Suspension polymerization of poly(methyl methacrylate)/clay nanocomposites

Polymer/clay nanocomposites (PCNs) of poly(methyl methacrylate) and an organically modified clay, Cloisite 15a, were synthesized in situ with a suspension polymerization technique. The amount of clay present in the PCNs was varied to provide a better understanding of the effect of the clay on the properties of the polymer matrix. However, unexpectedly, we found that the concentration of clay had a dramatic impact on the molecular weight of the polymer matrix, and a relationship between the clay concentration and polymer molecular weight was determined. The PCNs were characterized with size exclusion chromatography (SEC), X‐ray diffraction, transmission electron microscopy, and oscillatory shear rheology. From oscillatory shear rheology, the full master curves for the PCNs were obtained by application of the time–temperature superposition principle. To enable the effect of the clay on the rheology to be quantified, the experimental data was compared to the time‐dependent diffusion model of des Cloizeaux for polydisperse polymer melts, which enabled the polydispersity to be incorporated through the use of the molecular weight distribution obtained via SEC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(methyl acrylate-co-methyl methacrylate)/montmorillonite nanocomposites fabricated by soap-free emulsion polymerization

The exfoliated poly(methyl acrylate-co-methyl methacrylate)/montmorillonite (MMT) nanocomposite latex solutions fabricated by soap-free emulsion polymerization were able to cast into a film. The films were transparent and ductile unless more than 5 wt% of MMT was incorporated. With the MMT content higher than 5 wt%, the inflammable residuals of nanocomposites after combustion could preserve their original film profile acting like an inflammable scaffold. Moreover, as 20 wt% MMT was incorporated, the yield strength of the films was increased up to 20 times and Young’s modulus up to 2,000 times. However, the water vapor permeability coefficient of the films was only decreased down to its half value. This unexpected behavior of permeability was associated with the decrease of T _g as the content of MMT was increased, owing to the large difference of the reactivity ratios between methyl acrylate and methyl methacrylate monomers and their differential absorption to the MMT during copolymerization.     

Synthesis and characterization of poly(methyl methacrylate)/montmorillonite nanocomposites by in situ bulk polymerization

Poly(methyl methacrylate)/montmorillonite (MMT) nanocomposites were prepared by in situ bulk polymerization. The results showed that the silicone coupling agent affected the structure and properties of hybrid materials. XRD analysis showed that the dispersion of clay in nanocomposites with silicone‐modified organophilic MMT was more ordered than that in nanocomposites with unmodified organophilic MMT. The glass transition temperature (T_g) of the nanocomposites was 6–15°C higher and the thermal decomposition temperature (T_d) was 100–120°C higher than those of pure PMMA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2256–2260, 2003     

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     

Synthesis of poly(butyl acrylate‐co‐methyl methacrylate)/montmorillonite waterborne nanocomposite via semibatch emulsion polymerization

Poly(butyl acrylate‐co‐methyl methacrylate)‐montmorillonite (MMT) waterborne nanocomposites were successfully synthesized by semibatch emulsion polymerization. The syntheses of the nanocomposites were performed in presence of sodium montmorillonite (Na‐MMT) and organically modified montmorillonite (O‐MMT). O‐MMT was used directly after the modification of Na‐MMT with dimethyl dioctadecyl ammonium chloride. Both Na‐MMT and O‐MMT were sonified to obtain nanocomposites with 47 wt % solids and 3 wt % Na‐MMT or O‐MMT content. Average particle sizes of Na‐MMT nanocomposites were measured as 110–150 nm while O‐MMT nanocomposites were measured as 200–350 nm. Both Na‐MMT and O‐MMT increased thermal, mechanical, and barrier properties (water vapor and oxygen permeability) of the pristine copolymer explicitly. X‐ray diffraction and transmission electron microscope studies show that exfoliated morphology was obtained. The gloss values of O‐MMT nanocomposites were found to be higher than that of the pristine copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42373.     

