Synthesis and characterization of poly(propylene)/montmorillonite nanocomposites by simultaneous grafting‐intercalation

A novel process for the preparation of poly(propylene)/montmorillonite (PP/MMT) nanocomposites was developed via simultaneous solution grafting‐intercalation in the presence of a reactive ammonium cation that can be grafted onto poly(propylene). Partially introducing this reactive cation into long alkyl ammonium modified MMT interlayers can transfer a conventional microcomposite into intercalated/exfoliated nanocomposites, which was evidenced by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The PP chains were tethered onto the clay surface through the bridge of the reactive ammonium cations, which can be characterized by FTIR. The bridged chemical bonding also results in a good interface adhesion between PP and MMT, as confirmed by SEM investigation. The enhanced thermal properties of PP/MMT nanocomposites were characterized by thermogravimetric analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1018–1023, 2004     

Studies on the poly(styrene‐b‐butadiene‐b‐styrene)/clay nanocomposites prepared by melt intercalation

Two types of SBS/OMMT composites are prepared by melt blending using a twin‐screw extruder. An X‐ray diffractometer indicates that polymer chains have intercalated into the gallery of the clay. It is shown in TEM photos that the thickness of the layer aggregate in the SBS1301 matrix is approximately 200 Å, but in the SBS4402 matrix the size of the filler particle is in micrometers. When SBS1301 is intermingled into SBS4402/OMMT, the particle size is reduced obviously. The tensile strength and elongation at break of the nanocomposite, SBS1301/OMMT, increase with the addition of OMMT; and when addition is 5phr, they achieve maximum. A small content of OMMT (less than 5phr) can prevent the deterioration of the mechanical properties of the SBS1301/MMT. In addition, a small content of SBS4402 (less than 20 wt %) can improve the mechanical properties of the SBS1301/OMMT composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 146–152, 2005     

熔体插层制备硅橡胶/蒙脱土纳米复合材料的性能研究

通过熔体插层成功制备了硅橡胶／蒙脱土纳米复合材料，通过XRD和SEM分析可知，在所选择的两步工艺务件下。蒙脱土被硅橡胶分子链插层剥离。获得剥离型的纳米复合材料。同时，测试了其力学性能和耐热性能。所得到的复合物的性能较纯硅橡胶有很大的提高，且与气相法白炭黑填充体系的性能相当。并且研究了硅烷偶联剂对填料-硅橡胶之间的增强作用。     

Poly(ε-caprolactone)/clay nanocomposites prepared by melt intercalation: mechanical, thermal and rheological properties

(Nano)composites of poly(ε-caprolactone) (PCL) were prepared by melt blending the polymer with natural Na⁺ montmorillonite and montmorillonite modified by hydrogenated tallowalkyl (HTA)-based quaternary ammonium cations, such as dimethyl 2-ethylhexyl HTA ammonium and methyl bis(2-hydroxyethyl) HTA ammonium. Microcomposites or nanocomposites were prepared depending on whether neat or modified montmorillonites was used, as assessed by X-ray diffraction and transmission electron microscopy. Mechanical and thermal properties were studied as a function of the filler content by tensile testing, Izod impact testing, thermogravimetric analysis and differential scanning calorimetry. The rheological behaviour at 80 °C was also analysed in relation to the structure and content of the layered silicate. Effect of exfoliated silicates on the mechanical properties, thermal stability and flame resistance of PCL was considered. Stiffness and thermal stability improved with the filler loading until a content of 5 wt%. Further loading resulted in the levelling off and possibly in a decrease of these properties. A marked charring effect was observed upon exposure to a flame.     

