Synthesis and characterization of dextrin‐grafted polypropylene

We carried out the graft copolymerization of the water‐soluble natural polymer dextrin onto preirradiated polypropylene (PP) in an aqueous medium using benzoyl peroxide (BPO) as the radical initiator. PP was irradiated by γ rays from a Co⁶⁰ source at a constant dose rate of 3.40 kGy/h to introduce hydroperoxide linkages, which served as the sites for grafting. The graft copolymerization was studied as a function of different reaction parameters, and the maximum percentage grafting (P_g; 55%) of dextrin onto PP was obtained at optimum conditions of [BPO] = 5.165 × 10⁻² mol/L, temperature = 60°C in 120 min with 15 mL of water. Different grafting parameters, such as the percentage apparent grafting, percentage grafting, and percentage true grafting have been evaluated. The graft copolymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Swelling studies were carried out in pure, binary, ternary, and quaternary solvent systems composed of water, ethanol (EtOH), dimethyl sulfoxide (DMSO), and N,N‐dimethylformamide (DMF) at different ratios. The maximum swelling percentage PP‐g‐dextrin (both composite and true graft) was observed in pure DMSO and DMF followed by EtOH and water. Water‐retention studies of PP and PP‐g‐dextrin (both composite and true graft) were investigated at different time periods, temperatures, and pH values. The maximum percentage water retention of PP‐g‐dextrin (composite, 124%) was observed at 8 h and 50°C in a neutral medium (pH 7). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of the talc filler content on the mechanical properties of polypropylene composites

This research examines the effect of a microsize/nanosize talc filler on the physicochemical and mechanical properties of filled polypropylene (108MF10 and 33MBTU from Saudi Basic Industries Corp. and HE125MO grade from Borealis) composite matrices. A range of mechanical properties were measured [tensile properties, bending properties, fracture toughness, notched impact strength (at the ambient temperature and ?20°C), strain at break, and impact strength] along with microhardness testing and thermal stability testing from 40 to 600°C as measured by differential thermal analysis and thermogravimetric analysis. Increasing filler content lead to an increase in the mechanical strength of the composite material with a simultaneous decrease in the fracture toughness. The observed increase in tensile strength ranged from 15 to 25% (the maximum tensile strength at break was found to be 22 MPa). The increase in mechanical strength simultaneously led to a higher brittleness, which was reflected in a decrease in the mean impact strength from the initial 18 kJ/m² (for the virgin polypropylene sample) to 14 kJ/m², that is, a 23% decrease. A similar dependency was also obtained for the samples conditioned at ?20°C (a decrease of 12.5%). With increasing degree of filling of the talc–polypropylene composite matrix, the thermooxidative stability increased; the highest magnitude was obtained for the 20 wt % sample (decomposition temperature = 482°C, cf. 392°C for the virgin polymer). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of the Hierarchical Structure in Poly(propylene)/Clay Composites on their Thermal Stability: From Single‐ to Multi‐Step Degradation Processes

Composites with several hierarchical structures were prepared by using different clays, compatibilizers, and PPs. TGA showed that the thermal stability of the composites can be strongly improved, under either inert or thermo‐oxidative conditions, depending on the type of clay and its morphology. Drastic increases in the temperature of the maximum rate of weight loss (ΔT_peak ≈ 170 °C) under thermo‐oxidative conditions were observed depending on the clay dispersion. Furthermore, some composites had a complex multi‐step degradation behavior instead of a single‐step process related with different clay morphologies that can be present simultaneously. Finally, it was concluded that the TGA has a higher sensitivity toward the composite morphology than the mechanical properties.

