Influence of metal‐oxide‐supported bentonites on the pyrolysis behavior of polypropylene and high‐density polyethylene

In this article, we report on the pyrolysis of polypropylene (PP) and high‐density polyethylene (HDPE) in the absence and presence of plain and metal‐oxide‐impregnated bentonite clays [BCs; acid‐washed bentonite clay (AWBC), Zn/AWBC, Ni/AWBC, Co/AWBC, Fe/AWBC, and Mn/AWBC] into useful products. Thermal and catalytic runs were performed at 300°C in the case of PP and at 350°C in the case of HDPE for a contact time of 30 min. The effects of different catalysts and their concentrations on the overall yields and the yields of liquid, gas, and residue were studied. The efficacy of each catalyst is reported on the basis of the highest liquid yields (in weight percentage). The derived liquid products were analyzed by Fourier transform infrared spectroscopy and gas chromatography–mass spectroscopy; this confirmed the presence of paraffins, olefins, and naphthenes. The results indicate the catalytic role of impregnated BCs compared to plain BC with the optimum efficiency shown by Co/AWBC in the case of PP and Zn/AWBC in the case of HDPE toward the formation of liquid products in a desirable C range with the enrichment of olefins and naphthenes in the case of PP and paraffins and olefins in the case of HDPE compared to the thermal run. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41221.     

Rheological assessment of variable molecular chain structures of linear low‐density polyethylene under reactive modification

The aim of this study was to investigate how changes in the molecular structure of linear low‐density polyethylene (LLDPE) during peroxide modification can be detected by a simple rheological method. For this purpose, a commercial‐grade LLDPE (Exxon Mobile LL4004EL) was reacted with different doses of dicumyl peroxide (DCP). The samples were analyzed by size exclusion chromatography coupled with a light‐scattering detector. With increasing DCP dose, at a roughly constant molar mass, an increasing number of long‐chain branches were found. The dynamic shear oscillatory measurements showed a deviation of the phase angle–complex shear modulus curve from that of the linear LLDPE, which was attributed to the presence of long‐chain branching. By the use of a simple rheological method that used melt rheology, transformations in the molecular architecture induced on the original LLDPE during the early stages of reactive modification were indicated. Reasonable and consistent estimates of the degree of long‐chain branching (x) and the volume fraction of the various molecular species produced in the peroxide modification of LLDPE were obtained. Various three‐dimensional plots were constructed to exhibit the correlation between the process parameters and x. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39617.     

Flame‐retardant and thermal degradation mechanism of low‐density polyethylene modified with aluminum hypophosphite and microencapsulated red phosphorus

Aluminum hypophosphite (AHP), a novel flame retardant, was used to improve the flame retardancy of low‐density polyethylene (LDPE) with microencapsulated red phosphorus (MRP). The synergistic effect between MRP and AHP was investigated by the limiting oxygen index (LOI), vertical burning test (UL‐94), and thermogravimetric analysis. When the contents of MRP and AHP were 10 and 30 phr, the LOI of LDPE/10MRP/30AHP composite was 25.5%, and it passed the UL‐94 V‐0 rating (the number before “MRP” and “AHP” is the loading of MRP and AHP, In LDPE/10MRP/30AHP, the content of the LDPE, MRP and AHP is 100phr, 10phr and 30phr, where phr refers to parts per hundreds of resin). The results of cone calorimetry testing show that the heat release rate of the composites was significantly reduced, and the strength of the char layer improved when the loading of AHP increased. The thermal stability of the LDPE/10MRP/30AHP composite was enhanced. The structure of the char was investigated by Fourier transform infrared spectrometry and scanning electron microscopy/energy‐dispersive spectrometry. The results indicate that AHP promoted the formation of stable char. This research provided a good way to prepare flame‐retardant materials with a halogen‐free flame retardant and contributed to environmental protection. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43225.     

Surface oxidation of low‐density polyethylene films to improve their susceptibility toward environmental degradation

