Styrene‐assisted grafting of maleic anhydride onto polypropylene by reactive processing

The grafting of maleic anhydride (MA) onto polypropylene (PP) was performed in the presence of the electron‐donating monomer styrene (ST) according to a central composite experimental design, in which the initial MA and ST concentrations were varied. The grafting of MA onto PP in the absence of ST was also performed. All reactions were carried out in the molten state in a Haake rheometer. The amount of reacted MA and the extent of degradation in PP were determined by means of Fourier transform infrared spectroscopy and melt flow index (MFI) measurements, respectively. The results showed that the presence of ST in the reactive processing caused a reduction in MFI and an increase in the level of reacted MA when the initial MA concentration equaled the initial ST concentration. An increase in the initial MA concentration presented distinct behavior that depended on the ST content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melt grafting of maleic anhydride onto polypropylene with 1‐decene as a second monomer

The influence of 1‐decene as the second monomer on the melt‐grafting behavior of maleic anhydride (MAH) onto polypropylene (PP) was studied with differential scanning calorimetry and Fourier transform infrared spectroscopy. We found that the value of the grafting degree increased from 0.68% for pure MAH‐g‐PP to 1.43% for the system with a 1‐decene/MAH molar ratio of 0.3, whereas the maximum value with styrene (St) as the second monomer was 0.98% under an St/MAH molar ratio of 1.0. Compared with the contribution of St/MAH‐g‐PP to the peeling strength between the PP and polyamide (PA) layer for a PP/PA laminated film, the introduction of 1‐decene/MAH‐g‐PP increased the peeling strength from 180 g/15 mm to 250 g/15 mm. 1‐Decene inhibited the chain scission behavior of PP. 1‐Decene reacted with MAH to form a 1‐decene/MAH copolymer or the Alder‐ene reaction product before the two monomers grafted onto PP. The grafting of the reactive product onto PP greatly improved the grafting degree of MAH. What is more, because of the similar chemical structures of 1‐decene and PP, the affinity of 1‐decene with PP was higher than that of St. Compared with St, the introduction of less 1‐decene led to a higher grafting degree and higher peeling strength. Therefore, we concluded that 1‐decene was more effective for improving the grafting degree of MAH onto PP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification of isotactic polypropylene by the free‐radical grafting of 1,1,1‐trimethylolpropane trimethacrylate

The chemical modification of isotactic polypropylene was performed by the free‐radical‐promoted grafting of 1,1,1‐trimethylolpropane trimethacrylate (TMPTMA) in the presence of dicumyl peroxide (DCP) as the initiator. The reaction was carried out both in a batch internal mixer and in a corotating twin‐screw extruder; the effects of the peroxide and monomer concentrations on the extent of modification in terms of the grafting efficiency and polymer chain structure variations were investigated. The modified samples were characterized with Fourier transform infrared to determine the structure of the grafted groups and the degree of functionalization, with gel permeation chromatography and the melt flow index to evaluate changes in the molecular weight, and with differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis to measure the final thermal properties. In addition, solvent extraction with xylene was performed to highlight the presence of gel and its extent. The structure of the grafted groups was determined, and the number of grafted groups was quantitatively evaluated. The degree of functionalization increased with an increasing TMPTMA/DCP molar ratio. Thermal analysis results hinted at the presence of grafted chains with an increased percentage of TMPTMA. Although degradation reactions predominated at high amounts of peroxide, grafting and branching processes became competitive at high levels of TMPTMA. The balance between competing β‐scission and grafting/branching reactions could be adjusted on the basis of feed conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 950–958, 2007     

Free‐radical grafting of acrylic acid onto isotactic polypropylene using styrene as a comonomer in supercritical carbon dioxide