     

Thermal stability and crystallization kinetics of isotactic polypropylene/organomontmorillonite nanocomposites

The thermal stability and crystallization kinetics of isotactic polypropylene (iPP) and iPP/organomontmorillonite (organo‐MMT) nanocomposites were investigated with differential scanning calorimetry and thermogravimetry. The incorporation of organo‐MMT up to a concentration of 4 wt % did not affect the melting temperature of iPP but did increase the peak thermal degradation temperature by 60°C. The isothermal crystallization kinetics showed that the addition of organo‐MMT increased the crystallization rate of iPP but reduced the isothermal Avrami exponent. The crystallization temperature of the nanocomposites measured with nonisothermal crystallization was higher than that of plain iPP, and this indicated an enhanced crystallization rate. The nonisothermal Avrami exponent, like the isothermal exponent, decreased with the addition of organo‐MMT, and this suggested changes in the crystallite growth geometry. Subsequently, the tensile yield strength and the tensile modulus both increased, but the elongation at break and the notched Izod impact strength did not change significantly. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3404–3415, 2003     

Electron‐beam‐radiation‐induced grafting of acrylonitrile onto polypropylene fibers: Influence of the synthesis conditions

Electron‐beam‐radiation‐induced grafting of acrylonitrile onto polypropylene fibers was investigated with a pre‐irradiation method. Grafting conditions such as the solvents, additives, monomer concentration, radiation dose, and temperature were varied, and the effects on the degree of grafting were studied. The nature of the reaction medium and additives had a considerable influence on the degree of grafting. The dilution of acrylonitrile with N,N‐dimethylformamide significantly enhanced the degree of grafting in comparison with other solvents. The addition of sulfuric acid to the reaction mixture led to an increase in the degree of grafting and an acceleration of the rate of grafting. The order of dependence of the rate of grafting on the pre‐irradiation dose and monomer concentration was found to be 1.31 and 1.21, respectively, in the presence of sulfuric acid. The activation energy for grafting was calculated to be 21.9 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal degradation of epoxy resin reinforced with polypropylene fibers

The influence of polypropylene fibers on the thermal degradation of epoxy composites was investigated with thermogravimetric analysis. Three composites with 5, 10, or 15 wt % polypropylene fibers were prepared with epoxy as a matrix material. The polypropylene fibers, used as reinforcing materials, retarded the thermal decomposition, and increasing the weight percentage of the fiber material increased the thermal stability to a certain extent. Of the three composites, the 10 wt % polypropylene fiber/epoxy resin composite showed very good thermal stability, which was indicated by the increase in the resin decomposition temperature from 280°C for the 5 wt % polypropylene fiber/epoxy resin composite to 375°C for the 10 wt % polypropylene fiber/epoxy resin composite. The Horowitz–Metzger method was used to calculate the activation energies, and the results were tabulated. A morphological analysis was carried out with scanning electron microscopy to evaluate the dispersion of the fibers in the epoxy matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 500–503, 2007     

Phase‐transfer‐agent‐aided polymerization and graft copolymerization of acrylamide

The use of phase‐transfer catalysts, with water‐insoluble initiators, for polymerization and graft copolymerization reactions was explored. The polymerization of a water‐soluble vinyl monomer, acrylamide (AAm), and the graft copolymerization of AAm onto a water‐insoluble polymer backbone, isotactic polypropylene (IPP), with a water‐insoluble initiator, benzoyl peroxide (BPO), and a phase‐transfer catalyst, tetrabutyl ammonium bromide (Bu₄N⁺Br^?), were carried out in a water/xylene binary solvent system. The conversion percentage of AAm into polyacrylamide (PAAm) and the percentage of grafting of AAm onto IPP were determined as functions of various reaction parameters, such as the BPO, AAm, and phase‐transfer‐catalyst concentrations, the amounts of water and xylene in the water/xylene mixture, the time, and the temperature. The graft copolymer, IPP‐g‐PAAm, was characterized with IR spectroscopy and thermogravimetric analysis. By a comparison of the results of the phase‐transfer‐catalyzed graft copolymerization of AAm onto IPP and the preirradiation method, it was observed that the optimum reaction conditions were milder for the phase‐transfer‐catalyst‐aided graft copolymerization. Milder reaction conditions, including the temperature, the time of reaction, and a moderate initiator (BPO), in comparison with high‐energy γ‐rays, led to better quality products, and the reaction proceeded smoothly with high productivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2364–2375, 2004     