Polyethylene wastes, particularly as films, have accumulated over the last several decades resulting in a major visual litter problem. The aim of this study was to investigate the ability of chemical reagents to oxidize the low‐density polyethylene (LDPE) film surface to increase their susceptibility toward photodegradation and thermal degradation. Three chemical agents, namely, potassium permanganate, potassium persulfate, and benzoyl peroxide, were used to oxidize the film surface to generate chromophoric groups, such as carbonyl groups, which are the main reason for the enhanced environmental degradation of photolytic polymers, such as ethylene–carbon monoxide and ethylene–vinyl ketone copolymers. For the chemical treatment, LDPE films of 70 ± 5 μm thickness were prepared by a film‐blowing technique and subsequently reacted with the aforementioned oxidizing agents. To aid the oxidation process, the reaction with potassium persulfate and potassium permanganate was performed under microwave irradiation heating. In the case of benzoyl peroxide aided oxidation, the films were subjected to repeated coating–heating treatments up to a maximum of 10 cycles. The treated films were subjected to accelerated aging, that is, xenon‐arc weathering and air‐oven aging (at 70°C), for extended time periods. The chemical and physical changes induced as a result of aging were followed by the monitoring of changes in the mechanical, structural, and thermal properties. The results indicate that the surface‐oxidized LDPE films exhibited enhanced susceptibility toward degradation; however, the extent was reduced as compared to photolytic or other degradable compositions. The ability of the chemicals to initiate degradation followed the order potassium persulfate < potassium permanganate < benzoyl peroxide. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal analysis of high‐density polyethylene and low‐density polyethylene with enhanced biodegradability

The thermal properties of high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) filled with different biodegradable additives (Mater‐Bi AF05H, Cornplast, and Bioefect 72000) were investigated with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The DSC traces of the additives indicated that they did not undergo any significant phase change or transition in the temperature region typically encountered by a commercial composting system. The TGA results showed that the presence of the additive led to a thermally less stable matrix and higher residue percentages. The products obtained during the thermodegradation of these degradable polyolefins were similar to those from pure polyethylenes. The LDPE blends were thermally less stable than the HDPE blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 764–772, 2002     

Releasing polyacrylonitrile from poor biodegradability by insertion of a highly biodegradable chemical structure into the main chain

Polyacrylonitrile turned biodegradable by incorporation of N‐benzyl‐4‐vinylpyridinium chloride (BVP), a highly biodegradable chemical structure, into the main chain. Oligomers of acrylonitrile are biodegradable dissimilar to polyacrylonitrile, and connection of them by BVP produced biodegradable polymers. The half‐life of a copolymer of acrylonitrile with BVP (PAN‐co‐BVP) in a molar ratio of 97 : 3 was 21 days when treated with activated sludge in soil. The average number of acrylonitrile units in the oligo‐acrylonitrile portion was 32. Degradation at the BVP portion appeared predominant, but the oligo‐acrylonitrile portion also underwent exhaustive degradation when the portion was sufficiently short. Even though biodegradable, oligo‐acrylonitriles are not useful as polymeric materials, but connection of them by BVP produces useful polymeric materials possessed of sufficient biodegradability. Such bridged polymer is different from conventional polyacrylonitrile, and its utility may be different to some extent, but it possesses sufficient biodegradability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 852–857, 2006     

Processability‐enhanced bimodal high‐density polyethylene with comb‐branched high‐density polyethylene

Two solution reactors in series were utilized to synthesize comb‐branched high‐density polyethylene (HDPE), cbHDPE, where the first reactor prepares vinyl‐terminated HDPE macromers catalyzed by an organometallic catalyst favoring beta hydride transfer and the second reactor copolymerizes HDPE macromers with ethylene using a different organometallic catalyst capable of incorporating macromers. A bimodal HDPE, biHDPE with bimodalities in molecular weight, and hexene content of the desired composition distribution was also prepared in a gas phase reactor using silica supported dual organometallic catalysts. By blending 3% solution‐made cbHDPE into the gas‐phase biHDPE, the resulting trimodal HDPE preserves the excellent stiffness and toughness of the bimodal HDPE while having exceptional melt strength and processability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45755.     

Surface modification of linear low‐density polyethylene film by amphiphilic graft copolymers based on poly(higher α‐olefin)‐graft‐poly(ethylene glycol)

In this article, a series of amphiphilic graft copolymers, namely poly(higher α‐olefin‐co‐para‐methylstyrene)‐graft‐poly(ethylene glycol), and poly(higher α‐olefin‐co‐acrylic acid)‐graft‐poly(ethylene glycol) was used as modifying agent to increase the wettability of the surface of linear low‐density polyethylene (LLDPE) film. The wettability of the surface of LLDPE film could be increased effectively by spin coating of the amphiphilic graft copolymers onto the surface of LLDPE film. The higher the content of poly(ethylene glycol) (PEG) segments, the lower the water contact angle was. The water contact angle of modified LLDPE films was reduced as low as 25°. However, the adhesion between the amphiphilic graft copolymer and LLDPE film was poor. To solve this problem, the modified LLDPE films coated by the amphiphilic graft copolymers were annealed at 110° for 12 h. During the period of annealing, heating made polymer chain move and rearrange quickly. When the film was cooled down, the alkyl group of higher α‐olefin units and LLDPE began to entangle and crystallize. Driven by crystallization, the PEG segments rearranged and enriched in the interface between the amphiphilic graft copolymer and air. By this surface modification method, the amphiphilic graft copolymer was fixed on the surface of LLDPE film. And the water contact angle was further reduced as low as 14.8°. The experimental results of this article demonstrate the potential pathway to provide an effective and durable anti‐fog LLDPE film. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Additives for ultraviolet‐induced oxidative degradation of low‐density polyethylene