Synthesis of poly(methyl methacrylate)/silica nanocomposite through emulsion polymerization using dimethylaminoethyl methacrylate

Polymer/Silica nanocomposite latex particles were prepared by emulsion polymerization of methyl methacrylate (MMA) with dimethylaminoethyl methacrylate (DM). The reaction was performed using a nonionic surfactant and in the presence of silica nanoparticles as the seed. The polymer‐coated silica nanoparticles with polymer content and number average particle sizes ranged from 32 to 93 wt % and 114–310 nm, respectively, were obtained depending on reaction conditions. Influences of some synthetic conditions such as MMA, DM, surfactant concentration, and the nature of initiator on the coating of the silica nanoparticles were studied. Electrostatic attraction between anionic surface of silica beads and cationic amino groups of DM is the main driving force for the formation of the nanocomposites. It was demonstrated that the ratio of DM/MMA is important factor in stability of the system. The particle size, polymer content, efficiency of the coating reaction, and morphology of resulted nanocomposite particles showed a dependence on the amount of the surfactant. Zeta potential measurements confirmed that the DM was located at the surface of the nanocomposites particles. Thermogravimeteric analysis indicated a relationship between the composition of polymer shell and polymer content of the nanocomposites. The nanocomposites were also characterized by FTIR and differential scanning calorimetry techniques. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation,structural characterization,and properties of poly(methyl methacrylate)/montmorillonite nanocomposites by bulk polymerization

Poly(methyl methacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were synthesized by a simple technique of a monomer casting method, bulk polymerization. The products were purified by hot acetone extraction and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), examination of their mechanical properties, and light transmittance testing. Although XRD data did not show any apparent order of the MMT layers in the nanocomposites, TEM revealed parallel MMT layers with interlamellar spacings of an average of 9.8 nm and the presence of remnant multiplets of nonexfoliated layers. Therefore, PMMA chains were intercalated in the galleries of MMT. DSC and TGA traces also corroborated the confinement of the polymer in the inorganic layer by exhibiting the increase of glass‐transition temperatures and mass loss temperatures in the thermogram. Both the thermal stability and the mechanical properties of the products appeared to be substantially enhanced, although the light transmittances were not lost. Also, the materials had excellent mechanical properties. Measurement of the tensile properties of the PMMA/MMT nanocomposites indicated that the tensile modulus increased up to 1013 MPa with the addition of 0.6 wt % MMT, which was about 39% higher than that of the corresponding PMMA; the tensile strength and Charpy notched impact strength increased to 88 MPa and 12.9 kJ/m², respectively. As shown by the aforementioned results, PMMA/MMT nanocomposites may offer new technology and business opportunities. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 348–357, 2005     

Synthesis and properties of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposites

PMMA/MMT nanocomposites were successfully synthesized via in situ intercalative polymerization, and characterized by means of wide‐angle X‐ray diffractometry, transmission electron microscopy, thermal gravimetric analysis, dynamic mechanical analysis and Fourier‐transform infrared analysis. The nanocomposites possess partially exfoliated and partially intercalated structure, in which the silicate layers are exfoliated into nanometre secondary particles with thickness of less than 20 nm and uniformly dispersed in the polymer matrix. In comparison with pure PMMA, the thermal stability, glass transition temperature, and mechanical properties of the polymer are notably improved by the presence of the nanometric silicate layers. It was found that part of the PMMA chains in the nanocomposites are well immobilized inside and/or onto the layered silicates and, therefore, the unique properties of the nanocomposites result from the strong interactions between the nanometric silicate layers and the polymer chains. Copyright © 2003 Society of Chemical Industry     

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.     

Synthesis and characterization of poly(glycidyl methacrylate)/Na‐montmorillonite nanocomposites

Poly(glycidyl methacrylate)/Na–montmorillonite nanocomposites were synthesized by free‐radical polymerization of glycidyl methacrylate containing dispersed montmorillonite. By changing the concentration of glycidyl methacrylate several polymer–clay nanocomposites were prepared and the resulting nanocomposites were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The results indicated that the properties of the composite were significantly improved. The thermogravimetric analysis results revealed that the degradation temperatures of nanocomposites were higher than that of pure polymer and the thermal degradation rates decreased. Examination of these materials by scanning electron microscopy showed that the clay layers are dispersed homogenously in the polymer matrix and the formation of intercalation nanostructure. Furthermore, adsorptive, moisture regain, and water uptake properties of nanocomposites were also investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1532–1538, 2004     

The effect of clay modification on the mechanical properties of poly(methyl methacrylate)/organomodified montmorillonite nanocomposites prepared by in situ suspension polymerization