Multienzyme‐immobilized modified polypropylene membrane for an amperometric creatinine biosensor

Creatinine has become an important clinical analyte that is used for the determination of renal and muscular dysfunction. It is essential to determine its concentration in the serum of patients suffering from renal insufficiency. Therefore, an amperometric creatinine biosensor fabricated from a covered platinum/silver electrode with a thin layer of an immobilized multienzyme membrane was studied. Poly(acrylic acid) was introduced onto an argon‐plasma‐treated porous polypropylene membrane surface by graft copolymerization. Subsequently, three different enzymes (sarcosine oxidase, creatinase, and creatininase) were immobilized onto this novel grafted membrane simultaneously via a carbodiimine agent to form a thin layer. The sensor performance was evaluated with a biochemistry analyzer. Moreover, attenuated total reflection/Fourier transform infrared, electron spectroscopy for chemical analysis, and scanning electron microscopy were used to confirm the progression of these reactions. The developed sensor showed a linear detection range of 3.2–320 μM for creatinine in a pH 7.4 buffered solution with 0.1M phosphate. The immobilized multienzyme membrane could be used for at least 3 weeks. The results obtained in our study will hopefully lead to the successful application of modified polypropylene for the development of a creatinine sensor. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3126–3134, 2004     

Stress‐induced crystallization of biaxially oriented polypropylene

The hot stretching of thick, extruded sheets at high temperatures is a very important process in the production of finished biaxially oriented polypropylene (BOPP) films with special inner structures. Through a simulation of hot stretching in the machine direction (MD) of the processing of BOPP films, it was found that at high temperatures, the stretching ratio greatly influenced the obtained crystalline structure, as observed by differential scanning calorimetry (DSC). Also, in MD hot stretching, the crystallinity increased by an average of 20%. Wide‐angle X‐ray diffraction patterns of extruded sheet samples with and without stretching confirmed the structural changes shown by DSC, and the results proved that β‐crystal modification did not occur during the MD hot‐stretching process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 686–690, 2003     

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     

Some features of phenolic inhibitor consumption in oxidized polypropylene in the presence of synergists–hydroperoxide decomposers

The influence of sulfur and phosphors containing substances, hydroperoxide decomposers, on the kinetics of the consumption of two phenolic antioxidants in polypropylene (PP) was studied. The induction periods of PP autoxidation at 130°C were measured in the presence of inhibiting compositions that consisted of phenolic inhibitors and decomposers of hydroperoxide. The obtained results indicated that the influence of the hydroperoxide decomposer became significant when the concentration of the phenolic antioxidant became close to a critical value. It was shown also that the influence of the hydroperoxide decomposer significantly depended on the mechanism of the phenolic inhibitor transformation: first of all, on the nature of its transformation products. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2226–2229, 2003     

Evolution of the peroxide‐induced degradation of polypropylene along a twin‐screw extruder: Experimental data and theoretical predictions

This article reports an experimental and theoretical study of the peroxide‐induced degradation of polypropylene in a corotating twin‐screw extruder. Experiments were performed with different peroxide concentrations and different operating conditions. The evolution of the chemical reaction along the extruder was monitored with specific sampling devices. Material changes were characterized by rheological measurements and via the determination of the molecular weights of samples collected at the same locations. The theoretical results were obtained with a model that coupled the interactions between flow conditions encountered in the extruder, the kinetics of the reaction, and the changes in the viscosity induced by changes in the molecular weight. The experimental results evidenced the relationships between the process conditions (peroxide concentration and processing parameters) and material properties (rheological properties and molecular structure of the modified polypropylene). Good agreement between the theoretical and experimental results was obtained. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Compatibilization of polypropylene/nylon 6 blends with a polypropylene solid‐phase graft