Free‐radical grafting of acrylic acid (AAc) onto isotactic polypropylene (iPP) using styrene (St) as a comonomer in supercritical carbon dioxide (SCCO₂) medium was studied. The effects of temperature and pressure of reaction on functionalization degree (grafting degree of AAc) of the products were analyzed. The increase of reaction temperature increases the diffusion of monomers and radicals in the disperse reaction system of SCCO₂. In addition, the increase of temperature accelerates the decomposition rate of 2,2′‐azobisisobutyronitrile (AIBN), thus promoting grafting reaction. It was also observed that functionalization degree of the products decreases with the increase of pressure of SCCO₂ in the range of experiment. The effects of comonomer St on the functionalization degree of the products were investigated. The AAc graft degree of the resulting polymer was drastically higher in the present of St. It reached a maximum when the mass ratio of St and AAc was about 0.7 : 1. Because AAc is not sufficiently reactive toward iPP macroradicals, it would be helpful to use a second monomer that can react with them much faster than AAc. St preferentially reacts with the iPP macroradicals to form more stable styrene macroradicals, which then copolymerize with AAc to form branches. The highest functionalization degree was obtained when the AIBN was 0.75 wt %. When the initiator was used excessively, the functionalization degree decreased because of severe chain degradation of the iPP backbone. The morphologies of pure iPP and grafted iPP are different under the polarizing optical microscope. The diameter of the pure iPP spherulites is 20–38 μ and that of the grafted iPP spherulites is reduced with the increase of the functionalization degree of the products. This is proposed to be because the polar grafts formed during the reaction would have a tendency to associate in the hydrophobic PP environment. This might preserve some of the local crystalline order that existed during the reaction in the swollen iPP phase. It can be proven by a DSC cooling investigation that the crystallization temperature increased as the functionalization degree increased. This is proposed to be because the side‐chain of grafting polymer helps to bring about the heterogeneous nucleation in grafting polymer. Therefore, a large number of nuclei can emerge to a lesser supercooling degree. It can be also proven that the percent crystallization decreased as the functionalization degree increased, probably due to the grafted branches, which disrupted the regularity of the chain structure and increased the spacing between the chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2203–2210, 2004     

Comparison of maleic anhydride grafting onto powder and granular polypropylene in the melt by reactive extrusion

The grafting of powder and granular polypropylene (PP) with maleic anhydride (MA) was investigated in a reactive extrusion process with dicumyl peroxide (DCP) as an initiator. The effects of the MA and DCP contents in the feed on grafting were investigated. Under the experimental conditions applied in this study, the grafted monomer unit content was varied from 0.023 to 0.5%. The MA grafting efficiency of powder PP was higher than that obtained for the granular form of PP. In general, the grafting degree first increased with the MA or DCP content in the feed, then reached a maximum value, and finally decreased because of several possible alternative reactions during the grafting. The grafting of powder PP was more successful because of better initial mixing and less diffusional resistance during the grafting. An increase in the MA content in the feed caused significant reductions in the melt‐flow index of the graft copolymers. The results obtained with Fourier transform infrared, differential scanning calorimetry, and X‐ray powder diffraction analyses indicated that the structure, macrotacticity, crystallinity, crystallization, and thermal behavior of PP changed with grafting and depended on the grafting degree. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3675–3684, 2004     

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     

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     

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     

Chemical modification process of an atactic polypropylene by p‐phenylen‐bismaleamic acid in the melt

This study was concerned with the chemical modification process of an atactic polypropylene from polymerization reactor byproducts with p‐phenylen‐bismaleamic acid to obtain a new grafted polymer supposed to play an important role as an interfacial agent in heterogeneous systems based on polymers. The grafting process was undertaken with the aid of the Box–Wilson experimental worksheet, with two independent variables (or controlled factors), the level of polar monomer to be grafted in the polymer and the concentration of the initiator, and with the agitation rate kept constant. Each item of the experimental design was performed at four different reaction times. This latter let us ascertain the transient nature of the process and the existence of a critical point in the concentration of both reactants conducting the system to the maximum grafting yield. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2202–2209, 2003     

Surface modification of polypropylene film by radiation‐induced grafting and its blood compatibility