Poly(methylmethacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were prepared by in situ suspension polymerization. MMT was previously organically modified by different modification agents [dioctadecyl dimethyl ammonium chloride (DODAC) and methacrylatoethyltrimethyl ammonium chloride (MTC)] and different modification method (cation‐exchange reaction and grafting reaction), ultimately giving rise to five kinds of organomodified MMT (OMMT). The structure of the OMMT was studied by Wide angle X‐ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR). Meanwhile, the structure of the PMMA/MMT nanocomposites microspheres was also investigated by WAXD. The molecular weight of the polymers extracted from PMMA/MMT nanocomposites was measured by gel permeation chromatograph (GPC). Finally, the mechanical properties of these PMMA/MMT nanocomposites were studied in detail. It was found that large interlayer spacing (d₀₀₁) of OMMT could not entirely ensure an exfoliated structure of resultant PMMA/MMT nanocomposites, while OMMT with relative small d₀₀₁ could still yield exfoliated structure as long as the compatibility between OMMT and polymer matrix was favorable. In addition, the results of mechanical investigation indicated that the compatibility between OMMT and PMMA matrix turned out to be the dominant factor deciding the final mechanical properties of PMMA/MMT nanocomposites. POLYM. COMPOS., 37:1705–1714, 2016. © 2014 Society of Plastics Engineers     

Synthesis of chitosan‐modified poly(methyl methacrylate) by emulsion polymerization

Emulsion polymerization of methyl methacrylate (MMA) in the presence of chitosan was studied and a reaction mechanism was proposed. It was proved in the companion article that potassium persulfate (KPS) free radicals can degrade chitosan chains into chain free radicals. Therefore, it is possible to produce a chitosan copolymer when the monomer and the KPS initiator are added into the chitosan solution. According to the proposed mechanism, concentrations of different species such as the initiator, total free radicals, and degraded chitosan chain were calculated with the reaction time. All the results agreed with the experimental observation. The results showed that the polymerization rate varied with 0.83‐ and 0.82‐order of the total free‐radical concentration and chitosan repeating unit concentration, respectively. It was also verified that chitosan played multiple roles in the reaction system. If the monomer was added into the chitosan solution before the addition of KPS, chitosan served mainly as a surfactant. Consequently, the polymer particle number was increased with the chitosan addition and so was the polymerization rate. However, if the monomer was added into the solution where the chitosan was already degraded by KPS, the polymerization rate was decreased with the predegradation time of chitosan. In both cases, the final polymer particles consisted of the poly(methyl methacrylate) (PMMA) homopolymer and the chitosan‐PMMA copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3047–3056, 2002     

Preparation and characterization of poly(methyl methacrylate)/reactive montmorillonite nanocomposites

The poly(methyl methacrylate) (PMMA)/reactive montmorillonite nanocomposites were prepared by emulsion polymerization. The double bonds were introduced to both the surfaces and interlayers of the montmorillonites to obtain the reactive montmorillonites. The structure of the nanocomposites measured by wide angle X‐ray diffraction (WAXD) indicated that the montmorillonites were exfoliated. The average molecular weight of the nanocomposites revealed by gel permeation chromatography (GPC) was larger than that of pure PMMA. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicated that the thermal properties of the nanocomposites were enhanced and could be affected by the amount of the reactive montmorillonites. In addition, the tensile properties of the nanocomposites measured by an Instron testing machine improved and the nanocomposites including 3 wt% reactive montmorillonites showed the best tensile strength. The Young's modulus increased with the addition of the reactive montmorillonites. The aging properties of the nanocomposites had an improvement compared with pure PMMA. The optical properties assessed by UV‐Visible spectroscopy revealed that the transmittance decreased as the amount of the reactive montmorillonites increased. Finally, the mechanism to prepare PMMA/reactive montmorillonite nanocomposites was proposed. POLYM. COMPOS., 37:2396–2403, 2016. © 2015 Society of Plastics Engineers     

Poly(methyl methacrylate)/clay nanocomposites by photoinitiated free radical polymerization using intercalated monomer

A series of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposite were prepared by successfully dispersing the inorganic nanolayers of MMT clay in an organic PMMA matrix via in situ photoinitiated free radical polymerization. Methyl methacrylate monomer was first intercalated into the interlayer regions of organophilic clay hosts by “click” chemistry followed by a typical photoinitiated free radical polymerization. The intercalated monomer was characterized by FT-IR spectroscopy, elemental analysis and thermogravimetric analysis methods. The intercalation ability of the modified monomer and exfoliated nanocomposite structure were confirmed by X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Thermal stability of PMMA/MMT nanocomposites was also studied by both differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).     

