Preparation and characterization of maleic anhydride‐g‐polypropylene/diamine‐modified clay nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by compounding maleic anhydride‐g‐polypropylene (MAPP) with MMT modified with α,ω‐diaminododecane. Structural characterization confirmed the formation of characteristic amide linkages and the intercalation of MAPP between the silicate layers. In particular, X‐ray diffraction patterns of the modified clay and MAPP/MMT composites showed 001 basal spacing enlargement as much as 1.49 nm. Thermogravimetric analysis revealed that the thermal decomposition of the composite took place at a slightly higher temperature than that of MAPP. The heat of fusion of the MAPP phase decreased, indicating that the crystallization of MAPP was suppressed by the clay layers. PP/MAPP/MMT composites showed a 20–35% higher tensile modulus and tensile strength compared to those corresponding to PP/MAPP. However, the elongation at break decreased drastically, even when the content of MMT was as low as 1.25–5 wt %. The relatively short chain length and loop structure of MAPP bound to the clay layers made the penetration of MAPP molecules into the PP homopolymer phase implausible and is thought to be responsible for the decreased elongation at break. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 307–311, 2005     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004     

Effect of exfoliation and dispersion on the yield behavior of melt‐compounded polyethylene–montmorillonite nanocomposites

The yield behavior of melt‐mixed nanocomposites containing 5 wt % organically modified montmorillonite in matrices of a linear low‐density polyethylene (LLDPE) or a modified polyethylene was studied as a function of the temperature and strain rate. In the melt‐mixed LLDPE nanocomposite, the montmorillonite showed a slight increase in the clay spacing, which suggested that the clay was at best intercalated. Transmission electron microscopy (TEM) images showed that the dispersion in this nanocomposite was poor. The use of the modified polyethylene promoted exfoliation of the clay tactoids in the nanocomposite, as assessed by X‐ray diffraction and TEM. In both nanocomposites, the yield mechanisms were insensitive to the addition of the organoclay, even though modest increases in the modulus were produced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3044–3049, 2006     

Preparation of polyethylene–clay nanocomposites directly from Na+ montmorillonite by a melt intercalation method

Polyethylene (PE)/clay nanocomposites were prepared directly from Na⁺ montmorillonite by a melt intercalation technique, using hexadecyl trimethyl ammonium bromide (C16) as a reactive compatibilizer. Three other polymer–clay nanocomposites were also prepared by this new technique. Their structures were characterized by X‐ray diffraction and transmission electron microscopy. The mechanism of this new method was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2583–2585, 2003     

Study on the properties of polyethylene–octene elastomer/wood flour blends

In the present study, the properties of metallocene polyethylene–octene elastomer (POE) and wood flour (WF) blends were examined by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), an Instron mechanical tester, and scanning electron microscopy (SEM). The results showed that the mechanical properties of POE were obviously lowered, due to the poor compatibility between the two phases, when it was blended with WFs. A fine dispersion and homogeneity of WF in the polymer matrix could be obtained when acrylic acid‐grafted POE (POE‐g‐AA) was used to replace POE for manufacture of the blends. This better dispersion is due to the formation of branched and crosslinked macromolecules since the POE‐g‐AA copolymer had carboxyl groups to react with the hydroxyls. This is reflected in the mechanical and thermal properties of the blends. In comparison with a pure POE/WF blend, the increase in tensile strength at break was remarkable for the POE‐g‐AA/WF blend. The POE‐g‐AA/WF blends are more easily processed than are the POE/WF blends, since the former had a lower melt viscosity than that of the latter. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1919–1924, 2003     

Photochemistry of low‐density polyethylene–montmorillonite composites

Photo‐oxidation at the exposed surfaces of low‐density polyethylene/montmorillonite composites was analyzed with attenuated total reflection/Fourier transform infrared spectroscopy. It was found that the clay particles were dispersed but not exfoliated in the polymer matrix. The extent of oxidative degradation of the low‐density polyethylene matrix was slightly greater when montmorillonite was present and was greatest for the blend of low‐density polyethylene and organically modified montmorillonite. The Fourier transform infrared measurements demonstrated that the rate of photo‐oxidation in the bulk was lower than that observed at the surface, but the oxidation chemistry was similar at the surface and in the bulk. The distribution of the photo‐oxidation products was somewhat modified in the presence of montmorillonite and organically modified montmorillonite in comparison with pure low‐density polyethylene, with the yield of acidic products higher and the yield of double bonds lower. These observations were attributed to a slightly higher yield of radicals and some modification of the quantum yield for the processes leading to the formation of double bonds when the clay filler was present. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of polyethylene–clay nanocomposites by an in situ graft method

