemical emissions during polymerization. Using ring-opening polymerization of ETCs with organically modified montmorillonite (OMMT), we intend to ascertain the possibility of preparing high performance PET/clay nanocomposites. Due to the low molecular weight and viscosity, ETCs are successfully intercalated to the clay gallerys, what is evidenced by XRD showing a down-shift of basal plane peak of layered silicate along with TEM investigation. Subsequent ring-opening polymerization of ETCs in-between silicate layers yielded a PET matrix of high molecular weight along with high disruption of layered silicate structure and homogeneous dispersion of the latter in the matrix. Although co-existence of exfoliation and intercalation states of silicate layers after polymerization of ETCs rather than perfect exfoliation was observed, a dramatic increase in d-spacing along with fast polymerization presents us a great potential of cyclic oligomer process in producing a thermoplastic polymer-clay nanocomposites of extremely well-dispersed silicate nanoplatelets and the corresponding high performances.     

Synthesis and characterization of exfoliated poly(styrene-co-methyl methacrylate)/clay nanocomposites via emulsion polymerization with AMPS

A method was described for synthesis of exfoliated poly(styrene-co-methyl methacrylate)/clay nanocomposites through an emulsion polymerization with reactive surfactant, 2-acrylamido-2-methyl-1-propane sulfonic (AMPS) which made the polymer end-tethered on pristine Na-MMT.AMPS widened the gap between clay layers and facilitates comonomers penetrate into clay. Silicate layers affect the composition of comonomers, for example A0.3M10S10T5 showed the elevated composition of MMA end tethered on silicate when compared to the feed ratio and polar methyl methacrylate (MMA) was considered to have the stronger interaction with clay layers than styrene.The exfoliated structure of extracted nanocomposite was confirmed by XRD and transmission electron microscopy. The onset of thermal decomposition for nanocomposites shifted to a higher temperature than that for neat copolymer. The dynamic moduli of nanocomposites increase with clay content. Dynamic storage modulus and complex viscosity increased as the clay content increased. In low frequency region all prepared nanocomposites exhibited apparent low-frequency plateaus in the linear storage modulus. Complex viscosity showed shear-thinning behavior as the clay content increases.     

Biodegradable polyester layered silicate nanocomposites based on poly(ϵ‐caprolactone)

Nanocomposites based on biodegradable poly(?‐caprolactone) (PCL) and layered silicates (montmorillonite, MMT) were prepared either by melt interaction with PCL or by in situ ring‐opening polymerization of ?‐caprolactone as promoted by the so‐called coordination‐insertion mechanism. Both non‐modified clays (Na⁺ ‐MMT) and silicates modified by various alkylammonium cations were studied. Mechanical and thermal properties were examined by tensile testing and thermogravimetric analysis. Even at a filler content as low as 3 wt% of inorganic layered silicate, the PCL‐layered silicate nanocomposites exhibited improved mechanical properties (higher Young's modulus) and increased thermal stability as well as enhanced flame retardant characteristics as a result of a charring effect. It was shown that the formation of PCL‐based nanocomposites depended not only on the nature of the ammonium cation and related functionality but also on the selected synthetic route, melt intercalation vs. in situ intercalative polymerization. Interestingly enough, when the intercalative polymerization of ?‐caprolactone was carried out in the presence of MMT organo‐modified with ammonium cations bearing hydroxyl functions, nanocomposites with much improved mechanical properties were recovered. Those hybrid polyester layered silicate nanocomposites were characterized by a covalent bonding between the polyester chains and the clay organo‐surface as a result of the polymerization mechanism, which was actually initiated from the surface hydroxyl functions adequately activated by selected tin (II) or tin (IV) catalysts.     

Polymer/layered silicate nanocomposites by combined intercalative polymerization and melt intercalation: a masterbatch process

Poly(ε-caprolactone) (PCL) and poly(vinyl chloride) (PVC) layered silicate nanocomposites were prepared by combination of intercalative polymerization and melt intercalation. In a first step, high clay content PCL nanocomposites were prepared by in situ polymerization of ε-caprolactone intercalated between selected organo-modified silicate layers. The polymerization was catalyzed with dibutyltin dimethoxide in the presence of montmorillonites, the surface of which were previously exchanged with (functionalized) long alkyl chains ammonium cations. Then, these highly filled PCL nanocomposites were added as masterbatches in commercial PCL and PVC by melt blending. The intercalation of PCL chains within the silicate layers by in situ polymerization proved to be very efficient, leading to the formation of intercalated and/or exfoliated structures depending on the organo-clay. These masterbatches were readily dispersed into the molten PCL and PVC matrices yielding intercalated/exfoliated layered silicate nanocomposites which could not be obtained by melt blending the matrix directly with the same organo-modified clays. The formation of nanocomposites was assessed both by X-ray diffraction and transmission electronic microscopy. Interestingly, this so-called ‘masterbatch’ two-step process allowed for preparing PCL nanocomposites even with non-modified natural clay, i.e. sodium montmorillonite, which showed a material stiffness much higher than the corresponding microcomposites recovered by direct melt intercalation. The thermal stability of PCL nanocomposites as a function of clay content was investigated by thermogravimetry (TGA).     