The compatibilization of polypropylene (PP)/nylon 6 (PA6) blends with a new PP solid‐phase graft copolymer (gPP) was systematically studied. gPP improved the compatibility of PP/PA6 blends efficiently. Because of the reaction between the reactive groups of gPP and the NH₂ end groups of PA6, a PP‐g‐PA6 copolymer was formed as a compatibilizer in the vicinity of the interfaces during the melting extrusion of gPP and PA6. The tensile strength and impact strength of the compatibilized PP/PA6 blends obviously increased in comparison with those of the PP/PA6 mechanical blends, and the amount of gPP and the content of the third monomer during the preparation of gPP affected the mechanical properties of the compatibilized blends. Scanning electron microscopy and transmission electron microscopy indicated that the particle sizes of the dispersed phases of the compatibilized PP/PA6 blends became smaller and that the interfaces became more indistinct in comparison with the mechanical blends. The microcrystal size of PA6 and the crystallinity of the two components of the PP/PA6 blends decreased after compatibilization with gPP. The compatibilized PP/PA6 blends possessed higher pseudoplasticity, melt viscosity, and flow activation energy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 420–427, 2004     

Nonisothermal crystallization behavior of glass‐bead‐filled polypropylene

The effects of the glass‐bead content and size on the nonisothermal crystallization behavior of polypropylene (PP)/glass‐bead blends were studied with differential scanning calorimetry. The degree of crystallinity decreased with the addition of glass bead, and the crystallization temperature of the blends was marginally higher than that of pure PP at various cooling rates. Furthermore, the half‐time for crystallization decreased with an increase in the glass‐bead content or particle size, implying the nucleating role of the glass beads. The nonisothermal crystallization data were analyzed with the methods of Avrami, Ozawa, and Mo. The validity of various kinetic models for the nonisothermal crystallization process of PP/glass‐bead blends was examined. The approach developed by Mo successfully described the nonisothermal crystallization behavior of PP and PP/glass‐bead blends. Finally, the activation energy for the nonisothermal crystallization of pure PP and PP/glass‐bead blends based on the Kissinger method was evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2026–2033, 2006     

Morphology and mechanical properties of polypropylene and poly(ethylene‐co‐methyl acrylate) blends

The morphology and mechanical properties of isotactic polypropylene (iPP) and poly(ethylene‐co‐methyl acrylate) (EMA) blends were investigated. Various EMA copolymers with different methyl acrylate (MA) comonomer content were used. iPP and EMA formed immiscible blends over the composition range studied. The crystallization and melting reflected that of the individual components and the crystallinity was not greatly affected. The size of the iPP crystals was larger in the blends than those of pure iPP, indicating that EMA may have reduced the nucleation density of the iPP; however, the growth rate of the iPP crystals was found to remain constant. The tensile elongation at break was greatly increased by the presence of EMA, although the modulus remained approximately constant until the EMA composition was greater than 20%. EMA with a 9.0% MA content provided the optimum effect on the mechanical properties of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 175–185, 2003     

Fracture properties of nanoclay‐filled polypropylene

Maleic anhydride‐modified polypropylene was compounded with commercially available surface‐modified montmorillonite in a twin‐screw extruder. Recompounding ensured the removal of visible tactoids from the extrudate but TEM and XRD techniques showed nonuniform dispersion of clay platelets. In this study, we investigated the mechanical and fracture properties of nanoclay‐filled polypropylene. Emphasis was placed on the fracture characterization of the clay‐filled polypropylene. Tensile strength and stiffness increased steadily with an increase in the clay loading. The toughness of compounded materials was characterized using rigorous fracture mechanics. J‐integral fracture resistance decreased with an increase in the clay content. The resistance against stable crack growth was compared using the slopes derived from the J–R curve and the tearing modulus concept. A significant amount of crack growth resistance was evident in the nanoclay‐filled polypropylene as opposed to other brittle nanocomposites such as the nylon–clay systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3298–3305, 2003     