The polyethylene–clay nanocomposites were prepared by the in situ graft copolymerization of styrene containing twin‐benzyldimethyldioctadecylammonium bromine modified montmorillonite (TBDO‐MMT) in polyethylene with dicumyl peroxide (DCP) as an initiator in molten state. XRD and TEM analysis indicated that intercalated polyethylene/MMT nanocomposites are obtained. The mechanics performance, crystal behavior, thermal properties, and the effect of MMT contents on PE/MMT nanocomposite were also studied. As comparison, polyethylene/montmorillonite composites prepared by a simply melt compounding without styrene were studied as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4921–4927, 2006     

Preparation and characterization of polypropylene/clay nanocomposites with polypropylene‐graft‐maleic anhydride

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by the esterification of propylene‐g‐maleic anhydride (MAPP) with MMT modified with α,ω‐hydroxyamines. The structural characterization confirmed the formation of ester linkages and the interaction between the silicate layers. In particular, X‐ray diffraction patterns of the modified clays and MAPP/MMT composites showed 001 basal spacing enlargement as great as 0.14–0.62 nm according to the type of α,ω‐hydroxyamine. Thermal characterization by thermogravimetric analysis for the composites revealed increased onset temperatures of thermal decomposition. The melting peak temperature decreased, and the crystallization peak temperature increased; this indicated that MMT retarded the crystallization of MAPP. Compounding PP with MAPP/MMT composites enhanced the tensile modulus and tensile strength of PP. However, the elongation at break decreased drastically even when the MMT content was as low as 0.4–2.0 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1229–1234, 2005     

Poly(propylene)–poly(propylene)‐grafted maleic anhydride–organic montmorillonite (PP–PP‐g‐MAH–Org‐MMT) nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of poly(propylene) (PP), PP–organic‐montmorillonite (Org‐MMT) composite, and PP–PP‐grafted maleic anhydride (PP‐g‐MAH)–Org‐MMT nanocomposites were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny and a method developed by Mo well‐described the nonisothermal crystallization process of these samples. The difference in the exponent n between PP and composite (either PP–Org‐MMT or PP–PP‐g‐MAH–Org‐MMT) indicated that nonisothermal kinetic crystallization corresponded to tridimensional growth with heterogeneous nucleation. The values of half‐time, Z_c; and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PP and composites, but the crystallization rate of composites was faster than that of PP at a given cooling rate. The method developed by Ozawa can also be applied to describe the nonisothermal crystallization process of PP, but did not describe that of composites. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The results showed that the activation energy of PP–Org‐MMT was much greater than that of PP, but the activation energy of PP–PP‐g‐MAH–Org‐MMT was close to that of pure PP. Overall, the results indicate that the addition of Org‐MMT and PP‐g‐MAH may accelerate the overall nonisothermal crystallization process of PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3093–3099, 2003     

Grafting of maleic anhydride onto polyethylene through a green chemistry approach

The grafting of a polymer can lead to the improvement and modification of the polymer and thus expand its applications. Grafting methods include solution grafting in organic solvents, melt grafting at high temperatures, and light grafting with radioactive sources. These methods have their advantages and disadvantages. The disadvantages include waste treatment, consumption of energy, and so on. In this study, a hydrothermal process which is called the green approach, was developed to prepare graft copolymers. The effect of various factors on the grafting degree was investigated in detail. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of a maleic anhydride grafted polypropylene–butadiene copolymer and its application in polypropylene/styrene–butadiene–styrene triblock copolymer/organophilic montmorillonite composites as a compatibilizer

A maleic anhydride grafted propylene–butadiene copolymer (MPPB) was prepared. Fourier transform infrared spectroscopy and ¹H‐NMR results indicate that the maleic anhydride molecules reacted with the double bond in the butadiene unit of the propylene–butadiene copolymer (PPB), and the grafting percentage increased with the butadiene content in the initial copolymer. The gel permeation chromatography results show that the introduction of butadiene in the copolymer prevented the degradation of PPB. The MPPB was applied in polypropylene (PP)/styrene‐butadiene‐styrene triblock copolymer (SBS)/organophilic montmorillonite (OMMT) composites as a compatibilizer. In the presence of 10‐phr MPPB, the impact strength of the composite was improved by about 20%. X‐ray diffraction patterns indicated the formation of the β‐phase crystallization of PP in the presence of MPPB, and a significant decrease in the spherulite size was observed. Transmission electron microscopy (TEM) images showed that the OMMT was better dispersed in the matrix upon the inclusion of MPPB. A better distribution of the rubber phase and a rugged fracture surface were observed in the scanning electron microscopy images as the MPPB proportion was increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and applicability of functionalized polyethylene with an ethylene/1,7‐octadiene copolymer