Polyethylene (PE) is one of the most widely produced and widely used plastics in the world. Saturated hydrocarbons cannot absorb the energy of the light reaching earth, so the degradation process is rather slow; this, in return, causes disposal problems. On the other hand, it was observed that in the presence of oxygen and impurities in the polymer matrix, the degradation could be reduced to shorter time intervals. In this study, vanadium(III) acetyl acetonate (VAc), serpentine (SE), and Cloisite 30B (CL) were used as additives, both together and alone, and we followed the photodegradation of PE. The amount of VAc was kept constant at 0.2 wt %, whereas the amounts of SE and CL were varied between 1 and 4 wt %. The samples were irradiated by UV light for up to 500 h. Mechanical and spectroscopic measurements were carried out during certain time intervals to monitor the degradation. VAc containing PE showed the fastest degradation. The elongation at break values of these samples were reduced to half of the initial value of elongation at break within five days. Combinations of the CL and SE additives were also proven to accelerate the degradation of PE; this was followed by an increase in the carbonyl index, which was observed to be at least 10 times greater than that of pure PE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43354.     

Ultraviolet preirradiation of high‐density polyethylene for the grafting of maleic anhydride during reactive extrusion

High‐density polyethylene was irradiated with ultraviolet light for various exposure times, as a prestep for hydroperoxide production, before a bulk grafting reaction with maleic anhydride in the melt phase by reactive extrusion. This method was compared with a traditional grafting procedure using peroxides optimized by an evaluation of the grafting level versus the screw speed; the highest speed showed the greatest grafting value. The reaction was followed by Fourier transform infrared, the gel percentage, and the grafting degree, which was evaluated by titration. The effect of grafting for both methods under the established processing conditions on the thermal properties was observed with differential scanning calorimetry via their heating and cooling thermograms; there were notorious changes in the fusion peak temperatures, indicating differences in the crystallization process after the grafting reaction. The latter was confirmed by NMR spectroscopy, which showed succinic anhydride rings attached to the polyethylene chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2882–2888, 2006     

Photodegradation of thermodegraded polypropylene/high‐impact polystyrene blends: Mechanical properties

The influence of the addition of high‐impact polystyrene (HIPS) on polypropylene (PP) photodegradation was studied with blends obtained by extrusion with and without styrene–butadiene–styrene (SBS) copolymer (10 wt % with respect to the dispersed phase). The concentrations of HIPS ranged from 10 to 30 wt %. The blends and pure materials were exposed for periods of up to 15 weeks of UV irradiation; their mechanical properties (tensile and impact), fracture surface, and melt flow indices were monitored. After 3 weeks of UV exposure, all of the materials presented mechanical properties of the same order of magnitude. However, for times of exposure greater than 3 weeks, an increasing concentration of HIPS resulted in a better photostability of PP. These results were explained in light of morphological observations. This increase of photostability was even greater when SBS was added to the blends. It was more difficult to measure the melt flow index of the binary PP/HIPS blends than that of PP for low concentrations of HIPS; this was most likely due to energy transfer between the blend domains during photodegradation. This phenomenon was not observed for the ternary blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and properties of polypropylene/high‐density polyethylene blends by solid equal channel angular extrusion

The solid equal channel angular extrusion (ECAE) process on polypropylene (PP)/high‐density polyethylene (HDPE) blends was carried out. Scanning electron microscopy (SEM) was used to observe the sample structures. Results showed that ECAE process could make PP/HDPE blends to produce orientation structure. Impact performance of ECAE‐PP/HDPE samples after ECAE process improved remarkably, especially for ECAE‐PP/HDPE (90/10)‐O whose impact strength reached 91.91 kJ/m², 18.1 times higher than that of pure PP and 11.2 times higher than that of PP/HDPE (90/10). The mechanism of enhancing between HDPE and PP was discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39759.     