熔融插层法制备聚合物/蒙脱土纳米复合材料

综述了熔融插层法制备聚合物,蒙脱土纳米复合材料的新进展。熔融插层法制备聚合物,蒙脱土纳米复合材料具有设备简单、无单体限制和不需要溶剂的优点,并从热力学角度探讨了熔融插层法制备聚合物,蒙脱土纳米复合材料的不足以及改进措施。     

聚合物/蒙脱土纳米复合材料的研究进展

综述了聚合物/蒙脱土纳米复合材料的制备、结构类型等,并以尼龙、聚丙烯、聚苯乙烯等聚合物为例,介绍了纳米复合材料的最新研究进展。     

Studies of particle dispersion in plasticized poly(vinyl chloride)/montmorillonite nanocomposites

Poly(vinyl chloride)(PVC) and dioctyl phthalate (DOP) were mixed with 5 and 10 wt % of Cloisite Na⁺, Cloisite 30B or Cloisite 93A. The obtained nanocomposites were characterized by thermal analysis using a thermogravimetric analyzer which showed that addition of 5 wt % of nanoclay to PVC increased its thermal stability in the sequence: Cloisite Na⁺< Cloisite 93A< Cloisite 30B. The electrical conductivity of these composites was studied as a function of temperatures and showed that the conductivity of PVC was enhanced upon using 5 wt % of nanoclay in the sequence: Cloisite Na⁺< Cloisite 30B < Cloisite 93A. The activation energy of interaction of PVC with nanoclay was found to be lowest for the composite containing 5 wt % of nanoclay in the same sequence. The tensile strength, elongation (%), and Young's modulus were considerably enhanced upon increasing the clay content to 5 wt % in the sequence: Cloisite Na⁺< Cloisite 93A < Cloisite 30B. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) were used to study these nanocomposite structures, and it was found that the organoclay layers are homogeneously dispersed in the PVC matrix when 5 wt % of Cloisite 30B or Cloisite 93A was used. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Electron beam synthesis and characterization of poly(vinyl alcohol)/montmorillonite nanocomposites

Poly(vinyl alcohol) (PVA)/montmorillonite clay (MMT) nanocomposites in the form of films were prepared under the effect of electron beam irradiation. The PVA/MMT nanocomposites gels were characterized by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and mechanical measurements. The study showed that the appropriate dose of electron beam irradiation to achieve homogeneous nanocomposites films and highest gel formation was 20 kGy. The introduction of MMT (up to 4 wt %) results in improvement in tensile strength, elongation at break, and thermal stability of the PVA matrix. In addition, the intercalation of PVA with the MMT clay leads to an impressive improved water resistance, indicating that the clay is well dispersed within the polymer matrix. Meanwhile, it was proved that the intercalation has no effect on the metal uptake capability of PVA as determined by a method based on the color measurements. XRD patterns and SEM micrographs suggest the coexistence of exfoliated intercalated MMT layers over the studied MMT contents. The DSC thermograms showed clearly that the intercalation of PVA polymer with these levels of MMT has no influence on the melting transitions; however, the glass transition temperature (T_g) for PVA was completely disappeared, even at low levels of MMT clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1129–1138, 2006     

Comparison of solution intercalation and melt intercalation of polymer-clay nanocomposites

Polymer-clay nanocomposites of poly(ethylene oxide)/Na-montmorillonite (PEO/MMT) and PEO/organo-modified bentonite (B34) systems prepared via solution intercalation and melt intercalation have been compared by X-ray diffraction and Fourier transform infrared (FTIR) analysis. The gallery size of solution-intercalated hybrids in both PEO/MMT and PEO/B34 systems increases with PEO content up to a plateau level at 15%. However, the gallery size of melt-intercalated PEO/MMT and PEO/B34 hybrid remains the same regardless of the PEO concentration. FTIR analysis shows no difference in spectrum of samples prepared by solution intercalation compared to melt intercalation. The PEO conformation in the PEO/clay intercalated hybrids is concluded to be a distorted helical structure.     