Poly(methyl methacrylate)/montmorillonite nanocomposites prepared by bulk polymerization and melt compounding

This article focuses on structural, thermal, and mechanical properties of nanocomposites in dependence of preparation method and poly(methyl mathacrylate) (PMMA)/organically modified montmorillonite (OMMT) ratio. PMMA/OMMT nanocomposites were prepared by bulk polymerization and by melt compounding. Properties of nanocomposites of the same composition prepared by the two methods were compared. It was observed that nanocomposites prepared via melt compounding at 200°C had a highly oriented structure with lower interlayer spacing values than nanocomposites prepared via bulk polymerization. Two reasons for the observed smaller interlayer spacing obtained by melt compounding were identified. The first is enhanced PMMA penetration and/or formation between layers in the case of bulk polymerization, which was confirmed by determination of stronger interactions between OMMT and PMMA by Soxhlet extraction, infrared spectroscopy, and differential dynamic calorimery. The second reason for smaller interlayer spacing for nanocomposites prepared by melt compounding is organic modifier degradation during melt compounding process, which was confirmed by thermogravimetric analysis. Both reasons lead to the fracture of melt compounded nanocomposites on the OMMT‐polymer interface, which was observed by scanning electron microscopy. For nanocomposites with disoriented structure and larger interlayer spacing prepared via bulk polymerization the fracture occurred in the polymer matrix. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Effect of organoclays on the rheological and morphological properties of poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate)/ clay nanocomposites

Using the rheological measurements, the effect of three types of organoclays on the morphology and nanoclay dispersion in the poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate) (ABS/PMMA) blends was investigated. For this purpose, polymers were melt blended with 2 and 4 wt% of organoclays in a twin‐screw extruder. Structural analysis of the blends and nanocomposites through the rheometery, theoretical approach, X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy revealed that the clay content and interaction level between clays and the polymers dominated the morphology. While the morphology of the blends varied by PMMA content, smaller PMMA domains were observed for blends containing clay particles. Better‐interacted and intercalated nanoclays were mainly located within the interface at lower content. While, at higher content, they tended to migrate into the dispersed phase. Theoretical calculations of interfacial tensions and wetting coefficients confirmed this kind of migration. POLYM. COMPOS., 33:1893–1902, 2012. © 2012 Society of Plastics Engineers     

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

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

Synthesis of poly(methylmethacrylate)/montmorillonite nanocomposites via in situ intercalative suspension and emulsion polymerization

Summary Na-montmorillonite (MMT) with cation exchange capacity (CEC) of 90 mEq/100g was converted to MMT-CTAB and MMT-CPC forms by the intercalation of Cetyltrimethylammonium bromide (CTAB) and Cetylpyridinium chloride (CPC), respectively. The intercalation of these surfactants onto the basal space of the montmorillonite was evidenced by fourier transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD). The intercalation of the CPC expanded the basal space from 12.19 A^o to 21.47 A^o while in case of CTAB it was expanded to 19.35 A^o only. The (MMT-CPC) was subsequently used as a host for the preparation of PMMA nanocomposites via intercalative suspension and emulsion polymerization of methylmethacrylate (MMA) using benzoyl peroxide (BPO) and potassium persulphate (PPS) individually and simultaneously. The use of BPO and PPS together invoked better exfoliation but the yield did not change appreciably in comparison with using either of the initiators alone. Different structures were obtained with the variation of the preparation conditions; exfoliated and intercalated nanocomposites which were characterized by XRD, transmission electron microscope (TEM), thermal gravimetric analysis (TGA), and differential scanning calorimeter (DSC). The resultant nanocomposites exhibited improved thermal stability relative to the equivalent macrocomposites. No glass transition temperature (Tg) could be detected for the prepared nanocomposites which was assumed to result from the restricted molecular motion of the polymer chains.     

Synthesis and properties of poly(ethylene terephthalate)/clay nanocomposites by in situ polymerization

Poly(ethylene terephthalate) (PET)/clay nanocomposites (PCNs) with N‐methyl diethanol amine (MDEA)‐based organoclays are synthesized by using in situ polymerization. Four kinds of MDEA‐based materials are prepared and used as organifiers of pristine montmorillonite. The clay treated with the organifiers has a d‐spacing range that is about 14–21 Å. The PCNs with these organoclays are characterized by using wide‐angle X‐ray diffraction, scanning and transmission electron microscopy, atomic force microscopy, capillary rheometry, and tensile and barrier testing. The PCNs form an intercalated and delaminated structure. The well‐stacked nanoclays are broken down into small pieces in the PET matrix and the thickness of the clay bundle decreases to 20 nm. The melt viscosity and tensile strength of these PCNs increases with only 0.5 wt % clay. In oxygen barrier testing, the PCN with 1 wt % well‐dispersed organoclay shows a twofold higher barrier property than pure PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1262–1271, 2007