A Comparative Study of Polystyrene/Layered Silicate Nanocomposites,Synthesized by Emulsion and Bulk Polymerization Methods

Polystyrene/clay (PS/clay) nanocomposites were synthesized by insitu emulsion and bulk polymerization methods. Sodium montmorillonite (Na-MMT) and two organically modified clays (Cloisite 30B and Cloisite 15A) were employed. The effect of clay swelling method and sonication on the d-spacing of silicate layers was also investigated. The surface morphology of pure PS and PS/clay nanocomposites were comparatively investigated using scanning electron microscopy (SEM). Thermogravimetric analysis (TGA) of PS and PS/clay nanocomposites revealed the improved thermal stability of PS/clay nanocomposites compared to pure PS. Results of optical transparency tests showed the better transparency of nanocomposite films compared to the pure PS film.     

Polymer layered silicate nanocomposites

Polymers filled with low amounts of layered silicate dispersed at nanoscale level are most promising materials characterized by a combination of chemical, physical and mechanical properties that cannot be obtained with macro‐ or microscopic dispersions of inorganic fillers. Polymer layered silicate nanocomposites can be obtained by insertion of polymer molecules in the galleries between the layers of phyllosilicate. Here, hydrated alkaline or alkaline earth metal cations are hosted which neutralize the negative charge resulting from isomorphous substitutions of Mg or Al cations within the silicate. Insertion of polymer molecules to prepare “intercalation hybrids” can be carried out by replacing the water hydration molecules in the galleries by polymers containing polar functional groups, using the so called ion‐dipole method. A more general technique involves compatibilization of the silicate by intercalation of an organic molecule, typically an organic alkylammonium salt, that replaces the cations in the interlayer galleries to form an organically modified layered silicate (OLS). The aliphatic chain of the OLS favors the intercalation of any type of polymer. Intercalated or delaminated polymer‐silicate hybrids are obtained depending on whether the stack organization of the silicate layers is preserved or is lost, with single sheets being distributed in the polymer matrix. The methods currently used for preparing polymer layered silicate (PLS) nanocomposites are: in situ polymerization, from polymer solution, or from polymer melt. Although PLS nanocomposites have been known for a long time, it is the possibility of preparing them by melt intercalation of OLS in processing that is boosting the present interest in these materials and their properties. So far PLS nanocomposites have been characterized by X‐ray diffractometry, transmission electron microscopy, differential scanning calorimetry, and NMR. Published results on PLS nanocomposites are reviewed concerning their characterization and properties with particular reference to fire retardant behavior.     

Preparation, characterization and antimicrobial activity of chitosan/layered silicate nanocomposites

Chitosan/layered silicate nanocomposites with different ratios were successfully prepared via solution-mixing processing technique. Unmodified Ca²⁺-rectorite and organic rectorite modified by cetyltrimethyl ammonium bromide were used. Their structures were characterized by XRD, TEM and FT-IR techniques. The results showed that chitosan chains were inserted into silicate layers to form the intercalated nanocomposites. The interlayer distance of the layered silicates in the nanocomposites enlarged as its amount increased. When the weight ratio between chitosan and organic rectorite was 12:1, the largest interlayer distance of 8.24 nm was obtained. However, with further increase of its amount, the interlayer distance of the layered silicates in the nanocomposites reduced. In vitro antimicrobial assay showed that pristine rectorite could not inhibit the growth of bacteria, but chitosan/layered silicate nanocomposites had stronger antimicrobial activity than pure chitosan, particularly against Gram-positive bacteria. With the increase of the amount and the interlayer distance of the layered silicates in the nanocomposites, the nanocomposites showed a stronger antibacterial effect on Gram-positive bacteria, while the nanocomposites showed a weaker antibacterial effect on Gram-negative bacteria. The lowest minimum inhibition concentration (MIC) value of the nanocomposites against Staphylococcus aureus and Bacillus subtilis was 0.00313% (w/v), and the relative inhibition time (RIT) against B. subtilis with concentration of 0.00313% (w/v) was >120 h.     