PVC/黏土纳米复合材料研究进展

文章简要概述了黏土的有机改性机理,聚氯乙烯/黏土纳米复合材料的特性及其制备方法、结构与表征方面的研究进展。对熔融插层共混法、溶液插层共混法、原位聚合法和插层聚合法进行了介绍和比较,对聚氯乙烯/黏土纳米复合材料的重点研究领域和发展趋势提出了具有前瞻性的预测。     

Prepared hydrogenated nitrile rubber (HNBR)/organo–montmorillonite nanocomposites by the melt intercalation method

The polymer, Hydrogenated Nitrile‐Butadiene Rubber (HNBR) was melt compounded with organophilic montmorillonite (OMMT). The dispersion of the OMMT in the HNBR matrix was characterized by X‐ray diffraction (XRD), which indicated that at the temperature of 100°C, the organoclay belong to the exfoliated and interlayer structure. The effect of sulfur on the dispersion of OMMT in the polymer matrix was also studied. The vulcanization changed the dispersion of OMMT in polymer matrix greatly and the basal spacing of clay layers is decreased after vulcanization. The mechanical properties, Akron abrasion and the crude oil medium aging‐resistant of HNBR nanocomposites were examined as a function of the OMMT content in the matrix of polymer. The results of the test show remarkable improvement in tensile strength, tear strength, aging‐resistant, and hardness of HNBR nanocomposites than that of unfilled HNBR. It is obvious that the 10 phr of OMMT filled nanocomposites have the best mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An investigation of melt rheology and thermal stability of poly(lactic acid)/ poly(butylene succinate) nanocomposites

A systematic investigation of the rheological and thermal properties of nanocomposites prepared with poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and organically modified layered silicate was carried out. PLA/PBS/Cloisite 30BX (organically modified MMT) clay nanocomposites were prepared by using simple melt extrusion process. Composition of PLA and PBS polymers were fixed at a ratio of 80 to 20 by wt % for all the nanocomposites. Rheological investigations showed that high clay (> 3 wt %) contents strongly improved the viscoelastic behavior of the nanocomposites. Percolation threshold region was attained between 3 and 5 wt % of clay loadings. With the addition of clay content for these nanocomposites, liquid‐like behavior of PLA/PBS blend gradually changed to solid‐like behavior as shown by dynamic rheology. Steady shear showed that shear viscosity for the nanocomposites decreased with increasing shear rates, exhibiting shear‐thinning non‐Newtonian behavior. At higher clay concentrations, pseudo‐plastic behavior was dominant, whereas pure blend showed almost Newtonian behavior. Thermogravimetric analysis revealed that both initial degradation temperature (at a 2% weight loss) and activation energy of thermal decomposition nanocomposite containing 3 wt % of C30BX were superior to those of other nanocomposites as well as to those of PLA/PBS blend. Nanocomposite having 1 wt % of C30BX did not achieve expected level of thermal stability due to the thermal instability of the surfactant present in the organoclay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of novel poly(o‐toluidine) montmorillonite nanocomposites: Effect of surfactant on intercalation

The investigation of clay based polymer nanocomposites has opened the door for the development of novel, ecofriendly advanced nano materials that can be safely recycled. Because of their nanometer size dispersion, these nanocomposites often have superior physical and mechanical properties. In this study, novel nanocomposites of poly(o‐toluidine) (POT) and organically modified montmorillonite (MMT) were synthesized using camphor sulfonic acid (CSA), cetyl pyridinum chloride (CPCl), and N‐cetyl‐N,N,N‐trimethyl ammonium bromide (CTAB) to study the role of surfactant modification on the intercalation. The in situ intercalative polymerization of POT within the organically modified MMT layers was analyzed by FTIR, UV–visible, XRD, SEM as well as TEM studies. The average particle size of the nanocomposites was found to be in the range 80–100 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Dispersion of nanoclays with poly(ethylene terephthalate) by melt blending and solid state polymerization

Melt intercalation of clay with poly(ethylene terephthalate; PET) was investigated in terms of PET chain mobilities, natures of clay modifiers, their affinities with PET, and nanocomposite solid state polymerization (SSP). Twin screw extrusion was used to melt blend PET resins with intrinsic viscosities of 0.48, 0.63, and 0.74 dL/g with organically modified Cloisite 10A, 15A, and 30B montmorillonite clays. Clay addition caused significant molecular weight reductions in the extruded PET nanocomposites. Rates of SSP decreased and crystallization rates increased in the presence of clay particles. Cloisite 15A blends showed no basal spacing changes, whereas the basal spacings of Cloisite 10A and Cloisite 30B nanocomposites increased after melt extrusion, indicating the presence of intercalated nanostructures. After SSP these nanocomposites also exhibited new lower angle X‐ray diffraction peaks, indicating further expansion of their basal spacings. Greatest changes were seen for nanocomposites prepared from the lowest molecular weight PET and Cloisite 30B, indicating its greater affinity with PET and that shorter more mobile PET chains were better able to enter its galleries and increase basal spacing. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal stability of poly(vinyl chloride)/layered double hydroxide nanocomposites