To endow blood‐compatible properties onto polypropylene (PP) film, we grafted 2,3‐epoxypropyl methacrylate (EPMA) to PP film with a preirradiation grafting technique and then introduced various functional groups onto the grafted PP film. The EPMA grafting extent was dependent on the absorbed dose, reaction time, and temperature. The reactions of hydroxylation, iminodiacetation, sulfonation, phosphonation, and amination were performed under various conditions to introduce functional groups into the epoxy group of EPMA‐grafted PP films, respectively. We also immobilized heparin on aminated PP film to compare blood compatibility with various functionalized samples. The grafting, functionalization, and heparinization reaction were confirmed by Fourier transform infrared spectroscopy in the attenuated total reflectance mode and electron spectroscopy for chemical analysis. The blood compatibility of various functional groups and heparin‐introduced samples as well as control samples was examined by the determination of platelet adsorption and thrombus formation. For the examination of the blood compatibility of functionalized PP samples, acid citrate dextrose human whole blood and platelet‐rich plasma were used. The amount of the formed thrombus and the adherent platelets on functionalized PP sample surfaces were evaluated by an in vitro method following Imai and Nose's technique and by scanning electron microscopy, respectively. The blood compatibility of various functional‐group‐introduced PP films after grafting was better than that of the PP control. Phosphoric‐acid‐group‐ and heparin‐introduced PP films had especially good blood compatibility. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1726–1736, 2003     

Effect of maleic anhydride grafted polypropylene on the mechanical and morphological properties of chemically modified short‐pineapple‐leaf‐fiber‐reinforced polypropylene composites

With the rising cost of petroleum‐based fibers, the utilization of plant fibers in the manufacture of polymer–matrix composites is gaining importance worldwide. The scope of this study was to examine the perspective of the use of pineapple leaf fibers (PALFs) as reinforcements for polypropylene (PP). These fibers are environmentally friendly, low‐cost byproducts of pineapple cultivation and are readily available in the northeastern region of India. Here, both untreated and treated pineapple fibers were used. Maleic anhydride grafted polypropylene (MA‐g‐PP) was used as a compatibilizing agent. The polymer matrix of PP was used to prepare composite specimens with different volume fractions (5–20%) of fibers by the addition of 5% of MA‐g‐PP. These specimens were tested for their mechanical properties, and additional assessments were made via observations by scanning electron microscopy, thermogravimetric analysis, and IR spectroscopy. Increase in the impact behavior, flexural properties, and tensile moduli of the composites were noticed, and these were more appreciable in the treated fibers mixed with MA‐g‐PP. PALF in 10 vol % in PP mixed with MA‐g‐PP was the optimum and recommended composition, where the flexural properties were the maximum. The impact strength and the tensile modulus were also considerably high. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Different factors in the supercritical CO2‐assisted grafting of poly(acrylic acid) to polypropylene

The grafting of poly(acrylic acid) to polypropylene was realized with supercritical CO₂ as a substrate swelling agent and a monomer/initiator carrier. The effects of different supercritical CO₂‐assisted impregnation conditions on the substrate mass increment and grafting efficiency were studied. The original isotactic polypropylene and the grafting product were characterized through IR spectroscopy, differential scanning calorimetry, and scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4280–4285, 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     

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     

Strategies for maximizing free‐radical grafting reaction yields

It is very challenging to obtain very large amounts of vinyl monomers grafted onto polymer backbones in the melt through a free‐radical mechanism. The objective of this study was to develop strategies that would allow one to maximize the amount of 3‐isopropenyl‐α,α‐dimethylbenzene isocyanate (TMI) grafted onto polypropylene (PP) by reactive extrusion processes. For that purpose, an internal batch mixer was used to simulate potential reactive extrusion processes. Two strategies were studied: The first one was to apply the comonomer concept developed in previous studies. More specifically, styrene (St) was used as a comonomer to control the grafting yield and the molar mass of TMI‐grafted PP. The second strategy delt with the feeding mode of the reactants. Two feeding modes were investigated: (a) one‐pot feeding, that is, the total amount of TMI, St, and a peroxide were premixed with PP and the whole mixture was then charged to the reactor at once; (b) stepwise feeding, that is, the total amount of TMI, St, and the peroxide was divided in several equal fractions. The first fraction of the mixture was premixed with PP and then charged to the reactor. After a certain reaction time, the other fractions were charged to the reactor one after another in certain time intervals. Both strategies were shown to be very good at maximizing free‐radical grafting reaction yields. They can be easily adopted if free‐radical grafting is to be carried out by reactive extrusion in a screw extruder. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1799–1807, 2003     

Crystallization and dynamic mechanical properties of polypropylene/polystyrene blends modified with maleic anhydride and styrene