High performance epoxy‐layered silicate nanocomposites

High performance epoxy‐layered silicate nanocomposites based on tetra‐glycidyl4,4'‐diamino‐dipheny1 methane (TGDDM) resin cured with 4,4'‐diaminodipheny1 sulfone (DDS) have been successfully synthesized. Fluorohectorites modified by means of interlayer cation exchange of sodium cations for protonated dihydro‐imidazolines and octadecylamine were used. Fluorohectorite exchanged with 1‐methy12‐norsteary1‐3‐stearinoacid‐amidoethy1‐dihydro‐imidazolinium ions was immiscible with the epoxy matrix. In contrast, fluorohectorites exchanged with hydroxyethy1‐dihydro‐imidazolinium (HEODI) and riciny1‐dihydro‐imidazolinium ions (RDI) favored the formation of a nanocomposite structure. This is most likely due to the presence of ‐OH groups in their molecular structure, which has a catalytic effect on the polymerization occurring between the silicate layers. The diffusion of epoxy and curing agent molecules between the silicate layers is also promoted. Microscopy observations revealed that the dispersion of the silicate aggregates on a microscale was proportional to the degree of separation of the silicate layers on a nanoscale. Decreased apparent glass transition temperature was observed in all the nanocomposites. Finally, mechanical property studies showed that epoxy‐layered silicate nanocomposite formation could simultaneously improve fracture toughness and Young's modulus, without adversely affecting tensile strength.     

Preparation of exfoliated high‐impact polystyrene/MMT nanocomposites via in situ polymerization under controlling viscosity of the reaction medium

Exfoliated high‐impact polystyrene (HIPS)/montmorillonite (MMT) nanocomposites were prepared via in situ polymerization of styrene in the presence of polybutadiene, using an intercalated cationic radical initiator‐MMT hybrid (organoclay). In the solution polymerization in toluene, the silicate layers of the clay were well exfoliated, due to the low extra‐gallery viscosity that can facilitate the diffusion of styrene monomers into the clay layers during the polymerization. The exfoliated HIPS/MMT nanocomposites were also successfully prepared by controlling the viscosity of the reaction medium with prolong swelling of the organoclay in styrene, prior to bulk polymerization. The HIPS/MMT nanocomposites, obtained from bulk polymerization, exhibited a significant improvement in thermal stability, compared to those obtained from solution polymerization as well as the pure polymer counterparts. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Synergistic reinforcement of nanoclay and mesoporous silicate fillers in polycaprolactone: The effect of nanoclay on the compatibility of the components

Biodegradable nanocomposites based on poly(ε-caprolactone) (PCL) reinforced by mesoporous silicate (MCM) were prepared by a melt-extrusion process using a second nanoclay, i.e. modified organophilic silicate layers as compatibilizer. The compatibilizing role of the nanoclay was studied with respect to the morphological, melt-rheological and dynamic mechanical properties of these nanocomposites. Transmission electron microscopy showed that a homogeneous dispersion of MCM had been achieved with addition of the nanoclay (0.5 wt.%) to the PCL/MCM composite. Oscillatory frequency sweep measurements showed that addition of about 3.0 wt.% MCM, in the presence of silicate layers (0.5 wt.%), led to a solid-like response where a percolated network structure is formed. As a result, the Elastic modulus (E), in the rubbery plateau, increased significantly with the filler contents at all temperatures studied, having, at a loading level of only 4 wt.%, values approximately 50% higher than the neat PCL. This reinforcement is probably due to a synergistic effect that arises from the combination of the modified layered clays and the mesoporous silicate particles. In comparison, in the absence of silicate layers, the mesoporous silicate aggregates inside the PCL matrix, and the reinforcement was negligible.     

Microstructural evolution of electrically activated polypropylene/layered silicate nanocomposites investigated by in situ synchrotron wide-angle X-ray scattering and dielectric relaxation analysis

Electric field was found to facilitate the destruction of layer stacking and separation of silicate layers in polypropylene (PP)/layered silicate nanocomposites, resulting in the penetration of polymer chains into silicate galleries. In this study, we describe the real-time microstructural evolution of PP/clay nanocomposites under electric field investigated by in situ synchrotron wide-angle X-ray scattering (WAXS) analysis. We were able to identify two distinctive mechanisms for the formation of nanocomposites depending on the type of electric field. We observed that the exfoliation process prevails in the AC field, while the alignment of silicates parallel to the electric field predominates in the DC field. Dielectric relaxation analysis showed that the different mechanisms originate from different charge distributions of bound ions attached to the clay surfaces due to the applied electric field.     