Effects of nanoscale dispersed layered double hydroxides (LDHs) on thermal stability of poly(vinyl chloride) (PVC) in thermal and thermooxidative degradation processes are investigated by dynamic and isothermal thermogravimetric analysis (TGA), discoloration test, fourier transform infrared (FTIR), and ultraviolet‐visible (UV‐vis) spectroscopic techniques. During both stages of thermal degradation, the degradation temperatures, including onset degradation temperature and temperature of the maximum degradation rate, increase, and the final residue yield of the PVC/LDH nanocomposites reaches 14.7 wt %, more than double that for neat PVC. The thermooxidative degradation process is more complex. During the first two stages, the presence of nanoscale dispersed LDH particles enhances the thermal stability, whereas in the last stage accelerates the thermal degradation possibly due to the accumulation of heat released. Additionally, the studies of the isothermal thermooxidative degradation process by FTIR and UV‐vis spectra indicate that both polyene backbone formation and some carbonyl groups are simultaneously developed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of alkylammonium salt on the dispersion and properties of Poly(p‐phenylene sulfide)/clay nanocomposites via melt intercalation

To explore the possibility of making poly(p‐phenylene sulfide) (PPS) nanocomposites via melt intercalation and improving the mechanical properties of PPS, in this study we first modified clay (montmorillonite) with alkylammonium salt by cation exchange and then mixed the modified clay together with the PPS matrix by twin‐screw extrusion. Because the PPS/clay composites were made at a high temperature (300°C), thermogravimetric analysis experiments were carried out first to check the thermal stability of the alkylammonium salt treated clay and the obtained composites. Possible degradation of the alkylammonium salt during processing caused a decrease in the interlayer spacing of the clay. Scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction were used to investigate the dispersion of the clay sheet in the matrix. The clay layers were homogeneously dispersed in the PPS matrix with a nanometer scale, and an exfoliated structure was achieved at a low load of clay. The alkylammonium salt modifier enhanced the interaction between the PPS and clay on the one hand, but on the other hand, it also acted as a plasticizer and caused decreases in the glass‐transition temperature and tensile properties. More work is needed to find a modifier and processing conditions by which the modifier can help the dispersion of clay and also be completely degraded after the formation of an exfoliated structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1724–1731, 2006     

熔融插层法制备累托石/聚碳酸亚丙酯纳米复合材料的研究

采用熔融插层法制备了有机化累托石/聚碳酸亚丙酯纳米复合材料,通过X射线衍射、原子力显微镜、热重分析法测试了复合材料的结构与热性能。结果表明:聚碳酸亚丙酯能插层于累托石片层中,累托石/聚碳酸亚丙酯纳米复合材料的耐热性有了很大程度的提高。     

The effects of metallic derivatives released from montmorillonite on the thermal stability of poly(ethylene terephthalate)/montmorillonite nanocomposites

By in situ polycondensation, poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites was prepared, which were characterized via X‐ray diffraction and transmission electron microscope. The processing stability of these nanocomposites was investigated by the change of number–average molecular weight and carboxyl terminal group content during injection molding, and the thermal stability of the nanocomposites was investigated via thermogravimetric analysis. It was found that some metallic derivatives released from MMT during polycondensation had a great influence on the processing and thermal stabilities of the nanocomposites. The quantity of these metallic derivatives was determined by inductively coupled plasma. The stabilization effect of phosphorous compounds generated from MMT modified with phosphonium was observed. Processing stability and thermal stability of these nanocomposites exhibited similar trend because of almost the same causes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1692–1699, 2006     

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