Polypropylene (PP)/polystyrene (PS) blends modified with reactive monomers, such as maleic anhydride (MAH) and styrene (St), and in situ formed PP/PS blends were prepared by melting extrusion. The crystallization and melting behavior and the dynamic mechanical properties of the PP/PS blends, including the structure of the grafted copolymer, were investigated with differential scanning calorimetry, dynamic mechanical analysis, and Fourier transform infrared. The results indicated that the addition of MAH hardly influenced the crystallization temperature of PP in the blends, but the addition of MAH and St increased the crystallization temperature of PP in its blends. The blends showed no remarkable variety for the melting temperature, but the shapes of the melting peaks were influenced by the addition of the reactive monomers. In addition, a significant increase in the storage and loss moduli of all the modified PP/PS blends was observed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2038–2045, 2005     

Crystallization kinetics of polypropylene composites filled with nano calcium carbonate modified with maleic anhydride

The subject of this study was the crystallization behavior and thermal properties of polypropylene (PP)/maleic anhydride (MAH) modified nano calcium carbonate (nano‐CaCO₃) composites. In this study, 5 wt % nano‐CaCO₃ modified with different contents of MAH was filled into a PP matrix. X‐ray diffraction and differential scanning calorimetry were used to characterize the crystal morphology and crystallization kinetics of a series of composites. The results demonstrate that the nano‐CaCO₃ modified with MAH had an important effect on the thermal and morphological properties of the nanocomposites. The Avrami exponent of the pure PP was an integer, but those of the composites were not integers, but the crystallization rate constant decreased as the content of MAH in the nano‐CaCO₃ filler increased in isothermal crystallization. In nonisothermal crystallization, the kinetic parameter F(T) and the degree of crystallinity of pure PP were compared with those of the PP composites filled with nano‐CaCO₃. We suggest that heterogeneous nucleation existed in the PP composites and that the transformation and retention of the β‐form crystal into the α‐form crystal took place in the composite system and the β‐form crystal had a higher nucleation rate and growth process than the α‐form crystal in the PP composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Environmentally responsive amphiphilic cationic block copolymers synthesized by 2,2,6,6‐Tetramethylpiperidinyloxy mediated living free‐radical polymerization

Polychloromethylstyrene (PCMS)‐block‐polystyrene (PS) copolymers were prepared by controlled free‐radical polymerization in the presence of 2,2,6,6‐tetramethylpiperidinooxy and 2,2′‐azobisisobutyronitrile (AIBN) initiator. The PCMS‐b‐PS copolymers had narrow molecular weight distributions, and the block lengths were controlled by the reaction time and the molar ratios of chloromethylstyrene/AIBN and styrene/PCMS macroinitiator. The block copolymers were further quaternized with triethylamine. The amphiphilic cationic block copolymers formed colloidal particles; the effects of the pH value, salt concentration, and solvent polarity on the particle size were investigated with a dynamic light scattering analyzer. The average colloid size increased with increasing pH value and salt concentration. This implied that the colloid formed a protonated hydrophilic shell and hydrophobic styrene core in water. Furthermore, with the addition of tetrahydrofuran to the aqueous solution, the styrene segments in the core could be inverted to the outside of the colloid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Determination of monomer reactivity ratios using in situ FTIR spectroscopy for maleic anhydride/norbornene‐free‐radical copolymerization

Monomer reactivity ratios for maleic anhydride (MAH) and norbornene (Nb) free‐radical copolymerizations were estimated by using a linear graphical method, which is based upon the terminal model developed by Mayo and Lewis. Reactions were performed by using optimized reaction conditions that were previously determined. MAH/Nb copolymerizations (3 mol % AIBN initiator, 60% solids in THF, 65°C, 24 h). Copolymerization data were collected via in situ FTIR to low degrees of conversion (～ 10%) for copolymerizations of MAH and Nb. The following five different MAH/Nb comonomer feed molar ratios were analyzed: 40/60, 45/55, 50/50, 55/45, and 60/40. Conversion data that were measured with in situ FTIR were employed in the rearranged copolymer composition equation to estimate MAH and Nb reactivity ratios. Both of the reactivity ratios were determined to be near 0 (r_MAH = 0.02, r_Nb = 0.01), which was indicative of an alternating copolymerization mechanism. The highest observed rate constant for copolymerization was obtained at an equal molar concentration of monomers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3240–3246, 2004     

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