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     

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     

Selective plasma‐induced grafting of polystyrene onto polyolefin blends

Plasma pretreatment has been used to generate reactive radicals and oxygenated groups on polymer surfaces for graft polymerization. The polymer substrates studied were composed of a polypropylene–polyethylene (PP–PE) copolymer, which was predominantly PP, and also contained blended ethylene–propylene rubber (EPR) as either about 15 or about 60 mol %. A pure PP substrate was also studied for comparison. The grafted polymer was polystyrene (PS). Raman microspectroscopic 2‐dimensional mapping was used to elucidate the role of crystallinity and EPR in the plasma treatment and graft polymerization process. It was found that the plasma pretreatment favored the EPR component of the substrate and the graft yield was related to the EPR content. Crystallinity seemed to have a much less significant effect on the grafting reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1643–1652, 2003     

Preparation of antimicrobial sutures by preirradiation grafting of acrylonitrile onto polypropylene monofilament. II. Mechanical,physical, and thermal characteristics

Polypropylene‐g‐polyacrylonitrile sutures were prepared by graft polymerization of acrylonitrile onto polypropylene monofilament by preirradiation method. Sutures with various graft levels were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Density, Birefriengence, X‐ray Diffraction, Scanning Electron Microscopy (SEM), and Differential Scanning Calorimetry (DSC). Mechanical properties of the unmodified and grafted sutures were also evaluated. The physical characteristics of sutures were markedly affected by the graft levels. Density of the polypropylene sutures increased with an increased in the degree of grafting. The heat of fusion and heat of crystallization decreased with the increase in the degree of grafting. X‐ray diffraction also revealed decrease in crystallinity with the increase in the graft levels. Tenacity of the monofilament improved, whereas the elongation at break decreased in grafted samples. Scanning electron microscopy showed significant variation in surface morphology in the grafted samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1224–1229, 2004     

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     

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     

Influence of an annealing treatment on the solid‐state grafting of styrene onto spherical isotactic polypropylene granules

The main place of solid‐state graft polymerization in polypropylene (PP) granules has been believed to be the amorphous region of PP. In this work, the solid‐phase morphology of nascent spherical PP (N‐PP) granules was found to be markedly changed by an annealing treatment. The crystallinity of PP granules was almost doubled after annealing at 150°C for 12 h, whereas the porosity of the granules was unchanged. Solid‐state grafting polymerizations of styrene initiated by tert‐butyl perbenzoate in both N‐PP and annealed polypropylene (A‐PP) granules were compared under different reaction conditions. The formation of gel in the product could be completely depressed at a low concentration of the initiator when A‐PP granules were used as the matrix and graft‐polymerized at 120°C. Both the introduction of styrene and the annealing treatment of the PP granules led to a depression of polymer degradation in the process of the grafting reaction. However, using A‐PP as the matrix caused an increase in the grafting degree at a relatively high concentration of the initiator. A reduction in the amorphous phase in the PP granules was thought to be the main reason for the effects of the annealing treatment on the structure of the graft polymerization products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactive grafting of glycidyl methacrylate onto polypropylene

This work explored the melt‐phase grafting of glycidyl methacrylate (GMA) onto polypropylene on a closely intermeshing corotating twin‐screw extruder (16‐mm screws, 40 : 1 length/diameter ratio). The modification of the base polypropylene to produce GMA‐grafted polypropylene was achieved via peroxide‐induced hydrogen abstraction from the polypropylene followed by the grafting of the GMA monomer or by the grafting of styrene followed by copolymerization with the GMA. In this study, both the position and order of the reactant addition were investigated as a route to improving graft yields and reducing side reactions (degradation). For the peroxide–GMA system, adding GMA to the melt before the peroxide resulted in significant improvements in the graft levels because of the improved dispersion of GMA in the melt. The addition of a comonomer (styrene) was explored as a second route to improving the graft yield. Although the addition of the comonomer led to a considerable rise in the level of grafted GMA, altering the order of the reactant addition was not found to contribute to an increase in the grafted GMA levels. However, variable levels of grafted styrene were achieved, and this may play an important role in the development of grafted polymers to suit specific needs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Functionalization of industrial polypropylene films via the swift‐heavy‐ion‐induced grafting of glycidyl methacrylate

Swift‐silver‐ion irradiation was explored as a means of forming chemically active sites on the surface of biaxially oriented polypropylene films. The active species, formed in air, was used to induce the graft copolymerization of glycidyl methacrylate in an aqueous solution. The surface structure, crystallinity, morphology, and hydrophilicity of the grafted samples were characterized with Fourier transform infrared, UV, wide‐angle X‐ray diffraction, scanning electron microscopy, and contact‐angle measurements. Glycidyl methacrylate could be grafted onto biaxially oriented polypropylene after swift‐heavy‐ion irradiation without an additional initiator. The contact angle of the modified films decreased with the grafting percentage of glycidyl methacrylate on the polypropylene. The swift silver ions induced significant grafting only in small regions (i.e., the latent tracks) of the polymer. Furthermore, as the fluence of swift heavy ions increased beyond an optimum value, the overlapping of the latent tracks reduced the grafting yield. The observed findings could be very useful in developing an initiator‐free grafting system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