Grafting of glycidyl methacrylate onto high‐density polyethylene with reaction time in the batch mixer

The melt grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene (HDPE) in the presence of free radical initiators was investigated in the batch mixer. The graft content was determined with the titration and FTIR spectroscopy. The graft content increased with the increase of peroxide and initially introduced GMA concentration. Increase of the grafted GMA content resulted in decrease of the melt index. Interestingly, there was a sudden drop of GMA grafting content with the reaction time. It is assumed that depolymerization of GMA have taken place over the ceiling temperature. The crystallinity of the prepared glycidyl methacrylate grafted high density polyethylene (HDPE‐g‐GMA) was determined by the measurement of the heat of fusion. GMA grafted site acted as defect and crystallinity of the HDPE‐g‐GMA decreased with the increase of grafting reaction. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of isotactic polypropylene/high‐density polyethylene/carbon black conductive films with strain‐sensing behavior

Novel conductive films with a unique strain (ε)‐sensing behavior and based on a blend of isotactic polypropylene (iPP), high‐density polyethylene (HDPE), and carbon black (CB) were fabricated by an extrusion casting method. The morphology and ε‐sensing behavior of the films were investigated. Scanning electron microscope images showed that the oriented lamellae with a growing direction perpendicular to the extrusion direction were obtained in the HDPE phase and were accompanied by a cocontinuous structure of the iPP phase and HDPE/CB phase. The conductive percolation threshold (m_c) and resistivity–ε behavior of the thin films are affected by the drawing ratio during the process of film preparation. The m_c and electrical resistance of the iPP/HDPE/CB composite films increased with the drawing ratio. The gauge factor of the films within the elastic region decreased with increasing drawing ratio. Furthermore, the result of iPP/(HDPE/CB) 40/60 with a high drawing ratio shows that a reversible conductivity was obtained during the cyclic tensile testing (ε = 10%), but an irreversible conductivity makes the film fail during use at the applied ε values of up to 15%. This makes them good piezoresistive candidates for ε‐sensing materials. Moreover, a simple structural model was proposed to describe the reversible and irreversible phenomena in the electrical resistance behavior of the iPP/HDPE/CB films under tensile loading. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40686.     

Preparation and application of sulfonated poly(1‐octene‐co‐styrene)

In this article, 1‐octene and styrene was copolymerized by the supported catalyst (TiCl₄/ID/MgCl₂). Subsequently, by sulfonation reaction, sulfonated poly(1‐octene‐co‐styrene)s which were amphiphilic copolymers were prepared. The copolymerization behavior between 1‐octene and styrene is moderate ideal behavior. Copolymers prepared by this catalyst contain appreciable amounts of both 1‐octene and styrene. Increase in the feed ratio of styrene/1‐octene leads to increase in styrene content in copolymer and decrease in molecular weight. As the polymerization temperature increases, the styrene content in the copolymers increases, however, the molecular weight decreases. Hydrogen is an efficient regulator to lower the molecular weights of poly(1‐octene‐co‐styrene)s. The sulfonation degree of the sulfonated poly(1‐octene‐co‐styrene)s increased as the styrene content in copolymer increased or the molecular weight decreased. Thirty‐six hour is long enough for sulfonation reaction. The sulfonated poly(1‐octene‐co‐styrene)s can be used as effective and durable modifying agent to improve the wettability of polyethylene film and have potential application in emulsified fuels and for the stabilization of dispersions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of nonleaching antimicrobial polypropylene wax and its application in polypropylene

Antimicrobial polypropylene (PP) has been widely used. Its highly effective antimicrobial activities and nonleaching characteristics remain concerns. In this study, polypropylene wax (PPW) grafted with maleic anhydride was first prepared; this was followed by a melting reaction with polyhexamethylene guanidine hydrochloride (PHMG) to obtain antimicrobial PPW [polypropylene wax grafted with polyhexamethylene guanidine hydrochloride (PPW‐g‐PHMG)]. PPW‐g‐PHMG was then melt‐blended with PP to prepare antimicrobial PP. Fourier transform infrared spectra confirmed that PHMG was covalently bonded on the PPW chains, and transmission electron microscopy images showed a uniform distribution of PHMG in the PPW matrix. The resulting antimicrobial PP exhibited excellent antimicrobial activity against Escherichia coli. The ring‐diffusion test further disclosed its nonleaching characteristics. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44190.     