Hydrolytic aging of polypropylene studied by X‐ray photoelectron spectroscopy

X‐ray photoelectron spectroscopy (XPS) was used to study the hydrolytic aging of polypropylene according to the pHs of degrading buffer solutions and the time of aging. The study was concentrated over periods of 3, 6, and 9 months for values of pH close to the real environments of use of the material (pH of 6, 7, and 8). The polypropylene underwent an oxidation of its polymeric matrix, independently of the range of pH values, by the production of C? OH, C?O, and O?C? O groups. These chemical functions were observed in high resolution XPS spectra around C1s and O1s peaks. Beginning with these results and from mechanisms of (photochemical, thermal, and others) aging proposed in the literature, it was then possible to propose mechanisms of hydrolytic ageing of polypropylene. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3830–3838, 2004     

Effects of rosin‐type cocrystal nucleating agents on the crystallization process and the properties of polypropylene

A new kind of rosin‐type nucleating agent for polypropylene (PP), the cocrystal of dehydroabietic acid, potassium dehydroabietate, and sodium dehydroabietate, was prepared, and the effects of the nucleating agents on the mechanical and crystallization properties of PP were also studied. The results of differential scanning calorimetry and X‐ray diffraction proved that the cocrystal of dehydroabietic acid and compound alkali dehydroabietate was formed rather than a simple blend of dehydroabietic acid and single alkali dehydroabietate. When it was added to PP, the size of the PP spherulite decreased; the mechanical properties, crystallization temperature, and transparency of PP were substantially improved. Thus, the cocrystal of dehydroabietic acid, potassium dehydroabietate, and sodium dehydroabietate acted as a more effective nucleating agent for PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2137–2141, 2003     

Radiation‐induced grafting of pentamethyl hindered amine light stabilizer 1,2,2,6,6‐pentamethyl‐4‐piperidinyl methacrylate onto polypropylene

The γ‐radiation‐induced grafting of 1,2,2,6,6‐pentamethyl‐4‐piperidinyl methacrylate (PMPM) onto polypropylene (PP) was investigated with a simultaneous irradiation technique. The effects of the solvent, dose, monomer concentration, and photoinitiator on the grafting were investigated. The grafting was easier in a benzene solution than in chloroform and acetone solutions. The grafting percentage first increased almost linearly with the irradiation dose until 20 kGy and then increased slowly or remained constant. The grafting percentage increased with the monomer concentration until 1.1 mol/L. The grafting percentage was higher when the proper amount of benzophenone was added. The grafted samples were characterized with Fourier transform infrared spectroscopy and thermogravimetric analysis. Carbonyl groups were found on grafted PP samples, and the carbonyl index increased with the grafting percentage. Thermogravimetric analyses proved the existence of grafted materials on PP, and grafted PMPM thermally decomposed at a lower temperature than PP. The radiation resistance of PP with grafted PMPM was better than that of pristine PP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2157–2164, 2005     

Development and performance study of polypropylene/polyester bicomponent melt‐blowns for filtration

In this study, a new type of polypropylene (PP)/polyester (PET) bicomponent melt‐blown (bi‐MB) for filtration was developed through the melt‐blowing process with raw materials of melt‐blown (MB)‐grade PP and PET chips. The structure, porosity, and filtration performance of the bi‐MBs were tested through relevant instruments. The results show that the average fiber diameter in the bi‐MBs was 2–3.5 μm, the average pore size was 12.3–15.6 μm, and the porosity was 90–94%. The results also show that the filtration efficiency of the bi‐MBs was much higher than that of monocomponent PP MBs. It reached the highest value of 97.34% when the PP/PET ratio was 50/50 and could be used as high‐performance filter media. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012