Influence of intercalated organoclay on the phase structure and physical properties of PTT–PTMO block copolymers

Poly(trimethylene terephthalate-block-tetramethylene oxide) (PTT–PTMO) copolymer/organoclay nanocomposites were prepared by in situ polymerization. They showed an intercalated silicate structure, as determined by X-ray diffraction and transmission electron microscopy. The influence of intercalated organoclay on the two-phase structure and mechanical properties of PTT–PTMO block copolymer was examined by using DSC and tensile tests. The DSC results imply that the silicate layers (Nanofil 32) in PTT–PTMO act as nucleation agents and accelerate the crystallization of PTT hard phase during the cooling down process from the melt. The introduction of silicate layers does not have great effect on the glass transition temperature of PTMO-rich soft phase, melting temperature of PTT hard phase, and degree of crystallinity of the nanocomposites. As the organoclay loading in the nanocomposites increase, the enhanced tensile modulus and yield stress was observed. The cyclic tensile tests showed that obtained nanocomposites have values of permanent set comparable to the neat PTT–PMO copolymer.     

Polymethacrylic acid/Na-montmorillonite/SiO<Subscript>2</Subscript> nanoparticle composites structures and thermal properties

In this article, polymethacrylic acid/Na-montmorillonite/SiO₂ nanoparticle (PMAA/Na-MMT/SiO₂) composites were prepared via in situ polymerization. Fourier transform infrared spectroscopy (FTIR) indicated that the polymerization of SiO₂ nanoparticle and MAA have been taken place. X-ray diffraction (XRD) results suggest that Na-MMT layers are exfoliated during the polymerization process. As evidenced by the transmission electron microscopy (TEM), the Na-MMT layers and SiO₂ nanoparticles exhibit good dispersion in the polymer matrix. It was found that the PMAA/Na-MMT/SiO₂ composite exhibit considerably enhanced thermal properties compared with the PMAA/Na-MMT.     

Determination of the glass transition temperature of polymer/layered silicate nanocomposites from positron annihilation lifetime measurements

The glass transitions of acrylonitrile-butadiene rubber (NBR)/organoclay nanocomposites with various silicate contents were investigated using positron annihilation lifetime spectroscopy (PALS). The nanocomposites were prepared through melt intercalation of NBR with various concentrations of organoclay (OC30B) modified with the organic modifier, methyl tallow bis(2-hydroxyethyl) quaternary ammonium (MT2EtOH), i.e., Cloisite^® 30B. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) measurements of the NBR/OC30B nanocomposites showed that the NBR chains were intercalated between the silicate layers, thereby increasing the gallery heights of the organosilicates. The glass transition temperature of NBR was determined using differential scanning calorimetry (DSC). However, it seemed to be very difficult to clearly resolve the very small differences in T_gs caused from various loading of nanosized silicate in NBR/OC30B nanocomposites. Hence, we performed positron annihilation lifetime spectroscopy (PALS) on NBR/OC30B nanocomposites containing various amounts of OC30B (1-10 wt%). Significant changes in the temperature dependencies of free volume parameters (i.e., lifetimes and intensities) were observed at the transition temperature, T_g,PALS, and the T_g,PALS values were found to increase with increasing organoclay content in the samples. These observations are consistent with PALS having a higher sensitivity in the detection of very small changes in free volume properties. The present findings thus highlight the usefulness of PALS for studying phase transition phenomena in polymeric materials with nanoscale structural variations.     

Synthesis and characterization of poly(acrylonitrile)/montmorillonite nanocomposites from surface‐initiated redox polymerization

We have developed a facile method to prepare polyacrylonitrile/montmorillonite (PAN/MMT) nanocomposites using the surface‐initiated redox polymerization of acrylonitrile (AN) in the aqueous phase. The MMT silicate surfaces were first treated with diethanolamine, and the modified MMT (DEA‐MMT) was subsequently used together with the Ce(IV) salt to serve as a redox system. The PAN chains growing on a surface‐tethered DEA expand the interlayer space, and thus lead to intercalated/exfoliated nanocomposites. The nano‐morphology of the prepared nanocomposites depends on the AN/OH molar ratio in feed. An exfoliated PAN/MMT nanocomposite was obtained when the feeding AN/OH molar ratio = 300 was used. The molecular weight of PAN in the nanocomposites prepared by the present method is also dependent on the AN/OH molar ratio in feed and can be up to ca. 160,000 g/mol. The differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) analyses show that the increasing fraction of exfoliated silicate structures should enhance the contact interface between the silicate and polymer, resulting in the higher glass transition temperature and thermal stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010