High‐performance antistatic ethylene–vinyl acetate copolymer/high‐density polyethylene composites with graphene nanoplatelets coated by polyaniline

Graphene nanoplatelets coated by polyaniline (GNP@PANI) and ethylene–vinyl acetate (EVA) copolymer–high‐density polyethylene (HDPE) were used for the first time to prepare high‐performance antistatic composites through an effective method that combined solution mixing and melt blending. GNP@PANI nanocomposites were fabricated by in situ polymerization to improve the dispersion of graphene nanoplatelets (GNPs) in the EVA–HDPE matrix and the compatibility between the GNPs and the EVA–HDPE matrix. The GNP@PANI nanocomposites and EVA were first prepared as a premix through solution mixing, and then, the premix and HDPE were prepared as highly antistatic composites through melt blending. The dispersion of the GNPs in the EVA–HDPE matrix and the compatibility between the GNPs and the EVA–HDPE matrix were confirmed by field emission scanning electron microscopy and transmission electron microscopy observations. The GNP@PANI–EVA–HDPE composites met the requirements for antistatic materials when the content of the GNP@PANI nanocomposites was 5 wt % with only about 1 wt % GNPs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45303.     

Radical grafting of polar monomers onto polypropylene by reactive extrusion

Polypropylene (PP) was functionalized in the melt by grafting polar monomers using an internal mixer and a corotating twin‐screw extruder. 2,5‐Bis(tertbutylperoxy)‐2,5‐dimethylhexane (Luperox 101) and dicumyl peroxide (DP) were the used radical initiators. The polar monomers were itaconic acid (IAc), 2‐octen‐1‐ylsuccinic anhydride (OY), 2‐hydroxyethyl methacrylate (HEMA), and 3‐allyloxy‐1,2‐propanediol (AP). Grafting was quantified by FTIR combined to Elemental Analysis. Grafting degree depends mainly on monomer and initiator natures and concentrations. Grafting degree maxima were 3.9, 2, 9.5, and 3.9 wt %, respectively, for IAc, OY, HEMA, and AP. Some properties of the modified PP were evaluated. Thermal analysis indicated that the polarity of PP increased by grafting reaction and size‐exclusion chromatography showed that the grafting was not accompanied by a significant M_w and viscosity decrease. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystallization and fracture behaviors of high‐density polyethylene/linear low‐density polyethylene blends: The influence of short‐chain branching

Two commercial polyethylene samples, linear high‐density polyethylene (HDPE) and branched linear low‐density polyethylene with almost the same molecular weight distribution but different contents of short‐chain branching (SCB) were melt blended based on the consideration of practical application. Dynamic rheology analysis indicated good compatibility of all the blends with different compositions. Common differential scanning calorimeter (DSC) tests and successive self‐nucleation and annealing (SSA) treatment showed several interesting phenomena. First, without consideration of the effect of molecular weight and molecular weight distribution impact, co‐crystallization occurred at all ratios even the two components had a considerable difference in SCB distribution. Second, in SSA curves the area of the first two melting peaks, i.e., the amount of the thick lamellas of the two components showed an obvious positive deviation with the increase of HDPE content owing to the crystal perfection improved by the co‐crystallization. Essential Work of Fracture tests proved the co‐crystallization effects had a positive effect on the improvement of the resistance to crack propagation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Impact of the starch source on the physicochemical properties and biodegradability of different starch‐based films

Concern about environmental issues has motivated research into the development of biodegradable packaging from renewable sources. Natural polymers such as starch constitute a good alternative for diminishing the use of nonbiodegradable and nonrenewable components in the packaging industry. However, depending on the botanical source, films with different properties are formed. The aim of this study was to evaluate the film‐forming capacity of different starch sources (cassava, corn, potato, and wheat) by casting with starch contents from 2 to 6%. Principal component analysis methodology was used to evaluate the correlation between the formulations and their physicochemical and mechanical properties. It was not possible to produce continuous films based on potato starch, probably because of its very low amylose content (10%). The corn‐, cassava‐, and wheat‐starch‐based films were characterized by their thicknesses (0.06–0.22 mm), moisture contents (19–26%), water solubilities (13.7–26.5%), water‐vapor permeabilities (WVPs; 0.19–0.48 g mm h^?1 m^?2 kPa^?1), wettabilities (35–106°), biodegradabilities in soil, and thermal and mechanical properties (tensile strength = 1.9–6.7 MPa, elongation = 41–166%, and Young's modulus = 8–127 MPa). The wheat starch films presented higher WVPs and lower mechanical properties. The cassava starch films presented lower wettabilities and good mechanical properties; this suggested that their use in packaging for products, such as fruits and vegetables, with higher water activities could be feasible. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46564.