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     

Styrene‐assisted free‐radical graft copolymerization of maleic anhydride onto polypropylene in supercritical carbon dioxide

The free‐radical graft copolymerization of maleic anhydride (MAH) onto polypropylene (PP) with the assistance of styrene (St) in supercritical carbon dioxide (CO₂) was studied. The effects of the St concentration and initiator concentration on the functionality degree of the grafted PP in supercritical CO₂ were investigated. The addition of St drastically increased the MAH functionality degree, which reached a maximum when the molar ratio of MAH and St was 1:1. St, an electron‐donating monomer, could interact with MAH through charge‐transfer complexes to form the St–MAH copolymer (SMA), which could then react with PP macroradicals to produce branches by termination between radicals. There was SMA in the grafting reaction system characterized by Fourier transform infrared and differential scanning calorimetry. Furthermore, the highest MAH functionality degree was obtained when the concentration of 2,2′‐azobisisobutyronitrile (AIBN) was 0.6 wt % based on PP. The effects of the temperature and pressure of supercritical CO₂ on the functionality degree of the grafted PP were analyzed. An increase in the temperature accelerated the decomposition rate constant of AIBN, thereby promoting the grafting reaction. In addition, an increase in the temperature increased the diffusion of monomers and radicals in the disperse reaction system of supercritical CO₂. The highest degree of functionality was found at 80°C. Also, the functionality degree of grafted PP decreased with an increase in the pressure of supercritical CO₂ within the experimental range. The morphologies of pure PP and grafted PP were significantly different under polarizing optical microscopy. The PP spherulites were about 38 μm in size, and the grafted PP spherulites were significantly reduced because of heterogeneous nucleation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 853–860, 2003     

Yttria–polystyrene–polypropylene composite for fine dyeable fibers

Fine polypropylene fiber has many excellent properties, but it is difficult to dye because of the absence of dye sites in the molecular chain and high crystallinity. Fine polypropylene/hybrid polystyrene (yttria) fiber melt‐spun from blends of polypropylene and a small amount of nanohybrid polystyrene with modified yttria incorporated was prepared to improve the dyeing properties. The dyeability, orientation, degree of crystallinity, phase morphology, and mechanical properties of pure polypropylene and the blend fibers were investigated. It was found that the crystallinity and morphology of these phases in the blend systems were different. With the existence of nanohybrid polystyrene, the fine modified polypropylene filaments had practical mechanical properties, the amorphous region of the polypropylene/hybrid polystyrene (yttria) fiber increased, and the modified polypropylene fiber dyed easily and had good fastness to soaping because of the complexation of the disperse dye and yttrium in the blend system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

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     

Polymorphism in polypropylene fibers

The structure of polypropylene fibers formed by different spinning conditions was studied. The investigations were carried out using wide‐angle X‐ray scattering (WAXS) and small‐angle X‐ray scattering (SAXS) methods. It was stated that in noncolored fibers the mesophase and the monoclinic α forms were formed. The highest content of the mesophase was observed for fibers extruded at the higher temperature and taken at the medium take‐up velocity. In fibers colored with quinacridone pigment the structure containing the monoclinic α and the trigonal β forms was obtained. The highest content of the β form occurred in fibers taken at the lowest take‐up velocity. The increase of the take‐up velocity caused a rapid drop in β form content. In fibers taken at higher velocities only the α form was formed. It was found that the content of different forms as well lamellar thickness depends on crystallization conditions, which were influenced by the formation parameters. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3364–3370, 2003     

Effect of the delignification of wood fibers on the mechanical properties of wood fiber–polypropylene composites

The effect of the delignification of hornbeam fibers on the mechanical properties of wood fiber–polypropylene (PP) composites was studied. Original fibers and delignified fibers at three levels of delignification were mixed with PP at a weight ratio of 40:60 in an internal mixer. Maleic anhydride (0.5 wt %) as the coupling agent and dicumyl peroxide (0.1 wt %) as the initiator were applied. The produced composites were then hot‐pressed, and specimens for physical and mechanical testing were prepared. The results of the properties of the composite materials indicate that delignified fibers showed better performance in the enhancement of tensile strength and tensile modulus, whereas the hardness of the composites was unaffected by delignification. Delignified fibers also exhibited better water absorption resistance. Notched impact strength was higher for delignified fiber composites, but it was reduced at higher delignification levels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4759–4763, 2006     

Milling‐induced esterification between cellulose and maleated polypropylene

The ball milling of cellulose and maleic anhydride grafted polypropylene (MAPP) induced the formation of ester bonds between OH groups of cellulose and maleic anhydride groups of MAPP, in marked contrast to the melt mixing of the original cellulose and MAPP, through which the esterification was hardly observed. This esterification was hardly dependent on the chemical structure of MAPP. In agreement with the enhanced interfacial adhesion due to the formation of ester bonds, a composite prepared via ball milling revealed an improvement in the tensile strength with respect to a melt‐mixed composite. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1703–1709, 2004