The copolymerization of ethylene and 1,7‐octadiene was carried out to synthesize polyethylene with unreacted vinyl groups. The prepared copolymer [poly (ethylene‐co‐1,7‐octadiene) (PEOD)] was epoxidized with peracetic acid, m‐chloroperbenzoic acid, or formic acid/H₂O₂. Of these, peracetic acid gave the best results. Epoxidized PEOD was subjected to a reaction with 2‐mercaptobenzimidazole and poly(L ‐lactic acid). The bromination of PEOD was also performed in the presence of a Br₂/HBr solution at room temperature. The brominated poly(ethylene‐co‐1,7‐octadiene) (PEOD‐Br) was used as a macroinitiator for atom transfer radical polymerization. The polymerization of styrene, butyl methacrylate, and glycidyl methacrylate was performed in bulk or solution at 120°C with a PEOD‐Br/CuBr/2,2′‐dipyridyl initiator system. The thermal properties of the graft copolymers and the efficiency of the graft polymerization were investigated. These graft copolymers have potential applications as interfacial modifiers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of polyethylene‐graft‐poly(styrene‐co‐maleic anhydride) and its compatibilizing effects on polyethylene/starch blends

Low density polyethylene (LDPE) was reacted with benzoyl peroxide (BPO) and 2,2,6,6‐tetramethyl‐l‐piperidinyloxy (TEMPO) to prepare a latent macroinitiator, PE–TEMPO. Little polymer was synthesized when maleic anhydride (MAH) was bulk polymerized in the presence of the PE–TEMPO. However, addition of styrene accelerated the polymerization rate and PE‐grafted‐poly(styrene‐co‐maleic anhyride) [PE‐g‐P(ST‐co‐MAH)] was produced to a high yield. Chemical reaction between MAH units and hydroxyl groups of starch was nearly undetectable in the PE/PE‐g‐P(ST‐co‐MAH)/starch blend system, and the tensile properties of the blend were not enhanced significantly. However, addition of tetrabutyl titanate (TNBT) during the blending procedure improved the tensile properties significantly through an increased interfacial adhesion between the components in the blend system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2434–2438, 2003     

Reactive extrusion process for the grafting of maleic anhydride onto linear low‐density polyethylene with ultraviolet radiation

In this work, we chemically modified linear low‐density polyethylene with maleic anhydride in the molten state using, in a first step, different doses of ultraviolet irradiation to generate hydroperoxide groups, which were highly reactive at the processing temperature. Then, in a second reactive extrusion step, maleic anhydride was grafted to the linear low‐density polyethylene under different processing conditions. Characterization of the modified and unmodified linear low‐density polyethylene material was performed with Fourier transform infrared spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of ion‐exchange membranes by hydrolysis of radiation‐grafted polyethylene‐g‐polyacrylamide membranes

Polyethylene‐g‐polyacrylamide membranes were prepared by graft polymerization of acrylamide onto polyethylene films using a preirradiation method. The ion‐exchange membranes were obtained by the hydrolysis of grafted films so as to transform amide groups into carboxyl groups. The fraction of amide groups transformed into carboxyl groups was limited to ～0.5. The characterization and thermal behavior of membranes with different degrees of grafting were evaluated by FTIR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) measurements. The heat of fusion and the crystallinity of polyethylene decreased considerably in the hydrolyzed membranes depending on the degree of grafting. It was found that the grafting of acrylamide led to the reduction in crystallinity due to disruption of the crystallites (crystal defects) and dilution of the inherent crystallinity (dilution effect). The contribution of the hydrolysis step to the crystallinity decrease was negligible. The thermal stability of the membranes as obtained from TGA showed considerable enhancement after hydrolysis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 149–154, 2003     

Processing and characterization of epoxy–anhydride‐based intercalated nanocomposites

A study of the kinetic and thermal characterization of an epoxy resin (DGEBA) polymerized with a methyl tetrahydrophthalic anhydride reinforced with montmorillonite‐layered silicates is presented. The nanoreinforcement used was compatibilized by exchanging the cations between the silicate layers with alkylammonium salts, containing long hydrocarbon chains. The aim of this study was to develop new nanocomposites based on thermoset resins with improved thermal stability, suitable for electronic applications. Differential scanning calorimetry was used here to produce the polymerization kinetics data, while thermogravimetric analysis was used to evaluate the effects of the nanoreinforcements on the thermal stability and to analyze the degradation kinetics. Unexpected strong effects of the nanocomposite on the polymerization kinetics of the epoxy–anhydride system were detected and evaluated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2532–2539, 2003     

Parameters affecting the free‐radical melt grafting of maleic anhydride onto linear low‐density polyethylene in an internal mixer

Our main objective of this study was to study the parameters affecting the free‐radical melt grafting of maleic anhydride (MA) onto linear low‐density polyethylene (LLDPE) with dicumyl peroxide (DCP) in an internal mixer. The degree of grafting (DG) was measured with titrometry and Fourier transform infrared spectroscopy. The extent of chain‐branching/crosslinking was evaluated with gel content and melt flow index measurements. The flow behavior and melt viscoelastic properties of the grafted samples were measured by using rheometric mechanical spectrometry. Feeding order, DCP and MA concentration, reaction temperature, rotor speed, and grade of LLDPE were among parameters studied. The results show that the reactant concentration (MA and DCP) played a major role in the determination of the grafting yield and the extent of the chain‐branching/crosslinking as competitive side reactions. The order of feeding also had an appreciable effect on the DG and the side reactions. Increasing the rotor speed increased the grafting yield and reduced side reactions by means of intensification of the mixing of reactants into the polyethylene (PE) melt. Chain‐branching dominated the side reactions for lower molecular weight PE, whereas for higher molecular weight PE, chain‐branching led to crosslinking and gel formation. The results of the melt viscoelastic measurements on the grafted samples provided great insight into the understanding of the role of influential parameters on the extent of side reactions and resulting changes in the molecular structure of the grafted samples. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 141–149, 2006     

Modification of acrylonitrile–butadiene–styrene terpolymer by grafting with maleic anhydride in the melt. I. Preparation and characterization

The graft copolymerization of maleic anhydride (MAH) onto acrylonitrile–butadiene–styrene terpolymer (ABS) was carried out with dicumyl peroxide (DCP) and benzoyl peroxide (BPO) as the binary initiators and with styrene as the comonomer in the molten state. IR spectra confirmed that MAH was successfully grafted onto the ABS backbone. A reaction mechanism was proposed: the grafting most likely took place through the addition of MAH radicals to the double bond of the butadiene region of ABS. Influences such as the MAH concentration, the initiators and their concentrations, the reaction temperature, the rotating speed, and the comonomer concentration were studied. The results indicated that using styrene as a comonomer and DCP/BPO as binary initiators was beneficial for the graft copolymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1249–1254, 2003     

Biodegradation of montmorillonite filled oxo‐biodegradable polyethylene

Oxo‐biodegradation of polyethylene has been well studied with different pro‐oxidants and it has been shown that pro‐oxidants have limited role in the oxidation of polyethylene and do not have any role in microbial growth. However, in few recent studies, montmorillonite clay has been reported to promote the growth of microbes by keeping the pH of the environment at levels conducive to growth. In an attempt to improve the overall oxo‐biodegradation of polyethylene, montmorillonite nanoclay has been used in this study along with a pro‐oxidant. Film samples of oxo‐biodegradable polyethylene (OPE) and oxo‐biodegradable polyethylene nanocomposite (OPENac) were subjected to abiotic oxidation followed by microbial degradation using microorganism Pseudomonas aeruginosa. The progress of degradation was followed by monitoring the chemical changes of the samples using high‐temperature gel permeation chromatography (GPC) and infrared spectroscopy (FTIR). The growth of bacteria on the surface of the polymer was monitored using environmental scanning electron microscopy. GPC data and FTIR results have shown that the abiotic oxidation of polyethylene is influenced significantly by the pro‐oxidant but not by nanoclay. But, the changes in molecular weight distribution and FTIR spectra for the biodegraded samples indicate that the growth rate of P. aeruginosa on OPENac is significantly greater than that on OPE. It indicates that nanoclay, by providing a favourable environment, helps in the growth of the microorganism and its utilisation of the polymer surface and the bulk of the polymer volume. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009